CN114507339B - Preparation method of vanillin-based polyester - Google Patents
Preparation method of vanillin-based polyester Download PDFInfo
- Publication number
- CN114507339B CN114507339B CN202210097450.1A CN202210097450A CN114507339B CN 114507339 B CN114507339 B CN 114507339B CN 202210097450 A CN202210097450 A CN 202210097450A CN 114507339 B CN114507339 B CN 114507339B
- Authority
- CN
- China
- Prior art keywords
- vanillin
- bromo
- monomer
- reaction
- iodo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of vanillin-based polyester, which comprises the following steps: preparing corresponding alditol monomer M1 from vanillin and halogenated alkyl alcohol, and generating corresponding diol monomer M2 from M1 under the action of a reducing agent; the M1 and M2 monomers are respectively dehydrogenated and condensed under the action of a Milstein catalyst to generate the bio-based polyester containing aromatic groups, and the yield is higher than 90%. Compared with the traditional polycondensation, the reaction monomer of the process method is easier to prepare, the reaction condition is milder, the byproduct is only hydrogen, the requirement on production equipment is low, and the process method conforms to the principle of green, efficient and safe production.
Description
Technical Field
The invention belongs to the technical field of bio-based polymer synthesis, and particularly relates to a preparation method of vanillin-based polyester.
Background
The use of fossil-based polymeric materials has increasingly severe environmental impact. The "white pollution" is formed by the non-degradable waste high polymer materials accumulated year by year. Meanwhile, coal, petroleum and the like belong to non-renewable resources, and the use of a large amount of coal, petroleum and the like can cause fossil energy exhaustion; and the carbon dioxide discharged in the preparation process of the fossil-based high polymer material can also cause the greenhouse effect. In recent years, the preparation of bio-based polymer materials by using renewable resources has been receiving more and more attention in view of environmental protection and sustainable development.
Bio-based polyesters, which are one of the most important types of bio-based polymer materials, polylactic acid (PLA), polyhydroxyalkanoate (PHA), polybutylene succinate (PBS), and the like, which have been commercialized at present, have good biocompatibility and degradability, but their properties in terms of strength, toughness, heat resistance, gas barrier property, and the like, need to be further improved due to the lack of a rigid structure in the molecular chain, as compared to conventional petroleum-based polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT). Therefore, there is an urgent need to develop a method for preparing bio-based polyester containing rigid groups.
Vanillic Acid (VA) derived from biomass has become one of the candidate compounds for aryl monomers from which fully biobased or partially biobased polyesters can be prepared. VA-based polyesters have been studied more and more so far, but the synthesis process thereof requires the conversion of vanillin to the corresponding hydroxy acid first, followed by further polycondensation to obtain a vanillyl acid based polyester; the polycondensation reaction needs to be carried out under the harsh conditions of high temperature, even vacuum and the like, the energy consumption is large, and the obtained polymer has low molecular weight and uncontrollable molecular weight distribution. Therefore, there is an urgent need to develop a new polymerization method to realize the polymerization of vanillin monomers under mild conditions to synthesize aromatic polyesters.
In 2005 and 2007, the millstein task group of the scientist israel uses a pincer-type ruthenium complex (PNN-Ru) as a catalyst, and respectively realizes that alcohol is dehydrogenated and coupled to generate ester and alcohol is dehydrogenated and coupled to generate amide, the catalytic efficiency is high, only hydrogen is generated as a byproduct, and the two reactions provide a chance for preparing polyester and polyamide by efficient dehydrogenation and polycondensation of alcohol compounds. In 2011, a catalytic system of Milstein is applied to a Guan subject group of American scientists, so that the direct dehydrogenation and polycondensation of diol and diamine are realized, and the polyamide is successfully prepared. In 2012, the Milstein task group also studied this reaction and further expanded the variety of reaction substrates. In the same year, the Robertson project group uses the catalytic system to realize the bulk dehydrogenation and polycondensation of long-chain diol to obtain polyester, and the number average molecular weight of the obtained polymer can reach 145kg/mol at most. The mechanism of the two types of dehydrogenocondensation reactions is shown in FIG. 1: reacting alcohol with a pyridine ring dearomatized PNN-Ru complex to generate a pyridine ring re-aromatized Ru-OR intermediate, wherein the intermediate obtains a pyridine ring aromatized ruthenium double hydrogen compound by eliminating hydrogen on an alkoxy alpha-carbon atom, and simultaneously releases a molecule of aldehyde; while unstable ruthenium dihydrogenates are obtained by removing one molecule of H 2 The catalyst for dearomatization of the pyridine ring is recovered (process A). The resulting aldehyde is reacted with an alcohol or amine to form a hemiacetal or hemiaminal (process B), and the newly formed hydroxyl group is further reacted with a catalyst to finally form an ester or amide (process C). This is a new type of metal and ligand concerted catalytic reaction, and as can be seen from fig. 1, in the whole catalytic process, besides the central metal, the ligand coordinated with it also participates in the activation process of the reaction substrate. Compared with the traditional homogeneous catalysis, the metal-ligand synergetic catalysis remarkably expands the range of catalytic reaction and promotes a plurality of environment-friendly effectsThe occurrence of type catalytic reactions, such as: catalytic hydrogenation of polar unsaturated groups under mild conditions, acceptor-free dehydrogenation, and the like. The catalytic reactions have important significance in organic synthesis and development of petrochemical energy substitutes.
In view of the above, the present invention is expected to further apply such catalytic reaction to the dehydrogenation and polycondensation of biomass monomer vanillin derivatives, and prepare biodegradable polyester materials with different structural properties.
Disclosure of Invention
In order to solve the problems that the existing aliphatic polyester has poor performances such as strength, toughness, heat resistance, gas barrier property and the like, and the polymerization reaction conditions are harsh and the like, the invention provides a method for preparing a series of aromatic polyester from biological vanillin derivatives. The method can use the alcohol aldehyde derivative or the diol derivative of the vanillin as raw materials to efficiently prepare the bio-based polyester containing aromatic groups under mild conditions; meanwhile, vanillin does not need to be converted into vanillic acid, and only hydrogen is generated as a byproduct, so that the reaction is more green and economical.
The invention is realized by the following technical scheme:
the preparation method of the vanillin-based polyester comprises the following steps:
1) Preparation of vanillin monomers: reacting vanillin with halogenated alkyl alcohol to generate a monomer M1 containing aldehyde and hydroxyl, and reducing the aldehyde of the monomer M1 to obtain a monomer M2 containing dihydroxy;
the preparation method of the vanillin monomer comprises the following steps:
2) Preparing vanillin biodegradable polyester: dissolving a Milstein catalyst in an organic solvent to prepare a catalytic system, then adding the monomer M1 or M2 prepared in the step 1), and heating to polymerize the monomer to prepare the vanillin-based biodegradable polyester.
Preferably, in the halogenated alkyl alcohol in the step 1), X is selected from any one of chlorine, bromine and iodine.
Preferably, in the halogenated alkyl alcohol in the step 1), R is linear alkane with the chain length of 1-11, branched alkane or alkane containing unsaturated bonds or heteroatoms.
Preferably, the haloalkyl alcohol is selected from the group consisting of 4-chloro-1-butanol, 5-chloro-1-pentanol, 6-chloro-1-hexanol, 7-chloro-1-heptanol, 8-chloro-1-octanol, 9-chloro-1-nonanol, 10-chloro-1-decanol, 2-bromoethanol, 3-bromo-1-propanol, 4-bromo-1-butanol, 5-bromo-1-pentanol, 6-bromo-1-hexanol, 7-bromo-1-heptanol, 8-bromo-1-octanol, 9-bromo-1-nonanol, 10-bromo-1-decanol, 11-bromo-1-undecanol, 12-bromo-1-dodecanol, 2-iodoethanol, 3-iodo-1-propanol, 4-iodo-1-butanol, 5-iodo-1-pentanol, 6-iodo-1-hexanol, 7-iodo-1-heptanol, 8-iodo-1-octanol, 9-iodo-1-nonanol, 10-iodo-1-decanol.
Preferably, the ratio of vanillin monomer M1 or M2 to catalyst in step 2) is (50-5000): 1 (concentration ratio).
Preferably, the polymerization temperature in the step 2) is 80-180 ℃, and the polymerization reaction time is 1-5 days.
According to the invention, an ester bond is generated by dehydrogenation of an aldehyde group and a hydroxyl group of an aldol monomer M1, or an ester bond is generated by twice dehydrocondensation of a diol monomer, so that the polymerization method is novel; adjusting the carbon chain length of the halogenated alkyl alcohol so as to adjust the property of the polymer; due to the difference of regioselectivity during polymerization, the chain structure of the resulting polyester is more diverse, and the properties are greatly different from those of the vanillyl polyester.
Vanillyl polyester is a very useful polymer and is expected to replace the traditional petroleum-based polyester PET and derivatives thereof; the starting material vanillin is derived from lignin and has been industrialized. The method has the advantages of relatively mild reaction conditions, simple process operation, easy separation of the polymer, and recyclable solvent, and avoids environmental problems caused in the process.
Compared with the prior art, the invention has the beneficial effects that:
(1) The vanillin is derived from biomass, the operation of preparing the biodegradable polyester from the vanillin derivatives is simple, the environmental problems caused by the preparation process and the use of the polymer are avoided, and the high-efficiency utilization of resources is realized.
(2) The invention does not need to convert vanillin into vanillic acid, has milder reaction conditions compared with the traditional polycondensation, has low requirements on production equipment, and accords with the principle of safe production.
(3) The invention adopts a metal catalyst with more energy saving and environmental protection, so that only the target polymer and hydrogen are generated in the whole polymerization process, the hydrogen can be used as clean energy, the product is easy to separate and purify, and the method has very large potential industrial application.
Drawings
FIG. 1 shows the reaction mechanism of "metal-ligand synergy" for catalyzing alcohol dehydrogenation condensation to prepare ester or amide.
FIG. 2 shows the NMR spectra of M1-C10 and M2-C10.
FIG. 3 shows the NMR spectra of the polyester prepared with M2-C10 as monomers.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Example 1
Synthesis of 4- (2-hydroxyethoxy) -3-methoxybenzaldehyde: adding 0.1mol of vanillin and 200mL of acetonitrile into a 500mL reaction bottle, stirring to completely dissolve the vanillin and the acetonitrile, adding 0.2mol of anhydrous potassium carbonate, stirring at room temperature for 30 minutes, adding 0.3mol of 2-bromoethanol, and stirring and refluxing for reaction for 16 hours. The reaction was stopped, the temperature was lowered to room temperature, filtered, purified by column chromatography and the yield calculated. Nuclear magnetic resonance and mass spectrometry confirmed the structure.
Example 2
Synthesis of 4- (3-hydroxypropoxy) -3-methoxybenzaldehyde: adding 0.1mol of vanillin and 200mL of acetonitrile into a 500mL reaction bottle, stirring to completely dissolve the vanillin and the acetonitrile, adding 0.2mol of anhydrous potassium carbonate, stirring at room temperature for 30 minutes, adding 0.3mol of 3-bromopropanol, and stirring and refluxing for reaction for 16 hours. The reaction was stopped, the temperature was lowered to room temperature, filtered, purified by column chromatography and the yield calculated. Nuclear magnetic resonance and mass spectrometry confirmed the structure.
Example 3
Synthesis of 4- (4-hydroxybutoxy) -3-methoxybenzaldehyde: adding 0.1mol of vanillin and 200mL of acetonitrile into a 500mL reaction flask, stirring to completely dissolve the vanillin and the acetonitrile, adding 0.2mol of anhydrous potassium carbonate, stirring at room temperature for 30 minutes, adding 0.3mol of 4-bromobutanol, and stirring and refluxing for reaction for 16 hours. The reaction was stopped, the temperature was lowered to room temperature, filtered, purified by column chromatography and the yield calculated. Nuclear magnetic resonance and mass spectrometry confirmed the structure.
Example 4
Synthesis of 4- (5-hydroxypentyloxy) -3-methoxybenzaldehyde: adding 0.1mol of vanillin and 200mL of acetonitrile into a 500mL reaction flask, stirring to completely dissolve the vanillin and the acetonitrile, adding 0.2mol of anhydrous potassium carbonate, stirring at room temperature for 30 minutes, adding 0.3mol of 5-bromopentanol, and stirring and refluxing for reaction for 16 hours. The reaction was stopped, the temperature was lowered to room temperature, filtered, purified by column chromatography and the yield calculated. Nuclear magnetic resonance and mass spectrometry confirmed the structure.
Example 5
Synthesis of 4- (6-hydroxyhexyloxy) -3-methoxybenzaldehyde: adding 0.1mol of vanillin and 200mL of acetonitrile into a 500mL reaction flask, stirring to completely dissolve the vanillin and the acetonitrile, adding 0.2mol of anhydrous potassium carbonate, stirring at room temperature for 30 minutes, adding 0.3mol of 6-bromohexanol, and stirring and refluxing for reaction for 16 hours. The reaction was stopped, the temperature was lowered to room temperature, filtered, purified by column chromatography and the yield calculated. Nuclear magnetic resonance and mass spectrometry confirmed the structure.
Example 6
Synthesis of 4- (7-hydroxyheptyloxy) -3-methoxybenzaldehyde: adding 0.1mol of vanillin and 200mL of acetonitrile into a 500mL reaction flask, stirring to completely dissolve the vanillin and the acetonitrile, adding 0.2mol of anhydrous potassium carbonate, stirring at room temperature for 30 minutes, adding 0.3mol of 7-bromoheptanol, and stirring and refluxing for reaction for 16 hours. The reaction was stopped, the temperature was lowered to room temperature, filtered, purified by column chromatography and the yield calculated. Nuclear magnetic resonance and mass spectrometry confirmed the structure.
Example 7
Synthesis of 4- (8-hydroxyoctyloxy) -3-methoxybenzaldehyde: adding 0.1mol of vanillin and 200mL of acetonitrile into a 500mL reaction bottle, stirring to completely dissolve the vanillin and the acetonitrile, adding 0.2mol of anhydrous potassium carbonate, stirring at room temperature for 30 minutes, adding 0.3mol of 8-bromooctanol, and stirring and refluxing for reaction for 16 hours. The reaction was stopped, the temperature was lowered to room temperature, filtered, purified by column chromatography and the yield calculated. Nuclear magnetic resonance and mass spectrometry confirmed the structure.
Example 8
Synthesis of 4- (9-hydroxynonanyloxy) -3-methoxybenzaldehyde: adding 0.1mol of vanillin and 200mL of acetonitrile into a 500mL reaction bottle, stirring to completely dissolve the vanillin and the acetonitrile, adding 0.2mol of anhydrous potassium carbonate, stirring at room temperature for 30 minutes, adding 0.3mol of 9-bromononanol, and stirring and refluxing for reaction for 16 hours. The reaction was stopped, the temperature was lowered to room temperature, filtered, purified by column chromatography and the yield calculated. Nuclear magnetic resonance and mass spectrometry confirmed the structure.
Example 9
Synthesis of 4- (10-hydroxydecyloxy) -3-methoxybenzaldehyde: adding 0.1mol of vanillin and 200mL of acetonitrile into a 500mL reaction flask, stirring to completely dissolve the vanillin and the acetonitrile, adding 0.2mol of anhydrous potassium carbonate, stirring at room temperature for 30 minutes, adding 0.3mol of 10-bromodecanol, and stirring and refluxing for reaction for 16 hours. The reaction was stopped, the temperature was lowered to room temperature, filtered, purified by column chromatography and the yield calculated. Nuclear magnetic resonance and mass spectrometry confirmed the structure.
Example 10
Synthesis of 4- (2-hydroxyethoxy) -3-methoxybenzyl alcohol: a500 mL reaction flask was charged with 0.05mol of 4- (2-hydroxyethoxy) -3-methoxybenzaldehyde in methanol (300 mL), followed by slow addition of 0.1mol of sodium borohydride in an ice-water bath. After the addition, the mixture was removed from the ice water bath and stirred at room temperature for 5 hours. The reaction was stopped, filtered, purified by column chromatography and the yield calculated. Nuclear magnetic resonance and mass spectrometry confirmed the structure.
Example 11
Synthesis of 4- (3-hydroxypropoxy) -3-methoxybenzyl alcohol: a500 mL reaction flask was charged with 0.05mol of 4- (3-hydroxypropoxy) -3-methoxybenzaldehyde in methanol (300 mL), followed by slow addition of 0.1mol of sodium borohydride in an ice-water bath. After the addition, the mixture was removed from the ice water bath and stirred at room temperature for 5 hours. The reaction was stopped, filtered, purified by column chromatography and the yield calculated. Nuclear magnetic resonance and mass spectrometry confirmed the structure.
Example 12
Synthesis of 4- (4-hydroxybutoxy) -3-methoxyphenylmethanol: a500 mL reaction flask was charged with 0.05mol of 4- (4-hydroxybutoxy) -3-methoxybenzaldehyde in methanol (300 mL), followed by slow addition of 0.1mol of sodium borohydride in an ice-water bath. After the addition, the mixture was removed from the ice water bath and stirred at room temperature for 5 hours. The reaction was stopped, filtered, purified by column chromatography and the yield calculated. Nuclear magnetic resonance and mass spectrometry confirmed the structure.
Example 13
Synthesis of 4- (5-hydroxypentyloxy) -3-methoxybenzyl alcohol: a500 mL reaction flask was charged with 0.05mol of a solution of 4- (5-hydroxypentyloxy) -3-methoxybenzaldehyde in methanol (300 mL), followed by slow addition of 0.1mol of sodium borohydride in an ice-water bath. After the addition, the mixture was removed from the ice water bath and stirred at room temperature for 5 hours. The reaction was stopped, filtered, purified by column chromatography and the yield calculated. Nuclear magnetic resonance and mass spectrometry confirmed the structure.
Example 14
Synthesis of 4- (6-hydroxyhexyloxy) -3-methoxybenzyl alcohol: a500 mL reaction flask was charged with 0.05mol of 4- (6-hydroxyhexyloxy) -3-methoxybenzaldehyde in methanol (300 mL), followed by slow addition of 0.1mol of sodium borohydride in an ice-water bath. After the addition, the mixture was removed from the ice water bath and stirred at room temperature for 5 hours. The reaction was stopped, filtered, purified by column chromatography and the yield calculated. Nuclear magnetic resonance and mass spectrometry confirmed the structure.
Example 15
Synthesis of 4- (7-hydroxyheptyloxy) -3-methoxybenzyl alcohol: a500 mL reaction flask was charged with 0.05mol of a solution of 4- (7-hydroxyheptyloxy) -3-methoxybenzaldehyde in methanol (300 mL), followed by slow addition of 0.1mol of sodium borohydride in an ice-water bath. After the addition, the mixture was removed from the ice water bath and stirred at room temperature for 5 hours. The reaction was stopped, filtered, purified by column chromatography and the yield calculated. Nuclear magnetic resonance and mass spectrometry confirmed the structure.
Example 16
Synthesis of 4- (8-hydroxyoctyloxy) -3-methoxybenzyl alcohol: a500 mL reaction flask was charged with 0.05mol of 4- (8-hydroxyoctyloxy) -3-methoxybenzaldehyde in methanol (300 mL), followed by slow addition of 0.1mol of sodium borohydride in an ice-water bath. After the addition, the mixture was removed from the ice water bath and stirred at room temperature for 5 hours. The reaction was stopped, filtered, purified by column chromatography and the yield calculated. Nuclear magnetic resonance and mass spectrometry confirmed the structure.
Example 17
Synthesis of 4- (9-hydroxynonanyloxy) -3-methoxybenzyl alcohol: a500 mL reaction flask was charged with 0.05mol of a solution of 4- (9-hydroxynonanyloxy) -3-methoxybenzaldehyde in methanol (300 mL), followed by slow addition of 0.1mol of sodium borohydride in an ice-water bath. After the addition, the mixture was removed from the ice water bath and stirred at room temperature for 5 hours. The reaction was stopped, filtered, purified by column chromatography and the yield calculated. Nuclear magnetic resonance and mass spectrometry confirmed the structure.
Example 18
Synthesis of 4- (10-hydroxydecyloxy) -3-methoxybenzyl alcohol: a500 mL reaction flask was charged with 0.05mol of 4- (10-hydroxydecyloxy) -3-methoxybenzaldehyde in methanol (300 mL), followed by slow addition of 0.1mol of sodium borohydride in an ice-water bath. After the addition, the mixture was removed from the ice water bath and stirred at room temperature for 5 hours. The reaction was stopped, filtered, purified by column chromatography and the yield calculated. Nuclear magnetic resonance and mass spectrometry confirmed the structure.
Example 19 (Polymer Synthesis method)
In a glove box, a 25mL reaction vessel was charged with Milstein catalyst (9.8 mg, 0.02mmol) and potassium tert-butoxide (2.2mg, 0.02mmol), followed by toluene or anisole (1.0 mL), and the mixture was stirred at room temperature for 5 minutes to activate the catalyst. Then monomer M1 or M2 (1 mmol, in this amount for example) was added, the vessel was sealed and removed from the glove box and the solution was heated to 120 ℃ with stirring in an oil bath. The reaction was stirred under nitrogen for 12 hours, then the solvent was removed under reduced pressure and the reaction was carried out in vacuo for 4 days. After cooling to room temperature, the reaction vessel was removed from the oil bath, and the resulting polymer was dissolved in a small amount of toluene, which was then precipitated in methanol. The dissolution-precipitation was repeated three times and the polymer was dried in vacuo. Nuclear magnetic resonance, GPC, DSC, TGA characterize the polymer.
TABLE 1 polyester data generated by Vanillyl monomers M1 and M2 in the presence of a catalyst
Remarking: m1 is an alditol monomer; m2 is a diol monomer; C2-C12 represent the number of carbon atoms linking the alkyl alcohol.
The embodiments described above merely represent some preferred embodiments of the present invention, which are described in more detail and detail, but are not intended to limit the present invention. It should be understood that various changes and modifications can be made by those skilled in the art, and any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (5)
1. The preparation method of the vanillin-based polyester is characterized by comprising the following steps of:
1) Preparation of vanillin monomer: reacting vanillin with halogenated alkyl alcohol to generate a monomer M1 containing aldehyde group and hydroxyl;
the preparation method of the vanillin monomer comprises the following steps:
in the halogenated alkyl alcohol, R is straight-chain alkane, branched-chain alkane or alkane containing unsaturated bonds or heteroatoms with the chain length of 1-11;
2) Preparing vanillin biodegradable polyester: dissolving a Milstein catalyst in an organic solvent to prepare a catalytic system, then adding the monomer M1 prepared in the step 1), and heating to polymerize the monomer to prepare the vanillin-based biodegradable polyester.
2. The method for preparing vanillin-based polyester according to claim 1, wherein X in the alkyl halide in step 1) is selected from any one of chlorine, bromine and iodine.
3. The method for preparing vanillin-based polyester according to claim 1, wherein the alkyl halide is selected from the group consisting of 4-chloro-1-butanol, 5-chloro-1-pentanol, 6-chloro-1-hexanol, 7-chloro-1-heptanol, 8-chloro-1-octanol, 9-chloro-1-nonanol, 10-chloro-1-decanol, 2-bromoethanol, 3-bromo-1-propanol, 4-bromo-1-butanol, 5-bromo-1-pentanol, 6-bromo-1-hexanol, 7-bromo-1-heptanol, 8-bromo-1-octanol, 9-bromo-1-nonanol, 10-bromo-1-decanol, 11-bromo-1-undecanol, 12-bromo-1-dodecanol, 2-iodoethanol, 3-iodo-1-propanol, 4-iodo-1-butanol, 5-iodo-1-pentanol, 6-iodo-1-hexanol, 7-iodo-1-heptanol, 8-iodo-1-heptanol, and 9-iodo-1-nonanol.
4. The method for preparing vanillin-based polyester according to claim 1, wherein the ratio of vanillin monomer M1 to catalyst in step 2) is (50-5000): 1.
5. The method for preparing vanillin-based polyester according to claim 1, wherein the polymerization temperature in the step 2) is 80-180 ℃ and the polymerization time is 1-5 days.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210097450.1A CN114507339B (en) | 2022-01-27 | 2022-01-27 | Preparation method of vanillin-based polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210097450.1A CN114507339B (en) | 2022-01-27 | 2022-01-27 | Preparation method of vanillin-based polyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114507339A CN114507339A (en) | 2022-05-17 |
| CN114507339B true CN114507339B (en) | 2023-04-07 |
Family
ID=81550495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210097450.1A Active CN114507339B (en) | 2022-01-27 | 2022-01-27 | Preparation method of vanillin-based polyester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114507339B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115772258B (en) * | 2022-11-24 | 2024-04-30 | 江南大学 | Preparation method of intrinsic type degradable bioactive polyester |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897157B (en) * | 2012-12-25 | 2016-03-30 | 杜邦公司 | The method of aliphatic polyester is prepared by glycol |
| CN112341652B (en) * | 2020-11-23 | 2022-06-07 | 苏州大学 | Chiral azobenzene polymer film and preparation method and application thereof |
-
2022
- 2022-01-27 CN CN202210097450.1A patent/CN114507339B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114507339A (en) | 2022-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114507339B (en) | Preparation method of vanillin-based polyester | |
| Kasmi et al. | Effective and facile solvent-free synthesis route to novel biobased monomers from vanillic acid: Structure–thermal property relationships of sustainable polyesters | |
| JP5618040B2 (en) | High molecular weight aliphatic polyester ether using bio-based raw material and process for producing the same | |
| CN113788793B (en) | Sulfonic acid functionalized imidazole ionic liquid catalyst and preparation method and application thereof | |
| US8759545B2 (en) | Method of preparing lactide from lactate | |
| WO2020168177A1 (en) | Methods and compositions for biorenewable polyesters derived from camphoric acid | |
| US10662289B2 (en) | Polymers from bio-derived dicarboxylic acids | |
| EP3119750B1 (en) | Pendant furyl containing bisphenols, polymers therefrom and a process for the preparation thereof | |
| WO2006124899A2 (en) | Production of derivatives of lactide, production of lactides, and use of lactide in foods and to produce polymers | |
| CN113461926A (en) | Chemical synthesis method of poly beta-hydroxy fatty acid ester | |
| WO2018236218A1 (en) | Production and use of furan compounds | |
| KR20130099623A (en) | A method for lactide synthesis from lactic acid | |
| US11987567B2 (en) | Synthesis method of lactide by confinement effect catalysis of crystalline porous polymer material | |
| CN114315728B (en) | Imidazole ionic liquid and application thereof in alcoholysis polymerization of 2, 5-furandicarboxylic acid ester | |
| US10745375B2 (en) | Adipate-type compounds and a process of preparing it | |
| CN105524257B (en) | A kind of full bio-based polyester of ketone group containing and preparation method thereof | |
| CN109678822B (en) | Preparation method of 2, 5-furan diformic acid ester compound | |
| Rahim et al. | Synthesis of bio-based monomer from vegetable oil fatty acids and design of functionalized greener polyester | |
| CN114315790B (en) | Preparation method of cyclic carbonate | |
| CN109053383B (en) | Method and catalyst for efficiently alcoholysis of polycarbonate under mild condition | |
| EP3733733A1 (en) | Polyesters from lignin-based monomers | |
| JP2024066910A (en) | Epoxy compound, epoxy resin composition, and epoxy compound production method | |
| CN114539510A (en) | Preparation method of poly-6-benzyl caprolactone | |
| CN118496093A (en) | Method for preparing alcohol compound by chemical recovery of polylactic acid and application thereof | |
| CN118479965A (en) | Synthesis method of dimethyl terephthalate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |