CN108129667B - Phosphate/polyurethane modified waterborne alkyd resin and preparation method thereof - Google Patents
Phosphate/polyurethane modified waterborne alkyd resin and preparation method thereof Download PDFInfo
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Abstract
The invention relates to phosphate/polyurethane modified waterborne alkyd resin, wherein a polyurethane and phosphate functional monomer are introduced into an alkyd resin structure, and the alkyd resin is prepared by reacting vegetable oil fatty acid, isophthalic acid, organic acid anhydride, dihydric alcohol, branched polyol, dimethylolpropionic acid, alkyl acrylate phosphate, polyisocyanate and a neutralizer; the alkyl acrylate phosphate is prepared from hydroxyethyl methacrylate and R6‑8OH and phosphorus pentoxide are obtained by reaction. The phosphate/polyurethane modified waterborne alkyd resin prepared by the invention has a glass transition temperature Tg of 20-40 ℃, a molecular weight of 10000-12000 and a particle size of 200-300 nm; the paint has excellent adhesive force, water resistance, chemical resistance, aging resistance, corrosion resistance and salt spray resistance; the paint is widely used for water-based anticorrosive paint, water-based steel structure paint, water-based engineering machinery paint, water-based woodenware paint, water-based plastic paint and the like.
Description
Technical Field
The invention relates to a modified waterborne alkyd resin, in particular to a preparation method of a phosphate/polyurethane modified waterborne alkyd resin, belonging to the technical field of waterborne resin synthesis.
Background
The alkyd resin modified by vegetable oil or fatty acid and synthesized by esterification of polyalcohol and polybasic acid comprises drying, semi-drying and non-drying oleoresin, has long oil length and oil length, has good gloss and dispersibility, is a main film forming substance of many types of coatings such as alkyd, amino, nitro, polyurethane and the like, is a resin for traditional coatings, has excellent durability, gloss retention, color retention, hardness and flexibility and excellent brushing property, and therefore, occupies an extremely important position and a great share in solvent-based coatings. In addition, the production of the alkyd resin does not depend on the petroleum industry, is not easily influenced by the international petroleum price, has the advantages of low price, adjustable components of the alkyd resin, variable branching degree and functionality, short cycle of product transformation input turnover and the like, and is incomparable with other resins.
In recent years, along with the vigorous development of national economy in China, the application demand of the coating in daily production and life is increased year by year, when the coating is used in large amount, because a large amount of organic volatile matters exist in the coating, the coating seriously pollutes the atmosphere, and also seriously damages the life and ecological environment of human beings, therefore, in order to protect the environment where the people live and the health of the human beings, more and more strict standards are already made by most developed countries to limit the use of organic solvent coatings and accelerate the development of solvent-based coatings to the direction of low pollution, along with the addition of the world trade organization in China, the pollution-free green environment-friendly coating development is also reflected, so most scientific research organizations and colleges have started to develop pollution-free green environment-friendly coatings.
The water-soluble alkyd paint takes water as a solvent, so that a film-forming substance is uniformly dispersed or dissolved in the water, and the water-soluble alkyd paint does not contain benzene and other organic solvents, and is beneficial to reducing environmental pollution and harm to human health. Therefore, the water-based alkyd resin is an environment-friendly coating with wide market development prospect.
The polyurethane is a polymer polymerized by polyisocyanate, macromolecular polyester polyol or polyether polyol, micromolecular polyol and polyamine chain extender, and has the advantages of high hardness, wear resistance, excellent adhesion property and the like, so that the polyurethane is widely applied to the fields of coatings, adhesives, foamed plastics, printing ink, rubber and the like; phosphate is a common adhesion promoter, is suitable for various substrates such as copper, iron, aluminum, wood, plastics and the like, and particularly has an obvious promoting effect on the adhesion of metal substrates such as copper, iron, aluminum and the like because strong polarity of phosphate groups generates strong chemical bonding action with the substrates, but the phosphate has a high acid value, and the water resistance of a coating is influenced by excessive addition amount which cannot be excessive.
The synthesis and performance research of phosphate modified water-based alkyd resin is disclosed by He Li Fan, Cheng Xing Guang, etc., wherein maleic anhydride, acrylate and phosphate free radical solution are copolymerized to synthesize a prepolymer with low relative molecular mass, then the prepolymer is esterified with monoglyceride, phthalic anhydride and dimethylolpropionic acid monomers to synthesize modified alkyd resin, triethylamine is added to neutralize and form salt, and water is added to stir at high speed to prepare clear and transparent water-dispersed alkyd resin with the particle size distribution of 20-100 nm. The process comprises the steps of synthesizing water-based alkyd resin by a monoglyceride method, firstly improving the compatibility of reactants through alcoholysis reaction, then copolymerizing maleic acid with acrylate and phosphate to synthesize a novel modified prepolymer, and esterifying and synthesizing the acrylate-modified water-based alkyd resin by using an anhydride bond in the structure of the prepolymer; because the adhesive force of the alkyd resin is poor, the adhesive force of the modified alkyd resin can only reach grade 1, the modified alkyd resin has low hardness, is not easy to polish, has insufficient crosslinking density and poor waterproofness, and the alkyl carbon number of the used phosphate ester monomer is less, so that the compatibility of the synthetic emulsion is poor.
The prior water-based alkyd resin coating has the problems of poor anti-corrosion performance, easy flash corrosion after coating, poor acid resistance and weather resistance, low adhesive force, low hardness, poor stability and the like, and no phosphate ester/polyurethane modified water-based alkyd resin data is available.
Disclosure of Invention
The invention aims to provide a phosphate/polyurethane modified waterborne alkyd resin and a preparation method thereof.
The phosphate group in the phosphate functional monomer has strong polarity and can generate strong chemical bonding effect with the base material, and the phosphorus and the metal base material can form a compact protective film to phosphorize the metal base material and increase the adhesive force and the crosslinking density of the metal base material and the base material, thereby improving the corrosion resistance and the salt spray resistance of the metal base material.
The introduced phosphate functional monomer is alkyl acrylate phosphate, and the length of an alkyl carbon chain influences the performance of the resin, for example, the carbon chain is too long, the steric hindrance is large during free radical polymerization, and the purity of the alkyl acrylate phosphate is influenced; the carbon chain length is selected to be 6-8 because of the poor compatibility due to too short carbon chain.
In order to solve the problems of the alkyd resin such as non-lasting weather resistance, poor adhesion, low hardness and the like, the aliphatic isocyanate is introduced into the molecular structure of the alkyd resin, so that the hardness, the crosslinking density and the adhesion of a paint film of the water-based alkyd resin are improved; and the aliphatic isocyanate has yellowing resistance and chemical resistance, and a coating film has flexibility and high mechanical strength.
The phosphate ester/polyurethane modified waterborne alkyd resin is synthesized step by step in the synthesis technology, the polyurethane modified alkyd resin prepolymer is synthesized firstly, and the phosphate ester structure is finally and independently dropwise added for reaction, so that the phosphate ester structure is positioned on the end position of a resin molecule and is not easily coated in the resin molecule structure, and in the resin film forming process, a phosphate ester functional monomer is easier to enrich the surface and is fully combined with a substrate, the characteristics of the phosphate ester functional monomer and the polyurethane structure are fully exerted, and the advantages of the alkyd resin are kept.
The invention relates to a self-emulsifying water-based alkyd resin, which avoids the influence of the use of an emulsifier on the water resistance, the transparency and the gloss of a coating film.
Because the hydrolysis resistance of the isophthalic acid is better than that of the phthalic acid (phthalic anhydride), the isophthalic acid is partially used for replacing the phthalic acid (phthalic anhydride) so as to improve the hydrolysis resistance of the water-based alkyd. The more branched chains of the polyol, the better the hydrolysis resistance, the more reasonably the proportion of the branched chain polyol and the dihydric alcohol is adjusted to control the functionality, so that the reaction is stably carried out, more hydroxyl groups left in the resin after the esterification reaction are primary hydroxyl groups, the steric hindrance is small, the crosslinking density is favorably improved, and the good dryness can be obtained without a film-forming assistant; in addition, the viscosity of the resin is favorably reduced under the condition of high relative molecular mass, and the branched chain structure of the resin is favorable for reducing the polarity of the resin and improving the hydrolysis resistance of the resin; further, the more hydroxyl groups in the resin molecule, the smaller the particle size of the emulsion after dispersion, and the more stable the emulsion.
The phosphate/polyurethane modified waterborne alkyd resin comprises the following components in parts by weight: 6.0-12.0 parts of vegetable oil fatty acid, 4.0-8.0 parts of isophthalic acid, 2.0-5.0 parts of organic acid anhydride, 1.5-3.0 parts of dihydric alcohol, 2.0-5.0 parts of branched chain polyol, 1.5-3.0 parts of dimethylolpropionic acid, 1.5-6.0 parts of alkyl acrylate phosphate, 4.0-6.0 parts of polyisocyanate, 1.5-3.0 parts of neutralizer, 0.02-0.08 part of dibutyltin dilaurate, 0.04-0.1 part of azodiisobutyronitrile and 42.0-60.0 parts of deionized water; wherein the molar ratio of the isophthalic acid to the organic acid anhydride is 1: 1/3-1/2; the molar ratio of the branched chain polyol to the dihydric alcohol is 1: 1/3-1/2.
The organic acid anhydride is one or a combination of more of phthalic anhydride, adipic acid, maleic anhydride and acetic anhydride.
The dihydric alcohol is one or a combination of more of ethylene glycol, propylene glycol, butanediol, hexanediol and dipropylene glycol; the branched chain polyalcohol is one or a combination of more of neopentyl glycol, isoprene glycol, trimethylolpropane, glycerol, trimethylolethane and pentaerythritol.
The vegetable oil fatty acid is subjected to double bleaching and refining treatment and is one or a combination of more of linseed oil, soybean oil, castor oil, tall oil, coconut oil and rapeseed oil.
The neutralizing agent is one or a combination of more of triethylamine, ammonia water and dimethylethanolamine.
The polyisocyanate is one or a combination of isophorone diisocyanate, hexamethylene diisocyanate and cyclohexane dimethylene diisocyanate.
The synthesis reaction formula of the alkyl acrylate phosphate is shown as follows:
wherein R is C6-8The carbon chain can provide good compatibility of alkyl acrylate phosphate, and the hydroxyethyl methacrylate adopted by the invention has lower double bond activity than hydroxyethyl acrylate, so that the hydroxyethyl methacrylate can react in the subsequent reaction processLess polymerization.
The alkyl acrylate phosphate comprises the following components in parts by weight: 35.0-45.0 parts of hydroxyethyl methacrylate and R6-830-40.0 parts of OH, 0.1-0.5 part of hydroquinone and 20-30.0 parts of phosphorus pentoxide.
Said R6-8OH is a carbon chain of C6-8The mono-alcohol of (1).
The preparation method of the alkyl acrylate phosphate comprises the following steps:
adding a certain amount of hydroxyethyl methacrylate and a certain amount of hydroquinone into a flask, uniformly stirring and heating to about 50 ℃, and simultaneously adding phosphorus pentoxide and R in batches6-8And (3) adding OH within 1.5h, heating the mixed system to 82 ℃, carrying out heat preservation reaction for 3h, measuring the acid value, stopping the reaction when the acid value is consistent with the designed value, cooling, and discharging to obtain the alkyl acrylate phosphate.
The invention provides a preparation method of phosphate/polyurethane modified waterborne alkyd resin, which comprises the following preparation steps:
a) adding weighed polyalcohol and dimethylolpropionic acid into a four-opening reactor with a thermometer, a condenser pipe and a stirrer, dropwise adding polyisocyanate at a constant speed of 60-70 ℃ under the stirring condition for 1h, then continuously heating to 80 ℃, and carrying out heat preservation reaction for 2h to obtain an active intermediate;
b) sequentially adding vegetable oil fatty acid, organic acid anhydride, dihydric alcohol, branched chain polyol and reflux solvent xylene into a four-port reactor provided with a thermometer, a condensation pipe, a water separator and a stirrer according to the weight part ratio of the formula, heating to 100 ℃, keeping the temperature for 0.5h, removing part of water, continuously heating to 140 ℃, stirring at a low speed, heating to 180 ℃ after 1h, keeping the temperature for 2h, continuously heating to 210-220 ℃ when the water is little, measuring the acid value after 1h, and evaporating the solvent xylene under vacuum when the acid value reaches a theoretical design value; cooling to 80 ℃, adding a catalyst dibutyltin dilaurate, dropwise adding an appropriate amount of acetone to adjust viscosity, dropwise adding the active intermediate at a constant speed under stirring, continuously reacting for 2h after the dropwise adding is finished, measuring the NCO content, stopping the reaction when the NCO content is close to a theoretical design value, cooling to below 50 ℃, adding a neutralizing agent, stirring for 0.5h, adding a formula amount of deionized water, filtering, and removing the acetone under vacuum to obtain the polyurethane modified alkyd resin;
c) adding the polyurethane modified alkyd resin into a reactor, heating to 82 ℃, and dropwise adding a mixed solution of alkyl acrylate phosphate and azodiisobutyronitrile at a constant speed for 3-5 hours while stirring; and after the dropwise addition, continuously heating to 85 ℃, keeping the temperature for reaction for 1 hour, cooling, and filtering to obtain the phosphate/polyurethane modified waterborne alkyd resin.
The phosphate/polyurethane modified waterborne alkyd resin prepared by the invention has narrow molecular weight distribution, small particle size of 200-300 nm, glass transition temperature Tg of 20-40 ℃ and molecular weight of 10000-12000.
The phosphate/polyurethane modified waterborne alkyd resin disclosed by the invention has excellent adhesive force, water resistance, chemical resistance, aging resistance, corrosion resistance and salt spray resistance; the paint is widely used for water-based anticorrosive paint, water-based steel structure paint, water-based engineering machinery paint, water-based woodenware paint, water-based plastic paint and the like.
Detailed Description
The invention is further described with reference to the following examples for the preparation of phosphate/polyurethane modified waterborne alkyds. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
Example 1
An alkyl acrylate phosphate A is prepared by the following steps:
weighing 35.0 parts of hydroxyethyl methacrylate and 0.2 part of hydroquinone, adding into a flask, uniformly stirring, heating to about 50 ℃, simultaneously adding 28.0 parts of phosphorus pentoxide and 36.8 parts of heptanol in batches, adding within 1.5h, heating the mixed system to 82 ℃, carrying out heat preservation reaction for 3h, measuring the acid value, stopping the reaction when the acid value reaches the designed value, cooling, and discharging to obtain the alkyl acrylate phosphate A.
Example 2
An alkyl acrylate phosphate ester B is prepared by the following steps:
weighing 40.0 parts of hydroxyethyl methacrylate and 0.2 part of hydroquinone, adding into a flask, uniformly stirring, heating to about 50 ℃, simultaneously adding 26.0 parts of phosphorus pentoxide and 33.8 parts of hexanol in batches, adding within 1.5h, heating the mixed system to 82 ℃, carrying out heat preservation reaction for 3h, measuring the acid value, stopping the reaction when the acid value reaches the designed value, cooling, and discharging to obtain the alkyl acrylate phosphate B.
Example 3
An alkyl acrylate phosphate ester C is prepared by the following steps:
weighing 38.0 parts of hydroxyethyl methacrylate and 0.2 part of hydroquinone, adding into a flask, uniformly stirring, heating to about 50 ℃, simultaneously adding 30.0 parts of phosphorus pentoxide and 31.8 parts of hexanol in batches, adding within 1.5h, heating the mixed system to 82 ℃, carrying out heat preservation reaction for 3h, measuring the acid value, stopping the reaction when the acid value reaches the designed value, cooling, and discharging to obtain the alkyl acrylate phosphate C.
Example 4
A phosphate/polyurethane modified waterborne alkyd resin X is prepared by the following process:
a) adding 1.5 parts of weighed butanediol and 1.2 parts of dimethylolpropionic acid into a four-opening reactor with a thermometer, a condenser pipe and a stirrer, dropwise adding 5.0 parts of isophorone diisocyanate at a constant speed at 60-70 ℃ under the stirring condition for 1h, then continuously heating to 80 ℃, and carrying out heat preservation reaction for 2h to obtain the active intermediate;
b) sequentially adding 10.0 parts of castor oil, 2.0 parts of phthalic anhydride, 1.5 parts of trimethylolpropane, 2.2 parts of neopentyl glycol, 5.0 parts of isophthalic acid and 8.0 parts of dimethylbenzene into a four-port reactor provided with a thermometer, a condenser pipe, a water separator and a stirrer according to the weight part ratio of a formula, heating to 100 ℃, keeping the temperature for 0.5h, removing part of water, continuously heating to 140 ℃, stirring slowly, heating to 180 ℃ after 1h, keeping the temperature for about 2h, continuously heating to 210-220 ℃ when the water is little, measuring the acid value after 1h, and evaporating the solvent under vacuum when the acid value reaches a theoretical design value; cooling to 80 ℃, adding 0.05 part of dibutyltin dilaurate serving as a catalyst, dropwise adding 6.0 parts of acetone to adjust viscosity, dropwise adding the active intermediate at a constant speed under stirring, continuously reacting for 2 hours after dropwise adding, measuring the NCO content, stopping the reaction when the NCO content is close to a theoretical design value, cooling to below 50 ℃, adding 1.3 parts of a neutralizing agent, stirring for 0.5 hour, adding 53.39 parts of deionized water, filtering, and removing acetone to obtain the polyurethane modified alkyd resin;
c) adding the polyurethane modified alkyd resin into a reactor, heating to 82 ℃, and dropwise adding a mixed solution of 2.8 parts of alkyl acrylate phosphate A and 0.06 part of azodiisobutyronitrile at a constant speed under stirring for 3-5 hours; and after the dropwise addition, continuously heating to 85 ℃, carrying out heat preservation reaction for 1h, cooling, and filtering to obtain the phosphate/polyurethane modified waterborne alkyd resin X.
Example 5
A phosphate/polyurethane modified waterborne alkyd resin Y is prepared by the following steps:
a) adding 2.0 parts of weighed neopentyl glycol and 1.8 parts of dimethylolpropionic acid into a four-opening reactor with a thermometer, a condenser tube and a stirrer, dropwise adding 6.0 parts of isophorone diisocyanate at a constant speed at 60-70 ℃ under the stirring condition for 1h, then continuously heating to 80 ℃, and carrying out heat preservation reaction for 2h to obtain the active intermediate;
b) sequentially adding 12.0 parts of soybean oil, 2.4 parts of phthalic anhydride, 2.6 parts of trimethylolethane, 2.2 parts of propylene glycol, 4.6 parts of isophthalic acid and 10.0 parts of xylene into a four-port reactor provided with a thermometer, a condenser pipe, a water separator and a stirrer according to the weight part ratio of a formula, heating to 100 ℃, keeping the temperature for 0.5h, removing part of water, continuously heating to 140 ℃, stirring slowly, heating to 180 ℃ after 1h, keeping the temperature for about 2h, continuously heating to 210-220 ℃ when the water is little, measuring the acid value after 1h, and distilling off the solvent under vacuum when the acid value reaches a theoretical design value; cooling to 80 ℃, adding 0.05 part of dibutyltin dilaurate serving as a catalyst, dropwise adding 7.0 parts of acetone to adjust viscosity, dropwise adding the active intermediate at a constant speed under stirring, continuously reacting for 2 hours after dropwise adding, measuring the NCO content, stopping the reaction when the NCO content is close to a theoretical design value, cooling to below 50 ℃, adding 1.6 parts of a neutralizing agent, stirring for 0.5 hour, adding 44.48 parts of deionized water, filtering, and removing acetone to obtain the polyurethane modified alkyd resin;
c) adding the polyurethane modified alkyd resin into a reactor, heating to 82 ℃, and dropwise adding a mixed solution of 3.2 parts of alkyl acrylate phosphate B and 0.07 part of azodiisobutyronitrile at a constant speed for 3-5 hours while stirring; and after the dropwise addition, continuously heating to 85 ℃, keeping the temperature for reaction for 1 hour, cooling, and filtering to obtain the phosphate/polyurethane modified waterborne alkyd resin Y.
Example 6
A phosphate/polyurethane modified waterborne alkyd resin Z is prepared by the following steps:
a) adding 2.1 parts of weighed hexanediol and 1.5 parts of dimethylolpropionic acid into a four-opening reactor with a thermometer, a condenser pipe and a stirrer, dropwise adding 4.5 parts of hexamethylene diisocyanate at a constant speed at 60-70 ℃ under the stirring condition for 1h, then continuously heating to 80 ℃, and carrying out heat preservation reaction for 2h to obtain an active intermediate;
b) sequentially adding 8.0 parts of castor oil, 2.2 parts of maleic anhydride, 2.0 parts of trimethylolethane, 2.0 parts of pentaerythritol, 4.0 parts of isophthalic acid and 6.0 parts of xylene into a four-port reactor provided with a thermometer, a condenser pipe, a water separator and a stirrer according to the weight part ratio of the formula, heating to 100 ℃, keeping the temperature for 0.5h, removing part of water, continuously heating to 140 ℃, stirring slowly, heating to 180 ℃ after 1h, keeping the temperature for about 2h, continuously heating to 210-220 ℃ when the water is little, measuring the acid value after 1h, and distilling off the solvent under vacuum when the acid value reaches the theoretical design value; cooling to 80 ℃, adding 0.05 part of dibutyltin dilaurate serving as a catalyst, dropwise adding 5.0 parts of acetone to adjust viscosity, dropwise adding the active intermediate at a constant speed under stirring, continuously reacting for 2 hours after dropwise adding, measuring the NCO content, stopping the reaction when the NCO content is close to a theoretical design value, cooling to below 50 ℃, adding 1.5 parts of a neutralizing agent, stirring for 0.5 hour, adding 58.69 parts of deionized water, filtering, and removing acetone to obtain the polyurethane modified alkyd resin;
c) adding the polyurethane modified alkyd resin into a reactor, heating to 82 ℃, and dropwise adding a mixed solution of 2.4 parts of alkyl acrylate phosphate and 0.06 part of azodiisobutyronitrile at a constant speed under stirring for 3-5 hours; and after the dropwise addition, continuously heating to 85 ℃, carrying out heat preservation reaction for 1h, cooling, and filtering to obtain the phosphate/polyurethane modified waterborne alkyd resin Z.
The phosphate ester/polyurethane modified waterborne alkyd X, Y, Z of the example of the invention and the comparative example (phosphate ester modified waterborne alkyd D) were formulated as waterborne anticorrosive paint X according to the following formulation1、Y1、Z1And comparative example D2。
The formula of the water-based anticorrosive paint comprises the following components: 30-50% of water-based alkyd resin, 10-18% of filler (talcum powder and mica powder), 10-20% of iron oxide red, 20-30% of composite zinc phosphate, 0.5-2.0% of dispersant, 1.0-5.0% of auxiliary agent and the balance of deionized water.
According to the relevant standards, the performance of the water-based anticorrosive paint is compared and detected, and the performance technical indexes are shown in table 1.
Table 1: technical performance index of water-based anticorrosive paint
As seen from Table 1, the water-based anticorrosive paint prepared from the emulsion of the invention has better water resistance, salt fog resistance and adhesion than the comparative example, which is based on the dual functions (passivation effect and high water resistance) of the phosphatide/polyurethane modified water-based alkyd resin of the invention, the adhesion and compactness between a coating film and a base material are high, water molecules, chloride ions, sodium ions and the like are effectively isolated from entering between the resin and the base material, and the adhesion and flash rust resistance of the coating film are effectively improved, so that the water resistance, the salt fog resistance and the corrosion resistance of the coating film are improved.
Although the present invention has been described in detail and with reference to exemplary embodiments thereof, it will be apparent to one skilled in the art that various changes, modifications and variations can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (4)
1. A preparation method of phosphate/polyurethane modified waterborne alkyd resin is characterized by comprising the following steps: a) adding 1.5 parts of butanediol and 1.2 parts of dimethylolpropionic acid into a four-opening reactor with a thermometer, a condenser pipe and a stirrer, dropwise adding 5.0 parts of isophorone diisocyanate at a constant speed at 60-70 ℃ under the stirring condition for 1h, then continuously heating to 80 ℃, and carrying out heat preservation reaction for 2h to obtain an active intermediate; b) sequentially adding 10.0 parts of castor oil, 2.0 parts of phthalic anhydride, 1.5 parts of trimethylolpropane, 2.2 parts of neopentyl glycol, 5.0 parts of isophthalic acid and 8.0 parts of reflux solvent xylene into a four-port reactor provided with a thermometer, a condenser pipe, a water separator and a stirrer according to the weight parts of the formula, heating to 100 ℃, keeping the temperature for 0.5h, removing part of water, continuously heating to 140 ℃, stirring slowly, heating to 180 ℃ after 1h, keeping the temperature for 2h, continuously heating to 210-220 ℃ when the water is little, measuring the acid value after 1h, and when the acid value reaches the theoretical design value, evaporating off the solvent xylene under vacuum; cooling to 80 ℃, adding 0.05 part of dibutyltin dilaurate, dropwise adding acetone to adjust viscosity, dropwise adding an active intermediate at a constant speed under stirring, continuously reacting for 2 hours after the dropwise adding is finished, measuring the NCO content, stopping the reaction when the NCO content is close to a theoretical design value, cooling to below 50 ℃, adding 1.3 parts of a neutralizing agent, stirring for 0.5 hour, adding 53.39 parts of deionized water, filtering, and removing acetone under vacuum to obtain the polyurethane modified alkyd resin; c) adding the polyurethane modified alkyd resin into a reactor, heating to 82 ℃, and dropwise adding a mixed solution of 2.8 parts of alkyl acrylate phosphate A and 0.06 part of azodiisobutyronitrile at a constant speed for 3-5 hours while stirring; after the dripping is finished, continuously heating to 85 ℃, keeping the temperature for reaction for 1 hour, cooling and filtering to obtain the phosphate/polyurethane modified waterborne alkyd resin; the preparation method of the alkyl acrylate phosphate A comprises the following steps: adding 35.0 parts of hydroxyethyl methacrylate and 0.2 part of hydroquinone into a flask, uniformly stirring and heating to about 50 ℃, simultaneously adding 28.0 parts of phosphorus pentoxide and 36.8 parts of heptanol in batches, adding within 1.5h, then heating a mixed system to 82 ℃, carrying out heat preservation reaction for 3h, measuring the acid value, stopping the reaction when the acid value reaches the designed value, cooling, discharging, and obtaining the alkyl acrylate phosphate A.
2. A preparation method of phosphate/polyurethane modified waterborne alkyd resin is characterized by comprising the following steps: a) adding 2.0 parts of neopentyl glycol and 1.8 parts of dimethylolpropionic acid into a four-opening reactor with a thermometer, a condenser tube and a stirrer, dropwise adding 6.0 parts of isophorone diisocyanate at a constant speed at 60-70 ℃ under the stirring condition for 1h, then continuously heating to 80 ℃, and carrying out heat preservation reaction for 2h to obtain an active intermediate; b) sequentially adding 12.0 parts of soybean oil, 2.4 parts of phthalic anhydride, 2.6 parts of trimethylolethane, 2.2 parts of propylene glycol, 4.6 parts of isophthalic acid and 10.0 parts of dimethylbenzene into a four-port reactor provided with a thermometer, a condenser pipe, a water separator and a stirrer according to the weight parts of the formula, heating to 100 ℃, keeping the temperature for 0.5h, removing part of water, continuously heating to 140 ℃, stirring slowly, heating to 180 ℃ after 1h, keeping the temperature for 2h, continuously heating to 210-220 ℃ when the water is little, measuring the acid value after 1h, and evaporating the solvent dimethylbenzene under vacuum when the acid value reaches the theoretical design value; cooling to 80 ℃, adding 0.05 part of dibutyltin dilaurate, dropwise adding 7.0 parts of acetone to adjust viscosity, dropwise adding an active intermediate at a constant speed under stirring, continuously reacting for 2 hours after dropwise adding, measuring NCO content, stopping reaction when the NCO content is close to a theoretical design value, cooling to below 50 ℃, adding 1.6 parts of a neutralizing agent, stirring for 0.5 hour, adding 44.48 parts of deionized water, filtering, and removing acetone to obtain polyurethane modified alkyd resin; c) adding the polyurethane modified alkyd resin into a reactor, heating to 82 ℃, and dropwise adding a mixed solution of 3.2 parts of alkyl acrylate phosphate B and 0.07 part of azodiisobutyronitrile at a constant speed for 3-5 hours while stirring; after the dripping is finished, continuously heating to 85 ℃, keeping the temperature for reaction for 1 hour, cooling and filtering to obtain the phosphate/polyurethane modified waterborne alkyd resin; wherein, the preparation steps of the alkyl acrylate phosphate ester B are as follows: adding 40.0 parts of hydroxyethyl methacrylate and 0.2 part of hydroquinone into a flask, uniformly stirring and heating to about 50 ℃, simultaneously adding 26.0 parts of phosphorus pentoxide and 33.8 parts of hexanol in batches, adding within 1.5h, then heating a mixed system to 82 ℃, carrying out heat preservation reaction for 3h, measuring the acid value, stopping the reaction when the acid value is consistent with the designed value, cooling, discharging, and preparing the alkyl acrylate phosphate B.
3. A preparation method of phosphate/polyurethane modified waterborne alkyd resin is characterized by comprising the following steps: a) adding 2.1 parts of hexanediol and 1.5 parts of dimethylolpropionic acid into a four-port reactor with a thermometer, a condenser tube and a stirrer, dropwise adding 4.5 parts of hexamethylene diisocyanate at a constant speed at 60-70 ℃ under the stirring condition for 1h, then continuously heating to 80 ℃, and carrying out heat preservation reaction for 2h to obtain an active intermediate; b) sequentially adding 8.0 parts of castor oil, 2.2 parts of maleic anhydride, 2.0 parts of trimethylolethane, 2.0 parts of pentaerythritol, 4.0 parts of isophthalic acid and 6.0 parts of xylene according to the weight parts of the formula into a four-port reactor provided with a thermometer, a condenser pipe, a water separator and a stirrer, heating to 100 ℃, keeping the temperature for 0.5h, removing part of water, continuously heating to 140 ℃, stirring slowly, heating to 180 ℃ after 1h, keeping the temperature for 2h, continuously heating to 210-220 ℃ when the water is little, measuring the acid value after 1h, and evaporating the solvent xylene under vacuum when the acid value reaches the theoretical design value; cooling to 80 ℃, adding 0.05 part of dibutyltin dilaurate, dropwise adding 5.0 parts of acetone to adjust viscosity, dropwise adding an active intermediate at a constant speed under stirring, continuously reacting for 2 hours after dropwise adding, measuring the NCO content, stopping the reaction when the NCO content is close to a theoretical design value, cooling to below 50 ℃, adding 1.5 parts of a neutralizing agent, stirring for 0.5 hour, adding 58.69 parts of deionized water, filtering, and removing acetone to obtain the polyurethane modified alkyd resin; c) adding the polyurethane modified alkyd resin into a reactor, heating to 82 ℃, and dropwise adding a mixed solution of 2.4 parts of alkyl acrylate phosphate and 0.06 part of azodiisobutyronitrile at a constant speed for 3-5 hours while stirring; after the dripping is finished, continuously heating to 85 ℃, keeping the temperature for reaction for 1 hour, cooling and filtering to obtain the phosphate/polyurethane modified waterborne alkyd resin; wherein, the preparation steps of the alkyl acrylate phosphate ester C are as follows: adding 38.0 parts of hydroxyethyl methacrylate and 0.2 part of hydroquinone into a flask, uniformly stirring and heating to about 50 ℃, simultaneously adding 30.0 parts of phosphorus pentoxide and 31.8 parts of hexanol in batches, adding within 1.5h, then heating a mixed system to 82 ℃, carrying out heat preservation reaction for 3h, measuring the acid value, stopping the reaction when the acid value is consistent with the designed value, cooling, discharging, and preparing the alkyl acrylate phosphate C.
4. The preparation method according to claims 1-3, wherein the neutralizing agent is one or more of triethylamine, ammonia water, and dimethylethanolamine.
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| CN109627392A (en) * | 2018-11-29 | 2019-04-16 | 合众（佛山）化工有限公司 | Fluoro- phosphate modified aqueous alkide resin of one kind and preparation method thereof |
| CN109608975A (en) * | 2018-11-29 | 2019-04-12 | 合众（佛山）化工有限公司 | A kind of fluoro- phosphate modified alkyd water-based anticorrosive paint |
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| CN113174025B (en) * | 2021-04-19 | 2022-12-27 | 陕西科技大学 | Phosphate functional monomer modified waterborne polyurethane composite emulsion and preparation method thereof |
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| CN116554823B (en) * | 2023-07-10 | 2023-09-05 | 山东凯恩新材料科技有限公司 | Waterproof polyurethane adhesive and preparation method thereof |
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