CN110591056B - Method for synthesizing polyurethane by promoting nano palladium-catalyzed Heck coupling reaction through visible light - Google Patents
Method for synthesizing polyurethane by promoting nano palladium-catalyzed Heck coupling reaction through visible light Download PDFInfo
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Abstract
The invention belongs to the technical field of polyurethane preparation, and particularly relates to a method for synthesizing polyurethane by promoting nano palladium-catalyzed Heck coupling reaction under visible light, which comprises the following steps: preparing a monomer mixed solution; preparing a nano palladium catalyst system; preparing a polyurethane primary product; post-treatment such as cleaning; the method adopts a catalytic system with the synergistic effect of visible light (LED blue light), a nano palladium catalyst and quaternary ammonium salt, improves the polymerization reaction rate, and realizes the polycondensation of two monomers into polyurethane under mild conditions in the Heck coupling reaction. The introduction of the nano palladium catalyst with good dispersibility simplifies the operation steps; the introduction of visible light accelerates the polymerization reaction rate and shortens the synthesis time; the introduction of the quaternary ammonium salt enables the traditional Heck reaction to be realized under mild conditions. The invention directly synthesizes the polyurethane with the cinnamate structure on the main chain, and provides a new high-efficiency synthetic approach for synthesizing the functional polyurethane.
Description
Technical Field
The invention belongs to the technical field of polyurethane preparation, and particularly relates to a synthetic method of polyurethane with a cinnamate structure in a main chain.
Background
Polyurethane resins of Bayer invention have been known for eighty years since 1937 in Germany. At present, polyurethane becomes the fifth plastic in the world industry after polyethylene, polyvinyl chloride, polypropylene and polystyrene, has wide application fields, and relates to buildings, industry, traffic, packaging, refrigerators, freezers and the like, in particular to coating, adhesives, clothes, shoes and caps, high-end artificial blood vessels, artificial heart valves and the like. Polyurethane plays an important role as a multipurpose material in infrastructure, and the demand thereof is rapidly increasing.
At present, the most common method for synthesizing polyurethane is to use isocyanate as raw material to directly perform polycondensation reaction with polyol, and the method has certain limitation on the synthesis of functional polymer, and especially has certain challenge on synthesizing functional polyurethane with unsaturated double bond in main chain. It is well known that the biggest feature of the Heck reaction is that the reaction product contains unsaturated double bonds. Thus, the introduction of this reaction creates sufficient conditions for the synthesis of unsaturated polymers. In addition, isocyanate is easy to react with water in the air to deteriorate, which puts high demands on storage and transportation of raw materials, and therefore, how to protect the isocyanate groups in the raw materials without affecting further use of the raw materials is also a problem.
Disclosure of Invention
The invention aims to provide a method for synthesizing polyurethane with a cinnamate structure in a main chain by promoting a Mizoroki-Heck coupling reaction under a mild condition by using visible light.
The method for synthesizing polyurethane provided by the invention comprises the following specific steps:
(1) preparing a monomer mixed solution: dissolving 100 parts of AA monomer and BB monomer in 750 parts of solvent 350-750 parts, and uniformly stirring to obtain a monomer mixed solution; here, the AA monomer is prepared from isocyanate acrylate and different carbon chain lengths (C)3~C18) The BB monomer is selected from 1, 4-diiodobenzene, 4 '-diiodobiphenyl, 4' -diiododiphenyl ether, diiodophenyl derivatives thereof and the like;
(2) preparing a nano palladium catalyst system: placing 5-20 parts of palladium acetate, 10-50 parts of polyethylene glycol, 50-200 parts of quaternary ammonium salt and 100 parts of alkali in a two-mouth bottle, vacuumizing for 5-20 minutes by using a pump, and introducing Ar2Under the protection of gas, adding 350 parts of solvent 120-plus, placing the mixture into an oil bath pot, gradually heating to 40-120 ℃ under the stirring condition, reacting for 10-30 minutes, and then cooling the system to room temperature to obtain a well-dispersed nano palladium catalyst system;
(3) preparing a polyurethane primary product: adding the monomer mixed solution prepared in the step (1) into the nano-catalyst system obtained in the step (2); placing the system under LED blue light to perform illumination reaction at the reaction temperature of 25-30 ℃ for 12-24 hours to obtain a polyurethane primary product;
(4) and (3) post-treatment: washing the crude product with ionized water by centrifugation for more than 3 times; drying to obtain pure product.
Wherein the components are calculated according to parts by mass.
In the present invention, the solvent is preferably N, N-Dimethylformamide (DMF) or N, N-dimethylformamide (DMAc).
In the invention, the quaternary ammonium salt is selected from one of tetra-tert-butyl ammonium bromide, tetra-tert-butyl ammonium iodide and tetra-tert-butyl ammonium chloride. The introduction of the quaternary ammonium salt can realize polymerization under mild conditions.
In the invention, the alkali is at least one of potassium carbonate, cesium carbonate, sodium acetate, silver acetate, triethylamine, potassium phosphate, sodium phosphate and sodium carbonate.
In step (1) of the present invention, it is preferable that: 500 portions of solvent 350.
In step (2) of the present invention, it is preferable that: 5-10 parts of palladium acetate, 10-30 parts of polyethylene glycol, 50-100 parts of quaternary ammonium salt, 100 parts of alkali and 200 parts of solvent.
In the invention, the used AA monomer is relatively stable, so that the raw materials are convenient to store and transport, and meanwhile, the carbon chain lengths (C) are different3~C18) The alkyl diols of (a) can provide conditions for diversification and functionalization of the synthetic monomer AA. The introduction of the functional monomer provides conditions for the functionalization of the polymer.
In the invention, the synthesis of BB monomer can also be designed functionally, and the introduction of the functional monomer provides conditions for the functionalization of polymer.
In the present invention, the molecular weight of polyethylene glycol (PEG)M w= 500-5000 g/mol; the introduction of the polyethylene glycol can reduce palladium acetate and can also be used as a carrier of nano palladium, so that the preparation operation of the nano catalyst system is simple and easy.
In the invention, the introduction of the quaternary ammonium salt can realize the polymerization reaction under mild conditions.
In the invention, the blue light irradiation of the LED is used, the visible light lambda = 430-480 nm, and the irradiation of the wavelength light source can greatly improve the speed of the polymerization reaction.
The method has mild reaction conditions, and utilizes visible light to promote the nano palladium to catalyze the Mizoroki-Heck coupling reaction to synthesize the polyurethane with the cinnamate structure in the main chain.
The invention has the beneficial effects that: the method provides a new synthesis way for preparing the functionalized polyurethane, improves the convenience of storage and transportation of raw materials, and has very high functional design on the synthesis of monomers; meanwhile, the organic combination of visible light, quaternary ammonium salt and a nano palladium catalytic system realizes Heck coupling polycondensation reaction under mild conditions, greatly reduces production energy consumption, reduces production cost in industrialization, and has wide application prospect.
Drawings
FIG. 1 shows the GPC measurement results of the polymer in example 1.
FIG. 2 is a diagram of the characterization results of the nano-palladium catalyst. Wherein, (a) is a TEM image; (b) the particle size distribution diagram is shown.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The used materials are: 15 parts of palladium acetate and polyethylene glycol(s) (II)M w25 parts of =1000 g/mol), 150 parts of tetra-tert-butylammonium bromide, 220 parts of potassium carbonate and monomer AA (carbon = C)3) 100 parts, 100 parts of monomer BB (4, 4' -diiododiphenyl ether), 800 parts of solvent N, N-Dimethylformamide (DMF), and blue LED light (lambda =465 nm).
The structural formulas of the monomer AA and the monomer BB are as follows:
the synthesis steps of the polyurethane are as follows:
(1) dissolving 100 parts of the monomers AA and BB in 600 parts of DMF solvent respectively, and stirring uniformly for later use;
(2) placing 15 parts of palladium acetate, 25 parts of polyethylene glycol, 150 parts of quaternary ammonium salt and 220 parts of alkali into a 250ml two-mouth bottle, vacuumizing for 5 minutes by using a pump, and introducing Ar2Under the protection of gas, adding 200 parts of DMF (dimethyl formamide) solvent, placing the mixture into an oil bath kettle, gradually heating to 90 ℃ under the stirring condition, reacting for 10 minutes, and then cooling the system to room temperature to prepare a well-dispersed nano palladium catalyst system;
(3) and (3) adding the monomer mixed solution prepared in the step (1) into the nano catalyst system in the step (2). Placing the system in LED illumination and reacting at the temperature of 25-30 ℃ for 20 hours to obtain a polymerization product;
(4) 15ml of the crude product is taken as a metering unit and is respectively added into a 50ml centrifuge tube, then 30ml of deionized water is added, and the centrifugation is carried out. Repeatedly washing with water for three times or more, centrifuging, and finally drying to obtain a pure product.
Example 2
The materials used were: 10 parts of palladium acetate and polyethylene glycolM w50 parts of =2000 g/mol), 100 parts of tetra-tert-butylammonium bromide, 200 parts of potassium carbonate and monomer AA (carbon = C)10) 100 parts, 100 parts of monomer BB (4, 4' -diiododiphenyl ether), 1000 parts of solvent N, N-Dimethylformamide (DMF), LED blue light (λ =465 nm).
The structural formulas of the monomer AA and the monomer BB are as follows:
the synthesis steps of the polyurethane are as follows:
(1) dissolving 100 parts of monomers AA and BB in 750 parts of DMF solvent respectively, and stirring uniformly for later use;
(2) putting 10 parts of palladium acetate, 50 parts of polyethylene glycol, 100 parts of quaternary ammonium salt and 200 parts of alkali into a 250ml two-mouth bottle, vacuumizing for 5 minutes by using a pump, and introducing Ar2Adding 250 parts of DMF (dimethyl formamide) solvent under gas protection, placing the mixture in an oil bath pot, gradually heating to 70 ℃ under the stirring condition, reacting for 15 minutes, and then cooling the system to room temperature to prepare a well-dispersed nano palladium catalyst system;
(3) and (3) adding the monomer mixed solution prepared in the step (1) into the nano catalyst system in the step (2). Placing the system in LED illumination and reacting for 24 hours at the reaction temperature of 25-30 ℃ to obtain a polymerization product;
(4) 15ml of the crude product is taken as a metering unit and is respectively added into a 50ml centrifuge tube, then 30ml of deionized water is added, and the centrifugation is carried out. Repeatedly washing with water for three times or more, centrifuging, and finally drying to obtain a pure product.
Example 3
The materials used were: palladium acetate 5 parts, polyethylene glycol: ( M w10 parts of =2000 g/mol), 50 parts of tetra-tert-butylammonium bromide, 300 parts of potassium carbonate and monomer AA (carbon = C)10) 100 parts, 100 parts of monomer BB (4, 4' -diiododiphenyldecyldiether), 600 parts of solvent N, N-Dimethylformamide (DMF), and LED blue light (lambda =465 nm).
The structural formulas of the monomer AA and the monomer BB are as follows:
the polyurethane synthesis steps are as follows:
(1) dissolving 100 parts of the monomers AA and BB in 400 parts of DMF solvent respectively, and stirring uniformly for later use;
(2) putting 10 parts of palladium acetate, 50 parts of polyethylene glycol, 100 parts of quaternary ammonium salt and 200 parts of alkali into a 250ml two-mouth bottle, vacuumizing for 5 minutes by using a pump, and introducing Ar2Under the protection of gas, adding 200 parts of DMF (dimethyl formamide) solvent, placing the mixture into an oil bath kettle, gradually heating to 50 ℃ under the stirring condition, reacting for 20 minutes, and then cooling the system to room temperature to prepare a well-dispersed nano palladium catalyst system;
(3) and (3) adding the monomer mixed solution prepared in the step (1) into the nano catalyst system in the step (2). Placing the system in LED illumination and reacting for 15 hours at the reaction temperature of 25-30 ℃ to obtain a polymerization product;
(4) 15ml of the crude product is taken as a metering unit and is respectively added into a 50ml centrifuge tube, then 30ml of deionized water is added, and the centrifugation is carried out. Repeatedly washing with water for three times or more, centrifuging, and finally drying to obtain a pure product.
Example 4
The materials used were: palladium acetate 5 parts, polyethylene glycol: (M w35 parts of =2000 g/mol), 50 parts of tetra-tert-butyl ammonium bromide, 200 parts of potassium carbonate and monomer AA (carbon)=C10) 100 parts of monomer BB (4, 4' -diiododiphenyl ether) 100 parts, solvent N, N-Dimethylformamide (DMF) 900 parts, and LED blue light (lambda =465 nm).
The structural formulas of the monomer AA and the monomer BB are as follows:
the synthesis steps of the polyurethane are as follows:
(1) dissolving 100 parts of the monomers AA and BB in 700 parts of DMF solvent respectively, and stirring uniformly for later use;
(2) placing 5 parts of palladium acetate, 35 parts of polyethylene glycol, 50 parts of quaternary ammonium salt and 200 parts of alkali into a 250ml two-mouth bottle, vacuumizing for 5 minutes by using a pump, and introducing Ar2Under the protection of gas, adding 200 parts of DMF (dimethyl formamide) solvent, placing the mixture into an oil bath kettle, gradually heating to 80 ℃ under the stirring condition, reacting for 15 minutes, and then cooling the system to room temperature to prepare a well-dispersed nano palladium catalyst system;
(3) and (3) adding the monomer mixed solution prepared in the step (1) into the nano catalyst system in the step (2). Placing the system in LED illumination and reacting at the temperature of 25-30 ℃ for 12 hours to obtain a polymerization product;
(4) 15ml of the crude product is taken as a metering unit and is respectively added into a 50ml centrifuge tube, then 30ml of deionized water is added, and the centrifugation is carried out. Repeatedly washing with water for three times or more, centrifuging, and finally drying to obtain a pure product.
Example 5 (comparative example 1) (no light comparison)
The materials used were: 15 parts of palladium acetate and polyethylene glycol(s) (II)M w25 parts of =1000 g/mol), 150 parts of tetra-tert-butylammonium bromide, 220 parts of potassium carbonate and monomer AA (carbon = C)3) 100 parts of monomer BB (4, 4' -diiododiphenyl ether) 100 parts, and 800 parts of solvent N, N-Dimethylformamide (DMF).
Example 6 (comparative example 1) (comparative without Quaternary ammonium salt)
The materials used were: 15 parts of palladium acetate and polyethylene glycol(s) (II)M w25 parts of (1000 g/mol), 220 parts of potassium carbonate and monomer AA (carbon = C)3) 100 parts, 100 parts of monomer BB (4, 4' -diiododiphenyl ether), 800 parts of solvent N, N-Dimethylformamide (DMF), and blue LED light (lambda =465 nm).
The polyurethane synthesis method is the same as the step of example 1.
The polymers of examples 1-3 were analyzed by molecular weight measurement using gel chromatography GPC, and the results of characterization are shown in Table 1:
TABLE 1
Example 1 compared to comparative example 5, LED illumination was higher in molecular weight than the polymer obtained in the absence of illumination, indicating that LED illumination promotes the polymerization rate and thus higher molecular weight products. Example 1 in comparison to comparative example 6, no polymer was formed without the addition of quaternary ammonium salt tetra-t-butylammonium bromide, indicating that the addition of quaternary ammonium salt allows the polymerization to proceed under mild conditions. FIG. 1 shows the GPC results of the polymer in example 1, from which it is apparent that a polymer having a high molecular weight portion is formed with a small amount of oligomer formation, and a broad molecular weight curve peak is a typical characteristic of the polycondensation reaction. Fig. 2 (a) and (b) are a TEM image and a particle size distribution calculation result image of the nano-palladium catalyst, respectively, and it can be seen from the images that a nano-palladium catalyst system with good dispersibility can be obtained by using the nano-palladium catalyst preparation method of the present invention and the particle size distribution of the catalyst is about 7 nm. In examples 1 to 4, polyurethane products having corresponding molecular weights were obtained, which demonstrates that the process of the present invention can be used to synthesize polyurethanes. In addition, the final polymer main chain contains cinnamate structure, which provides conditions for further post-modification of the polymer, such as ultraviolet crosslinking and cross-linking by adding polythiol, and it is emphasized that the invention only provides a polymerization method, and the work of post-modification of the polymer is not repeated herein.
The above description is not intended to limit the present invention, but rather, the present invention is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the present invention.
Claims (4)
1. A method for synthesizing polyurethane by promoting nano palladium-catalyzed Heck coupling reaction with visible light is characterized by comprising the following specific steps:
(1) preparing a monomer mixed solution: dissolving 100 parts of AA monomer and BB monomer in 750 parts of solvent 350-750 parts, and uniformly stirring to obtain a monomer mixed solution; here, the AA monomer is composed of isocyanate acrylate and carbon chain length of C3~C18The BB monomer is 1, 4-diiodobenzene, 4 ' -diiodobiphenyl or 4 ', 4 ' -diiododiphenyl ether;
(2) preparing a nano palladium catalyst system: placing 5-20 parts of palladium acetate, 10-50 parts of polyethylene glycol, 50-200 parts of quaternary ammonium salt and 100 parts of alkali in a two-mouth bottle, vacuumizing for 5-20 minutes by using a pump, and introducing Ar2Under the protection of gas, adding 350 parts of solvent 120-plus, placing the mixture into an oil bath pot, gradually heating to 40-120 ℃ under the stirring condition, reacting for 10-30 minutes, and then cooling the system to room temperature to obtain a well-dispersed nano palladium catalyst system;
(3) preparing a polyurethane primary product: adding the monomer mixed solution prepared in the step (1) into the nano-catalyst system obtained in the step (2); placing the system under LED blue light to perform illumination reaction at the reaction temperature of 25-30 ℃ for 12-24 hours to obtain a polyurethane primary product;
(4) and (3) post-treatment: centrifugally washing the primary product obtained in the step (3) with ionized water, and repeating for more than 3 times; drying to obtain a pure product;
wherein the components are calculated according to parts by mass.
2. The method of claim 1, wherein the solvent is N, N-dimethylformamide.
3. The method of claim 1, wherein the quaternary ammonium salt is selected from one of tetra-tert-butylammonium bromide, tetra-tert-butylammonium iodide, and tetra-tert-butylammonium chloride.
4. The method of claim 1, wherein the base is at least one of potassium carbonate, cesium carbonate, sodium acetate, silver acetate, triethylamine, potassium phosphate, sodium carbonate.
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| 聚乙二醇作为溶剂和催化剂载体在有机合成中的应用;车阳等;《化学世界》;20171231(第8期);第490-503页 * |
| 钯纳米颗粒制备方法的研究进展;崔泽琳等;《化学与黏合》;20161231;第38卷(第4期);第290-293页 * |
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