CN102061058B - 无卤阻燃玻纤增强聚甲醛复合材料及其制备方法 - Google Patents

无卤阻燃玻纤增强聚甲醛复合材料及其制备方法 Download PDF

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CN102061058B
CN102061058B CN2010105959079A CN201010595907A CN102061058B CN 102061058 B CN102061058 B CN 102061058B CN 2010105959079 A CN2010105959079 A CN 2010105959079A CN 201010595907 A CN201010595907 A CN 201010595907A CN 102061058 B CN102061058 B CN 102061058B
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glass fiber
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halogen
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polyoxymethylene
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CN102061058A (zh
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陈英红
王琪
刘渊
于奋飞
华正坤
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Sichuan University
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Abstract

本发明公开的无卤阻燃玻纤增强聚甲醛复合材料及其制备方法，其特点是按比例先将三聚氰胺、聚磷酸铵、聚合物成炭剂、聚硅氧烷、酰亚胺类化合物和聚甲醛热稳定剂于高速混合器中混合2～4分钟，然后再向上述混合物中加入聚甲醛和增韧剂继续混合3～6分钟，再将混合物加入双螺杆挤出机中于温度165～200℃熔融挤出，同时于挤出机的侧喂料口加入玻璃纤维，挤出物造粒后干燥即可。本发明提供的制备方法工艺简单，原料易得，成本较低，易于实施，所制备的无卤阻燃玻纤增强聚甲醛复合材料阻燃和力学性能优异，环保无卤，应用前景广阔。

Description

无卤阻燃玻纤增强聚甲醛复合材料及其制备方法
技术领域
本发明属于阻燃聚甲醛复合材料及其制备技术领域，具体涉及一种无卤阻燃玻纤增强聚甲醛复合材料及其制备方法。
背景技术
工程塑料聚甲醛(POM)的结构特点是分子链柔顺性好，链结构规整度高，易结晶且结晶度高，因而赋予了其硬度大、模量高，尺寸稳定性好，良好的热电性能，耐疲劳性突出，耐磨和自润滑性能好，着色性强，使用温度范围广等诸多优点。然而，因聚甲醛分子内的含氧量高达53％，极限氧指数低(仅15％)，极易燃烧，因而极大地限制了其应用领域。此外，聚甲醛对酸碱稳定性差，少量酸碱的存在即可引起聚甲醛的剧烈降解，使得传统的卤-锑协效阻燃体系对聚甲醛大多无效，而大量加入其他阻燃剂又会大幅降低聚甲醛的力学性能。因此，改善聚甲醛的阻燃性能十分困难，一直是世界性难题，同时也是具有重要意义的研究课题。
随着研究的进行，对非玻纤增强聚甲醛的阻燃，国内外已有较多文献报道。如美国专利6699923 B2公开了利用红磷/酚醛树脂或聚碳酸酯/脂肪酸盐阻燃聚甲醛，并在一定程度上改善了聚甲醛的阻燃性能。美国Celanese公司将NH4H2PO4或(NH4)2HPO4加入聚甲醛中制备了自熄聚甲醛。日本三重大学Harashina H等采用红磷、酚醛树脂、三聚氰胺的三组分体系阻燃POM，所得阻燃POM材料的极限氧指数达到37.5，垂直燃烧性能达到UL94 V-1级别[Harashina H，Tajima Y，Itoh T，Polymer Degradation andStability，2006，91(9)，1996-2002]。国内刘鹏波等采用Mg(OH)2阻燃POM，发现60％的Mg(OH)2可使POM的极限氧指数提高至40[刘鹏波，徐闻，李英杰，高分子材料科学与工程，2004，20(6)，120-123]。谢代义等采用聚氨酯包覆三聚氰胺氰尿酸盐阻燃聚甲醛，所得阻燃POM样品极限氧指数可达26，力学性能较好[谢代义，刘渊，王琪，塑料工业，2006，34(4)，17-19]。
然而，对玻纤增强聚甲醛体系的阻燃，一般而言，要比聚甲醛的非玻纤增强体系更难阻燃，其原因在于玻纤在聚甲醛体系中产生了类似于“烛芯”效应，因而会加速聚甲醛体系的熔融有焰滴落和燃烧。对玻纤增强聚甲醛体系的阻燃，文献报道很少，目前仅见美国专利3884867报道了采用5～15％的包覆型红磷微粉和1～40％偶联剂预处理的玻纤与聚甲醛复合制备自熄型聚甲醛，但由于添加的红磷颜色深，使其阻燃的聚甲醛体系的适用范围大为受限，加之包覆型红磷微粉制备工艺复杂，一定程度上解决了阻燃玻纤增强聚甲醛体系中的玻纤“烛芯”效应问题，其阻燃性能根据美国标准ASTM D 635-63仅达水平燃烧HB级(自熄)水平，故其阻燃性能提高有限。此外，本发明人在前期研究中还发现，如果在填充阻燃剂的聚甲醛体系中单纯添加玻纤所得材料的力学性能(拉伸强度和缺口冲击强度一般分别为36.0MPa和2.4kJ/m2)甚至比不加玻纤的材料(拉伸强度和缺口冲击强度一般分别为52.0MPa和4.5kJ/m2)还要差。
发明内容
本发明的首要目的是针对现有技术的不足，提供一种无卤阻燃玻纤增强聚甲醛复合材料。
本发明的另一目的是提供一种制备上述无卤阻燃玻纤增强聚甲醛复合材料的方法。
本发明首要目的提供的无卤阻燃玻纤增强聚甲醛复合材料，其特征在于该复合材料按重量百分比计是由以下组分经熔融共混而成：
聚甲醛            20～70％
玻璃纤维          5～40％
三聚氰胺          1～25％
聚磷酸铵          5～40％
聚合物成炭剂      0.05～10％
聚硅氧烷          0.1～5％
增韧剂            0～30％
酰亚胺类化合物    0.1～5％
聚甲醛热稳定剂    0.1～2％。
上述复合材料中聚甲醛可选用均聚型聚甲醛和共聚型聚甲醛中的至少一种；玻璃纤维可选用短切玻璃纤维或连续长玻璃纤维中任一种；聚磷酸铵选用聚合度10～3000的结晶I型或结晶II型中的任一种；聚合物成炭剂可选用三聚氰胺甲醛树脂、脲醛树脂和热塑性酚醛树脂中的至少一种；聚硅氧烷可选用数均分子量10000～5000000的硅油、硅橡胶和硅酮粉中的至少一种；增韧剂可选用聚烯烃弹性体(POE)、聚氧化乙烯(PEO)、聚醚型热塑性聚氨酯(ET-TPU)和聚酯型热塑性聚氨酯(ES-TPU)中的至少一种；酰亚胺类化合物可选用邻苯二甲酰亚胺、丁二酰亚胺、双马来酰亚胺和N-苯基马来酰亚胺中的至少一种；聚甲醛热稳定剂可选用2，6-二叔丁基对甲酚(抗氧剂264)、四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(抗氧剂1010)、二缩三乙二醇双[β-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯](抗氧剂245)、己二醇双[3-(3，5-二叔丁基-4-羟基苯基)丙酸酯](抗氧剂259)和双-[β-3，5-二叔丁基-4-羟基苯基]丙酸三甘醇酯(抗氧剂719)中的至少一种。
以上各组分的配比优选为：聚甲醛30～65％；玻璃纤维5～30％；三聚氰胺1～20％；聚磷酸铵10～30％；聚合物成炭剂0.2～5％；聚硅氧烷0.1～3％；增韧剂0～25％；酰亚胺类化合物0.1～3％；聚甲醛热稳定剂0.1～1.5％。
本发明另一目的提供的制备上述无卤阻燃玻纤增强聚甲醛复合材料的方法，其特征在于该方法的工艺步骤和条件如下：
(1)先将1～25％的三聚氰胺、5～40％的聚磷酸铵、0.05～10％的聚合物成炭剂、0.1～5％的聚硅氧烷、0.1～5％的酰亚胺类化合物和0.1～2％的聚甲醛热稳定剂放入高速混合器中混合2～4分钟，然后再加入20～70％的聚甲醛和0～30％的增韧剂继续混合3～6分钟，得到各组分均匀混合的混合物；
(2)将所得混合物加入双螺杆挤出机中于温度165～200℃熔融共混挤出，同时于双螺杆挤出机主加料口前方的侧喂料口加入5～40％的玻璃纤维，挤出机转速为30～500转/分，挤出物过水冷却后切粒，并于60～90℃干燥4～8小时即可得到阻燃复合材料粒料，
其中所用物料的百分比均为重量百分比。
上述制备方法中所用的聚甲醛为均聚型聚甲醛和共聚型聚甲醛中的至少一种；玻璃纤维为短切玻璃纤维或连续长玻璃纤维中任一种；聚磷酸铵为聚合度10～3000的结晶I型或结晶II型中的任一种；聚合物成炭剂为三聚氰胺甲醛树脂、脲醛树脂和热塑性酚醛树脂中的至少一种；聚硅氧烷为数均分子量10000～5000000的硅油、硅橡胶和硅酮粉中的至少一种；增韧剂为聚烯烃弹性体(POE)、聚氧化乙烯(PEO)、聚醚型热塑性聚氨酯(ET-TPU)和聚酯型热塑性聚氨酯(ES-TPU)中的至少一种；酰亚胺类化合物为邻苯二甲酰亚胺、丁二酰亚胺、双马来酰亚胺和N-苯基马来酰亚胺中的至少一种；聚甲醛热稳定剂为2，6-二叔丁基对甲酚(抗氧剂264)、四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(抗氧剂1010)、二缩三乙二醇双[β-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯](抗氧剂245)、己二醇双[3-(3，5-二叔丁基-4-羟基苯基)丙酸酯](抗氧剂259)和双-[β-3，5-二叔丁基-4-羟基苯基]丙酸三甘醇酯(抗氧剂719)中的至少一种。
以上各物料的配比优选为：聚甲醛30～65％；玻璃纤维5～30％；三聚氰胺1～20％；聚磷酸铵10～30％；聚合物成炭剂0.2～5％；聚硅氧烷0.1～3％；增韧剂0～25％；酰亚胺类化合物0.1～3％；聚甲醛热稳定剂0.1～1.5％。
本发明具有以下优点：
1、由于本发明在玻纤增强聚甲醛体系中不仅加入的是氮磷膨胀型阻燃体系(聚磷酸铵/三聚氰胺复合物)，而且还加入了聚合物成炭剂和酰亚胺类化合物，因而一方面避免了现有技术添加的红磷阻燃剂颜色深，制备工艺复杂等带来的问题，另一方面可利用聚合物成炭剂的协效阻燃和酰亚胺类化合物的交联成炭作用，使阻燃玻纤增强聚甲醛材料在一开始燃烧时就瞬即形成包覆于玻纤表面的膨胀炭层，既解决了体系中玻纤产生的“烛芯”效应问题，其中的玻纤又同时起到了支撑膨胀炭层的增强体作用，从而达到大幅改善凝聚相膨胀炭层质量，提高阻燃玻纤增强聚甲醛材料阻燃性能的目的。
2、由于本发明中采用的三聚氰胺和聚甲醛热稳定剂能产生协同作用，因而不仅可显著改善阻燃玻纤增强聚甲醛体系的热稳定性，保证体系的稳定加工，且其中的三聚氰胺既可发挥膨胀型阻燃剂的气源作用，又能起到酸碱稳定剂的作用，以避免聚甲醛受酸碱影响引起的剧烈降解。
3、由于本发明中加入的酰亚胺类化合物和增韧剂能分别通过其与界面的聚甲醛、玻纤表面发生键合反应和界面增容作用，因而大大提高了阻燃玻纤增强聚甲醛体系的界面粘接作用力，可在不牺牲材料阻燃性能的同时又能显著改善材料的冲击性能，从而提高整个体系的综合性能。
4、由于本发明中加入的聚硅氧烷的使用不仅显著改善了阻燃玻纤增强聚甲醛体系的加工流动性能，使得整个体系的加工得以顺利进行，而且还能在一定程度上通过燃烧过程中分解产生的不燃性二氧化硅参与凝聚相炭层的形成而起到协效阻燃作用。
5、本发明所采用的原料易得，环保无卤，且所提出的阻燃玻纤增强聚甲醛材料的制备工艺简单，易于实施，成本较低，所制备的阻燃材料综合性能优良，应用前景广阔。
具体实施方式
下面通过实施例对本发明进行具体描述。有必要在此指出的是以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，该领域的技术熟练人员可以根据上述发明内容对本发明作出一些非本质的改进和调整。
值得说明的是，以下实施例所制备的复合材料测试的垂直燃烧性能是按UL94测试标准进行的，试样尺寸为127mm×12.7mm×1.6mm；极限氧指数(LOI)是按GB/T8924-88标准进行的，试样尺寸120mm×6.5mm×3.2mm；拉伸强度是按GB/T 1040-92进行的，试样尺寸采用I型样，拉伸速度为50mm/min；简支梁缺口冲击强度是按GB/T1043-93进行的，试样尺寸为80mm×10mm×4mm，缺口深度为2.0mm。
实施例1
先将三聚氰胺60g、聚合度为1000的II型聚磷酸铵240g、三聚氰胺甲醛树脂5g、硅油(数均分子量10000)10g、邻苯二甲酰亚胺10g和抗氧剂264 5g于高速混合器中混合2分钟，然后再加入均聚聚甲醛470g继续混合5分钟。随后将所得混合物加入至双螺杆挤出机中于温度180℃熔融挤出，同时于挤出机主加料口前方的侧喂料口均匀加入短切玻璃纤维200g，挤出机转速30转/分，挤出物过水冷却后切粒，并于60℃干燥4小时即得阻燃复合材料粒料。取该粒料经注塑机注塑成标准测试样条，注塑温度为190℃。经检测，样条的垂直燃烧性能达到1.6mm UL94 V-0级，极限氧指数(LOI)为63，拉伸强度为70.0MPa，简支梁缺口冲击强度为6.3kJ/m2。
实施例2
先将三聚氰胺10g、聚合度为10的I型聚磷酸铵190g、热塑性酚醛树脂8g、三聚氰胺甲醛树脂2g、硅酮粉(数均分子量1500000)1g、丁二酰亚胺20g、邻苯二甲酰亚胺10g、抗氧剂245 6g和抗氧剂1010 4g于高速混合器中混合3分钟，然后再加入共聚聚甲醛649g、POE 45g和ET-TPU 5g继续混合4分钟。随后将所得混合物加入至双螺杆挤出机中于温度190℃熔融挤出，同时于挤出机主加料口前方的侧喂料口均匀加入连续长玻璃纤维50g，挤出机转速100转/分，挤出物过水冷却后切粒，并于80℃干燥8小时即得阻燃复合材料粒料。取该粒料经注塑机注塑成标准测试样条，注塑温度为195℃。经检测，样条的垂直燃烧性能达到1.6mm UL94 V-1级，极限氧指数(LOI)为55，拉伸强度为60.0MPa，简支梁缺口冲击强度为6.7kJ/m2。
实施例3
先将三聚氰胺50g、聚合物度为1500的II型聚磷酸铵300g、脲醛树脂50g、硅橡胶(数均分子量1000000)20g、双马来酰亚胺1g、N-苯基马来酰亚胺1g、抗氧剂264 4g和抗氧剂719 4g于高速混合器中混合4分钟，然后再加入均聚聚甲醛200g、共聚聚甲醛150g、PEO 60g和POE 40g继续混合6分钟。随后将所得混合物加入至双螺杆挤出机中于温度195℃熔融挤出，同时于挤出机主加料口前方的侧喂料口均匀加入短切玻璃纤维120g，挤出机转速500转/分，挤出物过水冷却后切粒，并于90℃干燥6小时即得阻燃复合材料粒料。取该粒料经注塑机注塑成标准测试样条，注塑温度为200℃。经检测，样条的垂直燃烧性能达到1.6mm UL94 V-0级，极限氧指数(LOI)为66，拉伸强度为63.0MPa，简支梁缺口冲击强度为7.2kJ/m2。
实施例4
先将三聚氰胺200g、聚合物度为3000的II型聚磷酸铵150g、热塑性酚醛树脂15g、三聚氰胺甲醛树脂5g、硅油(数均分子量50000)3g、硅酮粉(数均分子量5000000)4g、N-苯基马来酰亚胺8g、抗氧剂259 6g和抗氧剂2459g于高速混合器中混合3分钟，然后再加入均聚聚甲醛300g继续混合3分钟。随后将所得混合物加入至双螺杆挤出机中于温度200℃熔融挤出，同时于挤出机主加料口前方的侧喂料口均匀加入连续长玻璃纤维300g，挤出机转速300转/分，挤出物过水冷却后切粒，并于70℃干燥5小时即得阻燃复合材料粒料。取该粒料经注塑机注塑成标准测试样条，注塑温度为200℃。经检测，样条的垂直燃烧性能达到1.6mm UL94 V-0级，极限氧指数(LOI)为68，拉伸强度为80.0MPa，简支梁缺口冲击强度为5.9kJ/m2。
实施例5
先将三聚氰胺95g、聚合物度为90的I型聚磷酸铵100g、三聚氰胺甲醛树脂5g、硅橡胶(数均分子量800000)10g、硅油(数均分子量100000)5g、丁二酰亚胺15g和抗氧剂719 1g于高速混合器中混合4分钟，然后再加入均聚聚甲醛250g和共聚聚甲醛119g继续混合6分钟。随后将所得混合物加入至双螺杆挤出机中于温度165℃熔融挤出，同时于挤出机主加料口前方的侧喂料口均匀加入短切玻璃纤维400g，挤出机转速200转/分，挤出物过水冷却后切粒，并于80℃干燥4小时即得阻燃复合材料粒料。取该粒料经注塑机注塑成标准测试样条，注塑温度为175℃。经检测，样条的垂直燃烧性能达到1.6mm UL94 V-1级，极限氧指数(LOI)为63，拉伸强度为75.0MPa，简支梁缺口冲击强度为5.2kJ/m2。
实施例6
先将三聚氰胺60g、聚合物度为1500的II型聚磷酸铵160g、热塑性酚醛树脂40g、脲醛树脂10g、硅酮粉(数均分子量4000000)40g、邻苯二甲酰亚胺50g和抗氧剂24510g于高速混合器中混合4分钟，然后再加入共聚聚甲醛320g、ES-TPU 100g、PEO 100g和POE 50g继续混合5分钟。随后将所得混合物加入至双螺杆挤出机中于温度195℃熔融挤出，同时于挤出机主加料口前方的侧喂料口均匀加入连续长玻璃纤维60g，挤出机转速150转/分，挤出物过水冷却后切粒，并于70℃干燥5小时即得阻燃复合材料粒料，经注塑机注塑成标准测试样条，注塑温度为195℃。经检测，样条的垂直燃烧性能达到1.6mm UL94V-1级，极限氧指数(LOI)为55，拉伸强度为57.0MPa，简支梁缺口冲击强度为7.3kJ/m2。
实施例7
先将三聚氰胺128g、聚合物度为2000的II型聚磷酸铵50g、热塑性酚醛树脂0.5g、硅酮粉(数均分子量4000000)30g、硅油(数均分子量100000)20g、N-苯基马来酰亚胺1g和抗氧剂264 20g于高速混合器中混合3分钟，然后再加入均聚聚甲醛400g和共聚聚甲醛300.5g继续混合5分钟。随后将所得混合物加入至双螺杆挤出机中于温度190℃熔融挤出，同时于挤出机主加料口前方的侧喂料口均匀加入连续长玻璃纤维50g，挤出机转速100转/分，挤出物过水冷却后切粒，并于80℃干燥5小时即得阻燃复合材料粒料。取该粒料经注塑机注塑成标准测试样条，注塑温度为200℃。经检测，样条的垂直燃烧性能达到1.6mm UL94 V-1级，极限氧指数(LOI)为50，拉伸强度为62.0MPa，简支梁缺口冲击强度为6.0kJ/m2。
实施例8
先将三聚氰胺20g、聚合物度为1500的II型聚磷酸铵400g、热塑性酚醛树脂60g、三聚氰胺甲醛树脂40g、硅油(数均分子量60000)30g、N-苯基马来酰亚胺7g和抗氧剂245 3g于高速混合器中混合4分钟，然后再加入共聚聚甲醛350g和PEO 20g继续混合6分钟。随后将所得混合物加入至双螺杆挤出机中于温度200℃挤出，同时于挤出机主加料口前方的侧喂料口均匀加入连续长玻璃纤维70g，挤出机转速200转/分，挤出物过水冷却后切粒，并于90℃干燥4小时即得阻燃复合材料粒料。取该粒料经注塑机注塑成标准测试样条，注塑温度为200℃。经检测，样条的垂直燃烧性能达到1.6mmUL94 V-0级，极限氧指数(LOI)为70，拉伸强度为60.0MPa，简支梁缺口冲击强度为5.6kJ/m2。
实施例9
先将三聚氰胺250g、聚合物度为1500的II型聚磷酸铵130g、三聚氰胺甲醛树脂2g、硅橡胶(数均分子量500000)2g、硅油(数均分子量80000)3g、N-苯基马来酰亚胺5g、丁二酰亚胺4g和抗氧剂719 4g于高速混合器中混合3分钟，然后再加入均聚聚甲醛200g、POE 100g、PEO 100g和ES-TPU 100g继续混合6分钟。随后将所得混合物加入至双螺杆挤出机中于温度190℃熔融挤出，同时于挤出机主加料口前方的侧喂料口均匀加入短切玻璃纤维100g，挤出机转速200转/分，挤出物过水冷却后切粒，并于80℃干燥5小时即得到阻燃复合材料粒料。取该粒料经注塑机注塑成标准测试样条，注塑温度为195℃。经检测，样条的垂直燃烧性能达到1.6mm UL94 V-0级，极限氧指数(LOI)为62，拉伸强度为58.0MPa，简支梁缺口冲击强度为7.5kJ/m2。

Claims (6)

1.一种无卤阻燃玻纤增强聚甲醛复合材料，其特征在于该复合材料按重量百分比计是由以下组分经熔融共混而成：
Figure FDA0000134036140000011
其中聚合物成炭剂为三聚氰胺甲醛树脂、脲醛树脂和热塑性酚醛树脂中的至少一种；酰亚胺类化合物为邻苯二甲酰亚胺、丁二酰亚胺、双马来酰亚胺和N-苯基马来酰亚胺中的至少一种。
2.根据权利要求1所述的无卤阻燃玻纤增强聚甲醛复合材料，其特征在于该复合材料中的聚硅氧烷为数均分子量10000～5000000的硅油、硅橡胶和硅酮粉中的至少一种。
3.根据权利要求1或2所述的无卤阻燃玻纤增强聚甲醛复合材料，其特征在于该复合材料中的增韧剂为聚烯烃弹性体、聚氧化乙烯和聚醚型热塑性聚氨酯和聚酯型热塑性聚氨酯中的至少一种。
4.一种制备权利要求1所述的无卤阻燃玻纤增强聚甲醛复合材料的方法，其特征在于该方法的工艺步骤和条件如下：
(1)先将1～25％的三聚氰胺、5～40％的聚磷酸铵、0.05～10％的聚合物成炭剂、0.1～5％的聚硅氧烷、0.1～5％的酰亚胺类化合物和0.1～2％的聚甲醛热稳定剂放入高速混合器中混合2～4分钟，然后再加入20～70％的聚甲醛和0～30％的增韧剂继续混合3～6分钟，得到各组分均匀混合的混合物；
(2)将所得混合物加入双螺杆挤出机中于温度165～200℃熔融共混挤出，同时于双螺杆挤出机主加料口前方的侧喂料口加入5～40％的玻璃纤维，挤出机转速为30～500转/分，挤出物过水冷却后切粒，并于60～90℃干燥4～8小时即可得到阻燃复合材料粒料，
其中所用物料的百分比均为重量百分比；所用的聚合物成炭剂为三聚氰胺甲醛树脂、脲醛树脂和热塑性酚醛树脂中的至少一种；所用的酰亚胺类化合物为邻苯二甲酰亚胺、丁二酰亚胺、双马来酰亚胺和N-苯基马来酰亚胺中的至少一种。
5.根据权利要求4所述的制备无卤阻燃玻纤增强聚甲醛复合材料的方法，其特征在于该方法中所用的聚硅氧烷为数均分子量10000～5000000的硅油、硅橡胶和硅酮粉中的至少一种。
6.根据权利要求4或5所述的制备无卤阻燃玻纤增强聚甲醛复合材料的方法，其特征在于该方法中所用的增韧剂为聚烯烃弹性体、聚氧化乙烯、聚醚型热塑性聚氨酯和聚酯型热塑性聚氨酯中的至少一种。
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