CN104672420A - 一种高强度聚氨酯硬质泡沫及其制备方法和用途 - Google Patents

一种高强度聚氨酯硬质泡沫及其制备方法和用途 Download PDF

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CN104672420A
CN104672420A CN201510067505.4A CN201510067505A CN104672420A CN 104672420 A CN104672420 A CN 104672420A CN 201510067505 A CN201510067505 A CN 201510067505A CN 104672420 A CN104672420 A CN 104672420A
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董国鹏
朱霞林
李雪艳
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Wanhua Chemical Ningbo Rongwei Polyurethane Co Ltd
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Abstract

本发明公开了一种高强度聚氨酯硬质泡沫塑料与及其制备方法和用途。本发明引进了一种具有刚性结构的苯酰亚胺增强的聚氨酯改性剂，其与相应的高粘度芳香胺类聚醚多元醇、低官能度聚醚多元醇，利于提高泡沫各向同性的特种硅油，特定结构的催化剂、水以及发泡剂等制备成组合聚醚，并与多异氰酸酯反应生成高强度的聚氨酯泡沫。本发明中的聚氨酯硬质泡沫具有投料密度低、抗压强度高、较低的导热系数、低温下尺寸稳定性好等特点，可用于冰箱、冷柜、太阳能、燃气热水器、消毒柜等家电内部保温材料中。

Description

一种高强度聚氨酯硬质泡沫及其制备方法和用途
技术领域
本发明属于高分子材料泡沫塑料技术领域，具体涉及一种高强度聚氨酯硬质泡沫塑料。
技术背景
聚氨酯硬质泡沫作为一种保温材料，其具有较好的隔热性能、阻燃性能、较高的力学性能等，已广泛应用到冰箱、太阳能、热水器、建筑、管道、集装箱等领域。近年来，受到国家环保政策、原料成本、生产效率、质量要求等方面的影响，客户厂家对聚氨酯硬质泡沫的性能要求越来越高。
聚氨酯泡沫在一定芯密度的情况下，需保持较高的抗压强度，高强度保证了冰箱在制冷时不会出现局部“收缩”现象且有力地支撑箱体结构。为降低灌注量，节省原料成本，“低密度”在国内冰箱客户现场比较普遍，这就需要在降低泡沫灌注量(泡沫模塑密度降低)的情况下，泡沫的强度性能尽量保持不变。在泡沫芯密度一定的情况下，如何尽可能提高泡沫的压缩强度成为聚氨酯硬泡行业内的技术挑战。
中国公开专利CN103755908A公开了通过使用填料空心玻璃珠改性聚氨酯硬质泡沫来提高抗压强度，但此方法会引起组合料黏度过高，不利于泡沫的流动性。中国公开专利CN1900132公开了使用纳米级无机材料来提高泡沫的强度，此举同样会引起泡沫的流动性变差。可以看出通过添加无机填料的方式(即物理共混方法)，对泡沫的强度改善明显，但会对泡沫的流动性能造成影响。
现有聚氨酯硬质泡沫配方中多使用聚酯多元醇，中国公开专利CN10338468A公开了一种基于芳族二元酸的聚酯多元醇以及由其制备的硬质聚氨酯泡沫。中国公开专利CN102718957A公开了一种用于制备聚氨酯泡沫的芳烃聚酯多元醇及其制备方法。聚酯多元醇的使用会使得硬质泡沫的泡孔变得细腻，导热系数数值降低；普通聚酯多元醇中苯环含量相对不高，对泡沫的抗压强度改善不大；同时普通聚酯多元醇的粘度较低，使得泡沫的脱模性能变差、泡沫后期熟化变慢，这需要增加三聚催化剂的用量，但会使得泡沫的流动性变差。作为运用于家电体系的保温材料，客户对泡沫的阻燃性能要求越来越高，配方中聚酯多元醇、反应型阻燃聚醚、阻燃性添加剂的使用量增加，其使用使得泡沫的熟化、脱模、强度、流动性等性能变差。
因此，需找具有特殊结构的反应型物质用于组合聚醚多元醇，用于提升聚氨酯泡沫的整体性能。
发明内容
本发明的目的在于提供了一种适合于现有家电“低密度”体系的高强度聚氨酯硬质泡沫。通过引进具有刚性结构的苯酰亚胺类聚氨酯改性剂和高粘度芳香胺类聚醚多元醇为主要原料，与高粘度多异氰酸酯反应制得高强度聚氨酯硬质泡沫，使得聚氨酯泡沫的强度大幅提升，同时泡沫具有较好的粘结力、低温尺寸稳定性好、泡孔细腻、较好的隔热与一定的阻燃性能。
本发明的另一目的在于提供一种高强度聚氨酯硬质泡沫的制备方法。
为实现以上发明目的，本发明采用的技术方案如下：
一种高强度聚氨酯硬质泡沫塑料，由组合多元醇组分与多异氰酸酯组分在高压机混合下进行发泡制得，其特征在于，以组合聚醚多元醇组份总重量份数为100计，组合聚醚多元醇中各组分重量份数分别为：
本发明中，所述多异氰酸酯组分与组合多元醇组分的质量比为140:100～110:100，优选为130:100～120:100。
本发明中，所述的苯酰亚胺类改性剂是具有刚性结构的苯酰亚胺聚酯多元醇，其羟值为250～350mg KOH/g，结构式为：
其中n为聚合度，1≤n≤3。
本发明中，所述苯酰亚胺类改性剂是由偏苯三酐与对氨基苯乙酸在催化剂作用下经氨化反应与脱水环化，形成含氮五元杂环二元羧酸，所述含氮五元杂环二元羧酸结构式为：该二元羧酸再与过量的环氧氯丙烷进行开环聚合得到的。反应过程如下所示：
其中，所述偏苯三酐与对氨基苯乙酸的摩尔比为1:1，氨化、脱水反应的催化剂为无水醋酸钠，60～80℃下反应2-4h，催化剂用量为基于偏苯三酐和对氨基苯乙酸总用量的0.8wt％～2.5wt％；反应所用溶剂为丙酮、醋酸乙酯或DMF；环氧氯丙烷与含氮五元杂环二元羧酸开环聚合反应中，两者的摩尔比为1.2～2.5:1，以三苯基膦为开环聚合的催化剂，用量为基于环氧氯丙烷与含氮五元杂环二元酸总量的0.5wt％～1wt％，聚合反应温度为70～90℃，反应时间为8～10h。
本发明中，所述苯酰亚胺类改性剂结构中存在稳定的含氮五元杂环结构，在高分子链中可以增加大分子链的内旋阻力，从而提高聚氨酯硬质泡沫的的刚性及耐热性，泡孔结构的强度得到改善。
本发明中，所述的芳香胺类聚醚多元醇是一种高羟值、高粘度聚醚多元醇，其羟值为410～450mg KOH/g，官能度为3.5～4，25℃时的粘度为45000～55000mPa.s，是以芳香族二胺4,4’-二苯甲烷二胺(MDA)与甘油、丙二醇、乙二胺中的一种或两种作为复合起始剂，以氧化乙烯(EO)或氧化丙烯(PO)作为聚合单体制备而成。高羟值、高粘度芳香胺类聚醚多元醇的使用使得泡沫的泡孔变得细腻、降低了泡沫的导热系数数值、改善了泡沫的脱模性能，同时其结构中的苯环结构提高了聚氨酯泡沫的强度，具有较好的尺寸稳定性。
本发明中，所述山梨醇类聚醚多元醇的羟值为450～500mg KOH/g，官能度为4～5，是以山梨醇与季戊四醇、二甘醇和甘油中的一种或两种或多种作为复合起始剂，以氧化丙烯为聚合单体制备而成，其结构中较长的链段结构和较高的官能度使得泡沫具有较好的粘结性能与强度性能。
本发明中，所述低官能度聚醚多元醇的平均分子量为700～1000g/mol，官能度为2～3；是以低官能度醇为起始剂，以氧化乙烯或氧化丙烯作为聚合单体制备而成，其中所述低官能度醇为丙三醇、丙二醇、二乙二醇和乙二醇中的一种或两种或多种。低官能度聚醚多元醇的加入使得泡沫的流动性与泡沫韧性得到改善。
本发明中，所述泡沫稳定剂是由亲油的非极性硅氧烷主链与亲水的极性聚醚支链组成，包括但不限于德美公司的AK-8818、AK8830、迈图公司的L6860、L6900和L5466的一种或两种或多种。此类泡沫稳定剂有利于泡沫的流动性，同时改善了泡沫的各向同性，即在垂直于或平行于泡沫生长方向上的强度得到改善。
本发明中，所述复合型催化剂同时含有发泡型催化剂、凝胶型催化剂和三聚型催化剂三种催化剂。其中，发泡型催化剂包含但不限于双(二甲胺基乙基)醚、五甲基二乙烯三胺和HP1038中的一种或两种或三种，优选五甲基二乙烯三胺；凝胶型催化剂包含但不限于N,N-二甲基环己胺、三乙烯二胺、三亚己基二胺、二甲基乙醇胺和二甲基苄胺中的一种或两种或多种，优选N，N-二甲基环己胺；三聚型催化剂包含但不限于TMR-2、醋酸钾、异辛酸钾、辛酸亚锡、1，3，5-三(二甲氨基丙基)六氢三嗪、BX407和Debco PT304中的一种或两种或多种，优选醋酸钾。复合型催化剂的加入，使得泡沫在流动的过程中具有良好的流动性；加快了泡沫后期的熟化；三聚反应中三聚体结构的转化率得到提高，提高了泡沫的强度与脱模性能。
本发明中，所述发泡剂为环戊烷和1-氯-3,3,3-三氟丙烯(LBA)，两者的比例为7.5～12.5:13.5～3.5。
本发明中，所述多异氰酸酯为多亚甲基多苯基多异氰酸酯，NCO含量为31～32.5wt％，官能度为2.0～2.5；所述多异氰酸酯包括但不限于万华化学的产品PM200和PM400，优选为PM400。
本发明中，所述多异氰酸酯组分与组合多元醇组分的质量比为140:100～110:100，优选为130:100～120:100。
本发明所述的高强度聚氨酯硬质泡沫塑料的制备方法，包括以下步骤：
1)将多异氰酸酯组分与组合多元醇组分按照质量比为140:100～110:100，优选130:100～120:100，通过高压发泡机设备进行充分混合；
2)充分混合后的多异氰酸酯组分与组合多元醇组分经发泡机枪头注入到金属模具，泡沫在模具内熟化后进行开模，室温静置24h后，得到高强度聚氨酯硬质泡沫塑料。
其中，所述发泡机枪头压力为120～130bar下，金属模具的模温维持在35～45℃，熟化时间为10min，多异氰酸酯与组合聚醚多元醇混合温度为18～22℃。
本发明的高强度聚氨酯硬质泡沫塑料可应用于冰箱、冷柜、太阳能、燃气热水器和消毒柜等家电内部保温材料。
本发明的有益效果是：
1)引入了苯酰亚胺类聚氨酯改性剂，可作为聚酯多元醇，其刚性结构提高了聚氨酯泡沫的强度，同时泡沫的阻燃性能与耐热性得到提高。
2)组合聚醚多元醇中使用一种高羟值、高粘度的芳香胺类聚醚多元醇，由于其本身的刚性结构，赋予泡沫较高的强度，同时具有较好的脱模性能与较细腻的泡孔结构。
3)本发明中使用的多异氰酸酯如PM400具有更高的官能度且黏度指标略高，约为400mPa.s左右(现有技术用于家电保温的聚合MDI的黏度指标均在200mPa.s左右，如巴斯夫44V20，亨斯曼5005)，使得聚氨酯结构的交联程度增强，聚氨酯泡沫中硬段结构更显刚性，泡沫的强度得到提高，同时泡沫具有较好的脱模与隔热性能。
具体实施方式
为了更好的理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明的内容不仅仅局限于以下的实施例。
苯酰亚胺类改性剂：
将摩尔比为1:1的偏苯三酐与对氨基苯乙酸、300ml丙酮溶剂加入到反应釜中，待完全溶解再加入基于偏苯三酐和对氨基苯乙酸总量的2.0wt％的催化剂无水醋酸钠于70℃下进行氨化脱水环化反应3h，形成含氮五元杂环二元羧酸。该二元酸再与环氧氯丙烷(摩尔比＝1:2.0)通过0.6wt％三苯基磷的催化作用进行反应，得到羟值为220±25mgKOH/g，官能度为2。
芳香胺类聚醚多元醇的制备：
将4,4’-二苯甲烷二胺、甘油、催化剂KOH置于反应釜中，经氮气置换，试压合格后温度升至90～100℃，连续投入环氧丙烷，其中4,4’-二苯甲烷二胺、甘油和环氧丙烷的质量比20.4：9.6：70，催化剂KOH用量为4,4’-二苯甲烷二胺与甘油总用量的1.5wt％～2.5wt％。经反应完全后，脱除未反应的小分子进行精制，待合成的聚醚多元醇中水份合格后(水份含量小于1.0wt％)，进行压滤，最后得到芳香胺类聚醚多元醇，其羟值为410～450mg KOH/g，25℃时的粘度为50000±1000mPa.s。
山梨醇类聚醚多元醇：R6246；低官能度聚醚多元醇：R2303，均购于万华化学(宁波)容威聚氨酯有限公司；PM400，万华化学。
聚酯多元醇PS3152，Stepan；泡沫稳定剂：L6900，Momentive；LBA即1-氯-3,3,3-三氟丙烯，Honeywell；
凝胶型催化剂：三聚型催化剂：均购于AirProducts；发泡型催化剂，HP1038，上海宏璞化工科技有限公司；
按照表1五种配方，配置好聚氨酯硬泡组合料。在高压发泡机下，模具温度35～45℃，料温维持在18～22℃，枪头压力120～130bar下在模具内进行混合发泡，待泡沫熟化10min后开模，等室温下静置熟化24h后进行聚氨酯硬质泡沫的性能测试。压缩强度测试泡沫的尺寸为50mm×50mm×30mm，导热系数测试泡沫的尺寸为200mm×200mm×25mm。
实施例配方和泡沫体性能详见表1(以组合聚醚多元醇组份总重量份数为100计)。
表1聚氨酯硬质泡沫配方和泡沫体性能数据表
由表中实施例可以看出，发明产品具有较高的的压缩强度，泡孔细腻、具有较低的导热系数、泡沫的阻燃性能得到一定提高。
上述实施例中提到的内容并非是对本发明的限定，在不脱离本发明的发明构思的前提下，任何显而易见的替换均在本发明的保护范围之内。

Claims (10)

1.一种高强度聚氨酯硬质泡沫塑料，由组合多元醇组分与多异氰酸酯组分在高压机混合下进行发泡制得，其特征在于，以组合多元醇组份总重量份数为100计，所述组合多元醇中各组分重量份数分别为：
2.根据权利要求1所述的高强度聚氨酯硬质泡沫塑料，其特征于，所述苯酰亚胺类改性剂是具有刚性结构的苯酰亚胺聚酯多元醇，羟值为250～350mgKOH/g，其结构式为：
3.根据权利要求1或2所述的高强度聚氨酯硬质泡沫塑料，其特征在于，所述苯酰亚胺类改性剂是由偏苯三酐与对氨基苯乙酸在催化剂作用下经过氨化反应后脱水环化形成含氮五元杂环二元羧酸，该含氮五元杂环二元羧酸再与过量的环氧氯丙烷开环聚合而成。
4.根据权利要求1-3中任一项所述的高强度聚氨酯硬质泡沫塑料，其特征在于，所述芳香胺类聚醚多元醇羟值为410～450mg KOH/g,25℃时的黏度为45000～55000mPa·s，官能度为3.5～4；是以芳香族二胺优选4,4’-二苯甲烷二胺，与甘油、丙二醇和乙二胺中的一种或两种作为复合起始剂，以氧化乙烯或氧化丙烯作为聚合单体制备而成。
5.根据权利要求1-4中任一项所述的高强度聚氨酯硬质泡沫塑料，其特征在于，所述山梨醇类聚醚多元醇的羟值为450～500mg KOH/g；官能度为4～5，是以山梨醇与季戊四醇、二甘醇和甘油中的一种或两种作为复合起始剂，以氧化丙烯为聚合单体制备而成。
6.根据权利要求1-5中任一项所述的高强度聚氨酯硬质泡沫塑料，其特征在于，所述的低官能度聚醚多元醇平均分子量为700～1000g/mol，官能度为2～3，是以低官能度醇类为起始剂，与氧化乙烯或氧化丙烯作为聚合单体制备而成，其中，所述低官能度醇类为丙三醇、丙二醇、二乙二醇和乙二醇中的一种或两种或多种，优选为二乙二醇和/或丙二醇。
7.根据权利要求1-6中任一项所述的高强度聚氨酯硬质泡沫塑料，其特征在于，所述发泡剂为环戊烷和1-氯-3,3,3-三氟丙烯；所述复合催化剂同时含有发泡型催化剂、凝胶型催化剂和三聚型催化剂；其中，所述发泡型催化剂是双(二甲胺基乙基)醚、五甲基二亚乙基三胺和HP1038中的一种或两种或三种，优选五甲基二乙烯三胺；凝胶型催化剂是N,N-二甲基环己胺、三乙烯二胺、三亚己基二胺、二甲基乙醇胺和二甲基苄胺中的一种或两种或多种，优选N，N-二甲基环己胺；三聚型催化剂是TMR-2、醋酸钾、油酸钾、异辛酸钾、辛酸亚锡、1，3，5-三(二甲氨基丙基)六氢三嗪、BX407和Debco PT304的一种或两种或多种，优选醋酸钾。
8.根据权利要求1-7中任一项所述的高强度聚氨酯硬质泡沫塑料，所述多异氰酸酯组分与组合多元醇组分的质量比为140:100～110:100，优选为130:100～120:100。
9.一种制备权利要求1-8中任一项所述的高强度聚氨酯硬质泡沫塑料的方法，包括以下步骤：
1)将多异氰酸酯组分与组合多元醇组分按照140:100～110:100的比例，优选130:100～120:100通过高压发泡机设备进行充分混合发泡；
2)充分混合后的多异氰酸酯组分与组合多元醇组分经发泡机枪头注入到金属模具，泡沫在模具内熟化后进行开模，室温静置24h后，得到高强度聚氨酯硬质泡沫塑料。
10.权利要求1-8中任一项所述的高强度聚氨酯硬质泡沫塑料或由权利要求9所述方法制备的高强度聚氨酯硬质泡沫塑料在冰箱、冷柜、太阳能、燃气热水器和消毒柜家电内部保温材料中的用途。
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106700119A (zh) * 2016-12-26 2017-05-24 青岛海尔股份有限公司 发泡剂组合物和聚氨酯硬质泡沫
CN106832188A (zh) * 2017-01-23 2017-06-13 山东诺威新材料有限公司 集装箱用聚氨酯泡沫塑料保温材料及其制备方法
CN107200827A (zh) * 2017-07-24 2017-09-26 合肥美菱股份有限公司 一种用于冰箱门体翻转梁的发泡聚氨酯及其应用
WO2018093709A1 (en) * 2016-11-17 2018-05-24 Covestro Llc Polyurethane foams co-blown with a mixture of a hydrocarbon and a halogenated olefin
CN109627746A (zh) * 2018-11-23 2019-04-16 贵州航天天马机电科技有限公司 一种大负压聚氨酯前端易碎式保护盖及其成型方法
CN111518251A (zh) * 2020-04-08 2020-08-11 上海抚佳精细化工有限公司 一种聚氨酯硬质泡沫及其制备方法
CN111909339A (zh) * 2020-08-10 2020-11-10 万华化学（烟台）容威聚氨酯有限公司 烷烃类发泡b1级阻燃聚氨酯硬质泡沫及其制备方法
CN112708094A (zh) * 2020-12-28 2021-04-27 上海东大聚氨酯有限公司 环境友好型超低温保温箱用组合聚醚、聚氨酯泡沫及其制备方法
CN114479006A (zh) * 2022-01-28 2022-05-13 万华节能科技(烟台)有限公司 适用于冷库滑雪场建筑内保温的结构性阻燃聚氨酯泡沫材料
CN114835872A (zh) * 2022-06-07 2022-08-02 格力电器（武汉）有限公司 一种高阻燃低导热聚氨酯泡沫材料及其制备方法
EP3548533B1 (de) 2016-11-29 2022-10-05 Covestro Intellectual Property GmbH & Co. KG Polyurethan-hartschaumstoffe, ein verfahren zu deren herstellung und deren verwendung

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3933700A (en) * 1973-03-12 1976-01-20 Standard Oil Company Modified polyurethane foams containing imide groups
CN1176968A (zh) * 1996-08-13 1998-03-25 住友拜尔乌拉坦株式会社 生产硬质聚氨酯泡沫塑料的方法和用来生产硬质聚氨酯泡沫塑料的组合物
CN104151523A (zh) * 2014-08-07 2014-11-19 合肥华凌股份有限公司 硬质聚氨酯泡沫组合物、制备该泡沫的方法及保温组件

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3933700A (en) * 1973-03-12 1976-01-20 Standard Oil Company Modified polyurethane foams containing imide groups
CN1176968A (zh) * 1996-08-13 1998-03-25 住友拜尔乌拉坦株式会社 生产硬质聚氨酯泡沫塑料的方法和用来生产硬质聚氨酯泡沫塑料的组合物
CN104151523A (zh) * 2014-08-07 2014-11-19 合肥华凌股份有限公司 硬质聚氨酯泡沫组合物、制备该泡沫的方法及保温组件

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
左晓兵等: "乙醇胺改性酰亚胺聚酯聚氨酯的合成及性能", 《高分子材料科学与工程》 *
蔡克林等: "含酰亚胺官能团二羧酸单体的合成", 《化学试剂》 *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018093709A1 (en) * 2016-11-17 2018-05-24 Covestro Llc Polyurethane foams co-blown with a mixture of a hydrocarbon and a halogenated olefin
US11505670B2 (en) 2016-11-17 2022-11-22 Covestro Llc Polyurethane foams co-blown with a mixture of a hydrocarbon and a halogenated olefin
EP3548533B1 (de) 2016-11-29 2022-10-05 Covestro Intellectual Property GmbH & Co. KG Polyurethan-hartschaumstoffe, ein verfahren zu deren herstellung und deren verwendung
CN106700119B (zh) * 2016-12-26 2020-03-17 青岛海尔股份有限公司 发泡剂组合物和聚氨酯硬质泡沫
CN106700119A (zh) * 2016-12-26 2017-05-24 青岛海尔股份有限公司 发泡剂组合物和聚氨酯硬质泡沫
CN106832188A (zh) * 2017-01-23 2017-06-13 山东诺威新材料有限公司 集装箱用聚氨酯泡沫塑料保温材料及其制备方法
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