CN112373161A - 一种高导热、高耐热的多层复合管材及其制备方法 - Google Patents
一种高导热、高耐热的多层复合管材及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种高导热、高耐热的多层复合管材及其制备方法,管材分为内、中、外三层,内层材料为氟烯烃聚合物,中间层材料为包含梳形相容剂的高分子合金,外层材料为耐热聚乙烯。管材使用三层共挤一次成型技术,所得管材具有耐热温度高,导热性好,层间结合紧密,生产工艺简便,使用寿命长等优点,在此基础上还具有聚偏氟乙烯管材环保、析出性小、化学稳定性好;抗冲击强度高、耐磨耗,耐蠕变、机械强度及韧性好;耐热性佳、长期使用温度‑20‑100℃;表面光滑,流体阻力小,阻氧性能突出等优秀品质。
Description
技术领域
本发明属于地暖管技术领域,具体涉及一种高导热、高耐热的多层复合管材及其制备方法。
背景技术
耐热聚乙烯(PE-RT)管材是一种多用于热水输送的非交联聚乙烯(PE)管材,其主要成分耐热聚乙烯(PE-RT)为乙烯和辛烯的共聚物,特点是在PE长链聚合了辛烯使主链上带有辛烯短支链,是一种具有独特的分子结构的中密度共聚聚乙烯材料,在保留PE大部分优秀性能的基础上提高了PE的耐热性能和耐压性能,是目前市面上最常见的地暖管材料。
然而受限于耐热聚乙烯(PE-RT)材料本身的特点,耐热聚乙烯(PE-RT)管材的长期使用温度为60-80℃,管道内通常使用60℃以下的低温热水循环加热,在对较大室内空间进行采暖施工时,存在管材用量较大,升温速度慢,传热效率不高,房间整体温度不高等缺点。
这些缺点通常可以通过改用高温热水加热,利用高温热水和室温较大的温差同时解决管材用量、升温速率和传热效率的问题。而由于耐热聚乙烯(PE-RT)材料本身的限制,使用高温热水加热会导致耐热聚乙烯(PE-RT)管材强度下降,进而导致管材使用寿命随之下降。为解决耐热聚乙烯(PE-RT)管材存在的上述问题,一种显而易见的办法即为耐热聚乙烯(PE-RT)管材添加一个耐热稳定的内层,通过制成复合管材的方式打破耐热聚乙烯(PE-RT)材料本身的限制,使管材具备在更高温度下长期使用的能力。
聚偏氟乙烯(PVDF)是一种性能优良的材料,具有环保、析出性小、化学稳定性好;抗冲击强度高、耐磨耗,耐蠕变、机械强度及韧性好;耐热性佳、不燃性、长期使用温度-40-150℃;表面光滑,流体阻力小,阻氧性能突出等优秀品质,特别适用于液体输送等领域,可以完全满足高温地暖管材的需要,然而聚偏氟乙烯高昂的价格使该材料难以进入民用领域,鉴于耐热聚乙烯(PE-RT)的价格远低于PVDF,将PVDF与耐热聚乙烯(PE-RT)制成复合管材可以充分利用两者的优势,使管材在具有高耐热性的同时大幅降低PVDF的使用成本。而提高循环热水的温度可以减少地暖系统整体管材用量,提高升温速率和传热效率,从而控制整个管路系统的造价和使用成本,并具备使较大空间保持人体舒适温度的能力。
从性能和用途上看,PVDF是非常适合与耐热聚乙烯(PE-RT)进行复合的材料之一,而从相容性角度看,PVDF与耐热聚乙烯(PE-RT)是两种热力学不相容的材料,耐热聚乙烯(PE-RT)/PVDF复合管材的界面结合力极差,通常制备无规聚丙烯/聚偏氟乙烯合金也常常需要对耐热聚乙烯(PE-RT)和PVDF分别作出增容改性,制备过程复杂,并且导致耐热聚乙烯(PE-RT)和聚偏氟乙烯的性能都有不同程度的下降,高品质的耐热聚乙烯(PE-RT)/PVDF复合管材制作难度很大,目前在市面上并无品质优秀的商业化产品。
现阶段,国内外公司都做了一些相关产品研究开发工作,简要列举如下:
专利CN110204820A,公开了一种聚偏氟乙烯-聚乙烯复合材料及其制备方法,使用增容剂包括EVA、EAA或EMA中的一种或几种,相容剂包括PE-g-GMA、POE-g-MAH或EMA-g-GMA中的一种或几种达到对PVDF和PE材料的增容效果。该复合材料首先应用于绝缘子保护套领域,在管材领域尚无对应应用;其次使用的增容剂和相容剂均为主要针对PE的改性,对PVDF的增容效果有限,粘结效果不明,易吸水,容易导致复合管材层间脱落,降低管材整体强度,且通常需对PVDF进行较多改性导致不同程度的性能下降;第三所用的增容剂和相容剂部分为弹性体,使用这些增容剂和相容剂可能导致PE与PVDF的界面强度较低,从而使材料整体弹性增加,用于管材中会导致管材在水压下形变较大,壁厚变薄进而影响管材耐压性能。
专利CN109253320A,公开了一种无规聚丙烯/聚偏氟乙烯复合管材,本发明公开了一种多层复合管材及其制备方法。管材分为内、中、外三层,内层材料为氟烯烃聚合物,中间层材料为包含梳形相容剂的高分子合金,外层材料为无规聚丙烯。该专利中使用的梳形相容剂可规避专利CN110204820A中存在的部分问题,但首先聚丙烯和聚乙烯存在结构上的本质区别,聚丙烯主链上存在大量叔氢原子,活性较高,耐老化性和改性难度均低于没有叔氢原子的聚乙烯和只具有少量叔氢原子的耐热聚乙烯(PE-RT),适用于聚丙烯的改性方法难以直接套用于聚乙烯和耐热聚乙烯(PE-RT),对应的相容剂需要重新开发,其次该专利中的相容剂为主链上带有两种不同侧链的双梳齿型相容剂,即在主链上接枝了2种不同的支链,通过支链实现对PVDF和PPR的相容性,主链利用较少,且双梳齿型梳形相容剂存在加工困难等问题;其次聚丙烯的导热性远低于耐热聚乙烯(PE-RT),使该复合管材通常不适用于地暖管材领域;第三该复合管材内层使用纯PVDF,导热性能难以达到要求。
纵观相关技术领域,目前现有的技术方案普遍存在下列缺点:
1、内外层材料粘结性不够,导致管材内外层容易脱离;
2、进行过多改性会导致材料性能下降;
3、材料导热性能不足。
因此需要研制一种新型复合管材,具有层间结合紧密,使用温度高,使用寿命长,生产工艺简便等优点,结合并充分利用耐热聚乙烯(PE-RT)和PVDF两者的优势,达到性能最大化。
发明内容
本发明目的在于针对现有技术所存在的不足而一种高导热、高耐热的多层复合管材及其制备方法,具有层间结合紧密,使用温度高,使用寿命长,生产工艺简便等优点。
为了解决上述技术问题,本发明采用如下技术方案:
一种高导热、高耐热的多层复合管材,其特征在于:由内层、紧贴于内层外侧的中间层和紧贴于中间层外侧的外层组成,内层为改性氟烯烃聚合物内层,中间层为合金粒料中间层,合金粒料中间层中包含相容剂,外层为聚烯烃外层。
进一步,无规聚烯烃外层为耐热聚乙烯外层。
进一步,合金粒料中间层由相容剂、氟烯烃聚合物和无规聚烯烃的大分子缠结形成。
进一步,相容剂的质量分数为10%-30%,氟烯烃聚合物的质量分数为20%-70%,聚乙烯的质量分数为20%-70%。
进一步,相容剂为主链为聚酯,侧链含有C4及以上的烃基的梳形聚合物。
该梳形相容剂利用主链结构实现对聚偏氟乙烯的增容效果,利用侧链实现对耐热聚乙烯的增容效果,减少侧链的数量可增强大分子运动能力,从而在不会大幅降低增容效果的基础上有效提高材料的加工性能。
进一步,合金粒料由相容剂、改性氟烯烃聚合物和耐热聚乙烯混合后,经挤出造粒获得。
在相容剂作用下将改性氟烯烃聚合物和耐热聚乙烯熔融共混形成一种合金材料,利用改性氟烯烃聚合物对复合管材内层材料的相容性和耐热聚乙烯对复合管外层材料的相容性,使中间层材料介于管外层和管内层之间起到良好的粘结作用。
进一步,改性氟烯烃内层由聚偏氟乙烯、导热剂、抗氧剂进行熔融共混得到的混合物材料。
进一步,导热剂为短切碳纤维、石墨、碳纳米管、石墨烯中的一种或混合物。导热剂的添加量为2-15wt%,优选5-10wt%。
一种高导热、高耐热的多层复合管材的制备方法,其特征在于,包括如下步骤:
(1)将不同物料分别加入挤出形成内层、中间层和外层的三台挤出机中,其中用于形成内层的挤出机中加入氟烯烃聚合物粒料,用于形成外层的挤出机中加入聚乙烯粒料,用于形成中间层的挤出机中加入合金粒料;
(2)使用三台挤出机分别挤出内层、中间层和外层,并通过同一复合挤出模头一次成型得到未定型的三层复合管材;
(3)未定型的三层复合管材通过真空定径后切割,再用烘箱进行热定型后得到三层复合管材。
优选的,步骤(2)中的三台挤出机的机筒均分为6个加热段,用于内层的挤出机的机筒各段加热温度为:1段加热温度为210±5℃,2段加热温度为220±5℃,3段加热温度为225±5℃,4段加热温度为230±5℃,5段加热温度为230±5℃,6段加热温度为235±5℃;用于中间层的挤出机的机筒各段加热温度为:1段加热温度为200±5℃,2段加热温度为205±5℃,3段加热温度为210±5℃,4段加热温度为215±5℃,5段加热温度为220±5℃,6段加热温度为225±5℃;用于外层的挤出机的机筒各段加热温度为:1段加热温度为195±5℃,2段加热温度为200±5℃,3段加热温度为205±5℃,4段加热温度为210±5℃,5段加热温度为215±5℃,6段加热温度为220±5℃。
优选的,步骤(3)中,共挤出后的复合管材在0.01-0.04的真空中,在20℃下进行水冷定径后,置于烘箱中24h消除内应力,即得到本发明多层复合管材。
由于采用上述技术方案,本发明具有以下有益效果:
本发明公开了一种高导热、高耐热多层复合管材及其制备方法,解决了耐热聚乙烯和PVDF的不相容问题,有效提高了中间层材料对耐热聚乙烯和聚偏氟乙烯的粘结性,同时改善了聚偏氟乙烯的导热性能,所得管材具有耐热温度高,导热性好,层间结合紧密,生产工艺简便,使用寿命长等优点,在此基础上还具有聚偏氟乙烯管材环保、析出性小、化学稳定性好;抗冲击强度高、耐磨耗,耐蠕变、机械强度及韧性好;耐热性佳、长期使用温度-20-100℃;表面光滑,流体阻力小,阻氧性能突出等优秀品质。
具体实施方式
一种高导热、高耐热的多层复合管材的制备方法,其特征在于,包括如下步骤:
(1)将不同物料分别加入挤出形成内层、中间层和外层的三台挤出机中,其中用于形成内层的挤出机中加入氟烯烃聚合物粒料,用于形成外层的挤出机中加入聚乙烯粒料,用于形成中间层的挤出机中加入合金粒料;
(2)使用三台挤出机分别挤出内层、中间层和外层,并通过同一复合挤出模头一次成型得到未定型的三层复合管材,三台挤出机的机筒均分为6个加热段,用于内层的挤出机的机筒各段加热温度为:1段加热温度为210±5℃,2段加热温度为220±5℃,3段加热温度为225±5℃,4段加热温度为230±5℃,5段加热温度为230±5℃,6段加热温度为235±5℃;用于中间层的挤出机的机筒各段加热温度为:1段加热温度为200±5℃,2段加热温度为205±5℃,3段加热温度为210±5℃,4段加热温度为215±5℃,5段加热温度为220±5℃,6段加热温度为225±5℃;用于外层的挤出机的机筒各段加热温度为:1段加热温度为195±5℃,2段加热温度为200±5℃,3段加热温度为205±5℃,4段加热温度为210±5℃,5段加热温度为215±5℃,6段加热温度为220±5℃;
(3)共挤出后的复合管材在0.01-0.04的真空中,在20℃下进行水冷定径后,置于烘箱中24h消除内应力,即得到本发明多层复合管材。
实施例1
外层材料使用耐热聚乙烯(PE-RT),按重量计使用量为100份;中间层材料使用聚偏氟乙烯和耐热聚乙烯(PE-RT)的合金,按重量计使用量为20份,包括质量分数为65%的聚偏氟乙烯、10%的相容剂材料和25%的耐热聚乙烯(PE-RT);内层材料为改性聚偏氟乙烯,按重量计使用量为20份,添加2份短切碳纤维作为导热剂。经三层共挤出一次成型得到复合管材。
实施例2
外层材料使用耐热聚乙烯(PE-RT),按重量计使用量为100份;中间层材料使用聚偏氟乙烯和无规聚丙烯的合金,按重量计使用量为30份,包括质量分数为60%聚偏氟乙烯、20%相容剂材料和20%的耐热聚乙烯(PE-RT);内层材料为改性聚偏氟乙烯,按重量计使用量为40份,添加3份短切碳纤维作为导热剂。经三层共挤出一次成型得到复合管材。
实施例3:
外层材料使用耐热聚乙烯(PE-RT),按重量计使用量为100份;中间层材料使用聚偏氟乙烯和无规聚丙烯的合金,按重量计使用量为30份,包括质量分数为60%聚偏氟乙烯、20%相容剂材料和20%的耐热聚乙烯(PE-RT);内层材料为改性聚偏氟乙烯,按重量计使用量为40份,添加2份短切碳纤维作为导热剂。经三层共挤出一次成型得到复合管材。
实施例4:
外层材料使用耐热聚乙烯(PE-RT),按重量计使用量为100份;中间层材料使用聚偏氟乙烯和无规聚丙烯的合金,按重量计使用量为40份,包括质量分数为40%聚偏氟乙烯、20%相容剂材料和40%的耐热聚乙烯(PE-RT);内层材料为改性聚偏氟乙烯,按重量计使用量为50份,添加5份石墨作为导热剂。经三层共挤出一次成型得到复合管材。
实施例5:
外层材料使用耐热聚乙烯(PE-RT),按重量计使用量为100份;中间层材料使用聚偏氟乙烯和无规聚丙烯的合金,按重量计使用量为80份,包括质量分数为45%聚偏氟乙烯、10%相容剂材料和45%无规聚丙烯;内层材料为改性聚偏氟乙烯,按重量计使用量为50份,添加4份石墨作为导热剂。经三层共挤出一次成型得到复合管材。
对比例1:
外层材料使用无规聚丙烯,按重量计使用量为100份;中间层材料使用聚偏氟乙烯和无规聚丙烯的合金,按重量计使用量为40份,包括质量分数为40%聚偏氟乙烯、20%相容剂材料和40%无规聚丙烯;内层材料为偏氟乙烯均聚物,按重量计使用量为40份。经三层共挤出一次成型得到复合管材。
对比例2:
外层材料使用耐热聚乙烯(PE-RT),按重量计使用量为100份;中间层材料使用聚偏氟乙烯、耐热聚乙烯(PE-RT)、EMA基相容剂的合金,按重量计使用量为40份,包括质量分数为45%聚偏氟乙烯、10%的EVA材料和45%的耐热聚乙烯(PE-RT);内层材料为聚偏氟乙烯,按重量计使用量为40份。经三层共挤出一次成型得到复合管材。
性能测试结果:
编号 | T型剥离强度 | 热水耐内压实验 | 导热系数 |
实施例1 | 500N/m | 8760h无破裂渗漏 | 0.52 |
实施例2 | 650N/m | 8760h无破裂渗漏 | 0.46 |
实施例3 | 650N/m | 8760h无破裂渗漏 | 0.42 |
实施例4 | 1100N/m | 8760h无破裂渗漏 | 0.50 |
实施例5 | 400N/m | 8760h无破裂渗漏 | 0.47 |
对比例1 | 1200N/m | 8760h无破裂渗漏 | 0.16 |
对比例2 | 200N/m | 5621h破裂 | 0.22 |
实施例中样品性能测试标准:
热水耐内压实验:GB/T 28799.1-2012;
本发明解决了耐热聚乙烯(PE-RT)和PVDF的不相容问题,同时对PVDF的导热性能进行了改善,所得管材具有耐热温度高,导热性好,层间结合紧密,生产工艺简便,使用寿命长等优点,在此基础上还具有聚偏氟乙烯管材环保、析出性小、化学稳定性好;抗冲击强度高、耐磨耗,耐蠕变、机械强度及韧性好;耐热性佳、长期使用温度-20-100℃;表面光滑,流体阻力小,阻氧性能突出等优秀品质。
以上仅为本发明的具体实施例,但本发明的技术特征并不局限于此。任何以本发明为基础,为解决基本相同的技术问题,实现基本相同的技术效果,所作出地简单变化、等同替换或者修饰等,皆涵盖于本发明的保护范围之中。
Claims (10)
1.一种高导热、高耐热的多层复合管材,其特征在于:由内层、紧贴于所述内层外侧的中间层和紧贴于所述中间层外侧的外层组成,所述内层为改性氟烯烃聚合物内层,所述中间层为合金粒料中间层,所述合金粒料中间层中包含相容剂,所述外层为聚烯烃外层。
2.根据权利要求1所述一种高导热、高耐热的多层复合管材,其特征在于:所述无规聚烯烃外层为耐热聚乙烯外层。
3.根据权利要求1所述一种高导热、高耐热的多层复合管材,其特征在于:所述合金粒料中间层由相容剂、氟烯烃聚合物和无规聚烯烃的大分子缠结形成。
4.根据权利要求3所述一种高导热、高耐热的多层复合管材,其特征在于:所述相容剂的质量分数为10%-30%,所述氟烯烃聚合物的质量分数为20%-70%,所述聚乙烯的质量分数为20%-70%。
5.根据权利要求3所述一种高导热、高耐热的多层复合管材,其特征在于:所述相容剂为主链为聚酯,侧链含有C4及以上的烃基的梳形聚合物。
6.根据权利要求3所述一种高导热、高耐热的多层复合管材,其特征在于:所述合金粒料由相容剂、改性氟烯烃聚合物和耐热聚乙烯混合后,经挤出造粒获得。
7.根据权利要求6所述一种高导热、高耐热的多层复合管材,其特征在于:所述改性氟烯烃内层由聚偏氟乙烯、导热剂、抗氧剂进行熔融共混得到的混合物材料。
8.根据权利要求6所述一种高导热、高耐热的多层复合管材,其特征在于:所述导热剂为短切碳纤维、石墨、碳纳米管、石墨烯中的一种或混合物。
9.如权利要求1所述一种高导热、高耐热的多层复合管材的制备方法,其特征在于,包括如下步骤:
(1)将不同物料分别加入挤出形成内层、中间层和外层的三台挤出机中,其中用于形成内层的挤出机中加入氟烯烃聚合物粒料,用于形成外层的挤出机中加入聚乙烯粒料,用于形成中间层的挤出机中加入合金粒料;
(2)使用三台挤出机分别挤出内层、中间层和外层,并通过同一复合挤出模头一次成型得到未定型的三层复合管材;
(3)未定型的三层复合管材通过真空定径后切割,再用烘箱进行热定型后得到三层复合管材。
10.根据权利要求9所述一种高导热、高耐热的多层复合管材的制备方法,其特征在于:所述步骤(2)中的三台挤出机的机筒均分为6个加热段,用于内层的挤出机的机筒各段加热温度为:1段加热温度为210±5℃,2段加热温度为220±5℃,3段加热温度为225±5℃,4段加热温度为230±5℃,5段加热温度为230±5℃,6段加热温度为235±5℃;用于中间层的挤出机的机筒各段加热温度为:1段加热温度为200±5℃,2段加热温度为205±5℃,3段加热温度为210±5℃,4段加热温度为215±5℃,5段加热温度为220±5℃,6段加热温度为225±5℃;用于外层的挤出机的机筒各段加热温度为:1段加热温度为195±5℃,2段加热温度为200±5℃,3段加热温度为205±5℃,4段加热温度为210±5℃,5段加热温度为215±5℃,6段加热温度为220±5℃。
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