CN106928430B - 一种热塑性脂肪族聚脲弹性体及其制备方法 - Google Patents

一种热塑性脂肪族聚脲弹性体及其制备方法 Download PDF

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CN106928430B
CN106928430B CN201710188559.5A CN201710188559A CN106928430B CN 106928430 B CN106928430 B CN 106928430B CN 201710188559 A CN201710188559 A CN 201710188559A CN 106928430 B CN106928430 B CN 106928430B
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王伟
王宝柱
李永岗
郭焱
温喜梅
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Qingdao Aier Jia New Materials Ltd By Share Ltd
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Abstract

本发明属于聚脲弹性体技术领域，具体来说是一种热塑性脂肪族聚脲弹性体及其制备方法。所述热塑性脂肪族聚脲弹性体由以下重量份的各原材料制成：脂肪族二异氰酸酯30～40份，多元醇5～15份，端氨基聚醚25～40份，扩链剂2～8份，紫外线吸收剂0.1～0.5份，色浆1.0～3.0份。本发明将传统的喷涂聚脲材料制备成了可进行挤塑成型的热塑性聚脲弹性体材料，可采用传统的挤塑机进行施工，材料浪费率极低，且材料的可设计性强，具有非常好的拉伸强度、耐磨性能、耐冲击性能、防腐性能，优异的低温柔韧性，优异的绝缘性能，可以用于各种规格的管道、线缆、钢索的防腐防护。

Description

一种热塑性脂肪族聚脲弹性体及其制备方法
技术领域
本发明属于聚脲弹性体技术领域，具体来说是一种热塑性脂肪族聚脲弹性体及其制备方法。
背景技术
聚脲弹性体是由异氰酸酯与氨基化合物反应生成的一种弹性体物质，常见的聚脲弹性体一般为MDI预聚物与端氨基化合物组成的喷涂反应型材料(喷涂聚脲弹性体材料)，具有固化速度快，施工效率高，以及非常好的力学性能、防腐性能和电学性能，被广泛应用于工程防水、工业防腐领域。
但是对于一些特殊的工业防腐领域，如直径小于40cm的线缆、小口径管道等，传统的喷涂型聚脲弹性体的应用却受到限制，主要表现在以下几个方面：
(1)线缆及小口径的管道截面积较小，采用喷涂聚脲弹性体技术浪费非常大，损耗率在85％以上，特别是管道或线缆的直径小于40cm的时候；
(2)管道或线缆由于是圆柱体，喷涂时厚度很难精确控制，而且常常会出现厚度不均匀现象；
(3)MDI预聚物为芳香族异氰酸酯，含有大量的苯环结构，在紫外线照射下很容易变色粉化，因而不适合户外应用。
另外，挤塑工艺可以精确控制材料的厚度，几乎没有损耗，非常适合各种管道线缆的外壁涂装，但是要求材料为热塑性材料。
脂肪族聚脲弹性体具有非常好的耐候性、防腐性能及力学性能，但是喷涂施工的时候浪费同样很严重，并且由于其固化反应速比芳香族聚脲慢，容易出现流挂现象。
发明内容
为解决现有技术中存在的上述问题，本发明提供一种可以采用挤塑工艺施工的热塑性脂肪族聚脲弹性体及其制备方法。
一种热塑性脂肪族聚脲弹性体，由以下重量份的各原材料制成：
所述的脂肪族二异氰酸酯为异佛尔酮二异氰酸酯IPDI、二环己基甲烷二异氰酸酯HMDI、六亚甲基二异氰酸酯HDI中的一种或几种的混合物。
所述的多元醇为分子量在500-2000之间的聚四氢呋喃二醇PTMEG、聚己内酯二醇PCL、聚碳酸酯二醇PCDL中的一种或任意几种的混合物。
所述的端氨基聚醚为D400、D2000、T5000中的一种或两种的混合物。
所述的扩链剂为小分子量二元胺，所述的二元胺为脂肪族二元胺，优选氢化间苯二甲胺1,3BAC、异佛尔酮二胺IPDA、亨斯曼公司JEFFLINKTM754、UOP公司CLEARLINK1000中的一种或几种的混合物。
所述的紫外线吸收剂为苯并三唑类、取代丙烯腈类、三嗪类和受阻胺类化合物中的一种或几种的复配物。
所述的色浆为聚氨酯专用色浆，其含水量≤0.5％(重量比)。
所述热塑性脂肪族聚脲弹性体的制备方法，包括以下步骤：
(1)先将端氨基聚醚、扩链剂、紫外线吸收剂、色浆加入到1#反应釜中混合均匀，抽真空脱水备用；
(2)将多元醇加入到2#反应釜中，抽真空脱水备用；
(3)将脂肪族二异氰酸酯加入到3#反应釜中，将1#反应釜中制备的混合物用计量泵加入到3#反应釜中，制备含脲基的异氰酸酯预聚物；
(4)将步骤(3)制备的预聚物和经(2)脱水后的多元醇分别用计量泵加入到双螺杆反应器中，经反应后由机头挤出胶条，经冷却、切粒、干燥、冷却后，即可包装。
所述步骤(1)(2)均在100～120℃温度下抽真空脱水2～3h备用。
所述步骤(4)中双螺杆反应器的温度为120～140℃，干燥温度为100～110℃。
所述含脲基的异氰酸酯预聚物的-NCO含量为13～16％。
综上，本发明经不同分段温度先用过量的异氰酸酯与端氨基聚醚、扩链剂反应生成含有大量脲键的异氰酸酯预聚物，然后用多元醇对其封端，将异氰酸酯指数控制在0.94-0.99之间，最终得到热塑性的脂肪族聚脲弹性体。
本发明将传统的喷涂聚脲材料制备成了可进行挤塑成型的热塑性聚脲弹性体材料，可采用传统的挤塑机进行施工，材料浪费率极低，且在选用原材料的时候通过选用耐候性好的脂肪族异氰酸酯、扩链剂以及高性能的多元醇，使制备出的材料具有非常优异的性能，主要包括以下几点：
1)绿色环保，边角料可以反复使用，几乎没有废料产生；
2)不含催化剂，材料的耐老化性能、耐候性能优异，可满足户外长期使用；
3)与喷涂聚脲材料一样具有强度高，耐水、耐腐蚀、耐油性能优异等特点；
4)材料的可设计性强，可以通过调整异氰酸酯、端氨基聚醚、扩链剂、多元醇等主要原材料的种类及数量，异氰酸酯指数的大小来调整材料的性能和加工性能；
5)具有非常好的拉伸强度、耐磨性能、耐冲击性能、防腐性能，优异的低温柔韧性，优异的绝缘性能，可以用于各种规格的管道、线缆、钢索的防腐防护。
具体实施方式
下面将结合具体实施例作进一步说明。
实施例1
(1)先将30份D2000、5份IPDA、0.1份紫外线吸收剂、3份色浆加入到1#反应釜中混合均匀，在100～120℃温度下抽真空脱水2～3h备用；
(2)将分子量为1000的PTMEG多元醇加入到2#反应釜中在100～120℃温度下抽真空脱水2～3h备用；
(3)然后将HMDI加入到3#反应釜中，将1#反应釜中制备的混合物用计量泵加入到3#反应釜中，制备含脲基的异氰酸酯预聚物，其-NCO含量为13％；
(4)将步骤(3)制备的预聚物和经(2)脱水后的PTMEG分别用计量泵加入到120～140℃左右的双螺杆反应器中，异氰酸酯指数为0.97，在一定的螺杆转速下，连续反应和移动，经双螺杆反应器的不同分段温度反应一定时间后由机头挤出胶条，并引入水槽冷却。造粒冷却后的胶条经造粒机切粒，胶粒在100～110℃的烘箱中干燥，冷却后，即可包装。实施例1所制备的热塑性脂肪族聚脲弹性体的主要性能指标如表1所示：
表1实施例1热塑性脂肪族聚脲弹性体主要性能
编号 项目 指标 结果
1 加工温度，℃ 180-190 180-190
2 硬度(邵D) ≥30 D/15:38
3 拉伸强度，MPa ≥15 19.4
4 撕裂强度，KN/m ≥40 45
5 断裂伸长率，％ ≥400 413
6 密度，g/cm<sup>3</sup> 1.0±0.02 0.98
7 耐磨性，cm<sup>3</sup> ≤0.05 0.02
实施例2
(1)先将20份D2000、5份D400、3份T5000、8份CLEARLINK1000、0.3份紫外线吸收剂、1份色浆加入到1#反应釜中混合均匀，在100～120℃温度下抽真空脱水2～3h备用；
(2)将分子量为1000的PCDL多元醇加入到2#反应釜中在100～120℃温度下抽真空脱水2～3h备用；
(3)然后将IPDI加入到3#反应釜中，将1#反应釜中制备的混合物用计量泵加入到3#反应釜中，制备含脲基的异氰酸酯预聚物，其-NCO含量为16％；
(4)将步骤(3)制备的预聚物和经(2)脱水后的PCDL分别用计量泵加入到120～140℃左右的双螺杆反应器中，异氰酸酯指数为0.94，在一定的螺杆转速下，连续反应和移动，经双螺杆反应器的不同分段温度反应一定时间后由机头挤出胶条，并引入水槽冷却。造粒冷却后的胶条经造粒机切粒，胶粒在100～110℃的烘箱中干燥，冷却后，即可包装。实施例2所制备的热塑性脂肪族聚脲弹性体的主要性能指标如表2所示：
表2实施例2热塑性脂肪族聚脲弹性体主要性能
编号 项目 指标 结果
1 加工温度，℃ 180-190 180-190
2 硬度(邵D) ≥30 D/15:32
3 拉伸强度，MPa ≥15 21.6
4 撕裂强度，KN/m ≥40 47
5 断裂伸长率，％ ≥400 500
6 密度，g/cm<sup>3</sup> 1.0±0.02 0.99
7 耐磨性，cm<sup>3</sup> ≤0.05 0.01
实施例3
(1)先将25份D2000、5份D400、7份JEFFLINKTM754、0.5份紫外线吸收剂、2份色浆加入到1#反应釜中混合均匀，在100～120℃温度下抽真空脱水2～3h备用；
(2)将分子量为2000的PCL多元醇加入到2#反应釜中在100～120℃温度下抽真空脱水2～3h备用；
(3)然后将HDI加入到3#反应釜中，将1#反应釜中制备的混合物用计量泵加入到3#反应釜中，制备含脲基的异氰酸酯预聚物，其-NCO含量为14％；
(4)将步骤(3)制备的预聚物和经(2)脱水后的PTMEG分别用计量泵加入到120～140℃左右的双螺杆反应器中，异氰酸酯指数为0.98，在一定的螺杆转速下，连续反应和移动，经双螺杆反应器的不同分段温度反应一定时间后由机头挤出胶条，并引入水槽冷却。造粒冷却后的胶条经造粒机切粒，胶粒在100～110℃的烘箱中干燥，冷却后，即可包装。实施例3所制备的热塑性脂肪族聚脲弹性体的主要性能指标如表3所示：
表3实施例3热塑性脂肪族聚脲弹性体主要性能
编号 项目 指标 结果
1 加工温度，℃ 180-190 180-190
2 硬度(邵D) ≥30 D/15:33
3 拉伸强度，MPa ≥15 15.4
4 撕裂强度，KN/m ≥40 41
5 断裂伸长率，％ ≥400 506
6 密度，g/cm<sup>3</sup> 1.0±0.02 1.00
7 耐磨性，cm<sup>3</sup> ≤0.05 0.02
实施例4
(1)先将30份D2000、5份1,3BAC、0.2份紫外线吸收剂、2.3份色浆加入到1#反应釜中混合均匀，在100～120℃温度下抽真空脱水2～3h备用；
(2)将分子量为2000的PTMEG多元醇和分子量为500的PCL按照重量比1:1加入到2#反应釜中在100～120℃温度下抽真空脱水2～3h备用；
(3)然后将HMDI加入到3#反应釜中，将1#反应釜中制备的混合物用计量泵加入到3#反应釜中，制备含脲基的异氰酸酯预聚物，其-NCO含量为14％；
(4)将步骤(3)制备的预聚物和经(2)脱水后的PTMEG分别用计量泵加入到120～140℃左右的双螺杆反应器中，异氰酸酯指数为0.99，在一定的螺杆转速下，连续反应和移动，经双螺杆反应器的不同分段温度反应一定时间后由机头挤出胶条，并引入水槽冷却。造粒冷却后的胶条经造粒机切粒，胶粒在100～110℃的烘箱中干燥，冷却后，即可包装。实施例4所制备的热塑性脂肪族聚脲弹性体的主要性能指标如表4所示：
表4实施例4热塑性脂肪族聚脲弹性体主要性能
编号 项目 指标 结果
1 加工温度，℃ 180-190 180-190
2 硬度(邵D) ≥30 D/15:35
3 拉伸强度，MPa ≥15 16.4
4 撕裂强度，KN/m ≥40 42
5 断裂伸长率，％ ≥400 453
6 密度，g/cm<sup>3</sup> 1.0±0.02 0.98
7 耐磨性，cm<sup>3</sup> ≤0.05 0.02
实施例5
(1)先将18份D2000、10份D400、4份T5000、2份IPDA、0.3份紫外线吸收剂、3份色浆加入到1#反应釜混合均匀，在100～120℃温度下抽真空脱水2～3h备用；
(2)将分子量为2000的PTMEG多元醇加入到2#反应釜中在100～120℃温度下抽真空脱水2～3h备用；
(3)然后将HMDI和IPDI按照质量比1:1加入到3#反应釜中，将1#反应釜中制备的混合物用计量泵加入到3#反应釜中，制备含脲基的异氰酸酯预聚物，其-NCO含量为13％；
(4)将步骤(3)制备的预聚物和经(2)脱水后的PTMEG分别用计量泵加入到120～140℃左右的双螺杆反应器中，在一定的螺杆转速下，异氰酸酯指数为0.99，连续反应和移动，经双螺杆反应器的不同分段温度反应一定时间后由机头挤出胶条，并引入水槽冷却。造粒冷却后的胶条经造粒机切粒，胶粒在100～110℃的烘箱中干燥，冷却后，即可包装。实施例5所制备的热塑性脂肪族聚脲弹性体的主要性能指标如表5所示：
表5实施例5热塑性脂肪族聚脲弹性体主要性能
编号 项目 指标 结果
1 加工温度，℃ 180-190 180-190
2 硬度(邵D) ≥30 D/15:35
3 拉伸强度，MPa ≥15 22.3
4 撕裂强度，KN/m ≥40 47
5 断裂伸长率，％ ≥400 456
6 密度，g/cm<sup>3</sup> 1.0±0.02 0.98
8 耐磨性，cm<sup>3</sup> ≤0.05 0.01

Claims (9)

1.一种热塑性脂肪族聚脲弹性体，其特征在于，由以下重量份的各原材料制成：
所述的多元醇为分子量在500-2000之间的聚四氢呋喃二醇PTMEG、聚己内酯二醇PCL、聚碳酸酯二醇PCDL中的一种或任意几种的混合物；
所述各原材料按照异氰酸酯指数在0.94-0.99之间进行配合使用。
2.根据权利要求1所述的一种热塑性脂肪族聚脲弹性体，其特征在于，所述的脂肪族二异氰酸酯为异佛尔酮二异氰酸酯IPDI、二环己基甲烷二异氰酸酯HMDI、六亚甲基二异氰酸酯HDI中的一种或几种的混合物。
3.根据权利要求1所述的一种热塑性脂肪族聚脲弹性体，其特征在于，所述的端氨基聚醚为D400、D2000、T5000中的一种或两种的混合物。
4.根据权利要求1所述的一种热塑性脂肪族聚脲弹性体，其特征在于，所述的扩链剂为小分子量二元胺。
5.根据权利要求4所述的一种热塑性脂肪族聚脲弹性体，其特征在于，所述的二元胺为脂肪族二元胺，包括氢化间苯二甲胺1,3BAC、异佛尔酮二胺IPDA、JEFFLINKTM754、CLEARLINK1000中的一种或几种的混合物。
6.根据权利要求1所述的一种热塑性脂肪族聚脲弹性体，其特征在于，所述的紫外线吸收剂为苯并三唑类、取代丙烯腈类、三嗪类和受阻胺类化合物中的一种或几种的复配物。
7.一种如权利要求1-6任意一项所述热塑性脂肪族聚脲弹性体的制备方法，其特征在于，包括以下步骤：
(1)先将端氨基聚醚、扩链剂、紫外线吸收剂、色浆加入到1#反应釜中混合均匀，抽真空脱水备用；
(2)将多元醇加入到2#反应釜中，抽真空脱水备用；
(3)将脂肪族二异氰酸酯加入到3#反应釜中，将1#反应釜中制备的混合物用计量泵加入到3#反应釜中，制备含脲基的异氰酸酯预聚物；
(4)将步骤(3)制备的预聚物和经(2)脱水后的多元醇分别用计量泵加入到双螺杆反应器中，经反应后由机头挤出胶条，经冷却、切粒、干燥、冷却后，即可包装。
8.根据权利要求7所述热塑性脂肪族聚脲弹性体的制备方法，其特征在于，所述步骤(1)(2)均在100～120℃温度下抽真空脱水2～3h备用；所述步骤(4)中双螺杆反应器的温度为120～140℃，干燥温度为100～110℃。
9.根据权利要求7或8所述热塑性脂肪族聚脲弹性体的制备方法，其特征在于，所述含脲基的异氰酸酯预聚物的-NCO含量为13～16％。
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