CN1824689A - Synthesis method of silicane coupling agent having long chain polyether chain section - Google Patents
Synthesis method of silicane coupling agent having long chain polyether chain section Download PDFInfo
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- CN1824689A CN1824689A CN 200610049525 CN200610049525A CN1824689A CN 1824689 A CN1824689 A CN 1824689A CN 200610049525 CN200610049525 CN 200610049525 CN 200610049525 A CN200610049525 A CN 200610049525A CN 1824689 A CN1824689 A CN 1824689A
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- chain
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 25
- 229920000570 polyether Polymers 0.000 title claims abstract description 25
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000007822 coupling agent Substances 0.000 title abstract description 5
- 238000001308 synthesis method Methods 0.000 title 1
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 229910000077 silane Inorganic materials 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 9
- 239000013067 intermediate product Substances 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 238000010189 synthetic method Methods 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- -1 amine compound Chemical class 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- 101150065749 Churc1 gene Proteins 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- 102100038239 Protein Churchill Human genes 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 238000007259 addition reaction Methods 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 239000011347 resin Substances 0.000 abstract description 8
- 229920005989 resin Polymers 0.000 abstract description 8
- 239000003960 organic solvent Substances 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 4
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- VOLGAXAGEUPBDM-UHFFFAOYSA-N $l^{1}-oxidanylethane Chemical compound CC[O] VOLGAXAGEUPBDM-UHFFFAOYSA-N 0.000 abstract 1
- 239000004925 Acrylic resin Substances 0.000 abstract 1
- 229920000178 Acrylic resin Polymers 0.000 abstract 1
- 101100027898 Homo sapiens OCR1 gene Proteins 0.000 abstract 1
- 102100026725 Ovarian cancer-related protein 1 Human genes 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 239000003822 epoxy resin Substances 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 229920000647 polyepoxide Polymers 0.000 abstract 1
- 239000004814 polyurethane Substances 0.000 abstract 1
- 229920002635 polyurethane Polymers 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 14
- 238000003756 stirring Methods 0.000 description 12
- 238000009835 boiling Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 6
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 6
- NPSSWQJHYLDCNV-UHFFFAOYSA-N prop-2-enoic acid;hydrochloride Chemical compound Cl.OC(=O)C=C NPSSWQJHYLDCNV-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- RLUJQBLWUQZMDG-UHFFFAOYSA-N toluene;hydrochloride Chemical compound Cl.CC1=CC=CC=C1 RLUJQBLWUQZMDG-UHFFFAOYSA-N 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BMIKLEQSSDZJEN-UHFFFAOYSA-N NC(=O)CCO[Si](OCC)(OCC)CCC Chemical compound NC(=O)CCO[Si](OCC)(OCC)CCC BMIKLEQSSDZJEN-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910008326 Si-Y Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 229910006773 Si—Y Inorganic materials 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Polyethers (AREA)
Abstract
The present invention discloses a method for synthesizing silane coupling agent with long-chain polyether chain segment. Said method includes the following steps: (1), using allyl polyether whose general formula is CH2=CHCH2O(CH2CH2)n(CH2CH(CH3)mH and alkoxyhydrogensilane whose general formula is His(OR)3 as raw material, in which n and m are equal to 1-20, R is methyl or ethyl; adopting chloro-platinic acid solution as catalyst, and utilizing silicon-hydrogen addition synthesis to obtain the hydrosiliconized silane inter-mediate product, then making reduced pressure extraction, purification and separation; and (2), making the obtained hydrosiliconized silane intermediate product and unsaturated acyl chloride whose general formula is CH2=CR1C=OCl implement esterization reaction in solvent, in which R1 is H or methyl, to obtain the long-chain silane coupling agent whose general formula is (RO)3SiCH2CH2CH2O(CH3CH2O)n (CH2CH(CH3)O)mC=OCR1=CH2 and whose one end has double bond and contains a certain polyether chain segment. Said coupling agent can be used for modification of nano SiO2, and can greatly raise dispersivity and stability of SiO2 in organic solvent and organic resins of polyurethane, epoxy resin and acrylic resin, etc.
Description
Technical field
The present invention relates to a kind of synthetic method of organic silane compound, relate to a kind of synthetic method that has long-chain polyether segment silane coupling agent specifically, it belongs to the synthetic and applied research field of organosilicon functional compounds intermediate.
Background technology
Silane coupling agent is the silane compound product that has the inorganic and close organic two kinds of functional groups of parent in the molecule simultaneously, and it is widely used in many industrial circles such as glass fibre, plastics industry, cable, rubber, organic resin and coating.The silane coupling agent of existing in the market many different trades mark and different application type is sold.Yet, better to be used in variant production and different application environment in order to make silane coupling agent, the research of the silane coupling agent of synthetic new molecular structure is all the time also continuing, to reach the purpose of abundant raising product use properties.
Using the chemical modification treatment process, to nanometer SiO
2Carry out study of surfaces and application facet Deng particle, silane coupling agent is a kind of properties-correcting agent commonly used, and (Y can be Cl, OCH to the Si-Y key that it has
3, OC
2H
5Deng) can with SiO
2The Si-OH key on surface carries out chemical condensation reaction, makes SiO
2The surface is transformed into lipophilicity from wetting ability.Nanometer SiO through modification
2Because surface hydroxyl is replaced by organic group, between particle mutually agglomeration reduce, thereby can be evenly and stably be dispersed in organic solvent and the polymeric matrix.
Tradition is usually used in nanometer SiO
2Modified silane coupler is mainly vinyltriethoxysilane, gamma-methyl allyl acyloxypropyl trimethoxysilane, aminocarbonyl propyl triethoxyl silane etc., and these coupling agents are for improving nanometer SiO
2The lipophilicity on surface promotes nanometer SiO
2And the consistency between organic solvent and polymkeric substance are basic reduces SiO
2Reunite and all have certain effect.But above-mentioned coupling agent molecule chain is shorter, thereby to SiO
2When particle surface effectively wraps up, often need to cover more coupling agent molecule.SiO after the modification
2Though particle can be evenly and stably is dispersed in the organic solvent system, still exists the part agglomeration in organic resin or polymeric matrix, can not well be disperseed.
In sum, adopt silane coupling agent to handle nanometer SiO
2Particle exists above shortcoming, and the present invention has designed a kind of long-chain polyether type silane coupler, the enoyl-that its end has can with a lot of vinyl monomer or polymeric matrix generation chemical reactions, promote nanometer SiO
2Consistency with organic matrix.The long-chain polyether segment that it has both can play nanometer SiO
2Modifying functions such as the parcel of particle surface, spatial stability reduce nanometer SiO
2The possibility of reuniting by mutually combining of its surface active groups between particle can also be improved the consistency with organic matrix simultaneously.Thereby improve nanometer SiO greatly
2In organic solvent especially in organic matrix as the dispersiveness in the resins such as urethane, Resins, epoxy with stability.
Summary of the invention
The purpose of this invention is to provide a kind of novel synthetic method that has long-chain polyether segment silane coupling agent.
Its concrete steps are as follows:
1) with the general formula is CH
2=CHCH
2O (CH
2CH
2O)
n(CH
2CH (CH
3) O)
mThe allyl polyether of H and general formula are HSi (OR)
3The alkoxyl group hydrogen silane is a raw material, wherein, n, m=1～20, R is methyl or ethyl; The employing platinum acid chloride solution is a catalyzer, catalyzer is 1～1000ppm of reaction system concentration, allyl polyether and alkoxyl group hydrogen silane mol ratio are 1: 1～1: 1.5, temperature of reaction is 20～100 ℃, reaction times is 1.0～5.0h, by the synthetic hydrogen silication silane intermediate product that obtains of addition reaction of silicon with hydrogen, separate through the decompression extracting and purifying;
2) hydrogen silication midbody product and the general formula with gained is CH
2=CR
1The unsaturated acyl chlorides of C=OCl carries out esterification in solvent, wherein, and R
1Be H or methyl; Adopting organic amine compound is the chlorine absorption agent, and the mol ratio of hydrogen silication silane intermediate product and unsaturated acyl chlorides is 1: 1～1: 1.6, and temperature of reaction is 0～30 ℃, and the reaction times is 3～5h, and the formula of obtaining is: (RO)
3SiCH
2CH
2CH
2O (CH
2CH
2O)
n(CH
2CH (CH
3) O)
mC=OCR
1=CH
2One end has two keys, and contains the long chain silane coupling agent that certain polyether chain is forged.
The solvent of platinum acid chloride solution adopts benzene, toluene, Virahol, tetrahydrofuran (THF) in the step 1) of the present invention.
Step 2 of the present invention) organic amine compound in is triethylamine, pyridine, urea.
Step 2 of the present invention) solvent in is acetone, tetrahydrofuran (THF), toluene, methylene dichloride, trichloromethane.
The present invention can obtain the long-chain polyether type silane coupler of higher yields, and conversion unit is simple, the synthesis condition gentleness.The resulting long-chain polyether type silane coupler of method provided by the invention is mainly in order to nanometer SiO
2Modification, can greatly improve nanometer SiO
2In organic solvent, especially the dispersiveness in organic resin system such as the resins such as urethane, Resins, epoxy is with stable.
Embodiment
The present invention describes with following embodiment, but can not limit content of the present invention.
Embodiment 1
Step 1: have thermometer, condenser, agitator, N
2Feed in the dry four-hole boiling flask of 250mL of mouth, add allyl polyether 100g (molecular weight 400) and HSi (OC
2H
5)
336.9g its mol ratio is 1: 1.11, stirs and be warming up to 60 ℃, splash into 0.4mL concentration and be 4 ‰ Platinic chloride toluene solution (the about 10ppm of catalyst levels), temperature rises rapidly, and controlled temperature is lower than 100 ℃, continue reaction 2h, unreacted HSi (OC is removed in normal temperature discharging, underpressure distillation
2H
5)
3, obtaining product 125.4g, the intermediates yield is 91.60%.Step 2: the 125.4g silicon hydrogen adduct that obtains in the step 1 and 50mL tetrahydrofuran (THF), 25.2g triethylamine are mixed the back add and have thermometer, condenser, agitator, in the dry four-hole boiling flask of the 250mL of constant pressure funnel, the 31.2g methacrylic chloride is dissolved in the 30ml tetrahydrofuran (THF), pours in the constant pressure funnel.Stirring and controlled temperature slowly drip the tetrahydrofuran solution of methacrylic chloride at 5 ℃, and controlled temperature is about 5 ℃, and about 0.5h drips off, and continue stirring reaction 3.5h.Remove by filter the triethylamine hydrochloride of generation, filtrate obtains product 141.4g in 50 ℃ of following removal of solvent under reduced pressure and unreacted methacrylic chloride, and the finished product yield is 90.30%.
Embodiment 2
Step 1: have thermometer, condenser, agitator, N
2Feed in the dry four-hole boiling flask of 250mL of mouth, add allyl polyether 200g (molecular weight 1000) and HSi (OCH
3)
327.4g its mol ratio is 1: 1.13, stirs and be warming up to 70 ℃, splash into 0.6mL concentration and be 4 ‰ Platinic chloride toluene solution (the about 15ppm of catalyst levels), temperature rises rapidly, and controlled temperature is lower than 100 ℃, continue reaction 1.5h, unreacted HSi (OCH is removed in normal temperature discharging, underpressure distillation
3)
3, obtaining product 218.8g, the intermediates yield is 96.22%.Step 2: the 218.8g silicon hydrogen adduct that obtains in the step 1 is mixed with 50mL toluene, 20.2g triethylamine, add and have thermometer, condenser, agitator is in the dry four-hole boiling flask of the 250mL of constant pressure funnel, the 21.7g acrylate chloride is dissolved in the 30ml toluene, pours in the constant pressure funnel.Stirring and controlled temperature slowly drip the toluene solution of acrylate chloride at 5 ℃, and controlled temperature is about 5 ℃, and about 0.75h drips off, and continue stirring reaction 3.25h.Remove by filter the triethylamine hydrochloride of generation, filtrate obtains product 232.8g in 60 ℃ of following removal of solvent under reduced pressure and unreacted acrylate chloride, and the finished product yield is 96.78%.
Embodiment 3
Step 1: have thermometer, condenser, agitator, N
2Feed in the dry four-hole boiling flask of 250mL of mouth, add allyl polyether 100g (molecular weight 400) and HSi (OC
2H
5)
349.2g its mol ratio is 1: 1.20, stirs and be warming up to 70 ℃, splash into 0.25mL concentration and be 4 ‰ Platinic chloride toluene solution (the about 17.5ppm of catalyst levels), temperature rises rapidly, and controlled temperature is lower than 100 ℃, continue reaction 2.5h, unreacted HSi (OC is removed in normal temperature discharging, underpressure distillation
2H
5)
3, obtaining product 134.8g, the intermediates yield is 90.35%.Step 2: the 134.8g silicon hydrogen adduct that obtains in the step 1 is mixed with 50mL tetrahydrofuran (THF), 20g pyridine, add and have thermometer, condenser, agitator, in the dry four-hole boiling flask of the 250mL of constant pressure funnel, the 36.6g methacrylic chloride is dissolved in the 30ml tetrahydrofuran (THF), pours in the constant pressure funnel.Stirring and controlled temperature slowly drip the tetrahydrofuran solution of methacrylic chloride at 5 ℃, and controlled temperature is about 5 ℃, and about 0.5h drips off, and continue stirring reaction 4h.Remove by filter the pyridine hydrochloride of generation, filtrate obtains product 153.8g in 70 ℃ of following removal of solvent under reduced pressure and unreacted methacrylic chloride, and the finished product yield is 89.73%.
Embodiment 4
Step 1: have thermometer, condenser, agitator, N
2Feed in the dry four-hole boiling flask of 250mL of mouth, add allyl polyether 300g (molecular weight 600) and HSi (OCH
3)
330.5g its mol ratio is 1: 1.25, stirs and be warming up to 60 ℃, splash into 0.8mL concentration and be 4 ‰ Platinic chloride toluene solution (the about 10ppm of catalyst levels), temperature rises rapidly, and controlled temperature is lower than 100 ℃, continue reaction 2h, unreacted HSi (OCH is removed in normal temperature discharging, underpressure distillation
3)
3, obtaining product 308.1g, the intermediates yield is 93.22%.Step 2: the 308.1g silicon hydrogen adduct that obtains in the step 1 is mixed with 50mL toluene, 39.6g triethylamine, add and have thermometer, condenser, agitator is in the dry four-hole boiling flask of the 250mL of constant pressure funnel, the 54.3g acrylate chloride is dissolved in the 30ml toluene, pours in the constant pressure funnel.Stirring and controlled temperature slowly drip the toluene solution of acrylate chloride at 5 ℃, and controlled temperature is about 5 ℃, and about 1h drips off, and continue stirring reaction 4h.Remove by filter the triethylamine hydrochloride of generation, 60 ℃ of following removal of solvent under reduced pressure of filtrate and unreacted acrylate chloride obtain product 320.2g, and the finished product yield is 88.36%.
Claims (4)
1. a synthetic method that has long-chain polyether segment silane coupling agent is characterized in that, the step of method is as follows:
1) with the general formula is CH
2=CHCH
2O (CH
2CH
2O)
n(CH
2CH (CH
3) O)
mThe allyl polyether of H and general formula are HSi (OR)
3The alkoxyl group hydrogen silane is a raw material, wherein, n, m=1～20, R is methyl or ethyl; The employing platinum acid chloride solution is a catalyzer, catalyzer is 1～1000ppm of reaction system concentration, allyl polyether and alkoxyl group hydrogen silane mol ratio are 1: 1～1: 1.5, temperature of reaction is 20～100 ℃, reaction times is 1.0～5.0h, by the synthetic hydrogen silication silane intermediate product that obtains of addition reaction of silicon with hydrogen, separate through the decompression extracting and purifying;
2) hydrogen silication midbody product and the general formula with gained is CH
2=CR
1The unsaturated acyl chlorides of C=OCl carries out esterification in solvent, wherein, and R
1Be H or methyl; Adopting organic amine compound is the chlorine absorption agent, and the mol ratio of hydrogen silication silane intermediate product and unsaturated acyl chlorides is 1: 1～1: 1.6, and temperature of reaction is 0～30 ℃, and the reaction times is 3～5h, and the formula of obtaining is: (RO)
3SiCH
2CH
2CH
2O (CH
2CH
2O)
n(CH
2CH (CH
3) O)
mC=OCR
1=CH
2One end has two keys, and contains the long chain silane coupling agent that certain polyether chain is forged.
2. a kind of synthetic method that has long-chain polyether segment silane coupling agent according to claim 1 is characterized in that the solvent of platinum acid chloride solution is benzene, toluene, Virahol, tetrahydrofuran (THF) in the described step 1).
3. a kind of synthetic method that has long-chain polyether segment silane coupling agent according to claim 1 is characterized in that described step 2) in organic amine compound be triethylamine, pyridine, urea.
4. a kind of synthetic method that has long-chain polyether segment silane coupling agent according to claim 1 is characterized in that described step 2) in solvent be acetone, tetrahydrofuran (THF), toluene, methylene dichloride, trichloromethane.
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|---|---|---|---|
| CNB200610049525XA CN100366661C (en) | 2006-02-17 | 2006-02-17 | Synthesis method of silicane coupling agent having long chain polyether chain section |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610049525XA CN100366661C (en) | 2006-02-17 | 2006-02-17 | Synthesis method of silicane coupling agent having long chain polyether chain section |
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|---|---|
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| CN100366661C CN100366661C (en) | 2008-02-06 |
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ID=36935546
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|---|---|---|---|
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805365A (en) * | 2010-03-17 | 2010-08-18 | 浙江大学 | Dihydromyrcenol base silane coupling agent and synthetization method thereof |
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| CN113861406A (en) * | 2021-11-01 | 2021-12-31 | 江西晨光新材料股份有限公司 | Method for preparing silane modified polyether by using dichlorosilane |
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| JPH03160022A (en) * | 1989-11-17 | 1991-07-10 | Sanraizu Meisei Kk | Moisture-curing silicon-terminated polymer and its production |
| DE4003621C1 (en) * | 1990-02-07 | 1990-12-20 | Th. Goldschmidt Ag, 4300 Essen, De | Silane poly:oxy:alkylene glycidyl ether - for improving e.g. epoxy] resins and inorganic materials e.g. glass fibres |
| US5830970A (en) * | 1995-12-22 | 1998-11-03 | Dow Corning Corporation | Silicone polyether surfactants |
| CN1320600A (en) * | 2000-04-21 | 2001-11-07 | 江苏日出(集团)公司 | Preparation method of vinyl trimethoxy silane |
| GB0118858D0 (en) * | 2001-08-02 | 2001-09-26 | Dow Corning | Hydrosilylation process |
| CN1239506C (en) * | 2003-02-28 | 2006-02-01 | 中国石油化工股份有限公司 | Organic silicate comprising ether, preparing process and application thereof |
| DE102004027003A1 (en) * | 2004-06-03 | 2005-12-22 | Wacker-Chemie Gmbh | Hydrophilic siloxane copolymers and process for their preparation |
| CN1312160C (en) * | 2005-05-23 | 2007-04-25 | 南京工业大学 | Process for preparing allyl silicane |
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| CN101070380B (en) * | 2007-05-10 | 2010-08-18 | 浙江大学 | Long-chain polyether type silane coupler of glycidol-ether-radical end-capping |
| CN101805365A (en) * | 2010-03-17 | 2010-08-18 | 浙江大学 | Dihydromyrcenol base silane coupling agent and synthetization method thereof |
| CN101805365B (en) * | 2010-03-17 | 2012-03-07 | 浙江大学 | Dihydromyrcenol base silane coupling agent and synthetization method thereof |
| CN104744684A (en) * | 2013-12-30 | 2015-07-01 | 辽宁奥克化学股份有限公司 | Block polyether, air entrained type polycarboxylate water reducing agent prepared by block polyether and preparation method thereof |
| CN105503028A (en) * | 2015-08-18 | 2016-04-20 | 江苏苏博特新材料股份有限公司 | In-situ reaction-type concrete air entraining agent |
| CN105503029A (en) * | 2015-08-18 | 2016-04-20 | 江苏苏博特新材料股份有限公司 | Concrete air-entraining agent |
| CN105503028B (en) * | 2015-08-18 | 2017-11-24 | 江苏苏博特新材料股份有限公司 | A kind of reaction in-situ type concrete air-entrainer |
| CN107973936A (en) * | 2017-12-08 | 2018-05-01 | 江苏麒祥高新材料有限公司 | A kind of preparation method of modified precipitated silica |
| CN111040418A (en) * | 2019-12-26 | 2020-04-21 | 刘大刚 | Color-homogenizing high-toughness plastic film and preparation process thereof |
| CN111040418B (en) * | 2019-12-26 | 2021-11-12 | 浙江永正包装有限公司 | Color-homogenizing high-toughness plastic film and preparation process thereof |
| CN112143269A (en) * | 2020-09-07 | 2020-12-29 | 中国石油大学胜利学院 | Water-based inorganic zinc-rich coating and preparation method thereof |
| CN112143269B (en) * | 2020-09-07 | 2022-07-12 | 中国石油大学胜利学院 | Water-based inorganic zinc-rich coating and preparation method thereof |
| CN113410516A (en) * | 2021-08-02 | 2021-09-17 | 清远萨菲安新材料有限公司 | Organic silicon electrolyte and preparation method and application thereof |
| CN113861406A (en) * | 2021-11-01 | 2021-12-31 | 江西晨光新材料股份有限公司 | Method for preparing silane modified polyether by using dichlorosilane |
| CN113861406B (en) * | 2021-11-01 | 2024-03-29 | 江西晨光新材料股份有限公司 | Method for preparing silane modified polyether by utilizing dichlorosilane |
| CN115322381A (en) * | 2022-07-27 | 2022-11-11 | 安徽壹石通材料科学研究院有限公司 | Polyether type organic silicon resin microsphere and preparation method and application thereof |
| CN115322381B (en) * | 2022-07-27 | 2024-04-26 | 安徽壹石通材料科学研究院有限公司 | Polyether type organic silicon resin microsphere and preparation method and application thereof |
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