CN1732197A - 聚氨酯反应性组合物 - Google Patents
聚氨酯反应性组合物 Download PDFInfo
- Publication number
- CN1732197A CN1732197A CNA2003801073353A CN200380107335A CN1732197A CN 1732197 A CN1732197 A CN 1732197A CN A2003801073353 A CNA2003801073353 A CN A2003801073353A CN 200380107335 A CN200380107335 A CN 200380107335A CN 1732197 A CN1732197 A CN 1732197A
- Authority
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- China
- Prior art keywords
- isocyanate
- polyester
- polyurethane
- glycol
- reactive compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
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Abstract
本发明涉及含有异氰酸酯、异氰酸酯反应性聚合物和用于使异氰酸酯与异氰酸酯反应性化合物反应的催化剂的聚氨酯反应性组合物。所述异氰酸酯反应性化合物是聚酯、聚酯聚氨酯、聚碳酸酯或其混合物的二醇或多官能多元醇,该聚酯得自羟基化羧酸或其相应内酯,且催化剂为具有空间位阻效应的铋化合物。
Description
根据权利要求1,本发明涉及可热固化的聚氨酯反应性(reactive)组合物,该组合物包含异氰酸酯、异氰酸酯反应性化合物和使异氰酸酯与异氰酸酯反应性化合物反应的催化剂;根据权利要求18,本发明涉及包含所述组合物的粘合剂;根据权利要求20,本发明涉及对所述组合物进行热固化而得到的聚氨酯;并根据权利要求21或22,本发明涉及制备可热固化的聚氨酯反应性组合物的方法。
可热固化的聚氨酯反应性组合物是可以通过热固化而制得聚氨酯的单组分组合物。其包括异氰酸酯和作为异氰酸酯反应性化合物的二醇或多官能(higher functional)(即超过两个官能团)多元醇。聚氨酯反应性组合物可以进行复合材料的简单加工,如建筑板材和层压材料、交通工具的缓冲垫、以及船舶和航空器的增强结构。其可以用作粘合剂、密封材料、涂敷材料、灌封材料等。例如,聚氨酯反应性组合物作为粘合剂的使用在汽车工业上尤为受到关注。
欧洲专利第B-0062780号和欧洲专利第B-0103323号公开了固体异氰酸酯悬浮物的使用,通过表面上的聚加合物结构使其钝化。
欧洲专利第B-0598873号描述了一种聚氨酯反应性组合物,其包含作为催化剂的叔胺或有机金属化合物,以提高反应速率。
欧洲专利第A-0431414号描述了一种聚氨酯反应性组合物,其包含聚醚多元醇和聚酯多元醇。
按照惯例,用于聚氨酯反应性组合物的二醇或多官能多元醇是羟端基聚醚。这种聚醚便宜,且易于处理。另一方面,已知聚醚聚氨酯具有较低的机械性能。对于在迫切需要机械性能较高的应用中,可以使用含有由聚酯聚氨酯产生的聚酯二醇或多元醇的聚氨酯反应性组合物。
聚酯聚氨酯显示出比聚醚聚氨酯高的拉伸强度。但是,已知聚酯聚氨酯的耐水解能力较低。在用于在暴露的湿气中产生出聚酯聚氨酯的应用中,聚酯聚氨酯是不适合的。
与传统的聚酯聚氨酯相比,环氧树脂通常表现出较高的耐水解能力。并且,环氧树脂的拉伸强度和抗拉剪切强度(lap shear strength)通常比传统聚酯聚氨酯的高。由于这些有利因素,环氧树脂通常优选于传统的聚氨酯反应性组合物。然而,经固化的环氧树脂易脆。其断裂伸长率很低。当在静电和动态负载下材料的性能均很重要的情况中,经固化的环氧树脂的抗冲性能常常难以令人满意。在将环氧树脂用于外包覆基层,如汽车工业中的这类应用时,由于其断裂伸长很低,且抗冲性能很差,所以环氧树脂并不适合。因此,非常需要一种产品,其能够将好的拉伸强度与断裂伸长率、和抗拉剪切强度、及良好的耐水解性能相互结合
本发明的目的是提供一种聚氨酯反应性组合物,在经过固化,能够得到具有特别高的拉伸和抗拉剪切强度以及高断裂伸长率和良好耐水解性能的聚氨酯反应性组合物。
根据本发明,通过以下所述来解决这个问题:根据权利要求1,产生可热固化的聚氨酯反应性组合物,包含异氰酸酯、异氰酸酯反应性化合物,以及用于异氰酸酯与异氰酸酯反应性化合物反应的催化剂;其中异氰酸酯反应性化合物是二醇或多官能多元醇,该多元醇属于聚酯、聚酯聚氨酯、聚碳酸酯或其混合物。聚酯得自羟基化羧酸或相应的内酯,而催化剂是具有空间位阻效应的铋化合物。
这里的术语“其混合物”意味着由所有给出组分的一种或多种组成的混合物。
在权利要求2到17中对本发明组合物的进一步优选实施方案进行定义。
根据本发明的聚氨酯反应性组合物可以产生具有超过17MPa的相当高拉伸强度,和在底层涂层上超过14MPa的抗拉剪切强度的聚氨酯。所述聚氨酯的断裂伸长率超过了300%。
令人惊奇的是,从根据本发明的聚氨酯反应性组合物中产生的聚氨酯具有明显提高的耐水解性能。因此,在用于暴露于潮湿环境的情况中,本发明的组合物能够得到极好的效果。即甚至在暴露于95%的相对湿度以及70℃下保持7天、并继而于-40℃下保持16小时和室温下保持2小时后,仍能达到超过17MPa的拉伸强度、在外包覆的基层上超过14MPa的抗拉剪切强度、超过了300%的断裂伸长率的上述拉伸性质。在外包覆的基层上,本发明的组合物产生的聚氨酯的冲击强度超过环氧树脂的冲击强度。钢铁外包覆聚氨酯的抗拉剪切失败方式显示出,毫无例外地,将外包覆材料或钢铁基层完全暴露在95%的相对湿度和70℃下保持7天、并继而于-40℃下保持16小时和室温下保持2小时后,聚氨酯会断裂。
根据本发明的聚氨酯反应性组合物可以得到将传统聚氨酯所需的性质与环氧树脂的强拉伸强度和耐水解能力以及良好的断裂伸长率相结合的固化产品。根据本发明的组合物特别适用于需暴露于潮湿环境以及承受静力和动力的情况,例如作为汽车工业应用中的粘合剂。
另外,根据本发明的聚氨酯反应性组合物显示出与固化峰较高端和较低端之间温差相关的较窄固化峰。采用差式扫描量热计以10℃/分钟的加热速度进行测量,固化峰较高端与较底端的温差小于30℃。较窄的固化范围使固化反应迅速且易于控制。
本发明的一方面,可热固化的聚氨酯反应性组合物包含固态表面钝化的异氰酸酯、异氰酸酯反应性聚合物以及用于异氰酸酯与异氰酸酯反应性化合物反应的催化剂。其中,异氰酸酯反应性化合物是聚酯或聚碳酸酯或其混合物的二醇或多元醇。聚酯得自羟基化羧酸或其相应的内酯,而催化剂是具有空间位阻效应的铋化合物。
这样的组合物通常是热塑性的,且在室温下是固体。其在室温下稳定,所以易于贮藏。
在除包含固态的聚酯多元醇外,还包含聚碳酸酯的液态二醇或多官能多元醇的热塑性聚氨酯反应性组合物中,“pop-off现象”,即在应用之后的冷却时,通常能够观察到的未固化组合物从基层裂开的问题,会明显减小。
在一个优选的具体化实施方案中,聚氨酯反应性的组合物除包含热塑性的聚酯多元醇外,还包含聚碳酸酯的二醇或多官能多元醇,其至少为多元醇总重量的30%,优选地为至少50%。
根据本发明,异氰酸酯反应性化合物的例子为:聚己内酯二醇,其平均分子量为200~20000,优选为1000~4000,最优选为2000;聚己内酯三醇,其平均分子量为200~20000,优选为1000~9000;γ-聚丁内酯二醇,其平均分子量为200~20000,优选为1000~4000,最优选为2000;γ-聚丁内酯三醇,其平均分子量为200~20000,优选为1000~9000;δ-聚戊内酯二醇,其平均分子量为200~20000,优选为1000~4000,最优选为2000;δ-聚戊内酯三醇,其平均分子量为200~20000,优选为1000~9000;聚碳酸酯二醇,其平均分子量为200~20000,优选为1000~4000,最优选为2000;以及聚碳酸酯三醇,其平均分子量为200~20000,优选为1000~9000。
对于具有专业技术的人员来说,合适的异氰酸酯是已知的。例子为甲苯二异氰酸酯和异佛乐酮二异氰酸酯。在一个异氰酸酯为固态表面钝化的异氰酸酯的具体化实施方案中,优选地,异氰酸酯为甲苯二异氰酸酯的脲或uretdion。
当使用固态表面钝化的异氰酸酯来制备组合物时,由含有至少两个伯胺基、优选聚合的二伯胺的化合物钝化固态异氰酸酯。合适的二伯胺聚合物是Jeffamin D-400(Huntsmann,聚乙二醇二胺,重均分子量400)、Jeffamin D-230(Huntsmann,聚乙二醇二胺,重均分子量230)、Jeffamin ED-600(Huntsmann,聚乙二醇二胺,重均分子量600)。更合适的二胺是N,N’-二(3-胺基丙基)-乙烯基二胺、乙烯基二胺、1,3-丙烯基二胺、1,4-丁烯基二胺,新戊烯基二胺、1,5-二胺基-2-甲基-戊烷、1,7-二胺基庚烷、1,8-二胺基辛烷、1,9-二胺基壬烷、1,10-二胺基癸烷、4,7-二氧癸烷-1,10-二胺,4,9-二氧癸烷-1,12-二胺、4,7,10-三氧癸烷-1,13-二胺、4,4-二胺基二环己基甲烷、3,3-二甲基-4,4-二胺基二环己基甲烷、4,4-二胺基联苯甲烷、二胺基-m-二甲苯、二胺基-p-二甲苯、异佛乐酮二胺、1,2-二胺基正己烷、4,4-二胺基-联苯醚、1,8-二胺基萘、2,3-二胺基甲苯。进一步地,以下化合物能够通过灌封方式用于固态异氰酸酯的钝化:三胺,例如二乙烯基三胺、1,5,11-三胺基癸烷、Jeffamin T-403(聚乙二醇三胺重均分子量400)、3-(2-胺基乙烷)胺基丙胺、三丙烯基三胺,4-胺乙基-1,8-二胺基辛烷;四胺,例如三乙基四胺;以及六胺,例如五乙烯基六胺。
在一个优选的具体化实施方案中,催化剂是具有空间位阻效应的铋化合物,其中铋含量为0.05%~0.5%。优选地,具有空间位阻效应的铋催化剂为新癸酸铋。进一步优选地,组合物包含具有空间位阻效应的锑化合物.另一种合适的催化剂是具有空间位阻效应的锆化合物,例如新癸酸锆。
合适的添加剂对于专业技术人员来说是已知的。其包括稳定剂,如聚合的三元伯胺;填料,如炭黑、碳酸钙和粘土;干燥剂,如分子筛;粘合助剂,如氨基或环氧硅烷;流变助剂,如发烟硅石;低分子异氰酸酯反应性扩链剂;增塑剂等等。
更进一步来说,在本发明中特别优选的具体化实施方案中,组合物是悬浮液状的液体,其中异氰酸酯是固态表面钝化的异氰酸酯,而异氰酸酯反应性化合物是聚酯聚氨酯的二醇或多官能多元醇。
在这里使用的术语“液体”包括可以在室温下泵送的任何粘度的液体,即也包括浆料。
根据本发明的液态组合物并未显示出恒定的熔点,或者当通过使用差式扫描量热计以10℃/分钟的加热速度从-40℃开始加热时进行分析时显示出低于室温的温度。
所述稳定的液态组合物可以在室温下无需熔融在基层上,以及在无需固定的情况下放置在基层上来便于施用。由于组合物在室温下为液体的事实,所以观察不到“pop off现象”。
在这样一个液态组合物中,优选地,聚酯聚氨酯的数均分子量为1500Da~3000Da。优选地,通过使聚己内酯二醇或多元醇与不对称二异氰酸酯反应得到聚酯聚氨酯。在这样一个具体化实施方案中,优选地,聚己内酯二醇或多元醇的数均分子量为500Da~1500Da。优选地,不对称二异氰酸酯为甲苯二异氰酸酯或异佛乐酮二异氰酸酯或其混合物。进一步优选地,聚己内酯二醇或多元醇的羟基与不对称二异氰酸酯的异氰酸酯基的比率为1.2~3,更优选为1.5~2.5。
由于前述的理想特性,即易于在室温下加工、不存在“pop off现象”,优选包含这种液态组合物的粘合剂。
进一步地,优选包含热塑性组合物和液态组合物的粘合剂。也被指定为“快速固定组合物”的这种粘合剂,具有非常小的收缩率和“pop-off”特性。
由于在使用粘合剂之后的玻璃基层没有应力,所以上述粘合剂特别适用于金属与玻璃的粘合,例如在安装铰链和螺栓的情况中,或将其用于车身顶盖模块的粘合。上述的粘合剂液体还特别适合于工程用聚合物的粘合,特别是聚碳酸酯混合物。
实施例:
通过下述方法,可获得稳定的聚氨酯反应性组合物:
将聚酯、聚碳酸酯及其混合物的二醇或多官能多元醇作为异氰酸酯反应性化合物;聚酯得自于羟基化羧酸或其相应的内酯,且以液态方式存在;并向其中加入含有至少两个伯胺基的化合物。然后加入固态异氰酸酯。最后加入含有异氰酸酯反应性化合物和具有空间位阻效应的铋催化剂的混合物。如果在添加固态异氰酸酯后,再添加含有异氰酸酯反应性化合物以及具有至少两个胺基的化合物的混合物,就可以得到尤为稳定的聚氨酯反应性组合物。在一个优选的具体化实施方案中,在添加含有异氰酸酯反应性化合物和具有空间位阻效应的铋催化剂的混合物之前,先添加聚合的三元伯胺。
实施例1到10
按如下步骤制备根据本发明的聚氨酯反应性组合物:
预混物:在60℃下,在实验用行星式混合器中熔融173.25g重均分子量为2000的聚己内酯二醇(TONE 1241,DOW),并混入72.19g干燥炭黑(Printex 30,Degussa)、22.79g分子筛3A(Purmol 3A,Chemische Fabrik Uetikon)和5.25g催化剂(见下面所列出)。将该混合物在60℃、20mbar压力下进行30分钟的脱气处理。
制备可热固化的聚氨酯反应性组合物:在60℃下,在实验用行星式混合器中熔融83.62g重均分子量为2000的聚己内酯二醇(TONE1241,DOW);在60℃和1013mbar压力下,用5分钟时间混入3.50gJeffamin D-400(聚乙二醇二胺);然后在60℃和1013mbar压力下,用10分钟时间混入47.92g二聚2,4-甲苯二异氰酸酯(Metalink U,Acima)并且在氮气、60℃和1013mbar压力下,加入25.74g混合物,该混合物为含有4.82%聚乙二醇二胺的重均分子量为2000的熔融聚己内酯二醇;在60℃和20mbar压力下,用10分钟时间加入6.90g重均分子量为5000的聚乙二醇三胺(Jeffamine T-5000,Huntsman);最后,将182.32g预混物在60℃和20mbar压力下混合20分钟。
催化剂(见预混物)
根据本发明的催化剂为:
1、新癸酸铋(Neobi 200,Shepherd)
对比实施例:
2、辛酸铋(Chem.Fabrik Uetikon)
3、羧酸铋混合物(BiCat VM,Shepherd)
4、二月桂酸二丁基锡(Fluka)
5、二乙酸二丁基锡(Fluka)
6、二羧酸二丁基锡(UL-8Witco)
7、新癸酸锌(BiCat ZM,Shepherd)
8、新癸酸钴(NeoCo 205PR,9%甲苯溶液,Shepherd)
9、辛酸钴(OctCo 120XL,Shepherd)
10、双吗啉基二乙基醚(DMDEE,Chem.Fabrik Schweizerhalle)
为了用于测试,将这些组合物填满至加热筒中,并将其加热至热塑性组合物的软化温度之上,并挤出基层,如表1、2和3所示。
在不同条件下,测定固化后的拉伸强度,抗拉剪切强度和断裂伸长率。为了测定模量和断裂伸长率,根据DIN方法53504制备哑铃状样品。根据EN 1465方法,以10mm/分钟速度测试2mm厚样品的抗拉剪切强度。结果见表1。
表1
催化剂 | 拉伸强度a.7dRT(*)/(MPa) | 断裂伸长率a.7dRT(*)/(%) | 拉伸强度a.7dCata(**)/(MPa) | 断裂伸长率a.7dCata(**)/(%) | 抗拉剪切强度a.7dRT(*)/(MPa) | 抗拉剪切强度a.7dCata(**)/(MPa) | DSC测量的反应峰/(℃) | DSC固化范围/(℃) |
1(见本 | 29.8 | 389 | 21.8 | 399 | 19.0 | 17.9 | 111 | 101-126 |
发明) | ||||||||
2(参考) | 23.2 | 339 | 23.0 | 343 | 15.0 | 10.4 | 111 | 104-122 |
3(参考) | 26.8 | 370 | 20.3 | 367 | 16.9 | 11.7 | 108 | 101-118 |
4(参考) | 29.1 | 410 | 0.1 | --- | 20.2 | 0.7 | 111 | 101-123 |
5(参考) | 16.2 | --- | 分解 | 分解 | 14.9 | 分解 | 109 | 102-121 |
6(参考) | 21.6 | 450 | 分解 | 分解 | 18.9 | 分解 | 102 | 81-119 |
7(参考) | 不稳定(在室温下日后在加热筒中固化) | 94/122 | 82-200 | |||||
8(参考) | 14.9 | 195 | 16.8 | 231 | 11.7 | 8.4 | 113 | 99-153 |
9(参考) | 18.6 | 276 | 18.9 | 312 | 13.0 | 12.7 | 102 | 89-145 |
10(参考) | 23.7 | 400 | 19.4 | 419 | 14.3 | 11.0 | 121 | 101-185 |
(*)采用在23℃和50%相对湿度进行老化7天后对固化样品测量。
(**)采用在23℃和50%相对湿度进行老化7天后,并继而于-40℃停放16小时和室温下停放2小时后对固化样品的测量。
实施例11至19
预混物1:在氮气下,在实验用行星式混合器中,用5分钟时间以高速混合(x)g组分A和(x)g组分B(组分和(x)值的定义如下)来制备预混物1。
预混物2:在20mbar压力下,在实验用行星式混合器中,用30分钟时间混合(x)g组分A(以及在实施例15中的(x)g组分A1)、(x)g组分E、(x)g组分F和(x)g组分G(组分和(x)值的定义如下)来制备预混物2。
可热固化的聚氨酯反应性组合物的制备:在氮气和1013mbar压力下,在实验用行星式混合器中,用5分钟的时间将(x)g组分A和(x)g组分B混合均匀。然后在氮气、1013mbar压力下,用10分钟的时间将(x)g组分C混入并混合均匀,并且用5分钟时间将(x)g预混物1混入。随后在20mbar压力下,用10分钟时间将(x)g组分D混入。最后,在20mbar压力下,用20分钟时间将(x)g预混物2混入。
组分B:Jeffamin D-400(聚乙二醇二胺,重均分子量400)
组分C:Metalink U(二聚2,4-甲苯二异氰酸酯)
组分D:Jeffamin T-5000(聚乙二醇三胺,重均分子量5000)
组分E:Printex 30(碳黑)
组分F:Purmol 3A(分子筛3A)
组分G:Neobi 200(新癸酸铋)
根据本发明的实施例
实施例11
组分A:Tone 1241DOW,(聚己内酯二醇(起始于1,4-丁二醇),重均分子量2000)
实施例12
组分A:TONE 0240 DOW,(聚己内酯二醇(起始于二乙烯基乙二醇),重均分子量2000)
实施例13
组分A:Ravecarb 107,Enichem,(聚碳酸酯二醇(基于二甲基碳酸酯),重均分子量1850)
参考实施例
实施例14
组分A:Dynacoll 7360,Degussa Hüls,(聚酯二醇(基于1.6-二羟基正己烷,脂肪酸),重均分子量3500)
实施例15
组分A:TONE 2241 DOW,(聚己内酯二醇(起始于新戊基乙二醇),重均分子量2000)
组分A1:Tegomere H5002Goldschmidt,(聚丙烯酸酯多元醇(几种不同的丙烯酸酯),重均分子量467)
实施例16
组分A:Desmophen 1800 Bayer,(轻度支化的聚酯多元醇,重均分子量944)
实施例17
组分A:Desmophen 1652 Bayer,(直链聚酯多元醇,重均分子量1063)
实施例18
组分A:Desmophen 1700 Bayer,(直链聚酯多元醇,重均分子量1308)
实施例19
组分A:Acclaim 2200 Lyondell,(PO-聚醚二醇,重均分子量2000)
混合温度:固态(热塑性的)多元醇:60℃;液态多元醇:40℃
Ex.11 | Ex.12 | Ex.13 | Ex.14 | Ex.15 | Ex.16 | Ex.17 | Ex.18 | Ex.19 | |
g | g | g | g | g | g | g | g | g | |
预混物1组分A组分B | 36.751,86 | 36.751,86 | 36.751,86 | 36.751,86 | 35.442.21 | 36.751,86 | 36.751,86 | 36.751,52 | 36.751,86 |
预混物2组分A组分A1组分E组分F组分G | 173.25---72.1922.795.25 | 173.25---72.1922.795.25 | 163.96---72.1936.755.25 | 209.84---78.7526.255.25 | 70.9396.2369.6221.955.04 | 173.25---84.0026.155.25 | 173.25---72.1922.795.25 | 173.25---84.0026.155.25 | 173.25---72.1922.795.25 |
混合物组分A组分B组分C预混物1组分D预混物2 | 83.623.5047.9225.746.90182.32 | 83.623.5047.9225.746.90182.32 | 80.503.5047.9225.746.90185.43 | 70.003.5030.4525.746.90213.40 | 80.714.2457.4025.106.72175.84 | 73.503.5047.9225.746.90192.43 | 83.623.5047.9225.746.90182.32 | 83.622.8138.5025.526.90192.68 | 83.623.5047.9225.746.90182.32 |
总计 | 350 | 350 | 350 | 350 | 350 | 350 | 350 | 350 | 350 |
通过下面的方法,可以获得稳定的液态聚氨酯反应性组合物:
使用液态聚酯聚氨酯的二醇或多官能多元醇来作为异氰酸酯反应性化合物。通过使聚酯二醇或多元醇与不对称二异氰酸酯反应,而得到具有两个或更多个功能性羟基的所述聚酯聚氨酯。优选地,聚酯二醇或多元醇,作为聚酯聚氨酯的基本原料,为聚己内酯二醇或多元醇。更优选地,聚己内酯二醇或多元醇的数均分子量为500Da~1500Da。
然后加入固态异氰酸酯。最后,加入包含异氰酸酯反应性化合物和具有空间位阻效应的铋催化剂的混合物。
下述实施例20和21均涉及根据本发明的液态聚氨酯反应性组合物的制备方法。
实施例20和21
通过下述方法制备下述液态预聚物A和B:
a)预聚物A的制备(聚己内酯二醇与异佛乐酮二异氰酸酯的化学计量比为2∶1)
将435.01gTONE 32C8(起始于1,6-正己烷二醇的聚己内酯二醇,重均分子量750,DOW),0.50g新癸酸铋(NeoBi200,Shepherd和64.49g异佛乐酮二异氰酸酯加入到实验用反应器中,并在氮气、80℃下混合及加热120分钟,得到不含NCO基的聚己内酯-聚氨酯。所得到的预聚物具有下列性质:室温下为液态,数均分子量=1720(通过OH滴定法计算)。
b)预聚物B的制备(聚己内酯二醇和甲苯二异氰酸酯的化学计量比为3∶2)
将432.45gTONE 32C8(起始于1,6-正己烷二醇的聚己内酯二醇,重均分子量750,DOW),0.66g新癸酸铋(NeoBi200,Shepherd)和66.89g甲苯二异氰酸酯加入到实验用反应器中,并在氮气、80℃下混合及加热120分钟,得到不含NCO基的聚己内酯-聚氨酯。所得到的预聚物具有下列性质:室温下为液态,数均分子量=2600(通过OH滴定法计算)。
作为一个对比实施例,使用不对称的异氰酸酯制备固态预聚物C。
c)预聚物C的制备(聚己内酯二醇和己烯二异氰酸酯的化学计量比为2∶1)
将449.00g TONE 32C8(起始于1,6-正己烷二醇的聚己内酯二醇,重均分子量750,DOW),0.65g新癸酸铋(NeoBi200,Shepherd)和50.35g 1,6-己烯二异氰酸酯加入到实验用反应器中,并在氮气、80℃下混合及加热120分钟,得到不含NCO基的聚己内酯-聚氨酯。所得到的预聚物具有下列性质:室温下为固态、晶体,数均分子量=1670(通过OH滴定法计算)。
实施例20:
在60℃、真空(20mbar)下,使169.05g从步骤a)中得到的预聚物A、70.40g炭黑(Printex 30,Degussa)、22.21g分子筛3A和5.25g新癸酸铋(NeoBi200,Shepherd)在行星式混合器中混合30分钟,得到预混物。然后,在行星式混合器中按下面步骤制得聚氨酯反应性组合物:使81.59g从步骤a)中获得的预聚物和4.10gJeffamine D-400(聚乙二醇二胺,重均分子量400,Huntsman)在50℃下混合5分钟。然后在氮气、50℃下,使54.30gMetalink U(2,4-甲代亚苯基二异氰酸酯的脲化物,Acima)高速混入10分钟。然后在氮气下,高速加入6.15%Jeffamine D-400的在步骤a)中获得的预聚物A溶液25.37g。接着,将混合物的压力从常压减小至20mbar,并以中速在50℃下混入6.72gJeffamine T-5000(聚乙二醇三胺,重均分子量5000,Huntsman)10分钟。最后,加入177.92g上述预混物并搅拌20分钟。压力逐渐回到常压,并且得到液态的高粘度聚氨酯反应性组合物。
实施例21:
在60℃、真空(20mbar)下,将从步骤b)中得到的180.02g预混物、74.97g炭黑(Printex 30,Degussa)、22.00g分子筛3A和5.25g新癸酸铋(NeoBi200,Shepherd)在行星式混合器中混合30分钟。然后,在行星式混合器中按下面步骤制得聚氨酯反应性组合物:使86.89g从步骤a)中得到的预聚物和3.15gJeffamine D-400(聚乙二醇二胺,重均分子量400,Huntsman)在50℃下混合5分钟。使38.50g MetalinkU(2,4-甲代亚苯基二异氰酸酯的脲化物,Acima)在氮气、50℃下高速混入10分钟。然后,在氮气下,高速加入2.75%Jeffamine D-400的在从步骤b)中得到的预聚物B溶液26.15g。接着,将混合物的压力从常压减小至20mbar,并在50℃下,以中速混入7.14gJeffamine T-5000(聚乙二醇三胺,重均分子量5000,Huntsman)10分钟。最后,加入188.17g上述预混物并搅拌20分钟。压力逐渐回到常压,并得到液态的高粘度聚氨酯反应性组合物。
在不同条件下,测定固化后的拉伸强度,抗拉剪切强度和断裂伸长率。结果见表2。
实施例22
从实施例11中得到的粘合剂可用于挂钩或将柱头螺栓安装到汽车门玻璃上的粘合。柱头螺栓用于门闩原件的支撑作用。首先在玻璃的粘接一面上使用Betaprime 435.26(Dow汽车的玻璃底漆)涂抹玻璃并使其在标准环境下干燥4小时。用钢铁制造挂钩,并且用酚醛树脂涂抹其直径为40mm的原形底盘以使其粘接于其上。在使用粘合剂之前,用丙酮清洗粘接面。将温度为60℃的粘合剂挤到圆盘上,并且快速将挂钩与玻璃的粘接面融紧密结合且固定,以使粘合剂层的厚度为1mm。
通过使用以挂钩面积来定形的线圈中发生的电磁感应固化粘合剂。在固化周期中,用10秒钟将粘合剂加热至80℃,并在该温度下保持30秒,然后用20秒钟加热至150℃,并在该温度下保持2分钟,随后冷却。
需要对这种材料测试在常温下1天后承受负荷的附着力。将弹性测试夹具与柱头螺栓的螺纹端相连,并外加100Kg的拉力。将该装置放置于95℃的循环烘箱中,在两天的测试期之前,如果发生失败,记下失败时间。粘合剂在95℃下的48小时内不会失败。
表2
催化剂 | 拉伸强度a.7dRT(*)/(MPa) | 断裂伸长率a.7dRT(*)/( | 拉伸强度a.7dCata(**)/(MPa) | 断裂伸长率a.7dCata | 抗拉剪切强度a.7dRT(*)/( | 抗拉剪切强度a.7dCata | 熔融峰/(℃) | 固化峰/(℃) |
%) | (**)/(%) | MPa) | (**)/(MPa) | |||||
11(根据本发明) | 29.8 | 389 | 21.8 | 399 | 19.0 | 17.9 | 51 | 111 |
12(根据本发明) | 26.2 | 402 | 19.0 | 392 | 19.4 | 16.3 | 51 | 113 |
13(根据本发明) | 29.7 | 471 | 19.8 | 401 | 20.0 | 16.8 | --- | 109 |
14(参考) | 13.3 | 391 | 6.7 | --- | 19.1 | 4.1 | 59 | 105 |
15(参考) | 13.9 | 163 | 9.7 | 148 | 10.4 | 8.7 | 48 | 114 |
16(参考) | 8.6 | 118 | 6.0 | 135 | 9.9 | 3.6 | --- | 113 |
17(参考) | 22.3 | 983 | 2.5 | 545 | 16.7 | 2.5 | --- | 112 |
18(参考) | 19.3 | 545 | 1.6 | 393 | 14.0 | 0.9 | --- | 114 |
19(参考) | --- | --- | --- | --- | 7.8 | 5.6 | --- | 123 |
20(根据本发明) | 331 | 429 | 19.0 | 498 | 17.4 | 15.1 | --- | 102 |
21(根据本发明) | 32.3 | 509 | 18.0 | 506 | 20.3 | 16.2 | --- | 94 |
表3给出实施例11到19在抗拉剪切测试中的失败方式
表3
外涂层在抗拉剪切测试中的失败方式 | ||
7dRT(*) | 7d Cata(**) | |
实施例11 | 75%cf/25%e-coat | 20%cf/80%e-coat |
实施例12 | 55%cf/45%e-coat | 85%cf/15%e-coat |
实施例13 | 50%steel/50%e-coat | 45%cf/55%e-coat |
实施例14 | 60%cf/40%af | 100%af |
实施例15 | 100%cf | 95%cf/5%af |
实施例16 | 100%cf | 35%cf/65%af |
实施例17 | 35%cf/50%steel/15%af | 100%af |
实施例18 | 75%cf/25%e-coat | 50%cf/50%bf |
实施例19 | 100%cf | 80%cf/20%af |
cf:固化材料的粘结失败
steel:钢铁破裂
e-coat:外包覆破裂
bf:边界失败(接近界面处破裂)
af:粘合剂失败
冲击测试性能:
将测试实施例1和13的组合物的抗冲击性。通过使用相应的组合物来作为粘合剂,将电镀的外包覆钢盘放置在一起组成所谓“匣形梁”。对匣形梁进行“自由下落冲击”测试。使用冲击锤以给定速度击打匣形梁,测定冲击后的变形。图1显示出所谓“匣形梁”(1),即用粘合剂(3)将两个钢盘(2)粘接在一起。钢盘(2)的尺寸如下:A=22.5mm,B=46mm,C=200mm,D=15mm。钢盘(2)的厚度为0.62mm,粘合剂(3)的厚度为1mm。图2显示出匣形梁(1)和冲击砝码(4)的排列方式。自由下落的高度分别是5m或8m。结果见表4。
表4
H=5m自由下落 | H=8m自由下落 | |||||||
粘合剂厚度 | 固化后的保存期 | 冲击后变形率(%) | G* | 粘结失败 | 冲击后变形率(%) | G | 粘结失败 | |
实施例1 | 1mm | RT | 43.0 | 58.1 | 无 | 65.5 | 61.1 | 无 |
实施例1 | 1mm | Cata-plasma | 36.0 | 69.4 | 无 | --- | --- | --- |
实施例13 | 1mm | RT | 32.0 | 78.1 | 无 | 51.0 | 78.4 | 无 |
热结构EP粘合剂 | 0.2mm | RT | 全部失败 | 全部失败 |
*G=减速
冲击砝码重量 | 冲击速度 | 冲击能 | |
自由下落 | 33.3Kg | 35.7km/h | 1633J |
自由下落 | 33.3Kg | 45.1km/h | 2613J |
实施例1、11和13的断裂伸长率、拉伸强度在图中画出,并将其与传统的环氧树脂和传统的聚氨酯进行对比。图3显示出,根据本发明的组合物经固化后生产的聚氨酯(PU)显示出高断裂伸长率,并同时具备在环氧树脂(EP)拉伸强度范围内的拉伸强度。在图3中的缩写具有下列含义
PU-DG:用于直接上光的高模量聚氨酯
PU-SS:半结构聚氨酯
PU-S:结构聚氨酯
EP-S:结构环氧树脂
E.1/11:实施例1/11
E.13:实施例13
图4进一步表示了根据本发明的组合物经固化后生产的聚氨酯同时具备高断裂伸长率和高拉伸强度。
Claims (26)
1.一种可热固化的聚氨酯反应性组合物,包含异氰酸酯、异氰酸酯反应性化合物,以及用于使异氰酸酯与异氰酸酯反应性化合物反应的催化剂;其中,异氰酸酯反应性化合物是聚酯、聚酯聚氨酯、聚碳酸酯或其混合物的二醇或多官能多元醇;其中聚酯得自于羟基化羧酸或相应的内酯,而催化剂是具有空间位阻效应的铋化合物。
2.一种可热固化的聚氨酯反应性组合物,包含固态表面的钝化异氰酸酯、异氰酸酯反应性化合物、以及用于异氰酸酯与异氰酸酯反应性化合物反应的催化剂;其中,异氰酸酯反应性化合物是聚酯或聚碳酸酯的二醇或多官能多元醇或其混合物;其中聚酯得自于羟基化羧酸或相应的内酯,而催化剂是具有空间位阻效应的铋化合物。
3.根据权利要求2所述的组合物,其中固态表面的钝化异氰酸酯是甲苯二异氰酸酯脲或uretdion。
4.根据权利要求2或3所述的组合物,包含固态表面钝化的异氰酸酯,其表面被没有空间位阻效应的二元或三元伯胺或其混合物所钝化。
5.根据上述权利要求任一所述的组合物,其中聚酯是聚己内酯、聚丁内酯、聚戊内酯或其混合物。
6.根据上述权利要求任一所述的组合物,所述组合物为热塑性的,且在室温下为固态。
7.根据上述权利要求任一所述的组合物,所述组合物为热塑性的,且在室温下为固态,并且除热塑性的聚酯之外,还包含至少30%,优选地,包含至少为多元醇总重量的50%的聚碳酸酯的液态二醇或多官能多元醇。
8.根据权利要求1所述的组合物,所述组合物在室温下为液态,其中异氰酸酯是固态表面钝化的异氰酸酯,并且异氰酸酯反应性化合物是聚酯聚氨酯的二醇或多官能多元醇。
9.根据权利要求8的组合物,其中聚酯聚氨酯数均分子量为1500Da~3000Da。
10.根据权利要求8或9所述的组合物,其中异氰酸酯反应性化合物是聚酯聚氨酯的二醇或更高官能多元醇,通过使聚己内酯二醇或多元醇与不对称二异氰酸酯反应可以得到该聚酯聚氨酯。
11.根据权利要求10所述的组合物,其中聚己内酯二醇或多元醇的数均分子量为500Da~1500Da.。
12.根据权利要求10或11所述的组合物,其中不对称二异氰酸酯是甲苯二异氰酸酯或异佛乐酮二异氰酸酯或者其混合物。
13.根据权利要求10到12任一所述的组合物,其中聚己内酯二醇或多元醇的羟基与不对称二异氰酸酯的异氰酸酯基的比率为1.2~3。
14.根据权利要求13所述的组合物,其中聚己内酯二醇或多元醇的羟基与不对称二异氰酸酯的异氰酸酯基的比率为1.5~2.5。
15.根据上述权利要求任一所述的组合物,其中催化剂是新癸酸铋。
16.根据上述权利要求任一所述的组合物,包含具有空间位阻效应的锑化合物。
17.根据上述权利要求任一所述的组合物,包含一种或多种组分,选自:填料、稳定剂、干燥剂、粘合促进剂、低分子异氰酸酯反应性扩链剂、流变助剂或增塑剂。
18.一种含有根据上述权利要求所述组合物的粘合剂。
19.根据权利要求18所述的粘合剂,包含根据权利要求6所述的固态热塑性组合物和根据权利要求8所述的液态组合物。
20.一种可通过对根据权利要求1到19所述组合物进行热固化而得到的聚氨酯。
21.一种制备根据权利要求2所述的可热固化的聚氨酯反应性组合物的方法,包括以下a到c三个连续步骤:
a)使聚酯或聚碳酸酯或其混合物的二醇或多官能多元醇作为异氰酸酯反应性化合物;聚酯得自羟基化羧酸或其相应的内酯,且为液态;并加入含有至少两个伯胺基的化合物;
b)加入固态异氰酸酯;以及
c)加入含有异氰酸酯反应性化合物和具有空间位阻效应的铋催化剂的混合物。
22.一种制备根据权利要求8所述的可热固化的聚氨酯反应性组合物的方法,包括以下a到c三个连续步骤:
a)使聚酯聚氨酯的液态二醇或多官能多元醇作为异氰酸酯反应性化合物;
b)加入固态异氰酸酯;以及
c)加入含有异氰酸酯反应性化合物和具有空间位阻效应的铋催化剂的混合物。
23.根据权利要求22所述的方法,其中聚酯聚氨酯的数均分子量为1500Da~3000Da。
24.根据权利要求22或23所述的方法,其中异氰酸酯反应性化合物是聚己内酯聚氨酯的二醇或多官能多元醇。
25.根据权利要求21到24任一所述的方法,其中在步骤b)加入固态异氰酸酯之后,加入含有异氰酸酯反应性化合物和具有两个或更多个胺基的化合物的混合物。
26.根据权利要求25所述的方法,其中在加入异氰酸酯反应性化合物和具有空间位阻效应的铋催化剂的混合物之前,加入聚合的三元伯胺。
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Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102005013329A1 (de) * | 2005-03-23 | 2006-11-16 | Degussa Ag | Niedrigviskose uretdiongruppenhaltige Polyadditionsverbindungen, Verfahren zur Herstellung und Verwendung |
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US9133377B2 (en) * | 2010-05-20 | 2015-09-15 | A. Raymond Et Cie | Adhesive polyurethane powder capable of being activated by heat |
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WO2016085938A1 (en) * | 2014-11-26 | 2016-06-02 | Cytec Industries Inc. | Multi-part polyurethane compositions, articles thereof, and method of making |
DE102015012015A1 (de) * | 2015-08-05 | 2017-02-09 | Ewald Dörken Ag | Mehrschichtverbundfolie, vorzugsweise für den Baubereich |
JP6576166B2 (ja) * | 2015-08-31 | 2019-09-18 | 日本カーバイド工業株式会社 | インキ及び積層体 |
BR112018016197A2 (pt) | 2016-02-17 | 2018-12-18 | Dow Global Technologies Llc | composições contendo pré-polímeros com funcionalidade isocianato e nanoargilas modificadas com amônio quaternário |
EP3430065A1 (de) | 2016-03-18 | 2019-01-23 | Basf Se | Feinteilige wässrige mehrstufige polymerisatdispersion, verfahren zu deren herstellung und deren verwendung als bindemittel |
US11505638B2 (en) | 2017-04-28 | 2022-11-22 | Derrick Corporation | Thermoplastic compositions, methods, apparatus, and uses |
AU2021293105B2 (en) * | 2020-06-18 | 2024-01-25 | Derrick Corporation | Thermoplastic compositions, methods, apparatus, and uses |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MY102340A (en) * | 1986-03-27 | 1992-06-17 | Ashland Oil Inc | Tin or bismuth complex catalysts and trigger cure of coatings therewith. |
US4788083A (en) * | 1986-03-27 | 1988-11-29 | Ashland Oil, Inc. | Tin or bismuth complex catalysts and trigger cure of coatings therewith |
DE3820705A1 (de) * | 1988-06-18 | 1989-12-21 | Basf Ag | Lagerstabile, hitzehaertbare stoffmischungen, enthaltend oberflaechenmodifizierte polyisocyanate und verbindungen mit reaktiven wasserstoffatomen, und ihre verwendung zur herstellung von folien |
DE4111655A1 (de) * | 1991-04-10 | 1992-10-15 | Bayer Ag | Einkomponenten-reaktivklebstoffe auf polyurethanbasis |
DE4113416A1 (de) * | 1991-04-25 | 1992-10-29 | Bayer Ag | Polyisocyanatsuspensionen in gegenueber isocyanatgruppen reaktionsfaehigen verbindungen und ihre verwendung |
WO1993025599A1 (de) * | 1992-06-15 | 1993-12-23 | Abend Thomas P | Verfahren und stoffmischung zur herstellung reaktiver schmelzmassen |
DE4407490A1 (de) * | 1994-03-07 | 1995-09-14 | Bayer Ag | Verfahren zur Herstellung heißhärtender Einkomponenten-Polyurethan-Reaktivmassen |
WO1996000754A1 (en) * | 1994-06-30 | 1996-01-11 | Minnesota Mining And Manufacturing Company | Polyurethane/urea elastomeric sealants |
DE19532294A1 (de) * | 1995-09-01 | 1997-03-06 | Huels Chemische Werke Ag | Flüssige Einkomponenten-PUR-Einbrennlacke |
JPH10204379A (ja) * | 1997-01-22 | 1998-08-04 | Sanyo Chem Ind Ltd | 耐チッピング塗料用組成物 |
US6258918B1 (en) * | 1998-04-22 | 2001-07-10 | 3M Innovative Properties Company | Flexible polyurethane material |
JP3936813B2 (ja) * | 1998-10-29 | 2007-06-27 | 三洋化成工業株式会社 | 摺動性ウレタンエラストマー成形体 |
JP3873269B2 (ja) * | 2000-01-25 | 2007-01-24 | 日本ポリウレタン工業株式会社 | 低硬度ポリウレタンエラストマー形成性一液組成物からなる密封容器用シール素材 |
JP2002060727A (ja) * | 2000-08-21 | 2002-02-26 | Nippon Polyurethane Ind Co Ltd | 天蓋パッキン用組成物及び該組成物を用いた天蓋パッキンの製造方法 |
DE10106630A1 (de) * | 2001-02-12 | 2002-08-22 | Jowat Lobers U Frank Gmbh & Co | Selbsttragendes reaktives Schmelzklebeelement und seine Verwendung |
-
2002
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Cited By (7)
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CN104110246A (zh) * | 2013-04-19 | 2014-10-22 | 中国石油集团长城钻探工程有限公司 | 至少检测三维阵列感应测井仪轴向线圈同心度的平台 |
CN105793327A (zh) * | 2013-10-28 | 2016-07-20 | 亨茨曼国际有限公司 | 金属化的多面体低聚倍半硅氧烷催化剂组合物的合成及用途 |
CN105793327B (zh) * | 2013-10-28 | 2019-12-17 | 亨茨曼国际有限公司 | 金属化的多面体低聚倍半硅氧烷催化剂组合物的合成及用途 |
CN103897132A (zh) * | 2014-04-02 | 2014-07-02 | 全洪晖 | 一种柔性的水性异氰酸酯固化剂的制备方法 |
CN103897132B (zh) * | 2014-04-02 | 2016-02-03 | 全洪晖 | 一种柔性的水性异氰酸酯固化剂的制备方法 |
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KR20050084463A (ko) | 2005-08-26 |
EP1671996A2 (en) | 2006-06-21 |
US20050137376A1 (en) | 2005-06-23 |
EP1433802A1 (en) | 2004-06-30 |
EP1578834A1 (en) | 2005-09-28 |
BR0317204B1 (pt) | 2013-04-30 |
EP1433802B1 (en) | 2007-10-17 |
WO2004056903A1 (en) | 2004-07-08 |
KR101087946B1 (ko) | 2011-11-28 |
BR0317204A (pt) | 2005-11-01 |
AU2003296249A1 (en) | 2004-07-14 |
JP2006511639A (ja) | 2006-04-06 |
CA2508259A1 (en) | 2004-07-08 |
US6965008B2 (en) | 2005-11-15 |
ATE376015T1 (de) | 2007-11-15 |
EP1671996A3 (en) | 2008-11-26 |
CN1318472C (zh) | 2007-05-30 |
EP1578834B1 (en) | 2015-02-18 |
ES2291434T3 (es) | 2008-03-01 |
EP1671996B1 (en) | 2017-09-13 |
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