CN109679325A - 多孔陶瓷用有机泡沫体及其制备方法 - Google Patents
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Abstract
本发明公开了一种多孔陶瓷用有机泡沫体,由聚醚、聚酯或者其他多元醇中的一种或多种与多异氰酸酯在催化剂、泡沫稳定剂、蛋白以及水体系中反应而成,其制备原料按照重量份计算包括:多元醇80~100份,多异氰酸酯40~50份,催化剂1~2份,泡沫稳定剂2~4份,水3‑5份。本发明采用聚醚、聚酯或者其他多元醇中的一种或多种与多异氰酸酯作为原料,在催化剂、泡沫稳定剂、蛋白体系中反应生成泡沫体,并在制备有机泡沫体时通过控制原料加入顺序和加入时间来控制泡沫体的成孔率和破孔率,尤其是蛋白的加入能够提高开孔的孔筋强度,同时增加孔筋的粗糙程度以提高有机泡沫体的亲水性能,使有机泡沫体挂浆性能良好。
Description
技术领域
本发明涉及一种有机泡沫体,尤其是涉及一种多孔陶瓷用有机泡沫体,同时涉及其制备方法。
背景技术
三维网状多孔陶瓷是一种具有高气孔率的陶瓷,气孔相互贯通,是一种重要的功能材料。因其具有均匀透过性、较大的比表面积、低密度、低热传导率以及耐高温、耐腐蚀等特性,作为一类新型陶瓷材料,已广泛应用于冶金、化工、环保、能源、生物等各个部门作为过滤、分离、布气、吸音、化工填料、生物陶瓷和催化剂载体等材料,例如熔融金属过滤、高温烟气处理,固体热交换器,催化剂载体,多孔燃烧器等。制备多孔陶瓷的制备方法有很多种,包括有机泡沫浸渍法、发泡法、溶胶凝胶法等。其中有机泡沫浸渍工艺是制备高气孔率(70-90%)多孔陶瓷的一种有效工艺,它凭借了有机泡沫体所具有的开孔三维网状骨架的特殊结构,将制备好的浆料均匀地涂覆在有机泡沫网状体上,干燥后烧掉有机泡沫体而获得一种网眼多孔陶瓷,并且此类多孔陶瓷具有开孔三维网状骨架结构,这种特殊结构使其作为过滤材料具有显著优点:(a)通过流体时,压力损失小;(b)表面积大和流体接触效率高;(c)重量轻。该类多孔陶瓷被用于流体过滤尤其是熔融金属过滤时,与传统使用的陶瓷颗粒烧结体、玻璃纤维布相比,不但操作简单、节省能源、降低成本,而且过滤效率较高。因此通过有机泡沫体浸渍工艺来制备多孔陶瓷是重要的多孔陶瓷制备方法。现有的有机泡沫体浸渍工艺需要提高有机泡沫体的挂浆性能,此外有机泡沫体本身的通孔率需要提高,制备有机泡沫体时应当减少泡沫网筋间的隔膜形成。
发明内容
为解决上述技术问题,本发明提供一种用于多孔陶瓷制备时能够提高浆料挂浆性能,且通孔率良好的有机泡沫体。
本发明的技术方案是提供一种多孔陶瓷用有机泡沫体,由聚醚、聚酯或者其他多元醇中的一种或多种与多异氰酸酯在催化剂、泡沫稳定剂、蛋白以及水体系中反应而成,其制备原料按照重量份计算包括:多元醇80~100份,多异氰酸酯40~50份,催化剂1~2份,泡沫稳定剂2~4份,水3-5份。
所述多元醇为聚氧烯烃类聚醚多元醇、己二酸聚酯多元醇、接枝聚合物多元醇、高活性聚醚多元醇、亲水性聚醚多元醇中的一种或多种。
所述多元醇为聚酯多元醇与聚醚多元醇的混合物,其中聚酯多元醇与聚醚多元醇的质量比为5~7:2。
所述催化剂为叔胺与有机金属化合物混合或者不同叔胺化合物混合的复合催化剂;当为叔胺与有机金属化合物混合时,叔胺与有机金属化合物的质量浓度比为2~5:1;当为不同叔胺化合物混合时,优选四甲基丁二胺和三亚乙基二胺以质量浓度比为2~3:1混合。
制备原料还包括开孔剂0.5~1.5份,所述开孔剂为石蜡、聚氧化乙烯、聚氧化乙烯-氧化丙烯共聚物、聚氧化烯烃-聚硅氧烷共聚物中的一种或者多种。
本发明还提供一种多孔陶瓷用有机泡沫体的制备方法,步骤包括:
S1.按照上述配比称取原料;
S2.将多元醇、催化剂、泡沫稳定剂,置于容器内,搅拌混合均匀,将多异氰酸酯和水依次倒入上述容器中,快速搅拌并将混合物加至发泡池内;
S3.待泡沫体发起并稳定后出模,熟化。
步骤S2中多异氰酸酯和水的加入时间相错1~10s,即多异氰酸酯先加入,经过1~10s后再加入水。
步骤S2中在加入多异氰酸酯后通入空气或者氮气作为助泡气。
步骤S2中在加入水后加入打发的蛋白,打发的蛋白体积与步骤S2中原料混合物的体积比为0.5~1:1。加入打发蛋白后,采用上下翻拌使蛋白充分融入混合物体系,并保持蛋白泡沫依旧成型,避免破坏蛋白泡沫。
本发明的优点和有益效果:采用聚醚、聚酯或者其他多元醇中的一种或多种与多异氰酸酯作为原料,在催化剂、泡沫稳定剂、蛋白体系中反应生成泡沫体,其中水能够作为链增长剂以及二氧化碳气泡的来源,催化剂促进反应体系中中间产物的链增长并且促进发泡以及聚合物形成凝胶体系,泡沫稳定剂能够使聚合物中产生的泡沫稳定,通过泡沫稳定剂还能控制泡沫的大小和孔径;打发的蛋白通入体系后由于其本身具有大量较细的气泡结构因此在发泡初期能够作为支撑进一步保证聚合物产生的泡沫稳定,此外蛋白的气泡结构脆性较大发泡后期随着聚合物气泡胀大,蛋白气泡随之破裂与聚合物气泡一起形成最终所需的开孔泡沫结构,此阶段蛋白气泡所受各向张力相对均匀因此聚合物开孔泡沫结构上附着的蛋白量较为均匀,而通过显微镜观察发现破裂后的蛋白液成粗糙颗粒状附着在开孔泡沫的孔筋上,一方面增大了聚合物开孔泡沫孔筋的孔筋粗度提高了孔筋的强度,另一方面增大了聚合物开孔泡沫孔筋的粗糙程度,而且蛋白具有较大的亲水性,在有机泡沫体熟化后能够改善泡沫体对多孔陶瓷浆料的亲和性从而提高有机泡沫体的挂浆性能。
附图说明
图1为本发明的多孔陶瓷用有机泡沫体的挂浆前后重量变化
具体实施方式
下面结合具体实施方式对本发明作进一步说明。
实施例1
按照如下重量份配比称取原料:官能度为3~4、相对分子量为5000~6000、伯羟基摩尔数在70~80%的高活性聚醚多元醇100份,其与水及多异氰酸酯的混溶性良好,反应活性适宜;甲苯二异氰酸酯40份,其中2,4-与2,6-异构体的质量比为80:20;催化剂1份,为三乙烯亚胺和辛酸亚锡以质量浓度比2:1混合的复合催化剂;有机硅泡沫稳定剂2份,水2份。
将高活性聚醚多元醇、三乙烯亚胺和辛酸亚锡复合催化剂、有机硅泡沫稳定剂加入容器内,搅拌混合均匀,将甲苯二异氰酸酯先倒入上述容器中后通入空气作为助泡气,经过5s后再将水倒入上述容器中,快速搅拌,然后加入此时混合物体积0.5倍的打发蛋白,上下翻拌,并将混合物倒入发泡池内;待泡沫体发起并稳定后出模,熟化。
实施例2
按照如下重量份配比称取原料:聚醚三醇90份,其官能度为2~3、相对分子量为4000~5000、由甘油(丙三醇)为起始剂并由1,2-环氧丙烷与环氧乙烷共聚而成;二苯基甲烷二异氰酸酯50份;催化剂2份,为双(二甲氨基乙基)醚和羧酸铋以质量浓度比5:1混合的复合催化剂;有机硅泡沫稳定剂4份,水3份。
将聚醚三醇、双(二甲氨基乙基)醚和羧酸铋复合催化剂、有机硅泡沫稳定剂加入容器内,搅拌混合均匀,将二苯基甲烷二异氰酸酯先倒入上述容器中后通入空气作为助泡气,经过3s后再将水倒入上述容器中,快速搅拌,然后加入此时混合物体积1倍的打发蛋白上下翻拌,并将混合物倒入发泡池内;待泡沫体发起并稳定后出模,熟化。
实施例3
按照如下重量份配比称取原料:乙烯基改性聚酯多元醇58份,其相对分子量为2000~3000,聚醚三醇29份,相对分子量为3000~3500;甲苯二异氰酸酯45份,其中2,4-与2,6-异构体的质量比为80:20;催化剂3份,为三亚乙基二胺和异辛酸锌以质量浓度比4:1混合的复合催化剂;有机硅泡沫稳定剂4份,聚氧化烯烃-聚硅氧烷共聚物0.5份,水4份。
将乙烯基改性聚酯多元醇、聚醚三醇、三亚乙基二胺和异辛酸锌复合催化剂、有机硅泡沫稳定剂、聚氧化烯烃-聚硅氧烷共聚物加入容器内,搅拌混合均匀,将甲苯二异氰酸酯先倒入上述容器中后通入空气作为助泡气,经过5s后再将水倒入上述容器中,快速搅拌,然后加入此时混合物体积0.5倍的打发蛋白上下翻拌,并将混合物倒入发泡池内;待泡沫体发起并稳定后出模,熟化。
实施例4
按照如下重量份配比称取原料:官能度为3~4、相对分子量为5000~6000、伯羟基摩尔数在70~80%的高活性聚醚多元醇95份,其与水及多异氰酸酯的混溶性良好,反应活性适宜;甲苯二异氰酸酯45份,其中2,4-与2,6-异构体的质量比为80:20;催化剂1.5份,为四甲基丁二胺和三亚乙基二胺以质量浓度比为3:1混合的复合催化剂;有机硅泡沫稳定剂2.5份,水3份。
将高活性聚醚多元醇、四甲基丁二胺和三亚乙基二胺复合催化剂、有机硅泡沫稳定剂加入容器内,搅拌混合均匀,将甲苯二异氰酸酯先倒入上述容器中后通入空气作为助泡气,经过5s后再将水倒入上述容器中,快速搅拌,然后加入此时混合物体积0.8倍的打发蛋白上下翻拌,并将混合物倒入发泡池内;待泡沫体发起并稳定后出模,熟化。
本发明的多孔陶瓷用有机泡沫体性能测试结果如下:
由上表可知,本发明产品总体上来说密度较低,单位长度上的开孔数量高,同时具有一定的压缩强度和拉伸强度能够满足多孔陶瓷挂浆支撑要求。且由图1可知本发明的多孔陶瓷用有机泡沫体的挂浆前后的增重明显,而且堵孔率较低,说明对浆料的亲和力强,能够制成孔隙率较高的多孔陶瓷载体。
本发明实施例涉及到的材料、试剂和实验设备,如无特别说明,均为符合塑料发泡领域的市售产品。
以上所述,仅为本发明的优选实施例,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明的核心技术的前提下,还可以做出改进和润饰,这些改进和润饰也应属于本发明的专利保护范围。与本发明的权利要求书相当的含义和范围内的任何改变,都应认为是包括在权利要求书的范围内。
Claims (10)
1.一种多孔陶瓷用有机泡沫体,由多元醇与多异氰酸酯在催化剂、泡沫稳定剂、蛋白以及水体系中反应而成,其主要制备原料按照重量份计算包括:多元醇80~100份,多异氰酸酯40~50份,催化剂1~2份,泡沫稳定剂2~4份,水3-5份。
2.根据权利要求1所述的多孔陶瓷用有机泡沫体,其特征在于,所述多元醇为聚氧烯烃类聚醚多元醇、己二酸聚酯多元醇、接枝聚合物多元醇、高活性聚醚多元醇、亲水性聚醚多元醇中的一种或多种。
3.根据权利要求1所述的多孔陶瓷用有机泡沫体,其特征在于,所述多元醇为聚酯多元醇与聚醚多元醇的混合物,其中聚酯多元醇与聚醚多元醇的质量比为5~7:2。
4.根据权利要求1所述的多孔陶瓷用有机泡沫体,其特征在于,所述催化剂为叔胺与有机金属化合物混合的复合催化剂,并且叔胺与有机金属化合物的质量浓度比为2~5:1。
5.根据权利要求1所述的多孔陶瓷用有机泡沫体,其特征在于,所述催化剂为四甲基丁二胺和三亚乙基二胺以质量浓度比为2~3:1混合的复合催化剂。
6.根据权利要求1所述的多孔陶瓷用有机泡沫体,其特征在于,制备原料包括开孔剂0.5~1.5份,所述开孔剂为石蜡、聚氧化乙烯、聚氧化乙烯-氧化丙烯共聚物、聚氧化烯烃-聚硅氧烷共聚物中的一种或者多种。
7.权利要求1所述的多孔陶瓷用有机泡沫体的制备方法,步骤包括:
S1.按照上述配比称取原料;
S2.将多元醇、催化剂、泡沫稳定剂,置于容器内,搅拌混合均匀,将多异氰酸酯和水依次倒入上述容器中,快速搅拌并将混合物加至发泡池内;
S3.待泡沫体发起并稳定后出模,熟化。
8.根据权利要求7所述的多孔陶瓷用有机泡沫体的制备方法,其特征在于,所述步骤S2中先加入多异氰酸酯,经过1~10s后再加入水。
9.根据权利要求7所述的多孔陶瓷用有机泡沫体的制备方法,其特征在于,所述步骤S2中在加入多异氰酸酯后通入空气或者氮气作为助泡气。
10.根据权利要求7所述的多孔陶瓷用有机泡沫体的制备方法,其特征在于,所述步骤S2中在加入水后还包括加入打发的蛋白,打发的蛋白体积与步骤S2中的原料混合物体积比为0.5~1:1;加入打发的蛋白后,采用上下翻拌使蛋白充分融入混合物体系。
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