BLENDS OF POLY(ETHERIMIDES) AND POLYAMIDES

Abstract: Described herein are compositions suitable for molding comprising a blend of poly(etherimide) polymer and a crystalline polyamide polymer. Also described herein is a poly(etherimide)-polylactam block copolymer.

Description: BLENDS OF POLY(ETHERIMIDES) XD POLYAMIDES This invention is directed to a composition suitable for molding comprising a blend of a poly(etherimide) polymer and a crystalline polyamide polymer. Also, this invention is directed to poly(etherimide)-polylactam block copolymer. Poly(etherimide) polymers are higt. performance engineering polymers. These polymers have a hign continuous-use temperature, flame retardance, low smoke evolution, creep resistance, and good electrical properties. Tnese resins can be in2ection molded1 extruded into profiles, sheets or films and blow molded. However, -poly(etherimide) polymers are susceptible to premature failure in -certain environments such as in chlorinated hydrocarbons. -Poly(etnerimide) polymers are molded at temperatures of from about 750 to about 820 F. These high molding temperatures tend to have a - detrimental effect upon the properties of the polymer. Thus, there is a desire to improve the chemical resistance of poly(etherimide) polymers to make them more useful in environments where tney are susceptible to premature failure without essentially effecting their mechanical properties. Also, there is a desire to lower the molding temperature of the poly(etherimide) polymers by use of an additive which does not adversely affect their mechanical properties, It has now been fount that by adding a crystalline polyamide polymer to a poly(etherimide) polymer, the resulting blend, when molded, has improved chemical resistance in environments such as in chlorinated hydrocarbons. The mechanical properties of the poly(etherimide) polymer are not adversely affected by addition of the crystalline polyamide polymer. Also, the addition of a crystalline polyamide polymer to the poly(etherimide) polymer significantly lowers the molding temperature of the poly(etherimide) without essentially affecting its mechanical properties. - The composition of this invention comprises a blend of a poly(etherimide) polymer and a crystalline polyamide polymer. Also, this invention is directed-to novel block copolymers derived from a lactam monomer and a poly(etherimide) polymer. In another embodiment or tnis invention, a reinforcing fiber and/or mineral filler'may be added to the blend or block copolymer. The poly(etherimide) polymers suitable for use in this invention are known in the art.and are described in for example, U.S. Patents 3,847,867, 3,838,09i and 4,107,147. The polytetherimide) polymers are of the EMI2.1 <tb> following <SEP> formula: <tb> <SEP> o <SEP> . <SEP> 0 <tb> <SEP> -Il <SEP> II <SEP> <tb> (I) <SEP> N <tb> <SEP> c/I/ <tb> <SEP> 0 <SEP> O-R1-OO <SEP> a <tb> wherein a is an integer greater than 1, preferably from about 10 to about 10,000 or more, -O-R1-O- is attached to the 3 or 4 and 3 ' or 4' positions and R1 is selected from (a) a substituted or unsubstituted aromatic radical'of the formula: EMI3.1 (b) a divalent radical of, the formula: : EMI3.2 wherein R3 is independently C1 to C6 alkyl, or halogen and R4 is selected from -O-, -S-, EMI3.3 -SO-, -SO2alkylene of 1 to 6 carbon atoms, cycloalkylene of 4 to 8 carbon atoms, alkylidene of l to 6 carbon atoms or cycloal-kylidene of. 4 to 8 carbon atoms, R2 is selected from an aromatic hydrocarbon radical having from 6-20 carbon atoms and halogenated derivatives thereof, or alkyl substituted derivatives thereof, wherein the alkyl. group contains 1 to 6 carbon atom, alkylene and cycloalkylene radicals having from 2 to 20, carbon atoms, C2-C8 alkylene terminated' polydiorganosiloxane and a divalent radical of the formula EMI4.1 wherein R3 are as previously defined, and R5 may be a direct bond. EMI4.2 wherein -0-Z is a member selected from EMI4.3 wherein R6 is independently hydrogen, lower alkyl or lower alkoxy EMI4.4 wherein the oxygen may be attached to either ring and located ortho or para to one of the bonds of the imide carbonyl groups, R1 and R2 and a are as previously defined. These polyetherimides are prepared by methods well known in the art as set forth in, for example, U.S. Patents 3,833,544, 3,887,588, 4,017,511, 3,965,125 and 4,024,110. The polyetherimides of Formula (I) can, for example, be obtained by any of the methods well-known to tbose skilled in the art including the reaction of any aromatic bis(ether anhydride)s of the formula EMI5.1 where R1 is as defined hereinbefore, with a diamino compound of the formula (IV) H2N-R2-NH2 where R2 is as defined hereinbefore. In general, the reactions can be advantageously carried out employing well-known solvents, e.g., o-dichloro- benzene, m-cresol/toluene, N,N-dimethylacetamide, etc., in which to effect interaction between the dianhydrides and diamines, at temperatures of from about 20 to about 2500C. Alternatively, the polyetherimides can be prepared by melt, polymerization of any dianhydride of Formula tII . with any diamino-compound of Formula IV while heating the mixture of the ingredients at elevated temperatures with concurrent intermixing. Generally, melt polymerization temperatures between about 200 to 4000C and preferably 2300,to 300-C can be employed. Any order of addition of chain stoppers ordinarily employed in-melt polymerization can be employed. The conditions of the reaction qnd the proportions of ingredients can be varied widely depending on the desired molecular weight, intrinsic viscosity, and solvent resistance. In general, eguimolar amounts of diamine and dianhydride are employed for hiqh molecular weight polyetherimides, however, in certain instances, a slight molar excess (about 1 to 5 mole percent) of diamine or dianhydride can be employed. The polyetherimides of Formula I have an intrinsic viscosity [#] greater than 0.2 deciliters per, gram, preferably 0.35 to 0.60, or 0.7 deciliters per gram or even higher when measured in m-cresol at 250C, The aromatic bis(ether anhydride)s of Formula III include, for example, 2r2-bis14-(2,3-dicarboxyphenoxy)phenyl]- propane dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride; 1,3-bis(2,3-dicarboxyphenoxy)benzene dianhydride; 4,4-bfs(2,3-dicarboxyphenoxy)dipheny'l. sulfide dianhydride; 1,4-bis(2,3-dicarboxyphenoxy)benzene dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)benzophenone dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfone dianhydride; 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride; - 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride; 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxy- phenoxy)diphenyl-2,3-propane dianhydride; etc. and mixtures of such dianhydrides. The organic diamines-of Formula IV include, for example, m-,phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, benzidine., 4,4'-diaminodiphenyl sulfide, 4,4' -diaminodiphenyl sulfone, one, '-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3 '-dimethyl- benzidine and, 3,3'-dimethoxybenzidine. The polyetherimides of formula (II) may, for example, be prepared by affecting reaction in the presence of a dipolar aprotic solvent of a mixture-of ingredients comprising, for instance, (1) a bis(nitrophthalimide) of. the general formula: EMI7.1 wherein R2, is defined: as hereinabove, and (2) an alkali metal salt of an organic compound of the. general formula: (VI) MO-R1-OM wherein M is an alkali metal and R@ is defined as hereinabove. The bis(nitrophthalimide) used in preparing the polymer is formed by reacting a diamine of the formula described above, NH2-R1-NH2, with a nitro-substituted aromatic anhydride of the formula: EMI8.1 The molar ratio of diamine to anhydride should ideally be about 1:2 respectively. The initial reaction product is a bis(amide-acid) which is subsequently dehydrated to the corresponding bis(nitrophthalimide). The diamines are described, supra. The preferred nitrophthalic anhydrides useful herein are 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, and mixtures thereof. These reactants are commercially available in reagent grade. They may-also be prepared by the nitration of phthalic anhydride using procedures described in Organic Syntheses, Collective Vol.- I, Wiley (1948), page 408. Certain other closely related nitroaromatic anhydrides-may also be-used in the reaction and are illustrated for exampie by 2-nitrophthalic anhydride, - 1-nitro-2,3-naphthalene- dicarboxylic acid anhydride, 3-methoxy-6-nitrophthalic anhydride, and the like. With reference to the alkali metal' salts of formula VI among the.divalent carbocyclic aromatic radicals which R1 may represent mixtures of such radicals are also included) are, for instance, divalent aromatic hydrocarbon radicals of from 6 to 20 carbon atoms, such as phenylene, biphenylene, naphthylene, etc.' Included are residues of, e.g. hydroguinone, resorcinol, chlorohydroquinone, etc. In addition, R1 may be a residue of a dihydroxy diarylene compound in which the aryl nuclei are joined by either an aliphatic group, a sulfoxide group, sulfonyl group, sulfur, carbonyl group, oxygen, the -C(CH3)(CH2)2(COOH) group, etc. Typical of such' diarylene compounds are the following: 2,4-dihydroxydiphenylmethane; bis(2-hydroxyphenyl)methane; .2,2-bis(4-hydroxyphenyl)propane; bis(4-hydroxyphenyl)methane; bis(4-hydroxy-5-nitrophenyl)methane; bis(4-hydroxy-2,6-dimethyl-3-methoxy phenyl )methane; 1,1-bis(4-hydroxyphenyl)ethane; 1,2-bis(4-hydroxyphenyl)ethane; ,r-bis(4-hydroxy-2-chlorophenyl)ethane 1,1-bis(2,5-dimethyl-4-hydroxyphenyl)ethane; 1,3-bis(3-methyl-4-hydroxyphenyl)propane; 2,2-bis(3-phenyl-4-hydroxyphenyl)propane; 2,2-bis(3-isopropyl-4-hydroxyphenyl)propane; 2,2-bis(4-hydroxynaphthyl)propane; hydroquinone naphthalene diols; bis(4-hydroxyphenyl)ether; bis(4-hydroxyphenyl)sulfide; bis(4-hydroxyphenyl)sulfone; and the like. When dialkali metal salts of formula V: are used with the compound illustrated by formula V, the ingredients are advantageously present in an equal molar ratio for optimum molecular weight and properties of the polymer. Slight molar excesses, e.g., about 0.001 to 0.10 molar excess of either the dinitro-substituted organic compound or of the dialkali metal salt of formula VI may be employed. When the molar ratios are approximately equal, the polymer is substantially terminated by Z-N02 at one end and a phenolic group at the other end. If there is a molar excess of one compound, that particular terminal group will predominate. The conditions of reaction whereby the alkali-metal salt of formula VI is reacted with the dinitro-substituted organic compound of formulA V can be varied widely. Generally, temperatures of the order of about 25-1500C are advantageously employed, although it is possible to employ lower or higher temperature conditions depending on the ingredients used, the reaction product sought, time of reaction, solvent employed, etc. In addition to atmospheric pressure, superatmospheric pressures and subatmospheric pressures may be employed depending upon the other conditions of reaction, the ingredients used, the speed at which it is desired to effect reaction, etc. The time of reaction also can be varied widely depending on the ingredients used, tie temperature, the desired yield, etc. - It ha-s been found that times varying from about 5 minutes to as much as 30 tb;40 ho.urs are advantageously employed to obtain the maximum yield and desired molecular weight. Thereafter the reaction product can be treated in the, appropriate manner required to effect precipitation and/or, separation of the desired polymeric reaction product. Generally, common solvents such as alcohols (e.g. methanol, ethanol, isopropyl alcohol, etc.) and aliphatic hydrocarbons (e.g. pentane, hexane, octane, cyclohexane, etc.) may be employed as precQpitants for this purpose. It is important that- the reaction between the dinitro-substituted organic compound of formula V and the alkali-metal salt of formula VI (mixtures of such alkali-metal gales can also be used) be carried out in the presence of a dipolar aprotic solvent. The polymerization is performed under anhydrous conditions usually using dipolar aprotic solvents such as dimethylsulfoxide which are added in varying amounts depending upon the particular polymerization. A total quantity of. solvent, dipolar aprotic solvent or mixture of such solvent with an aromatic solvent sufficient to give a final 'solution containing 10-20% by w'eight. of polymer is preferably employed. The preferred poly(etherimide) polymers include those having repeating units of the following formula: EMI11.1 -The -crystalline polyamide polymers which may be used herein are well known in the art. The polyamide polymers include homopolymers as well as copolymers. These polymers may be formed by conventional methods from the condensation of bifunctional monomers, by the condensation of diamines and dibasic acids, as well as by addition polymerization. Numerous combinations of-diacids, such as carbonic acid, oxalic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, isophthalic acid, tere.phtnalic acid, and the like, diamines, such as hydrazine, ethylenediamine, hexamethylenediamine, 1,8-octanediamine, piperazine, and the like, and amino acids are possible. The chains between functional groups in tne reactants may comprise linear or branched aliphatic hydrocarbons, or alicyclic or aromatic rings. They may also contain hetero atoms such as oxygen, sulfur, and nitrogen. Secondary diamines lead to the formation of N-substituted polyamides Also, included herein are the aromatic polyamide polymers which are aromatic in both the diamine and the dibasic acid. Tne dibasic acias include terephthal-ic acid, isophthalic acid, phthalic acid, and the like. The aromatic diamines include 0-phenylenediamine, 2,4-diaminotoluene, 4,4'-methylenedianiline, and the like. -The polyamiae polymers are prepared by methods well Known in the art, such as by direct amidation which is the reaction of amine groups with carboxyls accompanied by elimination of wÅater; low temperature polycondensation of diamines- and diacid chlorides, ring-opening - polyme,rization, addition of amines to activated double bonds, polymerization of isocyanates and reaction, of formaldehyde with dinitriles. The polyamide polymers include polyhexamethyleneadipamide, i.e., nylon 6,6; poly -caprolactam), i.e., nylon-6; polypropiolactam, i.e., nylon-3; poly(pyrrolidin-2-one), i.e.; nylpn-4; poly@@-enanthamide), i.e., nylon-7; polycapryllactam, i.e., nylon; poly( -pelargonamide), i.e., nylon-9; poly(ll-aminodecanoic acid), i.e., nylon-10; poly(undecaneamide), i.e., nylon-ll; polynexamethyleneterephthalamide, i.e., nylon-6,T, nylon 6,10, and tne like Tne reinforcing fibers which may be use herein include fiberglass, carbon fibers, aromatic polyamide fibers, and the like. The mineral fillers which may be used incluae calcium carbonate, wollastonite, silicates and the like. The blend of poly(etherimide) polymer and crystalline polyamide' polymer may be alloyed witn a variety'of thermoplastic polymers such as aromatic polyesters, aromatic polycarbonates, poly (ester carbonates), poly(aryl ether) S, polyhydroxyether, polyarylates and the like. Other additives may be included with the blend and include pigments; tnermal stabilizers; ultraviolet light stabilizers, plasticizers, and tne like. The polyamide polymer is used in amounts of trom about 95 to about 5, preferably from about 80 to about.20 weight percent. The poly(et,herimide) polymer is used in amounts of from about 5 to about 95, preferably from about 20 to about 80 weight percent. The reinforcing fiber, or mineral filler or thermoplastic polymer, is used in amounts of from O to about 50, preferably from 0 to about 30 weight percent. The composition of this invention is prepared by any conventional mixing method. For example, a preferred method comprises mixing the polyamide polymer, poly(etherimide) polymer and optionally, thermoplastic polymer, and/or reinforcing fiber, and/or mineral fiber in powder or granular form in an extruder and extruding the mixture into strands, chopping tte strands into pellets and molding the pellets into the desired article. The novel poly(etherimide) -polylactam tlock copolymer may be prepared from lactam monomer and poly(etherimide) by anionically polymerizing the lactam monomer with a catalyst-initiator system which comprises, as the initiator or activator, one or more poly(etherimides). The lactams which may be used according to the present invention are all those which are capable ot being polymerized anionically and are preferably those lactam monomers which contains at least one ring group of the structure EMI14.1 herein b is a whole number which is 3 to 15, and preferably 3 to 10, and R7 and R8 may be the same or different radicals. on each carbon atom and may be H or C1 to C10 hydrocarbon. Such lactams would include those having a single ring structure such as 2-pyrrolidone, 2-piperidone, 6-metnyl-2-piperidone, -caprolactam, enantholactam, capryllactam, lauryllactam, decanolactam, undecanolactam, dodecanolactam, pentadecanolactam, hexadecanolactam, alkyl substituted caprolactams, aryl substituted lactams, and the like. Lactams having a plurality of ring structures which may be used in the present invention include bis-lactams such as alkylene bis-lactams of the formula: EMI15.1 wherein b' and b@ are independently integers of from 1 to about 14; R7 and R8 are as defined above, and R9 may be C1 to C4 alkylene such as methylene, ethylene, propylene, and butylene; phenylene and substituted phenylene; O and S. Other lactams having a plurality of ring structures include bicyclic lactams, such as those represented by the formulae: EMI15.2 The lactams to be polymerized can be used individually or in any. combination thereof. The initiators. are poly(etherimides). selected, from the, following formulae: . EMI15.3 EMI16.1 wherein R1, R2 Z and a are as previously defined and X and X' are independently halogen, NO2 or an anhydride terminated moiety. The poly(etherimide) terminated by X and X' may be obtained by the procedure described above using a slight excess of the corresponding reagent in the polymerization reaction. The block copolymers of tne present invention are block copolymer's of the-AB and ABA types, wherein A represents a block of lactam polymer and B represents the'poly(etherim,id,e) block. In the usual-case these two types of block copolymers are concurrently prepared in the polymerization reaction. These two types of-block cppolymers may also be represented by the structures EMI16.2 for the ABA copolymers and EMI17.1 for the AB type block copolymers.. R1, R2' Z, a and X are as defined above. X1 and X2 are residues of the reaction between the initiator terminals X and X', respectively, and the salt of the lactam being polymerized. For example, when X is Hal and X' is Hal, then X or X1 are Hal and X2 is a chemical bond. The A chains of lactam monomer attach to the initiator at the site of, and upon the removal during the initiating reaction of, all or part of one or both of the terminal groups. Most of the above described X and X' terminal groups are active enough to serve us initiating sites, although with a given polymeric initiator not all of such individual X and X' sites will react. In the case where X is R or ArOR and X' is OH or OR these terminal groups are not very reactive, per se. Where such groups are present it is believed that a scission of the chain of the polymeric initiator takes place, with the creation of a more active terminal group at the site of the cleaved polymer chain. The block copolymers of the present invention formed from the poly(etherimide) and lact,amsdisclosed. above are unique semi-crystalline materials which have physical properties which-are superior. in various resp-ects to either a homopolymer of the corresponding lactam or to the poly(etherimide) polymers. They are superior, for example, to the lactam homopolymers because they have higher heat.disortion temperatures, particularly in the case where tne lactam is #-caprolactam and the lactam homopolymer is thus a nylon-6 polymer. In such instances of comparison the block copolymers of tne present invention would have heat distortion temperatures up to about 600C. or more higher than the heat' distortion temperature of the nylon-6 hoopolymer where the block copolymer contains at least 10 to 15 weight percent of the poly(etherimide) as a block of the copolymer. The block copolymers also, have lower bydrophilicity and better thermal stability properties than the corresponding lactam homopolymers. The block copolymers are also better than the poly(etherimide) m.aterials.from which they are formed because they have in;,roved stress crack resistance properties and $approved resistance to various types of environments. The flock copolymers also have improved processability in that the.y may be processed at temperatures which are up to 1000C. lower than the temperatures at which the .poly(etherimide) materials may be processed. Blends of the block copolymer with poly(etherimide) would provide a useful property profile. The block copolymer blend with poly(etherimide) will offer improved mechanical compatibility over simple blends of polyamides and poly(etherimides). The preferred copolymers of the present invention are those which contain about 20 to 80 weight percent of the lactam monomer in the form' of block segments therein, and 80 to 20 weight percent of the poly(etherimide) materials as block segments therein. The catalysts which, may be employed in the anionic polymerization reactipn of the present invention include all anionic catalyst materials which, may be employed in the anionic polyrerization of lactams. The catalyst-m.aterial is usually a'salt of the lactam being polymerized although any other lactam may be used to-form the catalyst. The salt is usually prepared by reacting the lactam with a strong base, i.e., a base strong enough to convert the lactam to its salt. Such bases would include alkali and alkaline earth metals or basic derivatives of such metals such as the hydroxides, oxides, alkoxides, phenoxides, hydrides, alkyls, arylA, amides, borohydrides and weak acid salts, i.e., acetates, carbonates, bicarbonates, benzoates, sulfites and bisulfites; Grignard reagents, and various other organo-metallic compounds. Such bases would include, therefore, metals such as lithium, sodium, potassium, magnesium, calcium, strontium, barium, and aluminum and derivatives of such metals, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide,-calcium hydroxide, strontium hydroxide, barium hydroxide, lithium hydride, sodium hydride, sodium oxide, sodium methoxide, sodium phenoxide, sodium methyl, sodium ethyl, sodium phenyl, sodium naphthyl, and sodamide; Grignard reagents such as ethyl magnesium chloride, methyl magnesium bromide, and phenyl magnesium bromide; and other compounds such as zinc diethyl, trijospropyl aluminum, diisobutyl aiuminum hydride, and lithium aluminum hydride. About 0.2 to 20, and preferably 0.5 to 4, mole percent of catalyst is used per mole of monomer being polymerized. The catalyst and initiator are employed in a mole ratio to each other of about 2 to 200, and preferably, 3 to 10. When the strong base is reacted with the lactam to form the catalyst a by-product is usually formed. For example, hydroten.is formed as a by-product when the metal hydrides or the elemental metals are used; water is formed as a by-product when metal hydroxides are used; alcohols are formed when alkoxides are used and water and CO2 are formed when carbonate or bicarbonate salts are used. The preferred catalysts are those which result in the most readily removable by-products, since some of the by-products, such as H2 0, may have a deleterious effect on the polymerization reaction. The polymerization reaction is preferably conducted in bulk. Under such bulk polymerization procedures the poly(etherimide) initiator is preferably dissolved in the monomeric lactam. This can be accomplished easily at temperatures between 800C. and 2500C. When initiators are used which contain less reactive end groups, e.g., hydroxyl or halogen then the solution of initiator in lactam monomer may be stored in the liquid or molten state at temperatures which are slightly above the melting point of the monomeric lactam, i.e.-, about 70-750C. for -caprolactam monomers, for up to about 40 hours without any.appreciable change in the viscosity o-f the system or potency of the catalyst-initiator system. This provides. an unusually long pot life. for the molten system at such temperatures. The pot life is shorter at higher temperatures, i.e., between about 800C. and about 130 C. for ±-caprolactam, and at temperatures of about 1300-2400C. the ±-caprolactam polymerization reaction proceeds within a few minutes when using polymeric initiators having.such OH and halogen terminals. The reactions will proceed even faster under such temperature conditions when other terminal groups are used on the initiator. The bulk polymerization reaction is usually conducted at atmospheric pressure and at,a temperature of about 1300 to 260µC. The reaction can be conducted at a temperature which is Above or below the melting point of the resulting polymer, and above that of the monomer. The use.of elevated pressure is not regoired for the polymerization reaction. The bulk polymerization reaction requires a polymerization period of about 30 to 100 minutes at 1300-2200C. depending on the lactam(s) employed, the catalyst concentration, and the polymerization temperature. The bulk polymerization reaction should be carried out under anhydrous conditions, i.e., in the presence of no more than about 0.2 weight percent, and preferably no more than 0.03 weight percent, of water or other active hydrogen containing by-product. Where a catalyst is used which would generate water or other active hydrogen containing by-products, such as the hydroxide, alkoxide or phenoxide cat-alysts, the excess amounts of such by-product materials should be removed before the polymerization reaction is conducted, The polymerization is preferably carried out under an inert blanket of gas, such as, nitrogen, argon or helium in order- to prevent oxidative degradation of the monomer and of destruction of the catalyst by moisture. The reaction may be carried out batchwise or continuously. An advantageous method of carrying out the reaction of the present invention is to conduct the bulk polymerizÅatin in conventional molding equipment such as a rotational casting device or a compression molding machine, or an extruder. In this way the polymer and the molded objects can both be formed in one step. Where the polymerization is conducted in such molding devices, conventional molding pressures may be employed in order to simultaneously form the molded object with the in -s'itu formed polymer. Since the lactams are normally solid materials at room temperatures, the bulk polymerization reactions may be carried out by various procedures. In one procedure, the lactam may be melted, and both the catalyst and the initiator admixed with it and then the reaction may be caused to proceed by bringing the reaction mixture to polymerization temperatures. In another procedure, the catalyst and initiator may b dissolved separately in the lactam monomer, after wnich the two separate solutions may be combined to cause the polymerization to proceed at polymerization temperatuXes. Where the polymerization is conducted in molding equipment, the equipment may be heated to the desired polymerization temperature in order to effect polymerization upon injection therein of the polymerization reaction system. In addition to being conducted in bulk, the polymerization may also be conducted in high boiling inert organic solvents, i.e., those having boiling points of above 100 C., such as chlorobenzene, ichlorobenzene, xylene, trichlorobenzene, Nakyl pyrrolidones and hexamethylphosphoramide, at temperatures of about 100 C. up to the boiling point of the solvent; or at temperatures of about 130 to 240.0 C. in dispersion systems such as those disclosed in U.S. 3,061,592 and 3,383,352,' and by G.B. Gechele and G.P. Martins in J. Applied Polymer Science, 9, 2939 (1965). The polymerization reaction of the present invention may also be conducted in the presence of various types of materials which are normally employed with the types of polymers prepared by the present invention, or the material may be added to the polymer after it is formed. Such materials would include fillers, stabilizers, fibrous reinforcing agents such as glass fiber, and pigmenting materials. The reaction can also be carried out in the presence of thermoplastic polymers which are inert under tne reaction conditions such as polyolefins and copolymers tnereof, aromatic vinyl polymers and copolymers thereof, polyphenylene oxides, poly(arylethers), and the like. EXAMPLES The following example-s serve to give specific illustrations of the practice of this invention but they are not intended in any way to limit tne scope of this invention. In these examples, all parts and percentages are on a weignt basis unless otherwise specified. Control A Control A was a poly(etherimide) polymer having repeating units of the following formula: EMI24.1 This po'ly(etnerimide) polymer has a reduced viscosity of 0.51 as measured in chloroform (0.5 g. per 100 ml) at 250C. Tne poly(etnerimide) polymer was injection molded into-ASTM test specimens in a 1 1/4 ounce Newbury screw injection molding machine under the molding conditions shown in Table I. The test specimens were tested for the following properties: tensile strength and modulus according to ASTM D-638; elongation at break according to ASTM D-638; notched izod impact strength according to ASTM D-256; heat distortion temperature measured at 264 psi on a 1/8 inch thick unannealed test bar according to ASTM D-635. The melt flow of the polymer was measured according to a-procedure similar to ASTM D-1238. The results are shown in Table I. Also, test specimens (1/8 inch wide and 25 mils thick cast from a compression molded sample) were placed under the stress snown in Table II. A . cotton swab saturated with the chemical environment, as identified in Table II, was attached to tne center of the test specimen. The time for the specimen to rupture was then recorded. The results are shown in Table II. Example 1 80 weight percent of, the poly(etnerimia',e) of Control A was blended with 20 weight percent of nylon 6,6 (Zytel 101 obtained from E.I. DuPont De Nemours L Co.) having a melting point of 255 C (as measured by ASTM D-789), a specific gravity of 1.14 (as measured by ASTM D-792) and a flexural modulus of 410,0,00 psi, dry 23 C (as measured by ASTM D-790) in a one inch laboratory extruder having a 24 L/D at a temperature of 270 to 2900C.' - The resultant proauct was molded and tested as described in Control A. The results are shown .Tables I and II. Example 2 60 weight percent of the polytetherimide) of Control A-was blended with 40 weight percent of the nylon 6,6 of Example 1 by the procedure described in Example 1. Tne resultant product was molded and tested as described in Control A. The results are shown in Tables I and II. Example 3 60 weight percent of the poly(etherimide) of Control A was blended with 40 wight percent of nylon 12 (Grilamid L25 Natural obtained from Emserwerke) having a melting range of 176 to 1800C (as measured by a polarization microscope), a specific gravity of 1.01 (as measured by ASTM D-792) and a flexural modulus of 180,000 psi, dry, 230C (as measurea by ASTM D-790) by the procedure described in Example 1. The resultant product was molded and tested as described in Control A. The results are shown in Tables I ana II. TABLE I Example Control A 1 2 3 Description of the Composition Polyetherimide 100 80 60 60 (wt.8) Nylon (wt.%) - 20 40 40 Properties Tensile Modulus 462,000 475,000 409,000 344,000 (psi) Tensile. strength 15,200 12,800 11,000 9,010 (psi) Elongation (percent) 50 5.1 14.2 16.7 Notched Izod Impact 1.2 0.8 1.1 1.5 Strength (ft-lbs/in of notch) Heat Distortion 1950C 1860C 1450C 148 C Temperature Melt Flow (dg/min) No Flow 4.5 43.9 6.5 at 3000C and 44 psi Molding Conditions Cylinder Temperature Rear F 710 580 550 550 Mid F 700 - 570 540 540 Nozzle. F 690 560 530 530 Screw (revolutions per 80 80 120 80 minute) Injection Pressure 1.050 900 800 900 (psi, gauge) Cycle Time (sec) 52 52 52 52 Mold Temperature ( C) 140 140 80 90 TABLE II TIME TO RUPTURE RESULTS Chemical EXAMPLES Environment Stress (psi) Control A2 1 2 3 Trichlorethylene 1000 2 seconds (R) 0.29 hours (R) 2 hours (NCNB) 2 hours (NCNB) 1,1,1-trichloroethane 4000 0.35 hours (R) 2.53 hours (R) 6 hours (NCNB) 5000 1.90 hours (R) Skydrol 500A 4000 0.3 hours (R) 4.14 hours (R) CELLOSOLVE Acetate 2000 0.091 hours (R) 4 hours (NCNB) 4 hours (NCNB) 4 hours (NCNB) Xylene 3000 0.056 hours (R) 0.30 hours (R) 4 hours (NCNB) 4 hours (NCNB) Toluene 3000 0.012 hours (R) 0.14 hours (R) 2 hours (NCNB) 2 hours (NCNB) 50/50 Toluene/Heptane@ 5000 0.19 hours R 0.48 hours R 2.73 hours R 1.44 hours R 1Skydrol 500A = aircraft fuel 2R = ruptured NCNB = not crazed, not ruptured Control B 80 weight percent of the poly(etherimide) of Control A was blended with 20 weight percent of fiberglass (1/8 inch chopped strands, P1978-XI obtained from Owens-Corning Piberglas Corp.) by the procedure described in Example 1. The resultant product was molded and tested as described in Control A. The results are shown in Table III. Control B 80 weight percent of the nylon 6,6 of Example 1 was blended with 20 weight percent of the fiberglass of.Control B by the procedure described in Example 1. The resultant product was molded and tested as described in Control A. The results are shown in Table III Example 4 48 weight percent of the pol-y(etherimide) of Control A was blended with 32 weight percent of the nylon 6,6 of Example 1 and 20 weight percent.of the fiberglass of Control B. The resultant product was molded and tested as described-in Control A. The results are shown in Table 1II. TABLE III Example Control B 3 Control C Description of the Composition Polyetherimide (wt.%) 80 48 - Nylon (wt.%) -- 32 80 Fiberglass (wt.%) 20 20 20 Properties Flexural Modulus (psi) 961,000 879,000 747,000 Flexural Strength (psi) 29,700 28,400 26,700 Tensile Modulus (psi) 978,000 949,000 866,000 Tensile Strength (psi) 18,500 18,000 16,100 Elongation (percent) 2.6 .3.4 2.4 Notched Izod Impact 1.1 1.1 1.3 Strength (ft-lbs/in of notch) Heat Distortion Tem perature 2070C 2120C 2420C Melt Flow (dg/min) No Flow 10.4 at 3000C and 44 psi Molding Conditions - Cylinder Temperature Rear OF 710 550 540 Mid OF 700 540 530 Nozzle F 690 530 520 Screw (revolutions per minute) 120 120 130 Injection Pressure (psi, gauge) 1,000 1,000 1,000 Cycle Time (sec) 52 52 52 Mold Temperature ( C) 140 90 90 Example 5 Preparation of the poly(etherimide)-polylactam block copolymer To a dry 500 milliliter (ml), three neck flask fittea witn a mechanical stirrer, nitrogen. inlet tube and a distillate receiver attached to a condenser were added 62.5 grams of the poly(etherimide) depicted in Control A, supra, 100 ml. of chlorobenzene, and 220 ml. of distilled ± -caprolactam (1.95 moles a 220 gms) Stirring ana circulation of dry Nitrogen were started. The solution was heated (oil-bath) and 90% of the chlorobenzene was distilled off (time of dis,tillation: 2.0 hours). A substantially dry solution of the polymer in the lactam was left in the flask as the residue. In a separate, dry 100 ml. flask fitted with a magnetic stirrer, a nitrogen-inlet tube, and a condenser were placed 30 ml of distilled #-caprolactam. Beating of this material was accomplished via an oil bath. To the partially solidified S -caprolactam was added 0.48 grams (0.8 gm of a 60-4Q by weight dispersion in mineral oil) of sodium hydride (0.02 moles). The flask was slowly heated to 800C, and. the hydrogen gradually evolved to yield a clear solution of the catalyst (1 hour). Twenty-seven milliliters of this catalyst solution (1.80 x 10-2 moles) were transferred via syringe to the polymer solution in ± -caprolactam. The oil bath temperature was kept at 1850C for 40 minutes, and no visible increase in viscosity was observed. The mixture was cooled to 1400C, and another 0.48 g (0.8 gm of a 60-40 by weight dispersion in mineral 'oil) of solid sodium hydride (0.02 mole) was added. The oil bath temperature was raised to 2200C. A rapid increase in viscosity was observed and at the end of a 75 minute period the reaction was considered completE. The resulting block copolymer product was cooler under nitrcgen. The solid cold copolymer was highly -rystallind and tougn. A mechanical grinder. was usea to break-the material into small particles. The yield of tnis crude product was quantitative. The crude material was extracted with methanol in a soxhlet apparatus. The extracted material was vacuum dried till constant weight at 100 C. The yield of methanol-insoluble block copolymer was 91.1%. It's RV was 0.69 as measured in m cresol at 25 C (0.1 gm/lOOml). - Example 6 The polY(etherimide) -polylactam block copolymer synthesized in Example 5 was compression molded in a 4 x 4 inch x 20 mil cavity mold. The mechanical properties measured on the resultant sheet conditioned at 230C and 50% relative humidity are listed below using t,esting'procedures similar to that described for Control A but modified to handle the smaller.specimen size (1/8 inch wide strips). 1% Secant Modulus (psi) = 118,000 yield Strength (psi) = 2,250 Tensile Strength '(psi)' = 3,660 Elongation (8) = 192 Example 7 The poly (etberimide) -polylactam block copolymer synthesized in Example 5 was blended with tne poly(etherimide) described in Control A. The mixing equipment used was a Brabender operated at 280 -300 C. The blend of 50% poly(etherimide) polylactam block copolymer and 50% poly(etherimide) was compression molded at 2700C into a 4" x 4" x 20 mil sample. using the procedures described in Example 5, the following mechanical properties were o@tained for this blend. 1% Secant Modulus (psi) = 224,000 Tensile Strength (psi) = 6,680 e Elongation = 19 Melt Flow (3G00C, 44 psi) - 16.8 dg/min Example 8 25 wt z of the poly(etherimide)-nylon 6 block copolymer described in Example 5 was mixed with 75 wt % of the poly(etherimide) described in Control A. Tne melt flow (300 C; 44 psi) of the resultant blend was 14.1 dg/min.

Claims: CLAIMS: 1. A composition suitable for molding comprising a poly(etherimide) polymer and a crystalline polyamide polymer. 2. A composition as defined in claim 1 wherein the poly(etherimide) polymers is of the EMI34.1 <tb> following <SEP> formulae <SEP> (I) <SEP> or <SEP> (II): <tb> <SEP> 0 <SEP> 0 <tb> <SEP> II <SEP> - <SEP> II <SEP> <tb> C <SEP> /CCN-- <SEP> ' <SEP> C <tb> ( <SEP> ss <SEP> / <SEP> N- <SEP> R; <tb> <SEP> O <SEP> O-Rl-O <SEP> O <SEP> a wherein a is an integer greater than 1, -O-R1-O- is attached to the 3 or 4 and '3' or 4' positions-and R1 is selected from (a) a substituted.or unsubstituted aromatic radical of the formula: EMI34.2 (b) a divalent radical of the formula: : EMI34.3 wherein R3 is independently C1 to C6 alkyl, or halogen and R4 is selected from -0-, -S-, EMI35.1 -SO-, -SO2alkylene of 1 to 6 carbon atoms, cycloalkylene of 4 to.8 carbon atoms, alkylidene of 1 to 6 carbon atoms or cycloalkylidene of ,4 to 8 carbon atoms, R2 is selected from an aromatic hydrocarbon radical having from 6-20 carbon atoms and halogenated derivatives thereof, or alkyl substituted derivatives thereof, wherein the alkyl group contains I to 6 carbon .atoms, -alkylen,e and cycloalkylene radicals having from 2 to 20 carbon atoms, C2-C8 alkylene terminated polydiorganosiloxane and a divalent radical of the formula EMI35.2 wherein R3 are as previously defined, and R5 may be a direct bond; ; EMI35.3 wherein -0-Z is a member selected from EMI36.1 wherein R6 is independently hydrogen, lower alkyl or lower alkoxy . EMI36.2 wherein- the oxygen may be attached to either ring and located ortho or, para to one of the bonds of the imide carbonyl groups, Ri and R2 and a are as -defined above; 3. A composition as defined in claim 1 or 2 wherein the poly(etherimide) has repeating units o the following formula: EMI36.3 4, A composition as defined in claims 1 - 3 wherein the polyamide is selected from one or, more of the following:. nylon-6,6, nylon-6, nylon-3, nylon-4, nylon-7, nylon-8, nylon-9, nylon-10, nylon-ll, nylon-6,T, and nylon-6,10. 5. A composition as defined in claims 1 - 4 wherein the crystalline polyamide polymer is used in amounts of Erom.about 5 to about 95 weight percent. 6. A composition as defined in claims 1 - 5 wherein the poly(ethert'nide) polymer is used in amounts of from about 5 to about 95 weight percent. 7. A composition as defined in claims 1 - 6 which contains a reinforcing fiber such-as carbon fibers, fiberglass and/or aromatic polyamide fibers. 8. A composition as defined in claims 1 - 7 which contains a mineral filler such as calcium carbonate, wollastonite and/or silicates. 9. A composition as defined in claims 1 - 8 which contains a thermoplastic polymer; e.g. a polycarbonate or a poly(ester carbonate). 10. A block copolymer comprising at least one block of lactam polymer and at least one block of a poly(etherimide) polymer, 11. A block copolymer as defined in claim 10 wherein the poly(etherimidej polymer has repeating units of the following formula: EMI37.1 12. A blend of a block copolymer as defined in claim 10 or 11 with a thermoplastic polymer. 13. A blend as defined in claim 12 wherein the thermoplastic polymer is nylon-6 or a poly(etherimide) polymer.

Inventors: MATZNER, MARKUS, ROBESON, LLOYD MAHLON
Applicants: AMOCO CORPORATION
Application year: 1983
Main classification: C08L79
IPC codes: C08L67, C08L77, C08G73, C08L79