CN106188942B - 一种聚氯乙烯耐高低温软管及其制备方法 - Google Patents
一种聚氯乙烯耐高低温软管及其制备方法 Download PDFInfo
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Abstract
一种聚氯乙烯耐高低温软管,其原料组成及重量份比为:聚氯乙烯树脂SH‑200 30~50、聚氯乙烯树脂WS‑1300 30~50、丁腈粉末P83 8~10、乙烯‑醋酸乙烯羰基共聚物E/VA/CO 8~10、增塑剂50~65、稳定剂6~8、交联助剂8~10、抗氧剂0.8~1、防老剂0.3~0.5、润滑剂1~2、填料9~12,制备时,先将上述原料熔融共混,再依次经由挤制工艺、电子加速器辐照交联即可。该设计具有良好的耐高低温性能。
Description
技术领域
本发明属于新型高分子材料领域,具体涉及一种聚氯乙烯耐高低温软管及制备方法。
背景技术
目前,聚氯乙烯软管用途非常广泛,如车用套管、电线电缆保护软管、工业耐酸碱软管、耐高温输送软管等领域。虽然聚氯乙烯软管具有如下优点:⑴重量轻,仅为同尺寸钢重量的六分之一;⑵耐腐蚀性能好;⑶电绝缘性能好;⑷摩擦阻力小;⑸导热系数小;⑹着色方便;⑺生产能耗低,但其在使用过程中也存在如下缺陷:⑴低温下易***,发脆;⑵高温下易老化,***;⑶使用温度范围窄,一般在-15~70℃之间;⑷热变形较大。
发明内容
本发明的目的是克服现有技术存在的在高、低温下性能较差的问题,提供一种可耐高低温的聚氯乙烯软管及其制备方法。
为实现以上目的,本发明提供了以下技术方案:
一种聚氯乙烯耐高低温软管,该软管的原料组成及其重量份比为:聚氯乙烯树脂SH-20030~50、聚氯乙烯树脂WS-130030~50、丁腈粉末P838~10、乙烯-醋酸乙烯羰基共聚物E/VA/CO 8~10、增塑剂50~65、稳定剂6~8、交联助剂8~10、抗氧剂0.8~1、防老剂0.3~0.5、润滑剂1~2、填料9~12;
所述软管由上述原料按所需比例通过辐照交联改性制得。
所述增塑剂由癸二酸二辛酯DOS、邻苯二甲酸二辛酯DOP按10~15:40~50的重量比混合而成,所述稳定剂为钙锌复合稳定剂8890,所述交联助剂为三羟甲基丙烷三甲基丙烯酸酯TMPTMA,所述抗氧剂为双酚A,所述防老剂为4010NA,所述润滑剂为聚乙烯蜡,所述填料由纳米碳酸钙、色母料按8~10:1~2的重量比混合而成。
一种聚氯乙烯耐高低温软管的制备方法,依次包括以下步骤:
原料熔融共混:先将聚氯乙烯树脂SH-200、聚氯乙烯树脂WS-1300、丁腈粉末P83、乙烯-醋酸乙烯羰基共聚物E/VA/CO、增塑剂、稳定剂、交联助剂、抗氧剂、防老剂、润滑剂、填料按所需比例加入高速混合机中混合均匀以得到混合物料,再将混合物料排入双阶式挤出造粒机组中熔融挤出、风冷切料以得到管材粒子;
软管的制备:先将所述管材粒子于单螺杆挤出机中挤制得到内、外壁均光滑的管材,再用电子加速器对挤制的管材进行辐照交联,即得到聚氯乙烯耐高低温软管。
所述原料熔融共混步骤中,混合温度为70~90℃,混合时间为7~8min,
双阶式挤出造粒机的工艺温度为:
平行双螺杆:一区125~135℃,二区135~145℃,三区145~155℃,四区155~165℃,五区160~170℃,六区165~175℃,机头155~165℃,
单螺杆:一区135~145℃,二区140~150℃,三区145~155℃,四区155~165℃,五区160~170℃,机头155~165℃;
所述软管的制备步骤中,辐照剂量为15~18兆拉德,
单螺杆挤出机的工作温度为:一区130~140℃,二区140~150℃,三区150~160℃,四区160~170℃,五区165~175℃,机头160~170℃。
所述增塑剂由癸二酸二辛酯DOS、邻苯二甲酸二辛酯DOP按10~15:40~50的重量比混合而成,所述稳定剂为钙锌复合稳定剂8890,所述交联助剂为三羟甲基丙烷三甲基丙烯酸酯TMPTMA,所述抗氧剂为双酚A,所述防老剂为4010NA,所述润滑剂为聚乙烯蜡,所述填料由纳米碳酸钙、色母料按8~10:1~2的重量比混合而成。
与现有技术相比,本发明的有益效果为:
本发明一种聚氯乙烯耐高低温软管的原料组成包括高聚合度的聚氯乙烯树脂SH-200、丁腈粉末P83以及乙烯-醋酸乙烯羰基共聚物E/VA/CO,聚氯乙烯树脂SH-200的低温韧性良好,丁腈粉末P83不仅可有效降低产品的低温脆化温度,而且具有增塑的效果,乙烯-醋酸乙烯羰基共聚物E/VA/CO在提高聚氯乙烯的低温韧性的同时也能起到增塑的作用,三者联合使用保证了产品能够在零下50℃的条件下正常使用并保持较高的柔软度,将上述原料通过电子束辐照交联改性,可使聚氯乙烯交联形成网状分子结构,由热塑性材料转变成热固性材料,保证了产品能够在105℃的环境下长期使用。因此,本发明具有良好的耐高低温性能。
具体实施方式
下面结合具体实施方式对本发明作进一步说明。
一种聚氯乙烯耐高低温软管,该软管的原料组成及其重量份比为:聚氯乙烯树脂SH-20030~50、聚氯乙烯树脂WS-130030~50、丁腈粉末P838~10、乙烯-醋酸乙烯羰基共聚物E/VA/CO 8~10、增塑剂50~65、稳定剂6~8、交联助剂8~10、抗氧剂0.8~1、防老剂0.3~0.5、润滑剂1~2、填料9~12;
所述软管由上述原料按所需比例通过辐照交联改性制得。
所述增塑剂由癸二酸二辛酯DOS、邻苯二甲酸二辛酯DOP按10~15:40~50的重量比混合而成,所述稳定剂为钙锌复合稳定剂8890,所述交联助剂为三羟甲基丙烷三甲基丙烯酸酯TMPTMA,所述抗氧剂为双酚A,所述防老剂为4010NA,所述润滑剂为聚乙烯蜡,所述填料由纳米碳酸钙、色母料按8~10:1~2的重量比混合而成。
一种聚氯乙烯耐高低温软管的制备方法,依次包括以下步骤:
原料熔融共混:先将聚氯乙烯树脂SH-200、聚氯乙烯树脂WS-1300、丁腈粉末P83、乙烯-醋酸乙烯羰基共聚物E/VA/CO、增塑剂、稳定剂、交联助剂、抗氧剂、防老剂、润滑剂、填料按所需比例加入高速混合机中混合均匀以得到混合物料,再将混合物料排入双阶式挤出造粒机组中熔融挤出、风冷切料以得到管材粒子;
软管的制备:先将所述管材粒子于单螺杆挤出机中挤制得到内、外壁均光滑的管材,再用电子加速器对挤制的管材进行辐照交联,即得到聚氯乙烯耐高低温软管。
所述原料熔融共混步骤中,混合温度为70~90℃,混合时间为7~8min,
双阶式挤出造粒机的工艺温度为:
平行双螺杆:一区125~135℃,二区135~145℃,三区145~155℃,四区155~165℃,五区160~170℃,六区165~175℃,机头155~165℃,
单螺杆:一区135~145℃,二区140~150℃,三区145~155℃,四区155~165℃,五区160~170℃,机头155~165℃;
所述软管的制备步骤中,辐照剂量为15~18兆拉德,
单螺杆挤出机的工作温度为:一区130~140℃,二区140~150℃,三区150~160℃,四区160~170℃,五区165~175℃,机头160~170℃。
所述增塑剂由癸二酸二辛酯DOS、邻苯二甲酸二辛酯DOP按10~15:40~50的重量比混合而成,所述稳定剂为钙锌复合稳定剂8890,所述交联助剂为三羟甲基丙烷三甲基丙烯酸酯TMPTMA,所述抗氧剂为双酚A,所述防老剂为4010NA,所述润滑剂为聚乙烯蜡,所述填料由纳米碳酸钙、色母料按8~10:1~2的重量比混合而成。
本发明的原理说明如下:
聚氯乙烯树脂:
高聚合度的聚氯乙烯树脂SH-200虽然具有较好的耐热和耐低温性能,但其弹性大,加工性能较差,因此本发明在其基础上加入了低聚合度的聚氯乙烯树脂WS-1300,以保证在满足产品性能的同时还能满足挤出工艺的要求。
丁腈粉末P83:
为改性丁腈橡胶,当P83弹性体分散于聚氯乙烯基体中时,P83弹性体会把聚氯乙烯包覆在中间,形成连续的网状结构。材料受到冲击时,连续的网状结构能够吸收大量的冲击能量,从而保护材料,使材料避免受到破坏;即使所述连续的网状结构不足以吸收全部的冲击能量,聚氯乙烯初级粒子在破裂时也能吸收很多能量以保护材料,从而显著改善材料的低温韧性。另外,P83弹性体还可作为高分子固体增塑剂,尤其当材料处于低温时,该高分子固体增塑剂不会像小分子液体增塑剂那样容易迁移析出,这样保证了聚氯乙烯的低温柔韧性,提高了低温冲击强度,降低了脆化温度。
乙烯-醋酸乙烯羰基共聚物E/VA/CO:
该共聚物作为柔韧性的增塑剂,其体系中引入了酮羰基,与聚氯乙烯的相容性极好,作为改性剂分散在聚氯乙烯基体中可形成网络结构,聚氯乙烯初级粒子位于网络内。当材料受到外力冲击时,该网络结构可以吸收大量的冲击能量,提高材料的低温冲击强度;另外,乙烯-醋酸乙烯羰基共聚物E/VA/CO同样可作为高分子固体增塑剂,使材料在持续低温环境中保持良好的性能。
耐寒增塑剂癸二酸二辛酯DOS:
耐寒增塑剂的耐寒性与其结构有着密切的关系。一般相溶性良好的增塑剂耐寒性都较差,特别是当含有环状结构时,耐寒性显著降低。癸二酸二辛酯DOS作为以直链亚甲基(-CH2-)为主体的脂肪族酯类具有良好的耐寒性,其引入可降低聚氯乙烯的玻璃化转变温度,从而降低聚氯乙烯的低温脆化温度,提高材料的耐寒性能。
原料熔融共混步骤:
该步骤将混合温度控制在70~90℃,易于聚氯乙烯树脂对液体增塑剂的吸收,在该温度范围混合7~8min,可保证增塑剂完全被聚氯乙烯树脂吸收。
实施例1:
一种聚氯乙烯耐高低温软管,该软管的原料组成及其重量份比为:聚氯乙烯树脂SH-200 30、聚氯乙烯树脂WS-1300 30、丁腈粉末P83 8、乙烯-醋酸乙烯羰基共聚物E/VA/CO8、癸二酸二辛酯DOS 10、邻苯二甲酸二辛酯DOP 40、钙锌复合稳定剂8890 6、三羟甲基丙烷三甲基丙烯酸酯TMPTMA 8、抗氧剂双酚A 0.8、防老剂4010NA 0.3、聚乙烯蜡1、纳米碳酸钙8、色母料1。
所述聚氯乙烯耐高低温软管依次采用以下步骤制得:
原料熔融共混:先将聚氯乙烯树脂SH-200、聚氯乙烯树脂WS-1300、丁腈粉末P83、乙烯-醋酸乙烯羰基共聚物E/VA/CO、增塑剂、稳定剂、交联助剂、抗氧剂、防老剂、润滑剂、填料按上述比例加入高速混合机中于70℃下混合7min以得到混合物料,再将混合物料排入双阶式挤出造粒机组中熔融挤出、风冷切料以得到管材粒子,其中,所述双阶式挤出造粒机的工艺温度为:
平行双螺杆:一区125~135℃,二区135~145℃,三区145~155℃,四区155~165℃,五区160~170℃,六区165~175℃,机头155~165℃,
单螺杆:一区135~145℃,二区140~150℃,三区145~155℃,四区155~165℃,五区160~170℃,机头155~165℃;
软管的制备:先将所述管材粒子于单螺杆挤出机中挤制得到内、外壁均光滑的管材,再用电子加速器对挤制的管材进行辐照交联,即得到聚氯乙烯耐高低温软管,其中,所述单螺杆挤出机的工作温度为:一区130~140℃,二区140~150℃,三区150~160℃,四区160~170℃,五区165~175℃,机头160~170℃,所述辐照剂量为16兆拉德。
实施例2:
步骤同实施例1,不同之处在于:
所述聚氯乙烯耐高低温软管的原料组成及其重量份比为:聚氯乙烯树脂SH-20050、聚氯乙烯树脂WS-130050、丁腈粉末P8310、乙烯-醋酸乙烯羰基共聚物E/VA/CO 10、癸二酸二辛酯DOS 15、邻苯二甲酸二辛酯DOP 50、钙锌复合稳定剂88908、三羟甲基丙烷三甲基丙烯酸酯TMPTMA 10、抗氧剂双酚A 1、防老剂4010NA 0.5、聚乙烯蜡2、纳米碳酸钙10、色母料2。
所述原料熔融共混步骤中,混合温度为90℃,混合时间为8min;
所述软管的制备步骤中,辐照剂量为18兆拉德。
实施例3:
步骤同实施例1,不同之处在于:
所述聚氯乙烯耐高低温软管的原料组成及其重量份比为:聚氯乙烯树脂SH-20040、聚氯乙烯树脂WS-130040、丁腈粉末P839、乙烯-醋酸乙烯羰基共聚物E/VA/CO 9、癸二酸二辛酯DOS 12.5、邻苯二甲酸二辛酯DOP 45、钙锌复合稳定剂8890 7、三羟甲基丙烷三甲基丙烯酸酯TMPTMA 9、抗氧剂双酚A 0.9、防老剂4010NA 0.4、聚乙烯蜡1.5、纳米碳酸钙9、色母料1.5。
所述原料熔融共混步骤中,混合温度为75℃,混合时间为8min;
所述软管的制备步骤中,辐照剂量为15兆拉德。
将采用上述实施例制备的聚氯乙烯耐高低温软管进行了性能检测,结果如下:
拉伸强度≥16.3MPa;
断裂伸长率≥389%;
低温冲击脆化温度达零下56℃;
200℃时热稳定时间:186分钟;
热老化实验(135℃×240h):老化后拉伸强度≥16.1MPa,老化后断裂伸长率≥376%;
热老化质量损失(115℃×240h)≤9.8g/m2;
20℃时体积电阻率:3.8×1010Ω·m;
热变形≤22.7%。
Claims (5)
1.一种聚氯乙烯耐高低温软管,其特征在于:
所述软管的原料组成及其重量份比为:聚氯乙烯树脂SH-20030~50、聚氯乙烯树脂WS-130030~50、丁腈粉末P838~10、乙烯-醋酸乙烯羰基共聚物E/VA/CO 8~10、增塑剂50~65、稳定剂6~8、交联助剂8~10、抗氧剂0.8~1、防老剂0.3~0.5、润滑剂1~2、填料9~12;
所述软管由上述原料按所需比例通过辐照交联改性制得。
2.根据权利要求1所述的一种聚氯乙烯耐高低温软管,其特征在于:所述增塑剂由癸二酸二辛酯DOS、邻苯二甲酸二辛酯DOP按10~15:40~50的重量比混合而成,所述稳定剂为钙锌复合稳定剂8890,所述交联助剂为三羟甲基丙烷三甲基丙烯酸酯TMPTMA,所述抗氧剂为双酚A,所述防老剂为4010NA,所述润滑剂为聚乙烯蜡,所述填料由纳米碳酸钙、色母料按8~10:1~2的重量比混合而成。
3.一种权利要求1所述的聚氯乙烯耐高低温软管的制备方法,其特征在于:
所述制备方法依次包括以下步骤:
原料熔融共混:先将聚氯乙烯树脂SH-200、聚氯乙烯树脂WS-1300、丁腈粉末P83、乙烯-醋酸乙烯羰基共聚物E/VA/CO、增塑剂、稳定剂、交联助剂、抗氧剂、防老剂、润滑剂、填料按所需比例加入高速混合机中混合均匀以得到混合物料,再将混合物料排入双阶式挤出造粒机组中熔融挤出、风冷切料以得到管材粒子;
软管的制备:先将所述管材粒子于单螺杆挤出机中挤制得到内、外壁均光滑的管材,再用电子加速器对挤制的管材进行辐照交联,即得到聚氯乙烯耐高低温软管。
4.根据权利要求3所述的一种聚氯乙烯耐高低温软管的制备方法,其特征在于:
所述原料熔融共混步骤中,混合温度为70~90℃,混合时间为7~8min,
双阶式挤出造粒机的工艺温度为:
平行双螺杆:一区125~135℃,二区135~145℃,三区145~155℃,四区155~165℃,五区160~170℃,六区165~175℃,机头155~165℃,
单螺杆:一区135~145℃,二区140~150℃,三区145~155℃,四区155~165℃,五区160~170℃,机头155~165℃;
所述软管的制备步骤中,辐照剂量为15~18兆拉德,
单螺杆挤出机的工作温度为:一区130~140℃,二区140~150℃,三区150~160℃,四区160~170℃,五区165~175℃,机头160~170℃。
5.根据权利要求3或4所述的一种聚氯乙烯耐高低温软管的制备方法,其特征在于:所述增塑剂由癸二酸二辛酯DOS、邻苯二甲酸二辛酯DOP按10~15:40~50的重量比混合而成,所述稳定剂为钙锌复合稳定剂8890,所述交联助剂为三羟甲基丙烷三甲基丙烯酸酯TMPTMA,所述抗氧剂为双酚A,所述防老剂为4010NA,所述润滑剂为聚乙烯蜡,所述填料由纳米碳酸钙、色母料按8~10:1~2的重量比混合而成。
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