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CN1654499A - 抗冲击聚氨酯及其制造方法 - Google Patents

抗冲击聚氨酯及其制造方法 Download PDF

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CN1654499A
CN1654499A CNA2004101006196A CN200410100619A CN1654499A CN 1654499 A CN1654499 A CN 1654499A CN A2004101006196 A CNA2004101006196 A CN A2004101006196A CN 200410100619 A CN200410100619 A CN 200410100619A CN 1654499 A CN1654499 A CN 1654499A
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E·C·斯莱格勒
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Abstract

本发明是一种光学透明的高硬度抗冲击聚氨酯，它具有特别高的热变形温度和优良的耐化学剂性。本发明尤其适合要求优良的抗冲击性和高热变形温度的透明用途，例如建筑物窗玻璃、机动车窗玻璃、防暴盾、飞机座舱罩、面罩、挡板、眼镜和太阳镜、护目镜和透明装甲。

Description

抗冲击聚氨酯及其制造方法
本发明专利申请是国际申请号为PCT/US98/21250，国际申请日为1998年10月7日的PCT国际申请进入中国国家阶段后的申请，申请号为98814299.6，发明名称为“抗冲击聚氨酯及其制造方法”的发明专利申请的分案申请。
本申请是美国专利申请08/595,262的部分继续申请，所述美国专利部分继续申请又是美国专利申请08/382,562的部分继续申请，这两个在先申请均在此引为参考。
背景技术
发明的领域
本发明涉及一种刚性的、光学透明的耐热抗冲击聚氨酯。
发明的背景
目前用于比较所有光学透明的塑料的抗冲击性的标准材料是聚碳酸酯。这些材料可用抗冲击性和材料发生变形的温度和压力来表征。在264psi纤维应力下聚碳酸酯的热变形温度约为280°F。
厚度为0.25英寸的聚碳酸酯挤出片其0.22口径FSP(碎片模拟射弹)V-50冲击速度为925英尺/秒。V-50是速度测量值，在此速度下50％的22口径射弹射穿0.25英寸厚的聚碳酸酯片，进入放置在该聚碳酸酯片背面6英寸处的20毫米厚2024 T6铝板(参考片材)。
美国专利3,866,242(在此引为参考)公开了一种聚氨酯聚合物防护罩。所述聚氨酯是如下制得的：
(a)使分子量约为700-1000的聚醚二醇或聚酯二醇与亚甲基二(环己基异氰酸酯)以约三个NCO对一个羟基的当量比进行反应，形成预聚物；
(b)以0.90-1.04 NH2/1.0 NCO的当量比使所述预聚物与两个芳环之间具有亚甲基桥的芳香胺固化剂(如4，4’-亚甲基二(2-氯苯胺))反应。
美国专利4,808,690(在此引为参考)公开了一种由多元醇固化的预聚物制得的透明聚氨酯聚合物。所述预聚物是由多异氰酸酯和至少一种多官能含羟基的中间体制得的。
美国专利4,208,507公开了一种挠性聚氨酯-脲弹性体，它是使：(A)由分子量为600-10,000的主要二官能的多羟基化合物与至少一个NCO基团连接在脂环结构上的有机二异氰酸酯反应，其用量使得OH∶NCO的总比例为1∶1.2-1∶10，得到的预聚物与(B)3，3’，5，5’-四甲基-4，4’-二氨基二苯基甲烷反应制得的，A与B反应的摩尔比约为1∶0.8-1∶1.2。
发明的概述
本发明光学透明的聚氨酯可如下制得：使重均分子量约为400-2000的一种或多种聚酯二醇、聚己内酯二醇、聚醚二醇或者聚碳酸酯二醇与脂环族二异氰酸酯以约2.5-4.0个NCO比一个OH的当量比进行反应，先制得预聚物。随后使该预聚物与芳香二元胺固化剂(如二乙基甲苯二胺)反应，两者的当量比约为0.85-1.02NH2/1.0 NCO，较好约0.90-1.0 NH2/1.0 NCO，更好约0.92-0.96NH2/1.0 NCO。
本发明聚氨酯尤其适用于需要优良抗冲击性和高热变形温度的透明用途，例如建筑物窗玻璃、机动车窗玻璃、防暴盾、飞机座舱罩、面罩、挡板、眼镜和太阳镜、护目镜和透明装甲。
本发明的一个目的是提供透明的聚氨酯，与现有的材料相比它具有优良的光学透明度、优良的抗冲击性能、高的耐化学剂性和高的热变形温度。
本发明的另一个目的是提供一种低成本透明抗冲击聚氨酯用于商业用途。
本发明再一个目的是通过降低反应时间、加工温度和模具滞留时间来提高透明抗冲击聚氨酯的生产加工。
本发明的详细描述、实施例和所附权利要求书将更详细地描述本发明的这些和其它目的。
发明的详细描述
本发明聚氨酯是由脂环族二异氰酸酯、含羟基的中间体以及芳香二元胺固化剂制得的。下面将详细描述这些组分。
含羟基的中间体
适合制造本发明聚氨酯的含羟基的中间体包括重均分子量约为400-2000，较好约为400-1000的聚酯二醇、聚己内酯二醇、聚醚二醇和聚碳酸酯二醇。
适用的聚酯二醇包括具有4-10个碳原子的一种或多种二元羧酸(如己二酸、琥珀酸和癸二酸)与一种或多种具有2-10个碳原子的低分子量二元醇(如乙二醇、丙二醇、二甘醇、1，4-丁二醇、新戊二醇、1，6-己二醇和1，10-癸二醇)的酯化产物。较好的聚酯二醇是己二酸与具有2-10个碳原子的二元醇的酯化产物。
适用的聚己内酯二醇包括ε-己内酯与一种或多种上述低分子量二元醇的反应产物。另外，适用的含羟基的中间体包括一种或多种低分子量二元羧酸(如己二酸)和己内酯与一种或多种上述低分子量二元醇制得的三元酯(teresters)。
较好的聚酯二醇和聚己内酯二醇可例如如D.M.Young，F.Hostettler等的“Polyesters from Lactone”Union Carbide F-40，p147文献所述用已知的酯化或酯交换方法制得。
适用的聚醚二醇包括聚四亚甲基醚二醇。
适用的聚碳酸酯二醇包括脂族聚碳酸酯二醇。较好的脂族聚碳酸酯二醇是Enichem制造的并以Ravecarb 102(分子量为1000)和Ravecarb 106(分子量为2000)的商品名出售的聚碳酸酯二醇。
最好的含羟基的中间体是：(a)己二酸与一种或多种选自1，4-丁二醇、1，6-己二醇、新戊二醇和1，10-癸二醇的二元醇的酯化产物；(b)ε-己内酯与一种或多种选自1，4-丁二醇、1，6-己二醇、新戊二醇和1，10-癸二醇的二元醇的反应产物；(c)聚1，4-丁二醇；(d)脂族聚碳酸酯二醇和(e)这些含羟基中间体的混合物。
二异氰酸酯
适用于制造本发明聚氨酯的脂环族二异氰酸酯包括二环己基甲烷二异氰酸酯，较好是约含20-100％4，4’-亚甲基二(环己基异氰酸酯)(下面称为PICM，对异氰酸酯基环己基甲烷)的反式，反式异构体的异构体混合物。通常存在于用于本发明的二环己基甲烷二异氰酸酯的位置和/或立体异构体的混合物中的其它组分有PICM的顺式，反式和顺式，顺式异构体以及2，4’-亚甲基二(环己基异氰酸酯)立体异构体。这些异构体以及反式，反式PICM异构体的含量可通过用于制造二环己基甲烷二异氰酸酯的方法来控制。较好的二异氰酸酯是PICM异构体混合物。更好的混合物中反式，反式异构体的含量不少于约20％，4，4’-亚甲基二(环己基异氰酸酯)的顺式，顺式异构体不超过约20％。4，4’-亚甲基二(环己基异氰酸酯)的三种异构体如下：
                    反式，反式
                    顺式，反式
Figure A20041010061900101
                    顺式，顺式
适用于本发明的PICM是用例如美国专利2,644,007、2,680,127和2,908,703(在此引为参考)所述的本领域众所周知的方法通过对相应的4，4’-亚甲基二(环己胺)(PACM)进行光气化制得的。PACM异构体混合物在室温在液相、部分液相或固相经光气化后形成PICM。所述PACM异构体混合物可由亚甲基二苯胺氢化和/或在水和醇(如甲醇和乙醇)的存在下PACM异构体混合物分级结晶而制得。
其它适用的脂环族二异氰酸酯包括购自Arco Chemical的3-异氰酸甲酯基-3，5，5-三甲基环己基异氰酸酯(IPDI)，它具有如下结构：
以及购自Cytex，Inc.，的间四甲基二甲苯二异氰酸酯(TMXDI)，它具有下列结构：
Figure A20041010061900103
二元胺固化剂
用于制造本发明聚氨酯的较好的芳香二元胺固化剂是2，4-二氨基-3，5-二乙基甲苯、2，6-二氨基-3，5-二乙基甲苯及其混合物(通称二乙基甲苯二胺或DETDA)，它可以Ethacure 100的商品名购自Albemarle Corporation。DETDA在室温是液态的，在25℃的粘度为156cs。DETDA是异构体，其中2，4-异构体为75-81％，而2，6-异构体为18-24％。DETDA具有下列结构：
                        2，6-异构体
Figure A20041010061900112
                        2，4-异构体
特别好的是以Ethacure 100S的商品名购得的色稳定的Ethacure 100。
适用于本发明的其它二元胺固化剂包括具有下列化学式的化合物：
其中，R1和R2各自选自甲基、乙基、丙基和异丙基，R3选自氢和氯。这种二元胺固化剂的例子有Lonza Ltd.(Basel，Switzerland)制造的下列化合物：
LONZACUREM-DIPA R1＝C3H7；R2＝C3H7；R3＝H
LONZACUREM-DMA R1＝CH3；R2＝CH3；R3＝H
LONZACUREM-MEA R1＝CH3；R2＝C2H5；R3＝H
LONZACUREM-DEA R1＝C2H5；R2＝C2H5；R3＝H
LONZACUREM-MIPA R1＝CH3；R2＝C3H7；R3＝H
LONZACUREM-CDEA R1＝C2H5；R2＝C2H5；R3＝Cl
其中R1、R2和R3对应于上式的R1、R2和R3。其中，较好的二元胺固化剂是4，4’-亚甲基二(3-氯-2，6-二乙基苯胺)(LONZACUREM-CDEA)，它可购自Air Productsand Chemical，Inc.(Allentown，Pennsylvania)。上述二元胺固化剂可以是附加的或者用于代替DETDA作为聚氨酯固化剂。
制备本发明聚氨酯
本发明聚氨酯可用本领域已知的准预聚物法或全预聚物法制得。本发明聚氨酯的较好制备方法如下：以约2.5-4.0 NCO/1.0 OH，较好以约3.0 NCO/1.0 OH的当量比例先将二异氰酸酯与含OH的中间体相混合，随后在212-230°F使之反应3-5小时，或者在260-265°F反应5-10分钟，或者在275-290°F反应3-5分钟。随后移去热源，使预聚物冷却至约160°F，并在该温度稳定约24小时，接着测定预聚物中的NCO百分数。随后可加入附加的二异氰酸酯以达到确定的当量。接着以约0.85-1.02NH2/1.0 NCO，较好以约0.90-1.0 NH2/1.0 NCO，更好约0.92-0.96NH2/1.0 NCO的当量比在约160-180°F使预聚物与芳香二元胺固化剂反应。随后将预聚物在230-275°F固化4-24小时。在较低温度下固化时间较长，在较高温度下固化时间较短。
本发明聚氨酯聚合物可铸塑或模压。铸塑是较好的方法，因为它制得的聚氨酯聚合物具有最佳的光学特性。
可将预聚物和固化剂混合物铸塑在模具中，随后固化。可选择适当的固化时间和温度部分固化本发明聚氨酯材料，随后从铸塑模具中移出之，并制成所需的形状。使用这种方法，可将聚氨酯材料制成简单或复杂的形状，随后完全固化之。
可向预聚物中加入三元醇，其加入量足以产生约1％(按反应物的当量计)的交联，例如以总反应物重量计4-8％发生交联。适用于本发明的三元醇包括三羟甲基乙烷和三羟甲基丙烷。向预聚物中加入三元醇提高了热变形温度，并在某些情况下改进了固化聚氨酯的冲击性能。
在制造本发明聚氨酯时可使用各种抗氧剂、紫外光稳定剂、抗变色剂、光学增亮剂、和脱模剂。例如，按反应物总重量计可在预聚物中最多加入5％的一种或多种抗氧剂。适用于本发明的抗氧剂包括多官能位阻酚型抗氧剂。多官能位阻酚型抗氧剂的一个例子是购自Ciba Geigy的Irganox 1010，它的化学式如下：
Figure A20041010061900121
还可在固化步骤前或固化过程中向预聚物中加入紫外光稳定剂，按反应物总重量计其加入量最多约为5.0％，较好约0.5-4.0％。适用于本发明的紫外光稳定剂包括苯并三唑。苯并三唑紫外光稳定剂的例子包括Cyasorb 5411和Tinuvin328。购自American Cyanamid的Cyasorb 5411具有下列化学式：
Figure A20041010061900131
购自Ciba Geigy的Tinuvin 328具有下列化学式：
Figure A20041010061900132
另一种适用的紫外光稳定剂是购自American Cyanamid的Cyasorb 3604，它具有下列化学式：
除了苯并三唑以外，可加入位阻胺光稳定剂以进一步增强紫外光防护性能。位阻胺光稳定剂的例子是购自Ciba-Geigy的Tinuvin 765，其化学式如下：
实施例I-VII
将脂环族二异氰酸酯与一种或多种聚酯二醇、聚己内酯二醇、聚醚二醇或聚碳酸酯二醇相混合。在干燥的氮气下将反应物加热至275-290°F，在该温度下保温3-5分钟，使之反应成预聚物。将该预聚物冷却至220-250°F，加入紫外光稳定剂、抗氧剂、抗变色剂和/或光学增亮剂。将预聚物进一步冷却至170-200°F，随后进行评价并在160°F储存24小时。测定NCO的百分数。
接着在160-180°F使该预聚物与芳香二元胺固化剂以0.85-1.02NH2比1.0NCO的当量比进行反应。接着将聚合物在230-275°F固化4-24小时。
实施例所用的反应物如下表I所示：
                                                表I
  成分 说明 生产公司
  Ruco S-105-110 由己二酸和1，6-己二醇制得的聚酯二醇，当量约为500 Ruco Polymer Corp.
  Ruco S-105-210 由己二酸和1，6-己二醇制得的聚酯二醇，当量约为268 Ruco Polymer Corp.
  Solvay Interox 396-005 由ε-己内酯和1，6-己二醇制得的聚酯二醇，当量约387 Solvay Interox
  Solvay Interox 524-021 由ε-己内酯和1，6-己二醇制得的聚酯二醇，当量约200 Solvay Interox
  Solvay Interox 439-045 由ε-己内酯和1，6-己二醇制得的聚酯二醇，当量约954 Solvay Interox
  Ravecarb 102 脂族聚碳酸酯二醇，当量约255 Enichem
  Desmodur W 含20％反式，反式异构体和80％顺式，顺式及顺式，反式异构体的4，4’-亚甲基二(环己基二异氰酸酯) Bayer Corp.
  Ethacure 100 2，4-二氨基-3，5-二乙基甲苯和2，6-二氨基-3，5-二乙基甲苯 Albemarle Corporation
  Ethacure 100S 含色稳定剂的2，4-二氨基-3，5-二乙基甲苯和2，6-二氨基-3，5-二乙基甲苯 Albemarle Corporation
  LonzacureM-CDEA 4，4’-亚甲基二(3-氯-2，6-二乙基苯胺) Lonza Ltd.(Bascl，Switzer-land)；Air Products和Chemical，Inc.(Allentown，Pennsylvania)
  Tinuvin 328 紫外光稳定剂，参见上面化学式 Ciba Geigy
  Tinuvin 765 紫外光稳定剂，参见上面化学式 Ciba Geigy
  Irganox 1010 抗氧剂，参见上面化学式 Ciba Geigy
  Exalite Blue 78-13 作为抗变色剂的染料 Exciton
  Uvitex OB 光学增亮剂 Ciba Geigy
在各实施例中各反应物的用量如下表II所示。
                                                        表II
    实施例I     实施例II     实施例III     实施例IV     实施例V     实施例VI     实施例VII     实施例VIII
Ruco S-105-110(当量)     1.0     0.7     0.4
Ruco S-105-210(当量)     0.3     0.6
Solvay Interox 396-005(当量)     0.5
Solvay Interox 524-021(当量)     0.4
Solvay Interox 439-045(当量)     0.1
Ravecarb 102(当量)     1.0     1.0     0.8     0.8
1，6-己二醇(当量)     0.2     0.2
Desmodur W(当量)     3.0     3.0     3.0     3.0     3.0     3.5     3.0     3.25
Ethacure 100S1(当量)     0.93     0.93     0.93     0.93     0.93     0.93     0.93     0.93
Tinuvin 328(重量％)     1.0     1.0     0.75     0.75     0.75     0.75     0.75     0.75
Tinuvin 765(重量％)     0.75     0.75     0.75     0.75     0.75     0.75
Irganox1010(重量％)     0.40     0.40     0.40     0.40     0.40     0.40     0.40     0.40
Exalite Blue 78-13(ppm)     1.25     1.25     1.25     1.25     1.25     1.25
Uvitex OB(ppm)     0.60     0.60     0.60     0.60     0.60     0.60
1给出的Ethacure 100S(DETDA)的量为预聚物中测得的每1.0当量NCO中NH2的当量数。
评价形成的材料的光学性能、硬度、耐溶剂性、热变形性和抗冲击性。
实施例I-IV的聚氨酯材料均具有优良的光学性能，雾度低至0.3％，在厚度为0.080-0.250英寸时透光度高达95％。实施例I-IV试样的肖氏D硬度为79-82。对于实施例V-VIII试样，其肖氏D硬度为77-82。
当使用异丙醇测定时，实施例I、II和III的聚氨酯材料的耐应力银纹性大于7000磅/英寸2。
使用0.25英寸厚的片材和0.22口径的碎片模拟射弹评价实施例I-IV试样的V-50速度。经多次试验后，平均V-50速度约为1210英尺/秒。
对于实施例I-III的试样，0.25英寸厚的试样在264psi纤维应力的热变形温度范围为290-305oF，在264psi纤维应力实施例IV材料的相似试样的热变形温度为270-280oF。
0.25英寸厚的实施例V-VIII的试样的热变形温度及抗冲击性如下表所示：
表III
  性能   实施例V   实施例VI   实施例VII   实施例VIII
  热变形温度，264psi纤维应力   126℃(259oF)   155℃(311oF)   145℃(293oF)   157℃(315oF)
  V-50 0.22口径DSP速度   1183英尺/秒   1233英尺/秒   1207英尺/秒   1169英尺/秒
上面本发明实施例和其它实例的描述仅出于说明和叙述的目的。不应将本发明限制在所述实施例和实例。在阅读了上面描述以后本领域的普通技术人员显然会对所述实施例和实例进行各种变化和改进。本发明的范围仅由所附权利要求书及其等同内容所限定。

Claims (54)

1.一种透明的、非弹性高硬度抗冲击聚氨酯材料，它包括以下(a)与(b)进行反应的反应产物：
(a)一种预聚物，它是由脂族或脂环族二异氰酸酯与至少一种重均分子量约为约400-2000的含羟基的中间体反应制得的，所述中间体选自聚酯二醇、聚己内酯二醇、聚醚二醇和聚碳酸酯二醇及其混合物；与
(b)至少一种第一芳香二元胺固化剂，所述固化剂选自2，4-二氨基-3，5-二乙基甲苯、2，6-二氨基-3，5-二乙基甲苯及其混合物。
2.如权利要求1所述的聚氨酯材料，其特征在于所述聚氨酯由准预聚物法制得。
3.如权利要求1所述的聚氨酯材料，其特征在于所述聚氨酯由全预聚物法制得。
4.如权利要求3所述的聚氨酯材料，其特征在于所述二异氰酸酯与至少一种含羟基的中间体以约2.5-4.0 NCO/1.0 OH的当量比进行反应。
5.如权利要求4所述的聚氨酯材料，其特征在于所述二元胺固化剂与所述预聚物以约0.85-1.02 NH2/1.0 NCO的当量比进行反应。
6.如权利要求1所述的聚氨酯材料，其特征在于所述聚氨酯材料是所述预聚物、所述至少一种第一芳香二元胺固化剂和至少一种第二二元胺固化剂的反应产物，所述第二二元胺固化剂选自具有下式的化合物：
其中R1和R2各自选自甲基、乙基、丙基和异丙基，R3选自氢和氯。
7.如权利要求1所述的聚氨酯材料，其特征在于所述二异氰酸酯选自4，4’-亚甲基二(环己基异氰酸酯)、3-异氰酸甲酯基-3，5，5-三甲基环己基异氰酸酯、间四甲基二甲苯二异氰酸酯及其混合物。
8.如权利要求1所述的聚氨酯材料，其特征在于所述聚氨酯材料在264psi的热变形温度为210-325°F。
9.如权利要求1所述的聚氨酯材料，其特征在于所述聚氨酯材料在264psi的热变形温度至少为250°F。
10.如权利要求1所述的聚氨酯材料，其特征在于所述聚氨酯材料在264psi的热变形温度至少为300°F。
11.如权利要求1所述的聚氨酯材料，其特征在于所述聚氨酯材料是光学透明的，厚度为0.08-0.25英寸时的透光度至少约80％。
12.如权利要求1所述的聚氨酯材料，其特征在于0.25英寸厚的聚氨酯材料片的V-50 0.22口径FSP速度至少为1100英尺/秒。
13.如权利要求4所述的聚氨酯材料，其特征在于所述二元胺固化剂与所述预聚物以约0.90-1.0 NH2/1.0 NCO的当量比进行反应。
14.如权利要求1所述的聚氨酯材料，其特征在于所述含羟基中间体的重均分子量约为400-1000。
15.如权利要求1所述的聚氨酯材料，其特征在于所述含羟基的中间体选自(a)己二酸与一种或多种选自1，4-丁二醇、1，6-己二醇、新戊二醇和1，10-癸二醇的二元醇的酯化产物；(b)ε-己内酯与一种或多种选自1，4-丁二醇、1，6-己二醇、新戊二醇和1，10-癸二醇的二元醇的反应产物；(c)聚1，4-丁二醇；(d)脂族聚碳酸酯二醇和(e)这些含羟基中间体的混合物。
16.如权利要求1所述的聚氨酯材料，其特征在于所述脂环族二异氰酸酯是4，4’-亚甲基二(环己基异氰酸酯)的异构体混合物，它至少包括20％4，4’-亚甲基二(环己基异氰酸酯)的反式，反式异构体。
17.如权利要求1所述的聚氨酯材料，其特征在于所述聚氨酯还包括紫外光稳定剂。
18.如权利要求17所述的聚氨酯材料，其特征在于所述紫外光稳定剂选自苯并三唑、位阻胺光稳定剂及其混合物。
19.如权利要求1所述的聚氨酯材料，其特征在于所述预聚物还包括抗氧剂。
20.如权利要求19所述的聚氨酯材料，其特征在于所述抗氧剂是多官能位阻酚。
21.如权利要求1所述的聚氨酯材料，其特征在于当用异丙醇测定时，所述聚氨酯材料的耐应力银纹性大于7000磅/英寸2。
22.如权利要求1所述的聚氨酯材料，其特征在于所述聚氨酯还包括三元醇，其用量足以产生以反应物当量计1％的交联。
23.如权利要求22所述的聚氨酯材料，其特征在于所述三元醇选自三羟甲基乙烷、三羟甲基丙烷及其混合物。
24.用权利要求1所述聚氨酯材料制得的眼镜镜片。
25.如权利要求24所述的镜片，其特征在于所述镜片选自太阳眼镜镜片、眼镜镜片和防护眼镜镜片。
26.如权利要求1所述的聚氨酯材料，其特征在于所述二元胺固化剂是色稳定的。
27.一种透明的、非弹性高硬度抗冲击聚氨酯材料，它包括以下(a)与(b)进行反应的反应产物：
(a)一种预聚物，它是由二异氰酸酯与至少一种重均分子量约为400-2000的含羟基的中间体反应制得的，所述二异氰酸酯选自4，4’-亚甲基二(环己基异氰酸酯)、3-异氰酸甲酯基-3，5，5-三甲基环己基异氰酸酯、间四甲基二甲苯二异氰酸酯及其混合物；所述中间体选自(a)己二酸与一种或多种选自1，4-丁二醇、1，6-己二醇、新戊二醇和1，10-癸二醇的二元醇的酯化产物；(b)ε-己内酯与一种或多种选自1，4-丁二醇、1，6-己二醇、新戊二醇和1，10-癸二醇的二元醇的反应产物；(c)聚1，4-丁二醇；(d)脂族聚碳酸酯二醇和(e)这些含羟基中间体的混合物；与
(b)至少一种二元胺固化剂，所述固化剂选自2，4-二氨基-3，5-二乙基甲苯、2，6-二氨基-3，5-二乙基甲苯及其混合物，其中所述聚氨酯材料在264psi的热变形温度至少为300°F。
28.如权利要求27所述的聚氨酯材料，其特征在于所述聚氨酯由准预聚物法制得。
29.如权利要求27所述的聚氨酯材料，其特征在于所述聚氨酯由全预聚物法制得。
30.如权利要求29所述的聚氨酯材料，其特征在于所述二异氰酸酯与至少一种含羟基的中间体以约2.5-4.0 NCO/1.0 OH的当量比进行反应。
31.如权利要求30所述的聚氨酯材料，其特征在于所述二元胺固化剂与所述预聚物以约0.85-1.02NH2/1.0 NCO当量比进行反应。
32.由权利要求27所述聚氨酯材料制得的眼镜镜片。
33.如权利要求32所述的镜片，其特征在于所述镜片是太阳眼镜镜片、眼镜镜片和防护眼镜镜片。
34.如权利要求27所述的聚氨酯材料，其特征在于所述二元胺固化剂是色稳定的。
35.如权利要求27所述的聚氨酯材料，其特征在于所述聚氨酯材料是光学透明的，厚度为0.08-0.25英寸时的透光度至少约80％。
36.如权利要求27所述的聚氨酯材料，其特征在于0.25英寸厚的聚氨酯材料片的V-50 0.22口径FSP速度至少为1100英尺/秒。
37.如权利要求27所述的聚氨酯材料，其特征在于所述含羟基中间体的重均分子量约为400-1000。
38.如权利要求27所述的聚氨酯材料，其特征在于所述二异氰酸酯是4，4’-亚甲基二(环己基异氰酸酯)的异构体混合物，它至少包括20％4，4’-亚甲基二(环己基异氰酸酯)的反式，反式异构体。
39.如权利要求27所述的聚氨酯材料，其特征在于所述预聚物还包括紫外光稳定剂。
40.如权利要求39所述的聚氨酯材料，其特征在于所述紫外光稳定剂选自苯并三唑、位阻胺光稳定剂及其混合物。
41.如权利要求27所述的聚氨酯材料，其特征在于所述预聚物还包括抗氧剂。
42.如权利要求41所述的聚氨酯材料，其特征在于所述抗氧剂是多官能位阻酚。
43.如权利要求27所述的聚氨酯材料，其特征在于当用异丙醇测定时，所述聚氨酯材料的耐应力银纹性大于7000磅/英寸2。
44.如权利要求27所述的聚氨酯材料，其特征在于所述预聚物还包括三元醇，其用量足以产生以反应物当量计1％的交联。
45.如权利要求44所述的聚氨酯材料，其特征在于所述三元醇选自三羟甲基乙烷、三羟甲基丙烷及其混合物。
46.如权利要求1所述的聚氨酯材料，其特征在于所述聚氨酯材料是光学透明的，厚度为0.08-0.25英寸时的透光度至少约95％。
47.如权利要求1所述的聚氨酯材料，其特征在于所述聚氨酯材料是光学透明的，厚度为0.08-0.25英寸时的雾度为约0.3％或更低。
48.如权利要求1所述的聚氨酯材料，其特征在于所述聚氨酯材料的肖氏D硬度至少77。
49.如权利要求1所述的聚氨酯材料，其特征在于所述聚氨酯材料的肖氏D硬度至少79。
50.如权利要求27所述的聚氨酯材料，其特征在于所述聚氨酯材料的光学透明的，厚度为0.08-0.25英寸时的透光度至少约95％。
51.如权利要求27所述的聚氨酯材料，其特征在于所述聚氨酯材料是光学透明的，厚度为0.08-0.25英寸时的雾度为约0.3％或更低。
52.如权利要求27所述的聚氨酯材料，其特征在于所述聚氨酯材料的肖氏D硬度至少77。
53.如权利要求27所述的聚氨酯材料，其特征在于所述聚氨酯材料的肖氏D硬度至少79。
54.一种透明的、非弹性高硬度抗冲击聚氨酯材料，它基本上如本文实施例所述。
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1908698B (zh) * 2006-08-23 2010-10-06 黄则煌 丙烯基二甘醇碳酸酯护目镜片及其制造方法
CN101130597B (zh) * 2007-09-29 2011-06-01 山东东大一诺威聚氨酯有限公司 一种耐溶剂型聚氨酯弹性体的合成方法
CN101407572B (zh) * 2008-11-14 2011-07-20 上海维凯化学品有限公司 一种聚氨酯-聚脲水分散体及其制备方法
CN107383328A (zh) * 2017-06-27 2017-11-24 烟台观复光电材料有限公司 具有阻隔防护功能的柔性可弯折聚氨酯光学材料及其制备方法、透明柔性光学部件及其应用

Families Citing this family (108)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030158369A1 (en) * 1995-02-02 2003-08-21 Slagel Edwin C. Impact resistant polyurethane and method of manufacture thereof
US7247676B2 (en) * 1997-05-27 2007-07-24 Acushnet Company For golf balls with non-ionomer casing layer
US7005479B2 (en) * 1997-05-27 2006-02-28 Acushnet Company Golf ball with rigid intermediate layer
US7002744B2 (en) * 1999-11-22 2006-02-21 Younger Mfg. Co. Dba Younger Optics Polarized optical part using high impact polyurethane-based material
US7473754B1 (en) 2000-10-17 2009-01-06 Ppg Industries Ohio, Inc. Optical resin composition
US7087698B1 (en) * 1999-11-18 2006-08-08 Ppg Industries Ohio, Inc. Method of preparing an optical polymerizate
US7098290B1 (en) * 1999-11-18 2006-08-29 Ppg Industries Ohio, Inc. Method of preparing an optical polymerizate
WO2001057106A1 (en) * 2000-02-04 2001-08-09 Ppg Industries Ohio, Inc. Photochromic coated articles
JP2003523049A (ja) * 2000-02-11 2003-07-29 ミッドトロニクス インコーポレイテッド 統合的な電池試験器を有する蓄電池
DE10041414A1 (de) * 2000-08-23 2002-03-07 Basf Ag Verfahren zur Herstellung von kompakten, transparenten Schuhteilen
AU782220B2 (en) † 2000-10-13 2005-07-14 Talex Optical Co., Ltd. Polyurethane resin composition and optical lens having impact resistance
JP3698984B2 (ja) * 2000-11-10 2005-09-21 ヤマウチ株式会社 シュープレス用ベルト
TW593450B (en) 2001-03-21 2004-06-21 Hoya Corp Transparent molded articles, optical components, plastic lenses and preparation method thereof
US6525131B1 (en) * 2001-09-18 2003-02-25 Crompton Corporation Aromatic diamine polyurethane curatives with improved stability
US6562932B1 (en) * 2001-10-12 2003-05-13 Bayer Corporation Light stable one-shot urethane-urea elastomers
US7767779B2 (en) 2001-11-14 2010-08-03 Essilor International Compagnie Generale D'optique High index and high impact resistant polythiourethane/urea material, method of manufacturing same and its use in the optical field
US8822623B2 (en) * 2001-11-14 2014-09-02 Essilor International (Compagnie Generale D'optique) High index and high impact resistant poly(thio)urethane/urea material, method of manufacturing same and its use in the optical field
US7144969B2 (en) * 2001-11-16 2006-12-05 Ppg Industries Ohio, Inc. Impact resistant polyureaurethane and polyureaurethane prepolymer having low NCO/OH ratio
US8017720B2 (en) 2005-12-16 2011-09-13 Ppg Industries Ohio, Inc. Sulfur-containing oligomers and high index polyurethanes prepared therefrom
US20070142606A1 (en) * 2005-12-16 2007-06-21 Bojkova Nina V Polyurethane (ureas) and sulfur-containing polyurethane (ureas) methods of preparation
US20030096935A1 (en) * 2001-11-16 2003-05-22 Nagpal Vidhu J. Impact resistant polyureaurethane and method of preparation
US20040138401A1 (en) * 2002-11-05 2004-07-15 Nina Bojkova High impact poly (urethane urea) polysulfides
FR2832717B1 (fr) * 2001-11-26 2004-07-09 Essilor Int Composition polymerisable par voie radicalaire conduisant a des verres organiques resistants au choc
US7682531B2 (en) * 2002-04-08 2010-03-23 Hoya Corporation Process for producing optical member
JP3905409B2 (ja) * 2002-04-10 2007-04-18 タレックス光学工業株式会社 光学レンズ成型用ポリウレタン樹脂組成物および耐衝撃性合成樹脂レンズ
US6623419B1 (en) * 2002-04-25 2003-09-23 Access Business Group International Llc Therapeutic back belt and related method of manufacture
JP2003340698A (ja) * 2002-05-30 2003-12-02 Hoya Corp レンズ加工装置及びレンズ加工方法
US20040087754A1 (en) * 2002-10-31 2004-05-06 Paul Foley Polyurethane compounds and articles prepared therefrom
US7465414B2 (en) 2002-11-14 2008-12-16 Transitions Optical, Inc. Photochromic article
EP2325234B1 (en) * 2002-12-20 2017-03-29 PPG Industries Ohio, Inc. High impact poly(urethane urea) polysulfides
US6939939B2 (en) * 2003-02-24 2005-09-06 Younger Mfg. Polyurea/urethane optical material and method for making it
AU2004245410A1 (en) * 2003-06-09 2004-12-16 Hoya Corporation Polyol compound, transparent molded article and method of manufacturing transparent molded article
JP4506932B2 (ja) * 2003-06-11 2010-07-21 三菱瓦斯化学株式会社 新規なアミン化合物およびその製造方法
US20080097045A1 (en) * 2004-06-23 2008-04-24 Yoshinori Isahaya Polymerizable Composition
US8859680B2 (en) * 2004-09-01 2014-10-14 Ppg Industries Ohio, Inc Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same
US20070149749A1 (en) * 2004-09-01 2007-06-28 Rukavina Thomas G Polyurethanes prepared from polycarbonate polyols, articles and coatings prepared therefrom and methods of making the same
US8933166B2 (en) * 2004-09-01 2015-01-13 Ppg Industries Ohio, Inc. Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same
US20070148471A1 (en) * 2004-09-01 2007-06-28 Rukavina Thomas G Impact resistant polyurethane and poly(ureaurethane) articles and methods of making the same
US20070167601A1 (en) * 2004-09-01 2007-07-19 Rukavina Thomas G Polyurethanes prepared from polycarbonate polyols, articles and coatings prepared therefrom and methods of making the same
US20090280709A1 (en) 2004-09-01 2009-11-12 Ppg Industries Ohio, Inc. Polyurethanes, Articles and Coatings Prepared Therefrom and Methods of Making the Same
US11248083B2 (en) 2004-09-01 2022-02-15 Ppg Industries Ohio, Inc. Aircraft windows
US20090280329A1 (en) 2004-09-01 2009-11-12 Ppg Industries Ohio, Inc. Polyurethanes, Articles and Coatings Prepared Therefrom and Methods of Making the Same
US11149107B2 (en) 2004-09-01 2021-10-19 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US20070173601A1 (en) * 2004-09-01 2007-07-26 Rukavina Thomas G Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US8207286B2 (en) 2004-09-01 2012-06-26 Ppg Industries Ohio, Inc Methods for preparing polyurethanes
US11591436B2 (en) 2004-09-01 2023-02-28 Ppg Industries Ohio, Inc. Polyurethane article and methods of making the same
US8349986B2 (en) * 2004-09-01 2013-01-08 Ppg Industries Ohio, Inc. Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same
US20070167600A1 (en) * 2004-09-01 2007-07-19 Rukavina Thomas G Polyurethanes prepared from polycaprolactone polyols, articles and coatings prepared therefrom and methods of making the same
US20070225468A1 (en) * 2004-09-01 2007-09-27 Rukavina Thomas G Polyurethanes prepared from polyester polyols and/or polycaprolactone polyols, articles and coatings prepared therefrom and methods of making the same
US9598527B2 (en) * 2004-09-01 2017-03-21 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US8399094B2 (en) * 2004-09-01 2013-03-19 Ppg Industries Ohio, Inc. Multilayer laminated articles including polyurethane and/or poly(ureaurethane) layers and methods of making the same
US9464169B2 (en) 2004-09-01 2016-10-11 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US8653220B2 (en) * 2004-09-01 2014-02-18 Ppg Industries Ohio, Inc. Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same
US11008418B2 (en) 2004-09-01 2021-05-18 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US20070251421A1 (en) * 2004-09-01 2007-11-01 Rukavina Thomas G Powder coatings prepared from polyurethanes and poly(ureaurethane)s, coated articles and methods of making the same
US8927675B2 (en) * 2004-09-01 2015-01-06 Ppg Industries Ohio, Inc. Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same
US8734951B2 (en) * 2004-09-01 2014-05-27 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US8889815B2 (en) * 2004-09-01 2014-11-18 Ppg Industries Ohio, Inc. Reinforced polyurethanes and poly(ureaurethane)s, methods of making the same and articles prepared therefrom
US8399559B2 (en) * 2004-09-01 2013-03-19 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US8604153B2 (en) * 2004-09-01 2013-12-10 Ppg Industries Ohio, Inc. Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same
US7687147B2 (en) * 2004-09-15 2010-03-30 Specialty Products, Inc. Composite article providing blast mitigation and method for manufacturing same
BRPI0516321B1 (pt) * 2004-10-21 2016-03-15 Dow Global Technologies Inc elastômero de poliuretano, artigo, sistema bi-componente adequado para a preparação de elastômeros de poliuretano e processo para preparar um elastômero de poliuretano fundido
FR2877006B1 (fr) * 2004-10-26 2007-01-26 Essilor Int Resines polyurethanes, leur procede de fabrication, et les lentilles optiques obtenues a partir de ces resines
MX2007012743A (es) * 2005-04-12 2008-01-11 Arkema France Lamina acrilica transparente resistente a balas.
US7771782B2 (en) * 2005-07-29 2010-08-10 Intercast Europe, srl Method of manufacturing a high impact polarized optical element and polarized optical element including an integrally bonded polarizing film
BRPI0520467A2 (pt) * 2005-08-04 2010-06-29 Resal S R L processo e composição para a preparação de poliuretanas transparentes e poliuretanas assim obtidas e artigos
US7666331B2 (en) * 2005-08-31 2010-02-23 Transitions Optical, Inc. Photochromic article
US20070100112A1 (en) * 2005-10-27 2007-05-03 Bayer Materialscience Llc Polyurethane-urea elastomers
KR20080074111A (ko) * 2005-10-27 2008-08-12 히다치 가세고교 가부시끼가이샤 수지 조성물 및 그것을 이용한 광학 부재
EP2004719B1 (en) * 2005-12-16 2012-06-13 PPG Industries Ohio, Inc. Impact resistant polyurethane and poly(ureaurethane) articles and methods of making the same
WO2007139586A2 (en) * 2005-12-16 2007-12-06 Ppg Industries Ohio, Inc. Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same
FR2896506B1 (fr) * 2006-01-20 2008-04-04 Essilor Int Composition polymerisable a base de polyurethane-uree et de copolymeres a blocs et materiau transparent obtenu a partir de celle-ci
EP1987377A2 (en) * 2006-02-24 2008-11-05 ESSILOR INTERNATIONAL Compagnie Générale d'Optique Process for manufacturing a polarized poly(thio)urethane optical lens
CN101054434B (zh) * 2006-04-13 2012-06-13 于子洲 紫外光快速固化水性聚氨酯树脂加工工艺
US7687597B2 (en) 2006-05-05 2010-03-30 Ppg Industries Ohio, Inc. Thioether functional oligomeric polythiols and articles prepared therefrom
US20080071016A1 (en) * 2006-09-14 2008-03-20 Ppg Industries Ohio, Inc. Polyureaurethane composition having improved color stability
WO2008108280A1 (ja) 2007-02-28 2008-09-12 Hoya Corporation プラスチックレンズ原料液注入方法および注入装置、ならびにプラスチックレンズの製造方法
ES2552107T3 (es) * 2007-05-04 2015-11-25 Essilor International (Compagnie Générale d'Optique) Método para la fabricación de un elemento óptico hecho de material plástico termoestable para su uso en dispositivos de protección de los ojos y elemento óptico así obtenido
US20090105013A1 (en) * 2007-09-28 2009-04-23 Edwin Charles Slagel Ultraviolet light resistant polymer compositions and methods of making and using
US8178644B2 (en) * 2008-01-02 2012-05-15 Polyplexx, Llc Impact-resistant polyurethane
US20090263651A1 (en) * 2008-02-06 2009-10-22 Cook Richard L Optically transparent resilient laminate materials and methods of manufacture
US20090258974A1 (en) * 2008-02-06 2009-10-15 Edwin Slagel Optically transmissive resilient polymers and methods of manufacture
EP2351638B1 (en) 2008-10-31 2016-11-23 Hoya Corporation Plastic lens manufacturing method and manufacturing device
DE102009005711A1 (de) 2009-01-22 2010-07-29 Bayer Materialscience Ag Polyurethanvergussmassen
KR101051316B1 (ko) * 2010-11-22 2011-07-22 한국수자원공사 내오존성 폴리우레탄 조성물 및 그 제조방법
US8608988B2 (en) 2010-11-23 2013-12-17 Transitions Optical, Inc. Curable photochromic compositions and optical articles prepared therefrom
WO2012135407A1 (en) 2011-04-01 2012-10-04 Am General Llc Transparent armor structure
KR102057746B1 (ko) 2012-04-23 2019-12-19 코베스트로 도이칠란드 아게 내광성 폴리우레탄 조성물
US9568643B2 (en) 2012-12-13 2017-02-14 Ppg Industries Ohio, Inc. Polyurethane urea-containing compositions and optical articles and methods for preparing them
EP4235273A3 (en) 2013-07-31 2023-09-27 Essilor International Additive manufacturing processes for transparent ophthalmic lens
US9500445B2 (en) * 2013-09-10 2016-11-22 The United States Of America As Represented By The Secretary Of The Army Multi-layer matrix composite having improved energy absorption, dissipation and shock wave mitigation capabilities
US20150166717A1 (en) 2013-12-17 2015-06-18 Bayer Materialscience Llc Polyurethaneureas or polyureas
US9994666B2 (en) 2013-12-17 2018-06-12 Covestro Llc Polyurethane/polyureas
JP6357910B2 (ja) * 2014-06-25 2018-07-18 Dic株式会社 光学用ポリウレタン組成物、薄膜成形体、光学フィルム、及び薄膜成形体の製造方法
BR112016028998B1 (pt) 2014-07-08 2021-10-05 Mitsui Chemicals, Inc. Composição polimerizável para material ótico, seu método de produção, produto moldado, material ótico e lente plástica
DE102015102012A1 (de) 2015-02-12 2016-08-18 Carl Zeiss Smart Optics Gmbh Optikelement
US11059746B2 (en) 2015-08-10 2021-07-13 America as represented by the Secretary of the Army Thermoplastic cycloaliphatic polyamide matrix resins for next-generation energy absorbing applications
CN105111404A (zh) * 2015-08-27 2015-12-02 厦门明睐科技有限公司 一种聚氨酯弹性体的制备方法
CN105237712A (zh) * 2015-11-12 2016-01-13 淄博德信联邦化学工业有限公司 聚氨酯护目镜及其制备方法
US9733488B2 (en) 2015-11-16 2017-08-15 Younger Mfg. Co. Composite constructed optical lens
EP3430467A1 (en) 2016-03-14 2019-01-23 Younger Mfg. Co., DBA Younger Optics Photochromic optical lens with selective blue light attenuation
EP3455659A4 (en) 2016-05-13 2020-02-12 Vision Ease LP POURED LENS
JP2018070865A (ja) 2016-10-25 2018-05-10 三井化学株式会社 光学材料用重合性組成物、該組成物から得られた光学材料及びその製造方法
US11073360B2 (en) * 2017-02-16 2021-07-27 Barrday Inc. Ballistic resistant article with thermoset polyurethane matrix
CA3051702C (en) * 2017-03-01 2022-02-01 Younger Mfg. Co. Dba Younger Optics Optical articles comprising photochromic poly(urea-urethane)
WO2019139193A1 (ko) * 2018-01-12 2019-07-18 주식회사 유창하이텍 열가소성 폴리우레탄 조성물 및 이의 제조방법
EP3768658B1 (en) 2018-03-21 2024-06-26 Rohm and Haas Company Method for preparing acrylic acid
EP3564286A1 (en) 2018-04-30 2019-11-06 Essilor International Blue light cutting optical material having a bluish appearance

Family Cites Families (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB731071A (en) * 1951-07-19 1955-06-01 Du Pont Preparation of elastomers from polyalkylene ether glycols and diisocyanates
US2644007A (en) * 1951-10-08 1953-06-30 Du Pont Preparation of polyamine hydrochlorides and polyisocyanates
US2680127A (en) * 1952-01-02 1954-06-01 Monsanto Chemicals Method of making organic isocyanates
US2830037A (en) * 1953-06-30 1958-04-08 Du Pont Poly
US2929804A (en) * 1955-01-31 1960-03-22 Du Pont Elastic filaments of linear segmented polymers
US2908703A (en) * 1955-08-16 1959-10-13 Harold K Latourette Preparation of aromatic isocyanates
NL126837C (zh) * 1958-01-17
BE589613A (zh) * 1959-04-10
US3127855A (en) * 1960-08-02 1964-04-07 Instr For Res & Industry Laboratory apparatus shields
US3456037A (en) * 1964-12-14 1969-07-15 Du Pont Polyurethane-polyureas
US3428711A (en) * 1966-02-01 1969-02-18 Du Pont Hindered polymeric tertiary amines as stabilizers for polyurethanes
US3370302A (en) * 1966-02-25 1968-02-27 Albert A. Karlyn Protective shield assembly
US3369836A (en) * 1966-08-01 1968-02-20 Gerald E. Haycock Removable protective shield for motorcycles
GB1292301A (en) * 1968-11-06 1972-10-11 Monsanto Co A helically crimped bicomponent polyamidepolyurethane filament
US3600358A (en) * 1969-01-28 1971-08-17 Allied Chem Polyurethane-urea elastomers prepared from 4,4'-methylene bis (cyclohexyl-isocyanate),neopentyl adipate and an aromatic diamine
US3620905A (en) * 1969-10-21 1971-11-16 Du Pont Optically clear thermoplastic polyurethanes
US3849360A (en) * 1970-09-03 1974-11-19 Textron Inc Polyurea-urethanes produced from a mixture of two polyamines
US3755262A (en) * 1971-01-15 1973-08-28 Goodyear Aerospace Corp Transparent high-impact polyurethane products
US3766148A (en) * 1971-05-17 1973-10-16 Allied Chem Polyurethane elastomers prepared from 4,4 - methylene-bis(cyclohexyl isocyanate),polyol and methylene dianiline
US3789032A (en) * 1971-06-22 1974-01-29 Du Pont Polyurethane-polyurea elastomers based on high trans-trans,4,4'-methylenebis-(cyclohexyl isocyanate)
US3718624A (en) * 1971-08-27 1973-02-27 Quaker Oats Co Method of curing polyurethane prepolymers with liquid extender comprising 4,4{40 -methylenebis (2-chloroaniline) and low molecular weight polytetramethylene ether glycol
US3866242A (en) * 1972-10-27 1975-02-18 Goodyear Aerospace Corp Protective shield
US3798200A (en) * 1972-12-13 1974-03-19 Bridgestone Tire Co Ltd Polyether urethane elastomer having an improved cut growth and flex crack resistance and the process for preparation thereof
IN141398B (zh) * 1973-05-16 1977-02-26 Ethicon Inc
JPS532199B2 (zh) * 1973-07-03 1978-01-26
US3932360A (en) * 1974-03-14 1976-01-13 Polaroid Corporation Polyurethane elastomers prepared from diamine curing agents
US3947426A (en) * 1974-04-12 1976-03-30 Story Chemical Corporation Solid particle-form polymerizable polymeric material and compositions, structures and methods of employing and producing the same
US4071492A (en) * 1976-04-07 1978-01-31 The Firestone Tire & Rubber Company Polyurethane-urea elastomers based on propylene oxide-tetrahydrofuran copolymers
US4088627A (en) * 1976-06-07 1978-05-09 Shell Oil Company Multicomponent polyurethane-block copolymer blends
DE2731815A1 (de) * 1977-07-14 1979-02-01 Basf Ag Polyurethan-harnstoff-elastomere
US4374210A (en) * 1981-09-18 1983-02-15 The Upjohn Company Polyurea-polyurethane from a mixture of a polyol, an aromatic diamine, and an isocyanate-terminated prepolymer
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
US4523005A (en) * 1981-10-30 1985-06-11 Thermedics, Inc. Extrudable polyurethane for prosthetic devices prepared from a diisocyanate, a polytetramethylene ether polyol, and 1,4-butane diol
US4447590A (en) * 1981-10-30 1984-05-08 Thermo Electron Corporation Extrudable polyurethane for prosthetic devices prepared from a diisocyanate, a polytetramethylene ether polyol and 1,4 butane diol
US4476292A (en) * 1984-01-30 1984-10-09 Ciba-Geigy Corporation Castable polyurethane systems
US4546167A (en) * 1984-07-30 1985-10-08 American Cyanamid Company P-TMXDI Polyurethane elastomers with good compression set properties
CH666260A5 (de) * 1985-10-23 1988-07-15 Lonza Ag Substituierte p,p'-methylen-bis-aniline und deren verwendung als kettenverlaengerungsmittel oder vernetzungsmittel fuer polyurethane.
DE3613790A1 (de) * 1986-04-24 1987-10-29 Bayer Ag Verfahren zur herstellung von thermoplastischen polyurethanen fuer die strahlenvernetzung und ihre verwendung
US4810749A (en) * 1987-05-04 1989-03-07 Corvita Corporation Polyurethanes
US4877856A (en) * 1987-08-31 1989-10-31 The Bf Goodrich Company Soft thermoplastic polyurethane for blown film application
US4808690A (en) * 1988-02-29 1989-02-28 Loral Corporation High heat distortion temperature transparent polyurethanes
US4927901A (en) * 1988-11-21 1990-05-22 Ciba-Geigy Corporation Curable polyurethane casting systems and amine hardeners therefor
US5066761A (en) * 1988-11-21 1991-11-19 Ciba-Geigy Corporation Curable polyurethane casting systems and amine hardeners therefor
US5011409A (en) * 1990-01-11 1991-04-30 Aukland (Usa), Inc. Polyurethane intraoral dam
EP1293525A3 (en) * 1990-06-26 2005-09-07 AorTech Biomaterials Pty Ltd Polyurethane or polyurethan-urea elastomeric compositions
JP3220873B2 (ja) * 1992-07-02 2001-10-22 イハラケミカル工業株式会社 ポリウレタンウレアエラストマー
US5266669A (en) * 1992-10-26 1993-11-30 Becton, Dickinson And Company Softening non-swelling polyurethane
GB9413327D0 (en) * 1994-07-01 1994-08-24 Medical Res Council Assay for inhibitors of dp-1
US5962617A (en) * 1995-02-02 1999-10-05 Simula Inc. Impact resistant polyurethane and method of manufacture thereof
IL116963A (en) * 1995-02-02 2000-02-17 Simula Inc Impact resistant polyurethane and methods for the manufacture thereof
ES2131411T3 (es) * 1995-09-05 1999-07-16 Phoenix Ag Tubo flexible de seguridad.
US5811506A (en) * 1997-02-03 1998-09-22 Simula Inc. Extrudable thermoplastic elastomeric urea-extended polyurethane
US5962619A (en) * 1998-03-16 1999-10-05 Arco Chemical Technology, L.P. Process for making clear polyurethane/urea elastomers

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1908698B (zh) * 2006-08-23 2010-10-06 黄则煌 丙烯基二甘醇碳酸酯护目镜片及其制造方法
CN101130597B (zh) * 2007-09-29 2011-06-01 山东东大一诺威聚氨酯有限公司 一种耐溶剂型聚氨酯弹性体的合成方法
CN101407572B (zh) * 2008-11-14 2011-07-20 上海维凯化学品有限公司 一种聚氨酯-聚脲水分散体及其制备方法
CN107383328A (zh) * 2017-06-27 2017-11-24 烟台观复光电材料有限公司 具有阻隔防护功能的柔性可弯折聚氨酯光学材料及其制备方法、透明柔性光学部件及其应用

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