CN1259150A - 热塑性聚醚型聚氨酯 - Google Patents

热塑性聚醚型聚氨酯 Download PDF

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CN1259150A
CN1259150A CN98805925A CN98805925A CN1259150A CN 1259150 A CN1259150 A CN 1259150A CN 98805925 A CN98805925 A CN 98805925A CN 98805925 A CN98805925 A CN 98805925A CN 1259150 A CN1259150 A CN 1259150A
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R·R·维杜拉
S·R·高斯维斯基
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Lubrizol Advanced Materials Inc
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Abstract

一种回弹性好、滞后性低的热塑性聚醚型聚氨酯,其制备是用二异氰酸酯与重均分子量至少为1,400的羟基终端的聚醚和二醇扩链剂进行反应。聚醚含有2—6个碳原子的氧化烯烃重复单元,二醇扩链剂具有2—16个碳原子。二醇扩链剂的量为每摩尔聚醚约0.25—约2摩尔。

Description

热塑性聚醚型聚氨酯
本发明涉及具有回弹值很高并且滞后值低的热塑性聚醚型聚氨酯，更特别涉及衍生自高分子量羟基终端的聚醚型中间体以及优选的芳香族二异氰酸酯和芳香族二醇扩链剂的聚氨酯。
至今为止，热塑性聚氨酯一般具有涉及耐磨性等的适合性能。但这样的聚氨酯一般不适合在有下列要求性能的应用中使用：高熔点；低密度；低拉伸残余变形；低压缩变形；以及特别好的回弹性和低的滞后性。
本发明涉及物理性能好的聚醚型聚氨酯，这种聚氨酯是用羟基终端的聚醚中间体和一扩链剂与二异氰酸酯经熔融聚合制备的。本发明的一个重要的方面是聚醚的重均分子量至少为1,400，其分子量较高得到的结果较好。许多不同的二异氰酸酯都是可以使用的。二异氰酸酯相对于羟基终端的聚醚和扩链剂的摩尔量或比率一般为约0.95-约1.05。本发明的另一个重要方面是，扩链剂基本上是非支化的二醇，优选芳香族二醇。
本发明的热塑性聚氨酯要求有含2-6个碳原子(理想的是2-4个碳原子)的氧化烯烃重复基团的羟基终端的聚醚中间体，例如氧化乙烯或氧化丙烯基团(优选4个碳原子的基团，即氧化四亚甲基或氧化丁烯)或它们的组合。理想的聚醚中间体是均聚物并优选重均分子量高的均聚物，这样能得到好的性能。其重均分子量至少为约1,400，理想的至少为约2,000，优选的至少为约2,500-约5,000或10,000。也可以使用这类分子量的聚合物的混合体，但要避免含低分子量组分的混合体，因为它们的氨基甲酸酯聚合物产生诸如滞后和回弹之类的极差的物理性能。用作中间体的羟基终端的聚醚是本技术领域和文献中悉知的，也有商品供应，例如Quaker Oats公司的Polymeg 2000或DuPont公司的Terethane 2900。
本发明的热塑性聚醚型聚氨酯一般是用所谓的一步法生产的，例如将羟基终端的聚醚中间体、扩链剂和二异氰酸酯加到一起，进行混合和聚合。聚醚和扩链剂以一个物料流加入、二异氰酸酯以另一物料流加入是理想的。
脂肪族二异氰酸酯是可以使用的，而芳香族二异氰酸酯是高度优选的。另外，多官能异氰酸酯化合物即三异氰酸酯等的使用能引起交联，应该避免，因此其量一般少于4mol％，优选少于2mol％，基于所有的各种异氰酸酯的总摩尔量计算。二异氰酸酯可含约4-约20个碳原子，优选约6或约6-16个碳原子。脂肪族二异氰酸酯的实例包括六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯(IPDI)，亚甲基双(4-环己异氰酸酯)、1，4-环己基二异氰酸酯(CHDI)等。优选的芳香族二异氰酸酯的实例包括1，4-二异氰酸根合苯(PPDI)、1，5-萘二异氰酸酯(NDI)、二甲苯二异氰酸酯(XDI)、甲苯二异氰酸酯异构体(TDI)，特别优选的是集称为MDI的4，4’-亚甲基双(苯基异氰酸酯)、其异构体或其低聚物。
本发明中所用的二醇扩链剂最好是直链和结晶的。即所用的所有扩链剂的任何支化部分的重量一般低于15％(重量)，优选低于10％(重量)，基于所有扩链剂总重计算。结晶性有助于防止发粘并在其碳原子数为奇数时可较好地完成结晶。扩链剂可以是脂肪族的，但优选芳香族二醇扩链剂，并含有碳原子总数为约2-约16，优选约6-约12。适合的二醇扩链剂的实例包括乙二醇、丙二醇、丁二醇、戊二醇、己二醇、苯二醇和二甲苯二醇，后者是1，4-二(羟甲基)苯和1，2-二(羟甲基)苯的混合物。苯二醇是优选的，并具体包括氢醌，即双(β-羟乙基)醚，也称为1，4-双(2-羟乙氧基)苯、间苯二酚，即双(β-羟乙基)醚，也称为1，3-双(2-羟乙基)苯、邻苯二酚，即双(β-羟乙基)醚，也称为1，2-双(2-羟乙氧基)苯、以及它们的组合。二醇扩链剂的量一般为每摩尔羟基终端的聚醚中间体约0.25-约2.0、理想的是约0.5-约1.5、并优选约0.70-约1.0摩尔。
一种或多种不同的二异氰酸酯的总摩尔量或摩尔比一般约为0.95-约1.05，优选约0.98-约1.03，基于一种或多种羟基终端的聚醚中间体和一种或多种扩链剂的总摩尔量计算。
如上所述，羟基终端的聚醚中间体、二异氰酸酯和扩链剂一般是一起加入的，并按任何常规的聚氨酯反应方法进行反应。将本发明的热塑性聚醚型聚氨酯形成组分在适合的混合器诸如Banbury或最好是挤压机存在下进行熔融聚合是优选的。将二异氰酸酯分别加入挤压机并将聚醚中间体以与扩链剂的混合体形式加入挤压机是理想的。二异氰酸酯适合的加工或聚合起始温度是约100℃-约200℃，理想的是100℃-150℃；二醇扩链剂和聚醚中间体的混合体的起始温度是约100℃-约220℃，优选约150℃-约200℃。使各种组分进行反应并形成本发明的热塑性聚醚型聚氨酯的适合混合时间一般是约2-约10分钟，理想的是约3-约5分钟。
催化剂是常常要求使用的，诸如使用羧酸亚锡或其它羧酸金属盐以及叔胺。羧酸金属盐催化剂的实例包括辛酸亚锡、二月桂酸二丁基锡、丙酸苯汞、辛酸铅、乙酰丙酮铁、乙酰丙酮镁以及类似物，而叔胺催化剂的实例包括三亚乙基二胺以及类似物。此一种或多种催化剂的用量是较低的，通常是每百万重量份所形成的最终聚合物约50-约100重量份。
聚合的本发明热塑性聚醚型聚氨酯的重均分子量范围一般在约100,000-约500,000，理想的是约150,000-约400,000，优选的是原175,000-约300,000。
本发明的热塑性聚醚型聚氨酯可与各种常规添加剂或配料混合，诸如填料、触变剂、扩链剂、颜料、增塑剂、润滑剂、UV吸收剂等。填料包括滑石、硅酸盐、粘土、碳酸钙等。上述的添加剂和配料可以本技术领域和文献中已知的常规用量使用。
已经发现，本发明的热塑性聚醚型聚氨酯具有许多好的和/或预料不到的性能，例如其中之一是回弹性，用Bay Shore回弹试验即ASTM No.D-2632测定，回弹值到达了至少60％，理想的是至少65％、优选至少70％甚至75％。另一个好的性能是此热塑性的组合物具有低的滞后现象，即在室温下(23℃)10％伸长的滞后损失为15％或更低，一般为12％或更低，理想的是9％或更低，优选6％或更低。在室温下20％伸长的滞后损失为30％或更低，一般为25％或更低，理想的是20％或更低，优选15％或更低。此热塑性塑料也有改进的低的拉伸残余变形(ASTM D-412)，即一般为10％或更低，理想的是8％或更低，优选的是6％或更低。按照ASTM D-395测定23℃下22小时的压缩变形，得到了25％或更低、12％或更低并优选15％或更低的低压缩变形值。希望的70℃下22小时的压缩变形一般为40％或更低，理想的是30％或更低，优选25％或更低。与现有的聚醚型聚氨酯不同，根据差示扫描量热计的测定，本发明的聚氨酯具有高的熔点，例如约170℃-230℃，优选约180℃-约220℃。本发明的聚合物也有低的密度，例如比重为1.10或更低，理想的是1.08或更低，甚至是1.06或1.04和更低。另外，此热塑性聚醚型聚氨酯聚合物的肖氏D硬度至少为15或20，甚至至少为25、30或35-约50或60。
除上述的性能外，本发明的聚醚型聚氨酯还具有常规热塑性聚氨酯所呈现的优良性能，诸如好的抗撕裂性、好的耐磨性、水解稳定性等。
本发明的聚合物可用在要求有这类优良性能的地方，例如可用作高尔夫球的硬芯；用作鞋底；可以熔纺并用作袜子、运动器具、工作服装的纤维和在诸如腿带和尿布之类的弹性边口中使用；诸如电话绳之类的圈形绳；制成动力气管；用作小型马达的型带或其它驱动或惰性带；用作诸如一列式溜冰轮(轮式冰刀)、四轮冰鞋或滑板之类的娱乐用滚轮。
参考下面的实施例将对本发明有更好的理解。下面的实施例只是为了进行说明，而不限制本发明的范围。
实施例
聚酯多元醇的合成：所有涉及聚酯多元醇的例子均为1，4-丁二醇(BDO)和己二酸的缩合产物。这些己二酸酯的制备是用己二酸与BDO进行反应，总二醇/酸的摩尔比大于1.0，并取决于所要求的聚酯多元醇的分子量而有变化。将反应物在干氮气保护下加入反应器并在大气压下保持在125℃，直至停止产生缩合的初始水。施以真空并提高温度并在需要时加15ppm氯化亚锡催化剂，除去附加的缩合水直至酸值降至0.8以下，冷却反应产物并回收。
聚合物的制备是用无规熔融聚合法。此方法是将多元醇和扩链剂在约60℃下混合在一起，然后按要求将混合物加热至100-200℃。按要求将二苯基甲烷二异氰酸酯(MDI)分别加热至100-150℃，然后与混合物混合。将反应物剧烈混合约3分钟，此时温度一般增至200-250℃。将聚合物熔融体排放至冷却盘中，然后在70℃固化一星期。此后测试聚合物的各种性能。
实施例1
在110℃下将186.83克分子量(MW)为870(端基分析法)的聚(己二酸四亚甲基酯)二醇(PTMAG)和13.17克1，4-丁二醇(BDO)混合在一起，得到的混合体分子量(BMW)为555。将90.09克4，4’-二苯基甲烷二异氰酸酯(MDI)加热至110℃，然后与混合体反应，得到的聚合物标示为实例1。
实施例2
在110℃下将180.24克MW为2100(端基分析法)的PTMAG和19.76克BDO混合在一起，得到的BMW为655。将76.33克MDI加热至110℃，然后与混合体反应，得到的聚合物标示为实例2。
实施例3
在110℃下将168.90克MW为2159(端基分析法)的PTMAG和31.10克苯二醇(BG)混合在一起，得到的BMW为850。将59.04克MDI加热至110℃，然后与混合体反应，得到的聚合物标示为实例3。
实施例4
在110℃下将178.67克MW为2159(端基分析法)的PTMAG和21.33克BG混合在一起，得到的BMW为1050。将47.74克MDI加热至110℃，然后与混合体反应，得到的聚合物标示为实例4。
实施例5
在110℃下将185.32克MW为2159(端基分析法)的PTMAG和14.68克BG混合在一起，得到的BMW为1250。将40.20克MDI加热至110℃，然后与混合体反应，得到的聚合物标示为实例5。
实施例6
在120℃下将119.23克MW为670(端基分析法)的聚(四亚甲基醚)二醇(PTMEG)和30.76克BG混合在一起，得到的BMW为450。将60.72克MDI加热至120℃，然后与混合体反应，得到的聚合物标示为实例6。
实施例7
在100℃下将120克MW为990(端基分析法)的PTMEG和30克BG混合在一起，得到的BMW为550。将55.37克MDI加热至100℃，然后与混合体反应，得到的聚合物标示为实例7。
实施例8
在110℃下将182.29克MW为1000(端基分析法)的PTMEG和17.71克BG混合在一起，得到的BMW为736。将67.93克MDI加热至110℃，然后与混合体反应，得到的聚合物标示为实例8。
实施例9
在110℃下将191.29克MW为1000(端基分析法)的PTMEG和8.71克BG混合在一起，得到的BMW为850。将58.82克MDI加热至110℃，然后与混合体反应，得到的聚合物标示为实例9。
实施例10
在110℃下将268.71克MW为1040(端基分析法)的PTMEG和31.29克BG混合在一起，得到的BMW为495。将101.27克MDI加热至110℃，然后与混合体反应，得到的聚合物标示为实例10。
实施例11
在110℃下将178.22克MW为1422(端基分析法)的PTMEG和21.77克BG混合在一起，得到的BMW为850。将58.82克MDI加热至110℃，然后与混合体反应，得到的聚合物标示为实例11。
实施例12
在130℃下将178.23克MW为1422(端基分析法)的PTMEG和21.77克BG混合在一起，得到的BMW为850。将58.93克MDI加热至110℃，然后与混合体反应，得到的聚合物标示为实例12。
实施例13
在110℃下将200克MW为1422(端基分析法)的PTMEG和13.91克BG混合在一起，得到的BMW为1014.28。将52.99克MDI加热至110℃，然后与混合体反应，得到的聚合物标示为实例13。
实施例14
在130℃下将178.32克MW为1761(端基分析法)的PTMEG和21.64克BG混合在一起，得到的BMW为950。将52.71克MDI加热至130℃，然后与混合体反应。从反应开始经过2分钟后向反应中加入一滴辛酸亚锡(催化剂)，得到的聚合物标示为实例14。
实施例15
在150℃下将182.83克MW为1761(端基分析法)的PTMEG和17.17克BG混合在一起，得到的BMW为1050。将47.64克MDI加热至150℃，然后与混合体反应。从反应开始经过2分钟后向反应中加入一滴辛酸亚锡(催化剂)，得到的聚合物标示为实例15。
实施例16
在150℃下将277.83克MW为2025(端基分析法)的PTMEG和22.17克BG混合在一起，得到的BMW为1204。将62.47克MDI加热至150℃，然后与混合体反应。从反应开始经过2分钟后向反应中加入一滴辛酸亚锡(催化剂)，得到的聚合物标示为实例16。
实施例17
在150℃下将150克MW为2226(端基分析法)的聚亚丙基醚二醇(PPG)和11.21克BG混合在一起，得到的BMW为1300。将31.25克MDI加热至120℃，然后与混合体反应。从反应开始经过2分钟后向反应中加入一滴辛酸亚锡(催化剂)，得到的聚合物标示为实例17。
实施例18
在170℃下将200克MW为2953(端基分析法)的PTMEG和11.26克BG混合在一起，得到的BMW为1696。将31.29克MDI加热至140℃，然后与混合体反应。从反应开始经过2分钟后向反应中加入一滴辛酸亚锡(催化剂)，得到的聚合物标示为实例18。
实施例19
在170℃下将200克MW为2953(端基分析法)的PTMEG和12.61克BG混合在一起，得到的BMW为1618。将33.05克MDI加热至140℃，然后与混合体反应。从反应开始经过2分钟后向反应中加入一滴辛酸亚锡(催化剂)，得到的聚合物标示为实例19。
实施例20
在170℃下将200克MW为2953(端基分析法)的PTMEG和9.92克BG混合在一起，得到的BMW为1782。将29.64克MDI加热至140℃，然后与混合体反应。从反应开始经过2分钟后向反应中加入一滴辛酸亚锡(催化剂)，得到的聚合物标示为实例20。
现将实施例1-20的有关资料与回弹数据叙述于表I；所选择的实施例的各种物理性能的有关资料叙述于表II；表III涉及所选择的实施例的滞后数据。
                                                                     表1
实施例号 多元醇类型   多元醇源 多元醇分子量   扩链剂     扩链剂/聚醚摩尔比   混合体分子量   混合体温度℃     MDI温度℃ 回弹值(％)   肖尔D
    1     酯    BFG     870     BDO     0.68     555     110     110     34     35
    2     酯    BFG     2100     BDO     2.56     655     110     110     37     33
    3     酯    BFG     2159     8G     2.01     850     110     110     41     36
    4     酯    BFG     2159     BG     1.30     1050     110     110     53     29
    5     酯    BFG     21 59     BG     0.86     1250     110     110     56     23
    6     PTMEG    Quaker Oats(QO)POLYMEG     670     BG     0.87     450     120     120     24     50
    7     PTMEG    QOPOLYMEG     990     BG     1.25     550     100     100     44     50
    8     PTMEG    QOPOLYMEG     1000     BG     0.49     736     110     110     57     30
    9     PTMEG    QOPOLYMEG     1000     BG     0.23     850     110     110     56     13
    10     PTMEG    QOPOLYMEG     1040     BDO     1.35     495     110     110     40     33
    11     PTMEG    QOPOLYMEG     1422     BG     0.87     850     110     110     59     30
    12     PTMEG    QOPOLYMEG     1422     BG     0.87     850     130     130     63     35
    13     PTMEG    QOPOLYMEG     1422     BG     0.49     1014     110     110     54     19
    14     PTMEG    QOPOLYMEG     1761     BG     1.08     950     150     150     62     37
    15     PTMEG    QOPOLYMEG     1761     BG     0.84     1050     150     150     67     33
    16     PTMEG    QOPOLYMEG     2025     BG     0.84     1204     150     150     72     28
  实施例号 多元醇类型     多元醇源   多元醇分子量   扩链剂     扩链剂/聚醚摩尔比   混合体分子量     混合体温度℃     MDI温度℃   回弹值(％)   肖尔D
    17     PPG     Arco R2446     2226     BG     0.84     1300     150     120     58     19
    18     PTMEG     DuPontT2900     2953     BG     0 84     1696     170     140     77     23
    19     PTMEG     DuPontT2900     2953     BG     0.94     1618     170     140     73     21
    20     PTMEG     DuPontT2900     2953     BG     0.74     1782     170     140     73     21
                                                            表II
    性能   测试方法   实施例2     实施例10     实施例8     实施例16     实施例18
    肖氏硬度D     ASTM D-2240     33     33     30     28     23
    比重(g/cc)     ASTM D-792     1.20     1.12     1.10     1.06     1.04
    拉伸强度(psi)     ASTMD-412/D-638     6500     7000     3400     3599     4266
    伸长率(％)     ASTMD-412/D-638     550     570     710     748     752
拉伸残余变形(％)     ASTMD-412     10     13     10     5.6     -
    压缩变形(％)     ASTM D-395-22hrs@23℃     23     22     18     7.8     -
    ASTM D395-22hrs@70℃     65     70     61     22.9     -
    撕裂强度(lb/in)     ASTM D624，DieC     500     475     315     389     -
    熔点(℃)     DSC     151     160     170     189     211
    玻璃转化温度(℃)     DSC     -32     -40     -45     -69     -70
回弹力(％)     ASTMD-2632     37     40     57     72     77
    挠曲模量(psi)     ASTMD-790     4000     4530     2480     2330     -
                          表III
                          滞后
    实施例号                   ％滞后
    10％伸长     20％伸长     200％伸长
    8     14.2     26.3     51.0
    16     10.6     24.7     49.3
    18     5.6     11.9     39.7
滞后测试：滞后效果定量为变形周期中的能量损失。其测定是用从应力-应变图中伸长曲线下的面积减去松弛曲线下的面积，并将此差以位于伸长曲线下的面积的百分数表示。应力-应变图绘制在Instron 5500R上，十字头的速度为2英寸/分钟，在伸长曲线的末端无任何时间延迟。所有样品均为相同厚度0.075英寸。
从表I明显可见，用酯中间体制备的热塑性聚氨酯即实施例1-5的回弹性很差，甚至是使用高分子量聚酯中间体和苯二醇作为扩链剂。用本发明以外的低分子量(即低于1,400)的聚醚中间体制备的热塑性聚氨酯的回弹性一般也很差，即实施例6-10。但涉及本发明的实施例11-20则具有很好的回弹性能，较高的聚醚中间体分子量值一般具有较高的回弹值。
表II显示用本发明的热塑性聚醚型聚氨酯得到了改进的物理性能，即实施例16和18与使用聚酯中间体的实施例2相比，或与使用低分子量聚醚中间体的实施例8和10相比。但实施例16和18仍保留着其它的热塑性能，诸如好的撕裂强度。
表III显示用本发明的热塑性聚醚型聚氨酯得到了好的低滞后值。
根据专利法，本发明已叙述了最好的模式和最佳具体实施方案，但本发明的范围并不限于此，而是在所附的权利要求书的范围。

Claims (28)

1.一种热塑性聚合物，该聚合物包括
得自二异氰酸酯与羟基终端的聚醚和二醇扩链剂进行反应的聚醚型聚氨酯，
所说的羟基终端的聚醚具有含2-6个碳原子的氧化烯烃重复单元，其重均分子量至少为1,400，
所说的扩链剂是含2-16个碳原子的基本上非支化的二醇，其量是每摩尔所说的羟基终端的聚醚约0.25-约2摩尔。
2.权利要求1的热塑性聚合物，其中所说的聚醚具有含2-4个碳原子的氧化烯烃重复单元。
3.权利要求2的热塑性聚合物，其中所说的二异氰酸酯具有总共4-20个碳原子，其中所说的二异氰酸酯相对所说的羟基终端的聚醚和所说的二醇扩链剂的摩尔比为约0.95-约1.05。
4.权利要求3的热塑性聚合物，其中所说的二醇扩链剂中的任何分支的重量为15％或更少，基于所有扩链剂的总重量计算；其中所说的扩链剂是具有总数为6-12个碳原子的芳香族化合物；其中所说的二异氰酸酯是具有总数为8-16个碳原子的芳香族二异氰酸酯。
5.权利要求4的热塑性聚合物，其中所说羟基终端的聚醚的重均分子量为至少2,500；其中所说的聚醚是聚四亚甲基二醇；其中所说的扩链剂对所说的羟基终端的聚醚的摩尔比为约0.5-约1.5，并且其中所说的热塑性聚合物的重均分子量为约100,000-约500,000。
6.权利要求5的热塑性聚合物，其中所说的聚四亚甲基二醇的分子量为约2,500-约10,000；其中所说的扩链剂对所说的羟基终端的聚醚的摩尔比为约0.7-约1.0；其中所说的扩链剂是苯二醇；其中所说的二异氰酸酯是MDI。
7.权利要求1的热塑性聚合物，其中所说的聚合物的回弹值为至少60％。
8.权利要求4的热塑性聚合物，其中所说的聚合物的回弹值为至少65％。
9.权利要求6的热塑性聚合物，其中所说的聚合物的回弹值为至少70％。
10.权利要求1的热塑性聚合物，其中所说的聚合物的10％伸长时的滞后值为15％或更低。
11.权利要求4的热塑性聚合物，其中所说的聚合物的10％伸长时的滞后值为12％或更低。
12.权利要求6的热塑性聚合物，其中所说的聚合物的10％伸长时的滞后值为6％或更低。
13.权利要求1的热塑性聚合物，其中所说的聚合物的回弹值为至少60％，其中所说的聚合物的10％伸长时的滞后值为15％或更低。
14.权利要求5的热塑性聚合物，其中所说的聚合物的回弹值为至少70％，其中所说的聚合物的10％伸长时的滞后值为9％或更低。
15.一种高尔夫球芯，该球芯包括权利要求1的热塑性聚合物。
16.一种高尔夫球芯，该球芯包括权利要求5的热塑性聚合物。
17.一种绳索，该绳索包括权利要求1的热塑性聚合物。
18.一种绳索，该绳索包括权利要求6的热塑性聚合物。
19.一种娱乐用轮，该轮包括权利要求1的热塑性聚合物。
20.一种娱乐用轮，该轮包括权利要求6的热塑性聚合物。
21.一种型带，该型带包括权利要求1的热塑性聚合物。
22.一种型带，该型带包括权利要求6的热塑性聚合物。
23.一种含纤维的制件，该制件包括权利要求1的热塑性聚合物。
24.一种含纤维的制件，该制件包括权利要求6的热塑性聚合物。
25.一种生产热塑性聚醚型聚氨酯的方法，该方法包括如下步骤：
将羟基终端的聚醚、二醇扩链剂和二异氰酸酯进行混合并反应；所说的羟基终端的聚醚具有含2-6个碳原子的氧化烯烃重复单元，其重均分子量为至少1,400。
26.权利要求25的方法，其中所说的聚醚具有含2-4个碳原子的氧化烯烃重复单元，其中所说的二异氰酸酯具有总共为4-20个的碳原子；其中所说的二异氰酸酯对所说的羟基终端的聚醚和所说的二醇扩链剂的摩尔比为约0.95-约1.05。
27.权利要求26的方法，其中所说的扩链剂是具有总数为6-12个碳原子的芳香族二醇；其中所说的二异氰酸酯是具有总数为8-16个碳原子的芳香族二异氰酸酯；其中所说的扩链剂对所说的聚醚的摩尔比为约0.5-约1.5。
28.权利要求27的方法，其中所说的羟基终端的聚醚的重均分子量至少为2,500；其中所说的聚醚是聚四亚甲基二醇；其中所说的扩链剂是苯二醇；其中所说的二异氰酸酯是MDI。
CN98805925A 1997-06-10 1998-06-03 热塑性聚醚型聚氨酯 Expired - Lifetime CN1125104C (zh)

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CN101959920B (zh) * 2008-01-24 2016-02-17 路博润高级材料公司 软质热塑性弹性体组合物
CN107158688A (zh) * 2017-05-03 2017-09-15 阜南县邰氏宇崴运动器材有限公司 一种能够减少对冰面破坏的冰刀鞋冰刀及其生产工艺
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CN109438644A (zh) * 2018-09-29 2019-03-08 张海军 一种高弹力聚氨酯的制备方法
CN109749411A (zh) * 2019-01-16 2019-05-14 荆晓东 新型聚氨酯复合材料绳索的制备方法
CN110300820A (zh) * 2017-02-10 2019-10-01 巴斯夫欧洲公司 制备弹性纤维的方法、制备弹性纤维制品的方法、弹性纤维和弹性纤维制品

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CN100535211C (zh) * 2001-02-23 2009-09-02 路博润高级材料公司 聚氨酯弹性体纤维的制备方法
CN100348638C (zh) * 2003-01-27 2007-11-14 大日精化工业株式会社 热塑性聚氨酯及其用途
CN101959920B (zh) * 2008-01-24 2016-02-17 路博润高级材料公司 软质热塑性弹性体组合物
CN110300820A (zh) * 2017-02-10 2019-10-01 巴斯夫欧洲公司 制备弹性纤维的方法、制备弹性纤维制品的方法、弹性纤维和弹性纤维制品
CN107158688A (zh) * 2017-05-03 2017-09-15 阜南县邰氏宇崴运动器材有限公司 一种能够减少对冰面破坏的冰刀鞋冰刀及其生产工艺
CN107158688B (zh) * 2017-05-03 2018-11-13 阜南县邰氏宇崴运动器材有限公司 一种能够减少对冰面破坏的冰刀鞋冰刀及其生产工艺
CN107723836A (zh) * 2017-11-08 2018-02-23 浙江华峰氨纶股份有限公司 一种轻质聚氨酯弹性纤维及其制备方法
CN107723836B (zh) * 2017-11-08 2020-05-01 浙江华峰氨纶股份有限公司 一种轻质聚氨酯弹性纤维及其制备方法
CN109438644A (zh) * 2018-09-29 2019-03-08 张海军 一种高弹力聚氨酯的制备方法
CN109749411A (zh) * 2019-01-16 2019-05-14 荆晓东 新型聚氨酯复合材料绳索的制备方法

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EP0988334B1 (en) 2002-09-11
US5959059A (en) 1999-09-28
DE69807872D1 (en) 2002-10-17
AU7810898A (en) 1998-12-30
CN1125104C (zh) 2003-10-22
KR100507007B1 (ko) 2005-08-09
DE69807872T2 (de) 2003-05-28
KR20010013545A (ko) 2001-02-26
WO1998056845A1 (en) 1998-12-17
DE69807872T3 (de) 2005-12-29
JP2002503284A (ja) 2002-01-29
JP4341990B2 (ja) 2009-10-14
HK1028056A1 (en) 2001-02-02
EP0988334B2 (en) 2005-07-27
EP0988334A1 (en) 2000-03-29

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