CN111333814A - 一种热塑性聚氨酯、其制备方法及应用 - Google Patents

一种热塑性聚氨酯、其制备方法及应用 Download PDF

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CN111333814A
CN111333814A CN202010278870.0A CN202010278870A CN111333814A CN 111333814 A CN111333814 A CN 111333814A CN 202010278870 A CN202010278870 A CN 202010278870A CN 111333814 A CN111333814 A CN 111333814A
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diisocyanate
carbonate
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CN111333814B (zh
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杨磊
黄岐善
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Wanhua Chemical Group Co Ltd
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Abstract

一种热塑性聚氨酯、其制备方法及应用，所述热塑性聚氨酯包括a)多元醇60～92wt％，b)扩链剂2～15wt％，c)多异氰酸酯5～35wt％，d)催化剂0.01～0.2wt％，本发明的粘合剂和表面涂层用热塑性聚氨酯具有快表干、低温活化、快速流平特性，而且，所得的聚氨酯还具有高溶解性、高强度、高回弹性和良好的耐热性，适用于鞋材、建筑、包装、印刷等领域。

Description

一种热塑性聚氨酯、其制备方法及应用
技术领域
本发明涉及聚氨酯材料领域，特别涉及一种热塑性聚氨酯、其制备方法及应用。
技术背景
热塑性聚氨酯(TPU)是一类加热可以塑化、溶剂可以溶解的聚氨酯弹性体，具有运输方便、性能优异、加工多样性等特点。按加工工艺分为熔融加工和溶液加工；按制品用途可分为各种机械零件、管材、护套、薄膜以及胶黏剂、涂料和纤维等。
当热塑性聚氨酯作为粘合剂时，具有溶解性优异、粘结强度高、耐热性好、可反复加工等特点，但目前热塑性聚氨酯在使用时仍然需要高温活化，而且，表干时间长，一定程度上影响了施工时间。中国专利CN101423598A公开了一种高光泽、高溶解性聚氨酯树脂及其制备方法，然而这些溶剂成本较高，且有毒性和易燃性，在酯类溶剂中溶解困难。中国专利CN101760166A公开了一种非黄变热塑性聚氨酯树脂热熔胶及其制备方法，但该热熔胶加工温度较高。中国专利CN102906146A公开了一种热塑性聚氨酯的热熔粘接，该热熔胶结晶速率可达 35min，熔点63℃。但是该热熔胶耐热性欠佳。
发明内容
本发明提供一种热塑性聚氨酯及其制备方法，所得的聚氨酯具备高溶解性、高耐热性，还具有低活化温度、快速表干、快速流平等特性。
本发明还提供上述热塑性聚氨酯的应用，尤其是用于粘合剂和各种表面涂层。
为达此目的，本发明采用以下技术方案：
一种热塑性聚氨酯，由包括以下组分的反应聚合而成：
Figure BDA0002445793400000021
以上所有组分质量的和为基准。
进一步的，所述组分a)多元醇的数均分子量为800～6000g/mol，优选1000～4000g/mol；
进一步的，所述组分a)多元醇可以是聚酯多元醇、聚醚多元醇、聚己内酯多元醇、聚碳酸酯多元醇或其组合物。
所述聚酯多元醇是由二元酸与二元醇通过行业公知的聚酯多元醇合成工艺制得；其中二元酸可以是丁二酸、己二酸、癸二酸中一种或多种，二元醇可以是乙二醇、二乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、一缩二乙二醇、一缩二丙二醇、新戊二醇中一种或多种。优选的，所述聚酯多元醇为聚己二酸丁二醇酯、聚己二酸己二醇酯、聚己二酸乙二醇丁二醇酯中一种或多种。
所述聚醚多元醇是在含活泼氢化合物作为起始剂和催化剂存在下由环氧化合物开环聚合制得；其中环氧化合物可以是环氧丙烷、四氢呋喃、环氧乙烷中一种或多种，在一些优选实施例中，所述聚醚多元醇为聚四亚甲基醚二醇 (PTMG)。
所述催化剂可选用已知的常用的聚醚制备催化剂。
所述聚己内酯多元醇是由单体ε-己内酯和起始剂经开环聚合而成。其中起始剂可以是1,4-丁二醇、新戊二醇、1,6-己二醇、二乙二醇、乙二醇中一种或多种；优选的，起始剂为新戊二醇。
所述聚碳酸酯多元醇是由小分子二元醇和小分子碳酸酯经酯交换反应制得。其中小分子二元醇可以是1,6-己二醇、1,4-丁二醇、1,4-环己烷二甲醇、1,5-戊二醇、3-甲基戊二醇中一种或多种，优选的，小分子二元醇为1,6-己二醇。小分子碳酸酯可以是碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸二苯酯、碳酸亚乙酯或碳酸亚丙酯中一种或多种，优选的，小分子碳酸酯为碳酸亚乙酯。
所述扩链剂包括具有如下结构式的特种二元胺与双酚A类二元醇。
Figure BDA0002445793400000031
进一步的，所述扩链剂中，特种二元胺与双酚A类二元醇的重量比0.5～2：1。其中特种二元胺根据文献(汪称意,李光,江建明.一种含三氟甲基取代不对称芳香二胺及其可溶性透明聚醚酰亚胺的合成与表征[J].化学学报，2013， 66(22):2569-2573)所记载的方法制备而成。
本发明采用特种二元胺和与双酚A类二元醇混合作为扩链剂，可能由于特殊混配扩链体系，使得硬链段之间氢键作用不强，因此不易形成硬段聚集，不产生相分离。相反硬链段与软链段之间有一定的氢键作用，使得软/硬段分布较均匀，易形成均相体系，分子链分布更均匀，使得到的聚氨酯表干时间更短、活化温度更低、流平更快，而且，所得的聚氨酯还具有高溶解性和良好的耐热性。
其中双酚A类二元醇可以是双酚A-二羟乙基醚、双酚A-二羟丙基醚、双酚A (2,3-二羟丙基)甘油醚、双酚A聚氧乙烯醚或双酚A聚氧丙烯醚中的一种或两者混合。
进一步的，所述多异氰酸酯中包括不低于50wt％的甲苯二异氰酸酯，基于多异氰酸酯总重量。本发明选用甲苯二异氰酸酯，是由于其不对称分子结构，协同上述扩链剂组分提高聚氨酯的溶解性。
进一步的，所述的甲苯二异氰酸酯中包含质量分数为30～100％的2,4-甲苯二异氰酸酯。
优选的，所述的甲苯二异氰酸酯为2,4-甲苯二异氰酸酯与2,6-甲苯二异氰酸酯的异构体混合物。所述甲苯二异氰酸酯可以通过TDI-100(100％2,4-甲苯二异氰酸酯)、TDI-80(80％2,4-甲苯二异氰酸酯+20％2,6-甲苯二异氰酸酯)或TDI-65 (65％2,4-甲苯二异氰酸酯+35％2,6-甲苯二异氰酸酯)以一定比例混合得到。
所述二异氰酸酯还可包含4,4-二苯基甲烷二异氰酸酯、4,4-二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯、对苯二亚甲基二异氰酸酯、3,3-二甲基-4,4-联苯二异氰酸酯、3,3-二甲基-4,4-二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、间苯二亚甲基二异氰酸酯、环己烷间二亚甲基二异氰酸酯中一种或多种。
进一步的，所述组分d)催化剂包括叔胺类的三乙胺、三亚乙基二胺、二甲基环己胺等，有机锡类的二月桂酸二丁基锡、辛酸亚锡、二(十二烷基硫)二丁基锡、二乙酸二丁基锡等，有机重金属类催化剂，如异辛酸铅、乙酸苯汞、异辛酸锌、异辛酸锌铋、新癸酸铋中一种或多种，优选辛酸亚锡、二月桂酸二丁基锡或两者混合。
本发明进一步提供了上述热塑性聚氨酯的制备方法，包括将多元醇组分，二异氰酸组分，扩链剂组分，催化剂组分按配方比例混合均匀，再经双螺杆反应挤出制得。
所述热塑性聚氨酯可以采用一步法或间歇法制得。
一步法或间歇法的反应条件为：挤出温度120～230℃，异氰酸酯指数0.5～ 1.2。
本发明还涉及上述热塑性聚氨酯或上述制备方法制备的热塑性聚氨酯的应用，其可以用作粘合剂和表面涂层材料。
本发明的热塑性聚氨酯可以适用于各种类型的粘合剂，如热熔型聚氨酯粘合剂、单组分溶剂型聚氨酯粘合剂、双组分溶剂型聚氨酯粘合剂、水性聚氨酯粘合剂及压敏型聚氨酯粘合剂等。
本发明的粘合剂和表面涂层用热塑性聚氨酯具有快表干、低温活化、快速流平特性，而且，所得的聚氨酯还具有高溶解性、高强度、高回弹性和良好的耐热性，适用于鞋材、建筑、包装、印刷等领域。
具体实施方式
以下结合实例对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
本发明实施例中所用的TDI-80(80wt％2,4-甲苯二异氰酸酯+20wt％2,6-甲苯二异氰酸酯)，MDI(二苯基甲烷二异氰酸酯)，HDI(六亚甲基二异氰酸酯)， HMDI(4,4-二环己基甲烷二异氰酸酯)均来自烟台万华化学股份有限公司。
特种二元胺：(4'-(4”-胺基-2”-三氟甲基苯氧基)-1',3'-二甲基苯)-(4-胺基苯)甲酮(T-A)，按下述方法自制
具体制备方法：
1、(4'-羟基-1',3'-二甲基苯)-(4-硝基苯)甲酮的合成：在-5～0℃下，将244g(2mol)1,3-二甲基苯酚和560g(42mol)三氯化铝分别加入到装有2400mL1,2-二氯乙烷的5L三口烧瓶中，搅拌半小时后，再分批加入37.2g(2mol)4-硝基苯甲酰氯，充分搅拌3h后升温至15℃继续反应2h，倒入5000mL盐酸冰水混合溶液中分解产物，水蒸气蒸馏除去溶剂并用热的甲醇∶水(体积比1∶1)反复多次清洗，得到中间体A：(4'-羟基-1',3'-二甲基苯)-(4-硝基苯)甲酮。
2、(1',3'-二甲基-4'-(4”-硝基-2”-三氟甲基苯氧基)苯)-(4-硝基苯)甲酮(2)的合成：
将326g(1.2mol)中间体A，272g(1.2mol)2-氯-5-硝基三氟甲苯和200g (1.44mol)碳酸钾分别加入到5L三口烧瓶中，加入适量的N,N-二甲基甲酰胺溶剂使其溶解充分。升温至120℃反应15h后，倒入冰水浴中，析出大量黄色固体，再用N,N-二甲基甲酰胺/乙醇混合溶剂(体积比1∶1)重结晶，得到中间体B二硝基化合物：(1',3'-二甲基-4'-(4”-硝基-2”-三氟甲基苯氧基)苯)-(4-硝基苯)甲酮。
3、(4'-(4”-胺基-2”-三氟甲基苯氧基)-1',3'-二甲基苯)-(4-胺基苯)甲酮(3)的合成：
将368g(0.8mol)中间体B二硝基化合物和6g 10％钯碳催化剂加入到5L三口烧瓶中，加入2500mL乙醇加热至回流；再用恒压滴液漏斗30min内滴加300 mL80％的水合肼，继续回流反应4～6h，热过滤得到含氟不对称芳香二胺单体即为(4'-(4”-胺基-2”-三氟甲基苯氧基)-1',3'-二甲基苯)-(4-胺基苯)甲酮(T-A)。
Figure BDA0002445793400000061
含氟二元胺：3，5-二氨基-4-三氯甲基苯乙醚(CUA-24)，购于日本乳化剂株式会社。
双酚A：双酚A-二羟乙基醚(BA-2)、双酚A-二羟丙基醚(BA-P2)购于日本乳化剂株式会社。
双酚A(2,3-二羟丙基)甘油醚(BA-G)，购于南京协诺生物技术有限公司。
双酚A聚氧乙烯醚(BA-E)，购于美国西格玛奥德里奇公司。
PHA(聚己二酸己二醇酯)分子量为2000g/mol，烟台万华化学股份有限公司
PHA(聚己二酸己二醇酯)分子量为3000g/mol，烟台万华化学股份有限公司
PBA(聚己二酸丁二醇酯)分子量为3000g/mol，烟台万华化学股份有限公司
NPG-PCL(新戊二醇引发聚己内酯二醇)分子量为4000g/mol，烟台万华化学股份有限公司
实施例1：
将90wt％分子量为4000g/mol的NPG-PCL(新戊二醇引发聚己内酯二醇)， 7.6wt％TDI-80(80wt％2,4-甲苯二异氰酸酯+20wt％2,6-甲苯二异氰酸酯)，2.35wt％扩链剂组合(T-A/BA-2＝1)，0.05wt％二月桂酸二丁基锡混合均匀，再经双螺杆反应挤出(挤出机温度130℃)制得热塑性聚氨酯弹性体。
实施例2：
将76wt％分子量为2000g/mol的PHA(聚己二酸己二醇酯)，15.46wt％ TDI-80(80wt％2,4-甲苯二异氰酸酯+20wt％2,6-甲苯二异氰酸酯)，5wt％ MDI(4,4-二苯基甲烷二异氰酸酯)，3.51wt％扩链剂组合(T-A/BA-2＝1/2)，0.03wt％二乙酸二丁基锡混合均匀，再经双螺杆反应挤出(挤出机温度160℃)制得热塑性聚氨酯弹性体。
实施例3：
将79.5wt％分子量为3000g/mol的PBA(聚己二酸丁二醇酯)，18.23wt％ TDI-80(80wt％2,4-甲苯二异氰酸酯+20wt％2,6-甲苯二异氰酸酯)，2.2wt％扩链剂组合(T-A/BA-G＝1.5)，0.07wt％辛酸亚锡混合均匀，再经双螺杆反应挤出(挤出机温度160℃)制得热塑性聚氨酯弹性体。
实施例4：
将82wt％分子量为3000g/mol的PHA(聚己二酸己二醇酯)，9.64wt％ TDI-80(80wt％2,4-甲苯二异氰酸酯+20wt％2,6-甲苯二异氰酸酯)，5.4wt％ HDI(六亚甲基二异氰酸酯)，2.95wt％扩链剂组合(T-A/BA-E＝1)，0.01wt％新癸酸铋混合均匀，再经双螺杆反应挤出(挤出机温度165℃)制得热塑性聚氨酯弹性体。
实施例5：
将65wt％分子量为3000g/mol的PBA(聚己二酸丁二醇酯)，17wt％ TDI-80(80wt％2,4-甲苯二异氰酸酯+20wt％2,6-甲苯二异氰酸酯)，11.4wt％ HMDI(4,4-二环己基甲烷二异氰酸酯)，6.5wt％扩链剂组合(T-A/BA-P2＝2)，0.1wt％异辛酸铋混合均匀，再经双螺杆反应挤出(挤出机温度170℃)制得热塑性聚氨酯弹性体。
对比例1：
将79.5wt％分子量为3000g/mol的PBA(聚己二酸丁二醇酯)，18.23wt％ TDI-80(80wt％2,4-甲苯二异氰酸酯+20wt％2,6-甲苯二异氰酸酯)，2.2wt％T-A，0.07wt％辛酸亚锡混合均匀，再经双螺杆反应挤出(挤出机温度160℃)制得热塑性聚氨酯弹性体。
对比例2：
将76wt％分子量为2000g/mol的PHA(聚己二酸己二醇酯)，15.46wt％ TDI-80(80wt％2,4-甲苯二异氰酸酯+20wt％2,6-甲苯二异氰酸酯)，5wt％ MDI(4,4-二苯基甲烷二异氰酸酯)，3.51wt％BA-2，0.03wt％二乙酸二丁基锡混合均匀，再经双螺杆反应挤出(挤出机温度160℃)制得热塑性聚氨酯弹性体。
对比例3：
将90wt％分子量为4000g/mol的NPG-PCL(新戊二醇引发聚己内酯聚)，7.6wt％TDI-80(80wt％2,4-甲苯二异氰酸酯+20wt％2,6-甲苯二异氰酸酯)，2.35wt％扩链剂组合(CUA-24/BA-2＝1)，0.05wt％二月桂酸二丁基锡混合均匀，再经双螺杆反应挤出(挤出机温度130℃)制得热塑性聚氨酯弹性体。
表1、表2为各实施例的组成及样品测试性能。
表1
Figure BDA0002445793400000091
对应上述实施例所制得热塑性聚氨酯弹性体，按以下配方组成分别加入到5000ml三口烧瓶中，快速机械搅拌8h至聚氨酯完全溶解，待气泡消除后，将溶液倒入广口瓶中密封存储，制得溶剂型聚氨酯粘合剂，并进行下表各项性能测试。
Figure BDA0002445793400000101
表2
Figure BDA0002445793400000102
活化温度测试：参照标准EN 12961
表干时间测试：参照标准ASTM D4497
流平性测试：参照标准GB/T 1750
粘结强度测试：参照标准ASTM D-1876
耐热性测试：参照标准ASTM-D816。

Claims (10)

1.一种热塑性聚氨酯，其特征在于，由包括以下组分的反应聚合而成：
Figure FDA0002445793390000011
以以上所有组分质量的和为基准。
2.根据权利要求1所述的热塑性聚氨酯，其特征在于，所述组分a)多元醇的数均分子量为800～6000g/mol，优选1000～4000g/mol。
3.根据权利要求1所述的热塑性聚氨酯，其特征在于，所述组分a)多元醇是聚酯多元醇、聚醚多元醇、聚己内酯多元醇、聚碳酸酯多元醇或其组合物；
所述聚酯多元醇是由二元酸与二元醇通过行业公知的聚酯多元醇合成工艺制得；其中二元酸是丁二酸、己二酸、癸二酸中一种或多种，二元醇是乙二醇、二乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、一缩二乙二醇、一缩二丙二醇、新戊二醇中一种或多种；优选的，所述聚酯多元醇为聚己二酸丁二醇酯、聚己二酸己二醇酯、聚己二酸乙二醇丁二醇酯中一种或多种；
所述聚醚多元醇是在含活泼氢化合物作为起始剂和催化剂存在下由环氧化合物开环聚合制得；其中环氧化合物是环氧丙烷、四氢呋喃、环氧乙烷中一种或多种，优选的，所述聚醚多元醇为聚四亚甲基醚二醇；
所述聚己内酯多元醇是由单体ε-己内酯和起始剂经开环聚合而成，其中起始剂是1,4-丁二醇、新戊二醇、1,6-己二醇、二乙二醇、乙二醇中一种或多种；优选的，起始剂为新戊二醇；
所述聚碳酸酯多元醇是由小分子二元醇和小分子碳酸酯经酯交换反应制得；其中小分子二元醇是1,6-己二醇、1,4-丁二醇、1,4-环己烷二甲醇、1,5-戊二醇、3-甲基戊二醇中一种或多种，优选的，小分子二元醇为1,6-己二醇；小分子碳酸酯是碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸二苯酯、碳酸亚乙酯或碳酸亚丙酯中一种或多种，优选的，小分子碳酸酯为碳酸亚乙酯。
4.根据权利要求1所述的热塑性聚氨酯，其特征在于，所述扩链剂包括具有如下结构式的特种二元胺和双酚A类二元醇；
Figure FDA0002445793390000021
优选的，所述扩链剂中，特种二元胺与双酚A类二元醇的重量比0.5～2：1。
5.根据权利要求4所述的热塑性聚氨酯，其特征在于，所述双酚A类二元醇为双酚A-二羟乙基醚、双酚A-二羟丙基醚、双酚A(2,3-二羟丙基)甘油醚、双酚A聚氧乙烯醚或双酚A聚氧丙烯醚中的一种或两者混合。
6.根据权利要求4所述的热塑性聚氨酯，其特征在于，所述多异氰酸酯中包括不低于50wt％的甲苯二异氰酸酯，基于多异氰酸酯总重量；
优选的，所述的甲苯二异氰酸酯中包含质量分数为30～100％的2,4-甲苯二异氰酸酯。
7.根据权利要求1所述的热塑性聚氨酯，其特征在于，所述二异氰酸酯还包含4,4-二苯基甲烷二异氰酸酯、4,4-二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯、对苯二亚甲基二异氰酸酯、3,3-二甲基-4,4-联苯二异氰酸酯、3,3-二甲基-4,4-二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、间苯二亚甲基二异氰酸酯、环己烷间二亚甲基二异氰酸酯中一种或多种。
8.根据权利要求1所述的热塑性聚氨酯，其特征在于，所述组分d)催化剂包括叔胺类的三乙胺、三亚乙基二胺、二甲基环己胺等，有机锡类的二月桂酸二丁基锡、辛酸亚锡、二(十二烷基硫)二丁基锡、二乙酸二丁基锡等，有机重金属类催化剂，如异辛酸铅、乙酸苯汞、异辛酸锌、异辛酸锌铋、新癸酸铋中一种或多种，优选辛酸亚锡、二月桂酸二丁基锡或两者混合。
9.根据权利要求1-8任一项所述的热塑性聚氨酯的制备方法，其特征在于，将多元醇组分，二异氰酸组分，扩链剂组分，催化剂组分按配方比例混合均匀，再经双螺杆反应挤出制得；
优选的，所述热塑性聚氨酯采用一步法或间歇法制得；
反应条件为：挤出温度120～230℃。
10.根据权利要求1-8任一项所述的热塑性聚氨酯或权利要求9所述制备方法制备的热塑性聚氨酯的应用，其用作粘合剂和表面涂层材料。
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