CN1183164C - 低卤素含量的卤化丁基橡胶 - Google Patents
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Abstract
本发明提供新的具有一定的卤素含量、一定的未卤化双键含量和一定的抗附聚/硫化控制剂含量的丁基橡胶。它表现出优异的机械性能和生理学性能，因而适宜用来生产轮胎、特别是轮胎内衬、轮胎侧壁或轮胎胎面和用于药用橡胶制品中。
Description
本发明涉及新的具有低卤素含量的卤化丁基橡胶、其生产方法及其在生产硫化橡胶材料中的用途。
人们知道，卤化丁基橡胶特别用来生产轮胎，因为卤化丁基橡胶被证明在粘合行为、挠曲强度和使用寿命方面特别优异并且不透空气和水。考虑到上述物理性能之间的平衡，卤化丁基橡胶适用于轮胎制造，特别适用于轮胎内衬的生产。由于使用基于卤化丁基橡胶的内衬，轮胎中所用的轮胎胎体和钢帘线和编织帘布便不受空气膨胀中包含的潮气和氧气的侵害。这对于充气轮胎、特别那些高应力卡车轮胎的寿命具有积极的影响。
人们一直在尝试提高卤化丁基橡胶的物理性能，例如通过增加丁基橡胶中卤素含量(改善粘合性能)。在这方面，可参见美国专利说明书2,698,041和英国专利申请GB 2 072 576和欧洲专利申请EP 0 385760，其中描述了卤化丁基橡胶在轮胎制造中的用途和应用。
由于使用纯卤化丁基橡胶作内衬的橡胶材料的具有众多的优点(参见EP 0 385 760)，最近有人提出使用包含卤化丁基橡胶的纯丁基橡胶的胶料。据说这样可以减少由于热固化过程而在内衬中产生的裂缝，最终对充气轮胎的寿命产生积极影响。
上述先有技术所述的卤化丁基橡胶或包含卤化丁基橡胶和纯丁基橡胶的胶料的缺点有例如，老化性能不能令人满意、在交联过程中生成腐蚀性的卤化氢、所述共混物的交联速率低，这不利于轮胎制造过程中的生产率。
因此，本发明的目的是提供能够确保上述性能的总体改善的卤化丁基橡胶，而不必使用卤化丁基橡胶的未卤化丁基橡胶的共混物。
该目的通过提供具有一定的低含量的卤素、一定含量的未卤化双键和一定含量的抗附聚/硫化控制剂的新的卤化丁基橡胶而得以实现。
因此，本发明涉及卤化丁基橡胶，其特征在于，相对于卤化丁基橡胶的总量计，卤素含量为0.5-2.5％并且未卤化双键的含量大于0.7％(摩尔)，其抗附聚/硫化控制剂的含量为1.0-2.2％(重量)。
在本发明中，卤化丁基橡胶应理解为被氯和/或溴(优选溴)卤化的丁基橡胶。
根据本发明，优选的卤化丁基橡胶是未溴化双键含量为0.7-1.0％(摩尔)、特别是0.75-0.95％(摩尔)，并且抗附聚/硫化控制剂含量为1.25-2.0％(重量)、特别是1.45-2.0％(重量)的卤化丁基橡胶。
本发明的丁基橡胶的卤素含量优选0.8-1.9％。对于溴化丁基橡胶来说，溴含量优选1.4-1.8％。
根据本发明，术语“丁基橡胶”应理解为是指基于异烯烃和烯烃的共聚物，例如在上述美国专利2,698,041和其它专利文献中所述的那些。丁基橡胶的特征是含有70-99.5％(重量)具有4-8个碳原子的异烯烃(例如异丁烯、3-甲基丁烯-1，4/甲基戊烯1，2、乙基丁烯-1和/或4-乙基戊烯-1，特别是异丁烯)和0.5-30％(重量)具有4-18个碳原子的二烯(例如异戊二烯、丁二烯-1，3、2，4-二甲基丁二烯-1，3、1，3-戊二烯、3-甲基戊二烯-1，3、己二烯-1，4、2-新戊基丁二烯-1，3、2-甲基己二烯-1，5、2-甲基戊二烯-1，4、2-甲基庚二烯-1，6、环戊二烯、环己二烯、1-乙烯基环己二烯及其混合物)。此外，也可以使用常规量的其它单体例如苯乙烯、氯代苯乙烯和/或α-甲基苯乙烯。
特别优选异烯烃含量为95-99.9％(重量)、二烯含量为0.5-5.0％(重量)的丁基橡胶。就此而论，特别优选使用基于异丁烯和异戊二烯的丁基橡胶。
本发明的卤化丁基橡胶的特征在于，它具有一定含量的未卤化双键、一定含量的抗附聚/硫化控制剂和一定含量的卤素。因此，重要的是从上述单体出发生产丁基橡胶如何获得所需的含量。丁基橡胶可以以通常的方式生产，通过溶液聚合、气相聚合、或淤浆聚合的方法生产。聚合优选在悬浮液中进行(淤浆法)(例如参见，Bayer Handbook forthe Rubber Industry，Section A 9.1，p.208(1991))。
下面是特别适宜的抗附聚/硫化控制剂：基于含有8-22个碳原子(优选12-18个碳原子)的脂肪酸的盐，例如硬脂酸和棕榈酸以及油酸的钙盐、镁盐钾盐和铵盐。硅酸盐例如硅酸钙也是适宜的抗附聚/硫化控制剂。抗附聚/硫化控制剂可以分别使用，也可以相互混合使用。最优选的混合比可以通过适当的初步试验容易地测得。优选使用硬脂酸钙和/或棕榈酸钙。
在用作本发明的卤化丁基橡胶的原材料的丁基橡胶的生产过程中，必须确保抗附聚/硫化控制剂的用量在上述定量的范围内。
本发明还涉及生产上述本发明的的卤化丁基橡胶的方法，其特征在于在气相中或者在有机溶剂的存在下，用卤化剂处理抗附聚/硫化控制剂的含量为所用的丁基橡胶总量的1.0-2.2％重量的丁基橡胶，直至丁基橡胶的卤素含量为0.5-2.5％重量并且未卤化双键含量大于0.7％摩尔。
本发明的卤化丁基橡胶可以通过用卤化剂(例如氯或溴，优选溴)处理细碎分散的丁基橡胶来制备，或者在混合设备中将溴化剂例如N-溴代琥珀酰亚胺与作为基础的丁基橡胶剧烈混合来制备，或者通过用对应的溴化剂处理作为基础的丁基橡胶的有机溶剂溶液或分散体来制备(例如参见，Bayer Handbook for the Rubber Industry，Section A9.1，p.208(1991))。
在该方法的过程中，挤出丁基橡胶的卤化应加以控制，使得残余的未卤化或未溴化双键的含量保持在一定的范围内。同时，卤素(优选溴)的含量落在上述范围内。
本发明的卤化丁基橡胶可以用来生产硫化橡胶材料，例如通过将卤化丁基橡胶与炭黑、水合二氧化硅或其它已知的成分(添加剂)混合并以通常的方式例如用硫磺进行交联。
卤化丁基橡胶主要用来生产轮胎，特别是用来生产轮胎内衬和轮胎侧壁，并且也用来生产轮胎胎面。此外，卤化丁基橡胶也用于药物应用，例如软管和瓶塞。此外，也可用常规量的卤化丁基橡胶所有已知的合成橡胶和天然橡胶加上常规填充剂(例如炭黑或水合二氧化硅)进行混炼。
与迄今为止已知的卤化丁基橡胶或其与纯丁基橡胶的胶料相比，本发明的卤化丁基橡胶具有如下优点：轮胎内衬对胎体的附着力不变，交联速率高，在内衬的寿命期内裂缝生长的减少，以及轮胎内衬的使用寿命较长。
实施例1
用市售的丁基橡胶(Bayer-Rubber N.V.，Antwerp，Belgium，牌号Polysar Butyl 301)生产本发明的卤化丁基橡胶。该丁基橡胶具有如下组成和物理性能：
异戊二烯含量：1.55-1.95％(摩尔)
异丁烯含量：97.5-98.0
门尼粘度(ML 1+8，125℃)：51±5
以下述方式溴化起始丁基橡胶：
首先制备上述丁基橡胶在己烷中的15-20％(重量)溶液。在小心控制的条件下，每1000公斤丁基橡胶将36公斤溴加到丁基橡胶聚合物溶液中。在50℃下，通过将聚合物的己烷溶液剧烈混合进行溴化。反应完全后，将溶剂用50％(重量)氢氧化钠溶液中和，每1000公斤丁基橡胶向该混合物中加入21公斤硬脂酸钙，并且每1000公斤还加入13.5公斤环氧化的大豆油作为稳定剂。然后使常规方式将溶剂蒸发。残余物构成了橡胶悬浮液，从中以常规方式获得固体橡胶。相对于所用的丁基橡胶的总量计，所得溴化丁基橡胶的溴含量为1.76％，未卤化双键的含量为0.77％(摩尔)，脂肪酸盐的含量为2.10％(重量)(溴化丁基橡胶)。
用与上述相同的方法制备溴化丁基橡胶B，C和D。比较例E和F是以相同方式制备的溴化丁基橡胶。橡胶E具有标准PolysarBrombutyl 2030的性能，其卤素含量和脂肪酸盐高于本发明橡胶的含量。橡胶F具有比本发明橡胶较低的卤素含量和脂肪酸盐含量。橡胶G由70份PolysarBrombutyl 2030和30份PolysarBrombutyl 402的共混物构成。胶料M(A)到M(G)是用表1的溴化丁基橡胶配制的(表2)。表2中的化合物成分是炭黑(Corax N660，得自Degussa)、矿物油(Sunpar 2280，得自Sun Oil)、树脂(Pentalyn A，得自Hercules)、硬脂酸(得自Henkel)和MBTS(Vulkacit DM/MG，得自Bayer)。
将这些化合物在Werner & Pflerderer GK 1.5E密炼机中混合。然后将氧化锌和硫磺加到滚筒上。在用滚筒最后混合后，得到试验料。用MDR 2000流变仪(Flexsys提供)测定硫化行为(焦烧时间t90，最大扭矩)。在各种性能中，力学性能、抗动态撕裂性和对胎体的附着力作为硫化性能来测定。
抗动态撕裂性是用Bayer撕裂分析仪进行的(描述于U.Eisele，S.A.Kelbch和H.W.Engels in Kautsch.，Gummi，Kunstst.45，1064(1992))。该机器能够模拟工作状态的轮胎的橡胶成分的负荷和环境条件。已经表明，可以获得该特定实验室试验与一系列不同轮胎部件(包括内衬混合料)之间的良好关系(参见A.J.M.Sumner，S.A.Kelbch和U.G.Eisele，Proceedings of the 146th ACS Rubber Division Meeting，1994年10月，Pirrsburgh，Paper 18)。用带有横向划痕(大约1毫米深)的橡胶条(60×15×1.5mm)作试样。试验在控制的轮胎对应的环境条件下进行。
用伺服-水力驱动带有下部试样支架的往复活塞。可以在伺服-水力的能力范围内使试样经受任何所需的随时间变化的负荷。对于轮胎胶料通常采用脉冲形负荷。各(黑色)试样(最多同时有10个)从后面照亮，与负荷池连接，而负荷池又与步进式电动机驱动装置相连。用负荷池，首先将材料中随时间变化的应力测定出来，然后，用步进式电动机调节最小力(初始应力)。除了最大和最小应力和应变外，还测定了试样的储能密度和拉伸变定。用用步进式电动机操作的x/y滑片相连的CCD视觉快门照相机记录撕裂照片。然后根据图表转变为图象并数字化，然后在通过精确计量撕裂的黑色面/线确定了撕裂唇(TEAR LIP)和撕裂底后，用软件测定撕裂轮廓长度。从撕裂轮廓长度对负荷周期的依赖性测定撕裂增长速率dlnc/dn＝1/c(dc/dn)并用来给出在出现灾难性撕裂生长前测定数据的范围。
通过对轮胎试验的关联表明(参见A.J.M.Summer，S.A.Kelbch，U.G.Eisele Rubber World 213，No.2，38(1975))，在轮胎工作时，内衬胶料经受恒定的应变负荷，所以必须进行在恒定应变下撕裂增长速率的比较。
受试胶料的抗撕裂性用未老化的和老化的(168小时，120℃，循环空气室内)的试样测定。
对胎体的附着力是用带有纺织背底的夹层试样(丁基胶料/胎体胶料)进行的，该试样已经在166℃和加压条件下硫化了30分钟。粘合强度定义为将两种胶料分开所必须的力。
表3的结果表明：
包含比较橡胶F的、溴和硬脂酸钙含量低且双键比例高的胶料M(F)对胎体的附着力比本发明的胶料M(A)至M(D)的低得多。然而，它未表现出老化后模量的增加并表现出良好的抗动态撕裂性。另一方面，具有常规溴、硬脂酸钙和双键含量的胶料M(E)表现出良好的附着力，但也表现出老化后模量的增加，并且抗撕裂性极差。
从表中可以看出，老化后模量的增加对于内衬胶料的抗撕裂性具有消极的影响。
包含比较用橡胶G的胶料M(G)是丁基橡胶与溴化丁基橡胶的共混物，表现出较好的抗老化性，但也表现出硫化速率的降低。当采用正常温度和时间时，硫化速率的降低导致对胎体附着力的降低。
从胶料M(A)至M(D)的数据可以明显看出降低溴和硬脂酸钙的含量不会改变模量和未老化试样的渗透性。仅在溴和硬脂酸钙含量最低的情况下(1.2％Br，1.05％硬脂酸钙)才观察到附着力的降低。与标准试样相比；撕裂增长速率大幅度降低，这一点在老化后变得更明显。
溴化丁基橡胶A至C是特别推荐用作长期工作的卡车的内衬胶料，它具有关键性能的适当比例的平衡。
表1：所用的丁基橡胶
| BIIR | 溴含量，％ | 非卤素双键含量，％ | 脂肪酸盐含量，％ | 钙盐含量，％ | 钠盐含量，％ | 稳定剂，％ |
| A | 1.76 | 0.07 | 2.10 | ＜0.02 | ＜0.02 | 1.35 |
| B | 1.66 | 0.82 | 1.88 | ＜0.02 | ＜0.02 | 1.28 |
| C | 1.37 | 0.93 | 1.45 | ＜0.02 | ＜0.02 | 1.10 |
| D | 1.21 | 1.02 | 1.05 | ＜0.02 | ＜0.02 | 0.95 |
| 比较例A1 | 1.94 | 0.65 | 2.45 | ＜0.02 | ＜0.02 | 1.50 |
| 比较例F | 1.05 | 1.10 | 0.95 | ＜0.02 | ＜0.02 | 0.85 |
| 比较例G2 | 1.40 | 1.12 | 1.85 | ＜0.02 | ＜0.02 | 1.05 |
1.Polysar Bromobutly 2030(Bayer提供)
2.70份Polysar Bromobutyl 2030和30份Polysar Butyl 4023的共混物(Bayer提供)
3.Polysar Butyl 402未溴化，双键含量为2.2％；Mooney(ML1+8100℃)47
表2：溴化丁基橡胶胶料的组成
| 胶料 | BIIR A | BIIR B | BIIR C | BIIR D | BIIR E | BIIR F | BIIRG | 炭黑 | 矿物油 | 树脂 | 硬脂酸 | MBTS | 氧化锌 | 硫磺 |
| M(A) | 100 | 60 | 7 | 4 | 1 | 1.3 | 3 | 0.5 | ||||||
| M(B) | 100 | 60 | 7 | 4 | 1 | 1.3 | 3 | 0.5 | ||||||
| M(C) | 100 | 60 | 7 | 4 | 1 | 1.3 | 3 | 0.5 | ||||||
| M(D) | 100 | 60 | 7 | 4 | 1 | 1.3 | 3 | 0.5 |
| M(E) | 100 | 60 | 7 | 4 | 1 | 1.3 | 3 | 0.5 | ||||||
| M(F) | 100 | 60 | 7 | 4 | 1 | 1.3 | 3 | 0.5 |
| M(G) | 100 | 60 | 7 | 4 | 1 | 1.3 | 3 | 0.5 |
表3：硫化橡胶材料的物理性能
| 化合物的性能 | 硫化橡胶材料的物理性能 | ||||||||
| 流变仪测定 | 50％模量，Mpa | 撕裂生长速率1/c(dc/dn)，应变为20％时的Mc-1；T＝70℃ | 对外胎的粘合力，kN/m；65℃ | 对气体(空气)的渗透率，m2/spa；65℃ | |||||
| 焦烧时间ts1，分钟 | 硫化时间t90，分钟 | 最大扭矩，dNm | 未老化 | 于120℃老化168小时 | 未老化 | 于120℃老化168小时 | 未老化 | 未老化 | |
| M(A) | 1.83 | 7.05 | 5.18 | 0.8 | 1.2 | 3.23 | 26.15 | 14.08 | 3.0 |
| M(B) | 1.92 | 8.32 | 4.99 | 0.8 | 1.1 | 2.35 | 15.67 | 13.94 | 3.1 |
| M(C) | 2.18 | 9.15 | 4.95 | 0.8 | 1.0 | 1.83 | 5.21 | 11.34 | 3.0 |
| M(D) | 2.22 | 10.8 | 4.89 | 0.8 | 0.9 | 1.25 | 2.98 | 7.44 | 3.1 |
| M(E) | 1.79 | 5.83 | 5.98 | 0.9 | 1.3 | 5.44 | 55.54 | 13.60 | 2.9 |
| M(F) | 2.38 | 11.77 | 5.42 | 0.8 | 0.8 | 2.50 | 3.34 | 4.19 | 3.0 |
| M(G) | 2.35 | 11.53 | 5.68 | 0.8 | 1.0 | 2.42 | 10.74 | 5.9 | 3.0 |
Claims (7)
1.卤化丁基橡胶，其特征在于，相对于卤化丁基橡胶的总量计，其卤素含量为0.5-2.5％并且未卤化双键的残余含量大于0.7％摩尔，其抗附聚/硫化控制剂的含量为1.0-2.2％重量，其中所述的卤化丁基橡胶是根据如下方法制备的：在气相中或者在有机溶剂的存在下，用卤化剂处理抗附聚/硫化控制剂的含量为所用的丁基橡胶总量的1.0-2.2％重量的丁基橡胶，直至丁基橡胶的卤素含量为0.5-2.5％重量并且未卤化双键含量大于0.7％摩尔。
2.权利要求1的卤化丁基橡胶在生产硫化橡胶材料中的用途。
3.权利要求1的卤化丁基橡胶在生产轮胎中的用途。
4.权利要求1的卤化丁基橡胶在生产轮胎内衬中的用途。
5.权利要求1的卤化丁基橡胶在生产轮胎侧壁中的用途。
6.权利要求1的卤化丁基橡胶在生产轮胎胎面中的用途。
7.权利要求1的卤化丁基橡胶在生产药学上使用的橡胶制品中的用途。
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| US08/841,070 US5886106A (en) | 1996-08-06 | 1997-04-29 | Halogenated butyl rubbers having a low halogen content |
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| US6710116B1 (en) | 2000-10-18 | 2004-03-23 | Exxonmobil Chemical Patents Inc. | Abrasion resistant transparent and colorable elastomeric compositions |
| CA2315830A1 (en) * | 2000-07-27 | 2002-01-27 | Bayer Inc. | Butylpolymer composition having improved cold flow properties |
| US7425591B2 (en) | 2001-10-16 | 2008-09-16 | Exxonmobil Chemical Patents Inc | Elastomeric composition |
| US6705327B2 (en) | 2000-12-06 | 2004-03-16 | Jan Beaver Tilson | Method and system to polish and protect natural nails |
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| US6672350B2 (en) | 2001-09-06 | 2004-01-06 | The Goodyear Tire & Rubber Company | Tire with shock absorbing configured rubber tread |
| US6939921B2 (en) | 2001-10-16 | 2005-09-06 | Exxonmobil Chemical Patents Inc. | Colorable elastomeric composition |
| CN100455605C (zh) * | 2001-12-10 | 2009-01-28 | 埃克森美孚化学专利公司 | 卤化异烯烃类三元共聚物 |
| CN1602320B (zh) * | 2001-12-10 | 2011-06-15 | 埃克森美孚化学专利公司 | 弹性体组合物 |
| US7329697B2 (en) | 2001-12-10 | 2008-02-12 | Exxonmobil Chemical Patents Inc. | Elastomeric compositions |
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| CN100443506C (zh) * | 2006-12-20 | 2008-12-17 | 福州大学 | 低酸值溶剂法氯化天然橡胶制备方法 |
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| EP2527373A1 (en) * | 2011-05-26 | 2012-11-28 | LANXESS International S.A. | Process and apparatus for production of halogenated butyl rubber with reduced emissions |
| RU2706122C2 (ru) * | 2013-12-23 | 2019-11-14 | Арланксео Сингапур Пте. Лтд. | Каучуки с регулируемым содержанием металлсодержащих антиагломерантов |
| JP6328773B2 (ja) * | 2013-12-23 | 2018-05-23 | アランセオ・シンガポール・プライヴェート・リミテッド | 高純度ハロゲン化ゴム |
| SG10201803709WA (en) | 2013-12-23 | 2018-06-28 | Arlanxeo Singapore Pte Ltd | NOVEL ANTI-AGGLOMERANTS FOR ELASTOMERIC ETHYLENE/α-OLEFIN COPOLYMERS |
| WO2015095959A1 (en) | 2013-12-23 | 2015-07-02 | Lanxess Butyl Pte. Ltd. | Novel anti-agglomerants for the rubber industry |
| RU2554343C1 (ru) * | 2014-04-01 | 2015-06-27 | Публичное Акционерное общество "Нижнекамскнефтехим"(ПАО "Нижнекамскнефтехим") | Способ получения бромбутилкаучука |
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| EP3181596A1 (en) | 2015-12-17 | 2017-06-21 | Lanxess Inc. | Process for epoxidation of unsaturated polymer |
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| EP3181598A1 (en) | 2015-12-17 | 2017-06-21 | Lanxess Inc. | Butyl rubber containing allylic alcohol |
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| SG11202105842XA (en) | 2018-12-27 | 2021-07-29 | Arlanxeo Singapore Pte Ltd | Process for producing chlorinated butyl rubber |
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| EP0823454B1 (de) | 2001-01-10 |
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| BR9704261A (pt) | 1998-09-01 |
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| DE19631731A1 (de) | 1998-02-12 |
| US5886106A (en) | 1999-03-23 |
| JP3709264B2 (ja) | 2005-10-26 |
| JPH1077376A (ja) | 1998-03-24 |
| DE59702887D1 (de) | 2001-02-15 |
| CA2204051C (en) | 2005-02-01 |
| CA2204051A1 (en) | 1998-02-06 |
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