CN103937257B - Organic silicone thixotropic agent and thixotropy addition type liquid silicone rubber - Google Patents
Organic silicone thixotropic agent and thixotropy addition type liquid silicone rubber Download PDFInfo
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- CN103937257B CN103937257B CN201410112176.6A CN201410112176A CN103937257B CN 103937257 B CN103937257 B CN 103937257B CN 201410112176 A CN201410112176 A CN 201410112176A CN 103937257 B CN103937257 B CN 103937257B
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- 239000013008 thixotropic agent Substances 0.000 title claims abstract description 56
- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 44
- 229920001296 polysiloxane Polymers 0.000 title abstract description 25
- 239000004944 Liquid Silicone Rubber Substances 0.000 title abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 230000004048 modification Effects 0.000 claims abstract description 20
- 238000012986 modification Methods 0.000 claims abstract description 20
- 125000004185 ester group Chemical group 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims description 72
- 239000001257 hydrogen Substances 0.000 claims description 62
- 229910052739 hydrogen Inorganic materials 0.000 claims description 62
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 45
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 36
- 239000004593 Epoxy Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 16
- 150000003254 radicals Chemical class 0.000 claims description 16
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 12
- 229920005601 base polymer Polymers 0.000 claims description 10
- 239000003112 inhibitor Substances 0.000 claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 9
- 125000003368 amide group Chemical group 0.000 claims description 8
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 229910003978 SiClx Inorganic materials 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- -1 polysiloxane Polymers 0.000 abstract description 45
- 125000003700 epoxy group Chemical group 0.000 abstract description 2
- 125000003277 amino group Chemical group 0.000 abstract 1
- 238000005538 encapsulation Methods 0.000 abstract 1
- 125000001033 ether group Chemical group 0.000 abstract 1
- 229920000260 silastic Polymers 0.000 description 36
- 229920002545 silicone oil Polymers 0.000 description 22
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 21
- 229920002554 vinyl polymer Polymers 0.000 description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 19
- 229910052710 silicon Inorganic materials 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000000377 silicon dioxide Substances 0.000 description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 16
- 125000000217 alkyl group Chemical group 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- 230000009974 thixotropic effect Effects 0.000 description 15
- 239000010703 silicon Substances 0.000 description 14
- 150000002431 hydrogen Chemical class 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 11
- 238000007711 solidification Methods 0.000 description 11
- 230000008023 solidification Effects 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 7
- 239000004945 silicone rubber Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000005292 vacuum distillation Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 125000003944 tolyl group Chemical group 0.000 description 5
- 125000005250 alkyl acrylate group Chemical group 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 125000002769 thiazolinyl group Chemical group 0.000 description 4
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical class O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- QTTMOCOWZLSYSV-QWAPEVOJSA-M equilin sodium sulfate Chemical compound [Na+].[O-]S(=O)(=O)OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4C3=CCC2=C1 QTTMOCOWZLSYSV-QWAPEVOJSA-M 0.000 description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 125000004344 phenylpropyl group Chemical group 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003376 silicon Chemical class 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RSNQKPMXXVDJFG-UHFFFAOYSA-N tetrasiloxane Chemical compound [SiH3]O[SiH2]O[SiH2]O[SiH3] RSNQKPMXXVDJFG-UHFFFAOYSA-N 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- 0 **(C1CC(C*2)C2CC1)N Chemical compound **(C1CC(C*2)C2CC1)N 0.000 description 1
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical group C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-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
- 239000004952 Polyamide Substances 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000013006 addition curing Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- MJULMZZKFYNTHK-UHFFFAOYSA-N ethenyl(phenyl)silicon Chemical compound C=C[Si]C1=CC=CC=C1 MJULMZZKFYNTHK-UHFFFAOYSA-N 0.000 description 1
- ARLJCLKHRZGWGL-UHFFFAOYSA-N ethenylsilicon Chemical compound [Si]C=C ARLJCLKHRZGWGL-UHFFFAOYSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010237 hybrid technique Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 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 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920002631 room-temperature vulcanizate silicone Polymers 0.000 description 1
- 150000003384 small molecules Chemical group 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Abstract
The invention discloses an organic silicone thixotropic agent and a thixotropy addition type liquid silicone rubber. The organic silicone thixotropic agent comprises modified polysiloxane and modified cyclosiloxane; and the modification groups in the modified polysiloxane and modified cyclosiloxane at least comprise one group of epoxy group, ether group, hydroxyl group, amine group, and ester group. The modification group content of the modified polysiloxane is 0.01 to 0.80 mol/100g, and the modification group content of the modified cyclosiloxane is 0.10 to 0.60 mol/100g. The organic silicone thixotropic agent can further comprise silicone dioxide. The invention further discloses a thixotropy addition type liquid silicone rubber containing the organic silicone thixotropic agent. After the provided organic silicone thixotropic agent is mixed with liquid silicone rubber, the thixotropy of liquid silicone rubber can be improved, and thus the liquid silicone rubber can satisfy the specific application occasion such as mould-free encapsulation, and the like.
Description
Technical field
The invention belongs to organosilicon material technical field, it is related to a kind of organosilicon thixotropic agent and thixotropy add-on type liquid silicon
Rubber.
Technical background
Liquid silastic is by polymer complex filler based on the linear polysiloxane of intermediate degree of polymerisation, various helps
What agent and additive were prepared has self-leveling or thixotropic base material, can according to kind and purposes extrusion, note type, coat after,
In an atmosphere or the lower vulcanization forming of heating is elastomer, including condensed room temperature vulcanized silicone rubber, condensed type one pack system rtv silicon rubber
Glue, add-on type liquid silicon rubber etc..Wherein, add-on type liquid silicon rubber is generally by base polymer, cross-linking agent, catalyst and suppression
Preparation forms, and needs typically also to include filler, additive etc. according to practical application and function, the vinyl in base polymer and
There is catalytic addition reaction in the si-h base in cross-linking agent, be cross-linked to form the product with network structure, can be divided according to manner of packing
For one-component and bi-component.Base polymer is the vinyl polysiloxane or vinyl silicon containing two or more vinyls
Oil, cross-linking agent is mainly the siloxane oligomer containing more than 3 si-h keys, i.e. low viscosity linear methyl silicone oil, catalyst
It is usually platinum group catalyst, the such as platinum catalyst of oxolane coordination, platinum-alkynes basigamy compound etc., inhibitor can postpone silicon hydrogen
Change additive reaction, extend storage period and the working life of silicone rubber, such as compound, filler and the additive containing alkynyl and many vinyls
Main reinforced filling, heat filling, conductive filler, coloring agent, tackifier, fire retardant, releasing agent etc. of including makes silicone rubber have
Specific function or the material meeting special process requirement, wherein reinforced filling can be mq type silicones, gas-phase silica etc..
Add-on type liquid silicon rubber needs with thixotropy in particular application, when thixotropy refers to that material is sheared
Denseness diminishes, and stopping denseness during shearing increases, or when being sheared, denseness becomes big, stops the phenomenon that during shearing, denseness diminishes, liquid
Body silicone rubber has higher requirements to its thixotropy in some special applications, for example Making mold, electronic module embedding,
The fields such as led lens packages, have the extruded rear straight forming of thixotropic liquid silastic, keep shape, are heating and curing
In journey and cured glue body does not deform, subsides, from without by mould assistant formation, its application can greatly simplify
Silicone rubber construction technology, reduces cost, improve production efficiency.At present, the thixotropic agent using in field of liquid silicone rubber includes two
Silicon oxide, white carbon black, organobentonite and castor oil hydrogenated, polyamide etc..Wherein, silicon dioxide is the most frequently used thixotropic agent, two
Silicon oxide particle aggregation can connect formation three dimensional silica network by the hydrogen bond between surface hydroxyl, so that liquid is wrapped in
In network structure, and lead to viscosity to increase thus molding, but the hydrogen bond between aggregation is weaker, the power that can be sheared is broken, and works as shearing
When power removes, hydrogen bond recovers, and makes liquid molding again.But silicon dioxide is powder body, complicated with the hybrid technique of liquid silastic,
High cost, can produce harmful effect to light transmittance of silicone rubber etc., the scope of application is restricted simultaneously, and organic molecule thixotroping
Agent is then usually present not good with liquid silastic Miscibility, bad dispersibility defect, leads to thixotropic improvement to system
Limited use.
Content of the invention
For above-mentioned the deficiencies in the prior art, the present invention provides a kind of organosilicon thixotropic agent and thixotropy add-on type liquid silicon
Rubber, described organosilicon thixotropic agent is grouped into by modified polyorganosiloxane, the modified group such as cyclosiloxane and silicon dioxide, with liquid silicon
Thixotropy add-on type liquid silicon rubber is obtained so as to thixotropy is significantly improved after the mixing of rubber base component, simultaneously organic
Silicon thixotropic agent is good with the liquid silastic base polymer compatibility, to its extrudability and solidification after Effect on Mechanical Properties less,
Beneficial to the combination property improving liquid silastic.
The purpose of the present invention is achieved through the following technical solutions:
A kind of organosilicon thixotropic agent, comprises modified polyorganosiloxane and modified cyclosiloxane, described modified polyorganosiloxane and changing
Modified group in property cyclosiloxane is the group containing one or more of epoxy radicals, ether, hydroxyl, amido, ester group, institute
The content stating modified group in modified polyorganosiloxane is 0.01～0.80mol/100g, modified group in described modification cyclosiloxane
Content be 0.10～0.60mol/100g.
The content of modified group be the modified group that contains in 100g modified polyorganosiloxane or modified cyclosiloxane mole
Amount.Preferably, the modified group in described modified polyorganosiloxane and modified cyclosiloxane is containing in epoxy radicals, ether, ester group
The group of one or more.
Preferably, shown in the average composition formula of described modified polyorganosiloxane such as formula ():
r1 asio(4-a)/2(ⅰ)
In formula (), a is the positive number of satisfaction 1.5≤a≤2.8, r1For identical or different monovalent hydrocarbon, hydrogen or modified base
Group.
Preferably, in formula (), 2≤a≤2.3.
Preferably, in described modified polyorganosiloxane, the content of modified group is 0.10～0.50mol/100g.
Preferably, the hydrogen content of described modified polyorganosiloxane is 0.1-0.5%.
Preferably, the end-capping group of described modified polyorganosiloxane includes modified group.
Preferably, described modified polyorganosiloxane is modified methyl containing hydrogen silicone oil or modified methyl phenyl hydrogen-containing silicon oil.
Preferably, the viscosity of described modified polyorganosiloxane is 30～12000mpa s.
Preferably, shown in the structural formula such as formula () of described modification cyclosiloxane:
In formula (), b is the integer of satisfaction 3≤b≤10, r2For identical or different monovalent hydrocarbon, hydrogen or modified group.
Preferably, described modification cyclosiloxane is the hydrogeneous cyclosiloxane of modified methyl or modified methyl phenyl hydrogeneous ring silica
Alkane.
It is highly preferred that described modification cyclosiloxane is modified tetramethyl-ring tetrasiloxane and/or modified methyl hydrogen ring silica
Alkane mixture.
Preferably, the hydrogen content of described modification cyclosiloxane is 0.05～0.5%.It is furthermore preferred that described modification cyclosiloxane
Hydrogen content be 0.1～0.5%.
Preferably, described organosilicon thixotropic agent includes the modified polyorganosiloxane of 1～5 weight portion and changing of 0.1～5 weight portion
Property cyclosiloxane.
Preferably, described modified polyorganosiloxane and the weight ratio of modified cyclosiloxane are (0.2-10): 1.
Preferably, also contain aerosil in described organosilicon thixotropic agent.
Preferably, the particle diameter of described aerosil is 20～50nm.
It is highly preferred that the consumption of described aerosil is 0.5-5 weight portion.
A kind of thixotropy add-on type liquid silicon rubber, containing base polymer, cross-linking agent, inhibitor, catalyst and have
Machine silicon thixotropic agent, described organosilicon thixotropic agent comprises modified polyorganosiloxane and modified cyclosiloxane, described modified polyorganosiloxane and
Modified group in modified cyclosiloxane is the group containing one or more of epoxy radicals, ether, hydroxyl, amido, ester group,
In described modified polyorganosiloxane, the content of modified group is 0.01～0.80mol/100g, modified base in described modification cyclosiloxane
The content of group is 0.10～0.60mol/100g.
The content of modified group be the modified group that contains in 100g modified polyorganosiloxane or modified cyclosiloxane mole
Amount.Preferably, the modified group in described modified polyorganosiloxane and modified cyclosiloxane is containing in epoxy radicals, ether, ester group
The group of one or more.
Preferably, shown in the average composition formula of described modified polyorganosiloxane such as formula ():
r1 asio(4-a)/2(ⅰ)
In formula (), a is the positive number of satisfaction 1.5≤a≤2.8, r1For identical or different monovalent hydrocarbon, hydrogen or modified base
Group.
Preferably, in formula (), 2≤a≤2.3.
Preferably, in described modified polyorganosiloxane, the content of modified group is 0.10～0.50mol/100g.
Preferably, the end-capping group of described modified polyorganosiloxane includes modified group.
Preferably, the hydrogen content of described modified polyorganosiloxane is 0.1～0.5%.
Preferably, described modified polyorganosiloxane is modified methyl containing hydrogen silicone oil or modified methyl phenyl hydrogen-containing silicon oil.
Preferably, the viscosity of described modified polyorganosiloxane is 30～12000mpa s.
Preferably, shown in the structural formula such as formula () of described modification cyclosiloxane:
In formula (), b is the integer of satisfaction 3≤b≤10, r2For identical or different monovalent hydrocarbon, hydrogen or modified group.
Preferably, described modification cyclosiloxane is the hydrogeneous cyclosiloxane of modified methyl or modified methyl phenyl hydrogeneous ring silica
Alkane.
Preferably, described modification cyclosiloxane is modified tetramethyl-ring tetrasiloxane and/or modified methyl hydrogen cyclosiloxane
Mixture.
Preferably, the hydrogen content of described modification cyclosiloxane is 0.05～0.5%.It is furthermore preferred that described modification cyclosiloxane
Hydrogen content be 0.1～0.5%.
Preferably, described organosilicon thixotropic agent includes the modified polyorganosiloxane of 1～5 weight portion and changing of 0.1～5 weight portion
Property cyclosiloxane.
Preferably, described modified polyorganosiloxane and the weight ratio of modified cyclosiloxane are (0.2-10): 1.
Preferably, also contain aerosil in described organosilicon thixotropic agent.
Preferably, the particle diameter of described aerosil is 20～50nm.
It is highly preferred that the consumption of described aerosil is 0.5-5 weight portion.
Preferably, the quality of described organosilicon thixotropic agent accounts for the 0.5～8% of thixotropy add-on type liquid silicon rubber quality.
Preferably, described base polymer includes vinyl polysiloxane and vinyl silicone oil, and described cross-linking agent includes hydrogeneous
Silicone oil.
The invention has the benefit that the organosilicon thixotropic agent that the present invention provides is by modified polyorganosiloxane, modified ring silica
The group such as alkane and silicon dioxide is grouped into, and wherein modified polyorganosiloxane and modified cyclosiloxane contains and can form hydrogen bond and three-dimensional network
The modified group of structure, plays synergistic function after mixing with silicon dioxide, after mixing with liquid silastic component, can be notable
Improve the thixotropy of liquid silastic, obtain thixotropy and extrusion performance is good, and the thixotropy of molding before and after solidification, can be stablized
Add-on type liquid silicon rubber, meets the requirement of the no concrete application occasion such as die package, and the adaptability of organosilicon thixotropic agent is good,
Preparation method is simple, beneficial to the popularization and application promoting thixotropy add-on type liquid silicon rubber, and the no liquid silicon such as die package
The improvement of rubber applications technique.
Specific embodiment
The present invention provides a kind of organosilicon thixotropic agent and the thixotropy add-on type liquid silicon rubber containing this organosilicon thixotropic agent
Glue.Wherein, organosilicon thixotropic agent comprises modified polyorganosiloxane and modified cyclosiloxane, modified polyorganosiloxane and modified cyclosiloxane
In modified group be the group containing one or more of epoxy radicals, ether, hydroxyl, amido, ester group, modified polyorganosiloxane
The content of middle modified group be 0.01～0.80mol/100g, in modified cyclosiloxane the content of modified group be 0.10～
0.60mol/100g.
The content of modified group be the modified group that contains in 100g modified polyorganosiloxane or modified cyclosiloxane mole
Amount, can be measured modified group content by analysis of experiments, or be obtained by the consumption conversion of reaction raw materials.
Preferably shown in the average composition formula such as formula () of modified polyorganosiloxane:
r1 asio(4-a)/2(ⅰ)
In formula (), a is the positive number of satisfaction 1.5≤a≤2.8, r1For identical or different monovalent hydrocarbon, hydrogen or modified base
Group.
In the average composition formula of modified polyorganosiloxane, r1For identical or different monovalent hydrocarbon, hydrogen or monovalence function base,
I.e. modified polyorganosiloxane is to have different r1Same in the mixing of the modified polyorganosiloxane of group, and modified polyorganosiloxane molecule
R on silicon atom1Substituent group can be identical or different above-mentioned substituent group.
A represents substituent group r in molecular structure1Mean number, by the two sense silica forming modified polyorganosiloxane molecule
The relative usage of alkane unit, the Mono-functional siloxanes' unit for end-blocking and a small amount of trifunctional siloxane units determines.Preferred
In embodiment, 2≤a≤2.3.
Preferably, in modified polyorganosiloxane, the content of modified group is 0.10～0.50mol/100g.
In the organosilicon thixotropic agent that the present invention provides, modified polyorganosiloxane is the replacement being combined with silicon atom on polysiloxanes
Base is obtained by after modified group part replacement, and experiment shows, the modified polyorganosiloxane with certain modified group content has and changes
It is apt to thixotropic effect.Polysiloxanes as modified substrates have linear molecular structure beneficial to modification, can be specifically modified
Introduce a small amount of side chain or network structure in technique, the thixotropic effects of organosilicon thixotropic agent are had no significant effect, be i.e. modified poly- silicon
Oxygen alkane is preferably modified silicon oil, can directly be commercially available, for example epoxide modified containing hydrogen silicone oil, polyether modified silicon oil, acrylate
Modified silicon oil, acrylic acid modified silicone oil etc., more preferably modified methyl containing hydrogen silicone oil or modified methyl phenyl hydrogen-containing silicon oil.
The molecular weight of modified polyorganosiloxane does not limit, and preferably its viscosity is 30～12000mpa s.
Correspondingly, the modified group in modified polyorganosiloxane is preferably containing one or more of ether, epoxy radicals, ester group
Modified group, more preferably OrOne or more of, r3、
r4、r5For h, or the alkyl of identical or different c1～c5, r6Alkylidene for c2～c5, n, r are and are less than or equal to 3 more than zero
Integer, x be more than zero be less than 20 integer.
In above modified group,For polyethers function base, r6Asia for c2～c5
Alkyl, specifically includes-ch2ch2-、-ch2ch(ch3The mixing of the identical or different segment of)-wait, r6Be preferably be ethylidene (-
ch2ch2-), x is preferably 10, the modified polyorganosiloxane containing this group and liquid silastic can be made to have the preferable compatibility, profit
In the thixotropic property improving liquid silastic.
In a preferred embodiment, n, r are 1.r3、r4、r5For the alkyl of identical or different c1～c5, concretely methyl,
The saturated alkyl that ethyl, propyl group, tert-butyl group etc. are similar to, preferably methyl.
Monovalent hydrocarbon can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl or similar alkyl；Ring penta
Base, cyclohexyl or similar cycloalkyl；Phenyl, tolyl, xylyl or similar aryl；Benzyl, phenethyl, phenylpropyl or
Similar aralkyl；3,3,3- trifluoro propyl, 3- chloropropyl or similar haloalkyl；Below most preferably alkyl and virtue
Base, especially methyl and phenyl.
In a preferred embodiment, the hydrogen content of modified polyorganosiloxane is 0.1～0.5% so as to addition in liquid silastic
Participate in hydrosilylation in solidification, beneficial to the mechanical performance improving after liquid silastic solidification, obtain high comprehensive performance
Thixotropy add-on type liquid silicon rubber.Hydrogen content is in the substituent group being connected with silicon atom, and the weight/mass percentage composition of hydrogen-based, to change
Property polysiloxanes quality be 100% meter.
In a preferred embodiment, the end-capping group of modified polyorganosiloxane includes modified group, that is, modified polyorganosiloxane by
Mono-functional siloxanes containing modified group are unit terminated, can unexpectedly improve the thixotropic property of liquid silastic.
In organosilicon thixotropic agent, modified cyclosiloxane is small-molecule substance, is the organic group being connected with silicon in cyclosiloxane
Obtain after being replaced by modified group part, experiment shows, modified cyclosiloxane also has certain thixotropy improvement result, but with
After modified polyorganosiloxane combination, thixotropy improvement result is notable, and synergy projects.
Shown in the structural formula such as formula () of preferably modified cyclosiloxane:
In formula (), b is the integer of satisfaction 3≤b≤10, r2For identical or different monovalent hydrocarbon, hydrogen or modified group.
In the structural formula of modified cyclosiloxane, b represents the number of silica unit in molecular structure, b be satisfaction 3≤b≤
10 integer, that is, modified cyclosiloxane include modified cyclotetrasiloxane, modified D5, modified ring six siloxanes etc..?
In preferred embodiment, b=4, as modified cyclotetrasiloxane.
R in formula ()2With the r in formula ()1There are identical meanings, but there is no corresponding relation.r2For identical or different one
Valency alkyl, hydrogen and modified group, that is, modified cyclosiloxane is to have different r2The mixing of the modified cyclosiloxane of group, and modified
R on same silicon atom in cyclic siloxane molecules2Substituent group can be identical or different above-mentioned substituent group.
In formula (), modified group is preferably the modified group containing one or more of ehter bond, epoxy radicals, ester group, enters one
Step is preferably
OrOne or more of, r3、r4、r5For h, or identical or different c1～c5
Alkyl, r6Alkylidene for c2～c5, n, r are the integer being less than or equal to 3 more than zero, and x is the integer more than zero less than 20.
In above modified group,For polyethers function base, r6Asia for c2～c5
Alkyl, specifically includes-ch2ch2-、-ch2ch(ch3The mixing of the identical or different segment of)-wait, r6Be preferably be ethylidene (-
ch2ch2-), x is preferably 10, the modified cyclosiloxane containing this group and liquid silastic can be made to have the preferable compatibility, profit
In the thixotropic property improving liquid silastic.
In a preferred embodiment, in formula (), n, r are 1.r3、r4、r5For the alkyl of identical or different c1～c5, specifically
The saturated alkyl being similar to for methyl, ethyl, propyl group, tert-butyl group etc., preferably methyl.
In the molecular structure of modified cyclosiloxane, monovalent hydrocarbon can enumerate methyl, ethyl, propyl group, butyl, amyl group, oneself
Base, heptyl or similar alkyl；Cyclopenta, cyclohexyl or similar cycloalkyl；Phenyl, tolyl, xylyl or similar
Aryl；Benzyl, phenethyl, phenylpropyl or similar aralkyl；3,3,3- trifluoro propyl, 3- chloropropyl or similar alkyl halide
Base；Below most preferably alkyl and aryl, especially methyl and phenyl.Modified cyclosiloxane is preferably the hydrogeneous ring of modified methyl
Siloxanes or the hydrogeneous cyclosiloxane of modified methyl phenyl.
In a preferred embodiment, the hydrogen content of modified cyclosiloxane is 0.05～0.5%, more preferably 0.1～0.5%, makes
It participates in hydrosilylation in the addition curing of liquid silastic, beneficial to the mechanicalness improving after liquid silastic solidification
Can, obtain the thixotropy add-on type liquid silicon rubber of high comprehensive performance.Hydrogen content is hydrogen in the substituent group being connected with silicon atom
The weight/mass percentage composition of base, is counted with the quality of modified cyclosiloxane for 100%.
In the organosilicon thixotropic agent that the present invention provides, the modified group in modified polyorganosiloxane and modified cyclosiloxane be containing
There is the group of one or more of epoxy radicals, ether, hydroxyl, amido, ester group, contain in modified group and can form hydrogen bond
Function base, makes to interact by modified group between siloxane molecule, forms thixotropy network structure, improves liquid silicon
The thixotropic property of rubber.Modified group is preferably the group containing one or more of epoxy radicals, ether or ester group.
In a preferred embodiment, organosilicon thixotropic agent includes the modified polyorganosiloxane of 1-5 weight portion and 0.1-5 weight portion
Modified cyclosiloxane.
In a preferred embodiment, the organosilicon thixotropic agent of the present invention also comprises silicon dioxide, concrete such as aerosil
Deng, particle diameter preferably 20～50nm, consumption is preferably 0.5-5 weight portion.Silicon dioxide and modified polyorganosiloxane and modified ring silicon
Being applied in combination of oxygen alkane presents prominent synergistic function, is remarkably improved the thixotropic property of liquid silastic.
It is pointed out that modified polyorganosiloxane and modified cyclosiloxane all can be according in the organosilicon thixotropic agent of the present invention
Prepared by existing method, or buy acquisition.Wherein, the preferred preparation method of modified polyorganosiloxane, including following operating procedure:
By containing hydrogen silicone oil and containing holding the modified-reaction thing of thiazolinyl in inert gas environment and organic solvent, at 85-95 DEG C
Lower through platinum catalyst catalytic reaction 6～12h, after completion of the reaction, vacuum distillation, that is, obtain modified polyorganosiloxane.
In method made above, the synthesis of containing hydrogen silicone oil is referred to existing method and carries out, to adjust dividing of modified polyorganosiloxane
Minor structure, such as viscosity, phenyl content etc.；Modified-reaction thing containing end thiazolinyl is containing epoxy radicals, ether, hydroxyl, amido or ester group etc.
Group and the compound holding position unsaturated double-bond that additive reaction can occur with si-h bond, specifically can enumerate allyl glycidol
Ether (age), 1,2- epoxy -4- vinyl cyclohexane, alkyl acrylate, allyl polyethenoxy ether (ch2=chch2o(ch2ch2o)x0H), methyl allyl polyoxyethylene ether, ethylene glycol monovinyl etherVinyl
PolyethersDeng wherein x0、x1、
x2Value no particular restriction, the alkyl in alkyl acrylate includes methyl, ethyl, butyl etc..
Include the modified polyorganosiloxane of modified group in order to obtain end-capping group, the preparation side of the art can be adopted
Method prepares hydrogen end-blocking containing hydrogen silicone oil, then obtains modified polyorganosiloxane with reacting containing the modified-reaction thing holding thiazolinyl.
In organosilicon thixotropic agent, the preferred preparation method of modified cyclosiloxane, including following operating procedure:
By hydrogeneous cyclosiloxane and containing holding the modified-reaction thing of thiazolinyl in inert gas environment and organic solvent, in 85-
Through platinum catalyst catalytic reaction 6～12h at 95 DEG C, after completion of the reaction, vacuum distillation, that is, obtain modified cyclosiloxane.
In this preparation method, the synthesis of hydrogeneous cyclosiloxane is referred to existing method synthesis or is commercially available, the alkene containing end
The modified-reaction thing of base is containing groups such as epoxy radicals, ether, hydroxyl, amido or ester groups and can to occur to add with si-h bond
Become the compound of the end position unsaturated double-bond of reaction, specifically can enumerate allyl glycidyl ether (age), 1,2- epoxy -4-
Vinyl cyclohexane, alkyl acrylate, allyl polyethenoxy ether (ch2=chch2o(ch2ch2o)x0H), methacrylic gathers
Oxygen vinyl Ether, ethylene glycol monovinyl etherVinyl polyetherDeng wherein x0、
x1、x2Value no particular restriction, the alkyl in alkyl acrylate includes methyl, ethyl, butyl etc..
The embodiment of the present invention further provides for a kind of thixotropy add-on type liquid silicon rubber, containing base polymer, crosslinking
Agent, inhibitor, catalyst and organosilicon thixotropic agent, this organosilicon thixotropic agent comprises modified polyorganosiloxane and modified ring silica
Modified group in alkane, modified polyorganosiloxane and modified cyclosiloxane is containing in epoxy radicals, ether, hydroxyl, amido, ester group
The group of one or more, in modified polyorganosiloxane, the content of modified group is 0.01～0.8mol/100g, modified cyclosiloxane
The content of middle modified group is 0.10～0.60mol/100g.The preferred structure of modified polyorganosiloxane and modified cyclosiloxane is as above
State, repeat no more.
In a preferred embodiment, the quality of organosilicon thixotropic agent accounts for the 0.5 of thixotropy add-on type liquid silicon rubber quality
～8%.Wherein, the basic components of the add-on type liquid silicon rubbers such as base polymer, cross-linking agent, inhibitor and catalyst are not had
Particular restriction, may also be employed the basic components of condensed type liquid silastic, accordingly obtains thixotropy condensed type liquid silastic.Right
In add-on type liquid silicon rubber, base polymer includes vinyl polysiloxane, vinyl silicone oil etc., and cross-linking agent includes Silicon Containing Hydrogen
Oil, inhibitor and catalyst all no particular restriction, also can contain in this thixotropy add-on type liquid silicon rubber simultaneously as needed
Filler and additive, such as heat filling, conductive filler, fire retardant etc..
In practice, directly can add organosilicon thixotropic agent in existing liquid silastic product, obtain thixotropic liquid silicon
Rubber, easy to use, the composition of liquid silastic is not particularly limited simultaneously, all can improve its thixotropy.
The present invention provides preferred thixotropy add-on type liquid silicon rubber, is bi-component addition type liquid silastic, including
The vinyl polysiloxane of 35-55 weight portion, the vinyl silicone oil of 35-55 weight portion, the containing hydrogen silicone oil of 2-15 weight portion, organosilicon
Thixotropic agent 5-10 part and inhibitor and catalyst.Give the composition of preferred thixotropy add-on type liquid silicon rubber herein,
Promising viscosifier meeting application request addition etc. also can be contained.Wherein, organosilicon thixotropic agent includes the modification of 1-5 weight portion
Polysiloxanes, the modified cyclosiloxane of 0.1-5 weight portion and 0.5-5 weight portion aerosil.
In a preferred embodiment, vinyl polysiloxane medium vinyl content be 0.1-2%, including vinyl methyl silicones,
The vinyl polysiloxanes commonly used in the art such as Vinylphenyl silicon resin, vinyl methyl phenyl polysiloxane；Vinyl silicone oil viscous
Spend for 5000～10000mpa s, contents of ethylene is 0.5-2%；The viscosity of containing hydrogen silicone oil is 15～50mpa s, hydrogen content
For 0.8-1.6%.Meanwhile, inhibitor and catalyst are not particularly limited, and can be selected according to practical situation, and such as inhibitor is second
Alkynyl Hexalin, consumption is 0.025-0.035 weight portion, and catalyst is vinyl double-seal head platinum complex, and consumption is 5-
10ppm.
The present invention can pass through examples below further instruction, but embodiment is not the limit to the scope of the present invention
System.In following embodiments, me represents methyl, and ph represents phenyl, and r ' represents the modified group in modified polyorganosiloxane, Silicon Containing Hydrogen
The hydrogen content of oil, modified polyorganosiloxane, modified cyclosiloxane etc. is the weight/mass percentage composition of hydrogen in material institute silicon-hydrogen bond containing, test
Method refers to document: Zhang Donghui, Zhang Songlin, Fan Hui army etc., and the synthesis of amino-polyether modified organosilicon is studied with antifoam performance,
Chemical Engineering and Technology, 2013,3:122-126；The epoxy group content method of testing of modified cyclosiloxane and modified polyorganosiloxane
Refer to document: Liu Jie, Tang Li, Li Yan, a kind of determination of epoxide number of Fast Practical, leather and chemical industry, 2012,29(1):
26-28.
Embodiment 1
The modified cyclosiloxane of preparation:
In four-hole bottle, it is passed through dry n2, add d4 h(24.00g, 0.10mol, hydrogen content is 1.6125%), petroleum ether
(100.00g) and pt/ipa(0.15g, 60 μ g/g), stirring be warmed up to 85 DEG C, with constant pressure funnel Deca allyl glycidyl ether
(age) (57.08g, 0.50mol), after completion of dropping, reacts 6h at 85 DEG C, after completion of the reaction, vacuum distillation, obtain modification
Cyclosiloxane.
The hydrogen content recording modified cyclosiloxane is 0.1568%, the modified group containing epoxy radicalsContent is 0.53mol/100g.
Embodiment 2
The modified cyclosiloxane of preparation:
In four-hole bottle, it is passed through dry n2, add d4 h(24.00g, 0.10mol, hydrogen content is 1.6125%), to benzene two
Phenol monomethyl ether (0.09g, 0.00072mol), (petroleum ether (100.00g) and pt/ipa(0.16g, 60 μ g/g), stirring is warmed up to
85 DEG C, with constant pressure funnel Deca butyl acrylate (64.08g, 0.5mol), after completion of dropping, react 10h, reaction at 85 DEG C
After finishing, vacuum distillation, obtain modified cyclosiloxane.
The hydrogen content recording modified cyclosiloxane is 0.2486%, the modified group containing ester groupContent is 0.45mol/100g.
Embodiment 3
Prepare modified polyorganosiloxane:
A, weigh 74.16g(0.25mol) octamethylcy-clotetrasiloxane (d4), 60g containing hydrogen silicone oil (0.025mol, siloxanes
Unit number is 40, and molecular weight is 2400), 3.43g(0.1mol) hydrogeneous double-seal head and 7.38g cationic resin, heat up after mixing
To 45 DEG C, stirring reaction, after 9 hours, filters, and removes cationic resin, vacuum distillation, removes low-boiling-point substance, obtains hydrogen end-blocking hydrogeneous
Silicone oil, viscosity is 35mpa s；
B, 29.48g hydrogen is blocked containing hydrogen silicone oil and 0.072g isopropyl alcohol solution of chloroplatinic acid (platinum content is 0.0072g) and add
In 50.00g petroleum ether, it is passed through dry n2, stir and be warmed up to 85 DEG C, Deca 10.26g allyl glycidyl ether while stirring
(age) at 85 DEG C, react 10h, after completion of the reaction, vacuum distillation, obtain modified polyorganosiloxane.
The composition formula of modified polyorganosiloxane is (r ' me2sio1/2)0.09(r’mesio)0.15(me2sio)0.45
(hmesio)0.31, r ' is γ-glycidyl ether oxygen propylRespectively
The viscosity that mensure obtains modified polyorganosiloxane is 45mpa s, and hydrogen content is 0.3455%, the modified group content containing epoxy radicals
For 0.26mol/100g.
Embodiment 4
Prepare modified polyorganosiloxane:
Hydrogen prepared by 29.48g embodiment 3 blocks containing hydrogen silicone oil and 0.073g isopropyl alcohol solution of chloroplatinic acid, and (platinum content is
0.0073g) add in 60.00g petroleum ether, be passed through dry n2, stir and be warmed up to 85 DEG C, Deca 59.76g molecule while stirring
Measure the allyl polyethenoxy ether for 500, react 10～12h at 85 DEG C, after completion of the reaction, vacuum distillation, obtain modified poly-
Siloxanes.
Gained modified polyorganosiloxane composition formula is (r ' me2sio1/2)0.09(r’mesio)0.13(me2sio)0.45
(hmesio)0.33, r ' is polyoxyethylene ether oxygen propyl (- ch2ch2ch2o(ch2ch2o)10h), and end-capping group includes polyoxy second
Alkene ether oxygen propyl (- ch2ch2ch2o(ch2ch2o)10H).The viscosity that mensure obtains modified polyorganosiloxane respectively is 130mpa
S, hydrogen content is 0.2122%, and polyoxyethylene ether oxygen propyl content is 0.12mol/100g.
Embodiment 5
Prepare dual composition addition type liquid silastic, including a, b component, form as follows:
A component:
25 parts of vinyl polysiloxane
23.544 parts of vinyl silicone oil
Catalyst 6ppm, each component mix homogeneously obtains a component.
B component:
Wherein, the contents of ethylene of vinyl polysiloxane is 1.15%, and the viscosity of vinyl silicone oil is 7000mpa s, second
Amount vinyl content is 1.06%, and the viscosity of containing hydrogen silicone oil is 25mpa s, and hydrogen content is 1.37%, and inhibitor is ethynylcyclohexanol,
Catalyst is vinyl double-seal head platinum complex.
With the modified cyclosiloxane of embodiment 1-2 preparation and the modified polyorganosiloxane of embodiment 3-4 preparation and silicon dioxide
Preparation obtains organosilicon thixotropic agent 1-5#, and proportioning is shown in Table 1, and wherein silicon dioxide is the aerosil of 40nm for particle diameter.
Table 1
Use banbury banburying according to proportioning by after aerosil, modified polyorganosiloxane and modified cyclosiloxane mixing,
Obtain 1～4# organosilicon thixotropic agent, modified polyorganosiloxane and modified cyclosiloxane are uniformly mixed according to a ratio, obtain 5# organosilicon
Thixotropic agent.
A, b component mix homogeneously of above-mentioned add-on type liquid silicon rubber is obtained the liquid silastic of 100 weight portions, respectively
Add 2.5 weight portion 1-5# organosilicon thixotropic agent, be uniformly mixed, obtain 1-5# thixotropy add-on type liquid silicon rubber.
As a comparison, 1 weight portion aerosil is added in the above-mentioned add-on type liquid silicon rubber of 100 weight portions,
Through banbury banburying 10min, obtain 6# thixotropy add-on type liquid silicon rubber, the add-on type liquid silicon rubber of thixotropic agent will be not added with
Glue is designated as blank sample.
Testing example
1～6# thixotropy add-on type liquid silicon rubber (abbreviation liquid silastic) that embodiment 5 is prepared and blank sample are used
Make led packaging plastic, and it is carried out with performance test, investigate the extrudability and thixotropy before liquid silastic solidification, and solidification
Hardness afterwards, observes when this liquid silastic is using encapsulating by the way of pouring into a mould, the formed bodies before and after solidification are meanwhile
No subside or deform.
Wherein, thixotropic index ndj-1 type rotating cylinder viscometer, is tested by gb7193.1-87, is taken same rotor,
Measure the viscosity of liquid silastic under 6r/min and 60r/min respectively, be calculated thixotropic index, thixotropic index k=η1/η2(η1
For viscosity number during 6r/min, η2Viscosity number for during 60r/min).
Extrudability method of testing is: after liquid silastic vacuum defoamation, loads in pe pipe, puts same syringe needle,
20kg/cm2Continuously extrude under air pressure, the continuous gel quantity extruding 5s of record.
After liquid silastic vacuum defoamation, encapsulated by the way of cast, make liquid silastic form lenticular hemisphere
Body, solidified through 100 DEG C × 1 hour+150 DEG C × 3 hours, observes formed bodies and height before and after solidification, is designated as thixotroping stable
Property.
After liquid silastic vacuum defoamation, in encapsulating to 2835 lamp bead of 0.2w by the way of cast, in heat sink temperature
Under conditions of 25 DEG C and operating current 60ma of degree, measure its luminous flux.
Test result is shown in Table 2.
Table 2
From the data in table 2, it can be seen that the organosilicon thixotropic agent of the present invention is added in add-on type liquid silicon rubber can be notable
Improve the thixotropic property of liquid silastic, and the modified polyorganosiloxane in organosilicon thixotropic agent, modified cyclosiloxane and titanium dioxide
There is synergistic function in silicon, after mixing, the thixotropy improvement of liquid silastic is projected.Gained thixotropy silicone rubber warp
Moulding by casting, can form hemispherical lens shape before solidification, substantially can maintain original shape after solidification, and thixotroping has good stability, and
Extrudability disclosure satisfy that use requirement, after applying, very little, i.e. the thixotropy addition of the present invention are affected on the luminous flux of lamp bead simultaneously
Type liquid silastic can straight forming, without using mould, when encapsulating, can directly replace traditional mould top package work for led
Skill, it is easy to operation, simple process, simplifies the production of support, makes that application cost is low, production efficiency is high.
Finally it should be noted that above example only in order to illustrate technical scheme rather than to the present invention protect
The restriction of scope.It will be understood by those of skill in the art that can carry out to technical scheme some deducing or waiting
With replacing, without deviating from the spirit and scope of technical solution of the present invention.
Claims (7)
1. a kind of organosilicon thixotropic agent is it is characterised in that by modified polyorganosiloxane, modified cyclosiloxane and aerosil group
Become, the modified group in described modified polyorganosiloxane and modified cyclosiloxane is containing epoxy radicals, ether, hydroxyl, amido, ester group
One or more of group, in described modified polyorganosiloxane the content of modified group be 0.01～0.80mol/100g, institute
The content stating modified group in modified cyclosiloxane is 0.10～0.60mol/100g.
2. organosilicon thixotropic agent as claimed in claim 1 is it is characterised in that described modified polyorganosiloxane and modified cyclosiloxane
In modified group be the group containing one or more of epoxy radicals, ether, ester group.
3. organosilicon thixotropic agent as claimed in claim 1 or 2 is it is characterised in that the viscosity of described modified polyorganosiloxane is 30
～12000mpa s.
4. organosilicon thixotropic agent as claimed in claim 3 is it is characterised in that the hydrogen content of described modified polyorganosiloxane is 0.1
～0.5%.
5. organosilicon thixotropic agent as claimed in claim 1 is it is characterised in that the hydrogen content of described modification cyclosiloxane is 0.05
～0.5%.
6. organosilicon thixotropic agent as claimed in claim 1 is it is characterised in that described organosilicon thixotropic agent is by 1～5 weight portion
Modified polyorganosiloxane, the modified cyclosiloxane of 0.1～5 weight portion, 0.5-5 weight portion aerosil composition.
7. a kind of thixotropy add-on type liquid silicon rubber, containing base polymer, cross-linking agent, inhibitor and catalyst, its feature
It is also to contain organosilicon thixotropic agent, described organosilicon thixotropic agent is by modified polyorganosiloxane, modified cyclosiloxane and gas phase dioxy
SiClx forms, and the modified group in described modified polyorganosiloxane and modified cyclosiloxane is containing epoxy radicals, ether, hydroxyl, amine
The group of one or more of base, ester group, in described modified polyorganosiloxane, the content of modified group is 0.01～0.80mol/
100g, in described modification cyclosiloxane, the content of modified group is 0.10～0.60mol/100g.
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| CN201410112176.6A CN103937257B (en) | 2014-03-24 | 2014-03-24 | Organic silicone thixotropic agent and thixotropy addition type liquid silicone rubber |
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| WO2018206995A1 (en) * | 2017-05-10 | 2018-11-15 | Elkem Silicones France Sas | Method for manufacturing a silicone elastomer article using a 3d printer |
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| JP7432519B2 (en) * | 2018-10-18 | 2024-02-16 | ダウ・東レ株式会社 | Curable organopolysiloxane composition with excellent cold resistance, pattern forming method, electronic components, etc. |
| US11845869B2 (en) | 2019-06-21 | 2023-12-19 | Dow Silicones Corporation | Method for producing thixotropic curable silicone composition |
| CN110229523B (en) * | 2019-07-10 | 2020-07-17 | 河南大学 | Multiple network liquid silicone rubber and preparation method thereof |
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| CN112979963B (en) * | 2020-12-30 | 2022-04-15 | 北京康美特科技股份有限公司 | Reactive silicone thixotropic agent, silicone packaging adhesive and LED element |
| CN114133743B (en) * | 2021-12-15 | 2023-08-01 | 东莞市贝特利新材料有限公司 | Addition type flame-retardant heat-resistant liquid silicone rubber composition and preparation method thereof |
| CN114517016B (en) * | 2022-02-21 | 2023-01-24 | 江西蓝星星火有机硅有限公司 | High-resilience low-pressure variable rubber compound and preparation method thereof |
| CN115141491A (en) * | 2022-06-28 | 2022-10-04 | 中国工程物理研究院化工材料研究所 | Multi-component silica gel suitable for direct-writing 3D printing, mixing device and printing method |
| CN115073512B (en) * | 2022-08-23 | 2022-11-25 | 广州硅芯材料科技有限公司 | Organic silicon thixotropic agent, organic silicon composition, and preparation method and application thereof |
| CN115678497A (en) * | 2023-01-04 | 2023-02-03 | 北京康美特科技股份有限公司 | Organic silicon packaging adhesive for micro LED element and packaging method and application thereof |
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Denomination of invention: Organic silicon thixotropic agent and thixotropic additive liquid silicone rubber Effective date of registration: 20231106 Granted publication date: 20170125 Pledgee: China Construction Bank Corporation Huizhou Dayawan Branch Pledgor: HUIZHOU ANPIN SILICONE MATERIAL Co.,Ltd. Registration number: Y2023980064214 |
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