EP0369604A2
Expired / Lapsed
EP
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Grafted polymers and process for their preparation
Assignee: DuPont Canada Inc
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Filing: 1989-10-16
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Granted: —
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Expires: 2009-10-16
Abstract
Abstract A process for the catalytic grafting of an ethylenically unsaturated monomer onto a copolymer in the presence of a catalyst is disclosed. The monomer is a selected from the group consisting of ethylenically unsaturated carboxylic acids, anhydrides esters and other derivatives thereof. The copolymer is selected from the group consisting of copolymers of ethylene with at least one monomer selected from the group consisting of vinyl alkylates, carbon monoxide, acrylic acid, methacrylic acid, acrylate esters and methacrylate esters, and mixtures thereof, and ionomers of such copolymers. The catalyst is comprised of a mixture of (a) water and (b) at least one phosphorus-containing compound selected from the group consisting of (i) phosphorus compounds of the formula HPO(OR₁)₂, where each R₁ is independently selected from H, alkyl, aryl and alkaryl, (ii) phosphite compounds of the formula P(OR₂)₃, where each R₂ is independently selected from alkyl, aryl and alkaryl, (iii) phosphite compounds of the formula (OR₃)₂P-O-R₄-O- P(OR₅)₂, where each of R₃, R₄ and R₅ is independently selected from alkyl, aryl and alkaryl, and (iv) di-substituted pentaerythritol diphosphites of the formula (R₆O)P-O₂R PE O₂-P(OR₇), where each of R₆ and R₇ is independently selected from alkyl, aryl and alkaryl and O₂R PE O₂ represents the pentaerythritol moiety. The amount of water being about 0.01-10 parts by weight per part of phosphorus-containing compound, with the proviso that if the phosphorus-containing compound is phosphorous acid then the amount of water is 0.001-10 parts. The process comprises admixing copolymer, monomer, at least 15 ppm of catalyst and 25-2500 ppm of an organic peroxide having a half-life of from about 1 minute to about 120 minutes at 150°C, and admixing at a temperature above the melting point of said copolymer for a period of time that is at least 4 times the half-life of the organic peroxide so as to obtain a uniform distribution of monomer, catalyst and peroxide in the copolymer. The resultant grafted copolymer may then be extruded into a shaped article. The grafted polymer which has improved colour is useful in adhesive systems and as a compatibilizer for polymers and other materials, and is also claimed.
Inventors
- 👤 David John Mitchel
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-11-07 15:16
CPC Classifications
C; C08; C08F; C08F255/00; C08F255/02; C08F4/00; C08F4/28; C08F4/32
Claims Analysis
Total Claims: 20
Claim 1
Independent Claim
320 words
A process for the grafting of ethylenically unsaturated monomers onto a copolymer in the presence of a catalyst, said monomers being selected from the group consisting of ethylenically unsaturated carboxylic acids, anhydrides, esters and other derivatives thereof, and mixtures thereof, said copolymer being selected from the group consisting of copolymers of ethylene with at least one monomer selected from the group consisting of vinyl alkylates, carbon monoxide, acrylic acid, methacrylic acid, acrylate esters and methacrylate esters, and mixtures thereof, and ionomers of such copolymers, and said catalyst being comprised of a mixture of (a) water and (b) at least one phosphorus-containing compound selected from the group consisting of (i) phosphorus compounds of the formula HPO(OR₁)₂, where each R₁ is independently selected from H, alkyl, aryl and alkaryl, (ii) phosphite compounds of the formula P(OR₂)₃, where each R₂ is independently selected from alkyl, aryl and alkaryl, (iii) phosphite compounds of the formula (OR₃)₂P-O-R₄-O- P(OR₅)₂, where each of R₃, R₄ and R₅ is independently selected from alkyl, aryl and alkaryl, and (iv) di-substituted pentaerythritol diphosphites of the formula (R₆O)P-O₂R PE O₂-P(OR₇), where each of R₆ and R₇ is independently selected from alkyl, aryl and alkaryl and O₂R PE O₂ represents the pentaerythritol moiety, the amount of water being about 0.01-10 parts by weight per part of phosphorus-containing compound, with the proviso that if the phosphorus-containing compound is phosphorous acid then the amount of water is 0.001-10 parts, said process comprising: (i) admixing copolymer, monomer, at least ppm of catalyst and 25-5000 ppm of an organic peroxide having a half-life of from about 1 minute to about 120 minutes at 150°C, at a temperature above the melting point of said copolymer for a period of time that is at least 4 times the half-life of the organic peroxide so as to obtain a uniform distribution of monomer, catalyst and peroxide in the copolymer; (ii) extruding the resultant grafted copolymer into a shaped article.
Claim 2
Dependent Claim
320 words
A process for the grafting of ethylenically unsaturated monomers onto a copolymer in the presence of a catalyst, said monomers being selected from the group consisting of ethylenically unsaturated carboxylic acids, anhydrides, esters and other derivatives thereof, and mixtures thereof, said copolymer being selected from the group consisting of copolymers of ethylene with at least one monomer selected from the group consisting of vinyl alkylates, carbon monoxide, acrylic acid, methacrylic acid, acrylate esters and methacrylate esters, and mixtures thereof, and ionomers of such copolymers, and said catalyst being comprised of a mixture of (a) water and (b) at least one phosphorus-containing compound selected from the group consisting of (i) phosphorus compounds of the formula HPO(OR₁)₂, where each R₁ is independently selected from H, alkyl, aryl and alkaryl, (ii) phosphite compounds of the formula P(OR₂)₃, where each R₂ is independently selected from alkyl, aryl and alkaryl, (iii) phosphite compounds of the formula (OR₃)₂P-O-R₄-O- P(OR₅)₂, where each of R₃, R₄ and R₅ is independently selected from alkyl, aryl and alkaryl, and (iv) di-substituted pentaerythritol diphosphites of the formula (R₆O)P-O₂R PE O₂-P(OR₇), where each of R₆ and R₇ is independently selected from alkyl, aryl and alkaryl and O₂R PE O₂ represents the pentaerythritol moiety, the amount of water being about 0.01-10 parts by weight per part of phosphorus-containing compound, with the proviso that if the phosphorus-containing compound is phosphorous acid then the amount of water is 0.001-10 parts, said process comprising: (i) admixing copolymer, monomer, at least ppm of catalyst and 25-5000 ppm of an organic peroxide having a half-life of from about 1 minute to about 120 minutes at 150°C, at a temperature above the melting point of said copolymer for a period of time that is at least 4 times the half-life of the organic peroxide so as to obtain a uniform distribution of monomer, catalyst and peroxide in the copolymer; (ii) extruding the resultant grafted copolymer into a shaped article.
Claim 3
Dependent Claim
20 words
The process of Claim 1 in which the ethylenically unsaturated acid and anhydride are maleic acid and maleic anhydride, respectively.
Claim 4
Dependent Claim
29 words
The process of Claim 1 or Claim 1 in which the catalyst is in the form of a concentrate in a polymer, said polymer being compatible with the copolymer.
Claim 5
Dependent Claim
24 words
The process of any one of Claims 1-3 in which the organic peroxide is selected from dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butyl peroxy) hexane 2,5-dimethyl-2,5-di(t-butyl peroxy) hexyne-3.
Claim 6
Dependent Claim
21 words
The process of any one of Claims 1-4 in which the amount of organic peroxide is in the range 100-2500 ppm.
Claim 7
Dependent Claim
18 words
The process of Claim 5 in which the amount of organic peroxide is in the range 500-2000 ppm.
Claim 8
Dependent Claim
24 words
The process of any one of Claims 1-6 in which the amount of water is in the range of about 0.001-10 parts by weight.
Claim 9
Dependent Claim
21 words
The process of Claim 7 in which the amount of water is in the range of about 0.01-1 parts by weight.
Claim 10
Dependent Claim
21 words
The process of Claim 8 in which the amount of water is in the range of about 0.03-0.5 parts by weight.
Claim 11
Dependent Claim
20 words
The process of any one of Claims 1-9 in which the amount of phosphorus-containing compound is at least 120 ppm.
Claim 12
Dependent Claim
19 words
The process of Claim 10 in which the amount of phosphorus-containing compound is in the range of 100-1000 ppm.
Claim 13
Dependent Claim
30 words
The process of any one of Claims 1-11 in which the phosphorus-containing compound is of the formula HPO(OR₁)₂, where each R₁ is independently selected from H, alkyl, aryl and alkaryl.
Claim 14
Dependent Claim
12 words
The process of Claim 12 in which the catalyst is phosphorous acid.
Claim 15
Dependent Claim
29 words
The process of any one of Claims 1-11 in which the phosphorus-containing compound is of the formula P(OR₂)₃, where each R₂ is independently selected from alkyl, aryl and alkaryl.
Claim 16
Dependent Claim
34 words
The process of any one of Claims 1-11 in which the phosphorus-containing compound is of the formula (OR₃)₂P-O-R₄-O- P(OR₅)₂, where each of R₃, R₄ and R₅ is independently selected from alkyl, aryl and alkaryl.
Claim 17
Dependent Claim
47 words
The process of any one of Claims 1-11 in which the phosphorus-containing compound is a di-substituted pentaerythritol diphosphite of the formula (R₆O)P-O₂R PE O₂- P(OR₇), where each of R₆ and R₇ is independently selected from alkyl, aryl and alkaryl and O₂R PE O₂ represents the pentaerythritol moiety.
Claim 18
Dependent Claim
294 words
A grafted copolymer composition having 0.5 to 5% by weight of monomer grafted thereon, said copolymer being selected from the group consisting of copolymers of ethylene with at least one monomer selected from the group consisting of vinyl alkylates, carbon monoxide, acrylic acid, methacrylic acid, acrylate esters and methacrylate esters, and mixtures thereof, and ionomers of such copolymers, and said monomer being selected from the group consisting of ethylenically unsaturated carboxylic acids, anhydrides, esters and other derivatives thereof, and mixtures thereof, said grafted polymer having a melt index that is 20-140% of the melt index of the copolymer prior to grafting, said grafted copolymer having been formed by grafting the monomer onto molten copolymer in the presence of 25-5000 ppm of an organic peroxide having a half-life of from about 1 minute to about 120 minutes at 150°C and at least 15 ppm of a catalyst comprised of a mixture of (a) water and (b) at least one phosphorus-containing compound selected from the group consisting of (i) phosphorus compounds of the formula HPO(OR₁)₂, where each R₁ is independently selected from H, alkyl, aryl and alkaryl, (ii) phosphite compounds of the formula P(OR₂)₃, where each R₂ is independently selected from alkyl, aryl and alkaryl, (iii) phosphite compounds of the formula (OR₃)₂P-O-R₄-O- P(OR₅)₂, where each of R₃, R₄ and R₅ is independently selected from alkyl, aryl and alkaryl, and (iv) di-substituted pentaerythritol diphosphites of the formula (R₆O)P-O₂R PE O₂- P(OR₇), where each of R₆ and R₇ is independently selected from alkyl, aryl and alkaryl and O₂R PE O₂ represents the pentaerythritol moiety, the amount of water being about 0.01-10 parts by weight per part of phosphorus-containing compound, with the proviso that if the phosphorus-containing compound is phosphorous acid then the amount of water is 0.001-10 parts.
Claim 19
Dependent Claim
294 words
A grafted copolymer composition having 0.5 to 5% by weight of monomer grafted thereon, said copolymer being selected from the group consisting of copolymers of ethylene with at least one monomer selected from the group consisting of vinyl alkylates, carbon monoxide, acrylic acid, methacrylic acid, acrylate esters and methacrylate esters, and mixtures thereof, and ionomers of such copolymers, and said monomer being selected from the group consisting of ethylenically unsaturated carboxylic acids, anhydrides, esters and other derivatives thereof, and mixtures thereof, said grafted polymer having a melt index that is 20-140% of the melt index of the copolymer prior to grafting, said grafted copolymer having been formed by grafting the monomer onto molten copolymer in the presence of 25-5000 ppm of an organic peroxide having a half-life of from about 1 minute to about 120 minutes at 150°C and at least 15 ppm of a catalyst comprised of a mixture of (a) water and (b) at least one phosphorus-containing compound selected from the group consisting of (i) phosphorus compounds of the formula HPO(OR₁)₂, where each R₁ is independently selected from H, alkyl, aryl and alkaryl, (ii) phosphite compounds of the formula P(OR₂)₃, where each R₂ is independently selected from alkyl, aryl and alkaryl, (iii) phosphite compounds of the formula (OR₃)₂P-O-R₄-O- P(OR₅)₂, where each of R₃, R₄ and R₅ is independently selected from alkyl, aryl and alkaryl, and (iv) di-substituted pentaerythritol diphosphites of the formula (R₆O)P-O₂R PE O₂- P(OR₇), where each of R₆ and R₇ is independently selected from alkyl, aryl and alkaryl and O₂R PE O₂ represents the pentaerythritol moiety, the amount of water being about 0.01-10 parts by weight per part of phosphorus-containing compound, with the proviso that if the phosphorus-containing compound is phosphorous acid then the amount of water is 0.001-10 parts.
Claim 20
Dependent Claim
21 words
The grafted polymer of Claim 17 in which the ethylenically unsaturated acid and anhydride are maleic acid and maleic anhydride, respectively.
References Cited (Backward Citations)
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