CN102924847B - 一种热可逆交联pvc电缆料及其制备方法 - Google Patents
一种热可逆交联pvc电缆料及其制备方法 Download PDFInfo
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract
本发明涉及一种热可逆交联PVC电缆料及其制备方法，所述PVC电缆料由以下组分及重量份数的原料制成：PVC树脂100份；稳定剂2-4份；增塑剂10-40份；无机填料10-50份；热可逆交联剂0.5-5份；润滑剂0.5-2份；抗氧剂0.2-2份；阻燃剂10-30份；该PVC电缆料的制备方法包括配料、高速共混、挤出造粒、干燥等工艺步骤；相对于现有技术，本发明的突出特点是采用一种能发生热可逆交联的PVC专用交联剂与PVC进行共混，然后通过与PVC链上活性氯发生反应引发交联剂、PVC共价交联，从而提高PVC电缆的热稳定性、耐热性并保持原有热塑性。
Description
技术领域
本发明为一种热可逆交联PVC电缆料及其制备方法，属于材料技术领域。
背景技术
随着经济的迅速发展，电线电缆在各个行业、领域中都得到广泛的应用。PVC电缆料价格低廉，性能优良，在电线电缆绝缘保护材料中长期占有重要地位，但是以 PVC为基础的电缆料存在热稳定性差、易老化、耐热性低(Tg～80℃)及软制品的回弹率低等固有缺陷。改善其热稳定性的常用方法是加入铅盐、钙锌稳定剂等，以吸收、稳定分解放出的HCl，而提高其耐热性的常用方法有物理改性(填充、共混)和化学改性(共聚、接枝及交联)。从PVC精细分子结构的观点，PVC的热分解往往是从含活性氯(烯丙基氯或叔碳氯等)的结构处开始，引起自催化脱HCl的连续老化过程，因此设法消除或取代这种(少量)活性氯将可有效地提高PVC材料的热稳定性。PVC的交联是改善其热稳定性并提高力学性能的方法之一。
合理有效的交联可提高PVC材料的使用等级，对PVC电缆料而言，目前研究应用最多的方法是辐照交联法。辐照交联PVC的关键问题是在低辐照剂量下提高凝胶含量，但是PVC材料辐照后存在变色的问题，尤其对于浅色料，辐照后会变色，影响外观，往往不被客户所接受，产生纠纷，增加不必要的生产成本。从另一个方面来讲，传统的交联虽可有效地提高PVC的强度和耐热性，但其最严重的后果是使PVC材料发生永久交联，从而丧失了宝贵的热塑性，由此使PVC变为不可再次回收利用的热固性塑料。
发明内容
本发明的目的主要是解决现有技术所存在的PVC电缆热稳定性差、耐热性不好及形成热固性塑料等问题，提供了一种热可逆交联PVC电缆料及其制备方法。
为实现上述目的，本发明采用如下技术方案：
一种热可逆交联PVC电缆料，由以下组分及重量份数的原料制成：PVC树脂100份；稳定剂2-4份；增塑剂10-40份；无机填料10-50份；热可逆交联剂0.5-5份；润滑剂0.5-2份；抗氧剂0.2-2份；阻燃剂10-30份。
优选地，其中所述PVC树脂为PVC SG-3，所述稳定剂为钙锌稳定剂、稀土稳定剂或有机锡稳定剂中的至少一种。
优选地，所述增塑剂为二辛脂类增塑剂、环氧类增塑剂中的至少一种。
优选地，所述无机填料为粉煤灰或玻璃微珠中的至少一种，其中所述粉煤灰的粒径为5.8μm，比表面积2.230m2/cm3，所述玻璃微珠的粒径为300目。
优选地，所述润滑剂为PE蜡、石蜡、金属皂类或硬脂酸类中的至少一种。
优选地，所述热可逆交联剂为双环戊二烯二羧酸盐DCPD(COOM)2，其中M为K、Na或Li。
优选地，所述抗氧剂为抗氧剂1010。
优选地，所述阻燃剂为氢氧化镁和氢氧化铝中的至少一种。
本发明还提供上述热可逆交联PVC电缆料的制备方法，包括以下步骤：
1)常温下将PVC树脂、稳定剂、增塑剂按比例投入高速混合机混合4-6分钟，升温到90-100℃，然后将无机填料、交联剂、润滑剂、抗氧剂、阻燃剂按比例投入高速混合机中混合3-5分钟，搅拌至100-110℃，立即将混合料进入冷却混合机，混合3-5分钟，出料温度30-40℃；
2)将步骤1)所得混合料送入双螺杆挤出机中进行混炼；
3)最后经双螺杆挤出机挤出、冷却水冷却、切粒机切粒、鼓风干燥得到所述热可逆交联PVC电缆料。
优选地，其中所述双螺杆挤出机的参数设定如下：一区 140-150℃、二区 150-160℃、三区 160-170℃、四区 170-180℃；机头温度 160-170℃；螺杆转速 10-40r/min。
本发明相对于现有技术，其突出特点是采用一种能发生热可逆交联剂与PVC树脂、无机填料等进行共混，通过与活性氯反应引发PVC共价交联，凝胶含量增大，从而提高PVC的热稳定性、耐热性并保持其热塑性；此外，这种交联剂在常温下处于交联状态，而在加工温度下可以解交联，具有热可逆特性，因此，具有良好的可加工性。而且该制备方法更为简便有效，应用更为安全可靠。
具体实施方式
为详细说明本发明的各种有效组分组成、制备方法，列举如下实施例详细说明。
下面结合实施例对本发明作进一步详细说明。
实施例1
常温下将PVC(SG3)(内蒙古亿利化学工业有限公司)100份、钙锌稳定剂(河北精信化工集团有限公司)3份、DOP (邻苯二甲酸二辛酯) (濮阳市诚意增塑剂有限公司)30份投入高速混合机混合4-6分钟升温到90℃左右，然后将粉煤灰(亿利资源集团有限公司自有电厂排放的粉煤灰，粒径约5.8μm，比表面积2.230m2/cm3)20份、热可逆交联剂(成分为双环戊二烯二羧酸盐DCPD(COOM)2，M为K、Na、Li，制备方法请参考Eli Ruckenstein, Xiaonong Chen. Crosslinking of Chlorine-Containing Polymers by Dicyclopentadiene Dicarboxylic Salts[J]. Journal of Polymer Science: Part A: Polymer Chemistry, 2000 (38): 818-825.）1份、PE蜡(PE-Wax，D1100A) (上海纳多化工有限公司)0.5份、抗氧剂1010(北京极易化工有限公司)1.0份、氢氧化镁(大连亚泰科技新材料有限公司)10份投入高速混合机中混合3-5分钟，搅拌至100-110℃，立即放料进入冷却混合机，混合3-5分钟，出料温度30-40℃。将所得混合料送入双螺杆挤出机中进行混炼，双螺杆挤出机各段的加工温度设定如下，一区 145℃、二区 155℃、三区 170℃、四区 180℃、机头温度 170℃、螺杆转速 20 r/min，最后经双螺杆挤出机挤出、冷却水冷却、切粒机造粒、鼓风干燥即得到所需的热可逆交联PVC电缆料。按照国家标准检测，各项指标如表2所示。
实施例2
常温下将PVC(SG3)( 内蒙古亿利化学工业有限公司)100份、钙锌稳定剂(河北精信化工集团有限公司)3份、DOP (邻苯二甲酸二辛酯) (濮阳市诚意增塑剂有限公司)30份投入高速混合机混合4-6分钟升温到90℃左右，然后将粉煤灰(亿利资源集团有限公司自有电厂排放的粉煤灰，粒径约5.8μm，比表面积2.230m2/cm3)20份、热可逆交联剂(成分为双环戊二烯二羧酸盐DCPD(COOM)2，M为K、Na、Li，制备方法请参考Eli Ruckenstein, Xiaonong Chen. Crosslinking of Chlorine-Containing Polymers by Dicyclopentadiene Dicarboxylic Salts[J]. Journal of Polymer Science: Part A: Polymer Chemistry, 2000 (38): 818-825.）2份、PE蜡(PE-Wax，D1100A) (上海纳多化工有限公司)0.5份、抗氧剂1010(北京极易化工有限公司)1.0份、氢氧化镁(大连亚泰科技新材料有限公司)10份投入高速混合机中混合3-5分钟，搅拌至100-110℃，立即放料进入冷却混合机，混合3-5分钟，出料温度30-40℃。将所得混合料送入双螺杆挤出机中进行混炼，双螺杆挤出机各段的加工温度设定如下，一区 145℃、二区 155℃、三区 170℃、四区 180℃、机头温度 170℃、螺杆转速 20 r/min，最后经双螺杆挤出机挤出、冷却水冷却、切粒机造粒、鼓风干燥 即得到所需的热可逆交联PVC电缆料。按照国家标准检测，各项指标如表2所示。
实施例3
常温下将PVC(SG3)( 内蒙古亿利化学工业有限公司)100份、钙锌稳定剂(河北精信化工集团有限公司)3份、环氧大豆油 (河北翰兴化工有限公司)40份投入高速混合机混合4-6分钟升温到90℃左右，然后将粉煤灰(亿利资源集团有限公司自有电厂排放的粉煤灰，粒径约5.8μm，比表面积2.230m2/cm3)20份、热可逆交联剂(成分为双环戊二烯二羧酸盐DCPD(COOM)2，M为K、Na、Li，制备方法请参考Eli Ruckenstein, Xiaonong Chen. Crosslinking of Chlorine-Containing Polymers by Dicyclopentadiene Dicarboxylic Salts[J]. Journal of Polymer Science: Part A: Polymer Chemistry, 2000 (38): 818-825.）2份、PE蜡(PE-Wax，D1100A) (上海纳多化工有限公司)0.5份、抗氧剂1010(北京极易化工有限公司)1.0份、氢氧化镁(大连亚泰科技新材料有限公司)10份投入高速混合机中混合3-5分钟，搅拌至100-110℃，立即放料进入冷却混合机，混合3-5分钟，出料温度30-40℃。将所得混合料送入双螺杆挤出机中进行混炼，双螺杆挤出机各段的加工温度设定如下，一区 145℃、二区 155℃、三区 170℃、四区 180℃、机头温度 170℃、螺杆转速 20 r/min，最后经双螺杆挤出机挤出、冷却水冷却、切粒机造粒、鼓风干燥即得到所需的热可逆交联PVC电缆料。按照国家标准检测，各项指标如表2所示。
实施例4
常温下将PVC(SG3)( 内蒙古亿利化学工业有限公司)100份、钙锌稳定剂(河北精信化工集团有限公司)3份、环氧大豆油 (河北翰兴化工有限公司)30份投入高速混合机混合4-6分钟升温到90℃左右，然后将粉煤灰(亿利资源集团有限公司自有电厂排放的粉煤灰，粒径约5.8μm，比表面积2.230m2/cm3)30份、热可逆交联剂(成分为双环戊二烯二羧酸盐DCPD(COOM)2，M为K、Na、Li，制备方法请参考Eli Ruckenstein, Xiaonong Chen. Crosslinking of Chlorine-Containing Polymers by Dicyclopentadiene Dicarboxylic Salts[J]. Journal of Polymer Science: Part A: Polymer Chemistry, 2000 (38): 818-825.）1份、PE蜡(PE-Wax，D1100A) (上海纳多化工有限公司)0.5份、抗氧剂1010(北京极易化工有限公司)1.0份、氢氧化铝(大连亚泰科技新材料有限公司)20份投入高速混合机中混合3-5分钟，搅拌至100-110℃，立即放料进入冷却混合机，混合3-5分钟，出料温度30-40℃。将所得混合料送入双螺杆挤出机中进行混炼，双螺杆挤出机各段的加工温度设定如下，一区 145℃、二区 155℃、三区 170℃、四区 180℃、机头温度 170℃、螺杆转速 10 r/min，最后经双螺杆挤出机挤出、冷却水冷却、切粒机造粒、鼓风干燥即得到所需的热可逆交联PVC电缆料。按照国家标准检测，各项指标如表1所示。
表1热可逆交联PVC电缆料性能检测结果
| 性能指标 | 实施例1 | 实施例2 | 实施例3 | 实施例4 |
| 凝胶含量(%) | 41 | 67 | 60 | 75 |
| 拉伸强度(MPa) | 19.27 | 20.21 | 19.75 | 22.08 |
| 冲击强度(KJ/m2) | 4.06 | 8.17 | 7.65 | 10.33 |
| 断裂伸长率(%) | 192 | 168 | 175 | 143 |
| 维卡软化温度(℃) | 70.12 | 73.56 | 65.39 | 76.47 |
由表1可以看出，随着交联剂用量的增加，PVC制品的凝胶含量、拉伸强度、冲击强度和维卡软化温度随之提高，断裂伸长率减小，说明交联剂的添加使PVC分子发生交联，力学性能和热性能得到增强。当增塑剂用量增多时，PVC制品较软，力学性能较低。当加工时间，即混合料在双螺杆挤出机中停留时间延长时，有利于交联剂引发PVC分子链进行交联，从而使力学性能和热性能得到增强。
以上所述，仅为本发明的实施例，应当指出，对于本技术中的普通技术人员来说，在不脱离本发明的核心技术特征的前提下，还可以做若干的改进和润饰，这些润饰和改进也应属于本发明的专利保护范围。
Claims (1)
1.一种热可逆交联PVC电缆料，其特征在于，所述热可逆交联PVC电缆料由以下组分及重量份数的原料制成：PVC树脂100份；稳定剂2-4份；增塑剂10-40份；无机填料10-50份；热可逆交联剂0.5-5份；润滑剂0.5-2份；抗氧剂0.2-2份；阻燃剂10-30份；其中，
所述PVC树脂为PVC SG-3；所述稳定剂为钙锌稳定剂、稀土稳定剂或有机锡稳定剂中的至少一种；所述增塑剂为二辛脂类增塑剂、环氧类增塑剂的至少一种；所述无机填料为粉煤灰和玻璃微珠中的至少一种，其中所述粉煤灰的粒径为5.8μm，比表面积为2.230m2/cm3；所述玻璃微珠的粒径为300目；所述热可逆交联剂为双环戊二烯二羧酸盐DCPD(COOM)2，其中M为K、Na或Li；所述润滑剂为PE蜡、石蜡、金属皂类或硬脂酸类中的至少一种；所述抗氧剂为抗氧剂1010；所述阻燃剂为氢氧化镁或氢氧化铝中的至少一种；
通过以下步骤制得：
1)常温下将PVC树脂、稳定剂、增塑剂按比例投入高速混合机混合4-6分钟升温到90-100℃，然后将无机填料、交联剂、润滑剂、抗氧剂、阻燃剂按比例投入高速混合机中混合3-5分钟，搅拌至100-110℃，立即将混合料进入冷却混合机，混合3-5分钟，出料温度30-40℃；
2)将步骤1)所得混合料送入双螺杆挤出机中进行混炼；
3)最后经双螺杆挤出机挤出、冷却水冷却、切粒机切粒、鼓风干燥得到所述热可逆交联PVC电缆料；其中所述双螺杆挤出机的参数设定如下：一区 140-150℃、二区 150-160℃、三区 160-170℃、四区 170-180℃；机头温度 160-170℃；螺杆转速 10-40r/min。
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Effective date of registration: 20220412 Address after: 014300 Dalate circular economy industrial park of Yili Group, Shulinzhao Town, Dalate Banner, Ordos City, Inner Mongolia Autonomous Region Patentee after: INNER MONGOLIA ELION CHEMICAL INDUSTRY CO.,LTD. Address before: 100031 6th Floor, Kaichen World Trade Center East Block, 28 Fuxing Mennei Street, Xicheng District, Beijing Patentee before: ELION RESOURCES Group |