CN1402758A - 相容树脂共混物和其制备方法 - Google Patents

相容树脂共混物和其制备方法 Download PDF

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CN1402758A
CN1402758A CN00816605A CN00816605A CN1402758A CN 1402758 A CN1402758 A CN 1402758A CN 00816605 A CN00816605 A CN 00816605A CN 00816605 A CN00816605 A CN 00816605A CN 1402758 A CN1402758 A CN 1402758A
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H·法拉
F·小勒马
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Abstract

本发明为聚合烃和热塑性聚氨酯的共混物，其为含低浓度异氰酸酯活性基团的相容聚合物烃。该相容剂可通过具有侧基或引入的胺活性基团的改性聚合物与羟胺、二胺或聚醚单胺反应制备。该相容共混物还包括非－TPU工程热塑性材料，由此形成聚合物烃与非－TPU工程热塑性材料的相容共混物。在此情况下，TPU用作共相容剂。

Description

相容树脂共混物和其制备方法
本发明涉及通常不相容聚合物的相容树脂共混物和这些共混物的制备方法。
用于某些聚合物共混物的相容剂是本领域已知的。例如，US5,959,032(Evans等人)描述了制备(用于聚丙烯和热塑性聚烯烃的)相容剂的方法，所述相容剂为酸酐官能化聚丙烯和聚醚胺的反应产品。
JP专利申请3-231963公开了热塑性聚氨酯与聚烯烃的共混物，该共混物与用羧基、酸酐基团和/或环氧基团改性的聚烯烃相容。据报道该相容共混物具有高耐热性、高机械强度和高耐磨损性。
现有相容共混物存在的缺点是：具有不合适的低熔接线强度，该强度对于例如汽车仪表板或保险杠杆应用是重要的；其制备方法通常需要多浇口或复杂的注塑设计。因此，需要具有克服此缺陷的有效相容剂。
本发明为一种组合物，它包括a)热塑性聚氨酯和b)相容剂的共混物或反应产品，所述相容剂为含异氰酸酯活性基团或聚氧亚烷基的第一聚合烃。
第二方面，本发明为一种组合物，它包括a)热塑性聚氨酯、b)相容剂的共混物或反应混合物和c)第二聚合物烃，所述相容剂为含异氰酸酯活性基团或聚氧亚烷基基团的第一聚合物烃，其中第一和第二聚合物烃各自独立地选自聚丙烯、高密度聚乙烯、低密度聚乙烯、线性低密度聚乙烯、基本上线性乙烯/α-烯烃共聚物、聚苯乙烯、聚α-甲基苯乙烯、聚乙烯基甲苯和乙烯-苯乙烯共聚体。
第三方面，本发明为制备相容组合物的方法，包括在反应条件下配混a)热塑性聚氨酯和b)相容剂，所述相容剂为含异氰酸酯活性基团的第一聚合物烃。
在第一方面中，本发明为包括a)热塑性聚氨酯和b)相容剂的共混物或反应产品的组合物。该相容剂，其为含异氰酸酯活性基团或聚氧亚烷基的第一聚合物烃，有利地通过将a)具有侧基或引入的胺活性基团的第一聚合物烃与b)含至少一个胺基和至少一个异氰酸酯活性基团的化合物或c)含胺基和聚氧亚烷基的化合物在反应条件下接触制备。
这里使用的术语聚合物烃是指聚烯烃、链烯基芳烃的聚合物、或由烯烃和链烯基芳烃单体制备的聚合物。术语异氰酸酯活性基团是指与异氰酸酯基团反应的基团，优选氨基或羟基。
聚烯烃的例子包括聚丙烯、高密度聚乙烯(HDPE)、低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLDPE)或基本上线性乙烯/α-烯烃共聚物，如描述于US5,272,236和5,278,272中的那些共聚物。链烯基芳烃聚合物的例子包括苯乙烯、α-甲基苯乙烯和乙烯基甲苯的聚合物。由烯烃和链烯基芳烃单体制备的聚合物的例子是乙烯-苯乙烯共聚体。
可通过将烯属不饱和胺活性化合物接枝到聚合物烃的主链上，使胺活性基团成为第一聚合物烃主链的侧基。此外，可通过将烯烃或链烯基芳烃单体或这两者与烯属不饱和胺活性化合物共聚，将胺活性基团引入聚合物烃的主链中。接枝为将胺活性基团引入聚合物烃链中的优选方式。
这里使用的术语“烯属不饱和胺活性化合物”是指这样一种化合物：a)该化合物可通过接枝或共聚与聚合物烃连接，b)该化合物对胺化学活性。类似地，这里使用的术语“胺活性基团”是指通过接枝或共聚形成的残基。可被接枝到聚合物烃主链上或与烯烃或链烯基芳烃单体共聚的烯属不饱和胺活性化合物的例子包括，烯属不饱和羧酸如马来酸、富马酸、衣康酸、丙烯酸、甲基丙烯酸和巴豆酸；酸酐如马来酸酐和衣康酸酐；乙烯基苄基卤化物如乙烯基苄基氯和乙烯基苄基溴；丙烯酸和甲基丙烯酸的烷基酯如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸月桂酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯和甲基丙烯酸月桂基酯；和烯属不饱和环氧乙烷如丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯和乙基丙烯酸缩水甘油酯。优选的烯属不饱和胺活性化合物包括马来酸酐、丙烯酸、甲基丙烯酸、丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯，更优选马来酸酐。用马来酸酐接枝的聚丙烯是更优选的改性聚合物烃。市购的改性聚合物烃的一个例子是EPOLENETM PP 3003蜡(Eastman Chemical Co.的商标)，其为含约0.5至1wt％接枝马来酸酐单元的聚丙烯蜡。
结合或接枝胺活性基团的程度取与用途有关，但优选不大于10wt％，更优选不大于5wt％，更优选不大于2wt％，最优选不大于1wt％；优选不低于0.01wt％，更优选不低于0.1wt％，最优选不低于0.2wt％，按相容剂的重量计。
羟胺为含胺基和至少一个羟基，但优选仅一个羟基的化合物。胺可为伯胺或仲胺，优选伯胺。多胺为含至少两个胺基，优选仅两个胺基的化合物。合适的羟胺或多胺的一个例子由如下通式表示：
Figure A0081660500071
其中X为O或NH，其中各R独立地为H、-CH3或-CH2CH3；和其中x为0至50。羟胺的公开和制备可在US3,231,619、4,612,335和4,888,446中找到，其公开的内容这里作为参考引入。优选的氧链烷醇胺的例子包括2-氨基乙醇、1-氨基-2-丙醇、2-氨基-1-丙醇、3-氨基-1-丙醇、2-(2-氨乙氧基)乙醇、1-氨基-2-丁醇、2-氨基-3-丁醇和聚氧亚烷基二醇胺。2-氨基乙醇是优选的链烷醇胺。
多胺为具有至少两个胺基的化合物。合适的多胺的例子包括α，ω-亚烷基二胺如乙二胺、1，3-丙二胺、1，4-丁二胺和1，6-己二胺，以及聚氧亚烷基二胺，市购的如JEFFAMINETM聚氧亚烷基二胺(HuntsmanPetrochemical的商标)。当悬挂于第一聚合物烃主链上的胺活性基团为马来酸酐基团时，使用多胺或链烷醇胺制备的相容剂含具有如下结构特征的侧基：
其中X为NH或O，各R独立地为H、-CH3或-CH2CH3；和其中x为0至50。
聚氧亚烷基主链可通过将胺活性基团与例如Evans等人在US5,959,032中描述的和以JEFFAMINETM M-1000和JEFFAMINETM 2005树脂(Huntsman Petrochemical的商标)市购的聚醚单胺反应引入第一聚合物烃主链中。用聚醚单胺制备的相容剂优选含具有如下结构特征的侧基：
其中R1为C1-C4烷基，各R独立地为H、-CH3或-CH2CH3；和其中x为0至50。
使用化学计量过量的羟胺、多胺或聚醚单胺，以确保胺活性基团完全或基本上完全转化。
热塑性聚氨酯(TPU)可为工程热塑性聚氨酯或ETPU(又称为硬质TPU)或软质TPU。ETPU具有玻璃转化温度(Tg)大于50℃并含有低于25wt％的高分子量二醇单元(换言之，具有分子量不低于500amu的二醇)。高分子量二醇单元优选构成不大于10wt％的ETPU，更优选构成不大于5wt％的ETPU，和更优选构成不大于1wt％的ETPU。最优选的ETPU含零高分子量二醇单元。
市购ETPU例子包括ISOPLASTTM树脂(The Dow Chemical Company的商标)，其制备方法例如公开于Goldwasser等人的US4,376,834和Oriani的US5,627,254中，其公开的内容这里作为参考引入。ETPU含扩链剂如1，6-己二醇或1，4-丁二醇和聚乙二醇的共混物的结构单元。扩链剂优选为1，4-丁二醇和聚乙二醇，更优选1，4-丁二醇与二甘醇或三甘醇，和最优选1，4-丁二醇与三甘醇的共混物。
TPU还可为具有Tg低于25℃和肖氏A硬度不超过95的软质TPU。市购的软质TPU的一个例子为PELLETHANETM热塑性聚氨酯树脂。(PELLETHANE为The Dow Chemical Company的商标。)
TPU可与相容剂掺混或反应。例如，若相容剂含异氰酸酯活性基团，则该共混物可在加热和剪切下配混以使TPU，特别是ETPU解聚形成异氰酸酯基团和羟基。冷却后，异氰酸酯基团可与相容剂的异氰酸酯活性基团反应形成新的氨基甲酸酯链。例如，当相容剂通过马来酸酐接枝的聚丙烯和2-氨基乙醇或乙二胺反应制备时，相容剂和ETPU的反应产品假定具有如下结构属性：
其中X为NH或O。此外，若相容剂含不与异氰酸酯反应的聚氧亚烷基基团，则据信TPU不与相容剂反应。
在第二方面，本发明为包括a)TPU、b)相容剂的共混物或反应混合物和c)第二聚合物烃的组合物。该组合物优选为TPU在第二聚合物烃基质中的相容分散体，或第二聚合物烃在聚氨酯基质中的分散体。对于TPU在第二聚合物烃中的相容分散体，TPU，优选ETPU的浓度为约10至约40wt％，按TPU、第二聚合物烃和相容剂的重量计。对于第二聚合物烃在TPU，优选ETPU中的相容分散体，第二聚合物烃在TPU中的浓度优选不低于5wt％，和不大于40，更优选不大于30，和最优选不大于20wt％，按TPU、第二聚合物烃和相容剂的重量计。
使用的相容剂的量与应用相关，但通常以与不含相容剂的第二聚合物烃和热塑性聚氨酯共混物相比足够提高熔合线处的无缺口伊佐德冲击强度或拉伸强度的量使用。相容剂的量优选不低于约0.5wt％，更优选不低于1wt％，和最优选不低于2wt％；及优选不大于20wt％，更优选不大于15wt％，和最优选不大于10wt％，按第二聚合物烃、TPU和相容剂的总重量计。
本发明的相容剂还可用于形成第二聚合物烃和除TPU外的宽范围工程热塑性材料(以下称为第二工程热塑性材料)的分散体，条件是该共混物包含共相容量的TPU。其它工程热塑性材料的例子包括聚酯如聚对苯二甲酸乙二醇酯(PET)和聚对苯二甲酸丁二醇酯(PBT)、聚碳酸酯如双酚-A-聚碳酸酯、聚酰胺如尼龙、聚甲醛如聚缩醛、聚砜、聚丙烯酸酯、聚芳基化物、聚亚芳基氧化物如聚苯醚(PPO)、聚乙烯醇、聚乙酸乙烯酯、及乙烯-乙酸乙烯酯共聚物、乙烯-乙烯基醇共聚物和聚醚内酯。
这里使用的“共相容量”是指与不含TPU的组合物相比提高含第二聚合物烃、第二工程热塑性材料和相容剂的组合物的熔合线强度或伸长率所需的TPU量。相容剂与TPU的重量比优选不低于1∶10，更优选不低于1∶5，和最优选不低于1∶2；及优选不大于10∶1，更优选不大于5∶1，和最优选不大于2∶1。当TPU用作共相容剂时，其用量优选不低于0.1wt％，更优选不低于1wt％，和最优选不低于2wt％；及优选不大于20wt％，和更优选不大于10wt％，按聚合物烃、第二工程热塑性材料、TPU和相容剂的总重量计。
尽管可将相容剂和TPU在与其它工程热塑性材料和聚烯烃接触之前反应性挤出，但不是必须这样做。可方便地将相容剂、第二工程热塑性材料、聚合物烃和TPU在解聚温度，优选不低于180，更优选不低于200℃；及优选不大于300℃，更优选不大于250℃下一起掺混并反应性挤出。
本发明的相容共混物与不相容的共混物相比，通常呈现改进的可印刷性、拉伸强度、落镖冲击和熔合线强度等性能。这些共混物可用于生产汽车部件如保险杠、汽车偏导器、挡泥板，以及工具、用品、运动器具和管连接器。
下面的实施例仅用于说明目的，并不用于限制本发明范围。
实施例1-聚丙烯和聚氨酯工程热塑性树脂的相容化
A.制备相容剂
通过将EPOLENETM PP 300蜡(用约0.5至约1wt％马来酸酐接枝的聚丙烯)与2-氨基乙醇(1wt％)在塑料袋中滚动混合，制备用于聚丙烯和聚氨酯工程热塑性树脂的相容剂。将该混合物通过34-mm双螺杆挤出机在保持200rpm下并在220℃下挤出。停留时间为约20秒。通过IR光谱证实马来酸酐向相应的酰亚胺-链烷醇的转化。
B.制备相容PP-ISOPLAST混合物
将一部分按步骤A制备的相容剂(5wt％)与HIDMONTTM PD 701聚丙烯(Hidmont的商标，65wt％)和干燥的XUS 72301.00L工程热塑性聚氨酯(30wt％)滚动混合，该热塑性聚氨酯基本上按照US5,627,254中的描述按如下制备：将4，4′-二异氰酸根合二苯基甲烷(68wt％)、三甘醇(16.2wt％)、1，4-丁二醇(14.6wt％)、亚磷酸三壬苯基酯(0.13wt％)、FOMREZTM UL-22催化剂(WitcoCorporation的商标，0.06wt％)、ADVAWAXTM 280(Morton Indutries的商标，0.25wt％)、IRGANOXTM 1010稳定剂(Ciba-Geigy的商标，0.25wt％)和UVTEXTM OB 328稳定剂(Ciba-Geigy的商标，0.002％)反应挤出。将该混合物在双螺杆挤出机中在220℃下配混。将所得共混物在干燥器中干燥4小时，然后切割为6″×0.5″×0.125″(15cm×1.3cm×0.3cm)试样并在220℃下模塑。熔合线强度(自熔合线的拉伸强度)为4200psi。测得断裂伸长率为420％。
实施例2-聚对苯二甲酸乙二醇酯与乙烯-辛烯共聚物的相容化
将用约0.8至约1wt％马来酸酐接枝的高密度聚乙烯与2-氨基乙醇(1wt％)在双螺杆挤出机上在220℃下配混形成相容剂前体。将一部分该前体(5wt％)与TRAYTUFTM 5900 PET(Shell Chemical的商标，70wt％)、AFFINITYTM 8180乙烯-辛烯共聚物(The Dow ChemicalCompany的商标，20wt％)和XUS 7230l.00L工程热塑性聚氨酯(5wt％)滚动混合，将该共混物按如上所述在双螺杆挤出机上配混。按实施例1中的描述将该试样切割并模塑。测得在熔合线处的无缺口IZOD冲击强度为6.5ft-lb/in。
实施例3-聚对苯二甲酸乙二醇酯与高密度聚乙烯的相容化
将按实施例2制备的相容剂前体(5wt％)与TRAYTUFTM 5900 PET(70wt％)、LUPOLENTTM L426 1 AQ 404高密度聚乙烯(The DowChemical Company的商标，20wt％)和XUS 72301.00L工程热塑性聚氨酯(5wt％)滚动混合。将该共混物按如上所述在双螺杆挤出机上配混。测得在熔合线处的无缺口IZOD冲击强度为10.8ft-lb/in。
实施例4-聚丙烯与热塑性聚氨酯弹性体相容化
通过将EPOLENETM PP 3003蜡与JEFFAMINETM M-2005聚醚单胺(Huntsman Petrochemical Corp.的商标，1wt％)在塑料袋中滚动混合，制备用于聚丙烯和热塑性聚氨酯弹性体的相容剂。将该混合物通过34-mm双螺杆挤出机在保持200rpm下并在220℃下挤出。停留时间为约20秒。通过IR光谱证实马来酸酐向相应的酰亚胺-氧亚烷基的转化。将一部分该相容剂与HIDMONTTM PP 701聚丙烯(Hidmont公司的商标，75wt％)和基于VORANOLTM的TPU XU 63142(The DowChemical Company的商标，20％)配混。测得在25℃时的落镖冲击为445in-lb。在15℃时，落镖冲击为358in-lb。在0℃时，落镖冲击为338in-lb。拉伸强度为3900psi。
实施例5-乙烯-辛烯共聚物与热塑性聚氨酯的相容化
FUSABONDTM MN-493 D树脂(du Pont de Nemours的商标，0.5wt％接枝乙烯-1-辛烯共聚物)和AFFINITYTM乙烯-l-辛烯共聚物(TheDow Chemical Company的商标)的50∶50wt％混合物与乙二胺(0.25wt％)一起加入保持200rpm和220℃下的34-mm双螺杆挤出机中配混。停留时间为约20秒。在配混期间将乙二胺通过侧面注射加入。通过IR光谱证实马来酸酐向相应的酰亚胺的转化。将此稀释的相容剂(4wt％)与ISOPLAST XUS72301工程热塑性聚氨酯(88wt％)和AFFINITY8180乙烯-1-辛烯共聚物混合。该组合物模塑后的无缺口IZOD冲击强度为41ft-lb/in。

Claims (10)

1.一种组合物，它包括a)热塑性聚氨酯和b)相容剂的共混物或反应产品，所述相容剂为含异氰酸酯活性基团或聚氧亚烷基基团的第一聚合烃。
2.根据权利要求1的组合物，其中第一聚合物烃选自选自聚丙烯、高密度聚乙烯、低密度聚乙烯、线性低密度聚乙烯、基本上线性乙烯/α-烯烃共聚物、聚苯乙烯、聚α-甲基苯乙烯、聚乙烯基甲苯和乙烯-苯乙烯共聚体，其中相容剂含具有如下结构的异氰酸酯活性基团侧基：
其中X为NH或O，R1为H或C1-C4烷基；各R独立地为H、-CH3或-CH2CH3；和其中x为0至50，其中侧基的浓度不低于0.1wt％，且不大于2wt％，按相容剂的重量计。
3.权利要求2的组合物，其中热塑性聚氨酯为具有Tg大于50℃的工程热塑性聚氨酯，第一聚合物烃为聚丙烯或乙烯-1-辛烯共聚物，x为0，及R1和R各自为H。
4.权利要求2的组合物，其中热塑性聚氨酯为具有Tg低于25℃的软质热塑性聚氨酯，R1为甲基和R为H。
5.权利要求1-4任何一项的组合物，其中还包括第二聚合物烃，它选自选自聚丙烯、高密度聚乙烯、低密度聚乙烯、线性低密度聚乙烯、基本上线性乙烯/α-烯烃共聚物、聚苯乙烯、聚α-甲基苯乙烯、聚乙烯基甲苯和乙烯-苯乙烯共聚体。
6.一种组合物，包括a)热塑性聚氨酯、b)相容剂的共混物或反应混合物和c)第二聚合物烃，所述相容剂为含异氰酸酯活性基团或聚氧亚烷基的第一聚合物烃，其中第一和第二聚合物烃各自独立地选自聚丙烯、高密度聚乙烯、低密度聚乙烯、线性低密度聚乙烯、基本上线性乙烯/α-烯烃共聚物、聚苯乙烯、聚α-甲基苯乙烯、聚乙烯基甲苯和乙烯-苯乙烯共聚体。
7.根据权利要求6的组合物，其中热塑性聚氨酯为具有Tg大于50℃的工程热塑性聚氨酯，第二聚合物烃为聚丙烯、乙烯-1-辛烯共聚物或高密度聚乙烯，相容剂为含具有如下结构的异氰酸酯活性侧基的聚丙烯、乙烯-1-辛烯共聚物或高密度聚乙烯：
Figure A0081660500031
其中X为NH或O，和其中侧基的浓度不低于0.1wt％，且不大于2wt％，按相容剂的重量计，条件是当第二聚合物烃为聚丙烯时，相容剂含聚丙烯。
8.权利要求6或7任何一项的组合物，还包括选自聚酯、聚碳酸酯、聚酰胺、聚甲醛、聚砜、聚芳基化物、聚亚芳基氧化物、聚乙烯醇、聚乙酸乙烯酯、乙烯-乙酸乙烯酯共聚物、乙烯-乙烯醇醇共聚物和聚醚内酯的第二工程热塑性材料，和其中热塑性聚氨酯为Tg大于50℃的工程热塑性聚氨酯。
9.一种制备相容组合物的方法，包括在反应条件下配混a)热塑性聚氨酯和b)相容剂，所述相容剂为含异氰酸酯活性基团的第一聚合物烃，其中相容剂含具有如下结构的异氰酸酯活性侧基：
其中X为NH或O；各R独立地为H、-CH3或-CH2CH3；和其中x为0至50，其中侧基的浓度不低于0.1wt％，且不大于2wt％，按相容剂的重量计。
10.权利要求10的方法，其中热塑性聚氨酯为具有Tg大于50℃的工程热塑性聚氨酯，其中x为0和R为H，该方法还包括将第二聚合物烃与热塑性聚氨酯和相容剂配混的步骤，其中加入共混物中的热塑性聚氨酯的浓度为1至10wt％，按相容剂、热塑性聚氨酯、第二聚合物烃和第二工程热塑性材料的重量计；其中加入共混物中的相容剂的浓度为1至10wt％，按相容剂、热塑性聚氨酯、第二聚合物烃和第二工程热塑性材料的重量计。
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CN104947243B (zh) * 2015-06-24 2017-05-17 北京服装学院 一种含镧系元素聚丙烯/聚氨酯x射线屏蔽复合纤维的制备方法
CN106280404A (zh) * 2016-08-15 2017-01-04 吴冰滢 一种防噪音阻燃聚氨酯泡沫材料及其制备方法
CN106366479A (zh) * 2016-08-23 2017-02-01 无锡市永亿精密铸造有限公司 一种用于超声波足浴机的复合材料
CN107177194A (zh) * 2017-07-06 2017-09-19 浙江工贸职业技术学院 一种汽车内饰高分子材料及其制备方法
CN115386166A (zh) * 2022-09-19 2022-11-25 成都金发科技新材料有限公司 一种聚丙烯复合材料及制备方法和应用
CN115386166B (zh) * 2022-09-19 2023-08-29 成都金发科技新材料有限公司 一种聚丙烯复合材料及制备方法和应用

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EP1235879B2 (en) 2010-08-25
EP1235879B1 (en) 2004-05-19
DE60010926T2 (de) 2005-05-25
ZA200203868B (en) 2003-05-15
BR0015767A (pt) 2002-08-06
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