# US 10,479,848 B2 · Addition-fragmentation oligomers

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- Number: US 10,479,848 B2
- Document ID: US10479848B2
- Status: Granted
- Kind: B2
- Application number: 15/549,681
- Filed: 2016-01-28
- Published: 2018-02-15
- Granted: 2019-11-19
- Earliest claimed: 2015-02-20
- Assignees: 3M Innovative Properties Company
- Applicants: 3M Innovative Properties Company
- Inventors: William H. Moser; Ann R. Fornof; Guy D. Joly; Serkan Yurt; Larry R. Krepski; Ahmed S. Abuelyaman; Afshin Falsafi; Bradley D. Craig; Joel D. Oxman; Babu N. Gaddam
- Web page: https://patentgrep.com/patent/US10479848B2

## CPC

- C08F 22/1006: {of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate}
- A61K 6/62: Photochemical radical initiators
- A61K 6/71: Fillers
- A61K 6/887: Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C07C 69/602: Dicarboxylic acid esters having at least two carbon-to-carbon double bonds
- C07F 7/1804: {Compounds having Si-O-C linkages (Si-O-acyl linkages C07F7/1896)}
- C07F 9/091: {with hydroxyalkyl compounds with further substituents on alkyl}
- C08F 292/00: Macromolecular compounds obtained by polymerising monomers on to inorganic materials
- C09D 4/00: Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond {; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16}
- C09D 7/61: inorganic
- C09J 4/06: {Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond} in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
- C08K 3/36: Silica
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- A61K: PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES (devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms A61J3/00; chemical aspects of, or use of materials for deodorisation of air, for disinfection or sterilisation, or for bandages, dressings, absorbent pads or surgical articles A61L; soap compositions C11D)
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- 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)
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)

## Abstract

Novel stress-reducing crosslinking oligomers that have application in dental restoratives, thin films, hardcoats, composites, adhesives, and other uses subject to stress reduction are described. The addition-fragmentation process of crosslinking results in a chain-transfer event that provides novel polymers that may be further functionalized. In addition, the addition-fragmentation oligomer comprises pendent functional groups that bond to a substrate by forming an ionic or covalent bond, or etch the substrate by chemically removing some material from the substrate.

## Claims

### Claim 1

An addition-fragmentation oligomer of the formula:
wherein
RA is non-directionally a 1-methylene-3,3-dimethyl propyl group,
RB is hydrocarbyl group, wherein at least two RA and/or RB groups are substituted with a pendent functional group D that bonds or etches a substrate to which it adheres;
X1 is —O— or NR5—, where R5 is H or C1-C4 alkyl;
Z comprises an ethylenically unsaturated polymerizable group;
y is 0 or 1; and
x is 0 to 60;
wherein the D group that bonds or etches a substrate is selected from monophosphate, phosphonate, phosphonic acid, hydroxamic acid, carboxylic acid, acetoacetate, anhydride, isonitrile, silyl, disulfide, thiol, amino sulfinic acid, sulfonic acid, and phosphine groups.

### Claim 2 (depends on 1)

The addition-fragmentation oligomer of claim 1 wherein the RB units comprise a 1-methylene-3,3-dimethyl propyl group.

### Claim 3 (depends on 1)

The addition-fragmentation oligomer of claim 1, wherein at least 50% of the RA and/or RB units are substituted by a D group.

### Claim 4 (depends on 1)

The addition-fragmentation oligomer of claim 1 wherein Z comprises a (meth)acrylate or vinyl group.

### Claim 5 (depends on 1)

The addition-fragmentation oligomer of claim 1 derived from A compounds of the formula:
R1—O—CO—RA—CO—O—R1, wherein RA is a 1-methylene-3,3-dimethylpropyl group and R1 is H, alkyl, aryl or RFG, where RFG is an aryl or an alkyl further substituted with a nucleophilic or electrophilic functional group, derived from B compounds of the formula:
X2—RB—X2, wherein RB is a hydrocarbyl group that further comprises a functional group D and X2 is functional group reactive with the functional groups of the A compound.

### Claim 6 (depends on 5)

The addition-fragmentation oligomer of claim 5 wherein the compound of the formula X2—RB—X2 is selected from difunctional epoxides, diols, aziridines, isocyanates and diamines.

### Claim 7 (depends on 5)

The addition fragmentation of claim 5 where reaction between the A compounds and B compounds yields an intermediate oligomer of the formula:
wherein
RA is non-directionally a 1-methylene-3,3-dimethyl propyl group;
RB is a hydrocarbyl group, wherein at least two RB groups are substituted with a functional group D that bonds or etches a substrate to which it adheres;
X1 is —O— or NR5—, where R5 is H or C1-C4 alkyl;
X5 is a terminal functional group selected from —OR1 of the A compounds or X2 of the B compounds;
y is 0 or 1; and
x is 0 to 60.

### Claim 8 (depends on 1)

The addition-fragmentation oligomer of claim 1 where x+y is 0 to 20.

### Claim 9 (depends on 1)

The addition-fragmentation oligomer of claim 1 where the Z group is derived from an ethylenically unsaturated compound of the formula:
(Z)d—X3, where Z comprises an ethylenically unsaturated group, and X3 is a functional group reactive with the terminal functional groups of the intermediate oligomer.

### Claim 10 (depends on 9)

The addition-fragmentation oligomer of claim 9 wherein the compound of the formula (Z)d—X3 is of the formula:
Y1—R3—O—CO—CR2═CH2, where Y1 is an electrophilic functional group reactive with terminal electrophilic functional groups of the intermediate oligomer, R3 is an alkylene, R2 is H or CH3.

### Claim 11 (depends on 1)

The addition-fragmentation oligomer of claim 1 wherein the D group is derived from a compound represented by
Y1—(R13)q—X7-D or Y2—(R13)q—X7-D, wherein:
Y1 is an electrophilic functional group reactive with nucleophilic X2 groups on a B compound,
Y2 is a nucleophilic functional group reactive with electrophilic X2 groups on a B compound,
R13 is a (hetero)hydrocarbyl group,
q is 0 or 1,
X7 is selected from a covalent bond or a divalent linking group,
D is a functional group that bonds or etches the underlying substrate, and
the B compound has the formula X2—B—X2 wherein RB is a hydrocarbyl group and X2 comprises a functional group reactive with Y1 or Y2.

### Claim 12 (depends on 1)

A polymerizable composition comprising the addition-fragmentation oligomer of claim 1, at least one free-radically polymerizable monomer, and an initiator.

### Claim 13 (depends on 12)

The polymerizable composition of claim 12 comprising:
a) 85 to 100 parts by weight of an (meth)acrylic acid ester;
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 100 parts of a multifunctional (meth)acrylate;
based on 100 parts by weight total monomer a) to d), and
f) 0.1 to 12 parts by weight of the addition-fragmentation oligomer, based on 100 parts by weight of a) to e), and
g) an initiator.

### Claim 14 (depends on 13)

The polymerizable composition of claim 13 further comprising 0.01 to 100 parts of a multifunctional (meth)acrylate.

### Claim 15 (depends on 12)

The polymerizable composition of claim 12 further comprising an inorganic filler.

### Claim 16 (depends on 12)

An article comprising a layer of the polymerizable composition of claim 12 on a substrate.

### Claim 17 (depends on 1)

A hardcoat composition comprising one or more multifunctional (meth)acrylate monomers or (meth)acrylate oligomers, and the addition-fragmentation oligomer of claim 1.

### Claim 18 (depends on 17)

The hardcoat composition of claim 17 comprising:
a) 0.1-10 wt. % of the addition fragmentation oligomer of Formula I;
b) 20-80 wt. % of multifunctional (meth)acrylate monomers and/or multifunctional (meth)acrylate oligomers,
c) 0 to 25 wt. % (meth)acrylate diluent; and
d) 20 to 75 wt. % of silica.

### Claim 19 (depends on 1)

A curable dental composition comprising:
a) at least one dental resin comprising at least two ethylenically unsaturated group;
b) an addition-fragmentation oligomer of claim 1; and
c) optionally an inorganic oxide filler.

### Claim 20 (depends on 19)

The dental composition of claim 19 wherein the dental resin is an isocyanurate resin, a tricyclodecane resin, cyclic allylic sulfide resins; methylene dithiepane silane resins; and poly(meth)acryloyl-containing resins, or mixtures thereof.

### Claim 21 (depends on 19)

The dental composition of claim 19 wherein the dental composition further comprises at least one other (meth)acrylate monomer is selected from ethoxylated bisphenol A dimethacrylate, 2-hydroxyethyl methacrylate, bisphenol A diglycidyl dimethacrylate, urethane dimethacrylate, triethlyene glycol dimethacrylate, glycerol dimethacrylate, ethylenegylcol dimethacrylate, neopentylglycol dimethacrylate (NPGDMA), polyethyleneglycol dimethacrylate, and mixtures thereof.