Back to results
US 2003/0216494 A1Published application
Hydroxylamine esters as polymerization initiators
AssigneeCiba Specialty Chemicals Corporation
InventorsMichael Roth, Rudolf Pfaendner, Peter Nesvadba, Marie-Odile Zink
Life of this patent
Estimating the term…
Abstract
The invention relates to novel cyclic and open-chain hydroxylamine esters and polymerizable compositions comprising these hydroxylamine esters and an ethylenically unsaturated monomer or oligomer. The invention also relates to use as polymerization initiators and to the use of known hydroxylamine esters selected from the group consisting of HALS compounds and the novel hydroxylamine esters for the controlled degradation of polypropylene and for achieving a controlled increase in the molecular weight of polyethylene.
Claims18
A compound
- a) of the formula:
- 111
- Ra is an acyl radical selected from the group consisting of —C(═O)—H, —C(═O)—C1-C19alkyl, —C(═O)—C2-C19alkenyl, —C(═O)—C2-C4alkenyl-C6-C10aryl, —C(═O)—C6-C10aryl, —C(═O)—O—C1-C6alkyl, —C(═O)—O—C6-C10aryl, —C(═O)—NH—C1-C6alkyl, —C(═O)—NH—C6-C10aryl and —C(═O)—N(C1-C6alkyl)2;
- R1-R4 are each C1-C6alkyl;
- R5 and R6 are each, independently of one another, hydrogen, C1-C6alkyl or C6-C10aryl;
- or
- R5 and R6 are together oxygen;
- Q is a direct bond or a bivalent radical —(CR7R8)— or —(CR7R8—CR9R10)—, where
- R7, R8, R9 and R10 are each, independently of one another, hydrogen or C1-C6alkyl;
- and
- Z1 is oxygen or a bivalent radical —NR11—, where
- R11 is hydrogen, C1-C6alkyl, C6-C10aryl or the acyl radical Ra having one of the abovementioned meanings;
- or
- b) of the formula Ia, where
- Ra is an acyl radical selected from the group consisting of —P(═O)—C1-C19alkyl, —P(═O)2—C1-C19alkyl, —P(═O)—C6-C10aryl, —P═O(—C1-C19alkyl)2, —P═O(—C6-C10aryl)2, —P(═O)—O—C1-C6alkyl, —P(═O)—O—C6-C10aryl, —P═O(—O—C0-C6alkyl)2, —P═O(—O—C6-C10aryl)2, —P(—O—C1-C6alkyl)2 and —P(—O—C6-C10aryl)2;
- R1-R4 are each C1-C6alkyl;
- R5 and R6 are each, independently of one another, hydrogen, C1-C6alkyl or C6-C10aryl;
- or
- R5 and R6 are together oxygen;
- Q is a direct bond or a bivalent radical —(CR7R8)— or —(CR7R8—CR9R10)—, where
- R7, R8, R9 and R10 are each, independently of one another hydrogen or C1-C6alkyl;
- and
- Z1 is oxygen or a bivalent radical —NR11— or —(CR12R13)—, where
- R11 is hydrogen, C1-C6alkyl or C6-C10aryl or, independently of one another,
- one of the radicals R12 and R13 is hydrogen or C1-C6alkyl and the other is C1-C6alkyl, C1-C6alkoxy, C6-C10aryloxy, acyloxy selected from the group consisting of —O—C(═O) —H, —O—C(═O)—C1-C19alkyl, —O—C(═O)—C1-C54alkenyl, —O—C(═O)—C6-C10aryl, —O—C(═O)—C1-C36alkenyl-C6-C10aryl, —O—C(═O)—O—C1-C19alkyl, —O—C(═O)—O—C6-C10aryl, —O—C(═O)—NH—C1-C6alkyl, —O—C(═O)—NH—C6-C10aryl and —O—C(═O)—N(C1-C6alkyl)2, C1-C6alkylamino, di-C1-C6alkylamino, C6-C10arylamino, acylamino selected from the group consisting of —NH—C(═O)—H, —NH—C(═O)—C1-C19alkyl, —NH—C(═O)—C1-C54alkenyl, —NH—C(═O)—C6-C10aryl, —NH—C(═O)—C1-C36alkenyl-C6-C10aryl, —NH—C(═O)—O—C1-C19alkyl, —NH—C(═O)—O—C6-C10aryl, —NH—C(═O)—NH—C1-C6alkyl, —NH—C(═O)—NH—C6-C10aryl and —NH—C(═O)—N(C1-C6alkyl)2, diacylamino selected from the group consisting of —N[—C(═O)—C1-C19alkyl]2 and —N[—C(═O)—C6-C10aryl]2, or N-acyl-N—C1-C6alkylamino;
- or
- the two radicals R12 and R13 are together oxo;
- or
- c) of the formula:
- 112
- Ra is an acyl radical selected from the group consisting of —C(═O)—H, —C(═O)—C1-C19alkyl, —C(═O)—C2-C19alkenyl, —C(═O)—C2-C4alkenyl-C6-C10aryl, —C(═O)—C6-C10aryl, —C(═O)—O—C1-C6alkyl, —C(═O)—O—C6-C10aryl, —C(═O)—NH—C1-C6alkyl, —C(═O)—NH—C6-C10aryl and —C(═O)—N(C1-C6alkyl)2;
- R1-R4 are each C1-C6alkyl;
- A is a substituent on the phenyl rings;
- and
- m is zero or an integer from one to four;
- or
- d) of the formula:
- 113
- Ra is an acyl radical selected from the group consisting of —C(═O)—H, —C(═O)—C1-C19alkyl, —C(═O)—C2-C19alkenyl, —C(═O)—C2-C4alkenyl-C6-C10aryl, —C(═O)—C6-C10aryl, —C(═O)—O—C1-C6alkyl, —C(═O)—O—C6-C10aryl, —C(═O)—NH—C1-C6alkyl, —C(═O)—NH—C6-C10aryl, —C(═O)—N(C1-C6alkyl)2, —P (═O)—C1-C19alkyl, —P(═O)2—C1-C19alkyl, —P(═O)—C6-C10aryl, —P═O(—C1-C19alkyl)2, —P═O(—C6-C10aryl)2, —P(═O)—O—C1-C6alkyl, —P(═O)—O—C6-C10aryl, —P═O(—O—C1-C6alkyl)2, —P═O(—O—C6-C10aryl)2, —P(—O—C1-C6alkyl)2 and —P(—O—C6-C10aryl)2;
- Rb is as defined for Ra or is carbamoyl, C1-C6akylcarbamoyl or di-C1-C6alkylcarbamoyl;
- Rc and Rd are each, independently of one another, hydrogen, C1-C6alkyl or C6-C10aryl;
- and
- R1-R3 are each, independently of one another, C1-C6alkyl or C6-C10aryl.
40 more elements
A composition comprising
- A) at least one ethylenically unsaturated, polymerizable monomer or oligomer;
- and
- B) at least one of the above-described compounds a)-d).
A process for preparing an oligomer, a cooligomer, a polymer or a copolymer by free-radical polymerization, characterised in that a composition comprising
- α) at least one ethylenically unsaturated, polymerizable monomer or oligomer;
- and
- β) one of the above-defined novel compounds a)-d) is subjected to the reaction conditions of a free-radical polymerization.
A process for reducing the molecular weight of polypropylene, propylene copolymers or polypropylene blends, characterised in that at least one hydroxylamine ester or a polymer of a hydroxylamine ester of the formula:
- 114
- Ra′ is a monoacyl or diacyl radical;
- R1-R4 are each C1-C6alkyl;
- and
- R5 and R6 are each, independently of one another, hydrogen, C1-C6alkyl or C6-C10aryl;
- or
- R5 and R6 are together oxygen,
- is added to the polypropylene, propylene copolymer or polypropylene blend to be degraded and the mixture is heated.
5 more elements
A process for the controlled increase in the molecular weight of polyethylenes or polyethylene blends, characterised in that a compound (Ia), where
- Ra is an acyl radical selected from the group consisting of —C(═O)—H, —C(═O)—C1-C19alkyl, —C(═O)—C2-C119alkenyl, —C(═O)—C2-C4alkenyl-C6-C10aryl, —C(═O)—C6-C10aryl, —C(═O)—O—C1-C6alkyl, —C(═O)—O—C6-C10aryl, —C(═O)—NH—C1-C6alkyl, —C(═O)—NH—C6-C10aryl, —C(═O)—N(C1-C6alkyl)2, —P(═O)—C1-C19alkyl, —P(═O)2—C1-C19alkyl, —P(═O)—C6-C10aryl, —P═O(—C1-C19alkyl)2, —P═O(—C6-C10aryl)2, —P(═O)—O—C1-C6alkyl, —P(═O)—O—C6-C10aryl, —P═O(—O—C1-C6alkyl)2, —P═O(—O—C6-C10aryl)2, —P(—O—C1-C6alkyl)2 and —P(—O—C6-C10aryl)2;
- R1-R4 are each C1-C6alkyl;
- R5 and R6 are each, independently of one another, hydrogen, C1-C6alkyl or C6-C10aryl;
- or
- R5 and R6 are together oxygen;
- Q is a direct bond or a bivalent radical —(CR7R8)— or —(CR7R8—CR9R10)—, where
- R7, R8, R9 and R10 are each, independently of one another, hydrogen or C1-C6alkyl;
- and
- Z1 is oxygen or a bivalent radical —NR11— or —(CR12R13)—, where
- R11 is hydrogen, C1-C6alkyl, C6-C10 aryl or the acyl radical Ra having the abovementioned meanings;
- or, independently of one another,
- R12 and R13 are each hydrogen or C1-C6alkyl, or
- one of the radicals R12 and R13 is hydrogen or C1-C6alkyl and the other is C1-C6alkyl, C1-C6alkoxy, aryloxy, acyloxy selected from the group consisting of —O—C(═O)—H, —O—C(═O)—C1-C19alkyl, —O—C(═O)—C6-C10aryl, —O—C(═O)—O—C1-C6alkyl, —O—C(═O)—O—C6-C10aryl, —O—C(═O)—NH—C1-C6alkyl, —O—C(═O)—NH—C6-C10aryl and —O—C(═O)—N(C1-C6alkyl)2, C1-C6alkylamino, di-C1-C6alkylamino, C6-C10arylamino, acylamino selected from the group consisting of —NH—C(═O)—H, —NH—C(═O)—C1-C19alkyl, —NH—C(═O)—C6-C10aryl, —NH—C(═O)—O—C1-C6alkyl, —NH—C(═O)—O—C6-C10aryl, —NH—C(═O)—NH—C1-C6alkyl, —NH—C(═O)—NH—C6-C10aryl and —NH—C(═O)—N(C1-C6alkyl)2, diacylamino selected from the group consisting of —N[—C(═O)-C1-C19alkyl]2, —N[—C(═O)—C6-C10aryl]2, —N[—C(═O)—C1-C6alkylene-C(═O)—], —N[—C(═O)—C2-C6alkenylene-C(═O)—] and phthalimido or N-acyl-N—C1-C6alkylamino;
- or the two radicals R12 and R13 are together oxo;
- is added to the polyethylene or polyethylene blend.
12 more elements
Dependencies are inferred from the claim text.