CN110154476A - 一种新型多层复合聚氯乙烯抗菌管道 - Google Patents
一种新型多层复合聚氯乙烯抗菌管道 Download PDFInfo
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Abstract
本发明涉及一种新型多层复合聚氯乙烯抗菌管道,包括由外至内依次设置的外层、中间层、内层,所述中间层包括如下重量份的组分:PVC树脂60‑80份,抗冲改性剂10‑30份,增韧改性剂10‑30份,稳定剂3‑6份,润滑剂1‑3份,偶联剂2‑5份,填充剂0‑15份,六甲基磷酰三胺1‑4份。本发明在增加PVC管的韧性的同时,赋予其抗菌的效果,并同时提升PVC管的抗老化能力,使得PVC管具有较强的综合性能。
Description
技术领域
本发明属于复合材料领域,尤其涉及一种新型多层复合聚氯乙烯抗菌管道。
背景技术
聚氯乙烯,英文简称PVC,是世界上产量极大的通用塑料,应用非常广泛,其在建筑材料、工业制品、日用品等各等方面均有广泛应用。相对于其他材料而言,PVC加工原料丰富,加工工艺简单,且本身材质较轻,防水防潮,阻燃隔热,还具有一定的抗化学腐蚀性与优异的电绝缘性。
但PVC材料普遍存在抗冲击强度差与韧性不足的问题,由于这些方面的不足,导致该材料制备的管道的脆性较大,在产品运输、安装以及使用的过程中极易发生脆性破坏;其次,PVC材料在太阳光、紫外线的照射下易老化,导致以此材料所制管道在户外长期使用易出现管道漏水,渗水、破裂,因此大大限制了该材料在户外产品的应用。例如公开号为CN201610598731.X的专利公开了一种高抗冲击PVC管,包括以下重量份的组分制成:PVC树脂100份、钛白粉5~10份、CPE 0.1~0.3份、ACM 0.1~0.3份。虽然有添加一定组分的ACM和钛白粉,一定程度上提高了PVC管的抗冲击强度,但并不具备良好的综合性能,未解决管道易老化和抗菌的问题。
因此制造出具有良好的综合性能的PVC管道显得尤为重要。
发明内容
为了解决目前存在的问题,本发明提供了一种新型多层复合聚氯乙烯抗菌管道,抗菌管道不仅抗冲击强度高、韧性好、抗老化。
本发明的技术方案是这样实现的:
一种新型多层复合聚氯乙烯抗菌管道,包括由外至内依次设置的外层、中间层、内层,所述中间层包括如下重量份的组分:PVC树脂60-80份,抗冲改性剂10-30份,增韧改性剂10-30份,稳定剂3-6份,润滑剂1-3份,偶联剂2-5份,填充剂0-15份,六甲基磷酰三胺1-4份。
进一步的,抗冲改性剂为抗菌ABS。
进一步的,增韧改性剂选自HDPE、CPE、MBS、ACR、PP、SBR、NBR中的一种或多种。
上述技术方案中,PVC树脂本身坚硬而脆的材料,抗冲击强度较低。加入抗冲改性剂后,抗冲改性剂的弹性体粒子可以降低总的银纹引发应力,并利用粒子自身的变形和剪切带,阻止银纹扩大和增长,吸收掉传入材料体内的冲击能,从而达到抗冲击的目的。现有的抗冲改性剂ACR、MBS、ABS基本上都能达到,而且不影响PVC树脂本身的硬度。
但是对于需要提供抗菌性的管道来说,目前的做法是在管道本身的内层涂布抗菌层,或者是在管道本身的组分中加上抗菌剂,对于前者,抗菌层很容易脱落损坏,导致抗菌效果差,后者,加入抗菌剂会影响冲击改性剂的效果,甚至影响PVC树脂本身的硬度,导致管材的形成变差,本申请的上述方案中,通过选择抗菌ABS作为抗冲改性剂,在赋予管道抗菌的同时又保证了管体的硬度和韧性。
进一步的,抗菌ABS包含ABS、载铜磷酸锆、载银磷酸锆,对大肠杆菌和金葡菌抗菌率达到99%。
进一步的,抗菌ABS包含ABS、载铜磷酸锆、载银磷酸锆、热塑性弹体。加入热塑性弹体,可以协助ABS发挥其抗冲改性剂的功能,并能减低抗菌分子对管道性能的影响。
更进一步的,抗菌ABS包含ABS 92-97重量份、载铜磷酸锆0.5-2重量份、载银磷酸锆1-3重量份、热塑性弹体0.5-3重量份。
进一步的,热塑性弹体为聚酰胺类热塑性弹性体、苯乙烯类热塑性弹体、氯乙烯类热塑性弹体中的一种或几种。
进一步的,热塑性弹体为氯化聚乙烯。氯化聚乙烯不仅能较好的提高PVC管的韧性,且该材料成本低廉。
进一步的,增韧改性剂为抗菌PP,包含PP 91-95重量份、季铵盐高分子抗菌剂5-9重量份。
进一步的,外层、中间层与内层的厚度比例为1-2:3-5:1-2。如此可根据管道的总厚度在适当调整各层的厚度,以保障PVC管各层的厚度,从而保证PVC管的强度、韧性、抗老化及抗菌性能。
进一步的,填充剂为纳米级轻钙或纳米级轻钙与金属氧化物的混合物。纳米级轻钙作为填充剂具有化学性质稳定、成本低廉、粒径和粒子形状可以控制等优势,且添加纳米轻碳酸钙还可以起到增韧、增强的作用,增强管材的耐热性。金属氧化物,可以在一定程度上抗击紫外线,使得管材具有很好的耐候性,且加入金属氧化物可以一定程度上提高管材的阻燃性能。
进一步的,填充剂中金属氧化物为钛白粉、氧化铝、氧化锆、氧化镁中的一种或几种。
进一步的,填充剂为纳米级轻钙与金属氧化物的混合物,金属氧化物的使用量不超过5wt%。
进一步的,偶联剂选自硅烷偶联剂或钛酸酯偶联剂。
进一步的,润滑剂选自氧化聚氯乙烯、聚乙烯蜡、高级脂肪酸盐、硅油中的一种或多种。
优选的,润滑剂为R1CONX1CH2-CH2NX2COR2,X1、X2为相同或不相同的高级脂肪酸根;R1、R2为相同或不相同的高级烷烃基。以此做为润滑剂在本申请中润滑效果最为出众。
进一步的,稳定剂为稀土稳定剂。稀土稳定剂具有相当好的热稳定性、光稳定性和透明性及着色力,且有着净化杂质作用,可促使高分子,聚合提高和分子量增加,产品结构致密,各种性能得到改善。
进一步的,外层为抗氧化PVC层,抗氧化PVC层包括如下的重量组分:PVC树脂60-80份,抗冲改性剂10-30份,增韧改性剂10-30份,稳定剂3-6份,润滑剂1-3份,偶联剂2-5份,填充剂0-15份,六甲基磷酰三胺10-20份。所添加的六甲基磷酰三胺不但可以大大提高PVC管材的抗氧化性能,从而有效防止和缓解管道在使用过程中老化,以适应在户外、高温等环境下的稳定应用,而且六甲基磷酰三胺成本比较低,适于广泛使用。
通过实施上述技术方案,本发明的有益效果:本发明在增加PVC管的韧性的同时,赋予其抗菌的效果,并同时提升PVC管的抗老化能力,使得PVC管具有较强的综合性能。
具体实施方式
下面将对本申请的技术方案进行清楚、完整的描述,显然,所描述的实施例仅仅是本申请一部分实施例,而不是全部的实施例。基于本申请的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本申请保护的范围。
实施例1
一种新型多层复合聚氯乙烯抗菌管道,包括外层、中间层、内层,外层与内层分别形成在中间层的外表面与内表面上,外层、中间层与内层的厚度比例为1:3:1。
外层包括抗氧化PVC层11,包括重量组分:PVC树脂60份,ACR树脂10份,MBS树脂10份,稀土稳定剂3份,氧化聚氯乙烯1份,硅烷偶联剂2份,六甲基磷酰三胺4份。
中间层包括:PVC树脂60份、抗菌ABS 10份、MBS10份、稀土稳定剂3份,氧化聚氯乙烯1份,硅烷偶联剂2份,六甲基磷酰三胺10份。
内层采用抗菌ABS。
其中,抗菌ABS包含ABS 92重量份、载铜磷酸锆2重量份、载银磷酸锆1重量份、热塑性弹体0.5重量份。热塑性弹体为聚酰胺类热塑性弹性体。
实施例2
一种新型多层复合聚氯乙烯抗菌管道,包括外层、中间层、内层,外层与内层分别形成在中间层的外表面与内表面上,外层、中间层与内层的厚度比例为2:5:2。
中间层2包括重量组分:PVC树脂80份,抗菌ABS 30份,CPE树脂30份,稀土稳定剂6份,聚乙烯蜡3份,钛酸酯偶联剂5份,纳米级轻钙15份,六甲基磷酰三胺1份。其中,抗菌ABS包含ABS 92-97重量份、载铜磷酸锆0.5-2重量份、载银磷酸锆1-3重量份、热塑性弹体0.5-3重量份。热塑性弹体为苯乙烯类热塑性弹体。
外层1为抗氧化PVC层11,抗氧化PVC层11包括重量组分:PVC树脂80份,ABS树脂30份,CPE树脂30份,稀土稳定剂6份,聚乙烯蜡3份,钛酸酯偶联剂5份,纳米级轻钙15份,六甲基磷酰三胺15份。
内层采用抗菌PP,包含PP 95重量份、季铵盐高分子抗菌剂5重量份。
实施例3
一种新型多层复合聚氯乙烯抗菌管道,包括外层、中间层、内层,外层与内层分别形成在中间层的外表面与内表面上,外层、中间层与内层的厚度比例为2:5:2。
中间层2包括重量组分:PVC树脂80份,抗菌ABS 30份,CPE树脂30份,稀土稳定剂6份,聚乙烯蜡3份,钛酸酯偶联剂5份,纳米级轻钙10份、钛白粉0.5份,六甲基磷酰三胺1份。
内层采用抗菌ABS。
其中,抗菌ABS包含ABS 95重量份、载铜磷酸锆1重量份、载银磷酸锆3重量份、热塑性弹体3重量份。热塑性弹体为苯乙烯类热塑性弹体。
外层1为抗氧化PVC层11,抗氧化PVC层11包括重量组分:PVC树脂80份,ABS树脂30份,CPE树脂30份,稀土稳定剂6份,聚乙烯蜡3份,钛酸酯偶联剂5份,钛白粉15份,六甲基磷酰三胺15份。
实施例4
一种新型多层复合聚氯乙烯抗菌管道,包括外层、中间层、内层,外层与内层分别形成在中间层的外表面与内表面上,外层、中间层与内层的厚度比例为1:5:1。
中间层2包括重量组分:PVC树脂75份,抗菌ABS 25份,抗菌PP30份,稀土稳定剂5份,聚乙烯蜡3份,钛酸酯偶联剂4份,纳米级轻钙12、氧化镁0.2份,六甲基磷酰三胺12份。
内层采用抗菌ABS。
其中,抗菌ABS包含ABS 7重量份、载铜磷酸锆2重量份、载银磷酸锆2重量份、热塑性弹体1重量份。热塑性弹体为苯乙烯类热塑性弹体。抗菌PP包含PP 91重量份、季铵盐高分子抗菌剂9重量份。
外层1为抗氧化PVC层11,抗氧化PVC层11包括重量组分:PVC树脂75份,ACR树脂25份,HDPE树脂25份,稀土稳定剂5份,聚氯乙烯2.7份,硅烷偶联剂4份,氧化镁12份,六甲基磷酰三胺20份。
实施例5
一种新型多层复合聚氯乙烯抗菌管道,包括外层、中间层、内层,外层与内层分别形成在中间层的外表面与内表面上,外层、中间层与内层的厚度比例为2:4:1。
中间层包括重量组分:PVC树脂75份,抗菌ABS 25份,抗菌PP30份,稀土稳定剂5份,聚乙烯蜡3份,钛酸酯偶联剂4份,纳米级轻钙3、氧化锆0.1份,六甲基磷酰三胺12份。
内层采用抗菌ABS。
其中,抗菌ABS包含ABS 92-97重量份、载铜磷酸锆0.5-2重量份、载银磷酸锆1-3重量份、热塑性弹体0.5-3重量份。热塑性弹体为氯乙烯类热塑性弹体。抗菌PP包含PP 91-95重量份、季铵盐高分子抗菌剂5-9重量份。
外层1为抗氧化PVC层11,抗氧化PVC层11包括重量组分:PVC树脂75份,ACR树脂25份,HDPE树脂25份,稀土稳定剂5份,聚氯乙烯2.7份,硅烷偶联剂4份,氧化镁12份,六甲基磷酰三胺20份。
对比例1
一种新型多层复合聚氯乙烯抗菌管道,包括外层、中间层、内层,外层与内层分别形成在中间层的外表面与内表面上,外层、中间层与内层的厚度比例为1:3:1。
外层包括抗氧化PVC层11,包括重量组分:PVC树脂60份,ACR树脂10份,MBS树脂10份,稀土稳定剂3份,氧化聚氯乙烯1份,硅烷偶联剂2份,六甲基磷酰三胺4份。
中间层包括:PVC树脂60份、ACR树脂10份、MBS树脂10份、稀土稳定剂3份,氧化聚氯乙烯1份,硅烷偶联剂2份,六甲基磷酰三胺10份。
内层采用ABS抗菌层。
对比例2
一种新型多层复合聚氯乙烯抗菌管道,包括外层、中间层、内层,外层与内层分别形成在中间层的外表面与内表面上,外层、中间层与内层的厚度比例为2:5:2。
中间层包括重量组分:PVC树脂80份,抗菌ABS 30份,抗菌PP 45份,稀土稳定剂6份,聚乙烯蜡3份,钛酸酯偶联剂5份,钛白粉15份,六甲基磷酰三胺1份。其中,抗菌ABS包含ABS 92-97重量份、载铜磷酸锆0.5-2重量份、纳米氧化锌1-3重量份。
外层1为抗氧化PVC层,抗氧化PVC层包括重量组分:PVC树脂80份,ABS树脂30份,CPE树脂30份,稀土稳定剂6份,聚乙烯蜡3份,钛酸酯偶联剂5份,钛白粉15份,六甲基磷酰三胺4份。
内层采用上述抗菌ABS。
对比例3
一种新型多层复合聚氯乙烯抗菌管道,包括外层、中间层、内层,外层与内层分别形成在中间层的外表面与内表面上,外层、中间层与内层的厚度比例为2:5:2。
中间层包括抗菌PVC层,抗菌PVC层包括重量组分:PVC树脂85份,抗菌ABS 5份,CPE树脂30份,稀土稳定剂6份,聚乙烯蜡3份,钛酸酯偶联剂5份,钛白粉15份,六甲基磷酰三胺1份。其中,抗菌ABS包含ABS 92重量份、载银磷酸锆0.5重量份。
外层为抗氧化PVC层11,抗氧化PVC层包括重量组分:PVC树脂80份,ABS树脂30份,CPE树脂30份,稀土稳定剂6份,聚乙烯蜡3份,钛酸酯偶联剂5份,钛白粉15份,六甲基磷酰三胺30份。
内层采用上述抗菌ABS。
对比例4
一种新型多层复合聚氯乙烯抗菌管道,包括外层、中间层、内层,外层与内层分别形成在中间层的外表面与内表面上,外层、中间层与内层的厚度比例为2:5:2。
中间层包括抗菌PVC层,抗菌PVC层包括重量组分:PVC树脂80份,抗菌ABS 30份,羧基丁腈橡胶30份,稀土稳定剂6份,聚乙烯蜡3份,钛酸酯偶联剂5份,六甲基磷酰三胺1份。其中,抗菌ABS包含ABS 92重量份、载铜磷酸锆0.1重量份、载银磷酸锆0.5重量份。
外层为抗氧化PVC层11,抗氧化PVC层包括重量组分:PVC树脂80份,ABS树脂30份,CPE树脂30份,稀土稳定剂6份,聚乙烯蜡3份,钛酸酯偶联剂5份,云母粉15份,六甲基磷酰三胺30份。
内层采用上述抗菌ABS。
将本发明实施例1-5、对比例1-4的PVC管材做如下测试:
(1)抗菌性能:采用贴膜法,按QB/T 2591-2003中的“抗细菌性能试验方法”,以抗菌管道与供试细菌接触24小时后的抑菌率考察抗菌效果,抗菌率计算公式为:R=(B-C)/B*100%。式中,R为抗菌率,B为空白对照样品平均回收菌数,C为抗菌管道平均回收菌数。
供试菌种:大肠杆菌与金葡菌,均为市售。
在37℃下培养24h,根据1.44c㎡上所生长的菌落数目计算抗菌率,结果如下:
实施例1:大肠杆菌R=99.15%;金葡菌R=99.3%。
实施例2:大肠杆菌R=99.92%;金葡菌R=99.95%。
实施例3:大肠杆菌R=99.30%;金葡菌R=99.41%。
实施例4:大肠杆菌R=99.57%;金葡菌R=99.59%。
实施例5:大肠杆菌R=99.68%;金葡菌R=99.83%。
对比例1:大肠杆菌R=92.42%;金葡菌R=93.83%。
对比例2:大肠杆菌R=96.23%;金葡菌R=95.38%。
对比例3:大肠杆菌R=96.75%;金葡菌R=97.26%。
对比例4:大肠杆菌R=96.51%;金葡菌R=94.91%。
(2)维卡软化温度测定实验
将本发明实施例1-5的样品取试样用维卡软化温度测定仪测定其维卡软化温度,依次为96℃、98℃、96℃、105℃、100℃、90℃、93℃、92℃、93℃。
(3)抗冲击强度测定试验
根据GB 1943-2007测定本发明实施例1-5、对比例1-4的样品的抗冲击能力,测定结果依次为:42kJ/m2、50kJ/m2、46kJ/m2、44kJ/m2、48kJ/m2、38 kJ/m2、40 kJ/m2、41 kJ/m2、41 kJ/m2。
根据以上测试结果,可以看出本发明的新型多层复合聚氯乙烯抗菌管道优异的抗菌、高强度、高韧性的特点。
Claims (10)
1.一种新型多层复合聚氯乙烯抗菌管道,包括由外至内依次设置的外层、中间层、内层,其特征在于,所述中间层包括如下重量份的组分:PVC树脂60-80份,抗冲改性剂10-30份,增韧改性剂10-30份,稳定剂3-6份,润滑剂1-3份,偶联剂2-5份,填充剂0-15份,六甲基磷酰三胺1-4份。
2.根据权利要求1所述一种新型多层复合聚氯乙烯抗菌管道,其特征在于,抗冲改性剂为抗菌ABS。
3.根据权利要求2所述一种新型多层复合聚氯乙烯抗菌管道,其特征在于,抗菌ABS包含ABS、载铜磷酸锆、载银磷酸锆。
4.根据权利要求3所述一种新型多层复合聚氯乙烯抗菌管道,其特征在于,抗菌ABS包含ABS、载铜磷酸锆、载银磷酸锆、热塑性弹体。
5.根据权利要求4所述一种新型多层复合聚氯乙烯抗菌管道,其特征在于,抗菌ABS包含ABS 92-97重量份、载铜磷酸锆0.5-2重量份、载银磷酸锆1-3重量份、热塑性弹体0.5-3重量份。
6.根据权利要求5所述一种新型多层复合聚氯乙烯抗菌管道,其特征在于,热塑性弹体为聚酰胺类热塑性弹性体、苯乙烯类热塑性弹体、氯乙烯类热塑性弹体中的一种或几种。
7.根据权利要求1所述一种新型多层复合聚氯乙烯抗菌管道,其特征在于,增韧改性剂选自HDPE、CPE、MBS、ACR、PP、SBR、NBR中的一种或多种。
8.根据权利要求7所述一种新型多层复合聚氯乙烯抗菌管道,其特征在于,增韧改性剂为抗菌PP,包含PP 91-95重量份、季铵盐高分子抗菌剂5-9重量份。
9.根据权利要求1所述一种新型多层复合聚氯乙烯抗菌管道,其特征在于,填充剂为纳米级轻钙或纳米级轻钙与金属氧化物的混合物。
10.根据权利要求9所述一种新型多层复合聚氯乙烯抗菌管道,其特征在于,填充剂中金属氧化物为钛白粉、氧化铝、氧化锆、氧化镁中的一种或几种。
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