CN1262553C - 封端的巯基硅烷 - Google Patents
封端的巯基硅烷 Download PDFInfo
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- CN1262553C CN1262553C CNB021433399A CN02143339A CN1262553C CN 1262553 C CN1262553 C CN 1262553C CN B021433399 A CNB021433399 A CN B021433399A CN 02143339 A CN02143339 A CN 02143339A CN 1262553 C CN1262553 C CN 1262553C
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- MCEBKLYUUDGVMD-UHFFFAOYSA-N [SiH3]S(=O)=O Chemical compound [SiH3]S(=O)=O MCEBKLYUUDGVMD-UHFFFAOYSA-N 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 18
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- 239000005995 Aluminium silicate Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
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- PDEDQSAFHNADLV-UHFFFAOYSA-M potassium;disodium;dinitrate;nitrite Chemical compound [Na+].[Na+].[K+].[O-]N=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PDEDQSAFHNADLV-UHFFFAOYSA-M 0.000 description 2
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- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
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- 229940123208 Biguanide Drugs 0.000 description 1
- 101100008047 Caenorhabditis elegans cut-3 gene Proteins 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
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- 244000043261 Hevea brasiliensis Species 0.000 description 1
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- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
- NQGIJDNPUZEBRU-UHFFFAOYSA-N dodecanoyl chloride Chemical class CCCCCCCCCCCC(Cl)=O NQGIJDNPUZEBRU-UHFFFAOYSA-N 0.000 description 1
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- ARBOVOVUTSQWSS-UHFFFAOYSA-N hexadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCC(Cl)=O ARBOVOVUTSQWSS-UHFFFAOYSA-N 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- AGVKXDPPPSLISR-UHFFFAOYSA-N n-ethylcyclohexanamine Chemical compound CCNC1CCCCC1 AGVKXDPPPSLISR-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
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- NTQYXUJLILNTFH-UHFFFAOYSA-N nonanoyl chloride Chemical compound CCCCCCCCC(Cl)=O NTQYXUJLILNTFH-UHFFFAOYSA-N 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
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- 150000003512 tertiary amines Chemical class 0.000 description 1
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- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003558 thiocarbamic acid derivatives Chemical class 0.000 description 1
- PIZNQHDTOZMVBH-UHFFFAOYSA-N thionylimide Chemical compound N=S=O PIZNQHDTOZMVBH-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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Classifications
-
- 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
- C08K5/5406—Silicon-containing compounds containing elements other than oxygen or nitrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Abstract
相应于通式I的封端的巯基硅烷，(R1O)3Si-R2-S-C(＝O)-C17H35(I)其生产是将相应的式(R1O)3Si-R2-SH的巯基硅烷与硬脂酰氯在辅助碱的存在下在适合的有机溶剂中反应，混合物加热至沸点以完成反应，滤除生成的固体残留物，蒸除溶剂。该封端的巯基硅烷可用于橡胶化合物。
Description
本发明涉及封端的巯基硅烷、其制备方法和其应用。
从WO99/09036可知式[[(ROC(O＝))p-(G)j]k-Y-S]r-G-(SiX3)s和[(X3Si)q-G]a-[Y-[S-G-SiX3]b]c的封端的巯基硅烷。
另外，从US6127468可知制备填充橡胶的方法，其中将橡胶、封端的巯基硅烷和无机填料混合，向混合物中加入式R2NC(＝S)-Sn-C(＝S)NR2的解封剂并硫化混合物。
已知的封端的巯基硅烷的缺点是它们的增强性低并且加工性能差。
本发明的目的是开发一种封端的巯基硅烷，其可便宜地生产并具有高模量和增强性以及良好的加工性和动态性能。
本发明提供封端的巯基硅烷，其特征在于它们相应于通式I
(R1O)3Si-R2-S-C(＝O)-C17H35 (I)
其中
R1彼此独立地表示H或(C1-C8)烷基，优选甲基或乙基，
R2表示直链或支链、饱和或不饱和的(C1-C8)二价烃基，优选CH2，CH2CH2，CH2CH2CH2，CH2CH2CH2CH2，CH(CH)3，CH2CH(CH3)，C(CH3)2，CH(C2H5)，CH2CH2CH(CH3)，CH2CH(CH3)CH2，或
和烷基C17H35是支链或直链的。
在本发明具体的实施方案中，R1可以是乙基，R2是CH2CH2CH2，烷基C17H35是直链((CH2)16CH3)。
根据本发明的式(I)封端的巯基硅烷的例子可以是：(CH3O)3Si-CH2-S-C(＝O)-C17H35，(CH3O)3Si-CH2CH2-S-C(＝O)-C17H35，(CH3O)3Si-CH2CH2CH2-S-C(＝O)-C17H35，(CH3O)3Si-CH2CH2CH2CH2-S-C(＝O)-C17H35，(CH3O)3Si-CH2CH2CH2CH2CH2-S-C(＝O)-C17H35，(C2H5O)3Si-CH2-S-C(＝O)-C17H35，(C2H5O)3Si-CH2CH2-S-C(＝O)-C17H35，(C2H5O)3Si-CH2CH2CH2-S-C(＝O)-C17H35，(C2H5O)3Si-CH2CH2CH2CH2-S-C(＝O)-C17H35，或(C2H5O)3Si-CH2CH2CH2CH2CH2-S-C(＝O)-C17H35。
本发明还提供生产通式I的封端的巯基硅烷的方法，其特征在于相应的式(R1O)3Si-R2-SH巯基硅烷与硬脂酰氯在辅助碱的存在下在适合的有机溶剂中反应，混合物加热至沸点以完成反应，滤除生成的固体残留物，蒸除溶剂。
式(R1O)3Si-R2-SH巯基硅烷的例子可以是：(CH3O)3Si-CH2-SH，(CH3O)3Si-CH2CH2-SH，(CH3O)3Si-CH2CH2CH2-SH，(CH3O)3Si-CH2CH2CH2CH2-SH，(CH3O)3Si-CH2CH2CH2CH2CH2-SH，(C2H5O)3Si-CH2-SH，(C2H5O)3Si-CH2CH2-SH，(C2H5O)3Si-CH2CH2CH2-SH，(C2H5O)3Si-CH2CH2CH2CH2-SH，或(C2H5O)3Si-CH2CH2CH2CH2CH2-SH。
三乙胺或其它胺可用作辅助碱。
烷烃可用作有机溶剂。
根据本发明的封端的巯基硅烷特别适用于橡胶化合物。
本发明还提供橡胶化合物，其含有橡胶、填料——优选沉淀二氧化硅——和任选的其它橡胶助剂以及至少一种根据本发明的式I封端的巯基硅烷和任选的解封剂，基于所用的氧化填料的量，封端的巯基硅烷的量为0.1-15wt％，优选5-10wt％。
根据本发明的封端的巯基硅烷的加入和填料的加入可优选在100-200℃的料温进行，但是也可以在之后较低的温度(40-100℃)进行，例如与其它橡胶助剂一起加入。
根据本发明的封端的巯基硅烷可均以纯净的形式加入到混合过程中，并应用到惰性有机或无机载体上。优选的载体材料可以是二氧化硅、天然的或合成的硅酸盐、蜡、热塑塑料、氧化铝或碳黑。
下述可作为填料用于根据本发明的橡胶化合物：
-炭黑：在此使用的炭黑通过灯黑、炉黑或气黑法生产，具有BET表面积20-200m2/g。碳黑还可任选含有杂原子，例如Si。
-高分散性二氧化硅，通过例如从硅酸盐的溶液沉淀或卤化硅火焰裂解生成，比表面积为5-1000，优选20-400m2/g(BET表面积)，基本颗粒尺寸10-400nm。二氧化硅还可任选作为与其它金属氧化物混合的氧化物存在，其它金属氧化物是诸如Al、Mg、Ca、Ba、Zn和钛的氧化物。
-合成的硅酸盐，诸如硅酸铝，碱土金属硅酸盐，诸如硅酸镁或硅酸钙，BET表面积是20-400m2/g，基本颗粒直径10-400nm。
-合成的或天然的氧化铝和氢氧化物。
-天然硅酸盐，诸如高岭土和其它天然生成的二氧化硅。
-玻璃纤维和玻璃纤维产品(垫、绳)或微玻璃珠。
基于100份橡胶，BET表面积20-400m2/g的碳黑或从硅酸盐溶液沉淀生成的BET表面积20-400m2/g的高分散性的硅酸盐可优选分别以5-150重量份的量使用。
所述的填料可单独使用或作为混合物使用。在该方法特别优选的实施方案中，基于100重量份所使用的填料，可使用10-150重量份的浅色填料，任选与0-100重量份碳黑以及0.1-15重量份、优选5-10重量份的式(I)化合物一起使用生产混合物。
为了生产根据本发明的橡胶化合物，除了天然橡胶，合成橡胶也适用。优选的合成橡胶是W.Hofmann，Kautschuktechnologie，GenterVerlag，Stuttgart 1980中所述的。除了别的之外，它们包括：
-聚丁二烯(BR)，
-聚异戊二烯(IR)，
-苯乙烯/丁二烯共聚物，苯乙烯的含量为1-60wt％，优选2-50wt％(SBR)，
-异丁烯/异戊二烯共聚物(IIR)，
-丁二烯/丙烯腈共聚物，丙烯腈含量为5-60wt％，优选10-50wt％(NBR)，
-部分氢化或完全氢化的NBR橡胶(HNBR)，
-乙烯/丙烯/二烯烃共聚物(EPDM)，和这些橡胶的混合物。对于生产载重轮胎，玻璃化转变温度大于-50℃的阴离子催化的聚合S-SBR橡胶(溶液SBR)和它们与二烯橡胶的混合物是非常有利的。
作为解封剂，可使用叔胺、路易斯酸、硫醇或亲核试剂，诸如伯胺、仲胺或含C＝N-的胺。解封剂的例子可以是R2NC(＝S)-Sn-C(＝S)NR2，其中n＝1-4，R是C1-C4烷基、N，N’-二苯基胍、N，N’，N”-三苯基胍、N，N’-二邻甲苯基胍、邻双胍、六亚甲基四胺、环己基乙基胺、二丁基胺、秋兰姆和4，4’-二氨基二苯基甲烷。
根据本发明的橡胶化合物可含有其它橡胶助剂产品，诸如反应促进剂、抗氧化剂、热稳定剂、光稳定剂、抗臭氧剂、加工助剂、增塑剂、增粘剂、发泡剂、染料、蜡、补充剂、有机酸、抑制剂、金属氧化物、活化剂，如三乙醇胺、聚乙二醇和己三醇，它们对于橡胶工业是已知的。
橡胶助剂可以常规量使用，其取决于预期的应用，除了别的之外。常规用量是例如基于橡胶的0.1-50wt％。封端的巯基硅烷可独立地用作交联剂。一般推荐加入其它交联剂。硫或过氧化物可用作其它已知的交联剂。根据本发明的橡胶化合物另外可含有硫化促进剂。适合的硫化促进剂的例子是巯基苯并噻唑、亚磺酰胺、胍、秋兰姆、二硫氨基甲酸酯、硫脲和硫代碳酸酯。基于橡胶，硫化促进剂和硫或过氧化物的用量为0.1-10wt％，优选0.1-5wt％。
根据本发明的橡胶化合物的硫化可在100-200℃进行，优选130-180℃，任选在10-200巴的压力下。
橡胶或橡胶混合物、填料、任选的橡胶助剂、根据本发明的封端的巯基硅烷和任选的解封剂可在混合设备中混合，诸如滚筒、密闭式混合机和混合挤出机。根据本发明的橡胶硫化产品适用于模塑生产，例如用于生产充气轮胎、轮胎胎面、电缆护层、软管、传动皮带、传送带、辊涂层、轮胎、鞋底、密封环和阻尼元件。
当根据本发明的封端的巯基硅烷用于橡胶化合物，与根据现有技术的化合物相比，优点表现在增加了补强作用，降低了混合物的粘度和有更好的加工性能。
实施例1-4封端的巯基硅烷的制备
实施例1(比较例)
制备(EtO)3Si-(CH2)3-S-C(＝O)-C8H17
在5℃，加入57.78g三乙胺后，将87.73g壬酰氯滴加到118.39g3-巯基丙基三乙氧基硅烷在820ml石油醚(沸程50-70℃)中的溶液中。回流加热90分钟，过滤冷却的悬浮液，滤饼用石油醚再洗涤两次，合并得到的滤液，除去溶剂。得到187.74g液体产物，用1H-NMR光谱证实其特性。
实施例2(比较例)
制备(EtO)3Si-(CH2)3-S-C(＝O)-C15H31
在8℃，加入48.15g三乙胺后，将113.75g十六酰氯滴加到98.66g3-巯基丙基三乙氧基硅烷在1300ml石油醚(沸程50-70℃)中的溶液中。回流加热60分钟后，过滤冷却的悬浮液，滤饼用石油醚再洗涤两次，合并得到的滤液，除去溶剂。得到183.30g液体产物，用1H-NMR光谱证实其特性。
实施例3
制备(EtO)3Si-(CH2)3-S-C(＝O)-C17H35
在5℃，加入48.15g三乙胺后，将125.35g硬脂酰氯用可加热的滴液漏斗滴加到98.66g 3-巯基丙基三乙氧基硅烷在1300ml石油醚(沸程50-70℃)中的溶液中。回流加热90分钟，过滤冷却的悬浮液，滤饼用石油醚再洗涤两次，合并得到的滤液，除去溶剂。得到186.71g液体产物，用1H-NMR光谱证实其特性。
实施例4(比较例)
制备(EtO)3Si-(CH2)3-S-C(＝O)-C21H43
在5℃，加入48.15g三乙胺后，将148.57g二十二酰氯用固体计量装置加入到98.66g 3-巯基丙基三乙氧基硅烷在1300ml石油醚(沸程50-70℃)中的溶液中。回流加热90分钟，过滤冷却的悬浮液，滤饼用石油醚再洗涤两次，合并得到的滤液，除去溶剂。得到213.55g低熔点产物，用1H-NMR光谱证实其特性。
实施例5-9：橡胶测试
下表1给出了用于橡胶化合物的一般配方。单位phr在此的意思是重量份数，基于所用的100份粗橡胶。
在实施例5-9中硅烷以等摩尔的量计量。
表1
| 物质 | 实施例5 | 实施例6 | 实施例7 | 实施例8 | 实施例9 |
| 第一阶段 | [phr] | [phr] | [phr] | [phr] | [phr] |
| Buna VSL 4515-0Buna CB 24Ultrasil 7000 GRSi 69硅烷实施例1硅烷实施例2硅烷实施例3硅烷实施例4ZnO硬脂酸Naftolen ZDVulkanox 4020保护剂G35P | 75.025.080.07.0----2.51.032.52.01.5 | 75.025.080.0-9.95---2.51.032.52.01.5 | 75.025.080.0--12.53--2.51.032.52.01.5 | 75.025.080.0---13.26-2.51.032.52.01.5 | 75.025.080.0----14.742.51.032.52.01.5 |
| 第三阶段 | |||||
| 第二阶段批次DPGCBS硫 | 2.01.72.2 | 2.01.72.2 | 2.01.72.2 | 2.01.72.2 | 2.01.72.2 |
聚合物VSL 4515-0是购自Bayer AG的溶液聚合的SBR共聚物，苯乙烯含量为15wt％，丁二烯含量为85wt％。丁二烯单体单元的45wt％为1，2-连接的。
聚合物Buna CB 24是购自Bayer AG的顺-1，4-聚丁二烯，顺-1，4含量至少为96％，Mooney粘度在44-50之间。
Ultrasil 7000 GR是购自Degussa AG的二氧化硅，BET比表面积为170m2/g。
Si 69是购自Degussa AG的二(3-三乙氧基甲硅烷基丙基)四硫烷。
购自Chemetall的Naftolen ZD用作芳香油。Vulkanox 4020是购自Bayer AG的PPD。保护剂G35P是购自HB-Fuller GmbH的抗臭氧蜡。Vulkacit D(DPG)和Vulkacit CZ(CBS)是购自Bayer AG的市售产品。
在密闭式混合机中根据表2给出的数据以三个阶段制备橡胶化合物。
表2
| 阶段1 | |
| 装置 | |
| 混合设备摩擦速度冲压空体积装料高度物流速度 | Werner & Pfleiderer GK 1.5E1∶170min-15.5bar1.5810.5570℃ |
| 混合操作 | |
| 0～1分钟1～3分钟3～4分钟4分钟4～5分钟5分钟5～6分钟储存 | 聚合物1/2二氧化硅，碳黑，ZnO，硬脂酸，硅烷，油1/2二氧化硅，抗氧化剂精炼混合精炼混合并分送室温24h |
| 阶段2 | |
| 装置 | |
| 混合设备速度装料高度物流温度 | 除了变量外，与阶段1相同0.5180℃ |
| 混合操作 | |
| 0～2分钟2～5分钟5分钟批产品温度 | 阶段1的批产品在145～155℃混合分送并在实验室轧制机上形成轧制的片(直径200mm，长450mm，物流温度50℃)，然后成片100～110℃ |
| 阶段3 | |
| 装置 | |
| 混合设备速度装料高度物流温度 | 如阶段2，除了：40min-10.4950℃ |
| 混合操作 | |
| 0～2分钟2分钟 | 阶段2的批产品，用硫处理，加速剂分送并在实验室轧制机上匀化(直径200mm，长450mm，物流温度50℃)，左右各切去3*，通过8*长、3*宽的轧制机，然后成片 |
试验片材的硫化阶段是在165℃进行20分钟。
橡胶的试验通过表3给出的试验方法进行。
表3
| 物理试验 | 标准条件 |
| ML 1+4，100℃ | DIN 53523/3，ISO 667 |
| 硫化试验，165℃ | DIN 53529/3，ISO 6502 |
| 在环上的抗拉试验，23℃拉伸强度模量断裂时的伸长率 | DIN 53504，ISO 37 |
| 肖氏A硬座，23℃ | DIN 53 505 |
| 球反弹，0和60℃ | ASTM D 5308 |
| 粘弹性，0和60℃，16Hz，50N起始力和25N振幅力复数模量E*，损耗系数tanδ | DIN 53 513，ISO 2856 |
| Goodrich挠度计，在23℃和0.175英寸冲程25分钟 | DIN 53 533，ASTM D 623 A |
| DNA磨损，10N力 | DIN 53 516 |
| 压缩变形，在70℃，22小时 | DIN 53 517，ISO 815 |
| 分散 | ISO/DIS 11345 |
测定下列粗混合物和硫化产品的技术数据(表4)：
表4
| 粗混合物的结果 | ||||||
| 特性： | 单位 | 实施例5 | 实施例6 | 实施例7 | 实施例8 | 实施例9 |
| Hitec 165℃Dmax-Dmint10％t90％ | [dNm]minmin | 6.65.510.8 | 6.95.38.3 | 6.25.48.3 | 5.95.28.9 | 5.56.410.0 |
| ML1+4 100℃第三阶段 | [ME] | 53 | 35 | 32 | 33 | 32 |
| 硫化产品结果 | ||||||
| 特性： | 单位 | 实施例5 | 实施例6 | 实施例7 | 实施例8 | 实施例9 |
| 在环上的抗拉试验拉伸强度模量100％模量300％断裂时的伸长率模量300％/100％ | [Mpa][Mpa][Mpa][％][-] | 14.71.910.13805.3 | 13.81.99.53905.0 | 13.61.77.74404.5 | 13.91.78.14304.8 | 13.71.56.65004.4 |
| 肖氏A硬度(23℃) | [SH] | 64 | 60 | 58 | 58 | 57 |
| 球反弹60℃ | [％] | 60.1 | 58.9 | 61.1 | 60.3 | 60.4 |
| DIN磨损 | [mm3] | 62 | 76 | 93 | 89 | 103 |
| Goodrich挠度计，0.175英寸冲程，25分钟，23℃接触温度刺穿温度永久变形 | [℃][℃]％ | 48952.9 | 44842.0 | 43821.4 | 44851.5 | 44841.4 |
| MTS，16Hz，50N+/-25NE*，0℃E*，60℃损耗系数tanδ，0℃损耗系数tanδ，60℃ | [Mpa][Mpa][-][-] | 15.17.50.3290.148 | 12.47.70.2780.123 | 12.67.20.2780.127 | 10.36.70.2700.129 | 15.76.90.3200.134 |
| 菲利普分散 | [-] | 8 | 8 | 8 | 9 | 7 |
如表4所示，当等摩尔计量时，实施例8的根据本发明的硅烷给出了最低的E*(0℃)值，这表明在轮胎胎面中改进了冬季特性。另外，混合物8具有最好的分散值，与混合物7和9相比，表现出高模量。
实施例10-14：橡胶测试
下表5给出了用于橡胶化合物的一般配方。单位phr在此的意思是重量份数，基于100份所用的粗橡胶。
表5
| 物质 | 实施例10 | 实施例11 | 实施例12 | 实施例13 | 实施例14 |
| 第一阶段 | [phr] | [phr] | [phr] | [phr] | [phr] |
| Buna VSL 4515-0Buna CB 24Ultrasil 7000 GRSi 69硅烷实施例1硅烷实施例2硅烷实施例3硅烷实施例4ZnO硬脂酸Naftolen ZDVulkanox 4020保护剂G35P | 75.025.080.07.0----2.51.032.52.01.5 | 75.025.080.0-7.0---2.51.032.52.01.5 | 75.025.080.0--7.0--2.51.032.52.01.5 | 75.025.080.0---7.0-2.51.032.52.01.5 | 75.025.080.0----7.02.51.032.52.01.5 |
| 第三阶段 | |||||
| 第二阶段批次DPGCBS硫 | 2.01.72.2 | 2.01.72.2 | 2.01.72.2 | 2.01.72.2 | 2.01.72.2 |
在实施例10-14中硅烷以等重量计量。
在密闭式混合机中根据表2给出的数据以三个阶段制备橡胶化合物，在165℃进行20分钟硫化。
根据表3给出的试验方法进行橡胶测试。
确定下列粗混合物和硫化产品的技术数据(表6)：
表6
| 粗混合物的结果 | ||||||
| 特性 | 单位 | 实施例10 | 实施例11 | 实施例12 | 实施例13 | 实施例14 |
| Hitec 165℃Dmax-Dmint10％t90％ | [dNm]minmin | 6.65.510.8 | 6.65.711.9 | 6.55.617.8 | 6.45.217.5 | 6.35.518.4 |
| ML 1+4100℃第三阶段 | [ME] | 53 | 39 | 39 | 40 | 38 |
| 硫化产品结果 | ||||||
| 特性： | 单位 | 实施例10 | 实施例11 | 实施例12 | 实施例13 | 实施例14 |
| 在环上的抗拉试验拉伸强度模量100％模量300％断裂时的伸长率模量300％/100％ | [Mpa][Mpa][Mpa][％][-] | 14.71.910.13805.3 | 13.41.99.63705.1 | 14.42.211.13505.0 | 14.22.111.23505.3 | 13.82.110.23704.9 |
| 肖氏A硬度(23℃) | [SH] | 64 | 60 | 61 | 61 | 62 |
| 球反弹60℃ | [％] | 60.1 | 60.5 | 62.0 | 62.6 | 60.5 |
| DIN磨损 | [mm3] | 62 | 71 | 55 | 57 | 63 |
| Goodrich挠度计，0.175英寸冲程，25分钟，23℃接触温度刺穿温度永久变形 | [℃][℃]％ | 48952.9 | 45851.8 | 47901.5 | 45871.4 | 46891.6 |
| MTS，16Hz，50N+/-25NE*，0℃E*，60℃损耗系数tanδ，0℃损耗系数tanδ，60℃ | [Mpa][Mpa][-][-] | 15.17.50.3290.148 | 12.47.50.2710.123 | 13.17.90.2710.119 | 15.78.40.3080.124 | 12.57.60.2740.119 |
| 菲利普分散 | [-] | 8 | 8 | 8 | 8 | 7 |
如表6所示，当等重量计量时，实施例13的根据本发明的硅烷给出了最短的t10％时间，最高的300％模量和最高的球反弹60℃值，这表明在轮胎胎面中改进了耐延压性。另外，根据本发明的实施例13的300％/100％增强系数高于含有更短或更长烷基链的硅烷(实施例11、12和14)的增强系数，与Si 69参照相同。根据本发明的实施例13随烷基链长的变化表现出损耗系数tanδ0℃的最高值，这表明改进了轮胎的湿刹车性能。
Claims (6)
1.封端的巯基硅烷，其特征在于它们相应于通式I
(R1O)3Si-R2-S-C(＝O)-C17H35 (I)
其中
R1彼此独立地表示H或C1-C8烷基，
R2表示直链或支链、饱和或不饱和的C1-C8二价烃基，并且烷基C17H35是支链或直链的。
2.根据权利要求1的封端的巯基硅烷，其特征在于R1是乙基，R2是CH2CH2CH2，并且烷基C17H35是直链的。
3.生产根据权利要求1的通式I的封端的巯基硅烷的方法，其特征在于相应的式(R1O)3Si-R2-SH巯基硅烷与硬脂酰氯在辅助碱的存在下在适合的有机溶剂中反应，其中，R1彼此独立地表示H或C1-C8烷基，R2表示直链或支链、饱和或不饱和的C1-C8二价烃基，并且烷基C17H35是支链或直链的；将混合物加热至沸点以完成反应，滤除生成的固体残留物，蒸除溶剂。
4.橡胶化合物，其含有橡胶、填料和任选存在的其它橡胶助剂以及至少一种根据权利要求1的封端的巯基硅烷和任选存在的解封剂，基于所用的氧化填料的量，封端的巯基硅烷的量为0.1-15wt％。
5.生产根据权利要求4的橡胶化合物的方法，其特征在于将橡胶或橡胶混合物、填料、根据式I的封端的巯基硅烷和任选存在的解封剂在混合设备中混合。
6.根据权利要求1的封端的巯基硅烷在充气轮胎、轮胎胎面、电缆护层、软管、传动皮带、传送带、辊涂层、轮胎、鞋底、密封环和阻尼元件中的用途。
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10147520.9 | 2001-09-26 | ||
| DE10147520 | 2001-09-26 | ||
| DE10163945A DE10163945C1 (de) | 2001-09-26 | 2001-12-22 | Geblockte Mercaptosilane, ein Verfahren zu ihrer Herstellung sowie ihre Verwendung |
| DE10163945.7 | 2001-12-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1408715A CN1408715A (zh) | 2003-04-09 |
| CN1262553C true CN1262553C (zh) | 2006-07-05 |
Family
ID=26010234
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021433399A Expired - Fee Related CN1262553C (zh) | 2001-09-26 | 2002-09-26 | 封端的巯基硅烷 |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20030130388A1 (zh) |
| EP (1) | EP1298163B1 (zh) |
| JP (1) | JP2003201295A (zh) |
| CN (1) | CN1262553C (zh) |
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| AU2003287405A1 (en) | 2002-11-04 | 2005-02-04 | General Electric Company | Process for manufacture of blocked mercaptosilane coupling agents |
| DE10327624B3 (de) * | 2003-06-20 | 2004-12-30 | Degussa Ag | Organosiliciumverbindungen, Verfahren zu ihrer Herstellung, sowie ihre Verwendung |
| JPWO2005049493A1 (ja) * | 2003-11-18 | 2007-06-07 | 横浜ゴム株式会社 | シランカップリング剤処理シリカ及びそれを含むゴム組成物 |
| DE10354616A1 (de) * | 2003-11-21 | 2005-06-23 | Degussa Ag | Kautschukmischungen |
| US20050245753A1 (en) * | 2004-05-03 | 2005-11-03 | Cruse Richard W | Cyclic diol-derived blocked mercaptofunctional silane compositions |
| JP2005320374A (ja) * | 2004-05-06 | 2005-11-17 | Yokohama Rubber Co Ltd:The | タイヤトレッド用ゴム組成物 |
| US7531588B2 (en) * | 2004-07-30 | 2009-05-12 | Momentive Performance Materials Inc. | Silane compositions, processes for their preparation and rubber compositions containing same |
| US7928258B2 (en) | 2004-08-20 | 2011-04-19 | Momentive Performance Materials Inc. | Cyclic diol-derived blocked mercaptofunctional silane compositions |
| JP5433233B2 (ja) * | 2005-03-24 | 2014-03-05 | 株式会社ブリヂストン | 揮発性有機化合物（ｖｏｃ）の放出が少ないシリカ補強ゴムの配合 |
| DE102005038794A1 (de) * | 2005-08-17 | 2007-02-22 | Degussa Ag | Kautschukmischungen |
| DE102005038791A1 (de) * | 2005-08-17 | 2007-02-22 | Degussa Ag | Organosiliciumverbindungen, ihre Herstellung und ihre Verwendung |
| DE102005043201A1 (de) * | 2005-09-09 | 2007-03-15 | Degussa Ag | Fällungskieselsäuren mit einer besonderen Porengrößenverteilung |
| DE102005043202A1 (de) | 2005-09-09 | 2007-03-15 | Degussa Ag | Fällungskieselsäuren mit besonderer Porengrößenverteilung |
| JP5108528B2 (ja) * | 2005-11-25 | 2012-12-26 | 株式会社ブリヂストン | 有機珪素化合物及びそれを用いたゴム組成物 |
| US7560513B2 (en) * | 2005-12-16 | 2009-07-14 | Continental Ag | Polyorganosiloxane composition for use in unsaturated elastomer, article made therefrom, and associated method |
| US7776967B2 (en) * | 2005-12-16 | 2010-08-17 | Continental Ag | Polyorganosiloxane composition for use in unsaturated elastomer, article made therefrom, and associated method |
| US7652162B2 (en) * | 2005-12-16 | 2010-01-26 | Momentive Performance Materials Inc. | Polyorganosiloxane composition, and associated method |
| US7504456B2 (en) * | 2006-02-21 | 2009-03-17 | Momentive Performance Materials Inc. | Rubber composition containing organofunctional silane |
| US7718819B2 (en) * | 2006-02-21 | 2010-05-18 | Momentive Performance Materials Inc. | Process for making organofunctional silanes and mixtures thereof |
| US7510670B2 (en) | 2006-02-21 | 2009-03-31 | Momentive Performance Materials Inc. | Free flowing filler composition based on organofunctional silane |
| US7919650B2 (en) * | 2006-02-21 | 2011-04-05 | Momentive Performance Materials Inc. | Organofunctional silanes and their mixtures |
| US7550540B2 (en) * | 2006-08-14 | 2009-06-23 | Momentive Performance Materials Inc. | Rubber composition and articles therefrom both comprising mercapto-functional silane |
| US8008519B2 (en) * | 2006-08-14 | 2011-08-30 | Momentive Performance Materials Inc. | Process for making mercapto-functional silane |
| US7368584B2 (en) | 2006-08-14 | 2008-05-06 | Momentive Performance Materials Inc. | Mercapto-functional silane |
| US8097744B2 (en) * | 2006-08-14 | 2012-01-17 | Momentive Performance Materials Inc. | Free flowing filler composition comprising mercapto-functional silane |
| US7968634B2 (en) * | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing silated core polysulfides |
| US7968633B2 (en) * | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
| US7968636B2 (en) * | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing silated cyclic core polysulfides |
| US7737202B2 (en) * | 2006-12-28 | 2010-06-15 | Momentive Performance Materials Inc. | Free-flowing filler composition and rubber composition containing same |
| US8592506B2 (en) * | 2006-12-28 | 2013-11-26 | Continental Ag | Tire compositions and components containing blocked mercaptosilane coupling agent |
| US7687558B2 (en) * | 2006-12-28 | 2010-03-30 | Momentive Performance Materials Inc. | Silated cyclic core polysulfides, their preparation and use in filled elastomer compositions |
| US7960460B2 (en) * | 2006-12-28 | 2011-06-14 | Momentive Performance Materials, Inc. | Free-flowing filler composition and rubber composition containing same |
| US7968635B2 (en) * | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
| US7696269B2 (en) | 2006-12-28 | 2010-04-13 | Momentive Performance Materials Inc. | Silated core polysulfides, their preparation and use in filled elastomer compositions |
| US7781606B2 (en) * | 2006-12-28 | 2010-08-24 | Momentive Performance Materials Inc. | Blocked mercaptosilane coupling agents, process for making and uses in rubber |
| US8501895B2 (en) * | 2007-05-23 | 2013-08-06 | Bridgestone Corporation | Method for making alkoxy-modified silsesquioxanes and amino alkoxy-modified silsesquioxanes |
| US7915368B2 (en) * | 2007-05-23 | 2011-03-29 | Bridgestone Corporation | Method for making alkoxy-modified silsesquioxanes |
| US7816435B2 (en) * | 2007-10-31 | 2010-10-19 | Momentive Performance Materials Inc. | Halo-functional silane, process for its preparation, rubber composition containing same and articles manufactured therefrom |
| US8962746B2 (en) | 2007-12-27 | 2015-02-24 | Bridgestone Corporation | Methods of making blocked-mercapto alkoxy-modified silsesquioxane compounds |
| US8513371B2 (en) * | 2007-12-31 | 2013-08-20 | Bridgestone Corporation | Amino alkoxy-modified silsesquioxanes and method of preparation |
| US8794282B2 (en) * | 2007-12-31 | 2014-08-05 | Bridgestone Corporation | Amino alkoxy-modified silsesquioxane adhesives for improved metal adhesion and metal adhesion retention to cured rubber |
| FR2940302B1 (fr) * | 2008-12-22 | 2012-07-27 | Michelin Soc Tech | Composition de caoutchouc comportant un agent de couplage mercaptosilane bloque |
| FR2940290B1 (fr) * | 2008-12-22 | 2010-12-31 | Michelin Soc Tech | Agent de couplage mercaptosilane bloque |
| US8642691B2 (en) | 2009-12-28 | 2014-02-04 | Bridgestone Corporation | Amino alkoxy-modified silsesquioxane adhesives for improved metal adhesion and metal adhesion retention to cured rubber |
| US9447262B2 (en) | 2011-03-02 | 2016-09-20 | Momentive Performance Materials Inc. | Rubber composition containing blocked mercaptosilanes and articles made therefrom |
| FR2985730B1 (fr) * | 2011-12-16 | 2014-01-10 | Michelin Soc Tech | Composition de caoutchouc comprenant un agent de couplage mercaptosilane bloque |
| JP6297669B2 (ja) | 2013-03-29 | 2018-03-20 | モメンティブ パフォーマンス マテリアルズ インコーポレイテッド | チオカルボキシラートシランの調製のための触媒プロセス |
| KR102340560B1 (ko) | 2013-07-10 | 2021-12-21 | 모멘티브 퍼포먼스 머티리얼즈 인크. | 티오카복실레이트 실란의 연속 제조 방법 |
| CN103694744B (zh) * | 2013-12-06 | 2015-10-28 | 江西晨光新材料有限公司 | 一种表面含硫硅烷修饰的二氧化硅微球及其合成方法 |
| WO2016109625A1 (en) | 2014-12-31 | 2016-07-07 | Bridgestone Corporation | Amino alkoxy-modified silsesquioxane adhesives for adhering steel alloy to rubber |
| CN109517006B (zh) * | 2018-11-13 | 2021-03-16 | 江西宏柏新材料股份有限公司 | 塔式有机法连续生产3-辛酰基硫代丙基三乙氧基硅烷的方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0617460B2 (ja) * | 1987-04-02 | 1994-03-09 | 信越化学工業株式会社 | 半導体装置封止用エポキシ樹脂組成物 |
| JPH068366B2 (ja) * | 1987-04-23 | 1994-02-02 | 株式会社ブリヂストン | タイヤ用ゴム組成物 |
| CA2072040C (en) * | 1992-06-23 | 2002-06-11 | Charles Borg | Method and device to facilitate the cognitive development of alternative response behaviour |
| US5285430A (en) * | 1992-12-28 | 1994-02-08 | Decker Neil W | Behavior modification wristwatch |
| EP0958298B2 (en) * | 1997-08-21 | 2008-10-22 | Momentive Performance Materials Inc. | Blocked mercaptosilane coupling agents for filled rubbers |
| US6567785B2 (en) * | 1999-06-19 | 2003-05-20 | John Richard Clendenon | Electronic behavior modification reminder system and method |
| US6305839B1 (en) * | 1999-12-16 | 2001-10-23 | Duje Krstulovic | Wristwatch to aid in smoking cessation program |
| US6635700B2 (en) * | 2000-12-15 | 2003-10-21 | Crompton Corporation | Mineral-filled elastomer compositions |
| US6777569B1 (en) * | 2003-03-03 | 2004-08-17 | General Electric Company | Process for the manufacture of blocked mercaptosilanes |
-
2002
- 2002-08-29 EP EP02019344A patent/EP1298163B1/de not_active Expired - Lifetime
- 2002-09-25 JP JP2002279869A patent/JP2003201295A/ja not_active Withdrawn
- 2002-09-26 CN CNB021433399A patent/CN1262553C/zh not_active Expired - Fee Related
- 2002-09-26 US US10/254,658 patent/US20030130388A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003201295A (ja) | 2003-07-18 |
| EP1298163B1 (de) | 2005-07-06 |
| CN1408715A (zh) | 2003-04-09 |
| EP1298163A1 (de) | 2003-04-02 |
| US20030130388A1 (en) | 2003-07-10 |
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