CN106432730B - One kind containing Me2The cyclic methyl phenylpolysiloxane preparation method of SiO chain link - Google Patents
One kind containing Me2The cyclic methyl phenylpolysiloxane preparation method of SiO chain link Download PDFInfo
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- CN106432730B CN106432730B CN201610835373.XA CN201610835373A CN106432730B CN 106432730 B CN106432730 B CN 106432730B CN 201610835373 A CN201610835373 A CN 201610835373A CN 106432730 B CN106432730 B CN 106432730B
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- chain link
- preparation
- sio
- cyclic methyl
- toluene
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- -1 siloxanes Chemical class 0.000 claims abstract description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 230000000694 effects Effects 0.000 claims abstract description 7
- 238000007233 catalytic pyrolysis Methods 0.000 claims abstract description 6
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 claims abstract description 6
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- 238000013517 stratification Methods 0.000 claims abstract description 6
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 abstract description 6
- YZFXSGHGWNCLLH-UHFFFAOYSA-N [O].NC[Si]C1=CC=CC=C1 Chemical group [O].NC[Si]C1=CC=CC=C1 YZFXSGHGWNCLLH-UHFFFAOYSA-N 0.000 abstract description 3
- 229920002379 silicone rubber Polymers 0.000 abstract description 3
- 238000005336 cracking Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- NOKUWSXLHXMAOM-UHFFFAOYSA-N hydroxy(phenyl)silicon Chemical compound O[Si]C1=CC=CC=C1 NOKUWSXLHXMAOM-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000010079 rubber tapping Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 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 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- IRVZFACCNZRHSJ-UHFFFAOYSA-N 2,4,6,8-tetramethyl-2,4,6,8-tetraphenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si]1(C)C1=CC=CC=C1 IRVZFACCNZRHSJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
One kind containing Me2The cyclic methyl phenylpolysiloxane preparation method of SiO chain link, is related to a kind of silicon rubber centre preparation, and under hydrochloric acid and toluene effect cohydrolysis reaction is occurred for the dimethyldichlorosilane and dichloromethyl phenylsilane of different mol ratio by the present invention；The reaction obtains the siloxanes mixing liquid of the straight-chain of three ring bodies, four ring bodies, five ring body annular siloxanes and molecular weight with phenyl not etc.；By the liquid after hydrolysis after stratification, upper layer oily liquids is taken to remove water in a rotary evaporator and toluene, it is put into reaction kettle after three hours, the LiOH powder of addition makes its catalytic pyrolysis, control heating rate guarantees to be gradually warmed up under the premise of not slug, after cracking until not having liquid outflow；It is pure in receiving flask containing Me2The cyclic methyl phenylpolysiloxane of SiO chain link is mainly used for synthesizing dimethyl silica chain link and the equally distributed phenyl silicone oil of aminomethyl phenyl silicon oxygen chain link or silicon rubber.
Description
Technical field
The present invention relates to preparations among a kind of silicon rubber, contain Me more particularly to one kind2The ring-type of SiO chain link is poly-
Methyl phenyl siloxane preparation method.
Background technique
Methyl phenyl vinyl silicone oil refers to that a part of silicon atom on main chain is connected with dimethyl and another part is connected with one
The silicone oil of a methyl and a phenyl, special chemical structure assign a series of its excellent properties, are widely used to LED encapsulation
The every field such as material, high-temperaure coating, heat-conducting glue, electronic apparatus, industry light industry textile industry, building materials.Not with its application field
Disconnected to expand, traditional phenyl silicone oil can no longer meet increasingly harsh requirement, and its basic reason is to lead
The uneven distribution of phenyl ring on chain.Current methyl phenyl vinyl silicone oil be by tetramethyl tetraphenyl cyclotetrasiloxane with
Octamethylcy-clotetrasiloxane is copolymerized and is obtained, and dimethyl silica chain link can not be uniform with aminomethyl phenyl silicon oxygen chain link in product
It is alternately distributed, therefore the refractive index of different segments on strand is different, so that homogeneous transparent cannot be obtained, had excellent performance
Phenyl silicone oil.Shown in its structure is generally as follows:
。
Summary of the invention
The purpose of the present invention is to provide one kind to contain Me2The cyclic methyl phenylpolysiloxane preparation method of SiO chain link, this
Invention passes through the product of the available different phenyl contents of proportion of two kinds of ring bodies of control, by adjusting vinyl double seal head agent
The different product of the available molecular weight of additional amount, to adapt to different use conditions, viscosity is than common phenyl siloxane rubber
Low, machinability is good, and heat resisting temperature is higher, mechanical property is more preferable.
The purpose of the present invention is what is be achieved through the following technical solutions:
One kind containing Me2The cyclic methyl phenylpolysiloxane preparation method of SiO chain link, the method includes following synthesis steps
It is rapid:
(1) by the dimethyldichlorosilane of different mol ratio and dichloromethyl phenylsilane, under hydrochloric acid and toluene effect,
Cohydrolysis reaction occurs；The reaction obtains three ring bodies, four ring bodies, five ring body annular siloxanes and molecular weight with phenyl and differs
Straight-chain siloxanes mixing liquid；
(2) by the liquid after hydrolysis after stratification, upper layer oily liquids is taken to remove for 60-70 DEG C in a rotary evaporator
Water and toluene are put into reaction kettle after three hours, and the LiOH powder of addition makes its catalytic pyrolysis, and control heating rate guarantees not
It is gradually heated to 250 DEG C under the premise of slug, is warming up to 300 DEG C again until not having liquid outflow after cracking one hour at 250 DEG C
Until；It is pure in receiving flask containing Me2The cyclic methyl phenylpolysiloxane of SiO chain link.
Described one kind contains Me2The cyclic methyl phenylpolysiloxane preparation method of SiO chain link, the concentration of hydrochloric acid are
1 ~ 10mol/L, the molar ratio of water and ring body is 5 ~ 20:1 in hydrochloric acid.
Described one kind contains Me2The cyclic methyl phenylpolysiloxane preparation method of SiO chain link, the toluene additional amount
For 0.1 ~ 10 times for theoretically 100% generation cyclotetrasiloxane molal quantity.
Described one kind contains Me2The cyclic methyl phenylpolysiloxane preparation method of SiO chain link, the LiOH powder add
Entering amount is mixing liquid quality 0.1 ~ 5%.
The advantages and effects of the present invention are:
The present invention contains Me2What the cyclic methyl phenylpolysiloxane and octamethylcy-clotetrasiloxane of SiO chain link were copolymerized
Polysiloxanes, dimethyl silica chain link in product with aminomethyl phenyl silicon oxygen chain link be it is equally distributed, structure is as follows:
The difference of refractive index, in identical phenyl content, viscosity is not present in the polysiloxane polymer of this structure
Lower than common phenyl siloxane rubber, machinability is good, and heat resisting temperature is higher, mechanical property is more preferable.By controlling two kinds of ring bodies
The available different phenyl contents of proportion product, pass through the available molecular weight of additional amount for adjusting vinyl double seal head agent
Different product, to adapt to different use conditions.
Specific embodiment
The following describes the present invention in detail with reference to examples.
Embodiment 1
(1) by the dimethyldichlorosilane and dichloromethyl phenylsilane of equimolar ratio, in the hydrochloric acid of 6mol/L and certain
It measures under toluene effect, cohydrolysis reaction occurs, wherein the molar ratio of water and mix monomer is 10:1 in hydrochloric acid.The reaction obtains band
There is the siloxanes mixing liquid of the straight-chain of three ring bodies, four ring bodies, five ring body annular siloxanes and the molecular weight of phenyl not etc..
(2) by the liquid after hydrolysis after stratification, upper layer oily liquids is taken to remove for 60-70 DEG C in a rotary evaporator
Remaining liq is put into reaction kettle by water and toluene after three hours, and the LiOH powder that institute's tapping body mass ratio 1.5% is added makes
Its catalytic pyrolysis, control heating rate guarantees to be gradually heated to 250 DEG C under the premise of not slug, after 250 DEG C crack one hour
It is warming up to 300 DEG C again until not having liquid outflow.It is pure in receiving flask containing Me2The cyclomethicones of SiO chain link
Phenyl siloxane, structure DnDP m (D=Me2SiO;DP=MePhSiO) (n=1,2,3;m=1,2,3;3"n+m"6 ).Wherein first
The amount of benzene is as follows to yield impact according to theoretically 100% 0.5 times to 2.5 times for generating cyclotetrasiloxane molal quantity:
。
Embodiment 2
(1) by the dimethyldichlorosilane and dichloromethyl phenylsilane of equimolar ratio, in certain density hydrochloric acid and first
Benzene (additional amount is according to theoretically 100% 1 times for generating cyclotetrasiloxane molal quantity).Under effect, cohydrolysis reaction occurs, wherein
The molar ratio of water and mix monomer is 10:1 in hydrochloric acid.It is cyclic annular that the reaction obtains three ring bodies, four ring bodies, five ring bodies with phenyl
The siloxanes mixing liquid of the straight-chain of siloxanes and molecular weight not etc..
(2) by the liquid after hydrolysis after stratification, upper layer oily liquids is taken to remove for 60-70 DEG C in a rotary evaporator
Remaining liq is put into reaction kettle by water and toluene after three hours, and the LiOH powder that institute's tapping body mass ratio 1.5% is added makes
Its catalytic pyrolysis, control heating rate guarantees to be gradually heated to 250 DEG C under the premise of not slug, after 250 DEG C crack one hour
It is warming up to 300 DEG C again until not having liquid outflow.It is pure in receiving flask containing Me2The cyclomethicones of SiO chain link
Phenyl siloxane, structure DnDP m (D=Me2SiO;DP=MePhSiO) (n=1,2,3;m=1,2,3;3"n+m"6 ).Wherein salt
Influence of the acid concentration to yield is as follows:
。
Embodiment 3
(1) by the dimethyldichlorosilane and dichloromethyl phenylsilane of equimolar ratio, in the hydrochloric acid and first of 6mol/L
Benzene (additional amount is according to theoretically 100% 1 times for generating cyclotetrasiloxane molal quantity).Under effect, cohydrolysis reaction occurs, wherein
The molar ratio of water and mix monomer is 10:1 in hydrochloric acid.It is cyclic annular that the reaction obtains three ring bodies, four ring bodies, five ring bodies with phenyl
The siloxanes mixing liquid of the straight-chain of siloxanes and molecular weight not etc..
(2) by the liquid after hydrolysis after stratification, upper layer oily liquids is taken to remove for 60-70 DEG C in a rotary evaporator
Remaining liq is put into reaction kettle by water and toluene after three hours, and the LiOH powder that institute's tapping body certain mass ratio is added makes
Its catalytic pyrolysis, control heating rate guarantees to be gradually heated to 250 DEG C under the premise of not slug, after 250 DEG C crack one hour
It is warming up to 300 DEG C again until not having liquid outflow.It is pure in receiving flask containing Me2The cyclomethicones of SiO chain link
Phenyl siloxane, structure DnDP m (D=Me2SiO;DP=MePhSiO) (n=1,2,3;m=1,2,3;3"n+m"6 ).Wherein
Influence of the LiOH powder addition to yield is as follows:
。
The above specific embodiments are only exemplary, is to preferably make skilled artisans appreciate that originally
Invention is not to be construed as the limitation to the present invention including range；As long as made of disclosed spirit according to the present invention
How with change or modification, range by the invention is each fallen within.
Claims (3)
1. one kind contains Me2The cyclic methyl phenylpolysiloxane preparation method of SiO chain link, which is characterized in that the method includes with
Lower synthesis step:
(1) dimethyldichlorosilane of different mol ratio and dichloromethyl phenylsilane are occurred under hydrochloric acid and toluene effect
Cohydrolysis reaction；The reaction obtains three ring bodies, four ring bodies, five ring body annular siloxanes and molecular weight with phenyl not etc. straight
The siloxanes mixing liquid of chain；
(2) by the liquid after hydrolysis after stratification, take upper layer oily liquids in a rotary evaporator 60-70 DEG C water removal and
Toluene is put into reaction kettle after three hours, and the LiOH powder of addition makes its catalytic pyrolysis, and control heating rate guarantees not slug
Under the premise of be gradually heated to 250 DEG C, 250 DEG C crack one hour after be warming up to again 300 DEG C until do not have liquid outflow until；
It is pure in receiving flask containing Me2The cyclic methyl phenylpolysiloxane of SiO chain link.
2. according to claim 1 a kind of containing Me2The cyclic methyl phenylpolysiloxane preparation method of SiO chain link, feature
It is, the toluene additional amount is 0.1 ~ 10 times of theoretically 100% generation cyclotetrasiloxane molal quantity.
3. according to claim 1 a kind of containing Me2The cyclic methyl phenylpolysiloxane preparation method of SiO chain link, feature
It is, the LiOH powder addition is mixing liquid quality 0.1 ~ 5%.
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| CN201610835373.XA CN106432730B (en) | 2016-09-21 | 2016-09-21 | One kind containing Me2The cyclic methyl phenylpolysiloxane preparation method of SiO chain link |
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| CN106432730B true CN106432730B (en) | 2019-07-05 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110358089A (en) * | 2018-04-11 | 2019-10-22 | 苏州润特新材料科技有限公司 | A kind of preparation method of alkylaryl modified silicon oil |
| CN109400881A (en) * | 2018-10-22 | 2019-03-01 | 浙江衢州正邦有机硅有限公司 | A kind of preparation method of methyl phenyl silicone rubber |
| CN110669221B (en) * | 2019-10-31 | 2021-11-30 | 河北科盛瑞化工有限公司 | Hydrolysis method of high-boiling silicone oil |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935328A (en) * | 2010-07-28 | 2011-01-05 | 杭州师范大学 | Preparation method of methyl phenyl mixed cyclosiloxane |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935328A (en) * | 2010-07-28 | 2011-01-05 | 杭州师范大学 | Preparation method of methyl phenyl mixed cyclosiloxane |
Non-Patent Citations (2)
| Title |
|---|
| 甲基苯基环硅氧烷制备工艺的研究;栾文卉等;《化学反应工程与工艺》;20110228;第27卷(第1期);16-20 |
| 甲基苯基环硅氧烷的制备工艺研究;罗蒙贤等;《精细与专用化学品》;20080706;第16卷(第13期);13-16 |
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