CN112575589A - 一种高耐磨玻璃纤维布及其制备方法 - Google Patents

一种高耐磨玻璃纤维布及其制备方法 Download PDF

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Publication number
CN112575589A
CN112575589A CN202011457967.4A CN202011457967A CN112575589A CN 112575589 A CN112575589 A CN 112575589A CN 202011457967 A CN202011457967 A CN 202011457967A CN 112575589 A CN112575589 A CN 112575589A
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China
Prior art keywords
parts
glass fiber
fiber cloth
resistant
wear
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Pending
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CN202011457967.4A
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Inventor
周威
杨正喜
但小华
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Jiujiang Xinxing Glass Fiber Material Co ltd
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Jiujiang Xinxing Glass Fiber Material Co ltd
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Priority to CN202011457967.4A priority Critical patent/CN112575589A/zh
Publication of CN112575589A publication Critical patent/CN112575589A/zh
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    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
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Abstract

本发明涉及一种高耐磨玻璃纤维布及其制备方法。包括按重量份计，由以下组分制备而成：玻璃纤维40‑55份、合成树脂4‑8份、氧化锌5‑8份、十二烷基硫酸钠8‑15份、氧化铝1‑3份、邻苯二甲酸二丁酯0.3‑0.5份、聚乙烯醇2‑4份、偶联剂4‑6份、抗氧剂3‑6份、消泡剂5‑8份、空心玻璃珠3‑7份、耐磨微粉5‑10份、抗冲击改质剂1‑5份、耐酸碱改性剂1‑4份、稳定剂0.5‑2份、抗静电剂0.6‑2.5份。本发明选用合理的原料配比，各原料协同作用，有效的改善了玻璃纤维布的整体性能，使其具有较强的防水、耐磨、耐酸碱等特性，机械强度高、稳定性高，增加了玻璃纤维布的使用寿命，降低了使用成本。

Description

一种高耐磨玻璃纤维布及其制备方法
技术领域
本发明涉及玻璃纤维布领域，尤其涉及一种高耐磨玻璃纤维布及其制备方法。
背景技术
玻璃纤维是一种性能优异的无机非金属材料，是非常好的金属替代材料，在建筑、船舶、化工管道、汽车、航空、风力发电等领域有着广阔的应用前景，并且其应用领域仍在不断拓展，全球市场空间巨大。
现有玻璃纤维布种类繁多，具有绝缘性好、耐热性强、抗腐蚀性好和机械强度高等优点。但是，玻璃纤维材料还有一个致命缺点，其耐磨性较差，在长时间使用后容易损坏，这缺点严重影响其使用寿命，导致玻璃纤维布的使用成本高。如何提供一种高耐磨玻璃纤维布及其制备方法是十分重要的。
发明内容
针对现有技术玻璃纤维布本身存在的不足，在实际使用过程中造成的影响，本发明提供一种高耐磨玻璃纤维布及其制备方法，已解决现有技术存在的缺陷。
为实现上述目的，本发明提供的高耐磨玻璃纤维布，包括以下重要成分：
玻璃纤维40-55份、合成树脂4-8份、氧化锌5-8份、十二烷基硫酸钠8-15份、氧化铝1-3份、邻苯二甲酸二丁酯0.3-0.5份、聚乙烯醇2-4份、偶联剂4-6份、抗氧剂3-6份、消泡剂5-8份、空心玻璃珠3-7份、耐磨微粉5-10份、抗冲击改质剂1-5份、耐酸碱改性剂1-4份、稳定剂0.5-2份、抗静电剂0.6-2.5份。
优选地，抗冲击改质剂为氯化聚乙烯。
优选地，所述耐磨微粉由下述原料组成：
白刚玉、玻璃粉、滑石粉、陶瓷粉、石英粉，碳纳米管、碳纤维、聚酰亚胺、纳米二氧化钛、聚四氟乙烯
优选地，所述耐磨微粉由下述原料组成：
白刚玉45-50份、玻璃粉15-25份、滑石粉3-6份、陶瓷粉15-25份、石英粉25-35份，碳纳米管4-8份、碳纤维4-7份、聚酰亚胺3-7份、纳米二氧化钛4-8份、聚四氟乙烯3-7份。
上述耐磨微粉中，白刚玉、玻璃粉、滑石粉、陶瓷粉、石英粉、纳米二氧化钛属于高硬度材料，起骨架抗磨作用；碳纳米管、碳纤维、聚酰亚胺、聚四氟乙烯属于软性耐磨添加剂，主要起到减磨作用，二者耐磨材料的组合使用，可大大提升玻璃纤维布的耐磨性。
优选地，所述耐酸碱改性剂由以下重量份的原料组成：
聚酯树脂20-35份、聚乙烯醇5-10份、丙烯酰胺3-9份、多孔无机硅4-8份、碱式碳酸镁2-5份、碳酸钙3-7份、纳米氧化硅2-6份、纳米氮化硅3-9份、无水乙醇5-15份、丁酸丁酯2-6份、苯甲酸钠3-10份、氢氧化钡4-8份、碳纤维3-7份。
上述耐酸碱改性剂中，多孔无机硅对碱式碳酸镁和碳酸钙有极强的吸附作用，碱式碳酸镁和碳酸钙在玻璃纤维布受酸碱冲击时起缓冲作用，这显著的提高了玻璃纤维布的耐酸碱性。
优选地，所述消泡剂为氨水、辛醇、有机硅类消泡剂的一种或多种。
优选地，所述稳定剂由以下重量份的原料组成：
玻璃球70-80份、二氧化锆10-15份、二氧化钛8-12份、石墨5-10份、碳纤维3-8份。
优选地，所述抗静电剂为单硬脂酸甘油酯。
另一方面，本发明提供一种高耐磨玻璃纤维布的制备方法，所述制备方法包括以下步骤:
S1:玻璃纤维单丝平织，得到基础玻璃纤维布；
S2:将玻璃纤维、合成树脂、氧化锌、十二烷基硫酸钠、氧化铝、邻苯二甲酸二丁酯、聚乙烯醇、偶联剂、抗氧剂、消泡剂、空心玻璃珠、耐磨微粉、抗冲击改质剂、耐酸碱改性剂、稳定剂、抗静电剂置于容器中，加一定量水搅拌，得浆料备用；
S3:将基础玻璃纤维布置于浆料中浸泡一段时间；
S4:将S3中浸泡好的基础玻璃纤维布从浆料中取出，挤压出基础玻璃纤维布中的多余浆料，使用工具排出基础玻璃纤维布内部的气泡，得到预成玻璃纤维布；
S5:以玻璃纤维单丝经平行集束得到原丝，将原丝切割成50～60mm长，并将其随机均匀铺设于预成型玻纤布上，接着涂覆粘结剂，加热固化，得到基材；
S6:在基材的两侧均匀涂覆步骤S1中的浆料，然后将其进行紫外固化，即得产物。
优选地，步骤S6中，紫外固化的处理时间为1.5～2.5h。
优选地，步骤S6中，紫外固化的处理时间为2h。
优选地，步骤S5中，在浸泡处理时，尽量保证基础玻璃纤维布处于平铺状态，使得基础玻璃纤维布与浸泡溶液能够充分的接触，浸泡时温度应为20-30℃。
优选地，步骤S5中，使用的粘接剂为聚氨酯粘接剂、环氧树脂粘接剂、丙烯酸酯粘接剂、有机硅粘接剂的一种或多种。
优选地，步骤S5中，使用的粘接剂为聚氨酯粘接剂。
优选地，步骤S3中基础玻纤布置于浆料中浸渍时间为1.5～2.5h。
优选地，步骤S3中基础玻纤布置于浆料中浸渍时间为2h。
优选地，步骤S2中，使用的偶联剂为酞酸酯类偶联剂、烷基偶联剂类中的任意一种。
优选地，步骤S2中，添加了空心玻璃珠，大大提升了玻璃纤维布的防水性能。
优选地，步骤S1中各原料的具体重量份数如下：
玻璃纤维40-55份、合成树脂4-8份、氧化锌5-8份、十二烷基硫酸钠8-15份、氧化铝1-3份、邻苯二甲酸二丁酯0.3-0.5份、聚乙烯醇2-4份、偶联剂4-6份、抗氧剂3-6份、消泡剂5-8份、空心玻璃珠3-7份、耐磨微粉5-10份、抗冲击改质剂1-5份、耐酸碱改性剂1-4份、稳定剂0.5-2份、抗静电剂0.6-2.5份。
与现有技术相比，本发明的效果和益处在于：
(1)本发明的高耐磨玻璃纤维布，以玻璃纤维单丝平织制成基材，表面涂覆以抗冲击改质剂、耐酸碱改性剂、稳定剂、耐磨微粉等混合的浆料，加热固化制得。制备工艺简单，对设备要求小，可满足工业化生产的要求。
(2)本发明选用合理的原料配比，各原料协同作用，有效的改善了玻璃纤维布的整体性能，使其具有较强的防水、耐磨、耐酸碱等特性，机械强度高、稳定性高，增加了玻璃纤维布的使用寿命，降低了使用成本。
具体实施方式
下面，结合具体实施方式，对本发明做进一步描述，需要说明的是，在不相冲突的前提下，以下描述的各实施例之间或各技术特征之间可以任意组合形成新的实施例。在本发明中，若非特指，所有的份、百分比均为重量单位，所采用的设备和原料等均可从市场购得或是本领域常用的。下述实施例中的方法，如无特别说明，均为本领域的常规方法。
实施例1
一种高耐磨玻璃纤维布，其组分为：
玻璃纤维40份、合成树脂6份、氧化锌6份、十二烷基硫酸钠9份、氧化铝2份、邻苯二甲酸二丁酯0.4份、聚乙烯醇3份、偶联剂5份、抗氧剂4份、消泡剂5份、空心玻璃珠4份、耐磨微粉6份、抗冲击改质剂1份、耐酸碱改性剂1份、稳定剂1份、抗静电剂1份。
实施例2
一种高耐磨玻璃纤维布，其组分为：
玻璃纤维45份、合成树脂8份、氧化锌8份、十二烷基硫酸钠6份、氧化铝3份、邻苯二甲酸二丁酯0.2份、聚乙烯醇3份、偶联剂5份、抗氧剂4份、消泡剂7份、空心玻璃珠5份、耐磨微粉8份、抗冲击改质剂0.8份、耐酸碱改性剂2份、稳定剂1份、抗静电剂1.2份。
实施例3
一种高耐磨玻璃纤维布，其组分为：
玻璃纤维55份、合成树脂10份、氧化锌10份、十二烷基硫酸钠8份、氧化铝3份、邻苯二甲酸二丁酯0.5份、聚乙烯醇4份、偶联剂6份、抗氧剂6份、消泡剂8份、空心玻璃珠5份、耐磨微粉10份、抗冲击改质剂2份、耐酸碱改性剂3份、稳定剂2份、抗静电剂1.5份。
实施例4
一种高耐磨玻璃纤维布，其组分为：
玻璃纤维40份、合成树脂6份、氧化锌6份、十二烷基硫酸钠9份、氧化铝2份、邻苯二甲酸二丁酯0.4份、聚乙烯醇3份、偶联剂5份、抗氧剂4份、消泡剂5份、空心玻璃珠7份、耐磨微粉2份、抗冲击改质剂1份、耐酸碱改性剂1份、稳定剂1份、抗静电剂1份。
实施例5
一种高耐磨玻璃纤维布，其组分为：
玻璃纤维40份、合成树脂6份、氧化锌6份、十二烷基硫酸钠9份、氧化铝2份、邻苯二甲酸二丁酯0.4份、聚乙烯醇3份、偶联剂5份、抗氧剂4份、消泡剂5份、空心玻璃珠1份、耐磨微粉10份、抗冲击改质剂1份、耐酸碱改性剂1份、稳定剂1份、抗静电剂1份。
实施例6
一种高耐磨玻璃纤维布，其组分为：
玻璃纤维40份、合成树脂6份、氧化锌6份、十二烷基硫酸钠9份、氧化铝2份、邻苯二甲酸二丁酯0.4份、聚乙烯醇3份、偶联剂5份、抗氧剂4份、消泡剂5份、空心玻璃珠4份、耐磨微粉6份、抗冲击改质剂1份、耐酸碱改性剂2份、稳定剂2份、抗静电剂1份。
实施例7
一种高耐磨玻璃纤维布，其组分为：
玻璃纤维40份、合成树脂6份、氧化锌6份、十二烷基硫酸钠9份、氧化铝2份、邻苯二甲酸二丁酯0.4份、聚乙烯醇3份、偶联剂5份、抗氧剂4份、消泡剂5份、空心玻璃珠4份、耐磨微粉6份、抗冲击改质剂1份、耐酸碱改性剂4份、稳定剂2份、抗静电剂1份。
实施例8
一种高耐磨玻璃纤维布，其组分为：
玻璃纤维40份、合成树脂6份、氧化锌6份、十二烷基硫酸钠9份、氧化铝2份、邻苯二甲酸二丁酯0.4份、聚乙烯醇3份、偶联剂5份、抗氧剂4份、消泡剂5份、空心玻璃珠1份、耐磨微粉10份、抗冲击改质剂1份、耐酸碱改性剂4份、稳定剂0.5份、抗静电剂1份。
对比例1
一种高耐磨玻璃纤维布，其组分为：
玻璃纤维40份、合成树脂6份、氧化锌6份、十二烷基硫酸钠9份、氧化铝2份、邻苯二甲酸二丁酯0.4份、聚乙烯醇3份、偶联剂5份、抗氧剂4份、消泡剂5份、耐磨微粉6份、抗冲击改质剂1份、耐酸碱改性剂1份、稳定剂1份、抗静电剂1份。
对比例2
一种高耐磨玻璃纤维布，其组分为：
玻璃纤维40份、合成树脂6份、氧化锌6份、十二烷基硫酸钠9份、氧化铝2份、邻苯二甲酸二丁酯0.4份、聚乙烯醇3份、偶联剂5份、抗氧剂4份、消泡剂5份、空心玻璃珠4份、抗冲击改质剂1份、耐酸碱改性剂1份、稳定剂1份、抗静电剂1份。
对比例3
一种高耐磨玻璃纤维布，其组分为：
玻璃纤维40份、合成树脂6份、氧化锌6份、十二烷基硫酸钠9份、氧化铝2份、邻苯二甲酸二丁酯0.4份、聚乙烯醇3份、偶联剂5份、抗氧剂4份、消泡剂5份、空心玻璃珠4份、耐磨微粉6份、抗冲击改质剂1份、稳定剂1份、抗静电剂1份。
对比例4
一种高耐磨玻璃纤维布，其组分为：
玻璃纤维40份、合成树脂6份、氧化锌6份、十二烷基硫酸钠9份、氧化铝2份、邻苯二甲酸二丁酯0.4份、聚乙烯醇3份、偶联剂5份、抗氧剂4份、消泡剂5份、空心玻璃珠4份、耐磨微粉6份、抗冲击改质剂1份、耐酸碱改性剂1份、抗静电剂1份。
测试例
1.力学性能
分别根据GB/T 8805-1988、GB 1697-82、GB/T6739-2006和JIS L1092-2009中的方法对实施例1～4高耐磨玻璃纤维布进行弯曲度、抗冲击强度、硬度、防水性和耐酸碱腐蚀性进行测试，结果见表1。
表1.高耐磨玻璃纤维布的机械性能、耐磨性、防水性测试
弯曲度MPa 抗冲击强度/(Kj/m<sup>2</sup>) 硬度 防水性能(分)
实施例1 669 750 5H 96
实施例2 669 750 5H 96
实施例3 673 778 5H 97
实施例4 670 758 5H 98
实施例5 670 752 5H 88
实施例6 675 780 5H 96
实施例7 675 782 5H 96
实施例8 636 665 5H 87
对比例1 674 780 4H 75
对比例2 671 777 3H 96
对比例3 669 780 4H 96
对比例4 647 658 4H 96
表1中，综合分析实施例1-8及对比例2，由硬度测试结果可以看出，本发明的玻璃纤维具有较高的硬度，反映了其具有优异的耐磨性。
本发明的玻璃纤维布添加了耐磨微粉，其中，耐磨微粉中含有高硬度材料和软性耐磨添加剂。高硬度材料起骨架抗磨作用；软性耐磨添加剂，主要起到减磨作用，二者耐磨材料的组合使用，可大大提升玻璃纤维布的耐磨性。
从实施例1～8可以看出，本发明的玻璃纤维布具有较好弯曲度和抗冲击强度，说明本发明的高耐磨玻璃纤维布具有较好的机械强度。
从实施例1～8及对比例1可以看出，本发明的玻璃纤维布添加了空心玻璃珠，大大提升了玻璃纤维布的防水性能，说明其具有良好的防水性。
2.耐腐蚀性能
参照GB/T 20102-2006公开的方法，对如上各实施例及对比例制耐酸碱腐蚀性进行测试。具体地，测试方法为：
酸液：配制浓度为10％的盐酸溶液置于容器中，密封保存。使实施例1～8及对比例1-5制备的玻璃纤维布能够很好的浸润到盐酸溶液，保持溶液的温度为50℃。在上述条件下浸泡7天后取出，干燥。
碱液：配制浓度为5％的氢氧化钠溶液置于容器中，使实施例1～8及对比例1-5制备的玻璃纤维布能够很好的浸润到氢氧化钠溶液中，保持溶液的温度为50℃。在上述条件下浸泡7天后取出，干燥。
检测经碱液/酸液浸泡处理后的玻璃纤维布的力学性能，并计算强力损耗率。
强力损耗率计算方法如下：
酸性条件下：强力损耗率＝(未经处理纤维布断裂强度-经酸液浸泡后的纤维布断裂强度)/未经处理纤维布力学强度*100％。
碱性条件下：强力损耗率＝(未经处理纤维布断裂强度-经碱液浸泡后的纤维布断裂强度)/未经处理纤维布力学强度*100％。
经测试，本发明制备的玻璃纤维布在浓度为5％的氢氧化钠溶液、浓度为10％的盐酸溶液中，50℃条件下浸泡7天后取出，干燥，不发生力学强度变低的现象。本发明制备的玻璃纤维布中，添加了耐酸碱改性剂，耐酸碱改性剂中含有多孔无机硅和碳酸钙等材料，多孔无机硅对碱式碳酸镁和碳酸钙有极强的吸附作用，碱式碳酸镁和碳酸钙在玻璃纤维布受酸碱冲击时起缓冲作用，这显著的提高了玻璃纤维布的耐酸碱性。说明本发明制备的玻璃纤维布具有良好的耐酸碱腐蚀性能。
本发明选用合理的原料配比，各原料协同作用，有效的改善了玻璃纤维布的整体性能，使其具有较强的防水、耐磨、耐酸碱等特性，机械强度高、稳定性高，增加了玻璃纤维布的使用寿命，降低了使用成本。
本发明的高耐磨玻璃纤维布，以玻璃纤维单丝平织制成基材，表面涂覆以抗冲击改质剂、耐酸碱改性剂、稳定剂、耐磨微粉等混合的浆料，加热固化制得。制备工艺简单，对设备要求小，可满足工业化生产的要求。
本发明通过上述实施例来说明本发明的详细方法，但本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (8)

1.一种高耐磨玻璃纤维布，其特征在于，按重量份计，包括下述组分：
玻璃纤维40-55份、合成树脂4-8份、氧化锌5-8份、十二烷基硫酸钠8-15份、氧化铝1-3份、邻苯二甲酸二丁酯0.3-0.5份、聚乙烯醇2-4份、偶联剂4-6份、抗氧剂3-6份、消泡剂5-8份、空心玻璃珠3-7份、耐磨微粉5-10份、抗冲击改质剂1-5份、耐酸碱改性剂1-4份、稳定剂0.5-2份、抗静电剂0.6-2.5份。
2.根据权利要求1所述的高耐磨玻璃纤维布，其特征在于，所述耐磨微粉由下述原料组成：
白刚玉、玻璃粉、滑石粉、陶瓷粉、石英粉，碳纳米管、碳纤维、聚酰亚胺、纳米二氧化钛、聚四氟乙烯。
3.根据权利要求1所述的高耐磨玻璃纤维布，其特征在于，所述耐酸碱改性剂由以下重量份的原料组成：
聚酯树脂20-35份、聚乙烯醇5-10份、丙烯酰胺3-9份、多孔无机硅4-8份、碱式碳酸镁2-5份、碳酸钙3-7份、纳米氧化硅2-6份、纳米氮化硅3-9份、无水乙醇5-15份、丁酸丁酯2-6份、苯甲酸钠3-10份、氢氧化钡4-8份、碳纤维3-7份。
4.根据要求1所述的高耐磨玻璃纤维布，其特征在于，所述稳定剂由以下重量份的原料组成：
玻璃球70-80份、二氧化锆10-15份、二氧化钛8-12份、石墨5-10份、碳纤维3-8份。
5.一种高耐磨玻璃纤维布的制备方法，其特征在于，采用如下原料：
玻璃纤维、合成树脂、氧化锌、十二烷基硫酸钠、氧化铝、邻苯二甲酸二丁酯、聚乙烯醇、偶联剂、抗氧剂、消泡剂、空心玻璃珠、耐磨微粉、抗冲击改质剂、耐酸碱改性剂、稳定剂、抗静电剂。
6.根据权利要求5所述的一种高耐磨玻璃纤维布的制备方法，其特征在于，包括以下步骤：
S1:玻璃纤维单丝平织，得到基础玻璃纤维布；
S2:将玻璃纤维、合成树脂、氧化锌、十二烷基硫酸钠、氧化铝、邻苯二甲酸二丁酯、聚乙烯醇、偶联剂、抗氧剂、消泡剂、空心玻璃珠、耐磨微粉、抗冲击改质剂、耐酸碱改性剂、稳定剂、抗静电剂置于容器中，加一定量水搅拌，得浆料备用；
S3:将基础玻璃纤维布置于浆料中浸泡一段时间；
S4:将S3中浸泡好的基础玻璃纤维布从浆料中取出，挤压出基础玻璃纤维布中的多余浆料，使用工具排出基础玻璃纤维布内部的气泡，得到预成玻璃纤维布；
S5:以玻璃纤维单丝经平行集束得到原丝，将原丝切割成50～60mm长，并将其均匀铺设于预成型玻纤布上，接着涂覆粘结剂，加热固化，得到基材；
S6:在基材的两侧均匀涂覆步骤S1中的浆料，然后将其进行紫外固化，即得产物。
7.根据权利要求6所述的所述的一种高耐磨玻璃纤维布的制备方法，其特征在于，所述步骤S2中使用的偶联剂为酞酸酯类偶联剂、烷基偶联剂类中的任意一种。
8.根据权利要求7所述的所述的一种高耐磨玻璃纤维布的制备方法，其特征在于，所述步骤S5中使用的粘接剂为聚氨酯粘接剂、环氧树脂粘接剂、丙烯酸酯粘接剂、有机硅粘接剂的一种或多种。
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