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CN107955122B - 一种co2超临界辅助发泡硬质聚氨酯泡沫及其制备方法 - Google Patents

一种co2超临界辅助发泡硬质聚氨酯泡沫及其制备方法 Download PDF

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CN107955122B
CN107955122B CN201711282839.9A CN201711282839A CN107955122B CN 107955122 B CN107955122 B CN 107955122B CN 201711282839 A CN201711282839 A CN 201711282839A CN 107955122 B CN107955122 B CN 107955122B
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CN107955122A (zh
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罗振扬
沈晨光
相明华
陈金炎
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Zhejiang Huachuang Carbon Intelligent Manufacturing Co ltd
Nanjing Forestry University
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Abstract

本发明公开了一种CO2超临界辅助发泡硬质聚氨酯泡沫及其制备方法，属于聚氨酯技术领域。针对液态CO2无法得到真正实际应用的问题，本发明提供一种采用低沸点的液态CO2与高沸点的物理发泡剂混合发泡制备的硬质聚氨酯泡沫，并采用了以氨醚、聚碳酸酯为主体聚醚的配方体系，本发明的硬质聚氨酯泡沫具备良好的强度、绝热性能和尺寸稳定性，并且本领域技术人员还可在本发明的基础上衍生出性能各异的CO2超临界辅助发泡硬质聚氨酯泡沫，并且本发明的泡沫制备方法对设备的要求不高，制备方法简单可靠。

Description

一种CO2超临界辅助发泡硬质聚氨酯泡沫及其制备方法
技术领域
本发明属于聚氨酯技术领域，更具体地说，涉及一种CO2超临界辅助发泡硬质聚氨酯泡沫及其制备方法。
背景技术
硬质聚氨酯泡沫塑料采用化学发泡剂或物理发泡剂发泡。化学发泡剂主要以水为主，水同异氰酸酯反应生成使反应物膨胀的二氧化碳气体。物理发泡剂与所用任何组份不起化学反应，一般是惰性的低沸点有机氟化合物，这类低沸点化合物吸收异氰酸酯和多元醇反应放出的热量而气化，达到发泡的目的。
过去三十年中聚氨酯行业广泛使用的物理发泡剂HCFC-141b(1，1-二氯-1-氟代乙烷)是一种过渡性替代发泡剂，但在全球日益严峻的环境压力下，包括HCFC-141b的这类含氢氯氟烃发泡剂将在全球范围内被完全替代。可以用作HCFC-141b的替代发泡剂主要有烷烃化合物 (正戊烷、异戊烷或环戊烷)、氢氟烷烃(HFC)、氢氟烯烃化合物(HFO)、水(即反应后形成的CO2)或CO2。烷烃化合物因臭氧消耗潜值(ODP值)为零、温室效应很小、无毒、对环境影响极小而受到重视，其中环戊烷发泡技术已被广泛采用；HFC是一种零ODP值的发泡剂，但由于较高的全球变暖潜值(GWP值)，仍然不是理想的聚氨酯发泡剂；HFO不破坏臭氧层，GWP值也很低，但成本较高，；以上诸多种类的发泡剂仍存在影响环境或成本较高的缺点，相比来说，CO2具有ODP值为0、GWP值极低、发泡效率高、不燃、无毒等优良的特性，是一种具有广阔应用前景的低成本发泡剂。除了水作为化学发泡剂外，由于CO2沸点极低，在空气中极易挥发，所以需要探索利用液态CO2进行聚氨酯发泡的可行工艺。
发明内容
针对液态CO2无法得到实际应用的难题，本发明提供一种CO2超临界辅助发泡硬质聚氨酯泡沫及其制备方法，本发明的硬质聚氨酯泡沫采用低沸点的液态CO2与其他环保型物理发泡剂混合发泡制备，并采用了特殊的配方体系，使本发明的硬质聚氨酯泡沫具备良好的强度、绝热性能和尺寸稳定性，另外本发明还同时提供了该硬质聚氨酯泡沫的制备方法，该方法将液态CO2以超临界状态制备组合聚醚，进而制备出该硬质聚氨酯泡沫，制备方法简单可靠，适于实际推广应用。
为了解决上述问题，本发明所采用的技术方案如下：
一种CO2超临界辅助发泡硬质聚氨酯泡沫，由组合聚醚与聚合MDI混合后制得，所述组合聚醚包含多元醇、催化剂、阻燃剂、发泡剂和表面活性剂，所述组合聚醚与所述聚合MDI 的质量比为1∶(1.1～1.3)，以多元醇的总质量为100份计，所述发泡剂包括化学发泡剂和超临界CO2，所述超临界CO2在所述组合聚醚中的质量份数为0.5～3份，所述化学发泡剂在所述组合聚醚中的质量份数为1～4份，所述化学发泡剂为水。
更进一步地，所述发泡剂还包含物理发泡剂，所述物理发泡剂在所述组合聚醚中的质量份数为6～30份，所述物理发泡剂为HFC-245fa、HFC-365mfc、HFO-1233zd(E)、HFO-1336mzz 中的一种或一种以上。
更进一步地，所述多元醇至少包括以下质量份数的各物质：5～30份多元醇A，2～10份多元醇B；
所述多元醇A是以至少乙二胺、丙二胺、甲苯二胺、二苯基甲烷二胺、二乙烯三胺、三乙烯四胺中的一种为起始剂的聚醚多元醇或以至少一乙醇胺、二乙醇胺、三乙醇胺、三异丙醇胺或苯酚、甲醛、二乙醇胺经Mannich反应得到的加成物中的一种为起始剂的聚醚多元醇；所述多元醇B是以至少碳酸二(二丙二醇)酯、碳酸二(二乙二醇)酯中的一种为原料的聚酯多元醇。
更进一步地，所述多元醇还包括起始剂中包含蔗糖和二甘醇的聚醚多元醇。
更进一步地，所述催化剂包括常规聚氨酯用有机胺催化剂和有机金属催化剂，所述有机胺催化剂在所述组合聚醚中所占质量份数为2～4份，所述有机金属催化剂在所述组合聚醚中所占质量份数为1～2.5份；所述阻燃剂为常规硬质聚氨酯泡沫用阻燃剂，所述阻燃剂在所述组合聚醚中所占质量份数为15～25份；所述表面活性剂为常规硬质聚氨酯泡沫用有机硅表面活性剂，所述表面活性剂在所述组合聚醚中所占质量份数为0.2～2份。
更进一步地，包括以下步骤：
步骤1，将多元醇、催化剂、阻燃剂、表面活性剂、化学发泡剂和物理发泡剂进行物理混配；
步骤2，将高压罐装的液态CO2通过减压气化和降温增压液化的方式转变为超临界状态；
步骤3，按比例将步骤2)得到的超临界CO2与步骤1)得到的混合物充分混合，成为组合聚醚；
步骤4，在一定的物料温度和环境温度下，将聚合MDI与步骤3)所述组合聚醚经高压泵输送至混合枪头混合后进行发泡；
步骤5，经过一定固化时间后，得到CO2超临界辅助发泡硬质聚氨酯泡沫。
更进一步地，所述步骤3中的超临界CO2在组合聚醚中的质量分数为0.5％～3％。
更进一步地，所述步骤4中的物料温度为35～45℃，所述步骤4中的环境温度为-10～35 ℃。
更进一步地，所述步骤5中的固化时间为10～20秒。
相比于现有技术，本发明的有益效果为：
(1)本发明的硬质聚氨酯泡沫的组合聚醚采用氨醚、聚碳酸酯作为主体聚醚，以超临界的液态CO2、水和其他一些物理发泡剂共用，配方中各组分协同作用得到各方面性能良好的硬质聚氨酯泡沫，使CO2超临界辅助发泡技术从理论走向实际应用；
(2)本发明的发泡配方专用于CO2超临界辅助发泡，必选聚醚(聚酯)与超临界CO2的相容性好，同时起到降粘的作用；在本发明的基础上还可另外添加一些其他种类聚醚，以满足各种各样的泡沫性能需求；
(3)本发明采用零ODP的环保型发泡剂，对环境友好，顺应国际环境公约的要求；
(4)本发明的施工环境宽容度高，可满足低温施工环境，应用范围广；硬质聚氨酯泡沫的制备方法对设备的要求不高，制备方法简单可靠。
具体实施方式
下面结合具体实施例对本发明进一步进行描述。以下实施例仅用于更加清楚地说明本发明的技术方案，而不能以此来限制本发明的保护范围。
各对比例及实施例所采用的发泡设备为中国专利201710062491.6的实施例所述的发泡设备，各对比例及实施例中的硬质聚氨酯泡沫的制备方法如下：
1)将多元醇、催化剂、阻燃剂、表面活性剂、物理发泡剂(不含液态CO2)和化学发泡剂水经物理混配成组合聚醚；
2)混配后的组合聚醚通过提料泵和输送管输送至聚氨酯高压发泡机组合聚醚设备罐中，同时聚合MDI通过提料泵和输送管输送至MDI设备罐中；
3)液态CO2通过减压气化、降温增压液化后以恒定比例输送至组合聚醚设备罐中，在超临界状态下与组合聚醚充分混合；
4)在物料温度为35～45℃和环境温度为-10～35℃下，聚氨酯高压发泡设备将组合聚醚与聚合MDI以固定比例输送至预混喷枪，混合均匀后呈雾状喷出；
5)经过一定固化时间，得到硬质聚氨酯泡沫。
对比例和实施例中的液态CO2均以超临界状态添加，由于组合聚醚与聚合MDI的质量比在1∶(1.1～1.3)时，泡沫性能不会出现显著性区别，所以在本发明的对比例和实施例中组合聚醚与聚合MDI的质量比均设定为代表性的1∶1.2。
对比例1
聚醚多元醇A为乙二胺作为起始剂，羟值770mgKOH/g的聚醚多元醇；
聚酯多元醇B为碳酸二(二乙二醇)酯二元醇，羟值460mgKOH/g；
聚酯多元醇D为苯酐聚酯多元醇，羟值230mgKOH/g；
发泡剂为HFC-245fa、水和液态CO2。
发泡配方和工艺见表1。
对比例2
聚醚多元醇A为乙二胺作为起始剂，羟值770mgKOH/g的聚醚多元醇；
聚酯多元醇B为碳酸二(二丙二醇)酯二元醇，羟值390mgKOH/g；
聚酯多元醇D为苯酐聚酯多元醇，羟值210mgKOH/g；
发泡剂为HFC-245fa、水和液态CO2。
发泡配方和工艺见表1。
对比例3
聚醚多元醇A为乙二胺作为起始剂，羟值570mgKOH/g的聚醚多元醇；
聚酯多元醇B为碳酸二(二丙二醇)酯二元醇，羟值375mgKOH/g；
聚酯多元醇D为苯酐聚酯多元醇，羟值250mgKOH/g；
发泡剂为HFC-245fa、水和液态CO2。
发泡配方和工艺见表1。
对比例4
聚醚多元醇A为乙二胺作为起始剂，羟值770mgKOH/g的聚醚多元醇；
聚酯多元醇B为碳酸二(二丙二醇)酯二元醇，羟值为380mgKOH/g；
聚酯多元醇D为苯酐聚酯多元醇，羟值230mgKOH/g；
发泡剂为HFC-245fa、水和液态CO2。
发泡配方和工艺见表1。
对比例5
聚醚多元醇A为乙二胺作为起始剂，羟值770mgKOH/g的聚醚多元醇；
聚酯多元醇B为对苯二甲酸芳族聚酯多元醇，羟值190mgKOH/g；
发泡剂为HFC-245fa、水和液态CO2。
发泡配方和工艺见表1。
对比例6
聚醚多元醇A为乙二胺作为起始剂，羟值470mgKOH/g的聚醚多元醇；
聚酯多元醇B为碳酸二(二丙二醇)酯二元醇，羟值385mgKOH/g；
聚酯多元醇D为苯酐聚酯多元醇，羟值190mgKOH/g；
发泡剂为水和液态CO2。
发泡配方和工艺见表1。
实施例1
聚醚多元醇A为乙二胺作为起始剂，羟值570mgKOH/g的聚醚多元醇；
聚酯多元醇B为碳酸二(二丙二醇)酯二元醇，羟值为365mgKOH/g；
聚酯多元醇D为苯酐聚酯多元醇，羟值230mgKOH/g；
发泡剂为HFO-1336mzz、水和液态CO2。
发泡配方和工艺见表1。
实施例2
聚醚多元醇A为甲苯二胺作为起始剂，羟值340mgKOH/g的聚醚多元醇；
聚酯多元醇B为聚碳酸二(二丙二醇)酯二元醇，羟值为400mgKOH/g；
聚酯多元醇D为苯酐聚酯多元醇，羟值250mgKOH/g；
发泡剂为HFC-245fa、HFC-365mfc、水和液态CO2。
发泡配方和工艺见表1。
实施例3
聚醚多元醇A为乙二胺作为起始剂，羟值570mgKOH/g的聚醚多元醇；
聚酯多元醇B为碳酸二(二乙二醇)酯二元醇，羟值为430mgKOH/g；
聚酯多元醇D为苯酐聚酯多元醇，羟值230mgKOH/g；
发泡剂为HFC-245fa、水和液态CO2。
发泡配方和工艺见表1。
实施例4
聚醚多元醇A为苯酚、甲醛、二乙醇胺经Mannich反应得到的加成物作为起始剂，羟值 550mgKOH/g的聚醚多元醇；
聚酯多元醇B为碳酸二(二乙二醇)酯二元醇，羟值为430mgKOH/g；
聚醚多元醇C为蔗糖、二甘醇作为起始剂，羟值380mgKOH/g的聚醚多元醇；
聚酯多元醇D为苯酐聚酯多元醇，羟值230mgKOH/g；
发泡剂为HFC-245fa、HFO-1233zd(E)、水和液态CO2。
发泡配方和工艺见表1。
表1各对比例和实施例的原料配方及工艺参数
Figure BDA0001496502120000061
各对比例和实施例所得到的硬质聚氨酯泡沫性能见表2，由表中数据可知，本发明的硬质聚氨酯泡沫具有较低的组合聚醚粘度，较低的导热系数，较高的压缩强度。
以超临界CO2作为物理发泡剂之一，将液态CO2转化为超临界状态后直接添加到组合聚醚体系中，低沸点的CO2作为辅助发泡剂添加后会迅速气化，有效改善了全水发泡时水与异氰酸酯反应生成含脲基的高聚物产生的起发慢、泡沫脆、强度低和尺寸稳定性差的不足，同时液态CO2挥发时会带走部分反应热，避免了全水发泡易烧芯的问题；由于液态CO2沸点远低于室温，发泡过程为沫状发泡，与高沸点的物理发泡剂和化学发泡剂水混合发泡时，泡沫物理力学性能接近各向同性，泡沫的力学性能和绝热性能有所提高，所以制品在较低的密度下高温和超低温状态时保持较好的尺寸稳定性；现有的一些液态CO2的发泡技术，其配方比例如对比例5所示，该技术采用了大量的芳族聚酯，发泡剂选用的是液态CO2和水，可以看出，泡沫的尺寸稳定性较差，而且，组合聚醚的粘度过大，需要另外添加非反应型降粘剂才可使用，而非反应型降粘剂的使用会大大劣化泡沫性能，故其实际应用价值并不高。
聚酯多元醇B为碳酸二(二乙二醇)酯二元醇或碳酸二(二丙二醇)酯二元醇，该类型高分子聚酯一般用于弹性体领域，发明人偶然发现该类型多元醇适合于硬质聚氨酯泡沫的液态CO2发泡体系。对比例1和实施例3比较可知，在组合聚醚中的聚酯多元醇B减少(低于2质量份数)，其余各组分一致时，表现为所发泡沫的密度、导热系数增大，闭孔率降低，其原因是所述聚酯多元醇B与液态CO2有良好的相容性，配方中使用这类聚酯多元醇可以使 CO2与组合聚醚在出料后仍保持良好的相容性，使泡沫泡孔生长过程中CO2气体可以较好的溶于液相中，进而使获得的泡沫具有较高的闭孔率；另外，所述聚酯多元醇B的粘度较小，尤其在与液态CO2相容后，具有较强的降粘作用，所以对比例1的组合聚醚的粘度较大而实施例3的组合聚醚粘度较小；但是所述聚酯多元醇B并非越多越好，当添加量达到10份以上时(对比例2)，会发现泡沫的强度和尺寸稳定性急剧下降。
所以，本发明的聚酯多元醇B不光参与反应，还具有提高液态CO2相容性以及降粘的作用，配方中无需额外添加降粘剂。
由对比例3、对比例4和实施例3可知，增加聚醚多元醇A的含量，泡沫的闭孔率增加，尺寸稳定性增强，压缩强度增加，其原因在于，所述聚醚多元醇A为氨醚，氨醚对液态CO2也具有较好的相容性，另外氨醚使泡沫泡孔细密，其交联结构能够增加泡沫的强度，提高其稳定性；由于聚醚多元醇A与液态CO2的相容性还不够理想，所以聚醚多元醇A与聚酯多元醇B相辅相成，在保证泡沫性能的基础上提高液态CO2的相容性。
液态CO2和水共用的发泡体系，还存在CO2的导热系数高、扩散快的问题，由对比例6和实施例3对比可知，添加除液态CO2之外的一些物理发泡剂，大大降低了组合聚醚的粘度，显著降低了泡沫的导热系数，提高了泡沫的闭孔率。
实施例1～4是采用不同种类和用量的聚醚多元醇A、聚酯多元醇B和聚醚多元醇C、D 以及不同助剂的发泡试验，可以看出，在本发明所公开的范围内，均制备得到了较为理想的 CO2超临界辅助发泡硬质聚氨酯泡沫。
表2各对比例和实施例得到的硬质聚氨酯泡沫性能
Figure BDA0001496502120000071
Figure BDA0001496502120000081
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和变形，这些改进和变形也应视为本发明的保护范围。例如，本发明是以喷涂的发泡方式制备硬质聚氨酯泡沫，本领域技术人员不经过创造性劳动即可在本喷涂发泡体系的基础上衍生出其他发泡方式(如浇注、板材等) 制备的硬质聚氨酯泡沫，这些衍生出的硬质聚氨酯泡沫及其制备方式应视为本发明的保护范围。

Claims (4)

1.一种CO2超临界辅助发泡硬质聚氨酯泡沫，由组合聚醚与聚合MDI混合后制得，所述组合聚醚包含多元醇、催化剂、阻燃剂、发泡剂和表面活性剂，所述组合聚醚与所述聚合MDI的质量比为1：(1.1～1.3)，其特征在于，以多元醇的总质量为100份计，所述发泡剂包括化学发泡剂和超临界CO2，所述超临界CO2在所述组合聚醚中的质量份数为0.5～3份，所述化学发泡剂在所述组合聚醚中的质量份数为1～4份，所述化学发泡剂为水；
所述多元醇至少包括以下质量份数的各物质：5～30份多元醇A，2～10份多元醇B；
所述多元醇A是以至少乙二胺、丙二胺、甲苯二胺、二苯基甲烷二胺、二乙烯三胺、三乙烯四胺中的一种为起始剂的聚醚多元醇或以至少一乙醇胺、二乙醇胺、三乙醇胺、三异丙醇胺或苯酚、甲醛、二乙醇胺经Mannich反应得到的加成物中的一种为起始剂的聚醚多元醇；所述多元醇B是以至少碳酸二(二丙二醇)酯、碳酸二(二乙二醇)酯中的一种为原料的聚酯多元醇。
2.根据权利要求1所述的CO2超临界辅助发泡硬质聚氨酯泡沫，其特征在于，所述发泡剂还包含物理发泡剂，所述物理发泡剂在所述组合聚醚中的质量份数为6～30份，所述物理发泡剂为HFC-245fa、HFC-365mfc、HFO-1233zd(E)、HFO-1336mzz中的一种或一种以上。
3.根据权利要求1所述的CO2超临界辅助发泡硬质聚氨酯泡沫，其特征在于，所述多元醇还包括起始剂中包含蔗糖和二甘醇的聚醚多元醇。
4.根据权利要求1～3中任一项所述的CO2超临界辅助发泡硬质聚氨酯泡沫，其特征在于，所述催化剂包括常规聚氨酯用有机胺催化剂和有机金属催化剂，所述有机胺催化剂在所述组合聚醚中所占质量份数为2～4份，所述有机金属催化剂在所述组合聚醚中所占质量份数为1～2.5份；所述阻燃剂为常规硬质聚氨酯泡沫用阻燃剂，所述阻燃剂在所述组合聚醚中所占质量份数为15～25份；所述表面活性剂为常规硬质聚氨酯泡沫用有机硅表面活性剂，所述表面活性剂在所述组合聚醚中所占质量份数为0.2～2份。
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