Composite and laminate articles and polymerizable systems for producing the same

Patent metadata

Field	Value
Publication number	US-10913875-B2
Application number	US-201314388601-A
Country	US
Kind code	B2
Filing date	Mar 29, 2013
Priority date	Mar 30, 2012
Publication date	Feb 9, 2021
Grant date	Feb 9, 2021

Abstract

A composite material comprises a reinforcing material carried in a polymer matrix material which is the polymerization product of a polymerizable composition comprising a di-activated vinyl compound, with the proviso that the di-activated vinyl compound is not a cyanoacrylate. The reinforcing materials may be a wide variety of substrates including thermally sensitive materials. Exemplary composites can be molded and cured at ambient temperatures. Also disclosed are laminate materials having layered materials adhered by curing a di-activated vinyl polymerizable composition.

First claim

What is claimed is:

1. A composite material comprising:
a polymer material formed from one or more monomers, the one or more monomers selected from the group consisting of a methylene malonate monomer, a methylene betaketoester monomer, and a methylene betadiketone monomer; and
a filler material, the filler material comprising one or more of glass, natural and synthetic fiber, carbon, clay, fiberglass, carbon fiber, wood particles, wood shavings, wood flour, alumina, sand, plastics, polycarbonate, acrylonitrile butadiene styrene, aluminized fiberglass, polyethylene fibers, polypropylene fibers, and aramid fiber; and
wherein each of the methylene malonate monomer, the methylene betaketoester monomer, and the methylene betadiketone monomer are multifunctional monomers.

2. The composite material according to claim 1 , wherein the methylene malonate monomer is represented by the formula: R 1 —OC(O)—C(═CH 2 )—C(O)—O—R 2 ; and
wherein R 1 and R 2 are independently C1-C15 alkyl, C2-C15 alkenyl, halo-(C1-C15 alkyl), C3-C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl-(C1-C15 alkyl), aryl, aryl-(C1-C15 alkyl), heteroaryl, heteroaryl-(C1-C15 alkyl), or alkoxy-(C1-C15 alkyl), each of which may be optionally substituted by C1-C15 alkyl, halo-(C1-C15 alkyl), C3-C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl-(C1-C15 alkyl), -aryl, aryl-(C1-C15 alkyl), heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio, hydroxyl, nitro, azido, acyloxy, carboxy, ester or sulfonyl; or
wherein R and R 2 are taken together with the atoms to which they are bound to form a 5-7 membered heterocyclic ring which may be optionally substituted by C1-C15 alkyl, halo-(C1-C15 alkyl), C3-C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl-(C1-C15 alkyl), aryl, aryl-(C1-C15 alkyl), heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio, hydroxyl, nitro, azido, acyloxy, carboxy, ester or sulfonyl.

3. The composite material according to claim 1 , wherein the methylene betaketoester monomer is represented by the formula: R 3 —C(O)—C(═CH 2 )—C(O)—O—R 4 ; and
wherein R 3 and R 4 are independently C1-C15 alkyl, C2-C15 alkenyl, halo-(C1-C15 alkyl), C3-C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl-(C1-C15 alkyl), aryl, aryl-(C1-C15 alkyl), heteroaryl, heteroaryl-(C1-C15 alkyl), or alkoxy-(C1-C15 alkyl), each of which may be optionally substituted by C1-C15 alkyl, halo-(C1-C15 alkyl), C3-C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl-(C1-C15 alkyl), aryl, aryl-(C1-C15 alkyl), heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio, hydroxyl, nitrol, azido, acyloxy, carboxy, ester or sulfonyl; or
wherein R 3 and R 4 are taken together with the atoms to which they are bound to form a 5-7 membered heterocyclic ring which may be optionally substituted by C1-C15 alkyl, halo-(C1-C15 alkyl), C3-C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl-(C1-C15 alkyl), aryl, aryl-(C1-C15 alkyl), heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio, hydroxyl, nitro, azido, acyloxy, carboxy, ester or sulfonyl.

4. The composite material according to claim 1 , wherein the methylene betadiketone monomer is represented by the formula: R 5 —C(O)—C(═CH 2 )—C(O)—R 6 ; and
wherein R 5 and R 6 are independently C1-C15 alkyl, C2-C15 alkenyl, halo-(C1-C15 alkyl), C3-C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl-(C1-C15 alkyl), aryl, aryl-(C1-C15 alkyl), heteroaryl, or heteroaryl-(C1-C15 alkyl), or alkoxy-(C1-C15 alkyl), each of which may be optionally substituted by C1-C15 alkyl, halo-(C1-C15 alkyl), C3-C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl-(C1-C15 alkyl), aryl, aryl-(C1-C15 alkyl), heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio, hydroxyl, nitro, azido, acyloxy, carboxy, ester or sulfonyl; or
wherein R 5 and R 6 are taken together with the atoms to which they are bound to form a 5-7 membered heterocyclic ring which may be optionally substituted by C1-C15 alkyl, halo-(C1-C15 alkyl), C3-C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl-(C1-C15 alkyl), aryl, aryl-(C1-C15 alkyl), heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio, hydroxyl, nitro, azido, acyloxy, carboxy, ester or sulfonyl.

5. The composite material according to claim 1 , wherein the multifunctional monomer comprises two or more units represented by the structure: —W—C(O)—C(═CH 2 )—C(O)—W—, where W represents —O— or a direct bond.

6. The composite material according to claim 1 , wherein the polymer material is formed from two or more multifunctional monomers.

7. The composite material according to claim 1 , wherein the polymer material is formed from one or more monofunctional monomers and one or more multifunctional monomers.

8. An article of manufacture comprising the composite material of claim 1 .

9. The article of manufacture according to claim 8 comprising one or more thermally sensitive materials unable to withstand applied heat of greater than 100° C.

10. The composite material according to claim 1 , further comprising a polymerization activator.

11. The composite material according to claim 10 , wherein the polymerization activator is present in or on the filler material.

12. The composite material according to claim 10 , wherein the polymerization activator is in the form of a base, a base precursor, a base creator, or a base enhancer.

13. The composite material according to claim 12 , wherein the polymerization activator comprises one or more of an organic material, an inorganic material and an organometallic material.

14. The composite material according to claim 10 , wherein the polymerization activator comprises one or more of: sodium acetate; potassium acetate; acid salts of sodium, potassium, lithium, copper, and cobalt; tetrabutyl ammonium fluoride, chloride, and hydroxide; an amine whether primary, secondary or tertiary; an amide; salts of polymer bound acids; benzoate salts; 2,4-pentanedionate salts; sorbate salts; propionate salts; secondary aliphatic amines; piperidene, piperazine, N-methylpiperazine, dibutylamine, morpholine, diethylamine, pyridine, triethylamine, tripropylamine, triethylenediamine, N,N-dimethylpiperazine, butylamine, pentylamine, hexylamine, heptylamine, nonylamine, decylamine; salts of amines with organic monocarboxylic acids; piperidine acetate; metal salt of a lower monocarboxylic acid; copper(II) acetate, cupric acetate monohydrate, potassium acetate, zinc acetate, zinc chloracetate, magnesium chloracetate, magnesium acetate; and salts of polyacrylic acid copolymers.

15. The composite material according to claim 1 , further comprising a formulation additive.

16. The composite material according to claim 15 , wherein the formulation additive comprises one or more of plasticizers, thixotropic agents, adhesion promoters, antioxidants, light stabilizers, UV stabilizers, fillers, surfactants, wetting agents, viscosity modifiers, extenders, dispersants, anti-blocking agents, defoamers, air release agents, anti-sagging agents, anti-setting agents, matting agents, flattening agents, waxes, anti-mar additives, anti-scratch additives, and inert resins.

17. A method for preparing a laminate material, the method comprising:
providing a first substrate;
applying to the first substrate a laminate adhesive comprising a polymer material formed from one or more monomers, the one or more monomers selected from the group consisting of a methylene malonate monomer, a methylene betaketoester monomer, and a methylene betadiketone monomer; and
adhering a second substrate to the first substrate by curing of the laminate adhesive; and
wherein

Assignees

• Sirrus Inc

Inventors

• Malofsky Bernard M
• Malofsky Adam G
• Ellison Matthew M

Classifications

• C08J5/249

  characterised by the additives used in the prepolymer mixture · CPC title

• C08J5/246

  using polymer based synthetic fibres · CPC title

• C08J5/244

  using glass fibres · CPC title

• C08J5/243

  using carbon fibres · CPC title

• C08F222/14

  Esters having no free carboxylic acid groups {, e.g. dialkyl maleates or fumarates} · CPC title