CN1208423A - 聚氨酯弹性体 - Google Patents

聚氨酯弹性体 Download PDF

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CN1208423A
CN1208423A CN96199896A CN96199896A CN1208423A CN 1208423 A CN1208423 A CN 1208423A CN 96199896 A CN96199896 A CN 96199896A CN 96199896 A CN96199896 A CN 96199896A CN 1208423 A CN1208423 A CN 1208423A
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elastomerics
polyhydric alcohol
loss tangent
storage modulus
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G·J·布莱斯
A·J·哈米尔顿
J·W·勒恩斯拉
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Abstract

具有于0.75与1.5之间的于20℃的储能模量(E′)与于120℃的储能模量(E′)之比例、低于0.1的于100℃的损耗角正切(tanδ)及超过0.8的损耗角正切的最高值的一种多异氰酸酯－基的弹性体,损耗角正切是损耗模量(E″)与储能模量(E′)之比例。

Description

聚氨酯弹性体
发明详述
本发明是涉及新型的聚氨酯弹性体及用于其之制备的一种方法。
聚氨酯弹性体是经由用高分子量多元醇(诸如聚酯多元醇或聚醚多元醇)、及低分子量多元醇或多胺(诸如乙二醇或丁二醇)与二异氰酸酯(诸如二异氰酸甲苯酯(TDI)、二异氰酸1,5萘酯(NDI)或二异氰酸4,4′-二苯基甲烷酯(4,4′- MDI)反应而制造。
主要使用的高分子量聚醚多元醇是聚四氢呋喃或聚环氧丙烷。
自包含次要数量的环氧乙烷(EO)-基之聚醇多元醇的弹性体聚氨酯之制备亦是已知的，见例如欧洲专利-A-13487。
已使用包含高数量的4,4′-MDI及具有高EO含量的聚醚多元醇之配制物以制备挠性聚氨酯泡沫，见例如欧洲专利A-547764、欧洲专利-A-547765及欧洲专利-A-549120。
然而，已知的异氰酸酯-基的弹性体于广泛的温度范围内皆未显示令人满意的动态模量性质。
现已发现，于广泛的温度范围内显示半完美的弹性体性质的一种新颖的聚氨酯弹性体。
因此，本发明是关于具有于0.75与1.5之间的于20℃的储能模量(E′)与于120℃的储能模量(E′)之比例、低于0.1的于100℃的损耗角正切及超过0.8的损耗角正切的最高值的聚异氰酸酯-基的弹性体，损耗角正切是损耗模量(E″)与储能模量(E′)之比例。
较优选地，损耗角正切的最高值是超过1.0。
于20℃的储能模量(E′)与于120℃的储能模量(E′)之比例较优选地为于0.8与1.2之间，更优选地为于0.85与1.1之间。优选地具有低于0.05的于100℃的损耗角正切。最优选地，于100℃的损耗角正切为低于0.03。
损耗角正切的主要最高值较优选地于低于0℃的温度发生，最优选地为低于-10℃。
储能及损耗模量是经由动态机械热分析〔按照ISO/DIS 6721 -5测量的DMTA(动态机械热分析)〕而测量。
此类新型的聚氨酯弹性体可以自包含具有高氧亚乙基含量的多元醇或包含聚酯多元醇及高浓度的具有高氧亚乙基含量的多元醇之多元醇掺合物、基本上纯净的4,4′-MDI或其一种衍生物、及一种低分子量链增长剂及任选的一种交联剂的配制剂而制造。
因此，按照本发明，亦提供从包含一种多异氰酸酯成分、一种多元醇组合物、一种链增长剂及任选的一种交联剂的一种反应混合物制备聚氨酯弹性体的一种方法，其中多异氰酸酯成分包含至少85％(重量)的二异氰酸4,4′-二苯基甲烷酯或其一种变体，多元醇组合物包含至少一种包含氧亚乙基残基的聚氧亚烷基多元醇，该多元醇组合物具有2至4的平均标称羟基官能度、500至7000的平均羟基当量及于50％与85％(重量)之间的平均氧亚乙基含量，及链增长剂具有至多250的平均羟基当量。
于本发明中使用的多异氰酸酯成分可以是任何芳族或脂族多异氰酸酯，诸如TDI、NDI或纯净的二异氰酸4,4′-二苯基甲烷酯或该二异氰酸酯与一种或一种以上其他有机多异氰酸酯的混合物，特别是其他的多异氰酸二苯基甲烷酯异构物，例如，任选连同2,2′-异构物的2,4′-异构物。多异氰酸酯成分也可以是自包含至少85％(重量)的二异氰酸4,4′-二苯基甲烷酯的一种多异氰酸酯组合物衍生的一种MDI变型。MDI变型于此领域中是熟知的，并且，对于按照本发明之用途，特别地包括经由引进uretonimine和/或碳化二亚胺基进入该多异氰酸酯组合物中和/或经由与一种或一种以上多元醇反应而获得的液体产物。
作为多异氰酸酯成分，较优选的是包含至少90％(重量)的二异氰酸4,4′二苯基甲烷酯的多异氰酸酯组合物。包含至少95％(重量)的二异氰酸4,4′-二苯基甲烷酯的多异氰酸酯组合物是最优选的。
多元醇组合物可以是由任选掺和其他多元醇(诸如聚酯多元醇)的一种或一种以上聚醚多元醇组成。
组合物可包含一种单一之聚氧亚烷基多元醇，其较优选地是具有需要的官能度、当量及氧亚乙基含量的一种聚(氧亚乙基-氧亚丙基)多元醇。此等多元醇于此领域中是已知的及可以采用习用之方法经由用一种引发剂诸如水、一种多元醇、一种羟胺、具有2至4个活性氢原子的一种多元胺及其类似物同时地和/或以任何次序连续地与环氧乙烷及环氧丙烷反应而获得。
或者，多元醇组合物可包含两种或两种以上聚氧亚烷基多元醇的一种混合物，以使总组合物具有需要的平均官能度、当量及氧亚乙基含量。于此等混合物中存在的聚氧亚烷基多元醇较优选地是聚(氧亚乙基-氧亚丙基)多元醇，但亦可以存在一种或一种以上聚氧亚乙基多元醇和/或聚氧亚丙基多元醇。
较优选的聚醚多元醇组合物包含：
a)75-100％(重量)之包含至少一种包含氧亚乙基残基的聚氧亚烷基多元醇之第一种多元醇成分，该多元醇成分具有2至4的平均标称羟基官能度、1000至5000的平均羟基当量及60至85％(重量)的平均氧亚乙基含量，及
b)25至0％(重量)的另一种多元醇成分。
多元醇成分(b)适合地具有2至4的平均官能度、1000至3000的平均当量及可以是，例如，一种聚氧亚丙基多元醇、一种聚氧亚乙基多元醇或者包含低于60％(重量)或高于85％(重量)的氧亚乙基残基之一种聚(氧亚乙基-氧亚丙基)多元醇。
术语“平均标称羟基官能度”被使用于本文中以表示多元醇组合物的平均官能度(每分子中羟基的数目)，假定在多元醇组合物中存在的聚氧亚烷基多元醇的平均官能度是完全相同于在彼等之制备中使用的引发剂的平均官能度(每分子中活性氢原子的数目)(虽然于实务上由于部分末端不饱和作用，因此该值常将是略微较低)。
最好多元醇组合物的平均标称羟基官能度为2至3。
倘若需要，聚氧亚烷基多元醇(或当使用一种混合物时，一种或一种以上之聚氧亚烷基多元醇)可包含分散的聚合物粒子。此种聚合物改性的多元醇在现有技术中已充分地描述，其包括经由于聚氧亚烷基多元醇中一种或一种以上乙烯基单体(例如丙烯腈及苯乙烯)的就地聚合作用或经由于聚氧亚烷基中于一种多异氰酸酯与一种胺基或羟基-官能化合物(例如三乙醇胺)之间的就地反应而获得的产物。
亦适合于作为多元醇(b)者是聚酯多元醇。
可使用的聚酯多元醇包括多羟基醇(诸如乙二醇、丙二醇、二甘醇、一缩二(丙二醇)、1,4-丁二醇、对苯二甲酸双(羟乙基)酯、甘油、三羟甲基丙烷、己二醇、新戊二醇、甲基戊二醇、季戊四醇或者聚醚多元醇或此类多羟基醇的混合物)与多元羧酸(特别是二羧酸或它们的成酯衍生物，例如，丁二酸、戊二酸及己二酸或它们的二甲基酯、癸二酸、邻苯二甲酸酐、四氯邻苯二甲酸酐或对苯二甲酸二甲酯或其混合物)之羟基-封端的反应产物。
较优选的聚酯具有750-4000的数均分子量，特别是750-2500，及2-3的平均标称官能度。
适合之链增长剂包括低分子量二醇、胺基醇或二醇诸如乙二醇、二甘醇、一缩二(丙二醇)、二缩三丙二醇、丙二醇、丁二醇、戊二醇、己二醇、3-甲基戊-1,5-二醇、乙醇胺或二乙基甲苯二胺。
可将具有3或3以上的平均官能度的低分子量异氰酸酯-反应性化合物，诸如甘油，季戊四醇或三乙醇胺作为交联剂加入。
最好将少量水，最优选的是，以异氰酸酯-反应性物质的总重量为基准，低于2％(重量)的水，加入配制物中。反应体系的异氰酸酯指数，考虑多元醇组合物、水及任何其他异氰酸酯-反应性物种(例如链增长剂及任选用之交联剂)，可为低至85或高至120。较优选地，异氰酸酯-指数为于90与110之间。最优选的并氰酸酯指数为于95-105之间。
生成弹性体的反应混合物可包含对于此等反应混合物习用的一种或一种以上添加剂。此等添加剂包括催化剂(例如叔胺及锡化合物)、表面活性剂及泡沫稳定剂(例如，硅氧烷-氧亚烷基共聚物)、阻燃剂、有机及无机填充剂、颜料，及内脱模剂。
另外本发明提供一种包含下列物料的反应体系：
(a)包含至少85％(重量)的二异氰酸酯4,4′-二苯基甲烷酯或其一种变体的一种多异氰酸酯成分；
(b)包含至少一种包含氧亚乙基残基的聚氧亚烷基多元醇的一种多元醇组合物，该多元醇组合物具有2至4的平均标称羟基官能度、500至7000的平均羟基当量及于50％至85％(重量)之间的平均氧乙烯含量：
(c)具有至多250的平均羟基当量的一种链增长剂，及任选的
(d)水，
(e)一种交联剂，及
(f)对于弹性体配制物习用的一种或一种以上添加剂。
此种反应体系被使用以制造聚氨酯弹性体。
在实施本发明时，可以将已知的单程(one-shot)、半-预聚合物或完全预聚合物工艺与弹性体之制备中习惯使用的混合设备一起应用。
按照本发明的弹性体特别适合于在其中需要良好的能量-吸收及疲劳性质并要求在较宽的温度范围具有良好的弹性体行为之应用场合中(例如，于汽车及鞋工业中)使用。
用下列实例举例说明本发明，其中所有份数、百分比及比例均以重量计。
列出下面的材料词汇表，以区分实施例中未另外明示其它意义的反应成分。词汇多异氰酸酯Ⅰ：纯净的4,4′-MDI(Suprasec M PR；帝国化学工业公司(Imperial Chemical Industries PLC)有售；Suprasee是帝国化学工业公司的一种商标)。多异氰酸酯Ⅱ：uretonimine-改性的MDI(Suprasec 2020；自帝国化学工业公司市售的)。多异氰酸酯Ⅲ：MDI-基预聚合物(Suprasec 2433；自帝国化学工业公司市售的)。多异氰酸酯Ⅳ：经由使多异氰酸酯Ⅰ与多元醇B反应而制造的多异氰酸酯预聚合物(NCO-含量=8.66％)。多元醇A：    具有70％无规EO-基；42毫克KOH/克的OH-值及约45％伯OH-基之EO/PO三元醇。多元醇B：    具有75％无规EO-基及27毫克KOH/克的OH-值之EO/PO二醇。多元醇C：    一种EO/PO二醇(22％EO tip；OH-值=35毫克KOH/克)与一种EO/PO三元醇(15％EOtip；OH-值=32毫克KOH/克)之一种70/30掺混物。多元醇D：    聚合物-改性的多元醇(具有OH-值=34毫克KOH/克；15％EO-tip；75％伯OH-基及包含20％苯乙烯-丙烯腈共聚物粒子的甘油引发之多醇)。多元醇E：    具有27％EO-tip及30毫克KOH/克的OH-值之EO/PO二醇。催化剂1：    Dabco EG；自空气产品公司(Air Products)市售。催化剂2：    Niax Al；自联合碳化物公司(Union Carbide)市售。EG：         乙二醇实例实例1、2、3及4及比较实例1及2
在一种15×10×1厘米模具中，按照习惯使用的方法，使用表Ⅰ中所示配方分组地模制，并测量出于表1中所示性质。
表1
    1     2     3     4 比较1 比较2
多异氰酸酯Ⅰ    36.4    42.7     -     -     -     -
多异氰酸酯Ⅱ     -     -     46.8     -     -     42.9
多异氰酸酯Ⅲ     -     -     -     -     109     -
多异氰酸酯Ⅳ     -     -     -     100     -     -
多元醇A  100.0    50.0     -     -     -     -
多元醇B     -    50.0    100.0     -     -     -
多元醇C     -     -     -     -     100.0     -
多元醇D     -     -     -     -     28.3     -
多元醇E     -     -     -     -     -     100.0
乙二醇     5.0    7.0     7.0     4.55     8.9     6.0
水     0.3    0.3     0.3     0.21     0.6     0.3
催化剂1     1.0    0.5     1.0     0.7     2.6     1.0
催化剂2     -     -     -     -     0.4     -
模制物密度(千克/立方米)     450     440     440     580     490     585
硬度     46(Asker C)     51(Asker C)     41(Asker C)     62(Asker C)     47(肖耳A)     N.M.*
E′(20℃)/E′(120℃)比例     0.95     1.01     0.98     0.86     1.69     2.19
tan δ(100℃)     0.002     0.013     0.024     0.005     0.070     0.078
tan δ MAX(于℃之温度)     -23     -26     -11     -11     -43     -45
tan δ MAX(值)     1.08     0.86     1.01     1.22     0.42     0.37
*N.M.=未测量
按照比较实例的弹性体的E′(20℃)/E(120℃)比例高于1.5，而其损耗角正切最高值低于0.8。DMTA-试验
按照ISO/DIS6721-5于一种流变测定科学公司(RheometricScientific)DMTA装置上使用一种三点弯曲方法进行测量，试验样品尺寸为：长度1.0厘米、宽度1.3厘米、厚度0.4厘米。施加之应变振幅64×10-4厘米、频率1赫兹、加热速率2℃/分钟。于试验之前，于23℃/50％相对湿度预调节弹性体样品历时24小时。于开始加热样品之前，骤冷弹性体样品至-120℃(冷却速率8.5℃/分钟)及维持于此温度历时5分钟。
图1-4表示实例1-4的DMTA-曲线。比较实例1及2的DMTA-曲线示于图5及6中。

Claims (19)

1．一种具有于0.75与1.5之间的于20℃的储能模量(E′)与于120℃的储能模量(E″)之比例、低于0.1的于100℃的损耗角正切(tanδ)及超过0.8的损耗角正切的最高值的多异氰酸酯基的弹性体，损耗角正切是损耗模量(E″)与储能模量(E′)之比例。
2．按照权利要求1的弹性体，其中多异氰酸酯包含至少90％(重量)的二异氰酸4,4′-二苯基甲烷酯。
3．按照权利要求2的弹性体，其中多异氰酸酯包含至少95％(重量)的二异氰酸4,4′-二苯基甲烷酯。
4．按照前述权利要求1中任何一项的弹性体，具有于0.8与1.2之间的于20℃的储能模量(E′)与于120℃的储能模量(E′)之比例。
5．按照权利要求4的弹性体，具有于0.85与1.1之间的于20℃的储能模量(E′)与于120℃的储能模量(E′)之比例。
6．按照前述权利要求中任何一项的弹性体，具有低于0.05的于100℃的损耗角正切。
7．按照权利要求6的弹性体，具有低于0.03的于100℃的损耗角正切。
8．按照前述权利要求中任何一项的弹性体，具有超过1.0的损耗角正切的最高值。
9．按照前述权利要求中任何一项的弹性体，具有于低于0℃的温度的损耗角正切的主要最高值。
10．按照权利要求9的弹性体，具有于低于10℃的温度的损耗角正切的主要最高值。
11．一种自包含一种多异氰酸酯成分、一种多元醇组合物、一种链增长剂及任选一种交联剂的反应混合物制备按照前述权利要求中任何一项的弹性体的方法，其中多异氰酸酯成分包含至少85％(重量)之二异氰酸4,4′-二苯基甲烷酯或其一种变型、多元醇组合物包含至少一种包含氧亚乙基残基的聚氧亚烷基多元醇，该多元醇组合物具有2至4的平均标称羟基官能度、500至7000之平均羟基当量及于50％至85％(重量)之间的平均氧亚乙基含量，及链增长剂具有至多250之平均羟基当量。
12．按照权利要求11的方法，其中多元醇组合物包含至少一种聚(氧亚乙基-氧亚丙基)多元醇。
13．按照权利要求12的方法，其中多元醇组合物包含：
a)75-100％(重量)的包含至少一种包含氧亚乙基残基的聚氧亚烷基多元醇之第一种多元醇成分，该多元醇成分具有2至4的平均标称羟基官能度、1000至5000的平均羟基当量及60％至85％(重量)的平均氧亚乙基含量，及
b)25％至0％(重量)的另一种多元醇成分。
14．按照权利要求11～13中任何一项的方法，其中多元醇组合物具有2至3的平均标称羟基官能度。
15．按照权利要求11～14中任何一项的方法，其中反应混合物另外包含水。
16．按照权利要求15的方法，其中以异氰酸酯反应性化合物的总重量为基准，水的数量为低于2％(重量)。
17．按照权利要求11-16中任何一项的方法，其于90与110之间的异氰酸酯-指数下进行。
18．按照权利要求17的方法，其于95与105之间的异氰酸酯-指数下进行。
19．一种反应体系，包含：
(a)包含至少85％(重量)的二异氰酸酯4,4′-二苯基甲烷酯或其一种变型的一种多异氰酸酯成分；
(b)包含至少一种包含氧亚乙基残基的聚氧亚烷基多元醇的一种多元醇组合物，该多元醇组合物具有2至4的平均名目羟基官能度、500至7000的平均标称羟基当量及于50％至85％(重量)之间的平均氧亚乙基含量；
(c)具有至多250的平均羟基当量的一种链增长剂；，
(d)水，
(e)一种交联剂，及
(f)对于弹性体配制物习用的一种或一种以上添加剂。
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100381478C (zh) * 2001-02-12 2008-04-16 路博润高级材料公司 由具有高仲羟基含量的多元醇制成的高分子量热塑性聚氨酯
CN101148494B (zh) * 2007-10-26 2010-07-21 张勇 一种聚氨酯弹性体的生产方法及应用
CN101160210B (zh) * 2005-04-05 2010-09-22 陶氏环球技术公司 刚性聚氨酯-异氰脲酸酯增强泡沫
CN106164122A (zh) * 2013-04-09 2016-11-23 陶氏化学墨西哥股份公司 快速固化的粘合剂组合物
CN108351050A (zh) * 2015-11-30 2018-07-31 株式会社润工社 聚氨酯管

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000055232A1 (en) * 1999-03-17 2000-09-21 Huntsman International Llc Process for preparing moulded polyurethane material
EP1172387A1 (en) * 2000-07-14 2002-01-16 Huntsman International Llc Process for preparing an elastomer
US7687548B2 (en) 2002-07-01 2010-03-30 Huntsman International Llc Process for preparing a moulded polyurethane material
DE10303172A1 (de) * 2003-01-27 2004-07-29 Basf Ag Verfahren zur Herstellung von Polyurethanintegralschaumstoffen
US7168880B2 (en) * 2004-11-17 2007-01-30 Battelle Memorial Institute Impact attenuator system
DE102004062539A1 (de) * 2004-12-24 2006-07-20 Bayer Materialscience Ag Verstärkte Polyurethanharnstoffelastomere und deren Verwendung
US20060258831A1 (en) * 2005-05-10 2006-11-16 Nigel Barksby High molecular weight thermoplastic polyurethanes made from polyols having high secondary hydroxyl content
US20090035350A1 (en) 2007-08-03 2009-02-05 John Stankus Polymers for implantable devices exhibiting shape-memory effects
JP5759364B2 (ja) * 2008-03-17 2015-08-05 バテル・メモリアル・インスティテュートＢａｔｔｅｌｌｅ Ｍｅｍｏｒｉａｌ Ｉｎｓｔｉｔｕｔｅ リバウンド制御材
US9259515B2 (en) 2008-04-10 2016-02-16 Abbott Cardiovascular Systems Inc. Implantable medical devices fabricated from polyurethanes with grafted radiopaque groups
ES2715837T3 (es) * 2011-05-16 2019-06-06 Ashland Licensing & Ip Llc Adhesivo de poliurea-uretano de dos partes con módulo de almacenamiento elevado a alta temperatura
CN102250313B (zh) 2011-06-03 2012-09-26 山东东大一诺威聚氨酯有限公司 一种用于聚氨酯发泡轮胎的自结皮微孔弹性体组合物
WO2014052331A2 (en) 2012-09-26 2014-04-03 Dow Global Technologies Llc Polyurethane bend stiffener
US8720921B1 (en) * 2012-10-30 2014-05-13 SuperSprings International, Inc. Vehicular suspension enhancement
JP6253942B2 (ja) * 2013-10-10 2017-12-27 ヤマハ株式会社 発泡ウレタンゴム及び発泡ウレタンゴム形成用組成物
WO2017094699A1 (ja) * 2015-11-30 2017-06-08 株式会社 潤工社 ポリウレタンチューブ

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE31671E (en) 1974-09-09 1984-09-11 The Upjohn Company Thermoplastic polyurethane elastomers from polyoxypropylene polyoxyethylene block copolymers
US3983094A (en) * 1975-09-11 1976-09-28 Uniroyal, Inc. Thermally stable polyurethane elastomers produced from poly(oxypropylene)-poly(oxyethylene)glycols of high oxyethylene group content
US4010146A (en) * 1975-09-29 1977-03-01 Samuel Moore And Company Polyol blends and polyurethane prepared therefrom
US4124572A (en) 1977-07-05 1978-11-07 Uniroyal, Inc. Thermoplastic polyurethane elastomer
US4312973A (en) 1978-08-10 1982-01-26 Union Carbide Corporation Polyurethane elastomers prepared from polyol or polymer/polyol-chain extender mixtures
AU532047B2 (en) * 1978-12-11 1983-09-15 Ici Ltd. Modified isocyanate
US4379904A (en) 1980-11-24 1983-04-12 The Upjohn Company Novel polyurethane product
DE3113690A1 (de) * 1981-04-04 1982-10-28 Elastogran GmbH, 2844 Lemförde "verfahren zur herstellung von geschlossenzelligen polyurethan-formteilen mit einer verdichteten randzone"
DE3219759A1 (de) 1982-05-26 1983-12-01 Bayer Ag, 5090 Leverkusen Einphasig lagerstabile polyolkompositionen mit hohem ethylenglykol-anteil und ihre verwendung zur herstellung von polyurethanen
US4524102A (en) 1984-02-15 1985-06-18 Fritz Hostettler Microcellular polyurethane foams having integral skin
JPH0680105B2 (ja) * 1985-04-16 1994-10-12 旭硝子株式会社 ポリウレタン系エラストマ−の製造方法
US4767825A (en) 1986-12-22 1988-08-30 Kimberly-Clark Corporation Superabsorbent thermoplastic compositions and nonwoven webs prepared therefrom
JPH0794523B2 (ja) 1987-09-02 1995-10-11 東洋ゴム工業株式会社 高透湿性、低膨潤性、高モジュラス等のすぐれた特性を有するポリウレタン重合体の製造方法
US5001167A (en) 1989-03-21 1991-03-19 The Dow Chemical Company Solvent resistant polyetherpolyurethane products
JP2566472B2 (ja) 1989-12-04 1996-12-25 株式会社エポゾール 耐熱性かつ熱可塑性の、ポリウレタンエラストマー及びその製造法
ES2102472T3 (es) * 1991-12-17 1997-08-01 Ici Plc Espumas de poliuretano.
US5418261A (en) 1993-01-25 1995-05-23 Imperial Chemical Industries Plc Polyurethane foams
JP2733180B2 (ja) * 1993-02-09 1998-03-30 東洋製罐株式会社 フレキシブル包装用ラミネート、その製造方法及びそれに用いる接着剤
US5459170A (en) 1993-04-13 1995-10-17 Imperial Chemical Industries Plc Polyurethane foams
US5591779A (en) 1994-11-22 1997-01-07 Imperial Chemical Industries Plc Process for making flexible foams
EP1172387A1 (en) * 2000-07-14 2002-01-16 Huntsman International Llc Process for preparing an elastomer

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100381478C (zh) * 2001-02-12 2008-04-16 路博润高级材料公司 由具有高仲羟基含量的多元醇制成的高分子量热塑性聚氨酯
CN101160210B (zh) * 2005-04-05 2010-09-22 陶氏环球技术公司 刚性聚氨酯-异氰脲酸酯增强泡沫
CN101148494B (zh) * 2007-10-26 2010-07-21 张勇 一种聚氨酯弹性体的生产方法及应用
CN106164122A (zh) * 2013-04-09 2016-11-23 陶氏化学墨西哥股份公司 快速固化的粘合剂组合物
CN108351050A (zh) * 2015-11-30 2018-07-31 株式会社润工社 聚氨酯管
CN108351050B (zh) * 2015-11-30 2020-06-19 株式会社润工社 聚氨酯管
US10823314B2 (en) 2015-11-30 2020-11-03 Junkosha Inc. Polyurethane tube

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TW419489B (en) 2001-01-21
EP0865458B2 (en) 2005-08-31
PL327198A1 (en) 1998-11-23
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JP3892042B2 (ja) 2007-03-14
MX9804599A (es) 1998-10-31
TR199801042T2 (xx) 1998-09-21
ATE198756T1 (de) 2001-02-15
EP0865458A1 (en) 1998-09-23
JP2006316281A (ja) 2006-11-24
DE69611623T3 (de) 2006-03-16
US20020103325A1 (en) 2002-08-01
JP3889435B2 (ja) 2007-03-07
DK0865458T3 (da) 2001-01-29
DE69611623D1 (en) 2001-02-22
ES2153601T3 (es) 2001-03-01
DE69611623T2 (de) 2001-06-28
ID19591A (id) 1998-07-23
PL187124B1 (pl) 2004-05-31
EP0865458B1 (en) 2001-01-17
CN1210324C (zh) 2005-07-13
AU7625896A (en) 1997-07-03
PT865458E (pt) 2001-04-30
KR100441926B1 (ko) 2005-01-15
BR9611977A (pt) 1999-02-17
AU718820B2 (en) 2000-04-20
CA2239482A1 (en) 1997-06-19
MY129258A (en) 2007-03-30
AR005001A1 (es) 1999-04-07
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KR19990071971A (ko) 1999-09-27
WO1997021750A1 (en) 1997-06-19
DK0865458T4 (da) 2005-09-19
CA2239482C (en) 2008-03-18

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