CN1296989A - 含羟基和羧基的二烯烃橡胶及无硫交联剂的橡胶混合物 - Google Patents
含羟基和羧基的二烯烃橡胶及无硫交联剂的橡胶混合物 Download PDFInfo
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- CN1296989A CN1296989A CN00128452A CN00128452A CN1296989A CN 1296989 A CN1296989 A CN 1296989A CN 00128452 A CN00128452 A CN 00128452A CN 00128452 A CN00128452 A CN 00128452A CN 1296989 A CN1296989 A CN 1296989A
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Abstract
本发明涉及橡胶混合物,其包括至少一种含羟基或羧基的橡胶和10至800重量份填料,按100重量份橡胶计,和0.001至40重量份的能够通过橡胶的羟基或羧基交联橡胶的化合物,和非必要的另一些橡胶、橡胶助剂和交联剂。本发明的橡胶混合物和其硫化产品适宜制备高增强的成形橡胶制品、特别是轮胎,该制品具有特别高的耐热性和耐机械性、高的耐湿滑性、低滚动阻力、及高的耐开炼机性。
Description
本发明涉及含羟基和/或羧基的二烯烃橡胶、填料、和可通过羟基或羧基交联橡胶的无硫交联剂的橡胶混合物,以及其在制备具有改进的动态阻尼、改进的机械强度、抗硫化返原性和与补强支撑物的粘结性的橡胶硫化产品中的用途。这些橡胶混合物和硫化产品适合生产具有特别高的耐热和机械应力、高而湿滑、低滚动阻力和高耐开炼机性的高补强成型橡胶制品,特别是轮胎。
已提出了用于生产具有低滚动阻力、改进的而湿滑性、低开炼机蚀性和较高耐热性的汽车轮胎的多种途径。已证明使用阴离子聚合含双键的溶聚橡胶,如溶液聚丁二烯和溶液苯乙烯/丁二烯橡胶特别有利的。这些优点特别在于可控制乙烯基含量,以及相关的玻璃化转变温度、有利的顺/反双键比和分子支化。实际使用时,由此获得的特别优点在于轮胎而湿滑与滚动阻力之间的比例。US-A 5 227 425描述了由溶聚SBR橡胶和二氧化硅生产胎面的方法。
含羟基的乳液和溶聚橡胶描述于例如EP-A 806 452中,但其中的橡胶不通过羟基交联,而是按常规方式通过用硫交联硫化。按照这种方法,这里描述的用于溶聚橡胶的羟基含量在特别低范围内(0.009至0.061%),因此该含量对于有效交联太低。
DE-A 2 653 144中特别描述了一种制备含羟基和/或羧基(3.9至8.9wt%)的溶聚聚丁二烯橡胶的方法。这些橡胶也是仅用硫交联的,由于其强度太低,且其模量太低,因此它们不适合在轮胎中作为主组分。
EP-A 464 478中也描述了一种通过橡胶与特定长链羟基硫醇反应制备含羟基溶聚橡胶的方法。未给出制备具有与羟基反应的无硫交联剂的橡胶混合物和相应的硫化产品方法的参考文献。
用不饱和羧酸的金属盐接枝的不饱和橡胶描述于US-A-5 962,593中。其中橡胶交联也是通过硫硫化进行的。此外,羧酸基团的含量相当高。
德国专利申请198 32 459.6、198 52 648.2、199 14 848.1、19920 788.7和199 20 894.8描述了含羟基和/或羧基的具有有利的羟基和/或羧基含量(0.1至3wt%)的溶聚橡胶。然而,该专利申请未给出与官能基团反应的改进交联体系。
因此,本发明的一个目的是提供一种含羟基和/或羧基的橡胶,特别优选溶聚橡胶和与羟基或羧基在硫化条件下化学反应的特定交联剂的混合物,由该混合物可生产具有改进的而湿滑、低滚动阻力、高机械强度和耐热性、及改进的耐开炼机性的轮胎。
本发明提供一种橡胶混合物,其包括至少一种橡胶和10至800重量份填料(按100重量份橡胶计),其中橡胶通过聚合二烯烃和非必要的另一些乙烯基芳族单体并引入羟基和/或羧基制备,该橡胶具有总含量0.05至5wt%的键合羟基和/或羧基或其盐,并具有含量0至50wt%的已聚合乙烯基芳族单体和含量45至99.95wt%的二烯烃,1,2-键合的二烯烃含量(乙烯基含量)为0至80wt%,和0.001至40重量份的能够通过橡胶的羟基或羧基交联橡胶的化合物(所谓无硫交联剂),和非必要的另一些橡胶、橡胶助剂和交联剂。
本发明优选的橡胶混合物是这样一些混合物,即其中橡胶组分具有总含量0.1至3wt%的键合羟基和/或羧基或其盐,并具有含量0至40wt%,特别优选10至40wt%的已聚合乙烯基芳族单体和含量99.9至60wt%的二烯烃,1,2-键合的二烯烃含量(乙烯基含量)为5至55wt%,且该混合物具有含量0.1至20重量份的上述类型的无硫交联剂。
填料量优选为20至200重量份。
本发明用于聚合的二烯烃为1,3-丁二烯、异戊二烯、1,3-戊二烯、2,3-二甲基丁二烯、1-乙烯基-1,3-丁二烯和/或1.3-己二烯。特别优选使用1,3-丁二烯和异戊二烯。
可提及的用于聚合的乙烯基芳族单体的例子是苯乙烯,邻-、间-和对-甲基苯乙烯,对叔丁基苯乙烯、α-甲基苯乙烯、乙烯基萘、二乙烯基苯、三乙烯基苯和/或二乙烯基萘。特别优选使用苯乙烯。
本发明可用于橡胶混合物中的基于二烯烃和非必要的另一些乙烯基芳族单体的橡胶具有平均分子量(数均)50,000至2,000,000,优选100,000至1,000,000,和玻璃化转变温度-110℃至+20℃,优选-100℃至0℃,和门尼粘度ML 1+4(100℃)为10至200,优选30至150。
除了羟基和羧酸基团或其盐外,本发明的橡胶还可具有另一些已知的官能基团,如羧酸酯、羧酸酰胺或磺酸基团。
含羟基和羧基的溶聚橡胶是特别优选的,尤其是例如描述于上述德国专利申请DE-A 2 653 144和EP-A 464 478中的那些。
根据本发明,可能的无硫交联剂是能够对橡胶混合物进行硫化,即仅通过羟基或羧基交联形成共价化学键的所有多官能化合物。在此情况下,术语“无硫”应理解为该化合物不包括硫化活性的含硫基团。根据本发明,还可使用具有在硫化条件下稳定的含硫基如砜或单硫基醚基的交联剂。本发明中适宜的交联剂尤其是多异氰酸酯、polyuretdiones、封闭型多异氰酸酯和/或聚环氧化物。特别优选的交联剂类是:
(A)多异氰酸酯,如六亚甲基二异酸酯(HDI)、异佛尔酮-二异氰酸酯(IPDI)、甲苯-二异氰酸酯(TDI)、4,4′-二异氰酸二苯基甲烷(MDI)、1,6-二异氰酸2,2,4-三甲基己烷(IPDI)、三-(4-异氰酸苯基)-甲烷、磷酸三-(4-异氰酸-苯基酯)、硫代磷酸三-(4-异氰酸-苯基酯)和其低聚产物,该低聚产物通过上述低分子量二异氰酸酯与二醇或多醇、特别是乙二醇、1,4-丁二醇、1,6-己二醇、三羟甲基丙烷或季戊四醇反应而制备且具有残余量的游离异氰酸酯基;另外的低聚产物,该低聚产物通过上述低分子量二异氰酸酯与含有羟基且具有分子量400-3,000的聚酯如基于己二酸和丁二醇及己二醇的聚酯的反应而制备,或通过与含有羟基其分子量为150-3,000的聚醚如聚乙二醇或聚丙二醇或聚四氢呋喃反应而制备,且具有残余量的游离异氰酸酯基;另外的低聚物,该低聚产物通过上述低分子量二异氰酸酯与胺或多胺,特别是氨水、二氨基丁烷或二氨基己烷反应而制备,其具有残余量的游离异氰酸酯基;或另外的低聚产物,该低聚产物通过上述低分子量二异氰酸酯与水反应或通过二聚或三聚反应而制备,如二聚的甲苯二异氰酸酯(Desmodur TT)和三聚的甲苯二异氰酸酯,或含有异氰酸酯基的脂族uretdione和聚uretdione,如基于异佛尔酮-二异氰酸酯的,并有残余量的游离异氰酸酯基。优选的游离异氰酸酯基的含量为2.5-25wt%。这些多异氰酸酯是公知的并可以商购,在本申请中可参见:Houben-Weyl,Methoden der Organischen Chemie[有机化学方法],ⅪⅤ卷,56-98页,Geory Thieme Verlag Stuttgart 1963,和Desmodur和Crelan系列(Bayer AG)的商购产品;
(B)在硫化条件下与橡胶的羟基和/或羧基反应的封闭型多异氰酸酯。其包括所有在(A)中提到多异氰酸酯,在每一种情况下异氰酸酯基用适当的分离基团封闭,该分离基团在较高温度下分离从而释放出异氰酸酯基。适当的分离基团特别是,己内酰胺、丙二酸酯、苯酚和烷基酚如壬基酚,以及咪唑和亚硫酸氢钠。特别优选的是用己内酰胺、丙二酸酯和烷基酚封闭的多异氰酸酯,尤其是基于甲苯-二异氰酸酯或三聚的甲苯-二异氰酸酯和异佛尔酮-二异氰酸酯的那些多异氰酸酯。优选的封闭型多异氰酸酯还可通过将异氰酸酯基二聚至uretdione和polyuretdione得到。封闭异氰酸酯基的优选含量是2.5-20wt%。这些封闭型多异氰酸酯是公知的并可以商购,在本申请中可参见:Houben-Weyl,Methoden der Organischen Chemie[有机化学方法],ⅪⅤ卷,56-98页,Geory Thieme Verlag Stuttgart 1963,和Desmodur和Crelan系列(Bayer AG)的商购产品;
(C)在硫化条件下与橡胶的羟基或羧基反应的聚环氧化物。优选的聚环氧化物是通过表氯醇与二和多苯酚反应而制备的,具体是双酚A或三-4-羟苯基甲烷的缩水甘油醚、和苯酚树脂的缩水甘油醚,如分子量350-5,000的苯酚/甲醛酚醛清漆、苯酚/二甲苯/甲醛树脂和苯酚/羟甲基脲树脂。另一些优选的聚环氧化物是通过表氯醇与二和多胺反应而制备的,如基于环己胺或苯胺的二环氧化物、或基于双-(4-氨苯基)-甲烷的四环氧化物或基于含N-杂环化合物的环氧化物,特别是异氰脲酸三缩水甘油酯(TGIC)和三缩水甘油基尿唑。另一些优选的聚环氧化物是不饱和烃或不饱和酯的环氧产物,如环氧化大豆油和环氧化环己烯-3-羧酸酯,及环氧化的橡胶如环氧化的天然橡胶,其中10-70mol%的双键被环氧化。优选的聚环氧化物的环氧当量,即含有16g环氧键合氧的树脂量以克计(DIN 16945)为100g-1,000g。这些聚环氧化物是公知的并可以商购,在本申请中可参见:Houben-Weyl,Methoden der Organischen Chemie[有机化学方法],ⅪⅤ卷,56-98页,Geory Thieme Verlag Stuttgart 1963。
如果需要,交联即羟基或羧基与交联剂的反应可用已知的催化剂例如借助于胺如二氮杂双环辛烷(DABCO)、或路易斯酸如二月桂酸二丁基锡(DBTL)促进。催化剂的量取决于所需的硫化动力学、硫化温度及交联剂和羟基或羧基的量,并可通过初步实验很容易测定。基于交联剂,催化剂常规量为0-3wt%。
硫化温度为室温至220℃,优选100℃至180℃。硫化时间为几分钟至数小时。硫化也可在常规交联剂存在下分两段进行,因为在这种情况下这只是单独的交联处理问题而已,即,例如,通过由无硫交联剂的预交联和用己知的硫化剂(具体是硫、硫供体或过氧化物)的后交联。
本发明用于橡胶的可用填料是所有的用于橡胶工业的公知填料,其包括活性和非活性填料。可提到:
-如由沉淀硅酸盐溶液或卤化硅的火焰水解而制备的高分散氧化硅,其比表面积为5-1,000,优选20-400m2/g(BET表面积),初级粒径为10-400nm。该氧化硅也可非必要地呈与其它金属氧化物如Al、Mg、Ca、Ba、Zn、Zr或Ti的氧化物的混合氧化物形式。
-合成的硅酸盐如硅酸铝或碱土金属硅酸盐如硅酸镁或硅酸钙,其BET表面积为20-400m2/g,初级粒径为10-400nm;
-天然存在的硅酸盐如高岭土和其它天然存在的氧化硅;
-玻璃纤维和玻璃纤维产品(垫、绳)或玻璃微珠;
-金属氧化物,如氧化锌、氧化钙、氧化镁或氧化铝;
-金属碳酸盐,如碳酸镁、碳酸钙或碳酸锌;
-金属氢氧化物,如氢氧化铝或氢氧化镁;
-炭黑。用于本发明的炭黑是通过火焰炭黑或炉法或气黑法而制备的,并具有20-200m2/g的BET表面积,如SAF,ISAF,HAF,FEF或GPE炭黑;
-橡胶凝胶
-通过例如研开炼机橡胶硫化产品而制备的橡胶粉未。
优选使用高分散的氧化硅和/或炭黑作为填料。
提到的填料可单独或作为混合物使用。在一个特别优选的实施方案中,橡胶混合物含有浅色填料如高分散氧化硅和炭黑的混合物作为填料,浅色填料和炭黑的混合比为0.05-20,优选0.1-10。
除了提到的含有羟基和羧基的溶聚橡胶外,本发明的橡胶混合物也可含有其它橡胶,如天然橡胶和其它合成橡胶。
优选的合成橡胶描述于例如W.Hofmann,Kautschuktechnologie[橡胶工艺],Gentner Verlag,Stuttgart 1980和I.Franta,弹性体和配合剂(Elastomers and Rubber Compounding Materials),Elsevier,Amsterdam 1989中。这些合成橡胶尤其包括:
BR-聚丁二烯
ABR-丁二烯/丙烯酸C1-4烷基酯共聚物
CR-聚氯丁二烯
IR-聚异戊二烯
SBR-苯乙烯/丁二烯共聚物,其苯乙烯含量为1-60,优选20-50wt%
IIR-异丁烯/异戊二烯共聚物
NBR-丁二烯/丙烯腈共聚物,其丙烯腈含量为5-60,优选10-40wt%
HNBR-部分氢化或完全氢化的NBR橡胶
EPDM-乙烯/丙烯/二烯共聚物和这些橡胶的混合物。为了制备汽车轮胎,特别优选玻璃化转变温度高于-50℃的可非必要地用甲硅烷基醚或其它官能基根椐EP-A 447.066改性的天然橡胶、乳液SBR和溶聚SBR、具有高1,4-顺式含量的(大于90%)的用基于Ni、Co、Ti或Nd的催化剂制备的聚丁二烯橡胶、和乙烯含量高达75%的聚丁二烯橡胶以及其混合物。
本发明橡胶混合物当然可含有其它橡胶助剂,如用于进一步交联由该橡胶混合物制备的硫化产品,或为了其特定用途而改善由本发明的橡胶混合物而制备的硫化产品的物理性能的助剂。
用硫或硫供体化合物或过氧化物作为另外的交联剂。特别优选的硫或硫供体化合物的量为0.01-3重量份,以橡胶重量计。另外,如提到的,本发明的橡胶混合物可含有另外的助剂,如公知的反应促进剂、防老剂、热稳定剂、光稳定剂、臭氧稳定剂、加工助剂、补强剂如苯酚树脂、钢丝帘布粘合剂如氧化硅/间苯二酚/六亚甲基四胺或环烷酸钴、增塑剂、增粘剂、发泡剂、染料、颜料、蜡、增量剂、有机酸、抑制剂、金属氧化物和活化剂。
本发明的橡胶助剂以常规公知的量加以使用,所用的量取决于该橡胶混合物的后继预定用途。例如,常规的橡胶助剂的量为2-70重量份,以100重量份的橡胶计。
如上提到的,除了含羟基和羧基的溶聚橡胶外,其它的橡胶也可混入本发明的橡胶混合物。其常规量为0.5-70%、优选10-50wt%,以橡胶混合物中橡胶的总量计。另外加入的橡胶的量同样取决于本发明的橡胶混合物的特定预计用途。
对于本发明的具有高活性氧化硅的填料的橡胶混合物,特别优选使用另外的填料活化剂。优选的填料活化剂是含硫甲硅烷基醚,特别是双-(三烷氧基甲硅烷基-烷基)多硫化物,如在DE-A 2141159和DE-A 2255577中描述的。对应于DE-A4435311和EP-A670347描述的低聚的和/或聚合的含硫甲硅烷基醚也是可使用的。另外也可使用巯基烷基三烷氧基硅烷,特别是巯基丙基三乙氧基硅烷和氰硫基烷基甲硅烷基醚(参见DE-A19,544,469)和含有氨基的甲硅烷基醚,如3-氨基丙基三乙氧基硅烷和N-油酰基-N-丙基三甲氧基硅烷。该填料活化剂以常规量加以使用,即0.1-15重量份,以100重量份橡胶计。
本发明的橡胶混合物可例如通过在适宜的混炼机如捏合机、开炼机或挤出机中通过混合含有羟基和羧基的溶聚橡胶和相应的填料和无硫的交联剂而制备。
本发明还提供用本发明的橡胶混合物制备硫化产品的用途,该硫化产品接着用来制备高补强成形橡胶制品,特别是用于制备轮胎制备品。
实施例
实施例1:含有羟基的溶聚SBR橡胶
将2.25kg巯基乙醇和0.18kg二月桂酰过氧化物在80℃下加入到45kg Buna VSL 5020-0(溶聚SBR橡胶,其苯乙烯含量为20wt%,乙烯含量为50wt%,由Bayer AG制造)在275kg环己环中的溶液中,将混合物在80℃下搅拌2小时。加入0.23kg Vulkanox 4020(6-PPD型稳定剂,由Bayer AG制造)和17.72kg Enerthene 1849(芳族矿物油,制造商BP),并用蒸汽汽提除去溶剂。70℃真空干燥后,得到用37.5phr芳族矿物油增量的溶聚SBR橡胶,其羟基含量为1wt%(基于无油橡胶)、OH值为24(油增量的橡胶)、玻璃化转变温度为-24℃、粘度ML 1+4(100℃)为55。
实施例2:含有羧基的溶聚SBR橡胶
将0.563kg 3-巯基丙酸和0.045kg二月桂酰过氧化物在80℃下加入45kg Buna VSL 5020-0(溶聚SBR橡胶,其苯乙烯含量为20wt%,乙烯含量为50wt%,由Bayer AG制造)在275kg环己环中的溶液中,将混合物在80℃下搅拌2小时。加入0.23kg Vulkanox 4020(6-PPD型稳定剂,由Bayer AG制造)和17.12kg Enerthene 1849(芳族矿物油,制造商BP),并用蒸汽汽提除去溶剂。70℃真空干燥后,得到用37.5phr芳族矿物油增量的溶聚SBR橡胶,其羧基含量为0.5wt%(基于无油橡胶)、酸值为5(油增量的橡胶)、玻璃化转变温度为-29℃、粘度ML 1+4(100℃)为38。
实施例3:无硫交联剂
用己内酰胺封闭的环脂族多异氰酸酯,NCO的总量为11.5%。商品名:Crelan UI,制造商:Bayer AG。
实施例4:无硫交联剂
不带封闭剂的环脂族polyuretdione,NCO的总量为13.5%。商品名:Crelan VP LS 2147,制造商:Bayer AG。
实施例5:无硫交联剂异氰脲酸三缩水甘油酯
(CAS-RN 2451-62-9)
实施例6:橡胶混合物
在130-140℃下在1.5升密炼机中制备下列橡胶混合物。最后在50℃的开炼机上掺混促进剂和交联剂。
组分 | 实施例6.1 | 比较例6.A |
在密炼机中混合: | ||
实施例1的含羟基溶聚SBR橡胶 | 137.5 | 0 |
油增量的溶聚SBR橡胶Buna VSL 5025-1(Bayer AG) | 0 | 137.5 |
炭黑Coraxx N339(Degussa-Hüls AG) | 50 | 50 |
氧化锌 | 2.5 | 2.5 |
抗氧剂ulkanox 4020 | 1 | 1 |
臭氧保护蜡Antilux 654(Rheinchemie) | 1.5 | 1.5 |
在开炼机上掺混: | ||
实施例3的无硫交联剂 | 15 | 15 |
硫 | 0.5 | 0.5 |
二苯基胍Vulkacit D(Bayer AG) | 1 | 1 |
该橡胶混合物接着在170℃下硫化30分钟。得到下列硫化物性能:
实施例6.1 | 比较例6.A | |
拉伸强度(MPa) | 18.1 | 5.4 |
300%伸长时的模量(MPa) | 8.5 | 1.4 |
断裂伸长(%) | 519 | 975 |
在23℃的回弹性(%) | 21 | 29 |
在70℃的回弹性(%) | 54 | 45 |
23和70℃回弹性之差 | 33 | 16 |
23℃时硬度(邵氏A) | 54 | 40 |
70℃时硬度(邵氏A) | 50 | 24 |
该结果表明:相比于未改性的SBR橡胶和无硫交联剂的组合,羟基改性的SBR橡胶和无硫交联剂(封闭型异氰酸酯)的橡胶混合物有很强的补强效果(通过硬度、模量、拉伸强度测试)和优良的动态阻尼性能。
Claims (6)
1.橡胶混合物,其包括至少一种橡胶和按100重量份橡胶为基础计10至800重量份的填料,其中橡胶通过聚合二烯烃和非必要的另一些乙烯基芳族单体并引入羟基和/或羧基而制备,该橡胶具有总含量0.05至5重量%的键合羟基和/或羧基或其盐,并具有含量0至50重量%的已聚合乙烯基芳族单体和含量45至99.95重量%的二烯烃,1,2-键合的二烯烃含量(乙烯基含量)为0至80重量%,和0.001至40重量份的能够通过橡胶的羟基或羧基交联橡胶的化合物,和非必要的另一些橡胶、橡胶助剂和交联剂。
2.根据权利要求1的橡胶混合物,其特征在于该橡胶混合物包括20至200重量份填料,按100重量份橡胶为基础计。
3.根据权利要求1的橡胶混合物,其特征在于该橡胶具有总含量为0.1至3重量%的键合羟基和/或羧基或其盐。
4.根据权利要求1的橡胶混合物,其特征在于该橡胶具有含量0至40重量%的已聚合乙烯基芳族单体和含量99.9-60重量%的二烯烃,其中1,2-键合的二烯烃含量(乙烯基含量)为5至55重量%。
5.根据权利要求1的橡胶混合物,其特征在于所用的无硫交联剂是多异氰酸酯、polyuretdione、封闭型多异氰酸酯和/或聚环氧化物。
6.根据权利要求1的橡胶混合物在制备高补强成形橡胶制品、特别是在制备轮胎中的用途。
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DE19956118A DE19956118A1 (de) | 1999-11-22 | 1999-11-22 | Kautschukmischungen aus hydroxyl- und carboxylgruppenhaltigen Dienkautschuken und schwefelfreien Vernetzern |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101395013B (zh) * | 2006-03-03 | 2010-07-21 | 倍耐力轮胎股份公司 | 轮胎和可交联的弹性体组合物 |
CN102449049A (zh) * | 2009-05-27 | 2012-05-09 | 朗盛德国有限责任公司 | 由功能化的二烯基橡胶与三羟甲基丙烷和脂肪酸组成的混合物、其生产方法及其用途 |
CN104903356A (zh) * | 2013-01-09 | 2015-09-09 | 东洋橡胶工业株式会社 | 改性二烯类聚合物及其制造方法、以及橡胶组合物及充气轮胎 |
CN110724475A (zh) * | 2019-10-23 | 2020-01-24 | 青岛东方雨虹建筑材料有限公司 | 一种改性包覆胶粉的反应粘层及其制备方法和预铺高分子防水卷材 |
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DE10060519A1 (de) * | 2000-08-07 | 2002-02-28 | Continental Ag | Vulkanisierbare Kautschukmischung zur Herstellung eines Fahrzeugluftreifens |
KR100429071B1 (ko) * | 2001-06-25 | 2004-04-29 | 한국타이어 주식회사 | 타이어 트래드용 고무 조성물 |
JP4552551B2 (ja) * | 2004-07-20 | 2010-09-29 | 横浜ゴム株式会社 | タイヤトレッド用ゴム組成物 |
JP4639875B2 (ja) * | 2005-03-18 | 2011-02-23 | 住友化学株式会社 | 変性ジエン系重合体ゴム、その製造方法及びゴム組成物 |
JP5374803B2 (ja) * | 2006-03-13 | 2013-12-25 | 横浜ゴム株式会社 | タイヤトレッド用ゴム組成物 |
DE102007044175A1 (de) * | 2007-09-15 | 2009-03-19 | Lanxess Deutschland Gmbh | Funktionalisierte Hochvinyl-Dienkautschuke |
EP3241853A1 (de) | 2016-05-04 | 2017-11-08 | Trinseo Europe GmbH | Elastomere polymere mit thioether-modifiziertem rückgrat |
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US4042619A (en) * | 1965-05-03 | 1977-08-16 | E. I. Du Pont De Nemours And Company | Derivatives of carboxy-terminated polybutadienes |
ZA733319B (en) * | 1972-06-08 | 1974-04-24 | Firestone Tire & Rubber Co | Tire treads |
US4104265A (en) * | 1975-01-30 | 1978-08-01 | Compagnie Generale Des Etablissements Michelin | Vulcanization process for preparation of polyurethane tires |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101395013B (zh) * | 2006-03-03 | 2010-07-21 | 倍耐力轮胎股份公司 | 轮胎和可交联的弹性体组合物 |
CN102449049A (zh) * | 2009-05-27 | 2012-05-09 | 朗盛德国有限责任公司 | 由功能化的二烯基橡胶与三羟甲基丙烷和脂肪酸组成的混合物、其生产方法及其用途 |
CN105348597A (zh) * | 2009-05-27 | 2016-02-24 | 朗盛德国有限责任公司 | 可固化的橡胶混合物、其生产方法及其用途 |
CN104903356A (zh) * | 2013-01-09 | 2015-09-09 | 东洋橡胶工业株式会社 | 改性二烯类聚合物及其制造方法、以及橡胶组合物及充气轮胎 |
CN104903356B (zh) * | 2013-01-09 | 2017-04-26 | 东洋橡胶工业株式会社 | 改性二烯类聚合物及其制造方法、以及橡胶组合物及充气轮胎 |
CN110724475A (zh) * | 2019-10-23 | 2020-01-24 | 青岛东方雨虹建筑材料有限公司 | 一种改性包覆胶粉的反应粘层及其制备方法和预铺高分子防水卷材 |
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