CN105037672B - 一种异氰酸酯微孔聚合物材料及其制备方法与应用 - Google Patents
一种异氰酸酯微孔聚合物材料及其制备方法与应用 Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 16
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 8
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- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical group C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 28
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- NXHXNTAEDQTBLD-UHFFFAOYSA-N n,n-dimethyl-3-(triazinan-1-yl)propan-1-amine Chemical compound CN(C)CCCN1CCCNN1 NXHXNTAEDQTBLD-UHFFFAOYSA-N 0.000 claims 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种异氰酸酯微孔聚合物材料及其制备方法与应用，涉及有机多孔聚合物。原料组成为单体0.264g，三聚共催化剂7.4～14.8μL，溶剂1.5～3.0g。制备方法：1)将单体、高温三聚共催化剂和溶剂混合后，加入到玻璃试管中，将玻璃试管充放氮气三次后封管；2)将步骤1)封管后的玻璃试管放到程序控温箱中进行聚合反应后，即得微孔聚合物产物；3)将步骤2)得到的微孔聚合物产物，用四氢呋喃洗涤并抽提去除催化剂和固体溶剂，干燥后，即得所述异氰酸酯微孔聚合物材料。异氰酸酯微孔聚合物材料可在制备催化剂载体、储气材料、气体分离与吸附剂等中应用。生产条件温和，生产效率高，工艺简单。
Description
技术领域
本发明涉及有机多孔聚合物，尤其是涉及一种异氰酸酯微孔聚合物材料及其制备方法与应用。
背景技术
近几年来，有机多孔聚合物材料的合成得到了迅速的发展，以其在吸附与分离、多相催化、气体存储等领域的广泛应用，受到国内外研究人员的极大关注。与传统的多孔材料如活性炭，分子筛和无机-有机杂化金属有机骨架相比，有机聚合物骨架材料一般由较轻的碳、氢、氧、氮构成，具有更轻的骨架密度，且具有更高的比表面积、更好的物理化学稳定性。而且，有机多孔材料的结构、性能和功能可以通过合理的化学设计、选择合适的结构单元和多种化学合成途径进行调节。
制备有机聚合物多孔材料的传统方法有模板法、嵌段共聚物自组装法、高内相乳液聚合法和分散聚合法等。模板法通过改变模板的形状和大小来控制多孔材料孔的形貌和大小。文献“Gaseous infiltration method for preparation of three-dimensionallyordered macroporous polyethylene”(Polymer 49(2008)5446-5451)提出以二氧化硅为模板，向二氧化硅微球规整堆积形成的胶体晶体的空隙中充入乙烯单体，进行聚合反应，用氢氟酸去除模板，得到孔径大小均一且三维有序的聚乙烯多孔材料。高内相乳液聚合是以高体积分数的内相为孔隙模板，在含有聚合单体的外相中进行聚合，之后将内相去除从而得到多孔聚合物。专利CN201210086598提出了以甲基丙烯酸甲酯的高内相乳液聚合来制得互通多孔材料。上述方法都是较为成熟的技术，但是都存在一些缺陷。模板法过于依赖附加的模板，模板的选择限制了孔径的变化，且制备过程复杂，不利于所得多孔材料的规模化生产和应用。自组装法制备多孔材料，嵌段共聚物价格较高受到限制，也不易进行规模化生产和应用。高内相乳液聚合和分散聚合法需要加入乳化剂、分散剂及制孔剂等等，过程复杂，残留的杂物也限制其发展应用。
发明内容
本发明的目的在于基于上述现有技术制备多孔材料，依赖模板、稳定剂、制孔剂或其他辅助试剂、过程繁琐且耗时、功能改性复杂、原料价格高、工业化生产困难等问题，提供一种异氰酸酯微孔聚合物材料及其制备方法。
本发明的另一目的在于提供异氰酸酯微孔聚合物材料在制备气体吸附剂中的应用。
所述异氰酸酯微孔聚合物材料的原料组成为：
单体0.264g，所述单体为二甲基联苯二异氰酸酯；
高温三聚共催化剂(7.4～14.8)μL，所述高温三聚共催化剂为三(二甲氨基丙基)六氢三嗪(PC-41)；
溶剂(1.5～3.0)g，所述溶剂为二苯砜；
其中，单体和溶剂以质量计算，高温三聚共催化剂以体积计算。
所述异氰酸酯微孔聚合物材料的制备方法如下：
1)将单体、高温三聚共催化剂和溶剂混合后，加入到玻璃试管中，将玻璃试管充放氮气三次后封管；
2)将步骤1)封管后的玻璃试管放到程序控温箱中进行聚合反应后，即得微孔聚合物产物；
3)将步骤2)得到的微孔聚合物产物，用四氢呋喃洗涤并抽提去除催化剂和固体溶剂，干燥后，即得所述异氰酸酯微孔聚合物材料。
在步骤1)中，所述玻璃试管可采用15mm×150mm的单口玻璃试管；所述封管可在离玻璃试管管口50～70mm处进行封口。
在步骤2)中，所述聚合反应的条件可为：以5℃/min的升温速率升温至150℃保温2h，再以10℃/min的升温速率升温至250℃保温2h，再以10℃/min的升温速率升温至320℃保温12h。
将制得的异氰酸酯微孔聚合物材料进行应用测试，分别在压力1.13bar，温度77K下测试N2吸附，在压力1.0bar，温度273K下测试CO2的吸附，比表面积在535～1025m2/g。
所述异氰酸酯微孔聚合物材料可在制备催化剂载体、储气材料、气体分离与吸附剂等中应用；所述储气材料如储氢材料等，气体分离与吸附剂如二氧化碳分离与吸附剂等。
实验表明，利用上述方法制备的异氰酸酯微孔聚合物材料应用在气体吸附上，尤其，对于CO2的吸附，有着优良的性能。
本发明利用二甲基联苯二异氰酸酯中的—N＝C＝O，在催化剂和高温作用下，发生环三聚聚合交联形成一个六元环，当交联度较大时，得到的三维网络结构的微孔聚合物材料。
本发明制备的异氰酸酯微孔聚合物材料，具有如下优点：
1、本发明所涉及的原材料配方对于生产设备无特殊要求，生产条件温和，生产效率高，工艺简单。
2、本发明的微孔聚合物材料中含有大量的纳米级的微孔，并且这些孔是相通的，有利于CO2的传输和吸附；且具有较高的比表面积，利于CO2充分接触和吸附。
3、本发明的微孔聚合物材料，含有大量的-C＝N-双键有利CO2的捕捉和吸附。
4、本发明的微孔聚合物材料，将低毒物质转化为无毒物质，且具有优良的应用功能和性能，扩大了对多异氰酸酯类的单体使用和应用领域。
5、本发明的微孔聚合物材料，工艺简单，成本低，可以应用于工业化的生产。应用也较为广泛，特别是气体吸附的应用。因此，本发明具有广泛的工业应用前景。
附图说明
图1为本发明实施例1～5制备的异氰酸酯微孔聚合物材料的氮气吸附-脱附等温线。
图2为本发明实施例1～5制备的异氰酸酯微孔聚合物材料的0.5～10nm之间的孔径分布图。
图3为本发明实施例1～5制备的异氰酸酯微孔聚合物材料在1bar压力下，273K时，对CO2吸附的吸附-脱附曲线。
具体实施方式
下面通过具体实施方式来说明本发明，但并不限于此。
实施例1
一种异氰酸酯微孔聚合物材料制备方法，如以下步骤：
(1)制备原料混合物：称取0.264g的二甲基联苯二异氰酸酯和1.5g的二苯砜，量取7.4μL的PC-41，混合均匀后，加入到一根15×150mm的单口玻璃试管，将玻璃试管充放氮气三次，在离试管口60mm左右处进行封口(封管)；
(2)微孔聚合物材料的制备：将步骤(1)封好的试管放到程序控温箱，进行程序控温，以5℃/min的升温速率升温至150℃保温2h，再以10℃/min的升温速率升温至250℃保温2h，再以10℃/min的升温速率升温至320℃保温12h，得到未后处理的微孔聚合物产物；
(3)微孔聚合物材料的后处理：将步骤(2)得到的产物，用四氢呋喃洗涤三次并抽提12h去除催化剂，和固体溶剂后，进行干燥，得到所述的异氰酸酯微孔聚合物材料。
按照所述异氰酸酯微孔聚合物材料制备方法制备的异氰酸酯微孔聚合物材料，其平均孔径在1.7nm，孔体积为0.44cm3/g，其总的比表面积为1025m2/g。在1bar压力时，273K下，其CO2的吸附量为15.6wt％。其氮气吸附-脱附曲线见附图1，孔径在0～10nm的分布图见附图2，CO2吸附-脱附曲线见附图3。
实施例2
一种异氰酸酯微孔聚合物材料制备方法，如以下步骤：
(1)制备原料混合物：称取0.264g的二甲基联苯二异氰酸酯和2.0g的二苯砜，量取7.4μL的PC-41，混合均匀后，加入到一根15×150mm的单口玻璃试管，将玻璃试管充放氮气三次，在离试管口60mm左右处进行封口(封管)；
(2)微孔聚合物材料的制备：将步骤(1)封好的试管放到程序控温箱，进行程序控温，以5℃/min的升温速率升温至150℃保温2h，再以10℃/min的升温速率升温至250℃保温2h，再以10℃/min的升温速率升温至320℃保温12h，得到未后处理的微孔有机聚合物产物；
(3)微孔聚合物材料的后处理：将步骤(2)得到的产物，用四氢呋喃洗涤三次并抽提12h去除催化剂，和固体溶剂后，进行干燥，得到所述的异氰酸酯微孔聚合物材料。
按照所述异氰酸酯微孔聚合物材料制备方法制备的异氰酸酯微孔聚合物材料，其平均孔径在1.7nm，孔体积为0.39cm3/g，其总的比表面积为908m2/g。在1bar压力时，273K下，其CO2的吸附量为12.9wt％。其氮气吸附-脱附曲线见附图1，孔径在0～10nm的分布图见附图2，CO2吸附-脱附曲线见附图3。
实施例3
一种异氰酸酯微孔聚合物材料制备方法，如以下步骤：
(1)制备原料混合物：称取0.264g的二甲基联苯二异氰酸酯和3.0g的二苯砜，量取7.4μL的PC-41，混合均匀后，加入到一根15×150mm的单口玻璃试管，将玻璃试管充放氮气三次，在离试管口60mm左右处进行封口(封管)；
(2)微孔聚合物材料的制备：将步骤(1)封好的试管放到程序控温箱，进行程序控温，以5℃/min的升温速率升温至150℃保温2h，再以10℃/min的升温速率升温至250℃保温2h，再以10℃/min的升温速率升温至320℃保温12h，得到未后处理的微孔有机聚合物产物；
(3)微孔聚合物材料的后处理：将步骤(2)得到的产物，用四氢呋喃洗涤三次并抽提12h去除催化剂，和固体溶剂后，进行干燥，得到所述的异氰酸酯微孔聚合物材料。
按照所述异氰酸酯微孔聚合物材料制备方法制备的异氰酸酯微孔聚合物材料，其平均孔径在1.7nm，孔体积为0.35cm3/g，其总的比表面积为821m2/g。在1bar压力时，273K下，其CO2的吸附量为12.4wt％。其氮气吸附-脱附曲线见附图1，孔径在0～10nm的分布图见附图2，CO2吸附-脱附曲线见附图3。
实施例4
一种异氰酸酯微孔聚合物材料制备方法，如以下步骤：
(1)制备原料混合物：称取0.264g的二甲基联苯二异氰酸酯和3.0g的二苯砜，量取14.8μL的PC-41混合均匀后，加入到一根15×150mm的单口玻璃试管，将玻璃试管充放氮气三次，在离试管口60mm左右处进行封口(封管)；
(2)微孔聚合物材料的制备：将步骤(1)封好的试管放到程序控温箱，进行程序控温，以5℃/min的升温速率升温至150℃保温2h，再以10℃/min的升温速率升温至250℃保温2h，再以10℃/min的升温速率升温至320℃保温12h，得到未后处理的微孔有机聚合物产物；
(3)微孔聚合物材料的后处理：将步骤(2)得到的产物，用四氢呋喃洗涤三次并抽提12h去除固体溶剂后，进行干燥，得到所述的异氰酸酯微孔聚合物材料。
按照所述异氰酸酯微孔聚合物材料制备方法制备的异氰酸酯微孔聚合物材料，其平均孔径在1.7nm，孔体积为0.23cm3/g，其总的比表面积为535m2/g。在1bar压力时，273K下，其CO2的吸附量为8.5wt％。其氮气吸附-脱附曲线见附图1，孔径在0～10nm的分布图见附图2，CO2吸附-脱附曲线见附图3。
实施例5
一种异氰酸酯微孔聚合物材料制备方法，如以下步骤：
(1)制备原料混合物：称取0.264g的二甲基联苯二异氰酸酯和1.5g的二苯砜，量取14.8μL的PC-41，混合均匀后，加入到一根15×150mm的单口玻璃试管，将玻璃试管充放氮气三次，在离试管口60mm左右处进行封口(封管)；
(2)微孔聚合物材料的制备：将步骤(1)封好的试管放到程序控温箱，进行程序控温，以5℃/min的升温速率升温至150℃保温2h，再以10℃/min的升温速率升温至250℃保温2h，再以10℃/min的升温速率升温至320℃保温12h，得到未后处理的微孔有机聚合物产物；
(3)微孔聚合物材料的后处理：将步骤(2)得到的产物，用四氢呋喃洗涤三次并抽提12h去除催化剂，和固体溶剂后，进行干燥，得到所述的异氰酸酯微孔聚合物材料。
按照所述异氰酸酯微孔聚合物材料制备方法制备的异氰酸酯微孔聚合物材料，其平均孔径在1.7nm，孔体积为0.24cm3/g，其总的比表面积为576m2/g。在1bar压力时，273K下，其CO2的吸附量为10.2wt％。其氮气吸附-脱附曲线见附图1，孔径在0～10nm的分布图见附图2，CO2吸附-脱附曲线见附图3。
Claims (6)
1.一种异氰酸酯微孔聚合物材料，其特征在于其原料组成为：
单体0.264g，所述单体为二甲基联苯二异氰酸酯；
三聚共催化剂(7.4～14.8)μL，所述三聚共催化剂为三(二甲氨基丙基)六氢三嗪(PC-41)；
溶剂(1.5～3.0)g，所述溶剂为二苯砜；
其中，单体和溶剂以质量计算，三聚共催化剂以体积计算；
所述异氰酸酯微孔聚合物材料的制备方法如下：
1)将单体、三聚共催化剂和溶剂混合后，加入到玻璃试管中，将玻璃试管充放氮气三次后封管；
2)将步骤1)封管后的玻璃试管放到程序控温箱中进行聚合反应后，即得微孔聚合物产物；所述聚合反应的条件为：以5℃/min的升温速率升温至150℃保温2h，再以10℃/min的升温速率升温至250℃保温2h，再以10℃/min的升温速率升温至320℃保温12h；
3)将步骤2)得到的微孔聚合物产物，用四氢呋喃洗涤并抽提去除催化剂和固体溶剂，干燥后，即得所述异氰酸酯微孔聚合物材料。
2.如权利要求1所述异氰酸酯微孔聚合物材料，其特征在于在步骤1)中，所述玻璃试管采用15mm×150mm的单口玻璃试管。
3.如权利要求1所述异氰酸酯微孔聚合物材料，其特征在于在步骤1)中，所述封管在离玻璃试管管口50～70mm处进行封口。
4.如权利要求1所述异氰酸酯微孔聚合物材料在制备催化剂载体、储气材料、气体分离与吸附剂中应用。
5.如权利要求4所述应用，其特征在于所述储气材料为储氢材料。
6.如权利要求4所述应用，其特征在于所述气体分离与吸附剂为二氧化碳分离与吸附剂。
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| WO2006022641A1 (en) * | 2004-07-28 | 2006-03-02 | Huntsman International Llc | Process for the production of polyisocyanates |
| CN102617782A (zh) * | 2012-03-29 | 2012-08-01 | 中国烟草总公司郑州烟草研究院 | 一种聚甲基丙烯酸甲酯互通多孔材料的制备方法及其应用 |
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| CN1125955A (zh) * | 1993-06-22 | 1996-07-03 | 帝国化学工业公司 | 微孔聚氨酯材料 |
| CN1129948A (zh) * | 1993-07-07 | 1996-08-28 | 陶氏化学公司 | 微孔异氰酸酯基聚合物组合物及其制备方法 |
| WO2006022641A1 (en) * | 2004-07-28 | 2006-03-02 | Huntsman International Llc | Process for the production of polyisocyanates |
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