CN107956125A - 一种改性乳液碳纤维上浆剂及其制备方法 - Google Patents

一种改性乳液碳纤维上浆剂及其制备方法 Download PDF

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CN107956125A
CN107956125A CN201711162289.7A CN201711162289A CN107956125A CN 107956125 A CN107956125 A CN 107956125A CN 201711162289 A CN201711162289 A CN 201711162289A CN 107956125 A CN107956125 A CN 107956125A
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sizing agent
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阳绪容
王文新
史玉玲
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Changzhou Lanxu Chemical Co Ltd
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Abstract

本发明涉及一种改性乳液碳纤维上浆剂及其制备方法，属于碳纤维生产技术领域。本发明通过碳纳米管表面的羧基与上浆剂中的主浆料发生反应后生成的—C—O键引入纤维表面，提高了纤维的表面活性，有利于纤维与树脂基体间形成化学键合，同时再填充纤维表面沟槽缺陷的同时和纤维成为一体，提高碳纤维拉伸强度，提高了纤维表面的亲水性，有利于环氧树脂对炭纤维表面的吸附和润湿，两者协同作用，共同改善了复合材料的界面性能，从而可增强纤维与基体间的物理锚锭作用，增大纤维表面与基体树脂间的有效接触面积，进而增强碳纤维与树脂之间的机械啮合作用，对界面处的树脂滑移起到一定的限制作用，进而有利于提高复合材料界面粘结性能。

Description

一种改性乳液碳纤维上浆剂及其制备方法
技术领域
本发明涉及一种改性乳液碳纤维上浆剂及其制备方法，属于碳纤维生产技术领域。
背景技术
碳纤维是一种拥有高比模量、优异耐烧蚀性能、高比强度、优良抗疲劳性、低热膨胀系数、强耐腐蚀性的高性能纤维。碳纤维是以沥青基、丙烯腈基、黏胶基等纤维通过预氧化、碳化及石墨化等加工处理过程获得的高含碳量（含碳质量分数大于90%）纤维，作为先进复合材料的增强体被广泛应用于航空航天、体育器材、船舶制造业以及汽车制造业等多个领域。碳纤维的比模量较普通钢铝合金高出 2-5倍，其比强度也较钢铝合金高出3倍多，而它的密度却只有钢材的四分之一左右。因此，碳纤维的广泛使用很大程度上推动了轻量化领域的发展。
由于未处理的碳纤维表面较为平滑且含有极少的极性官能团，这就导致碳纤维与树脂基体的粘合性不佳，从而严重限制了其树脂基复合材料中碳纤维分散应力的。因此，人们通常采用碳纤维表面改性的方法来提高碳纤维的被润湿能力以及其与树脂基体的相容性进而提高二者的界面粘合。
按照制备方法的不同能将上浆剂分为乳液型上浆剂和溶剂型上浆剂。早期的上浆剂以溶剂型为主，溶剂型上浆剂是简单地按一定配比把成膜剂树脂溶解在匹配的溶剂中制得。溶剂型上浆剂的使用存在很大的局限性和危害：（1）溶剂型上浆剂的主要成分是易挥发、有毒性和易燃性的有机溶剂，大量使用不仅有害环境还威胁人们的身体健康。（2）在碳纤维上浆处理环节，由于溶剂易挥发造成成膜剂树脂经常粘附于装置导辊表面，这会在后续上浆过程中严重损害碳纤维表面结构和力学性能。（3）大量地使用有机溶剂会大大提高生产成本。随着人们环保低耗意识的提高，溶剂类上浆剂在国内外几乎已经放弃使用。另一种是乳液型上浆剂，它以树脂作为成膜剂并加入一定量的乳化剂、稀释剂、渗透剂等外加助剂，通过高速机械搅拌而得的乳液。乳液型上浆剂以水为连续相，相当大程度上减少了有机溶剂的使用，具有低成本、低污染及低残留等优点。然而，由于乳化剂这一弱键助剂之使用，会在一定程度上阻碍碳纤维与树脂基体的粘合强度以及复合材料界面耐水性和耐热性。因此，如何在尽量低乳化剂用量条件下制得稳定的上浆剂乳液也成为科研工作者的一个热点研究方向。
发明内容
本发明所要解决的技术问题：针对目前乳化剂的使用阻碍碳纤维及复合材料的粘合强度，耐水性、耐热性能差的问题，提供了一种改性乳液碳纤维上浆剂及其制备方法。
为解决上述技术问题，本发明采用的技术方案是：
一种改性乳液碳纤维上浆剂，包括下述重量份原料：
150～300份环氧树脂，1.5～3.0份复合乳化剂，1.5～3.0份羧基化多壁碳纳米管，50～100份含硅溶胶，500～750份去离子水。
所述环氧树脂为环氧树脂E-51、环氧树脂E-55、环氧树脂E-44、环氧树脂E-20中的一种或多种。
所述复合乳化剂为山梨醇酐单硬脂酸酯、聚氧乙烯脱水山梨醇单油酸酯、十二烷基苯磺酸钠按质量比（6～12）：（10～20）：（5～10）。
所述含硅溶胶为对甲苯磺酸、正硅酸乙酯、甲基三乙氧基硅烷、硅烷偶联剂KH-550、无水乙醇保温反应制得。
所述含硅溶胶各物料重量份为0.3～0.6份对甲苯磺酸，20～40份正硅酸乙酯，5～10份甲基三乙氧基硅烷，15～30份硅烷偶联剂KH-550，800～1600份无水乙醇。
所述保温反应温度为40～50℃。
所述的改性乳液碳纤维上浆剂具体步骤为：
（1）取对甲苯磺酸、正硅酸乙酯、甲基三乙氧基硅烷加入无水乙醇中，搅拌加热至40～50℃，保温反应20～30min，得反应液；
（2）取硅烷偶联剂KH-550加入无水乙醇中搅拌20～30min，再以1～2mL/min滴加入反应液中，持续保温搅拌至滴加完毕，静置1～2h，得含硅溶胶；
（3）将山梨醇酐单硬脂酸酯、聚氧乙烯脱水山梨醇单油酸酯、十二烷基苯磺酸钠按质量比（6～12）：（10～20）：（5～10）混合，得复合乳化剂；
（4）取环氧树脂、复合乳化剂、去离子水，装入乳化机中以800～1200r/min搅拌30～40min，再加入羧基化多壁碳纳米管、含硅溶胶，并以100W超声波超声分散2～3h，超声结束后以800～1200r/min搅拌10～15h，得改性乳液碳纤维上浆剂。
本发明与其他方法相比，有益技术效果是：
本发明通过碳纳米管表面的羧基与上浆剂中的主浆料发生反应后生成的—C—O键引入纤维表面，从而使炭纤维表面含氧活性基团的数量明显增加，炭纤维表面含氧官能团的增加提高了纤维的表面活性，有利于纤维与树脂基体间形成化学键合，同时再在纤维表面形成一层散布有颗粒物的包覆层，颗粒是由硅溶胶缩聚成的二氧化硅形成，填充纤维表面沟槽缺陷的同时和纤维成为一体，提高碳纤维拉伸强度，提高了纤维表面的亲水性，有利于环氧树脂对炭纤维表面的吸附和润湿，两者协同作用，共同改善了复合材料的界面性能，且增加碳纤维比表面积，提高纤维粗糙度，从而可增强纤维与基体间的物理锚锭作用，提高复合材料界面层的载荷传递效率，增大纤维表面与基体树脂间的有效接触面积，从而缓解纤维大缺陷处的应力集中，吸收一定量的脆性断裂能量，改变裂纹扩展方向和路径，进而增强碳纤维与树脂之间的机械啮合作用，对界面处的树脂滑移起到一定的限制作用，进而有利于提高复合材料界面粘结性能。
具体实施方式
取0.3～0.6g对甲苯磺酸，20～40g正硅酸乙酯，5～10g甲基三乙氧基硅烷，加入400～800g无水乙醇中，以300～400r/min搅拌加热至40～50℃，保温反应20～30min，得反应液，取15～30g硅烷偶联剂KH-550，加入400～800g无水乙醇中，以300～400r/min搅拌20～30min，再以1～2mL/min滴加入反应液中，持续保温搅拌至滴加完毕，静置1～2h，得含硅溶胶，取3～6g山梨醇酐单硬脂酸酯，5～10g聚氧乙烯脱水山梨醇单油酸酯，2.5～5.0g十二烷基苯磺酸钠，装入研钵中研磨20～30min，得复合乳化剂，取150～300g环氧树脂，1.5～3.0g复合乳化剂，500～750mL去离子水，装入乳化机中以800～1200r/min搅拌30～40min，再加入1.5～3.0g羧基化多壁碳纳米管，50～100g含硅溶胶，并以100W超声波超声分散2～3h，超声结束后以800～1200r/min搅拌10～15h，得改性乳液碳纤维上浆剂。
实例1
取0.3g对甲苯磺酸，20g正硅酸乙酯，5g甲基三乙氧基硅烷，加入400g无水乙醇中，以300r/min搅拌加热至40℃，保温反应20min，得反应液，取15g硅烷偶联剂KH-550，加入400g无水乙醇中，以300r/min搅拌20min，再以1mL/min滴加入反应液中，持续保温搅拌至滴加完毕，静置1h，得含硅溶胶，取3g山梨醇酐单硬脂酸酯，5g聚氧乙烯脱水山梨醇单油酸酯，2.5g十二烷基苯磺酸钠，装入研钵中研磨20min，得复合乳化剂，取150g环氧树脂，1.5g复合乳化剂，500mL去离子水，装入乳化机中以800r/min搅拌30min，再加入1.5g羧基化多壁碳纳米管，50g含硅溶胶，并以100W超声波超声分散2h，超声结束后以800r/min搅拌10h，得改性乳液碳纤维上浆剂。
实例2
取0.45g对甲苯磺酸，30g正硅酸乙酯，7g甲基三乙氧基硅烷，加入600g无水乙醇中，以350r/min搅拌加热至45℃，保温反应25min，得反应液，取23g硅烷偶联剂KH-550，加入600g无水乙醇中，以350r/min搅拌25min，再以1mL/min滴加入反应液中，持续保温搅拌至滴加完毕，静置1h，得含硅溶胶，取4g山梨醇酐单硬脂酸酯，7g聚氧乙烯脱水山梨醇单油酸酯，3.7g十二烷基苯磺酸钠，装入研钵中研磨25min，得复合乳化剂，取225g环氧树脂，2.3g复合乳化剂，625mL去离子水，装入乳化机中以1000r/min搅拌35min，再加入2.2g羧基化多壁碳纳米管，75g含硅溶胶，并以100W超声波超声分散2h，超声结束后以1000r/min搅拌13h，得改性乳液碳纤维上浆剂。
实例3
取0.6g对甲苯磺酸，40g正硅酸乙酯，10g甲基三乙氧基硅烷，加入800g无水乙醇中，以400r/min搅拌加热至50℃，保温反应30min，得反应液，取30g硅烷偶联剂KH-550，加入800g无水乙醇中，以400r/min搅拌30min，再以2mL/min滴加入反应液中，持续保温搅拌至滴加完毕，静置2h，得含硅溶胶，取6g山梨醇酐单硬脂酸酯，10g聚氧乙烯脱水山梨醇单油酸酯，5.0g十二烷基苯磺酸钠，装入研钵中研磨30min，得复合乳化剂，取300g环氧树脂，3.0g复合乳化剂， 750mL去离子水，装入乳化机中以1200r/min搅拌40min，再加入3.0g羧基化多壁碳纳米管，100g含硅溶胶，并以100W超声波超声分散3h，超声结束后以1200r/min搅拌15h，得改性乳液碳纤维上浆剂。
将本发明制备的水改性乳液碳纤维上浆剂及安徽某公司生产的乳液碳纤维乳化剂进行检测，具体检测结果如下表表1：
表1改性乳液碳纤维上浆剂性能表征
由表1可知本发明制备的改性乳液碳纤维上浆剂，耐热性能大幅度提高，层间剪切强度增大，提高了复合材料界面粘结性能，耐磨次数增大，毛丝量减少，该产品具有最佳的综合性能。本发明制备的改性乳液碳纤维上浆剂具有良好的贮存稳定性和耐热性，其上浆处理的碳纤维后加工性能得到明显提高，碳纤维增强复合材料的界面黏结力也因上浆胶层的嵌入大大改善。

Claims (7)

1.一种改性乳液碳纤维上浆剂，其特征在于，包括下述重量份原料：
150～300份环氧树脂，1.5～3.0份复合乳化剂，1.5～3.0份羧基化多壁碳纳米管，50～100份含硅溶胶，500～750份去离子水。
2.如权利要求1所述的一种改性乳液碳纤维上浆剂，其特征在于，所述环氧树脂为环氧树脂E-51、环氧树脂E-55、环氧树脂E-44、环氧树脂E-20中的一种或多种。
3.如权利要求1所述的一种改性乳液碳纤维上浆剂，其特征在于，所述复合乳化剂为山梨醇酐单硬脂酸酯、聚氧乙烯脱水山梨醇单油酸酯、十二烷基苯磺酸钠按质量比（6～12）：（10～20）：（5～10）。
4.如权利要求1所述的一种改性乳液碳纤维上浆剂，其特征在于，所述含硅溶胶为对甲苯磺酸、正硅酸乙酯、甲基三乙氧基硅烷、硅烷偶联剂KH-550、无水乙醇保温反应制得。
5.如权利要求1所述的一种改性乳液碳纤维上浆剂，其特征在于，所述含硅溶胶各物料重量份为0.3～0.6份对甲苯磺酸，20～40份正硅酸乙酯，5～10份甲基三乙氧基硅烷，15～30份硅烷偶联剂KH-550，800～1600份无水乙醇。
6.如权利要求1所述的一种改性乳液碳纤维上浆剂，其特征在于，所述保温反应温度为40～50℃。
7.如权利要求1～6任一项所述的一种改性乳液碳纤维上浆剂的制备方法，其特征在于，具体步骤为：
（1）取对甲苯磺酸、正硅酸乙酯、甲基三乙氧基硅烷加入无水乙醇中，搅拌加热至40～50℃，保温反应20～30min，得反应液；
（2）取硅烷偶联剂KH-550加入无水乙醇中搅拌20～30min，再以1～2mL/min滴加入反应液中，持续保温搅拌至滴加完毕，静置1～2h，得含硅溶胶；
（3）将山梨醇酐单硬脂酸酯、聚氧乙烯脱水山梨醇单油酸酯、十二烷基苯磺酸钠按质量比（6～12）：（10～20）：（5～10）混合，得复合乳化剂；
（4）取环氧树脂、复合乳化剂、去离子水，装入乳化机中以800～1200r/min搅拌30～40min，再加入羧基化多壁碳纳米管、含硅溶胶，并以100W超声波超声分散2～3h，超声结束后以800～1200r/min搅拌10～15h，得改性乳液碳纤维上浆剂。
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