Method of forming an exfoliated or intercalated filler material

Patent metadata

Field	Value
Publication number	US-11248106-B2
Application number	US-201816499028-A
Country	US
Kind code	B2
Filing date	Mar 28, 2018
Priority date	Mar 28, 2017
Publication date	Feb 15, 2022
Grant date	Feb 15, 2022

Abstract

According to the present disclosure, a method of forming an exfoliated or intercalated filler material is provided, wherein the said method comprises the steps of mixing particles of filler material such as montmorillonite (MMT), mica, layered double hydroxide (LDH), and attapulgite (AT) dispersed in an aqueous medium with cationic acrylate monomers to form modified particles comprising positively charged ions, dispersing the modified particles in organic medium to form a dispersion, contacting said dispersion with an organo-silicate such as tetraethyl orthosilicate (TEOS) and a functionalizing agent comprising an organo-silane such as aminopropyltrimethoxysilane (APTMS), in the presence of a basic catalyst to form a layer of silica on the modified particles. The present disclosure also relates to an exfoliated or intercalated filler material obtained by the said method as well as a method of forming a resin/clay nanocomposite.

First claim

The invention claimed is:

1. A method of forming an exfoliated or intercalated filler material, comprising:
mixing a suspension comprising particles of a filler material dispersed in an aqueous medium with cationic acrylate monomers to form modified particles comprising positively charged ions;
dispersing the modified particles in an organic medium to form a dispersion; and
contacting the dispersion with an organo-silicate and a functionalizing agent comprising an organo-silane in the presence of a basic liquid catalyst to form a layer of silica on the modified particles, thereby forming the exfoliated or intercalated filler material.

2. The method of claim 1 , wherein the cationic acrylate monomers comprise 2-aminoethyl methacrylate hydrochloride, N-(3-Aminopropyl)methacrylamide hydrochloride, (2-Boc-amino)ethyl methacrylate, methyl 3-(3-amino-5-methoxypyridin4-yl)acrylate, 3-(trimethoxysilyl)propyl acrylate, 2-[[(butylamino)carbonyl]oxy]ethyl acrylate, ethyl 3-(2-amino-5-bromo-3-pyridyl)acrylate, [2-(acryloyloxy)ethyl] trimethylammonium chloride, or methyl 2-[(5-chloro-2-nitrophenoxy)methyl]acrylate.

3. The method of claim 1 , wherein the suspension contains 2 to 30 wt % of the cationic acrylate monomers, wherein the wt % is based on weight of the particles of the filler material.

4. The method of claim 1 , wherein the aqueous medium comprises deionized water or purified water.

5. The method of claim 1 , wherein the mixing occurs at 20 to 90° C.

6. The method of claim 1 , wherein the organic medium comprises a ketone group, an alcohol group, or a hydrocarbon.

7. The method of claim 6 , wherein the organic medium comprises acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone.

8. The method of claim 6 , wherein the organic medium comprises methanol, ethanol, propanol, n-butanol, i-butanol, sec-butanol, tert-butanol, ethylene glycol, propylene glycol, or butylene glycol.

9. The method of claim 6 , wherein the organic medium comprises hexane, heptane, octane, benzene, toluene, or xylene.

10. The method of claim 1 , wherein the organo-silicate has a formula of SiX 4 and X is C 1-6 alkoxy.

11. The method of claim 1 , wherein the organo-silane is represented by the formula (Y—R) n SiX m , wherein R is C 3-6 alkyl, X is C 1-6 alkoxy, Y is a chemical moiety capable of forming covalent bonds with a resin or polymer matrix, and sum of n and m is 4.

12. The method of claim 11 , wherein Y comprises an amine.

13. The method of claim 11 , wherein the organo-silane comprises β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-(N,N-dimethyl)aminopropyltrimethoxysilane, γ-(N,N-diethyl)aminopropyltrimethoxysilane, γ-(N,N-dibutyl)aminopropyltrimethoxysilane, γ-(N-methyl)anilinopropyltrimethoxysilane, γ-(N-ethyl)anilinopropyltrimethoxysilane, γ-(N,N-dimethyl)aminopropyltriethoxysilane, γ-(N,N-diethyl)aminopropyltriethoxysilane, γ-(N,N-dibutyl)aminopropyltriethoxysilane, 7-(N-methyl)aminopropyltriethoxysilane, γ-(N-ethyl)aminopropyltriethoxysilane, γ-(N,N-dimethyl)aminopropylmethyldimethoxysilane, γ-(N,N-diethyl)aminopropylmethyldimethoxysilane, γ-(N,N-dibutyl)aminopropylmethyldimethoxysilane, γ-(N-methyl)aminopropylmethyldimethoxysilane, γ-(N-ethyl)aminopropylmethyldimethoxysilane, N-(trimethoxysilylpropyl)ethylenediamine, N-(dimethoxymethylsilylisopropyl)ethylenediamine, and/or γ-mercaptopropylmethyldimethoxysilane.

14. The method of claim 1 , wherein 10 to 30 wt % of the organo-silane is added to the dispersion, wherein the wt % is based on weight of the organo-silicate.

15. The method of claim 1 , wherein the basic liquid catalyst comprises ammonia, ammonium hydroxide, or alkylamine.

16. The method of claim 1 , wherein 20 to 65 wt % of the basic liquid catalyst is added to the dispersion, wherein the wt % is based on weight of the organo-silicate.

17. The method of claim 1 , further comprising removing the organic medium and excess basic liquid catalyst under vacuum.

18. The method of claim 1 , further comprising drying the exfoliated or intercalated filler material.

19. An exfoliated or intercalated filler material obtained by a method comprising:
mixing a suspension comprising particles of a filler material dispersed in an aqueous medium with cationic acrylate monomers to form modified particles comprising positively charged ions;
dispersing the modified particles in an organic medium to form a dispersion; and
contacting the dispersion with an organo-silicate and a functionalizing agent comprising an organo-silane in the presence of a basic liquid catalyst to form a layer of silica on the modified particles, thereby forming the exfoliated or intercalated filler material,
wherein the exfoliated or intercalated filler material comprises the layer of silica which is formed in situ.

20. A method of forming a nanocomposite, comprising:
mixing a suspension comprising particles of a filler material dispersed in an aqueous medium with cationic acrylate monomers to form modified particles comprising positively charged ions;
dispersing the modified particles in an organic medium to form a dispersion;
contacting the dispersion with an organo-silicate and a functionalizing agent comprising an organo-silane in the presence of a basic liquid catalyst to form a layer of silica on the modified particles, thereby forming the exfoliated or intercalated filler material;
mixing the exfoliated or intercalated filler material with a resin to form a mixture;
adding a hardener to the mixture; and
curing the mixture.

Assignees

• Agency Science Tech & Res

Inventors

• Thitsartarn Warintron
• He Chaobin
• Yeo Jayven Chee Chuan

Classifications

• C01B33/44 Primary

  Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material · CPC title

• C01P2002/77

  by unit-cell parameters, atom positions or structure diagrams · CPC title

• C01P2004/04

  obtained by TEM, STEM, STM or AFM · CPC title

• C08K9/06 Primary

  with silicon-containing compounds · CPC title

• C08K9/02

  Ingredients treated with inorganic substances · CPC title