CN105153391A - 用能源草沼渣制备可生物降解聚氨酯硬泡的方法 - Google Patents
用能源草沼渣制备可生物降解聚氨酯硬泡的方法 Download PDFInfo
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Abstract
本发明公开了一种用能源草沼渣制备可生物降解聚氨酯硬泡的方法,其是利用能源草沼气发酵后的沼渣为主要原料,先将能源草经沼气发酵、干燥、粉碎、烘干后制得能源草沼渣,然后通过油浴液化成多元醇,调pH值为7,将液化的多元醇与化工聚醚多元醇、匀泡剂、催化剂和水按一定比例调配,再与多异氰酸酯混合搅拌,发泡,制得所述可生物降解的聚氨酯硬泡,其表观密度为24~92Kg/m3,抗压强度为0.05~0.25MPa。本发明不仅降低了聚氨酯硬泡的生产成本,有效的处理了能源草沼气发酵的废弃物,实现了能源草沼渣的高值化利用;而且还可减少现有聚氨酯硬泡制备过程中对石油产品的依赖和产生的白色污染。
Description
技术领域
本发明属于高分子化学领域,具体涉及一种用能源草沼渣制备可生物降解聚氨酯硬泡的方法。
背景技术
聚氨酯是由聚物多元醇与异氰酸酯反应,扩链交链而成的一种介于塑料和橡胶之间的新型合成材料。目前,聚氨酯材料广泛应用于交通运输、冶金、建筑、轻工(造纸、制鞋、皮革)和医学等领域,其消费量也越来越大。
用于制备聚氨酯的多元醇大部分是以石化产品为原料制成。随着石油资源的日益枯竭和石油价格的不断上涨,人们积极寻求基于天然产物的聚醚多元醇以部分或者全部取代提取的聚醚多元醇。现有报道显示,植物油、淀粉、糖、单宁、甘蔗渣等物质都可用作制备植物多元醇的原料。如戈进杰等在专利号为98100914.X的中国发明专利中,用单宁与环氧丙烷等反应,制得一种新型的聚醚多元醇;谌凡更等在专利号为101429282.B的中国发明专利中,利用甘蔗渣制得聚醚多元醇。
能源草系指一类以禾本科植物为主,一年生或多年生的,高产量、高纤维素含量的能源植物。能源草作为一种可再生的生物质资源,在厌氧发酵生产沼气方面具有很大的发展前景,而产生的沼渣作为能源草沼气发酵的废弃物含有大量的木质素、纤维素和半纤维素,适用于植物纤维聚醚多元醇的生产。
发明内容
本发明的目的在于提供一种用能源草沼渣制备可生物降解聚氨酯硬泡的方法,其是利用能源草沼气发酵后的沼渣为主要原料制备植物基聚酯多元醇,以部分替代化工聚醚多元醇,从而制备出可生物降解的聚氨酯硬泡。
为实现上述目的,本发明采用如下技术方案:
一种用能源草沼渣制备可生物降解聚氨酯硬泡的方法,其包括如下步骤:
1)将生长2~8个月的能源草粉碎后进行沼气发酵;
2)将发酵后的能源草沼渣捞出,用水冲洗至清洗液基本澄清为止;
3)将步骤2)所得能源草沼渣干燥后进行粉碎,过30~60目样品筛;
4)将步骤4)所得能源草沼渣粉末烘干至恒重后,置于干燥皿中保存待用;
5)将80~120重量份的混合多元醇、2~6重量份的酸混合均匀,得到液化试剂;
6)将所得液化试剂加热至130~180℃,加入20~40重量份处理好的能源草沼渣,搅拌均匀,保温反应1.2~3h;
7)加入固体碱,调节反应体系的pH值至7,得液化多元醇;
8)将液化多元醇40~90重量份与聚醚多元醇10~60重量份、发泡剂10~30重量份、匀泡剂1~4重量份、催化剂1~5重量份和水1~3重量份搅拌混匀,再与100~200重量份的多异氰酸酯搅拌混匀,发泡,获得所述可生物降解的聚氨酯硬泡。
所述能源草为类芦、斑茅、芦苇、五节芒、象草、皇竹草、巨菌草、狼尾草、大米草、拟高粱、甜高粱、青贮玉米、香茅、互花米草中的一种或几种。
步骤1)所述沼气发酵的条件为34~42℃下发酵18~35天,或53~57℃下发酵8~16天。
步骤5)所述混合多元醇是按重量比1:1~4:1将聚乙二醇与乙二醇或丙三醇混合而成。
步骤5)所述的酸为硫酸或磷酸。
步骤7)所述固体碱为氢氧化钾、氢氧化钠或氧化镁。
步骤8)所述聚醚多元醇的羟值为350~760mgKOH/g,平均官能度在3~8之间,包括聚醚多元醇4110、聚醚多元醇405E、聚醚多元醇403、聚醚多元醇8205中的一种或两种;
所述发泡剂为HCFC-141b、二氯甲烷、HFC-245fa、环戊烷中任意的一种;
所述催化剂为三乙烯二胺、二月桂酸二丁基锡、环己基甲基叔胺,四甲基亚烷基二胺、辛酸亚锡、二乙酸二丁基锡中的任意两种;
所述匀泡剂为有机硅泡沫稳定剂。
本发明的显著优点在于:沼气发酵后的沼渣作为生产中的废弃物来源广泛、价格低廉,利用沼渣制备植物纤维基聚醚多元醇并合成聚氨酯硬泡,不仅降低了聚氨酯生产的成本,实现了资源的高效利用和附加值提升,还可减少对石油化工产品的依赖及白色污染;同时,本发明制备植物纤维基聚醚多元醇的液化时间短,残渣率低,所得硬质泡沫性能优良,具有突出的创新性和实际应用价值。
利用植物纤维基聚醚多元醇替代一部分化工聚醚多元醇合成的聚氨酯硬泡不仅性能良好而且更容易被降解。本发明在保证原料高转化率和产物高收率的前提下,制得具有较高相对分子质量和羟值的植物纤维基聚醚多元醇,再将其用于制备可生物降解的聚氨酯硬泡。其所得植物纤维基聚醚多元醇的残渣率在3%左右,粘度在1000~15000mPa·S,羟值在300~700mgKOH/g之间,合成的硬质泡沫的表观密度为24~92Kg/m3,抗压强度为0.05~0.25MPa。
具体实施方式
为了使本发明所述的内容更加便于理解,下面结合具体实施方式对本发明所述的技术方案做进一步的说明,但是本发明不仅限于此。
实施例1
1)将生长6个月的类芦、斑茅类芦、斑茅、芦苇于35℃左右沼气发酵35天;
2)将发酵后的沼渣捞出,用水冲洗至清洗液基本澄清为止;
3)再将所得物料干燥后进行粉碎,过30目样品筛;
4)将所得能源草沼渣粉末烘干至恒重,置于干燥皿中保存待用;
5)将60gPEG400与40g丙三醇混合制成混合多元醇,加入5g质量浓度为98%的浓硫酸,混合均匀得液化试剂;
6)将所得液化试剂转移到装有搅拌棒、分水器和温度计的250ml三口烧瓶中,加热至160℃后,加入35g预处理好的能源草沼渣,搅拌均匀,保温反应1.5h;
7)加入固体氢氧化钠,调节反应体系的pH值为7,得黑色粘稠的植物多元醇,其羟值约为360mgKOH/g;
8)将60g液化的多元醇与20g聚醚多元醇4110、20g聚醚多元醇403、10gHCFC-141b、2gSD-501、0.5g三乙烯二胺、1g二月桂酸二丁基锡和1.5g水搅拌混匀,再与100gPM200混匀,快速搅拌10s后发泡,得所述可生物降解聚氨酯硬泡。
实施例2
1)将生长2个月的狼尾草于55℃左右沼气发酵16天;
2)将发酵后的沼渣捞出,用水冲洗至清洗液基本澄清为止;
3)再将所得物料干燥后进行粉碎,过40目样品筛;
4)将所得能源草沼渣粉末烘干至恒重,置于干燥皿中保存待用;
5)将70gPEG400与30g乙二醇混合制成混合多元醇,加入2g质量浓度为98%的浓硫酸,混合均匀得液化试剂;
6)将所得液化试剂转移到装有搅拌棒、分水器和温度计的250ml三口烧瓶中,加热至130℃后,加入20g预处理好的能源草沼渣,搅拌均匀,保温反应3h;
7)加入固体氧化镁,调节反应体系的pH值为7,得黑色粘稠的植物多元醇,其羟值约为460mgKOH/g;
8)将40g液化的多元醇与10g聚醚多元醇8205、11g二氯甲烷、1g二甲基硅氧烷、0.5g环己基甲基叔胺、0.5g二乙酸二丁基锡和1g水搅拌混匀,再与134gPAPI混匀,快速搅拌12s后发泡,得所述可生物降解聚氨酯硬泡。
实施例3
1)将生长3个月的五节芒、7个月的巨菌草、3个月的青贮玉米于40℃左右沼气发酵18天;
2)将发酵后的沼渣捞出,用水冲洗至清洗液基本澄清为止;
3)再将所得物料干燥后进行粉碎,过60目样品筛;
4)将所得能源草沼渣粉末烘干至恒重,置于干燥皿中保存待用;
5)将96gPEG600与24g丙三醇混合制成混合多元醇,加入6g磷酸,混合均匀得液化试剂;
6)将所得液化试剂转移到装有搅拌棒、分水器和温度计的250ml三口烧瓶中,加热至180℃后,加入40g预处理好的能源草沼渣,搅拌均匀,保温反应1.2h;
7)加入固体氢氧化钾,调节反应体系的pH值为7,得黑色粘稠的植物多元醇,其羟值约为490mgKOH/g;
8)将90g液化的多元醇与30g聚醚多元醇405E、30g聚醚多元醇8205、30g环戊烷、4gSD-501、2g三乙烯二胺、3g辛酸亚锡和3g水搅拌混匀,再与200gPM200混匀,快速搅拌15s后发泡,得所述可生物降解聚氨酯硬泡。
将实施例3制得的可生物降解聚氨酯硬泡与传统化工聚氨酯泡沫进行性能对比,其结果见表1。
表1聚氨酯泡沫的性能对比
由表1可见,本发明可生物降解聚氨酯泡沫不仅具有化工聚氨酯泡沫的优良性能,而且具有更好的生物降解性能。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (7)
1.一种用能源草沼渣制备可生物降解聚氨酯硬泡的方法,其特征在于:包括如下步骤:
1)将生长2~8个月的能源草粉碎后进行沼气发酵;
2)将发酵后的能源草沼渣捞出,用水冲洗至清洗液基本澄清为止;
3)将步骤2)所得能源草沼渣干燥后进行粉碎,过30~60目样品筛;
4)将步骤4)所得能源草沼渣粉末烘干至恒重后,置于干燥皿中保存待用;
5)将80~120重量份的混合多元醇、2~6重量份的酸混合均匀,得到液化试剂;
6)将所得液化试剂加热至130~180℃,加入20~40重量份处理好的能源草沼渣,搅拌均匀,保温反应1.2~3h;
7)加入固体碱,调节反应体系的pH值至7,得液化多元醇;
8)将液化多元醇40~90重量份与聚醚多元醇10~60重量份、发泡剂10~30重量份、匀泡剂1~4重量份、催化剂1~5重量份和水1~3重量份搅拌混匀,再与100~200重量份的多异氰酸酯搅拌混匀,发泡,获得所述可生物降解的聚氨酯硬泡。
2.根据权利要求1所述用能源草沼渣制备可生物降解聚氨酯硬泡的方法,其特征在于:所述能源草为类芦、斑茅、芦苇、五节芒、象草、皇竹草、巨菌草、狼尾草、大米草、拟高粱、甜高粱、青贮玉米、香茅、互花米草中的一种或几种。
3.根据权利要求1所述用能源草沼渣制备可生物降解聚氨酯硬泡的方法,其特征在于:步骤1)所述沼气发酵的条件为34~42℃下发酵18~35天,或53~57℃下发酵8~16天。
4.根据权利要求1所述用能源草沼渣制备可生物降解聚氨酯硬泡的方法,其特征在于:步骤5)所述混合多元醇是按重量比1:1~4:1将聚乙二醇与乙二醇或丙三醇混合而成。
5.根据权利要求1所述用能源草沼渣制备可生物降解聚氨酯硬泡的方法,其特征在于:步骤5)所述的酸为硫酸或磷酸。
6.根据权利要求1所述用能源草沼渣制备可生物降解聚氨酯硬泡的方法,其特征在于:步骤7)所述固体碱为氢氧化钾、氢氧化钠或氧化镁。
7.根据权利要求1所述用能源草沼渣制备可生物降解聚氨酯硬泡的方法,其特征在于:步骤8)所述聚醚多元醇的羟值为350~760mgKOH/g,平均官能度在3~8之间,包括聚醚多元醇4110、聚醚多元醇405E、聚醚多元醇403、聚醚多元醇8205中的一种或两种;
所述发泡剂为HCFC-141b、二氯甲烷、HFC-245fa、环戊烷中任意的一种;
所述催化剂为三乙烯二胺、二月桂酸二丁基锡、环己基甲基叔胺,四甲基亚烷基二胺、辛酸亚锡、二乙酸二丁基锡中的任意两种;
所述匀泡剂为有机硅泡沫稳定剂。
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