CN114179446A - 具有远红外辐射功能的长效阻氧地暖管道及其制备方法 - Google Patents
具有远红外辐射功能的长效阻氧地暖管道及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种具有远红外辐射功能的长效阻氧地暖管道及其制备方法,管道由外到内共三层,依次为具有远红外辐射性能的阻氧层,以及粘结层和聚烯烃树脂层,阻氧层、粘结层和聚烯烃树脂层的厚度比为1.5:0.5:8;阻氧层的具体成分及质量分数为:EVOH树脂100份、改性剂1‑8份;其中,所述改性剂的成分为:石墨烯、海藻碳、陶瓷粉体和二氧化硅四种材料的混合物,四种材料的质量分数比为:(1‑2):(2‑5):(2‑5):(1‑3);粘结层为马来酸酐接枝聚乙烯材质;聚烯烃树脂层为耐热聚乙烯材质。本发明所述的具有远红外辐射功能的长效阻氧地暖管道及其制备方法,通过对阻氧层进行共混改性提高其表面硬度,以及吸湿后的阻隔性的同时,提升阻氧层的远红外辐射性能,起到节能的目的。
Description
技术领域
本发明涉及一种功能型塑料管道及其制备技术领域,尤其是涉及一种具有远红外辐射功能的长效阻氧地暖管道及其制备方法。
背景技术
地暖的全称是低温热水地板辐射采暖,是一种以水为介质,通过管道内的低温热水加热地板,然后地板将热量以辐射的方式散发到房间内,以此来提高房间的舒适度。相比于传统的散热片采暖,地暖更加高效节能,而且由于其自下而上的梯度式加热方法,会给人一种脚暖头凉的舒适感,符合“温足而凉顶”的中医健身理论。因此,地暖受到越来越多家庭的青睐。
由于普通的阻氧PE-RT地暖管道的阻氧层表面硬度较低容易被划伤且其吸湿后阻隔性能会大幅降低,从而无法起到有效阻隔氧气的作用。并且根据文献记载,人体辐射和吸收红外线的波长主要集中在8-15μm。而地暖主要以热辐射的方式来加热室内空气,通过引入改性材料来增加波长在8-15μm范围内的红外线数量占比,既提高了房间内的舒适度,还能通过共振现象提高人体的热感知,间接的起到节能的效果。
因此,为了提高传统阻氧地暖管道的表面硬度及吸湿后的阻隔性能,延缓地暖系统中金属配件的腐蚀,降低漏水事故发生的概率,并且提高人体的热感知和舒适度,需要开发一种能够提高聚烯烃管道阻隔氧气性能,并具备远红外辐射性能的新型地暖管道。
发明内容
有鉴于此,本发明旨在提出一种具有远红外辐射功能的长效阻氧地暖管道及其制备方法,通过对阻氧层进行共混改性提高其表面硬度,以及吸湿后的阻隔性的同时,提升阻氧层的远红外辐射性能,起到节能的目的。
本发明的另一目的在于提供该具有远红外辐射功能的长效阻氧地暖管道的制备方法。
为达到上述目的,本发明的技术方案是这样实现的:
一种具有远红外辐射功能的长效阻氧地暖管道,管道由外到内共三层,依次为具有远红外辐射性能的阻氧层,以及粘结层和聚烯烃树脂层,所述阻氧层、粘结层和聚烯烃树脂层的厚度比为1.5:0.5:8;
所述阻氧层的具体成分及质量分数为:EVOH树脂100份、改性剂1-8份;其中,所述改性剂的成分为:石墨烯、海藻碳、陶瓷粉体和二氧化硅四种材料的混合物,四种材料的质量分数比为:(1-2):(2-5):(2-5):(1-3);
所述粘结层为马来酸酐接枝聚乙烯材质;所述聚烯烃树脂层为耐热聚乙烯材质。
优选的,所述石墨烯、海藻碳、陶瓷粉体和二氧化硅的质量分数比为:2:4:3:1。
进一步地,所述石墨烯的片层为2-8层;所述石墨烯的片径为20-800nm。
进一步地,所述海藻碳的粒径为50-100nm;所述海藻碳的表面经过硅烷偶联剂KH-550处理。
进一步地,所述海藻碳的表面处理方法为:称取8g海藻碳于超声波清洗器中分散30-50min,在三口烧瓶中加入200mL的乙醇溶液,水浴搅拌加热至70-80℃,缓慢滴加2-5滴偶联剂KH-550,水解20-30min后,加入分散好的海藻碳反应1-2h,反应结束后,经真空抽滤并用乙醇反复洗涤后在真空干燥箱中于120℃下烘干6h,经研磨后得到表面改性的海藻碳粉末。
进一步地,所述陶瓷粉体为MgO-Al2O3-TiO2-ZrO2系的陶瓷粉;所述陶瓷粉体的粒径为20-30nm;所述陶瓷粉体经过硅烷偶联剂KH-550的表面处理。
进一步地,所述陶瓷粉体的表面处理方法为:将硅烷偶联剂KH-550溶解在体积比为1:4的水和乙醇的混合溶液中,超声分散30min后,用乙酸调节溶液的PH为3-4。向溶液中加入10g干燥后的纳米陶瓷粉,超声分散20min后继续水浴(70℃)加热30min,反应结束后,经真空抽滤并用乙醇反复洗涤后在真空干燥箱中于120℃下烘干6h,经研磨后得到表面改性的陶瓷粉末。
进一步地,所述二氧化硅为气相二氧化硅;所述二氧化硅的粒径为20-30nm。
一种地暖管道的制备方法,包括如下步骤:按照配方将EVOH树脂和石墨烯、表面处理后的海藻碳、表面处理后的MgO-Al2O3-TiO2-ZrO2系的陶瓷粉、气相二氧化硅分别从主喂料口和侧喂料口加入到双螺杆挤出机中进行熔融共混,温度为190-200℃,采用全螺纹等距不等深螺杆,螺杆长径比为23-28,压缩比为3.0-4.0,加料段、压缩段和计量段约各占1/3,经剪切造粒后得到具有远红外辐射性能的改性EVOH树脂;
利用三台挤出机采用三层共挤的方式,经过口芯模、真空定径、冷却定型等步骤后得到具有远红外辐射性能的长效阻氧地暖管道。其中,外层具有远红外性能的阻氧层的模头温度为195-205℃,机筒温度为190-200℃;中间层马来酸酐接枝聚乙烯粘结层的模头温度为190-200℃,机筒温度为185-195℃;内层耐热聚乙烯树脂层的模头温度为195-205℃,机筒温度为185-195℃;管道在挤出过程中的牵引速度为20-30m/min,口模内径尺寸为30-45mm。
相对于现有技术,本发明所述的具有远红外辐射功能的长效阻氧地暖管道及其制备方法具有以下有益效果:
(1)本发明所述的一种具有远红外辐射功能的长效阻氧地暖管道,由于在外层引入了石墨烯、海藻碳和陶瓷粉体等多种在波长范围为8-15μm具有较高发射率的远红外材料,从而增加了地暖管道热辐射时易于被人体所吸收红外线波段(8-15μm)的占比,提高了人体的热感知和热舒适度。相比于普通地暖管道,可以在较低的供暖水温下起到同样的热舒适效果,达到节能的目的。
(2)本发明所述的一种具有远红外辐射功能的长效阻氧地暖管道,添加的石墨烯为片层结构,可以增加EVOH阻氧层的阻氧性能,即便外层吸湿后,确保其仍然能起到很好的阻氧效果;添加的气相二氧化硅可以很好的分散在EVOH树脂中,起到异相成核的作用,提高EVOH树脂的结晶度,增加其表面硬度,防止阻氧层被擦伤。
上述说明仅是本发明技术方案的概述,为了能够更清楚了解本发明的技术手段,而可依照说明书的内容予以实施,而且为了让本发明的上述和其他目的、特征和优点能够更明显易懂,以下特举本发明的具体实施方式。
附图说明
构成本发明的一部分的附图用来提供对本发明的进一步理解,本发明的示意性实施例及其说明用于解释本发明,并不构成对本发明的不当限定。在附图中:
图1为本发明所述的具有远红外辐射功能的长效阻氧地暖管道的剖面结构示意图。
附图标记说明:
1-聚烯烃树脂层;2-粘结层;3-阻氧层。
具体实施方式
除有定义外,以下实施例中所用的技术术语具有与本发明所属领域技术人员普遍理解的相同含义。以下实施例中所用的试验试剂,如无特殊说明,均为常规生化试剂;所述实验方法,如无特殊说明,均为常规方法。
下面将参考附图并结合实施例来详细说明本发明。
具体实施例1
一种具有远红外辐射功能的长效阻氧地暖管道,包括从内到外设置的聚烯烃树脂层1、粘结层2和阻氧层3,所述聚烯烃树脂层1、粘结层2和阻氧层3的层厚比为8:0.5:1.5。
所述聚烯烃树脂层1由耐热聚乙烯材料挤塑而成。
所述粘结层2由马来酸酐接枝聚乙烯材料挤塑而成。
所述阻氧层3由具有远红外辐射性能的阻氧材料挤塑而成;具有远红外辐射性能的长效阻氧材料的组成成分及其质量份数为:聚乙烯乙烯醇(EVOH树脂)100份、改性剂4份;其中改性剂为石墨烯、海藻碳、陶瓷粉体和二氧化硅四种材料的混合物,质量分数比为:2:4:3:1。
将聚烯烃树脂层1的耐热聚乙烯材料加入到第一台挤出机中。
将中间层粘结层2的马来酸酐接枝聚乙烯材料加入到第二台挤出机中。
将远红外辐射功能长效阻氧层3的具有远红外辐射性能的阻氧材料加入到第三台挤出机中。
利用三台挤出机采用三层共挤的方式,经过口芯模、真空定径、冷却定型等步骤后得到具有远红外辐射功能的长效阻氧地暖管道。
具体实施例2
一种具有远红外辐射功能的长效阻氧地暖管道,包括从内到外设置的聚烯烃树脂层1、粘结层2和阻氧层3,所述聚烯烃树脂层1、粘结层2和阻氧层3的层厚比为8:0.5:1.5。
所述聚烯烃树脂层1由耐热聚乙烯材料挤塑而成。
所述粘结层2由马来酸酐接枝聚乙烯材料挤塑而成。
所述远红外辐射功能长效阻氧层3由具有远红外辐射性能的阻氧材料挤塑而成;具有远红外辐射性能的长效阻氧材料的组成成分及其质量份数为:聚乙烯乙烯醇(EVOH)100份、改性剂6份;其中改性剂为石墨烯、海藻碳、陶瓷粉体和二氧化硅四种材料的混合物,质量分数比为:2:4:3:1。
将聚烯烃树脂层1的耐热聚乙烯材料加入到第一台挤出机中。
将中间层粘结层2的马来酸酐接枝聚乙烯材料加入到第二台挤出机中。
将远红外辐射功能长效阻氧层3的具有远红外辐射性能的阻氧材料加入到第三台挤出机中。
利用三台挤出机采用三层共挤的方式,经过口芯模、真空定径、冷却定型等步骤后得到具有远红外辐射功能的长效阻氧地暖管道。
具体实施例3
一种具有远红外辐射功能的长效阻氧地暖管道,包括从内到外设置的聚烯烃树脂层1、粘结层2和阻氧层3,所述聚烯烃树脂层1、粘结层2和阻氧层3的层厚比为8:0.5:1.5。
所述聚烯烃树脂层1由耐热聚乙烯材料挤塑而成。
所述粘结层2由马来酸酐接枝聚乙烯材料挤塑而成。
所述远红外辐射功能长效阻氧层3由具有远红外辐射性能的阻氧材料挤塑而成;具有远红外辐射性能的长效阻氧材料的组成成分及其质量份数为:聚乙烯乙烯醇(EVOH)100份、改性剂8份;其中改性剂为石墨烯、海藻碳、陶瓷粉体和二氧化硅四种材料的混合物,质量分数比为:2:4:3:1;
将聚烯烃树脂层1的耐热聚乙烯材料加入到第一台挤出机中。
将中间层粘结层2的马来酸酐接枝聚乙烯材料加入到第二台挤出机中。
将远红外辐射功能长效阻氧层3的具有远红外辐射性能的阻氧材料加入到第三台挤出机中。
利用三台挤出机采用三层共挤的方式,经过口芯模、真空定径、冷却定型等步骤后得到具有远红外辐射功能的长效阻氧地暖管道。
具体实施例4
一种具有远红外辐射功能的长效阻氧地暖管道,包括从内到外设置的聚烯烃树脂层1、粘结层2和阻氧层3,所述聚烯烃树脂层1、粘结层2和阻氧层3的层厚比为8:0.5:1.5。
所述聚烯烃树脂层1由耐热聚乙烯材料挤塑而成。
所述粘结层2由马来酸酐接枝聚乙烯材料挤塑而成。
所述远红外辐射功能长效阻氧层3由具有远红外辐射性能的阻氧材料挤塑而成;具有远红外辐射性能的长效阻氧材料的组成成分及其质量份数为:聚乙烯乙烯醇(EVOH)100份、改性剂8份;其中改性剂为石墨烯、海藻碳、陶瓷粉体和二氧化硅四种材料的混合物,质量分数比为:1:4:3:2;
将聚烯烃树脂层1的耐热聚乙烯材料加入到第一台挤出机中。
将中间层粘结层2的马来酸酐接枝聚乙烯材料加入到第二台挤出机中。
将远红外辐射功能长效阻氧层3的具有远红外辐射性能的阻氧材料加入到第三台挤出机中。
利用三台挤出机采用三层共挤的方式,经过口芯模、真空定径、冷却定型等步骤后得到具有远红外辐射功能的长效阻氧地暖管道。
具体实施例5
一种具有远红外辐射功能的长效阻氧地暖管道,包括从内到外设置的聚烯烃树脂层1、粘结层2和阻氧层3,所述聚烯烃树脂层1、粘结层2和阻氧层3的层厚比为8:0.5:1.5。
所述聚烯烃树脂层1由耐热聚乙烯材料挤塑而成。
所述粘结层2由马来酸酐接枝聚乙烯材料挤塑而成。
所述远红外辐射功能长效阻氧层3由具有远红外辐射性能的阻氧材料挤塑而成;具有远红外辐射性能的长效阻氧材料的组成成分及其质量份数为:聚乙烯乙烯醇(EVOH)100份、改性剂8份;其中改性剂为石墨烯、海藻碳、陶瓷粉体和二氧化硅四种材料的混合物,质量分数比为:2:5:2:1;
将聚烯烃树脂层1的耐热聚乙烯材料加入到第一台挤出机中。
将中间层粘结层2的马来酸酐接枝聚乙烯材料加入到第二台挤出机中。
将远红外辐射功能长效阻氧层3的具有远红外辐射性能的阻氧材料加入到第三台挤出机中。
利用三台挤出机采用三层共挤的方式,经过口芯模、真空定径、冷却定型等步骤后得到具有远红外辐射功能的长效阻氧地暖管道。
具体实施例6
一种具有远红外辐射功能的长效阻氧地暖管道,包括从内到外设置的聚烯烃树脂层1、粘结层2和阻氧层3,所述聚烯烃树脂层1、粘结层2和阻氧层3的层厚比为8:0.5:1.5。
所述聚烯烃树脂层1由耐热聚乙烯材料挤塑而成。
所述粘结层2由马来酸酐接枝聚乙烯材料挤塑而成。
所述远红外辐射功能长效阻氧层3由具有远红外辐射性能的阻氧材料挤塑而成;具有远红外辐射性能的长效阻氧材料的组成成分及其质量份数为:聚乙烯乙烯醇(EVOH)100份、改性剂8份;其中改性剂为石墨烯、海藻碳、陶瓷粉体和二氧化硅四种材料的混合物,质量分数比为:2:2:5:1;
将聚烯烃树脂层1的耐热聚乙烯材料加入到第一台挤出机中。
将中间层粘结层2的马来酸酐接枝聚乙烯材料加入到第二台挤出机中。
将远红外辐射功能长效阻氧层3的具有远红外辐射性能的阻氧材料加入到第三台挤出机中。
利用三台挤出机采用三层共挤的方式,经过口芯模、真空定径、冷却定型等步骤后得到具有远红外辐射功能的长效阻氧地暖管道。
具体实施例1-6的任一实施例中挤出机的工艺条件如表1所示:
表1
根据GB/T34437-2017多层复合塑料管材氧气渗透性能测试方法,按照实施例1-6中的配方制备测试样品(对比例选用市售三层阻氧管材),温度为40℃且湿度分别为50%和80%的条件下测试氧气透过系数,测试结果如表2、表3所示:
表2温度为40℃,湿度为40%
表3温度为40℃,湿度为90%
由表2和表3的测试结果可知,所制样品的氧气透过系数随着体系中远红外辐射功能材料的加入均有不同程度的变化。在温度为40℃,湿度为40%的环境条件下,各实施例中样品的氧气透过系数均满足GB/T 28799-2020中小于等于0.32mg/(m2 d)的要求;并且相比于未改性的普通三层阻氧管材,实施例中样品的氧气透过系数有不同幅度的降低。当环境温度为40℃,湿度为90%时,由于EVOH中含有较多羟基使其具有较强的吸水性能,吸水后导致EVOH的气体阻隔性能大幅降低,因此各实施例中样品的氧气透过系数均有不同程度提高,但仍远低于未改性的普通三层阻氧管道;其中实施例3、5、6中样品的氧气透过系数符合GB/T 28799-2020中小于等于0.32mg/(m2 d)的要求。表明石墨烯能够在湿度较大的环境中弥补EVOH因吸水导致的气体阻隔性大幅降低。
根据GB/T7287-2008红外辐射加热器实验方法,按照实施例1-6中的配方制备测试样品,在室温25℃下测试波长为8-15μm下样品的法相发射率。测试结果如表4所示:
表4
由表4测试结果可知,实施例1-6中样品的法向发射率相比于未改性的市面常用三层阻氧管材均有不同程度提高,最大为0.9341。相比于市面常用三层阻氧管材的0.88,提高了6.15%。
本发明所制备的一种具有远红外辐射性能的长效阻氧地暖管道,由于在外层EVOH中引入了气相二氧化硅、石墨烯、陶瓷粉、海藻碳等四种具有较高远红外(8-15μm)发射率的改性材料,从而提高了管材外表面在8-15μm波长区间的热辐射红外线占比,提高了人体的热感知和热舒适度,一定程度上起到节能的效果。同时,体系中的石墨烯由于其独特的片层结构,除了能提高EVOH阻氧层的氧气阻隔性能外,还能在EVOH吸水导致阻隔性能降低时,维持阻氧层的氧气阻隔性能,确保管材仍能起到良好的阻氧效果。此外,添加的气相二氧化硅等纳米颗粒,可以很好的分散在EVOH树脂中,起到异相成核的作用,提高EVOH树脂的结晶度,增加其表面硬度。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种具有远红外辐射功能的长效阻氧地暖管道,其特征在于,管道由外到内共三层,依次为具有远红外辐射性能的阻氧层,以及粘结层和聚烯烃树脂层,所述阻氧层、粘结层和聚烯烃树脂层的厚度比为1.5:0.5:8;
所述阻氧层的具体成分及质量分数为:EVOH树脂100份、改性剂1-8份;其中,所述改性剂的成分为:石墨烯、海藻碳、陶瓷粉体和二氧化硅四种材料的混合物,四种材料的质量分数比为:(1-2):(2-5):(2-5):(1-3);
所述粘结层为马来酸酐接枝聚乙烯材质;所述聚烯烃树脂层为耐热聚乙烯材质。
2.根据权利要求1所述的具有远红外辐射功能的长效阻氧地暖管道,其特征在于:所述石墨烯、海藻碳、陶瓷粉体和二氧化硅的质量分数比为:2:4:3:1。
3.根据权利要求1所述的具有远红外辐射功能的长效阻氧地暖管道,其特征在于:所述石墨烯的片层为2-8层;所述石墨烯的片径为20-800nm。
4.根据权利要求1所述的具有远红外辐射功能的长效阻氧地暖管道,其特征在于:所述海藻碳的粒径为50-100nm;所述海藻碳的表面经过硅烷偶联剂KH-550处理。
5.根据权利要求4所述的具有远红外辐射功能的长效阻氧地暖管道,其特征在于:所述海藻碳的表面处理方法为:将海藻碳放于超声波清洗器中分散,在三口烧瓶中加入乙醇溶液,水浴搅拌加热至70-80℃,缓慢滴加2-5滴偶联剂KH-550,水解后,加入分散好的海藻碳,反应结束后,经真空抽滤并用乙醇反复洗涤后,在真空干燥箱中烘干,经研磨后得到表面改性的海藻碳粉末。
6.根据权利要求1所述的具有远红外辐射功能的长效阻氧地暖管道,其特征在于:所述陶瓷粉体为MgO-Al2O3-TiO2-ZrO2系的陶瓷粉;所述陶瓷粉体的粒径为20-30nm;所述陶瓷粉体经过硅烷偶联剂KH-550的表面处理。
7.根据权利要求6所述的具有远红外辐射功能的长效阻氧地暖管道,其特征在于:所述陶瓷粉体的表面处理方法为:将硅烷偶联剂KH-550溶解在体积比为1:4的水和乙醇的混合溶液中,超声分散后,用乙酸调节溶液的PH为3-4,向溶液中加入干燥后的纳米陶瓷粉,超声分散后继续于70℃下水浴加热,反应结束后,经真空抽滤并用乙醇反复洗涤后在真空干燥箱中烘干,经研磨后得到表面改性的陶瓷粉末。
8.根据权利要求1所述的具有远红外辐射功能的长效阻氧地暖管道,其特征在于:所述二氧化硅为气相二氧化硅;所述二氧化硅的粒径为20-30nm。
9.一种根据权利要求1-8任一项所述地暖管道的制备方法,其特征在于,包括如下步骤:
按照配方将EVOH树脂和石墨烯、海藻碳、陶瓷粉体和二氧化硅分别从主喂料口和侧喂料口加入到双螺杆挤出机中进行熔融共混,经剪切造粒后得到具有远红外辐射性能的改性EVOH树脂;
利用三台挤出机采用三层共挤的方式,经过口芯模、真空定径、冷却定型等步骤后得到具有远红外辐射性能的长效阻氧地暖管道。
10.根据权利要求9所述的制备方法,其特征在于:
熔融共混的温度为190-200℃;所述挤出机采用全螺纹等距不等深螺杆;螺杆长径比为23-28;压缩比为3.0-4.0;加料段、压缩段和计量段约各占1/3;
外层阻氧层的模头温度为195-205℃,机筒温度为190-200℃;
中间层粘结层的模头温度为190-200℃,机筒温度为185-195℃;
内层聚烯烃树脂层的模头温度为195-205℃,机筒温度为185-195℃;
管道在挤出过程中的牵引速度为20-30m/min,口模内径尺寸为30-45mm。
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