CN115506151B - 一种水性上浆剂及其制备方法和一种针对碳纤维/聚丙烯纤维混合毡的上浆方法 - Google Patents
一种水性上浆剂及其制备方法和一种针对碳纤维/聚丙烯纤维混合毡的上浆方法 Download PDFInfo
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- CN115506151B CN115506151B CN202211341327.6A CN202211341327A CN115506151B CN 115506151 B CN115506151 B CN 115506151B CN 202211341327 A CN202211341327 A CN 202211341327A CN 115506151 B CN115506151 B CN 115506151B
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
本发明涉及上浆剂技术领域,提供了一种水性上浆剂及其制备方法和一种针对碳纤维/聚丙烯纤维混合毡的上浆方法。本发明提供的上浆剂包括成膜乳液和硅烷偶联剂。成膜乳液包括质量比为75:25~95:5的改性聚丙烯水性乳液和聚氨酯水性乳液,其中,改性聚丙烯水性乳液由酸酐接枝改性聚丙烯、乳化剂、氨甲基丙醇和水制备得到。在本发明中,改性聚丙烯具有较高的活性,能够和碳纤维表面的官能团结合,改性聚丙烯和聚丙烯树脂基体间的相容性更好,提高了碳纤维和树脂基体之间的界面结合力。本发明采用聚氨酯水性乳液降低表面能,提高上浆剂对于碳纤维的包覆作用,并采用硅烷偶联剂进一步提高碳纤维与树脂基体之间的结合作用。
Description
技术领域
本发明涉及上浆剂技术领域,特别涉及一种水性上浆剂及其制备方法和一种针对碳纤维/聚丙烯纤维混合毡的上浆方法。
背景技术
碳纤维增强树脂基复合材料(CFRP)结合了两相材料各自的优良特性,其中,作为分散相的碳纤维作为增强部分用于承担大部分的载荷,发挥其高强高模的特性,连续相基体树脂能够将碳纤维黏结在一起,起到传递应力的作用,两相材料之间的结合使复合材料整体的性能实现了“1+1>2”效果。因此,CFRP在汽车零部件、航空航天、风力发电叶片、船舶制造、建筑补强、休闲运动器材等领域受到重视。
在碳纤维复合材料中,界面作为连接两相、传递应力的重要“桥梁”,结合作用的强弱影响着复合材料的整体性能。在纤维增强热塑性复合材料中,由于热塑性树脂的主链结构大多是线性分子链,缺少活性的官能团与纤维表面发生反应,进而无法形成紧密的化学键结合,碳纤维与热塑性树脂基体的界面结合较弱,因此需要对碳纤维进行表面改性以达到增强界面结合力的目的。
对碳纤维来说,目前,上浆处理是成本较低且被广泛应用于工业生产的表面改性手段。对于初生的碳纤维来说,上浆是碳纤维在卷绕前的最后一道工艺。上浆后的碳纤维的表面会包覆一层浆膜,该浆膜不仅可以减少碳纤维与机器间的磨损,保护碳纤维防止其发生断裂,还能够在碳纤维表面引入活性基团。但是现有的上浆剂,如环氧树脂类上浆剂,与缺少活性官能团的热塑性树脂基体之间的相容性差,对碳纤维表面改性效果不佳,导致碳纤维与热塑性树脂基体间的界面结合力不高。
发明内容
有鉴于此,本发明提供了一种水性上浆剂及其制备方法和一种针对碳纤维/聚丙烯纤维混合毡的上浆方法。本发明提供的水性上浆剂对碳纤维表面具有较好的改性效果,有利于提高碳纤维与聚丙烯热塑性树脂基体间的界面结合力。
为了实现上述发明目的,本发明提供以下技术方案:
一种水性上浆剂,包括成膜乳液和硅烷偶联剂;
所述成膜乳液与所述硅烷偶联剂的质量比为90:10~95:5;
所述成膜乳液包括改性聚丙烯水性乳液和聚氨酯水性乳液;所述改性聚丙烯水性乳液和聚氨酯水性乳液的质量比为75:25~95:5;
所述改性聚丙烯水性乳液,以质量分数计,包括:
所述聚氨酯水性乳液,以质量分数计,包括45%~50%的聚氨酯和50%~55%的水。
优选的,所述马来酸酐接枝改性聚丙烯,以质量分数计,包括以下制备原料:
优选的,所述马来酸酐接枝改性聚丙烯的制备方法包括以下步骤:
将聚丙烯、马来酸酐、苯乙烯、引发剂、二甲苯、水和分散剂混合,依次进行溶胀和接枝反应,得到所述酸酐接枝改性聚丙烯;所述溶胀的温度为65℃~70℃,时间为2h~3h,所述接枝反应的温度为90℃~100℃,时间为5h~8h。
优选的,所述改性聚丙烯水性乳液的制备方法包括以下步骤:将马来酸酐接枝改性聚丙烯、乳化剂、氨甲基丙醇和水进行乳化,得到所述改性聚丙烯水性乳液;所述乳化在搅拌条件下进行,所述搅拌的转速为750r/min~1000r/min,所述乳化的温度为164℃~169℃,时间为60min~100min。
优选的,所述聚氨酯,以质量分数计,包括以下制备原料:
优选的,所述聚氨酯的制备方法包括以下步骤:
将异佛尔酮二异氰酸酯与聚醚二醇和聚酯二醇的混合物进行预聚反应,得到预聚物;
将所述预聚物和丁二醇以及二羟甲基丙酸混合进行第一反应,得到第一反应产物;
将所述第一反应产物和丙酮及三乙胺混合进行第二反应,得到所述聚氨酯。
本发明还提供了上述方案所述水性上浆剂的制备方法,包括以下步骤:将改性聚丙烯水性乳液、聚氨酯水性乳液和硅烷偶联剂混合,得到所述水性上浆剂。
本发明还提供了一种上浆方法,采用上浆液对碳纤维/聚丙烯纤维混合毡进行上浆;所述上浆液由上述方案所述水性上浆剂或上述方案所述制备方法得到的水性上浆剂经水稀释得到。
优选的,所述碳纤维/聚丙烯纤维混合毡为碳纤维/聚丙烯纤维针刺毡,所述上浆液的含固率为0.13%~0.15%,所述上浆为喷涂上浆。
优选的,所述碳纤维/聚丙烯纤维针刺毡的克重为250g/mm2~290g/mm2,纤维长度为20mm~70mm。
本发明提供了一种水性上浆剂,包括成膜乳液和硅烷偶联剂;所述成膜乳液与所述硅烷偶联剂的质量比为90:10~95:5;所述成膜乳液包括改性聚丙烯水性乳液和聚氨酯水性乳液;所述改性聚丙烯水性乳液和聚氨酯水性乳液的质量比为75:25~95:5;所述改性聚丙烯水性乳液,以质量分数计,包括以下制备原料:马来酸酐接枝改性聚丙烯20%~25%;乳化剂7%~10%;氨甲基丙醇1%~3%;水62%~72%;所述聚氨酯水性乳液,以质量分数计,包括45%~50%的聚氨酯和50%~55%的水。本发明采用马来酸酐接枝改性聚丙烯和乳化剂制备改性聚丙烯水性乳液,将其作为水性上浆剂的组分,一方面改性聚丙烯具有较高的活性,能够和碳纤维表面的官能团结合,另一方面,上浆剂中的改性聚丙烯和聚丙烯树脂基体之间的相容性更好,从而提高了上浆后的碳纤维和聚丙烯热塑性基体树脂之间的界面结合力。本发明还采用特定含量的聚氨酯水性乳液降低表面能,提高上浆剂对于碳纤维的包覆作用,同时,采用硅烷偶联剂进一步提高碳纤维与聚丙烯树脂基体之间的结合作用。
进一步的,本发明采用异佛尔酮二异氰酸酯(IPDI)为聚氨酯的原料之一,并将聚醚二醇和聚酯二醇作为聚氨酯的软段构成,使制备得到的聚氨酯水性乳液的成膜性更好,更有利于上浆剂对碳纤维表面进行均匀的成膜包覆。
本发明还提供了上述方案所述水性上浆剂的制备方法。本发明提供的制备方法步骤简单,容易操作,容易进行工业化生产。
本发明还提供了一种针对碳纤维/聚丙烯纤维混合毡的上浆方法,采用上浆液对碳纤维/聚丙烯纤维混合毡进行上浆;所述上浆液由上述方案所述上浆剂或上述方案所述制备方法得到的水性上浆剂经水稀释得到。本发明制备得到的上浆剂有利于提高碳纤维/聚丙烯纤维混合毡中碳纤维和聚丙烯基体树脂之间的结合力,且成膜性好,将上浆后的碳纤维/聚丙烯纤维混合毡铺层压制碳纤维/聚丙烯复合材料时,有利于提高碳纤维增强树脂基复合材料的力学性能。
进一步的,本发明采用喷涂上浆的方法可以在不影响碳纤维针刺毡基本物理结构的基础上进行均匀上浆。
附图说明
图1为实施例1中上浆前的碳纤维针刺毡和CF/PP针刺毡透光性对比结果图。
具体实施方式
本发明提供了一种水性上浆剂,组分包括:成膜乳液和硅烷偶联剂;所述成膜乳液与所述硅烷偶联剂的质量比为90:10~95:5;所述成膜乳液包括改性聚丙烯水性乳液和聚氨酯水性乳液;所述改性聚丙烯水性乳液和聚氨酯水性乳液的质量比为75:25~95:5;所述改性聚丙烯水性乳液,以质量分数计,包括以下制备原料:
所述聚氨酯水性乳液,以质量分数计,包括45%~50%的聚氨酯和50%~55%的水。
如无特殊说明,本发明使用的制备原料均为市售。
在本发明中,所述水性上浆剂的组分包括:成膜乳液和硅烷偶联剂;所述成膜乳液与所述硅烷偶联剂的质量比为90:10~95:5,优选为93:7~95:5,更优选为95:5。在本发明中,所述成膜乳液包括改性聚丙烯水性乳液和聚氨酯水性乳液。在本发明中,所述改性聚丙烯水性乳液和聚氨酯水性乳液的质量比为75:25~95:5,优选为80:20~92:8,更优选为85:15~90:10。
在本发明中,所述改性聚丙烯水性乳液,以质量分数计,包括以下制备原料:马来酸酐接枝改性聚丙烯20%~25%;乳化剂7%~10%;氨甲基丙醇1%~3%;水62%~72%。
在本发明中,以质量分数计,所述改性聚丙烯水性乳液的制备原料优选包括马来酸酐接枝改性聚丙烯20%~25%,更优选为23%~25%,进一步优选为25%。在本发明中,所述马来酸酐接枝改性聚丙烯,以质量分数计,优选包括以下制备原料:聚丙烯26~30%;马来酸酐1~3%;苯乙烯1%~3%;引发剂1%~5%;二甲苯0.5~3%;水65%~70%;分散剂0.5%~1%。
在本发明中,以质量分数计,所述马来酸酐接枝改性聚丙烯的制备原料优选包括聚丙烯26%~30%,更优选为27%~28%,进一步优选为27%。在本发明中,所述聚丙烯优选包括聚丙烯料粒,更优选为工业级聚丙烯料粒。
在本发明中,以质量分数计,所述马来酸酐接枝改性聚丙烯的制备原料优选包括马来酸酐1%~3%,更优选为1%~2%,进一步优选为1%。
在本发明中,以质量分数计,所述马来酸酐接枝改性聚丙烯的制备原料优选包括苯乙烯1%~3%,更优选为1%~2%,进一步优选为1%。本发明优选苯乙烯对聚丙烯有一定的润湿和溶胀作用,有利于接枝反应的进行。
在本发明中,以质量分数计,所述马来酸酐接枝改性聚丙烯的制备原料优选包括引发剂1%~5%,更优选为1%~3%,进一步优选为1%~2%,更优选为1%。在本发明中,所述引发剂优选包括过氧化苯甲酰。
在本发明中,以质量分数计,所述马来酸酐接枝改性聚丙烯的制备原料优选包括二甲苯0.5%~3%,更优选为0.5%~2%,进一步优选为0.5%~1%,最优选为0.5%。本发明优选上述含量的二甲苯作为界面剂,有利于接枝反应的进行。
在本发明中,以质量分数计,所述马来酸酐接枝改性聚丙烯的制备原料优选包括水65%~70%,更优选为67%~69%,进一步优选为69%。在本发明中,所述水优选为去离子水。
在本发明中,以质量分数计,所述马来酸酐接枝改性聚丙烯的制备原料优选包括分散剂0.5%~1%,更优选为0.5%。在本发明中,所述分散剂优选包括阴离子型表面活性剂,所述阴离子型表面活性剂优选包括十二烷基苯磺酸钠。
在本发明中,所述马来酸酐接枝改性聚丙烯的制备方法优选包括以下步骤:聚丙烯、马来酸酐、苯乙烯、引发剂、二甲苯、水和分散剂混合,依次进行溶胀和接枝反应,得到所述马来酸酐接枝改性聚丙烯。在本发明中,所述混合优选在室温下进行,所述混合的方式优选为搅拌,所述搅拌的转速优选为380~480r/min,所述搅拌的时间以能够使所述聚丙烯、马来酸酐、苯乙烯、引发剂和二甲苯形成的混合物形成均一溶液即可。在本发明中,所述溶胀的温度优选为65℃~70℃,更优选为66℃~68℃,所述溶胀的时间优选为2h~3h,更优选为2.5h~2.7h。在本发明中,所述接枝反应的温度优选为90℃~100℃,更优选为93℃~98℃,进一步优选为95℃。在本发明中,所述接枝反应的时间优选为5h~8h,更优选为6h~7.5h,进一步优选为7h。本发明优选通过溶胀有利于聚丙烯在水相中发生接枝过程,进而有利于改性后的聚丙烯与碳纤维表面官能团的结合。在本发明中,所述接枝反应后还优选对所述接枝反应得到的体系进行干燥。在本发明中,所述干燥的温度优选为103℃~107℃,更优选为105℃,所述干燥的时间优选为1.8h~2.2h,更优选为2h。本发明优选通过上述反应使改性聚丙烯产物的接枝率达到3%~10%。
在本发明中,以质量分数计,所述改性聚丙烯水性乳液的制备原料优选包括乳化剂7%~10%,更优选为7.5%~9%,进一步优选为8%。在本发明中,所述乳化剂优选包括己基苯磺酸钠、脂肪醇聚氧乙烯醚和异构十醇聚氧乙烯醚中的一种或多种,更优选包括己基苯磺酸钠、脂肪醇聚氧乙烯醚和异构十醇聚氧乙烯醚中的两种或三种。在本发明的具体实施例中,所述乳化剂优选为己基苯磺酸钠和脂肪醇聚氧乙烯醚的混合物,所述己基苯磺酸钠和脂肪醇聚氧乙烯醚的质量比优选为2:1。
在本发明中,以质量分数计,所述改性聚丙烯水性乳液的制备原料优选包括氨甲基丙醇1%~3%,更优选为1.5%~2.5%,进一步优选为2%。本发明优选氨甲基丙醇用于形成表面活性剂,进一步提高上浆剂的成膜性。
在本发明中,以质量分数计,所述改性聚丙烯水性乳液的制备原料优选包括水62%~72%,更优选为63%~68%,进一步优选为65%~67%。在本发明中,所述水优选为去离子水。
在本发明中,所述改性聚丙烯水性乳液的制备方法优选包括以下步骤:将马来酸酐接枝改性聚丙烯、乳化剂、氨甲基丙醇和水进行乳化反应,得到所述改性聚丙烯水性乳液。
在本发明中,所述乳化优选在高压反应釜中进行,所述乳化优选在搅拌条件下进行,所述搅拌的转速优选为750r/min~1000r/min,更优选为780r/min~900r/min,进一步优选为800r/min~850r/min。在本发明中,所述乳化的压力优选为0.2MPa~0.4MPa,更优选为0.3MPa。在本发明中,所述乳化的温度优选为164℃~169℃,更优选为165℃~167℃,所述乳化的时间优选为60min~100min,更优选为65min~80min,进一步优选为70~75min。在本发明中,升至所述乳化的温度的升温速率优选为1.5℃/min~2℃/min,更优选为1.5℃/min。在本发明中,所述乳化结束后优选将所述改性聚丙烯水性乳液的温度降至室温,所述降至室温的速率优选为3~5℃/min,更优选为4℃/min。
在本发明中,所述聚氨酯水性乳液,以质量分数计,包括45%~50%的聚氨酯和50%~55%的水。
在本发明中,以质量分数计,所述聚氨酯水性乳液的制备原料包括聚氨酯45%~50%,更优选为47%~49%,进一步优选为48%。在本发明中,所述聚氨酯,以质量分数计,优选包括以下制备原料:异佛尔酮二异氰酸酯17%~18%;聚醚二醇和聚酯二醇的混合物70%~73%;2,2-二羟甲基丙酸2.7%~2.9%;三乙胺2.5%~2.6%;丁二醇1%~3%;丙酮4%~6%。
在本发明中,以质量分数计,所述聚氨酯的制备原料包括异佛尔酮二异氰酸酯17%~18%,更优选为17%。
在本发明中,以质量分数计,所述聚氨酯的制备原料包括聚醚二醇和聚酯二醇的混合物70%~73%,更优选为70%~71%,进一步优选为70%。在本发明中,所述聚醚二醇和聚酯二醇的质量比优选为3:1~4:1,更优选为4:1。在本发明中,所述聚醚二醇优选包括聚丙二醇,所述聚丙二醇的分子量优选为1500~2500,更优选为2000~2500。在本发明的具体实施例中,所述聚醚二醇优选为PPG-2000。在本发明中,所述聚酯二醇优选包括由丁二酸和己二醇聚合得到的聚酯二醇,所述聚酯二醇的分子量优选为1500~2500,更优选为2000~2500。在本发明的具体实施例中,所述聚酯二醇优选为CMA-2066。
在本发明中,以质量分数计,所述聚氨酯的制备原料包括2,2-二羟甲基丙酸2.7%~2.9%,更优选为2.7%~2.8%,进一步优选为2.8%。
在本发明中,以质量分数计,所述聚氨酯的制备原料包括三乙胺2.5%~2.6%,更优选为2.5%。
在本发明中,以质量分数计,所述聚氨酯的制备原料包括丁二醇1%~3%,更优选为1.5%~2.5%,进一步优选为1.7%~2%。
在本发明中,以质量分数计,所述聚氨酯的制备原料包括丙酮4%~6%,更优选为5%~6%,进一步优选为6%。
在本发明中,以质量分数计,所述聚氨酯水性乳液的制备原料包括水50%~55%,更优选为51%~53%,进一步优选为52%。在本发明中,所述水优选为去离子水。
本发明优选异佛尔酮二异氰酸酯作为原料之一,并采用聚醚二醇和聚酯二醇的组合物作为软段构成,制备得到聚氨酯水性乳液。该水性乳液可以降低表面能,增加上浆剂对碳纤维的浸润效果,有利于提高水性上浆剂在碳纤维上的成膜性。
在本发明中,所述聚氨酯水性乳液的制备方法包括以下步骤:将异佛尔酮二异氰酸酯以及聚醚二醇和聚酯二醇的混合物进行预聚反应,得到预聚物;将所述预聚物和丁二醇以及二羟甲基丙酸混合进行第一反应,得到第一反应产物;将所述第一反应产物和丙酮及三乙胺混合进行第二反应,得到所述聚氨酯体系;将所述聚氨酯体系和水进行乳化,得到所述聚氨酯水性乳液。
本发明将异佛尔酮二异氰酸酯以及聚醚二醇和聚酯二醇的混合物进行预聚反应,得到预聚物。在本发明中,所述预聚反应前还优选包括将所述聚醚二醇和聚酯二醇的混合物进行脱水。在本发明中,所述脱水优选为真空脱水,所述真空脱水优选在氮气气氛下进行,所述真空脱水的温度优选为113℃~115℃,所述真空脱水的时间优选为3.5h~4.5h。在本发明中,所述脱水能够去除混合物中的水分,有利于防止聚醚二醇和聚酯二醇发生水解。在本发明中,所述预聚反应优选包括以下步骤:将所述异佛尔酮二异氰酸酯以及所述聚醚二醇和聚酯二醇的混合物进行混合,之后搅拌升温进行预聚反应。在本发明中,所述混合的温度优选为55℃~60℃,所述预聚反应的温度优选为75℃~85℃,更优选为78℃~82℃,进一步优选为80℃。所述预聚反应的时间优选为1.8h~2.2h,更优选为2h。
得到预聚物后,本发明将所述预聚物和丁二醇以及二羟甲基丙酸混合进行第一反应,得到第一反应产物。在本发明中,所述第一反应的温度优选为73℃~77℃,更优选为75℃,所述第一反应的时间优选为60min~120min,更优选为65~90min。
得到第一反应产物后,本发明优选将所述第一反应产物和丙酮及三乙胺混合进行第二反应,得到所述聚氨酯。本发明优选将第一反应产物的温度降至48℃~52℃时再和丙酮及三乙胺混合进行第二反应。在本发明中,所述丙酮和三乙胺优选通过缓慢滴加的方式与所述第一反应产物进行混合。本发明对所述缓慢滴加的方式没有特别要求,为本领域技术人员熟知的技术手段。在本发明中,所述第二反应的温度优选为48℃~52℃,所述第二反应的时间优选为25min~35min。在本发明中,所述第二反应的时间自所述第一反应产物和丙酮及三乙胺混合完毕时开始计算。
得到所述聚氨酯后,本发明将所述聚氨酯和水进行乳化,得到所述聚氨酯水性乳液。本发明优选将所述聚氨酯体系的温度降至室温再进行乳化。在本发明中,所述乳化的方式优选为高速剪切搅拌,所述高速剪切搅拌的速度优选为16000r/min~18000r/min,所述高速剪切搅拌的时间优选为20min~30min,更优选为25~30min。
本发明对所述硅烷偶联剂的种类没有特别要求,为本领域技术人员所熟知的种类。本发明优选硅烷偶联剂有利于提高碳纤维和聚丙烯树脂之间的结合力。
本发明还提供了上述方案所述水性上浆剂的制备方法,包括以下步骤:将改性聚丙烯水性乳液、聚氨酯水性乳液和硅烷偶联剂混合,得到所述水性上浆剂。本发明优选将改性聚丙烯水性乳液和聚氨酯水性乳液混合,得到成膜乳液,之后向所述成膜乳液中加入硅烷偶联剂混合,得到所述水性上浆剂。本发明优选通过添加硅烷偶联剂能够进一步增加碳纤维与聚丙烯树脂基体的结合作用。
本发明还提供了一种针对碳纤维/聚丙烯纤维混合毡的上浆方法,采用上浆液对碳纤维/聚丙烯纤维混合毡进行上浆;所述上浆液由上述方案所述上浆剂或上述技术方案所述制备方法得到的水性上浆剂经水稀释得到。在本发明中,所述水优选为去离子水。在本发明中,所述碳纤维/聚丙烯纤维混合毡为碳纤维/聚丙烯纤维针刺毡,所述碳纤维/聚丙烯纤维针刺毡的克重优选为250g/mm2~290g/mm2,所述碳纤维/聚丙烯纤维针刺毡的纤维长度优选为20mm~70mm。在本发明中,所述上浆液的含固率优选为0.13%~0.15%,更优选为0.14%。在本发明中,所述上浆后还优选包括将上浆后所得针刺毡进行干燥,所述干燥的温度优选为115℃~120℃,所述上浆的上浆率优选为0.9%~1.5%,更优选为1.0~1.2%。
下面将结合本发明中的实施例,对本发明中的技术方案进行清楚、完整地描述。
实施例1
1)制备马来酸酐接枝改性聚丙烯,以质量分数计,制备原料为:聚丙烯料粒27%、马来酸酐1%、苯乙烯1%、过氧化苯甲酰1%、二甲苯0.5%、去离子水69%、分散剂0.5%,分散剂为十二烷基苯磺酸钠。将上述原料在400r/min的转速下充分混合,在67℃下溶胀2.5h,之后在95℃恒温水浴下接枝反应5h,将接枝反应后的体系在105℃干燥2h,得到马来酸酐接枝改性聚丙烯。
2)制备改性聚丙烯水性乳液,以质量分数计,将1)中得到的马来酸酐接枝改性聚丙烯25%、乳化剂组合物(己基苯磺酸钠和脂肪醇聚氧乙烯醚质量比为2:1)8%、氨甲基丙醇2%以及65%的去离子水加入高压反应釜进行乳化,乳化压力为0.3MPa,乳化在搅拌的条件下进行,搅拌速率为800r/min,乳化时间为70min,乳化温度为165℃,其中升温速率设为1.5℃/min,降温速率为4℃/min,得到改性聚丙烯水性乳液。
3)制备聚氨酯水性乳液:聚氨酯质量分数配比为:异佛尔酮二异氰酸酯(IPDI)17%,多元醇组合物(聚醚二醇:聚酯二醇质量比=4:1)70%,2,2-二羟甲基丙酸2.8%,三乙胺2.5%,丁二醇1.7%,丙酮6%。将上述多元醇组合物投入反应容器中并在115℃下的氮气条件下进行真空脱水4h。脱水后将体系温度降低到55℃时加入IPDI,搅拌后升温至80℃进行预聚反应2h,继续加入丁二醇以及二羟甲基丙酸,并搅拌均匀,在75℃反应65min,之后降温至50℃,此时缓慢滴入丙酮及三乙胺,在50℃下反应30min,之后将得到的产物降温至室温后,逐渐加入去离子水,在高速剪切搅拌(转速为16000r/min,时间30min)的作用下,得到聚氨酯水性乳液,聚氨酯水性乳液中去离子水的质量分数为52%。其中,聚醚二醇的型号为PPG-2000,聚酯二醇的型号为CMA-2066。
4)配制上浆剂,将改性聚丙烯水性乳液和聚氨酯水性乳液按照90:10的质量比进行混合复配,得到成膜乳液,之后向成膜乳液中加入的硅烷偶联剂,硅烷偶联剂为乙烯基硅烷偶联剂,硅烷偶联剂与成膜乳液的质量比为5:95,得到上浆剂。
5)针对碳纤维/聚丙烯纤维(CF/PP)针刺毡上浆:所用碳纤维/聚丙烯纤维针刺毡的克重为260g/mm2,纤维长度为60mm。上浆前将CF/PP针刺毡裁剪成250mm*150mm的尺寸,并在120℃下干燥30min,记录上浆前的克重以及每块针刺毡的质量,计算出针刺毡的质量变化的CV值,以衡量其上浆的均匀性。针对CF/PP针刺毡的物理结构,将4)中得到的上浆剂加入去离子水进行稀释制备得到含固率为0.14%的上浆液。将上浆液加入到喷壶中,采用喷壶对CF/PP针刺毡正反两面进行喷涂,喷涂距离为3~10cm,直至针刺毡被上浆液完全润湿,共喷涂20块纤维针刺毡,每块CF/PP针刺毡的上浆液的平均用量为100mL。将上浆后的针刺毡在120℃下进行干燥处理,干燥处理后,采用相同的方法测量上浆后的克重以及每块针刺毡的质量并测量上浆后CF/PP针刺毡的CV值。
其中,测量并计算得到每块CF/PP针刺毡的平均上浆率为1%,CF/PP针刺毡上浆后的质量增加率为0.95%~1.07%,表明本发明提供的喷涂上浆法的上浆率可控性良好。上浆前,CF/PP针刺毡的透气性(透气性测试参考标准为GB_T5453:1997,每种试样取10个不同的位置进行测试)的CV值的平均值为6.6%,上浆后,CF/PP针刺毡的透气率的CV值的平均值为4.1%,透气性相差不多。同时,CF/PP针刺毡平均克重的CV值的平均值为3.7%。
对上浆前的碳纤维针刺毡和上浆后所得CF/PP针刺毡透光性进行对比,对比结果如图1所示,图1为实施例1中上浆前的碳纤维针刺毡和CF/PP针刺毡透光性对比结果图。图1中上侧三张图为上浆前碳纤维针刺毡的透光性结果,下侧三张图分别对应碳纤维针刺毡上浆后所得的CF/PP针刺毡。从图1中可以看出,采用本发明制备得到的上浆液对碳纤维针刺毡喷涂上浆后,对于碳纤维针刺毡主体的透光性影响较小。从图1和上述透气性的对比结果来看,均未发生上浆液阻塞纤维孔眼等现象,表明本发明采用的喷涂上浆法可以在不影响碳纤维针刺毡基本物理结构的基础上进行均匀上浆。
应用例1
将实施例1制备得到的CF/PP针刺毡采用热压成型制备CF/PP复合材料板材。将8块实施例1制备得到的CF/PP针刺毡沿着相同的方向堆叠。在230℃、5MPa的条件下热压90s,之后在5MPa压强下冷压90s后取出制成厚度为1.8mm的CF/PP复合材料板材。将8块实施例1中上浆前的碳纤维针刺毡采用相同的制备条件得到碳纤维板材,将该碳纤维板材作为对比例,对应用例1制备得到的CF/PP复合材料板材和对比例进行力学性能测试。与对比例相比,应用例1制备得到的CF/PP复合材料板材中碳纤维与聚丙烯树脂间的界面剪切强度提高19%,冲击强度提高了39.06%,拉伸强度提高了22.52%,拉伸模量提高了28.45%。表明本申请制备得到的上浆剂具有良好的上浆效果,能够有效提高上浆剂和碳纤维之间的界面结合力,增加碳纤维聚丙烯复合材料的力学性能。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (9)
1.一种水性上浆剂,其特征在于,包括成膜乳液和硅烷偶联剂;
所述成膜乳液与所述硅烷偶联剂的质量比为90:10~95:5;
所述成膜乳液包括改性聚丙烯水性乳液和聚氨酯水性乳液;所述改性聚丙烯水性乳液和聚氨酯水性乳液的质量比为75:25~95:5;
所述改性聚丙烯水性乳液,以质量分数计,包括:
所述聚氨酯水性乳液,以质量分数计,包括45%~50%的聚氨酯和50%~55%的水;
所述聚氨酯,以质量分数计,包括以下制备原料:
2.根据权利要求1所述的水性上浆剂,其特征在于,所述马来酸酐接枝改性聚丙烯,以质量分数计,包括以下制备原料:
3.根据权利要求2所述的水性上浆剂,其特征在于,所述马来酸酐接枝改性聚丙烯的制备方法包括以下步骤:
将聚丙烯、马来酸酐、苯乙烯、引发剂、二甲苯、水和分散剂混合,依次进行溶胀和接枝反应,得到所述酸酐接枝改性聚丙烯;所述溶胀的温度为65℃~70℃,时间为2h~3h,所述接枝反应的温度为90℃~100℃,时间为5h~8h。
4.根据权利要求1~3任一项所述的水性上浆剂,其特征在于,所述改性聚丙烯水性乳液的制备方法包括以下步骤:将马来酸酐接枝改性聚丙烯、乳化剂、氨甲基丙醇和水进行乳化,得到所述改性聚丙烯水性乳液;所述乳化在搅拌条件下进行,所述搅拌的转速为750r/min~1000r/min,所述乳化的温度为164℃~169℃,时间为60min~100min。
5.根据权利要求4所述的水性上浆剂,其特征在于,所述聚氨酯的制备方法包括以下步骤:
将异佛尔酮二异氰酸酯与聚醚二醇和聚酯二醇的混合物进行预聚反应,得到预聚物;
将所述预聚物和丁二醇以及二羟甲基丙酸混合进行第一反应,得到第一反应产物;
将所述第一反应产物和丙酮及三乙胺混合进行第二反应,得到所述聚氨酯。
6.权利要求1~5任一项所述水性上浆剂的制备方法,其特征在于,包括以下步骤:将改性聚丙烯水性乳液、聚氨酯水性乳液和硅烷偶联剂混合,得到所述水性上浆剂。
7.一种针对碳纤维/聚丙烯纤维混合毡的上浆方法,其特征在于,采用上浆液对碳纤维/聚丙烯纤维混合毡进行上浆;所述上浆液由权利要求1~5任一项所述水性上浆剂或权利要求6所述制备方法得到的水性上浆剂经水稀释得到。
8.根据权利要求7所述的上浆方法,其特征在于,所述碳纤维/聚丙烯纤维混合毡为碳纤维/聚丙烯纤维针刺毡,所述上浆液的含固率为0.13%~0.15%,所述上浆为喷涂上浆。
9.根据权利要求8所述的上浆方法,其特征在于,所述碳纤维/聚丙烯纤维针刺毡的克重为250g/mm2~290g/mm2,纤维长度为20mm~70mm。
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JP2012007280A (ja) * | 2010-05-27 | 2012-01-12 | Teijin Ltd | 炭素繊維束及びその製造方法、ならびにそれからの成形品 |
CN102597360A (zh) * | 2009-09-09 | 2012-07-18 | 三菱丽阳株式会社 | 碳纤维束及其制造方法 |
CN112709071A (zh) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | 聚丙烯-碳纤维复合材料用热塑性乳液上浆剂及其制备方法 |
CN113463393A (zh) * | 2021-08-10 | 2021-10-01 | 长春工业大学 | 一种适用于碳纤维的水性改性氯化聚丙烯上浆剂及其制备方法和应用 |
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CN102597360A (zh) * | 2009-09-09 | 2012-07-18 | 三菱丽阳株式会社 | 碳纤维束及其制造方法 |
JP2012007280A (ja) * | 2010-05-27 | 2012-01-12 | Teijin Ltd | 炭素繊維束及びその製造方法、ならびにそれからの成形品 |
CN112709071A (zh) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | 聚丙烯-碳纤维复合材料用热塑性乳液上浆剂及其制备方法 |
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