CA1133164A - Toughened thermoplastic polyamide matrix with micron sized dispersed soft polymer - Google Patents
Toughened thermoplastic polyamide matrix with micron sized dispersed soft polymerInfo
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- CA1133164A CA1133164A CA253,067A CA253067A CA1133164A CA 1133164 A CA1133164 A CA 1133164A CA 253067 A CA253067 A CA 253067A CA 1133164 A CA1133164 A CA 1133164A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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Abstract
ABSTRACT OF THE DISCLOSURE
Toughened multi-phase thermoplastic composition consisting essentially of one phase containing 60 to 99 percent by weight of a polyamide matrix resin of number average molecular weight of at least 5000, and 1 to 40 percent by weight of at least one other phase containing particles of at least one polymer having a particle size in the range of 0.1 to 3.0 micron and being adhered to the polyamide, the at least one polymer having a tensile modulus in the range of 1.0 to 50,000 psi, the ratio of the tensile modulus of the polyamide matrix to tensile modulus of said at least one polymer being greater than 10 to 1. Said at least one polymer is either a branched or straight chain polymer. The toughened compositions are useful for making molded and extruded parts. Such parts possess greater ductility, less reduction in tough-ness from scratches and molded in notches and reduced susceptibility to catastrophic failure when compared to known melt fabricated materials.
Toughened multi-phase thermoplastic composition consisting essentially of one phase containing 60 to 99 percent by weight of a polyamide matrix resin of number average molecular weight of at least 5000, and 1 to 40 percent by weight of at least one other phase containing particles of at least one polymer having a particle size in the range of 0.1 to 3.0 micron and being adhered to the polyamide, the at least one polymer having a tensile modulus in the range of 1.0 to 50,000 psi, the ratio of the tensile modulus of the polyamide matrix to tensile modulus of said at least one polymer being greater than 10 to 1. Said at least one polymer is either a branched or straight chain polymer. The toughened compositions are useful for making molded and extruded parts. Such parts possess greater ductility, less reduction in tough-ness from scratches and molded in notches and reduced susceptibility to catastrophic failure when compared to known melt fabricated materials.
Description
~:~3~
Field of the Invention -This in~ention relates to thermoplastic poly-amide compositions, and more particularly to such composi-tions having improved ductility or toughness, and to the processes for prepa~ing such compositions~
Unmodified thermoplastic polyamides are generally regarded as "tough"~ For example, the po]yamides have good elongation; high energy to break, as dernonstrated in tensile tests; high tensile impact strength and high energy absorption as demonstrated in falling dart tests, e~g., the Gardner impact test. In one aspect of toughness the po~yamide materials are quite deficien~; namely, resistance to crack propagation. This de~iciency is reflected in notch sensitivity~ bri-ttle breaks and occasional catastrophic failure of molded or extruded parts. The tendency of polyamides to break in a brittle rakher than ductile fashion is a significant limitation of utili-ty. A resin may be characterized in its tendency toward ductility by the notched Izod test ~Sl~I D~256 56.
With the normal notch radius of 10 mils, polyhexamethylene adipamide (66 nylon), dry as molded~
will have a notched Izod value of about 1 fto lb./inch of' notch~
There is much prior ~rt concerned with improving the impact strength Or polyamides~ ~ variety of additives have been added to polyamides with some impro~ement in toughness being obtained. British Patent 99~4399 for example~ discloses a thermoplastic co.rnposition comprising " .
. .
~ 3 ~ ~6 ~
a mixture of 50 to 99 percent linear polyamide and 1 to 50 percent of olefin copolymer particles) the olefin copolymer containing from 0.1 to 10 mole percent of acid groups. Many olefin copolymers are disclosed, but it is not required that the olefin copolymers have a tensile modulus of 50,000 or less. The dry as molded notch sensitivity increases ko 4.6 fto lbsO/inch as the copolymer is increased to ~0 percent by weight as described in Example 1.
Murch U. S. Patent 3,~5,163 discloses blends of 60 to ~5 percent by weight polyamide and an acid-containing olefin polymer in which the acid is derived from an ~ ethylenically unsaturated carboxylic acid and in which at least 10 percent of the acid groups have been neutralized with metal ions~ Murch is concerned primarily with weld-line toughness which does not have a specific relation with blend toughness. The Murch blend, however, also demonstrates impro~ement over the composi-- tion of British Patent 99~9~39 with respect to blend toughness. Murch did not recognize that improved blend toughness of polyamide compositions can be achieved at lower concentration levels of polymer addition provided that at least one polymer present has a tensile modulus o 50,000 or less and the ratio of the tensile modulus of the polyamide to the tensile modulus of said polymer is greater than 10 to 1.
Two U. S. Patents, Kray et al. 3~3g~91g6 and Seven et al. 3,~65jo59 disclose polyamide compositions ~hich possess high impact strength~ some values being greater than 10 ft~ lbs./inch~ The disclosed compositions ~-~3.,~
are graft copolymers prepared from an ethylene containing copolymer. The disclosed copolymers do not contain sites which adhere to the polyamide through sites of the poly-amide. There is also no recognition that the tensile modulus of the ethylene containing copolymer is no greater than 50,000 p.s.i. or that particle size is importantO Furthermore, the Izod impact strength is determined with samples held at 50 percent relative humidity for 3 days prior to testing as disclosed in UO S. Patent 3,3g~ 6~ In some composition$ moisture causes sharp increases in the notched Izod value. This is shown in Table 1J page 6 of British Patent 99~439 Owens et al~ U. S~ Patent 3,66~,274 teaches modestly improved impact strength of polycarbonamides modified with ~A) a first elastomer phase of copolymers or terpolymers and (B) a final rigid phase thermoplastic stage containing amine-reactive moieties9 preferably carboxylic acid groups. The soft modifier is coated ~ith a rigid layer thus negating a large impro~ement in poly~
amide toughness that could be achieved with a copolymer rnodifier.
SU~,~
According to this invention, there is provided a toughened multi-phase thermoplastic composition consisting essentially of one phase containing ~0 to 99 percent by ~Jeight of a polyamide matrix resin of number average molecular weight of at least 5000, and 1 to ~0 percent by weight of at least one other phase containing particles of at least one polymer taken from the class consisting of branched and straight chain polyrners having a particle ~3~
CYL~
size in the range of 0.01 to ~. n -~1~3~and being adhered to the polyamide matrix resin, and said at least one polymer having a tensile modulus in the range of about 1.0 to 50,000 psi, the ratio of the tensile modulus of the polyamide matrix resin to tensile modulus of said at least one polymer beiny greater than 10 to 1.
The term "consisting essentially of" means that in addition to the required polyamide matrix resin and the at least one polymer other components can be present in the toughened composition provided that the basic and essential characteristics of the toughened composition are not materially affected thereby.
The term "branched and straight chain polymers"
means that -the polymers are not crosslinked to a degree which will increase their modulus to greater than 50,000 psi or decrease their melt flow to a level which prevents effective dispersion.
According to another aspect of this invention, there is provided a process for the preparation of a toughened multi-phase thermoplastic composition which comprises, in a closed system, (a) admi~ing (1) 60 to 99 percent by weight of a polyamide matrix resin of number average molecular weight of at least 5000, and
Field of the Invention -This in~ention relates to thermoplastic poly-amide compositions, and more particularly to such composi-tions having improved ductility or toughness, and to the processes for prepa~ing such compositions~
Unmodified thermoplastic polyamides are generally regarded as "tough"~ For example, the po]yamides have good elongation; high energy to break, as dernonstrated in tensile tests; high tensile impact strength and high energy absorption as demonstrated in falling dart tests, e~g., the Gardner impact test. In one aspect of toughness the po~yamide materials are quite deficien~; namely, resistance to crack propagation. This de~iciency is reflected in notch sensitivity~ bri-ttle breaks and occasional catastrophic failure of molded or extruded parts. The tendency of polyamides to break in a brittle rakher than ductile fashion is a significant limitation of utili-ty. A resin may be characterized in its tendency toward ductility by the notched Izod test ~Sl~I D~256 56.
With the normal notch radius of 10 mils, polyhexamethylene adipamide (66 nylon), dry as molded~
will have a notched Izod value of about 1 fto lb./inch of' notch~
There is much prior ~rt concerned with improving the impact strength Or polyamides~ ~ variety of additives have been added to polyamides with some impro~ement in toughness being obtained. British Patent 99~4399 for example~ discloses a thermoplastic co.rnposition comprising " .
. .
~ 3 ~ ~6 ~
a mixture of 50 to 99 percent linear polyamide and 1 to 50 percent of olefin copolymer particles) the olefin copolymer containing from 0.1 to 10 mole percent of acid groups. Many olefin copolymers are disclosed, but it is not required that the olefin copolymers have a tensile modulus of 50,000 or less. The dry as molded notch sensitivity increases ko 4.6 fto lbsO/inch as the copolymer is increased to ~0 percent by weight as described in Example 1.
Murch U. S. Patent 3,~5,163 discloses blends of 60 to ~5 percent by weight polyamide and an acid-containing olefin polymer in which the acid is derived from an ~ ethylenically unsaturated carboxylic acid and in which at least 10 percent of the acid groups have been neutralized with metal ions~ Murch is concerned primarily with weld-line toughness which does not have a specific relation with blend toughness. The Murch blend, however, also demonstrates impro~ement over the composi-- tion of British Patent 99~9~39 with respect to blend toughness. Murch did not recognize that improved blend toughness of polyamide compositions can be achieved at lower concentration levels of polymer addition provided that at least one polymer present has a tensile modulus o 50,000 or less and the ratio of the tensile modulus of the polyamide to the tensile modulus of said polymer is greater than 10 to 1.
Two U. S. Patents, Kray et al. 3~3g~91g6 and Seven et al. 3,~65jo59 disclose polyamide compositions ~hich possess high impact strength~ some values being greater than 10 ft~ lbs./inch~ The disclosed compositions ~-~3.,~
are graft copolymers prepared from an ethylene containing copolymer. The disclosed copolymers do not contain sites which adhere to the polyamide through sites of the poly-amide. There is also no recognition that the tensile modulus of the ethylene containing copolymer is no greater than 50,000 p.s.i. or that particle size is importantO Furthermore, the Izod impact strength is determined with samples held at 50 percent relative humidity for 3 days prior to testing as disclosed in UO S. Patent 3,3g~ 6~ In some composition$ moisture causes sharp increases in the notched Izod value. This is shown in Table 1J page 6 of British Patent 99~439 Owens et al~ U. S~ Patent 3,66~,274 teaches modestly improved impact strength of polycarbonamides modified with ~A) a first elastomer phase of copolymers or terpolymers and (B) a final rigid phase thermoplastic stage containing amine-reactive moieties9 preferably carboxylic acid groups. The soft modifier is coated ~ith a rigid layer thus negating a large impro~ement in poly~
amide toughness that could be achieved with a copolymer rnodifier.
SU~,~
According to this invention, there is provided a toughened multi-phase thermoplastic composition consisting essentially of one phase containing ~0 to 99 percent by ~Jeight of a polyamide matrix resin of number average molecular weight of at least 5000, and 1 to ~0 percent by weight of at least one other phase containing particles of at least one polymer taken from the class consisting of branched and straight chain polyrners having a particle ~3~
CYL~
size in the range of 0.01 to ~. n -~1~3~and being adhered to the polyamide matrix resin, and said at least one polymer having a tensile modulus in the range of about 1.0 to 50,000 psi, the ratio of the tensile modulus of the polyamide matrix resin to tensile modulus of said at least one polymer beiny greater than 10 to 1.
The term "consisting essentially of" means that in addition to the required polyamide matrix resin and the at least one polymer other components can be present in the toughened composition provided that the basic and essential characteristics of the toughened composition are not materially affected thereby.
The term "branched and straight chain polymers"
means that -the polymers are not crosslinked to a degree which will increase their modulus to greater than 50,000 psi or decrease their melt flow to a level which prevents effective dispersion.
According to another aspect of this invention, there is provided a process for the preparation of a toughened multi-phase thermoplastic composition which comprises, in a closed system, (a) admi~ing (1) 60 to 99 percent by weight of a polyamide matrix resin of number average molecular weight of at least 5000, and
(2) 1 to 40 percent by weight of at least one polymer at a temperature in the range of about 5 to 100C above the melting point of sa.id polyamide matrix resin and (b) shearing to disperse the polymer in said matrix to a particle size in the range of 0.01 to 3.0 micron, said at least one polymer being adhered to said matrix and having a tensile modulus in the range of 1.0 to 50,000 ~'~
, ....
p-Soi~ ~ the ratio of the tensile modulus of` said matrix to tensile modulus of said at least one polymer being greater than 10 to 1.
~=~ .
The polyamide matrix resin of the tou~hcned compositions of this invention is well known in the art and embraces those semi-crystalline and arnorphous resins having a mo]ecular weight of at least 5000 and commonly ref`erred to as nylons. Suitable polyamides include those described in U. S. Patents 2~0719250; 2,071,251; 2,130~5239 29130,9~; 2,241~322; 2,3129966; 29512,606; and 39393,210D
me polyamide resin can be produced by condensation of equimolar amounts of a sat~rated dicarboxylic acid con-taining from 4 to 12 carbon atoms with a diamine, in which the diamine contains from L~ to 14 carbon atomsO
~xcess diamine can be employed to provide an excess of amine end groups over carboxyl end groups in the polyamide.
~xamples of polyamides include polyhexamethylene adipamide (66 nylon)~ polyhexamethylene azelaamide (69 nylon)~
polyhexamethylene sebacamide (610 nylon)~ and polyhexa-methylene dodecanoamlde (~12 nylon)~ the polyamide produced by ring opening of lactams~ i~e. 7 polycaprolac-tam7 polylauric lactam, poly~ amino~undecanoic acid 9 bis(para-aminocyclohexyl) methane dodecanoami~e. It is also possible to use in this inven~ion polyamides prepared by thc copolymeriæation of two of the above polymers or ter-polymerization of the above polymers or their components9 e.g~y for example, an adipic~ isophthalic acid hexa-methylene diamine copolyrner~ Preferably the poly~nides ~ are linear with a melting point in excess o~ 200C. As ~6--great as 99 percent by weight of the composition can be composed of polyamide; however, preferred compositions contain from 60 to 99 percent, and more narrowly 80 to 95 percent, by weight oi polyamide.
The composition is toughened by the combination of at least one polymer with the polyamide. The term "at least one polymer" means one or more polymers which co-exist in single discrete particles having a particle size ranging from 0.01 to 3.0 microns, preferably 0.02 to 1 micron, within the matrix, so that either the mixture of polymers or at least one of the polymers in the mixture meets the following criteria:
(a) sites which adhere to the polyamide matrix;
(b) tensile modulus, as added, in the range of about 1.0 to 20,000 psi, preferably about 5 to 20,000 psi, the ratio of tensile modulus of the polyarnide matrix resin to tensile modulus of said at least one polymer being greater than 10 to 1, preferably greater than 20 to 1.
The polyamide is the continuous phase in the composition and the polymer performs the function of a soft dispersed phase which is adhered to the polyamide matrix. The polymer may be elastomeric, but it has been found that thermoplastic polymers which are not elastomeric are also effective in the compositions.
The polymers are branched or straight chain and are of such composition that crosslinking other than by reaction with the polyamide matrix is not necessary to their function and excessive crosslinking ~ay, in fact, , . ~ . . .
, ....
p-Soi~ ~ the ratio of the tensile modulus of` said matrix to tensile modulus of said at least one polymer being greater than 10 to 1.
~=~ .
The polyamide matrix resin of the tou~hcned compositions of this invention is well known in the art and embraces those semi-crystalline and arnorphous resins having a mo]ecular weight of at least 5000 and commonly ref`erred to as nylons. Suitable polyamides include those described in U. S. Patents 2~0719250; 2,071,251; 2,130~5239 29130,9~; 2,241~322; 2,3129966; 29512,606; and 39393,210D
me polyamide resin can be produced by condensation of equimolar amounts of a sat~rated dicarboxylic acid con-taining from 4 to 12 carbon atoms with a diamine, in which the diamine contains from L~ to 14 carbon atomsO
~xcess diamine can be employed to provide an excess of amine end groups over carboxyl end groups in the polyamide.
~xamples of polyamides include polyhexamethylene adipamide (66 nylon)~ polyhexamethylene azelaamide (69 nylon)~
polyhexamethylene sebacamide (610 nylon)~ and polyhexa-methylene dodecanoamlde (~12 nylon)~ the polyamide produced by ring opening of lactams~ i~e. 7 polycaprolac-tam7 polylauric lactam, poly~ amino~undecanoic acid 9 bis(para-aminocyclohexyl) methane dodecanoami~e. It is also possible to use in this inven~ion polyamides prepared by thc copolymeriæation of two of the above polymers or ter-polymerization of the above polymers or their components9 e.g~y for example, an adipic~ isophthalic acid hexa-methylene diamine copolyrner~ Preferably the poly~nides ~ are linear with a melting point in excess o~ 200C. As ~6--great as 99 percent by weight of the composition can be composed of polyamide; however, preferred compositions contain from 60 to 99 percent, and more narrowly 80 to 95 percent, by weight oi polyamide.
The composition is toughened by the combination of at least one polymer with the polyamide. The term "at least one polymer" means one or more polymers which co-exist in single discrete particles having a particle size ranging from 0.01 to 3.0 microns, preferably 0.02 to 1 micron, within the matrix, so that either the mixture of polymers or at least one of the polymers in the mixture meets the following criteria:
(a) sites which adhere to the polyamide matrix;
(b) tensile modulus, as added, in the range of about 1.0 to 20,000 psi, preferably about 5 to 20,000 psi, the ratio of tensile modulus of the polyarnide matrix resin to tensile modulus of said at least one polymer being greater than 10 to 1, preferably greater than 20 to 1.
The polyamide is the continuous phase in the composition and the polymer performs the function of a soft dispersed phase which is adhered to the polyamide matrix. The polymer may be elastomeric, but it has been found that thermoplastic polymers which are not elastomeric are also effective in the compositions.
The polymers are branched or straight chain and are of such composition that crosslinking other than by reaction with the polyamide matrix is not necessary to their function and excessive crosslinking ~ay, in fact, , . ~ . . .
3:3~6i~
be harmful.
Branched and straight chain polymers useful as the soft phase of the composition are represented by the formula:
A(a~ B(b)-C(C)-D(d3~E(~) F(f~ G(g)-H(h) derived in any order9 e~g~, random9 from monomers A ~o H where A is ethylene~
: B is C0;
, C is an unsaturated monomer taken from the class consisting of ~ ethylenically unsaturated carboxylic acids having from 3 to ~ carbon atoms, and derivatives thereof taken from ~he class consisting of monoesters of alcohol.s of 1 to 29 carbon atoms and the,dicarboxylic acids ' - and anhydrides of the dicarboxylic acid~ and the metal salts of the monocarboxylic, di-; carboxylic acids and the monoester of the di-carboxylic acid having from 0 to 100 percent of the carboxylic acid groups ionized by neutralization with metal ions and dicarboxylic acids and monoesters of the dicarboxylic acid neutralized by amine-ended caprolactam oligomers having a DP of 6 to-24;
D is an unsa.turated epoxide of 4 to 11 carbon atoms;
E is the residue derived by the loss of nitrogen from an aromatic sulfonyl azide substituted by carboxyli.c acids taken from the clas,s consisting of monocarhoxyl,ic and dicarboxylic acids having from 7 to 12 carbon atoms and derivatlves ~3~
thereof taken from the class consisting of monoeskers of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and-anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic~ dicarboxylic acids and the monoester of the dicarboxylic acid having from 0. to lO0 percent of the carboxylic acid groups ioni~ed by neutralization with metal ions;
F is an unsaturated monomer taken from the class consisting of acrylate esters having ~rom 4 to 2~ carbon atoms~ vinyl esters of acids ha~i~g from l to 20 carbon atoms (substantially no residual acid)~ vinyl ethers of 3 to 20 carbon atoms, and vinyl and vinylidene halides,and nitriles having from 3 to 6 carbon atoms;
G is an unsaturated monomer having pendant hydro-carbon chains of l to 12 carbon a-tom~ capable of being graf~ed with monomers having at least one reactive group of the type defined in C9 D and ~, and pendant aroma~ic groups which may have l to 6 substituent groups having a total o~ 14 carbon atoms9 and H is an unsaturated monomer taken from the class consisting of branched~ straight chain and cyclic compounds having from 4 to 14 carbon atoms and at least one additional nonconjugated unsaturated carbon-carbon bond capable of being grafted with a monomer having at least one reactive group of the type defined in C, D and E.
~9-~3~
The aforementioned monomers may be present in the polymer in the following mole fraction:
(a) 0 to 0095;
(b) 0 to 0.3;
~c) 0 to 0.5;
(d) 0 to 0~59 (ej 0 to 0~5, (f) 0 to 0~99;
(g) to 0O~9; and (h) 0 to 0~99 so that the total of all components is a mole fraction of l~Oo Pre~erably ~a) to (h~ are present in the following mole fraction:
(a) 0 to 0.9;
~b) 0 to 0.2~ most pr~ferably O.l to 0.2 - (c~ 0.0002 to 0~2, most pre~erably 0.002 to 0O05;
(d~ 0~005 to 002, most preferably OoOl ~0 to O.l;
(e) 0.0002 to O.l, most preferably 0~002 to 0,Ol;
(f) 0 ~o 0.9~, (g~ 0 to 0~9g; and.
(h~ 0 to 0~9~ .
In place of the aforementi.oned polymers can be used either:
I apolyurethane which is the reaction product ~ of at least one glycol taken from the class cons-isting of' polyester glycol ha~ing an average molecular weight of' 300 to 6,000 and a polyether --:LO--~33~
g1YGO1 having an a~erage molecular weight of 300 to 6~ooo and optionally at least one diol having a molecular weight of less than 3009 and at least one diisocyanate having 4 to 21 carbon atoms; or J a polymer containing polyether repeat uni-ts taken from the class consisting of the reaction product -~
of epoxide~containing monomers having 2 to 3 carbon atoms~ an epoxide-containing monomer having pendant groups taken from the class consisting of methyl or chloromethyl groups, and mixtures of said epo~ide monomersO
Each of polymers I or J; when present, replace the polymer containing components A to H. Preferably Polymer I is used with polya~ides which melt at temperatures below 200C~ whereas preferably Polymer J is used with poly-amides which melt at tempera~ures below 225C.
At least one of Bt Cp D and E is present in all polymeric systems wi~h the exception of I and J. When A
is present9 in addition to at least one of B9 C~ D and E being present7 at least one of F9 G and H is also present. A mixture of two or more polymers can be used with the proviso that at least one of B, C9 D and E is present in at least one of the polymersO Since I and J
are polymers which contain adherent sites9 the presence Of BJ C~ D and E is not necessary.
The polymeric component of the toughened composition may be prepared by standard copolymerization reaction or by a grafting reacti.on. Thus B, C~ D and E
may be copolymerized with A, F7 G and H and C, D and E
may be added by a grafting reacti.on, ~ 3~
Illustratire of monomers C to H of the above formula are:
C is maleic acid~ maleic anhydride~ maleic acid monoethyl esterJ metal salts of acid monoethyl ester7 fumarlc acid, fumaric acid monoethyl ester, itaconic acid9 vinyl benzoic acid, vinyl phthalic acid~ metal salts of fumaric acid monoethyl ester7 monoesters of maleic, ~umaric~ itaconic acids with R
where R is up to 29 carbon atoms~ e.g~, methyl, propyl, isopropylS butyl, isobutyl, hexyl9 cyclohexyl~ octyl, 2-ethyl hexyl, decyl9 stearyl9 methoxy ethyl, ethoxy ethyl, hydroxy ethyl~ etc a D is glycidyl methacrrlate9 glycidyl acrylate9 allyl glycidyl ether, vinyl glycidyl ether, glycidyl itaconate9 etcO
E is phthalic anhydride sulfonyl azide~ methyl ester and monooctadecyl ester of phthalîc ~ - anhydride sulfonyl azide, benzoic acid sulfonyl a~ide, naphthoic acid sulfonyl azide~ naphthoic - diacid sulfonyl azide~ R-monoesters (and metal salts thereof) of phthalic acid and naphthoic diacid sulfonyl azide, ~here R is up to 29 carbon atoms9 etc.;
. F is methyl methacrylate~ butyl acrylate, ethyl acrylateg vinyl acetate9 methyl vinyl ether, zinc methacrylate, acr~lonitrile, R - esters ~ of acrylic, methacrylic acids; ~ - vinyl ethers9 vinyl benzoate, vinyl naphthoate, ~12-vinyl esters of R acids, where R is up to l~
carbon atoms, vinyl chlorideS vinylidene fluoride, etc O;
G is styrene, propylene9 isobutylene9 vinyl naph~halene 9 vinyl pyridine, vinyl pyrrolidone, mono-, di-, ~richloro styrene9 R'-styrene where R' is 1 to lO carbon atoms~ butene, hexene~
octene~ decene, etc.; and X is hexadiene~ norbornadiene, butadiene~ iso~
~0 prene, divinyl, allyl styrene9 etc.
Polymer I includes: reaction products of diiso-cyanates, e~g., 2,4- or 2~6-toluene diisocyanate and mixtures, ~ methylene bis phenyl isocyanate, hexa- -methylene diisocyanate, 4g~'-methylene bis cyclohexyliso-cyanatej glycols, e~g~, di(betaoxyethyl~ ether of hydroquinone~ poly~ethylene adipate) ~lycol9 poly~l9~-butylene adipate glycolS polypropylene ether glycol~
polytetramethylene ether glycol; diols~ e.g., ethylene gl~col, l~-butanediol, etcO Polymer J includes~ 0 ethylene oxide, propylene oxide, epichlorohydrin, etcO
Useful polymers for toughening polyamide compositions are the following alternating or primarily random polymers:
zinc salt of ethylene/isobutyl acrylate/methacrylic acid; ethylene/methyl acrylate/monoethyl ester of maleic anhydride and 0 to 100 percent neutralized zinc, sodium, calcium, lithium7 antimony, and potassium salts thereof;
ethylene/methyl acrylate/monoethyl ester of maleic anhydride partially neutralized with an amine ended oligomer of caprolactam; mixture of ethylene/isobutyl ~13-~ 33 ~
acrylate/methacrylic acid and ethylene/methyl acrylate/
monoethyl ester of maleic anhydride and zinc salts thereof;
~thylene/methyl acrylate/methacrylic acid and zinc salts thereof; ethylene/vinyl acetate/methacrylic acid and zinc salts thereof; ethylene/methyl methacrylate/methacrylic acid and zinc salts thereof; ethylene/vinyl acetate/
carbon monoxide; mixtures of ethylene/vinyl acetate/
carbon monoxide and a zinc salt of ethylene/isobutyl acrylate/methacrylic acid; mixtures of ethylene/vinyl acetate and a zinc salt of ethylene/isobutyl acrylate/
methacrylic acid; mixtures o~ ethylene/isob~tyl acrylate and a zinc salt of ethylene/isobutyl acrylate/methacrylic acid; mixtures of ethylene/acrylic acid and'ethylene/
vinyl acetate; ethylene/isobutyl acrylate/carbon monoxide;
ethylene/stearyl methacrylate/car'bon monoxide; ethylene/
n butyl acrylate/carbon monoxide; ethylene/2-ethyl hexyl methacrylate/carbon monoxide; ethylene/methyl vinyl ether/
carbon monoxide; ethylene/vinyl acetate/maleic anhydride?
ethylene/vinyl acetate monoethyl ester of maleic anhydride; ethylene/~inyl acetate/glycidyl methacrylate;
ethylene/propylene/],4 hexadiene-g~maleic anhydride;
mixtures of ethylene/propylene/1,4 hexadiene and ethylene/
maleic anhydride; ethylene/propylene/norbornadiene/
1,4 hexadiene-g-benæoic acid sulfonyl azide; ethylene/
propylene/1~1~ hexadiene-g~phthalic anhydride sulfonyl azide; mixtures o~ ethylene/propy].ene/1,4 hexadiene and ethylene/propylene/1,4 hexadiene-g-maleic anhydride;
ethylene/propylene/194 hexadiene-g~maleic anhydride neutraliz.ed with amine ended oligomer of caprolactam;
3 ethylene/propylene/1~4 hexadiene/maleic anhydride ~ ~3~
neutralized with zinc rosinake; ethylene/propylene/
1,4 hexadiene-g-fumaric acid; ethylene/propylene/
194 hexadiene/norbornadiene~g maleic anhydride; ethylene/
propylene/1,4 hexadiene/norbornadiene-g-monoethyl ester of maleic anhydride; ethylene/propyl.ene/194 hexadiene/
norbornadiene-g-fumaric acid; ethylene/propylene/
1,~ hexadiene/glycidyl methacrylate; ethylene/propylene/
19~ hexadiene/norbornadiene-g-phthalic anhydride sulfonyl azide; mixtures of ethylene/propylene/194 hexadiene and ethylene/monoethyl ester of maleic anhydride; mixtures.
of ethylene/propylene/1,4 hexadiene and ethylene/butyl.
hydrogen maleate; mixtures of ethylene/propylene/
1,4 hexadiene and ethylene/maleic anhydride9 mixtures of butadiene/acrylonitrile and styrene/maleic anhydride;
mixtures of styrene/~utadiene and ethylene/maleic anhydride; isobutylene/isoprene-g-phthalic anhydride sulfonyl azide; poly(isobutylene)-g-phthalic anhydride sulfonyl azide; mixtures of ethylene/propylene/1,4-hexadiene/
norbornadiene and styrene/maleic anhydride; isoprene/
ph~halic anhydride; mixture~ of natural rubber and ethylene/monoethyl ester o~ maleic anhydride; butyl acrylate/monoethyl ester of fumaric acid~ ethyl acrylate/
fumaric acid; epichlorohydrin/ethylene oxide; mixtures of ethylene/propylene and ethylene/monoethyl ester of maleic anhydride; ethylene/propylene-g-phthalic anhydride sulfonyl azi.de; ethylene/propylene/5~ethylidene~2-norbornene-g fumaric acid, ethylene/propylene/dicyclo pen~adiene-g monoethyl ester of maleic acid~ ethylene/
propylene/5-propenyl-2~norbornene-g-maleic anhydride, ethylene/propylene/tetrahydroindene-g-f~maric acid, ~ 33 ~
ethylene/propylene/1,4-hexadiene/5-ethylidene~-norbornene-g-fumaric acid.
The improvement in ductility of a compssi~ion characterized by a higher notched Izod value is approximately proportiona] to the concentration of adherent sites in the polymeric component as well as to the melt viscosity which is a measure of the molecular weight9 and molecular weight distribution within the limits of effective dispersion. ~Jhere high concentrations of adherent sites are utilized, it ls generally possible to mix two polymers together, i e., one as the source of adherent sites~ and the other as a diluent. Mixing may be accomplished by combining the polymers with the polyamide separately or in combination with the proviso that the polymer containing the adherent sites must not be combined with the polyamide matrix resin prior to combination of any other pol~ners~ In ethylene/
propy].ene/diene polymers molecular weights equivalent to melt flow of 0.5 to ~00 g./10 mins. and more by-ASI~
D 123~ but at 2~0C. and a total l.oad of 2160 g~ are effective~ In the variety of polymers employed a melt flow range of more than 0.1 to 1~000 may be employed but a range of 0~5 to 100 is preferredO
While not being limited to any theory, it is believed that t~e soft phase polymer only has to adhere with the polyamide matrix at the interface or sur~ace of the two phases. The mechanism of adhesion is not fully understood and may be achieved by bonds which vary in energy from hydrogen bonding to covalent bonding.
The notched Izod test further characterizes -lG~
~ ~ 3~
the composition with regard to its ductility~ Expressed in fta lb./inch Or notch, notched Izod values in the dry as molded condition for preferred polymers are at least the values represented by the *ormula:
B ~ 0~2 C
~ ~ 2.0 ~ 0.5 (C2-lO~
B ~ 12.0 where B is the notched I~od of the polyamide matrix polymer, CI is 2 to lO percent by weight of the at least one polymer, and C2 is lO to 30 percent by weight of the at least one pol~merO B ~ 12cO applies between 30 and 40 percent9 It has been found generally that dry as molded notched Izod ~alues of at least ~ ftD lbs./inch are readily achieved at lower concentration values than is achieved by prior art materials.
The melt flow of the thermoplastic composition is in the range of 0.01 to 200 grams per minute by 20 ASTM D-123~ at 2~0~Co and 2160 g. load, preferably 0.1 to lS0 grams per minute. Since the viscosity is highly shear sensitive the compositions of the invention are well suited for extrusion applications~
It is apparent from the above description that a variety of polymers are effective in toughening polyamides and a substantially large nl~ber of combina-tions are usefulO It is therefore not surprising that the limits of effectiveness of some components of the compositions depend on the other components~ For ~ 3~
example, th~ lower limit of concentration of an effective adhering site, e.g., maleic anhydride9 will probably be lower than a less effective adhering sitej e.g., methacrylic acid. Similarly the balance between amine and carboY~yl end groups in a matrix will influence the comparative effecti~eness of different adherent sites of the at least one polymer. Polymers or polymeric mixtures in the lower modulus range tend to be more effecti~e than those polymers or polymeric mixtures in the hi~her modulus range and may be useful at lower concentrations of adherent site. The equation describing the relation-ship between notched Izod and concentration of pol-ymer is applicable only for polymers ~ith an optirnum combina-tion of adherence, modulus9 and particle size~ It is also understood that the mixtures described herein are effective only when the components of -the mixture co-exist in the same discrete particles in the polyamide matrix~ Howe~erD more than one such polymeric mixture can be present in the toughaned thermoplastic composition.
The compositions of the invention may be modi-fied by one or more conventional additives such as stabilizers and inhibitors of oxidati~e, thermal, and ultraviolet light degradation; lubricants and mold release agents~ colorants including dyes and pigments, fibrous and particulate fillers and rein~orcemen~s, nucleating agents, plasticizers~ etc.
The stabilizers can be incorporated into the composltion at any stage in -the preparation of the thermoplastic cornposition. Preferably the stabilizers are included early to preclude the initiation of ~L~l3~L6~
degradation before the composition can be protected.
Such stabilizers must be compatible with the compositionO
The oxidati~e and thermal stabilizers useful in the materials of the present invention include those used in addition polymers generally. They include, for example~ up to 1 percent by weight9 based on the weight of polyamide of Group I metal halides, e.g~, sodium, potassium, lithium with cuprous halides9 eOg~, chloride, bromide, iodide~ hindered phenols, hydroquinones, and varieties of substi~uted members of those groups and combinations thereof~
The ultraviolet light stabilizers7 e~g~, up to 2.0 percent~ based on the weight of polyamide~ can also be those used in addition pol~ners generally. Examples of ultra~iolet light stabilizers include various substituted resorcinols, salicylates, benzotriazoles~ benzophenonesg and the like.
Suitable lubricants and mold release agents9 e.g.~ up to loO percent~ based on the weight o~ the composition; are stearic acid, stearic alcohol, stearamides;
organic dyes such as nigrosine2 etc.; pigments, e.gO 9 titanium dioxide9 cadmium sulfide9 cadmium sulfide selenide, phthalocyanines9 ultramarine blue~ carbon black, etc.; up-to 50 percent9 based on the weight of the composition, of fibrous and particulate fillers and rein-forcernents, e~g., carbon fibers~ glass fibers~ amorphous silica9 asbestos9 calci~ silicate~ aluminum silicate, magnesium carbonate~ kaolin~ chalk, powdered quartz7 micaJ feldspar, etc.; nucleating agents~ eOg~, talc, calcium fluoride9 sodlum phenyl phosphinate~ alumina, and finely divided polytetrafluoroekhylene, etc.;
-19~
~ 33 ~ ~ ~
plasticizers9 up to about 20 percent9 based on the weight of the composition~ e~g.~ dioctyl phthalate, dibenzyl phthalate~ butyl benz~l phthalate~ hydrocarbon-oils, N-normal butyl benzene sulfonamide t ortho and para toluene ethyl sulfonamide~ etc. The colorants (dyes and pigments) can be present in an amount of up to about 590 percent by weight, based on the weight o~ the composi tion, The toughened compositions of ~his invention can be prepared by melt blending, in a closed systemD a polyamide and at ~east one polymer into a uniform mixture in a multi-screw extruder such as a Werner ~fleiderer extruder having generally 2-5 kneading blocks and at l~ast one reverse pitch to generate high shear, or other conventional plasticating devices such as a Brabender,.
- Banbury mill, or the like. Alternatively~ the blends may be made by coprecipitation from solution9 blending.or ~y dry mixing together of the components followed by melt fabrication of the dry mixture by extrusion~
The compositions described in the examples are prepared with a Werner Pfleiderer twin screw eY.truder. The constituents are dry blended and extruded under vacuum 5 to lOO~C~ above the melting point of the matrix resin~ preferably 310~C. or belowO Higher temperatures have been used successfully~ The extrudate, hich is opaque at temperatures less than 20~C. above the melting point, denotin.g a two phase system, is cooled in a water bath, cut, vacuum dried and molded into *est pieces~ Of course9 many process variations are possib].e~
~20 ~ ~ 3~
It may be desirable to f'orm a concentrate of the toughened thermoplastic composition. This is accomplished by admixing the polyamide in higher concentrations based on the weight Or total composition~ e.g.~ up to about 50 percent by weight9 with the at leask one polymer.
Additional polyamide is admixed with the composition to yield the desired concentrate, such as a toughened composition containing 1 to 20 percent by weight of at least one polymerO
It has been found useful to increase the molecular weight o~ the toughened thermoplastic composi-tions during the preparation of the composition. By way of illustration~ an admixture of low molecular wPight polyamide~ eOg.~ 5,000 to 15,000~ and at least one polymer is prepared in a plasticating device as described above and the molecular weight is increased either in tha melt or at an elevated temperature below the melting point (solid phase) of the polyamide~ By way of illustration5 after melt blending the composition is either ~1) held in the melt a~ a temperature about 10 to ~0C~
above the melting point a~ a pressure of about 1 to 25 mm Hg absolute for up to one hour, or (2) in the solid phase, after cuttingp quenching and drying7 at an elevated temperature at least 15C~ below the melt temperature of the polyamide in an inert gas stream for at least two hours. Beaton U. S~ Patent 3~21S171 describes solid phase polymerization~
The toughened thermoplastic compositions can be ~ made into a wide range of useful articles by conventional moldlng methods employed in the fabrication of` thermo-L33~&~
plastic articles9 iOe~, as molde~ parts, extruded shapes~ e.gO~ tubing, films~ sheets9 fibers and oriented fibers, laminates and wire coating. "Molding" means forming an ar-ticle by deforming the blend in the heated plastic stateO
The compositions of this invention are characterized by an outsta~ding combination of properties~
foremost of ~hich is outstanding toughness properties in ~iew of the quantity of at least one polymer present with the polyamidc matrix~ The unusually high toughness pro~
vides greater ductility, less sensitivity to scratches and molded in notches, and vastly reduced susceptibility to catastrophic failure when compared with previously ~nown compositions in molded parts~ Injection molded parts often are of varying thicknesses and may have s~ratches9 molded-in notches of varying radii, and molded in stresses. In addition9 orientation effects may cause varied ductility throughout a molded part~
The maintenance of high uniform values of notched I~od toughness throughout such molded parts characterizes the improved compositions resistance to brittle breaks.
The compositions are of suff cient toughness that the effect of minor changes in processing conditions will not cause significant variations in toughness from lot to lot quantities of compositionO
~XAMPLES OF T~ INV~NTION
The followjng examples illustrate the invention wherein the percentages are by weight unless indicated.
The toughened polyamide compositions are pre~
pared as follows: -The polyamide matriY~ and pol~mer(s) in dry form~22~
~3~4 are mixed after weighin~ in the proper proportions by tumbling in a polyethylene bag. The mixture is then blended in a 2~ mm Werner Pfleiderer extruder in ~hich the hopper is blanketed with nitrogen and the vacuum port main~ained at about 25 to 30 inches vacuumO
Ex~ruder barrel temperatures are set at about the melting point of the polyamide matrix (~ 10Co~ level condition~ yielding melt temperatures in the range of 5 to about lOO~C. abo~e the melt mg point of the matrixO
The beading exiting the extruder is water quenched 9 cut and vacuum dried overnight at ~0CO prior to molding~ Test bars~ 1/2 x 5 x 1/~ inch are molded ; in 3 oz. and 6 oz~ injection molcling machines at melt temperatures 10 to 30C. above the melting point of the polyamide matrix. The mold temperature is about 90C.
with fast injection and a 20/20 or 20/30 molding cycle ~;~
(seconds r~m ~orward/second ho3cl). The molded bars are tested using the follo~ng test procedures in the dry-as~molded state:
Notched Izod toughness: at each end ASTM D-256-56 - Tensile Strength: ASTM ~-63~-5~T
Elongation: ASTM D-63~5~T
Flexural Modulus: ASTM D-790-5~T
Tensile Modulus of the matrices~ ASTM D~63~-5~T (dry) Tensile Modulus o~ the pol~aers: ASTM D-~2 ~50% RH) Mel~ Flow: ASTM D~123~73 Condition G (except where noted~0 Particle Size: Electron micrographs of microtomed or fractured surfacesO
Information relatlng to the poly~aide ma~rix and ~23~
~3~
pol,~ers u~ed in con~unei;ior~ wlth the polyamide matrlx are ~et for~h in Table~ l-A and l-B, respecti:vely~ The a~ron~n~ used herel~a~ter are ~t :eorth in Table 2.
TABIE 1-~
1. 66 Pol~ramld~ inher~nt vi.~eosit~ about 1.25 ~ 0.10 me~ured ~s 0.5 g. per 100 ml. o~
m-cr~sol at 25C.~ C00~: 65-73 ~q./~6 g.;
~2 47; 53 ~q./10 g.
2... 66 Polya~i~e lnherent visco~ ty about 0 . 86 measured ~s 0.5 g. per 100 ml. o~ m cre~ol at 25c", COOH: ea 110 e~./10~ g.; ~H2:
ca 85 ~ o6g~
3. 75 per~ent 66 Polyamide descrlbed in 1 abov~
25 percent 66 Poly~mide l~here:nt viscosity about 1.95 ~ OD1O me~æur~d a~ 0.5 g. per 100 ml. Or m-cresol at 25C.
be harmful.
Branched and straight chain polymers useful as the soft phase of the composition are represented by the formula:
A(a~ B(b)-C(C)-D(d3~E(~) F(f~ G(g)-H(h) derived in any order9 e~g~, random9 from monomers A ~o H where A is ethylene~
: B is C0;
, C is an unsaturated monomer taken from the class consisting of ~ ethylenically unsaturated carboxylic acids having from 3 to ~ carbon atoms, and derivatives thereof taken from ~he class consisting of monoesters of alcohol.s of 1 to 29 carbon atoms and the,dicarboxylic acids ' - and anhydrides of the dicarboxylic acid~ and the metal salts of the monocarboxylic, di-; carboxylic acids and the monoester of the di-carboxylic acid having from 0 to 100 percent of the carboxylic acid groups ionized by neutralization with metal ions and dicarboxylic acids and monoesters of the dicarboxylic acid neutralized by amine-ended caprolactam oligomers having a DP of 6 to-24;
D is an unsa.turated epoxide of 4 to 11 carbon atoms;
E is the residue derived by the loss of nitrogen from an aromatic sulfonyl azide substituted by carboxyli.c acids taken from the clas,s consisting of monocarhoxyl,ic and dicarboxylic acids having from 7 to 12 carbon atoms and derivatlves ~3~
thereof taken from the class consisting of monoeskers of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and-anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic~ dicarboxylic acids and the monoester of the dicarboxylic acid having from 0. to lO0 percent of the carboxylic acid groups ioni~ed by neutralization with metal ions;
F is an unsaturated monomer taken from the class consisting of acrylate esters having ~rom 4 to 2~ carbon atoms~ vinyl esters of acids ha~i~g from l to 20 carbon atoms (substantially no residual acid)~ vinyl ethers of 3 to 20 carbon atoms, and vinyl and vinylidene halides,and nitriles having from 3 to 6 carbon atoms;
G is an unsaturated monomer having pendant hydro-carbon chains of l to 12 carbon a-tom~ capable of being graf~ed with monomers having at least one reactive group of the type defined in C9 D and ~, and pendant aroma~ic groups which may have l to 6 substituent groups having a total o~ 14 carbon atoms9 and H is an unsaturated monomer taken from the class consisting of branched~ straight chain and cyclic compounds having from 4 to 14 carbon atoms and at least one additional nonconjugated unsaturated carbon-carbon bond capable of being grafted with a monomer having at least one reactive group of the type defined in C, D and E.
~9-~3~
The aforementioned monomers may be present in the polymer in the following mole fraction:
(a) 0 to 0095;
(b) 0 to 0.3;
~c) 0 to 0.5;
(d) 0 to 0~59 (ej 0 to 0~5, (f) 0 to 0~99;
(g) to 0O~9; and (h) 0 to 0~99 so that the total of all components is a mole fraction of l~Oo Pre~erably ~a) to (h~ are present in the following mole fraction:
(a) 0 to 0.9;
~b) 0 to 0.2~ most pr~ferably O.l to 0.2 - (c~ 0.0002 to 0~2, most pre~erably 0.002 to 0O05;
(d~ 0~005 to 002, most preferably OoOl ~0 to O.l;
(e) 0.0002 to O.l, most preferably 0~002 to 0,Ol;
(f) 0 ~o 0.9~, (g~ 0 to 0~9g; and.
(h~ 0 to 0~9~ .
In place of the aforementi.oned polymers can be used either:
I apolyurethane which is the reaction product ~ of at least one glycol taken from the class cons-isting of' polyester glycol ha~ing an average molecular weight of' 300 to 6,000 and a polyether --:LO--~33~
g1YGO1 having an a~erage molecular weight of 300 to 6~ooo and optionally at least one diol having a molecular weight of less than 3009 and at least one diisocyanate having 4 to 21 carbon atoms; or J a polymer containing polyether repeat uni-ts taken from the class consisting of the reaction product -~
of epoxide~containing monomers having 2 to 3 carbon atoms~ an epoxide-containing monomer having pendant groups taken from the class consisting of methyl or chloromethyl groups, and mixtures of said epo~ide monomersO
Each of polymers I or J; when present, replace the polymer containing components A to H. Preferably Polymer I is used with polya~ides which melt at temperatures below 200C~ whereas preferably Polymer J is used with poly-amides which melt at tempera~ures below 225C.
At least one of Bt Cp D and E is present in all polymeric systems wi~h the exception of I and J. When A
is present9 in addition to at least one of B9 C~ D and E being present7 at least one of F9 G and H is also present. A mixture of two or more polymers can be used with the proviso that at least one of B, C9 D and E is present in at least one of the polymersO Since I and J
are polymers which contain adherent sites9 the presence Of BJ C~ D and E is not necessary.
The polymeric component of the toughened composition may be prepared by standard copolymerization reaction or by a grafting reacti.on. Thus B, C~ D and E
may be copolymerized with A, F7 G and H and C, D and E
may be added by a grafting reacti.on, ~ 3~
Illustratire of monomers C to H of the above formula are:
C is maleic acid~ maleic anhydride~ maleic acid monoethyl esterJ metal salts of acid monoethyl ester7 fumarlc acid, fumaric acid monoethyl ester, itaconic acid9 vinyl benzoic acid, vinyl phthalic acid~ metal salts of fumaric acid monoethyl ester7 monoesters of maleic, ~umaric~ itaconic acids with R
where R is up to 29 carbon atoms~ e.g~, methyl, propyl, isopropylS butyl, isobutyl, hexyl9 cyclohexyl~ octyl, 2-ethyl hexyl, decyl9 stearyl9 methoxy ethyl, ethoxy ethyl, hydroxy ethyl~ etc a D is glycidyl methacrrlate9 glycidyl acrylate9 allyl glycidyl ether, vinyl glycidyl ether, glycidyl itaconate9 etcO
E is phthalic anhydride sulfonyl azide~ methyl ester and monooctadecyl ester of phthalîc ~ - anhydride sulfonyl azide, benzoic acid sulfonyl a~ide, naphthoic acid sulfonyl azide~ naphthoic - diacid sulfonyl azide~ R-monoesters (and metal salts thereof) of phthalic acid and naphthoic diacid sulfonyl azide, ~here R is up to 29 carbon atoms9 etc.;
. F is methyl methacrylate~ butyl acrylate, ethyl acrylateg vinyl acetate9 methyl vinyl ether, zinc methacrylate, acr~lonitrile, R - esters ~ of acrylic, methacrylic acids; ~ - vinyl ethers9 vinyl benzoate, vinyl naphthoate, ~12-vinyl esters of R acids, where R is up to l~
carbon atoms, vinyl chlorideS vinylidene fluoride, etc O;
G is styrene, propylene9 isobutylene9 vinyl naph~halene 9 vinyl pyridine, vinyl pyrrolidone, mono-, di-, ~richloro styrene9 R'-styrene where R' is 1 to lO carbon atoms~ butene, hexene~
octene~ decene, etc.; and X is hexadiene~ norbornadiene, butadiene~ iso~
~0 prene, divinyl, allyl styrene9 etc.
Polymer I includes: reaction products of diiso-cyanates, e~g., 2,4- or 2~6-toluene diisocyanate and mixtures, ~ methylene bis phenyl isocyanate, hexa- -methylene diisocyanate, 4g~'-methylene bis cyclohexyliso-cyanatej glycols, e~g~, di(betaoxyethyl~ ether of hydroquinone~ poly~ethylene adipate) ~lycol9 poly~l9~-butylene adipate glycolS polypropylene ether glycol~
polytetramethylene ether glycol; diols~ e.g., ethylene gl~col, l~-butanediol, etcO Polymer J includes~ 0 ethylene oxide, propylene oxide, epichlorohydrin, etcO
Useful polymers for toughening polyamide compositions are the following alternating or primarily random polymers:
zinc salt of ethylene/isobutyl acrylate/methacrylic acid; ethylene/methyl acrylate/monoethyl ester of maleic anhydride and 0 to 100 percent neutralized zinc, sodium, calcium, lithium7 antimony, and potassium salts thereof;
ethylene/methyl acrylate/monoethyl ester of maleic anhydride partially neutralized with an amine ended oligomer of caprolactam; mixture of ethylene/isobutyl ~13-~ 33 ~
acrylate/methacrylic acid and ethylene/methyl acrylate/
monoethyl ester of maleic anhydride and zinc salts thereof;
~thylene/methyl acrylate/methacrylic acid and zinc salts thereof; ethylene/vinyl acetate/methacrylic acid and zinc salts thereof; ethylene/methyl methacrylate/methacrylic acid and zinc salts thereof; ethylene/vinyl acetate/
carbon monoxide; mixtures of ethylene/vinyl acetate/
carbon monoxide and a zinc salt of ethylene/isobutyl acrylate/methacrylic acid; mixtures of ethylene/vinyl acetate and a zinc salt of ethylene/isobutyl acrylate/
methacrylic acid; mixtures o~ ethylene/isob~tyl acrylate and a zinc salt of ethylene/isobutyl acrylate/methacrylic acid; mixtures of ethylene/acrylic acid and'ethylene/
vinyl acetate; ethylene/isobutyl acrylate/carbon monoxide;
ethylene/stearyl methacrylate/car'bon monoxide; ethylene/
n butyl acrylate/carbon monoxide; ethylene/2-ethyl hexyl methacrylate/carbon monoxide; ethylene/methyl vinyl ether/
carbon monoxide; ethylene/vinyl acetate/maleic anhydride?
ethylene/vinyl acetate monoethyl ester of maleic anhydride; ethylene/~inyl acetate/glycidyl methacrylate;
ethylene/propylene/],4 hexadiene-g~maleic anhydride;
mixtures of ethylene/propylene/1,4 hexadiene and ethylene/
maleic anhydride; ethylene/propylene/norbornadiene/
1,4 hexadiene-g-benæoic acid sulfonyl azide; ethylene/
propylene/1~1~ hexadiene-g~phthalic anhydride sulfonyl azide; mixtures o~ ethylene/propy].ene/1,4 hexadiene and ethylene/propylene/1,4 hexadiene-g-maleic anhydride;
ethylene/propylene/194 hexadiene-g~maleic anhydride neutraliz.ed with amine ended oligomer of caprolactam;
3 ethylene/propylene/1~4 hexadiene/maleic anhydride ~ ~3~
neutralized with zinc rosinake; ethylene/propylene/
1,4 hexadiene-g-fumaric acid; ethylene/propylene/
194 hexadiene/norbornadiene~g maleic anhydride; ethylene/
propylene/1,4 hexadiene/norbornadiene-g-monoethyl ester of maleic anhydride; ethylene/propyl.ene/194 hexadiene/
norbornadiene-g-fumaric acid; ethylene/propylene/
1,~ hexadiene/glycidyl methacrylate; ethylene/propylene/
19~ hexadiene/norbornadiene-g-phthalic anhydride sulfonyl azide; mixtures of ethylene/propylene/194 hexadiene and ethylene/monoethyl ester of maleic anhydride; mixtures.
of ethylene/propylene/1,4 hexadiene and ethylene/butyl.
hydrogen maleate; mixtures of ethylene/propylene/
1,4 hexadiene and ethylene/maleic anhydride9 mixtures of butadiene/acrylonitrile and styrene/maleic anhydride;
mixtures of styrene/~utadiene and ethylene/maleic anhydride; isobutylene/isoprene-g-phthalic anhydride sulfonyl azide; poly(isobutylene)-g-phthalic anhydride sulfonyl azide; mixtures of ethylene/propylene/1,4-hexadiene/
norbornadiene and styrene/maleic anhydride; isoprene/
ph~halic anhydride; mixture~ of natural rubber and ethylene/monoethyl ester o~ maleic anhydride; butyl acrylate/monoethyl ester of fumaric acid~ ethyl acrylate/
fumaric acid; epichlorohydrin/ethylene oxide; mixtures of ethylene/propylene and ethylene/monoethyl ester of maleic anhydride; ethylene/propylene-g-phthalic anhydride sulfonyl azi.de; ethylene/propylene/5~ethylidene~2-norbornene-g fumaric acid, ethylene/propylene/dicyclo pen~adiene-g monoethyl ester of maleic acid~ ethylene/
propylene/5-propenyl-2~norbornene-g-maleic anhydride, ethylene/propylene/tetrahydroindene-g-f~maric acid, ~ 33 ~
ethylene/propylene/1,4-hexadiene/5-ethylidene~-norbornene-g-fumaric acid.
The improvement in ductility of a compssi~ion characterized by a higher notched Izod value is approximately proportiona] to the concentration of adherent sites in the polymeric component as well as to the melt viscosity which is a measure of the molecular weight9 and molecular weight distribution within the limits of effective dispersion. ~Jhere high concentrations of adherent sites are utilized, it ls generally possible to mix two polymers together, i e., one as the source of adherent sites~ and the other as a diluent. Mixing may be accomplished by combining the polymers with the polyamide separately or in combination with the proviso that the polymer containing the adherent sites must not be combined with the polyamide matrix resin prior to combination of any other pol~ners~ In ethylene/
propy].ene/diene polymers molecular weights equivalent to melt flow of 0.5 to ~00 g./10 mins. and more by-ASI~
D 123~ but at 2~0C. and a total l.oad of 2160 g~ are effective~ In the variety of polymers employed a melt flow range of more than 0.1 to 1~000 may be employed but a range of 0~5 to 100 is preferredO
While not being limited to any theory, it is believed that t~e soft phase polymer only has to adhere with the polyamide matrix at the interface or sur~ace of the two phases. The mechanism of adhesion is not fully understood and may be achieved by bonds which vary in energy from hydrogen bonding to covalent bonding.
The notched Izod test further characterizes -lG~
~ ~ 3~
the composition with regard to its ductility~ Expressed in fta lb./inch Or notch, notched Izod values in the dry as molded condition for preferred polymers are at least the values represented by the *ormula:
B ~ 0~2 C
~ ~ 2.0 ~ 0.5 (C2-lO~
B ~ 12.0 where B is the notched I~od of the polyamide matrix polymer, CI is 2 to lO percent by weight of the at least one polymer, and C2 is lO to 30 percent by weight of the at least one pol~merO B ~ 12cO applies between 30 and 40 percent9 It has been found generally that dry as molded notched Izod ~alues of at least ~ ftD lbs./inch are readily achieved at lower concentration values than is achieved by prior art materials.
The melt flow of the thermoplastic composition is in the range of 0.01 to 200 grams per minute by 20 ASTM D-123~ at 2~0~Co and 2160 g. load, preferably 0.1 to lS0 grams per minute. Since the viscosity is highly shear sensitive the compositions of the invention are well suited for extrusion applications~
It is apparent from the above description that a variety of polymers are effective in toughening polyamides and a substantially large nl~ber of combina-tions are usefulO It is therefore not surprising that the limits of effectiveness of some components of the compositions depend on the other components~ For ~ 3~
example, th~ lower limit of concentration of an effective adhering site, e.g., maleic anhydride9 will probably be lower than a less effective adhering sitej e.g., methacrylic acid. Similarly the balance between amine and carboY~yl end groups in a matrix will influence the comparative effecti~eness of different adherent sites of the at least one polymer. Polymers or polymeric mixtures in the lower modulus range tend to be more effecti~e than those polymers or polymeric mixtures in the hi~her modulus range and may be useful at lower concentrations of adherent site. The equation describing the relation-ship between notched Izod and concentration of pol-ymer is applicable only for polymers ~ith an optirnum combina-tion of adherence, modulus9 and particle size~ It is also understood that the mixtures described herein are effective only when the components of -the mixture co-exist in the same discrete particles in the polyamide matrix~ Howe~erD more than one such polymeric mixture can be present in the toughaned thermoplastic composition.
The compositions of the invention may be modi-fied by one or more conventional additives such as stabilizers and inhibitors of oxidati~e, thermal, and ultraviolet light degradation; lubricants and mold release agents~ colorants including dyes and pigments, fibrous and particulate fillers and rein~orcemen~s, nucleating agents, plasticizers~ etc.
The stabilizers can be incorporated into the composltion at any stage in -the preparation of the thermoplastic cornposition. Preferably the stabilizers are included early to preclude the initiation of ~L~l3~L6~
degradation before the composition can be protected.
Such stabilizers must be compatible with the compositionO
The oxidati~e and thermal stabilizers useful in the materials of the present invention include those used in addition polymers generally. They include, for example~ up to 1 percent by weight9 based on the weight of polyamide of Group I metal halides, e.g~, sodium, potassium, lithium with cuprous halides9 eOg~, chloride, bromide, iodide~ hindered phenols, hydroquinones, and varieties of substi~uted members of those groups and combinations thereof~
The ultraviolet light stabilizers7 e~g~, up to 2.0 percent~ based on the weight of polyamide~ can also be those used in addition pol~ners generally. Examples of ultra~iolet light stabilizers include various substituted resorcinols, salicylates, benzotriazoles~ benzophenonesg and the like.
Suitable lubricants and mold release agents9 e.g.~ up to loO percent~ based on the weight o~ the composition; are stearic acid, stearic alcohol, stearamides;
organic dyes such as nigrosine2 etc.; pigments, e.gO 9 titanium dioxide9 cadmium sulfide9 cadmium sulfide selenide, phthalocyanines9 ultramarine blue~ carbon black, etc.; up-to 50 percent9 based on the weight of the composition, of fibrous and particulate fillers and rein-forcernents, e~g., carbon fibers~ glass fibers~ amorphous silica9 asbestos9 calci~ silicate~ aluminum silicate, magnesium carbonate~ kaolin~ chalk, powdered quartz7 micaJ feldspar, etc.; nucleating agents~ eOg~, talc, calcium fluoride9 sodlum phenyl phosphinate~ alumina, and finely divided polytetrafluoroekhylene, etc.;
-19~
~ 33 ~ ~ ~
plasticizers9 up to about 20 percent9 based on the weight of the composition~ e~g.~ dioctyl phthalate, dibenzyl phthalate~ butyl benz~l phthalate~ hydrocarbon-oils, N-normal butyl benzene sulfonamide t ortho and para toluene ethyl sulfonamide~ etc. The colorants (dyes and pigments) can be present in an amount of up to about 590 percent by weight, based on the weight o~ the composi tion, The toughened compositions of ~his invention can be prepared by melt blending, in a closed systemD a polyamide and at ~east one polymer into a uniform mixture in a multi-screw extruder such as a Werner ~fleiderer extruder having generally 2-5 kneading blocks and at l~ast one reverse pitch to generate high shear, or other conventional plasticating devices such as a Brabender,.
- Banbury mill, or the like. Alternatively~ the blends may be made by coprecipitation from solution9 blending.or ~y dry mixing together of the components followed by melt fabrication of the dry mixture by extrusion~
The compositions described in the examples are prepared with a Werner Pfleiderer twin screw eY.truder. The constituents are dry blended and extruded under vacuum 5 to lOO~C~ above the melting point of the matrix resin~ preferably 310~C. or belowO Higher temperatures have been used successfully~ The extrudate, hich is opaque at temperatures less than 20~C. above the melting point, denotin.g a two phase system, is cooled in a water bath, cut, vacuum dried and molded into *est pieces~ Of course9 many process variations are possib].e~
~20 ~ ~ 3~
It may be desirable to f'orm a concentrate of the toughened thermoplastic composition. This is accomplished by admixing the polyamide in higher concentrations based on the weight Or total composition~ e.g.~ up to about 50 percent by weight9 with the at leask one polymer.
Additional polyamide is admixed with the composition to yield the desired concentrate, such as a toughened composition containing 1 to 20 percent by weight of at least one polymerO
It has been found useful to increase the molecular weight o~ the toughened thermoplastic composi-tions during the preparation of the composition. By way of illustration~ an admixture of low molecular wPight polyamide~ eOg.~ 5,000 to 15,000~ and at least one polymer is prepared in a plasticating device as described above and the molecular weight is increased either in tha melt or at an elevated temperature below the melting point (solid phase) of the polyamide~ By way of illustration5 after melt blending the composition is either ~1) held in the melt a~ a temperature about 10 to ~0C~
above the melting point a~ a pressure of about 1 to 25 mm Hg absolute for up to one hour, or (2) in the solid phase, after cuttingp quenching and drying7 at an elevated temperature at least 15C~ below the melt temperature of the polyamide in an inert gas stream for at least two hours. Beaton U. S~ Patent 3~21S171 describes solid phase polymerization~
The toughened thermoplastic compositions can be ~ made into a wide range of useful articles by conventional moldlng methods employed in the fabrication of` thermo-L33~&~
plastic articles9 iOe~, as molde~ parts, extruded shapes~ e.gO~ tubing, films~ sheets9 fibers and oriented fibers, laminates and wire coating. "Molding" means forming an ar-ticle by deforming the blend in the heated plastic stateO
The compositions of this invention are characterized by an outsta~ding combination of properties~
foremost of ~hich is outstanding toughness properties in ~iew of the quantity of at least one polymer present with the polyamidc matrix~ The unusually high toughness pro~
vides greater ductility, less sensitivity to scratches and molded in notches, and vastly reduced susceptibility to catastrophic failure when compared with previously ~nown compositions in molded parts~ Injection molded parts often are of varying thicknesses and may have s~ratches9 molded-in notches of varying radii, and molded in stresses. In addition9 orientation effects may cause varied ductility throughout a molded part~
The maintenance of high uniform values of notched I~od toughness throughout such molded parts characterizes the improved compositions resistance to brittle breaks.
The compositions are of suff cient toughness that the effect of minor changes in processing conditions will not cause significant variations in toughness from lot to lot quantities of compositionO
~XAMPLES OF T~ INV~NTION
The followjng examples illustrate the invention wherein the percentages are by weight unless indicated.
The toughened polyamide compositions are pre~
pared as follows: -The polyamide matriY~ and pol~mer(s) in dry form~22~
~3~4 are mixed after weighin~ in the proper proportions by tumbling in a polyethylene bag. The mixture is then blended in a 2~ mm Werner Pfleiderer extruder in ~hich the hopper is blanketed with nitrogen and the vacuum port main~ained at about 25 to 30 inches vacuumO
Ex~ruder barrel temperatures are set at about the melting point of the polyamide matrix (~ 10Co~ level condition~ yielding melt temperatures in the range of 5 to about lOO~C. abo~e the melt mg point of the matrixO
The beading exiting the extruder is water quenched 9 cut and vacuum dried overnight at ~0CO prior to molding~ Test bars~ 1/2 x 5 x 1/~ inch are molded ; in 3 oz. and 6 oz~ injection molcling machines at melt temperatures 10 to 30C. above the melting point of the polyamide matrix. The mold temperature is about 90C.
with fast injection and a 20/20 or 20/30 molding cycle ~;~
(seconds r~m ~orward/second ho3cl). The molded bars are tested using the follo~ng test procedures in the dry-as~molded state:
Notched Izod toughness: at each end ASTM D-256-56 - Tensile Strength: ASTM ~-63~-5~T
Elongation: ASTM D-63~5~T
Flexural Modulus: ASTM D-790-5~T
Tensile Modulus of the matrices~ ASTM D~63~-5~T (dry) Tensile Modulus o~ the pol~aers: ASTM D-~2 ~50% RH) Mel~ Flow: ASTM D~123~73 Condition G (except where noted~0 Particle Size: Electron micrographs of microtomed or fractured surfacesO
Information relatlng to the poly~aide ma~rix and ~23~
~3~
pol,~ers u~ed in con~unei;ior~ wlth the polyamide matrlx are ~et for~h in Table~ l-A and l-B, respecti:vely~ The a~ron~n~ used herel~a~ter are ~t :eorth in Table 2.
TABIE 1-~
1. 66 Pol~ramld~ inher~nt vi.~eosit~ about 1.25 ~ 0.10 me~ured ~s 0.5 g. per 100 ml. o~
m-cr~sol at 25C.~ C00~: 65-73 ~q./~6 g.;
~2 47; 53 ~q./10 g.
2... 66 Polya~i~e lnherent visco~ ty about 0 . 86 measured ~s 0.5 g. per 100 ml. o~ m cre~ol at 25c", COOH: ea 110 e~./10~ g.; ~H2:
ca 85 ~ o6g~
3. 75 per~ent 66 Polyamide descrlbed in 1 abov~
25 percent 66 Poly~mide l~here:nt viscosity about 1.95 ~ OD1O me~æur~d a~ 0.5 g. per 100 ml. Or m-cresol at 25C.
4. 50 p~rce~t 66 Poly~mlde described in 1 above 50 pore~nt 66 Poly~mide described in 3 above
5. 100 percent 66 polyamid~ inherent visc9si~g about 1.95 + 0.10 mea~ured as 0.5 g. p~r 1~0 m10 Q~ m-cresol at 25~. :
6. 66 Pol~mide inherent vlscosity about 1.25 + 0.10 mea~ured as 0,5 g. per 1OO mlr of m cres01 at 25C.~; C00~: 34-46 eq.,/106g.;
2- 73~93 eq.~/10 g.
2- 73~93 eq.~/10 g.
7. 66 Poly~mid~ inhorent vl~;c08ity about 0.98 measur~ 0.5 g. per 100 ml" o~ m-cresol at 25C., COOH: ca 44 eq./106g.; ~H2: ca 94 eq./106g,
8., 612 P~lyamid~ rent vlscosity ~bout 0.95 ~ 0,10 measured a5 0~5 g, p~r 100 ml. o~ m-cresol ~t 25C.
9~ 612 Polyamlde inhere~t ~iscosit~ about 1.,17 ~ 0.10 measured as 0~5 g. per 100 - ml. ~F m-cre~ol ~t 25C.
.J.
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10. Plasko~ 8200 - 6 nylon sold by All~ed Chemical Co.
11.. Hul~ nylon 12 inherent viscosity about 1. 20 measured as O . 5 g. per 100 ml . of m-cresol at 25~C.
12. ~ILSA~ nylon 11 lnher~nt ~lscosity about 1.17 measured as O ~, 5 g. per 100 ml. of m-cresol at 25~C. sold by Aquitane Chemicals, Inc.
13. 66/6 (80/20)copolymer inherent ~i~cosity about 1~ 33 m~asur~d as O . 5 g. per 100 ml. o~ m creqol.
14. Trogami~ T poly(trimethyl he~came~hylene terephthalam:Lde) sold by Dynamlt Nobel inherent viscoslty about 0.95 measured as 0.5 g. per 100 ml. of m-cre~ol at 25C., COOH: ~a 59 eq./106g~; ~2: ca 57 eq./106g.
15. PACM-12 polyamide containlng bis(para-aminocyc~ohexyl) m~thane and dodecane-dloic ~cid lnherent ~lscosity about 0.95 measured as 0.5 g. per 100 ml, o~
:: cr~sol at 25C., COOH: ca 57 ~3q./106g.;
~I2: ca 60 eq./106g.
:: cr~sol at 25C., COOH: ca 57 ~3q./106g.;
~I2: ca 60 eq./106g.
16. Pla~or~ 8252 ~modlfied 6 nylon) ~old by Allied Chem ~al Co.
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Polymers 1, 2, 6to 13, 28 t4 31 are prepared as described in Rees U. S. Pa~ent 3 ,264,272 .
Polymer 5 is prepared as described in Greene Belgian Patent 818~609 with the neutralizations using the procedure described in Rees [J.S. Pater~t 3~264,272 ~rlth -the exception of the ~D neutralization (Example 23) whlch is described in Rees U~,S. Patent 3,471/460.
Polymers 3" 49 14J 15, 19, 20, 21 are made by high preæsure, free radical polymerization, Polymers 16 to 183 23 ~o 27 are p:repared as described in EIammer U.S. Patent 3,780,140.
Pol~mer 22 is COMER~ 9300 ~ade by UN on Car~ide.
Polymers 32, 51 are the ind cated base polymer gra~ted aceording ~o Example 13B o~ Caywood Canadian P~tent 1~032J688~ which issued 1978 June o6.
1'he base polymers o:~ the indicated polymers are ~ollows:
Polymer 33 ethylene/propyle~e/1~4-he~adiene (64/32/~ ~ooney vlscoslty ASTM D-1646 ~ML-1~4~121C.) o~ about 45.
Polymers 34, 35 ethylene/propylene/194~hexadiene/
2~5-norb~die~e (54/40/6/0.35) Mooney viscosity about 25.
Polymers 36-38, 46-49, 70~ 71 ethylene/
propylene/1~4-hexadiene (62/32/6) Mooney viscosity abou~
Polymers 399 41-45~ 50~ 57~ 66, 73, 77 ethylene~
propylene/1~4-hexadiene/2~5-norbornadiene (68/26/6~0.15) Mooney viscosity about 33.
Pol~mer 40 e~hylene/propylene/1,4-hexadlene/
~ ~ 33 ~ ~
295-norbornadiene ~71/23/6/0.5) Mooney viscosity about . 2S.
All the above base polymers are prepared by co-polymerizing the monomers in the presence of a coordina-tion catalys~ system such as diisobu-~ylaluminu~ chloride.
and vanadium oxytrichloride~ Copolymerization may be con~
duc~ed in an inert solvent or in a slurry or particle form reactorO Details of their preparation are given, for exam~le ? in U~ S. Patents 2,933,4~0; 2 7 962 9 451;
3~000,~; 3,093~620; 3,093 7 621; 3 9 063p973; 3p1~7~230, 3,154,52~; 3~260,70~; and in M. Sittig; "Stereo Rubber and Other Elastomer Processes", Noyes DeYelopment Cor-portion~ Park Ride, N~J. 9 1967~ as well as U.S. 3,~199591.
Polymer 33 is a mixture of the above base pol~mer and ethylene/maleic anhydride (~9/11) made by high pressure9 free radical polyrnerization.
Polymer 34 is tumbled overnight with 7 weight p~rcent of MAME on 1/4 inch cubes of base polymer and ~:
extruded on a 2~ mm Werner Pfleiderer extruder fitted ~ith a vacuum port and 4 kneading blocksO The melt temperature is about 315C. and hold~up time 2 to 4 minutes. The product is quenched~ cut and driedO
Polymer 35 is a mixture of 9~2 grams of m-carboxy benzene sulfonyl azide and 3600 grams of blanc fixe added to 350 grams of the base polymer and 0~7 gram of 173,5-tri.methyl 2~4,6-tris~395~di tert-butyl-l~
hydroxybenzyl) benzene (~thy~ Antioxidant 330~ on an unheated rubber roll mill at ambi.ent temperature~ Sixty-gram portions of the resulting composit.ion are sheared for 10 minutes at 145C~ and then ~or 10 minutes at ~'~ 3~
170C. in a ~rabender plastograph.
Polymer 36 is prepared as follows: A 5-gram portion of phthalic anhydride sulfonyl azide and ~ grams of 1~ 3 9 5-trimethyl-2~L~ 9 6-tris(3,5-di-tert-butyl-4~
hydroxybenzyl) ~enzene 9 (Ethy~Antioxidant 330) are added to 499 grams of the base polymer on an unheated rubber roll mill at ambient temperature. Sixty-gr~n portions of the resulting composition are sheared for 10 minutes at 170Co in a Brabender plastographO
Polymer 37 is prepared by the procedure described below for polymer 3~ using 150 grams of the base polymer of ~olymer 36 and 120 grams of maleic anhydride. Note: Polymer 37 varies between Examples and 90 as follows: Example ~ - 40 perce~t ungrafted, 60 percent grafted ~ 1 percent graft; Example 90 - 60 percent ungrafted, ~0 percent grafted - 1.5 percent graft.
Polymer 3~ is prepared as follows: A Werner Pfleiclerer 53-mm twin screw extruder is assembled by end~
to-end attachmen~ o~ 16 barrel sections of 0~5-inch diameker~ Follo~ng a short feed section are four reaction sec-tions (zones 1-4)p one vacuum extraction section (zone 5)g a cooling section (zone 6), and a die section.
Provisions are made for the metering of molten maleic anhydride at the forward part of zone 1. The screws are composed of kneading bloc~;s9 reverse pitch screws; and transport screws arranged to generate 100~200 p.s.1~
pressure in zones 1-4~ no pressure in zone 5, and 500~700 p.s~i. die pressure. The free volume of zones 1-5 is equivalent to two pounds of polymer at the operating temperature. Zones 1-l~ are preheated to 300C~, zone 5 ~3~
to 250Co and zon~ 6, the ero~-h~adg and th~ die to 165~C~
Th~3 Qla~to~r 1~ ~ed to the extru~r in the ~orm o~ chip~ whlch ?aS~ a 0.5~1nch screen. Maleic ar~dride i~ ~et~r~ to th~ extruder ak ~n average f'eed rate o~ 2~1~4015% of the polymer weight. For e~rery 1~0 :~ part~ o~ reac~ant~, 6.,1; part~ of a 1~,5~ ~olutiorl o~
1, 3 ~ 5 ~imeth yl-2, 4, 6 -txiæ ( 3, 5-di ~tert 4-bydro~benzyl benzen~ th;yl@}~ntiox~dant 330) in a¢etone t ~ p~mped 1~ ~nto a mlx~nEs ~eeti~ Ju~t ahead o~ the exl;ra~tion æectlon. m~ extruder ~rew ~p~e~ iæ 12.5 rpm a~d the ~racuu~n ~ection i~ operated at about 25 inch~ Or H~.
The pro~t, extruded at the rate o~ 5.8-6.1 lbs./
~. ha~ a maloi~ anl~d;rid~ ccsn1;ent o~ a~out 1.,5% b~
weight, Four ba~¢he~ totallllig 117.0 gram~ o~ monoamlnQ-t~rminated pol~rcaprolacta~ ~ith an aver~3;e degree o~
poX~merizatlvn o~ 15.3 are added (a~ a powder) to ~our bat¢hes o~ th~ a~ove produet totalling 45~.,8 gram3 on a ru~ber roll m~ll a~ 110C. The~e m~tur~s are then trar~-20 ~rred to an ~l~ctri~all~ heated roll mill and ~orm~d i~toa ~mooth band ~y milling at 225a~Co :E~or 10 minute~"
J?olyner~ 39, 41-45 are 3?repared b~ th~ method Or the a~orem~ntior~ed CaIladian Pater}t 1 032 688 Or Ca~wood but usi~g a varie~y o~ un~aturated ~on~mer~ al; peak reaction ~e~era~ure o~ 325-400~C~ and u~ing a ~tatle mlx~r ~uch as tho~e marketed b~ the Kenic~ Co~apany between the extruder ~crew( 8) and the di.e .
Polymer 40 is prepaxed a~ ln Polg~mer 34 uælng 2~ ~marie acid on the ba~3e pol~mer o~ Polymer 40~e me ~L3~
extruder has 5 kneading blocks and melt temperature was about 350C.
Polymer ~6 is prepared as rOllOws:
Ao Ethylene/Ethyl Hydrogen Maleate Copolymer The random ethylene/ethyl hydrogen maleate copolymer analyzes for 7~2 weight percent incorporated ethyl hydrogen maleate9 007 weigl~ percent incorporated maleic anhydride~ and 0.4 weight percent incorporated maleic acid made by high pressure free radical polymeriza-tionO
B. Blend of Base Polymer and Ethylene/~thyl Hydrogen Maleake A blend is prepared by mixing 12~ grams of the ; ethylene/ethyl hydrogen maleate copolymer of A with 192 - grams of the base polymer on a rubber roli mill at 150C~
for about 5-10 minutes.
Polymer 47 is prepared as follows.
A~ ~thylene/~thyl Hydrogen Maleate Copolymer The random ethylene/ethyl hydrogen maleate copolymer analyzes for 7.0 weight percent ineorporated ethyl hydrogen maleate, 0.~ weight percen~ incorporated maleic anhydride, and 0~4 weight percent incorporated maleic acid made by hi~h pressure free radical polymeriza-tion.
B 2 Blend of Base Polymer and Ethylene/~thyl Hydrogen Maleate A blend is prepared by mi~lng 64 grams of the e~hylene/ethyl hydrogen maleate copolymer of A with 256 grams of the base polymer on a rubber roll mill at 150C.
for abou~ 5~10 minutes.
~37 ~ 3~
Polymer 4~ Blend of Base l'olymer and Ethylene/
Ethyl Hydrogen Maleate Copolymer The general procedure of Example 99 is repeated using 12~ ~rams of the copolymer and 192 grams of the base polymerO
Polymer ~9 is prepared as follows:
A. Ethylene/n-Butyl Hydrogen Maleate Copolymer ~ The random ethylene/n-butyl hydrogen maleate ; copol~ner analyzes for 11~ weight percent incorporated n-butyl hydrogen maleate, 1~2 weight percent incorporated maleic anhydride9 and 0.3 weight percent incorporated maleic acid made by high pressure ~ree radical polymeriza-tionO
B. Blend Or Base Polymer and Ethylene/n-Butyl Hydrogen Maleate A blend is prepared by mixing 64 gra~s of the ethylene/n~butyl hydrogen maleate copolymer of A with 256 gr~ns of the base polymer on a rubber roll mill at 150Co for about 5-10 minutes~
Polymer 50 Base polymer grafted by the method of Polymer 39~ .
Polymer 52 is a mixture of two commercial polymers butadiene/acrylonitrile (BAN) is Firestone FRN
606 and styrene/maleic anhydride made by ARC0 SMA-30009 mixed on a 6" roll mill-Polymer 53 is the BAN described as Polymer 52 Polymer 54 is a blend of styrene butadiene rubber FRS 211 sold by Firestone and ethylene/maleic anhydride (~9/11) made as described :in Polymer 33 Polymer 55 is prepared as follows:
A~ Isobutylene/Isoprene Copol~er~ ~njay ~utyl 3~5 ~3~
The butyl rubber employed is an isobutylene copolymer con~aining about 200 mole percent isoprene uni~s7 The Mooney ~iscosity (ML~ /100C.) is about 45. A.non-- staining antioxidant is present, 000S~0.15% zinc dibutyl-dithiocarbamateO
B~ Phthalic Anhydride Sulfonyl Azide Modified Isobutylene/Isoprene Copolymer Six grams of phthalic anhydride sulfonyl azide are added to 300 grams of the isobutylene/isoprene copolymer of A on an unheated rubber roll mill at ambient temperature.
Grafting is accomplished by heating the resulting composi-tion on a 200Co mill for 10 minutes.
Polymer 56 is prepared as follows:
A~ Polyisobutylene9 Enjay Vistane~ L-~0 The polyisobutylene employed has a Staudinger molecular weight of 709000 and contains a non-staining antioxidant, butylated hydroxyto].ueneO
B~ Phthalic Anhydride Sulfonyl Azide Modified Polyisobutylene Six grams of phthalic anhydride sulfonyl azide : are added to 300 grams of the polyisobutylene of A on an unheated rubber roll mill at ambient temperature. Graft ing is accomplished by heating the resulting composition on a 200C. mill for 10 minutes.
Polymer 57 is a mixture of the base polymer and styrene/maleic anhydride (5/1~ Lytron~ g20 made by Monsanto prepared on a 6" roll millO
Polymer 5~ is a mixture of cis-1,4~polyisoprene having a Mooney viscosity (ML-~/100C.) of about ~59 3 Natsy~ 410 sold by Goodyear Tire & Rubber CoO, and ~1 3~
ethylene/maleis anhydride (90/lO) copolymer made by high pressure, free radical pol~nerization~
Polymer 59 is a mixture of natural rubber Harte~ ~0 sold by ~irestone and ethylene/maleic anhydride described in Polymer 5~0 Polymer 60 is a control of natural rubber used in the blend of Pol~mer 59.
Polymer 61 is prepared as follows: A one-liter 4-neck round-bottom glass flask is charged at room temperature with 375 ml of water~ 300 ml of etllyl ac~late, 12 grams of f~naric acid, 6 ml of a 3Q% of sodium lauryl sulfate in water, 002 gram of sodium hydrosulfite5 and 0~1 ml of dodecyl mercaptan. After the resulting mixture has been sparged with nitrogen, it is heated to 600C.
Copolymeriæation is initiated and rnaintained for two hours at 600C. by gradual addition of a 2% solution of kert-butyl hydroperoxide in water frorn a syringe pump. The emulsion obtained is strained to remove coagulum (35 gra~s) and then coagulated with acetone. Afker the copolymer c~umbs havebeen washed with water three times, they are squeezed and dried in a vacuum oven at ~0C. for 20 hours. A 2~5 gram yield of white copolymer is obtained displaying an inherent viscosity of 4006 deciliters/gram at 30C~
(measured on a solution of 0.1 gram of copolymer in lO0 milliliters of chloroform)0 Pvlymer 62 is prepared as follows^ A one-liter, four-neck round-bottom glass flask is charged at room temperature with 450 ml of water, 360 ml of ethyl acrylate, 144 gr~ms of ethyl hydrogen fumarate? 3.6 ml of ethylene dimethacrylate, 7.2 ml of 30% sodium laurrl sulfate in ~Jater9 0~24 gram of sod:ium hydrosulfite~ and 102 1~0-~ ~ 3~
ml of dodecylmercaptan. After the resulting mixture has been sparged with nitrogen for a half-hour9 it is heated to 43C. Copolymerization is initiated and maintained for six hours at about ~3C~ by gradual addition of about lo 5 ml of a 2~ solution of tert-butyl hydroperoxide in water from a syringe pumpO Heat evolution lessensO
After the mixture has been heated to 40C.~ a one-milliliter portion of the hydroperoxide is added over a one-hour period. There is only a trace of coagulum to remove~ The latex is coagulated with acetone and the crumbs of terpolymer obtained are rinsed three times wikh water and dried in a vacuum oven at ~0C0 for three da~s. The yield: 296~5 grams. Inherent viscosity (measured on a solution of 0.1 gram of terpolymer in chloroform at 30C~) 0.7~ Composition: ethyl acrylate, 95 weight percent; ethyl hydrogen fumarate, 4 weight percent; ethylene dimethacrylate~ 1 weight percentO
Polymer 63 is prepared as follows: A one~
liter four neck round-bottom glass ~lask is charged at room temperature with 450 ml of water, 360 ml of n-butyl acrylateg 1404 gram~ of ethyl hydrogen fumarate, 702 ml of a 30~o solution of sodium lauryl sulfate in watex9 0024 gram of sodium hydrosulfite, and 0.1 ml of dodecyl mercaptanO After the resulting mi~ture has been sparged with nitrogen for a half-hour7 it is heated to 43C. and 2 ml of a 2% solution of tert-butyl hydro~
peroxide are addedO During the next four hours 2 ml Or a lO~o solution of tert~bu-tyl h~droperoxide are introduced. After addition of 0~2~ gram of sodium hydrosulfite and one more milliliter of tert-butyl hydroperoxide~ the mixture is heated to ~0C0 and stirred ~41-~:~3~
30 minu~es longer~ The mixture is once again heatèd to 40~C~; during the final hour at 40Co still another millili~er of te~t-butyl hydroperoxide is addedO After the latex thus prepared has been strained free from 15 grams of coagulum~ the copolymer is obtained by treating .
~he latex with acetone~ The copol~mer crwnbs obtained are ~ashed three times with water and dried in a vacuum oven at ~0C~ The white product weighs 2~3~5 grams and has an i.nherent viscosity of 3.60 (measured at 30Co on a solution of 0.1 gram of copolymer in chloroform)0 It contains 4 weight percent ethyl hydrogen fumarate .
monomer unitsO
Polymer 64 is prepared as follows:
Ao Ethylene/Ethyl Hydrogen Maleate Copol~ner The random copolymer contains about 90 weight percent ethylene monomer units and 10 weight percent ethyl hydrogen maleate monomer units~
B. Ethylene/Propylene Copolymer The random elastomeric ethylene/propylene 20 monomer units and has a Mooney (Ml~ /121Co ) viscosity ~ .
of 51~ It is made in solution in hexane at about 50 Co in an evaporatively cooled continuous reactor in the presence of a coordination catalyst made in situ by introducing VCl~ and dii.sobutyl-aluminum monochloride ~Al:V atomic ratio = 6), C. Preparation of Blend of Ethylene/~thyl Hydrogen Maleate Copolymer and Ethylene/Propylene Copolymer A blend is prepared on a 150Co roll mill using 64 grams of the ethylene/ethyl hydrogen maleate copolymer of' A and 256 grams of the ethylene/propylene copolymcr of B~ Mixing takes about 5 to 10 minutes~ Analysis ~42~
3~6~
indicates that the blend contains lu2 weight percent ethyl hydrogen maleate monomer units~ 0036 weight percent of maleic anhydride monomer units, and less th~n 0.1 weight percent of maleic acid monomer units.
Polymer 65 is prepared as follows~ A 3 gram portion of phthalic anhydride sulfonyl azide is mixed with 300 grams of the el.as~omeric ethylene/propylene copolymer of Part B of Polymer 64 on an unheated rubber roll mill at ambient temperature~ The resulting compositio~ is transferred to 200C~ roll mill and sheared at 200CO for 10 minutes to engraft phthalic anhydride sulfonyl groups onto the ethylene/propylene dipolymer.
Polymer 66 is prepared as follows: The base polymer grafted to ca~ o fumaric acid by method.
of Polymer 39~ The melt flow rate of the grafted polymer is ca. 3 grams/10 minutes by the method of ASTM D~123~ at 2~0C. with a 2160 gram load.
Polymer 67 is a random elastomeric copolymer having a melt index of 10.0 grams/10 minutes4 Polymer 6~ is polyurethan.e elastomer prepared as described in U~ S. Patent 2J729p61~ Texin~ 4gO sold by Mobay.
Polymer 69 contains Herchlo~ C sold by Hercules Inc.
Polymer 70 is prepared as follows~ A 3~54 gram portion of.the monoethyl ester of phthalic anhydride sulfonyl. azide was added to 300 grams of the base polymer on an unhea-ted rubber roll mill at ambient temperature~
One hundred fiI'ty gram portions of the resulting composition are sheared for 10 minu-tes at 200C~
~l~3 Polymer 71 is prepared as Pollow~: A 6.21 gram portion o~ th~ n~nooctadecyl ester of phthalic anhydr~ de sul~onyl azlde was add~d to 300 grams of the ba~e polymer of an unheated rubber roll mill at ambi ent ~emperature. One hundred fifty gram portlons o~ the resulk~rlg compo~ition ~re sheared for 10 minutes at 200 C .
Polymer r2 ls prepared by:~:hi~h pressure :Eree radical polymerization~
Polymer 73 ls the ba~e polymer.
Polymer 74 i~ an ethylene-butene copolymer made by the Du Pont high der~slty lo~ pressure process;
polymer d~nsity 0.937 gms/cc.
Polymer 75 is an ethylene homopolymer made by high pre~sure ~ree rad~cal polymeriz~.tion, polymer denslty O, 920 g;m~/cc .
Polymer 76 is an ethylene homopolymer ~ade by .
the Du Pont h~gh density low presæure process3 polymer den~ity 0.957 gms/cc and melt index (Condition E) o~
20 ~.8 before graftlng~ Grafted by the me~od of Poly~er 39.
Polymer 77 is grafted by method o~ Polymer 39.
Polymer 78 iæ DIENE* 35 sold by Firestone Rubber Co.
* denotes trade mark 3)?164 TABI.E ~
_ABLE OF ACRONYMS
E ethylene IBA i.sobutyl acrylate MAA methacrylic acid MA methyl acrylate MAME monoethyl ester of maleic anhydride HMD hexarnethylene diamine VA vinyl acetate MMA methyl methacrylate CO carbon monoxide AA acrylic acid HEMA hydroxyeth~L methacrylate SMA stearyl methacrylate nBA normal butyl acrylate 2EHMA 2--ethyl hexy1.methacrylate MVE methyl vinyl ether P~Anh maleic anhydride G~ glycidyl methacrylate EDM~ ethylene glycol dimethacrylate EA ethyl acryla.te ~A fumaric acid BuHM butyl hydrogen maleate PASA phthalic anhydricle sulfonyl azide SMA (3000) styrene maleic anhydride copolymer FA~E monoethyl ester of furnaric acid P propylene BASA benzoic acid sulfonyl azide BAN butadiene acl~lonitrile 3 SBR styrene butadiene rubber -g- graft These Examples prepared according to the procedure described above.are set forth in Table 30 ~l45-~ 33 ~ ~ ~
Control A is molded of an inter~ediate molecular weight 66 nylon. Examples l through 5 are a concentration series using a terpol~mer of ethylene7 isobutyl acrylate and methacrylic acid partially neutralized wi~h zinc~ At the 30~ concentration the notched Izod of a molded bar is over lO ft. lbs./inch at the gate end and the far endO At 20~o the material is tough at one end of the molded bar and at lower concentra-tions toughness is in the range of prior art materials at higher concentrations. Controls B through E are from the prior art and show that the higher modulus copolymer of ethylene and methacrylic acid is less effective in toughening polyamide matrix l than is the lower modulus terionomer O
Example 6 in comparison with Example 5 shows that reduction in molecular weight of` the matrix causes reduced notched Izod in a composite structure. F.xamples 7 to lO
show the e~fect of increasing molecular weight of the . .
matrix toughened with 20 weight percent Or the terionomer.
EY.ample lO with the highest molecular weight matrix pro-vides toughening with the ethylene terpolymer ionomer so that at the 20~o level toughness is approximately e~uivalent to that obtained at the 30~ level in matrix l.
Examples ll and l2 should be compared with Examples 4 and 5 to show the range of reproducibility in what were supposed to be identical materials. Comparing Controls F and G with Controls D and E show similar reproducibility in prior art materials.
Controls H, I and J show that low ethylene, low modulus materials are not eff'ective toughening ~1~6~
~.~ 33~
agents when no adherent site is present. In comparison9 Example 13 where an adherent site is present, gives very high toughness. Note that in comparison with Example lk the only major difference between the polymers is the presence of the ionomer group in Example 13.
Examples 14 and 15 show the strong toughening effect of the unneutralized maleic acid monoethyl ester terpol~mer in both an intermediate molecular weight polyamide with balanced end groups (Example 14) and in ~xample 15 a polyamide matrix with high amine ends. The high amine ends apparently ~rovide more effective interactisn with the dispersed acid toughening agent than the polyamide with a normal balance o~ end groups.
. When an ionomeric pol.ymer is used there is generally less advantage in toughening a high amine ended nylon~
Compare Example 16 with Example 4~
Examples 17 through 20 comprise a concentration series of the free acid toughening agent in high amine ended polyamideO ~t a concentration of 5% significant toughening is obtained. In fact, the material of Example 1~ achieves ~ery close to the toughness of prior art material (Control C) at 1/4 the toughener concentration and with consequently substantially better tensile strength and modulus~ Examples 19 and 21 illustrate the effect of the difference in concentration of amine ends in the polyamide~ The effect at the 10% toughener concentration le~el is more dramatic than at the 20%
level where the maximum in ductility as characteriæed by notched Izod is attained~
~xample 23 shows thak the acid polymer slightly -~7--~ 3~
neutralized with hexamethylene diamine is an effective toughening agent for nylon.
Examples 229 25 and 26 show the effect of various degrees of neutralization to prepare ionomers used for toughening polyamides with balanced end groups.
In a nylon rnatrix with balanced ends the zinc ionomer is a more effective pol~ner than the free acid polymer.
Examples 2~ and 2S differ primarily in details of the neutralization procedure which was carried out on a two roll mill and show that proper neutralizakion must be obtained in order to develop the most effective toughen~
ing. Conditions fo~ neutralization are given in Table lo Xt will be obvious to those skilled in the art that for any particular combination of pol~ner and matrix~
optimization of processing conditions must be used to - obtain the best resultO
Examples 2~ through Control L include three additional series where zinc neutralization was carried out from O to 100% or higher for three different toughening systems. In all three cases where a nylon with balanced ends was used preferred neutralization is in the range of lOO~ or below. Example 36 and Control L
illustrate that neutralization at 125% can give reduced toughness, so that for practical purposes neutralization in the range of 100% or below for toughening agents used in an amide with balanced ends is preferred~
Examples ~2 through ~5 show that calcium, lithi~nJ potassiurn and sodium ionomers can also be effective toughening agents whcn a soft organic moieky~
e.g., ethy]ene/methyl acrylate/monoethyl ester of maleic ~3~ 4 anhydride (E/MA/MA~ is used with them. Example ~6 illustrates that the antimony ionomer has some toughening effect~ In most of the ionomerization experiments either the metal hydroxide or ace~ate was used as the neutrali~ing agent but other salts would also be effective. Examples ~7 and 4~ illustrate that organic salts of the metal ions may also.be used.
Examples 49 and 50 in comparison with Examples 3 and 4 show that mixing small amounts of ethylene/methyl acrylate/maleic anhydride ester ionomers with ethylene/
; isobutylacrylate/methacrylic acid ionomers substantially improve the uniformity of compositions of the latter ionomer and polyamide aloneO
Examples 51 and 52 illustrate that lower molecular weight polyamide can be effectively toughenecl by the E/MA/MAME system. The improvement in notched I~od above the base resin shown in Example 53 suggests that moderately greater concentration of polymer would give substa~tial toughness in nylon of this low molecular 20 - weigh~.
Examples 5~ through 5~ illustrate the potential of several different ethylene terpolymer ionomers ~or toughening polyamides4 The results of Examples 59 and 60 suggest that higher molecular weight polymers are more effective than lower molecular weight materials.
A broad range of molecular weights can be employed~
Example 61 iIl comparison with Example 62 demons~rates the effectiveness of an ethylene/vinyl acetate/methacrylic - acid terpolymer ionomer in a high amine end nylon in comparison with the same polymer in a nylon with balanced ~ 3 amine ends~
Examples 63 and 61~ demonstrate the effectiveness o~ an aclditional ethylene terpolymerg the free acid in high amine end nylon and the ionomer in nylon with ~alanced end groups.
Controls M and N again show the need for an : adherenk siteO In ~xample 6~ ethylene/vinyl acetate/C0 terpGlymer has modest toughening effect on nylon with balanced end groupsO In comparison~ Examples 66 and 67 illustrate more effective toughening where amine ended nylon is believed to offer more effective interaction.
than balanced nylon with the carbonyl groups in the ter~
polymer. (Results with E/VA polymers have been less reproducible than with other pol~nersa apparently because o~ marginal stability at processing temperatures for 6~
nylonO) Example 69 illustrates the effect of a blend of two previously used polymers with the mixture providing good uni~ormity of toughness. ~xarnple 70 illustrates mixing two pol~ners, the polymers used in Control N and Examples 3 and ~ t~ provide substantially better tough~
ness than when either pol~er is used alone~ Similar effects of the mixtures of two pol~ners are shown in Examples 71 and 720 Cornparison of Example 73 with Control N shows that addition Or a small arnount of an adherent polymer with a low ~odulus nonadherent polymer can substan-tially increase its toughening capaci~y~
~ xamples 74 to 7~ cornprise a variety of ethylene terpolymers with C0 as the reactive agent for the polyamide matriY~. Several of' these examples illustra-te toughness ~5o ~ 3~
approaching notched I~od of 10 at both ends of the bar and suggest that many of these materials could achieve 10 ~otched ~zod uniformly with optimization of composition and processing, or some increase in toughener concentra-tionO
Examples 79$ ~0 and ~1 are ethylene/vinylacetate terpolymers with a variety of functional groups all of which show improvement in toughening compared with Control No Example ~2 is a polymer containing ~
monomeric en-tities which also indicates that optimiza-tion would yield notched Izods over 10 throughout the length of the molded bar9 though the cross-linking effect Or ethylene glycol dimethacrylate ~Control Q) may be deleterious~
Examples ~3 through 103 illustrate the wide toughening capability of ethylene~propylene copolymers which contain small amounts of dienes suitable for attaching adherent sites. As the examples show a variety of these polymers of various molecular weight and ratios o~ ethyiene to propylene and diene content may be employed. mey may be used in polyamide with balanced end groups or high amine ends and a wide variety of adherent groups may be grafted thereto. Example ~69 in comparison with Example ~79 illustrates that at low concentrations of adherent sites, the monoacid is less effective than the dicarboxylic acid~
Example 102 illustrates that an ionomer Or said copolymer is effective9 and Example 103 illustrates that said copolymers toughen low molecular weight nylon.
ExampleslO4 through 112 illustrate that a wide variety - ~33~64 of low modulus polymers can be used to toughen nylon as long as an adherent group is present. The examples include most of the commonly available low cost synthetic and natural rubbers including butadiene/acrylonitrile rubberS styrene/butadiene rubber, buna rubber, isobutylene, isoprene9 natural rubber9 ethyl acrylate9 butyl acrylate rubbers, etc~ Controls 0 and P for Examples 104 and 1109 respectively9 show the importance of a site for adhesion to the matrix.
Examples 113 and 114 illustrate that ethylene/
propylene copolymer can produce results similar to ethylene/propylene/diene terpolymer (~xamples ~3 to 103) provided that polymer with sites for adherence to the matrix are mixed in (~xample 113) or the appropriate ! ,:
site is grafted onto the copolymer ~Example 11~) by appropriate means~
The concentration serles of the ethylene/
isobutyl acrylate/methacrylic acid ionomer in matrix 1 comprising Examples 3~ 5~ 115$ Control R and Control S
discloses that notched Izod well over 20 ft. lbs./inch can be obtained at high loadings of polymer~ Significant loss in tensile strength and stiffness occur at high loadings with drastic loss over 50%p presumably because of phase inversion.
Examples 1169 117 and 11~ show that 612 nylon can also be toughened with an ionomeric system~
Consisten~ results are obtained in Samples 119 and 120 and Control T.
Nylon 6 is very effectively toughened by the zinc neutralized ionomer of E/MA/~AME~ Control U and Example 121~ Lower levels of tou~hener can be used.
Huls nylon 129 Control V is also effectively toughened by E/MA/MAME ionomer9 Exarnple 122~ and E/IBA/
MAA9 Example 123. Urethane rubbers are sufficiently stable at the melt temperature of nylon 12 to be ef*ec~ive polymers~ Example 124 : ~ylon 11 is toughened by E/P/diene-g-FA~
Examples 125 and 126.
Example 127 is an example of toughening a nylon copolyrnerO
~xample 12~ illustrates toughening of 66 nylon with balanced ends by an ethylene/propylene/1,4-hexadiene/
norbornadiene polymer which contains approximately 1D4 weight percent fumaric acid. Similar results, Examples 129 and 130, are ob~ained with similar type polymers which are grafted with esters of phthalic anhydride sulfonyl azide~
Toughening of an amorphous pol~amide with previously disclosed polymers is shown in Examples 131~133.
The same polymers toughen a polyamide contain-ing a cyclic aliphatic structure (Examples 134-136).
Examples 137-141 in comparison with Control Y
illustrate the toughening effectiveness of fumaric acid grafted ethylene/propylene/1,4~hexadiene/norborna-diene pol~ner at low concentrations~
Example 142 shows the effectiveness of a mixture of a soft (ethylene/methacrylate 46/54) and an adherent polymer (ethylene/acrylic acid ~0/20).
Examples 144 to 149 and Controls Z and AA
illustrate the effect of mixing branched pol.yethylenes -~3-~ ~ ~ 3 ~;4 of varying density wikh fumaric acid gra~ted e-thylene/
propylene/l~ hexadiene/norbornadiene polymer. Examples 14~ and Control Z were prepared by dry blending all the components and feeding to the twin screw extruder; Con~rol AA and Examples 145 to 149 were prepared by milling the hy~rocarbon polymers together before feeding to the extruder with the polyamideO Despite some variability in results9 the examples illustrate the following points.
1~ mixtures with softer polyethylene are more effective thall those with higher modulus polyethylene~ (2) a soft adherent polymer can render a mixture effecti~eg (3) comparisonwith Control BBp which was prepared by first extruding the soft adherent polymer with the matrix and then reextruding to add the polyethylene~ shows -thak the materials of the mixture must coexisk in the same particles to provide ef`~ective toughening~ Control CC
shows that S~o of this polymer alone is not enough to confer very high levels o~ toughening on the matrix (comparison with Example 141 reflects the influence of amine ends on the matrix~
Comparison of Control DD and Example 150 illustrates the effect of difference in polymer modulus when degree of adherence is about identical.
Example 151 illustrates an effective mixture of butadiene rubber and an adherent material.
Examples 15~ and 154, in comparison with Example 152, and F~amples 156 through 160; in comparison with Example 1559 illustrate that a variety of additives, eOg~ up to about 405~0 by weight, can be compounded into a toughPned composition without materially affecting ~51,-~ 6 ~
mechanical propertiesO Example 153 contains a lubricant, ~xample 154 a heat stabilizer and ~xamples 156~160 contain colorants~ In these experiments the additives were com-pounded into ~xamples 152 and 155 in a twin screw extruder with a vacuum port~ .
~ xample 162 was prepared by compounding 33 weight percent chopped glass fiber into the product of Example 161, on a single screw extruder with a vacuum port. The resultant product has a notched Izod nearly twice that of commercially available glass reinforced 66 nylon while -reta.ining strength and stiffness approaching that of untoughened materiaI~ ~xample 163 illustrates similar improvement when mineral filler is added to polyamideO
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These ~xamples illustrate uniformity o~
toughness in a 3 inch by five inch by 1/~ inch thick molded plaque. Samples are cut from this plaque so that notched Izod may be determined near and far from the gate in the flow and transvers~ directions. Utilizing the procedure described previously above thermoplastic compo-sitions are prepared having the composition set f orth in Table 40 Controls 1 and 3 represent toughened prior art 10 polya~lide compositionsc E~.amples 164 to 167 represent composi~ions of this invention. Examples 166 and 1679 in particular, have uniformly high toughness with 20 percent by weight polymer added to the polyamide matrixO
The data in Table 5 illustrate the effect of - decreasing notch radius on certain prior art compositions and preferred compositions of the invention. The results show that the prior art materials are more sensitive to this effect than the pre~erred compositions of this invention.
A further test which demonstrates the effec~ of notched radius on toughness is as follGws~ Each of the following materials was scra~ched to a depth of 20 mils with a raæox blade which gives a notch radius of about 0.~ mil and was tested using a Gardner Impact Tester IG~1115 manufactured by Gardner Laboratories9 IncO, Bethesda, Maryland~ The break occurred at the following loadings.
Matrix 1 6 inch pounds Control B ~ inch pounds Using the same procedure a material as described in Example 5 of the present invention broke at 69 inch pvunds.
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A blend of ~5 weight percent of Matrix 1 and 15 weight percent of Polymer 66 containing additives of Example 15L~ was melt extruded into the form of a film.
The blend was extruded at a temperature in the range of 2~0-2~5C. in a Sterling extruder through an ~-inch (20~32 centimeters~ wide Johnson die maintained at a temperature of about 290-295C. The molten film was extruded onto the surface of a rotating (at about 15 feet (4.57~ meters) per minute) quench drum maintained at a temperature of.about 70Co Full wire electros-tatic pinning was used to insure uniform quenching of the cast film which was 10 mils (250 microns) in thickness~ Sheets9 ~ inc~es by 4 inches (10.16 centimeters by 10.16 centi~-meters)9 cut from the roll of cast film were stretched simultaneousiy ~in a T. M. Long Co. stretcher) 2.5X in mutually perpendicular directions at a tempera~ure of about 230C~ The cast film stretched uniformly in all directions. Matrix 1 is extremely difficult to cast into a film hence a control of Matxix 5 was utilized. A
cast film of Matrix 5 without Polymer 66 was difficult, to stretch uniformly and tended to exhihit line drawingO
Another sample of` the cast f'ilm was thermo~
formed7 after being preheated for about ~0 seconds in an oven heated to about 210C., into the shape of a dish 1~5 inches (3.~1 centimeters) deep by 5 inches (12.7 centimeters) in diameter. The male portion of the dish mold was heated to about ~00C. and the female portion.
was at about 160C~
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Polymers 1, 2, 6to 13, 28 t4 31 are prepared as described in Rees U. S. Pa~ent 3 ,264,272 .
Polymer 5 is prepared as described in Greene Belgian Patent 818~609 with the neutralizations using the procedure described in Rees [J.S. Pater~t 3~264,272 ~rlth -the exception of the ~D neutralization (Example 23) whlch is described in Rees U~,S. Patent 3,471/460.
Polymers 3" 49 14J 15, 19, 20, 21 are made by high preæsure, free radical polymerization, Polymers 16 to 183 23 ~o 27 are p:repared as described in EIammer U.S. Patent 3,780,140.
Pol~mer 22 is COMER~ 9300 ~ade by UN on Car~ide.
Polymers 32, 51 are the ind cated base polymer gra~ted aceording ~o Example 13B o~ Caywood Canadian P~tent 1~032J688~ which issued 1978 June o6.
1'he base polymers o:~ the indicated polymers are ~ollows:
Polymer 33 ethylene/propyle~e/1~4-he~adiene (64/32/~ ~ooney vlscoslty ASTM D-1646 ~ML-1~4~121C.) o~ about 45.
Polymers 34, 35 ethylene/propylene/194~hexadiene/
2~5-norb~die~e (54/40/6/0.35) Mooney viscosity about 25.
Polymers 36-38, 46-49, 70~ 71 ethylene/
propylene/1~4-hexadiene (62/32/6) Mooney viscosity abou~
Polymers 399 41-45~ 50~ 57~ 66, 73, 77 ethylene~
propylene/1~4-hexadiene/2~5-norbornadiene (68/26/6~0.15) Mooney viscosity about 33.
Pol~mer 40 e~hylene/propylene/1,4-hexadlene/
~ ~ 33 ~ ~
295-norbornadiene ~71/23/6/0.5) Mooney viscosity about . 2S.
All the above base polymers are prepared by co-polymerizing the monomers in the presence of a coordina-tion catalys~ system such as diisobu-~ylaluminu~ chloride.
and vanadium oxytrichloride~ Copolymerization may be con~
duc~ed in an inert solvent or in a slurry or particle form reactorO Details of their preparation are given, for exam~le ? in U~ S. Patents 2,933,4~0; 2 7 962 9 451;
3~000,~; 3,093~620; 3,093 7 621; 3 9 063p973; 3p1~7~230, 3,154,52~; 3~260,70~; and in M. Sittig; "Stereo Rubber and Other Elastomer Processes", Noyes DeYelopment Cor-portion~ Park Ride, N~J. 9 1967~ as well as U.S. 3,~199591.
Polymer 33 is a mixture of the above base pol~mer and ethylene/maleic anhydride (~9/11) made by high pressure9 free radical polyrnerization.
Polymer 34 is tumbled overnight with 7 weight p~rcent of MAME on 1/4 inch cubes of base polymer and ~:
extruded on a 2~ mm Werner Pfleiderer extruder fitted ~ith a vacuum port and 4 kneading blocksO The melt temperature is about 315C. and hold~up time 2 to 4 minutes. The product is quenched~ cut and driedO
Polymer 35 is a mixture of 9~2 grams of m-carboxy benzene sulfonyl azide and 3600 grams of blanc fixe added to 350 grams of the base polymer and 0~7 gram of 173,5-tri.methyl 2~4,6-tris~395~di tert-butyl-l~
hydroxybenzyl) benzene (~thy~ Antioxidant 330~ on an unheated rubber roll mill at ambi.ent temperature~ Sixty-gram portions of the resulting composit.ion are sheared for 10 minutes at 145C~ and then ~or 10 minutes at ~'~ 3~
170C. in a ~rabender plastograph.
Polymer 36 is prepared as follows: A 5-gram portion of phthalic anhydride sulfonyl azide and ~ grams of 1~ 3 9 5-trimethyl-2~L~ 9 6-tris(3,5-di-tert-butyl-4~
hydroxybenzyl) ~enzene 9 (Ethy~Antioxidant 330) are added to 499 grams of the base polymer on an unheated rubber roll mill at ambient temperature. Sixty-gr~n portions of the resulting composition are sheared for 10 minutes at 170Co in a Brabender plastographO
Polymer 37 is prepared by the procedure described below for polymer 3~ using 150 grams of the base polymer of ~olymer 36 and 120 grams of maleic anhydride. Note: Polymer 37 varies between Examples and 90 as follows: Example ~ - 40 perce~t ungrafted, 60 percent grafted ~ 1 percent graft; Example 90 - 60 percent ungrafted, ~0 percent grafted - 1.5 percent graft.
Polymer 3~ is prepared as follows: A Werner Pfleiclerer 53-mm twin screw extruder is assembled by end~
to-end attachmen~ o~ 16 barrel sections of 0~5-inch diameker~ Follo~ng a short feed section are four reaction sec-tions (zones 1-4)p one vacuum extraction section (zone 5)g a cooling section (zone 6), and a die section.
Provisions are made for the metering of molten maleic anhydride at the forward part of zone 1. The screws are composed of kneading bloc~;s9 reverse pitch screws; and transport screws arranged to generate 100~200 p.s.1~
pressure in zones 1-4~ no pressure in zone 5, and 500~700 p.s~i. die pressure. The free volume of zones 1-5 is equivalent to two pounds of polymer at the operating temperature. Zones 1-l~ are preheated to 300C~, zone 5 ~3~
to 250Co and zon~ 6, the ero~-h~adg and th~ die to 165~C~
Th~3 Qla~to~r 1~ ~ed to the extru~r in the ~orm o~ chip~ whlch ?aS~ a 0.5~1nch screen. Maleic ar~dride i~ ~et~r~ to th~ extruder ak ~n average f'eed rate o~ 2~1~4015% of the polymer weight. For e~rery 1~0 :~ part~ o~ reac~ant~, 6.,1; part~ of a 1~,5~ ~olutiorl o~
1, 3 ~ 5 ~imeth yl-2, 4, 6 -txiæ ( 3, 5-di ~tert 4-bydro~benzyl benzen~ th;yl@}~ntiox~dant 330) in a¢etone t ~ p~mped 1~ ~nto a mlx~nEs ~eeti~ Ju~t ahead o~ the exl;ra~tion æectlon. m~ extruder ~rew ~p~e~ iæ 12.5 rpm a~d the ~racuu~n ~ection i~ operated at about 25 inch~ Or H~.
The pro~t, extruded at the rate o~ 5.8-6.1 lbs./
~. ha~ a maloi~ anl~d;rid~ ccsn1;ent o~ a~out 1.,5% b~
weight, Four ba~¢he~ totallllig 117.0 gram~ o~ monoamlnQ-t~rminated pol~rcaprolacta~ ~ith an aver~3;e degree o~
poX~merizatlvn o~ 15.3 are added (a~ a powder) to ~our bat¢hes o~ th~ a~ove produet totalling 45~.,8 gram3 on a ru~ber roll m~ll a~ 110C. The~e m~tur~s are then trar~-20 ~rred to an ~l~ctri~all~ heated roll mill and ~orm~d i~toa ~mooth band ~y milling at 225a~Co :E~or 10 minute~"
J?olyner~ 39, 41-45 are 3?repared b~ th~ method Or the a~orem~ntior~ed CaIladian Pater}t 1 032 688 Or Ca~wood but usi~g a varie~y o~ un~aturated ~on~mer~ al; peak reaction ~e~era~ure o~ 325-400~C~ and u~ing a ~tatle mlx~r ~uch as tho~e marketed b~ the Kenic~ Co~apany between the extruder ~crew( 8) and the di.e .
Polymer 40 is prepaxed a~ ln Polg~mer 34 uælng 2~ ~marie acid on the ba~3e pol~mer o~ Polymer 40~e me ~L3~
extruder has 5 kneading blocks and melt temperature was about 350C.
Polymer ~6 is prepared as rOllOws:
Ao Ethylene/Ethyl Hydrogen Maleate Copolymer The random ethylene/ethyl hydrogen maleate copolymer analyzes for 7~2 weight percent incorporated ethyl hydrogen maleate9 007 weigl~ percent incorporated maleic anhydride~ and 0.4 weight percent incorporated maleic acid made by high pressure free radical polymeriza-tionO
B. Blend of Base Polymer and Ethylene/~thyl Hydrogen Maleake A blend is prepared by mixing 12~ grams of the ; ethylene/ethyl hydrogen maleate copolymer of A with 192 - grams of the base polymer on a rubber roli mill at 150C~
for about 5-10 minutes.
Polymer 47 is prepared as follows.
A~ ~thylene/~thyl Hydrogen Maleate Copolymer The random ethylene/ethyl hydrogen maleate copolymer analyzes for 7.0 weight percent ineorporated ethyl hydrogen maleate, 0.~ weight percen~ incorporated maleic anhydride, and 0~4 weight percent incorporated maleic acid made by hi~h pressure free radical polymeriza-tion.
B 2 Blend of Base Polymer and Ethylene/~thyl Hydrogen Maleate A blend is prepared by mi~lng 64 grams of the e~hylene/ethyl hydrogen maleate copolymer of A with 256 grams of the base polymer on a rubber roll mill at 150C.
for abou~ 5~10 minutes.
~37 ~ 3~
Polymer 4~ Blend of Base l'olymer and Ethylene/
Ethyl Hydrogen Maleate Copolymer The general procedure of Example 99 is repeated using 12~ ~rams of the copolymer and 192 grams of the base polymerO
Polymer ~9 is prepared as follows:
A. Ethylene/n-Butyl Hydrogen Maleate Copolymer ~ The random ethylene/n-butyl hydrogen maleate ; copol~ner analyzes for 11~ weight percent incorporated n-butyl hydrogen maleate, 1~2 weight percent incorporated maleic anhydride9 and 0.3 weight percent incorporated maleic acid made by high pressure ~ree radical polymeriza-tionO
B. Blend Or Base Polymer and Ethylene/n-Butyl Hydrogen Maleate A blend is prepared by mixing 64 gra~s of the ethylene/n~butyl hydrogen maleate copolymer of A with 256 gr~ns of the base polymer on a rubber roll mill at 150Co for about 5-10 minutes~
Polymer 50 Base polymer grafted by the method of Polymer 39~ .
Polymer 52 is a mixture of two commercial polymers butadiene/acrylonitrile (BAN) is Firestone FRN
606 and styrene/maleic anhydride made by ARC0 SMA-30009 mixed on a 6" roll mill-Polymer 53 is the BAN described as Polymer 52 Polymer 54 is a blend of styrene butadiene rubber FRS 211 sold by Firestone and ethylene/maleic anhydride (~9/11) made as described :in Polymer 33 Polymer 55 is prepared as follows:
A~ Isobutylene/Isoprene Copol~er~ ~njay ~utyl 3~5 ~3~
The butyl rubber employed is an isobutylene copolymer con~aining about 200 mole percent isoprene uni~s7 The Mooney ~iscosity (ML~ /100C.) is about 45. A.non-- staining antioxidant is present, 000S~0.15% zinc dibutyl-dithiocarbamateO
B~ Phthalic Anhydride Sulfonyl Azide Modified Isobutylene/Isoprene Copolymer Six grams of phthalic anhydride sulfonyl azide are added to 300 grams of the isobutylene/isoprene copolymer of A on an unheated rubber roll mill at ambient temperature.
Grafting is accomplished by heating the resulting composi-tion on a 200Co mill for 10 minutes.
Polymer 56 is prepared as follows:
A~ Polyisobutylene9 Enjay Vistane~ L-~0 The polyisobutylene employed has a Staudinger molecular weight of 709000 and contains a non-staining antioxidant, butylated hydroxyto].ueneO
B~ Phthalic Anhydride Sulfonyl Azide Modified Polyisobutylene Six grams of phthalic anhydride sulfonyl azide : are added to 300 grams of the polyisobutylene of A on an unheated rubber roll mill at ambient temperature. Graft ing is accomplished by heating the resulting composition on a 200C. mill for 10 minutes.
Polymer 57 is a mixture of the base polymer and styrene/maleic anhydride (5/1~ Lytron~ g20 made by Monsanto prepared on a 6" roll millO
Polymer 5~ is a mixture of cis-1,4~polyisoprene having a Mooney viscosity (ML-~/100C.) of about ~59 3 Natsy~ 410 sold by Goodyear Tire & Rubber CoO, and ~1 3~
ethylene/maleis anhydride (90/lO) copolymer made by high pressure, free radical pol~nerization~
Polymer 59 is a mixture of natural rubber Harte~ ~0 sold by ~irestone and ethylene/maleic anhydride described in Polymer 5~0 Polymer 60 is a control of natural rubber used in the blend of Pol~mer 59.
Polymer 61 is prepared as follows: A one-liter 4-neck round-bottom glass flask is charged at room temperature with 375 ml of water~ 300 ml of etllyl ac~late, 12 grams of f~naric acid, 6 ml of a 3Q% of sodium lauryl sulfate in water, 002 gram of sodium hydrosulfite5 and 0~1 ml of dodecyl mercaptan. After the resulting mixture has been sparged with nitrogen, it is heated to 600C.
Copolymeriæation is initiated and rnaintained for two hours at 600C. by gradual addition of a 2% solution of kert-butyl hydroperoxide in water frorn a syringe pump. The emulsion obtained is strained to remove coagulum (35 gra~s) and then coagulated with acetone. Afker the copolymer c~umbs havebeen washed with water three times, they are squeezed and dried in a vacuum oven at ~0C. for 20 hours. A 2~5 gram yield of white copolymer is obtained displaying an inherent viscosity of 4006 deciliters/gram at 30C~
(measured on a solution of 0.1 gram of copolymer in lO0 milliliters of chloroform)0 Pvlymer 62 is prepared as follows^ A one-liter, four-neck round-bottom glass flask is charged at room temperature with 450 ml of water, 360 ml of ethyl acrylate, 144 gr~ms of ethyl hydrogen fumarate? 3.6 ml of ethylene dimethacrylate, 7.2 ml of 30% sodium laurrl sulfate in ~Jater9 0~24 gram of sod:ium hydrosulfite~ and 102 1~0-~ ~ 3~
ml of dodecylmercaptan. After the resulting mixture has been sparged with nitrogen for a half-hour9 it is heated to 43C. Copolymerization is initiated and maintained for six hours at about ~3C~ by gradual addition of about lo 5 ml of a 2~ solution of tert-butyl hydroperoxide in water from a syringe pumpO Heat evolution lessensO
After the mixture has been heated to 40C.~ a one-milliliter portion of the hydroperoxide is added over a one-hour period. There is only a trace of coagulum to remove~ The latex is coagulated with acetone and the crumbs of terpolymer obtained are rinsed three times wikh water and dried in a vacuum oven at ~0C0 for three da~s. The yield: 296~5 grams. Inherent viscosity (measured on a solution of 0.1 gram of terpolymer in chloroform at 30C~) 0.7~ Composition: ethyl acrylate, 95 weight percent; ethyl hydrogen fumarate, 4 weight percent; ethylene dimethacrylate~ 1 weight percentO
Polymer 63 is prepared as follows: A one~
liter four neck round-bottom glass ~lask is charged at room temperature with 450 ml of water, 360 ml of n-butyl acrylateg 1404 gram~ of ethyl hydrogen fumarate, 702 ml of a 30~o solution of sodium lauryl sulfate in watex9 0024 gram of sodium hydrosulfite, and 0.1 ml of dodecyl mercaptanO After the resulting mi~ture has been sparged with nitrogen for a half-hour7 it is heated to 43C. and 2 ml of a 2% solution of tert-butyl hydro~
peroxide are addedO During the next four hours 2 ml Or a lO~o solution of tert~bu-tyl h~droperoxide are introduced. After addition of 0~2~ gram of sodium hydrosulfite and one more milliliter of tert-butyl hydroperoxide~ the mixture is heated to ~0C0 and stirred ~41-~:~3~
30 minu~es longer~ The mixture is once again heatèd to 40~C~; during the final hour at 40Co still another millili~er of te~t-butyl hydroperoxide is addedO After the latex thus prepared has been strained free from 15 grams of coagulum~ the copolymer is obtained by treating .
~he latex with acetone~ The copol~mer crwnbs obtained are ~ashed three times with water and dried in a vacuum oven at ~0C~ The white product weighs 2~3~5 grams and has an i.nherent viscosity of 3.60 (measured at 30Co on a solution of 0.1 gram of copolymer in chloroform)0 It contains 4 weight percent ethyl hydrogen fumarate .
monomer unitsO
Polymer 64 is prepared as follows:
Ao Ethylene/Ethyl Hydrogen Maleate Copol~ner The random copolymer contains about 90 weight percent ethylene monomer units and 10 weight percent ethyl hydrogen maleate monomer units~
B. Ethylene/Propylene Copolymer The random elastomeric ethylene/propylene 20 monomer units and has a Mooney (Ml~ /121Co ) viscosity ~ .
of 51~ It is made in solution in hexane at about 50 Co in an evaporatively cooled continuous reactor in the presence of a coordination catalyst made in situ by introducing VCl~ and dii.sobutyl-aluminum monochloride ~Al:V atomic ratio = 6), C. Preparation of Blend of Ethylene/~thyl Hydrogen Maleate Copolymer and Ethylene/Propylene Copolymer A blend is prepared on a 150Co roll mill using 64 grams of the ethylene/ethyl hydrogen maleate copolymer of' A and 256 grams of the ethylene/propylene copolymcr of B~ Mixing takes about 5 to 10 minutes~ Analysis ~42~
3~6~
indicates that the blend contains lu2 weight percent ethyl hydrogen maleate monomer units~ 0036 weight percent of maleic anhydride monomer units, and less th~n 0.1 weight percent of maleic acid monomer units.
Polymer 65 is prepared as follows~ A 3 gram portion of phthalic anhydride sulfonyl azide is mixed with 300 grams of the el.as~omeric ethylene/propylene copolymer of Part B of Polymer 64 on an unheated rubber roll mill at ambient temperature~ The resulting compositio~ is transferred to 200C~ roll mill and sheared at 200CO for 10 minutes to engraft phthalic anhydride sulfonyl groups onto the ethylene/propylene dipolymer.
Polymer 66 is prepared as follows: The base polymer grafted to ca~ o fumaric acid by method.
of Polymer 39~ The melt flow rate of the grafted polymer is ca. 3 grams/10 minutes by the method of ASTM D~123~ at 2~0C. with a 2160 gram load.
Polymer 67 is a random elastomeric copolymer having a melt index of 10.0 grams/10 minutes4 Polymer 6~ is polyurethan.e elastomer prepared as described in U~ S. Patent 2J729p61~ Texin~ 4gO sold by Mobay.
Polymer 69 contains Herchlo~ C sold by Hercules Inc.
Polymer 70 is prepared as follows~ A 3~54 gram portion of.the monoethyl ester of phthalic anhydride sulfonyl. azide was added to 300 grams of the base polymer on an unhea-ted rubber roll mill at ambient temperature~
One hundred fiI'ty gram portions of the resulting composition are sheared for 10 minu-tes at 200C~
~l~3 Polymer 71 is prepared as Pollow~: A 6.21 gram portion o~ th~ n~nooctadecyl ester of phthalic anhydr~ de sul~onyl azlde was add~d to 300 grams of the ba~e polymer of an unheated rubber roll mill at ambi ent ~emperature. One hundred fifty gram portlons o~ the resulk~rlg compo~ition ~re sheared for 10 minutes at 200 C .
Polymer r2 ls prepared by:~:hi~h pressure :Eree radical polymerization~
Polymer 73 ls the ba~e polymer.
Polymer 74 i~ an ethylene-butene copolymer made by the Du Pont high der~slty lo~ pressure process;
polymer d~nsity 0.937 gms/cc.
Polymer 75 is an ethylene homopolymer made by high pre~sure ~ree rad~cal polymeriz~.tion, polymer denslty O, 920 g;m~/cc .
Polymer 76 is an ethylene homopolymer ~ade by .
the Du Pont h~gh density low presæure process3 polymer den~ity 0.957 gms/cc and melt index (Condition E) o~
20 ~.8 before graftlng~ Grafted by the me~od of Poly~er 39.
Polymer 77 is grafted by method o~ Polymer 39.
Polymer 78 iæ DIENE* 35 sold by Firestone Rubber Co.
* denotes trade mark 3)?164 TABI.E ~
_ABLE OF ACRONYMS
E ethylene IBA i.sobutyl acrylate MAA methacrylic acid MA methyl acrylate MAME monoethyl ester of maleic anhydride HMD hexarnethylene diamine VA vinyl acetate MMA methyl methacrylate CO carbon monoxide AA acrylic acid HEMA hydroxyeth~L methacrylate SMA stearyl methacrylate nBA normal butyl acrylate 2EHMA 2--ethyl hexy1.methacrylate MVE methyl vinyl ether P~Anh maleic anhydride G~ glycidyl methacrylate EDM~ ethylene glycol dimethacrylate EA ethyl acryla.te ~A fumaric acid BuHM butyl hydrogen maleate PASA phthalic anhydricle sulfonyl azide SMA (3000) styrene maleic anhydride copolymer FA~E monoethyl ester of furnaric acid P propylene BASA benzoic acid sulfonyl azide BAN butadiene acl~lonitrile 3 SBR styrene butadiene rubber -g- graft These Examples prepared according to the procedure described above.are set forth in Table 30 ~l45-~ 33 ~ ~ ~
Control A is molded of an inter~ediate molecular weight 66 nylon. Examples l through 5 are a concentration series using a terpol~mer of ethylene7 isobutyl acrylate and methacrylic acid partially neutralized wi~h zinc~ At the 30~ concentration the notched Izod of a molded bar is over lO ft. lbs./inch at the gate end and the far endO At 20~o the material is tough at one end of the molded bar and at lower concentra-tions toughness is in the range of prior art materials at higher concentrations. Controls B through E are from the prior art and show that the higher modulus copolymer of ethylene and methacrylic acid is less effective in toughening polyamide matrix l than is the lower modulus terionomer O
Example 6 in comparison with Example 5 shows that reduction in molecular weight of` the matrix causes reduced notched Izod in a composite structure. F.xamples 7 to lO
show the e~fect of increasing molecular weight of the . .
matrix toughened with 20 weight percent Or the terionomer.
EY.ample lO with the highest molecular weight matrix pro-vides toughening with the ethylene terpolymer ionomer so that at the 20~o level toughness is approximately e~uivalent to that obtained at the 30~ level in matrix l.
Examples ll and l2 should be compared with Examples 4 and 5 to show the range of reproducibility in what were supposed to be identical materials. Comparing Controls F and G with Controls D and E show similar reproducibility in prior art materials.
Controls H, I and J show that low ethylene, low modulus materials are not eff'ective toughening ~1~6~
~.~ 33~
agents when no adherent site is present. In comparison9 Example 13 where an adherent site is present, gives very high toughness. Note that in comparison with Example lk the only major difference between the polymers is the presence of the ionomer group in Example 13.
Examples 14 and 15 show the strong toughening effect of the unneutralized maleic acid monoethyl ester terpol~mer in both an intermediate molecular weight polyamide with balanced end groups (Example 14) and in ~xample 15 a polyamide matrix with high amine ends. The high amine ends apparently ~rovide more effective interactisn with the dispersed acid toughening agent than the polyamide with a normal balance o~ end groups.
. When an ionomeric pol.ymer is used there is generally less advantage in toughening a high amine ended nylon~
Compare Example 16 with Example 4~
Examples 17 through 20 comprise a concentration series of the free acid toughening agent in high amine ended polyamideO ~t a concentration of 5% significant toughening is obtained. In fact, the material of Example 1~ achieves ~ery close to the toughness of prior art material (Control C) at 1/4 the toughener concentration and with consequently substantially better tensile strength and modulus~ Examples 19 and 21 illustrate the effect of the difference in concentration of amine ends in the polyamide~ The effect at the 10% toughener concentration le~el is more dramatic than at the 20%
level where the maximum in ductility as characteriæed by notched Izod is attained~
~xample 23 shows thak the acid polymer slightly -~7--~ 3~
neutralized with hexamethylene diamine is an effective toughening agent for nylon.
Examples 229 25 and 26 show the effect of various degrees of neutralization to prepare ionomers used for toughening polyamides with balanced end groups.
In a nylon rnatrix with balanced ends the zinc ionomer is a more effective pol~ner than the free acid polymer.
Examples 2~ and 2S differ primarily in details of the neutralization procedure which was carried out on a two roll mill and show that proper neutralizakion must be obtained in order to develop the most effective toughen~
ing. Conditions fo~ neutralization are given in Table lo Xt will be obvious to those skilled in the art that for any particular combination of pol~ner and matrix~
optimization of processing conditions must be used to - obtain the best resultO
Examples 2~ through Control L include three additional series where zinc neutralization was carried out from O to 100% or higher for three different toughening systems. In all three cases where a nylon with balanced ends was used preferred neutralization is in the range of lOO~ or below. Example 36 and Control L
illustrate that neutralization at 125% can give reduced toughness, so that for practical purposes neutralization in the range of 100% or below for toughening agents used in an amide with balanced ends is preferred~
Examples ~2 through ~5 show that calcium, lithi~nJ potassiurn and sodium ionomers can also be effective toughening agents whcn a soft organic moieky~
e.g., ethy]ene/methyl acrylate/monoethyl ester of maleic ~3~ 4 anhydride (E/MA/MA~ is used with them. Example ~6 illustrates that the antimony ionomer has some toughening effect~ In most of the ionomerization experiments either the metal hydroxide or ace~ate was used as the neutrali~ing agent but other salts would also be effective. Examples ~7 and 4~ illustrate that organic salts of the metal ions may also.be used.
Examples 49 and 50 in comparison with Examples 3 and 4 show that mixing small amounts of ethylene/methyl acrylate/maleic anhydride ester ionomers with ethylene/
; isobutylacrylate/methacrylic acid ionomers substantially improve the uniformity of compositions of the latter ionomer and polyamide aloneO
Examples 51 and 52 illustrate that lower molecular weight polyamide can be effectively toughenecl by the E/MA/MAME system. The improvement in notched I~od above the base resin shown in Example 53 suggests that moderately greater concentration of polymer would give substa~tial toughness in nylon of this low molecular 20 - weigh~.
Examples 5~ through 5~ illustrate the potential of several different ethylene terpolymer ionomers ~or toughening polyamides4 The results of Examples 59 and 60 suggest that higher molecular weight polymers are more effective than lower molecular weight materials.
A broad range of molecular weights can be employed~
Example 61 iIl comparison with Example 62 demons~rates the effectiveness of an ethylene/vinyl acetate/methacrylic - acid terpolymer ionomer in a high amine end nylon in comparison with the same polymer in a nylon with balanced ~ 3 amine ends~
Examples 63 and 61~ demonstrate the effectiveness o~ an aclditional ethylene terpolymerg the free acid in high amine end nylon and the ionomer in nylon with ~alanced end groups.
Controls M and N again show the need for an : adherenk siteO In ~xample 6~ ethylene/vinyl acetate/C0 terpGlymer has modest toughening effect on nylon with balanced end groupsO In comparison~ Examples 66 and 67 illustrate more effective toughening where amine ended nylon is believed to offer more effective interaction.
than balanced nylon with the carbonyl groups in the ter~
polymer. (Results with E/VA polymers have been less reproducible than with other pol~nersa apparently because o~ marginal stability at processing temperatures for 6~
nylonO) Example 69 illustrates the effect of a blend of two previously used polymers with the mixture providing good uni~ormity of toughness. ~xarnple 70 illustrates mixing two pol~ners, the polymers used in Control N and Examples 3 and ~ t~ provide substantially better tough~
ness than when either pol~er is used alone~ Similar effects of the mixtures of two pol~ners are shown in Examples 71 and 720 Cornparison of Example 73 with Control N shows that addition Or a small arnount of an adherent polymer with a low ~odulus nonadherent polymer can substan-tially increase its toughening capaci~y~
~ xamples 74 to 7~ cornprise a variety of ethylene terpolymers with C0 as the reactive agent for the polyamide matriY~. Several of' these examples illustra-te toughness ~5o ~ 3~
approaching notched I~od of 10 at both ends of the bar and suggest that many of these materials could achieve 10 ~otched ~zod uniformly with optimization of composition and processing, or some increase in toughener concentra-tionO
Examples 79$ ~0 and ~1 are ethylene/vinylacetate terpolymers with a variety of functional groups all of which show improvement in toughening compared with Control No Example ~2 is a polymer containing ~
monomeric en-tities which also indicates that optimiza-tion would yield notched Izods over 10 throughout the length of the molded bar9 though the cross-linking effect Or ethylene glycol dimethacrylate ~Control Q) may be deleterious~
Examples ~3 through 103 illustrate the wide toughening capability of ethylene~propylene copolymers which contain small amounts of dienes suitable for attaching adherent sites. As the examples show a variety of these polymers of various molecular weight and ratios o~ ethyiene to propylene and diene content may be employed. mey may be used in polyamide with balanced end groups or high amine ends and a wide variety of adherent groups may be grafted thereto. Example ~69 in comparison with Example ~79 illustrates that at low concentrations of adherent sites, the monoacid is less effective than the dicarboxylic acid~
Example 102 illustrates that an ionomer Or said copolymer is effective9 and Example 103 illustrates that said copolymers toughen low molecular weight nylon.
ExampleslO4 through 112 illustrate that a wide variety - ~33~64 of low modulus polymers can be used to toughen nylon as long as an adherent group is present. The examples include most of the commonly available low cost synthetic and natural rubbers including butadiene/acrylonitrile rubberS styrene/butadiene rubber, buna rubber, isobutylene, isoprene9 natural rubber9 ethyl acrylate9 butyl acrylate rubbers, etc~ Controls 0 and P for Examples 104 and 1109 respectively9 show the importance of a site for adhesion to the matrix.
Examples 113 and 114 illustrate that ethylene/
propylene copolymer can produce results similar to ethylene/propylene/diene terpolymer (~xamples ~3 to 103) provided that polymer with sites for adherence to the matrix are mixed in (~xample 113) or the appropriate ! ,:
site is grafted onto the copolymer ~Example 11~) by appropriate means~
The concentration serles of the ethylene/
isobutyl acrylate/methacrylic acid ionomer in matrix 1 comprising Examples 3~ 5~ 115$ Control R and Control S
discloses that notched Izod well over 20 ft. lbs./inch can be obtained at high loadings of polymer~ Significant loss in tensile strength and stiffness occur at high loadings with drastic loss over 50%p presumably because of phase inversion.
Examples 1169 117 and 11~ show that 612 nylon can also be toughened with an ionomeric system~
Consisten~ results are obtained in Samples 119 and 120 and Control T.
Nylon 6 is very effectively toughened by the zinc neutralized ionomer of E/MA/~AME~ Control U and Example 121~ Lower levels of tou~hener can be used.
Huls nylon 129 Control V is also effectively toughened by E/MA/MAME ionomer9 Exarnple 122~ and E/IBA/
MAA9 Example 123. Urethane rubbers are sufficiently stable at the melt temperature of nylon 12 to be ef*ec~ive polymers~ Example 124 : ~ylon 11 is toughened by E/P/diene-g-FA~
Examples 125 and 126.
Example 127 is an example of toughening a nylon copolyrnerO
~xample 12~ illustrates toughening of 66 nylon with balanced ends by an ethylene/propylene/1,4-hexadiene/
norbornadiene polymer which contains approximately 1D4 weight percent fumaric acid. Similar results, Examples 129 and 130, are ob~ained with similar type polymers which are grafted with esters of phthalic anhydride sulfonyl azide~
Toughening of an amorphous pol~amide with previously disclosed polymers is shown in Examples 131~133.
The same polymers toughen a polyamide contain-ing a cyclic aliphatic structure (Examples 134-136).
Examples 137-141 in comparison with Control Y
illustrate the toughening effectiveness of fumaric acid grafted ethylene/propylene/1,4~hexadiene/norborna-diene pol~ner at low concentrations~
Example 142 shows the effectiveness of a mixture of a soft (ethylene/methacrylate 46/54) and an adherent polymer (ethylene/acrylic acid ~0/20).
Examples 144 to 149 and Controls Z and AA
illustrate the effect of mixing branched pol.yethylenes -~3-~ ~ ~ 3 ~;4 of varying density wikh fumaric acid gra~ted e-thylene/
propylene/l~ hexadiene/norbornadiene polymer. Examples 14~ and Control Z were prepared by dry blending all the components and feeding to the twin screw extruder; Con~rol AA and Examples 145 to 149 were prepared by milling the hy~rocarbon polymers together before feeding to the extruder with the polyamideO Despite some variability in results9 the examples illustrate the following points.
1~ mixtures with softer polyethylene are more effective thall those with higher modulus polyethylene~ (2) a soft adherent polymer can render a mixture effecti~eg (3) comparisonwith Control BBp which was prepared by first extruding the soft adherent polymer with the matrix and then reextruding to add the polyethylene~ shows -thak the materials of the mixture must coexisk in the same particles to provide ef`~ective toughening~ Control CC
shows that S~o of this polymer alone is not enough to confer very high levels o~ toughening on the matrix (comparison with Example 141 reflects the influence of amine ends on the matrix~
Comparison of Control DD and Example 150 illustrates the effect of difference in polymer modulus when degree of adherence is about identical.
Example 151 illustrates an effective mixture of butadiene rubber and an adherent material.
Examples 15~ and 154, in comparison with Example 152, and F~amples 156 through 160; in comparison with Example 1559 illustrate that a variety of additives, eOg~ up to about 405~0 by weight, can be compounded into a toughPned composition without materially affecting ~51,-~ 6 ~
mechanical propertiesO Example 153 contains a lubricant, ~xample 154 a heat stabilizer and ~xamples 156~160 contain colorants~ In these experiments the additives were com-pounded into ~xamples 152 and 155 in a twin screw extruder with a vacuum port~ .
~ xample 162 was prepared by compounding 33 weight percent chopped glass fiber into the product of Example 161, on a single screw extruder with a vacuum port. The resultant product has a notched Izod nearly twice that of commercially available glass reinforced 66 nylon while -reta.ining strength and stiffness approaching that of untoughened materiaI~ ~xample 163 illustrates similar improvement when mineral filler is added to polyamideO
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These ~xamples illustrate uniformity o~
toughness in a 3 inch by five inch by 1/~ inch thick molded plaque. Samples are cut from this plaque so that notched Izod may be determined near and far from the gate in the flow and transvers~ directions. Utilizing the procedure described previously above thermoplastic compo-sitions are prepared having the composition set f orth in Table 40 Controls 1 and 3 represent toughened prior art 10 polya~lide compositionsc E~.amples 164 to 167 represent composi~ions of this invention. Examples 166 and 1679 in particular, have uniformly high toughness with 20 percent by weight polymer added to the polyamide matrixO
The data in Table 5 illustrate the effect of - decreasing notch radius on certain prior art compositions and preferred compositions of the invention. The results show that the prior art materials are more sensitive to this effect than the pre~erred compositions of this invention.
A further test which demonstrates the effec~ of notched radius on toughness is as follGws~ Each of the following materials was scra~ched to a depth of 20 mils with a raæox blade which gives a notch radius of about 0.~ mil and was tested using a Gardner Impact Tester IG~1115 manufactured by Gardner Laboratories9 IncO, Bethesda, Maryland~ The break occurred at the following loadings.
Matrix 1 6 inch pounds Control B ~ inch pounds Using the same procedure a material as described in Example 5 of the present invention broke at 69 inch pvunds.
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~XAMPLE 16~
A blend of ~5 weight percent of Matrix 1 and 15 weight percent of Polymer 66 containing additives of Example 15L~ was melt extruded into the form of a film.
The blend was extruded at a temperature in the range of 2~0-2~5C. in a Sterling extruder through an ~-inch (20~32 centimeters~ wide Johnson die maintained at a temperature of about 290-295C. The molten film was extruded onto the surface of a rotating (at about 15 feet (4.57~ meters) per minute) quench drum maintained at a temperature of.about 70Co Full wire electros-tatic pinning was used to insure uniform quenching of the cast film which was 10 mils (250 microns) in thickness~ Sheets9 ~ inc~es by 4 inches (10.16 centimeters by 10.16 centi~-meters)9 cut from the roll of cast film were stretched simultaneousiy ~in a T. M. Long Co. stretcher) 2.5X in mutually perpendicular directions at a tempera~ure of about 230C~ The cast film stretched uniformly in all directions. Matrix 1 is extremely difficult to cast into a film hence a control of Matxix 5 was utilized. A
cast film of Matrix 5 without Polymer 66 was difficult, to stretch uniformly and tended to exhihit line drawingO
Another sample of` the cast f'ilm was thermo~
formed7 after being preheated for about ~0 seconds in an oven heated to about 210C., into the shape of a dish 1~5 inches (3.~1 centimeters) deep by 5 inches (12.7 centimeters) in diameter. The male portion of the dish mold was heated to about ~00C. and the female portion.
was at about 160C~
-^73-., ~
Claims (79)
1. A toughened multiphase thermoplastic composition consisting essentially of one phase containing 60 to 99 percent by weight of a polyamide matrix resin of number average molecu-lar weight 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 taken from the class consisting of branched and straight chain polymers having a particle size in the range of 0.01 to 1.0 microns and having sites which adhere to the poly-amide matrix resin, and said at least one polymer having a ten-sile modulus in the range of about 1.0 to 20,000 psi, the ratio of the tensile modulus of the polyamide matrix resin to tensile modulus of said at least one polymer being greater than 10 to 1, wherein said at least one polymer is represented by the formula:
A(a)-B(b)-C(c)-D(d)-E(e)-F(f)-G(g)-H(h) derived in any order from monomers A to El wherein A is ethylene;
is CO;
C is an unsaturated monomer taken from the class consisting .alpha.,.beta.-ethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms, and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ionized by neutralization with metal ions and dicarboxylic acids and monoesters of the dicarboxylic acid neutralized by amine-ended caprolactam oligomers having a DP of 6 to 24;
D is an unsaturated epoxide of 4 to 11 carbon atoms;
E is the residue derived by the loss of nitrogen from an aromatic sulfonyl azide substituted by carboxylic acids taken from the class consisting of monocarboxylic and dicarbox-ylic acids having from 7 to 12 carbon atoms and derivatives thereof taken from the class consisting of monoesters of alco-hols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxy-lic acid groups ionized by neutralization with metal ions;
F is an unsaturated monomer taken from the class consisting of acrylate esters having from 4 to 22 carbon atoms, vinyl esters of acids having from 1 to 20 carbon atoms, vinyl ethers of 3 to 20 carbon atoms, vinyl and vinylidene halides, and nitriles having from 3 to 6 carbon atoms;
G is an unsaturated monomer having at least one substituent selected from the group consisting of pendant hydrocarbon chains of 1 to 12 carbon atoms and pendant aromatic groups which may have 1 to 6 substituent groups having a total of 14 carbon atoms; and H is an unsaturated monomer taken from the class consisting of branched, straight chain and cyclic compounds having from 4 to 14 carbon atoms and at least one additional unsaturated carbon-carbon bond capable of being grafted with a monomer having at least one reactive group of the type defined in C, D and E;
monomers A to H being present in the following mole fraction:
(a) 0 to 0.95, (b) 0 to 0.30, (c) 0 to 0.5, (d) 0 to 0.5, (e) 0 to 0.5, (f) 0 to 0.99, (g) 0 to 0.99, and (h) 0 to 0.99;
said at least one polymer having present at least one of mono-mers B, C, D and E with the proviso that when monomer A is present, in addition to at least one of monomers B, C, D and E, at least one of monomers F, G and H is also present.
A(a)-B(b)-C(c)-D(d)-E(e)-F(f)-G(g)-H(h) derived in any order from monomers A to El wherein A is ethylene;
is CO;
C is an unsaturated monomer taken from the class consisting .alpha.,.beta.-ethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms, and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ionized by neutralization with metal ions and dicarboxylic acids and monoesters of the dicarboxylic acid neutralized by amine-ended caprolactam oligomers having a DP of 6 to 24;
D is an unsaturated epoxide of 4 to 11 carbon atoms;
E is the residue derived by the loss of nitrogen from an aromatic sulfonyl azide substituted by carboxylic acids taken from the class consisting of monocarboxylic and dicarbox-ylic acids having from 7 to 12 carbon atoms and derivatives thereof taken from the class consisting of monoesters of alco-hols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxy-lic acid groups ionized by neutralization with metal ions;
F is an unsaturated monomer taken from the class consisting of acrylate esters having from 4 to 22 carbon atoms, vinyl esters of acids having from 1 to 20 carbon atoms, vinyl ethers of 3 to 20 carbon atoms, vinyl and vinylidene halides, and nitriles having from 3 to 6 carbon atoms;
G is an unsaturated monomer having at least one substituent selected from the group consisting of pendant hydrocarbon chains of 1 to 12 carbon atoms and pendant aromatic groups which may have 1 to 6 substituent groups having a total of 14 carbon atoms; and H is an unsaturated monomer taken from the class consisting of branched, straight chain and cyclic compounds having from 4 to 14 carbon atoms and at least one additional unsaturated carbon-carbon bond capable of being grafted with a monomer having at least one reactive group of the type defined in C, D and E;
monomers A to H being present in the following mole fraction:
(a) 0 to 0.95, (b) 0 to 0.30, (c) 0 to 0.5, (d) 0 to 0.5, (e) 0 to 0.5, (f) 0 to 0.99, (g) 0 to 0.99, and (h) 0 to 0.99;
said at least one polymer having present at least one of mono-mers B, C, D and E with the proviso that when monomer A is present, in addition to at least one of monomers B, C, D and E, at least one of monomers F, G and H is also present.
2. A composition according to Claim 1 wherein the tensile modulus of said at least one polymer is about 5.0 to 20,000 psi and the ratio of tensile modulus is greater than 20 to 1.
3. A composition according to Claim 1 wherein the ratio of tensile modulus is greater than 20 to 1.
4. A composition according to Claim 1 wherein the polyamide matrix resin melts above 200°C.
5. A composition according to Claim 2 wherein the polyamide matrix resin melts above 200°C.
6. A toughened multiphase thermoplastic composition consisting essentially of one phase containing 60 to 99 percent by weight of a polyamide matrix resin of number average molecu-lar weight 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 taken from the class consisting of branched and straight chain polymers having a particle size in the range of 0.01 to 1.0 microns and having sites which adhere to the poly-amide matrix resin, and said at least one polymer having a ten-sile modulus in the range of about 1.0 to 20,000 psi, the ratio of the tensile modulus of the polyamide matrix resin to tensile modulus of said at least one polymer being greater than 10 to 1 wherein the polyamide melts below 200°C. and the said at least one polymer is a polyurethane which is the reaction product of at least one glycol taken from the class consisting of poly-ester glycol having an average molecular weight of 300 to 6000 and a polyether glycol having an average molecular weight of 300 to 6000, and at least one diisocyanate having 4 to 21 carbon atoms.
7. A toughened multiphase thermoplastic composition consisting essentially of one phase containing 60 to 99 percent by weight of a polyamide matrix resin of number average molecu-lar weight 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 taken from the class consisting of branched and straight chain polymers having a particle size in the range of 0.01 to 1.0 microns and having sites which adhere to the poly-amide matrix resin, and said at least one polymer having a ten-sile modulus in the range of about 1.0 to 20,000 psi, the ratio of the tensile modulus of the polyamide matrix resin to tensile modulus of said at least one polymer being greater than 10 to 1 wherein the polyamide melts below 225°C and the said at least one polymer is a polymer containing polyether repeat units taken from class consisting of the reaction product of epoxide-containing monomers having 2 to 3 carbon atoms, an epoxide-containing monomer having pendant groups taken from the class consisting of methyl or chloromethyl groups, and mixtures of said epoxide monomers.
8. A composition according to Claim 4 wherein the notched Izod in the dry as molded condition is at least the values (expressed in ft. lb./inch of notch) represented by the formulae:
B + 0.2 C1 B + 2.0 + 0.5 (C2-10), B + 12.0 where B is the notched Izod of the polyamide matrix resin, C1 is 2 to 10 percent by weight of the one polymer, and C2 is 10 to 30 percent by weight of the at least one polymer, and the notched Izod is at least B +
12.0 when the concentration of the at least one polymer is between 30 and 40 percent by weight.
B + 0.2 C1 B + 2.0 + 0.5 (C2-10), B + 12.0 where B is the notched Izod of the polyamide matrix resin, C1 is 2 to 10 percent by weight of the one polymer, and C2 is 10 to 30 percent by weight of the at least one polymer, and the notched Izod is at least B +
12.0 when the concentration of the at least one polymer is between 30 and 40 percent by weight.
9. A composition according to Claim 5 wherein the notched Izod in the dry as molded condition is at least the values (expressed in ft. lb./inch of notch) represented by the formulae:
B + 0.2 C1 B + 2.0 + 0.5 (C2-10), B + 12.0 where B is the notched Izod of the polyamide matrix resin, C1 is 2 to 10 percent by weight of the at least one polymer, and C2 is 10 to 30 percent by weight of the at least one polymer, and the notched Izod is at least B +
12.0 when the concentration of the at least one polymer is between 30 and 40 percent by weight.
B + 0.2 C1 B + 2.0 + 0.5 (C2-10), B + 12.0 where B is the notched Izod of the polyamide matrix resin, C1 is 2 to 10 percent by weight of the at least one polymer, and C2 is 10 to 30 percent by weight of the at least one polymer, and the notched Izod is at least B +
12.0 when the concentration of the at least one polymer is between 30 and 40 percent by weight.
10. A composition according to Claim 4 wherein the notched Izod value, dry as molded, is greater than 8 ft.
lbs./inch when the concentration of said at least one polymer is from 5 to 20 percent by weight.
lbs./inch when the concentration of said at least one polymer is from 5 to 20 percent by weight.
11. A composition according to Claim 5 wherein the notched Izod value, dry as molded, is greater than 8 ft.
lbs./inch when the concentration of said at least one polymer is from 5 to 20 percent by weight.
lbs./inch when the concentration of said at least one polymer is from 5 to 20 percent by weight.
12. A composition according to Claim 1 wherein the polyamide is a condensation reaction product of a dicarboxylic acid of 4 to 12 carbon atoms and a diamine of 4 to 14 carbon atoms.
13. A composition according to Claim 2 wherein the polyamide is the condensation reaction product of a dicarboxy-lic acid of 4 to 12 carbon atoms and a diamine of 4 to 14 carbon atoms.
14. A composition according to Claim 1 wherein the polyamide is polycaprolactam.
15. A composition according to Claim 2 wherein the polyamide is polycaprolactam.
16. A composition according to Claim 1 wherein there is present up to 5.0 percent by weight, based on the weight of the composition, of at least one colorant.
17. A composition according to Claim 1 wherein there is present up to 50 percent by weight, based on the weight of the composition, of glass fibers.
18. A composition according to Claim 1 wherein there is present up to 50 percent by weight, based on the weight of the composition, of fibrous and particulate mineral fillers and reinforcements.
19. A composition according to Claim 1 wherein there is present up to 1.0 percent by weight, based on the weight of polyamide, of a stabilizer.
20. A composition according to Claim 1 wherein said at least one polymer has present carbon monoxide.
21. A composition according to Claim 1 wherein said at least one polymer has present an unsaturated monomer taken from the class consisting of .alpha.,.beta.-ethylenically unsaturated car-boxylic acids having from 3 to 8 carbon atoms, and derivatives thereof taken from the class consisting of monoesters of alco-hols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxy-lic acid groups ionized by neutralization with metal ions and dicarboxylic acids and monoesters of the dicarboxylic acid neutralized by amine-ended caprolactam oligomers having a DP of 6 to 24.
22. A composition according to Claim 1 wherein said at least one polymer has present an unsaturated epoxide of 4 to 11 carbon atoms.
23. A composition according to Claim 1 wherein said at least one polymer has present the residue derived by the loss of nitrogen from an aromatic sulfonyl azide substituted by carboxylic acids taken from the class consisting of monocarbox-ylic and dicarboxylic acids having from 7 to 12 carbon atoms and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicar-boxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ionized by neutralization with metal ions.
24. A composition according to Claim 5 wherein said at least one polymer has present carbon monoxide.
25. A composition according to Claim 5 wherein said at least one polymer has present an unsaturated monomer taken from the class consisting of .alpha.,.beta.-ethylenically unsaturated car-boxylic acids having from 3 to 8 carbon atoms, and derivatives thereof taken from the class consisting of monoesters of alco-hols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxy-lic acid groups ionized by neutralization with metal ions and dicarboxylic acids and monoesters of the dicarboxylic acid neutralized by amine-ended caprolactam oligomers having a DP of 6 to 24.
26. A composition according to Claim 5 wherein said at least one polymer has present an unsaturated epoxide of 4 to 11 carbon atoms.
27. A composition according to Claim 5 wherein said at least one polymer has present the residue derived by the loss of nitrogen from an aromatic sulfonyl azide substituted by carboxylic acids taken from the class consisting of monocarbox-ylic and dicarboxylic acids having from 7 to 12 carbon atoms and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicar-boxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ionized by neutralization with metal ions.
28. A composition according to Claim 1 wherein said at least one polymer has present an unsaturated monomer taken from the class consisting of acrylate esters having from 4 to 22 carbon atoms, vinyl esters of acids having from 1 to 20 car-bon atoms, vinyl ethers of 3 to 20 carbon atoms, vinyl and vinylidene halides, and nitriles having from 3 to 6 carbon atoms.
29. A composition according to Claim 1 wherein said at least one polymer has present an unsaturated monomer having pendant hydrocarbon chains of 1 to 12 carbon atoms capable of being grafted with monomers having at least one reactive group of the type defined in C, D and E, and pendant aromatic groups which may have 1 to 6 substituent groups having a total of 14 carbon atoms.
30. A composition according to Claim 1 wherein said at least one polymer has present an unsaturated monomer taken from the class consisting of branched, straight chain and cyclic compounds having from 4 to 14 carbon atoms and at least one additional nonconjugated unsaturated carbon-carbon bond capable of being grafted with a monomer having at least one reactive group of the type defined in C, D and E.
31. A composition according to Claim 5 wherein said at least one polymer has present an unsaturated monomer taken from the class consisting of acrylate esters having from 4 to 22 carbon atoms, vinyl esters of acids having from 1 to 20 car-bon atoms, vinyl ethers of 3 to 20 carbon atoms, vinyl and vinylidene halides, and nitriles having from 3 to 6 carbon atoms.
32. A composition according to Claim 5 wherein said at least one polymer has present an unsaturated monomer having pendant hydrocarbon chains of 1 to 12 carbon atoms capable of being grafted with monomers having at least one reactive group of the type defined in C, D, and E, and pendant aromatic groups which may have 1 to 6 substituent groups having a total of 14 carbon atoms.
33. A composition according to Claim 5 wherein said at least one polymer has present an unsaturated monomer taken from the class consisting of branched, straight chain and cyclic compounds having from 4 to 14 carbon atoms and at least one additional nonconjugated unsaturated carbon-carbon bond capable of being grafted with a monomer having at least one reactive group of the type defined in C, D and E.
34. A composition according to Claim 3 wherein said at least one polymer consists essentially of polymerized ethy-lene, at least one polymerized .alpha.-olefin of 3 to 6 carbon atoms, and at least one polymerized unsaturated monomer taken from the class consisting of branched, straight chain and cyclic com-pounds having from 4 to 14 carbon atoms and at least one addi-tional nonconjugated unsaturated carbon-carbon bond, and grafted thereto an unsaturated monomer taken from the class consisting of .alpha.,.beta.-ethylenically unsaturated dicarboxylic acids having from 3 to 8 carbon atoms, and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms, anhydrides of the dicarboxylic acids, the metal salts of the dicarboxylic acids and the monoesters of said dicarboxylic acid having from 0 to 100 percent of the carboxylic groups ionized by neutralization with metal ions.
35. A composition according to Claim 34 wherein said at least one polymer is a copolymer of ethylene, propylene and 1,4-hexadiene having grafted thereto an unsaturated monomer taken from the class consisting of fumaric acid, maleic acid, maleic anhydride and the monoalkyl ester of said acids in which the alkyl group of the ester has 1 to 3 carbon atoms, said at least one polymer having an after grafting melt flow rate of 0.1 to 100 g./10 minutes, ASTM D 1238 at 280°C. and a total load of 2160 grams.
36. A composition according to Claim 34 wherein said at least one polymer is a tetrapolymer of ethylene, propylene, 1,4-hexadiene and 2,5-norbornadiene having grafted thereto an unsaturated monomer taken from -the class consisting of fumaric acid, maleic acid, maleic anhydride and the monoalkyl ester of said acids in which the alkyl group of the ester has 1 to 3 carbon atoms, said at least one polymer having an after grafting melt flow rate of 0.1 to 100 g./10 minutes, ASTM D
1238 at 280°C. and a total load of 2160 grams.
1238 at 280°C. and a total load of 2160 grams.
37. A composition according to Claim 35 wherein said polyamide matrix resin is polyhexamethylene adipamide.
38. A composition according to Claim 36 wherein said polyamide matrix resin is polyhexamethylene adipamide.
39. A composition according to Claim 37 wherein said polyamide matrix resin is polycaprolactam.
40. A composition according to Claim 38 wherein said polyamide matrix resin is polycaprolactam.
41. A composition according to Claim 3 wherein said at least one polymer is a random copolymer consisting essen-tially of polymerized ethylene, alkyl acrylate selected from methyl and ethyl acrylate, and from about 0.0025-0.077 mole/100 g. polymer of a mono alkyl ester of 1,4-butene-dioic acid in which the alkyl group of the ester has 1 to 6 carbon atoms, said copolymer having from about 0.64-0.80 mole of (-CO2-1 units per 100 grams of copolymer, and having 0 to 100 percent of the esters of 1,4-butene-dioic acid ionized by neutrali-zation with metal ions selected from lithium, sodium, potas-sium, calcium and zinc ions, said copolymer having a melt index at 190°C. and a total load of 2160 grams of about 0.3 to 100 grams/10 minutes, and when neutralized having a melt flow rate of 0.04 to 100 grams/10 minutes under condition G of ASTM D
1238.
1238.
42. A composition according to Claim 41 wherein said mono alkyl ester of 1,4-butene-dioic acid consists essentially of ethyl hydrogen maleate.
43. A composition according to Claim 42 wherein said polyamide matrix resin is polyhexamethylene adipamide.
44. A composition according to Claim 43 wherein said polyamide matrix resin is polycaprolactam.
45. A process for the preparation of a toughened multi-phase thermoplastic composition which comprises, in a closed system, (a) admixing (1) 60 to 99 percent by weight of a polyamide matrix resin of number average molecular weight of at least 5000, and (2) 1 to 40 percent by weight of at least one polymer taken from the class consisting of branched and straight chain polymers and having sites which adhere to the polyamide matrix, the components being mixed at a temperature in the range of about 5 to 100°C. above the melting point of said polyamide matrix resin and (b) shearing to disperse said at least one polymer in said matrix comprising particles of a size in the range of 0.01 to 1.0 microns, said at least one polymer having a tensile modulus in the range of 100 to 20,000 psi, the ratio of the tensile modulus of said matrix to tensile modulus of said at least one polymer being greater than 10 to 1, wherein said at least one polymer is represented by the formula:
A(a)-B(b)-C(c)-D(d)-E(e)-F(f)-G(g)-E(h) derived in any order from monomers A to H wherein A is ethylene:
B is CO;
C is an unsaturated monomer taken from the class consisting of .alpha.,.beta.,-ethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms, and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ion-ized by neutralization with metal ions and dicarboxylic acids and monoesters of the dicarboxylic acid neutralized by amine-ended caprolactam oligomers having a DP of 6 to 24;
D is an unsaturated epoxide of 4 to 11 carbon atoms;
E is the residue derived by the loss of nitrogen from an aromatic sulfonyl azide substituted by carboxylic acids taken from the class consisting of monocarboxylic and dicarbox-ylic acids having from 7 to 12 carbon atoms and derivatives thereof taken from the class consisting of monoesters of alco-hols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxy-lic acid groups ionized by neutralization with metal ions;
F is an unsaturated monomer taken from the class consisting of acrylate esters having from 4 to 22 carbon atoms, vinyl esters of acids having from 1 to 20 carbon atoms, vinyl ethers of 3 to 20 carbon atoms, vinyl and vinylidene halides, and nitriles having from 3 to 6 carbon atoms;
G is an unsaturated monomer having at least one substituent selected from the group consisting of pendant hydrocarbon chains of 1 to 12 carbon atoms and pendant aromatic groups which may have 1 to 6 substituent groups having a total of 14 carbon atoms; and H is an unsaturated monomer taken from the class consisting of branched, straight chain and cyclic compounds having from 4 to 14 carbon atoms and at least one additional unsaturated carbon-carbon bond capable of being grafted with a monomer having at least one reactive group of the type defined in C, D and E;
monomers A to H being present in the following mole fraction:
(a) 0 to 0.95, (b) 0 to 0.30, (c) 0 to 0.5, (d) 0 to 0.5, (e) 0 to 0.5, (f) 0 to 0.99, (g) 0 to 0.99, and (h) 0 to 0.99; said at least one polymer having present at least one of monomers B, C, D and E with the proviso that when monomer A is present, in addition to at least one of monomers B, C, D and E, at least one of monomers F, G and H is also present.
A(a)-B(b)-C(c)-D(d)-E(e)-F(f)-G(g)-E(h) derived in any order from monomers A to H wherein A is ethylene:
B is CO;
C is an unsaturated monomer taken from the class consisting of .alpha.,.beta.,-ethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms, and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ion-ized by neutralization with metal ions and dicarboxylic acids and monoesters of the dicarboxylic acid neutralized by amine-ended caprolactam oligomers having a DP of 6 to 24;
D is an unsaturated epoxide of 4 to 11 carbon atoms;
E is the residue derived by the loss of nitrogen from an aromatic sulfonyl azide substituted by carboxylic acids taken from the class consisting of monocarboxylic and dicarbox-ylic acids having from 7 to 12 carbon atoms and derivatives thereof taken from the class consisting of monoesters of alco-hols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxy-lic acid groups ionized by neutralization with metal ions;
F is an unsaturated monomer taken from the class consisting of acrylate esters having from 4 to 22 carbon atoms, vinyl esters of acids having from 1 to 20 carbon atoms, vinyl ethers of 3 to 20 carbon atoms, vinyl and vinylidene halides, and nitriles having from 3 to 6 carbon atoms;
G is an unsaturated monomer having at least one substituent selected from the group consisting of pendant hydrocarbon chains of 1 to 12 carbon atoms and pendant aromatic groups which may have 1 to 6 substituent groups having a total of 14 carbon atoms; and H is an unsaturated monomer taken from the class consisting of branched, straight chain and cyclic compounds having from 4 to 14 carbon atoms and at least one additional unsaturated carbon-carbon bond capable of being grafted with a monomer having at least one reactive group of the type defined in C, D and E;
monomers A to H being present in the following mole fraction:
(a) 0 to 0.95, (b) 0 to 0.30, (c) 0 to 0.5, (d) 0 to 0.5, (e) 0 to 0.5, (f) 0 to 0.99, (g) 0 to 0.99, and (h) 0 to 0.99; said at least one polymer having present at least one of monomers B, C, D and E with the proviso that when monomer A is present, in addition to at least one of monomers B, C, D and E, at least one of monomers F, G and H is also present.
46. A process according to Claim 45 wherein the tensile modulus of said at least one polymer is about 5.0 to 20,000 psi and the ratio of tensile modulus is greater than 20 to 1.
47. A process according to Claim 45 wherein the ratio of tensile modulus is greater than 20 to 1.
48. A process according to Claim 45 wherein the polyamide matrix resin melts above 200°C.
49. A process according to Claim 48 wherein the notched Izod in the dry as molded condition is at least the values (expressed in ft. lb./inch of notch) represented by the formulae:
B + 0.2 C1 B + 2.0 + 0.5 (C2-10) B + 12.0 where B is the notched Izod of the polyamide matrix resin, C1 is 2 to 10 percent by weight of the at least one polymer, and C2 is 10 to 30 percent by weight of the at least one polymer, and the notched Izod is at least B + 12.0 when the concen-tration of the at least one polymer is between 30 and 40 percent by weight.
B + 0.2 C1 B + 2.0 + 0.5 (C2-10) B + 12.0 where B is the notched Izod of the polyamide matrix resin, C1 is 2 to 10 percent by weight of the at least one polymer, and C2 is 10 to 30 percent by weight of the at least one polymer, and the notched Izod is at least B + 12.0 when the concen-tration of the at least one polymer is between 30 and 40 percent by weight.
50. A process according to Claim 48 wherein the notched Izod value, dry as molded, is greater than 8 ft.
lbs/inch when the concentration of said at least one polymer is from 5 to 20 percent by weight.
lbs/inch when the concentration of said at least one polymer is from 5 to 20 percent by weight.
51. A process according to Claim 47 wherein said at least one polymer consists essentially of polymerized ethylene, at least one polymerized .alpha.-olefin of 3 to 6 carbon atoms, and at least one polymerized unsaturated monomer taken from the class consisting of branched, straight chain and cyclic com-pounds having from 4 to 14 carbon atoms and at least one addi-tional nonconjugated unsaturated carbon-carbon bond, and grafted thereto an unsaturated monomer taken from the class consisting of .alpha.,.beta.-ethylenically unsaturated dicarboxylic acids having from 3 to 8 carbon atoms, and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms, anhydrides of the dicarboxylic acids, the metal salts of the dicarboxylic acids and the monoesters of said dicarboxylic acids having from 0 to 100 percent of the carboxylic groups ionized by neutralization with metal ions.
52. A process according to Claim 51 wherein said polyamide matrix resin is polyhexamethylene adipamide.
53. A process according to Claim 51 wherein said polyamide matrix resin is polycaprolactam.
54. A process according to Claim 47 wherein said at least one polymer is a random copolymer consisting essentially of polymerized ethylene, alkyl acrylate selected from methyl and ethyl acrylate, and from about 0.0025-0.077 mole/100 g.
polymers of a mono alkyl ester of 1,4-butene-dioic acid in which the alkyl group of the ester has 1 to 6 carbon atoms, said copolymer having from about 0.64-0.80 mole of (-C02-) units per 100 grams of copolymer, and having 0 to 100 percent of the esters of 1,4-butene-dioic acid ionized by neutrali-zation with metal ions selected from lithium, sodium, potas-sium, calcium and zinc ions, said copolymer having a melt index at 190°C. and a total load of 2160 grams of about 0.3 to 100 grams/10 minutes, and when neutralized having a melt flow rate of 0,04 to 100 grams/10 minutes under condition G of ASTM D
1238.
polymers of a mono alkyl ester of 1,4-butene-dioic acid in which the alkyl group of the ester has 1 to 6 carbon atoms, said copolymer having from about 0.64-0.80 mole of (-C02-) units per 100 grams of copolymer, and having 0 to 100 percent of the esters of 1,4-butene-dioic acid ionized by neutrali-zation with metal ions selected from lithium, sodium, potas-sium, calcium and zinc ions, said copolymer having a melt index at 190°C. and a total load of 2160 grams of about 0.3 to 100 grams/10 minutes, and when neutralized having a melt flow rate of 0,04 to 100 grams/10 minutes under condition G of ASTM D
1238.
55. A process according to Claim 54 wherein said polyamide matrix resin is polyhexamethylene adipamide.
56. A process according to Claim 54 wherein said polyamide matrix resin is polycaprolactam.
57. Process for preparing a toughened multiphase thermoplastic composition consisting essentially of one phase containing 80 to 99 percent by weight of a polyamide matrix resin of number average molecular weight of at least 5000, and 1 to 20 percent by weight of at least one other phase contain-ing particles of at least one polymer taken from the class con-sisting of branched and straight chain polymers having sites which adhere to the polyamide matrix and comprise a particle size in the range of 0.01 to 1.0 microns, and said at least one polymer having a tensile modulus in the range of about 1.0 to 20,000 psi, the ratio of the tensile modulus of the polyamide matrix resin to tensile modulus of said at least one polymer being greater than 10 to 1, wherein said at least one polymer is represented by the formula A(a)-B(b)-C(c)-D(d)-E(e)-F(f)-G(g)-H(h) derived in any order from monomers A to H wherein A is ethylene;
B is CO;
C is an unsaturated monomer taken from the class consisting of .alpha.,.beta.-ethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms, and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ionized by neutralization with metal ions and dicarboxylic acids and monoesters of the dicarboxylic acid neutralized by amine ended caprolactam oligomers having a DP of 6 to 24;
D is an unsaturated epoxide of 4 to 11 carbon atoms;
E is the residue derived by the loss of nitrogen from an aromatic sulfonyl azide substituted by carboxylic acids taken from the class consisting of monocarboxylic and dicarboxylic acids having from 7 to 12 carbon atoms and deriva-tives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxy-lic acid groups ionized by neutralization with metal ions;
F is an unsaturated monomer taken from the class con-sisting of acrylate esters having from 4 to 22 carbon atoms, vinyl esters of acids having from 1 to 20 carbon atoms, vinyl ethers of 3 to 20 carbon atoms, vinyl and vinylidene halides, and nitriles having from 3 to 6 carbon atoms;
G is an unsaturated monomer having at least one substituent selected from the group consisting of pendant hydrocarbon chains of 1 to 12 carbon atoms and pendant aromatic groups which may have 1 to 6 substituent groups having a total of 14 carbon atoms; and H is an unsaturated monomer taken from the class con-sisting of branched, straight chain and cyclic compounds having from 4 to 14 carbon atoms and at least one additional unsaturated carbon-carbon bond capable of being grafted with a monomer having at least one reactive group of the type defined in C, D and E;
monomers A to H being present in the following mole fraction:
(a) 0 to 0.95, (b) 0 to 0.30, (c) 0 to 0.5, (d) 0 to 0.5, (e) 0 to 0.5, (f) 0 to 0.99, (g) 0 to 0.99, and (h) 0 to 0.99; said at least one polymer having present at least one of monomers B, C, D and E with the proviso that when monomer A is present, in addition to at least one of monomers B, C, D and E, at least one of monomers F, G and H is also present; which com-prises initially admixing said polyamide matrix resin and up to about 40 percent by weight of said at least one polymer and additionally admixing said polyamide matrix resin until said desired concentration is achieved.
B is CO;
C is an unsaturated monomer taken from the class consisting of .alpha.,.beta.-ethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms, and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ionized by neutralization with metal ions and dicarboxylic acids and monoesters of the dicarboxylic acid neutralized by amine ended caprolactam oligomers having a DP of 6 to 24;
D is an unsaturated epoxide of 4 to 11 carbon atoms;
E is the residue derived by the loss of nitrogen from an aromatic sulfonyl azide substituted by carboxylic acids taken from the class consisting of monocarboxylic and dicarboxylic acids having from 7 to 12 carbon atoms and deriva-tives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxy-lic acid groups ionized by neutralization with metal ions;
F is an unsaturated monomer taken from the class con-sisting of acrylate esters having from 4 to 22 carbon atoms, vinyl esters of acids having from 1 to 20 carbon atoms, vinyl ethers of 3 to 20 carbon atoms, vinyl and vinylidene halides, and nitriles having from 3 to 6 carbon atoms;
G is an unsaturated monomer having at least one substituent selected from the group consisting of pendant hydrocarbon chains of 1 to 12 carbon atoms and pendant aromatic groups which may have 1 to 6 substituent groups having a total of 14 carbon atoms; and H is an unsaturated monomer taken from the class con-sisting of branched, straight chain and cyclic compounds having from 4 to 14 carbon atoms and at least one additional unsaturated carbon-carbon bond capable of being grafted with a monomer having at least one reactive group of the type defined in C, D and E;
monomers A to H being present in the following mole fraction:
(a) 0 to 0.95, (b) 0 to 0.30, (c) 0 to 0.5, (d) 0 to 0.5, (e) 0 to 0.5, (f) 0 to 0.99, (g) 0 to 0.99, and (h) 0 to 0.99; said at least one polymer having present at least one of monomers B, C, D and E with the proviso that when monomer A is present, in addition to at least one of monomers B, C, D and E, at least one of monomers F, G and H is also present; which com-prises initially admixing said polyamide matrix resin and up to about 40 percent by weight of said at least one polymer and additionally admixing said polyamide matrix resin until said desired concentration is achieved.
58. A process according to Claim 45 wherein said composition prepared using a polyamide matrix resin having an initial number average molecular weight of 5,000 to 15,000 is held at a temperature about 10 to 40°C. above the melting point of said polyamide matrix resin for up to one hour at a pressure of about 1 to 25 mm Hg absolute.
59. A process according to Claim 45 wherein said composition prepared using a polyamide matrix resin having an initial number average molecular weight of 5,000 to 15,000 is extruded through a die into the form of beading, cut, quenched, dried and is held at an elevated temperature at least 15°C.
below the melting point of said polyamide matrix resin for at least two hours in a stream of inert gas.
below the melting point of said polyamide matrix resin for at least two hours in a stream of inert gas.
60. A toughened multiphase thermoplastic composition consisting essentially of one phase containing 60 to 99 percent by weight of a polyamide matrix resin of number average molecu-lar weight 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 taken from the class consisting of branched and straight chain polymers having a particle size in the range of 0.01 to 1.0 microns and having sites which adhere to the poly-amide matrix resin, and said at least one polymer having a ten-sile modulus in the range of about 1.0 to 20,000 psi, the ratio of the tensile modulus of the polyamide matrix resin to tensile modulus of said at least one polymer being greater than 10 to 1, said compositions being selected from the group consisting of compositions wherein (i) said at least one polymer is represented by the formula:
A(a)-B(b)-C(c)-D(d)-E(e)-F(f)-G(g)-H(h) derived in any order from monomers A to H wherein A is ethylene;
B is CO;
C is an unsaturated monomer taken from the class consisting of .alpha.,.beta.-ethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms, and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ion-ized by neutralization with metal ions and dicarboxylic acids and monoesters of the dicarboxylic acid neutralized by amine-ended caprolactam oligomers having a DP of 6 to 214;
D is an unsaturated epoxide of 4 to 11 carbon atoms;
E is the residue derived by the loss of nitrogen from an aromatic sulfonyl azide substituted by carboxylic acids taken from the class consisting of monocarboxylic and dicarbox-ylic acids having from 7 to 12 carbon atoms and derivatives thereof taken from the class consisting of monoesters of alco-hols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxy-lic acid groups ionized by neutralization with metal ions;
F is an unsaturated monomer taken from the class consisting of acrylate esters having from 4 to 22 carbon atoms, vinyl esters of acids having from 1 to 20 carbon atoms, vinyl ethers of 3 to 20 carbon atoms, vinyl and vinylidene halides, and nitriles having from 3 to 6 carbon atoms;
G is an unsaturated monomer having at least one substituent selected from the group consisting of pendant hydrocarbon chains of 1 to 12 carbon atoms and pendant aromatic groups which may have 1 to 6 substituent groups having a total of 14 carbon atoms; and H is an unsaturated monomer taken from the class consisting of branched, straight chain and cyclic compounds having from 4 to 14 carbon atoms and at least one additional unsaturated carbon-carbon bond capable of being grafted with a monomer having at least one reactive group of the type defined in C, D and E:
monomers A to H being present in the following fraction:
(a) 0 to 0.95, (b) 0 to 0.30, (c) 0 to 0.5, (d) 0 to 0.5, (e) 0 to 0.5, (f) 0 to 0.99, (g) 0 to 0.99, and (h) 0 to 0.99;
said at least one polymer having present at least one of mono-mers B, C, D and E with the proviso that when monomer A is present, in addition to at least one of monomers B, G, D and E, at least one of monomers F, G and H is also present; (ii) the polyamide melts below 200°C and the said at least one polymer is a polyurethane which is the reaction product of at least one glycol taken from the class consisting of polyester glycol having an average molecular weight of 300 to 6000 and a polyether glycol having an average molecular weight of 300 to 6000, and at least one diisocyanate having 4 to 21 carbon atoms; and (iii) the polyamide melts below 225°C and the said at least one polymer is a polymer containing polyether repeat units taken from the class consisting of the reaction product of epoxide-containing monomers having 2 to 3 carbon atoms, an epoxide-containing monomer having pendant groups taken from the class consisting of methyl or chloromethyl groups, and mixtures of said epoxide momomers.
A(a)-B(b)-C(c)-D(d)-E(e)-F(f)-G(g)-H(h) derived in any order from monomers A to H wherein A is ethylene;
B is CO;
C is an unsaturated monomer taken from the class consisting of .alpha.,.beta.-ethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms, and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ion-ized by neutralization with metal ions and dicarboxylic acids and monoesters of the dicarboxylic acid neutralized by amine-ended caprolactam oligomers having a DP of 6 to 214;
D is an unsaturated epoxide of 4 to 11 carbon atoms;
E is the residue derived by the loss of nitrogen from an aromatic sulfonyl azide substituted by carboxylic acids taken from the class consisting of monocarboxylic and dicarbox-ylic acids having from 7 to 12 carbon atoms and derivatives thereof taken from the class consisting of monoesters of alco-hols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxy-lic acid groups ionized by neutralization with metal ions;
F is an unsaturated monomer taken from the class consisting of acrylate esters having from 4 to 22 carbon atoms, vinyl esters of acids having from 1 to 20 carbon atoms, vinyl ethers of 3 to 20 carbon atoms, vinyl and vinylidene halides, and nitriles having from 3 to 6 carbon atoms;
G is an unsaturated monomer having at least one substituent selected from the group consisting of pendant hydrocarbon chains of 1 to 12 carbon atoms and pendant aromatic groups which may have 1 to 6 substituent groups having a total of 14 carbon atoms; and H is an unsaturated monomer taken from the class consisting of branched, straight chain and cyclic compounds having from 4 to 14 carbon atoms and at least one additional unsaturated carbon-carbon bond capable of being grafted with a monomer having at least one reactive group of the type defined in C, D and E:
monomers A to H being present in the following fraction:
(a) 0 to 0.95, (b) 0 to 0.30, (c) 0 to 0.5, (d) 0 to 0.5, (e) 0 to 0.5, (f) 0 to 0.99, (g) 0 to 0.99, and (h) 0 to 0.99;
said at least one polymer having present at least one of mono-mers B, C, D and E with the proviso that when monomer A is present, in addition to at least one of monomers B, G, D and E, at least one of monomers F, G and H is also present; (ii) the polyamide melts below 200°C and the said at least one polymer is a polyurethane which is the reaction product of at least one glycol taken from the class consisting of polyester glycol having an average molecular weight of 300 to 6000 and a polyether glycol having an average molecular weight of 300 to 6000, and at least one diisocyanate having 4 to 21 carbon atoms; and (iii) the polyamide melts below 225°C and the said at least one polymer is a polymer containing polyether repeat units taken from the class consisting of the reaction product of epoxide-containing monomers having 2 to 3 carbon atoms, an epoxide-containing monomer having pendant groups taken from the class consisting of methyl or chloromethyl groups, and mixtures of said epoxide momomers.
61. The composition of Claim 6 wherein said polyurethane is the reaction product of said at least one gly-col, said at least one diisocyanate and at least one diol having a molecular weight of less than 300.
62. A process for the preparation of a toughened multi-phase thermoplastic composition, said process being selected from the group consisting of (i) a process which com-prises, in a closed system, (a) admixing (1) 60 to 99 percent by weight of a polyamide matrix resin of number average molecu-lar weight of at least 5000, and (2) 1 to 40 percent by weight of at least one polymer taken from the class consisting of branched and straight chain polymers and having sites which adhere to the polyamide matrix, the components being mixed at a temperature in the range of about 5 to 100°C. above the melting point of said polyamide matrix resin and (b) shearing to dis-perse said at least one polymer in said matrix comprising par-ticles of a size in the range of 0.01 to 1.0 microns, said at least one polymer having a tensile modulus in the range of 1.0 to 20,000 psi, the ratio of the tensile modulus of said matrix to tensile modulus of said at least one polymer being greater than 10 to 1, wherein said at least one polymer is represented by the formula:
A(a)-B(b)-C(c)-D(d)-E(e)-F(f)-G(g)-H(h) derived in any order from monomers A to H wherein A is ethylene;
B is CO;
C is an unsaturated monomer taken from the class consisting of .alpha.,.beta.-ethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms, and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ion-ized by neutralization with metal ions and dicarboxylic acids and monoesters of the dicarboxylic acid neutralizd by amine-ended caprolactam oligomers having a DP of 6 to 24;
D is an unsaturated epoxide of 4 to 11 carbon atoms:
E is the residue derived by the loss of nitrogen from an aromatic sulfonyl azide substituted by carboxylic acids taken from the class consisting of monocarboxylic and dicarbox-ylic acids having from 7 to 12 carbon atoms and derivatives thereof taken from the class consisting of monoesters of alco-hols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxy-lic acid groups ionized by neutralization with metal ions;
F is an unsaturated monomer taken from the class consisting of acrylate esters having from 4 to 22 carbon atoms, vinyl esters of acids having from 1 to 20 carbon atoms, vinyl ethers of 3 to 20 carbon atoms, vinyl and vinylidene halides, and nitriles having from 3 to 6 carbon atoms;
G is an unsaturated monomer having at least one substituent selected from the group consisting of pendant hydrocarbon chains of 1 to 12 carbon atoms and pendant aromatic groups which may have 1 to 6 substituent groups having a total of 14 carbon atoms; and H is an unsaturated monomer taken from the class consisting of branched, straight chain and cyclic compounds having from 4 to 14 carbon atoms and at least one additional unsaturated carbon-carbon bond capable of being grafted with a monomer having at least one reactive group of the type defined in C, D and E;
monomers A to H being present in the following mole fraction:
(a) 0 to 0.95, (b) 0 to 0.30, (c) 0 to 0.5, (d) 0 to 0.5, (e) 0 to 0.5, (f) 0 to 0.99, (g) 0 to 0.99, and (h) 0 to 0.99;
said at least one polymer having present at least one of mono-mers B, C, D and E with the proviso that when monomer A is present, in addition to at least one of monomers B, C, D and E, at least one of monomers F, G and H is also present; and (ii) when the composition consists essentially of one phase contain-ing 80 to 99 percent by weight of a polyamide matrix resin of number average molecular weight of at least 5000, and 1 to 20 percent by weight of at least one other phase containing parti-cles of at least one polymer taken from the class consisting of branched and straight chain polymers having sites which adhere to the polyamide matrix and comprise a particle size in the range of 0.01 to 1.0 microns, and said at least one polymer having a tensile modulus in the range of about 1.0 to 20,000 psi, the ratio of the tensile modulus of the polyamide matrix resin to tensile modulus of said at least one polymer being greater than 10 to 1, wherein said at least one polymer is represented by the above formula, a process which comprises initially admixing said polyamide matrix resin and up to about 40 percent by weight of the said at least one polymer and additionally admixing said polyamide matrix resin until said desired concentration is achieved,
A(a)-B(b)-C(c)-D(d)-E(e)-F(f)-G(g)-H(h) derived in any order from monomers A to H wherein A is ethylene;
B is CO;
C is an unsaturated monomer taken from the class consisting of .alpha.,.beta.-ethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms, and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ion-ized by neutralization with metal ions and dicarboxylic acids and monoesters of the dicarboxylic acid neutralizd by amine-ended caprolactam oligomers having a DP of 6 to 24;
D is an unsaturated epoxide of 4 to 11 carbon atoms:
E is the residue derived by the loss of nitrogen from an aromatic sulfonyl azide substituted by carboxylic acids taken from the class consisting of monocarboxylic and dicarbox-ylic acids having from 7 to 12 carbon atoms and derivatives thereof taken from the class consisting of monoesters of alco-hols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxy-lic acid groups ionized by neutralization with metal ions;
F is an unsaturated monomer taken from the class consisting of acrylate esters having from 4 to 22 carbon atoms, vinyl esters of acids having from 1 to 20 carbon atoms, vinyl ethers of 3 to 20 carbon atoms, vinyl and vinylidene halides, and nitriles having from 3 to 6 carbon atoms;
G is an unsaturated monomer having at least one substituent selected from the group consisting of pendant hydrocarbon chains of 1 to 12 carbon atoms and pendant aromatic groups which may have 1 to 6 substituent groups having a total of 14 carbon atoms; and H is an unsaturated monomer taken from the class consisting of branched, straight chain and cyclic compounds having from 4 to 14 carbon atoms and at least one additional unsaturated carbon-carbon bond capable of being grafted with a monomer having at least one reactive group of the type defined in C, D and E;
monomers A to H being present in the following mole fraction:
(a) 0 to 0.95, (b) 0 to 0.30, (c) 0 to 0.5, (d) 0 to 0.5, (e) 0 to 0.5, (f) 0 to 0.99, (g) 0 to 0.99, and (h) 0 to 0.99;
said at least one polymer having present at least one of mono-mers B, C, D and E with the proviso that when monomer A is present, in addition to at least one of monomers B, C, D and E, at least one of monomers F, G and H is also present; and (ii) when the composition consists essentially of one phase contain-ing 80 to 99 percent by weight of a polyamide matrix resin of number average molecular weight of at least 5000, and 1 to 20 percent by weight of at least one other phase containing parti-cles of at least one polymer taken from the class consisting of branched and straight chain polymers having sites which adhere to the polyamide matrix and comprise a particle size in the range of 0.01 to 1.0 microns, and said at least one polymer having a tensile modulus in the range of about 1.0 to 20,000 psi, the ratio of the tensile modulus of the polyamide matrix resin to tensile modulus of said at least one polymer being greater than 10 to 1, wherein said at least one polymer is represented by the above formula, a process which comprises initially admixing said polyamide matrix resin and up to about 40 percent by weight of the said at least one polymer and additionally admixing said polyamide matrix resin until said desired concentration is achieved,
63. The composition of Claim 1 wherein the said at least one polymer is present as part of a mixture, the components of the mixture co-existing in the same discrete particles in the polyamide matrix, said particles having a par-ticle size in the range of 0.01 to 1.0 microns and wherein a constituent selected from the group consisting of said at least one polymer and said mixture has sites which adhere to the polyamide matrix resin, a tensile modulus in the range of about 1.0 to 20,000 psi and a ratio of the tensile modulus of the polyamide matrix resin to tensile modulus of said constituent of greater than 10 to 1.
64. The composition of Claim 63 wherein the said at least one polymer comprises at least 20 percent by weight o*
said at least one other phase.
said at least one other phase.
65. The composition of Claim 34 wherein the said at least one polymer is present as part of a mixture, the compon-ents of the mixture co-existing in the same discrete particles in the polyamide matrix, said particles having a particle size in the range of 0.01 to 1.0 microns and wherein a constituent selected from the group consisting of said at least one polymer and said mixture has sites which adhere to the polyamide matrix resin, a tensile modulus in the range of about 1.0 to 20,000 psi and a ratio of the tensile modulus of the polyamide matrix resin to tensile modulus of said constituent of greater than 10 to 1.
66. The composition of Claim 65 wherein the said at least one polymer comprises at least 20 percent by weight of said at least one other phase.
67. The composition of Claim 65 or Claim 66 wherein said at least one polymer is a copolymer of ethylene, propylene and 1,4-hexadiene having grafted thereto an unsaturated monomer taken from the class consisting of fumaric acid, maleic acid, maleic anhydride and the Monoalkyl ester of said acids in which the alkyl group of the ester has 1 to 3 carbon atoms, said at least one polymer having an after grafting melt flow rate of 0.1 to 100 g./10 minutes, ASTM D 1238 at 280°C. and a total load of 2160 grams.
68. The composition of Claim 65 or Claim 66 wherein said at least one polymer is a tetrapolymer of ethylene, propy-lene, 1,4-hexadiene and 2,5-norbornadiene having grafted there-to an unsaturated monomer taken from the class consisting of fumaric acid, maleic acid, maleic anhydride and the monoalkyl ester of said acids in which the alkyl group of the ester has 1 to 3 carbon atoms, said at least one polymer having an after grafting melt flow rate of 0.1 to 100 g./10 minutes, ASTM D
1238 at 280°C. and a total load of 2160 grams.
1238 at 280°C. and a total load of 2160 grams.
69. The composition of Claim 65 or Claim 66 wherein said polyamide matrix resin is polyhexamethylene adipamide and wherein said at least one polymer is a copolymer of ethylene, propylene and 1,4-hexadiene having grafted thereto an unsatu-rated monomer taken from the class consisting of fumaric acid, maleic acid, maleic anhydride and the monoalkyl ester of said acids in which the alkyl group of the ester has 1 to 3 carbon atoms, said at least one polymer having an after grafting melt flow rate of 0.1 to 100 g./10 minutes, ASTM D 1238 at 280°C.
and a total load of 2160 grams.
and a total load of 2160 grams.
70. The composition of Claim 65 or Claim 66 wherein said polyamide matrix resin is polyhexamethylene adipamide and wherein said at least one polymer is a tetrapolymer of ethy-lene, propylene, 1,4-hexadiene and 2,5-norbornadiene having grafted thereto an unsaturated monomer taken from the class consisting of fumaric acid, maleic acid, maleic anhydride and the monoalkyl ester of said acids in which the alkyl group of the ester has 1 to 3 carbon atoms, said at least one polymer having an after grafting melt flow rate of 0.1 to 100 g./10 minutes, ASTM D 1238 at 280°C. and a total load of 2160 grams.
71. The composition of Claim 65 or Claim 66 wherein said polyamide matrix resin is caprolactam and wherein said at least one polymer is a copolymer of ethylene, propylene and 1,4-hexadiene having grafted therto an unsaturated monomer taken from the class consisting of a fumaric acid, maleic acid, maleic anhydride and the monoalkyl ester of said acids in which the alkyl group of the ester has 1 to 3 carbon atoms, said at least one polymer having an after grafting melt flow rate of 0.1 to 100 g./10 minutes, ASTM D 1238 at 280°C. and a total load of 2160 grams.
72. The composition of Claim 65 or Claim 66 wherein said polyamide matrix resin is caprolactam and wherein said at least one polymer is a tetrapolymer of ethylene, propylene, 1,4-hexadiene and 2,5-norbornadiene having grafted thereto an unsaturated monomer taken from the class consisting of fumaric acid, maleic acid, maleic anhydride and the monoalkyl ester of said acids in which the alkyl group of the ester has 1 to 3 carbon atoms, said at least one polymer having an after graft-ing melt flow rate of 0.1 to 100 g./10 minutes, ASTM D1238 at 280°C. and a total load of 2160 grams.
73. The composition of Claim 41 wherein the said at least one polymer is present as part of a mixture, the compon-ents of the mixture co-existing in the same discrete particles in the polyamide matrix, said particles having a particle size in the range of 0.01 to 1.0 microns and wherein a constituent selected from the group consisting of said at least one polymer and said mixture has sites which adhere to the polyamide matrix resin, a tensile modulus in the range of about 1.0 to 20,000 psi and a ratio of the tensile modulus of the polyamide matrix resin to tensile modulus of said constituent of greater than 10 to 1.
74. The composition of Claim 73 wherein the said at least one polymer comprises at least 20 percent by weight of said at least one other phase.
75. The composition of Claim 73 or Claim 74 wherein said mono alkyl ester of 1,4-butene-dioic acid consists essentially of ethyl hydrogen maleate.
76. The composition of Claim 73 or Claim 74 wherein said polyamide matrix resin is polyhexamethylene adipamide.
77. The composition of Claim 73 or Claim 74 wherein said polyamide matrix resin is polycaprolactam.
78. The composition of Claim 60 wherein the said at least one polymer is present as part of a mixture, the compon-ents of the mixture co-existing in the same discrete particles in the polyamide matrix, said particles having a particle size in the range of 0.01 to 1.0 microns and wherein a constituent selected from the group consisting of said at least one polymer and said mixture has sites which adhere to the polyamide matrix resin, a tensile modulus in the range of about 1.0 to 20,000 psi and a ratio of the tensile modulus of the polyamide matrix resin to tensile modulus of said constituent of greater than 10 to 1.
79. The composition of Claim 78 wherein the said at least one polymer comprises at least 20 percent by weight of said at least one other phase.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US58051375A | 1975-05-23 | 1975-05-23 | |
| US580,513 | 1975-05-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1133164A true CA1133164A (en) | 1982-10-05 |
Family
ID=24321410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA253,067A Expired CA1133164A (en) | 1975-05-23 | 1976-05-21 | Toughened thermoplastic polyamide matrix with micron sized dispersed soft polymer |
Country Status (8)
| Country | Link |
|---|---|
| JP (2) | JPS51143061A (en) |
| CA (1) | CA1133164A (en) |
| CH (1) | CH649566A5 (en) |
| DE (1) | DE2622973B2 (en) |
| FR (1) | FR2311814A1 (en) |
| GB (1) | GB1552352A (en) |
| IT (1) | IT1061385B (en) |
| NL (1) | NL168540B (en) |
Families Citing this family (56)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2654168C2 (en) * | 1976-11-30 | 1986-02-06 | Bayer Ag, 5090 Leverkusen | Polyamide alloys |
| DE2713537B2 (en) * | 1977-03-26 | 1981-04-16 | Bayer Ag, 5090 Leverkusen | Polyamide alloys |
| DE2734693A1 (en) * | 1977-08-02 | 1979-02-15 | Bayer Ag | HIGH-IMPACT POLYAMIDE ALLOYS |
| JPS5439458A (en) * | 1977-09-02 | 1979-03-26 | Hitachi Ltd | Friction material |
| JPS5493043A (en) * | 1977-12-29 | 1979-07-23 | Unitika Ltd | Resin composition and its production |
| JPS5536279A (en) * | 1978-09-08 | 1980-03-13 | Mitsubishi Chem Ind Ltd | Production of polyamide resin composition |
| US4320213A (en) * | 1978-10-30 | 1982-03-16 | Monsanto Company | High-impact polyamide molding resin compositions |
| JPS55139450A (en) * | 1979-04-18 | 1980-10-31 | Ube Ind Ltd | Impact-resistant polyamide composition |
| US4283502A (en) * | 1979-04-30 | 1981-08-11 | E. I. Du Pont De Nemours And Company | Polyamide resins |
| US4220733A (en) | 1979-05-01 | 1980-09-02 | E. I. Du Pont De Nemours And Company | Thermally stable, flame-retardant polymers |
| JPS55157650A (en) * | 1979-05-29 | 1980-12-08 | Ube Ind Ltd | Polyamide composition with high impact strength |
| JPS6059257B2 (en) * | 1979-11-14 | 1985-12-24 | 旭化成株式会社 | Glass fiber reinforced resin composition |
| GB2060649B (en) * | 1979-10-04 | 1983-07-13 | Asahi Dow Ltd | Co-grafted polymers |
| US4387184A (en) * | 1979-12-10 | 1983-06-07 | Rhone-Poulenc Industries | Heat stable polyphase polyamide compositions and preparation thereof |
| JPS56109247A (en) * | 1980-01-22 | 1981-08-29 | Du Pont | Polyamide blend |
| US4410653A (en) * | 1980-04-08 | 1983-10-18 | E. I. Du Pont De Nemours And Company | Flame-retardant polyamide blends |
| JPS578246A (en) * | 1980-06-19 | 1982-01-16 | Mitsubishi Chem Ind Ltd | Polyamide resin composition |
| JPS5778453A (en) * | 1980-11-05 | 1982-05-17 | Mitsubishi Chem Ind Ltd | Polyamide resin composition |
| GB2092600A (en) * | 1981-02-11 | 1982-08-18 | Du Pont | Mineral reinforced polyamides |
| DE3204455A1 (en) * | 1981-02-14 | 1982-09-09 | Basf Ag, 6700 Ludwigshafen | Impact-resistant thermoplastic moulding compositions |
| JPS57160612A (en) * | 1981-03-30 | 1982-10-04 | Toray Ind Inc | Thermoplastic film |
| JPS57200448A (en) * | 1981-06-03 | 1982-12-08 | Mitsubishi Chem Ind Ltd | Polyamide resin composition |
| US4394459A (en) | 1981-09-18 | 1983-07-19 | E. I. Du Pont De Nemours & Co. | Fast-curing foamable composition based on ethylene terpolymers |
| US4370423A (en) | 1981-09-18 | 1983-01-25 | Bata Limited | Fast-curing foamable composition based on ethylene terpolymers |
| DE3220380A1 (en) * | 1982-05-29 | 1983-12-01 | Basf Ag, 6700 Ludwigshafen | IMPACT POLYAMIDE MOLDS |
| JPS5924751A (en) * | 1982-08-02 | 1984-02-08 | Toray Ind Inc | Polyamide resin composition |
| JPS5927948A (en) * | 1982-08-06 | 1984-02-14 | Toray Ind Inc | Resin composition |
| JPS59151008U (en) * | 1983-03-28 | 1984-10-09 | 松下電器産業株式会社 | heating cooking device |
| NL8302602A (en) * | 1983-07-20 | 1985-02-18 | Stamicarbon | IMPACT RESISTANT POLYAMIDE COMPOSITION. |
| DE3417476A1 (en) * | 1984-05-11 | 1985-11-14 | Bayer Ag, 5090 Leverkusen | POLYAMIDE MOLDS WITH HIGH TOUGHNESSES |
| DE3576965D1 (en) * | 1984-09-15 | 1990-05-10 | Huels Chemische Werke Ag | MOLDS BASED ON THERMOPLASTICS. |
| JPS61152782A (en) * | 1984-12-27 | 1986-07-11 | Ube Ind Ltd | Polyamide adhesive composition and laminate |
| JPS61296079A (en) * | 1985-06-25 | 1986-12-26 | Ube Ind Ltd | Polyamide adhesive composition and laminate |
| EP0265070B1 (en) * | 1986-09-26 | 1991-10-09 | Ube Industries, Ltd. | Fiber-reinforced rubber composition and production process and use thereof |
| DE3700330A1 (en) * | 1987-01-08 | 1988-07-21 | Basf Ag | IMPACT POLYAMIDE MOLDS |
| DE3711730A1 (en) * | 1987-04-10 | 1988-10-27 | Ter Hell Plastic Gmbh | Process for the preparation of polymer alloys, and polymer alloys of this type |
| US4987017A (en) * | 1987-06-26 | 1991-01-22 | Japan Synthetic Rubber Co., Ltd. | Thermoplastic elastomer composition and Freon gas hose made thereof |
| CH672495A5 (en) * | 1987-07-17 | 1989-11-30 | Inventa Ag | |
| CA1332013C (en) * | 1987-08-17 | 1994-09-13 | Yuichi Orikasa | Thermoplastic resin composition and method for preparing the same |
| DE3810519C1 (en) * | 1988-03-28 | 1989-10-12 | Ems-Inventa Ag, Zuerich, Ch | |
| CA1338025C (en) * | 1988-08-29 | 1996-01-30 | Andri Elia Elia | Toughened nylons characterized by low mold deposit |
| JPH0284453A (en) * | 1988-09-20 | 1990-03-26 | Japan Synthetic Rubber Co Ltd | Thermoplastic elastomer composition and rubber component for cooler |
| DE3926904A1 (en) * | 1989-08-16 | 1991-02-21 | Basf Ag | METHOD FOR PRODUCING REINFORCED, TOOTH-MODIFIED THERMOPLASTIC MOLDS |
| JPH0385104A (en) * | 1989-08-29 | 1991-04-10 | Asahi Corp | Tiptoe reinforcing rubber piece for tennis shoe |
| DE4214383C2 (en) * | 1992-04-30 | 1996-08-14 | Inventa Ag | Coextruded multilayer polymer tube |
| US5486594A (en) * | 1994-07-11 | 1996-01-23 | Shell Oil Company | Polyketone polymers as nylon toughners |
| DE4425437A1 (en) | 1994-07-19 | 1996-01-25 | Basf Ag | Glass-reinforced polyamide molding compounds for blow molding applications |
| DE19653042A1 (en) | 1996-12-19 | 1998-06-25 | Basf Ag | Flame retardant molding compounds |
| EP1057870A1 (en) | 1999-06-02 | 2000-12-06 | Atofina | Compositions of polyolefin and a low melting point polyamide |
| US20020004555A1 (en) * | 2000-01-21 | 2002-01-10 | Silvia Di-Benedetto | Impact modified polyamide composition |
| US6420481B2 (en) | 2000-01-21 | 2002-07-16 | E. I. Du Pont De Nemours And Comapny | Impact modified polyamide compositions |
| AU2001229642A1 (en) * | 2000-01-21 | 2001-07-31 | E.I. Du Pont De Nemours And Company | Impact modified polyamide composition |
| GB2410308B (en) † | 2004-01-20 | 2008-06-25 | Uponor Innovation Ab | Multilayer pipe |
| JP7311338B2 (en) * | 2019-07-11 | 2023-07-19 | 旭化成株式会社 | Method for producing polyamide resin composition and molded article |
| WO2021049511A1 (en) | 2019-09-12 | 2021-03-18 | 東洋紡株式会社 | Polyamide resin composition and polyamide resin molded article |
| US20240174822A1 (en) * | 2021-03-23 | 2024-05-30 | Toray Industries, Inc. | Fibre-reinforced resin, porous structure, and molded member |
Family Cites Families (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA742299A (en) * | 1966-09-06 | H. Halliwell Ronald | Blends of polyamide resins with acid-containing methacrylate polymers | |
| NL237027A (en) * | 1958-08-28 | |||
| US3274289A (en) * | 1959-05-12 | 1966-09-20 | Canadian Ind | Homogeneous blends of polyamides with carboxylate copolymers containing a neutral monomer comprising butadiene-1, 3, vinyl chloride, or a mixture of butadiene-1, 3 and methyl methacrylate |
| NL302805A (en) * | 1962-12-31 | |||
| GB1047069A (en) * | 1963-08-21 | 1966-11-02 | Du Pont | Blends of polyamide resins with acrylic resins |
| CH441742A (en) * | 1964-01-31 | 1967-08-15 | Igo Plast Faigle & Co | Plastic material, preferably for bearings and similar machine elements, as well as processes for their manufacture |
| GB1116202A (en) * | 1964-10-24 | 1968-06-06 | Ici Ltd | Improvements in or relating to the dispersion of polyolefins in non-compatible synthetic polymers and to the products obtained thereby |
| US3388186A (en) * | 1965-03-02 | 1968-06-11 | Allied Chem | Carboxy terminated graft copolymers of amino-carboxylic acids or lactams on acrylic copolymers |
| US3845163A (en) * | 1966-01-24 | 1974-10-29 | Du Pont | Blends of polyamides and ionic copolymer |
| JPS4810380B1 (en) * | 1967-07-27 | 1973-04-03 | ||
| GB1189029A (en) * | 1967-08-14 | 1970-04-22 | Du Pont | Oriented Polyamide Articles |
| DE1900636B2 (en) * | 1968-01-08 | 1972-01-13 | Monsanto Co , St Louis, Mo (V St A ) | MIXTURES OF POLYAMIDES AND MIXED POLYMERISATES OF ETHYLENE |
| FR1570562A (en) * | 1968-03-22 | 1969-06-13 | ||
| DE1941228A1 (en) * | 1968-08-16 | 1970-02-19 | Dart Ind Inc | Polymer mixtures |
| GB1241361A (en) * | 1969-03-11 | 1971-08-04 | Ici Ltd | Thermoplastic polymer blends |
| NL7003304A (en) * | 1969-03-11 | 1970-09-15 | ||
| US3668274A (en) * | 1970-09-10 | 1972-06-06 | Rohm & Haas | Acrylic modifiers for polycarbonamides |
| US3821171A (en) * | 1971-07-01 | 1974-06-28 | Du Pont | Continuous,solid-phase polymerization of polyamide granules |
| US3735607A (en) * | 1971-07-21 | 1973-05-29 | G Jeney | Knitting apparatus |
| US3780140A (en) * | 1971-08-06 | 1973-12-18 | Du Pont | Ethylene/carbon monoxide polymer compositions |
| DE2217527C3 (en) * | 1972-04-12 | 1980-02-14 | Basf Ag, 6700 Ludwigshafen | Filaments or fibers of polyamides formed from the melt and containing an antistatic agent, and a process for their production |
| JPS497061A (en) * | 1972-05-08 | 1974-01-22 | ||
| IT989816B (en) * | 1972-11-14 | 1975-06-10 | Ford Motor Co | THERMOPLASTIC MATERIAL BASED ON RUBBER REINFORCED POLYAMIDE AND PROCEDURE FOR ITS PRODUCTION |
| JPS5038658B2 (en) * | 1973-01-12 | 1975-12-11 | ||
| DE2343693C2 (en) * | 1973-08-30 | 1982-06-16 | Hoechst Ag, 6000 Frankfurt | Thermoplastic polyamide molding compounds |
| JPS51125451A (en) * | 1975-04-03 | 1976-11-01 | Asahi Chem Ind Co Ltd | Polyamide composition |
-
1976
- 1976-05-21 IT IT2353376A patent/IT1061385B/en active
- 1976-05-21 NL NL7605495A patent/NL168540B/en not_active Application Discontinuation
- 1976-05-21 JP JP5801576A patent/JPS51143061A/en active Granted
- 1976-05-21 DE DE19762622973 patent/DE2622973B2/en not_active Ceased
- 1976-05-21 CH CH644376A patent/CH649566A5/en not_active IP Right Cessation
- 1976-05-21 CA CA253,067A patent/CA1133164A/en not_active Expired
- 1976-05-24 FR FR7615621A patent/FR2311814A1/en active Granted
- 1976-05-24 GB GB2150276A patent/GB1552352A/en not_active Expired
-
1983
- 1983-11-24 JP JP21966583A patent/JPS59131649A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| IT1061385B (en) | 1983-02-28 |
| JPS6354308B2 (en) | 1988-10-27 |
| JPS5544108B2 (en) | 1980-11-10 |
| CH649566A5 (en) | 1985-05-31 |
| JPS51143061A (en) | 1976-12-09 |
| NL7605495A (en) | 1976-11-25 |
| FR2311814A1 (en) | 1976-12-17 |
| DE2622973B2 (en) | 1979-09-20 |
| NL168540B (en) | 1981-11-16 |
| GB1552352A (en) | 1979-09-12 |
| FR2311814B1 (en) | 1979-07-13 |
| JPS59131649A (en) | 1984-07-28 |
| DE2622973A1 (en) | 1976-12-09 |
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