CA1211585A - Impact resistant polymeric compositions containing polyamides, maleic anhydride adducts of hydrogenated polymers and graft copolymers thereof - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Polymeric compositions having resistance to impact comprising (a) from about 50 to about 90 percent by weight of a polyamide having a number average molecular weight of at least 10,000 and (b) from about 10 to about 50 percent by weight of a maleic anhydride adduct of a hydro-genated polymer of one or more conjugated dienes or a hydr-genated copolymer of a conjugated diene and a vinyl aromatic hydrocarbon, said hydrogenated polymer or copolymer having a residual unsaturation content of from about 0.5 to about 20%
of its original unsaturation content prior to hydrogenation;
wherein at least 5 percent by weight of components (a) and (b) are present in the form of a graft copolymer containing at least 20 percent of polyamide. The compositions exhibit especially advantageous properties, particularly high im-pact strength and are useful in a variety of molding appli-cations such as molded bushings, gears, cams, valves and a variety of other products.

Description

IMPACT RESISTANT POLYMERIC COMPOSITIONS CONTAINING
POLYAMIDES, MILWAUKEE ANDROID DAKOTAS OF HYDROGENATED
_ POLYMERS AND GRAFT POLYMERS THEREOF

background of the Invention The invention relates to impact resistant polyp metric compositions containing polyamides, Molly android audits of hydrogenated polymers and graft eopolymers thereof. More particularly, the invention relates to impact resistant polymeric compositions containing polyamides and lo Molly android adduces of hydrogenated polymers of eon-jugated dines and hydrogenated eopolymers of conjugated dines and vinyl aromatic hydrocarbons in wow at least 5 percent by weight of the polyamide and the malefic android adduce are present in the form of a graft copolymer containing at least 20 percent polyamide.
USE Patents 3,236,914 and 3,274,289 to Burdock et at disclose blends of polyamides and earboxylated eopoly-mews which are said to produce molded products having high impact resistance and good thermal rigidity. These patents leach that the earboxylated eopolymers contain from 1 to 25 percent of free earboxyl groups and that they may be derived from unsaturated neutral monomers such as ethylene, propylene, styrenes 1,3-butadiene, vinyl monomers, acrylates, and the like, and unsaturated carboxylic acids such as acrylic acid, motherly acid, Molly acid, itaeonie acid and the like. however, the patents do not disclose or suggest compositions containing Molly android audits of hydrogenated polymers or eopolymers and graft eopolymers A
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I.

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polyamides and malefic android adduces of hydrogenated polymers or copolymers. Moreover, blend compositions such as those described in the Burdock et at patents are difficult to blend on a mill and often result in the production of rough molding or extradites.
U. SO Patent 3,842,029 to Swept et at discloses synthetic resin compositions comprising glass fiber, polyamides and thermoplastic block copolymers of conjugated dolphins and monovinyl aromatic hydrocarbons However, the patent does not disclose or suggest compositions contain-in malefic ~nhydride adduces of hydrogenated polymers or copol~mers and graft copolymers of polyamides and malefic android adduces of hydrogenated polymers or copolymers~
U. S. Patent 4~041,103 to Davison et at discloses polymer blend of certain selectively hydrogenated bloc co-polymers and polyamides. However the patent does not disclose or suggest compositions containing malefic android adduces of hydrogenated polymers or copolymers and graft copolymers of polyamides and malefic android adduces of hydrogenated polymers or copolymers.
U. S. Patent 4,085,163 to Gorgon et at discloses multi component blends comprising polyamides, selectively hydrogenated block copolymers of conjugated dines and moo-alkenyl crones and at least one dissimilar engineering thermos plastic which may be selected from polyolefins, polyesters~poly(aryl ethers), polyurethane poly(aryl sulfones) etc.
However, the patent does not disclose or suggest compositions containing malefic android addicts of hydrogenated polymers or copolymers and graft copol~mers of polyamides and malefic I android adduces of hydrogenated polymers or copolymers.
Us S. Patent 49174,35~ to Epstein discloses multi-phase thermoplastic compositions consisting essentially of one phase containing 60 to 99 percent by weight ox a polyp aside having a number average molecular weigh-t of at least 5,000 and 1 to 40 percent by weight of at least one other phase containing particles of at least one polymer having a number average molecular weight of at let 5,000 and 1 to 40 percent by weight of at least one other phase con-tenon particles of at least one polymer having a particle size in the range of 0.01 to 3~0 microns and being adhered to the polyamide. An extremely road range of polymer or polymer mixtures which can be utilized as the at least one other phase polymer are described. However, the patent does not disclose or suet compositions containing malefic android adduces of hydrogenated polymers Of conjugated dines or hydrogenated copolymers of keynoted dines and vinyl aromatic hydrocarbons end graft copolvmers of polyp asides with malefic android adequate of shah hydrogenated polymers or copolymers as is the case in the cG~positions of the present inventio71, In accordance with this invention, impact resistant polymeric compositions are provided which comprise (a) from about 50 to about 90 percept by weight of a polyamide having a umber average molecular weight ox at least 10,000 and (b) from about 10 to about 50 percent by weight of a malefic android adduce of a hydrogenated polymer of a conjugated Dunn or a hydrogenated copolymer of a conjugated dine and a vinyl aromatic hydrocarbon, said hydrogenated polymer or copol~mer having a residual unsaturation content of from I about 0.5 to about 20 percent of its original unsaturation content prior to hydrogenation, wherein at least 5 percept by weight of components pa) and (b) are present in the form of a graft copolymer containing it least 20 percent of polyamide. the compositions exhibit especially ad van-tsgeous properties, particularly high impact strengths.

The compositions of the invention are character iced by their relatively simple process owe preparation which obviates the necessity for complex copolymerization and grafting procedures.
In accordance with another aspect the present invention provides a malefic android adduce of a hydrogenated polymer of one or more conjugated dines or hydrogenated copolymer of a conjugated dine and a vinyl aromatic hydrocarbon, said hydrogenated polymer or copolymer having a residual unsaturation content of from about 0.5 to about 20~ of its original unsaturation content prior to hydrogenation Detailed Description of the Invention As indicated, the polymeric compositions of this invention, which are thermoplastic in nature, contain polyamides, malefic android adduces of hydrogenated polymers or copolymers and a proportion of graft copolymer formed from these components.
A The Pal aside Component .
2Q my polyamide is meant a condensation product which contains recurring aromatic and/or aliphatic aside groups as integral parts of the main polymer chain, such products being known generically as nylons. These may be obtained by polymerizing a monoaminomonocarboxylic acid or an internal lactam thereof having at least two carbon atoms between the amino and carboxylic acid groups or by polymerizing substantially equimolar proportions of a Damon which contains at least two carbon atoms between the amino groups and a dicarboxylic acid; or by polymerizing a monoaminocarboxylic acid or an internal lactam thereof as defined above together with substantially equimolecular proportions of a Damon and a dicarboxylic acid. The dicarboxylic acid may be used in the form of a functional derivative thereof, for example, an ester.
I

The term substantially equimolecularproportions to the Damon and of the dicarboxylic acid) is used to cover both strict equimolecular proportions and the slight .

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departures therefrom which are involved in conventional techniques for stabilizing the viscosity of the resultant polyamides.
As examples of the said monoaminomonocarboxylic acids or lactams thereof there ma be mentioned those compounds containing from 2 to I carbon atoms between the amino and carboxylic acid groups, said carbon atoms forming a ring with the -CO NO group in the case of a l~ctam. As particular example of aminocarboxylic acids and lactams, there may be mentioned ~-aminocaproic acid butyrolactam, pi~alolactam, caprolactam, capryl-lac-tam, enantholactam, us-decanolactam, dodecanolactam old the like Examples of the said dominoes are Damon of the H2N(CH2)n~H2 wherein n is an integer of from

2 to 16 7 such as trimethylenediamine,-tetramethylenediamine, pentamethylenediamine, octamethylenediamine 9 decamethylene-Damon, dodecamethylenediamine t hexadecamethylenediamine, and the like.
Calculated dominoes e.g., 2,2~-dimethylpenta-methylenediamine and 2,2,4- and 2,4,4-trimeth~lhexamethylene-Damon are further examples. Other dominoes which may be mentioned as examples are aromatic dominoes, ego, p-phen~lenediamine, 4,4'-diaminodiphenyl sulphonel 4~4l_ diaminodiph~nyl ether and 4~4'-diaminodiphenyl cellophane, 4,4'-diaminodiphen~l ether and 4,4'-diaminodiphenylmethane;
and cycloaliphatic Damon, for employ t diaminodic~clo-he~ylmethane.
he dicarbo~ylic acids may be aromatic for example, isophthalic and terephthalic acids. Preferred dip carboxylic acids are of the formula HOOT Y COO wherein Y
represents a diva lent aliphatic radical containing at least 2 carbon atom, and examples of such acids are sebacic acid, octadecanediolcacid~ ~uberic acid, azelaic acid, undecane-Dick acid, glutaric acid, pimelic acid, adipic acid, and the like I Illustrative examples of polyamides which may be incorporated in the polymeric compositions of the invention I By include: pol~hexamethylene adipamide nylon Go polyp pyrrolidone (nylon lo polycaprolac~am nylon 6), polyp heptolactam (nylon I), polycapryllactam (nylon 8), polyp nonanolactam (nylon 9), polyundecanolactam (nylon 11), polyp dodecanolactam nylon 12), polyhexamethylene azelaamide nylon 6:9~, polyhex~methylene sebacamide (nylon 6:10), polyhexamethylene isophthalamide nylon zip polymetaxylyl-one adipamide (nylon MXD:6), polyamide of hex~methy~ene-Damon and n-dodecanedioic acid (nylon 6.,~2~, polyamide of dodecamethylenediamine and n-dodecanedioic acid (nylon 12:12).
Nylon copolymer~ may also be used for example, copolymers of the following hexamethylene adipamide/caprolactam (nylon 6:6~6~, hexamethylene adipamide/hexamethylene-iRophthalamide (nylon 6:6 it), hexamethylene adipamide~hexamethyleneterephthalamide (nylon 6 6/6~r), hexamethylene adipamide/hexamethylene-azelaamide (nylon 6:6/6:9), hexameth~lene adipamide/hexamethyleneazela~mide/caprolactam (nylon 6:6/6:9/6~.
Preferred nylons include 6,6:6, 11 and 12~
the polyamide which are employed in the compost itchiness of the invention must have number average molecular weight (My) of at least 10,000 and may have molecular weight My ox from 10,000 to OWE Preferred polyamides are those having number average molecular weights (on) of at least 15,000. In addition/ such polyamides should have amine equivalent contents of 0~1 milliequivalents per gram or less.
he amount of polyamide included in the compositions of the invention may vary widely depending upon the pro parties desired in the composition. In general, the amounts of polyamide included in the composition may range prom 5 about 50 to about 90 percent by weight bayed on total weight .

of composition Preferred amount of polyamide are prom 70 to 85 percent by weight with a particularly preferrer amount being Roy 80 to 85 percent by White, as these amounts appear to impart excellent impact resistance to the finished compassion the Malefic nh~dride Adduce Coy en he term Milwaukee android adduce" a employed herein refer to polymer products containing pendant sue-ionic android groups which are formed by reacting malefic android with hydrogenated polymers of conjugated Dunn or hydrogenated copol~mer~ of conjugated dines and vinyl aromatic hydrocarbon containing a residual unsaturation level of from I to 20.0 percent of their original unset- ¦
unction laurel prior two hydrogenation The reaction which 15 it conducted by heating a mixture of the malefic an drive and hydrogenated polymer or copolymer containing residual maturation proceeds by means of a reaction mechanist referred to as a "EYE" type reaction the reaction Skye e in simplified Norm utilizing; a hydrogenated polybutadierle 20 containing residual Imsaturation Ion illustrative purpose proceeds as else:

VVlJV CH2-CH~ CAKEWALK HO
I; H I -C~2 I I
I o O
OR

GH2~ r-CH2-C _

3 by 2 HUG oboe by In the above formula 9 the aye lines represent the no maunder of the hydrogenated polybutadîene polymer chain.
As indicated by the above reaction scheme the residual unsaturation of the hydrogenated polybutadiene undergoes a Lyon" type reaction with the malefic android to produce a polymer product containing pendant succinic android groups. As will be discussed hereinafter, this polymer by virtue of the presence of the pendant succi~c android group can be reacted under appropriate conditions with the mud or amine groups of the polyamide to produce a proportion of graft copolymer~
As indicated the malefic android adduce is pro-pared by reacting malefic android with a hydrogenated polyp men containing residual unsaturation. the amounts of malefic android employed it the reaction Jan vary considerably depending on the specific nature of the hydrogenated polymer and the properties desired in the polymer product In gent oral, the mount of malefic adored employed ma range from about 0.1 to about 25 percent by weight based on total weigh of malefic aDhydride and hydrogenated polymer with a preferred amount being from 0~2 to 5 percept weight Various polymers of co~ugated dyes and Capella-mews of conjugated dines and vinyl aromatic hydrocarbon may be hydrogenated for use in preparing the malefic android adduce component of the co~po8itions of the mention Polyp mews of conjugated dines which may be hydrogenated include polymers derived from one or more conjugated dine monomers.
use polymers derived from a jingle conjugated dine such as 1,3~butadiene (i.e., a homopolymer) or polygamy derived from two or more conjured Dunn such as for example 1,3 butadiene and isoprene or 1~-bu-tadiene and 1~3-pentadiene it a copol~mer)a~d the like may be utilized. Copolymers which may be hydrogenated include random copvlyme:rs of con-jugated dines and vinyl aromatic hydrocarbons and block co-polymers of conjugated dines and vinyl aromatic hydrocarbons which exhibit elastomeric properties . :

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Polymers of conjugated dines which may be utilized include those having prior to hydrogenation, 1,2- and 304 micro structure contents of from about 100% to about 0.1% and 1,4-microstructure contents of from about 99% to about 0.1%.
A preferred polymer of a conjugated dine is a medium vinyl polybutadiene which prior to hydrogenation has a 1~2-micro structure content of from about 40 to about 60 mole percent. Such polymers of conjugated dines can be prepared by any well known process. Thus, for example, polymers of conjugated dines having relatively low vinyl or 1,2-micro structure contents may be prepared in known manner by anionic ally polymerizing the dine monomer using a lithium-based catalyst and an inert hydrocarbon delineate. Medium vinyl polybutadienes may be prepared in known manner by anionic ally polymerizing the dine monomer in the presence of a catalyst system consisting of an alkyd lithium initiator such as n-butyl lithium and a modifier such as NOAH
tetramethyl-1,2-ethanediamine (TMEDA), 1,2-dipiridyl ethanes (DYE) or 1,2-di-(N-methyl-piperazinyl-N')-ethane (DUPE) and an inert hydrocarbon delineate. Typical procedures for pro-paring medium vinyl or high vinyl polybutadienes are described in U S. Patents 3,45]~988 and 4,226,952.
Random copolymers of conjugated dines and vinyl aromatic hydrocarbons which may be utilized include those having 1,2-microstructure contents prior to hydrogenation of from about 10% to about 100%. Tune copolymers may contain up to about 60 percent by weight of vinyl aromatic hydrocarbon.
Such copolymers are well known in the art. They may be pro-duped by any well known process. For example, the random copolymer can be prepared by charging a mixture of conjugated dine and vinyl aromatic hydrocarbon monomers to a polymer-ization reactor at a rate slower than the normal polymer-ization rate as described in US. Patent 3,094,512 or by copolymerizing a mixture of the monomers in the presence of a randomizing agent such as an ether, amine, chelating pi ' 10 -Damon or other polar compound as illustrated in US.
Patent 3,451,9880 Block copolymers of conjugated dines and vinyl aromatic hydrocarbons which may be utilized include any of those which exhibit elastomeric properties and which have 1,2 micro structure contents prior to hydrogenation of from about 7% to about 100%. Such block copolymers may be multi-block copolymers of varying structures containing various ratios of conjugated dines to vinyl aromatic hydrocarbons including those containing up to about 60 percent by weight of vinyl aromatic hydrocarbon. Thus, multi block copolymers may be utilized which have structures represented by the formulae A-B, A-B-A, A-B-A-B, B-A, BRA B, B-A-B-A and the like wherein A is a polymer bloc-k of a vinyl aromatic hydra-carbon or a conjugated diene/vinyl aromatic hydrocarbon tapered copolymer block and B is a polymer block of a con-jugated dine.
The block copolymers may be produced by any well known block polymerization or copolymerization procedures in-eluding the well known sequential addition of monomer tech-piques, incremental addition of monomer technique or coupling technique as illustrated in, for example, US. Patents 3,251,905; 3;390,207; 3,598,887 and 4,219,627. As is well known in the block copolymer art, tapered copolymer blocks can be incorporated in the multi block copolymer by Capella-meriting a mixture of conjugated dine and vinyl aromatic hydrocarbon monomers utilizing the difference in their co-polymerization reactivity rates. Various patents describe the preparation of multi block copolymers containing tapered copolymer blocks including US. Patents 3,251,905; 3,265,765;
3,639,521 and 4,208,356.
Conjugated dines which may be utilized to pro-pare the polymers and copolymers are those having from 4 to 8 carbon atoms and include 1,3~butadiene, 2-methyl-1,3-Jo butadiene (isopropene], 2,3-dimethyl-1,3 quotidian , 1,3 pentadiene, 1,3-hexadiene, and the like. Mixtures of such conjugated dines may also be used. The preferred conjugated dine is 1,3 butadiene.
Vinyl aromatic hydrocarbons which may be utilized to pxepar4 copolymers include styrenes o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, alpha-methylstyrene, vinylnaphtalene, vinylanthracene and the like. The preferred vinyl aromatic hydrocarbon is styrenes It should be observed that the above-described polymers and copolymers may, if desired, be readily prepared by the methods set forth above. However, since many of these polymers and copolymers are commercially available, it is usually preferred to employ the commercially available polymer as this serves to reduce the number of processing steps involved in the overall process. The hydrogenation of these polymers and copolymers may be carried out by a variety of well established processes including hydrogen-Shea in the presence of such catalyst as Rangy Nickel, noble metals such as platinum, palladium and the like and soluble transition metal catalysts. Suitable hydrogenation processes which can be used are ones wherein the diene-containing polymer or copolymer is dissolved in an inert hydrocarbon delineate such as cyclohexane and hydrogenated by reaction with hydrogen in the presence of a soluble hydrogenation catalyst.
Such processes are disclosed in US. Patents 3~113,986 and

4,226,952. The polymers and copolymers are hydrogenated in such a manner as to produce hydrogenated polymers and copolymers having a residual unsaturation content of from about 0.5 to about 20 percent of their original unsaturation content prior to hydrogenation.
As indicated heretofore, the malefic android ad-duct component of the compositions of the invention is prey pared by a relatively uncomplicated process which does not require complex copolymerization or grafting procedures.
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- ha -Thus, the malefic android adduce can be prepared by f first .

forming a homogeneous mixture or solution of the malefic an-hydra and the hydrogenated polymer or copol~mer containing residual unsaturation and then reacting the resultant mixture or solution under appropriate condition of time and tempt eratureO In forming the homogeneous mixture the maleicanhydride preferably in particle form and the hydrogenated polymer or copolymer in solid form can be mixed in any con lenient mixing apparatus such as, for example a two-roll mill or a mixing extrude In the solution muted 9 -the malefic android and the hydrogenated polymer or copolymer cay be separately disallowed in aliphatic or aromatic solvents such as Tulane, Hutton, zillion, chlorobenzene or the like and the solutions then combined or both components may be dissolved together in on appropriate sol~entr Zen the I solution method it employed, the lent can be removed following the reaction by any convenient drying method such a, for example, drum drying.
The specific conditions employed in reacting the resultant mixture or solution of malefic android and hydra-jointed polymer or copolymer can vary considerably depending on factors such as the specific Monet of ingredients and the nature of the hydrogenated polymer or copolymer and its reactivity. thus, temperatures may range from 130 to 320 C
with a preferred range being from 170 Jo 300C~ Time may range from 0.00~ hour to 200 hours, depending on the specific temperature utilized, nature ox the hydrogenated polymer or copol~mer9 etc. In addition, it it preferred to conduct the reaction under an irlert gas such as nitrogen.
the mounts of malefic android Dakota component I included in the compositions of the invention may vary some-what depending upon the properties desired in the finished composition. In general, the amounts of Alec android adduce included in the composition may range from about 10 to about 50 percent by weight bayed on total weight of composition Preferred amounts of malefic android adduce are from 15 to 30 percent by weight with a particularly preferred mount being from 15 to 20 percent by weight.

C Pro aeration of Finished Coy position he finished composition of the in~enticn which includes a proportion of graft copol~mer can be prepared by an uncomplicated process which involves mixing the polyp aside and malefic android adduce and then homogenizing the resultant mixture in a suitable homogenizing apparatlls under appropriate conditions of time and temperature. the process result in the production of a finished composition con-twining a graft copolymer component without the necessity of using complex grating techniques In forming the mixture of polyamide and malefic android adduce, the polyamide and malefic android adduce components, preferably in the Norm of small particles, are mixed together using any convenient mixing apparatus the resultant mixture is then homogenized in a suitable home jouncing apparatus, preferably a mixing extrude containing twin screws the extrude temperature and residence time can vary somewhat depending on the specific composition so the mixture and the degree of grating desired Thus, tempt erasures may range from 180 to 320C and residence times may range from less than 1 minute to 150 minutes.
As indicated the homogenizing process results in the production of a proportion of grant copol~mer formed from the polyamide and Molly android adduce components. the reason for this fact is that under appropriate temperature and time conditions, the pendant succinic android groups of the malefic android adduce will react with either the aside groups or terminal amino groups of the polyamide to form Ann . amount of graft copolymer containing aside or ibid Lange. the specific amount of graft copolymer which is formed is dependent on a number of factors including the specific proportions of polyamide and malefic android modified polymer, -the mixing or homogenizing temperature, the residence time and the nature of the malefic android adduce (i.e., proportion of pendant succinic shuddered groups).

he reaction scheme (in simplified form) my which the graft copolymer is formed from the malefic adored adduce and polyamide (ego polyca~rolack~) component is believed to proceed along either of the following path:

I I o I O
/ t it H(CH2)sC SHEA

SCHICK OH

I
2. -C O
2(CH2)sa-7~N~H(cH2) Go (SCHICK -7f~H(CH2)5C ' H2 I
In the above formulas, the my lives represent the remainder of the Lyon polymer chain.
As mentioned above and as indicated it the fore-going reaction scheme, the pendant succinic android groups of the malefic android adduce can react with either the mud groups pathway (1) of the reaction scheme) an the amino groups (pathway (2) of the reaction scheme) of the polyamide Under ordinary circumstances the reaction very likely proceeds along the path designated (2) due to the I

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treater reactivity of the amino group. Louvre, in the absence of tunnel amine groups and if sufficient time is provided, the reaction can also proceed along the pathway designated (1) in the reaction scheme (isle with the aside groups It should be observed at this time that residence times appear to be a major factor in both the amount of graft copolymer formed and the properties obtained if. the finished composition thus, under constant temperatures in-creased residence times often produce improved propertiesinc~uding higher impact resistance.
In preparing the compositions ox the present I've lion, it is preferred to produce a finished composition con-twining at least 5 percept by weight of the polyamide and malefic ~nhydride adduce components in the form of a graft copolymer containing at least 20 percent of polyamide. The upper limit in the amount of graft copolymer included in the compositio~ it governed by the properties desired ion the finished composition, particularly the level ox impact no-sweetness. It general, the compositions may contain from about 5 percent to about 75 percept by weight of the graft oopolymer component with a preferred range being from 5 to 40 percent by weight;
Following the homogenization procedure, the result ant product is then cooled rapidly as by water quenching, chopped into particles (preferably pellets) and then dried.
the resulting particles or pellets can then be injection molded to form valuable molded product the following tests were used in the examples to I provide physical property measurements of the compositions of the invention.
The Rockwell M value is a hardness test determined by the standard ASTM D-785 test. the Idea impact strength test was determined by standard ASTM D-256-73. Samples are 35 injection molded at ~190-220C in the form of bars 5 inches ¦ X 0.5 inch X 0.125 inch or 0.250 inch into which notches are machined and cut into length as specified in ASTM D-256-73.
Samples are allowed to condition at room temperature for 16 to 24 hour after cutting and notching before testing jive bars of each sample are tested and the average value

5 reported as the Issued impact strength in ft~lbs./inch of notch.
Flexural modulus is measured it pi by standard ASSUME D-790-71 samples are melded at 190 to 220C in a laboratory press or injection molded in the form of 3 inch X 100 inch X 0.125 bars.
the bars are conditioned at room temperature for 16 to 24 hours before testing. The test is conducted using a 2 inch span at a crosshead speed of 0~50 inch/minH eye flexural modulus and strength are calculated using the equations given in the ASSUME
procedure. The heat distortion temperature (ED determined by the standard test ASTM D-548 using 264 psi and 66 psi loads.
The finished compositions were analyzed for amount of graft copolymer~ amount of nylon in the graft copolymer and amount of free rubber Leo hydrogenated polymer or polymer adduce) using a coacervation procedure. In this procedure, 1.50 grams of composition were first dissolved in I ml. of m-crossly when, the resultant solution was diluted with 120 ml.
of cycloh~xaneO the resultant suspension was then centrifuged to produce large clear c~clohexa~e rich top layer and a small crossly rich lower layer. The top layer was removed by siphon-in or recantation and then coagulated in ~00 ml of methanol filtered, washed in methanol, dried and weighed the tree rubber was obtained from this fraction by extracting the mat trial with refluxing Tulane for 48 hour. Then 150 ml of an 81/~9 cyclohexane/m-cre~ol mixture way added to the solution in the cresol-rich lower Lowry The centrifugation and siphon-I in procedure was repeated and a second fraction way obtained Subsequent fractions were obtained with 150 ml of 80/~0 79 . 5/20 . 5 79~21, 78/22; 77/2~ , 76/24 , 75/25 and 65~35 cyclohexane/m-crossly mixtures. All fractions were collated by adding them slowly to methanol and were collected on tared funnels.
After washing with methanol the samples were dried and weight of material was obtained . a For a more detailed description of this type procedure, reference may be made to the article entitled:
"Block Polymers prom ~socyanate-Terminated Intimidates IT Preparation of Butadiene~ caprols.ctam and Steinway Caprolactam Block Polymers" by William Lo Hergenrother and Richard J. Ambrose appearing in the Journal of Polymer Science, Polymer Chemistry Edition Volume 12~ pages 2613 2622 (1974~ particularly page 2615 under the headirlg fractionation Procedures the following examples are submitted for the pun-pose ox further illustrating the nature of the present in-mention and are not intended as a limitation on the scope thereof. Parts and percentages referred to in the examples are by weight unless otherwise indicated A hydrogenated pol~butadiene polymer having a weight average molecular weight My of 170,000 was prepared by hydra-jointing a polybutadiene originally containing 99 percent 1,2-micro structure content to a 90 percept saturation level it 8-10 percent residual unsaturation content). The hydrogenated polymer was dissolved ill Tulane to produce a I percent solids solution of the polgmerO Jo this solution was added a solution of malefic android in Tulane containing 5 percent weight of malefic android based on the weight of hydrogenated polymer. the combined solution was heated at 200C for 24 hours, then cooled and drum dried. the no-sultan malefic android abduct was chopped into particles and combined with pellets Go polycaprolactam (Nylon 6) to produce a mixture containing 15 percent by weight of malefic I ~nhydride adduce. the resultant mixture was then homogenized in a twin screw extrude at 200-230~C using a residence time of 8 minutes. Following the homogenization, the extradite from this mixture was water quenched and chopped into pellets which were dried at 100C under vacuum (< 0.1 mm Hug Samples of the poulticed composition were then injection molded at 250~C. The molded samples were then analyzed for graft co-polymer content, amount of nylon in the graft copolymer end amount of free rubber by the coacervatio~ procedure desk cried above and subjected to various physical propriety tests Results are shown in table I.
In this evaluation, a control was included for comparative purposes. eye control was polycæprolactam (Nylon 6) alone and was prepared by drying pellets of yule 6 and then injection molding them a 250C~. Molded samples of the control were then evaluated for the same physical pro parties as in example 1.
TIE I
exam to Control Nylon 6 (wt. %) 100 85 15 Mohawk adduce of H2-PBd (White - 15 MCKEE. charged for addiction (White) 5 Analysis of Finished Composition Graft copolymer (wt. %) , - 37,2 Nylon in Graft copolymer (wt. %) - 68 . 7 20 Free rubber (we. Jo - 1.3 Properties - Molded Samples Rockwell M 53 I
Notched Issued (1/8" thick bar) 1.1 1~5 ft.-lb./in.
Notched Issued (1/4" thick bar) 0.2~ 4,5 ft.-lb./in.
laurel Modulus, psi X 10-~ 3.56 2.46 strength, psi X 10 1.58 0.99 Jo ~64 psi load 62 58 66 psi load 151 102 mounts charged to extrude from % nitrogen ye s 2 - 4 These examples illustrate compositions of the ion-mention contai~Lng malefic android adduces of various hydra-jointed polybutadiene polymers (defined -in table II). The 5 example composition were prepared in accordance with the following general procedure:
A solution of the hydrogenated poller was pro-pared by dissolving 200 grams ox the poller in 1272 grams of distilled Tulane in a reactor equipped with heating means 9 thermometer, stirrer and nitrogen inlet by healing to 93C
under nitrogen Lath stirring. Jo the reactor containing this solution was added a solution consisting of 10 grams of malefic android (MA.) in 60 milliliters (mls) of Tulane (i.e., 5 percent by weight MA. based ox polymer White the come brined solutions were then heated to 17oo-l9ooG with stirring until addiction of Mao it 9 reactions of MA. with pendant unsaturated groups of polymer) reached a desired level as determined by infrared analysis (IRE.). The reactor way when cooled and the contents removed and dried by drum drying or extrude drying the resultant MA. adduce was chopped into particles, dried in a vacuum oven at 80C ornate and come wined with pellets of Lyon 6 which had also been dried in a vacuum oxen at 80~C overnight. the resultant mixture was then homogenized by passing it through a twin screw extrude at 75 RPM using heating profile of 232-2~-288~C. hollowing homogenization, the extradites from these mixtures were water quenched and chopped into pullets which were dried at 100C
under vacuum ~0.1 mm Hug The sample were then injection molded at 220 C.
Example 3 was analyzed for graft copolymer content 9 amount of nylon in the graft copnlymer and amount of free rubber using the procedure of Example I the molded samples were tested for various physical properties.
For comparative purposes, a control example con-icing of nylon 6 alone was prepared by drying pellets of nylon 6 and then injection molding them under the same condo-I

_ 20 =

Chinese Compositional formulations, the analysis of Example and physical property results are shown it Table IT
TABLE II
Exam to Control 2 3 4 I__ _ __ ___ _ Nylon 6 (White %) 100 80 80 80 Moat adduce ox polymer - 20 20 20 (we. Jo Amt. MOE addicted - 0.670~40 OWE
(wt. %) Type H2~Polymer H2-P~d H2-PBd H~-PBd (by (c) (do nays s of Finished Composition Graft copolymer (wt. %) - - 35-6 15 Nylon in graft ~opol~mer (wt. 57~6 Free rubber (wt. %) %) - - 2 9 Pro reties (molded samples oily OWE 2.20 notched Issued (1/8" thick bar) 0,80 17~4718.96 17~93 ft.lb./in.
notched Issued (1/4" thick bar) 0.68 15.0018.36 15.36 ft~lb.~in.

pa) Amount of malefic android (Mao ) incorporated in adequate (b) A 95% hydrogenated polybutadiene polymer having a residual unsaturation level of 5% prepared by hydrogenating to a 95% level a polybutadiene originally containing 44%
1~2 content end 56% 194-c~ntent.
I An I hydrogenated polybutadiene polymer hazing a no-swaddle unsaturation level of I prepared by hydra-I jointing to an 88% level a polybutadiene originally containing 44% 1,2-content and 56% 1,4 content.
(d) An 88% hydrogenated polybutadiene polymer having a no-swaddle unsaturation level of 12% prepared by hydra-jointing to an 88% level a polybutadiene originally containing 11% 1,2-content and 89% cantata.
(vote: the terms H2-polymer and -Pod above mean hydrogenated polymer and hydrogenated p~lybutadiene respec~ively)0 These examples illustrate co~po~i.tions Or the in-mention containing malefic android adduces of a huller jointed polyiAoprene (En. I a hydrogerlated triblock co-5 polymer of ~tyrene/butadiene/styrene (Err 6) and hydra-jointed high cis~polybutadiene Rex. I
The MOE. adduces of examples 5 old 6 were prepared by reacting 5% by weight of malefic android based on pclym~r weight with the hydrogenated polymers using substantially the same procedure set forth in examples I the Mao adduce of Example 7 was prepared by heating the hydrogenated high cis-polybutadiene swollen with o-dichlorobenzene in a sealed tube in the presence of 5% by weight of Mao at 200C
overnight. the mixture was treated with acetone and the o-dichloroben~ene was removed by distillation The MA. adduce was then chopped into particles and dried as set forth in Examples 2-4.
The MA. adduce of Examples 5-7 were blended with pellets ox nylon 6 and homogenized in a Bra bender Plastic order at 260 - 275C, The extradites were then chopped into particles, pressed into plaques and compression molded.
Samples of the molded examples were tested for various physical properties in accordance with the procedure set forth in Example 2-4. the finished composition of Example G
was analyzed or graft copol~mer content amount of Pylon in the graft end amount of free rubber as it example 1.
Composition formulation , analysis of Employ 6 and physical property results art shown in Table III.

ABEL III
_._ Example __~ ___ 6 _ 7 Nylon 6 (White %) 80 80 80 Mao adduce of polymer 20 20 20 (Waco %) Amity Moat adduced (White %) 001 0.97 1,0 type polymer H2-PI(a) H2-SBS(b) H2-cis Pod Graft copolymer (White %) 17.0 10 pylon in graft copol~mer - 53~ -tree rubber (woo %) ( 1~2 Pro reties (molded samples) Flexu~al modulus g 10-5 2.39 1.61 psi Notched Issued (1/8" thick bar) 2.06 1.82 1~59 ft~lb.~in.
Notched Issued (1/4" thick bar) 1.87 1.48 ft.lbO~in.
OWE_ ___________~_______ ___ _________ ______ ___ .__________ (a) A I% hydrogenated polyisoprene polymer having a residual unsaturation level of 2%.
by A owe hydrogenated triblock copolymer of st~rene/butadiene~
Sterno hazing a residual unsaturation level of 8%
prepared by hydrogenating to a owe level a block co-polymer of styrene/butadiene/styrene having a ratio of I butadiene:styrene of 70:30 . this copolymer was commercial bloc copolymer available from Shell Chum-teal Co. under the designation Keaton 1101.
I A 9~/0 hydrogenated polybutadiene polymer having a residual unsaturation level of I

, a - 10 hose examples further illustrate composition of the invention containing MOE adduces of hydrogenated polyp butadiene polymers in which varying amulet I malefic an-hydrides were incorporated into the adduce.

The compositions were prepared and molded sub-staunchly in accordance with the procedure set forth in Example 2~4~ samples of the molded compositions were tested for physical properties as in Expel 2 4. Compost it ion formulations and test result are one in table IVY.

TABLE IV
Example 8 9 10 pylon 6 (wt. %) Jo 80 80 MA. adduce of -polymer 20 20 20 (wt. Jo 2 Amt. MOE adduced (White %) 0~96 east 0~36 Type H2~Polymer I Pod H2-P~d Ho Pod pa) (by (c) P operetta Notched Idea RUT. (ft.lbs~/in.) 1~8" thick bar 19.4 16.4 15.4 1/4'l thick bar 18~4 1105 13.0 Notched Xzod~ 30C (ft.lbs~/in.
1/8" thick bar 5.72 I 1/4" think bar 3.51 1.81 (a) A 92% hydrogenated polybutadiene polymer having a no swaddle unsaturation level of 8% prepared by hydra-jointing to a owe level a polybutadiene originally containing 44% continuity.
(b) A 9~/0 hydrogenated polybutadiene having a residual unsatur~tion level ox o prepared by hydrogenating to a owe level a polybutadiene containing 11% 1,2-co~tentG
(C) tame hydrcge~ated polymer a it (a).

These examples illustrate compositions of the invention in which the malefic android adduce was prepared in a twin-screw extrude and then homogenized with nylon 6 in a twin-screw extrude. the compositions were prepared in accord-arc with the following general procedure:

went (20) lo samples of the hydrogenated polymer in the form of particles we're fed to a twin-screw extrude operating at a barrel temperatllre of 280C and a screw speed of 150 PI and having a throughput of 30 lbsO/hr.
5 ennui, 0,4 lobs. of molteIl MA. were added to the barrel through a metering pump at the rate of 6~0 trams per minute.
the amounts of malefic android incorporated into the polyp men were determined by IT optical ratios The Ire ought c.
ratio of the MA. adduce of Example 11 was 3.31 indicating 10 an approximate bound android content of 0.77 weight per-cent while that of the Moan adduce of Example 12 was 2.62 indicating an approximate bound aD~lydride content of OWE
he MOE adequate in particle form were then blended with pellet of nylon 6 in a tin screw extrude having a barrel temperature of 300C, a screw speed of 80 RPM and a throughput of 45 lbs.~hrO Samples of the extradites from these examples were then chopped into particles and in-section molded.
Samples of the molded compositions were analyzed for compositional components and ~u~aected to various physical property tests. Composition formulations analysis OX
finished compositions and physical property results are shown in Table V.

TUB V
example 11 12 ._ ____ Nylon 6 (woo %) 80 80 Mao adduce of H2-Pol~mer (White Jo 20 20 5 type polymer H2-PBd(~) H~-PBd(b) ~~--~_ Graft copolymer (wt. Jo 35.7 3~.7 pylon in graft c~pol~mer (wt. %) 61~6 owe Free rubber (White %) 6~2 101 . r I-ensoul at yield 10 , Sue 7.6 tensile at break 10 3, Sue I
elongation at break, /0 110 130 ~lexural strength X 10 3, Sue 1007 Flexura`l modulus X 10-5~ Sue 2.73 Issued Impact, ftolb yin notched 1/8" thick bar Wright 17.9 notched 1~4" thick bar ROY 13~2 Notched 1/4" thick bar, 0C16~9 6~2 notched 1/4" thick bar, -10C16.2 4.0 Notched 1/41' thick bar, -20C17.1 306 Notched ~/411 thick bar, -30C6.6 2~2 itched 1~4" thick bar -40C 3~8 2.1 (a A 92.% hydrogenated polybutadiene polymer having a no-swaddle unsaturation level of 8% prepared by hydra-jointing to a 92% level a polybutadiene originally collating JJ.0% catenate Leo medium renewal pod by A 90% hydrogenated polybutadiene polymer having a no-swaddle saturation level of owe prepared by hydra-jointing to a 9~/0 reel a polybutadiene originally containing 11% continuity.
amounts as originally charged As the above data indicates, the low temperature impact resistance of these compositions is excellent, -- I

In this example, a composition was prepared. from a formulation originally containing 50 parts by weight of nylon 6 and 50 parts by weight of the malefic android adduce of an 88% h~drogeIlated polybutadiene originally containing 44/0 1,2-content, said adduce having an average Molly android content of 0.61 weight percept. The composition was prepared and molded substantially in accordance with the procedure set forth in Examples 2-4.
A sample of the molded composition was elated for Issued impact strength at room temperature as in examples 2-4. The sample flexed but did not break during the test indicating a err high impact resistance.

Claims (21)

CLAIMS:

1. Impact resistant polymeric compositions comprising:
(a) from about 50 to about 90 percent by weight of a polyamide having a number average molecular weight of at least 10,000; and (b) from about 10 to about 50 percent by weight of a maleic anhydride adduct of a hydrogenated polymer of a con-jugated diene or hydrogenated copolymer of a conjugated diene and a vinyl aromatic hydrocarbon, said hydrogenated polymer or copolymer having a residual unsaturation content of from about 0.5 to about 20% of its original unsaturation content prior to hydrogenation, wherein at least 5 percent by weight of components (a) and (b) are present in the form of a graft copolymer containing at least 20 percent of polyamide.

2. The composition of claim 1 wherein said poly-amide is selected from the group consisting of polycapro-lactam, polyhexamethylene adipamide, polyundecanolactam and polydodecanolactam.

3. The composition of claim 1 wherein said poly-amide is polycaprolactam.

4. The composition of claim 1 wherein said maleic anhydride adduct contains from 0.1 to 25 percent by weight of maleic anhydride.

5. The composition of claim 4 wherein said maleic anhydride adduct contains from 0.2 to 5 percent by weight of maleic anhydride.

6. The composition of claim 1 wherein said maleic anhydride adduct is a maleic anhydride adduct of a hydro-genated polybutadiene.

7. The composition of claim 1 wherein said maleic anhydride adduct is a maleic anhydride adduct of a hydrogenated random copolymer of butadiene and styrene.

8. The composition of claim 7 wherein said random copolymer contains up to 60 percent by weight of styrene.

9. The composition of claim 1 wherein said maleic anhydride adduct is a maleic anhydride adduct of a hydro-genated block copolymer of butadiene and styrene.

10. The composition of claim 1 wherein said maleic anhydride adduct is a maleic anhydride adduct of a hydrogenated multiblock copolymer of butadiene and styrene.

11. The composition of claim 10 wherein said multiblock copolymer is a styrene/butadiene/styrene block copolymer.

12. The composition of claim 1 wherein component (a) is present in an amount of from 80 to 85 percent by weight and component (b) is present in an amount of from 15 to 20 percent by weight.

13. A maleic anhydride adduct of a hydrogenated polymer of one or more conjugated dienes or hydrogenated co-polymer of a conjugated diene and a vinyl aromatic hydro-carbon, said hydrogenated polymer or copolymer having a residual unsaturation content of from about 0.5 to about 20% of its original unsaturation content prior to hydro-genation.

14. The adduct of claim 13 containing from 0.1 to 25 percent by weight of maleic anhydride.

15. The adduct of claim 13 containing from 0.2 to 5 percent by weight of maleic anhydride.

16. The adduct of claim 13 wherein said hydro-genated polymer is a hydrogenated polybutadiene.

17. The adduct of claim 13 wherein said hydro-genated copolymer is a hydrogenated random copolymer of butadiene and styrene.

18. The adduct of claim 17 wherein said random copolymer contains up to 60 percent by weight of styrene.

19. The adduct of claim 13 wherein said hydro-genated copolymer is a hydrogenated block copolymer of butadiene and styrene.

20. The adduct of claim 13 wherein said hydro-genated copolymer is a hydrogenated multiblock copolymer of butadiene and styrene.

21. The adduct of claim 20 wherein said multi-block copolymer is a styrene/butadiene/styrene block co-polymer.