# US 5,705,589 A · Organosilane and organopolysiloxane free radical initiators and macromonomers and graft copolymers which can be prepared with them

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- Number: US 5,705,589 A
- Document ID: US5705589A
- Status: Granted
- Kind: A
- Application number: 08/501,750
- Filed: 1995-07-12
- Granted: 1998-01-06
- Earliest claimed: 1994-07-28
- Assignees: Wacker Chemie AG
- Inventors: Jochen Dauth; Bernward Deubzer; Oskar Nuyken; Brigette Voit; Ralf Kollefrath
- Web page: https://patentgrep.com/patent/US5705589A

## CPC

- C08G 77/392: containing sulfur
- C07F 7/1804: {Compounds having Si-O-C linkages (Si-O-acyl linkages C07F7/1896)}
- C08F 4/04: Azo-compounds
- C08F 283/12: on to polysiloxanes
- C08G 77/388: containing nitrogen
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

The organosilanes and organopolysiloxanes containing groups which form free radicals and are soluble in organic solvents, processes for their preparation, macromonomers and graft copolymers from the organosilanes and organopolysiloxanes according to the invention as free radical initiators and organic monomers which can be polymerized by free radicals, a process for the preparation of the macromonomers and graft copolymers and their use.

## Claims

### Claim 1

An organosilane or organopolysiloxane containing groups which form free radicals and consisting essentially of from 0.1% to 100.0% by weight of units of the formula
(R.sub.a Si(O.sub.(3-a)/2) --R.sup.1 --C.sub.6 H.sub.4-x --R.sup.5.sub.x --N.dbd.N--S.sub.y --R.sup.1 --R.sup.2) (1),
0% to 80.0% by weight of units of the formula
(R.sup.2.sub.3 SiO.sub.1/2) (2),
0% to 99.9% by weight of units of the formula
(R.sup.2.sub.2 SiO.sub.2/2) (3)
0% to 80.0% by weight of units of the formula
(R.sup.2 SiO.sub.3/2) (4)
and
0% to 80.0% by weight of units of the formula
(SiO.sub.4/2) (5),
in which
R is identical or different chlorine or bromine atoms, hydroxyl groups, C.sub.1 - to C.sub.18 -alkoxy radicals, or monovalent C.sub.1 - to C.sub.18 -hydrocarbon radicals which are optionally substituted by halogen atoms, amino groups, hydroxyl groups, epoxyalkyl radicals or cyano groups,
R.sup.1 is a chemical bond, or identical or different divalent C.sub.1 - to C.sub.18 - saturated, optionally branched alkylene radical or an unsaturated alkylene radical which is optionally substituted by halogen atoms, amino groups, hydroxyl groups, acyloxy groups, epoxyalkyl radicals or cyano groups and can be interrupted by divalent radicals, bonded to carbon atoms on both sides, from the group consisting of --O--, --S--, --COO--, --OOC--, --CONR.sup.2 --, --NR.sup.2 CO--, --NR.sup.2 -- and --CO--,
R.sup.5 is identical or different halogen atoms, cyano groups, nitro groups, or radicals --R, --OR or --C(O)R,
R.sup.2 is a hydrogen atom or a radical R and
a is 0, 1, 2 or 3,
x is 0, 1, 2, 3 or 4 and
y is0or 1, with the proviso that if 100% by weight of units of formula (I) are present, a has the value 3.

### Claim 2 (depends on 1)

A process for the preparation of an organosilane or organopolysiloxane containing groups which form free radicals as claimed in claim 1, in which an organosilane or organopolysiloxane built up from 0.1% to 100.0% by weight of units of the formula
(R.sub.a Si(O.sub.(3-a)/2)--A) (14),
and the amounts of units of formulae (2) to (5) are reacted with a compound of the formula
B--C.sub.6 H.sub.4-x R.sup.5.sub.x --N.dbd.N--S.sub.y --R.sup.1 --R.sup.2 ( 15),
in which
A is identical or different monovalent C.sub.1 - to C.sub.17 -hydrocarbon radicals which contain a carboxylic acid anhydride or epoxide group or a group --COCl or --NCO and are optionally substituted by halogen atoms, amino groups, hydroxyl groups, epoxy alkyl radicals or cyano groups, and can be interrupted by divalent radicals, bonded to carbon atoms on both sides, from the group consisting of --O--, --S--, --COO--, --OOC--, --CONR.sup.2 13 , --NR.sup.2 CO--, --NR.sup.2 -- and --CO--,
B is --(CH.sub.2).sub.c OH, --(CH.sub.2).sub.c NHR.sup.1, --(CH.sub.2).sub.c COOH, --(CH.sub.2).sub.c SH,
c is an integer having a value from 0 to 10 and
R, R.sup.5, a, x, y, R.sup.1 and R.sup.2 have the above meanings, with the proviso that the sum of the carbon atoms in A and B is not more than 18.

### Claim 3 (depends on 1, 2)

A process as claimed in claim 2 for the preparation of an organosilane or organopolysiloxane containing groups which form free radicals as claimed in claim 1, in which, in formulae (14) and (15)
B is a carboxylic acid anhydride or epoxide group, a group --COCl, --COOH or --NCO, or identical or different monovalent C.sub.1 - to C.sub.17 -hydrocarbon radicals which contain a carboxylic acid anhydride or epoxide group or a group --COCl or --NCO and are optionally substituted by halogen atoms, amino groups, hydroxyl groups, epoxyalkyl radicals or cyano groups and can be interrupted by divalent radicals, bonded to carbon atoms on both sides, from the group consisting of --o--, --S--, --COO--, --OOC--, --CONR.sup.2 --, --NR.sup.2 CO--, --NR.sup.2 -- and --CO--,
A is --(CH.sub.2).sub.2 OH, --(CH.sub.2).sub.c CH.sub.2 NHR.sup.1, --(CH.sub.2).sub.c CH.sub.2 COOH or --(CH.sub.2).sub.c CH.sub.2 SH and
R, a, c, R.sup.1 and R.sup.2 have the above meanings, with the proviso that the sum of the carbon atoms in A and B is not more than 18.

### Claim 4 (depends on 1)

A process for the preparation of an organosilane or organopolysiloxane containing groups which form free radicals as claimed in claim 1, in which an organosilane or organopolysiloxane built up from 0.1% to 100.0% by weight of units of the formula
(R.sub.a SiH(O.sub.(3-a)/2) (16),
and the amounts of units of formulae (2) to (5), are reacted in the presence of platinum, rhodium or compounds thereof with com pounds of the formula
R.sup.4 --C.sub.6 H.sub.4-x R.sup.5.sub.x --N.dbd.N--S.sub.y --R.sup.1 --R.sup.2 ( 17),
in which
R.sup.4 is identical or different monovalent C.sub.1 - to C.sub.18 -hydrocarbon radicals which contain an olefinic double bond or acetylenic triple bond and are optionally substituted by halogen atoms, amino groups, hydroxyl groups, acyloxy groups, epoxyalkyl radicals or cyano groups and can be interrupted by diva lent radicals, bonded to carbon atoms on both sides, from the group consisting of --O--, --S--, --COO--, --OOC--, --CONR.sup.2 --, --NR.sup.2 CO--, --NR.sup.2 -- and --CO--, and
R, R.sup.5, a, x, y, R.sup.1 and R.sup.2 have the above meanings.

### Claim 5 (depends on 1)

The process for the preparation of an organosilane or organopolysiloxane containing groups which form free radicals as claimed in claim 1, in which a mixture of the components
(A) organosilane of the formula
(R.sub.a Si(O.sub.(3-a)/2)--R.sup.1 --C.sub.6 H.sub.4-x R.sup.5.sub.x --N.dbd.N--S.sub.y --R.sup.1 --R.sup.2) (1),
(B) organosilicon compounds which are chosen from
(B1) organosilanes of the formula
R.sup.2.sub.d Si(R.sup.6).sub.(4-d) ( 18)
and
(B2) organosiloxanes of units of the formula
R.sup.2.sub.e (R.sup.6).sub.f SiO.sub.(4-e-f)/2 ( 19),
where
R.sup.6 is a chlorine or bromine atom or an optionally halogen-substituted C.sub.1 -C.sub.10 -alkoxy radical,
d, e and f have the values 0, 1, 2 or 3 and
R, R.sup.1, R.sup.2 and a the above meanings, with the proviso that component B contains at least 0.01 mole of alk oxy groups or chlorine or bromine atoms per mole of silicon atoms, optionally,
(C) at least 0.5 mole of water per mole of alkoxy groups, chlorine atoms or bromine atoms in components A and B and option ally
(D) a water-miscible solvent, is reacted.

### Claim 6 (depends on 1)

An organopolysiloxane containing groups which form free radicals as claimed in claim 1, wherein units of formula (1) are present in amounts of from 0.5% to 20% by weight.

### Claim 7 (depends on 1)

An organopolysiloxane containing groups which form free radicals as claimed in claim 1, wherein units of formula (3) are present in amounts of at least 90% by weight and remaining units are units of formulae (1) and (2).