KR100361367B1 - Process for preparing an oxime type crosslinking agent used for silicone sealants - Google Patents
Process for preparing an oxime type crosslinking agent used for silicone sealants Download PDFInfo
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- KR100361367B1 KR100361367B1 KR1019950002215A KR19950002215A KR100361367B1 KR 100361367 B1 KR100361367 B1 KR 100361367B1 KR 1019950002215 A KR1019950002215 A KR 1019950002215A KR 19950002215 A KR19950002215 A KR 19950002215A KR 100361367 B1 KR100361367 B1 KR 100361367B1
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- Prior art keywords
- oxime
- formula
- silane
- crosslinking agent
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- 150000002923 oximes Chemical class 0.000 title claims abstract description 43
- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 28
- 239000004590 silicone sealant Substances 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 229910000077 silane Inorganic materials 0.000 claims abstract description 77
- -1 oxime compound Chemical class 0.000 claims abstract description 76
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000011541 reaction mixture Substances 0.000 claims description 10
- 230000001588 bifunctional effect Effects 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 9
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 abstract 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000005055 methyl trichlorosilane Substances 0.000 description 8
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 8
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 6
- 239000005457 ice water Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- FZENGILVLUJGJX-IHWYPQMZSA-N (Z)-acetaldehyde oxime Chemical compound C\C=N/O FZENGILVLUJGJX-IHWYPQMZSA-N 0.000 description 1
- JHNRZXQVBKRYKN-VQHVLOKHSA-N (ne)-n-(1-phenylethylidene)hydroxylamine Chemical compound O\N=C(/C)C1=CC=CC=C1 JHNRZXQVBKRYKN-VQHVLOKHSA-N 0.000 description 1
- VTWKXBJHBHYJBI-VURMDHGXSA-N (nz)-n-benzylidenehydroxylamine Chemical compound O\N=C/C1=CC=CC=C1 VTWKXBJHBHYJBI-VURMDHGXSA-N 0.000 description 1
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- KXJLGCBCRCSXQF-UHFFFAOYSA-N [diacetyloxy(ethyl)silyl] acetate Chemical compound CC(=O)O[Si](CC)(OC(C)=O)OC(C)=O KXJLGCBCRCSXQF-UHFFFAOYSA-N 0.000 description 1
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0892—Compounds with a Si-O-N linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
- C08K5/5465—Silicon-containing compounds containing nitrogen containing at least one C=N bond
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Sealing Material Composition (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
본 발명은 실리콘 실란트용 옥심형 가교제의 제조방법에 관한 것으로서, 더욱 상세하게는 탈옥심형 실리콘 실란트 제조시 물성향상을 위하여 사용되는 실리콘 실란트용 옥심형 가교제의 제조방법에 관한 것이다.The present invention relates to a method for producing an oxime crosslinking agent for a silicone sealant, and more particularly, to a method for preparing an oxime crosslinking agent for a silicone sealant used for improving physical properties in the manufacture of a oxime type silicone sealant.
현재 사용되어지고 있는 실리콘 실란트로는 탈초산형, 탈옥심형, 탈알콜형 등이 있다. 일반적으로 실리콘 실란트의 조성은 베이스 폴리머, 가교제, 커플링제, 촉매, 가소제, 그리고 충진제 등으로 되어 있다. 실리콘 실란트의 자체 반응과 경화과정을 살피보면, 먼저 조성 중의 베이스 폴리머와 가교제가 반응을 진행한 후 공기 중의 수분에 의하여 경화가 진행되어 고무 성질의 탄성체가 부여되어진다. 탈옥심형 실리콘 실란트는 공기 중의 수분과 반응하여 옥심이 빠져 나오면서 경화가 이루어진다. 탈옥심형 실리콘 실란트는 탈초산형 실리콘 실란트보다 사용시 냄새가 거의 없는 장점이 있으나, 동계 금속을 부식시키는 단점이 있다.Silicone sealants currently used include deacetic acid type, oxime type, and dealcohol type. In general, the silicone sealant is composed of a base polymer, a crosslinking agent, a coupling agent, a catalyst, a plasticizer, and a filler. Looking at the self-reaction and curing process of the silicone sealant, first, the base polymer and the crosslinking agent in the composition proceed with the reaction and then the curing proceeds by the moisture in the air to give a rubbery elastomer. The jailbroken silicone sealant reacts with moisture in the air and hardens as the oxime exits. The oxime-type silicone sealant has an advantage of almost no smell when used than the deacetic acid-type silicone sealant, but has a disadvantage of corrosive to copper-based metals.
일반적으로 실리콘실란트의 물성을 향상시키기 위해서는 가교제로서 메틸트리스(메틸에틸케톡시모) 실란과 비닐트리스(메틸에틸케톡시모) 실란 등을 단독 또는 2종 이상 혼합하여 사용하고 있는데, 1종의 가교제를 사용하는 것에 비하여 2종또는 그 이상을 혼합 사용하는 것이 가교밀도 향상 및 초기 경화속도 증가 등에 도움이 되는 것으로 알려져 있다.In general, in order to improve the physical properties of the silicone sealant, methyltris (methylethylketoxymo) silane and vinyltris (methylethylketoxymo) silane or the like are used alone or as a mixture of two or more kinds thereof as a crosslinking agent. It is known that the use of two or more kinds of mixtures is helpful in improving the crosslinking density, increasing the initial curing rate, and the like.
현재까지 보고되어진 일반적인 가교제 합성방법의 일예로, 미국 특허 제 4,400,527호, 제5,087,718호, 제4,380,660호 및 제4,918,209호 등에서는 메틸트리스(메틸에틸케톡시모) 실란, 메틸알콕시비스(메틸에틸케톡시모) 실란, 비닐트리스(메틸에틸케톡시모) 실란 등과 같은 가교제를 1종 또는 2종을 각각 합성한 후, 다시 이들 가교제를 1종 또는 2종 이상 블렌딩하여 사용하고 있다. 이럴 경우 합성된 가교제의 수율이 저하되며, 또한 대기와의 접촉에 의한 가수분해 현상으로 가교제의 순도가 저하되는 등 공정상 불합리하고 어려운 점이 따를 수밖에 없다.As an example of a general method for synthesizing crosslinking agents reported to date, US Pat. Nos. 4,400,527, 5,087,718, 4,380,660, 4,918,209 and the like are methyltris (methylethylketoxymo) silane, methylalkoxybis (methylethylketoxymo) After synthesize | combining 1 type or 2 types of crosslinking agents, such as a silane and a vinyl tris (methyl ethyl methoxymo) silane, respectively, these crosslinking agents are blended and used 1 or 2 or more types, respectively. In this case, the yield of the synthesized crosslinking agent is lowered, and the purity of the crosslinking agent is lowered due to hydrolysis due to contact with the atmosphere.
이에 본 발명에서는 통상 메틸트리스(메틸에틸케톡시모) 실란과 같은 3관능성 옥심실란을 주성분으로 제조한 다음, 실란트의 경화속도 및 가교밀도를 조절하기 위하여 2관능성 옥심실란이나 4관능성 옥심실란을 일정량 첨가해야 하는 종래 기술의 문제점을 해결하고자 한 것으로, 2관능성, 3관능성 및 4관능성 옥심실란을 한꺼번에 제조하여 별도로 2관능성이나 4관능성 옥심실란을 따로 첨가할 필요없이 전 공정을 하나의 반응기내에서 실시할 수 있도록 함으로써 우수한 수율로 가교제를 수득할 수 있도록 한 실리콘 실란트용 옥심형 가교제의 제조방법을 제공하는 데 그 목적이 있다.Accordingly, in the present invention, trifunctional oxime silanes such as methyltris (methylethylketoxymo) silane are usually prepared as main components, and then bifunctional oxime silanes or tetrafunctional oxime silanes are used to control the curing rate and crosslinking density of the sealant. To solve the problems of the prior art that a certain amount must be added, bi-, tri- and tetra-functional oxime silanes are prepared all at once, without the need to add bi- or tetra-functional oxime silanes separately. It is an object of the present invention to provide a method for preparing an oxime crosslinking agent for a silicone sealant, in which the crosslinking agent can be obtained in an excellent yield by allowing the to be carried out in one reactor.
상기와 같은 목적을 달성하기 위한 본 발명의 실리콘 실란트용 옥심형 가교제의 제조방법은 다음 화학식 3으로 표시되는 옥심 화합물, 다음 화학식 4로 표시되는 알코올 및 유기용제를 혼합 교반하면서 화학식 2로 표시되는 반응성 실란 및 테트라클로로실란을 상온에서 서서히 적가하는 1단계(여기서, 알코올: (상기 화학식 2로 표시되는 반응성 실란 및 테트라클로로실란 총량)=1:3～5 몰비임); 상기 1단계의 혼합물을 가온 반응시켜 유기용제, 옥심실란, 옥심화합물 및 미량의 옥심하이드로클로라이드로 이루어진 생성물층과 옥심하이드로클로라이드층으로 이루어진 반응혼합물을 수득하는 2단계; 상기 2단계의 반응혼합물을 층분리시키는 3단계; 및 상기 3단계에서 층분리된 상부 생성물층에 포함되어 있는 미량의 옥심하이드로클로라이드를 암모늄하이드로클로라이드로 중화시킨 후 여과시키고 승온감압증류로 유기용제 및 옥심화합물을 제거하여 다음 화학식 1로 표시되는 옥심실란 화합물 중에서 n=1이고 m=0인 3관능성 옥심실란 화합물, n, m=1인 2관능성 옥심실란 화합물 및 n, m=0인 4관능성 옥심실란 화합물을 함께 수득하는 4단계로 구성되는 것을 그 특징으로 한다.Method for producing an oxime crosslinking agent for a silicone sealant of the present invention for achieving the above object is a reaction represented by the formula (2) while mixing and stirring the oxime compound represented by the following formula (3), the alcohol represented by the following formula (4) and an organic solvent One step of slowly dropping silane and tetrachlorosilane at room temperature (wherein alcohol: (total amount of reactive silane and tetrachlorosilane represented by Formula 2) = 1: 3 to 5 molar ratio); Heating and reacting the mixture of step 1 to obtain a reaction mixture comprising an organic solvent, an oxime silane, an oxime compound, and a trace amount of an oxime hydrochloride and an oxime hydrochloride layer; Three steps of separating the reaction mixture of the two steps; And neutralizing the trace amount of oxime hydrochloride contained in the upper product layer separated in step 3 with ammonium hydrochloride, followed by filtration and removing the organic solvent and oxime compound by depressurizing distillation under reduced pressure. Consists of four steps to obtain a trifunctional oxime silane compound of n = 1 and m = 0, a bifunctional oxime silane compound of n, m = 1 and a tetrafunctional oxime silane compound of n, m = 0 It is characterized by that.
R1은 CH3, C2H5, C6H5또는 CH=CH2이고, R2는 H, CH3, OCH3, OC2H5또는 OC3H7이며, R' 는 H, CH3, C2H5, C3H7또는 C6H5이고, R"는 CH3, C2H5, C3H7또는 C6H5이고, n은 0～3의 정수이고, m은 0 또는 1이다.R 1 is CH 3 , C 2 H 5 , C 6 H 5 or CH = CH 2 , R 2 is H, CH 3 , OCH 3 , OC 2 H 5 or OC 3 H 7 , and R 'is H, CH 3 , C 2 H 5 , C 3 H 7 or C 6 H 5 , R ″ is CH 3 , C 2 H 5 , C 3 H 7 or C 6 H 5 , n is an integer from 0 to 3, m Is 0 or 1.
상기 식에서, R3는 Cl, CH3, C2H5또는 CH=CH2이고, R4는 Cl 또는 COOCH3이며,은 1～3의 정수이다.Wherein R 3 is Cl, CH 3 , C 2 H 5 or CH = CH 2 , R 4 is Cl or COOCH 3 , Is an integer of 1 to 3.
상기 식에서, R'와 R''는 상기 화학식 1에서 정의한 것과 같다.In the above formula, R 'and R' 'are as defined in the formula (1).
상기 식에서, R5는 CH3, C2H5또는 C3H7이다.Wherein R 5 is CH 3 , C 2 H 5 or C 3 H 7 .
이와 같은 본 발명의 제조방법을 더욱 상세하게 설명하면 다음과 같다.The production method of the present invention will be described in more detail as follows.
먼저, 1단계에서는 상기 화학식 3으로 표시되는 옥심화합물과 상기 화학식 4으로 표시되는 알코올 및 유기용제를 수분이 완전히 건조된 반응기에 투입하고 이 혼합물을 마그네틱 스터러로 교반하면서 적가장치를 사용하여 화학식 2로 표시되는 실란과 테트라클로로실란을 혼합하여 서서히 적가한다.First, in step 1, the oxime compound represented by the formula (3), the alcohol and the organic solvent represented by the formula (4) are added to a reactor in which moisture is completely dried, and the mixture is stirred using a magnetic stirrer to add the formula (2). The silane represented by and tetrachlorosilane are mixed and added dropwise gradually.
그리고, 상기 화학식 2로 표시되는 실란으로는 메틸트리클로로실란, 에틸트리클로로실란, 비닐트리클로로실란, 메틸트리아세톡시실란, 에틸트리아세톡시실란, 비닐트리아세톡시실란 중에서 1종을 선택하여, 테트라클로로실란과 혼합사용하는것이 바람직하다. 이때, 화학식 2로 표시되는 반응성 실란에 대해 테트라클로로실란을 7～28몰%로 사용하는 것이 바람직하다.As the silane represented by Formula 2, one kind is selected from methyltrichlorosilane, ethyltrichlorosilane, vinyltrichlorosilane, methyltriacetoxysilane, ethyltriacetoxysilane, and vinyltriacetoxysilane. Preference is given to using in combination with tetrachlorosilane. At this time, it is preferable to use tetrachlorosilane at 7-28 mol% with respect to the reactive silane represented by General formula (2).
여기서, 상기 화학식 3으로 표시되는 옥심화합물의 예로는, 아세트알데히드옥심, 아세토논옥심, 1-부틸알데히드옥심, 메틸에틸케톤옥심(부타논옥심), 벤즈알데히드옥심, 아세토페논옥심 등의 사용이 가능한데, 실란(상기 화학식 2로 표시되는 반응성 실란과 테트라클로로실란 포함) 1몰에 대해 5.7～8.2몰비로 사용하는 것이 바람직하다.Here, examples of the oxime compound represented by Formula 3 include acetaldehyde oxime, acetonone oxime, 1-butylaldehyde oxime, methyl ethyl ketone oxime (butanone oxime), benzaldehyde oxime, acetophenone oxime, etc. It is preferable to use it with 5.7-8.2 molar ratio with respect to 1 mol of silane (including reactive silane represented by the said Formula (2) and tetrachlorosilane).
아울러, 상기 화학식 4로 표시되는 알코올류로는 메틸알코올, 에틸알코올 또는 프로필알코올 등이 사용가능하고, 유기용제로는 끓는점이 높지 않은 카본류 또는 케톤류 즉, 노르말펜탄, 노르말헥산, 사이클로헥산, 디에틸에테르, 톨루엔 또는 크실렌 등을 사용할 수 있는데, 유기용제는 중량비로 실란(화학식 2로 표시되는 반응성 실란과 테트라클로로실란 포함)의 1～2.5배로 사용하는 것이 바람직하다.In addition, methyl alcohol, ethyl alcohol or propyl alcohol may be used as the alcohols represented by Formula 4, and as the organic solvent, carbons or ketones having high boiling points, that is, normal pentane, normal hexane, cyclohexane, and di Ethyl ether, toluene or xylene may be used, but the organic solvent is preferably used in 1 to 2.5 times the silane (including reactive silane and tetrachlorosilane represented by the formula 2) by weight.
여기서, 알코올과 상기 화학식 2로 표시되는 반응성 실란 및 테트라클로로실란 총량의 사용비는 1:3～5 몰비인 것이 바람직하다. 이같은 알코올의 소량 첨가로 알콕시기를 갖는 2관능성 옥심실란을 생성물질로서 얻을 수 있다.Here, it is preferable that the use ratio of alcohol, the reactive silane represented by the said Formula (2), and the total amount of tetrachlorosilane is 1: 3-5 molar ratio. By addition of such a small amount of alcohol, a bifunctional oxime silane having an alkoxy group can be obtained as a product.
1단계의 반응시 실란을 20～240분, 바람직하게는 60～120분간에 걸쳐 서서히 적가하는데, 이때 반응기내 혼합물과 격렬한 발열반응이 일어나므로 얼음-물 중탕 (Ice-Water Bath)을 사용하여 반응온도를 15～40℃, 바람직하게는 20～30℃로 조절하여야 한다.In the first stage of reaction, the silane is slowly added dropwise over 20-240 minutes, preferably 60-120 minutes. At this time, a vigorous exothermic reaction occurs with the mixture in the reactor, so the reaction is carried out using an ice-water bath. The temperature should be adjusted to 15 to 40 ° C, preferably 20 to 30 ° C.
다음, 2단계에서는 상기와 같이 실란을 적가한 후 반응물을 50～130℃, 바람직하게는 60～100℃로 가온하여 10～240분, 바람직하게는 30～120분 반응시키면 두층으로 분리된다.In the second step, the silane is added dropwise as described above, and then the reactant is heated to 50 to 130 ° C., preferably 60 to 100 ° C., and reacted for 10 to 240 minutes, preferably 30 to 120 minutes, to be separated into two layers.
이때, 상층은 생성물층으로서, 유기용제, 옥심실란, 옥심화합물 및 미량의 옥심하이드로클로라이드가 포함되어 있으며; 하층은 액상 또는 고상인 옥심하이드로클로라이드(oxime HCI salt)층으로, 부산물인 옥심하이드로클로라이드와 미량의 옥심화합물, 유기용제 및 옥심실란이 포함되어 있다.At this time, the upper layer is a product layer, which contains an organic solvent, oxime silane, oxime compound and a small amount of oxime hydrochloride; The lower layer is a liquid or solid oxime hydrochloride (oxime HCI salt) layer, and includes by-product oxime hydrochloride and trace amounts of oxime compounds, organic solvents and oxime silanes.
3단계에서는 상기 2단계에서 수득된 두 층으로 분리된 반응물을 층분리시키는데, 이때에 층분리는 원심분리기를 이용하거나 또는 상부층을 조심스럽게 다른 반응기로 옮길 수 있으나, 이때 대기와의 접촉으로 상층 생성물(옥심실란)이 가수분해될 수 있는 바, 질소분위기하에서 더블 팁 니들(Doubls Tip Neelde)을 사용하여 층분리시키는 것이 바람직하다.In step 3, the reactants separated into two layers obtained in step 2 are separated, where the separation can be carried out using a centrifuge or the top layer can be carefully transferred to another reactor, but the upper layer product is brought into contact with the atmosphere. Since (oximesilane) can be hydrolyzed, it is preferable to separate the layers using a double tip needle (Doubls Tip Neelde) under a nitrogen atmosphere.
그런 다음, 4단계에서는 옥심형 가교제를 수득하기 위해서 층분리된 상층, 즉 생성물층에서 유기용제, 옥시화합물 및 옥심하이드로클로라이드를 제거한다. 감압증류를 통해 유기용제와 옥심화합물이 제거되나 감압증류시 옥심하이드로클로라이드가 폭발할 위험이 있는 것으로 보고된 바 있으므로(1974. 9.2.자 케미컬&엔지니어링 뉴스(Chemical & Engeneering News), p3 참조), 먼저 분리된 생성물층에 암모니아 가스를 충분히 통과시켜 부산물인 옥심하이드로클로라이드를 중화시키면 암모늄하이드로클로라이드로 전환되어 백색침전되므로, 이를 여과하여 제거한 후 승온 감압증류로 옥심화합물과 유기용제를 증류시켜 제거하면 옥심실란, 즉 옥심형 가교제를 수득할 수 있다.Then, in step 4, the organic solvent, the oxy compound and the oxime hydrochloride are removed from the separated layer, that is, the product layer, to obtain an oxime crosslinking agent. Decompression distillation removes organic solvents and oxime compounds, but it has been reported that oxime hydrochloride may explode during distillation (see Chemical & Engeneering News, p. 3, September 2, 1974). First, the ammonia gas is sufficiently passed through the separated product layer to neutralize oxime hydrochloride, which is a by-product, and is converted to ammonium hydrochloride. Thus, the precipitate is white precipitated. Therefore, the oxime compound and the organic solvent are distilled off under elevated pressure and distillation to remove oxime. Silanes, ie oxime crosslinkers, can be obtained.
이와 같은 방법을 통해 얻어진 옥심형 가교제는 통상의 제조방법에서와 같은 3관능성 옥심실란 단독 화합물이 아니라, 2관능성 옥심실란과 4관능성 옥심실란이 동시에 얻어지는 바, 일예로 메틸트리스(메틸에틸케톡시모) 실란을 주로 하여, 메틸메톡시비스(메틸에틸케톡시모) 실란과 테트라키스(메틸에틸케톡시모) 실란이 함께 얻어진다.The oxime crosslinking agent obtained through such a method is not a trifunctional oxime silane compound as in the conventional manufacturing method, but a bifunctional oxime silane and a tetrafunctional oxime silane are simultaneously obtained. For example, methyltris (methylethyl Mainly a methoxymo) silane, a methylmethoxybis (methylethyl methoxymo) silane and a tetrakis (methylethyl methoxymo) silane are obtained together.
본 발명에 있어서, 반응의 진행정도는 통상적인 방법, 즉 가스크로마토그래피, 질량분석기, 적외선 분광기 및 핵자기공명분석기 등을 사용하여 확인한다.In the present invention, the progress of the reaction is confirmed using conventional methods, ie, gas chromatography, mass spectrometry, infrared spectroscopy and nuclear magnetic resonance analyzer.
한편, 하층인 옥심하이드로클로라이드층은 중화시켜 암모늄하이드로클로라이드와 옥심화합물을 회수할 수 있다. 옥심하이드로클로라이드를 중화시키기 위해서는 먼저 암모니아가스를 옥심하이드로클로라이드에 통과시킨다. 이때 심한 발열반응이 진행되므로 얼음-물 중탕을 사용하여 반응온도를 10～30℃로 조절하여야 하고, 반응 중에 완전한 중화를 위하여 pH 측정기를 사용하여 혼합물의 산도를 수시로 측정하는 데, 혼합물의 산도가 7이 되면 옥심하이드로클로라이드를 회수하고, 그 나머지는 상온에서 감압하여 옥심화합물과 유기용제는 증류시켜 소량의 옥심실란을 수득한다.On the other hand, the lower oxime hydrochloride layer can be neutralized to recover the ammonium hydrochloride and oxime compound. To neutralize oxime hydrochloride, ammonia gas is first passed through oxime hydrochloride. At this time, since the exothermic reaction proceeds, the reaction temperature should be adjusted to 10 ~ 30 ℃ using ice-water bath, and the pH of the mixture is often measured by using a pH meter for complete neutralization during the reaction. When 7, the oxime hydrochloride is recovered, and the remainder is reduced at room temperature to distill the oxime compound and the organic solvent to obtain a small amount of oxime silane.
옥심하이드로클로라이드를 중화시키기 위한 또 다른 방법으로는 염기, 즉 10～50% 소듐하이드록사이드 용액 또는 포타슘하이드록사이드 용액, 바람직하게는 20～40%의 소듐하이드록사이드 용액을 사용하는 방법이 있다. 이 방법을 사용하여 옥심하이드로클로라이드층에 소듐하이드록사이드 용액을 천천히 적가하면 반응이 진행되면서 심한 발열반응이 발생되므로 얼음-물 중탕을 이용하여 반응온도를 10～30℃로 조절한다. 반응의 정도를 확인하기 위하여 pH 측정기로 혼합물의 산도를 수시로 측정하여 혼합물의 pH가 7이 되면 옥심하이드로클로라이드는 완전히 중화되어 옥심화합물과 소듐클로라이드가 생성된다. 옥심화합물의 정제를 위해 소듐클로라이드를 여과하고 25～100℃에서 감압(0.1～1.0torr) 증류한다.Another method for neutralizing oxime hydrochloride is to use a base, i.e. a 10-50% sodium hydroxide solution or a potassium hydroxide solution, preferably a 20-40% sodium hydroxide solution. . When the sodium hydroxide solution is slowly added dropwise to the oxime hydrochloride layer using this method, a severe exothermic reaction occurs as the reaction proceeds, so the reaction temperature is adjusted to 10 to 30 ° C. using an ice-water bath. In order to check the degree of reaction, the pH of the mixture was frequently measured by using a pH meter. When the pH of the mixture reached 7, the oxime hydrochloride was completely neutralized to form an oxime compound and sodium chloride. To purify the oxime compound, sodium chloride is filtered and distilled under reduced pressure (0.1 to 1.0 torr) at 25 to 100 ° C.
본 발명에서 회수되는 옥심화합물은 다시 옥심가교제의 제조에 재사용할 수 있다.The oxime compound recovered in the present invention can be reused to prepare the oxime crosslinker.
이하, 본 발명을 실시예에 의거 상세히 설명하면 다음과 같은 바, 본 발명이 이에 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the following Examples, but the present invention is not limited thereto.
실시예 1Example 1
온도계, 질소투입계, 적가장치 및 콘덴서가 설치된 500㎖ 3구 플라스크에 메틸에틸케톤옥심(CH3CH2CH2C=NOH) 173.4g(1.990몰)과 메틸알코올(CH3OH) 3.040g(0.095몰) 및 유기용제인 톨루엔 112.1g을 투입한 후, 마그네틱 스터러로 천천히 교반하면서 반응성 실란으로 메틸트리클로로실란(CH3SiCl3) 47.2g(0.316몰)을 적가장치를 통하여 서서히 혼합물에 적가하였다. 이때 얼음-물 중탕을 사용하여 반응온도를 20～30℃ 사이로 유지시켰다. 그런 다음 반응혼합물의 온도를 20～30℃로 유지시키면서 반응성 실란인 테트라클로로실란(Cl4Si) 8.87g(0.024몰)을 서서히 적가하고 반응혼합물의 온도를 70℃로 승온하여 60분간 반응시켰더니 상온에서 두 층, 즉 투명한 저점도의 생성물층인 상층과 고점도의 옥심하이드로클로라이드층인 하층으로 분리되었다. 두 층을 질소분위기 하에서 더블 팁 니들을 사용하여 분리한 후 상층에 암모니아 가스를 통과시켜 침전된 암모늄하이드로클로라이드를 여과시킨 다음, 60℃, 0.5torr로 40분간 승온감압하여 생성물(옥심실란)을 얻었다. 그리고, 하층은 40% 소듐하이드록시 수용액을 이용하여 pH 7로 중화시켜 84.6g(93.1%)의 메틸에틸케톤을 회수하였다. 가스크로마토그래피와 질량분석기를 이용하여 생성물을 확인한 결과, 메틸트리스(메틸에틸케톡시모) 실란 78.0g(83.5%), 메틸메톡시비스(메틸에틸케톡시모) 실란 7.3g(7.8%) 및 테트라키스(메틸에틸케톡시모) 실란 8.1g(8.7%)으로 확인되었으며, 수율은 91.0%이었다.173.4 g (1.990 mole) of methyl ethyl ketone oxime (CH 3 CH 2 CH 2 C = NOH) and 3.040 g of methyl alcohol (CH 3 OH) in a 500 ml three-necked flask equipped with a thermometer, a nitrogen input system, a dropping device and a condenser. 0.095 mol) and 112.1 g of toluene, an organic solvent, were added thereto, and then 47.2 g (0.316 mol) of methyl trichlorosilane (CH 3 SiCl 3 ) was slowly added dropwise to the mixture with a reactive silane while stirring slowly with a magnetic stirrer. It was. At this time, the reaction temperature was maintained between 20 ~ 30 ℃ using ice-water bath. Then, while maintaining the temperature of the reaction mixture at 20-30 ° C, 8.87 g (0.024 mol) of tetrachlorosilane (Cl 4 Si), which is a reactive silane, was slowly added dropwise, and the reaction mixture was heated to 70 ° C for 60 minutes to react. In two layers, the upper layer which is the transparent low viscosity product layer and the lower layer which is the high viscosity oxime hydrochloride layer. The two layers were separated using a double tip needle under a nitrogen atmosphere, and ammonia gas was passed through the upper layer, and the precipitated ammonium hydrochloride was filtered and then decompressed at 60 ° C. and 0.5 torr for 40 minutes to obtain a product (oxime silane). . The lower layer was neutralized to pH 7 using 40% aqueous sodium hydroxy solution to recover 84.6 g (93.1%) of methyl ethyl ketone. The product was identified using gas chromatography and mass spectrometry. 78.0 g (83.5%) of methyltris (methylethylketoxymo) silane, 7.3g (7.8%) of methylmethoxybis (methylethylketoxymo) silane and tetrakis (Methylethylketoxymo) silane was identified as 8.1g (8.7%), yield was 91.0%.
실시예 2Example 2
메틸에틸케톤옥심 219.1g(2.515몰), 메틸알코올 2.56g(0.080몰), 톨루엔 101.3g, 메틸트리클로로실란 46.1g(0.266몰) 및 테트라클로로실란 4.57g(0.027몰)을 사용한 것 이외에는 상기 실시예 1과 동일한 방법으로 옥심실란을 제조하였다. 메틸에틸케톤 73.2g(92.8%)을 회수하였으며, 옥심실란을 분석하였더니 메틸트리스(메틸에틸케톡시모) 실란 66.2g(81.3%), 메틸메톡시비스(메틸에틸케톡시모) 실란 5.98g(7.3%) 및 테트라키스(메틸에틸케톡시모) 실란 9.20g(11.3%)로 확인되었으며, 수율은 91.0%이었다.The above procedure was carried out except that 219.1 g (2.515 mol) of methyl ethyl ketone oxime, 2.56 g (0.080 mol) of methyl alcohol, 101.3 g of toluene, 46.1 g (0.266 mol) of methyltrichlorosilane and 4.57 g (0.027 mol) of tetrachlorosilane were used. An oxime silane was prepared in the same manner as in Example 1. 73.2 g (92.8%) of methyl ethyl ketone was recovered, and 66.2 g (81.3%) of methyltris (methylethylketoxymo) silane and 5.98 g (7.3% of methyl methoxybis (methylethylketoxymo) silane were analyzed. %) And 9.20 g (11.3%) of tetrakis (methylethylketoxymo) silane with a yield of 91.0%.
실시예 3Example 3
메틸에틸케톤옥심 198.9g(2.283몰), 메틸알코올 3.18g(0.090몰), 톨루엔 135.8g, 메틸트리클로로실란 49.5g(0.331몰) 및 테트라클로로실란 18.4g(0.049몰)을 사용한 것 이외에는 상기 실시예 1과 동일한 방법으로 옥심실란을 제조하였다. 메틸에틸케톤 95.6g(92.2%)을 회수하였으며, 옥심실란을 분석하였더니 메틸트리스(메틸에틸케톡시모) 실란 81.7g(77.1%), 메틸메톡시비스(메틸에틸케톡시모) 실란 7.42g(6.3%) 및 테트라키스(메틸에틸케톡시모) 실란 16.8g(15.9%)로 확인되었으며, 수율은 91.0%이었다.The above procedure was carried out except that 198.9 g (2.283 mole) of methyl ethyl ketone oxime, 3.18 g (0.090 mole) of methyl alcohol, 135.8 g of toluene, 49.5 g (0.331 mole) of methyltrichlorosilane and 18.4 g (0.049 mole) of tetrachlorosilane were used. An oxime silane was prepared in the same manner as in Example 1. 95.6 g (92.2%) of methyl ethyl ketone was recovered, and oxime silane was analyzed. As a result, 81.7 g (77.1%) of methyltris (methyl ethyl methoxymo) silane and 7.42 g (6.3 of methyl methoxybis (methyl ethyl methoxymo) silane were obtained. %) And 16.8 g (15.9%) of tetrakis (methylethylketoxymo) silane. The yield was 91.0%.
실시예 4Example 4
메틸에틸케톤옥심 201.0g(2.307몰), 메틸알코올 3.12g(0.097몰), 톨루엔 139.6g, 메틸트리클로로실란 48.5g(0.324몰) 및 테트라클로로실란 21.3g(0.057몰)을 사용한 것 이외에는 상기 실시예 1과 동일한 방법으로 옥심실란을 제조하였다. 메틸에틸케톤 96.8g(92.8%)을 회수하였으며, 옥심실란을 분석하였더니 메틸트리스(메틸에틸케톡시모) 실란 81.4g(75.0%), 메틸메톡시비스(메틸에틸케톡시모) 실란 7.39g(6.8%) 및 테트라키스(메틸에틸케톡시모) 실란 19.70g(18.2%)로 확인되었으며, 수율은 92.5%이었다.The above procedure was carried out except that 201.0 g (2.307 mol) of methyl ethyl ketone oxime, 3.12 g (0.097 mol) of methyl alcohol, 139.6 g of toluene, 48.5 g (0.324 mol) of methyltrichlorosilane and 21.3 g (0.057 mol) of tetrachlorosilane were used. An oxime silane was prepared in the same manner as in Example 1. 96.8 g (92.8%) of methyl ethyl ketone was recovered, and oxime silane was analyzed, and 81.4 g (75.0%) of methyltris (methylethyl methoxymo) silane and 7.39 g (6.8 of methyl methoxybis (methylethyl methoxymo) silane were obtained. %) And 19.70 g (18.2%) of tetrakis (methylethylketoxymo) silane with a yield of 92.5%.
실시예 5Example 5
메틸에틸케톤옥심 227.1g(2.607몰), 메틸알코올 3.25g(0,101몰), 톨루엔 129.9g, 메틸트리클로로실란 50.6g(0.399몰) 및 테트라클로로실란 14.4g(0.085몰)을 사용한 것 이외에는 상기 실시예 1과 동일한 방법으로 옥심실란을 제조하였다. 메틸에틸케톤 109.4g(92.7%)을 회수하였으며, 옥심실란을 분석하였더니 메틸트리스 (메틸에틸케톡시모) 실란 83.9g(69.7%), 메틸메톡시비스(메틸에틸케톡시모) 실란 7.6g(6.3%) 및 테트라키스(메틸에틸케톡시모) 실란 28.8g(23.9%)로 확인되었으며, 수율은 91.3%이었다.The above procedure was carried out except that 227.1 g (2.607 mol) of methyl ethyl ketone oxime, 3.25 g (0,101 mol) of methyl alcohol, 129.9 g of toluene, 50.6 g (0.399 mol) of methyltrichlorosilane and 14.4 g (0.085 mol) of tetrachlorosilane were used. An oxime silane was prepared in the same manner as in Example 1. 109.4 g (92.7%) of methyl ethyl ketone was recovered and 83.9 g (69.7%) of methyltris (methylethyl methoxymo) silane and 7.6 g (6.3 g) of methyl methoxybis (methyl ethyl methoxymo) silane were analyzed. %) And 28.8 g (23.9%) of tetrakis (methylethylketoxymo) silane with a yield of 91.3%.
비교예 1Comparative Example 1
상기 실시예 1과 동일한 장치에 메틸에틸케톤옥심 187.1g(2.148몰)과 노르말헥산 80.3g을 투입한 후 마그네틱 스터러로 천천히 교반함과 동시에 반응혼합물의 온도를 얼음-물 중탕을 사용하여 20～30℃로 유지하면서 메틸트리클로로실란 53.5g(0.358몰)을 적가장치를 통해 천천히 적가하고, 반응혼합물을 60℃로 가온하여 60분간 반응시켰더니 상온에서 두층, 즉 저점도의 생성물층인 상층과 고점도의 옥심하이드로클로라이드층인 하층으로 분리되었다. 두 층을 분리한 후, 상층에 암모니아 가스를 통과시켜 침전된 백색의 암모늄하이드로클로라이드를 여과시킨 다음, 40℃, 0.5torr로 승온감압하에 60분간 방치하여 생성물을 수득하였다. 하층은 40% 소듐하이드록시 수용액을 이용하여 중화(pH=7)시켜 메틸에틸케톤 84.7g(90.6%)를 회수하였다. 가스크로마토그래피와 질량분석기를 이용하여 생성물을 분석하였더니 메틸트리스(메틸에틸케톡시모) 실란 90.7g으로 확인되었으며, 수율은 84.1%이었다.187.1 g (2.148 mol) of methyl ethyl ketone oxime and 80.3 g of normal hexane were added to the same apparatus as in Example 1, and the mixture was stirred slowly with a magnetic stirrer and the temperature of the reaction mixture was adjusted from 20 to 20 using an ice-water bath. 53.5 g (0.358 mol) of methyltrichlorosilane was slowly added dropwise while maintaining at 30 DEG C, and the reaction mixture was allowed to react for 60 minutes by heating to 60 DEG C. At room temperature, two layers, that is, the upper layer, which is the product layer of low viscosity, and high viscosity It separated into the lower layer which is the oxime hydrochloride layer of. After separating the two layers, the white layer of ammonium hydrochloride precipitated by passing ammonia gas through the upper layer was filtered, and left for 60 minutes under reduced pressure at 40 ℃, 0.5torr to obtain a product. The lower layer was neutralized using a 40% aqueous sodium hydroxy solution (pH = 7) to recover 84.7 g (90.6%) of methyl ethyl ketone. The product was analyzed using gas chromatography and mass spectrometry. As a result, 90.7 g of methyltris (methylethylketoxymo) silane was obtained. The yield was 84.1%.
비교예 2Comparative Example 2
메틸에틸케톤옥심 175.4g(2.013몰), 메틸알코올 3.39g(0.106몰), n-헥산 78.2g 및 메틸트리클로로실란 52.8g(0.353몰)을 사용한 것 이외에는 상기 비교예 1과 같은 방법으로 가교제 옥심실란을 수득하였다. 메틸에틸케톤 84.5g(91.5%)를 회수하였으며, 생성물을 분석하였더니 메틸트리스(메틸에틸케톡시모) 실란 83.8g(90.0%)와 메틸메톡시비스(메틸에틸케톡시모) 실란 7.37g(10.0%)로 확인되었으며, 수율은 87.5%이었다.Crosslinking agent oxime in the same manner as in Comparative Example 1 except that 175.4 g (2.013 mol) of methyl ethyl ketone oxime, 3.39 g (0.106 mol) of methyl alcohol, 78.2 g of n-hexane and 52.8 g (0.353 mol) of methyltrichlorosilane were used. Silane was obtained. 84.5 g (91.5%) of methyl ethyl ketone was recovered, and the product was analyzed, and 83.8 g (90.0%) of methyltris (methylethylketoxymo) silane and 7.37 g (10.0%) of methylmethoxybis (methylethylketoxymo) silane were recovered. ), Yield was 87.5%.
상기의 본 발명에 따른 실시예와 종래 비교예에 의한 가교제의 수율을 비교해보면, 본 발명에 의한 것이 91.0% 이상인 반면에, 종래기술에 의한 것은 85% 정도임을 알 수 있다. 무엇보다도, 3관능성 옥심실란, 즉 메틸트리스(메틸에틸케톡시모) 실란만을 단독으로 생성하는 것이 아니라 2관능성 옥심실란과 4관능성 옥심실란이 함께 생성되므로, 3관능성 옥심실란을 실리콘실란트 제조시 가교제로 사용함에 있어서 실란트의 경화속도 및 가교밀도를 조절하기 위해 별도로 2관능성 옥심실란과 4관능성 옥심실란을 첨가하는 번거로움이 없고 별도로 3관능성 옥심실란을 분리한 후 혼합하지 않아도 되므로 높은 수율로 옥심형 가교제를 수득할 수 있는 장점이 있다.Comparing the yield of the crosslinking agent according to the embodiment according to the present invention and the conventional comparative example, it can be seen that while according to the present invention is 91.0% or more, about 85% according to the prior art. First of all, trifunctional oxime silanes, i.e., not only methyltris (methylethylketoxymo) silane, but bifunctional oxime silanes and tetrafunctional oxime silanes are produced together. In use as a crosslinking agent in the manufacturing process, there is no need to add bifunctional oxime silane and tetrafunctional oxime silane separately to control the curing rate and crosslinking density of the sealant, and the trifunctional oxime silane is not separated and mixed separately. Therefore, there is an advantage to obtain an oxime crosslinking agent in a high yield.
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