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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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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ATE274004T1 (de) 2004-09-15
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EP1137684A4 (en) 2002-03-20
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