# US 10,246,540 B2 · Rapid azeotropic photo-copolymerization of styrene and methacrylate derivatives and uses thereof

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- Number: US 10,246,540 B2
- Document ID: US10246540B2
- Status: Granted
- Kind: B2
- Application number: 15/276,821
- Filed: 2016-09-27
- Published: 2017-03-30
- Granted: 2019-04-02
- Earliest claimed: 2015-09-29
- Assignees: ADA Foundation
- Applicants: ADA Foundation
- Inventors: Jirun Sun
- Web page: https://patentgrep.com/patent/US10246540B2

## CPC

- C08F 222/1065: {of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates}
- A61K 6/30: Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
- A61K 6/62: Photochemical radical initiators
- A61K 6/887: Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- B33Y 70/00: Materials specially adapted for additive manufacturing
- C08F 12/34: Monomers containing two or more unsaturated aliphatic radicals
- C08F 212/08: Styrene
- C08F 212/34: Monomers containing two or more unsaturated aliphatic radicals
- C08F 216/125: {Monomers containing two or more unsaturated aliphatic radicals, e.g. trimethylolpropane triallyl ether or pentaerythritol triallyl ether}
- C08F 220/14: Methyl esters {, e.g. methyl (meth)acrylate}
- C08F 220/68: Esters
- C08F 236/20: unconjugated
- C08K 3/36: Silica
- C09D 11/101: Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
- C09D 11/107: from unsaturated acids or derivatives thereof
- C09D 129/10: Homopolymers or copolymers of unsaturated ethers (C09D135/08 takes precedence)
- C09D 133/14: of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09J 129/10: Homopolymers or copolymers of unsaturated ethers (C09J135/08 takes precedence)
- C09J 133/14: of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- B33Y 70/10: Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
- 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)
- B33Y: ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- 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)

## Abstract

A composition of matter includes a mixture of styrene derivative monomers and methacrylate/acrylate derivative monomers, which have one or more urethane, carbamate, amide, and/or amine functional groups, and initiators, and the compositions are used to achieve composition control of the forming polymer, with the mole fraction of acrylate/methacrylate and styrene moieties in the forming polymer determined preferably by the chemistry and composition of the feeding monomers rather than the viscosity of the monomers.

## Claims

### Claim 1

A composition of matter, comprising:
two or more vinyl-containing monomers consisting of at least two different types of vinyl functional monomers, wherein the two or more vinyl-containing monomers are triethyleneglycol divinylbenzyl ether (TEG-DVBE) and methacrylate derivatives; and
one or more initiators;
wherein the two or more vinyl-containing monomers undergo vinyl conversion to form a composition-controlled cross-linked resin.

### Claim 2 (depends on 1)

The composition of matter of claim 1, wherein the methacrylate derivatives have functional groups selected from a group consisting of:
one or more carbamate groups and/or derivatives;
one or more urethane groups and/or derivatives; and
one or more amine groups and/or derivatives.

### Claim 3 (depends on 1)

The composition of matter of claim 1, wherein the one or more initiators are selected from a group consisting of:
photoinitiator(s) comprising camphorquinone or derivatives,
a combination of cam phorquinone and amine(s) derivatives, phenylpropanedione or derivatives, bisacylphosphine oxide or derivatives, or 1-hydroxycyclohexyl phenyl ketone,
wherein the initiators may be used:
with/without diary iodonium derivatives, and
with/without boryl radicals.

### Claim 4 (depends on 1)

The composition of matter in claim 1, wherein a mole fraction of methacrylate derivatives and TEG-DVBE moieties in the composition-controlled cross-linked resin is determined by the mole fraction corresponding to the methacrylate derivatives and TEG-DVBE.

### Claim 5 (depends on 1)

The composition of matter of claim 1, wherein the composition is used as dental materials that are used with or without fillers as restorative materials, laminate veneers, denture, denture repairing materials, dental adhesives, resin reinforce cements, placement of ceramic restorations, and sealants.

### Claim 6 (depends on 1)

The composition of matter of claim 1, wherein the composition is used in 3D printing.

### Claim 7 (depends on 1)

The composition of matter of claim 1, wherein the composition controlled cross-linked resin is stable against environmental challenges consisting of hydrolysis, corrosion, enzymatic degradation, and bacterial challenges.

### Claim 8 (depends on 1)

The composition of matter of claim 1, wherein the composition is used to make polymers as packaging materials, coating materials and adhesives.

### Claim 9 (depends on 1)

The composition of matter of claim 1, wherein the composition is used to make composition-controlled polymers with alternating methacrylate derivatuves/TEG-DVBE moieties in the chain of the polymers.

### Claim 10 (depends on 1)

A composition of matter made by polymerizing the composition of claim 1 with or without fillers using methods comprising of light irradiation and/or heating.

### Claim 11 (depends on 10)

The composition of matter of claim 10, wherein the fillers are selected from a group consisting of:
metal oxide particles, ceramic particles, chitosan, polysaccharide particles, and
the particles are in nano-scale and micro-scale.

### Claim 12 (depends on 10)

The composition of matter of claim 10, wherein the composition is used as dental materials, restorative materials, laminate veneers, denture, denture repairing materials, dental adhesives, inlays and onlays, fixed bridges, implants, resin reinforce cements, placement of ceramic restorations, and sealants.

### Claim 13 (depends on 1)

A composition of matter made by polymerizing the composition of claim 1 after the composition infiltrates into pores of porous objects using methods comprising of light irradiation and/or heating.

### Claim 14 (depends on 13)

The composition of matter of claim 13, wherein the porous objects are selected from a group consisting of:
metal oxide, ceramic, chitosan, polysaccharide particles, metal, and wood.

### Claim 15 (depends on 13)

The composition of matter of claim 13, wherein the composition is used as dental materials, restorative materials, laminate veneers, denture, denture repairing materials, dental adhesives, inlays and onlays, fixed bridges, implants, resin reinforce cements, placement of ceramic restorations, and sealants.

### Claim 16 (depends on 1)

A composition of matter made by polymerizing the composition of claim 1 to make vinyl-free polymers, polymers with no polymerizable vinyl groups, using methods comprising light irradiation and/or heating.

### Claim 17 (depends on 16)

The composition of matter of claim 16, wherein the composition is used independently or as a component in medical devices, electronic devices, and solar cells.

### Claim 18 (depends on 1)

The composition of matter of claim 1, wherein a copolymer of methacrylate derivatives and TEG-DVBE generates less stress than a bisphenol A glycidyl methacrylate/triethylene glycol dimethacrylate (BisGMA/TEGDMA) copolymer at the same degree of vinyl conversion when initiated by a combination of camphorquinone and amine.