CN1050853C - 脂肪族聚碳酸酯丁苯橡胶的改性方法 - Google Patents
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Abstract
本发明属于丁苯橡胶的改性方法。
现有技术是用高聚苯乙烯树脂改性丁苯橡胶，本发明提供一种采用脂肪族聚碳酸酯改良丁苯橡胶的方法。所得改性弹性体与原纯弹性体比较具有良好的力学性能，拉伸强度提高3倍以上，耐热空气老化性能也大幅提高。成本与纯丁苯橡胶相近，而且工艺简单，又能利用大气中丰富的二氧化碳资源，缓解化工原料的短缺状况，同时对于降低大气中二氧化碳的含量，缓解全球性的温室效应，保护生态环境具有积极的意义。
Description
本发明属于丁苯橡胶改性。
一般纯丁苯橡胶力学性能较差，而有效的补强填充剂为碳黑，由于颜色较深，限制了制品的用途。为了制造浅色制品一般可以加入二氧化硅、陶土等，但补强效果不大，加入过多二氧化硅和陶土又会影响制品的物理性能。曾有人采用其它聚合物与丁苯橡胶并用对其补强，例如用短丝纤维补强SBR(D.K.Setua，《K.G.K.》，1984，Vo137)，并用体系的拉伸强度提高，但不理想，而且硬度大，伸长率低(30％)；用聚乙烯改性SBR(朱玉俊等，《特种橡胶制品》，1985，Vo16)，并用体系拉伸强度提高，但所得并用弹性体永久变形大，断裂伸长率较低，而且加工温度高，工艺复杂。还有采用高苯乙烯树脂改性SBR(什瓦尔茨等，《橡胶与塑料及合成树脂的并用》，石油工业出版社，1976)所得弹性体力学性能尚可，但是并用弹性体硬度高，永久变形大，加工温度也较高，而且高苯乙烯树脂价格昂贵，成本无法过关。
本发明的目的在于采用廉价的脂肪族聚碳酸酯改性丁苯橡胶。该脂肪族聚碳酸酯系由二氧化碳共聚合成。使用脂肪族聚碳酸酯还可以改善弹性体的物理机械性能和耐热老化性能。
本发明通过下述步骤实现：在100份(重量)丁苯橡胶中加入脂肪族聚碳酸酯1～100份，主交联剂0.2～50份，促进剂0.1～50份，辅助交联剂0.1～80份和活性剂0.1～20份，在90℃～200℃下加压硫化2-200分钟。所用脂肪族聚碳酸酯分子量为2000～300000，分子链含端羟基的饱和树脂，所用的主交联剂是硫磺或过氧化物，如过氧化苯甲酰，特丁基过氧化苯甲酰，过氧化二异丙苯，二特丁基过氧化物，1，1-特丁基过氧-3，3，5三甲基环己烷等，所用促进剂为次磺酰胺类，秋兰姆类，二烷基二硫代氨基甲酸盐类，噻唑类和胍类促进剂，如N-环己基-2-苯并噻唑次磺酰胺(CZ)，二硫化二苯并噻唑(DM)，二硫醇基苯并噻唑(M)，二硫化四甲基秋兰姆(TMTD)，乙基苯基二硫代氨基甲酸锌(PX)，二苯胍(D)等。所用辅助交联剂是酸酐或异氰酸酯类，如丁二酸酐，顺丁烯二酸酐，四氢邻苯二甲酸酐，六氢邻苯二甲酸酐，三烯丙基异氰酸酯等，所用活性剂是金属氧化物和脂肪酸，如氧化锌和硬脂酸。本发明实施的特点是可以直接将脂肪族聚碳酸酯加到丁苯橡胶中，加工过程在常温下进行，不需要特殊加工设备。弹性体在交联剂以及物理缠结作用下，形成网状交联。交联助剂则通过与羟基反应，进一步改善交联网络的结构，从而提高弹性体的力学性能和耐热性能。
本发明提供的丁苯橡胶改性方法不但提供具有优异的耐热性能和力学性能的改性丁苯橡胶，而且本改性方法加工工艺简单，所采用的脂肪族聚碳酸酯是由二氧化碳共聚合成，改良后产品成本与纯丁苯橡胶相近。该脂肪族聚碳酸酯的广泛应用不仅可以开辟新资源，缓解化工原料的短缺状况，而且对于控制大气中二氧化碳的含量，缓解全球性的温室效应，保护生态环境具有重大意义。
实例1
将100克丁苯橡胶(苯乙烯含量23.5％)与脂肪族聚碳酸酯(分子量100000)10克用双辊混炼机混合均匀，混合温度40℃～50℃，时间5分钟，然后加入氧化锌3克，硬脂酸1克，促进剂CZ1.2克，硫磺1.8克，顺丁烯二酸酐4克，充分混合后放入模具中加压硫化，压力15MPa，温度150℃，时间30分钟。所得改性弹性体拉伸强度9.3MPa，断裂伸长率1321％，扯断永久变形52.8％，硬度32度(邵A)。70℃热空气老化24hr后拉伸强度10.8MPa，断裂伸长率870％，扯断永久变形14.4％。硬度35度(邵A)。实例2
将100克丁苯橡胶(苯乙烯含量23.5％)与脂肪族聚碳酸酯(分子量17000)20克用双辊混炼机混合均匀，混合温度40℃～50℃，时间5分钟，然后加入氧化锌3克，硬脂酸1克，促进剂DM1.0克，促进剂D0.7克，硫磺1.8克，过氧化物DCP1.5克，充分混合后放入模具中加压硫化，压力15MPa，温度150℃，时间20分钟。所得丁苯橡胶弹性体拉伸强度6.5MPa，断裂伸长率902％，硬度39度(邵A)，扯断永久变形24.8％。70℃热空气老化24hr后拉伸强度10.2MPa，断裂伸长率791％，扯断永久变形5％。硬度40度(邵A)。
Claims (6)
1、一种用脂肪族聚碳酸酯改性丁苯橡胶的方法，其特征在于100份(重量)丁苯橡胶中加入脂肪族聚碳酸酯1～100份，硫磺或过氧化物为主交联剂0.2～50份，促进剂次磺酰胺类，或秋兰姆类，或二烷基二硫代氨基甲酸盐类，或噻唑类，或胍类0.1～50份，以及辅助交联剂酸酐或异氰酸酯类0.1～80份，活性剂金属氧化物和脂肪酸0.1～20份，在90℃～200℃下加压硫化2～200分钟。
2、根据权利要求1中所述的改性方法，其特征在于所述的脂肪族聚碳酸酯是分子量为2000～300000的分子链含端羟基的饱和树脂。
3、根据权利要求1中所述的改性方法，其特征在于所述的主交联剂是硫磺，过氧化苯甲酰，特丁基过氧化苯甲酰，过氧化二异丙苯，二特丁基过氧化物，1，1-特丁基过氧-3，3，5三甲基环己烷。
4、根据权利要求1中所述的改性方法，其特征在于所述的促进剂是N-环己基-2-苯并噻唑次磺酰胺，二硫化二苯并噻唑，二硫醇基苯并噻唑，二硫化四甲基秋兰姆，乙基苯基二硫代氨基甲酸锌，二苯胍。
5、根据权利要求1中所述的改性方法，其特征在于所述的辅助交联剂是丁二酸酐，或顺丁烯二酸酐，或四氢邻苯二甲酸酐，或六氢邻苯二甲酸酐，三烯丙基异氰酸酯，
6、根据权利要求1中所述的改性方法，其特征在于所述的活性剂是氧化锌和硬脂酸。
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| CN103881078B (zh) | 2014-04-17 | 2016-02-03 | 中国科学院长春应用化学研究所 | 氯化聚丙撑碳酸酯及其制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5817153A (ja) * | 1981-07-24 | 1983-02-01 | Idemitsu Petrochem Co Ltd | ポリカ−ボネ−ト樹脂組成物 |
| US4444949A (en) * | 1981-02-26 | 1984-04-24 | General Electric Company | Composition of a polycarbonate, a butadiene-styrene copolymer and a (meth)acrylate interpolymer |
| CA1266340A (en) * | 1986-09-16 | 1990-02-27 | Hajime Sakano | Thermoplastic resin composition |
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| US4444949A (en) * | 1981-02-26 | 1984-04-24 | General Electric Company | Composition of a polycarbonate, a butadiene-styrene copolymer and a (meth)acrylate interpolymer |
| JPS5817153A (ja) * | 1981-07-24 | 1983-02-01 | Idemitsu Petrochem Co Ltd | ポリカ−ボネ−ト樹脂組成物 |
| CA1266340A (en) * | 1986-09-16 | 1990-02-27 | Hajime Sakano | Thermoplastic resin composition |
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