CN111154071B - Multifunctional epoxy vegetable oil-based UV curing prepolymer and preparation method and application thereof - Google Patents
Multifunctional epoxy vegetable oil-based UV curing prepolymer and preparation method and application thereof Download PDFInfo
- Publication number
- CN111154071B CN111154071B CN201911390353.6A CN201911390353A CN111154071B CN 111154071 B CN111154071 B CN 111154071B CN 201911390353 A CN201911390353 A CN 201911390353A CN 111154071 B CN111154071 B CN 111154071B
- Authority
- CN
- China
- Prior art keywords
- vegetable oil
- acid
- curing
- epoxy vegetable
- multifunctional epoxy
- 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
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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1472—Fatty acids
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1494—Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/10—Epoxy resins modified by unsaturated compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Emergency Medicine (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a multifunctional epoxy vegetable oil-based UV curing prepolymer and a preparation method and application thereof. The preparation method comprises the following steps: uniformly mixing the epoxy vegetable oil, the catalyst and the reaction solvent, heating and preserving heat, dropwise adding the vegetable oleic acid, and after dropwise adding, preserving heat and continuously reacting to obtain an intermediate product; and (3) uniformly mixing the intermediate product, the double-bond monomer, the catalyst, the polymerization inhibitor and the reaction solvent, and reacting at 60-70 ℃ for 1-5 hours to obtain the multifunctional epoxy vegetable oil-based UV curing prepolymer. The UV curing prepolymer prepared by the invention has the advantages of high functionality, large molecular weight, high curing speed, excellent mechanical property after film forming, strong chemical resistance, good biodegradability and the like, and has very high UV curing activity, and the required UV curing energy is less than or equal to 1500mJ cm‑2The curing film has excellent service performance and can meet the application requirement of the UV curing material.
Description
Technical Field
The invention belongs to the technical field of UV curing materials, and particularly relates to a multifunctional epoxy vegetable oil-based UV curing prepolymer and a preparation method and application thereof.
Background
The natural vegetable oil is used as a renewable resource, has wide source, easy regeneration, low price and certain chemical reaction activity, and completely has the structural basis of replacing petrochemical raw materials and preparing high polymer materials. At present, vegetable oil derivatives such as epoxidized soybean oil, epoxidized castor oil, castor oil-based polyol and the like have been industrialized and commercialized, and are gradually replacing petrochemical raw materials to be used in the field of high molecular materials. UV curing coating and water-based coating are two types of environment-friendly coating which are vigorously developed at present and are gradually replacing solvent-based coating. Castor oil-based polyols have been widely used in the synthesis of materials such as waterborne polyurethanes, and thus can be applied in the field of waterborne coatings. Epoxy vegetable oil such as epoxidized soybean oil, epoxidized castor oil and the like has certain cationic photopolymerization activity, so that the epoxy vegetable oil can be applied to cationic photocuring materials. However, the radical photo-curing material is widely applied at present, and although the vegetable oil also contains unsaturated double bonds, the reaction activity is low, and the application of the vegetable oil in the radical photo-curing material system is limited. Although there are many reports on the synthesis of vegetable oil-based UV-curable prepolymers, the molecular weights of the synthesized prepolymers are not large, and generally the molecular weights are not more than 1500, and no report is found on the preparation of vegetable oil-based UV-curable prepolymers with larger molecular weights and higher vegetable oil contents. Although the plant oil-based UV curing prepolymer with small molecular weight prepared at present can be cured to form a film, the cured film is brittle and has poor flexibility due to the fact that molecular chains between double bonds of the plant oil-based UV curing prepolymer are short, and therefore a certain amount of petroleum-based UV curing prepolymer needs to be added to modify the plant oil-based UV curing prepolymer to obtain a film with good comprehensive performance, and the use amount of the plant oil-based UV curing prepolymer in the industry is limited to a certain extent.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the invention provides a preparation method of a multifunctional epoxy vegetable oil-based UV curing prepolymer.
According to the invention, epoxy vegetable oil is used as a basic raw material, a prepolymer with the molecular weight about twice that of the vegetable oil is obtained through ring-opening grafting of vegetable oleic acid, and then a double bond with high UV curing activity is connected to obtain the multifunctional epoxy vegetable oil-based UV curing prepolymer, the prepared prepolymer has a large molecular weight which is more than 1500, the consumption of petroleum-based raw materials in the UV curing prepolymer can be obviously reduced, and the multifunctional epoxy vegetable oil-based UV curing prepolymer has the advantages of low pollution, low production cost, simple process and the like.
It is another object of the present invention to provide a multifunctional epoxy vegetable oil-based UV curing prepolymer prepared by the above method. The UV curing prepolymer disclosed by the invention has the advantages of large molecular weight, high reactivity, high biodegradation speed and the like.
Still another object of the present invention is to provide the use of the above multifunctional epoxy vegetable oil-based UV curing prepolymer in the field of UV curing materials.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a multifunctional epoxy vegetable oil-based UV curing prepolymer comprises the following steps:
(1) uniformly mixing epoxy vegetable oil, a catalyst and a reaction solvent, heating to a reaction temperature, preserving heat, dropwise adding vegetable oleic acid, preserving heat after dropwise adding, and continuously reacting for a period of time to obtain an intermediate product;
(2) uniformly mixing the intermediate product, the catalyst, the polymerization inhibitor and the reaction solvent, reducing the temperature to 60-70 ℃, reacting for 1-5 h, dropwise adding the double bond monomer at the dropping flow rate of 1-10 drops/second, and performing rotary evaporation to remove the solvent to obtain the multifunctional epoxy vegetable oil-based UV curing prepolymer.
In the step (1), 5-10 parts of epoxy vegetable oil and 20-60 parts of vegetable oil acid are calculated according to molar parts.
In the step (1), the dosage of the catalyst is 0.5-1% of the total mass of the epoxy vegetable oil and the vegetable oleic acid, and the dosage of the reaction solvent is 1-3 times of the total mass of the epoxy vegetable oil and the vegetable oleic acid.
In the step (1), the epoxidized vegetable oil is at least one of epoxidized soybean oil, epoxidized castor oil and epoxidized linseed oil.
In the step (1), the vegetable oil acid is at least one of soybean oil acid, ricinoleic acid, eleostearic acid, linoleic acid, rapeseed oil acid and corn oil acid.
In the step (1), the catalyst may be at least one of triethylamine and N, N-dimethylethanolamine.
In the steps (1) and (2), the reaction solvent is at least one of acetone, butanone, tetrachloromethane and tetrahydrofuran.
In the step (1), the reaction temperature is 110-130 ℃, and the vegetable oil acid is kept warm and continuously reacts for 3-5 hours after being dripped; the dropping flow rate of the vegetable oil acid is 1-10 drops/second.
In the step (1), after the reaction is finished, the method also comprises the step of purifying an intermediate product, which comprises the following steps: filtering the solution when the solution is hot after the reaction is finished, transferring the solution to a separating funnel, and dissolving the solution by using a solvent; washing with saturated sodium bicarbonate solution and saturated sodium chloride solution, separating to obtain upper organic phase, drying with desiccant, filtering, and vacuum distilling to obtain intermediate product.
The solvent can be at least one of n-hexane, diethyl ether and petroleum ether.
In the step (2), 5-10 parts of intermediate product and 40-120 parts of double bond monomer are calculated according to molar parts.
In the step (2), the dosage of the catalyst is 0.5-1% of the total mass of the intermediate product and the double-bond monomer, the dosage of the polymerization inhibitor is 0.5-1% of the total mass of the intermediate product and the double-bond monomer, and the dosage of the reaction solvent is 1-3 times of the total mass of the intermediate product and the double-bond monomer.
In the step (2), the double-bond monomer is at least one of acrylic acid, methacrylic acid, chloropropene and bromopropylene.
In the step (2), the polymerization inhibitor may be at least one of p-hydroxyanisole, 2-tert-butylhydroquinone and hydroquinone.
In the step (2), when the double bond monomer is acrylic acid or/and methacrylic acid, the catalyst may be at least one of p-toluenesulfonic acid, boron trifluoride diethyl etherate solution, concentrated sulfuric acid, concentrated hydrochloric acid and concentrated nitric acid.
The concentrated acid is a common product sold in the market, and the mass fraction of the concentrated sulfuric acid is greater than or equal to 70%, the mass fraction of the concentrated hydrochloric acid is 36-38%, and the mass fraction of the concentrated nitric acid is 68%.
In the step (2), when the double-bond monomer is chloropropene or/and bromopropylene, the catalyst can be tetrabutylammonium chloride.
In the step (2), after the reaction is finished, the method also comprises the step of purifying the product, which comprises the following steps: and transferring the mixture to a separating funnel while the mixture is hot after the reaction is finished, dissolving the mixture by using a solvent, repeatedly washing the mixture by using a saturated sodium bicarbonate solution until no bubbles are generated, washing the mixture by using a saturated sodium chloride solution, separating the solution to obtain an upper organic phase, drying and filtering the organic phase by using a drying agent, and finally distilling the organic phase under reduced pressure to obtain the multifunctional epoxy vegetable oil-based UV curing prepolymer.
The solvent can be at least one of n-hexane, diethyl ether and petroleum ether.
The stock of vegetable oil resources in China is huge, and products developed by taking the vegetable oil resources as raw materials have good economic value and are applied to many fields, wherein the most main application fields comprise coatings, 3D printing, biological medicines and the like. The vegetable oil derivative can replace petrochemical products in many fields, and has important value in theoretical research and practical application. According to the invention, vegetable oil is subjected to ring-opening grafting by vegetable oil acid, and then reacts with a double-bond monomer to synthesize a multifunctional epoxy vegetable oil-based UV curing prepolymer, and the vegetable oil is used as a raw material to prepare a UV curing material, so that the dependence of a UV curing material system on petroleum-based raw materials is reduced, and the effects of energy conservation and emission reduction are achieved.
The multifunctional epoxy vegetable oil-based UV curing prepolymer prepared by the invention is prepared by grafting 3-6 vegetable oleic acids on each epoxy vegetable oil molecule, so that the molecular weight of the prepolymer is distributed between 1800 and 2700, and is much higher than the molecular weight of about 1000 of the vegetable oil-based UV curing prepolymer commonly reported in the literature. In addition, the resin contains 3-6 double bonds, so that the resin has high UV curing activity, and the required UV curing energy is less than or equal to 1500 mJ-cm-2The curing film has excellent service performance and can meet the application requirement of the UV curing material.
The invention also provides application of the multifunctional epoxy plant oil-based UV curing prepolymer in the field of UV curing materials, in particular application in the fields of UV curing materials such as UV curing coatings, UV curing printing ink, UV curing adhesives and 3D printing.
Compared with the prior art, the invention has the following advantages and beneficial effects: (1) the invention introduces vegetable oil with wide source into a UV curing material system to synthesize a multifunctional epoxy vegetable oil-based UV curing prepolymer, so that the content of vegetable oil in the UV curing prepolymer exceeds 80 percent, thereby greatly reducing the proportion of the traditional petroleum-based raw material in the UV curing prepolymer, opening up a new application direction for vegetable oil resources, improving the economic value of the vegetable oil resources and reducing the production cost. (2) The preparation method is simple, mild in condition, stable in product quality, high in yield and suitable for large-scale production. (3) The UV curing prepolymer disclosed by the invention has the advantages of high functionality, large molecular weight, high curing speed, excellent mechanical property after film forming, strong chemical resistance, good biodegradability and the like.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. The materials referred to in the following examples are commercially available. The raw materials in the following examples are in parts by mole, concentrated sulfuric acid with a mass fraction of 70% or more, concentrated hydrochloric acid with a mass fraction of 36-38%, and concentrated nitric acid with a mass fraction of 68%.
Example 1
Preparation of epoxidized soybean oil-castor oil acid based UV curable prepolymer:
(1) the preparation method comprises the following steps of sequentially adding 5 parts of epoxidized soybean oil (purchased from Shanghai Aladdin Biotechnology Co., Ltd.), triethylamine and acetone (the dosage is respectively 0.5% and 1 time of the total mass of the epoxy vegetable oil and the vegetable oil acid) into a four-neck flask with a mechanical stirring device, a condensation reflux device and a thermometer, uniformly stirring, heating an oil bath to 120 ℃, keeping the temperature, dropwise adding 20 parts of ricinoleic acid (purchased from Shanghai Aladdin Biotechnology Co., Ltd.), wherein the dropwise adding flow rate is 1 drop per second, keeping the temperature after the dropwise adding is finished, continuously reacting for 5 hours, filtering while hot after the reaction is finished, transferring liquid to a separating funnel and dissolving the liquid with petroleum ether. The mixture was washed with a saturated sodium bicarbonate solution and a saturated sodium chloride solution three times, and the organic phase was separated to obtain an upper organic phase, then dried over anhydrous magnesium sulfate and filtered, and finally the organic phase was subjected to distillation under reduced pressure to obtain an intermediate product with a yield of 94.7%.
(2) Adding 5 parts of intermediate product, p-toluenesulfonic acid, p-hydroxyanisole and tetrahydrofuran (the dosage of the intermediate product is 1%, 0.6% and 2 times of the total mass of the intermediate product and the double bond monomer respectively) into a four-neck flask with a mechanical stirring device, a condensation reflux device and a thermometer in sequence, uniformly stirring, heating in a water bath to 60 ℃, preserving heat, dropwise adding 40 parts of acrylic acid at the dropping flow rate of 10 drops per second, and preserving heat and continuing to react for 1 hour after dropwise adding. And after the reaction is finished, transferring the mixture to a separating funnel while the mixture is hot, dissolving the mixture by using ether, repeatedly washing the mixture by using a saturated sodium bicarbonate solution until no bubbles are generated, washing the mixture for three times by using a saturated sodium chloride solution, separating the solution to obtain an upper organic phase, drying and filtering the organic phase by using anhydrous magnesium sulfate, and finally distilling the organic phase under reduced pressure to obtain the multifunctional epoxy vegetable oil-based UV curing prepolymer, wherein the yield of the final product is 90.2%.
Example 2
Preparation of epoxidized soybean oil-soybean oleic acid based UV curing prepolymer:
(1) sequentially adding 10 parts of epoxidized soybean oil (purchased from Shanghai Arlatin Biotechnology Co., Ltd.), N-dimethylethanolamine and butanone (the use amounts of which are respectively 1% and 3 times of the total mass of the epoxidized vegetable oil and the vegetable oleic acid) into a four-neck flask with a mechanical stirring device, a condensation reflux device and a thermometer, uniformly stirring, heating the oil bath to 110 ℃ for heat preservation, dropwise adding 60 parts of soybean oleic acid (purchased from Shanghai Lisson chemical Co., Ltd.), wherein the dropwise adding flow rate is 10 drops per second, after the dropwise adding is finished, keeping the temperature and continuously reacting for 5 hours, filtering while the reaction is hot after the reaction is finished, transferring the liquid to a separating funnel and dissolving the liquid with petroleum ether. The mixture was washed with a saturated sodium bicarbonate solution and a saturated sodium chloride solution three times, and the organic phase was separated to obtain an upper organic phase, then dried over anhydrous magnesium sulfate and filtered, and finally the organic phase was subjected to distillation under reduced pressure to obtain an intermediate product with a yield of 93.8%.
(2) Sequentially adding 10 parts of intermediate product, tetrabutylammonium chloride, 2-tert-butylhydroquinone and acetone (the dosage of the intermediate product is 1%, 1% and 3 times of the total mass of the double bond monomer) into a four-neck flask with a mechanical stirring device, a condensation reflux device and a thermometer, uniformly stirring, heating in a water bath to 70 ℃, preserving heat, dropwise adding 120 parts of chloropropene at the dropping flow rate of 1 drop per second, and preserving heat and continuously reacting for 1 hour after the dropwise adding is finished. And after the reaction is finished, transferring the mixture to a separating funnel while the mixture is hot, dissolving the mixture by using ether, repeatedly washing the mixture by using a saturated sodium bicarbonate solution until no bubbles are generated, washing the mixture for three times by using a saturated sodium chloride solution, separating the solution to obtain an upper organic phase, drying and filtering the organic phase by using anhydrous magnesium sulfate, and finally distilling the organic phase under reduced pressure to obtain the multifunctional epoxy vegetable oil-based UV curing prepolymer, wherein the yield of the final product is 91.0%.
Example 3
Preparation of epoxidized soybean oil-tung oil acid based UV curing prepolymer:
(1) the method comprises the following steps of sequentially adding 5 parts of epoxidized soybean oil (purchased from Shanghai Aladdin Biotechnology limited company), triethylamine and tetrahydrofuran (the dosage is respectively 0.7% and 2 times of the total mass of the epoxidized vegetable oil and the vegetable oil acid) into a four-neck flask with a mechanical stirring device, a condensation reflux device and a thermometer, uniformly stirring, heating the oil bath to 130 ℃ for heat preservation, dropwise adding 30 parts of eleostearic acid (purchased from Shandong Green City chemical limited company), wherein the dropwise adding flow rate is 5 drops per second, after the dropwise adding is finished, keeping the temperature and continuously reacting for 5 hours, filtering while the temperature is hot after the reaction is finished, transferring liquid to a separating funnel and dissolving the liquid with petroleum ether. The mixture was washed with a saturated sodium bicarbonate solution and a saturated sodium chloride solution three times, and the organic phase was separated to obtain an upper organic phase, then dried over anhydrous magnesium sulfate and filtered, and finally the organic phase was subjected to distillation under reduced pressure to obtain an intermediate product with a yield of 93.9%.
(2) Adding 7.5 parts of intermediate product, boron trifluoride diethyl etherate solution, hydroquinone and tetrachloromethane (the dosage of which is respectively 0.8%, 0.7% and 2.5 times of the total mass of the intermediate product and the double bond monomer) into a four-neck flask with a mechanical stirring device, a condensation reflux device and a thermometer in sequence, uniformly stirring, heating in a water bath to 60 ℃, preserving heat, dropwise adding 60 parts of methacrylic acid at the dropwise adding flow rate of 6 drops per second, and preserving heat and continuing to react for 1 hour after the dropwise adding is finished. And after the reaction is finished, transferring the mixture to a separating funnel while the mixture is hot, dissolving the mixture by using ether, repeatedly washing the mixture by using a saturated sodium bicarbonate solution until no bubbles are generated, washing the mixture for three times by using a saturated sodium chloride solution, separating the solution to obtain an upper organic phase, drying and filtering the organic phase by using anhydrous magnesium sulfate, and finally distilling the organic phase under reduced pressure to obtain the multifunctional epoxy vegetable oil-based UV curing prepolymer, wherein the yield of the final product is 90.8%.
Example 4
Preparation of epoxidized castor oil-soy oleic acid based UV curing prepolymer:
(1) adding 7.5 parts of epoxy castor oil (purchased from Guangzhou Shangde chemical Co., Ltd.), N-dimethylethanolamine and tetrachloromethane (the use amounts of which are respectively 0.6% and 1.5 times of the total mass of epoxy vegetable oil and vegetable oleic acid) into a four-neck flask with a mechanical stirring device, a condensation reflux device and a thermometer in sequence, uniformly stirring, heating an oil bath to 110 ℃ for heat preservation, dropwise adding 50 parts of soybean oleic acid (purchased from Shanghaisen chemical Co., Ltd.), wherein the dropwise adding flow rate is 8 drops per second, after the dropwise adding is finished, keeping the temperature and continuously reacting for 5 hours, filtering while the reaction is hot after the reaction is finished, transferring the liquid to a separating funnel and dissolving the liquid with petroleum ether. The mixture was washed with a saturated sodium bicarbonate solution and a saturated sodium chloride solution three times, and the organic phase was separated to obtain an upper organic phase, then dried over anhydrous magnesium sulfate and filtered, and finally the organic phase was subjected to distillation under reduced pressure to obtain an intermediate product with a yield of 93.5%.
(2) Sequentially adding 10 parts of intermediate product, tetrabutylammonium chloride, p-hydroxyanisole and butanone (the dosage of the intermediate product is 0.5 percent, 1 percent and 2 times of the total mass of the intermediate product and the double bond monomer respectively) into a four-neck flask with a mechanical stirring device, a condensation reflux device and a thermometer, uniformly stirring, heating in a water bath to 70 ℃, preserving heat, dropwise adding 80 parts of bromopropylene, keeping the dropwise adding flow rate at 7 drops per second, and preserving heat and continuously reacting for 1 hour after the dropwise adding is finished. And after the reaction is finished, transferring the mixture to a separating funnel while the mixture is hot, dissolving the mixture by using ether, repeatedly washing the mixture by using a saturated sodium bicarbonate solution until no bubbles are generated, washing the mixture for three times by using a saturated sodium chloride solution, separating the solution to obtain an upper organic phase, drying and filtering the organic phase by using anhydrous magnesium sulfate, and finally distilling the organic phase under reduced pressure to obtain the multifunctional epoxy vegetable oil-based UV curing prepolymer, wherein the yield of the final product is 90.6%.
Example 5
Preparation of epoxy linseed oil-ricinoleic acid based UV curable prepolymer:
(1) the method comprises the following steps of sequentially adding 10 parts of epoxy linseed oil (purchased from carbofuran technologies, Inc.), triethylamine and tetrahydrofuran (the using amounts of the epoxy vegetable oil and the vegetable oil are respectively 0.9% and 3 times of the total mass) into a four-neck flask with a mechanical stirring device, a condensation reflux device and a thermometer, uniformly stirring, heating an oil bath to 125 ℃, keeping the temperature, dropwise adding 60 parts of ricinoleic acid (purchased from Shanghai Aladdin biochemistry technologies, Inc.), wherein the dropwise adding flow rate is 4 drops per second, keeping the temperature after the dropwise adding is finished, continuing to react for 5 hours, filtering while the temperature is hot after the reaction is finished, transferring the liquid to a separating funnel and dissolving the liquid with petroleum ether. The mixture was washed with a saturated sodium bicarbonate solution and a saturated sodium chloride solution three times, and the organic phase was separated to obtain an upper organic phase, then dried over anhydrous magnesium sulfate and filtered, and finally the organic phase was subjected to distillation under reduced pressure to obtain an intermediate product with a yield of 94.0%.
(2) Adding 5 parts of intermediate product, concentrated sulfuric acid, 2-tert-butyl hydroquinone and acetone (the dosage of the intermediate product is 1 percent, 0.8 percent and 3 times of the total mass of the double bond monomer) in sequence into a four-neck flask with a mechanical stirring device, a condensation reflux device and a thermometer, uniformly stirring, heating in a water bath to 60 ℃, preserving heat, dropwise adding 120 parts of methacrylic acid at the dropping flow rate of 10 drops per second, and preserving heat and continuing to react for 4 hours after the dropwise adding is finished. And after the reaction is finished, transferring the mixture to a separating funnel while the mixture is hot, dissolving the mixture by using ether, repeatedly washing the mixture by using a saturated sodium bicarbonate solution until no bubbles are generated, washing the mixture for three times by using a saturated sodium chloride solution, separating the solution to obtain an upper organic phase, drying and filtering the organic phase by using anhydrous magnesium sulfate, and finally distilling the organic phase under reduced pressure to obtain the multifunctional epoxy vegetable oil-based UV curing prepolymer, wherein the yield of the final product is 90.2%.
Example 6
Preparation of epoxidized castor oil-castor oil acid based UV curable prepolymer:
(1) adding 5 parts of epoxy castor oil (purchased from Guangzhou Shangde chemical Co., Ltd.), N-dimethylethanolamine and tetrahydrofuran (the use amounts of which are respectively 0.5% and 2 times of the total mass of the epoxy vegetable oil and the vegetable oleic acid) into a four-neck flask with a mechanical stirring device, a condensation reflux device and a thermometer in sequence, uniformly stirring, heating an oil bath to 130 ℃, preserving heat, dropwise adding 30 parts of ricinoleic acid (purchased from Shanghai Arlatin Biotechnology Co., Ltd.), keeping the dropwise adding flow rate of 10 drops per second, preserving heat after the dropwise adding is finished, continuously reacting for 3 hours, filtering while the heat is still after the reaction is finished, transferring the liquid to a separating funnel and dissolving the liquid with petroleum ether. The mixture was washed with a saturated sodium bicarbonate solution and a saturated sodium chloride solution three times, and the organic phase was separated to obtain an upper organic phase, then dried over anhydrous magnesium sulfate and filtered, and finally the organic phase was subjected to distillation under reduced pressure to obtain an intermediate product with a yield of 94.2%.
(2) Sequentially adding 10 parts of intermediate product, concentrated nitric acid, hydroquinone and tetrahydrofuran (the dosage of the intermediate product is 0.5 percent, 0.6 percent and 1 time of the total mass of the double bond monomer and the intermediate product) into a four-neck flask with a mechanical stirring device, a condensation reflux device and a thermometer, uniformly stirring, heating in a water bath to 70 ℃, preserving heat, dropwise adding 40 parts of acrylic acid at the dropping flow rate of 10 drops per second, and preserving heat and continuing to react for 5 hours after the dropwise adding is finished. And after the reaction is finished, transferring the mixture to a separating funnel while the mixture is hot, dissolving the mixture by using ether, repeatedly washing the mixture by using a saturated sodium bicarbonate solution until no bubbles are generated, washing the mixture for three times by using a saturated sodium chloride solution, separating the solution to obtain an upper organic phase, drying and filtering the organic phase by using anhydrous magnesium sulfate, and finally distilling the organic phase under reduced pressure to obtain the multifunctional epoxy vegetable oil-based UV curing prepolymer, wherein the yield of the final product is 90.8%.
Multifunctional epoxy vegetable oil-based UV-curable prepolymer and UV-curable film property test examples thereof
The multifunctional epoxy vegetable oil-based UV curing prepolymer prepared in each example was uniformly mixed with 5% by mass of a photoinitiator 1173 (2-hydroxy-2-methyl-1-phenyl-1-propanone), and then coated on the surface of a tin plate with a film coater, and a 365nm UV-LED point light source was used to cure the prepolymerThe light intensity is 115.8mW cm-2Curing for a certain time, and carrying out a series of performance tests on the obtained photocured film.
Testing the surface drying time of the curing film according to a method of determination method for drying time of paint films and putty films (GB/T1728-: curing energy (mJ. cm)-2) Dry time (1) is expressed as illumination intensity.
Adhesion test the adhesion test was performed according to the method of the scratch test for paint, varnish and lacquer film (GB/T9286-1998). Hardness test the hardness test was carried out according to the method of determination of paint film hardness by the colored paint and varnish pencil method (GB/T6739-2006).
Thermal stability analysis (TGA analysis), the cured film was measured using a thermogravimetric analyzer model STA449C of Netzsch, germany, and the rate of temperature rise: 10 ℃/min; atmosphere: nitrogen gas; temperature range: the initial decomposition temperature at which the mass loss of each example reached 5% was recorded in Table 1 at 35 to 660 ℃.
Dynamic thermomechanical analysis (DMA) the cured films were tested using a dynamic mechanical analyzer, DMA242C, Netzsch, germany, sample holder: stretching the bracket; oscillation frequency: 1 Hz; sample size: 20mm × 6mm × 0.5 mm; the heating rate is as follows: 3 ℃/min; temperature range: -80 to 180 ℃. The measured glass transition temperature (T) of the cured filmg) Are shown in Table 1.
Mechanical properties analysis the cured film was tested using an AGS-X1 kN universal tester manufactured by Shimadzu corporation, japan, crosshead speed: 10 mm/min; sample size: 40 mm. times.10 mm. times.0.5 mm.
The biodegradability of the cured film is tested according to a sealed compost biodegradation test, and the decomposition degree of the cured film is determined by the mineralization rate.
Table 1 results of comprehensive property test of final products of each example
As can be seen from Table 1, the multifunctional epoxy vegetable oil-based UV curing prepolymer curing film prepared by the invention has the advantages of high curing speed, good adhesion, high hardness, good thermal stability, good mechanical property, good biodegradability and the like.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A preparation method of a multifunctional epoxy vegetable oil-based UV curing prepolymer is characterized by comprising the following steps:
(1) uniformly mixing epoxy vegetable oil, a catalyst and a reaction solvent, heating to a reaction temperature, preserving heat, dropwise adding vegetable oleic acid, preserving heat after dropwise adding, and continuously reacting for a period of time to obtain an intermediate product; the vegetable oil acid is at least one of soybean oil acid, ricinoleic acid, eleostearic acid, linoleic acid, rapeseed oil acid and corn oil acid; the reaction temperature is 110-130 ℃, and the vegetable oil acid is kept warm and continuously reacts for 3-5 hours after being dripped; the dropping flow rate of the vegetable oil acid is 1-10 drops/second;
(2) uniformly mixing the intermediate product, the double-bond monomer, the catalyst, the polymerization inhibitor and the reaction solvent, reducing the temperature to 60-70 ℃, and reacting for 1-5 hours to obtain a multifunctional epoxy vegetable oil-based UV curing prepolymer; the double-bond monomer is one of acrylic acid, methacrylic acid, chloropropene and bromopropylene; 5-10 parts of intermediate product and 40-120 parts of double bond monomer according to molar parts.
2. The preparation method of the multifunctional epoxy vegetable oil-based UV-curable prepolymer according to claim 1, wherein in the step (1), 5-10 parts by mole of epoxy vegetable oil and 20-60 parts by mole of vegetable oil acid are added; the dosage of the catalyst in the step (1) is 0.5-1% of the total mass of the epoxy vegetable oil and the vegetable oleic acid, and the dosage of the reaction solvent is 1-3 times of the total mass of the epoxy vegetable oil and the vegetable oleic acid.
3. The method for preparing the multifunctional epoxy vegetable oil-based UV-curable prepolymer according to claim 1, wherein the epoxy vegetable oil in the step (1) is at least one of epoxidized soybean oil, epoxidized castor oil and epoxidized linseed oil;
the catalyst in the step (1) can be at least one of triethylamine and N, N-dimethylethanolamine.
4. The method for preparing the multifunctional epoxy vegetable oil-based UV-curable prepolymer according to claim 1, wherein the amount of the catalyst used in the step (2) is 0.5-1% of the total mass of the intermediate product and the double bond monomer, the amount of the polymerization inhibitor used is 0.5-1% of the total mass of the intermediate product and the double bond monomer, and the amount of the reaction solvent used is 1-3 times of the total mass of the intermediate product and the double bond monomer.
5. The method of preparing a multifunctional epoxy vegetable oil-based UV curable prepolymer according to claim 1,
the polymerization inhibitor in the step (2) can be at least one of p-hydroxyanisole, 2-tertiary butyl hydroquinone and hydroquinone;
in the step (2), when the double bond monomer is acrylic acid or/and methacrylic acid, the catalyst can be at least one of p-toluenesulfonic acid, boron trifluoride diethyl etherate solution, concentrated sulfuric acid, concentrated hydrochloric acid and concentrated nitric acid; when the double-bond monomer is chloropropene or/and bromopropylene, the catalyst can be tetrabutylammonium chloride.
6. The method for preparing the multifunctional epoxy vegetable oil-based UV-curable prepolymer according to claim 1, wherein in the step (1), the intermediate product is purified and then subjected to the next step of reaction, and the purification steps are as follows: filtering the solution when the solution is hot after the reaction is finished, transferring the solution to a separating funnel, and dissolving the solution by using a solvent; washing with saturated sodium bicarbonate solution and saturated sodium chloride solution respectively, separating to obtain upper organic phase, drying the organic phase with desiccant, filtering, and distilling the organic phase under reduced pressure to obtain intermediate product;
in the step (2), after the reaction is finished, the method also comprises the step of purifying the product, which comprises the following steps: and transferring the mixture to a separating funnel while the mixture is hot after the reaction is finished, dissolving the mixture by using a solvent, repeatedly washing the mixture by using a saturated sodium bicarbonate solution until no bubbles are generated, washing the mixture by using a saturated sodium chloride solution, separating the solution to obtain an upper organic phase, drying and filtering the organic phase by using a drying agent, and finally distilling the organic phase under reduced pressure to obtain the multifunctional epoxy vegetable oil-based UV curing prepolymer.
7. The method for preparing the multifunctional epoxy vegetable oil-based UV-curable prepolymer according to claim 1, wherein in the steps (1) and (2), the reaction solvent is at least one of acetone, butanone, tetrachloromethane and tetrahydrofuran.
8. A multifunctional epoxy vegetable oil-based UV curable prepolymer made by the method of any one of claims 1-7.
9. Use of the multifunctional epoxy vegetable oil-based UV curable prepolymer according to claim 8 in the field of UV curable materials.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911390353.6A CN111154071B (en) | 2019-12-30 | 2019-12-30 | Multifunctional epoxy vegetable oil-based UV curing prepolymer and preparation method and application thereof |
| PCT/CN2020/107053 WO2021135222A1 (en) | 2019-12-30 | 2020-08-05 | Multifunctional-epoxy-vegetable-oil-based uv-curable prepolymer, preparation method therefor and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911390353.6A CN111154071B (en) | 2019-12-30 | 2019-12-30 | Multifunctional epoxy vegetable oil-based UV curing prepolymer and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111154071A CN111154071A (en) | 2020-05-15 |
| CN111154071B true CN111154071B (en) | 2021-03-26 |
Family
ID=70559339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911390353.6A Active CN111154071B (en) | 2019-12-30 | 2019-12-30 | Multifunctional epoxy vegetable oil-based UV curing prepolymer and preparation method and application thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN111154071B (en) |
| WO (1) | WO2021135222A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111154071B (en) * | 2019-12-30 | 2021-03-26 | 华南农业大学 | Multifunctional epoxy vegetable oil-based UV curing prepolymer and preparation method and application thereof |
| CN112011271B (en) * | 2020-08-04 | 2021-07-27 | 华南农业大学 | Organic-inorganic hybrid photocuring plant oil-based coating and preparation method and application thereof |
| GB2620458A (en) * | 2020-08-04 | 2024-01-10 | Univ South China Agricult | Photo-induced cationic polymerization pure vegetable oil-based polymer, preparation method therefor and application thereof |
| CN112442318A (en) * | 2020-11-24 | 2021-03-05 | 中国林业科学研究院林产化学工业研究所 | Bio-based self-repairing photocureable coating and preparation method and application thereof |
| CN113292516B (en) * | 2021-05-28 | 2023-10-24 | 华南农业大学 | Multifunctional epoxy vegetable oil-based acrylate and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106832196A (en) * | 2016-12-15 | 2017-06-13 | 湖北大学 | A kind of preparation method of soybean oil base water polyurethane light-cured resin |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100503680C (en) * | 2003-01-08 | 2009-06-24 | 得克萨斯科技大学 | Castor oil/epoxidized soybean oil based elastomeric compositions |
| WO2006014483A2 (en) * | 2004-07-08 | 2006-02-09 | Archer-Daniels-Midland Company | Epoxidized esters of vegetable oil fatty acids as reactive diluents |
| US7863485B2 (en) * | 2004-12-10 | 2011-01-04 | Omnitech Environmental, Llc | Additive and vehicle for inks, paints, coatings and adhesives |
| CN104211931B (en) * | 2014-08-12 | 2016-05-11 | 江西科技师范大学 | A kind of pure plant oil based polyenoid class UV-curable prepolymer |
| CN106967015A (en) * | 2017-03-30 | 2017-07-21 | 中国林业科学研究院林产化学工业研究所 | A kind of contracting fatty acid ester of epoxy two and its preparation method and application |
| CN107540820A (en) * | 2017-07-28 | 2018-01-05 | 华南农业大学 | A kind of bio-oil base epoxy and its preparation method and application |
| CN109160999B (en) * | 2018-08-03 | 2021-01-05 | 华南农业大学 | Vegetable oil-based epoxy prepolymer and UV curing prepolymer, and preparation method and application thereof |
| CN110396176B (en) * | 2019-07-31 | 2022-03-25 | 中国林业科学研究院林产化学工业研究所 | Vegetable oil-based epoxy acrylate resin and preparation method and application thereof |
| CN111154071B (en) * | 2019-12-30 | 2021-03-26 | 华南农业大学 | Multifunctional epoxy vegetable oil-based UV curing prepolymer and preparation method and application thereof |
-
2019
- 2019-12-30 CN CN201911390353.6A patent/CN111154071B/en active Active
-
2020
- 2020-08-05 WO PCT/CN2020/107053 patent/WO2021135222A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106832196A (en) * | 2016-12-15 | 2017-06-13 | 湖北大学 | A kind of preparation method of soybean oil base water polyurethane light-cured resin |
Non-Patent Citations (3)
| Title |
|---|
| "UV固化环氧大豆油丙烯酸酯的合成研究";张秀云等;《中国油脂》;20110120;第36卷(第1期);第45-49页 * |
| "植物油基紫外光固化涂料研究进展";李鹏等;《涂料工业》;20160501;第46卷(第5期);第81-87页 * |
| "羟基化倍半硅氧烷改性植物油基聚氨酯的制备及性能研究";闻月;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20191215(第12期);B016-112 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111154071A (en) | 2020-05-15 |
| WO2021135222A1 (en) | 2021-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111154071B (en) | Multifunctional epoxy vegetable oil-based UV curing prepolymer and preparation method and application thereof | |
| AU2016354296B2 (en) | Curable polymers | |
| CN101928508B (en) | Polyethylene glycol-modified epoxy acrylate coating and preparation method thereof | |
| CN107759757B (en) | Preparation method of hyperbranched polyurethane acrylate and ultraviolet-curable coating | |
| CN107189032B (en) | Multifunctional UV (ultraviolet) curing polyurethane vegetable oleate prepolymer and preparation method and application thereof | |
| CN111138290B (en) | Aromatic ring-containing benzophenone derivative and preparation method and application thereof | |
| CN108314773B (en) | Low-viscosity hyperbranched polyurethane acrylic resin and preparation method and application thereof | |
| CN111732679B (en) | Photosensitive resin based on vegetable oil and citric acid and preparation method and application thereof | |
| AU2020101245A4 (en) | A Benzophenone Derivative Containing Aromatic Ester Group and Preparation Method and Application Thereof | |
| CN110396176B (en) | Vegetable oil-based epoxy acrylate resin and preparation method and application thereof | |
| CN106905151B (en) | Modified rosin resin, preparation method and ink adopting modified rosin resin | |
| CN111205203B (en) | Benzophenone derivative containing diphenyl carbamate group and preparation and application thereof | |
| CN111440082A (en) | Plant oil-based UV resin and pressure-sensitive adhesive | |
| CN112048077B (en) | Castor oil-based aqueous photocuring nonionic emulsion and preparation method and application thereof | |
| CN108689853B (en) | Vegetable oil-based multifunctional UV curing active monomer and preparation method and application thereof | |
| CN107779095B (en) | Preparation method of urushiol acrylate photocuring film | |
| CN107936846B (en) | Modified rosin resin and preparation method and application thereof | |
| CN108530990B (en) | Bio-based modified UV (ultraviolet) curing ink-jet ink and preparation method and application thereof | |
| CN109160999B (en) | Vegetable oil-based epoxy prepolymer and UV curing prepolymer, and preparation method and application thereof | |
| CN109776347B (en) | Thermosetting vegetable oil-based acrylate derivative and preparation method and application thereof | |
| CN102826995B (en) | Low-viscosity turpentine-based monoterpene vinyl ester resin monomer and preparation method and application thereof | |
| CN111056943B (en) | Multifunctional flax oil-based UV curing prepolymer and preparation method and application thereof | |
| CN111019418A (en) | Multifunctional cardanol-based UV curing reactive diluent and preparation method and application thereof | |
| CN110305086B (en) | Benzophenone derivative containing five-membered heterocycle and preparation method and application thereof | |
| CN107189031B (en) | UV-cured polyurethane plant oleate prepolymer and preparation method and application thereof |
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 |