CA1075398A - Manufacture of polyurethane compositions - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE: Polyurethane compositions - which may or may not be foamed - having improved mechanical properties are manu-factured from organic polyisocyanates, polyhydroxy compounds and one or more at least partially crosslinked, particulate polymers of particle size from 500 to 5,000 .ANG., of which polymer from 1 to 40% by weight are dispersed in the polyhydroxy compound.

Description

OOZ. 31,016/017 ~a3753~
MANUFACTURE OF POLYURETHANE COMPOSITIONS

The present invention relates to a process for the manufacture of polyurethane compositions - which may or may not be foamed - by poly- -addition of organic polyisocyanates and polyhydroxy compounds from the group of polyether-polyols and/or polyester-polyols, in the pre-sence of one or more at least partially crosslinked particulate polymers~
It is known to manufacture polyurethane plastics having a variety of physical properties by reacting compounds having a plurality of active hydrogen atoms, in particular polyhydroxy compounds, with poly-isocyanates, if desired in the presence of chain extenders, cross-linking agents, blowing agents, activators, emulsifiers and other adjuvants~ If the component~ are s~itably chosen, both elastic and rigid foams, surface coatings, impregnat:ions, covering layers and elastomers can be manufactured by this method Since, furthermore, in numerous applicationæ the polyhydroxy com-pounds cannot be employed in.the ~orm of solutions, the viscosity o~
the polymer~polyol mixtures uJed plays an important role in the manu-facture Or polyurethane plastics~ This is particularly true when manu-facturing polyurethane foams, in which case it must be possible to feed, and meter, the polymer/polyol mixture satisfactorily by means of pumps and to mix it, homogeneously and very rapidly, in mixing chambers, with the isocyanate component and the adjuvants~ e.g acti-vators, emulsifiers, water and/or blowing agents. For this reason, very low viscosities are desirable when manufacturing polyurethane foams.

~.

OoZo 31~016/017 ~C~7~ 3~ ~
Ifs in the manufacture of polyurethanes, the reactants are mixed unsatisfactorily, because of their high viscosities, the product is inhomogeneous and/or foaming takes pl~ace unsatisfactorily, to the .. detriment of the quality of the productsO
It has also been disclosed, in German Published Application

2~249~094~ that the load-bearing capacity of flexible polyurethane foams of low density can be increased by adding polymer latices wi.th particle sizes of from 200 to 800 ~ and having glass transition tem-peratures above 50Co It is true that using this methodg the aqueous emulsions of brittle polymers, described in the above German Published Application, can be used, but even at relatively low concentrations of the polymer in the polyhydroxy compound the viscosity of the mixture increases greatly and therefore these mixtures are difficult to handle since they are no longer free-flowing~
UOSo Patent 39523~093 discloses that the polymers described therein can no longer be used if they exceed a certain molecular weight, since in that case theviscosity of the polymer/polyol mixture rises to an extent which prevents their use for the manufacture of ~20 polyurethanesO
Very viscous polymer/polyol mixtures cannot be used for pro-cessing on, eOgO~ high pressure foaming apparatus The above U S0 Patent furthermore discloses that the pulverulent . reactive polymer must be redispersible in the polyhydroxy compound.
This method requires increased effort~ After polymerization, the polymer must first be isolated by conventional methods and then be driedO Thereafter, the filler is uniformly distributed in the poly-hydroxy compoundO Hence, the process involves three stages and demands considerable expenditure of equipment and time~ Redispersi~
: 30 bility is an important factor with regard to marketability, since polymer~polyol mixtures must prove stable on storage for prolonged periods without even partial macroscopic sedimentation of the dis-persed polymer~ If this requirement is not met, the metering of the polymer/polyol mixture presents (~ifficulties. Furthermore, uniform distribution of the filler, which is essential for achieving optimum properties of, e.g., a polyurethane foam, can no longer be relied upon. To conform to this requirement, the polymer must be isolated in a very finely divided form.
This again entails increased technical effort.
It is an object of the present inven-tion to provide polymer/polyol mixtures which combine good processability with an improvement in polyurethane properties.
It is a further object of the present invention to simplify the introduction of polymer par-ticles into the polyol preferably by mixing aqueous dispersions with the polyol and then entirely or partially abstracting the water from the mixture.
We have found, surprisingly, that this object is achieved by using crosslinked polymers which, in contrast to the corresponding non-crosslinked polymers, give polymer/polyol mixtures which are o~
low viscosity and are therefore more easily processable.
~ Surprisingly, this con-tradicts the teaching of U.S.
; Patent 3,523,093, since crosslinking in particular gives polymers of very high molecular weight.
We have furthermore found that when using crosslinked polymers the average diameter of the par-ticles in the polymer dispersion used may, in contrast to the teaching of German Published Application 2,249,094, be substantially in excess of 800 ~ without a detectable lowering of the mechanical properties of the end products.
The present invention relates to a process for the ; manufacture of polyurethanes which comprises:
I. mixing 1. a polyhydroxy compound (B) having a molecular weight of from about 500 to 7000 and a hydroxyl number of from 20 to 1000 and selected from the group consisting oE
polyether-polyols and polyester-polyols, with ~, 75~
2. an aqueous polymer disp~rsion containing a cross-linked particulate polymer (C) having a particle size of from 500 to 5000 A and a gel content of no-t less than 5~ and comprising homopolymers, copolymers, graft polymers or mixtures thereof, said crosslinked polymer (C) being obtained by the emulsion or suspension polymerization of a. unsaturated compounds with straight-chain or branched polyhydric alcohols of mean molecular weights from 50 to 6000, in which at least one OH group of the polyhydric alcohol is no-t esterified, unsaturated copolymerizable polyols with mean molecular weights of from 200 to 6000, acrylamide, methacrylamide, butadiene, isoprene, piperylene and chloroprene, and b. crosslinking agents incorporated in the polymerized form in an amount of from 0.1 to about 20~o by weight and selected from the group consisting of divinylbenzene, diallyl maleate, diallyl fumara-te, diallyl adipate, allyl acrylate, allyl methacrylate, diacrylates and dimethacrylates of polyhydroxyalcohols and butadiene, wherein said homopolymers and copolymers have a glass transition temperature of from 40 to 130C and said graft polymers have two glass transition temperatures, one of from -40 to -90C and the other of from 40 to 130C;
II. removing the water from the mixture to produce a dispersion of 1 to 40% by weight of polymer(s) (C) in 99 to 60% by weight of polyhydroxy compound (B); and III. reacting the resultant mix-ture of (B) and (C) wi-th an organic polyisocyanate (A) to form the polyurethanes, the ratio of the NCO equivalent of polyisocyana-te to radica:ls of said mixture (B) and (C) which are rea(tive w:i-th isocyanato radicals being .in the ran~e of abou-t 0.7 - 1.3 ,Ai '75;~
It is an essentlal advan-tage of the process according -to the inven-tion that by using crosslinked polymersthe resistance of the polyurethane composition to organic solvents is significantly improved.
It is surprisingly that using the process according to the invention, significant improvements in the mechanical properties of the various polyurethane compositions can also be achieved.
The following are some details relating to the starting materials used in the process according to the invention:
(A) The polyisocyanates (A) may be aliphatic or aromatic polyfunctional isocyanates, e.g. alkylenediisocyanates, such as tetramethylenediisocyanate and hexamethylenediisocyana-te, arylene-diisocyanates and their alkylation products, such as the phenylene-diisocyanates, naphthylenediisocyanates, diphenylmethanediisocyanates, toluylenediisocyanates, diisopropylbenzenediisocyanates and triiso-; propylbenzenediisocyanates, triphenylmethanetriisocyanates, poly-- phenylpolymethylenepolyisocyanates, tri-(p-isocyanatophenyl) thio-phosphate and tri-(p-isocyanatophenyl) phosphate, aralkyldiiso-cyanates, such as l-(isocyanatophenyl)-ethylisocyanate or xylylene-diisocyanates, and polyisocyanates substituted by a great variety of substituents, e.g. alkoxy, nitro and/or chlorine, as well as polyisocyanates modified with minor amounts of polyhydroxy compounds, such as trimethylolpropane, hexanetriol, glycerol or butanediol.
It is further possible to use, e.g., polyisocyanates blocked with phenols or bisulfite, acetal-modified isocyanates and amide-, acyl-urea- and isocyanurate-modified polyisocyanates.
Preferred isocyanates to use are -toluylenediisocyanates, 2,2'-, 2,41- and 4,4'-diphenylmethanediisocyanate and the correspon-ding - 4~ -:' .
: ~ , O.Z. 31,016/017 1~5;~98 isomer mixtures, mixtures of diphenylmethanediisocyanates and poly-phenylpolymethylenepolyisocyanates, polyisocyanates modified with polyhydroxy compounds, polyisocyana~es containing isocyanurate rings and, particularly~ mixtures of toluylenediisocyanates, diphenyl-methanediisocyanates and polyphenylpolymethylenepolyisocyanates.
The polyisocyanates (A) are suitably used in amounts correspon-ding to from 70 to 130%, preferably from ~5 tG 115%, o~ the amount required theoretically for reaction with all hydrogen atoms, reactive toward isocyanate groups, which are present in the reaction mixture.
(B) The polyhydroxy compounds (B) used in the process o~ the invention are, eOgo ~ the conventional linear or branched polyesters which are manufactured, eOgO, from polybasic, preferably dibasic, carboxylic acids and polyhydric alcohols~ Examples of suitable dibasic carboxylic acids are aliphatic dicarboxylic acids, e.g. succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid and maleic acid, and aromatic dicarboxylic acids, eOg. phthalic acid, isophthalic acid, halogenated phthalic acids and terephthalic acidO The acids may be used as individual compounds or as mixtures.
In manu~acturing the polyester-polyols it may at times be advanta~eous to employ~ not the carboxylic acids, but the corresponding carboxylic acid derivatives, e.g. carboxylic acid esters with alcohols of 1 to 4 carbon atoms, carboxylic acid anhydrides or carboxylic acid chlorides.
Examples of polyhydric alcohols are glycols, e.g. ethylene glycol~
diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1910-decanediol, 2,2-dimethylpropane-1,3-diol and 2,2,4-trimethyl-pentane 1,3-diol~ triols, e.gO glycerol and trimethylolpropane~ and polyols, eOg. pentaerythritol, sorbitol and sucroseO Depending on the desired properties, the polyester-polyols may be used as individual compounds or as mixtures in various ratiosO
3o Suitable polyether-polyols may be manufactured by reacting one or more alkylene oxides of 2 to 4 carbon atoms in the alkylene radical with a starter molecule which contains several chemically bonded active hydrogen atoms. Exarnples o~ suitable alkylene oxides are ethylene ` OOZ. 31,016/017 lV~7~
oxide, 1,2-propylene oxide, epichlorohydri~,1,2 butylene oxide and 2~3-butylene oxide The alkylene oxides may be used as individual compounds, or in alternating succession, or as mixtures. Examples of suitable starter molecules are water, phosphoric acid, amines, eOg.
ammonia, hydrazine, ethylenediamine, hexamethylenediamine~ toluylene-diamine, diaminodiphenylmethane and melamine, aminoalcohols, eOg.
monoethanolamine and diethanolamine, polycarboxylic acids, e.g. adipic acid and terephthalic acid, and polyhydroxy compounds, e,g~ ethylene glycol~ propylene glycol, diethylene glycol, glycerol, trimethylol-propane, pentaerythritol, sorbitol and sucroseO The polyether-polyols may have a straight-chain, partially branched, or branched structure.
Further polyhydroxy compounds (B) which may be used are paly-merization products of tetrahydrofuran, and polyacetals, in particu-lar polyoxymethylenes containing hydroxyl groupsO
Preferably, polyhydroxy compounds based on linear and branohed polye~hers obtained from propylene oxide and ethylene oxide are used.
Such polyethers are manu~actured by conventional methods, e.g. as disclosed in German Published Application 2,220,7239 page 4, The hydroxyl number of the polyols used can vary within a broad 20 range, In general, it is from about 20 or less to about 1,000 or ; more, preferably from about 20 to about 600 and in particular from about 25 to about 4500 The hydroxyl number i9 defined as the number of mg of potassium hydroxide required for complete hydrolysis of the completely acetylated derivative prepared from 1 g of polyol. The hydroxyl number can also be defined by the following equatian:
,~
OH - 56-1~ x where:
OH is the hydroxyl number of the polyol, f is the functionality, iOeO the average number of hydroxyl groups per molecule of polyol and MW is the molecular weight of the polyolO

The choice of the polyol used depends on the ultimate use of ' O.Z. 31,016/017 the polyurethane product to be manufactured there~rom. The molecular weight or hydroxyl number is suitably selected to give flexible, semi-flexible or rigid foams or elastomers when the polymer~polyol mixture - prepared from the polyol is converted to a polyurethane foam or elastomer. The polyols preferably have a hydroxyl number of from about 200 to about 1,000 if they are to be used for rigid foams, a hydroxyl number of from about 50 to about 150 if they are to be used for the manufacture of semi-flexible foams and from about 20 to about 70 or above if they are to be used for the manufacture of flexible foams.
However, these limits in no way restrict the present invention and instead merely serve to illustrate the large number of possible com-binations of the above polyol co-reactantsq In general, the polyhydroxy compounds (B) are employed in such amounts that the hydroxyl groups of the component (B) are present in amounts which are about equivalent to the isocyanato groups of the component (A), though in order to achieve special properties it may be appropriate to use amounts which are up to about 30% above, or below, the equivalent amountsO
(C) Suitable polymers (C) to be used according to the invention are homopolymers and copolymers which contain no groups which can react with isocyanates or, preferably, which contain at least one group which can react with isocyanates, eOgO OH, NH2, NH, COOH~ SONH2 ; and the like, and which, furthermore, are partially crosslinked and have a gel content of not less than 5%, preferably of from 15 to 90%
and in particular of from 30 to 80%o The gel content is calculated as ~ollows from the proportion of polymer which is insoluble in the particular solvent, e~g~ cyclohexanone:

Weight of undissolved material (dried) Gel content (%) - x 100 Total weight of polymer These homopolymers and copolymers are manufactured by conven~
tional methods from polymerizable olefinic monomers.
Suitable polymerizable unsaturated compounds for the manufacture of homopolymers and copolymers which do not contain groups which ~75398 o. z. 31,016/017 react with isocyanates are monomeric compounds containin~ one or more polymerizable double bonds= Examples are vinyl-aromatics, such as styrene, ~-alkylated styrenes, eOg ~-methylstyrene, nuclear-substi-tuted styrenes, e~gO vinyltoluene, o-, m- and p-ethylstyrene and tert~-butylstyrene, and halogen-substituted styrenes, e~g. o-chloro-styrene, 2,4-dichlorostyrene and o-bromostyrene, olefinic nitriles, e g. acrylonitrile and methacrylonitrile~ vinyl halides7 e.g. vinyl chloride, vinylidene chloride and vinyl bromide, vinyl esters, e.g, vinyl acetate, vinyl propionate and vinyl pivalate, and esters of ~- or R-unsaturated carboxylic acids, eOg~ esters of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and crotonic acid with aliphatic or cycloaliphatic alcohols of 1 to 10 carbon atoms, eOgO methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, tertO-butyl, hexenyl, octyl, ethylhexyl and lauryl acrylate and meth-acrylateO Mixtures of such vinyl compounds may also be used.
However, as already mentioned, homopolymers and copolymers whichcontain groups which react with isocyanates are preferred. Suitable monomers which contain groups which react with isocyanates and which may be used as the starting material for such homopolymers and co-polymers are unsaturated polymerizable alcohols, e.g. vinyl-glycol, but-2-ene-1,4-diol, butenol and/or allyl alcohol, esters of unsatu-rated carboxylic acids, eOgO acrylic acid or substituted acrylic acids, crotonic acid, fumaric acid and itaconic acid, with straight-chain or branched polyhydric alcohols which may contain ether groups, in particular with diols and triols of mean molecular weights from 50 to ~,000, preferably from 50 to 2,000, in which at least one OH
group of the polyhydric alcohol is not esterified, unsaturated co-polymerizable polyols with mean mo~ecular weights of from 200 to ; 6,000, preferably from 500 to 2,000, amides of unsaturated carboxylic acids, e~gO acrylamide and methacrylamide, or other derivatives which react with NCO groups and/or unsaturated monocarboxylic acids or di-carboxylic acids, e~g~ acrylic acid, methacrylic acid, fumaric acid and the like, or their mixtures.
These monomers containing groups which react with isocyanates O Z. 31,016/017

3~1~
may be used either by themselves or as mixtures with the above poly-merizable monomers which do not contain reactive groups, for the synthesis of the polymer (C)O
In general, the polymer is manufactured by conventional pro-cesses, eOgO solution polymerization or suspension polymerization, but preferably emulsion polymerizationO
The emulsion polymerization in an aqueous medium is carried out by conventional methods at from 30 to 100C, in general in the pre-~ sence of emulsifiers, e~gO alkali metal salts, especially sodium -~ 10 salts of alkylsulfonic acids or alkylarylsulfonic acids, alkyl-sul-: furic acids, fatty alcohol-sulfonic acids or fatty acids; preferred emulsifiers are sodium salts of alkylsulfonic acids or fatty acids of 12 to 18 carbon atomsO The emulsifiers are generally used in amounts of from 003 to 5~ especially of from 1~0 to 2DO~ per cent by weight, based on the monomersO Where appropriate, conventional buffer salts, eOgO sodium bicarbonate and sodium pyrophosphate, are also . presentO
. Equally, the conventional polymerization initiators may be used, eOgO persulfates or organic peroxides, :if appropriate together with 20 reducing agentsO The weight ratio of water to monomer is preferably .
: ~rom 2:1 to 007:1 The polymerization is preferably taken to almost complete conversion, iOeO to more than 90%, and in particular more :; than 96%, conversion of the monomers~
The size of the latex particles may be varied by conventional methods, e gO seeding, variation of emulsifier concentration, addition of the emulsi~ier in stages, liquor ratio, (rate of) :~ addition of emulsion and addition of agglomerating agentsO The par-ticle size (iOe diameter) may be from 500 to 5,000 ~ However, poly mers with a mean particle size (d50 value of the weight distribution) 30 of from lgOOO to 2,500 2 are preferred; this mean value may be deter-mined by counting from electron microphotographs~ or by ultracentri-fuge measurementsO The "d50 value" represents a value such that 50%, by weight, of the polymer particles have a diameter above this value , .
,, .

~53~ oOz 31,016/017 and 50%, by weight, of the polymer particles have a diameter below this value~ The breadth of the weight distribution of the dispersed polymer particles may vary within wide limits, but polymer dispersions in which at least 20% by weight, and preferably from 30 to 70% by weight, of the polymer particles have diameters of from 1,000 to 2~500 ~ are preferredO
The crosslinking which is an essential feature of the invention may be brought about by introducing up to about 20% by weight, pre-ferably from Ool to 18% by weight, and especially from 1 to 10% by weight, of a crosslinking agent in the course of polymeriæing the monomersO Alternatively, the crosslinking may be effected subsequent to the manufacture of the polymer, by heating, addition of peroxides or other crosslinking agents, or irradiation Suitable crosslinking agents which may be copolymerized with monoolefinic monomers are, eOgo 9 divinylbenzene, diallyl maleate, diallyl fumarate, diallyl adipate, allyl acrylate, allyl methacrylate, diacrylates and dimeth-acrylates of polyhydroxy-alcohols, e,gO ethylene glycol dimethacrylate, and other poly-olefinically unsaturated monomersO Divinylbenzene is the preferred crosslinking agentO
In order to achieve t~e desired ef~ect of improving the load-bearing capacity of foamed polyurethane compositions, the composition of polymer (C) is so chosen that the polymer has a glass transition temperature of at least L!0C, pre~erably from 50C to 130C.
In order to achieve special properties, eOgO for applications which demand high elasticity even at low temperatures~ coupled with improved load-bearing capacity, graft polymers having two glass transition temperatures, one below -20C, preferably at from -40C
to -90C, and the other above ~40C5 preferably at from 50 to 130C, : are used~
The graft copolymers are manufactured by polymerizing grafting monomers in the presence of the previously formed rubber backbone, in general using conventional graft polymerization methods In such reactions, the monomers are generally added to the previously formed 0 Z0 31,016/017 ~75i~9~
rubber backbone and this mixture is polymerized in order chemically to bind, or graft, at least a part of the copolymer onto the rubber backboneO
The weight ratio of the graft backbone to the grafted-on monomer may be from 90:10 to 10090 and preferably from 80:20 to 40:60.
Various crosslinkable rubbers onto which the copolymer can be grafted may be used as the backbone of the graft copolymer; they include diene rubbers, acrylate rubbers, polyisoprene rubbers and mixtures thereofO
The preferred rubbers are diene rubbers or mixtures of diene rubbers, iOeO all rubbery polymers (i~eq polymers having glass tran-sition temperatures not above 20C, according to ASTM test D-746-52 T) of one or more conjugated 1,3~dienes, eOg~ butadiene, isoprene, : piperylene, chloroprene and the likeO Such rubbers include homopoly-mers o~ conjugated 1,3-dienes and copolymers of these 1,3-dienes with up to equal amounts by weight o~ one or more copolymerizable mono-ethylenic monomersO
The gra~ting monomers used may be t;he monomers mentioned above 3 of which the homopolymers have a glass transition temperature above ~40C.
For spe~ial applications it is entirely possible to use mixtures of graft polymers and polymer~ with glass transition temperatures above 40Co The graft polymers to be used according to the invention also have a gel content of more than 30% 9 preferably from 30 to 90% and especially from 50 to 80~.
The polymer (C) to be used according to the invention is employed in amounts of from 1 to 40 per cent by wei~ht, preferably from 5 to 20 per cent by weight, based on the polyhydroxy compound (B).
. 30 The preferred method of introducing the polymer (C) into the polyhydroxy compound and uniformly distributing it therein is to mix the preferably aqueous polymer dispersion with the polyhydroxy com-pound in conventional apparatuses which permit thorough mixing, such O Z. 31,016/017 1~7S~9~
as continuous or batchwise mixers, eOgO stirred vessels or ISG mixers~
~hereafter, the water and/or other dispersion medium is removed, at least partially~ by the use of conventional physical methods of separation, e.gO at elevated temperatures and/or under reduced pressureO
(D) Assistants and adjuvants (D) which may be used in the pro-cess according to the invention are chain extenders, crosslinking agents, blowing agents or other assistants, eOgO activators, emulsi-fiers, stabilizers, dyes, fillers, flame~proofing agents and the likeO If the product is to be foamed, water and/or other blowing agents, eOgO azo compounds, low-boiling hydrocarbons, halogenated methanes or ethanes or vinylidene chloride, may be usedO The reaction may be carried out in the presence of catalysts, e~gO amines such as triethylamine, dimethylbenzylamineg 1-dimethylamino-3-ethoxypropane, tetramethyl-ethylenediamine, N-alkylmorpholine and triethylenedi-amine and/or metal salts, eOg. tin-(II) acylates, dialkyl-tin-(IV) acylates, acetylacetonates o~ heavy metals, and molybdenum glycolate.
Examples of emulsifiers to be mentioned are oxyethylated phenols or diphenols, higher sulfonic acids, sulfuric acid esters of castor oil or r~cinoleic acid and ammonium salts of oleic acid, .~whilst e~amples of ~oam stabilizers are those containing siloxane and alkylene oxide units, as well as basic silicone oilsO
~Further detailq relating to the above conventional adjuvants ;and assistants (D) are to be found in the specialist literature, e,g.
in the book by Saunders and Frisch, "High Polymers~ Polyurethanes", volumes 1 and 2 (1967)~
We have found, surprisingly, that on removing the water from mixtures of polyols and emulsions of graft polymers, stable disper-sions are obtained, whilst if non-grafted rubber emulsions are used, ~ 30 a macroscopic phase separation takes placeO
: If the polymer/polyol mixtures (C)/(B) described above are used, . in accordance with the invention, to manufacture polyurethane plastics, products having particularly advantageous properties are obtained. - 12 -0 Z0 31,016/017 :~O~
The addition of such polymers results in an improvement in the kensile strength measured according to DIN 53,571 and of the tear resistance and permanent set, measured according to DIN 53,572, of the polyurethane foams In addition to these properties of great practical importance, the addition of such polymers may be used, whilst keeping the density of the product (measured according to DIN 53,420) constant~ in order substantially to increase the indentation hardness (measured accor-ding to DIN 53,577) of cellular flexible polyurethane compositions and foamsO
This improvement in properties offers both commercial and tech-nological advantages in the manufacture of foams used for cushioning, e~g for automobile seats, upholstered furniture and the likeO How-ever, the indentation hardness of soft foams of high density, such as are used, e g , in polyurethane crash pads and fenders, e.g. in automotive construction, may also be improved substantially.
In addition, an increase in the compression ratio (the ratio of the indentation hardness at 60~ compress:ion to that at 20% com-pression) may be achieved by adding the above polymers. This resultq in gradual compressive behavior, iOe. soft resilience under low com~
pressive load but substantially increased load-bearing capacity at greater compressionO This gradual compressive pattern is not only important for cushioning foams, but also a desirable feature in foams of high density, used, eOg , in fenders in automotive construction, shoe soles and similar applications ~ Equally, the compression ratio for conventional hot block foams, - which is about 2, can be increased significantly by adding such poly-mers~ so that hot block foams of improved compression characteristics may be obtained by this method~
If graft polymers having two glass transition temperatures, ob-tained by grafting a hard polymer with a glass transition tempera-ture of above 40 C onto a polymer having a glass transition tempera-ture below 20C, are employed 9 an improvement in the low-temperature 0.~ 31,016/017 ~07~39~1 strength is achieved in addition to the advantages described above~
This means that at low use temperatures the polyurethane composition - which may or may not be foamed - remains flexibleO The retention of flexibility at low use temperatures is particularly desirable in the case of surface coatings, elastomers and foaMs, eOg for applications in automotive construction, the manufacture of shoes, shoe soles and numerous other applicationsO
The parts and percentages mentioned in the Examples are by weightO
EXAMPLES 1 AND 2, AN~ COMPARATIVE EXAMPLE~S
(a) Manufacture of the polystyrene and 80:20 styrene/acrylonitrile copolymer dispersions-150 parts of desalinated water, 005 part of sodium alkylsulfo-nate, eOgO Mersolat K 30, and 002 part of sodium pyrophosphate are first introduced into a stirred kettle, under nitrogenO The rnixture is heated to ~0C and Ool part of potassium persulfate and 10 parts of styrene monomer or o~ an ~0:20 mixture of styrene monomer and acrylonitrile are then addedO 90 parts of styrene monomer or of the 80:20 mixture of styrene monomer and acrylonitrile are run in over 2 hours, and the polymerization is then continued f`or a further hour.
Identical batches are polymerized by the same method, but intro-ducing a regulator (Oo6 part of tert5-dodecyl mercaptan) or cross-linking agent (2 parts of divinylbenzene) in the monomer run in.
(b) r~anufacture of a mlxture o~ the above polymer with a polyether-polyol based on trimethylolpropane, propylene oxide and ethylene oxide (mean molecular weight 4,80o; 0~3 number about 35):
lOO parts of the polyether-polyol are mixed, in a stirred - vessel, with 25 parts of the above dispersions and the water is then removed almost completely on a thin film evaporator at 60C and 5 mm Hgo (c) The viscosity of the mixtures was measured on a Brookrield visco-meter at 23C and 50 rpm; the results are shown in the Table which follows:

* Tradcmark o~ Bayer ~G, Leverkusen, Germany.
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(d) Manufacture of the sa~`t polyureihane foams, and tests thereon:
1~0 parts of a polymer/polyol mixture containing 10 parts of polymers 1 A to 2 C and 100 parts of a polyether-polyol based on tri-methylolpropane, propylene oxide and ethylene oxide~ the mixture having an 0l~ number of 32, 2 8 parts of water, 1 2 parts of silicone : foam stabilizer, 0.08 parts of diazo-bicyclo-2,2,2~octane, 0.5 part of N-ethylmorpholine, 0003 part Or dibutyl-tin dilaurate, 0.08 part of Niax A 1 (a solution of 2,2'-dimethylaminodiethyl ether) as the catalyst, and 36.2 parts of a mixture of 80 parts of toluylenediiso-10 cyanate, comprising 80% of the 2,4 lsomer and 20% of the 2,6-isomer, and 20 parts of a mixture of diphenylmethanediisocyanates and poly-phenylpolymethylenepolyisocyanates are mixed in the mixing chamber of a commercial foaming apparatus and introduced into a closed alurninum mold in which the mixture foams up The polyurethane foams have the fo1lowing properties:

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* Trademark of Union Carbide Corp., U.S.A.

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' ,: i ~ ~7 0,~0 31~016/017 (a) 150 parts of water, 1,2 parts o~ the sodium salt of a paraf~insulfonic acid of 12 to 18 carbon atoms, O. 3 part of potassium persulfate, 003 part of sodium bicarbonate and 0 15 part of sodium pyrophosphate were introduced into a V2A steel kettle designed for 10 atmospheres gauge pressure and equipped with a paddle stirrer; to remove the oxygen, the kettle was flushed twice with nitrogen and the solution was then heated to 65C under nitrogenO 0 5 part of tertO-dodecyl mercaptan and 1607 parts of butadiene were then intro-duced into the solutionO One hour after the start of the polymeri-zation~ the addition of a further 830 3 parts of butadiene in thecourse of 5 hours was startedO After a total reaction time of 19 hours~
the conversion was 96% and a polybutadiene emulsion having a solids content of 39~2%, based on emulsion, was obtained. The polybutadiene obtained from the latex had a glass transition temperature of about .~` 80Co The emulsion was diluted with 100 parts of water, heated to 70C and mixed, at this temperature, with 0~13 part of potassium per-sulfate (in the ~orm of a three per cent strength aqueous solution) and with 11 parts of a mix~ure of styrene and acrylonitrile. The . . .
weight ra~io of styrene to acryloni~rile in this mixture was 7:3.
10 minutes after starting the grafting reaction, the addition of a mixture of a further 39 parts of styrene and 17 parts of acrylo-nitrile in the course of 2 3/4 hours was startedu The reaction tem- ~
perature assumed a value o~ 750CD When all the monomer had been ~ :
added, the reaction was continued for a further hour~
(b) 10 parts (based on solids) of the aqueous emulsion thus ob-tained and 100 parts of a polyether-polyol based on trimethylolpro-pane, propylene oxide and ethylene oxide and having a mean molecular weight of about 4,800 and an OH number of 35 are mixed at about 40C
and the water is then removed alrnost completely, under reduced : 30 pressure The viscosity of the polymer/polyol mixture was about 3,000 cp (measured on a Brookfield viscometer at 50 rpm and 23C) Manufacture of a foam, and tests thereon:

0,Z0 31,016/()17 ~ 3~ ~
(a) 100 parts of a polymer/polyol mixture of 10 parts of the : above graft polymer and 90 parts of a polyether-polyol based on tri-methylolpropane, propylene oxide and ethylene oxide, the OH number of the mixture being 32, 10 parts of 1,4-butanediol, 0.02 part of diaza-bicyclo-2,2-octane and 6 parts of fluorotrichloromethane are mixed i with 47 parts of a prepolymer based on 4J4~-diphenylmethanediiso-cyanate and a polyalkylene oxide and having an NC0 content of 23.3%, and the mixture is foamed in a closed moldO
(b) The mixture is as under (a), but using only 90 parts Or polyol, without graft polymerO
The cellular polyurethane has the following properties:

(a) with polymer (b) without according to the polymer invention Density (kg/m3) (DIN 53,420) 600 600 Shore hardness A
, (DIN 53,505) at +20C 64 62 at ~20C 68 72 at -40C 69 85 .. . . . .. _ . _ . ..... . . . .. ... . _ The polyurethane manufactured according to the invention thus substantially retains its flexibility even at low temperatures.

(a) Manufacture of the copolymer dispersions A mixture of 50 parts of water and 005 part of Na alkylsulfonate, e.gO Mersolat K 30 ,is introduced, under nitrogen, into an autoclave equipped with feed vessels and a paddle stirrer, and is heated therein to 80 C. When this temperature has been reached, 0~1 part of potassiwn persulfate and 1/5 of a preemulsified mixture Or 100 parts 20 of the monomer mixture, 100 parts of desalinated water, 0~5 part of Mersolat K 30 and, optionally, a regulator or crosslinking agent, * Tradem~r]~.

.~

OOZ, 31,016/017 ~0~5~8 are addedO When the polymerization has started, the remaining 4/5 of the pre-emulsified mixture are added in the course of 2 hours and the polymerization is then continued for a further hourO The Table given in (c) shows the composition of the copolymers and the regulators or crosslinking agents used in the polymerizationO
(b) Manufacture of the mixtures with a polyether-polyol:
100 parts of a polyether-polyol based on trimethylolpropane, propylene oxide and ethylene oxide, and having a mean molecular weight of 4,800 and an OH number of 35, are mixed with 25 parts of the emulsion manufactured according to (a) in a stirred vessel and the water is then removed completely under reduced pressure?
(c) The viscosities of the mixtures were measured on a Brookfield viscometer at 23C and 50 rpmO The results are summarized in the . Table which follows:

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O o Z ~ 31 ,016 /017 ~5~9~1 I~
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.
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m ~ ~ m ~-~07~;3~19 (d) Manufacture of the soft polyurethane foams, and tests thereon:
110 parts of a polymer/polyol mixture containing 10 parts of any one polymers from the group of polymers 4A to - 6C and 100 parts of a polyether-polyol based on trime-thylol-propane, propylene oxide and ethylene oxide, the mix-ture having an OH number of 32, 2.8 parts of water, 1.2 parts of silicone foam stabilizer, 0.08 part oE diazo-bicyclo-2,2,2-: octane, 0.5 part of N-ethylmorpholine, 0.3 part of dibutyl-tin 10 dilaurate, 0.08 part of Niax A 1 (a solution of 2,2'-dimethyla-minodiethyl ether) as the cat6alyst, and 36.2 parts of a mixture :' of 80 parts of tuluylenediisocyanate, comprising 80% of the 2,4-isomer and 20% of the 2,6-isomer, and 20 parts of a ~ mixture of diphenylmethanediisocyanatesand polyphenylpolymethylene-polyisocyanates are mixed in the mixing chamber of a commercial foaming apparatus and introduced into a closed aluminum mold, in which the mixture foams up.

* Trademark.

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~ ~ 7S3 ~ ~ OOZ 31,016/017 ` (a) The following products were first introduced into a V2A steel kettle, designed for 10 atmospheres gauge pressure and equipped with a paddle stirrerO
150 parts of water, 1.2 parts of the sodium salt of a paraffin-sulfonic acid of 12 to 18 carbon atoms, 003 part of potassium persul-~ate, 0.3 part of sodium bicarbonate and 0u15 part of sodium pyro-phosphateO
To remove the oxygen3 the kettle was flushed twice with nitrogen and the solution was then heated to 65C in a nitrogen atmosphere~
10 0.5 part of tertO-dodecyl mercaptan and 1607 parts of butadiene were then introduced into the solution. Beginning one hour after the start of the polymerization, a further 83.3 parts of butadiene were added in the course of 5 hoursO After a total reaction time of 19 hours, the conversion was 96% and a polybutadiene emulsion having a solids con-tent of 3902%, based on emulsion, was obtainedO The polybutadiene la~ex had a glass transition temperature of about -80C.
The polybutadiene emulsion thus obtained was diluted with 100 parts of water and heated to 70C3 and at this temperature 0.13 part of potas~ium persulfate (in the form of a 3~ strength aqueous solution) and 11 parts of a mixture of styrene and acrylonitrile were added.
The weight ratio of styrene to acrylonitrile in this mixture was 7:3.
Beginning 10 minute~ after the start of the grafting reaction, a mixture of a further 38 parts of styrene, 1~ parts of acrylonitrile and 2 parts of hydroxypropyl acrylate was metered in over 2 3/4 hours.
In the course thereof, the reaction temperature assumed a value of 75Co After all the monomer had been added, the reaction was con-tinued for a further hour, (b) 10 parts (based on solids) of the aqueous emulsion thus ob-;~ tained are mixed, at about 40C, with 100 parts of a polyether-polyol ; 30 based on trimethylolpropane, propylene oxide and ethylene oxide and -' having a mean molecular weight of about 4,800 and an OH number of 35, and thereafter the water is removed virtually completely under reduced - 2 1J - ' .
~ ~ .

OOZ. 31,016/017 ~L~7~
pressure. The viscosity of the polymer/polyol mixture was about 2,500 (measured on a Brookfield viscometer at 50 rpm and 23C).
(c) Manufacture of the foam:
(1) 100 parts of a polymer~polyol mixture of 10 parts of the above graft polymer and 90 parts of a polyether~polyol based on tri-methylolpropane, the mixture having an OH number of 32, 10 parts of 1,4-butanediol, 0.02 part of diaza-bicyclo-2,2,2-octane and 6 parts of monofluorotrichloromethane, and 47 parts of a prepolymer having an NCO content of 2303% and based on 4,4'-diphenylmethanediisocyanate and a polyalkylene oxide, are foamed in a closed aluminum mold~
(2) The mixture used is as under (1)9 but with only 90 parts of polyether-polyol, without graft polymerO
.~ The cellular polyurethane has the following properties:

1) with polymer (c) 2) without (according to the polymer (c) invention) Density (kg/m3) (DIN 53,420) 600 600 : .Shore hardness A
. (DIN 53,505) . at ~20C 66 63 at -20C 68 72 at -40C 70 85 . The polyurethane manufactured according to the invention thus substantially retains its flexibility even at low temperatures.

.~ :
. EXAMPLE 8 A AND COMPARATIVE EXAMPLE 8 B

: If a procedure analogous to that described for Example 4 C and

4 A is used~ but with different emulsifier concentrations, the follo~

wing copolymer latices are obtained:
:

~7S3~9~ oO z. 31,016/017 Example Na alkylsulronate Gel Particle size distribu-~i (Mersolat K 30 ) content tion (R) % by weight Initially Subse- d~o d50 dgo :: added quently run in 4 C 0~5 5 781~0001~230 1~560 -:~ 8 A loO 1~0 7605720 880 990 . Cornpara-tive Example 8 B 2,5 205 7301310 420 550 The mixture with the polyether-polyol was prepared analogously - to 4 b, and the polyurethane foam was produced analogously to ; Example 4 do The rollowing test results are obtained:
A comparison of Example 8 A with Comparative Example 8 ~ shows that in the presence of crosslinked polymer particles Or size less ~ than 500 ~ polyurethane foams are not obtained.
Polymer according to Example 4 C 8 A
Comparative Example 8 B
::.:
- Vis cOs ity ( cP ) 1 ~ 800 2 ~ 700 2 ~ 600 - Density (kg/m3) 50 50 ` (DIN 53~420) Tensile strength (kp/cm2) 1065 lo 78 : (DIN 53~571) ~longation at break (%) 157 158 0 (DIN 539571) Compressive strength (p/cm2) (DIN 53~577) 20% compression 40 38 40% compression 58 54 60% compression 110 92 (a) Manuracture Or the copolymer In a stirred kettle, 1 part Or a dispersion manuractured *Trad~mark.
~ - 26 -:

~ O.Z0 31,016/017 ~i7S;~
according to ~xample 4 C is diluted with 145 parts of water and heated to 85C, after which 20 parts of a monomer mixture cr 18.5 parts of styrene, 1 part of hydroxypropyl acrylate, 0.5 part o~ divinylbenzene and 0.05 part of potassium persulfate are added. After the polymeri-zation has started (after about 20 minutes), 80 parts of the monomer mixture and 0.1 part of potassium persulfate, 1 part of Mersolat K 30 and 5 parts of water are run in as two separate streams in the course of 3 hoursO The reaction mixture is then polymerized for a further 2 hoursO After completion of the polymeri~ation, a latex ha~ing a solids content of 3905% and an average particle size (d50 value of`
the wei~ht distribution) of 4,100 R is obtained. 'l'he ~el content (at 170 strength in cyclohexanone) is 7806% and the swelling index is '~.6.
The mixture with the polyether-polyol was prepared analogously to 4 b, and the foam was produced analogously to Example 4 d. The following test results were obtained:
Viscosity (cP) 1,350 Density (kg/m3) (DIN 53,420) 50 Tensile strength (kp/cm2) (DIN 53,571) lo 78 hlongation at break (%) (DIN 53,571) 147 20 Compressive strength (p/cm ) (DIN 53,577) - 20% compression 41 40% " 57 60% " 98 (a) Manufacture of the copolymer The copolymer i5 manufactured analogously to Example 9 except that in place Or 145 parts Or water, 60 parts were used, and instead of 1 part of Mersolat K 30 , 105 parts were usedO This method gives a latex with a broad particle size distributionO The weignt distr;-bution is:
30 d1o 1,690 R; d50 2,350 R; d90 4,720 R; The solids content :is 59~6'io, (b) Manufacture of the mixture with the polyether-polyol *Trademark. - 27 -t '' , , OOZo 31,016/017 ~)7~3~
A polyether-polyol based on trimethylolpropane, propylene oxide and ethylene oxide, and having a mean molecular weight of about 4,800 and a hydroxyl number of 35 is mixed, in a stirred vessel, with the ernulsion prepared according to (a), in a ratio such that after removing the water, under reduced pressure~ a mixture o~ 100 parts of polyether-polyol and 3 parts of polymer is obtained The hydroxyl number of the mixture was 330 (c) Manufacture o~ the polyurethane foam, and tests thereon:
The foam was manu~actured analogously to Example 4 d, with 108 parts of the above polyether-polyol/polymer mixtureO Tests on the foam gave the following results:
Viscosity (cP) 1,420 Density (kg/m3) (DIN 53,420) 48u9 .. ~ Tensile strength (kp/cm ) (DIN 53,571) 1076 Elongation at break (%) (DIN 53,571) 158 ~ Compressive strength (p/cm ) (DIN 53,577) : 20% compression 33 : -40% " 45 60% " 78 Tear resistance (kp/cm) (DIN 53,575) 0,64 A mixture of 100 parts of a polyether-polyol based on trimethylol-j., propane, propylene oxide and ethylene oxide, and having a mean mole-cular weight of 6,200 and a hydroxyl number of 27, and 8 parts of a polymer which was manufactured analogously to Example 4 C and 4 a, is foamed analogously to Example 4 d, For oomparison purposes, a poly-urethane foam without added polymer was manufactured, The test results obtained are summarized in the Table which follows:

Example 11 Comparative Example _ without_added polymer Density (kg/m3) 4801 48~5 (DIN 53,420) Tensile strength (kp/cm2) 1093 1.66 (DIN 53,571) - 2~ -OOZ 31,016/017 ~(~753~1~
Elongation at break (%) 172 228 (DIN 53,571) 2 Compressive strength (p/cm ) (DIN 53,577) 20% compression 26 18 40% " 38 28 60~ ~ 65 1,7 100 parts of a polymer/polyether-polyol mixture of 8 parts of a polymer, manufactured according to Example 4 C and ll a, and 92 parts of a polyether-polyol based on trimethylolpropane, propylene oxide and ethylene oxide, the mixture having a hydroxyl number of 32, 10~4 parts of an alkylenediamine/propylene oxide adduct o~ molecular weight about 500, 2094 parts of water, 0~41 part of diaza-bicyclo-2,2,2-octane, 0O82 part o~ dimethylbenzylamine and 54 parts o~ a mixture o~
diphenylmethanediisocyanate and polyphenolpolymethylenepolyisocyanate are mixed in the mixing chamber of a commercial foaming apparatus and introduced into a closed aluminum mold, in which the mixture foams upO
In a parallel experiment, a polyurethane foam was manu~actured from the same starting components~ but without added polymer, Tests on the foams gave the ~ollowing results:

Example 12 Comparative Example without added polymer .... ~
Density (kg/m3) 4709 40 6 (DIN 53,420) Tensile strength (kp/cm2) lo 30 0~69 (DIN 53,571) Elongation at break (%) 50 51 (DIN 53,571) Compressive strength (p/cm2) (DIN 53,577) 20% compression 42 16 40% compression 63 24 - 0,Z0 31,016/017 1 ~7~
60% compression 124 44 Tear resistance (kp/cm) 0 33 0.17 (DIN 53~575) : 100 parts of a polymer/polyether-polyol mixture of 8 parts of a polymer~ manu~actured according to Example 4 C and 4 a, and 92 parts of a polyether-polyol based on trimethylolpropane, propylene oxide and ethylene oxide, the mixture having a hydroxyl number of 32, 1.8 parts of water, 0018 part of diaza-bicyclo-2,2,2-octane, 00092 part of a polyoxypropylene-siloxane copolymer, 0O138 part of tin-II
octoate, 406 parts of monorluorotrichloromethane and 2406 parts of toluylenediisocyanate, consisting of 80% of the 2,4-isomer and 20% :
of the 2,6-isomer, are mixed in the mixing chamber of a commercial foaming apparatus and introduced into a closed aluminum mold, in ~hich the mixture ~oams upO
In a parallel experiment, a polyurethane foam was manufactured from the same starting components, but without added polymerO
The foams had the following mechanical propçrties:

Example 13 Comparative Example ` without added polymer Density (kg/m3) 3802 3800 ~DIN 53,420) 4 ~ Tensile strength (kp/cm2) 0~82 0,71 (DIN 53,571) Elongation at break (%) 127 126 (DIN 53,571) Compressive strength (ptcm2) (DIN 53,577) 20% compression 25 20 40% " 35 25 60% " 58 40 Tear resistance (kp/cm) 0046 oO38 (DIN 53,575) - O~Z0 31,016/017 ~ ~ 7 9207 parts of a polymer/polyether-polyol mixture of 903 parts of a polymer, manufactured according to Example 4 C and 4 a, and 83.4 parts of a polyether-polyol based on trimethylolpropane, propylene oxide and ethylene oxide, the mixture having a hydroxyl number of 32, 3 parts of an alkylenediamine/propylene oxide adduct having a mole-cular weight of about 500, 3 parts of water, lo 15 parts of a catalyst mixture of diaza-bicyclo~-2,2,2-octane and a mixture of linear tertiary amines, 0~2 part o~ a stabilizer based on an adduct of a siloxane and propylene oxide, and 48 parts of a prepolymer, having an NC0 content of 39% by weight and manufactured from a mix of a crude mixture of diphenylmethanedi.isocyanates and polyphenylpolymethylene-polyisocyanates and crude toluylenediisocyanate and a polyether~poly-ol having a mean molecular weight of 1,000, are mixed in the mixing chamber of a commercial foaming apparatus and introduced into a closed aluminum mold, in which the mixture ~.oams upO
In a parallel experiment, a polyurethane foam was manufactured ~rom the same ~tarting components, but without added polymer, The foams had the following mechanical properties:

Example 14 Comparative Example without added polymer Density (kg/m3) 4805 48,8 (DIN 53,420) Tensile strength (kp/cm )2003 lo 73 (DIN 53,571) Elongation at break (%) 110 128 . (DIN 53,571) Compressive strength (p/cm2) 20~ compression 49 33 40% " 66 46 60% " 111 79 Tear resistance (kp/cm) 0.48 Oo38 (DIN 53,575) ~ 31 ~

^- OOZ 31,016/017 ~S3~
EXAMPLE 1~
(a) A monomer mixture of 39 parts of vinyl chloride and 1 part of pentaerythritol triallyl ether was polymerized in the presence of 60 parts of desalinated water, 004 part of Mersolat K 30 ,002 part of`
stearyl alcohol, oO08 part of potassium persulfate, o 04 part Or sodium pyrophosphate and 0~04 part of trisodium phosphate, at 50C in a stirred autoclave, with exclusion of oxygen, until the pressure droppedO Arter removing the residual monomer, a latex with the follo-wing characteristics was obtained- solids content 3804~, particle size d50 1,500 ~, gel content ~%0 10 (b) Manufacture of the mixture with a polyether-polyol:
100 parts of a polyether-polyol based on trimethylolpropane~
propylene oxide and ethylene oxideg and having a mean molecular weight Or 4,800 and an OH number of 35, are mixed with 25 parts of ~ the emulsion manufactured according to (a), in a stirred vessel, and the water is then removed completely under reduced pressurec The : polymer had a Brookfield viscosity (23C/50 rpm) of 3,650 cP
The foam is manufactured analogously to Example 4 d, using 110 parts of the polyether-polyol/polymer mixture described under (b).
'i'he foam obtained had the following properties;
-: 20 Density (k~/m3) (DIN 53,420) 44 4 'I'ensile strength (kp/cm2) (DIN 53~571)1 3 Elongation at break (%) (DIN 53,571) 144 Compressive stren~th (p/cm2) (DIN 53,577) 20% compression 26 l~O% " 37 60% " 65 '~ . ' :
: .
* Trademark.

~7 1 ~

Claims (2)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A process for the manufacture of polyurethanes which comprises:
I. mixing 1. a polyhydroxy compound (B) having a molecular weight of from about 500 to 7000 and a hydroxyl number of from 20 to 1000 and selected from the group consisting of polyether-polyols and polyester-polyols, with 2. an aqueous polymer dispersion containing a cross-linked particulate polymer (C) having a particle size of from 500 to 5000 .ANG. and a gel content of not less than 5% and comprising homopolymers, copolymers, graft polymers or mixtures thereof, said crosslinked polymer (C) being obtained by the emulsion or suspension polymerization of a. unsaturated compounds with straight-chain or branched polyhydric alcohols of mean molecular weights from 50 to 6000, in which at least one OH group of the polyhydric alcohol is not esterified, unsaturated copolymerizable polyols with mean molecular weights of from 200 to 6000, acrylamide, methacrylamide, butadiene, isoprene, piperylene and chloroprene, and b. crosslinking agents incorporated in the poly-merized form in an amount of from 0.1 to about 20% by weight and selected from the group consisting of divinylbenzene, diallyl malcate, diallyl fumarate, diallyl adipate, allyl acrylate, allyl methacrylate, diacrylates and dimethacrylates of polyhydroxyalcohols and butadiene, wherein said homopolymers and copolymers have a glass transition temperature of from 40 -to 130°C and said graft polymers have two glass transition temperatures, one of from -40° to -90°C and the other of from 40°
to 130°C;
II. removing the water from the mixture to produce a dispersion of 1 to 40% by weight of polymer(s) (C) in 99 to 60% by weight of polyhydroxy compound (B); and III. reacting the resultant mixture of (B) and (C) with an organic polyisocyanate (A) to form the polyurethanes, -the ratio of the NCO equivalent of polyisocyanate to radicals of said mixture (B) and (C) which are reactive with isocyanato radicals being in the range of about 0.7 - 1.3:1.
2. A process as claimed in claim 1, wherein the polymer (C) has a glass transition temperature of from 40°C to 130°C.

3. A process as claimed in claim 1, wherein the polymer (C) which is used is a graft polymer which has two glass transition temperatures, of which one is from -40° to -90°C and the other from 40° to 130°C, or is a mixture of this graft polymer with a polymer which has a glass transition temperature of from 40°
to 130°C.
4. A process as claimed in claim 1, wherein the organic polyisocyanate is selected from the group consisting of toluylenediisocyanates, mixtures of diphenylmethanediisocyanates and polyphenylpolymethylenepolyisocyanates and mixtures of toluylen-diisocyanates with a mixture of diphenylmethanediisocyanates and polyphenylpolyrlethylenepolyisocyanates.

5. A process as claimed in claim 1, wherein the poly-hydroxy compound(s) used are polyether-polyols having a molecular weight of from 500 to 7,000 and a hydroxyl number of from 20 to 150.

6. A process as claimed in claim 1, wherein the cross-linked, particulate polymer(s) (C) have a particle size of from about 1,000 to 2,500 .ANG..

7. A process as claimed in claim 1, wherein the polymer(s) (C) contain from 0.1 to 18% by weight, based on their weight, of a crosslinking agent.

8. A process as claimed in claim 7, wherein the crosslinking agent used is divinylbenzene, a diallyl maleate, a diallyl fumarate, a diallyl adipate, an allyl acrylate, an allyl methacrylate or a diacrylate or dimethacrylate of a polyhydroxyalcohol.

9. A process as claimed in claim 8, wherein the crosslinking agent used is divinylbenzene.

10. A process as claimed in claim 1, wherein the polymer(s) (C) contain at least one hydroxy group which can react with isocyanates.

11. A process as claimed in claim 10, wherein the polymer(s) (C) contain polymerized units of hydroxypropyl acrylate, butanediol monoacrylate or a reaction product of 1 mole of maleic anhydride and 1 mole of polyether-polyol based on polypropylene glycol with a mean molecular weight of 2,000.

12. A process as claimed in claim 1, wherein the polymer(s) (C) are obtained by polymerization of styrene with divinylbenzene or styrene with acrylonitrile and divinylbenzene, the acrylonitrile content being from 0.1 to 50% by weight, based on the weight of styrene and acrylonitrile.

13. A process as claimed in claim 12, wherein the polymer(s) (C) contain, as additional monomers, hydroxypropyl acrylate, butanediol monoacrylate or a reaction product of 1 mole of maleic anhydride and 1 mole of a polyether-polyol based on polypropylene glycol with a mean molecular weight of 2,000.

14. A process as claimed in claim 1, wherein the gel content of polymer(s) (C) is from 15 to 90%.

15. A process as claimed in claim 1, wherein the polyurethane is foamed.

16. Polyurethane compositions - which may or may not be foamed - manufactured by I. mixing

1. a polyhydroxy compound (B) having a molecular weight of from about 500 to 7000 and a hydroxyl number of from 20 to 1000 and selected from the group consisting of polyether-polyols and polyester-polyols, with

2. an aqueous polymer dispersion containing a crosslinked particulate polymer (C) having a particle size of from 500 to 5000 .ANG. and a gel content of not less than 5% and comprising homopolymers, copolymers, graft polymers or mixtures thereof, said crosslinked polymer (C) being obtained by the emulsion or suspension polymerization of a. unsaturated compounds with straight-chain or branched polyhydric alcohols of mean molecular weights from 50 to 6000, in which at least one OH group of the polyhydric alcohol is not esterified, unsaturated copolymerizable polyols with mean molecular weights of from 200 to 6000, acrylamide, methacrylamide, butadiene, isoprene, piperylene and chloroprene, and b. crosslinking agents incorporated in the polymerized form in an amount of from 0.1 -to about 20% by weight and selected from the group consisting of divinyl-benzene, diallyl maleate, diallyl fumarate, diallyl adipate, allyl acrylate, allyl methacrylate, diacrylates and dimethacrylates of polyhydroxyalcohols and buta-diene, wherein said homopolymers and copolymers have a glass transition temperature of from 40° to 130°C and said graft polymers have two glass transition temperatures, one of from -40° to -90°C and the other of from 40° to 130°C;
II. removing the water from the mixture to produce a dispersion of 1 to 40% by weight of polymer(s) (C) in 99 to 60% by weight of polyhydroxy compound (B); and III. reacting the resultant mixture of (B) and (C) with an organic polyisocyanate (A) to form the polyurethanes, the ratio of the NCO equivalent of polyisocyanate to radicals of said mixture (B) and (C) which are reactive with isocyanato radicals being in the range of about 0.7 -1.3:1.