KR20050035764A - Method for preparing 3-[N-(2-aminoethyl)]aminopropylalkoxysilane - Google Patents
Method for preparing 3-[N-(2-aminoethyl)]aminopropylalkoxysilane Download PDFInfo
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- KR20050035764A KR20050035764A KR1020030071537A KR20030071537A KR20050035764A KR 20050035764 A KR20050035764 A KR 20050035764A KR 1020030071537 A KR1020030071537 A KR 1020030071537A KR 20030071537 A KR20030071537 A KR 20030071537A KR 20050035764 A KR20050035764 A KR 20050035764A
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- Prior art keywords
- ethylenediamine
- aminoethyl
- aminopropylalkoxysilane
- chloropropylalkoxysilane
- layer
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 18
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 63
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 60
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 claims abstract description 31
- 239000006227 byproduct Substances 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 24
- 239000007795 chemical reaction product Substances 0.000 claims description 14
- 239000011780 sodium chloride Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- -1 3-chloropropyl Chemical group 0.000 claims description 4
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- OHHBFEVZJLBKEH-UHFFFAOYSA-N ethylenediamine dihydrochloride Chemical compound Cl.Cl.NCCN OHHBFEVZJLBKEH-UHFFFAOYSA-N 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
- AZDDBRPDIWQGEK-UHFFFAOYSA-N 3-chloropropyl-diethoxy-ethylsilane Chemical compound CCO[Si](CC)(OCC)CCCCl AZDDBRPDIWQGEK-UHFFFAOYSA-N 0.000 claims description 2
- KEZMLECYELSZDC-UHFFFAOYSA-N 3-chloropropyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(OCC)CCCCl KEZMLECYELSZDC-UHFFFAOYSA-N 0.000 claims description 2
- YFWCTOVRAUWJCK-UHFFFAOYSA-N 3-chloropropyl-diethyl-methoxysilane Chemical compound CC[Si](CC)(OC)CCCCl YFWCTOVRAUWJCK-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
- IIFBEYQLKOBDQH-UHFFFAOYSA-N 3-chloropropyl-ethoxy-dimethylsilane Chemical compound CCO[Si](C)(C)CCCCl IIFBEYQLKOBDQH-UHFFFAOYSA-N 0.000 claims description 2
- GHTXEZLVNCEWTK-UHFFFAOYSA-N 3-chloropropyl-ethoxy-ethyl-methylsilane Chemical compound CCO[Si](C)(CC)CCCCl GHTXEZLVNCEWTK-UHFFFAOYSA-N 0.000 claims description 2
- PSHXXWFZFWEZTB-UHFFFAOYSA-N 3-chloropropyl-ethyl-dimethoxysilane Chemical compound CC[Si](OC)(OC)CCCCl PSHXXWFZFWEZTB-UHFFFAOYSA-N 0.000 claims description 2
- TZFYOTWRAKEZLU-UHFFFAOYSA-N 3-chloropropyl-ethyl-methoxy-methylsilane Chemical compound CC[Si](C)(OC)CCCCl TZFYOTWRAKEZLU-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
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 claims description 2
- CBRIQVFXGOWUJI-UHFFFAOYSA-N ethoxy(ethyl)silicon Chemical compound CCO[Si]CC CBRIQVFXGOWUJI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 1
- HCFPRFJJTHMING-UHFFFAOYSA-N ethane-1,2-diamine;hydron;chloride Chemical compound [Cl-].NCC[NH3+] HCFPRFJJTHMING-UHFFFAOYSA-N 0.000 abstract description 20
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 229910000077 silane Inorganic materials 0.000 abstract description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011230 binding agent Substances 0.000 abstract description 2
- 238000004821 distillation Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 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 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
본 발명은 실란결합제인 3-[N-(2-아미노에틸)]아미노프로필알콕시실란의 제조방법에 관한 것으로, 좀 더 상세하게는 3-클로로프로필알콕시실란과 과량의 에틸렌디아민을 반응시켜 3-[N-(2-아미노에틸)]아미노프로필알콕시실란을 수득할 때 반응부산물인 에틸렌디아민수화염화물을 수산화나트륨으로 분해시켜 다량 사용된 에틸렌디아민를 최대한 회수함으로써 제조 원가를 감소시킬 수 있는 3-[N-(2-아미노에틸)]아미노프로필알콕시실란의 제조방법에 관한 것이다.The present invention relates to a process for preparing 3- [N- (2-aminoethyl)] aminopropylalkoxysilane, which is a silane binder. More specifically, 3-chloropropylalkoxysilane is reacted with an excess of ethylenediamine to 3- When obtaining [N- (2-aminoethyl)] aminopropylalkoxysilane, 3- [N can be reduced by decomposing the reaction byproduct ethylenediamine hydrochloride with sodium hydroxide to recover as much of the used ethylenediamine as possible. A method for producing-(2-aminoethyl)] aminopropylalkoxysilane.
Description
본 발명은 3-[N-(2-아미노에틸)]아미노프로필알콕시실란의 제조방법에 관한 것으로, 좀 더 상세하게는 3-클로로프로필알콕시실란과 과량의 에틸렌디아민을 반응시켜 3-[N-(2-아미노에틸)]아미노프로필알콕시실란을 수득한 후, 반응부산물인 에틸렌디아민 수화염화물을 수산화나트륨으로 분해시켜 에틸렌디아민을 최대한 회수하여 3-[N-(2-아미노에틸)]아미노프로필알콕시실란을 경제적으로 제조하는 방법에 관한 것이다.The present invention relates to a process for preparing 3- [N- (2-aminoethyl)] aminopropylalkoxysilane, and more particularly, 3- [N- (2-aminoethyl)] aminopropylalkoxysilane was obtained, and then ethylenediamine hydrochloride, a reaction byproduct, was decomposed with sodium hydroxide to recover ethylenediamine as much as possible, thereby obtaining 3- [N- (2-aminoethyl)] aminopropylalkoxy. A method of economically preparing silanes.
일반적으로, 3-[N-(2-아미노에틸)]아미노프로필알콕시실란은 유기-무기계면 사이의 접착력을 향상시키거나 유, 무기물의 표면 개질, 수지의 테일링(tailing) 등 여러 가지 물성 향상에 효과적으로 사용되는 결합제(coupling agent)로 많이 사용되고 있으며, 특히 실리콘분야 중 실란트 같은 실리콘 화합물의 결합제로 널리 사용되고 있다.Generally, 3- [N- (2-aminoethyl)] aminopropylalkoxysilane is used to improve the adhesion between organic-inorganic surfaces or to improve various physical properties such as surface modification of oils, inorganic materials, and tailing of resins. It is widely used as a coupling agent (coupling agent) that is effectively used, and is widely used as a binder of a silicone compound such as a sealant, especially in the silicone field.
3-[N-(2-아미노에틸)]아미노프로필알콕시실란을 제조할 경우, 에틸렌디아민의 두가지 반응기작으로 인해 3-[N-(2-아미노에틸)]아미노프로필알콕시실란이 생성된 후 다시 한번 3-클로로프로필알콕시실란과 반응하여 비스-생성물이 합성되므로, 3-클로로프로필알콕시실란에 비해 과량의 에틸렌디아민을 사용하여 3-[N-(2-아미노에틸)]아미노프로필알콕시실란과 3-클로로프로필알콕시실란의 반응을 억제하고, 또한 부생되는 염산과 반응하여 에틸렌디아민수화염화물을 생성시키는 방향으로 연구가 진행되어 왔다.When 3- [N- (2-aminoethyl)] aminopropylalkoxysilane was prepared, two reaction mechanisms of ethylenediamine produced 3- [N- (2-aminoethyl)] aminopropylalkoxysilane and then again Since the bis-product is synthesized once by reacting with 3-chloropropylalkoxysilane, an excess of ethylenediamine is used with 3- [N- (2-aminoethyl)] aminopropylalkoxysilane and 3 compared to 3-chloropropylalkoxysilane. Research has been conducted in the direction of inhibiting the reaction of -chloropropylalkoxysilane and reacting with byproduct hydrochloric acid to produce ethylenediamine hydrochloride.
이와 관련하여, 미국특허 제4,064,155호에는 3-클로로프로필알콕시실란 당량비의 4∼6배의 에틸렌디아민을 사용하여 3-[N-(2-아미노에틸)]아미노프로필알콕시실란을 제조하는 방법이 개시되어 있으나, 비스-생성물의 억제 효과가 미흡하였으며, 생성물의 수율도 낮은 단점이 있었다.In this regard, U.S. Patent No. 4,064,155 discloses a process for preparing 3- [N- (2-aminoethyl)] aminopropylalkoxysilane using ethylenediamine four to six times the equivalent ratio of 3-chloropropylalkoxysilane. However, the inhibitory effect of the bis-product was insufficient, and the yield of the product was also low.
미국특허 제5,446,181호에는 U자형 반응기와 에틸렌디아민 증류장치를 혼합한 반응장치가 소개되어 있다. 상기 특허에서는 3-클로로프로필알콕시실란과 3-클로로프로필알콕시실란의 당량대비 12배 이상의 에틸렌디아민을 U자형 반응기에서 반응시킨 후 에틸렌디아민 증류장치로 바로 이송하여 미반응 에틸렌디아민을 증류하고, 이를 다시 U자형 반응기로 투입하여 재활용하며, 끊는점이 높은 생성물과 에틸렌디아민수화염화물은 에틸렌디아민 증류장치에 계속적으로 남게 하는 연속식 제조 방법을 개발하였다. 이는 결과적으로 3-클로로프로필알콕시실란의 당량대비 3∼5배의 에틸렌디아민을 사용하는 효과가 있으나, 에틸렌디아민 증류장치가 미반응 에틸렌디아민의 증류를 위해 항상 120∼145℃가 유지되므로, 축적되어지는 3-[N-(2-아미노에틸)]아미노프로필알콕시실란이 고온으로 인하여 고비점으로 진행되어 제품의 순도가 낮아지는 단점이 있었다. 또한 부생물인 에틸렌디아민수화염화물의 처리방법에 대해서 언급되어 있지 않았다.U. S. Patent No. 5,446, 181 introduces a reactor in which a U-shaped reactor and an ethylene diamine distillation apparatus are mixed. In this patent, more than 12 times of ethylenediamine relative to the equivalent of 3-chloropropylalkoxysilane and 3-chloropropylalkoxysilane is reacted in a U-shaped reactor, and then transferred directly to an ethylenediamine distillation unit to distill unreacted ethylenediamine, and again. A continuous production method was developed in which a U-shaped reactor was recycled and the product having a high breaking point and ethylene diamine hydrochloride remained continuously in the ethylene diamine distillation unit. This has the effect of using 3 to 5 times ethylenediamine relative to the equivalent of 3-chloropropylalkoxysilane, but since the ethylenediamine distillation apparatus is always maintained at 120 to 145 ° C for distillation of unreacted ethylenediamine, The paper has a disadvantage in that 3- [N- (2-aminoethyl)] aminopropylalkoxysilane proceeds to a high boiling point due to high temperature, thereby lowering the purity of the product. In addition, there is no mention of the method of treating the by-product ethylenediamine hydrochloride.
또한, 미국특허 제6,452,033호에는 3-클로로프로필알콕시실란과 3-클로로프로필알콕시실란의 당량대비 12배 이상의 에틸렌디아민을 반응시킨 후 반응생성물층과 부산물층으로 분리하기 위해 에틸렌디아민을 일차적으로 증류하는 공정을 생략할 수 있는 제조방법이 개시되어 있다. 상기 특허에 따른 방법은 반응초기에 에틸렌디아민수화염화물을 첨가하여 제품 합성 종료시점에서 에틸렌디아민의 제거 없이 바로 층분리가 일어날 수 있도록 반응생성물층과 염화물층의 비율을 맞추어 주는 방법이다. 이는 결과적으로 일차 에틸렌디아민 증류공정을 생략함으로써 작업시간을 단축시키는 효과가 있으나, 원료 이외에 에틸렌디아민수화염화물을 합성시 투입하므로 생산효율이 낮은 단점이 있었다. 또한 부생물인 에틸렌디아민수화염화물의 처리방법에 대해서 언급되어 있지 않았다.In addition, US Pat. No. 6,452,033 discloses that ethylenediamine is first distilled to react 12-fold or more ethylenediamine relative to the equivalent of 3-chloropropylalkoxysilane and 3-chloropropylalkoxysilane and separated into a reaction product layer and a by-product layer. A manufacturing method is disclosed in which the step can be omitted. The method according to the patent is a method of adjusting the ratio of the reaction product layer and the chloride layer so that the ethylene diamine hydride chloride is added at the beginning of the reaction so that the phase separation can occur immediately without removing the ethylene diamine at the end of the product synthesis. This resulted in shortening the working time by omitting the primary ethylenediamine distillation process, but in addition to the raw material was added to the synthesis of ethylene diamine hydrochloride had a disadvantage of low production efficiency. In addition, there is no mention of the method of treating the by-product ethylenediamine hydrochloride.
전술한 바와 같이, 종래 기술에서는 비스-생성물을 줄이기 위해 과량의 에틸렌디아민을 사용함으로써 야기되는 단점을 보완하고 공정을 단순화하기 위한 연구가 진행되어 왔으나, 에틸렌디아민수화염화물의 처리방법에 대해서는 언급하고 있지 않다. 또한, 층분리과정을 통해 분리되는 염화물층에는 에틸렌디아민수화염화물 외에도 다량의 에틸렌디아민이 잔존하고 있으므로 이를 회수하는 것이 필요하다. 따라서, 염화물층의 처리과정을 통해 에틸렌디아민의 회수율을 증대하여 전체적인 사용량을 줄이고 폐기하기 용이한 부산물로 변환하는 과정이 시급히 요구되고 있는 실정이다.As described above, researches to simplify the process and to solve the disadvantages caused by using an excess of ethylenediamine to reduce the bis-product have been conducted, but there is no mention of a method for treating ethylenediamine hydrochloride. not. In addition, in the chloride layer separated through the layer separation process, since a large amount of ethylenediamine remains in addition to ethylenediamine hydrochloride, it is necessary to recover it. Therefore, there is an urgent need to increase the recovery rate of ethylenediamine through the treatment of the chloride layer, thereby reducing the overall amount of use and converting it into by-products that are easy to dispose of.
이에 본 발명에서는 전술한 바와 같은 문제점을 해결하기 위하여 다양한 연구를 거듭한 결과, 3-클로로프로필알콕시실란과 과량의 에틸렌디아민을 반응시킨 후 일정량의 에틸렌디아민을 증류하여 반응생성물층과 부산물층으로 분리시키고, 반응생성물층은 함유된 에틸렌디아민을 증류 조작으로 제거시켜 3-[N-(2-아미노에틸)]아미노프로필알콕시실란을 얻고, 부산물층은 수산화나트륨과 물을 첨가하여 반응시켜 에틸렌디아민수화염화물을 염화나트륨과 에틸렌디아민으로 분해하여 에틸렌디아민을 회수할 수 있는 방법을 발견하였고, 본 발명은 이에 기초하여 완성되었다.Accordingly, in the present invention, various researches have been conducted to solve the problems described above. After the reaction of 3-chloropropylalkoxysilane and an excess of ethylenediamine, a certain amount of ethylenediamine is distilled to separate the reaction product layer and the byproduct layer. The reaction product layer is distilled to remove the contained ethylenediamine to obtain 3- [N- (2-aminoethyl)] aminopropylalkoxysilane, and the byproduct layer is reacted by adding sodium hydroxide and water to ethylenediamine hydration. A method has been found in which chlorides can be decomposed into sodium chloride and ethylenediamine to recover ethylenediamine, and the present invention has been completed based on this.
따라서, 본 발명의 목적은 3-[N-(2-아미노에틸)]아미노프로필알콕시실란의 제조시 생성되는 부산물인 에틸렌디아민수화염화물을 수산화나트륨을 첨가 분해 시켜 에틸렌디아민과 염화나트륨으로 회수하여 3-[N-(2-아미노에틸)]아미노프로필알콕시실란을 경제적으로 제조하는 방법을 제공하는데 있다.Accordingly, an object of the present invention is to recover ethylenediamine hydrochloride, which is a by-product produced in the production of 3- [N- (2-aminoethyl)] aminopropylalkoxysilane, by addition decomposition of sodium hydroxide to recover ethylenediamine and sodium chloride 3- A method for economically preparing [N- (2-aminoethyl)] aminopropylalkoxysilane.
상기 목적을 달성하기 위한 본 발명에 따른 3-[N-(2-아미노에틸)]아미노프로필알콕시실란의 제조방법은 (a) 3-클로로프로필알콕시실란의 당량대비 7∼12배의 에틸렌디아민을 반응기에 넣고 60∼120℃의 온도하에서 3-클로로프로필알콕시실란을 0.1∼5시간동안 적가하여 하기 반응식 1에 따라 3-[N-(2-아미노에틸)]아미노프로필알콕시실란을 합성하는 단계; (b) 상기 (a) 단계의 반응물로부터 에틸렌디아민을 증류하여 반응생성물층과 부산물층으로 층분리하는 단계; (c) 상기 (b) 단계에서 분리된 반응생성물층에서 에틸렌디아민을 증류하여 3-[N-(2-아미노에틸)]아미노프로필알콕시실란을 정제하는 단계; (d) 상기 (b) 단계에서 분리된 부산물층에 존재하는 에틸렌디아민수화염화물의 당량대비 1∼4배의 수산화나트륨을 넣고 60∼120℃에서 1∼6시간동안 하기 반응식 2에 따라 반응시켜 에틸렌디아민수화염화물을 분해시키는 단계; 및 (e) 상기 (d) 단계의 반응물을 상온으로 냉각시킨 후 부생되는 염화나트륨은 여과 제거하고 에틸렌디아민은 물로부터 추출하여 회수하는 단계를 포함하는 것을 특징으로 한다:Method for producing 3- [N- (2-aminoethyl)] aminopropylalkoxysilane according to the present invention for achieving the above object is (a) 7 to 12 times the ethylenediamine equivalent to the equivalent of 3-chloropropylalkoxysilane Putting 3-chloropropylalkoxysilane dropwise into the reactor at a temperature of 60 to 120 ° C. for 0.1 to 5 hours to synthesize 3- [N- (2-aminoethyl)] aminopropylalkoxysilane according to Scheme 1 below; (b) distilling ethylenediamine from the reactants of step (a) to separate the reaction product layer and the byproduct layer; (c) distilling ethylenediamine from the reaction product layer separated in step (b) to purify 3- [N- (2-aminoethyl)] aminopropylalkoxysilane; (d) 1 to 4 times the sodium hydroxide equivalent to the equivalent of ethylenediamine hydrochloride chloride present in the by-product layer separated in step (b) and reacted at 60 to 120 ° C. for 1 to 6 hours according to the following Equation 2 Decomposing the diamine hydrochloride; And (e) cooling the reaction product of step (d) to room temperature to remove by-product sodium chloride and extracting and recovering ethylenediamine from water.
NH2CH2CH2NHCH2CH2CH2SiR1 3- n (OR2) n + NH2CH2CH 2NH2·ClNH 2 CH 2 CH 2 NHCH 2 CH 2 CH 2 SiR 1 3- n (OR 2 ) n + NH 2 CH 2 CH 2 NH 2 Cl
상기 식에서, n은 1∼3의 정수이고, R1 및 R2는 서로 같거나 다르게 탄소수가 1∼6인 알킬기이다.Wherein n is an integer of 1 to 3, R 1 and R 2 are the same or different alkyl groups having 1 to 6 carbon atoms.
이하 본 발명을 좀 더 구체적으로 살펴보면 다음과 같다.Looking at the present invention in more detail as follows.
전술한 바와 같이, 본 발명에서는 3-클로로프로필알콕시실란과 비스-생성물을 억제할 수 있는 당량대비 7∼12배의 에틸렌디아민을 반응시켜 3-[N-(2-아미노에틸)]아미노프로필알콕시실란을 수득한 후, 반응부산물인 에틸렌디아민 수화염화물을 수산화나트륨으로 분해하여 다량 사용된 에틸렌디아민을 최대한 회수함으로써 원가 부담을 줄이는 3-[N-(2-아미노에틸)]아미노프로필알콕시실란의 제조방법이 제공된다.As mentioned above, in the present invention, 3- [N- (2-aminoethyl)] aminopropylalkoxy is reacted with 3-chloropropylalkoxysilane and 7-12 times ethylenediamine relative to the equivalent of the bis-product. After obtaining the silane, the production of 3- [N- (2-aminoethyl)] aminopropylalkoxysilane to reduce the cost burden by decomposing the reaction by-product ethylenediamine hydrochloride with sodium hydroxide to recover the most used ethylenediamine A method is provided.
본 발명의 3-[N-(2-아미노에틸)]아미노프로필알콕시실란은 3-클로로프로필알콕시실란과 당량대비 7∼12배의 에틸렌디아민을 반응시켜 하기 반응식 1에 따라 제조된다:3- [N- (2-aminoethyl)] aminopropylalkoxysilane of the present invention is prepared according to Scheme 1 by reacting 3-chloropropylalkoxysilane with 7-12 times ethylenediamine relative to the equivalent:
반응식 1Scheme 1
ClCH2CH2CH2SiR1 3- n (OR2 ) n + 2NH2CH2CH2NH2 →ClCH 2 CH 2 CH 2 SiR 1 3- n (OR 2 ) n + 2 NH 2 CH 2 CH 2 NH 2 →
NH2CH2CH2NHCH2CH2CH2SiR1 3- n (OR2) n + NH2CH2CH 2NH2·ClNH 2 CH 2 CH 2 NHCH 2 CH 2 CH 2 SiR 1 3- n (OR 2 ) n + NH 2 CH 2 CH 2 NH 2 Cl
상기 식에서, n은 1∼3의 정수이고, R1 및 R2는 서로 같거나 다르게 탄소수가 1∼6인 알킬기이다.Wherein n is an integer of 1 to 3, R 1 and R 2 are the same or different alkyl groups having 1 to 6 carbon atoms.
상기 반응의 전 과정은 수분의 유입을 막기 위해 질소가스 분위기하에서 실시한다. 좀 더 상세하게는, 먼저 에틸렌디아민을 반응기에 투입한 후 60∼120℃의 온도하에서 3-클로로프로필알콕시실란을 0.1∼5시간 동안 적가하면서 반응시켜 3-[N-(2-아미노에틸)]아미노프로필알콕시실란을 합성한다.The whole process of the reaction is carried out in a nitrogen gas atmosphere to prevent the inflow of moisture. More specifically, ethylenediamine is first introduced into the reactor, and then 3-chloropropylalkoxysilane is added dropwise for 0.1 to 5 hours at a temperature of 60 to 120 캜 to react with 3- [N- (2-aminoethyl)]. Aminopropylalkoxysilane is synthesized.
여기서, 상기 반응온도가 60℃ 미만이면 반응속도가 느려 반응시간이 길어지므로 작업시간이 늘어나는 문제점이 있고, 120℃를 초과하면 합성된 3-[N-(2-아미노에틸)]아미노프로필알콕시실란이 고분자화가 진행되어 고비점 생성물이 증가하는 문제점이 있다.Here, if the reaction temperature is less than 60 ℃ the reaction time is slow, the reaction time is long, there is a problem that the working time increases, and if it exceeds 120 ℃ synthesized 3- [N- (2-aminoethyl)] aminopropyl alkoxysilane This polymerization proceeds, there is a problem that the high boiling point product increases.
그 다음, 과량 투입된 에틸렌디아민을 반응시와 동일한 온도에서 1∼600torr 감압하에서 일차증류를 실시한다. 일정량의 에틸렌디아민을 반응계에서 제거한 후 서서히 냉각시키면 비중차이에 의해 반응생성물층과 부산물층으로 층분리가 일어난다. 맑고 투명한 상층인 반응생성물층은 3-[N-(2-아미노에틸)]아미노프로필알콕시실란과 에틸렌디아민의 혼합물이며, 불투명하고 점성이 있는 하층은 에틸렌디아민수화염화물과 에틸렌디아민의 혼합물층이다.Subsequently, firstly distillation of the excessively added ethylenediamine under reduced pressure of 1 to 600 torr at the same temperature as in the reaction. If a certain amount of ethylenediamine is removed from the reaction system and then gradually cooled, layer separation occurs into the reaction product layer and the by-product layer due to the specific gravity difference. The reaction product layer, which is a clear transparent upper layer, is a mixture of 3- [N- (2-aminoethyl)] aminopropylalkoxysilane and ethylenediamine, and the opaque, viscous lower layer is a mixture layer of ethylenediamine hydrochloride and ethylenediamine.
층분리가 완료된 후 부산물층을 용기에서 제거하고, 반응생성물층은 일차증류와 동일한 조건으로 이차증류를 실시하여 에틸렌디아민을 제거하면 고순도의 3-[N-(2-아미노에틸)]아미노프로필알콕시실란을 수득할 수 있다.After layer separation is completed, the by-product layer is removed from the vessel, and the reaction product layer is subjected to secondary distillation under the same conditions as the primary distillation to remove ethylenediamine. Thus, 3- [N- (2-aminoethyl)] aminopropyl alkoxy of high purity is obtained. Silanes can be obtained.
본 발명에서 사용되는 3-클로로프로필알콕시실란류로는 3-클로로프로필트리메톡시실란, 3-클로로프로필메틸디메톡시실란, 3-클로로프로필디메틸메톡시실란, 3-클로로프로필트리에톡시실란, 3-클로로프로필메틸디에톡시실란, 3-클로로프로필디메틸에톡시실란, 3-클로로프로필에틸디메톡시실란, 3-클로로프로필디에틸메톡시실란, 3-클로로프로필에틸디에톡시실란, 3-클로로프로필대에틸에톡시실란, 3-클로로프로필에틸메틸메톡시실란, 3-클로로프로필에틸메틸에톡시실란 등이 있고, 이중 하나를 선택하여 사용할 수 있다.3-chloropropylalkoxysilanes used in the present invention include 3-chloropropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyldimethylmethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropylmethyldiethoxysilane, 3-chloropropyldimethylethoxysilane, 3-chloropropylethyldimethoxysilane, 3-chloropropyldiethylmethoxysilane, 3-chloropropylethyldiethoxysilane, 3-chloropropyl Large ethyl ethoxysilane, 3-chloropropyl ethyl methyl methoxy silane, 3-chloropropyl ethyl methyl ethoxy silane, etc. can be used, and one of these can be selected and used.
상술한 바와 같이 3-[N-(2-아미노에틸)]아미노프로필알콕시실란을 수득한 후, 층분리과정에서 제거된 부산물층의 에틸렌디아민수화염화물은 수산화나트륨과 반응시켜 하기 반응식 2에 따라 에틸렌디아민과 염화나트륨 및 물로 분해시킨다:After obtaining 3- [N- (2-aminoethyl)] aminopropylalkoxysilane as described above, the ethylenediamine hydrochloride chloride of the by-product layer removed in the layer separation process is reacted with sodium hydroxide to make ethylene according to Scheme 2 below. Decompose with diamine, sodium chloride and water:
반응식 2Scheme 2
NH2CH2CH2NH2HCl + NaOH → NH2CH2CH 2NH2 + NaCl + H2ONH 2 CH 2 CH 2 NH 2 HCl + NaOH → NH 2 CH 2 CH 2 NH 2 + NaCl + H 2 O
좀 더 상세하게는, 에틸렌디아민수화염화물과 에틸렌디아민의 혼합물인 부산물층을 반응용기에 투입한 후, 에틸렌디아민수화염화물의 당량대비 1∼4배의 고체 수산화나트륨을 투입하고 1∼6시간 동안 교반하면서 60∼120℃의 온도하에서 반응시키면 에틸렌디아민수화염화물이 분해되어 염화나트륨의 결정이 생성된다.More specifically, the by-product layer, which is a mixture of ethylenediamine hydrochloride and ethylenediamine, is added to the reaction vessel, and then 1-4 times of solid sodium hydroxide is added to the equivalent of ethylenediamine hydrochloride and stirred for 1-6 hours. While the reaction is carried out at a temperature of 60 to 120 ° C., ethylenediamine hydrochloride is decomposed to form crystals of sodium chloride.
여기서, 상기 반응온도가 60℃ 미만이면 반응에 참여하기 위한 충분한 수산화나트륨이 물에 용해되지 못하는 문제점이 있고, 120℃를 초과하면 에틸렌디아민이 산화되는 문제점이 있다.Here, if the reaction temperature is less than 60 ℃ there is a problem that does not dissolve enough sodium hydroxide in water to participate in the reaction, if it exceeds 120 ℃ there is a problem that ethylenediamine is oxidized.
한편, 이로부터 얻어진 반응물을 상온으로 냉각시킨 후 염화나트륨을 여과하면 에틸렌디아민과 수산화나트륨 수용액의 혼합물이 남게 된다. 이 혼합물에 분해 전 에틸렌디아민수화염화물의 당량대비 1∼3배의 물을 넣고 40∼120℃의 온도하에서 분해 전 에틸렌디아민수화염화물의 당량대비 1∼4배의 고체 수산화나트륨을 용해시키면 층분리가 일어난다. 상층은 에틸렌디아민층이고, 하층은 수산화나트륨 수용액층이 된다. 여기서 얻어진 에틸렌디아민층은 소량의 수분을 함유하고 있으므로 금속 나트륨을 첨가하고 에틸렌디아민을 증류하여 용기에서 제거하면 고순도로 회수할 수 있다.On the other hand, after cooling the reaction product obtained from room temperature and filtered sodium chloride, a mixture of ethylenediamine and sodium hydroxide aqueous solution remains. In this mixture, 1 to 3 times the amount of water equivalent to ethylenediamine hydrochloride prior to decomposition, and 1 to 4 times the amount of solid sodium hydroxide equivalent to the equivalent of ethylenediamine hydrochloride prior to decomposition at a temperature of 40 to 120 DEG C. Happens. The upper layer is an ethylenediamine layer, and the lower layer is an aqueous sodium hydroxide solution layer. Since the ethylenediamine layer obtained here contains a small amount of water, it can be recovered with high purity by adding metal sodium and distilling ethylenediamine out of the container.
전술한 바와 같이, 본 발명의 방법에 따르면, 3-[N-(2-아미노에틸)]아미노프로필알콕시실란 합성 중 제거되는 부산물층을 재처리과정을 통하여 에틸렌디아민수화염화물로부터 분해되어 얻어지는 에틸렌디아민을 회수함으로써 3-[N-(2-아미노에틸)]아미노프로필알콕시실란의 합성 과정 중, 일, 이차 증류과정에서 회수되는 에틸렌디아민과 더불어 과량 투입된 미반응 에틸렌디아민을 90% 이상 회수할 수 있다. 결과적으로 3-클로로프로필알콕시실란의 당량대비 1.5∼3배의 에틸렌디아민만을 소비하고 3-[N-(2-아미노에틸)]아미노프로필알콕시실란을 얻을 수 있는 경제적인 방법이다.As described above, according to the method of the present invention, ethylenediamine obtained by decomposing the byproduct layer removed during the synthesis of 3- [N- (2-aminoethyl)] aminopropylalkoxysilane from the ethylenediamine hydrochloride by reprocessing By recovering more than 90% of the unreacted ethylenediamine added in addition to the ethylenediamine recovered during the second and second distillation during the synthesis of 3- [N- (2-aminoethyl)] aminopropylalkoxysilane can be recovered. . As a result, it is an economical method to consume only 1.5 to 3 times ethylenediamine relative to the equivalent of 3-chloropropylalkoxysilane and to obtain 3- [N- (2-aminoethyl)] aminopropylalkoxysilane.
이하 실시예를 통하여 본 발명을 좀 더 구체적으로 살펴보지만, 하기 예에 본 발명의 범주가 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the following examples.
실시예 1Example 1
교반기, 적가 깔대기, 환류콘덴서, 온도계 및 질소 공급장치가 부착된 6ℓ- 5구 반응기를 질소 분위기로 한 후, 에틸렌디아민 3,306ｇ(55몰)을 주입하고 교반하면서 적가 깔대기를 통하여 실란화합물로 3-클로로프로필트리메톡시실란 1,093ｇ(5.5몰)을 1∼3시간 동안 적가하였다. 물중탕을 사용하여 반응온도를 80∼100℃의 범위로 조절하였다. 반응 종료 후 60∼100℃의 온도 및 1∼600torr 감압하에서 에틸렌디아민을 증류하여 1,586g을 회수하였다. 증류 후 남은 혼합물을 상온으로 냉각하면 층분리가 일어나고 부산물층인 하층을 배출시킨 후 반응생성물층인 상층을 60∼100℃의 온도 및 1∼600torr 감압하에서 잔여 에틸렌디아민을 증류하여 450g을 회수하고, 순도 98%, 수율 92%의 3-[N-(2-아미노에틸)]아미노프로필트리메톡시실란을 얻었다. 배출된 부산물층은 반응기에 넣고 수산화나트륨 264g을 투입한 후 1∼6시간 동안 교반하면서 60∼120℃의 온도하에서 반응시켜 에틸렌디아민수화염화물을 염화나트륨 결정으로 변환시켰다. 염화나트륨은 여과를 통해 분리 제거하고, 물 197g과 수산화나트륨 502g을 넣고 40∼120℃에서 용해시키면 에틸렌디아민으로부터 물이 추출되어 에틸렌디아민층인 상층과 수산화나트륨수용액층인 하층으로 층분리가 되고, 하층을 제거하면 상층으로부터 782g의 에틸렌디아민을 회수할 수 있었다.A 6 liter 5-necked reactor equipped with a stirrer, a dropping funnel, a reflux condenser, a thermometer, and a nitrogen supply device was placed in a nitrogen atmosphere, and then 3,306 g (55 mol) of ethylenediamine was injected into the silane compound through a dropping funnel. 1,093 g (5.5 mole) of chloropropyltrimethoxysilane was added dropwise for 1 to 3 hours. The reaction temperature was adjusted to the range of 80-100 degreeC using the water bath. After completion of the reaction, ethylenediamine was distilled off at a temperature of 60 to 100 ° C. and 1 to 600 torr under reduced pressure to recover 1,586 g. When the mixture remaining after distillation is cooled to room temperature, layer separation occurs and the lower layer, which is a byproduct layer, is discharged. 3- [N- (2-aminoethyl)] aminopropyltrimethoxysilane was obtained with a purity of 98% and a yield of 92%. The discharged by-product layer was placed in a reactor, 264 g of sodium hydroxide was added thereto, and then reacted at a temperature of 60 to 120 ° C. while stirring for 1 to 6 hours to convert ethylenediamine hydrochloride into sodium chloride crystals. Sodium chloride is separated and removed by filtration, 197 g of water and 502 g of sodium hydroxide are added and dissolved at 40 to 120 ° C., water is extracted from ethylenediamine, and the layers are separated into an upper layer of ethylenediamine and a lower layer of sodium hydroxide aqueous solution. Removal of 782 g of ethylenediamine was recovered from the upper layer.
전술한 바와 같이, 본 발명의 방법에 따르면, 3-[N-(2-아미노에틸)]아미노프로필알콕시실란 제조시 부산물층에 잔존하는 에틸렌디아민과 에틸렌디아민수화염화물을 수산화나트륨과 반응시킨 후 이로부터 얻어지는 에틸렌디아민을 각각 회수하여 비스-생성물의 억제를 위해 과량 사용한 에틸렌디아민의 회수율을 높여 에틸렌디아민의 소모량을 줄임으로써 3-[N-(2-아미노에틸)]아미노프로필알콕시실란을 경제적으로 제조할 수 있다.As described above, according to the method of the present invention, the ethylenediamine and ethylenediamine hydrochloride remaining in the by-product layer during the preparation of 3- [N- (2-aminoethyl)] aminopropylalkoxysilane are reacted with sodium hydroxide and then Economically produced 3- [N- (2-aminoethyl)] aminopropylalkoxysilane by reducing the consumption of ethylenediamine by increasing the recovery rate of excess ethylenediamine used for the inhibition of bis-products, respectively can do.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102009000678A1 (en) | 2009-02-06 | 2010-08-19 | Wacker Chemie Ag | Producing ethylenediamine from ethylenediamine hydrochloride comprises mixing ethylenediamine hydrochloride with amine-A, and distillatively separating the produced ethylenediamine from the obtained mixture |
| CN102898460A (en) * | 2012-10-21 | 2013-01-30 | 荆州市江汉精细化工有限公司 | Technology for preparing double-amino silane and treating by-product |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102009000678A1 (en) | 2009-02-06 | 2010-08-19 | Wacker Chemie Ag | Producing ethylenediamine from ethylenediamine hydrochloride comprises mixing ethylenediamine hydrochloride with amine-A, and distillatively separating the produced ethylenediamine from the obtained mixture |
| CN102898460A (en) * | 2012-10-21 | 2013-01-30 | 荆州市江汉精细化工有限公司 | Technology for preparing double-amino silane and treating by-product |
| CN102898460B (en) * | 2012-10-21 | 2015-03-11 | 荆州市江汉精细化工有限公司 | Technology for preparing double-amino silane and treating by-product |
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