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US 2016/0237264 A1Published application
Alkylphenol-free Polymeric Polyphosphite Stabilizer for Polyolefin Compositions for Film, Fiber and Molded Articles
AssigneeDover Chemical Corporation
InventorsMichael R. Jakupca, Jacob M. Lance, Donald Stevenson, John T. Regula, Jacob J. Weingart
Life of this patent
Estimating the term…
Abstract
The invention pertains generally to an improved polymer composition which contains at least one liquid polymeric polyphosphite additive containing no alkylphenols. Alkylphenol-free polymeric polyphosphites offer distinct advantages over conventional phosphite technology in polyolefin films. Polymeric polyphosphites offer improved performance in regards to the prevention of color formation during high temperature processing, NOx aging, and gamma irradiation.
Claims7
A process to improve the NOx stability of a polyolefin film wherein the Yellowness Index remains less than or equal to 18 after exposure to NOx at 50° C. for a minimum of 20 days, comprising the step of adding at least one homopolymer polyphosphite and copolymer polyphosphite of Formulas (I), (II) or (III) to the polyolefin:
- wherein in Formula (I)
- each R1, R2, R3 and R4 can be the same or different and independently selected from the group consisting of C12-20 alkyl, C12-22 alkenyl, C12-40 cycloalkyl, C12-40 cycloalkylene, C12-20 alkyl glycol ethers and Y—OH as an end-capping group;
- each Y is independently selected from the group consisting of C2-40 alkylene, C7-40 cycloalkylene, C3-20 alkyl glycol ethers, C3-40 alkyl lactone, and —R7—N(R8)—R9—;
- R7, R8 and R9 are independently selected from the group consisting of C1-20 alkyl, C2-22 alkenyl, C6-40 cycloalkyl, C7-40 cycloalkylene and H;
- m is an integral value ranging from 1 to 100 inclusive;
- x is an integral value ranging from 2 to 1,000 with the proviso that when —O—Y is a C3-20 alkyl glycol ether, x is an integral value no less than 7;
- and further wherein
- no more than two of R1, R2, R3 and R4 are terminated with an hydroxyl group;
- wherein in Formula (II)
- each R1, R2, R3, R4 and R5 can be the same or different and independently selected from the group consisting of C12-20 alkyl, C12-22 alkenyl, C12-40 cycloalkyl, C12-40 cycloalkenyl, C12-20 alkyl glycol ethers and A-OH and B—OH as an end-capping groups;
- each A and B are different and independently selected from the group consisting of C2-40 alkylene, C7-40 cycloalkylene, C3-20 alkyl glycol ethers, C3-40 alkyl lactone, and —R7—N(R8)—R9— wherein R7, R8 and R9 are independently selected from the group C1-20 alkyl, C2-22 alkenyl, C6-40 cycloalkyl, C7-40 cycloalkylene and H;
- m and n are integral values ranging from 1 to 100 inclusive;
- x and y are integral values ranging from 1 to 1,000 wherein x+y sum to at least 3, with the proviso that when —O-A or —O—B are C3-20 alkyl glycol ethers, at least one of x or y is an integral value no less than 7;
- and further wherein
- no more than two of R1, R2, R3, R4 and R5 are terminated with an hydroxyl group;
- or Formula (III)
- wherein in Formula (III)
- each R1, R2, R3, R4, R5 and R6 can be the same or different and independently selected from the group consisting of C1-20 alkyl, C2-22 alkenyl, C6-40 cycloalkyl, C7-40 cycloalkylene, C3-20 methoxy alkyl glycol ethers, C3-20 alkyl glycol ethers or Y—OH (serving as an end capping moiety) for R1, R2, R3, R4, R5 and R6;
- Y is selected from the group consisting of C2-40 alkylene, C2-40 alkyl lactone, and C2-40 cycloalkyl and further comprises C2-20 alkyl glycol ethers when Y is in the polyphosphite backbone (e.g., ethylene, propylene, caprylactone, polyalkylene glycol);
- x is an integral value ranging from 8 to 1,000;
- z is an integral value ranging from 0 to 1,000 with the proviso that when z is 8 or greater, then x is an integral value ranging from 1 to 1,000;
- m is an integral value ranging from 1 to 20;
- w is an integral value ranging from 1 to 1,000;
- and
- combinations of formula (I) or Formula (II) or Formula (III).
22 more elements
A process to improve the long term heat aging of a polyolefin film compared to the addition of tris-2,4-di-tert-butylphenol phosphite, comprising the step of adding at least one homopolymer polyphosphite and copolymer polyphosphite of Formulas (I), (II) or (Ill) to the polyolefin:
- wherein in Formula (I)
- each R1, R2, R3 and R4 can be the same or different and independently selected from the group consisting of C12-20 alkyl, C12-22 alkenyl, C12-40 cycloalkyl, C12-40 cycloalkylene, C12-20 alkyl glycol ethers and Y—OH as an end-capping group;
- each Y is independently selected from the group consisting of C2-40 alkylene, C7-40 cycloalkylene, C3-20 alkyl glycol ethers, C3-40 alkyl lactone, and —R7—N(R8)—R9—;
- R7, R8 and R9 are independently selected from the group consisting of C1-20 alkyl, C2-22 alkenyl, C6-40 cycloalkyl, C7-40 cycloalkylene and H;
- m is an integral value ranging from 1 to 100 inclusive;
- x is an integral value ranging from 2 to 1,000 with the proviso that when —O—Y is a C3-20 alkyl glycol ether, x is an integral value no less than 7;
- and further wherein
- no more than two of R1, R2, R3 and R4 are terminated with an hydroxyl group;
- wherein in Formula (II)
- each R1, R2, R3, R4 and R5 can be the same or different and independently selected from the group consisting of C12-20 alkyl, C12-22 alkenyl, C12-40 cycloalkyl, C12-40 cycloalkenyl, C12-20 alkyl glycol ethers and A-OH and B—OH as an end-capping groups;
- each A and B are different and independently selected from the group consisting of C2-40 alkylene, C7-40 cycloalkylene, C3-20 alkyl glycol ethers, C3-40 alkyl lactone, and —R7—N(R8)—R9— wherein R7, R8 and R9 are independently selected from the group C1-20 alkyl, C2-22 alkenyl, C6-40 cycloalkyl, C7-40 cycloalkylene and H;
- m and n are integral values ranging from 1 to 100 inclusive;
- x and y are integral values ranging from 1 to 1,000 wherein x+y sum to at least 3, with the proviso that when —O-A or —O—B are C3-20 alkyl glycol ethers, at least one of x or y is an integral value no less than 7;
- and further wherein
- no more than two of R1, R2, R3, R4 and R5 are terminated with an hydroxyl group;
- or Formula (III)
- wherein in Formula (III)
- each R1, R2, R3, R4, R5 and R6 can be the same or different and independently selected from the group consisting of C1-20 alkyl, C2-22 alkenyl, C6-40 cycloalkyl, C7-40 cycloalkylene, C3-20 methoxy alkyl glycol ethers, C3-20 alkyl glycol ethers or Y—OH (serving as an end capping moiety) for R1, R2, R3, R4, R5 and R6;
- Y is selected from the group consisting of C2-40 alkylene, C2-40 alkyl lactone, and C2-40 cycloalkyl and further comprises C2-20 alkyl glycol ethers when Y is in the polyphosphite backbone (e.g., ethylene, propylene, caprylactone, polyalkylene glycol);
- x is an integral value ranging from 8 to 1,000;
- z is an integral value ranging from 0 to 1,000 with the proviso that when z is 8 or greater, then x is an integral value ranging from 1 to 1,000;
- m is an integral value ranging from 1 to 20;
- w is an integral value ranging from 1 to 1,000;
- and
- combinations of formula (I) or Formula (II) or Formula (III).
22 more elements
A process to reduce gel formation of a polyolefin film compared to the addition of tris(nonylphenyl)phosphite comprising the step of adding at least one homopolymer polyphosphite and copolymer polyphosphite of Formulas (I), (II) or (Ill) to the polyolefin:
- wherein in Formula (I)
- each R1, R2, R3 and R4 can be the same or different and independently selected from the group consisting of C12-20 alkyl, C12-22 alkenyl, C12-40 cycloalkyl, C12-40 cycloalkylene, C12-20 alkyl glycol ethers and Y—OH as an end-capping group;
- each Y is independently selected from the group consisting of C2-40 alkylene, C7-40 cycloalkylene, C3-20 alkyl glycol ethers, C3-40 alkyl lactone, and —R7—N(R8)—R9—;
- R7, R8 and R9 are independently selected from the group consisting of C1-20 alkyl, C2-22 alkenyl, C6-40 cycloalkyl, C7-40 cycloalkylene and H;
- m is an integral value ranging from 1 to 100 inclusive;
- x is an integral value ranging from 2 to 1,000 with the proviso that when —O—Y is a C3-20 alkyl glycol ether, x is an integral value no less than 7;
- and further wherein
- no more than two of R1, R2, R3 and R4 are terminated with an hydroxyl group;
- wherein in Formula (II)
- each R1, R2, R3, R4 and R5 can be the same or different and independently selected from the group consisting of C12-20 alkyl, C12-22 alkenyl, C12-40 cycloalkyl, C12-40 cycloalkenyl, C12-20 alkyl glycol ethers and A-OH and B—OH as an end-capping groups;
- each A and B are different and independently selected from the group consisting of C2-40 alkylene, C7-40 cycloalkylene, C3-20 alkyl glycol ethers, C3-40 alkyl lactone, and —R7—N(R8)—R9— wherein R7, R8 and R9 are independently selected from the group C1-20 alkyl, C2-22 alkenyl, C6-40 cycloalkyl, C7-40 cycloalkylene and H;
- m and n are integral values ranging from 1 to 100 inclusive;
- x and y are integral values ranging from 1 to 1,000 wherein x+y sum to at least 3, with the proviso that when —O-A or —O—B are C3-20 alkyl glycol ethers, at least one of x or y is an integral value no less than 7;
- and further wherein
- no more than two of R1, R2, R3, R4 and R5 are terminated with an hydroxyl group;
- or Formula (III)
- wherein in Formula (III)
- each R1, R2, R3, R4, R5 and R6 can be the same or different and independently selected from the group consisting of C1-20 alkyl, C2-22 alkenyl, C6-40 cycloalkyl, C7-40 cycloalkylene, C3-20 methoxy alkyl glycol ethers, C3-20 alkyl glycol ethers or Y—OH (serving as an end capping moiety) for R1, R2, R3, R4, R and R6;
- Y is selected from the group consisting of C2-40 alkylene, C2-40 alkyl lactone, and C2-40 cycloalkyl and further comprises C2-20 alkyl glycol ethers when Y is in the polyphosphite backbone (e.g., ethylene, propylene, caprylactone, polyalkylene glycol);
- x is an integral value ranging from 8 to 1,000;
- z is an integral value ranging from 0 to 1,000 with the proviso that when z is 8 or greater, then x is an integral value ranging from 1 to 1,000;
- m is an integral value ranging from 1 to 20;
- w is an integral value ranging from 1 to 1,000;
- and
- combinations of formula (I) or Formula (II) or Formula (III).
22 more elements
A process to improve the melt processing of a polyolefin film synergistically with the primary antioxidant Vitamin E, comprising the step of adding at least one homopolymer polyphosphite and copolymer polyphosphite of Formulas (I), (II) or (III) to the polyolefin:
- wherein in Formula (I)
- each R1, R2, R3 and R4 can be the same or different and independently selected from the group consisting of C12-20 alkyl, C12-22 alkenyl, C12-40 cycloalkyl, C12-40 cycloalkylene, C12-20 alkyl glycol ethers and Y—OH as an end-capping group;
- each Y is independently selected from the group consisting of C2-40 alkylene, C7-40 cycloalkylene, C3-20 alkyl glycol ethers, C3-40 alkyl lactone, and —R7—N(R8)—R9—;
- R7, R8 and R9 are independently selected from the group consisting of C1-20 alkyl, C2-22 alkenyl, C6-40 cycloalkyl, C7-40 cycloalkylene and H;
- m is an integral value ranging from 1 to 100 inclusive;
- x is an integral value ranging from 2 to 1,000 with the proviso that when —O—Y is a C3-20 alkyl glycol ether, x is an integral value no less than 7;
- and further wherein
- no more than two of R1, R2, R3 and R4 are terminated with an hydroxyl group;
- wherein in Formula (II)
- each R1, R2, R3, R4 and R5 can be the same or different and independently selected from the group consisting of C12-20 alkyl, C12-22 alkenyl, C12-40 cycloalkyl, C12-40 cycloalkenyl, C12-20 alkyl glycol ethers and A-OH and B—OH as an end-capping groups;
- each A and B are different and independently selected from the group consisting of C2-40 alkylene, C7-40 cycloalkylene, C3-20 alkyl glycol ethers, C3-40 alkyl lactone, and —R7—N(R8)—R9— wherein R7, R8 and R9 are independently selected from the group C1-20 alkyl, C2-22 alkenyl, C6-40 cycloalkyl, C7-40 cycloalkylene and H;
- m and n are integral values ranging from 1 to 100 inclusive;
- x and y are integral values ranging from 1 to 1,000 wherein x+y sum to at least 3, with the proviso that when —O-A or —O—B are C3-20 alkyl glycol ethers, at least one of x or y is an integral value no less than 7;
- and further wherein
- no more than two of R1, R2, R3, R4 and R5 are terminated with an hydroxyl group;
- or Formula (III)
- wherein in Formula (III)
- each R1, R2, R3, R4, R5 and R6 can be the same or different and independently selected from the group consisting of C1-20 alkyl, C2-22 alkenyl, C6-40 cycloalkyl, C7-40 cycloalkylene, C3-20 methoxy alkyl glycol ethers, C3-20 alkyl glycol ethers or Y—OH (serving as an end capping moiety) for R1, R2, R3, R4, R5 and R6;
- Y is selected from the group consisting of C2-40 alkylene, C2-40 alkyl lactone, and C2-40 cycloalkyl and further comprises C2-20 alkyl glycol ethers when Y is in the polyphosphite backbone (e.g., ethylene, propylene, caprylactone, polyalkylene glycol);
- x is an integral value ranging from 8 to 1,000;
- z is an integral value ranging from 0 to 1,000 with the proviso that when z is 8 or greater, then x is an integral value ranging from 1 to 1,000;
- m is an integral value ranging from 1 to 20;
- w is an integral value ranging from 1 to 1,000;
- and
- combinations of formula (I) or Formula (II) or Formula (III).
22 more elements
A process to improve the resistance of an antioxidant to migrate out to a surface of a polyolefin film compared to tris-nonylphenol phosphite or tris-2,4-di-tert-butylphenol phosphite comprising the step of adding at least one homopolymer polyphosphite and copolymer polyphosphite of Formulas (I), (II) or (Ill) to the polyolefin:
- wherein in Formula (I)
- each R1, R2, R3 and R4 can be the same or different and independently selected from the group consisting of C12-20 alkyl, C12-22 alkenyl, C12-40 cycloalkyl, C12-40 cycloalkylene, C12-20 alkyl glycol ethers and Y—OH as an end-capping group;
- each Y is independently selected from the group consisting of C2-40 alkylene, C7-40 cycloalkylene, C3-20 alkyl glycol ethers, C3-40 alkyl lactone, and —R7—N(R8)—R9—;
- R7, R8 and R9 are independently selected from the group consisting of C1-20 alkyl, C2-22 alkenyl, C6-40 cycloalkyl, C7-40 cycloalkylene and H;
- m is an integral value ranging from 1 to 100 inclusive;
- x is an integral value ranging from 2 to 1,000 with the proviso that when —O—Y is a C3-20 alkyl glycol ether, x is an integral value no less than 7;
- and further wherein
- no more than two of R1, R2, R3 and R4 are terminated with an hydroxyl group;
- wherein in Formula (II)
- each R1, R2, R3, R4 and R5 can be the same or different and independently selected from the group consisting of C12-20 alkyl, C12-22 alkenyl, C12-40 cycloalkyl, C12-40 cycloalkenyl, C12-20 alkyl glycol ethers and A-OH and B—OH as an end-capping groups;
- each A and B are different and independently selected from the group consisting of C2-40 alkylene, C7-40 cycloalkylene, C3-20 alkyl glycol ethers, C3-40 alkyl lactone, and —R7—N(R8)—R9— wherein R7, R8 and R9 are independently selected from the group C1-20 alkyl, C2-22 alkenyl, C6-40 cycloalkyl, C7-40 cycloalkylene and H;
- m and n are integral values ranging from 1 to 100 inclusive;
- x and y are integral values ranging from 1 to 1,000 wherein x+y sum to at least 3, with the proviso that when —O-A or —O—B are C3-20 alkyl glycol ethers, at least one of x or y is an integral value no less than 7;
- and further wherein
- no more than two of R1, R2, R3, R4 and R5 are terminated with an hydroxyl group;
- or Formula (III)
- wherein in Formula (III)
- each R1, R2, R3, R4, R5 and R6 can be the same or different and independently selected from the group consisting of C1-20 alkyl, C2-22 alkenyl, C6-40 cycloalkyl, C7-40 cycloalkylene, C3-20 methoxy alkyl glycol ethers, C3-20 alkyl glycol ethers or Y—OH (serving as an end capping moiety) for R1, R2, R3, R4, R5 and R6;
- Y is selected from the group consisting of C2-40 alkylene, C2-40 alkyl lactone, and C2-40 cycloalkyl and further comprises C2-20 alkyl glycol ethers when Y is in the polyphosphite backbone (e.g., ethylene, propylene, caprylactone, polyalkylene glycol);
- x is an integral value ranging from 8 to 1,000;
- z is an integral value ranging from 0 to 1,000 with the proviso that when z is 8 or greater, then x is an integral value ranging from 1 to 1,000;
- m is an integral value ranging from 1 to 20;
- w is an integral value ranging from 1 to 1,000;
- and
- combinations of formula (I) or Formula (II) or Formula (III).
22 more elements
A process to improve the Yellowness Index of a polyolefin film when exposed to gamma irradiation in comparison to the addition of tris-di-tert-butyl phenol phosphite, comprising the step of adding at least one homopolymer polyphosphite and copolymer polyphosphite of Formulas (I), (II) or (III) to the polyolefin:
- wherein in Formula (I)
- each R1, R2, R3 and R4 can be the same or different and independently selected from the group consisting of C12-20 alkyl, C12-22 alkenyl, C12-40 cycloalkyl, C12-40 cycloalkylene, C12-20 alkyl glycol ethers and Y—OH as an end-capping group;
- each Y is independently selected from the group consisting of C2-40 alkylene, C7-40 cycloalkylene, C3-20 alkyl glycol ethers, C3-40 alkyl lactone, and —R7—N(R8)—R9—;
- R7, R8 and R9 are independently selected from the group consisting of C1-20 alkyl, C2-22 alkenyl, C6-40 cycloalkyl, C7-40 cycloalkylene and H;
- m is an integral value ranging from 1 to 100 inclusive;
- x is an integral value ranging from 2 to 1,000 with the proviso that when —O—Y is a C3-20 alkyl glycol ether, x is an integral value no less than 7;
- and further wherein
- no more than two of R1, R2, R3 and R4 are terminated with an hydroxyl group;
- wherein in Formula (II)
- each R1, R2, R3, R4 and R5 can be the same or different and independently selected from the group consisting of C12-20 alkyl, C12-22 alkenyl, C12-40 cycloalkyl, C12-40 cycloalkenyl, C12-20 alkyl glycol ethers and A-OH and B—OH as an end-capping groups;
- each A and B are different and independently selected from the group consisting of C2-40 alkylene, C7-40 cycloalkylene, C3-20 alkyl glycol ethers, C3-40 alkyl lactone, and —R7—N(R8)—R9— wherein R7, R8 and R9 are independently selected from the group C1-20 alkyl, C2-22 alkenyl, C6-40 cycloalkyl, C7-40 cycloalkylene and H;
- m and n are integral values ranging from 1 to 100 inclusive;
- x and y are integral values ranging from 1 to 1,000 wherein x+y sum to at least 3, with the proviso that when —O-A or —O—B are C3-20 alkyl glycol ethers, at least one of x or y is an integral value no less than 7;
- and further wherein
- no more than two of R1, R2, R3, R4 and R5 are terminated with an hydroxyl group;
- or Formula (III)
- wherein in Formula (III)
- each R1, R2, R3, R4, R5 and R6 can be the same or different and independently selected from the group consisting of C1-20 alkyl, C2-22 alkenyl, C6-40 cycloalkyl, C7-40 cycloalkylene, C3-20 methoxy alkyl glycol ethers, C3-20 alkyl glycol ethers or Y—OH (serving as an end capping moiety) for R1, R2, R3, R4, R5 and R6;
- Y is selected from the group consisting of C2-40 alkylene, C2-40 alkyl lactone, and C2-40 cycloalkyl and further comprises C2-20 alkyl glycol ethers when Y is in the polyphosphite backbone (e.g., ethylene, propylene, caprylactone, polyalkylene glycol);
- x is an integral value ranging from 8 to 1,000;
- z is an integral value ranging from 0 to 1,000 with the proviso that when z is 8 or greater, then x is an integral value ranging from 1 to 1,000;
- m is an integral value ranging from 1 to 20;
- w is an integral value ranging from 1 to 1,000;
- and
- combinations of formula (I) or Formula (II) or Formula (III).
22 more elements
A process to reduce the bloom exudation of a polyolefin film in comparison to the addition of tris-di-tert-butylphenol phosphite comprising the step of adding at least one homopolymer polyphosphite and copolymer polyphosphite of Formulas (I), (II) or (Ill) to the polyolefin:
- wherein in Formula (I)
- each R1, R2, R3 and R4 can be the same or different and independently selected from the group consisting of C12-20 alkyl, C12-22 alkenyl, C12-40 cycloalkyl, C12-40 cycloalkylene, C12-20 alkyl glycol ethers and Y—OH as an end-capping group;
- each Y is independently selected from the group consisting of C2-40 alkylene, C7-40 cycloalkylene, C3-20 alkyl glycol ethers, C3-40 alkyl lactone, and —R7—N(R8)—R9—;
- R7, R8 and R9 are independently selected from the group consisting of C1-20 alkyl, C2-22 alkenyl, C6-40 cycloalkyl, C7-40 cycloalkylene and H;
- m is an integral value ranging from 1 to 100 inclusive;
- x is an integral value ranging from 2 to 1,000 with the proviso that when —O—Y is a C3-20 alkyl glycol ether, x is an integral value no less than 7;
- and further wherein
- no more than two of R1, R2, R3 and R4 are terminated with an hydroxyl group;
- wherein in Formula (II)
- each R1, R2, R3, R4 and R5 can be the same or different and independently selected from the group consisting of C12-20 alkyl, C12-22 alkenyl, C12-40 cycloalkyl, C12-40 cycloalkenyl, C12-20 alkyl glycol ethers and A-OH and B—OH as an end-capping groups;
- each A and B are different and independently selected from the group consisting of C2-40 alkylene, C7-40 cycloalkylene, C3-20 alkyl glycol ethers, C3-40 alkyl lactone, and —R7—N(R5)—R9— wherein R7, R5 and R9 are independently selected from the group C1-20 alkyl, C2-22 alkenyl, C6-40 cycloalkyl, C7-40 cycloalkylene and H;
- m and n are integral values ranging from 1 to 100 inclusive;
- x and y are integral values ranging from 1 to 1,000 wherein x+y sum to at least 3, with the proviso that when —O-A or —O—B are C3-20 alkyl glycol ethers, at least one of x or y is an integral value no less than 7;
- and further wherein
- no more than two of R1, R2, R3, R4 and R5 are terminated with an hydroxyl group;
- or Formula (III)
- wherein in Formula (III)
- each R1, R2, R3, R4, R5 and R6 can be the same or different and independently selected from the group consisting of C1-20 alkyl, C2-22 alkenyl, C6-40 cycloalkyl, C7-40 cycloalkylene, C3-20 methoxy alkyl glycol ethers, C3-20 alkyl glycol ethers or Y—OH (serving as an end capping moiety) for R1, R2, R3, R4, R5 and R6;
- Y is selected from the group consisting of C2-40 alkylene, C2-40 alkyl lactone, and C2-40 cycloalkyl and further comprises C2-20 alkyl glycol ethers when Y is in the polyphosphite backbone (e.g., ethylene, propylene, caprylactone, polyalkylene glycol);
- x is an integral value ranging from 8 to 1,000;
- z is an integral value ranging from 0 to 1,000 with the proviso that when z is 8 or greater, then x is an integral value ranging from 1 to 1,000;
- m is an integral value ranging from 1 to 20;
- w is an integral value ranging from 1 to 1,000;
- and
- combinations of formula (I) or Formula (II) or Formula (III).
22 more elements
Dependencies are inferred from the claim text.