CN109824903A - A kind of high refractive index boracic organic silicon rigidity-increasing stick and preparation method thereof - Google Patents
A kind of high refractive index boracic organic silicon rigidity-increasing stick and preparation method thereof Download PDFInfo
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- CN109824903A CN109824903A CN201910145484.1A CN201910145484A CN109824903A CN 109824903 A CN109824903 A CN 109824903A CN 201910145484 A CN201910145484 A CN 201910145484A CN 109824903 A CN109824903 A CN 109824903A
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- refractive index
- organic silicon
- high refractive
- preparation
- increasing stick
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 44
- 239000010703 silicon Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000000376 reactant Substances 0.000 claims abstract description 16
- 229910052796 boron Inorganic materials 0.000 claims abstract description 7
- 230000006837 decompression Effects 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000706 filtrate Substances 0.000 claims description 14
- 229920002545 silicone oil Polymers 0.000 claims description 14
- 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 13
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 239000003729 cation exchange resin Substances 0.000 claims description 12
- YBHBEZSZXFLQMW-UHFFFAOYSA-N [dimethoxy(phenyl)silyl]methanamine Chemical compound CO[Si](CN)(OC)C1=CC=CC=C1 YBHBEZSZXFLQMW-UHFFFAOYSA-N 0.000 claims description 11
- -1 alkoxy silane Chemical compound 0.000 claims description 11
- 238000000746 purification Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 229910000077 silane Inorganic materials 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 238000013517 stratification Methods 0.000 claims description 7
- 238000005292 vacuum distillation Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- BXQOGTHSKFRGDV-UHFFFAOYSA-N C(CC)[Si](OCC)(OCC)C.[O] Chemical compound C(CC)[Si](OCC)(OCC)C.[O] BXQOGTHSKFRGDV-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 claims description 3
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 claims description 2
- RDSFIYKNDOPAHY-UHFFFAOYSA-N C(CC)[Si](OC)(OC)C.[O] Chemical compound C(CC)[Si](OC)(OC)C.[O] RDSFIYKNDOPAHY-UHFFFAOYSA-N 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 claims description 2
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 2
- YAGBAUUBKBTRNY-UHFFFAOYSA-N CO[SiH](OC)OC.C(C=C)(=O)OCCC[SiH2]OCC Chemical compound CO[SiH](OC)OC.C(C=C)(=O)OCCC[SiH2]OCC YAGBAUUBKBTRNY-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 125000003342 alkenyl group Chemical group 0.000 claims 1
- 125000002091 cationic group Chemical group 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims 1
- 229920002379 silicone rubber Polymers 0.000 abstract description 16
- 239000004954 Polyphthalamide Substances 0.000 abstract description 11
- 229920006375 polyphtalamide Polymers 0.000 abstract description 11
- 229920001971 elastomer Polymers 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 2
- 231100000572 poisoning Toxicity 0.000 abstract description 2
- 230000000607 poisoning effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 19
- 238000013019 agitation Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 7
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 5
- 239000003957 anion exchange resin Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- ZDWQSEWVPQWLFV-UHFFFAOYSA-N C(CC)[Si](OC)(OC)OC.[O] Chemical compound C(CC)[Si](OC)(OC)OC.[O] ZDWQSEWVPQWLFV-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- NAYYNDKKHOIIOD-UHFFFAOYSA-N phthalamide Chemical compound NC(=O)C1=CC=CC=C1C(N)=O NAYYNDKKHOIIOD-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Abstract
The invention belongs to the additive agent fields of organic silicon rubber, and in particular to a kind of high refractive index boracic organic silicon rigidity-increasing stick and preparation method thereof.The tackifier rubber compatibility is good, there is no catalyst poisoning phenomenons, boron atom therein can mutually attract with by the electron cloud on the phenyl in viscous substrate polyphthalamide (PPA), improve the adhesive property of silicon rubber and polyphthalamide (PPA).Its preparation process is simple, and repeatability and controllability are good, and the catalyst of use is easy to filter by decompression and remove, and reaction condition is mild, and reaction process does not use organic solvent, it is easy to accomplish industrialization.By changing reaction condition and reactant ratio, for the viscosity of resulting organic silicon rigidity-increasing stick down to 56.8~73.6mPas, refractive index is up to 1.5078~1.5203, the additional organosilicon rubber suitable for high refractive index.
Description
Technical field
The invention belongs to the additive agent fields of organic silicon rubber, and in particular to a kind of high refractive index boracic organic silicon rigidity-increasing stick
And preparation method thereof.
Background technique
Add-on type liquid silicon rubber is that development is very fast, class is higher, product technology content is larger in recent years, and has higher
A kind of organosilicon product of added value.Such product has excellent weatherability and electrical insulating property, high production efficiency, overall cost
The features such as low.It is applied to the industries such as electronic apparatus, machinery, automobile, building more and more widely at present.However, add-on type silicon
Rubber due to molecule itself be in nonpolarity, as encapsulating, coating, inserts injecting forming material in use, cementability is very poor.Mesh
Before, there are mainly three types of the methods that improve the cementability of silicon rubber and a variety of materials: first is that with silane coupling agent to substrate surface at
Reason, the method increase production process and production time, reduce production efficiency, while silane coupling agent uses flammable solvent more, cause
Peril of transportation and environmental pollution；Second is that enhancing cementability by changing base rubber molecular structure, but this method is due to actual production
Process is more complicated, and the cost is relatively high, not yet industrializes at present；Third is that cementability is improved by addition tackifier, the method
Have many advantages, such as composite component that is easy to operate, easily controllable, can be applied to production complexity, there is vast potential for future development.
Chinese patent CN102898972A, which is disclosed, a kind of prepares a kind of additional organosilicon casting glue with metatitanic acid ester catalysis
With the method for tackifier, use crylic acid hydroxy ester and glycidol ether alkoxy silane for raw material, in the catalysis item of titanate esters
Under part, then product is sloughed low-boiling-point substance by heating stirring, and organic silicon rigidity-increasing stick is made.
Chinese patent CN108164705A discloses a kind of preparation method of odorlessness add-on type liquid silicon rubber tackifier,
It is anti-that Si―H addition reaction is carried out with the organic compound containing phenyl and vinyl under conditions of platinum catalyst by phenyl hydrogen-containing silicon oil
A kind of scentless organic silicon rigidity-increasing stick should be made.
The synthesis technology of above-mentioned traditional organic silicon rigidity-increasing stick mostly uses greatly organic solvent as the solvent of reaction process, after
Phase needs to wash or organic solvent is distilled off, and is easy to produce a large amount of waste water and pollution environment, not environmentally friendly enough.And anti-
The later period should be caused to be difficult to remove using homogeneous catalyst in the process, the performance of tackifier is had adverse effect on.Therefore provide one
Kind of synthesis technology is simple, production process environmental protection and energy saving and easily removes the synthetic method of catalyst in reaction process to being prepared with
Machine silicon tackifier have great significance.
Summary of the invention
In order to solve the above-mentioned technical problem, the primary purpose of the present invention is that providing a kind of high refractive index boracic organic silicon rigidity-increasing
The preparation method of stick.
Another object of the present invention is to provide a kind of high refractive index boracic organic silicon rigidity-increasings obtained by above-mentioned preparation method
Stick.The tackifier solve the problems, such as that addition-type silicon rubber is weak to polyphthalamide (PPA) cementability.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A kind of preparation method of high refractive index boracic organic silicon rigidity-increasing stick, includes the following steps:
(1) preparation of the end hydroxyl silicone oil with active group
Aminomethyl phenyl dimethoxysilane, vinyl methyl dimethoxysilane and deionized water are mixed, reacted
Object is added acidic catalyst, condensation reaction is hydrolyzed under condition of heating and stirring, obtains the terminal hydroxy group silicon with active group
Oil；
(2) preparation of high refractive index boracic organic silicon rigidity-increasing stick
End hydroxyl silicone oil with active group is instilled into boron alkyl acid esters, the alkoxy silane containing epoxy group and is contained
In the mixture for having the alkoxy silane of vinyl, obtain reactant, basic catalyst be added, under conditions of heating stirring into
The reaction of row non-hydrolytic sol-gel arrives the high refractive index boracic organic silicon rigidity-increasing stick after reaction product is purified.
It preferably, further include terminal hydroxy group after the end hydroxyl silicone oil with active group is obtained described in step (1)
The purification step of silicone oil, specific purification step are as follows: the end hydroxyl silicone oil with active group being depressurized and is filtered, acid sun is removed
Filtrate is moved into separatory funnel, adds water to be neutralized to neutrality, stratification 30min takes lower layer's oily liquid by ion exchange resin
Body, vacuum distillation removes moisture under the conditions of 90 DEG C and -0.096MPa.
Preferably, aminomethyl phenyl dimethoxysilane described in step (1) and vinyl methyl dimethoxysilane
The molar ratio of summation and deionized water is 1:10~1:16.
Preferably, aminomethyl phenyl dimethoxysilane described in step (1) and vinyl methyl dimethoxysilane
Molar ratio is 1:1~4:1.
Preferably, acidic catalyst described in step (1) is the acid cation tree in Nankai Univ. chemical plant
Rouge.
Preferably, acidic catalyst described in step (1) accounts for the 0.5%~3% of reactant quality.
Preferably, the temperature of hydrolysis-condensation reaction described in step (1) is 70 DEG C~95 DEG C, and the reaction time is 1~4 small
When.
Preferably, the mode of instillation described in step (2) is that constant pressure is added in the end hydroxyl silicone oil with active group
In dropping funel, constant pressure funnel piston is adjusted, liquid is added dropwise in 2h.
Preferably, boron alkyl acid esters described in step (2) be trimethylborate, triethyl borate, triproylborate or
Butyl borate.
Preferably, the alkoxy silane containing epoxy group described in step (2) is γ-glycidyl ether oxygen propyl front three
Oxysilane, γ-glycidoxypropyltrietandysilane andysilane, γ-glycidyl ether oxygen propyl methyl dimethoxysilane
Or γ-glycidyl ether oxygen propyl methyldiethoxysilane.
Preferably, the alkoxy silane containing vinyl described in step (2) is vinyltrimethoxysilane, ethylene
Ethyl triethoxy silicane alkane, vinyl methyl dimethoxysilane, γ-methacryloxypropylmethyl dimethoxysilane or
γ-methacryloxypropyl trimethoxy silane.
Preferably, the molar ratio of hydroxyl and alkoxy is 2:3~1:5 in reactant described in step (2).
Preferably, basic catalyst described in step (2) is basic anionic resin.
Preferably, basic catalyst described in step (2) accounts for the 0.5%~3% of reactant quality.
Preferably, the temperature of the reaction of non-hydrolytic sol-gel described in step (2) is 80 DEG C~100 DEG C, the reaction time
It is 3~6 hours.
Preferably, purification step described in step (2) is that reaction product is carried out to decompression to filter removing catalyst, then
Filtrate decompression is distilled, the low-boiling-point substance under the conditions of 100 DEG C and -0.096MPa in removing system.
The present invention further provides a kind of high refractive index boracic organic silicon rigidity-increasing sticks obtained by above-mentioned preparation method.
Compared with the existing technology, beneficial effects of the present invention are as follows:
Contain boron atom in the tackifier that the present invention synthesizes, with stronger electron-withdrawing ability, and by the poly- neighbour of viscous substrate
Contain a large amount of phenyl in benzenedicarboxamide (PPA), has a large amount of electron cloud on phenyl, pass through the electron attraction of boron atom
The adhesive property of silicon rubber Yu polyphthalamide (PPA) can be significantly improved.Using acid in the preparation process of the tackifier
Property cation exchange resin and alkalescence anion-exchange resin as reaction catalyst, after reaction be easy by decompression take out
It filters out.Its preparation process is simple, and repeatability and controllability are good, and reaction condition is mild, and reaction process is without using organic molten
Agent, it is easy to accomplish industrialization.By changing reaction condition and reactant ratio, the high refractive index boracic organic silicon rigidity-increasing reacted
The viscosity of stick is up to 1.5078~1.5203 down to 56.8~73.6mPas, refractive index, the addition suitable for high refractive index
Type organic silicon rubber, and it is good with rubber compatibility, catalyst poisoning phenomenon is not present.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
For not specifically specified technological parameter, routine techniques progress can refer to.
Embodiment 1
The present embodiment provides a kind of high refractive index boracic organic silicon rigidity-increasing sticks and preparation method thereof.
(1) 18.22g aminomethyl phenyl dimethoxysilane, 13.22g vinyl methyl dimethoxysilane and 43.21g are taken
Deionized water is added in the 250ml three-necked flask equipped with magnetic agitation and temperature controller, is then added and is accounted for overall reaction substance
The acid cation exchange resin of amount score 1% reacts 2h under the conditions of 85 DEG C.After reaction, product at reduced pressure is filtered, is removed
Acid cation exchange resin is removed, filtrate is moved into separatory funnel, adds water to be neutralized to neutrality, stratification 30min takes lower layer
Oily liquids, vacuum distillation removes moisture under the conditions of 90 DEG C and -0.096Mpa.
(2) by the product after above-mentioned purification in a manner of being added dropwise with 23.62g γ-glycidyl ether oxygen propyl trimethoxy
Silane, 11.72g γ-methacryloxypropyl trimethoxy silane and 18.80g triproylborate are mixed to join and are equipped with
In the 250ml three-necked flask of magnetic agitation and temperature controller, then be added account for total reactant quality score 1% alkalinity yin from
Sub-exchange resin reacts 4h under the conditions of 95 DEG C, after reaction, product at reduced pressure is filtered and removes alkalescence anion-exchange resin,
Then filtrate is transferred in round bottom distilling flask, the by-product under the conditions of 100 DEG C and -0.096MPa in removing system, from
And colorless and transparent high refractive index boracic organic silicon rigidity-increasing stick is made.
Embodiment 2
The present embodiment provides a kind of high refractive index boracic organic silicon rigidity-increasing sticks and preparation method thereof.
(1) 18.22g aminomethyl phenyl dimethoxysilane, 13.22g vinyl methyl dimethoxysilane and 43.21g are taken
Deionized water is added in the 250ml three-necked flask equipped with magnetic agitation and temperature controller, is then added and is accounted for overall reaction substance
The acid cation exchange resin of amount score 1% reacts 2h under the conditions of 85 DEG C.After reaction, product at reduced pressure is filtered, is removed
Acid cation exchange resin is removed, filtrate is moved into separatory funnel, adds water to be neutralized to neutrality, stratification 30min takes lower layer
Oily liquids, vacuum distillation removes moisture under the conditions of 90 DEG C and -0.096Mpa.
(2) by the product after above-mentioned purification in a manner of being added dropwise with 18.89g γ-glycidyl ether oxygen propyl trimethoxy
Silane, 18.75g γ-methacryloxypropyl trimethoxy silane and 15.05g triproylborate are mixed to join and are equipped with
In the 250ml three-necked flask of magnetic agitation and temperature controller, then be added account for total reactant quality score 1% alkalinity yin from
Sub-exchange resin reacts 4h under the conditions of 95 DEG C, after reaction, product at reduced pressure is filtered and removes alkalescence anion-exchange resin,
Then filtrate is transferred in round bottom distilling flask, the by-product under the conditions of 100 DEG C and -0.096MPa in removing system, from
And colorless and transparent high refractive index boracic organic silicon rigidity-increasing stick is made.
Embodiment 3
The present embodiment provides a kind of high refractive index boracic organic silicon rigidity-increasing sticks and preparation method thereof.
(1) 18.22g aminomethyl phenyl dimethoxysilane, 13.22g vinyl methyl dimethoxysilane and 43.21g are taken
Deionized water is added in the 250ml three-necked flask equipped with magnetic agitation and temperature controller, is then added and is accounted for overall reaction substance
The acid cation exchange resin of amount score 1% reacts 2h under the conditions of 85 DEG C.After reaction, product at reduced pressure is filtered, is removed
Acid cation exchange resin is removed, filtrate is moved into separatory funnel, adds water to be neutralized to neutrality, stratification 30min takes lower layer
Oily liquids, vacuum distillation removes moisture under the conditions of 90 DEG C and -0.096Mpa.
(2) by the product after above-mentioned purification in a manner of being added dropwise with 24.84g γ-glycidyl ether oxygen propyl methyl diethyl
Oxysilane, 26.04g γ-methacryloxypropyl methyl diethoxysilane and the mixing of 23.02g butyl borate add
Enter into the 250ml three-necked flask equipped with magnetic agitation and temperature controller, is then added and accounts for total reactant quality score 1%
Alkalescence anion-exchange resin reacts 4h under the conditions of 95 DEG C, after reaction, product at reduced pressure is filtered and removes alkali anion
Then filtrate is transferred in round bottom distilling flask by exchanger resin, under the conditions of 100 DEG C and -0.096MPa in removing system
By-product, so that colorless and transparent high refractive index boracic organic silicon rigidity-increasing stick be made.
Embodiment 4
The present embodiment provides a kind of high refractive index boracic organic silicon rigidity-increasing sticks and preparation method thereof.
(1) 18.22g aminomethyl phenyl dimethoxysilane, 13.22g vinyl methyl dimethoxysilane and 43.21g are taken
Deionized water is added in the 250ml three-necked flask equipped with magnetic agitation and temperature controller, is then added and is accounted for overall reaction substance
The acid cation exchange resin of amount score 1% reacts 4h under the conditions of 80 DEG C.After reaction, product at reduced pressure is filtered, is removed
Acid cation exchange resin is removed, filtrate is moved into separatory funnel, adds water to be neutralized to neutrality, stratification 30min takes lower layer
Oily liquids, vacuum distillation removes moisture under the conditions of 90 DEG C and -0.096Mpa.
(2) by the product after above-mentioned purification in a manner of being added dropwise with 23.62g γ-glycidyl ether oxygen propyl trimethoxy
Silane, 11.72g γ-methacryloxypropyl trimethoxy silane and 18.80g triproylborate are mixed to join and are equipped with
In the 250ml three-necked flask of magnetic agitation and temperature controller, then be added account for total reactant quality score 1% alkalinity yin from
Sub-exchange resin reacts 5h under the conditions of 90 DEG C, after reaction, product at reduced pressure is filtered and removes alkalescence anion-exchange resin,
Then filtrate is transferred in round bottom distilling flask, the by-product under the conditions of 100 DEG C and -0.096MPa in removing system, from
And colorless and transparent high refractive index boracic organic silicon rigidity-increasing stick is made.
Embodiment 5
The present embodiment provides a kind of high refractive index boracic organic silicon rigidity-increasing sticks and preparation method thereof.
(1) 18.22g aminomethyl phenyl dimethoxysilane, 13.22g vinyl methyl dimethoxysilane and 43.21g are taken
Deionized water is added in the 250ml three-necked flask equipped with magnetic agitation and temperature controller, is then added and is accounted for overall reaction substance
The acid cation exchange resin of amount score 1% reacts 2h under the conditions of 90 DEG C.After reaction, product at reduced pressure is filtered, is removed
Acid cation exchange resin is removed, filtrate is moved into separatory funnel, adds water to be neutralized to neutrality, stratification 30min takes lower layer
Oily liquids, vacuum distillation removes moisture under the conditions of 90 DEG C and -0.096Mpa.
(2) by the product after above-mentioned purification in a manner of being added dropwise with 23.62g γ-glycidyl ether oxygen propyl trimethoxy
Silane, 11.72g γ-methacryloxypropyl trimethoxy silane and 18.80g triproylborate are mixed to join and are equipped with
In the 250ml three-necked flask of magnetic agitation and temperature controller, then be added account for total reactant quality score 1% alkalinity yin from
Sub-exchange resin reacts 2h under the conditions of 100 DEG C, after reaction, product at reduced pressure is filtered and removes alkali anion exchange tree
Then filtrate is transferred in round bottom distilling flask by rouge, the by-product under the conditions of 100 DEG C and -0.096MPa in removing system,
To which colorless and transparent high refractive index boracic organic silicon rigidity-increasing stick be made.
Testing example
84g Vinyl MQ silicon resin, 6g containing hydrogen silicone oil, 0.9g inhibitor and 0.45g chloroplatinic acid catalyst are mixed, stirring
Add-on type liquid silicon rubber sizing uniformly is made, sizing is divided into 6 equal parts, every part of 15g is respectively labeled as embodiment
1, embodiment 2, embodiment 3, embodiment 4, embodiment 5 and blank sample are separately added into the increasing of each embodiment preparation by corresponding relationship
Stick 0.23g, blank sample are not added other any additives, each style are stirred evenly, and are put into deaeration in vacuum oven
30min is subsequently filled in tensile bars, be placed in baking oven be 90 DEG C in temperature at solidify 1h, temperature is to solidify at 150 DEG C
2h.Shear strength test is carried out to each style using universal testing machine, test result is as shown in table 1.
The test method of sample performance is as follows in table 1:
1, the viscosity of the organic silicon rigidity-increasing stick obtained according to GB/T2794-1995 measurement synthesis；
2, the refraction of the organic silicon rigidity-increasing stick and add-on type liquid silicon rubber obtained according to GB/T614-2006 measurement synthesis
Rate；
3, according to the shear strength of GB/T13936-1992 measurement addition-type silicon rubber and Nian Jie substrate.
Table 1
As seen from the data in Table 1, after high refractive index boracic organic silicon rigidity-increasing stick of the invention is added in silicon rubber, with silicon rubber
The compatibility of glue is preferable, and can be obviously improved silicon rubber to the adhesive strength of copper sheet and polyphthalamide (PPA).
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by change, modification, substitution, combination and simplify,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of high refractive index boracic organic silicon rigidity-increasing stick, which comprises the steps of:
(1) preparation of the end hydroxyl silicone oil with active group
Aminomethyl phenyl dimethoxysilane, vinyl methyl dimethoxysilane and deionized water are mixed, reactant is obtained, adds
Enter acidic catalyst, condensation reaction is hydrolyzed under condition of heating and stirring, obtains the end hydroxyl silicone oil with active group；
(2) preparation of high refractive index boracic organic silicon rigidity-increasing stick
End hydroxyl silicone oil with active group is instilled into boron alkyl acid esters, the alkoxy silane containing epoxy group and contains second
In the mixture of the alkoxy silane of alkenyl, reactant is obtained, basic catalyst is added, is carried out under conditions of heating stirring non-
Hydrolytic sol gel reaction arrives the high refractive index boracic organic silicon rigidity-increasing stick after reaction product is purified.
2. the preparation method of high refractive index boracic organic silicon rigidity-increasing stick according to claim 1, which is characterized in that in step
(1) obtaining after having the end hydroxyl silicone oil of active group described in, further includes the purification step of end hydroxyl silicone oil, specifically mentions
Pure steps are as follows: the end hydroxyl silicone oil with active group being depressurized and is filtered, acid cation exchange resin is removed, filtrate is moved
Enter in separatory funnel, water is added to be neutralized to neutrality, stratification 30min takes lower layer's oily liquids, in 90 DEG C and -0.096MPa item
Vacuum distillation removes moisture under part.
3. the preparation method of high refractive index boracic organic silicon rigidity-increasing stick according to claim 1, it is characterised in that:
The summation and deionization of aminomethyl phenyl dimethoxysilane described in step (1) and vinyl methyl dimethoxysilane
The molar ratio of water is 1:10~1:16；
The molar ratio of aminomethyl phenyl dimethoxysilane described in step (1) and vinyl methyl dimethoxysilane is 1:1
~4:1.
4. the preparation method of high refractive index boracic organic silicon rigidity-increasing stick according to claim 1, it is characterised in that:
Acidic catalyst described in step (1) is the acidic cationic resin in Nankai Univ. chemical plant；
Acidic catalyst described in step (1) accounts for the 0.5%~3% of reactant quality.
5. the preparation method of high refractive index boracic organic silicon rigidity-increasing stick according to claim 1, it is characterised in that: step
(1) temperature of the hydrolysis-condensation reaction described in is 70 DEG C~95 DEG C, and the reaction time is 1~4 hour.
6. the preparation method of high refractive index boracic organic silicon rigidity-increasing stick according to claim 1, it is characterised in that:
Boron alkyl acid esters described in step (2) is trimethylborate, triethyl borate, triproylborate or butyl borate；
Alkoxy silane containing epoxy group described in step (2) be γ-glycidyl ether oxygen propyl trimethoxy silicane,
γ-glycidoxypropyltrietandysilane andysilane, γ-glycidyl ether oxygen propyl methyl dimethoxysilane or γ-shrink
Glycerol ether oxygen propyl methyldiethoxysilane；
Alkoxy silane containing vinyl described in step (2) is vinyltrimethoxysilane, vinyl triethoxyl
Silane, vinyl methyl dimethoxysilane, γ-methacryloxypropylmethyl dimethoxysilane or γ-methyl-prop
Alkene acryloxypropylethoxysilane trimethoxy silane.
7. the preparation method of high refractive index boracic organic silicon rigidity-increasing stick according to claim 1, it is characterised in that:
The molar ratio of hydroxyl and alkoxy is 2:3~1:5 in reactant described in step (2)；
Basic catalyst described in step (2) is basic anionic resin；
Basic catalyst described in step (2) accounts for the 0.5%~3% of reactant quality.
8. the preparation method of high refractive index boracic organic silicon rigidity-increasing stick according to claim 1, it is characterised in that: step
(2) temperature of the non-hydrolytic sol-gel reaction described in is 80 DEG C~100 DEG C, and the reaction time is 3~6 hours.
9. the preparation method of high refractive index boracic organic silicon rigidity-increasing stick according to claim 1, it is characterised in that:
The mode of instillation described in step (2) is that the end hydroxyl silicone oil with active group is added in constant pressure funnel,
Constant pressure funnel piston is adjusted, liquid is added dropwise in 2h；
Purification step described in step (2) is that reaction product is carried out to decompression to filter removing catalyst, then by filtrate decompression
Distillation, the low-boiling-point substance under the conditions of 100 DEG C and -0.096MPa in removing system.
10. a kind of high refractive index boracic organic silicon rigidity-increasing stick, it is characterised in that: by preparation according to any one of claims 1 to 9
Method obtains.
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