CN1237988A - 作为含有异单烯烃/对－烷基苯乙烯卤化共聚物的组合物的硫化剂的丙烯酸或甲基丙烯酸金属盐 - Google Patents
作为含有异单烯烃/对－烷基苯乙烯卤化共聚物的组合物的硫化剂的丙烯酸或甲基丙烯酸金属盐 Download PDFInfo
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- CN1237988A CN1237988A CN97198075A CN97198075A CN1237988A CN 1237988 A CN1237988 A CN 1237988A CN 97198075 A CN97198075 A CN 97198075A CN 97198075 A CN97198075 A CN 97198075A CN 1237988 A CN1237988 A CN 1237988A
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Abstract
本发明提供可硫化组合物，该组合物含有C4～C7异单烯烃如异丁烯和对－烷基苯乙烯如对－甲基苯乙烯的卤化共聚物，并且还含有作为硫化剂的有效量金属盐如不饱和羧酸如甲基丙烯酸的锌盐。该组合物还含有作为助硫化剂的有机过氧化物和能与卤化共聚物共硫化的一种饱和或烯属不饱和聚合物共混组分或几种组分的混合物。
Description
本发明的背景
本发明的领域
本发明涉及含有异单烯烃/对-烷基苯乙烯的卤化共聚物弹性体及其与其它聚合物的共混物的组合物的硫化体系。
相关技术的说明
在现有技术中已经知道，丙烯酸或甲基丙烯酸的锌盐与有机过氧化物的混合物可用于将含有饱和或不饱和弹性体组合物及其共混物的橡胶组合物进行硫化。
例如，美国专利4,713,409公开了可硫化的聚合物组合物，该组合物包括橡胶状聚合物如天然橡胶、乙丙橡胶、乙烯/丙烯/二烯烃橡胶、GR-S、丁腈橡胶、氯丁橡胶及其共混物，使用至少25重量份/100份橡胶(phr)的二甲基丙烯酸锌与有效硫化量的过氧化物硫化剂的混合物将该组合物进行硫化。
同样，美国专利4,857,571公开了一种用于饱和及不饱和弹性体组合物的自由基硫化体系，该体系基于自由基产生试剂如有机过氧化物和多官能单体活性助剂的混合物，该多官能单体活性助剂能与该自由基产生剂进行反应从而将该弹性体组合物进行交联。在美国专利5,288,446中也公开了同样的组合物。
美国专利4,987,192公开了着色的轮胎胶料，该胶料优选基于氯丁基橡胶、天然橡胶和EPDM橡胶的共混物，使用含有传统的含硫硫化剂和二甲基丙烯酸锌及有机过氧化物的混合物的硫化体系使其同时以共价键和离子键发生交联。
在这些及其类似的体系中，交联一般与聚合物链上自由基位置的产生和在这些位置双官能丙烯酸盐或甲基丙烯酸盐单体的加入以进行交联有关。
美国专利5,162,445公开了卤化的弹性无规共聚物，它为异单烯烃如聚异丁烯和对-烷基苯乙烯如对-甲基苯乙烯的无规共聚物，在本说明书中称为BIMS橡胶。这些共聚物没有乙烯不饱和度，因此它们的耐热性、耐溶剂性和耐臭氧性得到提高，并且容易在聚合物链上存在的苄基卤的参与下通过亲核或离子反应进行交联。适宜的交联剂包括氧化锌和硬脂酸的混合物或单独的硬脂酸锌，其用量高于约3.0重量份/100份橡胶(phr)。二乙基二硫代氨基甲酸锌也是BIMS橡胶的有效硫化剂。如在1995年5月3日提交的共同未决美国专利申请SN08/433,773公开的，硬脂酸锌也作为基于BIMS橡胶与不饱和二烯烃橡胶如聚异戊二烯、天然橡胶或聚丁二烯的共混物的弹性体组合物的有效硫化剂。用于这些可硫化共混物中的硬脂酸锌的硫化剂量为约0.05～低于3重量份phr。
开发BIMS弹性体的硫化体系的主要目标之一是发现一种硫化剂，该硫化剂不仅能将BIMS弹性体本身有效进行硫化，而且也能硫化BIMS弹性体与其它化学性能不同的聚合物如饱和或烯属不饱和弹性体或塑性体的共混物，结果对于这种共混物的每一种单独的弹性组分均能相对均衡地进行硫化。
本发明概要
本发明提供一种可硫化的聚合物组合物，该组合物包括C4～C7异单烯烃和对-烷基苯乙烯共聚单体的氯化或溴化弹性无规共聚体和硫化有效量的硫化剂混合物的混合物，该硫化剂混合物包括有机过氧化物及不饱和羧酸的弹性体可溶的多价金属盐，该不饱和羧酸含有3～300个碳原子，更优选为含有3～6个碳原子的α或β不饱和一元羧酸。
本发明还提供可硫化的聚合物共混物组合物，它含有上述组分，且还含有至少一种其它可为饱和或烯属不饱和聚合物的可共硫化聚合物组分。
当与有机过氧化物混合使用时，本发明的多价金属盐硫化剂在C4～C7异单烯烃/对-烷基苯乙烯的卤化弹性体体系中提供快速硫化和低硫化返原(10W reversion cure)，同时也能将基于卤化共聚物和第二种饱和或不饱和聚合物组分的共混物的组合物有效硫化。本发明的详细说明
在本发明使用的C4～C7异单烯烃/对-烷基苯乙烯卤化弹性体(BIMS)为C4～C7异单烯烃例如异丁烯和对-烷基苯乙烯共聚单体的无规共聚物的卤化产品，该对-烷基苯乙烯共聚单体优选为含有至少约80wt.％、更优选至少约90wt.％对位异构体的对-甲基苯乙烯，并且其中至少一些在苯乙烯单体单元中存在的烷基取代基含有卤素。优选的材料可表征为含有下述在聚合物链上无规分开的单体单元的异丁烯共聚体：
其中R和R’各自独立地为氢、低级烷基，优选为C1～C4烷基，并且X为溴或氯，且其中该共聚体基本上没有环上卤素或在聚合物主链上的卤素。优选R和R’均为氢。在该共聚体结构中，至多约65摩尔％的对-烷基苯乙烯可为上述卤化结构(2)，更优选为约5～60摩尔％。
这些材料中最有用的为异丁烯和对-甲基苯乙烯的弹性无规共聚物，该共聚物含有约0.5～20wt.％对-甲基苯乙烯，其中至多约60摩尔％的位于苄基环上的甲基取代基含有溴原子或氯原子，优选为含有溴原子。这些共聚物的组成分布基本上均匀，结果在至少95wt.％的聚合物中，对-烷基苯乙烯含量在聚合物的对-烷基苯乙烯平均含量的10％以内。它们的特征还在于分子量分布(Mw/Mn)窄，少于约7，更优选少于约5.0，粘均分子量优选为约300,000～2,000,000，并且用凝胶渗透色谱测定的数均分子量优选为从约10,000、更优选25,000到约1,000,000。
也可以用路易斯酸催化剂通过将单体混合物进行淤浆聚合，接着在卤素和自由基引发剂例如热和/或光和/或化学引发剂存在下在溶液中进行卤化，优选进行溴化，从而制备共聚物。
优选的溴化共聚物一般含有约0.01～10摩尔％的溴甲基，且绝大多数为单溴甲基，在共聚物中二溴甲基取代基的存在量少于0.05摩尔％。美国专利5,162,445更加具体地公开了这些共聚物、它们的制备方法、它们的硫化和接枝方法或由其衍生的官能化聚合物，其全部公开内容在这里引作参考。
在本发明中，适于用作BIMS弹性体组合物硫化剂组分的不饱和羧酸金属盐能溶于有机溶剂和橡胶介质中，并且从含有3～300个碳原子、更优选为3～20个碳原子的不饱和酸衍生而来。优选地，这些酸为含有3～6个碳原子(包括羧基碳)的α或β不饱和一元羧酸。适宜的酸包括丙烯酸、甲基丙烯酸、油酸、亚油酸和巴豆酸，最优选为丙烯酸和甲基丙烯酸。金属阳离子可选自多-(二或三)价金属例如锌、铁、镉、铋、铝、镁和钙，最优选为锌。
加入到组合物中的金属盐硫化剂量为能硫化或共硫化聚合物组合物的有效量。基于该组合物的聚合物含量，该量一般为约0.5～10wt.％，优选为约1～7.5wt.％，最优选为约2～6wt.％。
可以使用的过氧化物交联助硫化剂包括有机过氧化物如过氧化二枯基、过氧化苯甲酰、二-(叔丁基过氧化)二异丙基苯、叔丁基过氧化物、过苯甲酸叔丁酯、2,5-二甲基-2,5-二叔丁基过氧化己烷及类似物。优选的有机过氧化物为过氧化二枯基和二-(叔丁基过氧化)二异丙基苯。
过氧化物助硫化剂也可以加入足够的量，从而将聚合物组合物进行共硫化。一般而言，基于组合物的弹性体含量，该量为约0.2～6wt.％，更优选为约1～5wt.％。
当与也用于共硫化含有BIMS弹性体和一种或多种饱和或烯属不饱和聚合物的共混体系的有机过氧化物一起混合使用时，不饱和酸的金属盐作为助硫化剂。
适宜的共混聚合物包括一种饱和聚合物或几种饱和聚合物的混合物。饱和聚合物在这里包括那些有饱和骨架，但可有不饱和侧基的聚合物。这些聚合物的例子有低、中或高密度聚乙烯或乙烯与至多约50wt.％的C3～C8单烯烃如丙烯、1-丁烯、1-己烯及类似物的共聚物。优选的乙烯聚合物为聚乙烯和含有至多约35wt.％聚合的丙烯的乙烯弹性共聚物以及EPDM如乙烯、丙烯与非共轭二烯如亚乙基-降冰片烯的弹性共聚物。特别优选的乙烯共聚物为用金属茂聚合催化剂聚合的塑性体，例如乙烯与约5～30wt.％的1-己烯或1-丁烯的共聚物，例如可从Exxon化学公司买到，其商标为EXACTTM。
可使用作为共混物组分的适宜乙烯聚合物的熔融指数一般在约0.5～600范围内，更优选为约1～25。
第二种聚合物组分或聚合物组分混合物在组合物中的存在量为每99～1重量份BIMS弹性体约1～99重量份。最优选的共混物为基于共混物中的聚合物含量含有约20～80wt.％BIMS弹性体的共混物。
还含有烯属不饱和聚合物组分的本发明组合物也可选择性地含有辅助硫化剂如促进剂硫黄硫化体系，从而可改良硫化性能。这些辅助硫化剂包括硫或硫与含硫促进剂和/或酚醛树脂的混合物。适宜的促进剂包括二硫化苯并噻唑、N-氧联二乙基苯并噻唑-1-亚磺酰胺、2-巯基苯并噻唑、二硫化烷基苯酚、硫化烷基秋兰姆、间-亚苯基双马来酰亚胺、N,N’-二芳基胍类、二烷基和二芳基二硫代氨基甲酸盐、N-环己基-2-苯并噻唑亚磺酰胺及其类似的化合物。
适宜的二烷基二硫代氨基甲酸盐包括其中烷基含有1～5个碳原子的二烷基二硫代氨基甲酸的锌、铋、镉、铜、铅、硒和碲盐、五亚甲基二硫代氨基甲酸基哌啶鎓及其混合物。
适宜的二芳基二硫代氨基甲酸盐包括二芳基二硫代氨基甲酸的锌、铋、镉、铜、铅、硒和碲盐及其混合物。
适宜的硫化烷基秋兰姆包括四硫化双五亚甲基秋兰姆、二硫化四丁基秋兰姆、二硫化四乙基秋兰姆、单硫化四甲基秋兰姆、二硫化四苄基秋兰姆及其混合物。
加入到组合物中的硫及硫化促进剂的量通常基于组合物中存在的弹性体重量为约0.5～8wt.％。
促进剂硫黄硫化体系也可以作为还含有作为辅助硫化剂的氧化锌或其类似物的硫化体系中的助硫化剂。氧化锌在该类体系中的使用量通常为每100重量份弹性体约0.2～约7重量份。本发明提供特别好的低硫化返原体系，其中氧化锌的加入量为每100重量份弹性体约0.5～约5重量份。
弹性体聚合物组合物也可以含有其它添加剂，例如润滑剂、填料、增塑剂、增粘剂、着色剂、发泡剂和抗氧化剂。
填料的例子包括无机填料如增强炭黑、二氧化硅、碳酸钙、滑石和粘土，和有机填料如高苯乙烯树脂、苯并呋喃-茚树脂、酚醛树脂、木素、改性密胺树脂和石油树脂。
润滑剂的例子包括石油类润滑剂如油、石蜡和液体石蜡，煤焦油类润滑剂如蓖麻油、亚麻子油、菜油和椰子油；妥尔油；蜡类如蜂蜡、巴西棕榈蜡和羊毛脂；脂肪酸及脂肪酸盐如亚油酸、棕榈酸、硬脂酸钡、硬脂酸钙和月桂酸锌；以及合成聚合物如石油树脂。
增塑剂的例子包括烃油如石蜡、芳香油和环烷油、苯二甲酸酯类、己二酸酯类、癸二酸酯类和磷酸类增塑剂。
增粘剂的例子包括石油树脂、苯并呋喃-茚树脂、萜烯苯酚树脂和二甲苯/甲醛树脂。
着色剂的例子包括无机和有机颜料。
发泡剂的例子包括碳酸氢钠、碳酸铵、N,N’-二亚硝基五亚甲基四胺、偶氮甲酰胺(azocarbonamide)、偶氮二异丁腈、苯磺酰肼、甲苯磺酰肼、氨化钙、对-甲苯磺酰叠氮化物、水杨酸、苯二甲酸和脲。
使用任何适宜的混合装置例如密闭式混合机(布雷本登塑性记录仪)、班伯里密炼机、粉碎混合机、捏合机或类似的混合装置，可以制备并共混可硫化组合物。共混温度和时间可分别为约35℃～180℃和4～10分钟。当弹性体和任选的填料、加工助剂、抗氧化剂及其类似物形成均匀的混合物后，通过在较低的温度下进一步混入交联剂，接着将所得到的共混物加热到约100～200℃，更优选约110-180℃的温度并保持约1～60分钟而硫化该混合物。通过使用挤出机或模具将预硫化的配料成型并将该组合物在上述温度和硫化时间下进行处理，制备得到例如带状物、轮胎组件和软管等模制品。
为了说明本发明，给出下述实施例。在下述实施例中使用的材料说明如下：
BIMS --并丁烯和对-甲基苯乙烯的无规溴化共聚物，其
含有约7.5wt.％对-甲基苯乙烯、1.2摩尔％的
苄基溴，门尼粘度ML(1+8)在125℃时约为
45。
EXACTTM 5008 --乙烯和丁烯的共聚物，熔融指数为10，密度
为0.865。
EXACTTM 3028 --乙烯和丁烯的共聚物，熔融指数为1.0，密度
为0.900。
SLP-9053 --乙烯和丁烯的共聚物，熔融指数为4，密度为
0.865。
VISTALONTM 2504 -乙烯(57.5wt.％)、丙烯和亚乙基-降冰片烯
(4.7wt.％)的弹性三元共聚物，门尼粘度(1+4)
在125℃时为25。
FLEXONTM 815 --链烷加工油。
SARETTM 634 --从Westchester,Pa.的Sartomer公司购得的
二甲基丙烯酸锌。
DICUPTM 40KE --过氧化二枯基。
SANTOCURETM --N-环己基-2-苯并噻唑亚磺酰胺。
VULTACTM-5 --从Pennwalt公司购得的二硫化烷基苯酚。
实施例1
将BIMS共聚物、炭黑和加工油(重量份)在两辊磨上于约90℃共混约3分钟，制备如表1公开的橡胶母炼胶。然后将部分母炼胶与示于表1的交联剂通过在两辊磨中于60℃混合约10分钟而混合，得到样品A、B和C。
然后用Monsanto振荡盘式流变计在示于表Ⅰ的硫化和MDR条件下评价这些组合物各自的硫化行为。将挤出颗粒模制成模塑试条，根据下述ASTM程序进行测试，得到其物理性能：
抗张强度-ASTM D-638
伸长率 -ASTM D-638
模量 -ASTM D-790
表Ⅰ
| A | B | C | |
| 母炼胶 | |||
| BIMS | 100 | 100 | 100 |
| 炭黑N-550 | 60 | 60 | 60 |
| Flexon 815 | 10 | 10 | 10 |
| 促进剂 | |||
| SARET 634 | 2 | 2 | |
| DICUP 40 KE | 2 | 2 | |
| 总PHR | 172 | 174 | 172 |
| 硫化条件 | |||
| 时间，分钟 | 30 | 30 | |
| 温度，℃ | 171 | 171 | |
| 物理性能 | |||
| MDR171C,1Arc,30分钟 | |||
| ML，磅-英寸 | 3.74 | 3.52 | 3.01 |
| MH，磅-英寸 | 22.4 | 20.22 | 3.4 |
| ts2，分钟 | 1.17 | 1.2 | 没有 |
| t90，分钟 | 12.14 | 20.27 | 27.65 |
| 速率，磅-英寸/分钟 | 6.9 | 3.2 | 0.3 |
| 应力应变 | |||
| 100％模量，MPa | 5.5 | 5.5 | |
| 300％模量，MPa | 无 | 无 | |
| 断裂拉伸强度，MPa | 14.7 | 13.6 | |
| 断裂伸长率，％ | 195 | 192 | |
表Ⅰ中的硫化数据表明二甲基丙烯酸锌/过氧化物硫化体系能将BIMS聚合物组合物有效硫化。单独使用过氧化物作为硫化剂(样品C)没有发生硫化。
实施例2
将示于表Ⅱ中的BIMS(样品D)及一系列其与饱和聚合物的六种共混物(样品E～J)同二甲基丙烯酸锌和过氧化物硫化剂一起形成配料，然后除了样品G在两辊磨中在140℃而不是60℃进行混合外，按实施例1所述评价它们的硫化效果及其物理性能。
表Ⅱ中的数据表明BIMS和所述聚合物的共混物的初始硫化效果和物理性能良好且热老化后的物理性能得到良好保持。
表Ⅱ
| D | E | F | G | H | I | J | |
| 母炼胶 | |||||||
| BIMS | 100 | 50 | 75 | 50 | 50 | 75 | 50 |
| EXACT 5008 | 50 | 25 | |||||
| EXACT 3028 | 50 | ||||||
| SLP 9053 | 50 | 25 | |||||
| VISTALON 2504 | 50 | ||||||
| 炭黑N-550 | 60 | 60 | 60 | 60 | 60 | 60 | 60 |
| FLEXON 815 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
| 促进剂 | |||||||
| DICUP 40KE | 4 | 4 | 2 | 4 | 4 | 2 | 4 |
| SARET 634 | 4 | 4 | 2 | 4 | 4 | 2 | 4 |
| 总PHR | 178 | 178 | 174 | 178 | 178 | 174 | 178 |
| MDR@165C，1Arc，60分钟 | |||||||
| ML，磅-英寸 | 3.70 | 1.67 | 2.18 | 4.87 | 1.97 | 2.67 | 3.03 |
| MH，磅-英寸 | 24.51 | 15.76 | 17.38 | 28.23 | 16.89 | 18.88 | 22.38 |
| ts2，分钟 | 1.04 | 1.04 | 1.38 | 0.68 | 0.92 | 1.26 | 0.79 |
| t90，分钟 | 39.19 | 31.09 | 42.08 | 19.52 | 22.19 | 42.53 | 31.84 |
| 最大速率，磅-英寸/分钟 | 4.00 | 3.40 | 2.50 | 5.80 | 4.10 | 3.00 | 5.20 |
| MH-ML，磅-英寸 | 20.81 | 14.10 | 15.20 | 23.37 | 14.92 | 16.20 | 19.35 |
| 硫化条件 | |||||||
| 时间，分钟 | 45 | 45 | 45 | 30 | 30 | 45 | 45 |
| 温度，C | 165 | 165 | 165 | 165 | 165 | 165 | 165 |
| 物理性能 | |||||||
| 初始性能@室温 | |||||||
| 100％模量，MPa | 6.6 | 5.0 | 5.8 | 9.5 | 4.2 | 5.0 | 3.9 |
| Psi | 951 | 723 | 846 | 1384 | 608 | 720 | 559 |
| 断裂拉伸强度，MPa | 11.1 | 9.5 | 12.4 | 15.2 | 11.4 | 11.9 | 10.7 |
| Psi | 1608 | 1384 | 1800 | 2206 | 1654 | 1724 | 1558 |
| 断裂伸长率，％ | 134 | 267 | 187 | 175 | 377 | 198 | 218 |
| 肖氏A硬度 | 60.9 | 73.7 | 67.3 | 86.7 | 71.9 | 69.1 | 59.5 |
| 在125℃下老化70小时 | |||||||
| 100％模量，MPa | - | 7.7 | - | 12.8 | 6.3 | 8.6 | 7.9 |
| Psi | - | 1117 | - | 1849 | 916 | 1253 | 1141 |
| 断裂拉伸强度，MPa | 11.7 | 10.6 | 8.3 | 16.6 | 13.6 | 13.0 | 13.0 |
| Psi | 1697 | 1538 | 1205 | 2400 | 1976 | 1884 | 1884 |
| 断裂伸长率，％ | 96 | 162 | 85 | 135 | 255 | 139 | 157 |
| 肖氏A硬度 | 73.3 | 79.3 | 74.1 | 88.1 | 78.7 | 75.5 | 70.1 |
| 在150℃下老化70小时 | |||||||
| 100％模量，MPa | - | 8.6 | - | 14.3 | 7.9 | 10.5 | 9.6 |
| Psi | - | 1241 | - | 2072 | 1143 | 1515 | 1388 |
| 断裂拉伸强度，MPa | 9.9 | 10.8 | 11.8 | 17.5 | 13.0 | 13.0 | 12.2 |
| Psi | 1431 | 1559 | 1707 | 2536 | 1886 | 1878 | 1773 |
| 断裂伸长率，％ | 78 | 131 | 99 | 126 | 186 | 119 | 124 |
| 肖氏A硬度 | 76.3 | 79.5 | 76.7 | 90.1 | 80.5 | 75.5 | 71.3 |
对比例
将示于表Ⅲ的BIMS(样品K)及一系列其与烯属不饱和聚合物的六种共混物(样品L～Q)如实施例1所述形成配料并评价其硫化和物理性能。样品K、L、N和P含有本发明的硫化剂，而样品M、O和Q含有传统的硫促进氧化锌硫化体系。
表Ⅲ中的数据表明BIMS和所述烯属不饱和聚合物的共混物的耐热老化性能差。
本发明的交联硫化组合物的物理性能有不同寻常的均衡，可作为涂料、粘合剂并用于模塑及挤出机械、汽车和工业制品如轮胎、软管、带状物等及其类似的应用。
表Ⅲ
| K | L | M | N | O | P | Q | |
| 母炼胶 | |||||||
| BIMS | 100 | 20 | 20 | 20 | 20 | 30 | 30 |
| 天然橡胶(SMR) | 80 | 80 | |||||
| 丁二烯橡胶(BUDENE) | 80 | 80 | 70 | 70 | |||
| 炭黑N-550 | 60 | 60 | 60 | 60 | 60 | 60 | 60 |
| FLEXON 815 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
| 促进剂 | |||||||
| DICUP 40KE | 4 | 4 | 4 | 4 | |||
| SARET 634 | 4 | 4 | 4 | 4 | |||
| 氧化锌 | 2 | 2 | 2 | ||||
| SANTOCURE | 2 | 2 | 2 | ||||
| 硫 | 0.5 | 0.5 | 0.5 | ||||
| VULTAC 5 | 1.5 | 1.5 | 1.5 | ||||
| 总PHR | 178 | 178 | 176 | 178 | 176 | 178 | 176 |
| MDR@165C,1Arc,60分钟 | |||||||
| ML，磅-英寸 | 3.7 | 1.6 | 4.6 | 4.4 | |||
| MH，磅-英寸 | 24.5 | 22.8 | 72.6 | 67.9 | |||
| ts2，分钟 | 1.0 | 0.7 | 0.5 | 0.6 | |||
| t90，分钟 | 39.2 | 12.9 | 14.3 | 16.4 | |||
| 最大速率，磅-英寸/分钟 | 4.0 | 6.8 | 22.2 | 18.4 | |||
| MH-ML，磅-英寸 | 20.8 | 21.1 | 67.8 | 63.5 | |||
| MDR@160C,1Arc，30分钟 | |||||||
| ML，磅-英寸 | 2.5 | 5.3 | 4.9 | ||||
| MH，磅-英寸 | 20.5 | 35.3 | 31.9 | ||||
| ts2，分钟 | 2.9 | 2.5 | 2.4 | ||||
| t90，分钟 | 5.1 | 7.4 | 8.2 | ||||
| 最大速率，磅-英寸/分钟 | 11.4 | 10.7 | 7.6 | ||||
| MH-ML，磅-英寸 | 18.0 | 30.0 | 27.1 | ||||
| 硫化条件 | |||||||
| 时间，分钟 | 45 | 20 | 7 | 20 | 9.5 | 20 | 10 |
| 温度，C | 165 | 165 | 160 | 165 | 160 | 165 | 160 |
| 物理性能 | |||||||
| 初始性能@室温 | |||||||
| 100％模量，MPa | 6.56 | 3.942 | 2.792 | - | 3.918 | - | 3.977 |
| Psi | 951 | 572 | 405 | - | 568 | - | 577 |
| 300％模量，MPa | - | - | 14.631 | - | - | - | - |
| Psi | - | - | 2121 | - | - | - | - |
| 断裂拉伸强度，MPa | 11.1 | 15.3 | 20.2 | 8.8 | 15.7 | 7.5 | 14.3 |
| Psi | 1608 | 2218 | 2935 | 1273 | 2274 | 1081 | 2070 |
| 断裂伸长率，％ | 134 | 237 | 397 | 78 | 293 | 72 | 278 |
| 肖氏A硬度 | 60.9 | 59.7 | 57.7 | 78.1 | 67.9 | 77.5 | 65.5 |
| 在125℃下老化70小时 | |||||||
| 100％模量，MPa | - | 1.91 | - | - | - | - | - |
| Psi | - | 277 | - | - | - | - | - |
| 断裂拉伸强度，MPa | 11.7 | 3.2 | 1.9 | 2.4 | 4.3 | 3.6 | 7.0 |
| Psi | 1697 | 463 | 271 | 342 | 626 | 528 | 1018 |
| 断裂伸长率，％ | 96 | 152 | 90 | 16 | 50 | 33 | 81 |
| 肖氏A硬度 | 73.3 | 46.9 | 45.3 | 82.5 | 75.5 | 81.9 | 74.5 |
| 在150℃下老化70小时 | |||||||
| 断裂拉伸强度，MPa | 9.9 | 失败 | 失败 | 失败 | 失败 | 失败 | 失败 |
| Psi | 1431 | ||||||
| 断裂伸长率，％ | 78 | ||||||
| 肖氏A硬度 | 76.3 | 69.7 | 61.9 | 91.9 | 89.9 | 92.3 | 90.3 |
Claims (30)
1．一种可硫化的聚合物组合物，主要含有C4～C7异单烯烃和对-烷基苯乙烯共聚单体的氯化或溴化弹性无规共聚体，任选可有可无的饱和聚合物及硫化有效量的硫化剂混合物的混合物，该硫化剂混合物包括含有3～300个碳原子的不饱和羧酸的弹性体可溶的多价金属盐与有机过氧化物。
2．根据权利要求1的组合物，其中所述羧酸为含有3～6个碳原子的α或β不饱和一元羧酸。
3．根据权利要求2的组合物，其中所述一元羧酸选自丙烯酸、甲基丙烯酸和巴豆酸。
4．根据权利要求3的组合物，其中所述一元羧酸为甲基丙烯酸。
5．根据权利要求2的组合物，其中所述多价金属选自锌、铁、镉、铋、铝、镁和钙。
6．根据权利要求5的组合物，其中多价金属为锌。
7．根据权利要求2的组合物，其中所述硫化剂为二丙烯酸锌或二甲基丙烯酸锌。
8．根据权利要求1的组合物，其中所述共聚体为含有至少约80wt.％异丁烯和约0.5～20wt.％对-甲基苯乙烯的溴化共聚体。
9．根据权利要求8的组合物，其中约5～60摩尔％的对-甲基苯乙烯单体单元含有单溴甲基。
10．根据权利要求8的组合物，其中所述共聚体中溴甲基的含量为约0.01～10摩尔％。
11．根据权利要求1的组合物，其中所述多价金属盐在所述组合物中的存在量基于所述组合物中聚合物重量为约0.5～10wt.％。
12．根据权利要求1的组合物，其中所述任选可有可无的饱和聚合物在所述组合物中的存在量为每99～1重量份所述卤化共聚体1～99重量份。
13．根据权利要求12的组合物，其中所述任选可有可无的聚合物为EPDM橡胶。
14．根据权利要求12的组合物，其中所述任选可有可无的聚合物选自聚乙烯和乙烯与至多约50wt.％的C3～C8单烯烃的共聚物。
15．根据权利要求1的组合物，其中所述有机过氧化物在所述组合物中的存在量基于所述组合物中聚合物含量为约0.2～6wt.％。
16．根据权利要求12的组合物，其中所述羧酸为含有3～6个碳原子的α或β不饱和一元羧酸。
17．根据权利要求16的组合物，其中所述一元羧酸选自丙烯酸、甲基丙烯酸和巴豆酸。
18．根据权利要求17的组合物，其中所述一元羧酸为甲基丙烯酸。
19．根据权利要求16的组合物，其中多价金属选自锌、铁、镉、铋、铝、镁和钙。
20．根据权利要求19的组合物，其中多价金属为锌。
21．根据权利要求12的组合物，其中硫化剂为二丙烯酸锌或二甲基丙烯酸锌。
22．根据权利要求12的组合物，其中共聚体为含有至少约80wt.％异丁烯和约0.5～20wt.％对-甲基苯乙烯的溴化共聚体。
23．根据权利要求22的组合物，其中约5～60摩尔％的对-甲基苯乙烯单体单元含有单溴甲基。
24．根据权利要求22的组合物，其中共聚体中溴甲基的含量为约0.01～10摩尔％。
25．根据权利要求12的组合物，其中多价金属盐在所述组合物中的存在量基于所述组合物中聚合物重量为约0.5～10wt.％。
26．根据权利要求12的组合物，其中有机过氧化物在所述组合物中的存在量基于所述组合物中聚合物含量为约0.2～6wt.％。
27．一种制备硫化组合物的方法，该方法包括将根据权利要求1的组合物在一定的温度下加热足以将所述组合物进行硫化的一段时间。
28．一种制备硫化组合物的方法，该方法包括将根据权利要求12的组合物在一定的温度下加热足以将所述组合物进行硫化的一段时间。
29．一种根据权利要求28所述的方法制备的硫化橡胶。
30．一种根据权利要求29所述的方法制备的硫化橡胶。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US71703396A | 1996-09-20 | 1996-09-20 | |
| US08/717,033 | 1996-09-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1237988A true CN1237988A (zh) | 1999-12-08 |
Family
ID=24880437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97198075A Pending CN1237988A (zh) | 1996-09-20 | 1997-09-19 | 作为含有异单烯烃/对－烷基苯乙烯卤化共聚物的组合物的硫化剂的丙烯酸或甲基丙烯酸金属盐 |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0929601A1 (zh) |
| JP (1) | JP2001500911A (zh) |
| KR (1) | KR20000036212A (zh) |
| CN (1) | CN1237988A (zh) |
| AT (1) | AT410094B (zh) |
| BR (1) | BR9711520A (zh) |
| CA (1) | CA2263341A1 (zh) |
| EA (1) | EA199900270A1 (zh) |
| HU (1) | HUP9904170A3 (zh) |
| PL (1) | PL332320A1 (zh) |
| WO (1) | WO1998012251A1 (zh) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11310762A (ja) * | 1998-04-17 | 1999-11-09 | Minnesota Mining & Mfg Co <3M> | 粘着剤組成物及びそれを使用した粘着剤製品 |
| US6626219B2 (en) * | 1999-12-28 | 2003-09-30 | Exxonmobil Chemical Patents Inc. | Inner tube compositions having improved heat resistance characteristics |
| MXPA02006907A (es) * | 2000-01-13 | 2003-05-23 | Exxonmobil Chem Patents Inc | Articulos laminares que contienen capas de resinas que contienen elastomeros de polimero que contiene etileno. |
| US6525128B2 (en) | 2001-02-01 | 2003-02-25 | The Goodyear Tire & Rubber Company | Composition of organophosphite, isobutylene copolymer and silica and tire thereof |
| WO2002096679A2 (en) * | 2001-05-29 | 2002-12-05 | Societe De Technologie Michelin | Tire and support |
| US6602956B2 (en) | 2001-11-13 | 2003-08-05 | Solvay Engineered Polymers | Melt strength thermoplastic elastomers and methods for making same |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5162445A (en) * | 1988-05-27 | 1992-11-10 | Exxon Chemical Patents Inc. | Para-alkylstyrene/isoolefin copolymers and functionalized copolymers thereof |
| US4987192A (en) * | 1989-05-19 | 1991-01-22 | Oberster Arthur E | Colored tire stocks having improved abrasion resistance, color and color stability |
| US5288446A (en) * | 1990-04-23 | 1994-02-22 | Sumitomo Rubber Industries, Ltd. | Production of rubber article |
| US5063268A (en) * | 1990-06-08 | 1991-11-05 | Exxon Chemical Patents Inc. | Composition for tire treads (E-235) |
| JP3030467B2 (ja) * | 1990-11-28 | 2000-04-10 | バンドー化学株式会社 | 水素化ニトリルゴム配合物と繊維との接着方法 |
| US5298562A (en) * | 1991-08-19 | 1994-03-29 | Sartomer Company, Inc. | Calcium di(meth)acrylate cured halogenated polyethylene polymers |
| JPH07116339B2 (ja) * | 1992-11-10 | 1995-12-13 | 横浜ゴム株式会社 | ゴム組成物 |
| US5473017A (en) * | 1993-09-30 | 1995-12-05 | Exxon Chemical Patents Inc. | Intervulcanized elastomer blends |
| US5656694A (en) * | 1995-05-03 | 1997-08-12 | Exxon Chemical Patents Inc. | Interpolymer cures of blends comprising halogenated isoolefin/para-alkylstyrene elastomers and unsaturated elastomers |
-
1997
- 1997-09-19 CA CA002263341A patent/CA2263341A1/en not_active Abandoned
- 1997-09-19 CN CN97198075A patent/CN1237988A/zh active Pending
- 1997-09-19 AT AT0911597A patent/AT410094B/de not_active IP Right Cessation
- 1997-09-19 PL PL97332320A patent/PL332320A1/xx unknown
- 1997-09-19 EP EP97942661A patent/EP0929601A1/en not_active Withdrawn
- 1997-09-19 EA EA199900270A patent/EA199900270A1/ru unknown
- 1997-09-19 HU HU9904170A patent/HUP9904170A3/hu unknown
- 1997-09-19 BR BR9711520A patent/BR9711520A/pt unknown
- 1997-09-19 JP JP10514989A patent/JP2001500911A/ja active Pending
- 1997-09-19 WO PCT/US1997/016963 patent/WO1998012251A1/en not_active Application Discontinuation
- 1997-09-19 KR KR1019997002273A patent/KR20000036212A/ko not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001500911A (ja) | 2001-01-23 |
| BR9711520A (pt) | 1999-08-24 |
| WO1998012251A1 (en) | 1998-03-26 |
| EA199900270A1 (ru) | 1999-12-29 |
| HUP9904170A3 (en) | 2000-05-29 |
| AT410094B (de) | 2003-01-27 |
| HUP9904170A2 (hu) | 2000-04-28 |
| KR20000036212A (ko) | 2000-06-26 |
| PL332320A1 (en) | 1999-08-30 |
| EP0929601A1 (en) | 1999-07-21 |
| CA2263341A1 (en) | 1998-03-26 |
| ATA911597A (de) | 2002-06-15 |
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