CN101386218A - 聚苯硫醚纤维复合层压板材的制造方法 - Google Patents
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Abstract
本发明公开了一种聚苯硫醚纤维复合层压板材的制造方法，采用高频电加热层压模生产聚苯硫醚纤维复合层压板材，所述复合层压板以A层/B层单元结构顺序叠合，A层为聚苯硫醚PPS树脂构织物；B层为增强长纤维层；A与B层间为起粘合作用的热塑性EVA薄膜层；复合层经冷压后，在高频电加热层压模中在290－330℃熔融热压成型。聚苯硫醚PPS树脂构织物采用经热牵伸定形处理后的PPS树脂纤维。该层压板兼具有很高的机械强度和聚苯硫醚纤维的阻燃、电绝缘，耐化学性，耐辐射性好的优点，适宜用于航天航空，坦克装甲，印刷电路基板，高温隔热材料及低温绝热材料等极端领域。
Description
所属技术领域
本发明属于特种功能纤维板生产领域。
背景技术
中国专利公开号：CN1212652A的发明中所用的是聚苯硫醚树脂组合物(A层)，PPS树脂和选自环氧基、酸酐基、羧基及其盐、碳酸酯基的热塑性树脂(B层)，然后层压层的多层模制品，其制造工艺采用单螺杆或双螺杆挤出机的熔混工艺，先将聚苯硫醚树脂和填料挤条切割造粒，然后再经过单螺杆或双螺杆挤出机共挤出，在模具内成形，最后层压层的制造出多层模制品。该工艺主要是制造多层管状物，制成的管状物主要是用于汽车的燃油管线，或冷却系统的管线，以及民房取暖管线等，不适用于航天航空或军事领域以及电子印刷电路板等板材消费行业。
为了得到兼具PPS树脂以外之热塑性树脂的机械性质、成型性、经济性等特点和PPS树脂的耐热性、耐热水性、耐化学品性的特点的模制品，把两种材料层复合在一起一直是国内外研究者的追求目标，在日本专利特开平5—193060中提出了在PPS树脂层与聚烯烃树脂层中间加有粘合层的层压结构物。其插入粘合层的方法，是采用共挤出成型得到的多层结构，这使得使用挤出机的数目增多，加工设备变得复杂，而且加工时间变长，从经济考虑是不合算的，在工业上使用的希望也不大。
鉴于现有技术的以上缺点，提出本发明的解决方案。
发明内容
本发明的目的是通过以下的手段实现的。
聚苯硫醚纤维复合层压板材的制造方法，采用高频电加热层压模生产聚苯硫醚纤维复合层压板材，所述复合层压板以A层/B层单元结构顺序叠合，复合层压板面层采用A层；
(1)A层为聚苯硫醚PPS树脂构织物，可为聚苯硫醚短纤维纸、聚苯硫醚薄膜、聚苯硫醚纤维毛毡布之一；B层为增强长纤维层；A与B层间为起粘合作用的热塑性EVA薄膜层；增强材料长纤维B层相邻层间纤维呈交叉成90度角密植排列；(2)由(1)得到的复合层经冷压后，在高频电加热层压模中在290-330℃熔融热压成型；(3)所述聚苯硫醚PPS树脂构织物采用经热牵伸定形处理后切断成0.20—80毫米的PPS树脂纤维。
本发明中所使用的聚苯硫醚纤维是它的短纤维纸、或用熔融粘度较低的聚苯硫醚树脂，或聚苯硫醚薄膜或聚苯硫醚纤维毛毡。其使用量大致在50—80％，最好在60—70％，增强材料使用的是碳纤维、玻璃纤维、芳纶纤维、陶瓷纤维、碳化硅纤维、石棉纤维、石膏纤维、金属纤维等短纤维、纤维长丝或纤维布或丝云母中的一种或多种纤维的混合物，所使用的热塑性粘合剂或热塑性材料是可以是EVA热熔胶，聚酰胺热熔胶，聚酯热熔胶，聚氨酯热熔胶，橡胶型热压敏胶，丙烯酸酯型热压敏胶等，或聚碳酸酯，聚四氟乙烯，聚乙烯酮，聚硫醚酮，聚酰胺，聚芳酰亚胺，聚酯，聚丙烯酸酯，聚甲基丙烯酸酯，聚丙烯腈，聚乙烯酮，聚砜，聚甲醛，聚甲基丙烯酸甲酯，聚甲基丙烯酸乙酯，丙烯酸共聚物，聚苯醚等树脂的纤维或树脂粉末；无机填料可以添加钛白粉、轻质碳酸钙、硫酸钙、滑石粉，粘土，硅藻土，碳黑，高岭土，云母，石棉，氧化铝，氧化硅，氧化镁，氧化锆，碳酸镁，白云石，硫酸镁，硫酸钡，纳米级石英砂，氮化硼，萤石，沸石所使用的增效剂可以是：超高分子量聚硅氧烷，或有机硅增效剂。在热塑性树脂中还可以添加晶体成核剂，脱模剂，抗氧化剂，热稳定剂，润滑剂，紫外线防护剂，染色剂，阻燃剂、塑料增韧剂等助剂。
本发明中聚苯硫醚纤维层压板材的制造工艺是采用增强材料的长纤维在层与层之间交叉成90度角密植排列，或其短纤维混乱铺平，或其纤维布平铺。该层压板是用其短纤维纸、或用熔融粘度较低的聚苯硫醚树脂，或聚苯硫醚薄膜或聚苯硫醚短纤维制成的毛毡与增强材料和热塑性粘合剂互相交叉叠合热压制成的。即：聚苯硫醚材料→热塑性粘合剂→增强材料→聚苯硫醚材料→热塑性粘合剂→增强材料→热塑性粘合剂→聚苯硫醚材料→……→聚苯硫醚材料。
本发明中的聚苯硫醚纤维层压板材的热压方法是采用高频电加热层压模，使聚苯硫醚材料和热塑性粘合剂在模具中熔融平流热压，从而使聚聚苯硫醚材料和增强材料充分粘合在一起，在这种情况下制造的层压板材具有很好的抗拉强度，抗冲击强度，抗弯曲强度，抗压强度，同时具有密度轻，阻燃、电绝缘，耐化学性好，耐辐射性好，热稳定性好，吸水率低，在200℃的高温下长期使用不变形，在-20℃的低温下韧性好等特点，广泛用于航天航空，坦克装甲，印刷电路基板，高温隔热材料及低温绝热材料等高科技领域。
具体实施方式
下面结合实施例对本发明的工艺作进一步的详述。
实施例1
以硫化钠与对二氯苯为原料合成生产的聚苯硫醚树脂熔融纺丝纺织成的聚苯硫醚纤维原丝；纤维原丝经热牵伸定形处理成成品纤维；切成52mm的成品纤维构织为纤维布层。在模具最低表面铺一层该聚苯硫醚纤维构织物纤维布层，然后铺上一层起粘合作用的热塑性EVA薄膜，再铺上一层玻璃纤维的增强材料，玻璃纤维采用排丝板将其一根一根的密植排列，在玻璃纤维的上面铺上聚苯硫醚材料和热塑性树脂材料及增效剂，再铺上聚苯硫醚材料……玻璃纤维采用排丝板将其一根一根的密植排列，这一层玻璃纤维与上面一层玻璃纤维交叉成90度角，即：Bi和Bi+1之间呈90°角，在玻璃纤维的上面铺上聚苯硫醚材料和EVA热塑性树脂材料及增效剂，分别一层一层的叠加到层压板厚度12mm，与模具相接触的面层均采用聚苯硫醚纤维构织物。复合板用10kg/cm2的压力冷压成形，在层压板的成份中含有50％(质量)的聚苯硫醚构织材料。然后接通电源，采用高频电加热层压模加热，加热温度频率是10-30C°/min，使温度达到290℃，同时使层压板中的聚苯硫醚材料和热塑性粘合剂在模具中充分熔融，模具的加压压力是1.0kg/cm2，当层压板达到需要的厚度时，停止加热，切断电源，并在模具中通入冷却水，使其慢慢冷却，其冷却频率为5-10℃/min。像这样制成的聚苯硫醚纤维层压板表面光滑，没有细小的突状物出现，其机械性能很好。经过检测10mm的层压板其拉伸强度为1200GPa，比强度为600*106，密度为2.0g/cm3。且具有良好的阻燃、电绝缘，耐化学性和耐辐射性。
实施例2
热压温度330℃，其它采用实例1的制造工艺流程、工艺条件，其增强材料采用碳纤维，用低熔融黏度聚苯硫醚树脂粉作为聚苯硫醚纤维构织物，制成的聚苯硫醚纤维10mm层压板其中聚苯硫醚含量50％，其拉伸强度为1300GPa，比强度为810*106，密度为1.6g/cm3，
实施例3
采用实例1的制造工艺流程、除冷压成形压力为200kg/cm2，其余工艺条件与实例1相同，聚苯硫醚含量80％，其增强材料采用碳化硅纤维，制成的聚苯硫醚纤维层压板其拉伸强度为1250GPa，比强度为820*106，密度为1.7g/cm3。
实施例4
采用实例1的制造工艺流程，除热压压力为100kg/cm以外其余工艺条件与实例1相同，聚苯硫醚含量80％，其增强材料分别采用陶瓷纤维，制成的聚苯硫醚纤维层压板其拉伸强度分别为1220GPa，比强度为800*106，密度为1.9g/cm3。
在本发明的基本方案下，其增强材料分别采用芳纶1313、1414、芳杂环纤维、高阻燃性芳杂环纤维，像这样制成的聚苯硫醚纤维层压板10—200mm，其中聚苯硫醚含量为60％和70％时具有很高的拉伸强度、抗冲击强度，抗弯曲强度等特性，可以用于坦克装甲。
在实际操作过程中采用实例1的制造工艺流程，工艺条件，其增强材料分别采用石棉纤维、石膏纤维、丝云母、金属纤维像这样制成的聚苯硫醚纤维层压板也能够获得很好的效果，可以得到不同强度的聚苯硫醚层压板以满足不同的需求。
如果在实际操作过程中采用实例1的制造工艺流程，工艺条件，B层热塑性树脂还可以采用聚碳酸酯，聚四氟乙烯，聚乙烯酮，聚硫醚酮，聚酰胺，聚芳酰亚胺，聚酯，聚丙烯酸酯，聚甲基丙烯酸酯，聚丙烯腈，聚乙烯酮，聚砜，聚甲醛，聚甲基丙烯酸甲酯，聚甲基丙烯酸乙酯，丙烯酸共聚物，聚苯醚等树脂的纤维。
采用实施例1的制造工艺流程、工艺条件，其层压板的材料中分别加入20％的钛白粉，轻质碳酸钙，硫酸钙；还可以在层压板中分别加入滑石粉，粘土，硅藻土，碳黑，高岭土，云母，石棉，氧化铝，氧化硅，氧化镁，氧化锆，碳酸镁，白云石，硫酸镁，硫酸钡，纳米级石英砂，氮化硼，萤石，沸石等作为填料。
采用本发明方法，在冷压成形压力为10-200kg/cm2，热压定形压力为1.0-100kg/cm2，得到10—200mm厚度的复合层压板材。
Claims (4)
1、聚苯硫醚纤维复合层压板材的制造方法，采用高频电加热层压模生产聚苯硫醚纤维复合层压板材，所述复合层压板以A层/B层单元结构顺序叠合，复合层压板面层采用A层；
(1)A层为聚苯硫醚PPS树脂构织物，可为聚苯硫醚短纤维纸、聚苯硫醚薄膜、聚苯硫醚纤维毛毡布之一；B层为增强长纤维层；A与B层间为起粘合作用的热塑性EVA薄膜层；增强材料长纤维B层相邻层间纤维呈交叉成90度角密植排列；
(2)由(1)得到的复合层经冷压后，在高频电加热层压模中在290-330℃熔融热压成型；(3)所述聚苯硫醚PPS树脂构织物采用经热牵伸定形处理后切断成0.20—80毫米的PPS树脂纤维。
2、根据权利要求1所述之聚苯硫醚纤维复合层压板材的制造方法，其特征在于，所述之增强长纤维B层是用采用以下纤维之一：碳纤维、玻璃纤维、芳纶纤维、陶瓷纤维。
3、根据权利要求1所述之聚苯硫醚纤维复合层压板材的制造方法，其特征在于，在冷压成形压力为10-200kg/cm2，热压定形压力为1.0-100kg/cm2，得到10—200mm厚度的复合层压板材。
4、根据权利要求1所述之聚苯硫醚纤维复合层压板材的制造方法，其特征在于，该层压板含有高性能聚苯硫醚纤维构织物50-80％。
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