CA1074494A - Compositions having good hydrolytic stability and improved strength properties - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Polyurethane compositions having good hydrolytic stability and improved strength properties are prepared by reacting polyester polyols or polyether polyols with poly-isocyanates in the presence of about 5 to 40%, based on the total weight of reactants, of a polyhydroxyl-containing diene polymer. Conventional reaction procedures are employed.

Description

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BACKGROUND OF THE INVENTION
This invention relates to polyurethane compositions and more particularly to polyurethane compositions having good hydrolytic stability and improved physical properties.
Polyurethane compositions are conventionally prepared by reacting polyisocyanates with polyhydroxyl- ~ -containing compounds. Polyester polyols and polyether polyols are frequently chosen as the polyhydroxyl-containing component for use in the manufacture of polyurethanes because of their general availability and low cost and because molded articles made from them usually exhibit superior physical properties. However, when polyester polyols or polyether polyols are used in the preparation of polyurethane compositions, the resulting compositions generally have poor hydrolytic stability. It is believed -that the poor hydrolytic stability is caused by the pre-sence of ether or ester linkages existing in the polymer chain. In confirmation of this belief, it has been dis-covered that polyurethanes prepared from polyhydroxyl-containing compounds which have ~ew or no ether or ester linkages have good hydrolytic stability~
U.S. Patent 2,877,212 issued to Seligman on March 10, 1959 describes a class of polyurethanes prepared from difunctional polymers of conjugated dienes. me com-positions of ~eligman have no ester or ether linkages and consequently have good hydrolytic stability but the Seligman compositions are rubbery polymers, ho~ever, and are not generally suitable for molding articles which are desirably rigid and have hard surfaces. U.S~ Patents 3,427,366 and 3,674,743 issued on February 11, 1969 and - . ., . , , ~ .

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July 4, 1972 respectively to Verdol et al also describe polyurethane compositions prepared from polyhydroxyl-containing diene polymers and polyisocyanates. The compo-sitions described in the Verdol et al patents are likewise rubbery polymers and do not have generally good molding properties. m e above-described hydrolytically stable polyurethanes are not widely used because of their higher cost and because some of their physical properties are considerably poorer than those of conventional polyurethanes.
Polyurethane compositions have now been discovered which are prepared from polyester polyols or polyether polyols and yet have good hydrolytic stability. Furthermore, the physical strength properties of the new compositions described herein are superior to those of conventional polyurethanes prepared from polyester polyols or polyether ~ ;
polyols. The compositions of this invention can be made in the form of rubbery polyurethane composi-tions or ~ resinous molding compositions which can be cured to hard ; durable polymeric compositions.
Accordingly, it is an object of this invention j to present inexpensive polyurethane compositions which have -, excellen-t hydrolytic stability and improved physical pro-perties. It is another object of the invention to present polyurethane compositions prepared from polyester polyols ' or polyether polyols which have good hydrolytic stability.
-Lt is another object of this invention to present poly-urethane compositions having good molding properties. It is another object of this invention to present new poly-urethane compositions which can be used to produce molded articles ha~ing good hardness and strength properties. It ... .. . : . . : . .
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is another object of this invention to present a method of improving the hydrolytic stability of polyurethane com-positions prepared from polyester polyols or polyether polyolsO It is another object of this invention to present ; a method for preparing inexpensive polyurethane compositions which have good hydrolytic stability and good molding properties. It is another object of this invention to present a method of improving the hardness and physical -strength properties of moldable polyurethane compositions.
These and other objects of the invention will become apparent from the following description and examples.
SU~ARY OF I~IE INVENTION
The improved polyurethane compositions of the invention are prepared by reacting a polyisocyanate with a polyester polyol or a polyether polyol in the presence of about 5 to 40~ based on the total weight of reactants of a polyhydroxyl polymer of a 1,3-diene hydrocarbon of 4 to 12 carbon atoms having a number average molecular weight of about 400 to 25,000 and about 1.8 to 3.0 predominantly primary terminal allylic hydroxyl groups per molecule. The relative amounts of polyisocyanate and polyhydroxyl-contain-ing compounds used to prepare the compositions of the invention are such that the ratio of isocyanate groups to total hydroxyl groups in the reaction mixture is about 0.85 to 2~0:1. In preferred embodiments of the invention, the polyisocyanate is an aromatic diisocyanate; the polyhydroxyl polymer of a 1,3-diene hydrocarbon is hydroxylated poly-butadiene containing about 2 to 2.L~ hydroxyl groups per molecule; the ratio of isocyanate groups to hydroxyl groups in the reaction mixture is about 0.95 to 1.3:1, and the ;
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amount o~ polyhydroxyl polymer of the 1~3-diene present in the reaction mixture is about 10 to 35~ based on the total weight of reactants.
DESCRIPTION OF THE INV NTION
The compositions o~ this invention may be prepared according to any one o~ the well known procedures for pre-paring polyurethanes. Thus, the "one shot method" in which all o~ the reactants are combined in a suitable reaction vessel and heated with continued agitation in the presence o~ a suitable polymeriza-tion catalyst can be used. Likewise, under certain conditions it may be desirable to employ the prepolymer method in which a portion of one o~ the reactants is combined with another reactant to ~orm a prepolymer and the remaining part of the first reactant is combined with the prepolymer in a subsequent polymerization step. For example, it may be desirable to react one or more of the hydroxyl components with the polyisocyanate component to form an isocyanate-terminated prepolymer. The prepolymer can then be reacted with the remaining polyhydroxyl contain-ing components to ~orm the ~inished product. This method can be used to advantage in the present invention when relatively large amounts of hydroxylated diene polymer are employed in the reaction mixture, thereby raising the possibility o-~ a compatability prob]em. I~ the diene polymer component is reacted with the polyisocyanate to ~orm a pre-polymer, and the resulting prepolymer reacted with the remaining polyhydroxyl-containing components, the ~inal composition is completely homogeneous In any event, workers skilled in the art will be easily able to determine the optimum reaction conditions for preparing the composi-tions of the invent on.

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THE POLYISOCYANATE COMPOUNDS
The organic polyisocyanates employed in the reaction o~ the invention may be any of the polyisocyanates conventionally used to prepare polyurethanes. Polyisocya-nates used to prepare polyurethanes include saturated and unsaturated aliphatic and cycloaliphatic compounds, aromatic compounds, aliphatic-substituted aromatic compounds, and aryl-substituted aliphatic compounds, etc. The polyiso-; cyanates used in the invention generally have a functionality of at least 2 and generally of about 2 to 6 isocyanate groups per molecule. It is preferred to use diisocyanates, .
i.e., those which have 2 functional groups per molecule as these are more economical to produce than organic isocyanates having more than two isocyanate groups per molecule. If it is desired to produce highly cross-linked material, it is generally preferred that one or more of the polyhydroxyl components contain in excess of two functional groups per molecule rather than the isocyanate component as ~hey are less expensive to prepare than isocyanates containing more than two functional groups per molecule. Aromatic poly-isocyanates are preferred over aliphatic isocyanates as they are considerably less toxic and, therefore, present fewer handling problems and, furthermore, they are generally more reactive than the aliphatic isocyanates. l~e poly-isocyanates used in the invention may contain substituents provided they do no-t interfere with the desired reaction between the polyisocyanates and the polyols.
Included among the aliphatic isocyanates useable ~-~
in the invention are alkylene diisocyanates such as 1,3-trimethylene diisocyana-te, 1,4-tetramethylene diisocyanate; ~
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1,6-hexamethylene diisocyanate; 1,3,5-pentamethylene tri-isocyanate; 1,4-cyclohexane diisocyanate; 1,~-cyclohexylene diisocyanate; 1,4-diisocyanako butene-2. Examples of aromatic isocyanates are tolylene diisocyanate; p-phenylene diisocyanate; diphenyl methane diisocyanate; dimethyl diphenyl methane diisocyanate; bibenzyl diisocyanate; bitolyl diisocyanate; benzene triisocyanate; 1,5-tetrahydronaphthalene diisocyanate; 4-chloro-1,3-phenylene diisocyanate; etc.
In the case of aromatic isocyanates, the isocyanate groups may be attached to the same or different rings.
THE POLYESTER AND POLYETHER POLYOL COMPOUNDS
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The polyester and polyether polyols useful in the preparation of the compositions of the invention are those having two or more hydroxyl groups per molecule. In pre-paring high molecular weight polyurethanes, it is preferable that the hydroxyl group content of the polyester or polyether be in the range of about 2 to 3 groups per molecule. When ; more highly cross-linked polymeric products are to be prepared, the hydroxyl functionality of these compounds may be somewhat higher than 2 and generally up to about 6 or more groups per molecule. It is preferred that the concen-tration of materials having hydroxyl ~unctionality greater than about 6 be kept low to prevent premature setting of ~ the polyurethane composition.
; The polyester and polyether polyols used may be any of the polyester or polyether polyols generally used in the preparation of polyurethanes including saturated or ethyl-enically unsaturated aliphatic or cycloaliphatic, aromatic, ; aliphatic substituted aromatic or aryl substituted alipha~

tic compounds. The polyester and polyether polyols : ' ~ .
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may also contain mixtures of aliphatic and aromatic groups as in the case in which polyesters are prepared from aliphatic diacids and aromatic diols or vice versa.
I'he molecular weight of useful polyester and polyether polyols may range up to about 75,000 or higher although the molecular weight range of the most widely used polyester and polyether polyols varies from about 550 to 4,000 and those having average molecular weights of about 600 to 3,000 are preferred for use in the compositions of the invention. me hydroxyl number of suitable polyester and polyether polyols varies from about 12 to 1~100 or more. In the preferred polyester and polyether polyols the hydroxyl number is about 40 to 150 me hydroxy-containing polyesters may be obtained by the reaction of aliphatic or aromatic polycarboxylic acids, preferably dicarboxylic acids, with aliphatic or aromatic polyhydric alcohols, in the manner well known to the art in proportions that result in esters having at ; least two reactive hydroxy groups per molecule. Any poly-hydric alcohols generally used to prepare polyesters may be used to form the hydroxy esters, and illustrative of such alcohols are ethylene glycol; diethylene glycol; pro-pylene glycol; 1,3-butylene glycol, 1,6~hexanediol;
butenediol; butynediol; amylene glycols; 2-methylpentanediol-

2,4; 1,7-heptanediol; glycerine; neopentyl glycol; tri-methylol propane; pentaerythritol; cyclohexane dimethanol;
sorbitol; mannitol; glactitol; talitol; xylito~j 1,2,5,6-tetrahydroxyhexane; styrene glycol; bis ~-hydroxyethyl)-diphenyl-dimethylmethane, and 1,4-dihydroxybenzene.

:, '' ' ' "' ' ' ' Any of the polybasic carboxylic acids generally used in the preparation of polyesters may be used in the invention including, e.g., saturated aliphatic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, etcj unsaturated aliphatic acids such as maleic acid, fumaric acid, itaconic acid, aconitic acid, etc.; arylene acids such as phthalic acid, isophthalic acid, tetrachloro-phthalic acid, trimellitic acid, etc.; and mixtures of these.
me anhydrides of appropriate acids may also be used in preparing polyesters useful in the invention.
Also included within the suitable esters are the diglycerides of hydroxyl-containing castor oil, tall oil, soya oil, linseed oil, etc. These esters are usually pre-polymers prepared by the reaction of the fatty glyceride ~
with low molecular weight polyols. Illustrative~ for ~- -instance, of castor oil-based prepolymers are propylene glycol monoricinoleate, propylene glycol mono-12-hydroxy-stearate, neopentyl glycol monoricinoleate, dehydrated castor oil, ethylene glycol monoricinoleate, ethylene glycol mono-12-hydroxystearate, triglyceride o~ ricinoleic acid, epoxidized castor oil, and pentaerythritol tetraricinoleate.
Polyester polyols made from lactones such as ~-caprolactone, ~ -may also be used in the preparation of the compositions of ~ ~:
the invention.
me polyether polyols useful in preparing the polyurethane compositions of the invention may be prepared by any of the well-known procedures, e.g., they may be prepared by polymerizing alkylene oxides such as ethylene oxide or propylene oxide or cyclic ethers such as dioxane or tetrahydrofuran or by condensing polyhydroxyl-containi~g ~ -. : ~ , , . : ., :

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compounds such as ethylene glycol or propylene glycol, etc.
Polyethers derived from epoxides such as epichlorohydrin can also be used but these compounds are less desirable because of their high rate of reactivity which causes them to set very rapidly into a highly crosslinked material.
The details of the preparation of the polyester polyols and polyether polyols is well known and forms no part o~ the present inventionO The preparation of poly-esters, polylactones, and polyethers is described in U.S.
Patents 2,871,218j 2,899,411; 3,169,945; and 3,L~93,634.
THE POLYHYDROXYL ~IENE POLYMERS
The polyhydroxyl diene polymers used in the pre-paration novel to compositions of the invention have at least 1.8 predominantly primary, allylic, terminal hydroxyl groups per polymer molecule. m e diene polymer has about 1.8 to 3~ and preferably 2.0 to 2.4 hydroxyl groups per molecule~ The hydroxyl-terminated diene polymers which produce compositions having the greatest utility are those having primary hydroxyl groups in terminal allylic positions on the main, generally longest, hydrocarbon chain of the molecule. By "allylic" configuration is meant the alpha-allylic grouping of allylic alcohol, that is, terminal hydroxyls o~ the intermediate diene polymer attached to a carbon ad~acent to a double bond carbon. By terminal hydroxyl is meant that the hydroxyl is attached to a terminal carbon atom, that is, the carbon atoms at the end of the polymer chain.
~ydroxylated diene polymers used in preparing the compositions of the invention may have a viscosity at 30C.

3 of about 5 to 20,000 poises~ preferably about 15 to 5,000 . :
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poises. When the hydroxylated diene polymer is a homopolymer, the viscosity is o~ten in the range of about 20 to 500 poises at 30C. Preferred hydroxylated homopolymers are those of butadiene ha~ing a viscosity of about 35 to 60 poises and preferred hydroxylated copolymers are those of butadiene and another vinyl monomer having a viscosity of about 150 to 300 poises at 30C. The intermediate polymers are . , .
essentially li~uids, including semi--solids flowable under moderate pressure at ambient temperatures or at temperatures in the range of -100~ to ~OO~F. The hydroxyl-containing -diene polymers used in the invention have a number average molecular weight in the range of about 400 to 25,000 as determined by cryoscopic, ebullioscopic or osmometric methods.
The preferred hydroxyl-containing diene homopolymers and copolymers ha~e a molecular weight range of about 900 to 10, ooo, ,; ,..... .
Dienes which are employed to make the hydroxylated 1,3-diene polymers are unsubsti-tuted, 2-substitu-ted or 3,3-disubstituted 1,3-dienes of up to about 12 carbon atoms. -m e diene preferably has up to about 6 carbon atoms and the -substituents in the 2- and/or 3- position may be hydrogen, alkyl, generally lower alkyl, e.g., of 1 to 4 carbon atoms, aryl (substituted or unsubstituted), halogen, nitro, nitrile, etc. Typical dienes which may be employed are 1,3-butadiene;
isoprene, chloroprenej 2-cyano-1,3-butadiene; 2,3-dimethyl-1,3-butadiene; etc. The choice of diene will usually depend upon the properties desired in the finished product, e.g., chloroprene may be used, alone or in admixture with other dienes to produce oil-resistant and flame-proof rubbers.

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The number and location of the hydroxyl groups and the molecular weight of the hydroxylated diene polymer are, for the most part, a function of polymerization tem-perature and the type of addition polymerization system employed in forming the polymer. It has been ~ound that diene polymers of the desired configuration may be obtained using hydrogen peroxide as the catalyst for polymerization.
The free-radical addition polymerization usually takes place at a temperature of about 100 to 200~C., preferably about 100 to 150C. The preparation of the hydroxylated diene -polymer is described in detail in U.S. Patents 3,427,366 and 3,674,743.
Although the preparation of the compositions of this invention may be carried out without a catalyst, i.e., by thermal initiation, it is preferred to carry out the polymerization in the presence of a catalyst in order to ~-accelerate curing. Conventional catalysts for the forma-tion of polyurethanes from isocyanates and polyols may be used including basic compounds such as tertiary amines, e.g., triethylamine, diazobicyclooctane, and triethylene diamine, and organometallic compounds such as dibutyltin dilaurate, stannous octoate, lead octoate, cobalt naphthenate, aluminum isopropoxide, etc. The catalyst is generally used at a concentration of about 0.05 to 5% and preferably about 0.1 to 2% based on the weight of total reactive components in the reaction mixture.
The reaction may be carried out in the presence or absence of a solvent. When a solvent is used, it is preferred to use a volatile organic liquid in which the : ' . , ~ -12- ~

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reactants are soluble such as cellosolve acetate, methylene chloride, dimethyl formamide. It is often not necessary that a solvent be used since the reactants are generally miscible liquids.
The reaction is generally carried out at a tem-perature of about 20C. to 350C. and preferably at a temperature of about 25C. to 120C~
Other additives including fillers such as carbon, silica, silicalumina, zinc oxide, clays, talc, etc~; extend-ing agents such as polyols or other low molecular weight polymeric materials, plasticizers such as adipate or phthalate ` esters or esters of trimethylol5 glycerine, etc.; anti-oxidants, coloring agents; etc. These materials may be ~
incorporated into the compositions of the invention by -addition to the reaction formulation or by inclusion into the composition during or subsequently to curing.
In a preferred embodiment the compositions are prepared by combining the polyes~er polyol or polyether polyol~ polyisocyanate, polyhydroxyl-containing diene poly-mer, and other additives which it is desired to include at this point in a suitable reaction vessel equipped with a thermometer, and an agitator. An effective amount of ; catalyst is added to the reaction mixture and the mixture is heated to and maintained at the reaction temperature until the desired degree of conversion takes place. This is usually indicated by a change in the viscosity of the reacting mixture. ~hen it is desired to produce molded products3 the reaction mixture may be poured into a suitable mold and heated until the desired degree of curing occurs.
It may be desired to use the reaction mixture as a coating .

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material. In this case it may be applied directly to the surface to be coated and cured by heating.
The products of the inventio~ have been found to possess, in addition to superior hydro~Lytic stability, improved tensile, modulus, tear, and hardness properties.
mis is contrary to the classical polymer theory that the ~ -addition o~ a rubbery polymeric component to a polymeric composition generally reduced the tensile and hardness properties of the composition. me improved product of the invention has utility in various types of construction application, e.g., in the manufacture of molded parts, waterproof membranes, seals~ gaskets, etc., and electrical applications such as potting compounds, encapsulants~ cable fillers, electrical connectors, etc.
The following examples illustrate specific embodi-ments of the invention. Unless otherwise specified, parts and percentages are on a weight basis. me follo~ing ASTM
procedures were followed:
Tensile streng~th, modulus, and elohgation -ASTM D-412 61T;
Tear - ASTM D~624-54, Die ;~,~and Hardness - ASTM D-2240-6~.
EXAMPLE I
Polymeric compositions are prepared by the following procedure: The polyhydroxyl components of the ~ ~`
formulations tabulated in Table I and the catalyst are added to a closed glass vessel and deaerated under vacuum at room temperature. rme isocyanate component is then added to the . .
vessel and the mixture is agitated vigorously for three -..: :
minutes under vacuum. The contents of the vessel are then ;

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poured into open molds shaped to produce regantular slabs.
The molds are placed in an oven and the samp`Les are cured at 100-110C. for three hours. The cured samples are cooled, removed from the molds, and aged overnight at 65-70C. The slabs are cut into test specimens for ASTM
testing. Physical tests are run on the samp:Les in accor- ;
dance with ASTM procedures and the test results are reported in Table I. In Runs 1-4, the amounts of the ingredients are adjusted as the amount of R45M is varied to maintain the NCO/OH ratio at 0.~9.

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EXAMPLE I I
A series of polymeric polyester-polyurethane samples is prepared and tested in accordance with the pro-cedure of Example I except that the formulations shown in Table II are used. The results of the physical tests conducted on samples made from these compositions are re-ported in Table II~ In Runs 1-4 the amoun-ts of the ingre-dients are adjusted as the R45M content is varied to maintain the NCO/OH ratio at 0.99.

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A series of polyester polyurethane samples is pr~pared and tested following the procedure of Example I
except that the formulations shown in Table III are used.
The results of the physical tests conducted on samples made from these compositions are reported in Table III.
In Runs 1-4 the amounts of ingredients are ad]usted as the R45M content varies to maintain the NCO/OH ratio at 1.00.

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EX~MPLE IV
A series of polymeric polyether polyurethane samples is prepared in accordance with the procedure of Example I except that the ~ormulations in Table IV are used.
The results of the physical tests conducted on physical test specimens made from these compositions are reported in Table IV. In Runs 1-4 the amounts of ingredients are adjusted as the R45M content varies to maintain the NCO/OH
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EXAMPLE V
A series of polymeric polyester polyurethane samples is prepared in accordance with the procedure of Example I except that the formulations shown in Table V
are used. The resutls of physical tests conducted on test : specimens prepared from these compositions are reported in Table V. In Runs 1-4 the amounts of the ingredients are varied as the R45M content varies to mai.ntain the NCO/OH
ratio at 1.01.

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EXAMPLE VI
A polyether polyurethane sample is prepared and tested in accordance with the procedure o~ Example I except that the formulation in Table VI is used. The results of the physical testing are reported in Table VI. m e NC0/OH
ratio is 1.01 :

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TABLE VI
Ingredient (gms) CS-15(a) 250 Pluracol GP3030 116.7 Pluracol GP2010 201.5 Dipropylene Glycol 160.6 Pluracol TP-340 9-94 Mondur T-80 261.3 Super-Ad-It 5.0 Properties -~ .
Tensile Strength (PSI) 2330 ~ 100% Modulus (PSI) 870 .~ Elongation (%) 420 Tear Pli 350 Hardness, Shore A,D 48D ;
. , (a) A~lantic Richfield Company trade-mark for ~: hydroxylated butadiene-styrene copolymer ~:
~ containing 25% styrene, hydroxyl content 0.65 ::
meq/gm. ; :

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Examples I-VI illustrate embodiments of the invention in which the polymeric samples are prepared by the "one shot" method, i.e., all of the ingredients are reacted at the same time. Examples I, IV~ and VI illustrate the improvement of polyetherpolyurethanes and Examples II, III, and V illustrate the improvement of polyester polyols by the substitution of hydroxylated diene polymer for some of the polyether or polyester polyols. In Example V the polyester polyol is polycaprilactone. Examples I-V show the improvement obtained by the use of hydroxylated poly-butadiene homopolymer and Example VI shows the use of hydroxylated butadiene-Styrene in the invention. The ; tabulated physical properties illustrate that une~pected improvement in one or more of the tensile strength, modulus, tear strength, and hardness properties is obtained by the incorporation of hydroxylated butadiene polymer into the sample formulations.
EXAMPLE VII
A polyester polyol was prepared by the prepolymer method according to the following procedure:
To a closed glass reaction vessel are added 259 gm. of R45HT (Atlantic Richfield Company trademark for hydroxylated pol~butadiene, mw 2,700, hydroxyl content *
0.80 meq/gm.) and 150 gm. of Mondur TD-80. The reaction ~-vessel is heated to and maintained at a temperature of 75-80C. for two hours with constant agitation. After one hour the contents are cooled.
In a separate reaction vessel are weighed 16.1 .. ..
*
sm. Pluracol TP-340, 392.7 gm. o~ Pluracol P-lO10 (Wyandotte Chemical Company trademark for poly(oxypropylene)diol, ' -,', .
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Trade Mark mw 1,000, OH number 107), and 101.2 gm. of dipropylene glycol. The contents are agitated at room temperature and 90.0 gm. of Mondur TD-80 is added. The contents of the reaction vessel are heated to and maintained at 80~.
for 90 minutes and then cooled. Then 0.1~ gm. of lead octoate (24% solution) is added to the reaction vessel.
The contents of the reaction vessels are combined and thoroughly mixed and poured into molds shaped to pro-duce rectangular slabs. The slabs are cooled and cut into ~ -test specimens according to the procedure of Example I.
Physical tests are conducted on the samples and the test results are reported in Table ~II.
Example VII illustrates that polyester polyurethane compositions of the invention can be prepared by the pre-polymer procedure.

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T~BI,E VII

Properties Tensile Strength (PSI) 1933 .
~ Modulus (PSI) 233 : Elongation (~) 540 : Tear pli 117 :~
Har~less, Shore A 83 ',''';

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- , 3~7~4 Althou~h the invention has been described with reference to specific examples, it is understood that the breadth of the invention is not limited thereto but is only determined by the scope of the appended claims.

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34.

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Claims (14)

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

1. A method of improving the physical properties of a urethane polymer of (a) a polyisocyanate and (b) a polyhydroxyl component selected from polyester polyols, polyether polyols, and mixtures of these, comprising reacting (a) with (b) in the presence of about 5 to 40%, based on the total weight of reactants, of a polyhydroxyl polymer of a 1,3-diene hydrocarbon of 4 to 12 carbon atoms having a number average molecular weight of about 400 to 25,000 and having about 1.8 to 3.0 predominantly primary, terminal, allylic hydroxyl groups per molecule, the rela-tive amounts of polyisocyanate and total polyhydroxyl compounds in the reaction mixture being such as to provide an isocyanate group to hydroxyl group ratio of 0.85 to 2.0:1.

2. The method of claim 1 wherein the polyhydroxyl polymer-is of butadiene and it is present in an amount of about 10 to 35% based on the total weight of reactants.

3. The method of claim 1 wherein the polyhydroxyl polymer is of butadiene and it has an average of about 2 to 2.4 hydroxyl groups per molecule.

4. me method of claim 3 wherein said polyiso-cyanate is a diisocyanate.

5. A method of improving the hydrolytic stability of a urethane polymer of a diisocyanate and a polyester 35.

polyol comprising reacting the diisocyanate and polyester polyol in the presence of about 5 to 40%, based on the total weight of reactants, of a polyhydroxyl polymer of a 1,3-diene hydrocarbon of 4 to 12 carbon atoms having a number average molecular weight of about 400 to 25,000 and about 1.8 to 3.0 predominantly primary, terminal, allylic hydroxyl groups per molecule.

6. The method of claim 5 wherein said diisocyanate is aromatic in structure.

7. The method of claim 5 wherein said polyester polyol has an hydroxyl number of about 40 to 150 and a molecular weight of about 600 to 3,000.

8. The method of claim 5 wherein said diene is butadiene.

9. A polyurethane composition having improved physical properties comprised of a urethane polymer of (a) An organic polyisocyanate containing about 2 to 6 isocyanate groups per molecule, (b) An organic polyhydroxyl compound selected from polyester polyols, polyether polyols, and mixtures of these, and (c) About 5 to 40% based on the total weight of reactants of a polyhydroxyl polymer of a 1,3-diene hydrocarbon of 4 to 12 carbon atoms having a number average molecular weight of about 400 to 25,000 and about 1.8 to 3.0 predominantly primary, terminal allylic hydroxyl groups per molecule, the relative amounts of polyisocyanate and total polyhydroxyl components being such as to provide an isocyanate group to hydroxyl group ratio of about 0.85 to 2.0:1.

10. The composition of claim 9 wherein said 1,3-diene hydrocarbon is butadiene.

11. me composition of claim 9 wherein said organic polyhydroxyl compound is a polyester polyol.

12. The composition of claim 9 wherein said organic diisocyanate is an aromatic compound containing 2 isocyanate groups per molecule.

13. The composition of claim 10 wherein (c) is present in an amount of about 10 to 35%, based on the total weight of reactants.

14. A polyester polyurethane having improved hydrolytic stability comprised of a urethane polymer of an aromatic diisocyanate, a polyester polyol having an hydroxyl number of about 40 to 150, and a molecular weight of about 600 to 3,000, and about 10 to 35%, based on the total weight of reactants of a butadiene polymer containing an average of about 2 to 2.4 hydroxyl groups per molecule and a number average molecular weight of about 400 to 3,000, the relative amounts of diisocyanate to total hydroxyl-containing com-pounds being such as to provide an isocyanate group to hydroxyl group ratio of about 0.95 to 1.3:1.

37.