# US 10,370,322 B2 · Addition-fragmentation agents

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- Number: US 10,370,322 B2
- Document ID: US10370322B2
- Status: Granted
- Kind: B2
- Application number: 15/410,919
- Filed: 2017-01-20
- Published: 2017-07-27
- Granted: 2019-08-06
- Earliest claimed: 2011-02-15
- Assignees: 3M Innovative Properties Company
- Applicants: 3M Innovative Properties Company
- Inventors: Guy D. Joly; Larry R. Krepski; Ann R. Fornof; Serkan Yurt; Babu N. Gaddam; Ahmed S. Abuelyaman
- Web page: https://patentgrep.com/patent/US10370322B2

## CPC

- C07C 67/26: with an oxirane ring
- C07C 67/14: from carboxylic acid halides
- C07C 69/593: Dicarboxylic acid esters having only one carbon-to-carbon double bond
- C07C 269/02: from isocyanates with formation of carbamate groups
- C07C 271/16: to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
- C08F 220/68: Esters
- C08K 3/22: of metals
- C08K 3/36: Silica
- C08K 5/04: Oxygen-containing compounds {(C08K5/0091 takes precedence)}
- C08K 5/11: of acyclic polycarboxylic acids
- C08K 5/12: of cyclic polycarboxylic acids
- C08K 5/205: Compounds containing [IMAGE cpc-sch-C08K-1010.gif] groups, e.g. carbamates
- C09D 133/08: Homopolymers or copolymers of acrylic acid esters
- C09J 4/00: Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond {; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16}
- C09J 5/00: Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J 133/08: Homopolymers or copolymers of acrylic acid esters
- C08F 220/1808: {C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate}
- C08L 33/10: Homopolymers or copolymers of methacrylic acid esters
- C09D 7/63: organic
- C09J 2433/00: Presence of (meth)acrylic polymer
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

Addition-fragmentation agents of the formula are disclosed: wherein R1, R2 and R3 are each independently Z-Q-, a (hetero)alkyl group or a (hetero)aryl group with the proviso that at least one of R1, R2 and R3 is Zm-Q-, Q is a linking group have a valence of m+1; Z is an ethylenically unsaturated polymerizable group, m is 1 to 6; each X1 is independently —O— or —NR4—, where R4 is H or C1-C4 alkyl, and n is 0 or 1.

## Claims

### Claim 1

A non-aqueous polymerizable composition comprising at least one free-radically polymerizable monomer, an initiator and an addition-fragmentation agent of the formula:
wherein
R1, R2 and R3 are each independently Zm-Q-, a (hetero)alkyl group or a (hetero)aryl group with the proviso that at least two of R1, R2 and R3 is Zm-Q-,
Q is a linking group having a valence of m+1;
Z is an ethylenically unsaturated polymerizable group,
m is 1 to 6;
each X1 is independently —O— or —NR4—, where R4 is H or C1-C4 alkyl, and
n is 0 or 1.

### Claim 2 (depends on 1)

The polymerizable composition of claim 1 where Z comprises a vinyl, vinyloxy, (meth)acryloxy, (meth)acrylamido, styrenic and acetylenic functional groups.

### Claim 3 (depends on 1)

The polymerizable composition of claim 1 where Z is selected from:
wherein R4 is H or C1-C4 alkyl.

### Claim 4 (depends on 1)

The polymerizable composition of claim 1 wherein Q is selected from
from —O—, —S—, —NR4—, —SO2—, —PO2—, —CO—, —OCO—, —R6—, —NR4—CO—NR4—, —NR4—CO—O—, —NR4—CO—NR4—, —CO—O—R6—, —CO—NR4—R6—, —R6—CO—O—R6—, —O—R6—, —S—R6—, —NR4—R6—, —SO2—R6—, —PO2—R6—, —CO—R6—, —OCO—R6—, —NR4—CO—R6—, and NR4—R6—CO—O—, wherein each R4 is hydrogen, a C1 to C4 alkyl group, or aryl group, each R6 is an alkylene group having 1 to 6 carbon atoms, a 5- or 6-membered cycloalkylene group having 5 to 10 carbon atoms, or a divalent arylene group having 6 to 16 carbon atoms, with the proviso that Q-Z does not contain peroxidic linkages.

### Claim 5 (depends on 1)

The polymerizable composition of claim 1 where Q is an alkylene.

### Claim 6 (depends on 5)

The polymerizable composition of claim 5 wherein Q is an alkylene of the formula —CrH2r—, where r is 1 to 10.

### Claim 7 (depends on 1)

The polymerizable composition of claim 1 where Q is a hydroxyl-substituted alkylene.

### Claim 8 (depends on 1)

The polymerizable composition of claim 1 where Q is —CH2—CH(OH)—CH2—.

### Claim 9 (depends on 1)

The polymerizable composition of claim 1 where Q is an aryloxy-substituted alkylene.

### Claim 10 (depends on 1)

The polymerizable composition of claim 1 where R5 is an alkoxy-substituted alkylene.

### Claim 11 (depends on 1)

The polymerizable composition of claim 1 wherein R1—X1— groups and R3—X1— groups are selected from H2C═C(CH3)C(O)—O—CH2—CH(OH)—CH2—O—, H2C═C(CH3)C(O)—O—CH2—CH(O—(O)C(CH3)═CH2)—CH2—O—, H2C═C(CH3)C(O)—O—CH(CH2OPh)-CH2—O—, H2C═C(CH3)C(O)—O—CH2CH2—N(H)—C(O)—O—CH(CH2OPh)-CH2—O—, H2C═C(CH3)C(O)—O—CH2—CH(O—(O)C—N(H)—CH2CH2—O—(O)C(CH3)C═CH2)—CH2—O—, H2C═C(H)C(O)—O—(CH2)4—O—CH2—CH(OH)—CH2—O—, H2C═C(CH3)C(O)—O—CH2—CH(O—(O)C—N(H)—CH2CH2—O—(O)C(CH3)C═CH2)—CH2—O—, CH3—(CH2)7—CH(O—(O)C—N(H)—CH2CH2—O—(O)C(CH3)C═CH2)—CH2—O—, H2C═C(H)C(O)—O—(CH2)4—O—CH2—CH(—O—(O)C(H)═CH2)—CH2—O— and H2C═C(H)C(O)—O—CH2—CH(OH)—CH2—O—.

### Claim 12 (depends on 1)

The polymerizable composition of claim 1 comprising:
a) 85 to 100 parts by weight of an (meth)acrylic acid ester of non-tertiary alcohol;
b) 0 to 15 parts by weight of an acid functional ethylenically unsaturated monomer;
c) 0 to 10 parts by weight of a non-acid functional, ethylenically unsaturated polar monomer;
d) 0 to 5 parts vinyl monomer; and
e) 0 to 5 parts of a multifunctional (meth)acrylate;
based on 100 parts by weight total monomer, and
f) 0.1 to 10 parts by weight of the addition-fragmentation agent, based on 100 parts by weight of a) to e).

### Claim 13 (depends on 12)

The polymerizable composition of claim 12 further comprising 0.01 to 5 parts of a multifunctional (meth)acrylate.

### Claim 14 (depends on 1)

The polymerizable composition of claim 1 further comprising an organic solvent.

### Claim 15 (depends on 1)

The polymerizable composition of claim 1 having less than 0.1 wt. % water.

### Claim 16 (depends on 1)

An article comprising a layer of the polymerizable composition of claim 1 on a substrate.

### Claim 17 (depends on 1)

An article comprising the cured polymerizable composition of claim 1 on a substrate.

### Claim 18 (depends on 1)

A method of bonding two substrates together comprising the steps of coating the polymerizable composition of claim 1 to a surface of one or both substrates, contacting the coated surfaces, optionally with pressure, and curing the polymerizable composition.

### Claim 19 (depends on 1)

A method of bonding two substrates together comprising the steps of coating the polymerizable composition of claim 1 to a surface of one or both substrates, wherein the coating of polymerizable composition is at least partially cured, contacting the coated surfaces optionally with pressure, and further curing the polymerizable compositions if necessary.