CN105885393A - 一种可用于海水淡化的tpu薄膜及其制备方法 - Google Patents

一种可用于海水淡化的tpu薄膜及其制备方法 Download PDF

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CN105885393A
CN105885393A CN201610403599.2A CN201610403599A CN105885393A CN 105885393 A CN105885393 A CN 105885393A CN 201610403599 A CN201610403599 A CN 201610403599A CN 105885393 A CN105885393 A CN 105885393A
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tpu film
diisocyanate
glycol
micropowder
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何建雄
王良
王一良
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Dongguan Xionglin New Materials Technology Co Ltd
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Abstract

本发明涉及一种可用于海水淡化的TPU薄膜及其制备方法，所述TPU薄膜，按重量份包括以下原料：端羟基聚醚二元醇50‑100份、二异氰酸酯15‑30份、扩链剂5‑35份、高炉矿渣微粉1‑3份、二硫化钼微粉1‑5份、鳞片状石墨1‑5份、蓖麻油2‑3份、巴西棕榈蜡2‑6份、三氧化二铝4‑9份、滑石粉3‑9份、氨基硅油1‑5份、松香改性酚醛树脂1‑3份、轻质碳酸钙1‑3份和壳聚糖1‑5份。本发明所提供的TPU薄膜具有优异的机械性能、耐低温性能、耐腐蚀性能和热氧老化性能，适用于海水淡化工程。

Description

一种可用于海水淡化的TPU薄膜及其制备方法
技术领域
本发明涉及聚氨酯材料领域，尤其涉及一种可用于海水淡化的TPU薄膜及其制备方法。
背景技术
热塑性聚氨酯弹性体(又称为TPU)新材料被称为“划时代的新型高分子材料”，是当前世界六大具有发展前途的合成材料之一，其既具有橡胶的弹性又有塑料的硬度，而且还具有良好的机械性能、耐磨性能和回弹性能，因此已被广泛应用。
研究聚氨酯弹性体的机械性能、耐低温性能、耐腐蚀性能和热氧老化性能，使其适用于海水淡化工程，无论是对社会还是聚氨酯工业，都具有非常重要的意义。
发明内容
为解决上述技术问题，本发明提供了一种可用于海水淡化的TPU薄膜及其制备方法。
为达此目的，本发明采用了以下技术方案：
第一方面，本发明提供了一种可用于海水淡化的TPU薄膜，按重量份包括以下原料：端羟基聚醚二元醇50-100份、二异氰酸酯15-30份、扩链剂5-35份、高炉矿渣微粉1-3份、二硫化钼微粉1-5份、鳞片状石墨1-5份、蓖麻油2-3份、巴西棕榈蜡2-6份、三氧化二铝4-9份、滑石粉3-9份、氨基硅油1-5份、松香改性酚醛树脂1-3份、轻质碳酸钙1-3份和壳聚糖1-5份。
本发明的TPU薄膜的原料中，所述端羟基聚醚二元醇的含量为50-100份，例如可以是50份、60份、65份、70份、72份、78份、80份、90份、95份或100份，优选为60-80份，进一步优选为72份。
本发明的TPU薄膜的原料中，所述二异氰酸酯的含量为15-30份，例如可以是15份、18份、20份、22份、25份、28份或30份，优选为16-30份，进一步优选为23份。
本发明的TPU薄膜的原料中，所述扩链剂的含量为5-35份，例如可以是5份、6份、8份、10份、12份、15份、18份、22份、30份或35份，优选为7-32份，进一步优选为25份。
本发明的TPU薄膜的原料中，所述高炉矿渣微粉的含量为1-3份，例如可以是1份、1.5份、2份、2.5份或3份；所述二硫化钼微粉的含量为1-5份，例如可以是1份、1.5份、2份、2.5份、3份或5份；所述鳞片状石墨的含量为1-5份，例如可以是1份、2份、3份、4份或5份；所述蓖麻油的含量为2-3份，例如可以是1份、1.5份、2份、2.5份或3份；所述巴西棕榈蜡的含量为2-6份，例如可以是2份、3份、4份、5份或6份；所述三氧化二铝的含量为4-9份，例如可以是4份、5份、6份、7份、8份或9份；所述滑石粉的含量为3-9份，例如可以是3份、5份、6份、7份、8份或9份；所述氨基硅油的含量为1-5份，例如可以是1份、1.5份、2份、2.5份、3份或5份；所述松香改性酚醛树脂的含量为1-3份，例如可以是1份、1.5份、2份、2.5份或3份；所述轻质碳酸钙的含量为1-3份，例如可以是1份、1.5份、2份、2.5份或3份；所述壳聚糖的含量为1-5份，例如可以是1份、1.5份、2份、2.5份、3份或5份。
作为本发明优选的技术方案，所述TPU薄膜按重量份包括以下原料：端羟基聚醚二元醇60-80份、二异氰酸酯16-30份、扩链剂7-32份、高炉矿渣微粉1-2份、二硫化钼微粉1-3份、鳞片状石墨1-2份、蓖麻油2-3份、巴西棕榈蜡2-5份、三氧化二铝4-8份、滑石粉3-7份、氨基硅油1-3份、松香改性酚醛树脂1-2份、轻质碳酸钙1-2份和壳聚糖1-4份。
进一步优选地，所述TPU薄膜按重量份包括以下原料：端羟基聚醚二元醇72份、二异氰酸酯23份、扩链剂25份、高炉矿渣微粉1份、二硫化钼微粉1份、鳞片状石墨2份、蓖麻油2份、巴西棕榈蜡5份、三氧化二铝5份、滑石粉5份、氨基硅油3份、松香改性酚醛树脂2份、轻质碳酸钙1份和壳聚糖1份。
根据本发明，所述端羟基聚醚二元醇为聚己内酯二醇、聚四氢呋喃二醇和聚己二酸乙二醇酯二醇的混合物；所述聚己内酯二醇、聚四氢呋喃二醇和聚己二酸乙二醇酯二醇的质量比为1:(1-5):(3-7)，优选为1:3:6。
根据本发明，所述聚己内酯二醇的数均相对分子质量为5000-8000，所述聚四氢呋喃二醇的数均相对分子质量为5000-8000，所述聚己二酸乙二醇酯二醇的数均相对分子质量为8000-10000。
根据本发明，所述二异氰酸酯为2，4-甲苯二异氰酸酯、4，4’-二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯或六亚甲基二异氰酸酯中的任意一种或至少两种的混合物。
根据本发明，所述扩链剂为二羟甲基丙酸、二羟基半酯、二氨基苯甲酸或N-甲基二乙醇胺中的任意一种或至少两种的混合物。
第二方面，本发明还提供了所述的TPU薄膜的制备方法，其包括以下步骤：
将端羟基聚醚二元醇、二异氰酸酯、扩链剂、高炉矿渣微粉、二硫化钼微粉、鳞片状石墨、蓖麻油、巴西棕榈蜡、三氧化二铝、滑石粉、氨基硅油、松香改性酚醛树脂、轻质碳酸钙和壳聚糖进行混合，通过一步法本体聚合制备TPU颗粒，使用双螺杆挤出机挤出，再采用吹膜法或者流延成膜技术，使用单螺杆机挤出机制备得到所述TPU薄膜。
本发明所述TPU薄膜的制备方法中不加入溶剂。
与现有技术相比，本发明至少具有以下有益效果：
本发明所提供的TPU薄膜具有优异的机械性能、耐低温性能、耐腐蚀性能和热氧老化性能，适用于海水淡化工程。
具体实施方式
为便于理解本发明，本发明列举实施例如下。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
实施例1
将端羟基聚醚二元醇72kg(由数均相对分子质量为5000的聚己内酯二醇、数均相对分子质量为6000的聚四氢呋喃二醇和数均相对分子质量为9000的聚己二酸乙二醇酯二醇三者按质量比为1:3:6组成)、2，4-甲苯二异氰酸酯23kg、二氨基苯甲酸25kg、高炉矿渣微粉1kg、二硫化钼微粉1kg、鳞片状石墨2kg、蓖麻油2kg、巴西棕榈蜡5kg、三氧化二铝5kg、滑石粉5kg、氨基硅油3kg、松香改性酚醛树脂2kg、轻质碳酸钙1kg和壳聚糖1kg进行混合，通过一步法本体聚合制备TPU颗粒，使用双螺杆挤出机挤出，再采用吹膜法或者流延成膜技术，使用单螺杆机挤出机制备得到所述TPU薄膜。
实施例2
将端羟基聚醚二元醇60kg(由数均相对分子质量为5000的聚己内酯二醇、数均相对分子质量为7000的聚四氢呋喃二醇和数均相对分子质量为10000的聚己二酸乙二醇酯二醇三者按质量比为1:3:7组成)、4，4’-二苯基甲烷二异氰酸酯23kg、二羟基半酯25kg、高炉矿渣微粉1kg、二硫化钼微粉3kg、鳞片状石墨2kg、蓖麻油2kg、巴西棕榈蜡5kg、三氧化二铝5kg、滑石粉5kg、氨基硅油3kg、松香改性酚醛树脂2kg、轻质碳酸钙4kg和壳聚糖4kg进行混合，通过一步法本体聚合制备TPU颗粒，使用双螺杆挤出机挤出，再采用吹膜法或者流延成膜技术，使用单螺杆机挤出机制备得到所述TPU薄膜。
实施例3
将端羟基聚醚二元醇80kg(由数均相对分子质量为8000的聚己内酯二醇、数均相对分子质量为5000的聚四氢呋喃二醇和数均相对分子质量为9000的聚己二酸乙二醇酯二醇三者按质量比为1:1:5组成)、异佛尔酮二异氰酸酯20kg、二羟基半酯20kg、高炉矿渣微粉2kg、二硫化钼微粉1kg、鳞片状石墨2kg、蓖麻油2kg、巴西棕榈蜡2kg、三氧化二铝5kg、滑石粉5kg、氨基硅油3kg、松香改性酚醛树脂2kg、轻质碳酸钙4kg和壳聚糖4kg进行混合，通过一步法本体聚合制备TPU颗粒，使用双螺杆挤出机挤出，再采用吹膜法或者流延成膜技术，使用单螺杆机挤出机制备得到所述TPU薄膜。
对比例1
与实施例1相比，除将端羟基聚醚二元醇中的聚己内酯二醇替换为数均相对分子质量是4000的聚己内酯二醇以外，其它与实施例1相同。
对比例2
与实施例1相比，除将端羟基聚醚二元醇中的聚四氢呋喃二醇替换为数均相对分子质量是9000的聚四氢呋喃二醇以外，其它与实施例1相同。
对比例3
与实施例1相比，除将端羟基聚醚二元醇中的聚己二酸乙二醇酯二醇替换为数均相对分子质量是5000的聚己二酸乙二醇酯二醇以外，其它与实施例1相同。
对比例4
与实施例1相比，除将端羟基聚醚二元醇中各组分的重量配比替换为2:3:6外，其它与实施例1相同。
对比例5
与实施例1相比，除将端羟基聚醚二元醇中各组分的重量配比替换为2:4:9外，其它与实施例1相同。
对比例6
与实施例1相比，除不加入高炉矿渣微粉、二硫化钼微粉、鳞片状石墨、蓖麻油、巴西棕榈蜡、三氧化二铝、滑石粉、氨基硅油、松香改性酚醛树脂、轻质碳酸钙和壳聚糖这些组分外，其它与实施例1相同。
对比例7-17
与实施例1相比，除依次不加入高炉矿渣微粉、二硫化钼微粉、鳞片状石墨、蓖麻油、巴西棕榈蜡、三氧化二铝、滑石粉、氨基硅油、松香改性酚醛树脂、轻质碳酸钙和壳聚糖这些单独组分外，例如对比例7为不加入高炉矿渣微粉组分，对比例8为不加入二硫化钼微粉组分，其它与实施例1相同。
耐腐蚀性能测试：
采用高温热碱法来测试TPU薄膜的耐腐蚀性，将上述实施例和对比例的TPU薄膜置于耐压、密闭的消化罐中，分别称其质量，然后在150℃的5％NaOH溶液中水解8h后，用蒸馏水洗涤，干燥，称量其剩余质量，计算样品的质量损失率，结果如表1所示。
表1
综上可以得出，本发明所提供的TPU薄膜具有优异的机械性能、耐低温性能、耐腐蚀性能和热氧老化性能，适用于海水淡化工程。
申请人声明，本发明通过上述实施例来说明本发明的详细工艺设备和工艺流程，但本发明并不局限于上述详细工艺设备和工艺流程，即不意味着本发明必须依赖上述详细工艺设备和工艺流程才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (8)

1.一种可用于海水淡化的TPU薄膜，其特征在于，按重量份包括以下原料：端羟基聚醚二元醇50-100份、二异氰酸酯15-30份、扩链剂5-35份、高炉矿渣微粉1-3份、二硫化钼微粉1-5份、鳞片状石墨1-5份、蓖麻油2-3份、巴西棕榈蜡2-6份、三氧化二铝4-9份、滑石粉3-9份、氨基硅油1-5份、松香改性酚醛树脂1-3份、轻质碳酸钙1-3份和壳聚糖1-5份。
2.根据权利要求1所述的TPU薄膜，其特征在于，按重量份包括以下原料：端羟基聚醚二元醇60-80份、二异氰酸酯16-30份、扩链剂7-32份、高炉矿渣微粉1-2份、二硫化钼微粉1-3份、鳞片状石墨1-2份、蓖麻油2-3份、巴西棕榈蜡2-5份、三氧化二铝4-8份、滑石粉3-7份、氨基硅油1-3份、松香改性酚醛树脂1-2份、轻质碳酸钙1-2份和壳聚糖1-4份。
3.根据权利要求1或2所述的TPU薄膜，其特征在于，按重量份包括以下原料：端羟基聚醚二元醇72份、二异氰酸酯23份、扩链剂25份、高炉矿渣微粉1份、二硫化钼微粉1份、鳞片状石墨2份、蓖麻油2份、巴西棕榈蜡5份、三氧化二铝5份、滑石粉5份、氨基硅油3份、松香改性酚醛树脂2份、轻质碳酸钙1份和壳聚糖1份。
4.根据权利要求1-3之一所述的TPU薄膜，其特征在于，所述端羟基聚醚二元醇为聚己内酯二醇、聚四氢呋喃二醇和聚己二酸乙二醇酯二醇的混合物；所述聚己内酯二醇、聚四氢呋喃二醇和聚己二酸乙二醇酯二醇的质量比为1:(1-5):(3-7)。
5.根据权利要求4所述的TPU薄膜，其特征在于，所述聚己内酯二醇的数均相对分子质量为5000-8000，所述聚四氢呋喃二醇的数均相对分子质量为5000-8000，所述聚己二酸乙二醇酯二醇的数均相对分子质量为8000-10000。
6.根据权利要求1-5之一所述的TPU薄膜，其特征在于，所述二异氰酸酯为2，4-甲苯二异氰酸酯、4，4’-二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯或六亚甲基二异氰酸酯中的任意一种或至少两种的混合物。
7.根据权利要求1-6之一所述的TPU薄膜，其特征在于，所述扩链剂为二羟甲基丙酸、二羟基半酯、二氨基苯甲酸或N-甲基二乙醇胺中的任意一种或至少两种的混合物。
8.根据权利要求1-7之一所述的TPU薄膜的制备方法，其特征在于，包括以下步骤：
将端羟基聚醚二元醇、二异氰酸酯、扩链剂、高炉矿渣微粉、二硫化钼微粉、鳞片状石墨、蓖麻油、巴西棕榈蜡、三氧化二铝、滑石粉、氨基硅油、松香改性酚醛树脂、轻质碳酸钙和壳聚糖进行混合，通过一步法本体聚合制备TPU颗粒，使用双螺杆挤出机挤出，再采用吹膜法或者流延成膜技术，使用单螺杆机挤出机制备得到所述TPU薄膜。
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CN1191471A (zh) * 1995-06-07 1998-08-26 耐克国际有限公司 基于包括聚酯多元醇的聚氨酯的隔膜材料
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