JP6817039B2 - Processing aids and polymer formulations containing them and methods for producing them - Google Patents

Description

The present invention relates to a multi-stage emulsion processing aid polymer, a foamable halogenated polymer formulation containing a processing aid polymer, a method for producing a processing aid, and a method for producing an foamable polymer formulation.

Halogenated polymers, such as polyvinyl chloride (“PVC”), are used as building materials to replace wood in a variety of applications, such as nasal concealment boards, edging and decorative molded and rolled products. As used herein, "halogenated polymers" include (1) homopolymers or copolymers containing greater than 80% vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride or combinations, and (2) chlorinated poly. It means vinyl chloride, chlorinated polyethylene or a combination thereof. The most industrially common of these polymers is polyvinyl chloride (PVC), so the general description herein will focus on PVC and foamed PVC as examples. PVC foam is also used for signs, deckboards, and in the cores of some types of PVC pipes.

Foamed PVC for these various applications is typically produced by continuous extrusion. The most common extrusion process involves free foaming from the die, followed by some type of calibration and Celuka or integrated skin process. These PVC
The foaming process and typical compounding ingredients are described in D.I. Klemner and V. Send
ijarevic, "PVC Foams", Chapter 9, Handbo
ok of Polymer Foams and Foam Technology
y, 2nd Ed. , Hanser Publishers, Munich (20)
It can be found in 04).

Important components of the foamed PVC formulation are PVC, heat stabilizers, lubricants, one or more foaming agents and (co) polymer additives such as impact modifiers and processing aid polymers. Processing aid polymers are copolymers that are compatible with PVC and are high in methyl methacrylate,
Alternatively, they tend to be other compositions compatible with PVC, such as styrene acrylonitrile copolymers. U.S. Pat. No. 2,646,417, No. 3975315, No. 5206296 and No. 6765033, and European Patent No. 115.
Specification 3936 describes the types of polymeric compositions used as processing aids for PVC. As used herein, "compatibility" refers to the processing aid polymer P during heat treatment.
It means that it is uniformly mixed or dispersed in the VC.

The high molecular weight processing aid causes expansion or die well of the polymer during the polymer processing process at the time the heated polymer exits the extruder die. This expansion is important, for example, in processes where polymer expansion is required to fill the cavity, such as in the Celuka process, or in free foaming where a given sheet thickness is required.
These processing aid polymers also increase melt extensibility and strength due to their high molecular weight compatibility with PVC. It also helps control the expansion of foam cells and provides a small, uniform cell size. In addition, the high melt strength helps prevent the foam from collapsing while cooling the extruded foam sheet and helps to secure the foam structure.
The high melt strength also allows the high temperature extruded material to be drawn through a sizing or calibration device. All scraps or edgings can be ground and reused in the extrusion process because the foaming material is thermoplastic and not a crosslinked thermosetting material. The ability to recycle this material as a milled and recycled material is important for economic implications and waste disposal.

It is not uncommon for these processing aids to have a weight average molecular weight in the range of 500,000 to 150,000, and higher MW (molecular weight) materials show higher efficiency (B).
.. Haworth et al. , Plastics, Rubber and C
applications Processing and Applications, v
ol. 22, p. 159, 1994). The concentration used may be in the range of 0.5-20 parts per 100 parts of PVC in the formulation, depending on the MW of the processing aid, the desired density and the sheet thickness. The lower the density and the larger the sheet thickness, the higher the concentration of processing aid used.

An alternative to the use of high MW processing aids to enable the foaming process is to use crosslinkers for the matrix polymer. The crosslinker must cure at a temperature and rate similar to the decomposition of the chemical foaming agent that cures the foam. This approach is used in the industry to produce polyurethanes, epoxy resin foams, etc. (D. Klem)
pener and V. Sendijarevik, Handbook of Po
lymeric Foams and Foam Technology, 2nd E
d. , Hanser Publishers, Munich (2004)).

This curing approach has also been used for halogenated polymers such as PVC. In a typical approach, PVCs, foaming agents and cross-linking agents are combined into one and placed in a mold under pressure. The mold is heated to a temperature that induces the foaming agent to produce a gas,
When the pressure is released, it causes foaming and hardening within the same time frame. In this method, the foam structure is fixed and a thermosetting material having high heat resistance and resistance to compression set is produced, but the scrap derived from the foam cannot be easily reprocessed. In addition, this type of approach is not useful for extrusion-type foaming processes, as hardening tends to occur inside the extruder.

An example of this type of approach is included in US Pat. No. 3,261785, in which a non-polymerizable polyfunctional sulfone azide is used as a cross-linking agent for PVC. U.S. Patent No. 4
In 965222, the isocyanate curing agent is used with a plasticized PVC in which PVC contains an active hydrogen functional group, or an acrylic polymer with an active hydrogen functional group is blended with PVC and cured with isocyanate. Be done. European
Polymer Journal, vol. 36, p. In 2235 (2000)
Crosslinking of PVC foams with the use of peroxides and trimethacrylate monomers has been described. These approaches have the limitation that scrap cannot be reprocessed.
Moreover, this type of approach is not useful for extrusion foaming steps because it is difficult to control the cure rate so that the material does not cure in the extruder and does not induce melt viscosity problems.

The present invention is a method for producing a processing aid, an effervescent halogenated polymer formulation containing a processing aid, and a processing aid and a polymer formulation. By stepping the addition of the functionalized ethylenically unsaturated monomer in one step of the multistage polymerization, the inventors of the present invention
Claimed priority over U.S. Provisional Patent Application No. 60/997880 filed October 5, 2007 by increasing the molecular weight of the polymer at a constant functionalized ethylenically unsaturated monomer concentration. Publication 12/2 of US Patent Application Filed on 17th March
It has been found that the usefulness of the specification 83934 can be further increased.

The present invention comprises 25-75% by weight first-stage polymers comprising units derived from non-functional ethylenically unsaturated monomers into an emulsion polymerization reactor; as well as units derived from one or more functionalized ethylenically unsaturated monomers. It is a multi-stage emulsion processing aid polymer containing 25 to 75% by weight of the second-stage polymer containing, and the functional groups are β-ketoester, β-ketoamide, β-diketone, cyanoacetate, malonate, nitroalkane, β. Selected from the group consisting of −nitroesters, sulfon azides, thiols, thiols-s-triazines and amines.
Functional groups are incorporated into the polymer by the step of polymerizing an ethylenically unsaturated monomer containing these functional groups, or by post-functionalization of the polymer using an additional reaction after polymerization, the processing aid polymer is 700, Provided is a multi-stage emulsion processing aid polymer having Mw of 000 or more. In this embodiment, the first stage does not contain units derived from functionalized monomers.

In yet another embodiment, the present invention comprises a processing aid polymer in which the functional group is in the first stage of the multistage polymer, a foamable halogenated polymer formulation containing the processing aid of the present invention, and a processing aid and foaming. Provided is a method for producing a sex halogenated polymer formulation.

The present invention is a method for producing a multi-stage emulsion processing aid polymer, an effervescent halogenated formulation containing a processing aid polymer, a method for producing a processing aid, and a method for producing an effervescent halogenated polymer formulation containing the same substance. is there.

A first embodiment of a multi-stage emulsion processing aid polymer is a 25-75% by weight first-stage polymer comprising units derived from a non-functional ethylenically unsaturated monomer in an emulsion polymerization reactor; as well as one or more non-stage polymers. 25-75% by weight containing 0-99.6 mol% units from functional ethylenically unsaturated monomers and 0.4-100 mol% units from one or more functionalized ethylenically unsaturated monomers. It contains a two-stage polymer, and the functional groups are β-ketoester and β-.
Selected from the group consisting of ketoamides, β-diketones, cyanoacetates, malonates, nitroalkanes, β-nitroesters, sulfon azides, thiols, thiol-s-triazines and amines, the functional groups contain these functional groups. Incorporated into the polymer by the step of polymerizing the ethylenically unsaturated monomer or by post-functionalization of the polymer using an additional reaction after polymerization, the processing aid polymer has a Mw of 700,000 or more. In this embodiment, the first stage does not contain units derived from functionalized monomers.

A second embodiment of the multi-stage emulsion processing aid polymer is a unit of 0-99.6 mol% derived from one or more non-functional ethylenically unsaturated monomers and one or more functionalization into an emulsion polymerization reactor. 2 containing 0.4-100 mol% units derived from ethylenically unsaturated monomers
It is a first-stage polymer of 5 to 75% by weight, and the functional groups are β-ketoester, β-ketoamide, β-diketone, cyanoacetate, malonate, nitroalkane, β-nitroester, sulfon azide, thiol, thiol. Within the polymer by the step of polymerizing an ethylenically unsaturated monomer selected from the group consisting of −s-triazine and amine, the functional groups containing these functional groups, or by post-functionalization of the polymer using an additional reaction after polymerization. Contains 25-75% by weight second-stage polymer containing units derived from non-functional ethylenically unsaturated monomers, as well as 700,000 processing aid polymers.
It has the above MW. In this embodiment, the second stage does not contain units derived from the functionalized monomer.

All individual values and subranges of the first stage of 25-75 wt% are included herein and disclosed herein. For example, the first stage in a multistage polymer is 25, 30, 35, 40,
From the lower limit of 45, 50, 55, 60, 65 or 70% by weight 30, 35, 40, 45,
It may be up to an upper limit of 50, 55, 60, 65, 70 or 75% by weight. For example, the weight% of the first stage may be in the range of 25-75% by weight, or 25-50% by weight in another example, or 40-70% by weight in another example.

All individual values and subranges of the 25 to 75 percent percent second stage by are included herein and disclosed herein. For example
The weight% of the second stage in the multi-stage polymer is 25, 30, 35, 40, 45, 50, 55, 60.
, 65 or 70% by weight to 30, 35, 40, 45, 50, 55, 60, 65
, 70 or up to 75% by weight. For example, the weight% of the second stage (the)
The weight percentage of weight of) may be in the range of 25-75% by weight, or 50-75% by weight in another example, or 30-60% by weight in another example.

The processing aid polymer may have a weight average molecular weight (Mw) of 700,000 or more. All over 700,000 individual values and subranges are included herein and disclosed herein. For example, the processing aid polymer Mw is 700,000; 800,000.
900,000; 1,000,000; 1,200,000; 1,400,000; 1
, 600,000; or may be greater than or equal to the lower limit of 1,800,000.

In the present invention, the functionalized ethylenically unsaturated monomer is β-ketoester and amide, β-.
Further provided is a multi-stage emulsion processing aid polymer according to any one of the above embodiments, selected from the group of diketone, cyanoacetate, malonate, nitroalkane and β-nitroester.

In the present invention, the functionalized ethylenically unsaturated monomer is acetoacetoxyethyl (meth) acrylate (AAEM), acetoacetoxypropyl (meth) acrylate, acetoacetoxybutyl (meth) acrylate, 2,3-di (acetoacetoxy) propyl. (Meta) acrylate, acetoacetoxyethyl (meth) acrylamide, 2-cyanoacetoxyethyl (meth) acrylate, 2-cyanoacetoxyethyl (meth) acrylamide, N-
A multi-stage emulsion processing aid polymer according to any one of the above embodiments, selected from the group of cyanoacetyl-N-methylaminoethyl (meth) acrylate, N- (2propionylacetoxybutyl) (meth) acrylamide, is further added. provide.

The present invention further provides a multi-stage emulsion processing aid polymer according to any one of the above embodiments, wherein the functionalized ethylenically unsaturated monomer is AAEM.

Suitable for use as a non-functional comonomer (with the functionalized monomers described above) in the processing aid polymer is a monoethylene unsaturated monomer, eg, an alkyl group with 18
Alkyl acrylate containing less than 8 carbon atoms, preferably less than 8 carbon atoms; alkyl methacrylate containing 18 or less carbon atoms, preferably 8 or less carbon atoms in the alkyl moiety; acrylonitrile; methacrylonitrile; Acrylic acid; methacrylic acid;
Styrene; and substituted styrenes, especially alkyl substituted styrenes containing no more than 14 carbon atoms in the alkyl group, and other vinyl monomers such as vinyl chloride, ethylene, vinyl acetate and vinyl versite. Typical suitable comonomeres are ethyl acrylate, butyl acrylate (BA) , 2-ethylhexyl acrylate, methyl methacrylate (MMA) , butyl methacrylate (BMA ) .
) , tert-Butyl methacrylate, cyclohexyl methacrylate, hydroxyethyl methacrylate, acrylonitrile, methacrylic nitrile, acrylic acid, methacrylic acid, styrene, o-chlorostyrene and α-methylstyrene. Styrene, acrylonitrile, butyl acrylate, butyl methacrylate, ethyl acrylate, methyl methacrylate and combinations thereof are preferred monomers. Similarly, functional groups can be polymerized within a polyethylene copolymer, followed by a processing aid polymer PV.
It is chlorinated to make it compatible with C or other halogenated polymers.

In another embodiment, the invention supplies water, at least one non-functional ethylenically unsaturated monomer and a surfactant into an emulsion polymerization reactor, thereby forming a first-stage polymer of a multi-stage emulsion polymer. a step, the first stage polymer process constitutes 25% to 75% by weight of the total weight of the multistage emulsion polymer; presence of the first stage polymer
In the present, it is a step of supplying one or more functionalized ethylenically unsaturated monomers into the emulsion polymerization reactor to form a second stage polymer , wherein the functional groups are β-ketoester and β.
-Ketamide, β-diketone, cyanoacetic acid ester, malonate, nitroalkane, β-
Nitro esters, sulfonic azide, thiol, is selected from the group consisting of thiol -s- triazine and an amine, that functional group, or polymerizing ethylenically unsaturated monomers containing these functional groups, or post-Polymerization The step of incorporating into the polymer by post-functionalization of the polymer using an additional reaction, the second-stage polymer making up 25% to 75% by weight of the total weight of the multi-stage emulsion polymer; and the multi-stage emulsion polymer. Do you want to dry
Further provides a multi-step emulsion polymerization method comprising the steps of forming a multi-step emulsion polymer processing aid , or letting it dry.

In another embodiment, the present invention supplies water, one or more functionalized ethylenically unsaturated monomers and a surfactant into an emulsion polymerization reactor to provide a first stage of a multistage emulsion polymer.
In the step of forming a polymer , the functional groups thereof are β-ketoester, β-ketoamide,
It is selected from the group consisting of β-diketone, cyanoacetate, malonate, nitroalkane, β-nitroester, sulfone azide, thiol, thiol-s-triazine and amine, the functional group of which is ethylene containing these functional groups. Polymerize sex unsaturated monomer
Or incorporated into the polymer by functionalization after the polymers using additional reactions after polymerization, whereby 25% by weight of the total weight of the first stage polymer multistage emulsion polymer -
Steps constituting 75% by weight; at least one non-functional ethylenically unsaturated monomer is supplied into the emulsion polymerization reactor in the presence of the first stage polymer to form the second stage polymer.
In this step, the second-stage polymer is 25 to 7 of the total weight of the multi-stage emulsion polymer.
5 steps constituting wt%; or drying and multistage emulsion polymer, or <br/> allowed to dry, thereby further providing a multistage emulsion polymerization process comprising the step of forming a multi-stage emulsion polymer processing aid ..

In yet another embodiment, the present invention comprises (a) at least 80 weights of at least 80 weights of one or more monomers selected from vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride and chlorinated polyvinyl chloride and chlorinated polyethylene. 0.5-20% by weight of one or more of 20-99% by weight selected from homopolymers or copolymers containing% halogenated polymer according to one embodiment of the method of the invention. Further provided is a method for producing an effervescent halogenated polymer formulation, comprising blending with one or more multi-stage emulsion processing aids.

In yet another embodiment, the present invention selects the functionalized ethylenically unsaturated monomer from the group of β-ketoesters and amides, β-diketones, cyanoacetic acid esters, malonates, nitroalkanes and β-nitroesters. Further provided is a method according to any one of the above embodiments. In yet another embodiment, the substituted ethylenically unsaturated monomer is acetoacetoxyethyl (meth) acrylate, acetoacetoxypropyl (meth) acrylate, acetoacetoxybutyl (meth) acrylate, 2,3-di (acet). Acetoxy) propyl (meth) acrylate, acetoacetoxyethyl (meth) acrylamide, 2-cyanoacetoxyethyl (meth) acrylate, 2-cyanoacetoxyethyl (meth) acrylamide, N-cyanoacetyl-N-methylaminoethyl (meth) acrylate , N- (2 propionylacetoxybutyl) (meth) acrylamide further provides a method according to any one of the above embodiments, selected from the group.

In yet another embodiment, the invention further provides a method according to any one of the above embodiments, wherein the functionalized ethylenically unsaturated monomer is acetoacetoxyethyl methacrylate (AAEM).

The functional groups are incorporated into the processing aid polymer by copolymerization of the ethylenically unsaturated monomer containing these functional groups with other ethylenically unsaturated monomers used for producing the processing aid polymer. be able to. The polymerization may be carried out by solution polymerization, suspension polymerization, emulsion polymerization or bulk polymerization on the premise that the polymerization gives rise to a random copolymer. The functional group concerned is an activated methylene group or methine group that can participate in the Michael addition reaction. Such functional groups include β-ketoesters and amides, β-diketones, cyanoacetic acid esters, malonates, nitroalkanes and β-nitroesters.

Alternatively, the functional group can be incorporated into the processing aid polymer by the step of producing the polymer and then post-functionalizing the polymer using a subsequent reaction. For example, a polymer containing a β-ketoester functional group can be produced by a step of post-functionalizing a hydroxyl-containing polymer with diketene.

Another useful additional functional group that can be incorporated into the monomer for polymerization is sulfone azide (also known as sulfone azide). Examples of methods for producing these sulfone azide-containing monomers are presented in UK Pat. No. 11,328,929. Vinyl, vinylidene and styryl compounds containing sulfone azide groups are suitable monomers of interest. A particularly interesting example of such a monomer described in UK Pat. No. 11,328,929 is
m- and p-methacryloylaminophenyl sulfone azide, m- and p-acryloyl aminophenyl sulfone azide, and 1 mol of vinyl or vinylidene monomer containing 1 mol of 3- or 4-sulfone azidophenyl isocyanate and a hydroxyl group, eg It is a reaction product with hydroxypropyl (meth) acrylate or hydroxyethyl (meth) acrylate.

Other reactive functional groups for incorporation into processing aid polymers by post-functionalization of suitable monomers or post-polymerization polymers are thiols, thiol-s-triazines and amino functional groups.

The functional monomer is used at a concentration of 0.4-100 mol% within the polymer stage containing the functional monomer. All individual values and subranges of 0.4-100 mol% are included herein and disclosed herein. For example, the amount of units derived from functional monomers
From the lower limit of 0.4, 10, 20, 30, 40, 50, 60, 70, 80 or 90 mol% to the upper limit of 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100 mol% May be. For example, the amount of units derived from functional monomers is 0.4-100 mol%,
Alternatively, it may be in the range of 10 to 90 mol% in another example, or 0.5 to 20 mol% in another example.

In the stage containing one or more functional monomers, one or more non-functional monomers are 0-9.
It is used at a concentration of 9.6 mol%. All individual values and subranges of 0-99.6 mol% units from one or more non-functional ethylenically unsaturated monomers are included herein and disclosed herein. For example, the amount of units derived from one or more non-functional unsaturated monomers is 0.
From the lower limit of 10, 20, 30, 40, 50, 60, 70, 80 or 90 mol% to 10
, 20, 30, 40, 50, 60, 70, 80, 90 or up to the upper limit of 99.6 mol%. For example, the amount of non-functional ethylenically unsaturated monomer is 0-99.6 mol%.
, Or in the range of 20-90 mol% in another example, 30-80 mol% in another example, or 0-75 mol% in another example.

Since the cross-linking or curing reaction is considered to occur between the functional group of the processing aid and the halogenated polymer as a means for lightly cross-linking the system in order to control the melt viscosity, processing per 100 g of the halogenated polymer is considered. There is a desired range of functional groups with respect to the number of moles of functional groups provided by the auxiliaries.

If the concentration of functional groups is too low, the desired increase in melt viscosity will not occur. The concentration of functional groups becomes too high, resulting in an excessively large amount of insoluble gel, which makes the halogenated polymer no longer processable as a thermoplastic resin. The desired range is 1 per 100 g of halogenated polymer.
The monomer repeating unit of one or more listed functional groups is 0.00040 to 0.0056 mol. To deliver the functional groups, 0.5 to 0.5 per 100 parts based on the halogenated polymer
A loading concentration of 20 parts of the processing aid can be used, and the percentage used depends on the concentration of functional groups in the processing aid.

In some embodiments, the processing aid polymer is 700,000, -13,000,000.
, Or 1,000,000 to 1,000,000 in another example, or 1 in another example
, 600,000 to 13,000,000 with a weight average molecular weight. The definition of weight average molecular weight is The Elements of Polymer Science.
and Engineering, Alfred Rudin, Academic
Press, p. Found in 42, 1982. The method for measuring the molecular weight is presented in the section of experimental method below.

The processing aid polymer preferably has a Tg higher than 10 ° C and lower than 150 ° C. A much more desirable range is 55 ° C to 150 ° C, as this temperature range facilitates isolation of the polymer as a powder or pellet. "Tg" is the "glass transition temperature" of the polymer phase. The glass transition temperature of a polymer is the temperature at which the polymer transitions from a rigid glass state at a temperature lower than its Tg to a fluid or rubber state at a temperature higher than Tg. The Tg of the polymer is measured by differential scanning calorimetry (DSC) using the midpoint in the heat flow for temperature transition as a Tg value. For this measurement, the heating rate for DSC measurement is 20 ° C./min.

The processing aid polymer must be compatible with the foaming base halogenated polymer. "Compatibility" means that the processing aid polymer is uniformly mixed or dispersed in the base polymer during the heat treatment. The mixture does not have to be optically transparent, but generally a single glass transition temperature Tg is observed for the blended polymer. At a minimum, if separate Tgs are found for the blended polymers, those Tgs will vary with the presence of other polymers.

Processing aid polymers are typically isolated to form free-flowing powders or pellets, with powder particles having an average diameter of 50-500 μm . This processing aid polymer is subsequently added to the thermoplastic foam formulation.

The effervescent polymer formulation of the present invention optionally further comprises 0.1-6% by weight of a foaming agent. All individual values and subranges of 0.1 to 6% by weight are included herein and disclosed herein. For example, the amount of foaming agent in the formulation is 0.1, 1.5, 2, 2.5,
From the lower limit of 3, 3.8, 4, 4.5, 5 or 5.8 wt% to 0.5, 1.2, 2.6,
It may be up to an upper limit of 3.9, 4, 5.3 or 6% by weight. For example, the amount of foaming agent in the polymer formulation may be in the range of 0.1 to 6% by weight, or 1 to 5% by weight in another example.

In yet another embodiment, the present invention relates to (a) at least 80 weights of one or more monomers selected from vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride and chlorinated polyvinyl chloride and chlorinated polyethylene. 20-99% by weight of one or more halogenated polymers selected from homopolymers or copolymers (A) containing% halogenated polymers; (b) having one functional group monomer incorporated in the second stage. 1. The step of blending with one or more multi-stage emulsion processing aid polymers, wherein the one or more processing aid polymers are monomer repeating units of one or more functional groups per 100 g of halogenated polymer in the formulation. Provided are methods for making foamable halogenated polymer formulations used at concentrations providing 0.000 to 0.0056 mol.

In yet another embodiment, the present invention relates to (a) at least 80 weights of one or more monomers selected from vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride and chlorinated polyvinyl chloride and chlorinated polyethylene. 20-99% by weight of one or more halogenated polymers selected from homopolymers or copolymers (A) containing% halogenated polymers; (b) having one functional group monomer incorporated in the first stage. 1. The step of blending with one or more multi-stage emulsion processing aid polymers, wherein the one or more processing aid polymers are monomer repeating units of one or more functional groups per 100 g of halogenated polymer in the formulation. Provided are methods for making foamable halogenated polymer formulations used at concentrations providing 0.000 to 0.0056 mol.

Monomer repeating unit of one or more functional groups per 100 g of halogenated polymer 00.0
All numerical values and subranges from 0040 to 0.0056 mol are included herein and disclosed herein. For example, the concentration of the processing aid used in forming the effervescent halogenation processing aid is such that the monomer repeating unit of one or more functional groups per 100 g of the halogenated polymer is 0.000040, 0.00095, 0.0015. , 0.0025, 0.0035,
Monomer repeating units of one or more functional groups per 100 g of halogenated polymer from the lower limit of 0.0045 or 0.005 mol 0.00095, 0.0015, 0.0025, 0
.. It may be up to an upper limit of 0035, 0.0045, 0.005 or 0.0056 mol. For example, the amount of processing aid polymer used in the effervescent halogenated polymer formulation is
Monomer repeating unit of one or more functional groups per 100 g of halogenated polymer 00.00
It may be 040 to 0.0056 mol, or 0.00065 to 0.0015 mol in another example, or 0.0095 to 0.005 mol in another example.

The chemical foaming agent may be any of a variety of chemical foaming agents that release a gas after thermal decomposition.
The effervescent agent or mixture of effervescent agents can be selected from chemicals containing degradable groups such as azo groups, N-nitroso groups, carboxylate groups, carbonate groups, heterocyclic nitrogen-containing groups and sulfonylhydrazide groups. .. In general, they are solid substances that liberate a gas when heated or decomposed by a chemical reaction. Typical compounds include Plus
tic Additives Handbook, Ch. 16, eds. R. G
achter, H. et al. Muller, and P.M. P. Klemchuk, Ha
nser Gardener Publishers, Cincinnati (1996)
), Azodicarbonamides and derivatives, bicarbonates, hydrazine derivatives,
Includes semicarbazide, tetrazole, benzoxazine and borohydride. Examples of these chemical foaming agents are azodicarboxylic amide, 4,4-oxybis (benzenesulfohydrazide), diphenylsulfone-3,3-disulfohydrazide, trihydrazinotriadine, p-toluylenesulfonyl semicarbazide, 5-phenyl. Tetrazole, isatoic acid anhydride, sodium bicarbonate and sodium hydride. In addition to chemical foaming agents
Physical foaming agents such as gases and volatile liquids can also be used. Foaming can be generated by a supercritical gas such as CO ₂ injected into the extruder.

The foaming agent is applied to the polymer by several methods known to those skilled in the art, for example, to the resin in the extruder, while the resin is in a molten state to obtain uniform dispersion of the foaming agent in the molten plastic. It can be added directly to by the step of adding a solid powder, liquid or gaseous foaming agent. Preferably, the foaming agent is added prior to the extrusion step and is solid. The temperature and pressure that the effervescent composition of the present invention receives to provide the effervescent composition will vary over a wide range, depending on the amount and type of foaming agent used.

In addition to matrix halogenated polymers, functional polymer processing aids and foaming agents, the formulations are heat stabilizers, light stabilizers, antioxidants, impact modifiers, lubricants, waxes, plasticizers, fillers, fibers. , Pigments, conventional or non-functional processing aid polymers and other common additives.

The following examples demonstrate the invention in detail, but are not intended to limit the scope of the invention.

Examples 1 and 3 of the present invention are AA added in the first stage of multistage emulsion polymerization.
It was blended by the step of synthesizing a processing aid polymer having EM. The multi-stage emulsion polymerization was carried out as follows.

Example 1: 0.000224 mol of AAEM per 1.0 g of processing aid polymer
A stir bar, temperature controller, nitrogen line and condenser were attached to a 5 L round bottom flask. 1
, 245 g of deionized (DI) water, 0.1 g of sodium hydroxide (50% aqueous solution) and 9.84 g of DOWNFAX 2A1 (46% active) were loaded into the reaction vessel. The mixture was heated to 40 ° C. under nitrogen diffusion. Switched diffusion to sweep. 27.05g BMA, 81
.. A monomer mixture of 16 g of BA, 569.54 g of MMA and 77.66 g of AAEM was mixed and then added to the reaction vessel. Next, 0.30 g of Sequence (5)
% Activity), 0.11 g EDTA disodium and 10 g DI water solution were added to the reactor. Next, 0.83 g of sodium persulfate in 10 g of DI water was added. Next, a mixture of 0.10 g Lykopon and 0.09 g sodium formaldehyde sulfonelate in 10 g DI water was added. This reaction was observed to increase in temperature to 41.2 ° C. over 63 minutes. After reaching peak exotherm, the reaction was cooled to 40 ° C. Then 2
39.38 g DOWNFAX 2A1 (46% active) in 0 g DI water was added to the reaction vessel. Then 34.43 g of BMA, 103.29 g of BA, and 724.86 g of MMA.
The monomer mixture was mixed and added to the reaction vessel. Next, 0.08 g of sodium formaldehyde sulfoxylate in 10 g of DI water was added to the reaction vessel. Next, 0.13 g of t-butyl hydroperoxide (70% active) in 10 g of DI water was added to the reaction vessel. The reaction was observed to rise to 45.3 ° C. over 33 minutes. 75 this reaction solution
The mixture was cooled to ° C. and 10.82 g DOWNFAX 2A1 (46% active) in 10 g DI water was added. The reaction was cooled to 60 ° C., 0.70 g of sodium persulfate in 10 g of DI water was added, and the reaction was kept at 60 ° C. for 30 minutes. The reaction was cooled to 50 ° C. and 0.63 g sodium sulfate in 10 g DI water was added. The reaction was cooled to 40 ° C. and filtered through a mesh cloth (52.5% solid).

Example 3: 0.000112 mol of AAEM per 1.0 g of processing aid polymer
A stir bar, temperature controller, nitrogen line and condenser were attached to a 5 L round bottom flask. 1
, 245 g of deionized (DI) water, 0.1 g of sodium hydroxide (50% aqueous solution) and 9.84 g of DOWNFAX 2A1 (46% active) were loaded into the reaction vessel. The mixture was heated to 40 ° C. under nitrogen diffusion. Switched diffusion to sweep. 27.05g BMA, 92
.. A monomer mixture of 55 g of BA, 575.23 g of MMA and 38.83 g of AAEM was blended and then added to the reaction vessel. Next, 0.30 g of Sequence (5)
% Activity), 0.11 g EDTA disodium and 10 g DI water solution were added to the reactor. Next, 0.83 g of sodium persulfate in 10 g of DI water was added. Next, a mixture of 0.10 g Lykopon and 0.09 g sodium formaldehyde sulfonelate in 10 g DI water was added. This reaction was observed to rise to 39.3 ° C. over 61 minutes. After reaching peak exotherm, the reaction was cooled to 40 ° C. Then 2
39.38 g DOWNFAX 2A1 (46% active) in 0 g DI water was added to the reaction vessel. Then 34.43 g of BMA, 117.79 g of BA, and 732.11 g of MMA.
The monomer mixture was mixed and added to the reaction vessel. Next, 0.08 g of sodium formaldehyde sulfoxylate in 10 g of DI water was added to the reaction vessel. Next, 0.13 g of t-butyl hydroperoxide (70% active) in 10 g of DI water was added to the reaction vessel. This reaction was observed to increase in temperature to 49.0 ° C. over 39 minutes. 75 this reaction solution
The mixture was cooled to ° C. and 10.82 g DOWNFAX 2A1 (46% active) in 10 g DI water was added. The reaction was cooled to 60 ° C., 0.70 g of sodium persulfate in 10 g of DI water was added, and the reaction was kept at 60 ° C. for 30 minutes. The reaction was cooled to 50 ° C. and 0.63 g sodium sulfate in 10 g DI water was added. The reaction was cooled to 40 ° C. and filtered through a mesh cloth (52.8% solid).

Examples 2 and 4 of the present invention are AA added in the second stage of multi-stage emulsion polymerization.
It was blended by the step of synthesizing a processing aid polymer having EM. Multi-stage emulsion polymerization was carried out as follows.

Example 2: 0.000224 mol of AAEM per 1.0 g of processing aid polymer
A stir bar, temperature controller, nitrogen line and condenser were attached to a 5 L round bottom flask. 1
, 245 g of deionized (DI) water, 0.1 g of sodium hydroxide (50% aqueous solution) and 9.84 g of DOWNFAX 2A1 (46% active) were loaded into the reaction vessel. The mixture was heated to 40 ° C. under nitrogen diffusion. Switched diffusion to sweep. 27.05g BMA, 81
.. A monomer mixture of 16 g of BA and 569.54 g of MMA was added to the reaction vessel. Next, 0.30 g of Sequence (5% activity) and 0.11 g of EDTA.
A solution of disodium and 10 g of DI water was added to the reactor. Next, 0.83 g of sodium persulfate in 10 g of DI water was added. Then 0.10 g Lyko in 10 g DI water
A mixture of pon and 0.09 g of sodium formaldehyde sulfoxylate was added. The reaction was observed to rise to 37.9 ° C. over 88 minutes. After reaching peak exotherm, the reaction was cooled to 40 ° C. Next, 39.38 g of DOWNFAX 2A1 (46% active) in 20 g of DI water was added to the reaction vessel. Next, 34.43 g of BMA,
A monomer mixture of 103.29 g of BA, 724.86 g of MMA and 77.66 g of AAEM was added to the reaction vessel. Next, 0.08 g of sodium formaldehyde sulfoxylate in 10 g of DI water was added to the reaction vessel. Next, 0.1 in 10 g of DI water
3 g of t-butyl hydroperoxide (70% active) was added to the reaction vessel. This reaction is 4
The temperature was observed to rise to 49.6 ° C. over 2 minutes. The reaction was cooled to 75 ° C. and 10.82 g DOWNFAX 2A1 (46% active) in 10 g DI water was added.
The reaction was cooled to 60 ° C., 0.70 g of sodium persulfate in 10 g of DI water was added, and the reaction was kept at 60 ° C. for 30 minutes. The reaction solution is cooled to 50 ° C. and 10
0.63 g of sodium sulfate in g of DI water was added. The reaction was cooled to 40 ° C. and filtered through a mesh cloth (52.2% solid).

Example 4: 0.000112 mol of AAEM per 1.0 g of processing aid polymer
A stir bar, temperature controller, nitrogen line and condenser were attached to a 5 L round bottom flask. 1
, 245 g of deionized (DI) water, 0.1 g of sodium hydroxide (50% aqueous solution) and 9.84 g of DOWNFAX 2A1 (46% active) were loaded into the reaction vessel. The mixture was heated to 40 ° C. under nitrogen diffusion. Switched diffusion to sweep. 27.05g BMA, 92
.. A monomer mixture of 55 g of BA and 575.23 g of MMA was added to the reaction vessel. Next, 0.30 g of Sequence (5% activity) and 0.11 g of EDTA.
A solution of disodium and 10 g of DI water was added to the reactor. Next, 0.83 g of sodium persulfate in 10 g of DI water was added. Then 0.10 g Lyko in 10 g DI water
A mixture of pon and 0.09 g of sodium formaldehyde sulfoxylate was added. The reaction was observed to rise to 38.6 ° C. over 82 minutes. After reaching peak exotherm, the reaction was cooled to 40 ° C. Next, 39.38 g of DOWNFAX 2A1 (46% active) in 20 g of DI water was added to the reaction vessel. Next, 34.43 g of BMA,
A monomer mixture of 117.79 g of BA, 732.11 g of MMA and 38.83 g of AAEM was added to the reaction vessel. Next, 0.08 g of sodium formaldehyde sulfoxylate in 10 g of DI water was added to the reaction vessel. Next, 0.1 in 10 g of DI water
3 g of t-butyl hydroperoxide (70% active) was added to the reaction vessel. This reaction is 3
The temperature was observed to rise to 49.2 ° C. over 5 minutes. The reaction was cooled to 75 ° C. and 10.82 g DOWNFAX 2A1 (46% active) in 10 g DI water was added.
The reaction was cooled to 60 ° C., 0.70 g of sodium persulfate in 10 g of DI water was added, and the reaction was kept at 60 ° C. for 30 minutes. The reaction solution is cooled to 50 ° C. and 10
0.63 g of sodium sulfate in g of DI water was added. The reaction was cooled to 40 ° C. and filtered through a mesh cloth (52.8% solid).

Comparative Examples 1 and 2 were blended by the step of synthesizing a processing aid polymer having AAEM added in both the first and second stages of multistage emulsion polymerization. The multi-stage emulsion polymerization was carried out as follows.

Comparative Example 1: 0.000224 mol of AAEM per 1.0 g of processing aid polymer
A stir bar, temperature controller, nitrogen line and condenser were attached to a 5 L round bottom flask. 1
, 245 g of deionized (DI) water, 0.1 g of sodium hydroxide (50% aqueous solution) and 9.84 g of DOWNFAX 2A1 (46% active) were loaded into the reaction vessel. The mixture was heated to 40 ° C. under nitrogen diffusion. Switched diffusion to sweep. 27.05g BMA, 81
.. A monomer mixture of 16 g of BA, 569.54 g of MMA and 34.17 g of AAEM was mixed and then added to the reaction vessel. Next, 0.30 g of Sequence (5)
% Activity), 0.11 g EDTA disodium and 10 g DI water solution were added to the reactor. Next, 0.83 g of sodium persulfate in 10 g of DI water was added. Next, a mixture of 0.10 g Lykopon and 0.09 g sodium formaldehyde sulfonelate in 10 g DI water was added. This reaction was observed to rise to 42.4 ° C. over 75 minutes. After reaching peak exotherm, the reaction was cooled to 40 ° C. Then 2
39.38 g DOWNFAX 2A1 (46% active) in 0 g DI water was added to the reaction vessel. Next, a monomer mixture of 34.43 g of BMA, 103.29 g of BA, 724.86 g of MMA and 43.49 g of AAEM was added to the reaction vessel. Next, 10g of D
I Add 0.08 g of sodium formaldehyde sulfoxylate in water to the reaction vessel. Next, 0.13 g of t-butyl hydroperoxide (70% active) in 10 g of DI water was added to the reaction vessel. This reaction was observed to rise to 47.4 ° C. over 34 minutes. The reaction was cooled to 75 ° C. and 10.82 g DOWNFAX in 10 g DI water.
2A1 (46% active) was added. The reaction solution was cooled to 60 ° C. and 0.
70 g of sodium persulfate was added and the reaction was kept at 60 ° C. for 30 minutes. The reaction was cooled to 50 ° C. and 0.63 g sodium sulfate in 10 g DI water was added.
The reaction was cooled to 40 ° C. and filtered through a mesh cloth (52.5% solid).

Comparative Example 2: 0.000112 mol of AAEM per 1.0 g of processing aid polymer
A stir bar, temperature controller, nitrogen line and condenser were attached to a 5 L round bottom flask. 1
, 245 g of deionized (DI) water, 0.1 g of sodium hydroxide (50% aqueous solution) and 9.84 g of DOWNFAX 2A1 (46% active) were loaded into the reaction vessel. The mixture was heated to 40 ° C. under nitrogen diffusion. Switched diffusion to sweep. 27.05g BMA, 92
.. A monomer mixture of 55 g of BA, 575.23 g of MMA and 17.09 g of AAEM was mixed and then added to the reaction vessel. Next, 0.30 g of Sequence (5)
% Activity), 0.11 g EDTA disodium and 10 g DI water solution were added to the reactor. Next, 0.83 g of sodium persulfate in 10 g of DI water was added. Next, a mixture of 0.10 g Lykopon and 0.09 g sodium formaldehyde sulfonelate in 10 g DI water was added. This reaction was observed to increase in temperature to 40.3 ° C. over 80 minutes. After reaching peak exotherm, the reaction was cooled to 40 ° C. Then 2
39.38 g DOWNFAX 2A1 (46% active) in 0 g DI water was added to the reaction vessel. Next, a monomer mixture of 34.43 g of BMA, 117.79 g of BA, 732.11 g of MMA and 21.75 g of AAEM was added to the reaction vessel. Next, 10g of D
I Add 0.08 g of sodium formaldehyde sulfoxylate in water to the reaction vessel. Next, 0.13 g of t-butyl hydroperoxide (70% active) in 10 g of DI water was added to the reaction vessel. This reaction was observed to rise to 49.2 ° C. over 42 minutes. The reaction was cooled to 75 ° C. and 10.82 g DOWNFAX in 10 g DI water.
2A1 (46% active) was added. The reaction solution was cooled to 60 ° C. and 0.
70 g of sodium persulfate was added and the reaction was kept at 60 ° C. for 30 minutes. The reaction was cooled to 50 ° C. and 0.63 g sodium sulfate in 10 g DI water was added.
The reaction was cooled to 40 ° C. and filtered through a mesh cloth (52.6% solid).

The emulsion was converted to powder by oven drying at 60 ° C. Similarly, the emulsion can be dried by any method known in the art, such as spray drying, fluidized bed drying, coagulation followed by drying.

Each of the Examples and Comparative Examples was blended with a masterbatch formulated as specified in Table 1.

The ingredients were blended in a Henschel blender to create a masterbatch. After loading the PVC and the blades began to rotate, the temperature of the blender rose from frictional heat at approximately 3-5 ° C./min. After loading the PVC, the remaining components were added through the addition port when the temperature reached the temperatures listed below.

The blender was loaded with PVC at 25 ° C. and the lid was closed. Switch on the mixing blade at about 1,000 rpm. Monitor the temperature. Do not cool. ADVASTAB TM-18
1 Stabilizer is added at 52 ° C. ADVALUBE B3310, paraffin wax, XL
-165, AC-629A and calcium stearate are added at 66 ° C. Lubricating processing aid PARALOID K-175 and foaming agent Ficel ES55 HVC at 77 ° C.
Add with. Titanium dioxide and calcium carbonate are added at 90 ° C. The flow of cooling water is started at 100 ° C. Reduce the blade speed to near the minimum value (about 200 rpm). 45 ° C
Cool to, switch off the blade, and remove the masterbatch powder from the blender.

The compounded PVC was extruded on a Hake, Polylab contra-rotating screw extruder. Zone 1 was set at 1,550 ° C. Zone 2 was set at 175 ° C. Zone 3 was set to 180 ° C. The die was a coat hanger type die with a 50 mm wide opening and a 1 mm gap between the lips. The die temperature was set to 150 ° C. Extruder 4
Run at 5 rpm and the PVC powder was fed into the extruder throat by gravity feed. The foamed PVC that came out of the extruder was run through a 3-roll type laminated cooling device set at 20 ° C. The gap between the cooling rolls was 2.79 mm.

The processing aids of the Examples were post-added to the masterbatch at a concentration of 10 parts per 100 parts (PHR) on PVC and mixed by shaking in a bag to produce the Formulations of the Examples.

Definition:
Concentration of AAEM: AA in the polymer composition, expressed as% by weight of the polymer processing aid.
Total amount of EM.
Placement of AAEM: Where AAEM is added to the polymerization, first stage, second stage or both (
This is a two-stage polymer example).

Test method:
The test method includes:
Molecular weight measurement by size exclusion chromatography (SEC) was performed as follows.
Samples were formulated in tetrahydrofuran at a concentration of about 1.0 mg / mL. Samples were shaken on a shaker at room temperature for at least overnight. The sample solution was filtered using a 0.45 μm PTFE filter prior to SEC analysis.

Separation was performed at 40 ° C. on a liquid chromatograph consisting of an Agilent (Santa Clara, Calif.) 1100 series pump, autosampler and index of refraction (RI) detector. System control, data collection and data processing were performed using Chemstation software (Agilent).

SEC separation is carried out in tetrahydrofuran at a flow rate of 1.0 mL / min, Polymer L.
This was performed using two PLGel Mixed A columns (300 times, inner diameter 7.5 mm) filled with polystyrene-divinylbenzene gel purchased from aboratories (one business unit of Agilent). A 100 μL sample solution with a concentration of about 1.0 mg / mL was subjected to SEC separation. Weight average and number average molecular weights were recorded for each example.

Calibration: 580-7,500 with a concentration of about 0.5 mg / mL in tetrahydrofuran
Builds a polystyrene (PS) 10 points calibration curve using standard substances (primary) with M _p which is within the range of 000 g / mol, relative molecular weight of the samples analyzed using this (
M) was evaluated.

Solution viscosity in acetone: 24 g 40.5% solid emulsion, 156 with mixing
It was added to an 8 ounce wide-mouthed jar containing g of acetone. After mixing for 2 hours, the clay was measured by Brookfield DV-II viscosity counting using a No. 3 spindle set at room temperature at 60 rpm. Solution viscosity is another indicator of molecular weight with high viscosity corresponding to high molecular weight.

The density is 0.75 inches x 1.25 inches (1.905 cm x 3.17) from the strip.
Measured on an extruded foam strip by cutting a piece of foam ( 5 cm) . Density is
It was determined using the ASTM D792 method. The thickness of the foam strip was determined by measuring the maximum thickness of the strip using a digital caliper. Gloss is Gard
It was measured using a 75 degree microgloss meter manufactured by ner.

The present invention can be embodied in other forms without departing from the spirit of the present invention and the essential properties of the present invention, and thus, rather than the above specification, an attachment indicating the scope of the present invention. You should refer to the claims of.
Specific examples of the invention of the present application provided by the above disclosure include the following inventions.
[1] Units derived from non-functional ethylenically unsaturated monomers in an emulsion polymerization reactor
25-75 wt% first stage polymer including;
0-99.6 mol% units from one or more non-functional ethylenically unsaturated monomers and
2 Containing 0.4-100 mol% units from one or more functionalized ethylenically unsaturated monomers
A multi-stage emulsion processing aid polymer containing 5 to 75% by weight of a second stage polymer.
The functional groups are β-ketoester, β-ketoamide, β-diketone, and cyanoacetic acid esthetics.
Le, malonate, nitroalkane, β-nitroester, sulfone azide, thiol, thio
Selected from the group consisting of all-s-triazines and amines, said functional groups are these functional groups.
Additional by the step of polymerizing an ethylenically unsaturated monomer containing a functional group, or after polymerization
Incorporated into the polymer by post-functionalization of the polymer using an additive reaction; and
The processing aid polymer has a Mw of 700,000 or more.
Multi-stage emulsion processing aid polymer.
[2] The functionalized ethylenically unsaturated monomer is β-ketoester and amide, β-di.
Of ketones, cyanoacetic acid esters, malonates, nitroalkanes and β-nitroesters
The multistage emulsion processing aid polymer according to [1], which is selected from the group.
[3] The functionalized ethylenically unsaturated monomer is acetoacetoxyethyl (meth) acrylic.
Rate, acetoacetoxypropyl (meth) acrylate, acetoacetoxybutyl (me)
A) Acrylate, 2,3-di (acetoacetoxy) propyl (meth) acrylate, a
Setoacetoxyethyl (meth) acrylamide, 2-cyanoacetoxyethyl (meth) a
Clilate, 2-cyanoacetoxyethyl (meth) acrylamide, N-cyanoacetyl
-N-Methylaminoethyl (meth) acrylate, N- (2 propionylacetoxybuty)
L) The multiple according to any one of [1] to [2] selected from the group of (meth) acrylamide.
Step emulsion processing aid polymer.
[4] The functionalized ethylenically unsaturated monomer is AAEM, and the processing aid polymer is
The multistage emulgi according to any one of [1] to [3], which has a Tg between 10 ° C and 150 ° C.
Processing aid polymer.
[5] The functionalized ethylenically unsaturated monomer is AAEM, and the processing aid polymer is
The multistage emulsion processing aid polymer according to [4], which has a Tg between 55 ° C. and 150 ° C.
..
[6] The functionalized ethylenically unsaturated monomer is AAEM, and the processing aid polymer is
The multi-stage emulsion processing aid polymer according to [1], which has an Mw of 1,600,000 or more.
-.
[7] One or more non-functional ethylenically unsaturated monomers in an emulsion polymerization reactor
Derived from the coming 0-99.6 mol% units and one or more functionalized ethylenically unsaturated monomers
25-75% by weight first-stage polymer containing 0.4-100 mol% units, said
Noh groups are β-ketoester, β-ketoamide, β-diketone, cyanoacetic acid ester, malo.
Nate, nitroalkane, β-nitroester, sulfone azide, thiol, thiol-
Selected from the group consisting of s-triazines and amines, said functional groups are these functional groups.
Additional reactions by or after the step of polymerizing the ethylenically unsaturated monomers contained
The first stage polymer is incorporated into the polymer by post-functionalization of the polymer using
Bini
25-75% by weight second stage polymer containing units derived from non-functional ethylenically unsaturated monomers
A multi-stage emulsion processing aid polymer containing
The processing aid polymer is a multi-stage emulsion processing aid having an Mw of 700,000 or more.
polymer.
[8] The functionalized ethylenically unsaturated monomer is AAEM, and the processing aid polymer is
The multistage emulsion processing aid polymer according to [7], which has a Tg between 10 ° C. and 150 ° C.
..
[9] The functionalized ethylenically unsaturated monomer is AAEM, and the processing aid polymer is
The multistage emulgi according to any one of [7] to [8], which has a Tg between 55 ° C and 150 ° C.
Processing aid polymer.
[10] The functionalized ethylenically unsaturated monomer is AAEM, and the processing aid polymer.
The multi-stage emma according to any one of [7] to [9], which has an Mw of 1,600,000 or more.
Lujon processing aid polymer.
[11] (a) For vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene chloride
And one or more monomers selected from chlorinated polyvinyl chloride and chlorinated polyethylene
Homopolymers or copolymers containing at least 80% by weight of halogenated polymers (
20-99% by weight of one or more halogenated polymers selected from A); and (b) Contract
A formulation containing 0.5 to 20% by weight of one or more multi-step processing aid polymers according to claim 1.
Therefore, the one or more processing aid polymers are 100 g of the halogenated polymer in the formulation.
Per functionalized monomer at a concentration providing 0.00040-0.0056 mol of repeating units
The formulation used.
[12] The functionalized ethylenically unsaturated monomer is β-ketoester and amide, β-.
Diketone, cyanoacetate, malonate, nitroalkane and β-nitroester
The formulation according to [11], which is selected from the group of.
[13] The functionalized ethylenically unsaturated monomer is acetoacetoxyethyl (meth) ac.
Relate, acetoacetoxypropyl (meth) acrylate, acetoacetoxybutyl (
Meta) acrylate, 2,3-di (acetoacetoxy) propyl (meth) acrylate,
Acetacetoxyethyl (meth) acrylamide, 2-cyanoacetoxyethyl (meth)
Acrylate, 2-cyanoacetoxyethyl (meth) acrylamide, N-cyanoacetyl
Lu-N-methylaminoethyl (meth) acrylate, N- (2 propionylacetoxyb)
The formulation according to [11], selected from the group of chill) (meth) acrylamide.
[14] (a) For vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene chloride
And one or more monomers selected from chlorinated polyvinyl chloride and chlorinated polyethylene
Homopolymers or copolymers containing at least 80% by weight of halogenated polymers (
20-99% by weight of one or more halogenated polymers selected from A); and (b) Contract
A formulation containing 0.5 to 20% by weight of one or more multi-step processing aid polymers according to claim 7.
Therefore, the one or more processing aid polymers are 100 g of the halogenated polymer in the formulation.
Per functionalized monomer at a concentration providing 0.00040-0.0056 mol of repeating units
The formulation used.
[15] Water in the emulsion polymerization reactor, at least one non-functional ethylenically unsaturated
The first stage poly of the multistage emulsion polymer is supplied by supplying the monomer and surfactant.
In the step of forming the mer, the first-stage polymer is the total of the multi-stage emulsion polymers.
Steps that make up 25% to 75% by weight of weight;
One or more functionalizations in the emulsion polymerization reactor in the presence of the first stage polymer.
A step of supplying a chillene unsaturated monomer to form a second-stage polymer, wherein the functionalization is performed.
The functional groups of the ethylenically unsaturated monomer are β-ketoester, β-ketoamide, and β-diketo.
, Cyanoacetic acid ester, malonate, nitroalkane, β-nitroester, sulfone
Selected from the group consisting of azides, thiols, thiol-s-triazines and amines, pre
The functional groups polymerize or polymerize ethylenically unsaturated monomers containing these functional groups.
Incorporated into the polymer by post-functionalization of the polymer with an additional reaction after polymerization, said
The second-stage polymer comprises 25% by weight to 75% by weight of the total weight of the multi-stage emulsion polymer.
Process to be done;
The multi-stage emulsion polymer is dried or left to dry, thereby multiplying
Step Emulsion Polymer A multi-step emulsion polymerization method comprising the step of forming a processing aid.

Claims (11)

35-65% by weight of the multistage polymer comprising units derived from a non-functional ethylenically unsaturated monomers
1st stage polymer moiety within ; as well as 0-99.6 mol% units from one or more non-functional ethylenically unsaturated monomers and 0.4 to 0.4 from one or more functionalized ethylenically unsaturated monomers. 3 containing 100 mol% units
5 to a multi-stage Emarujo emission port Rimmer containing second stage polymer portion <br/> in 65 wt% of the multistage polymer,
The non-functional ethylenically unsaturated monomer is ethyl acrylate or butyl acrylate.
, 2-Ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, t
ert-Butyl methacrylate, cyclohexyl methacrylate, hydroxyethyl meta
Crylate, acrylonitrile, methacrylic acid, acrylic acid, methacrylic acid, sty
Is it a group consisting of len, o-chlorostyrene, α-methylstyrene and combinations thereof?
Selected from
The functionalized ethylenically unsaturated monomer is acetoacetoxyethyl (meth) acryley.
To (AAEM), acetoacetoxypropyl (meth) acrylate, acetoacetoxyb
Chill (meth) acrylate, 2,3-di (acetoacetoxy) propyl (meth) acryle
Ethyl, acetoacetoxyethyl (meth) acrylamide, 2-cyanoacetoxyethyl (
Meta) acrylate, 2-cyanoacetoxyethyl (meth) acrylamide, N-cyano
Acetyl-N-methylaminoethyl (meth) acrylate, N- (2 propionyl aceto)
Kishibuchiru) (meth) the multi Dan'e Mar John polymer is selected from the group of acrylamide have a weight average molecular weight of more than 700,000 (Mw)
, Compatible with polyvinyl chloride,
The first-stage polymer portion of the multi-stage emulsion polymer is the functionalized ethylenically unsaturated
Does not contain monomer-derived units,
Multi-stage Emarujo down port Rimmer. Wherein the functionalized ethylenically unsaturated monomer is AAEM, before Kipo Rimmer 10 ° C. to 15
With a Tg of between 0 ° C., multistage Emarujo down port Rimmer of claim 1. Wherein the functionalized ethylenically unsaturated monomer is AAEM, before Kipo Rimmer 55 ° C. to 15
With a Tg of between 0 ° C., multistage Emarujo down port Rimmer of claim 2. Wherein the functionalized ethylenically unsaturated monomer is AAEM, before Kipo Rimmer 1,600,
000 having the above Mw, multistage Emarujo down port Rimmer of claim 1. Comprises one or more nonfunctional ethylenically unsaturated monomers derived from 0 to 99.6 mol% of the unit and one or more units of 0.4-100 mole% derived from functionalized ethylenically unsaturated monomers,
35 The first stage polymer portion in the multi-stage polymer to 65 wt%; and 35 to 65% by weight of the multistage polymer comprising units derived from a non-functional ethylenically unsaturated monomers
A multistage Emarujo emission port Rimmer containing second stage polymer portion <br/> of the inner,
The non-functional ethylenically unsaturated monomer is ethyl acrylate or butyl acrylate.
, 2-Ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, t
ert-Butyl methacrylate, cyclohexyl methacrylate, hydroxyethyl meta
Crylate, acrylonitrile, methacrylic acid, acrylic acid, methacrylic acid, sty
Is it a group consisting of len, o-chlorostyrene, α-methylstyrene and combinations thereof?
Selected from
The functionalized ethylenically unsaturated monomer is acetoacetoxyethyl (meth) acryley.
To (AAEM), acetoacetoxypropyl (meth) acrylate, acetoacetoxyb
Chill (meth) acrylate, 2,3-di (acetoacetoxy) propyl (meth) acryle
Ethyl, acetoacetoxyethyl (meth) acrylamide, 2-cyanoacetoxyethyl (
Meta) acrylate, 2-cyanoacetoxyethyl (meth) acrylamide, N-cyano
Acetyl-N-methylaminoethyl (meth) acrylate, N- (2 propionyl aceto)
Kishibuchiru) (meth) prior selected from the group of acrylamide Kipo Rimmer has a weight average molecular weight of more than 700,000 (Mw),
The second-stage polymer portion of the multi-stage emulsion polymer is the functionalized ethylenically unsaturated
Does not contain monomer-derived units,
Multi-stage emulsion polymer. Wherein the functionalized ethylenically unsaturated monomer is AAEM, before Kipo Rimmer 10 ° C. to 15
With a Tg of between 0 ° C., multistage Emarujo down port Rimmer of claim 5. Wherein the functionalized ethylenically unsaturated monomer is AAEM, before Kipo Rimmer 55 ° C. to 15
With a Tg of between 0 ° C., multistage Emarujo down port Rimmer according to claim 5 or 6. Wherein the functionalized ethylenically unsaturated monomer is AAEM, before Kipo Rimmer 1,600,
000 having the above Mw, multistage Emarujo emission port Li <br/> mer according to any one of claims 5-7. (A) Homopolymers or copolymers comprising at least 80% by weight of halogenated polymers of one or more monomers selected from vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride and chlorinated polyvinyl chloride and chlorinated polyethylene. 20-99% by weight of one or more halogenated polymers selected from (A); and
(B) A formulation containing 0.5 to 20% by weight of one or more multi-stage emulsion polymers according to claim 1, wherein the one or more multi-stage emulsion polymers are halogenated polymers in the formulation. Functionalized monomer repeating unit per 100 g 0.00040 to 0.00
Used at a concentration to provide 56 mole formulation. (A) Homopolymers or copolymers comprising at least 80% by weight of halogenated polymers of one or more monomers selected from vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride and chlorinated polyvinyl chloride and chlorinated polyethylene. 20-99% by weight of one or more halogenated polymers selected from (A); and
(B) A formulation containing 0.5 to 20% by weight of one or more multi-stage emulsion polymers according to claim 5 , wherein the one or more multi-stage emulsion polymers are halogenated polymers in the formulation. Functionalized monomer repeating unit per 100 g 0.00040 to 0.00
Used at a concentration to provide 56 mole formulation. Water in the emulsion polymerization reactor, feeding at least one non-functional ethylenically unsaturated monomer and surfactant, whereby the first stage polymer of the multistage emulsion polymer
As Engineering to form a minute;
One or more functionalized ethylenically unsaturated monomers are supplied into the emulsion polymerization reactor in the presence of the first stage polymer portion of the multistage polymer to provide the multistage emulsion polymer portion.
And forming a second stage polymer portion,
The first stage polymer portion is 35% by weight to 6% by weight of the total weight of the multistage emulsion polymer.
Consisting of 5% by weight, the second stage polymer portion is the total weight of the multistage emulsion polymer.
Consisting of 35 % to 65 % by weight , the polymer has a Mw of 700,000 or more.
Step; and the allowed to or dried drying the multistage emulsion polymer, thereby forming a multi-stage emulsion polymer as a processing aid for halogenated polymers,
Only including,
The non-functional ethylenically unsaturated monomer is ethyl acrylate or butyl acrylate.
, 2-Ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, t
ert-Butyl methacrylate, cyclohexyl methacrylate, hydroxyethyl meta
Crylate, acrylonitrile, methacrylic acid, acrylic acid, methacrylic acid, sty
Is it a group consisting of len, o-chlorostyrene, α-methylstyrene and combinations thereof?
Selected from
The functionalized ethylenically unsaturated monomer is acetoacetoxyethyl (meth) acryley.
To (AAEM), acetoacetoxypropyl (meth) acrylate, acetoacetoxyb
Chill (meth) acrylate, 2,3-di (acetoacetoxy) propyl (meth) acryle
Ethyl, acetoacetoxyethyl (meth) acrylamide, 2-cyanoacetoxyethyl (
Meta) acrylate, 2-cyanoacetoxyethyl (meth) acrylamide, N-cyano
Acetyl-N-methylaminoethyl (meth) acrylate, N- (2 propionyl aceto)
Selected from the group of xybutyl) (meth) acrylamide
The first-stage polymer portion of the multi-stage emulsion polymer is the functionalized ethylenically unsaturated
Multi-stage emulsion polymerization method that does not contain units derived from monomers .