Method for manufacturing polysilsesquioxane by using carbon dioxide solvent and polysilsesquioxane manufactured using the same

Patent metadata

Field	Value
Publication number	US-9534087-B2
Application number	US-201314350564-A
Country	US
Kind code	B2
Filing date	Apr 18, 2013
Priority date	Dec 13, 2012
Publication date	Jan 3, 2017
Grant date	Jan 3, 2017

Abstract

Disclosed is a method for manufacturing the polysilsesquioxane (PSSQ) within the carbon dioxide solvent through the control of the pressure and temperature within a reactor by the state changes, e.g., a liquid state or supercritical state, of carbon dioxide as a solvent which is environmentally friendly and pollution-free, that is to say, by making use of the fact that the solubility of reactant and product is changed according to the pressure and temperature in manufacturing the polysilsesquioxane (PSSQ).

First claim

What is claimed is:

1. A method for manufacturing polysilsesquioxane (PSSQ), the method comprising:
(i) preparing a silane compound;
(ii) preparing a carbon dioxide solvent;
(iii) injecting the silane compound into a reactor;
(iv) increasing a pressure and temperature within the reactor, and changing a state of the carbon dioxide solvent into a liquid state or a supercritical state by injecting the carbon dioxide solvent into the reactor, wherein the pressure and temperature are increased from 1,000 to 5,000 psi and from 30 to 80° C., respectively;
(v) supplying water and a catalyst to the reactor;
(vi) inducing hydrolysis and a condensation reaction by increasing the temperature within the reactor;
(vii) precipitating a polysilsesquioxane (PSSQ) product substituted with a functional group by controlling the temperature and pressure within the reactor; and
(viii) separating the silane compound of an unreacted material within the reactor from the polysilsesquioxane (PSSQ) of a product.

2. The method of claim 1 , wherein the silane compound is represented by RSiZ 3 ,
wherein R is an organic substituent and corresponds to hydrogen, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, a substituted or unsubstituted alicyclic hydrocarbon group having 3 to 30 carbon atoms, a substituted or unsubstituted silyl group having 1 to 30 carbon atoms, a substituted or unsubstituted allyl group having 3 to 30 carbon atoms, a substituted or unsubstituted acyl group having 2 to 30 carbon atoms, a substituted or unsubstituted vinyl group having 2 to 30 carbon atoms, a substituted or unsubstituted amine group having 1 to 30 carbon atoms, a substituted or unsubstituted acetate having 2 to 30 carbon atoms, or alkali metal, Z is a substituent which is hydrolyzed and corresponds to Cl, Br, I or alkoxy group.

3. The method of claim 1 , wherein the polysilsesquioxane (PSSQ) comprises a compound of the following chemical formula (1) as a monomer,
wherein R is an organic substituent and corresponds to hydrogen, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, a substituted or unsubstituted alicyclic hydrocarbon group having 3 to 30 carbon atoms, a substituted or unsubstituted silyl group having 1 to 30 carbon atoms, a substituted or unsubstituted allyl group having 3 to 30 carbon atoms, a substituted or unsubstituted acyl group having 2 to 30 carbon atoms, a substituted or unsubstituted vinyl group having 2 to 30 carbon atoms, a substituted or unsubstituted amine group having 1 to 30 carbon atoms, a substituted or unsubstituted acetate having 2 to 30 carbon atoms, or alkali metal

4. The method of claim 1 , wherein at least one of an acid catalyst and/or a base catalyst is selected as the catalyst in the step (v).

5. The method of claim 4 , wherein the acid catalyst in the step (v) further comprises at least one of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, phosphoric acid, phosphoric ester, activated clay, iron chloride, boric acid, trifluoro acetic acid, trifluoro methane sulfonic acid, and p-toluenesulfonic acid, and wherein the base catalyst in the step (v) further comprises at least one of hydroxide of alkali metal or alkali earth metal, alkoxide of alkali metal or alkali earth metal, tetra alkyl ammonium hydroxide, and amine compounds.

6. The method of claim 1 , wherein, in the step (vi), the temperature within the reactor is increased to 30 to 80° C. and the reaction is performed for 18 to 30 hours.

7. The method of claim 1 , wherein, in the step (vi), after the water and catalyst are supplied, the temperature of the reactor is increased, so that a solubility within the carbon dioxide of the silane compound is increased and reaction of the product in the liquid or supercritical carbon dioxide is also promoted.

8. The method of claim 1 , wherein, in the step (vii), the temperature is controlled to less than 45° C. and the pressure is controlled to be less 1,700 psi, so that the polysilsesquioxane (PSSQ) of the product is precipitated and the silane compound of the unreacted material remains dissolved in the carbon dioxide solvent.

9. The method of claim 1 , wherein, in the step (viii), the silane compound of the unreacted material, which has been melted in an upper portion of the reactor, is removed by flowing the liquid carbon dioxide to the reactor.

10. The method of claim 1 , further comprising, after the step (viii), controlling the pressure to a normal pressure by opening a valve connected to the outside of the reactor, discharging the carbon dioxide in the form of gas, which remains in the reactor, and obtaining the polysilsesquioxane (PSSQ) of the product precipitated on the bottom of the reactor.

11. The method of claim 1 , wherein the silane compound corresponds to at least any one selected from the group consisting of (3-Chloropropyl)trimethoxysilane, (3-bromopropyl)trimethoxysilane, (3-Iodopropyl) trimethoxysilane, (3-Aminopropyl)trimethoxysilane, (3-Mercaptopropyl)trimethoxysilane, Trimethoxy [3-(methylamino) propyl] silane, Trimethoxy (7-octen-1-yl) silane, [3-(2-aminoethylamino) propyl] trimethoxysilane, N1-(3-trimethoxysilylpropyl) diethylene triamine, 3-(trimethoxysilyl) propyl methacrylate, (3-glycidyloxy-propyl) trimethoxysilane, 3-(trimethoxysilyl) propyl acrylate, N-[3-(trimethoxysilyl) propyl] aniline, (3-chloropropyl) triethoxysilane, (3-aminopropyl) triethoxysilane, (3-Mercaptopropyl)trimethoxysilane, and (3-glycidyloxy-propyl) triethoxysilane.

12. The method of claim 1 , wherein the silane compound corresponds to at least any one selected from the group consisting of Trimethoxy (propyl) silane, Isobutyl(trimethoxy)silane, Trimethoxy (octyl) silane, Hexadecyl trimethoxysilane, Trimethoxy (octadecyl) silane, [3-(diethylamino) propyl] trimethoxysilane, (N,N-dimethylaminopropyl) trimethoxysilane, Trimethoxy (3,3,3-trifluoropropyl) silane, Trimethoxy-(2-phenylethyl) silane, 1-[3-(trimethoxysilyl) propyl] urea, Trimethoxy [2-(7-oxa-bicyclo [4,1,0] hept-3-yl) ethyl]silane, n-propyltriethoxysilane, 3-(triethoxysilyl) propionitrile, Triethoxy (isobutyl) silane, Triethoxy Pentyl silane, Hexyl triethoxysilane, Triethoxy (octyl) silane, 3-cyano-propyltriethoxysilane, N-octadecyl triethoxysilane, cyclo pentyl trimethoxysilane, (Triethoxysilyl) cyclohexane, 3-[bis (2-hydroxyethyl) amino] propyl-triethoxysilane, 1H, 1H, 2H, 2H-Perfluorooctyl triethoxysilane, 1H, 1H, 2H, 2H-Perfluorodecyl triethoxysilane, [3-[tri (ethoxy) silyl] propyl] urea or [3-[tri (methoxy) silyl] propyl] urea.

Assignees

• Korea Ind Tech Inst

Inventors

• Park In
• Hwang Ha Soo

Classifications

• C08G77/08 Primary

  characterised by the catalysts used · CPC title

• C08G77/24

  halogen-containing groups · CPC title

• C08G77/28

  sulfur-containing groups · CPC title

• C08G77/06 Primary

  Preparatory processes · CPC title

• Y02P20/544

  Cross-Sectional Technologies · mapped topic