CN101161657B - Method for synthesizing isocynate silane coupling agent - Google Patents
Method for synthesizing isocynate silane coupling agent Download PDFInfo
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- CN101161657B CN101161657B CN2007101563916A CN200710156391A CN101161657B CN 101161657 B CN101161657 B CN 101161657B CN 2007101563916 A CN2007101563916 A CN 2007101563916A CN 200710156391 A CN200710156391 A CN 200710156391A CN 101161657 B CN101161657 B CN 101161657B
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- silane coupling
- coupling agent
- synthetic method
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- tetrahydrofuran
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- 239000006087 Silane Coupling Agent Substances 0.000 title claims description 19
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate Chemical compound [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 title claims description 18
- 238000000034 method Methods 0.000 title description 2
- 230000002194 synthesizing effect Effects 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- -1 silane isocyanate Chemical class 0.000 claims abstract description 21
- 229910000077 silane Inorganic materials 0.000 claims abstract description 12
- 238000010189 synthetic method Methods 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 180
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 90
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 54
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 27
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 150000001721 carbon Chemical group 0.000 claims description 5
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- BMHWGDAMBPGVFR-UHFFFAOYSA-N 4-(1h-pyrrol-2-yl)pyridine Chemical compound C1=CNC(C=2C=CN=CC=2)=C1 BMHWGDAMBPGVFR-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 2
- 229940043232 butyl acetate Drugs 0.000 claims description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 2
- 229940093499 ethyl acetate Drugs 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 abstract description 8
- 239000012948 isocyanate Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000007822 coupling agent Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 44
- 150000002148 esters Chemical class 0.000 description 23
- 238000009835 boiling Methods 0.000 description 22
- 238000004821 distillation Methods 0.000 description 22
- 238000010907 mechanical stirring Methods 0.000 description 22
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- 238000010992 reflux Methods 0.000 description 22
- 238000003756 stirring Methods 0.000 description 22
- 238000010792 warming Methods 0.000 description 22
- UIDUKLCLJMXFEO-UHFFFAOYSA-N propylsilane Chemical compound CCC[SiH3] UIDUKLCLJMXFEO-UHFFFAOYSA-N 0.000 description 21
- NSSIZMPQSZKECB-UHFFFAOYSA-N (diethoxyamino)oxyethane Chemical compound CCON(OCC)OCC NSSIZMPQSZKECB-UHFFFAOYSA-N 0.000 description 19
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 16
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- HCUYBXPSSCRKRF-UHFFFAOYSA-N diphosgene Chemical compound ClC(=O)OC(Cl)(Cl)Cl HCUYBXPSSCRKRF-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PQLFROTZSIMBKR-UHFFFAOYSA-N ethenyl carbonochloridate Chemical compound ClC(=O)OC=C PQLFROTZSIMBKR-UHFFFAOYSA-N 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 2
- VXMQKONTARQGPP-UHFFFAOYSA-N (ethoxyamino)oxyethane Chemical compound CCONOCC VXMQKONTARQGPP-UHFFFAOYSA-N 0.000 description 1
- NHOWREQLQRFDRW-UHFFFAOYSA-N (methoxyamino)oxymethane Chemical compound CONOC NHOWREQLQRFDRW-UHFFFAOYSA-N 0.000 description 1
- DXYQYRMJJABZTO-UHFFFAOYSA-N C[SiH](OC)OC.C(CC)Cl Chemical compound C[SiH](OC)OC.C(CC)Cl DXYQYRMJJABZTO-UHFFFAOYSA-N 0.000 description 1
- KSXGWZKRGZDNCY-UHFFFAOYSA-N C[SiH](OCC)OCC.C(CC)Cl Chemical compound C[SiH](OCC)OCC.C(CC)Cl KSXGWZKRGZDNCY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- SRJIXIZHNHRTTQ-UHFFFAOYSA-N [SiH4].C(C)[SiH3] Chemical compound [SiH4].C(C)[SiH3] SRJIXIZHNHRTTQ-UHFFFAOYSA-N 0.000 description 1
- VILWJZBKNUMVBJ-UHFFFAOYSA-N [SiH4].C(CC)[SiH3] Chemical compound [SiH4].C(CC)[SiH3] VILWJZBKNUMVBJ-UHFFFAOYSA-N 0.000 description 1
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229960001701 chloroform Drugs 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
- 230000002498 deadly effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000011208 reinforced composite material Substances 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Abstract
The present invention relates to a synthetic method for a coupling agent of silane isocyanate, and aims to provide a chemical synthetic method which is environmental friendly with reasonable technics, reliability and safety in production, high reaction yield, without the three wastes to thoroughly solve the issue of phosgene. The invention is characterized in that amino silane and carbonyldiimidazole are adopted as the raw materials, which undergo adequate reaction under -10 DEG C to 100 DEG C in an organic solvent under the action of a catalyzer, and then the product is treated to obtain thecoupling agent of silane isocyanate with the general formula as RX (R<1>O) 3-XSi(CH2)nNCO.
Description
Technical field
The present invention relates to organic chemistry filed, specifically is a kind of synthetic method of isocynate silane coupling agent.
Background technology
Containing isocynate silane coupling agent is a kind of special coupling agent, it has very good effect when surface treatment organic materials and inorganic metal, particularly in the tackifier of glass fiber reinforced composite materials, processing inorganic powder filler and coating and printing ink significant effect is arranged all.
The existing synthetic chemical process that contains isocynate silane coupling agent mainly contains following several before the present invention:
Pyrolysis method prepares isocynate silane coupling agent, and at relevant American-European patent US 5,393,910, DE10064086 among the US 7060849, adopts silicane amido formate compounds, and cracking at high temperature generates isocynate silane coupling agent.250 ℃-350 ℃ of this arts demand high temperature have very high requirement to generation equipment, and investment is big.In Japanese Patent JP9328489, adopt the synthetic corresponding urea of amino containing silane and isocyanate reaction such as MDI, and then cracking.
Poland Patent Pol 182009 (2001) is in organic solvent, adopts halogenated silanes with the synthetic isocynate silane coupling agent that obtains of isocyanic ester nak response.And isocyanic ester potassium also is a kind of deadly poisonous compound, to the threat of operator's formation life.
Described in US3584024, in organic solvent, as: benzene,toluene,xylene, chlorobenzene, methylene dichloride, trichloromethane, ether, tetrahydrofuran (THF) etc., obtain isocyanic ester by containing the direct photoreactive gas reaction of amine grade silane compounds, but phosgene has severe toxicity, and has and be not easy the shortcoming for preparing and store.No matter be laboratory work or industrial production, slave unit and environmental angle are seen all can bring very burden.The equipment of phosgene is produced and stored to necessary many covers on producing; If leak, bring immeasurable loss then for human life's property and environment.The substitute that the human phosgene arranged subsequently as, Vinyl chloroformate, trichloromethylchloroformate, two (trichloromethyl) carbonic ether etc. are described in Chinese patent CN 18878888, under alkaline condition, two (trichloromethyl) carbonic ethers and amino containing silane reaction have been adopted, the synthesizing isocyanate silane coupling agent.But still keep away the generation of unavoidable phosgene in the reaction process, there is very big threat in environment.Still there is bigger potential safety hazard in use.
Summary of the invention
The object of the invention has provided that a kind of technology is reasonable, environmentally friendly, production safety is reliable, reaction yield is high, the isocynate silane coupling agent chemical synthesis process of the no three wastes, with thorough solution phosgene problem.
The synthetic method of isocynate silane coupling agent of the present invention, it is characterized in that be raw material with amino containing silane (II) with carbonyl dimidazoles, the mol ratio of two raw materials is 1: 1～6.0, under catalyzer C effect, in organic solvent, be-10～100 ℃ (being preferably-10～70 ℃) fully reaction in temperature, it is R that aftertreatment promptly gets general formula
X(R
1O)
3-XSi (CH
2)
nThe isocynate silane coupling agent of NCO (I), reaction equation is:
X＝0，1，2，3，
n＝1，2，3，4，5，6，...12，
R is alkane or halogenated alkane, and alkane wherein is that carbon atom is the naphthenic hydrocarbon that 1～12 alkane or carbon atom are 5～8,
R
1Be that halogenated alkane or carbon atom are 1～4 alkane;
Catalyzer C is dicyclohexyl carbon imines (Dcc), L-first-2-halogen pyridinium salt, to Dimethylamino pyridine (DMAP), 4-pyrryl pyridine (PPY), Phenylsulfonic acid, aluminum chloride, to methylsulphonic acid, quinoline, N, a kind of in accelerine, the two carboxylic acid diethyl esters of azo, tributylphosphine, the fluoroform sulphonate;
Described organic solvent can be, lipid solvent such as ethyl acetate, propyl acetate, butylacetate, ether solvent such as tetrahydrofuran (THF), ether, propyl ether, isopropyl ether, butyl ether, hexyl ether, methyl tertiary butyl ether etc., ketones solvent such as acetone, butanone, pentanone etc., aliphatic hydrocarbon kind solvent such as hexanaphthene, normal hexane, sherwood oil etc., aromatic hydrocarbon solvent such as benzene,toluene,xylene, trimethylbenzene etc. (mass ratio of amino containing silane and organic solvent be preferably 1: 0.5～5).
As preferably, described amino containing silane (II): carbonyl dimidazoles: the mol ratio of catalyzer C is 1: 1～6.0: 0.005～0.02; More preferably 1: 1～6.0: 0.01～0.2.
Reaction times is 2～36h.
Beneficial effect compared with prior art of the present invention is:
1, used raw material is cheap and easy to get, has avoided hypertoxic raw material phosgene and trichloromethylchloroformate, phosgene substitutes such as Vinyl chloroformate, and safety simple to operate, reaction time is short, does not have the three wastes substantially;
2, the present invention compared with prior art, the operational path advanced person, processing condition are reasonable;
3, production cost is low, and the reaction yield height has bigger practicing and is worth and economic results in society.
Embodiment
Embodiment 1
Mechanical stirring is being housed; the exsiccant constant pressure funnel; in the 1000ml four-hole boiling flask of reflux condensing tube and thermometer; under nitrogen protection, add 0.1mol triethoxy amine propyl silane; 1% dicyclohexyl carbon imines (Dcc) and 350ml tetrahydrofuran (THF); open and stir; under 0-10 ℃; slowly drip the carbonyl dimidazoles 0.12mol solution that is dissolved in the 100ml tetrahydrofuran (THF); 0-10 ℃ of reaction 2 hours; be warming up to 40 ℃ of reactions 15 hours; steam tetrahydrofuran (THF); the thick product triethoxy amine propyl silane that obtains; through underpressure distillation; collect bp145-152 ℃/25mmHg; obtain thick product isocyanic ester propyl-triethoxysilicane; yield 76%, content are 97.8% (GC).
Embodiment 2
Mechanical stirring is being housed; the exsiccant constant pressure funnel; in the 1000ml four-hole boiling flask of reflux condensing tube and thermometer; under nitrogen protection, add 0.1mol triethoxy amine propyl silane; 1% dicyclohexyl carbon imines (Dcc) and 350ml tetrahydrofuran (THF); open and stir; under 0-10 ℃; slowly drip the carbonyl dimidazoles 0.15mol solution that is dissolved in the 100ml tetrahydrofuran (THF); 0-10 ℃ of reaction 1 hour; be warming up to 30 ℃ of reactions 6 hours; steam tetrahydrofuran (THF); the thick product isocyanic ester propyl-triethoxysilicane that obtains; through underpressure distillation; collect bp145-152 ℃/25mmHg, yield 78%, content are 97.1% (GC).
Embodiment 3
Mechanical stirring is being housed; the exsiccant constant pressure funnel; in the 1000ml four-hole boiling flask of reflux condensing tube and thermometer; under nitrogen protection, add 0.1mol triethoxy amine propyl silane; 1% dicyclohexyl carbon imines (Dcc) and 350ml tetrahydrofuran (THF); open and stir; under 0-5 ℃; slowly drip the carbonyl dimidazoles 0.20mol solution that is dissolved in the 100ml tetrahydrofuran (THF); 0-10 ℃ of reaction 2 hours; be warming up to 20 ℃ of reactions 15 hours; steam tetrahydrofuran (THF); the thick product isocyanic ester propyl-triethoxysilicane that obtains; through underpressure distillation; collect bp145-152 ℃/25mmHg, yield 85%, content are 97.9% (GC).
Embodiment 4
Mechanical stirring is being housed; the exsiccant constant pressure funnel; in the 1000ml four-hole boiling flask of reflux condensing tube and thermometer; under nitrogen protection, add 0.1mol triethoxy amine propyl silane; 1% dicyclohexyl carbon imines (Dcc) and 350ml tetrahydrofuran (THF); open and stir; under 0-10 ℃; slowly drip the carbonyl dimidazoles 0.25mol solution that is dissolved in the 100ml tetrahydrofuran (THF); 0-10 ℃ of reaction 4 hours; be warming up to 30 ℃ of reactions 12 hours; steam tetrahydrofuran (THF); the thick product isocyanic ester propyl-triethoxysilicane that obtains; through underpressure distillation; collect bp145-152 ℃/25mmHg, yield 86%, content are 97.5% (GC).
Embodiment 5
Mechanical stirring is being housed; the exsiccant constant pressure funnel; in the 1000ml four-hole boiling flask of reflux condensing tube and thermometer; under nitrogen protection, add 0.1mol triethoxy amine propyl silane; 0.1% dicyclohexyl carbon imines (Dcc) and 350ml tetrahydrofuran (THF); open and stir; under 0-10 ℃; slowly drip the carbonyl dimidazoles 0.20mol solution that is dissolved in the 100ml tetrahydrofuran (THF); 0-10 ℃ of reaction 2 hours; be warming up to 40 ℃ of reactions 15 hours; steam tetrahydrofuran (THF); the thick product isocyanic ester propyl-triethoxysilicane that obtains; through underpressure distillation; collect bp145-152 ℃/25mmHg, yield 76%, content are 97.1% (GC).
Embodiment 6
Mechanical stirring is being housed; the exsiccant constant pressure funnel; in the 1000ml four-hole boiling flask of reflux condensing tube and thermometer; under nitrogen protection, add 0.1mol triethoxy amine propyl silane; 0.5% dicyclohexyl carbon imines (Dcc) and 350ml tetrahydrofuran (THF); open and stir; under-5-0 ℃; slowly drip the carbonyl dimidazoles 0.20mol solution that is dissolved in the 100ml tetrahydrofuran (THF); 0-10 ℃ of reaction 4 hours; be warming up to 50 ℃ of reactions 8 hours; steam tetrahydrofuran (THF); the thick product isocyanic ester propyl-triethoxysilicane that obtains; through underpressure distillation; collect bp145-152 ℃/25mmHg, yield 79%, content are 97.6% (GC).
Embodiment 7
Mechanical stirring is being housed; the exsiccant constant pressure funnel; in the 1000ml four-hole boiling flask of reflux condensing tube and thermometer; under nitrogen protection, add 0.1mol triethoxy amine propyl silane; 3% dicyclohexyl carbon imines (Dcc) and 350ml tetrahydrofuran (THF); open and stir; under-5-0 ℃; slowly drip the carbonyl dimidazoles 0.20mol solution that is dissolved in the 100ml tetrahydrofuran (THF); 0-10 ℃ of reaction 2 hours; be warming up to 10 ℃ of reactions 21 hours; steam tetrahydrofuran (THF); the thick product isocyanic ester propyl-triethoxysilicane that obtains; through underpressure distillation; collect bp145-152 ℃/25mmHg, yield 85%, content are 97.7% (GC).
Embodiment 8
Mechanical stirring is being housed; the exsiccant constant pressure funnel; in the 1000ml four-hole boiling flask of reflux condensing tube and thermometer; under nitrogen protection, add 0.1mol triethoxy amine propyl silane; 5% dicyclohexyl carbon imines (Dcc) and 350ml tetrahydrofuran (THF); open and stir; under-5-0 ℃ ℃; slowly drip the carbonyl dimidazoles 0.20mol solution that is dissolved in the 100ml tetrahydrofuran (THF); 0-10 ℃ of reaction 1 hour; be warming up to 50 ℃ of reactions 6 hours; steam tetrahydrofuran (THF); the thick product isocyanic ester propyl-triethoxysilicane that obtains; through underpressure distillation; collect bp145-152 ℃/25mmHg, yield 88%, content are 97.6% (GC).
Embodiment 9
Mechanical stirring is being housed; the exsiccant constant pressure funnel; in the 1000ml four-hole boiling flask of reflux condensing tube and thermometer; under nitrogen protection, add 0.1mol triethoxy amine propyl silane; 3%L-first-2-halogen pyridinium salt and 350ml tetrahydrofuran (THF); open and stir; under 0-10 ℃; slowly drip the carbonyl dimidazoles 0.20mol solution that is dissolved in the 100ml tetrahydrofuran (THF); 0-10 ℃ of reaction 4 hours; be warming up to 20 ℃ of reactions 12 hours; steam tetrahydrofuran (THF); the thick product isocyanic ester propyl-triethoxysilicane that obtains; through underpressure distillation; collect bp145-152 ℃/25mmHg, yield 82%, content are 97.1% (GC).
Embodiment 10
Mechanical stirring is being housed; the exsiccant constant pressure funnel; in the 1000ml four-hole boiling flask of reflux condensing tube and thermometer; under nitrogen protection, add 0.1mol triethoxy amine propyl silane; 3% pair of Dimethylamino pyridine (DMAP) and 350ml tetrahydrofuran (THF); open and stir; under 0-10 ℃; slowly drip the carbonyl dimidazoles 0.20mol solution that is dissolved in the 100ml tetrahydrofuran (THF); 0-10 ℃ of reaction 3 hours; be warming up to 20 ℃ of reactions 1818 hours; steam tetrahydrofuran (THF); the thick product isocyanic ester propyl-triethoxysilicane that obtains; through underpressure distillation; collect bp145-152 ℃/25mmHg, yield 89%, content are 97.5% (GC).
Embodiment 11
Mechanical stirring is being housed; the exsiccant constant pressure funnel; in the 1000ml four-hole boiling flask of reflux condensing tube and thermometer; under nitrogen protection, add 0.1mol triethoxy amine propyl silane; 3%4-pyrryl pyridine (PPY) and 350ml tetrahydrofuran (THF); open and stir; under 0-10 ℃; slowly drip the carbonyl dimidazoles 0.20mol solution that is dissolved in the 100ml tetrahydrofuran (THF); 0-10 ℃ of reaction 2 hours; be warming up to 40 ℃ of reactions 15 hours; steam tetrahydrofuran (THF); the thick product isocyanic ester propyl-triethoxysilicane that obtains; through underpressure distillation; collect bp145-152 ℃/25mmHg, yield 86%, content are 97.7% (GC).
Embodiment 12
Mechanical stirring is being housed; the exsiccant constant pressure funnel; in the 1000ml four-hole boiling flask of reflux condensing tube and thermometer; under nitrogen protection, add 0.1mol triethoxy amine propyl silane; 3% aluminum chloride and 350ml tetrahydrofuran (THF); open and stir; under 0-10 ℃; slowly drip the carbonyl dimidazoles 0.20mol solution that is dissolved in the 100ml tetrahydrofuran (THF); 0-10 ℃ of reaction 2 hours; be warming up to 40 ℃ of reactions 15 hours; steam tetrahydrofuran (THF); the thick product isocyanic ester propyl-triethoxysilicane that obtains; through underpressure distillation; collect bp145-152 ℃/25mmHg, yield 73%, content are 97.0% (GC).
Embodiment 13
Mechanical stirring is being housed; the exsiccant constant pressure funnel; in the 1000ml four-hole boiling flask of reflux condensing tube and thermometer; under nitrogen protection, add 0.1mol triethoxy amine propyl silane; the 3% pair of methylsulphonic acid and 350ml tetrahydrofuran (THF); open and stir; under 0-10 ℃; slowly drip the carbonyl dimidazoles 0.20mol solution that is dissolved in the 100ml tetrahydrofuran (THF); 10-20 ℃ of reaction 1 hour; be warming up to 60 ℃ of reactions 7 hours; steam tetrahydrofuran (THF); the thick product isocyanic ester propyl-triethoxysilicane that obtains; through underpressure distillation; collect bp145-152 ℃/25mmHg, yield 83%, content are 97.8% (GC).
Embodiment 14
Mechanical stirring is being housed; the exsiccant constant pressure funnel; in the 1000ml four-hole boiling flask of reflux condensing tube and thermometer; under nitrogen protection, add 0.1mol triethoxy amine propyl silane; 3% tributylphosphine and 350ml tetrahydrofuran (THF); open and stir; under 0-10 ℃; slowly drip the carbonyl dimidazoles 0.20mol solution that is dissolved in the 100ml tetrahydrofuran (THF); 5-10 ℃ of reaction 2 hours; be warming up to 40 ℃ of reactions 5 hours; steam tetrahydrofuran (THF); the thick product isocyanic ester propyl-triethoxysilicane that obtains; through underpressure distillation; collect bp145-152 ℃/25mmHg, yield 85%, content are 97.3% (GC).
Embodiment 15
Mechanical stirring is being housed; the exsiccant constant pressure funnel; in the 1000ml four-hole boiling flask of reflux condensing tube and thermometer; under nitrogen protection, add 0.1mol triethoxy amine propyl silane; 3%4-pyrryl pyridine (PPY) and 350ml ethyl acetate; open and stir; under 0-5 ℃; slowly drip the carbonyl dimidazoles 0.20mol solution that is dissolved in the 100ml ethyl acetate; 10-20 ℃ of reaction 2 hours; be warming up to 50 ℃ of reactions 12 hours; steam ethyl acetate; the thick product isocyanic ester propyl-triethoxysilicane that obtains; through underpressure distillation; collect bp145-152 ℃/25mmHg, yield 81%, content are 98.6% (GC).
Embodiment 16
Mechanical stirring is being housed; the exsiccant constant pressure funnel; in the 1000ml four-hole boiling flask of reflux condensing tube and thermometer; under nitrogen protection, add 0.1mol triethoxy amine propyl silane; 3%4-pyrryl pyridine (PPY) and 350ml acetone; open and stir; under 0-10 ℃; slowly drip the carbonyl dimidazoles 0.20mol solution that is dissolved in 100ml acetone; 0-10 ℃ of reaction 2 hours; be warming up to 40 ℃ of reactions 10 hours; steam acetone; the thick product isocyanic ester propyl-triethoxysilicane that obtains; through underpressure distillation; collect bp145-152 ℃/25mmHg, yield 813%, content are 97.2% (GC).
Embodiment 17
Mechanical stirring is being housed; the exsiccant constant pressure funnel; in the 1000ml four-hole boiling flask of reflux condensing tube and thermometer; under nitrogen protection, add 0.1mol triethoxy amine propyl silane; 3%4-pyrryl pyridine (PPY) and 350ml normal hexane; open and stir; under 0-10 ℃; slowly drip the carbonyl dimidazoles 0.20mol solution that is dissolved in the 100ml normal hexane; 0-10 ℃ of reaction 4 hours; be warming up to 40 ℃ of reactions 6 hours; steam normal hexane; the thick product isocyanic ester propyl-triethoxysilicane that obtains; through underpressure distillation; collect bp145-152 ℃/25mmHg, yield 85%, content are 97.2% (GC).
Embodiment 18
Mechanical stirring is being housed; the exsiccant constant pressure funnel; in the 1000ml four-hole boiling flask of reflux condensing tube and thermometer; under nitrogen protection, add 0.1mol triethoxy amine propyl silane; 3%4-pyrryl pyridine (PPY) and 350ml toluene; open and stir; under 0-10 ℃; slowly drip the carbonyl dimidazoles 0.20mol solution that is dissolved in 100ml toluene; 10-20 ℃ of reaction 2 hours; be warming up to 40 ℃ of reactions 15 hours; steam toluene; the thick product isocyanic ester propyl-triethoxysilicane that obtains; through underpressure distillation; collect bp145-152 ℃/25mmHg, yield 88%, content are 97.1% (GC).
Embodiment 19
Mechanical stirring is being housed; the exsiccant constant pressure funnel; in the 1000ml four-hole boiling flask of reflux condensing tube and thermometer; under nitrogen protection, add 0.1mol trimethoxy amine propyl silane; 3%4-pyrryl pyridine (PPY) and 350ml toluene; open and stir; under 0-10 ℃; slowly drip the carbonyl dimidazoles 0.20mol solution that is dissolved in 100ml toluene; 0-10 ℃ of reaction 1 hour; be warming up to 70 ℃ of reactions 3 hours; steam toluene; the thick product isocyanic ester propyl trimethoxy silicane that obtains; through underpressure distillation; collect bp137-142 ℃/25mmHg, yield 85%, content are 97.0% (GC).
Embodiment 20
Mechanical stirring is being housed; the exsiccant constant pressure funnel; in the 1000ml four-hole boiling flask of reflux condensing tube and thermometer; under nitrogen protection, add 0.1mol chloromethyl dimethoxy amine propyl silane; 3% 4-pyrryl pyridine (PPY) and 350ml toluene; open and stir; under-5-0 ℃; slowly drip the carbonyl dimidazoles 0.20mol solution that is dissolved in 100ml toluene; 0-10 ℃ of reaction 1 hour; be warming up to 40 ℃ of reactions 15 hours; steam toluene; the thick product isocyanic ester propyl chloride methyl dimethoxysilane that obtains; through underpressure distillation; collect bp156-159 ℃/25mmHg, yield 81%, content are 97.3% (GC).
Embodiment 21
Mechanical stirring is being housed; the exsiccant constant pressure funnel; in the 1000ml four-hole boiling flask of reflux condensing tube and thermometer; under nitrogen protection, add 0.1mol chloromethyl diethoxy amine propyl silane silane; 3%4-pyrryl pyridine (PPY) and 350ml toluene; open and stir; under-5-0 ℃; slowly drip the carbonyl dimidazoles 0.20mol solution that is dissolved in 100ml toluene; 0-10 ℃ of reaction 2 hours; be warming up to 40 ℃ of reactions 6 hours; steam toluene; the thick product isocyanic ester propyl chloride methyldiethoxysilane that obtains; through underpressure distillation; collect bp167-171 ℃/25mmHg, yield 78%, content are 97.6% (GC).
Embodiment 22
Mechanical stirring is being housed; the exsiccant constant pressure funnel; in the 1000ml four-hole boiling flask of reflux condensing tube and thermometer; under nitrogen protection, add 0.1mol trimethoxy amine ethylsilane silane; 3%4-pyrryl pyridine (PPY) and 350ml toluene; open and stir; under-5-0 ℃; slowly drip the carbonyl dimidazoles 0.20mol solution that is dissolved in 100ml toluene; 0-10 ℃ of reaction 3 hours; be warming up to 40 ℃ of reactions 5 hours; steam toluene; the thick product isocyanic ester ethyl trimethoxy amine silane that obtains; through underpressure distillation; collect bp113-118 ℃/25mmHg, yield 78%, content are 97.6% (GC).
Claims (6)
1. the synthetic method of an isocynate silane coupling agent is characterized in that be raw material with amino containing silane (II) with carbonyl dimidazoles, and the mol ratio of two raw materials is 1: 1.2～2.5, under catalyzer C effect, in organic solvent, be 0～70 ℃ of fully reaction in temperature, it is R that aftertreatment promptly gets general formula
X(R
1O)
3-XSi (CH
2)
nThe isocynate silane coupling agent of NCO (I), reaction equation is:
X＝0，1，
n＝2，3，
R is that carbon atom is 1 alkane,
R
1Be that halogenated alkane or carbon atom are 1～4 alkane;
Described catalyzer C is dicyclohexyl carbon imines, L-first-2-halogen pyridinium salt, a kind of in Dimethylamino pyridine, 4-pyrryl pyridine, aluminum chloride, the tributylphosphine;
Described organic solvent is ethyl acetate, propyl acetate, butylacetate, tetrahydrofuran (THF), ether, propyl ether, isopropyl ether, butyl ether, hexyl ether, methyl tertiary butyl ether, acetone, butanone, pentanone, hexanaphthene, normal hexane, sherwood oil, a kind of in benzene,toluene,xylene, the trimethylbenzene.
2. the synthetic method of isocynate silane coupling agent according to claim 1, it is characterized in that described amino containing silane (II): carbonyl dimidazoles: the mol ratio of catalyzer C is 1: 1.2～2.5: 0.005～0.02.
3. the synthetic method of isocynate silane coupling agent according to claim 2, it is characterized in that described amino containing silane (II): carbonyl dimidazoles: the mol ratio of catalyzer C is 1: 1～6.0: 0.01～0.2.
4. according to the synthetic method of claim 1 or 2 or 3 described isocynate silane coupling agents, it is characterized in that described amino containing silane and organic solvent mass ratio 1: 0.5～5.
5. according to the synthetic method of claim 1 or 2 or 3 described isocynate silane coupling agents, it is characterized in that the described reaction times is 2～36h.
6. the synthetic method of isocynate silane coupling agent according to claim 4 is characterized in that the described reaction times is 2～36h.
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| CN109776593B (en) * | 2017-11-14 | 2023-05-09 | 河北圣泰材料股份有限公司 | Preparation method of 1, 3-dimethyl-1, 3-tetraethylenedisiloxane |
| CN113292591A (en) * | 2021-06-23 | 2021-08-24 | 唐山三孚新材料有限公司 | Synthesis method and application of 1, 3-bis (isocyanatoalkyl) -1,1,3, 3-tetramethyldisiloxane |
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| CN1887888A (en) * | 2006-07-27 | 2007-01-03 | 应城市德邦化工新材料有限公司 | Prepn of isocyanate-containing alkyl silane or alkyl siloxane |
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Non-Patent Citations (3)
| Title |
|---|
| CN 1887888 A,全文. |
| H.A.Staab.New Methods of Preparative Organic Chemistry.Angew.Chem.internat.Edit1 7.1962,1(7),全文. |
| H.A.Staab.New Methods of Preparative Organic Chemistry.Angew.Chem.internat.Edit1 7.1962,1(7),全文. * |
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