JP2004263168A - Three-component catalyst used for producing high molecular aliphatic polycarbonate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a three component catalyst used for producing a high molecular aliphatic polycarbonate, having a high catalytic effect and giving a high carbon dioxide-fixing ratio and excellent content of an alternate structure, and provide a method for producing the same. <P>SOLUTION: The three component catalyst is prepared from glycerol, a metal salt and zinc dihydrocarbyl as starting materials. The metal salt is a rare earth metal salt expressed by the general formula: MX<SP>1</SP><SB>n</SB>X<SP>2</SP><SB>m</SB>or a non-rare earth metal salt expressed by the general formula: ZX<SP>3</SP><SB>p</SB>X<SP>4</SP><SB>g</SB>, wherein X<SP>1</SP>expresses a carboxy group having ≥10<SP>-3</SP>K<SB>a</SB>or a sulfo group. The catalyst is produced by adding the metal to bring the ratio of the salt:glycerol to be 1-1.5:1-10 in an organic solvent, dropping zinc dihydrocarbyl so as to bring the molar ratio, zinc dihydrocarbyl:metal salt, to be 2-20:1-1.5 in carbon dioxide gas, and aging the product in the carbon dioxide atmosphere. The three component catalyst is used for producing the high molecular aliphatic polycarbonate. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to a three-way catalyst used in the production of a high molecular weight aliphatic polycarbonate. The present invention also relates to a method for producing the three-way catalyst and a method for producing a high molecular weight aliphatic polycarbonate using the three-way catalyst.

  In the production process of thermal power generation, steelmaking, oil production, cement, etc., a large amount of fossil fuel is burned, so a large amount of carbon dioxide gas is emitted, and the greenhouse effect due to this causes daily severe environmental pollution. . Therefore, carbon dioxide gas is recognized as one kind of environmental pollution gas. On the other hand, carbon dioxide is a resource that may be used under certain conditions. One of the main directions of using carbon dioxide gas is to synthesize a polymer material using it as a raw material. A copolymer having a highly alternating structure, that is, an aliphatic polycarbonate can be synthesized using carbon dioxide gas and an epoxy compound as raw materials. Since this polymer has an ester bond in the main chain, it can be photodegraded and is also a completely biodegradable plastic. Such a high molecular weight copolymer film has good transparency and has an excellent function of not allowing oxygen gas and water vapor to permeate. A wide range of applications are expected in areas such as pharmaceuticals and food packaging materials.

In recent years, various catalysts have been used for the copolymerization reaction of carbon dioxide and epoxy compounds. Patent Documents 1 to 3 produce dialkylzinc / active hydrogen-containing catalyst as an alternating copolymer of carbon dioxide and epoxy compound (Mn> 20,000), and various polyurethanes and polyethers having different molecular weights. A method is disclosed. Patent Document 4 discloses that high catalyst efficiency (10 ³ to 10 ⁴ g polymer / mol catalyst) can be obtained using a porphyrin metal complex compound catalyst. However, this method requires a polymer having a low molecular weight (about 5,000) and a polymerization reaction time of 10 days or longer. Patent Documents 5 and 6 disclose a polymer anion complex bimetallic catalyst system, and a catalyst having a catalyst efficiency of 10 ⁴ g polymer / mol was obtained. It is difficult to purify polycarbonate. Moreover, it is necessary to further improve the molecular weight.

  Non-Patent Documents 1 and 2 disclose techniques for producing polycarbonate using a rare earth three-way catalyst. The technique disclosed in the former is a method using a rare earth metal phosphonate catalyst system, but the obtained polycarbonate is a block copolymer, the catalyst efficiency is low, and the fixing rate of carbon dioxide gas is 30% by weight or less. The content of the alternating structure of the polycarbonate obtained by the latter is 95% or more, but the production of the complex is complicated, the cost is too high, and the catalyst efficiency is not satisfactory.

  Non-Patent Document 3 discloses a catalyst and a polymer system in a process for producing a polycarbonate. Except for a small number of zinc salt catalyst systems, the polymerization time is 40 hours, and most of them are polymerization processes using a system containing an organic solvent, and the solvents are tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane. , Dichloromethane, hexane, benzene, toluene or a mixed solvent thereof. When solvent-free polymerization is carried out using zinc glutarate as a catalyst, the catalyst efficiency for obtaining a polycarbonate is high, but the polymerization requires 40 hours, and the requirements for the polymerization conditions are extremely severe.

  Non-Patent Documents 4 to 7 disclose that the catalyst efficiency for the copolymerization reaction of carbon dioxide and epoxycyclohexane is high using a hindered phenol zinc salt as a catalyst. However, in the case of terpolymerization of carbon dioxide, epoxycyclohexane and propylene oxide, the catalytic efficiency is not good.

  Non-Patent Document 8 discloses that the catalytic efficiency of a zinc imide multidentate complex for the copolymerization reaction of carbon dioxide and propylene oxide is high.

  Patent Documents 7 and 8 provide a method for producing a rare earth-based three-way catalyst and a method for producing a high molecular weight aliphatic polycarbonate. Patent Documents 9 and 10 filed by the present applicant provide an efficient method for producing a high-molecular weight aliphatic polycarbonate. In these methods, a catalyst comprising a rare earth complex, an alkyl metal compound, a polyhydric alcohol, and a cyclic carbonate is selected, and an epoxy compound and carbon dioxide gas are copolymerized with no solvent under a medium pressure condition. The copolymer has a molecular weight of 80,000 to 200,000, an alternating structure content of 98% or more, and a fixed rate of carbon dioxide gas exceeding 40% by weight.

These conventional catalysts are less active if not used immediately after production. Moreover, the polymerization reaction using this requires a long time of 40 hours. Therefore, a catalyst that can be easily produced under milder conditions, can be stored, and has high catalyst efficiency has been demanded.
US Pat. No. 3,585,168 US Pat. No. 3,900,424 US Pat. No. 3,953,383 JP-A-2-142824 China open patent CN10444663A China published patent CN1060299A China open patent CN1257753A China published patent CN1257885A China open patent CN1306021A US Patent US2002 / 0082363 A1 Macromolecules: 24,5305,1991 Macromolecules: 30,3147,1997 J. Polym. Sci .: PartA: Polym. Chem. 37, 1863, 1999 Macromolecules: 28,7577,1995 Macromolecules: 32,2137,1999 Journal of American Chemical Society: 1998,120,4690 Journal of American Chemical Society: 1999,121,107 Journal of American Chemical Society: 1998,120,11018

  The object of the present invention is to produce a high-molecular weight aliphatic polycarbonate, which is easy to manufacture and handle, provides high catalyst efficiency, carbon dioxide immobilization rate, and has an excellent alternating structure content in the copolymer. It is to provide a three way catalyst. Another object of the present invention is to provide a method for producing such a three-way catalyst. Another object of the present invention is to provide a method for producing a high molecular weight aliphatic polycarbonate using the above three-way catalyst.

  As a result of repeated studies to achieve the above-mentioned problems, the present inventors have found that the problems can be achieved by combining dihydrocarbyl zinc with a specific metal salt and glycerin, and thus completed the present invention. I came to let you.

That is, the present invention
A three-way catalyst produced by the following method using glycerin, metal salt and dihydrocarbyl zinc as starting materials,
The metal salt is (1) a rare earth metal salt or (2) a non-rare earth metal salt;
(1) The rare earth metal salt has a general formula: MX ¹ _n X ² _m
(Where
M is a rare earth metal atom selected from the group consisting of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu;
n and m are each independently an integer from 0 to 3 and n + m = 3;
X ¹ is, _{K a} value be 10 ^-3 or more carboxyl group or a sulfonic group;
X ² is Cl or Br)
Indicated by;
(2) The non-rare earth metal salt has a general formula: ZX ³ _p X ⁴ _q
(Where
Z is zinc or aluminum;
When Z is zinc, p and q are each independently an integer from 0 to 2 and p + q = 2;
When Z is aluminum, p and q are each independently an integer from 0 to 3 and p + q = 3;
In any case, X ³ represents citric acid residue, tartaric acid residue, aminosulfonic acid residue, iminodiacetoxy, trifluoroacetoxy, chloroacetoxy, dichloroacetoxy, trichloroacetoxy, o-chlorobenzoic acid residue, benzene A group selected from the group consisting of a sulfonic acid residue and a naphthalenesulfonic acid residue;
X ⁴ is Cl or Br)
Indicated by;
A mixture containing glycerin and a metal salt is added to an organic solvent at a molar ratio of glycerin: metal salt of 1 to 10: 1 to 1.5, and the temperature of the reaction mixture is maintained at 25 ° C. or lower in the presence of carbon dioxide gas. The dihydrocarbyl zinc was dropped so that the molar ratio of metal salt: dihydrocarbyl zinc was 1 to 1.5: 2 to 20, and then aged in a carbon dioxide atmosphere to suspend the three-way catalyst. The present invention relates to a three-way catalyst used for producing a high molecular weight aliphatic polycarbonate produced by obtaining a liquid.

  The method for producing a three-way catalyst used for the production of the high molecular weight aliphatic polycarbonate of the present invention comprises a mixture containing glycerin and a metal salt in a molar ratio of glycerin: metal salt of 1 to 10: 1 to 1.5. In the presence of carbon dioxide, the temperature of the reaction mixture is maintained at 25 ° C. or lower, and the molar ratio of metal salt: dihydrocarbyl zinc is 1 to 1.5: 2 to 20. The hydrocarbyl zinc is dropped, and then aged in a carbon dioxide atmosphere to obtain a suspension of the three-way catalyst.

  Further, in the method for producing a high molecular weight aliphatic polycarbonate using the three-way catalyst of the present invention, the above-mentioned aged three-way catalyst and epoxy compound are respectively charged in a pressure cooker, and the pressure in the kettle is set to 2.0. Carbon dioxide gas is charged so as to maintain the pressure in a range of ˜5.0 MPa, copolymerization is performed at a reaction temperature of 50 to 90 ° C., and after the copolymerization reaction is completed, the reaction is stopped with an excessive amount of methanol, The polycarbonate is obtained by washing the coalescence.

  In the three-way catalyst produced according to the present invention, dihydrocarbyl zinc is a main catalyst and has a function of ensuring a high alternating structure of the copolymer. The metal salt is an auxiliary catalyst, shortens the induction period of the polymerization reaction, and improves the catalyst efficiency. Glycerin is an activator and ensures that the copolymerization reaction takes place quickly.

  Examples of dihydrocarbyl zinc used in the present invention include diethyl zinc, di n-propyl zinc, diisopropyl zinc, di n-butyl zinc, diisobutyl zinc, diphenyl zinc and dibenzyl zinc. Dialkyl zinc is preferred, diethyl zinc, di-zinc More preferred are n-propyl zinc, diisopropyl zinc, di n-butyl zinc and diisobutyl zinc. Moreover, depending on the case, it can also be used in the state of about 1 mol solution in hydrocarbons, such as n-hexane and toluene.

  The metal salt used in the present invention is the following specific (1) rare earth metal salt or (2) non-rare earth metal salt, and is represented by the following general formula.

(1) The rare earth metal salt is represented by the general formula: MX ¹ _n X ² _m .
Where
M is a rare earth metal atom selected from the group consisting of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and Y, La, Pr and Nd is preferred.
n and m are each independently an integer of 0 to 3, and n + m = 3.
X ¹ is, K _a value is ^10-3 or more carboxyl group or a sulfonic group, an amino sulfonic acid residue, trifluoroacetoxy, chloro acetoxy, dichloro acetoxy, trichloro acetoxy, o- chlorobenzoic acid residue, tartaric acid residue Groups, benzenesulfonic acid residues and naphthalenesulfonic acid residues are preferred.
X ² is Cl or Br, and Cl is preferred.

(2) The non-rare earth metal salt is represented by ZX ³ _p X ⁴ _q .
Where
Z is zinc or aluminum;
When Z is zinc, p and q are integers from 0 to 2 and p + q = 2;
When Z is aluminum, p and q are integers from 0 to 3 and p + q = 3;
X ³ is a citric acid residue, tartaric acid residue, aminosulfonic acid residue, iminodiacetoxy, trifluoroacetoxy, chloroacetoxy, dichloroacetoxy, trichloroacetoxy, o-chlorobenzoic acid residue, benzenesulfonic acid residue and It is a group selected from the group consisting of naphthalenesulfonic acid residues, and iminodiacetoxy, dichloroacetoxy, trichloroacetoxy and benzenesulfonic acid residues are preferred.
X ⁴ is Cl or Br, preferably Cl.

  The organic solvent used to prepare the catalyst of the present invention is preferably an aprotic solution such as 1,3-dioxolane, propylene oxide and 1,4-dioxane. The catalyst of the present invention is prepared in the form of a suspension in which the constituent components are dispersed in the organic solvent, and is directly subjected to the copolymerization reaction. The total content of active ingredients in the suspension is 0.2 to 20% by weight, preferably 0.5 to 15% by weight in the suspension.

  The method for producing the three-way catalyst of the present invention is as described above. The molar ratio of glycerin: metal salt is 1 to 10: 1 to 1.5, preferably 2 to 10: 1.3 to 1.5. The molar ratio of metal salt: dihydrocarbyl zinc is 1.3 to 1.5: 2 to 20, preferably 1.3 to 1.5: 2 to 10. The reaction temperature can be maintained at a temperature not exceeding 25 ° C. by controlling the dropping rate of dihydrocarbyl zinc. Aging in a carbon dioxide atmosphere is preferably 2 to 4 hours.

  A high molecular weight aliphatic polycarbonate (hereinafter referred to as a copolymer) can be synthesized by copolymerizing a carbon dioxide gas and an epoxy compound using the three-way catalyst of the present invention. The outline of the method is as described above. Examples of the epoxy compound include ethylene oxide, propylene oxide, 1,2-butylene oxide, cyclohexene oxide and the like, and propylene oxide and cyclohexene oxide are preferable. Propylene oxide is not only used as a raw material for the copolymerization reaction, but can also serve as a solvent for catalyst preparation as described above. It is sufficient that the copolymerization is performed for 5 to 10 hours, and the amount of methanol used for stopping the reaction is sufficient if it is 1.5 times the weight of the reaction product. The amount of methanol for washing the obtained copolymer is preferably 1 to 5 times that of the copolymer by weight.

  The catalytic efficiency of copolymerization with the catalyst of the present invention exceeds 4,000 g polymer / mol catalyst, the number average molecular weight of the polycarbonate is 50,000 or more, the fixing rate of carbon dioxide gas is 40% by weight or more, and the alternating structure is contained. The amount is 95% or more.

  According to the present invention, it is possible to obtain a three-way catalyst used in a reaction for synthesizing a high molecular weight aliphatic polycarbonate by reacting carbon dioxide gas produced as a by-product in various industries with an epoxy compound. The catalyst of the present invention can be easily produced by carrying out the reaction while stirring at a temperature of 25 ° C. or lower in an inert atmosphere. Further, the activity does not change even if the reaction is allowed to stand for 48 hours after the production and then used for the reaction. This catalyst has a high catalyst efficiency of 40 to 50 g of a high-molecular weight aliphatic polycarbonate per 1 g of the catalyst, usually from 8 to 10 hours of polymerization time, from carbon dioxide generated by combustion of fossil fuels in various industries. Due to the high immobilization rate of gas and excellent alternating structure content, it has the ability to produce high molecular weight aliphatic polycarbonate.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the examples,% indicating composition and concentration is% by weight. The present invention is not limited by these examples.

(Catalyst preparation example 1: 1,4-dioxane is used as a solvent)
The catalyst used in the examples was prepared as follows. That is, taking a case where a catalyst suspension having a metal salt-glycerin-dihydrocarbylzinc molar ratio of 1:10:20 as an example is prepared, glycerol: metal salt is added at a molar ratio of 1,4- The dihydrocarbyl zinc was added dropwise so that the molar ratio of metal salt: dihydrocarbyl zinc was 1:20 while being added to dioxane, keeping the temperature of the reaction mixture at 25 ° C. or less in the presence of carbon dioxide gas, Thereafter, various three-way catalyst suspensions used in the following examples were prepared by further aging in an atmosphere of carbon dioxide gas for 3 hours. The amount of 1,4-dioxane used was an amount corresponding to 40 ml with respect to 0.002 to 0.02 mol of dihydrocarbyl zinc.

(Catalyst preparation example 2: Propylene oxide is used as a solvent)
A similar three-way catalyst suspension was prepared in the same manner as in Catalyst Preparation Example 1 except that the solvent was changed. That is, a catalyst was prepared with the same blending ratio as above using propylene oxide instead of 1,4-dioxane as a solvent. The amount of propylene oxide used was the same as the amount of 1,4-dioxane. In this case, the propylene oxide used as the solvent was used as it was as a part of one raw material for the polycarbonate synthesis reaction. The obtained catalyst had the same catalytic ability as the catalyst obtained in Catalyst Preparation Example 1.

  In Examples 1 to 12 below, a catalyst prepared in accordance with Catalyst Preparation Example 1 using 1,4-dioxane as a solvent was used as a catalyst. In addition, according to Catalyst Preparation Example 2, when a catalyst prepared using propylene oxide as a solvent was used, almost the same result was obtained.

  Polypropylene carbonate was synthesized by the following procedure using yttrium trichloroacetate-glycerin-diethyl zinc having a molar ratio of 1:10:20 as a three-way catalyst. That is, first, 166 g of propylene oxide was charged into a 500 ml pressure kettle. Next, an amount of the catalyst suspension in which the effective amount of the above three-way catalyst is 8% is added to an effective catalyst amount of 3.0 g and immediately charged with carbon dioxide gas, and the temperature is set to 65 ° C. The reaction was started. The carbon dioxide gas consumed during the reaction was replenished, and the copolymerization reaction was carried out for 10 hours while maintaining the pressure in the kettle at 3.5 MPa (absolute pressure) and the temperature at 65 ° C. until the reaction was completed. Subsequently, 1.5 times by weight of methanol was added to the reaction product to stop the reaction, and the reaction product was washed with 5 times by weight of methanol to obtain 98.4 g of white polypropylene carbonate. The IR absorption spectrum is shown in FIG. 1, and the NMR chart is shown in FIG. The catalyst efficiency was 6,500 g polymer / mol diethyl zinc, the number average molecular weight of the polycarbonate was 180,000, the carbon dioxide fixation rate was 40% by weight or more, and the alternating structure content was 95% or more.

  According to Catalyst Preparation Example 2, except that propylene oxide was used as a solvent, a catalyst suspension prepared with the same raw material ratio and conditions was used, and the same conditions were used except that the amount of propylene oxide initially charged was 128.5 g. By carrying out a copolymerization reaction, 98.4 g of white polypropylene carbonate was obtained. The IR spectrum is shown in FIG. 3, and the NMR chart is shown in FIG.

  Polycarbonate was synthesized by the same procedure as in Example 1 except that the catalyst was changed. That is, trichloroacetic acid zinc-glycerin-diisopropyl zinc having a molar ratio of 1.5: 10: 20 was used as a three-way catalyst, and the aged catalyst and propylene oxide were respectively charged into a pressure cooker and immediately charged with carbon dioxide. Then, the pressure in the kettle was maintained at 3.5 MPa until the reaction was completed. The amount of catalyst used relative to propylene oxide was 1.8% by weight. The temperature was 65 ° C. and the copolymerization reaction was carried out for 10 hours. Next, 1.5 times by weight of methanol was added to the reaction product to stop the reaction, and the polymer was washed with 5 times by weight of methanol of the reaction product to obtain white polypropylene carbonate. The IR absorption spectrum is shown in FIG. 5, and the NMR chart is shown in FIG. The catalyst efficiency was 6,600 g polymer / mol diisopropyl zinc, the number average molecular weight of the polycarbonate was 160,000, the carbon dioxide fixation rate was 41% by weight, and the alternating structure content was 95% or more.

  According to Catalyst Preparation Example 2, white polypropylene carbonate was obtained by carrying out a copolymerization reaction under the same conditions using a catalyst suspension prepared under the same raw material ratio and conditions except that propylene oxide was used as a solvent. . The IR spectrum is shown in FIG. 7, and the NMR chart is shown in FIG.

  Polycarbonate was synthesized by the same procedure as in Example 1 except that the catalyst and the reaction time were changed. That is, as a three-way catalyst, a monochloroacetic acid zinc-glycerin-diethyl zinc having a molar ratio of 1:10:20 was used. Aged three-way catalyst and propylene oxide were charged into a pressure cooker and immediately filled with carbon dioxide. Then, the pressure in the kettle was maintained at 3.5 MPa until the reaction was completed. The amount of catalyst used relative to propylene oxide was 1.8% by weight. The temperature was 65 ° C. and the copolymerization reaction was carried out for 8 hours. Next, 1.5 times by weight of methanol was added to the reaction product to stop the reaction, and the polymer was washed with 5 times by weight of methanol of the reaction product to obtain white polypropylene carbonate. The catalyst efficiency was 4,050 g polymer / mol diethyl zinc, the number average molecular weight of the polycarbonate was 190,000, the carbon dioxide fixation rate was 41% by weight, and the alternating structure content was 95% or more.

  Polycarbonate was synthesized by the same procedure as in Example 1 except that the catalyst and the reaction time were changed. That is, as the three-way catalyst, zinc citrate-glycerin-di-n-butylzinc having a molar ratio of 1.3: 10: 20 was used, and the aged catalyst and propylene oxide were respectively charged into the pressure cooker, and immediately Carbon dioxide gas was charged into the tank, and the pressure in the kettle was maintained at 3.5 MPa until the reaction was completed. The amount of catalyst used relative to propylene oxide was 1.8% by weight. The temperature was 65 ° C. and the copolymerization reaction was carried out for 8 hours. Next, 1.5 times by weight of methanol was added to the reaction product to stop the reaction, and the polymer was washed with 5 times by weight of methanol of the reaction product to obtain white polypropylene carbonate. The catalyst efficiency was 5,200 g polymer / mol di-n-butyl zinc, the number average molecular weight of the polycarbonate was 80,000, the carbon dioxide fixation rate was 40% by weight, and the alternating structure content was 95% or more.

  Polycarbonate was synthesized by the same procedure as in Example 1 except that the catalyst and reaction conditions were changed. In other words, aluminum chloride-glycerin-diethyl zinc having a molar ratio of 1.5: 2: 2 was used as a three-way catalyst, and the aged catalyst and propylene oxide were respectively charged into a pressure kettle and immediately charged with carbon dioxide gas. The pressure in the kettle was maintained at 3.0 MPa until the reaction was completed. The amount of catalyst used relative to propylene oxide was 1.8% by weight. The temperature was set to 70 ° C. and the copolymerization reaction was carried out for 8 hours. Next, 1.5 times by weight of methanol was added to the reaction product to stop the reaction, and the polymer was washed with 5 times by weight of methanol of the reaction product to obtain white polypropylene carbonate. The catalyst efficiency was 9,400 g polymer / mol diethylzinc, the number average molecular weight of the polycarbonate was 120,000, the carbon dioxide fixation rate was 40% by weight, and the alternating structure content was 95% or more.

  Polycarbonate was synthesized by the same procedure as in Example 1 except that the catalyst and reaction temperature were changed. Namely, praseodymium (III) aminosulfonate having a molar ratio of 1: 8: 20 as a three-way catalyst, glycerin-diethyl zinc, and aged catalyst and propylene oxide containing 50% by weight of epoxycyclohexane, Was charged in a pressure kettle and immediately charged with carbon dioxide, and the pressure in the kettle was maintained at 3.0 MPa until the reaction was completed. The amount of catalyst used relative to propylene oxide was 1.8% by weight. The temperature was set to 70 ° C. and the copolymerization reaction was carried out for 10 hours. Next, 1.5 times the weight of methanol was added to the reaction product to stop the reaction, and the polymer was washed with 5 times the amount of methanol of the reaction product to obtain white polypropylene carbonate. The catalyst efficiency was 9,000 g polymer / mol diethyl zinc, the number average molecular weight of the polycarbonate was 51,000, and the fixing rate of carbon dioxide was 40% by weight.

  Polycarbonate was synthesized by the same procedure as in Example 1 except that the catalyst and reaction conditions were changed. That is, as a three-way catalyst, zinc benzenesulfonate-glycerin-di-n-propylzinc with a molar ratio of 1:10:20 was used, and the aged catalyst and propylene oxide were respectively charged into a pressure cooker, and carbon dioxide gas was immediately added. After charging, the pressure in the kettle was maintained at 3.0 MPa until the reaction was completed. The amount of catalyst used relative to propylene oxide was 1.8% by weight. The temperature was set to 70 ° C. and the copolymerization reaction was carried out for 8 hours. Next, 1.5 times by weight of methanol was added to the reaction product to stop the reaction, and the polymer was washed with 5 times by weight of methanol of the reaction product to obtain white polypropylene carbonate. The catalyst efficiency was 5,200 g polymer / mol di-n-propyl zinc, the number average molecular weight of the polycarbonate was 60,000, the carbon dioxide fixation rate was 40% by weight, and the alternating structure content was 95% or more.

  Polycarbonate was synthesized by the same procedure as in Example 1 except that the catalyst and reaction conditions were changed. That is, as a three-way catalyst, zinc dichloroacetate-glycerin-diisobutylzinc having a molar ratio of 1:10:20 was used, and the aged catalyst and propylene oxide were respectively charged into a pressure cooker, and immediately charged with carbon dioxide gas. The pressure in the kettle was maintained at 3.0 MPa until the reaction was completed. The amount of catalyst used relative to propylene oxide was 1.8% by weight. The temperature was set to 70 ° C. and the copolymerization reaction was carried out for 8 hours. Subsequently, 1.5 times by weight of methanol was added to the reaction product to stop the reaction, and the polymer was washed with 5 times by weight of methanol of the reaction product to obtain white polypropylene carbonate. The catalyst efficiency was 5,200 g polymer / mol diisobutyl zinc, the number average molecular weight of the polycarbonate was 60,000, the carbon dioxide fixation rate was 40% by weight, and the alternating structure content was 95% or more.

  Polycarbonate was synthesized by the same procedure as in Example 1 except that the catalyst and reaction conditions were changed. That is, lanthanum chloroacetate-glycerin-di-n-propylzinc having a molar ratio of 1:10:20 was used as a three-way catalyst, and an aged catalyst and propylene oxide were charged into a pressure cooker, and carbon dioxide was charged. Then, the pressure in the kettle was maintained at 3.0 MPa until the reaction was completed. The amount of catalyst used relative to propylene oxide was 1.8% by weight. The temperature was set to 70 ° C. and the copolymerization reaction was carried out for 8 hours. Next, 1.5 times by weight of methanol was added to the reaction product to stop the reaction, and the polymer was washed with 5 times by weight of methanol of the reaction product to obtain white polypropylene carbonate. The catalyst efficiency was 6,900 g polymer / mol di-n-propyl zinc, the number average molecular weight of the polycarbonate was 130,000, the carbon dioxide fixation rate was 41% by weight, and the alternating structure content was 95% or more.

  Polycarbonate was synthesized by the same procedure as in Example 1 except that the catalyst and reaction conditions were changed. That is, as a three-way catalyst, dl-zinc tartrate-glycerin-di-n-propylzinc having a molar ratio of 1:10:20 was used, and the aged catalyst and propylene oxide were respectively charged into a pressure cooker, and carbon dioxide gas was immediately added. After charging, the pressure in the kettle was maintained at 3.0 MPa until the reaction was completed. The amount of catalyst used relative to propylene oxide was 1.5% by weight. The temperature was set to 70 ° C. and the copolymerization reaction was carried out for 8 hours. Next, 1.5 times the weight of methanol was added to the reaction product to stop the reaction, and the polymer was washed with 5 times the amount of methanol of the reaction product to obtain white polypropylene carbonate. The catalyst efficiency was 4,900 g polymer / mol di-n-propyl zinc, the number average molecular weight of the polycarbonate was 70,000, the carbon dioxide fixation rate was 41% by weight, and the alternating structure content was 95% or more.

  Polycarbonate was synthesized by the same procedure as in Example 1 except that the catalyst was changed. That is, neodymium trichloroacetate-glycerin-diethyl zinc having a molar ratio of 1:10:20 was used as a three-way catalyst, and an aged catalyst and propylene oxide containing 12% by weight of epoxy ethane were respectively charged in a pressure cooker. Immediately, carbon dioxide gas was charged, and the pressure in the kettle was maintained at 3.5 MPa until the reaction was completed. The amount of catalyst used relative to propylene oxide was 1.7% by weight. The temperature was 65 ° C. and the copolymerization reaction was carried out for 10 hours. Next, 1.5 times by weight of methanol was added to the reaction product to stop the reaction, and the polymer was washed with 5 times by weight of methanol of the reaction product to obtain white polypropylene carbonate. The catalyst efficiency was 6,000 g polymer / mol diethylzinc, the number average molecular weight of the polycarbonate was 51,000, and the carbon dioxide fixation rate was 40% by weight or more.

  Polycarbonate was synthesized by the same procedure as in Example 1 except that the catalyst and reaction conditions were changed. That is, as a three-way catalyst, iminodiacetate zinc-glycerin-diethylzinc having a molar ratio of 1: 8: 20 was used, and a mixed epoxy comprising 80% propylene oxide and 20% epoxycyclohexane. Each compound was charged into a pressure kettle and immediately charged with carbon dioxide, and the pressure in the kettle was maintained at 3.0 MPa until the reaction was completed. The amount of catalyst used for propylene oxide and epoxycyclohexane was 1.2% by weight. The temperature was set to 70 ° C. and the copolymerization reaction was carried out for 8 hours. Subsequently, 1.5 times by weight of methanol was added to the reaction product to stop the reaction, and the polymer was washed with 5 times by weight of methanol of the reaction product to obtain a white aliphatic hybrid polycarbonate. The catalyst efficiency was 7,100 g polymer / mol diethyl zinc, the number average molecular weight of the polycarbonate was 64,000, and the fixing rate of carbon dioxide was 40% by weight. The IR spectrum was as shown in FIG. 9, and the NMR chart was as shown in FIG.

  The aliphatic polycarbonate produced using the catalyst of the present invention is a plastic having photodegradability and biodegradability, and is useful as a plastic used in applications such as disposable pharmaceuticals and food packaging materials.

It is IR spectrum of the polymer of Example 1 (solvent for catalyst preparation: 1,4-dioxane). It is a NMR chart of the polymer of Example 1 (solvent for catalyst preparation: 1,4-dioxane). It is IR spectrum of the polymer of Example 1 (solvent for catalyst preparation: propylene oxide). It is a NMR chart of the polymer of Example 1 (solvent for catalyst preparation: propylene oxide). It is IR spectrum of the polymer of Example 2 (Solvent for catalyst preparation: 1,4-dioxane). It is a NMR chart of the polymer of Example 2 (solvent for catalyst preparation: 1,4-dioxane). It is IR spectrum of the polymer of Example 2 (solvent for catalyst preparation: propylene oxide). It is a NMR chart of the polymer of Example 2 (solvent for catalyst preparation: propylene oxide). It is IR spectrum of the polymer of Example 12 (Solvent for catalyst preparation: 1,4-dioxane). It is a NMR chart of the polymer of Example 12 (solvent for catalyst preparation: 1,4-dioxane).

Claims (10)

A three-way catalyst produced by the following method using glycerin, metal salt and dihydrocarbyl zinc as starting materials,
The metal salt is (1) a rare earth metal salt or (2) a non-rare earth metal salt;
(1) The rare earth metal salt has a general formula: MX ¹ _n X ² _m
(Where
M is a rare earth metal atom selected from the group consisting of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu;
n and m are each independently an integer from 0 to 3 and n + m = 3;
X ¹ is, _{K a} value be 10 ^-3 or more carboxyl group or a sulfonic group;
X ² is Cl or Br)
Indicated by;
(2) The non-rare earth metal salt has a general formula: ZX ³ _p X ⁴ _q
(Where
Z is zinc or aluminum;
When Z is zinc, p and q are each independently an integer from 0 to 2 and p + q = 2;
When Z is aluminum, p and q are each independently an integer from 0 to 3 and p + q = 3;
In any case, X ³ represents citric acid residue, tartaric acid residue, aminosulfonic acid residue, iminodiacetoxy, trifluoroacetoxy, chloroacetoxy, dichloroacetoxy, trichloroacetoxy, o-chlorobenzoic acid residue, benzene A group selected from the group consisting of a sulfonic acid residue and a naphthalenesulfonic acid residue;
X ⁴ is Cl or Br)
Indicated by
A mixture containing glycerin and a metal salt is added to an organic solvent at a molar ratio of glycerin: metal salt of 1 to 10: 1 to 1.5, and the temperature of the reaction mixture is maintained at 25 ° C. or lower in the presence of carbon dioxide gas. The dihydrocarbyl zinc was dropped so that the molar ratio of metal salt: dihydrocarbyl zinc was 1 to 1.5: 2 to 20, and then aged in a carbon dioxide atmosphere to suspend the three-way catalyst. A three-way catalyst used for the production of a high molecular weight aliphatic polycarbonate produced by obtaining a liquid.   The ternary according to claim 1, wherein the dihydrocarbyl zinc is a zinc compound selected from the group consisting of diethyl zinc, di n-propyl zinc, diisopropyl zinc, di n-butyl zinc, diisobutyl zinc, diphenyl zinc and dibenzyl zinc. catalyst.   The three-way catalyst according to claim 1 or 2, wherein the dihydrocarbyl zinc is dialkyl zinc.   The three-way catalyst according to any one of claims 1 to 3, wherein the organic solvent is an aprotic solvent selected from the group consisting of 1,3-dioxolane, propylene oxide and 1,4-dioxane.   The three-way catalyst according to any one of claims 1 to 4, wherein the rare earth metal is Y, La, Pr or Nd. (1) In the general formula of the rare earth metal salt, X ¹ is a tartaric acid residue, an aminosulfonic acid residue, trifluoroacetoxy, chloroacetoxy, dichloroacetoxy, trichloroacetoxy, o-chlorobenzoic acid residue, benzenesulfonic acid The three-way catalyst according to any one of claims 1 to 5, which is a group selected from the group consisting of a residue or a naphthalenesulfonic acid residue. The three-way catalyst according to any one of claims 1 to 6, wherein X ² and X ⁴ are each Cl. A process for producing a three-way catalyst starting from glycerin, a metal salt and zinc dihydrocarbyl,
The metal salt is (1) a rare earth metal salt or (2) a non-rare earth metal salt;
(1) The rare earth metal salt has a general formula: MX ¹ _n X ² _m
(Where
M is a rare earth metal atom selected from the group consisting of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu;
n and m are each independently an integer from 0 to 3 and n + m = 3;
X ¹ is, _{K a} value be 10 ^-3 or more carboxyl group or a sulfonic group;
X ² is Cl or Br)
Indicated by;
(2) The non-rare earth metal salt has a general formula: ZX ³ _p X ⁴ _q
(Where
Z is zinc or aluminum;
When Z is zinc, p and q are each independently an integer from 0 to 2 and p + q = 2;
When Z is aluminum, p and q are each independently an integer from 0 to 3 and p + q = 3;
In any case, X ³ represents citric acid residue, tartaric acid residue, aminosulfonic acid residue, iminodiacetoxy, trifluoroacetoxy, chloroacetoxy, dichloroacetoxy, trichloroacetoxy, o-chlorobenzoic acid residue, benzene A group selected from the group consisting of a sulfonic acid residue and a naphthalenesulfonic acid residue;
X ⁴ is Cl or Br)
Indicated by
A mixture containing glycerin and a metal salt is added to an organic solvent at a molar ratio of glycerin: metal salt of 1 to 10: 1 to 1.5, and the temperature of the reaction mixture is maintained at 25 ° C. or lower in the presence of carbon dioxide gas. The dihydrocarbyl zinc was added dropwise so that the molar ratio of metal salt: dihydrocarbyl zinc was 1 to 1.5: 2 to 20, and then aged in a carbon dioxide atmosphere to obtain a suspension. A method for producing a three-way catalyst.   The method for producing a three-way catalyst according to claim 8, wherein the aging time is 2 to 4 hours. A method for producing a high-molecular-weight aliphatic polycarbonate using a three-way catalyst, wherein the aged three-way catalyst and an epoxy compound are charged into a pressure cooker, respectively. Carbon dioxide gas is charged so that the pressure in the kettle is maintained in the range of 2.0 to 5.0 MPa, copolymerization is performed at a reaction temperature of 50 to 90 ° C., and after the copolymerization reaction is completed, an excess amount of methanol is used. A method for producing an aliphatic polycarbonate, characterized in that the reaction is stopped and the polymer is washed with methanol to obtain an aliphatic polycarbonate.

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