CN1069748A - 制备可硫化的模制复合物的方法以及用该方法制得的模制复合物 - Google Patents
制备可硫化的模制复合物的方法以及用该方法制得的模制复合物 Download PDFInfo
- Publication number
- CN1069748A CN1069748A CN92109579A CN92109579A CN1069748A CN 1069748 A CN1069748 A CN 1069748A CN 92109579 A CN92109579 A CN 92109579A CN 92109579 A CN92109579 A CN 92109579A CN 1069748 A CN1069748 A CN 1069748A
- Authority
- CN
- China
- Prior art keywords
- molding compound
- thiuram
- consumption
- rubber
- promotor
- 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.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 20
- 238000000465 moulding Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims description 10
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229960002447 thiram Drugs 0.000 claims abstract description 16
- -1 3-thiocyano propyl Chemical group 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 229910000077 silane Inorganic materials 0.000 claims abstract description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 3
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 3
- 229920001194 natural rubber Polymers 0.000 claims abstract description 3
- 229920003051 synthetic elastomer Polymers 0.000 claims abstract description 3
- 239000005061 synthetic rubber Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000945 filler Substances 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 6
- 150000004659 dithiocarbamates Chemical class 0.000 claims description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 description 12
- 239000005060 rubber Substances 0.000 description 12
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 6
- 229920002943 EPDM rubber Polymers 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000010057 rubber processing Methods 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 3
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101100449067 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cbs-2 gene Proteins 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 208000036142 Viral infection Diseases 0.000 description 1
- 239000005870 Ziram Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- GWCGONFKYSQUBK-UHFFFAOYSA-N ethyl n-phenylcarbamodithioate Chemical compound CCSC(=S)NC1=CC=CC=C1 GWCGONFKYSQUBK-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 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
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- QBQOBZNQTAFENX-UHFFFAOYSA-N n-cyclohexylsulfanyl-1,3-benzothiazol-2-amine Chemical compound C1CCCCC1SNC1=NC2=CC=CC=C2S1 QBQOBZNQTAFENX-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical compound [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
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
- C08K5/548—Silicon-containing compounds containing sulfur
-
- 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
-
- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paper (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Tires In General (AREA)
Abstract
本发明涉及包含一种或多种天然橡胶，或合成橡
胶，或聚合物的可硫化模制复合物的生产方法。其中
通过使用3-氰硫基丙基三烷氧基硅烷使秋兰姆和/
或二硫代氨基甲酸盐类促进剂的用量减少到原来需
要量的一半。
Description
本发明涉及可硫化的模制复合物的生产方法以及用这种方法所生产的模制复合物。
近年来，在橡胶制品加工，硫化和贮存过程中生成挥发性致癌的正亚硝胺所带来的问题已受到橡胶加工工业的日益关注。在联邦德国已有一些初步的法规（例如“危险物质技术标准”（TRGS552））规定了工作环境中挥发性正亚硝胺的含量上限，并对超过这些上限的工厂的产量作了严格的限制。为了避免这种情况，橡胶加工工业正在日益致力于替代橡胶混合物中能生成正亚硝胺的成分，如果不能做到这一点，至少也要减少其需用量。
与此同时由各出版物（例如参见
R.H.Schuster，F.Nabholz，M.Gmünder，“Kautschuk，Gummi，Kunststoffe 2”（1990）95;W.Hoffmann，“Zum Problem der Herstellung N-nitrosaminfreier Gummiartikel”，paper presented before the DKG-Bezirksgruppe Süd-u.Südwestdeutschland，April 1990），
可以得知，亚硝胺是在橡胶混合物配料，处理和硫化所需的温度下，特别是通过混合物中能释放出仲胺的组分的分解以及这些仲胺与实际上无所不在的氮氧化物NOx的反应而生成的。
胺类的主要来源之一是目前主要用于橡胶工业中的次磺酰胺，秋兰姆和二硫代氨基甲酸盐这类硫化促进剂。因此，橡胶加工工业自然正在致力于用较安全的化合物替代这些有毒性的，能生成亚硝胺的促进剂，或者至少是减少其需用量，而同时又不使橡胶性能有重大改变。
本发明涉及可硫化的模制复合物的生产方法，该复合物中包含用硫或给硫体及促进剂进行硫化的一种或多种天然橡胶、合成橡胶或聚合物，填料，以及其它典型组分，至少一种促进剂属于目前所用的秋兰姆和/或二硫代氨基甲酸盐这一类，其特点在于同时还使用通式如下的3-氰硫基丙基三烷氧基硅烷：
式中R为C1-8烷基，与不含有机硅化合物的可硫化模制复合物中原来的用量相比，秋兰姆和/或二硫代氨基甲酸盐类促进剂的用量至少减低到一半。
本发明也涉及用这种方法所制得的硫化橡胶。
所述的促进剂尤指二硫化四甲基秋兰姆（TMTD）、一硫化四甲基秋兰姆（TMTM）、正二甲基二硫代氨基甲酸锌（ZDMC）、正二乙基二硫代氨基甲酸锌（ZDEC）、正乙苯基二硫代氨基甲酸锌（ZEPC）。
在先有技术中，这些促进剂的用量为0.2至10phr（每100份橡胶中的份数）。
相对于原来的用量而言，降低幅度以20%至50%较好，在
某些场合下甚至可到100%（参见实施例2）。
已经发现，按照本发明可以减少有害促进剂的数量而又不致于使橡胶的性能降低到通常的水平以下。
模制复合物用已知的方法生产和硫化。
其它典型的组分也是已知的，如增塑剂、稳定剂、活化剂、颜料、抗老化剂和加工助剂等。
所述的模制复合物一般含有已知的轻质硅酸盐填料（例如粘土、高岭土以及沉淀和热解的二氧化硅和硅酸盐等），填料的BET（低温氮吸附法）比表面积为1至1000平方米/克，以5至300平方米/克较好，本发明所述的复合物中的三烷氧基甲硅烷基与填料中的羟基反应消去醇，同时使填料与硅烷之间形成化学键。但是，已知的炭黑也用作填料。
相应于通式（Ⅰ）的氰硫基硅烷加入到可硫化模制复合物中的数量一般为0.1至20份（重量）（以100份橡胶或聚合物为基准），用量以0.1至10份（重量）较好，可以是直接加入，或者是以事先与填料已知键合的形式加入。
按照本发明除了降低促进剂用量之外，由于使用如式（Ⅰ）所示的有机硅化合物还会降低可硫化模制复合物的粘度，从而改善它们的加工性能。
尤其适用于本发明所述方法的橡胶和聚合物是双键含量较低的橡胶，如EPDM和EVA，但NBR，NR和SBR亦适用。
以下的实施例说明按本发明所述的复合物与先有技术相比的优点，同时也说明在毒性的能生成亚硝胺的促进剂至少减少一大部分
的情况下是可以操作的，并至少仍能得到通常的橡胶性能。
评估所用的测试标准
测试方法 单位
门尼粘度 DIN 53 523/524 兆帕斯卡
拉伸强度 DIN 53 504 兆帕斯卡
模量 DIN 53 504 兆帕斯卡
邵氏硬度 DIN 53 505 --
压缩变定 ASTM D 395 %
实施例中用到的一些名称与缩写的含义如下：
Keltan 578 用DSM法制得的EPDM
N 765 炉法炭黑，比表面积为34平方米/克
N 660 炉法炭黑，比表面积为36平方米/克
Ultrasil VN 3 沉淀二氧化硅，BET比表面积为175平方米/克
Suprex 粘土 硅酸钠
Omya 白垩 碳酸钙
Sunpar 150 石蜡增塑剂
Si 264 3-氰硫基丙基三乙氧基硅烷
DEG 二甘醇
CBS 苯并噻唑基-2-环己基次磺酰胺
TMTD 二硫化四甲基秋兰姆
Rhenocure CUT 二烷基二硫代磷酸铜
ZDBC 二丁基二硫代氨基甲酸锌
实施例1
在EPDM电缆护皮混合物中用Si264减少TMTD的用量。
混合物1 混合物2
Keltan 578 100 100
Ultrasil VN 3 25 25
Omya白垩 50 50
Suprex粘土 125 125
氧化锌,RS 5 5
硬脂酸 2 2
Sunpar 150 30 30
DEG 2 2
Si 264 - 2
CBS 2 2
TMTD 1 0.5
Rhenocure CUT 2.5 2.5
硫 1.5 1.5
流度仪测量:160℃
Dmax-Dmin (牛顿·米) 10.63 11.27
t90%-t10% 4.0 3.3
门尼粘度ML4(100℃)(MU) 78 58
硫化橡胶数据: 160℃,t95%
拉伸强度 兆帕斯卡 10.3 11.1
300%模量 兆帕斯卡 3.2 6.0
邵氏硬度 -- 74 78
压缩变定
22小时/70℃ % 26.3 19.4
70小时/100℃ % 73.2 67.5
本实施例表明，虽然秋兰姆的用量减少了50%，使用Si264（混合物2）至少也与现行工艺（混合物1）不相上下，在某些情况下甚至有所超过。
实施例2
在EPDM液压软管中用Si264替代TMTD。
混合物1 混合物2
Keltan 578 100 100
N 765 75 75
N 660 100 100
Suprex 粘土 90 90
氧化锌,RS 5 5
硬脂酸 1 1
Sunpar 150 100 100
Si 264 - 1
MBT 1.5 1.5
ZDBC 0.8 0.8
TMTD 0.7 -
Rhenocure CUT 0.7 0.7
硫 4 4
流变仪测量:160℃
Dmax-Smin (牛·米) 9.93 13.05
硫化橡胶数据:160℃,t95%
拉伸强度 兆帕斯卡 10.1 10.8
100%模量 兆帕斯卡 7.5 9.6
邵氏硬度 - 86 86
在ASTM2号油中贮存(70小时/160℃)
拉伸强度 兆帕斯卡 3.4 4.3
100%模量 兆帕斯卡 2.9 4.3
拉断伸长率 % 110 110
在实施例2中，通过使用Si 264可以完全取代TMTD而且对橡胶性能没有任何不利影响。
Claims (2)
1、可硫化的模制复合物的生产方法，该复合物中包含用硫或给硫体及促进剂进行硫化的一种或多种天然橡胶、合成橡胶或聚合物，填料，以及其它典型组分，至少一种促进剂属于目前所用的秋兰姆和/或二硫代氨基甲酸盐这一类，其特征在于同时还使用通式如下的3-氰硫基丙基三烷氧基硅烷：
式中R为C1-8烷基，与不含有机硅化合物的可硫化模制复合物中原来的用量相比，秋兰姆和/或二硫代氨基甲酸盐类促进剂的用量至少减低到一半。
2、用权利要求1中所述的方法所生产的可硫化模制复合物。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4128203A DE4128203C1 (zh) | 1991-08-26 | 1991-08-26 | |
| DEP4128203.5 | 1991-08-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1069748A true CN1069748A (zh) | 1993-03-10 |
| CN1067701C CN1067701C (zh) | 2001-06-27 |
Family
ID=6439104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92109579A Expired - Fee Related CN1067701C (zh) | 1991-08-26 | 1992-08-25 | 制备可硫化的模制复合物的方法以及用该方法制得的模制复合物 |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPH05214171A (zh) |
| KR (1) | KR960003827B1 (zh) |
| CN (1) | CN1067701C (zh) |
| DE (1) | DE4128203C1 (zh) |
| FR (1) | FR2680795B1 (zh) |
| GB (1) | GB2259303B (zh) |
| IT (1) | IT1256945B (zh) |
| TW (1) | TW203070B (zh) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19505650A1 (de) * | 1995-02-18 | 1996-08-22 | Freudenberg Carl Fa | Verhinderung oder Verringerung der Entstehung von Aminen und N-Nitrosaminen bei Fertigung und Gebrauch von Elastomeren |
| US6784255B1 (en) * | 1999-07-23 | 2004-08-31 | Mitsui Chemicals Inc. | Rubber composition for extrusion molding and for molding with mold and use thereof |
| US6359046B1 (en) | 2000-09-08 | 2002-03-19 | Crompton Corporation | Hydrocarbon core polysulfide silane coupling agents for filled elastomer compositions |
| DE60233962D1 (de) * | 2001-10-29 | 2009-11-19 | Dow Corning Toray Co Ltd | Härtbare organische harzzusammensetzung |
| US7781606B2 (en) | 2006-12-28 | 2010-08-24 | Momentive Performance Materials Inc. | Blocked mercaptosilane coupling agents, process for making and uses in rubber |
| US7696269B2 (en) | 2006-12-28 | 2010-04-13 | Momentive Performance Materials Inc. | Silated core polysulfides, their preparation and use in filled elastomer compositions |
| US7968636B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing silated cyclic core polysulfides |
| US8592506B2 (en) | 2006-12-28 | 2013-11-26 | Continental Ag | Tire compositions and components containing blocked mercaptosilane coupling agent |
| US7968633B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
| US7960460B2 (en) | 2006-12-28 | 2011-06-14 | Momentive Performance Materials, Inc. | Free-flowing filler composition and rubber composition containing same |
| US7737202B2 (en) | 2006-12-28 | 2010-06-15 | 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 |
| US7687558B2 (en) | 2006-12-28 | 2010-03-30 | Momentive Performance Materials Inc. | Silated cyclic core polysulfides, their preparation and use in filled elastomer compositions |
| US7968634B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing silated core polysulfides |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2035778C3 (de) * | 1970-07-18 | 1980-06-19 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Thiocyanatopropyl-organooxYsilane und sie enthaltende Formmmassen |
| DE2819638C3 (de) * | 1978-05-05 | 1986-11-13 | Degussa Ag, 6000 Frankfurt | Vulkanisierbare Halogenkautschuk-Mischungen |
| DE3305373C2 (de) * | 1983-02-17 | 1985-07-11 | Degussa Ag, 6000 Frankfurt | Elastische Formmasse, Verfahren zum Herstellen und Verformen und Verwendung derselben |
| JPS63199253A (ja) * | 1987-02-13 | 1988-08-17 | Shin Etsu Chem Co Ltd | ゴム組成物 |
| DE4004781A1 (de) * | 1990-02-16 | 1991-08-22 | Degussa | Verfahren zur herstellung von mit organosiliciumverbindungen modifizierten fuellstoffen, die so hergestellten fuellstoffe und deren verwendung |
| DE4023537A1 (de) * | 1990-07-25 | 1992-01-30 | Degussa | Mit organosiliciumverbindungen chemisch modifizierte russe, verfahren zu deren herstellung und deren verwendung |
-
1991
- 1991-08-26 DE DE4128203A patent/DE4128203C1/de not_active Expired - Fee Related
-
1992
- 1992-06-30 FR FR9208032A patent/FR2680795B1/fr not_active Expired - Fee Related
- 1992-08-11 TW TW081106326A patent/TW203070B/zh active
- 1992-08-19 GB GB9217649A patent/GB2259303B/en not_active Expired - Fee Related
- 1992-08-24 JP JP4223954A patent/JPH05214171A/ja active Pending
- 1992-08-25 KR KR1019920015253A patent/KR960003827B1/ko not_active IP Right Cessation
- 1992-08-25 CN CN92109579A patent/CN1067701C/zh not_active Expired - Fee Related
- 1992-08-26 IT ITTO920713A patent/IT1256945B/it active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| ITTO920713A0 (it) | 1992-08-26 |
| GB2259303B (en) | 1994-07-20 |
| DE4128203C1 (zh) | 1993-05-13 |
| GB9217649D0 (en) | 1992-09-30 |
| CN1067701C (zh) | 2001-06-27 |
| FR2680795B1 (fr) | 2002-01-25 |
| ITTO920713A1 (it) | 1994-02-26 |
| IT1256945B (it) | 1995-12-27 |
| JPH05214171A (ja) | 1993-08-24 |
| TW203070B (zh) | 1993-04-01 |
| KR960003827B1 (ko) | 1996-03-22 |
| GB2259303A (en) | 1993-03-10 |
| KR930004332A (ko) | 1993-03-22 |
| FR2680795A1 (fr) | 1993-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1067701C (zh) | 制备可硫化的模制复合物的方法以及用该方法制得的模制复合物 | |
| CN1294214C (zh) | 硅烷改性的氧化填料或类硅酸盐填料及其制备方法和应用 | |
| CN1120199C (zh) | 用于轮胎胎面的弹性体组合物 | |
| CN1067665A (zh) | 填充炭黑的塑料和橡胶化合物的制法 | |
| CN1250779A (zh) | 硫代硅烷 | |
| CN101041730A (zh) | 新型水下吸声橡胶制品及制备方法 | |
| CN1911991A (zh) | 用沉淀法白炭黑和硬度受控的炭黑粒料复合材料制备的橡胶以及具有由它衍生的构件的轮胎 | |
| CN1580106A (zh) | 炭黑 | |
| CN1303871A (zh) | 在丁基弹性体和填料之间化学结合性改进的弹性体的丁基复合物 | |
| JPS5836009B2 (ja) | 加硫可能なゴム混合物 | |
| CN1657558A (zh) | 橡胶组合物 | |
| JP5179732B2 (ja) | ゴム組成物およびそれを用いた特定の部材を有するタイヤ | |
| CN1529735A (zh) | 含有淀粉/苯乙烯丁二烯橡胶共聚物作为补强填充剂的可硫化弹性体组合物 | |
| JP2009019097A (ja) | タイヤ用ゴム組成物 | |
| JP2012144598A (ja) | タイヤ用ゴム組成物及び空気入りタイヤ | |
| CN1583858A (zh) | 橡胶组合物及使用该组合物的充气轮胎 | |
| CN1234331A (zh) | 塑胶场地材料 | |
| CN1032808A (zh) | 具有含改良加工助剂之胎面组合物的轮胎 | |
| US8735509B2 (en) | Use of polyorganosiloxanes in the processing and vulcanisation of rubber | |
| JP2006089526A (ja) | タイヤ用ゴム組成物 | |
| JP4574649B2 (ja) | ゴム組成物およびそれを用いたタイヤ | |
| CN1890313A (zh) | 适用于epdm型橡胶的固化剂 | |
| CN85105621A (zh) | 含有2-仲胺-4，6-二巯基-s-三嗪的可硫化卤化橡胶混炼胶 | |
| JP2013241482A (ja) | タイヤ用ゴム組成物及び空気入りタイヤ | |
| CN102585294A (zh) | 一种复合型橡胶粘结增进剂及其制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
| OR01 | Other related matters | ||
| 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 |