CN103819839B - 一种无卤素橡塑产品及其制备方法 - Google Patents

一种无卤素橡塑产品及其制备方法 Download PDF

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CN103819839B
CN103819839B CN201310589051.8A CN201310589051A CN103819839B CN 103819839 B CN103819839 B CN 103819839B CN 201310589051 A CN201310589051 A CN 201310589051A CN 103819839 B CN103819839 B CN 103819839B
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CN103819839A (zh
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秦伯军
秦天德
刘远斌
张君
吉娇
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Yingsheng Energy Saving Group Co ltd
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Winsun Jiangsu Energy Saving Co ltd
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Abstract

本发明涉及一种无卤素橡塑产品及其制备方法，按重量份数包括以下组份：分散剂HT-5168、硬脂酸钙、聚乙二醇、防老剂4020、活性氧化锌、硫磺粉、固体石蜡、三氧化二锑、硼酸锌、丁晴橡胶、氢氧化铝、聚氯乙烯树脂、二辛脂、环氧大豆油、炭黑N550、偶氮二甲酰胺、橡胶促剂。其制备工艺简单、方便，生产成本低，能兼顾橡塑产品性能、阻燃性能和使用安全性能。

Description

一种无卤素橡塑产品及其制备方法
技术领域
本发明涉及一种橡塑产品，具体说是一种无卤素的橡塑产品及其制备方法。
背景技术
含卤聚合物或与含卤阻燃剂组合而成的阻燃混合物具有优良的阻燃性能，曾作为阻燃材料被广泛应用。但是在火灾发生时，这类含卤阻燃材料会产生大量的烟雾和有毒的腐蚀性卤化氢气体，造成成二次危害。2003年2月，欧盟颁布了RoHs(TheRestrictionofHazardousSubstancesinElectricalandElectronicEquip-ment，Directive2002/95/EC)和WEEE(WasteElectri-caiandElectronicEquipment，Directive2002/96/EC)两个指令，前者是关于在电子电气设备中限制和禁止使用某些有毒、有害物质和元素的指令，后者是关于回收废弃电子电气设备的指令。这两个指令于2004年8月转换成欧盟15个成员国的法律(法规)，WEEE指令于2005年8月生效，RoHs指令于2006年7月生效。西欧即将在建材等行业实行新的阻燃分类方法和测试标准，中国也已报批建筑材料及制品燃烧性能等级的国家标准，此标准与上述的西欧新标准具有共同的特点，即在评价材料阻燃性能上，强调了释热速率、火灾发展速率、生烟性及燃烧产物的腐蚀性和毒性等。
市场上的橡塑材料大都为可燃或易燃胶种，存在潜在的火灾安全隐患。为了提高橡塑材料的阻燃性能，传统在橡塑材料练制过程中加入卤阻燃剂，该类橡塑材料在阻燃时会产生二恶英，二恶英在环境中能存在多年，甚至终身累积于生物体无法排出，同时含有二恶英的有毒气体易导致人员逃生困难，阻燃、使用安全性能低。现有采用三氧化二锑、氢氧化物作橡塑材料阻燃剂，以增加其环保、安全性能，其燃烧时发烟量小，不产生有毒、腐蚀性气体，但需加入的阻燃剂量较大，易提高练胶难度和胶料性能下降，同时部分阻燃剂价格昂贵，不适合工业大生产使用。
发明内容
针对现有技术中含卤素橡塑产品的不足，本发明提供了一种制作工艺简单、方便，生产成本低，能兼顾产品性能、阻燃性能和使用安全性能的无卤素橡塑产品及其制备方法。
本发明采用的技术方案是：一种无卤素橡塑产品，按重量份数包括以下组份：分散剂HT-51680.5-1.5、硬脂酸钙0.1-0.5、聚乙二醇0.9-1.8、防老剂40200.1-0.5、活性氧化锌0.5-0.8、硫磺粉0.1-0.2、固体石蜡２-３、三氧化二锑0.3-0.6、硼酸锌3-6、丁腈橡胶10-13、氢氧化铝20-30、聚氯乙烯树脂12-18、二辛脂10-20、环氧大豆油5-10、炭黑N5501.5-3、偶氮二甲酰胺10-15、橡胶促剂1.5-3。
所述橡胶促剂按重量份数包括以下组份：二甲基二硫代氨基甲酸锌40-60、四硫化双五甲撑秋兰姆5-10、丁腈橡胶10-20、二辛脂8-15、防焦剂CTP2-5。
一种无卤素橡塑产品的制备方法，包括以下步骤：
(1)按权利要求1所述组份的重量份数称取原料：
(2)大料密炼：将按重量份数称取的分散剂HT-5168、硬脂酸钙、聚乙二醇、防老剂4020、活性氧化锌、硫磺粉、固体石蜡、三氧化二锑、硼酸锌、丁腈橡胶、氢氧化铝、聚氯乙烯树脂、二辛脂、环氧大豆油、炭黑N550和偶氮二甲酰胺放入密炼室，密炼室温度为125℃±10℃，密炼10分钟后，密炼胶条温度为145℃±10℃出料；
(3)小料密炼：将按重量份数称取的所述橡胶促剂按重量份数包括以下组份：二甲基二硫代氨基甲酸锌、四硫化双五甲撑秋兰姆、丁腈橡胶、二辛脂、防焦剂CTP混合成的橡胶促剂放入密炼室，密炼室温度为80℃±5℃，密炼10分钟后，密炼胶条温度至95℃±10℃出料；(4)大料开炼：将步骤(2)的出料倒入开炼机，辊距调至7-8mm，自动翻料3分钟切片，切出的胶片厚度8-10mm，胶片宽度600-800mm，胶片长度2500-3000mm；
(5)小料开炼：将步骤(3)的出料倒入开炼机，辊距调至4-6mm，自动翻料3分钟切片，切出的胶片厚度5-8mm，胶片宽度400-600mm，胶片长度1500-2000mm；
(6)成型胶炼制：将炼制好的大料、小料按质量比80：1.5-3称重；
(7)成型胶开炼：将步骤(6)的大料一半先投入开炼机，辊距调至4-6mm，开炼至包辊后，加入小料及另一半大料开炼至包辊后自动翻料2分钟下料胶条至凉胶架，胶条厚度6-8mm、宽度15-20mm、长度不切断；
(8)挤出成型：将步骤(7)的胶条放入挤出机，依次调整挤出机的温度为：机头段20℃-40℃、挤出段30℃-50℃、塑化段30℃-50℃、螺杆段20℃-30℃，启动挤出机，调整转速15-20转/分，将胶条均匀喂入喂料口挤出成型；
(9)硫化发泡：将步骤(8)挤出成型料经引料棒送入有多节烘箱发泡成橡塑板或管;多节烘为6段，多节烘为6段：一段烘干温度90℃-130℃、一段转速为0.8m/分钟，二段烘干温度130℃-140℃、二段转速为0.88m/分钟，三段烘干温度140℃-150℃、三段转速为0.97m/分钟，四段烘干温度150℃-160℃、四段转速为1.06m/分钟，五段烘干温度160℃-170℃、五段转速为1.17m/分钟，六段烘干温度170℃-180℃、六段转速为1.29m/分钟；
(10)牵引冷却:将发泡出的橡塑板或管用引料棒将其引入水槽冷却3-5分钟后经传送带至切台；
(11)剪切包装：调整切台的速度，使其与冷却传送带一致，调节计米器，按尺寸要求进行剪切,包装。
采用上述技术方案，本发明的有益效果是：
1、传统增塑剂为氯化石蜡，是含氯类的增塑剂，在燃烧时会产生有毒气体，并且耐热性、耐寒性、耐水性都较差，采用二辛脂代替氯化石蜡，二辛脂与许多聚合物有良好的相溶性，增塑效率高，挥发性小，耐候性、耐水性、耐低温良好，并且具有低毒性，具有理想的综合性能，导热系数在0℃时由原来的0.034W/(m.k)提高到0.032W/(m.k),抗老化性由原来150h轻微起皱，无裂纹，不变形可提升至180h轻微起皱，无裂纹，不变形；采用增塑剂使PVC树脂熔融温度、熔融粘度降低，降低成型加工温度，有利于成型加工，并使制品在使用温度范围内，具有较好的柔韧性和弹性、耐低温性等相关性能。
2、采用硼酸锌作无机阻燃剂，具有热稳定性好，毒性低和消烟等良好的功能，使产品在保证良好的氧指数下并有较低的烟密度。烟密度由60降至44。
3、减少硫磺粉使用，降低对设备铜管表面的硫化腐蚀。
4、橡胶促进剂中不含二苯胍、疏基苯并噻唑，使其改变了硫化程序，使泡孔更均匀细腻。
具体实施方式
以下结合实施例对本发明作进一步说明。
实施例一
一种无卤素橡塑产品，按重量份数包括以下组份：分散剂HT-51680.5、硬脂酸钙0.1、聚乙二醇0.9、防老剂40200.1、活性氧化锌0.5、硫磺粉0.1、固体石蜡２、三氧化二锑0.3、硼酸锌3、丁腈橡胶10、氢氧化铝20、聚氯乙烯树脂12、二辛脂10、环氧大豆油5、炭黑N5501.5、偶氮二甲酰胺10、橡胶促剂1.5。
所述橡胶促剂按重量份数配比：二甲基二硫代氨基甲酸锌40、四硫化双五甲撑秋兰姆5、丁腈橡胶10、二辛脂8、防焦剂CTP2。
一种无卤素橡塑产品的制备方法，包括以下步骤：
(1)按权利要求1所述组份的重量份数称取原料：
(2)大料密炼：将按重量份数称取的分散剂HT-5168、硬脂酸钙、聚乙二醇、防老剂4020、活性氧化锌、硫磺粉、固体石蜡、三氧化二锑、硼酸锌、丁腈橡胶、氢氧化铝、聚氯乙烯树脂、二辛脂、环氧大豆油、炭黑N550和偶氮二甲酰胺放入密炼室，密炼室温度为115℃，密炼10分钟后，密炼胶条温度为135℃出料；
(3)小料密炼：将按重量份数称取的所述橡胶促剂按重量份数包括以下组份：二甲基二硫代氨基甲酸锌、四硫化双五甲撑秋兰姆、丁腈橡胶、二辛脂、防焦剂CTP混合成的橡胶促剂放入密炼室，密炼室温度为74℃，密炼10分钟后，密炼胶条温度至85℃出料；
(4)大料开炼：将步骤(2)的出料倒入开炼机，辊距调至7mm，自动翻料3分钟切片，切出的胶片厚度8mm，胶片宽度600mm，胶片长度2500mm；
(5)小料开炼：将步骤(3)的出料倒入开炼机，辊距调至4mm，自动翻料3分钟切片，切出的胶片厚度5mm，胶片宽度400mm，胶片长度1500mm；
(6)成型胶炼制：将炼制好的大料、小料按质量比80：1.5称重；
(7)成型胶开炼：将步骤(6)的大料一半先投入开炼机，辊距调至4mm，开炼至包辊后，加入小料及另一半大料开炼至包辊后自动翻料2分钟下料胶条至凉胶架，胶条厚度6mm、宽度15mm、长度不切断；
(8)挤出成型：将步骤(7)的胶条放入挤出机，依次调整挤出机的温度为：机头段20℃、挤出段30℃、塑化段30℃、螺杆段20℃，启动挤出机，调整转速15转/分，将胶条均匀喂入喂料口挤出成型；
(9)硫化发泡：将步骤(8)挤出成型料经引料棒送入有多节烘箱发泡成橡塑板或管;多节烘为6段，多节烘为6段：一段烘干温度90℃、一段转速为0.8m/分钟，二段烘干温度130℃、二段转速为0.88m/分钟，三段烘干温度140℃、三段转速为0.97m/分钟，四段烘干温度150℃、四段转速为1.06m/分钟，五段烘干温度160℃、五段转速为1.17m/分钟，六段烘干温度170℃、六段转速为1.29m/分钟；
(10)牵引冷却:将发泡出的橡塑板或管用引料棒将其引入水槽冷却3分钟后经传送带至切台；
(11)剪切包装：调整切台的速度，使其与冷却传送带一致，调节计米器，按尺寸要求进行剪切,包装。
实施例二
一种无卤素橡塑产品，按重量份数包括以下组份：分散剂HT-51681.5、硬脂酸钙0.5、聚乙二醇1.8、防老剂40200.5、活性氧化锌0.8、硫磺粉0.2、固体石蜡３、三氧化二锑0.6、硼酸锌6、丁腈橡胶13、氢氧化铝30、聚氯乙烯树脂18、二辛脂20、环氧大豆油10、炭黑N5503、偶氮二甲酰胺15、橡胶促剂3。
所述橡胶促剂按重量份数配比：二甲基二硫代氨基甲酸锌60、四硫化双五甲撑秋兰姆10、丁腈橡胶20、二辛脂15、防焦剂CTP5。
一种无卤素橡塑产品的制备方法，包括以下步骤：
(1)按权利要求1所述组份的重量份数称取原料：
(2)大料密炼：将按重量份数称取的分散剂HT-5168、硬脂酸钙、聚乙二醇、防老剂4020、活性氧化锌、硫磺粉、固体石蜡、三氧化二锑、硼酸锌、丁腈橡胶、氢氧化铝、聚氯乙烯树脂、二辛脂、环氧大豆油、炭黑N550和偶氮二甲酰胺放入密炼室，密炼室温度为135℃，密炼10分钟后，密炼胶条温度为155℃出料；
(3)小料密炼：将按重量份数称取的所述橡胶促剂按重量份数包括以下组份：二甲基二硫代氨基甲酸锌、四硫化双五甲撑秋兰姆、丁腈橡胶、二辛脂、防焦剂CTP混合成的橡胶促剂放入密炼室，密炼室温度为85℃，密炼10分钟后，密炼胶条温度至105℃出料；(4)大料开炼：将步骤(2)的出料倒入开炼机，辊距调至8mm，自动翻料3分钟切片，切出的胶片厚度10mm，胶片宽度800mm，胶片长度3000mm；
(5)小料开炼：将步骤(3)的出料倒入开炼机，辊距调至6mm，自动翻料3分钟切片，切出的胶片厚度8mm，胶片宽度600mm，胶片长度2000mm；
(6)成型胶炼制：将炼制好的大料、小料按质量比80：3称重；
(7)成型胶开炼：将步骤(6)的大料一半先投入开炼机，辊距调至6mm，开炼至包辊后，加入小料及另一半大料开炼至包辊后自动翻料2分钟下料胶条至凉胶架，胶条厚度8mm、宽度20mm、长度不切断；
(8)挤出成型：将步骤(7)的胶条放入挤出机，依次调整挤出机的温度为：机头段40℃、挤出段50℃、塑化段50℃、螺杆段30℃，启动挤出机，调整转速20转/分，将胶条均匀喂入喂料口挤出成型；
(9)硫化发泡：将步骤(8)挤出成型料经引料棒送入有多节烘箱发泡成橡塑板或管;多节烘为6段，多节烘为6段：一段烘干温度130℃、一段转速为0.8m/分钟，二段烘干温度140℃、二段转速为0.88m/分钟，三段烘干温度150℃、三段转速为0.97m/分钟，四段烘干温度160℃、四段转速为1.06m/分钟，五段烘干温度170℃、五段转速为1.17m/分钟，六段烘干温度180℃、六段转速为1.29m/分钟；
(10)牵引冷却:将发泡出的橡塑板或管用引料棒将其引入水槽冷却5分钟后经传送带至切台；
(11)剪切包装：调整切台的速度，使其与冷却传送带一致，调节计米器，按尺寸要求进行剪切,包装。
实施例三
一种无卤素橡塑产品，按重量份数包括以下组份：分散剂HT-51681、硬脂酸钙0.4、聚乙二醇1.5、防老剂40200.3、活性氧化锌0.6、硫磺粉0.15、固体石蜡２.5、三氧化二锑0.4、硼酸锌5、丁腈橡胶12、氢氧化铝25、聚氯乙烯树脂16、二辛脂15、环氧大豆油8、炭黑N5502.2、偶氮二甲酰胺13、橡胶促剂2。
所述橡胶促剂按重量份数配比：二甲基二硫代氨基甲酸锌50、四硫化双五甲撑秋兰姆8、丁腈橡胶15、二辛脂12、防焦剂CTP3。
一种无卤素橡塑产品的制备方法，包括以下步骤：
(1)按权利要求1所述组份的重量份数称取原料：
(2)大料密炼：将按重量份数称取的分散剂HT-5168、硬脂酸钙、聚乙二醇、防老剂4020、活性氧化锌、硫磺粉、固体石蜡、三氧化二锑、硼酸锌、丁腈橡胶、氢氧化铝、聚氯乙烯树脂、二辛脂、环氧大豆油、炭黑N550和偶氮二甲酰胺放入密炼室，密炼室温度为125℃，密炼10分钟后，密炼胶条温度为145℃出料；
(3)小料密炼：将按重量份数称取的所述橡胶促剂按重量份数包括以下组份：二甲基二硫代氨基甲酸锌、四硫化双五甲撑秋兰姆、丁腈橡胶、二辛脂、防焦剂CTP混合成的橡胶促剂放入密炼室，密炼室温度为80℃，密炼10分钟后，密炼胶条温度至95℃出料；(4)大料开炼：将步骤(2)的出料倒入开炼机，辊距调至7.5mm，自动翻料3分钟切片，切出的胶片厚度9mm，胶片宽度700mm，胶片长度2800mm；
(5)小料开炼：将步骤(3)的出料倒入开炼机，辊距调至5mm，自动翻料3分钟切片，切出的胶片厚度7mm，胶片宽度500mm，胶片长度1800mm；
(6)成型胶炼制：将炼制好的大料、小料按质量比40：1称重；
(7)成型胶开炼：将步骤(6)的大料一半先投入开炼机，辊距调至5mm，开炼至包辊后，加入小料及另一半大料开炼至包辊后自动翻料2分钟下料胶条至凉胶架，胶条厚度7mm、宽度18mm、长度不切断；
(8)挤出成型：将步骤(7)的胶条放入挤出机，依次调整挤出机的温度为：机头段30℃、挤出段40℃、塑化段40℃、螺杆段25℃，启动挤出机，调整转速18转/分，将胶条均匀喂入喂料口挤出成型；
(9)硫化发泡：将步骤(8)挤出成型料经引料棒送入有多节烘箱发泡成橡塑板或管;多节烘为6段，多节烘为6段：一段烘干温度120℃、一段转速为0.8m/分钟，二段烘干温度135℃、二段转速为0.88m/分钟，三段烘干温度145℃、三段转速为0.97m/分钟，四段烘干温度155℃、四段转速为1.06m/分钟，五段烘干温度165℃、五段转速为1.17m/分钟，六段烘干温度175℃、六段转速为1.29m/分钟；
(10)牵引冷却:将发泡出的橡塑板或管用引料棒将其引入水槽冷却4分钟后经传送带至切台；
(11)剪切包装：调整切台的速度，使其与冷却传送带一致，调节计米器，按尺寸要求进行剪切,包装。

Claims (2)

1.一种无卤素橡塑产品，其特征是：按重量份数包括以下组份：
分散剂HT-51680.5-1.5
硬脂酸钙0.1-0.5
聚乙二醇0.9-1.8
防老剂40200.1-0.5
活性氧化锌0.5-0.8
硫磺粉0.1-0.2
固体石蜡２-３
三氧化二锑0.3-0.6
硼酸锌3-6
丁腈橡胶10-13
氢氧化铝20-30
聚氯乙烯树脂12-18
二辛脂10-20
环氧大豆油5-10
炭黑N5501.5-3
偶氮二甲酰胺10-15
橡胶促剂1.5-3；
所述橡胶促剂按重量份数包括以下组份：二甲基二硫代氨基甲酸锌40-60、四硫化双五甲撑秋兰姆5-10、丁腈橡胶10-20、二辛脂8-15、防焦剂CTP2-5。
2.一种无卤素橡塑产品的制备方法，包括以下歩骤：
(1)按权利要求1所述组份的重量份数称取原料；
(2)大料密炼：将按重量份数称取的分散剂HT-5168、硬脂酸钙、聚乙二醇、防老剂4020、活性氧化锌、硫磺粉、固体石蜡、三氧化二锑、硼酸锌、丁腈橡胶、氢氧化铝、聚氯乙烯树脂、二辛脂、环氧大豆油、炭黑N550和偶氮二甲酰胺放入密炼室，密炼室温度为125℃±10℃，密炼10分钟后，密炼胶条温度为145℃±10℃出料；
(3)小料密炼：将按重量份数称取的所述橡胶促剂按重量份数包括以下组份：二甲基二硫代氨基甲酸锌、四硫化双五甲撑秋兰姆、丁腈橡胶、二辛脂、防焦剂CTP混合成的橡胶促剂放入密炼室，密炼室温度为80℃±5℃，密炼10分钟后，密炼胶条温度至95℃±10℃出料；
(4)大料开炼：将步骤(2)的出料倒入开炼机，辊距调至7-8mm，自动翻料3分钟切片，切出的胶片厚度8-10mm，胶片宽度600-800mm，胶片长度2500-3000mm；
(5)小料开炼：将步骤(3)的出料倒入开炼机，辊距调至6-7mm，自动翻料3分钟切片，切出的胶片厚度5-8mm，胶片宽度400-600mm，胶片长度1500-2000mm；
(6)成型胶炼制：将炼制好的大料、小料按质量比80：1.5-3称重；
(7)成型胶开炼：将步骤(6)的大料一半先投入开炼机开炼至包辊后，加入小料及另一半大料开炼至包辊后，辊距调至4-6mm，自动翻料2分钟下料胶条至凉胶架，胶条厚度6-8mm、宽度15-20mm、长度不切断；
(8)挤出成型：将步骤(7)的胶条放入挤出机，依次调整挤出机的温度为：机头段20℃-40℃、挤出段30℃-50℃、塑化段30℃-50℃、螺杆段20℃-30℃，启动挤出机，调整转速15-20转/分，将胶条均匀喂入喂料口挤出成型；
(9)硫化发泡：将步骤(8)挤出成型料经引料棒送入有多节烘箱发泡成橡塑板或管;多节烘为6段：一段烘干温度90℃-130℃、一段转速为0.8m/分钟，二段烘干温度130℃-140℃、二段转速为0.88m/分钟，三段烘干温度140℃-150℃、三段转速为0.97m/分钟，四段烘干温度150℃-160℃、四段转速为1.06m/分钟，五段烘干温度160℃-170℃、五段转速为1.17m/分钟，六段烘干温度170℃-180℃、六段转速为1.29m/分钟；
(10)牵引冷却:将发泡出的橡塑板或管用引料棒将其引入水槽冷却3-5分钟后经传送带至切台；
(11)剪切包装：调整切台的速度，使其与冷却传送带一致，调节计米器，按尺寸要求进行剪切,包装。
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CN109401123A (zh) * 2018-10-15 2019-03-01 瑞安市顺丰塑料助剂有限公司 一种含增韧稳定剂的鞋用聚氯乙烯及其制备方法
CN111763362A (zh) * 2020-07-28 2020-10-13 惠州优比贝柠科技股份有限公司 一种防火橡胶发泡板材及其制备方法
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CN113621185B (zh) * 2021-08-30 2023-06-06 华美节能科技集团有限公司 一种无卤橡塑保温材料及其制备方法

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