CN1114641C - 包括微孔聚氨酯泡沫塑料的模塑制品 - Google Patents
包括微孔聚氨酯泡沫塑料的模塑制品 Download PDFInfo
- Publication number
- CN1114641C CN1114641C CN98807553A CN98807553A CN1114641C CN 1114641 C CN1114641 C CN 1114641C CN 98807553 A CN98807553 A CN 98807553A CN 98807553 A CN98807553 A CN 98807553A CN 1114641 C CN1114641 C CN 1114641C
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- CN
- China
- Prior art keywords
- moulded parts
- diphenylmethane diisocyanate
- allophanate
- molecular weight
- alcohol
- 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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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 22
- 239000004814 polyurethane Substances 0.000 title description 11
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- 239000012948 isocyanate Substances 0.000 claims abstract description 35
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 34
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 22
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- 239000011496 polyurethane foam Substances 0.000 claims abstract description 5
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- 229920000570 polyether Polymers 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
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- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 5
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- 239000005056 polyisocyanate Substances 0.000 description 5
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- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical class CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 3
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
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- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 3
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Classifications
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- C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
本发明涉及包括微孔聚氨酯泡沫塑料、优选连皮泡沫塑料的模塑制品。这些模塑制品显示了改进的性能并且特别适用于鞋类中的鞋底体系。本发明还涉及生产这些模塑制品的方法。这些模塑制品包括(A)异氰酸酯与(B)异氰酸酯反应性组分在(C)至少一种吹塑剂存在下的反应产物,(A)中所述异氰酸酯包括稳定的液态MDI基预聚物,该预聚物包含脲基甲酸酯改性的MDI。
Description
发明背景
本发明涉及具有改进性能的连皮泡沫塑料及生产这种泡沫的方法。这些泡沫是由包括稳定的液态二苯基甲烷二异氰酸酯(MDI)基预聚物的异氰酸酯制备的,所述MDI基预聚物含有脲基甲酸酯改性的MDI。
液态二苯甲烷二异氰酸酯及其在制备连皮泡沫塑料方面的应用通常是本领域已知的。各种类型的液态二苯甲烷二异氰酸酯包括例如异氰酸酯预聚物、含有脲基甲酸酯基团的异氰酸酯、含有碳化二亚胺基团的异氰酸酯、含有缩二脲基团的异氰酸酯等。这些描述于例如美国专利3,644,457、4,055,548、4,115,429、4,118,411、4,160,080、4,261,852、4,490,300、4,7 38,991和4,866,103及GB994,890中。
由聚氨酯制备的连皮泡沫塑料在本领域也是为人熟知的。这些描述于例如美国专利3,523,918、3,72 6,952、3,836,487、3,925,527、4,020,001、4,024,090、4,065,410、4,305,991和5,166,183;及CA1,277,471。
美国专利3,644,457公开了由1mol二苯甲烷二异氰酸酯和0.1-0.3mol聚-1,2-亚丙基醚二醇衍生得到的室温稳定的液态异氰酸酯。
美国专利4,055,548公开了通过使包含约65-85wt%亚甲基二苯基异氰酸酯的聚亚甲基聚苯基异氰酸酯与分子量为200-600的聚氧乙二醇以0.0185-0.15∶1的当量比反应而获得的液态异氰酸酯预聚物组合物。
美国专利4,115,429和4,118,411公开了低温(低至-5℃)储存稳定的液态二苯基二异氰酸酯,它是通过使具有特定的2,4-异构体含量的二苯基二异氰酸酯与丙二醇或聚-1,2-亚丙基醚二醇反应制备的。
美国专利4,261,852公开了液态多异氰酸酯组合物,它们包括(a)90-50wt%二苯甲烷二异氰酸酯和羟基当量重量为750-3000的聚氧丙二醇或三醇的反应产物,所述反应产物的NC0含量为8-26wt%,和(b)约10-50wt%二苯甲烷二异氰酸酯,其中包含30-65wt%二苯甲烷二异氰酸酯,其余为多亚甲基多苯基多异氰酸酯。
美国专利4,490,300公开了室温稳定的液态异氰酸酯,它是通过使二苯甲烷二异氰酸酯与带有吊挂的芳族基团的脂肪族二醇例如2-甲基-2-苯基-1,3-丙二醇或苯基-1,2-乙二醇反应制得的。
美国专利4,490,301公开了室温稳定的液态异氰酸酯,它是通过使二苯甲烷二异氰酸酯与三羟甲基丙烷的单烯丙基醚反应制得的。
美国专利4,738,991公开了以脲基甲酸酯键为特征的有机多异氰酸酯,它们是在有机金属催化剂存在下通过使包含2,4-和4,4-亚甲基二苯基二异氰酸酯的有机多异氰酸酯与多-或单羟基醇反应制得的。然后使用诸如无机酸、有机酸、有机氯甲酸酯或有机酸酰氯之类的化合物将催化剂钝化。该文献还公开了软质泡沫塑料可由这些含有脲基甲酸酯基团的异氰酸酯制备。所有的实例均涉及TDI基的含有脲基甲酸酯基团的异氰酸酯,而其中只有一种可制备高回弹性的软质泡沫塑料。
美国专利4,866,103公开了用于以RIM方法生产弹性体的多异氰酸酯组合物。该多异氰酸酯组合物是平均官能度为约1.5-约4且平均当量重量至少为500的醇和/或三醇与对应每羟基和/或三醇当量至少2当量的有机多异氰酸酯的反应产物,所述有机多异氰酸酯包含二苯甲烷二异氰酸酯的4,4-和2,4-异构体。所公开的反应是在可使至少约20%开始时形成的氨基甲酸酯和/或硫代氨基甲酸酯基团转化为脲基甲酸酯和/或硫代脲基甲酸酯基团的条件下进行的。
另一个制备含有异氰酸酯的脲基甲酸酯的方法公开于英国专利994,890中,该专利涉及只通过热或者在催化剂存在下氨基甲酸酯异氰酸酯与过量二异氰酸酯的反应,其中的催化剂为例如金属羧酸盐、金属螯合物或叔胺,反应进行直至异氰酸酯含量减少到氨基甲酸酯基团全部反应时理论上可获得的量。
美国专利4,160,080公开了生产含有脂族和/或环脂族键接的异氰酸酯基团的脲基甲酸酯的方法。在该公开方法中,含有氨基甲酸酯基团的化合物与带有脂族和/或环脂族异氰酸酯基团的多异氰酸酯在强酸存在下反应。该过程一般在90℃-140℃进行约4-20小时。
日本专利申请1971-99176公开了通过使二苯甲烷二异氰酸酯与脂族一价醇反应制备液态二苯甲烷二异氰酸酯的方法。
美国专利4,305,991描述并制备了连皮泡沫塑料。这些泡沫是由含有多异氰酸酯的反应混合物制备的,其中异氰酸酯基团是脂族和/或环脂族键接的。这些多异氰酸酯可以含有诸如碳化二亚胺-、脲基甲酸酯-、异氰脲酸酯-、氮氧甲基二酮(uretdione)-、缩二脲-基团之类的加合物。用于制备这些泡沫的脂族异氰酸酯提供了耐紫外光及耐热分解性能。
美国专利5,166,183也描述了连皮泡沫塑料。其中所用的多异氰酸酯组合物的NCO含量约为16-25%,并且由i)10-100重量份的NCO含量约为16-22%的异氰酸酯组成,所述异氰酸酯是通过混合亚甲基二(苯基异氰酸酯)和由碳化二亚胺基团改性的亚甲基二(苯基异氰酸酯),随后与聚酯二醇反应形成产物而制备的。然后将该产物与ii)O-90重量份的NCO含量约为18-25%的改性异氰酸酯混合,所述改性异氰酸酯是通过使亚甲基二(苯基异氰酸酯)与聚-1,2-亚丙基醚二醇反应而制备的。预聚物中存在碳化二亚胺改性的异氰酸酯用来降低凝固点。
据述’183专利的连皮泡沫塑料显示了改进的耐磨性。这是因为在形成预聚物时使用了聚酯。但是聚酯增加了预聚物的成本并且降低了与聚醚的相容性(溶解性)以致使体系的加工困难。
在美国专利5,342,856中也公开了碳化二亚胺改性的异氰酸酯是生产连皮泡沫塑料适宜的异氰酸酯。这些异氰酸酯与异氰酸酯反应性组分及羧酸锌在脂族多元胺中的溶液反应。这些羧酸锌在脂族多元胺和水中的溶液是制备连皮泡沫塑料必需的。
美国专利4,477,602描述了生产具有改进的低温抗挠曲疲劳性和原始强度的聚氨酯的体系。该体系的关键组分为聚脲和/或聚联二脲在有机化合物中的分散体。实施例中也使用CFC-11作为主吹塑剂,水作为辅吹塑剂。
美国专利5,585,409描述了生产具有微孔芯及压实表面区的模塑聚氨酯的方法。这些聚氨酯是由包括异氰酸酯半预聚物和含有至少一个键合酯单元的支链二羟基化合物的体系制备的,所述半预聚物含有由聚酯多元醇制备的酯基团。
美国专利5,624,966描述了生产拉伸强度大于或等于450psi和/或泰伯磨耗(损耗的mg数)小于200的聚氨酯制品的聚氨酯组合物。
美国专利5,514,723描述了对美国专利5,166,183所公开的方法的改进方法。更具体而言,’723专利涉及这样的发现:催化剂的特殊组合提高了’183专利所述的连皮泡沫塑料皮的拉伸强度与芯的拉伸强度的比值。该催化剂组合包括:a)对应于特殊结构式的二有机锡硫化物,b)叔胺,和c)能够催化异氰酸酯基团和活性氢原子之间的反应的锡化合物,条件是c)不是a)中所述的二有机锡硫化物。
1996年7月15日提交的申请者共同未决的普通转让的申请08/680,094(序列号)涉及连皮泡沫塑料。这些泡沫是由包含稳定的液态MDI基预聚物的异氰酸酯制备的,所述预聚物含有脲基甲酸酯改性的MDI。与由不同的异氰酸酯制备的连皮泡沫塑料相比,本申请的连皮泡沫塑料具有卓越的耐磨性。但是这些连皮泡沫塑料未显示鞋类应用所要求的弯曲性能。
此外,当将脲基甲酸酯改性的异氰酸酯用于期望得到较好弯曲性能的配方中时,发现某些脲基甲酸酯改性的异氰酸酯预聚物比在此共同未决的申请中所要求的脲基甲酸酯改性的异氰酸酯更优越。
在上述共同未决的申请中所述的改进的耐磨性在本发明中实际上几乎是没有优势的,因为本发明体系已经通过其它方法获得了卓越的耐磨性。另一方面,在本申请中要求保护的模塑制品的改进的弯曲性能既不因所述的共同未决的申请变得显而易见也不能从中预期。
本发明的目的是开发一种特别适于鞋底或鞋的底面(即鞋类)应用的聚氨酯连皮体系。这要求该体系具有卓越的动态挠曲疲劳性能。优选这些体系使用包含水的吹塑剂。
另一个目的是避免由于使用聚酯扩链的预聚物所造成的缺点。这些缺点包括例如高粘度、高成本和易水解性。
发明概述
本发明涉及一种包括微孔聚氨酯泡沫的模塑制品,优选鞋底,并且涉及生产该包括微孔聚氨酯泡沫的模塑制品的方法。该聚氨酯产物是通过使(A)包含脲基甲酸酯改性的MDI的稳定液态MDI基预聚物与(B)异氰酸酯反应性组分及(C)吹塑剂反应而形成的。具有NCO含量为5-30%的稳定液态MDI基预聚物(A)包含脲基甲酸酯改性的MDI,并且包括1)和2)的反应产物:
1)脲基甲酸酯改性的MDI,它是通过i)和ii)反应制备的:
i)脂族醇或芳族醇,其中所述醇包含的碳原子少于17个,
ii)二苯甲烷二异氰酸酯,它包括约0-60wt%的2,4’-二苯甲烷二异氰酸酯、少于6wt%的2,2’-二苯甲烷二异氰酸酯、且剩余的为4,4’-二苯甲烷二异氰酸酯,
2)包含2-3个羟基基团、优选2个羟基基团且分子量约为750-10,000、优选约1,000-约6,000的聚醚多元醇,其中聚醚多元醇是由起始化合物与环氧乙烷及环氧丙烷以重量比10∶90-70∶30、优选13∶87-50∶50且最优选15∶85-35∶65制备的。
适宜的(B)异氰酸酯反应性组合物包括:
(1)以组分(B)的总重量为基准,约25-约92wt%的至少一种官能度为约2且分子量为约3,000-约8,000的聚醚多元醇,
(2)以组分(B)的总重量为基准,约5-约72wt%的填充多元醇(优选聚脲和/或聚联二脲在含有至少两个羟基基团的有机化合物中的分散体,或苯乙烯-丙烯腈共聚物(SAN)接枝多元醇),其中所述填充的多元醇的官能度为约2.5-3(优选3)且分子量为约3,000-约8,000(优选约4,800-约6,000),和
(3)以组分(B)的总重量为基准,约3-最多约30wt%的至少一种有机化合物,该化合物包含2-4个羟基基团并且分子量为约28-约250。
用作组分(B)(3)的优选化合物为1,4-丁二醇、乙二醇及其混合物,乙二醇是最优选的。
上述组分(A)和(B)在(C)优选包括水的吹塑剂及任选地(D)其它添加剂存在下反应。其它添加剂包括例如一种或多种催化剂和/或一种或多种表面活性剂。
组分(A)和(B)以可使异氰酸酯指数为约90-110、优选约96-103的量存在。
本发明还涉及生产这些包括微孔聚氨酯发泡产物的模塑制品的方法。发明详述
适宜的稳定液态MDI基预聚物的NCO含量为约5-30%,优选15-25%,更优选17-23%,且最优选18-20%,并且包含脲基甲酸酯改性的MDI。这些稳定的液态MDI基预聚物包括1)脲基甲酸酯改性的MDI和2)聚醚多元醇的反应产物。这些异氰酸酯预聚物是已知的并且描述于例如美国专利5,319,053,在此引入其公开内容作为参考。
适宜的1)用于制备稳定的液态MDI基预聚物的脲基甲酸酯改性的MDI包括(i)脂族醇或芳族醇和(ii)二苯甲烷二异氰酸酯的反应产物,其中所述醇包含少于17个的碳原子,优选约2-约8个碳原子,而所述二苯甲烷二异氰酸酯包括约0-60wt%的2,4’-二苯甲烷二异氰酸酯、少于6wt%的2,2’-二苯甲烷二异氰酸酯、且剩余的为4,4’-二苯甲烷二异氰酸酯。一些适于用作脂族醇(i)的化合物包括例如丁醇异构体、丙醇异构体、戊醇异构体、己醇异构体、环已醇、2-甲氧基乙醇、2-溴乙醇等。用于制备脲基甲酸酯改性的预聚物的适宜芳族醇包括例如苯酚、1-萘酚、间甲酚和对溴苯酚。优选的脂族醇为1-丁醇、1-戊醇和1-丙醇。优选的芳族醇为苯酚和间甲酚。脂族醇是特别优选的。
二苯甲烷二异氰酸酯优选包括约0-约6%的MDI的2,4’-异构体、约0-约2%的MDI的2,2’-异构体和约92-约100%的MDI的4,4’-异构体。优选1)脲基甲酸酯改性的MDI也是稳定的液体并且NCO含量约为15-30%。
将要与1)脲基甲酸酯改性的MDI反应形成本发明所要求的包含脲基甲酸酯改性的MDI的稳定液态MDI预聚物A)的适宜聚醚多元醇2)包括含有约1.5-3个羟基基团、优选1.8-3个羟基基团、更优选2-3个且最优选2个羟基基团并且分子量为约750-约10,000、优选约1,000-6,000的那些聚醚多元醇。这些聚醚多元醇包括具有低不饱和度、可由例如双金属氰化物催化剂制备者。这些具有低单醇含量的聚醚多元醇可由任何已知的方法制备,所述方法为例如描述于例如美国专利5,523,386、5,527,880、5,536,883、5,563,221、5,589,431、5,596,075和5,637,673中者,在此引入这些专利的公开内容作为参考。
这些聚醚多元醇可以以已知的方法通过使包含反应性氢原子的适宜起始化合物与环氧乙烷和环氧丙烷以重量比10∶90-70∶30、优选13∶87-50∶50且最优选15∶85-35∶65(EO∶PO比)反应而获得。包含反应性氢原子的适宜起始化合物包括例如多羟基醇如乙二醇、丙二醇-(1,2)和-(1,3);丁二醇-(1,4)和-(1,3);己二醇-(1,6);辛二醇-(1,8);新戊二醇、环己烷二甲醇(1,4-二羟基甲基环己烷);2-甲基-1,3-丙二醇;2,2,4-三甲基-1,3-戊二醇、三甘醇、四甘醇、聚乙二醇;一缩二丙二醇;聚丙二醇;一缩二丁二醇和聚丁二醇;丙三醇和三羟甲基丙烷;此外还有水、甲醇、乙醇、1,2,6-己三醇、1,2,4-丁三醇、三羟甲基乙烷、季戊四醇、甘露醇、山梨醇、甲基糖苷、蔗糖、苯酚、异壬基苯酚、间苯二酚、氢醌和1,1,1-或1,1,2-三-(羟基苯基)-乙烷。用于本发明的聚醚多元醇的优选起始化合物包括例如丙二醇、丙三醇、水、乙二醇、二甘醇和三羟甲基丙烷。
用于制备含有脲基甲酸酯基团的稳定液态MDI基预聚物的优选聚醚多元醇为官能度约为2、分子量为约1,000-约6,000者,它们是通过适宜的起始物(优选丙二醇)被环氧乙烷、环氧丙烷或其混合物以10∶90-70∶30、优选13∶87-50∶50且最优选15∶85-35∶65的EO∶PO重量比烷氧基化而制备的。
上述含有脲基甲酸酯基团的液态MDI基预聚物与异氰酸酯反应性组分(B)反应形成本发明的聚氨酯制品。适宜的异氰酸酯反应性组分包括(1)以组分(B)的总重量为基准,约25-约92wt%、优选65-85wt%的至少一种官能度为约2且分子量为约3,000-约8,000、优选约3,500-4,500的聚醚多元醇;(2)以组分(B)的总重量为基准,约5-约72wt%、优选5-25wt%的至少一种填充多元醇,其官能度为约2.5-约3、优选约3,且分子量为约3,000-约8,000、优选约4,800-约6,000;和(3)以组分(B)的总重量为基准,约3-约30wt%、优选3-15wt%的至少一种有机化合物,该化合物包含约2-约4个羟基基团、优选约2个羟基基团,并且分子量为约28-约250、优选60-110。
用作本发明的组分(B)(1)的适宜聚醚多元醇包括例如官能度为约2、优选2,且分子量为约3,000-约8,000、优选3500-4500者。合适的用于本发明的高分子量聚醚是已知的并且例如可以通过在适当的催化剂存在下聚合四氢呋喃或环氧化合物而获得,其中所述环氧化合物为例如环氧乙烷、环氧丙烷、环氧丁烷、苯乙烯氧化物或表氯醇,所述催化剂为例如BF3或KOH或双金属氰化物,或者通过化学法将这些环氧化合物,优选环氧乙烷和环氧丙烷混合地或连续地加入到含有反应性氢原子的组分如水、多元醇或胺中而获得。可以用作组分(B)(1)的起始化合物的适宜多元醇和胺的实例包括本领域中已知的低分子量二醇、二胺和氨基醇。下面列出这类化合物的适宜实例,包括丙二醇、乙二醇、水、双酚A、N,N’-二甲基乙二胺、N-甲基乙醇胺等。优选使用官能度为2、分子量为约3000-约8000的聚醚多元醇,它们是通过适宜的起始物被环氧乙烷,且优选环氧丙烷,或其混合物烷氧基化而制备的。优选的起始化合物包括丙二醇、水、乙二醇和二甘醇。
当然,也可以使用含有少量单醇、三醇、三胺等的二醇、二胺和/或氨基醇的混合物作为组分(B)(1)的起始化合物,条件是该混合物满足以上的官能度要求。
用作本发明中的组分(B)(2)的适宜化合物为填充多元醇。此处所用术语“填充多元醇”意指:(i)聚脲和/或聚联二脲在含有至少两个羟基的较高分子量的有机化合物中的分散体,(ii)通过在含有至少两个羟基的较高分子量的有机化合物中聚合一种或多种烯不饱和单体如苯乙烯或丙烯腈而制备的聚合物多元醇,和(iii)其混合物。这些填充多元醇是已知的并且可以表征为含有羟基的化合物,它们以细分散或溶解的形式含有高分子量加聚物、缩聚物或聚合物。
适用于本发明的聚合物多元醇是已知的。其制备方法描述于美国专利3,383,351、3,304,273、3,523,093、3,652,639、3,823,201和4,390,645中,此处引入其全部公开内容作为参考。适用于本发明的聚脲和/或聚联二脲分散体也是已知的并且是通过在较高分子量含羟基物质的存在下使有机多异氰酸酯与含有伯和/或仲胺基团、肼、酰肼或其混合物的多元胺反应而制备的。这些分散体描述于美国专利4,042,537、4,089,835、3,325,421、4,092,275、4,093,569、4,119,613、4,147,680、4,184,990、4,293,470、4,296,213、4,305,857、4,305,858、4,310,448、4,310,449、4,324,716、4,374,209、4,496,678、4,523,025、4,668,734、4,761,434和4,847,320中,此处引入其全部公开内容作为参考。这些分散体的固含量一般为1-40wt%,优选10-30wt%。优选地组分(B)(2)包含所谓的PHD(聚联二脲分散体)多元醇。
在异氰酸酯反应性组合物中用作组分(B)(3)的适宜有机化合物包括例如含有2-4个(优选约2个)羟基基团、氨基基团及其混合物并且分子量为约28-约250的有机化合物。适宜的化合物包括例如二醇、三醇、四醇、二胺、三胺、氨基醇及其混合物。
适宜的含羟基的化合物的一些实例包括二醇,例如乙二醇、丙二醇、1,2-和1,3-丙二醇、1,3-和1,4-及2,3-丁二醇、1,6-己二醇、一缩二丙二醇、二缩三丙二醇、二甘醇(即DEG)、三甘醇(即TEG)、四甘醇、三缩四丙二醇、六缩七丙二醇、2-甲基-1,3-丙二醇、1,10-癸二醇、新戊二醇、2,2,4-三甲基戊烷-1,3-二醇、二-(羟乙基)-氢醌、丙三醇、三羟甲基丙烷等。优选的低分子量化合物包括乙二醇。1,4-丁二醇及其混合物。乙二醇是最优选的。
本发明还要求至少一种吹塑剂。适宜的吹塑剂包括水以及物理吹塑剂例如低沸点烷烃、部分或全部氟化的烃等。适宜的低沸点烷烃包括诸如丙酮、戊烷、己烷、环戊烷之类的化合物。适宜的部分或全部氟化的烃的一些实例包括诸如HFC-134a(1,1,1,2-四氟乙烷)、HFC-245fa(1,1,1,3,3-五氟丙烷)、HFC-245ca(1,1,2,2,3-五氟丙烷)、HFC-236ca(1,1,1,2,3,3-六氟丙烷)之类的化合物。二氯甲烷也是一种本发明的适宜吹塑剂。这类吹塑剂的各种混合物也是适宜的。优选吹塑剂包括水。
当用水作为唯一的吹塑剂时,在本发明中其用量一般占配方中B方总重量的约0.05-1wt%,且优选约0.35-0.7wt%。当然,如上所述,水也可和其它吹塑剂联合使用。当在本发明中使用水和另一种吹塑剂的混合物时,上述水的用量范围要降低。例如,如果还使用一种物理吹塑剂,水的加入量为约0.05-0.3wt%(以配方中B方总重量为基准)。要求这类吹塑剂混合物以生产连皮泡沫塑料的常规方法中的典型用量存在。在本发明中,以生产所要求密度的泡沫塑料所必需的量加入吹塑剂,所要求的密度由其应用或最终用途所决定。例如,在微孔或连皮泡沫塑料中,且特别是在鞋底中,模塑泡沫的密度通常为约0.2-约0.6g/cc(即20-35pcf)。有时密度可高达约1g/cc,例如在高密度外底粘结到低密度中底上的双密度鞋底中。
还需要一种或多种催化剂存在于本发明的反应混合物中。适宜的催化剂包括例如叔胺催化剂和有机金属催化剂。
适宜的有机金属催化剂的一些实例包括例如锡、铅、铁、铋、汞等的有机金属化合物。优选的有机锡催化剂包括例如下列化合物:乙酸锡、辛酸锡、乙基己酸锡、油酸锡、月桂酸锡、二月桂酸二甲基锡、氧化二丁基锡、二氯化二丁基锡、二氯化二甲基锡、二乙酸二丁基锡、二乙酸二乙基锡、二乙酸二甲基锡、二月桂酸二丁基锡、二月桂酸二乙基锡、二月桂酸二甲基锡、马来酸二丁基锡、马来酸二甲基锡、二乙酸二辛基锡、二月桂酸二辛基锡、氧化二(2-乙基己基)锡等。其它适用于本发明的催化剂包括例如二硫醇二烷基锡如二硫醇二丁基锡、二异辛基巯基乙酸二丁基锡、二硫醇二甲基锡、二月桂基硫醇二丁基锡、二月桂基硫醇二甲基锡、二异辛基巯基乙酸二甲基锡、二(异辛基巯基乙酸)二(正丁基)锡和二(异辛基巯基乙酸)二(异辛基)锡,所有这些化合物都可从Witco Chemical Corp.购得,并且是特别优选的;并且二烷基锡二硫化物,例如硫化二丁基锡和硫化二辛基锡也是适宜的催化剂。也可以使用迟发型催化剂如戊二酮铁或羧酸铋,如美国专利4,611,044中所述的,在此引入该专利作为参考。
用于本发明的适宜的热激活催化剂为胺盐。这些催化剂包括脂族和芳族叔胺及叔胺的环氧加成物。描述于例如美国专利3,892,687、4,116,879和4,582,861的胺的季铵盐(即烷氧基化叔胺)在本发明中也是适宜的,在此引入这些专利的公开内容作为参考。适宜的热激活胺盐包括例如下列化合物:从Air Products购得的DABCO 8154、甲酸嵌段的三亚乙基二胺及其它迟发型催化剂如也是从AirProducts购得的DABCO WT;以及Polycat SA-1和Polycat SA-102,它们都是1,8-二氮杂双环[5.4.0]-十一碳烯-7(即Polycat DBU)的酸嵌段物并且是从Air Products购得的。三烷基胺和杂环胺也适用于本发明。适宜的化合物包括例如三甲基胺、三乙基胺、三丙基胺、三丁基胺、二甲基环己基胺、二丁基环己基胺、二甲基乙醇胺、三乙醇胺、二乙基乙醇胺、乙基二乙醇胺、二甲基异丙醇胺、三异丙醇胺、三亚乙基二胺、四甲基-1,3-丁二胺、N,N,N’,N’-四甲基乙二胺、N,N,N’,N’-四甲基己二胺-1,6、N,N,N’,N’,N”-五甲基二乙三胺、二(2-二甲基氨基乙氧基)-甲烷、N,N,N’-三甲基-N’-(2-羟基乙基)乙二胺、N,N-二甲基-N’N’-二(2-羟基乙基)乙二胺、四甲基胍、N-甲基哌啶、N-乙基哌啶、N-甲基吗啉、N-乙基吗啉、1,4-二甲基哌啶、1,2,4-三甲基哌啶、N-(2-二甲基氨基乙基)-吗啉、1-甲基-4-(2-二甲基氨基)-哌啶、1,4-二氮杂双环[2.2.2]辛烷、2-甲基-1,4-二氮杂双环[2.2.2]辛烷喹宁环、1,5-二氮杂双环[5.4.0]-5-十-碳烯和1,5-二氮杂双环[4.3.0]-5-壬烷。
有机金属催化剂通常以占配方中B方总重量约0.005-约0.5wt%、优选约0.02-0.4wt%的量使用。叔胺催化剂或其盐以占配方中B方总重量(100wt%)约0.05-约2wt%、优选约0.1-约0.5wt%的量使用是有利的。优选催化剂的总量为它们占配方中B方总重量的量少于3wt%,优选少于2wt%。
配方中也可包含各种添加剂和/或辅剂。适宜添加剂的一些实例包括表面活性添加剂如乳化剂和泡沫稳定剂。其实例包括N-硬脂酰基-N’,N’-二羟乙基脲、油烯基聚氧乙烯酰胺、硬脂酰基二乙醇酰胺、异硬脂酰基二乙醇酰胺、聚氧亚乙基二醇单油酸酯、季戊四醇/己二酸/油酸酯、油酸的羟乙基咪唑衍生物、N-硬脂酰基丙二胺及蓖麻油磺酸酯的或脂肪酸的钠盐。磺酸如十二烷基苯磺酸或二萘基甲磺酸的以及脂肪酸的碱金属或铵盐可以用作表面活性添加剂。
适宜的泡沫稳定剂包括水溶性聚醚硅氧烷。这些化合物的结构一般是环氧乙烷和环氧丙烷的共聚物与聚二甲基硅氧烷基团相连。这类泡沫稳定剂描述于美国专利2,764,565中。
除了表面活性剂,可用于本发明的模塑组合物中的其它添加剂包括已知的内脱模剂、颜料、单元调节剂、阻燃剂、增塑剂、染料、填料和增强剂如纤维或薄片或碳纤维形式的玻璃,以及抗静电剂。
本发明的模塑制品可由适于生产微孔泡沫的任何常规方法生产。这些方法包括例如开模法、闭模法和直接固定法。这可由高压和低压发泡设备实现。关于这些方法的其它细节可见例如《聚氨酯手册》,第2版,Gunter Oertel编著,第7章,329-386页,HanserPublishers,Munich,New York。
可使用常规的加工技术在异氰酸酯指数为约95-105(优选96-100)时将本发明的组合物模塑成型。术语“异氰酸酯指数”(通常也称作“NCO指数”)在此处定义为异氰酸酯的当量数除以含有异氰酸酯反应性氢的物质的总当量数,再乘以100。
如此处所用,短语“B方”指包含异氰酸酯反应性组分(B)(1)、(B)(2)和(B)(3),吹塑剂(C),及任何催化剂、表面活性剂或其它添加剂的混合物,所述添加剂在与异氰酸酯组分反应之前先与这些组分预混合。
此处所用术语“分子量”指由终端分析测定的数均分子量。
下列实施例进一步说明了本发明方法的细节。在前面公开中给出的发明在主旨或范围方面都不受这些实施例的限制。本领域技术人员易于理解,下列步骤的各种改变条件是可以使用的。除非另外指明,所有的温度都是摄氏度且所有的份都是重量份。
实施例
在所用实施例中使用下列组分:
多元醇A:OH值为约28的聚醚二醇,由丙二醇、环氧丙烷和环氧乙烷制备,环氧丙烷与环氧乙烷的重量比为70∶30,约100%的OH基团是伯羟基。
多元醇B:OH值为约28且由在丙三醇引发的环氧丙烷/环氧乙烷聚醚(OH值为约35,环氧丙烷与环氧乙烷的重量比为约5∶1)中的聚联二脲组成的分散体。该多元醇是通过在如美国专利4,042,537所述的丙三醇引发的聚醚存在下使甲苯二异氰酸酯与肼反应而制备的,在此引入所述专利的公开内容作为参考。所得分散体的固含量为约20wt%。
1,4-BD:1,4-丁二醇
EG:乙二醇
CAT A:三乙胺在1,4-丁二醇中的1∶3混合物,以Dabco S-25从Air Products购得
CATB:由30%胺和70%1,4-丁二醇组成的叔胺,以Dabco 1028从Air Products购得
CATC:二月桂基硫醇二丁基锡,以UL-1从witco购得
CATD:二月桂酸二丁基锡催化剂,以T-12从Air Products购得
CATE:正烷基取代的有机锡催化剂,以Topcat 190从TyloIndustries,Parsippany,NJ.购得
L5309:从OSi Specialties,Inc.购得的市售品聚氧化亚烷基二甲基硅氧烷共聚物表面活性剂
ISO A:异氰酸酯基团含量为约19wt%的异氰酸酯,是通过下列组分的反应制备的:
(i)56重量份亚甲基二(苯基异氰酸酯)的4,4’-异构体,
(ii)6重量份异氰酸酯基团含量为29.3%且25℃时的粘度小于100mpa.s的碳化二亚胺改性的亚甲基二(苯基异氰酸酯),
(iii)38重量份2000分子量的聚酯二醇,由己二酸、1,4-丁二醇和乙二醇反应制备,其中乙二醇与丁二醇的摩尔比为1∶1。(该异氰酸酯等同于美国专利5,514,723在栏目6,34-46行的实施例中所用的异氰酸酯)
ISO I:NCO含量为约18.9wt%、25℃时的粘度为440mpa.s的脲基甲酸酯改性的预聚物,该预聚物为透明的浅黄色产物。该预聚物是通过下列步骤制备的:将100重量份MDI(98wt%的4,4’-MDI和2wt%的2,4’-MDI)加入到氮气填充的反应器中。在50℃边搅拌MDI边加入3.2重量份1-丁醇。该反应放热至约60℃。向该60℃反应混合物中加入0.008重量份乙酰基丙酮酸锌(ZnAcAc)。然后将该混合物加热至90℃并保持约1.5小时。随后加入0.016重量份苯甲酰氯阻聚剂,并将反应混合物冷却至约60℃。形成NCO含量为约29.0wt%的脲基甲酸酯改性的MDI。最后,在60℃将48.9重量份多元醇A加入到脲基甲酸酯改性的MDI中。将此混合物在60℃保持约1.5小时,随后冷却到25℃。形成了透明的浅黄色产物,该产物为具有如上所列NCO含量和粘度的脲基甲酸酯改性的预聚物。
均为脲基甲酸酯改性的异氰酸酯预聚物的异氰酸酯B至L是使用与上述制备ISO I同样的基本步骤制备的,不同之处在于反应物等的相对量不同,如表1A和1B所示。
表1A
异氰酸酯1 | ISO B | ISO C | ISO D | ISO E | ISO F |
1-丁醇;pbw | 2.6 | 3.21 | 3.2 | 3.2 | 3.2 |
AMI2的NCO% | 29.9 | 29.0 | 29.0 | 29.0 | 29.0 |
聚醚的MW3 | 192 | 425 | 1000 | 2000 | 4000 |
EO∶PO的重量比4 | 0∶100 | 0∶100 | 0∶100 | 0∶100 | 0∶100 |
聚醚;pbw | 13.5 | 26.6 | 37.7 | 44.2 | 48.6 |
AMI预聚物的NCO% | 20.5 | 18.7 | 19.1 | 18.8 | 18.9 |
AMI预聚物在25℃的粘度,mpa.s | 1765 | 1724 | 691 | 388 | 404 |
1 每100重量份MDI1-丁醇和聚醚的份数
2 AMI:脲基甲酸酯改性的异氰酸酯
3 用于制备AMI预聚物的聚醚多元醇的分子量。丙二醇是制备所有聚醚的引发剂。
4 在用于制备预聚物的聚醚中环氧乙烷(EO)与环氧丙烷(PO)的重量比
表1B
异氰酸酯1 | ISO G | ISO H | ISO I | ISO J | ISO K | ISO L |
1-丁醇;pbw | 3.2 | 3.2 | 3.2 | 3.2 | 7.8 | 7.8 |
AMI2的NCO% | 29.0 | 29.0 | 29.0 | 29.0 | 23.0 | 23.0 |
聚醚的MW3 | 4000 | 4000 | 4000 | 2000 | 4000 | 4000 |
EO∶PO的重量比4 | 20∶80 | 13∶87 | 30∶70 | 50∶50 | 20∶80 | 30∶70 |
聚醚;pbw | 48.6 | 48.6 | 48.9 | 44.2 | 20.4 | 20.4 |
AMI预聚物的NCO% | 19.0% | 18.9% | 18.9% | 18.9% | 18.8% | 18.8% |
AMI预聚物在25℃的粘度,mPa.s | 446 | 425 | 440 | 428 | 1020 | 1050 |
1 每100重量份MDI 1-丁醇和聚醚的份数
2 AMI:脲基甲酸酯改性的异氰酸酯
3 用于制备AMI预聚物的聚醚多元醇的分子量。丙二醇是制备所有聚醚的引发剂。
4 在用于制备AMI预聚物的聚醚中环氧乙烷(EO)与环氧丙烷(PO)的重量比
异氰酸酯A、E和G与下表2所列的多元醇掺混物反应。挠曲数据是以100份多元醇掺混物与74份异氰酸酯的比例(即NCO指数为98)时由手工混合泡沫而获得的。将手工混合的泡沫在约24℃混合约5秒。表1-7中的实施例为手工混合的泡沫。
用于进行挠曲性研究的模具为铝板模具,内尺寸为15.24厘米×15.24厘米×1.59厘米(6英寸×6英寸×5/8英寸),并且从模具边缘1.27厘米(1/2英寸)处起带有一系列平行的隆脊而空出1.27厘米(1/2英寸)。每个隆脊为0.32厘米(1/8英寸)高×0.32厘米(1/8英寸)宽,并且遍布模具的整个15.24厘米(6英寸)宽。模具中这些隆脊造成板有焊口,这使得板在反复挠曲过程中更易开裂。板在约4-约5分钟脱模。挠曲试验是使用ASTM-D-1052的改进方法在罗斯挠曲试验机上进行的,其中试验样品未切割。
表2
实施例 | 实施例1 | 实施例2 | 实施例3 |
多元醇A | 73.44 | 73.44 | 73.44 |
多元醇B | 14.43 | 14.43 | 14.43 |
1,4-BD | 8.50 | 8.50 | 8.50 |
EG | 0.97 | 0.97 | 0.97 |
CAT A | 0.80 | 0.80 | 0.80 |
CAT B | 0.50 | 0.50 | 0.50 |
CAT C | 0.03 | 0.03 | 0.03 |
CAT E | 0.25 | 0.25 | 0.25 |
水 | 0.38 | 0.38 | 0.38 |
异氰酸酯 | ISOA | ISOE | ISOG |
异氰酸酯指数 | 98 | 98 | 98 |
脲基甲酸酯改性的预聚物E和G得到了具有如下表3所示的改进挠曲性能的模板。
表3
实施例1(对比例) | 第一对样品失败;两者经73,000次循环几乎完全破碎。第二对样品在约50,000次循环时显示破损;在63,000次循环时,一个样品出现开裂口;约70,000次循环后一个样品出现贯穿全部样品的浅裂口。 |
实施例2(对比例) | 直到约100,000次循环时未出现明显破损,随后一块板开始开裂;130,000次循环后裂口贯穿一个样品;其它的板显示有些破损,但尚未开裂。 |
实施例3 | 在130,000次循环后出现一些疲劳迹象(即拉伸痕迹),但未形成开裂。 |
表3中所列实施例的试验在运行130,000次循环后停止。
在实施例1、2和3中使用了尺寸为10.16厘米×12.70厘米×2.54厘米(4in.×5in.×1in.)的模塑部件。
表4:实施例1、2和3的物理性能
使用下列ASTM方法测定本申请实施例中的物理性能:硬度 D-2240拉伸强度 D-412伸长率 D-412模C撕裂 D-624和D-3489
实施例 | 1 | 2 | 3 |
密度(g/cc) | 0.44 | 0.44 | 0.45 |
硬度(邵氏A) | 50 | --- | 36 |
拉伸强度(psi) | 454.7 | 450.2 | 434.3 |
伸长率(%) | 401.1 | 416.5 | 404.8 |
模C撕裂 | --- | 74.2 | --- |
落球回弹率(%) | 46 | --- | 42.6 |
落球回弹率 D-3574
泰伯耐磨试验 D-3489
表2、3和4中的实施例清楚地表明本发明的脲基甲酸酯改性的预聚物异氰酸酯形成了特别适用于鞋底应用(见实施例3)的模塑聚氨酯部件(即泡沫塑料)。与实施例1中所列及美国专利5,514,723中所述的使用碳化二亚胺改性的聚酯扩链的异氰酸酯预聚物(见上述ISO A)的现有技术状态相比,并且与基于脲基甲酸酯改性的预聚物(其中用于制备预聚物的聚醚包含100%PO基团)的模塑部件相比,这些模塑部件显示了改进的耐挠曲疲劳性。
另一系列手工混合的发泡板是使用上述步骤形成的,但使用的是列于表5的不同多元醇配方,并且模具尺寸较小。更具体而言,在此系列实施例中所使用的模具尺寸只有0.95厘米(3/8英寸)厚,而不是1.59厘米(5/8英寸)厚。模具的所有其它方面均与上述模具相同。此外,在这些实施例中使用了异氰酸酯A、F和J。
表5
实施例 | 实施例4 | 实施例5 | 实施例6 |
多元醇A | 71.95 | 71.95 | 71.95 |
多元醇B | 14.43 | 14.43 | 14.43 |
1,4-BD | 9.14 | 9.14 | 9.14 |
EG | 0.97 | 0.97 | 0.97 |
CAT A | 1.28 | 1.28 | 1.28 |
CAT B | 1.05 | 1.05 | 1.05 |
CAT D | 0.03 | 0.03 | 0.03 |
L5309 | 0.7 | 0.7 | 0.7 |
水 | 0.45 | 0.45 | 0.45 |
异氰酸酯 | A | F | J |
异氰酸酯指数 | 98 | 98 | 98 |
与美国专利5,514,723的碳化二亚胺改性的异氰酸酯相比,由基于脲基甲酸酯改性的异氰酸酯预聚物的此系列实施例制成的模塑板也显示了改进的挠曲性能。挠曲试验的结果列与表6。挠曲试验是使用ASTM-D-1052的改进方法在罗斯挠曲试验机上进行的,其中试验样品未切割。
表6
实施例 | 说明 |
实施例4(对比例;基于碳化二亚胺改性的异氰酸酯) | 一个样品在经约58,000次循环后开始开裂。在约132,000次循环后,每个样品都有一个贯穿整个样品的深裂口(~1mm)。 |
实施例5(对比例;基于脲基甲酸酯改性的异氰酸酯预聚物,其中所用聚醚包含100%PO) | 在约160,000次循环后两个样品均出现“拉伸痕迹”(但未开裂)。一个样品在约300,000次挠曲试验后开始开裂;并且在350,000次循环后裂口贯穿整个样品。 |
实施例6(基于脲基甲酸酯改性的异氰酸酯预聚物,其中所用聚醚包含50wt%PO和50wt%EO | 在200,000次循环后两个样品均出现一些小针孔。700,000次挠曲试验(本实施例中试验终止点)后针孔逐渐长大,但未形成开裂。 |
列于表6的实施例的试验在运行700,000次后停止。这足以区分这些实施例。
表7
实施例 | 4 | 5 | 6 |
密度(g/cc) | 0.53 | 0.50 | 0.50 |
硬度(邵氏A) | 58 | 47 | 3 8 |
拉伸强度(psi) | 474 | 473 | 443 |
伸长率(%) | 368 | 358 | 389 |
泰伯磨耗(mg损耗/1000次循环) | 48 | 30.5 | 48.4 |
通过比较表6和7中的实施例6与实施例4和5的试验结果可见,获得了根据本发明生产的模塑部件在挠曲试验中的优势,而没有显著损失其它的物理/机械性能。
生产了另一系列模塑部件。(见表8和9。)但是这些部件是使用Kymofoam型KF-IS-202泡沫机在约26-33℃以约3800rpm的混合速度机械混合的,产出量为约60g/s。该系列模塑部件使用了列于表8的配方,下面的表9总结了表8的实施例的物理性能。
该系列实施例清楚地表明无论泡沫塑料是手工混合的或机械混合的,当异氰酸酯预聚物是基于含有100%环氧丙烷(PO)的聚醚时,尽管可以获得具有良好物理性能的模塑部件(泡沫塑料),但是机械混合泡沫塑料的尺寸稳定性照例会出问题。在脱模时机械混合的泡沫塑料严重变形,在某些区域严重收缩或缩陷,而在其它区域存在大的隆起。简而言之,模塑部件不符合模具的形状。
此中原因是未知的且现在尚不清楚。但似乎其中异氰酸酯为基于含有100%PO的聚醚的预聚物的手工混合配方倾向于掩盖机械混合时伴随发生的尺寸不稳定性。尽管手工混合适合于实验室和/或其它小规模的操作,但是在工业上是不被接受和/或切实可行的,因为伴随手工混合所带来的花费和/或时间限制。
表8
实施例 | 实施例7 | 实施例8 | 实施例9 | 实施例10 | 实施例11 | 实施例12 | 实施例13 | 实施例14 |
多元醇A | 73.71 | 73.71 | 73.71 | 73.71 | 71.95 | 71.95 | 71.95 | 71.95 |
多元醇B | 14.43 | 14.43 | 14.43 | 14.43 | 14.43 | 14.43 | 14.43 | 14.43 |
1,4-BD | 9.5 | 8.5 | 8.5 | 9.5 | 9.14 | 9.14 | 9.14 | 9.14 |
EG | 0.97 | 0.97 | 0.97 | 0.97 | 0.97 | 0.97 | 0.97 | 0.97 |
CAT A | 0.8 | 0.8 | 0.8 | 0.8 | 1.28 | 1.2B | 1.28 | 1.28 |
CAT B | 0.21 | 0.21 | 0.21 | 0.21 | 1.05 | 1.05 | 1.05 | 1.05 |
CAT C | 0.03 | 0.03 | 0.03 | 0.03 | 0 | 0 | 0 | 0 |
CAT D | 0 | 0 | 0 | 0 | 0.03 | 0.03 | 0.03 | 0.03 |
CAT E | 0.25 | 0.25 | 0.25 | 0.25 | 0 | 0 | 0 | 0 |
L5309 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 |
水 | 0.4 | 0.4 | 0.4 | 0.4 | 0.45 | 0.45 | 0.45 | 0.45 |
ISO | ISO B | ISO D | ISO D | ISO D | ISO G | ISO I | ISO K | ISO L |
异氰酸酯指数 | 98 | 98 | 98 | 98 | 98 | 98 | 98 | 98 |
表9
1 mg损耗/1000次循环2 模塑板符合模具的形状。没有明显的变形。
实施例 | 实施例7 | 实施例8 | 实施例9 | 实施例10 | 实施例11 | 实施例12 | 实施例13 | 实施例14 |
密度(g/cc) | 25.7 | 31.2 | 25.0 | 31 | 30.6 | 33.1 | 33.1 | 31.8 |
硬度(邵氏A) | 35 | 47 | 28 | 37 | 40 | 33 | 41 | 38 |
拉伸强度(psi) | 504 | 479 | 396 | 503 | 489 | 412 | 484.3 | 493 |
伸长率(%) | 406 | 463 | 529 | 408 | 462 | 392 | 392 | 473 |
模C撕裂(pli) | 75.4 | 92.6 | 67.6 | 82.2 | 83.1 | 104.1 | 95.8 | 86.9 |
落球回弹率(%) | 11.6 | 49.8 | 34.8 | 29.6 | 41.7 | 27.1 | 19.4 | 22.0 |
泰伯磨耗1 | 285.3 | 99.6 | 101.3 | 66.9 | 39.8 | 70.9 | 47.8 | 51.4 |
尺寸稳定性 | 非常差4 | 差3 | 差3 | 差3 | 良好2 | 良好2 | 良好2 | 良好2 |
3 模塑部件形状变形。边缘卷曲而非平直。
4 除模塑部件形状变形且边缘卷曲而非平直外,表面带有大的隆起和极度收缩的区域。
这些实施例的模具腔构成“矩形的平行六面体”,即基底是矩形的(实际为正方形的),带有垂直的面。因此,就尺寸稳定性而言,“良好”级是指符合模具形状,即为矩形平行六面体的部件;“差”级是指显示了变形以致例如面之间的角度不是90°,但表面较平的部件;“非常差”级是指显示了大的隆起和收缩或缩陷区域以及上述角度变形的部件。
表10和11中列出两个实施例。表10列出配方而表11列出性能。使用上述ASTM方法测定挠曲数据以外的性能。挠曲数据是根据ASTM-D-1052在罗斯挠曲试验机上测定的,试验样品是按该ASTM要求冲切的。进行挠曲试验的试验样品为15.24厘米×15.24厘米×1.27厘米(6in.×6in.×1/2in.)的板。实施例15为对比例,而实施例16是本发明的代表。这些泡沫塑料是根据表8和9中的配方如上所述机械混合的。
表10
实施例 | 15 | 16 |
多元醇A | 71.95 | 71.95 |
多元醇B | 14.43 | 14.43 |
1,4-BD | 9.14 | 9.14 |
EG | 0.97 | 0.97 |
CAT A | 1.28 | 1.28 |
CAT B | 1.05 | 1.05 |
CAT D | 0.03 | 0.03 |
L5309 | 0.7 | 0.7 |
水 | 0.45 | 0.45 |
ISO | A | G |
异氰酸酯指数 | 98 | 98 |
表11:实施例15和16的物理性能
实施例 | 15 | 16 |
密度 (g/cc) | 33.1 | 33.7 |
硬度(邵氏A) | 58 | 56 |
拉伸强度(psi) | 474 | 461 |
伸长率(%) | 368 | 410 |
模C撕裂(pli) | 71 | 81 |
泰伯磨耗1 | 48 | 43 |
罗斯挠曲(在-20℃) | 60,000次循环后900%切口增长 | 100,000次循环后无切口生长 |
1:mg损耗/1000次循环
虽然前面基于说明的目的已详细描述了本发明,但应该理解为这些细节仅是出于说明的目的,本领域技术人员可在不背离本发明精髓和范围的情况下作出各种改变,除了权利要求所限制者。
Claims (16)
1.包括微孔聚氨酯泡沫塑料的模塑制品,它是(A)与(B)在(C)存在下的反应产物:其中
(A)NCO含量为5-30%并包含脲基甲酸酯改性的二苯基甲烷二异氰酸酯的稳定液态二苯基甲烷二异氰酸酯基预聚物,其中所述预聚物包括(1)和(2)的反应产物:
(1)脲基甲酸酯改性的二苯基甲烷二异氰酸酯,它是通过i)和ii)反应制备的:
(i)脂族醇或芳族醇,其中所述醇包含的碳原子少于17个,
(ii)二苯甲烷二异氰酸酯,它包括0-60wt%的2,4’-二苯甲烷二异氰酸酯、少于6 wt%的2,2’-二苯甲烷二异氰酸酯、且剩余的为4,4’-二苯甲烷二异氰酸酯,
(2)含有2-3个羟基基团且分子量为750-10,000的聚醚多元醇,所述聚醚多元醇是由起始化合物与环氧乙烷及环氧丙烷以重量比10∶90-70∶30制备的;
(B)异氰酸酯反应性组合物,包括:
(1)以组分(B)的总重量为基准,25-92wt%的至少一种官能度为2且分子量为3,000-8,000的聚醚多元醇,
(2)以组分(B)的总重量为基准,5-72 wt%的填充多元醇,其中所述填充多元醇的官能度为2.5-3且分子量为3,000-8,000,该填充多元醇以细分散或溶解的形式包含高分子量加聚物、缩聚物或聚合物,和
(3)以组分(B)的总重量为基准,3-30wt%的至少一种有机化合物,该化合物包含2-4个羟基基团并且分子量为28-250;
(C)吹塑剂,
其中组分(A)和(B)的量为使异氰酸酯指数为90-110的量。
2.权利要求1的模塑制品,其中(A)(1)中所述的脲基甲酸酯改性的二苯基甲烷二异氰酸酯是通过(i)和(ii)反应制备的:
(i)脂族醇或芳族醇,其中所述醇含有2-8个碳原子,
(ii)二苯甲烷二异氰酸酯,它包括0-6wt%的2,4’-二苯甲烷二异氰酸酯、0-2wt%的2,2’-二苯甲烷二异氰酸酯且剩余的为4,4’-二苯甲烷二异氰酸酯。
3.权利要求1的模塑制品,其中(A)(2)中所述的聚醚多元醇含有2个羟基基团,分子量为1,000-6,000,并且是由起始化合物与环氧乙烷及环氧丙烷以重量比13∶87-50∶50制备的。
4.权利要求3的模塑制品,其中环氧乙烷与环氧丙烷的重量比为15∶85-35∶65。
5.权利要求1的模塑制品,其中(B)(2)中所述的填充多元醇包括聚脲和/或聚联二脲在含有至少两个羟基基团的有机化合物中的分散体。
6.权利要求1的模塑制品,其中(B)(2)中所述的填充多元醇包括苯乙烯-丙烯腈共聚物的接枝聚合物多元醇。
7.权利要求1的模塑制品,其中(B)(2)中所述的填充多元醇的官能度为3且分子量为4,800-6,000。
8.权利要求1的模塑制品,其中(B)(3)中所述的有机化合物选自1,4-丁二醇、乙二醇及其混合物。
9.权利要求1的模塑制品,其中(A)(1)中所述的脲基甲酸酯改性的二苯基甲烷二异氰酸酯是通过(i)正丁醇和(ii)包括0-6wt%的2,4’-二苯甲烷二异氰酸酯、0-2wt%的2,2’-二苯甲烷二异氰酸酯且剩余的为4,4’-二苯甲烷二异氰酸酯的二苯甲烷二异氰酸酯反应制备的。
10.权利要求1的模塑制品,其中(A)中所述稳定的液态二苯基甲烷二异氰酸酯基预聚物的NCO含量为14-20%。
11.权利要求9的模塑制品,其中(A)(1)中所述的脲基甲酸酯改性的二苯基甲烷二异氰酸酯的NCO含量为23-30%。
12.权利要求11的模塑制品,其中(A)(1)中所述的脲基甲酸酯改性的二苯基甲烷二异氰酸酯的NCO含量为29%。
13.权利要求1的模塑制品,其中(A)(2)中所述的聚醚多元醇的官能度为2,分子量为4,000,并且是由环氧乙烷和环氧丙烷以重量比20∶80-30∶70制备的。
14.权利要求1的模塑制品,其中(C)中所述吹塑剂包括水。
15.权利要求1的模塑制品,其中所述反应是在(D)包括一种或多种催化剂和/或一种或多种表面活性剂的添加剂存在下进行的。
16.权利要求1的模塑制品,其中组分(A)和(B)的量为使异氰酸酯指数为96-103的量。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/899,556 | 1997-07-24 | ||
US08/899,556 US5889068A (en) | 1997-07-24 | 1997-07-24 | Water blown polyurethane soling systems |
Publications (2)
Publication Number | Publication Date |
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CN1284092A CN1284092A (zh) | 2001-02-14 |
CN1114641C true CN1114641C (zh) | 2003-07-16 |
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CN98807553A Expired - Fee Related CN1114641C (zh) | 1997-07-24 | 1998-07-14 | 包括微孔聚氨酯泡沫塑料的模塑制品 |
Country Status (14)
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US (1) | US5889068A (zh) |
EP (1) | EP0998509B1 (zh) |
JP (1) | JP4198878B2 (zh) |
KR (1) | KR20010022144A (zh) |
CN (1) | CN1114641C (zh) |
AU (1) | AU8484198A (zh) |
BR (1) | BR9810786A (zh) |
CA (1) | CA2295639C (zh) |
DE (1) | DE69802287T2 (zh) |
ES (1) | ES2163285T3 (zh) |
HK (1) | HK1034984A1 (zh) |
IL (1) | IL133654A0 (zh) |
PL (1) | PL338185A1 (zh) |
WO (1) | WO1999005195A1 (zh) |
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-
1997
- 1997-07-24 US US08/899,556 patent/US5889068A/en not_active Expired - Lifetime
-
1998
- 1998-07-14 IL IL13365498A patent/IL133654A0/xx unknown
- 1998-07-14 PL PL98338185A patent/PL338185A1/xx unknown
- 1998-07-14 KR KR1020007000714A patent/KR20010022144A/ko not_active Application Discontinuation
- 1998-07-14 EP EP98935643A patent/EP0998509B1/en not_active Expired - Lifetime
- 1998-07-14 ES ES98935643T patent/ES2163285T3/es not_active Expired - Lifetime
- 1998-07-14 DE DE69802287T patent/DE69802287T2/de not_active Expired - Fee Related
- 1998-07-14 BR BR9810786-0A patent/BR9810786A/pt not_active IP Right Cessation
- 1998-07-14 AU AU84841/98A patent/AU8484198A/en not_active Abandoned
- 1998-07-14 WO PCT/US1998/014536 patent/WO1999005195A1/en not_active Application Discontinuation
- 1998-07-14 CA CA002295639A patent/CA2295639C/en not_active Expired - Fee Related
- 1998-07-14 CN CN98807553A patent/CN1114641C/zh not_active Expired - Fee Related
- 1998-07-14 JP JP2000504183A patent/JP4198878B2/ja not_active Expired - Fee Related
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2001
- 2001-08-09 HK HK01105539A patent/HK1034984A1/xx not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
DE69802287T2 (de) | 2002-05-16 |
CA2295639C (en) | 2007-09-18 |
JP4198878B2 (ja) | 2008-12-17 |
EP0998509A1 (en) | 2000-05-10 |
KR20010022144A (ko) | 2001-03-15 |
CA2295639A1 (en) | 1999-02-04 |
BR9810786A (pt) | 2000-07-25 |
JP2003524661A (ja) | 2003-08-19 |
US5889068A (en) | 1999-03-30 |
DE69802287D1 (de) | 2001-12-06 |
HK1034984A1 (en) | 2001-11-09 |
ES2163285T3 (es) | 2002-01-16 |
IL133654A0 (en) | 2001-04-30 |
WO1999005195A1 (en) | 1999-02-04 |
EP0998509B1 (en) | 2001-10-31 |
CN1284092A (zh) | 2001-02-14 |
AU8484198A (en) | 1999-02-16 |
PL338185A1 (en) | 2000-10-09 |
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