CN107987306B - 一种流体辅助注射制备橡胶发泡材料的方法及其制品 - Google Patents
一种流体辅助注射制备橡胶发泡材料的方法及其制品 Download PDFInfo
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Abstract
本发明公开了一种流体辅助注射制备橡胶发泡材料的方法,包括以下步骤:(1)通过备料、密炼、开炼、制粒,制备得发泡颗粒;(2)将发泡颗粒在射出机料筒中预热,将熔体注入到模具中,同时向模具中通入流体CO2,熔体在流体辅助下成型,其中,模具预抽真空预热预压;(3)将步骤(2)中成型的材料放入定型烘道,经定型得所述的橡胶发泡材料。本发明还公开了上述方法制备得到的橡胶发泡制品。本发明采用注射发泡工艺,具有加工效率高的优势,本发明方法制备的橡胶发泡制品具有轻量化、高回弹、低压缩形变的优势,可以应用于运动鞋发泡大底、自行车发泡轮胎、低速机动车发泡轮胎、自行车座垫、运动器材缓冲垫子等多个领域。
Description
技术领域
本发明涉及橡胶发泡材料制备方法领域,具体涉及一种流体辅助注射制备橡胶发泡材料的方法及其制品。
背景技术
聚合物软质发泡材料具有轻量化、缓冲、避震、隔热、隔音等优异性能,已广泛应用于鞋材、座垫、密封、阻尼、体育运动器材、家具等领域。
橡胶发泡材料具有优异的拉伸、撕裂、耐磨、耐温、耐老化性能。橡胶发泡材料的制备方法也已公开,其主要采用化学发泡剂和微球物理发泡剂,化学交联,通过模压发泡的方法制备。橡胶模压发泡时,需要预先制备混合坯料,然后在模具中边硫化边发泡,为了稳定材料性能,甚至需要二次硫化,因此存在效率低的问题,对于某些结构复杂的制件,坯料制备困难,导致应用领域受到限制;其次,对于轮胎等模压发泡橡胶制品,存在接头,而接头处材料性能差,易导致废品率高的问题。除此之外,采用模压发泡制备的橡胶发泡材料存在表面质量较差、颜色不鲜艳的问题。注射发泡相对于模压发泡生产效率高,且赋予橡胶发泡制品良好外观性能及复杂花纹设计的可实现性。
通常采用化学发泡剂制备的橡胶发泡材料,其泡孔尺寸较大,且泡孔分布不均一。对橡胶发泡材料的性能有一定的影响。高压流体制备微发泡聚合物材料的方法在1992年被提出。高压流体如高压CO2流体是一种清洁、廉价环境友好的物理发泡剂,根据需求,高压CO2流体可以为高压气体流体、高压液体流体和超临界流体。CO2的超临界状态可以在比较温和的条件下实现,如压力为7.37MPa,温度为31.1℃。高压流体作为物理发泡剂,制备的泡孔尺寸相对于化学发泡剂制备的小,且泡孔分布均匀。
发明内容
为了改善橡胶发泡材料的加工性能,提高橡胶发泡制品的生产效率和外观质量,提高橡胶发泡材料的力学性能,本发明提供一种高压流体辅助注射制备橡胶发泡材料的方法及其制品。
本发明采用的技术方案如下:
一种流体辅助注射制备橡胶发泡材料的方法,包括以下步骤:
(1)通过备料、密炼、开炼、制粒,制备得发泡颗粒;
(2)将发泡颗粒在射出机料筒中预热,将熔体注入到模具中,同时向模具中通入流体CO2,熔体在流体辅助下成型,其中,模具预抽真空预热预压;
(3)将步骤(2)中成型的材料放入定型烘道,经定型得所述的高硬度橡胶发泡材料。
本发明采用高压流体辅助注射发泡的方法,绿色环保,设备要求简单,具有可行性及经济性。
步骤(1)中,所述的发泡颗粒的制备包括:将除了交联剂和发泡剂以外的其他原料混合进行密炼,调整密炼温度控制为110~120℃,保持10~30min,然后加入交联剂和发泡剂,继续密炼升温,出料温度为120~125℃,密炼结束后进行开炼、造粒,得所述的高硬度橡胶发泡材料。优选地,所述的发泡颗粒的长度为3~6mm。
步骤(2)中,射出机料筒的温度为120~135℃,发泡颗粒在该温度下熔化为熔体。
作为优选,为了防止料筒中发泡剂分散和交联剂发生交联,所述射出机料筒的温度为120~128℃。
所述模具预抽真空预热预压至真空度为-0.1~-0.3MPa,模具的温度为175~190℃,硫化时间为450~600s。
作为优选,所述模具的真空度为-0.15~-0.25MPa,温度为180~185℃。
待熔体开始注入模具时,往模具中通入高压流体CO2,使熔体注入模具后,高压流体CO2与熔体充分混合并填满模具,所述的流体CO2的注入压力为0.5~5.0MPa,流体CO2的通入量为熔体质量的3~10%。
作为优选,所述流体CO2的注入压力为2~4MPa,流体CO2的通入量为熔体质量的5~8%。
发泡剂受热在模具中分解为N2、CO、CO2等,发泡剂分解产物以高压气体溶解在聚合物复合物基体中,发泡剂分解产物的溶解度为2~5wt%,交联剂受热分解使聚合物分子链发生交联反应。
步骤(2)中,所述模具的泄压速度为0.5~5.0MPa/s,将模具迅速打开,发泡剂处于过饱和状态,从而引发泡孔成核、增长。
作为优选,所述模具的泄压速度为0.8~4.0MPa/s。
步骤(3)中,所述定型烘道的温度阶梯下降,依次为130℃,120℃,100℃,停留时间为1~15min。
本发明还提供了上述方法制备得到的橡胶发泡制品。
作为第一种实施方式,所述的橡胶发泡制品,包括以下重量份比的原料:
乙烯-辛烯共聚物15~30份,VA含量为36~40%的乙烯-醋酸乙烯共聚物15~40份,塑化橡胶30~60份,硬脂酸1~3份,快熟剂1~3份,流动剂2~4份,耐磨剂5~10份,发泡剂1.5~2.5份,氧化锌2~4份,硬脂酸锌1~2份,交联剂1~2份,软化剂0~10份,颜料0~30份。
作为第二种实施方式,所述的橡胶发泡制品,包括以下重量份比的原料:
乙烯-辛烯共聚物20~40份,VA含量为36~40%的乙烯-醋酸乙烯共聚物15~30份,塑化橡胶20~50份,聚乙烯5~20份,无机填料1~10份,硬脂酸0.5~3.5份,快熟剂2~4份,流动剂2~4份,耐磨剂5~10份,发泡剂0.5~2.0份,氧化锌2~6份,硬脂酸锌2~4份,交联剂1~4份,软化剂0~6份,颜料0~30份。
上述两种实施方式中,所述的塑化橡胶为丁苯橡胶、异戊橡胶、三元乙丙橡胶、二元乙丙橡胶、氯磺化聚乙烯橡胶和氯化聚乙烯橡胶中的一种或者多种,塑化橡胶的门尼粘度为[ML(1+4)100℃]为30~80。
上述两种实施方式中,所述的快熟剂为三烯丙基异氰脲酸酯(TAIC)。
上述两种实施方式中,所述的流动剂为脂肪酸衍生物(JPL-12)和有机脂及脂肪酸衍生物的加成物(EBS)中的至少一种。
上述两种实施方式中,所述的耐磨剂为聚四氟乙烯(PTFE)。
上述两种实施方式中,所述的发泡剂为AC发泡剂,即偶氮二甲酰胺,所述发泡剂的分解温度为160~200℃。
上述两种实施方式中,所述的交联剂为双叔丁基过氧化二异丙基苯(BIPB)。
上述两种实施方式中,所述的软化剂为聚乙烯蜡(PE蜡)和白油中的至少一种,所述软化剂的软化温度不高于80℃,100℃的熔融指数为100~400g/10min。
上述两种实施方式中,所述颜料为无机颜料或有机颜料,其中无机颜料可以为炭黑、钛白粉等,其中有机颜料为高温颜料,如偶氮颜料等,高温颜料的挥发温度不低于180℃。
第二种实施方式中,所述的聚乙烯(PE)的熔点为95~120℃、结晶温度为75~100℃,可以为高密度聚乙烯(HDPE)、低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLDPE)、金属茂聚乙烯(MPE)等。
第二种实施方式中,所述的无机填料表面经过硅烷偶联剂改性,尺寸为0.5~5μm,具体可以为滑石、轻钙、陶土等。
第二种实施方式中,所述的橡胶发泡制品在室温下的表皮邵氏硬度为75~90C、芯层邵氏硬度为70~85C,温度为70℃下的表皮邵氏硬度为70~85C、芯层邵氏硬度为65~80C,温度为80℃下的表皮邵氏硬度为60~80C、芯层邵氏硬度为60~80C。
上述两种实施方式中,所述的橡胶发泡制品的密度为0.20~0.45g/cm3,泡孔尺寸为50~150μm,泡孔密度为107~109个/cm3。
与现有技术相比,本发明具有以下有益效果:
(1)本发明方法通过添加软化剂、选择高温发泡剂及配合高的料筒温度、选择可抽真空模具等方法来提供配方流动性,采用高压流体辅助注射发泡的方法制备了橡胶组份高的橡胶发泡制品,高的橡胶含量赋予发泡制品优异的拉伸、撕裂、耐磨、回弹、压缩性能。本发明采用注射发泡工艺,具有加工效率高的优势。本发明可以选择无机或者高温有机颜料,发泡制品具有颜色鲜艳的优势。
(2)本发明方法制备的橡胶发泡制品具有轻量化、高回弹、低压缩形变的优势,可以应用于运动鞋发泡大底、自行车发泡轮胎、低速机动车发泡轮胎、自行车座垫、运动器材缓冲垫子等多个领域。
具体实施方式
为了进一步解释本发明的技术方案,下面通过具体实施例来对本发明进行详细阐述。
实施例1
本实施例中,橡胶发泡制品由以下重量份比的原料:
SBR橡胶15份,IR橡胶35份,OBC树脂15份,EVA 35份,AC发泡剂1份,硬脂酸2份,TAIC 1.5份,PTFE 5份,氧化锌2份,硬脂酸锌2份,BIPB 1.5份,JPL-12 3份。
本实施例中,橡胶发泡制品通过以下方法制备:
(1)将经开炼机塑化后、门尼粘度[ML(1+4)100℃]为35的SBR橡胶15份和门尼粘度[ML(1+4)100℃]为50的IR橡胶35份与OBC树脂15份、熔指为200g/min的EVA为35份、硬脂酸2份、TAIC 1.5份、PTFE 5份、氧化锌2份、硬脂酸锌2份和JPL-12 3份混合,在115℃下密炼30min,然后加入分解温度为180℃的高温AC发泡剂1份和BIPB交联剂1.5份,继续密炼5min,出料温度为125℃。密炼结束后进行开炼、造粒,制备了门尼粘度[ML(1+4)100℃]为35,长度为3~6mm的射出发泡颗粒。
(2)将射出发泡颗粒喂入温度为125℃的射出机料筒中,经螺杆挤出注射到模具中,在熔体开始注入模具的同时,往模具中以2.5MPa通入高压流体CO2,高压流体的通入量为熔体质量的6%,使高压流体CO2与熔体充分混合并填满模具。熔体在模具温度为185℃、真空度为-0.15MPa、硫化时间为500s的条件下成型,发泡剂在此温度下分解产生的发泡剂分解产物的溶解度为3.5wt%,以泄压速度为3.0MPa/s的速度打开模具。
(3)将步骤(2)中成型的材料放入定型烘道中,经过温度梯度为130、120、100℃的烘道定型8min后,得到硬度为58C、密度为0.30g/cm3、泡孔尺寸为100μm、泡孔密度为108个/cm3的橡胶发泡制品。
测试结果表明:该橡胶发泡制品的拉伸强度为23kg/cm2、撕裂强度为19kg/cm、反弹率为50%、压缩变形为32%、DIN耐磨为80mm3。
实施例2
本实施例中,橡胶发泡制品由以下重量份比的原料:
异戊橡胶20份,CSM橡胶30份,OBC树脂25份,EVA 25份,白油5份,AC发泡剂2份,硬脂酸2份,TAIC 2.5份,PTFE 5份,氧化锌2份,硬脂酸锌1份,BIPB 2份,EBS 3份,颜料炭黑5份。
本实施例中,射出发泡橡胶材料通过以下方法制备:
(1)将经开炼机塑化后、门尼粘度[ML(1+4)100℃]为60的异戊橡胶20份和门尼粘度[ML(1+4)100℃]为30的CSM橡胶30份、OBC树脂25份、熔指为200g/min的EVA 25份、熔指为300g/min的白油5份,硬脂酸2份、TAIC 2.5份,PTFE 5份,氧化锌2份,硬脂酸锌1份,EBS 3份,颜料炭黑5份混合,在120℃下密炼20min,再加入分解温度为190℃的高温AC发泡剂2份,BIPB 2份,继续密炼5min,出料温度为120℃。密炼结束后进行开炼、造粒,制备了门尼粘度[ML(1+4)100℃]为40,长度为3~6mm的射出发泡颗粒。
(2)将射出发泡颗粒喂入温度为130℃的射出机料筒中,经螺杆挤出注射到模具中,在熔体开始注入模具的同时,往模具中通入以1.5MPa高压流体CO2,高压流体的通入量为熔体质量的6%,使高压流体CO2与熔体充分混合并填满模具。熔体在模具温度为183℃、真空度为-0.20MPa、硫化时间为520s的条件下成型,发泡剂在此温度下分解产生的发泡剂分解产物的溶解度为3.0wt%,以泄压速度为3.0MPa/s的速度打开模具。
(3)将步骤(2)中成型的材料放入定型烘道中,经过温度梯度为130、120、100℃的烘道定型7min后,得到硬度为68C、密度为0.38g/cm3、泡孔尺寸为130μm、泡孔密度为108个/cm3的橡胶发泡制品。
测试结果表明:该橡胶发泡制品的拉伸强度为33kg/cm2、撕裂强度为24kg/cm、反弹率为54%、压缩变形为26%、DIN耐磨为60mm3。
实施例3
本实施例中,发泡橡胶材料由以下重量份比的原料:
SBR橡胶15份、IR橡胶25份、OBC 25份、EVA 20份、HDPE10份、滑石粉5份、AC发泡剂1份、硬脂酸3份、TAIC 3份、EBS 3份、PTFE 6份、氧化锌4份、硬脂酸锌3份、BIPB 3份。
本实施例中,高硬度橡胶发泡材料通过以下方法制备:
(1)将经开炼机塑化后、门尼粘度[ML(1+4)100℃]为35的SBR橡胶15份和门尼粘度[ML(1+4)100℃]为50的IR橡胶25份、OBC树脂25份、熔指为200g/min的EVA为20份、HDPE 10份、滑石粉5份、硬脂酸3份、TAIC 3份、PTFE 6份、氧化锌4份、硬脂酸锌2份和EBS 3份混合,在115℃下密炼30min,然后加入分解温度为180℃的高温AC发泡剂1份和BIPB 3份,继续密炼5min,出料温度为125℃。密炼结束后进行开炼、造粒,制备了门尼粘度[ML(1+4)100℃]为32,长度为3~6mm的发泡颗粒。
(2)将射出发泡颗粒喂入温度为126℃的射出机料筒中,经螺杆挤出注射到模具中,在熔体开始注入模具的同时,往模具中以4.0MPa通入高压流体CO2,高压流体的通入量为熔体质量的7%,使高压流体CO2与熔体充分混合并填满模具。熔体在模具温度为184℃、真空度为-0.30MPa、硫化时间为520s的条件下成型,发泡剂在此温度下分解产生的发泡剂分解产物的溶解度为4.0wt%,以泄压速度为2.5MPa/s的速度打开模具。
(3)将步骤(2)中成型的材料放入定型烘道中,经过温度梯度为130、120、100℃的烘道定型8min后,得到硬度为78C、密度为0.32g/cm3、泡孔尺寸为105μm、泡孔密度为108个/cm3的橡胶发泡制品。
测试结果表明:该高硬度橡胶发泡材料的拉伸强度为17kg/cm2、撕裂强度为14kg/cm、反弹率为48%、压缩变形为30%、DIN耐磨为95mm3。
实施例4
本实施例中,发泡橡胶材料由以下重量份比的原料:
CSM橡胶20份、IR橡胶15份、OBC 23份、EVA 20份、LDPE15份、滑石粉7份、白油2份、AC发泡剂1份、硬脂酸3份、TAIC 2份、EBS 3份、PTFE 6份、氧化锌3份、硬脂酸锌3份、BIPB2.5份。
本实施例中,高硬度橡胶发泡材料通过以下方法制备:
(1)将经开炼机塑化后、门尼粘度[ML(1+4)100℃]为30的CSM橡胶20份和门尼粘度[ML(1+4)100℃]为60的IR橡胶15份、OBC树脂23份、熔指为200g/min的EVA为20份、LDPE 15份、滑石粉7份、熔指为300g/min的白油2份、硬脂酸3份、TAIC 2份、PTFE 6份、氧化锌3份、硬脂酸锌3份和EBS 3份混合,在115℃下密炼30min,然后加入分解温度为180℃的高温AC发泡剂1份和BIPB 2.5份,继续密炼5min,出料温度为125℃。密炼结束后进行开炼、造粒,制备了门尼粘度[ML(1+4)100℃]为35,长度为3~6mm的发泡颗粒。
(2)将射出发泡颗粒喂入温度为130℃的射出机料筒中,经螺杆挤出注射到模具中,在熔体开始注入模具的同时,往模具中以3.5MPa通入高压流体CO2,高压流体的通入量为熔体质量的8%,使高压流体CO2与熔体充分混合并填满模具。熔体在模具温度为182℃、真空度为-0.30MPa、硫化时间为550s的条件下成型,发泡剂在此温度下分解产生的发泡剂分解产物的溶解度为3.8wt%,以泄压速度为2.5MPa/s的速度打开模具。
(3)将步骤(2)中成型的材料放入定型烘道中,经过温度梯度为130、120、100℃的烘道定型7min后,得到硬度为68C、密度为0.33g/cm3、泡孔尺寸为105μm、泡孔密度为108个/cm3的橡胶发泡制品。
测试结果表明:该高硬度橡胶发泡材料的拉伸强度为23kg/cm2、撕裂强度为17kg/cm、反弹率为52%、压缩变形为26%、DIN耐磨为80mm3。
Claims (5)
1.一种流体辅助注射制备橡胶发泡材料的方法,其特征在于,包括以下步骤:
(1)通过备料、密炼、开炼、制粒,制备得发泡颗粒;
所述的发泡颗粒的制备包括:将除了交联剂和发泡剂以外的其他原料混合进行密炼,调整密炼温度控制为110~120℃,保持10~30min,然后加入交联剂和发泡剂,继续密炼升温,出料温度为120~125℃,密炼结束后进行开炼、造粒;
(2)将发泡颗粒在射出机料筒中预热,将熔体注入到模具中,同时向模具中通入流体CO2,熔体在流体辅助下成型,其中,模具预抽真空预热预压;
所述射出机料筒的温度为120~128℃,发泡颗粒在该温度下熔化为熔体;
所述流体CO2的注入压力为2~4MPa,流体CO2的通入量为熔体质量的5~8%;
所述模具预抽真空预热预压至真空度为-0.1~-0.3MPa,模具的温度为175~190℃;
所述模具的泄压速度为0.8~4.0MPa/s;
(3)将步骤(2)中成型的材料放入定型烘道,经定型得所述的橡胶发泡材料;
所述橡胶发泡材料包括以下重量份比的原料:
乙烯-辛烯共聚物15~30份, VA含量为36~40%的乙烯-醋酸乙烯共聚物15~40份,塑化橡胶30~60份,硬脂酸1~3份,快熟剂1~3份,流动剂2~4份,耐磨剂5~10份,发泡剂1.5~2.5份,氧化锌2~4份,硬脂酸锌1~2份,交联剂1~2份,软化剂0~10份,颜料0~30份;或者,
乙烯-辛烯共聚物20~40份,VA含量为36~40%的乙烯-醋酸乙烯共聚物15~30份,塑化橡胶20~50份,聚乙烯5~20份,无机填料1~10份,硬脂酸0.5~3.5份,快熟剂2~4份,流动剂2~4份,耐磨剂5~10份,发泡剂0.5~2.0份,氧化锌2~6份,硬脂酸锌2~4份,交联剂1~4份,软化剂0~6份,颜料0~30份;
所述的橡胶发泡制品的泡孔尺寸为50~150 μm,泡孔密度为107~109个/cm3。
2.根据权利要求1所述的流体辅助注射制备橡胶发泡材料的方法,其特征在于,步骤(2)中熔体在硫化时间为450~600s的条件下成型。
3.一种橡胶发泡制品,其特征在于,由权利要求1或2方法制备得到。
4.根据权利要求3所述的橡胶发泡制品,其特征在于,所述的塑化橡胶为丁苯橡胶、异戊橡胶、三元乙丙橡胶、二元乙丙橡胶、氯磺化聚乙烯橡胶和氯化聚乙烯橡胶中的一种或者多种,塑化橡胶的门尼粘度为[ML(1+4)100℃]为30~80。
5.根据权利要求3所述的橡胶发泡制品,其特征在于,所述的软化剂为聚乙烯蜡和白油中的至少一种,所述软化剂的软化温度不高于80℃,100℃的熔融指数为100~400g/10min。
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