CN111072901A - 一种超高硬度耐高温浇注型聚氨酯弹性体及其制备方法 - Google Patents

一种超高硬度耐高温浇注型聚氨酯弹性体及其制备方法 Download PDF

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CN111072901A
CN111072901A CN201911363144.2A CN201911363144A CN111072901A CN 111072901 A CN111072901 A CN 111072901A CN 201911363144 A CN201911363144 A CN 201911363144A CN 111072901 A CN111072901 A CN 111072901A
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polyurethane elastomer
diisocyanate
hardness
elastomer according
byk
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齐文斌
赵朝阳
刘朝索
靳祥娟
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Shanghai Hecheng Polymer Technology Co ltd
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Priority to IE20200257U priority patent/IE20200257U1/en
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Abstract

本发明涉及一种超高硬度耐高温浇注型聚氨酯弹性体及其制备方法，组分主要包括脂肪族异氰酸酯预聚物和芳香族胺扩链剂。本发明产品硬度为邵氏80～85D，外观透明，具有很好的回弹性，很好的抗拉、撕裂强度，很好的耐候性、耐紫外线、耐氧化等性能，而且在180℃的高温下，依然保持邵氏80D以上的硬度，具有良好的市场应用前景。

Description

一种超高硬度耐高温浇注型聚氨酯弹性体及其制备方法
技术领域
本发明属于聚氨酯弹性体领域，特别涉及一种超高硬度耐高温浇注型聚氨酯弹性体及其制备方法。
背景技术
浇注型聚氨酯弹性体材料是一种新兴的高分子材料，因其具有种类繁多的原料、不同的加工手段、弹性体组成中不同的软硬段比例、分子结构间各异的相排布等等，形成了从邵氏A0度到邵氏D85度的超宽硬度范围及具有各种各样的物理性能，比如可以有非常好的耐磨性，耐油性，也可以有很高的抗拉和撕裂强度，或者有很高的伸长率等等。通常浇注型聚氨酯弹性体材料硬度一般可以做到70D以下，而且在环境温度达到100℃以上时，硬度会急剧下降，无法保持较高的硬度和强度。这也极大的限制了聚氨酯弹性体材料在一些领域的应用。
常规的提高浇注型聚氨酯弹性体耐热性能的办法有这样几种：在多元醇方面，选取分子量较小的，或者含有苯环或酯环等环状结构来提高软段相的耐热性；在异氰酸酯方面，选取单苯环或者结构紧密的芳环异氰酸酯；在扩链剂方面，也是选取有苯环的胺类或者醇类扩链剂。这样的解决办法，主要是在弹性体分子主链上增加环状结构，来增大弹性体分子运动的位阻，以此来阻碍加热带给分子的相对运动。这样的主链上分布着环状结构的方式，在一定程度上可以满足弹性体材料的耐热性，但在遇到更高温度，比如在达到140℃以上时，弹性体主链的分子间作用力变弱，较易发生位移，导致弹性体外在表现为受到高热硬度急剧降低。
发明内容
本发明所要解决的技术问题是提供一种超高硬度耐高温浇注型聚氨酯弹性体及其制备方法，该聚氨酯弹性体在180℃的高温下，依然保持邵氏80D以上的硬度。
本发明提供了一种超高硬度耐高温浇注型聚氨酯弹性体，按质量百分比，由以下组分组成：
Figure BDA0002337727160000011
Figure BDA0002337727160000021
所述脂肪族异氰酸酯预聚物HC-100的原料为30～40％聚醚多元醇和60～70％脂肪族二异氰酸酯。
所述聚醚多元醇的分子量为300～4000，官能度为2～4，选自GE-204、RA-640、NT-403A、DV-125、MN-500、MN-700、MN-1000、MN-1500、MN-3050D、GE-303中的一种或几种；所述脂肪族二异氰酸酯为1,6-亚己基二异氰酸酯HDI、HDI三聚体、HDI缩二脲、3-异氰酸酯基亚甲基-3,5,5-三甲基环己基异氰酸酯IPDI、4,4'-二环己基甲烷二异氰酸酯HMDI、m-亚二甲苯基二异氰酸酯XDI、氢化苯二亚甲基二异氰酸酯HXDI、2,2,4-及2,4,4-三甲基-1,6-六亚甲基二异氰酸酯混合物TMHMDI、四甲基间二亚甲苯基二异氰酸酯m-TMXDI、降莰烷二异氰酸酯NBDI中的至少一种。
所述芳香族胺扩链剂为3,3’-二氯-4,4’-二苯基甲烷二胺MOCA、3,5-二甲硫基甲苯二胺DMTDA、3,5-二乙基甲苯二胺DETDA、4,4’-亚甲基双(3-氯-2,6-二乙基苯胺)MCDEA、4,4’-亚甲基双(2,6-二乙基)苯胺MDEA中的至少一种。
所述抗氧剂为2,6-二叔丁基-4-甲基苯酚BHT、四亚甲基(3,5-二-叔丁基-4-羟基苯丙酸)甲酯1010、亚磷酸三(2,4-二叔丁基苯基)酯中的至少一种。
所述紫外线吸收剂为4-[[(甲基苯氨基)亚甲基]氨基]苯甲酸乙酯(tinuvin101)、2-(2'-羟基-3',5'-二叔丁基苯基)-5-氯代苯并三唑(UV-327)、2-羟基-4-正辛氧基二苯甲酮(UV-531)中的至少一种。
所述水解稳定剂为2，2'，6,6'-四异丙基二苯基碳化二亚胺(stabaxol I)、多碳二亚胺(staboxol P)中的至少一种。
所述储存稳定剂为磷酸、苯甲酰氯中的至少一种。
所述消泡剂为BYK 052、BYK 053、BYK 056、BYK A560中的至少一种。
本发明还提供了一种超高硬度耐高温浇注型聚氨酯弹性体的制备方法，包括：
(1)依照30～40％聚醚多元醇和60～70％脂肪族二异氰酸酯的比例，在70～90℃下3～6小时，合成脂肪族异氰酸酯预聚物HC-100；
(2)按配方称取脂肪族异氰酸酯预聚物，升温至90～110℃，在真空度为-0.1MPa下抽真空20～30分钟；
(3)然后将温度降至68～72℃，加入抗氧剂、紫外线吸收剂、水解稳定剂、储存稳定剂和消泡剂，均匀搅拌10～20分钟，再次在真空度为-0.1MPa下抽真空10～20分钟；
(4)将芳香族胺扩链剂加入到步骤(2)的混合物中，搅拌均匀，再次抽真空1～2分钟后，倒入预先涂好脱模剂的模具中，放入100～105℃的鼓风烘箱中，硫化30～40分钟，脱模；
(5)脱模后，将制品继续在100～105℃的烘箱中硫化22～24小时，即得超高硬度耐高温的浇注型聚氨酯弹性体。
本发明的原理如下：
通过使用高官能度的脂肪族异氰酸酯预聚物，在形成网状结构的分子主链上，添加扩链剂所含有的环状结构，使整个弹性体分子链形成大量立体的网络贯穿结构，大大增加了弹性体材料的分子量和支化度，表观为弹性体形成超高的硬度；同时也加大了弹性体材料分子间的作用力，在受到高温时位阻效应阻止了大部分分子的位移，表观为弹性体可以在高温下保持硬度。
有益效果
本发明产品硬度为邵氏80～85D，外观透明，具有很好的回弹性，很好的抗拉、撕裂强度，很好的耐候性、耐紫外线、耐氧化等性能，而且在180℃的高温下，依然保持邵氏80D以上的硬度，具有良好的市场应用前景。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
按质量百分比，由以下组分组成：
Figure BDA0002337727160000031
Figure BDA0002337727160000041
实施例2
按质量百分比，由以下组分组成：
Figure BDA0002337727160000042
制备方法，包括如下步骤：
(1)依照NT-403A＝33.4％，HDI＝66.6％的比例在70～90℃下3～6小时，合成脂肪族异氰酸酯预聚物HC-100。
(2)按配方称取脂肪族异氰酸酯预聚物，升温至100℃，在真空度为-0.1MPa下抽真空25分钟；
(3)然后将温度降至70℃，加入抗氧剂、紫外线吸收剂、水解稳定剂、储存稳定剂和消泡剂，均匀搅拌15分钟，再次在真空度为-0.1MPa下抽真空15分钟；
(4)将芳香族胺扩链剂加入到步骤(2)的混合物中，搅拌均匀，再次抽真空2分钟后，倒入预先涂好脱模剂的模具中，放入105℃的鼓风烘箱中，硫化30分钟，脱模；
(5)脱模后，将制品继续在105℃的烘箱中硫化24小时，即得超高硬度耐高温的浇注型聚氨酯弹性体。
以上工艺得到的聚氨酯弹性体性能如下表所示：
Figure BDA0002337727160000043
Figure BDA0002337727160000051

Claims (10)

1.一种超高硬度耐高温浇注型聚氨酯弹性体，其特征在于：按质量百分比，由以下组分组成：
Figure FDA0002337727150000011
2.根据权利要求1所述的聚氨酯弹性体，其特征在于：所述脂肪族异氰酸酯预聚物HC-100的原料为30～40％聚醚多元醇和60～70％脂肪族二异氰酸酯。
3.根据权利要求2所述的聚氨酯弹性体，其特征在于：所述聚醚多元醇的分子量为300～4000，官能度为2～4，选自GE-204、RA-640、NT-403A、DV-125、MN-500、MN-700、MN-1000、MN-1500、MN-3050D、GE-303中的一种或几种；所述脂肪族二异氰酸酯为1,6-亚己基二异氰酸酯HDI、HDI三聚体、HDI缩二脲、3-异氰酸酯基亚甲基-3,5,5-三甲基环己基异氰酸酯IPDI、4,4'-二环己基甲烷二异氰酸酯HMDI、m-亚二甲苯基二异氰酸酯XDI、氢化苯二亚甲基二异氰酸酯HXDI、2,2,4-及2,4,4-三甲基-1,6-六亚甲基二异氰酸酯混合物TMHMDI、四甲基间二亚甲苯基二异氰酸酯m-TMXDI、降莰烷二异氰酸酯NBDI中的至少一种。
4.根据权利要求1所述的聚氨酯弹性体，其特征在于：所述芳香族胺扩链剂为3,3’-二氯-4,4’-二苯基甲烷二胺MOCA、3,5-二甲硫基甲苯二胺DMTDA、3,5-二乙基甲苯二胺DETDA、4,4’-亚甲基双(3-氯-2,6-二乙基苯胺)MCDEA、4,4’-亚甲基双(2,6-二乙基)苯胺MDEA中的至少一种。
5.根据权利要求1所述的聚氨酯弹性体，其特征在于：所述抗氧剂为2,6-二叔丁基-4-甲基苯酚BHT、四亚甲基(3,5-二-叔丁基-4-羟基苯丙酸)甲酯1010、亚磷酸三(2,4-二叔丁基苯基)酯中的至少一种。
6.根据权利要求1所述的聚氨酯弹性体，其特征在于：所述紫外线吸收剂为4-[[(甲基苯氨基)亚甲基]氨基]苯甲酸乙酯、2-(2'-羟基-3',5'-二叔丁基苯基)-5-氯代苯并三唑、2-羟基-4-正辛氧基二苯甲酮中的至少一种。
7.根据权利要求1所述的聚氨酯弹性体，其特征在于：所述水解稳定剂为2，2'，6,6'-四异丙基二苯基碳化二亚胺、多碳二亚胺中的至少一种。
8.根据权利要求1所述的聚氨酯弹性体，其特征在于：所述储存稳定剂为磷酸、苯甲酰氯中的至少一种。
9.根据权利要求1所述的聚氨酯弹性体，其特征在于：所述消泡剂为BYK 052、BYK 053、BYK 056、BYK A560中的至少一种。
10.一种如权利要求1所述的超高硬度耐高温浇注型聚氨酯弹性体的制备方法，包括：
(1)依照30～40％聚醚多元醇和60～70％脂肪族二异氰酸酯的比例，在70～90℃下3～6小时，合成脂肪族异氰酸酯预聚物HC-100；
(2)按配方称取脂肪族异氰酸酯预聚物，升温至90～110℃，在真空度为-0.1MPa下抽真空20～30分钟；
(3)然后将温度降至68～72℃，加入抗氧剂、紫外线吸收剂、水解稳定剂、储存稳定剂和消泡剂，均匀搅拌10～20分钟，再次在真空度为-0.1MPa下抽真空10～20分钟；
(4)将芳香族胺扩链剂加入到步骤(2)的混合物中，搅拌均匀，再次抽真空1～2分钟后，倒入预先涂好脱模剂的模具中，放入100～105℃的鼓风烘箱中，硫化30～40分钟，脱模；
(5)脱模后，将制品继续在100～105℃的烘箱中硫化22～24小时，即得超高硬度耐高温的浇注型聚氨酯弹性体。
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