CN115612085A - Method for synthesizing carbon dioxide-based multipolymer and co-producing PC (polycarbonate) - Google Patents
Method for synthesizing carbon dioxide-based multipolymer and co-producing PC (polycarbonate) Download PDFInfo
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Abstract
A method for synthesizing carbon dioxide-based multipolymer and co-producing PC (polycarbonate) belongs to the technical field of multipolymers. The preparation method is characterized by comprising the following preparation steps: putting epoxypropane, a comonomer and a nonmetal catalyst into a reactor, filling carbon dioxide to control pressure, and carrying out copolymerization reaction at a certain temperature; after reacting to a certain degree, maintaining the pressure, adding an organic solvent, and continuously reacting to obtain a glue solution; further dissolving the glue solution by using an organic solvent, adding alcohol to separate out a precipitate, and washing and devolatilizing the solid to obtain a carbon dioxide-based multipolymer; and rectifying, extracting and separating to obtain the PC. According to the invention, the carbon dioxide-based multipolymer is synthesized and the PC is co-produced by taking the epoxypropane and the carbon dioxide as raw materials, the reaction pressure is low, the temperature is low, no waste gas and no waste water are generated, and the co-production of the carbon dioxide-based multipolymer by using the non-metallic catalyst does not have residual metal, so that the method is an environment-friendly and energy-saving synthesis method and is more widely applied.
Description
Technical Field
A method for synthesizing carbon dioxide-based multipolymer and co-producing PC (polycarbonate) belongs to the technical field of multipolymers.
Background
The carbon dioxide-based multipolymer is a binary or multipolymer synthesized by copolymerizing carbon dioxide and monomers such as epoxide, acid anhydride and the like. The biodegradable polyester film has the characteristics of high barrier property, transparency, full biodegradation and the like, and is an excellent biodegradable material.
Propylene Carbonate (PC) is a high-boiling-point high-polarity organic solvent with excellent performance and is widely applied to various fields. The PC synthesis method mainly comprises a phosgene method, an ester exchange method, a cycloaddition method of propylene oxide and carbon dioxide, and the like. Most of catalysts used in the existing synthesis method are metal catalysts, and metal residues exist in the synthesized PC material; because lithium batteries are sensitive to metals, the problem of metal residues in PC materials limits the application of PC in the field of lithium batteries.
During the synthesis of the carbon dioxide-based multipolymer, if propylene oxide exists in the monomer, the propylene carbonate can be generated by cycloaddition reaction with carbon dioxide by adjusting the reaction condition and the catalyst proportion. However, in the conventional synthesis method of the carbon dioxide based multipolymer, due to the existence of the reaction, propylene oxide and carbon dioxide are consumed, so that the forward resistance of the copolymerization reaction is increased, the molecular weight of the obtained carbon dioxide based multipolymer is small, and a high molecular weight product is difficult to obtain.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art, and provides a method for simultaneously co-producing PC by synthesizing carbon dioxide-based multipolymer, which can improve the molecular weight of the multipolymer.
The technical scheme adopted by the invention for solving the technical problem is as follows: the method for synthesizing the carbon dioxide-based multipolymer and co-producing PC comprises a binary reaction taking propylene oxide and carbon dioxide as main reaction raw materials, a ternary synthesis reaction taking propylene oxide, carbon dioxide and phthalic anhydride as main reaction raw materials, and a quaternary or more than quaternary synthesis reaction adding other anhydride or/and epoxy olefin on the basis;
the preparation method is characterized by comprising the following preparation steps:
1) Putting epoxypropane, a comonomer and a nonmetal catalyst into a reactor, filling carbon dioxide for copolymerization reaction to prepare a glue solution, and keeping the reaction temperature to be 40-100 ℃ and the reaction pressure to be 0.1MPa-4.0 MPa during the copolymerization reaction; the mol ratio of the propylene oxide to the comonomer to the nonmetal catalyst is (800 to 2500): (0 to 2000): 1;
2) Further dissolving the glue solution prepared in the step 1) by using an organic solvent, adding alcohol to separate out a precipitate, and washing and devolatilizing solid obtained by solid-liquid separation to obtain a carbon dioxide-based multipolymer; and rectifying, extracting and separating the liquid after solid-liquid separation to obtain the PC.
In the process of carbon dioxide-based multicomponent copolymerization, the method is carried out by using a nonmetal catalyst, and the obtained PC material has no metal residue and can be applied to the field of lithium batteries. The viscosity of the reaction system can be reduced after the PC is co-produced, and uniform stirring and discharging in the reaction system are facilitated; can reduce or even prevent the polycarbonate products from adhering to the kettle wall.
Specifically, in the method for simultaneously co-producing PC by synthesizing the carbon dioxide-based multipolymer, the comonomer in the step 1) is one or more than two anhydride monomers and/or epoxides except propylene oxide.
PC is obtained by the synthetic reaction of propylene oxide and carbon dioxide.
In the binary reaction using propylene oxide and carbon dioxide as main reaction raw materials, polycarbonate and PC products can be obtained simultaneously by adjusting reaction conditions, catalyst proportion, adding a proper solvent and the like.
The ternary synthesis reaction of propylene oxide, carbon dioxide and phthalic anhydride, and the simultaneous addition of other anhydride or/and olefin oxide including the three raw materials, such as: 1,8 naphthalene anhydride, ethylene oxide, butylene oxide, cyclohexene oxide, etc., all of which can also simultaneously produce polycarbonate and PC and the corresponding alkenyl carbonates.
Such as: ethylene Carbonate (EC) is produced during the polymerization with ethylene oxide and cyclohexene carbonate (CHC) is produced during the polymerization with cyclohexene oxide. In the present invention, the other epoxides than propylene oxide include, but are not limited to, ethylene oxide, butylene oxide, cyclohexene oxide, epichlorohydrin.
In the present invention, the acid anhydride monomers include, but are not limited to, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, 1,8-naphthalic anhydride, tetrabromophthalic anhydride.
The carbon dioxide-based multipolymer for co-producing PC is preferably propylene oxide-carbon dioxide binary copolymer (PPC) and propylene oxide-phthalic anhydride-carbon dioxide ternary copolymer (PPCP), and valuable co-products PC can be obtained by fully utilizing side reactions in the copolymerization reaction of the carbon dioxide-based multipolymer.
Specifically, in the method for simultaneously co-producing PC by synthesizing the carbon dioxide-based multipolymer, the nonmetal catalyst in the step 1) is a composite catalyst formed by matching Lewis acid/alkali pairs. The Lewis acid/alkali can meet the basic requirement of the invention for the complex composite catalyst, and the PC is co-produced while the copolymerization is carried out.
The Lewis acid comprises: one or more of triethylboron, tripropylboron, tributylboron, tri-sec-butylborane, triphenylboron, tris (pentafluorophenyl) boron, diethylmethoxyborane, bis (trimethylphenyl) boron fluoride. Triethylboron is preferred.
Said lewis base comprises: one or more of tetra-n-butylammonium fluoride, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium iodide, tetra-n-propylammonium fluoride, tetra-n-propylammonium chloride, tetra-n-propylammonium bromide, tetra-n-propylammonium iodide, and bis (triphenylphosphoranylidene) ammonium chloride. Tetra-n-butylammonium chloride and tetra-n-butylammonium bromide are preferred.
The Lewis acid and Lewis base can be used as Lewis acid/alkali pairs to be matched to form the composite catalyst.
The invention can also adjust the output ratio of the carbon dioxide-based multipolymer and the coproduct PC by adjusting the ratio of the catalyst, can greatly increase the yield of the coproduct PC, and has controllable yield. Preferably, in the method for synthesizing the carbon dioxide-based multipolymer and co-producing PC, the nonmetal catalyst in the step 1) is a composite catalyst formed by mixing trialkyl boron and tetra-n-butyl ammonium halide according to a molar ratio of (1.3 to 3) to 1. The optimized composite catalyst is more suitable for the technological conditions of the copolymerization reaction of the invention, and can obtain the copolymer with larger molecular weight. The process of adding the solvent in the midway can be matched to simultaneously produce PC with high yield.
More preferably, in the method for simultaneously co-producing PC by synthesizing the carbon dioxide-based multipolymer, the nonmetal catalyst in the step 1) is a composite catalyst formed by combining trialkyl boron and tetra-n-butyl ammonium halide according to a molar ratio of (2.0-2.6): 1. The composite catalyst with further optimized proportion can achieve the best effect of co-producing PC by the carbon dioxide-based multipolymer, and simultaneously ensure the yield of the carbon dioxide-based multipolymer and the molecular weight of the multipolymer. The molar ratio of trialkylborons to tetra-n-butylammonium halide (chloride, bromide) is more preferably (2.1-2.5): 1.
Preferably, in the method for simultaneously co-producing PC by synthesizing the carbon dioxide-based multipolymer, the molar ratio of the propylene oxide to the nonmetal catalyst in the step 1) is (1600 to 2000): 1. preferably, in the method for synthesizing the carbon dioxide-based multipolymer and co-producing PC, the reaction temperature in the step 1) is 70-90 ℃, and the reaction pressure is 1MPa-2MPa. The preferable addition amount, reaction temperature and reaction pressure of the non-metal catalyst are all to control the rate of the polymerization reaction and the synthesis reaction in the reaction system of the invention, so that the yield of the co-product can be better improved. Further preferably, the reaction temperature is 75 ℃ to 80 ℃, and the reaction pressure is 1.1MPa to 1.5MPa.
Preferably, in the method for simultaneously co-producing PC by synthesizing the carbon dioxide-based multipolymer, after the copolymerization reaction in the step 1) is carried out for 2h to 5h, an organic solvent is added into the reaction system under the pressure maintaining condition, and the reaction temperature and the reaction pressure in the step 1) are kept for continuous reaction for 4h to 6h to obtain a glue solution; the mass ratio of the organic solvent to the propylene oxide in the step 1) is (0.01-2) to 1.
In the process of carbon dioxide-based multicomponent copolymerization, a certain proportion of organic solvent is added at a proper time, the concentrations of monomers and catalysts are reduced in the process of polymerization, the heat transfer efficiency and the mass transfer efficiency in a reaction system are increased, and the copolymerization reaction and the PC synthesis are more sufficient. Meanwhile, the molecular weight of the carbon dioxide-based multipolymer and the yield of PC are improved.
Specifically, in the method for simultaneously co-producing PC by synthesizing carbon dioxide-based multipolymer, the organic solvent is one or a mixed solvent of more than two of methyl acetate, ethyl acetate, dichloromethane, dichloroethane, dichloropropane, tetrahydrofuran and methyl tetrahydrofuran. The organic solvent can meet the process requirements of the invention, and the purposes of increasing the heat transfer efficiency and the mass transfer efficiency in the reaction system are achieved while the copolymerization reaction and the synthesis reaction are kept to be normally carried out after the organic solvent is added into the reaction system.
Preferably, in the method for simultaneously co-producing PC by synthesizing the carbon dioxide-based multipolymer, the organic solvent is methyl acetate and dichloromethane or dichloroethane according to the mass ratio of 1~7:93 to 99 parts of mixed solvent. The preferred organic solvent is added into the reaction system at a proper time, so that the yield of the co-produced PC is higher, the copolymer with higher molecular weight is obtained, and the total yield of the PC and the copolymer is higher.
Preferably, in the method for simultaneously co-producing PC by synthesizing the carbon dioxide-based multipolymer, the mass ratio of the organic solvent to the propylene oxide in the step 1) is (0.1-0.5): 1. When the viscosity of the glue solution is higher during the polymerization reaction, the organic solvent is added and the reaction is continued for a period of time. After the solvent is added, the yield of PC can be increased, the viscosity of the glue solution is reduced, and the conditions of heat transfer and mass transfer are good, so that the reaction is more complete. The preferred amount of solvent added is such that it achieves adequate heat and mass transfer while maintaining the reactant concentrations within the appropriate range, resulting in a higher molecular weight copolymer.
Compared with the prior art, the method for synthesizing the carbon dioxide-based multipolymer and co-producing the PC has the beneficial effects that: according to the invention, the carbon dioxide-based multipolymer is synthesized and the PC is co-produced by taking the epoxypropane and the carbon dioxide as raw materials, the reaction pressure is low, the temperature is low, no waste gas and no waste water are generated, and the co-production of the carbon dioxide-based multipolymer by using the non-metallic catalyst does not have residual metal, so that the method is an environment-friendly and energy-saving synthesis method and is more widely applied. The production ratio of the carbon dioxide-based multipolymer and the coproduct PC is controlled by adjusting the mixture ratio of each catalyst, adding a proper amount of solvent during reaction, performing segmented reaction under different pressures or different temperatures and the like.
Detailed Description
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an", and "the" are intended to include the plural forms as well, and furthermore, the terms "comprises" and "having", and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
The invention is further illustrated by the following specific examples, of which example 1 is the best mode of practice.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Example 1
In a dry kettle, nitrogen is adopted to replace air in the kettle, then the materials are fed, and the mol ratio of the propylene oxide to the nonmetal catalyst is 1800:1 into a 5L high pressure stirred reactor, the molar ratio of triethylboron to tetra-n-butylammonium chloride in the non-metallic catalyst was 2.3. Introducing carbon dioxide to 1.2MPa, stirring at 70 ℃ for reaction for 2 hours, and then adding an organic solvent under pressure, wherein the organic solvent is methyl acetate and dichloromethane in a mass ratio of 4:95 percent of mixed solvent, and the amount of the added organic solvent is 40 percent of the mass of the added propylene oxide; the reaction was continued for 6h while maintaining the temperature and pressure. Dissolving the prepared glue solution with dichloromethane, precipitating with ethanol, devolatilizing, granulating and drying to obtain a finished product PPC; washing machineAnd rectifying and filtering the washed supernatant and the solvent condensed and recovered after devolatilization to obtain the PC. Measuring the molecular weight of the PPC by GPC; testing the content of PC in the glue solution by using a nuclear magnetic resonance spectrometer, and testing the content of refined PC by using a weighing method; and testing the content of heavy metal in the PC by using an inductively coupled plasma emission spectrometry. Analyzed to obtain the number average molecular weight of PPCMn/PDI of 1.16X 10 5 g/mol/2.69; PC/(PC + PPC) =53%; the yield of PC is 94%; no heavy metals were detected in PC.
Example 2
In a dry kettle, nitrogen is adopted to replace air in the kettle, then the materials are fed, and the mol ratio of the propylene oxide to the nonmetal catalyst is 1800:1 is added into a 5L high-pressure stirring reactor, and the molar ratio of triethyl boron to tetra-n-butyl ammonium bromide in the nonmetal catalyst is 2.0. Carbon dioxide is charged to 1.2MPa, and the mixture is stirred and reacted for 2 hours at 70 ℃. Then, adding an organic solvent under pressure, wherein the organic solvent is methyl acetate and dichloromethane in a mass ratio of 1:99 percent of mixed solvent, and the amount of the added organic solvent is 50 percent of the mass of the added propylene oxide; the reaction was continued for 6h while maintaining the temperature and pressure. Dissolving the prepared glue solution with dichloromethane, precipitating with ethanol, devolatilizing, granulating and drying to obtain a finished product PPC; and (3) rectifying and filtering the washed supernatant and the solvent condensed and recovered after devolatilization to obtain the PC. Measuring the molecular weight of the PPC by GPC; testing the content of PC in the glue solution by using a nuclear magnetic resonance spectrometer, and testing the content of refined PC by using a weighing method; and testing the content of heavy metal in the PC by using an inductively coupled plasma emission spectrometry. Analyzed to obtain the number average molecular weight of PPCMn/PDI of 8.95 × 10 4 g/mol/2.69; PC/(PC + PPC) =51%; the yield of PC is 94%; no heavy metals were detected in PC.
Example 3
In a dry kettle, nitrogen is used for replacing air in the kettle, then the materials are fed, and the epoxy propane, phthalic anhydride and non-metal catalyst are mixed according to the mol ratio of 1800:560:1 into a 5L high pressure stirred reactor, the molar ratio of triethylboron to tetra-n-butylammonium chloride in the non-metallic catalyst was 2.6. Charging carbon dioxide to 1.5MPa, stirring at 75 ℃ for reaction for 4 hours, and then adding organic solvent under pressure, wherein the organic solvent is methyl acetate and dichloroethaneThe quantity ratio is 7:93 percent of mixed solvent, and the amount of the added organic solvent is 10 percent of the mass of the added propylene oxide; the reaction was continued for 5h while maintaining the temperature and pressure. Dissolving the prepared glue solution with dichloroethane, precipitating and separating out with ethanol, devolatilizing, granulating and drying to obtain a finished product PPCP; and (3) rectifying and filtering the washed supernatant and the solvent condensed and recovered after devolatilization to obtain the PC. Measuring the molecular weight of the PPCP by GPC; testing the content of PC in the glue solution by using a nuclear magnetic resonance spectrometer, and testing the content of refined PC by using a weighing method; and testing the content of heavy metal in the PC by using an inductively coupled plasma emission spectrometry. Analyzed to obtain the number average molecular weight of PPCPMn/PDI of 1.75X 10 5 g/mol/2.44; PC/(PC + PPCP) =35%; the yield of PC is 93%; no heavy metals were detected in PC.
Example 4
In a dry kettle, nitrogen is used for replacing air in the kettle, then the materials are fed, and the epoxy propane, phthalic anhydride and non-metal catalyst are mixed according to the mol ratio of 1800:430:1 is added into a 5L high-pressure stirring reactor, and the molar ratio of triethyl boron to tetra-n-butyl ammonium bromide in the nonmetal catalyst is 1.3. Introducing carbon dioxide to 2.0MPa, stirring at 70 ℃ for reaction for 4h, then adding dichloroethane under pressure, wherein the amount of the added dichloroethane is 1% of the mass of the added propylene oxide, and continuously reacting for 5h while keeping the temperature and the pressure unchanged. Dissolving the prepared glue solution with dichloroethane, precipitating and separating out with ethanol, devolatilizing, granulating and drying to obtain a finished product PPCP; and (3) rectifying and filtering the washed supernatant and the solvent condensed and recovered after devolatilization to obtain the PC. Measuring the molecular weight of PPCP by GPC; testing the content of PC in the glue solution by using a nuclear magnetic resonance spectrometer, and testing the content of refined PC by using a weighing method; and testing the content of heavy metal in the PC by using an inductively coupled plasma emission spectrometry. Analyzed to obtain the number average molecular weight of PPCPMn/PDI is 1.31X 10 5 g/mol/2.15; PC/(PC + PPCP) =38%; the yield of PC is 91%; no heavy metals were detected in PC.
Example 5
In a dry kettle, nitrogen is adopted to replace air in the kettle, then the materials are fed, and propylene oxide, ethylene oxide, phthalic anhydride and a nonmetal catalyst are mixed according to the mol ratio of 1080:720:560:1 adding 5L of high-pressure stirring reactionIn the reactor, the molar ratio of the triethylboron to the tetra-n-butylammonium bromide in the non-metallic catalyst is 3:1. Charging carbon dioxide to 1.0MPa, stirring at 90 ℃ for reaction for 4h, then adding dichloroethane under pressure, wherein the amount of the added dichloroethane is twice of the mass of the added propylene oxide, and continuously reacting for 4h while keeping the temperature and the pressure unchanged. Dissolving the prepared glue solution with dichloroethane, precipitating and separating out with ethanol, devolatilizing, granulating and drying to obtain a finished product PPCEP; and (3) rectifying and filtering the washed supernatant and the solvent condensed and recovered after devolatilization to obtain the PC. Measuring the molecular weight of the PPCEP by GPC; testing the content of PC in the glue solution by using a nuclear magnetic resonance spectrometer, and testing the content of refined PC by using a weighing method; and testing the content of heavy metal in the PC by using an inductively coupled plasma emission spectrometry. Analyzed to obtain the number average molecular weight of PPCEPMn/PDI of 1.54 × 10 5 g/mol/2.69; PC/(PC + PPCEP) =45%; the yield of PC is 83%; no heavy metals were detected in PC.
Example 6
In a dry kettle, nitrogen is adopted to replace air in the kettle, then the materials are fed, and the molar ratio of the epoxy propane, the epoxy cyclohexane, the phthalic anhydride and the nonmetal catalyst is 800:900:1100:1 into a 5L high pressure stirred reactor, the molar ratio of triethylboron to tetra-n-butylammonium chloride in the non-metallic catalyst was 2.3. Introducing carbon dioxide to 0.1MPa, stirring at 40 ℃ for reaction for 5 hours, then adding dichloropropane under pressure, wherein the amount of the added dichloroethane is twice of the mass of the added propylene oxide, and continuously reacting for 4 hours while keeping the temperature and the pressure unchanged. Dissolving the prepared glue solution with dichloropropane, precipitating with ethanol, devolatilizing, granulating and drying to obtain a finished product PPCCP; and (3) rectifying and filtering the washed supernatant and the solvent condensed and recovered after devolatilization to obtain the PC. Measuring the molecular weight of the PPCCP by GPC; testing the content of PC in the glue solution by using a nuclear magnetic resonance spectrometer, and testing the content of refined PC by using a weighing method; and testing the content of heavy metal in the PC by using an inductively coupled plasma emission spectrometry. Number average molecular weight of PPCCPMn/PDI is 1.07 x 10 5 g/mol/2.23; PC/(PC + PPCCP) =31%; the yield of PC is 75%; no heavy metal content was detected in the PC.
Example 7
In a dry kettleAnd after replacing air in the kettle with nitrogen, feeding materials, wherein the molar ratio of the propylene oxide to the nonmetal catalyst is 2500:1 into a 5L high pressure stirred reactor, the molar ratio of triethylboron to tetra-n-butylammonium chloride in the non-metallic catalyst was 2.3. Introducing carbon dioxide to 4.0MPa, stirring at 100 ℃ for reaction for 2h, then adding dichloroethane under pressure, wherein the amount of the dichloroethane is three times of the mass of the added propylene oxide, and continuously reacting for 6h while keeping the temperature and the pressure unchanged. Dissolving the prepared glue solution with dichloromethane, precipitating with ethanol, devolatilizing, granulating and drying to obtain a finished product PPC; and (3) rectifying and filtering the washed supernatant and the solvent condensed and recovered after devolatilization to obtain the PC. Measuring the molecular weight of the PPC by GPC; testing the content of PC in the glue solution by using a nuclear magnetic resonance spectrometer, and testing the content of refined PC by using a weighing method; and testing the content of heavy metal in the PC by using an inductively coupled plasma emission spectrometry. Analyzed to obtain the number average molecular weight of PPCMn/PDI is 1.08X 10 5 g/mol/2.16; PC/(PC + PPC) =61%; the yield of PC is 90%; no heavy metals were detected in PC.
Example 8
In a dry kettle, nitrogen is adopted to replace the air in the kettle, then the materials are fed, propylene oxide and a nonmetal catalyst are added into a 5L high-pressure stirring reactor according to the proportion of the embodiment 2, carbon dioxide is filled to 1.2MPa, and the stirring reaction is carried out for 10 hours at 70 ℃. Dissolving the prepared glue solution with dichloromethane, precipitating with ethanol, devolatilizing, granulating and drying to obtain a finished product PPC; and (3) rectifying and filtering the washed supernatant and the solvent condensed and recovered after devolatilization to obtain the PC. Measuring the molecular weight of the PPC by GPC; testing the content of PC in the glue solution by using a nuclear magnetic resonance spectrometer, and testing the content of refined PC by using a weighing method; and testing the content of the heavy metal in the PC by using an inductively coupled plasma emission spectrometry. Analyzed to obtain the number average molecular weight of PPCMn/PDI of 6.75X 10 4 g/mol/2.69; PC/(PC + PPC) =34%; the yield of PC is 92%; no heavy metals were detected in PC.
Example 9
In a dry kettle, the air in the kettle is replaced by nitrogen, then the materials are charged, and the epoxy propane, the phthalic anhydride and the non-metal catalyst are added into 5L of the mixture according to the proportion of the embodiment 3 and stirred under high pressureIn the reactor, the molar ratio of the triethylboron to the tetra-n-butylammonium chloride in the nonmetal catalyst is 5:1. Carbon dioxide is charged to 1.0MPa, and the mixture is stirred and reacted for 10 hours at the temperature of 75 ℃. Dissolving the prepared glue solution with dichloromethane, precipitating with ethanol, devolatilizing, granulating, and drying to obtain a finished product PPCP; and (4) rectifying and filtering the washed supernatant and the solvent condensed and recovered after devolatilization to obtain the PC. Measuring the molecular weight of the PPCP by GPC; testing the content of PC in the glue solution by using a nuclear magnetic resonance spectrometer, and testing the content of refined PC by using a weighing method; and testing the content of heavy metal in the PC by using an inductively coupled plasma emission spectrometry. Analyzed to obtain the number average molecular weight of PPCPMn/PDI of 7.61X 10 4 g/mol/2.18; PC/(PC + PPCP) =21%; the yield of PC is 93%; no heavy metals were detected in PC.
Comparative example 1
In a dry kettle, nitrogen is adopted to replace air in the kettle and then the materials are put into the kettle, propylene oxide and catalyst ZnCl are added 2 /PPh 3 C 10 H 21 Br was charged in a 5L high-pressure stirred reactor in a molar ratio of 1600. Introducing carbon dioxide to 1.5MPa, stirring at 120 ℃ and reacting for 3h to generate PC. Testing the content of the refined PC by a weighing method; and testing the content of heavy metal in the PC by using an inductively coupled plasma emission spectrometry. The yield of PC is 90% by analysis; the content of zinc (Zn) in PC was 0.66mg/kg.
And (3) performance testing:
molecular weight: the molecular weight of the polymer was analyzed by GPC, according to method "GB/T31124-2014 appendix B".
The content of PC: the weight of PC, polymer (Polymer) was determined by NMR spectroscopy and the PC content was expressed as PC/(PC + Polymer). Times.100%.
Yield of PC: the yield of PC was measured by NMR spectrometer, and the recovery of PC was weighed by weighing, and the ratio of the two was the yield of PC.
Heavy metal Zn: the Zn content in PC was tested according to the method of SJ/T11568-2016 appendix B.
The test results for example 1~9, comparative example 1 are shown in table 1:
TABLE 1 test results
From the above table, it is known that the production of PC can be significantly increased by adjusting the catalyst ratio and adding the solvent, and the production ratio of the copolymer and the co-product can be controlled, and high-quality PC can be obtained by rectification.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (10)
1. A method for synthesizing carbon dioxide-based multipolymer and co-producing PC comprises a binary reaction taking propylene oxide and carbon dioxide as main reaction raw materials, a ternary synthesis reaction taking propylene oxide, carbon dioxide and phthalic anhydride as main reaction raw materials, and a quaternary or more than quaternary synthesis reaction adding other anhydride or/and epoxy olefin on the basis;
the preparation method is characterized by comprising the following preparation steps:
1) Putting epoxypropane, a comonomer and a nonmetal catalyst into a reactor, filling carbon dioxide for copolymerization reaction to prepare a glue solution, and keeping the reaction temperature to be 40-100 ℃ and the reaction pressure to be 0.1MPa-4.0 MPa during the copolymerization reaction; the mol ratio of the propylene oxide to the comonomer to the nonmetal catalyst is (800 to 2500): (0 to 2000): 1;
2) Further dissolving the glue solution prepared in the step 1) by using an organic solvent, adding alcohol to separate out a precipitate, and washing and devolatilizing solid obtained by solid-liquid separation to obtain a carbon dioxide-based multipolymer; and (4) rectifying, extracting and separating the liquid after solid-liquid separation to obtain the PC.
2. The method for synthesizing carbon dioxide-based multipolymer and co-producing PC according to claim 1, characterized in that:
the comonomer in the step 1) is one or more than two anhydride monomers and/or other epoxides except propylene oxide.
3. The method for synthesizing carbon dioxide-based multipolymer and co-producing PC according to claim 1, characterized in that:
the nonmetal catalyst in the step 1) is a composite catalyst formed by matching Lewis acid/alkali pairs.
4. The method for synthesizing carbon dioxide-based multipolymer and co-producing PC according to claim 1, characterized in that:
the nonmetal catalyst in the step 1) is a composite catalyst formed by mixing trialkyl boron and tetra-n-butyl ammonium halide according to the mol ratio of (1.3 to 3) to 1.
5. The method for synthesizing carbon dioxide-based multipolymer and co-producing PC according to claim 1, characterized in that:
the molar ratio of the propylene oxide to the nonmetal catalyst in the step 1) is (1600 to 2000): 1.
6. the method for synthesizing carbon dioxide-based multipolymer and co-producing PC according to claim 1, characterized in that:
the reaction temperature in the step 1) is 70-90 ℃, and the reaction pressure is 1.0-2.0 MPa.
7. The method for synthesizing carbon dioxide-based multipolymer and co-producing PC according to claim 1, characterized in that:
after the copolymerization reaction in the step 1) is carried out for 2h to 5h, adding an organic solvent into a reaction system under a pressure maintaining condition, and continuously reacting for 4h to 6h while keeping the reaction temperature and the reaction pressure in the step 1) to obtain a glue solution; the mass ratio of the organic solvent to the propylene oxide in the step 1) is (0.01-2) to 1.
8. The method for synthesizing carbon dioxide-based multipolymer and co-producing PC according to claim 1 or 7, characterized in that:
the organic solvent is one or a mixed solvent of more than two of methyl acetate, ethyl acetate, dichloromethane, dichloroethane, dichloropropane, tetrahydrofuran and methyltetrahydrofuran.
9. The method for synthesizing carbon dioxide-based multipolymer and co-producing PC according to claim 1 or 7, characterized in that:
the organic solvent is methyl acetate and dichloromethane or dichloroethane according to the mass ratio of 1~7: 93-99 parts of mixed solvent.
10. The method for synthesizing carbon dioxide-based multipolymer and co-producing PC according to claim 1, characterized in that:
the mass ratio of the organic solvent to the propylene oxide in the step 1) is (0.1-0.5) to 1.
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