Polymerizable thioester synergists

• US 4,604,417 A
• Filed: 12/10/1984
• Issued: 08/05/1986
• Est. Priority Date: 12/10/1984
• Status: Expired due to Term

• Current Assignee: Eliokem
• Original Assignee: Goodyear Tire & Rubber Company
• Inventors: Cottman, Kirkwood S.
• Primary Examiner(s): Hoke, Veronica P.
• Application Number:
  US06/680,011
• Time in Patent Office: 603 Days
• Field of Search: 525/343, 525/351, 526/288, 526/289, 524/198, 524/199, 524/213, 524/217, 524/289, 524/302, 524/304, 560/9, 560/18, 560/17, 560/148, 560/153, 560/152
• US Class Current: 524/199
• CPC Class Codes: C08F 212/28 Amines
• CPC Class Codes: C08F 236/10 with vinyl-aromatic monomers
• CPC Class Codes: C08F 236/12 with nitriles

Abstract

There are disclosed polymerizable thioester synergists which have utility in enhancing the antioxidative activity of phenolic and amine stabilizers. The invention is also concerned with the thioesters themselves, their use in oxidizable organics, their combination with polymerizable and/or conventional antioxidants, and with polymers which contain these thioesters as physical admixtures or segmeric units of the polymer.

Claims

1. A composition comprising:

(1) an oxidizable diene containing polymer;

(2) a phenolic or amine antidegradant in physical admixture with the oxidizable organic material; and

(3) a synergist in physical admixture with the oxidizable organic material, the improvement comprising at least one synergist selected from the group of compounds having the structural formulae I-XII;

##STR7## wherein R is selected from hydrogen, methyl or phenyl radicals;

R¹ is selected from hydrogen, methyl or ethyl radicals;

R² is selected from hydrogen or methyl radicals;

R³ is selected from hydrogen, alkyl radicals of 1 to 12 carbon atoms, phenyl and substituted phenyl radicals;

R⁴ is an alkyl radical of 1 to 3 carbon atoms;

Q may be the same or different divalent radical selected from --O-- or --NH--;

β

is 0 or a whole number from 1 to 20;

n is a whole number from 2 to 20;

m is 0 or 1 or 2;

x is a whole number from 1 to 20;

α

is a monovalent radical selected from alkyl radicals of 1 to 30 carbon atoms, the radical ##STR8## or the radical ##STR9## wherein R², R³ and β

are defined as above and R⁵ is selected from hydrogen, hydroxyl and alkyl radicals of 1 to 10 carbon atoms.

2. A composition comprising:

(1) an oxidizable diene containing polymer;

(2) a phenolic or amine antidegradant in physical admixture with the oxidizable organic material; and

(3) a polymeric composition in physical admixture with the oxidizable organic material, the improvement comprising a polymeric composition obtained from polymerizing in a free radical polymerization system, a monomer system that contains at least one synergistic monomer selected from the structural formulae I-XII;

##STR10## wherein R is selected from hydrogen, methyl or phenyl radicals;

R¹ is selected from hydrogen, methyl or ethyl radicals;

R² is selected from hydrogen or methyl radicals;

R³ is selected from hydrogen, alkyl radicals of 1 to 12 carbon atoms, phenyl and substituted phenyl radicals;

R⁴ is an alkyl radical of 1 to 3 carbon atoms;

Q may be the same or different divalent radical selected from --O-- or --NH--;

β

is 0 or a whole number from 1 to 20;

n is a whole number from 2 to 20;

m is 0 or 1 or 2;

x is a whole number from 1 to 20;

α

is a monovalent radical selected from alkyl radicals of 1 to 30 carbon atoms, the radical ##STR11## or the radical ##STR12## wherein R², R³ and β

are defined as above and R⁵ is selected from hydrogen, hydroxyl and alkyl radicals of 1 to 10 carbon atoms.

3. A composition comprising:

(1) an oxidizable diene containing polymer; and

(2) a polymeric composition, the improvement comprising a polymeric composition that comprises (a) segmeric units of a free radical, polymerizable amine or phenolic antidegradant and (b) segmeric units derived from at least one free radical polymerizable compound having the structural formulae I-XII;

##STR13## wherein R is selected from hydrogen, methyl or phenyl radicals;

R¹ is selected from hydrogen, methyl or ethyl radicals;

R² is selected from hydrogen or methyl radicals;

R³ is selected from hydrogen, alkyl radicals of 1 to 12 carbon atoms, phenyl and substituted phenyl radicals;

R⁴ is an alkyl radical of 1 to 3 carbon atoms;

Q may be the same or different divalent radical selected from --O-- or --NH--;

β

is 0 or a whole number from 1 to 20;

n is a whole number from 2 to 20;

m is 0 or 1 or 2;

x is a whole number from 1 to 20;

α

is a monovalent radical selected from alkyl radicals of 1 to 30 carbon atoms, the radical ##STR14## or the radical ##STR15## wherein R², R³ and β

are defined as above and R⁵ is selected from hydrogen, hydroxyl and alkyl radicals of 1 to 10 carbon atoms.

4. A polymeric composition of matter that comprises (a) segmeric units derived from unsaturated, free radical polymerizable amine and phenolic antidegradants, and (b) segmeric units derived from at least one unsaturated free radical polymerizable compound having structural formulae I-XII:

##STR16## wherein R is selected from hydrogen, methyl or phenyl radicals;

R¹ is selected from hydrogen, methyl or ethyl radicals;

R² is selected from hydrogen or methyl radicals;

R³ is selected from hydrogen, alkyl radicals of 1 to 12 carbon atoms, phenyl and substituted phenyl radicals;

R⁴ is an alkyl radical of 1 to 3 carbon atoms;

Q may be the same or different divalent radical selected from --O-- or --NH--;

β

is 0 or a whole number from 1 to 20;

n is a whole number from 2 to 20;

m is 0 or 1 or 2;

x is a whole number from 1 to 20;

α

is a monovalent radical selected from alkyl radicals of 1 to 30 carbon atoms, the radical ##STR17## or the radical ##STR18## wherein R², R³ and β

are defined as above and R⁵ is selected from hydrogen, hydroxyl and alkyl radicals of 1 to 10 carbon atoms.

5. A polymeric composition according to claim 4 wherein the free radical polymerization is an emulsion polymerization, and the polymeric composition comprises 10-90 parts by weight of segmers derived from the group comprising acrylonitrile, styrene, α

-methylstyrene, 10-90 parts by weight of segmers derived from the group comprising 1,3-butadiene and isoprene, and 0.1∝

50 parts by weight of at least one segmer derived from structural formulae I-XII.

6. A polymeric composition of matter derived from the reaction of an a diene containing polymer, in the presence of a free radical initiator selected from the group consisting of azo systems, azonitrile systems, and redox systems, with a compound selected from the group consisting of structural formulae I-XII:

##STR19## wherein R is selected from hydrogen, methyl or phenyl radicals;

R¹ is selected from hydrogen, methyl or ethyl radicals;

R² is selected from hydrogen or methyl radicals;

R³ is selected from hydrogen, alkyl radicals of 1 to 12 carbon atoms, phenyl and substituted phenyl radicals;

R⁴ is an alkyl radical of 1 to 3 carbon atoms;

Q may be the same or different divalent radical selected from --O-- or --NH--;

β

is 0 or a whole number from 1 to 20;

n is a whole number from 2 to 20;

m is 0 or 1 or 2;

x is a whole number from 1 to 20;

α

is a monovalent radical selected from alkyl radicals of 1 to 30 carbon atoms, the radical ##STR20## or the radical ##STR21## wherein R², R³ and β

are defined as above and R⁵ is selected from hydrogen, hydroxyl and alkyl radicals of 1 to 10 carbon atoms.

7. A polymeric composition of matter derived from polymerizing in a free radical polymerization system a monomer system that comprises:

(1) at least one diene monomer; and

(2) at least one monomer selected from structural formulae I-XII;

##STR22## wherein R is selected from hydrogen, methyl or phenyl radicals;

R¹ is selected from hydrogen, methyl or ethyl radicals;

R² is selected from hydrogen or methyl radicals;

R³ is selected from hydrogen, alkyl radicals of 1 to 12 carbon atoms, phenyl and substituted phenyl radicals;

R⁴ is an alkyl radical of 1 to 3 carbon atoms;

Q may be the same or different divalent radical selected from --O-- or --NH--;

β

is 0 or a whole number from 1 to 20;

n is a whole number from 2 to 20;

m is 0 or 1 or 2;

x is a whole number from 1 to 20;

α

is a monovalent radical selected from alkyl radicals of 1 to 30 carbon atoms, the radical ##STR23## or the radical ##STR24## wherein R², R³ and β

are defined as above and R⁵ is selected from hydrogen, hydroxyl and alkyl radicals of 1 to 10 carbon atoms.

8. A composition of matter represented by structural formulae I-X:

##STR25## wherein R is selected from hydrogen, methyl or phenyl radicals;

R¹ is selected from hydrogen, methyl or ethyl radicals;

R² is selected from hydrogen or methyl radicals;

R³ is selected from hydrogen, alkyl radicals of 1 to 12 carbon atoms, phenyl and substituted phenyl radicals;

R⁴ is an alkyl radical of 1 to 3 carbon atoms;

Q may be the same or different divalent radical selected from --O-- or --NH--;

β

is 0 or a whole number from 1 to 20;

n is a whole number from 2 to 20;

m is 0 or 1 or 2;

x is a whole number from 1 to 20;

α

is a monovalent radical selected from alkyl radicals of 1 to 30 carbon atoms, the radical ##STR26## or the radical ##STR27## wherein R², R³ and β

are defined as above and R⁵ is selected from hydrogen, hydroxyl and alkyl radicals of 1 to 10 carbon atoms.