CN113462163B - Dealcoholized high-strength transparent flowing silicone rubber and preparation method thereof - Google Patents
Dealcoholized high-strength transparent flowing silicone rubber and preparation method thereof Download PDFInfo
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- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 56
- 239000004945 silicone rubber Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 39
- 229920002545 silicone oil Polymers 0.000 claims abstract description 34
- 239000006229 carbon black Substances 0.000 claims abstract description 32
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 32
- 239000004014 plasticizer Substances 0.000 claims abstract description 27
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 12
- 239000007822 coupling agent Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 26
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical group C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910002011 hydrophilic fumed silica Inorganic materials 0.000 claims description 9
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 6
- 230000002209 hydrophobic effect Effects 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 239000013522 chelant Substances 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 239000002981 blocking agent Substances 0.000 claims description 3
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims 2
- 239000000853 adhesive Substances 0.000 abstract description 8
- 230000001070 adhesive effect Effects 0.000 abstract description 8
- 238000007789 sealing Methods 0.000 abstract description 2
- 238000004078 waterproofing Methods 0.000 abstract description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract 1
- 229910052709 silver Inorganic materials 0.000 abstract 1
- 239000004332 silver Substances 0.000 abstract 1
- 238000004898 kneading Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- -1 silane compound Chemical class 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 description 7
- 239000004205 dimethyl polysiloxane Substances 0.000 description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 239000013464 silicone adhesive Substances 0.000 description 5
- 229920005601 base polymer Polymers 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 2
- GRWPYGBKJYICOO-UHFFFAOYSA-N 2-methylpropan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] GRWPYGBKJYICOO-UHFFFAOYSA-N 0.000 description 1
- ZRWNRAJCPNLYAK-UHFFFAOYSA-N 4-bromobenzamide Chemical compound NC(=O)C1=CC=C(Br)C=C1 ZRWNRAJCPNLYAK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000227425 Pieris rapae crucivora Species 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- HAAANJSJNWKVMX-UHFFFAOYSA-L [butanoyloxy(dimethyl)stannyl] butanoate Chemical compound CCCC(=O)O[Sn](C)(C)OC(=O)CCC HAAANJSJNWKVMX-UHFFFAOYSA-L 0.000 description 1
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical compound CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SDTDHTCWRNVNAJ-UHFFFAOYSA-L dimethyltin(2+);diacetate Chemical compound CC(=O)O[Sn](C)(C)OC(C)=O SDTDHTCWRNVNAJ-UHFFFAOYSA-L 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920002631 room-temperature vulcanizate silicone Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
- C09J183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
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Abstract
The invention relates to the technical field of adhesives, relates to dealcoholized silicone rubber, and particularly relates to dealcoholized high-strength transparent flowing silicone rubber and a preparation method thereof. The dealcoholized high-strength transparent flowing silicone rubber comprises the following raw materials in parts by weight: 100 parts of vinyl silicone oil, 5-30 parts of plasticizer, 15-30 parts of white carbon black, 0-6 parts of white carbon black treating agent, 2-5 parts of end-capping agent, 0.1-0.2 part of platinum complex, 2-7 parts of cross-linking agent, 1-4 parts of coupling agent and 0.2-5 parts of catalyst. The technical problem that the comprehensive performance of the existing adhesive for the electronic and electric appliances cannot meet the application requirements can be solved. The silicon rubber has the characteristics of transparency, self-leveling property, high strength and good adhesion, has the tensile strength of more than or equal to 3MPa and the viscosity of less than or equal to 50 Pa.s, can self-level, and can be used as an adhesive for electronic and electric appliances to be applied to practical operations of fixing circuit board leads and silver pins, sealing and waterproofing electronic products and the like.
Description
Technical Field
The invention relates to the technical field of adhesives, relates to dealcoholized silicone rubber, and particularly relates to dealcoholized high-strength transparent flowing silicone rubber and a preparation method thereof.
Background
With the continuous development of science and technology, electronic and electric products are applied more and more widely in various industries, the application environment is more and more complex, the product requirement standard is higher and higher, so the requirements of people on the performances of vibration resistance, water resistance and the like of the electronic products and the appearance of the products are higher and higher, and higher requirements of transparency, self-leveling, high strength, good adhesion and the like are provided for the adhesive for the electronic and electric products.
Currently common silicone adhesives for electronic and electrical devices are non-transparent alcohol-type silicone adhesives and some common transparent alcohol-type silicone rubbers. Chinese patent CN106854362A discloses a high-strength dealcoholized single-component RTV silicone rubber and a preparation method thereof, and the patent technology uses the mixture of white carbon black and calcium carbonate as a reinforcing filler to prepare the high-strength dealcoholized silicone rubber used in the field of electronic appliances. Although the silicone adhesive produced by the technical scheme has better mechanical properties, the patent technology does not research the transparency and the self-leveling property of the silicone adhesive, and does not consider whether an electronic product prepared from the silicone adhesive meets the requirements of consumers in appearance. Chinese patent CN104829642A discloses a silane compound and a preparation method thereof, and translucent dealcoholized room temperature cured silicone rubber and a preparation method thereof, the patent technology uses alkoxy-terminated polydimethylsiloxane as a base polymer and a specific tackifier to prepare dealcoholized translucent silicone rubber which has good adhesion, but has low strength, and the viscosity and the fluidity of the product are not researched. In order to satisfy the comprehensive requirements of consumers on adhesives for electronic products, it is necessary to develop an adhesive for electronic and electrical products which is transparent, self-leveling, high in strength and good in adhesion.
Disclosure of Invention
The invention aims to provide dealcoholized high-strength transparent flowing silicone rubber to solve the technical problem that the comprehensive performance of the existing adhesive for electronic appliances cannot meet the application requirements.
In order to achieve the purpose, the invention adopts the following technical scheme:
the dealcoholized high-strength transparent flowing silicone rubber comprises the following raw materials in parts by weight: 100 parts of vinyl silicone oil, 5-30 parts of plasticizer, 15-30 parts of white carbon black, 0-6 parts of white carbon black treating agent, 2-5 parts of end-capping agent, 0.1-0.2 part of platinum complex, 2-7 parts of cross-linking agent, 1-4 parts of coupling agent and 0.2-5 parts of catalyst.
The scheme also provides a preparation method of the dealcoholized high-strength transparent flowing silicone rubber: mixing vinyl silicone oil, white carbon black and white carbon black treating agent, and kneading to obtain a base material; adding a blocking agent into the base material, homogenizing and then adding a platinum complex; after temperature rising reaction and temperature reduction treatment, adding a plasticizer and a cross-linking agent, stirring, adding a catalyst and a coupling agent, and stirring to obtain the catalyst.
The principle and the advantages of the scheme are as follows: under the catalysis of a platinum complex, the end-capping reagent and the vinyl silicone oil undergo hydrosilylation to generate polyalkoxy end-capped silicone oil which can be subjected to crosslinking and curing under the action of moisture. The white carbon black is a reinforcing filler of the dealcoholized high-strength transparent flowing silicone rubber. The plasticizer is added into the silicone rubber to reduce the viscosity of the silicone rubber and improve the strength of the silicone rubber. The addition of the cross-linking agent enables the interior of the silicon rubber to form a net structure, thereby improving the strength and elasticity of the high polymer material. The use of the coupling agent can reduce the viscosity of the silicon rubber and improve the dispersion degree of the white carbon black, so that the silicon rubber product obtains good surface quality and mechanical property.
In conclusion, the dealcoholization type high-strength transparent flowing silicone rubber prepared by the invention has the advantages of tensile strength of more than or equal to 3MPa, viscosity of less than or equal to 50 Pa.s, self-leveling property, high bonding strength, good transparency and good appearance smoothness after glue application, and can be applied to fixing of circuit board leads and pins and sealing and waterproofing of electronic products.
In this case, the use of vinyl silicone oil as the base polymer has the advantages that: is not affected by moisture and hydrolysis in the process of preparing the base stock, and does not affect the storage stability. The vinyl silicone oil can not react with the white carbon black treating agent to influence the curing process of the base material. And the vinyl silicone oil does not contain hydroxyl, so that the structuring effect of the white carbon black (a large number of hydrogen bonds are generated among other components of the white carbon black) is not aggravated, and the dispersion of the silicone rubber in the scheme cannot be influenced by using the vinyl silicone oil.
Further, the viscosity of the vinyl silicone oil is 2000-20000 mPa & s; and two ends of the vinyl silicone oil are vinyl-terminated. The low viscosity of the vinyl silicone oil can cause poor flexibility of the prepared silicone rubber, so that the tensile strength and the elongation at break are low, and the high viscosity of the vinyl silicone oil can cause high viscosity of the base material, poor fluidity and difficulty in preparing the high-strength self-leveling silicone rubber. The ethylene end capping is not the conventional hydroxyl end capping, so that the vinyl silicone oil can be ensured not to aggravate the white carbon black structuring effect.
Further, the white carbon black is hydrophilic fumed silica or hydrophobic fumed silica; the specific surface area of the white carbon black is 120m2/g~400m2(ii) in terms of/g. The specific surface area of the common white carbon black on the market is 80m2/g~400m2However, the reinforcing effect of the white carbon black on the rubber is influenced by the fact that the specific surface area is too low, so that the specific surface area is selected to be 120m2/g~400m2White carbon black in a ratio of/g.
Further, the white carbon black treating agent is hexamethyldisilazane, tetramethyldivinylsilazane, octamethylcyclotetrasiloxane or hexadecyltrimethoxysilane. The white carbon black treating agent is a conventional agent in the prior art, has stable property and is easy to obtain. In addition, when the hydrophobic white carbon black treated by hexamethyldisilazane is directly used, no treating agent is added.
Further, the structural formula of the end-capping reagent is shown as formula (1):
wherein R is2Is H or a group shown as a formula (2); in the formula (2), n is an integer of 1-20, and m is 0 or 2; r3Is methoxy or ethoxy; r is4Is one of methyl, methoxy and ethoxy.
In the scheme, the end capping agent vinyl silicone oil has higher reactivity, and in order to ensure that the end capping agent has higher reactivity, R is ensured2Wherein n is an integer of 0 to 20. After the end capping agent is used for capping vinyl silicone oil, the whole system does not have residual unreacted hydroxyl, and the storage stability is better after the glue is prepared.
Further, the platinum complex is a platinum-vinyl complex or a platinum-alkynyl complex. These two platinum complexes are catalysts commonly used in the art. Under the catalysis of a platinum complex, the end-capping reagent and the vinyl silicone oil undergo hydrosilylation to generate polyalkoxy end-capped silicone oil which can be subjected to crosslinking and curing under the action of moisture.
Further, the structural formula of the plasticizer is shown as a formula (3):
wherein in the formula (3), n is an integer of 3-20, and m is an integer of 1-30; r1Is alkylene or arylene.
In the scheme, the plasticizer is added to reduce the viscosity of the base material, so that the viscosity of the plasticizer cannot be too high, n is required to be an integer of 3-20, and m is required to be an integer of 1-30. In addition, the plasticizer can participate in a crosslinking reaction in the curing process of the silicone rubber, imino and carbonyl are introduced into the polymer, and hydrogen bonds are formed through the imino and the carbonyl, so that the intermolecular force is increased, and the strength of the silicone rubber is improved.
Further, R1The structural formula of (A) is shown as formula (4) or (5).
R1The selection of the group plays a very important role in the exertion of the plasticizer effect, and the inventors tried various substituent groups and found that the effect of improving the strength of the silicone rubber obtained by using two substituent groups of formula (4) and formula (5) is the best.
Further, the crosslinking agent is alkoxy silane, and the alkoxy of the alkoxy silane is more than or equal to 3.
By adopting the scheme, the cross-linking agent is alkoxy silane containing three or more easily hydrolyzed alkoxy groups. The use of the cross-linking agent can enable the interior of the silicon rubber to form a network structure, thereby improving the strength and elasticity of the high polymer material. The cross-linking agent can be selected from one or a mixture of 2-3 of methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane and phenyltriethoxysilane.
Further, the coupling agent is one of KH-540, KH-550, KH-560, KH-570, KH-792 and Si-602 or a mixture of 2-3 substances. The use of the coupling agent can improve the interface performance of the synthetic resin and the inorganic filler or the reinforcing material, reduce the viscosity of the silicon rubber and improve the dispersion degree of the white carbon black, thereby leading the silicon rubber product to obtain good surface quality and mechanical performance.
Furthermore, the catalyst is a mixture of one or more of organic tin carboxylate and chelate thereof, organic titanate and chelate thereof. The catalyst is a substance for catalyzing esterification reaction in the prior art, and has stable property and easy acquisition.
Furthermore, the dealcoholized high-strength transparent flowing silicone rubber has the tensile strength of more than or equal to 3Mpa and the viscosity of less than or equal to 50 Pa.s. The silicon rubber prepared by the scheme has the characteristics of high strength and low viscosity.
Detailed Description
The following is further detailed by way of specific embodiments:
example 1
The preparation process of the dealcoholized high-strength transparent flowing silicone rubber comprises the following steps: adding 100 parts of vinyl silicone oil into a kneading machine, adding 15-30 parts of white carbon black and 0-6 parts of white carbon black treating agent 4 times, kneading at 80 ℃ for 2 hours under normal pressure, heating to 150 ℃, kneading in vacuum for 2 hours to prepare a base material, transferring the base material into a high-speed dispersion machine, adding 2-5 parts of a capping agent under the protection of nitrogen, stirring for 5 minutes, adding 0.1-0.2 part of a platinum complex, heating to 80 ℃ for reaction for 1 hour, cooling to below 50 ℃, adding 5-30 parts of a plasticizer and 2-7 parts of a cross-linking agent, stirring for 20 minutes under vacuum (not more than-0.08 MPa), adding 0.2-5 parts of a catalyst and 1-4 parts of a coupling agent, and stirring for 20 minutes under vacuum to obtain the dealcoholized high-strength transparent trickling silicone rubber.
The specific information of each raw material in the process is as follows:
the viscosity of the vinyl silicone oil is 2000-20000 mPa.s, and two ends of the vinyl silicone oil are vinyl-terminated.
(II) the white carbon black is hydrophilic fumed silica or hydrophobic fumed silica, and the specific surface area of the white carbon black is 120m2/g~400m2/g。
(III) the white carbon black treating agent is hexamethyldisilazane, tetramethyldivinylsilazane, octamethylcyclotetrasiloxane or hexadecyltrimethoxysilane.
(IV) the structural formula of the end capping reagent is shown as the formula (1):
wherein R is2Is H or a group shown as a formula (2); in the formula (2), n is an integer of 1-20, and m is 0 or 2; r3Is methoxy or ethoxy; r4Is one of methyl, methoxy and ethoxy.
(V) the platinum complex is a platinum-vinyl complex or a platinum-alkynyl complex.
(VI) the structural formula of the plasticizer is shown as the formula (3):
wherein in the formula (3), n is an integer of 3-20, and m is an integer of 1-30; r1 is alkylene or arylene.
The structural formula of R1 is shown as formula (4) or formula (5).
(VII) in this embodiment, a mixture of more than three moisture hydrolyzable alkoxysilanes, including one or 2-3 of methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane and phenyltriethoxysilane, can be used, all in accordance with conventional alternatives known in the art to obtain the desired product.
(VIII) in this embodiment, a variety of silane coupling agents can be used, including one of KH-540, KH-550, KH-560, KH-570, KH-792 and Si-602, or a mixture of 2-3, all according to conventional alternatives conventionally employed in the art, to obtain the desired product.
(IX) one or more of tin organic carboxylates and chelates thereof and organic titanates and chelates thereof may be used as a mixture, all in accordance with conventional alternatives in the art, to obtain the desired product. For example: one substance or a mixture of 2 to 3 substances of dibutyltin oxide, dimethyltin diacetate, dibutyltin diacetate, dimethyltin dibutyrate, dibutyltin dilaurate, dimethyltin dilaurate, dibutyltin dioctanoate and tert-butyl titanate.
In this embodiment, the following are specifically mentioned:
100 parts of vinyl silicone oil with viscosity of 20000 mPas are added into a kneader, and 25 parts of vinyl silicone oil with specific surface area of 150m are added in 4 times2The preparation method comprises the following steps of kneading hydrophilic fumed silica and 5 parts of hexamethyldisilazane at 80 ℃ for 2 hours under normal pressure, heating to 150 ℃, kneading for 2 hours under vacuum to prepare a base material, and transferring the base material to a reactorMoving to a high-speed dispersion machine, and adding 2 parts of end-capping reagent (R is adopted as the end-capping reagent) under the protection of nitrogen2Is H, R3Is methoxy, R4The methoxy group is shown in formula (6), the structural formula is shown in the specification, the materials are stirred for 5 minutes, 0.1 part of platinum-vinyl complex is added, the temperature is increased to 80 ℃ for reaction for 1 hour, then the temperature is reduced to below 50 ℃, 20 parts of plasticizer (n is 5, m is 5, R1 is shown in formula (4)) and 3 parts of methyltrimethoxysilane are added, the vacuum stirring is carried out for 20 minutes, then 0.6 part of dibutyltin dilaurate and 1 part of KH-550 are added, and the vacuum stirring is carried out for 20 minutes, so that the dealcoholized high-strength transparent trickling silicone rubber is obtained.
Examples 2-8 are essentially the same as example 1 except that the specific raw materials are selected for their type and amount, and the differences are detailed in tables 1, 2 and 3.
Table 1: selection of the types and amounts of vinyl Silicone, white carbon treating agent, and platinum Complex of examples 1-8
In table 1, the commercially available hydrophobic fumed silica treated with hexamethyldisilazane is shown.
Table 2: selection of the types and amounts of blocking and plasticizing Agents of examples 1-8
In table 2, the capping agent of example 3 is exemplified, and the structural formula thereof is shown in formula (7).
Table 3: selection of the type and amount of crosslinking agent, coupling agent and catalyst for examples 1-8
Comparative example 1
100 parts of trimethoxysilyloxy-terminated polydimethylsiloxane with viscosity of 20000 mPas are added into a kneader, 25 parts of polydimethylsiloxane with specific surface area of 150m are added in 4 times2Kneading hydrophilic fumed silica and 5 parts of hexamethyldisilazane at 80 ℃ for 2 hours under normal pressure, heating to 150 ℃, kneading under vacuum for 2 hours to prepare a base material, transferring the base material into a high-speed dispersion machine, and adding 20 parts of plasticizer (n is 5, m is 5, R is 20 parts of plasticizer)1Formula (4)) and 3 parts of methyltrimethoxysilane were stirred under vacuum for 20 minutes, and then 0.6 part of dibutyltin dilaurate and 1 part of KH-550 were added thereto and stirred under vacuum for 20 minutes to obtain a dealcoholized silicone rubber.
Comparative example 2
Adding 100 parts of hydroxyl-terminated polydimethylsiloxane with viscosity of 20000 mPas into a kneader, and adding 25 parts of polydimethylsiloxane with specific surface area of 150m in 4 times2Kneading hydrophilic fumed silica and 5 parts of hexamethyldisilazane at 80 ℃ for 2 hours under normal pressure, heating to 150 ℃, kneading under vacuum for 2 hours to prepare a base material, transferring the base material into a high-speed dispersion machine, and adding 20 parts of plasticizer (n is 5, m is 5, R is 20 parts of plasticizer)1To (4)) and 3 parts of methyltrimethoxysilane were stirred under vacuum for 20 minutes, and then 0.6 part of dibutyltin dilaurate and 1 part of KH-550 were added thereto and stirred under vacuum for 20 minutes to obtain a dealcoholized silicone rubber.
Comparative example 3
100 parts of vinyl silicone oil with the viscosity of 12000 mPas are added into a kneader, and 30 parts of vinyl silicone oil with the specific surface area of 300m are added into the kneader by 4 times2The preparation method comprises the following steps of kneading hydrophilic fumed silica and 6 parts of hexamethyldisilazane at 80 ℃ for 2 hours under normal pressure, heating to 150 ℃, kneading under vacuum for 2 hours to obtain a base material, transferring the base material into a high-speed dispersion machine, adding 3 parts of a blocking agent shown in formula (6) under the protection of nitrogen, stirring for 5 minutes, adding 0.1 part of a platinum-vinyl complex, heating to 80 ℃ for reaction for 1 hour, and then heating to 80 ℃ for reaction for 1 hourCooling to below 50 ℃, adding 30 parts of dimethyl silicone oil with the viscosity of 500mPa & s and 3 parts of methyltrimethoxysilane, stirring for 20 minutes in vacuum, adding 0.6 part of dibutyltin dilaurate and 1 part of KH-550, and stirring for 20 minutes in vacuum to obtain the dealcoholized high-strength transparent trickling silicone rubber.
Comparative example 4
100 parts of vinyl silicone oil with viscosity of 20000 mPas are added into a kneader, and 25 parts of vinyl silicone oil with specific surface area of 150m are added in 4 times2Kneading hydrophilic fumed silica and 5 parts of hexamethyldisilazane at normal temperature and normal pressure for 30 minutes, heating to 150 ℃, kneading in vacuum for 2 hours to obtain a base material, transferring the base material into a high-speed dispersion machine, and adding 2 parts of an end-capping reagent (the end-capping reagent adopts R) under the protection of nitrogen2Is H, R3Is methoxy, R4A methoxy group, a structural formula of which is shown in formula (6)), stirring for 5 minutes, adding 0.1 part of platinum-vinyl complex, heating to 80 ℃ for reaction for 1 hour, then cooling to below 50 ℃, adding 20 parts of plasticizer (n-5, m-5, R)1As shown in formula (4) and 3 parts of methyltrimethoxysilane are stirred for 20 minutes in vacuum, and then 0.6 part of dibutyltin dilaurate and 1 part of KH-550 are added and stirred for 20 minutes in vacuum, thus obtaining the dealcoholized high-strength transparent trickling silicone rubber.
Comparative example 5
100 parts of vinyl silicone oil with viscosity of 20000 mPas are added into a kneader, and 25 parts of vinyl silicone oil with specific surface area of 150m are added in 4 times2The preparation method comprises the following steps of kneading hydrophilic fumed silica and 5 parts of hexamethyldisilazane at 80 ℃ for 2 hours under normal pressure, heating to 150 ℃, kneading for 2 hours under vacuum to prepare a base material, transferring the base material into a high-speed dispersion machine, and adding 2 parts of an end-capping reagent (R is adopted as the end-capping reagent) under the protection of nitrogen gas2Is H, R3Is methoxy, R4A methoxy group, a structural formula of which is shown in formula (6)), stirring for 5 minutes, adding 0.1 part of platinum-vinyl complex, heating to 80 ℃ for reaction for 1 hour, then cooling to below 50 ℃, adding 20 parts of plasticizer (n-5, m-5, R)1As shown in formula (8) and 3 parts of methyltrimethoxysilane are stirred for 20 minutes in vacuum, then 0.6 part of dibutyltin dilaurate and 1 part of KH-550 are added and stirred for 20 minutes in vacuum, thus obtaining the dealcoholized high-strength transparent flowAnd (4) dripping silicon rubber.
Examples of the experiments
The silicone rubbers prepared in examples and comparative examples were subjected to performance tests, and the test results and reference standards are shown in table 4.
Table 4: results of Performance testing
From the above table (Table 4), it can be seen that in comparative example 1, which uses trimethoxysilyloxy-terminated polydimethylsiloxane as the base polymer, partial alkoxy groups are hydrolyzed during the preparation of the base material, resulting in a high viscosity and poor leveling property of the base material. Comparative example 2 using a hydroxy-terminated polydimethylsiloxane as the base polymer, the binder was terminated with hexamethyldisilazane during the binder preparation process, resulting in no curing of the binder. Comparative example 3 using dimethylsilicone oil as a plasticizer, both viscosity and prevalence were satisfactory, but strength was low. Comparative example 4 when the base material was prepared, the temperature was low (kneading was carried out at normal temperature and pressure for 30 minutes), the reaction time was insufficient, and the thickening of the base material after aging was significant. Comparative example 5 plasticizer R1The structure of the plasticizer is shown as formula (8), and the plasticizer of comparative example 5 is consistent with the plasticizer used in the scheme on the whole skeleton of the polymer, but the tensile strength is not obviously improved due to the difference of substituent groups. The inventors analyzed that R is not favorable for hydrogen bonding between carbonyl group and imino group because the substituent group of the present comparative example1The plasticizer having the structure of formula (8) does not effectively improve the strength of the silicone rubber. The silicone rubber prepared by the embodiment schemes 1-8 has low viscosity, good leveling property and strength which is more than or equal to 3 MPa.
The foregoing is merely an example of the present invention and common general knowledge in the art of designing and/or characterizing particular aspects and/or features is not described in any greater detail herein. It should be noted that, for those skilled in the art, without departing from the technical solution of the present invention, several variations and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (11)
1. The dealcoholized high-strength transparent flowing silicone rubber is characterized by comprising the following raw materials in parts by weight: 100 parts of vinyl silicone oil, 5-30 parts of plasticizer, 15-30 parts of white carbon black, 0-6 parts of white carbon black treating agent, 2-5 parts of end-capping agent, 0.1-0.2 part of platinum complex, 2-7 parts of cross-linking agent, 1-4 parts of coupling agent and 0.2-5 parts of catalyst;
the structural formula of the end-capping reagent is shown as the formula (1):
formula (1)
Formula (2)
Wherein R is2Is H or a group shown as a formula (2); in the formula (2), n is an integer of 1-20, and m is 0 or 2; r3Is methoxy or ethoxy; r4Is one of methyl, methoxy and ethoxy;
the structural formula of the plasticizer is shown as a formula (3):
formula (3)
Wherein in the formula (3), n is an integer of 3-20, and m is an integer of 1-30; r1Is alkylene or aryleneAnd (4) a base.
2. The dealcoholization type high-strength transparent trickling silicone rubber as claimed in claim 1, wherein the viscosity of the vinyl silicone oil is 2000-20000 mPa.s; and two ends of the vinyl silicone oil are vinyl-terminated.
3. The dealcoholized high-strength transparent flowing silicone rubber according to claim 1, wherein the silica is hydrophilic fumed silica or hydrophobic fumed silica; the specific surface area of the white carbon black is 120m2/g~400 m2/g。
4. The dealcoholized high strength transparent trickling silicone rubber according to claim 1, wherein the silica white treating agent is hexamethyldisilazane, tetramethyldivinylsilazane, octamethylcyclotetrasiloxane, or hexadecyltrimethoxysilane.
5. The dealcoholization type high-strength transparent flowing silicone rubber according to claim 1, wherein the platinum complex is a platinum-vinyl complex or a platinum-alkynyl complex.
7. The dealcoholization type high-strength transparent flowing silicone rubber as claimed in claim 1, wherein the crosslinking agent is an alkoxysilane, and the number of alkoxy groups of the alkoxysilane is not less than 3.
8. The dealcoholization type high-strength transparent flowing silicone rubber according to claim 1, wherein the coupling agent is one of KH-540, KH-550, KH-560, KH-570, KH-792 and Si-602 or a mixture of 2 to 3 substances.
9. The dealcoholized high-strength transparent trickling silicone rubber as claimed in claim 1, wherein the catalyst is one or a mixture of two or more of tin organic carboxylate and its chelate, organic titanate and its chelate.
10. The dealcoholization type high-strength transparent flowing silicone rubber according to any one of claims 1 to 9, wherein the tensile strength is not less than 3Mpa and the viscosity is not more than 50 pa.s.
11. The method for preparing the dealcoholized high-strength transparent flowing silicone rubber according to any one of claims 1 to 9, wherein the vinyl silicone oil, the white carbon black and the white carbon black treating agent are mixed and kneaded to obtain a base material; adding a blocking agent into the base material, homogenizing and then adding a platinum complex; after temperature rising reaction and temperature reduction treatment, adding a plasticizer and a cross-linking agent, stirring, adding a catalyst and a coupling agent, and stirring to obtain the catalyst.
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