CN111154036B - Preparation method of ethylene-silane copolymerized composite aerogel - Google Patents

Preparation method of ethylene-silane copolymerized composite aerogel Download PDF

Info

Publication number
CN111154036B
CN111154036B CN202010063530.6A CN202010063530A CN111154036B CN 111154036 B CN111154036 B CN 111154036B CN 202010063530 A CN202010063530 A CN 202010063530A CN 111154036 B CN111154036 B CN 111154036B
Authority
CN
China
Prior art keywords
silane
ethylene
vinyl
solution
silane copolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010063530.6A
Other languages
Chinese (zh)
Other versions
CN111154036A (en
Inventor
包艳华
孔伟
江国栋
沈晓冬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing Tech University
Original Assignee
Nanjing Tech University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing Tech University filed Critical Nanjing Tech University
Priority to CN202010063530.6A priority Critical patent/CN111154036B/en
Publication of CN111154036A publication Critical patent/CN111154036A/en
Application granted granted Critical
Publication of CN111154036B publication Critical patent/CN111154036B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
    • C08J2205/026—Aerogel, i.e. a supercritically dried gel
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2343/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Derivatives of such polymers
    • C08J2343/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Silicon Polymers (AREA)

Abstract

The invention discloses a preparation method of ethylene-silane copolymerization composite aerogel, which comprises the steps of carrying out free radical copolymerization on a vinyl-alkoxy silane monomer and a vinyl monomer to obtain an ethylene-silane copolymer, taking a copolymer solution as a precursor, taking tetraethyl orthosilicate or methyl orthosilicate as a curing agent, and preparing the organic silicon composite aerogel by adopting a sol-gel process and a supercritical drying or normal pressure drying mode. The aerogel has a double-cross-linked structure consisting of hydrocarbon chains and polysiloxane, and the toughness of the network structure is increased due to the side groups attached with vinyl monomers on the hydrocarbon chains, so that the mechanical strength of the obtained aerogel is obviously enhanced. The aerogel prepared by the invention has the advantages of high specific surface area, good hydrophobic property, good rebound resilience after compression and heat treatment, high strength under the same density and the like.

Description

Preparation method of ethylene-silane copolymerized composite aerogel
The technical field is as follows:
the invention relates to the field of aerogels, in particular to a preparation method of ethylene-silane copolymerized composite aerogel.
Background art:
aerogel is a nanoporous material with a continuous three-dimensional network structure. The unique structure of the aerogel gives it unique properties such as low density, high specific surface area, low thermal conductivity. Making them of great interest in catalyst supports, cerenkov radiators, adsorbents, and skylight and window insulation. But the inherent fragility of aerogels makes them difficult to apply in practical applications. The mechanical properties of silica aerogels have been enhanced by different strategies. (1) In the aging process of wet gel, the neck region between gel secondary particles is accumulated and thickened to achieve the purpose of aerogel reinforcement, (2) the aerogel prepared by adopting organic siloxane such as methyltrimethoxysilane (MTMS) and Vinyl Trimethoxysilane (VTMS) as precursors has better resilience; (3) polymer modified aerogels are usually prepared by grafting or compounding polymers such as polystyrene, polymethyl methacrylate, and polyester onto the surface of silica to improve the mechanical properties of the aerogel. Polymer reinforced aerogels are an effective strategy to improve these brittle materials, however, most polymer reinforced aerogels have been greatly limited in their commercial application at the expense of density and time.
The invention content is as follows:
the invention aims to solve the problem of brittleness of the existing aerogel and provides a preparation method of an ethylene-silane copolymerization composite aerogel, namely, the mechanical strength of the aerogel is improved on the premise of ensuring that the heat insulation performance of the aerogel is not reduced.
The technical scheme of the invention is as follows: the preparation method of the ethylene-silane copolymerized composite aerogel is characterized by comprising the following steps: the vinyl-alkoxy silane and vinyl monomer are subjected to free radical copolymerization to obtain an ethylene-silane copolymer solution A, an organic silicon composite wet gel B is prepared by adopting a sol-gel method process, and the organic silicon composite wet gel B can be dried under normal pressure or supercritical pressure to obtain the organic silicon composite aerogel.
The ethylene-silane copolymer solution A is prepared by the following steps of:
Figure BDA0002375259560000011
Figure BDA0002375259560000021
and (3) placing the mixture in an inert gas environment, and polymerizing at the temperature of 60-120 ℃ for 6-10 hours to obtain the ethylene-silane copolymer solution A.
Preferably, the radical initiator is any one of dicumyl peroxide, azobisisobutyronitrile, dibenzoyl peroxide or tert-butyl hydroperoxide; the solvent has certain compatibility with water, and comprises: dimethyl sulfoxide, N-dimethylformamide, ethanol, methanol, isopropanol, N-propanol, benzyl alcohol, N-butanol or acetone; the alkoxy in the vinyl-alkoxy silane has the characteristic of hydrolysis, and comprises the following components: any one or compound combination of vinyl dimethyl methoxy silane, vinyl methyl dimethoxy silane, vinyl trimethoxy silane, vinyl dimethyl ethoxy silane, vinyl methyl diethoxy silane or vinyl triethoxy silane; the vinyl monomer is any one of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, acrylonitrile or vinyl trimethylsilane and a compound combination.
The steps for preparing the organic silicon composite wet gel B by the sol-gel process are as follows: and dropwise adding the HF solution into the ethylene-silane copolymer solution A and the curing agent, fully and uniformly mixing, reacting at room temperature for 0.5-2 hours to hydrolyze and condense alkoxy in the ethylene-silane copolymer into sol, then dropwise adding ammonia water, adjusting the pH value to 7.5-8.5, and after gel is formed, sealing and aging at room temperature to obtain wet gel B.
Preferably, the mass concentration of the HF solution is 2-5%; the solvent of the HF solution is a mixed solvent of water and the same solvent in the ethylene-silane copolymer solution A, and the mass ratio of the water in the mixed solvent to the same solvent in the ethylene-silane copolymer solution A is 1-5: 10.
Preferably, the mass concentration of the ammonia water is 2-5%, the solvent of the ammonia water is a mixed solvent of water and the same solvent in the ethylene-silane copolymer solution A, and the mass ratio of the water in the mixed solvent to the same solvent in the ethylene-silane copolymer solution A is 1-5: 10.
Preferably, the curing agent is any one of tetraethoxysilane or methyl orthosilicate; the dosage of the curing agent is 10-40% of the mass of the ethylene-silane copolymer.
Preferably, the amount of the dropwise addition in the HF solution is such that the molar ratio of the water content in the HF solution to the hydrolyzed functional groups in the ethylene-silane copolymer and the curing agent is 1:0.8 to 1.5.
Has the advantages that:
the invention provides a preparation method of an organic silicon composite aerogel, which comprises the steps of carrying out free radical copolymerization on vinyl-alkoxy silane and a vinyl monomer to obtain an ethylene-silane copolymer solution, preparing an organic silicon composite wet gel by adopting a sol-gel method, and drying under normal pressure or supercritical drying to obtain the organic silicon composite aerogel. The composite aerogel prepared by the invention fully utilizes the copolymerization characteristic of the vinyl group, enhances the mechanical strength of the aerogel, particularly has better rebound resilience, and is expected to have great application prospect in the field of heat insulation in the future.
The specific implementation mode is as follows:
example 1
100 parts of vinyl dimethylethoxysilane, 10 parts of methyl acrylate and 120 parts of acetone are placed in a hydrothermal reaction kettle, then 0.5 part of dibenzoyl peroxide is added, air in the reaction kettle is removed by a nitrogen bubbling method, then the reaction is carried out for 10 hours under the closed condition at the temperature of 80 ℃, and a semitransparent ethylene-silane copolymer solution is obtained after cooling.
Example 2
100 parts of vinyl methyl diethoxysilane, 20 parts of ethyl methacrylate and 200 parts of benzyl alcohol are placed in a hydrothermal reaction kettle, then 0.4 part of azobisisobutyronitrile is added, air in the reaction kettle is removed by an argon bubbling method, then the reaction is carried out for 8 hours at 60 ℃, and the ethylene-silane copolymer solution is obtained after cooling.
Example 3
100 parts of vinyl dimethylmethoxysilane, 10 parts of acrylonitrile and 150 parts of N, N-dimethylformamide are placed in a reaction kettle, then 0.6 part of dicumyl peroxide is added, air in the reaction kettle is removed by a nitrogen bubbling method, then the reaction is carried out for 8 hours at the temperature of 120 ℃ under a closed condition, and the yellow semitransparent ethylene-silane copolymer solution is obtained after cooling.
Example 4
Placing 60 parts of vinyl methyl dimethoxysilane, 40 parts of vinyl dimethyl methoxysilane, 15 parts of methyl methacrylate and 150 parts of N, N-dimethylformamide into a reaction kettle, adding 0.8 part of azobisisobutyronitrile, removing air in the reaction kettle by using a nitrogen bubbling method, reacting for 6 hours at 80 ℃ under a closed condition, and cooling to obtain a semitransparent ethylene-silane copolymer solution.
Example 5
100 parts of the ethylene-silane copolymer solution obtained in example 1 and 15.5 parts of ethyl orthosilicate (the amount is 40 wt% based on the mass of the ethylene-silane copolymer) were mixed, 81mL of an HF solution (the mass ratio of water to acetone is 2:10, and the HF content is 5 wt%) was added dropwise, the mixture was mixed well and reacted at room temperature for 2 hours to hydrolyze and condense alkoxy groups in the ethylene-silane copolymer into a sol, an ammonia solution (the mass ratio of water to acetone is 2:10, and the ammonia content is 2 wt%) was added dropwise to a pH of 8.5, and after the gel was formed, the mixture was sealed at room temperature and aged for 24 hours to obtain wet gel B. Wherein the molar ratio of the water content in the HF solution to the alkoxy groups in the ethylene-silane copolymer solution and ethyl orthosilicate obtained in example 1 was 1: 1.5; replacing the aged wet gel with ethanol for 3 times, 8 hours each time, and passing CO2And (5) performing supercritical drying to obtain the aerogel. The obtained aerogel had a density of 0.24g/cm3Specific surface area 634m2(iv)/g, maximum specific compressive strength of 51.3 N.m/kg.
Example 6
100 parts of the ethylene-silane copolymer solution obtained in example 2 and 5.2 parts of ethyl orthosilicate (the amount of ethyl orthosilicate is 20 wt% based on the mass of the ethylene-silane copolymer) were mixed, 84mL of an HF solution (the mass ratio of water to benzyl alcohol is 1:10, and the HF content is 3 wt%) was added dropwise, the mixture was mixed well, reacted at room temperature for 1.5 hours to hydrolyze and condense alkoxy groups in the ethylene-silane copolymer into a sol, then an ammonia solution (the mass ratio of water to benzyl alcohol is 5:10, and the ammonia content is 4 wt%) was added dropwise to a pH of 8, and after the gel was formed, the mixture was hermetically aged at room temperature for 24 hours to obtain wet gel B. Wherein HF is dissolvedThe molar ratio of the water content in the solution to the alkoxy groups in the ethylene-silane copolymer solution and ethyl orthosilicate obtained in example 2 was 1: 1.1; replacing the aged wet gel with ethanol for 3 times, 8 hours each time, and passing CO2And (5) performing supercritical drying to obtain the aerogel. The obtained aerogel had a density of 0.18g/cm3Specific surface area of 515m2(iv)/g, maximum specific compressive strength of 48.2 N.m/kg.
Example 7
100 parts of the ethylene-silane copolymer solution obtained in example 3 and 7 parts of methyl orthosilicate (the amount is 20 wt% based on the mass of the ethylene-silane copolymer) were mixed, 26.2mL of an HF solution (the mass ratio of water: N, N-dimethylformamide is 5:10, the HF content is 5 wt%) was added dropwise, the mixture was mixed well, reacted at room temperature for 1 hour to hydrolyze and condense alkoxy groups in the ethylene-silane copolymer into a sol, then an ammonia solution (the mass ratio of water: N, N-dimethylformamide is 1:10, the ammonia content is 2.5 wt%) was added dropwise to a pH of 8, and after the gel was formed, the mixture was hermetically aged at room temperature for 24 hours to obtain wet gel B. Wherein the molar ratio of the water content in the HF solution to the alkoxy groups in the ethylene-silane copolymer solution and ethyl orthosilicate obtained in example 3 was 1: 1.5; replacing the aged wet gel with ethanol for 3 times, 8 hours each time, and passing CO2And (5) performing supercritical drying to obtain the aerogel. The obtained aerogel had a density of 0.28g/cm3Specific surface area 681m2(iv)/g, maximum specific compressive strength of 56.3 N.m/kg.
Example 8
100 parts of the ethylene-silane copolymer solution obtained in example 4 and 3.8 parts of methyl orthosilicate (the amount thereof is 10 wt% based on the mass of the ethylene-silane copolymer) were mixed, 74.5mL of an HF solution (the mass ratio of water to isopropyl alcohol is 1:10, the HF content is 2 wt%) was added dropwise, the mixture was mixed well and reacted at room temperature for 0.5 hour to hydrolyze and condense alkoxy groups in the ethylene-silane copolymer into a sol, an ammonia solution (the mass ratio of water to isopropyl alcohol is 2:10, the ammonia content is 5 wt%) was added dropwise to a pH of 7.5, and after the gel was formed, the mixture was hermetically aged at room temperature for 24 hours to obtain wet gel B. Wherein the HF solution contained water in an amount equivalent to that of the ethylene-silane copolymer solution and ethyl orthosilicate obtained in example 4The molar ratio of the alkoxy groups is 1: 0.8; and (3) replacing the aged wet gel with ethanol for 3 times, each time lasting for 8 hours, then replacing with n-hexane for 3 times, each time lasting for 8 hours, and finally drying under normal pressure to obtain the aerogel. The obtained aerogel had a density of 0.26g/cm3Specific surface area 433m2(iv)/g, maximum specific compressive strength of 65.6 N.m/kg.

Claims (5)

1. The preparation method of the ethylene-silane copolymerized composite aerogel is characterized by comprising the following steps: carrying out free radical copolymerization on vinyl-alkoxy silane and a vinyl monomer to obtain an ethylene-silane copolymer solution A, preparing an organic silicon composite wet gel B by adopting a sol-gel process, and drying the organic silicon composite wet gel B at normal pressure or supercritical pressure to obtain an organic silicon composite aerogel;
the ethylene-silane copolymer solution A is prepared by the following steps of:
Figure FDA0003247071590000011
placing the mixture in an inert gas environment, and polymerizing at the temperature of 60-120 ℃ for 6-10 hours to obtain an ethylene-silane copolymer solution A; wherein the solvent is dimethyl sulfoxide, N-dimethylformamide, ethanol, methanol, isopropanol, N-propanol, benzyl alcohol, N-butanol or acetone; the acrylic monomer is any one of methyl acrylate, ethyl acrylate, methyl methacrylate or ethyl methacrylate and a compound combination;
the preparation method of the organic silicon composite wet gel B by the sol-gel process comprises the following steps: dropwise adding an HF solution into the ethylene-silane copolymer solution A and a curing agent, fully and uniformly mixing, reacting at room temperature for 0.5-2 hours to hydrolyze and condense alkoxy in the ethylene-silane copolymer into sol, then dropwise adding ammonia water, adjusting the pH value to 7.5-8.5, and after gel is formed, sealing and aging at room temperature to obtain wet gel B; the curing agent is any one of ethyl orthosilicate or methyl orthosilicate; the dosage of the curing agent is 10-40% of the mass of the ethylene-silane copolymer.
2. The method according to claim 1, wherein the radical initiator is any one of dicumyl peroxide, azobisisobutyronitrile, dibenzoyl peroxide or tert-butyl hydroperoxide; the alkoxy in the vinyl-alkoxy silane is any one or a compound combination of vinyl dimethyl methoxy silane, vinyl methyl dimethoxy silane, vinyl trimethoxy silane, vinyl dimethyl ethoxy silane, vinyl methyl diethoxy silane or vinyl triethoxy silane.
3. The preparation method according to claim 1, wherein the HF solution has a mass concentration of 2-5%; the solvent of the HF solution is a mixed solvent of water and the same solvent in the ethylene-silane copolymer solution A, and the mass ratio of the water in the mixed solvent to the same solvent in the ethylene-silane copolymer solution A is 1-5: 10.
4. The method according to claim 1, wherein the aqueous ammonia has a mass concentration of 2 to 5%, and the aqueous ammonia has a solvent comprising a mixed solvent of water and the same solvent as that of the ethylene-silane copolymer solution A, and the mass ratio of water to the same solvent as that of the ethylene-silane copolymer solution A in the mixed solvent is 1 to 5: 10.
5. The method according to claim 1, wherein the amount of the dropwise addition in the HF solution is such that the molar ratio of the water content in the HF solution to the hydrolyzable functional groups in the ethylene-silane copolymer and the curing agent is 1:0.8 to 1.5.
CN202010063530.6A 2020-01-20 2020-01-20 Preparation method of ethylene-silane copolymerized composite aerogel Active CN111154036B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010063530.6A CN111154036B (en) 2020-01-20 2020-01-20 Preparation method of ethylene-silane copolymerized composite aerogel

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010063530.6A CN111154036B (en) 2020-01-20 2020-01-20 Preparation method of ethylene-silane copolymerized composite aerogel

Publications (2)

Publication Number Publication Date
CN111154036A CN111154036A (en) 2020-05-15
CN111154036B true CN111154036B (en) 2021-12-24

Family

ID=70564599

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010063530.6A Active CN111154036B (en) 2020-01-20 2020-01-20 Preparation method of ethylene-silane copolymerized composite aerogel

Country Status (1)

Country Link
CN (1) CN111154036B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111617304B (en) * 2020-06-15 2022-01-14 江苏阳生生物股份有限公司 High-moisture-absorption wound dressing and preparation method thereof
CN111892729B (en) * 2020-06-28 2024-07-12 浙江清华柔性电子技术研究院 Flexible aerogel and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1295496A (en) * 1998-03-26 2001-05-16 陶氏化学公司 Ion exchanged aluminium-magnesium or fluorinated magnesium silicate aerogels and catalyst supports therefrom
CN109354028A (en) * 2018-11-13 2019-02-19 江西宏柏新材料股份有限公司 A method of mixing silicon source copolymerization prepares flexible aeroge compound insulating material
CN109796018A (en) * 2019-01-29 2019-05-24 同济大学 A kind of preparation method of elasticity double cross connection aeroge

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1295496A (en) * 1998-03-26 2001-05-16 陶氏化学公司 Ion exchanged aluminium-magnesium or fluorinated magnesium silicate aerogels and catalyst supports therefrom
CN109354028A (en) * 2018-11-13 2019-02-19 江西宏柏新材料股份有限公司 A method of mixing silicon source copolymerization prepares flexible aeroge compound insulating material
CN109796018A (en) * 2019-01-29 2019-05-24 同济大学 A kind of preparation method of elasticity double cross connection aeroge

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Mechanical properties of polymer-modified silica aerogels dried under ambient pressure;Yang, Hailong等;《JOURNAL OF NON-CRYSTALLINE SOLIDS 》;20111031;第357卷(第19-20期);第3447-3453页 *
Transparent, Superflexible Doubly Cross-Linked Polyvinylpolymethylsiloxane Aerogel Superinsulators via Ambient Pressure Drying;Zu, Guoqing等;《ACS NANO》;20180131;第12卷(第1期);第521-532页 *
有机－无机杂化气凝胶隔热材料的研究进展;杨自春等;《海军工程大学学报》;20181231;第30卷(第6期);第42-49页 *

Also Published As

Publication number Publication date
CN111154036A (en) 2020-05-15

Similar Documents

Publication Publication Date Title
AU2006231371B2 (en) Process for the preparation, under subcritical conditions, of monolithic xerogels and aerogels of silica/latex hybrids, modified with alkoxysilane groups
CN111154036B (en) Preparation method of ethylene-silane copolymerized composite aerogel
KR100710887B1 (en) Method for manufacturing aerogel blanket
CN112143034B (en) Preparation method and application of hydrogen-containing polyborosiloxane modified white carbon black
CN110240746B (en) Anti-slip thermal-aging-resistant EVA (ethylene-vinyl acetate copolymer) and NR (NR) composite foaming material and preparation method thereof
CN114790342B (en) Silane modified carbon black composite filler and preparation method thereof
JP2010513597A (en) Hybrid polymer and method for producing the same
CN110787745A (en) Preparation method of silicon dioxide aerogel composite material and silicon dioxide aerogel composite material
CN111320967A (en) High-thermal-conductivity silicone sealant modified by multilevel-structure filler and preparation method thereof
CN111019595A (en) Sealant base adhesive, sealant and preparation method of sealant
CN110092939A (en) Polyorganoalkoxysilane-reinforced hybrid silica aerogel and method for producing same
CN109721330A (en) GO-SiO2Preparation method of composite ultrahigh molecular weight polyethylene fiber gas distribution gel
CN116589973B (en) High-temperature-resistant COB packaging adhesive and preparation method thereof
CN115785893B (en) Low-dielectric organosilicon sealant and preparation method thereof
CN109161289B (en) Antistatic coating and preparation method thereof
CN108047968A (en) A kind of high volume resistivity structural silicone adhesive of low modulus
CN114773679B (en) Modified carbon black composite material and preparation method thereof
CN114349390B (en) Organic silicon/inorganic nano material composite waterproof agent and preparation method thereof
US8933165B2 (en) Method for producing modified conjugated diene-based polymer, and method for producing polymer composition
CN115011195A (en) Water-based heat-insulation reflective composite coating with low heat conductivity coefficient and preparation process thereof
CN113680288A (en) Preparation method of hydrophobic attapulgite composite aerogel
CN114517016B (en) High-resilience low-pressure variable rubber compound and preparation method thereof
KR20040058539A (en) Coating compositions that manufactured by organic-inorganic crosslinked polymer for the protection of concrete structure and its manufacture method
KR20040058537A (en) Coating compositions of organic-inorganic crosslinked polymer for strengthening the adhesion in interface between old concrete and new concrete and its manufacture method
CN115678494B (en) High-temperature-resistant silicone adhesive and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant