CN113354769B - Plant oil-based hydrophilic polymer aqueous dispersion and preparation method and application thereof - Google Patents
Plant oil-based hydrophilic polymer aqueous dispersion and preparation method and application thereof Download PDFInfo
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/38—Esters containing sulfur
- C08F220/387—Esters containing sulfur and containing nitrogen and oxygen
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- 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
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- 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
- C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- 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
- C09J133/00—Adhesives based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
Abstract
The invention discloses a vegetable oil-based hydrophilic polymer aqueous dispersion, a preparation method and application thereof. The method comprises the steps of firstly, preparing castor oil based hydrophilic monomers by using ricinoleic acid and mercaptocarboxylic acid as raw materials; then, preparing a vegetable oil-based acrylate monomer by using vegetable oleic acid and acrylate as raw materials; uniformly mixing the castor oil-based hydrophilic monomer, the plant oil-based acrylate monomer, other monomers, the chain transfer agent and part of the initiator to obtain a mixed solution, reacting part of the mixed solution to prepare seeds, and dropwise adding the rest of the mixed solution into a reaction system to react to prepare the plant oil-based hydrophilic polymer; and finally, carrying out reduced pressure distillation, neutralization and water addition dispersion to obtain the vegetable oil-based hydrophilic polymer aqueous dispersion. The invention adopts the plant carbon source to replace more than half of the petroleum-based carbon source, thereby reducing the pressure of petrochemical resources; the usage amount of the acrylate volatile monomer is reduced, the VOC discharge amount is reduced, and the harm of irritant volatile matters to the body of an operator is eliminated.
Description
Technical Field
The invention belongs to the technical field of organic high molecular materials, and particularly relates to a plant oil-based hydrophilic polymer aqueous dispersion, and a preparation method and application thereof.
Background
Compared with the traditional solvent-based coating, the water-based coating has the advantages of low price, safe use, resource and energy conservation, environmental pollution and public nuisance reduction, and the like, thereby becoming the main development direction of the current coating industry. The water-based acrylic resin coating is the pollution-free coating which is the fastest in development and the most in variety in the water-based coatings. In recent years, people pay more attention to the development and application of acrylic resin aqueous dispersion, and the application of the acrylic resin aqueous dispersion in the fields of industrial coatings and civil coatings is continuously expanded. The emulsion is generally classified into a pure acrylic emulsion, a styrene-acrylic emulsion, an acrylic emulsion, a silicone-acrylic emulsion, a tertiary acrylic (tertiary carbonate-vinyl acetate) emulsion, a tertiary acrylic (tertiary carbonate-acrylate) emulsion, and the like, depending on the monomer composition. The raw material of acrylic ester for synthesizing the water-based acrylic resin is mainly from petrochemical resources, and most of acrylic ester substances have low boiling points, are easy to volatilize, have pungent odor and have certain harm to the environment and operators. The development of a bio-based polymerized monomer for replacing an acrylate monomer to prepare the bio-based waterborne acrylic resin becomes a research hotspot. Natural vegetable oil contains abundant double bonds, but the polymerization activity is low, and the high polymer cannot be synthesized by the traditional free radical polymerization methods such as emulsion polymerization or solution polymerization. The sulfydryl-alkene click reaction has many advantages, the sulfydryl reagent has wide sources, and meanwhile, the reaction method is simple, does not need to remove water and oxygen, has high yield and few byproducts, and therefore, the method has wide application in the fields of organic synthesis, material preparation and the like. Although the double bonds in the vegetable oil have low polymerization reaction activity, the double bonds participating in the mercapto-alkene click reaction have high activity, so that the mercapto groups and the double bonds in the vegetable oil or the vegetable oleic acid are initiated by ultraviolet light to generate the click reaction, and substances with special functional groups can be easily grafted to the vegetable oil, such as carboxyl, hydroxyl, amino and the like, so that the vegetable oil is endowed with higher chemical reaction activity and functionality, and the application of the vegetable oil in the field of synthetic polymer materials is further widened.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the invention provides a preparation method of a vegetable oil-based hydrophilic polymer aqueous dispersion.
Another object of the present invention is to provide the vegetable oil-based hydrophilic polymer aqueous dispersion prepared by the above method.
The invention also aims to provide application of the plant oil-based hydrophilic polymer aqueous dispersion in the fields of printing pastes, water-based coatings, water-based inks and water-based adhesives.
The purpose of the invention is realized by the following scheme:
a preparation method of a vegetable oil-based hydrophilic polymer aqueous dispersion comprises the following steps:
(1) adding ricinoleic acid, mercaptocarboxylic acid, a photoinitiator and a proper amount of solvent into a quartz tube, reacting in a photochemical reactor for 3-5 h to obtain castor oil-based polycarboxylic acid; then heating to 65-75 ℃, adding acrylic acid isocyanate, and reacting for 0.5-1.5 h to obtain the castor oil based hydrophilic monomer;
(2) adding vegetable oil acid into a reaction kettle, stirring, heating to 50-70 ℃, adding a tertiary ammonium salt catalyst, heating to 70-90 ℃, dropwise adding acrylic ester containing a polymerization inhibitor, reacting for 1-2 hours, heating to 80-100 ℃, and reacting for 3-5 hours to obtain a vegetable oil-based acrylic ester monomer;
(3) uniformly mixing a castor oil-based hydrophilic monomer, a plant oil-based acrylate monomer, other monomers, a chain transfer agent and a part of initiator according to a formula to obtain a mixed solution, adding 5-10% of the total amount of the mixed solution into a solvent preheated to 120-160 ℃, reacting for 20-40 min, dropwise adding the balance of the mixed solution into a reaction system, reacting for 1-2 h while keeping the temperature, adding the balance of the initiator into the reaction system, keeping the temperature for 1-2 h, and cooling to 50-60 ℃ to obtain a plant oil-based hydrophilic polymer;
the formula of each component is as follows according to the mass portion: 20-50 parts of a solvent; 20-50 parts of castor oil-based hydrophilic monomer; 20-70 parts of a vegetable oil-based acrylate monomer; 0-100 parts of other monomers; 1-10 parts of a chain transfer agent; 1-10 parts of an initiator; 50-150 parts of water;
(4) and (4) distilling the plant oil-based hydrophilic polymer prepared in the step (3) under reduced pressure to remove the solvent, adding water, stirring and dispersing, and adding a neutralizer to neutralize while dispersing to obtain the plant oil-based hydrophilic polymer aqueous dispersion.
In the step (1), the mercaptocarboxylic acid is at least one of mercaptoacetic acid, mercaptopropionic acid and mercaptosuccinic acid.
In the step (1), the molar ratio of ricinoleic acid to mercaptocarboxylic acid is 1: 2.5-1: 3.
In the step (1), the photoinitiator is 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 2,4, 6-trimethyl benzoyl phenyl phosphonic acid ethyl ester, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone, bis 2, 6-difluoro-3-pyrrol phenyl titanocene and benzoin dimethyl ether, wherein the dosage of the photoinitiator is 1-5% of the weight of ricinoleic acid.
In the step (1), the power of the photochemical reaction is 200-600W.
In the step (1), the isocyanate acrylate is at least one of isocyanoethyl acrylate and isocyanoethyl methacrylate.
In the step (1), the molar ratio of the acrylic isocyanate to the castor oil-based polycarboxylic acid is 1: 0.9-1: 1.
In the step (2), the vegetable oleic acid is at least one of eleostearic acid, ricinoleic acid, linoleic acid, soybean oleic acid, corn oleic acid, rapeseed oleic acid and cottonseed oleic acid, and can be products directly purchased in the market.
In the step (2), the molar ratio of the vegetable oil acid to the acrylate is 1: (1-1.1), the excess acrylate is not removed and may be left as a polymerization monomer.
In the step (2), the acrylate is at least one of glycidyl methacrylate, glycidyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate and hydroxypropyl acrylate.
In the step (2), the polymerization inhibitor is one of hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone and 2, 5-di-tert-butylhydroquinone, and the dosage of the polymerization inhibitor is 0.01-0.1% of the mass of the acrylate.
In the step (3), the initiator may be a solution polymerization initiator which is conventional in the art, and may be at least one of dibenzoyl peroxide, azobisisobutyronitrile, di-tert-butyl peroxide and di-tert-amyl peroxide.
In the step (3), the chain transfer agent is conventional in the art, and is preferably dodecyl mercaptan or mercaptoethanol.
In the step (3), the solvent is used for providing a solvent environment reaction, and may be at least one of n-butanol, isobutanol, sec-butanol, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol propyl ether, dipropylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol butyl ether, tripropylene glycol butyl ether, propylene glycol phenyl ether, propylene glycol methyl ether acetate and dipropylene glycol methyl ether acetate.
In the step (3), the part of the initiator accounts for 40-60 wt% of the total amount of the initiator.
In the step (3), the dripping speed is preferably 10-100 g/h.
In the step (3), an initiator accounting for 5-10 wt% of the total amount of the initiator is added into the solvent.
In the step (3), the reaction system is preferably reacted under the protection of inert gas.
In order to further achieve the aim of the invention, the using amount of the water is 0.6-1 time of the total mass of other components.
In the step (4), the rotation speed of stirring and dispersing is preferably 1000-2000 r/min, and the time of stirring and dispersing is preferably 20-60 min.
The neutralizing agent is at least one of ammonia water, triethylamine and N, N-dimethylethanolamine.
The neutralization degree of the neutralizing agent is 100-110%.
The plant oil-based hydrophilic polymer prepared by the invention can adjust the glass transition temperature of the plant oil-based hydrophilic polymer through formula design according to the requirements of the application field, and the specific formula adjustment mode is to adjust the formula by adding other monomers, wherein the other monomers comprise petroleum-based hard monomers and soft monomers; the hard monomer is at least one of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylamide, methacrylamide, propyl acrylate, propyl methacrylate, styrene, divinylbenzene, acrylonitrile, vinyl acetate and ethyl acetoacetate methacrylate; the soft monomer is at least one of butyl acrylate, butyl methacrylate, isobutyl acrylate, sec-butyl acrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, lauryl acrylate, lauryl methacrylate, n-octyl acrylate, n-octyl methacrylate, isooctyl acrylate and isooctyl methacrylate.
The invention also provides the plant oil-based hydrophilic polymer aqueous dispersion prepared by the method, wherein the solid content is 45-50%, the particle size is 50-200 nm, and the storage stability is more than 12 months. After the coating is cured into a film at room temperature, the adhesive force is 0-2 grade, the pencil hardness is 2H-4H, the impact resistance is 50-75 kg-cm, the flexibility is 2-3 mm, the water resistance is 150-180H, and the temperature resistance and the moisture resistance are more than 72H.
According to the invention, mercapto carboxylic acid is grafted on the double bond of ricinoleic acid through a light click reaction, so that more carboxyl groups are introduced into ricinoleic acid molecules, and then acrylic acid isocyanate is reacted with hydroxyl in ricinoleic acid, so that active polymerization double bonds are introduced into the ricinoleic acid molecules, thereby preparing the ricinoleic-based hydrophilic monomer. In the traditional preparation process of hydrophilic polyacrylate, (methyl) acrylic acid is generally used as a hydrophilic monomer, but the (methyl) acrylic acid mainly comes from petrochemical resources, has low boiling point, is volatile and has strong pungent smell. The castor oil-based hydrophilic monomer is adopted to replace the traditional (methyl) acrylic acid, so that on one hand, biomass resources are replaced by partial petrochemical resources, and on the other hand, the problems of VOC (volatile organic compounds) emission and pungent odor are solved.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention adopts the vegetable oleic acid to prepare the vegetable oleic acid acrylate which is used as a monomer for solution polymerization, on one hand, the natural renewable vegetable oil replaces the traditional acrylate monomer to prepare the high molecular polymer, thereby reducing the pressure of petrochemical resources and improving the additional value of the vegetable oil. On the other hand, in the process of preparing the high molecular polymer, the usage amount of the acrylate volatile monomer is reduced, the VOC emission is reduced, and the harm of irritant volatile matters to the body of an operator is eliminated.
(2) On the basis of preparing polyacrylate with the same molecular weight, the technology of the invention can reduce the dosage of acrylate monomers by more than half. The molecular weight of the polyacrylate prepared by the technology of the invention is increased by more than one time under the condition of the same polymerization degree. Meanwhile, the vegetable oil-based polyacrylate prepared by the invention has a hyperbranched molecular brush structure, and the solid content of the emulsion can be greatly improved in the process of preparing the emulsion on the premise of keeping low viscosity.
(3) The castor oil-based hydrophilic monomer with relatively large molecular weight is synthesized to be used as the hydrophilic monomer to replace the traditional micromolecular hydrophilic monomer such as acrylic acid and the like, so that on one hand, the prepared polymer has enough hydrophilicity, and on the other hand, the use of the acrylic hydrophilic monomer with volatility and pungent odor is avoided, and thus, the odorless polymer water dispersion can be prepared.
Drawings
FIG. 1 is a chemical reaction flow chart of example 1 of the preparation method of the present invention and a structural formula of the prepared vegetable oil-based polyacrylate resin.
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.
Example 1
Adding ricinoleic acid and thioglycollic acid into a quartz tube, adding a photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone accounting for 3% of the weight of the ricinoleic acid and butanone into the quartz tube to react in a photochemical reactor with the power of 360W for 4h, and removing the solvent to obtain the castor oil based polycarboxylic acid. Heating castor oil-based polycarboxylic acid to 65 ℃, adding isocyano ethyl acrylate, wherein the molar ratio of the castor oil-based polycarboxylic acid to the isocyano ethyl acrylate is 1:1, reacting for 0.5h under stirring to obtain the castor oil based hydrophilic monomer.
Adding ricinoleic acid into a reaction kettle, stirring and heating to 60 ℃, adding a tertiary ammonium salt catalyst N, N-dimethyl ethanolamine which is 1% of the weight of the ricinoleic acid, heating to 80 ℃, dropwise adding glycidyl methacrylate containing 0.01% of polymerization inhibitor hydroquinone, reacting for 1h, heating to 90 ℃, and reacting for 4h to obtain ricinoleic acid acrylate.
50g of propylene glycol butyl ether and 1g of initiator di-tert-butyl peroxide as a primer were added to a 500mL four-neck flask equipped with a stirrer, a condenser, a thermometer and an oil bath, and stirred and purged with nitrogen to raise the temperature to 120 ℃ at reflux temperature. 20g of castor oil-based hydrophilic monomer, 70g of ricinoleic acid acrylate, 3.5g of di-tert-butyl peroxide and 5g of dodecyl mercaptan are mixed, the mixture is magnetically stirred for 15min and uniformly mixed to prepare a mixed raw material, and after the temperature in a flask is raised to 120 ℃, 10wt% of the mixed raw material is pre-added into the flask with preheated bottom materials at one time to serve as reaction seeds. After half an hour, slowly dripping the residual mixed raw materials into the system by using a constant flow pump according to the ratio of 10-100 g/h, and finishing dripping within about 2 hours; and after the addition, keeping the temperature for about 1.5h, supplementing 1.5g of initiator, and keeping the temperature for about 2h to obtain the plant oil-based hydrophilic polymer.
Vacuum pumping and filtering out 25g of propylene glycol monobutyl ether as a solvent, cooling to 75 ℃, pouring the vegetable oil-based hydrophilic polymer into a 500mL flask, weighing and recording, then placing a beaker into a high-speed disc dispersion machine, rotating at a speed of 2000r/min, stirring, slowly dropping 110g of hot water with the same temperature as the weighed vegetable oil-based hydrophilic polymer for dispersion, dropping triethylamine for neutralization, wherein the neutralization degree is 100%, firstly regulating the speed to 4500r/min for high-speed dispersion for 5min, then reducing the speed to 2000r/min for dispersion for about 30min, and controlling the water addition amount to ensure that the solid content is 45-50% to obtain the vegetable oil-based hydrophilic polymer.
Example 2
Adding ricinoleic acid and mercaptopropionic acid into a quartz tube, adding 1% of photoinitiator 1-hydroxycyclohexyl phenyl ketone and butanone based on the weight of ricinoleic acid, reacting in a photochemical reactor with the power of 200W for 5h, and removing the solvent to obtain the castor oil based polycarboxylic acid. Heating castor oil-based polycarboxylic acid to 75 ℃, adding isocyano ethyl methacrylate, wherein the molar ratio of the castor oil-based polycarboxylic acid to the isocyano ethyl acrylate is 0.9: 1, reacting for 1.5 hours under stirring to obtain the castor oil based hydrophilic monomer.
Adding eleostearic acid into a reaction kettle, stirring and heating to 50 ℃, adding a tertiary ammonium salt catalyst N, N-dimethylethanolamine accounting for 1% of the weight of the eleostearic acid, heating to 70 ℃, dropwise adding acrylic acid glycidyl ester containing 0.05% of polymerization inhibitor p-benzoquinone, reacting for 2 hours, heating to 100 ℃ and reacting for 3 hours to obtain eleostearic acid acrylate.
A500 mL four-neck flask equipped with a stirrer, a condenser, a thermometer and an oil bath was charged with 25g of n-butanol and 1g of initiator di-tert-butyl peroxide as a primer, stirred, purged with nitrogen and warmed to reflux temperature of 120 ℃. 30g of castor oil-based hydrophilic monomer, 60g of eleostearic acid acrylate, 3.5g of di-tert-butyl peroxide and 5g of dodecyl mercaptan are added into a beaker and are magnetically stirred for 15min to be uniformly mixed to prepare a mixed raw material, and after the temperature in the flask is raised to 120 ℃, 10% of the mixed raw material is pre-added into the flask at one time to serve as reaction seeds. After half an hour, slowly dripping the residual mixed raw materials into the four-neck flask by using a constant flow pump, and finishing dripping within about 2 hours; after the addition, the temperature is kept for about 1.5h, 1.5g of initiator is supplemented, and the temperature is kept for about 2h, so that the plant oil-based hydrophilic polymer is obtained.
Vacuum pumping and filtering 20g of solvent n-butyl alcohol, cooling to 75 ℃, pouring the vegetable oil-based hydrophilic polymer into a 500mL flask, weighing and recording, then placing a beaker into a high-speed disc dispersion machine, rotating at a speed of 2000r/min, stirring, then slowly dropping 110g of hot water with the same temperature as the weighed vegetable oil-based hydrophilic polymer for dispersion, dropping ammonia water for neutralization, wherein the neutralization degree is 100%, firstly adjusting the speed to 4500r/min for high-speed dispersion for 5min, then reducing the speed to 2000r/min for dispersion for about 30min, and controlling the water addition amount to ensure that the solid content is 45-50% to obtain the vegetable oil-based hydrophilic polymer aqueous dispersion.
Example 3
Adding ricinoleic acid and mercaptosuccinic acid into a quartz tube, adding 2% of photoinitiator 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone and butanone based on the weight of ricinoleic acid, reacting in a photochemical reactor with the power of 300W for 5h, and removing the solvent to obtain the castor oil-based polycarboxylic acid. Heating castor oil-based polycarboxylic acid to 70 ℃, adding isocyano ethyl acrylate, wherein the molar ratio of the castor oil-based polycarboxylic acid to the isocyano ethyl acrylate is 1:1, reacting for 1 hour under stirring to obtain the castor oil based hydrophilic monomer.
Adding linoleic acid into a reaction kettle, stirring and heating to 70 ℃, adding a tertiary ammonium salt catalyst N, N-dimethylethanolamine accounting for 1% of the weight of the linoleic acid, heating to 90 ℃, dropwise adding hydroxyethyl methacrylate containing 0.1% of polymerization inhibitor methyl hydroquinone, reacting for 1h, heating to 100 ℃ and reacting for 3h to obtain the linoleic acid acrylate.
50g of propylene glycol monomethyl ether acetate and 1g of azodiisobutyronitrile as an initiator were added to a 500mL four-neck flask equipped with a stirrer, a condenser, a thermometer and an oil bath as primers, and the mixture was stirred and heated to a reflux temperature of 120 ℃ under nitrogen protection. Adding 40g of castor oil based hydrophilic monomer, 50g of linoleic acid acrylate, 3.5g of azodiisobutyronitrile and 5g of mercaptoethanol into a beaker, magnetically stirring for 15min, uniformly mixing to prepare a mixed raw material, and pre-adding 10% of the mixed raw material into the flask at one time after the temperature in the flask is raised to 160 ℃ to serve as reaction seeds. After half an hour, slowly dripping the residual mixed raw materials into the four-neck flask by using a constant flow pump, and finishing dripping within about 2 hours; after the addition, the temperature is kept for about 1.5h, 1.5g of initiator is supplemented, and the temperature is kept for about 2h, so that the plant oil-based hydrophilic polymer is obtained.
Vacuum pumping and filtering out 35g of propylene glycol monomethyl ether acetate as a solvent, cooling to 75 ℃, pouring the vegetable oil-based hydrophilic polymer into a 500mL flask, weighing and recording, placing a beaker into a high-speed disc dispersion machine, rotating at the speed of 1000r/min, stirring, slowly dropping 110g of hot water with the same temperature as the weighed vegetable oil-based hydrophilic polymer, dispersing, dropping ammonia water for neutralization, regulating the speed to 4500r/min, dispersing at the high speed for 5min, then reducing the speed to 2000r/min, dispersing for about 30min, and controlling the water addition amount to ensure that the solid content is 45-50% to obtain the vegetable oil-based hydrophilic polymer aqueous dispersion.
Example 4
Adding ricinoleic acid and thioglycollic acid into a quartz tube, adding a photoinitiator 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide accounting for 4% of the weight of the ricinoleic acid and butanone into the quartz tube, reacting in a photochemical reactor with the power of 400W for 4h, and removing the solvent to obtain the castor oil-based polycarboxylic acid. Heating castor oil-based polycarboxylic acid to 65 ℃, adding isocyano ethyl acrylate, wherein the molar ratio of the castor oil-based polycarboxylic acid to the isocyano ethyl methacrylate is 0.9: 1, reacting for 1.5 hours under stirring to obtain the castor oil based hydrophilic monomer.
Adding soybean oleic acid into a reaction kettle, stirring and heating to 55 ℃, adding a tertiary ammonium salt catalyst N, N-dimethylethanolamine accounting for 1% of the weight of the soybean amino acid, heating to 75 ℃, dropwise adding hydroxyethyl acrylate containing 0.03% of polymerization inhibitor p-hydroxyanisole, reacting for 2 hours, heating to 85 ℃, and reacting for 5 hours to obtain the soybean oleic acid acrylate.
50g of propylene glycol butyl ether and 1g of initiator di-tert-butyl peroxide as a primer were added to a 500mL four-neck flask equipped with a stirrer, a condenser, a thermometer and an oil bath, and stirred and purged with nitrogen to raise the temperature to 120 ℃ at reflux temperature. 50g of castor oil-based hydrophilic monomer, 40g of soybean oleic acid acrylate, 3.5g of di-tert-butyl peroxide and 10g of mercaptoethanol are added into a beaker and stirred magnetically for 15min to be mixed uniformly to prepare a mixed raw material, and after the temperature in the flask is raised to 120 ℃, 10% of the mixed raw material is pre-added into the flask at one time to serve as reaction seeds. After half an hour, slowly dripping the residual mixed raw materials into the four-neck flask by using a constant flow pump, and finishing dripping within about 2 hours; after the addition, the temperature is kept for about 1.5h, 1.5g of initiator is supplemented, and the temperature is kept for about 2h, so that the plant oil-based hydrophilic polymer is obtained.
Vacuum pumping and filtering out 20g of propylene glycol monobutyl ether as a solvent, cooling to 75 ℃, pouring the plant oil-based hydrophilic polymer into a 500mL flask, weighing and recording, then placing a beaker into a high-speed disc dispersion machine, rotating at a speed of 1500r/min, stirring, slowly dropping 100g of hot water with the same temperature as the weighed plant oil-based hydrophilic polymer, dispersing, dropping N, N-dimethylethanolamine for neutralization, regulating the neutralization degree to 100%, firstly regulating the speed to 4500r/min, dispersing at a high speed for 5min, then reducing the speed to 2000r/min, dispersing for about 30min, controlling the water addition amount to ensure that the solid content is 45-50%, and obtaining the plant oil-based hydrophilic polymer aqueous dispersion.
Example 5
Adding ricinoleic acid and mercaptopropionic acid into a quartz tube, adding a photoinitiator 2,4, 6-trimethylbenzoyl ethyl phenylphosphonate accounting for 5% of the weight of the ricinoleic acid and butanone into the quartz tube, reacting in a photochemical reactor with the power of 500W for 3h, and removing the solvent to obtain the castor oil-based polycarboxylic acid. Heating castor oil-based polycarboxylic acid to 70 ℃, adding isocyano ethyl acrylate, wherein the molar ratio of the castor oil-based polycarboxylic acid to the isocyano ethyl acrylate is 0.95: 1, reacting for 1 hour under stirring to obtain the castor oil based hydrophilic monomer.
Adding corn oleic acid into a reaction kettle, stirring and heating to 65 ℃, adding a tertiary ammonium salt catalyst N, N-dimethylethanolamine accounting for 1% of the weight of the corn oleic acid, heating to 85 ℃, dropwise adding hydroxypropyl methacrylate containing 0.07% of polymerization inhibitor 2-tert-butylhydroquinone, reacting for 2 hours, heating to 95 ℃ and reacting for 4 hours to obtain the corn oleic acid acrylate.
A500 mL four-neck flask equipped with a stirrer, a condenser, a thermometer and an oil bath was charged with 30g of propylene glycol monomethyl ether and 1g of initiator dibenzoyl peroxide as primers, stirred, purged with nitrogen and heated to a reflux temperature of 120 ℃. Adding 25g of castor oil-based hydrophilic monomer, 65g of corn oleic acid acrylate, 3.5g of dibenzoyl peroxide and 5g of dodecyl mercaptan into a beaker, magnetically stirring for 15min, uniformly mixing to prepare a mixed raw material, and pre-adding 10% of the mixed raw material into the flask at one time after the temperature in the flask is raised to 120 ℃ to serve as reaction seeds. After half an hour, slowly dripping the residual mixed raw materials into the four-neck flask by using a constant flow pump, and finishing dripping within about 2 hours; after the addition, the temperature is kept for about 1.5h, 1.5g of initiator is supplemented, and the temperature is kept for about 2h, so that the plant oil-based hydrophilic polymer is obtained.
Vacuum pumping 10g of propylene glycol methyl ether as a solvent, cooling to 75 ℃, pouring the vegetable oil-based hydrophilic polymer into a 500mL flask, weighing and recording, then placing a beaker into a high-speed disc dispersion machine, rotating at a speed of 2000r/min, stirring, slowly dropping 110g of hot water with the same temperature as the weighed vegetable oil-based hydrophilic polymer for dispersion, dropping triethylamine for neutralization, wherein the neutralization degree is 105%, firstly adjusting the speed to 4500r/min for high-speed dispersion for 5min, then reducing the speed to 2000r/min for dispersion for about 30min, and controlling the water addition amount to ensure that the solid content is 45-50% to obtain the vegetable oil-based hydrophilic polymer.
Example 6
Adding ricinoleic acid and mercaptosuccinic acid into a quartz tube, adding a photoinitiator 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone accounting for 3 percent of the weight of the ricinoleic acid, reacting with butanone in a photochemical reactor with the power of 600W for 5 hours, and removing the solvent to obtain the castor oil-based polycarboxylic acid. Heating castor oil-based polycarboxylic acid to 75 ℃, adding isocyano ethyl methacrylate, wherein the molar ratio of the castor oil-based polycarboxylic acid to the isocyano ethyl acrylate is 0.9: 1, reacting for 0.5h under stirring to obtain the castor oil based hydrophilic monomer.
Adding rapeseed oleic acid into a reaction kettle, stirring and heating to 50 ℃, adding a tertiary ammonium salt catalyst N, N-dimethylethanolamine accounting for 1% of the weight of the rapeseed oleic acid, heating to 90 ℃, dropwise adding hydroxypropyl acrylate containing 0.04% of a polymerization inhibitor 2, 5-di-tert-butylhydroquinone, reacting for 2 hours, heating to 100 ℃ and reacting for 5 hours to obtain the rapeseed oleic acid acrylate.
50g of isobutanol and 2g of initiator di-tert-amyl peroxide are added into a 500mL four-neck flask provided with a stirrer, a condenser, a thermometer and an oil bath kettle to be used as a bottom material, and the mixture is stirred and is heated to the reflux temperature of 120 ℃ under the protection of nitrogen. 30g of castor oil-based hydrophilic monomer, 60g of rapeseed oleic acid acrylate, 3.5g of di-tert-amyl peroxide and 10g of mercaptoethanol are added into a beaker and are magnetically stirred for 15min to be uniformly mixed to prepare a mixed raw material, and after the temperature in the flask is raised to 120 ℃, 10% of the mixed raw material is pre-added into the flask at one time to serve as reaction seeds. After half an hour, slowly dripping the residual mixed raw materials into the four-neck flask by using a constant flow pump, and finishing dripping within about 2 hours; after the addition, the temperature is kept for about 1.5h, 1.5g of initiator is supplemented, and the temperature is kept for about 2h, so that the plant oil-based hydrophilic polymer is obtained.
Vacuum pumping and filtering 40g of isobutanol as a solvent, cooling to 75 ℃, pouring the plant oil-based hydrophilic polymer into a 500mL flask, weighing and recording, then placing the beaker into a high-speed disc dispersing machine, rotating at a speed of 2000r/min, stirring, then slowly dropping 110g of hot water with the same temperature as the weighed plant oil-based hydrophilic polymer, dispersing, dropping N, N-dimethylethanolamine for neutralization, regulating the speed to 4500r/min, dispersing for 5min at a high speed, then reducing the speed to 1500r/min, dispersing for about 30min, and controlling the water addition amount to ensure that the solid content is 45-50% to obtain the plant oil-based hydrophilic polymer aqueous dispersion.
Example 7
Adding ricinoleic acid and mercaptopropionic acid into a quartz tube, adding a photoinitiator 2,4, 6-trimethylbenzoyl ethyl phenylphosphonate accounting for 5% of the weight of the ricinoleic acid and butanone into the quartz tube, reacting in a photochemical reactor with the power of 500W for 3h, and removing the solvent to obtain the castor oil-based polycarboxylic acid. Heating castor oil-based polycarboxylic acid to 70 ℃, adding isocyano ethyl acrylate, wherein the molar ratio of the castor oil-based polycarboxylic acid to the isocyano ethyl acrylate is 0.95: 1, reacting for 1 hour under stirring to obtain the castor oil based hydrophilic monomer.
Adding cottonseed oil acid into a reaction kettle, stirring and heating to 65 ℃, adding a tertiary ammonium salt catalyst N, N-dimethylethanolamine accounting for 1% of the weight of the cottonseed oil acid, heating to 85 ℃, dropwise adding hydroxypropyl methacrylate containing 0.07% of polymerization inhibitor 2-tert-butylhydroquinone, reacting for 2 hours, heating to 95 ℃ and reacting for 4 hours to obtain cottonseed oil acid acrylate.
A500 mL four-neck flask equipped with a stirrer, a condenser, a thermometer and an oil bath was charged with 30g of propylene glycol monomethyl ether and 1g of initiator dibenzoyl peroxide as primers, stirred, purged with nitrogen and heated to a reflux temperature of 120 ℃. 20g of castor oil-based hydrophilic monomer, 70g of cottonseed oleic acid acrylate, 10g of styrene, 10g of methyl methacrylate, 20g of butyl acrylate, 3.5g of dibenzoyl peroxide and 5g of dodecyl mercaptan are added into a beaker and are magnetically stirred for 15min to be uniformly mixed to prepare a mixed raw material, and after the temperature in the flask is raised to 120 ℃, 10% of the mixed raw material is pre-thrown into the flask at one time to serve as reaction seeds. After half an hour, slowly dripping the residual mixed raw materials into the four-neck flask by using a constant flow pump, and finishing dripping within about 2 hours; after the addition, the temperature is kept for about 1.5h, 1.5g of initiator is supplemented, and the temperature is kept for about 2h, so that the plant oil-based hydrophilic polymer is obtained.
Vacuum pumping 10g of propylene glycol methyl ether as a solvent, cooling to 75 ℃, pouring the vegetable oil-based hydrophilic polymer into a 500mL flask, weighing and recording, then placing a beaker into a high-speed disc dispersion machine, rotating at a speed of 2000r/min, stirring, slowly dropping 110g of hot water with the same temperature as the weighed vegetable oil-based hydrophilic polymer for dispersion, dropping triethylamine for neutralization, wherein the neutralization degree is 105%, firstly adjusting the speed to 4500r/min for high-speed dispersion for 5min, then reducing the speed to 2000r/min for dispersion for about 30min, and controlling the water addition amount to ensure that the solid content is 45-50% to obtain the vegetable oil-based hydrophilic polymer.
Example 8
Adding ricinoleic acid and mercaptosuccinic acid into a quartz tube, adding a photoinitiator 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone accounting for 3 percent of the weight of the ricinoleic acid, reacting with butanone in a photochemical reactor with the power of 600W for 5 hours, and removing the solvent to obtain the castor oil-based polycarboxylic acid. Heating castor oil-based polycarboxylic acid to 75 ℃, adding isocyano ethyl methacrylate, wherein the molar ratio of the castor oil-based polycarboxylic acid to the isocyano ethyl acrylate is 0.9: 1, reacting for 0.5h under stirring to obtain the castor oil based hydrophilic monomer.
Adding rapeseed oleic acid into a reaction kettle, stirring and heating to 50 ℃, adding a tertiary ammonium salt catalyst N, N-dimethylethanolamine accounting for 1% of the weight of the rapeseed oleic acid, heating to 90 ℃, dropwise adding hydroxypropyl acrylate containing 0.04% of a polymerization inhibitor 2, 5-di-tert-butylhydroquinone, reacting for 2 hours, heating to 100 ℃ and reacting for 5 hours to obtain the rapeseed oleic acid acrylate.
50g of isobutanol and 2g of initiator di-tert-amyl peroxide are added into a 500mL four-neck flask provided with a stirrer, a condenser, a thermometer and an oil bath kettle to be used as a bottom material, and the mixture is stirred and is heated to the reflux temperature of 120 ℃ under the protection of nitrogen. 50g of castor oil based hydrophilic monomer, 20g of rapeseed oleic acid acrylate, 15g of styrene, 25g of butyl acrylate, 3.5g of di-tert-amyl peroxide and 10g of mercaptoethanol are added into a beaker and are stirred magnetically for 15min to be mixed uniformly to prepare a mixed raw material, and after the temperature in the flask is raised to 120 ℃, 10% of the mixed raw material is pre-added into the flask at one time to serve as reaction seeds. After half an hour, slowly dripping the residual mixed raw materials into the four-neck flask by using a constant flow pump, and finishing dripping within about 2 hours; after the addition, the temperature is kept for about 1.5h, 1.5g of initiator is added, and the temperature is kept for about 2h, so that the plant oil-based hydrophilic polymer is obtained.
Vacuum-pumping and filtering 40g of isobutanol as a solvent, cooling to 75 ℃, pouring the vegetable oil-based hydrophilic polymer into a 500mL flask, weighing and recording, then placing a beaker into a high-speed disc dispersion machine, rotating at a speed of 2000r/min, stirring, then slowly dropping 110g of hot water with the same temperature as the weighed vegetable oil-based hydrophilic polymer, dispersing, dropping N, N-dimethylethanolamine for neutralization, regulating the neutralization degree to 110%, firstly regulating the speed to 4500r/min, dispersing at a high speed for 5min, then reducing the speed to 1500r/min, dispersing for about 30min, controlling the water addition amount to ensure that the solid content is 45-50%, and obtaining the vegetable oil-based hydrophilic polymer water dispersion.
Examples of Properties of aqueous Dispersion and cured film
The solid content test adopts a gravimetric method, about 10g of the plant oil-based hydrophilic polymer aqueous dispersion is weighed, and the weight m of the plant oil-based hydrophilic polymer aqueous dispersion is accurately weighed and recorded 1 Then placing the mixture in a 120 ℃ oven to dry until the mass does not change any more, and accurately weighing the mass and recording the mass as m 2 The aqueous dispersion has a solids content of m 2 /m 1 ×100％。
The storage stability test was carried out according to method of test method for storage stability of coating (GB/T6753.3-1986).
The viscosity was measured by means of a model NDJ-8S rotational viscometer available from Shanghai precision instruments and meters Co., Ltd. at a measurement temperature of 25 ℃.
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).
Mechanical Properties analysis the cured emulsion films of examples 1 to 8 were tested using a universal testing machine model AGS-X1 kN, Shimadzu corporation, Japan, crosshead speed: 10 mm/min; sample size: 40 mm. times.10 mm. times.0.5 mm. The measured tensile strength and elongation at break of the cured film are shown in Table 2.
Impact resistance was measured according to method of determination of impact resistance of paint film (GBT 1732-93). Flexibility test was carried out according to the method of paint film flexibility determination (GB/T1731-1993). Water resistance was tested according to method of determination of Water resistance of paint film (GB/T1733-1993). The temperature resistance and the moisture resistance of the paint film are tested according to the method of GB/T1735-1989, the temperature resistance and the moisture resistance are evaluated at the temperature of 80 ℃ and the humidity of 60 percent, and the paint film does not foam and does not fall off within 72 hours.
TABLE 1 results of comprehensive Properties testing of the aqueous dispersions of the examples
| Examples | Solids content/% | Viscosity/cps/25 deg.C | Storage stability | Appearance of the product |
| Example 1 | 46.2 | 1622 | More than 12 months | Milky white color |
| Example 2 | 45.3 | 1548 | More than 12 months | Milky white color |
| Example 3 | 40.8 | 1654 | For more than 12 months | Milky white color |
| Example 4 | 44.2 | 1621 | More than 12 months | Milky white color |
| Example 5 | 46.8 | 1788 | More than 12 months | Milky white color |
| Example 6 | 47.2 | 1692 | More than 12 months | Milky white color |
| Example 7 | 50.0 | 1720 | More than 12 months | Milky white color |
| Example 8 | 49.1 | 1624 | More than 12 months | Milky white color |
TABLE 2 results of comprehensive property test of aqueous dispersion-cured films of the respective examples
As can be seen from Table 2, the vegetable oil-based hydrophilic polymer aqueous dispersion disclosed by the invention is cured into a film, the adhesive force is 0-2 grade, the pencil hardness is 2H-4H, the impact resistance is 50-75 kg-cm, the flexibility is 2-3 mm, the water resistance is 150-180H, and the temperature resistance and the moisture resistance are more than 72H.
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 (10)
1. A preparation method of a plant oil-based hydrophilic polymer aqueous dispersion is characterized by comprising the following steps:
(1) adding ricinoleic acid, mercaptocarboxylic acid, a photoinitiator and a proper amount of solvent into a quartz tube, carrying out a light click reaction on the ricinoleic acid and the mercaptocarboxylic acid in a photochemical reactor, and reacting for 3-5 h to obtain castor oil-based polycarboxylic acid; then heating to 65-75 ℃, adding acrylic acid isocyanate, reacting castor oil-based polycarboxylic acid with-NCO groups on the acrylic acid isocyanate for 0.5-1.5 h to obtain a castor oil-based hydrophilic monomer;
(2) adding vegetable oil acid into a reaction kettle, stirring, heating to 50-70 ℃, adding a tertiary ammonium salt catalyst, heating to 70-90 ℃, dropwise adding acrylic ester containing a polymerization inhibitor, reacting for 1-2 hours, heating to 80-100 ℃, and reacting for 3-5 hours to obtain a vegetable oil-based acrylic ester monomer; the acrylate is at least one of glycidyl methacrylate, glycidyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate and hydroxypropyl acrylate;
(3) according to the formula, uniformly mixing a castor oil-based hydrophilic monomer, a plant oil-based acrylate monomer, other monomers, a chain transfer agent and part of an initiator to obtain a mixed solution, adding 5-10% of the total amount of the mixed solution into a solvent preheated to 120-160 ℃, reacting for 20-40 min, dropwise adding the rest of the mixed solution into a reaction system, reacting for 1-2 h while keeping the temperature, adding the rest of the initiator into the reaction system, keeping the temperature for 1-2 h, and cooling to 50-60 ℃ to obtain a plant oil-based hydrophilic polymer;
the formula of each component is as follows according to the mass portion: 20-50 parts of a solvent; 20-50 parts of castor oil-based hydrophilic monomer; 20-70 parts of a vegetable oil-based acrylate monomer; 0-100 parts of other monomers; 1-10 parts of a chain transfer agent; 1-10 parts of an initiator; 50-150 parts of water;
(4) and (4) distilling the plant oil-based hydrophilic polymer prepared in the step (3) under reduced pressure to remove the solvent, adding water, stirring and dispersing, and adding a neutralizer for neutralization while dispersing to obtain the plant oil-based hydrophilic polymer aqueous dispersion.
2. The method for preparing the plant oil-based hydrophilic polymer aqueous dispersion according to claim 1, wherein in the step (1), the mercaptocarboxylic acid is at least one of thioglycolic acid, mercaptopropionic acid, and mercaptosuccinic acid;
in the step (1), the molar ratio of ricinoleic acid to mercaptocarboxylic acid is 1: 2.5-1: 3;
in the step (1), the photoinitiator is 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 2,4, 6-trimethyl benzoyl phenyl phosphonic acid ethyl ester, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone, bis 2, 6-difluoro-3-pyrrol phenyl titanocene and benzoin dimethyl ether, wherein the dosage of the photoinitiator is 1-5% of the weight of ricinoleic acid.
3. The method for preparing the plant oil-based hydrophilic polymer aqueous dispersion according to claim 1, wherein in the step (1), the power of the photochemical reaction is 200-600W;
in the step (1), the isocyanate acrylate is at least one of isocyanoethyl acrylate and isocyanoethyl methacrylate;
in the step (1), the molar ratio of the acrylic isocyanate to the castor oil-based polycarboxylic acid is 1: 0.9-1: 1.
4. The method for preparing the vegetable oil-based hydrophilic polymer aqueous dispersion according to claim 1, wherein in the step (2), the vegetable oleic acid is at least one of eleostearic acid, ricinoleic acid, linoleic acid, soybean oleic acid, corn oleic acid, rapeseed oleic acid, and cottonseed oleic acid;
in the step (2), the molar ratio of the vegetable oil acid to the acrylate is 1: (1-1.1).
5. The method for preparing the plant oil-based hydrophilic polymer aqueous dispersion according to claim 1, wherein in the step (2), the polymerization inhibitor is one of hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tert-butyl hydroquinone and 2, 5-di-tert-butyl hydroquinone, and the amount of the polymerization inhibitor is 0.01-0.1% of the mass of the acrylate.
6. The method for preparing the plant oil-based hydrophilic polymer aqueous dispersion according to claim 1, wherein in the step (3), the initiator is at least one of dibenzoyl peroxide, azodiisobutyronitrile, di-tert-butyl peroxide and di-tert-amyl peroxide;
in the step (3), the chain transfer agent is dodecyl mercaptan or mercaptoethanol;
in the step (3), the solvent is at least one of n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol propyl ether, dipropylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol butyl ether, tripropylene glycol butyl ether, propylene glycol phenyl ether, propylene glycol methyl ether acetate and dipropylene glycol methyl ether acetate.
7. The method for preparing the plant oil-based hydrophilic polymer aqueous dispersion according to claim 1, wherein in the step (3), the part of the initiator accounts for 40-60 wt% of the total amount of the initiator;
in the step (3), the dripping speed is 10-100 g/h;
in the step (3), an initiator accounting for 5-10 wt% of the total amount of the initiator is added into the solvent;
in the step (3), the reaction system is reacted under the protection of inert gas.
8. The method for preparing the plant oil-based hydrophilic polymer aqueous dispersion according to claim 1, wherein in the step (4), the rotation speed of stirring and dispersing is 1000-2000 r/min, and the time of stirring and dispersing is 20-60 min;
in the step (4), the neutralizing agent is at least one of ammonia water, triethylamine and N, N-dimethylethanolamine.
9. An aqueous dispersion of a vegetable oil-based hydrophilic polymer made by the method of any one of claims 1-8.
10. Use of the aqueous vegetable oil-based hydrophilic polymer dispersion according to claim 9 in the fields of printing pastes, aqueous coatings, aqueous inks and aqueous adhesives.
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