CN102558199A - Tetradentate schiff base metal complexes, metal porphyrin complexes and preparing method of polycarbonate - Google Patents

Tetradentate schiff base metal complexes, metal porphyrin complexes and preparing method of polycarbonate Download PDF

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CN102558199A
CN102558199A CN2011104592546A CN201110459254A CN102558199A CN 102558199 A CN102558199 A CN 102558199A CN 2011104592546 A CN2011104592546 A CN 2011104592546A CN 201110459254 A CN201110459254 A CN 201110459254A CN 102558199 A CN102558199 A CN 102558199A
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CN102558199B (en
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秦玉升
王献红
赵晓江
王佛松
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention provides tetradentate schiff base metal complexes with formula (I) and metal porphyrin complexes with formula (II). The active centers of the two complexes are non-toxic zinc, magnesium, manganese or iron. The invention also provides a method for preparing polycarbonate by using the complexes as a catalyzer. The ligand of the two complexes contain at least one or more quaternary ammonium salt or strong sterically hindered organic base group, so the two complexes have higher catalytic activity, meanwhile the complexes have non-toxic active center metal like zinc, magnesium, manganese or iron, can effectively prevent the problem of the exceeding content of toxic metals in polycarbonate and ensure that the product does not contain toxic metal residues.

Description

Tetradentate schiff base metal complexes, metalloporphyrin title complex and prepare the method for polycarbonate
Technical field
The present invention relates to catalyst field, relate in particular to tetradentate schiff base metal complexes, metalloporphyrin title complex and prepare the method for polycarbonate.
Background technology
Carbonic acid gas is the main gas that causes Greenhouse effect, is again one of carbon source the abundantest on the earth simultaneously, also is a kind of carbon oxygen resource of cheapness.Carbonic acid gas is being an important research project as carbon oxygen resource aspect synthetic large Essential Chemistry article, fuel and the macromolecular material.Wherein, With carbonic acid gas and epoxide is raw material; Copolymerization synthetic aliphatic polycarbonate is a kind of full degraded type macromolecular material under catalyst action, has the good transparency, the good blocking oxygen and the performance of water; Can be used as engineering plastics, biodegradable nonpollution material, disposable medicine and packaging material for food, tackiness agent and matrix material etc., have application potential widely in fields such as food and medical packages.
Inoue had realized since carbonic acid gas and the propylene oxide copolymerization first in 1969; A series of catalystsystem such as zinc alkyl(s)/reactive hydrogen catalystsystem, zinc carboxylate system, DMC catalysts, rare-earth ternary catalyst, catalysis of metalloporphyrin agent, phenol zincum salts catalystsystem and diimine zinc class catalyzer have appearred in succession; The research and development of these catalystsystem has bigger pushing effect for synthetic complete biodegradable aliphatic polycarbonate; The system that has has been used for suitability for industrialized production; But above system still exists catalytic activity low, the problem of long reaction time.
Four tooth schiff bases cobalt complex (SelenCo) the catalystsystem development that began to occur in 2003 rapidly; Double-component catalyst system of being made up of SalenCo title complex and quaternary ammonium salt or quaternary alkylphosphonium salt and the difunctional SalenCo catalyzer of single-component that integrates active site and steric hindrance property organic bases group have successively occurred, these two types of catalyst activities reach 10 6Gram polymkeric substance/mol catalyst.But this type catalyzer is the active site with deleterious metal such as cobalt, chromium etc. generally; Cause toxic metal content overproof in the polycarbonate that catalyzed polymerization generates; Become the significant obstacle that polycarbonate material is applied to food, medical package field, so the four tooth schiff bases cobalt complex catalyzer that this type has a greater activity can't be applied to actual industrial production always.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of four chi schiff base metal complex catalyzer or a kind of metalloporphyrin composition catalyst that is used for polycarbonate synthesis that is used for polycarbonate synthesis; Make that catalyzer has high catalytic activity and product nontoxicity in preparation aliphatic polycarbonate process.
The invention discloses a kind of structure suc as formula the tetradentate schiff base metal complexes shown in (I):
Figure BDA0000128376200000021
Wherein, D 1, D 2, D 3, D 4, D 5, D 6, D 7, D 8Independently be selected from the substituting group of hydrogen, halogen, substituted aliphatic group, substituted assorted aliphatic group, substituted aryl, substituted heteroaryl or formula (III) structure separately, D 1, D 2, D 3, D 4, D 5, D 6, D 7, D 8In at least one is the substituting group of formula (III) structure:
Figure BDA0000128376200000022
Q is quaternary ammonium salt, quaternary alkylphosphonium salt or big sterically hindered organic bases group in the formula (III), and
Figure BDA0000128376200000023
is for connecting the linking group of tetradentate schiff base metal ligand and Q;
Ring A has formula (IV), formula V or formula (VI) structure:
Figure BDA0000128376200000024
D wherein 1a, D 2a, D 3a, D 4aIndependently be selected from hydrogen, halogen, substituted aliphatic group, substituted assorted aliphatic group, substituted aryl or substituted heteroaryl separately;
N is 1～4 positive integer in the formula V;
Y does not exist, or Y be halogen ,-NO 3, CH 3COO-, CCl 3COO-, CF 3COO-, C1O 4-, BF 4-, BPh 4-,-CN ,-N 3, p-methylbenzoic acid root, p-methyl benzenesulfonic acid root, o-NP oxygen, p-NP oxygen, m-nitrophenol oxygen, 2; 2, 4-dinitrophenol oxygen, 3-5 dinitrophenol(DNP) oxygen, 2; 4,6-trinitrophenol oxygen, 3,5-NSC 2879 oxygen, 3; 5-difluorophenol oxygen, 3,5-di-trifluoromethyl phenol oxygen or pentafluranol negative oxygen ion;
X is zinc, magnesium, manganese or iron.
Preferably, said X is zinc or magnesium.
The present invention discloses a kind of structure suc as formula the metalloporphyrin title complex shown in (II):
Wherein: R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20Independently be selected from the substituting group of hydrogen, halogen, substituted aliphatic group, substituted assorted aliphatic group, substituted aryl, substituted heteroaryl or formula (III) structure separately, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20In at least one is the substituting group of formula (III) structure:
Figure BDA0000128376200000032
Q is quaternary ammonium salt, quaternary alkylphosphonium salt or big sterically hindered organic bases group in the formula (III), and
Figure BDA0000128376200000033
is for connecting the linking group of metalloporphyrin part and Q;
M is zinc, magnesium, manganese or iron.
Preferably, said M is zinc or magnesium.
The invention also discloses a kind of method for preparing polycarbonate, comprising:
Under the katalysis of said formula (I) tetradentate schiff base metal complexes, carbonic acid gas and epoxide generation copolyreaction generate polycarbonate;
Figure BDA0000128376200000041
Wherein, D 1, D 2, D 3, D 4, D 5, D 6, D 7, D 8Independently be selected from the substituting group of hydrogen, halogen, substituted aliphatic group, substituted assorted aliphatic group, substituted aryl, substituted heteroaryl or formula (III) structure separately, D 1, D 2, D 3, D 4, D 5, D 6, D 7, D 8In at least one is the substituting group of formula (III) structure:
Figure BDA0000128376200000042
Q is quaternary ammonium salt, quaternary alkylphosphonium salt or big sterically hindered organic bases group in the formula (III), and
Figure BDA0000128376200000043
is for connecting the linking group of tetradentate schiff base metal ligand and Q;
Ring A has formula (IV), formula V or formula (VI) structure:
Figure BDA0000128376200000044
D wherein 1a, D 2a, D 3a, D 4aIndependently be selected from hydrogen, halogen, substituted aliphatic group, substituted assorted aliphatic group, substituted aryl or substituted heteroaryl separately;
N is 1～4 positive integer in the formula V;
Y does not exist, or Y be halogen ,-NO 3, CH 3COO-, CCl 3COO-, CF 3COO-, ClO 4-, BF 4-, BPh 4-,-CN ,-N 3, p-methylbenzoic acid root, p-methyl benzenesulfonic acid root, o-NP oxygen, p-NP oxygen, m-nitrophenol oxygen, 2; 2, 4-dinitrophenol oxygen, 3-5 dinitrophenol(DNP) oxygen, 2; 4,6-trinitrophenol oxygen, 3,5-NSC 2879 oxygen, 3; 5-difluorophenol oxygen, 3,5-di-trifluoromethyl phenol oxygen or pentafluranol negative oxygen ion;
X is zinc, magnesium, manganese or iron.
The invention also discloses a kind of method for preparing polycarbonate, comprising:
Under the katalysis of said formula (II) metalloporphyrin title complex, carbonic acid gas and epoxide generation copolyreaction generate polycarbonate;
Figure BDA0000128376200000051
Wherein: R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20Independently be selected from the substituting group of hydrogen, halogen, substituted aliphatic group, substituted assorted aliphatic group, substituted aryl, substituted heteroaryl or formula (III) structure separately, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20In at least one is the substituting group of formula (III) structure:
Figure BDA0000128376200000052
Q is quaternary ammonium salt, quaternary alkylphosphonium salt or big sterically hindered organic bases group in the formula (III), and is for connecting the linking group of metalloporphyrin part and Q;
M is zinc, magnesium, manganese or iron.
Preferably, the mol ratio of said title complex and epoxide is 1: (2000～200000).
Preferably, the pressure of said carbonic acid gas is 0.1～8MPa.
Preferably, the temperature of reaction of said copolyreaction is 20～120 ℃, and the reaction times is 1～12h.
Preferably, said epoxide is one or more in oxyethane, propylene oxide, 1-butylene oxide ring, 2-butylene oxide ring, epoxy cyclohexane, cyclopentane epoxide, epoxy chloropropane methyl propenoic acid glycidyl ether, methyl glycidyl ether, phenyl glycidyl ether and the vinylbenzene epoxy alkane.
Compared with prior art, tetradentate schiff base metal complexes provided by the invention and metalloporphyrin title complex have selected nontoxic zinc, magnesium, manganese or iron as the active site metal.In catalysis carbonic acid gas and epoxide copolymerization aliphatic polycarbonate process; Contain at least one or a plurality of quaternary ammonium salt, quaternary alkylphosphonium salt or big sterically hindered organic bases group in the part of catalyzer; Therefore catalyzer has advantages of high catalytic activity; Simultaneously owing to selected nontoxic active site metallic zinc, magnesium, manganese or iron; Can prevent the appearance of toxic metal content overproof problem in the polycarbonate material effectively, guarantee not contain deleterious metal residual in the product, make product can directly be used for food and medical package product.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The embodiment of the invention discloses a kind of structure suc as formula the tetradentate schiff base metal complexes shown in (I):
Figure BDA0000128376200000061
Wherein, D 1, D 2, D 3, D 4, D 5, D 6, D 7, D 8Independently be selected from the substituting group of hydrogen, halogen, substituted aliphatic group, substituted assorted aliphatic group, substituted aryl, substituted heteroaryl or formula (III) structure separately, D 1, D 2, D 3, D 4, D 5, D 6, D 7, D 8In at least one is the substituting group of formula (III) structure:
Figure BDA0000128376200000062
Q is quaternary ammonium salt, quaternary alkylphosphonium salt or big sterically hindered organic bases group in the formula (III), and
Figure BDA0000128376200000063
is for connecting the linking group of tetradentate schiff base metal ligand and Q;
Ring A has formula (IV), formula V or formula (VI) structure:
Figure BDA0000128376200000071
D wherein 1a, D 2a, D 3a, D 4aIndependently be selected from hydrogen, halogen, substituted aliphatic group, substituted assorted aliphatic group, substituted aryl or substituted heteroaryl separately;
N is 1～4 positive integer in the formula V;
Y does not exist, or Y be halogen ,-NO 3, CH 3COO-, CCl 3COO-, CF 3COO-, ClO 4-, BF 4-, BPh 4-,-CN ,-N 3, p-methylbenzoic acid root, p-methyl benzenesulfonic acid root, o-NP oxygen, p-NP oxygen, m-nitrophenol oxygen, 2; 2, 4-dinitrophenol oxygen, 3-5 dinitrophenol(DNP) oxygen, 2; 4,6-trinitrophenol oxygen, 3,5-NSC 2879 oxygen, 3; 5-difluorophenol oxygen, 3,5-di-trifluoromethyl phenol oxygen or pentafluranol negative oxygen ion;
X is zinc, magnesium, manganese or iron.
In the described tetradentate schiff base metal complexes, as preferred version, D 1, D 2, D 3, D 4, D 5, D 6, D 7, D 8Independently be selected from the substituting group of hydrogen, substituted aliphatic group or formula (III) structure separately, D 1, D 2, D 3, D 4, D 5, D 6, D 7, D 8In contain the substituting group of a formula (III) structure at least:
Q is preferably quaternary ammonium salt or big sterically hindered organic bases group in the formula (III), and
Figure BDA0000128376200000073
is preferably alkyl or the alkoxyl group that connects tetradentate schiff base metal ligand and Q.As preferred version, Y does not exist, or Y is chosen as CF 3COO-.X is preferably zinc or magnesium.
The invention also discloses a kind of structure suc as formula the metalloporphyrin title complex shown in (II):
Figure BDA0000128376200000081
Wherein: R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20Independently be selected from the substituting group of hydrogen, halogen, substituted aliphatic group, substituted assorted aliphatic group, substituted aryl, substituted heteroaryl or formula (III) structure separately, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20In at least one is the substituting group of formula (III) structure:
Figure BDA0000128376200000082
Q is quaternary ammonium salt, quaternary alkylphosphonium salt or big sterically hindered organic bases group in the formula (III), and
Figure BDA0000128376200000083
is for connecting the linking group of metalloporphyrin part and Q;
M is zinc, magnesium, manganese or iron.
According to the present invention, R 2, R 3, R 4, R 5, R 6, R 7, R 9, R 10, R 11, R 12, R 14, R 15, R 16, R 17Be preferably hydrogen, R 1, R 8, R 13And R 18Be preferably the substituting group of formula (III) structure:
Figure BDA0000128376200000084
The middle Q of formula (III) is preferably big sterically hindered organic bases group, and
Figure BDA0000128376200000085
is preferably the alkyl that connects metalloporphyrin part and Q; M is preferably zinc or magnesium.
The invention provides a kind of tetradentate schiff base metal complexes and a kind of metalloporphyrin title complex, two kinds of title complexs have all selected nontoxic zinc, magnesium, manganese or iron as the active site metal.Owing to contain at least one or a plurality of quaternary ammonium salt, quaternary alkylphosphonium salt or big sterically hindered organic bases group in the title complex; Therefore two kinds of title complexs have advantages of high catalytic activity respectively in catalysis carbonic acid gas and epoxide generation copolyreaction in the process of preparation polycarbonate; Two kinds of title complexs have all been selected nontoxic active site metallic zinc, magnesium, iron or manganese simultaneously; Can prevent the appearance of toxic metal content overproof problem in the polycarbonate material effectively; Thereby guaranteed not contain in the product deleterious metal residual, can directly be used for food, medical package product.
The invention provides a kind of method for preparing polycarbonate, comprising:
Under the katalysis of said formula (I) tetradentate schiff base metal complexes, carbonic acid gas and epoxide generation copolyreaction generate polycarbonate;
Figure BDA0000128376200000091
Wherein, D 1, D 2, D 3, D 4, D 5, D 6, D 7, D 8Independently be selected from the substituting group of hydrogen, halogen, substituted aliphatic group, substituted assorted aliphatic group, substituted aryl, substituted heteroaryl or formula (III) structure separately, D 1, D 2, D 3, D 4, D 5, D 6, D 7, D 8In at least one is the substituting group of formula (III) structure:
Figure BDA0000128376200000092
Q is quaternary ammonium salt, quaternary alkylphosphonium salt or big sterically hindered organic bases group in the formula (III), and
Figure BDA0000128376200000093
is for connecting the linking group of tetradentate schiff base metal ligand and Q;
Ring A has formula (IV), formula V or formula (VI) structure:
Figure BDA0000128376200000094
D wherein 1a, D 2a, D 3a, D 4aIndependently be selected from hydrogen, halogen, substituted aliphatic group, substituted assorted aliphatic group, substituted aryl or substituted heteroaryl separately;
N is 1～4 positive integer in the formula V;
Y does not exist, or Y be halogen ,-NO 3, CH 3COO-, CCl 3COO-, CF 3COO-, ClO 4-, BF 4-, BPh 4-,-CN ,-N 3, p-methylbenzoic acid root, p-methyl benzenesulfonic acid root, o-NP oxygen, p-NP oxygen, m-nitrophenol oxygen, 2; 2, 4-dinitrophenol oxygen, 3-5 dinitrophenol(DNP) oxygen, 2; 4,6-trinitrophenol oxygen, 3,5-NSC 2879 oxygen, 3; 5-difluorophenol oxygen, 3,5-di-trifluoromethyl phenol oxygen or pentafluranol negative oxygen ion;
X is zinc, magnesium, manganese or iron.
The present invention also provides a kind of preparation method of polycarbonate, comprising:
Under the katalysis of said formula (II) metalloporphyrin title complex, carbonic acid gas and epoxide generation copolyreaction generate polycarbonate;
Figure BDA0000128376200000101
Wherein: R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20Independently be selected from the substituting group of hydrogen, halogen, substituted aliphatic group, substituted assorted aliphatic group, substituted aryl, substituted heteroaryl or formula (III) structure separately, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20In at least one is the substituting group of formula (III) structure:
Figure BDA0000128376200000102
Q is quaternary ammonium salt, quaternary alkylphosphonium salt or big sterically hindered organic bases group in the formula (III), and
Figure BDA0000128376200000103
is for connecting the linking group of metalloporphyrin part and Q;
M is zinc, magnesium, manganese or iron.
In two kinds of methods of above-mentioned preparation polycarbonate, in order to obtain best polymerization effect, the mol ratio of title complex and epoxide is preferably 1: (2000～200000).CO 2Pressure be preferably 0.1～8MPa.Temperature of reaction is preferably 20～120 ℃, more preferably 20～100 ℃.Reaction times is preferably 1～12h, more preferably 4～8h.
According to the present invention; Epoxide is preferably one or more in oxyethane, propylene oxide, 1-butylene oxide ring, 2-butylene oxide ring, epoxy cyclohexane, cyclopentane epoxide, epoxy chloropropane methyl propenoic acid glycidyl ether, methyl glycidyl ether, phenyl glycidyl ether and the vinylbenzene epoxy alkane in the copolyreaction; More preferably propylene oxide, epoxy cyclohexane, 1, the mixture of 2-butylene oxide ring or propylene oxide and epoxy cyclohexane.
The embodiment of the invention also provides employing tetradentate schiff base metal complexes or metalloporphyrin title complex as catalyzer; Carbonic acid gas and epoxide generation copolyreaction; The number-average molecular weight scope of the polycarbonate that obtains is 32000～302000, and range of molecular weight distributions is 1.21～1.30, and the cyclic carbonate sub product is less than 3% simultaneously; Carbonate unit content is greater than 99%; Hence one can see that, and above-mentioned two kinds of title complexs have shown advantages of high catalytic activity, and it is residual not contain toxic metal in the polymerisate.
In order further to understand the present invention, below in conjunction with embodiment tetradentate schiff base metal complexes provided by the invention, metalloporphyrin title complex and the method for preparing polycarbonate are described in detail, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Preparation title complex CAT-1
In the 250ml round-bottomed flask, add 2.16g sodium hydride and 30ml THF, stirring and dissolving postcooling to 0 ℃.In above-mentioned round-bottomed flask, slowly drip the tetrahydrofuran solution that 20ml is dissolved with 3.0g TBD.Rise to room temperature after dropwising, continue reaction 2h, drip the tetrahydrofuran solution that 20ml is dissolved with the 5.39g 2-tertiary butyl-4-(4-brombutyl) methyl-phenoxide.After dropwising, rise to room temperature, react 20h again, transform fully until reactant.Remove by filter the insolubles in the reaction solution, removal of solvent under reduced pressure obtains safran oily matter.Safran oily matter is dissolved in a spot of ETHYLE ACETATE, adds the Hydrogen chloride of 80ml 2mol/L, vigorous stirring 0.5h, static phase-splitting, organic phase water extraction 3 times merges water, slowly adds sodium bicarbonate solid and makes its alkalization, with dichloromethane extraction three times.The organic phase that merges is behind saturated common salt water washing and anhydrous sodium sulfate drying, and removal of solvent under reduced pressure obtains the white solid compound 2-tertiary butyl-4-(4-(TBD yl) butyl) methyl-phenoxide.
Under nitrogen protection; The 1.43g 2-tertiary butyl-4-(4-(TBD yl) butyl) methyl-phenoxide is dissolved in the refining methylene dichloride of 50mL, is cooled to-78 ℃, slowly drip 10mL and be dissolved with 2.1mL; 0.02mol the dichloromethane solution of boron tribromide; After waiting to dropwise, keep-78 ℃ of reaction 1h, rise to room temperature reaction 12h then.Above-mentioned reaction solution slowly is added in the saturated sodium bicarbonate solution, keeps solution to be alkalescence, isolate organic phase, water is with 50ml dichloromethane extraction 3 times.The organic phase that merges is through the saturated common salt water washing, anhydrous sodium sulfate drying, and removal of solvent under reduced pressure obtains crude product.Use column chromatography and separate purification, obtain the white solid 2-tertiary butyl-4-(4-(TBD yl) butyl) phenol.
Under nitrogen protection, the 1.03g 2-tertiary butyl-4-(4-(TBD yl) butyl) phenol is dissolved in the 50mL purified tetrahydrofuran, adds 0.83mL; 0.006moI refining triethylamine and 0.57g Magnesium Chloride Anhydrous; After stirring 15min under the room temperature, add the 0.45g Paraformaldehyde 96, be warming up to back flow reaction 3h; TLC follows the tracks of to react to raw material does not have residue, stopped reaction.After question response liquid is cooled to room temperature, add 50mL water, dichloromethane extraction 3 times.The organic phase that merges is through the saturated common salt water washing, anhydrous sodium sulfate drying, and removal of solvent under reduced pressure obtains thick product.Use column chromatography and separate purification, obtain the yellow solid 2-tertiary butyl-4-(4-(TBD yl) butyl)-2-hydroxy benzaldehyde.
In the 100mL round-bottomed flask, 0.11g cyclohexanediamine and the 0.7492-tertiary butyl-4-(4-(TBD yl) butyl)-2-hydroxy benzaldehyde are dissolved in the 50mL anhydrous methanol heating reflux reaction 10h.Removal of solvent under reduced pressure obtains yellow solid and is part.Part is carried out the analysis of high resolution electrospray ionization mass spectrum, and analytical results is [C50H75N4O2] -: 820.182, found:820.056, hence one can see that, and part can successfully prepare.
Above-mentioned yellow solid part and 0.13g Glacial acetic acid zinc are dissolved in the 10mL anhydrous methanol, and the title complex of (VII) structure that stirring at room reaction 12h obtains having formula is numbered CAT-1.The reaction formula of above-mentioned reaction is formula as follows:
Figure BDA0000128376200000121
Preparation title complex CAT-2
Preparing method and CAT-1 are basic identical; Difference is: with the yellow solid 2-tertiary butyl-4-that obtains (4-(TBD yl) butyl)-2-hydroxy benzaldehyde and O-Phenylene Diamine reaction; The title complex of (VIII) structure that obtains having formula, the title complex of formula (VIII) structure is numbered CAT-2.
Figure BDA0000128376200000132
Preparation title complex CAT-3
Preparing method and CAT-1 are basic identical, and difference is: with the yellow solid 2-tertiary butyl-4-that obtains (4-(TBD yl) butyl)-2-hydroxy benzaldehyde and reacting ethylenediamine, other reaction conditionss are constant, the title complex of (IX) structure that obtains having formula.The title complex of formula (IX) structure is numbered CAT-3.
Figure BDA0000128376200000133
Preparation title complex CAT-4
Preparing method and CAT-1 are basic identical, and difference is: by quaternary ammonium salt substituted salicylic aldehydes and cyclohexanediamine reaction, use Mg (CF simultaneously 3COO) 2The title complex that replaces zinc acetate and part coordination promptly to obtain having formula (X) structure.Title complex with formula (X) structure is numbered CAT-4.
Figure BDA0000128376200000141
Preparation title complex CAT-5
Preparing method and CAT-1 are basic identical, and difference is: by quaternary ammonium salt substituted salicylic aldehydes and cyclohexanediamine reaction, use Mg (CF simultaneously 3COO) 2The title complex that replaces zinc acetate and part coordination promptly to obtain having formula (XI) structure.The title complex that will have formula (XI) structure is numbered CAT-5.
Figure BDA0000128376200000142
Embodiment 2
3.23g is dissolved in adding 1.088g pyrroles in back in the 1800ml trichloromethane to the brooethyl phenyl aldehyde.Under argon shield, add 0.6721ml BF 3/ OEt 2Add the 2.76g DDQ behind the reaction 1h fast, continue reaction 1h, removal of solvent under reduced pressure, the gained solid is colourless to filtrating with methanol wash, promptly obtains brilliant violet look solid CPD4-a, productive rate about 51%.
1.4g TBD and 0.96g sodium hydride are dissolved under room temperature in the THF of 30ml; Slowly add the tetrahydrofuran solution that 30ml contains 7.89g CPD4-a; Dropwise afterreaction 48h after-filtration, filtrating is separated the gained solid through vacuum-drying with silica gel column chromatography; Obtain 6.04g purple solid CPD4-b, productive rate about 62%.CPD4-b is carried out the analysis of high resolution electrospray ionization mass spectrum, and analytical results is [C78H81N16] -: 1218.562, found:1218.556.Hence one can see that, and CPD4-b can successfully prepare.
Under argon shield, 1.22gCPD4-b is dissolved in the 30ml trichloromethane, slowly drip the chloroform soln that 20ml contains the 0.124g zinc ethyl, stirring reaction 1h.Obtain having the title complex of formula (XII) structure after the removal of solvent under reduced pressure, be numbered CAT-6.The reaction formula of above-mentioned reaction is formula as follows:
Figure BDA0000128376200000151
Embodiment 3
The propylene oxide of 0.1mmolCAT-1 and 1mol is joined in the 500ml autoclave that process dewaters in advance, deoxygenation is handled, rapidly through having the CO of pressure regulatory function 2Supply line charges into CO in still 2To pressure be 2.0MPa, temperature was controlled at 20 ℃ of following stirring reactions 4 hours.Polyreaction is chilled to room temperature with reaction kettle after finishing, and slowly bleeds off carbonic acid gas, in-20 ℃ of cold-traps, collects unreacted epoxide simultaneously.In still, add a certain amount of methylene dichloride then; Make the copolymer mixture dissolving, add a certain amount of methanol extraction again and go out polycarbonate, the polymkeric substance that is settled out is used methanol wash; Multipolymer vacuum-drying after the washing obtains 22g white and gathers propylene carbonate to constant weight.Recording this polymkeric substance number-average molecular weight through gel permeation chromatography is 103000g/mol, and MWD is 1.25; 1The H-NMR analytical results shows that the cyclic carbonate by product is less than 2.0%, and carbonate unit content is higher than 99% in the polymkeric substance.
Embodiment 4
The propylene oxide of 0.5mmolCAT-1 and 1mol is joined in the 500ml autoclave that process dewaters in advance, deoxygenation is handled, rapidly through having the CO of pressure regulatory function 2Supply line charges into CO in still 2To 2.0MPa, temperature was controlled at 25 ℃ of following stirring reactions 1 hour.Polyreaction is chilled to room temperature with reaction kettle after finishing, and slowly bleeds off carbonic acid gas, in-20 ℃ of cold-traps, collects unreacted epoxide simultaneously.In still, add a certain amount of methylene dichloride then, make the copolymer mixture dissolving, add a certain amount of methanol extraction again and go out polycarbonate; The polymkeric substance that is settled out is used methanol wash; Multipolymer vacuum-drying after the washing obtains 16 grams and gathers propylene carbonate to constant weight, and recording this polymkeric substance number-average molecular weight through gel permeation chromatography is 32000; MWD 1.28 1The H-NMR analytical results shows that the cyclic carbonate by product is less than 2.0%, and carbonate unit content is higher than 99% in the polymkeric substance.
Embodiment 5
The propylene oxide of 0.01mmolCAT-1 and 2mol is joined in the 500ml autoclave that process dewaters in advance, deoxygenation is handled, rapidly through having the CO of pressure regulatory function 2Supply line charges into CO in still 2To 2.0MPa, temperature was controlled at 25 ℃ of following stirring reactions 12 hours.Polyreaction is chilled to room temperature with reaction kettle after finishing, and slowly bleeds off carbonic acid gas, in-20 ℃ of cold-traps, collects unreacted epoxide simultaneously.In still, add a certain amount of methylene dichloride then, make the copolymer mixture dissolving, add a certain amount of methanol extraction again and go out polycarbonate; The polymkeric substance that is settled out is used methanol wash; Multipolymer vacuum-drying after the washing obtains 32 grams and gathers propylene carbonate to constant weight, and recording this polymkeric substance number-average molecular weight through gel permeation chromatography is 302000; MWD 1.27 1The H-NMR analytical results shows that the cyclic carbonate by product is less than 2.0%, and carbonate unit content is higher than 99% in the polymkeric substance.
Embodiment 6
The propylene oxide of 0.1mmolCAT-1 and 1mol is joined in the 500ml autoclave that process dewaters in advance, deoxygenation is handled, rapidly through having the CO of pressure regulatory function 2Supply line charges into CO in still 2To 2.0MPa, temperature was controlled at 100 ℃ of following stirring reactions 4 hours.Polyreaction is chilled to room temperature with reaction kettle after finishing, and slowly bleeds off carbonic acid gas, in-20 ℃ of cold-traps, collects unreacted epoxide simultaneously.In still, add a certain amount of methylene dichloride then; Make the copolymer mixture dissolving, add a certain amount of methanol extraction again and go out polycarbonate, the polymkeric substance that is settled out is used methanol wash; Multipolymer vacuum-drying after the washing obtains 20g white and gathers propylene carbonate to constant weight.Recording this polymkeric substance number-average molecular weight through gel permeation chromatography is 92000, MWD 1.30, 1The H-NMR analytical results shows that the cyclic carbonate by product is less than 3.0%, and carbonate unit content is higher than 98% in the polymkeric substance.
Embodiment 7
The propylene oxide of 0.1mmol CAT-1 and 1mol is joined in the 500ml autoclave that process dewaters in advance, deoxygenation is handled, rapidly through having the CO of pressure regulatory function 2Supply line charges into CO in still 2To 0.1MPa, temperature was controlled at 20 ℃ of following stirring reactions 8 hours.Polyreaction is chilled to room temperature with reaction kettle after finishing, and slowly bleeds off carbonic acid gas, in-20 ℃ of cold-traps, collects unreacted epoxide simultaneously.In still, add a certain amount of methylene dichloride then; Make the copolymer mixture dissolving, add a certain amount of methanol extraction again and go out polycarbonate, the polymkeric substance that is settled out is used methanol wash; Multipolymer vacuum-drying after the washing obtains 12g white and gathers propylene carbonate to constant weight.Recording this polymkeric substance number-average molecular weight through gel permeation chromatography is 56000, MWD 1.21, 1The H-NMR analytical results shows that the cyclic carbonate by product is less than 2.0%, and carbonate unit content is higher than 98% in the polymkeric substance.
Embodiment 8
The propylene oxide of 0.1mmolCAT-1 and 1mol is joined in the 500ml autoclave that process dewaters in advance, deoxygenation is handled, rapidly through having the CO of pressure regulatory function 2Supply line charges into CO in still 2To 8.0MPa, temperature was controlled at 20 ℃ of following stirring reactions 6 hours.Polyreaction is chilled to room temperature with reaction kettle after finishing, and slowly bleeds off carbonic acid gas, in-20 ℃ of cold-traps, collects unreacted epoxide simultaneously.In still, add a certain amount of methylene dichloride then; Make the copolymer mixture dissolving, add a certain amount of methanol extraction again and go out polycarbonate, the polymkeric substance that is settled out is used methanol wash; Multipolymer vacuum-drying after the washing obtains 21g white and gathers propylene carbonate to constant weight.Recording this polymkeric substance number-average molecular weight through gel permeation chromatography is 105000, MWD 1.25, 1The H-NMR analytical results shows that the cyclic carbonate by product is less than 2.0%, and carbonate unit content is higher than 99% in the polymkeric substance.
Embodiment 9
The epoxy cyclohexane of 0.1mmolCAT-1 and 1mol is joined in the 500ml autoclave that process dewaters in advance, deoxygenation is handled, rapidly through having the CO of pressure regulatory function 2Supply line charges into CO in still 2To 2.0MPa, temperature was controlled at 60 ℃ of following stirring reactions 4 hours.Polyreaction is chilled to room temperature with reaction kettle after finishing, and slowly bleeds off carbonic acid gas, in-20 ℃ of cold-traps, collects unreacted epoxide simultaneously.In still, add a certain amount of methylene dichloride then; Make the copolymer mixture dissolving, add a certain amount of methanol extraction again and go out polycarbonate, the polymkeric substance that is settled out is used methanol wash; Multipolymer vacuum-drying after the washing obtains 31g white and gathers propylene carbonate to constant weight.Recording this polymkeric substance number-average molecular weight through gel permeation chromatography is 125000, MWD 1.30, 1The H-NMR analytical results shows that the cyclic carbonate by product is less than 1.0%, and carbonate unit content is higher than 99% in the polymkeric substance.
Embodiment 10
With 1 of 0.1mmolCAT-1 and 1mol, the 2-butylene oxide ring joins in the 500ml autoclave that process dewaters in advance, deoxygenation is handled, rapidly through having the CO of pressure regulatory function 2Supply line charges into CO in still 2To 2.0MPa, temperature was controlled at 25 ℃ of following stirring reactions 4 hours.Polyreaction is chilled to room temperature with reaction kettle after finishing, and slowly bleeds off carbonic acid gas, in-20 ℃ of cold-traps, collects unreacted epoxide simultaneously.In still, add a certain amount of methylene dichloride then; Make the copolymer mixture dissolving, add a certain amount of methanol extraction again and go out polycarbonate, the polymkeric substance that is settled out is used methanol wash; Multipolymer vacuum-drying after the washing obtains 18g white and gathers propylene carbonate to constant weight.Recording this polymkeric substance number-average molecular weight through gel permeation chromatography is 97000, MWD 1.28, 1The H-NMR analytical results shows that the cyclic carbonate by product is less than 2.0%, and carbonate unit content is higher than 99% in the polymkeric substance.
Embodiment 11
The propylene oxide of 0.1mmolCAT-1 and 1mol and the mixture of epoxy cyclohexane are joined in the 500ml autoclave that process dewaters in advance, deoxygenation is handled, rapidly through having the CO of pressure regulatory function 2Supply line charges into CO in still 2To 2.0MPa, temperature was controlled at 60 ℃ of following stirring reactions 4 hours.Polyreaction is chilled to room temperature with reaction kettle after finishing, and slowly bleeds off carbonic acid gas, in-20 ℃ of cold-traps, collects unreacted epoxide simultaneously.In still, add a certain amount of methylene dichloride then; Make the copolymer mixture dissolving, add a certain amount of methanol extraction again and go out polycarbonate, the polymkeric substance that is settled out is used methanol wash; Multipolymer vacuum-drying after the washing obtains 26g white and gathers propylene carbonate to constant weight.Recording this polymkeric substance number-average molecular weight through gel permeation chromatography is 113000, MWD 1.26, 1The H-NMR analytical results shows that the cyclic carbonate by product is less than 2.0%, and carbonate unit content is higher than 99% in the polymkeric substance.
Embodiment 12
With behind the 0.1mmolCAT-2 with the propylene oxide of 1mol join in advance through dewatering, in the 500ml autoclave that deoxygenation is handled, rapidly through having the CO of pressure regulatory function 2Supply line charges into CO in still 2To 2.0MPa, temperature was controlled at 25 ℃ of following stirring reactions 4 hours.Polyreaction is chilled to room temperature with reaction kettle after finishing, and slowly bleeds off carbonic acid gas, in-20 ℃ of cold-traps, collects unreacted epoxide simultaneously.In still, add a certain amount of methylene dichloride then; Make the copolymer mixture dissolving, add a certain amount of methanol extraction again and go out polycarbonate, the polymkeric substance that is settled out is used methanol wash; Multipolymer vacuum-drying after the washing obtains 20g white and gathers propylene carbonate to constant weight.Recording this polymkeric substance number-average molecular weight through gel permeation chromatography is 98000, MWD 1.24, 1The H-NMR analytical results shows that the cyclic carbonate by product is less than 2.0%, and carbonate unit content is higher than 99% in the polymkeric substance.
Embodiment 13
With behind the 0.1mmolCAT-3 with the propylene oxide of 1mol join in advance through dewatering, in the 500ml autoclave that deoxygenation is handled, rapidly through having the CO of pressure regulatory function 2Supply line charges into CO in still 2To 2.0MPa, temperature was controlled at 25 ℃ of following stirring reactions 4 hours.Polyreaction is chilled to room temperature with reaction kettle after finishing, and slowly bleeds off carbonic acid gas, in-20 ℃ of cold-traps, collects unreacted epoxide simultaneously.In still, add a certain amount of methylene dichloride then; Make the copolymer mixture dissolving, add a certain amount of methanol extraction again and go out polycarbonate, the polymkeric substance that is settled out is used methanol wash; Multipolymer vacuum-drying after the washing obtains 20g white and gathers propylene carbonate to constant weight.Recording this polymkeric substance number-average molecular weight through gel permeation chromatography is 98000, MWD 1.24, 1The H-NMR analytical results shows that the cyclic carbonate by product is less than 2.0%, and carbonate unit content is higher than 99% in the polymkeric substance.
Embodiment 14
The propylene oxide of 0.1mmolCAT-4 and 1mol is joined in the 500ml autoclave that process dewaters in advance, deoxygenation is handled, rapidly through having the CO of pressure regulatory function 2Supply line charges into CO in still 2To 2.0MPa, temperature was controlled at 25 ℃ of following stirring reactions 6 hours.Polyreaction is chilled to room temperature with reaction kettle after finishing, and slowly bleeds off carbonic acid gas, in-20 ℃ of cold-traps, collects unreacted epoxide simultaneously.In still, add a certain amount of methylene dichloride then; Make the copolymer mixture dissolving, add a certain amount of methanol extraction again and go out polycarbonate, the polymkeric substance that is settled out is used methanol wash; Multipolymer vacuum-drying after the washing obtains 15g white and gathers propylene carbonate to constant weight.Recording this polymkeric substance number-average molecular weight through gel permeation chromatography is 87000, MWD 1.23, 1The H-NMR analytical results shows that the cyclic carbonate by product is less than 2.0%, and carbonate unit content is higher than 99% in the polymkeric substance.
Embodiment 15
The propylene oxide of 0.1mmolCAT-5 and 1mol is joined in the 500ml autoclave that process dewaters in advance, deoxygenation is handled, rapidly through having the CO of pressure regulatory function 2Supply line charges into CO in still 2To 2.0MPa, temperature was controlled at 25 ℃ of following stirring reactions 6 hours.Polyreaction is chilled to room temperature with reaction kettle after finishing, and slowly bleeds off carbonic acid gas, in-20 ℃ of cold-traps, collects unreacted epoxide simultaneously.In still, add a certain amount of methylene dichloride then; Make the copolymer mixture dissolving, add a certain amount of methanol extraction again and go out polycarbonate, the polymkeric substance that is settled out is used methanol wash; Multipolymer vacuum-drying after the washing obtains 22g white and gathers propylene carbonate to constant weight.Recording this polymkeric substance number-average molecular weight through gel permeation chromatography is 106000, MWD 1.25, 1The H-NMR analytical results shows that the cyclic carbonate by product is less than 2.0%, and carbonate unit content is higher than 99% in the polymkeric substance.
Embodiment 16
The propylene oxide of 0.1mmolCAT-6 and 1mol is joined in the 500ml autoclave that process dewaters in advance, deoxygenation is handled, rapidly through having the CO of pressure regulatory function 2Supply line charges into CO in still 2To 2.0MPa, temperature was controlled at 25 ℃ of following stirring reactions 6 hours.Polyreaction is chilled to room temperature with reaction kettle after finishing, and slowly bleeds off carbonic acid gas, in-20 ℃ of cold-traps, collects unreacted epoxide simultaneously.In still, add a certain amount of methylene dichloride then; Make the copolymer mixture dissolving, add a certain amount of methanol extraction again and go out polycarbonate, the polymkeric substance that is settled out is used methanol wash; Multipolymer vacuum-drying after the washing obtains 25g white and gathers propylene carbonate to constant weight.Recording this polymkeric substance number-average molecular weight through gel permeation chromatography is 156000, MWD 1.25, 1The H-NMR analytical results shows that the cyclic carbonate by product is less than 2.0%, and carbonate unit content is higher than 99% in the polymkeric substance.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.

Claims (10)

1. a structure is suc as formula the tetradentate schiff base metal complexes shown in (I):
Wherein, D 1, D 2, D 3, D 4, D 5, D 6, D 7, D 8Independently be selected from the substituting group of hydrogen, halogen, substituted aliphatic group, substituted assorted aliphatic group, substituted aryl, substituted heteroaryl or formula (III) structure separately, D 1, D 2, D 3, D 4, D 5, D 6, D 7, D 8In at least one is the substituting group of formula (III) structure:
Figure FDA0000128376190000012
Q is quaternary ammonium salt, quaternary alkylphosphonium salt or big sterically hindered organic bases group in the formula (III), and
Figure FDA0000128376190000013
is for connecting the linking group of tetradentate schiff base metal ligand and Q;
Ring A has formula (IV), formula V or formula (VI) structure:
Figure FDA0000128376190000014
D wherein 1a, D 2a, D 3a, D 4aIndependently be selected from hydrogen, halogen, substituted aliphatic group, substituted assorted aliphatic group, substituted aryl or substituted heteroaryl separately;
N is 1～4 positive integer in the formula V;
Y does not exist, or Y be halogen ,-NO 3, CH 3COO-, CCl 3COO-, CF 3COO-, C1O 4-, BF 4-, BPh 4-,-CN ,-N 3, p-methylbenzoic acid root, p-methyl benzenesulfonic acid root, o-NP oxygen, p-NP oxygen, m-nitrophenol oxygen, 2; 2, 4-dinitrophenol oxygen, 3-5 dinitrophenol(DNP) oxygen, 2; 4,6-trinitrophenol oxygen, 3,5-NSC 2879 oxygen, 3; 5-difluorophenol oxygen, 3,5-di-trifluoromethyl phenol oxygen or pentafluranol negative oxygen ion;
X is zinc, magnesium, manganese or iron.
2. tetradentate schiff base metal complexes according to claim 1 is characterized in that, said X is zinc or magnesium.
3. a structure is suc as formula the metalloporphyrin title complex shown in (II):
Figure FDA0000128376190000021
Wherein: R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20Independently be selected from the substituting group of hydrogen, halogen, substituted aliphatic group, substituted assorted aliphatic group, substituted aryl, substituted heteroaryl or formula (III) structure separately, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20In at least one is the substituting group of formula (III) structure:
Figure FDA0000128376190000022
Q is quaternary ammonium salt, quaternary alkylphosphonium salt or big sterically hindered organic bases group in the formula (III), and
Figure FDA0000128376190000023
is for connecting the linking group of metalloporphyrin part and Q;
M is zinc, magnesium, manganese or iron.
4. metalloporphyrin title complex according to claim 3 is characterized in that, said M is zinc or magnesium.
5. method for preparing polycarbonate comprises:
Under the katalysis of said formula (I) tetradentate schiff base metal complexes, carbonic acid gas and epoxide generation copolyreaction generate polycarbonate;
Figure FDA0000128376190000031
Wherein, D 1, D 2, D 3, D 4, D 5, D 6, D 7, D 8Independently be selected from the substituting group of hydrogen, halogen, substituted aliphatic group, substituted assorted aliphatic group, substituted aryl, substituted heteroaryl or formula (III) structure separately, D 1, D 2, D 3, D 4, D 5, D 6, D 7, D 8In at least one is the substituting group of formula (III) structure:
Figure FDA0000128376190000032
Q is quaternary ammonium salt, quaternary alkylphosphonium salt or big sterically hindered organic bases group in the formula (III), and
Figure FDA0000128376190000033
is for connecting the linking group of tetradentate schiff base metal ligand and Q;
Ring A has formula (IV), formula V or formula (VI) structure:
Figure FDA0000128376190000034
D wherein 1a, D 2a, D 3a, D 4aIndependently be selected from hydrogen, halogen, substituted aliphatic group, substituted assorted aliphatic group, substituted aryl or substituted heteroaryl separately;
N is 1～4 positive integer in the formula V;
Y does not exist, or Y be halogen ,-NO 3, CH 3COO-, CCl 3COO-, CF 3COO-, ClO 4-, BF 4-, BPh 4-,-CN ,-N 3, p-methylbenzoic acid root, p-methyl benzenesulfonic acid root, o-NP oxygen, p-NP oxygen, m-nitrophenol oxygen, 2; 2, 4-dinitrophenol oxygen, 3-5 dinitrophenol(DNP) oxygen, 2; 4,6-trinitrophenol oxygen, 3,5-NSC 2879 oxygen, 3; 5-difluorophenol oxygen, 3,5-di-trifluoromethyl phenol oxygen or pentafluranol negative oxygen ion;
X is zinc, magnesium, manganese or iron.
6. method for preparing polycarbonate comprises:
Under the katalysis of said formula (II) metalloporphyrin title complex, carbonic acid gas and epoxide generation copolyreaction generate polycarbonate;
Figure FDA0000128376190000041
Wherein: R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20Independently be selected from the substituting group of hydrogen, halogen, substituted aliphatic group, substituted assorted aliphatic group, substituted aryl, substituted heteroaryl or formula (III) structure separately, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20In at least one is the substituting group of formula (III) structure:
Q is quaternary ammonium salt, quaternary alkylphosphonium salt or big sterically hindered organic bases group in the formula (III), and
Figure FDA0000128376190000043
is for connecting the linking group of metalloporphyrin part and Q;
M is zinc, magnesium, manganese or iron.
7. according to claim 5 or 6 described methods, it is characterized in that the mol ratio of said title complex and epoxide is 1: (2000～200000).
8. according to claim 5 or 6 described methods, it is characterized in that the pressure of said carbonic acid gas is 0.1～8MPa.
9. according to claim 5 or 6 described methods, it is characterized in that the temperature of reaction of said copolyreaction is 20～120 ℃, the reaction times is 1～12h.
10. according to claim 5 or 6 described methods; It is characterized in that said epoxide is one or more in oxyethane, propylene oxide, 1-butylene oxide ring, 2-butylene oxide ring, epoxy cyclohexane, cyclopentane epoxide, epoxy chloropropane methyl propenoic acid glycidyl ether, methyl glycidyl ether, phenyl glycidyl ether and the vinylbenzene epoxy alkane.
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