CN116925358A - Hydroxy-functionalized phenyl silicone oil and preparation method thereof, low-density foaming silica gel and preparation method thereof, and electronic instrument - Google Patents
Hydroxy-functionalized phenyl silicone oil and preparation method thereof, low-density foaming silica gel and preparation method thereof, and electronic instrument Download PDFInfo
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- CN116925358A CN116925358A CN202310939241.1A CN202310939241A CN116925358A CN 116925358 A CN116925358 A CN 116925358A CN 202310939241 A CN202310939241 A CN 202310939241A CN 116925358 A CN116925358 A CN 116925358A
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- phenyl
- silicone oil
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- 229920002545 silicone oil Polymers 0.000 title claims abstract description 135
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title claims abstract description 111
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000000741 silica gel Substances 0.000 title claims abstract description 52
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 238000005187 foaming Methods 0.000 title claims abstract description 39
- -1 enol compound Chemical class 0.000 claims abstract description 70
- 239000001257 hydrogen Substances 0.000 claims abstract description 52
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 52
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000007259 addition reaction Methods 0.000 claims abstract description 9
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 7
- 238000006482 condensation reaction Methods 0.000 claims abstract description 6
- 229920002050 silicone resin Polymers 0.000 claims description 34
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical class N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 32
- 239000000945 filler Substances 0.000 claims description 32
- 239000012763 reinforcing filler Substances 0.000 claims description 30
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 21
- 239000007822 coupling agent Substances 0.000 claims description 19
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 16
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 14
- 239000003112 inhibitor Substances 0.000 claims description 14
- 229910052697 platinum Inorganic materials 0.000 claims description 13
- 239000003063 flame retardant Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 9
- LBZNVMHSRIIVQE-UHFFFAOYSA-N C1(=CC=CC=C1)[Pt] Chemical compound C1(=CC=CC=C1)[Pt] LBZNVMHSRIIVQE-UHFFFAOYSA-N 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 7
- 238000001723 curing Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- BUEPLEYBAVCXJE-UHFFFAOYSA-N [ethenyl-methyl-(trimethylsilylamino)silyl]ethene Chemical compound C(=C)[Si](N[Si](C)(C)C)(C=C)C BUEPLEYBAVCXJE-UHFFFAOYSA-N 0.000 claims description 4
- 238000003490 calendering Methods 0.000 claims description 4
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 claims description 3
- UTISCLIDFORRJP-UHFFFAOYSA-N 1-prop-1-ynylcyclohexan-1-ol Chemical compound CC#CC1(O)CCCCC1 UTISCLIDFORRJP-UHFFFAOYSA-N 0.000 claims description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 3
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N Butanol Natural products CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- 239000006260 foam Substances 0.000 abstract description 15
- 230000036632 reaction speed Effects 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 229920002379 silicone rubber Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 5
- 101150065749 Churc1 gene Proteins 0.000 description 5
- 102100038239 Protein Churchill Human genes 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000006261 foam material Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000004945 silicone rubber Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 241001391944 Commicarpus scandens Species 0.000 description 2
- DDCDEKHXBABHHI-UHFFFAOYSA-N acetylene cyclohexanol Chemical compound C1(CCCCC1)O.C#C DDCDEKHXBABHHI-UHFFFAOYSA-N 0.000 description 2
- 230000007123 defense Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 241000872198 Serjania polyphylla Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- 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
- 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
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- 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
- C08J9/009—Use of pretreated compounding ingredients
-
- 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
- C08J9/02—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by the reacting monomers or modifying agents during the preparation or modification of macromolecules
-
- 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
- C08J2383/00—Characterised by the use 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; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
-
- 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
- C08J2483/00—Characterised by the use 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; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
-
- 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
- C08J2483/00—Characterised by the use 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; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/05—Polysiloxanes containing silicon bound to hydrogen
-
- 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
- C08J2483/00—Characterised by the use 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; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The application provides hydroxyl functional phenyl silicone oil and a preparation method thereof, low-density foaming silica gel and a preparation method thereof, and an electronic instrument. The hydroxy-functionalized phenyl silicone oil comprises- (CH) 2 ) a An OH group, the method of preparation comprising: carrying out condensation reaction on an enol compound and silazane to obtain a compound X; carrying out addition reaction on the compound X and double-end hydrogen-containing phenyl silicone oil to obtain a compound Y; and carrying out alcoholysis reaction on the compound Y and alcohol substances to obtain the hydroxyl functional phenyl silicone oil. The application also provides low-density foaming silica gel, which is prepared from the hydroxyl functional phenyl silicone oil by adopting a bi-component preparation method. The application improves the surface tension and the reaction speed of the foaming silica gel system by using the hydroxyl functional phenyl silicone oil, thereby forming uniform and fine foam with low density and high foaming multiplying power.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to hydroxyl functional phenyl silicone oil and a preparation method thereof, low-density foaming silica gel and a preparation method thereof, and an electronic instrument.
Background
With the increasing popularity of new energy electric vehicles, technological research of new energy electric vehicles is required to break through in the field of vehicles, and the key point of the break-through is the charge and discharge technology and safety performance of high energy density lithium batteries. Particularly, the safety performance is one obstacle restricting the development of the electric automobile, the lithium battery must keep excellent waterproof and dustproof effects in the use process, and the easy spontaneous combustion caused by heat is the first difficult problem affecting the safety performance. The liquid foaming silicon material has the advantages of good flame retardance, environmental protection, ageing resistance, good rebound resilience and the like, so that the liquid foaming silicon material can be used for improving the working environment of a lithium battery and provides a reliable foundation stone for the application of the lithium battery in new energy automobiles.
The silicon rubber foam material is a porous polymer elastomer with two characteristics of silicon rubber and foam material, and is widely applied to the fields of national defense, transportation, electronic and electrical appliances, furniture articles, sealing, electrical insulation and the like. Besides the excellent performance of the silicon rubber, the silicon rubber has the advantages of light weight, good damping effect and good heat insulation performance, and also has the advantages of high and low temperature resistance, weather resistance, environmental protection and the like which are not available in other foam materials. The surface tension of the a, w-dihydroxy polydimethylsiloxane used in the raw materials of the foaming silica gel disclosed in the market at present is low, so that the gas generated by foaming is easy to break foam, and the foaming silica gel is unfavorable for forming uniform and fine low-density high-foaming-rate foam.
Therefore, in order to improve the performance of the silicone rubber foam, the raw materials in the silicone rubber foam need to be improved to obtain a foamed silicone material with a high foaming rate.
Disclosure of Invention
The application aims to provide hydroxyl functional phenyl silicone oil and a preparation method thereof, low-density foaming silica gel and a preparation method thereof, and an electronic instrument.
In order to achieve the above object, the technical scheme of the present application is as follows:
in a first aspect, the present application provides a hydroxy-functionalized phenyl silicone oil comprising- (CH) 2 ) a OH groups, wherein a is an integer from 2 to 5.
With reference to the first aspect, in a preferred embodiment, the hydroxy-functionalized phenyl silicone oil has the chemical formula HO (CH) 2 ) a (CH 3 ) 2 SiO[(CH 3 ) 2 SiO] m [(C 6 H 5 ) 2 SiO] n Si(CH 3 ) 2 (CH 2 ) a OH, wherein m.gtoreq.1, n.gtoreq.1, and m and n are integers.
In a second aspect, the present application provides a method for preparing the hydroxy-functionalized phenyl silicone oil according to the first aspect, comprising:
carrying out condensation reaction on an enol compound and silazane to obtain a compound X;
carrying out addition reaction on the compound X and double-end hydrogen-containing phenyl silicone oil to obtain a compound Y;
and carrying out alcoholysis reaction on the compound Y and alcohol substances to obtain the hydroxyl functional phenyl silicone oil.
With reference to the second aspect, in a preferred embodiment, the preparation method satisfies at least one of the following conditions:
A. the enol compound comprises at least one of vinyl alcohol, allyl alcohol and allyl butanol;
B. the silazane comprises at least one of hexamethyldisilazane and tetramethyl divinyl disilazane;
C. the chemical structural formula of the double-end hydrogen-containing phenyl silicone oil is H (CH) 3 ) 2 SiO[(CH 3 ) 2 SiO] m [(C 6 H 5 ) 2 SiO] n Si(CH 3 ) 2 H, wherein m is greater than or equal to 1, n is greater than or equal to 1, and m and n are positive integers;
D. the phenyl content in the double-end hydrogen-containing phenyl silicone oil is 5-30wt%;
E. the hydrogen content in the double-end hydrogen-containing phenyl silicone oil is 0.01-0.1 wt%;
F. the alcohol substance comprises any one of methanol and ethanol;
G. a platinum-containing catalyst is also required to be added in the addition reaction, and the platinum content in the platinum-containing catalyst is 3000ppm-5000ppm.
In a third aspect, the present application also provides a low-density foamed silica gel, which comprises the following raw materials: the hydroxyl-functionalized phenyl silicone oil, modified reinforcing filler, modified flame retardant filler, phenyl vinyl silicone oil, phenyl MQ silicone resin, phenyl hydrogen silicone oil, catalyst and inhibitor of the first aspect.
With reference to the third aspect, in a preferred embodiment, the low-density foamed silica gel meets at least one of the following conditions:
H. the modified reinforcing filler is a reinforcing filler modified by a phenylsilane coupling agent;
I. the modified flame-retardant filler is flame-retardant filler modified by a phenylsilane coupling agent;
J. the chemical structural formula of the phenyl vinyl silicone oil is as follows: (CH) 2 ＝CH)(CH 3 ) 2 SiO[(CH 3 ) 2 SiO] m [(C 6 H 5 ) 2 SiO] n Si(CH 3 ) 2 (CH＝CH 2 )；
K. The chemical structural formula of the phenyl hydrogen-containing silicone oil is as follows: (CH) 3 ) 3 SiO[(CH 3 )HSiO] m [(C 6 H 5 ) 2 SiO] n Si(CH 3 ) 3 ；
L, the hydrogen content in the phenyl hydrogen-containing silicone oil is 0.1-1.6 wt%; the phenyl content is 5wt percent to 30wt percent;
the phenyl MQ silicone resin comprises at least one of phenyl vinyl MQ silicone resin and phenyl methyl MQ silicone resin;
the ratio of M chain link to Q chain link in the phenyl MQ silicone resin is (0.8-1): 1, a step of;
the catalyst comprises a phenyl platinum catalyst;
the inhibitor comprises at least one of ethynyl cyclohexanol and 1- (1-propynyl) cyclohexanol.
Further preferably, the low density foamed silica gel also satisfies at least one of the following conditions:
q. the phenylsilane coupling agent comprises at least one of phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane and methylphenyldimethoxysilane;
r, the reinforcing filler comprises at least one of gas-phase white carbon black and precipitated white carbon black;
s, the flame-retardant filler comprises at least one of aluminum hydroxide and magnesium hydroxide;
t, adding 25-50 g of the phenylsilane coupling agent into 1000g of the reinforcing filler to carry out the modification treatment;
u, adding 25-50 g of the phenylsilane coupling agent into 1000g of the flame-retardant filler to carry out the modification treatment;
and V. the platinum content in the phenyl platinum catalyst is 3000ppm-5000ppm.
In a fourth aspect, the present application provides a method for preparing the low-density foamed silica gel according to the third aspect, comprising:
mixing and grinding raw materials comprising the hydroxyl functional phenyl silicone oil, the phenyl MQ silicone resin, the phenyl vinyl silicone oil, the modified reinforcing filler and the modified flame retardant filler, and adding the catalyst to obtain a component A;
mixing and grinding raw materials comprising the hydroxyl functional phenyl silicone oil, the phenyl MQ silicone resin, the phenyl vinyl silicone oil, the modified reinforcing filler, the modified flame retardant filler, the phenyl hydrogen silicone oil and the inhibitor to obtain a component B;
and mixing the component A and the component B in proportion, calendaring into a sheet, and heating and curing to obtain the low-density foaming silica gel.
In combination with the fourth aspect, the preparation method of the low-density foamed silica gel meets at least one of the following conditions:
a. in the component A, the mass ratio of the hydroxyl functional phenyl silicone oil, the phenyl MQ silicone resin, the phenyl vinyl silicone oil, the modified reinforcing filler, the modified flame retardant filler and the catalyst is (25-40): (3-5): (10-15): (30-40): (40-55): (0.1-0.5);
b. in the component B, the mass ratio of the hydroxyl functional phenyl silicone oil, the phenyl MQ silicone resin, the phenyl vinyl silicone oil, the modified reinforcing filler, the modified flame retardant filler, the phenyl hydrogen silicone oil and the inhibitor is (25-40): (3-5): (10-15): (30-40): (40-55): (10-15): (0.1-0.3);
c. the fineness of the ground product is 80-100 meshes;
d. the mass ratio of the component A to the component B is 1: mixing the components in a ratio of (0.9-1.1);
e. the temperature of the heating and curing is 70-100 ℃.
In a fifth aspect, the present application also provides an electronic apparatus, comprising the low-density foamed silica gel of the third aspect.
The application has the beneficial effects that:
in the hydroxy-functionalized phenyl silicone oil of the application, the hydroxyl-functionalized phenyl silicone oil is prepared by introducing- (CH) 2 ) n OH group can raise the reaction activity and reaction speed of silicone oil, and the phenyl group in phenyl silicone oil can raise the surface tension of silicone rubber system greatly, so that when the hydroxy functional phenyl silicone oil is applied in foaming silica gel system, uniform and fine foam can be formedA body. The preparation method of the hydroxyl functional phenyl silicone oil has simple process, and the high-purity hydroxyl functional phenyl silicone oil is prepared by using common high-molecular compound raw materials and common chemical reaction mechanisms.
The low-density foamed silica gel greatly improves the surface tension of a system by using raw materials such as hydroxyl functional phenyl silicone oil, phenyl vinyl silicone oil, phenyl hydrogen-containing silicone oil and the like, further retains more gas in the system to form uniform and fine low-density high-foaming-rate foam, and can improve the tensile strength of the low-density foamed silica gel by introducing phenyl into the system. Further, the hydroxy-functionalized phenyl silicone oil in the starting material contains- (CH) 2 ) n The reaction speed of OH groups after functionalization is greatly improved, so that a large amount of gas can be generated in a short time, and a uniform and fine foam body with low density and high foaming multiplying power is formed. The preparation method of the low-density foamed silica gel has the advantages of simple process, short production period and high production efficiency, and can be used for large-scale production and preparation.
The low-density foamed silica gel can be widely applied to the fields of national defense, transportation, electronic appliances, furniture articles, sealing, electric insulation and the like, and particularly can be applied to foamed silica gel sealing gaskets for new energy automobile batteries and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is a photograph of a side of a low density foamed silica gel prepared in example 1 before being colored;
FIG. 2 is a side photograph of the low-density foamed silica gel prepared in example 1 and comparative example 5 after being colored.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited only; 9 ajpi 9ak [ em ] to those elements, but may include other elements not explicitly listed or inherent to such compositions, steps, methods, articles, or devices. The conjunction "consisting of … …" excludes any unspecified element, step or component.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g may be expressed, 2.689g may be expressed, and the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. alternatively, the mass of the A component is aK, and the mass of the B component is bK (K is an arbitrary number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
Aiming at the conventional a, w-dihydroxyl polydimethylsiloxane in the market at presentThe application provides a method for preparing foaming silica gel by reacting alkane and hydrogen-containing silicone oil to generate hydrogen, which is characterized in that the surface tension of a, w-dihydroxyl polydimethylsiloxane is low, so that the gas generated by foaming is easy to break foam, and the foaming is unfavorable for forming uniform and fine foam with low density and high foaming multiplying power, and the application firstly provides hydroxyl functional phenyl silicone oil which comprises- (CH) 2 ) a OH groups, wherein a is an integer from 2 to 5. More preferably, a=3.
In a preferred embodiment, the hydroxy-functionalized phenyl silicone oil has the chemical formula HO (CH) 2 ) a (CH 3 ) 2 SiO[(CH 3 ) 2 SiO] m [(C 6 H 5 ) 2 SiO] n Si(CH 3 ) 2 (CH 2 ) a OH, wherein m.gtoreq.1, n.gtoreq.1, and m and n are positive integers.
In addition, the application also provides a preparation method of the hydroxyl functional phenyl silicone oil, which comprises the following steps:
s1, carrying out condensation reaction on an enol compound and silazane to obtain a compound X;
s2, carrying out addition reaction on the compound X and double-end hydrogen-containing phenyl silicone oil to obtain a compound Y;
s3, carrying out alcoholysis reaction on the compound Y and alcohol substances to obtain the hydroxyl functional phenyl silicone oil.
In a preferred embodiment, the enol compound in S1 comprises at least one of vinyl alcohol, allyl alcohol, and allyl alcohol, more preferably allyl alcohol.
In a preferred embodiment, the silazane in S1 comprises at least one of hexamethyldisilazane, tetramethyldivinyl disilazane.
In view of the fact that silazanes containing specific groups may carry reactive groups, such as tetramethyl divinyl disilazane, which contains vinyl groups, interfere with subsequent reactions and can also react with hydrogen-containing silicone oils, hexamethyldisilazane is preferred for the reaction with enol compounds according to the application.
Wherein, the chemical structural formula of the hexamethyldisilazane is as follows:
then, when the enol compound is allyl alcohol, the condensation reaction process in S1 is:
2CH 2 ＝CHCH 2 OH+(CH 3 ) 3 SiNHSi(CH 3 ) 3 →2CH 2 ＝CHCH 2 OSi(CH 3 ) 3 +NH 3 。
in the reaction process of S1, the silazane is hydrolyzed firstly, then deamination condensation reaction is carried out on the silazane and hexamethyldisilazane, and the prepared compound X is CH 2 ＝CHCH 2 OSi(CH 3 ) 3 The main purpose of this reaction is to protect the hydroxyl groups in the allyl alcohol with silazanes.
In a preferred embodiment, the double-ended hydrogen-containing phenyl silicone oil in S2 has the chemical formula H (CH) 3 ) 2 SiO[(CH 3 ) 2 SiO] m [(C 6 H 5 ) 2 SiO] n Si(CH 3 ) 2 H, wherein m is greater than or equal to 1, n is greater than or equal to 1, and m and n are positive integers.
Further, the phenyl content in the double-end hydrogen-containing phenyl silicone oil is 5-30wt%; the hydrogen content is 0.01wt% to 0.1wt%.
In a preferred embodiment, the addition reaction in S2 also requires the addition of a platinum-containing catalyst, the platinum content of which is 3000ppm to 5000ppm.
Specifically, the process of the addition reaction in S2 is: h (CH) 3 ) 2 SiO[(CH 3 ) 2 SiO] m [(C 6 H 5 ) 2 SiO] n Si(CH 3 ) 2 H+CH 2 ＝CHCH 2 OSi(CH 3 ) 3 →(CH 3 ) 3 SiO(CH 2 ) 3 (CH 3 ) 2 SiO[(CH 3 ) 2 SiO] m [(C 6 H 5 ) 2 SiO] n Si(CH 3 ) 2 (CH 2 ) 3 OSi(CH 3 ) 3 。
The compound Y prepared through the addition reaction is phenyl silicone oil, but no special group is used for reaction and foaming in the functional group, so that the hydroxyl functional phenyl silicone oil is prepared through the alcoholysis reaction in S3.
In a preferred embodiment, the alcohol in S3 comprises any one of methanol and ethanol, and more preferably methanol.
Specifically, the process of the alcoholysis reaction in S3 is: (CH) 3 ) 3 SiO(CH 2 ) 3 (CH 3 ) 2 SiO[(CH 3 ) 2 SiO] m [(C 6 H 5 ) 2 SiO] n Si(CH 3 ) 2 (CH 2 ) 3 OSi(CH 3 ) 3 +CH 3 OH→HO(CH 2 ) 3 (CH 3 ) 2 SiO[(CH 3 ) 2 SiO] m [(C 6 H 5 ) 2 SiO] n Si(CH 3 ) 2 (CH 2 ) 3 OH。
The application also provides low-density foaming silica gel, which comprises the raw materials of the hydroxyl functional phenyl silicone oil, modified reinforcing filler, modified flame retardant filler, phenyl vinyl silicone oil, phenyl MQ silicone resin, phenyl hydrogen silicone oil, catalyst and inhibitor.
In a preferred embodiment, the modified reinforcing filler is a reinforcing filler modified with a phenylsilane coupling agent; the modified flame-retardant filler is flame-retardant filler modified by a phenylsilane coupling agent.
In the modification process, the method specifically includes: firstly, mixing reinforcing filler or flame-retardant filler with water, then spraying a phenylsilane coupling agent into the mixed filler by using a spraying device, continuously stirring in the spraying process, continuously stirring after the spraying is finished, ensuring that the filler and the phenylsilane coupling agent are fully and uniformly mixed, filtering out water by using a filter screen, and drying the powder in an oven until the weight is constant, thus obtaining the modified reinforcing filler or modified flame-retardant filler.
Further preferably, the reinforcing filler comprises at least one of fumed silica and precipitated silica, and more preferably, the fumed silica is 1500 mesh.
The flame retardant filler comprises at least one of aluminum hydroxide and magnesium hydroxide, and more preferably 2000 mesh aluminum hydroxide.
The phenylsilane coupling agent comprises at least one of phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane and methylphenyldimethoxysilane.
In the modification treatment, 20g to 50g of the phenylsilane coupling agent is added to 1000g of the reinforcing filler or the flame-retardant filler, and for example, 20g, 25g, 30g, 35g, 40g, 45g, 50g or any value between 20g and 50g may be added. More preferably, 25g to 35g of phenyltriethoxysilane coupling agent is added per 1000 g.
In a preferred embodiment, the phenyl vinyl silicone oil in the starting material has the chemical formula: (CH) 2 ＝CH 2 )(CH 3 ) 2 SiO[(CH 3 ) 2 SiO] m [(C 6 H 5 ) 2 SiO] n Si(CH 3 ) 2( CH 2 ＝CH 2 )。
The kinematic viscosity of the phenyl vinyl silicone oil at 25 ℃ is 5000 mPas-10000 mPas, and the phenyl content is 5-30 w%.
In a preferred embodiment, the phenyl hydrogen containing silicone oil in the starting material has the chemical formula: (CH) 3 ) 3 SiO[(CH 3 )HSiO] m [(C 6 H 5 ) 2 SiO] n Si(CH 3 ) 3 。
The hydrogen content in the phenyl hydrogen-containing silicone oil is 0.1 to 1.6 weight percent; the phenyl content is 5wt% to 30wt%.
In a preferred embodiment, the phenylmq silicone resin comprises at least one of phenylvinyl MQ silicone resin, phenylmethyl MQ silicone resin, and more preferably phenylvinyl MQ silicone grease.
The phenyl content in the phenyl MQ silicon resin is 15-45 wt%; the ratio of M chain link to Q chain link is (0.8-1): 1, more preferably M: q=0.8: 1.
in a preferred embodiment, the catalyst comprises a phenyl platinum catalyst.
Further preferably, the platinum content in the phenyl platinum water is 3000ppm to 5000ppm.
In a preferred embodiment, the inhibitor comprises at least one of ethynyl cyclohexanol, 1- (1-propynyl) cyclohexanol.
The application provides a preparation method of the low-density foaming silica gel, which comprises the following steps:
(1) Mixing and grinding raw materials comprising the hydroxyl functional phenyl silicone oil, phenyl MQ silicone resin, phenyl vinyl silicone oil, modified reinforcing filler and modified flame retardant filler, and adding a catalyst to obtain a component A;
(2) Mixing and grinding raw materials comprising the hydroxyl functional phenyl silicone oil, phenyl MQ silicone resin, phenyl vinyl silicone oil, modified reinforcing filler, modified flame retardant filler, phenyl hydrogen silicone oil and inhibitor to obtain a component B;
(3) And mixing the component A and the component B in proportion, calendaring into a sheet, and heating and curing to obtain the low-density foaming silica gel.
In a preferred embodiment, the mass ratio of hydroxy-functional phenyl silicone oil, phenyl MQ silicone resin, phenyl vinyl silicone oil, modified reinforcing filler, modified flame retardant filler and the catalyst in the a component is (25-40): (3-5): (10-15): (30-40): (40-55): (0.1-0.5), for example, 25:3:10:30:40:0.1, 28:3.5:11:32:42:0.2, 30:4:12:35:45:0.3, 32:4.5:13:38:48:0.4, 35:5:14:40:50:0.5, 38:5:15:40:52:0.5, 40:5:15:40:55:0.5 or (25-40): (3-5): (10-15): (30-40): (40-55): (0.1-0.5).
In a preferred embodiment, the mass ratio of the hydroxy-functionalized phenyl silicone oil, phenyl MQ silicone resin, phenyl vinyl silicone oil, modified reinforcing filler, modified flame retardant filler, phenyl hydrogen silicone oil and inhibitor in the B component is (25-40): (3-5): (10-15): (30-40): (40-55): (10-15): (0.1-0.3), for example, 25:3:10:30:40:10:0.1, 28:3.5:11:32:42:11:0.2, 30:4:12:35:45:12:0.3, 32:4.5:13:38:48:13:0.4, 35:5:14:40:50:14:0.5, 38:5:15:40:52:15:0.5, 40:5:15:40:55:15:0.5 or (25-40): (3-5): (10-15): (30-40): (40-55): (10-15): (0.1-0.5).
In a preferred embodiment, in the preparation of the component A, after the raw materials including the hydroxyl functional phenyl silicone oil, the phenyl MQ silicone resin, the phenyl vinyl silicone oil, the modified reinforcing filler and the modified flame retardant filler are mixed, the mixture is stirred for 40min at a stirring speed of 800r/min, then the mixture is ground on a three-roll machine until the fineness reaches 80-100 meshes, and finally the catalyst is added, and after the mixture is fully and uniformly stirred, the component A is obtained by filtering.
In a preferred embodiment, in the preparation of component B, the mixed material is stirred for 60min at a stirring speed of 800r/min, then ground on a three-roll mill until the fineness reaches 80-100 meshes, and finally, the component B is obtained by filtering after full stirring.
In the preparation of the two components, different types of vacuum mixers on the market can be selected for mixing and stirring, and the mixing and stirring are carried out under vacuum conditions, wherein the vacuum conditions are-0.1 MPa to-0.08 MPa. This is mainly to ensure that bubbles in the stirred raw materials are removed as much as possible during the mixing process of the raw materials, so that large bubbles in the low-density foamed silica gel prepared later are prevented, and a uniform and fine foam with low density and high foaming ratio is difficult to form.
In a preferred embodiment, the A component and the B component have a mass ratio of 1: the ratio of (0.9 to 1.1) is preferably 1: 1.
After the two components are mixed, the two components are required to be stirred uniformly at a stirring speed of 1500-1800r/min, dynamic stirring is performed by dynamic mixing equipment, and large bubbles in a system can be cut into more small bubbles, so that uniform and fine foam bodies are formed; the roll was then pressed onto a calender by a platen, and the thickness of the calender was controlled by the roll gap.
In a preferred embodiment, the temperature of the heat curing after calendaring into sheets is from 70℃to 100℃and may be, for example, from 70℃80℃90℃100℃or any value between 70℃and 100 ℃.
Embodiments of the present application will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
This example provides a hydroxy-functionalized phenyl silicone oil, the preparation method of which comprises the following steps:
mixing allyl alcohol and hexamethyldisilazane, and reacting to obtain CH 2 ＝CHCH 2 OSi(CH 3 ) 3 Then the mixture is reacted with double-end hydrogen-containing phenyl silicone oil (the chemical structural formula is H (CH) 3 ) 2 SiO[(CH 3 ) 2 SiO] m [(C 6 H 5 ) 2 SiO] n Si(CH 3 ) 2 H) Adding a platinum catalyst having a platinum content of 3000ppm to prepare (CH) 3 ) 3 SiO(CH 2 ) 3 (CH 3 ) 2 SiO[(CH 3 ) 2 SiO] m [(C 6 H 5 ) 2 SiO] n Si(CH 3 ) 2 (CH 2 ) 3 OSi(CH 3 ) 3 Finally, carrying out alcoholysis reaction with methanol to prepare hydroxyl functional phenyl silicone oil with a chemical structural formula of HO (CH) 2 ) 3 (CH 3 ) 2 SiO[(CH 3 ) 2 SiO] m [(C 6 H 5 ) 2 SiO] n Si(CH 3 ) 2 (CH 2 ) 3 OH。
The embodiment also provides a low-density foaming silica gel, which comprises the following raw materials: the hydroxyl-functional phenyl silicone oil, phenyl vinyl silicone oil (kinematic viscosity at 25 ℃ C. Is 5000 mPa.s, phenyl content is about 10 wt%), phenyl MQ silicone resin (M: Q=0.8, phenyl content is about 20 wt%), phenyl hydrogen-containing silicone oil (hydrogen content is about 1wt%; phenyl content is 10%), phenyl triethoxysilane modified fumed silica, phenyl triethoxysilane modified aluminum hydroxide, inhibitor acetylene cyclohexanol and catalyst phenyl platinum complex prepared in this example.
The preparation method of the phenyl triethoxysilane modified gas-phase white carbon black comprises the following steps: mixing 1000g of 1500-mesh gas-phase white carbon black with 10kg of distilled water, stirring for 10min at a rotation speed of 500rpm, adding 30g of phenyl triethoxysilane coupling agent by using a spraying device, continuously mixing for 20min at a rotation speed of 2000rpm, filtering the mixed material by using a filter screen to remove water, putting the filtered material in a vacuum oven, and drying at 105 ℃ to constant weight to obtain the phenyl triethoxysilane modified gas-phase white carbon black.
The preparation method of the phenyltriethoxysilane modified aluminum hydroxide comprises the following steps: 1000g of 2000-mesh aluminum hydroxide and 10kg of distilled water are mixed, stirred for 10min at a rotation speed of 500rpm, 30g of phenyl triethoxysilane coupling agent is added by a spraying device, then mixing is continued for 20min at a rotation speed of 2000rpm, then the mixed material is filtered by a filter screen to remove water, the filtered material is placed in a vacuum oven after filtration, and drying is carried out at 105 ℃ to constant weight, so that the phenyl triethoxysilane modified aluminum hydroxide is obtained.
The preparation method of the low-density foaming silica gel comprises the following steps:
step one: preparing a component A, firstly mixing 30g of modified gas-phase white carbon black, 25g of hydroxyl functional phenyl silicone oil, 4g of phenyl MQ silicone resin, 12g of phenyl vinyl silicone oil and 50g of modified aluminum hydroxide, stirring for 40min at a stirring speed of 800r/min, grinding on a three-roller machine until the fineness is 80 meshes, finally adding 0.3g of high-activity phenyl platinum complex, fully and uniformly stirring, and filtering to obtain the component A.
Step two: the preparation of the component B, firstly, mixing 30g of modified gas-phase white carbon black, 25g of hydroxyl functional phenyl silicone oil, 4g of phenyl MQ silicone resin, 12g of phenyl vinyl silicone oil, 50g of modified aluminum hydroxide, 12g of phenyl hydrogen silicone oil and 0.1g of inhibitor acetylene cyclohexanol, stirring for 60min at a stirring speed of 800r/min, grinding to 80 meshes on a three-roller machine, and finally, filtering after fully and uniformly stirring to obtain the component B.
Step three: preparing glue, namely mixing A, B components according to the mass ratio of 1:1, uniformly stirring at a stirring speed of 1800r/min, pressing on a calender by air pressure, controlling the thickness by a roller gap, and heating and curing at 100 ℃ to prepare the low-density foaming silica gel.
Example 2
The difference from example 1 is that: in the preparation method of the low-density foamed silica gel, the addition amount of the hydroxyl-functional phenyl silicone oil in the A, B component was 40g.
Example 3
The difference from example 1 is that: in the preparation method of the low-density foamed silica gel, the addition amount of the phenyl hydrogen-containing silicone oil of the component B is 15g.
Example 4
The difference from example 1 is that: in the preparation method of the low-density foamed silica gel, the hydrogen content of the phenyl hydrogen-containing silicone oil of the component B is 0.4wt%.
Example 5
The difference from example 1 is that: in the preparation method of the low-density foamed silica gel, the addition amount of the modified fumed silica in the A, B component is 40g.
Comparative example 1
The difference from example 1 is that: in the preparation raw materials and the preparation method of the low-density foaming silica gel, the hydroxy functional phenyl silicone oil is replaced by conventional hydroxy phenyl silicone oil with the same viscosity.
Comparative example 2
The difference from example 1 is that: replacing the double-end hydrogen-containing phenyl silicone oil with the double-end hydrogen-containing silicone oil to prepare hydroxyl functional silicone oil; and simultaneously, hydroxyl functional silicone oil is used for preparing the foaming silica gel.
Comparative example 3
The difference from example 1 is that: in the preparation raw materials and the preparation method of the low-density foaming silica gel, the hydroxy functional phenyl silicone oil is replaced by conventional hydroxy silicone oil with the same viscosity.
Comparative example 4
The difference is as in comparative example 2: in the preparation raw materials and the preparation method of the low-density foaming silica gel, phenyl vinyl silicone oil is replaced by conventional vinyl silicone oil with the same viscosity, phenyl MQ silicone resin is replaced by conventional MQ silicone resin with the same viscosity, and phenyl hydrogen silicone oil is replaced by conventional hydrogen silicone oil with the same viscosity and the same hydrogen content.
Comparative example 5
As in comparative example 3, the difference is that: in the preparation raw materials and the preparation method of the low-density foaming silica gel, phenyl vinyl silicone oil is replaced by conventional vinyl silicone oil with the same viscosity, phenyl MQ silicone resin is replaced by conventional MQ silicone resin with the same viscosity and the same M/Q ratio, and phenyl hydrogen silicone oil is replaced by conventional hydrogen silicone oil with the same viscosity and the same hydrogen content.
The surface tension of the silicone oil of different types was tested first, the test standard was measured according to the standard in GB/T18396-2008 Ring method for surface tension, and the test results are shown in Table 1, and the unit of the surface tension is mN/m.
TABLE 1 results of surface tension test of different types of Silicone oils
From the results of Table 1, it is evident that the surface tension of the silicone oil is greatly increased after the addition of the phenyl rigid group.
FIG. 1 shows a photograph of the side of the foamed silica gel prepared in example 1 before being colored, and FIG. 2 shows a photograph of the side of the foamed silica gel prepared in example 1 and comparative example 5 after being colored with a black ink pen. From the comparison in fig. 2, it is evident that: the silica gel system of example 1 has smaller and finer cells, is a foam body with low density and high foaming multiplying power, and has compact ink lines; while comparative example 5 uses conventional silicone oil for bonding, the generated cells are larger, and it is difficult to form a fine foam with high foaming ratio, so that the ink lines are more dispersed. The foaming silica gel prepared by the technical scheme of the application has uniform and fine foam bodies with low density and high foaming multiplying power.
The performance of the foamed silica gels prepared in examples 1 to 5 and comparative examples 1 to 5 was examined, and the results are shown in Table 2, and specific detection criteria are as follows:
specific gravity after curing: according to the standards in ASTM D792-2007 plastics Density and relative Density test method, in g/cc;
pressure offset: force in psi measured at 25% deflection according to ASTM D1056 rubber sponge compression set standard;
compression set (maximum): according to ASTM D1056 rubber sponge compression deformation standard, after compression of 70%, standing for 30min at 100 ℃ for 22 hours at normal temperature, wherein the unit is;
tensile strength: vulcanized rubber and thermoplastic elastomer in psi according to ASTM D412, standard in tensile test method;
elongation rate: the units are in accordance with the ASTM D412 standard in tensile testing methods for vulcanizates and thermoplastic elastomers;
flame retardant rating: according to UL94 flame retardant rating judgment standard;
breakdown voltage: ASTM D149-2009 in KV/mm;
thermal conductivity coefficient: the unit is W/mK according to the standard in ASTM C518.
TABLE 2 test results for different Properties of examples 1-5 and comparative examples 1-5
As can be seen from Table 2, the foamed silica gel prepared by the present application has a low specific gravity and a good tensile strength, which means that the density of the foamed silica gel prepared by the present application is low and the tensile strength is good by the hydroxy-functionalized phenyl silicone oil.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, any of the above-described claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. A hydroxy-functionalized phenyl silicone oil, characterized by comprising- (CH) 2 ) a OH groups, wherein a is an integer from 2 to 5.
2. The hydroxy-functional phenyl silicone oil of claim 1, wherein the hydroxy-functional phenyl silicone oil has the chemical formula HO (CH 2 ) a (CH 3 ) 2 SiO[(CH 3 ) 2 SiO] m [(C 6 H 5 ) 2 SiO] n Si(CH 3 ) 2 (CH 2 ) a OH, wherein m.gtoreq.1, n.gtoreq.1, and m and n are integers.
3. A process for the preparation of a hydroxy-functionalized phenyl silicone oil according to claim 1 or 2, comprising:
carrying out condensation reaction on an enol compound and silazane to obtain a compound X;
carrying out addition reaction on the compound X and double-end hydrogen-containing phenyl silicone oil to obtain a compound Y;
and carrying out alcoholysis reaction on the compound Y and alcohol substances to obtain the hydroxyl functional phenyl silicone oil.
4. A method of preparing as claimed in claim 3, wherein at least one of the following conditions is met:
A. the enol compound comprises at least one of vinyl alcohol, allyl alcohol and allyl butanol;
B. the silazane comprises at least one of hexamethyldisilazane and tetramethyl divinyl disilazane;
C. the chemical structural formula of the double-end hydrogen-containing phenyl silicone oil is H (CH) 3 ) 2 SiO[(CH 3 ) 2 SiO] m [(C 6 H 5 ) 2 SiO] n Si(CH 3 ) 2 H, wherein m is greater than or equal to 1, n is greater than or equal to 1, and m and n are positive integers;
D. the phenyl content in the double-end hydrogen-containing phenyl silicone oil is 5-30wt%;
E. the hydrogen content in the double-end hydrogen-containing phenyl silicone oil is 0.01-0.1 wt%;
F. the alcohol substance comprises any one of methanol and ethanol;
G. a platinum-containing catalyst is also required to be added in the addition reaction, and the platinum content in the platinum-containing catalyst is 3000ppm-5000ppm.
5. The low-density foamed silica gel is characterized by comprising the following raw materials: the hydroxy-functionalized phenyl silicone oil, modified reinforcing filler, modified flame retardant filler, phenyl vinyl silicone oil, phenyl MQ silicone resin, phenyl hydrogen-containing silicone oil, catalyst, and inhibitor of claim 1 or 2.
6. The low density foamed silica gel of claim 5, wherein at least one of the following conditions is satisfied:
H. the modified reinforcing filler is a reinforcing filler modified by a phenylsilane coupling agent;
I. the modified flame-retardant filler is flame-retardant filler modified by a phenylsilane coupling agent;
J. the chemical structural formula of the phenyl vinyl silicone oil is as follows: (CH) 2 ＝CH)(CH 3 ) 2 SiO[(CH 3 ) 2 SiO] m [(C 6 H 5 ) 2 SiO] n Si(CH 3 ) 2 (CH＝CH 2 )；
K. The chemical structural formula of the phenyl hydrogen-containing silicone oil is as follows: (CH) 3 ) 3 SiO[(CH 3 )HSiO] m [(C 6 H 5 ) 2 SiO] n Si(CH 3 ) 3 ；
L, the hydrogen content in the phenyl hydrogen-containing silicone oil is 0.1-1.6 wt%; the phenyl content is 5wt percent to 30wt percent;
the phenyl MQ silicone resin comprises at least one of phenyl vinyl MQ silicone resin and phenyl methyl MQ silicone resin;
the ratio of M chain link to Q chain link in the phenyl MQ silicone resin is (0.8-1): 1, a step of;
the catalyst comprises a phenyl platinum catalyst;
the inhibitor comprises at least one of ethynyl cyclohexanol and 1- (1-propynyl) cyclohexanol.
7. The low density foamed silica gel of claim 6, further satisfying at least one of the following conditions:
q. the phenylsilane coupling agent comprises at least one of phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane and methylphenyldimethoxysilane;
r, the reinforcing filler comprises at least one of gas-phase white carbon black and precipitated white carbon black;
s, the flame-retardant filler comprises at least one of aluminum hydroxide and magnesium hydroxide;
t, adding 25-50 g of the phenylsilane coupling agent into 1000g of the reinforcing filler to carry out the modification treatment;
u, adding 25-50 g of the phenylsilane coupling agent into 1000g of the flame-retardant filler to carry out the modification treatment;
and V. the platinum content in the phenyl platinum catalyst is 3000ppm-5000ppm.
8. A method for preparing the low-density foamed silica gel according to any one of claims 5 to 7, comprising:
mixing and grinding raw materials comprising the hydroxyl functional phenyl silicone oil, the phenyl MQ silicone resin, the phenyl vinyl silicone oil, the modified reinforcing filler and the modified flame retardant filler, and adding the catalyst to obtain a component A;
mixing and grinding raw materials comprising the hydroxyl functional phenyl silicone oil, the phenyl MQ silicone resin, the phenyl vinyl silicone oil, the modified reinforcing filler, the modified flame retardant filler, the phenyl hydrogen silicone oil and the inhibitor to obtain a component B;
and mixing the component A and the component B in proportion, calendaring into a sheet, and heating and curing to obtain the low-density foaming silica gel.
9. The method of manufacturing of claim 8, wherein at least one of the following conditions is satisfied:
a. in the component A, the mass ratio of the hydroxyl functional phenyl silicone oil, the phenyl MQ silicone resin, the phenyl vinyl silicone oil, the modified reinforcing filler, the modified flame retardant filler and the catalyst is (25-40): (3-5): (10-15): (30-40): (40-55): (0.1-0.5);
b. in the component B, the mass ratio of the hydroxyl functional phenyl silicone oil, the phenyl MQ silicone resin, the phenyl vinyl silicone oil, the modified reinforcing filler, the modified flame retardant filler, the phenyl hydrogen silicone oil and the inhibitor is (25-40): (3-5): (10-15): (30-40): (40-55): (10-15): (0.1-0.3);
c. the fineness of the ground product is 80-100 meshes;
d. the mass ratio of the component A to the component B is 1: mixing the components in a ratio of (0.9-1.1);
e. the temperature of the heating and curing is 70-100 ℃.
10. An electronic instrument comprising the low-density foamed silicone as set forth in any one of claims 5 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310939241.1A CN116925358A (en) | 2023-07-28 | 2023-07-28 | Hydroxy-functionalized phenyl silicone oil and preparation method thereof, low-density foaming silica gel and preparation method thereof, and electronic instrument |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310939241.1A CN116925358A (en) | 2023-07-28 | 2023-07-28 | Hydroxy-functionalized phenyl silicone oil and preparation method thereof, low-density foaming silica gel and preparation method thereof, and electronic instrument |
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| CN116925358A true CN116925358A (en) | 2023-10-24 |
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| CN (1) | CN116925358A (en) |
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