CN105399763A - Synthetic method for glycidyl ether oxysilane - Google Patents
Synthetic method for glycidyl ether oxysilane Download PDFInfo
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- CN105399763A CN105399763A CN201510918452.2A CN201510918452A CN105399763A CN 105399763 A CN105399763 A CN 105399763A CN 201510918452 A CN201510918452 A CN 201510918452A CN 105399763 A CN105399763 A CN 105399763A
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- glycidol
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- glycidyl ether
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- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000010189 synthetic method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 13
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005052 trichlorosilane Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 52
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 9
- 238000003379 elimination reaction Methods 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 abstract 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 15
- 239000007788 liquid Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- -1 polyethylene Polymers 0.000 description 6
- 229920003002 synthetic resin Polymers 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000000057 synthetic resin Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 2
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 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
- 239000002994 raw material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- ALJXKSOYHMOQSF-UHFFFAOYSA-N 2-[(3,5-dimethylphenoxy)methyl]oxirane Chemical compound CC1=CC(C)=CC(OCC2OC2)=C1 ALJXKSOYHMOQSF-UHFFFAOYSA-N 0.000 description 1
- YPTQLANVAZZAJF-UHFFFAOYSA-N CCO[SiH2]c1cc(C)cc(C)c1 Chemical compound CCO[SiH2]c1cc(C)cc(C)c1 YPTQLANVAZZAJF-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- YBHBEZSZXFLQMW-UHFFFAOYSA-N [dimethoxy(phenyl)silyl]methanamine Chemical compound CO[Si](CN)(OC)C1=CC=CC=C1 YBHBEZSZXFLQMW-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 150000002118 epoxides Chemical group 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- KIRWIETUDITSMO-UHFFFAOYSA-N trihydroxy(phenoxy)silane Chemical compound O[Si](O)(O)OC1=CC=CC=C1 KIRWIETUDITSMO-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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses a synthetic method for glycidyl ether oxysilane. The method comprises the following steps: adding glycidol, an acid binding agent and a solvent into a reaction container so as to obtain a mixed solution and then subjecting the mixed solution to cooling and heat preservation; then adding di-substituent dichlorosilane or monosubstituent trichlorosilane dissolved in a solvent and continuing to stir for a reaction after completion of addition; and carrying out treatment so as to obtain a glycidyl ether oxysilane product. The one-step synthetic method provided by the invention overcomes the disadvantages of high cost, low yield and a long preparation period of conventional multistep methods for preparation of glycidyl ether oxysilane and has the advantages of easiness, fastness and high yield.
Description
Technical field
The present invention relates to a kind of chemical synthesis process, especially relate to the synthetic method of serial glycidyl ether TMOS.
Background technology
High molecular synthetic resin, can be divided into addition polymer resin and polycondensate resin by synthetic method.Addition polymer is mainly obtained through polyaddition reaction by the monomer containing unsaturated link(age), the chemical formula of its key joint structure is identical with the molecular formula of monomer, as polyethylene (PE), polystyrene (PS), polycondensate contains two or more active function groups monomer primarily of two or more end is obtained through condensation polymerization reaction, the chemical formula of its key joint structure is different from the molecular formula of monomer, as resol, vibrin, polyamide resin etc.These resins are widely used in the fields such as chemical fibre, traffic, tackiness agent, matrix material, aerospace, become the indispensable material closely bound up with people's productive life.
Up to the present, synthetic resins research tendency forward variation and high performance aspect develop.Wherein, improve synthetic resins flame retardant properties, particularly improve polycondensate resins fire retardant performance and day by day become the focus that government and investigators pay close attention to.Silicon, is only second to the element of oxygen (49.5%) as content in the earth's crust, be large, the nontoxic novel flame-retardant element of a kind of amount, its existence form is various, easy to use.Glycidyl ether TMOS, as a kind of micromolecular compound containing epoxide group, under the catalysis of acid, alkali with other active group in resin (as-OH ,-NH
2) there is ring-opening reaction, element silicon is incorporated in the matrix of synthetic resins with the form of covalent linkage, greatly can improves the heat-proof combustion-resistant performance of resin.Meanwhile, the introducing of Si-O-, can also improve the toughness of synthetic resins greatly.As L.A.MERCADO (Reactivityofsilicon-basedepoxymonomersasstudiedbynear-in fraredspectroscopyandmultivariatecurveresolutionmethods [J] .JournalofPolymerSciencePartA:PolymerChemistry, 2006, 44 (4): 1447-1456) etc. people is from 3,5-dimethylphenyl Ethoxysilane, make it to generate 3,5-dimethylphenyl allyloxy silane with vinyl carbinol generation transesterification reaction by titanium isopropylate catalysis, then under the effect of metachloroperbenzoic acid, oxidation generates 3,5-dimethylphenyl glycidyl ether TMOS.L.A.MERCADO (Flameretardantepoxyresinsbasedondiglycidyloxymethylpheny lsilane [J] .JournalofPolymerSciencePartA:PolymerChemistry, 2006,44 (19): 5580-5587) etc. people is from aminomethyl phenyl dimethoxysilane, make it to generate aminomethyl phenyl diene npropoxysilane with vinyl carbinol generation transesterification reaction by Louis acid catalysis, under the effect of metachloroperbenzoic acid, oxidation generates aminomethyl phenyl diglycidylether TMOS then.W.J.Wanga (Characterizationandpropertiesofnewsilicone-containingepo xyresin [J] .Polymer, 2000,4 (16): 6113-6122) etc. people is from phenyltrimethoxysila,e, under tosic acid effect, hydrolysis generates phenyl trihydroxy-silanol intermediate, then generates phenyl triglycidyl ether TMOS with epichlorohydrin reaction.In addition, tetrabutyl titanate is used as catalyst for ester exchange reaction by them, directly phenyltrimethoxysila,e and R-GLYCIDOL is reacted and prepares phenyl triglycidyl ether oxygen base phenyl silane as improving improving one's methods of productive rate.
Summary of the invention
In order to overcome the deficiencies in the prior art, object of the present invention is intended to the synthetic method of the glycidyl ether TMOS providing single stage method high yield.This single stage method is raw material with chlorosilane, overcomes the shortcoming that cost is high, productive rate is low, the cycle is long that traditional multi-step preparation exists.
The invention provides the synthetic method of glycidyl ether TMOS, concrete steps are as follows:
1) in reaction vessel, add R-GLYCIDOL, acid binding agent and solvent, obtain mixing solutions;
2) above-mentioned mixing solutions cooled and be incubated 20 ~ 40min, then adding dissolving disubstituted dichlorosilane in a solvent or monosubstituted base trichlorosilane wherein; After adding, control temperature is 0 DEG C ~ 25 DEG C, continues stirring reaction 8 ~ 24h;
3) after reaction terminates, filter, the solid that elimination reaction generates, collect filtrate;
4) pump the most of solvent in filtrate with Rotary Evaporators, solvent unnecessary in remainder and excessive R-GLYCIDOL be 60-100 DEG C of removing in vacuum drying oven;
5) be cooled to room temperature, obtain glycidyl ether TMOS product; Wherein:
Step 1) in, the mol ratio of R-GLYCIDOL and acid binding agent is 1:0.95 ~ 1:1.05;
Step 2) in, the mol ratio of disubstituted dichlorosilane and R-GLYCIDOL is 1:1.95 ~ 1:2.05, and the mol ratio of monosubstituted base trichlorosilane and R-GLYCIDOL is 1:2.95 ~ 1:3.05.
Above-mentioned steps 1) in, described acid binding agent is pyridine or triethylamine.
Above-mentioned steps 2) in, the structural formula of described disubstituted dichlorosilane, monosubstituted base trichlorosilane is as follows respectively:
Wherein: R
1, R
2for methyl or phenyl.
Above-mentioned steps 2) in, be cooled to 0-10 DEG C.
Above-mentioned steps 1) and step 2) in, described solvent is toluene or THF.
Above-mentioned steps 1) in, the mass volume ratio of R-GLYCIDOL and solvent is 0.1g/ml-1g/ml; Step 2) in, the mass volume ratio of disubstituted dichlorosilane or monosubstituted base trichlorosilane and solvent is 0.1g/ml-1g/ml.
Reaction expression of the present invention is as follows:
R
1, R
2for methyl or phenyl.
Beneficial effect of the present invention is: the present invention with disubstituted dichlorosilane or monosubstituted base trichlorosilane for raw material, under the effect of acid binding agent, glycidyl ether TMOS is obtained with stoichiometric reaction such as R-GLYCIDOLs, one-step synthesis method of the present invention overcomes the shortcoming that cost is high, productive rate is low, the cycle is long that traditional multistep processes prepares the existence of this series compound, synthetic method is simple, quick, and productive rate is high.
Embodiment
Below by embodiment, the invention will be further described.
Chlorosilane in embodiment selects phenyl-trichloro-silicane, diphenyl dichlorosilane, dichloromethyl phenylsilane to be example.
Embodiment 1
Be furnished with in the 500ml two-mouth bottle of dropping funnel, prolong and magnetic stir bar and add 29.6g R-GLYCIDOL (0.4mol), 40.4g triethylamine (0.4mol) and 200ml toluene, mixing solutions is cooled to 0 DEG C, in half an hour, with dropping funnel, 50.4g (0.2mol) diphenyl dichlorosilane dissolving in 100ml toluene is joined in above-mentioned mixing solutions; Temperature controls at 0 DEG C, stirring reaction 8h; Reaction mixture body is filtered, the chloride solid that elimination reaction generates, collect filtrate; Pump toluene solvant with Rotary Evaporators, obtain light yellow transparent liquid, this liquid is put into vacuum drying oven, vacuumize and be warming up to 60 DEG C of unnecessary toluene solvants of removing and excessive R-GLYCIDOL; Be cooled to room temperature, obtain 57.73g phenylbenzene diglycidylether TMOS (productive rate 88%).
Product adopts nuclear magnetic resonance measuring, result following (
1hNMR [DMSO/TMS, δ (ppm)]): 7.42 ~ 7.65ppm (10H, Ar-H), 3.75 ~ 4.03ppm (4H, Si-O-CH
2), 2.65 ~ 3.15ppm (6H, the H on oxyethane ring).
Embodiment 2
Be furnished with in the 500ml two-mouth bottle of dropping funnel, prolong and magnetic stir bar and add 29.6g R-GLYCIDOL (0.4mol), 40.4g triethylamine (0.4mol) and 200ml toluene, mixing solutions is cooled to 10 DEG C, in half an hour, with dropping funnel, 25.8g (0.2mol) dimethyldichlorosilane(DMCS) dissolving in 100ml toluene is joined in above-mentioned mixing solutions; Temperature controls at 25 DEG C, stirring reaction 24h; Reaction mixture body is filtered, the chloride solid that elimination reaction generates, collect filtrate; Pump toluene solvant with Rotary Evaporators, obtain light yellow transparent liquid, this liquid is put into vacuum drying oven, vacuumize and be warming up to 100 DEG C of unnecessary toluene solvants of removing and excessive R-GLYCIDOL; Be cooled to room temperature, obtain 57.73g phenylbenzene diglycidylether TMOS (productive rate 88%).
Product adopts nuclear magnetic resonance measuring, result following (
1hNMR [DMSO/TMS, δ (ppm)]): 3.75 ~ 4.03ppm (4H, Si-O-CH
2), 2.65 ~ 3.15ppm (6H, the H on oxyethane ring), 0.42ppm (6H, Si-CH
3).
Embodiment 3
Be furnished with in the 500ml two-mouth bottle of dropping funnel, prolong and magnetic stir bar and add 29.6g R-GLYCIDOL (0.4mol), 40.4g triethylamine (0.4mol) and 200ml toluene, mixing solutions is cooled to 0 DEG C, in half an hour, with dropping funnel, 38.2g (0.2mol) dichloromethyl phenylsilane dissolving in 100ml toluene is joined in above-mentioned mixing solutions; Temperature controls at 10 DEG C, stirring reaction 16h; Reaction mixture body is filtered, the chloride solid that elimination reaction generates, collect filtrate; Pump toluene solvant with Rotary Evaporators, obtain light yellow transparent liquid, this liquid is put into vacuum drying oven, vacuumize and be warming up to 80 DEG C of unnecessary toluene solvants of removing and excessive R-GLYCIDOL; Be cooled to room temperature, obtain 57.73g phenylbenzene diglycidylether TMOS (productive rate 88%).
Product adopts nuclear magnetic resonance measuring, result following (
1hNMR [DMSO/TMS, δ (ppm)]): 7.42 ~ 7.65ppm (5H, Ar-H), 3.75 ~ 4.03ppm (4H, Si-O-CH
2), 2.65 ~ 3.15ppm (6H, the H on oxyethane ring), 0.42ppm (3H, Si-CH
3).
Embodiment 4
Be furnished with in the 500ml two-mouth bottle of dropping funnel, prolong and magnetic stir bar and add 29.6g R-GLYCIDOL (0.4mol), 31.6g pyridine (0.4mol) and 200ml toluene, mixing solutions is cooled to 0 DEG C, in half an hour, with dropping funnel, 42.3g (0.2mol) phenyl-trichloro-silicane dissolving in 100ml toluene is joined in above-mentioned mixing solutions; Temperature controls at 0 DEG C, stirring reaction 12h; Reaction mixture body is filtered, the pyridine hydrochloride solid that elimination reaction generates, collect filtrate; Pump toluene solvant with Rotary Evaporators, obtain light yellow transparent liquid, this liquid is put into vacuum drying oven, vacuumize and be warming up to 60 DEG C of unnecessary toluene solvants of removing and excessive R-GLYCIDOL; Be cooled to room temperature, obtain 55.08g phenyl triglycidyl ether TMOS (productive rate 85%).
Product adopts nuclear magnetic resonance measuring, result following (
1hNMR [DMSO/TMS, δ (ppm)]): 7.07 ~ 7.48ppm (5H, Ar-H), 3.28 ~ 3.92ppm (6H, Si-O-CH
2), 2.60 ~ 3.21ppm (9H, the H on oxyethane ring).
Embodiment 5
Be furnished with in the 500ml two-mouth bottle of dropping funnel, prolong and magnetic stir bar and add 29.6g R-GLYCIDOL (0.4mol), 40.4g triethylamine (0.4mol) and 200mlTHF, mixing solutions is cooled to 0 DEG C, in half an hour, with dropping funnel, 29.9g (0.2mol) METHYL TRICHLORO SILANE of dissolving in 100mlTHF is joined in above-mentioned mixing solutions; Temperature controls at 0 DEG C, stirring reaction 12h; Reaction mixture body is filtered, the chloride solid that elimination reaction generates, collect filtrate; Pump THF solvent with Rotary Evaporators, obtain light yellow transparent liquid, this liquid is put into vacuum drying oven, vacuumize and be warming up to 60 DEG C of unnecessary THF solvents of removing and excessive R-GLYCIDOL; Be cooled to room temperature, obtain 46.28g aminomethyl phenyl diglycidylether TMOS (productive rate 87%).
Product adopts nuclear magnetic resonance measuring, result following (
1hNMR [DMSO/TMS, δ (ppm)]): 3.28 ~ 3.92ppm (6H, Si-O-CH
2), 2.60 ~ 3.21ppm (9H, the H on oxyethane ring), 0.42ppm (3H, Si-CH
3).
Claims (6)
1. the synthetic method of glycidyl ether TMOS, is characterized in that, concrete steps are as follows:
1) in reaction vessel, add R-GLYCIDOL, acid binding agent and solvent, obtain mixing solutions;
2) above-mentioned mixing solutions cooled and be incubated 20 ~ 40min, then adding dissolving disubstituted dichlorosilane in a solvent or monosubstituted base trichlorosilane wherein; After adding, control temperature is 0 DEG C ~ 25 DEG C, continues stirring reaction 8 ~ 24h;
3) after reaction terminates, filter, the solid that elimination reaction generates, collect filtrate;
4) pump the solvent in filtrate with Rotary Evaporators, solvent unnecessary in remainder and excessive R-GLYCIDOL be 60-100 DEG C of removing in vacuum drying oven;
5) be cooled to room temperature, obtain glycidyl ether TMOS product; Wherein:
Step 1) in, the mol ratio of R-GLYCIDOL and acid binding agent is 1:0.95 ~ 1:1.05;
Step 2) in, the mol ratio of disubstituted dichlorosilane and R-GLYCIDOL is 1:1.95 ~ 1:2.05; The mol ratio of monosubstituted base trichlorosilane and R-GLYCIDOL is 1:2.95 ~ 1:3.05.
2. synthetic method according to claim 1, is characterized in that, step 1) in, described acid binding agent is pyridine or triethylamine.
3. synthetic method according to claim 1, is characterized in that, step 2) in, the structural formula of described disubstituted dichlorosilane, monosubstituted base trichlorosilane is as follows respectively:
Wherein: R
1, R
2for methyl or phenyl.
4. synthetic method according to claim 1, is characterized in that, step 2) in, be cooled to 0-10 DEG C.
5. synthetic method according to claim 1, is characterized in that, step 1) and step 2) in, described solvent is toluene or THF.
6. synthetic method according to claim 1, is characterized in that, step 1) in, the mass volume ratio of R-GLYCIDOL and solvent is 0.1g/ml-1g/ml; Step 2) in, the mass volume ratio of disubstituted dichlorosilane or monosubstituted base trichlorosilane and solvent is 0.1g/ml-1g/ml.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110511354A (en) * | 2019-08-30 | 2019-11-29 | 苏州科技大学 | A kind of phosphorus silicon synergistic fire retardant and preparation method thereof containing epoxy group |
| CN111370765A (en) * | 2020-03-14 | 2020-07-03 | 北京化工大学 | Preparation method of cyclic ether phosphazene polymer electrolyte membrane with excellent film-forming performance |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2730532A (en) * | 1953-07-20 | 1956-01-10 | Shell Dev | Epoxy-substituted esters of silicon acids and their preparation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US2730532A (en) * | 1953-07-20 | 1956-01-10 | Shell Dev | Epoxy-substituted esters of silicon acids and their preparation |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110511354A (en) * | 2019-08-30 | 2019-11-29 | 苏州科技大学 | A kind of phosphorus silicon synergistic fire retardant and preparation method thereof containing epoxy group |
| CN110511354B (en) * | 2019-08-30 | 2021-11-16 | 苏州科技大学 | Phosphorus-silicon synergistic flame retardant containing epoxy group and preparation method thereof |
| CN111370765A (en) * | 2020-03-14 | 2020-07-03 | 北京化工大学 | Preparation method of cyclic ether phosphazene polymer electrolyte membrane with excellent film-forming performance |
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