CN113717374A - 一种生物基阻燃聚醚多元醇的制备方法及用途 - Google Patents
一种生物基阻燃聚醚多元醇的制备方法及用途 Download PDFInfo
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Abstract
本发明公开了一种生物基阻燃聚醚多元醇的制备方法，以玉米淀粉或麦芽糊精等为原料，磷酸硼为催化剂和阻燃剂，环氧大豆油和丙三醇混合物为液化剂，通过水热反应进行液化来制备生物基阻燃聚醚多元醇，在适宜的条件下，原料的液化率高达96.8%,羟值400.7‑453.3mgKOH/g，粘度680±20mPa•s，用此多元醇制备的聚氨酯泡沫，极限氧指数可达30.5，材料达到离火自熄，其他性能指标优于国家标准（GBT8813‑2008、GBT6343‑2009）标准的质量要求。
Description
技术领域
本发明涉及化工新材料及生物质高质化利用技术领域,具体涉及一种淀粉或麦芽糊精阻燃聚醚多元醇的制备方法。
背景技术
聚氨酯是目前应用广泛的第五大高分子材料，由多元醇与异氰酸酯缩聚而成，2020年我国聚氨酯材料的产量已近2200万吨，随着材料使用量的不断增大，目前我国废旧聚氨酯产品（制冷保温领域的聚氨酯保温材料）和材料加工中下角料（一般约为制品质量的5~10%）的数量不断增大，目前除少部分直接利用外（约10%），绝大部分通过焚烧进行处理，带来了严重的资源浪费及环境污染问题；另外由于密度低，质量轻及不可降解性，造成了产品报废后的运输及后处理需要较高的费用支出（4000元/吨）。因此开发可降解性聚氨酯材料就成为上述问题解决的关键措施。并且由于聚氨酯本身属于易燃材料，随着对材料使用安全性要求的不断提高，因此阻燃聚氨酯材料更是市场应用的亟需产品。
目前聚氨酯泡沫材料的阻燃主要通过两种方式来实现：1）使用反应型阻燃剂和具有阻燃性质的聚醚多元醇，使多元醇与异氰酸酯及反应型阻燃剂进行反应，从而将起阻燃作用的氯、溴、磷、氮等原子直接接到聚氨酯泡沫的高分子链上，成为PU分子的一部分，赋予材料阻燃性能。2）添加型阻燃聚氨酯，含有氯、溴、磷、氮、铝等阻燃元素的阻燃剂，不与多元醇及异氰酸酯进行反应，以细小粉末的形式分散在体系中，含有这些元素的物质能够延缓燃烧、抑制烟气甚至使火焰自熄。添加型阻燃一般需要较高的阻燃剂添加量（40%），因此对目标材料的综合性能影响较大，因此反应型阻燃成为业界推崇的产品。
多元醇是合成聚氨酯泡沫材料两大主要原料之一，目前广泛使用的多元醇原料均来自石化原料，不具备可降解性，因此为推动聚氨酯行业的可持续性发展，开发生物基多元醇用于制备生物基聚氨酯材料与产品，已成为聚氨酯行业的未来发展方向。在聚氨酯泡沫材料领域，对生物质的利用研究主要集中在淀粉、植物油、木质素、木材和农作物废弃物等，主要有两种方式：（1）将生物质通过一系列的反应制成分子链段上带有多个羟基的液化多元醇，用作后续聚氨酯泡沫材料生产的多元醇原料；（2）将生物质粉末化，用作聚氨酯泡沫材料的改性填料。但这两种多元醇制备的泡沫不具备阻燃性，仍需进行阻燃改性才可达到阻燃产品性能要求。
张立强用制备的环氧甘油醇解蓖麻油与磷酸二乙酯，甲苯作溶剂，三苯基膦为催化剂条件下，合成了蓖麻油磷酸酯阻燃多元醇；并用制备的蓖麻油磷酸酯阻燃多元醇和甘油醇解蓖麻油多元醇与磷酸三乙酯（TEP）和膨胀石墨（EG）制备了生物基阻燃聚氨酯泡沫，蓖麻油基阻燃聚氨酯泡沫的氧指数达29.7%。（张立强. 蓖麻油基磷酸酯阻燃多元醇的合成及聚氨酯泡沫的制备[D].中国林业科学研究院,2014.）。
发明内容
针对上述存在的问题，本发明采用具有阻燃功效的环保磷酸硼作催化剂，在反应釜中直接催化液化生物质原料，所得的生物质基阻燃聚醚多元醇满足制备阻燃硬质聚氨酯保温材料的要求。为了实现上述目的，本发明采用以下的技术方案：
将淀粉或麦芽糊精、环氧大豆油、丙三醇和磷酸硼，按照设计好的比例依次加入到高压反应釜中，在120-160℃温度下反应1-5h，得生物基阻燃聚醚多元醇。
优选的，所述液化剂为质量比为5：5的环氧大豆油与丙三醇的混合物，液化剂与淀粉或麦芽糊精原料的质量比为2-7：1，优选为2.5-3.5：1。
液化反应温度为120-160℃，优选为130-150℃。
催化剂为磷酸硼，其添加量为液化剂质量的10.0-20.0%，优选15.0-18.0%。
由于采用上述的技术方案,本发明的有益效果是：
1）设计采用具有催化阻燃双重功能的磷酸硼用于产品的一步合成，催化剂不需要回收，因此工艺过程简单，易于实现工业化生产；同时磷酸硼的制备工艺简单、生产成本低、属于环保阻燃剂产品。
2）本发明采用的玉米淀粉、麦芽糊精、环氧大豆油及植物基甘油均属于生物质原料，赋予产品优良的生物可降解性。
3）本发明采用催化溶剂热法,以磷酸硼为催化剂，催化效果优异，避免了使用硫酸带来的腐蚀及副反应问题，不需脱除催化剂，过程工艺清洁。无腐蚀及环境负效应。
4）优异的产品综合性能：所制备的生物基阻燃聚醚多元醇可以直接用于制备阻燃聚氨酯泡沫，在无外加阻燃剂的条件下，表现出优异的阻燃性能，极限氧指数最高达30.5%；泡沫的其他性能指标为：压缩强度0.26-0.38MPa，平均表观密度为50-58kg/m3,导热系数为0.016—0.026W/m•K。均优于阻燃硬质聚氨酯保温材料的使用要求。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述。基于本发明的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1.
称取50.0g玉米淀粉、100.0g环氧大豆油、100.0g植物基丙三醇和10.0g磷酸硼在500mL容器中混合均匀，倒入磁力驱动反应釜中，在140℃条件下反应3h，经过减压蒸馏除水得阻燃聚醚多元醇P1，经测定玉米淀粉的液化率88.5%，羟值为400.7mgKOH/g，粘度683mPa·s。
实施例2.
称取50.0g玉米淀粉、75.0g环氧大豆油、75.0g丙三醇和20.0g磷酸硼在500mL容器中混合均匀，倒入磁力驱动反应釜中，在转速600r/min，140℃条件下反应3h，经过减压蒸馏除水得阻燃聚醚多元醇P2，经测定玉米淀粉的液化率92.3%，羟值为425.2mgKOH/g，粘度691mPa·s。
实施例3.
称取50.0g麦芽糊精、62.5g环氧大豆油、62.5g丙三醇和30.0g磷酸硼在500mL容器中混合均匀，倒入磁力驱动反应釜中，在转速600r/min，140℃条件下反应2h，经过减压蒸馏除水得阻燃聚醚多元醇P3，经测定麦芽糊精的液化率96.8%，羟值为453.3mgKOH/g，粘度690mPa·s。
实施例4.
称取50.0g玉米淀粉、125.0g环氧大豆油、125.0g丙三醇和40.0g磷酸硼在500mL容器中混合均匀，倒入磁力驱动反应釜中，在转速600r/min，150℃条件下反应3h，经过减压蒸馏除水得阻燃聚醚多元醇P4，经测定玉米淀粉的液化率95.5%，羟值为448.7mgKOH/g，粘度688mPa·s。
实施例5.由液化产物制备硬质聚氨酯泡沫材料的综合性能
分别称取20.0g实施例1-4的液化产物制备聚氨酯泡沫记为P1、P2、P3、P4，0.3g硅油L-580，催化剂二月桂酸二丁基锡0.016g，于500mL烧杯中混合均匀，向其中加入30.0gMDI，充分搅拌待体系均匀且有泡沫上升时停止搅拌，让其室温下自由发泡，待泡沫固化后得到阻燃硬质聚氨酯泡沫。经测定所得阻燃聚氨酯硬质泡沫压缩强度为0.26-0.38MPa, 平均表观密度为50-58kg/m3,导热系数为0.016—0.026W/m•K，泡沫的极限氧指数为23.5~30.5。表明利用液化产物制备的阻硬质聚氨酯泡沫的性能符合国家标准（GB/T6343-2009和GB/T8813-2008）的要求，阻燃性达到离火自熄。
表1.不同实施例制备的阻燃聚氨酯泡沫的力学及阻燃性能
实施例6.由本发明多元醇制备的阻燃聚氨酯泡沫的可降解性能
本发明采用土埋法测试聚氨酯泡沫的生物降解性能，具体步骤如下：制备0.15mm的聚氨酯泡沫薄片，将此薄片掩埋于土壤中，4~5周内，泡沫薄片会被微生物降解率超过60%以上，证明所合成的生物基聚氨酯泡沫具有优良的降解性能。
表2.不同实施例制备的阻燃聚氨酯泡沫的降解性能指标
以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。
Claims (7)
1.一种生物基阻燃聚醚多元醇的制备方法，以玉米淀粉或麦芽糊精等为原料，磷酸硼为催化剂和阻燃剂，环氧大豆油和丙三醇混合物为液化剂，通过水热反应进行液化来制备生物基阻燃聚醚多元醇;具体步骤如下：分别称取50.0g玉米淀粉或麦芽糊精，2-7倍质量的环氧大豆油和丙三醇作液化剂、液化剂质量10-20%的磷酸硼在500mL的容器中搅拌均匀倒入反应釜中，在120-160℃下反应1-5h，液化完成后将液化产物过滤，固体残渣收集后用作下次反应的原料；液化产物进行减压蒸馏除水，即得生物基阻燃聚醚多元醇。
2.根据权利要求1所述的一种生物基阻燃聚醚多元醇的制备方法，其特征在于，所述的催化剂磷酸硼既作为反应的催化剂，同时又作为产品的阻燃成份，其用量为原料总质量的10-20%, 其可通过液相沉淀法、微波法及水热法制备。
3.根据权利要求1所述的一种生物基阻燃聚醚多元醇的制备方法，其特征在于：所述液化剂为质量比为5：5的环氧大豆油和丙三醇的混合物，液化剂与淀粉或麦芽糊精的质量比为2-7：1。
4.根据权利要求1所述的一种生物基阻燃聚醚多元醇的制备方法，其特征在于：催化液化反应温度为120-160℃。
5.根据权利要求1所述的一种生物基阻燃聚醚多元醇的制备方法，其特征在于：催化液化反应时间为1-5h。
6.根据权利要求1所述的一种生物基阻燃聚醚多元醇的制备方法,催化剂溶于反应体系中，并具有阻燃功能, 不需要通过中和或其他方式脱除催化剂。
7.根据权利要求1-6任一项所述的一种生物基阻燃聚醚多元醇的应用,其特征在于：适用于阻燃硬质聚氨酯保温材料的制备，其所制备的聚氨酯材料可达到离火自熄的阻燃性能。
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