CN114381111A - 戊烷型多组分高阻燃聚氨酯复合酚醛连续板组合料及其制备方法 - Google Patents

戊烷型多组分高阻燃聚氨酯复合酚醛连续板组合料及其制备方法 Download PDF

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CN114381111A
CN114381111A CN202111441692.XA CN202111441692A CN114381111A CN 114381111 A CN114381111 A CN 114381111A CN 202111441692 A CN202111441692 A CN 202111441692A CN 114381111 A CN114381111 A CN 114381111A
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flame
phenolic
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pentane
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白维坤
殷晓峰
李金伟
刘继红
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Shandong Inov New Material Co Ltd
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Abstract

本发明涉及一种戊烷型多组分高阻燃聚氨酯复合酚醛连续板组合料及其制备方法，属于聚氨酯复合改性技术领域。本发明所述的戊烷型多组分高阻燃聚氨酯复合酚醛连续板组合料，包括A组分、B组分、C组分、D组分，其中：A组分包括聚醚、聚酯、酚醛树脂、匀泡剂、水、阻燃剂和胺类催化剂；B组分包括钾盐类催化剂、酚醛固化剂和小分子交联剂；C组分为戊烷发泡剂；D组分为异氰酸酯。本发明制备的连续板具有优异的阻燃性能和韧性，显著降低了成本；同时本发明提供了一种简单便捷、易于工业化生产的制备方法。

Description

戊烷型多组分高阻燃聚氨酯复合酚醛连续板组合料及其制备 方法
技术领域
本发明涉及一种戊烷型多组分高阻燃聚氨酯复合酚醛连续板组合料及其制备方法，属于聚氨酯复合改性技术领域。
背景技术
传统的聚氨酯硬泡具有质轻、低密度、高强度、低导热系数等优点，但现有技术条件存在许多不足，比如聚氨酯泡沫价格高、塑料易燃，耐热性差，并且燃烧后会产生有毒烟雾，这一点严重制约了聚氨酯保温材料的应用及广泛推广，由此越来越多的研究人员针对性开发具有较强阻燃性能聚氨酯保温材料。随着环保形势的压力，聚氨酯硬泡的发泡剂替代正在向着无氟环保、导热系数低的方向进行，戊烷是国际上公认的HCFC-141B的替代品。
酚醛树脂由酚类化合物与醛类化合物缩聚而成。酚醛泡沫是一种新型难燃、防火低烟的保温材料，它是由酚醛树脂加入发泡剂、固化剂及其它助剂制成的闭孔硬质泡沫塑料。酚醛保温材料具有较多优势：耐热、耐燃，可自熄，不会产生有毒烟雾，具有极佳的防火性能；制品尺寸稳定性好，不会出现收缩、变形；原料价格便宜；化学稳定性好，耐酸性强等。酚醛泡沫也有严重的缺点：物理性能不理想，整体的粘结性不好，抗压抗折能力极低；酚醛本身很脆，易粉化，不大适应于外墙，还需再加工，施工损耗比较大。
CN106496540A公开了一种用于阻燃型聚氨酯硬质泡沫塑料的酚醛聚醚多元醇的合成方法，并应用到聚氨酯硬泡中，能够提高泡沫的氧指数，使其具有阻燃的性能，该技术引入酚醛结构至聚醚多元醇中，然后再用于聚氨酯产品中，制备过程繁琐、工艺复杂、技术要求较高，现实推广困难；CN105218782B公开了一种可膨胀石墨改性高阻燃聚氨酯硬泡的制备方法，通过复配石墨等提高了聚氨酯硬泡的氧指数，燃烧性能可达到不燃级，该技术通过复配石墨的方式提高聚氨酯制品的阻燃性，但是膨胀石墨为固体颗粒，现实使用时会影响制品的流动性、降低产品其他性能，存在很多局限性。
酚醛保温泡沫已经大规模应用于工业建筑保温领域，且产品阻燃性能优良、价格低廉，缺点是泡沫偏脆、易粉化；而聚氨酯保温泡沫也已经大规模应用于工业建筑保温领域，通过添加阻燃剂提高产品阻燃性，成本较高。
发明内容
本发明的目的是克服现有技术的不足，提供一种戊烷型多组分高阻燃聚氨酯复合酚醛连续板组合料，用其制备的连续板具有优异的阻燃性能和韧性，显著降低了成本；同时本发明提供了一种简单便捷、易于工业化生产的制备方法。
本发明所述的戊烷型多组分高阻燃聚氨酯复合酚醛连续板组合料，包括A组分、B组分、C组分、D组分，其中：
A组分包括聚醚、聚酯、酚醛树脂、匀泡剂、水、阻燃剂和胺类催化剂；
B组分包括钾盐类催化剂、酚醛固化剂和小分子交联剂；
C组分为戊烷发泡剂；
D组分为异氰酸酯。
优选的，聚醚为蔗糖硬泡聚醚，官能度为3-5，羟值为200-500mgKOH/g。
所述聚酯为常规苯酐聚酯，优选为含有阻燃元素的苯酐聚酯，羟值为150-300mgKOH/g。
所述酚醛树脂为为规热固性酚醛树脂，优选为线型甲醛苯酚共聚物。
优选的，匀泡剂为Si-C型硬泡聚氨酯硅油；阻燃剂为TCPP、TCEP或TE中的一种或多种；胺类催化剂为环己胺、苄胺或三乙烯二胺中的一种或多种。
优选的，A组分包括以下质量份数的原料：
聚醚0-20份，聚酯40-60份，酚醛树脂10-20份，匀泡剂1.0-2.0份，水0.1-1.0份，阻燃剂10-30份，胺类催化剂0.5-2.5份。
优选的，钾盐类催化剂为乙酸钾或异辛酸钾中的一种或两种；酚醛固化剂为甲酸、乙酸或磷酸中的一种或多种；小分子交联剂为乙二醇、二乙二醇或三乙二醇中的一种或多种。
优选的，组分B中，钾盐类催化剂、酚醛固化剂、小分子交联剂的质量之比为5-30：5-30：0-50。
优选的，戊烷发泡剂为正戊烷、异戊烷或环戊烷中的一种或多种；异氰酸酯为多异氰酸酯，为市售常规聚合MDI，为含有一定量较高官能度的异氰酸酯与二苯基甲烷二异氰酸酯的混合物。例如万华PM200、巴斯夫M20S、科思创44v20等，聚合MDI官能度约2.5-3。
所述的戊烷型多组分高阻燃聚氨酯复合酚醛连续板组合料的制备方法，包括以下步骤：
(1)将聚醚、聚酯、酚醛树脂、匀泡剂、水、阻燃剂和胺类催化剂混合搅拌，得到A组分；
(2)将钾盐类催化剂、酚醛固化剂和小分子交联剂混合搅拌，得到B组分；
(3)使用时，将A组分、B组分、C组分、D组分按质量比100：1～6：3～20：100～200混合反应，酚醛可以与异氰酸酯反应，同时可以在固化剂的作用下自身固化为泡沫结构；聚醚、聚酯与异氰酸酯反应为PU泡沫结构；异氰酸酯自身在三聚催化剂的作用下反应得到PIR泡沫结构，最终制得所述的戊烷型多组分高阻燃聚氨酯复合酚醛连续板。
酚醛保温板是以酚醛树脂和阻燃剂、抑烟剂、固化剂、发泡剂、及其它助剂等多种物质，经科学配方制成的闭孔型硬质泡沫塑料。最突出的优势是防火和保温。本发明采用聚氨酯复合酚醛树脂的方式，通过使用特殊固化剂，解决了酚醛在聚氨酯中的固化问题，该添加剂同时还是聚氨酯反应的特种催化剂，保证了酚醛在复合材料中既可以与异氰酸酯反应、又可以自身固化成泡沫结构，大大提高了产品的综合性能，使聚氨酯复合酚醛泡沫成本低、阻燃效果好、固化后强度高、韧性优良、尺寸稳定性优异。
本发明与现有技术相比，具有以下有益效果：
(1)本发明通过多组分配方、连续线混合发泡，成功使得聚氨酯与酚醛泡沫均匀复合在一起，达到了优良性能；
(2)本发明通过一步法使聚氨酯与酚醛泡沫成功复合反应到一起，解决戊烷型聚氨酯板材的阻燃问题、降低聚氨酯板材成本，同时解决酚醛保温材料的脆性问题，提高产品韧性；
(3)本发明提供的制备方法简单便捷、能耗低，且易于大规模工业化生产。
具体实施方式
以下结合实施例对本发明作进一步描述。
对比例1
步骤一、A组分的制备：将40份4110聚醚多元醇、60份苯酐聚酯、2份硬泡硅油匀泡剂、1.0份水、30份阻燃剂、2份叔胺胺类催化剂按配比搅拌均匀，得到A组分。
步骤二、B组分的制备：将3份醋酸钾催化剂、3份甲酸固化剂、3份乙二醇等按配比搅拌均匀，得到B组分。
步骤三、取15份环戊烷作为C组分；取251份异氰酸酯(万华产品PM200)作为D组分。
步骤四、将A组分、B组分、C组分、D组分按质量比135:3:15:251混合均匀，倒入30cm*30cm*10cm的方形模具中进行反应，得到样块1。
对比例2
步骤一、A组分的制备：将40份4110聚醚多元醇、30份苯酐聚酯、30份酚醛树脂、2份硬泡硅油匀泡剂、1.0份水、30份阻燃剂、2份叔胺胺类催化剂按配比搅拌均匀，得到A组分。
步骤二、B组分的制备：将3份醋酸钾催化剂、3份乙二醇等按配比搅拌均匀，得到B组分。
步骤三、取15份环戊烷作为C组分；取251份异氰酸酯(万华产品PM200)作为D组分。
步骤四、将A组分、B组分、C组分、D组分按质量比135:3:15:251混合均匀，倒入30cm*30cm*10cm的方形模具中进行反应，得到样块2。
实施例1
步骤一、A组分的制备：将40份4110聚醚多元醇、30份苯酐聚酯、30份酚醛树脂、2份硬泡硅油匀泡剂、1.0份水、30份阻燃剂、2份叔胺胺类催化剂按配比搅拌均匀，得到A组分。
步骤二、B组分的制备：将3份醋酸钾催化剂、3份甲酸固化剂、3份乙二醇等按配比搅拌均匀，得到B组分。
步骤三、取15份环戊烷作为C组分；取251份异氰酸酯(万华产品PM200)作为D组分。
步骤四、将A组分、B组分、C组分、D组分按质量比135:3:15:251混合均匀，倒入30cm*30cm*10cm的方形模具中进行反应，得到样块3。
实施例2
步骤一、A组分的制备：将40份4110聚醚多元醇、20份苯酐聚酯、40份酚醛树脂、2份硬泡硅油匀泡剂、1.0份水、30份阻燃剂、2份叔胺胺类催化剂按配比搅拌均匀，得到A组分。
步骤二、B组分的制备：将3份醋酸钾催化剂、4份甲酸固化剂、3份乙二醇等按配比搅拌均匀，得到B组分。
步骤三、取15份环戊烷作为C组分；取251份异氰酸酯(万华产品PM200)作为D组分。
步骤四、将A组分、B组分、C组分、D组分按质量比135:3:15:251混合均匀，倒入30cm*30cm*10cm的方形模具中进行反应，得到样块4。
实施例3
步骤一、A组分的制备：将40份4110聚醚多元醇、10份苯酐聚酯、50份酚醛树脂、2份硬泡硅油匀泡剂、1.0份水、30份阻燃剂、2份叔胺胺类催化剂按配比搅拌均匀，得到A组分。
步骤二、B组分的制备：将3份醋酸钾催化剂、5份甲酸固化剂、3份乙二醇等按配比搅拌均匀，得到B组分。
步骤三、取15份环戊烷作为C组分；取251份异氰酸酯(万华产品PM200)作为D组分。
步骤四、将A组分、B组分、C组分、D组分混合按质量比135:3:15:251混合均匀，倒入30cm*30cm*10cm的方形模具中进行反应，得到样块5。
实施例4
步骤一、A组分的制备：将40份4110聚醚多元醇、60份酚醛树脂、2份硬泡硅油匀泡剂、1.0份水、30份阻燃剂、2份叔胺胺类催化剂按配比搅拌均匀，得到A组分。
步骤二、B组分的制备：将3份醋酸钾催化剂、6份甲酸固化剂、3份乙二醇等按配比搅拌均匀，得到B组分。
步骤三、取15份环戊烷作为C组分；取251份异氰酸酯(万华产品PM200)作为D组分。
步骤四、将A组分、B组分、C组分、D组分按质量比135:3:15:251混合均匀，倒入30cm*30cm*10cm的方形模具中进行反应，得到样块6。
产品强度、氧指数、尺寸变化率测试：
对制备的样块分别测试氧指数和压缩强度。
氧指数测试参考国标：GBT24093塑料燃烧性能测试方法氧指数法测试标准；
压缩强度测试参考国标：GB/T 8813-2008硬质泡沫塑料压缩性能的测定；
尺寸变化率测试方式为：样块置于0.1MPa的恒压设备30min，测试样块前后体积变化。
检测结果如下表1所示：
表1 样块压缩强度及氧指数数据
Figure BDA0003383595130000051
对比例1由于未加酚醛，产品压缩强度较低、尺寸稳定性较差，氧指数低；对比例2虽然添加了酚醛，但是未添加固化剂，到时无法形成有效泡沫；实施例1、2、3、4，考察了酚醛树脂添加量对体系的影响，实施例2号产品综合性能最好，得到了理想的结果。
结合上述数据可知，本发明制备的戊烷型多组分高阻燃聚氨酯复合酚醛保温板在阻燃性及泡沫强度方面达到理想效果，适合大规模生产和应用。
应指出的是上述实例仅作为说明本发明的技术思路和特点，其目的在于其他人能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明思路实质所做的等效变化或完善，都应该涵盖在本发明的保护范围之内。

Claims (10)

1.一种戊烷型多组分高阻燃聚氨酯复合酚醛连续板组合料，其特征在于：包括A组分、B组分、C组分、D组分，其中：
A组分包括聚醚、聚酯、酚醛树脂、匀泡剂、水、阻燃剂和胺类催化剂；
B组分包括钾盐类催化剂、酚醛固化剂和小分子交联剂；
C组分为戊烷发泡剂；
D组分为异氰酸酯。
2.根据权利要求1所述的戊烷型多组分高阻燃聚氨酯复合酚醛连续板组合料，其特征在于：聚醚为蔗糖硬泡聚醚，官能度为3-5，羟值为200-500mgKOH/g。
3.根据权利要求1所述的戊烷型多组分高阻燃聚氨酯复合酚醛连续板组合料，其特征在于：聚酯为含有阻燃元素的苯酐聚酯，羟值为150-300mgKOH/g。
4.根据权利要求1所述的戊烷型多组分高阻燃聚氨酯复合酚醛连续板组合料，其特征在于：酚醛树脂为线型甲醛苯酚共聚物。
5.根据权利要求1所述的戊烷型多组分高阻燃聚氨酯复合酚醛连续板组合料，其特征在于：匀泡剂为Si-C型硬泡聚氨酯硅油；阻燃剂为TCPP、TCEP或TE中的一种或多种；胺类催化剂为环己胺、苄胺或三乙烯二胺中的一种或多种。
6.根据权利要求1所述的戊烷型多组分高阻燃聚氨酯复合酚醛连续板组合料，其特征在于：A组分包括以下质量份数的原料：
聚醚0-20份，聚酯40-60份，酚醛树脂10-20份，匀泡剂1.0-2.0份，水0.1-1.0份，阻燃剂10-30份，胺类催化剂0.5-2.5份。
7.根据权利要求1所述的戊烷型多组分高阻燃聚氨酯复合酚醛连续板组合料，其特征在于：钾盐类催化剂为乙酸钾或异辛酸钾中的一种或两种；酚醛固化剂为甲酸、乙酸或磷酸中的一种或多种；小分子交联剂为乙二醇、二乙二醇或三乙二醇中的一种或多种。
8.根据权利要求1所述的戊烷型多组分高阻燃聚氨酯复合酚醛连续板组合料，其特征在于：组分B中，钾盐类催化剂、酚醛固化剂、小分子交联剂的质量之比为5-30：5-30：0-50。
9.根据权利要求1所述的戊烷型多组分高阻燃聚氨酯复合酚醛连续板组合料，其特征在于：戊烷发泡剂为正戊烷、异戊烷或环戊烷中的一种或多种；异氰酸酯官能度为2.5-3，为异氰酸酯与二苯基甲烷二异氰酸酯的混合物。
10.一种权利要求1-9任一所述的戊烷型多组分高阻燃聚氨酯复合酚醛连续板组合料的制备方法，其特征在于：包括以下步骤：
(1)将聚醚、聚酯、酚醛树脂、匀泡剂、水、阻燃剂和胺类催化剂混合搅拌，得到A组分；
(2)将钾盐类催化剂、酚醛固化剂和小分子交联剂混合搅拌，得到B组分；
(3)使用时，将A组分、B组分、C组分、D组分按质量比100：1～6：3～20：100～200混合反应，制得所述的戊烷型多组分高阻燃聚氨酯复合酚醛连续板。
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