Low-density gel product and production method therefor

Patent metadata

Field	Value
Publication number	US-11518855-B2
Application number	US-201816634800-A
Country	US
Kind code	B2
Filing date	Aug 23, 2018
Priority date	Aug 25, 2017
Publication date	Dec 6, 2022
Grant date	Dec 6, 2022

Abstract

A low-density gel product of the present disclosure has a skeleton containing a polysiloxane chain and an organic polymer chain. In the skeleton, the polysiloxane chain and the organic polymer chain are bonded to each other by covalent bonds at a plurality of positions on both of the chains with silicon atoms of the polysiloxane chain as bonding points. The organic polymer chain may be an aliphatic hydrocarbon chain. The polysiloxane chain may be a polyorganosiloxane chain. The low-density gel product of the present disclosure is a novel low-density gel product with improved mechanical properties including bending flexibility.

First claim

The invention claimed is:

1. A low-density gel product having a skeleton containing a polysiloxane chain and an organic polymer chain,
wherein the low-density gel product is an aerogel, a xerogel, or a cryogel,
wherein in the skeleton, the polysiloxane chain and the organic polymer chain are bonded to each other by covalent bonds at a plurality of positions on both of the chains with silicon atoms of the polysiloxane chain as bonding points,
wherein the polysiloxane chain and the organic polymer chain are bonded to each other via a linking part L of the repeating unit that is included in the organic polymer chain and is represented by the following formula (2):

wherein R 4 in formula (2) is a hydrogen atom, an alkyl group that may have a branch, a phenyl group that may have a substituent, a hydroxyl group, or a halogen atom,
R 5 and R 6 are each independently a hydrogen atom, an alkyl group that may have a branch, a phenyl group that may have a substituent, a hydroxyl group, a halogen atom, an N,N-dimethylamide group, or an N-isopropylamide group,
the linking part L is selected from the group consisting of: an alkylene group that may be cyclic or may have a branch and has 1 to 10 carbon atoms; a phenylene group that may have a substituent; an amide group; an ether group; a combination thereof; or a bond, and
when the linking part L is a bond, the silicon atom of the polysiloxane chain is directly bonded to C* in formula (2).

2. The low-density gel product according to claim 1 , wherein the polysiloxane chain is a polyorganosiloxane chain.

3. The low-density gel product according to claim 2 , wherein an organo group bonded to the silicon atom of the polyorganosiloxane chain is an alkyl group having 1 to 4 carbon atoms.

4. The low-density gel product according to claim 3 , wherein the organo is a methyl group.

5. The low-density gel product according to claim 1 , wherein the organic polymer chain has a degree of polymerization of 2 to 10000.

6. The low-density gel product according to claim 1 ,
wherein, when the low-density gel product is made into a sheet having a thickness of 2 mm, a transmittance for light having a wavelength of 550 nm in a thickness direction is 70% or more.

7. The low-density gel product according to claim 1 , wherein the low-density gel product has a thermal conductivity of 20 mW/(m·K) or less.

8. A method for producing a low-density gel product, comprising:
(A) gelling, in which
in a solution system containing an organic precursor chain having repeating units A, wherein the organic precursor chain has, in a side chain, a silicon atom to which two or more hydrolyzable functional groups are bonded, a hydrolysis reaction of the functional groups located in the side chains of the repeating units A and a polycondensation reaction between the side chains having the silicon atoms are caused to proceed by a sol-gel process,
an organic polymer chain having a main chain comprising the organic precursor chain and a polysiloxane chain that contains the silicon atoms is formed, wherein the polysiloxane chain is bonded to the organic polymer chain by a covalent bond at a position where the side chains are bonded to the organic polymer chain, and
a wet gel including a skeleton phase that is rich in the polysiloxane chain and the organic polymer chain, and a solution phase that is rich in a solvent of the solution system, is formed; and

(B) drying the wet gel to obtain a low-density gel product having pores and a skeleton containing the polysiloxane chain and the organic polymer chain bonded to each other,
wherein the low-density gel product is an aerogel, a xerogel, or a cryogel,
the aerogel is obtained by drying the wet gel by a drying method including supercritical drying,
the xerogel is obtained by drying the wet gel by a drying method including a normal-pressure drying, and
the cryogel is obtained by drying the wet gel by a drying method including freeze-drying,
wherein the skeleton phase becomes the skeleton and the solution phase becomes pores by the drying,
wherein the repeating unit A is a unit represented by the following formula (1):

wherein the formed polysiloxane chain and the formed organic polymer chain are bonded to each other via a linking part L in formula (1),
wherein R 1 in formula (1) is a hydrolyzable functional group or an organo group,
R 2 and R 3 are each a hydrolyzable functional group,
R 4 is a hydrogen atom, an alkyl group that may have a branch, a phenyl group that may have a substituent, a hydroxyl group, or a halogen atom,
R 5 and R 6 are each independently a hydrogen atom, an alkyl group that may have a branch, a phenyl group that may have a substituent, a hydroxyl group, a halogen atom, an N,N-dimethylamide group, or an N-isopropylamide group,
the linking part L is selected from the group consisting of: an alkylene group that may be cyclic or may have a branch and that has 1 to 10 carbon atoms; a phenylene group that may have a substituent; an amide group; an ether group; a combination thereof; and a bond, and
when the linking part L is a bond, the silicon atom of the polysiloxane chain and the carbon atom of the organic polymer chain are directly bonded to each other.

9. The method for producing a low-density gel product according to claim 8 , further comprising forming the organic precursor chain having repeating units A,
wherein in the forming, a silicon compound having a silicon atom to which the two or more hydrolyzable functional groups are bonded and further having a polymerizable group is caused to polymerize,
wherein the polymerizable groups on the silicon compound or a plurality of silicon compounds are caused to react with each other.

10. The method for producing a low-density gel product according to claim 9 , wherein the polymerizable group is at least one group selected from the group consisting of a vinyl group, a vinylidene group, an allyl group, and a (meth)acrylic group.

11. The method for producing a low-density gel product according to claim 8 , wherein
an organo group is bonded to the silicon atom, and
a polyorganosiloxane chain is formed as the polysiloxane chain.

12. The method for producing a low-density gel product according to claim 11 , wherein the organo group is an alkyl group having 1 to 4 carbon atoms.

13. The method for producing a low-density gel product according to claim 8 , wherein the solution system further comprises a basic catalyst.

14. The method for producing a low-density gel product according to claim 8 , wherein the solution system further comprises a phase separation inhibitor.

15. The method for producing a low-density gel product according to claim 8 , wherein the hydrolyzable functional groups are each an alkoxy group having 1 to 4 carbon atoms.

16. The method for producing a low-density gel product according to claim 8 , wherein a degree of polymerization of the repeating units A in the organic precursor chain is 2 to 10000.

17. The method for producing a low-density gel product according to claim 8 , wherein the wet gel is dried by a normal pressure drying so as to obtain a xerogel as the low-density gel product.

18. The method according to claim 10 , wherein the polymerizable group is a vinyl group

Assignees

• Univ Kyoto

Inventors

• Nakanishi Kazuki
• Kanamori Kazuyoshi
• Zu Guoqing

Classifications

• C08G77/42 Primary

  Block-or graft-polymers containing polysiloxane sequences (polymerising aliphatic unsaturated monomers on to a polysiloxane C08F283/12) · CPC title

• C08J2383/04

  Polysiloxanes · CPC title

• C08J2383/10

  Block- or graft-copolymers containing polysiloxane sequences · CPC title

• C08J2205/026

  Aerogel, i.e. a supercritically dried gel · CPC title

• C08J9/28

  by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum · CPC title