KR20190090875A - Aqueous polymer composition - Google Patents

Abstract

The present invention relates to a storage stable crosslinkable aqueous polymer composition comprising:
(a) an aqueous liquid; (b) a copolymer dissolved in an aqueous liquid by a volatizable non-gas acid, comprising: (i) an ethylenically unsaturated monomer comprising a basic functional group protonated by a volatility non-gas acid, wherein the monomer is polymerized. Monomers in which the moiety is present in an amount of less than 25 mole percent relative to the total moles of polymerized monomer moieties of the copolymer; (ii) ethylenically unsaturated monomers comprising functional groups for promoting crosslinking of the copolymer; And (iii) a polymerized moiety of a hydrophobic ethylenically unsaturated monomer; (c) a reversibly blocked crosslinker to promote crosslinking of (i) the copolymer, and (ii) a volatilizable crosslinking inhibitor to inhibit crosslinking of the copolymer by a reversibly blocked crosslinker.

Description

Aqueous polymer composition

The present invention generally relates to aqueous polymer compositions. In particular, the present invention relates to storage stable crosslinkable aqueous polymer compositions, methods for their preparation, polymer compositions derived therefrom and substrates coated therewith.

Polymer compositions such as adhesives, varnishes and paints have long been used to bond and / or undercoat and / or protect and / or decorate substrate surfaces.

Such polymer compositions typically contain so-called solvents, binders and optionally pigments.

The solvent functions to provide fluidity to the composition and promotes application of the composition on the substrate.

The binder is typically a polymer capable of coating the substrate surface and promoting adhesion of the composition to that surface. In the case of an adhesive, the polymer typically also promotes adhesion to the second substrate material. In the case of paints, the polymer may adhere to the substrate surface, decorate the substrate and / or protect it from abrasion or elements.

Pigments may be inorganic or organic and may provide color and / or opacity to the composition, and additionally serve to thicken the composition or protect the surface of the substrate.

Such polymer compositions typically fall into two broad categories, namely oily compositions and emulsion compositions.

Oily compositions typically contain a polymeric binder, such as an alkyd resin, dissolved in an organic solvent. Pigments may also be mixed in the composition. Polymeric binders used are generally of a type that can undergo crosslinking after application to a substrate to impart excellent durability to the cured polymer film. In the context of paint technology, such compositions are often referred to in the art as enamel paints, and they are famous for forming hard, water resistant and glossy polymer films.

The use of organic solvents in oily polymer compositions supports the beneficial properties derived from this class of compositions.

However, despite providing advantageous properties, the use of oily polymer compositions in modern society is decreasing because organic solvents present significant environmental and occupational, health and safety concerns.

In contrast, emulsion polymer compositions contain relatively low levels with little or no organic solvent, and as a result their use has increased significantly. The so-called "solvent" in the emulsion composition is mostly water. Technically, water does not function as a true solvent for the polymeric binder but as a liquid carrier. The water "solvent" in such compositions typically appears as a dispersed small droplet continuous liquid phase of vinyl and / or acrylic polymer particles (ie, polymer binder). The dispersed polymer particles are essentially insoluble in the aqueous liquid carrier. Pigments may also be mixed in the emulsion.

Emulsion polymer compositions are often referred to in the art as water-borne or latex polymer compositions.

When the emulsion polymer composition is applied to the substrate surface, water in the applied composition evaporates or is absorbed by the substrate, causing dispersed polymer droplets to agglomerate and form a continuous polymer mass or film.

While emulsion-based polymer compositions do not produce the same organic solvent content concerns as their oily counterparts (advantages), properties such as gloss, flow, applicability and water resistance of continuous polymer masses or films derived from such emulsion compositions are often It is considered inferior to those that can be derived from their meteor counterparts.

With this in mind, there has been considerable research and ongoing development of aqueous polymer compositions that provide continuous polymer masses or films exhibiting properties close to or exceeding those of polymers derived from oily polymer compositions.

In that context, the basic principle for emulsion-based techniques is the need for dispersed polymeric binder particles that aggregate and form a continuous polymer mass or film as water is removed (evaporated / absorbed) from the applied polymer composition. The type of polymer binder used in conventional emulsion polymer compositions may be replaced by polymer binders that produce improved properties of the resulting continuous polymer mass or film, which typically is a sufficient agglomeration and continuous polymer of dispersed polymer binder particles. There is a need for an organic solvent in combination with the polymer to facilitate subsequent formation of agglomerates or films. This approach thus requires the use of undesirable organic solvents and thus presents similar concerns as those of oily compositions.

At the liquid level, simply using a polymer binder soluble in water seems to be a viable alternative approach, as the oily polymer composition uses a polymer binder soluble in organic solvents. Borrowing this approach advantageously avoids the presence of dispersed polymer binder particles that need to aggregate and form a continuous polymer mass or film and, of course, also the need for organic solvents.

However, while this approach may possibly provide a continuous polymer mass or film that exhibits at least some of the advantageous properties (eg, high gloss) of the continuous polymer mass or film derived from the oily polymer composition, they generally have poor water resistance. It will be easy to have a temper.

In particular, selecting a polymeric binder that is soluble in water solves the problems associated with the need to use an organic solvent and the agglomeration of dispersed polymeric binder particles, but the inherent water solubility of the polymeric binder is generally incorporated into the obtained continuous polymer mass or film. It will be moved across, thus imparting poor water resistance properties to the continuous polymer mass or film.

Thus, there remains an opportunity to develop aqueous polymer compositions that address one or more problems associated with conventional polymer compositions.

The present invention provides a storage stable crosslinkable aqueous polymer composition comprising:

(a) an aqueous liquid;

(b) a copolymer dissolved in an aqueous liquid by a fugitive non-gas acid,

(i) an ethylenically unsaturated monomer comprising a basic functional group protonated by a volatilizable non-gas acid, wherein the polymerized moiety of the monomer is less than 25 mol% relative to the total moles of polymerized monomer moiety of the copolymer. Monomer present;

(ii) ethylenically unsaturated monomers comprising functional groups for promoting crosslinking of the copolymer; And

(iii) hydrophobic ethylenically unsaturated monomers

Copolymers comprising polymerized residues of; And

(c) a reversibly blocked crosslinker to promote crosslinking of (i) the copolymer, and (ii) a volatilizable crosslinking inhibitor to inhibit crosslinking of the copolymer by a reversibly blocked crosslinker.

The present invention further provides a process for preparing a storage stable crosslinkable aqueous polymer composition, the method comprising combining or forming the following in an aqueous liquid:

(a) a copolymer made soluble in an aqueous liquid by volatilizable non-gas acid,

(i) an ethylenically unsaturated monomer comprising a basic functional group protonated by a volatilizable non-gas acid, wherein the polymerized moiety of the monomer is less than 25 mol% relative to the total moles of polymerized monomer moiety of the copolymer. Monomer present;

(ii) ethylenically unsaturated monomers comprising functional groups for promoting crosslinking of the copolymer; And

(iii) hydrophobic ethylenically unsaturated monomers

Copolymers comprising polymerized residues of; And

(b) a reversible blocked crosslinker to promote crosslinking of (i) the copolymer, and (ii) a volatilizable crosslinking inhibitor to inhibit crosslinking of the copolymer by a reversibly blocked crosslinker.

Described herein are storage stable crosslinkable aqueous polymer compositions comprising:

(a) an aqueous liquid; And

(b) a copolymer dissolved in an aqueous liquid by volatilizable non-gas acid,

(i) an ethylenically unsaturated monomer comprising a basic functional group protonated by a volatilizable non-gas acid, wherein the polymerized moiety of the monomer is less than 25 mol% relative to the total moles of polymerized monomer moiety of the copolymer. Monomer present;

(ii) ethylenically unsaturated monomers comprising functional groups for promoting crosslinking of the copolymer; And

(iii) hydrophobic ethylenically unsaturated monomers

Copolymers comprising polymerized residues of;

Wherein the composition also comprises one or both of the following:

(c) a reversible blocked crosslinker to promote crosslinking of the copolymer, and (ii) a volatilizable crosslinking inhibitor to inhibit crosslinking of the copolymer by a reversibly blocked crosslinker; And

(d) dispersed particulate matter having a reversibly blocked crosslinker to promote crosslinking of the copolymer adsorbed thereon.

Also described herein are methods of preparing a storage stable crosslinkable aqueous polymer composition, comprising combining or forming the following in an aqueous liquid:

(a) a copolymer made soluble in an aqueous liquid by volatilizable non-gas acid,

(i) an ethylenically unsaturated monomer comprising a basic functional group protonated by a volatilizable non-gas acid, wherein the polymerized moiety of the monomer is less than 25 mol% relative to the total moles of polymerized monomer moiety of the copolymer. Monomer present;

(ii) ethylenically unsaturated monomers comprising functional groups for promoting crosslinking of the copolymer; And

(iii) hydrophobic ethylenically unsaturated monomers

Copolymers containing polymerized organs of

Wherein one or two of the following is combined or formed in the aqueous liquid:

(b) a reversible blocked crosslinker to promote crosslinking of the copolymer and (ii) a volatilizable crosslinking inhibitor to inhibit crosslinking of the copolymer by a reversibly blocked crosslinker; And

(c) dispersed particulate matter having a reversibly blocked crosslinker to promote crosslinking of the copolymer adsorbed thereon.

The dispersed particulate material having a reversibly blocked crosslinker to promote crosslinking of the copolymer adsorbed thereon may be combined or present in an aqueous liquid in combination with a volatilizing crosslinking inhibitor to inhibit crosslinking of the copolymer. have.

The present invention also provides a polymer composition derived through the loss of an aqueous liquid from the storage stable crosslinkable aqueous polymer composition according to the present invention.

The polymer composition derived through loss of aqueous liquid will typically be a solid polymer composition.

The invention further provides a substrate having a surface coated with a storage stable crosslinkable aqueous polymer composition according to the invention. In one embodiment, the substrate exhibits on its surface a polymer composition derived through the loss of an aqueous liquid from the storage stable crosslinkable aqueous polymer composition according to the invention.

It has now been found that it is possible to prepare aqueous polymer compositions using water soluble polymer binders that are surprisingly crosslinkable as well as storage stable in their crosslinkable form.

By means of a polymeric binder which can be dissolved in an aqueous liquid, the composition according to the invention can advantageously be produced with little or no organic solvent. The solubility of the polymer binder in the aqueous liquid also advantageously avoids the problems associated with dispersed polymer particles that form agglomerated, continuous polymer masses or films that are agglomerated and form a continuous polymer mass or film.

Compositions that are crosslinkable may form crosslinked continuous polymer masses or films having improved properties such as improved adhesion, hardness, or water resistance through loss of the aqueous liquid therein.

Aqueous polymer compositions are known in which (a) the polymer binder is soluble in an aqueous liquid and (b) provides a crosslinked polymer film, and such compositions are typically provided in two pack form. As a two pack composition, the water soluble polymer binder is provided in one pack and a suitable crosslinker is provided in another pack. To use such compositions, the contents of each pack are mixed together, the crosslinking reaction (initiated by mixing the two packs) produces a gel and / or increases beyond the point at which the viscosity of the composition can actually be applied to the substrate. The composition obtained must be applied to the substrate before the process. In the crosslinkable form, ready for use, such compositions thus exhibit a limited pot life and do not actually exhibit storage stability.

In contrast, the aqueous polymer compositions according to the invention are not only crosslinkable but they also provide the property of a "ready to use" storage stable state (ie no need to introduce additional formulation components to promote crosslinking). . In other words, although the aqueous polymer compositions according to the invention are in a crosslinkable ready state, they can advantageously remain in a storage stable state when not in use.

Crosslinking of the aqueous polymer composition according to the invention can be facilitated by simply applying it onto the surface of the substrate. The aqueous liquid (eg, water) and other volatilizing components present in the composition can then be absorbed and escape from the composition, for example via evaporation and / or onto the substrate, which in turn leads to a crosslinking process. It starts.

Accordingly, the present invention may also be described as providing or preparing a self-supporting or ready-to-use storage stable crosslinkable aqueous polymer composition. In the art, such "independent" or "ready to use" compositions are often referred to as "one pack" compositions.

Thus, the present invention may also be described as providing or preparing a one pack storage stable crosslinkable aqueous polymer composition.

As will be known to those skilled in the art, expressions such as "storage stability", "independent", "ready to use" and "one pack" are mixed together and stored in the same container but substantially during storage. It is used when describing compositions containing reactive components that remain unreacted.

Certain one pack storage stable crosslinkable polymer compositions are known. However, such compositions are typically formulated such that high temperatures are required to promote crosslinking upon application of the composition to a substrate. The storage stability of such compositions is feasible because the crosslinking process is not activated unless the composition is subjected to high temperatures (ie, temperatures much higher than typical ambient storage temperatures).

The storage stable crosslinkable aqueous polymer compositions according to the invention advantageously do not require the application of high temperatures to promote crosslinking. Thus, the compositions according to the invention may also be described as being storage stable ambient temperature crosslinkable aqueous polymer compositions, or alternatively storage stability one pack ambient temperature crosslinkable aqueous polymer compositions.

As used herein, the expression “ambient temperature” is intended to mean a temperature within the typical storage and application range of an aqueous polymer composition. Such temperatures will generally range from about 1 ° C to about 40 ° C.

In one embodiment, the composition according to the invention may be described as being a storage stable crosslinkable aqueous polymer composition capable of undergoing crosslinking within a temperature range of about 1 ° C to about 40 ° C.

Nevertheless, since the crosslinking of the aqueous polymer composition according to the invention is promoted through the loss of an aqueous liquid (eg water) and other volatilizable components, if such volatilized components remain in the composition (eg, It will be appreciated that when stored in a sealed container, it can withstand temperatures above 40 ° C. without undergoing premature crosslinking.

A one-pack aqueous polymer composition has also been recently disclosed in which (a) the polymer binder can be dissolved in an aqueous liquid and (b) provides a crosslinked polymer film. For example, WO 2016/191890 discloses a so-called "switchable" aqueous paint or coating composition. Such compositions are expected to promote aqueous solvation of protonable polymers when using acid gas. Upon application of the composition to the substrate, the dissolved acid gas is released into the atmosphere, which causes the conversion of the protonated polymer to its unprotonated form and reduces the solubility of the polymer in the aqueous liquid. The unprotonated form of the polymer then forms a film called substantially water insoluble. The composition may comprise a crosslinking agent to promote crosslinking of the obtained polymer film.

However, the compositions disclosed in WO 2016/191890 require the use of polymers having a high mole percent of polymerized monomer residues that protonate to cause the polymer to be solvated in an aqueous liquid. As described in WO 2016/191890, polymer films derived from the compositions according to the invention are characterized by common aqueous acidic components (e.g. juice, acid rain) through reprotonation of protonable polymers and solvation of polymer films. Susceptible to damage from exposure to water, sweat and cleaning fluids).

Crosslinking of the polymer film is said to reduce the reverse solvation effect of the polymer film in contact with common aqueous acidic components, and high mole percentages of protonable polymerized monomer residues in the polymer inherently make the reverse solvation effect more problematic. Make. In addition, high mole percent of protonable polymerized monomer residues in the polymer are expected to adversely affect other properties of the polymer film formed therefrom, such as stain resistance.

The storage stable crosslinkable aqueous polymer composition according to the invention is a copolymer comprising polymerized moieties of ethylenically unsaturated monomers containing basic functional groups in an amount of less than 25 mole% relative to the total moles of polymerized monomer moieties of the copolymer. Use Surprisingly, it has been found that the copolymer can still be sufficiently dissolved in the aqueous liquid if it contains a relatively low mole percent of protonable polymerized monomer residues. This was eventually found to impart improved properties such as water (including acidic water) resistance to polymer films derived from storage stable crosslinkable aqueous polymer compositions. Without wishing to be bound by theory, the ability to use copolymers containing relatively low mole percent of protonable polymerized monomer residues is believed to result at least in part from the use of volatilizable non-gas acids in the composition. do.

Polymer films derived from the storage stable crosslinkable aqueous polymer compositions according to the invention advantageously exhibit improved stain resistance properties, for example, compared to polymers derived from the compositions disclosed in WO 2016/191890.

"Switchable" aqueous paint or coating compositions according to WO 2016/191890 are envisaged when using acid gases. The use of acid gases in these compositions has also been found to be problematic. For example, acid gases can promote the formation of foam defects in polymer films formed using WO 2016/191890 compositions. Certain acid gases can also promote degradation of protonable polymers and can also be very toxic. Due to its gaseous nature, the presence of acid gases can also cause undesirable pressures that are created in closed containers in which the WO 2016/191890 composition is stored.

The storage stable crosslinkable aqueous polymer composition according to the present invention does not use or contain acid gases. Thus, the problems associated with the use of acid gases are advantageously avoided.

Unlike most conventional aqueous polymer compositions, those according to the present invention are capable of forming crosslinked polymers having multiple properties in close proximity when applied to a substrate, when not exceeding the polymer derived from the oily composition. Provide a stable crosslinkable composition.

Without wishing to be bound by theory, the ability of the aqueous polymer composition according to the invention to not suffer from an undesired degree of crosslinking during storage can be applied to aqueous liquids, polymeric binders (ie copolymers), volatilizable non-acid gases, And a unique combination of composition components, including combinations of reversibly blocked crosslinkers and volatilizable crosslinking inhibitors. This unique combination of composition components not only provides storage stability to the composition, but also allows crosslinking to be initiated when the composition is actually used, for example when applied to a substrate.

Without wishing to be bound by theory, the ability of the aqueous polymer composition according to the invention to not suffer from an undesirable degree of crosslinking during storage is also reversibly blocked crosslinking to promote crosslinking of the copolymer adsorbed thereon. It can result from the use of dispersed particulate matter with a binder.

The copolymer comprises polymerized moieties of ethylenically unsaturated monomers containing basic functional groups that are protonated by volatilizable non-gas acids. Suitable basic functional groups include those selected from amines, amidines, N-heterocycles and combinations thereof.

In one embodiment, the basic functional group comprises a tertiary amine basic functional group.

In another embodiment, the basic functional group consists essentially of tertiary amine functional groups.

Examples of ethylenically unsaturated monomers containing such basic functional groups include amino acrylate, amino methacrylate, acrylamide, methacrylamide, vinyl pyridine, vinyl imidazole, 1- (4-vinylphenyl) methanamine, amino maleimide And combinations thereof.

The copolymer comprises polymerized moieties of ethylenically unsaturated monomers containing functional groups to promote crosslinking of the copolymer. Suitable crosslinking functional groups include those selected from hydroxy, carboxylic acids, epoxy, ketones, aldehydes, alkenes, alkynes, amines, azides, halides (e.g., alkyl halides, benzyl halides), hydrazides and combinations thereof.

The copolymers used according to the invention comprise polymerized moieties of hydrophobic ethylenically unsaturated monomers.

Examples of hydrophobic ethylenically unsaturated monomers include styrene, alpha-methyl styrene, butyl (meth) acrylate, iso-butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, lauryl (meth) Acrylate, stearyl (meth) acrylate, ethyl hexyl (meth) acrylate, crotyl (meth) acrylate, cinnamil (meth) acrylate, oleyl (meth) acrylate, lysine oleyl (meth) acrylic Latex, cholesteryl (meth) acrylate, cholesteryl (meth) acrylate, vinyl butyrate, vinyl tert-butyrate, vinyl stearate, vinyl laurate, 2- (2-oxo-1-imidazolidinyl) Ethyl methacrylate (ethoxy ethyleneurea methacrylate) and combinations thereof.

In one embodiment, the copolymer may also include polymerized moieties of hydrophilic ethylenically unsaturated monomers.

Examples of hydrophilic ethylenically unsaturated monomers include (meth) acrylic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, oligo (alkylene glycol) methyl ether (meth) acrylate (OAG (M) A ), Itaconic acid, p-styrene carboxylic acid (s), p-styrene sulfonic acid (s), vinyl sulfonic acid, vinyl phosphonic acid, ethacrylic acid, alpha-chloroacrylic acid, crotonic acid, fumaric acid, citraconic acid, mesaconic acid , Maleic acid, sulfoethyl (meth) acrylate, phosphoethyl (meth) acrylate, phosphorylcholine (meth) acrylate and combinations thereof.

In one embodiment, the copolymer does not include polymerized moieties of hydrophilic ethylenically unsaturated monomers in an amount greater than 10 mole% relative to the total moles of polymerized monomer moieties of the copolymer.

In another embodiment, the copolymer does not include polymerized moieties of acid functionalized ethylenically unsaturated monomers in an amount greater than 10 mole% relative to the total moles of polymerized monomer moieties of the copolymer.

The copolymers used according to the invention are dissolved in aqueous liquids by volatilizable non-gas acids. Suitable volatizable non-gas acids include those selected from acetic acid, glycolic acid, lactic acid and combinations thereof.

In one embodiment, the volatilizable non-gas acid comprises acetic acid.

The aqueous polymer composition according to the invention comprises a reversibly blocked crosslinker. Examples of reversibly blocked crosslinkers include, but are not limited to, reversibly blocked multifunctional hydrazide compounds.

If the crosslinker is a multifunctional hydrazide that is reversibly blocked, it may be reversibly blocked, for example as it is converted to a hydrazone compound.

The aqueous polymer compositions described herein also contain (I) a reversibly blocked crosslinker to promote crosslinking of (i) the copolymer, and (ii) inhibiting crosslinking of the copolymer by a reversibly blocked crosslinker. One or two of a dispersed particulate material having a volatilizing crosslinking inhibitor, and (II) a reversibly blocked crosslinking agent to promote crosslinking of the copolymer adsorbed thereon.

Examples of volatilizable crosslinking inhibitors include ketones such as acetone, methyl ethyl ketone, diethyl ketone and combinations thereof.

If used, the particulate material must be dispersed or dispersible in the aqueous polymer composition. Thus, the particulate material will be of the type that can be dispersed or dispersible in an aqueous liquid comprising a copolymer dissolved therein. The dispersed or dispersible particulate material will typically be a solid particulate material.

Dispersible or dispersible particulate matter may be non-polymeric.

Examples of dispersed or dispersible particulate materials include, but are not limited to, inorganic pigments, organic pigments, extenders, solid fillers, and combinations thereof.

Further aspects and embodiments of the invention are set forth in the detailed description below.

The present invention provides a storage stable crosslinkable aqueous polymer composition. The composition according to the invention contains reactive components which are intimately mixed together. In particular, the composition comprises a copolymer exhibiting a functional group for promoting crosslinking of the copolymer and a reversibly blocked crosslinker for promoting crosslinking of the copolymer. Although such reactive components are present and mixed together, the compositions according to the invention are advantageously storage stable.

A composition that is "storage stable" is intended to mean that the composition will remain in practically usable form for a commercially acceptable period of time when properly stored (eg, in a closed container at ambient temperature).

Compositions according to the invention which remain in "actually usable form" during storage mean that the composition can be applied and function as originally intended upon use after storage. In practice, this would mean at least that the composition would experience little cross-linking during storage and consequently little increase in viscosity.

Other compositions in the present invention that are storage stable for a “commercially acceptable period” are intended to mean the period during which the composition is manufactured and sold to the consumer, including the period for which the consumer is expected to use the product. This, of course, assumes that the composition is properly stored during that time period. By "suitably stored" it is meant that the composition is stored in a sealed container containing a volume similar to the volume of the composition stored at ambient temperature.

The composition according to the invention will generally be storage stable for at least 1 month, or 2 months, or 4 months, or 6 months, or 8 months, or 10 months, or 12 months, or 14 months or more.

With respect to the components contained in the compositions of the present invention, those skilled in the art need to add additional formulation components to the composition in order for the reference to the composition to be storage stable and crosslinkable to allow the composition to form a crosslinked polymer. It will be appreciated that it is intended to mean that it is independent or ready for use in that it is not. Thus the composition may also be described as a one pack storage stable crosslinkable aqueous polymer composition.

The storage stable crosslinkable aqueous polymer composition according to the invention advantageously does not require the application of high temperatures to promote crosslinking. Thus, the compositions according to the invention may also be described as being storage stable ambient temperature crosslinkable aqueous polymer compositions, or alternatively storage stability one pack ambient temperature crosslinkable aqueous polymer compositions.

The nature of the formulation components present in the compositions according to the invention is explained in more detail below.

Aqueous liquid

The aqueous liquid used according to the invention is a solvent for the polymer binder (ie copolymer). Unlike emulsion or water based polymer compositions, the aqueous liquid component of the composition according to the invention functions as a true solvent for the polymer binder in that the polymer binder is soluble in the aqueous liquid.

The aqueous liquid will contain mostly (ie greater than 50% by weight) water. Generally, it will comprise more than 60%, or 70%, or 80%, or 90%, or more than 95% by weight water relative to the total amount of water / aqueous liquid present in the composition.

The aqueous liquid may comprise a water soluble organic solvent.

Examples of suitable water soluble organic solvents are monohydric alcohols (eg methanol and ethanol), polyhydric alcohols (eg ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, hexanediol , Pentanediol, glycerin, hexanetriol and thiodiglycol), acetonitrile, ketones (eg acetone and methyl ethyl ketone) and combinations thereof.

When used, water soluble organic solvents are generally less than 50%, or less than 40%, or less than 30%, or less than 20%, or less than 15% by weight relative to the total amount of water / aqueous liquid present in the composition. , Or less than 10 weight percent, or less than 8 weight percent, or less than 5 weight percent, or less than 3 weight percent.

In one embodiment, the aqueous liquid consists essentially of water.

Copolymers and Volatilizable Non-Gasic Acids

The copolymers used according to the invention are dissolved in aqueous liquids by volatilizable non-gas acids. The fact that the copolymer is "dissolved" in the aqueous liquid "by volatilizing non-gas acid" means that the presence of the volatility non-gas acid (as will be discussed in more detail below) associated with the copolymer is reduced to the copolymer in the aqueous liquid. Means to promote solubility. In other words, in the absence of volatilizable non-gas acids associated with the copolymer, the copolymer itself is substantially insoluble in the aqueous liquid.

The fact that the copolymer is “soluble” in an aqueous liquid, or that the copolymer “dissolves” in an aqueous liquid by volatilizing non-gaseous acid, means that the copolymer is aqueous in that it is not present as an organic phase dispersed in the aqueous liquid. It is dissolved in the liquid (via interaction with volatilizable non-gas acids).

The copolymers used are soluble or soluble in aqueous liquids, but there may be some copolymers that are not completely soluble in aqueous liquids, depending on their concentration in the aqueous liquid. In that case, some copolymers used may be present as organic phase dispersed in the aqueous liquid. Generally, more than 50%, or 60%, or 70%, or 80%, or 90%, or 95% by weight of the copolymer is soluble in the aqueous liquid relative to the total amount of copolymer used in the composition. Or dissolve.

If some of the copolymers used are not completely soluble or insoluble in the aqueous liquid, the copolymer may be described as being substantially soluble or soluble in the aqueous liquid. In any case, it is recognized that most of the copolymers used are soluble or will be soluble in aqueous liquids.

The copolymers used according to the invention comprise polymerized moieties of certain ethylenically unsaturated monomers which impart specific functions. The common function of certain polymerized residues of ethylenically unsaturated monomers in copolymers provides copolymers having a unique set of properties for use according to the present invention.

Copolymer comprising "polymerized moieties" of ethylenically unsaturated monomers is intended to mean "mer" units in the copolymer chain formed as a result of the polymerization of the monomers. The polymerized monomer residues thus collectively form at least the molecular backbone structure of the polymer chain.

The polymerized moiety is formed by polymerizing ethylenically unsaturated monomers. This polymerization is facilitated through the reaction of ethylenically unsaturated functional groups of the monomers. Those skilled in the art will recognize that the polymerization of ethylenically unsaturated monomers in this manner results in polymer chains having a skeleton based carbon atom (-C-C-) molecular structure.

According to the invention, the copolymer comprises polymerized moieties of ethylenically unsaturated monomers comprising basic functional groups. As used herein, the expression “basic functional group” is intended to mean a Bronsted Lowry base functional group in that it can accept protons.

Examples of suitable basic functional groups include those selected from amines, amidines, N-heterocycles and combinations thereof. The base functional group can be a primary, secondary or tertiary base functional group.

In one embodiment, suitable basic functional groups are selected from tertiary base functional groups.

In another embodiment, suitable basic functional groups are selected from tertiary amine functional groups.

A given polymerized ethylenically unsaturated monomer moiety will generally comprise one basic functional group, which may contain two or more basic functional groups depending on the particular ethylenically unsaturated monomer derived therefrom.

Examples of ethylenically unsaturated monomers that can provide polymerized monomer residues comprising basic functional groups include amino acrylate, amino methacrylate, acrylamide, methacrylamide, vinyl pyridine, vinyl imidazole, 1- (4-vinyl Phenyl) methanamine, amino maleimide and combinations thereof.

Examples of specific ethylenically unsaturated monomers that may be used to provide polymerized monomer moieties comprising basic functional groups are 2-aminoethyl (meth) acrylate, N- [3- (N, N-dimethylamino) propyl] (meth ) Acrylamide, N- (3-aminopropyl) (meth) acrylamide, N- [2- (N, N-dimethylamino) ethyl] (meth) acrylamide, 2-N-morpholinoethyl (meth) Acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate, 2- (N, N-diethylamino) ethyl (meth) acrylate, 2- (tert-butylamino) ethyl (meth) Acrylate, 2- (diethylamino) ethylstyrene, N, N-dimethyl-1- (4-vinylphenyl) methanamine, 2-vinylpyridine, 4-vinylpyridine, 1- (2- (dimethylamino) ethyl ) -1 H -pyrrole-2,5-dione and combinations thereof.

In one embodiment, the copolymers used according to the present invention comprise polymerized moieties of 2- (N, N-dimethylamino) ethyl (meth) acrylate.

For the avoidance of any doubt, references herein to "(meth) acrylate" type ethylenically unsaturated monomers are intended to include both methacrylate and acrylate ethylenically unsaturated monomers.

As mentioned, the copolymers used according to the invention are dissolved in aqueous liquids by volatilizable non-gas acids. In other words, the copolymer comprises polymerized moieties of ethylenically unsaturated monomers containing basic functional groups that are protonated by volatilizable non-gas acids.

As used herein, the expression “volatile non-gas acid” can be (i) dissolved and dissociated in an aqueous liquid to provide anionic species and protons, and (ii) the conditions under which the composition is commonly used. By means of compounds which are capable of leaving (eg, evaporating or being absorbed into the substrate to which the composition is applied) from the aqueous polymer composition according to (iii) and not being gas at standard temperature and pressure (STP).

Suitable volatilizable non-gas acids include those selected from acetic acid, glycolic acid, formic acid, lactic acid and combinations thereof.

In one embodiment, the volatilizable non-gas acid comprises or is acetic acid.

The expression “volatile non-gas acid” is intended to exclude gaseous acids such as CO ₂ , COS, CS ₂ and HCl.

Typical uses of the aqueous polymer composition typically occur at ambient temperatures and pressures, such as atmospheric pressure and temperatures in the range of about 1 ° C to about 40 ° C.

Those skilled in the art will recognize that protonation of basic functional groups provides salts that can promote water solubility.

The protonated form of the basic functional group of the polymerized monomer residue promotes the solubility of the copolymer in the aqueous liquid.

The copolymers used according to the invention, of course, once protonated by volatilizing non-gaseous acids, ensure that the obtained salt forms of the basic functional groups promote the required solubility of the copolymer in the aqueous liquid. Will have sufficient polymerized residue.

The copolymer may comprise about 1-25, or 1-20, of the polymerized moiety of the ethylenically unsaturated monomer comprising a basic functional group protonated by volatilizable non-gas acid, relative to the total moles of polymerized monomer moieties of the copolymer. Or 1-18, or 1-16 or 1-14, or 1-12, or 1-10 mol%.

In one embodiment, the copolymer used in accordance with the present invention comprises a polymerized moiety of an ethylenically unsaturated monomer comprising a basic functional group (protonated by a volatilizing non-gaseous acid) and a total of polymerized monomer moieties of the copolymer. In an amount of less than 25 mol%, or less than 20 mol%, or less than 15 mol%, or less than 10 mol% relative to the number of moles.

As used herein, reference to the mole percent of polymerized residues of the ethylenically unsaturated monomers of the copolymer refers to the polymerized residues of the ethylenically unsaturated monomers in the copolymer as determined by nuclear magnetic resonance (NMR) spectroscopy. It is intended to mean mole%.

Those skilled in the art will appreciate that the mole percent of the defined ethylenically unsaturated monomers (ie, introduced into the reaction medium) used to form the copolymer will not accurately reflect the mole percent of those monomers in the so formed copolymer as discussed below. You will recognize that you can. For example, an ethylenically unsaturated monomer that is hydrolytically sensitive during polymerization can be hydrolyzed and there can be no 100% conversion of that monomer to be polymerized because it is a hydrolyzed form of the monomer to be actually present in the copolymer so formed. have. Generally, copolymers will be prepared with monomer conversion close to 100% and minimal hydrolysis of hydrolytically sensitive ethylenically unsaturated monomers.

For example, when N- [2- (N, N-dimethylamino) ethyl] (meth) acrylamide (DMAEMA) is used to prepare the copolymer in an aqueous reaction medium, the amount of monomers used is partially during polymerization. Hydrolysis, eg, less than 5% or less than 3%. With this hydrolysis, the copolymer obtained may comprise a small portion of the polymerized moiety (derived from DMAEMA) of methacrylic acid. Thus, when 15 mole% of DMAEMA is used to prepare the copolymer, relative to the total mole% of the monomer used to prepare the copolymer, the copolymer obtained with 3% hydrolysis of that monomer during polymerization is obtained from DMAEMA. It may contain 0.45 mole percent of polymerized moieties of derived methacrylic acid. It was found that minor hydrolysis of the monomers during this polymerization did not adversely affect the performance of the copolymer obtained. Nevertheless, it is desirable to minimize any such hydrolysis of ethylenically unsaturated monomers that are hydrolytically sensitive during polymerization.

In the context of preparing the copolymers used according to the invention, reference to the mole% of ethylenically unsaturated monomers used in the polymerization process is directed to the total moles of ethylenically unsaturated monomers introduced during the polymerization to prepare the copolymers. It will be appreciated that it is intended to mean the mole percent of the defined ethylenically unsaturated monomer introduced during.

In order to avoid any doubt, the total mole% of polymerized residues of the ethylenically unsaturated monomers in the copolymers used according to the invention is 100 mole% in total. In addition, the total mole% of the ethylenically unsaturated monomer introduced during the polymerization to prepare the copolymer is 100 mole% in total.

To further illustrate the role and function of the polymerized moiety of an ethylenically unsaturated monomer comprising a basic functional group protonated by a volatizable non-gas acid and a volatilizable non-gas acid, the following schemes (i)-(iii ), The volatilized non-gas acid shown here is acetic acid, and the polymerized monomer residue in the copolymer comprising the basic functional group shown is derived from 2- (N, N-dimethylamino) ethyl methacrylate.

With respect to scheme (i), acetic acid is combined with water and dissociated to form acetate anions and H ⁺ . Copolymer (A) comprising a polymerized moiety of 2- (N, N-dimethylamino) ethyl methacrylate in Scheme (ii) interacts with a volatilized non-gaseous acid whose basic functional group is protonated. Form B). The protonated form (B) of the polymerized monomer moiety promotes the solubility of the copolymer in the aqueous liquid.

In Scheme (ii), the symbol * represents the remainder of the copolymer.

For convenience, according to the invention comprising a polymerized moiety of an ethylenically unsaturated monomer comprising a basic functional group protonated by a volatilizable non-gas acid (e.g., (B) in Scheme (ii) above) The copolymer used may be referred to herein as the protonated form of the copolymer.

According to the invention, the protonated form of the copolymer is soluble in an aqueous liquid. If an aqueous polymer composition is actually used, for example, when applied to the surface of a substrate, the water in the composition may evaporate or be absorbed by the substrate, which in turn results in the protonated form of the basic functional group of the copolymer in its free form. (For example, (A) in Scheme (ii)). Due to the volatility nature of the non-gaseous acids used, the loss of water from the composition also promotes the volatilization of the volatilizable non-gaseous acid from the composition. The loss of volatilizable non-gas acid from the composition leaves the copolymer in an unprotonated state and substantially water soluble. The substantially water soluble form of the copolymer advantageously promotes the water resistance of the polymer derived from the composition according to the invention.

The copolymers used according to the invention comprise polymerized moieties of ethylenically unsaturated monomers containing functional groups for promoting crosslinking of the copolymer.

References herein to "functional groups for promoting crosslinking of copolymers" will react with the unblocked forms of the reversible blocked crosslinkers used according to the present invention and the reversible blocked crosslinking used according to the present invention. It is intended to mean a functional group that does not react to any significant degree with the blocked form of the binder.

In one embodiment, the copolymer is selected from hydroxy, carboxylic acid, epoxy, ketone, aldehyde, alkene, alkyne, amine, azide, halides (e.g., alkyl halides, benzyl halides), hydrazides and combinations thereof And polymerized moieties of ethylenically unsaturated monomers containing functional groups to promote crosslinking of the copolymer.

Examples of ethylenically unsaturated monomers containing functional groups to promote crosslinking of the copolymer include glycidyl methacrylate, N -methylolacrylamide, (isobutoxymethyl) acrylamide, hydroxyethyl acrylate, t − Butyl-carbodiimidoethyl (meth) acrylate, (meth) acrylic acid, λ-methacryloxypropyl triisopropoxysilane, 2-isocyanoethyl (meth) acrylate, diacetone (meth) acrylamide, vinyl Methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, diacetone (meth) acrylate, maleic anhydride, (meth) acrolein, crotonaldehyde, aceto acetoxy ethyl methacrylate, vinyl aceto acetate and combinations thereof .

In one embodiment, the copolymer comprises polymerized moieties of crosslinked ethylenically unsaturated monomers (to facilitate crosslinking of the copolymer) selected from diacetone acrylamide.

One skilled in the art will be able to select a suitable functional group to promote crosslinking of the copolymer with respect to the nature of the reversibly blocked crosslinker used according to the present invention.

The amount in the copolymer of the polymerized moiety of the ethylenically unsaturated monomer comprising functional groups to promote crosslinking of the copolymer will of course represent the crosslink density of the polymer derived from the aqueous composition according to the invention.

Generally, the polymerized moiety of an ethylenically unsaturated monomer comprising a functional group to promote crosslinking of the copolymer is about 0.5-20, 0.5-15, 0.5-10, relative to the total moles of polymerized monomer moieties of the copolymer. Or in the copolymer in an amount ranging from 0.5-8, or 1-5 mole%.

Unprotonated forms of the copolymers used in accordance with the present invention will promote the water resistance of polymer agglomerates or films derived from aqueous polymer compositions as described herein, and the unprotonated basic functional groups of the copolymer in the polymer so formed For example, the polymer may be reprotonated when exposed to an acidic aqueous composition. In that case, the water resistance of the polymer thus formed may be impaired. To promote excellent water resistance properties, the copolymers used in the composition undergo crosslinking as described herein.

Those skilled in the art will appreciate that crosslinking of copolymers imparts improved properties, such as improved water resistance to the obtained polymers, and in turn impairs the water resistant properties that may arise from the basic functional groups of the copolymer in the polymer being protonated. Will recognize that it will reduce. Crosslinking of the copolymers used according to the invention in polymers derived from aqueous polymer compositions can also impart other improved properties to the polymer, such as improved durability, hardness and chemical resistance.

However, as discussed above, it has been found that the benefits derived from the crosslinking of the copolymer can be offset by copolymers comprising a high mole percent of protonable polymerized monomer residues (WO 2016/191890). As in).

The storage stable crosslinkable aqueous polymer composition according to the present invention is a copolymer comprising a polymerized moiety of an ethylenically unsaturated monomer comprising a basic functional group in an amount of less than 25 mol% relative to the total moles of polymerized monomer moieties of the copolymer. Use Surprisingly, it was found that the copolymer could still be sufficiently dissolved in the aqueous liquid if it contained a relatively low mole percent of protonable polymerized monomer residues. The relatively low mole percent of protonable polymerized monomer residues in the copolymer will eventually lead to improved properties such as water (including acidic water) resistance and stain resistance properties derived from storage stable crosslinkable aqueous polymer compositions. It was confirmed to give to a film. Without wishing to be bound by theory, the ability to use copolymers containing relatively low mole percent of protonable polymerized monomer residues is believed to result at least in part from the use of volatilizable non-gas acids in the composition. do.

The improved properties of the polymers derived from the aqueous polymer compositions according to the invention thus advantageously have a relatively low mole percent of the protonable polymerized monomer residue of the copolymer, the crosslinked form of the copolymer and the volatilization ratio in the composition. Can be collectively derived from the use of gas acids.

The copolymers used according to the invention comprise polymerized moieties of hydrophobic ethylenically unsaturated monomers.

Those skilled in the art will appreciate that terms such as "hydrophobic" and "hydrophilic" are intended to refer to the desirable or undesirable interaction of one component with respect to other components (e.g., attractive or aversive interactions such as solubility and insolubility). It will be appreciated that it is used in the art as an indicator and is not intended to define the absolute quality of the components themselves.

According to the invention, the terms "hydrophobic" and "hydrophilic" are intended to be used as an indicator of the tendency of ethylenically unsaturated monomers to be soluble or insoluble in water.

One skilled in the art is familiar with classifying ethylenically unsaturated monomers as hydrophobic or hydrophilic.

As a convenient point of reference only, the person skilled in the art considers that hydrophobic ethylenically unsaturated monomers have a solubility in water of 20 g / L or less at 25 ° C., while hydrophilic ethylenically unsaturated monomers have more than 20 g / L water at 25 ° C. It can be considered to have solubility in water.

Examples of hydrophobic ethylenically unsaturated monomers include styrene, alpha-methyl styrene, methyl methacrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, hexyl ( Meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, ethyl hexyl (meth) acrylate, crotyl (meth) acrylate, cinnamil (meth) acrylate, oleyl (meth) Acrylate, lysine oleyl (meth) acrylate, cholesteryl (meth) acrylate, cholesteryl (meth) acrylate, vinyl butyrate, vinyl tert-butyrate, vinyl stearate, vinyl laurate, 2- (2 -Oxo-1-imidazolidinyl) ethyl methacrylate (ethoxy ethyleneurea methacrylate) and combinations thereof, including, but not limited to.

Reference to an alkyl group having three or more carbon atoms that may be present in a compound defined as structural isomers herein is intended to include all such isomers. For example, reference to butyl (meth) acrylate is intended to include n-butyl (meth) acrylate, i-butyl (meth) acrylate and s-butyl (meth) acrylate.

In one embodiment, the copolymer comprises polymerized moieties of hydrophobic ethylenically unsaturated monomers selected from methyl methacrylate, i-butyl (meth) acrylate and combinations thereof.

Copolymers used according to the present invention generally comprise polymerized moieties of hydrophobic ethylenically unsaturated monomers in the range of about 50-90, 60-90, or 60-80 mole percent relative to the total moles of polymerized monomer moieties of the copolymer. Will include in quantity.

The introduction of polymerized moieties of hydrophobic ethylenically unsaturated monomers in the copolymers used according to the invention advantageously promotes the improved water resistance properties of the polymers derived from aqueous polymer compositions.

One skilled in the art will recognize that the glass transition temperature (Tg) of a polymer is a parameter that is often considered when formulating a polymer composition for a given application. "Tg" is a narrow temperature range in which an amorphous polymer (or an amorphous region of a partially crystalline polymer) changes from a relatively hard and unstable state to a relatively viscous or rubbery state. The Tg of the copolymer used in the present invention may conveniently be tailored to suit the intended application of the aqueous polymer composition according to the present invention.

Those skilled in the art will also recognize that ethylenically unsaturated monomers selected to form a given (co) polymer will strongly affect the Tg of the polymer.

In some embodiments, the copolymers used according to the present invention comprise polymerized moieties of hydrophobic ethylenically unsaturated monomers representing most polymerized monomer moieties in the copolymer. In other words, the polymerized moiety of the hydrophobic ethylenically unsaturated monomer may represent at least 50 mole% relative to the total moles of polymerized monomer moieties of the copolymer.

With this in mind, polymerized moieties of one or more other ethylenically unsaturated monomers can strongly affect the total Tg of the copolymer.

In one embodiment, the amount and type of polymerized moiety of the hydrophobic ethylenically unsaturated monomer is selected to provide a Tg of the copolymer in the range of about -25 ° C to about 100 ° C.

The Tg values mentioned herein are calculated and those relating to the copolymer are calculated according to the well known Fox equation (1 / Tg = W _n / Tg _(n) ).

As will be discussed, polymerized ethylenically unsaturated monomers containing basic functional groups protonated by volatilizable non-gas acids promote water solubility of the copolymer. By definition, a polymerized ethylenically unsaturated monomer comprising a basic functional group that is protonated by a volatilizable non-gas acid cannot be a polymerized hydrophobic ethylenically unsaturated monomer.

However, ethylenically unsaturated monomers comprising functional groups to promote crosslinking of the polymerized copolymers are protonated by (i) volatilizable non-gaseic acids and promote water solubility of the copolymer depending on the nature of the functional groups. It can function as a polymerized ethylenically unsaturated monomer comprising a basic functional group, or (ii) a polymerized hydrophobic ethylenically unsaturated monomer.

Nevertheless, it has been found that the desirable properties of the copolymers can be more readily obtained when the copolymers comprise residues polymerized exclusively from each particular category of ethylenically unsaturated monomers.

Thus, in one embodiment the copolymer is

(i) an ethylenically unsaturated monomer comprising a basic functional group protonated by a volatilizable non-gas acid, wherein the polymerized moiety of the monomer is less than 25 mol% relative to the total moles of polymerized monomer moiety of the copolymer. Monomer present;

(ii) ethylenically unsaturated monomers comprising functional groups for promoting crosslinking of the copolymer; And

(iii) hydrophobic ethylenically unsaturated monomers

Wherein the polymerized moiety is

(a) an ethylenically unsaturated monomer comprising a basic functional group does not comprise a functional group for promoting crosslinking of the copolymer;

(b) the hydrophobic ethylenically unsaturated monomer does not comprise a functional group for promoting crosslinking of the copolymer;

(c) The ethylenically unsaturated monomer comprising a functional group for promoting crosslinking of the copolymer does not include a basic functional group which is protonated by volatilizable non-gas acid.

Those skilled in the art will recognize that an ethylenically unsaturated monomer comprising a basic functional group protonated by a volatilizable non-gas acid cannot be a hydrophobic ethylenically unsaturated monomer and vice versa.

It is an important feature of the present invention to provide the copolymer in soluble form in an aqueous liquid. However, it is also important to provide the polymer with at least improved water resistance properties in the aqueous polymer composition according to the invention.

Although the unprotonated form of the copolymer promotes good water resistance properties for polymers derived from aqueous polymer compositions, the water resistance properties of the polymer may be compromised as too many basic functional groups in the copolymer are subsequently reprotonated. have.

The crosslinked nature of the resulting polymers and the introduction of polymerized moieties of hydrophobic ethylenically unsaturated monomers in the copolymer can advantageously offset some of the water resistance which may originate from the basic functional groups of the copolymer being reprotonated and As discussed, there is an advantage in minimizing the amount of polymerized moieties of ethylenically unsaturated monomers comprising basic functional groups in the copolymer. However, reducing the amount of these basic functionalized polymerized monomer residues in the copolymer will of course adversely affect the solubility of the copolymer in the aqueous liquid.

The storage stable crosslinkable aqueous polymer compositions according to the invention are advantageously formulated to have a relatively low mole percent of protonable polymerized monomer residues of the copolymer.

However, it has been found that the properties of the compositions according to the invention can be further improved by using a copolymer ratio of polymerized hydrophilic ethylenically unsaturated monomers. Without wishing to be bound by theory, the incorporation of polymerized hydrophilic ethylenically unsaturated monomers in the copolymer may help promote solubility of the copolymer in the aqueous liquid and may also include acidic water of the polymer derived from the composition. It is believed that solvation can be minimized.

In one embodiment, the copolymers used according to the invention further comprise polymerized moieties of hydrophilic ethylenically unsaturated monomers.

The copolymer further comprises polymerized residues of the hydrophilic ethylenically unsaturated monomer in an amount in the range of about 0.5-10, or about 0.5-5, or about 0.5-3 mole percent, relative to the total moles of polymerized monomer residues of the copolymer. can do.

In one embodiment, the copolymer used according to the present invention comprises a polymerized moiety of an ethylenically unsaturated monomer comprising a basic functional group that is protonated by a volatilizable non-gaseous acid, the total moles of polymerized monomer moieties of the copolymer. In an amount of less than about 15 mol%, or less than about 12 mol%, or less than about 10 mol%.

In another embodiment, the copolymers used according to the invention are further polymerized ethylenically unsaturated monomers comprising a polymerized moiety of a hydrophilic ethylenically unsaturated monomer and a basic functional group protonated by a volatilizable non-gas acid. The moiety is included in an amount of less than about 15 mole percent, or less than about 12 mole percent, or less than about 10 mole percent, relative to the total moles of polymerized monomer residues of the copolymer.

Examples of hydrophilic ethylenically unsaturated monomers include (meth) acrylic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, oligo (alkylene glycol) methyl ether (meth) acrylate (OAG (M) A ), Hydroxyl terminated oligoethylene glycol, (meth) acrylate, acrylamide, dimethyl acrylamide, methacrylamide, dimethyl methacrylamide, itaconic acid, p-styrene carboxylic acid (s), p-styrene sulfonic acid (s) , Vinyl sulfonic acid, vinyl phosphonic acid, ethyl acrylic acid, alpha-chloroacrylic acid, crotonic acid, fumaric acid, citraconic acid, mesaconic acid, maleic acid, sulfoethyl (meth) acrylate, phosphoethyl (meth) acrylate, Phosphorylcholine (meth) acrylates and combinations thereof.

In one embodiment, the copolymer comprises 10 mole percent, or 8 mole percent, or 5 mole percent of the polymerized moiety of the acid functionalized ethylenically unsaturated monomer relative to the total moles of polymerized monomer moieties of the copolymer. Does not contain in quantity.

In the case of the hydrophilic ethylenically unsaturated monomer OAG (M) A, the alkylene moiety will generally be a C ₂ -C ₆ , for example C ₂ or C ₃ , alkylene moiety. Those skilled in the art will recognize that the "oligo" nomenclature associated with "(alkylene glycol)" refers to the presence of a plurality of alkylene glycol units. Generally, the oligo component of OAG (M) A may contain about 2 to about 50, for example about 2 to about 40, or about 2 to about 30, or about 2 to about 20 alkylene glycol repeat units. Will include.

In one embodiment, the copolymer further comprises a polymerized moiety of a hydrophilic ethylenically unsaturated monomer selected from hydroxyethyl (meth) acrylate.

The polymerized moiety of an ethylenically unsaturated monomer comprising (i) a basic functional group that is protonated by a volatilizable non-gas acid, or (ii) a functional group to promote crosslinking of the copolymer may be hydrophilic or hydrophilic in nature. Given that there is, it is recognized that the copolymer "in addition" comprises polymerized moieties of hydrophilic ethylenically unsaturated monomers, intended to include different polymerized hydrophilic ethylenically unsaturated monomer residues already present in the copolymer. Will be.

In other words, when present in the copolymer, such further polymerized hydrophilic ethylenically unsaturated monomers are (i) ethylenically unsaturated monomers comprising a basic functional group protonated by polymerized volatilizable non-gaseous acid, and (ii ) Is intended to have a different primary function than ethylenically unsaturated monomers comprising functional groups to promote crosslinking of the polymerized copolymer. Of course the polymerized hydrophilic ethylenically unsaturated monomer may not function as the polymerized hydrophobic ethylenically unsaturated monomer.

Thus, when the copolymer further comprises polymerized moieties of hydrophilic ethylenically unsaturated monomers, the polymerized moieties of such hydrophilic ethylenically unsaturated monomers are generally (i) basic functional groups which are protonated by volatilizable non-gas acids. Or (ii) no functional groups capable of reacting with the reversibly blocked crosslinker to promote crosslinking of the copolymer.

The copolymers used according to the invention can be random or statistical copolymers.

In one embodiment, the copolymer used according to the invention is not a block copolymer.

If the copolymer used according to the invention can be dissolved in an aqueous liquid, there is no particular limitation on the number average molecular weight (Mn) of the copolymer.

Generally, the Mn of the copolymer will range from about 10,000 to about 50,000, or from about 10,000 to about 40,000.

Reference to Mn of a polymer comprising a copolymer used according to the invention herein is intended to mean that determined by gel permeation chromatography (GPC).

The copolymers used according to the invention can be described simply by the formulas (I) and (II):

Formulas (I) and (II) are basic functional groups (BFM) protonated by volatilizable non-gas acids, ethylenically unsaturated monomers (CFM) comprising functional groups to promote crosslinking of copolymers, hydrophobic ethylenic To a copolymer that can be used according to the invention comprising a polymerized moiety of an unsaturated monomer (HBM) (formula I), and optionally an ethylenically unsaturated monomer comprising a hydrophilic ethylenically unsaturated monomer (HLM) (formula II). Where * denotes the remainder of the copolymer and ad denotes the mole percent of each polymerized monomer residue. As shown in formulas (I) and (II), the features (BFM), (CFM), (HBM) and (HLM) are not intended to be limited to block copolymer structures. Rather, these features are intended to simply indicate the components present in the copolymer and not to show their relative orientation. In one embodiment, the copolymer is not a block copolymer. In another embodiment, the copolymer is a statistical or random copolymer.

The copolymers used according to the invention will generally be present in the composition in amounts ranging from about 5% by weight to about 60% by weight.

There are no specific restrictions on the polymerization techniques that can be used to form the copolymers used according to the invention. Those skilled in the art will be familiar with suitable polymerization techniques.

In general, copolymers will be prepared using free radical polymerization.

Ethylenically unsaturated monomers that can be used to prepare the copolymer include those described herein.

The polymerization technique used to prepare the copolymer can be carried out in an aqueous, non-aqueous hydrophilic or non-aqueous hydrophobic reaction medium or solvent.

The use of an aqueous reaction medium for preparing the copolymer is advantageous in that the copolymer is directly delivered in the aqueous medium for introduction into the aqueous formulation.

In one embodiment the copolymer is prepared using an aqueous reaction medium having a pH in the range of 4-7.

Examples of aqueous or non-aqueous hydrophilic reaction media include water, water miscible, organic solvents such as C ₁ -C ₃ alcohols, alkyl glycols, acetone, methyl ketones, tetrahydrofuran, dioxane, N-methylpyrroli Don, acetonitrile, dimethylformamide, dimethylsulfoxide and combinations thereof.

Examples of non-aqueous hydrophobic reaction media include benzene, toluene, xylene, alkylbenzenes, dialkylbenzenes, alkanes and combinations thereof.

Polymerization of ethylenically unsaturated monomers by free radical polymerization may require initiation from a source of free radicals. The source of starting radicals may be any suitable means for generating free radicals, for example thermally induced homogeneous separation of suitable compound (s) (thermal initiators such as peroxides, peroxyesters, or azo compounds). , Spontaneous generation from monomers (eg styrene), redox initiation systems, photochemical initiation systems or high energy radiation such as electron beams, X- or gamma-radiation.

Thermal initiators are generally selected to have a suitable half life at the temperature of polymerization. These initiators may comprise one or more of the following compounds:

2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-cyanobutane), dimethyl 2,2'-azobis (isobutyrate), 2,2'-azobis [ 2- (2-imidazolin-2-yl) propane], 4,4'-azobis (4-cyanovaleic acid), 1,1'-azobis (cyclohexanecarbonitrile), 2,2 ' Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (known as VA-0044), 2- (t-butylazo) -2-cyanopropane, 2,2 ' -Azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2'-azobis [2-methyl-N- (2-hydroxy Oxyethyl) propionamide], 2,2'-azobis (N, N'-dimethyleneisobutyramidine) dihydrochloride, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2 , 2'-azobis (N, N'-dimethyleneisobutyramidine), 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxy Ethyl] propionamide}, 2,2'-azobis {2-methyl-N- [1, 1-bis (hydroxymethyl) -2-ethyl] propionamide}, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis ( Isobutyramide) dihydrate, 2,2'-azobis (2,2,4-trimethylpentane), 2,2'-azobis (2-methylpropane), t-butyl peroxyacetate, t-butyl per Oxybenzoate, t-butyl peroxy neodecanoate, t-butylperoxy isobutyrate, t-amyl peroxy pivalate, t-butyl peroxy pivalate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydi Carbonate, dicumyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, potassium peroxydisulfate, ammonium peroxydisulfate, di-t-butyl hyponitrite, dicumyl hyponitrite, this list is not exhaustive .

Photochemical initiator systems are generally chosen to have a suitable quantum yield for radical generation under the conditions of polymerization. Examples include benzoin derivatives, benzophenones, acyl phosphine oxides, and photo-redox systems.

Redox initiator systems are generally selected to have a suitable rate of radical production under polymerization conditions; These initiation systems may include, but are not limited to, combinations of the following oxidizing and reducing agents:

Oxidizers: potassium, peroxydisulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl perbenzoate.

Reducing agents: iron (II), titanium (III), potassium thiosulfite, potassium bisulfite, sodium formaldehyde sulfoxylate, disodium 2-hydroxy-2-sulpineitoacetate, Brugolit FF06, Ascorbic acid, sodium ascorbate, sodium erythorbate.

Other suitable initiation systems are commonly described in the documentation available. See, for example, Moad and Solomon, "The Chemistry of Free Radical Polymerization", Pergamon, London, 1995, pp 53-95.

Initiators more easily solvated in hydrophilic reaction media are 4,4-azobis (cyanovalleic acid), 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis (N, N'-di Methyleneisobutyramidine), 2,2'-azobis (N, N'-dimethyleneisobutyramidine) dihydrochloride, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2 , 2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-ethyl] propionamide}, 2,2'-azobis [2- (2-imidazoline- 2-yl) propane] dihydrochloride (known as VA-044), 2,2'-azobis [2- (2-imidazolin-2-yl) propane] (known as VA-061), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis (isobutyramide) dihydrate, and derivatives thereof But this is not restrictive.

Initiators that more readily solvate in the hydrophobic reaction medium include azo compounds exemplified by 2,2'-azobisisobutyronitrile, a well known material. Other suitable initiator compounds include acyl peroxide classes such as acetyl and benzoyl peroxide as well as alkyl peroxides such as cumyl and t-butyl peroxide. Hydroperoxides such as t-butyl and cumyl hydroperoxides are also widely used.

In consumer products containing polymers, it may be important that the polymer used contains low levels of monomers that do not undergo polymerization during the manufacture of the polymer. Means for minimizing unreacted monomer residues in polymer products are known to those skilled in the art. For example, multistage addition of an initiator system during polymerization can be used to minimize unreacted monomer residues in the polymer so formed.

The free radical polymerization of the monomer can be carried out by conventional free radical polymerization or so-called living free radical polymerization. Living polymerization is generally considered to be a form of chain polymerization that is substantially free of irreversible chain termination in the art. An important feature of living polymerization is that the polymer chain will continue to grow while the monomers supporting the polymerization and the reaction conditions are provided.

If the free radical polymerization of the monomers is via living polymerization technique (also known as reversible inactive radical polymerization), it will generally be necessary to use a so-called living polymerizer. By "living polymerizer" is meant a compound that can participate in and control or mediate living polymerization of ethylenically unsaturated monomers to form living polymer chains (ie, polymer chains formed according to living polymerization techniques).

Examples of free radical living polymerization techniques include iniferter polymerization, safe free radical mediated polymerization (SFRP), atom transfer radical polymerization (ATRP), and reversible addition fragmentation chain transfer (RAFT) polymerization.

Molecular weight control of copolymers can be accomplished by conventional chain transfer agents such as thiols, allyls, allyl sulfides (Macromolecules 1988, 21, 3122-3124) styrene derivatives (polymers 2008, 49, 1079-1131), alkenes, for example For example, 2,4-diphenyl-4-methyl-1-pentene, terpenes and similar compounds such as terpinolene, gamma terpinene, 5-ethylidene-2-norbornene and perrylyl alcohol and combinations thereof It can be achieved by the use of.

Surprisingly, terpinolenes (also known as δ-terpinene, 4-isopropylidene-1-methylcyclohexene, or Nofmer TP), when prepared in water, have good control over the molecular weight of the copolymer. It was confirmed to provide.

In one embodiment, terpinolene is used as a chain transfer agent when preparing copolymers in an aqueous reaction medium. In further embodiments, terpinolene is used in an amount up to about 1.5 mole percent, or up to 1 mole percent, relative to the total moles of polymerized monomers.

Synthesis of the copolymer can be carried out in an organic solvent, water or a combination of the two. Since the copolymer solution obtained can then be used directly to prepare the composition according to the invention, it may be advantageous to prepare the polymer in an aqueous liquid.

Without limitation, the synthesis of the copolymer can be carried out with a non-aqueous or aqueous liquid, the required ethylenically unsaturated monomers, one or more initiators, one or more volatilizable non- Gas acid, molecular weight modifiers (eg, chain transfer agents).

Synthesis of the copolymer in the aqueous reaction medium can be advantageous. This allows formulator latitude in the addition of water miscible cosolvents or other ingredients as part of the process for preparing the composition according to the present invention.

The synthesis of the copolymer in an aqueous liquid using hydrophobic ethylenically unsaturated monomers is preferably carried out by minimizing the tendency to form separated monomer / copolymer droplets in the reaction medium. Of course the purpose here is to form an aqueous copolymer solution that is not a latex particle.

In one embodiment, the copolymer comprises polymerized moieties of hydrolysis sensitive ethylenically unsaturated monomers and the copolymer is prepared under acidic conditions in an aqueous liquid to (i) solubilize the copolymer through protonation of its basic functional groups. And (ii) prevent or minimize hydrolysis of any hydrolysis sensitive ethylenically unsaturated monomers used.

Examples of hydrolysis sensitive ethylenically unsaturated monomers include DMAEMA and methyl methacrylate (MMA).

The acid content of the aqueous liquid reaction medium may vary depending on the amount of basic functional groups of the copolymer and the hydrolysis sensitivity of the ethylenically unsaturated monomers used.

In general, the acid concentration [H ⁺ ] in the aqueous liquid reaction medium is 0.5 to 2, or 0.75-1.5, per mole of ethylenically unsaturated monomer comprising a basic functional group protonated by the volatilizable non-gaseous acid used, Or 0.8-1.2 molar equivalents.

Copolymers can be prepared in batch or by feed addition of reactants over time. The polymerization can be carried out under a suitable oxygen free atmosphere, as is commonly done for free radical polymerization. Without limiting the invention, it may be advantageous to deoxygenate in the reaction medium, all reactants and their solutions as is typically done in conventional free radical polymerizations.

In one embodiment, the copolymer is prepared by feed addition of ethylenically unsaturated monomers to the aqueous liquid.

In another embodiment, the copolymer is prepared by feed addition of ethylenically unsaturated monomers comprising volatilizable non-gaseous acid to an aqueous liquid.

Typical, non-limiting, general examples of aqueous copolymer synthesis processes are as follows.

The polymerization can be carried out by deoxygenation of the water in the reaction vessel, maintained under nitrogen, and part of the initiator added. The solution is stirred and heated to 60 ° C.

Small amounts of seed polymer (eg, previously prepared from previous synthetic batches) can be added. Such seed polymers may be of the same composition or different from the polymers produced, but should still contain polymerized ethylenically unsaturated monomers as described herein. Those skilled in the art will recognize that such seed polymers must be miscible with the bulk copolymer produced, but need not be the same overall composition.

Seed polymers may be used in amounts up to about 5%, or 4% or 3% (v / v).

Without wishing to be bound by theory, it is believed that the use of seed polymers assists in solubilizing the incoming ethylenically unsaturated monomers and provides a homogeneous reaction zone.

Copolymers can be prepared without the use of seed polymers.

Then, a supply of ethylenically unsaturated monomer, volatilizable non-gas acid and chain transfer agent (if necessary) is added to the reaction vessel via a pump for 4 hours. Concurrent with this supply, a separate supply of initiator (if necessary) in water is added via a pump for a 6 hour period. At the end of the addition of the initiator, additional batch initiators may be added if necessary.

Under these conditions, the conversion of ethylenically unsaturated monomers is generally completed essentially with only traces (about <0.5% mole) of residual unreacted ethylenically unsaturated monomers. This can be further reduced if necessary by conventional techniques, for example by the addition of redox couples such as t-butyl hydroperoxide and sodium formaldehyde sulfoxylate.

Some hydrolysis of hydrolysis sensitive ethylenically unsaturated monomers (eg DMAEMA) may occur during the polymerization. However, this will generally be less than about 5 mole percent of the monomers and does not have an apparent adverse effect on the performance of the composition according to the invention.

The aqueous solution obtained upon completion of the polymerization is advantageously suitable for direct use in preparing the aqueous polymer composition according to the invention. In that case, other components used in the composition are introduced as necessary.

Modifications and adjustments to the process can be made by those skilled in the art, depending on the scale, reaction time required, and the like. A further variation is that base can be added to the solution before, during or after the polymerization to control the viscosity of the solution. Without limiting the invention, the preferred salt for this process is ammonium acetate, other salts such as ammonium bicarbonate are also suitable.

The supply of ethylenically unsaturated monomers to the reaction vessel provides the ability to feed the monomers at an angle or add different monomers throughout the polymerization. This allows a high degree of alignment of the copolymer formed.

All ethylenically unsaturated monomers can also be added simultaneously in a constant ratio with each other.

Copolymers can also be synthesized in organic solvents. One advantage of synthesizing polymers in such solvents is that problems associated with monomer hydrolysis can be minimized or avoided. In that case, however, the solvent will of course need to be removed and the copolymer obtained will be isolated for use according to the invention and then dissolved in acidic water. As in the case of aqueous synthesis, the synthesis in a non-aqueous solvent can be carried out in batch or continuous feed.

The present invention also provides a process for preparing an aqueous copolymer composition comprising polymerization in an aqueous liquid comprising volatilized non-gas acid ethylenically unsaturated monomers selected from:

(i) an ethylenically unsaturated monomer comprising a basic functional group protonated by a volatilizable non-gas acid, wherein the monomer is 25 mole% relative to the total moles of ethylenically unsaturated monomer introduced during the polymerization to prepare the copolymer. Monomers used in amounts less than;

(ii) ethylenically unsaturated monomers comprising functional groups for promoting crosslinking of the copolymer; And

(iii) hydrophobic ethylenically unsaturated monomers;

Here, the copolymer so formed is soluble in an aqueous liquid.

The method comprises polymerizing an ethylenically unsaturated monomer selected from groups (i), (ii) and (iii), respectively, in an aqueous liquid comprising volatilizable non-gas acids.

The aqueous liquids, volatilizable non-gas acids and ethylenically unsaturated monomers used are as described herein.

In the preparation or formation of the copolymers, ethylenically unsaturated monomers comprising basic functional groups, which are generally protonated by volatilizable non-gaseous acids, are about about the total moles of ethylenically unsaturated monomers introduced during the polymerization to prepare the copolymer. It may be used in an amount ranging from 1-20 mol% or 1-15 mol%, or 1-10 mol%.

In one embodiment, the ethylenically unsaturated monomer comprising a basic functional group (protonated by volatilizing non-gas acid) is less than 20 mol% relative to the total moles of ethylenically unsaturated monomer introduced during the polymerization to prepare the copolymer. , Or less than 15 mol%, or less than 10 mol%.

In the preparation or formation of the copolymer, generally the ethylenically unsaturated monomer comprising functional groups to promote crosslinking of the copolymer is about 0.5-20 to the total moles of ethylenically unsaturated monomer introduced during the polymerization to prepare the copolymer. Molar%, 0.5-15 mole%, 0.5-10 mole%, or 0.5-8 mole%, or 1-5 mole%.

In the preparation or formation of the copolymer, generally the hydrophobic ethylenically unsaturated monomer is about 50-90 mol%, 60-90 mol%, or 60-to the total moles of ethylenically unsaturated monomer introduced during the polymerization to prepare the copolymer. It will be used in an amount in the range of 80 mol%.

In one embodiment, the method of making or forming the aqueous copolymer solution further comprises polymerizing a hydrophilic ethylenically unsaturated monomer.

In the preparation or formation of the copolymer, generally the hydrophilic ethylenically unsaturated monomer is about 0.5-10 mole percent, or about 0.5-5 mole percent, relative to the total moles of ethylenically unsaturated monomer introduced during the polymerization to prepare the copolymer, or It will be used in an amount in the range of about 0.5-3 mole%.

In one embodiment, the ethylenically unsaturated monomers comprise 10 mole percent, or 8 mole percent, based on the total moles of polymerized monomer residues of the copolymer, the polymerized moiety of the ethylenically unsaturated monomer in which the copolymer so formed is acid functionalized, Or not included in an amount of 5 mol%.

In one embodiment the copolymer is prepared or formed using an aqueous reaction medium having a pH in the range of 4-7.

In another embodiment, the acid concentration [H ⁺ ] in the aqueous liquid reaction medium is between 0.5 and 2, or 0.75, per mole of ethylenically unsaturated monomer comprising a basic functional group protonated by the volatilizable non-gas acid used. -1.5, or 0.8-1.2 molar equivalents.

Reversibly Blocked Crosslinker

The aqueous polymer composition according to the present invention comprises a reversibly blocked crosslinker to promote crosslinking of the copolymer. A reversibly blocked crosslinker is provided in the composition in combination with a volatilizable crosslinking inhibitor to inhibit crosslinking of the copolymer by the reversibly blocked crosslinker. As will be discussed in more detail below, providing a crosslinker that is reversibly blocked in that way surprisingly gives the composition excellent storage stability.

Reversibly blocked crosslinkers can be provided in the composition by adsorption on dispersed particulate matter.

“Reversibly blocking” a crosslinker is intended to mean that the crosslinker can be present in the composition according to the invention in blocked and unblocked form. In the blocked form, the crosslinker does not react to any significant extent even if it reacts with the polymerized monomer residues of the copolymer that provide a functional group to promote crosslinking of the copolymer. In the unblocked form, the crosslinking agent can readily react with the polymerized monomer residues of the copolymer providing functional groups to promote crosslinking of the copolymer, thereby crosslinking the copolymer.

Thus, the "reversibly" blocking of the crosslinker is intended to mean that the crosslinker may exist in equilibrium in the aqueous polymer composition between the blocked form and the unblocked form.

When preparing the aqueous polymer composition (discussed in more detail below), the reversibly blocked crosslinker can itself be introduced into the aqueous liquid or formed in situ.

This equilibrium between the blocked and unblocked forms of the crosslinker according to the invention can be made by the presence of water and the nature of the blocking group. This is shown schematically in the following equilibrium scheme:

In the above equilibrium scheme, BG represents the blocking group (s), CA represents the crosslinking agent, and P represents a copolymer having a functional group capable of reversibly reacting with CA. CA is understood to be multifunctional because it will be needed to crosslink the copolymer. For example, ADH has two hydrazide groups. Blockers, such as acetone, may react with one or more hydrazide groups to form hydrazones, thus preventing crosslinking of the copolymer with the reactor. In that example, the presence of water (eg from an aqueous liquid) can convert the blocked form (I) of the crosslinker to its unblocked form (II) with BG (acetone). However, back reactions can also occur and an equilibrium is established between the blocked and unblocked forms of the crosslinker.

In the context of the present invention, there should be a strong preference for the equilibrium as well as the formation of the blocked form (I) of the crosslinker during storage of the composition. In that case, the crosslinker may remain largely in its blocked form due to excess BG during storage of the composition (see also the discussion below for the function of volatilizable crosslinking inhibitors). However, when using the composition, the loss of BG, such as acetone, from the composition can promote the reaction of the copolymer with any unblocked form of the crosslinker to promote crosslinking. Thus, upon application of the composition on the substrate surface, BG from the composition may evaporate or be absorbed by the substrate to promote crosslinking of copolymer P, resulting in the formation of additional unblocked crosslinkers and copolymer P and its Equilibrate the reaction. In the following schemes (represented by (I)-(III)), the loss of BG (eg acetone) drives the reaction to the extreme right (III), which indicates crosslinking of polymer P. The central (II) and polar (I) positions represent uncrosslinked polymers present in the composition during storage and are favored by the presence of excess BG. It is understood that this description is a simplification of the many equilibria that occur and that there may be multiple reactive sites on individual copolymer chains.

Of course, in at least some of the unblocked forms of the crosslinker, it is possible to recombine with the blocker (s) to reconstruct the blocked crosslinker when the composition is applied to the substrate surface, the blocker being combined with water and volatilizable non-gas acid. Volatile blockers are preferred in that they can be easily released from the applied composition. Thus, as previously described, the loss of BG is driven to provide a crosslinker with no equilibrium blocked, which in turn promotes crosslinking of the copolymer.

In one embodiment, the reversibly blocked crosslinker to promote crosslinking of the copolymer is blocked by volatilizable blocker (s).

As used herein, the expression “volatile blocker (s)” (i) functions to block the reactivity of the crosslinking groups with the crosslinking functional groups of the copolymer, and (ii) the present invention under conditions under which the composition is commonly used. Is intended to mean compounds which can escape from the aqueous polymer composition (eg, by evaporation or absorbed into the substrate).

Those skilled in the art will recognize that in crosslinkers that crosslink a copolymer, the crosslinker will require two or more functional groups that can react with the functional groups to promote crosslinking to form part of the copolymer. . For convenience, functional groups of the crosslinker that can react with the functional groups of the copolymer to form crosslinks may be described herein as reactive functional groups of the crosslinker. Typically, two or more reactive functional groups of the crosslinker will each react with functional groups on two separate copolymer chains to form a crosslink.

All reactive functional groups of the crosslinker can be reversibly blocked as described herein and it is possible to carry out the invention with one of these reactors left unblocked. In that case the unblocked reactive functional groups of the crosslinker may react with the functional groups of the copolymer to promote crosslinking. However, because all residual reactive functional groups of the crosslinker are reversibly blocked, the crosslinker will not crosslink the copolymer until one or more reversibly blocked reactive functional groups are not blocked (and react with the copolymer). will be.

Thus, a "reversibly blocked" crosslinker covers the situation where all or one but all reactive functional groups are blocked from undergoing a reaction with the copolymer (reversibly) to form a crosslink as described herein. .

Those skilled in the art will recognize that the amount of reversibly blocked crosslinker used in accordance with the present invention will generally be tailored to react with substantially all of the functional groups provided by the copolymer to promote crosslinking.

Regarding the number of functional groups of the copolymer to promote crosslinking, the amount of crosslinker that is reversibly blocked will of course depend on the number of reactive functional groups provided by the crosslinker. For example, if the reversibly blocked crosslinker comprises two reactive functional groups, the number of moles of the reversibly blocked crosslinker will be approximately half the number of moles of functional groups provided by the copolymer to promote crosslinking. Similarly, if the reversibly blocked crosslinker comprises three reactive functional groups, the number of moles of the reversibly blocked crosslinker will be approximately one third of the number of moles of functional groups provided by the copolymer to promote crosslinking, and the like. to be.

In one embodiment, the molar ratio of the number of functional groups to promote crosslinking of the reversibly blocked crosslinker and the copolymer ranges from about 0.5 molar equivalents to about 1.5 molar equivalents.

One skilled in the art can react with (i) functional groups of the copolymer to promote crosslinking, and (ii) have reactive functional groups that can be reversibly blocked in the aqueous polymer composition according to the invention as described herein. Suitable crosslinkers may be selected.

Examples of suitable reversibly blocked crosslinkers include, but are not limited to, reversibly blocked multifunctional hydrazide compounds.

As used herein, the expression “multifunctional hydrazide compound” is intended to mean a compound having two or more hydrazide functional groups.

In one embodiment, the multifunctional hydrazide compound comprises two, three, or four hydrazide functional groups.

Those skilled in the art will recognize that the reactive (crosslinking) functional groups of such multifunctional hydrazide compounds are hydrazide functional groups.

Those skilled in the art will also recognize that hydrazide functional groups can react with functional groups containing carbonyl moieties such as ketones or aldehydes. Thus, when a reversibly blocked multifunctional hydrazide compound is used as a crosslinking agent according to the invention, the copolymer is capable of crosslinking of a copolymer selected from carbonyl containing functional groups such as ketones, aldehydes and combinations thereof. It will include polymerized moieties of ethylenically unsaturated monomers containing functional groups to promote.

Those skilled in the art will know suitable blockers for providing such reversibly blocked multifunctional hydrazide compounds.

In one embodiment, the multifunctional hydrazide compound is reversibly blocked in the form of a hydrazone compound.

In further embodiments, the reversibly blocked crosslinker is selected from a multifunctional hydrazone compound or a compound comprising one or more hydrazone functional groups and one hydrazide functional group.

As used herein, reference to “multifunctional hydrazone compound” is intended to mean a compound having two or more hydrazone functional groups. Multifunctional hydrazone compounds used according to the invention will generally contain up to one hydrazide functional group. In one embodiment, the multifunctional hydrazone compound used according to the present invention does not contain hydrazide functional groups.

In one embodiment, the reversibly blocked crosslinker used in accordance with the present invention comprises two hydrazone functional groups and no hydrazide functional groups.

In another embodiment, the reversibly blocked crosslinker used according to the invention comprises one hydrazone functional group and one hydrazide functional group.

Examples of reversible blocked crosslinkers that may be used in accordance with the present invention that include two hydrazone functional groups and no hydrazide functional groups, or include one hydrazone functional group and one hydrazide functional group, Including but not limited to those defined by the following formulas (I)-(IV).

In the compounds of formula (I)-(IV) directly above, R represents a divalent organic group or a covalent bond, and R ₁ -R ₄ are each independently selected from hydrogen and organic groups.

In one embodiment, R and R ₁ -R ₄ are each independently selected from optionally substituted alkyl, optionally substituted alkenyl, and optionally substituted alkynyl. In further embodiments, R and R ₁ -R ₄ each independently contain 1 to 24 carbon atoms, or 1 to 12 carbon atoms.

In further embodiments, R ₁ and R ₂ or R ₃ and R ₄ are independently joined together to form a cyclic group.

In another embodiment, R ₁ -R ₄ are each independently hydrogen or are independently selected from C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, and C ₁ -C ₆ alkynyl, and R is C ₁ -C _{12 is} optionally substituted alkyl.

In further embodiments, each R ₁ -R ₄ is a methyl group and R is selected from C ₁ -C ₁₂ optionally substituted alkyl.

In another embodiment, in each formula (I)-(IV), R is a divalent organic group as described substituted with an additional hydrazone functional group. For example, R can be divalent alkyl, alkenyl, or alkynyl substituted with a hydrazone functional group.

To further illustrate the reversibly blocked nature of the reversibly blocked crosslinkers used according to the invention, see Scheme (II) below.

In the above scheme (II), the dihydrazide compound (ie, the unblocked form of the crosslinker) is in equilibrium with acetone in the presence of water to form the dihydrazone compound. This equilibrium favors the formation of most Hydrazone compounds (see also the discussion below for the function of volatilizable crosslinking inhibitors). However, in the context of the present invention and in the above scheme (II), the loss of acetone promotes the crosslinking by promoting the reaction of any present dihydrazide compound with the copolymer (also containing acetone or aldehyde groups). can do. Thus, upon application of the aqueous polymer composition on the substrate surface, the loss of acetone from the composition may promote crosslinking of the copolymer, eventually driving equilibrium into the formation of additional dihydrazide compounds. In addition, of course, the formation of the dihydrazide compound also releases the blocker in acetone form. Acetone is volatilizable and can also escape from the applied composition with water, volatilizable non-gas acids and any other volatile components in the composition. The loss of acetone from the composition is the driving force in equilibrium to provide the dihydrazide compound, which in turn promotes crosslinking of the copolymer.

In one embodiment, the reversibly blocked crosslinker is succinic acid di (propylidene hydrazide), oxalic acid di (2-propylidene hydrazide), adipic acid di (2-propylidene hydrazide), Adipic di (2-butylidene hydrazide), adipic di (4-hydroxy-4-methyl-2pentylidene hydrazide, ethylenediaminetetraacetic acid tetrahydrazide (EDTA-tetrahai) Drajid) and combinations thereof.

Hydrazone compounds suitable for use as reversibly blocked crosslinkers according to the present invention can be prepared by techniques well known to those skilled in the art. For example, the multifunctional hydrazide compound can react with aldehydes or ketones. When preparing an aqueous polymer composition (discussed in more detail below), these hydrazone reversibly blocked crosslinkers can be prepared and introduced into the aqueous liquid, or they are advantageously formed in situ when preparing the composition. Can be.

Examples of multifunctional hydrazides that can be used to prepare reversibly blocked crosslinkers are C ₂ -C ₁₈ saturated dicarboxylic acid dihydrazides such as oxalic acid dihydrazide, malonic acid dihydrazide, Glutaric acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide; Monoolefin unsaturated dicarboxylic acid dihydrazides such as maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide; Terephthalic acid dihydrazide or isophthalic acid dihydrazide; Pyromellitic acid dihydrazide; Multifunctional hydrazides containing at least three hydrazide groups such as citri trihydrazide, nitrilo-acetic trihydrazide, ethylene diamine tetra-acetic tetrahydrazide; Nitrilotrihydrazide; 1,2,4-benzene trihydrazide; 1,4,5,8-naphthoic acid tetrahydrazide; N-methyliminodiacetic dihydrazide and combinations thereof, including but not limited to.

Multifunctional hydrazide can be readily derived from the reaction of hydrazine with methyl esters and hydrazine as described below:

This may allow access to hydrazides such as N-methyliminodiacetic acid, and those derived from EDTA. A two-step reaction is generally required to convert the acid to methyl ester and then give hydrazide by reaction with hydrazine. This is illustrated with the following EDTA:

Similarly, other polyhydrazides such as those derived from methyliminodiiacetic acid and nitrilotriacetic can be prepared:

The reaction can also be applied in the preparation of hydrazide functional polymers. Polymers containing methyl esters derived from methyl acrylate, methyl methacrylate or other polymerizable methyl esters can be converted to polyhydrazides by reaction of the hydrazine with the polymer. In this case, the polymer may contain other repeat units derived from other monomers, or alternatively it may be chosen such that the polymer may contain a portion of 1 to 100% of the hydrazide groups correspondingly available. Only some of the methyl esters can be reacted, for example:

Ketones or aldehydes that can be used to react with the multifunctional hydrazide to form the hydrazone compound include compounds of formula (V):

Wherein R ₅ and R ₆ are each independently selected from hydrogen and optionally substituted alkyl (eg, C 1 -C 6), provided that at least one of R ₅ and R ₆ is an optionally substituted alkyl group or together a cyclic ketone To form.

Examples of suitable aldehyde compounds include, but are not limited to, those selected from formaldehyde, acetaldehyde, butyraldehyde, benzaldehyde, cinnamic aldehyde, and toluylaldehyde.

Examples of suitable ketone compounds are acetone methyl ethyl ketone, diethyl ketone, isopropyl methyl ketone, n-propyl methyl ketone, diisopropyl and di-n-propyl ketone, tert-butyl methyl ketone, isobutyl methyl ketone, sec- Butyl methyl ketone and diisobutyl ketone, diacetone alcohol, cyclohexanone, cyclopentanone, 1-propanone, 2-propanone and acetophenone and combinations thereof, including but not limited to these.

Reversibly blocked crosslinkers can also be derived from multifunctional amines. Such amines can be reversibly blocked by reaction with carbon dioxide to form carbamates. The loss of carbon dioxide from the carbamate can reform the multifunctional amine, which can react with the polymerized monomer residues of the copolymer, providing a functional group to promote crosslinking of the copolymer.

Volatile Crosslinking Inhibitors

The aqueous polymer composition according to the invention may comprise a volatilizable crosslinking inhibitor for inhibiting crosslinking of the copolymer.

As used herein, the expression “volatile acidic crosslinking inhibitor” can inhibit (i) crosslinking of the copolymer by a reversibly blocked crosslinking agent, and (ii) the composition is typically as described herein. It is intended to mean compounds which can escape from the composition according to the invention under the conditions used.

As discussed above, the aqueous polymer composition according to the present invention comprises a reversibly blocked crosslinker to promote crosslinking of the copolymer. The reversibly blocked nature of the crosslinker helps to prevent premature crosslinking of the copolymer during storage of the composition (eg, when the composition is not used). However, although the use of the reversibly blocked crosslinker according to the invention helps to prevent such early crosslinking, it has been found that the use of the reversibly blocked crosslinker alone is not effective in imparting composition storage stability.

The use of reversibly blocked crosslinkers such as those described herein in aqueous emulsion polymer compositions is known. For example, multifunctional hydrazone compounds have been used as reversibly blocked crosslinkers in emulsion coating compositions.

As applied in such emulsion coating compositions, the hydrazone crosslinker dissolves in the continuous aqueous liquid phase and the polymeric binder appears as a dispersed phase in the aqueous liquid. The dispersed polymeric binder includes functional groups that can react with the unblocked form of the crosslinker. Such compositions may be described as being self-supporting, storage stable crosslinkable coating compositions. However, the storage stability characteristics of such crosslinkable compositions include (i) the use of a reversibly blocked crosslinker that is dissolved in the continuous aqueous liquid phase and has an equilibrium that favors most of the blocked form of the crosslinker, and (ii) the continuous aqueous phase. It originates from a polymeric binder comprising a functional group for promoting crosslinking which is isolated in the form of particles dispersed in it. Although the equilibrium of the reversibly blocked crosslinker provides at least some unblocked crosslinkers in the continuous aqueous phase, the reactive form of the crosslinker has functional groups to promote crosslinking in any substantial crosslinking that occurs. It is not simply exposed to sufficient polymer binder. Thus, such compositions are referred to as storage stability.

When such a storage stable crosslinkable emulsion coating composition is applied to a substrate, water can evaporate from the composition, thus making the dispersed polymer binder particles very close to the reversibly blocked crosslinker. This in turn promotes increased reactivity between any unblocked crosslinker and the functional groups of the polymer binder to promote crosslinking, resulting in a crosslinked polymer film. However, despite being freestanding, crosslinkable and storage stable, such emulsion coating compositions still tend to have problems associated with the need for dispersed polymer binder particles to aggregate and form a continuous polymer mass or film.

Attempts have been made to compound aqueous polymer compositions using only reversibly blocked crosslinkers in a manner similar to that employed in the emulsion coating compositions mentioned above in the development of the present invention. However, the composition obtained was surprisingly found to be not storage stable.

Without wishing to be bound by theory, it is believed that the lack of storage stability of these developing aqueous polymer compositions is due to the polymeric binders (ie, copolymers) used according to the invention that are soluble in aqueous liquids. Copolymers that are soluble in aqueous liquids (as opposed to being dispersed phases) as well as all of their functional groups are exposed to reversibly blocked crosslinkers that are dissolved in the aqueous liquid to promote crosslinking of the copolymers. This in turn facilitates easy access of any unblocked crosslinker that reacts with the functional groups of the copolymer to promote crosslinking. As mentioned, removal of the unblocked crosslinker from the reversibly blocked crosslinker equilibrium further drives more formation of the unblocked crosslinker and the crosslinking reaction proceeds.

Surprisingly, reactions that promote crosslinking between reversibly blocked crosslinkers and the copolymers used according to the invention employ volatilizable crosslinking inhibitors in combination with reversibly blocked crosslinkers to impart storage stability to the composition. It has now been identified that can be suppressed by.

In the context of using a volatilizable crosslinking inhibitor in combination with a reversibly blocked crosslinker, the reversibly blocked crosslinker may be present "freely" in solution (ie, dissolved in an aqueous liquid).

Thus, in one embodiment the composition according to the invention is reversibly blocked to promote crosslinking of the copolymer in combination with a volatilizing crosslinking inhibitor for inhibiting crosslinking of the copolymer by a reversibly blocked crosslinker. Crosslinkers.

Without wishing to be bound by theory, these volatilizable crosslinking inhibitors interact with the copolymer's functional groups and / or reversibly blocked crosslinking agents to promote crosslinking to more effectively and effectively prevent early crosslinking of the copolymer. It is considered to prevent.

It is contemplated that volatilizable crosslinking inhibitors can cause the reversibly blocked crosslinker to be substantially completely present in the composition in its blocked form by shifting the blocked / unblocked equilibrium in addition to the blocked form. For example, where the reversibly blocked crosslinker is a dihydrazone compound, the equilibrium favoring dehydrazone (blocked) can be promoted by including ketones, for example acetone, in the composition. Upon application of the composition to the substrate, the volatilizable crosslinking inhibitor (eg, acetone) can leave the composition to remove the barrier to crosslinking of the copolymer.

It is contemplated that volatilizable crosslinking inhibitors may also interact with functional groups of the copolymers that promote crosslinking and in effect make these groups incapable of undergoing crosslinking until the composition is used. For example, if the crosslinking functionality of the copolymer is a ketone or an aldehyde, such functional groups can be made temporarily to avoid crosslinking through reaction with a volatilizable crosslinking inhibitor that provides an amine. In that case, the amine can react with the ketone or aldehyde functional group to form an imine that can be reversibly returned back to the ketone or aldehyde. Upon application of the composition to the substrate, the imine so formed can return back to the ketone or aldehyde, which then releases the amine, which in turn can leave the composition to remove the barrier to crosslinking of the copolymer.

Accordingly, volatilizable crosslinking inhibitors are compounds that chemically interact with the functional and / or reversibly blocked crosslinking agent of the copolymer to promote crosslinking to inhibit crosslinking of the copolymer.

The role and function of volatilizable crosslinking inhibitors is further described with reference to Schemes (a) and (b):

Scheme (a)

Scheme (a) conceptually illustrates the protonated copolymer in an aqueous solution as a storage stable crosslinkable composition according to the present invention. Acetic acid is used as the volatilizable non-gas acid and protonates the tertiary amine basic functional groups of the copolymer to promote its solubility in aqueous liquids. The copolymer contains a ketone group to promote crosslinking of the copolymer. Crosslinkers are ADH which reversibly react with ketone groups (in this case, acetone) to produce hydrazones. Thus the reversibly blocked crosslinker is a reversibly blocked hydrazide. There is also an excess of acetone in the aqueous solution which functions as a volatilizing crosslinking inhibitor for hydrazide groups. It will be appreciated that the blocking groups and crosslinking inhibitors in Scheme (a) occur as being the same compound and are therefore functionally interchangeable. ADH is "blocked" partially or completely by acetone. As excess acetone is present relative to the amount of carbonyl groups in the copolymer, acetone prevents any significant reaction of the copolymer with ADH. If one functional group of ADH occurs to react with the ketone group of the copolymer in the presence of excess acetone (as during storage of the composition), it may react with the second ketone group of the copolymer to cause crosslinking of the copolymer There is little possibility. Free acetone in Scheme (a) can be considered to be a volatilizing crosslinking inhibitor. Its presence effectively prevents copolymers in solution from crosslinking by reacting with the free hydrazide groups of ADH.

Scheme (b)

Scheme (b) conceptually illustrates how the composition of the present invention produces crosslinked polymer masses or films. When the storage stable crosslinkable aqueous polymer composition of the present invention is applied to the substrate surface as shown in Scheme (a), water, acetone and acetic acid will evaporate from the applied composition. The loss of acetone (volatile acid crosslinking inhibitor) will increase the concentration and lead to non-blocking of the hydrazide groups that allow the reaction with the carbonyl groups of the copolymer, only the ketone groups are available for the current reaction. Loss of water will concentrate the copolymer solution, eventually resulting in a dry film or lump, and loss of acetic acid (volatile non-gas acid) will render the copolymer water insoluble as the amine groups of the copolymer deprotonate. . Complete drying of the film or mass will result in a crosslinked film or mass that is currently essentially water resistant.

The defined volatilizing crosslinking inhibitor will typically be selected based on the nature of the functional groups of the copolymer to promote (i) the reversibly blocked crosslinking agent used, and (ii) the crosslinking used in the composition. Those skilled in the art will be able to select suitable volatilizing crosslinking inhibitors to have with the crosslinking chemistry used.

Certain volatilizable crosslinking inhibitors may themselves directly interact with the functional groups and / or reversibly blocked crosslinking of the copolymer to promote crosslinking, or more effectively and efficiently prevent early crosslinking of the copolymer. In order to facilitate the crosslinking in situ in the composition, a compound can be produced which interacts with the functional groups and / or reversibly blocked crosslinkers of the copolymer. Examples of the latter case include volatilizing crosslinking inhibitors, such as ammonium acetate, introduced into the composition, where the ammonia is produced in situ, and the ammonia is functionally and / or reversibly blocked in the copolymer to promote crosslinking. Interact with the crosslinker.

Specific examples of volatilizing crosslinking inhibitors include, but are not limited to, ketones such as acetone, methyl ethyl ketone, isopropyl methyl ketone, diethyl ketone and combinations thereof.

In one embodiment, the volatilizing crosslinking inhibitor is acetone.

If present, volatilizable crosslinking inhibitors will generally be used in amounts ranging from 0.5 to 10 molar equivalents relative to the functional groups participating in the crosslinking of the copolymer in the composition according to the invention.

Dispersed particulate matter

The compositions described herein may also include dispersed particulate matter having reversibly blocked crosslinkers adsorbed thereon.

The particulate matter being dispersible in the composition means that the particulate material is substantially insoluble in the composition and forms a dispersed phase therein.

Dispersible particulate materials will typically be solid particulate materials.

The dispersed or dispersible particulate material may be nonpolymeric.

Examples of dispersed or dispersible particulate materials include, but are not limited to, inorganic pigments, organic pigments, extenders, solid fillers, and combinations thereof.

Examples of inorganic pigments include carbon black, titanium dioxide, iron oxide, zinc chromate, azurite, chromium oxide, cadmium sulfite, lithopone, calcium carbonate, hydrated magnesium silicate, barium sulfate, hydrated aluminum silicate, silica, hydrous aluminum potassium Silicates and combinations thereof, including but not limited to.

Examples of organic pigments include, but are not limited to, azo dyes, polycyclic pigments, and combinations thereof.

The dispersed or dispersible particulate material may have an average particle size described by the intended commercial application for the composition.

The dispersed or dispersible particulate material may be solid and non-porous or solid and porous. In that context, the term “porous” is intended to mean a hole or void in particulate matter having the effect of increasing its surface area.

The fact that a dispersed or dispersible particulate material has a reversibly blocked crosslinker adsorbed therein means that the reversibly blocked crosslinker is physically associated with the particulate material and is in its state during storage of the composition and at least until the composition is used. It is intended to mean keeping substantially.

The particulate material can be provided with a reversibly blocked crosslinker adsorbed using techniques known in the art. For example, a reversibly blocked crosslinker can be combined with and pulverized with particulate matter and conventional dispersion aids to provide the desired size or particulate matter.

As summarized above, the aqueous polymer compositions according to the invention comprising only the reversibly blocked crosslinking agent itself have been found to undergo early crosslinking and are not storage stable. Inclusion of volatilizable crosslinking inhibitors in the composition has surprisingly been found to prevent such early crosslinking and impart storage stability to the composition.

Such early crosslinking and imparting storage stability to the composition can also be achieved as the reversibly blocked crosslinker is present in the composition as adsorbed onto the particulate material.

Without wishing to be bound by theory, the adsorption of reversibly blocked crosslinkers on particulate matter may limit the access of the unblocked crosslinkers to the solubilized copolymer and thus prevent premature crosslinking. I think. Upon application of the composition to the substrate surface, water may leave the composition and, in fact, increase the concentration of copolymers and particulate matter in the composition. This concentration effect makes the copolymer more intimately contacted with the dispersed particulate material, which in turn promotes the reaction of the unblocked crosslinker adsorbed on the particulate material and advances the crosslinking of the copolymer.

In the context of using dispersed or dispersible particulate matter having a reversibly blocked crosslinker adsorbed thereon, the reversibly blocked crosslinker is not "freely" present in solution (ie, the reversibly blocked crosslinker is Bound to particulate matter).

Thus there are two unique techniques that can promote the imparting storage stability to the composition: (i) a volatilizable crosslinking inhibitor in combination with a reversibly blocked crosslinker, and (ii) a reversibly blocked adsorbed thereon. It may be made possible to introduce dispersed particulate matter with a crosslinking agent. Each technique can be used individually or the two techniques can be used in combination.

Two or more different reversibly blocked crosslinkers can be used.

Two or more different volatilizing crosslinking inhibitors may be used.

The present invention also contemplates the use of dispersed or dispersible particulate materials as described herein that do not have a reversibly blocked crosslinker adsorbed thereon.

In another embodiment, the composition according to the invention further comprises a dispersed particulate material having no reversibly blocked crosslinker adsorbed thereon.

In another embodiment, the composition according to the invention is prepared using dispersible particulate material which does not have a reversibly blocked crosslinker adsorbed thereon.

If present, particulate materials can generally be used in the compositions according to the invention in the amounts described by the intended commercial application of the compositions.

Preparation of the composition

The storage stable crosslinkable aqueous polymer composition according to the present invention comprises a reversibly blocked crosslinker for combining or forming a copolymer in an aqueous liquid and also (i) promoting crosslinking of the copolymer in an aqueous liquid, and (ii) ) Is prepared by combining or forming a volatilizable crosslinking inhibitor for inhibiting crosslinking of a copolymer by a reversibly blocked crosslinking agent.

The copolymer may be formed separately from the composition and then combined with other components in an aqueous liquid. Alternatively, the copolymer may be prepared or formed in an aqueous liquid as described herein, and other components of the composition may be combined with the copolymer solution so formed.

In one embodiment, a method of making a storage stable crosslinkable aqueous polymer composition comprises forming a copolymer in an aqueous liquid, the step comprising a volatilized non-gas acid ethylenically unsaturated monomer selected from: Polymerizations in aqueous liquids include:

(i) an ethylenically unsaturated monomer comprising a basic functional group protonated by a volatilizable non-gas acid, the monomer being less than 25 mol% relative to the total moles of ethylenically unsaturated monomer introduced during the polymerization to prepare the copolymer Monomers used in amounts of;

(ii) ethylenically unsaturated monomers comprising functional groups for promoting crosslinking of the copolymer; And

(iii) hydrophobic ethylenically unsaturated monomers.

When volatilizing crosslinking inhibitors are used in the preparation of the composition, apart from any particulate matter combined in the composition, which may or may not have a reversibly blocked crosslinker as well as a reversibly blocked crosslinker adsorbed thereon. And / or in addition thereto, may be combined or formed in an aqueous liquid.

Polymer derived from the composition

The composition according to the invention and the polymer mass / film derived therefrom can provide a number of advantages. The compositions are environmentally friendly because they are generally aqueous and are substantially free of the relatively toxic reagents used in conventional solvent based polymer compositions.

The polymer derived from the composition can advantageously be very hard and have a relatively high Tg. In contrast, polymers derived from emulsion compositions typically need to have a relatively low Tg, allowing for the aggregation of dispersed polymer particles and the formation of a continuous polymer mass or film. Thus, polymer films derived from conventional emulsion compositions are typically quite soft and can result in a painted surface that is sticky together, such as the frame of doors and windows on hot days.

The polymers derived from the composition according to the invention may have a relatively high Tg (eg> 70 ° C.) because the polymers in the composition are soluble in aqueous liquids, and the need for agglomeration of dispersed polymer particles is relevant. none. The polymers derived from the compositions according to the invention may thus be more durable due to their hardness.

The composition according to the invention was found to be able to easily penetrate and wet the wood surface when used as a clear coat. The resulting polymer film provides a hard shiny coating that emphasizes the particles of wood and provides the desired "gloss".

Traditional solvent based glowing enamel paints undergo an oxidative curing process to cure the film. However, the curing process never stops, and the film increases in hardness until cracking, delamination or other stress related failure mechanisms occur.

The polymers derived from the compositions according to the invention do not undergo constant curing since the "curing" is limited by the amount of crosslinking functional groups of the copolymer. The polymers derived from the compositions according to the invention are therefore expected to have a longer useful life than those derived from solvent based polymer compositions.

If necessary, the polymer film / lump derived from the composition according to the invention is advantageously reconstituted back into the liquid by applying a composition comprising a volatizable non-gas acid and a suitable volatilizing crosslinking inhibitor to the polymer film / lump so formed. Can be. In that case, the crosslinking chemistry of the polymer film / lump may be reversed to resolubilize the polymer in the aqueous liquid. Thus compositions comprising volatilizable non-gas acids and volatilizable crosslinking inhibitors can advantageously be used in the form of "paint strippers" to remove polymer films / lumps from the substrate.

The ability to reconstitute the dried crosslinked polymer composition means that the cured composition according to the invention can be shipped as a dried solid and reconstituted at the required destination. Therefore, the transportation cost is greatly reduced because the transportation of water is not paid. Without wishing to limit the invention, for example, DMAEMA (0.15 mol), MMA (0.45) and BMA (0.30) and DAAM (0.10) and acetic acid (0.15), acetone (5ME to DAAM, 0.5 mol) and ADH When a formulation consisting of (0.4 ME to DAAM, 0.04 mole) is dried as a coating or en-mass, it is advantageously water (88 wt.%), Acetic acid (2.9 wt.%) And acetone (9.1 wt. Can be reconstituted by the addition of a solution).

If desired, the composition according to the invention can also be "thinned" by adding to the composition a composition comprising a volatizable non-gas acid and a suitable volatility crosslinking inhibitor.

Application of the composition

The composition according to the invention can be used for various applications such as coating and adhesive applications.

Coatings can be used in the form of paints and clear coats for cosmetic, home or industrial use.

Decorative paints for home applications are suitable applications due to the high gloss and durability of the applied paint film, which is an important necessary property. Home high gloss applications are typically borders, windows, doors, furniture, stone and floor (as clear coats). High gloss can be a feature of the polymers derived from the compositions according to the invention, but the compositions can be formulated to provide a semi-gloss, satin or matte finish.

The composition according to the invention can also be applied to the substrate in the same way as conventional adhesives or paints are applied by, for example, caulking guns, spatula, brushes, rulers or spray guns. Depending on the substrate, typical surface preparations used in traditional paints can be used in the compositions of the present invention.

The composition according to the invention can be used as an adhesive or a component of an adhesive. The composition can provide good bonding to and between the substrate surface.

In makeup, the compositions according to the invention can be used as nail varnishes.

The invention also provides an adhesive, varnish or paint comprising the aqueous polymer composition according to the invention.

As used herein, the term "alkyl", alone or in the compound word, refers to straight chain, branched or cyclic alkyl, preferably C _1-20 alkyl, eg C _1-10 or C _1-6 Indicates. Examples of straight and branched alkyl are methyl, ethyl, n -propyl, isopropyl, n- butyl, sec -butyl, t -butyl, n- pentyl, 1,2-dimethylpropyl, 1,1-dimethyl-propyl, Hexyl, 4-methylpentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, l, l-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1,1,2-trimethylpropyl, heptyl, 5-methylhexyl, 1-methylhexyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl , 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethyl-pentyl, 1,2,3-trimethylbutyl, 1,1,2-trimethylbutyl, 1, 1,3-trimethylbutyl, octyl, 6-methylheptyl, 1-methylheptyl, 1,1,3,3-tetramethylbutyl, nonyl, 1-, 2-, 3-, 4-, 5-, 6- Or 7-methyloctyl, 1-, 2-, 3-, 4- or 5-ethylheptyl, 1-, 2- or 3-propylhexyl, decyl, 1-, 2-, 3-, 4-, 5- , 6-, 7- and 8-methylnonyl, 1-, 2-, 3-, 4-, 5- or 6-ethyloctyl, 1-, 2-, 3- or 4-propylheptyl, undecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-methyldecyl, 1-, 2-, 3-, 4-, 5-, 6- or 7-ethyl Nonyl, 1-, 2-, 3-, 4- or 5-propyloctyl, 1-, 2- or 3-butylheptyl, 1-pentylhexyl, dodecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-methylundecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-ethyldecyl, 1-, 2-, 3-, 4-, 5- or 6-propylnonyl, 1-, 2-, 3- or 4-butyloctyl, 1-2-pentylheptyl and the like. Examples of cyclic alkyls include monocyclic or polycyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like. Where an alkyl group is generally referred to as "propyl", butyl ", etc., it will be understood that where appropriate, it may refer to straight, branched and cyclic isomers. The alkyl group is optionally any one or more as defined herein. It may be substituted by a substituent.

As used herein, the term "alkenyl" refers to a straight, branched or cyclic containing one or more carbon-carbon double bonds, including ethylenically monounsaturated, diunsaturated or polyunsaturated alkyl or cycloalkyl groups as defined above. Group formed from a hydrocarbon moiety, preferably C _2-20 alkenyl (eg C _2-10 or C _2-6 ). Examples of alkenyl are vinyl, allyl, 1-methylvinyl, butenyl, iso-butenyl, 3-methyl-2-butenyl, 1-pentenyl, cyclopentenyl, 1-methyl-cyclopentenyl, 1- Hexenyl, 3-hexenyl, cyclohexenyl , 1-heptenyl, 3-heptenyl, 1-octenyl, cyclooctenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-decenyl , 3-decenyl, 1,3-butadienyl, 1,4-pentadienyl, 1,3-cyclopentadienyl, 1,3-hexadienyl, 1,4-hexadienyl, 1,3 -Cyclohexadienyl, 1,4-cyclohexadienyl, 1,3-cycloheptadienyl, 1,3,5-cycloheptatrienyl and 1,3,5,7-cyclooctatetraenyl Include. Alkenyl groups may be optionally substituted by one or more optional substituents as defined herein.

As used herein, the term “alkynyl” refers to a straight, branched or cyclic containing one or more carbon-carbon triple bonds comprising ethylenically monounsaturated, diunsaturated or polyunsaturated alkyl or cycloalkyl groups as defined above. Group formed from a hydrocarbon residue. Unless the number of carbon atoms is specified, the term preferably refers to C _2-20 alkynyl (eg C _2-10 or C _2-6 ). Examples include ethynyl, 1-propynyl, 2-propynyl, and butynyl isomers, and pentynyl isomers. Alkynyl groups may be optionally substituted by one or more optional substituents as defined herein.

The term "halogen" ("halo") denotes fluorine, chlorine, bromine or iodine (fluoro, chloro, bromo or iodo). Preferred halogens are chlorine, bromine or iodine.

The term “aryl” (or “carboaryl”) refers to any single, multinuclear, conjugated and fused moiety (eg, C _6-18 aryl) of an aromatic hydrocarbon ring system. Examples of aryl are phenyl, biphenyl, terphenyl, quarterphenyl, naphthyl, tetrahydronaphthyl, anthracenyl, dihydroanthracenyl, benzanthracenyl, dibenzanthracenyl, phenanthrenyl, fluorenyl, pyrenyl , Indenyl, azulenyl, chrysenyl. Preferred aryls include phenyl and naphthyl. The aryl group may or may not be optionally substituted by one or more optional substituents as defined herein. The term "arylene" is intended to denote the divalent form of aryl.

The term “carbocyclyl” includes any nonaromatic monocyclic, polycyclic, fused or conjugated hydrocarbon residue, preferably C _3-20 (eg C _3-10 or C _3-8 ). . The ring may be saturated, for example cycloalkyl, or may have one or more double bonds (cycloalkenyl) and / or one or more triple bonds (cycloalkynyl). Particularly preferred carbocyclyl moieties are 5-6 or 9-10 membered ring systems. Suitable examples are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, cyclopentadienyl, cyclohexadienyl, cyclo Octatetraenyl, indanyl, decalinyl and indenyl. Carbocyclyl groups may be optionally substituted with one or more substituents as defined herein. The term "carbocyclylene" is intended to denote the divalent form of carbocyclyl.

The term “heterocyclyl”, when used alone or in the compound word, refers to any monocyclic, polycyclic, fused or conjugated hydrocarbon residue, preferably C _3-20 (eg C _3-10 Or C _3-8 ), wherein one or more carbon atoms are replaced by heteroatoms to provide non-aromatic moieties. Suitable heteroatoms include O, N, S, P and Se, in particular O, N and S. If two or more carbon atoms are replaced, this may be by two or more of the same heteroatoms or different heteroatoms. Heterocyclyl groups may be saturated or partially unsaturated, that is, they may have one or more double bonds. Particularly preferred heterocyclyls are 5-6 and 9-10 membered heterocyclyls. Suitable examples of heterocyclyl groups are aziridinyl, oxiranyl, tyranyl, azetidinyl, oxetanyl, thietanyl, 2H-pyrrolyl, pyrrolidinyl, pyrrolinyl, piperidyl, piperazinyl, Morpholinyl, indolinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, thiomorpholinyl, dioxanyl, tetrahydrofuranyl, tetrahydropyranyl, tetrahydropyrrolyl, tetrahydrothiophenyl, Pyrazolinyl, dioxalanyl, thiazolidinyl, isoxazolidinyl, dihydropyranyl, oxazinyl, thiazinyl, thiomorpholinyl, oxathinyl, ditianyl, trioxanyl, thiadiazinyl, dithia Genyl, tritianyl, azefinyl, oxepinyl, thiepinyl, indenyl, indanyl, 3H-indolyl, isoindolinyl, 4H-quinolazinyl, chromenyl, chromanyl, isochromenyl, Pyranyl and dihydropyranyl. Heterocyclyl groups may be optionally substituted with one or more substituents as defined herein. The term "heterocyclylene" is intended to denote the divalent form of heterocyclyl.

The term “heteroaryl” includes any monocyclic, polycyclic, fused or conjugated hydrocarbon residue in which one or more carbon atoms have been replaced with heteroatoms to provide aromatic moieties. Preferred heteroaryls have 3-20, for example 3-10 ring atoms. Particularly preferred heteroaryls are 5-6 membered and 9-10 membered bicyclic ring systems. Suitable heteroatoms include O, N, S, P and Se, in particular O, N and S. When two or more carbon atoms are replaced, they may be two or more identical heteroatoms or different heteroatoms. Suitable examples of heteroaryl groups are pyridyl, pyrrolyl, thienyl, imidazolyl, furanyl, benzothienyl, isobenzothienyl, benzofuranyl, isobenzofuranyl, indolyl, isoindoleyl, pyrazolyl , Pyrazinyl, pyrimidinyl, pyridazinyl, indolinyl, quinolyl, isoquinolyl, phthalazinyl, 1,5-naphthyridinyl, quinazolinyl, quinazolinyl, quinolinyl, oxazolyl, Thiazolyl, isothiazolyl, isoxazolyl, triazolyl, oxadiazolyl, oxatriazolyl, triazinyl, and furazanyl. Heteroaryl groups may be optionally substituted with one or more substituents as defined herein. The term "heteroarylene" is intended to denote the divalent form of heteroaryl.

The term "acyl", alone or in the compound word, denotes a group containing moiety C═O (not a carboxylic acid, ester or amide). Preferred acyls include C (O) —R ^e , wherein R ^e is hydrogen or alkyl, alkenyl, alkynyl, aryl, heteroaryl, carbocyclyl, or heterocyclyl moiety. Examples of acyl are formyl, straight or branched alkanoyl (eg C _1-20 ), for example acetyl, propanoyl, butanoyl, 2-methylpropanoyl, pentanoyl, 2,2- Dimethylpropanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl, octa Decanoyl, nonadecanoyl and isosanoyl; Cycloalkylcarbonyl such as cyclopropylcarbonyl cyclobutylcarbonyl, cyclopentylcarbonyl and cyclohexylcarbonyl; Aroyl such as benzoyl, toluoyl and naphthoyl; Aralkanoyl, for example phenylalkanoyl (eg phenylacetyl, phenylpropanoyl, phenylbutanoyl, phenylisobutylyl, phenylpentanoyl and phenylhexanoyl) and naphthylalkanoyl (eg , Naphthylacetyl, naphthylpropanoyl and naphthylbutanoyl); Aralkenoyl, for example phenylalkenoyl (eg phenylpropenyl, phenylbutenoyl, phenylmethacryloyl, phenylpentenoyl and phenylhexenoyl and naphthylalkenoyl (eg naph Ylpropenoyl, naphthylbutenoyl and naphthylpentenoyl); aryloxyalkanoyl, such as phenoxyacetyl and phenoxypropionyl; arylthiocarbamoyl, such as phenylthiocarbamoyl; arylgly Oxyloyl, such as phenylglyoxyloyl and naphthylglyoxyloyl; arylsulfonyl, such as phenylsulfonyl and naphthylsulfonyl; heterocyclic carbonyl; heterocyclic alkanoyl, eg For example, thienylacetyl, thienylpropanoyl, thienylbutanoyl, thienylpentanoyl, thienylhexanoyl, thiazolylacetyl, thiadiazolylacetyl and tetrazolylacetyl; heterocyclic alkenoyl, for example , Heterocyclic propenoyl, hete R. Cyclobutenoyl, heterocyclicpentenoyl and heterocyclic hexenoyl and heterocyclicglyoxyloyls such as thiazoliglyoxyloyl and thienylglyoxyloyl R ^x The residue may be optionally substituted as described herein.

The term “sulfoxide”, alone or in the compound word, refers to the group —S (O) R ^f where R ^f represents hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl, And aralkyl. Examples of preferred R ^f include C _1-20 alkyl, phenyl and benzyl.

The term "sulfonyl", alone or in the compound word, refers to the S (O) ₂ -R ^f group, wherein R ^f is hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl And aralkyl. Examples of preferred R ^f include C _1-20 alkyl, phenyl and benzyl.

The term “sulfonamide”, alone or in the compound word, refers to the group S (O) NR ^f R ^f , wherein each R ^f is independently hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl , Carbocyclyl, and aralkyl. Examples of preferred R ^f include C _1-20 alkyl, phenyl and benzyl. In a preferred embodiment at least one R ^f is hydrogen. In another form, R ^f is both hydrogen.

The term “amino” is used herein in the broadest sense understood in the art and includes groups of formula NR ^a R ^b , wherein R ^a and R ^b are independently hydrogen, alkyl, alkenyl, alkynyl, aryl , Carbocyclyl, heteroaryl, heterocyclyl, arylalkyl, and acyl. R ^a and R ^b together with the nitrogen to which they are attached may form a monocyclic or polycyclic ring system, for example a 3-10 membered ring, in particular a 5-6 and 9-10 membered system. Examples of “amino” include NH ₂ , NHalkyl (eg C _1-20 alkyl), NHaryl (eg NHphenyl), NH aralkyl (eg NHbenzyl), NH acyl (eg For example, NHC (O) C _1-20 alkyl, NHC (O) phenyl), Nalkylalkyl (where each alkyl, eg C _1-20 may be the same or different) and optionally one or more 5 or 6 membered rings containing the same or different heteroatoms (eg, O, N and S).

The term “amido” is used herein in the broadest sense understood in the art and includes groups of formula C (O) NR ^a R ^b , wherein R ^a and R ^b are as defined above. Examples of amido are C (O) NH ₂ , C (O) NHalkyl (eg C _1-20 alkyl), C (O) NHaryl (eg C (O) NHphenyl), C (O) NH aralkyl (e.g. C (O) NHbenzyl), C (O) NH acyl (e.g. C (O) NHC (O) C _1-20 alkyl, C (O) NHC ( O) phenyl), C (O) Nalkylalkyl (where each alkyl, eg, C _1-20 may be the same or different) and optionally one or more identical or different heteroatoms (eg O 5 and 6 membered rings containing N and S).

The term “carboxy ester” is used herein in the broadest sense understood in the art and includes groups of the formula CO ₂ R ^g , wherein R ^g is alkyl, alkenyl, alkynyl, aryl, carbocyclyl, hetero And aryl, heterocyclyl, aralkyl, and acyl. Examples of carboxy esters include CO ₂ C _1-20 alkyl, CO ₂ aryl (eg CO ₂ phenyl), CO ₂ aralkyl (eg CO ₂ benzyl).

“Optionally substituted” herein means that the group may or may not be substituted or fused (to form a condensed polycyclic group) with one, two, three or more organic and inorganic groups, including those selected from: alkyl, Alkenyl, alkynyl, carbocyclyl, aryl, heterocyclyl, heteroaryl, acyl, aralkyl, alkaryl, alkheterocyclyl, alkheteroaryl, alkcarbocyclyl, halo, haloalkyl, haloalkenyl , Haloalkynyl, haloaryl, halocarcyclyl, haloheterocyclyl, haloheteroaryl, haloacyl, haloarylalkyl, hydroxy, hydroxyalkyl, hydroxyalkenyl, hydroxyalkynyl, hydroxycarcycle Reel, hydroxyaryl, hydroxyheterocyclyl, hydroxyheteroaryl, hydroxyacyl, hydroxyaralkyl, alkoxyalkyl, alkoxyalkenyl, alkoxyalkynyl, alkoxy Carbocyclyl, alkoxyaryl, alkoxyheterocyclyl, alkoxyheteroaryl, alkoxyacyl, alkoxyaralkyl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, carbocyclyloxy, aralkyloxy, heteroaryloxy, hetero Cyclyloxy, acyloxy, haloalkoxy, haloalkenyloxy, haloalkynyloxy, haloaryloxy, halocarbocyclyloxy, haloaralkyloxy, haloheteroaryloxy, haloheterocyclyloxy, haloacyloxy, Nitro, nitroalkyl, nitroalkenyl, nitroalkynyl, nitroaryl, nitroheterocyclyl, nitroheteroaryl, nitrocarbocyclyl, nitroacyl, nitroaralkyl, amino (NH ₂ ), alkylamino, dialkylamino, Alkenylamino, alkynylamino, arylamino, diarylamino, aralkylamino, diaralkylamino, acylamino, diacylamino, heterocycleamino, hetero Arylamino, carboxy, carboxyester, amido, alkylsulfonyloxy, arylsulphenyloxy, alkylsulphenyl, arylsulphenyl, thio, alkylthio, alkenylthio, alkynylthio, arylthio, aralkylthio, carbo Cyclylthio, heterocyclylthio, heteroarylthio, acylthio, sulfoxide, sulfonyl, sulfonamide, aminoalkyl, aminoalkenyl, aminoalkynyl, aminocarbocyclyl, aminoaryl, aminoheterocyclyl, amino Heteroaryl, aminoacyl, aminoaralkyl, thioalkyl, thioalkenyl, thioalkynyl, thiocarbocyclyl, thioaryl, thioheterocyclyl, thioheteroaryl, thioacyl, thioaralkyl, carboxyalkyl, carboxyl Kenyl, carboxyalkynyl, carboxycarbocyclyl, carboxyaryl, carboxyheterocyclyl, carboxyheteroaryl, carboxyxyl, carboxycyaralkyl, carboxyesteralkyl, carboxyesteralke Neyl, carboxy ester alkynyl, carboxy ester carbocyclyl, carboxy ester aryl, carboxy ester heterocyclyl, carboxy ester heteroaryl, carboxy ester acyl, carboxy ester aralkyl, amidoalkyl, amido alkenyl, amido alkynyl , Amidocarbocyclyl, amidoaryl, amidoheterocyclyl, amidoheteroaryl, amidoacyl, amidoaralkyl, formylalkyl, formylalkenyl, formylalkynyl, formylcarbocyclyl, formylaryl , Formyl heterocyclyl, formyl heteroaryl, formyl acyl, formyl aralkyl, acylalkyl, acyl alkenyl, acylalkynyl, acylcarbocyclyl, acylaryl, acyl heterocyclyl, acyl heteroaryl, acyl acyl, acyl ar Alkyl, sulfoxide alkyl, sulfoxide alkenyl, sulfoxide alkynyl, sulfoxide carbocyclyl, sulfoxidearyl, sulfoxide heterocyclyl, sulfoxide heteroa Reel, sulfoxide acyl, sulfoxide aralkyl, sulfonylalkyl, sulfonylalkenyl, sulfonylalkynyl, sulfonylcarbocyclyl, sulfonylaryl, sulfonylheterocyclyl, sulfonylheteroaryl, sulfonylacyl, sulfonyl Ponylaralkyl, Sulfonamidoalkyl, Sulfonamidoalkenyl, Sulfonamidoalkynyl, Sulfonamidocarbocyclyl, Sulfonamidoaryl, Sulfonamidoheterocyclyl, Sulfonamidoheteroaryl, Sulfonamidoacyl , Sulfonamidoaralkyl, nitroalkyl, nitroalkenyl, nitroalkynyl, nitrocarbocyclyl, nitroaryl, nitroheterocyclyl, nitroheteroaryl, nitroacyl, nitroaralkyl, cyano, sulfate and phosphate groups. Optional substitutions also allow the —CH ₂ — group in the chain or ring to be —O—, —S—, —NR ^a —, —C (O) — (ie carbonyl), —C (O) O— (ie ester), and -C (O) NR ^a - (i.e., can be referred to is replaced by a group selected from an amide), wherein R ^a is as defined above.

Preferred optional substituents are alkyl (eg, C _1-6 alkyl such as methyl, ethyl, propyl, butyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl), hydroxyalkyl (eg, Hydroxymethyl, hydroxyethyl, hydroxypropyl), alkoxyalkyl (e.g. methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, etc.) alkoxy (e.g. , C _1-6 alkoxy, for example methoxy, ethoxy, propoxy, butoxy, cyclopropoxy, cyclobutoxy), halo, trifluoromethyl, trichloromethyl, tribromomethyl, hydroxy , Phenyl (which itself is, for example, C _1-6 alkyl, halo, hydroxy, hydroxyC _1-6 alkyl, C _1-6 alkoxy, haloC _1-6 alkyl, cyano, nitro OC ( O) C _1-6 alkyl, and may be further substituted by amino), benzyl, wherein benzyl itself For example, C _1-6 alkyl, halo, hydroxy, hydroxyC _1-6 alkyl, C _1-6 alkoxy, haloC _1-6 alkyl, cyano, nitro OC (O) C _1-6 Alkyl, and may be further substituted with amino), phenoxy (where phenyl is, for example, C _1-6 alkyl, halo, hydroxy, hydroxyC _1-6 alkyl, C _{1- 6} may be further substituted with alkoxy, haloC _1-6 alkyl, cyano, nitro OC (O) C _1-6 alkyl, and amino), benzyloxy (where benzyl is itself, for example, Addition as C _1-6 alkyl, halo, hydroxy, hydroxyC _1-6 alkyl, C _1-6 alkoxy, haloC _1-6 alkyl, cyano, nitro OC (O) C _1-6 alkyl, and amino ), Amino, alkylamino (e.g., C _1-6 alkyl, e.g. methylamino, ethylamino, propylamino, etc.), dialkylamino (e.g., C _1-6 alkyl) , For example, dimethylamino, diethylamino, dipropylamino), acylami (E.g., NHC (O) CH _3), phenylamino (wherein phenyl is as such, for example, C _1-6 alkyl, halo, hydroxy, hydroxy C _1-6 alkyl, C _{1- 6} may be further substituted with alkoxy, haloC _1-6 alkyl, cyano, nitro OC (O) C _1-6 alkyl, and amino), nitro, formyl, -C (O) -alkyl (e.g. , C _1-6 alkyl, eg acetyl, OC (O) -alkyl (eg C _1-6 alkyl, eg acetyloxy), benzoyl (where the phenyl group is itself, eg For example, C _1-6 alkyl, halo, hydroxy hydroxyC _1-6 alkyl, C _1-6 alkoxy, haloC _1-6 alkyl, cyano, nitro OC (O) C _1-6 alkyl, and amino May be further substituted), replacement of CH ₂ by C═O, CO ₂ H, CO ₂ alkyl (eg C _1-6 alkyl, eg methyl ester, ethyl ester, propyl ester, Butyl ester), CO ₂ phenyl (where phenyl is itself, for example C _1-6 alkyl, halo, hydroxy, May be further substituted with hydroxyl C _1-6 alkyl, C _1-6 alkoxy, halo C _1-6 alkyl, cyano, nitro OC (O) C _1-6 alkyl, and amino), CONH ₂ , CONH Phenyl, where phenyl is itself, for example C _1-6 alkyl, halo, hydroxy, hydroxyl C _1-6 alkyl, C _1-6 alkoxy, halo C _1-6 alkyl, cyano, nitro OC (O) C _1-6 alkyl, and may be further substituted with amino), CONHbenzyl, where benzyl is itself, eg, C _1-6 alkyl, halo, hydroxy hydroxyl C _{1 Optionally} substituted with _-6 alkyl, C _1-6 alkoxy, halo C _1-6 alkyl, cyano, nitro OC (O) C _1-6 alkyl, and amino), CONH alkyl (e.g., C _1-6 alkyl, eg methyl ester, ethyl ester, propyl ester, butyl amide), CONHdialkyl (eg C _1-6 alkyl), aminoalkyl (eg HN C _1-6 alkyl -, C _1-6 alkylHN-C _1-6 alkyl- and (C _1-6 alkyl) ₂ NC _1-6 alkyl-), thioalkyl (example For example, HS C _1-6 alkyl-), carboxyalkyl (eg HO ₂ CC _1-6 alkyl-), carboxyesteralkyl (eg C _1-6 alkylO ₂ CC _1-6 alkyl- ), Amidoalkyl (eg H ₂ N (O) CC _1-6 alkyl-, H (C _1-6 alkyl) N (O) CC _1-6 alkyl-), formylalkyl (eg , OHCC _1-6 alkyl-), acylalkyl (eg C _1-6 alkyl (O) CC _1-6 alkyl-), nitroalkyl (eg O ₂ NC _1-6 alkyl-), sulfoxide Sidealkyls (eg R (O) SC _1-6 alkyl, eg C _1-6 alkyl (O) SC _1-6 alkyl-), sulfonylalkyl (eg R (O) ₂ ) SC _1-6 alkyl- such as C _1-6 alkyl (O) ₂ SC _1-6 alkyl-), sulfonamidoalkyl (eg ₂ HRN (O) SC _1-6 alkyl, H ( C _1-6 alkyl) N (O) SC _1-6 alkyl-).

As used herein in the broadest sense, the term “heteroatom” or “hetero” refers to any atom other than a carbon atom that may be the number of cyclic organic groups. Specific examples of heteroatoms include nitrogen, oxygen, sulfur, phosphorus, boron, silicon, selenium and tellurium, more particularly nitrogen, oxygen and sulfur.

In the monovalent substitution, the term described as "[A group] [group B]" refers to the group A connected by the divalent form of the group B. For example, "[A group] [alkyl]" refers to a specific A group (e.g., hydroxy, amino, etc.) linked by divalent alkyl, ie alkylene (e.g., hydroxyethyl Is intended to represent HO-CH ₂ -CH-. Thus, the term described as "[group] oxy" refers to a particular group linked by oxygen, for example the term "alkoxy" or "alkyloxy", "alkenyl" or "alkenyloxy", "alkynoxy" Or alkynyloxy "," aryloxy "and" acyloxy "refer to alkyl, alkenyl, alkynyl, aryl and acyl groups as defined above, each linked by oxygen. Similarly," [group] thio " The term described herein refers to specific groups linked by sulfur, for example, the terms "alkylthio", "alkenylthio", alkynylthio "and" arylthio "are each alkyl as defined above linked by sulfur , Alkenyl, alkynyl and aryl groups.

The invention below will be explained below with reference to the following non-limiting examples.

Example

Example 1

Synthesis of Copolymer in Water Under Nitrogen Atmosphere with Seed Polymer

DMAEMA: MMA: iBMA: DAAM 20: 50: 25: 5 ratio (30 wt% solids)

Water (1.975 L) was deoxygenated by N ₂ bubbling and added to a 5 L reactor under N ₂ atmosphere. Thus initiator 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (known as VA-044) (4.41 g, 13.6 mmol) and seed polymer solution (60 mL , 20: 50: 25: 5 molar ratio of DMAEMA: MMA: iBMA: DAAM polymer (solution with 30 wt% solids of about 20K Mn) was added. Stirring with an overhead stirrer (double propeller blades) was started at 250 rpm and the reaction temperature was raised to 62.5 ° C. 2- (dimethylamino) ethyl methacrylate (DMAEMA) (221.7 g, 1410 mmol), methyl methacrylate (MMA) (352.9 g, 3525 mmol), isobutyl methacrylate (iBMA) (250.6 g, 1763 mmol ), Diacetone acrylamide (DAAM) (59.65 g, 352.5 mmol), a mixture of glacial acetic acid (84.66 g, 1410 mmol) and terpinolene (4.80 g, 35.2 mmol) is deoxygenated by N ₂ bubbling and peristaltic pump Was injected for a 4 hour period. At the same time, VA-044 (13.23 g, 40.9 mmol) dissolved in H ₂ O (100 mL) was injected into the reaction for a 6 hour period using a syringe pump.

The reaction became more viscous after monomer injection and the stirring speed was increased to 300 rpm. 6 hours after the end of the initiator feed, a single VA-044 (2.21 g, 6.84 mmol) was added and stirring was increased to 350 rpm. The reaction solution can then be used as is.

Solid content 30% (weighing)

¹ H NMR (acetone-d ₆ ): MMA Broad 3.63 ppm, iBMA Broad 3.76 ppm, DMAEMA Broad 4.11 ppm. DMAEMA: MMA: iBMA Ratio 19.7: 49.3: 26.0: 5.0

Conversion (GC / MS): DMAEMA 100%, MMA 99.99%, iBMA 99.91%

GPC (DMAc, PMMA standard): M _n = 20.3 K, PD = 1.73

Shimadzu-DMAc GPC Molecular Weight Characterization.

Gel Permeation Chromatography (GPC) was applied to the CMB-20A regulator system, SIL-20A HT autosampler, LC-20AT tandem pump system, DGU-20A outgassing unit, CTO-20AC column oven, RDI-10A refractive index detector, and 4Х Waters It was performed on a Shimadzu system equipped with Styragel columns (HT2, HT3, HT4, and HT5, each providing an effective molar mass range of 300 mm 7.8 7.8 mm ² , 100-4 × 10 ⁶ ). N, N -dimethylacetamide (DMAc) (containing 4.34 g L- ¹ lithium bromide (LiBr)) was used as the eluent at a flow rate of 1 mL / min at 80 ° C. Number ( M _n ) and weight average ( M _w ) molar masses were evaluated using Shimadzu LC solution software. GPC columns were calibrated with low dispersion polystyrene (PSt) and poly (methyl methacrylate) (PMMA) standards (Polymer Laboratories) ranging from 575 to 3,242,000 g mol ⁻¹ and 1010 to 2,136,000 g mol ⁻¹ , respectively. Record in PSt and PMMA equivalents. A third order polynomial was used to fit the log M _p versus time calibration curve, which was nearly linear across the molar mass range.

This method was used in the analysis of polymers prepared in other examples.

Example 2

Synthesis of Copolymer in Water Under Carbon Dioxide Atmosphere with Seed Polymer

DMAEMA: MMA: iBMA: DAAM 20: 50: 25: 5 ratio (30 wt% solids)

Water (625 mL) was deoxygenated by CO ₂ bubbling and then added to a 2 L reactor under CO ₂ atmosphere, to which initiator 2,2′-azobis [2- (2-imidazolin-2-yl) propane ] 30 weight of dihydrochloride (known as VA-044) (1.47 g, 4.55 mmol) and seed polymer solution (20: 50: 25: 5 molar ratio of polymer of DMAEMA: MMA: iBMA: DAAM (about 20K Mn)) 20 mL of solution with% solids) was added. Stirring with an overhead stirrer (half moon blade) was started at 330 rpm and the reaction temperature was raised to 60 ° C. 2- (dimethylamino) ethyl methacrylate (73.89 g, 470 mmol), methyl methacrylate (117.6 g, 1175 mmol), isobutyl methacrylate (83.53 g, 587.5 mmol), diacetone acrylamide (19.88 g , 117.5 mmol), glacial acetic acid (28.22 g, 470 mmol) and terpinolene (1.60 g, 11.75 mmol) were deoxygenated with N ₂ bubbling and injected for a period of 4 hours using a peristaltic pump. At the same time, VA-044 (4.41 g, 13.6 mmol) dissolved in H ₂ O (50 mL) was injected into the reaction for a 6 hour period using a syringe pump.

The reaction became more viscous after monomer injection and the stirring speed was increased to 400 rpm. Six hours after the end of the initiator feed, a single VA-044 (735 mg, 2.27 mmol) was added and stirring was increased to 450 rpm. The reaction was decanted and used as is.

Solid content 30% (weighing)

¹ H NMR (acetone-d ₆ ): MMA broad 3.63 ppm, iBMA broad 3.76 ppm, DMAEMA broad 4.11 ppm DMAEMA: MMA: iBMA ratio 20.6: 46.3: 28.1

Conversion (GC / MS): DMAEMA 100%, MMA 99.99%, iBMA 99.91%

GPC (DMAc, PMMA standard): M _n = 22.7 K, PD = 1.61

Example 3

Synthesis of Copolymer in Water Under Carbon Dioxide Atmosphere with Seed Polymer

DMAEMA: MMA: iBMA: DAAM 20: 50: 25: 5 ratio (35 wt% solids)

To H ₂ O (82 mL) was added initiator 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (known as VA-044, 0.264 g) and the solution Was deoxygenated by bubbling with CO ₂ . This solution was added to a 500 mL reactor containing seed polymer solution (3 mL, from a pre-synthetic batch of polymer solution of the same composition with a 30 wt% solids loading) under CO ₂ atmosphere. Stirring with an overhead stirrer (half moon blade) was started at 350 rpm and the reaction temperature was raised to 60 ° C. Dimethylaminoethyl methacrylate (12.86 g, 81.8 mmol), methyl methacrylate (20.47 g, 205 mmol), isobutyl methacrylate (14.54 g, 102 mmol), diacetone acrylamide (3.46 g, 20.5 mmol) , A mixture of glacial acetic acid (4.91 g, 81.8 mmol) and terpinolene (0.19 g, 1.39 mmol) was deoxygenated by N ₂ bubbling and injected using a syringe pump for a 4 hour period. Additional aliquots of initiator solution (0.899 g in 10 g water) were added at t = 1.5, 3, 4.5 and 6 hrs (3.11, 3.11, 3.11, 1.56 mL, respectively). The reaction became more viscous after monomer injection and the stirring speed was increased to 400 rpm. The reaction was then decanted and used as is.

Solid content 35% (calculated); 36.3% by weight.

¹ H NMR (acetone-d ₆ ): MMA Broad 3.63 ppm, iBMA Broad 3.76 ppm, DMAEMA Broad 4.11 ppm.

Conversion ( ¹ H NMR, acetone-d ₆ ): DMAEMA 100%, MMA> 99.9%, iBMA 99.6%

GPC (DMAc, PMMA standard): M _n = 25.5 K, M _w = 46.5 K, PD = 1.82

Example 4

Synthesis of Copolymer in Water Under Carbon Dioxide Atmosphere without Seed Polymer

DMAEMA: MMA: iBMA: DAAM 20: 50: 25: 5 ratio (35 wt% solids)

To H ₂ O (82 mL) was added initiator 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (known as VA-044, 0.264 g) and the solution Was deoxygenated by bubbling with CO ₂ . This solution was added to a 500 mL reactor under CO ₂ atmosphere. Stirring with an overhead stirrer (half moon blade) was started at 350 rpm and the reaction temperature was raised to 60 ° C. Dimethylaminoethyl methacrylate (12.86 g, 81.8 mmol), methyl methacrylate (20.47 g, 205 mmol), isobutyl methacrylate (14.54 g, 102 mmol), diacetone acrylamide (3.46 g, 20.5 mmol) , A mixture of glacial acetic acid (4.91 g, 81.8 mmol) and terpinolene (0.19 g, 1.39 mmol) was deoxygenated by N ₂ bubbling and injected using a syringe pump for a 4 hour period. Additional aliquots of initiator solution (0.899 g in 10 g water) were added to t = 1.5, 3, 4.5 and 6 hours (3.11, 3.11, 3.11, 1.56 mL, respectively). The reaction became more viscous after monomer injection and the stirring speed was increased to 400 rpm. The reaction was then decanted and used as is.

Solid content 35% (calculated); 36.8% by weight.

¹ H NMR (acetone-d ₆ ): MMA Broad 3.63 ppm, iBMA Broad 3.76 ppm, DMAEMA Broad 4.11 ppm.

Conversion ( ¹ H NMR, acetone-d ₆ ): DMAEMA 100%, MMA> 99.9%, iBMA 99.7%

GPC (DMAc, PMMA standard): M _n = 22.4 K, M _w = 42.6 K, PD = 1.90

Example 5

Synthesis of Copolymer in Water Under Nitrogen Atmosphere with Seed Polymer

DMAEMA: MMA: iBMA: DAAM 15: 50: 30: 5 ratio (40 wt% solids)

To H ₂ O (75 mL) was added initiator 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (also known as VA-044, 0.304 g) and the solution Was deoxygenated by bubbling with N ₂ . This solution was added under nitrogen atmosphere to a 500 mL reactor containing seed polymer solution (3 mL of the pre-synthesized batch of polymer described in Example 3). Stirring with an overhead stirrer (half moon blade) was started at 350 rpm and the reaction temperature was raised to 60 ° C. Dimethylaminoethyl methacrylate (11.10 g, 70.6 mmol), methyl methacrylate (23.56 g, 235 mmol), isobutyl methacrylate (20.08 g, 141 mmol), diacetone acrylamide (4.24 g, 23.5 mmol) , A mixture of glacial acetic acid (4.24 g, 70.6 mmol) and terpinolene (0.15 g, 1.13 mmol) was deoxygenated by N ₂ bubbling and injected using a syringe pump for a 4 hour period. Additional initiator solution was prepared (1.035 g of VA-044 dissolved in 10 g water), deoxygenated by nitrogen bubbling, 9.46 mL of this was infused for a 6 hour period using a syringe pump, and the residue (1.58 mL). ) Was injected at one time at the 6 hour mark. Heating was continued for 7 hours. The reaction became more viscous after monomer injection and the stirring speed was increased to 400 rpm. The reaction was cooled to ambient temperature and poured into a sealed container.

Solid content: 40% (by weight)

¹ H NMR (acetone-d ₆ ): MMA Broad 3.63 ppm, iBMA Broad 3.76 ppm, DMAEMA Broad 4.11 ppm.

Conversion ( ¹ H NMR, acetone-d ₆ ): DMAEMA 100%, MMA> 99.9%, iBMA 99.4%

GPC (DMAc, PMMA standard): M _n = 26.5 K, M _w = 55.6 K, PD = 2.10

Example 6

Synthesis of Copolymer in Water Under Nitrogen Atmosphere without Seed Polymer

DMAEMA: MMA: iBMA: DAAM 15: 50: 30: 5 ratio (29 wt% solids)

To H ₂ O (90 mL) was added initiator 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (known as VA-044, 0.200 g) and the solution Was deoxygenated by N ₂ bubbling. This solution was added to a 500 mL reactor under a nitrogen atmosphere. Stirring with an overhead stirrer (half moon blade) was started at 350 rpm and the reaction temperature was raised to 60 ° C. Dimethylaminoethyl methacrylate (7.55 g, 48 mmol), methyl methacrylate (16.03 g, 160 mmol), isobutyl methacrylate (13.66 g, 96 mmol), diacetone acrylamide (2.71 g, 16 mmol) , A mixture of glacial acetic acid (2.88 g, 48 mmol) and terpinolene (0.218 g, 1.6 mmol) was deoxygenated with N ₂ bubbling and injected using a syringe pump for a 4 hour period. Additional initiator solution was prepared (0.600 g of VA-044 dissolved in 10 mL water), deoxygenated by nitrogen bubbling and injected for a 6 hour period using a syringe pump. Additional solid initiator (0.1-0 g of VA-044) was added in one at 6 hour mark. Heating was continued for 7 hours. The reaction was cooled to ambient temperature and poured into a sealed container.

Solids content: 29% (by weight)

¹ H NMR (acetonitrile-d ₃ ): MMA Broad 3.58 ppm, iBMA Broad 3.72 ppm, DMAEMA Broad 4.11 ppm.

Conversion ( ¹ H NMR, acetonitrile-d ₃ ): DMAEMA 100%, MMA> 99.9%, iBMA 99.3%

GPC (DMAc, PMMA standard): M _n = 24.8 K, M _w = 40.2 K, PD = 1.62

Tg (heating / cooling / heating cycle from -50 ° C. to 200 ° C. at 10K / min with dry polymer film, N ₂ ): 81.81 ° C.

Example 7

Synthesis of Copolymer in Water Under Nitrogen Atmosphere with Seed Polymer

DMAEMA: MMA: iBMA: DAAM 10: 50: 35: 5 ratio (29 wt% solids)

To H ₂ O (90 mL) was added initiator 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (known as VA-044, 0.200 g) and the solution Was deoxygenated by N ₂ bubbling. This solution was added under nitrogen atmosphere to a 500 mL reactor containing seed polymer solution (3 mL of the pre-synthesized batch of polymer described in Example 6). Stirring with an overhead stirrer (half moon blade) was started at 350 rpm and the reaction temperature was raised to 60 ° C. Dimethylaminoethyl methacrylate (5.03 g, 32 mmol), methyl methacrylate (16.02 g, 160 mmol), isobutyl methacrylate (15.92 g, 112 mmol), diacetone acrylamide (2.71 g, 16 mmol) , A mixture of glacial acetic acid (1.92 g, 32 mmol) and terpinolene (0.218 g, 1.6 mmol) was deoxygenated by N ₂ bubbling and injected using a syringe pump for a 4 hour period. Additional initiator solution was prepared (0.600 g of VA-044 dissolved in 10 mL water), deoxygenated by nitrogen bubbling and injected for a 6 hour period using a syringe pump. Additional solid initiator (0.1-0 g of VA-044) was added in one at 6 hour mark. Heating was continued for 7 hours. The reaction was cooled to ambient temperature and poured into a sealed container.

Solids content: 29% (by weight)

¹ H NMR (acetonitrile-d ₃ ): MMA Broad 3.56 ppm, iBMA Broad 3.70 ppm, DMAEMA Broad 4.05 ppm.

Conversion ( ¹ H NMR, acetonitrile-d ₃ ): DMAEMA 100%, MMA> 99.9%, iBMA 99.6%

GPC (DMAc, PMMA standard): M _n = 18.9 K, M _w = 36.1 K, PD = 1.91

Tg (heating / cooling / heating cycle from −50 ° C. to 200 ° C. at 10 K / min with dry polymer film, N ₂ ): 81.74 ° C.

Example 8

Synthesis of Copolymer in Water Under Nitrogen Atmosphere with Seed Polymer

DMAEMA: MMA: iBMA: DAAM 10: 50: 35: 5 ratio (35 wt% solids)

To H ₂ O (90 mL) was added initiator 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (known as VA-044, 0.200 g) and the solution Was deoxygenated by N ₂ bubbling. This solution was added under nitrogen atmosphere to a 500 mL reactor containing seed polymer solution (3 mL of the pre-synthesized batch of polymer described in Example 6). Stirring with an overhead stirrer (half moon blade) was started at 350 rpm and the reaction temperature was raised to 60 ° C. Dimethylaminoethyl methacrylate (6.80 g, 43 mmol), methyl methacrylate (21.65 g, 216 mmol), isobutyl methacrylate (21.53 g, 151 mmol), diacetone acrylamide (3.66 g, 22 mmol) , A mixture of glacial acetic acid (2.60 g, 43 mmol) and terpinolene (0.200 g, 1.47 mmol) was deoxygenated by N ₂ bubbling and injected using a syringe pump for a 4 hour period. Additional initiator solution was prepared (0.600 g of VA-044 dissolved in 10 mL water), deoxygenated by nitrogen bubbling and injected for a 6 hour period using a syringe pump. Additional solid initiator (0.1-0 g of VA-044) was added in one at 6 hour mark. Heating was continued for 7 hours. The reaction was cooled to ambient temperature and poured into a sealed container.

Solids content: 36% (by weight)

¹ H NMR (acetonitrile-d ₃ ): MMA Broad 3.56 ppm, iBMA Broad 3.71 ppm, DMAEMA Broad 4.03 ppm.

Conversion ( ¹ H NMR, acetonitrile-d ₃ ): DMAEMA 100%, MMA> 99.9%, iBMA 99.1%

GPC (DMAc, PMMA standard): M _n = 23.0 K, M _w = 48.9 K, PD = 2.12

Tg (heating / cooling / heating cycle from −50 ° C. to 200 ° C. at 10 K / min with dry polymer film, N ₂ ): 89.63 ° C.

Example 9

Synthesis of Copolymer in Water Under Nitrogen Atmosphere with Seed Polymer

DMAEMA: MMA: iBMA: DAAM 15: 50: 30: 5 ratio (45 wt% solids)

To H ₂ O (70 mL) was added initiator 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (known as VA-044, 0.333 g) and the solution Was deoxygenated by N ₂ bubbling. This solution was added under nitrogen atmosphere to a 500 mL reactor containing seed polymer solution (3 mL of a pre-synthetic batch of polymer in DMAEMA: MMA: iBMA: DAAM 15: 50: 30: 5 ratio (35 wt% solids)). . Stirring with an overhead stirrer (half moon blade) was started at 350 rpm and the reaction temperature was raised to 60 ° C. Dimethylaminoethyl methacrylate (12.80 g, 81 mmol), methyl methacrylate (27.17 g, 271 mmol), isobutyl methacrylate (23.16 g, 162 mmol), diacetone acrylamide (4.59 g, 27 mmol) , A mixture of glacial acetic acid (4.89 g, 81 mmol) and terpinolene (0.177 g, 1.30 mmol) was deoxygenated by N ₂ bubbling and injected using a syringe pump for a 4 hour period. Additional initiator solution was prepared (1.000 g of VA-044 dissolved in 10 mL water), deoxygenated by nitrogen bubbling and injected for a 6 hour period using a syringe pump. Additional solid initiator (VA-044 0.167 g) was added at one time in the 6 hour mark. Heating was continued for 7 hours. The reaction was cooled to ambient temperature and poured into a sealed container.

Solids content: 49% (by weight)

¹ H NMR (acetonitrile-d ₃ ): MMA Broad 3.56 ppm, iBMA Broad 3.70 ppm, DMAEMA Broad 4.04 ppm.

Conversion ( ¹ H NMR, acetonitrile-d ₃ ): DMAEMA 100%, MMA> 99.9%, iBMA 99.5%

GPC (DMAc, PMMA standard): M _n = 24.6 K, M _w = 53.7 K, PD = 2.18

Tg (heating / cooling / heating cycle from −50 ° C. to 200 ° C. at 10 K / min with dry polymer film, N ₂ ): 78.14 ° C.

Then, monomer reduction after polymerization was performed to minimize residual iBMA monomer content in the polymer solution. The polymer solution was heated to 40 ° C., to which tert -butyl hydroperoxide (0.2 mL of 70% aqueous solution) was added. Sodium formaldehyde sulfoxylate solution (0.0223 g in 1 mL water, 1 molar equivalent relative to hydroperoxide) was prepared and deoxygenated by nitrogen bubbling. Half of this solution was first added to the stirred polymer solution under nitrogen, followed by the other half after 30 minutes. Heating was continued for an additional hour. Analysis by ¹ H NMR (d ₆ -acetone) showed an increase in iBMA monomer conversion from initial 99.5% to> 99.9%.

Example 10

Synthesis of Copolymer in Water Under Carbon Dioxide Atmosphere with Seed Polymer

DMAEMA: MMA: iBMA: DAAM: UMA 20: 45: 25: 5: 5 ratio (28 wt% solids)

Ureido methacrylate was a 30% w / w solution in methyl methacrylate. In the synthesis, 10.57 g of UMA 30% w / w in MMA solution was additionally used for 7.02 g of pure MMA, resulting in a total MMA mass of 14.42 g and a total mass of 3.171 g UMA.

Water (90 mL) was deoxygenated by N ₂ bubbling and then added to a 500 mL reactor under N ₂ atmosphere, to which initiator 2,2′-azobis [2- (2-imidazolin-2-yl) propane ] 30 weight of dihydrochloride (known as VA-044) (0.200 g, 0.619 mmol) and seed polymer solution (20: 50: 25: 5 molar ratio of polymer of DMAEMA: MMA: iBMA: DAAM (about 20K Mn)) 3 mL of a solution with% solids) was added. Stirring with an overhead stirrer (half-moon blade) was started at 330 rpm and the reaction temperature was raised to 60 ° C. 2- (dimethylamino) ethyl methacrylate (10.06 g, 64 mmol), methyl methacrylate (14.42 g, 144 mmol), isobutyl methacrylate (11.38 g, 80 mmol), diacetone acrylamide (2.71 g , 16 mmol), ureido methacrylate (UMA) (3.17 g, 16 mmol), a mixture of glacial acetic acid (3.84 g, 64 mmol) and terpinolene (0.218 g, 1.6 mmol) deoxygenated by N ₂ bubbling And injected using a syringe pump for a 4 hour period. At the same time, VA-044 (0.600 g, 1.87 mmol) dissolved in N ₂ degassed H ₂ O (10 mL) was injected into the reaction using a syringe pump for a 6 hour period.

The reaction became more viscous after monomer injection and the stirring speed was increased to 400 rpm. Six hours after the end of the initiator feed, a single VA-044 (0.100 g, 0.309 mmol) was added and stirring was increased to 450 rpm. The reaction was decanted and used as is.

28% solids (by weight)

¹ H NMR (acetone-d ₆ ): MMA Broad 3.63 ppm, iBMA Broad 3.76 ppm, DMAEMA Broad 4.11 ppm. DMAEMA: MMA: iBMA Ratio 18.9: 43.3: 27.8

Conversion ( ¹ H NMR, acetone-d ₆ ): all monomers> 99.9%

GPC (DMAc, PMMA standard): M _n = 22.6 K, PD = 1.83

Example 11

Synthesis of Copolymer in Water Under Nitrogen Atmosphere with Seed Polymer Using VA-061 Initiator Acidified by Acetic Acid

DMAEMA: MMA: iBMA: DAAM 20: 50: 25: 5 ratio (35 wt% solids)

Initiator 2,2'-azobis [2- (2-imidazolin-2-yl) propane] (known as VA-061, 0.205 g) and glacial acetic acid (0.098 g, initiator in H ₂ O (82 mL) 2 mol eq) was added and the solution was deoxygenated by N ₂ bubbling. This solution was added under nitrogen atmosphere to a 500 mL reactor containing seed polymer solution (3 mL of the pre-synthesized batch of polymer described in Example 3). Stirring with an overhead stirrer (half moon blade) was started at 350 rpm and the reaction temperature was raised to 60 ° C. Dimethylaminoethyl methacrylate (12.86 g, 81.8 mmol), methyl methacrylate (20.47 g, 205 mmol), isobutyl methacrylate (14.54 g, 102 mmol), diacetone acrylamide (3.46 g, 20.5 mmol) , A mixture of glacial acetic acid (4.91 g, 81.8 mmol) and terpinolene (0.19 g, 1.39 mmol) was deoxygenated by N ₂ bubbling and injected using a syringe pump for a 4 hour period. Additional initiator solution was prepared (0.696 g of VA-061 dissolved in 9.5 g of water containing 0.334 g of glacial acetic acid), deoxygenated by nitrogen bubbling, and 9.03 mL of this was injected for 6 hours using a syringe pump , Residue (1.5 mL) was injected at a time on the 6 hour mark. Heating was continued for 7 hours. The reaction became more viscous after monomer injection and the stirring speed was increased to 400 rpm. The reaction was cooled to ambient temperature and a viscous but easily poured polymer mixture was obtained.

Solids content: 35.2% by weight.

¹ H NMR (acetone-d ₆ ): MMA Broad 3.63 ppm, iBMA Broad 3.76 ppm, DMAEMA Broad 4.11 ppm.

Conversion ( ¹ H NMR, acetone-d ₆ ): DMAEMA 100%, MMA> 99.9%, iBMA 99.8%

GPC (DMAc, PMMA standard): M _n = 22.8 K, M _w = 42.1 K, PD = 1.84

Example 12

Synthesis of Copolymer in Water Under Nitrogen Atmosphere by Replacing Isobutyl Methacrylate with n -Butyl Methacrylate and Seed Polymer

DMAEMA: MMA: n- BMA: DAAM 15: 50: 30: 5 ratio (40 wt% solids)

To H ₂ O (66.5 mL) was added initiator 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (known as VA-044, 0.274 g) and the solution Was deoxygenated by N2 bubbling. This solution was added under nitrogen atmosphere to a 500 mL reactor containing seed polymer solution (3 mL of the pre-synthetic batch of polymer described in Example 5). Stirring with an overhead stirrer (half moon blade) was started at 350 rpm and the reaction temperature was raised to 60 ° C. Dimethylaminoethyl methacrylate (10 g, 63.6 mmol), methyl methacrylate (21.23 g, 212 mmol), n -butyl methacrylate (18.09 g, 127 mmol), diacetone acrylamide (3.59 g, 21.2 mmol ), A mixture of glacial acetic acid (3.82 g, 63.6 mmol) and terpinolene (0.14 g, 1.02 mmol) was deoxygenated by N ₂ bubbling and injected using a syringe pump for a 4 hour period. Additional initiator solution was prepared (0.932 g of VA-044 dissolved in 10 g of water), deoxygenated by nitrogen bubbling, 9.4 mL of which was injected using a syringe pump for a 6 hour period, and the residue (about 1.5 mL) was injected at one time at the 6 hour mark. Heating was continued for 7 hours. The reaction became more viscous after monomer injection and the stirring speed was increased to 400 rpm. The reaction was cooled to ambient temperature and a viscous but pourable polymer mixture was obtained.

Solids content: 41.0% by weight.

¹ H NMR (acetone-d ₆ ): MMA Broad 3.63 ppm, nBMA Broad 3.94 ppm, DMAEMA Broad 4.11 ppm.

Conversion ( ¹ H NMR, acetone-d ₆ ): DMAEMA 100%, MMA> 99.9%, nBMA 99.8%

GPC (DMAc, PMMA standard): M _n = 23.3 K, M _w = 46.9 K, PD = 2.01

Example 13

Synthesis of Copolymer in Water Under Nitrogen Atmosphere with Seed Polymer

DMAEMA: MMA: iBMA: DAAM 15: 50: 30: 5 ratio (50 wt% solids)

To H ₂ O (70 mL) was added initiator 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (known as VA-044, 0.365 g) and the solution Was deoxygenated by N ₂ bubbling. This solution was added under nitrogen atmosphere to a 500 mL reactor containing seed polymer solution (3 mL of a pre-synthetic batch of polymer in DMAEMA: MMA: iBMA: DAAM 15: 50: 30: 5 ratio (29 wt% solids) polymer). . Stirring with an overhead stirrer (half moon blade) was started at 350 rpm and the reaction temperature was raised to 60 ° C. Dimethylaminoethyl methacrylate (14.00 g, 89 mmol), methyl methacrylate (29.72 g, 297 mmol), isobutyl methacrylate (25.33 g, 178 mmol), diacetone acrylamide (5.02 g, 30 mmol) , A mixture of glacial acetic acid (5.35 g, 89 mmol) and terpinolene (0.194 g, 1.42 mmol) was deoxygenated by N ₂ bubbling and injected using a syringe pump for a 4 hour period. Additional initiator solution was prepared (1.094 g of VA-044 dissolved in 10 mL of water), deoxygenated by nitrogen bubbling and injected for a 6 hour period using a syringe pump. Additional solid initiator (0.1-0 g of VA-044) was added at one time in the 6 hour mark. Heating was continued for 7 hours. The reaction was cooled to ambient temperature and poured into a sealed container.

Solids content: 52% by weight

¹ H NMR (acetonitrile-d ₃ ): MMA Broad 3.58 ppm, iBMA Broad 3.73 ppm, DMAEMA Broad 4.07 ppm.

Conversion ( ¹ H NMR, acetonitrile-d ₃ ): DMAEMA 100%, MMA> 99.9%, iBMA 99.2%

GPC (DMAc, PMMA standard): M _n = 22.2K, M _w = 42.1K, PD = 1.90

Tg (heating / cooling / heating cycle from −50 ° C. to 200 ° C. at 10 K / min with dry polymer film, N ₂ ): 79.55 ° C.

Example 14

N, N-di (propane-2-ylidene) adipohydrazide

Adipic acid dihydrazide (ADH) (16.0 g, 0.09 mol) was refluxed in acetone (50 mL) for 4 hours, and after cooling, excess acetone was removed under vacuum to remove N, N-di (propane-2). -Ylidene) adipohydrazide (23 g, 99%) was obtained. ¹ H NMR (DMSO): 9.86 (2H), 2.46 (2H) (under DMSO), 2.15 (2H), 1.87 (6H), 1.79 (6H) 1.49 (4H)

Example 15

Tetraacetic Acid Tetramethyl Ester

Tetraacetic acid tetramethyl esters are described by Keana et. al., John F W Keana and Jeffry S. Mann , J. Org. Chem ., 1990 , 55, 2868-2871.].

2,2 ', 2' ', 2' ''-(ethane-1,2-diylbis (azaneriyl)) tetraacetohydrazide

To ethylenedinitrile tetraacetic acid tetramethyl ester (3.32 g, 9.5 mmol) in 33 ml of ethanol was added hydrazine hydrate (50-60%) (Sigma-Aldrich) (2.6 g, 2.76 ml, 41-48 mmol). It was. The solution was O / N refluxed and the clear solution turned cloudy and after cooling, a white high crystalline solid precipitated out, the solid collected, washed with ethanol and dried. ¹ H NMR (D ₂ O): 3.12 (8H), 2.68 (4H).

Example 16

Polymeric hydrazide.

chapter 1. Poly (methyl acrylate)

Methyl acrylate (45 ml, 43.0 g, 0.50 mol), toluene (45 ml), dodecanethiol (3.55 ml, 3 g, 17.5 mmol) and 1,1'-azobis (cyclohexanecarbonitrile) (0.72 g 2.9 mmol) was degassed with bubbling nitrogen for 15 minutes. The solution was heated at 80 ° C. under N 2 for 18 h. After cooling, toluene (50 ml) was added, the polymer was precipitated with cold light oil and purified to remove unreacted monomer and other impurities (x2), resulting in a sticky yellow polymer (Mn = 4811, Mn (theoretical value) = 5346, Mw / Mn =). 1.52) was obtained.

Part 2. Poly (methyl acrylate-co-acryloyl hydrazine) (theoretically 50% reacted methoxy group)

~ 50: 50 molar ratio

To a solution of p (methyl acrylate) Mn = 4811 (6.85 g, 1.42 mmol) in ethanol (60 ml) was added 50-60% hydrazine hydrate (Sigma Aldrich) (2 g, 1.9 ml, 31-37 mmol) and the solution was 80 Heat at 48 ° C. The solution was initially cloudy and within 1 hour the solution became clear. After heating at 80 ° C. over the weekend, a clear solution was obtained, which formed a precipitate upon cooling (thick white solution). The solution was filtered to give a white solid. ¹ H NMR spectroscopy shows peaks at 4.20 pm broad and OMe reduction at 3.70 ppm. The ratio of -OMe peaks varies from 1.46: 1 to 1.1: 1 (relative to the peak at 1.55 ppm).

Part 3. Poly (methyl acrylate-co-N '-(propane-2-ylidene) acrylohydrazide

~ 50: 50 molar ratio

Poly (methyl acrylate-co-acryloyl hydrazine) (0.5 g, 0.10 mmol)

It was refluxed overnight in acetone (20 ml) and the acetone was removed in vacuo to give a sticky transparent polymer. NMR spectroscopy showed that the peak disappeared at 4.2.

Example 17

Stability of the crosslinkable solution.

In the sample of Example 1 (˜10-25 g), ammonium acetate (0 or 1 molar equivalent (relative to moles of pDMAEMA)), acetone (0-10 molar equivalents (relative to PDAAM)) and ADH (0.4 molar equivalents ( Relative to PDAAM (Table 1) Samples were vigorously stirred for 1 hour 48 hours later and weekly using Brookfield DV-II + Viscometer, S64 Spindle, 100, 50 and 30 rpm Visual and viscosity measurements were performed by Brookfield Standard 500 lot number 112801 provided 483.5 on a 100 rpm S64 spindle at 24 ° C. (expected 488 at 25 ° C.).

TABLE 1 Formulation Composition.

TABLE 2 Formulation Stability.

Polymer stability studies using Brookfield DV-II + Viscometer, S64 Spindle, 100, 50 and 30 rpm. ^# Polymer solution from Example 1. Molar equivalents of ammonium acetate relative to DMAEMA content of ^% polymer. * Molar equivalent ADH to DAAM content of polymer. ^& Molar equivalents to DAAM content of polymer.

Table 2 describes a number of important features of the present invention. Addition of ammonium acetate alone (item 3) to the polymer solution of the present invention reduces the viscosity (item 1) of the solution from 1494 mPa · s to 1038 mPa · s. While many other salts will do this, most of the actual salts used are volatile, otherwise the salt will remain in the coating and its performance may be compromised. Ammonium acetate is also most preferred along with the available ammonium carbonate. This viscosity reduction can be used in the synthesis of solutions of high loading to medium solution viscosity of the polymer. Ammonium cations may also contribute to the prevention of early crosslinking.

Samples containing ammonium acetate and ADH (Item 5) or ADH alone (Item 4) will quickly gel or solidify within 24 hours (typically much faster), which is an example of an unstable formulation. In order to prevent gelation and to provide good viscosity, at least 2 molar equivalents of acetone are required for the DAAM content of ammonium acetate, ADH and the polymer, 5 molar equivalents provide good stability (item 8), 10 molar equivalents (item 9) provides a further reduction in viscosity. 2 molar equivalents of acetone were not sufficient to prevent gelation under current conditions (item 7).

The use of ADH and acetone (5 molar equivalents) without ammonium acetate can provide a stable urea, but will have a higher viscosity than a formulation with ammonium acetate ADH and acetone.

Example 18

Properties of Unfilled Polymers and Coatings

Manufacture of coatings

Uncrosslinked Samples:

The aqueous polymer solution was used as described in the relevant examples without further addition or manipulation.

For crosslinked samples:

Samples were prepared for crosslinking by taking 20 g of the aqueous solution of the reaction described in the related examples.

The polymer of item 1 listed in Table 1 was synthesized according to the procedure of Example 6 at a controlled monomer feed ratio of DMAEMA: MMA: iBMA: DAAM 20: 50: 25: 5 at a 29 weight percent solids charge. 20 g of sample contained 2.22 mmoles of DAAM and 8.86 mmoles of DMAEMA. To this solution was added under stirring until 0.68 g (8.86 mmoles) of ammonium acetate and 0.52 g (8.86 mmoles) of acetone were dissolved. Then 0.15 g (0.89 mmoles) of ADH was added and mixed to give a homogeneous solution.

The polymer of item 2 shown in the table was prepared in Example 6. 20 g of sample contained 2.23 mmoles DAAM and 6.71 mmoles DMAEMA. To this solution was added 0.52 g (6.71 mmoles) of ammonium acetate and 0.52 g (8.94 mmoles) of acetone under stirring until dissolved. Then 0.16 g (0.89 mmoles) of ADH was added and mixed to give a homogeneous solution.

The polymer of item 3 shown in the table was prepared in Example 7. 20 g of sample contained 2.25 mmoles DAAM and 4.51 mmoles DMAEMA. To this solution was added 0.35 g (4.51 mmoles) of ammonium acetate and 0.52 g (9.01 mmoles) of acetone under stirring until dissolved. Then 0.16 g (0.90 mmoles) of ADH was added and mixed to give a homogeneous solution.

For measuring glass transition:

A small amount (1 mL) of polymer solution prepared as described in the related examples was coated onto a glass plate and allowed to dry for 24 hours under ambient conditions. The dried polymer film was scraped from the plate using a sharp blade and then 40 μL aluminum crucible with perforated leads on a Mettler Toledo DSC-3 with a Haake EK90 / MT intracooler. Analyze It uses a gas flow of 40 mL / min under an N ₂ inert atmosphere with a temperature profile heating from -50 ° C. to 200 ° C. at 10 ° C./min, cooling from 200 ° C. to −50 ° C., and heating from −50 ° C. to 200 ° C. It was performed by.

To measure gloss:

A small amount (1 mL) of polymer solution prepared as described in the related examples was drawn from the glass plate using a 152 micron draw-down frame. After allowing the film to dry under ambient conditions, film gloss was measured using a Star Instruments GRM-2000 gloss layer (Table 3).

Table 3. Gloss Measurement of Film

Item 1: The polymer was synthesized according to the procedure of Example 6 at a controlled monomer feed ratio of DMAEMA: MMA: iBMA: DAAM 20: 50: 25: 5 at a 29 weight percent solids charge.

Item 2: The polymer is as described in Example 6 at a monomer feed ratio of DMAEMA: MMA: iBMA: DAAM 15: 50: 30: 5 at 29 wt% solids loading.

Item 3: The polymer is as described in Example 7 with a monomer feed ratio of DMAEMA: MMA: iBMA: DAAM 10: 50: 35: 5 at 29 wt% solids loading.

Example 19

Synthesis of polymer in water under nitrogen atmosphere without seed polymer using gamma-terpinene as chain transfer agent

DMAEMA: EMA: DAAM 20: 75: 5 ratio (28 wt.% Solids)

Water (90 mL) was deoxygenated by N ₂ bubbling and then added to a 500 mL reactor under N ₂ atmosphere, to which initiator 2,2′-azobis [2- (2-imidazolin-2-yl) propane ] Dihydrochloride (known as VA-044) (0.100 g, 0.31 mmol) was added. Stirring with an overhead stirrer (half-moon blade) was started at 330 rpm and the reaction temperature was raised to 60 ° C. 2- (dimethylamino) ethyl methacrylate (10.06 g, 64 mmol), ethyl methacrylate (27.39 g, 240 mmol), diacetone acrylamide (2.71 g, 16 mmol), glacial acetic acid (3.84 g, 64 mmol) And a mixture of γ-terpinene (436 mg, 3.2 mmol) was deoxygenated with N ₂ bubbling and injected using a syringe pump for a 4 hour period. At the same time, VA-044 (300 mg, 0.93 mmol) dissolved in H ₂ O (10 mL) was injected into the reaction using a syringe pump for a 6 hour period.

The reaction became more viscous after monomer injection and the stirring speed was increased to 400 rpm. Six hours after the end of the initiator feed, a single VA-044 (100 mg, 0.31 mmol) was added and stirring was increased to 450 rpm. The reaction was decanted and used as is.

28% solids (by weight)

¹ H NMR (CDCl ₃ ): EMA Broad 4.01 ppm, DMAEMA Broad 4.07 ppm.

DMAEMA: EMA ratio 21.3: 73.6

Conversion ( ¹ H NMR): Residual monomer level too low to be measured by NMR

GPC (DMAc, PMMA standard): M _n = 22.4 K, PD = 1.84

Example 20

Synthesis of polymers containing HMA in water, under nitrogen atmosphere without seed polymer

DMAEMA: MMA: HMA: DAAM 15: 55: 25: 5 ratio (28 wt% solids)

Water (90 mL) was deoxygenated by N ₂ bubbling and then added to a 500 mL reactor under N ₂ atmosphere, to which initiator 2,2′-azobis [2- (2-imidazolin-2-yl) propane ] Dihydrochloride (known as VA-044) (0.200 g, 0.619 mmol) was added. Stirring with an overhead stirrer (half-moon blade) was started at 330 rpm and the reaction temperature was raised to 60 ° C. 2- (dimethylamino) ethyl methacrylate (DMAEMA) (7.55 g, 48 mmol), methyl methacrylate (MMA) (17.62 g, 176 mmol), hexyl methacrylate (HMA) (13.62 g, 80 mmol) , A mixture of diacetone acrylamide (DAAM) (2.71 g, 16 mmol), glacial acetic acid (2.88 g, 48 mmol) and terpinolene (0.218 g, 1.6 mmol) was deoxygenated by N ₂ bubbling and a 4-hour period While using a syringe pump. At the same time, VA-044 (0.600 g, 1.87 mmol) dissolved in N ₂ degassed H ₂ O (10 mL) was injected into the reaction using a syringe pump for a 6 hour period.

The reaction became more viscous after monomer injection and the stirring speed was increased to 400 rpm. Six hours after the end of the initiator feed, a single VA-044 (0.100 g, 0.309 mmol) was added and stirring was increased to 450 rpm. The reaction was decanted and used as is.

28% solids (by weight)

¹ H NMR (acetone-d ₆ ): MMA Broad 3.63 ppm, HMA Broad 4.01 ppm, DMAEMA Broad 4.11 ppm. DMAEMA: MMA: HMA: DAAM ratio 15.3: 52.1: 25.7: 6.9%

Conversion ( ¹ H NMR, acetone-d ₆ ): all monomers> 99.9%

GPC (DMAc, PMMA standard): M _n = 21.3 K, PD = 1.77

Example 21

Synthesis of polymers containing DEAEMA in water, under nitrogen atmosphere without seed polymer

DEAEMA: MMA: iBMA: DAAM 15: 50: 30: 5 ratio (28 weight percent solids)

Water (90 mL) was deoxygenated by N ₂ bubbling and then added to a 500 mL reactor under N ₂ atmosphere, to which initiator 2,2′-azobis [2- (2-imidazolin-2-yl) propane ] Dihydrochloride (known as VA-044) (0.200 g, 0.619 mmol) was added. Stirring with an overhead stirrer (half-moon blade) was started at 330 rpm and the reaction temperature was raised to 60 ° C. 2- (diethylamino) ethyl methacrylate (DEAEMA) (8.89 g, 48 mmol), methyl methacrylate (MMA) (16.02 g, 160 mmol), isobutyl methacrylate (iBMA) (13.65 g, 96 mmol), diacetone acrylamide (DAAM) (2.71 g, 16 mmol), glacial acetic acid (2.88 g, 48 mmol) and terpinolene (0.218 g, 1.6 mmol) were deoxygenated by N ₂ bubbling, 4 Injection was made using a syringe pump for a period of time. At the same time, VA-044 (0.600 g, 1.87 mmol) dissolved in N ₂ degassed H ₂ O (10 mL) was injected by reaction using a syringe pump for a 6 hour period.

The reaction became more viscous after monomer injection and the stirring speed was increased to 400 rpm. Six hours after the end of the initiator feed, a single VA-044 (0.100 g, 0.309 mmol) was added and stirring was increased to 450 rpm. The reaction was decanted and used as is.

28% solids (by weight)

¹ H NMR (acetone-d ₆ ): MMA Broad 3.63 ppm, iBMA Broad 3.76 ppm, DEAEMA Broad 4.05 ppm. DMAEMA: MMA: iBMA ratio 17: 49.1: 30

Conversion ( ¹ H NMR, acetone-d ₆ ): all monomers> 99.9%, iBMA 1900 ppm residual

GPC (DMAc, PMMA standard): M _n = 19.8 K, PD = 1.88

Example 22

Synthesis of polymers containing di (ethylene glycol) methyl ether methacrylate (DEGMMA) and hexyl methacrylate (HMA) in water under nitrogen atmosphere without seed polymer

DMAEMA: DEGMMA: HMA: DAAM 15: 40: 40: 5 ratio (30 wt% solids)

Di (ethylene glycol) methyl ether methacrylate (DEGMMA)

Water (90 mL) was deoxygenated by N ₂ bubbling and then added to a 500 mL reactor under N ₂ atmosphere, to which initiator 2,2′-azobis [2- (2-imidazolin-2-yl) propane ] Dihydrochloride (known as VA-044) (0.200 g, 0.619 mmol) was added. Stirring with an overhead stirrer (half-moon blade) was started at 330 rpm and the reaction temperature was raised to 60 ° C. 2- (dimethylamino) ethyl methacrylate (7.55 g, 48 mmol), di (ethylene glycol) methyl ether methacrylate (DEGMMA) (24.09 g, 128 mmol), hexyl methacrylate (21.79 g, 128 mmol) (HMA), diacetone acrylamide (2.71 g, 16 mmol), a mixture of glacial acetic acid (2.88 g, 48 mmol) and terpinolene (0.218 g, 1.6 mmol) were deoxygenated by N ₂ bubbling and a 4-hour period While using a syringe pump. At the same time, VA-044 (0.600 g, 1.87 mmol) dissolved in N ₂ degassed H ₂ O (10 mL) was injected by reaction using a syringe pump for a 6 hour period.

The reaction became more viscous after monomer injection and the stirring speed was increased to 400 rpm. Six hours after the end of the initiator feed, a single VA-044 (0.100 g, 0.309 mmol) was added and stirring was increased to 450 rpm. The reaction was decanted and used as is.

Solid content 30% (weighing)

1 H NMR (CDCl 3): DEGMMA multiple broad peak 3.53 ppm, HMA broad 3.89 ppm, DMAEMA broad 4.07 ppm.

DMAEMA: DEGMMA: HMA: DAAM ratio 15.5: 42.1: 38.2: 4.1%

Conversion (1H NMR, acetone-d6): all monomers> 99%

GPC (DMAc, PMMA standard): Mn = 30.6 K, PD = 2.02

Example 23

Synthesis of polymers containing IEMA in water, under nitrogen atmosphere without seed polymer

IEMA: MMA: iBMA: DAAM 20: 50: 25: 5 ratio (29 wt% solids)

2- ( 1H -imidazol-1-yl) ethyl methacrylate (IEMA)

2- (1H-imidazol-1-yl) ethyl methacrylate is described by Patrikios et. al., Maria Rikkou-Kalourkoti, Panayiota A. Panteli and Costas S. Patrickios, Polym. Chem., 2014, 5, 4339-4347]. Since 1- (2-hydroxyethyl) imidazole was obtained from Combi-Blocks, only the second step of the synthesis was followed and used as is.

Water (90 mL) was deoxygenated by N ₂ bubbling and then added to a 500 mL reactor under N ₂ atmosphere, to which initiator 2,2′-azobis [2- (2-imidazolin-2-yl) propane ] Dihydrochloride (known as VA-044) (0.200 g, 0.619 mmol) was added. Stirring with an overhead stirrer (half-moon blade) was started at 330 rpm and the reaction temperature was raised to 60 ° C. 2- ( 1H -imidazol-1-yl) ethyl methacrylate (11.53 g, 64 mmol), methyl methacrylate (16.02 g, 160 mmol), isobutyl methacrylate (11.38 g, 80 mmol), A mixture of diacetone acrylamide (2.71 g, 16 mmol), glacial acetic acid (3.84 g, 64 mmol) and terpinolene (0.218 g, 1.6 mmol) was deoxygenated with N ₂ bubbling and the syringe pump was Injection was carried out. At the same time, VA-044 (0.600 g, 1.87 mmol) dissolved in N ₂ degassed H ₂ O (10 mL) was injected using a syringe pump for a 6 hour reaction period.

The reaction became more viscous after monomer injection and the stirring speed was increased to 400 rpm. Six hours after the end of the initiator feed, a single VA-044 (0.100 g, 0.309 mmol) was added and stirring was increased to 450 rpm. The reaction was decanted and used as is.

29% solids (by weight)

¹ H NMR (acetone-d ₆ ): MMA Broad 3.62 ppm, iBMA Broad 3.75 ppm, IEMA Broad 4.45 ppm. IEMA: MMA: iBMA Ratio 21.3: 47.5: 26.3

Conversion ( ¹ H NMR, acetone-d ₆ ): all monomers> 99.9%

GPC (DMAc, PMMA standard): M _n = 12.2 K, PD = 1.70

Example 24

Synthesis of polymers containing trifluoroethyl methacrylate TFEMA in water, under nitrogen atmosphere without seed polymer

DMAEMA: MMA: TFEMA: DAAM 15: 50: 30: 5 ratio (30 wt% solids)

Trifluoroethyl methacrylate (TFEMA)

Water (90 mL) was deoxygenated by N ₂ bubbling and then added to a 500 mL reactor under N ₂ atmosphere, to which initiator 2,2′-azobis [2- (2-imidazolin-2-yl) propane ] Dihydrochloride (known as VA-044) (0.200 g, 0.619 mmol) was added. Stirring with an overhead stirrer (half-moon blade) was started at 330 rpm and the reaction temperature was raised to 60 ° C. 2-dimethylaminoethyl methacrylate (7.55 g, 48 mmol), methyl methacrylate (16.02 g, 160 mmol), trifluoroethyl methacrylate (16.14 g, 96 mmol), diacetone acrylamide (2.71 g , 16 mmol), glacial acetic acid (2.88 g, 48 mmol) and terpinolene (0.218 g, 1.6 mmol) were deoxygenated by N ₂ bubbling and injected using a syringe pump for a 4 hour period. At the same time, VA-044 (0.600 g, 1.87 mmol) dissolved in N ₂ degassed H ₂ O (10 mL) was injected using a syringe pump for a 6 hour reaction period.

The reaction became more viscous after monomer injection and the stirring speed was increased to 400 rpm. Six hours after the end of the initiator feed, a single VA-044 (0.100 g, 0.309 mmol) was added and stirring was increased to 450 rpm. The reaction was decanted and used as is.

Solid content 30% (weighing)

1 H NMR (acetone-d6): TFEMA Broad 4.62 ppm, DMAEMA Broad 4.12 ppm, MMA Broad 3.63 ppm. DMAEMA: MMA: TFEMA Ratio 15.8: 48.4: 32.1

Conversion (1H NMR, acetone-d6): all monomers> 99.9%

GPC (DMAc, PMMA standard): Mn = 21.6 K, PD = 1.65

Example 25

Synthesis of polymers containing trimethylsilylmethyl methacrylate TMSMMA in water, under nitrogen atmosphere without seed polymer

DMAEMA: MMA: TMSMMA: DAAM 15: 50: 30: 5 ratio (30 wt% solids)

Trimethylsilylmethyl methacrylate (TMSMMA)

Water (90 mL) was deoxygenated by N ₂ bubbling and then added to a 500 mL reactor under N ₂ atmosphere, to which initiator 2,2′-azobis [2- (2-imidazolin-2-yl) propane ] Dihydrochloride (known as VA-044) (0.200 g, 0.619 mmol) was added. Stirring with an overhead stirrer (half-moon blade) was started at 330 rpm and the reaction temperature was raised to 60 ° C. 2-dimethylaminoethyl methacrylate (7.55 g, 48 mmol), methyl methacrylate (16.02 g, 160 mmol), trimethylsilylmethyl methacrylate (16.54 g, 96 mmol), diacetone acrylamide (2.71 g, 16 mmol), glacial acetic acid (2.88 g, 48 mmol) and terpinolene (0.218 g, 1.6 mmol) were deoxygenated with N ₂ bubbling and injected using a syringe pump for a 4 hour period. At the same time, VA-044 (0.600 g, 1.87 mmol) dissolved in N ₂ degassed H ₂ O (10 mL) was injected using a syringe pump for a 6 hour reaction period.

The reaction became more viscous after monomer injection and the stirring speed was increased to 400 rpm. Six hours after the end of the initiator feed, a single VA-044 (0.100 g, 0.309 mmol) was added and stirring was increased to 450 rpm. The reaction was decanted and used as is.

Solid content 30% (weighing)

1 H NMR (CDCl 3): MMA Broad 3.56 ppm, TMSMMA Broad 3.49 ppm, DMAEMA Broad 4.07 ppm. DMAEMA: MMA: TMSMMA ratio 14.4: 52.6: 25.3

Conversion (1H NMR, acetone-d6): all monomers> 99.9%

GPC (DMAc, PMMA standard): Mn = 27.0 K, PD = 1.68

Example 26

Synthesis of polymers containing higher DAAM loading in water under nitrogen atmosphere with seed polymer

DMAEMA: MMA: iBMA: DAAM 10: 50: 30: 10 ratio (35 wt% solids)

Water (625 mL) was oxygenated with N ₂ bubbling and then added to a 2 L reactor under N ₂ atmosphere, to which initiator 2,2′-azobis [2- (2-imidazolin-2-yl) propane] Dihydrochloride (known as VA-044) (1.200 g, 5.29 mmol) was added. Stirring with an overhead stirrer (half-moon blade) was started at 250 rpm and the reaction temperature was raised to 60 ° C. 2- (dimethylamino) ethyl methacrylate (43.23 g, 275 mmol), methyl methacrylate (137.7 g, 1375 mmol), isobutyl methacrylate (117.3 g, 825 mmol), diacetone acrylamide (46.54 g , 275 mmol), glacial acetic acid (16.6 g, 275 mmol) and terpinolene (1.20 g, 8.81 mmol) were deoxygenated by N ₂ bubbling and injected using a peristaltic pump for a period of 4 hours. At the same time, VA-044 (5.14 g, 15.9 mmol) dissolved in N ₂ degassed H ₂ O (50 mL) was injected using a syringe pump for a 6 hour reaction period.

The reaction became more viscous after monomer injection and the stirring speed was increased to 350 rpm. Six hours after the end of the initiator feed, a single VA-044 (0.856 g, 2.63 mmol) was added and the agitation was increased to 380 rpm. After an additional hour, heating was turned off and t-butylhydroperoxide (70% by weight in water, 5.00 g, 3.88 mmol) was added. Brugolite (1.00 g, 5.52 mmol) dissolved in N ₂ degassed water (10 mL) was injected for the next 15 minutes. Once the reaction cooled to room temperature (45 minutes), it was decanted and used as is.

Solid content 35% (weighing)

1 H NMR (acetone-d6): MMA Broad 3.63 ppm, iBMA Broad 3.76 ppm, DMAEMA Broad 4.05 ppm. DMAEMA: MMA: iBMA ratio 10: 49.1: 30.7

Conversion (1H NMR, acetone-d6): all monomers> 99.9%

GPC (DMAc, PMMA standard): Mn = 23.7 K, PD = 1.72

Example 27

Synthesis of polymers containing higher DAAM loading in water under nitrogen atmosphere with seed polymer

DMAEMA: MMA: iBMA: DAAM 10: 45: 30: 15 ratio (35 wt% solids)

Water (625 mL) was deoxygenated by N ₂ bubbling and then added to a 2 L reactor under N ₂ atmosphere, to which initiator 2,2′-azobis [2- (2-imidazolin-2-yl) propane ] Dihydrochloride (known as VA-044) (1.200 g, 5.29 mmol) and seed polymer solution (10 g, 29% by weight in water, DMAEMA: MMA: iBMA: DAAM 10: 45: 30: 10) were added It was. Stirring with an overhead stirrer (half-moon blade) was started at 250 rpm and the reaction temperature was raised to 60 ° C. 2- (dimethylamino) ethyl methacrylate (43.23 g, 275 mmol), methyl methacrylate (123.9 g, 1237.5 mmol), isobutyl methacrylate (117.3 g, 825 mmol), diacetone acrylamide (69.8 g , 412.5 mmol), glacial acetic acid (16.6 g, 275 mmol) and terpinolene (1.20 g, 8.81 mmol) were deoxygenated by N ₂ bubbling and injected using a peristaltic pump for a period of 4 hours. At the same time, VA-044 (5.14 g, 15.9 mmol) dissolved in N ₂ degassed H ₂ O (50 mL) was injected using a syringe pump for a 6 hour reaction period.

The reaction became more viscous after monomer injection and the stirring speed was increased to 350 rpm. Six hours after the end of the initiator feed, a single VA-044 (0.856 g, 2.63 mmol) was added and the agitation was increased to 380 rpm. After an additional hour, heating was turned off and t-butylhydroperoxide (70% by weight in water, 5.00 g, 3.88 mmol) was added. Brugolite (1.00 g, 5.52 mmol) dissolved in N ₂ degassed water (10 mL) was injected for the next 15 minutes. Once the reaction cooled to room temperature (45 minutes), it was decanted and used as is.

Solid content 35% (weighing)

1 H NMR (acetone-d6): MMA Broad 3.63 ppm, iBMA Broad 3.76 ppm, DMAEMA Broad 4.05 ppm. DMAEMA: MMA: iBMA Ratio 9.4: 41.8: 34

Conversion (1H NMR, acetone-d6): all monomers> 99.9%

GPC (DMAc, PMMA standard): Mn = 22.1 K, PD = 1.98

Example 28

Synthesis of polymers containing 20 mol% DAAM in water, under nitrogen atmosphere without seed polymer

DMAEMA: MMA: iBMA: DAAM 10: 40: 30: 20 ratio (29 wt% solids)

Water (90 mL) was deoxygenated by N ₂ bubbling and then added to a 500 mL reactor under N ₂ atmosphere, to which initiator 2,2′-azobis [2- (2-imidazolin-2-yl) propane ] Dihydrochloride (known as VA-044) (0.200 g, 0.619 mmol) was added. Stirring with an overhead stirrer (half-moon blade) was started at 330 rpm and the reaction temperature was raised to 60 ° C. 2- (dimethylamino) ethyl methacrylate (5.03 g, 32 mmol), methyl methacrylate (12.82 g, 128 mmol), isobutyl methacrylate (13.65 g, 96 mmol), diacetone acrylamide (10.83 g , 48 mmol), glacial acetic acid (1.92 g, 32 mmol) and terpinolene (0.218 g, 1.6 mmol) were deoxygenated by N ₂ bubbling and injected using a syringe pump for a 4 hour period. At the same time, VA-044 (0.600 g, 1.87 mmol) dissolved in N ₂ degassed H ₂ O (10 mL) was injected using a syringe pump for a 6 hour reaction period.

The reaction became more viscous after monomer injection and the stirring speed was increased to 400 rpm. Six hours after the end of the initiator feed, a single VA-044 (0.100 g, 0.309 mmol) was added and stirring was increased to 450 rpm. The reaction was decanted and used as is.

29% solids (by weight)

1 H NMR (acetone-d6): MMA Broad 3.63 ppm, iBMA Broad 3.76 ppm, DMAEMA Broad 4.05 ppm. DMAEMA: MMA: iBMA ratio 9.0: 39.6: 32.6

Conversion (1H NMR, acetone-d6): all monomers> 99%

GPC (DMAc, PMMA standard): Mn = 23.0 K, PD = 1.70

Example 29

Synthesis of polymers containing higher DAAM loading and n- BMA in water, under nitrogen atmosphere without seed polymer

DMAEMA: MMA: n- BMA: DAAM 10: 50: 30: 10 ratio (35 wt% solids)

Water (625 mL) was deoxygenated by N ₂ bubbling and then added to a 2 L reactor under N 2 atmosphere, to which initiator 2,2′-azobis [2- (2-imidazolin-2-yl) propane] Dihydrochloride (known as VA-044) (1.200 g, 5.29 mmol) was added. Stirring with an overhead stirrer (half-moon blade) was started at 250 rpm and the reaction temperature was raised to 60 ° C. 2- (dimethylamino) ethyl methacrylate (43.23 g, 275 mmol), methyl methacrylate (137.7 g, 1375 mmol), n -butyl methacrylate (117.3 g, 825 mmol), diacetone acrylamide (46.54 g, 275 mmol), a mixture of glacial acetic acid (16.6 g, 275 mmol) and terpinolene (1.20 g, 8.81 mmol) were deoxygenated by N ₂ bubbling and injected using a peristaltic pump for a period of 4 hours. At the same time, VA-044 (5.14 g, 15.9 mmol) dissolved in N ₂ degassed H ₂ O (50 mL) was injected using a syringe pump for a 6 hour reaction period.

The reaction became more viscous after monomer injection and the stirring speed was increased to 350 rpm. Six hours after the end of the initiator feed, a single VA-044 (0.856 g, 2.63 mmol) was added and the agitation was increased to 380 rpm. After an additional hour, heating was turned off and t -butylhydroperoxide (70% by weight in water, 5.00 g, 3.88 mmol) was added. Brugolite (1.00 g, 5.52 mmol) dissolved in N ₂ degassed water (10 mL) was injected for the next 15 minutes. Once the reaction cooled to room temperature (45 minutes), it was decanted and used as is.

Solid content 35% (weighing)

¹ H NMR (acetone-d ₆ ): MMA Broad 3.63 ppm, n- BMA Broad 4.00 ppm, DMAEMA Broad 4.11 ppm. DMAEMA: MMA: n -BMA ratio 8.7: 49.3: 33.3

Conversion ( ¹ H NMR, acetone-d ₆ ): all monomers> 99.9%

GPC (DMAc, PMMA standard): M _n = 21.3 K, PD = 2.05

Example 30

Synthesis of polymers containing higher DAAM loading in water under nitrogen atmosphere with seed polymer

DMAEMA: MMA: n-BMA: DAAM 10: 45: 30: 15 ratio (35 wt% solids)

Water (625 mL) was deoxygenated by N ₂ bubbling and then added to a 2 L reactor under N ₂ atmosphere, to which initiator 2,2′-azobis [2- (2-imidazolin-2-yl) propane ] Dihydrochloride (known as VA-044) (1.200 g, 5.29 mmol) and seed polymer solution (10 g, 29% by weight in water, DMAEMA: MMA: n-BMA: DAAM 10: 50: 30: 10) Was added. Stirring with an overhead stirrer (half-moon blade) was started at 250 rpm and the reaction temperature was raised to 60 ° C. 2- (dimethylamino) ethyl methacrylate (43.23 g, 275 mmol), methyl methacrylate (123.9 g, 1237.5 mmol), n-butyl methacrylate (117.3 g, 825 mmol), diacetone acrylamide (69.8 g, 412.5 mmol), glacial acetic acid (16.6 g, 275 mmol) and terpinolene (1.20 g, 8.81 mmol) were deoxygenated by N ₂ bubbling and injected using a peristaltic pump for a period of 4 hours. At the same time, VA-044 (5.14 g, 15.9 mmol) dissolved in N ₂ degassed H ₂ O (50 mL) was injected into the reaction using a syringe pump for a 6 hour period.

The reaction became more viscous after monomer injection and the stirring speed was increased to 350 rpm. Six hours after the end of the initiator feed, a single VA-044 (0.856 g, 2.63 mmol) was added and the agitation was increased to 380 rpm. After an additional hour, heating was turned off and t-butylhydroperoxide (70% by weight in water, 5.00 g, 3.88 mmol) was added. Brugolite (1.00 g, 5.52 mmol) dissolved in N ₂ degassed water (10 mL) was injected for the next 15 minutes. Once the reaction cooled to room temperature (45 minutes) it was decanted and used as is.

Solid content 35% (weighing)

1 H NMR (CDCl 3): MMA Broad 3.58 ppm, n-BMA Broad 3.94 ppm, DMAEMA Broad 4.10 ppm. DMAEMA: MMA: n-BMA ratio 9.2: 44.2: 32.0

Conversion (1H NMR, acetone-d6): all monomers> 99.9%

GPC (DMAc, PMMA standard): Mn = 23.9 K, PD = 1.82

Example 31

RAFT chain transfer agent, synthesis of polymer in solvent with CTA = 4-cyano-4-(((dodecylthio) carbonothioyl) thio) pentanoic acid under nitrogen atmosphere and dissolution of the isolated polymer in an aqueous solution

DMAEMA: MMA: iBMA: DAAM 15: 50: 30: 5 ratio (29 wt% solids)

A three-necked reaction vessel equipped with a condenser, a thermocouple and a stirrer was charged with monomer in 40 ml of toluene, CTA 4-cyano-4-(((dodecylthio) carbonothioyl) thio) pentanoic acid (0.70 g, 1.74 mmol) and Fill with a solution of V88 (1,1'-azobis (cyclohexanecarbonitrile) = 0.16 g, 6.5x10-4 mol), degassing the solution, lowering to a heatblock heated to 90 ° C and heating at 90 ° C Continued for 18 hours. NMR showed ˜95% conversion and a second portion of Vazo-88 (0.049 g) was added and the solution was heated for an additional 8 hours. The polymer was isolated by precipitation in diesel oil and dried under vacuum.

Solids content: 29% (by weight)

1 H NMR (acetone-d6): 3.63 ppm MMA broad, 3.76 ppm iBMA broad, 4.11 ppm DMAEMA broad.

Conversion (1H NMR, acetone-d6): DMAEMA 100%, MMA> 99.9%, iBMA 99.0%

GPC (DMAc, PMMA standard): Mn = 17.6 K, Mw = 27.5 K, PD = 1.56

Formation of Polymer Solution from the Prepared Polymers.

Stock Solution 1: 2.88 g of acetic acid was slowly added to 90 g of water under stirring.

Solutions containing 10, 20 and 30% solids, made up to 20 ml by stock solution 1, were prepared as above. Samples were placed on shaker 400 / min until dissolved. The solid for the 10% solution dissolved effectively after 2 hours. The 20% solution was partially (-50%) dissolved (some gel particles remained undissolved after 2 hours). The 30% solution appeared to absorb water and after 2 hours a gel formed. Over night, 80% of the 30% solution was dissolved and the 20% solution was completely dissolved. It took 48 hours to complete dissolution of the 30% w / w solution.

Example 32

chapter 1

Synthesis of polymer in solvent with thiol chain transfer agent, CTA = dodecane thiol under nitrogen atmosphere.

DMAEMA: MMA: iBMA: DAAM 15: 50: 30: 5 ratio (29 wt% solids)

A three-necked reaction vessel equipped with a condenser, thermocouple and stirrer was loaded with monomer in 40 ml of toluene, dodecane thiol (0.42 ml, 0.36 g, 1.74 mmol) and V88 (1,1'-azobis (cyclohexanecarbonitrile) = 0.16 g, 6.5 × 10 ⁻⁴ mol), the solution was degassed, lowered to a heatblock heated to 90 ° C., and heating at 90 ° C. was continued for 18 hours. NMR showed unreacted iBM, a second portion of Vazo-88 (0.11 g) was added and the solution was heated for an additional 10 hours. IBM has been consumed. The polymer was isolated by precipitation in diesel oil and dried under vacuum.

Solids content: 29% (by weight)

¹ H NMR (acetone-d6): 3.63 ppm MMA broad, 3.76 ppm iBMA broad, 4.11 ppm DMAEMA broad.

Conversion (1H NMR, acetone-d6): DMAEMA 100%, MMA> 99.9%, iBMA 99.5%

GPC (DMAc, PMMA standard): M _n = 16.5 K, M _w = 28 K, PD = 1.68

Part 2.

An aqueous solution of the copolymer was then prepared using the polymer prepared in 1 part.

Stock Solution 1: 2.88 g of acetic acid was slowly added to 90 g of water under stirring.

A solution containing 10, 20 and 30% solids, made up to 20 ml by stock solution 1, was prepared from this part. Samples were placed on shaker 400 / min until dissolved. The solid for the 10% solution dissolved effectively after 2 hours. The 20% solution partially dissolved and some gel particles remained undissolved after 2 hours, the 30% solution appeared to absorb water, and after 2 hours a gel formed. Over night, 80% of the 30% solution was dissolved and the 20% solution was completely dissolved. After 48 hours, 30% sample was dissolved.

Example 33

Synthesis and Formulation Stability of 1,3,5-pentanetrihydrazide crosslinker

chapter 1. Synthesis of 1,3,5-pentanetrimethylcarbonate

The 250 mL round bottom flask was filled with 3 M methanolic HCl (100 mL) and 1,3,5-pentanecarboxylic acid (10 g, 49.0 mmol), fitted with a reflux condenser and refluxed for 8 hours. After the reaction cooled down, it was added to 1 M NaOH (200 mL) and the product was extracted with DCM (3 x 50 mL). The combined organic extracts were washed with water (100 mL), saturated brine (100 mL), passed through DryDisk ™, and the solvent was then evaporated in vacuo to afford the product as a clear oil (yield). : 12.06 g, 100%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 3.66 (s, 3H), 3.65 (s, 6H), 2.43 (m, 1H), 2.32 (m, 4H), 1.87 (m, 4H).

Part 2. Synthesis of 1,3,5-pentanetrihydrazide (PTH)

A 500 mL round bottom flask was charged with EtOH (200 mL), 1,3,5-pentanetrimethylcarbonate (12.06 g, 49.0 mmol) and a 50% by weight solution of hydrazine hydrate (25 mL, 250 mmol) in water and fitted with a reflux condenser And refluxed for 4 hours. After the reaction was cooled to room temperature, the product precipitated out and was filtered to give a fine white powder (yield: 10.16 g, 84.2%). ¹ H NMR (D ₂ O, 400 MHz): 2.07 (m, 5H), 1.70 (m, 4H).

The synthesized 1,3,5-pentanetrihydrazide crosslinker (1.2 g) was prepared using the polymer sample of Example 29 (50 g) and three different molar equivalent levels (8, 10 and 15 molar equivalents) of acetone. Was added. The sample was stirred under high shear for 1 hour. After 48 hours, visual measurements were performed. Variants with 8 molar equivalents of acetone were observed to gel completely after 48 hours. Ten equivalents and fifteen equivalents of acetone appeared to increase in viscosity but still flow.

Example 34 Preparation of TiO 2 Paint Formulations.

Opaque coating

Formulation A.

Mill bases containing Tiona 595, additol VXW 6208, BYK024, BYK1710 and RO water were prepared beforehand. It was prepared in the following manner. ADDITOL VXW 6208 (18.02 g), BYK 024 (0.9 g), BYK 1710 (1.025 g), and DOSED RO water (13.51 g) are added to a 250 ml paint can and mixed using an overhead stirrer. Thiona 595 (112.58 g) is gradually added to the paint cans while increasing the stirring speed to 800 rpm to provide a good dispersion of the pigment. 7.5 g of DOSED RO water is then added to the mill base as wash water. In this step the stirring speed is increased to 1600 rpm and the mill base is stirred for 30 minutes. An aqueous polymer solution (20 g) from Example 30 was mixed with mill base (8.71), butyl carbitol ™ (1.8 g) and acetone (1.07 g). Then ADH (640 mg) was added and the solution was stirred for 20 minutes to give a homogeneous solution. When painted with a coating, the solution provided a hard, white, opaque, high gloss finish.

Formulation B.

Calcium carbonate (3.3 g) was added to Formulation A to provide a hard, white, opaque, matte finish surface when used as a coating.

Formulation C.

Silicon dioxide (1.0 g) was added to Formulation A to provide a hard, white, opaque, matte finish surface when used as a coating.

Formulation D.

In another embodiment, a pre-made mill base (8.71 g) was added to the aqueous polymer solution (20 g), butyl carbitol ™ (1.8 g) and acetone (1.07 g) from Example 30. PTH (602 mg) was then added and the solution was stirred for 20 minutes to give a homogeneous solution. When painted as a coating, the solution provided a hard, white, opaque, high gloss finish.

Formulation E.

In another embodiment, commercial mill base Colortrend Plus White XC11 (2.0 g) was added to the aqueous polymer solution (20 g) and acetone (1.07 g) from Example 30. Then ADH (640 mg) was added and the solution was stirred for 20 minutes to give a homogeneous solution. When painted as a coating, the solution provided a hard, white, opaque, high gloss finish.

Rheology modifiers such as Natrosol Plus 330 may be added to increase viscosity, or alternatively ammonium acetate may be added to reduce viscosity.

Example 35 Stain Tolerance-Red Wine

All tests were performed on a hard, white, opaque, high gloss film that cured for at least one week. They were painted on untreated plywood (10 x 10 cm) and provided two coats. All tests used Stanley Cabernet Sauvignon (pH 3), which was applied to a paper swatch of approximately 1.5 cm x 1.5 cm until the wine had accumulated on top of the paper. The swatch was removed and the stain washed again with water, spray'n'wipe and finally water, and left for 1 hour.

A pre-made mill base containing thiona 595, Aditol VXW 6208, BYK024, BYK1710 and RO water was mixed to prepare item 1 paint, and the aqueous polymer solution from Example 2 (20 g) was added to the mill base (7.47). g), butyl carbitol ™ (1.5 g) and acetone (296 mg). Then ADH (177 mg) was added and the solution was stirred for 20 minutes to give a homogeneous solution. When painted as a coating, the solution provided a hard, white, opaque, high gloss finish.

A pre-made mill base containing thiona 595, Aditol VXW 6208, BYK024, BYK1710 and RO water was mixed to prepare item 2 paint, and the aqueous polymer solution from Example 26 (20 g) was added to the mill base (7.47). g), butyl carbitol ™ (1.5 g) and acetone (625 mg). Then ADH (375 mg) was added and the solution was stirred for 20 minutes to give a homogeneous solution. When painted as a coating, the solution provided a hard, white, opaque, high gloss finish.

A pre-made mill base containing thiona 595, Aditol VXW 6208, BYK024, BYK1710 and RO water was mixed to prepare item 3 paint, and the aqueous polymer solution from Example 27 (20 g) was added to the mill base (7.47). g), butyl carbitol ™ (1.5 g) and acetone (1.07 g). Then ADH (640 mg) was added and the solution was stirred for 20 minutes to give a homogeneous solution. When painted as a coating, the solution provided a hard, white, opaque, high gloss finish.

A pre-made mill base containing thiona 595, Aditol VXW 6208, BYK024, BYK1710 and RO water was mixed to prepare item 4 paint, and the aqueous polymer solution from Example 28 (20 g) was added to the mill base (7.47). g), butyl carbitol ™ (1.5 g) and acetone (1.19 g). Then ADH (711 mg) was added and the solution was stirred for 20 minutes to give a homogeneous solution. When painted as a coating, the solution provided a hard, white, opaque, high gloss finish.

DMAEMA / DAAM% content in the polymer Stain appearance

One. 20/5 Example 2 (above) Dark Gray / Brown

2. 10/10 yellow

3. 10/15 buff

4. 10/20 Barely noticeable

5. Dulux Aquanamel buff

6. Taubmans aqueous enamel No clear indication

Example 36 Contact Adhesive .

The contact adhesive was prepared by Example 22 by the addition of acetone (5 molar equivalents to the DAAM content of the composition provided by Example 22) and ADH (0.4 molar equivalents to the DAAM content of the composition provided by Example 22). It can be prepared from the provided composition. For example, acetone and ADH can be added to the composition provided by Example 22 by first adding the required amount of acetone under stirring and then adding the required amount of ADH under stirring. The resulting formulation can then be applied to the rough surface (grade 80 sandpaper) of two or more polypropylene substrates and left to dry (eg, a period of about 5 to 20 hours). The adhesive coated surfaces can be pressed together and left to cure for about 1 hour. Immediately after the substrates are pressed together, they can be easily separated, repositioned and contacted again. However, after about 1 hour, the adhesive must be substantially cured and the substrate will not be subjected to significant force and will not be able to be easily separated.

Example 37 Recirculation

Non-crosslinked dried polymers, not formulated or formulated with paints, coatings or adhesives, can be reconstituted by the application of a weakly acidic solution. Crosslinked dried polymers, which are not formulated or formulated with paints, coatings or adhesives, can be reconstituted by the application of a weakly acidic solution containing a small amount of acetone.

Mill bases containing Thiona 595, Aditol VXW 6208, BYK024, BYK1710 and RO water were prepared in advance. An aqueous polymer solution (20 g) from Example 28 was mixed with mill base (7.47 g), butyl carbitol ™ (1.5 g) and acetone (1.19 g). Then ADH (711 mg) was added and the solution was stirred for 20 minutes to give a homogeneous solution. A portion (15 g) of the formulated solution was left to dry for 48 hours and then mechanically ground into small pieces. A solution of glacial acetic acid (1 mL), acetone (0.2 mL) and water (10 mL) was added and the mixture was shaken for 4 hours to give a homogeneous solution.

Formulation consisting of DAAM (0.10), acetone (5ME to DAAM, 0.5 mole) and ADH (0.4 ME to DAAM, 0.04 mole) with DMAEMA (0.15 mole), MMA (0.45) and BMA (0.30) and acetic acid (0.15) When dried, is reconstituted by the addition of a solution consisting of water (88% by weight), acetic acid (2.9% by weight) and acetone (9.1% by weight).

Example 38 Ketones Stabilizing ADH

Ketone (5 molar equivalents to the DAAM content of the polymer) and ammonium acetate (1 mole relative to the DMAEMA content of the polymer) in a solution of the copolymer of the composition, which is the same as Example 6 but made on a 1 Kg scale (provides 18.5 K of Mn) Equivalent) was added under stirring for 2 minutes after each addition. ADH (0.4 molar equivalents ADH relative to the DAAM content of the polymer) was added and stirring continued until the ADH dissolved in the polymer solution (˜5-10 minutes). The formulations were then qualitatively evaluated for stability (Table 4).

Table 4. Stabilization of Crosslinkable Formulations by Ketones

Example 39 Gloss Level

All gloss readings were taken using a Starr GRM-2000 glossmeter at 60o. Ten readings were taken in different directions and areas on painted coupons. Coupons were prepared by applying two coats of paint with a brush to a bare plywood panel, 10 × 10 cm 2.

A pre-made mill base containing thiona 595, Aditol VXW 6208, BYK024, BYK1710 and RO water was mixed to prepare item 1 paint, and the aqueous polymer solution from Example 27 (20 g) was added to the mill base (7.47). g), butyl carbitol ™ (1.5 g) and acetone (1.07 g). Then ADH (640 mg) was added and the solution was stirred for 20 minutes to give a homogeneous solution. When painted as a coating, the solution provided a hard, white, opaque, high gloss finish.

A pre-made mill base containing Thiona 595, Aditol VXW 6208, BYK024, BYK1710 and RO water was mixed to prepare item 2 paint, and the aqueous polymer solution from Example 28 (20 g) was added to the mill base (7.47). g), butyl carbitol ™ (1.5 g) and acetone (1.19 g). Then ADH (711 mg) was added and the solution was stirred for 20 minutes to give a homogeneous solution. When painted as a coating, the solution provided a hard, white, opaque, high gloss finish.

A pre-made mill base containing thiona 595, Aditol VXW 6208, BYK024, BYK1710 and RO water was mixed to prepare item 3 paint, and the aqueous polymer solution from Example 30 (20 g) was added to the mill base (8.71). g), butyl carbitol ™ (1.8 g) and acetone (913 g). Then ADH (548 mg) was added and the solution was stirred for 20 minutes to give a homogeneous solution. When painted as a coating, the solution provided a hard, white, opaque, high gloss finish.

The lowest and highest readings were subtracted and the remainder averaged (Table 5).

Table 5. Gloss evaluation of films containing pigments.

Item coating Gloss Reading (GU)

One Prepared from Example 27 as described above 69.5

2 Prepared from Example 28 as described above 67.7

3 Prepared from Example 30 as described above 74.6

4 Durux Aqua enamel 67.1

5 Taubman's aqueous enamel 72.6

6 Durux Super Enamel (Oil) 83.0

7 Taubman's Ultra Enamel (Oil) 83.3

Example 40

Synthesis of polymers containing 15 mol% DMAEMA and 10 mol% DAAM under nitrogen atmosphere with seed polymer

DMAEMA: MMA: n-BMA: DAAM 15: 45: 30: 10 ratio (35 wt% solids)

Deionized water (521.79 g) and seed polymer solution (51.00 g, 35.86 wt%) were added to a 1 L round bottom reactor under N ₂ atmosphere. Stirring with an overhead stirrer (anchor blade) was started at 150 rpm and the reaction temperature was raised to 60 ° C. 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (known as VA-044) (1.10 g) is dissolved in 10.00 g of deionized water and fed to the reactor At 60 ° C. The stirring speed was raised to 160 rpm. After 10 minutes, 2- (dimethylamino) ethyl methacrylate (59.54 g, 378.75 mmol), methyl methacrylate (113.76 g, 1136.45 mmol), n-butyl methacrylate (107.57 g, 757.52 mmol), diacetone A mixture of acrylamide (42.73 g, 252.49 mmol), glacial acetic acid (22.74 g, 378.75 mmol) and terpinolene (1.08 g, 7.954 mmol) was injected using a peristaltic pump for a period of 4 hours. At the same time, VA-044 (5.40 g, 16.70 mmol) dissolved in deionized water (30.00 g) was injected using a syringe pump for the reaction 4 hour period. At the end of the monomer / initiator feed, a single Rhodoline DF 642 N1 (0.20 ml) was added to the reactor. 1.08 g of VA-044 was dissolved in 10.00 g of deionized water and injected into the reactor for 15 minutes. After another 1 hour and 45 minutes, t-butylhydroperoxide (70% by weight in water, 1.00 g) was added in a single shot. Brugolite (1.00 g) was dissolved in deionized water (20.00 g) and injected for 15 minutes. Immediately after this the heating was turned off. Once the reaction cooled to room temperature (45 minutes), it was decanted and filtered through 85 micron filter silk.

Solids content 35%

Example 41

Synthesis, TiO2 Formulation, and Stain Tolerance Testing of Polymers Containing 60 mol% DMAEMA and 15 mol% DAAM in a Nitrogen atmosphere with Seed Polymer

DMAEMA: MMA: n-BMA: DAAM 60: 17.2: 7.8: 15 ratio (35 wt% solids)

Deionized water (456.89 g) and seed polymer solution (51.00 g, 36.0 wt.%) Were added to a 1 L round bottom reactor under N 2 atmosphere. Stirring with an overhead stirrer (anchor blade) was started at 150 rpm and the reaction temperature was raised to 60 ° C. 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (known as VA-044) (1.10 g) is dissolved in 10.00 g of deionized water and reacted with a single reactor Was added at 60 ° C. The stirring speed was raised to 160 rpm. After 10 minutes, 2- (dimethylamino) ethyl methacrylate (206.24 g, 1311.87 mmol), methyl methacrylate (37.65 g, 376.12 mmol), n-butyl methacrylate (24.22 g, 170.54 mmol), diacetone A mixture of acrylamide (55.49 g, 327.94 mmol), glacial acetic acid (78.78 g, 1311.87 mmol) and terpinolene (0.95 g, 6.9956 mmol) was injected using a peristaltic pump for a period of 4 hours. At the same time, VA-044 (5.40 g, 16.70 mmol) dissolved in deionized water (30.00 g) was injected using a syringe pump for the reaction 4 hour period. At the end of the monomer / initiator feed, a single rodoline DF 642 N1 (0.20 ml) was added to the reactor. 1.08 g of VA-044 was dissolved in 10.00 g of deionized water and fed to the reactor for 15 minutes. After another 1 hour and 45 minutes, t-butylhydroperoxide (70% by weight in water, 1.00 g) was added in a single shot. Brugolite (1.00 g) was dissolved in deionized water (20.00 g) and injected for 15 minutes. Immediately after this the heating was turned off. Once the reaction cooled to room temperature (45 minutes), it was decanted and filtered through 85 micron filter silk.

Solid content 37%

Preparation of TiO2 Paint Formulations.

The mill base was prepared first. Thiona 595 (110.28 g) was dispersed in aditol VXW 6208 (17.64 g), BYK024 (0.88 g), BYK1710 (1.0 g) and RO water (13.24 g) under high shear (1600 rpm) mixing. 7.34 g of RO water was used as wash water. This formed a mill base.

The aqueous polymer solution prepared above (containing 60 mol% DMAEMA) (292.78 g) was mixed with mill base (135.36 g), butyl carbitol (27.33 g), propylene glycol (9.05 g) and acetone (22.38 g). Then, 1,3,5-pentanetrihydrazide crosslinker (9.59 g) was added. Natrosol PLUS 330 (2.80 g) was dissolved in RO water (27.94 g). After pH adjustment to pH 9, a natrosol-water mixture was added and stirred at 800 rpm.

Stain resistance test

All tests were performed on a hard, white, opaque, high gloss film that cured for 7 days. They were painted (2 coats) on the MDF timbre panel. Four different stain tests were performed: wine, coca cola, blue food coloring and water. All stains were applied to a cloth swatch about 1.5 cm x 1.5 cm until the solution had accumulated on top of the cloth. The swatch was removed, the stain washed with water, a spray and wipe and left for 1 hour. In all cases, the coating was partially peeled off, leaving dark stains on the paint in the case of wine, coca cola, and food coloring.

Example 42

Synthesis of a polymer containing 15.13 mol% MMA, 59.87 mol% BMA, 15 mol% DMAEMA and 10 mol% DAAM under nitrogen atmosphere with seed polymer. (T _g = 34.37 ° C.)

DMAEMA: MMA: n-BMA: DAAM 15: 15.13: 59.87: 10 ratio (36 wt% solids)

Deionized water (523.90 g) and seed polymer solution (51.00 g, 35.95 wt%) were added to a 1 L round bottom reactor under N ₂ atmosphere. Stirring with an overhead stirrer (anchor blade) was started at 150 rpm and the reaction temperature was raised to 60 ° C. 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (known as VA-044) (1.10 g) is dissolved in 10.00 g of deionized water and reacted with a single reactor Was added at 60 ° C. The stirring speed was raised to 160 rpm. After 10 minutes, 2- (dimethylamino) ethyl methacrylate (54.25 g, 345.06 mmol), methyl methacrylate (34.84 g, 348.07 mmol), n-butyl methacrylate (195.58 g, 1377.33 mmol), diacetone A mixture of acrylamide (38.93 g, 230.05 mmol), glacial acetic acid (20.72 g, 345.06 mmol) and terpinolene (1.00 g, 7.36 mmol) was injected using a peristaltic pump for a period of 4 hours. At the same time, VA-044 (5.40 g, 16.70 mmol) dissolved in deionized water (30.00 g) was injected using a syringe pump for the reaction 4 hour period. At the end of the monomer / initiator feed, a single rodoline DF 642 N1 (0.20 ml) was added to the reactor. 1.08 g of VA-044 was dissolved in 10.00 g of deionized water and fed to the reactor for 15 minutes. After another 1 hour and 45 minutes, t-butylhydroperoxide (70% by weight in water, 1.00 g) was added in a single shot. Brugolite (1.00 g) was dissolved in deionized water (20.00 g) and injected for 15 minutes. Immediately after this the heating was turned off. Once the reaction cooled to room temperature (45 minutes), it was decanted and filtered through 85 micron filter silk.

Solid content 36%

Example 43

General stain resistance test for paints using 1,3,5-pentanetrihydrazide crosslinker (from Example 33).

Preparation of TiO2 Paint Formulations.

The mill base was prepared first. Thiona 595 (133.1 g) was dispersed under high shear (1600 rpm) mixing in aditol VXW 6208 (21.3 g), BYK024 (1.1 g), BYK1710 (1.2 g) and RO water (16.0 g). 8.9 g of RO water was used as wash water. This forms a mill base.

The aqueous polymer solution (201.1 g) from Example 29 was mixed with mill base (90.8 g), butyl carbitol (18.3 g), propylene glycol (6.1 g) and acetone (11.0 g). Then, 1,3,5-pentanetrihydrazide crosslinker (Example 33) (4.7 g) was added. Natrosol PLUS 330 (1.9 g) was dissolved in RO water (18.8 g). After pH adjustment to pH 9, a Natrosol PLUS-water mixture was added and stirred at 800 rpm.

Stain resistance test

All tests were performed on a hard, white, opaque, high gloss film that cured for 7 days. They were painted (2 coats) on the MDF timbre panel. Four different stain tests were performed: wine, coca cola, blue food coloring and water. All stains were applied to a cloth swatch about 1.5 cm x 1.5 cm until the solution had accumulated on top of the cloth. The swatch was removed, the stain washed with water, a spray and wipe and left for 1 hour. The water did not leave the timbre panel defective. Wine, Coca Cola ™, and food coloring left lighter stains compared to the stains remaining when ADH was added to the same polymer variant.

In the following specification and claims, unless otherwise stated, the words “comprises” and variations, such as “comprising” and “comprising,” refer to any of the described integers or steps or groups of integers or steps. It will be understood to imply, but not exclude any other integer or step or group of integers or steps.

Reference to any prior document (or information derived therefrom), or any known material herein, is in the form of knowledge or acknowledgment or in any presentation form that prior document (or information derived therefrom) or known material It should not be taken without taking it as part of a common and general knowledge in the field of attempts related to this specification.

Claims (22)

A storage stable crosslinkable aqueous polymer composition,
(a) an aqueous liquid;
(b) a copolymer dissolved in an aqueous liquid by volatilizable non-gas acid,
(i) an ethylenically unsaturated monomer comprising a basic functional group protonated by a volatilizable non-gas acid, wherein the polymerized moiety of the monomer is less than 25 mol% relative to the total moles of polymerized monomer moiety of the copolymer. Monomer present;
(ii) ethylenically unsaturated monomers comprising functional groups for promoting crosslinking of the copolymer; And
(iii) hydrophobic ethylenically unsaturated monomers
Copolymers comprising polymerized residues of;
(c) a reversible blocked crosslinker to promote crosslinking of (i) the copolymer, and (ii) a volatilizable crosslinking inhibitor to inhibit crosslinking of the copolymer by a reversibly blocked crosslinker.
Storage stability crosslinkable aqueous polymer composition comprising a. The aqueous polymer composition of claim 1 wherein the ethylenically unsaturated monomer comprising a basic functional group comprises a tertiary basic functional group. The method of claim 1, wherein the ethylenically unsaturated monomer containing a basic functional group is amino acrylate, amino methacrylate, acrylamide, methacrylamide, vinyl pyridine, vinyl imidazole, 1- (vinylphenyl) methanamine, amino malee. An aqueous polymer composition selected from meads and combinations thereof. The ethylenically unsaturated monomer according to any one of claims 1 to 3, wherein the ethylenically unsaturated monomer comprising a functional group for promoting crosslinking of the copolymer is hydroxy, carboxylic acid, epoxy, ketone, aldehyde, alkene, alkyne, amine, aza. An aqueous polymer composition comprising a crosslinking functional group selected from id, halide, hydrazide and combinations thereof. The hydrophobic ethylenically unsaturated monomer according to any one of claims 1 to 4, wherein the hydrophobic ethylenically unsaturated monomer is styrene, alpha-methyl styrene, butyl (meth) acrylate, iso-butyl (meth) acrylate, amyl (meth) acrylate, Hexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, ethyl hexyl (meth) acrylate, crotyl (meth) acrylate, cinnamil (meth) acrylate, oleyl ( Meth) acrylate, lysine oleyl (meth) acrylate, cholesteryl (meth) acrylate, cholesteryl (meth) acrylate, vinyl butyrate, vinyl tert-butyrate, vinyl stearate, vinyl laurate, 2- (2-oxo-1-imidazolidinyl) ethyl methacrylate (ethoxy ethyleneurea methacrylate) and combinations thereof. 6. The aqueous polymer composition of claim 1, wherein the reversibly blocked crosslinker is a reversibly blocked multifunctional hydrazide compound. 7. The aqueous polymer composition of claim 1, wherein the volatilizing crosslinking inhibitor is selected from methyl ethyl ketone, diethyl ketone and combinations thereof. 8. The aqueous polymer composition of claim 1, wherein the volatilizable non-gas acid comprises acetic acid. 9. As a method for producing an aqueous copolymer composition,
(i) an ethylenically unsaturated monomer comprising a basic functional group protonated by a volatilizable non-gas acid, wherein the monomer is 25 mole% relative to the total moles of ethylenically unsaturated monomer introduced during the polymerization to prepare the copolymer. Monomers used in amounts less than;
(ii) ethylenically unsaturated monomers comprising functional groups for promoting crosslinking of the copolymer; And
(iii) hydrophobic ethylenically unsaturated monomers
Polymerizing in an aqueous liquid comprising a volatizable non-gas acid ethylenically unsaturated monomer selected from;
The copolymer so formed is soluble in an aqueous liquid. A process for preparing a storage stable crosslinkable aqueous polymer composition, wherein the process is in an aqueous liquid.
(a) (i) an ethylenically unsaturated monomer comprising a basic functional group protonated by a volatilizable non-gas acid, wherein the polymerized moiety of the monomer is 25 mole% relative to the total moles of polymerized monomer moiety of the copolymer. Monomers present in an amount less than;
(ii) ethylenically unsaturated monomers comprising functional groups for promoting crosslinking of the copolymer; And
(iii) hydrophobic ethylenically unsaturated monomers
Copolymers made soluble in aqueous liquids by volatilizable non-gas acids comprising polymerized moieties of; And
(b) a reversible blocked crosslinker to promote crosslinking of the copolymer, and (ii) a volatilizable crosslinking inhibitor to inhibit crosslinking of the copolymer by a reversibly blocked crosslinker.
Manufacturing method comprising combining or forming. The method of claim 10, further comprising forming a copolymer in an aqueous liquid, wherein the step comprises:
(i) an ethylenically unsaturated monomer comprising a basic functional group protonated by a volatilizable non-gas acid, wherein the monomer is 25 mole% relative to the total moles of ethylenically unsaturated monomer introduced during the polymerization to prepare the copolymer. Monomers used in amounts less than;
(ii) ethylenically unsaturated monomers comprising functional groups for promoting crosslinking of the copolymer; And
(iii) hydrophobic ethylenically unsaturated monomers
And polymerizing in an aqueous liquid comprising volatilized non-gas acid ethylenically unsaturated monomers selected from. The process according to any one of claims 9, 10 or 11, wherein the ethylenically unsaturated monomer comprising a basic functional group comprises a tertiary basic functional group. The method of claim 9, wherein the ethylenically unsaturated monomer comprising a functional group for promoting crosslinking of the copolymer is hydroxy, carboxylic acid, epoxy, ketone, aldehyde, alkene, alkyne, amine, aza. And a crosslinking functional group selected from id, halide, hydrazide and combinations thereof. 14. The hydrophobic ethylenically unsaturated monomer according to any one of claims 9 to 13, wherein the hydrophobic ethylenically unsaturated monomer is styrene, alpha-methyl styrene, butyl (meth) acrylate, iso-butyl (meth) acrylate, amyl (meth) acrylate, Hexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, ethyl hexyl (meth) acrylate, crotyl (meth) acrylate, cinnamil (meth) acrylate, oleyl ( Meth) acrylate, lysine oleyl (meth) acrylate, cholesteryl (meth) acrylate, cholesteryl (meth) acrylate, vinyl butyrate, vinyl tert-butyrate, vinyl stearate, vinyl laurate, 2- (2-oxo-1-imidazolidinyl) ethyl methacrylate (ethoxy ethyleneurea methacrylate) and a combination thereof. The process according to any one of claims 9 to 11, wherein the reversibly blocked crosslinker is a reversibly blocked multifunctional hydrazide compound. The process according to claim 9, wherein the volatilizing crosslinking inhibitor is selected from acetone, methyl ethyl ketone, diethyl ketone and combinations thereof. The method according to any one of claims 9 to 11, wherein the ethylenically unsaturated monomer containing a basic functional group is selected from amino acrylate, amino methacrylate, acrylamide, methacrylamide, vinyl pyridine, vinyl imidazole, 1- ( Vinylphenyl) methanamine, amino maleimide and combinations thereof. The process according to claim 9, wherein the volatilizable non-gas acid comprises acetic acid. The process according to claim 9 or 11, wherein the polymerization of ethylenically unsaturated monomers is carried out using terpinolene as a chain transfer agent. A polymer composition derived through the loss of an aqueous liquid in the storage stable crosslinkable aqueous polymer composition according to any one of claims 1 to 8. A substrate having a surface coated with the storage stable crosslinkable aqueous polymer composition according to claim 1. An adhesive, varnish or paint comprising the storage stable crosslinkable aqueous polymer composition according to any one of claims 1 to 8.