CN117535030A - Single-component solvent-free organic silicon three-proofing adhesive and preparation method thereof - Google Patents
Single-component solvent-free organic silicon three-proofing adhesive and preparation method thereof Download PDFInfo
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- CN117535030A CN117535030A CN202311616926.9A CN202311616926A CN117535030A CN 117535030 A CN117535030 A CN 117535030A CN 202311616926 A CN202311616926 A CN 202311616926A CN 117535030 A CN117535030 A CN 117535030A
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- silicone oil
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- 239000000853 adhesive Substances 0.000 title claims abstract description 53
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 53
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 20
- 239000010703 silicon Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims description 21
- 229920002545 silicone oil Polymers 0.000 claims abstract description 101
- -1 polysiloxane Polymers 0.000 claims abstract description 79
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 22
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 16
- 239000010936 titanium Substances 0.000 claims abstract description 16
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 13
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 9
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims abstract description 7
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 83
- 238000006243 chemical reaction Methods 0.000 claims description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 238000010438 heat treatment Methods 0.000 claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- 238000001914 filtration Methods 0.000 claims description 31
- 238000005406 washing Methods 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 25
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 21
- 239000012044 organic layer Substances 0.000 claims description 18
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 17
- 238000001179 sorption measurement Methods 0.000 claims description 16
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 12
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 10
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 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 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000003729 cation exchange resin Substances 0.000 claims description 7
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- NDRPHZPVTSFYLH-UHFFFAOYSA-N 2,4,6-tris(2-butoxyphenyl)-1,3,5-triazine Chemical compound C(CCC)OC1=C(C=CC=C1)C1=NC(=NC(=N1)C1=C(C=CC=C1)OCCCC)C1=C(C=CC=C1)OCCCC NDRPHZPVTSFYLH-UHFFFAOYSA-N 0.000 claims description 3
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 claims description 3
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-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 2
- 150000001565 benzotriazoles Chemical class 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 22
- 238000000576 coating method Methods 0.000 abstract description 22
- 238000007711 solidification Methods 0.000 abstract description 10
- 230000008023 solidification Effects 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 10
- 230000003993 interaction Effects 0.000 abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 20
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 229920002554 vinyl polymer Polymers 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000010410 layer Substances 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 8
- 239000003292 glue Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 6
- 229910000077 silane Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical class [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 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
- 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
- C09J183/10—Block or graft copolymers containing polysiloxane sequences
-
- 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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
Abstract
The invention provides a single-component solvent-free organic silicon three-proofing adhesive which is prepared from the following raw materials: 100 parts by weight of an alkoxy-terminated polysiloxane; 1-5 parts of cross-linking agent; 0.1 to 0.5 weight portion of titanium catalyst; 0.01 to 0.1 weight portion of ultraviolet indicator; 0.5 to 1.5 weight portions of tackifier; the alkoxy-terminated polysiloxane is prepared from MT silicone oil and modified silicone oil; the cross-linking agent is selected from one or more of methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane and tetraethoxysilane. Compared with the prior art, the single-component solvent-free organic silicon three-proofing adhesive provided by the invention adopts components with specific content, realizes better overall interaction, has the advantages of quick solidification and no solvent, has higher hardness while each performance meets the coating requirement of a circuit board, has very smooth surface after solidification, has excellent anti-friction performance, and can play a good role in protecting the circuit board by coating a very thin layer on the surface.
Description
Technical Field
The invention relates to the technical field of three-proofing glue, in particular to single-component solvent-free organosilicon three-proofing glue and a preparation method thereof.
Background
In the fields of electronics, electricians and electric appliances, in order to protect devices from corrosion of the environment, people often coat three-proofing glue, also called glue-coated products, on the surfaces of circuit boards, electronic components, electric appliance modules and the like; the cured transparent protective film has excellent insulating, dampproof, anticreep, shockproof, dustproof, antisulfide, salt fog preventing, anticorrosive, ageing preventing, corona resisting and other performances. At present, three-proofing glue products applied in industry mainly comprise three types of organic silicon, polyurethane and acrylic acid. The organic silicon three-proofing adhesive product has the excellent characteristics of high and low temperature resistance, electric insulation, ozone resistance, radiation resistance, flame retardance, hydrophobicity and the like, and is most widely applied to industry.
Chinese patent CN106566463a discloses a single-component, condensed, solvent-borne organosilicon phenyl coating adhesive and a preparation method thereof: the coating glue is prepared by compounding polymethylphenylsiloxane, linear aliphatic hydrocarbon solvent oil diluent, alkoxy silane cross-linking agent, catalyst, tackifier and the like. Condensation dealcoholization reaction is carried out on hydroxyl-terminated silicone oil and alkoxy silane, and surface drying is carried out within 2-10 min at room temperature; after 7 days of curing, the adhesive film is deeply cured, has higher hardness and certain toughness, friction resistance and bending resistance. However, the coating adhesive can be only used for spraying, dipping, brushing, flow coating and other processes due to the use of a large amount of diluents such as n-heptane, environment-friendly solvent oil and the like.
Chinese patent CN105585997a discloses a single component, condensed, solvent-free organosilicon phenyl coating adhesive and preparation method thereof: the coating adhesive is prepared by compounding dimethoxy-end-capped polydimethylsiloxane, trimethoxy-end-capped polydimethylsiloxane, epoxy-group-containing polydimethylsiloxane, a cross-linking agent, a catalyst and the like. The alkoxysilane reacts with water in the air at high temperature to generate hydroxyl-terminated silane, the hydroxyl-terminated silane and the alkoxysilane undergo condensation dealcoholization reaction, and the surface drying time is 3-6 min at 80 ℃. However, the curing time of the coating adhesive at room temperature is long, and the strength of the obtained coating is poor, so that the application of the organosilicon coating adhesive is severely limited.
Chinese patent CN110591557B discloses a single-component, solvent-borne organosilicon phenyl coating adhesive and a preparation method thereof: firstly synthesizing phenyl silicone resin containing hydroxyl through phenyl trimethoxy silane under the action of an acid catalyst, adding hydroxyl silicone oil and ferric chloride for reaction after washing, adding methyl trimethoxy silane and tetrabutyl titanate for reaction for end sealing, and finally removing excessive methyl trimethoxy silane and partial solvent through low removal to obtain the product with 80% of solid content. But the coating still has more toluene solvent.
In the conventional preparation process of the three-proofing adhesive, a large amount of organic solvents such as toluene and n-heptane are used in part of the patents, and the solvents have bad influence on the health of human bodies, so that the use of the three-proofing adhesive is greatly limited. In conclusion, developing an organosilicon three-proofing adhesive which is economical and environment-friendly, convenient to use, excellent in performance, fast in curing and excellent in storage stability becomes a technical problem to be solved urgently by those skilled in the art.
Disclosure of Invention
In view of the above, the invention aims to provide the single-component solvent-free organosilicon three-proofing adhesive and the preparation method thereof, and the single-component solvent-free organosilicon three-proofing adhesive provided by the invention has the advantages of quick solidification and no solvent, has higher hardness while each performance meets the coating requirement of a circuit board, has very smooth surface after solidification, has excellent anti-friction performance, and can play a good role in protecting the surface of the circuit board by coating a very thin layer.
The invention provides a single-component solvent-free organic silicon three-proofing adhesive which is prepared from the following raw materials:
100 parts by weight of an alkoxy-terminated polysiloxane;
1-5 parts of cross-linking agent;
0.1 to 0.5 weight portion of titanium catalyst;
0.01 to 0.1 weight portion of ultraviolet indicator;
0.5 to 1.5 weight portions of tackifier;
the alkoxy-terminated polysiloxane is prepared from MT silicone oil and modified silicone oil; the cross-linking agent is selected from one or more of methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane and tetraethoxysilane.
Preferably, the MT silicone oil has a general formula:
(Me 2 R 1 SiO 0.5 ) a (Me 2 R 2 SiO 0.5 ) b (R 3 SiO 1.5 ) c ；
wherein R is 1 Alkenyl of 2 to 10 carbon atoms, R 2 Is C2-10 alkyl, R 3 Is one or two of methyl, ethyl, propyl, phenyl and benzyl; (a+b)/c is more than or equal to 0.4 and less than or equal to 0.8.
Preferably, the preparation method of the MT silicone oil specifically comprises the following steps:
mixing alkyl trimethoxy silane and/or aryl trimethoxy silane, tetramethyl dienyl disiloxane, an organic solvent, acid and water, heating to 60-100 ℃ and reacting for 1-12 h; after standing and layering, washing an organic layer with water, adding an aqueous solution of alkali to adjust the pH to 8-14, heating to 120-130 ℃ for water diversion reflux reaction for 1-5 h, cooling, neutralizing and washing with water, taking the organic layer, standing, filtering and distilling under reduced pressure to obtain MT silicone oil.
Preferably, the general formula of the modified silicone oil is:
HMe 2 SiO(R 3 R 4 SiO 1.0 ) d -Me 2 Si-(CH 2 ) 2 -Si(OMe) 3 ；
wherein R is 3 Is methyl, ethyl, isopropyl or phenyl, R 4 Methyl, ethyl, isopropyl or phenyl; d is more than or equal to 10 and less than 100.
Preferably, the preparation method of the modified silicone oil specifically comprises the following steps:
mixing tetramethyl dihydro disiloxane, methyl ring and cation exchange resin, heating to 50-80 ℃ for reaction for 10-15 h, filtering and removing low pressure to obtain hydrogen-containing silicone oil; and then mixing the hydrogen-containing silicone oil and toluene, heating to 60-80 ℃, dropwise adding a mixed solution of vinyl trimethoxy silane and karstedt catalyst, wherein the reaction temperature is not more than 90 ℃ during dropwise adding, continuing to react for 0.5-1.5 h after dropwise adding, cooling, adding activated carbon for adsorption filtration, and distilling under reduced pressure to obtain the modified silicone oil with one end sealed by hydrogen and one end sealed by methoxy.
Preferably, the preparation method of the alkoxy-terminated polysiloxane specifically comprises the following steps:
mixing MT silicone oil and a catalyst, heating to 70-90 ℃, dropwise adding modified silicone oil, continuing to react for 0.5-1.5 h after dropwise adding, cooling, adding activated carbon for adsorption filtration, and distilling under reduced pressure to obtain alkoxy-terminated polysiloxane.
Preferably, the titanium catalyst is a titanate catalyst.
Preferably, the ultraviolet indicator is selected from one or more of 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2-hydroxy-3, 5-di-tert-phenyl) -5-chlorobenzotriazole and 2,4, 6-tris (2-n-butoxyphenyl) -1,3, 5-triazine.
Preferably, the tackifier is selected from one or more of gamma-glycidol ether oxypropyl trimethoxysilane, aminopropyl triethoxysilane and gamma-aminoethylaminopropyl trimethoxysilane.
The invention also provides a preparation method of the single-component solvent-free organosilicon three-proofing adhesive, which comprises the following steps:
and uniformly mixing the alkoxy-terminated polysiloxane, the cross-linking agent, the titanium catalyst, the ultraviolet indicator and the tackifier to obtain the single-component solvent-free organosilicon three-proofing adhesive.
The invention provides a single-component solvent-free organic silicon three-proofing adhesive which is prepared from the following raw materials: 100 parts by weight of an alkoxy-terminated polysiloxane; 1-5 parts of cross-linking agent; 0.1 to 0.5 weight portion of titanium catalyst; 0.01 to 0.1 weight portion of ultraviolet indicator; 0.5 to 1.5 weight portions of tackifier; the alkoxy-terminated polysiloxane is prepared from MT silicone oil and modified silicone oil; the cross-linking agent is selected from one or more of methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane and tetraethoxysilane. Compared with the prior art, the single-component solvent-free organic silicon three-proofing adhesive provided by the invention adopts components with specific content, realizes better overall interaction, has the advantages of quick solidification and no solvent, has higher hardness while each performance meets the coating requirement of a circuit board, has very smooth surface after solidification, has excellent anti-friction performance, and can play a good role in protecting the circuit board by coating a very thin layer on the surface.
In addition, the preparation method provided by the invention has the advantages of simple process, mild and easily controlled conditions and wide application prospect.
Drawings
FIG. 1 is a schematic representation of the synthesis of alkoxy-terminated polysiloxanes;
fig. 2 is a schematic curing diagram of the single-component solvent-free silicone three-proofing adhesive provided by the invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a single-component solvent-free organic silicon three-proofing adhesive which is prepared from the following raw materials:
100 parts by weight of an alkoxy-terminated polysiloxane;
1-5 parts of cross-linking agent;
0.1 to 0.5 weight portion of titanium catalyst;
0.01 to 0.1 weight portion of ultraviolet indicator;
0.5 to 1.5 weight portions of tackifier;
the alkoxy-terminated polysiloxane is prepared from MT silicone oil and modified silicone oil; the cross-linking agent is selected from one or more of methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane and tetraethoxysilane.
In the invention, the single-component solvent-free organosilicon three-proofing adhesive is prepared from raw materials comprising alkoxy-terminated polysiloxane, a cross-linking agent, a titanium catalyst, an ultraviolet indicator and a tackifier, and is preferably prepared from raw materials comprising alkoxy-terminated polysiloxane, a cross-linking agent, a titanium catalyst, an ultraviolet indicator and a tackifier.
In the invention, the alkoxy-terminated polysiloxane is prepared from MT silicone oil and modified silicone oil; wherein, the general formula of MT silicone oil is preferably:
(Me 2 R 1 SiO 0.5 ) a (Me 2 R 2 SiO 0.5 ) b (R 3 SiO 1.5 ) c ；
wherein R is 1 Alkenyl of 2 to 10 carbon atoms, R 2 Is C2-10 alkyl, R 3 Is one or two of methyl, ethyl, propyl, phenyl and benzyl; (a+b)/c is more than or equal to 0.4 and less than or equal to 0.8.
In the present invention, R 1 Alkenyl of 2 to 10 carbon atoms, wherein the alkenyl of 2 to 10 carbon atoms is directly bonded to a silicon atom and can be vinyl, allyl, butenyl, hexenyl and the like; vinyl groups are preferred from the viewpoints of reactivity in addition reaction and easiness of synthesis of organopolysiloxane.
In the present invention, R 2 The alkyl group having 2 to 10 carbon atoms, wherein the alkyl group having 2 to 10 carbon atoms is directly bonded to a silicon atom, and may be methyl, ethyl, isopropyl, n-propyl, etc., preferably methyl.
In the present invention, R 3 Methyl, ethyl, propyl, phenyl and benzyl, preferably phenyl or, a combination of methyl and phenyl; r is R 3 Is directly bonded to a silicon atom and is selected from substituted monovalent hydrocarbon radicals (e.g., alkyl or aryl, excluding alkenyl).
In the present invention, subscripts a and b represent the average number of alkenyl groups relative to the silicon atom in the formula of MT silicone oil; subscript c represents the average number of groups in the substituted monovalent hydrocarbon group relative to the silicon atom in the formula of the MT silicone oil; (a+b)/c is more than or equal to 0.4 and less than or equal to 0.8, namely, the value of (a+b)/c is between 0.4 and 0.8, preferably between 0.5 and 0.7; when the value is more than 0.8, the polysiloxane has a low molecular weight, and does not provide sufficient strength and properties to the cured resin; and when the value is less than 0.4, the polysiloxane appears as a solid to be ineffective for grafting; for ease of calculation, c=1 is preferably employed.
On this basis, the MT silicone oil can be expressed as:
(Me 2 ViSiO 0.5 ) a (Me 3 SiO 0.5 ) b (PhSiO 1.5 ) 1 ；
(Me 2 ViSiO 0.5 ) a (Me 3 SiO 0.5 ) b (MeSiO 1.5 ) 1 ；
(Me 2 ViSiO 0.5 ) a (Me 3 SiO 0.5 ) b (MeSiO 1.5 ) x (PhSiO 1.5 ) 1-x ；
wherein X is more than or equal to 0 and less than or equal to 1.
In the invention, the preparation method of the MT silicone oil preferably comprises the following specific steps:
mixing alkyl trimethoxy silane and/or aryl trimethoxy silane, tetramethyl dienyl disiloxane, an organic solvent, acid and water, heating to 60-100 ℃ and reacting for 1-12 h; after standing and layering, washing an organic layer with water, adding an alkali aqueous solution to adjust the pH to 8-14, heating to 120-130 ℃ to carry out water diversion reflux reaction for 1-5 h, cooling, neutralizing and washing with water, taking the organic layer, standing, filtering and distilling under reduced pressure to obtain MT silicone oil;
more preferably:
mixing alkyl trimethoxy silane and/or aryl trimethoxy silane, tetramethyl dienyl disiloxane, an organic solvent, acid and water, heating to 70-80 ℃ and reacting for 2-6 h; after standing and layering, washing an organic layer with water, adding an aqueous solution of alkali to adjust the pH to 10-12, heating to 120 ℃ for water diversion reflux reaction for 3h, cooling, neutralizing and washing with water, taking the organic layer, standing, filtering and distilling under reduced pressure to obtain MT silicone oil.
In the present invention, the organic solvent is preferably toluene; the acid is preferably trifluoromethanesulfonic acid. The sources of the above-mentioned alkyl trimethoxysilane, aryl trimethoxysilane, tetramethyl dienyl disiloxane, organic solvent and acid are not particularly limited, and commercially available products known to those skilled in the art may be used.
In a preferred embodiment of the invention, the mixing is performed by:
adding aryl trimethoxy silane and tetramethyl divinyl disiloxane into a reaction kettle, adding an organic solvent and acid, and gradually dropwise adding water into the reaction kettle within 2 hours under the protection of nitrogen.
In another preferred embodiment of the present invention, the mixing process is:
adding alkyl trimethoxy silane and tetramethyl divinyl disiloxane into a reaction kettle, adding an organic solvent and an acid, and gradually dropwise adding water into the reaction kettle within 2 hours under the protection of nitrogen.
In another preferred embodiment of the present invention, the mixing process is:
adding tetramethyl divinyl disiloxane into a reaction kettle, adding an organic solvent, acid and water, and gradually dropwise adding alkyl trimethoxy silane and aryl trimethoxy silane into the reaction kettle within 2 hours under the protection of nitrogen.
In the present invention, the washing process is preferably performed four to five times.
In the present invention, the aqueous alkali solution is preferably a 20wt% to 30wt% aqueous potassium hydroxide solution.
In the present invention, the general formula of the modified silicone oil is preferably:
HMe 2 SiO(R 3 R 4 SiO 1.0 ) d -Me 2 Si-(CH 2 ) 2 -Si(OMe) 3 ；
wherein R is 3 Methyl, ethyl, isopropyl or phenyl, preferably methyl; r is R 4 Methyl, ethyl, isopropyl or phenyl, preferably methyl; d is more than or equal to 10 and less than or equal to 100, preferably more than or equal to 20 and less than or equal to 50.
In the invention, the preparation method of the modified silicone oil preferably comprises the following specific steps:
mixing tetramethyl dihydro disiloxane, methyl ring and cation exchange resin, heating to 50-80 ℃ for reaction for 10-15 h, filtering and removing low pressure to obtain hydrogen-containing silicone oil; mixing the hydrogen-containing silicone oil and toluene, heating to 60-80 ℃, dropwise adding a mixed solution of vinyl trimethoxy silane and karstedt catalyst, wherein the reaction temperature is not more than 90 ℃ during dropwise adding, continuing to react for 0.5-1.5 h after dropwise adding, cooling, adding activated carbon for adsorption filtration, and distilling under reduced pressure to obtain modified silicone oil with one end sealed by hydrogen and one end sealed by methoxy;
more preferably:
mixing tetramethyl dihydro disiloxane, methyl ring and cation exchange resin, heating to 60 ℃, performing airtight reaction for 12 hours, filtering and removing low pressure to obtain hydrogen-containing silicone oil; and mixing the hydrogen-containing silicone oil with toluene, heating to 70 ℃, dropwise adding a mixed solution of vinyl trimethoxy silane and karstedt catalyst, wherein the reaction temperature is not more than 90 ℃ during dropwise adding, continuing to react for 1h after dropwise adding, cooling, adding activated carbon for adsorption filtration, and distilling under reduced pressure to obtain the modified silicone oil with one end blocked by hydrogen and one end blocked by methoxy.
In the present invention, the methyl ring is preferably octamethyl cyclotetrasiloxane. The sources of the tetramethyl dihydro disiloxane, methyl ring, cation exchange resin, vinyl trimethoxy silane, and karstedt catalyst are not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the invention, the target product of the hydrosilylation reaction is mono-hydrogen addition, and certain side reactions are necessarily present in the reaction to generate alkoxy-terminated silicone oil with both sides subjected to the hydrosilylation reaction; the value of the double addition product to the single addition product is preferably less than 0.3 after being tested by a gas chromatography mass spectrometer; and the hydrogen content of the modified silicone oil is tested by a titration method or nuclear magnetic resonance silicon spectrum, so that the subsequent synthesis of alkoxy-terminated polysiloxane is facilitated.
In the present invention, the preparation method of the alkoxy-terminated polysiloxane is preferably specifically:
mixing MT silicone oil and a catalyst, heating to 70-90 ℃, dropwise adding modified silicone oil, continuing to react for 0.5-1.5 h after dropwise adding, cooling, adding activated carbon for adsorption filtration, and distilling under reduced pressure to obtain alkoxy-terminated polysiloxane;
more preferably:
mixing MT silicone oil and a catalyst, heating to 80 ℃, dropwise adding modified silicone oil, reacting for 1h after dropwise adding, cooling, adding activated carbon for adsorption and filtration, and distilling under reduced pressure to obtain alkoxy-terminated polysiloxane. See fig. 1.
In the present invention, the catalyst is preferably a toluene solution of karstedt catalyst, in which the platinum content is preferably 0.1wt% to 1wt%. In the present invention, the catalyst is preferably added in an amount of 3 to 10ppm (calculated as platinum) to MT silicone oil.
In the present invention, the ratio of the MT silicone oil to the modified silicone oil is preferably such that the ratio of vinyl groups to hydrogen content is 1.05 to 2/1, so that a certain amount of MT silicone oil does not participate in the reaction.
In the present invention, the alkoxy-terminated polysiloxane may be represented by the following general formula:
(R 1 SiO 1.5 ) 1 [-Me 2 SiO-(CH 2 ) 2 -(MeSiO 1.0 ) d -(CH 2 ) 2 -Si(OMe) 3 ] a 。
in the present invention, the one-part solvent-free silicone tri-proof adhesive comprises 100 parts by weight of an alkoxy-terminated polysiloxane.
In the present invention, the crosslinking agent is preferably one or more selected from methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane and tetraethoxysilane, more preferably tetraethoxysilane. The source of the crosslinking agent is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the invention, the single-component solvent-free organosilicon three-proofing adhesive comprises 1 to 5 parts by weight of cross-linking agent, preferably 2 parts by weight.
In the present invention, the titanium catalyst is preferably a titanate-based catalyst; such as tetrabutyl titanate, isopropyl titanate, tetraethyl titanate, commercial titanate chelates, and the like; the source of the titanium catalyst is not particularly limited in the present invention, and commercially available products of the above-mentioned titanate-based catalysts, which are well known to those skilled in the art, may be used.
In the present invention, the one-component solvent-free silicone three-way adhesive comprises 0.1 to 0.5 part by weight of a titanium catalyst, preferably 0.2 part by weight.
In the present invention, the ultraviolet indicator is preferably selected from one or more of 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2-hydroxy-3, 5-di-tert-phenyl) -5-chlorobenzotriazole and 2,4, 6-tris (2-n-butoxyphenyl) -1,3, 5-triazine, more preferably 2, 4-dihydroxybenzophenone. The source of the ultraviolet indicator is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the one-component solvent-free silicone three-way adhesive comprises 0.01 to 0.1 part by weight of an ultraviolet indicator, preferably 0.012 part by weight.
In the present invention, the tackifier is preferably one or more selected from the group consisting of gamma-glycidoxypropyl trimethoxysilane, aminopropyl triethoxysilane, and gamma-aminoethylaminopropyl trimethoxysilane, more preferably aminopropyl trimethoxysilane. The source of the tackifier is not particularly limited and commercially available products known to those skilled in the art may be used.
In the present invention, the one-component solvent-free silicone three-way adhesive comprises 0.5 to 1.5 parts by weight of a tackifier, preferably 0.8 parts by weight.
The single-component solvent-free organosilicon three-proofing adhesive provided by the invention adopts components with specific content, realizes better overall interaction, has the advantages of quick solidification and no solvent, has higher hardness while each performance meets the coating requirement of a circuit board, has very smooth surface after solidification, has excellent anti-friction performance, and can play a good role in protecting by coating a very thin layer on the surface of the circuit board. A schematic curing is shown in fig. 2.
The invention also provides a preparation method of the single-component solvent-free organosilicon three-proofing adhesive, which comprises the following steps:
and uniformly mixing the alkoxy-terminated polysiloxane, the cross-linking agent, the titanium catalyst, the ultraviolet indicator and the tackifier to obtain the single-component solvent-free organosilicon three-proofing adhesive.
The preparation method provided by the invention has the advantages of simple process, mild and easily controlled conditions and wide application prospect.
The invention provides a single-component solvent-free organic silicon three-proofing adhesive which is prepared from the following raw materials: 100 parts by weight of an alkoxy-terminated polysiloxane; 1-5 parts of cross-linking agent; 0.1 to 0.5 weight portion of titanium catalyst; 0.01 to 0.1 weight portion of ultraviolet indicator; 0.5 to 1.5 weight portions of tackifier; the alkoxy-terminated polysiloxane is prepared from MT silicone oil and modified silicone oil; the cross-linking agent is selected from one or more of methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane and tetraethoxysilane. Compared with the prior art, the single-component solvent-free organic silicon three-proofing adhesive provided by the invention adopts components with specific content, realizes better overall interaction, has the advantages of quick solidification and no solvent, has higher hardness while each performance meets the coating requirement of a circuit board, has very smooth surface after solidification, has excellent anti-friction performance, and can play a good role in protecting the circuit board by coating a very thin layer on the surface.
In addition, the preparation method provided by the invention has the advantages of simple process, mild and easily controlled conditions and wide application prospect.
In order to further illustrate the present invention, the following examples are provided. The raw materials used in the following examples of the present invention are all commercially available.
Example 1
198.29g of phenyl trimethoxy silane and 55.92g of tetramethyl divinyl disiloxane are taken and added into a reaction kettle, 290g of toluene and 0.58g of trifluoro methanesulfonic acid are added, 54g of water is gradually added into the reaction kettle dropwise within 2 hours under the protection of nitrogen, and the temperature is raised to 80 ℃ for reaction for 3 hours after the completion of the dropwise addition; standing and layering are carried out after the reaction is finished,separating an upper water layer, washing with water for 4 times, adding 300g of water for each washing, taking an organic layer, adding 0.47g of 25wt% potassium hydroxide aqueous solution to adjust the pH to 10-12, heating to 120 ℃, and carrying out water diversion reflux reaction for 3h; cooling to 60 ℃ after the reaction is finished, adding 0.19g of acetic acid, and stirring for 1h at normal temperature; washing with water for 4 times, wherein the water adding amount of each washing is 300g; taking an organic layer, standing, filtering, heating to 120 ℃ and distilling under reduced pressure by an oil pump to remove low-boiling-point substances to obtain MT silicone oil products; the expression of the product is (Me) 2 ViSiO 0.5 ) 0.6 (PhSiO 1.5 ) 1 The vinyl content is 8.59% by the vinyl titration method, which is not much different from the theoretical value of 8.77%.
Example 2
136.22g of methyltrimethoxysilane and 46.6g of tetramethyl divinyl disiloxane are taken and added into a reaction kettle, 290g of toluene and 0.45g of trifluoromethanesulfonic acid are added, 54g of water is gradually added into the reaction kettle dropwise within 2 hours under the protection of nitrogen, and the temperature is raised to 80 ℃ for reaction for 3 hours after the completion of the dropwise addition; standing and layering after the reaction is finished, separating an upper water layer, washing for 4 times, adding 300g of water for each washing, taking an organic layer, adding 0.47g of 25wt% potassium hydroxide aqueous solution to adjust the pH to 10-12, heating to 120 ℃, and carrying out water diversion reflux reaction for 3h; cooling to 60 ℃ after the reaction is finished, adding 0.19g of acetic acid, and stirring for 1h at normal temperature; washing with water for 4 times, wherein the water adding amount of each washing is 300g; taking an organic layer, standing, filtering, heating to 120 ℃ and distilling under reduced pressure by an oil pump to remove low-boiling-point substances to obtain MT silicone oil products; the expression of the product is (Me) 2 ViSiO 0.5 ) 0.5 (MeSiO 1.5 ) 1 The vinyl content is 7.45% by the vinyl titration method, which is not much different from the theoretical value of 7.69%.
Example 3
Adding 55.92g of tetramethyl divinyl disiloxane into a reaction kettle, adding 290g of toluene, 0.58g of trifluoromethanesulfonic acid and 54g of deionized water, gradually dropwise adding 68.11g of methyltrimethoxysilane and 99.15g of phenyltrimethoxysilane into the reaction kettle within 2 hours under the protection of nitrogen, and heating to 80 ℃ for reaction for 3 hours after the dropwise adding of the alkoxy silane is completed; standing and separating after the reaction is finishedSeparating an upper water layer, washing with water for 4 times, adding 300g of water for each washing, taking an organic layer, adding 0.47g of 25wt% potassium hydroxide aqueous solution to adjust the pH to 10-12, heating to 120 ℃, and carrying out water diversion reflux reaction for 3h; cooling to 60 ℃ after the reaction is finished, adding 0.19g of acetic acid, and stirring for 1h at normal temperature; washing with water for 4 times, wherein the water adding amount of each washing is 300g; taking an organic layer, standing, filtering, heating to 120 ℃ and distilling under reduced pressure by an oil pump to remove low-boiling-point substances to obtain MT silicone oil products; the expression of the product is (Me) 2 ViSiO 0.5 ) 0.6 (MeSiO 1.5 ) 0.5 (PhSiO 1.5 ) 0.5 The vinyl titration method tests that the vinyl content is 10.21% and is not much different from the theoretical value of 10.53%.
Comparative example 1
136.22g of methyltrimethoxysilane and 18.64g of tetramethyl divinyl disiloxane are taken and added into a reaction kettle, 290g of toluene and 0.45g of trifluoromethanesulfonic acid are added, 54g of water is gradually added into the reaction kettle dropwise within 2 hours under the protection of nitrogen, and the temperature is raised to 80 ℃ for reaction for 3 hours after the completion of the dropwise addition; standing and layering after the reaction is finished, separating an upper water layer, washing for 4 times, adding 300g of water for each washing, taking an organic layer, adding 0.47g of 25wt% potassium hydroxide aqueous solution to adjust the pH to 10-12, heating to 120 ℃, and carrying out water diversion reflux reaction for 3h; cooling to 60 ℃ after the reaction is finished, adding 0.19g of acetic acid, and stirring for 1h at normal temperature; washing with water for 4 times, wherein the water adding amount of each washing is 300g; taking an organic layer, standing, filtering, heating to 120 ℃ and distilling under reduced pressure by an oil pump to remove low-boiling-point substances to obtain an MT silicon resin product; the expression of the product is (Me) 2 ViSiO 0.5 ) 0.2 (MeSiO 1.5 ) 1 The product is solid at room temperature, so the product is not called MT silicone oil, and is tested by a vinyl titration method, wherein the vinyl content is 6.24% and is not much different from the theoretical value of 6.31%.
Comparative example 2
136.22g of methyltrimethoxysilane and 186.4g of tetramethyl divinyl disiloxane are taken and added into a reaction kettle, 290g of toluene and 0.45g of trifluoromethanesulfonic acid are added, 54g of water is gradually added into the reaction kettle in a dropwise manner within 2 hours under the protection of nitrogen, and the mixture is lifted after the water drop is finishedReacting for 3 hours at the temperature of 80 ℃; standing and layering after the reaction is finished, separating an upper water layer, washing for 4 times, adding 300g of water for each washing, taking an organic layer, adding 0.47g of 25wt% potassium hydroxide aqueous solution to adjust the pH to 10-12, heating to 120 ℃, and carrying out water diversion reflux reaction for 3h; cooling to 60 ℃ after the reaction is finished, adding 0.19g of acetic acid, and stirring for 1h at normal temperature; washing with water for 4 times, wherein the water adding amount of each washing is 300g; taking an organic layer, standing, filtering, heating to 120 ℃ and distilling under reduced pressure by an oil pump to remove low-boiling-point substances to obtain MT silicone oil products; the expression of the product is (Me) 2 ViSiO 0.5 ) 2 (MeSiO 1.5 ) 1 The vinyl content of the product is 21.07% as measured by vinyl titration, which is not much different from the theoretical value of 21.34%.
Example 4
13.43g of tetramethyl dihydro disiloxane, 370g of octamethyl cyclo-tetrasiloxane and 19.17g of cation exchange resin are added into a flask, the temperature is raised to 60 ℃ for closed reaction for 12 hours, filtration and low removal are carried out, and the structure HMe is obtained 2 SiO(Me 2 SiO 1.0 ) 50 SiMe 2 H hydrogen-containing silicone oil; then adding 383.43g of hydrogen-containing silicone oil and 400g of toluene into a four-neck flask with a thermometer, heating to 70 ℃, dropwise adding 14.82g of vinyl trimethoxy silane and 0.41g of toluene solution of karstedt catalyst (wherein the platinum content is 0.5 wt%) at the reaction temperature of not more than 90 ℃, continuing to react for 1h after the dropwise adding, cooling, adding activated carbon for adsorption filtration, and distilling under reduced pressure to obtain the modified silicone oil with one end blocked by hydrogen and one end blocked by methoxy, wherein the expression of the product is HMe 2 SiO(Me 2 SiO 1.0 ) 50 -Me 2 Si-(CH 2 ) 2 -Si(OMe) 3 。
Example 5
13.43g of tetramethyl dihydro disiloxane, 148g of octamethyl cyclotetrasiloxane and 19.17g of cation exchange resin are added into a flask, the temperature is raised to 60 ℃ for closed reaction for 12 hours, filtration and low removal are carried out, and the structure HMe is obtained 2 SiO(Me 2 SiO 1.0 ) 20 SiMe 2 H hydrogen-containing silicone oil; then 161.43g of hydrogen-containing silicone oil and 400g of toluene were added to a four-port burner with thermometerIn a bottle, heating to 70 ℃, dropwise adding 14.82g of vinyltrimethoxysilane and 0.41g of toluene solution of karstedt catalyst (wherein the platinum content is 0.5 wt%) at the reaction temperature of not more than 90 ℃, continuing to react for 1h after the dropwise adding, cooling, adding active carbon for adsorption filtration, and distilling under reduced pressure to obtain modified silicone oil with one end being hydrogen-containing and one end being methoxy-terminated, wherein the expression of the product is HMe 2 SiO(Me 2 SiO 1.0 ) 20 -Me 2 Si-(CH 2 ) 2 -Si(OMe) 3 。
Example 6
277.2g of phenyl vinyl MT silicone oil in the above example 1, 200g of toluene and 0.41g of toluene solution of karstedt catalyst (wherein the platinum content is 0.5 wt%) were added, stirred uniformly, heated to 80 ℃, 3982g of modified silicone oil in the above example 4 was added dropwise, after the addition was completed, the reaction was continued for 1 hour at 80 ℃, activated carbon was added for adsorption filtration after cooling, and vacuum distillation was performed to obtain alkoxy-terminated phenyl polysiloxane, the expression of which is:
(PhSiO 1.5 ) 1 [-Me 2 SiO-(CH 2 ) 2 -(MeSiO 1.0 ) 50 -(CH 2 ) 2 -Si(OMe) 3 ] 0.6 。
the above-mentioned phenylvinyl MT silicone oil and modified silicone oil are fed in a molar ratio of vinyl group/hydrogen content of 1.5/1, so that a certain amount of phenylvinyl MT silicone oil does not participate in the reaction.
Adding 2wt% (the weight percent of the organosilicon three-proofing glue component is relative to the weight percent of the alkoxy-terminated polysiloxane, and the description is omitted below) of tetraethoxysilane, 0.2wt% of tetrabutyl titanate, 0.012wt% of 2, 4-dihydroxybenzophenone and 0.8wt% of aminopropyl trimethoxysilane into the obtained product, and uniformly mixing to obtain the organosilicon three-proofing glue.
Example 7
170.25g of methyl vinyl MT silicone oil in the above example 2, 200g of toluene and 0.41g of toluene solution of karstedt catalyst (the platinum content is 0.5 wt%) are added, stirring is uniform, the temperature is raised to 80 ℃, 3982g of modified silicone oil in the above example 4 is added dropwise, after the dropwise addition is finished, the reaction is continued for 1h at 80 ℃, activated carbon is added for adsorption filtration after cooling, and vacuum distillation is performed, so that alkoxy-terminated phenyl polysiloxane is obtained, and the expression of the product is:
(MeSiO 1.5 ) 1 [-Me 2 SiO-(CH 2 ) 2 -(MeSiO 1.0 ) 50 -(CH 2 ) 2 -Si(OMe) 3 ] 0.5 。
the above-mentioned methyl vinyl MT silicone oil and modified silicone oil are fed in a molar ratio of vinyl group/hydrogen content of 1.5/1, so that a certain amount of methyl vinyl MT silicone oil does not participate in the reaction.
Adding 2wt% of tetraethoxysilane, 0.2wt% of tetrabutyl titanate, 0.012wt% of 2, 4-dihydroxybenzophenone and 0.8wt% of aminopropyl trimethoxysilane into the obtained product, and uniformly mixing to obtain the organosilicon three-proofing adhesive.
Example 8
230.7g of methyl phenyl vinyl MT silicone oil in the above example 3, 200g of toluene and 0.41g of toluene solution of karstedt catalyst (the platinum content is 0.5 wt%) are added, stirring is uniform, the temperature is raised to 80 ℃, 3982g of modified silicone oil in the above example 4 is added dropwise, after the dropwise addition is finished, the reaction is continued for 1h at 80 ℃, activated carbon is added for adsorption filtration after cooling, and vacuum distillation is performed, so that alkoxy-terminated phenyl polysiloxane is obtained, and the expression of the product is:
(PhSiO 1.5 ) 0.5 (MeSiO 1.5 ) 0.5 [-Me 2 SiO-(CH 2 ) 2 -(MeSiO 1.0 ) 50 -(CH 2 ) 2 -Si(OMe) 3 ] 0.6 。
the ratio of the methyl phenyl vinyl MT silicone oil to the modified silicone oil is fed according to the mol ratio of vinyl/hydrogen content of 1.5/1, so that a certain amount of methyl phenyl vinyl MT silicone oil does not participate in the reaction.
Adding 2wt% of tetraethoxysilane, 0.2wt% of tetrabutyl titanate, 0.012wt% of 2, 4-dihydroxybenzophenone and 0.8wt% of aminopropyl trimethoxysilane into the obtained product, and uniformly mixing to obtain the organosilicon three-proofing adhesive.
Example 9
194.04g of phenyl vinyl MT silicone oil in the above example 1, 200g of toluene and 0.41g of toluene solution of karstedt catalyst (wherein the platinum content is 0.5 wt%) were added, stirred uniformly, heated to 80 ℃, 1762g of modified silicone oil in the above example 5 was added dropwise, after the addition was completed, the reaction was continued for 1 hour at 80 ℃, after cooling, activated carbon was added for adsorption filtration, and distillation under reduced pressure was performed to obtain alkoxy-terminated phenyl polysiloxane, the expression of which is:
(PhSiO 1.5 ) 1 [-Me 2 SiO-(CH 2 ) 2 -(MeSiO 1.0 ) 20 -(CH 2 ) 2 -Si(OMe) 3 ] 0.6 。
the above-mentioned phenylvinyl MT silicone oil and modified silicone oil are fed in a molar ratio of vinyl group/hydrogen content of 1.05/1, so that a certain amount of phenylvinyl MT silicone oil does not participate in the reaction.
Adding 2wt% of tetraethoxysilane, 0.2wt% of tetrabutyl titanate, 0.012wt% of 2, 4-dihydroxybenzophenone and 0.8wt% of aminopropyl trimethoxysilane into the obtained product, and uniformly mixing to obtain the organosilicon three-proofing adhesive.
Comparative example 3
89.88g of methyl vinyl MT silicone resin in the comparative example 1 is added with 200g of toluene and 0.41g of toluene solution of karstedt catalyst (the platinum content is 0.5 wt%) and stirred uniformly, the temperature is raised to 80 ℃, 1762g of modified silicone oil in the example 5 is added dropwise, after the dropwise addition is finished, the reaction is continued for 1h at 80 ℃, activated carbon is added for adsorption filtration after cooling, and vacuum distillation is carried out, thus obtaining alkoxy-terminated phenyl polysiloxane, and the expression of the product is as follows:
(MeSiO 1.5 ) 1 [-Me 2 SiO-(CH 2 ) 2 -(MeSiO 1.0 ) 20 -(CH 2 ) 2 -Si(OMe) 3 ] 0.2 。
the above-mentioned methyl vinyl MT silicone oil and modified silicone oil are fed in a molar ratio of vinyl group/hydrogen content of 1.05/1, so that a certain amount of methyl vinyl MT silicone oil does not participate in the reaction.
The above products are solid at room temperature and require the addition of solvents to dissolve, and thus the scheme is not suitable for the present invention.
Comparative example 4
265.65g of methyl vinyl MT silicone oil in the comparative example 2 is added with 200g of toluene and 0.41g of toluene solution of karstedt catalyst (the platinum content is 0.5 wt%) and stirred uniformly, the temperature is raised to 80 ℃, 1762g of modified silicone oil in the example 5 is added dropwise, after the dropwise addition is finished, the reaction is continued for 1h at 80 ℃, after cooling, activated carbon is added for adsorption filtration, and reduced pressure distillation is carried out, thus obtaining alkoxy-terminated phenyl polysiloxane, and the expression of the product is:
(MeSiO 1.5 ) 1 [-Me 2 SiO-(CH 2 ) 2 -(MeSiO 1.0 ) 20 -(CH 2 ) 2 -Si(OMe) 3 ] 2 。
the above-mentioned methyl vinyl MT silicone oil and modified silicone oil are fed in a molar ratio of vinyl group/hydrogen content of 1.05/1, so that a certain amount of methyl vinyl MT silicone oil does not participate in the reaction.
Adding 2wt% of tetraethoxysilane, 0.2wt% of tetrabutyl titanate, 0.012wt% of 2, 4-dihydroxybenzophenone and 0.8wt% of aminopropyl trimethoxysilane into the obtained product, and uniformly mixing to obtain the organosilicon three-proofing adhesive.
The silicone three-proofing adhesives provided in examples 6 to 9 of the present invention and comparative example 4 were tested for each property, and the results are shown in table 1.
Table 1 various performance data for the silicone tri-resist provided in inventive examples 6-9 and comparative example 4
As can be seen from table 1, the silicone three-proofing adhesive provided in examples 6, 8 and 9 of the present invention has higher hardness (more than 75A) while each performance meets the coating requirement of the circuit board, the cured adhesive surface is very smooth, has excellent anti-friction performance, and a very thin layer of the surface of the circuit board can play a very good role in protection; whereas example 7 is mainly used in scenes where the strength requirement is not high but the toughness requirement is high; comparative example 4 failed to test the remaining data due to too slow curing speed.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A single-component solvent-free organic silicon three-proofing adhesive is prepared from the following raw materials:
100 parts by weight of an alkoxy-terminated polysiloxane;
1-5 parts of cross-linking agent;
0.1 to 0.5 weight portion of titanium catalyst;
0.01 to 0.1 weight portion of ultraviolet indicator;
0.5 to 1.5 weight portions of tackifier;
the alkoxy-terminated polysiloxane is prepared from MT silicone oil and modified silicone oil; the cross-linking agent is selected from one or more of methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane and tetraethoxysilane.
2. The single-component solventless silicone tri-proof adhesive of claim 1, wherein the MT silicone oil has the general formula:
(Me 2 R 1 SiO 0.5 ) a (Me 2 R 2 SiO 0.5 ) b (R 3 SiO 1.5 ) c ；
wherein R is 1 Alkenyl of 2 to 10 carbon atoms, R 2 Is C2-10 alkyl, R 3 Is one or two of methyl, ethyl, propyl, phenyl and benzyl; (a+b)/c is more than or equal to 0.4 and less than or equal to 0.8.
3. The single-component solvent-free organosilicon three-proofing adhesive according to claim 2, wherein the preparation method of MT silicone oil is specifically as follows:
mixing alkyl trimethoxy silane and/or aryl trimethoxy silane, tetramethyl dienyl disiloxane, an organic solvent, acid and water, heating to 60-100 ℃ and reacting for 1-12 h; after standing and layering, washing an organic layer with water, adding an aqueous solution of alkali to adjust the pH to 8-14, heating to 120-130 ℃ for water diversion reflux reaction for 1-5 h, cooling, neutralizing and washing with water, taking the organic layer, standing, filtering and distilling under reduced pressure to obtain MT silicone oil.
4. The single-component solventless silicone tri-proof adhesive of claim 1, wherein the modified silicone oil has the general formula:
HMe 2 SiO(R 3 R 4 SiO 1.0 ) d -Me 2 Si-(CH 2 ) 2 -Si(OMe) 3 ；
wherein R is 3 Is methyl, ethyl, isopropyl or phenyl, R 4 Methyl, ethyl, isopropyl or phenyl; d is more than or equal to 10 and less than 100.
5. The single-component solvent-free silicone three-proofing adhesive according to claim 4, wherein the preparation method of the modified silicone oil is specifically as follows:
mixing tetramethyl dihydro disiloxane, methyl ring and cation exchange resin, heating to 50-80 ℃ for reaction for 10-15 h, filtering and removing low pressure to obtain hydrogen-containing silicone oil; and then mixing the hydrogen-containing silicone oil and toluene, heating to 60-80 ℃, dropwise adding a mixed solution of vinyl trimethoxy silane and karstedt catalyst, wherein the reaction temperature is not more than 90 ℃ during dropwise adding, continuing to react for 0.5-1.5 h after dropwise adding, cooling, adding activated carbon for adsorption filtration, and distilling under reduced pressure to obtain the modified silicone oil with one end sealed by hydrogen and one end sealed by methoxy.
6. The one-component solventless silicone tri-proof adhesive of claim 1, wherein the alkoxy-terminated polysiloxane is prepared by a method comprising:
mixing MT silicone oil and a catalyst, heating to 70-90 ℃, dropwise adding modified silicone oil, continuing to react for 0.5-1.5 h after dropwise adding, cooling, adding activated carbon for adsorption filtration, and distilling under reduced pressure to obtain alkoxy-terminated polysiloxane.
7. The single-component solventless silicone three-way adhesive of claim 1, wherein the titanium catalyst is a titanate type catalyst.
8. The one-part solvent-free silicone tri-proof adhesive of claim 1, wherein the ultraviolet indicator is selected from one or more of 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2-hydroxy-3, 5-di-tert-phenyl) -5-chlorinated benzotriazole, and 2,4, 6-tris (2-n-butoxyphenyl) -1,3, 5-triazine.
9. The one-part solvent-free silicone tri-proof adhesive of claim 1, wherein the tackifier is selected from one or more of gamma-glycidoxypropyl trimethoxysilane, aminopropyl triethoxysilane, and gamma-aminoethyl aminopropyl trimethoxysilane.
10. A method for preparing the single-component solvent-free organosilicon three-proofing adhesive according to any one of claims 1-9, comprising the following steps:
and uniformly mixing the alkoxy-terminated polysiloxane, the cross-linking agent, the titanium catalyst, the ultraviolet indicator and the tackifier to obtain the single-component solvent-free organosilicon three-proofing adhesive.
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