CN113087880B - Polyester and preparation method thereof - Google Patents
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
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Abstract
The invention provides a preparation method of polyester, which comprises the following steps: carrying out polymerization reaction on a bis (alpha-diazo-1, 3-dicarbonyl) compound monomer and a dicarboxylic acid monomer under the action of a rhodium catalyst to obtain the polyester. The method for preparing the polyester is a preparation method which is efficient, mild and good in functional group tolerance, is easy to operate, and the obtained polyester has a clear alternating sequence, medium to high molecular weight and rich framework structure. Can meet the application in biomedicine, engineering plastics, packaging materials and the like. Provides a feasible method for preparing the functionalized alternating polyester under mild conditions.
Description
Technical Field
The invention relates to the technical field of macromolecules, in particular to polyester and a preparation method thereof.
Background
Polyester is an important high molecular material, and has excellent mechanical property, low air humidity and easy processability. The semi-aromatic polyester is applied to packaging materials and engineering plastics. In addition, the aliphatic polyester can be applied to biomedical materials due to its biocompatibility, hydrolyzability and biodegradability. Polyesters are generally prepared by stepwise polymerization of diols with diacids or their derivatives, which have the advantage that the monomers are easily synthesized and structurally abundant. However, this process usually requires severe polymerization conditions, such as high temperature and vacuum conditions, and higher molecular weights and conversions can only be achieved by removing by-products. Thus, it is difficult to achieve precise control of sequence, molecular weight and polydispersity with polyesters obtained by step-wise polymerization. Moreover, under such stringent reaction conditions, functional groups are not present. In contrast, chain growth polymerization, including lactone ring-opening polymerization and alternate anhydride and epoxide ring-opening copolymerization, can yield polyesters of high molecular weight, controlled dispersibility, unsaturation, and tunable properties. However, the ring-opening polymerization of lactones still has the problems of side reactions (such as transesterification), limited structural diversity, high monomer cost, and low functional group tolerance. The alternating ring-opening copolymerization of epoxides and anhydrides produces polyesters with precise alternating sequences and desirable properties. However, alternating ring-opening copolymerization makes it difficult to synthesize functionalized polyesters, andmonomers suitable for alternating ring-opening copolymerization are limited to CO which forms 5-or 6-membered cyclic anhydrides2、SO2COS, dicarboxylic acids, and the like, and epoxides as 1, 2-diol derivatives. Olefin metathesis polymerization and Baylis-Hillman polymerization, have also been used in polyester synthesis, but monomer structural diversity, sequence control and functional group tolerance are still limited. Therefore, it remains challenging to develop new synthetic methods for polyesters with diverse monomer structures, mild polymerization conditions, precise sequence control, and good functional group tolerance.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a polyester and a preparation method thereof, which can prepare a polyester compound having an accurate alternating sequence distribution.
The invention provides polyester, which has a structure shown in a formula I:
wherein R is1Is H, C1-C10 alkyl, C6-C12 aryl or
R2Is C1-C10 alkylene;
R3is substituted or unsubstituted C1-C10 alkylidene, C2-C10 alkynylidene, C3-C10 cycloalkylidene or C6-C12 arylene;
R4is C1-C10 alkyl or C6-C12 aryl;
n is polymerization degree, and n is 10-54.
Preferably, said R is1Is H, C1-C5 alkyl, phenyl or
Further preferred is H, C1-C3 alkyl, phenyl or
The R is4Preferably a C1-C5 alkyl group or phenyl group, more preferably a C1-C3 alkyl group or phenyl group.
In some embodiments of the invention, R is1Is methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, phenyl, benzoyl
Formyl radical
Acetyl or propionyl. Further preferred is benzoyl or formyl.
The R is2Preferably a C1 to C6 alkylene group, and more preferably a C1 to C5 alkylene group.
In some embodiments of the invention, R is2Methylene, ethylene, propylene, isopropylene, butylene, isobutylene, tert-butylene, pentylene, isopentylene, 2-dimethylpropyl, 2, 3-dimethylpropyl, 1, 3-dimethylpropyl. Further preferred is methylene, propylene, butylene or pentylene.
In the present invention, R is3Is substituted or unsubstituted C1-C10 alkylidene, C2-C10 alkynylidene, C3-C10 cycloalkylidene or C6-C12 arylene.
The C1-C10 alkylene, C2-C10 alkynylene, C3-C10 cycloalkylene or C6-C12 arylene is optionally substituted by one or more of C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, hydroxyl, nitro, cyano, amino, BocNH-, halogen, sulfonyl, carboxyl and the like. More preferably by one or more of vinyl, alkynyl, hydroxy, Boc amino, trifluoromethyl.
The R is3Preferred are substituted or unsubstituted C1-C6 alkylene, C2-C6 alkynylene, C3-C6 cycloalkylene or phenyl.
The C1-C6 alkylene, C2-C6 alkynylene, C3-C6 cycloalkylene or phenyl can be optionally substituted by one or more of C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, hydroxyl, nitro, cyano, amino, BOCNH-, halogen, sulfonyl, carboxyl and the like. More preferably by one or more of vinyl, alkynyl, hydroxy, Boc amino, trifluoromethyl.
In some embodiments of the invention, R is3Is substituted or unsubstituted cyclohexylene, methylene, ethylene, propylene, isopropylene, butylene, isobutylene, tert-butylene, pentylene, isopentylene, 2-dimethylpropylene, 2, 3-dimethylpropylene, 1, 3-dimethylpropylene, ethynylene or
The above-mentioned cyclohexylene group, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, tert-butylene group, pentylene group, isopentylene group, 2-dimethylpropyl group, 2, 3-dimethylpropyl group, 1, 3-dimethylpropyl group, ethynylene group or ethynylene group
Optionally substituted by one or more of C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, hydroxyl, nitro, cyano, amino, BOCNH-, halogen, sulfonyl, carboxyl and the like. More preferably by one or more of vinyl, alkynyl, hydroxy, Boc amino, trifluoromethyl.
In some embodiments of the invention, R3Selected from any of the following structures:
in the present invention, when said R is3When substituted, the polyester has a branched functional group, which can be further represented by the following formula II:
the R is1、R2、R3The same scope is defined above, and is not described herein.
The FG above represents a branched functional group of the polyester, which may be one or more, may be attached to one carbon atom, or to a plurality of carbon atoms.
The FG is preferably a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a hydroxyl group, a nitro group, a cyano group, an amino group, a BocNH-, a halogen, a sulfonyl group, a carboxyl group and the like. More preferably one or more of vinyl, alkynyl, hydroxyl, Boc amino, trifluoromethyl.
The n is a polymerization degree, preferably 40.
The polyester provided by the invention has the advantages of abundant monomer structure, mild polymerization conditions, accurate sequence control, good functional group tolerance and the like. The glass transition temperature of the polyester is above-24 ℃, and the 5% weight loss temperature is above 180 ℃.
The invention provides a preparation method of polyester, which comprises the following steps:
carrying out polymerization reaction on a bis (alpha-diazo-1, 3-dicarbonyl) compound monomer and a dicarboxylic acid monomer under the action of a rhodium catalyst to obtain the polyester.
The polymerization reaction is specifically an OH insertion polycondensation reaction of carbene.
The polyester preferably has the structure shown in formula I:
in the structure of the formula I,
The R is1、R2、R3And n is as above, and is not described herein again.
In a preferred embodiment of the present invention, the bis (. alpha. -diazo-1, 3-dicarbonyl) compound is 1, 4-bis (. alpha. -diazoacetoacetoxy) butane or 1, 4-bis (. alpha. -diazobenzoylacetoxy) butane.
The structural formula is as follows in sequence:
the dicarboxylic acid monomer is preferably 1, 4-cyclohexanedicarboxylic acid, 1, 6-adipic acid, itaconic acid, butynedioic acid, 2-bis (4-carboxyphenyl) hexafluoropropane, 3-hydroxy-glutaric acid or Boc-L-glutamic acid.
The structural formula is as follows in sequence:
the rhodium catalyst is preferably rhodium acetate.
The dosage of the rhodium catalyst is preferably 1 to 5 percent of the mass of the bis (alpha-diazo-1, 3-dicarbonyl) compound monomer.
The solvent for the reaction is preferably an organic solvent such as 1, 2-dichloroethane, toluene, or dichloromethane.
The reaction temperature is preferably 25-60 ℃, and the reaction time is preferably 4-18 h.
After the polymerization reaction is finished, preferably, the reaction system is separated out by using a precipitator, the precipitate is collected, fully washed and dried, and then the yellow viscous solid polyester can be obtained.
The precipitant is preferably one or more of petroleum ether, methanol, diethyl ether and the like.
The reagent used for polymer washing is preferably one or more of saturated sodium bicarbonate solution, water, ethanol, and the like.
The invention provides a preparation method of the bis (alpha-diazo-1, 3-dicarbonyl) compound, which comprises the following steps (taking 1, 4-butanediol as an example):
mixing 1, 4-butanediol and an acetoacetoxy compound, and performing ester exchange reaction to obtain a bis (acetoacetoxy) compound monomer;
adding a bis (acetoacetoxy) compound monomer and an alkaline reagent into a polar organic solvent, and then dropwise adding a diazo transfer agent into a reaction system to carry out diazo transfer reaction to obtain a bis (alpha-diazo-1, 3-dicarbonyl) compound.
In the step (1), the solvent for the reaction is preferably toluene, the reaction temperature is preferably 100-140 ℃, and the reaction time is preferably 2-6 h.
After the reaction is finished, reduced pressure distillation is preferably carried out, and the obtained crude product is separated and purified by column chromatography.
In the step (2), the reaction temperature is preferably 10-60 ℃, and the reaction time is preferably 7-20 h.
The basic agent is preferably aqueous sodium hydroxide or triethylamine.
The polar organic solvent is preferably N, N-dimethylformamide and/or acetonitrile.
After the reaction is completed, the reaction system is preferably washed with water, extracted with an organic solvent, and rotary evaporated. And carrying out column chromatography separation and purification on the obtained crude product to obtain a pure product of the bis (alpha-diazo-1, 3-dicarbonyl) compound monomer.
The organic solvent used for the extraction is preferably ethyl acetate, dichloromethane or chloroform.
In column chromatography, preferably, the leacheate used is: petroleum ether/ethyl acetate.
In the diazo transfer reaction, preferably, the diazo transfer agent used is: p-toluenesulfonyl azide or methylsulfonyl azide.
The reaction route of the above reaction is as follows (taking 1, 4-butanediol as an example):
the reaction route of the above reaction is as follows:
in the present invention, a single bond represents a methyl group, a bent line
Indicating the location of the connection.
The method for preparing the polyester is a preparation method which is efficient, mild and good in functional group tolerance, is easy to operate, and the obtained polyester has a clear alternating sequence, medium to high molecular weight and rich framework structure. Can meet the application in biomedicine, engineering plastics, packaging materials and the like. Provides a feasible method for preparing the functionalized alternating polyester under mild conditions.
Drawings
FIG. 1 shows a polymer obtained in example 3 of the present invention1H NMR spectrum;
FIG. 2 shows a polymer obtained in example 3 of the present invention13C NMR spectrum;
FIG. 3 is a graph of the thermal weight loss of the polymer obtained in example 3 of the present invention;
FIG. 4 is a DSC spectrum of the polymer obtained in example 4 of the present invention.
Detailed Description
In order to further illustrate the present invention, the following examples are given to describe the polyester provided by the present invention and the preparation method thereof in detail.
In the following examples, only one of 2 bis (. alpha. -diazo-1, 3-dicarbonyl) compounds is taken as an example for illustration, and the structure of the bis (. alpha. -diazo-1, 3-dicarbonyl) compound is not limited thereto and can be adjusted by itself depending on the actual situation.
EXAMPLE 11 preparation of 4, 4-bis (. alpha. -diazoacetoacetoxy) butane
In the first step, 1, 4-bis (acetoacetoxy) butane is prepared. The reaction steps are as follows:
in a 100mL round bottom flask equipped with magnetic stirring, 2.3g of 1, 4-butanediol, 6.9mL of ethyl acetoacetate, 50mL of toluene solvent were added. The temperature of the reaction system is raised to 120 ℃ and the reaction is carried out for 4 hours. After the reaction is finished, the reaction product is subjected to reduced pressure rotary evaporation. The crude product is purified by column chromatography to obtain 1, 4-bis (acetoacetoxy) butane as yellow oil.
In the second step, 1, 4-bis (. alpha. -diazoacetoacetoxy) butane is prepared. The reaction steps are as follows:
in a 100mL round-bottom flask equipped with magnetic stirring, 6.5g of the above product and 4 times the amount of triethylamine were added, 50mL of acetonitrile was added, 6.7g of methylsulfonylazide diazo transfer agent was added dropwise to the reaction system, and the reaction was carried out at 25 ℃ for 10 hours. After the reaction was completed, the reaction mixture was washed with water. Extracted with 3X 200mL of dichloromethane. Drying the product with magnesium sulfate, rotary evaporating the product, and carrying out column chromatography separation and purification on the obtained crude product to obtain white crystal-shaped bis (alpha-diazo-1, 3-dicarbonyl) compound monomer 1, 4-bis (alpha-diazoacetoacetoxy) butane.
Example 2
In a polymerization flask equipped with magnetic stirring, 0.3103g of 1, 4-bis (. alpha. -diazoacetoacetoxy) butane, 0.1722g of 1, 4-cyclohexanedicarboxylic acid and 0.0050g of rhodium acetate catalyst were charged, 3mL of a methylene chloride solvent was further added, and the reaction was stirred at 40 ℃ for 6 hours. After the reaction is finished, filtering to remove unreacted 1, 4-cyclohexanedicarboxylic acid, then settling and separating out in 20mL petroleum ether, collecting the precipitate, washing with water and drying to obtain yellow viscous solid polyester.
The polyester has the following structural formula:
Example 3
In a polymerization flask equipped with a magnetic stirrer, 0.3103g of 1, 4-bis (. alpha. -diazoacetoacetoxy) butane, 0.3924g of 2, 2-bis (4-carboxyphenyl) hexafluoropropane and 0.0050g of rhodium acetate catalyst were charged, and 3mL of a methylene chloride solvent was added thereto, and the reaction was stirred at 40 ℃ for 8 hours. After the reaction, unreacted 2, 2-bis (4-carboxyphenyl) hexafluoropropane was removed by filtration, and then precipitated in 20mL of petroleum ether, and the precipitate was collected and washed with water and dried to obtain a yellow viscous solid polyester.
The polyester has the following structural formula:
The polymer structure was examined by NMR, and the results are shown in FIGS. 1 and 2, in which FIG. 1 shows the polymer1H NMR spectrum, FIG. 2 of the polymer13C NMR spectrum. Successful synthesis of the polymer can be demonstrated.
Thermogravimetric analysis detection is carried out on the prepared polyester, and a thermogravimetric graph is shown in fig. 3, which shows that the thermal property of the polymer can be changed according to different structures of the polymer.
Example 4
In a polymerization flask equipped with magnetic stirring, 0.3103g of 1, 4-bis (. alpha. -diazoacetoacetoxy) butane, 0.1482g of 3-hydroxy-glutaric acid and 0.0050g of rhodium acetate catalyst were added, 4mL of methylene chloride solvent was further added, and the reaction was stirred at 40 ℃ for 6 hours. After the reaction is finished, filtering to remove unreacted 3-hydroxy-glutaric acid, then settling and separating out in 20mL petroleum ether, collecting the precipitate, washing with water and drying to obtain yellow viscous solid polyester.
The polyester has the following structural formula:
The prepared polyester is subjected to differential scanning calorimetry analysis, the thermal property of the polymer is researched, and a DSC spectrogram is shown in figure 4, which shows that the thermal property of the polyester can be changed according to different structures of the synthesized polyester.
Example 5
In a polymerization flask equipped with a magnetic stirrer, 0.3103g of 1, 4-bis (. alpha. -diazoacetoacetoxy) butane, 0.1302g of itaconic acid and 0.0050g of rhodium acetate catalyst were charged, and 3mL of a methylene chloride solvent was added, followed by stirring at 40 ℃ for reaction for 9 hours. After the reaction is finished, filtering to remove unreacted itaconic acid, then settling out in 20mL petroleum ether, collecting the precipitate, washing with water and drying to obtain yellow viscous solid polyester.
The polyester has the following structural formula:
Example 6
0.3103g of 1, 4-bis (. alpha. -diazoacetoacetoxy) butane, 0.1462g of adipic acid and 0.0050g of rhodium acetate catalyst were charged into a polymerization flask equipped with magnetic stirring, and 5mL of a methylene chloride solvent was added thereto, and the reaction was stirred at 40 ℃ for 6 hours. After the reaction is finished, filtering to remove unreacted adipic acid, then settling and separating out in 20mL petroleum ether, collecting the precipitate, washing with water and drying to obtain yellow viscous solid polyester.
The polyester has the following structural formula:
Example 7
In a polymerization flask equipped with a magnetic stirrer, 0.3103g of 1, 4-bis (. alpha. -diazoacetoacetoxy) butane, 0.2472g of Boc-L-glutamic acid and 0.0050g of rhodium acetate catalyst were charged, and 3mL of a methylene chloride solvent was further added to stir the reaction at 40 ℃ for 12 hours. After the reaction is finished, filtering to remove unreacted Boc-L-glutamic acid, then settling and separating out in 20mL petroleum ether, collecting precipitate, washing with water and drying to obtain yellow viscous solid polyester.
The polyester has the following structural formula:
Example 8
1, 4-bis (benzoylacetoxy) butane was prepared from 1, 4-butanediol and ethyl benzoylacetate as starting materials in the same manner as in example 1;
1, 4-bis (. alpha. -diazobenzoylacetoxy) butane was then prepared according to the procedure of example 1.
In a polymerization flask equipped with magnetic stirring, 0.4344g of 1, 4-bis (. alpha. -diazobenzoylacetoxy) butane, 0.1722g of 1, 4-cyclohexanedicarboxylic acid and 0.0050g of rhodium acetate catalyst were charged, 3mL of 1, 2-dichloroethane were further added, and the reaction was stirred at 30 ℃ for 12 hours. After the reaction is finished, filtering to remove unreacted 1, 4-cyclohexanedicarboxylic acid, then settling and separating out in 20mL petroleum ether, collecting the precipitate, washing with water and drying to obtain yellow viscous solid polyester.
The polyester has the following structural formula:
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. 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.
Claims (10)
1. A polyester having the structure of formula I:
wherein R is1Is H, C1-C10 alkyl, C6-C12 aryl or
R2Is C1-C10 alkylene;
R3is a substituted or unsubstituted C1-C10 alkylene group, C2-C10 alkylidene groupAlkynyl, C3-C10 cycloalkylene, C6-C12 arylene,
R4Is C1-C10 alkyl or C6-C12 aryl;
n is polymerization degree, and n is 10-54.
2. The polyester according to claim 1, wherein the C1-C10 alkylene, C2-C10 alkynylene, C3-C10 cycloalkylene or C6-C12 arylene is optionally substituted with one or more of C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, hydroxy, nitro, cyano, amino, BocNH-, halogen, sulfonyl and carboxy.
3. The polyester according to claim 1, wherein R is1Is H, C1-C5 alkyl, phenyl or
R2Is C1-C6 alkylene;
R3is substituted or unsubstituted C1-C6 alkylidene, C2-C6 alkynylene, C3-C6 cycloalkylidene or phenyl;
R4is C1-C5 alkyl or phenyl.
4. The polyester according to claim 1, wherein R is1Is methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, phenyl, benzoyl, formyl, acetyl or propionyl;
R2is methylene, ethylene, propylene, isopropylene, butylene, isobutylene, tert-butylene, pentylene, isopentylene, 2-dimethylpropyl, 2, 3-dimethylpropyl, 1, 3-dimethylpropyl;
R3is substituted or unsubstituted cyclohexylene, methylene, ethylene, propylene, isopropyleneButylene, isobutylene, tert-butylene, pentylene, isopentylene, 2-dimethylpropylene, 2, 3-dimethylpropylene, 1, 3-dimethylpropylene, ethynylene, and the like,
5. The polyester according to claim 4, wherein R is1Is benzoyl or formyl;
R2is methylene, propylene, butylene or pentylene;
R3selected from any of the following structures:
6. a process for preparing a polyester as claimed in any one of claims 1 to 5, comprising the steps of:
carrying out polymerization reaction on a bis (alpha-diazo-1, 3-dicarbonyl) compound monomer and a dicarboxylic acid monomer under the action of a rhodium catalyst to obtain the polyester.
7. The method according to claim 6, wherein the bis (α -diazo-1, 3-dicarbonyl) compound is 1, 4-bis (α -diazoacetoacetoxy) butane or 1, 4-bis (α -diazobenzoylacetoxy) butane;
the dicarboxylic acid monomer is 1, 4-cyclohexanedicarboxylic acid, 1, 6-adipic acid, itaconic acid, butynedioic acid, 2-bis (4-carboxyphenyl) hexafluoropropane, 3-hydroxy-glutaric acid or Boc-L-glutamic acid;
the rhodium catalyst is rhodium acetate.
8. The preparation method according to claim 6, wherein the reaction temperature is 25-60 ℃ and the reaction time is 4-18 h.
9. The process according to claim 6, characterized in that, after the polymerization reaction is finished, the product is purified, in particular: the reaction system is separated out by a precipitator, the precipitate is collected, fully washed and dried, and the yellow viscous solid polyester is obtained.
10. The method of claim 9, wherein the precipitating agent is one or more of petroleum ether, methanol, and diethyl ether.
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