CN104788642A - 一种用于超低温保温的硬质聚氨酯泡沫及其制备方法 - Google Patents

一种用于超低温保温的硬质聚氨酯泡沫及其制备方法 Download PDF

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CN104788642A
CN104788642A CN201510237425.9A CN201510237425A CN104788642A CN 104788642 A CN104788642 A CN 104788642A CN 201510237425 A CN201510237425 A CN 201510237425A CN 104788642 A CN104788642 A CN 104788642A
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polyether
polyether glycol
foaming agent
hard polyurethane
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罗振扬
曹建鹏
傅东海
张从文
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Nanjing Forestry University
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Abstract

本发明公开了一种用于超低温保温的硬质聚氨酯泡沫，该聚氨酯泡沫采用反式-1,3,3,3-四氟丙烯单独或与环戊烷混合发泡制备硬质聚氨酯泡沫，利用HFO-1234ze低温下具有较高蒸汽压的特点，以使聚氨酯泡沫在超低温状态下具备良好的尺寸稳定性，可应用于超低温保温领域。本发明的用于超低温保温的硬质聚氨酯泡沫，由组合聚醚与聚合MDI混合后制得，其组合聚醚中包含物理和化学发泡剂，组合聚醚:聚合MDI质量比为1:1.1～1.3；所述的物理发泡剂为HFO-1234ze或HFO1234ze与环戊烷混合发泡剂，所述的化学发泡剂为水。

Description

一种用于超低温保温的硬质聚氨酯泡沫及其制备方法
技术领域
本发明涉及一种聚氨酯泡沫及其制备方法，更具体地说涉及一种用于超低温保温的硬质聚氨酯泡沫及其制备方法。
背景技术
聚氨酯是一类分子链中含有氨基甲酸酯基团(-NHCOO-)的高聚物。随着合成时原料、助剂及工艺条件的不同,可以合成性能各异的产品，诸如泡沫塑料、橡胶、涂料、黏合剂、弹性纤维等。近年来，我国聚氨酯工业飞速发展。硬质聚氨酯泡沫具有非常低的导热系数及水蒸汽透过性，质轻、比强度高，加之其与纸、金属、木材、水泥板、砖墙塑料板、沥青毡等具有很强的粘接性，不需另加其它粘合剂等优点，已为众多的工业及民用部门所采用。液化天然气(LNG)的贮存和运输、以及医疗卫生领域常常采用超低温保温技术。《低温工程》2014，(5)“泡沫玻璃砖超低温性能试验研究”公开了泡沫玻璃在LNG中的应用。泡沫玻璃是一种无机保温材料，密度低、强度相对较高、导热系数小、抗冻性能好、易加工，在LNG等低温领域得到了广泛应用。但泡沫玻璃在超低温状态下受力性能恶化、受压脆性明显，应用时仍然受限。《化工新型材料》2006,34(1)“聚氨酯硬泡在超低温下的应用研究”公开了以HCFC-141b发泡的聚氨酯泡沫在超低温保温中的应用。聚氨酯材料是典型的软硬段相结合的高分子材料，“刚性链段”保证了材料的强度、“柔性链段”保证了材料的韧性，因此也适合超低温液体的贮存和运输。
聚氨酯泡沫塑料采用化学发泡剂和物理发泡剂发泡。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(有时称“辅助发泡剂”)一般是惰性的低沸点有机化合物，尤其以氟代烃类化合物为代表。物理发泡剂与所用任何组份不起化学反应，这类低沸点化合物吸收了异氰酸酯和多元醇反应放出的热量使之气化而达到发泡的目的。1960年代至1990年左右，聚氨酯材料制造业广泛使用氯氟烃(CFC)作为物理发泡剂生产泡沫塑料。自1987年“蒙特利尔议定书”实施以来，CFC被全面禁止在聚氨酯泡沫生产中使用。含氢氯氟烃(HCFCs)类化合物含较少的氯原子，分子中含有氢，化学特性不稳定，比较容易分解，通常在较低大气层中已开始分解(例如HCFC-141b的大气层中寿命仅约8年，而CFC-11为60多年)。HCFCs化合物的ODP值及GWP值比CFC的低得多，对环境影响比CFC小，是CFC替代过程中的一类有价值的过渡性替代物。其中，HCFC-141b(1,1-二氯-1-氟代乙烷)是一种主要的硬质PU泡沫过渡性替代发泡剂，产品用于冰箱、冰柜等绝热泡沫及建筑、管道保温等。但在全球日益严峻的环境压力下，含氢氯氟烃在发展中国家的应用也将被限制并最终被替代。在可以用作硬质聚氨酯泡沫塑料发泡剂HCFC-141b的许多替代物中，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。目前，环戊烷发泡技术已被广泛采用。氢氟烷烃(HFC)也是一种零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。含氟烯烃化合物(HFO)不破坏臭氧层，GWP值也很低，一些HFO不燃，是HCFCs制冷剂、发泡剂及清洗剂的潜在替代品。环戊烷沸点为49℃，20℃时饱和蒸汽压为34kPa。在超低温应用时，一般需要提高泡沫密度，以使泡沫达到较高力学强度来保证超低温状态下泡沫良好的尺寸稳定性。这样造成泡沫成本较高。因此需要研制一种成本低、工艺简单的用于超低温保温的硬质聚氨酯泡沫及其制备方法
发明内容
本发明的目的在于解决上述现有技术中存在的不足和问题，提供了一种用于超低温保温的硬质聚氨酯泡沫，该聚氨酯泡沫采用反式-1,3,3,3-四氟丙烯(HFO-1234ze)单独或与环戊烷混合发泡制备硬质聚氨酯泡沫，利用HFO-1234ze低温下具有较高蒸汽压的特点，以使聚氨酯泡沫在超低温状态下具备良好的尺寸稳定性，可应用于超低温保温领域。
本发明同时还提供该硬质聚氨酯泡沫的制备方法，方法简单可靠。
本发明的技术方案如下：
本发明的用于超低温保温的硬质聚氨酯泡沫，由组合聚醚与聚合MDI混合后制得，其组合聚醚中包含物理和化学发泡剂，组合聚醚:聚合MDI质量比为1:1.1～1.3；所述的物理发泡剂为HFO-1234ze或HFO1234ze与环戊烷混合发泡剂，所述的化学发泡剂为水。
本发明上述的硬质聚氨酯泡沫，其进一步的技术方案是所述的物理发泡剂为HFO-1234ze时，其在组合聚醚中所占质量分数为12％wt～22％wt；所述的物理发泡剂为HFO1234ze与环戊烷混合发泡剂时，混合物理发泡剂在组合聚醚中所占质量分数为7％wt～17％wt，其中混合的比例为HFO1234ze:环戊烷＝25％wt～60％wt:75％wt～40％wt。
本发明上述的硬质聚氨酯泡沫，其进一步的技术方案还可以是所述的化学发泡剂水在组合聚醚中所占质量分数为1.0％wt～3.0％wt。
本发明上述的硬质聚氨酯泡沫，其进一步的技术方案还可以是所述的组合聚醚包含有多元醇成份、催化剂和有机硅表面活性剂，其中多元醇成份由以下质量分数各物质组成：
所述的3官能团羟值为300～500mgKOH/g聚醚多元醇A是以至少丙三醇或三羟甲基丙烷中的一种为起始剂的聚醚多元醇；所述6官能团羟值为350～500mgKOH/g聚醚多元醇B是以至少山梨醇、甘露醇或甲基葡萄糖甙中的一种为起始剂的聚醚多元醇；所述8官能团羟值为350～500mgKOH/g聚醚多元醇C为以蔗糖为起始剂的聚醚多元醇；所述羟值为300～500mgKOH/g胺基聚醚多元醇D是以至少乙二胺、三乙醇胺、甲苯二胺或苯酚、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氨基聚醚多元醇。更进一步的技术方案是所述的催化剂为常规聚氨酯用有机胺催化剂，在组合聚醚中所占质量分数为1.5％～3.5％wt；所述的有机硅表面活性剂为常规硬质聚氨酯泡沫用有机硅表面活性剂，在组合聚醚中所占质量分数为1.0％～2.0％wt。
本发明上述的硬质聚氨酯泡沫的制备方法，其包括以下步骤：
(1)将多元醇成份、催化剂、有机硅表面活性剂、物理发泡剂、化学发泡剂经物理混配成组合聚醚；
(2)在物料温度为15～25℃条件下，将组合聚醚与聚合MDI高速搅拌混合3～10秒后灌注；
(3)模温25～40℃，发泡物料在模具中过填充系数为15％～30％，制品经5～15分钟脱模。
与现有技术相比，本发明有益效果在于：
采用零ODP、低GWP环保发泡剂，顺应国际环境公约要求；发泡工艺要求的模温较低；物理发泡剂中含有含氟烯烃HFO-1234ze，由于其低于室温的沸点，发泡过程为沫状或接近沫状发泡，模塑发泡时配合合适的过填充系数，泡沫物理力学性能接近各向同性；含有HFO-1234ze的聚氨酯泡沫，在较低的密度下超低温状态时保持较好的尺寸稳定性。同时制备方法简单可靠。
具体实施方式
以下通过具体实施例说明本发明，但本发明并不仅仅限定于这些实施例。
实施例中其制备方法如下：
(1)将多元醇成份、催化剂、有机硅表面活性剂、物理发泡剂、化学发泡剂经物理混配成组合聚醚；
(2)在物料温度为15～25℃条件下，将组合聚醚与聚合MDI高速搅拌混合3～10秒后灌注；
(3)模温25～40℃，发泡物料在模具中过填充系数为15％～30％，制品经5～15分钟脱模。
实施例1
聚醚多元醇A为丙三醇作为起始剂，羟值350mgKOH/g聚醚多元醇；
聚醚多元醇B为山梨醇作为起始剂，羟值380mgKOH/g聚醚多元醇；
聚醚多元醇C为蔗糖作为起始剂，羟值420mgKOH/g聚醚多元醇；
聚醚多元醇D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370mgKOH/g聚醚多元醇。
发泡配方和工艺见下表。
实施例2
聚醚多元醇A为三羟甲基丙烷作为起始剂，羟值320mgKOH/g聚醚多元醇；
聚醚多元醇B为甲基葡萄糖甙作为起始剂，羟值390mgKOH/g聚醚多元醇；
聚醚多元醇C为蔗糖作为起始剂，羟值420mgKOH/g聚醚多元醇；
聚醚多元醇D为乙二胺作为起始剂，羟值350mgKOH/g聚醚多元醇。
发泡配方和工艺见下表。
实施例3
聚醚多元醇A为三羟甲基丙烷作为起始剂，羟值330mgKOH/g聚醚多元醇；
聚醚多元醇B为甘露醇作为起始剂，羟值420mgKOH/g聚醚多元醇；
聚醚多元醇C为蔗糖作为起始剂，羟值380mgKOH/g聚醚多元醇；
聚醚多元醇D为三乙醇胺作为起始剂，羟值390mgKOH/g聚醚多元醇。
发泡配方和工艺见下表。
实施例4
聚醚多元醇A为丙三醇作为起始剂，羟值360mgKOH/g聚醚多元醇；
聚醚多元醇B为山梨醇作为起始剂，羟值410mgKOH/g聚醚多元醇；
聚醚多元醇C为蔗糖作为起始剂，羟值400mgKOH/g聚醚多元醇；
聚醚多元醇D为甲苯二胺作为起始剂，羟值480mgKOH/g聚醚多元醇。
发泡配方和工艺见下表。
实施例5
聚醚多元醇A为丙三醇作为起始剂，羟值330mgKOH/g聚醚多元醇；
聚醚多元醇B为甲基葡萄糖甙作为起始剂，羟值450mgKOH/g聚醚多元醇；
聚醚多元醇C为蔗糖作为起始剂，羟值420mgKOH/g聚醚多元醇；
聚醚多元醇D为甲苯二胺作为起始剂，羟值400mgKOH/g聚醚多元醇。
发泡配方和工艺见下表。
实施例6
聚醚多元醇A为三羟甲基丙烷作为起始剂，羟值400mgKOH/g聚醚多元醇；
聚醚多元醇B为山梨醇作为起始剂，羟值410mgKOH/g聚醚多元醇；
聚醚多元醇C为蔗糖作为起始剂，羟值400mgKOH/g聚醚多元醇；
聚醚多元醇D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350mgKOH/g聚醚多元醇。
发泡配方和工艺见下表。
实施例中的原料配方及工艺参数如下表：
发泡配方 实施例1 实施例2 实施例3 实施例4 实施例5 实施例6
聚醚多元醇A 15 15 20 15 20 15
聚醚多元醇B 25 20 25 25 25 25
聚醚多元醇C 50 55 45 50 45 50
聚醚多元醇D 10 10 10 10 10 10
水 1.5 2.3 3.0 1.6 2.1 1.8
HFO-1234ze 25 20 15 14 10 7
环戊烷 0 0 0 8 7 13
有机胺催化剂 3.1 3.0 2.7 2.6 2.5 2.5
有机硅表面活性剂 2.2 2.0 2.0 2.0 2.0 2.2
聚合MDI指数 1.2 1.15 1.15 1.2 1.15 1.2
物料温度/℃ 16 17 18 18 20 21
搅拌混合时间/s 3 5 5 7 9 8
模温/℃ 25 28 28 28 30 35
过填充系数 25％ 30％ 20％ 30％ 20％ 15％
实施例中硬质聚氨酯泡沫性能如下表：

Claims (6)

1.一种用于超低温保温的硬质聚氨酯泡沫，由组合聚醚与聚合MDI混合后制得，其特征在于组合聚醚中包含物理和化学发泡剂，组合聚醚:聚合MDI质量比为1:1.1～1.3；所述的物理发泡剂为HFO-1234ze或HFO1234ze与环戊烷混合发泡剂，所述的化学发泡剂为水。
2.根据权利要求1所述的硬质聚氨酯泡沫，其特征在于所述的物理发泡剂为HFO-1234ze时，其在组合聚醚中所占质量分数为12％wt～22％wt；所述的物理发泡剂为HFO1234ze与环戊烷混合发泡剂时，混合物理发泡剂在组合聚醚中所占质量分数为7％wt～17％wt，其中混合的比例为HFO1234ze:环戊烷＝25％wt～60％wt:75％wt～40％wt。
3.根据权利要求1所述的硬质聚氨酯泡沫，其特征在于所述的化学发泡剂水在组合聚醚中所占质量分数为1.0％wt～3.0％wt。
4.根据权利要求1所述的硬质聚氨酯泡沫，其特征在于所述的组合聚醚包含有多元醇成份、催化剂和有机硅表面活性剂，其中多元醇成份由以下质量分数各物质组成：
所述的3官能团羟值为300～500mgKOH/g聚醚多元醇A是以至少丙三醇或三羟甲基丙烷中的一种为起始剂的聚醚多元醇；所述6官能团羟值为350～500mgKOH/g聚醚多元醇B是以至少山梨醇、甘露醇或甲基葡萄糖甙中的一种为起始剂的聚醚多元醇；所述8官能团羟值为350～500mgKOH/g聚醚多元醇C为以蔗糖为起始剂的聚醚多元醇；所述羟值为300～500mgKOH/g胺基聚醚多元醇D是以至少乙二胺、三乙醇胺、甲苯二胺或苯酚、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氨基聚醚多元醇。
5.根据权利要求4所述的硬质聚氨酯泡沫，其特征在于所述的催化剂为常规聚氨酯用有机胺催化剂，在组合聚醚中所占质量分数为1.5％～3.5％wt；所述的有机硅表面活性剂为常规硬质聚氨酯泡沫用有机硅表面活性剂，在组合聚醚中所占质量分数为1.0％～2.0％wt。
6.一种如权利要求1-5任一所述的硬质聚氨酯泡沫的制备方法，其特征在于包括以下步骤：
(1)将多元醇成份、催化剂、有机硅表面活性剂、物理发泡剂、化学发泡剂经物理混配成组合聚醚；
(2)在物料温度为15～25℃条件下，将组合聚醚与聚合MDI高速搅拌混合3～10秒后灌注；
(3)模温25～40℃，发泡物料在模具中过填充系数为15％～30％，制品经5～15分钟脱模。
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Application publication date: 20150722