CN113214420A - Vegetable oil-based polyacrylate anionic emulsion and preparation method and application thereof - Google Patents
Vegetable oil-based polyacrylate anionic emulsion and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a vegetable oil-based polyacrylate anionic emulsion and a preparation method and application thereof. The preparation method comprises the following steps: preparing a vegetable oil-based acrylate monomer, uniformly mixing the vegetable oil-based acrylate monomer, other monomers, a chain transfer agent and part of an initiator according to a formula to obtain a mixed solution, adding part of the total amount of the mixed solution into a preheated solvent, reacting for a period of time, dropwise adding the balance of the mixed solution into a reaction system, adding the balance of the initiator into the reaction system after heat preservation reaction, and cooling after heat preservation reaction; adding a mercapto monomer and a photoinitiator, and reacting in a photochemical reactor for 3-5 h; and distilling under reduced pressure to remove the solvent, adding water, stirring and dispersing, and adding a neutralizer for neutralization while dispersing to obtain the vegetable oil-based polyacrylate anionic emulsion. The invention replaces the traditional acrylate monomer with the natural renewable vegetable oil to prepare the high molecular polymer, thereby reducing the pressure of petrochemical resources and improving the added value of the vegetable oil.
Description
Technical Field
The invention belongs to the technical field of organic polymer materials, and particularly relates to a vegetable oil-based polyacrylate anionic emulsion, and a preparation method and application thereof.
Background
The aqueous acrylic resin comprises acrylic resin emulsion, acrylic resin aqueous dispersion and acrylic resin aqueous solution. The emulsion is synthesized by emulsifying oily vinyl monomers in water under the initiation of an aqueous radical initiator, and the resin aqueous dispersion is synthesized by different processes such as radical solution polymerization or stepwise solution polymerization. The solution polymerization is a polymerization reaction in which a monomer is dissolved in a proper solvent and an initiator is added in a solution state, and is an important synthesis method in the process of synthesizing a polymer. Generally, the reaction is carried out at the reflux temperature of the solvent, so that the reaction temperature can be effectively controlled, and the heat generated by the exothermic reaction can be dissipated by the evaporation of the solvent. The traditional acrylic resin is mainly prepared from acrylate monomers through free radical polymerization, and is generally divided into pure acrylic emulsion, styrene-acrylic emulsion, vinyl acetate-acrylic emulsion, silicone-acrylic emulsion, tertiary acetate (tertiary carbonate-vinyl acetate) emulsion, tertiary acrylic (tertiary carbonate-acrylate) emulsion and the like according to the monomer composition. But the acrylic ester is mainly from petrochemical resources, and most 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 polymeric monomer for replacing an acrylate monomer to prepare the bio-based waterborne acrylic resin becomes a hotspot of research. As a renewable biomass resource, the vegetable oil has rich sources, low price and easy regeneration, and although the vegetable oil also contains unsaturated double bonds, the vegetable oil has low polymerization reaction activity and cannot prepare a high molecular polymer by a traditional solution polymerization mode. However, the vegetable oil molecules often contain active hydroxyl, carboxyl and other groups, and the groups can be organically synthesized into segments, and acrylate double bonds with high polymerization activity are introduced into the vegetable oil molecules, so that the vegetable oil is introduced into the molecular chain of the acrylic resin, the using amount of petroleum-based acrylate monomers in the acrylic resin can be greatly reduced, and the pressure of petrochemical resources is reduced.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a preparation method of a vegetable oil-based polyacrylate anionic emulsion.
The invention also aims to provide the vegetable oil-based polyacrylate anionic emulsion prepared by the method.
The invention further aims to provide application of the vegetable oil-based polyacrylate anionic emulsion in the fields of printing mucilage, water-based paint, water-based ink and water-based adhesive.
The purpose of the invention is realized by the following scheme:
a preparation method of vegetable oil-based polyacrylate anionic emulsion comprises the following steps:
(1) 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;
(2) uniformly mixing a vegetable 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, and reacting for 1-2 h under heat preservation; adding the rest of initiator into the reaction system, preserving the heat for 1-2 h, and cooling to 50-60 ℃ to obtain the vegetable oil-based polyacrylate with the molecular brush structure;
the formula of each component is as follows according to the mass portion: 30-50 parts of a solvent; 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;
(3) adding a mercapto monomer and a photoinitiator into the plant oil-based polyacrylate with the molecular brush structure prepared in the step (2), and reacting in a photochemical reactor for 3-5 hours to obtain plant oil-based polyacrylate with the hydrophilic molecular brush structure;
(4) and (4) distilling the hydrophilic molecular brush structure vegetable oil-based polyacrylate prepared in the step (3) under reduced pressure to remove the solvent, adding water, stirring and dispersing, and adding a neutralizer while dispersing for neutralization to obtain the vegetable oil-based polyacrylate anionic emulsion.
In the step (1), the molar ratio of the vegetable oil acid to the acrylate is 1: (1-1.1), a small amount of excess acrylate is not removed and may be left as a polymerization monomer.
In the step (1), 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 (1), the acrylate is at least one of glycidyl methacrylate, glycidyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate and hydroxypropyl acrylate.
In the step (1), 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.
The initiator in the above preparation steps is 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 (2), the chain transfer agent is conventional in the art, and is preferably dodecyl mercaptan or mercaptoethanol.
In the step (2), 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 (2), the other monomers are hard monomers or soft monomers.
In the step (3), the mercapto monomer is at least one of thioglycolic acid, mercaptopropionic acid and mercaptosuccinic acid. The molar ratio of the mercapto monomer to the molecular brush structure vegetable oil-based polyacrylate is 3: 1-9: 1.
in the step (3), the photoinitiator is at least one of 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-trimethylbenzoyl phenyl ethyl phosphonate, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone, bis (2, 6-difluoro-3-pyrrolylphenyl titanocene) and benzoin dimethyl ether, the dosage of the photoinitiator is 1-5% of the weight of the vegetable oil-based polyacrylate with the molecular brush structure.
The power of the photochemical reaction is 200-600W.
In order to further achieve the aim of the invention, the using amount of the water is 0.8-1 time of the total mass of the monomers.
In the step (2), the part of the initiator accounts for 40-60 wt% of the total amount of the initiator.
In the step (2), the dripping speed is preferably 10-100 g/h.
In the step (2), an initiator accounting for 5-10 wt% of the total amount of the initiator is added into the solvent.
In the step (2), the reaction system is preferably reacted under the protection of inert gas.
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.
In the step (4), 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 vegetable oil-based polyacrylate with the molecular brush structure, which is prepared by the invention, can adjust the glass transition temperature thereof 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 vegetable oil-based polyacrylate anionic emulsion prepared by the method, wherein the solid content is 50-55%, 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 3H-5H, 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 traditional hydrophilic polyacrylate is prepared by directly adding hydrophilic monomers such as (methyl) acrylic acid and the like to participate in copolymerization in a polymerization stage to prepare a polymer containing hydrophilic groups. According to the invention, a polymer is prepared by solution polymerization of a hydrophobic monomer, and after the polymer is synthesized, through a light click reaction, mercaptocarboxylic acid reacts with residual double bonds in a reaction system, so that hydrophilic groups are introduced into hydrophobic polyacrylate. In the light click reaction, the mercapto carboxylic acid can react with double bonds in the vegetable oleic acid and also can react with double bonds in the residual acrylic ester in the polymerization reaction, so that on one hand, the residual amount of the double bonds in the resin can be reduced to the maximum extent, and the influence of the residual double bonds on the performance of the polymer is reduced. On the other hand, hydrophilic groups can be introduced into residual acrylate small molecules, so that the acrylate small molecules are converted into amphiphilic substances, and the acrylate small molecules play a self-emulsifying role in the emulsion. Secondly, because the double bond content of the drying oil such as tung oil, flax oil and the like is higher than that of other vegetable oil, more carboxyl groups can be introduced on a polymer chain by adopting a process of introducing carboxyl groups through light click reaction at the later stage, thereby improving the hydrophilicity of the polyacrylate. Therefore, the emulsion prepared by the invention can still obtain high solid content of more than 50 percent on the basis of higher storage stability. Thus, compared to other vegetable oil-based polyacrylates, the polyacrylates prepared according to the invention are completely free of double bonds.
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 doubled 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) According to the invention, after the synthesis of the acrylic resin is completed, the hydrophilic group is grafted on the acrylic resin by adopting the mercapto-alkene click reaction, so that the use of traditional micromolecule hydrophilic monomers such as acrylic acid is avoided, on one hand, the prepared polymer has enough hydrophilicity, on the other hand, the use of acrylic hydrophilic monomers with volatility and pungent odor is avoided, and thus, the odorless polymer emulsion without pungent odor 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 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 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, 10 wt% of the mixed raw material is pre-added into a flask with preheated bottom materials at one time after the temperature in the flask is raised to 120 ℃, and the mixed raw material is used as a reaction seed. 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; 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 vegetable oil-based polyacrylate with the molecular brush structure is obtained. Adding thioglycollic acid (the molar ratio of the thioglycollic acid to the plant oil-based polyacrylate with the molecular brush structure is 3:1) and 2-hydroxy-2-methyl-1-phenyl acetone serving as a photoinitiator (the using amount of the photoinitiator is 1% of the mass of the plant oil-based polyacrylate with the molecular brush structure), reacting in a photochemical reactor with the power of 600W for 3 hours to obtain the plant oil-based polyacrylate with the hydrophilic molecular brush structure.
Vacuum pumping and filtering out 25g of propylene glycol monobutyl ether as a solvent, cooling to 75 ℃, pouring the plant oil-based polyacrylate with the hydrophilic molecular brush structure into a 500mL flask, weighing and recording, then placing a beaker into a high-speed disc dispersion machine, rotating at 2000r/min for stirring, slowly dropping 110g of hot water with the same temperature as the plant oil-based polyacrylate with the hydrophilic molecular brush structure for dispersion, dropping triethylamine 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 adding amount to ensure that the solid content is 50-55% to obtain the plant oil-based polyacrylate anion emulsion.
Example 2
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 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, 10% of the mixed raw material is pre-added into the flask at one time after the temperature in the flask is raised to 120 ℃, and the mixed raw material is used as a reaction seed. 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 vegetable oil-based polyacrylate with the molecular brush structure is obtained. Adding mercaptopropionic acid (the molar ratio of the mercaptopropionic acid to the plant oil-based polyacrylate with the molecular brush structure is 9:1) and a photoinitiator 1-hydroxycyclohexyl phenyl ketone (the dosage is 5% of the mass of the plant oil-based polyacrylate with the molecular brush structure), reacting in a photochemical reactor with the power of 200W for 5h to obtain the plant oil-based polyacrylate with the hydrophilic molecular brush structure.
Vacuum pumping and filtering out 20g of solvent n-butyl alcohol, cooling to 75 ℃, pouring the hydrophilic molecular brush structure vegetable oil-based polyacrylate 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 for stirring, then slowly dropwise adding 110g of hot water with the same temperature as the weighed hydrophilic molecular brush structure vegetable oil-based polyacrylate for dispersion, dropwise adding ammonia water for neutralization, regulating the neutralization degree to 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 50-55% to obtain the vegetable oil-based polyacrylate anion emulsion.
Example 3
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 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-feeding 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 added, and the temperature is kept for about 2h, so that the vegetable oil-based polyacrylate with the molecular brush structure is obtained. Adding thiodibutyrylicacid (the molar ratio of the thiodibutyrylicacid to the plant oil-based polyacrylate with the molecular brush structure is 5:1) and 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone (the dosage is 3% of the mass of the plant oil-based polyacrylate with the molecular brush structure), reacting in a photochemical reactor with the power of 300W for 5h to obtain the plant oil-based polyacrylate with the hydrophilic molecular brush structure.
Vacuum pumping and filtering out 35g of propylene glycol methyl ether acetate as a solvent, cooling to 75 ℃, pouring the plant oil-based polyacrylate with the hydrophilic molecular brush structure into a 500mL flask, weighing and recording, then placing a beaker into a high-speed disc dispersion machine, rotating at the speed of 1000r/min, stirring, then slowly dropping 110g of hot water with the same temperature as that of the plant oil-based polyacrylate with the hydrophilic molecular brush structure, 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 50-55% to obtain the plant oil-based polyacrylate anionic emulsion.
Example 4
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. Adding 50g of soybean oleic acid acrylate, 3.5g of di-tert-butyl peroxide and 10g 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 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 added, and the temperature is kept for about 2h, so that the vegetable oil-based polyacrylate with the molecular brush structure is obtained. Adding thioglycollic acid (the molar ratio of the thioglycollic acid to the plant oil-based polyacrylate with the molecular brush structure is 5:1) and 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide serving as a photoinitiator (the using amount of the 2% of the mass of the plant oil-based polyacrylate with the molecular brush structure), reacting in a photochemical reactor with the power of 500W for 3 hours to obtain the plant oil-based polyacrylate with the hydrophilic molecular brush structure.
Vacuum pumping and filtering out 20g of propylene glycol monobutyl ether as a solvent, cooling to 75 ℃, pouring the plant oil-based polyacrylate with the hydrophilic molecular brush structure into a 500mL flask, weighing and recording, then placing a beaker into a high-speed disc dispersion machine, rotating at 1500r/min, stirring, slowly dropping 100g of hot water with the same temperature as the plant oil-based polyacrylate with the hydrophilic molecular brush structure, dispersing, dropping N, N-dimethylethanolamine for neutralization, regulating the speed to 4500r/min, dispersing at a 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 50-55% to obtain the plant oil-based polyacrylate anionic emulsion.
Example 5
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 ℃. 60g of corn oleic acid 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, 10 percent of the mixed raw material is pre-added into the flask at one time after the temperature in the flask is raised to 120 ℃, and the mixed raw material is used as a reaction seed. 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 vegetable oil-based polyacrylate with the molecular brush structure is obtained. Adding mercaptopropionic acid (the molar ratio of the mercaptopropionic acid to the plant oil-based polyacrylate with the molecular brush structure is 4:1) and 2,4, 6-trimethyl benzoyl phenyl ethyl phosphonate (the using amount is 4% of the mass of the plant oil-based polyacrylate with the molecular brush structure), reacting in a photochemical reactor with the power of 400W for 4 hours to obtain the plant oil-based polyacrylate with the hydrophilic molecular brush structure.
Vacuum pumping 10g of propylene glycol methyl ether as a solvent, cooling to 75 ℃, pouring the plant oil-based polyacrylate with the hydrophilic molecular brush structure 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 that of the plant oil-based polyacrylate with the hydrophilic molecular brush structure, dispersing, dropping triethylamine for neutralization, regulating the speed to 4500r/min, dispersing at a 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 50-55% to obtain the plant oil-based polyacrylate anion emulsion.
Example 6
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. 70g 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 percent 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 vegetable oil-based polyacrylate with the molecular brush structure is obtained. Adding thiodiglycolic acid (the molar ratio of the thiodiglycolic acid to the plant oil-based polyacrylate with the molecular brush structure is 6:1) and 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone (the using amount is 3 percent of the mass of the plant oil-based polyacrylate with the molecular brush structure), reacting in a photochemical reactor with the power of 600W for 3 hours to obtain the plant oil-based polyacrylate with the hydrophilic molecular brush structure.
Vacuum pumping and filtering 40g of isobutanol as a solvent, cooling to 75 ℃, pouring the vegetable oil-based polyacrylate with the hydrophilic molecular brush structure into a 500mL flask, weighing and recording, placing the beaker into a high-speed disc dispersion machine, rotating at a speed of 2000r/min for stirring, slowly dropping 110g of hot water with the same temperature as the vegetable oil-based polyacrylate with the hydrophilic molecular brush structure for dispersion, dropping N, N-dimethylethanolamine for neutralization, regulating the speed to 4500r/min for high-speed dispersion for 5min, then reducing the speed to 1500r/min for dispersion for about 30min, and controlling the water addition amount to ensure that the solid content is 50-55% to obtain the vegetable oil-based polyacrylate anionic emulsion.
Example 7
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 corn 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 the 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 ℃. Adding 40g of cottonseed 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 added, and the temperature is kept for about 2h, so that the vegetable oil-based polyacrylate with the molecular brush structure is obtained. Adding mercaptopropionic acid (the molar ratio of the mercaptopropionic acid to the plant oil-based polyacrylate with the molecular brush structure is 4:1) and 2,4, 6-trimethyl benzoyl phenyl ethyl phosphonate (the using amount is 4% of the mass of the plant oil-based polyacrylate with the molecular brush structure), reacting in a photochemical reactor with the power of 400W for 4 hours to obtain the plant oil-based polyacrylate with the hydrophilic molecular brush structure.
Vacuum pumping 10g of propylene glycol methyl ether as a solvent, cooling to 75 ℃, pouring the plant oil-based polyacrylate with the hydrophilic molecular brush structure 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 that of the plant oil-based polyacrylate with the hydrophilic molecular brush structure, dispersing, dropping triethylamine for neutralization, regulating the speed to 4500r/min, dispersing at a 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 50-55% to obtain the plant oil-based polyacrylate anion emulsion.
Example 8
Adding cottonseed 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. 60g of cottonseed 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, 10% of the mixed raw material is pre-added into the flask at one time after the temperature in the flask is raised to 120 ℃, and the mixed raw material is used as a reaction seed. 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 vegetable oil-based polyacrylate with the molecular brush structure is obtained. Adding thiodiglycolic acid (the molar ratio of the thiodiglycolic acid to the plant oil-based polyacrylate with the molecular brush structure is 6:1) and 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone (the using amount is 3 percent of the mass of the plant oil-based polyacrylate with the molecular brush structure), reacting in a photochemical reactor with the power of 600W for 3 hours to obtain the plant oil-based polyacrylate with the hydrophilic molecular brush structure.
Vacuum pumping and filtering 40g of isobutanol as a solvent, cooling to 75 ℃, pouring the vegetable oil-based polyacrylate with the hydrophilic molecular brush structure into a 500mL flask, weighing and recording, placing the beaker into a high-speed disc dispersion machine, rotating at a speed of 2000r/min for stirring, slowly dropping 110g of hot water with the same temperature as the vegetable oil-based polyacrylate with the hydrophilic molecular brush structure for dispersion, dropping N, N-dimethylethanolamine for neutralization, regulating the speed to 4500r/min for high-speed dispersion for 5min, then reducing the speed to 1500r/min for dispersion for about 30min, and controlling the water addition amount to ensure that the solid content is 50-55% to obtain the vegetable oil-based polyacrylate anionic emulsion.
Examples of emulsion and cured film Properties
The solid content test adopts a gravimetric method, about 10g of vegetable oil-based polyacrylate anionic emulsion is weighed, and the weight m of the vegetable oil-based polyacrylate anionic emulsion is accurately weighed and recorded1Then 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 m2Emulsion solid content ═ m2/m1×100％。
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 1.
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 emulsion performance test in each example
| Examples | Solids content/% | Viscosity/cps/25 deg.C | Storage stability | Appearance of the product |
| Example 1 | 53.8 | 1587 | More than 12 months | Milky white color |
| Example 2 | 52.7 | 1698 | More than 12 months | Milky white color |
| Example 3 | 50.0 | 1822 | Is greater than12 months old | Milky white color |
| Example 4 | 54.1 | 1698 | More than 12 months | Milky white color |
| Example 5 | 54.7 | 1720 | More than 12 months | Milky white color |
| Example 6 | 51.8 | 1766 | More than 12 months | Milky white color |
| Example 7 | 52.2 | 1624 | More than 12 months | Milky white color |
| Example 8 | 53.6 | 1788 | More than 12 months | Milky white color |
TABLE 2 results of comprehensive property test of emulsion cured films of the examples
As can be seen from tables 1 and 2, the vegetable oil-based polyacrylate anionic emulsion disclosed by the invention is cured at room temperature to form a film, the adhesive force is 0-2 grade, the pencil hardness is 3H-5H, 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 vegetable oil-based polyacrylate anionic emulsion is characterized by comprising the following steps:
(1) 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;
(2) uniformly mixing a vegetable 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, and reacting for 1-2 h under heat preservation; adding the rest of initiator into the reaction system, preserving the heat for 1-2 h, and cooling to 50-60 ℃ to obtain the vegetable oil-based polyacrylate with the molecular brush structure;
the formula of each component is as follows according to the mass portion: 30-50 parts of a solvent; 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;
(3) adding a mercapto monomer and a photoinitiator into the plant oil-based polyacrylate with the molecular brush structure prepared in the step (2), and reacting in a photochemical reactor for 3-5 hours to obtain plant oil-based polyacrylate with the hydrophilic molecular brush structure;
(4) and (4) distilling the hydrophilic molecular brush structure vegetable oil-based polyacrylate prepared in the step (3) under reduced pressure to remove the solvent, adding water, stirring and dispersing, and adding a neutralizer while dispersing for neutralization to obtain the vegetable oil-based polyacrylate anionic emulsion.
2. The method for preparing the vegetable oil-based polyacrylate anionic emulsion according to claim 1, wherein in the step (1), 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 (1), the acrylate is at least one of glycidyl methacrylate, glycidyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate and hydroxypropyl acrylate;
in the step (1), the molar ratio of the vegetable oil acid to the acrylate is 1: (1-1.1);
in the step (1), 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.
3. The method for preparing the vegetable oil-based polyacrylate anionic emulsion according to claim 1, wherein the initiator is at least one of dibenzoyl peroxide, azobisisobutyronitrile, di-tert-butyl peroxide and di-tert-amyl peroxide;
the chain transfer agent is dodecyl mercaptan or mercaptoethanol;
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.
4. The method for preparing the vegetable oil-based polyacrylate anionic emulsion according to claim 1, wherein in the step (2), the amount of the partial initiator is 40 to 60 wt% of the total amount of the initiator, the dropping speed is 10 to 100g/h, the amount of the initiator of 5 to 10 wt% of the total amount of the initiator is added to the solvent, and the reaction system is under the protection of inert gas.
5. The method for preparing the vegetable oil-based polyacrylate anionic emulsion according to claim 1, wherein in the step (3), the mercapto monomer is at least one of thioglycolic acid, mercaptopropionic acid and mercaptosuccinic acid; the molar ratio of the mercapto monomer to the molecular brush structure vegetable oil-based polyacrylate is 3: 1-9: 1.
6. the method for preparing the vegetable oil-based polyacrylate anionic emulsion according to claim 1, wherein in step (3), the photoinitiator is 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, bis (2, 6-difluoro-3-pyrrolylphenyltitanocene), bis (2-hydroxy-2-methyl-1-phenyl-1-propanone, bis (2-hydroxy-2-methyl-1-phenyl-acetonate), or bis (2-hydroxy-2-hydroxy-cyclohexyl-phenyl-acetonate), And the photoinitiator is 1-5% of the weight of the vegetable oil-based polyacrylate with the molecular brush structure.
7. The method for preparing the vegetable oil-based polyacrylate anionic emulsion 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.
8. The method for preparing the vegetable oil-based polyacrylate anionic emulsion according to claim 1, wherein in the step (4), 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%.
9. A vegetable oil-based polyacrylate anionic emulsion made by the method of any one of claims 1-8.
10. Use of the vegetable oil-based polyacrylate anionic emulsion of claim 9 in the fields of printing pastes, aqueous coatings, aqueous inks and aqueous adhesives.
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