WO2017201852A1 - 一种高性能轮胎用溶聚丁苯橡胶-聚氨酯弹性体材料及制备方法 - Google Patents

一种高性能轮胎用溶聚丁苯橡胶-聚氨酯弹性体材料及制备方法 Download PDF

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WO2017201852A1
WO2017201852A1 PCT/CN2016/090795 CN2016090795W WO2017201852A1 WO 2017201852 A1 WO2017201852 A1 WO 2017201852A1 CN 2016090795 W CN2016090795 W CN 2016090795W WO 2017201852 A1 WO2017201852 A1 WO 2017201852A1
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butadiene rubber
polymerized styrene
solution
polyurethane elastomer
soft segment
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French (fr)
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张立群
秦璇
韩丙勇
毛立新
吴晓辉
刘军
张宁
董栋
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北京化工大学
彤程新材料集团股份有限公司
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Priority to JP2019514157A priority Critical patent/JP6692988B2/ja
Priority to EP16902839.6A priority patent/EP3467000B1/en
Priority to KR1020187033816A priority patent/KR102132550B1/ko
Publication of WO2017201852A1 publication Critical patent/WO2017201852A1/zh
Priority to US16/197,073 priority patent/US10717854B2/en

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Abstract

本发明公开了一种高性能轮胎用溶聚丁苯橡胶-聚氨酯弹性体材料及制备方法。弹性体材料是由以下物质浇注成型而得：软段和硬段，二者的质量比为100:(20-50)；所述软段为采用阴离子聚合制备的羟基封端溶聚丁苯橡胶；所述硬段包括异氰酸酯、小分子多元醇扩链剂、交联剂；软段分子量为1000-8000；软段玻璃化转变温度为-20～-30℃。本发明的弹性体材料在传统聚氨酯弹性体合成的基础上，引入羟基封端的溶聚丁苯橡胶作为软段，调节了聚氨酯弹性体的玻璃化转变温度，克服了现有聚氨酯轮胎耐高温性差、抗湿滑抓着能力不尽如人意等缺点，综合使用性能优异。

Description

一种高性能轮胎用溶聚丁苯橡胶-聚氨酯弹性体材料及制备方法 技术领域
本发明涉及高分子合成领域，进一步地说，是涉及一种高性能轮胎用溶聚丁苯橡胶-聚氨酯弹性体材料及制备方法。
背景技术
轮胎工业是既具有悠久历史而又谱写着现代文明的产业。自l855年充气轮胎发明以来，经过数次技术上和理论上的重大变革，如今轮胎制造技术日臻完善，其制品广泛应用于交通运输等诸多领域。汽车工业和高速公路的飞速发展使轮胎成为产量最大、技术水平最高的高分子制品之一。然而，日趋严重的能源消耗、安全事故的增加以及因使用寿命短而产生大量的轮胎固体废弃物等社会发展和环境问题，对轮胎提出了更高的技术要求。轮胎的能耗与滚动阻力相关，安全性与抗湿滑性能相关，使用寿命与磨耗性能相关，这三者成为“魔鬼三角”，在现有材料和工艺条件下无法达到三者的平衡，因此必须开发新的材料。
不同于高结晶度或玻璃化温度较高的塑料，橡胶材料的自由体积大、分子间作用力小、玻璃化转变温度低和具有无定形的高弹态，因此绝大多数的橡胶不经过填料增强是无法应用的。炭黑作为传统的增强填料已经有100多年的应用历史，由于具有原生的纳米尺寸，炭黑能够明显的提高橡胶材料的物理机械性能、耐磨耗性能和耐疲劳性能，但是炭黑与橡胶间以强物理作用为主，虽然纳米增强效果好、轮胎耐磨性高，但是炭黑颗粒与橡胶分子间有摩擦，炭黑颗粒与颗粒间也有摩擦，因此材料的动态损耗大、生热高，轮胎油耗大。白炭黑由于能够用于制备“绿色轮胎”而被熟知，这是由于白炭黑表面存在大量硅羟基， 表面化学改性效果好，能够与橡胶形成较强的化学键，制备的轮胎滚动阻力明显降低，但是白炭黑的纳米粒子尺寸较小，聚集体的视密度较低，加之橡胶的黏度较高，因而不易被混入，易飞扬，混炼加工能耗高；同时，白炭黑硅羟基的有机改性必须经过高温(140-160℃)混炼一定的时间，温度太低起不到改性效果，温度太高橡胶高分子链可能热降解，因此此过程对加工设备的性能参数要求非常高，加工成本高，并且白炭黑制备的轮胎的耐磨耗性能较差，基于以上原因，限制了其大规模地应用。
聚氨酯弹性体材料与传统橡胶材料相比，具有更优异的耐磨性能、较高的抗撕裂强度和伸长率、硬度范围宽、滚动阻力低、负重容量非常大、以及它的吸振和减震效果好等特点，特别是浇注型聚氨酯弹性体是目前最耐磨的弹性体，具有高耐磨、可着色、高耐切割性、优良的耐油及耐化学品等优点，无需添加炭黑和芳烃油，成为制造高性能轮胎的理想材料。由聚氨酯材料制作的轮胎工艺简单、安全、耐用、环保，废旧轮胎可循环使用或用于制造其他工业产品，成本大大低于传统的橡胶轮胎，因此受到广大消费者的青睐，成为业内关注的焦点。
但是，目前聚氨酯轮胎的生产尚存在需要解决的技术难题，如耐高温性较差、抗湿滑抓着能力不尽如人意等。
发明内容
为解决现有技术中出现的问题，本发明提供了一种高性能轮胎用溶聚丁苯橡胶-聚氨酯弹性体材料及制备方法。本发明的弹性体材料在传统聚氨酯弹性体合成的基础上，引入羟基封端的溶聚丁苯橡胶作为软段，在保持聚氨酯弹性体材料本身环境友好、高耐磨、耐油、耐化学品、低滚动阻力优点的基础上，结合溶聚丁苯橡胶优良的耐屈挠性和优异的动态力学性能，调节了聚氨酯弹性体的玻璃化转变温度，克服了现有聚氨酯轮胎耐高温性差、抗湿滑抓着能力不尽如人意等缺点，综合使用性能优异，采用本发明所述的聚氨酯材料制备轮胎在 未来轮胎行业中势必有更加广阔的发展空间。
本发明的目的之一是提供一种高性能轮胎用溶聚丁苯橡胶-聚氨酯弹性体材料。
所述聚氨酯弹性体材料是由以下物质浇注成型而得：
软段和硬段，二者的质量比为100:(20-50)；优选100:(30-45)；
所述软段为采用阴离子聚合制备的羟基封端溶聚丁苯橡胶；
所述硬段包括异氰酸酯、小分子多元醇扩链剂、交联剂；
所述异氰酸酯为4,4-二苯基甲烷二异氰酸酯或1,5-萘二异氰酸酯或甲苯-2,4-二异氰酸酯；优选1,5-萘二异氰酸酯；
所述小分子多元醇扩链剂为1,4-丁二醇或乙二醇；优选1,4-丁二醇；
所述交联剂为三羟甲基丙烷或丙三醇；
软段与异氰酸酯的质量比为100：(15-45)；
(软段+异氰酸酯)与(扩链剂+交联剂)的质量比为100:(4-12)；
扩链剂和交联剂的质量比为：100：(15-50)；
所述软段分子量为1000-8000；优选4500-6500；
所述软段玻璃化转变温度为-20～-30℃。
所述溶聚丁苯橡胶-聚氨酯弹性体的玻璃化转变温度为-20～-30℃。
所述软段是由包括以下步骤的方法制备：
(1)双锂引发剂的制备：环己烷和四氢呋喃做溶剂，异戊二烯和金属锂在冰水浴条件下反应生成双锂引发剂；
(2)环氧乙烷蒸馏提纯；
(3)丁二烯、苯乙烯、双锂引发剂进行合成反应，反应温度为45-55℃，反应时间为3.5-4.5h，釜降至室温，加入环氧乙烷做封端剂，反应时间12-14h；制得羟基封端溶聚丁苯橡胶；
丁二烯：苯乙烯质量比＝100:(25-35)；
环氧乙烷与活性锂的质量比为100:(10-20)；
活性锂：(丁二烯+苯乙烯)的质量比为1：(90～790)。
双锂引发剂的浓度优选为0.5-1.0mol/L。
本发明的目的之二是提供一种高性能轮胎用溶聚丁苯橡胶-聚氨酯弹性体材料的制备方法。
包括：
a.预聚体的制备：将羟基封端溶聚丁苯橡胶在90-100℃、真空条件下搅拌2-3h，降温至80-90℃，加入异氰酸酯，反应2.5-3h，降温至65-75℃，取样，检测—NCO的质量含量，若—NCO的质量含量<5％-11％，则补加异氰酸酯，当—NCO的质量含量达到5％-11％时，出料；
b.溶聚丁苯橡胶-聚氨酯弹性体的制备：将预聚体在80-90℃、真空条件下搅拌2-3h，降温至65-75℃，加入小分子多元醇扩链剂、交联剂，高速搅拌2-3min，浇注成型后制得所述聚氨酯弹性体材料。
其中，优选：
所述搅拌速率150-250rad/min,高速搅拌速率400-600rad/min；
小分子多元醇扩链剂、交联剂的滴加速率为1-2s/滴。
本发明具体可采用以下技术方案：
1)双锂引发剂的制备：可采用现有技术的制备方法，选用环己烷和四氢呋喃配合做溶剂，异戊二烯和金属锂在冰水浴条件下反应生成双锂引发剂。可优选引发剂浓度0.5-1.0mol/L，四氢呋喃与活性锂的质量比100：(5-8)，四氢呋喃与环己烷体积比1:1左右，活性锂与异戊二烯物质的量100：(10-30)；为保证金属锂与异戊二烯完全反应，加入锂的量为理论值的5倍；
环己烷和四氢呋喃体积比1：1。将剥去氧化层的锂薄片和四氢呋喃加入三口瓶中，氩气保护，置于冰水浴，保证温度稳定在0℃左右。将异戊二烯和环己烷混合均匀，加入到恒压滴定漏斗中，逐滴缓慢加入至三口瓶，与金属锂充分反应。滴加完成后，在0℃下继续搅拌6-8h。反应完成后，低温静置22-26h。采用G4砂芯漏斗过滤上层澄清反应液，得到棕红色透明引发剂溶液。使用前， 采用双滴定法对引发剂浓度进行标定。
2)环氧乙烷的蒸馏：环氧乙烷作为封端剂，其中含有的杂质、水等会使活性锂离子失去活性，造成链终止，影响活性链末端改性。为提高纯度，将适量氢化钙研磨成粉末，加入环氧乙烷中浸泡24-26h，氮气气氛下常温将环氧乙烷蒸出。
3)羟基封端溶聚丁苯橡胶的制备：将反应釜升温至45-55℃，环己烷洗釜1.5-2.5h。丁二烯：苯乙烯质量比＝100:25-35，单体质量分数10％，丁苯胶合成时反应温度50℃，反应时间3.5-4.5h。使釜降至室温，加入环氧乙烷做封端剂，环氧乙烷与活性锂质量比为100:20，反应时间12-14h。氮气气氛下接出胶液，加入适量盐酸，常温搅拌4-6h，采用无水乙醇沉淀，得到羟基封端溶聚丁苯橡胶，密封保存。
4)预聚体的制备：将羟基封端溶聚丁苯橡胶在90-100℃、真空条件下搅拌2.5h，降温至80-90℃，加入异氰酸酯，反应2.5-3h，降温至65-75℃，取样，根据标准ASTM D2572-97检测—NCO的质量含量，若—NCO的质量含量<5％-11％，则补加异氰酸酯，当—NCO的质量含量达到5％-11％时，出料，密封保存。
5)溶聚丁苯橡胶-聚氨酯弹性体的制备：将预聚体在80-90℃、真空条件下搅拌2h，降温至65-75℃，加入小分子多元醇扩链剂、交联剂，高速搅拌2-3min，浇注成型，放入100℃烘箱固化20h，脱模后，常温放置7d。
作为优选，步骤3)中所述丁二烯：苯乙烯质量比＝100:30。
作为优选，步骤4)中所述搅拌速率200rad/min。
作为优选，步骤5)中所述搅拌速率200rad/min,高速搅拌速率500rad/min，小分子多元醇扩链剂、交联剂的滴加速率为1-2s/滴。
聚氨酯弹性体的玻璃化转变温度对其动态力学性能影响很大。聚氨酯弹性的玻璃化转变温度与软段玻璃化转变温度的关系非常大，本发明通过调整苯乙烯与1,2-丁二烯的含量来调整软段的玻璃化转变温度。因此，本发明中所制备 的溶聚丁苯橡胶-聚氨酯弹性体玻璃化转变温度为-20～-30℃，并对其进行动态力学性能测试，在较低温度(0℃左右)下其具有较高损耗因子(tanδ)，这一特点可改善制品的抗湿滑性能，达到绿色轮胎的使用标准。
本发明的有益效果如下：
1)本发明在传统聚氨酯弹性体合成的基础上，引入羟基封端的溶聚丁苯橡胶作为软段，在保持聚氨酯弹性体材料本身环境友好、高耐磨、耐油、耐化学品、低滚动阻力优点的基础上，结合溶聚丁苯橡胶优良的耐屈挠性和优异的动态力学性能，调整了聚氨酯弹性体的玻璃化转变温度，提高综合使用性能。
2)采用本发明所述的聚氨酯弹性体材料制备轮胎将克服现有聚氨酯轮胎耐高温性较差、抗湿滑抓着能力不尽如人意等缺点，为在可预见的未来实施工业应用奠定了基础。
附图说明
图1是实施例2的红外光谱图；
图2是实施例2的SEM图；
图3是实施例2的DMA图；
图4是对比例1的DMA图。
具体实施方式
下面结合实施例，进一步说明本发明。
实施例中所用原料均为市售；
玻璃化转变温度的测量采用瑞士METTLER TOLEDO公司的差示扫描量热仪进行测试。
实施例1
本实施例聚氨酯弹性体的制备过程如下：
1)双锂引发剂的制备：选用环己烷和四氢呋喃配合做溶剂，异戊二烯和 金属锂在冰水浴条件下反应生成双锂引发剂。取70g剥去氧化层的锂薄片与500ml四氢呋喃加入三口瓶中，氩气保护，置于冰水浴，保证温度稳定在0℃左右。将200ml异戊二烯与500ml环己烷混合均匀，加入到恒压滴定漏斗中，逐滴缓慢加入至三口瓶，与金属锂充分反应。滴加完成后，在0℃下继续搅拌6h。反应完成后，低温静置24h。采用G4砂芯漏斗过滤上层澄清反应液，得到棕红色透明引发剂溶液。使用前，采用双滴定法对引发剂浓度进行标定。双锂引发剂的浓度是0.8mol/L。
2)环氧乙烷的蒸馏：取10g氢化钙研磨成粉末，加入100ml环氧乙烷中浸泡24h，氮气气氛下常温将环氧乙烷蒸出。
3)羟基封端溶聚丁苯橡胶的制备：将反应釜升温至50℃，环己烷洗釜2h。丁二烯：苯乙烯质量比＝100:25，单体质量分数10％。活性锂：(丁二烯+苯乙烯)的质量比为1：280。丁苯胶合成时反应温度50℃，反应时间4h。使釜降至室温，加入环氧乙烷做封端剂，环氧乙烷与活性锂的质量比为100:18，反应时间12h。氮气气氛下接出胶液，加入适量盐酸，常温搅拌4h，采用无水乙醇沉淀，得到羟基封端溶聚丁苯橡胶(分子量3000，玻璃化转变温度-25.9℃)，密封保存。
4)预聚体的制备：取16g羟基封端溶聚丁苯橡胶在95℃、真空条件下搅拌(搅拌速率150rad/min)2.5h，降温至80℃，加入4.35g 4,4-二苯基甲烷二异氰酸酯(MDI)，反应3h，降温至65℃，取样，根据标准ASTM D2572-97检测—NCO的质量含量，当—NCO的质量含量达到7％时，出料，密封保存。
5)溶聚丁苯橡胶-聚氨酯弹性体的制备：取20.3g预聚体在80℃、真空条件下搅拌(搅拌速率150rad/min)2h，降温至65℃，加入0.92g 1,4-丁二醇(BDO)和0.16g三羟甲基丙烷(TMP)(滴加速率为1s/滴)，高速搅拌(搅拌速率400rad/min)3min，浇注成型，放入100℃烘箱固化20h，脱模后，常温放置7d。
实施例2
本实施例聚氨酯弹性体的制备过程如下：
1)双锂引发剂的制备：选用环己烷和四氢呋喃配合做溶剂，异戊二烯和金属锂在冰水浴条件下反应生成双锂引发剂。取60g剥去氧化层的锂薄片与500ml四氢呋喃加入三口瓶中，氩气保护，置于冰水浴，保证温度稳定在0℃左右。将200ml异戊二烯与500ml环己烷混合均匀，加入到恒压滴定漏斗中，逐滴缓慢加入至三口瓶，与金属锂充分反应。滴加完成后，在0℃下继续搅拌6h。反应完成后，低温静置24h。采用G4砂芯漏斗过滤上层澄清反应液，得到棕红色透明引发剂溶液。使用前，采用双滴定法对引发剂浓度进行标定。双锂引发剂浓度为0.8mol/L.
2)环氧乙烷的蒸馏：取10g氢化钙研磨成粉末，加入100ml环氧乙烷中浸泡24h，氮气气氛下常温将环氧乙烷蒸出。
3)羟基封端溶聚丁苯橡胶的制备：将反应釜升温至50℃，环己烷洗釜2h。丁二烯：苯乙烯质量比＝100:25，单体质量分数10％，活性锂：(丁二烯+苯乙烯)的质量比为1：430。丁苯胶合成时反应温度50℃，反应时间4h。使釜降至室温，加入环氧乙烷做封端剂，环氧乙烷与活性锂质量比为100:20，反应时间12h。氮气气氛下接出胶液，加入适量盐酸，常温搅拌4h，采用无水乙醇沉淀，得到羟基封端溶聚丁苯橡胶(分子量4500，玻璃化转变温度-28.5℃)，密封保存。
4)预聚体的制备：取16g羟基封端溶聚丁苯橡胶在95℃、真空条件下搅拌(搅拌速率200rad/min)2.5h，降温至90℃，加入4.58g 1，5-萘二异氰酸酯(NDI)，反应3h，降温至65℃，取样，根据标准ASTM D2572-97检测—NCO的质量含量，当—NCO的质量含量达到7％时，出料，密封保存。
5)溶聚丁苯橡胶-聚氨酯弹性体的制备：取20.5g预聚体在90℃、真空条件下搅拌(搅拌速率200rad/min)2h，降温至65℃，加入0.95g 1,4-丁二醇(BDO)和0.95g三羟甲基丙烷(TMP)(滴加速率为2s/滴)，高速搅拌(搅拌速率500rad/min)2min，浇注成型，放入100℃烘箱固化20h，脱模后，常温放置7d。
实施例3
本实施例聚氨酯弹性体的制备过程如下：
1)双锂引发剂的制备：选用环己烷和四氢呋喃配合做溶剂，异戊二烯和金属锂在冰水浴条件下反应生成双锂引发剂。取90g剥去氧化层的锂薄片与500ml四氢呋喃加入三口瓶中，氩气保护，置于冰水浴，保证温度稳定在0℃左右。将200ml异戊二烯与500ml环己烷混合均匀，加入到恒压滴定漏斗中，逐滴缓慢加入至三口瓶，与金属锂充分反应。滴加完成后，在0℃下继续搅拌6h。反应完成后，低温静置24h。采用G4砂芯漏斗过滤上层澄清反应液，得到棕红色透明引发剂溶液。使用前，采用双滴定法对引发剂浓度进行标定。双锂引发剂的浓度为0.8mol/L。
2)环氧乙烷的蒸馏：取10g氢化钙研磨成粉末，加入100ml环氧乙烷中浸泡24h，氮气气氛下常温将环氧乙烷蒸出。
3)羟基封端溶聚丁苯橡胶的制备：将反应釜升温至45℃，环己烷洗釜2h。丁二烯：苯乙烯质量比＝100:30，单体质量分数10％，活性锂：(丁二烯+苯乙烯)的质量比为1：90。丁苯胶合成时反应温度45℃，反应时间4h。使釜降至室温，加入环氧乙烷做封端剂，环氧乙烷与活性锂物质的量100:12，反应时间12h。氮气气氛下接出胶液，加入适量盐酸，常温搅拌4h，采用无水乙醇沉淀，得到羟基封端溶聚丁苯橡胶(分子量1000，玻璃化转变温度-28.1℃)，密封保存。
4)预聚体的制备：取15g羟基封端溶聚丁苯橡胶在95℃、真空条件下搅拌(搅拌速率200rad/min)2h，降温至90℃，加入5.7g 1，5-萘二异氰酸酯(NDI)，反应3h，降温至65℃，取样，根据标准ASTM D2572-97检测—NCO的质量含量，当—NCO的质量含量达到5％时，出料，密封保存。
5)溶聚丁苯橡胶-聚氨酯弹性体的制备：取20g预聚体在90℃、真空条件下搅拌(搅拌速率200rad/min)2h，降温至65℃，加入1.16g 1,4-丁二醇(BDO)和0.2g三羟甲基丙烷(TMP)(滴加速率为2s/滴)，高速搅拌(搅拌速率600 rad/min)2min，浇注成型，放入100℃烘箱固化20h，脱模后，常温放置7d。
实施例4
本实施例聚氨酯弹性体的制备过程如下：
1)双锂引发剂的制备：选用环己烷和四氢呋喃配合做溶剂，异戊二烯和金属锂在冰水浴条件下反应生成双锂引发剂。取55g剥去氧化层的锂薄片与500ml四氢呋喃加入三口瓶中，氩气保护，置于冰水浴，保证温度稳定在0℃左右。将200ml异戊二烯与500ml环己烷混合均匀，加入到恒压滴定漏斗中，逐滴缓慢加入至三口瓶，与金属锂充分反应。滴加完成后，在0℃下继续搅拌6h。反应完成后，低温静置24h。采用G4砂芯漏斗过滤上层澄清反应液，得到棕红色透明引发剂溶液。使用前，采用双滴定法对引发剂浓度进行标定。双锂引发剂的浓度为0.8mol/L。
2)环氧乙烷的蒸馏：取10g氢化钙研磨成粉末，加入100ml环氧乙烷中浸泡24h，氮气气氛下常温将环氧乙烷蒸出。
3)羟基封端溶聚丁苯橡胶的制备：将反应釜升温至50℃，环己烷洗釜2h。丁二烯：苯乙烯质量比＝100:35，单体质量分数10％，活性锂：(丁二烯+苯乙烯)的质量比为1：790。丁苯胶合成时反应温度55℃，反应时间4h。使釜降至室温，加入环氧乙烷做封端剂，环氧乙烷与活性锂质量比100:20，反应时间12h。氮气气氛下接出胶液，加入适量盐酸，常温搅拌4h，采用无水乙醇沉淀，得到羟基封端溶聚丁苯橡胶(分子量8000，玻璃化转变温度-28.3℃)，密封保存。
4)预聚体的制备：取15g羟基封端溶聚丁苯橡胶在95℃、真空条件下搅拌(搅拌速率250rad/min)3h，降温至90℃，加入2.3g 1，5-萘二异氰酸酯(NDI)，反应3h，降温至65℃，取样，根据标准ASTM D2572-97检测—NCO的质量含量，当—NCO的质量含量达到5％时，出料，密封保存。
5)溶聚丁苯橡胶-聚氨酯弹性体的制备：取17.3g预聚体在90℃、真空条件下搅拌(搅拌速率250rad/min)2h，降温至65℃，加入0.7g 1,4-丁二醇(BDO) 和0.13g三羟甲基丙烷(TMP)(滴加速率为2s/滴)，高速搅拌(搅拌速率600rad/min)2min，浇注成型，放入100℃烘箱固化20h，脱模后，常温放置7d。
对比例1
本对比例聚氨酯弹性体的制备过程如下：
1)预聚体的制备：取16g聚四氢呋喃醚二醇(PTMG，分子量2000)在80℃、真空条件下搅拌2.5h，降温至70℃，加入6.6g 4,4-二苯基甲烷二异氰酸酯(MDI)，反应3h，降温至60℃，取样，根据标准ASTM D2572-97检测—NCO的质量含量，若—NCO的质量含量<7％，则补加异氰酸酯，当—NCO的质量含量达到7％时，出料，密封保存。
5)聚氨酯弹性体的制备：取22g预聚体在80℃、真空条件下搅拌2h，降温至60℃，加入2.8g 1,4-丁二醇(BDO)和0.5g三羟甲基丙烷(TMP)，高速搅拌3min，浇注成型，放入100℃烘箱固化20h，脱模后，常温放置7d。
实施例和对比例的数据见表1.
表1
Figure PCTCN2016090795-appb-000001
聚氨酯的热分解一般分两段进行，首先是硬段的分解，之后是软的分解。表1数据表明，与对比例1中传统聚氨酯材料相比，本发明所制备的聚氨酯材料热稳定性明显更优异，热分解起始温度升高14-26℃。拉伸强度提升0.6-3.1MPa。具有可调节的硬度范围，满足不同轮胎的使用条件。
在较低温度(0℃左右)下具有较高损耗因子(tanδ)的聚合物可以改善制品抗湿滑性能,在较高温度下(60℃左右)具有较低tanδ的聚合物可以降低制品滚动阻力。对比附图3和4，传统聚氨酯0℃下tanδ0.1，本发明所制备的聚氨酯0℃下tanδ0.4，明显改善了材料的抗湿滑性能。同时，在100℃下，传统聚氨酯tanδ明显上升，本发明制备的聚氨酯tanδ仍保持在很低的水平，也进一步验证了本发明所制备的聚氨酯耐热性更优异。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定，对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动，这里无法对所有的实施方式予以穷举，凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。

Claims (8)

  1. 一种高性能轮胎用溶聚丁苯橡胶-聚氨酯弹性体材料，其特征在于：所述弹性体材料是由以下物质浇注成型而得：
    软段和硬段，二者的质量比为100:(20-50)；
    所述软段为采用阴离子聚合制备的羟基封端溶聚丁苯橡胶；
    所述硬段包括异氰酸酯、小分子多元醇扩链剂、交联剂；
    所述异氰酸酯为4,4-二苯基甲烷二异氰酸酯或1,5-萘二异氰酸酯或甲苯-2,4-二异氰酸酯；
    所述小分子多元醇扩链剂为1,4-丁二醇或乙二醇；
    所述交联剂为三羟甲基丙烷或丙三醇；
    软段与异氰酸酯的质量比为100：(15-45)；
    (软段+异氰酸酯)与(扩链剂+交联剂)的质量比为100:(4-12)；
    扩链剂和交联剂的质量比为：100：(17-100)；
    所述软段分子量为1000～8000；
    所述软段玻璃化转变温度为-20～-30℃。
  2. 如权利要求1所述的溶聚丁苯橡胶-聚氨酯弹性体材料，其特征在于：
    软段和硬段的质量比为100:(30-45)。
  3. 如权利要求1所述的溶聚丁苯橡胶-聚氨酯弹性体材料，其特征在于：
    所述软段分子量为4500～6500。
  4. 如权利要求1所述的溶聚丁苯橡胶-聚氨酯弹性体材料，其特征在于：
    所述软段是由包括以下步骤的方法制备：
    (1)双锂引发剂的制备：环己烷和四氢呋喃做溶剂，异戊二烯和金属锂在冰水浴条件下反应生成双锂引发剂；
    (2)环氧乙烷蒸馏提纯；
    (3)丁二烯、苯乙烯、双锂引发剂进行合成反应，反应温度为45～55℃， 反应时间为3.5～4.5h，釜降至室温，加入环氧乙烷做封端剂，反应时间12～14h；制得羟基封端溶聚丁苯橡胶；
    丁二烯：苯乙烯质量比＝100:(25-35)；
    环氧乙烷与活性锂的质量比为100:(10-20)；
    活性锂：(丁二烯+苯乙烯)的质量比为1：(90～790)。
  5. 如权利要求4所述的溶聚丁苯橡胶-聚氨酯弹性体材料，其特征在于：
    双锂引发剂的浓度为0.5-1.0mol/L。
  6. 如权利要求1所述的溶聚丁苯橡胶-聚氨酯弹性体材料，其特征在于：
    所述溶聚丁苯橡胶-聚氨酯弹性体的玻璃化转变温度为-20～-30℃。
  7. 一种如权利要求1～6之一所述的溶聚丁苯橡胶-聚氨酯弹性体材料的制备方法，其特征在于所述方法包括：
    a.预聚体的制备：将羟基封端溶聚丁苯橡胶在90-100℃、真空条件下搅拌2-3h，降温至80-90℃，加入异氰酸酯，反应2.5-3h，降温至65-75℃，取样，检测—NCO的质量含量，若—NCO的质量含量<5％-11％，则补加异氰酸酯，当—NCO的质量含量达到5％-11％时，出料；
    b.溶聚丁苯橡胶-聚氨酯弹性体的制备：将预聚体在80-90℃、真空条件下搅拌2-3h，降温至65-75℃，加入小分子多元醇扩链剂、交联剂，高速搅拌2-3min，浇注成型后制得所述聚氨酯弹性体材料。
  8. 如权利要求7所述的溶聚丁苯橡胶-聚氨酯弹性体材料的制备方法，其特征在于：
    所述搅拌速率150-250rad/min,高速搅拌速率400-600rad/min；
    小分子多元醇扩链剂、交联剂的滴加速率为1-2s/滴。
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