CN1261503C - A kind of silicone rubber composition and its preparation method and application - Google Patents
A kind of silicone rubber composition and its preparation method and application Download PDFInfo
- Publication number
- CN1261503C CN1261503C CN 03147830 CN03147830A CN1261503C CN 1261503 C CN1261503 C CN 1261503C CN 03147830 CN03147830 CN 03147830 CN 03147830 A CN03147830 A CN 03147830A CN 1261503 C CN1261503 C CN 1261503C
- Authority
- CN
- China
- Prior art keywords
- rubber composition
- weight
- metal
- parts
- silicone rubber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 36
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims description 3
- 239000004945 silicone rubber Substances 0.000 title description 23
- 229910000077 silane Inorganic materials 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 229910001369 Brass Inorganic materials 0.000 claims description 4
- 239000010951 brass Substances 0.000 claims description 4
- 239000007769 metal material Substances 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims 13
- 239000005060 rubber Substances 0.000 claims 13
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 5
- 229910052710 silicon Inorganic materials 0.000 claims 4
- 239000010703 silicon Substances 0.000 claims 4
- 239000003795 chemical substances by application Substances 0.000 claims 3
- 239000002184 metal Substances 0.000 abstract description 21
- 229910052751 metal Inorganic materials 0.000 abstract description 21
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000003431 cross linking reagent Substances 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000013522 chelant Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 15
- 239000006087 Silane Coupling Agent Substances 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- YMQXZQXPIJQWIN-UHFFFAOYSA-N 8-trimethoxysilyloctane-2,4-dione Chemical compound CO[Si](CCCCC(=O)CC(C)=O)(OC)OC YMQXZQXPIJQWIN-UHFFFAOYSA-N 0.000 description 3
- -1 γ-(3-Acetylacetonyl) Propyl Chemical group 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- DZXZGWVGWCAUND-UHFFFAOYSA-N CCO.CCC[Si](OC)(OC)OC Chemical compound CCO.CCC[Si](OC)(OC)OC DZXZGWVGWCAUND-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
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000002081 peroxide group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001709 polysilazane Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
技术领域technical field
本发明涉及一种硅橡胶组合物及其制备方法和用途。该组合物由硅生胶、交联剂、催化剂、填料以及γ-(3-乙酰丙酮基)丙基三烷氧基硅烷组成。该组合物的制备是将上述组分在室温(25～40℃)共混制备。该组合物可以用于与金属的粘接。The invention relates to a silicone rubber composition and its preparation method and application. The composition is composed of silica gel, crosslinking agent, catalyst, filler and gamma-(3-acetylacetonyl)propyltrialkoxysilane. The composition is prepared by blending the above components at room temperature (25-40° C.). The composition can be used for bonding with metals.
背景技术Background technique
硅橡胶具有耐高低温，耐气候老化及优良的电气性能，是重要的粘接密封材料。在现代工业中硅橡胶广泛地应用于建筑、运输工具和电子器件中。但是由于硅橡胶表面能低，它与金属表面，尤其是不锈钢、黄铜等难粘金属的粘接强度也很低，影响了许多粘接密封部件的使用寿命。因此改善硅橡胶，尤其是室温硫化硅橡胶与金属的粘接强度有重要的实际意义。Silicone rubber has high and low temperature resistance, weather aging resistance and excellent electrical properties, and is an important bonding and sealing material. Silicone rubber is widely used in construction, transportation and electronic devices in modern industry. However, due to the low surface energy of silicone rubber, its bonding strength with metal surfaces, especially difficult-to-bond metals such as stainless steel and brass, is also very low, which affects the service life of many bonded and sealed parts. Therefore, it is of great practical significance to improve the bonding strength of silicone rubber, especially room temperature vulcanized silicone rubber and metal.
采用硅烷偶联剂提高无机表面与有机高分子粘接强度的技术是已知的。硅烷偶联剂的主要研究者E.P.Plueddemann在专著《Silane Coupling Agents》(Plenum，1991，New York)中对硅烷偶联剂作了系统介绍。通常使用的硅烷偶联剂分子中含有能与各种树脂结合的氨基、环氧基、乙烯基、丙烯酸酯基、硫醇基、过氧化物基等；在硅烷分子中的烷氧基水解后与无机表面的羟基缩合形成氧桥键。因此用硅烷偶联剂改善高分子与无机表面的粘合通常是很成功的。但是由于Si-O-M(M代表金属原子)键不耐水解，已知的硅烷偶联剂对改善硅橡胶与难粘金属之间的粘接并不理想。It is known to use a silane coupling agent to improve the bonding strength between an inorganic surface and an organic polymer. E.P.Plueddemann, the main researcher of silane coupling agents, made a systematic introduction to silane coupling agents in the monograph "Silane Coupling Agents" (Plenum, 1991, New York). The commonly used silane coupling agent molecules contain amino groups, epoxy groups, vinyl groups, acrylate groups, thiol groups, peroxide groups, etc. that can be combined with various resins; after hydrolysis of the alkoxy groups in the silane molecule Condenses with hydroxyl groups on the inorganic surface to form oxygen bridges. Therefore, the use of silane coupling agents to improve the adhesion of polymers to inorganic surfaces is usually very successful. However, because the Si-O-M (M represents a metal atom) bond is not resistant to hydrolysis, known silane coupling agents are not ideal for improving the bonding between silicone rubber and difficult-to-bond metals.
发明内容Contents of the invention
本发明的硅橡胶组合物由硅生胶、交联剂、催化剂、填料以及γ-(3-乙酰丙酮基)丙基三烷氧基硅烷组成。其典型配方如下：
上述的硅生胶采用市售的硅生胶，如107硅橡胶、108硅橡胶等。交联剂可采用正硅酸乙酯、甲基三乙酰氧基硅烷、甲基三甲乙酮(wu)基硅烷，甲基聚硅氮烷等。催化剂可采用二丁基二月桂酸锡、辛酸亚锡等。填料可采用白碳黑、碳酸钙、二氧化钛、氧化锌、氧化铁等。The above-mentioned raw silicon rubber adopts commercially available raw silicon rubber, such as 107 silicon rubber, 108 silicon rubber, and the like. As the crosslinking agent, ethyl orthosilicate, methyl triacetoxysilane, methyl trimethyl ethyl ketone (wu) silane, methyl polysilazane and the like can be used. The catalyst can be dibutyltin dilaurate, stannous octoate, etc. Fillers can be white carbon black, calcium carbonate, titanium dioxide, zinc oxide, iron oxide, etc.
上述γ-(3-乙酰丙酮基)丙基的烷氧基硅烷的结构式如式(1)所示。其中R为含1-5个碳原子的烷基。The structural formula of the aforementioned γ-(3-acetylacetonyl)propyl alkoxysilane is shown in formula (1). wherein R is an alkyl group containing 1-5 carbon atoms.
该硅烷作为偶联剂，解决了室温硫化硅橡胶与难粘金属粘接的难题。实验表明乙酰丙酮基能在金属表面形成螫合物(式2)，因此采用含这种基团的偶联剂能有效地改善硅橡胶与金属的粘接强度。并使破坏形式由粘附破坏转变成内聚破坏。The silane, as a coupling agent, solves the problem of bonding room temperature vulcanized silicone rubber and difficult-to-bond metals. Experiments show that the acetylacetonate group can form a chelate (Formula 2) on the metal surface, so the use of a coupling agent containing this group can effectively improve the bonding strength between silicone rubber and metal. And change the form of failure from adhesive failure to cohesive failure.
按照本发明的方法，将γ-(3-乙酰丙酮基)丙基三烷氧基硅烷或它的水解物1-5％的乙醇溶液涂覆于金属表面上并晾干，在金属表面进行预处理。该硅橡胶组合物是将硅生胶100重量份，交联剂2～10重量份，催化剂0.2～2重量份，填料3～100重量份，γ-(3-乙酰丙酮基)丙基烷氧基硅烷1～5重量份在25～40℃共混制得。然后将该硅橡胶组合物涂覆于处理好的金属表面进行粘接。According to the method of the present invention, γ-(3-acetylacetonate) propyl trialkoxysilane or its hydrolyzate 1-5% ethanol solution is coated on the metal surface and dried, and the metal surface is pretreated. deal with. The silicone rubber composition comprises 100 parts by weight of raw silicon rubber, 2 to 10 parts by weight of a crosslinking agent, 0.2 to 2 parts by weight of a catalyst, 3 to 100 parts by weight of a filler, γ-(3-acetylacetonate) propyl alkoxy It is prepared by blending 1-5 parts by weight of base silane at 25-40°C. Then the silicone rubber composition is coated on the treated metal surface for bonding.
本发明的方法适用于钢铁、铝合金等常用的金属材料与硅橡胶的粘接，也适用于不锈钢、黄铜等难粘金属与硅橡胶的粘接。The method of the invention is suitable for the bonding of commonly used metal materials such as steel and aluminum alloys and silicon rubber, and is also suitable for the bonding of difficult-to-bond metals such as stainless steel and brass and silicon rubber.
采用本发明的方法能有效地改善硅橡胶与金属的粘接强度，并使破坏形式由粘附破坏转变成内聚破坏。经ASTM D1002-99标准测定剪切强度，硅橡胶与金属粘接的剪切强度可达2.46～2.95MPa。Adopting the method of the invention can effectively improve the bonding strength between the silicone rubber and the metal, and change the failure form from adhesion failure to cohesive failure. The shear strength measured by ASTM D1002-99 standard, the shear strength of silicone rubber and metal bonding can reach 2.46 ~ 2.95MPa.
具体实施方式Detailed ways
下面通过实施例进一步说明本发明的特点。Below further illustrate characteristics of the present invention by embodiment.
实施例1Example 1
按照下面的比例配制硅橡胶：
以浓度为1％γ-(3-乙酰丙酮基)丙基三甲氧基硅烷乙醇溶液涂覆于304#不锈钢表面上并晾干。在室温下放置24h后以上述硅橡胶粘接不锈钢试片。在室温下放置7天以使硅橡胶固化完全。剪切强度测试结果如下：
对照例1Comparative example 1
按照下面的比例配制硅橡胶：
以上述硅橡胶粘接不锈钢试片。在室温下放置7天以使硅橡胶固化完全。剪切强度测试结果如下：
实施例2Example 2
按照下面配方配制硅橡胶：
以上述硅橡胶粘接黄铜试片。在室温下放置24h，并在100℃处理6h。剪切强度测试结果如下：
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03147830 CN1261503C (en) | 2003-06-25 | 2003-06-25 | A kind of silicone rubber composition and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03147830 CN1261503C (en) | 2003-06-25 | 2003-06-25 | A kind of silicone rubber composition and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1566213A CN1566213A (en) | 2005-01-19 |
| CN1261503C true CN1261503C (en) | 2006-06-28 |
Family
ID=34472058
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03147830 Expired - Fee Related CN1261503C (en) | 2003-06-25 | 2003-06-25 | A kind of silicone rubber composition and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1261503C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101899779B (en) * | 2010-08-12 | 2013-04-24 | 浙江传化股份有限公司 | 100% of organic silicon coating finishing agent and application thereof |
| CN107474313B (en) * | 2017-09-19 | 2019-12-27 | 荆州市江汉精细化工有限公司 | Modified rubber additive and preparation method thereof |
| CN112920605A (en) * | 2020-11-10 | 2021-06-08 | 金冠电气股份有限公司 | Silicone rubber composite material for bonding polybutylene terephthalate |
| CN114836157A (en) * | 2022-05-09 | 2022-08-02 | 广东汇齐新材料有限公司 | High-viscosity weather-resistant hot melt adhesive film and preparation method thereof |
-
2003
- 2003-06-25 CN CN 03147830 patent/CN1261503C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1566213A (en) | 2005-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI403558B (en) | Room temperature hardened organopolysiloxane composition | |
| CN109135660B (en) | Dealcoholized bi-component sealant and preparation method thereof | |
| US6809136B2 (en) | Room temperature curable organopolysiloxane compositions | |
| CN110818904B (en) | A kind of tackifier, its preparation method and two-component liquid silicone rubber adhesive comprising the same | |
| CN112143446A (en) | Bi-component silicone sealant and preparation method and application thereof | |
| TWI417343B (en) | Room temperature hardened organopolysiloxane composition | |
| CN112239645A (en) | Silicone adhesive with antibacterial and mildewproof effects and preparation method thereof | |
| CN108546543A (en) | Organosilicon sealant and its preparation method and application | |
| KR20200079479A (en) | Curable surface-protective coating composition, method for its preparation and application to metal substrates and coated metal substrates | |
| JPH05125284A (en) | Curable silicone composition | |
| CN106190012A (en) | A kind of transparent high intensity Self-leveling piptonychia alcohol type single-component organic silicon glue and preparation method thereof | |
| WO2020209083A1 (en) | Room-temperature-curable organopolysiloxane composition for oil seal, and automotive part | |
| JP3469325B2 (en) | Adhesion-promoting additive and low-temperature-curable organosiloxane composition containing the additive | |
| CN1146627C (en) | Organosilicon composition | |
| CN111394052A (en) | Dealcoholized condensed type double-component room temperature vulcanized silicone rubber and preparation method thereof | |
| KR102009276B1 (en) | Curable resin composition and primer composition | |
| JP2014218558A (en) | Room temperature curable polyorganosiloxane composition | |
| CN109852338B (en) | Fluorosilicone rubber composition, method for producing the same, and sealant and coating prepared from the same | |
| JP4821958B2 (en) | Room temperature curable organopolysiloxane composition | |
| CN109054725A (en) | A kind of one-component heat cure glue that temperature tolerance is good | |
| CN112778965B (en) | Alcohol-type silicon rubber adhesive and preparation method thereof | |
| CN110791198A (en) | Coating material and preparation method thereof | |
| JP2020026492A (en) | Room temperature curable polyorganosiloxane composition and cured product thereof | |
| CN1566213A (en) | Silicon rubber composition and its preparation process and use | |
| CN114672274A (en) | A kind of acrylic modified MS sealant and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |