CN116162301A - 一种增强型聚乙烯管材及其生产方法 - Google Patents
一种增强型聚乙烯管材及其生产方法 Download PDFInfo
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Abstract
本发明公开了一种增强型聚乙烯管材,主要组分由高密度聚乙烯和增强母粒按照质量之比(2~4.5):1共混制得;按质量份数计,增强母粒的主要组成为:高密度聚乙烯7份、聚乙烯辛烯共弹性体3.5~6份、环氧基硅烷偶联剂0.2~0.8份、环氧基丙烯酸酯单体0.03~0.09份、云母粉10~20份、棒状氧化锌20~35份。该增强型聚乙烯管材采用云母粉和棒状氧化锌两种增强填料制得复合粉体;将复合粉体与高密度聚乙烯、聚乙烯辛烯共弹性体共混制得增强母粒,复合粉体中棒状氧化锌与云母粉的复合粉体利于载荷的传递和转移,在一定程度上提高聚乙烯复合材料的强度。本发明还公开了一种增强型聚乙烯管材的生产方法。
Description
技术领域
本发明涉及给排水管道生产领域,具体涉及一种增强型聚乙烯管材及其生产方法。
背景技术
高密度聚乙烯排水管具有耐腐蚀、水流阻力小、重量轻等优点,因此广泛用于市政工程排水、矿用排水、农田灌溉等领域。但是,聚乙烯具有较差的低温抗冲击性,并且非极性的聚乙烯材料与其他材料例如无机填料等的相容性较差,限制了高密度聚乙烯排水管的适用范围。
改进的技术方案多采用加入填料的方式增强增韧管道,例如在聚乙烯复合管材的基材高密度聚乙烯中添加无机填料和偶联剂,无机填料选自空心微珠、云母、玻璃纤维等,偶联剂选自Υ-氨丙基三乙氧基硅烷、Υ-氨丙基三乙氧基硅烷等,利用硅烷偶联剂提高无机填料在高密度聚乙烯中的分散性能。如何优化不同形态填料的分布,使不同种类的填料复合并互补地提高管材的强度,是聚乙烯填充改性复合材料的主要研发方向之一。
发明内容
本发明的目的之一在于克服现有技术中存在的缺陷,提供一种增强型聚乙烯管材,通过在原料中引入含环氧基团的硅烷偶联剂和丙烯酸酯单体,制备云母和棒状氧化锌的复合粉体,复合粉体利于提升增强型聚乙烯管材的低温抗冲击性。
为了实现上述技术效果,本发明的技术方案为:一种增强型聚乙烯管材,主要组分由高密度聚乙烯和增强母粒按照质量之比(2~4.5):1共混制得;
按质量份数计,所述增强母粒的主要组成为:高密度聚乙烯7份、聚乙烯辛烯共弹性体3.5~6份、环氧基硅烷偶联剂0.2~0.8份、环氧基丙烯酸酯单体0.03~0.09份、云母粉10~20份、棒状氧化锌20~35份。
进一步的,高密度聚乙烯和增强母粒按照质量之比(2.4~4):1;增强母粒的主要组成为:高密度聚乙烯7份、聚乙烯辛烯共弹性体4~6份、环氧基硅烷偶联剂0.45~0.7份、环氧基丙烯酸酯单体0.04~0.07份、云母粉12~18份、棒状氧化锌24~32份。
优选的技术方案为,所述云母粉的粒径为10~200μm;所述棒状氧化锌的直径为200~400nm,长度为8~10nm。更进一步的,云母粉的粒径为30~100μm。
优选的技术方案为,所述环氧基硅烷偶联剂由(3-环氧丙基丙氧基)三甲氧基硅烷和2-(3,4-环氧环己基)乙基三甲氧基硅烷组合而成,(3-环氧丙基丙氧基)三甲氧基硅烷与2-(3,4-环氧环己基)乙基三甲氧基硅烷的质量之比为(1.7~2.5):1。进一步的,(3-环氧丙基丙氧基)三甲氧基硅烷与2-(3,4-环氧环己基)乙基三甲氧基硅烷的质量之比为(1.9~2.3):1。
优选的技术方案为,所述增强母粒还包括润滑剂、抗氧剂、阻燃剂、抗菌剂中的至少一种。
本发明的目的之二在于提供一种增强型聚乙烯管材的生产方法,基于上述的增强型聚乙烯管材,包括以下步骤:
S1:将云母粉分散于水溶性极性有机溶剂和有机酸的混合溶液中,超声振荡和惰性气体保护下加入环氧基丙烯酸酯单体,升温至80~100℃反应至少5h,冷却至室温,滤出云母粉,清洗烘干至恒重,得预处理云母粉;
S2:将棒状氧化锌分散于环氧基硅烷偶联剂的醇溶液中,超声振荡混合加热至50~80℃反应至少30min,降温至室温后向反应体系加入S1的预处理云母粉和去离子水,调节pH至5.5~6.5,升温反应0.5~1h,冷却,滤出粉体,烘干至恒重、粉碎、过筛,得改性粉体;
S3:将S2的改性粉体与高密度聚乙烯、聚乙烯辛烯共弹性体按比例共混烘干,经双螺杆挤出机熔融挤出,切粒,得增强母粒。
S4:将S3的增强母粒与高密度聚乙烯进料至管材挤出机,经熔融挤出、冷却、牵引、切割,得增强型聚乙烯管材。
优选的技术方案为,S2中环氧基硅烷偶联剂溶液中溶质的质量浓度为1%~2%。
优选的技术方案为,S2中预处理云母粉加入反应体系后升温至45~55℃。进一步的反应体系升温至50~55℃。
优选的技术方案为,环氧基硅烷偶联剂的溶剂为异丙醇;S2中去离子水的加入量为溶剂体积的4%~10%。进一步的,S2中去离子水的加入量为溶剂质量的5%~8%。
优选的技术方案为,S1水溶性极性有机溶剂与有机酸的体积比为(15~25):1,所述云母粉的质量与所述混合溶液的体积比为1.5~2.5g/10ml。S1水溶性极性有机溶剂与有机酸的体积比为(18~22):1。
进一步的,水溶性极性有机溶剂为N,N-二甲基甲酰胺,有机酸为乙酸。
优选的技术方案为,S4中双螺杆挤出机的输送段温度为100~170℃,熔融段温度为170~190℃;均化段温度为190~220℃。
本发明的优点和有益效果在于:
该增强型聚乙烯管材采用云母粉和棒状氧化锌两种增强填料,云母粉具有二维片层结构,棒状氧化锌为短棒结构,利用含环氧基团的硅烷偶联剂和丙烯酸酯单体处理云母粉和棒状氧化锌制得复合粉体;
将复合粉体与高密度聚乙烯、聚乙烯辛烯共弹性体共混制得增强母粒,复合粉体中棒状氧化锌与云母粉的相互作用利于载荷的传递和转移,在一定程度上提高聚乙烯复合材料的强度,提升高密度聚乙烯管材的强度和低温抗冲击性。
具体实施方式
下面结合实施例,对本发明的具体实施方式作进一步描述。以下实施例仅用于更加清楚地说明本发明的技术方案,而不能以此来限制本发明的保护范围。
增强型聚乙烯管材的主要组分由高密度聚乙烯和增强母粒共混得到,除主要组分外,还包括润滑剂、抗氧剂、阻燃剂、抗菌剂等助剂,也即以上助剂可直接添加在聚乙烯管材的挤出进口料中,也可添加于增强母粒中。相较而言,将以上助剂添加于增强母粒中更有利于助剂在管材中的均匀分布。
环氧基丙烯酸酯单体选自丙烯酸缩水甘油酯和丙烯酸缩水甘油酯中的至少一种。
以下实施例所用高密度聚乙烯、(3-环氧丙基丙氧基)三甲氧基硅烷、2-(3,4-环氧环己基)乙基三甲氧基硅烷、甲基丙烯酸缩水甘油酯等均为市售,N,N-二甲基甲酰胺、异丙醇、乙酸、氢氧化钠、氯化锌、异丙醇等复合粉体制备所使用的药品均为商用分析纯;
云母粉:270目,径厚比30~50(对应粒径为53μm);
棒状氧化锌:采用直接沉淀法自制,氯化锌溶液和氢氧化钠溶液中溶质的摩尔比为1:10,将氯化锌溶液滴加至氢氧化钠溶液中,充分搅拌后将混合溶液置于80℃的烘箱保持24h,经过滤、洗涤过滤所得固体、离心、干燥;经表征,棒状氧化锌的直径为200~400nm、长度为8~10nm。
实施例1
制备改性粉体
S1:将乙酸滴加至N,N-二甲基甲酰胺中,N,N-二甲基甲酰胺与乙酸的体积比为20:1;将15份云母粉按照2g/10ml份质量体积比分散于混合溶液中,超声振荡和惰性气体保护下加入甲基丙烯酸缩水甘油酯单体0.06份,升温至90℃反应8h,冷却至室温,滤出云母粉,清洗烘干至恒重,得预处理云母粉;
S2:将28份棒状氧化锌分散于包含0.6份的(3-环氧丙基丙氧基)三甲氧基硅烷的异丙醇溶液中,棒状氧化锌的质量与异丙醇的体积比为1.67g/10ml;超声振荡混合加热至70℃反应3h,降温至室温后向反应体系加入S1的预处理云母粉15.06份和去离子水,去离子水的加入量为异丙醇体积的8%,乙酸调节pH至6,升温至50℃反应1h,冷却,滤出粉体,烘干至恒重、粉碎、过筛,得改性粉体。
制备增强母粒
将高密度聚乙烯7份、聚乙烯辛烯共弹性体5份、改性粉体43.66份、聚乙烯蜡2.735份、抗氧剂1.825份按比例高速混合烘干,经双螺杆挤出机熔融挤出,双螺杆挤出机的输送段温度为100~170℃,熔融段温度为170~190℃;均化段温度为190~220℃,切粒干燥,得增强母粒。
制备增强型聚乙烯管材
高密度聚乙烯与增强母粒按照质量比3:1进料至双螺杆挤出机,螺杆各段反应温度依次为:170℃、180℃、190℃、195℃、200℃、210℃、210℃、200℃、190℃,经熔融挤出、冷却得增强型聚乙烯管材,增强型聚乙烯管材用注射方法制成标准试样。
实施例2
实施例2的S1同实施例1;
S2:将28份棒状氧化锌分散于包含0.4份的(3-环氧丙基丙氧基)三甲氧基硅烷、0.2份的2-(3,4-环氧环己基)乙基三甲氧基硅烷的异丙醇溶液,棒状氧化锌的质量与异丙醇的体积比为1.67g/10ml;超声振荡混合,加热至70℃反应3h,降温至室温后向反应体系加入S1的预处理云母粉15.06份和去离子水,去离子水的加入量为异丙醇体积的8%,乙酸调节pH至6,升温至50℃反应1h,冷却,滤出粉体,烘干至恒重、粉碎、过筛,得改性粉体;
以S2的改性粉体和实施例1的生产工艺,制备增强型聚乙烯管材标准试样。
实施例3
实施例3的S1同实施例1;
S2:将28份棒状氧化锌分散于包含0.2份的(3-环氧丙基丙氧基)三甲氧基硅烷、0.4份的2-(3,4-环氧环己基)乙基三甲氧基硅烷的异丙醇溶液中,棒状氧化锌的质量与异丙醇的体积比为1.67g/10ml;超声振荡混合,加热至70℃反应3h,降温至室温后向反应体系加入S1的预处理云母粉15.06份和去离子水,去离子水的加入量为异丙醇体积的8%,乙酸调节pH至6,升温至50℃反应1h,冷却,滤出粉体,烘干至恒重、粉碎、过筛,得改性粉体;
以S2的改性粉体和实施例1的生产工艺,制备增强型聚乙烯管材标准试样。
实施例4
高密度聚乙烯与实施例1的增强母粒按照质量比2.5:1进至双螺杆挤出机,经熔融挤出、冷却得增强型聚乙烯管材,增强型聚乙烯管材用注射方法制成标准试样。
实施例5
实施例5的S2去离子水的加入量为异丙醇体积的12%,其他工艺参数同实施例1。
对比例1
将高密度聚乙烯187份、聚乙烯辛烯共弹性体5份、(3-环氧丙基丙氧基)三甲氧基硅烷0.6份、甲基丙烯酸缩水甘油酯0.06份、云母粉15份、棒状氧化锌28份、聚乙烯蜡2.375份、抗氧剂1.825份高速共混;基于实施例1的挤出工艺,共混料进料至双螺杆挤出机,得增强型聚乙烯管材,增强型聚乙烯管材用注射方法制成标准试样。
对比例2
将高密度聚乙烯187份、聚乙烯辛烯共弹性体5份、(3-环氧丙基丙氧基)三甲氧基硅烷0.4份、2-(3,4-环氧环己基)乙基三甲氧基硅烷0.2份、云母粉15份、棒状氧化锌28份、聚乙烯蜡2.375份、抗氧剂1.825份高速共混;基于实施例1的挤出工艺,共混料进料至双螺杆挤出机,得增强型聚乙烯管材,增强型聚乙烯管材用注射方法制成标准试样。
标准试样的检测:
1、按照GB/T 1040.1-2006《塑料拉伸性能的测定第1部分:总则》对标准试样进行拉伸强度及断裂伸长率的测试,拉伸速率50mm/min,实施例和对比例的试样测试结果见下表:
拉伸断裂强度/MPa | 断裂伸长率/% | |
实施例1 | 36.21 | 762 |
实施例2 | 37.38 | 785 |
实施例3 | 34.73 | 743 |
实施例4 | 38.34 | 794 |
实施例5 | 30.95 | 729 |
对比例1 | 27.75 | 707 |
对比例2 | 28.62 | 701 |
2、按照GB/T 1843-2008《塑料悬臂梁冲击强度的测定》对标准试样进行冲击性能测试,实施例和对比例的试样测试结果见下表:
悬臂梁冲击强度/KJ/m2 | |
实施例1 | 37.4 |
实施例2 | 40.1 |
实施例3 | 36.0 |
实施例4 | 42.8 |
实施例5 | 34.3 |
对比例1 | 31.7 |
对比例2 | 30.5 |
对比例1和对比例2的硅烷偶联剂与填料直接加入管材进料中,其中实施例1与对比例形成对照,实施例2与对比例2形成对照(对比例2中不包含甲基丙烯酸缩水甘油酯);结果表明,云母粉和棒状氧化锌经过预先处理制得的复合粉体有利于提升标准试样的拉伸断裂强度、断裂伸长率和耐冲击强度;
云母粉和棒状氧化锌复合粉体的制备过程中,环氧基丙烯酸酯单体的环氧基团开环并与云母面表面的羟基反应,得到环氧基丙烯酸酯单体改性的云母粉;环氧基硅烷偶联剂的烷氧基水解成烷氧基,取向于棒状氧化锌表面,与氧化锌表面的羟基发生水解缩聚反应,环氧基硅烷偶联剂的另一端环氧基在酸性条件下取向于环氧基丙烯酸酯单体改性的云母粉表面,环氧基丙烯酸酯单体取向于聚乙烯,使复合粉体与聚乙烯的界面具有充分的黏合力。片状云母粉和棒状氧化锌两种不同形态填料的复合粉体分均分散于聚乙烯基材中,当作用力施加于复合材料时,复合粉体结构能有效传递和分散载荷。
实施例1、实施例2和实施例3形成2-(3,4-环氧环己基)乙基三甲氧基硅烷含量的对照;实施例2试样的拉伸断裂强度、断裂伸长率和耐冲击强度优于实施例1和实施例3;2-(3,4-环氧环己基)乙基三甲氧基硅烷结构中环己基的位阻效应利于提高硅烷偶联剂改性氧化锌在云母表面的分布均匀程度,但是2-(3,4-环氧环己基)乙基三甲氧基硅烷的含量过大不利于片状云母粉和棒状氧化锌的复合,进而减弱复合粉体的增强效果。
实施例1与实施例4形成高密度聚乙烯与改性母粒共混比例的对照,测试结果表明,在优选范围内,聚乙烯复合材料的拉伸断裂强度、断裂伸长率和耐冲击强度随改性母粒的含量增加而提高。
实施例1与实施例5形成S2去离子水添加量的对照,在优选去离子水添加量的基础上,去离子水添加量过大则反应体系中醇含量减小,加热条件下硅醇缩合增加,不利于复合粉体的生成。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种增强型聚乙烯管材,其特征在于,主要组分由高密度聚乙烯和增强母粒按照质量之比(2~4.5):1共混制得;
按质量份数计,所述增强母粒的主要组成为:高密度聚乙烯7份、聚乙烯辛烯共弹性体3.5~6份、环氧基硅烷偶联剂0.2~0.8份、环氧基丙烯酸酯单体0.03~0.09份、云母粉10~20份、棒状氧化锌20~35份。
2.根据权利要求1所述的增强型聚乙烯管材,其特征在于,所述云母粉的粒径为10~200μm;所述棒状氧化锌的直径为200~400nm,长度为8~10nm。
3.根据权利要求1所述的增强型聚乙烯管材,其特征在于,所述环氧基硅烷偶联剂由(3-环氧丙基丙氧基)三甲氧基硅烷和2-(3,4-环氧环己基)乙基三甲氧基硅烷组合而成,(3-环氧丙基丙氧基)三甲氧基硅烷与2-(3,4-环氧环己基)乙基三甲氧基硅烷的质量之比为(1.7~2.5):1。
4.根据权利要求1所述的增强型聚乙烯管材,其特征在于,所述增强母粒还包括润滑剂、抗氧剂、阻燃剂、抗菌剂中的至少一种。
5.一种增强型聚乙烯管材的生产方法,其特征在于,基于权利要求1至4中任意一项所述的增强型聚乙烯管材,包括以下步骤:
S1:将云母粉分散于水溶性极性有机溶剂和有机酸的混合溶液中,超声振荡和惰性气体保护下加入环氧基丙烯酸酯单体,升温至80~100℃反应至少5h,冷却至室温,滤出云母粉,清洗烘干至恒重,得预处理云母粉;
S2:将棒状氧化锌分散于环氧基硅烷偶联剂的醇溶液中,超声振荡混合加热至50~80℃反应至少30min,降温至室温后向反应体系加入S1的预处理云母粉和去离子水,调节pH至5.5~6.5,升温反应0.5~1h,冷却,滤出粉体,烘干至恒重、粉碎、过筛,得改性粉体;
S3:将S2的改性粉体与高密度聚乙烯、聚乙烯辛烯共弹性体按比例共混烘干,经双螺杆挤出机熔融挤出,切粒,得增强母粒;
S4:将S3的增强母粒与高密度聚乙烯进料至管材挤出机,经熔融挤出、冷却、牵引、切割,得增强型聚乙烯管材。
6.根据权利要求5所述的增强型聚乙烯管材的生产方法,其特征在于,S2中环氧基硅烷偶联剂溶液中溶质的质量浓度为1%~2%。
7.根据权利要求5所述的增强型聚乙烯管材的生产方法,其特征在于,S2中预处理云母粉加入反应体系后升温至45~55℃。
8.根据权利要求6所述的增强型聚乙烯管材的生产方法,其特征在于,环氧基硅烷偶联剂的溶剂为异丙醇;S2中去离子水的加入量为溶剂体积的4%~10%。
9.根据权利要求5所述的增强型聚乙烯管材的生产方法,其特征在于,S1水溶性极性有机溶剂与有机酸的体积比为(15~25):1,所述云母粉的质量与所述混合溶液的体积比为1.5~2.5g/10ml。
10.根据权利要求5所述的增强型聚乙烯管材的生产方法,其特征在于,S4中双螺杆挤出机的输送段温度为100~170℃,熔融段温度为170~190℃;均化段温度为190~220℃。
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