CN112358607B - Preparation method of carbon dioxide-propylene oxide copolymer - Google Patents
Preparation method of carbon dioxide-propylene oxide copolymer Download PDFInfo
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Abstract
The invention provides a preparation method of a carbon dioxide-propylene oxide copolymer, which comprises the following steps: in the presence of a solvent and a heterogeneous catalyst, polymerizing carbon dioxide and propylene oxide to obtain a carbon dioxide-propylene oxide copolymer; the solvent comprises one or more of dimethyl carbonate, diethyl carbonate, ethyl acetate, acetone, dimethylformamide, dichloromethane, trichloromethane, tetrahydrofuran, 1, 3-dioxolane and dioxane. The invention solves the problem that the catalyst is difficult to disperse due to the increase of the system viscosity in the later reaction period of the heterogeneous catalysis system; the phenomenon of implosion caused by over violent reaction is avoided; the ultimate reaction temperature of the rare earth ternary catalytic system and the zinc carboxylate catalytic system is increased, the polymerization reaction rate is increased, and the conversion rate of the propylene oxide is increased; the generation of byproducts of a rare earth ternary catalytic system and a zinc carboxylate catalytic system is reduced; effectively improves the content of carbonate units in the chain segment of the polymerization product of the bimetallic catalytic system.
Description
Technical Field
The invention relates to the technical field of polymer synthesis, in particular to a preparation method of a carbon dioxide-propylene oxide copolymer.
Background
Carbon dioxide is the most main greenhouse gas and is a cheap and easily available carbon resource, and since the first discovery of ring-opening copolymerization reaction of carbon dioxide and epoxy compounds in Inoue in 1969, the conversion and fixation of carbon dioxide into high polymer materials has become an important research direction in the field of carbon dioxide utilization, wherein carbon dioxide (CO) is2) The ring-opening copolymerization (ROOP) of the PPC and Propylene Oxide (PO) is attractive, the fixed amount of carbon dioxide in the PPC obtained by copolymerization can reach more than 40 percent, and the PPC has high application value in the fields of disposable plastic packaging, agricultural mulching films and environment-friendly polyurethane raw materials.
In the field of industrial production of carbon dioxide-propylene oxide copolymers, catalytic systems which have been industrialized at present mainly comprise a rare earth ternary catalyst system, a zinc dicarboxylate catalytic system and a bimetallic catalytic system, wherein in the process of catalyzing polymerization of carbon dioxide and propylene oxide, the rare earth ternary catalytic system and the zinc dicarboxylate catalytic system generate more cyclic carbonate as a by-product along with the rise of reaction temperature, so that the reaction temperature for preparing the copolymer of carbon dioxide and propylene oxide is generally controlled below 70 ℃, the reaction time is generally controlled to be more than 8 hours in order to achieve proper conversion rate, and the conversion rate of propylene oxide is only 30-40%; although the emerging bimetallic catalytic system has higher monomer conversion rate in the process of catalyzing copolymerization of carbon dioxide and propylene oxide, the bimetallic catalytic system is easy to generate implosion phenomenon in the reaction process, the reaction degree is difficult to control, and the environment degradability of a product is seriously influenced because the content of ether in a high-molecular polymerization product is too high.
On the premise of ensuring the product quality, the defects of low monomer conversion rate and difficult control of the reaction degree of a bimetallic catalytic system existing in a rare earth ternary catalytic system and a zinc carboxylate catalytic system greatly limit the process selection of the polymerization of carbon dioxide and propylene oxide, and besides, in the polymerization process of carbon dioxide and propylene oxide, the rapid increase of the later system viscosity along with the progress of the polymerization reaction also becomes an adverse factor influencing the industrialization process of the carbon dioxide-propylene oxide copolymer.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for preparing a carbon dioxide-propylene oxide copolymer, which has high conversion rate, no implosion phenomenon and few byproducts.
The invention provides a preparation method of a carbon dioxide-propylene oxide copolymer, which comprises the following steps:
in the presence of a solvent and a heterogeneous catalyst, polymerizing carbon dioxide and propylene oxide to obtain a carbon dioxide-propylene oxide copolymer; the solvent comprises one or more of dimethyl carbonate, diethyl carbonate, ethyl acetate, acetone, dimethylformamide, dichloromethane, trichloromethane, tetrahydrofuran, 1, 3-dioxolane and dioxane.
Preferably, the solvent is a molecular sieve or CaH2Treated to a water content of less than 50ppm.
Preferably, the volume ratio of the solvent to the propylene oxide is (0.5-2) to 1; the mass ratio of the carbon dioxide to the propylene oxide is (30-300): 100.
Preferably, the heterogeneous catalyst is a rare earth ternary catalyst, a zinc dicarboxylate catalyst or a bimetallic catalyst.
Preferably, when the heterogeneous catalyst is a rare earth ternary catalyst, the polymerization temperature is 60-100 ℃; the polymerization pressure is 3MPa to 15MPa; the polymerization time is 8-30 h;
when the heterogeneous catalyst is a zinc dicarboxylate catalyst, the polymerization temperature is 60-100 ℃; the polymerization pressure is 3MPa to 15MPa; the polymerization time is 8-30 h.
Preferably, when the heterogeneous catalyst is a bimetallic catalyst, the polymerization temperature is 40-70 ℃; the polymerization pressure is 3MPa to 15MPa; the polymerization time is 8-30 h.
Preferably, the rare earth three-way catalyst comprises the following components:
a) The alkyl zinc is one of ethyl zinc, n-propyl zinc, isopropyl zinc, n-butyl zinc, isobutyl zinc and phenyl zinc or benzyl zinc;
b) Glycerol;
c) The metal salt is divided into rare earth salt and non-rare earth salt, and specifically comprises the following components:
(1) the structural formula of the rare earth salt is: MXnYm；
Wherein: n, m is a positive integer of 0-3, and n + m =3;
m is one of Y, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb and Lu; x is a carboxylic group or a sulfonic group with a Ka value of more than 10-3, namely one of an amino sulfonic group, a chloroacetic group, a dichloroacetic group, a trichloroacetic group, a trifluoroacetic group, an o-chlorobenzoic acid group, an alpha-tartaric acid group, a benzenesulfonic group or a naphthalenesulfonic group; y is-Cl;
(2) the non-rare earth salt has the structural formula: MXnYm；
Wherein M is zinc or aluminum; zn: n, m is a positive integer of 0-2, n + m =2; al: n, m is a positive integer of 0-3, and n + m =3; x is one of citric acid group, alpha-tartaric acid group, iminodiacetic acid group, chloroacetic acid group, dichloroacetic acid group, trichloroacetic acid group, aminosulfonic acid group, o-chlorobenzoic acid group, benzenesulfonic acid group or sulfonic acid group; y is-Cl.
Preferably, the zinc dicarboxylate catalyst is prepared according to the following method:
reacting the dicarboxylic acid monovalent metal salt and the zinc salt in water, and collecting the solid generated by the reaction to obtain the dicarboxylic acid zinc catalyst.
Preferably, the initial pH value of the reaction is 5.2-6.3; the end point pH value of the reaction is 3.8-4.7.
Preferably, the bimetallic catalyst is prepared as follows:
a) Mixing tert-butyl alcohol, water, a zinc salt compound and a rare earth salt compound to obtain a mixed salt solution;
wherein the zinc salt compound is ZnCl2、ZnBr2、Zn(CH3COO)2、Zn(ClCH2COO)2、Zn(Cl2CHCOO)2、Zn(Cl3CCOO)2、ZnSO4And Zn (NO)3)2One or more of the above; the rare earth salt compound is YCl3、LaCl3、NdCl3、PrCl3、Y(NO3)3、La(NO3)3、Nd(NO3)3、Pr(NO3)3、Y(ClCH2COO)3、La(ClCH2COO)3、Nd(ClCH2COO)3、Pr(ClCH2COO)3、Y(Cl2CHCOO)3、La(Cl2CHCOO)3、Nd(Cl2CHCOO)3、Pr(Cl2CHCOO)3、Y(Cl3CCOO)3、La(Cl3CCOO)3、Nd(Cl3CCOO)3、Pr(Cl3CCOO)3One or more of the above;
b) Adding K to the mixed salt solution3[Co(CN)6]The solution is stirred, separated, washed and dried to obtain the rare earth doped Zn-based alloy3[Co(CN)6]2Double metal cyanide compounds of (a).
Compared with the prior art, the invention provides a preparation method of a carbon dioxide-propylene oxide copolymer, which comprises the following steps: in the presence of a solvent and a heterogeneous catalyst, polymerizing carbon dioxide and propylene oxide to obtain a carbon dioxide-propylene oxide copolymer; the solvent comprises one or more of dimethyl carbonate, diethyl carbonate, ethyl acetate, acetone, dimethylformamide, dichloromethane, trichloromethane, tetrahydrofuran, 1, 3-dioxolane and dioxane. The invention solves the problem of difficult catalyst dispersion caused by the increase of system viscosity in the later reaction stage of a heterogeneous catalysis system, and effectively improves the conversion rate of the propylene oxide; the concentration of a reaction substrate is reduced, the phenomenon of implosion caused by over violent reaction is avoided, and the simple and controllable polymerization reaction is realized; the generation of byproducts in a rare earth ternary catalytic system and a zinc carboxylate catalytic system is effectively reduced; the ultimate reaction temperature of the rare earth ternary catalytic system and the zinc carboxylate catalytic system is greatly improved, so that the polymerization reaction rate is effectively improved; effectively improves the content of carbonate units in the chain segment of the polymerization product of the bimetallic catalytic system. Experimental results show that a solvent is introduced in the copolymerization reaction process of carbon dioxide and propylene oxide, the content of carbonate units in a copolymerization product obtained by catalyzing a rare earth ternary catalyst and a zinc dicarboxylate catalyst reaches 95-99%, the number average molecular weight is 80,000-190,000g/mol, the molecular weight distribution is 2.50-4.50, the content of cyclic carbonate serving as a byproduct is less than 5%, the reaction time is 12 hours, and the conversion rate of propylene oxide can reach 64.7%; the content of carbonate units in the copolymerization product obtained by catalysis of the bimetallic catalyst reaches 85-90 percent, the number average molecular weight is 100,000-250,000g/mol, the molecular weight distribution is 1.90-3.50, the content of cyclic carbonate as a byproduct is less than 4 percent, the reaction lasts for 10 hours, and the highest conversion rate of the propylene oxide can reach 98.7 percent.
Drawings
FIG. 1 shows the molecular weights of the products of example 6 of the present invention;
FIG. 2 shows the product of example 6 of the present invention1H-NMR spectrum.
Detailed Description
The invention provides a preparation method of a carbon dioxide-propylene oxide copolymer, and a person skilled in the art can use the content for reference and appropriately improve the process parameters to realize the preparation. It is specifically noted that all such substitutions and modifications will be apparent to those skilled in the art, and are intended to be within the scope of the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The invention provides a preparation method of a carbon dioxide-propylene oxide copolymer, which comprises the following steps:
in the presence of a solvent and a heterogeneous catalyst, polymerizing carbon dioxide and propylene oxide to obtain a carbon dioxide-propylene oxide copolymer; the solvent comprises one or more of dimethyl carbonate, diethyl carbonate, ethyl acetate, acetone, dimethylformamide, dichloromethane, trichloromethane, tetrahydrofuran, 1, 3-dioxolane and dioxane.
The carbon dioxide-propylene oxide copolymer provided by the invention is polypropylene carbonate (PPC).
The preparation method of the carbon dioxide-propylene oxide copolymer provided by the invention specifically comprises the steps of mixing a heterogeneous catalyst, propylene oxide and a solvent, introducing quantitative carbon dioxide, and heating for polymerization reaction.
The mixing method is not limited in the present invention, and the catalyst, the solvent, the propylene oxide and the carbon dioxide are preferably added in this order.
The polymerization reaction is preferably carried out in a high-pressure reaction kettle, the specific model and specification of the high-pressure reaction kettle are not limited, and the high-pressure reaction kettle is preferably a 500mL high-pressure reaction kettle with mechanical stirring.
The solvent comprises one or more of dimethyl carbonate, diethyl carbonate, ethyl acetate, acetone, dimethylformamide, dichloromethane, trichloromethane, tetrahydrofuran, 1, 3-dioxolane and dioxane. The present invention is not limited to the source, and may be commercially available. The solvent is required to pass through a molecular sieve or CaH2Treated to a water content of less than 50ppm. The present invention is not limited to a specific treatment method, and those skilled in the art will be familiar with the treatment method.
The invention firstly provides a heterogeneous catalyst which is divided into a rare earth ternary catalyst, a zinc dicarboxylate catalyst and a bimetallic catalyst. The invention is not limited in its origin, either commercially available or prepared according to methods known to those skilled in the art; preferably, the rare earth ternary catalyst is synthesized according to the method provided by the Chinese patent ZL 03105023.9; preferably, the zinc dicarboxylate catalyst is synthesized according to the method provided by Chinese patent 201510859248.8; the bimetallic catalyst is preferably synthesized according to the method provided in chinese patent 201210086834. X.
Specifically, the rare earth three-way catalyst comprises the following components:
a) The alkyl zinc is one of ethyl zinc, n-propyl zinc, isopropyl zinc, n-butyl zinc, isobutyl zinc, phenyl zinc or benzyl zinc;
b) Glycerol;
c) The metal salt is divided into rare earth salt and non-rare earth salt, wherein
(1) The structural formula of the rare earth salt is: MXnYm；
Wherein: n, m is a positive integer of 0-3, n + m =3;
m is one of Y, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb and Lu; x is a carboxylic acid group or a sulfonic acid group with Ka value of more than 10-3, namely one of an amino sulfonic acid group, a chloroacetic acid group, a dichloroacetic acid group, a trichloroacetic acid group, a trifluoroacetate group, an o-chlorobenzoic acid group, an alpha-tartaric acid group, a benzenesulfonic acid group or a naphthalenesulfonic acid group; y is-Cl;
(2) the non-rare earth salt has the structural formula: MXnYm；
Wherein M is zinc or aluminum; zn: n, m is a positive integer of 0-2, n + m =2; al: n, m is a positive integer of 0-3, and n + m =3; x is one of citric acid group, alpha-tartaric acid group, iminodiacetic acid group, chloroacetic acid group, dichloroacetic acid group, trichloroacetic acid group, aminosulfonic acid group, o-chlorobenzoic acid group, benzenesulfonic acid group or sulfonic acid group; y is-Cl;
the invention does not describe the specific preparation and composition of the rare earth three-way catalyst in detail, and the preparation method is prepared according to the method disclosed by the Chinese patent ZL 03105023.9.
Specifically, the zinc dicarboxylate catalyst is prepared by the following method:
reacting dicarboxylic acid monovalent metal salt and zinc salt in water, collecting solid generated by the reaction to obtain a dicarboxylic acid zinc catalyst, wherein the initial pH value of the reaction is 5.2-6.3; the end point pH value of the reaction is 3.8-4.7.
The specific preparation and composition of the zinc dicarboxylate catalyst are not described in detail, and the zinc dicarboxylate catalyst is prepared according to the method disclosed in Chinese patent 201510859248.8.
Specifically, the bimetallic catalyst is prepared by the following method:
(1) mixing tert-butyl alcohol, water, a zinc salt compound and a rare earth salt compound to obtain a mixed salt solution;
wherein the zinc salt compound is ZnCl2、ZnBr2、Zn(CH3COO)2、Zn(ClCH2COO)2、Zn(Cl2CHCOO)2、Zn(Cl3CCOO)2、ZnSO4And Zn (NO)3)2One or more of the above; the rare earth salt compound is YCl3、LaCl3、NdCl3、PrCl3、Y(NO3)3、La(NO3)3、Nd(NO3)3、Pr(NO3)3、Y(ClCH2COO)3、La(ClCH2COO)3、Nd(ClCH2COO)3、Pr(ClCH2COO)3、Y(Cl2CHCOO)3、La(Cl2CHCOO)3、Nd(Cl2CHCOO)3、Pr(Cl2CHCOO)3、Y(Cl3CCOO)3、La(Cl3CCOO)3、Nd(Cl3CCOO)3、Pr(Cl3CCOO)3One or more of them.
(2) Adding K to the mixed salt solution3[Co(CN)6]The solution is stirred, separated, washed and dried to obtain the rare earth doped Zn-based alloy3[Co(CN)6]2Double metal cyanide compounds of (a).
The specific preparation and composition of the bimetallic catalyst are not described in detail, and the bimetallic catalyst is prepared according to the method disclosed by Chinese patent 201210086834. X.
The volume ratio of the solvent to the propylene oxide is preferably (0.5-2) to 1; more preferably (0.8-1.5) 1; most preferably (0.9-1.2): 1.
According to the invention, the mass ratio of the rare earth three-way catalyst to the propylene oxide is preferably (0.5-5): 100; more preferably (1-3) 100; most preferably (1.5-2) 100.
The mass ratio of the zinc dicarboxylate catalyst to the propylene oxide is preferably (0.5-5): 100; more preferably (1-3) 100; most preferably (1.5-2): 100.
The mass ratio of the bimetallic catalyst to the propylene oxide is preferably (0.05-0.5): 100; more preferably (0.1 to 0.3): 100, and most preferably (0.15 to 0.2): 100.
The mass ratio of the carbon dioxide to the propylene oxide is preferably (30-300): 100; more preferably (100 to 250) 100; most preferably (150-200): 100.
According to the invention, when the heterogeneous catalyst is a rare earth ternary catalyst, the polymerization temperature is 60-100 ℃; more preferably 65 ℃ to 95 ℃; most preferably 70-90 ℃; particularly preferably 72 ℃ to 90 ℃; the polymerization pressure is 3MPa to 15MPa; more preferably 5 to 12MPa; most preferably 7 to 10MPa. The polymerization time is 8-30 h; more preferably 9 to 24 hours; most preferably 10 to 12 hours.
When the heterogeneous catalyst is a rare earth ternary catalyst, the polymerization temperature is 60-100 ℃; more preferably 65 ℃ to 95 ℃; most preferably 70-90 ℃; particularly preferably 72 ℃ to 90 ℃; the polymerization pressure is 3MPa to 15MPa; more preferably 5 to 12MPa; most preferably 7MPa to 10MPa. The polymerization time is 8-30 h; more preferably 9 to 24 hours; most preferably 10 to 12 hours.
When the heterogeneous catalyst is a bimetallic catalyst, the polymerization temperature is 40-70 ℃; more preferably 45 ℃ to 65 ℃; most preferably from 50 ℃ to 60 ℃. The polymerization pressure is 3MPa to 15MPa; more preferably 5 to 12MPa; most preferably 7MPa to 10MPa. The polymerization time is 8-30 h. More preferably 9 to 24 hours; most preferably 10 to 12 hours.
The polymerization reaction of the present invention further comprises cooling: after the polymerization reaction is finished, the high-pressure reaction kettle is placed in an ice-water bath, and cooling liquid is introduced into a cooling coil pipe in the reaction kettle to rapidly cool the reaction kettle to below 40 ℃ within 30 min. And (3) purification: the precipitate is washed several times with anhydrous alcohol to eliminate residual solvent in the product. And (3) drying: purifying the polymerization product, and drying the polymerization product in a vacuum oven at 40 ℃ and-0.1 MPa to constant weight to obtain the carbon dioxide-propylene oxide copolymer.
After cooling, taking a sample in the reaction kettle, and performing nuclear magnetic resonance hydrogen spectrum (1H-NMR) to determine the content of ether segments (PPO) in molecular chain segments of by-products of cyclic carbonate (CPC) and carbon dioxide-propylene oxide copolymer in the product; weighing the carbon dioxide-propylene oxide copolymer obtained after cooling, purifying and drying, and calculating the yield of the product; the molecular weight of the copolymerization product was determined by Gel Permeation Chromatography (GPC) using narrow distribution polystyrene as a standard and dichloromethane as a mobile phase.
Compared with the common bulk polymerization mode, the preparation method of the carbon dioxide-propylene oxide copolymer provided by the invention has the following obvious advantages while greatly reducing the system viscosity at the later stage of the polymerization reaction:
1) The molar percentage content of the by-product cyclic carbonate in the rare earth ternary catalysis system and the zinc carboxylate catalysis system is reduced by 3 to 5 percent;
2) The higher reaction pressure (7.5 MPa-10 MPa) can effectively improve the limit reaction temperature of the rare earth ternary catalyst system and the zinc carboxylate catalyst system, and the limit reaction temperature is increased to 90-100 ℃ under the premise of ensuring the product quality (the mole percentage of carbonate units in a chain segment of a polymerization product is higher than 90%), and under the condition, the monomer conversion rate of the propylene oxide reaches 64.7% after the reaction is carried out for 12 hours;
3) The content of Carbonate Units (CU) in a chain segment of a polymerization product of a bimetallic catalytic system is effectively improved due to higher reaction pressure (7.5-10 MPa), under the condition, after the reaction is carried out for 10 hours, the content of CU in the product can reach 86.7 percent at most, and is improved by 10 percent compared with the content of CU in a bulk polymerization product, and meanwhile, the conversion rate of the propylene oxide can reach 98.7 percent at most;
4) Effectively moderating the reaction degree of the bimetallic catalytic system, and no implosion phenomenon occurs in the polymerization reaction process.
The invention provides a preparation method of a carbon dioxide-propylene oxide copolymer, which achieves the following aims by introducing a solvent into a polymerization system for dispersion: 1) The problem that the catalyst is difficult to disperse due to the increase of the system viscosity in the later reaction stage of a heterogeneous catalytic system is solved, and the conversion rate of the propylene oxide is effectively improved; 2) The concentration of a reaction substrate is reduced, the phenomenon of implosion caused by over violent reaction is avoided, and the simple and controllable polymerization reaction is realized; 3) The generation of byproducts in a rare earth ternary catalytic system and a zinc carboxylate catalytic system is effectively reduced; 4) The ultimate reaction temperature of the rare earth ternary catalytic system and the zinc carboxylate catalytic system is greatly improved, so that the polymerization reaction rate is effectively improved; 5) Effectively improves the content of carbonate units in the chain segment of the polymerization product of the bimetallic catalytic system.
The content of carbonate units in a copolymerization product obtained by catalyzing the rare earth ternary catalyst and the zinc dicarboxylate catalyst reaches 95-99%, the number average molecular weight is 80,000-190,000g/mol, the molecular weight distribution is 2.50-4.50, the by-product cyclic carbonate is less than 5%, the reaction lasts for 12 hours, and the conversion rate of propylene oxide can reach 64.7%; the content of carbonate units in the copolymerization product obtained by catalysis of the bimetallic catalyst reaches 85-90 percent, the number average molecular weight is 100,000-250,000g/mol, the molecular weight distribution is 1.90-3.50, the content of the by-product cyclic carbonate is less than 4 percent, the reaction lasts for 10 hours, and the highest conversion rate of the propylene oxide can reach 98.7 percent.
In order to further illustrate the present invention, the following will describe in detail the preparation method of a carbon dioxide-propylene oxide copolymer provided by the present invention with reference to the examples.
Example 1
a) Preparing a ternary rare earth catalyst according to the Chinese patent ZL 03105023.9; 40mL rare earth three-way catalyst (0.001 molY (CCl)3COO)3+0.01mol of glycerol +0.02mol of ZnEt2+30mL1, 3-dioxolane) freeze drying to remove the solvent 1, 3-dioxolane, adding 150mL diethyl carbonate, mixing uniformly, putting into a 500mL high-pressure reaction kettle which is pretreated by anhydrous and oxygen-free, adding 150mL propylene oxide, charging 210g carbon dioxide, heating to 70 ℃, keeping the pressure in the reaction kettle to be 7MPa at most, timing, and keeping the temperature at 70 ℃ for reaction for 12h.
b) And after the reaction is finished, quickly transferring the reaction kettle to an ice water bath, introducing cooling liquid into an internal cooling coil in the kettle, quickly cooling the system to a temperature lower than 40 ℃, slowly relieving the pressure in the reaction kettle to normal pressure, opening the reaction kettle, taking out a mixed product in the kettle, washing and precipitating for 3 times by using absolute ethyl alcohol, removing the residual solvent in the product, then placing the product in a vacuum oven at 40 ℃, treating for 10 hours at-0.1 MPa, and drying to constant weight to obtain 80.7g of the carbon dioxide-propylene oxide copolymer. The number average molecular weight of the carbon dioxide-propylene oxide copolymer was determined by GPC as 95,800g/mol, with a narrow distribution polystyrene as the standard and methylene chloride as the mobile phase, and the molecular weight distribution was 3.63.1H-NMR showed that the ester content in the carbon dioxide-propylene oxide copolymer segment was 96%, the cyclic carbonate content as a by-product was 3.8%, and the propylene oxide conversion was 38.1%.
Example 2
a) Preparing dicarboxylic acid catalyst according to chinese patent 201510859248.8; weighing 2g of ZnGA, adding the ZnGA into 150mL of diethyl carbonate, uniformly mixing, putting the mixture into a 500mL high-pressure reaction kettle subjected to anhydrous and anoxic pretreatment, adding 150mL of propylene oxide, charging 210g of carbon dioxide, heating to 70 ℃, keeping the pressure in the reaction kettle to be 7MPa at the maximum, timing, and keeping the temperature of 70 ℃ for reaction for 12 hours.
b) And (3) after the reaction is finished, quickly transferring the reaction kettle to an ice water bath, introducing cooling liquid into a cooling coil in the kettle, quickly cooling the system to a temperature lower than 40 ℃, slowly relieving the pressure in the reaction kettle to normal pressure, opening the reaction kettle, taking out a mixed product in the kettle, washing and precipitating for 3 times by using absolute ethyl alcohol, removing the residual solvent in the product, treating for 10 hours at 40 ℃ and 0.1MPa in a vacuum oven, and drying to constant weight to obtain 84.6g of the carbon dioxide-epoxypropane copolymer. Narrow-distribution polystyrene is taken as a standard sample, dichloromethane is taken as a mobile phase,the carbon dioxide-propylene oxide copolymer had a number average molecular weight of 90,000g/mol and a molecular weight distribution of 3.53 as determined by GPC.1H-NMR showed that the ester content in the carbon dioxide-propylene oxide copolymer segment was 95.5%, the cyclic carbonate content as a by-product was 3.6%, and the propylene oxide conversion was 40%.
Example 3
a) Preparing a double metal catalyst DMC according to the Chinese patent 201210086834. X; weighing 0.2g of DMC, adding the DMC into 150mL of diethyl carbonate, uniformly mixing, putting into a 500mL high-pressure reaction kettle subjected to anhydrous and oxygen-free pretreatment, adding 150mL of propylene oxide, filling 260g of carbon dioxide, heating to 55 ℃, keeping the pressure in the reaction kettle to be 7MPa at the maximum, timing, and maintaining the temperature of 55 ℃ for reaction for 10 hours.
b) And (3) after the reaction is finished, quickly transferring the reaction kettle to an ice water bath, introducing cooling liquid into a cooling coil in the kettle, quickly cooling the system to a temperature lower than 40 ℃, slowly relieving the pressure in the reaction kettle to normal pressure, opening the reaction kettle, taking out a mixed product in the kettle, washing and precipitating for 3 times by using absolute ethyl alcohol, removing the residual solvent in the product, treating for 10 hours at 40 ℃ and 0.1MPa in a vacuum oven, and drying to constant weight to obtain 200.6g of the carbon dioxide-epoxypropane copolymer. The number average molecular weight of the carbon dioxide-propylene oxide copolymer was 178,300g/mol and the molecular weight distribution was 2.33 by GPC using narrow distribution polystyrene as the standard and methylene chloride as the mobile phase.1H-NMR showed that the ester content in the carbon dioxide-propylene oxide copolymer segment was 85.7%, the cyclic carbonate content as a by-product was 2.6%, and the propylene oxide conversion was 98.7%.
Example 4
a) Preparing a ternary rare earth catalyst according to a Chinese patent ZL 03105023.9; 40mL rare earth three-way catalyst (0.001 molY (CCl)3COO)3+0.01mol of glycerol +0.02mol of ZnEt2+30mL1, 3-dioxypentacyclic) freeze drying to remove the solvent 1, 3-dioxypentacyclic), adding 150mL of dichloromethane, uniformly mixing, adding into a 500mL high-pressure reaction kettle subjected to anhydrous oxygen-free pretreatment, adding 150mL of propylene oxide, charging 210g of carbon dioxide, heating to 70 ℃, keeping the pressure in the reaction kettle to be 7MPa at most, timing, and keeping the temperature at 70 ℃ for reaction for 12 hours.
b) Reaction(s) ofAnd after the reaction is finished, quickly transferring the reaction kettle to an ice water bath, introducing cooling liquid into an internal cooling coil in the kettle, quickly cooling the system to a temperature lower than 40 ℃, slowly relieving the pressure in the reaction kettle to normal pressure, opening the reaction kettle, taking out a mixed product in the kettle, washing and precipitating for 3 times by using absolute ethyl alcohol, removing residual solvent in the product, then placing the product in a vacuum oven at 40 ℃, treating for 10 hours at-0.1 MPa, and drying to constant weight to obtain 80.7g of the carbon dioxide-propylene oxide copolymer. The number average molecular weight of the carbon dioxide-propylene oxide copolymer measured by GPC was 180,700g/mol and the molecular weight distribution was 2.75 using narrow distribution polystyrene as the standard and dichloromethane as the mobile phase.1H-NMR showed that the ester content in the carbon dioxide-propylene oxide copolymer segment was 97.8%, the cyclic carbonate content as a by-product was 4.9%, and the propylene oxide conversion was 38%.
Example 5
a) Preparing dicarboxylic acid catalyst according to chinese patent 201510859248.8; weighing 2g of ZnGA, adding the ZnGA into 150mL of dichloromethane, uniformly mixing, putting the mixture into a 500mL high-pressure reaction kettle subjected to anhydrous and anoxic pretreatment, adding 150mL of propylene oxide, charging 210g of carbon dioxide, heating to 70 ℃, keeping the pressure in the reaction kettle to be 7MPa at the maximum, starting timing, and keeping the temperature of 70 ℃ for reaction for 12 hours.
b) And (3) after the reaction is finished, quickly transferring the reaction kettle to an ice water bath, introducing cooling liquid into a cooling coil in the kettle, quickly cooling the system to a temperature lower than 40 ℃, slowly relieving the pressure in the reaction kettle to normal pressure, opening the reaction kettle, taking out a mixed product in the kettle, washing and precipitating for 3 times by using absolute ethyl alcohol, removing the residual solvent in the product, treating for 10 hours at 40 ℃ and 0.1MPa in a vacuum oven, and drying to constant weight to obtain 80.5g of the carbon dioxide-epoxypropane copolymer. The number average molecular weight of the carbon dioxide-propylene oxide copolymer was 177,900g/mol and the molecular weight distribution was 3.09 by GPC using narrow distribution polystyrene as a standard and methylene chloride as a mobile phase.1H-NMR showed that the ester content in the carbon dioxide-propylene oxide copolymer segment was 98.5%, the cyclic carbonate content as a by-product was 2.7%, and the propylene oxide conversion was 37.4%.
Example 6
a) Preparing dicarboxylic acid catalyst according to chinese patent 201510859248.8; weighing 2g of ZnGA, adding the ZnGA into 150mL of dichloromethane, uniformly mixing, putting the mixture into a 500mL high-pressure reaction kettle subjected to anhydrous and anoxic pretreatment, adding 150mL of propylene oxide, charging 230g of carbon dioxide, heating to 90 ℃, keeping the pressure in the reaction kettle to be 9MPa at the maximum, starting timing, and keeping the temperature of 90 ℃ for reaction for 12 hours.
b) And (3) after the reaction is finished, quickly transferring the reaction kettle to an ice water bath, introducing cooling liquid into a cooling coil in the kettle, quickly cooling the system to a temperature lower than 40 ℃, slowly relieving the pressure in the reaction kettle to normal pressure, opening the reaction kettle, taking out a mixed product in the kettle, washing and precipitating for 3 times by using absolute ethyl alcohol, removing the residual solvent in the product, treating for 10 hours at 40 ℃ and 0.1MPa in a vacuum oven, and drying to constant weight to obtain 136.6g of the carbon dioxide-epoxypropane copolymer. The number average molecular weight of the carbon dioxide-propylene oxide copolymer was 117,200g/mol and the molecular weight distribution was 4.37 as determined by GPC using narrow distribution polystyrene as the standard and dichloromethane as the mobile phase.1H-NMR showed that the ester content in the carbon dioxide-propylene oxide copolymer segment was 96.4%, the cyclic carbonate content as a by-product was 4.8%, and the propylene oxide conversion was 64.7%.
Example 7
a) Preparing a bimetallic catalyst DMC according to Chinese patent 201210086834. X; 0.2g of DMC is weighed, added into 150mL of dichloromethane, uniformly mixed and then put into a 500mL high-pressure reaction kettle which is pretreated by anhydrous and oxygen-free, 150mL of propylene oxide is added, 260g of carbon dioxide is filled, the temperature is heated to 55 ℃, the pressure in the reaction kettle is up to 7MPa, timing is started, and the reaction is maintained at 55 ℃ for 10 hours.
b) And after the reaction is finished, quickly transferring the reaction kettle to an ice water bath, introducing cooling liquid into a cooling coil in the kettle, quickly cooling the system to a temperature lower than 40 ℃, slowly relieving the pressure in the reaction kettle to normal pressure, opening the reaction kettle, taking out a mixed product in the kettle, washing and precipitating for 3 times by using absolute ethyl alcohol, removing the residual solvent in the product, treating for 10 hours at 40 ℃ and 0.1MPa in a vacuum oven, and drying to constant weight to obtain 191.3g of the carbon dioxide-epoxypropane copolymer. Taking narrow-distribution polystyrene as a standard sample and dichloromethane as a mobile phase, the number average molecular weight of the carbon dioxide-propylene oxide copolymer is 156 as measured by GPC,300g/mol, molecular weight distribution 2.91.1H-NMR showed that the ester content in the carbon dioxide-propylene oxide copolymer segment was 86.7%, the cyclic carbonate content as a by-product was 2.3%, and the propylene oxide conversion was 93.5%.
Example 8
a) Preparing a ternary rare earth catalyst according to a Chinese patent ZL 03105023.9; 40mL rare earth three-way catalyst (0.001 molY (CCl)3COO)3+0.01mol of glycerol +0.02mol of ZnEt2+30mL1, 3-dioxolane) is added with 120mL1, 3-dioxolane, the mixture is put into a 500mL high-pressure reaction kettle which is pretreated by anhydrous and oxygen-free, 150mL propylene oxide is added, 210g carbon dioxide is filled, the temperature is heated to 70 ℃, the pressure in the reaction kettle is up to 7MPa, timing is started, and the reaction is maintained at 70 ℃ for 12 hours.
b) And (3) after the reaction is finished, quickly transferring the reaction kettle to an ice water bath, introducing cooling liquid into a cooling coil in the kettle, quickly cooling the system to a temperature lower than 40 ℃, slowly relieving the pressure in the reaction kettle to normal pressure, opening the reaction kettle, taking out a mixed product in the kettle, washing and precipitating for 3 times by using absolute ethyl alcohol, removing the residual solvent in the product, treating for 10 hours at 40 ℃ and 0.1MPa in a vacuum oven, and drying to constant weight to obtain 78.6g of the carbon dioxide-epoxypropane copolymer. The number average molecular weight of the carbon dioxide-propylene oxide copolymer was 108,100g/mol and the molecular weight distribution was 3.58 as determined by GPC using narrow distribution polystyrene as a standard and dichloromethane as a mobile phase.1H-NMR showed that the ester content in the carbon dioxide-propylene oxide copolymer segment was 96.5%, the cyclic carbonate content as a by-product was 3.0%, and the propylene oxide conversion was 36.9%.
Example 9
a) Preparing dicarboxylic acid catalyst according to chinese patent 201510859248.8; weighing 2g of ZnGA, adding the ZnGA into 150mL1, 3-dioxane, uniformly mixing, putting the mixture into a 500mL high-pressure reaction kettle subjected to anhydrous and anoxic pretreatment, adding 150mL of propylene oxide, filling 210g of carbon dioxide, heating to 70 ℃, keeping the pressure in the reaction kettle to be 7MPa at most, timing, and reacting for 12 hours at 70 ℃.
b) After the reaction is finished, the reaction kettle is quickly transferred into an ice-water bath, and cooling liquid is introduced into an inner cooling coil pipe in the kettle, so thatAnd quickly cooling the system to be lower than 40 ℃, slowly relieving the pressure in the reaction kettle to be normal pressure, opening the reaction kettle, taking out the mixed product in the reaction kettle, washing and precipitating for 3 times by using absolute ethyl alcohol, removing the residual solvent in the product, then placing the product in a vacuum oven at 40 ℃, treating for 10 hours at-0.1 MPa, and drying to constant weight to obtain 88.2g of the carbon dioxide-propylene oxide copolymer. The number average molecular weight of the carbon dioxide-propylene oxide copolymer was 94,700g/mol and the molecular weight distribution was 3.40 as determined by GPC using narrow distribution polystyrene as a standard and methylene chloride as a mobile phase.1H-NMR showed that the ester content in the carbon dioxide-propylene oxide copolymer segment was 96.4%, the cyclic carbonate content as a by-product was 2.9%, and the propylene oxide conversion was 41.4%.
Example 10
a) Preparing a bimetallic catalyst DMC according to Chinese patent 201210086834. X; weighing 0.2g of DMC, adding the DMC into 150mL1, 3-dioxane, uniformly mixing, putting the mixture into a 500mL high-pressure reaction kettle subjected to anhydrous and oxygen-free pretreatment, adding 150mL of propylene oxide, charging 260g of carbon dioxide, heating to 55 ℃, keeping the pressure in the reaction kettle to be 7MPa at the maximum, timing, and keeping the temperature of 55 ℃ for reaction for 10 hours.
b) And (3) after the reaction is finished, quickly transferring the reaction kettle to an ice water bath, introducing cooling liquid into a cooling coil in the kettle, quickly cooling the system to a temperature lower than 40 ℃, slowly relieving the pressure in the reaction kettle to normal pressure, opening the reaction kettle, taking out a mixed product in the kettle, washing and precipitating for 3 times by using absolute ethyl alcohol, removing the residual solvent in the product, treating for 10 hours at 40 ℃ and 0.1MPa in a vacuum oven, and drying to constant weight to obtain 197.2g of the carbon dioxide-epoxypropane copolymer. The number average molecular weight of the carbon dioxide-propylene oxide copolymer was 106,900g/mol and the molecular weight distribution was 3.25 by GPC using narrow distribution polystyrene as a standard and methylene chloride as a mobile phase.1H-NMR showed that the ester content in the carbon dioxide-propylene oxide copolymer segment was 85.8%, the cyclic carbonate content as a by-product was 2.0%, and the propylene oxide conversion was 96.7%.
Comparative example 1
a) Preparing a ternary rare earth catalyst according to a Chinese patent ZL 03105023.9; 40mL rare earth three-way catalyst (0.001 molY (CCl)3COO)3+0.01mol Glycerol +0.02molZnEt2+30mL1, 3-dioxolane) is frozen, dried and the solvent 1, 3-dioxolane is removed, 150mL of propylene oxide is added and mixed evenly, then the mixture is put into a 500mL high-pressure reaction kettle which is pretreated by anhydrous and oxygen-free, 190g of carbon dioxide is filled, the temperature is heated to 70 ℃, the pressure in the reaction kettle is up to 4.2MPa, the timing is started, and the reaction is maintained at 70 ℃ for 12 hours.
b) And (3) after the reaction is finished, quickly transferring the reaction kettle to an ice water bath, introducing cooling liquid into a cooling coil in the kettle, quickly cooling the system to a temperature lower than 40 ℃, slowly relieving the pressure in the reaction kettle to normal pressure, opening the reaction kettle, taking out a mixed product in the kettle, washing and precipitating for 3 times by using absolute ethyl alcohol, removing the residual solvent in the product, treating for 10 hours at 40 ℃ and 0.1MPa in a vacuum oven, and drying to constant weight to obtain 72.4g of the carbon dioxide-epoxypropane copolymer. The number average molecular weight of the carbon dioxide-propylene oxide copolymer was 96,200g/mol and the molecular weight distribution was 4.71 by GPC using narrow distribution polystyrene as a standard and dichloromethane as a mobile phase.1H-NMR showed that the ester content in the carbon dioxide-propylene oxide copolymer segment was 93.6%, the cyclic carbonate content as a by-product was 6.0%, and the propylene oxide conversion was 34.8%.
Comparative example 2
a) Preparing dicarboxylic acid catalyst according to chinese patent 201510859248.8; weighing 2g of ZnGA, adding the ZnGA into 150mL of propylene oxide, uniformly mixing, putting the mixture into a 500mL high-pressure reaction kettle subjected to anhydrous and anoxic pretreatment, introducing 190g of carbon dioxide, heating to 70 ℃, keeping the pressure in the reaction kettle to be 4.2MPa at most, timing, and keeping the temperature of 70 ℃ for reaction for 12 hours.
b) And (3) after the reaction is finished, quickly transferring the reaction kettle to an ice water bath, introducing cooling liquid into a cooling coil in the kettle, quickly cooling the system to a temperature lower than 40 ℃, slowly relieving the pressure in the reaction kettle to normal pressure, opening the reaction kettle, taking out a mixed product in the kettle, washing and precipitating for 3 times by using absolute ethyl alcohol, removing the residual solvent in the product, treating for 10 hours at 40 ℃ and 0.1MPa in a vacuum oven, and drying to constant weight to obtain 74.9g of the carbon dioxide-epoxypropane copolymer. The number average molecule of the carbon dioxide-propylene oxide copolymer is measured by GPC by taking narrow distribution polystyrene as a standard sample and dichloromethane as a mobile phaseThe amount was 88000g/mol and the molecular weight distribution was 4.75.1H-NMR showed that the ester content in the carbon dioxide-propylene oxide copolymer segment was 91.4%, the cyclic carbonate content as a by-product was 7.1%, and the propylene oxide conversion was 36.6%.
Comparative example 3
a) Preparing a double metal catalyst DMC according to the Chinese patent 201210086834. X; weighing 0.2g of DMC, adding the DMC into 150mL of propylene oxide, uniformly mixing, then putting the mixture into a 500mL high-pressure reaction kettle subjected to anhydrous and oxygen-free pretreatment, filling 270g of carbon dioxide, heating to 55 ℃, keeping the pressure in the reaction kettle to be 4.2MPa at most, timing, and maintaining the temperature of 55 ℃ for reaction for 10 hours.
b) And after the reaction is finished, quickly transferring the reaction kettle to an ice water bath, introducing cooling liquid into an internal cooling coil in the kettle, quickly cooling the system to a temperature lower than 40 ℃, slowly relieving the pressure in the reaction kettle to normal pressure, opening the reaction kettle, taking out a mixed product in the kettle, washing and precipitating for 3 times by using absolute ethyl alcohol, removing residual solvent in the product, then placing the product in a vacuum oven at 40 ℃, treating for 10 hours at-0.1 MPa, and drying to constant weight to obtain 178.7g of the carbon dioxide-propylene oxide copolymer. The number average molecular weight of the carbon dioxide-propylene oxide copolymer measured by GPC with narrow distribution polystyrene as a standard and dichloromethane as a mobile phase was 90800g/mol and the molecular weight distribution was 3.77.1H-NMR showed that the ester content in the carbon dioxide-propylene oxide copolymer segment was 76.7%, the cyclic carbonate content as a by-product was 3.9%, and the propylene oxide conversion was 92.1%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A method for preparing a carbon dioxide-propylene oxide copolymer, comprising:
in the presence of a solvent and a heterogeneous catalyst, polymerizing carbon dioxide and propylene oxide to obtain a carbon dioxide-propylene oxide copolymer; the mass ratio of the carbon dioxide to the propylene oxide is (30-300) to 100;
the solvent comprises one or more of dimethyl carbonate, diethyl carbonate, ethyl acetate, acetone, dimethylformamide, dichloromethane, trichloromethane, tetrahydrofuran, 1, 3-dioxolane and dioxane, and is prepared by passing through a molecular sieve or CaH2Treating until the water content is lower than 50ppm, wherein the volume ratio of the solvent to the propylene oxide is (0.5-2) to 1; the heterogeneous catalyst is a rare earth ternary catalyst, a zinc dicarboxylate catalyst or a bimetallic catalyst;
the content of carbonate units in a copolymerization product obtained by catalyzing a rare earth ternary catalyst and a zinc dicarboxylate catalyst reaches 95-99%, the number average molecular weight is 80,000-190,000 g/mol, the molecular weight distribution is 2.50-4.50, the content of a by-product cyclic carbonate is less than 5%, the reaction lasts for 12 hours, and the conversion rate of propylene oxide can reach 64.7%; the content of carbonate units in a copolymerization product obtained by catalysis of a bimetallic catalyst reaches 85% -90%, the number average molecular weight is 100,000-250,000 g/mol, the molecular weight distribution is 1.90-3.50, the content of a by-product cyclic carbonate is less than 4%, the reaction time is 10 hours, and the conversion rate of propylene oxide can reach 98.7% at most.
2. The preparation method of claim 1, wherein when the heterogeneous catalyst is a rare earth three-way catalyst, the polymerization temperature is 60 ℃ to 100 ℃; the polymerization pressure is 3-15 MPa; the polymerization time is 8 to 30h;
when the heterogeneous catalyst is a zinc dicarboxylate catalyst, the polymerization temperature is 60-100 ℃; the polymerization pressure is 3-15 MPa; the polymerization time is 8 to 30h.
3. The method of claim 1, wherein when the heterogeneous catalyst is a bimetallic catalyst, the polymerization temperature is from 40 ℃ to 70 ℃; the polymerization pressure is 3-15 MPa; the polymerization time is 8 to 30h.
4. The method according to claim 1, wherein the rare earth three-way catalyst has the following composition:
a) The alkyl zinc is one of ethyl zinc, n-propyl zinc, isopropyl zinc, n-butyl zinc, isobutyl zinc and phenyl zinc or benzyl zinc;
b) Glycerol;
c) The metal salt is divided into rare earth salt and non-rare earth salt, and specifically comprises the following components:
(1) the structural formula of the rare earth salt is: MXnYm；
Wherein: n, m is a positive integer of 0 to 3, and n + m =3;
m is one of Y, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb and Lu; x is Ka value of 10-3 The above carboxylic acid group or sulfonic acid group, i.e., one of an aminosulfonic acid group, a chloroacetic acid group, a dichloroacetic acid group, a trichloroacetic acid group, a trifluoroacetate group, an o-chlorobenzoic acid group, an α -tartaric acid group, a benzenesulfonic acid group or a naphthalenesulfonic acid group; y is-Cl;
(2) the non-rare earth salt has the structural formula: MXnYm；
Wherein M is zinc or aluminum; zn: n and m are positive integers from 0 to 2, and n + m =2; al: n, m is a positive integer of 0 to 3, and n + m =3; x is one of citric acid group, alpha-tartaric acid group, iminodiacetic acid group, chloroacetic acid group, dichloroacetic acid group, trichloroacetic acid group, aminosulfonic acid group, o-chlorobenzoic acid group, benzenesulfonic acid group or sulfonic acid group; y is-Cl.
5. The method according to claim 1, wherein the zinc dicarboxylate catalyst is prepared by the following method:
reacting the dicarboxylic acid monovalent metal salt and the zinc salt in water, and collecting the solid generated by the reaction to obtain the dicarboxylic acid zinc catalyst.
6. The method of claim 5, wherein the initial pH of the reaction is 5.2 to 6.3; the end point pH value of the reaction is 3.8 to 4.7.
7. The method of claim 1, wherein the bimetallic catalyst is prepared by the following method:
a) Mixing tert-butyl alcohol, water, a zinc salt compound and a rare earth salt compound to obtain a mixed salt solution;
wherein the zinc salt compound is ZnCl2、ZnBr2、Zn(CH3COO)2、Zn(ClCH2COO)2、Zn(Cl2CHCOO)2、Zn(Cl3CCOO)2、ZnSO4And Zn (NO)3)2One or more of the above; the rare earth salt compound is YCl3、LaCl3、NdCl3、PrCl3、Y(NO3)3、La(NO3)3、Nd(NO3)3、Pr(NO3)3、Y(ClCH2COO)3、La(ClCH2COO)3、Nd(ClCH2COO)3、Pr(ClCH2COO)3、Y(Cl2CHCOO)3、La(Cl2CHCOO)3、Nd(Cl2CHCOO)3、Pr(Cl2CHCOO)3、Y(Cl3CCOO)3、La(Cl3CCOO)3、Nd(Cl3CCOO)3、Pr(Cl3CCOO)3One or more of the above;
b) Adding K to the mixed salt solution3[Co(CN)6]The solution is stirred, separated, washed and dried to obtain the rare earth doped Zn-based alloy3[Co(CN)6]2Double metal cyanide compounds of (a).
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