CN113912829B - Method for catalyzing ring-opening copolymerization of epoxide and cyclic anhydride by metal organic framework - Google Patents

Method for catalyzing ring-opening copolymerization of epoxide and cyclic anhydride by metal organic framework Download PDF

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CN113912829B
CN113912829B CN202111344092.1A CN202111344092A CN113912829B CN 113912829 B CN113912829 B CN 113912829B CN 202111344092 A CN202111344092 A CN 202111344092A CN 113912829 B CN113912829 B CN 113912829B
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zif
epoxide
cyclic anhydride
anhydride
nitrate
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CN113912829A (en
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肖龙强
胡从意
邓称怀
杨植舜
刘亚彬
赖艺明
侯琳熙
赵玉来
蔡静宇
阴翔宇
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Qingyuan Innovation Laboratory
Fuzhou University
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Fuzhou University
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    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/826—Metals not provided for in groups C08G63/83 - C08G63/86
    • 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
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers

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  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention discloses a method for catalyzing epoxide and cyclic anhydride to carry out ring-opening copolymerization by using a metal organic framework, which comprises the steps of mixing ZIF-8/67, epoxide and cyclic anhydride and carrying out ring-opening copolymerization under the condition of no water and no oxygen. The invention has simple and green process, does not need to remove small molecular byproducts at high temperature, can realize mass production of polyesters with different types and functions, is easy to separate the catalyst from the product, and reduces metal pollution in the product.

Description

Method for catalyzing ring-opening copolymerization of epoxide and cyclic anhydride by metal organic framework
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for catalyzing ring-opening copolymerization of epoxide and cyclic anhydride by using a metal organic framework.
Background
The polyester is a degradable high molecular polymer, especially biodegradable polyester, which can meet the industrial requirement and lighten the environmental burden. Therefore, development and application of degradable polyester materials have been paid attention in recent years. Typical polyester synthesis processes include step growth polycondensation or Ring Opening Polymerization (ROP). The stepwise polymerization of diols and diacids/diesters generally requires high temperatures and long reaction times, and side reactions can occur as well as produce low molecular weight polymers. ROP of cyclic esters can be effective in producing polyesters of controlled structure and molecular weight, but the use of cyclic monomers may be limited. Catalytic Ring Opening Copolymerization (ROCOP) of epoxides and cyclic anhydrides is another polyester production technology that has received increasing attention in recent years. However, impurities from homogeneous catalysts in the polymer can limit the practical application of the polymer product produced. Solid catalysts that enable easy separation of the catalyst from the polymerization product are of great interest.
Metal Organic Frameworks (MOFs) exhibit well-defined structures with fixed porosity, consisting of nodes (metal ions or clusters) coordinated to organic bridging ligands to form a coordinated network. These assembled MOFs structures can be divided into three categories: one-dimensional (1D) chains, two-dimensional (2D) sheets and three-dimensional (3D) frames. The advantages of MOFs materials are the presence of pores of a suitable size and shape for the adsorption of the monomers and a framework that allows a controlled arrangement of the monomers to be polymerized. In particular, 3D MOFs often exhibit high specific surface area and large pore size and are useful as promising heterogeneous catalysts for ring-opening copolymerization of different monomers.
Disclosure of Invention
The invention aims to provide a method for catalyzing ring-opening copolymerization of epoxide and cyclic anhydride by using a metal organic framework, which has the advantages of simple and green process, no auxiliary catalyst, no small molecule by-product, capability of realizing mass production of polyesters with different types and functions and easy separation of catalysts.
In order to achieve the above purpose, the invention adopts the following technical scheme:
(1) Respectively dissolving nitrate and 2-methylimidazole in anhydrous methanol, slowly dripping a methanol solution of the nitrate into a methanol solution of the 2-methylimidazole under the action of magnetic stirring, and stirring the mixture solution at room temperature after the dripping is completed. After the reaction, the product was collected by centrifugation and washed with anhydrous methanol. Finally drying in a vacuum drying oven to obtain powdery solid.
(2) Taking the powdery solid prepared in the step (1) and epoxide and cyclic anhydride to obtain a mixture of 1:100-500: mixing in the molar ratio of 100-200, ring-opening polymerization in anhydrous and anaerobic condition for 0.4-12 hr and at 60-130 deg.c.
The preparation method comprises the following steps: the nitrate is zinc nitrate hexahydrate or cobalt nitrate hexahydrate;
the preparation method comprises the following steps: the molar ratio of nitrate to 2-methylimidazole is 1:8.
the preparation method comprises the following steps: the powdery solid is ZIF-8 or ZIF-67.
The preparation method comprises the following steps: the epoxide is epichlorohydrin, epoxybutane, styrene oxide, epoxycyclohexane and phenyl glycidyl ether, and the structural formula is shown as I;
Figure DEST_PATH_IMAGE001
the preparation method comprises the following steps: the cyclic anhydride is succinic anhydride, maleic anhydride, itaconic anhydride and phthalic anhydride, and the structural formula is shown as II;
Figure 783749DEST_PATH_IMAGE002
the invention has the beneficial effects that:
(1) Compared with the traditional polyester produced by polycondensation or transesterification, the method does not need high temperature to remove small molecular byproducts through ring-opening copolymerization of epoxide and cyclic anhydride, and accords with green chemistry and atom economy.
(2) Compared with lactone monomers, the preparation of the epoxide and the cyclic anhydride is simpler and more economical, and most of epoxide and cyclic anhydride raw materials can be produced in a large scale at present, so that the ring-opening copolymerization of the epoxide and the cyclic anhydride is more suitable for preparing polyesters with different types and functions.
(3) Compared with a homogeneous catalyst, a heterogeneous catalyst is easier to separate from a product, and metal pollution in the product is reduced.
Drawings
FIG. 1 is a powder XRD pattern for ZIF-8 and ZIF-67.
FIG. 2 is a polyester obtained in example 1 1 H NMR spectrum.
FIG. 3 is a GPC chart of the polyester obtained in example 1.
Detailed Description
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
The ZIF-8/67 and epoxide and cyclic anhydride are quantitatively put into a Schlenk tube by adopting Schlenk technology or operating in a glove box, stirred uniformly at room temperature, placed into a set constant temperature reaction bath, stirred and started, and polymerization is started after the specified temperature is reached. After a certain reaction time, the corresponding polyester can be obtained after precipitation by dissolving the product with methylene chloride, vacuum drying to constant weight at room temperature, and then sampling for relevant structure and performance testing. The proportions in the examples are molar ratios.
Example 1
ZIF-8, CHO, PA were prepared in an anhydrous and anaerobic environment at a ratio of 1:200:400 are added into a Schlenk tube in sequence, stirred uniformly at room temperature, placed into a set constant temperature reaction bath at 80 ℃ for reaction for 2 hours, and sampled for nuclear magnetic analysis. The polymer was obtained by precipitation with dichloromethane, dried in vacuo and tested for molecular weight, mn=1600 and pdi=1.14.
Example 2
ZIF-8, CHO, MA was prepared in an anhydrous and anaerobic environment at a ratio of 1:200:200 are sequentially added into a Schlenk tube, stirred uniformly at room temperature, placed into a set constant-temperature reaction bath at 80 ℃ for reaction for 0.5h, and sampled for nuclear magnetism analysis. The polymer was obtained by precipitation with dichloromethane, dried in vacuo and tested for molecular weight.
Example 3
ZIF-8, CHO, SA were prepared in an anhydrous and anaerobic environment at a ratio of 1:200:400 are added into a Schlenk tube in sequence, stirred uniformly at room temperature, placed into a set constant temperature reaction bath at 80 ℃ for reaction for 2 hours, and sampled for nuclear magnetic analysis. The polymer was obtained by precipitation with dichloromethane, dried in vacuo and tested for molecular weight.
Example 4
ZIF-8, CHO, IA were prepared in an anhydrous and anaerobic environment at a ratio of 1:200:200 are sequentially added into a Schlenk tube, stirred uniformly at room temperature, placed into a set constant-temperature reaction bath at 80 ℃ for reaction for 0.5h, and sampled for nuclear magnetism analysis. The polymer was obtained by precipitation with dichloromethane, dried in vacuo and tested for molecular weight.
Example 5
ZIF-8, ECH, PA were prepared in an anhydrous and anaerobic environment at a ratio of 1:200:400 are added into a Schlenk tube in sequence, stirred uniformly at room temperature, placed into a set constant temperature reaction bath at 80 ℃ for reaction for 6 hours, and sampled for nuclear magnetic analysis. The polymer was obtained by precipitation with dichloromethane, dried in vacuo and tested for molecular weight.
Example 6
ZIF-8, BO, PA was prepared in an anhydrous and anaerobic environment at a ratio of 1:200:400 are added into a flask in sequence, stirred at room temperature uniformly, placed into a set constant temperature reaction bath at 80 ℃ for reaction for 3 hours, and sampled for nuclear magnetic analysis. The polymer was obtained by precipitation with dichloromethane, dried in vacuo and tested for molecular weight.
Example 7
ZIF-8, SO, PA were prepared in an anhydrous and anaerobic environment according to a ratio of 1:200:400 are added into Schlenk in sequence, stirred uniformly at room temperature, placed into a set reaction bath with constant temperature of 110 ℃ for reaction for 1h, and sampled for nuclear magnetic analysis. The polymer was obtained by precipitation with dichloromethane, dried in vacuo and tested for molecular weight.
Example 8
ZIF-8, PGE and PA are mixed according to the following ratio of 1:200:400 are added into Schlenk in sequence, stirred uniformly at room temperature, placed into a set reaction bath with constant temperature of 110 ℃ for reaction for 1h, and sampled for nuclear magnetic analysis. The polymer was obtained by precipitation with dichloromethane, dried in vacuo and tested for molecular weight.
Example 9
ZIF-8, ECH, MA were prepared in an anhydrous and anaerobic environment at a ratio of 1:200:200 are sequentially added into a flask, stirred at room temperature uniformly, placed into a set constant temperature reaction bath at 80 ℃ for reaction for 1h, and sampled for nuclear magnetic analysis. The polymer was obtained by precipitation with dichloromethane, dried in vacuo and tested for molecular weight.
Example 10
ZIF-8, BO, MA were prepared in an anhydrous and anaerobic environment at a ratio of 1:200:200 are sequentially added into a flask, stirred at room temperature uniformly, placed into a set constant temperature reaction bath at 80 ℃ for reaction for 1h, and sampled for nuclear magnetic analysis. The polymer was obtained by precipitation with dichloromethane, dried in vacuo and tested for molecular weight.
Example 11
ZIF-67, CHO, PA were prepared in an anhydrous and anaerobic environment at a ratio of 1:200:400 are added into a Schlenk tube in sequence, stirred uniformly at room temperature, placed into a set reaction bath with constant temperature of 110 ℃ for reaction for 0.4h, and sampled for nuclear magnetism analysis. The polymer was obtained by precipitation with dichloromethane, dried in vacuo and tested for molecular weight.
Example 12
ZIF-67, CHO, MA was prepared in an anhydrous and anaerobic environment at a ratio of 1:200:200 are sequentially added into a Schlenk tube, stirred uniformly at room temperature, placed into a set constant-temperature reaction bath at 80 ℃ for reaction for 0.5h, and sampled for nuclear magnetism analysis. The polymer was obtained by precipitation with dichloromethane, dried in vacuo and tested for molecular weight.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (6)

1. A method for catalyzing ring-opening copolymerization of epoxide and cyclic anhydride by a metal organic framework is characterized in that: ZIF-8 or ZIF-67 is mixed with epoxide and cyclic anhydride, and ring-opening copolymerization is carried out under anhydrous and anaerobic conditions.
2. The method according to claim 1, characterized in that: the method comprises the following steps:
(1) Respectively dissolving nitrate and 2-methylimidazole in anhydrous methanol, slowly dripping a methanol solution of the nitrate into a methanol solution of the 2-methylimidazole under magnetic stirring, and continuously stirring at room temperature to fully react; centrifuging, washing with anhydrous methanol, and vacuum drying to obtain ZIF-8 or ZIF-67;
(2) The molar ratio of ZIF-8 or ZIF-67, epoxide and cyclic anhydride is 1:100-500:100-200, and carrying out ring-opening polymerization under anhydrous and anaerobic conditions, wherein the reaction time is 0.4-12 h, and the reaction temperature is 60-130 ℃.
3. The method according to claim 2, characterized in that: the nitrate is zinc nitrate hexahydrate or cobalt nitrate hexahydrate.
4. The method according to claim 2, characterized in that: the molar ratio of nitrate to 2-methylimidazole is 1:8.
5. the method according to claim 1 or 2, characterized in that: the epoxide is any one of epichlorohydrin, epoxybutane, styrene oxide, epoxycyclohexane and phenyl glycidyl ether.
6. The method according to claim 1 or 2, characterized in that: the cyclic anhydride is any one of succinic anhydride, maleic anhydride, itaconic anhydride and phthalic anhydride.
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