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Peroxide free radical initiators containing hindered amine light stabilizer groups

Assignee: Arkema Inc
•
Filing: 1987-01-16
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Granted: —
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Expires: 2007-01-16
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Abstract

Abstract Novel peroxide initiators contg. hindered amine light stabiliser gps. are of formula (I) where p = 1,2; n,m = 0, 1 except when m = 0, n = 0; R1 = H, 1-8C alkyl, 2-8C alkenyl, 2-8C alkynyl, 5-6C cycloalkyl, 7-15C aralkyl; R2, R3 = 1-12C alkyl, 6-10C aryl, 7-15C aralkyl and R and R together with the C to which they are attached form a 4-10C satd. alicyclic gp. opt. contg. N or O in the ring; R4, R5 = H, 1-8C alkyl, 6-10C aryl, 7-15C aralkyl; R6 = H, 1-8C alkyl, 2-8C alkenyl, 2-8C alkynyl, 5-6C cycloalkyl, 1-8C alkoxy, 2-7C alkoxycarbonyl, 6-10C aryl, 7-15C aralkyl, 1-8C acyl, 7-16C aroyl, 1-8C alkylsulphonyl, 6-10C arylsulphonyl, 1-7C acyloxy, 6-10C aroyloxy and R6 may be joined to R7 forming a 5-7 atom ring; x = -O-, -S-, -N(R9)-, -CO-, -SO2-, -OCO-, -OSO-, -OSO2-, -N-(R9)-CO-, -NHCONH-, -OCOO-; R7 is a diradical 1-20C alkylene, 6-10C arylene, 3-10C cycloalkylene, 7-20C aralkylene, 2-10C alkynylene, 4-10C alkadiynylene, 3-11C alkenylene, 5-11C alkadienylene opt. contg. O, S or N in the chain; Y = -CO-, -C(R10)(R11)-, -OCO-(R8), -N(R9)CO-(R8)-, -OCO-CO-; when p = 1, R8 = H, 2-20C acyl, 7-20C aroyl, 4-12C tert.alkyl, 4-12C tert.cycloalkyl, 9-15C tert.aralkyl, 2-20C alkoxycarbonyl, carbamoyl, etc., when p = 2, R8 is a diradical 7-15C di-tert.alkylene 8-16C ditert. alkenylene, 8-16C ditert. alkynylene, 12-20C ditert. aralkylene, 3-12C alkane dioyl, 8-16C aryl dicarbonyl, or 9-18C aralkyldicarbonyl; R9 = H, 1-8C alkyl, 2-8C alkenyl, 2-8C alkynyl, 5-6C cycloalkyl, 6-10C aryl, 1-8C acyl and R may be joined to R forming a 5-7C ring; R10 = 1-10C alkyl, 6-10C aryl, 2-10C alkynyl, 2-8C alkenyl, 5-6C cycloalkyl; R11 = R10 and R10 and R11 may be connected by a 4-9C alkylene diradical bridge and when R8 = tert.alkyl, tert.cycloalkyl or tert.aralkyl, R11 may be -OOR; substits. for R1, R2, R3, R4, R5, R6, R7,R8, R9, R10 and R11 = halogen, 1-4C alkyl, 1-4C alkoxy, etc..

Inventors

  • 👤 Terry N. Myers

Bibliographic Details

Application Number —
Jurisdiction EP
Data Source google_patents
Last Synchronized 2026-11-08 23:18
CPC Classifications
C; C08; C08K; C08K5/00; C08K5/16; C08K5/34; C08K5/3412; C08K5/3432; C08K5/3435; C07; C07D; C07D211/00; C07D211/04; C07D211/06; C07D211/36; C07D211/40; C07D211/44; C07D211/46; C08F; C08F299/00; C08F299/02; C08F299/04; C08F299/0442; C08F299/045; C08F4/00; C08F4/28; C08F4/32; C08F4/34

Claims Analysis

Total Claims: 13
Claim 1
Independent Claim 721 words
A peroxide initiator containing hindered amine light stabilizer group(s) having the formula: wherein: p is 1 or 2, n and m are independently selected from 0 and 1 with the proviso that when m is 0 then n is 0, R¹ is selected from hydrogen, alkyl of 1 to 8 carbons, alkenyl of 2 to 8 carbons, alkynyl of 2 to 8 carbons, cycloalkyl of 5 to 6 carbons in the ring, aralkyl of 7 to 15 carbons, R² and R³ may be the same or different, and are independently selected from alkyl of 1 to 12 carbons, aryl of 6 to 10 carbons, aralkyl of 7 to 15 carbons and R² and R³ can be taken together with the carbon to which they are attached forming a saturated alicyclic group of 4 to 10 carbons, optionally containing oxygen or nitrogen in the ring, R⁴ and R⁵ may be the same or different and are independently selected from hydrogen, alkyl of 1 to 8 carbons, aryl of 6 to 10 carbons, aralkyl of 7 to 15 carbons, R⁶ is selected from hydrogen, alkyl of 1 to 8 carbons, alkenyl of 2 to 8 carbons, alkynyl of 2 to 8 carbons, cycloalkyl of 5 to 6 carbons, alkoxy of 1 to 8 carbons, alkoxycarbonyl of 2 to 7 carbons, aryl of 6 to 10 carbons, aralkyl of 7 to 15 carbons, acyl of 1 to 8 carbons, aroyl of 7 to 16 carbons, alkylsulfonyl of 1 to 8 carbons, arylsulfonyl of 6 to 10 carbons, acyloxy of 1 to 7 carbons, and aroyloxy of 6 to 10 carbons, and R⁶ may be joined to R⁷ forming a cyclic structure of 5 to 7 atoms X is selected from -O-, -S-, -N(R⁹)-, -C(=O)-, -S(=O)-, -S(=O)₂-, -O-C(=O)-, -O-S(=O)-, -O-S(=O)₂-, -N(R⁹)-C(=O)-, -NH-C(=O)-NH-, -O-C(=O)-O-, R⁷ is a diradical selected from alkylene of 1 to 20 carbons, arylene of 6 to 10 carbons, cycloalkylene of 3 to 10 carbons, aralkylene of 7 to 20 carbons, alkynylene of 2 to 10 carbons, alkadiynylene of 4 to 10 carbons, alkenylene of 3 to 11 carbons, alkadienylene of 5 to 11 carbons, optionally containing oxygen, sulfur, or nitrogen atoms in the diradical chain. Y is selected from -C(=O)-, -S(=O)₂-, -C(R¹⁰)(R¹¹)-, -O-C(=O)-(R⁸), -N(R⁹)-C(=O)-(R⁸), -O-C(=O)-C(=O)-, When p is 1, R⁸ is selected from hydrogen, acyl of 2 to 20 carbons, aroyl of 7 to 20 carbons, t-alkyl of 4 to 12 carbons, t-cycloalkyl of 4 to 12 carbons, t-aralkyl of 9 to 15 carbons, alkoxycarbonyl of 2 to 20 carbons, carbamoyl, phenylcarbamoyl, alkylcarbamoyl of 2 to 13 carbons, cycloalkylcarbamoyl of 4 to 13 carbons, alpha-hydroxyalkyl of 2 to 10 carbons, alpha-hydroxycycloalkyl of 3 to 10 carbons, alkylsulfonyl of 4 to 20 carbons, cycloalkylsulfonyl of 3 to 12 carbons, t-(alkoxyalkyl) of 4 to 20 carbons, t-(alkoxycycloalkyl) of 4 to 20 carbons, monovalent organomineral, or when p is 2, R⁸ is a diradical selected from di-tertiary alkylene of 7 to 15 carbons, di-tertiary alkenylene of 8 to 16 carbons, di-tertiary alkynylene of 8 to 16 carbons, di-tertiary aralkylene of 12 to 20 carbons, alkanedioyl of 3 to 12 carbons, aryldicarbonyl of 8 to 16 carbons, or aralkyldicarbonyl of 9 to 18 carbons, R⁹ is selected from hydrogen, alkyl of 1 to 8 carbons, alkenyl of 2 to 8 carbons, alkynyl of 2 to 8 carbons, cycloalkyl of 5 to 6 carbons in the ring, aryl of 6 to 10 carbons, acyl of 1 to 8 carbons and R⁹ may be joined to R⁷ forming a cyclic structure of 5 to 7 atoms, R¹⁰ is selected from alkyl of 1 to 10 carbons, aryl of 6 to 10 carbons, alkynyl of 2 to 10 carbons, alkenyl of 2 to 8 carbons, cycloalkyl of 5 to 6 carbons in the ring, R¹¹ is selected from the definition of R¹⁰ and R¹⁰ and R¹¹ can be connected to each other by means of an alkylene diradical bridge containing 4 to 9 carbons and when R⁸ is t-alkyl, t-cycloalkyl, or t-aralkyl, R¹¹ may be -OO-R⁸, substituents for R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R9, R¹⁰, and R¹¹ include halogen, alkyl of 1 to 4 carbons, alkoxy of 1 to 4 carbons, -C=N, -OH, epoxy, carboxy, alkyoxycarbonyl of 2 to 6 carbons, acyloxy of 1 to 4 carbons, hydroxymethyl, hydroxyethyl, and alkylmercapto of 1 to 4 carbons.
Claim 2
Dependent Claim 721 words
A peroxide initiator containing hindered amine light stabilizer group(s) having the formula: wherein: p is 1 or 2, n and m are independently selected from 0 and 1 with the proviso that when m is 0 then n is 0, R¹ is selected from hydrogen, alkyl of 1 to 8 carbons, alkenyl of 2 to 8 carbons, alkynyl of 2 to 8 carbons, cycloalkyl of 5 to 6 carbons in the ring, aralkyl of 7 to 15 carbons, R² and R³ may be the same or different, and are independently selected from alkyl of 1 to 12 carbons, aryl of 6 to 10 carbons, aralkyl of 7 to 15 carbons and R² and R³ can be taken together with the carbon to which they are attached forming a saturated alicyclic group of 4 to 10 carbons, optionally containing oxygen or nitrogen in the ring, R⁴ and R⁵ may be the same or different and are independently selected from hydrogen, alkyl of 1 to 8 carbons, aryl of 6 to 10 carbons, aralkyl of 7 to 15 carbons, R⁶ is selected from hydrogen, alkyl of 1 to 8 carbons, alkenyl of 2 to 8 carbons, alkynyl of 2 to 8 carbons, cycloalkyl of 5 to 6 carbons, alkoxy of 1 to 8 carbons, alkoxycarbonyl of 2 to 7 carbons, aryl of 6 to 10 carbons, aralkyl of 7 to 15 carbons, acyl of 1 to 8 carbons, aroyl of 7 to 16 carbons, alkylsulfonyl of 1 to 8 carbons, arylsulfonyl of 6 to 10 carbons, acyloxy of 1 to 7 carbons, and aroyloxy of 6 to 10 carbons, and R⁶ may be joined to R⁷ forming a cyclic structure of 5 to 7 atoms X is selected from -O-, -S-, -N(R⁹)-, -C(=O)-, -S(=O)-, -S(=O)₂-, -O-C(=O)-, -O-S(=O)-, -O-S(=O)₂-, -N(R⁹)-C(=O)-, -NH-C(=O)-NH-, -O-C(=O)-O-, R⁷ is a diradical selected from alkylene of 1 to 20 carbons, arylene of 6 to 10 carbons, cycloalkylene of 3 to 10 carbons, aralkylene of 7 to 20 carbons, alkynylene of 2 to 10 carbons, alkadiynylene of 4 to 10 carbons, alkenylene of 3 to 11 carbons, alkadienylene of 5 to 11 carbons, optionally containing oxygen, sulfur, or nitrogen atoms in the diradical chain. Y is selected from -C(=O)-, -S(=O)₂-, -C(R¹⁰)(R¹¹)-, -O-C(=O)-(R⁸), -N(R⁹)-C(=O)-(R⁸), -O-C(=O)-C(=O)-, When p is 1, R⁸ is selected from hydrogen, acyl of 2 to 20 carbons, aroyl of 7 to 20 carbons, t-alkyl of 4 to 12 carbons, t-cycloalkyl of 4 to 12 carbons, t-aralkyl of 9 to 15 carbons, alkoxycarbonyl of 2 to 20 carbons, carbamoyl, phenylcarbamoyl, alkylcarbamoyl of 2 to 13 carbons, cycloalkylcarbamoyl of 4 to 13 carbons, alpha-hydroxyalkyl of 2 to 10 carbons, alpha-hydroxycycloalkyl of 3 to 10 carbons, alkylsulfonyl of 4 to 20 carbons, cycloalkylsulfonyl of 3 to 12 carbons, t-(alkoxyalkyl) of 4 to 20 carbons, t-(alkoxycycloalkyl) of 4 to 20 carbons, monovalent organomineral, or when p is 2, R⁸ is a diradical selected from di-tertiary alkylene of 7 to 15 carbons, di-tertiary alkenylene of 8 to 16 carbons, di-tertiary alkynylene of 8 to 16 carbons, di-tertiary aralkylene of 12 to 20 carbons, alkanedioyl of 3 to 12 carbons, aryldicarbonyl of 8 to 16 carbons, or aralkyldicarbonyl of 9 to 18 carbons, R⁹ is selected from hydrogen, alkyl of 1 to 8 carbons, alkenyl of 2 to 8 carbons, alkynyl of 2 to 8 carbons, cycloalkyl of 5 to 6 carbons in the ring, aryl of 6 to 10 carbons, acyl of 1 to 8 carbons and R⁹ may be joined to R⁷ forming a cyclic structure of 5 to 7 atoms, R¹⁰ is selected from alkyl of 1 to 10 carbons, aryl of 6 to 10 carbons, alkynyl of 2 to 10 carbons, alkenyl of 2 to 8 carbons, cycloalkyl of 5 to 6 carbons in the ring, R¹¹ is selected from the definition of R¹⁰ and R¹⁰ and R¹¹ can be connected to each other by means of an alkylene diradical bridge containing 4 to 9 carbons and when R⁸ is t-alkyl, t-cycloalkyl, or t-aralkyl, R¹¹ may be -OO-R⁸, substituents for R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R9, R¹⁰, and R¹¹ include halogen, alkyl of 1 to 4 carbons, alkoxy of 1 to 4 carbons, -C=N, -OH, epoxy, carboxy, alkyoxycarbonyl of 2 to 6 carbons, acyloxy of 1 to 4 carbons, hydroxymethyl, hydroxyethyl, and alkylmercapto of 1 to 4 carbons.
Claim 3
Dependent Claim 253 words
The compound of claim 1 in which R¹ is selected from hydrogen, alkyl of 1 to 4 carbons, aralkyl of 7 to 9 carbons, or cycloalkyl of 5 to 6 carbons, R² and R³ may be the same or different, and are independently selected from alkyl of 1 to 3 carbons, aralkyl of 7 to 10 carbons, and can be taken together with the carbon to which they are attached forming a saturated alicyclic group of 6 carbons, R⁶ is selected from hydrogen, alkyl of 1 to 4 carbons, alkoxycarbonyl of 2 to 5 carbons, acyloxy of 1 to 4 carbons, aryl of 6 carbons, or alkoxy of 1 to 3 carbons, X is -O-, -S-, -N(R⁹)-, -O-C(=O)-O-, -N(R⁹)-C(=O)-O-, -O-C(=O)-, -C(=O)-, R⁷ is selected from alkylene of 1 to 8 carbons, arylene of 6 to 10 carbons, aralkylene of 8 to 16 carbons, or cycloalkylene of 4 to 8 carbons, when p is 1, R⁸ is selected from acyl of 2 to 10 carbons, aroyl of 7 to 10 carbons, t-alkyl of 4 to 8 carbons, t-aralkyl of 9 to 16 carbons, or when p is 2, R⁸ is selected from di-tertiary alkylene of 8 to 12 carbons, di-tertiary aralkylene of 12 to 15 carbons, or alkanedioyl of 3 to 6 carbons, R⁹ is selected from hydrogen, alkyl of 1 to 4 carbons, cycloalkyl of 6 carbons, aryl of 6 carbons, and R¹⁰ is alkyl of 1 to 6 carbons, aryl of 6 to 10 carbons, or cycloalkyl of 5 to 6 carbons.
Claim 4
Dependent Claim 203 words
The compound of claim 2 in which R¹ is selected from hydrogen or alkyl of 1 to 4 carbons, R² and R³ may be the same or different and are selected from methyl, ethyl, or benzyl, R⁴ and R⁵ are the same or different and are selected from hydrogen, methyl, ethyl, or phenyl, R⁶ is selected from hydrogen, alkyl of 1 to 4 carbons, or alkoxy of 1 to 3 carbons, X is -O-, -N(R⁹)-, -O-C(=O)-O-, -N(R⁹)-C(=O)-O-, or -O-C(=O)-, R⁷ is selected from alkylene of 1 to 6 carbons, arylene of 6 carbons, aralkylene of 9 to 12 carbons, or cycloalkylene of 5 to 7 carbons, Y is selected from -C(=O)-, -C(R¹⁰)(R¹¹)-, or -O-C(=O)-, when p is 1, R⁸ is selected from acyl of 2 to 10 carbons, aroyl of 7 carbons, t-alkyl of 4 to 6 carbons, t-aralkyl of 9 to 12 carbons, or when p is 2, R⁸ is selected from di-tertiary alkylene of 8 to 10 carbons, di-tertiary aralkylene of 12 carbons, or alkanedioyl of 4 to 6 carbons, R⁹ is selected from hydrogen, or alkyl of 1 to 4 carbons, R¹⁰ is selected from alkyl of 1 to 4 carbons, aryl of 6 carbons, or cycloalkyl of 6 carbons.
Claim 5
Dependent Claim 35 words
The compound of claim 3 in which p is 1, n is 0, m is 0, R¹, R², and R³ are methyl, R⁴, R⁵ and R⁶ are hydrogen, Y is -O-C(=O)-, and R⁸ is t-butyl.
Claim 6
Dependent Claim 41 words
The compound of claim 3 in which p is 1, n is 1, m is 1, R1, R², and R³ are methyl, R⁴, R⁵, and R⁶ are hydrogen, X is -O-C(=O)-O-, R⁷ is -CH(CH₃)-CH₂, Y is -C(CH₃)₂-, and R⁸ is t-butyl.
Claim 7
Dependent Claim 35 words
The compound of claim 3 in which p is 1, n is 0, m is 0, R² and R³ are methyl, R¹, R⁴, R⁵, and R⁶ are hydrogen, Y is -O-C(=O)-, and R⁸ is t-butyl.
Claim 8
Dependent Claim 41 words
The compound of claim 3 in which p is 1, n is 1, m is 1, R¹, R², and R³ are methyl, R⁴, R⁵, and R⁶ are hydrogen, X is -O-C(=O)-O-, R⁷ is -CH₂-CH₂, Y is -C(=O)-, and R⁸ is t-butyl.
Claim 9
Dependent Claim 52 words
The compound of claim 3 in which p is 1, m is 1, n is 1, R² and R³ are methyl, R¹, R⁴, R⁵, and R⁶ are hydrogen, X is -N(R⁹)-C(=O)-, R⁷ is 1,4-phenylene additionally connected to R⁹ in the 2 position, Y is -C(=O)-, R⁸ is t-amyl, and R⁹ is -C(=O)-.
Claim 10
Dependent Claim 50 words
A process of preparing a homo- or copolymer containing hindered amine light stabilizer groups chemically connected to the backbone of said polymer comprising polymerizing one or more ethylenically unsaturated monomer capable of being polymerized by free radicals in the presence of an initiating amount of the compound of claim 1.
Claim 11
Dependent Claim 13 words
The stabilized homo- or copolymer product prepared by the process of claim 9.
Claim 12
Dependent Claim 46 words
A process of preparing a cured polyester containing hindered amine light stabilizer groups chemically connected to said polyester comprising curing an unsaturated polyester resin capable of being cured by free radicals in the presence of a sufficient amount to cure of the compound of claim 1.
Claim 13
Dependent Claim 12 words
The stabilized cured polyester product prepared by the process of claim 11.

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