DE1939911A1 - Sulphonated aromatic polyisocyanates and production of stable anionic polyurethane or polyurea latices from them - Google Patents

Description

'' i .: ι;.; ί λCULAR

IvI 2665

Minnesota Mining and Manufacturing Company, Saint Paul, Minnesota 551Ü1, V.St.A,

Sulphonated Aromatic Polyisocyanates and Manufacture of stable anionic polyurethane or polyurea latices

from it.

The present invention relates to anionic polyurethanes (including Polyurethane polyurea) or polyurea latices, a process for their production and sulfonated aromatic polyisocyanates, the. are used for their preparation »In particular, the invention relates to sulfonic acid salt groups containing prepolymers, which remain in stable aqueous emulsion after chain extension, without separate To need emulsifiers, and also the latices resulting therefrom and the process for their preparation.

In British patent specification 1 Ü? 8 202 of August 9, 1967 It has already been proposed to produce polyurethane latices that were free of emulsifiers by making salt-like Introduced groups into the polymer. Such incorporation was generally carried out in solution by a Prepolymer, άεα? Has isoyanate end groups, rail one

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Reacted component that reacts with two isocyanate groups and contains a salt-forming group, or inaera one the Chain of the prepolymer containing isocyanate end groups with a monofunctional component that contained a salt-forming group, partially broke off. In the former case the "' chemical structure of the polymer changed, often Changes in physical properties ultimately obtained difficult to control. The latter process prevents the chain degradation of that part of the prepolymer that is part of the rest of the prepolymer Extension has been prevented or blocked, which also results in changes in the physical properties, which in this case is due to a lower degree of polymerization. According to that in the present invention The process described is carried out uie polymerization in solution in an organic solvent, after which in an aqueous phase is transferred. In general, muli that organic solvents by a separate distillation process removed.

In British Patent 1,146,890 there are polyurethanes which contain oü. groups, but these are Groups easily split off, giving control of the physical Properties of the polymer finally obtained becomes complicated.

The present invention proposes a method of manufacture of stable latices made from chain-extended prepolymers with terminal isocyanate groups, through which the above-mentioned Difficulties can be avoided. According to the invention, sulfonic acid iialzgruppen in prepolymers with Isocyanate end groups introduced by simple measures and without changing the main polymer chain. It has been found to have stable anionic polyurethane, including polyurethane, polyurea, or polyurea latices

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can be easily produced by adding an aroma- '* table polyisocyanate or a prepolymer, the Isooyanatendgruppen with a strong sulfonating agent, which sulfuric acid, sulfur trioxide, chlorosulfonic acid or may be a mixture of these treated the sulfonic acid groups converted into sulfonic acid salt groups, emulsified in water and chain extension with simple polyfunctional (including bifunctional) molecules, whatever of water and polyamines.

The prepolymer with isocyanate end groups, which according to the invention contain sulfonic acid salt groups, can be easily dispersed in water, so that generally little or no inert solvent is required to reduce the viscosity of the prepolymer, so that the dispersion into small latex particles can be done. The invention proposes staoile polyurethane (including polyurethane polyurea) or Polyharnstofflatices BeFore ₅ aie no separate dispersing agents. The polymer latices according to the invention are anionic in nature and have excellent stability over a wide pH range. They are also stable against mechanical effects, against the addition of various additives such as pigments and thickeners, and against freezing. Films made from the latices according to the invention are resistant to yellowing.

The inventive method of sulfanic acid has the advantage that that the sulfonation is easy to proceed una as part of the ·· Process for the reaction of the diisocyanate with aera polyhydroxymaterial can be inserted, so that there is no separate boiler stage is required. Emulsification of the sulfonated prepolymer can be carried out with only a slightly increased amount of work.

The latices according to the invention have good mechanical stability and can easily be used as xiinamittel for latex-otreichf & raw

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BATH ORIGINAL

be used. In that regard, they have a good one Adhesion to bricks, for example, and the application devices can be cleaned by washing them in clear water will.

These latices are generally, as they are made, neutral, but they are stable under both acidic and alkaline conditions. You can borrow by adding the usual thickeners. No separate emulsifier is used in their manufacture, therefore are the properties of the films or coatings that are made of are produced by the presence of such raw materials not affected. Films cast from the latices are generally clear and colorless and excellent Physical Properties.

In the process according to the invention, a salt-forming Group introduced into aas prepolymer without changing its structure in any other way. This makes the structure of poly- i merisates with a minimum of complications by one: overshoe of urea or urethane or other groups in the; Polymer structure originate, allows.

The reaction of phenyl isocyanate with sulfuric acid to form sulfanilic acid is described by Bieber in "J.Am.Chem.tJoc. 75» 14Ü5 (1953) ": =

O + CO

* ⁴

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Bieber believed that the first reaction was the addition of the sulfuric acid to the isocyanate to form a mixed one Anhydrides. The sulfanilic acid then results either through intramolecular rearrangement or intermolecular Sulfonation. In any case, the overall effect is the sulfonation of the phenyl isocyanate by the sulfuric acid. the Sulphonation can also be carried out directly by using oleum, sulfur trioxide or chlorosulphonic acid as the sulphonating agent be performed. The term "sulfur trioxide", as used here, is intended to mean complexes thereof with other compounds, such as dioxane.

According to the invention, the reaction proceeds as follows: 0 ^NC0

OCN-R-OC ^ NH -

fl
OCN-ROC-NH-

NH :

so"

-CH

+ Base

QCN-R-Ü-CO-NH-

+ second prepolymer

NH-C-R-NCO

, where R is a prepolymer chain

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With Üleura, sulfur trioxide or chlorosulphonic acid, a direct sulphonation of a terminal benzene ring containing an isocyanate group or an inner benzene ring occurs, which ultimately leads to a similar sul- ^; Formed prepolymer leads, which can be emulsified in water containing a "-" · "base without the need to add any emulsifying agent. Similar reactions can be carried out with other aromatic polyisocyanates,

The reaction of sulfuric acid with prepolymers which have been prepared from toluene diisocyanate (TDI) and pulyoxypropylene glycols is generally carried out by heating to 75 ° C., the development of CU _{2 being} essentially complete after 5-10 minutes. The analysis of the product after cooling and neutralization shows that two equivalents of isocyanate per mole of added sulfuric acid have been consumed.The sulfonated prepolymers emulsify when stirred into water themselves to form stable latioes, due to the presence of sulfonic acid salt groups along the polymer chains .

Similar results are obtained by adding a percentage of the aromatic polyisocyanates with sulfuric acid, sulfur trioxide or chloric acid and converts the sulfonated product into one Add prepolymer. Those from such mixtures of sulfonated polyisocyanates and non-sulfonated prepolymers The latices formed appear to be completely equivalent to those produced by direct sulfonation of the prepolymer with the same sulfonic acid content have been. Aromatic polyisocyanates with a molecular weight between about 160 and 25,000, preferably up to 10,000, according to the invention, can be sulfonated into the sulfonic acids Salts are converted, chain-extended and self-emulsified to form latices. The designation. "Polyiso-

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cyanate ", as used herein, is intended to include both commercially available, relatively low molecular weight materials and include higher molecular prepolymers with polyisocyanate end groups. The low molecular weight sulfonated prepolymers are preferably mixed with higher molecular weight prepolymers in order to form rubber-like polymers. High molecular weight Pre-polymers may require dilution with volatile solvents in order to facilitate the emulsification.

The preferred ^ prepolymers with terminal isocyanate groups, which are used according to the invention, by reacting a hydroxyl-terminated material with a polyisocyanate produced. The hydroxyl-terminated material is usually a polyalkylene ether glycol, and the polyisocyanate is usually an aromatic diisocyanate. The ratio of wCu to ÜH groups in uen implementation participants is preferably between 1.5: 1 and 2.5: 1, although acidic ratios in the range of about 1.2: 1 to 1u: 1 used to achieve various effects

; can be. The implementation is carried out in a convenient way through

\ Su to the Jmaetzungsteilnehmer overheat ⁰ C for 3 otunden and then IVUE Uhj.en performed. Substantially longer heating or higher temperatures can lead to crosslinking ^! call forward.

\ The prepolymers used to prepare the polyoxyalkylene polyols generally have una lviolekulargewichte ranging from about 3ΰυ to about 5üüü and preferably 'from about 4üo · to 3000, more ruckfedernde polymers are usually obtained with the higher molecular weight glycols.

Examples of such polyoxyalkylene glycols are polyoxyethylene : glycol, polyoxypropylene glycol, polyoxytetramethylene glycol and higher polyoxyalkylene glycols. These are polyether glycols with the help of the well-known opening or conaensation poly-

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regeneration established. If these polyols contain repeating oxyethylene groups, the total weight fraction should be ^; such oxyethylene groups are regulated ^ since this structure tends to give the finished product a sensitivity to water. Other suitable polyols are, for example, castor oil, polybutadiene with hydroxyl end groups and vinyl polymers with hydroxyl groups, preferably with molecular weights in the range from 5U to 5000 of polyether urea prepolymers with isocyanate groups.

The polyester glycols or polyols can be used alone or in combination with polyether glycols for the production of polymers used according to the invention. Polyester glycols or polyols can, for example, by reacting dicarboxylic acids, esters or acid halides with simple. Glycols or polyols are produced. Suitable glycols are polymethylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tetramethylene glycol, decamethylene glycol, substituted polymethylene glycols such as 2,2-dimethyl-1,3-propanediol, and cyclic glycols such as cyclohexanediol. Polyols such as glycerol, pentaerythritol, trimethylolpropane and trimethylolethane can be used in limited amounts to introduce chain branching into the polyesters. These hydroxy compounds are reacted with aliphatic, cycloaliphatic or aromatic dicarboxylic acids or lower alkyl esters or ester-forming derivatives thereof in order to form polymers with terminal hydroxyl groups, which have melting points of less than about 7U ⁰ C and which are in the same approximate range as above for the polyoxyalkylene glycols specified are characterized; the colonic weights are preferably about 4μu to 4000, especially about 1000 to about 2000. Examples of suitable acids are

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—Q—

Succinic acid, adipic acid, suberic acid, sebacic acid, Phthalic acid, isophthalic acid, terephthalic acid, hexahydroterephthalic acid and the alkyl and halogen substituted derivatives of these acids.

A torpolymer can be prepared with or without a solvent, although the presence of a solvent can often facilitate mixing and handling. . Usual solvents which are inert to isocyanates can be used, for example toluene, xylene, etc. Various organic polyisocyanates, preferably aromatic polyisocyanates, can be used for the production of latices and / or prepolymers according to the invention. Because of their ready availability and the fact that they are liquid at room temperature, mixtures of the 2,4- and 2,6-toluene diisocyanate isomers are preferred. More preferred diisocyanates are 4,4 ^I -Diphenylenmethandiisocyanat and 3,3'-whore thyl-4,4'-diphenyl diisocyanate. Further examples of service _water: bare aromatic diisocyanates include p-phenylene diisocyanate, 'm-phenylene diisocyanate, 4,4 -Diphenyldiisocyanat ^I, 1,5-naphthalene diisocyanate, 4,4'-Mphenylätherdiisocyanat, 3,3 ~ dimethoxy ^I-4, 4'-diphenyl diide cyanate, xylylene diisocyanate and 4-chloro-1,3-phenylene diisocyanate.

If necessary, limited amounts of polyfunctional Material can be mixed with the glycol or the isocyanate to produce crosslinked polymers. Such networks in of the order of magnitude of about one crosslinking or less per 5UUÜÜ polymer atomic weight units have only one very little influence on the properties of the polymer. More than about one crosslinking per 3υυθ atomic weight units makes it more difficult maintaining good film forming properties. The crosslinking reduces aie thermoplasticity and the percentage elongation of the polymer and also tends to .zu a slight increase in the modulus if the polyfunctional one

BATH ORIGINAL

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-10-Vernetzurigsmaterial is a small iuolekül.

Small functional molecules, such as Diethylene glycol or diamines can be used as chain lengthening agents to increase the density of polar parts in the finished polymer, which increases physical properties such as modulus and tensile strength, accordingly. The prepolymer can be partially reacted with other glycols or other di- ._.- / functional or trifunctional materials, to the extent that the finished product still has isocyanate end groups, a detailed description of these prepolymers is given in the UiiA- U.S. Patent 3,178,310 issued April 13, 1965.

The prepolymer can be used directly or diluted with small amounts of an inert solvent such as toluene for the sulfonation stage. One-tenth to 2 G ew .- $ of sulfuric acid are added, and the mixture is heated for about 3Ü minutes at 75 C. It is then cooled to room temperature and a molar equivalent (based on the sulfuric acid) of a base such as triethylamine is added to the partially sulfonated prepolymer in order to neutralize the sulfonic acid groups. This sulfonated prepolymer has a reasonable shelf life and does not need to be used immediately. It can be stored for several days before being used to make a stable anionic latex with the same physical properties as a latex made from fresh material.

In summary, it can be said that the invention is the modification of an aromatic polyisocyanate (e.g. one or more of the diisocyanates already described or a copolymer with isocyanate end groups that is derived from such diisocyanates and one of the polyols given above]) with a strong Dulfonating agents, e.g. Ά ^ ϋ., ^ O ^, or Ci-oO-jH suggests. Wake up the neutralization of the modified

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Polyisocyanates with a base (e.g. an alkali hydroxide, a tertiary amine or a basic salt), the resulting product contains sulfonic acid salt groups and can be self-emulsified in water, whereby it is capable of chain extension. According to the invention, one of the above aromatic polyisocyanates with a molecular weight of less than 160 or one of the above prepolymers, which can have a molecular weight of up to 25½, is reacted with a smaller amount of one of the aforementioned sulfonating agents to form an aromatic polyisocyanate composition obtained which has a smaller i «en.ge (less than 0.5 and preferably more than U, U2 mol per mole of unreacted polyisocyanate) of the compound _m +

(1) OCIi-Ar ^

wherein Ar is an aromatic nucleus, for example a benzene, diphenyl, iphenylmethane, naphthalene or diphenyl ether nucleus; Examples fiir cores from the benzene type are toluene, and Aylol ChloTbenzolj Examples of Diphenylkerne are 3.3 ^I -Dimethyldiphenyl, 4,4'-Diphenyleη and J ^ '- dimethoxydiphenyl;

or, if the aromatic polyisocyanate is a prepolymer with terminal isocyanate groups, the compound

(2) UCN-HX-CO-HH-Ar ^

wherein Ar has the meaning described above and H represents a prepolymer chain; X has one of the meanings ü, ü, or K-alkyl;
having.

It should be clear to a person skilled in the art that the stereochemical relationship the oubsti attached to "Ar" (the aromatic nucleus)

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tuenten can be vadated, and that "Ar" can be a structure can, which has one, two or three aromatic hinge, which can be separate or condensed. It can be Example of any toluene nucleus can be used, including the 2,3-, 2,4-, 2,5- and 2,6-substituted toluenes. In a similar ' Both m- and p-phenylene can be used.

The compound (1), an ionomer, can be used in a prepolymer with Isocyanate end groups similar to compound (2) can be converted by reacting this monomer with any of the above Polyols, and both compound (1) and compound (2) can be neutralized with one of the above bases and thus be georacht to react with a second aromatic polyisocyanate, in the case of the compound (1)

(3) UCN - Ar - HH - CÜ - «Ή - Ar - NCO

SO3 [cation of the base] ⁺ ,

where Ar is as defined above,
or in the case of connection (2) ■

(4) UCN-R-X-Cu-Nri-Ar-NH-CÜ-NH-Ar-NH-Cü-X-R-IiCO

3Oj [cation of the base] » <

wherein Ar and H and A are as defined above.

Compounds (3) and (4) can be chain extended , however it is preferred in the practice of the invention to chain extend prepulmers having isocyanate end groups similar in structure to compound (4).

The compounds (1) and (2) are thus sulfonated, but not neutralized, and can be modified by their structural formula

(A) UCN - ^ r- RX-CG-iüi - ^ TT- Ar

009 808/16

-13-.

in which R, Ar and X are as defined above, and η is 0 or 1. If n = ü, the structure is monomeric, and when n = 1, the structure contains a prepolymer chain.

The compounds (3) and (4) are at least partially neutralized and can through the formula

(B) OCN - (- RX-CO-M Αχ-h H-CO-NH-Ar- £ -NH-C0-XR -) - NGO

; J [cation of base] +

, wherein R, Ar, X and η are as defined above will.

The chain extension of compounds according to formula (B) results in polyurethanes (as they have been defined here), polyureas or the dimercapto ^ equivalent of a polyurethane. For convenience, the terms "polyurethane" and '! Polyurea "have been used to polymers to designate according to the invention, the at least one smaller • Quantity (this amount being the by the amount of sulfonating \ j medium, the Dei method according to the invention was used, is determined) on recurring units of the following structure:

(C) - £ —R-X-Cü-iUl-Ar-MH-CÜ-i, H-Ar-NH-CO-X-R-NH-CO-NH-l · - /

f, [cation of the base] +

wherein R, Ar and X are defined as above and the others repeating units in the chain the usual polyurethane or Are polyurea units.

The preferred form of R (prepolymer chain) can through the the following structural formula can be represented:

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(D) -Ar-Ud-Cu-X ~ (Alkylenaxy) - _A lk: y le η-,

where Ar unä α are as defined above and m is such a number is that the molecular weight of formula (C) becomes less as 25ÜÜU results.

Various bases can be used as neutralizing agents for the sulfonated polyisocyanates. Suitable examples are sodium or other alkali hydroxides, tertiary amines, basic oil salts and the like. If the neutralizing agent is a tertiary amine, it can be added directly to the sulfonated polyisocyanate. In the case of other neutralizing agents, such as z.ii. of hydroxides and the like, the neutralizing agent should be stirred into the acid before emulsification of the sulfonated polyisocyanate. In each case, such an amount of base is added that practically all of the acidic groups contained in the sulfonated prepolymer are converted into sulfonic acid salt groups.

The solution of the neutralized sulfonated prepolymer is introduced into water at room temperature with vigorous stirring. Any high speed homogenizer is suitable for achieving the desired degree of agitation. If smaller amounts of sulfuric acid are used to sulfonate the prepolymer, greater energy is required to achieve good dispersion in water. Latex particles of a micron or smaller are easily obtained with the aid of this procedure. With less agitation, latices or dispersions with large particle sizes can be produced. In general, such an amount of water should be used that a dispersion is obtained which contains 10-70 wt. --- / ο solids, with 25 to 50 wt. Being preferred.

If desired, a certain amount of a "diamine, and up to almost one amino group per isocyanate

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* 'BAD ORIGINAL

group, to the water soon after emulsification of the prepolymer added to the chain extension of the '' To effect prepolymer. Such a diamine reacts with the isocyanate groups more easily than water, and it becomes a Polymer with higher tensile strength and higher modulus is produced than with simple chain extension with water. Typical examples for diamines. that can be used are phenylenediamine, Toluylenediamine, ivthylenediamine, propylenediamine, hydrazine, Piperazine, dimethylpiperaz'in, methylene-bis-3-chloro-4-aniline, Polyoxyalkylenediamines and the like. If desired, a small amount of a triamine or polyamine introduced into the water to obtain crosslinked polymers. *

When this chain extension reaction is brought about by i / water a significant amount of COp develops in the Reaction mixture causing considerable foaming. the

j chain extension reaction is exothermic, therefore the

Temperature of the reaction device slightly. The main part of the.

! Implementation expired after an hour, but experience has shown that the chain termination reaction in general is not complete in less than 24 hours. The chain extension either through water or a polyamide, poly-

urea cross-links in the polymer chain, whereby poly- ; urethane polyurea latices are produced. Such latices are usually referred to as "polyurethane" lati "ces, this means that the terms used here are interchangeable.

In the range from, 1 to 2, υ wt .- *> Sulphonating agents, latices can be obtained at all concentrations, wherein however, greater energy is required to make those too emulsify, uie with the smaller amount of oulxonating agent

■ are manufactured. In these cases a stronger pre-coagulation. With the higher amounts of acid it is

, easier to make good films from the obtained latex.

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j -16-

Sulfonated and non-sulfonated prepolymers can be mixed and used to produce latices similar to those made from sulfonated prepolymers with the same average acidity.

The latices according to the invention can also be used for impregnating Fabrics and textiles are used. They can also be used as overlays on a variety of flexible substrates including Fabrics, paper, wood and leather can be applied. You can use Holländer treatment methods to produce Reinforced papers, synthetic sheet materials and the like can be used and are also used in the manufacture of adhesives useful.

The prepolymers before the extension or the Emulsions before use can be mixed with other ingredients such as surfactants, plasticizers, dyes, Pigments, smaller amounts of other compatible polymers, or agents which impart resistance to light, heat or oxidation, and the like are modified.

The invention is further illustrated by the following examples, in which all parts are, unless otherwise stated, refer to weight.

example 1

A polyether polyurethane prepolymer was prepared by reacting 28.3 moles of a polyoxypropylene glycol of one molecular weight from 778 (Wyandotte P 710) and 5.23 moles of diethylene glycol with 53.7 mol of toluene diisocyanate (mixture in a weight ratio of 80/20 of the 2,4- and 2,6-isomers) up to an isocyanate equivalent weight manufactured by 783.

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3260 parts of this prepolymer were diluted with 1090 parts of toluene to a solids content of 75 ° h. 36.6 parts of 98% strength by weight sulfuric acid were added dropwise over a period of 5 minutes at 35 ^° C. An exothermic heat of about 4 C (35-39 C) was observed during the sulfuric acid addition along with the evolution of gas. The mixture was then heated to 75 ° C. and held there for 30 minutes, during which time the prepolymer turned a little brown in color and the evolution of gas ceased. The mixture was then cooled to 40 ⁰ C, and 37 g of triethylamine were eye sets. The color of the prepolymer became lighter after this addition.

The prepolymer was then dissolved in 4900 parts of deionized water with agitation on a 373 watt high speed homogenizer poured at maximum speed for 3 minutes. After the latex for 3 days at room temperature the toluene was obtained by azeotropic distillation; removed. A film was made that has the following proprietary!

shafts had: tensile strength: 129 kg / cm; Module at 100 # elongation: 25 kg / cm ² ; Elongation at break $ 900. The film was very clear and almost colorless and had a glass transition temperature (T_) of −2 ^° C. and a density (dry film) of 1.1 g / cm ³ .

Examination of the 3 latex under a microscope showed that practically all particles in the size range from 1 to 3, u lay. The latex had a pH of 5.8. The percentage of acid, calculated as sulfuric acid, became potentiometric determined and found to be less than 0.02% by weight.

Example 2

A diisocyanate sulfonic acid reaction product was prepared by loading _; treatment of 348 g of toluene diisocyanate (mixture by weight

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• -18-

ratio 8ü / 2ü of the 2,4- and 2,6-Isoraers) with 4ü g stabilized 30., (iJulfan Allied Chemicals) under anhydrous conditions manufactured. A crystalline precipitate was formed. It was isolated by filtration with anhydrous Washed toluene and then dried in a vacuum. The dried ones Crystals were found to be soluble in ketones and reacted violently with water.

A polyether polyurethane prepolymer was prepared by dissolving 7.80 g of the above product in 1 u g of dry acetone. 1ÜU g (u., 10 mol) of polyoxyalicylenediol with a molecular weight of 1UÜU (PPG 1025) were added together with 3 g of triethylamine. The reaction mixture was heated to the reflux temperature (6 ° C) and held there for 15 minutes, after which 31.3 g (18 mol) of toluene diisocyanate (mixture in a weight ratio of 80/20 of the 2,4- and 2,6- Isomers) were added. The mixture was again heated at the reflux temperature of acetone (60 ⁰ C) and held there for 70 minutes. The reactants were then allowed to cool and stand for 44 hours. 5u ml of dry toluene was added and the mixture was again heated to its reflux temperature (61 ° C.) and held there for 3 hours, after which it was cooled and dissolved in 500 g of water using an 187 watt Eppenbaeh homomixer (model L-1) for 3 hours Minutes at maximum speed. The freshly made latex was left to stand for several days. A small portion was diluted to a solids content of about 1 wt .- ^ for microscopic examination. The particle size was found to be 1; U to 5 / U, the latex being free of particles larger than 5 / U.

A small portion was poured into a petri dish and with Tree left to dry at temperature. A very clear and colorless FHm was obtained. The physical characteristics of the film were:

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BATH ORIGINAL

Tensile strength: 67 kg / cm

'Module at ΐυυ #: 12.7 kg / cm Elongation at break: 49U ^J h

Example 3

A polyether polyurethane prepolymer was prepared from 6.1 moles of polyoxyprop / lengiy.wl (molecular weight 1970), 1.55 moles of polyoxypropylenetriol (molecular weight 424) and 16.43 moles of toluene diisocyanate. The reaction was carried out at 85 ^° C. for 6 hours up to an isocyanate equivalent of 988.

Four portions of the product were treated with a solids content of 75% with 0.25, ½, 50, 1.0 and 2.0% by weight sulfuric acid. These 4 different prepolymers were neutralized with the corresponding molar equivalent of triethylarain and then emulsified in water. The properties of the latexes and the films made therefrom are given in Table 1 below.

-Table I-

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BATH

-20-Table I.

Viscose latex content of the solids IG wt .-% HpSO. Vorpolv- to Sntferizum Vorpol / - merisates tion of the • merisat trains- after 24 toluene sets std. (Cp)

Particle tensile strength of the latex of the

(■ - \ Films _o Filmigen V (kg / cm ^) shafts

0.25

0.50

1.0

2.0

348 42.0 Weight # Main set ~
<5, some
6-20 cracked,
Pieces
from 1-2cm 536 40.5 Weight # Main set -
<4, some
4-15 cracked, ι
Pieces
from 1-2cm 450 41.3 Wt .- ^ Main set 76
<4, some
4-15 few
Cracks 00000 37.7 Weight # Main set 100
< 6, some
7-200 more perfect
Movie

Thus, in the particular system for producing a latex having small uniform particles, sulfonation of 0.50 to 1.0 wt. ^-1 Io is preferred. On the other hand, a sulfonation with 1.0 to 2.0 weight ^i; S preferred if a good film formation is to be ensured. At the different concentrations of the HpSÜ. Treatment, there was no visible difference in terms of the color or clarity of the film.

Example 4 ^ '

A polymer polyurethane prepolymer was prepared as in Example 3. A portion thereof was treated with 1 wt .-% sulfuric acid, and the ^ APPROACH was heated to 75 ⁰ C, wherein aDgenommen three samples at this point and were neutralized with different molar ratios of Triäthanol and then emulsified in .Vasser. This stage was repeated again,

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BATH ORIGINAL

I after the reactants have been at 75 ° C for 30 minutes; hold and further repeated after being held at 75 ° C for 90 minutes.

Initial packing:

3000 g polymer (NCÜ equivalent weight = 1U13) 1000 g dry toluene

31.3 g of 96.0% strength by weight sulfuric acid

I The following samples were neutralized by the implementation participants, after they reached 75 C, and got final emulsification in water:

Parts (C ₂ Hj) ₃ N

3000 parts molar ratio parts

■ ^x prepolymer (C ₉ Hc) -JV-SO- »H water

1a 17.4 0.75 / 1 4070

1b 29.0 1.25 / 1 4070

1c 23.2 1/1 4070

1d 23.2 1/1 kept

After the reactants held oei .75 C for 30 minutes the following samples were taken, neutralized and emulsified in water:

Parts of (C ₂ H ^) ₃ N molar ratio Qi _el i _e

per 3000 parts of C ^C 2 ^H 5 ^ 3 ^{W //} ~ ^SÜ 3 ^H V / water sample prepolymer

2a 17.4 2 B 29.0 2c 23.2 2d 23.2

0.75 / 1 4070

1.25 / 1 4070

1/1 4070

1/1 kept

After the reaction participants ^{had been kept at 75 °} C. for 90 minutes, the following samples were taken, neutralized and emulsified in water:

'009808/1682 ^:

Parts

per 300υ parts > ^C 2 ^H 5O / ~ ^OÜ 3 Parts sample Prepolymer ^ 0.75 / 1 water 3a 17.4 1.25 / 1 4070 3b 29.0 Vl 4070 3c 23.2 1/1 4070 3d 23.2 υ, 75/1 kept 3e 17.4 t, 25 / l kept 3f 29.0 kept

The non-emulsified Vorpulymerisate were stored and from Examined from time to time. The following observations were made:

Viscose

sample At first-
viscosity
(Cp) did after
18 days
(Cp) initial
-NCO number NCO number
after 18
Days 1d 1770 1950 1280 1375 2d 2160 2140 1297 1381 3d 2120 2270 1302 1379 3e 2010 2320 -. _— 3f 2120 4800 -

O,

Films were cast and Del 21 C and 5u "J> relative humidity dried, further dried for 16 hours at 65 C, thermoset at 150 ⁰ C for 15 minutes and then held for at least 24 hours at 21 C and 50% relative humidity Films were examined and the following youths were found

009808/1682

BATH ORIGINAL

Tensile modulus at 100 #

I.
j sample speed j,
(kg / cm *) Strain.
(kg / cm ^z ) % Elongation up to
to break I 1a 39 6.5 760 ! 1b 61 10.5 670 ! ^ic 75 9.9 780 2a 30th 7th 620 2 B 70 9.9 760 I 2c 68 9.9 730 ^; 3a 31 7th 630 3b 64 9.9 790 3c 73 9.9 820 ; Example $ '

A polyether polyurethane prepolymer was made by reacting clay 1 mol. Polyoxypropylene glycol of one molecular weight of an average of 2000 and 0.262 moles of polyoxypropylenetriol ■ from an average molecular weight of 426 with 2.82 mol of toluene diisocyanate (semicircle with a weight ratio of 80/20 of 2,4- and 2,6-isomers) at 85 ° C. up to an NCO equivalent weight manufactured by 928. This was up to a solids content of 75.0 wt. Ίδ with dry toluene diluted, reacted with 1.00% by weight sulfuric acid and with the molar equivalent of triethylamine neutralized. 4uu g of the above prepolymer were in 500 g of water by stirring at the maximum speed using a j 187 Watt-Eppenbach-Eomomixers emulsified for 3 minutes, at this point 3.71 g of 64 wt.% hydrazine were added and the emulsification was carried out for a further 15 seconds * was carried out for a long time.

009808/1662

The freshly made latex was left to stand for several days. A film was produced by letting a portion of the latex dry at room temperature, after which a melting operation was carried out at 150 ^° C. for 10 minutes and then held at 50 ° relative humidity and 21 ^° C. The film had the following characteristics

Tensile strength: 78 kg / cm ²

Modulus at 10u%: 11 kg / cm ² ;

Elongation: 660 #

Example 6 ·;

A Polyätherpolyurethan was prepared by reacting 0.5 mole ■, polyoxypropylene glycol of an average molecular weight of from j 1000 with one mole of diphenylmethane diisocyanate at 85 ⁰ C for 3.5 otunden prepared. To reduce the viscosity somewhat, 87 g of toluene were added. To this end, 7.77 g of 96% strength by weight sulfuric acid were added during a

009808/1662

A period of one hour at 85.degree. C. and then 91.48 g of triethylamine were added. This corresponds to a molar ratio (O ₀ Hr -) -, N / H _o S0, _L of 1.25 / 1 · 107 g of toluene were converted into 226 g of des

d. ρ O d. "f

above prepolymer (60% solids) was added, and the solution was then dissolved in 500 g of water using an 18? Watt-Eppenbach homomixers at maximum speed! glee it emulsified for 1.5 minutes and then left to stand for several days. A portion of this product was melted in a flat Petri dish and dried at 65 ° C for 16 hours, followed by, reconditioned for 24 hours at 50% relative humidity and 21 ⁰ G. The product had the following properties:

Tensile strength: 96 kg / cm

Module at 100%: 17.6 kg / cm ²

Elongation at break: 1000% _:

Example 7 '

A polyester with terminal hydroxyl groups, which had a theoretical molecular weight of 1036, was converted by ^; reduction of 6 moles of adipic acid with 6.3 moles of ethylene glycol and 0.7 moles of propylene glycol in the presence of 0.05 wt .-% ZnGIp as cata- lyst · at 150 ⁰ C to 200 ⁰ G produced during a period of 10 hours.

5 · - ί

A prepolymer was then made by reacting 2 McI toluene | diisocyanate (mixture in a weight ratio of 80/20 of the 2,4- and \ 2,6-isomers) produced with the polyester after it had cooled down to room temperature. 24-5 g of the prepolymer were diluted with 164 g of toluene to a solids content of 60%. The reactants were heated to 50 ° C., 2.56 g of 96% strength by weight sulfuric acid were added, and the temperature was increased to 75 ° C. for 40 minutes. At this point, 2.52 g of triethylamine were added ; was allowed to cool to 65 ° G and submerged in 400 g of water

0098Q8 / 16'62--

- 26 Formation of a stable, non-film-forming latex emulsified.

example 8th

A polyether polyurethane prepolymer was prepared by reacting 385 parts of polyoxypropylene glycol with an average molecular weight of 2000 and 21.3 parts of polyoxypropylenetriol with an average molecular weight of 425 with 92.3 parts of toluene diisocyanate (mixture in a weight ratio of 80/20 of the 2.4 and 2.6 -Isomers) at 88 ° 0 up to an isocyanate equivalent weight of 930. 3000 parts of the prepolymer were diluted with dry toluene to a pesticide content of 75% by weight. and heated to 48 ^{° C. with mixing.} At this point 31.9 parts of 95.9% ise sulfuric acid were added. The mixture was then heated to 75 ° C. for 30 minutes and
Cooled to room temperature.

heated to 75 ° C for a long time and then with stirring overnight

To 400 parts of this sulfonated prepolymer, 2.40 parts of pyridine were added with stirring. It then became Mixed for one hour and then divided into 450 parts deionized water emulsified at room temperature. A stable latex was produced. A film made from it possessed a tensile strength of 391 ^ kg / em ", a modulus of 100 ^ ir-e Elongation of 8.4 kg / cm and an elongation at break of 620%.

Another latex was produced from the above sulfonated prepolymer _} by first adding 4.3 parts of Na ₂ HPO. were dissolved in 450 parts of deionized water. 400 parts ^of: non-neutralized sulfonated prepolymer were emulsified therein to form a stable latex. One of them

formed film had a tensile strength of 46.5 kg / cm, a

Module at 100% elongation of 11 kg / cm and an elongation at break of 570%.

Another latex was produced, using NaOH as a new

009808/1662

PAD ORIGINAL

; - 27 -

neutralization agent was used. It was made in the same way, with the modification, that 12.1 parts! j 10 wt .-% aqueous NaOH instead of the NapHPO ^ were used. A stable latex was also obtained here. One of them

produced film had a tensile strength of 66 kg / cm,

a module at 100% elongation of 12 kg / cm and an elongation at break of 650%.

Example 9

A Polyätherpolyurethanvorpolymerisat was prepared as in Example 8 and _# unsulfonated left. 200 parts were made with 6? Share diluted dry toluene. 6 parts of the diisocyanate sulfonic acid described in Example 2 were dissolved in 50 parts of dry acetone and mixed with the above dilute prepolymer. To this end, 5 parts of triethylamine were added. This mixture was then emulsified in 300 parts of deionized water at room temperature. Significant > foaming occurred, apparently due to rapid OOp development. A stable latex was produced, but the presence of a pre-coadulate was also observed.

Example 10

104.2 parts of toluene diisocyanate (mixture in a weight ratio of 80/20 of the 2,4- and 2,6-isomers) were mixed with 50 parts of anhydrous acetone. To this, 4.22 parts of 95.9% by weight sulfuric acid was added dropwise. An exothermic heat of 18 ° C. was observed (25-43 ° C.), during which time the reaction participants became cloudy and a precipitate then formed. The ingredients were heated to flux temperature (65 ° C) and held there for 30 minutes, after which the precipitate went into solution and changed color from pale yellow to very dark hot.

009808/1662

To this, 4.14 parts (C ₂ Hc) ^ N were added, which changed the color back to pale yellow. Then 300 parts of polyoxypropylene glycol with an average molecular weight of 1002 were added. A cloudy solution formed. The reactants were then heated to 80 ° and held there for 2 hours, after which time larger pieces of insoluble material had formed. The prepolymer was then emulsified in about 800 parts of room temperature deionized water using an Eppenbach homomixer (Model LI) at maximum speed for 3 minutes. The freshly made latex was allowed to stand for two weeks, during which time it remained stable.

Example 11

A polyether urethane prepolymer was obtained by reacting 3000 g of polyoxypropylene glycol with an average molecular weight of 1002 with 1042 g of toluene diisocyanate (mixture in a weight ratio of 80/20 of the 2,4- and 2,6-isomers) at 65 ° 0 produced for 4 hours. After the prepolymer was aged for 7 days, 300 g thereof became a solid content of 50 wt .-% diluted with 300 g of 1,1,1-trichloroethane. The diluted prepolymer was brought to 25 C, and then 1.27 ml of stabilized SO2 was pipetted into it, dropwise. Almost no color change was observed with very little charring. This mixture was for 30 minutes stirred at 25 C, after which 3 »09 giCpHc) ^ were added and stirring was continued for an additional 30 minutes. To During this time, the diluted sulfonated prepolymer was dissolved in 15ΟΟ g of water using a high-speed mixer emulsified. The freshly made latex was allowed to stand for several weeks, during which time it remained stable.

Example 12

A polyether urethane prepolymer was prepared by reacting j

009808/1662

3000 g of polyoxypropylene glycol of an average
Molecular weight of 1002 with 1042 g of toluene diisocyanate
(Mixture in a weight ratio of 80/20 of the 2,4- and 2,6-isomers) j prepared at 65 ° C. for 4 hours. After the prepolymer had aged for 10 days, 300 g of it were with
200 g of dry toluene diluted. 6 g of methyl diethanolamine, the
previously mixed with 100 g of toluene then became
added to the above diluted prepolymer and at 60 C! Reacted for 75 minutes. At this point were
8.29 g of 95-9% sulfuric acid were added dropwise and left to react at 75 ° 0 for 70 minutes. For this purpose, 8.19 g
Triethylamine added with stirring; it was then emulsified in 900 g of water to form a stable latex. An electrophoretic separation was carried out to determine the ionic character of the latex. In this procedure, a portion of the latex was diluted to a solids content of about 1% by weight and two nickel electrodes were inserted, marked with |

a 30 volt DC power source. The water near the anode was found to become clear, and ^; that the latex particles were attracted to the cathode and deposited there like a coating. This shows that the latex was anionic in character.

Example 13

A polyether urethane prepolymer was obtained by reacting
2.0 mol of polyoxytetramethylene glycol with an average molecular weight of 1060 and 0.10 mol of polypropylene ether triol of
423 average molecular weight at 4.3 moles
Toluene diisocyanate (mixture in the weight ratio · 80/20 of the 2,4- and 2,6-isomers) ^{prepared at 82 0} O for 4 hours. The j prepolymer was diluted to a solids content of 75% with I dry toluene, woxiaeh to 65 ° C was cooled and j 58.2 g of 96% H ₂ SO ₄ isurden added "at the 65-? Q ° G 45 \ Allowed to react for minutes. After this time it was observed that the prepolymer became very viscous - 60 g ^!

003808/1882

(GpH ₁ -), N were then added with stirring. At this point
it was observed that the viscosity decreased significantly. Of the
The batch was then mixed for 5 minutes and then

emulsified in 5 '+ 00 g of room temperature deionized water. j

The freshly made latex was left to stand for 48 hours.

let, after which the toluene by azeotropic distillation under j

Vacuum was evaporated. !

A film was made as in Example 4-. The own '

shafts of the film were:;

2
Tensile strength: 112 kg / cm

Module at 100%: 18 kg / cm ²

Elongation at break:, 830% ^:

example

A polyether urethane prepolymer was prepared by reacting

; 363 g polyoxypropylene glycol of an average mol

I kular weight of 976 with 137 6 xylyol diisocyanate at 85 ° C

j made during 5 hours. 250 g 1,1,1-trichloroethane was

'. added to reduce the viscosity and reduce the ",

j set to cool to 65 ° C. At this point, 2.12 ml of SO,

J added, after which dark brown bits of insoluble

ι material were formed. This was followed by the addition of 250 g,

Toluene and stirring at 65 ° C for 15 minutes. Then \

ι 5 »2 g of triethylamine added and at 85 0 during one

Stirred in for 1 hour, after which it was emulsified in 1500 g of water. -

j The prepolymer emulsified slightly and was at least 2 days _:

I long stable. '

! Example 15

A Polyätherizrethanvorpolymerisat was made by reacting
j 311 g of polyoxypropylene glycol with an average molecular weight of 976 with 189 g of dianisidine diisocyanate
I 7-5 ~ 85 0 produced during 25 SfromcLen. The prepolymer left wur- [en then stand and cool for another 20 hours.

009808/1662

It was then diluted with 250 g toluene, in order to reduce the viscosity, and heated to 50 ⁰ C, after which were added 9 _s 5% sulfuric acid "23 g 95th The reactants were further heated to 75 ° C. and held there for 30 "minutes, after which the mixture was cooled to 50 ° C. To this, 5-15 g of triethylamine were added, which was stirred in for one hour. The prepolymer was then added at 1130 g water to form a; stable latex emulsified · a therefrom had produced a film; tensile strength of 148 kg / cm, a modulus at 100% elongation '

ρ
of 20 kg / cm and an elongation at break of 440%.

Example 16

A polyether urethane prepolymer was prepared by reacting 368 g of polyoxypropylene glycol with an average molecular weight of 976 with 131 g of toluene diisocyanate (80/20 mixture of the 2,4- and 2,6-isomers) at 75 "to 90 ^° C. for 4 hours 250 g of toluene were added, and the batch was cooled to 20 ° C. At this point, 3.33 ml of C1SO, H were added and the mixture was heated to 105 ° C. The toluene was then stripped off under vacuum while the prepolymer was allowed to cool to 50 g. 5-2 g of triethylamine were then added and stirred in for 40 minutes, after which it was emulsified in 750 g of water to form a stable latex.

from produced film showed a tensile strength of 93 kg / cm,,

a module at 100% elongation of 20 kg / cm and an elongation at break of 860%.

The polyurethane (including the polyurethane polyurea) and Polyharastofflaticen according to the invention have numerous possible uses, e.g. as coatings, impregnations, or as film-forming masses. They are particularly useful on the; Areas of the manufacture of adhesives, textile printing pastes,; Stamp pads, plastic bandage materials, filters, storage, Leather substitutes, battery separators, or fabrics. So can the latices according to the invention alone or in combination with small-sized fillers, such as natural and / or synthetic fibers with the formation of leaves laid out in water,

009808/166 2

which can be heated and / or pressurized to rubbery, leathery, or inflexible, board-like Materials with different degrees of porosity, water absorption capacity and / or ion transfer properties to manufacture. Another type of fabric, filter sheet, leather substitute, or battery divider is made by impregnating a woven fabric or a non-woven mat or sheet with the latex. Other types j of fabrics, leather substitutes, filters, etc. can be achieved by layering the latex on a suitable substrate (or coating!

\ has been bind a preformed film, which generates from the latex may be prepared with such a substrate). · All of these modes of operation are known in the art; See, for example, U.S. Patents 2,112,529 dated March 29, 1938; 2 719 806, from 4-. October 1955; 2,723,935 of Nov. 15, 1955; 2,780,562 of Feb. 5, 1957; 3,436,303 of Apr. 1, 1969; and 3 44-5 272j dated May 20, 1969 · Leather substitutes made according to these procedures can be made sufficiently resistant to wear and flex fatigue and / or made sufficiently microporous to be used as soles or upper leather substitutes for shoes.

- Patent claims.

009808/1862

Claims (2)

Claims 1. Process for the production of a self-emulsifiable polyurethane or polyurea latex by introducing salt-like ones Groups in the polymer chain, characterized in that one a) an aromatic polyisocyanate known per se, which has a molecular weight in the range from 160 to 25,000, is reacted with 0.5 to 0.02 moles of sulfuric acid, sulfur trioxide, chlorosulfonic acid ¹ or a mixture thereof per mole of polyisocyanate, b) the sulfonated aromatic polyisocyanate obtained is reacted with a base and c) the obtained polyisocyanate compound containing sulfonic acid salt groups is mixed with an aqueous medium, in which the polyisocyanate compound is chain extended to form a polyurethane or polyurea and is emulsified to form a stable latex. j 2. The method according to claim 1, characterized in that the ! aqueous medium contains a dissolved organic polyamine. 3 · The method according to claim 1, characterized in that the known aromatic polyisocyanate is a prepolymer with a molecular weight in the range from 20 to 10,000. 4. The method according to claim 1, characterized in that the Base a tertiary amine, ice alkaline hydroxide or a basic one Salt is ο 5. The method according to claim 4-, characterized in that the Alkali hydroxide is dissolved in the aqueous medium of step (c). 6. The method according to claim 1, characterized in that the Polyurethane or the polyurea in the latex has a crosslinking per 3000 to 50,000 polymer atom weight units. 7. Chemical compound characterized by the following structural formula: ITH-GO-HH ^ OH ₃ wherein OCN-E-OCN-77-Λ means, and where η is a number such that ■ H— ^ 0CH ₀ CH ₀ CH ₀ -) - OH an average molecular weight in the range of · j ■ d. et e- a ! 778 to 2000, i.e. a has a value of at least I3, ! but not more than 35 ·. = 8 »Aqueous, self-emulsifiable polyurethane polyurea latex, characterized in that the polyurethane polyurea in the latent apart from recurring units known per se in the. Average 10-20% repeating units of the: Formula ''^:; 009808/1862 where H • 2) Vt / NH - CO - 40CH ₀ CH ₀ CH ₀ ^ -, where Ie is a number ■ fin C. C. C- Ά ■ with a mean value of 13, or 3) W / ~ NH-CO-OCH ₀ Ch ₀ OCH ₀ CH ₀ - means W / CH, or combinations of (2) ″ and (3); the stereochemical relationship of the nitrogenous Substituents on the toluene core of the formulas (1), (2) and (3) 80% 2.4- and 20% 2.6- is, and one from the latex vergostroxyteäeiy ° senerVPilm has the following properties: 2 tensile strength: 129 kg / cm Module at 100% elongation: 25 kg / cm Elongation at break: 9005a Glass transition temperature (T-)! -2 C Density: 1.1 g / cm 9 · polisher film obtained by casting an aqueous L _a tex, characterized in that the latex is a latex has been used according to Claim. 1 , i 10 · Leather substitute material, consisting of a non-woven \ hat which has been impregnated with an aqueous latex, or a * sheet laid out in water which has been made from a latex mixed with natural and / or synthetic fibers, characterized in that a latex according to claim 1 has been used as the aqueous latex » 0 0 9 8 0 8/1662 bad ORIGINAL