KR101165667B1 - Novel silane coupling agent and manufacturing method thereof - Google Patents
Novel silane coupling agent and manufacturing method thereof Download PDFInfo
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- KR101165667B1 KR101165667B1 KR1020100046251A KR20100046251A KR101165667B1 KR 101165667 B1 KR101165667 B1 KR 101165667B1 KR 1020100046251 A KR1020100046251 A KR 1020100046251A KR 20100046251 A KR20100046251 A KR 20100046251A KR 101165667 B1 KR101165667 B1 KR 101165667B1
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- 239000006087 Silane Coupling Agent Substances 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- -1 ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene Chemical group 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- 239000002635 aromatic organic solvent Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical group CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 5
- 125000003545 alkoxy group Chemical group 0.000 abstract description 4
- 125000004429 atom Chemical group 0.000 abstract description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 125000004434 sulfur atom Chemical group 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 23
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 239000000377 silicon dioxide Substances 0.000 description 12
- 229920001971 elastomer Polymers 0.000 description 9
- 125000000524 functional group Chemical group 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 8
- 229910010272 inorganic material Inorganic materials 0.000 description 7
- 239000011147 inorganic material Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000010399 physical interaction Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- JPPLPDOXWBVPCW-UHFFFAOYSA-N s-(3-triethoxysilylpropyl) octanethioate Chemical compound CCCCCCCC(=O)SCCC[Si](OCC)(OCC)OCC JPPLPDOXWBVPCW-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000004073 vulcanization 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- 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
- C08K5/548—Silicon-containing compounds containing sulfur
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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)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
Abstract
본 발명은 신규한 실란 커플링제 및 그의 제조방법을 제공하며, 상세하게는 실리콘(Si) 원자에 세 개의 알콕시기를 가지며, 한 개의 프로필렌기가 결합하며, 프로필렌기에 황(S) 원자가 결합하며, 황 원자에 카르보닐기(-CO-) 결합하며, 상기 카르보닐기에 결합한 알킬렌기를 중심으로 양쪽 대칭 구조를 같는 신규한 실란 커플링제 및 그의 제조방법을 제공한다.The present invention provides a novel silane coupling agent and a method for producing the same, specifically, having three alkoxy groups on silicon (Si) atoms, one propylene group, a sulfur (S) atom on a propylene group, a sulfur atom The present invention provides a novel silane coupling agent having a carbonyl group (-CO-) bonded thereto and having the same symmetrical structure in both symmetric structures with respect to the alkylene group bonded to the carbonyl group, and a method of preparing the same.
Description
본 발명은 신규한 실란 커플링제 및 그의 제조방법에 관한 것으로 자세하게는 종래의 실란 커플링제보다 저장 안정성이 우수하고, 양방향 구조로 결합력이 우수하여 폭넓은 용도의 실란 커플링제 및 그의 제조방법을 제공한다.The present invention relates to a novel silane coupling agent and a method for producing the same. Specifically, the present invention provides superior storage stability and superior binding force in a bidirectional structure to provide a silane coupling agent for a wide range of uses and a manufacturing method thereof. .
실란 커플링제는 분자 중에 2개 이상의 서로 다른 반응기(Reactive group)를 가지고 있어서, 통상적으로는 상당히 결부시키기 어려운 유기질 재료와 무기질 재료를 연결하는 중개역으로서 작용하고 있다. 반응기 중 하나는 유리, 금속, 모래 등의 무기질 재료와 화학결합하는 메톡시기 또는 에톡시기와 같은 반응기고, 또 다른 하나는 각종 합성수지와 같은 유기질 재료와 화학결합하는 비닐기, 에폭시기, 아미노기, 메타크릴기 또는 멀캅토기 등과 같은 반응기이다. 이와 같은 특성을 이용하여, 유기 수지와 무기 필러의 친화성을 높이기 위해서 혹은 매트릭스 수지로 이루어진 코팅층과 기재 사이의 접착성 발현을 위해서 다양한 실란 커플링제가 사용되고 있다. 즉, 실란 커플링제가 유기 수지와 무기 필러와의 친화성을 높이거나 기재 사이의 접착성을 높이기 위해서는 유기 수지의 관능기와 실란 커플링제의 유기 관능기의 화학적 결합 또는 물리적 상호작용이 있어야 하며, 실란 커플링제의 알콕시 실릴기와 무기 필러 또는 기재와의 화학적 결합이 필요하다. 따라서 실란 커플링제의 유기 관능기는 수지의 종류 및 관능기에 따라 다양한 형태가 사용되고 있다..Silane coupling agents have two or more different reactive groups in the molecule, and thus act as an intermediary linking organic and inorganic materials that are typically difficult to associate significantly. One of the reactors is a reactor such as a methoxy group or an ethoxy group which chemically bonds to an inorganic material such as glass, metal, sand, and the other is a vinyl group, an epoxy group, an amino group, or a methacryl that is chemically bonded to an organic material such as various synthetic resins. Group or a mercapto group and the like. By using such a property, various silane coupling agents are used to raise the affinity of an organic resin and an inorganic filler, or to develop adhesiveness between the coating layer which consists of matrix resin, and a base material. That is, in order for the silane coupling agent to increase the affinity between the organic resin and the inorganic filler or to improve the adhesion between the substrate, the silane coupling agent must have a chemical bond or physical interaction between the organic resin functional group and the organic functional group of the silane coupling agent. Chemical bonding of the alkoxy silyl group of the ring agent with the inorganic filler or the substrate is required. Therefore, various forms are used according to the kind of resin and functional group of the organic functional group of a silane coupling agent.
현재 많이 사용되는 실란 커플링제 중에는 우레탄기를 포함하는 실란 커플링제가 있다. 일본특허공보 특개평 10-67787호는 이소시아네이트 실란과 디에탄올아민을 가열 처리하여 실란 커플링제를 제조하는 방법을 개시하고 있고, 일본특허공보 특개평 11-335378호에는 아미노실란에 비닐벤질클로라이드 및 이소시아네이트를 반응시켜 실란 커플링제를 제조하는 방법을 개시하고 있다. 그러나 매트릭스 수지 내에 수산기(-OH)가 존재하는 경우에는 이에 대응하는 유기 관능기를 가진 실란 커플링제가 불충분한 실정이다. Among the silane coupling agents commonly used at present, there are silane coupling agents containing urethane groups. Japanese Patent Application Laid-open No. Hei 10-67787 discloses a method for producing a silane coupling agent by heat treatment of isocyanate silane and diethanolamine, and Japanese Patent Laid-Open No. Hei 11-335378 discloses vinylbenzyl chloride and isocyanate in aminosilane. A method of producing a silane coupling agent by reacting is disclosed. However, when hydroxyl group (-OH) exists in matrix resin, the silane coupling agent which has the corresponding organic functional group is insufficient.
현재 신개념 자동차 시장 증가에 따른 고성능 타이어가 요구 되면서 고성능 타이어용 고 기능성 유기탄성체 소재가 요구되고 있다. 그에 따라 흔히 쓰는 Si-69실란 커플링제를 대체 할 수 있는 실란을 제조하고자 이 발명이 시작되었다. 필러(filler)의 친화성을 높이기 위하거나 매트릭스(matrix) 수지로 이루어진 코팅층과 기재 사이의 접착성을 높이기 위한 목적의 실란 커플링제로서 다양하게 사용될 수 있는 신규한 실란 커플링제가 요구되고 있다.As high-performance tires are required in accordance with the increase of the new concept automobile market, high-functional organic elastomer materials for high-performance tires are required. Accordingly, the present invention was started to produce a silane that can replace the commonly used Si-69 silane coupling agent. There is a need for a new silane coupling agent that can be used in various ways as a silane coupling agent for the purpose of increasing the affinity of fillers or improving the adhesion between a substrate and a coating layer made of a matrix resin.
상기의 문제점을 해결하고자 본 발명은 화합물 내에 수산기(-OH)를 가지는 매트릭스와 결합이 있는 유기 그룹을 디자인하여 신규의 유용한 실란 커플링제 및 그의 제조방법을 제공하는 목적이 있다.In order to solve the above problems, an object of the present invention is to provide a novel useful silane coupling agent and a method of preparing the same by designing an organic group having a bond with a matrix having a hydroxyl group (-OH) in a compound.
상기의 목적을 달성하고자 본 발명은 하기 화학식 1로 표시되는 실란 커플링제를 제공한다.The present invention to achieve the above object provides a silane coupling agent represented by the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서, R1 내지 R3 은 서로 독립적으로 직쇄 또는 분지쇄의 (C1-C4)알킬기이며; R4 는 직쇄 또는 분지쇄의 (C2-C20)알킬렌기이며; R5는 직쇄 또는 분지쇄의 (C2-C6)알킬렌기이다.In Chemical Formula 1, R 1 to R 3 Are independently of each other a straight or branched chain (C 1 -C 4) alkyl group; R 4 Is a straight or branched chain (C 2 -C 20) alkylene group; R 5 is a straight or branched chain (C 2 -C 6) alkylene group.
본 발명의 상기 화학식 1의 실란 커플링제는 실리콘(Si) 원자에 세 개의 알콕시기를 가지며; 한 개의 프로필렌기가 결합하며; 프로필렌기에 황(S) 원자가 결합하며; 황 원자에 카르보닐기(-CO-) 결합하며; 상기 카르보닐기에 결합한 알킬렌기를 중심으로 양쪽 대칭 구조를 갖는 신규한 실란 커플링제이다..The silane coupling agent of Formula 1 of the present invention has three alkoxy groups at the silicon (Si) atom; One propylene group is bonded; Sulfur (S) atoms are bonded to the propylene group; A carbonyl group (—CO—) is bonded to a sulfur atom; It is a novel silane coupling agent which has both symmetrical structures centering on the alkylene group couple | bonded with the said carbonyl group.
본 발명의 상기 화학식 1에서, R1 내지 R3 은 서로 독립적으로 메틸기 또는 에틸기인 것이 바람직하며, 에틸기인 것이 가장 바람직하다.In Chemical Formula 1 of the present invention, R 1 to R 3 Is independently a methyl group or an ethyl group, and most preferably an ethyl group.
또한 본 발명의 상기 화학식 1에서, R4 는 직쇄 또는 분지쇄의 (C1-C10)알킬렌기인 것이 바람직하며, 에틸렌, 프로필렌, 부틸렌, 펜틸렌, 헥실렌, 헵틸렌, 옥틸렌, 노닐렌 및 데실렌으로부터 선택되는 것이 가장 바람직하다.In addition, in the general formula (1) of the present invention, R 4 is preferably a linear or branched (C1-C10) alkylene group, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene And decylene is most preferred.
본 발명의 상기 화학식 1의 신규한 실란 커플링제는 양쪽 대칭형 구조를 갖고 있어 고무 가황 시 한쪽은 실리카와 결합이 가능하게 함으로써, 실리카로 인한 물성, 즉 강도를 부여하거나, 내열성 및 내구성을 향상시킬 수 있는 장점이 있다. The novel silane coupling agent of the formula (1) of the present invention has a symmetrical structure of both sides so that one side can be bonded to silica when vulcanizing rubber, thereby giving physical properties, that is, strength due to silica, or improving heat resistance and durability. There is an advantage.
본 발명의 상기 화학식 1의 신규한 실란 커플링제를 제조하는 방법에 있어서, 본 발명은 하기 화학식 2의 화합물 및 화학식 3의 화합물을 유기용매 하에서 반응하여 상기 화학식 1의 신규한 실란 커플링제를 제조할 수 있으며, 공정이 매우 간단하여 대량 생산에 매우 적합하다.In the method for preparing a novel silane coupling agent of Formula 1 of the present invention, the present invention is to react the compound of Formula 2 and the compound of Formula 3 in an organic solvent to prepare a novel silane coupling agent of Formula 1 The process is very simple and suitable for mass production.
[화학식 2][Formula 2]
[화학식 3](3)
상기 화학식 2 및 화학식 3에서, R1 내지 R3 은 서로 독립적으로 직쇄 또는 분지쇄의 (C1-C4)알킬기이며; R5 는 직쇄 또는 분지쇄의 (C2-C6)알킬렌기이며; R6 및 R7 은 서로 독립적으로 직쇄 또는 분지쇄의 (C1-C10)알킬렌기이며; X는 할로겐 원자이다.In Formula 2 and Formula 3, R 1 to R 3 Are independently of each other a straight or branched chain (C 1 -C 4) alkyl group; R 5 Is a straight or branched chain (C 2 -C 6) alkylene group; R 6 and R 7 are each independently a straight or branched chain (C 1 -C 10) alkylene group; X is a halogen atom.
본 발명은 상기 화학식 2에서 R1 내지 R3 은 서로 독립적으로 메틸기 또는 에틸기인 것이 바람직하며, 에틸기인 것이 가장 바람직하다.. 또한 상기 화학식 2에서, R5 는 프로필렌기인 것이 바람직하고, R6은 메틸렌, 에틸렌, 부틸렌 및 펜틸렌으로부터 선택되는 것이 바람직하다.The present invention in the formula 2 R 1 to R 3 Is independently a methyl group or an ethyl group, and most preferably an ethyl group. In the above Formula 2, R 5 is preferably a propylene group, and R 6 is selected from methylene, ethylene, butylene and pentylene. It is preferable.
본 발명의 상기 화학식 3에서, R7은 메틸렌, 에틸렌, 부틸렌 및 펜틸렌으로부터 선택되는 것이 바람직하며, 상기 화학식 3에서, X는 염소(Cl)인 것이 바람직하다.In Formula 3 of the present invention, R 7 is preferably selected from methylene, ethylene, butylene and pentylene, and in Formula 3, X is preferably chlorine (Cl).
본 발명은 상기 유기용매로서, 특별히 한정하지 않지만, 본 발명의 반응물들에 대한 용해도가 높은 유기용매면 어떠한 것이든 무방하지만, 특별히 방향족 유기용매가 바람직하며, 벤젠을 이용하는 것이 가장 바람직하다..Although the present invention is not particularly limited as the organic solvent, any organic solvent having high solubility in the reactants of the present invention may be used, but an aromatic organic solvent is particularly preferable, and benzene is most preferably used.
본 발명은 반응 과정에서 부산물로서 산성 기체 또는 산성 화합물이 발생할 수 있고, 일례를 들어, 상기 화학식 3의 X가 염소인 경우, 염산이 발생할 수 있기 때문에 유리 반응기(Glass reactor)를 이용하는 것이 생성물의 순도를 높이거나, 불순물의 생성을 방지할 수 있다.In the present invention, an acid gas or an acid compound may be generated as a by-product in the reaction process, and, for example, when X in Chemical Formula 3 is chlorine, hydrochloric acid may be generated, and thus, the glass reactor may be used. It is possible to increase or to prevent the generation of impurities.
본 발명은 상기 화학식 2와 화학식 3의 화합물의 반응에 있어서, 저온에서 실시하며, 구체적으로는 -20 내지 0℃ 범위에서 실시하는 것이 바람직하다.In the reaction of the compounds of Formula 2 and Formula 3, the present invention is carried out at low temperature, specifically, it is preferably carried out in the range of -20 to 0 ℃.
본 발명의 상기 신규한 화학식 1의 실란 커플링제는 두 종류의 특별한 반응기(Reactive group)를 포함한다. 하나는 유기물질과 우수한 화학적 결합을 형성하고, 또 다른 하나는 무기 물질과 우수한 화학적 결합을 형성하는 반응기를 포함한다. 자세하게는 특별히 수산기를 가지는 실리카 수지 등의 무기질 재료와의 결합력을 증가시키기 위하여 실란 커플링제 내에 알콕시기를 도입함으로써 무기질 재료와의 결합력을 증가시켰으며, 황 원자를 도입함으로써 고무와의 결합력이 우수한 실란 커플링제를 제공한다. 예를 들어 고무와 실리카의 배합을 할 경우, 수산기로 인하여 결합력이 떨어지는 실리카를 알콕시기를 통하여 수산기를 제거해 줌으로써 고무와 반응하여 무기 물질과 화학적 결합을 형성한다. 즉, 본 발명의 상기 화학식 1의 신규한 실란 커플링제는 놀랍게도 실리카 필러와의 친화성을 높이고, 매트릭스 수지로 이루어진 코팅층과 기재 사이의 접착성을 크게 향상시킬 수 있다.The novel silane coupling agent of formula (I) of the present invention comprises two special reactive groups. One includes a reactor that forms a good chemical bond with the organic material and the other forms a good chemical bond with the inorganic material. Specifically, in order to increase the bonding strength with inorganic materials such as silica resins having hydroxyl groups, the bonding strength with inorganic materials was increased by introducing an alkoxy group into the silane coupling agent, and the silane couple having excellent bonding strength with rubber by introducing sulfur atoms. Provide a ring agent. For example, when rubber and silica are mixed, silica, which is inferior in bonding strength due to hydroxyl groups, is removed from the hydroxyl groups through an alkoxy group to react with rubber to form a chemical bond with the inorganic material. That is, the novel silane coupling agent of Formula 1 of the present invention may surprisingly increase the affinity with the silica filler, and greatly improve the adhesion between the coating layer made of the matrix resin and the substrate.
또한 결합시키는 매트릭스 수지 내에 포함된 관능기에 따라 상보하는 여러 가지 유기 관능기를 실란 커플링제에 도입할 수 있다. 이때 수지 내의 특정한 관능기와 선택적으로 화학결합을 형성시키기 위해서 실란 커플링제 내에 적합한 구조의 유기 그룹을 도입하여 제조할 수 있다.In addition, various organic functional groups complementary to the functional groups contained in the matrix resin to be bonded can be introduced into the silane coupling agent. At this time, it can be prepared by introducing an organic group having a suitable structure in the silane coupling agent in order to selectively form a chemical bond with a specific functional group in the resin.
본 발명의 상기 화학식 1의 신규한 실란 커플링제는 종래의 실란 커플링제를 대체할 수 있고, 종래의 실란 커플링제보다 유기 및 무기 재료와의 친화력이 뛰어나고, 매트릭스 수지로 이루어진 코팅층과 기재 사이의 접착성이 매우 우수하여 고성능 타이어용 고 기능성 유기탄성체를 제조하는데 매우 적합하다. 특히, 실리카 타이어의 제조 시 실리카 조성물에 사용되어 고무와 실리카의 결합력을 향상시킬 수 있으며, 이에 따른 무니점도(mooney viscosity)가 좋아져 가공성을 높일 수 있으며, 기계적 물성뿐만 아니라, 타이어에 있어서 가장 중요한 회전저항값을 개선시킬 수 있다.The novel silane coupling agent of Chemical Formula 1 of the present invention can replace the conventional silane coupling agent, has a better affinity with organic and inorganic materials than the conventional silane coupling agent, and the adhesion between the coating layer made of matrix resin and the substrate Due to its excellent properties, it is very suitable for producing high functional organic elastomers for high performance tires. In particular, it can be used in the silica composition in the manufacture of silica tires to improve the bonding strength of the rubber and silica, thereby improving the Mooney viscosity (workey viscosity) to improve the processability, as well as mechanical properties, the most important rotation in the tire The resistance value can be improved.
본 발명에 따른 신규한 실란 커플링제는 매트릭스 수지와의 결합력을 향상시켜 저장안정성이 우수하고, 유기 수지 및 무기 필러의 친화성을 높일 수 있어, 종래 물질에 기능성 있는 관능기 또는 화합물로 개질하기에 적합할 뿐만 아니라, 다양한 분야에서의 사용이 가능하다. 특히, 실리카 타이어 제조에 포함되어 타이어에 있어서 가장 중요한 회전저항값을 향상시킬 수 있다. 또한, 무니점도(mooney viscosity)가 우수하여 가공성을 향상시킬 수 있어 제조공정 상 비용과 시간에 대한 이점이 있다.The novel silane coupling agent according to the present invention improves the bonding strength with the matrix resin, has excellent storage stability, can enhance the affinity of the organic resin and the inorganic filler, and is suitable for modifying functional groups or compounds functionally in the conventional materials. In addition, it can be used in various fields. In particular, it is included in the production of silica tires to improve the rolling resistance value which is most important for tires. In addition, the Mooney viscosity (excellent) Mooney viscosity can be improved to improve the processability has the advantage of cost and time in the manufacturing process.
본 발명은 하기 실시예에 의해 보다 더 잘 이해될 수 있으며, 하기 실시예는 본 발명의 예시 목적을 위한 것으로서 본 발명의 범주 및 기술사상 범위 내에서 다양한 변형 및 수정이 가능함은 당업자에게 있어서 명백한 것이며 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.
The present invention can be better understood by the following examples, which are obvious to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention for the purpose of illustrating the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.
[제조예 1] [Production Example 1]
수조에 얼음을 이용하여 온도를 -5?로 유지하도록 하고, 상기 수조를 베이스로 하여 유리 반응기(glass reactor)내에 무수 벤젠 100g, 3-octanoylthio-1-propyltriethoxysilane 0.4 mole과 ethylene dichloride 0.15mole을 혼합한 후, 30분 동안 교반한 후 rotary evaporator로 진공 증류한 후 건조하여 하기 화학식 4의 실란 커플링제를 얻었다. Maintain the temperature at -5? By using ice in a water tank, and mix 100 g of anhydrous benzene, 0.4 mole of 3-octanoylthio-1-propyltriethoxysilane and 0.15 mole of ethylene dichloride in a glass reactor based on the water tank. Then, the mixture was stirred for 30 minutes and then vacuum distilled with a rotary evaporator, followed by drying to obtain a silane coupling agent of the following Chemical Formula 4.
(화학식 4)(Formula 4)
[실시예 1]Example 1
상기 제조예 1에서 얻은 신규한 실란 커플링제를 포함하는 실리카 컴파운드를 타이어 고무 조성물에 하기 표 1과 같이 배합한 후, 타이어의 물성을 측정하였으며, 그 결과를 하기 표 2에 나타내었다.
After blending the silica compound containing the novel silane coupling agent obtained in Preparation Example 1 to the tire rubber composition as shown in Table 1 below, the physical properties of the tire were measured, and the results are shown in Table 2 below.
[비교예 1]Comparative Example 1
신규한 실란 커플링제 대신 NXT silane을 사용한 것을 제외하고는 상기 실시예 1과 같은 방법으로 실시하였다.
The same procedure as in Example 1 was conducted except that NXT silane was used instead of the novel silane coupling agent.
표 1. 타이어 고무 조성물 배합표 (단위:중량부)Table 1. tire rubber composition formulation table (unit: parts by weight)
표 2. 물성 결과Table 2. Property Results
상기 표 2에서 보이는 바와 같이, 본 발명에 따른 신규 실란 커플링제를 타이어 제조 시, 사용되는 실리카 컴파운드 조성물에 배합한 것을 사용한 실시예 1의 경우는 비교예 1에 비해 무니점도, 가류도가 우수하여 공정상 가공이 용이하며, 경도, 신율 및 회전저항 값이 향상됨을 확인할 수 있었다. As shown in Table 2, Example 1 using the new silane coupling agent according to the present invention in combination with the silica compound composition used in the manufacture of tires is excellent in Mooney viscosity and vulcanization compared to Comparative Example 1 Processing was easy in the process, it was confirmed that the hardness, elongation and rotational resistance values are improved.
Claims (11)
[화학식 1]
[화학식 2]
[화학식 3]
[상기 화학식 1 내지 3에서, R1 내지 R3 은 서로 독립적으로 직쇄 또는 분지쇄의 (C1-C4)알킬기이며; R4 는 직쇄 또는 분지쇄의 (C2-C20)알킬렌기이며; R5 는 직쇄 또는 분지쇄의 (C1-C10)알킬렌기이며; R6 및 R7 은 서로 독립적으로 직쇄 또는 분지쇄의 (C1-C10)알킬렌기이며; X는 할로겐 원자이다.]A method for preparing a silane coupling agent of Formula 1, comprising the step of reacting a compound of Formula 2 with a compound of Formula 3:
[Formula 1]
(2)
(3)
[In Formulas 1 to 3, R 1 to R 3 Are independently of each other a straight or branched chain (C 1 -C 4) alkyl group; R 4 Is a straight or branched chain (C 2 -C 20) alkylene group; R 5 Is a straight or branched (C 1 -C 10) alkylene group; R 6 and R 7 are each independently a straight or branched chain (C 1 -C 10) alkylene group; X is a halogen atom.]
상기 화학식 1 내지 화학식 3에서, R1 내지 R3 은 메틸기 또는 에틸기이며; R4 는 에틸렌, 프로필렌, 부틸렌, 펜틸렌, 헥실렌, 헵틸렌, 옥틸렌, 노닐렌 및 데실렌으로부터 선택되며; R6 및 R7 은 서로 독립적으로 메틸렌, 에틸렌, 부틸렌 및 펜틸렌으로부터 선택되며; X는 염소인 것을 특징으로 하는 실란 커플링제의 제조방법.
The method of claim 5,
In Chemical Formulas 1 to 3, R 1 to R 3 Is a methyl group or an ethyl group; R 4 is selected from ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene and decylene; R 6 and R 7 are independently of each other selected from methylene, ethylene, butylene and pentylene; X is chlorine, The manufacturing method of the silane coupling agent characterized by the above-mentioned.
상기 반응은 방향족 유기용매 하에서 반응하는 실란 커플링제의 제조방법.
The method of claim 5,
The reaction is a method for producing a silane coupling agent reacts under an aromatic organic solvent.
상기 방향족 유기용매는 벤젠인 실란 커플링제의 제조방법.
The method of claim 7, wherein
The aromatic organic solvent is a benzene coupling method for producing a silane coupling agent.
상기 반응은 -20 내지 0℃의 저온에서 반응하는 실란 커플링제의 제조방법.
The method of claim 5,
The reaction is a method for producing a silane coupling agent is reacted at a low temperature of -20 to 0 ℃.
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| JP2007051146A (en) | 2005-08-17 | 2007-03-01 | Degussa Ag | Organosilicon compound, method for producing the same and use of the compound |
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| JP2006232917A (en) | 2005-02-23 | 2006-09-07 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
| JP2007051146A (en) | 2005-08-17 | 2007-03-01 | Degussa Ag | Organosilicon compound, method for producing the same and use of the compound |
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