CN1150243C - 含有丁二醇和聚乙二醇单元的硬质热塑性聚氨酯 - Google Patents

含有丁二醇和聚乙二醇单元的硬质热塑性聚氨酯 Download PDF

Info

Publication number
CN1150243C
CN1150243C CNB961802839A CN96180283A CN1150243C CN 1150243 C CN1150243 C CN 1150243C CN B961802839 A CNB961802839 A CN B961802839A CN 96180283 A CN96180283 A CN 96180283A CN 1150243 C CN1150243 C CN 1150243C
Authority
CN
China
Prior art keywords
unit
thermoplastic polyurethane
molecular weight
rtpu
glycol
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.)
Expired - Fee Related
Application number
CNB961802839A
Other languages
English (en)
Other versions
CN1217001A (zh
Inventor
S・R・奥里亚尼
S·R·奥里亚尼
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lubrizol Advanced Materials Inc
Original Assignee
Dow Global Technologies LLC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Publication of CN1217001A publication Critical patent/CN1217001A/zh
Application granted granted Critical
Publication of CN1150243C publication Critical patent/CN1150243C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

本发明涉及含有丁二醇(BDO)和HO-(CH2CH2O)n-H型聚乙二醇(PEG)单元的硬质热塑性聚氨酯(RTPU)，其中n为2～6的整数。本发明的RTPU通过提供一种为由己二醇制备的RTPU的潜在低成本替换物及进一步提供一种能调节到所需的韧性Tg。屈服强度和透明度的RTPU而解决本领域的问题。从一定摩尔比的BDO与PEG制得的RTPU具有惊人高的韧性，这表现在其断裂拉伸伸长率增加。

Description

含有丁二醇和聚乙二醇单元的硬质热塑性聚氨酯
硬质热塑性聚氨酯(RTPU)为单相或双相聚合物，能通过近乎化学计算量的a)二异氰酸酯和b)二醇的反应进行制备，二醇包括低分子量的二醇(分子量不大于300)和高分子量的二醇(分子量一般为500～8000)。这些RTPU的玻璃化转变温度(Tg)不低于50℃，一般情况下硬链段含量不少于75％。这些RTPU的公开及制备在例如Goldwasser等的美国专利4,376,834中进行了说明。
在有些情况下，希望制备光学透明的RTPU，即具有单一Tg的无定形RTPU。这些光学透明的RTPU通常是用己二醇作为低分子量的二醇进行制备的，它们可用于许多需要韧性、耐化学性和尺寸稳定性的应用中。从光学透明的RTPU制备的有用产品的例子有牙刷柄、滤水或滤油的组件、窗户、静脉输送系统的连接管。
虽然己二醇为制备光学透明的RTPU的有效单体，但是希望能用允许有更大的柔韧性的替代单体来调节RTPU的物理性能如Tg和屈服强度。另外，还希望这样的替代单体能使RTPU的成本降低。
本发明涉及硬质热塑性聚氨酯，它含有：a)二异氰酸酯单元、b)结构为HO-(CH2CH2O)n-H的聚乙二醇单元，其中n为2～6的整数、c)丁二醇单元和d)基于硬质热塑性聚氨酯总重不超过25wt.％的高分子量二醇单元，该硬质热塑性聚氨酯的特征还在于其Tg至少为50℃，条件是当聚乙二醇为三甘醇时，至少有下述限制之一：a)三甘醇单元与丁二醇单元的摩尔比为25∶75～90∶10、b)硬质热塑性聚氨酯包含不大于1.9wt％的高分子量二醇单元、或c)热塑性聚氨酯为光学透明的。
另一方面，本发明涉及硬质热塑性聚氨酯，它含有：a)二异氰酸酯单元、b)三甘醇单元、c)丁二醇单元和d)基于硬质热塑性聚氨酯总重不超过1.9wt％的高分子量二醇单元，该硬质热塑性聚氨酯的特征还在于其Tg至少为50℃。
再一方面，本发明涉及硬质热塑性聚氨酯，它含有：a)二异氰酸酯单元、b)二甘醇单元、c)丁二醇单元和d)基于硬质热塑性聚氨酯总重不超过25wt％的高分子量二醇单元，该硬质热塑性聚氨酯的特征还在于其Tg至少为50℃。
本发明通过提供一种为由己二醇制备的RTPU的潜代低成本替代物及进一步提供一种能调节到所需的韧性、Tg、屈服强度和透明度的RTPU解决本领域的问题。已经发现这样的RTPU能从二异氰酸酯与BDO及聚乙二醇(PEG)的反应制得。从一定摩尔比BDO与PEG制备的RTPU具有惊人高的韧性，这表现为其断裂拉伸伸长率增加。
图1为RTPU的断裂拉伸伸长率与用于制备RTPU的TEG与BDO的摩尔比的关系图。
图2为RTPU的断裂拉伸伸长率与用于制备RTPU的DEG与BDO的摩尔比的关系图。
图3为RTPU的断裂拉伸伸长率与用于制备RTPU的E-300与BDO的摩尔比的关系图。
术语说明
术语“PEG与BDO混合物”指聚乙二醇与丁二醇的掺混物，当与二异氰酸酯反应时，它形成含有具有PEG和BDO单元的骨架的聚合物。
术语“单元”在这里用来指在RTPU中的分子链段的重复序列。例如，术语“丁二醇单元”在这里用来指在RTPU中的下述重复序列：
                       -O-(CH2)4-O-
同样，术语“三甘醇单元”在这里用来指在RTPU中的下述重复序列：
-O-(CH2CH2O)3-
术语“二异氰酸酯单元”在这里用来指RTPU中的下述重复序列：
其中R为芳族、脂族或环脂族基团。
术语“丁二醇”在这里用来指1，4-丁二醇。
通过二异氰酸酯与PEG和BDO反应可以制备本发明的RTPU。PEG优选为TEG或DEG，更优选为TEG。当PEG为TEG时，在RTPU中TEG单元与BDO单元的摩尔比优选为从25∶75、更优选为从35∶65、最优选为从45∶55到90∶10、更优选为到75∶25、最优选为到60∶40。
当PEG为DEG时，DEG与BDO的摩尔比优选为从25∶75、更优选为从40∶60、最优选为从50∶50到70∶30、更优选为65∶35、最优选为到60∶40。
当PEG为六甘醇(E-300)时，E-300与BDO的摩尔比优选为从30∶70到60∶40。当E-300与BDO的摩尔比稍高于60∶40时，TPU的Tg降到50℃以下。
优选的二异氰酸酯包括芳族、脂族和环脂族的二异氰酸酯以及它们的混合物。在美国专利4,385,133、4,522,975和5,167,899中可以找到这些优选的二异氰酸酯的代表性实例。优选的二异氰酸酯包括4，4′-二异氰酸基二苯基甲烷、对亚苯基二异氰酸酯、1，3-二(异氰酸基甲基)-环己烷、1，4-二异氰酸基环己烷、六亚甲基二异氰酸酯、1，5-萘二异氰酸酯、3，3′-二甲基-4，4′-联苯二异氰酸酯、4，4′-二异氰酸基二环己基甲烷和2，4-甲苯二异氰酸酯。更优选为4，4′-二异氰酸基二环己基甲烷和4，4′-二异氰酸基二苯基甲烷。最优选为4，4′-二异氰酸基二苯基甲烷。
RTPU任意性可有可无地含有基于硬质热塑性聚氨酯总重不超过25wt％的高分子量二醇单元。术语“高分子量二醇”在这里用来指分子量不少于500原子质量单位的二醇。优选的高分子量二醇为聚酯和聚醚二醇。
高分子量二醇的分子量优选为不低于600且不高于8000原子质量单位。高分子量二醇单元在RTPU中的分数足够低，以使RTPU的Tg至少为50℃。高分子量二醇单元在RTPU中的重量百分比优选为从不大于10、更优选为不大于5、进一步优选为不大于1.9、更进一步优选为不大于1.5、最优选为不大于1到0。
光学透明的RTPU可以通过从RTPU中除去高分子量二醇进行制备，或只要一种或几种高分子量二醇单元的浓度低到足以保持Tg不低于50℃，也可以通过加入与RTPU的BDO和PEG单元形成单相的高分子量二醇或几种高分子量二醇的混合物进行制备。
可以用于形成光学透明的RTPU的高分子量二醇的实例包括聚醚二醇如聚丙二醇、聚乙二醇和聚四亚甲基二醇；和聚酯二醇如聚己酸内酯二醇以及能从脂族二元酸、二元酯或二(酰氯)与C2-C8线性、支化或环状二醇、或含有二醇的醚、或它们的混合物进行缩聚反应制备的化合物。用于形成光学透明的RTPU的高分子量二醇更优选包括聚己酸内酯二醇、聚己二酸亚乙基酯二醇和聚己二酸亚丁基酯二醇。
高分子量聚醚二醇的分子量优选为600～1000原子质量单位。高分子量聚酯二醇的分子量优选为不少于600，更优选不少于800、最优选为不少于1000到不大于2000、更优选为不大于1800、最优选为不大于1600原子质量单位。
在反应物中异氰酸酯与OH之比从0.95∶1、优选为从0.975∶1、更优选为0.985∶1到1.05∶1、优选为1.025∶1、更优选为1.015∶1之间变化。
本发明的RTPU有利地在适宜的催化剂存在下进行制备，例如在美国再颁发专利37,671的第5栏第46行到第6栏第5行中公开了这些催化剂。优选的催化剂包含辛酸亚锡、油酸亚锡、二辛酸二丁基锡、二月桂酸二丁基锡。所用催化剂的量足以提高异氰酸酯基团与OH基的反应活性，但又不会不希望地影响最终产品的性能，该量基于反应物总重优选为0.02～2.0wt.％。
用间歇式或连续方法如本领域已知的那些可以适当地制备本发明的RTPU。优选的连续混合方法为反应性挤出，例如美国专利3,642,964公开的双螺杆挤出法。
用这里说明的材料可以制备光学透明的RTPU。这些材料可以通过例如挤出或注塑进行加工，形成增韧的无定形透明制品如牙刷柄、滤水或滤油的组件、窗户及静脉输送系统的连接管。
适宜地，也可以在本发明没有具体公开的材料不存在下进行本发明的实施。
下述实施例是为了说明的目的而给出的，并不是特意来限制本发明的范围。
实施例1-用TEG和BDO制备光学透明的RTPU
将TEG(从Dow Chemical Company得到)和BDO(从E.I.duPont de Nemours & Co.，Inc.得到)分别装在两个1000升的容器中。在100kPa真空、105℃下将该两种试剂汽提处理4小时以使水分含量降到150ppm以下。汽提完成后，容器用干燥的氮气进行填充。将MDI(4，4′-二异氰酸基二苯基甲烷，对位-对位的含量大于98％)储存在通氮并保持在63℃下的容器中。只要每一种试剂的量足够用于适宜的实验，装入容器中的试剂的准确量并不重要。
将TEG、BDO和MDI与FOMREZTM UL-22催化剂(Witco公司的商标)及IrganoxTM 1010稳定剂(Ciba-Geigy公司的商标)一起计量加入配有啮合的、自清扫螺杆的Werner & Pfleiderer ZSK双螺杆挤出机的进料区。控制TEG、BDO和MDI的进料速率，使NCO基与OH基的摩尔比在1.0075～1.0125之间。挤出机螺杆的旋转速度在整个过程中固定不变。下表列出在不同的BDO与TEG摩尔比下试剂、催化剂和稳定剂的进料速率。在每一批中，制备大约40千克材料。
     试剂的摩尔当量                 进料速率(千克/小时)
  BDO   TEG   MDI   BDO   TEG   MDI   Irg1010   UL-22
  0   1   1.01   0   68.04   113.22   0.45   0.11
  0.1   0.9   1.01   4.10   62.18   114.98   0.45   0.11
  0.2   0.8   1.01   8.32   56.14   116.79   0.45   0.11
  0.3   0.7   1.01   12.69   49.91   118.66   0.45   0.11
  0.4   0.6   1.01   17.19   43.48   120.59   0.45   0.11
  0.5   0.5   1.01   21.84   36.83   122.58   0.45   0.11
  0.6   0.4   1.01   26.65   29.96   124.65   0.45   0.11
  0.7   0.3   1.01   31.62   22.85   126.78   0.45   0.11
  0.8   0.2   1.01   36.77   15.50   128.98   0.45   0.11
  0.9   0.1   1.01   42.10   7.89   131.27   0.45   0.11
  1   0   1.01   47.62   0.00   133.64   0.45   0.11
在运行过程中，为了优化料片处理和控制压力在挤出机中的分布，对机筒和模头温度稍微进行调整。温度设定在200～235℃的范围内。
RTPU通过模头从挤出机中排出，在骤冷并涂有聚四氟乙烯的金属带上形成15厘米×0.3厘米的料片。冷却1～2分钟后将料片切成小方粒，把所得的粒料装在防潮的金属箔衬里的袋子中。
将RTPU粒料放在去湿干燥器的料斗中，用露点约为-34℃的热空气通过这些粒料。将粒料干燥12小时后，转移到Arburg 221E/150注塑机的料斗中，按ASTM D638生产I型拉伸试条。在模塑过程中，用干燥氮气将注塑机的料斗保护起来，以防止RTPU吸潮。设定机筒温度，以使每一种RTPU都完全填满模具，所用的保压压力在4800～5500kPa。注射速度慢，低于注塑机容量的40％(旋钮设定为2或更少)。得到的拉伸样品看不出有污点、展出、合流线并且光学透明。这些样品具有单一玻璃化转变温度，用以20℃/分的加热模式操作的Mettler 30型差示扫描量热仪测定为在80℃(100％的TEG)～118℃(100％的BDO)的范围内。
在23℃、相对湿度为50％的条件下调节24小时后，用Instron 1120在十字头的速度为5厘米/分的条件下，每一RTPU拉10个拉伸样品。夹具的起始位移为11.4厘米，在标距为5厘米长的样品上用伸长计确定断裂伸长率。图1为断裂拉伸伸长率(根据ASTM D-638测定)与TEG/BDO掺混物中TEG的摩尔分数的关系图。用所描述的方法制备的RTPU为光学透明的，即它们具有单一玻璃化转变温度。

Claims (7)

1.具有至少50℃Tg的硬质透明热塑性聚氨酯，包含：
a)二异氰酸酯单元；
b)聚乙二醇单元，其为三甘醇或二甘醇；进一步特征为：
b.1)如果使用三甘醇，则三甘醇单元与丁二醇单元的摩尔比为25∶75～90∶10，或
b.2)如果使用二甘醇，则二甘醇单元与丁二醇单元的摩尔比为25∶75～65∶35；
c)丁二醇单元，以上述b)中规定的摩尔比；和
d)基于硬质热塑性聚氨酯总重不超过25wt.％且分子量不低于500原子质量单位的高分子量二醇单元。
2.根据权利要求1的热塑性聚氨酯，其中热塑性聚氨酯具有单一玻璃化转变温度。
3.根据权利要求1或2的热塑性聚氨酯，含有不超过1wt.％的高分子量二醇单元。
4.根据权利要求1或2的热塑性聚氨酯，含有0wt.％的高分子量二醇单元。
5.根据权利要求1或2的热塑性聚氨酯，其中高分子量二醇单元包含分子量在600～1800原子质量单位范围内的聚己二酸亚乙基酯二醇或聚己二酸亚丁基酯二醇单元或分子量在600～1000原子质量单位范围内的聚醚二醇单元。
6.根据权利要求1或2的热塑性聚氨酯，其中二异氰酸酯包含4，4′-二异氰酸基二苯基甲烷、对亚苯基二异氰酸酯、1，3-二(异氰酸基甲基)-环己烷、1，4-二异氰酸基环己烷、六亚甲基二异氰酸酯、1，5-萘二异氰酸酯、3，3′-二甲基-4，4′-联苯基二异氰酸酯、4，4′-二异氰酸基二环己基甲烷或2，4-甲苯二异氰酸酯或其混合物。
7.根据权利要求6的热塑性聚氨酯，其中二异氰酸酯包含4，4′-二异氰酸基二苯基甲烷。
CNB961802839A 1996-05-03 1996-05-09 含有丁二醇和聚乙二醇单元的硬质热塑性聚氨酯 Expired - Fee Related CN1150243C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/642,744 US5627254A (en) 1996-05-03 1996-05-03 Rigid thermoplastic plyurethane comprising units of butane diol and a polyethylene glycol
US08/642,744 1996-05-03

Publications (2)

Publication Number Publication Date
CN1217001A CN1217001A (zh) 1999-05-19
CN1150243C true CN1150243C (zh) 2004-05-19

Family

ID=24577823

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB961802839A Expired - Fee Related CN1150243C (zh) 1996-05-03 1996-05-09 含有丁二醇和聚乙二醇单元的硬质热塑性聚氨酯

Country Status (11)

Country Link
US (1) US5627254A (zh)
EP (1) EP0896601B1 (zh)
JP (1) JP2000509744A (zh)
KR (1) KR100431014B1 (zh)
CN (1) CN1150243C (zh)
BR (1) BR9612613A (zh)
CA (1) CA2252459A1 (zh)
DE (1) DE69620471T2 (zh)
ES (1) ES2171671T3 (zh)
TW (1) TW368508B (zh)
WO (1) WO1997042248A1 (zh)

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5645077A (en) * 1994-06-16 1997-07-08 Massachusetts Institute Of Technology Inertial orientation tracker apparatus having automatic drift compensation for tracking human head and other similarly sized body
WO1999039906A1 (en) * 1998-02-05 1999-08-12 The Dow Chemical Company Laminated glazings
US6352779B1 (en) 1999-11-18 2002-03-05 The Dow Chemical Company Electromagnetically welded composite and the preparation thereof
CA2400465C (en) 2000-02-15 2008-06-17 Dow Global Technologies Inc. Mold for reaction injection molding and reaction injection molding process
EP1309448A1 (en) 2000-06-09 2003-05-14 The Dow Chemical Company Fiber-reinforced thermoplastic composite bonded to wood
EP1178063A1 (en) * 2000-08-01 2002-02-06 Huntsman International Llc Process for preparing a polyurethane material
US6469099B1 (en) 2000-11-14 2002-10-22 Dow Global Technologies Inc. Compatibilized resin blends and the preparation thereof
US6824860B2 (en) 2001-01-16 2004-11-30 Avc Holdings Inc. Thermoplastic composite reinforced thermoform and blow-molded article
US6803096B2 (en) * 2001-02-05 2004-10-12 Avc Holdings Inc. Engineering thermoplastic polyurethane reinforced with glass mat
CN100592474C (zh) * 2001-11-13 2010-02-24 东洋橡胶工业株式会社 研磨垫及其制造方法
GB0222522D0 (en) 2002-09-27 2002-11-06 Controlled Therapeutics Sct Water-swellable polymers
US6984709B2 (en) 2002-12-20 2006-01-10 Noveon Ip Holdings Corp. Organometallic-free polyurethanes having low extractables
GB0417401D0 (en) 2004-08-05 2004-09-08 Controlled Therapeutics Sct Stabilised prostaglandin composition
GB0613333D0 (en) 2006-07-05 2006-08-16 Controlled Therapeutics Sct Hydrophilic polyurethane compositions
GB0613638D0 (en) 2006-07-08 2006-08-16 Controlled Therapeutics Sct Polyurethane elastomers
GB0620685D0 (en) 2006-10-18 2006-11-29 Controlled Therapeutics Sct Bioresorbable polymers
DE602008002592D1 (de) * 2007-05-21 2010-10-28 Lubrizol Advanced Mat Inc Harte, aliphatische thermoplastische Polyurethane
EP2516494B1 (en) 2009-12-23 2016-06-01 Essilor International (Compagnie Générale D'Optique) Method of converting a polymerizable composition into thermoplastic polyurethane of improved yellowness index and article obtained by this method
US9169373B2 (en) 2010-05-27 2015-10-27 Essilor International (Compagnie Générale d'Optique) Method for preparing a thermoplastic polyurethane of improved yellowness index, and optical articles made therefrom
EP3371236A1 (en) 2015-11-06 2018-09-12 Lubrizol Advanced Materials, Inc. Crystalline high modulus thermoplastic polyurethane
KR102544387B1 (ko) 2016-12-23 2023-06-15 바스프 에스이 투명 경질 열가소성 폴리우레탄의 제조 방법
WO2019243334A1 (de) 2018-06-19 2019-12-26 Basf Se Transparente harte thermoplastische polyurethane
WO2021110623A1 (en) 2019-12-03 2021-06-10 Basf Se A medical tubing comprising thermoplastic polyurethane
EP3838942A1 (de) 2019-12-17 2021-06-23 Covestro Deutschland AG Verfahren zur herstellung von polyurethanen mit hoher reaktionsenthalpie
EP3838943A1 (de) 2019-12-17 2021-06-23 Covestro Deutschland AG Verfahren zur herstellung von semikristallinen polyurethanen mit hoher reaktionsenthalpie

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE759829A (fr) * 1969-12-03 1971-06-03 Upjohn Co Preparation de polyurethanes
USRE31671E (en) * 1974-09-09 1984-09-11 The Upjohn Company Thermoplastic polyurethane elastomers from polyoxypropylene polyoxyethylene block copolymers
US4101529A (en) * 1976-02-04 1978-07-18 Ppg Industries, Inc. Hard, optically clear polyurethane articles
DE2817457A1 (de) * 1978-04-21 1979-10-31 Bayer Ag Thermoplastische polyurethane fuer die verarbeitung in extrudern oder/und auf kalandern
US4376834A (en) * 1981-10-14 1983-03-15 The Upjohn Company Polyurethane prepared by reaction of an organic polyisocyanate, a chain extender and an isocyanate-reactive material of m.w. 500-20,000 characterized by the use of only 2-25 percent by weight of the latter material
US4385133A (en) * 1982-06-07 1983-05-24 The Upjohn Company Novel compositions and process
US4567236A (en) * 1983-07-18 1986-01-28 The Upjohn Co. Novel polymer blends
DE3405531A1 (de) * 1984-02-16 1985-08-29 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von thermoplastischen polyurethanelastomeren und ihre verwendung
US4522975A (en) * 1984-06-01 1985-06-11 Olin Corporation Select NCO-terminated, uretdione group-containing polyurethane prepolymers and lignocellulosic composite materials prepared therefrom
US4822827A (en) * 1987-12-17 1989-04-18 The Dow Chemical Company Thermoplastic polyurethanes with high glass transition temperatures
US5167899A (en) * 1990-07-07 1992-12-01 The Dow Chemical Company Process for melt blowing microfibers of rigid polyurethane having hard segments

Also Published As

Publication number Publication date
KR20000010740A (ko) 2000-02-25
CA2252459A1 (en) 1997-11-13
JP2000509744A (ja) 2000-08-02
WO1997042248A1 (en) 1997-11-13
ES2171671T3 (es) 2002-09-16
BR9612613A (pt) 1999-07-20
US5627254A (en) 1997-05-06
DE69620471D1 (en) 2002-05-08
DE69620471T2 (de) 2002-11-21
TW368508B (en) 1999-09-01
KR100431014B1 (ko) 2004-08-09
CN1217001A (zh) 1999-05-19
EP0896601A1 (en) 1999-02-17
EP0896601B1 (en) 2002-04-03

Similar Documents

Publication Publication Date Title
CN1150243C (zh) 含有丁二醇和聚乙二醇单元的硬质热塑性聚氨酯
Lan et al. Synthesis and characterization of segmented polyurethanes based on amphiphilic polyether diols
US6008276A (en) Polymer blends containing starch and polyurethane
EP0080031B2 (en) Polyurethanes useful as engineering plastics
CN1210324C (zh) 聚氨酯弹性体
AU1531997A (en) One-part, low viscosity, moisture curable composition
CA1088697A (en) Polyol blends and polyurethane prepared therefrom
EP0415177A2 (en) Polyurethane for flexible fuel containers
CA2168938A1 (en) A thermoplastic polyurethane resin
CA2166122A1 (en) Thermoplastic urethane elastomeric alloys
JPH0651776B2 (ja) ポリエーテルのブレンドに基づくポリウレタン
CN110809591B (zh) 热塑性聚氨酯
US5574092A (en) Thermoplastic polyurethanes containing units derived from an aromatic diol
CN110072902A (zh) 具有高的抗撕裂蔓延强度的热塑性聚氨酯
EP0274319A1 (fr) Composition solide thermoplastique radioréticulable et produits durcissables obtenus avec cette composition
EP0684270A2 (en) Aliphatic polyester carbonate and process for producing the same
EP2294105B1 (en) Fiber reinforced tpu composites
CA2233664A1 (en) Process for the preparation of thermoplastic polyurethanes
EP0156941A2 (en) Polyurethane plastics with improved impact resistance
MXPA98009157A (en) Rigid thermoplastic polyurethane comprising butanodiolunities and a glycol polyethylene
JP3459283B2 (ja) デンプン含有樹脂組成物
CA1111984A (en) Polybutylene terephthalate/thermoplastic polyurethane molding compositions
WO2013032091A1 (ko) 생분해성 폴리에스테르-폴리아세탈 블록 공중합체
US5264620A (en) Prepolymer compositions derived from liquid methylene bis (phenylisocyanate) and polytetramethylene ether glycol
US20230174733A1 (en) Method for producing thermoplastic polyurethanes

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
ASS Succession or assignment of patent right

Owner name: DOW GLOBAL TECHNICAL COMPANY

Free format text: FORMER OWNER: THE DOW CHEMICAL CO.

Effective date: 20021228

C41 Transfer of patent application or patent right or utility model
TA01 Transfer of patent application right

Effective date of registration: 20021228

Address after: Michigan

Applicant after: Dow Global Technologies Inc.

Address before: Michigan

Applicant before: The Dow Chemical Co.

C14 Grant of patent or utility model
GR01 Patent grant
ASS Succession or assignment of patent right

Owner name: LUBORUN HIGH LEVEL MATERIALS CO., LTD.

Free format text: FORMER OWNER: DOW GLOBAL TECHNICAL COMPANY

Effective date: 20090814

C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20090814

Address after: American Ohio

Patentee after: Lubrizol Advanced Materials Inc.

Address before: Michigan

Patentee before: Dow Global Technologies Inc.

C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20040519

Termination date: 20110509