CN112646158A - Modification method and modification intermediate of waterborne alkyd resin and preparation method of modified waterborne alkyd resin - Google Patents
Modification method and modification intermediate of waterborne alkyd resin and preparation method of modified waterborne alkyd resin Download PDFInfo
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Abstract
The invention discloses a method for modifying water-based alkyd resin, which uses a monofunctional isocyanate curing agent and/or a difunctional isocyanate curing agent to modify the water-based alkyd resin. Also discloses a preparation method of the waterborne alkyd resin modified intermediate, which is characterized in that a monofunctional isocyanic acid curing agent and/or a modified intermediate of an isocyanate bifunctional curing agent are generated through the reaction of a unit alcohol and an isocyanate curing agent. The modified waterborne alkyd resin is prepared by reacting an alkyd resin prepolymer with a monofunctional isocyanate curing agent and/or a bifunctional isocyanate curing agent modified intermediate, and then performing a neutralization reaction. The modified waterborne alkyd resin prepared by the invention can improve the drying speed and hardness of the waterborne alkyd resin.
Description
Technical Field
The invention relates to a modification method of a waterborne alkyd resin, a modified intermediate and a preparation method of the modified waterborne alkyd resin, belonging to the technical field of production of waterborne alkyd resins.
Background
Alkyd resins are widely used in the coatings industry for their economical, inexpensive, easy to apply and air-crosslinking properties, and for their versatility. The traditional solvent-based alkyd resin contains a large amount of organic solvent, which causes air pollution and a large amount of waste of resources and energy. Therefore, the alkyd resin is in the development direction of the alkyd resin, and simultaneously meets the environmental protection requirement. However, compared with the traditional solvent-based alkyd resin, the waterborne alkyd resin has many defects, such as slow drying speed, low hardness, and incapability of meeting construction requirements on water resistance and solvent resistance.
Therefore, the modification of the waterborne alkyd resin is beneficial to the further development of the waterborne alkyd resin and practically meets the social development requirement. The commonly used waterborne alkyd resin modification at present comprises epoxy resin, acrylic acid, organosilicon, polyurethane, isocyanate and the like, for example, Chinese patent application 202010653041.6 adopts acrylic acid modified waterborne alkyd resin, 201710358226.2 adopts TDI modified waterborne alkyd resin, 201811346318.X adopts epoxy resin modified waterborne alkyd resin, 201610721348.9 adopts organosilicon modified waterborne alkyd resin, and 201510581851.4 adopts polyurethane-organosilicon modified waterborne alkyd resin. However, the modification by the above method can improve some properties of the waterborne alkyd resin, but still has a large room for improvement in hardness and dry speed.
The isocyanate curing agent is a hardener of two-component polyurethane, is made of isocyanate (TDI, MDI, HDI and the like) and comprises various types such as addition products, tripolymers, prepolymers, biuret, uretdione, blocked polyisocyanate and the like, and has 3 NCO groups; in the reaction, NCO groups in the curing agent and OH groups in the resin are cross-linked to form a network of macromolecules for curing, and thus the curing agent cannot be used to modify alkyd resins in the mind of those skilled in the art.
Disclosure of Invention
The invention aims to: aiming at the problems, the invention provides a modification method of the waterborne alkyd resin, a modified intermediate and a preparation method of the modified waterborne alkyd resin.
The technical scheme adopted by the invention is as follows:
a method for modifying water-based alkyd resin uses a monofunctional isocyanate curing agent and/or a difunctional isocyanate curing agent to modify the water-based alkyd resin.
It should be noted that, the common isocyanate curing agent contains 3 NCO functional groups, and can be cured by cross-linking reaction with the water-based alkyd resin to produce a network-like macromolecule, and is a hardener for alkyd resin, and the curing agent cannot be used to modify alkyd resin according to the inertia thinking of those skilled in the art.
In the present invention, the inventors have found through experiments that reducing the number of NCO functional groups of the isocyanate curing agent to 1 and/or 2 is capable of modifying alkyd resins. And the alkyd resin modified by the modified intermediate of the monofunctional isocyanate curing agent and/or the difunctional isocyanate curing agent has the characteristics of high drying speed, high hardness and the like.
A preparation method of a waterborne alkyd resin modified intermediate is characterized in that a modified intermediate of a monofunctional isocyanic acid curing agent and/or an isocyanate difunctional curing agent is generated through the reaction of a unit alcohol and an isocyanate curing agent.
In the invention, NCO group quantity in the curing agent is eliminated through the reaction of-OH of the unit alcohol and-NCO in the curing agent, and the monofunctional and/or difunctional isocyanate curing agent is obtained.
Preferably, the isocyanate curing agent comprises a trimer curing agent and/or an adduct curing agent.
Preferably, the isocyanate curing agent comprises a TDI curing agent and/or an HDI curing agent.
Preferably, the isocyanate curing agent is diluted with an organic solvent.
Preferably, the organic solvent is one or more of ethyl acetate, butyl acetate and PMA.
Preferably, the monohydric alcohol is a monohydric alcohol or an alcohol ether solvent.
Preferably, the alcohol ether compounds include ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, and propylene glycol butyl ether.
A preparation method of modified water-based alkyd resin comprises the steps of reacting an alkyd resin prepolymer with a monofunctional isocyanate curing agent and/or a bifunctional isocyanate curing agent modified intermediate, and then performing neutralization reaction to obtain the modified water-based alkyd resin.
A method for modifying a waterborne alkyd resin, a modified intermediate and a method for preparing a modified waterborne alkyd resin comprise the following steps:
step a, preparing alkyd resin prepolymer;
b, preparing a modified intermediate of the monofunctional isocyanic acid curing agent and/or the isocyanate difunctional curing agent;
c, reacting the alkyd resin prepolymer with a monofunctional isocyanic acid curing agent and/or an isocyanate difunctional curing agent;
and d, adding a neutralizing agent to perform salinization reaction to obtain a finished product.
When the monofunctional isocyanate curing agent and/or the difunctional isocyanate curing agent are used for modifying the waterborne alkyd resin, NCO groups in the isocyanate curing agent react with OH groups in the waterborne alkyd resin to generate urethane bonds, and the molecular chain of the isocyanate curing agent is connected to the waterborne alkyd resin, because the NCO groups are only 1 and/or 2, the crosslinking is avoided, and the curing cannot be realized.
The invention eliminates NCO functional group in isocyanate curing agent by pre-reacting unit alcohol and isocyanate curing agent, so that NCO functional group in isocyanate curing agent is only 1 and/or 2, and then reacts with alkyd resin prepolymer, thereby achieving the purpose of modification.
Preferably, the vegetable oil acid is one or more of soya oil acid, tall oil acid, linoleic acid, eleostearic acid, coconut oil acid and ricinoleic acid;
preferably, the dibasic acid is one or more of phthalic anhydride, maleic anhydride, isophthalic acid, terephthalic acid, adipic acid and azelaic acid;
preferably, the polyhydric alcohol is one or more of glycerol, pentaerythritol and trimethylolpropane;
preferably, the aqueous monomer is one of trimellitic anhydride, polyethylene glycol, 5-sodium isophthalic acid sulfonate, dimethylolpropionic acid, maleic anhydride and acrylic acid.
Preferably, the neutralizing agent is triethylamine or dimethylethanolamine.
Preferably, in the step a, each 100 parts of alkyd resin prepolymer comprises 9-12 parts of vegetable oleic acid, 0.5-2 parts of benzoic acid, 21-29 parts of dibasic acid, 16-24 parts of polyol, 5-7 parts of water-based monomer and the balance of xylene
Preferably, in the step a, the vegetable oleic acid, the benzoic acid, the dibasic acid and the xylene are put into a reaction kettle, the temperature is increased to 100-140 ℃ for dissolving the solid raw material, then the temperature is reduced to 80-120 ℃, the polyol is added, the temperature is increased to 160-200 ℃ for reacting for 40-80 minutes, the temperature is gradually increased to 210-230 ℃ for reacting for 3-5 hours until the acid value is less than or equal to 10KOH/mg, the temperature is reduced to 160-200 ℃ for reacting for 40-80 minutes until the mixture is completely clear and transparent, and then the temperature is reduced for later use.
Preferably, in the step a, 9-12 parts by weight of tall oil acid, 0.5-2 parts by weight of benzoic acid, 12-17 parts by weight of phthalic anhydride, 9-12 parts by weight of adipic acid and xylene are put into a reaction kettle, the temperature is raised to 100 ℃ and 140 ℃ to completely dissolve phthalic anhydride and benzoic acid, then the temperature is reduced to 70-110 ℃, 9-12 parts by weight of trimethylolpropane and 7-12 parts by weight of pentaerythritol are added, the temperature is raised to 160 ℃ and 200 ℃ to react for 40-80 minutes, the temperature is gradually raised to 210 ℃ and 230 ℃ to react for 3-5 hours until the acid value is less than or equal to 10KOH/mg, the temperature is reduced to 160 ℃ and 200 ℃ and 5-7 parts by weight of trimellitic anhydride are added to react for 40-80 minutes until the mixture is completely clear and.
Preferably, in step b, the isocyanate curing agent comprises an adduct curing agent and/or a trimer curing agent.
Preferably, in step b, the isocyanate curing agent comprises a TDI curing agent and/or an HDI curing agent.
Preferably, in the step b, the modified intermediate comprises 66-75 parts of finished isocyanate curing agent, 8-12 parts of unit alcohol and the balance of organic solvent per 100 parts of step b.
Preferably, the organic solvent is one or more of ethyl acetate, butyl acetate and PMA.
Preferably, in the step b, the isocyanate curing agent and the organic solvent are uniformly stirred according to the weight part and heated to 40-50 ℃, the polyalcohol is slowly dripped into the curing agent under the stirring condition, the temperature is raised to 55-65 ℃, the reaction is completely carried out until the NCO value and the viscosity are not changed any more, and then the temperature is reduced for standby application.
Preferably, in the step b, 22-25 parts of TDI adduct curing agent, 22-25 parts of TDI trimer curing agent, 22-25 parts of HDI trimer curing agent and butyl acetate are uniformly stirred and heated to 40-50 ℃, 8-12 parts of ethylene glycol monobutyl ether is dripped into the curing agent, and the temperature is raised to 55-65 ℃ for complete reaction.
Preferably, in step c, the alkyd resin prepolymer is reacted with the monofunctional isocyanate curing agent and/or the isocyanate difunctional curing agent at 60-70 ℃ until the viscosity is not changed any more.
Preferably, the step c and the step d comprise 100 parts of alkyd resin prepolymer, 80-120 parts of modified intermediate and 3-4 parts of neutralizer.
According to the modification method, the modified intermediate and the preparation method of the modified waterborne alkyd resin, the waterborne alkyd resin is modified by the monofunctional isocyanate curing agent and/or the difunctional isocyanate curing agent, a urethane bond is linked with the resin, the molecular weight of the resin is increased, the drying speed, the hardness and the fullness of the resin can be improved, and the modified resin has good storage property because the finished isocyanate curing agent does not contain free TDI.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that: the curing agent is used for modifying the waterborne alkyd resin, and the waterborne alkyd resin has the characteristics of high drying speed, high hardness, high fullness, good storage property and the like.
Detailed Description
All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
Any feature disclosed in this specification may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. That is, unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features.
Example 1
The present example includes a method of modifying a waterborne alkyd using a difunctional isocyanate curing agent to modify the waterborne alkyd.
A preparation method of a waterborne alkyd resin modified intermediate, which comprises the following step b.
A preparation method of a modified water-based alkyd resin comprises the following steps:
step a, putting 12 parts of linoleic acid, 9 parts of soya oil acid, 0.5 part of benzoic acid, 9 parts of azelaic acid, 12 parts of maleic anhydride and 48.5 parts of dimethylbenzene into a reaction kettle, heating to 100 ℃, dissolving the solid raw materials, cooling to 80 ℃, adding 16 parts of trimethylolpropane, heating to 160 ℃, reacting for 80 minutes, gradually heating to 210 ℃, reacting for 5 hours until the acid value is less than or equal to 10KOH/mg, cooling to 160 ℃, adding 5 parts of isophthalic acid-5-sodium sulfonate, reacting for 80 minutes until the materials are completely clear and transparent, and cooling for later use;
b, uniformly stirring 50 parts of TDI adduct curing agent, 25 parts of HDI trimer curing agent and 17 parts of PMA, heating to 40 ℃, slowly dripping 8 parts of ethylene glycol ethyl ether into the curing agent under the stirring condition, heating to 55 ℃, reacting until the viscosity and NCO are not changed any more, and cooling to normal temperature for later use;
step c, mixing 100 parts of alkyd resin prepolymer in the step a and 80 parts of curing agent in the step b, and reacting at 60 ℃ until the viscosity does not change;
and d, adding 3 parts of dimethylethanolamine for salinization reaction.
Evaporating the organic solvent and adding distilled water until the solid content is 60 percent to prepare the curing agent modified waterborne alkyd resin.
Example 2
This example includes a method of modifying a waterborne alkyd using a monofunctional isocyanate curing agent.
A preparation method of a waterborne alkyd resin modified intermediate, which comprises the following step b.
A preparation method of a modified water-based alkyd resin comprises the following steps:
step a, putting 12 parts of linoleic acid, 2 parts of benzoic acid, 12 parts of isophthalic acid, 17 parts of adipic acid and 26 parts of xylene into a reaction kettle, heating to 140 ℃, cooling to 120 ℃ after dissolving the solid raw materials, adding 12 parts of glycerol and 12 parts of pentaerythritol, heating to 200 ℃, reacting for 40 minutes, gradually heating to 230 ℃, reacting for 3 hours until the acid value is less than or equal to 10KOH/mg, cooling to 200 ℃, adding 7 parts of acrylic acid, reacting for 40 minutes until the mixture is completely clear and transparent, and cooling for later use;
b, uniformly stirring 36 parts by weight of TDI adduct curing agent, 30 parts by weight of TDI trimer curing agent and 22 parts by weight of ethyl acetate, heating to 50 ℃, slowly dripping 12 parts by weight of propylene glycol ether into the curing agent under the stirring condition, heating to 65 ℃, reacting until the viscosity and NCO are not changed any more, and cooling to normal temperature for later use;
step c, mixing 100 parts of alkyd resin prepolymer in the step a and 120 parts of curing agent in the step b at 70 ℃ to react until the viscosity does not change any more;
and d, adding 4 parts of triethylamine for salinization reaction.
Evaporating the organic solvent and adding distilled water until the solid content is 60 percent to prepare the curing agent modified waterborne alkyd resin.
Example 3
The present example includes a method of modifying a waterborne alkyd using a monofunctional isocyanate curing agent and a difunctional isocyanate curing agent.
A preparation method of a waterborne alkyd resin modified intermediate, which comprises the following step b.
A preparation method of a modified water-based alkyd resin comprises the following steps:
step a, putting 10 parts of tall oil acid, 1 part of benzoic acid, 10 parts of adipic acid, 15 parts of phthalic anhydride and 38 parts of xylene into a reaction kettle, heating to 120 ℃, dissolving a solid raw material, cooling to 80 ℃, adding 10 parts of trimethylolpropane, heating 10 parts of pentaerythritol to 180 ℃, reacting for 60 minutes, gradually heating to 220 ℃, reacting for 4 hours until the acid value is less than or equal to 10KOH/mg, cooling to 180 ℃, adding 6 parts of trimellitic anhydride, reacting for 60 minutes until the mixture is completely clear and transparent, and cooling for later use;
b, uniformly stirring 24 parts of TDI adduct curing agent, 23 parts of TDI tripolymer curing agent, 23 parts of HDI tripolymer curing agent and 20 parts of butyl acetate, heating to 45 ℃, slowly dripping 10 parts of ethylene glycol monomethyl ether into the curing agent under the stirring condition, heating to 60 ℃, reacting until the viscosity and NCO are not changed any more, and cooling to normal temperature for later use;
c, mixing 100 parts of alkyd resin prepolymer in the step a and 100 parts of curing agent in the step b at 65 ℃ to react until the viscosity does not change any more;
and d, adding 3 parts of dimethylethanolamine for salinization reaction.
Evaporating the organic solvent and adding distilled water until the solid content is 60 percent to prepare the curing agent modified waterborne alkyd resin.
Example 4
This example differs from example 3 in that the starting materials in step b are 10 parts of ethylene glycol monomethyl ether, 70 parts of TDI trimer curing agent and 20 parts of butyl acetate.
Example 5
This example differs from example 3 in that the raw materials in step b are ethylene glycol monomethyl ether 10 parts, TDI adduct curing agent 70 parts and butyl acetate 20 parts.
Example 6
This example differs from example 3 in that the raw materials in step b were 10 parts of ethylene glycol monomethyl ether, 70 parts of HDI trimer curing agent and 20 parts of butyl acetate.
Example 7
This example differs from example 3 in that the raw materials in step b are 10 parts of ethylene glycol monomethyl ether, 35 parts of TDI adduct curing agent, 35 parts of TDI trimer curing agent and 20 parts of butyl acetate.
Example 8
This example differs from example 3 in that the raw materials in step b were 10 parts of ethylene glycol monomethyl ether, 35 parts of TDI adduct curing agent, 35 parts of HDI trimer curing agent and 20 parts of butyl acetate.
Example 9
This example differs from example 3 in that the raw materials in step b were 10 parts of ethylene glycol monomethyl ether, 35 parts of TDI trimer curing agent, 35 parts of HDI trimer curing agent and 20 parts of butyl acetate.
Comparative example 1
This comparative example differs from example 3 in that the modification was carried out without using a curing agent.
Comparative example 2
This comparative example differs from example 3 in that the waterborne alkyd was modified in step c with a common curing agent.
Comparative example 3
This comparative example differs from example 3 in that the waterborne alkyd was modified with TDI in step c.
Comparative example 4
This comparative example differs from example 3 in that step a and step b were used without cooling.
Comparative example 5
The comparative example differs from example 3 in step b in that 24 parts of TDI adduct curing agent, 23 parts of TDI trimer curing agent, 23 parts of HDI trimer curing agent and 20 parts of butyl acetate are heated to 60 ℃ and 10 parts of ethylene glycol monomethyl ether is slowly dropped into the curing agent under stirring, and the temperature is raised to 70 ℃ to react until the viscosity and NCO do not change any more.
Comparative example 6
The comparative example differs from example 3 in step b in that 24 parts of TDI adduct curing agent, 23 parts of TDI trimer curing agent, 23 parts of HDI trimer curing agent and 20 parts of butyl acetate are heated to 70 ℃ and 10 parts of ethylene glycol monomethyl ether is slowly dropped into the curing agent under stirring, and the temperature is raised to 80 ℃ to react until the viscosity and NCO do not change any more.
Comparative example 7
This comparative example differs from example 3 in that 100 parts of alkyd resin prepolymer in step a and 100 parts of curing agent in step b were mixed and reacted at 80 ℃ until the viscosity did not change.
Comparative example 8
The difference between the comparative example and the example 3 is that in the step b, 10 parts of ethylene glycol monomethyl ether is added into the curing agent at one time under the stirring condition, and the temperature is increased to 60 ℃ to react until the viscosity and NCO are not changed any more, and then the temperature is reduced to normal temperature for standby.
Comparative example 9
This comparative example differs from example 3 in that in step b, no butyl acetate was added.
The resins of the above examples and comparative examples were tested for properties, wherein viscosity was measured using a rotational viscometer, storage stability was measured by the method of GB/T6753.3 for a heat storage test, surface drying time and actual drying time were measured using the method of GB/T1728, hardness was measured by the method of GB/T6739 for pencil hardness, yellowing resistance was measured using an ultraviolet lamp accelerated aging test for 2 hours, and color difference of the samples before and after the test was measured.
The measured properties are as follows:
| viscosity/25 deg.C | Storage stability | Time to surface dry | Actual drying time | Hardness of pencil | |
| Example 1 | 18000mpa.s | Is normal | 52min | 4.5h | HB+ |
| Example 2 | 13000mpa.s | Is normal | 65min | 6h | HB |
| Example 3 | 15000mpa.s | Is normal | 60min | 5h | HB |
| Example 4 | 14500mpa.s | Is normal | 50min | 4.3h | HB+ |
| Example 5 | 15000mpa.s | Is normal | 62min | 5.5h | HB |
| Example 6 | 16000mpa.s | Is normal | 70min | 7h | HB- |
| Example 7 | 15000mpa.s | Is normal | 58min | 5h | HB |
| Example 8 | 15000mpa.s | Is normal | 64min | 6.5h | HB |
| Example 9 | 14500mpa.s | Is normal | 60min | 6h | HB |
| Comparative example 1 | 13000mpa.s | Is normal | 100min | 20h | B- |
| Comparative example 2 | / | / | / | / | / |
| Comparative example 3 | 14000mpa.s | Crust formation | 80min | 10 | B+ |
| Comparative example 4 | 19000mpa.s | Gelling | 58min | 5.5h | HB |
| Comparative example 5 | 18000mpa.s | Gelling | 61min | 4.5h | HB |
| Comparative example 6 | 21000mpa.s | Gelling | 60min | 4.5h | HB |
| Comparative example 7 | 17000mpa.s | Gelling | 61min | 5h | HB |
| Comparative example 8 | / | / | / | / | / |
| Comparative example 9 | 19000mpa.s | Gelling | 58min | 5h | HB- |
Compared with the comparative example 1, the modified waterborne alkyd resin prepared by the preparation method of the modified waterborne alkyd resin can greatly improve the surface drying time and the actual drying time, and can improve the hardness and the scratch resistance of a paint film.
And the comparative example 2 adopts the common trifunctional curing agent for modification, and the modified failed resin is directly cured.
In contrast to comparative example 3, which is compared to example 3, it can be seen that the open time and the open time of example 3 are faster, with higher hardness; and in example 3, free TDI is not contained, in comparative example 3, more free TDI is contained, in example 3, the test result is normal, in comparative example 3, the surface of the test result is skinned, and the storage property of example 3 is better.
In comparative example 4, the synthesis was carried out without lowering the temperature in step a and step b, resulting in deterioration of the storage properties.
In examples 5 to 6, the reaction temperature in step b was too high, resulting in deterioration of storage properties.
In example 7, the reaction temperature in step c was high, resulting in deterioration of storage properties.
In example 8, ethylene glycol monomethyl ether was added to the isocyanate curing agent all at once, so that the NCO functional groups in the isocyanate curing agent reacted unevenly, part of the NCO groups of the isocyanate curing agent reacted entirely, and part of the NCO groups of the isocyanate curing agent unreacted, and the reacted isocyanate curing agent and the alkyd resin were cured by a crosslinking reaction in the modification of the aqueous alkyd resin.
In example 9, the modified waterborne alkyd resin prepared without adding organic solvent to dilute the isocyanate curing agent had poor storage properties.
The invention is not limited to the foregoing embodiments. The invention extends to any novel feature or any novel combination of features disclosed in this specification and any novel method or process steps or any novel combination of features disclosed.
Claims (10)
1. A method for modifying a water-based alkyd resin is characterized by comprising the following steps: the water-based alkyd resin is modified by using a monofunctional isocyanate curing agent and/or a difunctional isocyanate curing agent.
2. A preparation method of a waterborne alkyd resin modified intermediate is characterized by comprising the following steps: the modified intermediate of the monofunctional isocyanic acid curing agent and/or the isocyanate difunctional curing agent is generated by the reaction of the unit alcohol and the isocyanate curing agent.
3. A process for preparing a waterborne alkyd modified intermediate of claim 2, wherein: the isocyanate curing agent comprises a trimer curing agent and/or an adduct curing agent; preferably, the isocyanate curing agent comprises a TDI curing agent and/or a HDI curing agent; preferably, the isocyanate curing agent is diluted by an organic solvent, and preferably, the organic solvent is one or more of ethyl acetate, butyl acetate and PMA; preferably, the monohydric alcohol is a monohydric alcohol or an alcohol ether solvent.
4. A preparation method of modified water-based alkyd resin is characterized by comprising the following steps: the modified waterborne alkyd resin is prepared by reacting the alkyd resin prepolymer with a monofunctional isocyanate curing agent and/or a bifunctional isocyanate curing agent modified intermediate and then performing neutralization reaction.
5. A preparation method of modified water-based alkyd resin is characterized by comprising the following steps: the method comprises the following steps:
step a, preparing alkyd resin prepolymer;
b, preparing a modified intermediate of the monofunctional isocyanic acid curing agent and/or the isocyanate difunctional curing agent;
step c, reacting the alkyd resin prepolymer with a modified intermediate;
and d, adding a neutralizing agent to perform salinization reaction to obtain a finished product.
6. The method of claim 5, wherein the modified waterborne alkyd is prepared by: in the step a, each 100 parts of alkyd resin prepolymer comprise 9-12 parts of vegetable oleic acid, 0.5-2 parts of benzoic acid, 21-29 parts of dibasic acid, 16-24 parts of polyol, 5-7 parts of water-based monomer and the balance of xylene.
7. The method of claim 5, wherein the modified waterborne alkyd is prepared by: in the step a, plant oleic acid, benzoic acid, dibasic acid and xylene are put into a reaction kettle, the temperature is increased to 100-140 ℃ for dissolving solid raw materials, then the temperature is reduced to 80-120 ℃, polyhydric alcohol is added, the temperature is increased to 160-200 ℃ for reacting for 40-80 minutes, the temperature is gradually increased to 210-230 ℃ for reacting for 3-5 hours until the acid value is less than or equal to 10KOH/mg, the temperature is reduced to 160-200 ℃ for reacting for 40-80 minutes until the mixture is completely clear and transparent, and then the temperature is reduced for later use. Preferably, in the step a, 9-12 parts by weight of tall oil acid, 0.5-2 parts by weight of benzoic acid, 12-17 parts by weight of phthalic anhydride, 9-12 parts by weight of adipic acid and xylene are put into a reaction kettle, the temperature is raised to 100 ℃ and 140 ℃ to completely dissolve phthalic anhydride and benzoic acid, then the temperature is reduced to 70-110 ℃, 9-12 parts by weight of trimethylolpropane and 7-12 parts by weight of pentaerythritol are added, the temperature is raised to 160 ℃ and 200 ℃ to react for 40-80 minutes, the temperature is gradually raised to 210 ℃ and 230 ℃ to react for 3-5 hours until the acid value is less than or equal to 10KOH/mg, the temperature is reduced to 160 ℃ and 200 ℃ and 5-7 parts by weight of trimellitic anhydride are added to react for 40-80 minutes until the mixture is completely clear and.
8. The method of claim 5, wherein the modified waterborne alkyd is prepared by: in the step b, each 100 parts of the modified intermediate comprises 66-75 parts of finished isocyanate curing agent, 8-12 parts of unit alcohol and the balance of organic solvent.
9. The method of claim 5, wherein the modified waterborne alkyd is prepared by: in the step b, the isocyanate curing agent and the organic solvent are heated to 40-50 ℃, the polyalcohol is slowly dripped into the curing agent under the stirring condition, the temperature is raised to 55-65 ℃ for reaction until the NCO value and the viscosity are not changed any more, and then the temperature is reduced for standby application.
10. The method of claim 5, wherein the modified waterborne alkyd is prepared by: in the step c, the alkyd resin prepolymer and the modified intermediate react at the temperature of 60-70 ℃ until the viscosity does not change.
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