CN106632449A - Preparation method of alpha-amino triethoxysilane - Google Patents
Preparation method of alpha-amino triethoxysilane Download PDFInfo
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- CN106632449A CN106632449A CN201610878044.3A CN201610878044A CN106632449A CN 106632449 A CN106632449 A CN 106632449A CN 201610878044 A CN201610878044 A CN 201610878044A CN 106632449 A CN106632449 A CN 106632449A
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- triethoxysilane
- alpha
- preparation
- amido
- reaction
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001412 amines Chemical class 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- ZDOBWJOCPDIBRZ-UHFFFAOYSA-N chloromethyl(triethoxy)silane Chemical compound CCO[Si](CCl)(OCC)OCC ZDOBWJOCPDIBRZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000009835 boiling Methods 0.000 claims abstract description 12
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004821 distillation Methods 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- FYTPGBJPTDQJCG-UHFFFAOYSA-N Trichloro(chloromethyl)silane Chemical compound ClC[Si](Cl)(Cl)Cl FYTPGBJPTDQJCG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 238000005292 vacuum distillation Methods 0.000 claims description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 13
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 10
- 239000012467 final product Substances 0.000 claims description 7
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 6
- -1 silicane Alkane Chemical class 0.000 claims description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N anhydrous methyl chloride Natural products ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 5
- 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
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 238000002454 metastable transfer emission spectrometry Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 7
- 238000001914 filtration Methods 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 239000002250 absorbent Substances 0.000 abstract description 5
- 230000002745 absorbent Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- ROWWCTUMLAVVQB-UHFFFAOYSA-N triethoxysilylmethanamine Chemical compound CCO[Si](CN)(OCC)OCC ROWWCTUMLAVVQB-UHFFFAOYSA-N 0.000 description 31
- 229910000077 silane Inorganic materials 0.000 description 14
- 238000002329 infrared spectrum Methods 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 229920002379 silicone rubber Polymers 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 239000004945 silicone rubber Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 230000006837 decompression Effects 0.000 description 5
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000004971 Cross linker Substances 0.000 description 4
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 4
- 229960004756 ethanol Drugs 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 239000005055 methyl trichlorosilane Substances 0.000 description 4
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000006136 alcoholysis reaction Methods 0.000 description 3
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000005311 nuclear magnetism Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000003961 organosilicon compounds Chemical group 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 1
- HAAZMOAXEMIBAJ-UHFFFAOYSA-N 4-chloro-2-methylquinazoline Chemical compound C1=CC=CC2=NC(C)=NC(Cl)=C21 HAAZMOAXEMIBAJ-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 238000005844 autocatalytic reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- PJMICNUGBHGMKQ-UHFFFAOYSA-N ethane-1,1,2-triamine Chemical compound NCC(N)N PJMICNUGBHGMKQ-UHFFFAOYSA-N 0.000 description 1
- HCFPRFJJTHMING-UHFFFAOYSA-N ethane-1,2-diamine;hydron;chloride Chemical compound [Cl-].NCC[NH3+] HCFPRFJJTHMING-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ODYNBECIRXXOGG-UHFFFAOYSA-N n-butylbutan-1-amine;hydron;chloride Chemical compound [Cl-].CCCC[NH2+]CCCC ODYNBECIRXXOGG-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- CBPYOHALYYGNOE-UHFFFAOYSA-M potassium;3,5-dinitrobenzoate Chemical compound [K+].[O-]C(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 CBPYOHALYYGNOE-UHFFFAOYSA-M 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 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
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229920000260 silastic Polymers 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The invention relates to a preparation method of alpha-amino triethoxysilane. The method comprises the following steps: (1) dissolving sodium ethoxide in a sufficient amount of organic solvent, then uniformly dropwise adding the sodium ethoxide solution into chloromethyl trichlorosilane, allowing the raw materials to react for a period of time at normal temperature after the dropwise addition is completed, carrying out normal pressure distillation to remove ethanol and insoluble substances to obtain chloromethyl triethoxysilane; (2) heating organic amine under the protection of nitrogen until boiling, and then dropwise adding the chloromethyl triethoxysilane prepared in the step (1), allowing the raw materials to react for 1-8 hours at the temperature of 70-200 DEG C after the dropwise addition is completed; filtering the reactant to remove the generated salt after the reaction is ended, distilling at normal pressure to remove the low-boiling-point substance, and then collecting the product at a proper boiling point under reduced pressure distillation, so that the alpha-amino triethoxysilane is obtained. According to the invention, no additional acid absorbent needs to be added, organic solvent is not added, so that the subsequent separation is simple, and the generation of by-products such as polysubstituted compounds of organic amines is less, the utilization rate of the amine is relatively high, and the side reaction of the reaction system is easy to control; the product purity can reach more than 95%, and the yield is over 40%.
Description
Technical field
The present invention relates to a kind of preparation method of amine alkyl triethoxysilane, is connected with specifically a kind of alpha-position carbon
The preparation method of the triethoxysilane cross-linking agent of amino, belongs to organosilicon synthesis technical field.
Background technology
The cross-linking agent of single-component room-temperature vulcanized silicone rubber is the multi-functional silane compound containing hydrolyzable group, formula
For R4-nSiYn, wherein n=3 or n=4；R is carbon functional group, and Y is hydrolyzable group.In single-component room-temperature vulcanized silicone rubber
Play solidification crosslinking.
The small molecule thing difference removed during according to silicone rubber crosslinking can be roughly divided into decarboxylation acid type, and ketoxime removing type takes off
Alcohol type, takes off amine type, de amide type, deacetone and deshydroxy amine type.Different its hydrolysis rate of the small molecule thing of removing is different, and not
Same model silicone rubber property and purposes are also different.Wherein, dealcoholized type room temperature vulcanized silicone rubber curing rate is slower, in addition it is also necessary to add
Catalyst accelerates its curing rate.Conventional catalyst have organo-tin compound (such as dibutyl tin laurate, stannous octoate),
Amino silane etc..And organic tin has certain toxicity, be difficult to be sufficiently mixed in sizing material after adding due to catalyst it is uniform and
Appearance is localized gelling, causes cross-linking reaction not complete enough.
In organo-silicon compound structure, the position of substituent group can be different degrees of to the generation of the stability of organo-silicon compound
Affect.α-functional group's silane crosslinker is because between functional group and silicon atom every a carbon atom, thus the electronics of functional group is imitated
The impact of reply silicon atom is larger, and the silane crosslinker of α-functional group has been shown to have certain autocatalytic cleavage energy；Although
Silicon-carbon bonds are easily broken off under alkalescence condition, but its heat stability is higher；And synthetic method is simple, is not required to use precious metal catalyst
Agent.Therefore R and D α-silane crosslinker has very big using value.
Amino-carbon sense base silane is one of maximum silane crosslinker of consumption, by the room temperature vulcanization silicon rubber of its solidification crosslinking
Glue has excellent caking property, and amine propyl group alkoxy silane is modal amino-carbon sense base silane.But the ethoxy of alpha-amido three
Base silane is proven to have autocatalytic cleavage energy, greatly shortens can hardening time.But because synthesis technique complexity does not have
To industrialized production and extensively application.
Organic silicon monomer is the basis of Silicone Industry, and methylchlorosilane is the important original of synthesizing organo-silicon material
Material, dimethyldichlorosilane is maximum, the most widely used organic silicon monomer of consumption.In the process of direct synthesis methylchlorosilane
In, in addition to primary product dimethyldichlorosilane, methyl trichlorosilane is Main By product, account for gross product 5%～
15%, ratio is quite big.China's organosilicon industry development is rapidly abnormal, ends for the end of the year 2015, domestic methylchlorosilane aggregated capacity
Up to 8,000,000 tons/year, methyl trichlorosilane is also corresponding a large amount of overstocked.The new Application way of research methyl trichlorosilane, exploitation
Organosilicon new material, realizes recycling for organic silicon monomer, not only with important scientific meaning, and with important reality
With value.
Chinese patent document CN105131028A carries out alcoholysis reaction to prepare using methyl trichlorosilane and dehydrated alcohol
MTES, reaction will add catalyst also to give birth to a large amount of corrosivity hydrogen chloride gas, tend not to drain in time
Only, the presence etching apparatus of hydrogen chloride and alcoholysis reaction is complicated, occurs in that many side reactions, reduce yield.
Chinese patent document CN101768180A reacts life using chloropropyl triethoxysilane and ammonia in autoclave
Into aminopropyltriethoxywerene werene, this method power consumption is high, high cost.
Organic amine is added dropwise to the method for chloromethyl triethoxysilane to prepare the ethoxy of aminomethyl three by Yin Yigao, Zhang Yi etc.
Base silane, (referring to：" synthesis and performance study of autocatalysis cross-linking organosilicon seal glue ", Yin with high,《China's crosslinking
Agent》, the 5th phase in 2007).The method that this method drips acid using alkali, is also easy to produce polysubstituted by-product of Denging, and to add in reaction system
Enter substantial amounts of acid absorbent, also operation becomes complicated.
The content of the invention
For the deficiencies in the prior art, the present invention provides a kind of preparation method of alpha-amido triethoxysilane.
Technical scheme is as follows：
A kind of preparation method of alpha-amido triethoxysilane, including step is as follows：
(1) Sodium ethylate is dissolved in enough organic solvents, is then uniformly added drop-wise in Chloromethyltrichlorosilane, dripped
Afterwards for a period of time, air-distillation removes organic solvent and filters off insoluble matter normal-temperature reaction, and vacuum distillation obtains the ethoxy of chloromethyl three
Base silane；
(2) organic amine is heated under nitrogen protection boiling, then the ethoxy of chloromethyl three obtained by Deca step (1)
Base silane, at 70～200 DEG C after dripping, reacts 1～8 hour；Reaction filters out the salt of generation after terminating, air-distillation is removed
Low-boiling-point substance is removed, then vacuum distillation, obtain final product alpha-amido triethoxysilane.
, according to the invention it is preferred to, the organic solvent described in step (1) is the mol ratio of ethanol, ethanol and Sodium ethylate
For：(4～5)：1.
, according to the invention it is preferred to, the mol ratio of Sodium ethylate and Chloromethyltrichlorosilane described in step (1) for (2～
4)：1, further preferably (3～4)：1.
, according to the invention it is preferred to, the terminal of alcohol sodium solution Deca is reaction system pH in step (1) when being neutral
Wait；
Preferably, described reaction temperature is room temperature；Response time is：5min-1h；
Preferably, the rate of addition of alcohol sodium solution is：1 drop/sec.
, according to the invention it is preferred to, the pressure limit of vacuum distillation is 5mmHg～20mmHg in step (1).
, according to the invention it is preferred to, also include for the ethanol being evaporated recycling step in step (1), cross and filter
The insoluble matter for going is Sodium Chloride and slightly excessive Sodium ethylate.
, according to the invention it is preferred to, the speed that is passed through of nitrogen is in step (2)：0.1～2L/min, organic amine and chloromethane
The mol ratio of ethyl triethoxy silicane alkane is (2～8)：1, further preferably (4～6)：1.
, according to the invention it is preferred to, the organic amine described in step (2) is RaNH(3-a)Or RN2H4, R is containing 1-6 carbon
Alkane, a is 1 to 2 integer；Described nitrogen is the drying nitrogen of anhydrous and oxygen-free.
, according to the invention it is preferred to, the drop rate of chloromethyl triethoxysilane is (1.3～1.7) g/ in step (2)
Min, described reaction temperature is 100-180 DEG C, and the response time is 3-6 hours, the pressure limit of vacuum distillation be 5mmHg～
20mmHg。
, according to the invention it is preferred to, the organic amine described in step (2) is ethylenediamine, diethylamine, di-n-butylamine, just
Butylamine or cyclohexylamine.
After step (2) reaction terminates in the present invention, the hydrochlorate of organic amine is filtered to remove, air-distillation removes low-boiling-point substance,
Then product is collected in vacuum distillation, remaining for high boiling by-product.
The reaction scheme and principle of the present invention：
In the present invention, during Chloromethyltrichlorosilane is with Sodium ethylate reaction generation chloromethyl triethoxysilane and Sodium Chloride
Property, it is to avoid the process of extra addition acid absorbent；Then, chloromethyl triethoxysilane is anti-with excessive organic amine again
Should, alpha-amido triethoxysilane is generated, due to chloromethyl triethoxysilane is added drop-wise to into organic amine during reaction
In, ensure that the excess of organic amine, so in the reaction organic amine not only as reactant but also as acid absorbent, and chloromethane
Ethyl triethoxy silicane alkane is added dropwise in excessive organic amine, it is possible to reduce the life of the by-product such as polysubstituted thing of organic amine
Into.
Obtained alpha-amido triethoxysilane of the invention can be applied to room temperature vulcanization under conditions of without catalyst
The solidification crosslinking of raw-silastic continuously (107 glue).
Beneficial effects of the present invention are as follows：
1. in the preparation method of alpha-amido triethoxysilane of the present invention, with substantial amounts of industrial by-products chloromethyl trichlorine silicon
Alkane is starting material, environmental protection and energy saving, and both having accomplished to turn waste into wealth makes energy recycling, and the use of poisoned catalyst is reduced again,
Meet the theory of current environmental protection.
2. catalyst need not be added the step for alcoholysis in the preparation method of alpha-amido triethoxysilane of the present invention
Corrosive gas hydrogen chloride will not be produced so that reaction becomes simple and environmentally-friendly.The step for ammonolysis reaction, need not pressurize, also not
Extra addition acid absorbent is needed, and the utilization rate of amine is high, does not add organic solvent, later separation is simple, and reaction system is easy
In control.
3. boiling under reflux Deca chloromethyl triethoxy is adopted in the preparation method of alpha-amido triethoxysilane of the present invention
The method of silane, reaction temperature is easily controllable, and side reaction is less.
4., up to 95%, yield is more than 40% for alpha-amido triethoxysilane product purity obtained in the inventive method.
5. alpha-amido triethoxysilane product can be applied under conditions of without catalyst obtained in the inventive method
It is crosslinked in the solidification of room temperature vulcanized silicone rubber rubber (107 glue), the room temperature vulcanized silicone rubber for solidifying crosslinking has good gluing
Knot property and heat stability.
Description of the drawings
Fig. 1 is the infrared spectrum of chloromethyl triethoxysilane obtained in the embodiment of the present invention 1.
Fig. 2 is the proton nmr spectra of chloromethyl triethoxysilane obtained in the embodiment of the present invention 1.
Fig. 3 is the infrared spectrum of α obtained in the embodiment of the present invention 2-(N, N- diethyl) aminomethyl triethoxysilane.
Fig. 4 is the hydrogen nuclear magnetic resonance of α obtained in the embodiment of the present invention 2-(N, N- diethyl) aminomethyl triethoxysilane
Spectrum.
Fig. 5 is the infrared spectrum of α obtained in the embodiment of the present invention 3-(N- normal-butyls) aminomethyl triethoxysilane.
Fig. 6 is the proton nmr spectra of α obtained in the embodiment of the present invention 3-(N- normal-butyls) aminomethyl triethoxysilane.
Fig. 7 is the infrared spectrum of α obtained in the embodiment of the present invention 4-(N, N- di-n-butyl) aminomethyl triethoxysilane.
Fig. 8 is the nuclear magnetic resonance, NMR of α obtained in the embodiment of the present invention 4-(N, N- di-n-butyl) aminomethyl triethoxysilane
Hydrogen is composed.
Fig. 9 is the infrared spectrum of α obtained in the embodiment of the present invention 5-(N- cyclohexyl) aminomethyl triethoxysilane.
Figure 10 is the hydrogen nuclear magnetic resonance of α obtained in the embodiment of the present invention 5-(N- cyclohexyl) aminomethyl triethoxysilane
Spectrum.
Figure 11 is the infrared spectrum of α obtained in the embodiment of the present invention 6-(β-aminoethyl) aminomethyl triethoxysilane.
Figure 12 is the hydrogen nuclear magnetic resonance of α obtained in the embodiment of the present invention 6-(β-aminoethyl) aminomethyl triethoxysilane
Spectrum.
Specific embodiment
Below by specific embodiment, the present invention will be further described, but not limited to this.
It is raw materials used in embodiment to be convenient source, commercial products.
Embodiment 1
A kind of preparation method of chloromethyl triethoxysilane, including step is as follows：
19mL Chloromethyltrichlorosilanes are added in the there-necked flask of 250mL dryings, 31g Sodium ethylate is dissolved in into 110mL second
In alcohol, under nitrogen protection it is slowly added drop-wise in there-necked flask by constant pressure funnel, rate of addition is 1 drop/sec, works as body
The PH of system stops Deca when acidity is changed into neutrality.Reacting at room temperature after 30min carries out air-distillation, steams ethanol,
Then filtration from sodium chloride and the less Sodium ethylate of excess, vacuum distillation obtains chloromethyl triethoxysilane, uses after giving over to.
The infrared spectrum of chloromethyl triethoxysilane obtained in the present embodiment is as shown in figure 1, proton nmr spectra such as Fig. 2
It is shown.From Fig. 1,2, product obtained in the present embodiment is chloromethyl triethoxysilane.
Embodiment 2
A kind of preparation method of α-(N, N- diethyl) aminomethyl triethoxysilane, including step is as follows：
The diethylamine of 52.4mL is added in four-hole bottles of the 200mL equipped with condensing tube, boiling is heated under nitrogen protection
Rise, by constant pressure funnel in 35min uniform Deca 18.3mL chloromethyl triethoxysilane.After being added dropwise to complete, 62
6h is reacted at DEG C, after reaction terminates, mixture room temperature is cooled to into.Decompression sucking filtration is carried out, diethylamine hydrochloride is filtered off.Normal pressure steams
Excessive diethylamine is removed in distillation, then carries out vacuum distillation, and vacuum is 13mmHg, takes 99～107 DEG C of fraction, obtain final product α-(N,
N- diethyl) aminomethyl triethoxysilane.
The infrared spectrum of α obtained in the present embodiment-(N, N- diethyl) aminomethyl triethoxysilane is as shown in figure 3, core
Magnetic resonance hydrogen spectrum is as shown in Figure 4.The product by obtained in Fig. 3,4 understand the present embodiment is α-(N, N- diethyl) second of aminomethyl three
TMOS.
The purity of α obtained in the present embodiment-(N, N- diethyl) aminomethyl triethoxysilane is 96%, and yield is
63.5%.
Embodiment 3
A kind of preparation method of α-(N- normal-butyls) aminomethyl triethoxysilane, including step is as follows：
One n-butylamine of 40mL is added in four-hole bottles of the 200mL equipped with condensing tube, boiling is heated under nitrogen protection
Rise, by constant pressure funnel in 40min uniform Deca 20.3mL chloromethyl triethoxysilane.After being added dropwise to complete, 86
260min is reacted at DEG C, after reaction terminates, mixture room temperature is cooled to into.Decompression sucking filtration is carried out, a n-butylamine hydrochlorate is filtered off.
Air-distillation removes an excessive n-butylamine, then carries out vacuum distillation, and vacuum is 23mmHg, takes 114～122 DEG C of fraction,
Obtain final product α-(N- normal-butyls) aminomethyl triethoxysilane.
The infrared spectrum of α obtained in the present embodiment-(N- normal-butyls) aminomethyl triethoxysilane is as shown in figure 5, nuclear-magnetism
Resonance hydrogen spectrum is as shown in Figure 6.The product by obtained in Fig. 5,6 understand the present embodiment is α-(N- normal-butyls) aminomethyl triethoxy
Silane.
The purity of α obtained in the present embodiment-(N- normal-butyls) aminomethyl triethoxysilane is 97%, and yield is
43.5%.
Embodiment 4
A kind of preparation method of α-(N, N- di-n-butyl) aminomethyl triethoxysilane, including step is as follows：
The di-n-butylamine of 84.3mL is added in four-hole bottles of the 200mL equipped with condensing tube, is heated under nitrogen protection
Boiling, by constant pressure funnel in 43min uniform Deca 20.3mL chloromethyl triethoxysilane.After being added dropwise to complete,
265min is reacted at 155 DEG C, after reaction terminates, mixture room temperature is cooled to into.Decompression sucking filtration is carried out, di-n-butylamine hydrochloric acid is filtered off
Salt.Vacuum distillation is directly carried out, vacuum is 8mmHg, the low-boiling-point substance such as removing di-n-butylamine, then 122～130 DEG C of fraction is taken,
Obtain final product α-(N, N- di-n-butyl) aminomethyl triethoxysilane.
The infrared spectrum of α obtained in the present embodiment-(N, N- di-n-butyl) aminomethyl triethoxysilane as shown in fig. 7,
Proton nmr spectra is as shown in Figure 8.The product by obtained in Fig. 7,8 understand the present embodiment is α-(N, N- di-n-butyl) aminomethyl
Triethoxysilane.
The purity of α obtained in the present embodiment-(N, N- di-n-butyl) aminomethyl triethoxysilane is 96%, and yield is
70.1%.
Embodiment 5
A kind of preparation method of α-(N- cyclohexyl) aminomethyl triethoxysilane, including step is as follows：
The di-n-butylamine of 45.9mL is added in four-hole bottles of the 200mL equipped with condensing tube, is heated under nitrogen protection
Boiling, by constant pressure funnel in 55min uniform Deca 20.3mL chloromethyl triethoxysilane.After being added dropwise to complete,
5h is reacted at 140 DEG C, after reaction terminates, mixture room temperature is cooled to into.Decompression sucking filtration is carried out, cyclohexylamine hydrochloride is filtered off.Directly
Tap into row vacuum distillation, vacuum is 7mmHg, remove the low-boiling-point substance such as cyclohexylamine, then take 124～130 DEG C of fraction, obtain final product α-
(N- cyclohexyl) aminomethyl triethoxysilane.
The infrared spectrum of α obtained in the present embodiment-(N- cyclohexyl) aminomethyl triethoxysilane is as shown in figure 9, nuclear-magnetism
Resonance hydrogen spectrum is as shown in Figure 10.The product by obtained in Fig. 9,10 understand the present embodiment is α-(N- cyclohexyl) ethoxy of aminomethyl three
Base silane.
The purity of α obtained in the present embodiment-(N- cyclohexyl) aminomethyl triethoxysilane is 98%, and yield is
71.3%.
Embodiment 6
A kind of preparation method of α-(β-aminoethyl) aminomethyl triethoxysilane, including step is as follows：
The ethylenediamine amine of 54.0mL is added in four-hole bottles of the 200mL equipped with condensing tube, is heated under nitrogen protection
Boiling, by constant pressure funnel in 60min uniform Deca 20.0mL chloromethyl triethoxysilane.After being added dropwise to complete,
3h is reacted at 117 DEG C, after reaction terminates, mixture room temperature is cooled to into.Decompression sucking filtration is carried out, ethylenediamine-hydrochloride is filtered off.Often
Pressure is distilled off excessive ethylenediamine, then carries out vacuum distillation, and vacuum is 15mmHg, takes 120～132 DEG C of fraction, is obtained final product
α-(β-aminoethyl) aminomethyl triethoxysilane.
The infrared spectrum of α obtained in the present embodiment-(β-aminoethyl) aminomethyl triethoxysilane is as shown in figure 11, nuclear-magnetism
Resonance hydrogen spectrum is as shown in figure 12.The product by obtained in Figure 11,12 understand the present embodiment is α-(β-aminoethyl) second of aminomethyl three
TMOS.
The purity of α obtained in the present embodiment-(β-aminoethyl) aminomethyl triethoxysilane is 95%, and yield is
57.3%.
Claims (10)
1. a kind of preparation method of alpha-amido triethoxysilane, including step is as follows：
(1) Sodium ethylate is dissolved in enough organic solvents, is then uniformly added drop-wise in Chloromethyltrichlorosilane, after dripping often
Temperature reaction a period of time, air-distillation removes organic solvent and filters off insoluble matter, and vacuum distillation obtains chloromethane ethyl triethoxy silicane
Alkane；
(2) organic amine is heated under nitrogen protection boiling, then the chloromethane ethyl triethoxy silicane obtained by Deca step (1)
Alkane, at 70～200 DEG C after dripping, reacts 1～8 hour；Reaction filters out the salt of generation after terminating, air-distillation removes low
Boiling thing, then vacuum distillation obtains final product alpha-amido triethoxysilane.
2. the preparation method of alpha-amido triethoxysilane according to claim 1, it is characterised in that institute in step (1)
The organic solvent stated is ethanol；
Preferably, the mol ratio of ethanol and Sodium ethylate is：(4～5)：1.
3. the preparation method of alpha-amido triethoxysilane according to claim 1, it is characterised in that institute in step (1)
The mol ratio for stating Sodium ethylate and Chloromethyltrichlorosilane is (2～4)：1.
4. the preparation method of alpha-amido triethoxysilane according to claim 1, it is characterised in that second in step (1)
When the terminal of alcohol sodium solution Deca is neutral for reaction system pH；
Preferably, described reaction temperature is room temperature；Response time is：5min-1h；
Preferably, the rate of addition of alcohol sodium solution is：1 drop/sec.
5. the preparation method of alpha-amido triethoxysilane according to claim 1, it is characterised in that step subtracts in (1)
The pressure limit of pressure distillation is 5mmHg～20mmHg.
6. the preparation method of alpha-amido triethoxysilane according to claim 1, it is characterised in that step has in (2)
Machine amine is (2～8) with the mol ratio of chloromethyl triethoxysilane：1, preferably (4～6)：1.
7. the preparation method of alpha-amido triethoxysilane according to claim 1, it is characterised in that institute in step (2)
The organic amine stated is RaNH(3-a)Or RN2H4, R is the alkane containing 1-6 carbon, and a is 1 to 2 integer.
8. the preparation method of alpha-amido triethoxysilane according to claim 1, it is characterised in that chlorine in step (2)
The drop rate of MTES is (1.3～1.7) g/min.
9. the preparation method of alpha-amido triethoxysilane according to claim 1, it is characterised in that institute in step (2)
The reaction temperature stated is 100-180 DEG C, and the response time is 3-6 hours；
Preferably, the pressure limit of vacuum distillation is 5mmHg～20mmHg in step (2).
10. the preparation method of alpha-amido triethoxysilane according to claim 1, it is characterised in that institute in step (2)
The organic amine stated is ethylenediamine, diethylamine, di-n-butylamine, a n-butylamine or cyclohexylamine.
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| CN108409779A (en) * | 2018-05-15 | 2018-08-17 | 威海新元化工有限公司 | A kind of preparation method of γ-aminopropyl trisiloxane |
| CN109021006A (en) * | 2018-09-08 | 2018-12-18 | 杨秀莲 | A kind of pollution-free method for preparing diphenyl diethoxy silane |
| CN109053794A (en) * | 2018-09-13 | 2018-12-21 | 山东大学 | Trialkoxy silane and preparation based on thioether bond is connected on sulfydryl-alkene click-reaction α-carbon and containing different functional groups |
| CN109503649A (en) * | 2018-12-27 | 2019-03-22 | 山东硅科新材料有限公司 | A kind of preparation process of high-purity trimethylmethoxysilane |
| CN111184020A (en) * | 2020-02-29 | 2020-05-22 | 辽宁山水益农科技有限公司 | Preparation process of organic silicon plant growth regulator |
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| CN108409779B (en) * | 2018-05-15 | 2020-06-19 | 威海新元化工有限公司 | Preparation method of gamma-aminopropyl trisiloxane |
| CN109021006A (en) * | 2018-09-08 | 2018-12-18 | 杨秀莲 | A kind of pollution-free method for preparing diphenyl diethoxy silane |
| CN109053794A (en) * | 2018-09-13 | 2018-12-21 | 山东大学 | Trialkoxy silane and preparation based on thioether bond is connected on sulfydryl-alkene click-reaction α-carbon and containing different functional groups |
| CN109053794B (en) * | 2018-09-13 | 2020-10-09 | 山东大学 | Trialkoxysilane with thioether bond connected to alpha-carbon and different functional groups based on mercapto-alkene click reaction and preparation method thereof |
| CN109503649A (en) * | 2018-12-27 | 2019-03-22 | 山东硅科新材料有限公司 | A kind of preparation process of high-purity trimethylmethoxysilane |
| CN111184020A (en) * | 2020-02-29 | 2020-05-22 | 辽宁山水益农科技有限公司 | Preparation process of organic silicon plant growth regulator |
| CN112110952A (en) * | 2020-10-09 | 2020-12-22 | 山东大学 | Functionalized alpha-amino triethoxysilane and preparation method thereof |
| CN112110952B (en) * | 2020-10-09 | 2021-12-07 | 山东大学 | Functionalized alpha-amino triethoxysilane and preparation method thereof |
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| CN114478616A (en) * | 2022-01-12 | 2022-05-13 | 湖北江瀚新材料股份有限公司 | 3- (N-imidazole) propyl triethoxysilane and synthesis method thereof |
| CN114478616B (en) * | 2022-01-12 | 2024-05-10 | 湖北江瀚新材料股份有限公司 | 3- (N-imidazole) propyl triethoxysilane and synthesis method thereof |
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