CN109331877B - 一种离子型微孔聚合物催化剂及其制备方法和应用 - Google Patents
一种离子型微孔聚合物催化剂及其制备方法和应用 Download PDFInfo
- Publication number
- CN109331877B CN109331877B CN201811454881.9A CN201811454881A CN109331877B CN 109331877 B CN109331877 B CN 109331877B CN 201811454881 A CN201811454881 A CN 201811454881A CN 109331877 B CN109331877 B CN 109331877B
- Authority
- CN
- China
- Prior art keywords
- monomer
- catalyst
- microporous polymer
- preparation
- polymer catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/22—Magnesium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/31—Aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
- Polyesters Or Polycarbonates (AREA)
- Polyethers (AREA)
Abstract
本发明公开了一种离子型微孔聚合物催化剂及其制备方法和应用,属于催化剂制备技术领域。本发明使用便宜易得的单体,经由简单的有机合成反应制备了双功能催化剂,将双金属催化中心和亲核试剂同时引入到多孔聚合物中,并且亲核试剂分散密度高,该低成本的催化剂在0.1‑0.7MPa,25‑90℃条件催化二氧化碳转化为环碳酸脂。本发明利用简单的合成方法以及低成本的原料,达到与高成本的催化剂相近的催化效果,且该催化剂可以重复使用。
Description
技术领域
本发明涉及一种离子型微孔聚合物催化剂及其制备方法和应用,属于催化剂制备技术领域。
背景技术
二氧化碳的排放量正在逐年增加,设计制备对二氧化碳具有捕获与存储特性的材料以及关注CO2的化学利用迫在眉睫。二氧化碳作为便宜、易得的碳1构筑基元,以其为原料来制备高附加值化学产品也因此倍受关注。催化剂在二氧化碳转化过程中发挥着重要的作用。将催化中心和催化助剂同时引入到多孔聚合物中,以该双功能聚合物为非均相催化剂,催化二氧化碳与环氧烷烃的反应,使其转化为环碳酸脂,对于该种材料的制备是目前二氧化碳减排研究的热点。现有的能够在较温和条件下催化反应的催化剂制备步骤较多,单体需要合成,并且存在催化助剂不能回收再利用的问题。因此,开发一种合成方法简单,原料成本低,并且能够达到在较温和条件下进行催化的双功能催化剂,成为亟待解决的问题。
发明内容
为解决上述问题,本发明的催化剂在微孔聚合物中引入双金属催化中心,离子型聚合物内分散着高密度亲核试剂,如Br-或Cl-,利用双金属的协同催化作用,以及高密度分散的亲核试剂使该催化在较温和的反应条件下(0.1-0.7MPa,25-90℃),实现二氧化碳的催化转化。
本发明的第一个目的是提供一种离子型微孔聚合物催化剂,由单体A、单体B和单体C聚合而成;所述单体C作为连接基团;其中,单体A、单体B和单体C的结构式如下所示:
其中,M、P为两种不同的金属离子;
X、Y单独选自Cl、Br或OAc,a、b分别为2或3;
Z为Cl或Br。
在本发明的一种实施方式中,所述单体A和单体B的摩尔比为4:1-1:4,单体C的摩尔数为单体A和单体B的总摩尔数的2-5倍。
在本发明的一种实施方式中,所述催化剂的一种结构示意图如下所示:
在本发明的一种实施方式中,所述M、P单独选自Al、Zn、Mg、Ni、Cr、Cu或者Co,且M、P不相同。
在本发明的一种实施方式中,所述M优选为Al,所述P优选为Zn。
在本发明的一种实施方式中,所述离子型微孔聚合物催化剂的比表面积为25-100m2/g。
本发明的第二个目的是提供所述催化剂的制备方法,包括:将单体A和单体B在交联剂单体C的作用下,在60-120℃反应12-36h,聚合得到所述离子型微孔聚合物催化剂;其中,单体A、单体B和单体C的结构式分别如下所示:
其中,M、P为两种不同的金属离子;
X、Y单独选自Cl、Br或OAc,a、b分别为2或3;
Z为Cl或Br。
在本发明的一种实施方式中,所述方法按照如下步骤进行:
(1)采用咪唑分别与两种金属卤化物或醋酸盐进行反应,制备得到两种四咪唑基金属单体(单体A和单体B);
(2)将步骤(1)得到的两种四咪唑基金属单体溶入有机溶剂中,然后加入1,4-对二卤苄(单体C),反应得到所述催化剂。
在本发明的一种实施方式中,在步骤(1)中,咪唑与金属离子的摩尔比为4:1-8:1。
在本发明的一种实施方式中,在步骤(1)中,反应条件为25℃-40℃反应2-12小时。
在本发明的一种实施方式中,在步骤(2)中,单体A和单体B的摩尔比为1:4-4:1。
在本发明的一种实施方式中,在步骤(2)中,单体C的添加量,按摩尔数计,为四咪唑基金属单体总摩尔数的2-5倍。
在本发明的一种实施方式中,在步骤(2)中,反应条件为60-120℃反应12-36h。
在本发明的一种实施方式中,所述制备方法具体包括:
(1)咪唑与金属卤化物按照摩尔比4-5:1溶于甲醇中,25℃-40℃搅拌反应2-12小时,除去甲醇,然后用四氢呋喃冲洗,干燥后得到四咪唑基金属单体(单体A);
(2)按照步骤(1)的方法,采用与步骤(1)不相同的金属离子,制备另一种四咪唑基金属单体(单体B);
(3)按照摩尔比4:1-1:4将步骤(1)和步骤(2)制备得到的单体A和单体B溶于有机溶剂,然后加入单体A和单体B总摩尔数2-5倍的单体C,60-120℃搅拌反应12-36h;冷却过滤后,依次采用二氯甲烷和甲醇洗涤固体,再采用二氯甲烷与甲醇体积比为1-3:1的混合液进行索氏抽提12-36h,最后干燥得到催化剂。
在本发明的一种实施方式中,咪唑与金属卤化物的反应式为:
在本发明的一种实施方式中,所述有机溶剂为N-甲基吡咯烷酮或二甲基甲酰胺。
本发明的第三个目的是提供所述催化剂在二氧化碳减排中的应用。
在本发明的一种实施方式中,应用所述的离子型微孔聚合物催化剂催化二氧化碳与环氧烷烃反应转化为环碳酸脂。
本发明的有益效果在于:
本发明使用便宜易得的单体,经由简单的有机合成反应制备了双功能催化剂,将双金属催化中心和亲核试剂同时引入到多孔聚合物中,并且亲核试剂分散密度高,该低成本的催化剂在0.1-0.7MPa,25-90℃条件催化二氧化碳转化为环碳酸脂。本发明利用简单的合成方法以及低成本的原料,达到与高成本的催化剂相近的催化效果,且该催化剂可以重复使用。
附图说明
图1是苯基碳酸乙烯酯的氢谱。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明,以使本领域的技术人员可以更好地理解本发明并能予以实施,但所举实施例不作为对本发明的限定。
实施例1:催化剂cat-Al-Zn的制备
四咪唑基铝单体的制备:咪唑(4.2mmol,0.29g),三氯化铝(1mmol,133.4mg)溶于甲醇30ml,30℃搅拌12小时,除去甲醇,抽滤,用THF冲洗,干燥,得到单体1-Al。
四咪唑基锌单体的制备:咪唑(4.2mmol,0.29g),氯化锌(1mmol,136.3mg)溶于甲醇,30℃搅拌12小时,除去甲醇,抽滤,用THF冲洗,干燥,得到单体1-Zn。
1-Al(1mmol,0.41g),1-Zn(1mmol,0.41g)溶于25ml NMP中,加入1,4-对二氯苄(5mmol,0.9g)或1,4-对二溴苄,80℃搅拌30h,反应停止,冷却至室温,抽滤,依次用CH2Cl2和CH3OH洗涤固体,索氏提取30h(提取液为CH2Cl2与CH3OH体积比为1.5:1的混合液),最后70℃真空干燥12h即得催化剂cat-Al-Zn。
取50mg实施例1制备得到的cat-Al-Zn,1ml苯基环氧乙烷,二氧化碳压力为0.7MPa,90℃下反应48h,得到苯基碳酸乙烯酯的产率为85%。产物核磁如图1所示。
实施例2:
四咪唑基钴单体的制备:咪唑(4.2mmol,0.29g),醋酸钴(1mmol,177.0mg)溶于甲醇30ml,30℃搅拌12小时,除去甲醇,抽滤,用THF冲洗,干燥,得到单体1-Co。
四咪唑基锌单体的制备:咪唑(4.2mmol,0.29g),氯化锌(1mmol,136.3mg)溶于甲醇,30℃搅拌12小时,除去甲醇,抽滤,用THF冲洗,干燥,得到单体1-Zn。
1-Co(1mmol,0.45g),1-Zn(1mmol,0.41g)溶于25ml NMP中,加入1,4-对二氯苄(5mmol,0.9g)或1,4-对二溴苄,80℃搅拌30h,反应停止,冷却至室温,抽滤,依次用CH2Cl2和CH3OH洗涤固体,索氏提取30h(提取液为CH2Cl2与CH3OH体积比为1.5:1的混合液),最后70℃真空干燥12h即得催化剂cat-Co-Zn。
取50mg cat-Co-Zn,1mL苯基环氧乙烷,二氧化碳压力为0.7MPa,90℃下反应48h,得到苯基碳酸乙烯酯的产率为70%。
以上所述实施例仅是为充分说明本发明而所举的较佳的实施例,本发明的保护范围不限于此。本技术领域的技术人员在本发明基础上所作的等同替代或变换,均在本发明的保护范围之内。本发明的保护范围以权利要求书为准。
Claims (7)
2.根据权利要求1所述的方法,其特征在于,所述单体A或单体B的制备方法为:采用咪唑与金属的卤化物或者醋酸盐进行反应,得到单体A或单体B。
3.根据权利要求2所述的方法,其特征在于,所述咪唑与金属离子的摩尔比为4:1-8:1。
4.根据权利要求2所述的方法,其特征在于,所述咪唑与金属的卤化物或者醋酸盐进行反应的条件为25℃-40℃反应2-12小时。
5.一种权利要求1~4任一项所述的方法制备得到的离子型微孔聚合物催化剂。
6.权利要求5所述的离子型微孔聚合物催化剂在二氧化碳减排中的应用。
7.根据权利要求6所述的应用,其特征在于,应用所述的离子型微孔聚合物催化剂催化二氧化碳与环氧烷烃反应转化为环碳酸脂。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810651280 | 2018-06-22 | ||
CN2018106512800 | 2018-06-22 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109331877A CN109331877A (zh) | 2019-02-15 |
CN109331877B true CN109331877B (zh) | 2021-06-22 |
Family
ID=65318871
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811454881.9A Active CN109331877B (zh) | 2018-06-22 | 2018-11-30 | 一种离子型微孔聚合物催化剂及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109331877B (zh) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101270113A (zh) * | 2008-01-16 | 2008-09-24 | 兰州大学 | 多手性催化剂制备及在高光学活性环碳酸酯合成的应用 |
CN104667974A (zh) * | 2015-02-12 | 2015-06-03 | 中国科学院福建物质结构研究所 | 一种多孔有机材料的制备及催化转化二氧化碳应用 |
JP2018034152A (ja) * | 2016-08-23 | 2018-03-08 | 公立大学法人首都大学東京 | 多電子酸化還元触媒 |
-
2018
- 2018-11-30 CN CN201811454881.9A patent/CN109331877B/zh active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101270113A (zh) * | 2008-01-16 | 2008-09-24 | 兰州大学 | 多手性催化剂制备及在高光学活性环碳酸酯合成的应用 |
CN104667974A (zh) * | 2015-02-12 | 2015-06-03 | 中国科学院福建物质结构研究所 | 一种多孔有机材料的制备及催化转化二氧化碳应用 |
JP2018034152A (ja) * | 2016-08-23 | 2018-03-08 | 公立大学法人首都大学東京 | 多電子酸化還元触媒 |
Also Published As
Publication number | Publication date |
---|---|
CN109331877A (zh) | 2019-02-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN112341394B (zh) | 一种氢键供体功能化的聚合离子液体催化制备环状碳酸酯的方法 | |
CN113181962B (zh) | 钴卟啉交联聚季鏻盐离子液体及其制备和在催化二氧化碳与环氧化物环加成反应中的应用 | |
CN112521362B (zh) | 一种基于功能化金属卟啉/季鏻盐双催化体系合成环碳酸酯的方法 | |
CN109939731B (zh) | 一种用于常压co2环加成反应的介孔聚离子液体催化剂、制备方法及应用 | |
CN102580780B (zh) | 一种双组分双金属催化剂的合成方法及应用 | |
CN111138591B (zh) | 一种氮杂环卡宾/co2加合物功能化有机多孔聚合物、制备方法及应用 | |
CN101440159B (zh) | 脂肪族聚碳酸酯的合成方法 | |
CN105772091A (zh) | 一类用于co2还原的催化剂及其应用 | |
CN112409190B (zh) | 胺盐类离子液体高效催化合成环状碳酸酯的方法 | |
CN107400043A (zh) | 离子液体在丙二醇醚合成中的应用及丙二醇醚合成方法 | |
CN109331877B (zh) | 一种离子型微孔聚合物催化剂及其制备方法和应用 | |
CN111889141A (zh) | 一种催化二氧化碳与环氧化物环加成反应的离子液体功能化联吡啶类多孔聚合物催化剂 | |
KR102235012B1 (ko) | 비균일계 이미다졸린 기반 유기촉매 및 이를 이용한 고리형 카보네이트의 제조방법 | |
CN113185701B (zh) | 金属卟啉基多孔聚合物及其制备和在催化二氧化碳与环氧化物环加成反应中的应用 | |
CN112206808B (zh) | 一种用于合成异丁酸异丁酯的催化剂及其制备方法和应用 | |
Fierro et al. | I-LDH as a heterogeneous bifunctional catalyst for the conversion of CO2 into cyclic organic carbonates | |
CN112619705B (zh) | 环氧烷烃加成反应催化剂及其应用 | |
CN103897166B (zh) | 以硅烷化改性分子筛为载体的高分散性戊二酸锌催化剂的制备及其催化行为 | |
CN103657718B (zh) | 用于制备碳酸亚烷酯的树脂催化剂及其方法 | |
CN114276322A (zh) | 一种光引发聚合离子液体材料催化制备环状碳酸酯的方法 | |
CN112159386B (zh) | 一种离子液体交联聚合物温和催化合成环状碳酸酯的方法 | |
CN104877128B (zh) | 一种卤甲基化聚芳醚及其制备方法 | |
CN102671705B (zh) | 一种用于碳酸二甲酯合成的催化剂的制备方法及应用 | |
CN107586382B (zh) | 一种用于制备聚碳酸亚环己酯的锌类催化剂 | |
CN113429556B (zh) | 二氧化碳-环氧化合物共聚合成生物相容材料的催化剂 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |