CN111154036A - Preparation method of ethylene-silane copolymerized composite aerogel - Google Patents
Preparation method of ethylene-silane copolymerized composite aerogel Download PDFInfo
- Publication number
- CN111154036A CN111154036A CN202010063530.6A CN202010063530A CN111154036A CN 111154036 A CN111154036 A CN 111154036A CN 202010063530 A CN202010063530 A CN 202010063530A CN 111154036 A CN111154036 A CN 111154036A
- 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.)
- Granted
Links
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 57
- 239000004964 aerogel Substances 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920001577 copolymer Polymers 0.000 claims abstract description 45
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 8
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 7
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 7
- 150000003254 radicals Chemical class 0.000 claims abstract description 6
- 238000003980 solgel method Methods 0.000 claims abstract description 6
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000011240 wet gel Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000499 gel Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- NUFVQEIPPHHQCK-UHFFFAOYSA-N ethenyl-methoxy-dimethylsilane Chemical compound CO[Si](C)(C)C=C NUFVQEIPPHHQCK-UHFFFAOYSA-N 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 claims description 3
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 claims description 3
- JEWCZPTVOYXPGG-UHFFFAOYSA-N ethenyl-ethoxy-dimethylsilane Chemical compound CCO[Si](C)(C)C=C JEWCZPTVOYXPGG-UHFFFAOYSA-N 0.000 claims description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000000352 supercritical drying Methods 0.000 abstract description 5
- 239000002243 precursor Substances 0.000 abstract description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 2
- 230000006835 compression Effects 0.000 abstract 1
- 238000007906 compression Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 230000002209 hydrophobic effect Effects 0.000 abstract 1
- -1 polysiloxane Polymers 0.000 abstract 1
- 229920001296 polysiloxane Polymers 0.000 abstract 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 235000019445 benzyl alcohol Nutrition 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004965 Silica aerogel Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
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
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
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:
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-rich material obtained in example 2The silane copolymer solution was mixed with 5.2 parts of ethyl orthosilicate (the amount of which was 20 wt% based on the mass of the ethylene-silane copolymer), 84mL of an HF solution (the mass ratio of water to benzyl alcohol was 1:10, the HF content was 3 wt%) was added dropwise thereto, the mixture was mixed well, and 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 was 5:10, the ammonia content was 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 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 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 (used in an amount of 10 wt% based on the mass of the ethylene-silane copolymer)%) were mixed and then 74.5mL of HF solution (water: isopropanol was in a mass ratio of 1:10, and the HF content was 2 wt%), thoroughly mixed, reacted at room temperature for 0.5 hour to hydrolyze and condense alkoxy groups in the ethylene-silane copolymer into a sol, and then ammonia solution (water: isopropanol at a mass ratio of 2:10, ammonia content of 5 wt%) to a pH of 7.5, and after gel formation, hermetically aging 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 4 was 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 (8)
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 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 the organic silicon composite aerogel.
2. The production method according to claim 1, wherein the ethylene-silane copolymer solution A is prepared by mixing the following components in parts by mass:
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.
3. The method according to claim 2, wherein the radical initiator is any one of dicumyl peroxide, azobisisobutyronitrile, dibenzoyl peroxide or tert-butyl hydroperoxide; wherein the solvent is dimethyl sulfoxide, N-dimethylformamide, ethanol, methanol, isopropanol, N-propanol, benzyl alcohol, N-butanol or acetone; 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; the vinyl monomer is any one of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, acrylonitrile or vinyl trimethylsilane and a compound combination.
4. The preparation method according to claim 1, wherein the step of preparing the organosilicon composite wet gel B by the sol-gel process comprises: 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.
5. The preparation method according to claim 4, 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.
6. The method according to claim 4, 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.
7. The preparation method according to claim 4, characterized in that 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.
8. 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.
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 true CN111154036A (en) | 2020-05-15 |
| CN111154036B 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) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111617304A (en) * | 2020-06-15 | 2020-09-04 | 张玉花 | High-moisture-absorption wound dressing and preparation method thereof |
| CN111892729A (en) * | 2020-06-28 | 2020-11-06 | 浙江清华柔性电子技术研究院 | Flexible aerogel and preparation method thereof |
Citations (3)
| 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 |
-
2020
- 2020-01-20 CN CN202010063530.6A patent/CN111154036B/en active Active
Patent Citations (3)
| 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)
| Title |
|---|
| YANG, HAILONG等: "Mechanical properties of polymer-modified silica aerogels dried under ambient pressure", 《JOURNAL OF NON-CRYSTALLINE SOLIDS 》 * |
| ZU, GUOQING等: "Transparent, Superflexible Doubly Cross-Linked Polyvinylpolymethylsiloxane Aerogel Superinsulators via Ambient Pressure Drying", 《ACS NANO》 * |
| 杨自春等: "有机－无机杂化气凝胶隔热材料的研究进展", 《海军工程大学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111617304A (en) * | 2020-06-15 | 2020-09-04 | 张玉花 | High-moisture-absorption wound dressing and preparation method thereof |
| 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 |
| CN111892729A (en) * | 2020-06-28 | 2020-11-06 | 浙江清华柔性电子技术研究院 | Flexible aerogel and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111154036B (en) | 2021-12-24 |
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 | |
| Ikeda et al. | In situ formed silica particles in rubber vulcanizate by the sol-gel method | |
| JP5697336B2 (en) | Hybrid polymer and method for producing the same | |
| CN110240746B (en) | Anti-slip thermal-aging-resistant EVA (ethylene-vinyl acetate copolymer) and NR (NR) composite foaming material and preparation method thereof | |
| KR100710887B1 (en) | Method for manufacturing aerogel blanket | |
| Hashim et al. | Moisture cure and in‐situ silica reinforcement of epoxidized natural rubber | |
| CN112143034A (en) | Preparation method and application of hydrogen-containing polyborosiloxane modified white carbon black | |
| CN110092939B (en) | Polyorganoalkoxysilane-reinforced hybrid silica aerogel and method for producing same | |
| CN111019595A (en) | Sealant base adhesive, sealant and preparation method of sealant | |
| CN114539786A (en) | Preparation method of heat-resistant enhanced self-repairing polyborosiloxane composite material | |
| CN114790342A (en) | Silane modified carbon black composite filler and preparation method thereof | |
| CN116589973B (en) | High-temperature-resistant COB packaging adhesive and preparation method thereof | |
| CN109161289B (en) | Antistatic coating and preparation method thereof | |
| CN114349390B (en) | Organic silicon/inorganic nano material composite waterproof agent and preparation method thereof | |
| CN114773679B (en) | Modified carbon black composite material and preparation method thereof | |
| CN116532058A (en) | Inorganic silicon hybrid modified phenolic aerogel and preparation method thereof | |
| US8933165B2 (en) | Method for producing modified conjugated diene-based polymer, and method for producing polymer composition | |
| CN106380603A (en) | Bis-amino-containing MQ silicone resin, and preparation method and application thereof | |
| CN114316272A (en) | Preparation process of structure control agent | |
| KR100547389B1 (en) | Organic-inorganic cross-linked composite polymer coating composition and manufacturing method for strengthening interfacial adhesion of new and old concrete | |
| KR100502278B1 (en) | Coating compositions that manufactured by organic-inorganic crosslinked polymer for the protection of concrete structure and its manufacture method | |
| CN114517016B (en) | High-resilience low-pressure variable rubber compound and preparation method thereof | |
| CN111978669A (en) | High-strength sound insulation SiO2-maleic anhydride synergistically modified isoprene rubber and preparation method thereof | |
| CN115124319B (en) | High-compression silicon dioxide aerogel, aerogel felt 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 |