WO2024120011A1 - Procédé de co-production de pc tout en synthétisant un copolymère à composants multiples à base de dioxyde de carbone - Google Patents

Procédé de co-production de pc tout en synthétisant un copolymère à composants multiples à base de dioxyde de carbone Download PDF

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Publication number
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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English (en)
Chinese (zh)
Inventor
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/fr

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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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyethers (AREA)

Abstract

L'invention concerne un procédé de co-production de PC tout en synthétisant un copolymère à composants multiples à base de dioxyde de carbone, se rapportant au domaine technique des copolymères à composants multiples. Les étapes de préparation comprennent : la mise en place d'oxyde de propylène, d'un comonomère et d'un catalyseur non métallique dans un réacteur, le remplissage du réacteur avec du dioxyde de carbone pour la régulation de pression, et la réalisation d'une réaction de copolymérisation à une certaine température ; après que la réaction a été effectuée dans une certaine mesure, le maintien de la pression, et l'ajout d'un solvant organique pour continuer la réaction pour obtenir une solution de colle ; la dissolution supplémentaire de la solution de colle à l'aide du solvant organique, l'ajout d'alcool pour précipiter un précipité, et le lavage et la dévolatilisation du solide pour obtenir un copolymère à composants multiples à base de dioxyde de carbone ; et la réalisation d'une rectification, d'une extraction et d'une séparation pour obtenir du PC. Dans la présente invention, le PC est co-produit tandis que le copolymère à composants multiples à base de dioxyde de carbone est synthétisé en utilisant de l'oxyde de propylène et du dioxyde de carbone en tant que matières premières, la pression de réaction est faible, la température est faible, aucun gaz résiduaire n'est généré, et aucune eau résiduaire n'est générée ; la co-production de PC tout en synthétisant un copolymère à composants multiples à base de dioxyde de carbone à l'aide du catalyseur non métallique n'entraîne pas de résidus métalliques ; et le procédé est un procédé de synthèse écologique et économe en énergie et est plus largement appliqué.
PCT/CN2023/124401 2022-12-05 2023-10-13 Procédé de co-production de pc tout en synthétisant un copolymère à composants multiples à base de dioxyde de carbone WO2024120011A1 (fr)

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CN115612085B (zh) * 2022-12-05 2023-03-31 山东联欣环保科技有限公司 一种合成二氧化碳基多元共聚物同时联产pc的方法
CN115772321A (zh) * 2023-02-10 2023-03-10 山东联欣环保科技有限公司 一种生物可降解复合膜及其制备方法
CN116355189A (zh) * 2023-03-28 2023-06-30 山东联欣环保科技有限公司 一种用萘酐改性的二氧化碳基多元共聚物及其制备方法
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CN116496542B (zh) * 2023-06-13 2023-10-03 山东联欣环保科技有限公司 一种二氧化碳基生物降解发泡材料的制备方法

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