CN106349976A - 一种钢丝网增强聚乙烯热水管用粘接树脂及其制备方法 - Google Patents
一种钢丝网增强聚乙烯热水管用粘接树脂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种钢丝网增强聚乙烯热水管用粘接树脂，所述粘接树脂是由重量百分含量的以下组分组成：聚乙烯接枝物5‑50％；聚乙烯基体树脂20‑80％；耐热增强粒子5‑60％；弹性体增韧粒子1‑30％；上述各组分总的百分含量为100％。本发明还公开了粘接树脂的制备方法。本发明制备的粘接树脂耐热性能好，对钢丝粘接效果优异，维卡软化点达到120℃以上，热变形温度达到95℃以上，85℃高温剥离强度达到100N/cm以上。
Description
技术领域
本发明属于材料组合物制备技术领域，特别是涉及一种钢丝网增强聚乙烯热水管用粘接树脂及其制备方法。
背景技术
钢丝网增强聚乙烯复合管是十余年来发展迅速的一种增强热塑性塑料管(RTP)，具有承压力强、线性膨胀系数低、耐腐蚀、不结垢、重量轻、环保无毒等特点。钢丝网增强聚乙烯复合管兼具了热塑性塑料和金属增强层的各自优点，在性能上达到了塑料和金属材料的优势互补，广泛应用于市政、化工、消防等领域。通过长期且广泛的市场应用案例表明，钢丝网增强聚乙烯复合管是一种性能优异且得到市场认可的增强热塑性塑料管。目前，钢丝网增强聚乙烯复合管主要在冷水管领域应用，在热水管领域的应用未见报道及应用实例。
粘接树脂作为连接钢丝和内外层聚乙烯管材的关键原材料，其性能优劣直接影响到钢丝网增强聚乙烯复合管的品质。围绕钢丝网增强聚乙烯复合管的耐热水性能，通过对粘接树脂组成进行优化。耐热增强粒子的加入对提高高分子材料力学强度和耐热性能具有明显效果，同时存在粘接强度降低、柔韧性降低、扯断伸长率偏低等负面影响。在粘接树脂中复配经过处理过的耐热增强粒子及弹性体增韧粒子，在不影响粘接树脂粘接性能及柔韧性的前提下提高材料的耐热性，制备出钢丝网增强聚乙烯热水管专用粘接树脂。该粘接树脂能够改善复合管粘接界面的耐热性能，促进复合管在热水输送领域的应用，复合管能够通过高温高压静液压强度试验。
中国专利CN102161730A介绍了一种钢丝骨架增强聚乙烯管材专用粘接树脂，由高密度聚乙烯/线性聚乙烯/马来酸酐/过氧化物等组成，制得的粘接树脂可用于钢丝骨架增强聚乙烯管材，管材剥离强度能够达到500N/25mm以上。中国专利CN102181246A介绍了一种耐热性热熔胶及其制备方法和应用，由聚乙烯接枝马来酸酐、石油树脂、高熔点复合蜡、PE-RT、碳酸钙等组成，可用于输送热水的PE-RT类钢丝网骨架复合管。
但上述专利均未提到如何提高粘接树脂的耐热性，也未提及粘接树脂的热变性温度、高温剥离强度、复合管材的静液压强度等性能提升情况及对热水输送的影响，也未提及弹性体增韧粒子在粘接树脂组分中起到的作用及对复合管材性能的影响。
发明内容
为了克服现有技术的不足，本发明的目的之一在于提供一种钢丝网增强聚乙烯热水管用粘接树脂，该产品耐热性能非常优异，维卡软化点达到120℃以上，热变形温度达到95℃以上，85℃高温剥离强度达到100N/cm以上。
本发明的目的之二在于提供一种粘接树脂的制备方法，该方法采用双螺杆挤出工艺完成反应挤出及共混造粒，采用耐热增强粒子提高产品耐热性及热水输送性能，采用弹性体增韧粒子提高产品柔韧性及扯断伸长率，采用聚乙烯接枝物及聚乙烯基体树脂的优化选择提高产品的粘接性能。
本发明的目的之一采用以下技术方案实现：
一种钢丝网增强聚乙烯热水管用粘接树脂，其特征是，所述粘接树脂是由重量百分含量的以下组分组成：
上述各组分总的百分含量为100％。
优选的，所述粘接树脂是由重量百分含量的以下组分组成：
聚乙烯接枝物主要起到增加粘接树脂与钢丝剥离强度的效果，所述聚乙烯接枝物用量低于8wt％时粘接树脂对钢丝粘接强度不足，用量高于40wt％时对粘接树脂热稳定性有影响；聚乙烯基体树脂主要起到提高粘接树脂与聚乙烯材料剥离强度的作用，同时能够提高粘接树脂耐热性，所述聚乙烯基体树脂用量低于30wt％时与聚乙烯粘接效果减弱且耐热性变差，用量高于65wt％影响与金属粘接效果；所述弹性体增韧粒子主要起到提高粘接树脂柔韧性及扯断伸长率的作用，用量低于3wt％粘接树脂柔韧性变差，扯断伸长率偏低，用量高于25wt％时粘接树脂耐热性变差。
优选的，所述粘接树脂是由重量百分含量的以下组分组成：
优选的，所述耐热增强粒子为有机晶须、无机晶须、连续纤维、短纤维、云母中的一种或两种及以上的混合物。耐热增强粒子在加入所述组分前可根据具体要求及要达到的效果通过硬脂酸、硬脂酸钠、硅烷偶联剂等助剂进行预处理，以达到耐热增强粒子与产品中其它组分充分融合之目的。
优选的，所述聚乙烯接枝物为聚乙烯接枝甲基丙烯酸缩水甘油酯(PE-g-GMA)、聚乙烯接枝马来酸酐(PE-g-MAH)、高密度聚乙烯接枝丙烯酸丁酯(PE-g-BA)、丙烯酸接枝聚乙烯(PE-g-AA)中的一种或两种及以上的混合物。该聚乙烯接枝物种的聚乙烯优选高密度聚乙烯。
优选的，所述聚乙烯基体树脂为交联聚乙烯、超高分子量聚乙烯、耐热聚乙烯、线性低密度聚乙烯、中密度聚乙烯、低密度聚乙烯、茂金属聚乙烯中的一种或两种及以上的混合物。
优选的，所述弹性体增韧粒子为EVA、EPDM、EPR、EEA、EBA、POE、POP中的一种或两种及以上的共混物。
优选的，所述粘接树脂的维卡软化点≥120℃，热变形温度≥95℃。
本发明的目的之二采用以下技术方案实现：
一种制备钢丝网增强聚乙烯热水管用粘接树脂的方法，其特征是，将所述聚乙烯接枝物、聚乙烯基体树脂、耐热增强粒子、弹性体增韧粒子按配方量加入高混机预混，在经过双螺杆挤出机混炼得到粘接树脂颗粒。在制备过程中，可以根据产品需要添加少量抗氧剂、无机纳米碳酸钙、紫外线吸收剂等助剂，或添加色粉、色母、少许加工助剂等，用以改善粘接树脂色泽、防腐、防紫外和抗氧化性能。
优选地，所述双螺杆挤出机的挤出机温度为230℃，螺杆转速为300rpm，喂料为7Hz，双螺杆长径比L/D＝40:1。
相比现有技术，本发明的有益效果在于：
本发明制备的粘接树脂耐热性能好，对钢丝粘接效果优异，维卡软化点达到120℃以上，热变形温度达到95℃以上，85℃高温剥离强度达到100N/cm以上。采用该粘接树脂制备的钢丝网增强聚乙烯管典型特点为耐热性能优良，高温粘接强度优异，能够通过高温高压条件下的静液压强度试验，能够应用于热水输送领域。
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：
下述实施例中的HDPE-g-GMA、HDPE-g-BA和HDPE-g-GMA均为广州鹿山新材料股份有限公司所生产的；YEM-4705T为中国石化扬子石油化工有限公司所生产的；EBA 3107AC购买自Dupont公司；EPDM 8600购买自Exxonmobil公司；DGDA-2399购买自DOW公司。
一种钢丝网增强聚乙烯热水管用粘接树脂，所述粘接树脂是由重量百分含量的以下组分组成：
上述各组分总的百分含量为100％。
制备上述粘接树脂的方法是：将上述配方量的聚乙烯接枝物、聚乙烯基体树脂、耐热增强粒子、弹性体增韧粒子通过高混机预混，经过双螺杆挤出机混炼得到粘接树脂颗粒，挤出造粒时挤出机温度为230℃，螺杆转速300rpm，喂料7Hz，双螺杆长径比L/D＝40:1。
实施例1
粘接树脂配方(100％)如下：聚乙烯接枝物12％；聚乙烯基体树脂65％；耐热增强粒子20％；弹性体增韧粒子3％。
其中，聚乙烯接枝物为HDPE-g-GMA，聚乙烯基体树脂由重量比为3：2的DOW DGDA-2399和YEM-4705T配制而成，耐热增强粒子为SiC晶须，弹性体增韧粒子为EBA 3107AC。
实施例2
粘接树脂配方(100％)如下：聚乙烯接枝物36％；聚乙烯基体树脂45％；耐热增强粒子14％；弹性体增韧粒子5％。
其中，聚乙烯接枝物为HDPE-g-BA，聚乙烯基体树脂为DOW DGDA-2399，耐热增强粒子为SiC晶须，弹性体增韧粒子为EPDM 8600。
实施例3
粘接树脂配方(100％)如下：聚乙烯接枝物12％；聚乙烯基体树脂65％；耐热增强粒子20％；弹性体增韧粒子3％。
其中，聚乙烯接枝物为HDPE-g-GMA，聚乙烯基体树脂为DGDA-2399，耐热增强粒子为连续涤纶纤维，弹性体增韧粒子为EPDM 8600。
将上述实施例1-3按照本发明中的要求制备成粘接树脂粒料，其性能下表及制备出的钢丝网增强聚乙烯热水管的性能见下表1。
表1性能检测结果
对本领域的技术人员来说，可根据以上描述的技术方案以及构思，做出其它各种相应的改变以及形变，而所有的这些改变以及形变都应该属于本发明权利要求的保护范围之内。
Claims (10)
1.一种钢丝网增强聚乙烯热水管用粘接树脂，其特征是，所述粘接树脂是由重量百分含量的以下组分组成：
上述各组分总的百分含量为100％。
2.根据权利要求1所述的钢丝网增强聚乙烯热水管用粘接树脂，其特征是，所述粘接树脂是由重量百分含量的以下组分组成：
3.根据权利要求1所述的钢丝网增强聚乙烯热水管用粘接树脂，其特征是，所述粘接树脂是由重量百分含量的以下组分组成：
4.根据权利要求1所述的钢丝网增强聚乙烯热水管用粘接树脂，其特征是，所述耐热增强粒子为有机晶须、无机晶须、连续纤维、短纤维、云母中的一种或两种及以上的混合物。
5.根据权利要求1所述的钢丝网增强聚乙烯热水管用粘接树脂，其特征是，所述聚乙烯接枝物为PE-g-GMA、PE-g-MAH、PE-g-BA、PE-g-AA中的一种或两种及以上的混合物。
6.根据权利要求1所述的钢丝网增强聚乙烯热水管用粘接树脂，其特征是，所述聚乙烯基体树脂为交联聚乙烯、超高分子量聚乙烯、耐热聚乙烯、线性低密度聚乙烯、中密度聚乙烯、低密度聚乙烯、茂金属聚乙烯中的一种或两种及以上的混合物。
7.根据权利要求1所述的钢丝网增强聚乙烯热水管用粘接树脂，其特征是，所述弹性体增韧粒子为EVA、EPDM、EPR、EEA、EBA、POE、POP中的一种或两种及以上的共混物。
8.根据权利要求1所述的钢丝网增强聚乙烯热水管用粘接树脂，其特征是，所述粘接树脂的维卡软化点≥120℃，热变形温度≥95℃。
9.一种制备权利要求1所述的钢丝网增强聚乙烯热水管用粘接树脂的方法，其特征是，将所述聚乙烯接枝物、聚乙烯基体树脂、耐热增强粒子、弹性体增韧粒子按配方量加入高混机预混，在经过双螺杆挤出机混炼得到粘接树脂颗粒。
10.根据权利要求9所述的粘接树脂的制备方法，其特征是，所述双螺杆挤出机的挤出机温度为230℃，螺杆转速为300rpm，喂料为7Hz，双螺杆长径比L/D＝40:1。
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