CN104817683A - 一种聚氨酯弹性体及其制备方法 - Google Patents
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Abstract
本发明公开了一种聚氨酯弹性体及其制备方法,由两部分组成,以重量份计包括,A组分:大分子二元醇100份,1,5-萘二异氰酸酯(NDI)5~20份,对苯二异氰酸酯(PPDI)10~30份或3,3-二甲基-4,4-联苯二异氰酸酯(TODI)10~50份;B组分:大分子二元醇0~100份,扩链剂8~30份,催化剂0.02~0.5份;A/B重量比为100/8~30。本发明所制备的预聚体具有良好储存稳定性,黏度较低,改善了A/B组份间巨大的比例差异,不需采用特殊装备的弹性体浇注机,简化了预聚体的生产和浇注使用工艺,也直接降低了弹性体材料的成本。
Description
技术领域
本发明涉及一种聚氨酯(PU)弹性体及其制备方法,特别涉及具有良好的力学性能和优异耐疲劳性的高性能聚氨酯弹性体。
背景技术
众所周知,基于1,5-萘二异氰酸酯(NDI)型的聚氨酯弹性体在力学、回弹和耐疲劳性能等方面具有其他种类异氰酸酯的PU弹性体产品所无法企及的优势,一直以来作为聚氨酯弹性体领域的高端产品应用于特殊领域。但由于NDI本身的特性,使得所制备的NDI型预聚体无法长期储存,必须在短期(3~4h)内尽快进行下一步的反应,否则会极易发生副反应,导致预聚体黏度变大而变质,无法制备性能稳定的聚氨酯弹性体制品。同时预聚体不稳定的特性还造成无法采用半预聚法的聚氨酯弹性体浇注工艺,只能采用预聚法的工艺制备弹性体制品,导致预聚体黏度较大。CN 101265315A和CN1011861346A等专利中均公布了制备可稳定储存的NDI预聚体的方法,但是生产过程中需要快速冷却预聚体,这与普通预聚体的制备工艺相比,大大增加了预聚体生产工艺的复杂性、生产成本等。同时,其所开发的稳定储存型NDI预聚体使用1,4-丁二醇扩链,与普通的聚氨酯浇注机设备相比,NDI预聚体用浇注机必须能满足精确的温度控制和良好的脱泡装置并可充惰性气体,以保证预聚体的稳定性。并且由于混合比率大约是100份高黏度NDI预聚体比4份黏度相对较低的1,4-丁二醇,所以对浇注机计量泵压力的稳定性要求也极为苛刻。而为了保证NDI预聚体反应的一致性和稳定性,还需使用特殊的熔化设备来把固体预聚体融为液态而不妨碍其反应。这均大大提高了稳定储存NDI预聚体在浇注生产弹性体时的复杂性、增加了设备成本等。
为解决NDI预聚体价格昂贵、制备和使用工艺复杂等问题,王晓鸣,刘鸿慈,等.基于MDI/NDI的聚氨酯弹性体的结构与性能[J],合成橡胶工业,2007,30(2),107~110.合成了基于MDI/NDI的聚氨酯弹性体,但由于其中MDI的存在所造成的弹性体材料在动态负荷下形变较大、内生热大、磨损严重、耐疲劳性能差等问题无法解决。
发明内容
本发明要解决的第一个技术问题是提供一种聚氨酯弹性体,该弹性体具有良好的力学性能和优异的耐疲劳性。
本发明要解决的第二个技术问题是提供一种该聚氨酯弹性体的制备方法。
本发明聚氨酯弹性体由预聚体组分(A组分)和扩链剂组分(B组分)两部分组成,以重量份计包括:
(1)A组分
(2)B组分
大分子二元醇 0~100份
扩链剂 8~30份
催化剂 0.02~0.5份
A/B重量比为100/8~30。
本发明所述大分子二元醇选自分子量为500-3000的聚酯二元醇、聚碳酸酯二元醇或聚四氢呋喃二元醇(PTMG)或其组合,优选分子量650-2000。其中,聚酯二元醇包括小分子二元羧酸和小分子二元醇的反应产物,还包括各种内酯与二元醇反应得到的产物,如己内酯与乙二醇、二甘醇等反应制备的ε-聚己内酯二元醇(PCL)等,优选为分子量650-2000的聚己二酸系聚酯二元醇、ε-聚己内酯二元醇。
本发明所述的扩链剂为小分子二元醇、小分子三元醇、三官能度醇胺或氨类聚氨酯扩链交联剂。当A组分中添加PPDI时,使用小分子二元醇、小分子三元醇、三官能度醇胺或其组合,其中小分子二元醇扩链剂包含乙二醇、二乙二醇、丙二醇、1,4-丁二醇、己二醇、戊二醇、间苯二酚双(β-羟乙基)醚(HER)或对氢醌-双(β-羟乙基)醚(HQEE)等,小分子三元醇扩链剂如三羟甲基乙烷(TME)、甘油(GLY)、三羟甲基丙烷(TMP)或聚己内酯三醇等,三官能度醇胺类为三异丙醇胺(TIPA),优选使用1,4-丁二醇(BDO)、间苯二酚双(β-羟乙基)醚(HER)、对氢醌-双(β-羟乙基)醚(HQEE)、TIPA、TMP或其组合。当A组分中添加TODI时,使用小分子二元醇、小分子三元醇、芳香族二元胺、三官能度醇胺或其组合,其中小分子二元醇类扩链剂包含乙二醇、二乙二醇、丙二醇、1,4-丁二醇、己二醇、戊二醇,小分子三元醇扩链剂如三羟甲基乙烷(TME)、甘油(GLY)、三羟甲基丙烷(TMP)或聚己内酯三醇等,芳香族二元胺包含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)或2,4-二氨基-3,5-二甲硫基氯苯(TX-2)等,三官能度醇胺类为三异丙醇胺(TIPA),优选使用BDO、MOCA、TIPA、TMP或其组合。
本发明所述的催化剂为叔胺类、有机铋类或有机锡类化合物中的一种或多种混合物。叔胺类催化剂优选三乙烯二胺;有机铋类化合物选自异辛酸铋或羧酸铋或其组合,有机锡类化合物选自辛酸亚锡(T-9)、二辛酸二丁锡和二月桂酸二丁锡(T-12)等中的一种或多种。
本发明聚氨酯弹性体的制备方法,包括以下步骤:
(1)A组分的制备:将计量的大分子二元醇在95~120℃、-0.098~-0.1MPa下脱水2~3h,然后保持温度在110~130℃下加入计量的NDI,在该温度下反应10~30min,降温至60~80℃,再加入计量的PPDI或TODI,加入PPDI保持反应温度为70~80℃,加入TODI保持反应温度为90~100℃,反应时间均为1.5~2.5h,达到理论NCO%值后,抽真空脱泡,降温出料,密封保存;
(2)B组分的制备:将大分子二元醇、液体扩链剂或预先融化为液体的扩链剂、催化剂按计量进行搅拌,混合均匀,保持B组分为液体状态使用;
(3)弹性体的制备:物料浇注可采用机器浇注或手工浇注,A组分温度为75~90℃,B组分温度为45~120℃,将两组分充分混合均匀,注入温度为110~130℃的模具中,脱模时间30~60min,脱模后制品需在110~130℃温度下后硫化16~24h。
本发明所得高性能聚氨酯弹性体材料性能见表1。
表1高性能聚氨酯弹性体材料性能
硬度/邵A | 80~98 |
拉伸强度/MPa | 35~55 |
撕裂强度/N/mm | 90~125 |
伸长率/% | 400~600 |
回弹率/% | 40~65 |
车轮行走距离/km | >13 |
注:车轮行走距离测试方法:将弹性体制备成相同形状的其中轮芯内径为42mm、外径为99mm、高度为61mm、聚氨酯胶层厚度为14mm的承载轮,载荷600kg,在车轮测试机上以8km/h的速度测试,每间距1m有一高度为4mm、宽度为5cm的障碍物,以测试车轮破坏前的距离表示耐动态疲劳性,行走距离越长则意味着耐疲劳性能较好。
本发明聚氨酯弹性体材料,通过使用NDI改性大分子二元醇,而非制备纯NDI预聚体的方法在弹性体材料中引入NDI基团,在保证材料和制品优异性能的同时,使用的PPDI或TODI,降低了预聚体成本。所制备的预聚体具有良好储存稳定性,黏度较低,改善了A/B组份间巨大的比例差异,不需采用特殊装备的弹性体浇注机,简化了预聚体的生产和浇注使用工艺,也直接降低了弹性体材料的成本。
本发明的产品主要用于承受动态疲劳的高强度承载领域,如汽车、高铁等交通工具的缓冲减震元件和机械领域的承重轮等。
具体实施方式
以下结合实施例对本发明作详细说明。
实施例1
(1)A组分的制备:将400g数均分子量为2000的聚己二酸丁二醇酯二元醇在95~100℃、-0.1MPa条件下脱水2h,升温至120℃,加入21g NDI,保持该温度10min后,降温至60℃,加入50g PPDI,在70~80℃下反应1.5h,抽真空脱泡,出料备用。
(2)B组分的制备:将60g HER和30gHQEE在100℃融化后,与0.4g的催化剂(使用丙二醇配制的三乙基二胺含量为33%的溶液)混合均匀,并保持液体状态。
(3)弹性体的制备:将A组分保持在75~80℃,B组分保持在85~90℃,A/B组分按照重量比100/8.3混合均匀并脱泡后,浇入120℃的模具中,60min脱模,120℃后硫化20h,室温放置7天后测性能。测试结果见表2。
实施例2
(1)A组分的制备:将400g数均分子量为650的PTMG在95~100℃、-0.1MPa条件下脱水2h,升温至120℃,加入40g NDI,在保持该温度10min后,降温至80℃,加入200g TODI,在85~90℃下反应2h,真空脱泡,出料备用。
(2)B组分的制备:将100gMOCA在120℃融化,并保持在该温度。
(3)弹性体的制备:将A组分保持在80~85℃,B组分保持在115~120℃,A/B组分按照重量比100/12.9混合均匀并脱泡后,浇入120℃的模具中,60min脱模,120℃后硫化24h,室温放置7天后测性能。测试结果见表2。
实施例3
(1)A组分的制备:将400g数均分子量为500的PCL在95~100℃、-0.1MPa下脱水2h,升温至120℃,加入80g NDI,保持该温度10min后,降温至60℃,加入114.6g PPDI,在70~80℃下反应1.5h,抽真空脱泡,出料备用。
(2)B组分的制备:将50g HER、50g HQEE和15.7g TIPA在100℃融化后,与0.4g T12催化剂混合均匀,并保持液体状态。
(3)弹性体的制备:将A组分保持在75~80℃,B组分保持在85~90℃,A/B组分按照重量比100/8.3混合均匀并脱泡后,浇入120℃的模具中,60min脱模,120℃后硫化20h,室温放置7天后测性能。测试结果见表2。
实施例4
(1)A组分的制备:将400g数均分子量为1000的聚己二酸乙二醇酯二醇在100~110℃、-0.1MPa下脱水3h,升温至120℃,加入28g NDI,保持该温度10min后,降温至60℃,加入120g PPDI,在70~80℃下反应1.5h,抽真空脱泡,出料备用。
(2)B组分的制备:将100g数均分子量为1000的聚己二酸乙二醇酯二醇与20g BDO、0.45g的催化剂(使用丙二醇配制的三乙基二胺含量为33%的溶液)混合均匀,并保持液体状态。
(3)弹性体的制备:将A组分保持在75~80℃,B组分保持在55~60℃,A/B组分按照重量比100/27.3混合均匀并脱泡后,浇入120℃的模具中,60min脱模,120℃后硫化20h,室温放置7天后测性能。测试结果见表2。
对比例1
(1)A组分的制备:将400g数均分子量为2000的PCL在95~100℃、-0.1MPa下脱水2h,加入74g NDI,在110~130℃下反应20min,并迅速降温至70℃以下,抽真空脱泡,出料备用。
(2)弹性体的制备:将A组分保持在90~100℃,BDO保持为液体状态,A/B组分按照重量比100/2.5混合均匀并脱泡后,浇入120℃的模具中,60min脱模,120℃后硫化24h,室温放置7天后测性能。测试结果见表2。
对比例2
(1)A组分的制备:将400g数均分子量为1000的聚己二酸乙二醇酯二元醇在95~100℃、-0.1MPa下脱水2h,加入139.3g NDI,在110~130℃下反应25min,并迅速降温至70℃以下,抽真空脱泡,出料备用。
(2)弹性体的制备:将A组分保持在90~100℃,BDO保持为液体状态,A/B组分按照重量比100/3.9混合均匀并脱泡后,浇入120℃的模具中,60min脱模,120℃后硫化24h,室温放置7天后测性能。测试结果见表2。
表2实施例测试结果
Claims (10)
1.一种聚氨酯弹性体,由预聚体组分(A组分)和扩链剂组分(B组分)两部分组成,以重量份计包括:
(1)A组分
大分子二元醇 100份
1,5-萘二异氰酸酯(NDI) 5~20份
对苯二异氰酸酯(PPDI)10~30份或3,3-二甲基-4,4-联苯二异氰酸酯(TODI) 10~50份
(2)B组分
大分子二元醇 0~100份
扩链剂 8~30份
催化剂 0.02~0.5份
A/B重量比为 100/8~30
所述大分子二元醇选自分子量为500-3000的聚酯二元醇、聚碳酸酯二元醇或聚四氢呋喃二元醇(PTMG)或其组合。
2.根据权利要求1所述的聚氨酯弹性体,其特征是聚酯二元醇是指小分子二元羧酸和小分子二元醇的反应产物,或各种内酯与二元醇反应得到的产物。
3.根据权利要求2所述的聚氨酯弹性体,其特征是聚酯二元醇是指己内酯与乙二醇、二甘醇反应制备的ε-聚己内酯二元醇(PCL)。
4.根据权利要求1所述的聚氨酯弹性体,其特征是所述的扩链剂为小分子二元醇、小分子三元醇、三官能度醇胺或氨类聚氨酯扩链交联剂。
5.根据权利要求4所述的聚氨酯弹性体,其特征是A组分中异氰酸酯为1,5-萘二异氰酸酯(NDI)和对苯二异氰酸酯(PPDI),扩链剂为小分子二元醇、小分子三元醇、三官能度醇胺或其组合。
6.根据权利要求5所述的聚氨酯弹性体,其特征是小分子二元醇是指乙二醇、二乙二醇、丙二醇、1,4-丁二醇、己二醇、戊二醇、间苯二酚双(β-羟乙基)醚(HER)或对氢醌-双(β-羟乙基)醚(HQEE);三官能度醇胺是指三异丙醇胺(TIPA);小分子三元醇是指三羟甲基乙烷(TME)、甘油(GLY)、三羟甲基丙烷(TMP)或聚己内酯三醇。
7.根据权利要求4所述的聚氨酯弹性体,其特征是A组分中异氰酸酯为1,5-萘二异氰酸酯(NDI)和TODI,扩链剂为小分子二元醇、小分子三元醇、芳香族二元胺、三官能度醇胺或其组合。
8.根据权利要求7所述的聚氨酯弹性体,其特征是小分子二元醇是指乙二醇、二乙二醇、丙二醇、1,4-丁二醇、己二醇或戊二醇;小分子三元醇是指三羟甲基乙烷(TME)、甘油(GLY)、三羟甲基丙烷(TMP)或聚己内酯三醇;芳香族二元胺是指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)、2,4-二氨基-3,5-二甲硫基氯苯(TX-2);三官能度醇胺是指三异丙醇胺(TIPA)。
9.根据权利要求1所述的聚氨酯弹性体,其特征是所述的催化剂为叔胺类、有机铋类或有机锡类化合物中的一种或多种混合物。
10.一种制备权利要求1~10之一所述的聚氨酯弹性体的制备方法,包括以下步骤:
(1)A组分的制备:将计量的大分子二元醇在95~120℃、-0.098~-0.1MPa下脱水2~3h,然后保持温度在110~130℃下加入计量的NDI,在该温度下反应10~30min,降温至60~80℃,再加入计量的PPDI或TODI,若加入PPDI保持反应温度为70~80℃,若加入TODI保持反应温度为90~100℃,反应时间均为1.5~2.5h,达到理论NCO%值后,抽真空脱泡,降温出料,密封保存;
(2)B组分的制备:将大分子二元醇、液体扩链剂或预先融化为液体的扩链剂、催化剂按计量进行搅拌,混合均匀,保持B组分为液体状态使用;
(3)弹性体的制备:物料浇注可采用机器浇注或手工浇注,A组分温度为75~90℃,B组分温度为45~120℃,将两组分充分混合均匀,注入温度为110~130℃的模具中,脱模时间30~60min,脱模后制品需在110~130℃温度下后硫化16~24h。
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