CN113278143B - Efficient unsaturated carbon dioxide-based polyol and preparation method thereof - Google Patents
Efficient unsaturated carbon dioxide-based polyol and preparation method thereof Download PDFInfo
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Abstract
The invention provides an application of an aluminum porphyrin oligomer as a catalyst in preparation of unsaturated carbon dioxide-based polyol. The invention particularly adopts aluminum porphyrin oligomer with a specific structure shown in formula (III) to synthesize unsaturated carbon dioxide-based polyol with a specific structure shown in formula (I). The catalyst has excellent catalytic activity, polyol selectivity and proton tolerance in the synthesis process, breaks through the limitations of itaconic acid acidity and low-temperature polymerization, and enables efficient controllable synthesis of unsaturated carbon dioxide-based polyol to be possible. The synthesis method disclosed by the invention can accurately, efficiently and controllably synthesize unsaturated carbon dioxide-based polyol with active double bonds, and provides a convenient and feasible control platform for synthesis of various functionalized carbon dioxide-based polyurethane. And the method is simple and easy for industrial popularization and application.
Description
Technical Field
The invention belongs to the technical field of preparation of unsaturated carbon dioxide-based polyols, and relates to application of an aluminum porphyrin oligomer as a catalyst in preparation of unsaturated carbon dioxide-based polyols, an unsaturated carbon dioxide-based polyol and a preparation method thereof, in particular to high-efficiency unsaturated carbon dioxide-based polyol and a preparation method thereof, and application of the aluminum porphyrin oligomer as a catalyst in preparation of unsaturated carbon dioxide-based polyols.
Background
Carbon dioxide is a greenhouse gas and a renewable carbon-oxygen resource, and the high-value utilization of carbon dioxide in the chemical industry is a research hotspot in recent years. Among them, the research on the preparation of carbon dioxide-based polyols by telomerization of carbon dioxide and epoxides has received much attention. The carbon dioxide-based polyol has the structural characteristics of low molecular weight, hydroxyl end groups, coexistence of carbonate-ether and the like, can replace polyether or polyester polyol to synthesize carbon dioxide-based polyurethane, and is expected to become a next-generation basic raw material in the polyurethane industry. The proportion of the polyol in the polyurethane is more than 60%, so that the multidimensional effects of low cost, greenhouse gas emission reduction, petrochemical resource saving and the like on economic and environmental protection are brought. Furthermore, it is reported in the literature [ Green chem.,2016,18 (2): 524-530] that a polyurethane prepared from a carbon dioxide-based polyol has high mechanical strength and hydrolysis and oxidation resistance characteristics due to a special carbonate ether coexisting structure, in addition to the basic properties of a conventional polyurethane.
In the synthesis research of polyurethane, the functionalized unsaturated polyol can endow the polyurethane with special material properties to meet the requirements of specific applications. However, the varieties of the functionalized polyols are still single at present, the selectable range is limited to a multi-step synthesis method for introducing the functionalized additives, and the like, and the steps are complicated. Especially, the research on carbon dioxide-based polyol which can be used for post-modification is rarely reported, and the development of functionalized carbon dioxide-based polyurethane is limited. A universal strategy for synthesizing unsaturated polyol is to introduce a carbon-carbon double bond with high reaction activity, wherein the carbon-carbon double bond as a modifiable site can be crosslinked and solidified, and can also form a brush-type hyperbranched structure, or hydrophilic, antibacterial, flame-retardant and photoresponse functional groups are introduced through click chemistry, so that the polyol containing the carbon-carbon double bond is a platform for preparing various functional polyurethanes. The document [ Macromolecules,2020,53 (13): 5297-5307] reports that the terpolymerization of allyl glycidyl ether, propylene oxide and carbon dioxide can synthesize carbon dioxide-based polyols containing carbon-carbon double bonds, but the structure of the polyol prepared by the method is difficult to control accurately, and especially the position and the number of the double bonds are difficult to determine.
Therefore, finding a suitable method to accurately synthesize unsaturated carbon dioxide-based polyols is a major challenge in the development of this field and is one of the focuses of many researchers in this field.
Disclosure of Invention
The invention aims to provide unsaturated carbon dioxide-based polyol and a preparation method thereof, the unsaturated carbon dioxide-based polyol with a specific structure can be accurately, efficiently and controllably synthesized, and the method is simple and easy for industrial popularization and application.
The invention provides an application of an aluminum porphyrin oligomer as a catalyst in preparation of unsaturated carbon dioxide-based polyol;
the aluminum porphyrin oligomer has a structure shown in a formula (III);
x is selected from halo, -NO 3 、CH 3 COO-、CCl 3 COO-、CF 3 COO-、ClO 4 -、BF 4 -、BPh 4 -、-CN、-N 3 P-methylbenzoate, p-methylbenzenesulfonate, o-nitrophenol oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2, 4-dinitrophenol oxyanion, 3, 5-dinitrophenol oxyanion, 2,4, 6-trinitrophenol oxyanion, 3, 5-dichlorophenol oxyanion, 3, 5-difluorophenol oxyanion, 3, 5-bistrifluoromethylphenol oxyanion, pentafluorophenyl phenol oxyanion;
the R is 1 Selected from hydrogen, halogen, amino, nitro, cyano, substituted or unsubstituted C1-C10 aliphatic group, and substituted or unsubstituted C6-C30 aryl;
wherein n is the polymerization degree of the aluminum porphyrin oligomer.
Preferably, n is 4 to 20;
the preparation mode comprises telomerization;
the application specifically comprises the steps of taking an aluminum porphyrin oligomer as a catalyst and taking itaconic acid as an initiator;
the reactants for making the unsaturated carbon dioxide-based polyol include an epoxide and carbon dioxide.
The invention provides unsaturated carbon dioxide-based polyol which has a structure shown in a formula (I);
wherein x is the number of repeating units of carbonate units; y is the number of repeating units of the ether unit;
and R is selected from hydrogen, C1-C10 alkyl, phenyl, chloroalkyl, cyclohexyl and cyclopentyl.
Preferably, x is 2 to 25;
y is 2 to 25;
the R is methyl;
the unsaturated carbon dioxide-based polyol includes an ultra-low molecular weight unsaturated carbon dioxide-based polyol.
Preferably, the unsaturated carbon dioxide-based polyol has a structure in which an itaconate ester is used as a core and a carbonate segment and an ether segment coexist;
in the unsaturated carbon dioxide-based polyol, the content of a carbonic ester chain segment is 10-70%;
the molecular weight of the unsaturated carbon dioxide-based polyol is 1000-5000 g/mol.
The invention also provides a preparation method of the unsaturated carbon dioxide-based polyol, which comprises the following steps:
taking an aluminum porphyrin oligomer as a catalyst and itaconic acid as an initiator, and carrying out telomerization on epoxide and carbon dioxide to obtain unsaturated carbon dioxide-based polyol.
Preferably, the aluminum porphyrin oligomer has a structure shown in a formula (III);
x is selected from halo, -NO 3 、CH 3 COO-、CCl 3 COO-、CF 3 COO-、ClO 4 -、BF 4 -、BPh 4 -、-CN、-N 3 P-methylbenzoate, p-methylbenzenesulfonate, o-nitrophenol oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2, 4-dinitrophenol oxyanion, 3, 5-dinitrophenol oxyanion2,4, 6-trinitrophenol oxyanion, 3, 5-dichlorophenol oxyanion, 3, 5-difluorophenol oxyanion, 3, 5-bistrifluoromethylphenol oxyanion, pentafluorophenyl phenol oxyanion;
said R is 1 Selected from hydrogen, halogen, amino, nitro, cyano, substituted or unsubstituted C1-C10 aliphatic group, and substituted or unsubstituted C6-C30 aryl;
wherein n is the polymerization degree of the aluminum porphyrin oligomer.
Preferably, n is 4 to 20;
the aluminum porphyrin oligomer has a structure shown in a formula (III-1) or a formula (III-2);
preferably, the epoxide comprises one or more of ethylene oxide, propylene oxide, 1-butylene oxide, 2-butylene oxide, cyclohexene oxide, cyclopentane epoxide, epichlorohydrin, glycidyl methacrylate, methyl glycidyl ether, phenyl glycidyl ether, styrene alkylene oxide, 4-vinyl-1, 2-cyclohexene oxide and vinyl propylene oxide;
the molar ratio of the catalyst to the initiator is 50000: (10-50);
the molar ratio of the epoxy compound to the initiator is 1: (10 to 50).
Preferably, the pressure of the carbon dioxide is 0.1-10 MPa;
the temperature of the telomerization reaction is 25-80 ℃;
the telomerization time is 0.5-24 h;
the content of cyclic carbonate as a by-product of the telomerization reaction is less than 1%.
The invention provides an application of an aluminum porphyrin oligomer as a catalyst in preparation of unsaturated carbon dioxide-based polyol; the aluminum porphyrin oligomer has a structure shown in a formula (III). Unsaturated carbon dioxide-based polyols and methods of making the same are also provided. Compared with the prior art, the aluminum porphyrin oligomer with the specific structure of the formula (III) is particularly adopted for synthesizing the unsaturated carbon dioxide-based polyol with the specific structure of the formula (I). The catalyst has excellent catalytic activity, polyol selectivity and proton tolerance in the synthesis process. The aluminum porphyrin oligomer provided by the invention has highly controllable polymerization degree, and the catalyst is soluble in a reaction system and is a high-activity catalyst with homogeneous catalysis and multi-center catalysis; under the multi-center concerted catalysis, itaconic acid does not participate in the reaction under the action of chain transfer, but directly promotes the insertion polymerization of epoxide and carbon dioxide in the form of an initiator after being deprotonated directly; therefore, the aluminum porphyrin oligomer catalyst has good proton tolerance, breaks through the limitations of itaconic acid acidity and low-temperature polymerization, and makes the efficient and controllable synthesis of unsaturated carbon dioxide-based polyol possible.
Due to epoxide/CO 2 The telomerization reaction has the characteristic of active polymerization, namely, one initiator corresponds to one polymer chain, the proton of the initiator forms a terminal hydroxyl group, and the rest part of the initiator is positioned in the chain, so that the accuracy of the structure control of the unsaturated polyol can be greatly improved by selecting the proper initiator containing carbon-carbon double bonds. Based on the aluminum porphyrin oligomer catalyst provided by the invention, itaconic acid can be selected as an initiator, and the preparation of telomerization and polymerization functionalized carbon dioxide-based polyol is realized. And itaconic acid is unsaturated dicarboxylic acid of biological source, and the green chemical attribute of polyol synthesis can be further improved on the basis of carbon dioxide utilization by substituting itaconic acid for petrochemical initiator.
The invention carries out telomerization reaction on epoxide, carbon dioxide and itaconic acid under the action of a catalyst to obtain the carbon dioxide-based polycarbonate ether polyol containing unsaturated carbon-carbon double bonds. The aluminum porphyrin oligomer catalyst has excellent catalytic activity, polyol selectivity and proton tolerance. The unsaturated carbon dioxide-based polyol with the specific structure takes itaconic acid ester as a core, and has a structure in which a carbonate segment and an ether segment coexist, wherein the content of the carbonate segment is between 10 and 70 percent; the molecular weight of the polyhydric alcohol is between 1000 and 5000 g/mol; the content of cyclic carbonate as a by-product is less than 1%.
The synthesis method disclosed by the invention can accurately, efficiently and controllably synthesize the unsaturated carbon dioxide-based polyol with a specific structure and active double bonds, and provides a convenient and feasible control platform for synthesizing various functionalized carbon dioxide-based polyurethanes. And the method is simple and easy for industrial popularization and application.
Experimental results show that the synthesis of itaconic acid type unsaturated carbon dioxide-based polyol can be efficiently catalyzed by using the aluminum porphyrin oligomer under the condition of extremely low catalyst concentration with the mole ratio of propylene oxide/aluminum center of 50000/1, the monomer can realize nearly 100% conversion, and the content of the by-product cyclic carbonate is controlled within 1%; meanwhile, the aluminum porphyrin oligomer catalyst shows high activity, the catalytic efficiency is over 200 g/(g.h), and the conversion frequency (TOF) reaches 2080 to 2500h according to the mole number of aluminum centers -1 Left and right; the polyol product has an adjustable structure, wherein the content of a carbonic ester chain segment is between 10 and 70 percent, and the molecular weight is between 1000 and 5000g/mol, so that the accurate regulation and control can be realized, and different requirements of downstream polyurethane production can be met.
Drawings
FIG. 1 is a diagram of the product prepared in example 2 of the present invention 1 H NMR spectrum;
FIG. 2 is a time-of-flight mass spectrum characterization of the product prepared in example 2 of the present invention;
FIG. 3 is a DSC plot of the preparation of example 2 of the present invention;
FIG. 4 is a GPC characterization chart of the product prepared in example 4 of the present invention;
FIG. 5 is a graph of monomer/starter charge ratio versus product molecular weight for example 4 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All of the starting materials of the present invention are not particularly limited in their purity, and the present invention preferably employs the purity of conventional materials used in the field of analytically pure or carbon dioxide-based polyol synthesis.
All noun expressions, acronyms, and designations of the present invention are commonly known in the art and are clearly understood in the relevant fields of application, and a person skilled in the art can clearly, accurately, and uniquely understand the noun expressions, acronyms, and designations.
The invention discloses application of aluminum porphyrin oligomer as a catalyst in preparation of unsaturated carbon dioxide-based polyol;
the aluminum porphyrin oligomer has a structure shown in a formula (III);
x is selected from halo, -NO 3 、CH 3 COO-、CCl 3 COO-、CF 3 COO-、ClO 4 -、BF 4 -、BPh 4 -、-CN、-N 3 P-methylbenzoate, p-methylbenzenesulfonate, o-nitrophenol oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2, 4-dinitrophenol oxyanion, 3, 5-dinitrophenol oxyanion, 2,4, 6-trinitrophenol oxyanion, 3, 5-dichlorophenol oxyanion, 3, 5-difluorophenol oxyanion, 3, 5-bistrifluoromethylphenol oxyanion, pentafluorophenyl phenol oxyanion;
said R is 1 Selected from hydrogen, halogen, amino, nitro, cyano, substituted or unsubstituted C1-C10 aliphatic group, and substituted or unsubstituted C6-C30 aryl;
wherein n is the polymerization degree of the aluminum porphyrin oligomer.
In the present invention, the X is more preferably a halogen group, and may include one or more of fluorine, chlorine, bromine and iodine, and may be chlorine.
In the present invention, said R 1 Is selected from hydrogen, halogen, amino, nitro, cyano, substituted or unsubstituted C1-C10 aliphatic group and substituted or unsubstituted C6-C30 aryl. Among them, the aliphatic group having 1 to 10 carbon atoms is preferably an aliphatic group having 2 to 9 carbon atoms, more preferably an aliphatic group having 3 to 8 carbon atoms, still more preferably an aliphatic group having 4 to 7 carbon atoms, and particularly may be an aliphatic group having 1 to 6 carbon atoms. The aryl group having 6 to 30 carbon atoms is preferably an aryl group having 8 to 25 carbon atoms, more preferably an aryl group having 10 to 20 carbon atoms, and still more preferably an aryl group having 12 to 16 carbon atoms.
In the present invention, n is the polymerization degree of the aluminum porphyrin oligomer, and is preferably 4 to 20, more preferably 6 to 18, more preferably 8 to 16, and more preferably 10 to 14. And may be specifically 12.
In the present invention, the mode of preparation preferably includes telomerization.
In the present invention, the application is particularly preferably that aluminum porphyrin oligomer is used as a catalyst, and itaconic acid is used as an initiator.
In the present invention, the itaconic acid preferably has a structure represented by (II):
in the present invention, the reactants for preparing the unsaturated carbon dioxide-based polyol preferably comprise an epoxide and carbon dioxide.
One of the key points of the invention is to provide the catalyst with the structure shown in the formula (III), the aluminum porphyrin oligomer catalyst is prepared by an 'activity'/controllable free radical technology, and the polymerization degree of the catalyst is highly controllable, so that the catalyst is soluble in a reaction system and is a high-activity catalyst with homogeneous catalysis and multi-center catalysis; under the multi-center concerted catalysis, itaconic acid does not participate in the reaction under the action of chain transfer, but directly promotes the insertion polymerization of epoxide and carbon dioxide in the form of an initiator after being subjected to deprotonation; therefore, the aluminum porphyrin oligomer catalyst has good proton tolerance, breaks through the limitations of itaconic acid acidity and low-temperature polymerization, and makes efficient and controllable synthesis of unsaturated carbon dioxide-based polyol possible.
Therefore, the method is applied to the preparation of the carbon dioxide polyol with ultra-low molecular weight, and solves the difficulty that itaconic acid is used as an initiator and the catalytic technology is challenged. First, there is a problem of compatibility of the itaconic acid initiator with the catalyst, the pK of itaconic acid a1 3.84, the acidity is stronger, while the general double metal cyanide catalyst can generate a long induction period under the condition of strong acid, and the selectivity of the polyol is poorer; secondly, carbon-carbon double bonds in the itaconic acid and a carboxyl have a conjugated structure, so that the reaction activity of the itaconic acid is higher, and in order to avoid the complicated protection-deprotection operation, the one-pot preparation is carried out at a lower reaction temperature, so that the catalyst activity is greatly reduced.
The invention provides unsaturated carbon dioxide-based polyol which has a structure shown in a formula (I);
wherein x is the number of repeating units of carbonate units; y is the number of repeating units of the ether unit;
and R is selected from hydrogen, C1-C10 alkyl, phenyl, chloroalkyl, cyclohexyl and cyclopentyl. The alkyl group may be a C1-C8 alkyl group or a C1-C6 alkyl group. Specifically, R is preferably methyl.
In the unsaturated carbon dioxide-based polyol of the present invention, x is preferably 2 to 25, more preferably 3 to 20, more preferably 4 to 15, and more preferably 5 to 10. The y is preferably 2 to 25, more preferably 3 to 22, more preferably 4 to 18, and more preferably 5 to 15.
In the present invention, the unsaturated carbon dioxide-based polyol preferably has a structure in which an itaconate ester is used as a core and a carbonate segment and an ether segment coexist.
In the present invention, the content of the carbonate segment in the unsaturated carbon dioxide-based polyol is preferably 10% to 70%, more preferably 20% to 60%, and still more preferably 30% to 50%.
In the present invention, the unsaturated carbon dioxide-based polyol preferably includes an ultra-low molecular weight unsaturated carbon dioxide-based polyol, and specifically, the molecular weight of the unsaturated carbon dioxide-based polyol is preferably 1000 to 5000g/mol, more preferably 1500 to 4500g/mol, more preferably 2000 to 4000g/mol, and more preferably 2500 to 3500g/mol.
The invention provides a preparation method of unsaturated carbon dioxide-based polyol, which comprises the following steps:
taking an aluminum porphyrin oligomer as a catalyst and itaconic acid as an initiator, and carrying out telomerization on epoxide and carbon dioxide to obtain unsaturated carbon dioxide-based polyol.
In the present invention, the aluminoporphyrin oligomer has a structure represented by formula (III);
x is selected from halo, -NO 3 、CH 3 COO-、CCl 3 COO-、CF 3 COO-、ClO 4 -、BF 4 -、BPh 4 -、-CN、-N 3 P-methylbenzoate, p-methylbenzenesulfonate, o-nitrophenol oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2, 4-dinitrophenol oxyanion, 3, 5-dinitrophenol oxyanion, 2,4, 6-trinitrophenol oxyanion, 3, 5-dichlorophenol oxyanion, 3, 5-difluorophenol oxyanion, 3, 5-bistrifluoromethylphenol oxyanion, pentafluorophenyl phenol oxyanion;
the R is 1 Selected from hydrogen, halogen, amino, nitro, cyano, substituted or unsubstituted C1-C10 aliphatic group, and substituted or unsubstituted C6-C30 aryl;
wherein n is the polymerization degree of the aluminum porphyrin oligomer.
In the present invention, n is the polymerization degree of the aluminum porphyrin oligomer, and is preferably 4 to 20, more preferably 6 to 18, more preferably 8 to 16, and more preferably 10 to 14. And may be specifically 12.
In the present invention, the aluminum porphyrin oligomer preferably has a structure represented by the formula (III-1) or (III-2);
in the present invention, the epoxide preferably includes one or more of ethylene oxide, propylene oxide, 1-butylene oxide, 2-butylene oxide, cyclohexene oxide, cyclopentane oxide, epichlorohydrin, glycidyl methacrylate, methyl glycidyl ether, phenyl glycidyl ether, styrene alkylene oxide, 4-vinyl-1, 2-cyclohexene oxide, and vinyl propylene oxide, and more preferably one or more of ethylene oxide, propylene oxide, 1-butylene oxide, 2-butylene oxide, cyclohexane oxide, cyclopentane oxide, epichlorohydrin, glycidyl methacrylate, methyl glycidyl ether, phenyl glycidyl ether, styrene alkylene oxide, 4-vinyl-1, 2-cyclohexene oxide, or vinyl propylene oxide.
The source of the aluminum porphyrin oligomer is not particularly limited in principle, the aluminum porphyrin oligomer can be prepared or purchased by a preparation method well known to those skilled in the art, the invention is a complete and refined integral technical scheme, the structure of the prepared unsaturated carbon dioxide-based polyol is better ensured, the accurate, efficient and controllable synthesis of the unsaturated carbon dioxide-based polyol is ensured, and the preparation method of the aluminum porphyrin oligomer catalyst with the structure of the formula (III) preferably comprises the following steps: asymmetric porphyrin synthesis, porphyrin monomer preparation, reversible addition-fragmentation chain transfer polymerization and metallization:
specifically, the method comprises the following steps:
asymmetric porphyrin synthesis: the preparation method adopts a propionic acid one-pot method, namely, under the condition of propionic acid reflux, p-hydroxybenzaldehyde, substituted benzaldehyde and pyrrole are reacted in one pot to obtain 6 kinds of porphyrin, and after the reaction is finished, a second color band is collected by a column chromatography separation technology to obtain monohydroxy substituted porphyrin;
preparation of porphyrin monomer: acylation reaction is adopted, namely, the substitution reaction of hydroxyl and acyl chloride in tetrahydrofuran solution under alkaline condition;
reversible addition-fragmentation chain transfer polymerization: dissolving porphyrin monomer, RAFT reagent trithioester and initiator Azobisisobutyronitrile (AIBN) in THF under anhydrous and anaerobic conditions, wherein the dosage of the initiator is 1/2 of the trithioester, and the molar ratio of porphyrin monomer to trithioester is 10/1-20/1. Three times of freeze-drying and oxygen removal treatment are needed before polymerization, and after the polymerization is finished, the reaction bottle is placed in liquid nitrogen to quench free radicals. Dissolving the unreacted porphyrin monomer in diethyl ether, separating the monomer from the oligomer by a centrifugal method, dissolving the cold diethyl ether-dichloromethane precipitate for three times, and finishing the separation if the diethyl ether solution is in a light pink state;
metallization reaction: the basic operation steps are that oligomeric porphyrin ligand is dissolved in dichloromethane in a glove box, n-hexane solution of diethyl aluminum chloride is dripped to react for 3 hours at normal temperature, and after the reaction is finished, column chromatography separation and purification are carried out.
In the present invention, the molar ratio of the catalyst to the initiator is preferably 50000: (10 to 50), more preferably 50000: (12 to 40), more preferably 50000: (15 to 30).
In the present invention, the molar ratio of the epoxy compound to the initiator is preferably 1: (10 to 50), more preferably 1: (12 to 40), more preferably 1: (15 to 30).
In the present invention, the pressure of the carbon dioxide is preferably 0.1 to 10MPa, more preferably 0.1 to 8MPa, and still more preferably 0.1 to 6MPa.
In the present invention, the temperature of the telomerization is preferably 25 to 80 ℃, more preferably 35 to 70 ℃, preferably 45 to 60 ℃, and particularly 60 ℃.
In the present invention, the time for the telomerization is preferably 0.5 to 24 hours, more preferably 6 to 22 hours, and still more preferably 12 to 20 hours.
In the present invention, the content of cyclic carbonate as a by-product of the telomerization reaction is preferably less than 1%, more preferably less than 0.5%, and still more preferably less than 0.3%.
The preparation method of the unsaturated carbon dioxide-based polyol is a complete and refined integral preparation method, better ensures the structure of the unsaturated carbon dioxide-based polyol, and ensures the accurate, efficient and controllable synthesis of the unsaturated carbon dioxide-based polyol, and particularly comprises the following steps:
the polymerization was carried out in a high-pressure autoclave equipped with magnetic stirring. In a glove box, epoxide, aluminum porphyrin oligomer catalyst and required itaconic acid are added into a reaction kettle which is subjected to water removal treatment at room temperature, and then the reaction kettle is placed in a water bath at 60 ℃ and is filled with required CO 2 Cooling the reaction kettle to room temperature after the reaction is finished, and slowly releasing residual CO 2 Opening the reaction kettle to take out a few drops of reaction stock solution for 1 And (4) performing H-NMR test, dissolving the rest products by using a good solvent, settling in a poor solvent, centrifuging to remove a supernatant, dissolving and precipitating for three times, and then performing vacuum drying. For the experimental group with complete conversion of the epoxide, the polyol can be subjected to the next polyurethane synthesis without post-treatment, since there are only trace amounts of by-products.
The preparation technology of the ultra-low molecular weight carbon dioxide polyol provided by the invention has the difficulty that the itaconic acid is used as an initiator to face the challenge in the aspect of catalysis technology. First, there is a problem of compatibility of the itaconic acid initiator with the catalyst, the pK of itaconic acid a1 3.84, which is relatively strong in acidity, while the conventional double metal cyanide catalysts can generate a long induction period under the condition of strong acid, and the selectivity of the polyol is relatively poor; secondly, a carbon-carbon double bond in the itaconic acid and a carboxyl group have a conjugated structure, so that the reaction activity is higher, and in order to avoid the complex protection-deprotection operation, the one-pot preparation is carried out at a lower reaction temperature, so that the activity of the catalyst is greatly reduced.
The aluminum porphyrin oligomer catalyst with the structure of formula (III) is prepared by an 'activity'/controllable free radical technology, and the polymerization degree of the aluminum porphyrin oligomer catalyst is highly controllable, so that the catalyst is soluble in a reaction system and is a high-activity catalyst with both homogeneous catalysis and multi-center catalysis; under the multi-center concerted catalysis, itaconic acid does not participate in the reaction under the action of chain transfer, but directly promotes the insertion polymerization of epoxide and carbon dioxide in the form of an initiator after being subjected to deprotonation; therefore, the aluminum porphyrin oligomer catalyst has good proton tolerance, breaks through the limitations of itaconic acid acidity and low-temperature polymerization, and makes the high-efficiency controllable synthesis of unsaturated carbon dioxide-based polyol possible.
The invention provides application of an aluminum porphyrin oligomer as a catalyst in preparation of unsaturated carbon dioxide-based polyol, unsaturated carbon dioxide-based polyol and a preparation method thereof. The invention particularly adopts aluminum porphyrin oligomer with a specific structure to synthesize unsaturated carbon dioxide-based polyol with a specific structure. The catalyst has excellent catalytic activity, polyol selectivity and proton tolerance in the synthesis process. The aluminum porphyrin oligomer has highly controllable polymerization degree, and the catalyst is soluble in a reaction system and is a high-activity catalyst with homogeneous catalysis and multi-center catalysis; under the multi-center concerted catalysis, itaconic acid does not participate in the reaction under the action of chain transfer, but directly promotes the insertion polymerization of epoxide and carbon dioxide in the form of an initiator after being subjected to deprotonation; therefore, the aluminum porphyrin oligomer catalyst has good proton tolerance, breaks through the limitations of itaconic acid acidity and low-temperature polymerization, and makes the high-efficiency controllable synthesis of unsaturated carbon dioxide-based polyol possible.
Due to epoxide/CO 2 The telomerization reaction has the characteristic of active polymerization, namely, one initiator corresponds to one polymer chain, the proton of the initiator forms a terminal hydroxyl group, and the rest part of the initiator is positioned in the chain, so that the accuracy of the structure control of the unsaturated polyol can be greatly improved by selecting the proper initiator containing carbon-carbon double bonds. Based on the aluminum porphyrin oligomer catalyst provided by the invention, itaconic acid can be selected as an initiator, and the preparation of telomerization and polymerization functionalized carbon dioxide-based polyol is realized. And itaconic acid is unsaturated dicarboxylic acid of biological source, and the green chemical attribute of polyol synthesis can be further improved on the basis of carbon dioxide utilization by substituting itaconic acid for petrochemical initiator.
Under the action of a catalyst, epoxide, carbon dioxide and itaconic acid are subjected to telomerization reaction to obtain carbon dioxide-based polycarbonate ether polyol containing unsaturated carbon-carbon double bonds. The aluminum porphyrin oligomer catalyst has excellent catalytic activity, polyol selectivity and proton tolerance. The unsaturated carbon dioxide-based polyol with the specific structure takes itaconic acid ester as a core and has a structure in which a carbonate segment and an ether segment coexist, and the content of the carbonate segment is between 10 and 70 percent; the molecular weight of the polyalcohol is between 1000 and 5000 g/mol; the content of cyclic carbonate as a by-product is less than 1%.
The synthesis method disclosed by the invention can accurately, efficiently and controllably synthesize the unsaturated carbon dioxide-based polyol with a specific structure and active double bonds, and provides a convenient and feasible control platform for synthesizing various functionalized carbon dioxide-based polyurethanes. And the method is simple and easy for industrial popularization and application.
Experimental results show that the synthesis of itaconic acid type unsaturated carbon dioxide-based polyol can be efficiently catalyzed by adopting aluminum porphyrin oligomer under the condition of extremely low catalyst concentration with the mole ratio of propylene oxide/aluminum center of 50000/1, the monomer can realize near 100% conversion, and the content of by-product cyclic carbonate is controlled within 1%; meanwhile, the aluminum porphyrin oligomer catalyst shows high activity, the catalytic efficiency is over 200 g/(g.h), and the conversion frequency (TOF) reaches 2080 to 2500h according to the mole number of aluminum centers -1 Left and right; the polyol product has adjustable structure, wherein the content of the carbonic ester chain segment is between 10 and 70 percent, and the molecular weight is between 1000 and 5000g/mol, so that the accurate regulation and control can be realized, and different requirements of downstream polyurethane production can be met.
For further illustration of the present invention, the application of the aluminum porphyrin oligomer as a catalyst in the preparation of unsaturated carbon dioxide-based polyol, an unsaturated carbon dioxide-based polyol and a preparation method thereof are described in detail in the following with reference to the following examples, but it should be understood that the examples are carried out on the premise of the technical scheme of the present invention, and the detailed embodiments and specific procedures are given only for further illustration of the features and advantages of the present invention, but not for limitation of the claims of the present invention, and the scope of the present invention is not limited to the following examples.
Example 1
Preparation of aluminum porphyrin oligomer catalyst
Adding p-hydroxybenzaldehyde (13.2g, 108mmol) and p-bromobenzaldehyde (59.74g, 324mmol) into 500mL propionic acid, heating to 130 deg.C, adding pyrrole (30mL, 432mmol) dropwise, heating to 160 deg.C, refluxing for 2h, cooling to room temperature after reaction, adding methanol, cooling in refrigerator overnight, filtering to obtain product, and performing silica gel column chromatography (CHCl) 3 /CH 3 OH) to collect the second color band and yield approximately 12% of product EL 1.
1 H NMR(300MHz,CDCl 3 )δ＝8.91,8.10,7.92,7.15,-2.82MS(MALDI-ToF):[C44H27Br3N4O],m/z＝863.9[M+H] + (calcd.863.9)。
EL1 (0.86g, 1mmol), triethylamine (0.12g, 1.2mmol) and anhydrous tetrahydrofuran were charged into a 100-ml reaction flask, and the reaction flask was cooled in an ice-water bath. Methacryloyl chloride (0.124g, 1.2mmol) was dissolved in 10mL of anhydrous tetrahydrofuran and added dropwise to the reaction flask, and the reaction was stirred at room temperature overnight. After the reaction, the product was filtered, dried, dissolved in dichloromethane, washed 3 times with sodium chloride solution, dried over anhydrous magnesium sulfate, and the crude product was subjected to column chromatography using dichloromethane to obtain the product EL2 with a yield of 88.2%.
1 H NMR(300MHz,CDCl 3 )δ＝8.93,8.23,7.93,7.58,6.59,5.94,2.13,-2.83.MS(MALDI-ToF):[C48H31Br3N4O2],m/z＝935.5[M+H] + (calcd.935.5)。
EL2 (0.56g, 0.6 mmol), 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid (DDMAT) (11mg, 0.03mmol), AIBN (2.5mg, 0.015mmol) and 25mL tetrahydrofuran are added into a Schlenk reaction tube, oxygen is removed by freezing for 3 times, nitrogen is filled, reaction is carried out for 24 hours at 65 ℃, liquid nitrogen is quenched, precipitate is collected after centrifugation by cold ether precipitation, dichloromethane-cold ether is used for repeated dissolution and centrifugation for 5 times, and oligomeric porphyrin ligand EL3 is obtained after vacuum drying, wherein the yield is 45%.
Gel permeation chromatography (GPC, PS standard, CH) 2 Cl 2 ):Mn＝13600,PDI＝1.67。
Dissolving the ligand EL3 in dichloromethane, and dropwise adding equivalent AlEt 2 Cl (diethylaluminum chloride) (2 mol in hexane), the reaction was stirred at room temperature for 3h. And (4) vacuumizing the solvent and drying to obtain the aluminum porphyrin oligomer catalyst.
Example 2
Preparation of polyols
Propylene oxide (150mL, 2.14mol), itaconic acid (9.3g, 71.3mmol, i.e., [ propylene oxide ]]/[ itaconic acid]At a molar ratio of 30/1) and the aluminoporphyrin oligomer catalyst prepared in example 1 (0.043 g,0.043mmol, [ Al ], [ 0.043mmol ]]I.e., [ propylene oxide ]]/[Al]50000/1) is added into a 500ml high-pressure reaction kettle which is subjected to water removal and oxygen removal in advance, and CO with the pressure regulation function is rapidly passed through 2 The supply line is filled with CO into the kettle 2 The reaction was stirred for 20 hours at a pressure of 3MPa and a temperature of 60 ℃. After the polymerization reaction is finished, the reaction kettle is cooled to room temperature, and carbon dioxide is slowly discharged.
The crude product is first subjected to 1 H-NMR measurement gave a PO conversion of 96.2%, cyclic carbonate by-product of 0.4% and a carbonate segment content of 41.6%. The resulting product was dried under vacuum to remove unreacted propylene oxide and purified by gel permeation chromatography (GPC, PEG standard, CH) 2 Cl 2 ) The polymer was found to have a number average molecular weight of 2200g/mol and a molecular weight distribution of 1.10.
Referring to FIG. 1, FIG. 1 is a schematic representation of the product of example 2 of the present invention 1 H NMR spectrum.
The product prepared in example 2 of the invention was characterized by time-of-flight mass spectrometry, the results of which are shown in FIG. 2. FIG. 2 is a time-of-flight mass spectrum characterization of the product prepared in example 2 of the present invention.
The product prepared in example 2 of the present invention was subjected to DSC testing and the results are shown in figure 3. FIG. 3 is a DSC chart of the product of example 2 of the present invention.
Example 3
Carbonate content regulation of polyols
Propylene oxide (150mL, 2.14mol), itaconic acid (9.3g, 71.3mmol, i.e., [ propylene oxide ]]/[ itaconic acid]Has a molar ratio of 30/1) and the aluminum porphyrin oligomer catalyst prepared in example 1 (0.043g, 0.043mmol, [ 2 Al ], [ 2 ] Al]I.e., [ propylene oxide ]]/[Al]Is 50000/1) is added into a 500ml high-pressure reaction kettle which is subjected to water removal and oxygen removal in advance, and CO with the pressure regulation function is rapidly passed through 2 The supply line is filled with CO into the kettle 2 The reaction was stirred for 20 hours at a pressure of 0.8MPa and a temperature of 60 ℃. After the polymerization reaction is finished, the reaction kettle is cooled to room temperature, and carbon dioxide is slowly discharged.
The crude product is first subjected to 1 H-NMR measurements gave a close equivalent conversion of PO (99.9%), cyclic carbonate by-product of 0.6%, and carbonate segment content of 15.9%.
The resulting product was dried under vacuum to remove unreacted propylene oxide and purified by gel permeation chromatography (GPC, PEG standard, CH) 2 Cl 2 ) The polymer was found to have a number average molecular weight of 2000g/mol and a molecular weight distribution of 1.12.
In addition, other reaction conditions are ensured to be unchanged, and CO is changed 2 The pressure is 1.5MPa, 3.0MPa and 4.5MPa, and the content of the carbonic ester chain segment of the product is 32.2 percent, 41.6 percent and 51.7 percent respectively; thus by changing CO 2 The pressure can be adjusted to control the carbonate content of the polyol, and specific data are shown in table 1. Table 1 shows the parameters and the ratios of the reactions in example 3. Wherein PO/IA is the molar ratio of propylene oxide to itaconic acid, and CU% is the carbonate content.
TABLE 1
Example 4
Molecular weight control of polyols
Propylene oxide (150mL, 2.14mol), itaconic acid (11.6g, 89.2mmol, [ propylene oxide ]]/[ itaconic acid]Has a molar ratio of 24/1) and the aluminum porphyrin oligomer catalyst prepared in example 1 (0.043g, 0.043mmol, [ 2 Al ], [ 2 ] Al]I.e., [ propylene oxide ]]/[Al]50000/1) is added into a 500ml high-pressure reaction kettle which is subjected to water removal and oxygen removal in advance, and CO with the pressure regulation function is rapidly passed through 2 The supply line is filled with CO in the kettle 2 The reaction was stirred at 60 ℃ for 24 hours while the pressure was 4.5 MPa. After the polymerization reaction is finished, the reaction kettle is cooled to room temperature, and carbon dioxide is slowly discharged.
The crude product is first subjected to 1 H-NMR measurements gave a close equivalent conversion of PO (99.9%), cyclic carbonate by-product of 1.1% and carbonate segment content of 49.2%. The resulting product was dried under vacuum to remove unreacted propylene oxide and purified by gel permeation chromatography (GPC, PEG standard, CH) 2 Cl 2 ) The polymer was found to have a number average molecular weight of 1900g/mol and a molecular weight distribution of 1.07.
In addition, the molar ratios of propylene oxide and itaconic acid were varied to 30/1, 40/1 and 50/1, and the molecular weights and distributions of the products were 2200 (1.07), 3400 (1.09) and 3800 (1.10), respectively, while maintaining other reaction conditions.
The GPC chart is shown in FIG. 4. FIG. 4 is a GPC characterization of the product prepared in example 4 of the present invention.
The results show that the 4 groups of polymerization products have unimodal distribution and molecular weight distribution less than 1.10, and represent excellent living polymerization characteristics; because the monomer is completely converted and the selectivity is not fluctuated, the molar ratio of the propylene oxide/the itaconic acid and the molecular weight of the polyalcohol form a good linear relation, and the correlation coefficient R 2 Is 0.979, see fig. 5. FIG. 5 is a graph of monomer/starter charge ratio versus product molecular weight for example 4 of the present invention.
See table 2, table 2 for parameters and ratios of the reactions in example 4.
TABLE 2
Example 5
Reaction history monitoring
To more intuitively express the formation of unsaturated carbon dioxide based polyols under the action of aluminoporphyrin oligomers and itaconic acid, we used in situ infrared for reaction history monitoring. The three-dimensional spectrogram is displayed at 1800cm -1 The nearby characteristic peak attributed to the carbonyl group in the cyclic carbonate is not detected in the whole reaction process, which proves the high polyol selectivity of the aluminum porphyrin oligomer catalyst in the telomerization reaction. The first 30min belongs to the initiation period, 1104cm -1 The intensity of the characteristic peak ascribed to C-O in polyether was unchanged, whereas 1745cm -1 The signal intensity attributed to the carbonyl group in the linear carbonate increased slightly, and the signal change resulted from the increased concentration of itaconic acid in solution. Itaconic acid itself is slightly soluble in propylene oxide, a dissolution equilibrium exists before the reaction, and the reaction of itaconic acid with propylene oxide promotes the equilibrium to move towards the dissolution direction. After an initiation period of 30min, chain growth began. CO 2 2 The ring-opening copolymerization reaction of the propylene oxide and the homopolymerization reaction of the propylene oxide are simultaneously carried out and are also simultaneously close to finish, and the rate ratio of the two is not changed along with time, so that the structural sequence of the product has no obvious gradient change, and the stable and controllable preparation process is embodied.
Example 6
Substrate suitability for epoxides
1, 2-butylene oxide (150mL, 1.73mol), itaconic acid (7.5g, 57.6mmol, [ propylene oxide ]]/[ itaconic acid]In a molar ratio of 30/1) and the aluminoporphyrin oligomer catalyst prepared in example 1 (0.087g, 0.086mmol of [ Al ], [ 2 ] Al]I.e., [ epoxide ]]/[Al]Is 20000/1) is added into a 500ml high-pressure reaction kettle which is subjected to water removal and oxygen removal in advance, and CO with the pressure regulation function is rapidly passed through 2 The supply line is filled with CO in the kettle 2 The reaction was stirred at 60 ℃ for 18 hours, up to a pressure of 3 MPa. After the polymerization reaction is finished, the reaction kettle is cooled to room temperature, and carbon dioxide is slowly discharged. The crude product is first subjected to 1 H-NMR measurement gave a BO conversion of 95.3% by-product, cyclic carbonate 0.9% and carbonate segment content 57.2%. The resulting product was dried under vacuum to remove unreacted 1, 2-butylene oxide and purified by gel permeation chromatography (GPC, PEG standard, CH) 2 Cl 2 ) The number average molecular weight of the polymer was found to be 2400g/mol, with a molecular weight distribution of 1.09; the corresponding unsaturated carbon dioxide-based polyols can also be prepared by additionally replacing epoxides with ethylene oxide, 2-butylene oxide, cyclohexene oxide, cyclopentane oxide, etc., and will not be described in detail.
Comparative example 1
The inventor compares the effect of the zinc-cobalt double metal cyanide catalyst which is a common catalyst for preparing the carbon dioxide-based polyol to prepare the unsaturated carbon dioxide-based polyol. Propylene oxide (150mL, 2.14mol), itaconic acid (9.3g, 71.3mmol, i.e., [ propylene oxide ]]/[ itaconic acid]30/1) and a zinc-cobalt double metal cyanide catalyst (150 mg) were added to a 500ml high-pressure reaction vessel previously subjected to water removal and oxygen removal, and rapidly passed through CO having a pressure regulating function 2 The supply line is filled with CO into the kettle 2 The reaction was stirred for 20 hours while controlling the temperature at 60 ℃ until the pressure was 4.5 MPa. After the polymerization reaction is finished, the reaction kettle is cooled to room temperature, and carbon dioxide is slowly discharged.
The crude product is first subjected to 1 H-NMR measurement gave a PO conversion of 63.9%, cyclic carbonate by-product of 3.2% and a carbonate segment content of 59.7%. The resulting product was dried under vacuum to remove unreacted propylene oxide and purified by gel permeation chromatography (GPC, PEG standard, CH) 2 Cl 2 ) The polymer was found to have a number average molecular weight of 1400g/mol and a molecular weight distribution of 1.41.
It has been found that although zinc-cobalt double metal cyanide catalysts can be used to prepare unsaturated carbon dioxide-based polyols, there are significant disadvantages of poor selectivity, low catalytic activity, and broad molecular weight distribution of the product.
The foregoing detailed description of the present invention provides a highly efficient unsaturated carbon dioxide-based polyol, a method for making the same, and the use of an aluminoporphyrin oligomer as a catalyst in the preparation of an unsaturated carbon dioxide-based polyol, and the principles and embodiments of the present invention are described herein using specific examples, which are provided to facilitate an understanding of the methods of the present invention and their core concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any combination thereof. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. The application of the aluminum porphyrin oligomer as a catalyst in the preparation of unsaturated carbon dioxide-based polyol;
the aluminum porphyrin oligomer has a structure shown in a formula (III);
x is selected from halo, -NO 3 、CH 3 COO-、CCl 3 COO-、CF 3 COO-、ClO 4 -、BF 4 -、BPh 4 -、-CN、-N 3 P-methylbenzoate, p-methylbenzenesulfonate, o-nitrophenol oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2, 4-dinitrophenol oxyanion, 3, 5-dinitrophenol oxyanion, 2,4, 6-trinitrophenol oxyanion, 3, 5-dichlorophenol oxyanion, 3, 5-difluorophenol oxyanion, 3, 5-bistrifluoromethylphenol oxyanion, pentafluorophenyl phenol oxyanion;
the R is 1 Selected from hydrogen, halogen, amino, nitro, cyano, substituted or unsubstituted C1-C10 aliphatic group, and substituted or unsubstituted C6-C30 aryl;
wherein n is the polymerization degree of the aluminum porphyrin oligomer;
the application specifically comprises the steps of taking an aluminum porphyrin oligomer as a catalyst and taking itaconic acid as an initiator.
2. The use according to claim 1, wherein n is 4 to 20;
the preparation mode comprises telomerization;
the reactants for making the unsaturated carbon dioxide-based polyol include an epoxide and carbon dioxide.
3. An unsaturated carbon dioxide-based polyol for use according to any of claims 1-2, having the structure of formula (I);
wherein x is the number of repeating units of carbonate units; y is the number of repeating units of the ether unit;
and R is selected from hydrogen, C1-C10 alkyl, phenyl, chloroalkyl, cyclohexyl and cyclopentyl.
4. The unsaturated carbon dioxide-based polyol of claim 3, wherein x is from 2 to 25;
y is 2 to 25;
and R is methyl.
5. The unsaturated carbon dioxide-based polyol according to claim 3, wherein the unsaturated carbon dioxide-based polyol has a structure in which itaconate ester is a core and a carbonate segment and an ether segment coexist;
in the unsaturated carbon dioxide-based polyol, the content of a carbonate chain segment is 10-70 percent;
the molecular weight of the unsaturated carbon dioxide-based polyol is 1000-5000 g/mol.
6. The preparation method of the unsaturated carbon dioxide-based polyol is characterized by comprising the following steps:
taking an aluminum porphyrin oligomer as a catalyst and itaconic acid as an initiator, and carrying out telomerization on epoxide and carbon dioxide to obtain unsaturated carbon dioxide-based polyol;
the aluminum porphyrin oligomer has a structure shown in a formula (III);
x is selected from halo, -NO 3 、CH 3 COO-、CCl 3 COO-、CF 3 COO-、ClO 4 -、BF 4 -、BPh 4 -、-CN、-N 3 P-methylbenzoate, p-methylbenzenesulfonate, o-nitrophenol oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2, 4-dinitrophenol oxyanion, 3, 5-dinitrophenol oxyanion, 2,4, 6-trinitrophenol oxyanion, 3, 5-dichlorophenol oxyanion, 3, 5-difluorophenol oxyanion, 3, 5-bistrifluoromethylphenol oxyanion, pentafluorophenyl phenol oxyanion;
the R is 1 Selected from hydrogen, halogen, amino, nitro, cyano, substituted or unsubstituted C1-C10 aliphatic group, and substituted or unsubstituted C6-C30 aryl;
wherein n is the polymerization degree of the aluminum porphyrin oligomer.
7. The method according to claim 6, wherein the aluminum porphyrin oligomer has a structure represented by formula (III);
x is selected from halo, -NO 3 、CH 3 COO-、CCl 3 COO-、CF 3 COO-、ClO 4 -、BF 4 -、BPh 4 -、-CN、-N 3 P-methylbenzoate, p-methylbenzenesulfonate, o-nitrophenol oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2, 4-dinitrophenol oxyanion, 3, 5-dinitrophenol oxyanion, 2,4, 6-trinitrophenol oxyanion, 3, 5-dichlorophenol oxyanion, 3, 5-difluorophenol oxyanion, 3, 5-bistrifluoromethylphenol oxyanion, pentafluorophenyl phenol oxyanion;
the R is 1 Selected from hydrogen, halogen, amino, nitro, cyano, substituted or unsubstituted C1-C10 aliphatic group, and substituted or unsubstituted C6-C30 aryl;
wherein n is the polymerization degree of the aluminum porphyrin oligomer.
8. The method according to claim 7, wherein n is 4 to 20;
the aluminum porphyrin oligomer has a structure shown in a formula (III-1) or a formula (III-2);
9. the method of claim 6, wherein the epoxide comprises one or more of ethylene oxide, propylene oxide, 1, 2-butylene oxide, cyclohexene oxide, cyclopentane oxide, epichlorohydrin, glycidyl methacrylate, methyl glycidyl ether, phenyl glycidyl ether, styrene alkylene oxide, 4-vinyl-1, 2-cyclohexene oxide, and vinyl propylene oxide;
the molar ratio of the catalyst to the initiator is 50000: (10-50);
the molar ratio of the epoxy compound to the initiator is 1: (10 to 50).
10. The production method according to claim 6, wherein the pressure of the carbon dioxide is 0.1 to 10MPa;
the temperature of the telomerization reaction is 25-80 ℃;
the telomerization time is 0.5-24 h;
the content of cyclic carbonate as a by-product of the telomerization reaction is less than 1%.
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