CN106831849A - A kind of preparation method containing allyl based polysiloxane - Google Patents
A kind of preparation method containing allyl based polysiloxane Download PDFInfo
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- CN106831849A CN106831849A CN201710059357.0A CN201710059357A CN106831849A CN 106831849 A CN106831849 A CN 106831849A CN 201710059357 A CN201710059357 A CN 201710059357A CN 106831849 A CN106831849 A CN 106831849A
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- containing allyl
- acid
- based polysiloxane
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- -1 polysiloxane Polymers 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 title claims abstract description 16
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000012024 dehydrating agents Substances 0.000 claims abstract description 5
- 150000007524 organic acids Chemical class 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 18
- 229910052736 halogen Inorganic materials 0.000 claims description 14
- 150000002367 halogens Chemical class 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 3
- 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 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 239000003456 ion exchange resin Substances 0.000 claims description 2
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000003495 polar organic solvent Substances 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000011973 solid acid Substances 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- UIDUKLCLJMXFEO-UHFFFAOYSA-N propylsilane Chemical compound CCC[SiH3] UIDUKLCLJMXFEO-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 238000005292 vacuum distillation Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000012074 organic phase Substances 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- OWXJKYNZGFSVRC-UHFFFAOYSA-N 1-chloroprop-1-ene Chemical class CC=CCl OWXJKYNZGFSVRC-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- 229910002808 Si–O–Si Inorganic materials 0.000 description 4
- RMRFFCXPLWYOOY-UHFFFAOYSA-N allyl radical Chemical compound [CH2]C=C RMRFFCXPLWYOOY-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- DSAYAFZWRDYBQY-UHFFFAOYSA-N 2,5-dimethylhexa-1,5-diene Chemical group CC(=C)CCC(C)=C DSAYAFZWRDYBQY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000260 silastic Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0874—Reactions involving a bond of the Si-O-Si linkage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention provides a kind of preparation method containing allyl based polysiloxane, by R2R3Si(R4)2、RR 1(CH2=CHCH2)Si‑R4, organic acid is according to mol ratio 1：1‑2.5：0.005 0.01 mixing, react 5 30 minutes at 50 80 DEG C, add dehydrating agent, continue to be reacted 25 hours at 50 80 DEG C；Reaction is down to room temperature after terminating, and dilutes, and is washed to neutrality, and collection organic phase, dry, filtering, concentration, vacuum distillation is collected cut of the relevant pressure with a temperature of, obtains compound products containing Allyl Siloxane.Present invention process mild condition, simple and easy to do, product is relatively pure, it is easy to separate.
Description
Technical field
The invention belongs to organosilicon synthesis technical field, more particularly, to a kind of preparation containing allyl based polysiloxane
Method.
Background technology
The R of compound R containing Allyl Siloxane1(CH2=CHCH2)Si-R4Add because its unsaturated bond for containing may participate in silicon hydrogen
Into reaction, it is adaptable to produce the series such as liquid silastic, addition-type silicon rubber, high-temp glue, rubber, Silica hydrogel and pi-allyl silicone oil
Product, all occupies this essential status in many rubbers, is the important raw material of industry of a class.Especially in recent years
Come, with the development of LED organosilicon material for packaging, the Allyl Siloxane compound containing phenyl can improve silica gel refraction
Rate, reduces viscosity, has wide practical use.
Currently there are no to find to have and prepare the expanding production method containing Allyl Siloxane compound, to find out its cause, mainly
Be allylic silane monomer it is rare, in the market only has the mixture of allyl silicane monomer, due to mixture in it is various
Composition can not be segmented, and repetition stability is poor, caused the structure of the Allyl Siloxane of hydrolytic condensation and can not be stablized, therefore, no
Can expanding production.
The content of the invention
It is an object of the invention to according to deficiency of the prior art, there is provided a kind of preparation containing allyl based polysiloxane
Method.
The present invention it is homemade, stabilization, on the basis of the allyl silicane monomer that purity is very high, make to synthesize high-quality
Be guaranteed containing Allyl Siloxane.
Above-mentioned purpose of the present invention is achieved through the following technical solutions：
The invention provides a kind of preparation method containing allyl based polysiloxane, the structure containing allyl based polysiloxane
Formula is shown in formula (I)：
Wherein, n >=1, R, R1、R2And R3It is identical or differ, it is alkoxy, halogen, alkyl, pi-allyl, aryl, quilt
The monovalent hydrocarbon of the alkyl, acryloyl group and epoxy radicals of the substitution of one or more halogens；
The preparation method containing allyl based polysiloxane, comprises the following steps：
By R2R3Si(R4)2、RR1(CH2=CHCH2)Si-R4, organic acid, catalyst is according to mol ratio 1:1-1.5:1-2.5：
0.005-0.01 is added in reaction bulb, lower 50-80 DEG C of the intensification of stirring, stirring reaction 5-30 minutes at this temperature, is added de-
Aqua, continues to be reacted 2-5 hours at 50-80 DEG C；
Wherein, R, R1、R2And R3It is identical or differ, it is respectively and independently selected from alkoxy, halogen, alkyl, pi-allyl, virtue
The monovalent hydrocarbon of base, the alkyl replaced by one or more halogens, acryloyl group and epoxy radicals；R4 is halogen or alkoxy；
The RR1(CH2=CHCH2)Si-R4Preparation method be：
S1, under nitrogen atmosphere, by R1R2R3SiR4, magnesium chips, catalyst mixing, heating；
S2, a certain amount of halogen propylene is first added in the mixed solution of S1 to react；
S3, reactant in S2 is reacted into 4-6 hour at a reflux temperature；
S4, addition surplus halogen propylene, continue to react, and are incubated 30-50 minutes；After the completion of reaction, filtering, purification obtains final product institute
State allyl silicane.
Preferably, the addition of the dehydrating agent described in step B is R2R3Si(R4)20.5-1.5 times of mole.
Preferably, the organic acid described in step B is formic acid, acetic acid or propionic acid.
Preferably, catalyst described in step B is strong acid catalyst, selected from hydrochloric acid, the concentrated sulfuric acid, TFMS, strong acid
One or more in property ion exchange resin, solid acid.
Preferably, dehydrating agent used in step B is the concentrated sulfuric acid, acetic anhydride or N, N '-dicyclohexylcarbodiimide.
Preferably, the non-polar organic solvent described in step C is benzene,toluene,xylene, n-hexane, hexamethylene or just
Heptane.
Compared with prior art, the invention has the advantages that：
The preparation method raw material that the present invention is provided is cheap and easy to get, and process conditions are gentle, simple and easy to do, it is adaptable to industrial metaplasia
Produce, low production cost；The product purity for preparing is high, it is easy to separate, and yield is up to more than 85%.
Specific embodiment
The present invention is further illustrated below in conjunction with specific embodiment, but embodiment does not do any type of to the present invention
Limit.Unless stated otherwise, the reagent for using of the invention, method and apparatus are the art conventional reagent, method and apparatus.
Unless stated otherwise, agents useful for same of the present invention and material are purchased in market.
Embodiment 1：
(CH3)2(CH2=CHCH2)Si-O-(CH3)2Si-O-Si(CH2CH=CH2)(CH3)2Preparation method
(1) allyl dimethyl methoxylsilane is first prepared, method is as follows：
In the tetra- mouthfuls of glass round bottom of 250ml with reflux condensing tube, thermometer, agitator, heater and balance charging device
In flask, under nitrogen protection, 10 grams of magnesium chips, 21 grams of chloropropenes, 50 grams of dimethyldimethoxysil,nes and 0.6 gram of iodine are added
With the mixture (KI accounts for 30-55%) of KI, it is heated to reflux 5 hours, starts that remaining 10 grams of chloropropenes are added dropwise, utilizes
One hour all adds.30 minutes are incubated after adding, terminate reaction.Reaction solution analysis result is dimethallyl ylmethoxy
Silane yield is 91.51%.
(2) by dimethyldimethoxysil,ne (62 grams), TFMS (0.2 gram), allyl dimethyl ylmethoxy silicon
Alkane (60 grams), acetic acid (32.89 grams) is added in four-hole boiling flask, is warmed up to 65 DEG C, is reacted 35 minutes, and acetic anhydride is then added dropwise
(12.76 grams), continue to react 2 hours at 65 DEG C.Room temperature is cooled to after reaction completely, toluene is added, is washed with deionized
To neutrality.Toluene layer is collected, adds anhydrous calcium chloride to dry.Drier is filtered off, toluene is removed after filtrate concentration.Concentrate depressurizes
Distillation, collects 168-170 DEG C/4mmHg cuts, yield 51.2%, purity 99.12%.
Embodiment 2
(CH3)(CH2=CHCH2)2Si-O-(CH3)2Si-O-Si(CH2CH=CH2)2(CH3) preparation method
(1) in the tetra- mouthfuls of glass circles of 250ml with reflux condensing tube, thermometer, agitator, heater and balance charging device
In the flask of bottom, under nitrogen protection, 11 grams of magnesium chips, 20 grams of chloropropenes, 30 grams of MTMSs and 0.2 gram of iodine are added
Methane, 3 grams of ether make catalyst, are heated to reflux 5.5 hours, start that remaining 13 grams of chloropropenes are added dropwise, using a hour
All add.70 minutes are incubated after adding, terminate reaction.Reaction solution analysis result is methyl diallyl methoxy silane yield
It is 88.55%.
(2) by dimethyldimethoxysil,ne (35 grams), TFMS (0.17 gram), diallyl methyl methoxy base silicon
Alkane (89 grams), acetic acid (37.89 grams) is added in four-hole boiling flask, is warmed up to 75 DEG C, is reacted 55 minutes, and acetic anhydride is then added dropwise
(19.76 grams), continue to react 2 hours at 75 DEG C.Room temperature is cooled to after reaction completely, toluene is added, is washed with deionized
To neutrality.Toluene layer is collected, adds anhydrous calcium chloride to dry.Drier is filtered off, toluene is removed after filtrate concentration.Concentrate depressurizes
Distillation, collects 178-181 DEG C/4mmHg cuts, yield 50.2%, purity 98.56%.
Embodiment 3
(CH2=CHCH2)3Si-O-(C6H5)2Si-O-Si(CH2CH=CH2)3Preparation method
By dimethoxydiphenylsilane (65 grams), TFMS (0.17 gram), triallyl methoxy silane (92
Gram, with reference to the synthetic method of embodiment 1), acetic acid (35.89 grams) is added in four-hole boiling flask, is warmed up to 77 DEG C, is reacted 75 minutes,
Then acetic anhydride (22.76 grams) is added dropwise, continues to react 3 hours at 77 DEG C.Room temperature is cooled to after reaction completely, toluene is added,
Neutrality is washed with deionized.Toluene layer is collected, adds anhydrous calcium chloride to dry.Drier is filtered off, is removed after filtrate concentration
Toluene.Concentrate vacuum distillation, collects 180-183 DEG C/4mmHg cuts, yield 47.2%, purity 97.69%.
Embodiment 4
(CH2=CHCH2)3Si-O-(CH3)(CH2=CHCH2)Si-O-Si(CH2CH=CH2)3Preparation method
By methacrylic dimethoxysilane (45 grams, with reference to the method for embodiment 1), TFMS (0.17 gram), three
Allyl methoxyl silane (90 grams), acetic acid (31.89 grams) is added in four-hole boiling flask, is warmed up to 65 DEG C, reacts 55 minutes, so
Acetic anhydride (23.76 grams) is added dropwise afterwards, continues to react 2 hours at 65 DEG C.Room temperature is cooled to after reaction completely, toluene is added, used
Neutrality is arrived in deionized water washing.Toluene layer is collected, adds anhydrous calcium chloride to dry.Drier is filtered off, first is removed after filtrate concentration
Benzene.Concentrate vacuum distillation, collects 130-133 DEG C/4mmHg cuts, yield 55.21%, purity 99.69%.
Claims (6)
1. a kind of preparation method containing allyl based polysiloxane, it is characterised in that the structure containing allyl based polysiloxane is led to
Formula is shown in formula (I)：
Wherein, n >=1, R, R1、R2And R3It is identical or differ, it is respectively and independently selected from alkoxy, halogen, alkyl, pi-allyl, virtue
The monovalent hydrocarbon of base, the alkyl replaced by one or more halogens, acryloyl group and epoxy radicals；
The preparation method containing allyl based polysiloxane, comprises the following steps：
By R2R3Si(R4)2、RR1(CH2=CHCH2)Si-R4, organic acid, catalyst is according to mol ratio 1:1-1.5:1-2.5：
0.005-0.01 is added in reaction bulb, lower 50-80 DEG C of the intensification of stirring, stirring reaction 5-30 minutes at this temperature, is added de-
Aqua, continues to be reacted 2-5 hours at 50-80 DEG C；
Wherein, R, R1、R2And R3It is identical or differ, it is respectively and independently selected from alkoxy, halogen, alkyl, pi-allyl, aryl, quilt
The monovalent hydrocarbon of the alkyl, acryloyl group and epoxy radicals of the substitution of one or more halogens；R4 is halogen or alkoxy；
The RR1(CH2=CHCH2)Si-R4Preparation method be：
S1, under nitrogen atmosphere, by R1R2R3SiR4, magnesium chips, catalyst mixing, heating；
S2, a certain amount of halogen propylene is first added in the mixed solution of S1 to react；
S3, reactant in S2 is reacted into 4-6 hour at a reflux temperature；
S4, addition surplus halogen propylene, continue to react, and are incubated 30-50 minutes；After the completion of reaction, filtering, purification obtains final product the alkene
Propyl silane.
2. a kind of preparation method containing allyl based polysiloxane according to claim 1, it is characterized in that, described in step B
Dehydrating agent addition be R2R3Si(R4)20.5-1.5 times of mole.
3. a kind of preparation method containing allyl based polysiloxane according to claim 1, it is characterized in that, described in step B
Organic acid be formic acid, acetic acid or propionic acid.
4. a kind of preparation method containing allyl based polysiloxane according to claim 1, it is characterized in that, described in step B
Catalyst is strong acid catalyst, selected from hydrochloric acid, the concentrated sulfuric acid, TFMS, strong-acid ion exchange resin, solid acid
Plant or several.
5. a kind of preparation method containing allyl based polysiloxane according to claim 1, it is characterized in that, it is used in step B
Dehydrating agent be the concentrated sulfuric acid, acetic anhydride or N, N '-dicyclohexylcarbodiimide.
6. a kind of preparation method containing allyl based polysiloxane according to claim 1, it is characterized in that, described in step C
Non-polar organic solvent is benzene,toluene,xylene, n-hexane, hexamethylene or normal heptane.
Priority Applications (1)
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| CN109942614A (en) * | 2019-03-04 | 2019-06-28 | 矽时代材料科技股份有限公司 | A kind of preparation method of the based polysiloxane containing hexamethylene |
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