CN111647107B - Performance-adjustable castor oil-based vinyl ester thermosetting material and preparation method thereof - Google Patents
Performance-adjustable castor oil-based vinyl ester thermosetting material and preparation method thereof Download PDFInfo
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- CN111647107B CN111647107B CN202010407197.6A CN202010407197A CN111647107B CN 111647107 B CN111647107 B CN 111647107B CN 202010407197 A CN202010407197 A CN 202010407197A CN 111647107 B CN111647107 B CN 111647107B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
Abstract
The invention provides a performance-adjustable castor oil-based vinyl ester thermosetting material, which is prepared by taking double-bonded modified castor oil as matrix resin and double-bonded eugenol as an active diluent through free radical copolymerization reaction in the presence of an initiator. The castor oil-based vinyl ester thermosetting material has the advantages that the castor oil methacrylate serves as a soft monomer due to the flexible long-chain structure of the castor oil methacrylate, and the double-bonded eugenol serves as a hard monomer due to the rigid benzene ring structure of the double-bonded eugenol, so that the performance regulation and control of the castor oil-based vinyl ester thermosetting material can be realized by changing the proportion of the castor oil methacrylate and the double-bonded eugenol. The material not only has excellent mechanical properties of the traditional petroleum-based vinyl ester thermosetting material, but also has the advantages of simple preparation method, mild process conditions and capability of adopting a liquid molding technology, and the raw materials are all from renewable biomass resources, so that the high-added-value utilization of castor oil and eugenol is realized, and the development of a green sustainable new material with the advantages of environment friendliness and environmental friendliness is assisted.
Description
Technical Field
The invention belongs to the technical field of biomass-based thermosetting materials, and particularly relates to a castor oil-based vinyl ester thermosetting material and a preparation method thereof.
Background
The traditional vinyl ester thermosetting polymer material is widely applied to the fields of building infrastructure, marine oil industry, aerospace, automobiles and the like by virtue of the characteristics of excellent mechanical property, chemical stability, heat resistance and the like, and plays an important role in national production and life. However, most of raw materials used for preparing the vinyl ester thermosetting material are from non-renewable petrochemical resources, and the active diluent used for preparing the vinyl ester thermosetting material in the market at present is mainly styrene, which is a substance with high volatility at room temperature, is considered as a harmful air pollutant and a potential carcinogen, and poses threats to the natural environment and human health. Therefore, there is a need to develop vinyl ester thermosets based on renewable biomass resources to replace petroleum-based vinyl ester thermosets.
Castor oil is a triglyceride of fatty acids with long flexible segments in the molecular structure. It is an important inedible vegetable oil, called as renewable 'green petroleum', and has the characteristics of rich resources, low price and the like, and the molecular structure contains unsaturated carbon-carbon double bonds, hydroxyl, ester groups and other active reaction groups. Therefore, castor oil can be used as a raw material to prepare the castor oil-based vinyl ester resin through structural design, and the castor oil-based vinyl ester resin is used for replacing the traditional petroleum-based vinyl ester resin.
Eugenol is a biomass raw material with clove odor, and the molecular structure contains phenolic hydroxyl, allyl groups and a rigid benzene ring structure. The reactive diluent with a structure similar to that of styrene can be prepared by modifying the phenolic hydroxyl group of eugenol.
Disclosure of Invention
The double-bonded eugenol is prepared from eugenol and methacrylic anhydride by a one-step esterification method, is used for replacing styrene as an active diluent, and on one hand, the viscosity of a vinyl ester resin system can be adjusted, and the processing characteristics of the material are improved; on the other hand, the material can generate free radical copolymerization reaction with vinyl ester resin, and the crosslinking density and the mechanical property of the material after crosslinking and curing are improved. Therefore, the castor oil-based vinyl ester thermosetting material with adjustable and controllable performance can be prepared by carrying out free radical polymerization on the castor oil-based vinyl ester matrix resin prepared by using green and renewable castor oil through structural design and the double-bonded eugenol, the material not only reduces the dependence on non-renewable petrochemical resources, but also has important significance on green sustainable development, and is expected to solve the environmental and resource problems caused by the traditional petroleum-based vinyl ester thermosetting material.
The invention aims to provide a castor oil based vinyl ester thermosetting material with adjustable and controllable performance and a preparation method thereof. According to the method, castor oil methacrylate is used as matrix resin, double-bonded eugenol is used as an active diluent, and the castor oil-based vinyl ester thermosetting material is obtained through free radical copolymerization reaction and solidification under the action of an initiator. The performance of the castor oil-based vinyl ester thermosetting material can be regulated and controlled by regulating and controlling the proportion of the castor oil-based vinyl ester thermosetting material to the castor oil-based vinyl ester thermosetting material.
The technical principle is as follows:
compared with double-bonded eugenol, the synthesized castor oil methacrylate has longer molecular chains, higher molecular weight and more polar groups, so that the viscosity of the castor oil methacrylate is higher due to the acting forces such as van der Waals force, hydrogen bonds and the like, and in addition, the castor oil methacrylate contains high-activity unsaturated carbon-carbon double bonds (methacrylate ester bonds); meanwhile, the synthesized double-bonded eugenol monomer has the characteristics of short molecular chain and low molecular weight, so that the double-bonded eugenol monomer has low viscosity and can be used as an active diluent of castor oil methacrylate, meanwhile, the double-bonded eugenol contains two unsaturated carbon-carbon double bonds (methacrylate group and allyl group), and can be subjected to free radical polymerization reaction with the unsaturated carbon-carbon double bonds in the castor oil methacrylate to prepare the castor oil-based vinyl ester thermosetting material under a certain initiating condition, and the problem of crushing caused by internal stress in the material preparation process is solved by adopting a staged heating and curing process. The castor oil methacrylate has a flexible long-chain structure and serves as a soft segment, and the double-bonded eugenol serves as a hard segment due to a rigid benzene ring structure, so that the mechanical property and the thermodynamic property of the castor oil-based vinyl ester thermosetting material can be regulated and controlled by regulating and controlling the using amounts of the castor oil methacrylate and the double-bonded eugenol.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the castor oil-based vinyl ester thermosetting material with adjustable and controllable properties is characterized by comprising the following steps:
the method comprises the following steps: preparation of castor oil methacrylate
Uniformly mixing 1 part of castor oil, 25-30 parts of tetrahydrofuran and 3-4 parts of triethylamine, placing the mixture in an ice water bath, and stirring; then slowly dropwise adding a mixed solution of 4.5-6 parts of methacryloyl chloride and 12-16 parts of tetrahydrofuran, after dropwise adding, recovering the reaction mixed solution to room temperature (20-30 ℃), and reacting at room temperature for 6-12 h; after the reaction is finished, diluting the reaction solution with dichloromethane, and then extracting and washing with saturated sodium bicarbonate solution, 0.5-1 mol/L NaOH, 0.5-1 mol/L HCl and saturated saline respectively; and finally, drying by using anhydrous magnesium sulfate, carrying out suction filtration, carrying out reduced pressure rotary evaporation to remove dichloromethane, and drying in a vacuum oven at the temperature of 30-45 ℃ for 6-12 h to obtain the castor oil methacrylate.
Step two: preparation of double-bonded eugenol
Uniformly mixing 40-50 parts of eugenol and 1-1.5 parts of 4-dimethylaminopyridine at room temperature, placing the mixture in a three-neck flask, uniformly stirring, and introducing nitrogen for 1-2 hours to remove moisture and oxygen; slowly dropwise adding 45-60 parts of methacrylic anhydride into a three-neck flask, gradually increasing the temperature to 40-50 ℃, strongly stirring, and reacting for 24 hours; after the reaction is finished, diluting the product with dichloromethane, fully washing the product with saturated sodium bicarbonate solution, and then extracting and washing the product with 1 mol/L NaOH, 0.5 mol/L NaOH, 1 mol/L HCl and saturated saline solution; and finally, drying with anhydrous magnesium sulfate, carrying out suction filtration, carrying out reduced pressure rotary evaporation to remove the solvent, and drying in a vacuum oven at the temperature of 30-45 ℃ for 6-12 h to obtain the double-bonded eugenol.
Step three: preparation of castor oil based vinyl ester thermosetting material
Uniformly mixing the castor oil methacrylate and the double-bonded eugenol, adding an initiator, pouring into an aluminum alloy mould, removing bubbles in a vacuum oven, and curing. The curing conditions were: curing at 75-90 ℃ for 0.5-1.5 h, heating to 110-.
The invention is also characterized in that:
and in the step one, the mixed solution of the methacrylic chloride and the tetrahydrofuran is slowly dropped into the reactor within 30-60 min.
The initiator in the third step is one of tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, benzoyl peroxide and azobisisobutyronitrile.
10-100 parts of castor oil methacrylate, 10-100 parts of double-bonded eugenol and 1-5 parts of an initiator.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the castor oil-based vinyl ester thermosetting material prepared by the invention is a vinyl ester thermosetting material with high biomass content. The raw materials of castor oil and eugenol used for preparation have the characteristics of abundant resources, low cost, renewability, environmental protection and the like, and are beneficial to promoting the high-added-value utilization of biomass resources.
(2) The invention provides a castor oil-based vinyl ester thermosetting material with adjustable performance, which can realize the adjustment and control of the thermodynamic property and the mechanical property of a final solidified vinyl ester material by changing the proportion of castor oil methacrylate and double-bonded eugenol.
(3) The castor oil-based vinyl ester thermosetting material developed by the invention is expected to replace petroleum-based vinyl ester thermosetting materials in the future, and is helpful for promoting the development of green sustainable new materials.
(4) The method for preparing the castor oil-based vinyl ester thermosetting material provided by the invention is simple, has mild process conditions, and can be compounded with fibers and applied to a liquid molding technology to prepare the composite material.
Drawings
FIG. 1 is a synthetic route for castor oil methacrylate;
FIG. 2 is a synthetic route of double-bonded eugenol;
FIG. 3 is a nuclear magnetic map of castor oil methacrylate;
FIG. 4 is a nuclear magnetic spectrum of double-bonded eugenol.
Detailed Description
The present invention is further described with reference to the following specific embodiments, and the technical solutions of the present invention are not limited to the specific embodiments listed below, and include any combination of the specific embodiments.
Example 1
Preparation of castor oil based vinyl ester thermosetting material
The method comprises the following steps: uniformly mixing 1 part of castor oil, 27 parts of tetrahydrofuran and 3.2 parts of triethylamine, placing the mixture in an ice-water bath, and stirring; then slowly dropwise adding a mixed solution of 5 parts of methacryloyl chloride and 12 parts of tetrahydrofuran, after dropwise adding, recovering the reaction solution to room temperature, and reacting at room temperature for 6 hours; after the reaction is finished, diluting the reaction solution with dichloromethane, and then extracting and washing with saturated sodium bicarbonate, 0.5 mol/L NaOH, 0.5 mol/L HCl and saturated saline respectively; finally, the mixture is dried by anhydrous magnesium sulfate, filtered, decompressed, rotary-distilled to remove dichloromethane and dried in a vacuum oven at the temperature of 30 ℃ for 12 hours, and the castor oil methacrylate is prepared, wherein the yield is 49.51%.
Step two: uniformly mixing 40 parts of eugenol and 1 part of 4-dimethylaminopyridine, putting the mixture into a three-neck flask, uniformly stirring, and introducing nitrogen for 2 hours to remove moisture and oxygen; then slowly dripping 50 parts of methacrylic anhydride into the three-neck flask, gradually increasing the temperature to 45 ℃, strongly stirring, and reacting for 24 hours; after the reaction is finished, diluting the product with dichloromethane, washing the product with a large amount of saturated sodium bicarbonate, and then extracting and washing the product with 1 mol/L NaOH, 0.5 mol/L NaOH, 1 mol/L HCl and saturated salt water; and finally, drying by using anhydrous magnesium sulfate, carrying out suction filtration, carrying out reduced pressure rotary evaporation to remove the solvent, and drying in a vacuum oven at the temperature of 45 ℃ for 12 hours to obtain the double-bonded eugenol.
Step three: uniformly mixing 100 parts of castor oil methacrylate ACO and 10 parts of double-bonded eugenol, adding 1 part of initiator tert-butyl peroxybenzoate, pouring into a mold, removing bubbles in a vacuum oven, heating to 90 ℃ for curing for 1 hour, heating to 130 ℃ for curing for 5 hours, and finally curing at 170 ℃ for 2 hours to obtain the target product castor oil-based vinyl ester thermosetting material.
Example 2
Preparation of castor oil based vinyl ester thermosetting material
The method comprises the following steps: uniformly mixing 1 part of castor oil, 30 parts of tetrahydrofuran and 4 parts of triethylamine, placing the mixture in an ice-water bath, and stirring the mixture; then slowly dropwise adding a mixed solution of 5.4 parts of methacryloyl chloride and 12 parts of tetrahydrofuran, after dropwise adding, reducing the temperature of the reactant to room temperature, and reacting at the room temperature for 12 hours; after the reaction is finished, diluting the reaction solution with dichloromethane, and then extracting and washing with saturated sodium bicarbonate, 1 mol/L NaOH, 1 mol/L HCl and saturated saline respectively; finally, the intermediate product castor oil methacrylate is obtained by drying with anhydrous magnesium sulfate, filtering, decompressing and rotary steaming to remove dichloromethane and drying in a vacuum oven at 40 ℃ for 6h, wherein the yield is 58.9%.
Step two: uniformly mixing 47 parts of eugenol and 1 part of 4-dimethylaminopyridine, putting the mixture into a three-neck flask, uniformly stirring, and introducing nitrogen for 2 hours to remove moisture and oxygen; then slowly dripping 52 parts of methacrylic anhydride into the three-neck flask, gradually increasing the temperature to 45 ℃, strongly stirring, and reacting for 24 hours; after the reaction is finished, diluting the product with dichloromethane, washing the product with a large amount of saturated sodium bicarbonate, and then extracting and washing the product with 1 mol/L NaOH, 0.5 mol/L NaOH, 1 mol/L HCl and saturated salt water; and finally, drying by using anhydrous magnesium sulfate, carrying out suction filtration, carrying out reduced pressure rotary evaporation to remove the solvent, and drying in a vacuum oven at the temperature of 40 ℃ for 12 hours to obtain the double-bonded eugenol.
Step three: uniformly mixing 100 parts of castor oil methacrylate and 40 parts of double-bonded eugenol, adding 3 parts of initiator tert-butyl peroxybenzoate, pouring into a mold, removing bubbles in a vacuum oven, heating to 90 ℃, curing for 1 hour, curing for 5 hours at 130 ℃, and finally curing for 2 hours at 170 ℃, thus obtaining the target product castor oil-based vinyl ester thermosetting material.
Example 3
Preparation of castor oil based vinyl ester thermosetting material
The method comprises the following steps: uniformly mixing 1 part of castor oil, 25 parts of tetrahydrofuran and 4 parts of triethylamine, placing the mixture in an ice-water bath, and stirring the mixture; then slowly dropwise adding a mixed solution of 6 parts of methacryloyl chloride and 14 parts of tetrahydrofuran, after dropwise adding, reducing the temperature of the reactants to room temperature, and reacting at the room temperature for 12 hours; after the reaction is finished, diluting the reaction solution with dichloromethane, and then extracting and washing with saturated sodium bicarbonate, 1 mol/L NaOH, 1 mol/L HCl and saturated saline respectively; finally, the intermediate product castor oil methacrylate is obtained by drying with anhydrous magnesium sulfate, filtering, decompressing and rotary steaming to remove dichloromethane and drying in a vacuum oven at 30 ℃ for 6h, wherein the yield is 69.1%.
Step two: uniformly mixing 50 parts of eugenol and 1.5 parts of 4-dimethylaminopyridine, putting the mixture into a three-neck flask, uniformly stirring, and introducing nitrogen for 2 hours to remove moisture and oxygen; then slowly dripping 60 parts of methacrylic anhydride into the three-neck flask, gradually increasing the temperature to 45 ℃, strongly stirring, and reacting for 24 hours; after the reaction is finished, diluting the product with dichloromethane, washing the product with a large amount of saturated sodium bicarbonate, and then extracting and washing the product with 1 mol/L NaOH, 0.5 mol/L NaOH, 1 mol/L HCl and saturated salt water; and finally, drying by using anhydrous magnesium sulfate, carrying out suction filtration, carrying out reduced pressure rotary evaporation to remove the solvent, and drying in a vacuum oven at the temperature of 45 ℃ for 12 hours to obtain the double-bonded eugenol.
Step three: uniformly mixing 100 parts of castor oil methacrylate and 60 parts of double-bonded eugenol, adding 4 parts of initiator tert-butyl peroxybenzoate, pouring into a mold, removing bubbles in a vacuum oven, heating to 90 ℃, curing for 1.5 hours, curing for 6 hours at 130 ℃, and finally curing for 2 hours at 160 ℃, thereby obtaining the target product castor oil-based vinyl ester thermosetting material.
Comparative example 1
Compared with the example 1, the comparative example is different only in that the double-bonded eugenol in the step three is replaced by the same amount of styrene monomer, the castor oil-based vinyl ester thermosetting material is prepared by the free radical copolymerization reaction of the castor oil methacrylate and the styrene, and the rest of the raw materials and the process are the same as the example 1.
Comparative example 2
Compared with the example 1, the difference of the comparative example is that the double-bonded eugenol in the step three is removed, the castor oil-based vinyl ester thermosetting material is prepared by self polymerization only by using the castor oil methacrylate, the first step is omitted, and the rest of raw materials and processes are the same as those in the example 1.
Comparative example 3
Compared with the example 2, the comparative example is different only in that the curing process in the step three is replaced by the curing condition of curing for 6h at 160 ℃, omitting the curing for 1.5 h at 90 ℃, 6h at 130 ℃ and 2h at 160 ℃, and the rest of the raw materials and the process are the same as the example 2.
Comparison of application examples 1-3 and comparative examples 1-3 with castor oil based vinyl ester thermosets: compared with the embodiment 1, the castor oil-based vinyl ester thermosetting material prepared by using double-bonded eugenol to replace styrene has the advantages that the odor of the product is small in the preparation process, the content of biomass carbon is high, and the environmental friendliness is good; compared with the embodiment 1, the invention has the advantages that the invention can better use the liquid molding forming process, the process condition is simpler and milder, and the mechanical property of the prepared material is higher; compared with the embodiment 2, the castor oil-based vinyl ester thermosetting material obtained in the step-type heating and curing process adopted by the invention is not easy to break and has better performance.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements 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 castor oil-based vinyl ester thermosetting material with adjustable and controllable properties is characterized by comprising the following steps:
uniformly mixing 1 part of castor oil, 25-30 parts of tetrahydrofuran and 3-4 parts of triethylamine by mass, placing in an ice water bath, and stirring; slowly dropwise adding a mixed solution of 4.5-6 parts of methacryloyl chloride and 12-16 parts of tetrahydrofuran, after dropwise adding, recovering the reaction mixed solution to room temperature, and reacting at room temperature for 6-12 h; after the reaction is finished, diluting the reaction solution with dichloromethane, and then extracting and washing with saturated sodium bicarbonate solution, 0.5-1 mol/L NaOH, 0.5-1 mol/L HCl and saturated saline respectively; finally, drying by using anhydrous magnesium sulfate, carrying out suction filtration, carrying out reduced pressure rotary evaporation to remove dichloromethane, and drying in a vacuum oven at the temperature of 30-45 ℃ for 6-12 h to obtain castor oil methacrylate;
uniformly mixing 40-50 parts of eugenol and 1-1.5 parts of 4-dimethylaminopyridine at room temperature, placing the mixture in a three-neck flask, uniformly stirring, and introducing nitrogen for 1-2 hours to remove moisture and oxygen; slowly dropwise adding 45-60 parts of methacrylic anhydride into a three-neck flask, gradually increasing the temperature to 40-50 ℃, strongly stirring, and reacting for 24 hours; after the reaction is finished, diluting the product with dichloromethane, fully washing the product with saturated sodium bicarbonate solution, and then extracting and washing the product with 1 mol/L NaOH, 0.5 mol/L NaOH, 1 mol/L HCl and saturated saline solution; finally, drying with anhydrous magnesium sulfate, carrying out suction filtration, carrying out reduced pressure rotary evaporation to remove the solvent, and drying in a vacuum oven at the temperature of 30-45 ℃ for 6-12 h to obtain double-bonded eugenol;
according to the mass percent, 10-100 parts of castor oil methacrylate, 10-100 parts of double-bonded eugenol and 1-5 parts of initiator are uniformly mixed, cured for 0.5-1.5 h at 75-90 ℃, cured for 3-6 h at 110-130 ℃, cured for 1-2 h at 150-170 ℃, and cured through free radical polymerization reaction to obtain the castor oil-based vinyl ester thermosetting material with adjustable performance.
2. The method of claim 1, wherein the initiator is one of tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, benzoyl peroxide, azobisisobutyronitrile.
3. The method of claim 1, wherein the vacuum removes air bubbles prior to curing.
4. The method of claim 1, wherein the dropping of the mixture of methacryloyl chloride and tetrahydrofuran is controlled to be performed within 30-60 min.
5. A performance-controllable castor oil-based vinyl ester thermoset prepared by the method of any one of claims 1 to 4.
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