CN101508811A - 可注射可硫化苯乙烯系橡胶粒子及制备工艺 - Google Patents

可注射可硫化苯乙烯系橡胶粒子及制备工艺 Download PDF

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CN101508811A
CN101508811A CNA2009100474350A CN200910047435A CN101508811A CN 101508811 A CN101508811 A CN 101508811A CN A2009100474350 A CNA2009100474350 A CN A2009100474350A CN 200910047435 A CN200910047435 A CN 200910047435A CN 101508811 A CN101508811 A CN 101508811A
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styrene
injectable
vulcanizable
rubber particles
vinyl benzene
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叶孙勇
张爱民
梁红文
林昌武
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Priority to CNA2009100474350A priority Critical patent/CN101508811A/zh
Priority to CN2009101502911A priority patent/CN101624461B/zh
Priority to BRPI0924385A priority patent/BRPI0924385A2/pt
Priority to KR1020117021257A priority patent/KR20120001729A/ko
Priority to JP2011553245A priority patent/JP5753497B2/ja
Priority to PCT/CN2009/000850 priority patent/WO2010102432A1/zh
Priority to US13/255,872 priority patent/US20120041130A1/en
Priority to EP09841301.6A priority patent/EP2407509B1/en
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Abstract

本发明涉及一种可注射可硫化苯乙烯系橡胶粒子及制备工艺。其特征在于先将一定配比的苯乙烯－丁二烯共聚物、流动改性剂、再生料、软化油及各种加工助剂加入密炼机混合，然后加入硫化剂，混合好后用开炼机成片；或是先将流动改性剂和软化油加入密炼机混合然后再加入苯乙烯－丁二烯共聚物、再生料和各种加工助剂混合，然后加入硫化剂，混合后用开炼机成片，最后用挤出机挤出造粒，通过风环切粒或水环切粒。本发明的目的使橡胶粒子材料在正常的加工温度条件下，具有良好的流动性能，可以进行后期硫化，可以在室温下长期保存。与现有技术相比，橡胶粒子可直接通过注射成型，橡胶粒子不易自硫化，硫化速度容易控制，不需低温存放等优点。

Description

可注射可硫化苯乙烯系橡胶粒子及制备工艺
技术领域
本发明涉及一种橡胶粒子材料，特别是指一种可注射可硫化的苯乙烯系橡胶粒子及制备工艺，属于橡胶制造技术领域。
技术背景
橡胶是一种重要的高分子弹性体材料，大量应用于各种制品，如轮胎、鞋底、密封圈、及各种防护器材。应用于各种制品的材料要具有良好的耐磨性、耐弯折性能、耐水耐油性、耐热耐寒性能，高弹性、高撕裂强度，同时成本底，加工成型工艺简单稳定。各种橡胶制品主要是通过以下各种橡胶材料并用：天然橡胶、异戊二烯橡胶、丁二烯橡胶、丁苯橡胶、丁腈橡胶、氯丁橡胶、三元乙丙橡胶等。由于各种传统的橡胶材料分子量高，材料流动性差，只能通过模压成型，同时在橡胶硫化过程中，为了改善模温的均匀性，采用蒸汽加热的方式，而这种工艺需要配置复杂昂贵的高压锅炉设备，设备投资大，能耗高。传统橡胶分子量高，分子间缠结严重，导致橡胶在开炼或是密炼过程中大量生热，且热量不易传出，从而使得胶料容易部分硫化，从而导致制模压成型后的制品存在缺陷。同时，采用传统的硫磺硫化的胶料由于环境温度稍高即可发生自硫化，从而不能长期存放，如要长期存放需放置在低温环境中。正因为传统橡胶的的各种缺点，产生了热塑性弹性体，其中最主要的为苯乙烯系弹性体，这类弹性体可注射成型，加工工艺简单，可回收利用，因此得到了充分的发展，但是由于这类弹性体仅仅通过物理交联点来保持力学性能，不能满足某些高性能要求(如高耐磨、高撕裂强度)的制件。同时苯乙烯系热塑性弹性体很难有效的进行化学交联，因为苯乙烯系热塑性弹性体为嵌段共聚物，而各段的交联难易程度不同，导致交联不均匀。
发明内容
为了克服现有橡胶材料及其工艺的各种缺点，本发明提供一种可注射可硫化苯乙烯系橡胶粒子及制备工艺，使橡胶粒子材料在正常的加工温度条件下，具有良好的流动性能，可以直接通过注射成型，可以进行后期硫化，硫化速度容易控制，硫化均匀，并且橡胶粒子材料在常温下或是温度稍高条件下不会发生自硫化，可以在室温下长期保存，不需低温存放。
为了达到上述目的，本发明采用以下技术解决方案：
一种可注射可硫化苯乙烯系橡胶粒子，它按以下质量份配方组成：苯乙烯-丁二烯共聚物40～70份，流动改性剂10～30份，再生料0～30份，软化油10～50份，硫化剂0.1～1份。
所述的苯乙烯-丁二烯共聚物的分子结构为线形结构或多臂星形结构，该聚合物的分子链结构为苯乙烯类单体和二烯烃单体的完全无规共聚结构或为苯乙烯类单体和二烯烃单体的多次嵌段共聚形成的交替微嵌段结构，二烯烃结构中的1，2-结构含量为10～40％；苯乙烯-丁二烯共聚物的分子结构式为-(PSX-PBY)n-或(-(PSX-PBY)n-)MR，前者为线形结构，后者为多臂星形结构，其中PS为苯乙烯类聚合物，PB为二烯烃类聚合物，R为星形结构的“核”，X＝1-300，Y＝1-2000，n＝10-3000，M＝3-20；共聚物中苯乙烯类单体的重量百分含量为5-80％，共聚物的分子量为40000-500000(Mn)。
所述的流动改性剂可选用苯乙烯-丁二烯-苯乙烯共聚物、苯乙烯-乙烯-丁烯-苯乙烯共聚物、苯乙烯-乙烯-丙烯-苯乙烯共聚物中的至少一种。
所述的再生料可选用再生橡胶、PE再生料、EVA再生料、PP再生料中的至少一种。
所述的软化油可选用环烷油、烷烃油、芳烃油中的至少一种。
所述的硫化剂可选用过氧化苯甲酰、双对过氧化苯甲酰、二叔丁基过氧化物、过氧化二异丙苯、过氧化氢异丙苯。
所述的可注射可硫化苯乙烯系橡胶粒子制备工艺，可采用以下三种：
1、首先将一定配比的苯乙烯-丁二烯共聚物、流动改性剂、再生料、软化油同时放入密炼机中密炼，混合10～30分钟，然后加入硫化剂，混合3～10分钟，密炼机温度60～120℃，将密炼后的胶料用开炼机混合，薄通5～20次后下片。最后将胶料用挤出机挤出造粒，挤出机温度为60～110℃，通过风环切粒或是水环切粒。
2、首先将一定配比的流动改性剂、软化油放入密炼机中密炼，混合5～15分钟，然后加入苯乙烯-丁二烯共聚物、再生料，混合5～15分钟，再加入硫化剂，混合3～10分钟，密炼机温度60～120℃，将密炼后的胶料用开炼机混合，薄通5～20次后下片。最后将胶料用挤出机挤出造粒，挤出机温度为60～110℃，通过风环切粒或是水环切粒。
3、首先将一定配比的苯乙烯-丁二烯共聚物、流动改性剂、再生料、软化油同时放入密炼机中密炼，混合10～30分钟，密炼机温度100～160℃，将密炼后的胶料用开炼机成片，加入硫化剂，薄通10～30次后下片。最后将胶料用挤出机挤出造粒，挤出机温度60～110℃，通过风环切粒或是水环切粒。
在制备过程中，可根据不同制件的性能需要，添加各种加工助剂，如硫化促进剂、防老剂、脱模剂、补强剂、阻燃剂、增黏剂、防黏剂。
本发明的有益效果是使用了分子链结构为无规和嵌段混合的苯乙烯-丁二烯共聚物，由于此共聚物分子量较低，使得材料具有较好的流动性能，同时加入部分嵌段结构，能使得低分子量条件下还具有良好的机械性能，微嵌段结构也不会影响硫化的均匀性，微嵌段结构的存在使得材料在加入较少的硫化剂的情况下也能具有良好的力学性能，因此材料的半硫化状态，容易脱硫再生利用。当加入软化油后能进一步提高材料的流动性能，满足了注射工艺的要求。同时，在胶料中添加了再生料，能有效降低成本。同时再生料为半脱硫，与橡胶混合后再生料以微小的橡胶颗粒的形式存在，能对橡胶起到很好的增强增韧的效果。
具体实施方式
下面结合实施例对发明作进一步详细说明。
实施例1
实施例1的可注射可硫化苯乙烯系橡胶粒子，它按以下配比的组分及含量(质量份)进行制备：
苯乙烯-丁二烯共聚物                   70份
苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物     10份
环烷油                               19.9份
过氧化二异丙苯                        0.1份
其中，所述的苯乙烯-丁二烯共聚物的分子结构为线形结构或多臂星形结构，该聚合物的分子链结构为苯乙烯类单体和二烯烃单体的完全无规共聚结构或为苯乙烯类单体和二烯烃单体的多次嵌段共聚形成的交替微嵌段结构，二烯烃结构中的1，2-结构含量为10～40％；苯乙烯-丁二烯共聚物的分子结构式为-(PSX-PBY)n-或(-(PSX-PBY)n-)MR，前者为线形结构，后者为多臂星形结构，其中PS为苯乙烯类聚合物，PB为二烯烃类聚合物，R为星形结构的“核”，X＝1-300，Y＝1-2000，n＝10-3000，M＝3-20；共聚物中苯乙烯类单体的重量百分含量为5-80％，共聚物的分子量为40000-500000(Mn)。
制备时，首先将上述配比的苯乙烯-丁二烯共聚物、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物、环烷油同时放入密炼机中密炼，混合10分钟，然后加入过氧化二异丙苯，混合3分钟，密炼机温度100℃，将密炼后的胶料用开炼机混合，薄通10次后下片。最后将胶料用挤出机挤出造粒，挤出机温度为70℃，通过风环切粒。
实施例2
实施例2的可注射可硫化苯乙烯系橡胶粒子，它按以下配比的组分及含量(质量份)进行制备：
苯乙烯-丁二烯共聚物                    40份
苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物       20份
再生橡胶                               20份
芳烃油                                 19.5份
过氧化二异丙苯                         0.5份
制备时，首先将上述配比的苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物、芳烃油放入密炼机中密炼，混合5分钟，然后加入苯乙烯-丁二烯共聚物、再生橡胶，混合10分钟，再加入过氧化二异丙苯，混合5分钟，密炼机温度80℃，将密炼后的胶料用开炼机混合，薄通5次后下片。最后将胶料用挤出机挤出造粒，挤出机温度为60℃，通过风环切粒。
实施例3
实施例3的可注射可硫化苯乙烯系橡胶粒子，它按以下配比的组分及含量(质量份)进行制备：
苯乙烯-丁二烯共聚物                     60份
苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物        10份
再生PP                                  10份
环烷油                                  19份
过氧化二异丙苯                          1份
制备时，首先将上述配比的苯乙烯-丁二烯共聚物、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物、再生PP、环烷油同时放入密炼机中密炼，混合20分钟，密炼机温度160℃，将密炼后的胶料用开炼机成片，加入过氧化二异丙苯，薄通30次后下片。最后将胶料用挤出机挤出造粒，挤出机温度110℃，通过水环切粒。
实施例4
实施例4的可注射可硫化苯乙烯系橡胶粒子，它按以下配比的组分及含量(质量份)进行制备：
苯乙烯-丁二烯共聚物                  55份
苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物       15份
环烷油                                 29.7份
过氧化二异丙苯                         0.3份
制备时，首先将上述配比的苯乙烯-丁二烯共聚物、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物、环烷油同时放入密炼机中密炼，混合10分钟，然后加入过氧化二异丙苯，混合3分钟，密炼机温度100℃，将密炼后的胶料用开炼机混合，薄通10次后下片。最后将胶料用挤出机挤出造粒，挤出机温度为70℃，通过风环切粒。
实施例5
实施例5的可注射可硫化苯乙烯系橡胶粒子，它按以下配比的组分及含量(质量份)进行制备：
苯乙烯-丁二烯共聚物                        40份
苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物           9.5份
环烷油                                     50份
过氧化二异丙苯                             0.5份
首先将上述配比的苯乙烯-丁二烯共聚物、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物、环烷油同时放入密炼机中密炼，混合10分钟，然后加入过氧化二异丙苯，混合3分钟，密炼机温度100℃，将密炼后的胶料用开炼机混合，薄通10次后下片。最后将胶料用挤出机挤出造粒，挤出机温度为70℃，通过风环切粒。
在上述各实施例制备过程中，可根据不同制件的性能需要，添加各种加工助剂，如硫化促进剂、防老剂、脱模剂、补强剂、阻燃剂、增黏剂、防黏剂。
橡胶制品性能测试
将各实施例制得的橡胶粒子通过注射机注射成型，制得片材。注射机模具带有加热装置，能保持模具的温度为100～200℃。测试数据如下：
Figure A200910047435D00121
注：①熔融指数测试条件为200℃，5Kg；熔融指数测试时未加硫化剂。
②样品制备条件：注射温度70℃，硫化温度165℃，硫化时间300秒。
由以上测试数据可以看出，橡胶粒子的熔融指数都超过10g/10min，粒子的流动性完全达到注射的要求。材料都有较高的断裂伸长率，表明硫化后的橡胶具有很好的韧性，并且永久压缩变形性较小，表明橡胶具有较好的回弹性能和高弹性高韧性，并且具有一定的强度，这种材料完全满足橡胶材料的使用要求。

Claims (10)

1、一种可注射可硫化苯乙烯系橡胶粒子，其特征在于按质量份配方组成如下：
苯乙烯-丁二烯共聚物                           40～70份
流动改性剂                                    10～30份
再生料                                        0～30份
软化油                                        10～50份
硫化剂                                        0.1～1份
2、根据权利要求1所述的一种可注射可硫化苯乙烯系橡胶粒子，其特征在于所述的苯乙烯-丁二烯共聚物的分子结构为线形结构或多臂星形结构，该聚合物的分子链结构为苯乙烯类单体和二烯烃单体的完全无规共聚结构或为苯乙烯类单体和二烯烃单体的多次嵌段共聚形成的交替微嵌段结构，二烯烃结构中的1，2-结构含量为10～40％；苯乙烯-丁二烯共聚物的分子结构式为-(PSX-PBY)n-或(-(PSX-PBY)n-)MR，前者为线形结构，后者为多臂星形结构，其中PS为苯乙烯类聚合物，PB为二烯烃类聚合物，R为星形结构的“核”，X＝1-300，Y＝1-2000，n＝10-3000，M＝3-20；共聚物中苯乙烯类单体的重量百分含量为5-80％，共聚物的分子量为40000-500000(Mn)。
3、根据权利要求1所述的一种可注射可硫化苯乙烯系橡胶粒子，其特征在于所述的流动改性剂可选用苯乙烯-丁二烯-苯乙烯共聚物、苯乙烯-乙烯-丁烯-苯乙烯共聚物、苯乙烯-乙烯-丙烯-苯乙烯共聚物中的至少一种。
4、根据权利要求1所述的一种可注射可硫化苯乙烯系橡胶粒子，其特征在于再生料可选用再生橡胶、PE再生料、EVA再生料、PP再生料中的至少一种。
5、根据权利要求1所述的一种可注射可硫化苯乙烯系橡胶粒子，其特征在于所述的软化油可选用环烷油、烷烃油、芳烃油中的至少一种。
6、根据权利要求1所述的一种可注射可硫化苯乙烯系橡胶粒子，其特征在于所述的硫化剂可选用过氧化苯甲酰、双对过氧化苯甲酰、二叔丁基过氧化物、过氧化二异丙苯、过氧化氢异丙苯。
7、一种制备权利要求1所述的可注射可硫化苯乙烯系橡胶粒子的工艺，其特征在于首先将一定配比的苯乙烯-丁二烯共聚物、流动改性剂、再生料、软化油同时放入密炼机中密炼，混合10～30分钟，然后加入硫化剂，混合3～10分钟，密炼机温度60～120℃，将密炼后的胶料用开炼机混合，薄通5～20次后下片，最后将胶料用挤出机挤出造粒，挤出机温度为60～110℃，通过风环切粒或是水环切粒。
8、一种制造权利要求1所述的可注射可硫化苯乙烯系橡胶粒子的工艺，其特征在于首先将一定配比的流动改性剂、软化油放入密炼机中密炼，混合5～15分钟，然后加入苯乙烯-丁二烯共聚物、再生料，混合5～15分钟，再加入硫化剂，混合3～10分钟，密炼机温度60～120℃，将密炼后的胶料用开炼机混合，薄通5～20次后下片，最后将胶料用挤出机挤出造粒，挤出机温度为60～110℃，通过风环切粒或是水环切粒。
9、一种制造权利要求1所述的可注射可硫化苯乙烯系橡胶粒子的工艺，其特征在于首先将一定配比的苯乙烯-丁二烯共聚物、流动改性剂、再生料、软化油同时放入密炼机中密炼，混合10～30分钟，密炼机温度100～160℃，将密炼后的胶料用开炼机成片，加入硫化剂，薄通10～30次后下片，最后将胶料用挤出机挤出造粒，挤出机温度60～110℃，通过风环切粒或是水环切粒。
10、根据权利要求7、8或9所述的可注射可硫化苯乙烯系橡胶粒子制备工艺，其特征在于在制备过程中，可根据不同制件的性能需要，添加各种加工助剂，如硫化促进剂、防老剂、脱模剂、补强剂、阻燃剂、增黏剂、防黏剂。
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CN104974458A (zh) * 2015-07-23 2015-10-14 温州市宜和鞋材有限公司 一种新型高耐磨、免喷漆鞋底材料及其制备方法
CN105968676A (zh) * 2016-05-12 2016-09-28 广州市番禺旭升合成材料有限公司 一种具有复印功能的塑料改性剂及其制备方法
CN105968676B (zh) * 2016-05-12 2019-07-12 广州市番禺旭升合成材料有限公司 一种具有复印功能的塑料改性剂及其制备方法
CN113172784A (zh) * 2021-05-08 2021-07-27 青岛科技大学 一种密炼机用的橡胶终炼工艺

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CN101624461A (zh) 2010-01-13
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