CN111635517B - Method for removing catalyst in carbon dioxide-propylene oxide copolymer - Google Patents
Method for removing catalyst in carbon dioxide-propylene oxide copolymer Download PDFInfo
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- CN111635517B CN111635517B CN202010395153.6A CN202010395153A CN111635517B CN 111635517 B CN111635517 B CN 111635517B CN 202010395153 A CN202010395153 A CN 202010395153A CN 111635517 B CN111635517 B CN 111635517B
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- 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
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Abstract
The invention discloses a method for removing a catalyst in a carbon dioxide-epoxypropane copolymer, which is characterized by comprising the following steps of: (1) feeding the epoxypropane-carbon dioxide copolymer and a solvent into a PPC dissolving tank to dissolve to obtain an epoxypropane-carbon dioxide copolymer mixed solution, wherein the solvent comprises at least one of dichloromethane, trichloromethane, carbon tetrachloride, toluene and xylene; (2) sending the epoxypropane-carbon dioxide copolymer mixed solution into a static mixer to be uniformly mixed with acid liquor, and then sending into a high-speed mixing tank to be further blended to form emulsion; (3) and (3) feeding the emulsion into an oil-water separator for layering, washing the obtained bottom oil phase to be neutral, and drying to obtain the epoxypropane-carbon dioxide copolymer with the catalyst completely removed and the residual heavy metal content lower than 110 ppm.
Description
Technical Field
The invention relates to a method for removing a catalyst, in particular to a method for removing a catalyst in a carbon dioxide-epoxypropane copolymer.
Background
One of the main raw materials for synthesizing carbon dioxide-propylene oxide copolymer (PPC) is carbon dioxide, which is a greenhouse gas having the greatest effect on global warming, and thus it is a common consensus worldwide that the amount of carbon dioxide emission is controlled. The carbon dioxide-propylene oxide copolymer (PPC) can consume more than 40 percent of carbon dioxide in the total mass in the synthetic process, and can reduce the emission of a large amount of carbon dioxide. On the other hand, the carbon dioxide-propylene oxide copolymer (PPC) is a fully-degradable polymer, has the advantages of low cost, good transparency and gas barrier property, excellent processing performance and the like, can be widely applied to the field of films and packaging materials, replaces non-degradable plastic products, and has revolutionary significance for solving 'white pollution'.
The existing carbon dioxide-propylene oxide copolymer is directly synthesized by placing carbon dioxide (CO 2) and Propylene Oxide (PO) in a synthesis reaction kettle and reacting under the action of a catalyst, but the catalyst is not completely removed in a synthesized product, the heavy metal content is high, and the product performance is influenced. At present, no relevant research report about a method for removing a catalyst in a carbon dioxide-propylene oxide copolymer is published at home and abroad.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for removing a catalyst in a carbon dioxide-propylene oxide copolymer with low heavy metal content and high product purity.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for removing a catalyst in a carbon dioxide-propylene oxide copolymer comprises the following steps:
(1) feeding the epoxypropane-carbon dioxide copolymer and a solvent into a PPC dissolving tank, controlling the temperature in the PPC dissolving tank to be 45-70 ℃ and the pressure to be 0.2-0.5MpgG, and dissolving to obtain an epoxypropane-carbon dioxide copolymer mixed solution, wherein the solvent comprises at least one of dichloromethane, trichloromethane, carbon tetrachloride, toluene and xylene; the material viscosity is prevented from being too high after the temperature is too low and the pressure is too low, and the temperature and the pressure in the range ensure that the material has reliable fluidity;
(2) sending the epoxypropane-carbon dioxide copolymer mixed solution into a static mixer to be uniformly mixed with acid solution, and then sending the mixture into a high-speed mixing tank to be further blended to form emulsion, wherein the acid solution is an aqueous solution containing at least one of sulfuric acid, hydrochloric acid and benzenesulfonic acid;
(3) and (3) feeding the emulsion into an oil-water separator for layering, washing the obtained bottom oil phase with deionized water to be neutral, and drying to obtain the propylene oxide-carbon dioxide copolymer product with the catalyst removed and the residual heavy metal content in the product lower than 110 ppm.
A PPC polymer feeding hole and a solvent feeding hole are formed in the top of the PPC dissolving tank in the step (1), a porous plate is communicated with the bottom of the PPC polymer feeding hole, and a nozzle is communicated with the bottom of the solvent feeding hole; the PPC dissolving tank is provided with a hot water jacket at the periphery and a stirrer in the axial direction. The polymer has high viscosity and is difficult to dissolve, and the PPC polymer is dissolved in the solvent by arranging a polymer dispersing device, a nozzle, a stirrer and a hot water jacket.
The feeding mass of the solvent in the step (1) is 0.3 to 0.9 time of that of the propylene oxide-carbon dioxide copolymer. If the amount of the solvent is too small, the catalyst cannot be completely removed, and if too much, the load of the subsequent devolatilization section is too large.
The mass concentration of the acid component in the acid liquor in the step (2) is 0.5-5%, and the feeding mass of the acid liquor is 34-60% of that of the propylene oxide-carbon dioxide copolymer. The zinc-based catalyst reacts with the acid liquor and then enters the water phase to achieve the purpose of removing the catalyst, wherein the acid liquor is added in an excessive amount.
And (3) arranging a mixing stirrer in the high-speed mixing tank in the step (2), wherein the rotating speed of the mixing stirrer is 30-120 rpm. The acid liquor and the PPC solution are uniformly mixed, so that the aim of thoroughly removing the catalyst is fulfilled.
Compared with the prior art, the invention has the advantages that: the invention discloses a method for removing a catalyst from a carbon dioxide-propylene oxide copolymer for the first time, wherein the copolymer is subjected to static mixing, high-speed mixing and layering by a layering device in sequence to obtain the catalyst-removed copolymer, and the product obtained by the method has the advantages of low heavy metal content, high product purity and greenness and environmental friendliness.
Drawings
FIG. 1 is a schematic flow diagram of an apparatus for removing a catalyst from a carbon dioxide-propylene oxide copolymer according to the present invention.
Detailed Description
A method for removing a catalyst in a carbon dioxide-propylene oxide copolymer is shown in figure 1 and comprises the following steps:
(1) feeding the epoxypropane-carbon dioxide copolymer and a solvent into a PPC dissolving tank 1, controlling the temperature in the PPC dissolving tank 1 to be 45-70 ℃ and the pressure to be 0.2-0.5MpgG, and dissolving to obtain an epoxypropane-carbon dioxide copolymer mixed solution, wherein the solvent comprises at least one of dichloromethane, trichloromethane, carbon tetrachloride, toluene and xylene; the feeding mass of the solvent is 0.3-0.9 times of that of the propylene oxide-carbon dioxide copolymer;
(2) sending the epoxypropane-carbon dioxide copolymer mixed solution into a static mixer 2, uniformly mixing with an acid solution, and then sending into a high-speed mixing tank 3 for further blending to form emulsion, wherein the acid solution is an aqueous solution containing at least one of sulfuric acid, hydrochloric acid and benzenesulfonic acid; the mass concentration of the acid component in the acid liquor is 0.5-5%, and the feeding mass of the acid liquor is 34-60% of that of the propylene oxide-carbon dioxide copolymer; too low solubility will result in the catalyst not being removed, too high solubility will result in acid remaining in the finished product;
(3) and (3) delivering the emulsion into an oil-water separator 4 for layering, washing the obtained bottom oil phase to be neutral by using deionized water, and drying to obtain a propylene oxide-carbon dioxide copolymer product with the catalyst removed and the content of residual heavy metals in the product lower than 110 ppm.
In the specific embodiment, in the step (1), the top of the PPC dissolving tank 1 is provided with a PPC polymer feed port 6 and a solvent feed port 7, the bottom of the PPC polymer feed port 6 is communicated with a porous plate 8, and the bottom of the solvent feed port 7 is communicated with a nozzle 9; the periphery of the PPC dissolving tank 1 is provided with a hot water jacket 10, and the inner part of the PPC dissolving tank 1 is axially provided with a stirrer 11. The high-speed mixing tank 3 is internally provided with a mixing stirrer 5, and the rotating speed of the mixing stirrer 5 is 30-120 rpm.
Application examples
Example 1
Dissolving 1kg of propylene oxide-carbon dioxide copolymer with 1wt% of zinc content in 0.8kg of chloroform, adding 0.5kg of sulfuric acid solution with the mass concentration of 0.5wt%, emulsifying at a high speed for 5min, standing for 5min for layering, removing an upper aqueous solution, washing a lower solution with deionized water for 2 times until the solution is neutral, and drying to obtain a propylene oxide-carbon dioxide copolymer product with the catalyst completely removed and the zinc content of 105 ppm.
Example 2
Dissolving 1kg of propylene oxide-carbon dioxide copolymer with 0.7wt% of zinc content in 0.8kg of dichloromethane, adding 0.5kg of hydrochloric acid solution with the mass concentration of 2wt%, emulsifying at a high speed for 10min, standing for 10min for layering, removing an upper aqueous solution, washing a lower solution with deionized water for 2 times until the solution is neutral, and drying to obtain a propylene oxide-carbon dioxide copolymer product with the catalyst completely removed and the zinc content of 20 ppm.
Example 3
Dissolving 10kg of propylene oxide-carbon dioxide copolymer with 0.8wt% of zinc content in 8kg of chloroform, adding 5kg of benzenesulfonic acid solution with the mass concentration of 5wt%, emulsifying at a high speed for 5min, standing for 10min for layering, removing the upper-layer aqueous solution, washing the lower-layer solution with deionized water for 2 times until the solution is neutral, and drying to obtain a propylene oxide-carbon dioxide copolymer product with the catalyst completely removed and the zinc content of 50 ppm.
Example 4
Dissolving 1kg of propylene oxide-carbon dioxide copolymer with 0.8wt% of zinc content in 0.3kg of chloroform, adding 0.34kg of benzenesulfonic acid solution with the mass concentration of 3wt%, emulsifying at a high speed for 5min, standing for 10min for layering, removing the upper aqueous solution, washing the lower aqueous solution with deionized water for 2 times until the lower aqueous solution is neutral, and drying to obtain a propylene oxide-carbon dioxide copolymer product with the catalyst completely removed and the zinc content of 70 ppm.
Example 5
Dissolving 1kg of propylene oxide-carbon dioxide copolymer with 0.8wt% of zinc content in 0.9kg of carbon tetrachloride, adding 0.6kg of benzenesulfonic acid solution with the mass concentration of 1wt%, emulsifying at a high speed for 5min, standing for 10min for layering, removing an upper aqueous solution, washing a lower solution with deionized water for 2 times until the solution is neutral, and drying to obtain a propylene oxide-carbon dioxide copolymer product with the catalyst completely removed and the zinc content of 80 ppm.
In addition to the above embodiments, the solvent may be toluene or xylene or at least one or more of dichloromethane, chloroform, carbon tetrachloride, toluene and xylene.
The above description is not intended to limit the invention, nor is the invention limited to the examples set forth above. Those skilled in the art should also appreciate that they may make various changes, modifications, additions and substitutions within the spirit and scope of the invention.
Claims (4)
1. A method for removing a catalyst in a carbon dioxide-propylene oxide copolymer is characterized by comprising the following steps:
(1) feeding the epoxypropane-carbon dioxide copolymer and a solvent into a PPC dissolving tank, controlling the temperature in the PPC dissolving tank to be 45-70 ℃ and the pressure to be 0.2-0.5MpgG, and dissolving to obtain an epoxypropane-carbon dioxide copolymer mixed solution, wherein the solvent comprises at least one of dichloromethane, trichloromethane, carbon tetrachloride, toluene and xylene;
(2) sending the epoxypropane-carbon dioxide copolymer mixed solution into a static mixer, uniformly mixing the epoxypropane-carbon dioxide copolymer mixed solution with an acid solution, and then sending the mixture into a high-speed mixing tank for further blending to form emulsion, wherein the acid solution is an aqueous solution containing at least one of sulfuric acid, hydrochloric acid and benzenesulfonic acid, the mass concentration of an acid component in the acid solution is 0.5-5%, and the mass of an acid solution feed is 34-60% of the mass of the epoxypropane-carbon dioxide copolymer feed;
(3) and (3) delivering the emulsion into an oil-water separator for layering, washing the obtained bottom oil phase to be neutral by using deionized water, and drying to obtain the propylene oxide-carbon dioxide copolymer product with the catalyst completely removed and the residual heavy metal content of less than 110 ppm.
2. The method for removing the catalyst from the carbon dioxide-propylene oxide copolymer according to claim 1, wherein: a PPC polymer feeding hole and a solvent feeding hole are formed in the top of the PPC dissolving tank in the step (1), a porous plate is communicated with the bottom of the PPC polymer feeding hole, and a nozzle is communicated with the bottom of the solvent feeding hole; the PPC dissolving tank is provided with a hot water jacket at the periphery and a stirrer in the axial direction.
3. The method for removing the catalyst from the carbon dioxide-propylene oxide copolymer according to claim 1, wherein: the feeding mass of the solvent in the step (1) is 0.3 to 0.9 time of that of the propylene oxide-carbon dioxide copolymer.
4. The method for removing the catalyst from the carbon dioxide-propylene oxide copolymer according to claim 1, wherein: and (3) arranging a mixing stirrer in the high-speed mixing tank in the step (2), wherein the rotating speed of the mixing stirrer is 30-120 rpm.
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| CN114752045A (en) * | 2022-03-25 | 2022-07-15 | 山东联欣环保科技有限公司 | Post-treatment process and application of carbon dioxide-based biodegradable multipolymer |
| CN116693838B (en) * | 2023-05-10 | 2024-08-27 | 中国科学院长春应用化学研究所 | Compound stabilizer and application thereof in preparation of carbon dioxide-propylene oxide copolymerization crude product |
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| CN101397366B (en) * | 2007-09-28 | 2012-04-11 | 吉林金源北方科技发展有限公司 | Large-scale refining method of carbon dioxide-epoxide copolymer |
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