CN109721912A - 一种阻隔层、多层塑料复合管及制备方法 - Google Patents
一种阻隔层、多层塑料复合管及制备方法 Download PDFInfo
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Abstract
本发明公开了一种阻隔层,包括以下原料组份,以重量份数计为,聚乙烯醇100份,乙烯‑乙烯醇共聚物0.5‑50份,乙烯‑醋酸乙烯共聚物0.5‑25份,丙三醇0.1‑2份,钙锌稳定剂0‑8份,纳米玻璃纤维母料0.5‑30份,聚乙烯0.5‑35份,马来酸酐接枝共聚物0.5‑10份。本发明的阻隔层中,以聚乙烯醇为主要的成分,通过添加乙烯‑乙烯醇聚合物、乙烯‑醋酸乙烯共聚物以及纳米玻璃纤维母料,各组分之间相互作用,提高阻隔层加工性能、阻隔性都以及柔韧性,相对于单一的聚乙烯醇阻隔层,本发明的阻隔层的阻隔性能高提升了3‑10倍。
Description
技术领域
本发明属于管材技术领域,具体涉及一种具有阻隔功能的多层塑料复合管。
背景技术
目前塑料管道广泛使用在给水、输油、地暖等领域,由于通用塑料价格便宜,成本低,耐老化,生产加工容易,安装运输、维修方便,但塑料管材如PP-R安装在有涂料的地方,由于管材的阻隔性差,涂料气味进入管道,污染水质;PE输油管道在使用的过程中,也会因阻隔差,导致石油渗透到土壤中,污染地下水源;而普通地暖使用的管材,在长期的使用过程中,也会因管材的阻氧性差,腐蚀金属部件,管道系统使用寿命短,而目前阻氧地暖管材阻氧层采用的乙烯-乙烯醇共聚物成本高;给水管道也会因阻氧性差,导致管内容易滋生有害微生物,同时存在管材氧化快,使用寿命短的问题。
发明内容
本发明的目的之一在于,提供一种阻隔层,将该阻隔层应用在管材中,可明显的提高管材的阻隔性能,起到阻氧、防渗透的作用。阻隔层的刚性和韧性均优于单一的聚乙烯醇或乙烯-乙烯醇共聚物,并且阻隔层的抗撕裂性和抗低温性都较优异。
为了实现上述目的,本发明采用的技术方案为:一种阻隔层,包括以下原料组份,以重量份数计为,
在本发明的阻隔层的原料配方中,添加的聚乙烯醇具有很好的耐油性、阻隔性,但单一的聚乙烯醇加工性能差。而乙烯-乙烯醇加工性能优异,并且乙烯-乙烯醇与聚乙烯醇互溶,具有增容效果;同时乙烯-乙烯醇也具有一定的阻隔性能,通过乙烯-乙烯醇改善聚乙烯醇的加工性能。当乙烯-乙烯醇的添加量较多时,会导致阻隔性下降,因此将乙烯-乙烯醇的重量份数控制在0.5-50份,可同时具有优异的加工性能和阻隔性,
乙烯-醋酸乙烯共聚物可改善聚乙烯醇的韧性,又能与聚乙烯醇和聚乙烯相容,具有增容效果。聚乙烯和乙烯-醋酸乙烯共聚物共同作用,提高阻隔层的柔韧性。
丙三醇作为溶剂,可改善阻隔层的加工性能,但当丙三醇的用量较大时,使得熔融态的原料的流动性太好,导致制备的阻隔层的密度小、强度低,并且阻隔性能也会有所降低。
在阻隔层的配方中添加纳米玻璃纤维母料,以提高阻隔层的刚性,同时也提高阻隔性能,改变取向,使得各相同性。
较优选的,所述原料组份重量份数为,
较优选的,所述原料组份重量份数为,
较优选的,所述原料组份重量份数为,
进一步的,所述马来酸酐接枝共聚物为聚乙烯接枝马来酸酐共聚物、聚丙烯接枝马来酸酐共聚物、耐热聚乙烯接枝马来酸酐共聚物中的一种或多种的混合。
本发明的目的之二在于:提供一种阻隔性能优异的塑料复合管,该塑料复合管中制备有上述阻隔层,塑料复合管可应用在石油运输、给排水、地暖等领域中,相对于现有技术中的管材,其阻隔性能提升3-10倍。
为了实现上述目的,本发明采用的技术方案为:一种多层塑料复合管,包括承压层、粘结层和阻隔层,所述粘结层位于所述承压层和所述阻隔层之间。其中,阻隔层为上述任一阻隔层。
进一步的,复合管中的承压层、阻隔层和粘结层均可以为多个,承压层、粘结层和阻隔层交替间隔设置。复合管材由内向外依次为承压层、粘结层、阻隔层、粘结层和承压层。在实际的生产过程中,可根据实际的需求,设计合理的层数,阻隔层可以在最内层,可以位于最外层,也可以是中间层。
进一步的,所述复合管由内向外依次为阻隔层、粘结层和承压层。
进一步的,所述复合管由内向外依次为承压层、粘结层和阻隔层。
进一步的,所述承压层的材质为无规共聚聚丙烯(PP-R)、聚乙烯(PE)、耐热聚乙烯(PE-RT)、聚丁烯(PB)中的一种。
进一步的,所述粘结层的材质为马来酸酐接枝共聚物,所述马来酸酐接枝共聚物具体为聚乙烯接枝马来酸酐共聚物、聚丙烯接枝马来酸酐共聚物、耐热聚乙烯接枝马来酸酐共聚物中的一种或多种的混合。
在本发明中,粘结层主要起到粘结阻隔层和承压层的作用,承压层主要的作用是提供一定的强度,相应的,阻隔层主要是起到阻挡、隔离的作用。当阻隔层在外面时,如果经常与水接触时,可在阻隔层中加入交联剂和抗氧剂,防止阻隔层水解。
本发明的目的之三在于,提供一种上述多层塑料复合管材的制备方法,通过该方法结合本发明的阻隔层的原料配方,制备出的塑料复合管材阻隔性好,防渗透能力强,生产成本低。
为了实现上述目的,本发明采用的技术方案为:一种多层塑料复合管的制备方法,其特征在于:包括以下步骤,
S1:采用多层共挤机分别挤出阻隔层、粘结层和承压层;
S2:所述阻隔层、粘结层和所述承压层在多层共挤机的机头共挤出;
S3:经牵引、切割、冷却至室温、烘烤,得到所述复合管。
进一步的,所述阻隔层在挤出时,所述共挤机机筒的第一段温度为175-185℃,第二段温度为185℃-195℃,第三段温度为195℃-200℃。
进一步的,所述承压层在挤出时,所述共挤机机筒的第一段温度为160-185℃,第二段温度为185℃-190℃,第三段温度为190℃-200℃,第四段温度为200-210℃。
进一步的,在所述共挤出时,所述共挤机机筒的第一段温度为180-185℃,第二段温度为185-210℃,第三段温度为210-220℃。
进一步的,所述粘结层在挤出时,所述共挤机机筒的第一段温度为175-185℃,第二段温度为185-195℃,第三段温度为195-200℃
进一步的,所述牵引的速度为1-50m/min。
进一步的,所述烘烤温度为60-120℃,烘烤时间为0.15-4h。通过烘烤,消除复合管中的应力,同时去除复合管中的水分,烘烤后比烘烤前管材耐压强度提高10%以上。
由于采用了上述技术方案,本发明的有益效果是:
本发明的阻隔层中,以聚乙烯醇为主要的成分,通过添加乙烯-乙烯醇聚合物、乙烯-醋酸乙烯共聚物以及纳米玻璃纤维母料,各组分之间相互作用,提高阻隔层加工性能、阻隔性都以及柔韧性,相对于现有普通管材,本发明的阻隔层的阻隔性能高提升了3-10倍。
由本发明的塑料复合管包括阻隔层、粘结层和承压层,阻隔层和承压层通过粘结层连接,阻隔层起到阻挡隔离的作用,承压层提供一定的强度,阻隔层和承压层共同作用,使得本发明的塑料复合管材同时具有高强度和高阻隔性,并且本发明的阻隔层有现有的技术中的管材阻隔层相比,在达到相同阻隔效果时,本发明的阻隔层的厚度较薄;相同厚度的阻隔层,本发明的阻隔层的阻隔性能明显优于现有技术中的阻隔层;将本发明的塑料复合管作为给水管,可有效的阻隔管外的氧气,防止管内有害微生物滋生。本发明中塑料复合管材还可作为输油管、暖气管等使用。
本发明的塑料复合管材的生产成本低、管材的阻隔性能后,应用领域广泛。
具体实施方式
各实施例中,阻隔层的原料配比如下表1所示;
表1实施例1-6中阻隔层原料配比(重量份数)
需说明的是,在上述表1中,实施例1中的马来酸酐接枝共聚物为聚丙烯马来酸酐接枝共聚物;实施例2中为聚乙烯马来酸酐接枝共聚物,实施例3中为耐热聚乙烯接枝马来酸酐共聚物,实施例4中为聚丙烯马来酸酐接枝共聚物和聚乙烯马来酸酐接枝共聚物的混合物,实施例5中为聚乙烯马来酸酐接枝共聚物和耐热聚乙烯接枝马来酸酐共聚物的混合物;实施例6中为耐热聚乙烯接枝马来酸酐共聚物。
在本发明中,阻隔层中的所用到的聚乙烯醇的聚合度为超高聚合度(分子量25~30万),具有极性基团,表面能大,分子间间隙小。
实施例1:PP-R给水管
将阻隔层原料混合均匀;准备好聚丙烯接枝马来酸酐共聚物,加入2%的红色母料,常温搅拌混合均匀,作为粘结层;再准备好PP-R树脂,2%的白色母料,作为承压层;按第一段温度为175℃,第二段温度为185℃,第三段温度为195℃挤出阻隔层;按第一段温度为170℃,第二段温度为185℃,第三段温度为190℃,第四段温度为200℃挤出承压层;按第一段温度为175℃,第二段温度为185℃,第三段温度为195℃挤出粘结层;再将阻隔层、粘结层和承压层在机头共挤出,共挤出时第一段温度为180℃,第二段温度为185℃,第三段温度为210℃,在机头处以2m/min的牵引速度进行牵引,然后在经过切割、冷却至室温,得到复合管预成品,再将预成品管材置于80℃下烘烤30min,制得塑料管复合管材1号。
本实施例中塑料复合管材的主体即承压层为PP-R,可用作给水管,此类管材安装屋内屋外与涂料及其他化工原料接触的地方,有效防止其他成分渗透污染管材内水质;与现有技术中的单一的乙烯-乙烯醇共聚物做阻隔层,本实施例的管材的阻隔性能提高了60%,管材的防渗透能力提高了60%。
在本实施例中,以阻隔层作为最外层,阻隔层的厚度为0.12mm,复合管的外径为20mm,管壁的壁厚为2.3mm。
本实施例同样适用于聚丁烯(PB)管材,即将承压成用PB替换。
实施例2:PE石油管
将阻隔层原料混合均匀;准备好聚乙烯接枝马来酸酐共聚物,加入2%的红色母料,常温搅拌混合均匀,作为粘结层;再准备好PE树脂100级,作为承压层;按第一段温度为175℃,第二段温度为185℃,第三段温度为195℃挤出阻隔层;按第一段温度为168℃,第二段温度为185℃,第三段温度为195℃,挤出承压层;按第一段温度为180℃,第二段温度为185℃,第三段温度为200℃挤出粘结层;再将阻隔层、粘结层和承压层在机头共挤出,共挤出时第一段温度为180℃,第二段温度为185℃,第三段温度为212℃,在机头处以1m/min的牵引速度进行牵引,然后在经过切割、冷却至室温,得到复合管预成品,再将预成品管材置于80℃下烘烤45min,制得塑料管复合管材2号。
本实施例制备的复合管材,阻隔层作为内层,阻隔层的壁厚为2mm,管材的外径为110mm,管材壁厚为8.2mm。本实施例的复合管材可作为石油运输领域输油管使用,相比于现有的乙烯-乙烯醇共聚物做阻隔层,其耐油能力提高了200%,阻隔性能提高了60%。
实施例3:PE-RT阻氧管
将阻隔层原料混合均匀;准备好耐热聚乙烯接枝马来酸酐共聚物,加入2%的红色母料,常温搅拌混合均匀,作为粘结层;再准备好PE-RT树脂,作为承压层;按第一段温度为175℃,第二段温度为185℃,第三段温度为195℃挤出阻隔层;按第一段温度为160℃,第二段温度为175℃,第三段温度为190℃,第四段温度为185℃,挤出承压层;按第一段温度为180℃,第二段温度为185℃,第三段温度为190℃挤出粘结层;再将阻隔层、粘结层和承压层在机头共挤出,共挤出时第一段温度为180℃,第二段温度为185℃,第三段温度为200℃,在机头处以12m/min的牵引速度进行牵引,然后在经过切割、冷却至室温,得到复合管预成品,再将预成品管材置于75℃下烘烤40min,制得塑料管复合管材3号。
本实施例制备的复合管材,阻隔层作为内层,阻隔层的壁厚为0.15mm,管材的外径为20mm,管材壁厚为2mm。本实施例的复合管材在需隔氧的环境中使用,乙烯-乙烯醇共聚物做阻氧层生产的PE-RT阻氧管材,其阻氧层成本降低50%,阻氧能力提高35%,抗撕裂强度提高100%,制备的管材的成品率高。
实施例4:本实施例的管材的制备方法中所用的参数与实施例1的相同,不同之处在于,在本实施例中,阻隔层的配比不相同,阻隔层中的马来酸酐接枝共聚物为聚丙烯马来酸酐接枝共聚物和聚乙烯马来酸酐接枝共聚物的混合物,其余的与实施例1的相同。
由本实施例4制备的PP-R给水管,与现有技术中的单一的乙烯-乙烯醇共聚物做阻隔层,本实施例的管材的阻隔性能提高了85%,比其他普通管材的防渗透能力提高了9倍。
实施例5:本实施例5与实施例2的不同之处在于,在本实施例中,阻隔层的配方比例不同,在本实施例5中,阻隔层的原料中的马来酸酐接枝共聚物为聚乙烯马来酸酐接枝共聚物和耐热聚乙烯接枝马来酸酐共聚物的混合物,其他的制备方法以及参数与实施例2的相同。
本实施例的复合管材可作为石油运输领域输油管使用,相比于现有的乙烯-乙烯醇共聚物做阻隔层,其防石油渗透能力提高了120%,阻隔性能提高了76%。
实施例6:本实施例6与实施例3的不同之处在于,在本实施例中,阻隔层的配方比例不同,其他的制备方法以及参数与实施例2的相同。
本实施例的复合管材在需要隔氧的环境中使用,乙烯-乙烯醇共聚物做阻氧层生产的PE-RT阻氧管材,其阻氧层成本降低50%,阻氧能力提高50%,抗撕裂强度提高80%,制备的管材的成品率高。
在本发明的其他实施例中,还可以根据实际的使用环境,设计管材的具体层数,例如,可将管材设计层5层,由内向外依次为承压层、粘结层、阻隔层、粘结层和承压层。还可以是其他层数,阻隔层的相对位置也可根据实际的需求进行合理的调节。在本发明中,阻隔层的厚度也可根据实际的需求进行选择。本发明中的阻隔层,在较薄的厚度下,可达到优异的阻隔性能,降低生产成本。
本发明的阻隔层可配合现有技术中的其他材质为主体的管材使用,并还可根据实际的使用环境,可在阻隔层中加入抗氧化剂等功能性添加剂,也可加入一定量的5-15%盐酸水溶液或纯水等,提高阻隔层的加工性能。
实验例:1
采用实施例1中的制备方法及参数,以实施例1中的配方制备出不同厚度的阻隔层的复合管材,再以单一的乙烯-乙烯醇共聚物作为阻隔层原料(对比例见表2),制备不同厚度的阻隔层的复合管材,采用国标检测方法,检测各管材的阻隔性能。如下表所示:
表2不同厚度的阻隔层的阻隔性能
在上表中,阻隔层厚度的单位为mm。氧气渗透率的单位为g/(d.m)3,从上述表中,可以得出,本发明的实施例1的给水管的氧气渗透率明显小于对比例1中的给水管的氧气渗透率,并且,在达到同一的渗透率的条件下,本发明的实施例1中的管材的阻隔层的厚度明显较薄。
实验例2:
将上述实施例1-6中的管材制备成试样条,对实验条进行对折实验,即将试样条反复对折到两面贴合,统计每一试样条分层前被对折的次数,试样条长50mm,宽2mm。其结果如下表所示。
表3实施例1-6的粘结强度
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 | |
次数 | 19 | 31 | 21 | 27 | 33 | 25 |
实施例1的试样条在对折第20次后,试样条的阻隔层和粘结层出现分层,实施例2的试样条在对折第32次后,试样条的承压层和粘结成出现分层,阻隔层和粘结层之间也出现裂痕;实施例3中,粘结层和阻隔层出现分层;实施例4中,粘结层和阻隔层出现分层;实施例4、5、6中,均是粘结层和阻隔层分层。
从上述表中可以看出,本发明中的粘结层和阻隔层、粘结层和承压层之间的连接牢固。
实验例3:
采用实施例2中的制备方法,,以实施例2中的配方制备出不同厚度的阻隔层的复合管材,再以单一的乙烯-乙烯醇共聚物作为阻隔层原料(对比例),制备不同厚度的阻隔层的复合管材,采用国标检测方法,检测各管材的阻隔性能。如下表所示:
表3不同厚度的阻隔层的阻隔性能
在上表中,阻隔层厚度的单位为mm。氧气渗透率的单位为g/(d.m)3
从上表中可以得出,本发明中的具有阻隔层的PE石油管的氧气渗透率低,管材的阻隔性好,将该PE管应用到石油输送管路中,可明显降低对土壤、地下水的污染。
实验例4:
将实施例1-6中的复合管材制备成试样条,测试各实施例中的管材力学性能,其结果如下表所示:
表4管材力学性能
现有技术中的与实施例1中相同厚度的PP-R给水,在0℃低温冲击性能测试时采用2.8kg的锤重,管材有破裂现象。从上表中可以看出,本发明中的管材在提高阻隔性能的前提下,拉伸强度和低温性能、液压性能同时得到提高。
Claims (10)
1.一种阻隔层,其特征在于:包括以下原料组份,以重量份数计为,
2.根据权利要求1所述的阻隔层,其特征在于:所述原料组份重量份数为,
3.根据权利要求1所述的阻隔层,其特征在于:所述原料组份重量份数为,
4.根据权利要求1所述的阻隔层,其特征在于:所述原料组份重量份数为,
5.根据权利要求1-4任一所述的阻隔层,其特征在于:所述马来酸酐接枝共聚物为聚乙烯接枝马来酸酐共聚物、聚丙烯接枝马来酸酐共聚物、耐热聚乙烯接枝马来酸酐共聚物中的一种或多种的混合。
6.一种多层塑料复合管,其特征在于:包括承压层、粘接层和权利要求1-5任一所述阻隔层,所述粘接层位于所述承压层和所述阻隔层之间。
7.根据权利要求6所述的多层塑料复合管,其特征在于:所述粘结层的材质为马来酸酐接枝共聚物。
8.一种权利要求6-7任一所述多层塑料复合管的制备方法,其特征在于:包括以下步骤,
S1:采用多层共挤机分别挤出阻隔层、粘结层和承压层;
S2:所述阻隔层、粘结层和所述承压层在多层共挤机的机头共挤出;
S3:经牵引、切割、冷却至室温、烘烤,得到所述复合管。
9.根据权利要求8所述的多层塑料复合管,其特征在于:所述牵引的速度为1-50m/min。
10.根据权利要求8所述的多层塑料复合管,其特征在于:所述烘烤温度为60-120℃,烘烤时间为0.15-4h。
Priority Applications (3)
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CN201910152724.0A CN109721912B (zh) | 2019-02-28 | 2019-02-28 | 一种阻隔层、多层塑料复合管及制备方法 |
DE102019114125.7A DE102019114125A1 (de) | 2019-02-28 | 2019-05-27 | Verbundschlauch |
EP19178128.5A EP3702408A1 (en) | 2019-02-28 | 2019-06-04 | Barrier layer, multi-layer plastic composite pipe, and preparation method |
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Cited By (3)
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CN111349298A (zh) * | 2020-04-17 | 2020-06-30 | 江南大学 | 一种低成本可热塑加工的pva-evoh高阻隔组合物、制备方法及其应用 |
CN111716857A (zh) * | 2020-06-12 | 2020-09-29 | 江南大学 | 一种熔融共挤多层复合高阻隔薄膜、制备方法及其应用 |
CN112706484A (zh) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | 高阻隔性能的热塑性聚乙烯醇复合薄膜及其制备方法 |
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CN113715453B (zh) * | 2021-09-02 | 2023-04-11 | 四川厚诚新材料有限公司 | 一种抗冷冻流延pe膜及其制备方法 |
CN115028916A (zh) * | 2022-06-08 | 2022-09-09 | 广州丽盈塑料有限公司 | 一种塑料包装容器用高阻隔性轻质塑料及其制备方法 |
WO2024142049A1 (en) * | 2022-12-27 | 2024-07-04 | Solutum Technologies Ltd. | Biodegradable and barrier pvoh-based materials and products made therefrom |
CN116080191A (zh) * | 2023-02-15 | 2023-05-09 | 浙江鹏远新材料科技集团股份有限公司 | 一种高阻隔包装材料及其制备方法 |
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CN112706484A (zh) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | 高阻隔性能的热塑性聚乙烯醇复合薄膜及其制备方法 |
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DE102019114125A1 (de) | 2020-09-03 |
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