CN106317365B - 具有高含量生物基材料的生物基聚氨酯喷涂泡沫塑料 - Google Patents

具有高含量生物基材料的生物基聚氨酯喷涂泡沫塑料 Download PDF

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CN106317365B
CN106317365B CN201610707614.2A CN201610707614A CN106317365B CN 106317365 B CN106317365 B CN 106317365B CN 201610707614 A CN201610707614 A CN 201610707614A CN 106317365 B CN106317365 B CN 106317365B
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崔爱华
林永飞
魏建辉
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Nantong Xinyi Material Technology Co., Ltd
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Abstract

本发明公开了一种具有高含量生物基材料的生物基聚氨酯喷涂泡沫塑料，由以至少一种生物基聚醚多元醇为原料制备的聚氨酯喷涂组合白料组分与异氰酸酯组分混合发泡聚合生成的。本发明产品具有高含量的生物基材料，应用在墙面或屋顶的保温防水喷涂中，使泡沫材料具有与用全部石油基材料生产的泡沫类似的性能。

Description

具有高含量生物基材料的生物基聚氨酯喷涂泡沫塑料
本申请是申请号：201510660909.4、申请日：2015.10.14、名称“生物基聚氨酯喷涂泡沫塑料及其制备方法”的分案申请。
技术领域
本发明涉及聚氨酯喷涂泡沫塑料，具体涉及一种生物基多元醇制备聚氨酯喷涂泡沫及其制备方法。
背景技术
聚氨酯硬质泡沫因其优良的绝热性能被广泛应用于冰箱、冷柜、冷库板、夹心板、管道保温、冷藏集装箱、建筑节能等国民经济的多个领域，聚氨酯喷涂泡沫发泡成型是将双组分聚氨酯泡沫组合料直接喷射到物体表面发泡成型，其优点是：与基材粘接力强；加工简易，无论何种形状表面都可以通过喷涂形成保温隔热层，因而大大提高了劳动生产率；同时兼具防水、吸音、隔音等功能。
现有技术的聚氨酯硬质泡沫的组合白料的多羟基化合物，其主要的成分为石油提制产品，是不可再生资源，其加工生产过程复杂，成本高且污染环境，其价格也随石油价格的波动而波动。生物基聚醚多元醇是大豆油、菜籽油、棉籽油或棕榈油为起始原料合成的多元醇化合物，是种环保的、可再生的资源，并且已经实现了工业化生产。从环保以及资源循环利用角度来看，采用生物基聚醚多元醇是今后研究的主要方向。
由于生物基聚醚多元醇的分子量较大，羟值偏低，在聚氨酯方面主要应用在软质泡沫和聚异氰酸酯泡沫的改性方面。对于指数较低的硬质泡沫及喷涂聚氨酯中的应用于还相对较少，或者所引入的生物基聚醚多元醇的含量极低，仍然需要大量的石油基聚酯和聚酯多元醇。在聚氨酯喷涂泡沫塑料仍然需要一种聚氨酯硬质泡沫材料，该材料既具有高含量生物基材料，又具有与现有石油基原料制备的泡沫材料类似的性能特性。
发明内容
本发明的目的在于提供一种具有高含量的生物基材料，应用在墙面或屋顶的保温防水喷涂中，使泡沫材料具有与用全部石油基材料生产的泡沫类似的性能的生物基聚氨酯喷涂泡沫塑料及其制备方法。
本发明的技术解决方案是：
一种生物基聚氨酯喷涂泡沫塑料，其特征在于由以至少一种生物基聚醚多元醇为原料制备的聚氨酯喷涂组合白料组分与异氰酸酯组分混合发泡聚合生成的。
所述的聚氨酯组合白料的组分为至少一种生物基聚醚多元醇的多元醇组分，胺类和/或金属盐类催化剂、物理和/或化学发泡剂、泡沫稳定剂以及任选阻燃剂。其中所述的生物基多元醇占整个多元醇组分的重量比为5-75％，其中优选20％-50％。
所述的生物基聚醚多元醇可由各种生物基原料生产，包括但不限于：大豆油、麻风树油、棕榈油、玉米油、花生油、棉籽油、菜籽油、橄榄油和它们的混合物。特别优选的生物基聚醚多元醇是由大豆油多元醇。
所述的异氰酸酯组分为平均官能度在2.5-3.5之间的粗制聚合二苯基甲烷二异氰酸酯(PMDI)或改进的粗制多亚甲基多苯基多异氰酸酯；所述的聚氨酯喷涂组合白料组分与异氰酸酯组分的质量比为1：1～1.5，优选比例1：1。所述的喷涂泡沫塑料的平均密度在30-80kg/m3，优选密度在35-55kg/m3。
用于生物基聚氨酯喷涂泡沫塑料的催化剂包括胺类和/或金属盐类催化剂，其中胺类催化剂为叔胺类催化剂包括五甲基二乙烯三胺、N,N-二甲基环己胺、三乙烯二胺、三乙胺、双二甲胺基乙基醚中的一种两种或多种；所述金属盐类催化剂为包括异辛酸钾、甲酸季铵盐、醋酸钾、二月桂酸二丁基锡、辛酸亚锡和油酸钾的一种两种或多种。由于聚氨酯喷涂泡沫反应非常迅速，固化成型正常在十几秒内完成，因些所添加的催化剂的量较其它聚氨酯泡沫所需用量要大的多，占聚氨酯喷涂组合白料组分5％-15％的用量。
水和低沸点化合物的组合用作本发明的发泡剂。低沸点含氟化合物，例如HFC-245fa、HFC-365mfc和HFC-134a，它们单独使用或者组合使用。特别优选用于本发明的发泡剂是1,1-二氯-1-氟乙烷(HCFC-141B)、1,1,1,3,3-五氟丙烷(HFC-245fa)和1,1,1,3,3-五氟丁烷(HFC-365)和它们的混合物。正常烷类发泡剂因为安全问题很少用于聚氨酯喷涂泡沫中，比如环戊烷、异戊烷等。
聚氨酯喷涂发泡中可用到有利于发泡的少量泡沫稳定剂，以在聚合初始阶段稳定发泡反应混合物，有助于调节孔径，产生闭合的孔，从而改进绝热性能。所用的泡沫稳定剂为非水解硅碳类表面活性剂和非硅酮类表面活性剂中一种或两种。由于喷涂发泡的速度迅速，所以泡沫的泡孔相对较好，因此，所用的泡沫稳定剂所起的作用更偏向于聚氨酯喷涂组合白料组分在发泡之前的储存稳定性。
合适的阻燃剂包括膦酸酯/盐、亚磷酸酯/盐和磷酸酯/盐(例如甲基膦酸二甲酯、多磷酸铵、和各种环磷酸酯和膦酸酯可应用于生物基聚氨酯喷涂泡沫中。由于聚氨酯喷涂发泡成型是通过发泡枪头雾化混合发泡成型，因而在选用阻燃剂时更偏向于液态的，储存稳定性相对较好的原料，比如三(2-氯乙基)磷酸酯(TCEP)、三(2-氯丙基)磷酸酯(TCPP)、磷酸三乙酯(TEP)和甲基膦酸二甲酯(DMMP)的一种或多种，其中优选三(2-氯丙基)磷酸酯(TCPP)和磷酸三乙酯(TEP)。
所述的生物基聚氨酯喷涂泡沫塑料的制备方法，包括以下步骤：(1)将多元醇组合、催化剂、发泡剂、泡沫稳定剂以及任选阻燃剂按照比例混合均匀，制得聚氨酯组合白料组分；(2)将步骤(1)中制得的组合白料组分与异氰酸酯组分按固定比例，通过高压喷涂机喷在木板或者水泥板上，两组分快速反应固化成形，生成生物基聚氨酯喷涂泡沫塑料。
本发明产品具有高含量的生物基材料，应用在墙面或屋顶的保温防水喷涂中，使泡沫材料具有与用全部石油基材料生产的泡沫类似的性能。
下面结合实施例对本发明作进一步说明。
具体实施方式
通过以下实施例进一步说明本发明，但本发明不限于以下实施例，除非另有说明，否则，所有以“份数”和“百分比”给出的量都应该理解为是以重量计的。以下材料用于生产实施例的聚氨酯泡沫材料：
表1聚氨酯原料简介
按下表2中所列的重量份数的各组分混合，并异氰酸酯组分与白料组合重量比为1：1的情况下反应，产生自由发泡的泡沫材料。使用本领域普通技术人员已知的手动混合步骤制备这些泡沫材料，在泡沫固化成型后，检测泡沫性能。
表2聚氨酯泡沫组分配参数(重量份)
参考例1是用于GB50404-2007的聚氨酯喷涂泡沫的常用配方。在实施例中，用一种或两种生物基多元醇替代部分。如需调节发泡速度，可调节催化剂用量；如需调节泡沫密度，可调节水和物理发泡剂的用量。
将密度、导热系数、氧指数这样关键的泡沫性能与对照泡沫材料对比，有的好一些，有的差一些。但是通过各组合料的配比的调整可以达到的最为合适的原料配比，性能达标，成本最优化，生物基聚醚多元醇使用量最佳。
表3喷涂泡沫各项性能参数
从表3可以看出，生物基多元醇与脂肪族多元醇组合，在高官能度的脂肪族多元醇的配合下，保证聚氨酯喷涂泡沫的各项基本性能，将生物基多元醇的用量最大化，同时，在使用不同生物基多元醇时要根据不同的产品的特性使用不同的量。选取实例4进行喷涂现场发泡，根据表2制得聚氨酯喷涂组合白料组分，然后通过高压喷涂机将制得的组合白料组分与异氰酸酯组分按固定比例，喷在木板上，快速反应固化成形，生成生物基聚氨酯喷涂泡沫塑料。通过发泡机制得的泡沫性能较实验室发泡性能更佳。
前述的本发明的实施例是为了说明而非限制性的目的。文中所述的实施方式可在不背离本发明精神和范围的前提下进行各种变化或修改，这对本领域技术人员而言是显而易见的。本发明的范围由所附权利要求限定。

Claims (2)

1.一种具有高含量生物基材料的生物基聚氨酯喷涂泡沫塑料，其特征是：由包括生物基聚醚多元醇为原料制备的聚氨酯喷涂组合白料组分与异氰酸酯组分混合发泡聚合生成的；所述包括生物基聚醚多元醇为原料制备的聚氨酯喷涂组合白料组分由下列重量份的成分组成：
聚醚多元醇A 30份
聚醚多元醇B 20份
阻燃聚醚多元醇C 10份
聚酯多元醇D 20份
生物基多元醇E 20份
催化剂A 2份
催化剂B 2.5份
催化剂C 1份
泡沫稳定剂 2.5份
阻燃剂A 35份
水 1份
发泡剂 20份；
所述聚醚多元醇A是蔗糖起始的精制聚醚多元醇，羟值380mgKOH/g，在25℃的粘度为10000厘泊，羟基官能度为6；
所述聚醚多元醇B是乙二胺起始的聚醚多元醇，羟值760mgKOH/g，在25℃的粘度为25000厘泊，羟基官能度为4；
所述阻燃聚醚多元醇C是含溴起始的阻燃聚醚多元醇，羟值200mgKOH/g，在25℃的粘度为15000厘泊，羟基官能度为2；
所述聚酯多元醇D是邻苯二甲酸酯的芳族聚酯多元醇，羟值310mgKOH/g，25℃的粘度为3000厘泊，官能度为2；
所述生物基多元醇E是环氧大豆油基植物油多元醇，羟值380mgKOH/g，在25℃的粘度为5000厘泊，官能度为4.5；
所述催化剂A是五甲基二乙烯三胺；催化剂B是三乙烯二胺；催化剂C是二月桂酸二丁基锡；
所述泡沫稳定剂是硅氧烷表面活性剂；阻燃剂A是三（2-氯丙基）磷酸酯；发泡剂是1,1-二氯-1-氟乙烷(HCFC-141B)；
异氰酸酯的用量为150份。
2.根据权利要求1所述的具有高含量生物基材料的生物基聚氨酯喷涂泡沫塑料，其特征是：异氰酸酯是聚合二苯基甲烷二异氰酸酯，NCO基含量为32.4，25℃的粘度为25厘泊。
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