KR101767310B1 - Method for synthesizing terpolymer of epoxide containing electon withdrawing group, CO2 and epoxide non-contaning electon withdrawing group - Google Patents

Abstract

The present invention relates to a process for preparing a terpolymer of an epoxide comprising an electron withdrawing group using an asymmetric catalyst, an epoxide having no carbon dioxide and an electron withdrawing group. The method for preparing the terpolymer of the present invention can synthesize an eco-friendly high value-added polymer which facilitates catalyst recovery and reuse after the reaction by using an inhomogeneous catalyst as a copolymerization catalyst and includes an electron withdrawing group in the polymer, .

Description

FIELD OF THE INVENTION [0001] The present invention relates to a process for preparing an epoxide containing an electron withdrawing group, an epoxide containing no carbon dioxide and an electron withdrawing group, and an epoxide containing non-electron withdrawing group,

The present invention relates to a process for preparing copolymers, and more particularly, to a process for preparing terpolymers of epoxides containing an electron withdrawing group using an inhomogeneous catalyst, carbon dioxide and epoxides free of electron withdrawing groups.

Carbon dioxide (CO ₂₎ to the atmosphere, depending on the use of fossil fuels, methane (CH _4), and hydrogen sulfide (H ₂ S), carbonyl sulfide (COS), such as acid gas concentration is increased, there is a global warming and problems resulting. Especially, atmospheric carbon dioxide has been actively discussed worldwide since the 1992 Rio Environment Conference.

As a solution to this problem, research on Carbon Capture and Utilization (CCU), which is a carbon compound production technology for recycling carbon dioxide, is being carried out along with research on Carbon Dioxide Capture & Storage (CCS) . CCU technology is currently investing heavily in technology development, because it can overcome the limitations of carbon dioxide storage and convert carbon dioxide to other carbon compounds with high added value by using it as a carbon source rather than as a simple waste.

CCUs are divided into chemical conversion and biological conversion, and chemical conversion is divided into electrochemical conversion, photochemical conversion, and catalytic chemical conversion. Among them, catalytic chemical conversion is a technology that is highly commercialized because it reduces the total amount of energy used. It is possible to synthesize urea fertilizer, chemical form production, regenerated methanol production, concrete curing, decarboxylation mineralization, and polymer production with chemical conversion technology. Especially, polymer has various advantages such as food container, transparent film, Which is used in a wide range of fields.

The polyalkylene carbonate is a high-value-added raw material using carbon dioxide which can be produced using an epoxide compound and carbon dioxide. This is because the carbon dioxide gas is injected into the epoxide compound at a constant pressure to copolymerize it, and the environmentally friendly value is high because the poisonous compound phosgene is not used and carbon dioxide can be obtained at low cost. In addition, it is a biodegradable polymer, which is soft rubbery in nature and has excellent workability and is easy to control its decomposition characteristics, and thus has been extensively studied as a biodegradable polymer. However, it has a low glass transition temperature (Tg) and is easily decomposed at around 200 to exhibit poor heat resistance. In addition, its use is restricted due to its low elastic modulus due to its mechanical properties and its easily breaking property in thin film products.

In the process for preparing polyalkylene carbonate using carbon dioxide, the copolymerization catalyst uses a metal complex homogeneous catalyst or a metal-carboxylate heterogeneous catalyst. The uniform catalyst is difficult to synthesize, and it is troublesome to avoid exposure to moisture from the synthesis of the catalyst to the introduction of the catalyst, and recovery and reuse are not easy.

U.S. Patent Publication No. 2003-0013840 discloses a polyalkylene carbonate copolymer capable of hydrolysis or biodegradation by microorganisms in a natural environment and a manufacturing method thereof. The polyalkylene carbonate copolymer has a low pyrolysis temperature and an excellent biodegradability, but has a problem that its application range is limited due to its low flexibility.

Korean Patent Laid-Open Publication No. 2014-0035927 relates to a polyalkylene carbonate composition and method, and relates to a polymer composition comprising an aliphatic polycarbonate chain containing a functional group that increases the strength of a polymer to wet or adhere an inorganic material, and A manufacturing method is disclosed. However, this uses a homogeneous catalyst, which is a metal complex with a polymerization initiator and a ligand bound thereto.

Therefore, it is required to overcome the low thermal and mechanical properties of the polymer synthesized from the carbon dioxide as a raw material, and also to provide an economical and environmentally friendly manufacturing technique for the use of the catalyst.

U.S. Published Patent Application No. 2003-0013840 Korea Patent Publication No. 2014-0035927

In order to solve the above problems, the present invention is to provide a process for preparing an epoxide, carbon dioxide and an epoxide-containing terpolymer containing an electron withdrawing group, which comprises an electron withdrawing group using an inhomogeneous catalyst.

DISCLOSURE OF THE INVENTION In order to solve the above problems, the present inventors have found a process for producing a terpolymer of an epoxide containing no electron-withdrawing group, carbon dioxide and an electron-withdrawing group using an inhomogeneous catalyst, and accomplished the present invention.

The present invention relates to a process for preparing a terpolymer of an epoxide containing no epoxide, carbon dioxide and an electron withdrawing group, including an electron withdrawing group, comprising a metal-dicarboxylate copolymerizing catalyst, an epoxide comprising an electron withdrawing group and an electron withdrawing group ≪ RTI ID = 0.0 > epoxide < / RTI > Introducing carbon dioxide into the mixture at 10 to 30 bar and conducting a reaction at a temperature of 0 ° C to 60 ° C for 10 hours to 50 hours to synthesize a terpolymer; And purifying the terpolymer and recovering the copolymerization catalyst.

The present invention also relates to a process for preparing a metal-dicarboxylate-based copolymerization catalyst, wherein the metal-dicarboxylate-based copolymerization catalyst is an inhomogeneous catalyst and the dicarboxylate compound is selected from the group consisting of oxalate, malonate, succinate, glutarate, At least one aliphatic dicarboxylate selected from the group consisting of adipate, pimelate, and hexafluroglutarate; Or at least one aromatic dicarboxylate selected from the group consisting of terephthalate, isopthalate and homophthalate, and the metal is at least one selected from the group consisting of sodium (Na), magnesium (Mg), zinc (Zn) Wherein at least one selected from the group consisting of titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni) to provide.

The present invention also provides a process for producing the metal-dicarboxylate copolymerization catalyst, which comprises a transition metal salt coating layer formed on the surface of the particles by a transition metal salt.

The transition metal salt may be selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Tc, Ru, Rh, Pd and Ir. Wherein X is a metal ion selected from the group consisting of chloride, fluoride, bromide, sulfate, nitrate, trifluoromethanesulfonate, trifluoroacetate ^{), PF 6-, BF 4-,} ClO 4-, R-SO 3- , and an anion selected from the group consisting of PO-R ^3-, where R is hydrogen or a service of the alkyl group having 1 to 10 carbon atoms, the production method do.

The present invention also relates to compounds of formula (I) wherein said electron withdrawing group is selected from the group consisting of halogen, cyano, sulfonyl, carboxyl, amide, quaternary amino, alkyl halide Wherein the aryl group is at least one selected from the group consisting of an aryl halide, phenyl substituted with an electron withdrawing group, nitrosyl, nitro, and carbonyl.

In the present invention, the epoxide not containing the electron withdrawing group may be an alkylene oxide having 2 to 20 carbon atoms, a cycloalkylene oxide having 4 to 20 carbon atoms, an allyl glycidyl ether, a vinyl (vinyl) oxirane, and glycidol. < / RTI >

The present invention also relates to a process for preparing an epoxy resin composition, wherein the metal-dicarboxylate-based copolymerization catalyst is Zn (glutarate), the epoxide containing the electron withdrawing group is epichlorohydrin and the epoxide containing no electron withdrawing group is propylene Propylene oxide. ≪ / RTI >

The present invention also provides a process wherein the epoxide comprising the electron withdrawing group and the epoxide containing no electron withdrawing group are mixed in a molar ratio of 1: 100 to 100: 1.

The present invention also provides a process wherein the epoxide comprising the electron withdrawing group and the copolymerization catalyst are mixed in a molar ratio of 20: 1 to 300: 1.

The method for producing the terpolymer containing an electron withdrawing group of the present invention is an eco-friendly high value-added polymer which is easy to recover and reuse after catalyst reaction by using an inhomogeneous catalyst as a copolymerization catalyst and includes an electron withdrawing group, Can be synthesized.

Figure 1 is a 1H NMR analysis of a terpolymer synthesized according to one embodiment of the present invention.
2 shows the 1HNMR analysis results of a terpolymer synthesized without a solvent according to one embodiment of the present invention.

Prior to the detailed description of the present invention, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms. Therefore, the embodiments described in this specification and the configurations shown in the drawings are merely the most preferred embodiments of the present invention and do not represent all the technical ideas of the present invention. Therefore, It is to be understood that equivalents and modifications are possible.

In one aspect, the present invention is a process for preparing a terpolymer of an epoxide comprising an epoxide, carbon dioxide and an electron withdrawing group, the process comprising the reaction of a metal-dicarboxylate copolymerization catalyst, an epoxide comprising an electron withdrawing group ≪ / RTI > and an electron withdrawing group; Introducing carbon dioxide into the mixture at 10 to 30 bar and conducting a reaction at a temperature of 25 to 60 DEG C for 10 to 50 hours to synthesize a terpolymer; And purifying the terpolymer and recovering the copolymerization catalyst.

The copolymer of the present invention is a polymer formed of two or more monomers and is also referred to as a copolymer. The copolymer may be a random copolymer, an alternating copolymer, or the like depending on the arrangement method (chain distribution) Block copolymers, graft copolymers, and the like. The copolymers of the present invention are terpolymers of epoxides including electron withdrawing groups, epoxides which do not contain carbon dioxide and electron withdrawing groups, and are block copolymers, alternating copolymers, or random copolymers.

The electron withdrawing group is a functional group which tends to attract electrons elsewhere when hydrogen is used as a standard in the molecule. In the present invention, epoxides containing electron-withdrawing groups as monomers are used in the synthesis of the terpolymer. The epoxide containing the electron withdrawing group can produce a polymer having refractory properties and can also be easily crosslinked after the production of the polymer. In one embodiment, the electron withdrawing group is selected from the group consisting of halogen, cyano, sulfonyl, carboxyl, amide, quaternary amino, alkyl halide, Phenyl, substituted by an electron withdrawing group, nitrosyl, nitro, and carbonyl. The term " aryl " Phenyl is originally an electron donating group, but it can exhibit the property of attracting electrons when one or more of the substituents of the phenyl group is an electron withdrawing group. Therefore, the epoxide containing the electron withdrawing group of the present invention can use an epoxide compound in which the phenyl substituted with an electron withdrawing group is contained in the molecule. The electron withdrawing group substituted on the phenyl may be, for example, a halogen, a cyano, a sulfonyl, a carboxyl, an amide, a quarternary amino, a halogenated alkyl alkyl halide, and aryl halide. In one embodiment, the epoxide comprising said electron withdrawing group is epifluorohydrin, epichlorohydrin, epibromohydrin. The epoxide containing no electron withdrawing group may be an alkylene oxide having 2 to 20 carbon atoms, a cycloalkylene oxide having 4 to 20 carbon atoms, an allyl glycidyl ether, vinyloxirane, Glycidol, preferably propylene oxide may be used.

The terpolymer synthesis reaction using the epoxide compound and carbon dioxide of the present invention is synthesized in the presence of a copolymerization catalyst. The heterogeneous catalyst of the present invention is a heterogeneous catalyst. The heterogeneous catalyst is a solid catalyst which forms a heterogeneous mixture without mixing with reactants and products in a chemical reaction. When dealing with large amounts of reactants and products in industry, recovery of the catalyst is very important and recovery of the catalyst is indispensable especially when expensive noble metal catalysts such as platinum, iridium, and palladium are used. Therefore, the heterogeneous catalyst of the present invention can be easily recovered after the reaction and can be reused, thereby ensuring economical efficiency. In one embodiment, the copolymerization catalyst of the present invention is an inhomogeneous catalyst that is a metal-dicarboxylate compound and the dicarboxylate is selected from the group consisting of oxalate, malonate, succinate, glutarate, at least one aliphatic dicarboxylate selected from the group consisting of glutarate, adipate, pimelate, and hexafluroglutarate; Or at least one aromatic dicarboxylate selected from the group consisting of terephthalate, isopthalate and homophthalate. In addition, the dicarboxylate is at least one selected from the group consisting of various aliphatic or aromatic dicarboxylic acids having 3 to 20 carbon atoms Rate can be used. The metal is selected from the group consisting of Na, Mg, Zn, Ti, V, Cr, Mn, Fe, Ni) and copper (Cu). Preferably, the heterogeneous metal-dicarboxylate-based copolymerization catalyst of the present invention is Zn (glutarate).

The metal-dicarboxylate copolymerization catalyst may include a transition metal salt coating layer formed on the surface of the particles by a transition metal salt. The transition metal salt coating layer may be formed on at least a part of the surfaces of the metal-dicarboxylate-based catalyst particles, and may be formed by wrapping the catalyst particles. In particular, the transition metal salt coating layer is preferably a single molecular layer formed from the transition metal salt in view of the improvement of catalytic activity. In one embodiment, the transition metal salt is a compound represented by MX, wherein M is a metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Tc, Ru, Rh, Pd, Ion and X is selected from the group consisting of chloride, fluoride, bromide, sulfate, nitrate, trifluoromethanesulfonate, trifluoroacetate, ^{, PF 6-, BF 4-, ClO} 4-, R-SO 3- , and an anion selected from the group consisting of R-PO ^3-, wherein R is hydrogen or alkyl having 1 to 10 carbon atoms.

The terpolymer of the present invention is copolymerized with an epoxide containing an electron withdrawing group, an epoxide containing no electron withdrawing group, and carbon dioxide in the presence of the heterogeneous catalyst. The copolymerization is carried out in a solution, and a solvent, a metal-dicarboxylate copolymerization catalyst, an epoxide containing an electron withdrawing group, and an epoxide having no electron withdrawing group are added to the reactor to prepare a mixture, To synthesize a terpolymer. In one embodiment, the epoxide comprising the electron withdrawing group and the epoxide containing no electron withdrawing group may be mixed in a molar ratio of 1: 100 to 100: 1. The epoxide comprising the electron withdrawing group and the copolymerization catalyst may be mixed in a molar ratio of 20: 1 to 300: 1. If the ratio of the catalyst is too small, it is difficult to exhibit sufficient catalytic activity in solution polymerization. On the other hand, if the catalyst is excessively large, by-products may be produced inefficiently due to the use of an excessive amount of catalyst, -biting can occur. Examples of the solvent include methylene chloride, ethylene dichloride, trichloroethane, tetrachloroethane, chloroform, acetonitrile, propionitrile, dimethylformamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, But are not limited to, 1,4-dioxane, hexane, toluene, tetrahydrofuran, methyl ethyl ketone, methylamine ketone, methyl isobutyl ketone, acetone, cyclohexanone, trichlorethylene, methyl acetate, vinyl acetate, ethyl acetate, At least one selected from the group consisting of lactone, caprolactone, nitropropane, benzene, styrene, xylene, and methyl propasol may be used. Of these, the use of methylene chloride or ethylene dichloride as a solvent enables the polymerization reaction to proceed more effectively. In addition, if the epoxide used in the copolymerization reaction is a liquid, it can be used simultaneously as a solvent and a reactant.

Carbon dioxide is introduced into the mixture prepared by mixing the reactants at a pressure of 10 bar to 30 bar and reacted at a temperature of 0 ° C to 60 ° C for 10 hours to 50 hours to synthesize a terpolymer. The synthesized terpolymer of the present invention contains an electron withdrawing group in the molecule, which has fire resistance and biocompatibility and has an advantage of facilitating crosslinking due to an electron withdrawing group. In one embodiment, the weight average molecular weight of the terpolymer is from 5,000 to 350,000. The terpolymer containing the synthesized electron withdrawing group is recovered after refining after the reaction. The purification process is aimed at recovering the catalyst and removing impurities from the mixture containing the synthesized terpolymer and the copolymerization catalyst. The copolymerization catalyst may be produced by a conventional known solid-liquid separation method such as filtration, gravity sedimentation, And the synthesized copolymer is not limited to any conventional polymer purification method. In one embodiment, the copolymerization catalyst is obtained by recovering the heterogeneous catalyst in the reaction solution by a filtration method, forming a precipitate using the difference in solubility of the organic solvent in order to separate and purify the tertiary polymer in the solution from unreacted materials, Separation and purification.

Hereinafter, embodiments are provided to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited to the following examples.

Example  One Heterogeneity  Catalyzed An electron extractor  Included Epoxide , Carbon dioxide and electron withdrawing groups Epoxide Terpolymer  synthesis

A 100 mL autoclave reactor was completely dehydrated under vacuum condition at 100 < 0 > C for 12 hours. The dried autoclave reactor was transferred to a glove box filled with argon and then 0.200 g (1.02 mmol) of zinc glutarate (ZnGA), 7.95 mL (100.0 mmol) of propylene oxide (PO) 3.92 mL (50.0 mmol) of epichlorohydrin and 10.0 mL of methylene chloride anhydride were sealed in the reactor. After withdrawing the reactor from the glove box, CO ₂ was added at room temperature until the solution became saturated and the internal pressure of the reactor became 20 bar, followed by stirring at room temperature for 40 hours. After completion of the reaction, the internal pressure of the reactor was lowered to the atmospheric pressure. The mixed product in the reactor was dissolved in 50 mL of methylene chloride, and then filtered using Celite. The filtrate was washed successively with methylene chloride (~300 mL) during filtration and the filtrate was concentrated using a rotary evaporator to a volume of 2 mL to 3 mL. To purify the tertiary polymer thereafter, 1 mL of 1.25M Methanolic HCl (Sigma-Aldrich) was added, and the mixture was stirred for 5 minutes. During the stirring, 250 mL of methanol was added slowly and stirred for 45 minutes to form a precipitate. The supernatant was removed and the resulting precipitate was separated and purified as described above was repeated once. The purified product was dried for 12 hours under a vacuum of 50 < 0 > C to 60 < 0 > C to obtain a terpolymer.

[Chemical Formula 1]

A terpolymer was prepared in the same manner as above except that the mixing ratio of propylene oxide and epichlorohydrin, the reaction temperature, and the amount of solvent added were varied. The results are shown in Table 1. TON = number of conversions: weight of polymer relative to zinc catalyst mole number; PO = propylene oxide; ECH = Epichlorohydrin; PPC = poly (propylene carbonate); PCPC = poly (chloropropylene carbonate).

¹ HNMR was measured in order to analyze the synthesis results of the terpolymer. As shown in FIG. 1, the NMR spectra of the terpolymers synthesized under the conditions of Experimental Example SUD 287 showed that the effective peak a in the PCPC in the molecule and the effective peak b Was observed, indicating that a terpolymer was synthesized. Also, referring to FIG. 2, as a result of NMR measurement of a terpolymer synthesized under the conditions of Experimental Example SUD 241, the effective peak a in the PCPC in the molecule and the effective peak b in the PPC were observed, and it was judged that the terpolymer was synthesized.

Experimental Example SUD 293 and SUD 287 were compared with each other at a molar ratio of 2: 1. The reaction temperature was different between PO and ECH, and TON was measured to be high in Experimental Example SUD 287 having a reaction temperature of 60, The activity increased at higher temperature than room temperature. In addition, the ratio of PCPC in the obtained polymer was relatively high in the reaction at room temperature, but the ratio of PCPC in the molecule was relatively low in the reaction of 60. Therefore, PCPC in the molecule is considered to be synthesized at a higher rate when the reaction is performed at a temperature close to room temperature. Experimental Examples Glass transition temperatures of SUD 293 and SUD 287 were found to be 36.0 and 35.2, respectively, by differential scanning calorimetry (DSC) analysis.

Experimental Example SUD 241 was obtained by mixing PO and ECH at a ratio of 1: 1 without addition of a solvent. The yield and TON of the SUD 241 were measured relatively higher than those of the other experimental examples. On the other hand, the glass transition temperature was relatively low, and as the amount of ECH participated in the reaction increased, the ratio of PCPC in the synthesized polymer was increased, and the stretchability of the polymer was increased and the glass transition temperature was lowered accordingly.

[Table 1]

While the present invention has been described in connection with what is presently considered to be the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, .

All technical terms used in the present invention are used in the sense that they are generally understood by those of ordinary skill in the relevant field of the present invention unless otherwise defined. The contents of all publications referred to herein are incorporated herein by reference.

Claims (9)

A process for preparing a terpolymer of an epoxide comprising an electron withdrawing group, an epoxide containing no carbon dioxide and an electron withdrawing group,
Preparing a mixture of a metal-dicarboxylate-based copolymerization catalyst, an epoxide containing an electron withdrawing group and an epoxide containing no electron withdrawing group;
Introducing carbon dioxide into the mixture at 10 to 30 bar and conducting a reaction at a temperature of 0 ° C to 60 ° C for 10 hours to 50 hours to synthesize a terpolymer; And
Purifying the terpolymer and recovering the copolymerization catalyst,
Wherein the metal-dicarboxylate copolymerization catalyst comprises a transition metal salt coating layer formed on the surface of the particles by a transition metal salt.
The method according to claim 1,
The metal-dicarboxylate-based copolymerization catalyst is an inhomogeneous catalyst,
The dicarboxylate compound may be selected from the group consisting of oxalate, malonate, succinate, glutarate, adipate, pimelate, and hexafluoroglutarate at least one aliphatic dicarboxylate selected from the group consisting of hexafluroglutarate; Or at least one aromatic dicarboxylate selected from the group consisting of terephthalate, isopthalate and homophthalate,
The metal is selected from the group consisting of Na, Mg, Zn, Ti, V, Cr, Mn, Fe, Ni), and copper (Cu).
delete The method according to claim 1,
The transition metal salt is a compound represented by MX,
Wherein M is a metal ion selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Tc, Ru, Rh, Pd,
Wherein X is selected from the group consisting of chloride, fluoride, bromide, sulfate, nitrate, trifluoromethanesulfonate, trifluoroacetate, PF ^{6 -} , BF ^{4 -} , ClO ^{4 -} , R - SO ^{3 -} and R - PO ^{3 -}
Wherein R is hydrogen or alkyl having 1 to 10 carbon atoms.
The method according to claim 1,
The electron withdrawing group may be a halogen, a cyano, a sulfonyl, a carboxyl, an amide, a quarternary amino, an alkyl halide, a halogenated aryl aryl halide, phenyl substituted with an electron withdrawing group, nitrosyl, nitro, and carbonyl.
The method according to claim 1,
The epoxide containing no electron withdrawing group may be an alkylene oxide having 2 to 20 carbon atoms, a cycloalkylene oxide having 4 to 20 carbon atoms, an allyl glycidyl ether, vinyloxirane, Glycidol. ≪ / RTI >
The method according to claim 1,
The metal-dicarboxylate-based copolymerization catalyst is Zn (glutarate)
The epoxide comprising said electron withdrawing group is epichlorohydrin,
Wherein the epoxide containing no electron withdrawing group is propylene oxide.
The method according to claim 1,
Wherein the epoxide comprising the electron withdrawing group and the epoxide containing no electron withdrawing group are mixed in a molar ratio of 1: 100 to 100: 1.
The method according to claim 1,
Wherein the epoxide comprising the electron withdrawing group and the copolymerization catalyst are mixed in a molar ratio of 20: 1 to 300: 1.

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