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CN112160169A - 环保纤维浸胶液、制备方法及应用 - Google Patents

环保纤维浸胶液、制备方法及应用 Download PDF

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CN112160169A
CN112160169A CN202011056614.3A CN202011056614A CN112160169A CN 112160169 A CN112160169 A CN 112160169A CN 202011056614 A CN202011056614 A CN 202011056614A CN 112160169 A CN112160169 A CN 112160169A
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dipping solution
fiber dipping
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王文才
张博
田明
张立群
温世鹏
宁南英
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Abstract

本发明属于化学纤维加工领域，提供了一种环保纤维浸胶液、制备方法及应用。本发明是在酚胺水溶液中，添加一定比例的改性纳米填料和橡胶胶乳混合制备而成的环保纤维浸胶液。本发明所提供的环保纤维浸胶液能够代替传统RFL浸胶体系，保证满足纤维与橡胶基体之间的界面具有粘合性能的前提下，不使用有毒原材料和中间体，减少对人体和环境的危害，该环保纤维浸胶液的制备方法，操作简单，有利于工业化应用。本发明的制备方法适用于制备纤维浸胶液，尤其适用于制备环保纤维浸胶液，所得环保纤维浸胶液用作化学纤维浸渍体系过程中的二浴浸胶液。

Description

环保纤维浸胶液、制备方法及应用
技术领域
本发明属于化纤改性领域，涉及一种浸胶液、制备方法及应用,具体地说是一种环保纤维浸胶液、制备方法及应用。
背景技术
现有技术中纤维/橡胶复合材料是由增强纤维骨架材料和橡胶基体组合而成，其中橡胶良好的弹性用来承受复合材料受力时产生的大变形，而纤维骨架材料因其较高的强度和刚度用来抵抗应力对复合材料产生的破坏。纤维/橡胶复合材料广泛用于高速高载汽车/飞机轮胎、抗高压特种胶管和高强力特种橡胶输送带等领域。纤维与橡胶之间的界面粘合性能是决定高性能纤维增强发挥应力传递效率的关键，因此两者之间粘合性能的好坏，直接关系到橡胶制品在使用过程中的安全性和使用寿命。
在橡胶工业生产中，为了在纤维和橡胶基体之间进行粘合，最常用的处理手段就是对纤维骨架材料进行传统的间苯二酚-甲醛-胶乳（RFL）浸渍处理。虽然RFL浸渍技术已经相当的成熟且具有较低的生产成本，但是面对日益苛刻的环境保护迫切需求，发展纤维新型环保浸渍处理技术，替代工业上广泛使用的、有毒有害的间苯二酚-甲醛-胶乳（RFL）浸渍技术迫在眉捷。甲醛在2009年被国际癌症研究中心列为导致白血病的化学品之一。近几年，国内外就纤维骨架材料浸胶体系的去间苯二酚和甲醛化的研究进行了大量的报道。
美国专利2015/0314644 A1公开了一种由橡胶胶乳、环氧化合物和主链为聚醚型多胺组成的粘合体系。该粘合体系克服了胺对体系稳定性的影响。粘合体系中不含有有害的间苯二酚和甲醛等成分，且经该粘合体系处理后的纤维与橡胶之间的粘合强度达到了RFL浸胶处理的粘合水平。
美国专利US4472463公开了一种丙烯酸树脂-胶乳体系，用于非活化的聚酯纤维二浴浸渍处理。先由一种或两种丙烯酸类单体与少量苯乙烯共聚制得丙烯酸树脂，用此丙烯酸树脂与胶乳混合制得浸胶配方。用于非活化的聚酯纤维时，需要经过传统的一浴环氧化合物和/或封闭型异氰酸酯对纤维进行活化，再采用新型的丙烯酸树脂-胶乳体系进行二浴浸渍处理，其处理的纤维与橡胶之间的H抽出力略高于RFL浸渍的纤维。
美国专利US 2015/0259560A1公开了一种由丙烯酸树脂、环氧化合物、多异氰酸酯和胶乳组成的纤维骨架材料浸渍处理配方。该配方用于提高合成纤维和橡胶之间粘合性，而且该配方组成是环保无毒的。经该配方处理的纤维与橡胶之间的粘合效果能达到传统RFL处理的水平。
发明内容
为解决现有技术中存在的以上不足，本发明旨在提供一种环保纤维浸胶液、制备方法及应用，以保证在满足纤维与橡胶基体之间的界面粘合性能的前提下，有效地替代传统RFL浸胶体系，不使用有毒原材料和中间体，减少对人体和环境的危害。
为实现上述目的，本发明所采用的技术方案如下：
一种环保纤维浸胶液，所述环保纤维浸胶液的有效成分为酚胺水溶液、改性纳米填料粗品和橡胶胶乳按照质量比为1:0.1~10:1~1000混合而成；
作为本发明的限定，所述酚胺水溶液为多酚类化合物、多胺类化合物及水按照质量比为1:0.1~10:10~200混合而成；
作为本发明的另一种限定，所述改性纳米填料粗品为硅烷偶联剂和纳米填料按照质量比为1:10~30混合而成；
作为本发明的第三种限定，所述改性纳米填料粗品：多酚化合物和多胺化合物总量的质量比为1:0.1~10；所述环保纤维浸胶液中的改性纳米填料粗品与橡胶胶乳的质量比为1:10~100；
作为本发明的第四种限定，所述多酚类化合物为邻苯二酚、邻苯三酚、没食子酸、单宁酸、茶多酚、儿茶素及花青素中的至少一种；
所述多胺类化合物为二乙烯三胺、二丙烯三胺、辛二胺、多乙烯多胺、三乙烯四胺、四乙烯五胺、五乙烯六胺、聚乙烯亚胺及聚醚胺中的至少一种；
作为本发明的第五种限定，所述橡胶胶乳为丁苯胶乳、丁苯吡胶乳、羧基丁苯胶乳、羧基丁腈胶乳、氯磺化聚乙烯胶乳、氯丁胶乳、乙烯基吡啶胶乳、丁腈胶乳及氢化丁腈胶乳中的至少一种；
作为本发明的第六种限定，所述硅烷偶联剂为乙烯基三氯硅烷、乙烯基三乙氧基硅烷、乙烯基甲基二氯硅烷、γ-氨丙基三乙氧基硅烷、γ-氨丙基三甲氧基硅烷、γ-（2,3-环氧丙氧）丙基三甲氧基硅烷、γ-（2,3-环氧丙氧）丙基三乙氧基硅烷、γ-甲基丙烯酰氧丙基三氯硅烷、γ-甲基丙烯酰氧丙基甲基二甲氧基硅烷、γ-巯丙基三甲氧基硅烷及双-[γ-(三乙氧基硅)丙基]四硫化物中的至少一种；
所述纳米填料为白炭黑、炭黑、凹凸棒土、埃洛石、蒙脱土、氧化石墨烯、针状硅酸盐及纳米纤维素中的至少一种；
本发明还提供环保纤维浸胶液的一种制备方法，其制备方法包括以下步骤：
1）取硅烷基偶联剂和纳米填料，混匀后，经加热反应，得改性纳米填料粗品A；
2）取多酚类化合物和多胺类化合物加至水中混合均匀，调节pH至碱性，制得酚胺水溶液B；
3）酚胺水溶液B中加入改性纳米填料粗品A和橡胶胶乳，混匀，即得环保纤维浸胶液C；
作为本发明的所提供的制备方法的限定，所述pH的范围为8~12；
所述加热温度为100~180℃，其中，如果温度过低，则反应不能充分进行，使得纳米填料的改性效果变差；如温度过高，则会造成硅烷偶联剂的分解，不能有效增加纳米填料的表面活性基团，从而影响界面粘合性能；
所述加热反应时间为20~110min；
本发明还提供了一种环保纤维浸胶液的一种应用，所述环保纤维浸胶液作为纤维浸胶过程中的二浴浸胶液，以代替传统RFL浸胶体系，不使用有毒原材料和中间体，增强纤维与橡胶基体之间的粘合性能，减少对人体和环境的危害。
由于采用了上述的技术方案，本发明与现有技术相比，所取得的有益效果是：
（1）本发明所提供的环保纤维浸胶液不含有间苯二酚和甲醛，大幅度减少了对环境和人体的危害；
（2）本发明所提供的环保纤维浸胶液，其中含有的改性纳米填料具有增强纤维与橡胶基体间的界面粘合力的作用；
（3）本发明所提供的环保纤维浸胶液中含有的多酚类化合物和多胺类化合物，在碱性环境下形成网络结构，一方面使其中的极性基团与纤维发生反应，另一方面橡胶胶乳粒子在网络结构中参与橡胶基体共硫化，从而提高纤维材料和橡胶之间的粘合性能；
（4）本发明所提供的环保纤维浸胶液在制备过程中将多酚和多胺混合液调节至碱性，而对于橡胶胶乳在碱性环境中能够保持稳定状态，因此在室温条件下即使长期放置，粘度不会大幅增加，有利于纤维浸渍生产过程中的长期储存，有利于工业化应用；
（5）本发明所提供的环保纤维浸胶液的制备方法，操作简单，制备时间短，具有较高的使用价值，其推广使用能带来较大的经济效益和社会效益；
综上所述，本发明所提供的环保纤维浸胶液能够保证满足纤维与橡胶基体之间的界面粘合性能的前提下，有效地替代传统RFL浸胶体系中有毒原材料和中间体的使用，减少对人体和环境的危害，该环保纤维浸胶液的制备方法，操作简单，有利于工业化应用。
本发明适用于环保纤维浸胶液的制备，用于替代传统RFL浸胶体系中有毒原材料和中间体，减少对人体和环境的危害，同时，提高纤维材料与橡胶基体之间的界面粘合性能。
具体实施方式
以下结合优选实施例对本发明进行说明。应当理解，此处所描述的优选实施例仅用于说明和理解本发明，并不用于限定本发明。
实施例1 一种环保纤维浸胶液C1的制备方法
本实施例提供一种环保纤维浸胶液的制备方法，该方法如下步骤：
1）称取5gγ-巯丙基三甲氧基硅烷与100g白炭黑利用高速搅拌机混合均匀，随后在120℃烘箱中热处理30min，得改性白炭黑粗品A1;
2）称取200g单宁酸与200g聚醚胺，加入到4600g水中，混合均匀，调节pH为10.0，搅拌60min后，得酚胺水溶液B1；
3）向酚胺水溶液B1中分别加入改性白炭黑粗品A1和5250g丁苯吡胶乳，搅拌60min,即得环保纤维浸胶液C1。
实施例2~11 环保纤维浸胶液C2~C11的制备方法
本实施例2~11分别提供一种环保限位浸胶液的制备方法，该制备方法与实施例1中的制备方法基本相同，其区别仅在于所用原料、原料的用量以及部分相关工艺参数的不同，具体见表1。
表1 制备环保纤维浸胶液C2~C11的工艺参数一览表
Figure DEST_PATH_IMAGE001
Figure 948376DEST_PATH_IMAGE002
Figure DEST_PATH_IMAGE003
实施例2~11其它部分的内容，与实施例1相同。
实施例12 环保纤维浸胶液C1~C11的应用对比
本实施例采用二浴浸胶法，对芳纶纤维（1500D/2，初复捻度均为300T/m）进行浸渍处理处理，截取12段相同长度的化学纤维，随机选取一段作为对照例D，其他化学纤维分别作为实验例E1~E11，并对它们进行浸渍处理，所用的一浴浸胶液均为由封闭异氰酸酯和环氧树脂配制成的一浴浸胶液。将经过一浴浸渍过的对比例D，使用传统RFL浸胶液进行二浴浸渍处理；将经过一浴浸渍过的实验例E1~E11一一对应使用实施例1~11所制备的环保纤维浸胶液C1~C11进行二浴浸渍处理。
对实验例E1~E11和对比例D进行H抽出测试，H抽出力测试按国家标准GB/T 2942~2009中的方法来进行测试。制备H抽出力测试试样所使用的标准橡胶配方如下所示（按重量份计）：天然橡胶（烟片胶） 90份，丁苯橡胶（SBR 1500） 10份，炭黑N330 35份，间接法氧化锌（一级） 8份，硫磺 2.5份，硫化促进剂DM（优等品） 1.2份，硬脂酸（200型，一级） 2份，硫化促进剂 TMTD（优等品） 0.03份，粘合剂A 0.8份，粘合剂RS 0.96份。H抽出试样制备时所使用的硫化温度为150±2℃，硫化模具压力为3.0~5.0MPa，硫化时间为20min，测定结果如表2所示。
表2 化学纤维的H抽出力测定数据表
Figure 537620DEST_PATH_IMAGE004
由表2可知，化学纤维经过以上不同实验例处理后，仅有实验例E1和实验例E6的H抽出力低于对比例D，其余实验例均比对比例D高，且最高抽出力的实验例E10相比对比例D的H抽出力提高33.7%。这说明本发明能明显提高化学纤维与橡胶基体的粘合力，而且发明制备的浸胶液在不改变任何粘合及物理性能的情况下，能够替代含有污染和致癌的间苯二酚、甲醛有害物质的RFL浸胶液配方在化学纤维的二浴浸胶体系中使用。结果证明，本发明制备的浸胶液能够提升纤维骨架材料与橡胶的粘合性能，能够达到传统的间苯二酚-甲醛-胶乳(RFL)浸胶体系的粘合效果，且绿色无污染。足以证明，本发明所提供的环保纤维浸胶液，在改善传统RFL浸胶液对人体和环境危害的同时，可以进一步提高被本发明提供的环保纤维浸胶液浸渍处理过的化学纤维的界面粘合能力。
本实施例除了可以对芳纶纤维进行浸渍处理，还可以对多种化学纤维进行处理，如聚酯纤维、尼龙纤维和聚酰亚胺纤维等，实验所得结果与本实施例相同。
需要说明的是，以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照上述实施例对本发明进行了详细的说明，对于本领域技术人员来说，其依然可以对上述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

1.一种环保纤维浸胶液，其特征在于：所述环保纤维浸胶液的有效成分为酚胺水溶液、改性纳米填料粗品和橡胶胶乳按照质量比为1:0.1~10:1~1000混合而成。
2.根据权利要求1所述环保纤维浸胶液，其特征在于：所述酚胺水溶液为多酚类化合物、多胺类化合物和水按照质量比为1:0.1~10:10~200混合而成。
3.根据权利要求1所述环保纤维浸胶液，其特征在于：所述改性纳米填料粗品为硅烷偶联剂和纳米填料按照质量比为1:10~30混合而成。
4.根据权利要求1~3中任意一项所述环保纤维浸胶液，其特征在于：所述改性纳米填料粗品：多酚化合物和多胺化合物总量的质量比为1:0.1~10；所述改性纳米填料粗品与橡胶胶乳的质量比为1:10~100。
5.根据权利要求2所述环保纤维浸胶液，其特征在于：所述多酚类化合物为邻苯二酚、邻苯三酚、没食子酸、单宁酸、茶多酚、儿茶素及花青素中的至少一种；
所述多胺类化合物为二乙烯三胺、二丙烯三胺、辛二胺、多乙烯多胺、三乙烯四胺、四乙烯五胺、五乙烯六胺、聚乙烯亚胺及聚醚胺中的至少一种。
6.根据权利要求3所述环保纤维浸胶液，其特征在于：所述硅烷偶联剂为乙烯基三氯硅烷、乙烯基三乙氧基硅烷、乙烯基甲基二氯硅烷、γ-氨丙基三乙氧基硅烷、γ-氨丙基三甲氧基硅烷、γ-（2,3-环氧丙氧）丙基三甲氧基硅烷、γ-（2,3-环氧丙氧）丙基三乙氧基硅烷、γ-甲基丙烯酰氧丙基三氯硅烷、γ-甲基丙烯酰氧丙基甲基二甲氧基硅烷、γ-巯丙基三甲氧基硅烷及双-[γ-(三乙氧基硅)丙基]四硫化物中的至少一种;
所述纳米填料为白炭黑、炭黑、凹凸棒土、埃洛石、蒙脱土、氧化石墨烯、针状硅酸盐及纳米纤维素中的至少一种。
7.根据权利要4所述环保纤维浸胶液，其特征在于：所述橡胶胶乳为丁苯胶乳、丁苯吡胶乳、羧基丁苯胶乳、羧基丁腈胶乳、氯磺化聚乙烯胶乳、氯丁胶乳、乙烯基吡啶胶乳、丁腈胶乳及氢化丁腈胶乳中的至少一种。
8.根据权利要求1~7中任意一项所述环保纤维浸胶液的一种制备方法，其特征在于：所述制备方法还包括以下步骤：
1）取硅烷基偶联剂和纳米填料，混匀后，经加热反应，得改性纳米填料粗品A；
2）取多酚类化合物和多胺类化合物加入水中混匀，调节pH至碱性，制得酚胺水溶液B；
3）酚胺水溶液B中加入改性纳米填料粗品A和橡胶胶乳，混匀，即得环保纤维浸胶液C。
9.根据权利要求8所述环保纤维浸胶液的制备方法，其特征在于：所述加热反应的温度为100~180℃、时间为20~110min；所述pH值为8~12。
10.根据权利要求1~7中任意一项所述环保纤维浸胶液的一种应用，其特征在于：所述环保纤维浸胶液作为纤维浸胶过程中的二浴浸胶液。
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