CN116003771A - Synthesis method of alpha, beta-unsaturated carboxylic ester functionalized polymer - Google Patents

Synthesis method of alpha, beta-unsaturated carboxylic ester functionalized polymer Download PDF

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CN116003771A
CN116003771A CN202310005696.6A CN202310005696A CN116003771A CN 116003771 A CN116003771 A CN 116003771A CN 202310005696 A CN202310005696 A CN 202310005696A CN 116003771 A CN116003771 A CN 116003771A
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unsaturated carboxylic
beta
functionalized polymer
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赵俊鹏
赖涛
张广照
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South China University of Technology SCUT
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Abstract

The invention discloses a synthesis method of an alpha, beta-unsaturated carboxylic ester functionalized polymer, which comprises the following steps: and mixing epoxide containing alpha, beta-unsaturated carboxylic ester substituent, active hydrogen compound and catalyst to perform polymerization reaction, thus obtaining the alpha, beta-unsaturated carboxylic ester functionalized polymer. The synthesis method of the alpha, beta-unsaturated carboxylic ester functionalized polymer has the advantages of simple operation, atom economy, mild reaction condition, easy separation and purification of products, wide application range and the like, can obtain a series of alpha, beta-unsaturated carboxylic ester functionalized polymers with side groups, main chains and different topological structures, and has wide application prospect.

Description

Synthesis method of alpha, beta-unsaturated carboxylic ester functionalized polymer
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a synthesis method of an alpha, beta-unsaturated carboxylic ester functionalized polymer.
Background
The alpha, beta-unsaturated carboxylic acid esters are widely used in natural/synthetic organic small molecules and functional polymer structures, and the change of substituent structures thereof can generate different reactivities, so that various applications can be derived (for example, cinnamic acid esters and coumarin with beta-position replaced by benzene rings are often used as photosensitive group modified polymer materials, and can be used as photocuring materials, photoresists, liquid crystal display materials, self-repairing materials, shape memory materials and the like).
At present, the alpha, beta-unsaturated carboxylic ester structure is mainly introduced by post-modifying the polymer by a modifier, and the modifier comprises at least one group selected from hydroxyl, amino, carboxyl, halogen, isocyanate group, acyl halide and the like in addition to the alpha, beta-unsaturated carboxylic ester structure for the coupling reaction of the modified group and the active site of the target molecule. However, most of the coupling reactions are condensation reactions, small molecule byproducts are generated, the atom economy is low, and the separation and purification of the products are not facilitated. Furthermore, the reaction of hydroxyl (amino) and carboxyl (halogen) groups and the reaction of carboxyl and halogen groups need to be carried out under severe conditions such as strong acid/base catalysis and high temperature, and the unsaturated carboxylic acid ester structure suitable for modification is very limited. In addition, the initiator, terminator or difunctional monomer containing alpha, beta-unsaturated carboxylic ester can realize synchronous polymerization and modification, the method is more concise and efficient and has atom economy, but most of high-activity alpha, beta-unsaturated carboxylic ester is difficult to be compatible with the traditional ionic/free radical polymerization reaction conditions, only a few of cinnamic acid esters, coumarin and the like can be realized, and the application is greatly limited.
Therefore, the development of the synthesis method of the alpha, beta-unsaturated carboxylic ester functionalized polymer has the advantages of simple and convenient operation, atom economy, mild reaction conditions, easy separation and purification of products and wide application range.
Disclosure of Invention
The invention aims to provide a method for synthesizing an alpha, beta-unsaturated carboxylic ester functionalized polymer.
The technical scheme adopted by the invention is as follows:
a method for synthesizing an alpha, beta-unsaturated carboxylic acid ester functionalized polymer, which comprises the following steps: and mixing epoxide containing alpha, beta-unsaturated carboxylic ester substituent, active hydrogen compound and catalyst to perform polymerization reaction, thus obtaining the alpha, beta-unsaturated carboxylic ester functionalized polymer.
Preferably, the epoxide containing an α, β -unsaturated carboxylic acid ester substituent is at least one of glycidyl acrylate, glycidyl methacrylate, 3, 4-epoxycyclohexylmethyl acrylate, 3, 4-epoxycyclohexylmethyl methacrylate, 3- (2-furyl) glycidyl acrylate, glycidyl cinnamate, 7-epoxypropane oxy-4-methylcoumarin, glycidyl maleate, glycidyl crotonate, 2-methyl epoxypropyl crotonate, glycidyl 2-pentenoate, glycidyl 3, 3-dimethacrylate, glycidyl trans-2-hexenoate, glycidyl 2, 4-pentadienoate, and glycidyl 2, 4-hexadienoate.
The specific structural formula of the epoxide containing an alpha, beta-unsaturated carboxylic acid ester substituent is as follows:
Figure BDA0004036538890000021
further preferably, the epoxide containing an α, β -unsaturated carboxylic acid ester substituent is at least one of glycidyl acrylate, glycidyl methacrylate, 3, 4-epoxycyclohexylmethyl acrylate, and glycidyl 2, 4-hexadienoate.
Preferably, the active hydrogen compound is at least one of amine, water, alcohol, phenol, carboxylic acid, thiol, amide, and hydroxyl terminated polymer.
Further preferably, the active hydrogen compound is at least one of terephthalyl alcohol, acetic acid, pentaerythritol, and dihydroxypolyethylene glycol having a number average molecular weight of 2000.
Preferably, the catalyst is an organic base or a mixture of an organic base and an organoboron.
Preferably, the organic base is at least one of phosphazene base, triaminophosphine, tertiary amine, amidine, guanidine, lithium/sodium/potassium/cesium tert-butoxide, lithium/sodium/potassium/cesium/ammonium pivalate.
Preferably, the phosphazene base is BEMP, t BuP 1 、 t BuP 1 (pyrr)、 t BuP 2 、EtP 2 、 t BuP 4 At least one of them.
Preferably, the triaminophosphine is at least one of HMTP, HETP, TMAP, TIPAP.
Preferably, the tertiary amine is DABCO, PMDETA, ME 6 TREN, sparteine.
Preferably, the amidine is at least one of DBN and DBU.
Preferably, the guanidine is at least one of TBD, MTBD, TMG, PMG.
The specific structural formula of the organic base is as follows:
Figure BDA0004036538890000031
further preferably, the organic base is t BuP 1 、 t BuP 2 、 t BuP 4 At least one of DBU.
Preferably, the organic boron is at least one of trimethylboron, triethylboron, diethylmethoxyboron, triisopropylboron, tri-n-butylboron, tri-sec-butylboron, B-isoppinyl-9-borobicyclo [3.3.1] nonane, triphenylboron, tri (pentafluorophenyl) boron, C1-C8 trialkylborate and triphenylborate.
The specific structural formula of the organoboron is as follows:
Figure BDA0004036538890000032
further preferably, the organoboron is at least one of triethylboron and tri-n-butylboron.
Preferably, the molar ratio of the epoxide containing the alpha, beta-unsaturated carboxylic ester substituent to the active hydrogen compound to the catalyst is 1-1000:1:0.01-5.
Preferably, the polymerization reaction is carried out at 0-100 ℃ for 0.5-300 h.
Preferably, the starting materials for the polymerization reaction further comprise comonomers.
Preferably, the comonomer is at least one of other epoxides, cyclic anhydrides, and carbon dioxide.
Preferably, the other epoxide is at least one of ethylene oxide, C1-C20 linear alkyl ethylene oxide, styrene oxide, cyclohexane oxide, 4-vinyl cyclohexane oxide, limonene oxide, C1-C16 linear alkyl glycidyl ether, t-butyl glycidyl ether, epichlorohydrin, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, trifluoropropylene oxide, 3, 4-epoxy-1-butene.
Preferably, the cyclic anhydride is at least one of succinic anhydride, maleic anhydride, phenylmaleic anhydride, itaconic anhydride, glutaric anhydride, diglycolic anhydride, thiodiglycolic anhydride, hexahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, phthalic anhydride, 3-oxabicyclo [3.1.0] hexane-2, 4-dione, norbornene dianhydride, norbornane dicarboxylic anhydride, bicyclo [2.2.2] oct-5-ene-2, 3-dicarboxylic anhydride.
The specific structural formula of the other epoxides and cyclic anhydrides are as follows:
Figure BDA0004036538890000041
further preferably, the comonomer is ethylene oxide, propylene oxide, cyclohexane oxide, phthalic anhydride, CO 2 At least one of them.
Preferably, the molar ratio of the active hydrogen compound to the comonomer is 1:5-1000.
Preferably, the comonomer is added in at least one of a single addition, a batch multiple addition and a continuous addition.
Preferably, the raw materials for the polymerization reaction further include an organic solvent.
Preferably, the organic solvent is at least one of benzene, toluene, tetrahydrofuran, 2-methyltetrahydrofuran, N-hexane, cyclohexane, acetone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, ethyl acetate, cyclopentyl methyl ether, anisole and gamma-butyrolactone.
The beneficial effects of the invention are as follows: the synthesis method of the alpha, beta-unsaturated carboxylic ester functionalized polymer has the advantages of simple operation, atom economy, mild reaction condition, easy separation and purification of products, wide application range and the like, can obtain a series of alpha, beta-unsaturated carboxylic ester functionalized polymers with side groups, main chains and different topological structures, and has wide application prospect.
Specifically:
1) The invention adopts the alpha, beta-unsaturated carboxylic ester functionalized epoxy monomer to directly carry out ring-opening polymerization and copolymerization, has the advantages of simple operation, atom economy and the like, and avoids the complicated operations of pre-modification or protection, deprotection, re-modification and the like required by the conventional synthesis method of the functionalized polymer;
2) The polymerization reaction is mild and efficient, has excellent chemical selectivity and controllability, controllable molecular weight, narrow distribution and wide molecular weight range, and the functional group structure of the alpha, beta-unsaturated carboxylic ester after polymerization can be completely and completely maintained, and the functionalization efficiency can reach 100%;
3) The alpha, beta-unsaturated carboxylic ester functional group which can be introduced by the invention has extremely rich structure and larger chemical activity difference, can be flexibly designed according to application scenes, and meets different requirements;
4) The comonomer in the invention has the advantages of wide sources, rich structure, partial regeneration, and further the functionalized copolymer has the advantages of designable structure, degradability and the like;
5) The single-component and double-component catalysts in the invention are various, especially the double-component catalysts, and the catalytic activity, selectivity and copolymerization method can be flexibly adjusted and optimized according to different monomer combinations and target polymer structures through the combination, the proportion and the change of feeding modes of various organic bases and organic boron;
6) The invention can use the active hydrogen compound with abundant structures as an initiator to design and synthesize alpha, beta-unsaturated carboxylic ester functionalized macromolecules with end group functionalized, block, star, dendritic, hyperbranched and other topological structures;
7) The invention has no problems of catalyst metal poisoning, difficult product separation and purification and the like, and the functionalized product has natural advantages in the fields of biomedical and electronic appliances;
8) The invention can be carried out under the condition of no solvent or less solvent, has a wide operating temperature range, improves the simplicity, flexibility and safety of operation, and is suitable for industrial production.
Drawings
FIG. 1 is a MALDI-TOF MS of an α, β -unsaturated carboxylic acid ester functionalized polymer synthesized in example 2.
FIG. 2 is a SEC plot of an alpha, beta-unsaturated carboxylate functionalized polymer synthesized in example 2.
FIG. 3 is a schematic illustration of an alpha, beta-unsaturated carboxylic acid ester functionalized polymer synthesized in example 2 1 H NMR chart.
FIG. 4 is a MALDI-TOF MS of the α, β -unsaturated carboxylic acid ester functionalized polymer synthesized in example 3.
FIG. 5 is a SEC plot of an alpha, beta-unsaturated carboxylate functionalized polymer synthesized in example 3.
FIG. 6 is a schematic representation of an alpha, beta-unsaturated carboxylic acid ester functionalized polymer synthesized in example 3 1 H NMR chart.
FIG. 7 is a schematic illustration of an alpha, beta-unsaturated carboxylic acid ester functionalized polymer synthesized in example 4 1 H NMR chart.
FIG. 8 is a SEC plot of an α, β -unsaturated carboxylic acid ester functionalized polymer synthesized in example 5.
FIG. 9 is a schematic representation of an alpha, beta-unsaturated carboxylic acid ester functionalized polymer synthesized in example 5 1 H NMR chart.
FIG. 10 is a MALDI-TOF MS of the α, β -unsaturated carboxylic acid ester functionalized polymer synthesized in example 8.
FIG. 11 is a SEC plot of an α, β -unsaturated carboxylic acid ester functionalized polymer synthesized in example 8.
FIG. 12 is a schematic illustration of an alpha, beta-unsaturated carboxylic acid ester functionalized polymer synthesized in example 8 1 H NMR chart.
Detailed Description
The invention is further illustrated and described below in connection with specific examples.
Example 1:
a method for synthesizing an alpha, beta-unsaturated carboxylic acid ester functionalized polymer, which comprises the following steps:
under nitrogen atmosphere, 1mmol of acetic acid and 0.05mmol of acetic acid are added t BuP 1 Adding 0.2mmol of triethylboron-containing tetrahydrofuran solution (with the concentration of 1 mol/L) and 100mL of tetrahydrofuran into a glass reactor, adding 800mmol of glycidyl acrylate, sealing the glass reactor, starting a magnetic stirrer, reacting at room temperature (20-25 ℃) for 96 hours to obtain a primary product (colorless viscous liquid), adding dichloromethane to dilute the primary product, fully mixing the primary product with neutral alumina, filtering the primary product, adding 0.01wt% of tertiary butyl hydroquinone polymerization inhibitor into the filtrate, performing rotary evaporation to remove the solvent, collecting the solid, and drying the solid in a vacuum oven at the constant temperature of 50 ℃ for 12 hours to obtain the alpha, beta-unsaturated carboxylic ester functionalized polymer.
The conversion of glycidyl acrylate in this example was tested to be 100%, the theoretical number average molecular weight of the synthesized α, β -unsaturated carboxylic acid ester functionalized polymer was 102.6kg/mol, the number average molecular weight as measured by SEC (size exclusion chromatography) was 83.8kg/mol, and the molecular weight distribution was 1.09. In addition, in the case of the optical fiber, 1 h NMR test shows that the chemical shift signal of polyether hydride formed after ring-opening polymerization of glycidyl acrylate and the chemical shift signal of acrylate double bond are well preserved, and this shows that the functional polyether polymer is synthesized successfully and the retention of alpha, beta-unsaturated carboxylic acid ester functional group is 100%.
In summary, the structural formula of the α, β -unsaturated carboxylic acid ester functionalized polymer synthesized in this example is as follows:
Figure BDA0004036538890000061
note that: the conversion rate of the epoxide containing the alpha, beta-unsaturated carboxylic ester substituent and the comonomer and the structural characteristics of the alpha, beta-unsaturated carboxylic ester functionalized polymer are measured by a Bruker AV400 liquid nuclear magnetic resonance instrument, and the solvent is deuterated chloroform or deuterated dimethyl sulfoxide; the relative molecular weight and molecular weight dispersity of the alpha, beta-unsaturated carboxylic ester functionalized polymer are measured by a volume exclusion chromatograph of the model 1260 of Agilent, the mobile phase is tetrahydrofuran, the column temperature is 35 ℃, the flow rate is 1mL/min, and a series of polystyrene or polyethylene oxide standard samples are used as a calibration curve.
Example 2:
a method for synthesizing an alpha, beta-unsaturated carboxylic acid ester functionalized polymer, which comprises the following steps:
in a nitrogen atmosphere, adding 1mmol of terephthalyl alcohol, 0.1mmol of DBU, 0.5mmol of triethylboron-containing tetrahydrofuran solution (with the concentration of 1 mol/L) and 8mL of toluene into a glass reactor, adding 40mmol of glycidyl methacrylate, sealing the glass reactor, starting a magnetic stirrer, reacting at room temperature for 16 hours to obtain a primary product (colorless viscous liquid), adding methylene dichloride for dilution, fully mixing with neutral alumina, filtering, taking filtrate, adding 0.01wt% of tertiary butyl hydroquinone polymerization inhibitor, performing rotary evaporation to remove solvent, collecting solid, and drying at the constant temperature of 50 ℃ for 12 hours in a vacuum oven to obtain the alpha, beta-unsaturated carboxylic ester functionalized polymer.
Performance test:
the matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS) of the synthesized alpha, beta-unsaturated carboxylic acid ester functionalized polymer is shown in FIG. 1, the Space Exclusion Chromatography (SEC) is shown in FIG. 2, and the nuclear magnetic resonance hydrogen spectrum is [ ] 1 HNMR) diagram is shown in fig. 3.
As can be seen from fig. 1 and 2: in this example, the conversion of glycidyl methacrylate was 96%, the theoretical number average molecular weight of the synthesized α, β -unsaturated carboxylic acid ester-functionalized polymer was 5.6kg/mol, the number average molecular weight as measured by SEC was 4.6kg/mol, and the molecular weight distribution was 1.10.
As can be seen from fig. 3: the polymer is initiated by terephthalyl alcohol, and meanwhile, a polyether hydrogen chemical shift signal formed after ring-opening polymerization of glycidyl methacrylate is observed, and the chemical shift signal of a methacrylate double bond is well reserved, which indicates that the functionalized polyether polymer is successfully synthesized. Furthermore, the results of MALDI-TOF MS test are combined, which fully show that the product structure is clear, and the retention degree of the alpha, beta-unsaturated carboxylic ester functional group is 100%.
In summary, the structural formula of the α, β -unsaturated carboxylic acid ester functionalized polymer synthesized in this example is as follows:
Figure BDA0004036538890000071
example 3:
a method for synthesizing an alpha, beta-unsaturated carboxylic acid ester functionalized polymer, which comprises the following steps:
in a nitrogen atmosphere, adding 1mmol of terephthalyl alcohol, 0.1mmol of DBU, 0.5mmol of triethylboron-containing tetrahydrofuran solution (with the concentration of 1 mol/L) and 8mL of toluene into a glass reactor, adding 40mmol of 2, 4-hexadienoic acid glycidyl ester, sealing the glass reactor, starting a magnetic stirrer, reacting at room temperature for 16 hours to obtain a primary product (colorless viscous liquid), adding dichloromethane for dilution, fully mixing with neutral alumina, filtering, adding 0.01wt% of tertiary butyl hydroquinone polymerization inhibitor into the filtrate, performing rotary evaporation to remove the solvent, collecting the solid, and drying at the constant temperature of 50 ℃ for 12 hours in a vacuum oven to obtain the alpha, beta-unsaturated carboxylic ester functionalized polymer.
Performance test:
the MALDI-TOF MS diagram of the alpha, beta-unsaturated carboxylic acid ester functionalized polymer synthesized in the embodiment is shown in figure 4, the SEC diagram is shown in figure 5, 1 the H NMR chart is shown in FIG. 6.
As can be seen from fig. 4 and 5: in this example, the conversion of 2, 4-hexadienoic acid glycidyl ester was 99%, the theoretical number average molecular weight of the synthesized α, β -unsaturated carboxylic acid ester functionalized polymer was 6.8kg/mol, the number average molecular weight as measured by SEC was 6.0kg/mol, and the molecular weight distribution was 1.09.
As can be seen from fig. 6: the polymer is initiated by terephthalyl alcohol, and at the same time, a polyether hydrogen chemical shift signal formed after ring-opening polymerization of 2, 4-hexadienoic acid glycidyl ester is observed, and the chemical shift signal of 2, 4-hexadienoic acid glycidyl ester double bond is well reserved, which indicates that the functionalized polyether polymer is successfully synthesized. Furthermore, the results of MALDI-TOF MS test are combined, which fully show that the product structure is clear, and the retention degree of the alpha, beta-unsaturated carboxylic ester functional group is 100%.
In summary, the structural formula of the α, β -unsaturated carboxylic acid ester functionalized polymer synthesized in this example is as follows:
Figure BDA0004036538890000081
example 4:
a method for synthesizing an alpha, beta-unsaturated carboxylic acid ester functionalized polymer, which comprises the following steps:
1mmol of dihydroxypolyethylene glycol having a number average molecular weight of 2000, 0.02mmol are reacted under nitrogen t BuP 2 Adding 0.5mmol of triethylboron-containing tetrahydrofuran solution (with the concentration of 1 mol/L) and 5mL of tetrahydrofuran into a glass reactor, adding 2mmol of glycidyl methacrylate, sealing the glass reactor, starting a magnetic stirrer, reacting for 1h at room temperature to obtain a primary product (colorless viscous liquid), adding dichloromethane for dilution, fully mixing with neutral alumina, filtering, adding 0.01wt% of tert-butylhydroquinone polymerization inhibitor into filtrate, performing rotary evaporation to remove solvent, collecting solid, and drying at the constant temperature of 50 ℃ in a vacuum oven for 12h to obtain the alpha, beta-unsaturated carboxylic ester functionalized polymer.
Performance test:
the number average molecular weight of the alpha, beta-unsaturated carboxylic acid ester functionalized polymer synthesized in this example was 2.2kg/mol and the molecular weight distribution was 1.04 as measured by SEC.
The alpha, beta-unsaturated carboxylic acid ester functionalized polymer synthesized in the example 1 The H NMR chart is shown in FIG. 7.
As can be seen from fig. 7: the conversion of glycidyl methacrylate was 100% and the theoretical number average molecular weight was 2.3kg/mol, and all the primary hydroxyl groups of polyethylene glycol were converted to secondary hydroxyl groups, indicating that the polyethylene glycol ends were reacted with one glycidyl methacrylate monomer, i.e., m=0 in the structural formula of fig. 7. In addition, MALDI-TOF test results prove that the polymer chain structure is unique, the functionalized polyethylene glycol which simultaneously contains one methacrylate group and one hydroxyl group at the tail end, and the retention degree of the alpha, beta-unsaturated carboxylic ester functional group is 100 percent.
In summary, the structural formula of the α, β -unsaturated carboxylic acid ester functionalized polymer synthesized in this example is as follows:
Figure BDA0004036538890000091
example 5:
a method for synthesizing an alpha, beta-unsaturated carboxylic acid ester functionalized polymer, which comprises the following steps:
1mmol of terephthalyl alcohol and 0.05mmol of terephthalyl alcohol were stirred under nitrogen atmosphere t BuP 4 Adding 0.3mmol of triethylboron-containing tetrahydrofuran solution (with the concentration of 1 mol/L) and 5mL of tetrahydrofuran into a glass reactor, adding 50mmol of glycidyl methacrylate and 100mmol of propylene oxide, sealing the glass reactor, starting a magnetic stirrer for reacting for 24 hours at room temperature to obtain an initial product (colorless viscous liquid), adding methylene dichloride for dilution, fully mixing with neutral alumina, filtering, adding 0.01wt% of tert-butylhydroquinone polymerization inhibitor into the filtrate, performing rotary evaporation to remove the solvent, collecting the solid, and drying at the constant temperature of 50 ℃ in a vacuum oven for 12 hours to obtain the alpha, beta-unsaturated carboxylic ester functionalized polymer.
Performance test:
the SEC diagram of the alpha, beta-unsaturated carboxylic ester functionalized polymer synthesized in the example is shown in figure 8, 1 the H NMR chart is shown in FIG. 9.
As can be seen from fig. 8: the number average molecular weight as measured by SEC was 13.1kg/mol, the molecular weight distribution was 1.06, and the retention of the alpha, beta-unsaturated carboxylate functionality was 100%.
As can be seen from fig. 9: the conversion rate of the glycidyl methacrylate and the conversion rate of the propylene oxide are approximately equal within the same reaction time, the characteristics of random copolymerization are met, the conversion rate of the glycidyl methacrylate is 94%, the conversion rate of the propylene oxide is 96%, and the theoretical number average molecular weight is 12.4kg/mol.
In summary, the structural formula of the α, β -unsaturated carboxylic acid ester functionalized polymer synthesized in this example is as follows:
Figure BDA0004036538890000101
example 6:
a method for synthesizing an alpha, beta-unsaturated carboxylic acid ester functionalized polymer, which comprises the following steps:
1mmol of terephthalyl alcohol and 0.05mmol of terephthalyl alcohol were stirred under nitrogen atmosphere t BuP 1 Adding 0.2mmol of triethylboron-containing tetrahydrofuran solution (with the concentration of 1 mol/L) and 5mL of tetrahydrofuran into a glass reactor, cooling to-20 ℃ by using a liquid nitrogen-ethanol bath, adding 50mmol of ethylene oxide, sealing the glass reaction vessel, starting a magnetic stirrer to react for 0.5h at 0 ℃, adding 20mmol of glycidyl methacrylate, heating to 50 ℃ to continue the reaction for 24h to obtain an initial product (colorless viscous liquid), adding dichloromethane to dilute, fully mixing with neutral alumina, filtering, adding 0.01wt% of tertiary butyl hydroquinone polymerization inhibitor into the filtrate, performing rotary evaporation to remove the solvent, collecting the solid, and drying at the constant temperature of 50 ℃ for 12h in a vacuum oven to obtain the alpha, beta-unsaturated carboxylic ester functionalized polymer.
1 The H NMR test shows that the alpha, beta-unsaturated carboxylic ester functionalized polymer synthesized in the example is B m A n B m The retention of alpha, beta-unsaturated carboxylic ester functional groups of the block copolymer is 100 percent, and the structural formula is as follows:
Figure BDA0004036538890000102
example 7:
a method for synthesizing an alpha, beta-unsaturated carboxylic acid ester functionalized polymer, which comprises the following steps:
1mmol of terephthalyl alcohol and 0.05mmol of terephthalyl alcohol were stirred under nitrogen atmosphere t BuP 1 Tetrahydrofuran solution (1 mol/L) containing 0.2mmol of triethylboron and 8mL of tetrahydrofuranAdding the mixture into a glass reactor, cooling to 0 ℃ with an ice water bath, adding 20mmol of glycidyl methacrylate, sealing the glass reactor, starting a magnetic stirrer, dropwise adding 50mmol of ethylene oxide for 12 hours to obtain a primary product (colorless viscous liquid), adding methylene dichloride for dilution, fully mixing with neutral alumina, filtering, adding 0.01wt% of tertiary butyl hydroquinone polymerization inhibitor into filtrate, performing rotary evaporation to remove a solvent, collecting a solid, and drying at a constant temperature of 50 ℃ in a vacuum oven for 12 hours to obtain the alpha, beta-unsaturated carboxylic ester functionalized polymer.
The test shows that the retention degree of the alpha, beta-unsaturated carboxylic ester functional group in the embodiment is 100%, and the structural formula of the alpha, beta-unsaturated carboxylic ester functional polymer synthesized in the embodiment is as follows:
Figure BDA0004036538890000111
example 8:
a method for synthesizing an alpha, beta-unsaturated carboxylic acid ester functionalized polymer, which comprises the following steps:
under nitrogen atmosphere, 1mmol of terephthalyl alcohol and 0.1mmol of terephthalyl alcohol are mixed t BuP 1 Adding 20mmol of phthalic anhydride, 30mmol of glycidyl methacrylate and 10mL of tetrahydrofuran into a glass reactor, sealing the glass reactor, starting a magnetic stirrer, reacting for 10 hours at 80 ℃ to obtain a primary product (colorless viscous liquid), adding dichloromethane to dilute the primary product, fully mixing the primary product with neutral alumina, filtering the primary product, adding 0.01wt% of tertiary butyl hydroquinone polymerization inhibitor into filtrate, performing rotary evaporation to remove a solvent, collecting a solid, and drying the solid in a vacuum oven at a constant temperature of 50 ℃ for 12 hours to obtain the alpha, beta-unsaturated carboxylic ester functionalized polymer.
The MALDI-TOF MS diagram of the alpha, beta-unsaturated carboxylic acid ester functionalized polymer synthesized in the example is shown in FIG. 10, the SEC diagram is shown in FIG. 11, 1 the H NMR chart is shown in FIG. 12.
As can be seen from fig. 10 to 12: the conversion of phthalic anhydride was 82%, the retention of the α, β -unsaturated carboxylate functionality was 100%, and the α, β -unsaturated carboxylate functionalized polymer synthesized in this example was a polyester polymer of alternating structure.
The structural formula of the alpha, beta-unsaturated carboxylic ester functionalized polymer synthesized in the embodiment is as follows:
Figure BDA0004036538890000112
example 9:
a method for synthesizing an alpha, beta-unsaturated carboxylic acid ester functionalized polymer, which comprises the following steps:
under nitrogen atmosphere, 1mmol of pentaerythritol and 0.1mmol of the catalyst were added t BuP 1 Adding 20mmol of phthalic anhydride, 30mmol of glycidyl methacrylate and 10mL of tetrahydrofuran into a glass reactor, sealing the glass reactor, starting a magnetic stirrer, reacting for 10 hours at 80 ℃ to obtain a primary product (colorless viscous liquid), adding dichloromethane to dilute the primary product, fully mixing the primary product with neutral alumina, filtering the primary product, adding 0.01wt% of tertiary butyl hydroquinone polymerization inhibitor into filtrate, performing rotary evaporation to remove a solvent, collecting a solid, and drying the solid in a vacuum oven at a constant temperature of 50 ℃ for 12 hours to obtain the alpha, beta-unsaturated carboxylic ester functionalized polymer.
In this example, four hydroxyl groups of the initiator indifferently initiate ring-opening alternating copolymerization of glycidyl methacrylate and phthalic anhydride, the topology of the copolymerization product is star-shaped, and the retention of alpha, beta-unsaturated carboxylic acid ester functional groups is 100%.
The structural formula of the alpha, beta-unsaturated carboxylic ester functionalized polymer synthesized in the embodiment is as follows:
Figure BDA0004036538890000121
example 10:
a method for synthesizing an alpha, beta-unsaturated carboxylic acid ester functionalized polymer, which comprises the following steps:
1mmol of terephthalyl alcohol and 0.2mmol of the catalyst were stirred under nitrogen t BuP 2 Adding 0.4mmol of triethylboron-containing tetrahydrofuran solution (with the concentration of 1 mol/L) and 100mmol of acrylic acid-3, 4-epoxycyclohexylmethyl ester into a high-pressure reaction kettle, and filling CO 2 When the pressure in the high-pressure reaction kettle reaches 2MPa, starting a magnetic stirrer, reacting for 36 hours at 60 ℃, cooling the reaction kettle by using ice water bath, and slowly releasing the residual CO 2 Obtaining an initial product (colorless viscous liquid), adding methylene dichloride to dilute, fully mixing with neutral alumina, filtering, adding 0.01wt% of tertiary butyl hydroquinone polymerization inhibitor into filtrate, performing rotary evaporation to remove solvent, collecting solid, and drying at a constant temperature of 50 ℃ in a vacuum oven for 12 hours to obtain the alpha, beta-unsaturated carboxylic ester functionalized polymer.
1 H NMR test showed that the conversion of 3, 4-epoxycyclohexylmethyl acrylate was 100%, the polymer selectivity and carbonate structural unit content were both greater than 99%, and the theoretical number average molecular weight was 22.8kg/mol. The number average molecular weight as measured by SEC was 10.1kg/mol and the molecular weight distribution was 1.12.
The retention of the α, β -unsaturated carboxylate functionality in this example is 100%.
The structural formula of the alpha, beta-unsaturated carboxylic ester functionalized polymer synthesized in the embodiment is as follows:
Figure BDA0004036538890000122
example 11:
a method for synthesizing an alpha, beta-unsaturated carboxylic acid ester functionalized polymer, which comprises the following steps:
1mmol of terephthalyl alcohol and 0.2mmol of the catalyst were stirred under nitrogen t BuP 2 Adding tetrahydrofuran solution (concentration is 1 mol/L) containing 0.4mmol of tri-n-butyl boron and 100mmol of 3, 4-epoxycyclohexylmethyl acrylate into a high-pressure reaction kettle, and then filling CO 2 When the pressure in the high-pressure reaction kettle reaches 2MPa, starting a magnetic stirrer, reacting for 36 hours at 60 ℃, cooling the reaction kettle by using ice water bath, and slowly releasing the residual CO 2 To obtain the initial product (colorless viscous liquid), adding dichloromethaneAnd (3) fully mixing the diluted solution with neutral alumina, filtering, adding 0.01wt% of tertiary butyl hydroquinone polymerization inhibitor into the filtrate, performing rotary evaporation to remove the solvent, collecting the solid, and drying the solid in a vacuum oven at the constant temperature of 50 ℃ for 12 hours to obtain the alpha, beta-unsaturated carboxylic ester functionalized polymer.
The retention of the α, β -unsaturated carboxylate functionality in this example is 100%.
The structural formula of the alpha, beta-unsaturated carboxylic ester functionalized polymer synthesized in the embodiment is as follows:
Figure BDA0004036538890000131
example 12:
a method for synthesizing an alpha, beta-unsaturated carboxylic acid ester functionalized polymer, which comprises the following steps:
under nitrogen atmosphere, 1mmol of terephthalyl alcohol and 0.1mmol of terephthalyl alcohol are mixed t BuP 1 Adding 0.3mmol of triethylboron-containing tetrahydrofuran solution (with the concentration of 1 mol/L), 100mmol of phthalic anhydride, 150mmol of cyclohexene oxide and 20mL of tetrahydrofuran into a glass reactor, sealing the glass reactor, starting a magnetic stirrer, dropwise adding 20mmol of glycidyl methacrylate, finishing the addition for 36 hours to obtain a primary product (colorless viscous liquid), adding dichloromethane to dilute the primary product, fully mixing the primary product with neutral alumina, filtering, adding 0.01wt% of tertiary butyl hydroquinone polymerization inhibitor into filtrate, performing rotary evaporation to remove a solvent, collecting a solid, and drying the solid in a vacuum oven at the constant temperature of 50 ℃ for 12 hours to obtain the alpha, beta-unsaturated carboxylic ester functionalized polymer.
The retention of the α, β -unsaturated carboxylate functionality in this example is 100%.
The structural formula of the alpha, beta-unsaturated carboxylic ester functionalized polymer synthesized in the embodiment is as follows:
Figure BDA0004036538890000132
example 13:
a method for synthesizing an alpha, beta-unsaturated carboxylic acid ester functionalized polymer, which comprises the following steps:
1mmol of terephthalyl alcohol and 0.2mmol of the catalyst were stirred under nitrogen t BuP 2 Tetrahydrofuran solution (1 mol/L) containing 0.4mmol of triethylboron, 150mmol of epoxycyclohexane and 20mmol of glycidyl methacrylate are added into a high-pressure reaction kettle, and CO is filled 2 The pressure in the high-pressure reaction kettle is up to 2MPa, a magnetic stirrer is started, the reaction is carried out for 36 hours at 60 ℃ to obtain a primary product (colorless viscous liquid), methylene dichloride is added to dilute the primary product and then the primary product is fully mixed with neutral alumina, the primary product is filtered, the filtrate is taken to be added with 0.01 weight percent of tertiary butyl hydroquinone polymerization inhibitor and then is subjected to rotary evaporation to remove the solvent, and then the solid is collected and placed in a vacuum oven to be dried for 12 hours at the constant temperature of 50 ℃ to obtain the alpha, beta-unsaturated carboxylic ester functionalized polymer.
The retention of the α, β -unsaturated carboxylate functionality in this example is 100%.
The structural formula of the alpha, beta-unsaturated carboxylic ester functionalized polymer synthesized in the embodiment is as follows:
Figure BDA0004036538890000141
the above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (10)

1. A method for synthesizing an alpha, beta-unsaturated carboxylic ester functionalized polymer, which is characterized by comprising the following steps: and mixing epoxide containing alpha, beta-unsaturated carboxylic ester substituent, active hydrogen compound and catalyst to perform polymerization reaction, thus obtaining the alpha, beta-unsaturated carboxylic ester functionalized polymer.
2. The method for synthesizing an α, β -unsaturated carboxylic acid ester functionalized polymer according to claim 1, wherein: the epoxide containing alpha, beta-unsaturated carboxylic ester substituent is at least one of glycidyl acrylate, glycidyl methacrylate, 3, 4-epoxycyclohexylmethyl acrylate, 3, 4-epoxycyclohexylmethyl methacrylate, 3- (2-furyl) glycidyl acrylate, glycidyl cinnamate, 7-epoxypropane oxy-4-methylcoumarin, glycidyl maleate, glycidyl crotonate, 2-methyl glycidyl crotonate, glycidyl 2-pentenoate, glycidyl 3, 3-dimethacrylate, trans-2-hexenoate, glycidyl 2, 4-pentadienoate and glycidyl 2, 4-hexadienoate.
3. The method for synthesizing an α, β -unsaturated carboxylic acid ester functionalized polymer according to claim 1, wherein: the active hydrogen compound is at least one of amine, water, alcohol, phenol, carboxylic acid, mercaptan, amide and hydroxyl terminated polymer.
4. The method for synthesizing an α, β -unsaturated carboxylic acid ester functionalized polymer according to claim 1, wherein: the catalyst is organic base or a mixture of organic base and organic boron.
5. The method for synthesizing an α, β -unsaturated carboxylic acid ester-functionalized polymer according to claim 4, wherein: the organic base is at least one of phosphazene base, triamine, tertiary amine, amidine, guanidine, lithium/sodium/potassium/cesium tert-butoxide, lithium/sodium/potassium/cesium/ammonium pivalate; the organic boron is at least one of trimethyl boron, triethyl boron, diethyl methoxyl boron, triisopropyl boron, tri-n-butyl boron, tri-sec-butyl boron, B-isopiperazine-9-boron bicyclo [3.3.1] nonane, triphenyl boron, tri (pentafluorophenyl) boron, C1-C8 trialkyl borate and triphenyl borate.
6. The method for synthesizing an α, β -unsaturated carboxylic acid ester functionalized polymer according to claim 1, wherein: the molar ratio of the epoxide containing alpha, beta-unsaturated carboxylic ester substituent to the active hydrogen compound to the catalyst is 1-1000:1:0.01-5.
7. The method for synthesizing an α, β -unsaturated carboxylic acid ester functionalized polymer according to claim 1, wherein: the polymerization reaction is carried out at the temperature of 0-100 ℃ for 0.5-300 h.
8. The method for synthesizing an α, β -unsaturated carboxylic acid ester-functionalized polymer according to any one of claims 1 to 7, wherein: the raw materials of the polymerization reaction also comprise comonomers; the comonomer is at least one of other epoxides, cyclic anhydride and carbon dioxide.
9. The method for synthesizing an α, β -unsaturated carboxylic acid ester functionalized polymer according to claim 8, wherein: the other epoxide is at least one of ethylene oxide, C1-C20 linear alkyl ethylene oxide, styrene oxide, cyclohexene oxide, 4-vinyl cyclohexene oxide, limonene oxide, C1-C16 linear alkyl glycidyl ether, tertiary butyl glycidyl ether, epichlorohydrin, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, trifluoroepoxypropane and 3, 4-epoxy-1-butene; the cyclic anhydride is at least one of succinic anhydride, maleic anhydride, phenylmaleic anhydride, itaconic anhydride, glutaric anhydride, diglycolic anhydride, thiodiglycolic anhydride, hexahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, phthalic anhydride, 3-oxabicyclo [3.1.0] hexane-2, 4-dione, norbornene dianhydride, norbornane dicarboxylic anhydride and bicyclo [2.2.2] oct-5-ene-2, 3-dicarboxylic anhydride.
10. The method for synthesizing an α, β -unsaturated carboxylic acid ester-functionalized polymer according to any one of claims 1 to 7, wherein: the raw materials of the polymerization reaction also comprise an organic solvent; the organic solvent is at least one of benzene, toluene, tetrahydrofuran, 2-methyltetrahydrofuran, N-hexane, cyclohexane, acetone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, ethyl acetate, cyclopentyl methyl ether, anisole and gamma-butyrolactone.
CN202310005696.6A 2023-01-04 2023-01-04 Synthesis method of alpha, beta-unsaturated carboxylic ester functionalized polymer Pending CN116003771A (en)

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