# US 4,398,014 A · Sulfoxonium salts and their use as polymerization catalysts

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- Number: US 4,398,014 A
- Document ID: US4398014A
- Status: Granted
- Kind: A
- Application number: 06/314,275
- Filed: 1981-10-23
- Granted: 1983-08-09
- Earliest claimed: 1980-11-04
- Assignees: Ciba-Geigy Corporation
- Inventors: George E. Green; Edward Irving; Bernard P. Stark
- Web page: https://patentgrep.com/patent/US4398014A

## CPC

- G03F 7/029: Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
- C07C 381/00: Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C08G 59/687: {containing sulfur}
- C08G 65/105: {Onium compounds}
- C08G 85/00: General processes for preparing compounds provided for in this subclass
- C08K 5/42: Sulfonic acids; Derivatives thereof
- G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G)
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)

## Abstract

New aromatic sulfonylsulfoxonium salts are of formula ##STR1## where q is 1 to 4, R denotes an aliphatic, cycloaliphatic, or aromatic group, R.sup.6 denotes H, an alkyl or aralkyl group, or a group --COR.sup.9, --CO--NH--(CO).sub.r --R.sup.10, or --SO.sub.2 --R.sup.11, where r is zero or 1, one, but not both, of R and R.sup.6 denoting an aromatic group, R.sup.7 denotes an alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, or aralkyl group, R.sup.8 has the same meaning as R.sup.7 but may alternatively represent a dialkylamino group or, if R.sup.7 denotes alkyl, it may alternatively represent an arylamino group, R.sup.9, R.sup.10, and R.sup.11 each denote an alkyl, aryl, or aralkyl radical of 1 to 25 carbon atoms, t is 1, 2, or 3, and Z.sup.- denotes a t-valent anion of a protic acid. The salts, e.g., dimethyl-p-toluenesulfonylmethylsufoxonium hexafluorophosphate, are useful as catalysts for the polymerization of cationically polymerizable materials by means of actinic radiation and/or heat. Polyepoxides and resols may be photopolymerized in the presence of the salts and subsequently crosslinked with a latent heat-curing agent.

## Claims

### Claim 1

A polymerizable composition which comprises
(a) a compound, or mixture of compounds, capable of being transformed into a higher-molecular weight material under the influence of a cationic catalyst,
(b) an effective amount of an aromatic sulfonylsulfoxonium salt of the formula ##STR16## where q is an integer of from 1 to 4,
R denotes an aliphatic, cycloaliphatic or aromatic group of valency q, having from 1 to 25 carbon atoms and being directly linked through a carbon atom thereof to the sulfur atom of the indicated adjacent sulfonyl group,
R.sup.6 denotes a hydrogen atom, an alkyl or aralkyl group of 1 to 25 carbon atoms, an acyl group of formula --COR.sup.9 or a group of formula
--CO--NH--(CO).sub.r --R.sup.10 VII
or ##STR17## one, but not both, of R and R.sup.6 denoting a homocyclic aromatic group of 6 to 25 carbon atoms or a heterocyclic aromatic group of 4 to 25 carbon atoms containing one or more nitrogen, oxygen or sulfur atoms in the aromatic ring,
R.sup.7 denotes an alkyl group of 1 to 12 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms, a cycloalkylalkyl group of 4 to 10 carbon atoms, an aryl group of 6 to 24 carbon atoms, or an aralkyl group of 7 to 16 carbon atoms,
R.sup.8 has the same meaning as R.sup.7, or R.sup.8 is a dialkylamino group of 2 to 6 carbon atoms, or if R.sup.7 is alkyl of 1 to 12 carbon atoms, R.sup.8 may also be an arylamino group of 6 to 8 carbon atoms,
R.sup.9 denotes an alkyl, aryl, or aralkyl radical of 1 to 25 carbon atoms, directly linked through a carbon atom thereof to the indicated --CO-- group,
r is zero or 1,
R.sup.10 denotes an alkyl, aryl, or aralkyl radical of 1 to 25 carbon atoms, directly linked through a carbon atom thereof to, if r denotes zero, the indicated nitrogen atom, or if r denotes 1, the carbon atom of the indicated adjacent carbonyl group,
R.sup.11 denotes an alkyl, aryl, or aralkyl radical of 1 to 25 carbon atoms, directly linked through a carbon atom thereof to the indicated sulfur atom,
t represents 1, 2, or 3, and
Z.sup.t- denotes a t-valent anion of a protic acid.

### Claim 2 (depends on 1)

A composition according to claim 1, in which R represents a monocyclic or dicyclic homocyclic aryl or aralkyl group of 6 to 16 carbon atoms.

### Claim 3 (depends on 1)

A composition according to claim 1, in which R represents a monocyclic or dicyclic arylene or aralkylene group of 6 to 16 carbon atoms.

### Claim 4 (depends on 1)

A composition according to claim 1, in which R.sup.7 and R.sup.8 are each an alkyl group of 1 to 4 carbon atoms, a phenyl group, a naphthyl group, or a phenyl or a naphthyl group substituted in the aromatic ring or rings by one or two alkyl groups, each of 1 to 4 carbon atoms, or by one or two alkoxy groups, each of 1 to 4 carbon atoms, or by one or two fluorine, chlorine, or bromine atoms.

### Claim 5 (depends on 1)

A composition according to claim 1, in which R denotes an aromatic group and R.sup.9 denotes an aliphatic radical of 1 to 8 carbon atoms.

### Claim 6 (depends on 1)

A composition according to claim 1, in which R denotes an aromatic group and R.sup.10 denotes an aliphatic radical of 1 to 8 carbon atoms.

### Claim 7 (depends on 1)

A composition according to claim 1, in which R denotes an aromatic group and R.sup.11 denotes an aliphatic radical of 1 to 8 carbon atoms.

### Claim 8 (depends on 1)

A composition according to claim 1, wherein Z.sup.t- denotes an anion of an inorganic acid.

### Claim 9 (depends on 1)

A composition according to claim 1, where Z.sup.t- denotes Cl.sup.-, Br.sup.-, NO.sub.3.sup.-, HSO.sub.4.sup.-, HSO.sub.3.sup.-, ClO.sub.4.sup.-, CF.sub.3 SO.sub.3.sup.-, CF.sub.3 COO.sup.-, CH.sub.3 C.sub.6 H.sub.4 SO.sub.3.sup.-, H.sub.2 PO.sub.4.sup.-, SO.sub.4.sup.--, PO.sub.4.sup.---, SbF.sub.5 (OH).sup.-, or an anion of formula
MX.sub.n.sup.- XI
where
M denotes an atom of antimony, bismuth, boron, arsenic, or phosphorus,
X denotes a fluorine or chlorine atom, and
n is 4, 5, or 6 and is one more than the valency of m.

### Claim 10 (depends on 1)

A composition according to claim 1, in which (b) is dimethyl-p-toluenesulfonylmethylsulfoxonium hexafluorophosphate, dimethyltoluene-p-sulfonylmethylsulfoxonium hexafluoroantimonate, tris(dimethyltoluene-p-sulfonylmethylsulfoxonium)orthophosphate, or dimethylphenylsulfonylmethylsulfoxonium hexafluorophosphate.

### Claim 11 (depends on 1)

A composition according to claim 1, wherein (a) is a 1,2-epoxide, a vinyl monomer or prepolymer, an aminoplast, or a phenoplast.

### Claim 12 (depends on 1)

A composition according to claim 1, wherein (a) is either an epoxide resin or a resol made from a phenol and an aldehyde.

### Claim 13 (depends on 1)

A composition according to claim 1, containing 0.1 to 7.5 parts by weight of (b) per 100 parts by weight of (a).

### Claim 14 (depends on 12)

A composition according to claim 12, which also contains a curing amount of a latent heat-curing agent for epoxide resins or resol resins.