CN106478710A - A kind of preparation method of new isocyanate base silane - Google Patents
A kind of preparation method of new isocyanate base silane Download PDFInfo
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- CN106478710A CN106478710A CN201610788043.XA CN201610788043A CN106478710A CN 106478710 A CN106478710 A CN 106478710A CN 201610788043 A CN201610788043 A CN 201610788043A CN 106478710 A CN106478710 A CN 106478710A
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- Prior art keywords
- silane
- preparation
- base silane
- isocyanate base
- new isocyanate
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- 229910000077 silane Inorganic materials 0.000 title claims abstract description 50
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000012948 isocyanate Substances 0.000 title claims abstract description 19
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 15
- BUZRAOJSFRKWPD-UHFFFAOYSA-N isocyanatosilane Chemical class [SiH3]N=C=O BUZRAOJSFRKWPD-UHFFFAOYSA-N 0.000 claims abstract description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 239000002585 base Substances 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 17
- 239000002808 molecular sieve Substances 0.000 claims description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 13
- 238000005336 cracking Methods 0.000 claims description 10
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- -1 amino Alkoxy silane Chemical compound 0.000 claims description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- KIUCLRQNNKHLDB-UHFFFAOYSA-N [dimethoxy(methyl)silyl]methanamine Chemical compound CO[Si](C)(CN)OC KIUCLRQNNKHLDB-UHFFFAOYSA-N 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical group [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical group C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000001119 stannous chloride Substances 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical group CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- GTXWPZRNXZAPGM-UHFFFAOYSA-N NCCC[SiH](OC(OCC)(OCC)OCC)OC Chemical compound NCCC[SiH](OC(OCC)(OCC)OCC)OC GTXWPZRNXZAPGM-UHFFFAOYSA-N 0.000 claims description 2
- MEXATBHBIYUJGT-UHFFFAOYSA-N NCCNCCC[SiH](OCC(OCC)(OCC)OCC)OCC Chemical compound NCCNCCC[SiH](OCC(OCC)(OCC)OCC)OCC MEXATBHBIYUJGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- LTRPLRHNXPTOIN-UHFFFAOYSA-N [diethoxy(methyl)silyl]methanamine Chemical compound CCO[Si](C)(CN)OCC LTRPLRHNXPTOIN-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 claims description 2
- JMPVESVJOFYWTB-UHFFFAOYSA-N dipropan-2-yl carbonate Chemical compound CC(C)OC(=O)OC(C)C JMPVESVJOFYWTB-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- ARKBFSWVHXKMSD-UHFFFAOYSA-N trimethoxysilylmethanamine Chemical compound CO[Si](CN)(OC)OC ARKBFSWVHXKMSD-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims 1
- 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 1
- QMMBZOSZCYBCDC-UHFFFAOYSA-N NCCNCCC[SiH](OC(OCC)(OCC)OCC)OC Chemical compound NCCNCCC[SiH](OC(OCC)(OCC)OCC)OC QMMBZOSZCYBCDC-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 125000004185 ester group Chemical group 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 238000007873 sieving Methods 0.000 claims 1
- ROWWCTUMLAVVQB-UHFFFAOYSA-N triethoxysilylmethanamine Chemical compound CCO[Si](CN)(OCC)OCC ROWWCTUMLAVVQB-UHFFFAOYSA-N 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000012974 tin catalyst Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000945 filler Substances 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 5
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- ZHUWIYQJHBMTCY-UHFFFAOYSA-N 3-[ethoxy(2,2,2-triethoxyethoxy)silyl]propan-1-amine Chemical compound NCCC[SiH](OCC(OCC)(OCC)OCC)OCC ZHUWIYQJHBMTCY-UHFFFAOYSA-N 0.000 description 1
- RDKXOOCTKMIEGS-UHFFFAOYSA-N [SiH4].NC(O)=O Chemical compound [SiH4].NC(O)=O RDKXOOCTKMIEGS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 125000001891 dimethoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006166 lysate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 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
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
The present invention relates to a kind of preparation method of new isocyanate base silane, it includes step：(1) aminoalkoxysilane and dialkyl carbonate reaction at 30 DEG C～80 DEG C of temperature generates carbamate groups alkoxy silane；(2) carbamate groups alkoxy silane is cracked to form isocyanato silanes under the catalysis of catalyst.The isocyanato silanes that the present invention is obtained can greatly reduce resin viscosity, therefore can add more fillers, reduces impregnation cost, increase mechanical performance simultaneously, and improves resin activity, contributes to reducing the consumption of tin catalyst.The catalyst choice using is high, and feed stock conversion is high, product yield high.
Description
Technical field
The present invention relates to a kind of preparation method of new isocyanate base silane, belong to compound synthesis technical field.
Background technology
The binding agent of crosslinked with silicane and sealant include alkoxysilane-terminated polymer as binding agent.There is reaction
Property alkoxysilyl polymeric system be early it is known that but the Silante terminated resin material majority on market is γ
Type blocks, and this resinoid activity is relatively low, needs using poisonous tin catalyst during solidification.The Silante terminated then resin of α type is lived
Property higher it is not necessary to tin catalyst also can crosslinking curing well, but due to technical reason, α type silane cannot be carried out batch
Amount produces, and α type silane commercially cannot be commercially available.
The preparation of α type silane also has the open report of some patent documentations, such as：American documentation literature US5393910 discloses
A kind of method that carbamate silane Pintsch process generates isocyanato silanes, but the method is split under gas phase condition
Solution, equipment needed thereby high complexity, and do not specifically describe isocyanatomethyl alkoxy silane in patent prepare example.
American documentation literature US6008396 discloses a kind of decompression cracking carbamate base silane in the presence of lysate
The method producing isocyanato silanes, but product separates difficulty, the ultimate yield causing product is relatively low, and is only used for
Produce NCO propyl group alkoxy silane.
Preparing isocyanates by carbamate cracking is known in the industry.
In sum, there is presently no a kind of technical feasibility, the simply efficient, system of isocyanato silanes that are being easy to popularization
Preparation Method.
Content of the invention
For the deficiencies in the prior art, the present invention provides a kind of preparation method of new isocyanate base silane, the method
In being used special stanniferous molecular sieve as Cracking catalyst, selectivity is higher, and product yield is high.
Summary of the invention：
The present invention passes through primary amine groups methyl alkoxy silane and dialkyl carbonate reaction generates carbamate ylmethyl
Alkoxy silane, then at high temperature, is cracked to form isocyanatomethyl alkoxy silane in the presence of catalyst.By not
With silicon and aluminum source prepare molecular screen primary powder and add after active Xi Yuan prepares stanniferous molecular screen primary powder cracking is prepared by post processing
Catalyst, this catalyst choice is strong, high catalytic efficiency.
Detailed Description Of The Invention：
A kind of preparation method of new isocyanate base silane is as follows including step：
(1) aminoalkoxysilane and dialkyl carbonate reaction at 30 DEG C～80 DEG C of temperature generates carbamate groups
Alkoxy silane；
(2) carbamate groups alkoxy silane is cracked to form isocyanato silanes under the catalysis of catalyst.
Currently preferred, step (1) aminoalkoxysilane with the mass ratio of dialkyl carbonate is：(9～15)：(6
～12), the response time is 0.5-3h.
Currently preferred, the concrete preparation process of step (1) carbamate groups alkoxy silane is as follows：
Stir in methanol solution dimethyl carbonate being added under magnetic stirring Feldalat NM, then Deca aminomethyl
Methyl dimethoxysilane, aminoalkoxysilane with the mass ratio of dialkyl carbonate is：(9～15)：(6～12), Deca
Response time 0.5-3h after being warming up to 50 DEG C～70 DEG C after end, with the methanol solution of ammonium chloride and products therefrom, filtering, subtracting
Pressure distillation is obtained carbamate groups alkoxy silane；In the methanol solution of Feldalat NM, Feldalat NM mass content is 20～40%,
The addition of the methanol solution of Feldalat NM with the mass ratio of dimethyl carbonate is：(1～3)：(80～100).
Currently preferred, in step (1), described aminoalkoxysilane general structure is as follows：
OCN-A1-Si(R1)x(OR2)3-x
Wherein, x is 0,1 or 2, R1 to be methylene residue.
Currently preferred, in step (1), described dialkyl carbonate is selected from dimethyl carbonate, diethyl carbonate, carbonic acid
Dibutyl ester or diisopropyl carbonate one of which or arbitrarily two or more mixing.
Currently preferred, in step (2), described catalyst is stanniferous molecular sieve.
It is further preferred that the Na of described stanniferous molecular sieve：Al：Si：The mol ratio of O is 1：(1～4)：(1～3)：(1～
8).
It is further preferred that in described stanniferous molecular sieve, Theil indices are the 10～65% of stanniferous molecular sieve, with molar amount.
Currently preferred, in step (2), described stanniferous molecular sieve is processed under silane for stanniferous molecular screen primary powder
Obtain, described silane is amino silane, described amino silane is selected from aminopropyl trimethoxysilane, aminopropyl-triethoxy silicon
Alkane, aminopropyltriethoxy dimethoxysilane, aminopropyltriethoxy diethoxy silane, aminomethyl trimethoxy silane, aminomethyl three
Ethoxysilane, aminomethyl methyl dimethoxysilane, aminomethyl methyldiethoxysilane, N- β-aminoethyl-γ-aminopropyl
Trimethoxy silane, N- β-aminoethyl-gamma-aminopropyl-triethoxy-silane, N- β-aminoethyl-γ-aminopropyltriethoxy dimethoxy
Base silane or N- β-aminoethyl-γ-aminopropyltriethoxy diethoxy silane one of which or arbitrarily two or more mixing.
It is further preferred that the concrete processing method of stanniferous molecular sieve is, by molecular screen primary powder in mass content 10%
Hybrid reaction 3～5h under room temperature in the aqueous isopropanol of amino silane.
Currently preferred, the Xi Yuan of described stanniferous molecular screen primary powder is stannous chloride, and the Si source of molecular screen primary powder is silicon
Sour sodium and/or tetraethyl orthosilicate；Al source is arbitrarily two or more mixing in aluminum chloride, aluminium hydroxide or sodium metaaluminate.
Stanniferous molecular screen primary powder is prior art, can buy in market.
Currently preferred, in step (2), the cracking temperature of carbamate groups alkoxy silane is 100 DEG C～500
DEG C, preferably cracking temperature is 150 DEG C～300 DEG C, and more preferably cracking temperature is 180 DEG C～250 DEG C.
Currently preferred, in step (2), the addition of described catalyst is carbamate groups alkoxy silane quality
0.5～3%.
Beneficial effects of the present invention：
1st, the catalyst choice that the present invention uses is high, and feed stock conversion is high, product yield high.
2nd, the isocyanato silanes that the present invention is obtained can be used for the production of modified silane resin, improves intensity and reduces viscous
Degree.
3rd, the isocyanato silanes that the present invention is obtained can greatly reduce resin viscosity, therefore can add more
Filler, reduces impregnation cost, increases mechanical performance simultaneously, and improves resin activity, contributes to reducing the consumption of tin catalyst.
Specific embodiment
With reference to embodiment, the present invention will be further described, but not limited to this.
A kind of preparation method of new isocyanate base silane is as follows including step：
(1) preparation of carbamate base silane：
90g dimethyl carbonate is added to the four-hole bottle with magnetic agitation for the 500ml, adds the methanol of 2g30% Feldalat NM
Solution, then by 135g aminomethyl methyl dimethoxysilane Deca such as four-hole bottle in 30min, reaction temperature controls 30
℃.It is warming up to after completion of dropwise addition in the methanol solution use after continuing reaction 1h after 70 DEG C ammonium chloride and products therefrom, filter, reduce pressure
Distillation gained filtrate obtains 185g product, and yield is 95.8%.
(2) isocyanato silanes preparation
Stanniferous molecular screen primary powder a：
A) 30gCTAB is dissolved in stand-by in 200g deionized water.
B) 125g Na2SiO3 9H2O is dissolved in standby in 200g deionized water.
C) 60g SnCl22H2O is dissolved in standby in 45g water.
D) 50g NaAlO2 is dissolved in standby in 200g deionized water.
E) CTAB solution is added to 1000mlSUS304 stainless steel container, start dispersion at a high speed, dispersion impeller line
Speed is 8.6m/s.Then sodium silicate solution, sodium aluminate solution and stannous chloride solution are sequentially added.Disperse under room temperature
High pressure crystallizing kettle, crystallization 8h at 100 DEG C is poured into after 45min.By centrifuge by gained solid in Muffle furnace, 550 DEG C
Lower calcining 6h obtains stanniferous molecular screen primary powder a.
The preparation of catalyst a：
Take 30g above-mentioned molecular screen primary powder a to add to the aqueous isopropanol of 200g10% aminopropyl trimethoxysilane, heat
Filter to obtain solid after backflow 2h, 12h is dried at 120 DEG C standby.
200g carbamate groups methyl dimethoxysilane is added to heating with magnetic stirring apparatuss
In 500ml four-hole bottle, add 2g catalyst a, be heated rapidly to 150 DEG C, heat up after continuing reaction 3h, through GC detection, amino first
Acid esters methyl dimethoxysilane conversion ratio 100%, catalyst choice 98%, collect：155～160 DEG C of fraction 160g,
Purity 99%, yield is 95.5%.
Embodiment 2,
A kind of preparation method of new isocyanate base silane is as follows including step：
(1) preparation of carbamate base silane：
90g dimethyl carbonate is added to the four-hole bottle with magnetic agitation for the 500ml, adds the methanol of 2g30% Feldalat NM
Solution, then by 135g aminomethyl methyl dimethoxysilane Deca such as four-hole bottle in 30min, reaction temperature controls 30
℃.It is warming up to after completion of dropwise addition in the methanol solution use after continuing reaction 1h after 70 DEG C ammonium chloride and products therefrom, filter, reduce pressure
Distillation gained filtrate obtains 185g product, and yield is 95.8%.
(2) isocyanato silanes preparation
Stanniferous molecular screen primary powder b：
A) 15gCTAB is dissolved in stand-by in 150g deionized water.
B) 8.5gNaOH is dissolved in standby in 20g deionized water.
C) 71.6g SnCl22H2O is dissolved in standby in 59.6g water.
D) 26g NaAlO2 is dissolved in standby in 200g deionized water.
E) CTAB solution is added to 1000mlSUS304 stainless steel container, start dispersion at a high speed, dispersion impeller line
Speed is 8.6m/s.Then sodium hydroxide solution, 110g tetraethyl orthosilicate, sodium aluminate solution and stannous chloride are sequentially added molten
Liquid.High pressure crystallizing kettle, crystallization 8h at 80 DEG C is poured into after dispersion 45min under room temperature.By centrifuge by gained solid in horse
Not in stove, at 550 DEG C, calcining 6h obtains stanniferous molecular screen primary powder b.
The preparation of catalyst b：
30g above-mentioned molecular screen primary powder b is taken to add to 200g10%N- β-aminoethyl-γ-aminopropyltrimethoxysilane
Aqueous isopropanol, filters to obtain solid, 12h is dried standby at 120 DEG C after being heated to reflux 2h.
200g carbamate groups methyl dimethoxysilane is added to heating with magnetic stirring apparatuss
In 500ml four-hole bottle, add 1g catalyst b, be heated rapidly to 150 DEG C, heat up after continuing reaction 3h, substrate GC detects amino first
Perester radical methyl dimethoxysilane conversion ratio 100%, catalyst choice 99.2%, collect：155～160 DEG C of fractions
155g, purity 99%, yield is 93%.
Contrast case study on implementation：
200g carbamate groups methyl dimethoxysilane is added to the 500ml with heating and magnetic stirring apparatuss
In four-hole bottle, it is heated rapidly to 150 DEG C, reacts 3h at this temperature, through GC detection, carbamate groups methyl dimethoxy
The conversion ratio of base silane is 65%, and selectivity 62% collects 155～160 DEG C of fraction 70.5g, purity 99%, yield：41.9%.
Above-described embodiment is only example property.For those skilled in the art it is possible to understand that without departing from the present invention
Principle and spirit in the case of can carry out multiple changes, modification, replacement and degeneration, the scope of the present invention to these embodiments
Claims and its equivalent limit again.
Claims (10)
1. a kind of preparation method of new isocyanate base silane, as follows including step：
(1) aminoalkoxysilane and dialkyl carbonate reaction at 30 DEG C～80 DEG C of temperature generates carbamate groups alcoxyl
Base silane；
(2) carbamate groups alkoxy silane is cracked to form isocyanato silanes under the catalysis of catalyst.
2. the preparation method of new isocyanate base silane according to claim 1 is it is characterised in that step (1) amino
Alkoxy silane with the mass ratio of dialkyl carbonate is：(9～15)：(6～12), the response time is 0.5-3h.
3. the preparation method of new isocyanate base silane according to claim 1 is it is characterised in that step (1) amino
The concrete preparation process of formic acid ester group alkoxy silane is as follows：
Stir in methanol solution dimethyl carbonate being added under magnetic stirring Feldalat NM, then Deca aminomethyl methyl
Dimethoxysilane, aminoalkoxysilane with the mass ratio of dialkyl carbonate is：(9～15)：(6～12), completion of dropwise addition
After be warming up to 50 DEG C～70 DEG C after response time 0.5-3h, with the methanol solution of ammonium chloride and products therefrom, filtering, decompression is steamed
Evaporate prepared carbamate groups alkoxy silane；In the methanol solution of Feldalat NM, Feldalat NM mass content is 20～40%, methanol
The addition of the methanol solution of sodium with the mass ratio of dimethyl carbonate is：(1～3)：(80～100).
4. the preparation method of new isocyanate base silane according to claim 1 is it is characterised in that in step (1), institute
State aminoalkoxysilane general structure as follows：
OCN-A1-Si(R1)x(OR2)3-x
Wherein, x is 0,1 or 2, R1 to be methylene residue.
5. the preparation method of new isocyanate base silane according to claim 1 is it is characterised in that in step (1), institute
State dialkyl carbonate to be selected from dimethyl carbonate, diethyl carbonate, dibutyl carbonate or diisopropyl carbonate one of which or appoint
Anticipate two or more mixing.
6. the preparation method of new isocyanate base silane according to claim 1 is it is characterised in that in step (2), institute
Stating catalyst is stanniferous molecular sieve, the Na of described stanniferous molecular sieve：Al：Si：The mol ratio of O is 1：(1～4)：(1～3)：(1～
8)；In stanniferous molecular sieve, Theil indices are the 10～65% of stanniferous molecular sieve, with molar amount.
7. the preparation method of new isocyanate base silane according to claim 6 is it is characterised in that in step (2), institute
State stanniferous molecular sieve and carry out process under silane for stanniferous molecular screen primary powder and obtain, described silane is amino silane, described ammonia
Base silane is selected from aminopropyl trimethoxysilane, aminopropyl triethoxysilane, aminopropyltriethoxy dimethoxysilane, aminopropyl
Methyldiethoxysilane, aminomethyl trimethoxy silane, aminomethyl triethoxysilane, aminomethyl methyl dimethoxy epoxide silicon
Alkane, aminomethyl methyldiethoxysilane, N- β-aminoethyl-γ-aminopropyltrimethoxysilane, N- β-aminoethyl-γ-ammonia third
Ethyl triethoxy silicane alkane, N- β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane or N- β-aminoethyl-γ-aminopropyltriethoxy
Diethoxy silane one of which or arbitrarily two or more mixing.
8. the preparation method of new isocyanate base silane according to claim 1 is it is characterised in that stanniferous molecular sieve
Concrete processing method is, anti-by mixing under room temperature in the aqueous isopropanol of the amino silane in mass content 10% for the molecular screen primary powder
Answer 3～5h.
9. the preparation method of new isocyanate base silane according to claim 1 is it is characterised in that described stanniferous molecule
The Xi Yuan sieving former powder is stannous chloride, and the Si source of molecular screen primary powder is sodium silicate and/or tetraethyl orthosilicate；Al source be aluminum chloride,
Arbitrarily two or more mixing in aluminium hydroxide or sodium metaaluminate.
10. the preparation method of new isocyanate base silane according to claim 1 is it is characterised in that in step (2),
The cracking temperature of carbamate groups alkoxy silane is 100 DEG C～500 DEG C, and preferably cracking temperature is 150 DEG C～300 DEG C, more
Preferably cracking temperature is 180 DEG C～250 DEG C, and in step (2), the addition of described catalyst is carbamate groups alkoxyl silicone
The 0.5～3% of alkane quality.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109721734A (en) * | 2018-12-20 | 2019-05-07 | 上海东大化学有限公司 | A kind of both-end alkoxyl silicone ketone resin and preparation method thereof |
| CN111285898A (en) * | 2020-04-10 | 2020-06-16 | 秦振平 | Preparation method of isocyanate silane |
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| US5393910A (en) * | 1993-10-20 | 1995-02-28 | Osi Specialties, Inc. | Process for making isocyanatoorganosilanes |
| US6008396A (en) * | 1997-04-11 | 1999-12-28 | Osi Specialties, Inc. | Hot oil process for producing isocyanato organosilanes |
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| CN109721734A (en) * | 2018-12-20 | 2019-05-07 | 上海东大化学有限公司 | A kind of both-end alkoxyl silicone ketone resin and preparation method thereof |
| CN109721734B (en) * | 2018-12-20 | 2021-08-03 | 上海东大化学有限公司 | Double-end alkoxy silicone resin and preparation method thereof |
| CN111285898A (en) * | 2020-04-10 | 2020-06-16 | 秦振平 | Preparation method of isocyanate silane |
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