CN107189028A - 一种环保高性能快速脱模聚氨酯反应注射成型组合物及其自催化扩链剂的制备方法 - Google Patents

一种环保高性能快速脱模聚氨酯反应注射成型组合物及其自催化扩链剂的制备方法 Download PDF

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CN107189028A
CN107189028A CN201710529908.5A CN201710529908A CN107189028A CN 107189028 A CN107189028 A CN 107189028A CN 201710529908 A CN201710529908 A CN 201710529908A CN 107189028 A CN107189028 A CN 107189028A
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孙嘉鹏
董火成
李宁
赵修文
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Liming Research Institute of Chemical Industry Co Ltd
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Abstract

本发明公开了一种环保高性能快速脱模聚氨酯反应注射成型组合物及其自催化扩链剂的制备方法。组合物包括两组分，A组分包含1％～10％的自催化扩链剂和0.01％～2％复合催化剂，所述自催化扩链剂是指具有以下结构的物质：式中x＝2～5，R为CyH2y+1，y＝0～2；所述复合催化剂是异辛酸铋10份，异辛酸钾1～2份，双环脒类化合物15份，丙三醇10份。B组分：MDI 60％～95％，改性剂5％～40％，NCO含量23％～28％，所述改性剂包括至少一种二元醇和至少一种三元醇。自催化扩链剂的制备方法是将无水哌嗪加热至65±5℃，恒温状态下将环氧乙烷、环氧丙烷或环氧丁烷中的一种按照摩尔比缓慢滴加至反应容器中，滴加完毕升温至80～85℃反应4h，冷却出料。该组合物气味低、VOC低、耐候性好、脱模时间短。

Description

一种环保高性能快速脱模聚氨酯反应注射成型组合物及其自 催化扩链剂的制备方法
技术领域
本发明涉及聚氨酯反应注射成型材料及制备工艺。
背景技术
聚氨酯反应注射成型(PU-RIM)材料在汽车中的应用十分广泛，从应用部位上区分主要分内饰件和外饰件。处于汽车驾驶舱内的材料属于内饰件，如汽车座椅泡沫，该类产品对材料的环保性能如气味等级、可挥发性有机物含量等要求极为严格；处于驾驶舱外的部件为汽车外饰件，如天窗、大包围等，则对材料光老化性能要求更为严苛，环保性能的要求则相对较低。但随着产品的不断更新换代和对产品要求的不断提高，很多产品都对材料的耐候性和环保性能提出了双重的高要求，其中较为典型的就是汽车玻璃包边用PU-RIM材料，该材料既属于外饰件，需要较高的耐候性，同时由于直接与驾驶舱连接，对环保性能的要求也日益提高。因此，在保证高反应活性、高耐候性的前提下，降低可挥发性有机物含量、降低气味，是目前这类材料面临的主要问题。
聚氨酯材料按照所用异氰酸酯的不同可分为芳香族和脂肪族两大类，芳香族异氰酸酯作为传统的聚氨酯原料，应用较为广泛和深入。但由于芳香族异氰酸酯的结构中含有苯环，在光照的作用下易发生反应而黄变；而脂肪族异氰酸酯具有优异的耐光老化性能，但脂肪族异氰酸酯反应活性较低，难以满足PU-RIM对凝胶和脱模时间的要求。
专利文献CN1633454A、CN1455791A、CN1946756A、CN101061154A、CN101906200均涉及利用自催化多元醇生产聚氨酯材料的技术，但均需配合其他胺类催化剂，技术应用范围属于聚氨酯发泡材料，其反应速度、分子结构均不适于反应注射成型工艺；另外上述发明所涉及的多元醇黏度较大，流动性、充模性较差，必须配合大量发泡剂或水使用，亦无法直接应用于非发泡体系中。
专利文献CN103172822A公开了一种快速脱模耐候型聚氨酯反应注射成型用组合物及其制备方法。该发明通过使用有机金属复合催化剂，能够显著提高反应速率，大大缩短凝胶和脱模时间，凝胶时间为8～20s，脱模时间为45～600s。这种方法可实现较高的生产效率，但由于复合催化剂中含有一定量的溶剂，如丙酮、1，4-二氧六环、二甲苯或乙酸乙酯，且该复合催化剂在组合物体系中占比较大，材料的气味等级和VOC难以满足其应用领域对环保性能的要求。
发明内容
本发明要解决的第一个技术问题是提供一种环保高性能快速脱模聚氨酯反应注射成型组合物，该组合物气味低、VOC低、耐候性好、脱模时间短。
本发明要解决的第二个技术问题是提供一种该组合物所用自催化扩链剂的制备方法。该自催化扩链剂催化活性高，可以与脂肪族异氰酸酯配合使用。
为解决第一个技术问题，本发明提供一种环保高性能快速脱模聚氨酯反应注射成型组合物，该组合物包括A、B两组分，按质量分数计包括以下成分：
A组分：聚醚多元醇50％～90％，自催化扩链剂1％～10％，扩链剂1％～10％，交联剂1％～20％，颜料0～8％，抗老化剂1％～5％，复合催化剂0.01％～2％，优选0.5％～2％；
B组分：4，4’-二环己基甲烷二异氰酸酯60％～95％，改性剂5％～40％，异氰酸根(NCO)含量23％～28％。所述改性剂包括至少一种二元醇和至少一种三元醇。所述二元醇包括聚氧化丙烯二醇、聚四氢呋喃二醇等中的一种或多种，聚氧化丙烯二醇优选分子量400～4000，聚四氢呋喃二醇优选分子量650～2000。所述三元醇优选三羟甲基乙烷、三羟甲基丙烷、丙三醇等中的一种或多种。
所述自催化扩链剂是指具有以下结构的物质：
式中x＝2～5，R为CyH2y+1，y＝0～2。
所述复合催化剂是由异辛酸铋、异辛酸钾、双环脒类化合物与丙三醇复配而成，复配质量比为：异辛酸铋10份，异辛酸钾1～～2份，双环脒类化合物15份，丙三醇10份，所述双环脒类化合物具有以下通式：
式中R1＝CaH2a，a＝2～4；R2＝CbH2b，b＝3～7。
适宜的聚醚多元醇优选伯羟基含量＞70％，数均分子量3000～6500的环氧乙烷-环氧丙烷共聚醚三醇等中的一种或多种。
适宜的扩链剂优选乙二醇、1，4-丁二醇、1，3-丁二醇、一缩二乙二醇、二乙醇胺等中的一种或多种。
适宜的交联剂优选丙三醇、三羟甲基乙烷、三羟甲基丙烷、三羟乙基异氰脲酸酯等中的一种或多种。
适宜的抗老化剂优选2-(2′-羟基-3′，5′-二叔丁基苯基)-5-氯代苯并三氮唑、2-(2′-羟基-5′-甲基苯基)苯并三氮唑、双(3，5-三级丁基-4-羟基苯基)硫醚、双(1，2，2，6，6-五甲基-4-哌啶基)癸二酸酯、亚磷酸三辛酯等中的一种或多种。
一种制备本发明所述组合物的方法，包括：
A组分：将各物料加入反应釜中，25℃下混合均匀。
B组分：将异氰酸酯和改性剂同时加入反应容器，搅拌下加热升温至90℃，反应2～3h，冷却至室温，出料。
所述自催化型扩链剂可由哌嗪与环氧乙烷、环氧丙烷或环氧丁烷中的一种进行烷氧基化反应制得，反应式为：
其中n，m，h＝2～5。
产物用通式表示为：
式中x＝2～5，R为CyH2y+1，y＝0～2。
为解决第二个技术问题，本发明提供一种制备自催化扩链剂的方法，包括以下步骤：将无水哌嗪在带有冷凝回流装置的反应容器中加热至65±5℃，恒温状态下将环氧乙烷、环氧丙烷或环氧丁烷中的一种按照摩尔比缓慢滴加至反应容器中，滴加完毕升温至80～85℃反应4h，冷却至室温后出料。
本发明组合物相比现有技术具有以下有益效果：
1.采用发明所述的自催化扩链剂，在保证与脂肪族异氰酸酯反应速度的情况下降低了催化剂的用量，同时不含任何有机溶剂，不含胺类催化剂。相比现有技术CN103172822A，复合催化剂用量可降低20％～30％，因此具有更低的气味和VOC，环保性更佳。
2.采用发明所述的自催化扩链剂，可有效提高体系的反应活性，且采用的复合催化剂与自催化扩链剂均具有一定的热敏性，温度越高，对聚合的催化效果越好，由于聚氨酯聚合过程放热明显，因而该组合物的反应具有较好的自加速效果，缩短凝胶和脱模时间，能够有效提高反应速率。相比与现有技术CN103172822A具有更高的生产效率。
3.本发明组合物配方中应用自催化扩链剂所具有的特殊结构，在反应中可增进脲基团的生成，并提高交联度，可提高聚合物材料的力学性能。相比与现有技术CN103172822A具有更高的力学性能。
4.该组合物中不含溶剂、胺类催化剂，且由于自催化型扩链剂的存在可大大降低复合催化剂的总使用量，相比现有技术CN103172822A，复合催化剂用量可降低20％～30％，因此具有更低的气味和VOC，环保性更佳。
综上所述，本发明组合物具有反应活性高、脱模时间短的优点，可通过反应注射成型(RIM)工艺制作高性能聚氨酯材料，所得材料气味低、VOC低、耐候性好。
具体实施方式
以下结合实施实例对本发明做进一步说明，以下实施例所述份数为质量份。
实施例1
(1)自催化扩链剂的合成：将无水哌嗪在带有冷凝回流装置的反应容器中加热至65℃，在保持恒温状态下将环氧丙烷按照哌嗪∶环氧丙烷＝1∶4的摩尔比，滴加至反应容器中，滴加完毕升温至80～85℃再反应4h，冷却至室温后出料。反应得到产物结构为：
(2)复合催化剂的配制：异辛酸铋10份，异辛酸钾1份，双环脒类化合物15份，丙三醇10份，经充分搅拌混合均匀后待用。
(3)组合物的制备
330N：环氧乙烷-环氧丙烷共聚醚三醇，羟值33.5～36.5mgKOH/g
A组分：330N，77.5份，上述制备的自催化扩链剂8份，乙二醇4份，三羟甲基丙烷：8份，炭黑：0.5份，2-(2’-羟基-5’-甲基苯基)苯并三氮唑：0.6份，双(3，5-三级丁基-4-羟基苯基)硫醚：0.4份，复合催化剂1份。
B组分：4，4’-二环己基甲烷二异氰酸酯，90.3份，聚四氢呋喃二醇(分子量1000)：7.5份，三羟甲基丙烷：2.2份。NCO质量分数为26.2％。
(4)实施例组合物A、B通过高压注射机制备PU-RIM材料的工艺如下：
①加料：将A组分加入到高压机A罐中，将组合物B组分加入到B罐中；
②注射：设定物料温度A组分30～45℃，B组分30～45℃，注射压力15±3MPa，注射至模温已加热至110～120℃的模具中。
③脱模：当凝胶时间≤10s时，40s脱模；当凝胶时间10～15s时，90s脱模。
④后熟化：80℃下熟化1h。
对比例
对比例材料制作工艺与实施例相同，组合物成分不同，不加入本发明所述的自催化扩链剂及复合催化剂。
A组分：330N，76.5份，乙二醇10份，三羟甲基丙烷：10份，炭黑：0.5份，2-(2’-羟基-5’-甲基苯基)苯并三氮唑：0.6份，双(3，5-三级丁基-4-羟基苯基)硫醚：0.4份，对比专利CN103172822A中复合催化剂2份。
B组分：4，4’-二环己基甲烷二异氰酸酯，90.3份，聚四氢呋喃二醇(分子量1000)：7.5份，三羟甲基丙烷：2.2份。NCO质量分数为26.2％。
表1 实施例与对比例材料性能对比

Claims (7)

1.一种环保高性能快速脱模聚氨酯反应注射成型组合物，该组合物包括A、B两组分，按质量分数计包括以下成分：
A组分：聚醚多元醇50％～90％，自催化扩链剂1％～10％，扩链剂1％～10％，交联剂1％～20％，颜料0～8％，抗老化剂1％～5％，复合催化剂0.01％～2％；
B组分：4，4’-二环己基甲烷二异氰酸酯60％～95％，改性剂5％～40％，异氰酸根(NCO)含量23％～28％；所述改性剂包括至少一种二元醇和至少一种三元醇；所述二元醇是指聚氧化丙烯二醇或聚四氢呋喃二醇及其混合物；所述三元醇选自三羟甲基乙烷、三羟甲基丙烷、丙三醇中的一种或多种；
所述自催化扩链剂是指具有以下结构的物质：
式中x＝2～5，R为CyH2y+1，y＝0～2；
所述复合催化剂是由异辛酸铋、异辛酸钾、双环脒类化合物与丙三醇复配而成，复配质量比为：异辛酸铋10份，异辛酸钾1～2份，双环脒类化合物15份，丙三醇10份，所述双环脒类化合物具有以下通式：
式中式中R1＝CaH2a，a＝2～4；R2＝CbH2b，b＝3～7。
2.根据权利要求1所述的组合物，其特征是聚氧化丙烯二醇分子量为400～4000，聚四氢呋喃二醇分子量为650～2000。
3.根据权利要求1所述的组合物，其特征是聚醚多元醇选自伯羟基含量＞70％，数均分子量3000～6500的环氧乙烷-环氧丙烷共聚醚三醇中的一种或多种。
4.根据权利要求1所述的组合物，其特征是扩链剂选自乙二醇、1，4-丁二醇、1，3-丁二醇、一缩二乙二醇、二乙醇胺中的一种或多种。
5.根据权利要求1所述的组合物，其特征是交联剂选自丙三醇、三羟甲基乙烷、三羟甲基丙烷、三羟乙基异氰脲酸酯中的一种或多种。
6.根据权利要求1所述的组合物，其特征是抗老化剂选自2-(2′-羟基-3′，5′-二叔丁基苯基)-5-氯代苯并三氮唑、2-(2′-羟基-5′-甲基苯基)苯并三氮唑、双(3，5-三级丁基-4-羟基苯基)硫醚、双(1，2，2，6，6-五甲基-4-哌啶基)癸二酸酯、亚磷酸三辛酯中的一种或多种。
7.一种制备权利要求1～6之一所述的自催化扩链剂的方法，包括以下步骤：将无水哌嗪在带有冷凝回流装置的反应容器中加热至65±5℃，恒温状态下将环氧乙烷、环氧丙烷或环氧丁烷中的一种按照摩尔比缓慢滴加至反应容器中，滴加完毕升温至80～85℃反应4h，冷却至室温后出料。
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