KR100342576B1 - Process for preparing acetoxy type crosslinking agent for silicone silant - Google Patents
Process for preparing acetoxy type crosslinking agent for silicone silant Download PDFInfo
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- KR100342576B1 KR100342576B1 KR1019950002213A KR19950002213A KR100342576B1 KR 100342576 B1 KR100342576 B1 KR 100342576B1 KR 1019950002213 A KR1019950002213 A KR 1019950002213A KR 19950002213 A KR19950002213 A KR 19950002213A KR 100342576 B1 KR100342576 B1 KR 100342576B1
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- crosslinking agent
- type crosslinking
- general formula
- silane
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- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 title abstract 5
- 229920001296 polysiloxane Polymers 0.000 title abstract 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000077 silane Inorganic materials 0.000 claims abstract description 20
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000004590 silicone sealant Substances 0.000 claims description 12
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 10
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical group CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 9
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 8
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 claims description 8
- 239000012346 acetyl chloride Substances 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 2
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 2
- 238000007039 two-step reaction Methods 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 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 9
- 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 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- BTHCBXJLLCHNMS-UHFFFAOYSA-N acetyloxysilicon Chemical compound CC(=O)O[Si] BTHCBXJLLCHNMS-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- -1 polydimethylsiloxane Polymers 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OJKQPMBOMUDGDS-UHFFFAOYSA-N (acetyloxy-ethyl-propoxysilyl) acetate Chemical compound C(C)[Si](OC(C)=O)(OC(C)=O)OCCC OJKQPMBOMUDGDS-UHFFFAOYSA-N 0.000 description 1
- PVPZARMJQOEIBT-UHFFFAOYSA-N (acetyloxy-methyl-propoxysilyl) acetate Chemical compound CCCO[Si](C)(OC(C)=O)OC(C)=O PVPZARMJQOEIBT-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000005053 propyltrichlorosilane Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- DOEHJNBEOVLHGL-UHFFFAOYSA-N trichloro(propyl)silane Chemical compound CCC[Si](Cl)(Cl)Cl DOEHJNBEOVLHGL-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming 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
- C07F7/1896—Compounds having one or more Si-O-acyl linkages
-
- 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
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C 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)
- Silicon Polymers (AREA)
Abstract
Description
본 발명은 실리콘 실란트용 초산형 가교제에 관한 것으로서, 특히 수분 경화형 실란트에 사용되는 초산형 가교제의 제조방법에 관한 것이다.The present invention relates to an acetic acid type crosslinking agent for silicone sealants, and more particularly to a method for producing an acetic acid type crosslinking agent used in a moisture curable sealant.
일반적인 초산형 가교제는 상온에서 수분과 쉽게 반응하여 초산기가 떨어지면서 실란올, 실리카, 피착층 등의 하이드록시기와 반응하여 가교되는 것으로, 물 존재하에서 αω-하이드록시폴리디메틸실록산과 가수분해 및 축합반응을 하여 αω-비스(메틸디아세톡시실록시)폴리디메틸실록산이 된다.A common acetic acid crosslinking agent reacts easily with water at room temperature and falls with acetic acid, and crosslinks by reacting with hydroxyl groups such as silanol, silica, and adhesion layer, and hydrolysis and condensation reaction with αω-hydroxypolydimethylsiloxane in the presence of water. To (alpha) -bis (methyl diacetoxy siloxy) polydimethylsiloxane.
한편, 실리콘 실란트에 사용되는 초산형 가교제는 메틸트리아세톡시실란을 단독으로 초산형 가교제에 사용했을 경우에는 상온 및 저온에서 결정화 되기 때문에 사용이 어려우며, 에틸트리아세톡시실란을 단독으로 사용했을 경우에는 경화 속도가 떨어져 실리콘 실란트용으로 사용하기에는 부적합하기 때문에 메틸트리아세톡시 실란과 에틸트리아세톡시실란을 적정비율, 즉 5~40중량부 : 100중량부의 비율로 혼합 사용하여 제조하였다.On the other hand, the acetic acid type crosslinking agent used in the silicone sealant is difficult to use because it is crystallized at room temperature and low temperature when methyltriacetoxysilane is used alone in the acetic acid type crosslinking agent, and when ethyltriacetoxysilane is used alone, Since the curing rate was not suitable for use for the silicone sealant, methyltriacetoxy silane and ethyl triacetoxy silane were mixed and used in an appropriate ratio, that is, 5 to 40 parts by weight: 100 parts by weight.
그러나, 메틸트리아세톡시실란과 에틸트리아세톡시실란을 혼합하는 경우, 메틸트리아세톡시실란(녹는점:32℃)이 상온에서 고상이기 때문에 이를 녹이는 공정이필요하고, 아울러 대기와의 접촉에 의한 가수분해 현상으로 가교제의 순도가 저하되는 등의 문제점이 발생하였다.However, when methyltriacetoxysilane and ethyltriacetoxysilane are mixed, a process of melting the methyltriacetoxysilane (melting point: 32 ° C.) is a solid at room temperature, and a process for dissolving it is required. The hydrolysis phenomenon has caused a problem such that the purity of the crosslinking agent is lowered.
이러한 종래의 실리콘 실란트용 초산형 가교제의 제조방법으로는 미국특허 제3,974,198호로 메틸트리클로로실란, 무수초산 및 헥산을 사용하는 방법과, 미국특허 제4,329,484호로 메틸트리아세톡시실란을 연속적으로 생산하면서 제조하는 방법이 개시된 바 있으나, 이들 두 방법 모두는 메틸트리아세톡시실란의 녹는점이 높은 관계로 중간생성물의 증류시 증류관 내부에서, 그리고 저장중 상온에서 결정화되므로 반응기의 보온이 필요하며, 메틸트리아세톡시실란과 에틸트리아세톡시실란을 별도의 공정으로 생산한 후 혼합해야 하는 단점이 있고, 특히 전자의 경우 반응완료후 용제를 제거해야 하는 단점이 있다.As a conventional method for preparing an acetic acid type crosslinking agent for silicone sealant, a method using methyl trichlorosilane, acetic anhydride and hexane in US Pat. Although both methods have been disclosed, both of these methods have a high melting point of methyltriacetoxysilane, so crystallization is carried out inside the distillation tube during distillation of the intermediate product and at room temperature during storage. The oxysilane and ethyltriacetoxysilane have to be mixed and produced after a separate process, and in the former case, the solvent has to be removed after completion of the reaction.
따라서 본 발명은 상기한 종래기술의 문제점을 해결하고자 한 것으로, 그 목적은 메틸트리아세톡시실란과 에틸트리아세톡시실란 및 알콕시가 치환된 아세톡시실란을 한 공정에서 합성하여 메틸트리아세톡시실란이 반응기 안에서 결정화되는 것을 방지하고, 에틸트리아세톡시실란과 혼합하는 단계를 줄여 수율을 높이면서 제조공정을 단순화시킨 실리콘 실란트용 초산형 가교제의 제조방법을 제공하는데 있다.Therefore, the present invention is to solve the above problems of the prior art, the purpose of the synthesis of methyltriacetoxysilane, ethyl triacetoxysilane and aceoxysilane substituted alkoxy substituted in one step is methyl triacetoxysilane is The present invention provides a method for preparing an acetic acid type crosslinking agent for a silicone sealant which prevents crystallization in a reactor and reduces the mixing step with ethyltriacetoxysilane to increase the yield and simplify the manufacturing process.
상기 본 발명의 목적을 달성하기 위한 실리콘 실란트용 초산형 가교제의 제조방법은, 일반식(2)로 표시되는 실란과 일반식(3)으로 표시되는 산무수물을 질소분위기하에서 1:3~5의 몰비로 혼합 교반하면서 30~70℃ 70~170℃에서 0.5~3시간 반응시켜 일반식(1)의 m이 0인 실란을 수득하는 1단계와; 1단계에서 수득한 실란 1몰에 대하여 0.0054~0.16 몰비로 일반식(4)로 표시되는 알코올화합물을 적가하여 반응시키는 2단계; 및, 2단계의 반응혼합물을 승온감압하에 아세틸클로라이드 및 잔존 산무수물을 증류시켜 일반식(1)로 표시되는 초산형 가교제를 수득하는 3단계를 포함한다.The method for producing an acetic acid type crosslinking agent for a silicone sealant for achieving the object of the present invention, the silane represented by the general formula (2) and the acid anhydride represented by the general formula (3) of 1: 3 ~ 5 in a nitrogen atmosphere 1 step of reacting 0.5 to 3 hours at 30 to 70 ° C. and 70 to 170 ° C. while mixing and stirring at a molar ratio to obtain a silane having m of General Formula (1) 0; Two steps of reacting by dropwise addition of the alcohol compound represented by the general formula (4) at a molar ratio of 0.0054 to 0.16 to 1 mole of the silane obtained in the first step; And three steps of distilling the acetyl chloride and the remaining acid anhydride under reduced pressure in the reaction mixture of two steps to obtain an acetic acid type crosslinking agent represented by the general formula (1).
일반식(1)~(5)에서 R',R"는 탄소원자가 1~8인 알킬기이고,In formulas (1) to (5), R ', R "is an alkyl group having 1 to 8 carbon atoms,
n은 1~3 사이의 정수이며,n is an integer between 1 and 3,
m은 0 또는 1이다.m is 0 or 1;
상기에서 일반식(5)로 표시되는 초산류는 본 발명 제조방법의 1단계에서 일반식(3)으로 표시되는 산무수물 대신 사용 가능하나, 이를 사용하게 되면 일반식 (2)로 표시되는 실란과 반응시 염산이 발생하여 반응용기, 즉 반응기의 접착부 금속부분을 부식시키고 아울러 인체에 해를 줄 수 있으므로 이의 사용에는 주의해야 한다.Acetic acid represented by the general formula (5) above can be used in place of the acid anhydride represented by the general formula (3) in the first step of the production method of the present invention, and when used, the silane represented by the general formula (2) and During the reaction, hydrochloric acid may be generated, which may corrode the reaction vessel, that is, the metal part of the reactor, and damage the human body.
이하 본 발명을 더욱 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail.
일반식(1)로 표시되는 초산형 가교제를 제조하기 위해서는, 먼저 1단계에서 일반식(2)로 표시되는 실란류 1종 이상을 반응기에 투입하고 일반식(3)으로 표시되는 산무수물, 바람직하게는 아세트산 무수물을 1:3~5의 몰비로 투입하여 마그네틱스터러 등으로 교반하면서 30~70℃로 온도를 유지시키면서 반응시킨다. 이 반응에서는 실란의 관능기에 산무수물이 하나 이상 치환되어 실란이 증류되지 않게되며(예:메틸클로로실란의 경우 끊는점:66℃), 추후 부산물로 생성되는 아세틸클로라이드(끊는점:52℃)를 증류할 때 실란이 증류되지 않게 되므로 본 발명의 초산형 가교제 제조 수율을 높일 수 있다. 그런다음, 반응온도를 70~170℃로 승은시킨 후 0.5~3시간 반응시켜 부산물을 증류시키면 일반식(1)의 m이 0인 실란이 합성된다.In order to manufacture the acetic acid type crosslinking agent represented by the general formula (1), at least one silane represented by the general formula (2) in one step is first introduced into the reactor and an acid anhydride represented by the general formula (3), preferably Preferably, acetic anhydride is added in a molar ratio of 1: 3 to 5 and reacted while maintaining the temperature at 30 to 70 ° C. while stirring with a magnetic stirrer or the like. In this reaction, one or more acid anhydrides are substituted in the functional group of the silane so that the silane is not distilled (e.g., methyl chlorosilane break point: 66 ℃), and acetyl chloride (break point: 52 ℃) produced as a by-product later Since the silane is not distilled when distilling, it is possible to increase the yield of the acetate type crosslinking agent of the present invention. Then, after the reaction temperature is raised to 70 ~ 170 ℃ and reacted by 0.5 to 3 hours to distill the by-products silane of m in the general formula (1) is synthesized.
상기에서 일반식(2)의 실란류로는 메틸트리클로로실란, 에틸트리클로로실란, 프로필트리클로로실란, 비닐트리클로로실란의 사용이 가능하며, 에틸트리클로로실란에 메틸트리클로로실란이나 비닐트리클로로실란을 0.5~10:1의 몰비로 혼합하여 사용하는 것이 바람직하다.As the silanes of the general formula (2), methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane and vinyltrichlorosilane may be used, and methyltrichlorosilane or vinyltrichloro is used as ethyltrichlorosilane. It is preferable to mix and use a silane in the molar ratio of 0.5-10: 1.
2단계에서는 1단계에서 수득된 일반식(1)의 m이 0인 실란에 일반식(4)로 표시되는 알코올류를 1:0.0054~0.16의 몰비로 적가장치를 통하여 3~20분에 걸쳐 서서히 투입한 후 5~30분간 반응시키는데, 알코올을 상기 범위로 사용하는 경우 생성되는 실란, 예를 들어 메틸트리클로로실란과 에틸트리클로로실란의 작용기중에 하나 내지 둘이 알콜기로 치환되게 된다.In the second step, alcohols represented by the general formula (4) are gradually added to the silane having m of Formula (1) obtained in Step 1 in a molar ratio of 1: 0.0054 to 0.16 over 3-20 minutes through a dropping device. After the addition, the reaction is carried out for 5 to 30 minutes, when the alcohol is used in the above range, one or two of the functional groups of the produced silane, for example, methyltrichlorosilane and ethyltrichlorosilane, are substituted with an alcohol group.
3단계에서는 반응기의 압력을 10~30torr로 유지한 상태에서 온도를 0~70℃와80~120℃로 각각 유지시켜 부산물인 아세틸클로라이드와 일반식(3)으로 표시되는 산무수물 및 생성물인 일반식(1)로 표시되는 실란을 증류시켜 원하는 초산형 가교제를 얻을 수 있다.In the third step, the temperature is maintained at 0 to 70 ° C. and 80 to 120 ° C. while maintaining the pressure of the reactor at 10 to 30 torr, respectively, by-product acetyl chloride and acid anhydride and product represented by the general formula (3). The silane represented by (1) can be distilled off and a desired acetate type crosslinking agent can be obtained.
이하, 본 발명의 바람직한 실시예를 상세히 설명하고자 한다.Hereinafter, preferred embodiments of the present invention will be described in detail.
실시예1Example 1
증류관, 적가장치, 마그네틱스터러 및 질소투입계가 설치된 3구둥근플라스크에 메틸트리클로로 실란(CH3SiCl3) 150g(1몰)과, 에틸트리클로로실란(C2H5SiCl3) 818g(5몰)과, 산무수물 [(CH3CO)2O] 2,389g(23.4몰)을 질소분위기하에서 투입, 70℃로 가온하여 1시간 반응시킨 후, 온도를 120℃로 올려 30분, 150℃로 올려 30분 반응시킨다. 그런 다음, 프로필알콜(CH2CH2CH2OH) 24g(0.4몰)을 10분에 걸쳐 적가장치를 통해 주입하고 30분후에 반응을 완료하였다. 이때 반응의 완료 여부는 가스크로마토그래피를 이용하여 확인하였다. 그리고, 20torr 압력하에서 90℃로 서서히 가온시키면서 아세틸클로라이드와 과량 투입된 산무수물을 제거하고, 90~130℃까지 가온시켜 메틸프로폭시디아세톡시실란, 에틸트리아세톡시실란, 에틸프로폭시디아세톡시실란이 혼합된 아세톡시실란을 제조하였다. (수율:95%)150 g (1 mol) of methyl trichloro silane (CH 3 SiCl 3 ) and 818 g of ethyl trichlorosilane (C 2 H 5 SiCl 3 ) in a three-necked flask equipped with a distillation tube, a dropping device, a magnetic stirrer and a nitrogen input system. 5 moles) and 2,389 g (23.4 moles) of acid anhydride [(CH 3 CO) 2 O] were added under a nitrogen atmosphere, heated to 70 ° C. for 1 hour, and the temperature was increased to 120 ° C. for 30 minutes and 150 ° C. To 30 minutes of reaction. Then, 24 g (0.4 mol) of propyl alcohol (CH 2 CH 2 CH 2 OH) was injected through the dropper over 10 minutes, and the reaction was completed after 30 minutes. At this time, the completion of the reaction was confirmed using gas chromatography. Then, while slowly warming to 90 ° C. under 20torr pressure, acetyl chloride and excess acid anhydride were removed, and then heated to 90-130 ° C. to methylpropoxydiacetoxysilane, ethyltriacetoxysilane, and ethylpropoxydiacetoxysilane. This mixed acetoxysilane was prepared. (Yield: 95%)
실시예2Example 2
메틸트리클로로실란 293g(2몰), 에틸트리클로로실란 327g(2몰), 산무수물 [(CH3CO)2O] 1.593g(15.6몰) 및 프로필알콜 24g(0.4몰)을 사용한 것 이외에는 실시예1과 동일한 방법으로 아세톡시실란을 제조하였다. (수율:94%)Except that 293 g (2 mol) of methyltrichlorosilane, 327 g (2 mol) of ethyltrichlorosilane, 1.593 g (15.6 mol) of acid anhydride [(CH 3 CO) 2 O] and 24 g (0.4 mol) of propyl alcohol were used. Acetoxysilane was prepared in the same manner as in Example 1. (Yield: 94%)
실시예3Example 3
메틸트리클로로실란 598g(4몰), 에틸트리클로로실란 327g(2몰), 산무수물 [(CH3CO)2O] 2,389g(23.4몰) 및 프로필알콜 24g(0.4몰)을 사용한 것 이외에는 실시예1과 동일한 방법으로 아세톡시실란을 제조하였다. (수율:94%)598 g (4 moles) of methyltrichlorosilane, 327 g (2 moles) of ethyltrichlorosilane, 2,389 g (23.4 moles) of acid anhydride [(CH 3 CO) 2 O] and 24 g (0.4 moles) of propyl alcohol were used. Acetoxysilane was prepared in the same manner as in Example 1. (Yield: 94%)
비교예1Comparative Example 1
실시예1과 동일한 장치에 메틸트리클로로실란 149g(1몰)과 산무수물 [(CH3CO)2O] 398g(3.9몰)을 질소분위기하에서 투입한 후, 120℃로 가온하여 2시간 반응시킨 것 이외에는 실시예1과 동일한 방법으로 메틸트리아세톡시실란을 제조하였다. (수율: 93%)149 g (1 mol) of methyltrichlorosilane and 398 g (3.9 mol) of acid anhydride [(CH 3 CO) 2 O] were added to a device similar to Example 1 under a nitrogen atmosphere, and then heated to 120 ° C. for 2 hours to react. Methyltriacetoxysilane was prepared in the same manner as in Example 1. (Yield 93%)
비교예2Comparative Example 2
환류관, 마그네틱스터러, 질소투입계가 설치된 2구둥근바닥 플라스크에 메틸트리클로로실란 150g(1몰), 에틸트리클로로실란 818g(5몰) 및 산무수물 [(CH3CO)2O] 2,389g(23.4몰)을 질소분위기하에서 투입한 후, 70~l50℃로 가열하여 25시간후 반응을 종료하였다. 이때 반응의 종료여부는 가스크로마토그래피를 이용 매시간 마다 확인하였다. 그린다음, 20torr 압력하에서 90℃로 서서히 가열하여 아세틸클로라이드와 산무수물을 제거하고, 90~130℃로 보다 가열하여 메틸트리아세톡시실란과 에틸트리아세톡시실란을 증류시켜 아세톡시실란을 제조하였다. (수율:94%)150 g (1 mol) of methyltrichlorosilane, 818 g (5 mol) of ethyltrichlorosilane, and acid anhydride [(CH 3 CO) 2 O] 2,389 g (23.4 moles) was added under a nitrogen atmosphere, and the reaction was terminated after 25 hours by heating to 70 to 50 ° C. At this time, the completion of the reaction was confirmed every hour using gas chromatography. Then, the mixture was slowly heated to 90 ° C. under 20torr pressure to remove acetyl chloride and acid anhydride, and further heated to 90-130 ° C. to distill methyltriacetoxysilane and ethyltriacetoxysilane to prepare acetoxysilane. (Yield: 94%)
상기 본 발명에 따른 실시예와 종래기술에 의한 비교예에서 알 수 있듯이, 본 발명의 실리콘 실란트용 초산형 가교제의 제조방법은 하나의 반응기에서 원하는초산형 가교제를 간단한 공정에 의해 쉽게 제조할 수 있는 장점이 있다.As can be seen from the embodiment according to the present invention and the comparative example according to the prior art, the method for producing an acetic acid type crosslinking agent for a silicone sealant of the present invention can be easily prepared by a simple process to the desired acetate type crosslinking agent in one reactor There is an advantage.
Claims (5)
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3792071A (en) * | 1970-12-11 | 1974-02-12 | Wacker Chemie Gmbh | Process for the manufacture of alkoxysilanes and alkoxy-polysiloxanes |
| US3974198A (en) * | 1975-09-02 | 1976-08-10 | General Electric Company | Process for producing methyltriacetoxysilane |
| US4176130A (en) * | 1978-01-17 | 1979-11-27 | Wacker-Chemie Gmbh | Process for preparing acyloxysilanes and acyloxysiloxanes |
| US4239484A (en) * | 1978-09-13 | 1980-12-16 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Vacuum oven with gas cooling device |
| US4332956A (en) * | 1981-06-26 | 1982-06-01 | General Electric Company | Process for preparing acyloxysilanes |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3792071A (en) * | 1970-12-11 | 1974-02-12 | Wacker Chemie Gmbh | Process for the manufacture of alkoxysilanes and alkoxy-polysiloxanes |
| US3974198A (en) * | 1975-09-02 | 1976-08-10 | General Electric Company | Process for producing methyltriacetoxysilane |
| US4176130A (en) * | 1978-01-17 | 1979-11-27 | Wacker-Chemie Gmbh | Process for preparing acyloxysilanes and acyloxysiloxanes |
| US4239484A (en) * | 1978-09-13 | 1980-12-16 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Vacuum oven with gas cooling device |
| US4332956A (en) * | 1981-06-26 | 1982-06-01 | General Electric Company | Process for preparing acyloxysilanes |
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