# US 11,897,990 B2 · Curable poly(polyphenylene ether) oligomer compositions for coatings

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- Number: US 11,897,990 B2
- Document ID: US11897990B2
- Status: Granted
- Kind: B2
- Application number: 17/606,905
- Filed: 2020-04-03
- Published: 2022-06-30
- Granted: 2024-02-13
- Earliest claimed: 2019-04-30
- Assignees: Shpp Global Technologies B.V.
- Applicants: Shpp Global Technologies B.V.
- Inventors: Brian Jason Rice; Eylem Tarkin-Tas
- Web page: https://patentgrep.com/patent/US11897990B2

## CPC

- C08F 290/062: {Polyethers}
- C08G 65/485: {Polyphenylene oxides}
- C08F 290/068: {Polysiloxanes}
- C08J 5/249: {characterised by the additives used in the prepolymer mixture}
- C08L 71/126: {modified by chemical after-treatment}
- 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 151/085: {on to polysiloxanes}
- C09D 183/12: containing polyether sequences
- 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 151/085: {on to polysiloxanes}
- C08G 77/46: containing polyether sequences
- C08J 2351/08: grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- 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)

## Abstract

An ultraviolet light-curable coating composition includes 5-40 weight percent of an ultraviolet light-curable poly(polyphenylene ether) oligomer; 60-95 weight percent of an ultraviolet light-curable monomer, oligomer, polymer, or a combination thereof; and 0.01-3 weight percent of a photoinitiator.

## Claims

### Claim 1

An ultraviolet light-curable coating composition comprising:
5-40 weight percent of an ultraviolet light-curable poly(polyphenylene ether) oligomer;
60-95 weight percent of an ultraviolet light-curable monomer, oligomer, polymer, or a combination thereof, wherein the monomer comprises a linear or branched alkyl group, a non-aromatic cyclic group, or a partially aromatic group; and
0.01-3 weight percent of a photoinitiator activated by ultraviolet light.

### Claim 2 (depends on 1)

The ultraviolet light-curable coating composition of claim 1, wherein the ultraviolet light-curable poly(polyphenylene ether) oligomer comprises the structure
wherein
each occurrence of Q1 and Q2 is independently halogen, unsubstituted or substituted C1-12 primary or secondary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;
each occurrence of Q3 and Q4 is independently hydrogen, halogen, unsubstituted or substituted C1-C12 primary or secondary hydrocarbyl, C1-C12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;
x and y are each independently 0-30;
Z is hydrogen, allyl, vinyl, or (meth)acrylate provided that at least one Z is allyl, vinyl, or (meth)acrylate;
L is of the formula
wherein
each occurrence of R3, R4, R5, and R6 is independently hydrogen, halogen, unsubstituted or substituted C1-12 primary or secondary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;
w is 0 or 1; and
Y is
wherein
each occurrence of R7 is independently hydrogen or C1-12 hydrocarbyl,
each occurrence of R8 and R9 is independently hydrogen, C1-12 hydrocarbyl, or
R8 and R9 together form a C4-12 cyclohydrocarbylene with the carbon atom; or
L is of the formula
wherein
E is 6-100,
each occurrence of R is independently an unsubstituted or substituted C1-13 alkyl, C1-13 alkoxy, C3-6 cycloalkyl, C3-6 cycloalkoxy, C6-14 aryl, C6-10 aryloxy, C7-13 arylalkylene, or C7-13 alkylarylene; each p and q are independently 0 or 1,
R1 is a divalent C2-8 aliphatic group,
each occurrence of M is independently halogen, cyano, nitro, C1-8 alkylthio, C1-8 alkyl, C1-8 alkoxy, C2-8 alkenyl, C2-8 alkenyloxy, C3-8 cycloalkyl, C3-8 cycloalkoxy, C6-10 aryl, C6-10 aryloxy, C7-12 aralkyl, C7-12 aralkoxy, C7-12 alkylaryl, or C7-12 alkylaryloxy, and
each n is independently 0, 1, 2, 3, or 4.

### Claim 3 (depends on 1)

The ultraviolet light-curable coating composition of claim 1, wherein the ultraviolet light-curable poly(polyphenylene ether) oligomer comprises
at least one allyl, vinyl, or (meth)acrylate terminal group;
a poly(polyphenylene ether) block of the formula
wherein
each occurrence of Z1 is independently halogen, unsubstituted or substituted C1-12 primary or secondary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, and
each occurrence of Z2 is independently hydrogen, halogen, unsubstituted or substituted C1-12 primary or secondary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and a polysiloxane block comprising repeating units of the formula
a polysiloxane block comprising repeating units having the structure
wherein
each occurrence of R3 is independently C1-12 hydrocarbyl or C1-12 halohydrocarbyl, and the polysiloxane block further comprises a terminal unit of formula (6)
wherein
Y is hydrogen, halogen, C1-12 hydrocarbyl, or C1-12 hydrocarbyloxy, and
each occurrence of R3 is independently hydrogen, C1-12 hydrocarbyl, or C1-12 halohydrocarbyl.

### Claim 4 (depends on 1)

The ultraviolet light-curable coating composition of claim 1, wherein the ultraviolet light-curable poly(polyphenylene ether) oligomer comprises the polysiloxane block is of the formula
wherein n has an average value of 5-100.

### Claim 5 (depends on 1)

The ultraviolet light-curable coating composition of claim 1, wherein the poly(polyphenylene ether) oligomer comprises at least one terminal (meth)acrylate group.

### Claim 6 (depends on 1)

The ultraviolet light-curable coating composition of claim 1, wherein the ultraviolet light-curable poly(polyphenylene ether) comprises the formula
wherein
each occurrence of Q1 and Q2 is independently halogen, unsubstituted or substituted C1-6 primary or secondary hydrocarbyl, C1-6 hydrocarbylthio, C1-6 hydrocarbyloxy, or C2-6 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;
each occurrence of Q3 and Q4 is independently hydrogen, halogen, unsubstituted or substituted C1-C6 primary or secondary hydrocarbyl, C1-C6 hydrocarbylthio, C1-6 hydrocarbyloxy, or C2-6 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;
x and y are each independently 0-30; and
L is of the formula (3)
wherein
each occurrence of R3, R4, R5, and R6 is independently hydrogen, halogen, unsubstituted or substituted C1-6 primary or secondary hydrocarbyl, C1-6 hydrocarbylthio, C1-6 hydrocarbyloxy, or C2-6 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;
w is 0 or 1;
R10 is methyl or hydrogen; and
Y is
wherein
each occurrence of R7 is independently hydrogen or C1-6 hydrocarbyl,
each occurrence of R8 and R9 is independently hydrogen, C1-6 hydrocarbyl.

### Claim 7 (depends on 1)

The ultraviolet light-curable coating composition of claim 1, wherein the ultraviolet light-curable poly(polyphenylene ether) oligomer is of the formula
wherein
each occurrence of Q5 and Q6 is independently methyl, cyclohexyl, phenyl, di-n-butylaminomethyl, or morpholinomethyl;
each occurrence of a and b is independently 0-20, with the proviso that the sum of a and b is at least 2; and
each occurrence of R10 is methyl or hydrogen.

### Claim 8 (depends on 1)

The ultraviolet light-curable coating composition of claim 1, wherein the ultraviolet light-curable poly(polyphenylene ether) has a number average molecular weight of 500-7,000 g/mol, and a weight average molecular weight of 500-15,000 g/mol, as determined by gel permeation chromatography using polystyrene standards.

### Claim 9 (depends on 1)

The ultraviolet light-curable coating composition of claim 1, wherein the ultraviolet light-curable monomer, oligomer, or polymer is a (meth)acrylate.

### Claim 10 (depends on 9)

The ultraviolet light-curable coating composition of claim 9, wherein the curable monomer, oligomer or polymer is dipropylene glycol diacrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, isobornyl acrylate, isobornyl methacrylate a polyether acrylate, an amine-modified polyether acrylate, a polyester acrylate, a polyurethane acrylate, an aliphatic urethane acrylate, or a combination thereof.

### Claim 11 (depends on 1)

The ultraviolet light-curable coating composition of claim 1 comprising:
20-40 weight percent of the ultraviolet light-curable poly(polyphenylene ether) oligomer;
60-80 weight percent of the ultraviolet light-curable monomer, oligomer, polymer, or a combination thereof; and
0.1-3 weight percent of a photoinitiator.

### Claim 12 (depends on 1)

The ultraviolet light-curable coating composition of claim 1 comprising:
20-40 weight percent of a meth(acrylate)-endcapped poly(polyphenylene ether) oligomer;
60-80 weight percent of dipropylene glycol diacrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, a polyether acrylate, an amine-modified polyether acrylate, a polyester acrylate, a polyurethane acrylate, an aliphatic urethane acrylate, isobornyl acrylate, isobornyl methacrylate, or a combination thereof; and
0.1-3 weight percent of a photoinitiator.

### Claim 13 (depends on 1)

A cured product of the curable composition of claim 1, having
a glass transition temperature of 120-200° C.;
a water absorption of less than or equal to 1 weight percent measured after immersion in deionized water at 25° C. for 24 hours, or
a combination thereof.

### Claim 14 (depends on 1)

A method of forming a coated substrate, the method comprising
providing a substrate;
coating the substrate with an ultraviolet light-curable coating composition of claim 1 to provide a coated substrate; and
curing the coating composition with ultraviolet light.

### Claim 15 (depends on 13)

An article comprising the thermoset composition of claim 13, wherein the coating is in the form of a layer, an encapsulant, an adhesive, a sealant, a molded coating, a prepreg, a casing, or a laminate.

### Claim 16 (depends on 1)

The ultraviolet light-curable coating composition of claim 1 consisting of:
5-40 weight percent of the ultraviolet light-curable poly(polyphenylene ether) oligomer;
60-95 weight percent of the ultraviolet light-curable monomer, oligomer, polymer, or a combination thereof, wherein the monomer comprises a linear or branched alkyl group, a non-aromatic cyclic group, or a partially aromatic group;
0.01-3 weight percent of a photoinitiator activated by ultraviolet light; and
0-10 weight percent of an additive composition consisting of a stabilizer, mold release agent, a lubricant, a processing aid, a drip retardant, a nucleating agent, a UV blocker, a dye, a pigment, an antioxidant, an anti-static agent, a blowing agent, mineral oil, a metal deactivator, an anti-blocking agent, a solvent, or a combination thereof.

### Claim 17 (depends on 1)

The ultraviolet light-curable coating composition of claim 1 consisting of:
5-40 weight percent of the ultraviolet light-curable poly(polyphenylene ether) oligomer;
60-95 weight percent of the ultraviolet light-curable monomer, oligomer, polymer, or a combination thereof, wherein the monomer comprises a linear or branched alkyl group, a non-aromatic cyclic group, or a partially aromatic group;
0.01-3 weight percent of a photoinitiator activated by ultraviolet light; and
0-5 weight percent of an additive composition consisting of a stabilizer, mold release agent, a lubricant, a processing aid, a drip retardant, a nucleating agent, a UV blocker, a dye, a pigment, an antioxidant, an anti-static agent, a blowing agent, mineral oil, a metal deactivator, an anti-blocking agent, a solvent, or a combination thereof.

### Claim 18 (depends on 1)

The ultraviolet light-curable coating composition of claim 1, wherein the poly(polyphenylene ether) oligomer has an intrinsic viscosity of 0.05-0.1 deciliter per gram.