KR20060062438A - Process for preparing aminoalkoxysilanes - Google Patents
Process for preparing aminoalkoxysilanes Download PDFInfo
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- KR20060062438A KR20060062438A KR1020040101281A KR20040101281A KR20060062438A KR 20060062438 A KR20060062438 A KR 20060062438A KR 1020040101281 A KR1020040101281 A KR 1020040101281A KR 20040101281 A KR20040101281 A KR 20040101281A KR 20060062438 A KR20060062438 A KR 20060062438A
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- KR
- South Korea
- Prior art keywords
- ethylenediamine
- aminoethyl
- aminoalkylalkoxysilane
- reaction
- hydrogen chloride
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 34
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 94
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 claims abstract description 60
- 239000011541 reaction mixture Substances 0.000 claims abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 18
- 238000009835 boiling Methods 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000000706 filtrate Substances 0.000 claims abstract description 10
- -1 cyclic tertiary amine Chemical class 0.000 claims abstract description 9
- 238000005191 phase separation Methods 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 238000004064 recycling Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000003039 volatile agent Substances 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000012970 tertiary amine catalyst Substances 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 2
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims description 2
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 claims description 2
- JTWDWVCNOLORBR-UHFFFAOYSA-N 3-chloropropyl-methoxy-dimethylsilane Chemical compound CO[Si](C)(C)CCCCl JTWDWVCNOLORBR-UHFFFAOYSA-N 0.000 claims description 2
- VJPGPCCOXUQRLT-UHFFFAOYSA-N 4-chlorobutyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCCl VJPGPCCOXUQRLT-UHFFFAOYSA-N 0.000 claims description 2
- CKEZAUDJDIPPIB-UHFFFAOYSA-N 4-chlorobutyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCCl CKEZAUDJDIPPIB-UHFFFAOYSA-N 0.000 claims description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 14
- 238000004821 distillation Methods 0.000 abstract description 13
- 238000000926 separation method Methods 0.000 abstract description 11
- 239000000047 product Substances 0.000 abstract description 7
- 238000002845 discoloration Methods 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 4
- 230000001939 inductive effect Effects 0.000 abstract 1
- 229940012017 ethylenediamine Drugs 0.000 description 83
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 57
- 239000007788 liquid Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- HCFPRFJJTHMING-UHFFFAOYSA-N ethane-1,2-diamine;hydron;chloride Chemical compound [Cl-].NCC[NH3+] HCFPRFJJTHMING-UHFFFAOYSA-N 0.000 description 5
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229940087646 methanolamine Drugs 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 2
- ZLAOXGYWRBSWOY-UHFFFAOYSA-N 3-chloropropyl(methoxy)silane Chemical compound CO[SiH2]CCCCl ZLAOXGYWRBSWOY-UHFFFAOYSA-N 0.000 description 2
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- BGOUQWZWCWQOHF-UHFFFAOYSA-N C1CCN=C2CCCN21.C1CCN=C2CCCN21 Chemical compound C1CCN=C2CCCN21.C1CCN=C2CCCN21 BGOUQWZWCWQOHF-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002466 imines Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
본 발명은 γ-[N-(2-아미노에틸)]아미노프로필알킬알콕시실란의 제조방법에 관한 것으로, 상세하게는 a) 에틸렌디아민과 촉매로서 환형삼차아민을 반응기에 가하여 화학식 1로 표시되는 γ-클로로알킬알콕시실란을 적가반응시켜 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란을 50 내지 60℃의 저온에서 합성 제조하는 단계; b) 합성 제조된 반응 혼합물에 에틸렌디아민 · 염화수소 염을 투입한 후 반응혼합물을 정치시켜 2상의 분액으로 형성하는 단계; c) 2상으로 분액 분리된 반응 혼합물 중 에틸렌디아민 · 염화수소 염이 풍부한 하부층을 분리하는 단계; d) 여액인 상부층을 저온 진공 조건에서 에틸렌디아민이 포함된 저비점 휘발성 물질을 제거하고 하기의 화학식 2로 표시되는 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란을 제조하는 단계; e) 상기 c)단계에서 분리된 하부층을 d) 단계와 같이 진공증류하여 에틸렌디아민을 포함한 휘발성 물질을 제거한 후 남은 에틸렌디아민 · 염화수소 염을 상기 b) 단계의 반응 후 혼합액으로 재순환하여 투입하는 하는 단계;를 포함한 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란을 제조하는 방법에 관한 것이다.The present invention relates to a method for preparing γ- [N- (2-aminoethyl)] aminopropylalkylalkoxysilane, specifically, a) γ represented by the formula (1) by adding ethylenediamine and a cyclic tertiary amine as a catalyst to a reactor. Preparing γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane at a low temperature of 50 to 60 ° C. by reacting the chloroalkylalkoxysilane dropwise; b) adding ethylenediamine-hydrogen chloride salt to the synthetically prepared reaction mixture and then leaving the reaction mixture to form a two-phase separation; c) separating the lower layer rich in ethylenediamine-hydrogen chloride salt in the reaction mixture separated into two phases; d) removing the low boiling point volatile containing ethylenediamine from the upper layer of the filtrate under low temperature vacuum and preparing γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane represented by the following Chemical Formula 2; e) vacuum distilling the lower layer separated in step c) as in step d) to remove volatiles including ethylenediamine and recycling the remaining ethylenediamine and hydrogen chloride salts into the mixed solution after the reaction of step b). It relates to a method for producing γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane containing.
본 발명에 따른 제조방법은 γ-클로로알킬알콕시실란를 적가반응 시킴으로서 반응계 내에서 에틸렌디아민과의 몰비를 항상 12배 이상으로 확보되도록 하여 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란 제조 중 부생되는 비스실릴류의 생성량을 억제시키며, 촉매 하 저온에서 반응시켜 목표물을 제조함으로서 생성물의 변색을 방지할 수 있으며, 에틸렌디아민 · 염화수소를 반응 후 혼합액에 첨가하여 쉽게 분액분리를 유도함으로써 별도의 상분리기와 1차 증류공정을 생략한 단순화된 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란 정제공정을 가진 장점이 있다.In the preparation method according to the present invention, the molar ratio with ethylenediamine is always ensured at least 12 times in the reaction system by dropwise addition of γ-chloroalkylalkoxysilane to prepare γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane. It suppresses the production of by-product bissilyl, and reacts at low temperature under the catalyst to prepare the target product, thereby preventing discoloration of the product.Additional separation of ethylenediamine / hydrogen chloride into the mixed solution after inducing easy separation There is an advantage with a simplified γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane purification process that omits the phase separator and the first distillation process.
γ-[N-(2-아미노에틸)]아미노알킬알콕시실란, 아미노알킬알콕시실란γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane, aminoalkylalkoxysilane
Description
γ-[N-(2-아미노에틸)]아미노알킬알콕시실란류는 수지의 충전제면에 접착향상제, 실란카플링제, 프라이머 등으로 널리 사용되고 있으며 유기물과 무기물의 접촉면에서 역할로 접착력을 향상시키거나 변성실리콘으로 제조하여 다양한 화합물의 물성 개선에 많이 사용되고 있는 물질이다. γ-[N-(2-아미노에틸)]아미노알킬알콕시실란은 1몰의 γ-클로로알킬알콕시실란과 2몰의 에틸렌디아민을 적절한 조건하에서 반응시켜 제조하는 공정을 이용하고 있는바, 이 제조과정에서 반응부산물로 에틸렌디아민 · 염화수소가 1몰이 생성되고 비스실릴아미노화합물(Bis-silyl amino Chemicals; 비스실릴류)이 약간 생성된다. 부생된 에틸렌디아민 · 염화수소는 온도나 주위물질에 상관없이 상기 합성조건에서 안정하여 더 이상 반응에 영향을 미치지 않고 생성된 후 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란과 비중차로 인한 층분리로 제거되나, 생성된 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란은 원료로 사용한 γ-클로로알킬알콕시실란 및 에틸렌디아민과 반응하여 비스실릴류가 생성될 수 있으며, 생성된 비스실릴류 부산물은 γ-[N-(2-아미노에틸)]아미노알킬알콕시실 란의 순도 및 수율을 저하시키는 한 원인이 된다. 즉 합성 후 층분리 될 때 이 비스실릴류가 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란이 풍부한 상부층으로 분배되면 정제제거가 용이하지 않기 때문에 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란의 순도를 저하시키고, 반면 에틸렌디아민 · 염화수소가 풍부한 하부층으로 분배되면 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란이 손실되므로 수율이 저하하게 된다. 이와 같이 비스실릴류의 부생은 여러 가지 면에서 바람직하지 않으므로 합성반응시 비스실릴류의 부생을 방지하는 것이 매우 중요하며 이 방향으로 많은 기술의 진보가 이루어져 왔다. γ- [N- (2-aminoethyl)] aminoalkylalkoxysilanes are widely used as adhesive improvers, silane coupling agents, primers, etc. on the filler side of resins. It is made of silicon and is a material that is used for improving the physical properties of various compounds. γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane is prepared by reacting 1 mole of γ-chloroalkylalkoxysilane with 2 moles of ethylenediamine under appropriate conditions. 1 mole of ethylenediamine-hydrogen chloride is produced as a reaction by-product, and bissilyl amino chemicals (bisisylyls) are slightly produced. By-produced ethylenediamine hydrogen chloride is stable under the above synthesis conditions regardless of temperature or surrounding materials and is produced without affecting the reaction anymore. Therefore, the ethylenediamine hydrogen chloride has a specific gravity difference from γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane. The resulting γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane may be reacted with γ-chloroalkylalkoxysilane and ethylenediamine used as raw materials, thereby producing bissilyls. The resulting bissilyl by-products are a cause of lowering the purity and yield of γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane. In other words, when these bissilyls are partitioned into the upper layer rich in γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane when they are separated after synthesis, γ- [N- (2-amino is not easily removed. Lowering the purity of ethyl)] aminoalkylalkoxysilane, while distributing to the lower layer rich in ethylenediamine-hydrogen chloride, decreases the yield since γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane is lost. As such, by-products of bissilyls are not preferable in many respects. Therefore, it is very important to prevent by-products of bissilyls during the synthesis reaction, and many technological advances have been made in this direction.
한편 합성반응과 정제를 70℃ 이상의 고온에서 장시간 노출시켜 수행함으로써 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란이 노란색으로 변색되어 제품의 질이 떨어지게 되어 색을 제거해야 하는 문제를 초래해 왔다.On the other hand, the synthesis reaction and purification are performed by prolonged exposure at a high temperature of 70 ° C. or higher, so that the γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane discolors to yellow and the quality of the product deteriorates. It has been brought about.
미국특허 2,971,864호에서는 γ-클로로알킬알콕시실란과 약간 과잉의 에틸렌디아민을 반응시켜 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란을 제조하는 합성반응에서, 상압에서 환류중(~117℃)인 2.5몰의 에틸렌디아민에 1몰의 γ-클로로알킬알콕시실란을 서서히 첨가하여 합성시킬 때 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란 1몰이 에틸렌디아민 · 염화수소와 함께 생성되었다. 그러나 이 기술에서는 많은 비스실릴류의 생성으로 인해 순도와 수율이 낮은 단점이 있었다.U.S. Patent No. 2,971,864 discloses a synthetic reaction of γ-chloroalkylalkoxysilane with a slight excess of ethylenediamine to produce γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane, under reflux at atmospheric pressure (~ 117). 1 mole of γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane is formed together with ethylenediamine and hydrogen chloride when 1 mole of γ-chloroalkylalkoxysilane is synthesized by slowly adding 2.5 moles of ethylenediamine. It became. However, this technique has the disadvantage of low purity and yield due to the generation of many bissilyls.
또 비스실릴류를 감소시키기 위한 다른 시도로써 일본공고특허 소40-1185호에서는 4내지 6몰의 에틸렌디아민에 1몰의 γ-클로로알킬알콕시실란을 2시간 동안 적가한 후 135℃ 부근에서 3시간 이상 환류 반응시켜 γ-[N-(2-아미노에틸)]아미노 알킬알콕시실란을 합성하였으나, 부생성물인 비스실릴류를 억제하기 부족하였으며 그 결과 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란의 수율은 61%에 불과하였다.In another attempt to reduce bissilyls, Japanese Patent Application Publication No. 40-1185 discloses 1 mole of γ-chloroalkylalkoxysilane added dropwise to 4 to 6 moles of ethylenediamine for 2 hours, followed by 3 hours at 135 ° C. The reaction was conducted under reflux to synthesize γ- [N- (2-aminoethyl)] amino alkylalkoxysilane, but it was insufficient to inhibit bissilyl as a byproduct. As a result, γ- [N- (2-aminoethyl)] amino The yield of alkylalkoxysilane was only 61%.
일본공개특허 소56-104891호에서는 120℃ 부근에서 에틸렌디아민 7 내지 10몰과 γ-클로로알킬알콕시실란 1몰을 1시간 동안 반응시켜 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란 1몰을 합성할 때, 부생성물인 비스실릴류의 생성을 2.8%로 감소시키면서 88% 수율의 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란을 얻었다. 그러나 이 방법은 상당량의 에틸렌디아민을 사용하였으나 반응기에 γ-클로로알킬알콕시실란을 첨가하는 대신에 두 원료를 동시에 반응기에 주입시켜 고온에서 합성 반응시킴으로서 최종 제품이 노란색을 띄고 있을 뿐 아니라 비스실릴류를 충분히 감소시키지 못한 단점이 있었다. 즉 γ-클로로알킬알콕시실란 1몰에 대해 에틸렌디아민 10몰 까지 사용했을 때에도 본 합성조건에서는 비스실릴류를 충분히 제거하지 못하였다. JP-A-56-104891 discloses γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane by reacting 7-10 moles of ethylenediamine and 1 mole of γ-chloroalkylalkoxysilane for 1 hour at around 120 ° C. When synthesizing 1 mole, γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane was obtained in 88% yield while reducing the production of byproduct bissilyl to 2.8%. However, this method uses a considerable amount of ethylenediamine, but instead of adding γ-chloroalkylalkoxysilane to the reactor, two raw materials are injected into the reactor at the same time to synthesize the reaction at high temperature. There was a disadvantage that could not be reduced sufficiently. That is, even when up to 10 mol of ethylenediamine was used per 1 mol of γ-chloroalkylalkoxysilane, bissilyls could not be sufficiently removed under the present synthetic conditions.
미국공고특허 5,446,181호에서는 U자형 관형반응기와 증류장치 및 에틸렌디아민 환류 리사이클 장치를 연결시켜 연속적으로 목표화합물을 제조할 수 있는 장치를 발명하였다. γ-클로로알킬알콕시실란 1몰 당 에틸렌디아민을 12몰 이상을 상호 혼합하여 85 ~ 95℃로 유지되는 U관형 반응기를 통과시키면서 반응시켜 3-[N-(2-아미노에틸)]아미노알킬알콕시실란을 합성한 후 120℃에서 에틸렌디아민을 증류하고 재순환 시키면서 목표물질의 순도와 수율을 각각 99.4%와 91%로 연속식으로 정제할 때 높은 생산성으로 제조할 수 있는 장점과 γ-클로로알킬알콕시실란 몰당 12몰 이상(16.7배)의 에틸렌디아민을 사용하는 효과로 비스실릴류의 생성을 충분히 억제할 수 있는 장점이 있는 것으로 공지하였다. 반면, 제조장치가 다소 복잡하고 높은 반응온도(90℃)와 증류온도(120℃)로 인해 3-[N-(2-아미노에틸)]아미노알킬알콕시실란의 최종 정제 후 노랑색으로 변색되는 단점이 있었다.U.S. Patent No. 5,446,181 invents a device capable of continuously producing a target compound by connecting a U-shaped tubular reactor, a distillation apparatus and an ethylene diamine reflux recycling apparatus. At least 12 moles of ethylene diamine per 1 mole of γ-chloroalkylalkoxysilane are mixed with each other and reacted while passing through a U-tube reactor maintained at 85 to 95 ° C. to give 3- [N- (2-aminoethyl)] aminoalkylalkoxysilane After synthesizing and distilling and recycling ethylenediamine at 120 ° C., the high purity and yield of 99.4% and 91% of the target substance were continuously purified, and the high productivity and molar per γ-chloroalkylalkoxysilane were obtained. It is known that there is an advantage that the production of bissilyl can be sufficiently suppressed by the effect of using 12 mol or more (16.7 times) of ethylenediamine. On the other hand, the manufacturing apparatus is somewhat complicated, and due to the high reaction temperature (90 ° C) and distillation temperature (120 ° C), there is a disadvantage in that yellow color is changed after the final purification of 3- [N- (2-aminoethyl)] aminoalkylalkoxysilane. there was.
한편 미국특허 6,452,033호에서는 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란을 제조함에 있어서 반응원료로서 γ-클로로알킬알콕시실란과 에틸렌디아민뿐만 아니라 이전공정에서 미반응한 에틸렌디아민과 부생한 에틸렌디아민 · 염화수소를 적당량 재순환 시켜 반응에 재사용함으로써 2상(Phase)반응을 시키면서 비스실릴류의 생성을 충분히 억제토록 하는 공정으로서 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란 몰당 12몰의 에틸렌디아민을 사용하여 105℃에서 68분 동안 합성시켰을 때, 99.1%의 전환율과 만족할 정도의 수율을 획득한 것으로 공지되어 있다. 반응 후 층분리를 유도하기 위해 일정량의 에틸렌디아민을 증류제거하고 냉각시켜야 하는 종래공정에서는 단점을 극복하여 미국특허 6,452,033호의 공지공정은 반응 후 냉각 시 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란 층과 에틸렌디아민 · 염화수소층이 분리되어 1차 증류공정을 생략하여 제조공정을 단축시킨 장점이 있으나, 상기 제조방법 역시 반응규모가 커짐에 따라 2상간 긴밀한 접촉부족으로 반응속도가 저하되고 불순물이 생성되며, 반응온도(105℃)가 높아 제조된 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란이 노란색으로 변색되는 단점이 있었다.On the other hand, US Patent No. 6,452,033 discloses not only γ-chloroalkylalkoxysilane and ethylenediamine as reaction materials in the preparation of γ- [N- (2-aminoethyl)] aminoalkylalkoxysilanes, but also unreacted ethylenediamine and by-products in the previous process. Recycling an appropriate amount of ethylenediamine and hydrogen chloride and reusing it in the reaction to allow biphasic reaction to sufficiently suppress the production of bissilyls, per mole of γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane. When synthesized at 105 ° C. for 68 minutes using 12 moles of ethylenediamine, it is known that a conversion of 99.1% and a satisfactory yield are obtained. In the conventional process of distilling off and cooling a certain amount of ethylenediamine to induce layer separation after the reaction, the disadvantages of US Pat. No. 6,452,033 are known and the known process of γ- [N- (2-aminoethyl)] amino Although the alkylalkoxysilane layer and the ethylenediamine-hydrogen chloride layer are separated, the first distillation step is omitted, but the manufacturing process is shortened, but as the reaction scale increases, the reaction rate decreases due to the lack of intimate contact between two phases. Impurities are generated, and the reaction temperature (105 ° C.) is high, and thus the γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane has a disadvantage of discoloring yellow.
따라서 본 발명의 목적은 γ-클로로알킬알콕시실란를 적가반응 시킴으로서 반응계 내에서 에틸렌디아민과의 몰비를 항상 12배 이상으로 확보되도록 하여 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란 제조 중 부생되는 비스실릴류의 생성량을 억제시켜 생성물의 순도와 수율이 높은 제조방법을 제공하는 것이며, 또한 촉매 하 저온에서 반응시켜 목표물을 제조함으로서 생성물의 변색을 방지할 수 있도록 고품질의 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란류를 제조하는 방법을 제공하는 것을 발명의 목적으로 한다. Accordingly, an object of the present invention is to make a molar ratio with ethylenediamine at least 12 times in the reaction system by dropwise addition of γ-chloroalkylalkoxysilane, thereby preparing γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane. It is to provide a production method of high purity and yield of the product by suppressing the amount of by-product bissilyl production, and also to produce a target by reacting at low temperature under a catalyst to produce a high quality γ- [N- It is an object of the invention to provide a method for producing (2-aminoethyl)] aminoalkylalkoxysilanes.
본 발명의 또 다른 목적은 에틸렌디아민 · 염화수소를 반응 후 액에 첨가하여 쉽게 분액분리를 유도함으로서 1차 증류공정을 생략한 단순한 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란 정제공정을 제공하는 것이다.
Still another object of the present invention is a simple γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane refining process that omits the first distillation step by adding ethylenediamine hydrogen chloride to the liquid after reaction to easily separate the separation. To provide.
본 발명은 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란의 효율적인 제조방법에 관한 것으로, 상세하게는 원료로 γ-클로로알킬알콕시실란과 에틸렌디아민을 반응시켜 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란을 합성함에 있어, a) 에틸렌디아민과 촉매로서 환형삼차아민을 반응기에 가하여 화학식 1로 표시되는 γ-클로로알킬알콕시실란을 적가반응시켜 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란을 50 내지 60℃의 저온에서 합성 제조하는 단계; b) 합성 제조된 반응 혼합물에 에틸렌디아민 · 염화수소 염을 투입한 후 반응혼합물을 정치시켜 2상의 분액으로 형성하는 단계; c) 2상으로 분액 분리된 반응 혼합물 중 에틸렌디아민 · 염화수소 염이 풍부한 하부층을 분리하는 단계; d) 여액인 상부층을 저온 진공 조건에서 에틸렌디 아민이 포함된 저비점 휘발성 물질을 제거하고 하기의 화학식 2로 표시되는 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란을 제조하는 단계; e) 상기 c)단계에서 분리된 하부층을 d) 단계와 같이 진공증류하여 에틸렌디아민을 포함한 휘발성 물질을 제거한 후 남은 에틸렌디아민 · 염화수소 염을 상기 b) 단계의 반응 후 혼합액으로 재순환하여 투입하는 하는 단계;를 포함하는 것을 특징으로 한다.The present invention relates to an efficient method for preparing γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane, and specifically, γ- [N- (by reacting γ-chloroalkylalkoxysilane with ethylenediamine as a raw material. In the synthesis of 2-aminoethyl)] aminoalkylalkoxysilane, a) ethylenediamine and a cyclic tertiary amine as a catalyst are added to the reactor and the γ-chloroalkylalkoxysilane represented by the formula (1) is added dropwise to react γ- [N- ( 2-aminoethyl)] synthesizing the aminoalkylalkoxysilane at a low temperature of 50-60 ° C .; b) adding ethylenediamine-hydrogen chloride salt to the synthetically prepared reaction mixture and then leaving the reaction mixture to form a two-phase separation; c) separating the lower layer rich in ethylenediamine-hydrogen chloride salt in the reaction mixture separated into two phases; d) removing the low boiling point volatile material including ethylenediamine under low temperature vacuum conditions of the filtrate upper layer and preparing γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane represented by the following Chemical Formula 2; e) vacuum distilling the lower layer separated in step c) as in step d) to remove volatiles including ethylenediamine and recycling the remaining ethylenediamine and hydrogen chloride salts into the mixed solution after the reaction of step b). It characterized by including.
에틸렌디아민과 환형삼차아민 촉매를 반응기에 각각 넣어 45 내지 50℃로 가열하고 γ-클로로알킬알콕시실란을 적가하여 반응시킬 때, 촉매를 사용하여 저온에서 반응을 활성화시키면서도 변색이 미미하게 하고 적가반응을 통해 부생물인 비스실릴류의 생성을 충분히 억제하여 생성물의 순도와 수율이 높은 합성공정의 발명과, 미국특허 6,452,033호에서 반응원료로 γ-클로로알킬알콕시실란과 에틸렌디아민 이외에 에틸렌디아민 · 염화수소 염이 풍부한 2상 분리액의 하부층의 일부를 반응물에 2상으로 분액을 위해 사용하였으나 에틸렌디아민 · 염화수소 염과 함께 상당량의 에틸렌디아민과 메탄올이 함유되어 있어, 메탄올이 축적시 원료로 투입되는 γ-클로로알킬알콕시실란과 에틸렌디아민과 에틸렌디아민 · 염화수소 염의 비율을 잘 조정하기 어려운 단점이 있었으나, 본 발명에서는 2상으로 층분리를 위해 에틸렌디아민 · 염화수소 염만을 재순환 하므로 원료물질의 공급시 단순하게 된다. 또한 반응 후 혼합액이 있는 반응기에 에틸렌디아민 · 염화수소 적당량을 투입하여 2액으로 상분리를 유도함으로써 에틸렌디아민을 증류조작으로 제거하여 층분리를 유도하는 기존 1차 증류공정을 생략할 수 있는 장점과 또한 반응기에서 층분리를 수행함으로써 사용한 상분리기(phase separator)를 생략하여 제조공정을 단 순화한 효율적인 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란을 제조하는 방법이다.When the ethylenediamine and the cyclic tertiary amine catalyst were put in a reactor and heated to 45 to 50 ° C., and reacted by dropwise addition of γ-chloroalkylalkoxysilane, the catalyst was used to activate the reaction at low temperature while the discoloration was minimal and the dropwise reaction was carried out. Through the invention of the synthesis process of high purity and yield of the product by sufficiently inhibiting the formation of by-product bissilyl, and in addition to the γ-chloroalkylalkoxysilane and ethylenediamine in the US Patent 6,452,033, A part of the lower layer of the rich two-phase separation liquid was used to separate the reactants in two phases, but ethylene-diamine and hydrogen chloride salts contained a considerable amount of ethylenediamine and methanol, and thus γ-chloroalkyl, which was added as a raw material when methanol was accumulated, Difficult to adjust the ratio of alkoxysilane, ethylenediamine, ethylenediamine, and hydrogen chloride salts well But a disadvantage, since in the present invention, only the recycle ethylene diamine hydrogen chloride salt, for phase separation into two phases is simplified for supply of the raw material. In addition, by adding an appropriate amount of ethylenediamine and hydrogen chloride to the reactor with a mixed solution after the reaction to induce phase separation with two liquids, the existing primary distillation step of eliminating ethylenediamine by distillation operation can be omitted and also the reactor This method is to prepare an efficient γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane which simplifies the production process by omitting the phase separator used by performing the layer separation in.
상기 물질의 합성에 반응촉매로서 환형삼차아민계 화합물을 사용하여 낮은 반응온도에서도 충분한 반응속도를 얻을 수 있고, 에틸렌디아민에 γ-클로로알킬알콕시실란을 적가시킴으로서 γ-클로로알킬알콕시실란에 대한 에틸렌디아민의 몰비를 12배 이상 확보되도록 하여 부생되는 비스실릴류의 생성을 억제하고 상기 목적 화합물의 합성 순도와 제조 수율을 최대화할 수 있을 뿐 아니라 상기 저온에서 합성물을 제조함으로써 노란색으로 변색을 방지할 수 있었다. 반응 후 반응혼합액이 가장 효과적으로 2상으로 분리될 수 있도록 반응 혼합액에 에틸렌디아민 · 염화수소를 가함으로서 2상으로 분리하고, 하부의 에틸렌디아민 · 염화수소가 풍부한 층을 상이 분리된 반응기로부터 제거한 후, γ-[N-(2-아미노에틸)]아미노알킬알콕시실란이 풍부한 층을 증류장치로 옮겨 메탄올과 에틸렌디아민 같은 저비점분을 증류시켜 제거하면 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란을 획득할 수 있으며, 하층부의 에틸렌디아민 · 염화수소가 풍부한 액층도 증류하여 메탄올과 에틸렌디아민 같은 저비점분을 분리시켜 에틸렌디아민 · 염화수소를 수득하고 일부를 반응에 재사용 하는 효율적이고 경제적인 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란의 제조방법에 관한 발명이다.By using a cyclic tertiary amine compound as a reaction catalyst in the synthesis of the material, a sufficient reaction rate can be obtained even at a low reaction temperature, and ethylenediamine to γ-chloroalkylalkoxysilane by dropwise addition of γ-chloroalkylalkoxysilane to ethylenediamine. The molar ratio of was ensured more than 12 times to suppress the production of by-product bissilyl and maximize the synthesis purity and production yield of the target compound, as well as to prevent the discoloration to yellow by preparing the composite at a low temperature . After the reaction, the reaction mixture was separated into two phases by adding ethylenediamine and hydrogen chloride to the reaction mixture so that the reaction mixture could be separated into two phases most effectively.The lower ethylenediamine-hydrogen chloride-rich layer was removed from the phase separated reactor, and then γ- A layer rich in [N- (2-aminoethyl)] aminoalkylalkoxysilane is transferred to a distillation unit and distilled off a low boiling point such as methanol and ethylenediamine to remove γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane The lower layer of ethylenediamine-hydrogen chloride rich in distillation can be distilled to separate low boiling points such as methanol and ethylenediamine to obtain ethylenediamine-hydrogen chloride and reuse some of them in the reaction. The invention relates to a method for producing (2-aminoethyl)] aminoalkylalkoxysilane.
이하 본 발명을 예를 들어 상세히 설명한다.Hereinafter, the present invention will be described in detail by way of example.
본 발명에 따른 제조방법은 하기의 단계를 거친다.The manufacturing method according to the present invention goes through the following steps.
a) 에틸렌디아민과 촉매로서 환형삼차아민을 반응기에 가하여 화학식 1로 표 시되는 γ-클로로알킬알콕시실란을 적가반응시켜 화학식 2로 표시되는 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란을 합성 제조하는 단계.a) Ethylenediamine and a cyclic tertiary amine as a catalyst are added to the reactor, and the γ-chloroalkylalkoxysilane represented by the formula (1) is added dropwise to react the γ- [N- (2-aminoethyl)] aminoalkylalkoxy represented by the formula (2). Synthetically preparing the silanes.
[화학식 1][Formula 1]
Cl(CH2)aSi(R1)3-n(OR2)n Cl (CH 2 ) a Si (R 1 ) 3-n (OR 2 ) n
[화학식 2][Formula 2]
NH2CH2CH2NH(CH2)aSi(R1)3-n(OR 2)n NH 2 CH 2 CH 2 NH (CH 2 ) a Si (R 1 ) 3-n (OR 2 ) n
[상기 화학식 1 및 화학식 2에서 a는 3 또는 4인 정수이고, n은 1 내지 3인 정수이며, R1과 R2는 동일하거나 상이할 수 있으며 메틸기 혹은 에틸기를 나타낸다.][In Formula 1 and Formula 2, a is an integer of 3 or 4, n is an integer of 1 to 3, and R1 and R2 may be the same or different and represent a methyl group or an ethyl group.]
b) 제조된 반응 혼합물에 에틸렌디아민 · 염화수소 염을 가한 후 반응혼합물을 정치시켜 2상의 분액으로 형성하는 단계.b) adding ethylenediamine-hydrogen chloride salt to the prepared reaction mixture, and then leaving the reaction mixture to form a two-phase separation.
c) 2상의 분액으로 분리된 반응 혼합물 중 에틸렌디아민 · 염화수소 염이 풍부한 하부층을 분리하는 단계.c) separating the lower layer rich in ethylenediamine-hydrogen chloride salt in the reaction mixture separated into two phase aliquots.
d) 여액인 상부층을 저온 진공 조건에서 에틸렌디아민이 포함된 휘발성 물질을 제거하고 하기의 화학식 2로 표시되는 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란을 제조하는 단계.d) removing the volatiles including ethylenediamine in the upper layer of the filtrate at low temperature vacuum to prepare a γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane represented by the following formula (2).
e) 상기 c)단계에서 분리된 하부층을 d) 단계와 같이 진공증류하여 에틸렌디아민을 포함한 휘발성 물질을 제거한 후 남은 에틸렌디아민 · 염화수소 염을 상기 b) 단계의 반응 후 혼합액으로 재순환하여 투입하는 하는 단계를 포함한다.e) vacuum distilling the lower layer separated in step c) as in step d) to remove volatiles including ethylenediamine and recycling the remaining ethylenediamine and hydrogen chloride salts into the mixed solution after the reaction of step b). It includes.
본 발명은 에틸렌디아민과 환형삼차아민 촉매를 각각 반응기에 넣고 화학식 1로 표시되는 γ-클로로알킬알콕시실란을 적가하여 반응시켜 화학식 2로 표시되는 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란을 제조하는 것을 특징으로 하는 제조방법이다.In the present invention, an ethylenediamine and a cyclic tertiary amine catalyst are respectively added to a reactor, and γ- [N- (2-aminoethyl)] aminoalkyl represented by Formula 2 is reacted by dropwise addition of γ-chloroalkylalkoxysilane represented by Formula 1. It is a manufacturing method characterized by manufacturing an alkoxysilane.
[화학식 1][Formula 1]
Cl(CH2)aSi(R1)3-n(OR2)n Cl (CH 2 ) a Si (R 1 ) 3-n (OR 2 ) n
[화학식 2][Formula 2]
NH2CH2CH2NH(CH2)aSi(R1)3-n(OR 2)n NH 2 CH 2 CH 2 NH (CH 2 ) a Si (R 1 ) 3-n (OR 2 ) n
[상기 화학식 1 및 화학식 2에서 a는 3 또는 4인 정수이고, n은 1 내지 3인 정수이며, R1과 R2는 동일하거나 상이할 수 있으며 메틸기 혹은 에틸기를 나타낸다.][In Formula 1 and Formula 2, a is an integer of 3 or 4, n is an integer of 1 to 3, and R1 and R2 may be the same or different and represent a methyl group or an ethyl group.]
본 발명에서 사용하는 상기 화학식 1로 표시되는 γ-클로로알킬알콕시실란 화합물의 구체적인 예로는 3-클로로프로필트리메톡시실란, 3-클로로프로필트리에톡시실란, 4-클로로부틸트리메톡시실란, 4-클로로부틸트리에톡시실란, 3-클로로프로 필메틸디메톡시실란, 3-클로로프로필디메틸메톡시실란 등이 있으며, 상기 예로 제시된 화합물들이 본 발명의 범위를 한정하는 것은 아니다.Specific examples of the γ-chloroalkylalkoxysilane compound represented by Formula 1 used in the present invention include 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 4-chlorobutyltrimethoxysilane, 4 -Chlorobutyltriethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyldimethylmethoxysilane, and the like, and the compounds given above are not intended to limit the scope of the present invention.
또한 상기 화학식 2로 표시되는 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란 화합물은 상기 화학식 1의 화합물 1 분자와 에틸렌디아민 1분자가 반응하여 상응하는 생성물이 된 것으로서 구체적으로는 3-[N-(2-아미노에틸)]아미노프로필트리메톡시실란, 3-[N-(2-아미노에틸)]아미노프로필트리에톡시실란, 4-[N-(2-아미노에틸)]아미노부틸트리메톡시실란, 4-[N-(2-아미노에틸)]아미노부틸트리에톡시실란, 3-[N-(2-아미노에틸)]아미노프로필메틸디메톡시실란, 3-[N-(2-아미노에틸)]아미노프로필디메틸메톡시실란 등이 있으며, 이들 예가 본 발명을 한정하는 것은 아니다.In addition, the γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane compound represented by Chemical Formula 2 is reacted with one molecule of Compound 1 of Chemical Formula 1 and one molecule of ethylenediamine, and specifically, 3 -[N- (2-aminoethyl)] aminopropyltrimethoxysilane, 3- [N- (2-aminoethyl)] aminopropyltriethoxysilane, 4- [N- (2-aminoethyl)] amino Butyltrimethoxysilane, 4- [N- (2-aminoethyl)] aminobutyltriethoxysilane, 3- [N- (2-aminoethyl)] aminopropylmethyldimethoxysilane, 3- [N- ( 2-aminoethyl)] aminopropyldimethylmethoxysilane, and these examples do not limit the present invention.
앞서 언급한 바와 같이 γ-클로로알킬알콕시실란에 대한 에틸렌디아민의 몰비가 12배 이상 확보되어야만 비스실릴류의 생성이 억제되는 것으로 기존 기술들이 확인한바 종래의 제조방법에서 과도한 에틸렌아민을 사용할 수밖에 없었으나, 본 발명에 따른 제조방법에서는 원료를 동시에 반응기에 주입하는 대신 에틸렌디아민에 γ-클로로알킬알콕시실란을 적가시키는 방법을 채택함으로 인하여 종래기술보다 적은 량의 에틸렌디아민을 사용하면서도 반응계 내에서의 반응 순간 γ-클로로알킬알콕시실란에 대한 에틸렌디아민의 몰비가 12배 이상 지속적으로 확보되도록 하여 부생되는 비스실릴류의 생성을 충분히 억제할 수 있도록 하였다.As mentioned above, when the molar ratio of ethylenediamine to γ-chloroalkylalkoxysilane is more than 12 times secured, bissilyl production is inhibited. Existing techniques have confirmed that excessive ethyleneamine was used in the conventional manufacturing method. In the production method according to the present invention, instead of simultaneously injecting the raw materials into the reactor, γ-chloroalkylalkoxysilane is added dropwise to ethylenediamine, thereby using a smaller amount of ethylenediamine than the prior art, The molar ratio of ethylenediamine to γ-chloroalkylalkoxysilane was continuously ensured at least 12 times to sufficiently suppress the production of by-product bissilyls.
본 발명에 따른 제조방법에서 γ-클로로알킬알콕시실란 1몰 당 투입되는 에틸렌디아민은 6몰 내지 12몰이 적당하며, 특히 8몰 내지 10몰이 바람직하다. 에틸 렌디아민의 투입량이 6몰 보다 낮을 경우 부생 비스실릴류의 생성량이 증가되며, 12몰 보다 높을 경우에는 비스실릴류의 생성량이 미미한 반면 과잉 사용한 에틸렌디아민의 회수 비용 증가와 반응기의 용량이 증가하여 제조 생산성이 저하하게 된다. In the production method according to the present invention, 6 mol to 12 mol of ethylene diamine added per mol of γ-chloroalkylalkoxysilane is preferable, and 8 mol to 10 mol are particularly preferable. When the input amount of ethylenediamine is lower than 6 mol, the by-product bissilyl production is increased. When it is higher than 12 mol, bissilyl production is insignificant. Manufacturing productivity will fall.
에틸렌디아민 · 염화수소 염의 투입량은 γ-클로로알킬알콕시실란 1몰 당 1내지 6몰이 적절하고 특히 2.5 내지 5몰이 더 적절하며, 에틸렌디아민 · 염화수소 염이 지나치게 많을 경우 반응계 내의 점도가 상승 하는 등의 문제가 발생하며, 1몰 보다 적을 경우 반응생성물이 효과적으로 2상으로 분액되지 않는 문제가 발생한다.The amount of ethylenediamine / hydrochloride salt added is preferably 1 to 6 moles per 1 mole of γ-chloroalkylalkoxysilane, and particularly 2.5 to 5 moles is more appropriate. When too much ethylenediamine / hydrochloride salt is present, there is a problem such as an increase in viscosity in the reaction system. If less than 1 mole, the reaction product is not effectively separated into two phases occurs.
한편 본 발명에 따른 제조방법에서는 50 내지 60℃의 낮은 온도 조건 하에서도 충분한 반응활성도를 확보하기 위해 반응촉매로서 환형삼차아민류를 사용하였다. 환형삼차이민류로는 1,8-디아자비씨클로[5.4.0]언덱-7-엔 (1,8-diazabi cyclo[5.4.0]undec-7-ene), 1,4-디아자비씨클로[2.2.2]옥탄 (1,4-diazabicyclo [2.2.2]octane), 1,5-디아자비씨클로[4.3.0]-논-5-엔 (1,5-diazabicyclo[4.3.0]- non-5-ene)을 예시할 수 있으며, 특히 1,8-디아자비씨클로[5.4.0]언덱-7-엔이 바람직하나, 상기 예가 본 발명의 범위를 한정하는 것은 아니다. 상기 촉매의 사용량은 3-클로로알콕시실란 기준으로 10 내지 20000 ppm를 사용하는 것이 바람직하다.Meanwhile, in the production method according to the present invention, cyclic tertiary amines were used as reaction catalysts to ensure sufficient reaction activity even under low temperature conditions of 50 to 60 ° C. Cyclic tertiary imines include 1,8-diazabicyclo [5.4.0] undec-7-ene and 1,4-diazabicyclo. 2.2.2] octane (1,4-diazabicyclo [2.2.2] octane), 1,5-diazabicyclo [4.3.0] -non-5-ene (1,5-diazabicyclo [4.3.0] -non -5-ene) may be exemplified, in particular 1,8-diazabicyclo [5.4.0] undec-7-ene, although the above examples do not limit the scope of the invention. The amount of the catalyst used is preferably 10 to 20000 ppm based on 3-chloroalkoxysilane.
반응 중 발생하는 반응열은 외부 냉각수로 냉각시킴으로써 반응온도와 반응속도를 조절하며, 반응은 개방형 반응기를 사용하여 상압조건하에서 수행하여 반응 중 발생하는 메탄올과 폐 가스류를 제거한다.The reaction heat generated during the reaction is cooled by external cooling water to control the reaction temperature and reaction rate. The reaction is performed under atmospheric pressure using an open reactor to remove methanol and waste gas streams generated during the reaction.
한편 종래의 대부분의 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란의 제조는 85 내지 120℃의 반응온도에서도 1시간 내지 3시간 동안의 반응시간을 필요로 하였으나, 본 발명에서 채용된 상기의 환형삼차아민류 촉매는 에틸렌디아민과 3-클로로알킬알콕시실란의 염소 치환반응 시 염소이온이 쉽게 이탈되도록 활성화 시키는 작용을 하여 반응온도가 비교적 낮은 조건에서도 반응속도가 빠르게 유지되는 작용을 하므로 50℃ 내지 60℃의 저온의 조건에서도 무색의 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란을 효과적으로 제조할 수 있다. On the other hand, most of the conventional preparation of γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane required a reaction time of 1 to 3 hours even at a reaction temperature of 85 to 120 ° C, but it is employed in the present invention. The above cyclic tertiary amine catalysts have a function of activating the chlorine ion to be easily released during the chlorine substitution reaction of ethylenediamine and 3-chloroalkylalkoxysilane, so that the reaction rate is rapidly maintained even at a relatively low reaction temperature. Colorless gamma-[N- (2-aminoethyl)] aminoalkylalkoxysilane can be manufactured effectively also in the low temperature conditions of ° C-60 degreeC.
그러나 반응온도가 50℃ 이하이면 반응속도가 느려 제조 생산성이 저하되고, 60℃ 이상이면 최종 생성물의 아민기가 일부 산화됨으로 인하여 노란색으로 변색되어 더 정제가 필요한 단점이 있다. However, if the reaction temperature is 50 ℃ or less, the reaction rate is slow, the production productivity is lowered, and if the reaction temperature is 60 ℃ or more, the amine group of the final product is discolored yellow due to some oxidation, there is a disadvantage that requires further purification.
상기 반응온도에서 1시간 동안 적가시키고 10분간 숙성시켰을 때 γ-클로로알킬알콕시실란의 전환율은 92% 이었으며, 이는 적가 시의 반응속도가 매우 높음을 보여 주는 것이며, 이는 상기의 환형삼차아민류 촉매를 사용함으로서 비교적 낮은 반응온도에서도 반응속도가 빨라지는 것에 기인하는 것이며, 이는 에틸렌디아민과 촉매의 혼합물에 γ-클로로알킬알콕시실란을 적가함과 동시에 반응이 진행되도록 함으로서 반응계 내에 미반응된 γ-클로로알킬알콕시실란의 잔류 농도가 작아지도록 하여 반응이 진행되는 동안 반응계 내의 에틸렌디아민 과잉도가 지속적으로 12몰비 이상으로 유지시키고 이는 비스실릴류의 생성을 충분히 억제하는 데 기여하게 된다.When the reaction temperature was added dropwise for 1 hour and aged for 10 minutes, the conversion rate of γ-chloroalkylalkoxysilane was 92%, which shows that the reaction rate was very high at the time of addition, and the cyclic tertiary amine catalyst was used. This is because the reaction rate is accelerated even at a relatively low reaction temperature, and the reaction proceeds simultaneously with the addition of γ-chloroalkylalkoxysilane to the mixture of ethylenediamine and the catalyst, thereby allowing unreacted γ-chloroalkylalkoxy in the reaction system. The residual concentration of silane is made small so that the excess of ethylenediamine in the reaction system is continuously maintained at 12 molar ratio or more during the reaction, which contributes to sufficiently suppressing the production of bissilyls.
화학식 1로 표시되는 γ-클로로알킬알콕시실란을 적가반응시켜 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란을 제조하고 에틸렌디아민 · 염화수소 염을 가하여 형성된 반응 혼합물은 2상을 유지하게 되며, 2상의 분액 중 하부층은 에틸렌디아민 · 염화수소 염이 풍부한 층이며, 상부층은 반응생성물인 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란이 풍부한 층으로 형성된다. The γ-chloroalkylalkoxysilane represented by the formula (1) was added dropwise to prepare γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane and the reaction mixture formed by adding ethylenediamine / hydrogen chloride salt to maintain two phases. The lower layer of the two-phase separation is a layer rich in ethylenediamine hydrogen chloride salt, and the upper layer is formed of a layer rich in γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane, which is a reaction product.
그러나 통상 2상의 반응혼합물은 효율적으로 분리되지 아니하여 상층액과 하층액의 분액이 효과적으로 이루어지지 않으나, 본 발명자들은 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란, 에틸렌디아민 및 에틸렌디아민 · 염화수소 염의 특정 몰비에서 분액이 잘 이루어진다는 점을 확인하고 a) 단계에서 제조된 반응혼합물에 에틸렌디아민 · 염화수소 염을 가하여 몰비를 조정함으로서 2상의 분액이 효율적으로 분리할 수 있도록 하였다. 반응 혼합물이 분액 되기에 바람직한 반응물의 비율은 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란 : 에틸렌디아민 : 에틸렌디아민 · 염화수소의 몰비율이 1 : 6 내지 12 : 1 내지 6이다.However, two-phase reaction mixtures are not effectively separated, so the separation between the supernatant and the lower layer is not effective. However, the present inventors have found that γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane, ethylenediamine and ethylene It was confirmed that the separation was well performed at a specific molar ratio of diamine and hydrogen chloride salts, and the separation ratio of the two phases was efficiently separated by adjusting the molar ratio by adding ethylenediamine and hydrogen chloride salts to the reaction mixture prepared in step a). A preferable reactant ratio for separating the reaction mixture is a molar ratio of γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane: ethylenediamine: ethylenediamine and hydrogen chloride of 1: 6 to 12: 1 to 6.
상기 단계에서 제조된 반응 혼합물은 방치와 동시에 2층으로 분리되며 미세입자까지 완전히 분리가 유도되도록 하기 위해 40℃ 대로 내리면서 30분 이상 방치한 후, 상부층은 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란이 풍부한 층으로 에틸렌디아민과 소량의 메탄올이 함유되어 있어 50℃ 에서 70℃ 까지 승온과 함께 동시에 100torr에서 10torr 이하로 진공도를 낮추면서 에틸렌디아민과 메탄올을 회수하며, 메탄올을 제거한 에틸렌디아민은 반응물로서 재사용 하게 된다. 이때 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란이 포함된 상부층을 70℃ 이상으로 승온하면 노란색으로 변색하기 시작하므로 더 이상의 승온 대신 진공도를 낮추는 것이 바람직하다. The reaction mixture prepared in this step is separated into two layers at the same time as it is left and left for 30 minutes at 40 ° C. in order to completely induce separation to fine particles, and then the upper layer is γ- [N- (2-aminoethyl )] Aqueous layer rich in aminoalkylalkoxysilane, containing ethylenediamine and a small amount of methanol, recovering ethylenediamine and methanol while lowering the vacuum from 100torr to 10torr while increasing the temperature from 50 ℃ to 70 ℃. Ethylenediamine is reused as reactant. In this case, when the upper layer including γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane is heated to 70 ° C. or more, it starts to discolor yellow. Therefore, it is preferable to lower the vacuum degree instead of raising the temperature further.
반면 하부층은 에틸렌디아민 · 염화수소 염이 풍부한 층으로서 일부 함유되어 있는 에틸렌디아민과 메탄올과 이 70℃에서 100torr 에서 30torr로 진공도를 낮추어 에틸렌디아민과 메탄올을 회수한 후 메탄올이 제거된 에틸렌디아민은 원료로 재사용하고, 진공 증류 후 여액인 에틸렌디아민 · 염화수소 염의 일부는 반응혼합액의 2상을 유도하기 위해 재순환하여 사용 한다. 종래발명에서는 층분리 후 하부층의 에틸렌디아민과 메탄올 등 저비점분이 풍부한 혼합물을 그대로 반응계에 투입하여 2상을 유도하는데 사용하였으나 본 발명에서는 혼합물을 증류하여 메탄올과 저비점분을 제거시킴으로서 반응계내의 메탄올의 축적을 최소화 시켜 목적물 내 메탄올 함량을 최소화시킬 수 있다. On the other hand, the lower layer is a layer rich in ethylenediamine and hydrogen chloride salt, which partially contains ethylenediamine and methanol, and recovers ethylenediamine and methanol by reducing the vacuum degree from 100torr to 30torr at 70 ° C, and ethylenediamine without methanol is reused as a raw material. After vacuum distillation, a portion of the filtrate ethylenediamine hydrogen chloride salt is recycled to induce the two phases of the reaction mixture. In the present invention, after mixing the layers, a mixture rich in low boiling point such as ethylenediamine and methanol is added to the reaction system as it is and used to induce two phases. However, in the present invention, the mixture is distilled to remove methanol and low boiling point to accumulate methanol in the reaction system. It can be minimized to minimize the methanol content in the target.
한편 저비점분을 제거한 에틸렌디아민 · 염화수소 염에는 소량의 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란과 함께 고비점분이 포함될 수 있으며 반응 혼합물로 재순환이 거듭될수록 반응계 내에 축적될 수 있으므로 10회 정도 재순환 후에는 에틸렌디아민 · 염화수소 염을 에틸렌디아민으로 세척, 정제하여 고비점분을 제거한 후 재사용한다. 기존의 발명기술에서는 에틸렌디아민 · 염화수소 염과 함께 에틸렌디아민과 메탄올 등 저비점이 포함된 액과 고비점분 등 반응에 불필요한 불순물들을 정제하지 않고 재순환시켜 사용하였으므로 반응계에 축적될 가능성을 배제하고 있지 않았다. On the other hand, the low boiling point ethylenediamine and hydrogen chloride salts may contain a high boiling point together with a small amount of γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane and may accumulate in the reaction system as the recycle to the reaction mixture is repeated. After about 10 recycles, ethylenediamine and hydrogen chloride salts are washed and purified with ethylenediamine to remove high boiling point and reused. In the existing invention technology, ethylenediamine and hydrogen chloride salts were recycled without refining impurities containing low boiling point such as ethylenediamine and methanol and unnecessary impurities such as high boiling point, so that the possibility of accumulation in the reaction system was not excluded.
본 발명에 따른 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란의 제조방법을 상세하게 기술하면, 온도계 부착구, 환류 냉각기 부착구, 질소 투입구 및 반응물 투입구가 있는 4구 둥근 플라스크 반응기에 에틸렌디아민과 환형삼차아민계 촉매를 각각 넣고 질소로 분위기를 바꾼 후 교반기로 잘 교반시키면서 반응온도를 50℃로 상승시켜 유지시키고 γ-클로로알킬알콕시실란을 1시간 적가시키면서 반응시킨다. 반응 중 발생하는 발열로 인해 반응온도가 초기 50℃에서 시작하여 60℃ 부근까지 상승한다. 적가 후 1시간 동안 숙성시켜 반응을 완결시킨 후, 에틸렌디아민 · 염화수소 염을 투입하고 교반을 멈추고 냉각시키면서 방치하면 바로 두층으로 분액되며 미세입자 까지 완전히 분리하기 위해 40℃ 내지 50℃ 정도가 될 때 까지 냉각시킨다. 반응기 하부의 에틸렌디아민 · 염화수소가 풍부한 액층은 불투명한 우유빛의 끈적끈적한 점성액으로 반응기로 부터 제거하고, γ-[N-(2-아미노에틸)]아미노알킬알콕시실란이 풍부한 상부층은 무색 투명한 비점성액으로 증류장치에 옮기고 60 ~ 70℃ 온도와 1~100 torr 진공도 하에서 에틸렌디아민과 알코올 같은 저비점분을 제거하면 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란이 여액으로 획득되며, 핵자기 공명분석기와 가스크로마토그래피 분석기를 사용하여 해당물질임을 확인하였다.A method for producing γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane according to the present invention is described in detail. A four-necked round-necked flask reactor with thermometer inlet, reflux cooler inlet, nitrogen inlet and reactant inlet Ethylenediamine and a cyclic tertiary amine catalyst were respectively added to the mixture, and the atmosphere was changed to nitrogen. The reaction temperature was raised to 50 ° C. while stirring well with a stirrer, and the reaction was added dropwise with γ-chloroalkylalkoxysilane for 1 hour. Due to the exotherm generated during the reaction, the reaction temperature starts at an initial 50 ° C and rises to around 60 ° C. After completion of the dropwise addition, the reaction was completed for 1 hour to complete the reaction. Then, ethylenediamine / hydrogen chloride was added thereto, and the mixture was left to stand while stopping stirring and cooled until the solution was separated into two layers, until it reached 40 ° C. to 50 ° C. to completely separate the fine particles. Cool. The ethylenediamine-hydrogen chloride-rich liquid layer at the bottom of the reactor is removed from the reactor with an opaque milky sticky viscous liquid.The upper layer rich in γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane is colorless and transparent. Transfer the viscous liquid to the distillation unit and remove the low boiling point such as ethylenediamine and alcohol under the temperature of 60 ~ 70 ℃ and 1 ~ 100 torr vacuum degree to obtain γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane as filtrate. In addition, nuclear magnetic resonance and gas chromatography analyzers were used to identify the substance.
본 발명의 기술을 다음 실시예를 통해서 더 상세하게 기술하지만, 본 발명이 이에 한정되는 것은 아니다.Although the technique of the present invention is described in more detail through the following examples, the present invention is not limited thereto.
[실시예 1]Example 1
온도계, 환류냉각기, 질소투입구 및 적가 깔대기가 부착된 1ℓ 4구 둥근 플라스크 반응기를 잘 건조시켜 교반과 가열이 가능한 가열판(hot plate)위에 설치하 고 질소 분위기로 치환시켜 함수공기를 제거 킨 다음, 에틸렌디아민 420g(7.0몰)과 1,8-디아자비씨클로[5.4.0]언덱-7-엔 0.70g(1250 ppm)을 각각 상기 플라스크에 넣은 후, 다시 질소분위기로 치환시킨 다음 질소를 환류냉각기의 상부에 흘러 보내 함수공기의 반응계로 유입을 차단하면서 마그네틱 교반기로 반응액을 잘 교반하면서 반응기의 하부에 설치된 가열판으로 반응물의 온도를 50℃까지 상승시켜 유지시키고 적가 깔대기에 채워진 3-클로로프로필트리메톡시실란 140g(0.7몰)을 1시간 동안 적가시키면서 반응을 진행한다. 10분 정도가 지나면 반응열에 의해 반응온도가 상승하면서 반응속도가 증가하므로 플라스크의 외부를 수욕탕이나 얼음탕으로 냉각시켜 반응온도가 60℃가 넘지 않도록 하면서 적가를 완료한다. 적가 도중 잘 교반시켜 반응을 균일하게 해 줄 필요가 있다. 1시간 동안 적가시키면서 반응시킨 후, 3-클로로프로필메톡시실란의 전환율이 80 내지 90%에 도달되므로 상기 반응 온도에서 1시간 더 숙성시켜 반응을 완결시킨다. 반응이 완결된 혼합액에 에틸렌디아민 · 염화수소 염 220g을 투입하면 2상으로 액의 분리가 일어나며, 이 때 반응물은 상부층 216g과 하부층 559g의 비율로 획득할 수 있었으며, 3-[N-(2-아미노에틸)]아미노프로필트리메톡시실란 대 에틸렌디아민 · 염화수소 대 에틸렌디아민의 몰비율이 1:4.5:8.4 일 때 반응물의 상분리가 양호하였다. 반응액의 2상으로 분리 시 미세입자의 완전한 분리를 위해 실온하에서 액의 온도를 40℃ 대로 하강시킨다. 이 액을 30분 이상 방치하면 하부층에 우유빛 점성질의 에틸렌디아민 · 염화수소가 풍부한 혼합물층이 위치하고 상층부에는 무색 투명한 3-[N-(2-아미노에틸)]아미노프로필트리메톡시실란이 풍부한 혼합물층이 위치하게 된다. 하부층을 반응기로부터 분리하고 상부층의 3-[N-(2-아미노에틸)]아미노프로필트리메톡시실란이 풍부한 혼합액을 1ℓ 증류플라스크에 옮기고 마그네틱 교반기로 잘 교반시키면서 60 ~ 70℃로 가열시키면서 300torr에서 5torr까지 진공도를 하강시키면서 저비점인 메탄올과 에틸렌디아민을 제거하면 목적물의 여액을 획득할 수 있다. 여액은 핵자기 공명분석기로 목적물임을 확인하였고 가스크로마토그래피로 분석하였을 때 3-[N-(2-아미노에틸)]아미노프로필트리메톡시실란의 함량은 98.6%, 메탄올 1.2%, 기타 0.2% 로 각각 정량할 수 있었으며, 이 여액은 148g이었고 수율은 95%였다.Dry a 1 L four-necked round-necked reactor equipped with a thermometer, reflux condenser, nitrogen inlet, and dropping funnel, install on a hot plate that can be stirred and heated, replace with a nitrogen atmosphere to remove hydrous air, and then remove ethylene. 420 g (7.0 mol) of diamine and 0.70 g (1250 ppm) of 1,8-diazabicyclo [5.4.0] undec-7-ene were added to the flask, and then replaced with a nitrogen atmosphere. Nitrogen was then added to the reflux condenser. 3-Chloropropyltrime filled in the dropping funnel while keeping the temperature of the reactant heated to 50 ℃ with a heating plate installed in the lower part of the reactor while stirring the reaction solution well with a magnetic stirrer while blocking the inflow into the reaction system of the hydrous air. The reaction proceeds with dropwise addition of 140 g (0.7 mol) of oxysilane for 1 hour. After about 10 minutes, the reaction temperature is increased by the reaction heat and the reaction rate is increased, so the outside of the flask is cooled with a water bath or ice bath to complete the dropping while the reaction temperature does not exceed 60 ° C. It is necessary to make the reaction uniform by stirring well during the dropping. After the reaction was added dropwise for 1 hour, the conversion rate of 3-chloropropylmethoxysilane reached 80 to 90%, so that the reaction was completed for 1 hour at the reaction temperature to complete the reaction. When the reaction mixture was added to 220g of ethylenediamine-hydrogen chloride salt, the liquid was separated into two phases. At this time, the reaction product was obtained at a ratio of 216g in the upper layer and 559g in the lower layer, and 3- [N- (2-amino The phase separation of the reactants was good when the molar ratio of ethyl)] aminopropyltrimethoxysilane to ethylenediaminehydrogen chloride to ethylenediamine was 1: 4.5: 8.4. When the reaction solution is separated into two phases, the temperature of the solution is lowered to 40 ° C. at room temperature to completely separate the fine particles. After the solution is left for 30 minutes or more, a milky viscous ethylenediamine-hydrogen chloride-rich mixture layer is placed on the lower layer, and a colorless and transparent 3- [N- (2-aminoethyl)] aminopropyltrimethoxysilane mixture is placed on the upper layer. The floor is located. The lower layer was separated from the reactor and the mixed liquid rich in 3- [N- (2-aminoethyl)] aminopropyltrimethoxysilane in the upper layer was transferred to a 1L distillation flask and heated to 60-70 ° C with good stirring with a magnetic stirrer at 300torr. Removing the low boiling point methanol and ethylenediamine while lowering the vacuum degree to 5torr can obtain the desired filtrate. The filtrate was identified as a target by a nuclear magnetic resonance analyzer. The content of 3- [N- (2-aminoethyl)] aminopropyltrimethoxysilane was 98.6%, methanol 1.2%, and other 0.2% when analyzed by gas chromatography. Each could be quantified, the filtrate was 148g and the yield was 95%.
[실시예 2]Example 2
실시예1과 같은 실험장치를 질소 분위기로 치환시켜 함수공기를 제거 킨 다음, 에틸렌디아민 340g(5.6몰)과 1,8-디아자비씨클로[5.4.0]언덱-7-엔 0.7g (1458 ppm)을 각각 상기 플라스크에 넣은 후, 다시 질소분위기하에서 잘 교반하면서 반응물의 온도를 50℃까지 상승시켜 유지시키고 3-클로로프로필메톡시실란 140g(0.7몰)을 1시간 동안 적가시키면서 반응을 실시예 1과 같이 진행시켜 반응을 완결시킨 후 에틸렌디아민 · 염화수소 염 180g을 투입하고 냉각시키면서 2상으로 분액을 유도한다. 상기 반응액을 실온하에서 40℃ 대로 하강시키면서 30분 이상 방치하면 2상으로 잘 분리 되며, 상부층은 202g 및 하부층은 475g의 량으로 획득할 수 있었다. 반응기로 부터 하부층을 분리하여 증류 플라스크로 옮기고, 상부층 혼합액을 실시예1과 같이 증류하였을 때 3-[N-(2-아미노에틸)]아미노프로필트리메톡시실란의 함량은 98.0%, 메탄올 1.7%, 기타 0.3% 로 각각 정량할 수 있었으며, 이 여액은 146g 이었고 수율은 94%였다. 반응기에서 분리한 하부층액도 상부층액과 마찬가지의 조건에서 증류하고 메탄올과 에틸렌디아민 등 저비점분을 제거하여 에틸렌디아민 · 염화수소를 271g을 획득하였으며, 200g은 재순환하여 사용하고 나머지는 폐기하였다. Substituting the same experimental apparatus as in Example 1 to remove the aqueous air, 340 g (5.6 mol) of ethylenediamine and 0.7 g (1458 ppm of 1,8-diazabicyclo [5.4.0] undec-7-ene ) Were added to the flask, and the mixture was stirred under nitrogen atmosphere again while maintaining the temperature of the reactant to 50 ° C., and 140 g (0.7 mole) of 3-chloropropylmethoxysilane was added dropwise for 1 hour. After proceeding to complete the reaction, 180 g of ethylenediamine-hydrogen chloride salt is added and cooled to induce separation in two phases. The reaction solution was separated into two phases if left at room temperature for 30 minutes or more while lowering to 40 ° C. The upper layer was obtained in an amount of 202 g and the lower layer 475 g. The lower layer was separated from the reactor and transferred to a distillation flask. When the upper layer mixture was distilled as in Example 1, the content of 3- [N- (2-aminoethyl)] aminopropyltrimethoxysilane was 98.0% and methanol 1.7%. , And 0.3% of each other. The filtrate was 146g and the yield was 94%. The lower layer liquid separated from the reactor was also distilled under the same conditions as the upper layer liquid, and low boiling points such as methanol and ethylenediamine were removed to obtain 271 g of ethylenediamine and hydrogen chloride. 200 g was recycled and the rest was discarded.
상기한 실시예에 한정되지 아니하며, 청구범위에서 청구하는 본 발명의 요지를 벗어남이 없이 당해 본 발명이 속하는 분야에서 통상의 지식을 가진 자라면 누구든지 다양한 변형 실시가 가능한 것은 물론이고, 그와 같은 변경은 기재된 청구범위 내에 있게 된다.The present invention is not limited to the above embodiments, and various modifications can be made by those skilled in the art to which the present invention pertains without departing from the gist of the present invention as claimed in the claims. Changes are intended to fall within the scope of the claims set forth.
본 발명에 따른 γ-[N-(2-아미노에틸)]아미노알킬알콕시실란 제조방법은 적당량의 에틸렌디아민과 환형삼차아민 촉매의 혼합액에 γ-클로로알킬알콕시실란을 적가하여 저온에서 반응시킴으로서 부생물인 비스실릴류의 생성을 억제하면서 목적물을 고순도로 합성할 수 있으며, 저온에서 반응과 정제공정을 거치므로 변색을 방지할 수 있고, 반응 후 혼합액에 에틸렌디아민 · 염화수소을 투입하여 2상으로 분리를 유도함으로써 별도의 상분리기와 1차 증류공정을 배제하여 정제함으로써 제조공정을 단순화해 목적물을 고수율로 획득한 장점, 에틸렌디아민 · 염화수소이 풍부한 하부층 중 저비점과 고비점을 제거한 후 반응계에 재사용함으로서 메탄올과 고비점분의 축적을 최소화한 장점이 있다.In the method for preparing γ- [N- (2-aminoethyl)] aminoalkylalkoxysilane according to the present invention, γ-chloroalkylalkoxysilane is added dropwise to a mixture of an appropriate amount of ethylenediamine and a cyclic tertiary amine catalyst to react by-product at low temperature. The target product can be synthesized with high purity while suppressing the formation of inbissilyl, and it can be prevented from discoloration by reacting and purifying at low temperature.Induced separation in two phases by adding ethylenediamine and hydrogen chloride to the mixed solution after the reaction. By eliminating the separate phase separator and the first distillation process, the manufacturing process can be simplified and the target product can be obtained in high yield. This has the advantage of minimizing accumulation.
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| CN109415393A (en) * | 2016-07-01 | 2019-03-01 | 捷恩智株式会社 | The manufacturing method of N- silylamido alkyl silane cpd |
| CN113501840A (en) * | 2021-07-11 | 2021-10-15 | 浙江开化合成材料有限公司 | Method for preparing N- (2-aminoethyl) -3-aminopropyltrimethoxysilane by adopting pipeline reactor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109415393A (en) * | 2016-07-01 | 2019-03-01 | 捷恩智株式会社 | The manufacturing method of N- silylamido alkyl silane cpd |
| CN109415393B (en) * | 2016-07-01 | 2021-08-03 | 捷恩智株式会社 | Process for producing N-silylaminoalkylsilane compound |
| CN113501840A (en) * | 2021-07-11 | 2021-10-15 | 浙江开化合成材料有限公司 | Method for preparing N- (2-aminoethyl) -3-aminopropyltrimethoxysilane by adopting pipeline reactor |
| CN113501840B (en) * | 2021-07-11 | 2024-04-02 | 浙江开化合成材料有限公司 | Method for preparing N- (2-aminoethyl) -3-aminopropyl trimethoxy silane by adopting pipeline reactor |
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