Process for impact modification of high nitrile polymers

Claim 2

A PROCESS FOR PREPARING RUBBER MODIFIED NITRILE POLYMER COMPOSITIONS WHICH COMPRISES: A. ADMIXING

Claim 3

A RUBBERY POLYMER SUBSTRATE HAVING A BUTADIENE CONTENT OF 68 TO 72 PERCENT BY WEIGHT AND A STYRENE CONTENT OF 28 TO 32 PERCENT BY WEIGHT BASED ON THE TOTAL WEIGHT OF THE BUTADIENE-STYRENE RUBBERY SUBSTRATE WHICH RUBBERY SUBSTRATE IS FURTHER CHARACTERIZED AS HAVING A REFREACTIVE INDEX IN THE RANGE OF FROM 1.5375 TO 1.5425, A PARTICLE SIZE IN THE RANGE OF FROM 0.06 TO 0.2 MICRON, AA GEL CONTENT IN THE RANGE OF FROM 40 TO 95 PERCENT, A SWELLING INDEX IN THE RANGE OF FROM 10 TO 40, AND A SECOND ORDER TRANSITION TEMPERATURE (TG) LESS THAN -40*C, AND

Claim 4

A RUBBERY POLYMER SUBSTRATE HAVING A BUTADIENE CONTENT OF 68 TO 72 PERCENT BY WEIGHT AND A STYRENE CONTENT OF 28 TO 32 PERCENT BY WEIGHT BASED ON THE TOTAL WEIGHT OF THE BUTADIENE-STYRENE RUBBERY SUBSTRATE WHICH RUBBERY SUBSTRATE IS FURTHER CHARACTERIZED AS HAVING A REFREACTIVE INDEX IN THE RANGE OF FROM 1.5375 TO 1.5425, A PARTICLE SIZE IN THE RANGE OF FROM 0.06 TO 0.2 MICRON, AA GEL CONTENT IN THE RANGE OF FROM 40 TO 95 PERCENT, A SWELLING INDEX IN THE RANGE OF FROM 10 TO 40, AND A SECOND ORDER TRANSITION TEMPERATURE (TG) LESS THAN -40*C, AND

Claim 5

A FIRST POLYMERIZABLE MONOMER COMPOSITION CMPRISING: A. FROM 0.1 TO 2 PERCENT BY WEIGHT OF A NONCONJUGATED DIOLEFIN MONOMER: B. FROM 0 TO 30 PRECENT BY WEIGHT OF AN ETHYLENICALLY UNSATURATED NITRILE MONOMER SELECTED FROM THE GROUP CONSISTING OF ACRYLONITRILE, AND MIXTURES OF ACRYLONITRILE AND METRACRYLONITRILE, C. FROM 40 TO 60 PERCENT BY WEIGHT OF A VINYLIDENE AROMATIC HYDROCARBON MONOMER, AND D. FROM 20 TO 50 PERCENT BY WEIGHT OF AN ALKYL ESTER OF ACRYLIC OR METHACEYLIC ACID WHEREIN THE ALKYL GROUP CONTAINS FROM 1 TO 8 CARBON ATOMS, WHEREIN THE PRESENT BY WEIGHT IS BASED ON THE TOTAL WEIGHT OF THE MONOMER IN THE FIRST POLYMERIZABLE MONOMER MIXTURE, B. HEATING THE ADMIXTURE TO A TEMPERATURE IN THE RANGE OF FROM 30* TO 100*C. IN THE PRESENCE OF A POLYMERIZATION CATALYST TO EFFECT POLYMERIZATION OF SAID MONOMER FORMULATION AND GRAFTING OF THE POLYMER BEING PRODUCED ONTO THE RUBBERY POLYMER SUBSTRATE TO FORM A GRAFT COPOLYMER, SAID GRAFT COPOLYMER HAVING A SUPERSTRATE TO SUBSTRATE RATIO OF AT LEAST 10:100: C. ADMIXTURE SAID GRAFT COPLYMER WITH A SECOND POLYMERIZABLE COMPOSITION COMPRISING FROM 55 TO 85 PERCENT BY WEIGHT OF AN ETHYLENICALLY UNSATURATED NITRILE MONOMER SELECTED FROM THE GROUP CONSISTING OF ACRYLONITRILE AND MIXTURES OF ACRYLONITRILE AND METHACRYLONITRILE CONTAINS UP TO 20 PERCENT BY WEIGHT OF METHACRYLONITRILE BASED ON THE TOTAL WEIGHT OF ACRYLONITRILE AND MATHACRYLONYITRILE AND FROM 15 TO 45 PERCENT BY WEIGHT OF A MONOVINYLIDENE AROMATIC HYDROCARBON MONOMER WHEREIN THE PERCENT BY WEIGHT IS BASED ON THE TOTAL WEIGHT OF THE MONOMERS IN THE SECOND POLYMERIZABLE MONOMER MIXTURE, AND D. HEATING THE SECOND MENTIONED ADMIXTURE TO A TEMPERATURE IN THE RANGE OF FROM 30* TO 100*C. IN THE PRESENCE OF A POLYMERIZATION CATALYST TO EFFECT POLYMERIZATION OF THE MONOMERS THEREOF AND TO PRODUCE GRAFTING OF THE POLYMER BEING PRODUCED ONTO SAID GRAFT COPOLYMER TO FORM A COMPOSITE GRAFT COPOLYMER, SAID GRAFTED POLYMER OF SAID FIRST AND SECOND ADMIXTURES PROVIDING A GRAFTED SUPERSTRATE WHICH CONTAINS A TOTAL OF AT LEAST 40 PERCENT BY WEIGHT ETHYLENICALLY UNSATURATED NITRILE MONOMER AND WHEREIN THE RATIO OF GRAFTED SUPERSTRATE TO SUBSTRATE IS IN THE RANGE OF FROM 15-200:100, E. BLENDING THE POLYMERIZATION PRODUCT OF STEPS A TO D ABOVE WITH A MATRIX POLYMER WHICH COMPRISES FROM 55 TO 85 PERCENT BASED ON THE TOTAL WEIGHT OF THE POLYMER, OF AN ETHYLENICALLY UNSATURATED NITRILE MONOMER SELECTED FROM THE GROUP CONSISTING OF ACRYLONITRILE AND MIXTURES OF ACRYLONITRILE AND METHACRYLONITRILE WHICH CONTAIN UP TO 20 PERCENT BY WEIGHT OF METHACRYLONITRILE BASED ON THE TOTAL WEIGHT OF ACRYLONITRILE AND METHACRYLONITRILE AND FROM 15 TO 45 PRECENT OF A MONOVINYLIDENE AROMATIC HYDROCARBON MONOMER, WHEREIN THE RUSULTING BLEND CONTAINS FROM 3 TO 50% BY WEIGHT OF THE RUBBERY POLYMER SUBSTRATE.

Claim 6

A FIRST POLYMERIZABLE MONOMER COMPOSITION CMPRISING: A. FROM 0.1 TO 2 PERCENT BY WEIGHT OF A NONCONJUGATED DIOLEFIN MONOMER: B. FROM 0 TO 30 PRECENT BY WEIGHT OF AN ETHYLENICALLY UNSATURATED NITRILE MONOMER SELECTED FROM THE GROUP CONSISTING OF ACRYLONITRILE, AND MIXTURES OF ACRYLONITRILE AND METRACRYLONITRILE, C. FROM 40 TO 60 PERCENT BY WEIGHT OF A VINYLIDENE AROMATIC HYDROCARBON MONOMER, AND D. FROM 20 TO 50 PERCENT BY WEIGHT OF AN ALKYL ESTER OF ACRYLIC OR METHACEYLIC ACID WHEREIN THE ALKYL GROUP CONTAINS FROM 1 TO 8 CARBON ATOMS, WHEREIN THE PRESENT BY WEIGHT IS BASED ON THE TOTAL WEIGHT OF THE MONOMER IN THE FIRST POLYMERIZABLE MONOMER MIXTURE, B. HEATING THE ADMIXTURE TO A TEMPERATURE IN THE RANGE OF FROM 30* TO 100*C. IN THE PRESENCE OF A POLYMERIZATION CATALYST TO EFFECT POLYMERIZATION OF SAID MONOMER FORMULATION AND GRAFTING OF THE POLYMER BEING PRODUCED ONTO THE RUBBERY POLYMER SUBSTRATE TO FORM A GRAFT COPOLYMER, SAID GRAFT COPOLYMER HAVING A SUPERSTRATE TO SUBSTRATE RATIO OF AT LEAST 10:100: C. ADMIXTURE SAID GRAFT COPLYMER WITH A SECOND POLYMERIZABLE COMPOSITION COMPRISING FROM 55 TO 85 PERCENT BY WEIGHT OF AN ETHYLENICALLY UNSATURATED NITRILE MONOMER SELECTED FROM THE GROUP CONSISTING OF ACRYLONITRILE AND MIXTURES OF ACRYLONITRILE AND METHACRYLONITRILE CONTAINS UP TO 20 PERCENT BY WEIGHT OF METHACRYLONITRILE BASED ON THE TOTAL WEIGHT OF ACRYLONITRILE AND MATHACRYLONYITRILE AND FROM 15 TO 45 PERCENT BY WEIGHT OF A MONOVINYLIDENE AROMATIC HYDROCARBON MONOMER WHEREIN THE PERCENT BY WEIGHT IS BASED ON THE TOTAL WEIGHT OF THE MONOMERS IN THE SECOND POLYMERIZABLE MONOMER MIXTURE, AND D. HEATING THE SECOND MENTIONED ADMIXTURE TO A TEMPERATURE IN THE RANGE OF FROM 30* TO 100*C. IN THE PRESENCE OF A POLYMERIZATION CATALYST TO EFFECT POLYMERIZATION OF THE MONOMERS THEREOF AND TO PRODUCE GRAFTING OF THE POLYMER BEING PRODUCED ONTO SAID GRAFT COPOLYMER TO FORM A COMPOSITE GRAFT COPOLYMER, SAID GRAFTED POLYMER OF SAID FIRST AND SECOND ADMIXTURES PROVIDING A GRAFTED SUPERSTRATE WHICH CONTAINS A TOTAL OF AT LEAST 40 PERCENT BY WEIGHT ETHYLENICALLY UNSATURATED NITRILE MONOMER AND WHEREIN THE RATIO OF GRAFTED SUPERSTRATE TO SUBSTRATE IS IN THE RANGE OF FROM 15-200:100, E. BLENDING THE POLYMERIZATION PRODUCT OF STEPS A TO D ABOVE WITH A MATRIX POLYMER WHICH COMPRISES FROM 55 TO 85 PERCENT BASED ON THE TOTAL WEIGHT OF THE POLYMER, OF AN ETHYLENICALLY UNSATURATED NITRILE MONOMER SELECTED FROM THE GROUP CONSISTING OF ACRYLONITRILE AND MIXTURES OF ACRYLONITRILE AND METHACRYLONITRILE WHICH CONTAIN UP TO 20 PERCENT BY WEIGHT OF METHACRYLONITRILE BASED ON THE TOTAL WEIGHT OF ACRYLONITRILE AND METHACRYLONITRILE AND FROM 15 TO 45 PRECENT OF A MONOVINYLIDENE AROMATIC HYDROCARBON MONOMER, WHEREIN THE RUSULTING BLEND CONTAINS FROM 3 TO 50% BY WEIGHT OF THE RUBBERY POLYMER SUBSTRATE.

Claim 7

a first polymerizable monomer composition comprising: a. from 0.1 to 2 percent by weight of a nonconjugated diolefin monomer; b. from 20 to 30 percent by weight of an ethylenically unsaturated nitrile monomer selected from the group consisting of acrylonitrile; and mixtures of acrylonitrile and methacrylonitrile; c. from 40 to 60 percent by weight of a vinylidene aromatic hydrocarbon monomer selected from the group consisting of styrene and alpha methyl styrene; and d. from 20 to 50 percent by weight of methyl methacrylate; B. heating the admixture to a temperature in the range of from 30* to 100*C. in the presence of a polymerization catalyst to effect polymerization of said monomer formulation and grafting of the polymer being produced onto the rubbery polymer substrate to form a graft copolymer, said graft copolymer having a superstrate to substrate ratio of at least 10:100; C. admixing said graft copolymer with a second polymerizable composition comprising from 55 to 85 percent by weight of an ethylenically unsaturated nitrile monomer selected from the group consisting of acrylonitrile and mixtures of acrylonitrile and methacrylonitrile which contains up to 20 percent by weight of methacrylonItrile based on the total weight of acrylonitrile and methacrylonitrile and from 15 to 45 percent by weight of a monovinylidene aromatic hydrocarbon monomer wherein the percent by weight is based on the total weight of the monomers in the second polymerizable monomer mixture; and D. heating the second mentioned admixture to a temperature in the range of from 30* to 100*C. in the presence of a polymerization catalyst to effect polymerization of the monomers thereof and to produce grafting of the polymer being produced onto said graft copolymer to form a composite graft copolymer, said grafted polymers of said first and second admixtures providing a grafted superstrate which contains a total of at least 40 percent by weight ethylenically unsaturated nitrile monomer and wherein the ratio of grafted superstrate to substrate is in the range of from 15-200:100; E. blending the polymerization product of steps A to D above with a matrix polymer which is the polymerization product which comprises 60 to 85 percent by weight, based on the total weight of the polymer, of an ethylenically unsaturated nitrile monomer selected from the group consisting of acrylonitrile and mixtures of acrylonitrile and methacrylonitrile which contain up to 20 percent by weight of methacrylonitrile based on the total weight of acrylonitrile and methacrylonitrile and from 15 to 45 percent of a monovinylidene aromatic hydrocarbon monomer; wherein the resulting blend contains from 3 to 50% by weight of the rubbery polymer substrate.

Claim 8

a first polymerizable monomer composition comprising: a. from 0.1 to 2 percent by weight of a nonconjugated diolefin monomer; b. from 20 to 30 percent by weight of an ethylenically unsaturated nitrile monomer selected from the group consisting of acrylonitrile; and mixtures of acrylonitrile and methacrylonitrile; c. from 40 to 60 percent by weight of a vinylidene aromatic hydrocarbon monomer selected from the group consisting of styrene and alpha methyl styrene; and d. from 20 to 50 percent by weight of methyl methacrylate; B. heating the admixture to a temperature in the range of from 30* to 100*C. in the presence of a polymerization catalyst to effect polymerization of said monomer formulation and grafting of the polymer being produced onto the rubbery polymer substrate to form a graft copolymer, said graft copolymer having a superstrate to substrate ratio of at least 10:100; C. admixing said graft copolymer with a second polymerizable composition comprising from 55 to 85 percent by weight of an ethylenically unsaturated nitrile monomer selected from the group consisting of acrylonitrile and mixtures of acrylonitrile and methacrylonitrile which contains up to 20 percent by weight of methacrylonItrile based on the total weight of acrylonitrile and methacrylonitrile and from 15 to 45 percent by weight of a monovinylidene aromatic hydrocarbon monomer wherein the percent by weight is based on the total weight of the monomers in the second polymerizable monomer mixture; and D. heating the second mentioned admixture to a temperature in the range of from 30* to 100*C. in the presence of a polymerization catalyst to effect polymerization of the monomers thereof and to produce grafting of the polymer being produced onto said graft copolymer to form a composite graft copolymer, said grafted polymers of said first and second admixtures providing a grafted superstrate which contains a total of at least 40 percent by weight ethylenically unsaturated nitrile monomer and wherein the ratio of grafted superstrate to substrate is in the range of from 15-200:100; E. blending the polymerization product of steps A to D above with a matrix polymer which is the polymerization product which comprises 60 to 85 percent by weight, based on the total weight of the polymer, of an ethylenically unsaturated nitrile monomer selected from the group consisting of acrylonitrile and mixtures of acrylonitrile and methacrylonitrile which contain up to 20 percent by weight of methacrylonitrile based on the total weight of acrylonitrile and methacrylonitrile and from 15 to 45 percent of a monovinylidene aromatic hydrocarbon monomer; wherein the resulting blend contains from 3 to 50% by weight of the rubbery polymer substrate.

Claim 9

a first polymerizable monomer composition comprising: a. from 0.1 to 2 percent by weight of a nonconjugated diolefin monomer; b. from 0 to 30 percent by weight of an ethylenically unsaturated nitrile monomer selected from the group consisting of acrylonitrile, and mixtures of acrylonitrile and methacrylonitrile; c. from 40 to 60 percent by weight of a vinylidene aromatic hydrocarbon monomer; and d. from 20 to 50 percent by weight of an alkyl ester of acrylic or methacrylic acid wherein the alkyl group contains from 1 to 8 carbon atoms, wherein the percent by weight is based on the total weight of the monomer in the first polymerizable monomer mixture; B. heating the admixture to a temperature in the range of from 30* to 100*C. in the presence of a polymerization catalyst to effect polymerization of said monomer formulation and grafting of the polymer being produced onto the rubbery polymer substrate to form a graft copolymer, said graft copolymer having a superstrate to substrate ratio of at least 10:100; C. admixing said graft copolymer with a second polymerizable composition comprising from 55 to 85 percent by weight of an ethylenically unsaturated nitrile monomer selected from the group consisting of acrylonitrile and mixtures of acrylonitrile and methacrylonitrile which contains up to 20 percent by weight of methacrylonitrile based on the total weight of acrylonitrile and methacrylonitrile and from 15 to 45 percent by weight of a monovinylidene aromatic hydrocarbon monomer wherein the percent by weight is based on the total weight of the monomers in the second polymerizable monomer mixture; and D. heating the second mentioned admixture to a temperature in the range of from 30* to 100*C. in the presence of a polymerization catalyst to effect polymerization of the monomers thereof and to produce grafting of the poLymer being produced onto said graft copolymer to form a composite graft copolymer, said grafted polymers of said first and second admixtures providing a grafted superstrate which contains a total of at least 40 percent by weight ethylenically unsaturated nitrile monomer and wherein the ratio of grafted superstrate to substrate is in the range of from 15-200:100; E. blending the polymerization product of steps A to D above with a matrix polymer which comprises from 55 to 85 percent, based on the total weight of the polymer, of an ethylenically unsaturated nitrile monomer selected from the group consisting of acrylonitrile and mixtures of acrylonitrile and methacrylonitrile which contain up to 20 percent by weight of methacrylonitrile based on the total weight of acrylonitrile and methacrylonitrile and from 15 to 45 percent of a monovinylidene aromatic hydrocarbon monomer; wherein the resulting blend contains from 3 to 50% by weight of the rubbery polymer substrate.

Claim 10

a first polymerizable monomer composition comprising: a. from 0.1 to 2 percent by weight of a nonconjugated diolefin monomer; b. from 0 to 30 percent by weight of an ethylenically unsaturated nitrile monomer selected from the group consisting of acrylonitrile, and mixtures of acrylonitrile and methacrylonitrile; c. from 40 to 60 percent by weight of a vinylidene aromatic hydrocarbon monomer; and d. from 20 to 50 percent by weight of an alkyl ester of acrylic or methacrylic acid wherein the alkyl group contains from 1 to 8 carbon atoms, wherein the percent by weight is based on the total weight of the monomer in the first polymerizable monomer mixture; B. heating the admixture to a temperature in the range of from 30* to 100*C. in the presence of a polymerization catalyst to effect polymerization of said monomer formulation and grafting of the polymer being produced onto the rubbery polymer substrate to form a graft copolymer, said graft copolymer having a superstrate to substrate ratio of at least 10:100; C. admixing said graft copolymer with a second polymerizable composition comprising from 55 to 85 percent by weight of an ethylenically unsaturated nitrile monomer selected from the group consisting of acrylonitrile and mixtures of acrylonitrile and methacrylonitrile which contains up to 20 percent by weight of methacrylonitrile based on the total weight of acrylonitrile and methacrylonitrile and from 15 to 45 percent by weight of a monovinylidene aromatic hydrocarbon monomer wherein the percent by weight is based on the total weight of the monomers in the second polymerizable monomer mixture; and D. heating the second mentioned admixture to a temperature in the range of from 30* to 100*C. in the presence of a polymerization catalyst to effect polymerization of the monomers thereof and to produce grafting of the poLymer being produced onto said graft copolymer to form a composite graft copolymer, said grafted polymers of said first and second admixtures providing a grafted superstrate which contains a total of at least 40 percent by weight ethylenically unsaturated nitrile monomer and wherein the ratio of grafted superstrate to substrate is in the range of from 15-200:100; E. blending the polymerization product of steps A to D above with a matrix polymer which comprises from 55 to 85 percent, based on the total weight of the polymer, of an ethylenically unsaturated nitrile monomer selected from the group consisting of acrylonitrile and mixtures of acrylonitrile and methacrylonitrile which contain up to 20 percent by weight of methacrylonitrile based on the total weight of acrylonitrile and methacrylonitrile and from 15 to 45 percent of a monovinylidene aromatic hydrocarbon monomer; wherein the resulting blend contains from 3 to 50% by weight of the rubbery polymer substrate.

Claim 11

A process as in claim 1 wherein up to 5 percent by weight of the butadiene in the rubbery substrate is replaced with acrylonitrile.

Claim 12

A process as in claim 1 wherein said first-mentioned polymerizable monomer formulation contains acrylonitrile, a monovinylidene aromatic hydrocarbon monomer, methyl methacrylate and ethylene glycol dimethacrylate.

Claim 13

A process as in claim 1 wherein the second polymerizable monomer mixture contains acrylonitrile and styrene.

Claim 14

A process as in claim 1 wherein the nitrile monomer used in the first polymerizable monomer is a mixture of acrylonitrile and methacrylonitrile.

Claim 15

A process as in claim 1 wherein the nitrile monomer used in the second polymerizable monomer is a mixture of acrylonitrile and methacrylonitrile.

Claim 16

A process as in claim 1 wherein the graft polymerization is carried out in an aqueous medium.

Claim 17

A process for preparing rubber modified nitrile polymer compositions which comprises: A. admixing

Claim 18

A process for preparing rubber modified nitrile polymer compositions which comprises: A. admixing