CN112876665A - Method for synthesizing polyester or polyether ester containing polyunsaturated side group by using rare earth catalyst and post-modification method thereof - Google Patents
Method for synthesizing polyester or polyether ester containing polyunsaturated side group by using rare earth catalyst and post-modification method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
Abstract
The invention discloses a method for synthesizing polyester containing polyunsaturated side groups by using rare earth catalyst for catalysis and a subsequent modification method. The method is characterized in that rare earth trifluoromethanesulfonate is used as a catalyst for ring-opening copolymerization of 3-ethylene-6-vinyl tetrahydro-2H-pyran-2-one, cyclic lactone, oxirane monomer and homologues thereof, the reaction is carried out for a certain time at a certain temperature, polyester or polyether ester containing polyunsaturated side groups with high molecular weight is prepared, and then the post-modification is carried out on unsaturated bonds of side chains of the polyester or polyether ester through reactions such as mercaptoalkene clicking and the like. The catalyst of the invention is cheap and easy to prepare, the prepared product has polyunsaturated side groups and can be used as precursors of various functional polymer materials, and various properties of polyester or polyether ester are changed through modification, so that the catalyst has wide application prospect.
Description
Technical Field
The invention relates to a novel rare earth metal catalyst: triflic acid rare earth catalyst, a polysubstituted delta-valerolactone cyclic monomer: 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one, and two high ring-opening reactive comonomers: cyclic lactones and oxacycloalkanes, and polyester or polyether esters.
Background
3-Ethylidene-6-vinyl tetrahydro-2H-pyran-2-one (3-Ethylidene-6-vinyl tetrahydro-2H-pyran-2-one, EVL) is a disubstituted delta-valerolactone and is generated by the reaction of carbon dioxide and butadiene under the catalysis of a palladium catalyst. EVL was discovered as early as 1976, and its synthesis conditions were still well established, and its synthesis process has now achieved selectivity of 96% or more and yield of 86% or more (Chemistry Select 2020, 9404-9408.), and has achieved continuous production on a small scale (Chemical Engineering & Technology 2000, 952-955), which can be used as a raw material for the preparation of numerous basic chemicals. The main structure of EVL is a six-membered lactone, and the ring contains two ethylene substituents with different structures, so that direct polymerization is not easy to realize, and the polymerization reaction is only reported in documents. Few studies are limited to EVL double-bond free radical polymerization, and the polymerization process conditions are harsh (the temperature is higher than 180 ℃), so that the obtained product has a complex structure. In addition, because the double bond is consumed in the polymerization process, the obtained product has no space for further functionalization, and the practical value is low.
Rare earth catalysts are a very efficient class of ring-opening polymerization catalysts, commonly used for the polymerization of lactones, lactides, cyclic carbonates and cyclic ethers (Macromolecules 2003,36, 54-60; Macromolecules 2010,43, 6678-. Among them, rare earth trifluoromethanesulfonate (RE) as a Lewis acid has very excellent performance in ring-opening polymerization of lactone (Polymer 2012,53, 4112-4118). The synthesis and preparation methods thereof have also been reported in public. Up to now, there has been no report on ring-opening polymerization of EVL.
Disclosure of Invention
In order to solve the problem that the EVL can not carry out ring-opening polymerization, the invention aims to provide a method for realizing the ring-opening polymerization of the EVL.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for synthesizing polyester containing polyunsaturated side groups by catalysis of a rare earth catalyst comprises the following steps:
and (2) carrying out ring-opening copolymerization on the cyclic structure monomer or homologues thereof, 3-ethylene-6-vinyl tetrahydro-2H-pyran-2-one (EVL) and a rare earth catalyst to obtain the polyester or polyether ester.
Specifically, a ring structure monomer or a homologue thereof, 3-ethylene-6-vinyl tetrahydro-2H-pyran-2-one and a rare earth catalyst are added into a dry container, the mixture is uniformly vibrated, the rare earth catalyst is dissolved in the ring structure monomer or the homologue thereof, the mixture is sealed and placed in an oil bath for reaction, after the reaction, the mixture is poured into n-hexane for precipitation and filtration, and the obtained polymer is dried in vacuum to obtain polyester or polyether ester.
The rare earth catalyst is trifluoromethanesulfonic acid rare earth, and the structural formula of the trifluoromethanesulfonic acid rare earth is as follows:
in the formula, Ln represents a rare earth metal element, and Ln is any one of Sc, Y, La to Lu.
The ring structure monomer is a cyclic lactone or an oxirane monomer.
The structural formula of the 3-ethylidene-6-vinyl tetrahydro-2H-pyran-2-ketone is shown as the following formula:
the cyclic lactone has the following structural formula:
the structural formula of the oxacycloalkane is as follows:
in the formula, R is halogen atom, alkyl, halogenated alkyl, phenyl, halogenated phenyl, double-bond substituent or triple-bond substituent substituted at any number and any position.
The molar ratio of the 3-ethylene-6-vinyl tetrahydro-2H-pyran-2-one monomer, the rare earth catalyst and the ring structure monomer or the homologue thereof is 10-1000: 1:10 to 5000.
The polymerization reaction temperature is 0-120 ℃, and the polymerization reaction time is 0.5-10 days.
The polymerization reaction adopts bulk polymerization or solution polymerization.
The polymerization reaction adopts solution polymerization, and the solvent is dioxane, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, tetramethylurea, dimethyl sulfoxide, sulfolane, nitrobenzene, acetonitrile, benzonitrile, N-methylpyrrolidone, toluene, dichloromethane and trichloromethane.
During the bulk polymerization, the 3-ethylene-6-vinyl tetrahydro-2H-pyran-2-ketone monomer and the ring structure monomer or the homologue thereof are in solution, and the rare earth catalyst is in powder form.
Method for catalytically synthesizing and modifying polyester containing polyunsaturated side groups by rare earth catalyst
After the method for synthesizing the polyester containing the polyunsaturated side group, the polyester or the polyether ester is post-modified by a double bond reaction method to prepare the polyester or polyether ester product with various functionalized side chains.
The double bond reaction method is a method of mercaptoalkene clicking or Michael addition.
Carrying out the reaction of the polyester or polyether ester obtained by the method of claim 1 and a mercapto-containing monomer under the initiation of a free radical initiator and a solvent; the mercapto group-containing monomer has the following structure:
R-SH
wherein R is any number of alkyl, haloalkyl, phenyl, halophenyl, carboxylic acid, alcohol, and homologs thereof and does not contain double bond substituents or triple bond substituents.
The mercaptoalkene click reaction is carried out in a solvent, wherein the solvent is as follows: one of water, methanol, ethanol, dioxane, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, tetramethylurea, dimethyl sulfoxide, sulfolane, nitrobenzene, acetonitrile, benzonitrile, N-methylpyrrolidone, toluene, dichloromethane, and chloroform.
The free radical initiator is: azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, hydrogen peroxide, ammonium persulfate, potassium persulfate, benzoyl peroxide, benzoyl tert-butyl peroxide, methyl ethyl ketone peroxide, methyl benzoylformate, benzoin dimethyl ether, photoinitiator 1173, 1-hydroxycyclohexyl phenyl ketone, photoinitiator 907, (2, 4, 6-trimethylbenzoyl) diphenylphosphine oxide, ethyl 2, 4, 6-trimethylbenzoylphenylphosphonate, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, photoinitiator 2959, bis 2, 6-difluoro-3-pyrrolylphenyltitanocene, photoinitiator 379, benzophenone, tetraethyl michelson, 4-methylbenzophenone, 4-chlorobenzophenone, hydrogen peroxide, ammonium persulfate, potassium persulfate, benzoyl peroxide tert-butyl ester, methyl ethyl methyl ketone peroxide, methyl benzoin dimethyl ether, benzoin dimethyl benzoate, photoinitiator 2959, bis 2, 6-difluoro-3-pyrrolylphenyltitan, One of methyl o-benzoylbenzoate, 4-phenylbenzophenone, ethyl 4-dimethylaminobenzoate, isooctyl p-dimethylaminobenzoate, 2-isopropylthioxanthone, and 2, 4-diethylthiazolone.
Reacting the polyester or polyether ester obtained by the method of claim 1 with an amino group-containing monomer under the catalysis of alkali; the amino group-containing monomer has the following structure:
R-NH2
wherein R is any number of alkyl, haloalkyl, phenyl, halophenyl, carboxylic acid, alcohol, and homologs thereof and does not contain double bond substituents or triple bond substituents.
The alkali is: sodium methoxide, sodium ethoxide, sodium cyanide, sodium amide, triethylamine, pyridine and derivatives thereof, pyrrole and derivatives thereof, Triazabicyclo (TBD) and derivatives thereof, and Diazabicyclo (DBU) and derivatives thereof.
The invention uses triflate rare earth catalyst to catalyze EVL and cyclic lactone or oxacycloalkane to carry out ring-opening copolymerization.
The content of EVL segment of the polyester (polyether ester) polymer synthesized by the method can reach 50 percent, and more than 50 percent of structural units on the main chain of the polyester or polyether ester contain a side group containing two unsaturated bonds. The post-modification of the polyester or polyether ester leaves a very wide space, unsaturated bonds are modified through multiple convenient and rapid reactions such as Michael addition, mercaptoalkene click and the like, the property of the polymer is changed, and the polymer becomes a reliable precursor of a plurality of potential functional polymers.
Compared with the prior art, the invention has the beneficial effects that:
(1) firstly, the rare earth catalyst is used for ring-opening polymerization of an EVL monomer to obtain a polyester or polyether ester product; however, in the prior art, the EVL can only be subjected to double-bond free radical polymerization, and the obtained product has a complex structure and lacks a polymer with further functionalized space.
(2) The triflic acid rare earth catalyst used in the invention has the following characteristics:
(i) the raw materials for preparing the catalyst are cheap and easy to obtain, the preparation method is simple, and the catalyst is a single-component homogeneous catalyst;
(ii) the catalyst has high catalytic activity;
(3) the preparation method can prepare a polyester product with a polyunsaturated side group, can perform various simple and convenient post-modifications such as free radical crosslinking, mercaptoalkene click reaction and the like, and easily changes the physical and chemical properties of the polyester (polyether ester).
(4) When the thiol-ene click reaction is adopted for post-modification, two double bonds on the EVL structure have activity to the reaction, and a polyester (polyether ester) product with highly functionalized side chains can be prepared, so that the physical and chemical properties of the polymer can be greatly changed.
(5) When Michael addition reaction is adopted, selective addition can be carried out on two double bonds on an EVL structure. Wherein the exocyclic double bond does not react, and the alpha-beta unsaturated bond can react. By this mechanism, the polymer can be modified step by step to obtain polyester (polyetherester) products with more diverse functionality.
(6) The invention essentially takes EVL as an intermediate, realizes the copolymerization synthesis of the highly functionalized polyester (polyether ester) by taking carbon dioxide and butadiene as raw materials, and has very positive practical significance for the fixation and utilization of carbon dioxide which is a greenhouse gas.
Drawings
FIG. 1 is a hydrogen nuclear magnetic spectrum of a copolymerization product of EVL and beta-butyrolactone (beta-BL) catalyzed by scandium trifluoromethanesulfonate according to the present invention.
Detailed Description
The invention will be further described with reference to specific embodiments.
The examples of the invention are as follows:
the molecular weights and structures of the polyesters or polyetheresters obtained in the examples which follow are defined by SEC and SEC, respectively1H NMR measurement. The weight average relative molecular weight and molecular weight distribution of the polymer were determined in gel permeation chromatography (Waters 1515 Isocalatic high performance liquid chromatography pump, PLgel 5 μm MIEXD-C column, Wyatt DAWN DSP light scattering detector and Wyatt Optilab DSP) using Hexafluoroisopropanol (HFIP) containing 3mg/mL potassium trifluoroacetate as the mobile phase at 40 ℃ and a flow rate of 0.8 mL/min. Nuclear magnetic resonance in Bruker Avance DMX 400(1H:400MHz) on an instrument using deuterated chloroform (CDCl)3) As solvent Tetramethylsilane (TMS) was used as internal standard.
Example 1
Into a flame-dried reaction flask was charged 0.014g (0.028mmol) of Sc (OTf)3Then, 0.170g (1.118mmol) of EVL and 0.142g (1.654mmol) of beta-butyrolactone (. beta. -BL) were added thereto, and the mixture was shaken to dissolve the catalyst in the monomer. Sc (OTf)3The molar ratio to the monomer was 1: 100. Sealing, placing in an oil bath at 70 ℃ for reaction for 2 hours, pouring the mixture into n-hexane for precipitation and filtration after the reaction, and drying the obtained polymer in vacuum for 2 days to obtain the polyester, wherein the yield is 90%. The resulting polymer SEC has a weight average molecular weight of 2.9kDa and a molecular weight distribution of 2.87.
Dissolving the obtained product in deuterated chloroform, and performing1H NMR test shows that the nuclear magnetic hydrogen spectrum of the obtained product is shown in figure 1. In FIG. 1, it can be seen that at the low field of nuclear magnetic hydrogen spectrum, the hydrogen atom signals h, g, f on the unsaturated bonds in the EVL structural units are still present after polymerization, which indicates that the polymerization reaction is carried out in a ring-opening manner, and the double bonds are retained.
Example 2
Other polymerization conditions were the same as in example 1Except that Lu (OTf)3Is a catalyst. Monomer and Lu (OTf)3The molar ratio of (B)/(A) was 200:1, and the reaction was carried out in an oil bath at 50 ℃ for 24 hours to obtain a polyester yield of 93%. The weight-average molecular weight of the obtained polymer SEC was 3.9kDa, and the molecular weight distribution was 2.45.
Example 3
Other polymerization conditions were the same as in example 1 except that La (OTf)3Is a catalyst. Monomers with La (OTf)3The molar ratio of (1) was 300:1, and the reaction was carried out in a thermostat at 25 ℃ for 7 days to obtain a polyester yield of 95%. The weight-average molecular weight of the obtained polymer SEC was 5.9kDa, and the molecular weight distribution was 1.89.
Example 4
Other polymerization conditions were the same as in example 1, except that Sc (OTf)3In order to catalyze EVL and 3, 3-Chloromethyl Oxetane (CO) to carry out ring-opening copolymerization by using a catalyst, anhydrous acetonitrile is added as a solvent, the molar ratio of monomers is 100:1, the reaction is carried out in an oil bath at 70 ℃ for 4 hours, and the yield of the obtained polyether ester is 93 percent. The resulting polymer SEC had a weight average molecular weight of 5.9kDa and a molecular weight distribution of 1.94.
Example 5
Other polymerization conditions were the same as in example 1, except that Lu (OTf)3The catalyst is used for catalyzing EVL and 3, 3-Chloromethyl Oxetane (CO) to carry out ring-opening copolymerization, no solvent is added, the molar ratio of the monomers is 200:1, the reaction is carried out in an oil bath at 70 ℃ for 4 hours, and the yield of the obtained polyether ester is 95%. The resulting polymer SEC had a weight average molecular weight of 6.9kDa and a molecular weight distribution of 2.18.
Example 6
Other polymerization conditions were the same as in example 1, except that Lu (OTf)3In order to catalyze EVL and 3, 3-Chloromethyl Oxetane (CO) to carry out ring-opening copolymerization by using a catalyst, toluene is added as a solvent, the molar ratio of monomers is 20:1, the reaction is carried out in an oil bath at 50 ℃ for 24 hours, and the yield of the obtained polyether ester is 99%. The resulting polymer SEC had a weight average molecular weight of 2.7kDa and a molecular weight distribution of 1.56.
Example 7
Other polymerization conditions were the same as in example 1, except that Sc (OTf)3Catalyzing EVL, beta-BL and Tetrahydrofuran (THF) tris for catalystsAnd (3) ring-opening copolymerization, wherein the molar ratio of the monomers is 200:1, the reaction is carried out in an oil bath at 70 ℃ for 8 hours, and the yield of the obtained polyether ester is 96%. The weight-average molecular weight of the obtained polymer SEC was 4.7kDa, and the molecular weight distribution was 2.03.
Example 8
0.312g of the product obtained in example 1 was taken out of a quartz reaction flask, dissolved in 2mL of N, N-Dimethylformamide (DMF), 0.010g of benzophenone was added as a radical initiator, dissolved oxygen was removed by bubbling with argon, and the mixture was uniformly irradiated under ultraviolet light for 1 hour. The polymer undergoes free radical crosslinking to give a reddish-brown gel. The reddish-brown gel swells in THF solution and becomes voluminous. Shrinkage occurs in water and turns into an opaque white polymer solid. This shows that the double bond of the polymer side group has reactivity, and the polymer material with certain shape can be obtained through simple processing.
Example 9
The other conditions were the same as in example 8 except that the solvent was replaced with methanol and 0.423g of cysteine was added. After the reaction is finished, evaporating the methanol to dryness, washing the residual solid with water for 3 times, and drying for 72 hours under vacuum to obtain the polyester with cysteine on the side chain, wherein the polymer is changed into powder from a sticky state, the dissolubility is changed into an aqueous solution which is easy to dissolve in acid or alkali (pH <3 or pH >11) from insoluble in water, and the degradation does not occur within 108 hours. This indicates that the polymer can be modified by thiol-ene click reactions and changes the solubility of the polymer.
Example 10
0.312g of the product obtained in example 1 was taken out and dissolved in 5mL of methanol in a 25mL flask, and 0.200g of triethylamine as a base catalyst and 0.257g of glutamic acid were added simultaneously, followed by stirring and refluxing in an oil bath at 70 ℃ for 24 hours. After the reaction is finished, the methanol is evaporated to dryness, the residual solid is washed by water for 3 times and dried under vacuum for 72 hours, the polyester with glutamic acid on the side face is obtained, the polymer is changed into powder from a sticky state, and the dissolubility is changed into an aqueous solution which is easy to dissolve in acid or alkali (pH <3 or pH >11) from insoluble in water. This indicates that the polymer can be modified by the Michael addition reaction and the solubility of the polymer changed.
Therefore, the catalyst used in the invention is cheap and easy to prepare, has high catalytic activity, and the prepared polyester or polyether ester product has a polyunsaturated side group, can be used as a precursor of various functional polymer materials, and is further modified to change various properties of the polyester or polyether ester, so that the polyester or polyether ester has wide application prospects.
Claims (10)
1. A method for catalytically synthesizing polyester containing polyunsaturated side groups by using a rare earth catalyst is characterized in that:
and carrying out polymerization reaction on the cyclic structure monomer or homologues thereof, 3-ethylene-6-vinyl tetrahydro-2H-pyran-2-one and a rare earth catalyst to obtain the polyester or polyether ester.
2. The method for catalytically synthesizing polyester containing polyunsaturated side groups by using rare earth catalyst according to claim 1, characterized in that: the rare earth catalyst is trifluoromethanesulfonic acid rare earth, and the structural formula of the trifluoromethanesulfonic acid rare earth is as follows:
in the formula, Ln represents a rare earth metal element, and Ln is any one of Sc, Y, La to Lu.
3. The method for catalytically synthesizing polyester containing polyunsaturated side groups by using rare earth catalyst according to claim 1, characterized in that: the ring structure monomer is a cyclic lactone or an oxirane monomer.
The cyclic lactone has the following structural formula:
the structural formula of the oxacycloalkane is as follows:
in the formula, R is halogen atom, alkyl, halogenated alkyl, phenyl, halogenated phenyl, double-bond substituent or triple-bond substituent substituted at any number and any position.
4. The method for catalytically synthesizing polyester containing polyunsaturated side groups by using rare earth catalyst according to claim 1, characterized in that: the molar ratio of the 3-ethylene-6-vinyl tetrahydro-2H-pyran-2-one monomer, the rare earth catalyst and the ring structure monomer or the homologue thereof is 10-1000: 1:10 to 5000.
5. The method for catalytically synthesizing polyester containing polyunsaturated side groups by using rare earth catalyst according to claim 1, characterized in that: the polymerization reaction temperature is 0-120 ℃, and the polymerization reaction time is 0.5-10 days.
6. The method for catalytically synthesizing polyester containing polyunsaturated side groups by using rare earth catalyst according to claim 1, characterized in that: the polymerization reaction adopts bulk polymerization or solution polymerization.
7. A method for synthesizing and modifying polyester containing polyunsaturated side groups by using rare earth catalyst is characterized in that: after the method of any one of claims 1 to 6, the polyester or polyether ester is post-modified by a double bond reaction method to prepare a polyester or polyether ester product with multiple functionalized side chains.
8. The method for catalytically synthesizing and modifying polyester containing polyunsaturated side groups by using rare earth catalysts according to claim 1, wherein the method comprises the following steps: the double bond reaction method is a method of mercaptoalkene clicking or Michael addition.
9. The method for catalytically synthesizing and modifying polyester containing polyunsaturated side groups by using rare earth catalysts according to claim 1, wherein the method comprises the following steps: carrying out the reaction of the polyester or polyether ester obtained by the method of any one of claims 1 to 6 and a mercapto-containing monomer under the initiation of a free radical initiator and a solvent; the mercapto group-containing monomer has the following structure:
R-SH
wherein R is any number of alkyl, haloalkyl, phenyl, halophenyl, carboxylic acid, alcohol, and homologs thereof and does not contain double bond substituents or triple bond substituents.
10. The method for catalytically synthesizing and modifying polyester containing polyunsaturated side groups by using rare earth catalysts according to claim 1, wherein the method comprises the following steps: reacting the polyester or polyether ester obtained by the method of claim 1 with an amino group-containing monomer under the catalysis of alkali; the amino group-containing monomer has the following structure:
R-NH2
wherein R is any number of alkyl, haloalkyl, phenyl, halophenyl, carboxylic acid, alcohol, and homologs thereof and does not contain double bond substituents or triple bond substituents.
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