CN110283298B - 湿地止滑、耐磨型热塑性聚氨酯及其应用 - Google Patents
湿地止滑、耐磨型热塑性聚氨酯及其应用 Download PDFInfo
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- CN110283298B CN110283298B CN201910543321.9A CN201910543321A CN110283298B CN 110283298 B CN110283298 B CN 110283298B CN 201910543321 A CN201910543321 A CN 201910543321A CN 110283298 B CN110283298 B CN 110283298B
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- thermoplastic polyurethane
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Classifications
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Abstract
本发明公开了一种湿地止滑、耐磨型热塑性聚氨酯及其应用，湿地止滑、耐磨型热塑性聚氨酯，是采用包括如下质量份数的组份在催化剂的存在下制备的：(A)链末端为羟基封端的多元醇50～70份，(B)多异氰酸酯10～20份，(C)含有2至12个碳原子的线性二元醇1.5～3.5份，(D)链末端含有一个与异氰酸酯有反应活性的有机硅聚合物0.05～1份，(E)苯甲酸二醇酯15～30份，催化剂的为上述组份总重量的0.001～0.1％。本发明可用于制备一种或多种可能接触湿润表面的制品，本发明大大提高了软质TPU材料的湿止滑性能和耐磨性能，解决了软质TPU耐磨性能和湿止滑性能不能兼顾的问题。
Description
技术领域
本发明涉及一种热塑性聚氨酯及其应用。
背景技术
由软链段和硬链段构成的热塑性聚氨酯(TPU)同时具备橡胶和塑料的特性，其拉伸强度高、伸长率大，长期压缩永久变形率低等都是TPU的显著优点。然而，TPU虽具有很多优点，但针对特殊的应用领域如鞋底材料、户外用品、卫生用品等，其对材料不仅要求有柔软的触感、优良的耐磨性能，同时在鞋底接触湿滑地面时仍保持优异的止滑性能，而常规的TPU往往满足不了现有止滑与耐磨需求。
专利CN201810483005.2在TPU中混入碳纳米管、失水山梨醇脂肪酸酯以及2,2,4-三甲基-1,3-戊二醇双异丁酸酯来提高TPU的耐磨性。专利CN201310678454.X则是在TPU基材中加入十二烷基三甲基溴化铵、硬脂酸、羟基硅油等提高材料的低温耐磨性。专利CN200980106378.7报道了一种软质的TPU，在TPU分子结构中引入了支化的二聚脂肪酸作为憎水性的多元醇提高软质TPU的湿止滑性能。针对TPU鞋底、扶手等材料方面，增加材料止滑性能，常规做法是将材料硬度降低，使得材料在受力情况下与接触面的受力变形更加明显，但缺点是材料的耐磨性能会很差；而通过添加耐磨剂增加TPU的耐磨性能又会对材料本身硬度或者止滑性产生影响。
发明内容
本发明的目的是提供一种湿地止滑、耐磨型热塑性聚氨酯及其应用，以克服现有技术存在的缺陷。
所述的湿地止滑、耐磨型热塑性聚氨酯，是采用包括如下质量份数的组份在催化剂的存在下制备的：
(A)链末端为羟基封端的多元醇 50～70份
(B)多异氰酸酯 10～20份
(C)含有2至12个碳原子的线性二元醇 1.5～3.5份
(D)链末端含有一个与异氰酸酯有反应活性的有机硅聚合物 0.05～1份
(E)苯甲酸二醇酯 15～30份
催化剂的为上述组份总重量的0.001～0.1％；
优选的，还包括助剂，助剂的用量为上述组份总重量的0.05～5％，优选0.1～3％；
所述的链末端为羟基封端的多元醇(A)选自聚酯多元醇或聚醚多元醇的一种或几种混合物；
所述的聚酯多元醇由不超过6个碳原子的二元醇与不超过10个碳原子的二羧酸缩聚而成的分子量为1000～3000g/mol的聚酯多元醇，或由己内酯开环聚合而成的分子量为1000～3500g/mol的聚酯多元醇；
所述的不超过6个碳原子的二元醇包括：乙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、2-甲基-1,3丙二醇等，优选乙二醇、1,3-丙二醇、1,4-丁二醇，特别优选乙二醇；
所述的不超过10个碳原子的二羧酸包括脂肪族二酸或芳香族二酸，例如：乙二酸、丙二酸、丁二酸、戊二酸、己二酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸，优选戊二酸、己二酸、苯二甲酸；
所述的聚醚多元醇由不超过6个碳原子的环氧烷烃开环聚合而成的分子量为1000～3000g/mol的聚醚多元醇；
所述的不超过6个碳原子的环氧烷烃包括：环氧乙烷、环氧丙烷、四氢呋喃等；
所述的多异氰酸酯(B)选自脂肪族二异氰酸酯，芳香族二异氰酸酯，脂环族二异氰酸酯的一种或几种混合物，例如：4,4’-二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、4,4’-二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯、氢化苯二亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、三甲基己二异氰酸酯、氢化苯基甲烷二异氰酸酯、环己烷-1,4-二异氰酸酯等，优选4,4’-二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、4,4’-二环己基甲烷二异氰酸酯，特别优选4,4’-二苯基甲烷二异氰酸酯；
所述的含有2至12个碳原子的线性二元醇(C)包括：乙二醇，1,3-丙二醇，1,4-丁二醇，1,4-环己二醇，1,6-己二醇等，优选为1,4-丁二醇，乙二醇；
所述的链末端含有一个与异氰酸酯有反应活性的有机硅聚合物(D)结构式如下：
其中，
R分别为独立的具有1～4个碳原子的碳骨架或1～4个碳原子的含氟碳骨架，优选1～2个亚烷基或三氟甲基、三氟乙基、三氟丙基；
X是与异氰酸酯有反应活性的基团，例如：羟基、氨基、环氧基、羟基亚烷基、双羟基亚烷基、氨基亚烷基、环氧基亚烷基，优选羟基、羟基亚烷基；
n是10～55的整数，优选30～50的整数，进一步优选30～40的整数；
所述的链末端含有一个与异氰酸酯有反应活性的有机硅聚合物(D)可可参考采用文献“Y.Tezuka,A.Fukushima，K.Imai；Makromol.Chem.,186,1985,685-694.”中提及的制备方法文献公开的技术制备；
所述的苯甲酸二醇酯(E)由主碳链为2至5个碳原子的二元醇或缩聚为聚合度不超过5的低聚合聚醚二元醇与苯甲酸酯化反应形成的苯甲酸二醇酯；
优选的，聚合度不超过5的低聚合聚醚二元醇由包括：乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇等进行缩聚形成的聚合度不超多5的低聚物二元醇；
优选的，聚合度不超过5的低聚合聚醚二元醇由包括：乙二醇、1,2-丙二醇、1,3-丙二醇等进行缩聚形成的聚合度不超过3的低聚合聚醚二元醇；
优选的，聚合度不超过5的低聚物二元醇包括：二乙二醇、三乙二醇、三缩四乙二醇、二丙二醇等；
所述的助剂为本领域通用的，包括抗氧剂、增塑剂、紫外线吸收剂、光稳定剂、润滑剂、热稳定剂、耐水解剂等，具体可参见《聚氨酯原料及助剂手册》(刘益军编著，化学工业出版社，第二版)；
所述的湿地止滑、耐磨型TPU组合物的制备方法，包括如下步骤：
(1)将上述的各个组份，采用连续聚合法或间歇聚合法，获得所述的湿地止滑、耐磨型热塑性聚氨酯；
所述的连续聚合法或间歇聚合法为本领域公知的，如“朱长春,谷金河.热塑性聚氨酯的生产、加工与应用[J].化学推进剂与高分子材料,2005,3(2).”文献报道的方法；
采用上述方法制备获得的湿地止滑、耐磨型热塑性聚氨酯，按照ASTM D2240测试，邵氏硬度为45A～65A；
所述的湿地止滑、耐磨型热塑性聚氨酯，可用于制备一种或多种制品，包括如鞋底、滚轮、扶手等可能接触湿润表面的制品，这些制品可通过发泡、注塑、流延、吹塑等方法制备。
本发明的有益效果：发明人惊讶的发现，本发明采用的链末端含有一个与异氰酸酯有反应活性的有机硅聚合物在多元醇、多异氰酸酯、小分子线性二元醇以及苯甲酸二醇酯类物质的存在下，大大提高了软质TPU材料的湿止滑性能和耐磨性能，解决了软质TPU耐磨性能和湿止滑性能不能兼顾的问题，此外，在本发明中没有添加任何其他的耐磨助剂或者止滑助剂。
具体实施方式
通过以下仅用于说明目的，不认为限制本发明范围或其中可以实践他的方法的实施例说明发明。
示例中涉及的链末端为羟基封端的多元醇(A)中，多异氰酸酯(B)、线性二元醇(C)、苯甲酸二醇酯(E)均可采用商业化产品；
链末端含有一个与异氰酸酯有反应活性的有机硅聚合物(D)可参考文献“Y.Tezuka,A.Fukushima，K.Imai；Makromol.Chem.,186,1985,685-694.”中提及制备方法，先得到含端烯烃的聚硅氧烷，后经过反马氏加成得到相应卤代物，水解得到产物；
单端羟基聚硅氧烷的结构式：
n为36～39；
单端羟基含氟聚硅氧烷的结构式：
n为15～18；
通过控制聚合反应条件制备的单端羟基二甲基硅氧烷和单端羟基含氟二甲基硅氧烷数均分子量均在3000g/mol左右；
实施例中的助剂是40wt％的抗氧剂1010、20wt％的耐水解剂碳化二亚胺、20wt％的紫外线吸收剂UV-5411和20wt％的润滑剂EBS的混合物；上述均为市售产品，均可采用商业化产品；助剂添加量为反应组份总质量的0.5％。
示例中催化剂为的二月桂酸二丁基锡，催化剂添加量为反应组份总质量的0.005％。
示例中的实验制备的TPU材料和/或组合物均采用一步连续聚合方法相同的制备方法和条件：
将添加助剂提前按比例配置好混在链末端为羟基封端的多元醇(A)中，多异氰酸酯(B)、线性二元醇(C)、链末端含有一个与异氰酸酯有反应活性的有机硅聚合物(D)、苯甲酸二醇酯(E)通过灌注系统分别加入双螺杆挤出机中混合，螺杆温度控制在160～190℃，物料在螺杆停留时间约为1～5min，螺杆转速为100～300rpm；经过水下切粒、干燥后得到湿地止滑、耐磨型热塑性聚氨酯颗粒。
实施例1
组份重量份配比：
制备方法：
将混合助剂混在分子量为3000g/mol的聚己二酸-1,4-丁二醇酯二醇(A)中，4,4’-二苯基甲烷二异氰酸酯(B)、乙二醇(C)、单端羟基聚硅氧烷(D)、二乙二醇二苯甲酸酯(E)通过灌注系统分别加入双螺杆挤出机中混合，螺杆温度控制在170℃，物料在螺杆停留时间约为3min，螺杆转速为200rpm；经过水下切粒、干燥后得到湿地止滑、耐磨型热塑性聚氨酯颗粒。
实施例2
组份重量份配比：
将混合添加助剂混在分子量为3000g/mol的聚己二酸-1,4-丁二醇酯二醇(A)中，4,4’-二苯基甲烷二异氰酸酯(B)、乙二醇(C)、单端羟基聚硅氧烷(D)、二丙二醇二苯甲酸酯(E)通过灌注系统分别加入双螺杆挤出机中混合，螺杆温度控制在160℃，物料在螺杆停留时间约为1min，螺杆转速为100rpm；经过水下切粒、干燥后得到湿地止滑、耐磨型热塑性聚氨酯颗粒。
实施例3
组份重量份配比：
将混合添加助剂混在分子量为2000g/mol的聚己二酸-1,4-丁二醇酯二醇(A)中，4,4’-二苯基甲烷二异氰酸酯(B)、乙二醇(C)、单端羟基聚硅氧烷(D)、二乙二醇二苯甲酸酯(E)通过灌注系统分别加入双螺杆挤出机中混合，螺杆温度控制在190℃，物料在螺杆停留时间约为5min，螺杆转速为300rpm；经过水下切粒、干燥后得到湿地止滑、耐磨型热塑性聚氨酯颗粒。
实施例4
组份重量份配比：
将混合添加助剂混在分子量为3000g/mol的聚四氢呋喃醚(A)中，4,4’-二苯基甲烷二异氰酸酯(B)、乙二醇(C)、单端羟基含氟聚硅氧烷(D)、二丙二醇二苯甲酸酯(E)通过灌注系统分别加入双螺杆挤出机中混合，螺杆温度控制在180℃，物料在螺杆停留时间约为4min，螺杆转速为200rpm；经过水下切粒、干燥后得到湿地止滑、耐磨型热塑性聚氨酯颗粒。
实施例5
组份重量份配比：
将混合添加助剂混在分子量为3000g/mol的聚己二酸-1,4-丁二醇酯二醇(A)中，4,4’-二苯基甲烷二异氰酸酯(B)、乙二醇(C)、单端羟基含氟聚硅氧烷(D)、二丙二醇二苯甲酸酯(E)通过灌注系统分别加入双螺杆挤出机中混合，螺杆温度控制在160℃，物料在螺杆停留时间约为2min，螺杆转速为200rpm；经过水下切粒、干燥后得到湿地止滑、耐磨型热塑性聚氨酯颗粒。
实施例6
组份重量份配比：
将混合添加助剂混在分子量为1000g/mol的聚戊二酸丙二醇酯二醇(A)中，4,4’-二苯基甲烷二异氰酸酯(B)、乙二醇(C)、单端羟基聚硅氧烷(D)、二丙二醇二苯甲酸酯(E)通过灌注系统分别加入双螺杆挤出机中混合，螺杆温度控制在180℃，物料在螺杆停留时间约为4min，螺杆转速为200rpm；经过水下切粒、干燥后得到湿地止滑、耐磨型热塑性聚氨酯颗粒。
实施例7
组份重量份配比：
将混合添加助剂配置好混在分子量为2000g/mol的聚己二酸乙二醇酯二醇(A)中，4,4’-二苯基甲烷二异氰酸酯(B)、1,4-丁二醇(C)、单端羟基聚硅氧烷(D)、15kg二乙二醇二苯甲酸酯(E)通过灌注系统分别加入双螺杆挤出机中混合，螺杆温度控制在190℃，物料在螺杆停留时间约为5min，螺杆转速为200rpm；经过水下切粒、干燥后得到湿地止滑、耐磨型热塑性聚氨酯颗粒。
对比例1
组份重量份配比：
将混合添加助剂混在分子量为3000g/mol的聚己二酸-1,4-丁二醇酯二醇(A)中，4,4’-二苯基甲烷二异氰酸酯(B)、乙二醇(C)、二乙二醇二苯甲酸酯(E)通过灌注系统分别加入双螺杆挤出机中混合，螺杆温度控制在170℃，物料在螺杆停留时间约为3min，螺杆转速为200rpm；经过水下切粒、干燥后得到湿地止滑、耐磨型热塑性聚氨酯颗粒。
对比例2
各组分原料的重量份配比与实施例4一致，其中各组分原料的种类中链末端含有一个与异氰酸酯有反应活性的有机硅聚合物的组份(D)为市售分子量约在3000g/mol的二羟基聚二甲基硅氧烷，其他原料种类与实施例3一致。
将的混合添加助剂混在分子量为3000g/mol的聚四氢呋喃醚(A)中，4,4’-二苯基甲烷二异氰酸酯(B)、乙二醇(C)、市售分子量约在3000g/mol的二羟基聚二甲基硅氧烷、二丙二醇二苯甲酸酯(E)通过灌注系统分别加入双螺杆挤出机中混合，螺杆温度控制在180℃，物料在螺杆停留时间约为4min，螺杆转速为200rpm；经过水下切粒、干燥后得到湿地止滑、耐磨型热塑性聚氨酯颗粒。
对比例3
各组分原料的重量份配比与实施例4一致，其中各组分原料的种类中链末端含有一个与异氰酸酯有反应活性的有机硅聚合物的组份(D)为市售分子量约在3000g/mol的聚二甲基硅氧烷，其他原料种类与实施例3一致。
将混合添加助剂混在分子量为3000g/mol的聚四氢呋喃醚(A)中，4,4’-二苯基甲烷二异氰酸酯(B)、乙二醇(C)、市售分子量约在3000g/mol的聚二甲基硅氧烷、二丙二醇二苯甲酸酯(E)通过灌注系统分别加入双螺杆挤出机中混合，螺杆温度控制在180℃，物料在螺杆停留时间约为4min，螺杆转速为200rpm；经过水下切粒、干燥后得到湿地止滑、耐磨型热塑性聚氨酯颗粒。
实施例和对比例的各项性能检测数据详见下表1：
表1：实施例1～6各项性能一览表
续表1：对比例1～3各项性能一览表
*1：硬度按照ASTM D2240中规定的A型邵氏硬度进行测试；
*2：湿止滑系数测试方法按照SATRA TM144进行测试；
*3：耐磨按照ASTM D5963中规定的方法A(非旋转方法)进行测试。
从上述试验可以看出：实施例1～6的湿止滑系数都可以达到0.7以上，保持了优异的湿止滑性的前提下，耐磨性能非常优异，均在65mm3以下。对比例1与实施例1相比较，对比例1中并未添加任何链末端含有一个与异氰酸酯有反应活性的有机硅聚合物，其湿止滑系数和耐磨性能都较差；对比例2、对比例3与实施例4相比较，对比例2、3都是将链末端含有一个与异氰酸酯有反应活性的有机硅聚合物替换为本领域常用的有机硅聚合物，湿止滑性能有略微的下降，耐磨性能与实施例数据差距较大。
Claims (11)
1.湿地止滑、耐磨型热塑性聚氨酯，其特征在于，是采用包括如下质量份数的组 份在催化剂的存在下制备的：
（A）链末端为羟基封端的多元醇 50~70 份
（B）多异氰酸酯 10~20 份
（C）含有 2 至 12 个碳原子的线性二元醇 1.5~3.5 份
（D）链末端含有一个与异氰酸酯有反应活性的有机硅聚合物 0.05~1 份
（E）苯甲酸二醇酯 15~30 份
催化剂的为上述组份总重量的 0.001~0.1%；
所述的链末端含有一个与异氰酸酯有反应活性的有机硅聚合物（D）结构式如下：
其中，n是36~39的整数；
或
其中，n是15~18的整数。
2.根据权利要求 1 所述的湿地止滑、耐磨型热塑性聚氨酯，其特征在于，还包括助剂，助剂的用量为上述组份总重量的 0.05~5%。
3.根据权利要求 1 所述的湿地止滑、耐磨型热塑性聚氨酯，其特征在于，所述的链末端为羟基封端的多元醇（A）选自聚酯多元醇或聚醚多元醇的一种或几种混合物；
所述的聚酯多元醇由不超过 6 个碳原子的二元醇与不超过 10 个碳原子的二羧酸缩聚而成的分子量为1000~3000 g/mol 的聚酯多元醇，或由己内酯开环聚合而成的分子量为1000~3500 g/mol 的聚酯多元醇；
所述的聚醚多元醇由不超过 6 个碳原子的环氧烷烃开环聚合而成的分子量为1000~3000 g/mol 的聚醚多元醇；
所述的多异氰酸酯（B）选自脂肪族二异氰酸酯，芳香族二异氰酸酯，脂环族二异氰酸酯的一种或几种混合物；
所述的含有 2 至 12 个碳原子的线性二元醇（C）包括：乙二醇，1,3-丙二醇， 1,4-丁二醇，1,4-环己二醇或 1,6-己二醇；
所述的苯甲酸二醇酯（E）由主碳链为 2 至 5 个碳原子的二元醇或缩聚为聚合度不超过 5 的低聚合聚醚二元醇与苯甲酸酯化反应形成的苯甲酸二醇酯。
4. 根据权利要求 3 所述的湿地止滑、耐磨型热塑性聚氨酯，其特征在于，所述的不超过 6 个碳原子的二元醇包括：乙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己 二醇或 2-甲基-1,3 丙二醇；
所述的不超过 10 个碳原子的二羧酸包括脂肪族二酸或芳香族二酸为乙二酸、丙二酸、丁二酸、戊二酸、己二酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸；
所述的不超过 6 个碳原子的环氧烷烃包括环氧乙烷、环氧丙烷或四氢呋喃。
5.根据权利要求3所述的湿地止滑、耐磨型热塑性聚氨酯，其特征在于，聚合度不超过5 的低聚物聚醚二元醇由包括乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇进行缩聚形成的聚合度不超过 5 的低聚物二元醇。
6.根据权利要求3所述的湿地止滑、耐磨型热塑性聚氨酯，其特征在于，所述的聚合度不超过 5 的低聚物聚醚二元醇由包括乙二醇、1,2-丙二醇、1,3-丙二醇进行缩聚形成的聚合度不超过 3 的低聚物二元醇。
7.根据权利要求3所述的湿地止滑、耐磨型热塑性聚氨酯，其特征在于，所述的聚合度不超过 5 的低聚物聚醚二元醇包括二乙二醇、三乙二醇、三缩四乙二醇、 二丙二醇。
8.根据权利要求3所述的湿地止滑、耐磨型热塑性聚氨酯，其特征在于，多异氰酸酯（B）选自4,4’-二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、4,4’-二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯、氢化苯二亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、三甲基己二异氰酸酯、氢化苯基甲烷二异氰酸酯或环己烷-1,4-二异氰酸酯。
9.根据权利要求1~8任一项所述的湿地止滑、耐磨型热塑性聚氨酯，其特征在于， 按照ASTM D2240 测试，邵氏硬度为 45A~65A。
10.根据权利要求1~9任一项所述的湿地止滑、耐磨型热塑性聚氨酯的应用，其特征 在于，用于制备鞋底、滚轮或扶手。
11.根据权利要求10所述的应用，其特征在于，通过发泡、注塑、流延、吹塑方法制备。
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