WO2024120011A1 - Method for co-producing pc while synthesizing carbon dioxide-based multi-component copolymer - Google Patents

Method for co-producing pc while synthesizing carbon dioxide-based multi-component copolymer Download PDF

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WO2024120011A1
WO2024120011A1 PCT/CN2023/124401 CN2023124401W WO2024120011A1 WO 2024120011 A1 WO2024120011 A1 WO 2024120011A1 CN 2023124401 W CN2023124401 W CN 2023124401W WO 2024120011 A1 WO2024120011 A1 WO 2024120011A1
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carbon dioxide
reaction
based multi
propylene oxide
synthesizing
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PCT/CN2023/124401
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French (fr)
Chinese (zh)
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李洪国
魏怀建
李宜格
李峰
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山东联欣环保科技有限公司
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Publication of WO2024120011A1 publication Critical patent/WO2024120011A1/en

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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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock

Definitions

  • the invention discloses a method for synthesizing a carbon dioxide-based multi-polymer and simultaneously co-producing PC, belonging to the technical field of multi-polymers.
  • Carbon dioxide-based multi-polymers refer to binary or multi-polymers formed by copolymerization of carbon dioxide with monomers such as epoxides and acid anhydrides. They generally have high barrier properties, transparency, and full biodegradability, and are a type of excellent biodegradable material.
  • PC Propylene carbonate
  • the main methods for synthesizing PC include phosgene method, transesterification method, and cycloaddition method of propylene oxide and carbon dioxide.
  • the catalysts used in the current synthesis methods are mostly metal catalysts, and there are metal residues in the synthesized PC materials; 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.
  • the technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a method for synthesizing a carbon dioxide-based multi-polymer and simultaneously co-producing PC, which can increase the molecular weight of the copolymer.
  • the method for synthesizing carbon dioxide-based multi-polymers and simultaneously producing PC includes a binary reaction with propylene oxide and carbon dioxide as main reaction raw materials, a ternary synthesis reaction with propylene oxide, carbon dioxide and phthalic anhydride as main reaction raw materials, and a quaternary or higher synthesis reaction with other acid anhydrides and/or epoxy olefins added thereto;
  • step 2) The glue solution prepared in step 1) is further dissolved in an organic solvent, and then alcohol is added to precipitate a precipitate.
  • the solid separated from the solid and liquid is washed and devolatilized to obtain a carbon dioxide-based multi-polymer; the liquid separated from the solid and liquid is distilled and extracted to obtain PC.
  • the present invention uses a non-metallic catalyst in the process of carbon dioxide-based multi-component copolymerization, and the resulting PC material has no metal residue, which can be used in the field of lithium batteries. Moreover, after the co-production of PC, the viscosity of the reaction system can be reduced, which is more conducive to uniform stirring and discharging in the reaction system; it can reduce or even prevent the polycarbonate product from sticking to the reactor wall.
  • the comonomers in step 1) are one or more anhydride monomers and/or other epoxides other than propylene oxide.
  • PC is obtained by the synthesis reaction of propylene oxide and carbon dioxide.
  • the above binary reaction with propylene oxide and carbon dioxide as main reaction raw materials can simultaneously obtain polycarbonate and PC products by adjusting reaction conditions, catalyst ratio, adding appropriate solvent and the like.
  • ethylene oxide ethylene carbonate
  • CHC cyclohexene carbonate
  • other epoxides other than propylene oxide include but are not limited to ethylene oxide, butylene oxide, cyclohexyl oxide, and epichlorohydrin.
  • the acid anhydride monomers include but are not limited to maleic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, 1,8-naphthalene anhydride, and tetrabromophthalic anhydride.
  • the carbon dioxide-based multipolymer for co-producing PC in the present invention is preferably a propylene oxide-carbon dioxide binary copolymer (PPC) or a propylene oxide-phthalic anhydride-carbon dioxide terpolymer (PPCP), which can fully utilize side reactions in the copolymerization reaction of the carbon dioxide-based multipolymer to obtain valuable co-product PC.
  • PPC propylene oxide-carbon dioxide binary copolymer
  • PPCP propylene oxide-phthalic anhydride-carbon dioxide terpolymer
  • the non-metallic catalyst in step 1) is a composite catalyst formed by a Lewis acid/base pair.
  • the composite catalyst formed by a Lewis acid/base pair can meet the basic requirements of the present invention and simultaneously produce PC during copolymerization.
  • the Lewis acid includes one or more of triethylboron, tripropylboron, tributylboron, tri-sec-butylborane, triphenylboron, tri(pentafluorophenyl)boron, diethylmethoxyborane, and di(trimethylphenyl)boron fluoride, preferably triethylboron.
  • the Lewis base includes 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(triphenylphosphorane)ammonium chloride.
  • tetra-n-butylammonium chloride and tetra-n-butylammonium bromide are used.
  • Lewis acids and Lewis bases can be combined as Lewis acid/base pairs to form a composite catalyst.
  • the present invention can also adjust the output ratio of the carbon dioxide-based multi-polymer and the co-product PC by adjusting the ratio of the catalyst, which can greatly increase the production of the co-product PC, and the output is controllable.
  • the non-metallic catalyst described in step 1) is a composite catalyst formed by combining trialkylborane and tetra-n-butylammonium halide in a molar ratio of (1.3 to 3): 1.
  • the preferred composite catalyst is more suitable for the process conditions of the copolymerization reaction of the present invention, and a copolymer with a larger molecular weight can be obtained.
  • PC can be co-produced at a high yield at the same time.
  • the non-metallic catalyst described in step 1) is a composite catalyst formed by combining trialkylborons and tetra-n-butylammonium halide in a molar ratio of (2.0-2.6):1.
  • the composite catalyst with further optimized ratio can achieve the best effect of the carbon dioxide-based multi-polymer co-production of PC of the present invention, while ensuring the yield of both and the molecular weight of the copolymer.
  • the molar ratio of trialkylborons to tetra-n-butylammonium halide (chloride, bromide) is more preferably (2.1-2.5):1.
  • the molar ratio of propylene oxide to non-metallic catalyst in step 1) is (1600-2000):1.
  • the reaction temperature in step 1) is 70°C-90°C, and the reaction pressure is 1MPa-2MPa.
  • the preferred amount of non-metallic catalyst added, the reaction temperature and the reaction pressure are all for controlling the polymerization in the reaction system of the present invention.
  • the reaction and synthesis reaction rates can be increased, thereby better improving the yield of the co-product.
  • Further preferred reaction temperature is 75°C to 80°C, and the reaction pressure is 1.1MPa to 1.5MPa.
  • step 1) After the copolymerization reaction described in step 1) is carried out for 2h to 5h, an organic solvent is added to the reaction system under pressure, and the reaction temperature and reaction pressure of step 1) are maintained to continue the reaction for 4h to 6h to obtain a glue solution; the mass ratio of the organic solvent to the propylene oxide described in step 1) is (0.01 to 2):1.
  • the present invention selects an appropriate time to add a certain proportion of organic solvent, reduces the concentration of monomers and catalysts in the middle of the polymerization, increases the heat transfer and mass transfer efficiency in the reaction system, makes the copolymerization reaction and PC synthesis more complete, and simultaneously improves the molecular weight of the carbon dioxide-based multi-component copolymer and the yield of PC.
  • the organic solvent is one or a mixed solvent of two or more selected from methyl acetate, ethyl acetate, dichloromethane, dichloroethane, dichloropropane, tetrahydrofuran, and methyltetrahydrofuran.
  • the above-mentioned organic solvent can meet the process requirements of the present invention, and after being added to the reaction system, the copolymerization reaction and the synthesis reaction are kept to proceed normally, while achieving the purpose of increasing the heat transfer and mass transfer efficiency in the reaction system.
  • the organic solvent is a mixed solvent of methyl acetate and dichloromethane or dichloroethane in a mass ratio of 1 to 7:93 to 99.
  • the preferred organic solvent is added to the reaction system in a timely manner, the yield of the co-produced PC is higher, and a copolymer with a higher molecular weight is obtained, and the total yield of PC and the copolymer is higher.
  • the mass ratio of the organic solvent to the propylene oxide described in step 1) is (0.1-0.5):1.
  • an organic solvent is added and the reaction is continued for a period of time.
  • the output of PC can be increased, and the viscosity of the glue can be reduced, and the heat and mass transfer conditions are good, so that the reaction is more complete.
  • the preferred amount of solvent added can achieve appropriate heat and mass transfer effects, and at the same time keep the concentration of the reactants within a suitable range, so that a copolymer with a higher molecular weight can be obtained.
  • the method for synthesizing a carbon dioxide-based multi-polymer and co-producing PC of the present invention has the following beneficial effects: the present invention uses propylene oxide and carbon dioxide as raw materials to synthesize a carbon dioxide-based multi-polymer and co-produce PC at the same time, the reaction pressure and temperature are low, no waste gas and no waste water are generated, and the use of a non-metallic catalyst to synthesize a carbon dioxide-based multi-polymer and co-produce PC at the same time will not have residual metals, which is a green and energy-saving synthesis method with wider application.
  • the output ratio of the carbon dioxide-based multi-polymer and the co-product PC can be controlled by adjusting the ratio of each catalyst, adding an appropriate amount of solvent during the reaction, and performing staged reactions at different pressures or temperatures.
  • Embodiment 1 is the best implementation.
  • the organic solvent is a mixed solvent of methyl acetate and dichloromethane in a mass ratio of 4:95, and the amount of organic solvent added is 40% of the mass of propylene oxide added; the temperature and pressure are kept constant and the reaction is continued for 6h.
  • the prepared glue solution is dissolved in dichloromethane, precipitated with ethanol, devolatilized, granulated, and dried to obtain the finished PPC; the supernatant after washing and the solvent recovered by condensation after devolatilization are distilled and filtered to obtain PC.
  • the molecular weight of PPC is tested by GPC; the content of PC in the glue solution is tested by nuclear magnetic resonance spectrometer, and the content of refined PC is tested by weighing method; the content of heavy metals in PC is tested by inductively coupled plasma emission spectrometry.
  • Propylene oxide and non-metallic catalyst are added to a 5L high-pressure stirred reactor at a molar ratio of 1800:1.
  • the molar ratio of triethylboron to tetra-n-butylammonium bromide in the non-metallic catalyst is 2.0:1.
  • Carbon dioxide is charged to 1.2MPa and stirred at 70°C for 2h.
  • an organic solvent is added under pressure.
  • the organic solvent is a mixed solvent of methyl acetate and dichloromethane in a mass ratio of 1:99.
  • the amount of organic solvent added is 50% of the mass of propylene oxide added; the temperature and pressure are kept constant and the reaction is continued for 6h.
  • the prepared glue solution is dissolved in dichloromethane, precipitated with ethanol, devolatilized, granulated and dried to obtain the finished PPC; the supernatant after washing and the solvent recovered by condensation after devolatilization are distilled and filtered to obtain PC.
  • the molecular weight of PPC is tested by GPC; the content of PC in the glue solution is tested by nuclear magnetic resonance spectrometer, and the content of refined PC is tested by weighing method; the content of heavy metals in PC is tested by inductively coupled plasma emission spectroscopy.
  • the amount of organic solvent added is 10% of the mass of propylene oxide added; keep the temperature and pressure unchanged and continue the reaction for 5h.
  • the prepared glue is dissolved with dichloroethane, precipitated with ethanol, and the finished PPCP is obtained after devolatilization, granulation and drying; the supernatant after washing and the solvent recovered by condensation after devolatilization are distilled and filtered to obtain PC.
  • the prepared glue solution was dissolved with dichloroethane, precipitated with ethanol, devolatilized, granulated and dried to obtain the finished PPCP; the supernatant after washing and the solvent recovered by condensation after devolatilization were distilled and filtered to obtain PC.
  • the molecular weight of PPCP was tested by GPC; the content of PC in the glue solution was tested by nuclear magnetic resonance spectrometer, and the content of refined PC was tested by weighing method; the content of heavy metals in PC was tested by inductively coupled plasma emission spectrometry.
  • the prepared glue solution is dissolved with dichloroethane, precipitated with ethanol, devolatilized, granulated and dried to obtain the finished product PPCEP; the supernatant after washing and the solvent recovered by condensation after devolatilization are distilled and filtered to obtain PC.
  • the molecular weight of PPCEP is tested by GPC; the content of PC in the glue solution is tested by nuclear magnetic resonance spectrometer, and the content of refined PC is tested by weighing method; the content of heavy metals in PC is tested by inductively coupled plasma emission spectroscopy.
  • the molar ratio of propylene oxide, cyclohexene oxide, phthalic anhydride and non-metallic catalyst is 800:900:1100:1 and added to a 5L high-pressure stirred reactor.
  • the molar ratio of triethyl boron to tetra-n-butyl ammonium chloride in the non-metallic catalyst is 2.3:1.
  • Carbon dioxide is charged to 0.1MPa, stirred at 40°C for 5h, and then dichloropropane is added under pressure. The amount of dichloroethane added is twice the mass of propylene oxide added. The temperature and pressure are kept constant and the reaction is continued for 4h.
  • the prepared glue solution is dissolved with dichloropropane, precipitated with ethanol, devolatilized, granulated and dried to obtain the finished product PPCCP; the supernatant after washing and the solvent recovered by condensation after devolatilization are distilled and filtered to obtain PC.
  • the molecular weight of PPCCP is tested by GPC; the content of PC in the glue solution is tested by nuclear magnetic resonance spectrometer, and the content of refined PC is tested by weighing method; the content of heavy metals in PC is tested by inductively coupled plasma emission spectroscopy.
  • the prepared glue solution is dissolved with dichloromethane, precipitated with ethanol, and the finished PPC is obtained after devolatilization, granulation, and drying; the supernatant after washing and the solvent recovered by condensation after devolatilization are distilled and filtered to obtain PC.
  • the molecular weight of PPC is tested by GPC; the content of PC in the glue solution is tested by nuclear magnetic resonance spectrometer, and the content of refined PC is tested by weighing method; the content of heavy metals in PC is tested by inductively coupled plasma emission spectroscopy.
  • the molecular weight of PPC is tested by GPC; the content of PC in the glue solution is tested by nuclear magnetic resonance spectrometer, and the content of refined PC is tested by weighing method; the content of heavy metals in PC is tested by inductively coupled plasma emission spectrometry.
  • Example 3 In a dry kettle, nitrogen is used to replace the air in the kettle and then the feed is started.
  • Propylene oxide, phthalic anhydride and non-metallic catalyst are added to a 5L high-pressure stirred reactor according to the proportions of Example 3, wherein the molar ratio of triethylboron to tetra-n-butylammonium chloride in the non-metallic catalyst is 5:1.
  • Carbon dioxide is charged to 1.0MPa and stirred at 75°C for 10 hours.
  • the prepared glue solution is dissolved in dichloromethane, precipitated with ethanol, devolatilized, granulated and dried to obtain the finished PPCP; the supernatant after washing and the solvent condensed and recovered after devolatilization are distilled and filtered to obtain PC.
  • the molecular weight of PPCP is tested by GPC; the content of PC in the glue solution is tested by nuclear magnetic resonance spectrometer, and the content of refined PC is tested by weighing method; the content of heavy metals in PC is tested by inductively coupled plasma emission spectroscopy.
  • PC content The weight of PC and polymer is measured by nuclear magnetic resonance spectrometer, and the PC content is expressed as PC/(PC+Polymer) ⁇ 100%.
  • PC yield The amount of PC produced is tested by nuclear magnetic resonance spectrometer, and the amount of PC recovered is weighed by weighing method. The ratio of the two is the PC yield.
  • Heavy metal Zn The Zn content in PC was tested according to the method in Appendix B of SJ/T 11568-2016.

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Abstract

A method for co-producing PC while synthesizing a carbon dioxide-based multi-component copolymer, relating to the technical field of multi-component copolymers. Preparation steps comprise: putting propylene oxide, a comonomer and a nonmetal catalyst into a reactor, filling the reactor with carbon dioxide for pressure control, and performing a copolymerization reaction at a certain temperature; after the reaction is performed to a certain extent, maintaining the pressure, and adding an organic solvent to continue the reaction to obtain a glue solution; further dissolving the glue solution by using the organic solvent, adding alcohol to precipitate a precipitate, and washing and devolatilizing the solid to obtain a carbon dioxide-based multi-component copolymer; and performing rectification, extraction and separation to obtain PC. In the present invention, PC is co-produced while the carbon dioxide-based multi-component copolymer is synthesized by using propylene oxide and carbon dioxide as raw materials, the reaction pressure is low, the temperature is low, no waste gas is generated, and no wastewater is generated; co-producing PC while synthesizing a carbon dioxide-based multi-component copolymer by using the nonmetal catalyst does not result in metal residues; and the method is a green and energy-saving synthesis method and is more widely applied.

Description

一种合成二氧化碳基多元共聚物同时联产PC的方法A method for synthesizing carbon dioxide-based multi-polymers and simultaneously producing PC 技术领域Technical Field
一种合成二氧化碳基多元共聚物同时联产PC的方法，属于多元共聚物技术领域。The invention discloses a method for synthesizing a carbon dioxide-based multi-polymer and simultaneously co-producing PC, belonging to the technical field of multi-polymers.
背景技术Background technique
二氧化碳基多元共聚物是指二氧化碳与环氧化物、酸酐等单体共聚合成的二元或多元共聚物。普遍具有较高的阻隔性、透明性、全生物降解等特性，是一类优良的生物可降解材料。Carbon dioxide-based multi-polymers refer to binary or multi-polymers formed by copolymerization of carbon dioxide with monomers such as epoxides and acid anhydrides. They generally have high barrier properties, transparency, and full biodegradability, and are a type of excellent biodegradable material.
碳酸丙烯酯(PC)是一种性能优良的高沸点高极性有机溶剂，广泛的应用于各个领域。PC合成方法主要有光气法、酯交换法以及环氧丙烷与二氧化碳环加成法等。目前的合成方法中使用的催化剂多为金属催化剂，在合成的PC材料中有金属残留；因为锂电池对金属敏感，PC材料中有金属残留这一问题，就限制了PC在锂电池领域的应用。Propylene carbonate (PC) is a high-boiling point and high-polarity organic solvent with excellent performance, which is widely used in various fields. The main methods for synthesizing PC include phosgene method, transesterification method, and cycloaddition method of propylene oxide and carbon dioxide. The catalysts used in the current synthesis methods are mostly metal catalysts, and there are metal residues in the synthesized PC materials; 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.
二氧化碳基多元共聚物的合成时，若单体中存在环氧丙烷，通过调整反应条件和催化剂配比，可以与二氧化碳发生环加成反应产生碳酸丙烯酯。但是传统的二氧化碳基多元共聚物的合成方法中因为此反应的存在，消耗了环氧丙烷和二氧化碳，导致共聚反应的正向阻力增加，所得到的二氧化碳基多元共聚物的分子量较小，难以获得大分子量产物。发明内容When synthesizing carbon dioxide-based multi-polymers, if propylene oxide is present in the monomers, it can undergo a cycloaddition reaction with carbon dioxide to produce propylene carbonate by adjusting the reaction conditions and catalyst ratio. However, in the traditional synthesis method of carbon dioxide-based multi-polymers, due to the presence of this reaction, propylene oxide and carbon dioxide are consumed, resulting in an increase in the forward resistance of the copolymerization reaction. The molecular weight of the obtained carbon dioxide-based multi-polymer is relatively small, and it is difficult to obtain a high molecular weight product.
本发明要解决的技术问题是：克服现有技术的不足，提供一种能够提高共聚物分子量的合成二氧化碳基多元共聚物同时联产PC的方法。The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a method for synthesizing a carbon dioxide-based multi-polymer and simultaneously co-producing PC, which can increase the molecular weight of the copolymer.
本发明解决其技术问题所采用的技术方案是：该合成二氧化碳基多元共聚物同时联产PC的方法，包括以环氧丙烷、二氧化碳为主要反应原料的二元反应，以环氧丙烷、二氧化碳、苯酐为主要反应原料的三元合成反应，以及在此基础上添加其它酸酐或/和环氧烯烃的四元及四元以上合成反应；The technical solution adopted by the present invention to solve the technical problem is: the method for synthesizing carbon dioxide-based multi-polymers and simultaneously producing PC includes a binary reaction with propylene oxide and carbon dioxide as main reaction raw materials, a ternary synthesis reaction with propylene oxide, carbon dioxide and phthalic anhydride as main reaction raw materials, and a quaternary or higher synthesis reaction with other acid anhydrides and/or epoxy olefins added thereto;
其特征在于，制备步骤为：It is characterized in that the preparation steps are:
1)将环氧丙烷、共聚单体和非金属催化剂投入到反应器中，充入二氧化碳进行共聚反应制备胶液，共聚反应时保持反应温度为40℃～100℃、反应压力为0.1MPa～4.0MPa；所述的环氧丙烷、共聚单体和非金属催化剂的摩尔比为(800～2500)：(0～2000)：1；1) Putting propylene oxide, comonomer and non-metal catalyst into a reactor, charging carbon dioxide to carry out copolymerization reaction to prepare a glue solution, maintaining the reaction temperature at 40° C. to 100° C. and the reaction pressure at 0.1 MPa to 4.0 MPa during the copolymerization reaction; the molar ratio of propylene oxide, comonomer and non-metal catalyst is (800 to 2500): (0 to 2000): 1;
2)步骤1)制备的胶液用有机溶剂进一步溶解，再加入醇析出沉淀物，固液分离的固体经洗涤、脱挥后得到二氧化碳基多元共聚物；固液分离的液体经精馏、萃取分离后得到PC。2) The glue solution prepared in step 1) is further dissolved in an organic solvent, and then alcohol is added to precipitate a precipitate. The solid separated from the solid and liquid is washed and devolatilized to obtain a carbon dioxide-based multi-polymer; the liquid separated from the solid and liquid is distilled and extracted to obtain PC.
本发明在二氧化碳基多元共聚的过程中，利用非金属催化剂进行，所得PC材料中没有金属残留，可以在锂电池领域应用。而且在联产PC后能够降低反应体系的黏度，更有利于反应体系内搅拌均匀和出料；能够减少甚至防止聚碳酸酯类产物粘连釜壁。The present invention uses a non-metallic catalyst in the process of carbon dioxide-based multi-component copolymerization, and the resulting PC material has no metal residue, which can be used in the field of lithium batteries. Moreover, after the co-production of PC, the viscosity of the reaction system can be reduced, which is more conducive to uniform stirring and discharging in the reaction system; it can reduce or even prevent the polycarbonate product from sticking to the reactor wall.
具体的，上述合成二氧化碳基多元共聚物同时联产PC的方法中，步骤1)中所述的共聚单体为一种或两种以上的酸酐类单体和/或环氧丙烷以外的其它环氧化物。Specifically, in the above method for synthesizing carbon dioxide-based multi-polymers and simultaneously producing PC, the comonomers in step 1) are one or more anhydride monomers and/or other epoxides other than propylene oxide.
PC是由环氧丙烷与二氧化碳合成反应所得。 PC is obtained by the synthesis reaction of propylene oxide and carbon dioxide.
上述的以环氧丙烷、二氧化碳为主要反应原料的二元反应，通过调整反应条件、催化剂配比、加入合适的溶剂等方法，可以同时得到聚碳酸酯和PC产物。The above binary reaction with propylene oxide and carbon dioxide as main reaction raw materials can simultaneously obtain polycarbonate and PC products by adjusting reaction conditions, catalyst ratio, adding appropriate solvent and the like.
上述的以环氧丙烷、二氧化碳、苯酐的三元合成反应，以及包括这三种原料的同时添加其他酸酐或/和环氧烯烃，如：1，8萘酐、环氧乙烷、环氧丁烷、环氧环己烷等的四元及至四元以上合成反应，也都可以同时产生聚碳酸酯和PC及相应的碳酸烯烃基酯。The above-mentioned ternary synthesis reaction of propylene oxide, carbon dioxide and phthalic anhydride, as well as the quaternary and higher synthesis reactions involving the addition of other acid anhydrides and/or olefin oxides, such as 1,8-naphthalene anhydride, ethylene oxide, butylene oxide, cyclohexene oxide, etc., to these three raw materials, can also simultaneously produce polycarbonate and PC and the corresponding olefin carbonate esters.
比如：加入环氧乙烷的聚合反应过程会产生碳酸乙烯酯(EC)，加入环氧环己烷的聚合反应过程中会产生碳酸环己烯酯(CHC)。本发明中，所述的环氧丙烷以外的其它环氧化物包括但不限于环氧乙烷、环氧丁烷、环氧环己烷、环氧氯丙烷。For example, the polymerization process of adding ethylene oxide will produce ethylene carbonate (EC), and the polymerization process of adding cyclohexyl oxide will produce cyclohexene carbonate (CHC). In the present invention, other epoxides other than propylene oxide include but are not limited to ethylene oxide, butylene oxide, cyclohexyl oxide, and epichlorohydrin.
本发明中，所述的酸酐类单体包括但不限于马来酸酐、顺酐、邻苯二甲酸酐、四氢邻苯二甲酸酐、1,8-萘酐、四溴苯二甲酸酐。In the present invention, the acid anhydride monomers include but are not limited to maleic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, 1,8-naphthalene anhydride, and tetrabromophthalic anhydride.
本发明联产PC的二氧化碳基多元共聚物优选为环氧丙烷-二氧化碳二元共聚物(PPC)、环氧丙烷-邻苯二甲酸酐-二氧化碳三元共聚物(PPCP)，能够在二氧化碳基多元共聚物的共聚反应中，充分利用副反应得到了有价值的联产物PC。The carbon dioxide-based multipolymer for co-producing PC in the present invention is preferably a propylene oxide-carbon dioxide binary copolymer (PPC) or a propylene oxide-phthalic anhydride-carbon dioxide terpolymer (PPCP), which can fully utilize side reactions in the copolymerization reaction of the carbon dioxide-based multipolymer to obtain valuable co-product PC.
具体的，上述合成二氧化碳基多元共聚物同时联产PC的方法中，步骤1)中所述的非金属催化剂为路易斯酸/碱对配合形成的复合催化剂。路易斯酸/碱对配合的复合催化剂能够满足本发明的基本要求，在进行共聚的同时联产PC。Specifically, in the above-mentioned method for synthesizing carbon dioxide-based multi-polymers and simultaneously producing PC, the non-metallic catalyst in step 1) is a composite catalyst formed by a Lewis acid/base pair. The composite catalyst formed by a Lewis acid/base pair can meet the basic requirements of the present invention and simultaneously produce PC during copolymerization.
所述的路易斯酸包括：三乙基硼、三丙基硼、三丁基硼、三仲丁基硼烷、三苯基硼、三(五氟苯基)硼、二乙基甲氧基硼烷、二(三甲苯基)氟化硼中的一种或多种。优选为三乙基硼。The Lewis acid includes one or more of triethylboron, tripropylboron, tributylboron, tri-sec-butylborane, triphenylboron, tri(pentafluorophenyl)boron, diethylmethoxyborane, and di(trimethylphenyl)boron fluoride, preferably triethylboron.
所述的路易斯碱包括：四正丁基氟化铵、四正丁基氯化铵、四正丁基溴化铵、四正丁基碘化铵、四正丙基氟化铵、四正丙基氯化铵、四正丙基溴化铵、四正丙基碘化铵、双(三苯基正膦基)氯化铵的一种或多种。优选为四正丁基氯化铵、四正丁基溴化铵。The Lewis base includes 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(triphenylphosphorane)ammonium chloride. Preferably, tetra-n-butylammonium chloride and tetra-n-butylammonium bromide are used.
上述的路易斯酸和路易斯碱均可作为路易斯酸/碱对进行配合，形成的复合催化剂。The above-mentioned Lewis acids and Lewis bases can be combined as Lewis acid/base pairs to form a composite catalyst.
本发明还能够通过调整催化剂的比例来调整二氧化碳基多元共聚物和联产物PC的产出比例，可以大幅度的增加联产物PC的产生量，而且产量可控。优选的，上述合成二氧化碳基多元共聚物同时联产PC的方法中，步骤1)中所述的非金属催化剂为三烷基硼类与四正丁基卤化铵按摩尔比(1.3～3):1配合形成的复合催化剂。优选的复合催化剂更加适应本发明共聚反应的工艺条件，能够得到分子量更大共聚物。配合本发明的中途加入溶剂的工艺，能够同时高产率联产PC。The present invention can also adjust the output ratio of the carbon dioxide-based multi-polymer and the co-product PC by adjusting the ratio of the catalyst, which can greatly increase the production of the co-product PC, and the output is controllable. Preferably, in the above-mentioned method for synthesizing a carbon dioxide-based multi-polymer and co-producing PC, the non-metallic catalyst described in step 1) is a composite catalyst formed by combining trialkylborane and tetra-n-butylammonium halide in a molar ratio of (1.3 to 3): 1. The preferred composite catalyst is more suitable for the process conditions of the copolymerization reaction of the present invention, and a copolymer with a larger molecular weight can be obtained. In combination with the process of adding a solvent midway of the present invention, PC can be co-produced at a high yield at the same time.
进一步优选的，上述合成二氧化碳基多元共聚物同时联产PC的方法中，步骤1)中所述的非金属催化剂为三烷基硼类与四正丁基卤化铵按摩尔比(2.0-2.6):1配合形成的复合催化剂。进一步优化配比的复合催化剂能够达到本发明二氧化碳基多元共聚物联产PC的最佳效果，同时保证两者的产率和共聚物的分子量。三烷基硼类与四正丁基卤(氯、溴)化铵的摩尔比更优选为(2.1-2.5):1。Further preferably, in the method for synthesizing the carbon dioxide-based multi-polymer and simultaneously producing PC, the non-metallic catalyst described in step 1) is a composite catalyst formed by combining trialkylborons and tetra-n-butylammonium halide in a molar ratio of (2.0-2.6):1. The composite catalyst with further optimized ratio can achieve the best effect of the carbon dioxide-based multi-polymer co-production of PC of the present invention, while ensuring the yield of both and the molecular weight of the copolymer. The molar ratio of trialkylborons to tetra-n-butylammonium halide (chloride, bromide) is more preferably (2.1-2.5):1.
优选的，上述合成二氧化碳基多元共聚物同时联产PC的方法中，步骤1)中所述的环氧丙烷和非金属催化剂的摩尔比为(1600～2000)：1。优选的，上述合成二氧化碳基多元共聚物同时联产PC的方法中，步骤1)中所述的反应温度为70℃～90℃，反应压力为1MPa～2MPa。优选的非金属催化剂的加入量、反应温度和反应压力均是为了控制本发明反应体系中聚合 反应和合成反应的速率，从而能够更好的提高联产物的产率。进一步优选的反应温度为75℃～80℃，反应压力为1.1MPa～1.5MPa。Preferably, in the above method for synthesizing carbon dioxide-based multi-polymers and simultaneously producing PC, the molar ratio of propylene oxide to non-metallic catalyst in step 1) is (1600-2000):1. Preferably, in the above method for synthesizing carbon dioxide-based multi-polymers and simultaneously producing PC, the reaction temperature in step 1) is 70°C-90°C, and the reaction pressure is 1MPa-2MPa. The preferred amount of non-metallic catalyst added, the reaction temperature and the reaction pressure are all for controlling the polymerization in the reaction system of the present invention. The reaction and synthesis reaction rates can be increased, thereby better improving the yield of the co-product. Further preferred reaction temperature is 75°C to 80°C, and the reaction pressure is 1.1MPa to 1.5MPa.
优选的，上述合成二氧化碳基多元共聚物同时联产PC的方法中，步骤1)中所述的共聚反应进行2h～5h后，向反应体系中保压加入有机溶剂，保持步骤1)的反应温度和反应压力继续反应4h～6h得到胶液；所述有机溶剂与步骤1)中所述的环氧丙烷质量比为(0.01～2):1。Preferably, in the above-mentioned method for synthesizing carbon dioxide-based multi-copolymers and simultaneously producing PC, after the copolymerization reaction described in step 1) is carried out for 2h to 5h, an organic solvent is added to the reaction system under pressure, and the reaction temperature and reaction pressure of step 1) are maintained to continue the reaction for 4h to 6h to obtain a glue solution; the mass ratio of the organic solvent to the propylene oxide described in step 1) is (0.01 to 2):1.
本发明在二氧化碳基多元共聚的过程中，选择适当的时机加入一定比例的有机溶剂，在聚合中途降低单体和催化剂的浓度，使反应体系中传热、传质效率增加，使共聚反应和PC合成更充分。同时提高二氧化碳基多元共聚物的分子量和PC的产率。In the process of carbon dioxide-based multi-component copolymerization, the present invention selects an appropriate time to add a certain proportion of organic solvent, reduces the concentration of monomers and catalysts in the middle of the polymerization, increases the heat transfer and mass transfer efficiency in the reaction system, makes the copolymerization reaction and PC synthesis more complete, and simultaneously improves the molecular weight of the carbon dioxide-based multi-component copolymer and the yield of PC.
具体的，上述合成二氧化碳基多元共聚物同时联产PC的方法中，所述的有机溶剂为乙酸甲酯、乙酸乙酯、二氯甲烷、二氯乙烷、二氯丙烷、四氢呋喃、甲基四氢呋喃中的一种或两种以上的混合溶剂。上述的有机溶剂能够满足本发明的工艺要求，加入反应体系后保持共聚反应与合成反应正常进行的同时，达到增加反应体系中传热、传质效率的目的。Specifically, in the above-mentioned method for synthesizing carbon dioxide-based multi-component copolymers and simultaneously producing PC, the organic solvent is one or a mixed solvent of two or more selected from methyl acetate, ethyl acetate, dichloromethane, dichloroethane, dichloropropane, tetrahydrofuran, and methyltetrahydrofuran. The above-mentioned organic solvent can meet the process requirements of the present invention, and after being added to the reaction system, the copolymerization reaction and the synthesis reaction are kept to proceed normally, while achieving the purpose of increasing the heat transfer and mass transfer efficiency in the reaction system.
优选的，上述合成二氧化碳基多元共聚物同时联产PC的方法中，所述的有机溶剂为乙酸甲酯与二氯甲烷或二氯乙烷按质量比1～7：93～99配比的混合溶剂。优选的有机溶剂适时地加入反应体系后，联产PC的产率更高，同时得到更高分子量的共聚物，PC和共聚物的总产率更高。Preferably, in the above method for synthesizing carbon dioxide-based multi-component copolymers and simultaneously producing PC, the organic solvent is a mixed solvent of methyl acetate and dichloromethane or dichloroethane in a mass ratio of 1 to 7:93 to 99. After the preferred organic solvent is added to the reaction system in a timely manner, the yield of the co-produced PC is higher, and a copolymer with a higher molecular weight is obtained, and the total yield of PC and the copolymer is higher.
优选的，上述合成二氧化碳基多元共聚物同时联产PC的方法中，所述的有机溶剂与步骤1)中所述的环氧丙烷的质量比为(0.1～0.5):1。本发明在聚合反应到胶液黏度较高时，加入有机溶剂，继续反应一段时间。加入溶剂后可以增加PC的产量，同时降低胶液的黏度，传热、传质条件佳，使反应更充分。优选的溶剂加入量能够达到适当的传热、传质效果，同时使反应物的浓度保持在合适的范围内，能够得到分子量较高的共聚物。Preferably, in the above-mentioned method for synthesizing carbon dioxide-based multi-polymers and simultaneously co-producing PC, the mass ratio of the organic solvent to the propylene oxide described in step 1) is (0.1-0.5):1. In the present invention, when the viscosity of the glue is relatively high during the polymerization reaction, an organic solvent is added and the reaction is continued for a period of time. After the addition of the solvent, the output of PC can be increased, and the viscosity of the glue can be reduced, and the heat and mass transfer conditions are good, so that the reaction is more complete. The preferred amount of solvent added can achieve appropriate heat and mass transfer effects, and at the same time keep the concentration of the reactants within a suitable range, so that a copolymer with a higher molecular weight can be obtained.
与现有技术相比，本发明的一种合成二氧化碳基多元共聚物同时联产PC的方法所具有的有益效果是：本发明通过环氧丙烷、二氧化碳为原料合成二氧化碳基多元共聚物的同时联产PC，反应压力低、温度低，无废气、无废水产生，用非金属催化剂合成二氧化碳基多元共聚物的同时联产PC不会有残留金属，是一种绿色节能的合成方法，应用更为广泛。通过调整各催化剂的配比、反应时适量添加溶剂、不同压力或不同温度下分段反应等方法控制二氧化碳基多元共聚物和联产物PC的产出比例。Compared with the prior art, the method for synthesizing a carbon dioxide-based multi-polymer and co-producing PC of the present invention has the following beneficial effects: the present invention uses propylene oxide and carbon dioxide as raw materials to synthesize a carbon dioxide-based multi-polymer and co-produce PC at the same time, the reaction pressure and temperature are low, no waste gas and no waste water are generated, and the use of a non-metallic catalyst to synthesize a carbon dioxide-based multi-polymer and co-produce PC at the same time will not have residual metals, which is a green and energy-saving synthesis method with wider application. The output ratio of the carbon dioxide-based multi-polymer and the co-product PC can be controlled by adjusting the ratio of each catalyst, adding an appropriate amount of solvent during the reaction, and performing staged reactions at different pressures or temperatures.
具体实施方式Detailed ways
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本申请的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，术语“包括”和“具有”以及他们的任何变形，意图在于覆盖不排他的包含，例如，包含了一系列步骤或单元的过程、方法、系统、产品或设备不必限于清楚地列出的那些步骤或单元，而是可包括没有清楚地列出的或对于这些过程、方法、产品或设备固有的其它步骤或单元。It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present application. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, the terms "including" and "having" and any of their variations are intended to cover non-exclusive inclusions, for example, a process, method, system, product or device that includes a series of steps or units is not necessarily limited to those steps or units that are clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or devices.
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application may be combined with each other.
下面结合具体实施例对本发明做进一步说明，其中实施例1为最佳实施。 The present invention is further described below in conjunction with specific embodiments, wherein Embodiment 1 is the best implementation.
另外，如果没有其它说明，所用原料都是市售得到的。In addition, unless otherwise stated, all raw materials used were commercially available.
实施例1Example 1
在干燥的釜内，采用氮气置换出釜内空气后开始投料，将环氧丙烷和非金属催化剂按摩尔比1800：1加入5L高压搅拌反应器中，非金属催化剂中三乙基硼与四正丁基氯化铵的摩尔比为2.3:1。充入二氧化碳至1.2MPa，70℃搅拌反应2h，然后带压投入有机溶剂，有机溶剂为乙酸甲酯与二氯甲烷按质量比4：95配比的混合溶剂，加入有机溶剂的量为加入环氧丙烷质量的40％；保持温度、压力不变继续反应6h。制备的胶液用二氯甲烷溶解，用乙醇沉淀析出，脱挥、造粒、干燥后得到成品PPC；洗涤后的上清液以及脱挥后冷凝回收的溶剂，精馏、过滤得到PC。用GPC测试PPC的分子量；用核磁共振波谱仪测试胶液中PC的含量，用称重法测试精制PC的含量；用电感耦合等离子体发射光谱法测试PC中重金属的含量。分析得到，PPC的数均分子量Mn/PDI为1.16×105g/mol/2.69；PC/(PC+PPC)＝53％；PC的收率为94％；PC中未检出重金属。In a dry kettle, nitrogen is used to replace the air in the kettle and then the feed is started. Propylene oxide and non-metallic catalyst are added to a 5L high-pressure stirred reactor at a molar ratio of 1800:1. The molar ratio of triethylboron to tetra-n-butylammonium chloride in the non-metallic catalyst is 2.3:1. Carbon dioxide is charged to 1.2MPa, and the reaction is stirred at 70℃ for 2h, and then an organic solvent is added under pressure. The organic solvent is a mixed solvent of methyl acetate and dichloromethane in a mass ratio of 4:95, and the amount of organic solvent added is 40% of the mass of propylene oxide added; the temperature and pressure are kept constant and the reaction is continued for 6h. The prepared glue solution is dissolved in dichloromethane, precipitated with ethanol, devolatilized, granulated, and dried to obtain the finished PPC; the supernatant after washing and the solvent recovered by condensation after devolatilization are distilled and filtered to obtain PC. The molecular weight of PPC is tested by GPC; the content of PC in the glue solution is tested by nuclear magnetic resonance spectrometer, and the content of refined PC is tested by weighing method; the content of heavy metals in PC is tested by inductively coupled plasma emission spectrometry. The analysis showed that the number average molecular weight Mn/PDI of PPC was 1.16×10 5 g/mol/2.69; PC/(PC+PPC)=53%; the yield of PC was 94%; and no heavy metals were detected in PC.
实施例2Example 2
在干燥的釜内，采用氮气置换出釜内空气后开始投料，将环氧丙烷和非金属催化剂按摩尔比1800：1加入5L高压搅拌反应器中，非金属催化剂中三乙基硼与四正丁基溴化铵的摩尔比为2.0:1。充入二氧化碳至1.2MPa，70℃搅拌反应2h。然后带压投入有机溶剂，有机溶剂为乙酸甲酯与二氯甲烷按质量比1：99配比的混合溶剂，加入有机溶剂的量为加入环氧丙烷质量的50％；保持温度、压力不变继续反应6h。制备的胶液用二氯甲烷溶解，用乙醇沉淀析出，脱挥、造粒、干燥后得到成品PPC；洗涤后的上清液以及脱挥后冷凝回收的溶剂，精馏、过滤得到PC。用GPC测试PPC的分子量；用核磁共振波谱仪测试胶液中PC的含量，用称重法测试精制PC的含量；用电感耦合等离子体发射光谱法测试PC中重金属的含量。分析得到，PPC的数均分子量Mn/PDI为8.95×104g/mol/2.69；PC/(PC+PPC)＝51％；PC的收率为94％；PC中未检出重金属。In a dry kettle, nitrogen is used to replace the air in the kettle and then the feed is started. Propylene oxide and non-metallic catalyst are added to a 5L high-pressure stirred reactor at a molar ratio of 1800:1. The molar ratio of triethylboron to tetra-n-butylammonium bromide in the non-metallic catalyst is 2.0:1. Carbon dioxide is charged to 1.2MPa and stirred at 70℃ for 2h. Then an organic solvent is added under pressure. The organic solvent is a mixed solvent of methyl acetate and dichloromethane in a mass ratio of 1:99. The amount of organic solvent added is 50% of the mass of propylene oxide added; the temperature and pressure are kept constant and the reaction is continued for 6h. The prepared glue solution is dissolved in dichloromethane, precipitated with ethanol, devolatilized, granulated and dried to obtain the finished PPC; the supernatant after washing and the solvent recovered by condensation after devolatilization are distilled and filtered to obtain PC. The molecular weight of PPC is tested by GPC; the content of PC in the glue solution is tested by nuclear magnetic resonance spectrometer, and the content of refined PC is tested by weighing method; the content of heavy metals in PC is tested by inductively coupled plasma emission spectroscopy. The analysis showed that the number average molecular weight Mn/PDI of PPC was 8.95×10 4 g/mol/2.69; PC/(PC+PPC)=51%; the yield of PC was 94%; and no heavy metals were detected in PC.
实施例3Example 3
在干燥的釜内，采用氮气置换出釜内空气后开始投料，将环氧丙烷、邻苯二甲酸酐和非金属催化剂按摩尔比1800：560：1加入5L高压搅拌反应器中，非金属催化剂中三乙基硼与四正丁基氯化铵的摩尔比为2.6:1。充入二氧化碳至1.5MPa，75℃搅拌反应4h，然后带压投入有机溶剂，有机溶剂为乙酸甲酯与二氯乙烷按质量比7：93配比的混合溶剂，加入有机溶剂的量为加入环氧丙烷质量的10％；保持温度、压力不变继续反应5h。制备的胶液用二氯乙烷溶解，用乙醇沉淀析出，脱挥、造粒、干燥后得到成品PPCP；洗涤后的上清液以及脱挥后冷凝回收的溶剂，精馏、过滤得到PC。用GPC测试PPCP的分子量；用核磁共振波谱仪测试胶液中PC的含量，用称重法测试精制PC的含量；用电感耦合等离子体发射光谱法测试PC中重金属的含量。分析得到，PPCP的数均分子量Mn/PDI为1.75×105g/mol/2.44；PC/(PC+PPCP)＝35％；PC的收率为93％；PC中未检出重金属。In a dry kettle, nitrogen is used to replace the air in the kettle and then the feed is started. Propylene oxide, phthalic anhydride and non-metallic catalyst are added to a 5L high-pressure stirred reactor at a molar ratio of 1800:560:1. The molar ratio of triethyl boron to tetra-n-butyl ammonium chloride in the non-metallic catalyst is 2.6:1. Carbon dioxide is charged to 1.5MPa, and the reaction is stirred at 75℃ for 4h, and then an organic solvent is added under pressure. The organic solvent is a mixed solvent of methyl acetate and dichloroethane in a mass ratio of 7:93. The amount of organic solvent added is 10% of the mass of propylene oxide added; keep the temperature and pressure unchanged and continue the reaction for 5h. The prepared glue is dissolved with dichloroethane, precipitated with ethanol, and the finished PPCP is obtained after devolatilization, granulation and drying; the supernatant after washing and the solvent recovered by condensation after devolatilization are distilled and filtered to obtain PC. The molecular weight of PPCP was tested by GPC; the content of PC in the glue was tested by nuclear magnetic resonance spectrometer, and the content of refined PC was tested by weighing method; the content of heavy metals in PC was tested by inductively coupled plasma emission spectrometry. The analysis showed that the number average molecular weight Mn/PDI of PPCP was 1.75×10 5 g/mol/2.44; PC/(PC+PPCP)=35%; the yield of PC was 93%; no heavy metals were detected in PC.
实施例4Example 4
在干燥的釜内，采用氮气置换出釜内空气后开始投料，将环氧丙烷、邻苯二甲酸酐和非金属催化剂按摩尔比1800：430：1加入5L高压搅拌反应器中，非金属催化剂中三乙基硼与四正丁基溴化铵的摩尔比为1.3:1。充入二氧化碳至2.0MPa，70℃搅拌反应4h，然后带压投入二氯乙烷，加入二氯乙烷的量为加入环氧丙烷质量的1％，保持温度、压力不变继续反应 5h。制备的胶液用二氯乙烷溶解，用乙醇沉淀析出，脱挥、造粒、干燥后得到成品PPCP；洗涤后的上清液以及脱挥后冷凝回收的溶剂，精馏、过滤得到PC。用GPC测试PPCP的分子量；用核磁共振波谱仪测试胶液中PC的含量，用称重法测试精制PC的含量；用电感耦合等离子体发射光谱法测试PC中重金属的含量。分析得到，PPCP的数均分子量Mn/PDI为1.31×105g/mol/2.15；PC/(PC+PPCP)＝38％；PC的收率为91％；PC中未检出重金属。In a dry kettle, nitrogen is used to replace the air in the kettle and then the materials are added. Propylene oxide, phthalic anhydride and non-metallic catalyst are added to a 5L high-pressure stirred reactor at a molar ratio of 1800:430:1. The molar ratio of triethylboron to tetra-n-butylammonium bromide in the non-metallic catalyst is 1.3:1. Carbon dioxide is charged to 2.0MPa, and the reaction is stirred at 70℃ for 4h. Then dichloroethane is added under pressure. The amount of dichloroethane added is 1% of the mass of propylene oxide added. The temperature and pressure are kept unchanged and the reaction continues. 5h. The prepared glue solution was dissolved with dichloroethane, precipitated with ethanol, devolatilized, granulated and dried to obtain the finished PPCP; the supernatant after washing and the solvent recovered by condensation after devolatilization were distilled and filtered to obtain PC. The molecular weight of PPCP was tested by GPC; the content of PC in the glue solution was tested by nuclear magnetic resonance spectrometer, and the content of refined PC was tested by weighing method; the content of heavy metals in PC was tested by inductively coupled plasma emission spectrometry. The analysis showed that the number average molecular weight Mn/PDI of PPCP was 1.31×10 5 g/mol/2.15; PC/(PC+PPCP)=38%; the yield of PC was 91%; no heavy metals were detected in PC.
实施例5Example 5
在干燥的釜内，采用氮气置换出釜内空气后开始投料，将环氧丙烷、环氧乙烷、邻苯二甲酸酐和非金属催化剂按摩尔比1080：720：560：1加入5L高压搅拌反应器中，非金属催化剂中三乙基硼与四正丁基溴化铵的摩尔比为3:1。充入二氧化碳至1.0MPa，90℃搅拌反应4h，然后带压投入二氯乙烷，加入二氯乙烷的量为加入环氧丙烷质量的两倍，保持温度、压力不变继续反应4h。制备的胶液用二氯乙烷溶解，用乙醇沉淀析出，脱挥、造粒、干燥后得到成品PPCEP；洗涤后的上清液以及脱挥后冷凝回收的溶剂，精馏、过滤得到PC。用GPC测试PPCEP的分子量；用核磁共振波谱仪测试胶液中PC的含量，用称重法测试精制PC的含量；用电感耦合等离子体发射光谱法测试PC中重金属的含量。分析得到，PPCEP的数均分子量Mn/PDI为1.54×105g/mol/2.69；PC/(PC+PPCEP)＝45％；PC的收率为83％；PC中未检出重金属。In a dry kettle, nitrogen is used to replace the air in the kettle and then the feed is started. Propylene oxide, ethylene oxide, phthalic anhydride and non-metallic catalyst are added to a 5L high-pressure stirred reactor in a molar ratio of 1080:720:560:1. The molar ratio of triethylboron to tetra-n-butylammonium bromide in the non-metallic catalyst is 3:1. Carbon dioxide is charged to 1.0MPa, and the reaction is stirred at 90℃ for 4h, and then dichloroethane is added under pressure. The amount of dichloroethane added is twice the mass of propylene oxide added. The temperature and pressure are kept constant and the reaction is continued for 4h. The prepared glue solution is dissolved with dichloroethane, precipitated with ethanol, devolatilized, granulated and dried to obtain the finished product PPCEP; the supernatant after washing and the solvent recovered by condensation after devolatilization are distilled and filtered to obtain PC. The molecular weight of PPCEP is tested by GPC; the content of PC in the glue solution is tested by nuclear magnetic resonance spectrometer, and the content of refined PC is tested by weighing method; the content of heavy metals in PC is tested by inductively coupled plasma emission spectroscopy. The analysis showed that the number average molecular weight Mn/PDI of PPCEP was 1.54×10 5 g/mol/2.69; PC/(PC+PPCEP)=45%; the yield of PC was 83%; and no heavy metals were detected in PC.
实施例6Example 6
在干燥的釜内，采用氮气置换出釜内空气后开始投料，将环氧丙烷、环氧环己烷、邻苯二甲酸酐和非金属催化剂的摩尔比为800：900：1100：1加入5L高压搅拌反应器中，非金属催化剂中三乙基硼与四正丁基氯化铵的摩尔比为2.3:1。充入二氧化碳至0.1MPa，40℃搅拌反应5h，然后带压投入二氯丙烷，加入二氯乙烷的量为加入环氧丙烷质量的两倍，保持温度、压力不变继续反应4h。制备的胶液用二氯丙烷溶解，用乙醇沉淀析出，脱挥、造粒、干燥后得到成品PPCCP；洗涤后的上清液以及脱挥后冷凝回收的溶剂，精馏、过滤得到PC。用GPC测试PPCCP的分子量；用核磁共振波谱仪测试胶液中PC的含量，用称重法测试精制PC的含量；用电感耦合等离子体发射光谱法测试PC中重金属的含量。分析得到，PPCCP的数均分子量Mn/PDI为1.07×105g/mol/2.23；PC/(PC+PPCCP)＝31％；PC的收率为75％；PC中未检出重金属含量。In a dry kettle, nitrogen is used to replace the air in the kettle and then the feed is started. The molar ratio of propylene oxide, cyclohexene oxide, phthalic anhydride and non-metallic catalyst is 800:900:1100:1 and added to a 5L high-pressure stirred reactor. The molar ratio of triethyl boron to tetra-n-butyl ammonium chloride in the non-metallic catalyst is 2.3:1. Carbon dioxide is charged to 0.1MPa, stirred at 40℃ for 5h, and then dichloropropane is added under pressure. The amount of dichloroethane added is twice the mass of propylene oxide added. The temperature and pressure are kept constant and the reaction is continued for 4h. The prepared glue solution is dissolved with dichloropropane, precipitated with ethanol, devolatilized, granulated and dried to obtain the finished product PPCCP; the supernatant after washing and the solvent recovered by condensation after devolatilization are distilled and filtered to obtain PC. The molecular weight of PPCCP is tested by GPC; the content of PC in the glue solution is tested by nuclear magnetic resonance spectrometer, and the content of refined PC is tested by weighing method; the content of heavy metals in PC is tested by inductively coupled plasma emission spectroscopy. The analysis showed that the number average molecular weight Mn/PDI of PPCCP was 1.07×10 5 g/mol/2.23; PC/(PC+PPCCP)=31%; the yield of PC was 75%; and no heavy metal content was detected in PC.
实施例7Example 7
在干燥的釜内，采用氮气置换出釜内空气后开始投料，将环氧丙烷和非金属催化剂按摩尔比为2500：1加入5L高压搅拌反应器中，非金属催化剂中三乙基硼与四正丁基氯化铵的摩尔比为2.3:1。充入二氧化碳至4.0MPa，100℃搅拌反应2h，然后带压投入二氯乙烷，加入二氯乙烷的量为加入环氧丙烷质量的三倍，保持温度、压力不变继续反应6h。制备的胶液用二氯甲烷溶解，用乙醇沉淀析出，脱挥、造粒、干燥后得到成品PPC；洗涤后的上清液以及脱挥后冷凝回收的溶剂，精馏、过滤得到PC。用GPC测试PPC的分子量；用核磁共振波谱仪测试胶液中PC的含量，用称重法测试精制PC的含量；用电感耦合等离子体发射光谱法测试PC中重金属的含量。分析得到，PPC的数均分子量Mn/PDI为1.08×105g/mol/2.16；PC/(PC+PPC)＝61％；PC的收率为90％；PC中未检出重金属。In a dry kettle, nitrogen is used to replace the air in the kettle and then the feed is started. Propylene oxide and non-metallic catalyst are added to a 5L high-pressure stirred reactor at a molar ratio of 2500:1. The molar ratio of triethylboron to tetra-n-butylammonium chloride in the non-metallic catalyst is 2.3:1. Carbon dioxide is charged to 4.0MPa, and the reaction is stirred at 100℃ for 2h, and then dichloroethane is added under pressure. The amount of dichloroethane added is three times the mass of propylene oxide added. The temperature and pressure are kept constant and the reaction is continued for 6h. The prepared glue solution is dissolved with dichloromethane, precipitated with ethanol, and the finished PPC is obtained after devolatilization, granulation, and drying; the supernatant after washing and the solvent recovered by condensation after devolatilization are distilled and filtered to obtain PC. The molecular weight of PPC is tested by GPC; the content of PC in the glue solution is tested by nuclear magnetic resonance spectrometer, and the content of refined PC is tested by weighing method; the content of heavy metals in PC is tested by inductively coupled plasma emission spectroscopy. The analysis showed that the number average molecular weight Mn/PDI of PPC was 1.08×10 5 g/mol/2.16; PC/(PC+PPC)=61%; the yield of PC was 90%; and no heavy metals were detected in PC.
实施例8Example 8
在干燥的釜内，采用氮气置换出釜内空气后开始投料，将环氧丙烷和非金属催化剂按实施例2的比例加入5L高压搅拌反应器中，充入二氧化碳至1.2MPa，70℃搅拌反应10h。 制备的胶液用二氯甲烷溶解，用乙醇沉淀析出，脱挥、造粒、干燥后得到成品PPC；洗涤后的上清液以及脱挥后冷凝回收的溶剂，精馏、过滤得到PC。用GPC测试PPC的分子量；用核磁共振波谱仪测试胶液中PC的含量，用称重法测试精制PC的含量；用电感耦合等离子体发射光谱法测试PC中重金属的含量。分析得到，PPC的数均分子量Mn/PDI为6.75×104g/mol/2.69；PC/(PC+PPC)＝34％；PC的收率为92％；PC中未检出重金属。In a dry kettle, nitrogen was used to replace the air in the kettle and then the materials were added. Propylene oxide and non-metallic catalyst were added into a 5L high-pressure stirred reactor according to the proportion in Example 2. Carbon dioxide was filled to 1.2MPa and the reaction was stirred at 70°C for 10h. The prepared glue solution is dissolved with dichloromethane, precipitated with ethanol, devolatilized, granulated and dried to obtain the finished product PPC; the supernatant after washing and the solvent recovered by condensation after devolatilization are distilled and filtered to obtain PC. The molecular weight of PPC is tested by GPC; the content of PC in the glue solution is tested by nuclear magnetic resonance spectrometer, and the content of refined PC is tested by weighing method; the content of heavy metals in PC is tested by inductively coupled plasma emission spectrometry. The analysis shows that the number average molecular weight Mn/PDI of PPC is 6.75×10 4 g/mol/2.69; PC/(PC+PPC)=34%; the yield of PC is 92%; and no heavy metals are detected in PC.
实施例9Example 9
在干燥的釜内，采用氮气置换出釜内空气后开始投料，将环氧丙烷、邻苯二甲酸酐和非金属催化剂按实施例3的比例加入5L高压搅拌反应器中，其中非金属催化剂中三乙基硼与四正丁基氯化铵的摩尔比为5:1。充入二氧化碳至1.0MPa，75℃搅拌反应10h。制备的胶液用二氯甲烷溶解，用乙醇沉淀析出，脱挥、造粒、干燥后得到成品PPCP；洗涤后的上清液以及脱挥后冷凝回收的溶剂，精馏、过滤得到PC。用GPC测试PPCP的分子量；用核磁共振波谱仪测试胶液中PC的含量，用称重法测试精制PC的含量；用电感耦合等离子体发射光谱法测试PC中重金属的含量。分析得到，PPCP的数均分子量Mn/PDI为7.61×104g/mol/2.18；PC/(PC+PPCP)＝21％；PC的收率为93％；PC中未检出重金属。In a dry kettle, nitrogen is used to replace the air in the kettle and then the feed is started. Propylene oxide, phthalic anhydride and non-metallic catalyst are added to a 5L high-pressure stirred reactor according to the proportions of Example 3, wherein the molar ratio of triethylboron to tetra-n-butylammonium chloride in the non-metallic catalyst is 5:1. Carbon dioxide is charged to 1.0MPa and stirred at 75°C for 10 hours. The prepared glue solution is dissolved in dichloromethane, precipitated with ethanol, devolatilized, granulated and dried to obtain the finished PPCP; the supernatant after washing and the solvent condensed and recovered after devolatilization are distilled and filtered to obtain PC. The molecular weight of PPCP is tested by GPC; the content of PC in the glue solution is tested by nuclear magnetic resonance spectrometer, and the content of refined PC is tested by weighing method; the content of heavy metals in PC is tested by inductively coupled plasma emission spectroscopy. The analysis showed that the number average molecular weight Mn/PDI of PPCP was 7.61×10 4 g/mol/2.18; PC/(PC+PPCP)=21%; the yield of PC was 93%; and no heavy metals were detected in PC.
对比例1Comparative Example 1
在干燥的釜内，采用氮气置换出釜内空气后开始投料，将环氧丙烷、催化剂ZnCl2/PPh3C10H21Br按摩尔比1600:1加入5L高压搅拌反应器中。充入二氧化碳至1.5MPa，120℃搅拌反应3h，反应生成PC。用称重法测试精制PC的含量；用电感耦合等离子体发射光谱法测试PC中重金属的含量。分析得到，PC的产率为90％；PC中锌(Zn)的含量为0.66mg/kg。In a dry kettle, nitrogen was used to replace the air in the kettle and then the materials were added. Propylene oxide and catalyst ZnCl 2 /PPh 3 C 10 H 21 Br were added to a 5L high pressure stirred reactor at a molar ratio of 1600:1. Carbon dioxide was charged to 1.5MPa and stirred at 120℃ for 3h to generate PC. The content of refined PC was tested by weighing method; the content of heavy metals in PC was tested by inductively coupled plasma emission spectrometry. The analysis showed that the yield of PC was 90%; the content of zinc (Zn) in PC was 0.66mg/kg.
性能测试：Performance Testing:
分子量：用GPC分析聚合物的分子量，参照方法“GB/T 31124-2014附录B”。Molecular weight: The molecular weight of the polymer is analyzed by GPC, referring to the method "GB/T 31124-2014 Appendix B".
PC的含量：用核磁共振波谱仪测试出PC、聚合物(Polymer)的重量，PC的含量表示为PC/(PC+Polymer)×100％。PC content: The weight of PC and polymer is measured by nuclear magnetic resonance spectrometer, and the PC content is expressed as PC/(PC+Polymer)×100%.
PC的收率：用核磁共振波谱仪测试出PC的产生量，用称重法称量PC的回收量，两者的比值就是PC的收率。PC yield: The amount of PC produced is tested by nuclear magnetic resonance spectrometer, and the amount of PC recovered is weighed by weighing method. The ratio of the two is the PC yield.
重金属Zn：按照SJ/T 11568-2016附录B的方法测试PC中Zn的含量。Heavy metal Zn: The Zn content in PC was tested according to the method in Appendix B of SJ/T 11568-2016.
实施例1～9、对比实施例1的测试结果见表1：The test results of Examples 1 to 9 and Comparative Example 1 are shown in Table 1:
表1测试结果 Table 1 Test results
由上表得知，调整催化剂比例、添加溶剂均能显著增加PC的产生量，而且能够控制共聚物和联产物的产出比例，通过精馏可以得到优质的PC。It can be seen from the above table that adjusting the catalyst ratio and adding solvent can significantly increase the production of PC, and can control the output ratio of copolymers and co-products. High-quality PC can be obtained through distillation.
以上所述，仅是本发明的较佳实施例而已，并非是对本发明作其它形式的限制，任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更或改型为等同变化的等效实施例。但是凡是未脱离本发明技术方案内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与改型，仍属于本发明技术方案的保护范围。 The above is only a preferred embodiment of the present invention, and does not limit the present invention in other forms. Any technician familiar with the profession may use the above disclosed technical content to change or modify it into an equivalent embodiment with equivalent changes. However, any simple modification, equivalent change and modification made to the above embodiment according to the technical essence of the present invention without departing from the technical solution of the present invention still belongs to the protection scope of the technical solution of the present invention.

Claims (8)

  1. 一种合成二氧化碳基多元共聚物同时联产碳酸丙烯酯的方法，包括以环氧丙烷、二氧化碳为主要反应原料的二元反应，以环氧丙烷、二氧化碳、苯酐为主要反应原料的三元合成反应，以及在此基础上添加其它酸酐或/和环氧烯烃的四元及四元以上合成反应；A method for synthesizing a carbon dioxide-based multi-polymer and simultaneously producing propylene carbonate, comprising a binary reaction with propylene oxide and carbon dioxide as main reaction raw materials, a ternary synthesis reaction with propylene oxide, carbon dioxide and phthalic anhydride as main reaction raw materials, and a quaternary or higher synthesis reaction with other acid anhydrides and/or olefin oxides added thereto;
    其特征在于，制备步骤为：It is characterized in that the preparation steps are:
    1)将环氧丙烷、共聚单体和非金属催化剂投入到反应器中，充入二氧化碳进行共聚反应制备胶液，共聚反应时保持反应温度为40℃～100℃、反应压力为0.1MPa～4.0MPa；所述的环氧丙烷、共聚单体和非金属催化剂的摩尔比为(800～2500)：(0～2000)：1；1) Putting propylene oxide, comonomer and non-metal catalyst into a reactor, charging carbon dioxide to carry out copolymerization reaction to prepare a glue solution, maintaining the reaction temperature at 40° C. to 100° C. and the reaction pressure at 0.1 MPa to 4.0 MPa during the copolymerization reaction; the molar ratio of propylene oxide, comonomer and non-metal catalyst is (800 to 2500): (0 to 2000): 1;
    2)步骤1)制备的胶液用有机溶剂进一步溶解，再加入醇析出沉淀物，固液分离的固体经洗涤、脱挥后得到二氧化碳基多元共聚物；固液分离的液体经精馏、萃取分离后得到碳酸丙烯酯；2) The glue solution prepared in step 1) is further dissolved in an organic solvent, and then alcohol is added to precipitate a precipitate, and the solid separated from the solid and liquid is washed and devolatilized to obtain a carbon dioxide-based multi-polymer; the liquid separated from the solid and liquid is distilled and extracted to obtain propylene carbonate;
    步骤1)中所述的非金属催化剂为三烷基硼类与四正丁基卤化铵按摩尔比(1.3～3):1配合形成的复合催化剂。The non-metallic catalyst in step 1) is a composite catalyst formed by the coordination of trialkylborane and tetra-n-butylammonium halide in a molar ratio of (1.3-3):1.
  2. 根据权利要求1所述的一种合成二氧化碳基多元共聚物同时联产碳酸丙烯酯的方法，其特征在于：The method for synthesizing a carbon dioxide-based multi-polymer and simultaneously producing propylene carbonate according to claim 1, characterized in that:
    步骤1)中所述的共聚单体为一种或两种以上的酸酐类单体和/或环氧丙烷以外的其它环氧化物。The comonomers described in step 1) are one or more anhydride monomers and/or other epoxides other than propylene oxide.
  3. 根据权利要求1所述的一种合成二氧化碳基多元共聚物同时联产碳酸丙烯酯的方法，其特征在于：The method for synthesizing a carbon dioxide-based multi-polymer and simultaneously producing propylene carbonate according to claim 1, characterized in that:
    步骤1)中所述的环氧丙烷和非金属催化剂的摩尔比为(1600～2000)：1。The molar ratio of propylene oxide to the non-metallic catalyst in step 1) is (1600-2000):1.
  4. 根据权利要求1所述的一种合成二氧化碳基多元共聚物同时联产碳酸丙烯酯的方法，其特征在于：The method for synthesizing a carbon dioxide-based multi-polymer and simultaneously producing propylene carbonate according to claim 1, characterized in that:
    步骤1)中所述的反应温度为70℃～90℃，反应压力为1.0MPa～2.0MPa。The reaction temperature in step 1) is 70° C. to 90° C., and the reaction pressure is 1.0 MPa to 2.0 MPa.
  5. 根据权利要求1所述的一种合成二氧化碳基多元共聚物同时联产碳酸丙烯酯的方法，其特征在于：The method for synthesizing a carbon dioxide-based multi-polymer and simultaneously producing propylene carbonate according to claim 1, characterized in that:
    步骤1)中所述的共聚反应进行2h～5h后，向反应体系中保压加入有机溶剂，保持步骤1)的反应温度和反应压力继续反应4h～6h得到胶液；所述有机溶剂与步骤1)中所述的环氧丙烷质量比为(0.01～2):1。After the copolymerization reaction described in step 1) is carried out for 2h to 5h, an organic solvent is added to the reaction system under pressure, and the reaction temperature and reaction pressure of step 1) are maintained to continue the reaction for 4h to 6h to obtain a glue solution; the mass ratio of the organic solvent to the propylene oxide described in step 1) is (0.01 to 2):1.
  6. 根据权利要求1或5所述的一种合成二氧化碳基多元共聚物同时联产碳酸丙烯酯的方法，其特征在于：The method for synthesizing a carbon dioxide-based multi-polymer and simultaneously producing propylene carbonate according to claim 1 or 5, characterized in that:
    所述的有机溶剂为乙酸甲酯、乙酸乙酯、二氯甲烷、二氯乙烷、二氯丙烷、四氢呋喃、甲基四氢呋喃中的一种或两种以上的混合溶剂。The organic solvent is one or a mixed solvent of two or more of methyl acetate, ethyl acetate, dichloromethane, dichloroethane, dichloropropane, tetrahydrofuran and methyltetrahydrofuran.
  7. 根据权利要求1或5所述的一种合成二氧化碳基多元共聚物同时联产碳酸丙烯酯的方法，其特征在于：The method for synthesizing a carbon dioxide-based multi-polymer and simultaneously producing propylene carbonate according to claim 1 or 5, characterized in that:
    所述的有机溶剂为乙酸甲酯与二氯甲烷或二氯乙烷按质量比1～7：93～99配比的混合溶剂。The organic solvent is a mixed solvent of methyl acetate and dichloromethane or dichloroethane in a mass ratio of 1-7:93-99.
  8. 根据权利要求1所述的一种合成二氧化碳基多元共聚物同时联产碳酸丙烯酯的方法，其特征在于：The method for synthesizing a carbon dioxide-based multi-polymer and simultaneously producing propylene carbonate according to claim 1, characterized in that:
    所述的有机溶剂与步骤1)中所述的环氧丙烷的质量比为(0.1～0.5):1。 The mass ratio of the organic solvent to the propylene oxide in step 1) is (0.1-0.5):1.
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