CN107286315B - 一种高压缩强度的硬质聚氨酯泡沫塑料及其制备方法 - Google Patents

一种高压缩强度的硬质聚氨酯泡沫塑料及其制备方法 Download PDF

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CN107286315B
CN107286315B CN201610228371.4A CN201610228371A CN107286315B CN 107286315 B CN107286315 B CN 107286315B CN 201610228371 A CN201610228371 A CN 201610228371A CN 107286315 B CN107286315 B CN 107286315B
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祝丽娟
邢小刚
孔超
吴月辉
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Nanjing Hongbaoli New Materials Co ltd
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Abstract

本发明公开了一种高压缩强度的硬质聚氨酯泡沫塑料及其制备方法，高压缩强度的硬质聚氨酯泡沫塑料包括重量比为1:(1.2～2.5)的组分A和组分B；组分A包括多元醇100份、催化剂1.5～5.0份、发泡剂15～30份、水1.5～3.0份和泡沫稳定剂0.5～4.0份，其中，100份多元醇由聚醚多元醇50～80份和聚酯多元醇20～50份组成，所述份数为重量份数；组分B是多苯基多亚甲基多异氰酸酯。本发明高压缩强度的硬质聚氨酯泡沫塑料具有隔热保温、高强度、低密度特点，当密度为45kg/m3，压缩强度大于300kPa；制备工艺简单、生产效率高。

Description

一种高压缩强度的硬质聚氨酯泡沫塑料及其制备方法
技术领域
本发明涉及一种高压缩强度的硬质聚氨酯泡沫塑料及其制备方法，属于新材料领域。
背景技术
由于硬质聚氨酯泡沫塑料具有非常低的导热系数及透水蒸汽性，质轻、比强度高，一直以来被广泛应用于汽车工业、建筑工业及设备制造工业，在这些领域中对硬质聚氨酯泡沫塑料材料的压缩强度要求不是很高，故其原料配方和工艺方法相对简单。而在冻土地区路基、管道保温，冷库地坪，船舰以及航空、航天等特殊领域，越来越多地采用硬质聚氨酯泡沫塑料，以满足重量轻、强度高的要求。但现有的硬质聚氨酯泡沫材料的性能还不能很好地满足以上应用领域的要求，因此改进配方、实现快速连续生产工艺，以提升材料性能尤为迫切。
发明内容
为了解决现有技术中硬质聚氨酯泡沫存在的压缩强度低等缺陷，本发明提供一种高压缩强度的硬质聚氨酯泡沫塑料及其制备方法。
为解决上述技术问题，本发明所采用的技术方案如下：
一种高压缩强度的硬质聚氨酯泡沫塑料，包括重量比为1:(1.2～2.5)的组分A和组分B；
组分A包括多元醇100份、催化剂1.5～5.0份、发泡剂15～30份、水1.5～3.0份和泡沫稳定剂0.5～4.0份，其中，100份多元醇由聚醚多元醇50～80份和聚酯多元醇20～50份组成，所述份数为重量份数；
组分B是多苯基多亚甲基多异氰酸酯。
为了提高产品的阻燃性能，同时促进各原料组分之间的协同效应，所述的组分A中还包括5～30份的阻燃剂，阻燃剂为磷酸三(2-氯丙基)酯、三(2-羧乙基)膦、三(2，3-二氯丙基)磷酸酯、甲基磷酸二甲酯、三聚氰胺、三羟甲基氧化膦、N,N-二(2-羟异丙基)氨甲基膦酸二乙酯、氢氧化铝、氢氧化镁、磷酸铵、聚磷酸铵或硼酸锌中的至少一种，所述份数为重量份数。
为了进一步提高所得产品的压缩强度等综合性能，优选，聚醚多元醇的羟值为100～600mgKOH/g，粘度为500～10000mPa·s；聚酯多元醇的羟值为200～400mgKOH/g，粘度为2000～20000mPa·s。
为了控制反应速度从而使产品的质量达到最佳，优选，催化剂为胺类催化剂和有机金属类催化剂任意配比的混合物；进一步优选，所述胺类催化剂是三乙醇胺、二甲基环己胺、三亚乙基二胺、三乙烯二胺、2,4,6-三(二甲氨基甲基)苯酚、1,3,5-三(二甲氨基丙基)对称六氢三嗪、羧酸盐或季铵盐中的一种或两种以上任意比例的混合物；所述有机金属类催化剂是二丁基锡二月桂酸酯、辛酸亚锡或异辛酸钾-二丙二醇溶液中的一种或两种以上任意比例的混合物。
为了促进各组分之间的协同效应，从而使产品的综合性能达到最佳，优选，发泡剂为HCFC-141b、HFC-245fa、HFC-365mfc、环戊烷、异戊烷、正戊烷、水或二氧化碳中的至少一种；泡沫稳定剂为含Si-C结构的硅类表面活性剂。
为了进一步提高产品的压缩强度，优选，所述多苯基多亚甲基多异氰酸酯中的异氰酸酯基NCO的质量分数为30.0～32.0％。
上述高压缩强度的硬质聚氨酯泡沫塑料的制备方法，包括顺序相接的如下步骤：
(1)组分A的准备：将组分A的各原料混匀，得组分A；
(2)组分B的准备：取组分B备用；
(3)混合注射：将组分A、组分B分别打入高压发泡机料罐内，两组分分别经过过滤器、计量泵和高低压转换阀后在喷头位置充分混合，混合后的物料喷洒在下面层材料上，然后在所喷洒的物料上覆盖上面层材料，进入温度为50-80℃的双履带机内；
(4)层压固化：履带板沿导轨运动，带动上下面层材料向前输送，并通过垫块调整上下履带板间的距离，从而控制上下面层材料之间制品的厚度；
(5)铣边切割：泡沫塑料制品从双履带机出来后经过铣边装置，将宽度调整到合适尺寸后再进入盘锯切割机，盘锯横向移动切断制品，切断后的制品进入后辊道；
(6)熟化包装：在辊道出口处晾板熟化、堆垛、包装，即得。
上述高压缩强度的硬质聚氨酯泡沫塑料的制备方法实现了高压缩强度的硬质聚氨酯泡沫塑料的连续稳定生产，相对现有技术，生产效率提升显著。
为了能进一步控制所得产品的综合性能，步骤(3)中组分A、B混合后，乳白时间为6～30秒，拉丝时间为20～80秒，自由发泡倍率为制品实际体积的1.2～2倍；实际生产时，可通过小样调试各组分用量配比，将乳白时间、拉丝时间及发泡倍率调整在上述范围内，从而保证产品质量。
步骤(4)中双履带机温度为50～80℃，线速度为3～60米/分。
本发明未提及的技术均参照现有技术。
本发明高压缩强度的硬质聚氨酯泡沫塑料具有隔热保温、高强度、低密度特点，当密度为45kg/m3，压缩强度大于300kPa；制备工艺简单、生产效率高。
具体实施方式
为了更好地理解本发明，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下面的实施例。
下述实施例中，密度的测定按GB/T 6343-2009《泡沫塑料及橡胶表观密度的测定》进行。压缩强度的测定按GB/T 8813-2008《硬质泡沫塑料压缩性能的测定》进行。氧指数的测定按GB/T 2406.2-2009《塑料用氧指数法测定燃烧行为第2部分：室温试验》进行。尺寸稳定性的测定按GB/T8811-2008《硬质泡沫塑料尺寸稳定性试验方法》进行。
实施例1
制备密度为78kg/m3的高压缩强度的硬质聚氨酯泡沫塑料制品，其工艺步骤如下：
(1)组分A的准备：按重量取多元醇100份(其中HP3201聚醚多元醇60份，PS-2502A聚酯多元醇40份)；催化剂4.5份(其中二甲基环己胺2.3份，1,3,5-三(二甲氨基丙基)对称六氢三嗪1.0份，异辛酸钾-二丙二醇溶液1.2份)；发泡剂(HCFC-141b)23份；水2.0份；泡沫稳定剂(赢创德固赛，B8460)1.15份；阻燃剂20份(其中磷酸三(2-氯丙基)酯10份，甲基磷酸二甲酯10份)。在保持外界环境温度为23±2℃、相对湿度＜70％的条件下，将各原料机械混合，搅拌均匀，得组分A。
(2)组分B的准备：取多苯基多亚甲基多异氰酸酯(BASF，M20S)备用。
(3)混合注射：将组分A、组分B分别通过卸车泵打入储料罐，再分别用进料泵打入高压发泡机料罐内，两组分再分别经过过滤器、计量泵和高低压转换阀后在喷头位置充分混合，混合后的物料喷洒在下面层材料上(牛皮纸，与下钢板接触)，然后再在其上覆盖上面层材料(牛皮纸，与上钢板接触)后，进入温度为55℃、线速度为19米/分的双履带机内，组份A和组分B的质量比为1:1.4。乳白时间为11秒，拉丝时间为26秒，自由发泡倍率为制品实际体积的1.2倍。
(4)层压固化：履带板沿导轨运动，带动上下钢板向前输送，并通过垫块调整上下履带板间的距离，从而控制上下钢板之间制品的厚度。
(5)铣边切割：泡沫塑料制品从双履带机出来后经过铣边装置，将宽度调整到合适尺寸后再进入盘锯切割机，盘锯横向移动切断制品，切断后进入后辊道。
(6)熟化包装：在辊道出口处晾板熟化、堆垛、包装，再送入仓库储存。
表1：实施例1的高压缩强度的硬质聚氨酯泡沫塑料的性能测试结果
Figure BDA0000963869650000041
实施例2
制备密度为62kg/m3的高压缩强度的硬质聚氨酯泡沫塑料制品，其工艺步骤如下：
(1)组分A的准备：按重量取多元醇100份(其中HP2502聚醚多元醇73份，HF-8634聚酯多元醇27份)；催化剂3.5份(其中三亚乙基二胺2.0份，1,3,5-三(二甲氨基丙基)对称六氢三嗪1.5份)；发泡剂16份(其中环戊烷10份，HFC-245fa 6份)；水1.5份；泡沫稳定剂(南京德美世创化工有限公司，AK-8805)3.0份。在保持外界环境温度为23±2℃、相对湿度＜70％的条件下，将各原料机械混合，搅拌均匀，得组分A。
(2)组分B的准备：取多苯基多亚甲基多异氰酸酯(烟台万华聚氨酯集团公司，PM-200)备用。
(3)混合注射：将组分A、组分B分别通过卸车泵打入储料罐，再分别用进料泵打入高压发泡机料罐内，两组分再分别经过过滤器、计量泵和高低压转换阀后在喷头位置充分混合，混合后的物料喷洒在下面层材料(水泥玻纤毡，与下钢板接触)上，然后在其上覆盖上面层材料(水泥玻纤毡，与上钢板接触)后，进入温度为65℃、线速度为15米/分的双履带机内，组份A和组分B的质量比为1:2。乳白时间为22秒，拉丝时间为45秒，自由发泡倍率为制品实际体积的1.5倍。
(4)层压固化：履带板沿导轨运动，带动上下钢板向前输送，并通过垫块调整上下履带板间的距离，从而控制上下钢板之间制品的厚度。
(5)铣边切割：泡沫塑料制品从双履带机出来后经过铣边装置，将宽度调整到合适尺寸后再进入盘锯切割机，盘锯横向移动切断制品，切断后进入后辊道。
(6)熟化包装：在辊道出口处晾板熟化、堆垛、包装，再送入仓库储存。
表2：实施例2的高压缩强度的硬质聚氨酯泡沫塑料的性能测试结果
Figure BDA0000963869650000051
实施例3
制备密度为47kg/m3的高压缩强度的硬质聚氨酯泡沫塑料制品，其工艺步骤如下：
(1)组分A的准备：按重量取多元醇100份(其中ZS-4110聚醚多元醇51份，HF-8025聚酯多元醇49份)；催化剂2.3份(其中三乙醇胺1.5份，二丁基锡二月桂酸酯0.8份)；发泡剂26份(其中异戊烷12份，HCFC-141b 16份)；水2.2份；泡沫稳定剂(赢创德固赛，B8481)0.5份。在保持外界环境温度为23±2℃、相对湿度＜70％的条件下，将各原料机械混合，搅拌均匀，得组分A。
(2)组分B的准备：取多苯基多亚甲基多异氰酸酯(Huntsman，5005)备用。
(3)混合注射：将组分A、组分B分别通过卸车泵打入储料罐，再分别用进料泵打入高压发泡机料罐内，两组分再分别经过过滤器、计量泵和高低压转换阀后在喷头位置充分混合，混合后的物料喷洒在下面层材料(铝箔，与下钢板接触)上，然后在其上覆盖上面层材料(铝箔，与上钢板接触)后，进入温度为60℃、线速度为25米/分的双履带机内，组份A和组分B的质量比为1:1.3。乳白时间为7秒，拉丝时间为21秒，自由发泡倍率为制品实际体积的1.8倍。
(4)层压固化：履带板沿导轨运动，带动上下钢板向前输送，并通过垫块调整上下履带板间的距离，从而控制上下钢板之间制品的厚度。
(5)铣边切割：泡沫塑料制品从双履带机出来后经过铣边装置，将宽度调整到合适尺寸后再进入盘锯切割机，盘锯横向移动切断制品，切断后进入后辊道。
(6)熟化包装：在辊道出口处晾板熟化、堆垛、包装，再送入仓库储存。
表3：实施例3的高压缩强度的硬质聚氨酯泡沫塑料的性能测试结果
Figure BDA0000963869650000052

Claims (6)

1.一种高压缩强度的硬质聚氨酯泡沫塑料，其特征在于：包括重量比为1:(1.2～2.5)的组分A和组分B；
组分A包括多元醇100份、催化剂1.5～5.0份、发泡剂15～30份、水1.5～3.0份和泡沫稳定剂0.5～4.0份，其中，100份多元醇由聚醚多元醇50～73份和聚酯多元醇27～50份组成，所述份数为重量份数；
组分B是多苯基多亚甲基多异氰酸酯；
聚醚多元醇的羟值为100～600mgKOH/g，粘度为500～10000mPa·s；聚酯多元醇的羟值为200～400mgKOH/g，粘度为2000～20000mPa·s；
发泡剂为HCFC-141b、HFC-245fa、HFC-365mfc、环戊烷、异戊烷、正戊烷、水或二氧化碳中的至少一种；
其特征在于：包括顺序相接的如下步骤：
(1)组分A的准备：将组分A的各原料混匀，得组分A；
(2)组分B的准备：取组分B备用；
(3)混合注射：将组分A、组分B分别打入高压发泡机料罐内，两组分分别经过过滤器、计量泵和高低压转换阀后在喷头位置充分混合，混合后的物料喷洒在下面层材料上，然后在所喷洒的物料上覆盖上面层材料，进入双履带机内；
(4)层压固化：履带板沿导轨运动，带动上下面层材料向前输送，并通过垫块调整上下履带板间的距离，从而控制上下面层材料之间泡沫塑料制品的厚度；
(5)铣边切割：泡沫塑料制品从双履带机出来后经过铣边装置，将宽度调整到合适尺寸后再进入盘锯切割机，盘锯横向移动切断制品，切断后的制品进入后辊道；
(6)熟化包装：在辊道出口处晾板熟化、堆垛、包装，即得；
步骤(3)中组分A、B混合后，乳白时间为6～30秒，拉丝时间为20～80秒，自由发泡倍率为制品实际体积的1.2～2倍；
步骤(3)中双履带机温度为50～80℃，线速度为3～60米/分。
2.如权利要求1所述的高压缩强度的硬质聚氨酯泡沫塑料，其特征在于：所述的组分A中还包括5～30份的阻燃剂，阻燃剂为磷酸三（2-氯丙基）酯、三（2-羧乙基）膦、三(2，3-二氯丙基)磷酸酯、甲基磷酸二甲酯、三聚氰胺、三羟甲基氧化膦、N,N-二(2-羟异丙基)氨甲基膦酸二乙酯、氢氧化铝、氢氧化镁、磷酸铵、聚磷酸铵或硼酸锌中的至少一种，所述份数为重量份数。
3.如权利要求1或2所述的高压缩强度的硬质聚氨酯泡沫塑料，其特征在于：催化剂为胺类催化剂和有机金属类催化剂任意配比的混合物。
4.如权利要求3所述的高压缩强度的硬质聚氨酯泡沫塑料，其特征在于：胺类催化剂为三乙醇胺、二甲基环己胺、三亚乙基二胺、三乙烯二胺、2,4,6-三（二甲氨基甲基）苯酚、1,3,5-三(二甲氨基丙基)对称六氢三嗪、羧酸盐或季铵盐中的至少一种；有机金属类催化剂为二丁基锡二月桂酸酯、辛酸亚锡或异辛酸钾-二丙二醇溶液中的至少一种。
5.如权利要求1或2所述的高压缩强度的硬质聚氨酯泡沫塑料，其特征在于：泡沫稳定剂为含Si-C结构的硅类表面活性剂。
6.如权利要求1或2所述的高压缩强度的硬质聚氨酯泡沫塑料，其特征在于：所述多苯基多亚甲基多异氰酸酯中的异氰酸酯基NCO的质量分数为30.0～32.0%。
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