CN114958246B - Multifunctional auxiliary agent and preparation method thereof - Google Patents
Multifunctional auxiliary agent and preparation method thereof Download PDFInfo
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- CN114958246B CN114958246B CN202210808689.5A CN202210808689A CN114958246B CN 114958246 B CN114958246 B CN 114958246B CN 202210808689 A CN202210808689 A CN 202210808689A CN 114958246 B CN114958246 B CN 114958246B
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- silane
- silane coupling
- coupling agent
- auxiliary agent
- multifunctional auxiliary
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- 239000012752 auxiliary agent Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000003112 inhibitor Substances 0.000 claims abstract description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 46
- 229910000077 silane Inorganic materials 0.000 claims description 45
- 238000006460 hydrolysis reaction Methods 0.000 claims description 21
- 230000007062 hydrolysis Effects 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- 239000003957 anion exchange resin Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 claims description 9
- -1 methylbutynyl alcohol Chemical compound 0.000 claims description 8
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 claims description 3
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 3
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 claims description 2
- UDWIZRDPCQAYRF-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C=C UDWIZRDPCQAYRF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- MHNUEQUGTGMGFX-UHFFFAOYSA-N diethoxy-hexadecyl-methylsilane Chemical compound CCCCCCCCCCCCCCCC[Si](C)(OCC)OCC MHNUEQUGTGMGFX-UHFFFAOYSA-N 0.000 claims description 2
- DJVQMRRXRRBRIH-UHFFFAOYSA-N diethoxy-methyl-octadecylsilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](C)(OCC)OCC DJVQMRRXRRBRIH-UHFFFAOYSA-N 0.000 claims description 2
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 claims description 2
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 claims description 2
- UBCPEZPOCJYHPM-UHFFFAOYSA-N dimethoxy-methyl-octadecylsilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](C)(OC)OC UBCPEZPOCJYHPM-UHFFFAOYSA-N 0.000 claims description 2
- YGUFXEJWPRRAEK-UHFFFAOYSA-N dodecyl(triethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OCC)(OCC)OCC YGUFXEJWPRRAEK-UHFFFAOYSA-N 0.000 claims description 2
- AILBOMWJRYLVFG-UHFFFAOYSA-N dodecyl-diethoxy-methylsilane Chemical compound CCCCCCCCCCCC[Si](C)(OCC)OCC AILBOMWJRYLVFG-UHFFFAOYSA-N 0.000 claims description 2
- PELGKMTVNFFDDL-UHFFFAOYSA-N dodecyl-dimethoxy-methylsilane Chemical compound CCCCCCCCCCCC[Si](C)(OC)OC PELGKMTVNFFDDL-UHFFFAOYSA-N 0.000 claims description 2
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 claims description 2
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 claims description 2
- MCTWTUQSOKLGFJ-UHFFFAOYSA-N hexadecyl-dimethoxy-methylsilane Chemical compound CCCCCCCCCCCCCCCC[Si](C)(OC)OC MCTWTUQSOKLGFJ-UHFFFAOYSA-N 0.000 claims description 2
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical compound CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 claims description 2
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 claims description 2
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- OYGYKEULCAINCL-UHFFFAOYSA-N triethoxy(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC OYGYKEULCAINCL-UHFFFAOYSA-N 0.000 claims description 2
- FZMJEGJVKFTGMU-UHFFFAOYSA-N triethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC FZMJEGJVKFTGMU-UHFFFAOYSA-N 0.000 claims description 2
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 claims description 2
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 claims description 2
- OWRXWSVBJIIORE-UHFFFAOYSA-N 3,7,11-trimethyldodec-1-yn-3-ol Chemical compound CC(C)CCCC(C)CCCC(C)(O)C#C OWRXWSVBJIIORE-UHFFFAOYSA-N 0.000 claims 1
- 238000006757 chemical reactions by type Methods 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 66
- 239000000853 adhesive Substances 0.000 description 62
- 230000001070 adhesive effect Effects 0.000 description 62
- 239000000047 product Substances 0.000 description 25
- 239000000463 material Substances 0.000 description 18
- 229920002545 silicone oil Polymers 0.000 description 18
- 239000000945 filler Substances 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 5
- 238000007792 addition Methods 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- JQZGUQIEPRIDMR-UHFFFAOYSA-N 3-methylbut-1-yn-1-ol Chemical compound CC(C)C#CO JQZGUQIEPRIDMR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- MSVHFHIGXDZFQW-UHFFFAOYSA-N propan-2-yl 3-oxobutaneperoxoate Chemical compound CC(C)OOC(=O)CC(C)=O.CC(C)OOC(=O)CC(C)=O MSVHFHIGXDZFQW-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052990 silicon hydride Inorganic materials 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The application provides a multifunctional auxiliary agent and a preparation method thereof, wherein the multifunctional auxiliary agent comprises the following components in parts by mole: 100 parts of a silane coupling agent composition; 5-10 parts of alkynol; 1-5 parts of a catalyst; 50-100 parts of water; the silane coupling agent composition comprises the following components in parts by mole: 5-20 parts of a first silane coupling agent; 15-40 parts of a second silane coupling agent; 55-80 parts of a third silane coupling agent; the first silane coupling agent has the structure that: r is R 1 4‑(a+b) R 2 a Si(OR 3 ) b The method comprises the steps of carrying out a first treatment on the surface of the The second silane coupling agent has the structure that: r is R 4 4‑(c+d) R 5 c Si(OR 6 ) d The method comprises the steps of carrying out a first treatment on the surface of the The third silane coupling agent has the structure that: r is R 7 4‑(e+f) R 8 e Si(OR 9 ) f . The multifunctional auxiliary agent provided by the application has the functions of an inhibitor, a tackifier and a powder treating agent.
Description
Technical Field
The application relates to the technical field of multifunctional assistants, in particular to a multifunctional assistant and a preparation method thereof.
Background
In the production process of the heat-conducting adhesive, a plurality of auxiliary agents, such as auxiliary agents with inhibition effect, are often required to be added for ensuring the performance of the heat-conducting adhesive, so that the storage stability of the heat-conducting adhesive is enhanced, and the auxiliary agents with adhesion effect, the adhesion effect of the heat-conducting adhesive and the like are enhanced; however, different auxiliary agents may have mutual influence, the addition amount of each auxiliary agent, the addition ratio of the different auxiliary agents, the addition sequence and the like may have influence on the preparation of the heat-conducting adhesive, and the preparation process of the adhesive is relatively troublesome.
Disclosure of Invention
The application aims at providing a multifunctional auxiliary agent and a preparation method thereof.
In a first aspect, the application provides a multifunctional auxiliary agent, comprising the following components in parts by mole:
the silane coupling agent composition comprises the following components in parts by mole:
5-20 parts of a first silane coupling agent;
15-40 parts of a second silane coupling agent;
55-80 parts of a third silane coupling agent;
the first silane coupling agent has the structure that: r is R 1 4-(a+b) R 2 a Si(OR 3 ) b ；
The second silane coupling agent has the structure that: r is R 4 4-(c+d) R 5 c Si(OR 6 ) d ；
The third silane coupling agent has the structure that: r is R 7 4-(e+f) R 8 e Si(OR 9 ) f ；
Wherein R is 1 Is a vinyl-containing group; r is R 4 Is a group containing an epoxy group; r is R 7 Is a linear alkane group containing 8 to 20C; r is R 2 、R 5 、R 8 Respectively alkyl having 1 to 4C, such as methyl, ethyl, propyl and butyl, preferably methyl, R 2 、R 5 And R is 8 Not necessarily the same; considering that the end use is in the fields of electronics and the like, R 3 、R 6 、R 9 Alkyl groups containing 1 to 2C, i.e., methyl or ethyl, or alkoxy substituted alkyl groups, such as, but not limited to, methoxyethyl; a. c, e are 0 or 1, respectively, but not necessarily the same, b, d, f are 2 or 3, respectively, but not necessarily the same, and the following conditions are satisfied: a+b=2 or 3;c+d=2 or 3; e+f=2 or 3, the sum of the above three additions need not be the same;
alkynols are compounds with alkynyl and hydroxyl groups in the molecule, and the expression modes are as follows:
according to some embodiments of the present application, the first silane coupling agent is: any one or a mixture of two or more of vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, methacryloxypropyl trimethoxysilane and acryloxypropyl methyldiethoxysilane. Vinyl trimethoxysilane, vinyl triethoxysilane, methacryloxypropyl trimethoxysilane are preferred for cost reasons.
According to some embodiments of the present application, the second silane coupling agent is: any one or any two or more of gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, gamma-glycidoxypropyl methyl dimethoxy silane and gamma-glycidoxypropyl diethoxy silane. In view of cost, gamma-glycidoxypropyl trimethoxysilane and gamma-glycidoxypropyl triethoxysilane are preferred.
According to some embodiments of the present application, the third silane coupling agent is: any one of n-dodecyl trimethoxy silane, n-dodecyl triethoxy silane, n-dodecyl methyl dimethoxy silane, n-dodecyl methyl diethoxy silane, n-hexadecyl trimethoxy silane, n-hexadecyl triethoxy silane, n-hexadecyl methyl dimethoxy silane, n-hexadecyl methyl diethoxy silane, n-octadecyl trimethoxy silane, n-octadecyl triethoxy silane, n-octadecyl methyl dimethoxy silane, n-octadecyl methyl diethoxy silane, or a mixture of any two or more thereof. N-dodecyl trimethoxy silane, n-octadecyl trimethoxy silane is preferred for cost reasons.
According to the technical scheme provided by certain embodiments of the application, the alkynol is any one or mixture of any two or more of propargyl alcohol, methylbutynyl alcohol, 3-methyl-1-pentyn-3-ol, ethynyl cyclohexanol, 1, 3-triphenyl-2-propynyl-1-ol, 3,7, 11-trimethyldodecenyl-3-ol and 10-undecynyl alcohol.
According to certain embodiments of the present application, the catalyst is an anion exchange resin or titanate.
According to some embodiments of the present application, the anion exchange resin is a strong base anion exchange resin containing a strong reactive group, such as-N with tetrahedral ammonium functionality + (CH 3 ) 3 In the oxyhydrogen form, -N + (CH 3 ) 3 OH - The hydroxide ions in the silane can be released rapidly, and the anion exchange resin can catalyze the alkoxy hydrolysis and condensation of the silane.
The catalyst can be removed by filtration after the reaction is finished, and does not remain in the reaction product. The proportion of the anion exchange resin is less than 1 percent (weight ratio) of the total amount of the added silane mixture, and the catalysis speed is slower; above 5% by weight, the catalytic rate does not vary much, and it is not necessary to exceed 5% by weight from the viewpoint of cost.
According to the technical scheme provided by certain embodiments of the application, the titanate can be selected from all types of titanate capable of catalyzing silane hydrolysis and condensation, and the titanate is any one of tetraisopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, titanium diisopropoxy diacetylacetonate and titanium diisopropoxy diacetylacetate, or a mixture of any two or more of the titanium diisopropoxy diacetylacetate.
The titanate catalyst is homogeneously dispersed in the system after the reaction is finished, and cannot be removed in a simple way, and is not necessary to be removed. The proportion of the titanate catalyst is lower than 0.2 percent (weight ratio) of the total amount of the added silane mixture, and the catalytic speed is lower; above 2% by weight, catalytic velocity is not much variable, cost considerations are not economical, and excess titanate may adversely affect the physical properties of the target adhesive.
In a second aspect, the present application also provides a method for preparing the multifunctional auxiliary agent, which includes the following steps:
adding the first silane coupling agent, the second silane coupling agent and the third silane coupling agent into a preparation container according to a proportion, and uniformly mixing; the preparation container adopts a three-mouth bottle;
adding water and alkynol into the preparation container according to a certain proportion, and stirring uniformly again;
adding a catalyst into a preparation container according to a certain proportion, and heating for hydrolysis while stirring;
wherein the temperature is the boiling point of the corresponding alcohol generated by hydrolysis, and if the hydrolysis generates methanol, the temperature is 50-64.8 ℃; if ethanol is produced by hydrolysis, the temperature is 50-78.3 ℃; the temperature is lower than the boiling point of all reactants (silane, alkynol and water); if the hydrolysis time is less than 0.5 hour, the hydrolysis may be incomplete, and the alcohol produced by hydrolysis of the product after 3 hours of hydrolysis under the above conditions reaches the theoretical yield through GC test, and the increase of the hydrolysis time is unnecessary.
Removing alcohols generated by hydrolysis by adopting a circulating water vacuum pump to obtain a first product;
heating the first product, and removing components with higher volatility in the first product by adopting a vacuum oil pump until no distillate exists;
after the reaction is finished, continuously maintaining the reaction temperature, firstly extracting hydrolyzed micromolecular alcohol under the condition of 20 mmHg-50 mmHg of vacuum degree, and in the initial stage of vacuum extraction, volatilizing and absorbing heat of the alcohol to cause the abrupt reduction of the temperature of a reactant, and after the temperature of the reactant is risen to the reaction temperature again in the vacuum state, indicating that the internal alcohol is almost completely removed; maintaining for 5-10 min, raising the vacuum degree to 2-5 mmHg, and raising the temperature of the reactant to 100-120 ℃ until no distillate exists; wherein the aim of the vacuum degree is to reduce the oligomer content in the auxiliary agent.
And cooling and filtering to obtain a multifunctional auxiliary agent finished product.
Compared with the prior art, the application has the beneficial effects that: because the application adopts the technical proposal,
the multifunctional auxiliary agent prepared by the co-hydrolysis method of the functional silane has the functions of an inhibitor, a tackifier and a powder treatment agent, and when the multifunctional auxiliary agent is used for preparing the heat conduction agent, other auxiliary agents are not required to be additionally added, so that the preparation process of the heat conduction agent is simplified, and the heat conduction agent prepared by adopting the multifunctional auxiliary agent has the following excellent performances: the adhesive has good workability, low smell, no wrinkles in the curing process, and good adhesive force and adhesion with materials such as plastics, aluminum alloy, glass, ceramics and the like.
The multifunctional auxiliary agent provided by the application has the advantages that the inhibited molecular fragments are fixed on one larger molecule, so that the multifunctional auxiliary agent is free from volatility, has no excessively high requirement on the sealing property of a package, has low smell, and has no surface wrinkling phenomenon in the curing process, namely, the multifunctional auxiliary agent has the effect of an inhibitor; the polar segment of the multifunctional auxiliary agent acts with the base material to be bonded, and the vinyl segment on the multifunctional auxiliary agent can react with Si-H in the adhesive body to form connection, namely the multifunctional auxiliary agent has the function of a tackifier; the powder treatment agent fragments of the multifunctional auxiliary agent act with the powder, and the powder is also an important component part of the adhesive body, especially the organic silicon heat conduction adhesive with higher filling amount, and both effects increase the connection between the tackifier and the adhesive body; as powder treating agent, the multifunctional auxiliary agent is used for treating powder without heating treatment, so that the powder treatment process is simplified.
Detailed Description
The present application will be described in further detail with reference to examples. It is to be understood that the specific embodiments described herein are merely illustrative of the application and are not limiting of the application. It should be noted that, without conflict, embodiments of the present application and features of the embodiments may be combined with each other.
Example 1
The embodiment provides a multifunctional auxiliary agent, and the preparation method thereof is as follows:
s1, adding a first silane coupling agent, a second silane coupling agent and a third silane coupling agent into a three-mouth bottle according to a proportion, and uniformly mixing;
wherein the first silane coupling agent adopts vinyl trimethoxy silane, the second silane coupling agent adopts gamma-glycidol ether oxypropyl trimethoxy silane, and the third silane coupling agent adopts n-dodecyl trimethoxy silane; the mole percentages of the three silane coupling agents are respectively as follows: 5%, 15% and 80%.
S2, adding water and alkynol into the three-mouth bottle according to a proportion, and stirring uniformly again;
wherein, the alkynol adopts methyl butynol, and the dosage of the methyl butynol is 5 percent (mol) based on the total silane substances; the amount of water used was 50% based on the total mass of silane.
S3, adding a catalyst into the three-mouth bottle according to a proportion, and heating for hydrolysis while stirring;
wherein the catalyst adopts anion exchange resin, the specific model is 201 x 7, and the dosage is 3% based on the total mass of silane; in this step, the temperature was raised to 50℃and maintained for 1 hour.
S4, removing alcohols generated by hydrolysis by using a circulating water vacuum pump to obtain a first product;
maintaining heating power, removing alcohols generated by hydrolysis by using a circulating water vacuum pump, quickly reducing the temperature of reactants due to volatilization of the alcohols, and continuously pumping by using the circulating water vacuum pump for 8min after the temperature rises to the reaction temperature, wherein most of the alcohols are removed.
S5, heating the first product, and removing components with higher volatility in the first product by adopting a vacuum oil pump until no distillate exists;
the temperature of the first product was raised to 110 ℃, and the relatively high volatile components in the product were removed by a vacuum oil pump at a vacuum level of less than 5mmHg until no distillate was present.
S6, cooling and filtering to obtain a multifunctional auxiliary agent finished product.
And (3) cooling the product obtained in the step (S5) to room temperature, and filtering the ion exchange resin to obtain a multifunctional auxiliary product which is almost colorless and transparent.
Example 2
The main steps of the preparation method of the multifunctional auxiliary agent are the same as those adopted in the embodiment 1, and the same points are not repeated, except that:
in the step S1, the first silane coupling agent adopts methacryloxypropyl trimethoxy silane, the second silane coupling agent adopts gamma-glycidol ether oxypropyl trimethoxy silane, and the third silane coupling agent adopts n-hexadecyl trimethoxy silane; the mole percentages of the three silane coupling agents are respectively as follows: 5%, 40% and 55%.
In step S2, the alkynol is ethynyl cyclohexanol in an amount of 10% based on the total silane material (mol); the amount of water used was 60% based on the total mass of silane.
In step S3, the amount of the anion exchange resin is 3% based on the total mass of silane.
Example 3
The main steps of the preparation method of the multifunctional auxiliary agent are the same as those adopted in the embodiment 1, and the same points are not repeated, except that:
in the step S1, the mole percentages of the three silane coupling agents are respectively as follows: 20%, 25% and 55%.
In step S2, the alkynol is used in an amount of 7% based on the amount (mol) of the total silane material; the amount of water used was 70% based on the total mass of silane.
In step S3, the amount of the anion exchange resin is 5% based on the total mass of silane.
Example 4
The main steps of the preparation method of the multifunctional auxiliary agent are the same as those adopted in the embodiment 1, and the same points are not repeated, except that:
in the step S1, the mole percentages of the three silane coupling agents are respectively as follows: 10%, 22% and 68%.
In step S2, the alkynol is used in an amount of 7% based on the amount (mol) of the total silane material; the amount of water used was 70% based on the total mass of silane.
In step S3, the amount of the anion exchange resin is 4% based on the total mass of silane.
Comparative example 1
The main steps of the preparation method of the multifunctional auxiliary agent provided in the comparative example are the same as those adopted in the embodiment 1, and the same points are not repeated, except that:
in step S2, the amount of water is 40% based on the total mass of silane.
Comparative example 2
The main steps of the preparation method of the multifunctional auxiliary agent provided in the comparative example are the same as those adopted in the embodiment 1, and the same points are not repeated, except that:
in the step S1, the first silane coupling agent adopts methacryloxypropyl trimethoxy silane, the second silane coupling agent adopts gamma-glycidol ether oxypropyl trimethoxy silane, and the third silane coupling agent adopts n-hexadecyl trimethoxy silane; the mole percentages of the three silane coupling agents are respectively as follows: 20%, 40% and 40%.
In step S2, the alkynol is ethynyl cyclohexanol in an amount of 10% based on the total silane material (mol); the amount of water used was 120% based on the total mass of silane.
In step S3, the amount of the anion exchange resin is 4% based on the total mass of silane.
Comparative example 3
The main steps of the preparation method of the multifunctional auxiliary agent provided in the comparative example are the same as those adopted in the embodiment 1, and the same points are not repeated, except that:
in the step S1, the mole percentages of the three silane coupling agents are respectively as follows: 10%, 22% and 68%.
In step S2, the alkynol is used in an amount of 7% based on the amount (mol) of the total silane material; the amount of water used was 30% based on the total mass of silane.
In step S3, the amount of the anion exchange resin is 5% based on the total mass of silane.
Performance test 1
The viscosity and yield of the multifunctional assistants prepared in examples 1 to 4 and comparative examples 1 to 3 were tested respectively, and specifically using haake viscotesteriq.
For yield, let the theoretical yield be M 0 According to 1mol part of H 2 The relationship between O and sufficient silane to produce 2 mole parts of low molecular weight alcohol, and 1 mole of alkynol containing 1 hydroxyl group to produce 1 mole part of low molecular weight alcohol is calculated. The term "sufficient" as used above means H 2 The hydrolyzable alkoxy groups remain in the system after the O and alkynols have reacted completely with the silane.
The specific calculation formula of the yield is as follows: yield = M/M 0 ×100％。
Wherein M is 0 Theoretical yield (in grams); m is the mass (unit: g) of the target product, which remains after heating and vacuum removal of the small molecules.
M 0 ＝m 1 +m 2 +m 3 -m 2 /M w2 ×M w4 ×2-m 3 /M w3 ×M w4
m 1 、m 2 、m 3 The amounts of silane, water and alkynol (in grams), respectively;
M w2 、M w3 、M w4 the molecular weights of water, alkynol and alcohol produced by the reaction are respectively.
The test results are shown in Table 1.
TABLE 1
The above results show that when the ratio of water to the silane coupling agent composition in the raw materials is required to be within a certain range during the preparation of the multifunctional auxiliary agent, when the molar ratio of water to the silane coupling agent composition is low (as in comparative examples 1 and 3), the degree of condensation is insufficient after the hydrolysis of the silane, resulting in higher small molecular components and lower yield in the finished multifunctional auxiliary agent; when the molar ratio of water to the silane coupling agent composition is high (as in comparative example 2), the degree of condensation after the silane hydrolysis is too high, resulting in too high a viscosity of the finished multifunctional auxiliary; the viscosity of the multifunctional auxiliary agent is too high, so that the multifunctional auxiliary agent is unfavorable for preparing other substances, such as a heat conducting agent, because the multifunctional auxiliary agent with too high viscosity has poor effect on treating powder for preparing the heat conducting agent, the conventional inorganic filler particles for preparing the heat conducting agent have hydroxyl groups on the surfaces, the hydroxyl groups of the particles have hydrogen bonds, and the conventional inorganic filler particles have great resistance to be overcome if the conventional inorganic filler particles are detached, so that the preparation of the heat conducting agent with good performance is not realized if the viscosity of the auxiliary agent is relatively high.
The "small molecule component" includes silane which does not participate in the hydrolysis-condensation reaction, and molecules which are easily volatilized from each molecule formed after the hydrolysis condensation of silane, that is, molecules which can be extracted when vacuum is applied in step S5.
Example 5
The main steps of the preparation method of the multifunctional auxiliary agent are the same as those adopted in the embodiment 1, and the same points are not repeated, except that:
in the step S1, the mole percentages of the three silane coupling agents are respectively as follows: 10%, 22% and 68%.
In step S2, the alkynol is used in an amount of 7% based on the amount (mol) of the total silane material; the amount of water used was 70% based on the total mass of silane.
In the step S3, the catalyst adopts titanium ethyl diisopropoxy diacetoacetate, and the dosage of the catalyst is 1 percent based on the total mass of silane.
Comparative example 4
The main steps of the preparation method of the multifunctional auxiliary agent provided in the comparative example are the same as those adopted in the embodiment 5, and the same points are not repeated, except that:
in step S2, the alkynols are used in an amount of 13% based on the total mass (mol) of silane.
Comparative example 5
The main steps of the preparation method of the multifunctional auxiliary agent provided in the comparative example are the same as those adopted in the embodiment 5, and the same points are not repeated, except that:
in step S2, the alkynols are ethynyl cyclohexanol in an amount of 13% based on the total silane material (mol).
Comparative example 6
The main steps of the preparation method of the multifunctional auxiliary agent provided in the comparative example are the same as those adopted in the embodiment 5, and the same points are not repeated, except that:
in the step S1, the first silane coupling agent adopts vinyl trimethoxy silane, the second silane coupling agent adopts gamma-glycidol ether oxypropyl trimethoxy silane, and the third silane coupling agent adopts n-hexadecyl trimethoxy silane; the mole percentages of the three silane coupling agents are respectively as follows: 2%, 25% and 73%.
In step S2, the alkynols are ethynyl cyclohexanol in an amount of 7% based on the total silane material (mol).
Comparative example 7
The main steps of the preparation method of the multifunctional auxiliary agent provided in the comparative example are the same as those adopted in the embodiment 5, and the same points are not repeated, except that:
in the step S1, the first silane coupling agent adopts vinyl trimethoxy silane, the second silane coupling agent adopts gamma-glycidol ether oxypropyl trimethoxy silane, and the third silane coupling agent adopts n-hexadecyl trimethoxy silane; the mole percentages of the three silane coupling agents are respectively as follows: 12%, 10% and 78%.
In step S2, the alkynols are ethynyl cyclohexanol in an amount of 7% based on the total silane material (mol).
Comparative example 8
The main steps of the preparation method of the multifunctional auxiliary agent provided in the comparative example are the same as those adopted in the embodiment 5, and the same points are not repeated, except that:
in the step S1, the mole percentages of the three silane coupling agents are respectively as follows: 14%, 36% and 50%.
In step S2, the alkynols are ethynyl cyclohexanol in an amount of 7% based on the total silane material (mol).
Comparative example 9
The main steps of the preparation method of the multifunctional auxiliary agent provided in the comparative example are the same as those adopted in the embodiment 5, and the same points are not repeated, except that:
in the step S1, the mole percentages of the three silane coupling agents are respectively as follows: 25%, 15% and 60%.
In step S2, the alkynols are ethynyl cyclohexanol in an amount of 7% based on the total silane material (mol).
Performance test 2
The viscosity and yield of the multifunctional assistants prepared in examples, as well as comparative examples 4-9, were respectively tested, and specific test methods are referred to as methods in performance test 1, and test results are shown in table 2.
TABLE 2
| Viscosity (mPa. S) | Yield rate | |
| Example 5 | 68 | 98.2％ |
| Comparative example 4 | 65 | 97.7％ |
| Comparative example 5 | 66 | 98.1％ |
| Comparative example 6 | 68 | 97.2％ |
| Comparative example 7 | 70 | 97.1％ |
| Comparative example 8 | 71 | 97.9％ |
| Comparative example 9 | 68 | 98.0％ |
The above results show that when the amount of alkynol in the raw material is lower than the requirement of the present application (e.g., comparative example 4) or higher than the requirement of the present application (e.g., comparative example 5), or the amount of any one of the silane coupling agents in the raw material is lower than the requirement of the present application (e.g., comparative examples 6 to 8), or the amount of any one of the silane coupling agents in the raw material is higher than the requirement of the present application (e.g., comparative example 9), the effects on the viscosity and yield of the prepared multifunctional auxiliary are not large, i.e., the yield and viscosity of the multifunctional auxiliary are largely affected by the amount of water.
Example 6
The embodiment provides an adhesive, which is prepared by the following method:
s21, adding vinyl silicone oil, hydrogen-containing silicone oil and multifunctional auxiliary agent into the dispersing equipment according to a proportion, mixing and stirring uniformly to obtain a first product.
Wherein the vinyl silicone oil adopts vinyl-terminated silicone oil with the viscosity of 5000 mPas; the hydrogen-containing silicone oil adopts a multi-hydrogen silicone oil with the hydrogen content of 0.5% and the ends of a molecular chain of which are blocked by trimethylsilyl groups, and the viscosity of the multi-hydrogen silicone oil is 52 mPas; the multifunctional auxiliary agent is prepared from the embodiment 1.
100g of vinyl silicone oil, 3.6g of hydrogen-containing silicone oil and 10g of multifunctional auxiliary agent are mixed and stirred uniformly in a planetary stirrer to obtain a first product.
S22, adding the heat conducting filler into the dispersing equipment in batches at room temperature, and stirring to slowly mix the heat conducting filler into the first product to form a cluster, so as to obtain a second product.
The heat conducting filler is prepared by mixing spherical alumina with average diameters of 1um, 10um and 40um and the surface not subjected to hydrophobic treatment with the following components in percentage by weight: 2:4, slowly adding 1000g of the heat-conducting filler into the heat-conducting filler in batches at room temperature, and stirring to slowly mix the powder into the silicone oil for agglomeration.
S23, adding a platinum catalyst, slowly stirring, continuously stirring under a vacuum condition, and discharging after defoaming to obtain a finished adhesive product.
And (3) after continuously stirring slowly for 1 hour at room temperature, adding a platinum catalyst, stirring slowly for 10min, stirring continuously for 10min under vacuum condition, defoaming, and discharging to obtain the adhesive finished product.
The concentration of the platinum catalyst ranges from 1 to 30 ppm, preferably from 3 to 20ppm; the platinum catalyst may be a Karstedt catalyst, a Speier catalyst, an Ashby catalyst, a Lamoreaux catalyst, or a capsule type platinum catalyst; in this example, karstedt's catalyst was selected with a ppm concentration in the range of 10.
Example 7
The main steps of the preparation method of the adhesive provided in this embodiment are the same as those adopted in embodiment 6, and the same points are not repeated, except that:
in step S21, the multifunctional auxiliary agent is prepared from example 4.
Comparative example 10
The comparative example provides an adhesive, which is prepared by the same main steps as those adopted in example 6, except that:
the multifunctional auxiliary agent is replaced by inert silicone oil, the viscosity of the inert silicone oil is 50 mPas, and the polydimethylsiloxane is blocked by trimethyl siloxy and does not have the function of treating the surface of the filler.
Comparative example 11
The comparative example provides an adhesive, which is prepared by the same main steps as those adopted in example 6, except that:
the common filler hexadecyl trimethoxy silane is adopted to replace the multifunctional auxiliary agent.
Comparative example 12
The comparative example provides an adhesive, which is prepared by the same main steps as those adopted in example 6, except that:
in step S21, the multifunctional auxiliary agent is prepared from comparative example 2.
Performance test 3
The finished adhesive products prepared in example 6, example 7, comparative example 10, comparative example 11 and comparative example 12 were tested, in particular using Haake Viscotester iQ for viscosity; the adhesives were characterized for thermal conductivity prior to curing using Longwin9389, which meets ASTM5470 standards, and the test results are shown in table 3.
TABLE 3 Table 3
| Viscosity (mPa. S) | Thermal conductivity (W/(m.k)) | |
| Example 6 | 98000 | 3.2 |
| Example 7 | 102000 | 3.1 |
| Comparative example 10 | The filler cannot be mixed in | Failure to test |
| Comparative example 11 | 145800 | 2.8 |
| Comparative example 12 | 182300 | 2.6 |
The above results indicate that the adhesives prepared using the multifunctional adjuvant provided by the present application have lower viscosity and relatively higher thermal conductivity, and it can be inferred that when the limit filling is reached, the heat conductive adhesives using the present application will have greater heat conductive filling amount and thermal conductivity.
Example 8
The main steps of the preparation method of the adhesive provided in this embodiment are the same as those adopted in embodiment 6, and the same points are not repeated, except that:
in step S21, the multifunctional auxiliary agent is prepared from example 2;
the vinyl silicone oil in the step S21 adopts vinyl-terminated silicone oil with the viscosity of 500 mPas; the mass of the vinyl silicone oil, the hydrogen-containing silicone oil and the multifunctional auxiliary agent are respectively as follows: 100g, 9g and 48g;
the heat conductive filler in step S22 is spherical alumina with average diameters of 5um, 20um and 90um and surface not subjected to hydrophobic treatment, and the average diameter is 1:1:5, wherein the total mass of the heat conducting filler is 2400g;
the step S22 of adding the fumed silica which is a reinforcing filler and has a specific surface area of 150m into the planetary mixer 2 Per gram, the mass added was 3g.
Example 9
The main steps of the preparation method of the adhesive provided in this embodiment are the same as those adopted in embodiment 8, and the same points are not repeated, except that:
in step S21, the multifunctional auxiliary agent is prepared from example 5.
Comparative example 13
The main steps of the preparation method of the adhesive provided in the comparative example are the same as those adopted in the embodiment 8, and the same points are not repeated, except that:
in step S21, the multifunctional auxiliary agent is prepared from comparative example 6.
Comparative example 14
The main steps of the preparation method of the adhesive provided in the comparative example are the same as those adopted in the embodiment 8, and the same points are not repeated, except that:
in step S21, the multifunctional auxiliary agent is prepared from comparative example 7.
Comparative example 15
The main steps of the preparation method of the adhesive provided in the comparative example are the same as those adopted in the embodiment 8, and the same points are not repeated, except that:
in step S21, the multifunctional auxiliary agent is prepared from comparative example 8.
Comparative example 16
The main steps of the preparation method of the adhesive provided in the comparative example are the same as those adopted in the embodiment 8, and the same points are not repeated, except that:
in step S21, the multifunctional auxiliary agent is prepared from comparative example 9.
Performance test 4
The finished adhesive products prepared in example 8, example 9, comparative example 13-comparative example 16 were tested, in particular for viscosity using Haake Viscotester iQ; the thermal conductivity of the adhesive before curing was characterized by Longwin9389 meeting ASTM5470 standard, and at the same time, an aluminum sheet-aluminum sheet (aluminum alloy type 5025)) was also formed according to ASTM, cut into pieces, cured in an oven at 150 ℃ for 1 hour, cooled at room temperature for 24 hours, and the shear strength was measured at a speed of 5mm/min using a SUNS UTM4104 universal material tester, and the form of failure was observed to determine the quality of the bond, and the test results are shown in table 4.
TABLE 4 Table 4
Wherein cf in Table 4 indicates the failure of the bond line, i.e., the adhesive is present on the failure side of both substrates after failure; af represents interfacial failure, i.e., the adhesive drops off from the contact surface with the substrate after failure, leaving no adhesive on the failure surface of at least one substrate; the percentage before af indicates the proportion of interfacial failure occurring.
The results show that the adhesive prepared by the multifunctional auxiliary agent provided by the application can be used for obtaining the adhesive with relatively balanced performances such as construction performance, heat conduction effect and bonding strength. When the first silane coupling agent participating in the reaction with Si-H in the adhesive body is less, or the second silane coupling agent generating acting force with the substrate is less, the prepared adhesive composition has lower viscosity, but the shearing strength and the destruction mode of the bonding are not ideal; when the third silane coupling agent for reducing the friction force between the powder materials is insufficient, the viscosity of the adhesive composition is high, so that the adhesive composition is unfavorable for infiltrating the substrate to be bonded; when the first silane coupling agent is too much, the Si-H in the adhesive composition is too much connected with the powder, which is not beneficial to realizing the ideal bonding effect.
Comparative example 17
The main steps of the preparation method of the adhesive provided in the comparative example are the same as those adopted in the embodiment 8, and the same points are not repeated, except that:
in step S21, the multifunctional auxiliary agent is prepared from comparative example 4.
Comparative example 18
The main steps of the preparation method of the adhesive provided in the comparative example are the same as those adopted in the embodiment 8, and the same points are not repeated, except that:
in step S21, the multifunctional auxiliary agent is prepared from comparative example 5.
Performance test 5
The adhesive finished products prepared in example 8, example 9, comparative example 17 and comparative example 18 were tested, specifically, the adhesive finished products were coated on aluminum sheets to form circles with diameters of >100mm and thicknesses of more than 2mm, and after curing in an oven at 150 ℃ for 1 hour, the adhesive finished products were taken out to see whether the surfaces were flat or wrinkled; 200g of each finished adhesive was placed in an aluminum can with a volume of 150mL and sealed, and after 14 days of standing at 50 ℃ (half a year of storage at simulated room temperature), the viscosity of each sample was measured, and the difference from the initial viscosity was observed, and the test results are shown in Table 5.
TABLE 5
The results show that the addition amount of alkynol is too small in the process of preparing the multifunctional auxiliary agent, which can lead to insufficient storage stability of the adhesive prepared by the multifunctional auxiliary agent; and in the process of preparing the multifunctional auxiliary agent, too much alkynol is added, so that part of alkynol is still in a free state, and the phenomenon of surface layer wrinkling of the adhesive prepared by the multifunctional auxiliary agent after solidification is caused.
The multifunctional auxiliary agent is prepared in a functional silane cohydrolysis mode, and has the functions of an inhibitor, a tackifier and a powder treating agent; as the inhibitor, the molecular fragments with inhibition are fixed on a larger molecule, so that the inhibitor is not volatile, has no excessively high requirement on the tightness of the package, has low odor and has no surface wrinkling phenomenon in the curing process; as a tackifier, the polar segment of the multifunctional auxiliary agent acts with a substrate to be bonded, and the vinyl segment on the multifunctional auxiliary agent can react with Si-H in the adhesive body to form connection; the powder treatment agent segment of the multifunctional auxiliary agent acts with the powder, and the powder is also an important component of the adhesive body, in particular to an organosilicon heat-conducting adhesive with higher filling amount. Both effects increase the bond of the tackifier to the adhesive body; as powder treating agent, the multifunctional auxiliary agent is used for treating powder without heating treatment, so that the powder treatment process is simplified.
When the multifunctional auxiliary agent provided by the application is used for preparing the adhesive, the adhesive is directly added into vinyl silicone oil and hydrogen-containing silicone oil to be uniformly mixed, and then the heat-conducting filler with untreated surface is added, so that the multifunctional auxiliary agent rapidly acts with hydroxyl on the surface of the heat-conducting filler, the surface of the heat-conducting filler is wrapped, and the mutual friction between powder materials is effectively reduced; in the storage process of the adhesive, the multi-alkynyl structure contained in the multifunctional auxiliary agent can effectively inhibit the platinum catalyst so as to stabilize the adhesive; in the curing process of the adhesive, the epoxy groups on the multifunctional auxiliary agent react with the base material by virtue of the polarity, and the vinyl groups on the multifunctional auxiliary agent are combined with the silicon hydride by chemical reaction to generate adhesive force.
The adhesive prepared by the multifunctional additive disclosed by the application has good extrusion performance, can be stored for 6 months at normal temperature, has good construction performance, low smell, no wrinkles in the curing process, and has good adhesive force and adhesion with materials such as plastics, aluminum alloy, glass, ceramics and the like.
The principles and embodiments of the present application have been described herein with reference to specific examples, the description of which is intended only to facilitate an understanding of the method of the present application and its core ideas. The foregoing is merely illustrative of the preferred embodiments of this application, and it is noted that there is objectively no limit to the specific structure disclosed herein, since numerous modifications, adaptations and variations can be made by those skilled in the art without departing from the principles of the application, and the above-described features can be combined in any suitable manner; such modifications, variations and combinations, or the direct application of the inventive concepts and aspects to other applications without modification, are contemplated as falling within the scope of the present application.
Claims (9)
1. The multifunctional auxiliary agent is characterized by comprising the following components in parts by mass:
100 parts of a silane coupling agent composition;
1-5 parts of a catalyst;
50-100 parts of water;
the composition also comprises alkynol, wherein the dosage of the alkynol is 5%, 7% or 10% of the total matters of the silane coupling agent composition;
wherein the silane coupling agent composition consists of the following components in parts by mole:
5-20 parts of a first silane coupling agent;
15-40 parts of a second silane coupling agent;
55-80 parts of a third silane coupling agent;
the first silane coupling agent has the structure that: r is R 1 4-(a+b) R 2 a Si(OR 3 ) b ；
The second silane coupling agent has the structure that: r is R 4 4-(c+d) R 5 c Si(OR 6 ) d ；
The third oneThe structure of the silane coupling agent is as follows: r is R 7 4-(e+f) R 8 e Si(OR 9 ) f ；
Wherein R is 1 Is a vinyl-containing group; r is R 4 Is a group containing an epoxy group; r is R 7 Is a linear alkane group containing 8 to 20C; r is R 2 、R 5 、R 8 Respectively alkyl containing 1-4C; r is R 3 、R 6 、R 9 Respectively alkyl containing 1-2C; a. c, e are 0 or 1, b, d, f are 2 or 3, respectively, and the following conditions are satisfied: a+b=2 or 3; c+d=2 or 3; e+f=2 or 3;
the multifunctional auxiliary agent is prepared in a functional silane cohydrolysis mode, and the reaction type is silane hydrolysis-condensation reaction;
the multifunctional auxiliary agent has the functions of an inhibitor, a tackifier and a powder treating agent.
2. The multifunctional additive according to claim 1, wherein the first silane coupling agent is: any one or more of vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, methacryloxypropyl trimethoxysilane, acryloxypropyl methyldiethoxysilane.
3. The multifunctional auxiliary agent according to claim 1, wherein the second silane coupling agent is: any one or a mixture of a plurality of gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, gamma-glycidoxypropyl methyl dimethoxy silane and gamma-glycidoxypropyl diethoxy silane.
4. The multifunctional auxiliary agent according to claim 1, wherein the third silane coupling agent is: any one or a mixture of a plurality of n-dodecyl trimethoxy silane, n-dodecyl triethoxy silane, n-dodecyl methyl dimethoxy silane, n-dodecyl methyl diethoxy silane, n-hexadecyl trimethoxy silane, n-hexadecyl triethoxy silane, n-hexadecyl methyl dimethoxy silane, n-hexadecyl methyl diethoxy silane, n-octadecyl trimethoxy silane, n-octadecyl triethoxy silane, n-octadecyl methyl dimethoxy silane and n-octadecyl methyl diethoxy silane.
5. The multifunctional auxiliary agent according to claim 1, wherein the alkynol is any one or more of propargyl alcohol, methylbutynyl alcohol, 3-methyl-1-pentyn-3-ol, ethynyl cyclohexanol, 1, 3-triphenyl-2-propyn-1-ol, 3,7, 11-trimethyldodecyn-3-ol, 10-undecynyl alcohol.
6. The multifunctional auxiliary agent according to claim 1, wherein the catalyst is an anion exchange resin or titanate.
7. The functional aid according to claim 6, wherein the anion exchange resin is a strong base anion exchange resin.
8. The functional auxiliary agent according to claim 6, wherein the titanate is any one or more of tetraisopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, titanium diisopropoxy diacetylacetonate, and titanium diisopropoxy diacetylacetate.
9. A method of preparing a multifunctional adjuvant according to any one of claims 1-8, comprising the steps of:
adding the first silane coupling agent, the second silane coupling agent and the third silane coupling agent into a preparation container according to a proportion, and uniformly mixing;
adding water and alkynol into the preparation container according to a certain proportion, and stirring uniformly again;
adding a catalyst into a preparation container according to a certain proportion, and heating for hydrolysis while stirring;
removing alcohols generated by hydrolysis by adopting a circulating water vacuum pump to obtain a first product;
heating the first product, and removing components with higher volatility in the first product by adopting a vacuum oil pump until no distillate exists;
and cooling and filtering to obtain a multifunctional auxiliary agent finished product.
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|---|---|---|---|---|
| US5399651A (en) * | 1994-05-10 | 1995-03-21 | Dow Corning Corporation | Adhesion promoting additives and low temperature curing organosiloxane compositions containing same |
| CN104774333A (en) * | 2015-04-30 | 2015-07-15 | 绵阳惠利电子材料有限公司 | Addition type organic silicon rubber tackifier, preparation method and application thereof |
| CN113088244A (en) * | 2021-04-09 | 2021-07-09 | 绵阳惠利电子材料有限公司 | Low-viscosity flowing type high-heat-conductivity flame-retardant packaging material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5399651A (en) * | 1994-05-10 | 1995-03-21 | Dow Corning Corporation | Adhesion promoting additives and low temperature curing organosiloxane compositions containing same |
| CN104774333A (en) * | 2015-04-30 | 2015-07-15 | 绵阳惠利电子材料有限公司 | Addition type organic silicon rubber tackifier, preparation method and application thereof |
| CN113088244A (en) * | 2021-04-09 | 2021-07-09 | 绵阳惠利电子材料有限公司 | Low-viscosity flowing type high-heat-conductivity flame-retardant packaging material and preparation method thereof |
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