CN114752043A - Water-based alkyd resin composite material and preparation method and application thereof - Google Patents

Water-based alkyd resin composite material and preparation method and application thereof Download PDF

Info

Publication number
CN114752043A
CN114752043A CN202210364412.8A CN202210364412A CN114752043A CN 114752043 A CN114752043 A CN 114752043A CN 202210364412 A CN202210364412 A CN 202210364412A CN 114752043 A CN114752043 A CN 114752043A
Authority
CN
China
Prior art keywords
acid
alkyd resin
esterification product
reacting
resin composite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210364412.8A
Other languages
Chinese (zh)
Other versions
CN114752043B (en
Inventor
董强
路超
吴勇
李金玲
陈萍
何成淼
王利瑶
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Transfar Paint Co Ltd
Original Assignee
Zhejiang Transfar Paint Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang Transfar Paint Co Ltd filed Critical Zhejiang Transfar Paint Co Ltd
Priority to CN202210364412.8A priority Critical patent/CN114752043B/en
Publication of CN114752043A publication Critical patent/CN114752043A/en
Application granted granted Critical
Publication of CN114752043B publication Critical patent/CN114752043B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/46—Polyesters chemically modified by esterification
    • C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
    • C08G18/3895—Inorganic compounds, e.g. aqueous alkalimetalsilicate solutions; Organic derivatives thereof containing no direct silicon-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/68—Unsaturated polyesters
    • C08G18/683—Unsaturated polyesters containing cyclic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention relates to a water-based alkyd resin composite material and a preparation method and application thereof. The preparation method comprises the following steps: under the protective atmosphere, vegetable oleic acid, polybasic acid, polyalcohol, esterification catalyst and solvent are mixed and reacted to obtain an esterification productAn agent; reacting the esterification product with a half-end-capping reagent to obtain a half-end-capped esterification product, wherein the half-end-capping reagent is selected from at least one of o-hydroxybenzoic acid and o-hydroxynaphthoic acid; removing the solvent in the half-end-capping esterification product to react with acid anhydride to obtain the product with the acid value of 35mgKOH g‑1‑55mgKOH·g‑1The end-capped esterification product of (a); reacting the diluted end-capped esterification product with a neutralizer to obtain an alkyd resin polyol prepolymer; mixing the alkyd resin polyol prepolymer and the amino modified halloysite nanotube, and reacting with a diisocyanate solution to obtain the water-based alkyd resin composite material. When the water-based alkyd resin composite material prepared by the preparation method is used for paint, the surface drying speed and the initial water resistance of the paint can be obviously improved.

Description

Water-based alkyd resin composite material, and preparation method and application thereof
Technical Field
The invention relates to the technical field of chemical industry, in particular to a water-based alkyd resin composite material and a preparation method and application thereof.
Background
The water-based alkyd resin as an environment-friendly resin has the advantages of low VOC content, difficult combustion, safe use, low-temperature drying, flow line coating, energy conservation and the like. However, the paint based on the water-based alkyd resin has the defects of low surface drying speed, poor initial water resistance and the like, and when the paint is used for steel structure paint, the phenomenon of rusting caused by rainwater after a coated steel structure is transported outdoors is easy to occur, so that the requirement of outdoor coating cannot be met.
Disclosure of Invention
In view of the above, there is a need to provide a water-based alkyd resin composite material, a preparation method and applications thereof; the preparation method can obtain the water-based alkyd resin composite material with a certain space structure, has good drying property, and can remarkably improve the surface drying speed and the initial water resistance of the coating when being used for the coating.
A method of preparing a waterborne alkyd resin composite, the method comprising the steps of:
under the protective atmosphere, mixing vegetable oleic acid, polybasic acid, polyalcohol, an esterification catalyst and an organic solvent, and carrying out esterification reaction to obtain an esterification product;
reacting the esterification product with a half-capping reagent to obtain a half-capped esterification product, wherein the half-capping reagent is selected from at least one of o-hydroxybenzoic acid and o-hydroxynaphthoic acid;
removing the solvent in the semi-end-capping esterification product, and then reacting with acid anhydride to obtain the product with the acid value of 35mgKOH g-1-55mgKOH·g-1The end-capped esterification product of (a);
diluting the end-capped esterification product, and reacting with a neutralizer to obtain an alkyd resin polyol prepolymer; and
and mixing the alkyd resin polyol prepolymer with the amino modified halloysite nanotube, and then reacting with a diisocyanate solution to obtain the water-based alkyd resin composite material.
In one embodiment, the ortho-hydroxybenzoic acid is selected from at least one of 2, 3-dihydroxybenzoic acid, 2, 3-dihydroxy-5-methylbenzoic acid, 3, 4-dihydroxybenzoic acid, 2,3, 4-trihydroxybenzoic acid, 3,4, 5-trihydroxybenzoic acid; the o-hydroxynaphthoic acid is at least one selected from the group consisting of 2, 3-dihydroxynaphthoic acid, 6, 7-dihydroxynaphthoic acid, 7, 8-dihydroxynaphthoic acid, 5, 6-dihydroxy-2-naphthoic acid, 6, 7-dihydroxy-2-naphthoic acid, and 4,6, 7-dihydroxy-2-naphthoic acid.
In one embodiment, the half-capped esterified product has an acid value of 10mgKOH g-1-20mgKOH·g-1。
In one embodiment, in the step of mixing the vegetable oil acid, the polybasic acid, the polyhydric alcohol, the esterification catalyst and the solvent, the mass ratio of the vegetable oil acid, the polybasic acid and the polyhydric alcohol is (23-33): (16-24): (20-30);
and/or in the step of reacting the esterification product with a half-end capping agent, the mass ratio of the half-end capping agent to the polyol is 1:2-1: 6;
and/or removing the solvent in the half-end-capped esterification product, and reacting with anhydride, wherein the mass ratio of the anhydride to the polyol is 1:1.1-1: 3;
and/or diluting the end-capped esterification product, and reacting with a neutralizing agent, wherein the mass ratio of the neutralizing agent to the polyhydric alcohol is 1:2.5-1: 10;
and/or in the step of mixing the alkyd resin polyol prepolymer and the amino-modified halloysite nanotubes, the mass ratio of the amino-modified halloysite nanotubes to the polyol is 1:5.5-1: 20.
In one embodiment, the molar ratio of the hydroxyl content of the polyol to the carboxyl content of the vegetable oil acid is from 2:1 to 3:1, and the molar ratio of the hydroxyl content of the polyol to the carboxyl content of the polyacid is from 1:1 to 1.7: 1.
In one embodiment, the diisocyanate solution comprises diisocyanate and a solvent without nucleophilic functional groups, the mass ratio of the diisocyanate to the polyol is 1:2-1:15, and the mass ratio of the diisocyanate to the solvent without nucleophilic functional groups is 1:1-1.5: 1.
In one embodiment, the step of reacting the esterification product with a half-capping agent is carried out at a reaction temperature of 190 ℃ to 220 ℃.
In the preparation method of the water-based alkyd resin composite material, the adjacent hydroxyl is introduced through the end-capping reaction, so that on one hand, the grafting amount of the halloysite nanotube in the alkyd resin can be increased, and on the other hand, the water-based alkyd resin composite material prepared by the preparation method has a certain spatial structure by utilizing the adjacent-group steric hindrance effect, and the anisotropy of the molecular chain of the water-based alkyd resin composite material is favorably realized; on the other hand, abundant ortho-hydroxyl groups can ensure that isocyanate groups introduce urethane bonds and urea bonds into alkyd resin, so that the waterborne alkyd resin composite material has good drying property, and the isocyanate groups can extend the chain of the alkyd resin, thereby being beneficial to obtaining the waterborne alkyd resin composite material with a certain molecular weight.
The water-based alkyd resin composite material is prepared by the preparation method of the water-based alkyd resin composite material.
The application of the water-based alkyd resin composite material in paint.
In one embodiment, the mass fraction of the waterborne alkyd resin composite in the coating is 15% -30%.
The invention provides a water-based alkyd resin composite material with a certain space structure, which has good drying property, can be used in a coating, can improve the surface drying speed of the coating, enhances the roughness of the coating, further improves the initial water resistance of the coating, effectively avoids the problem that a coated steel structure is rusted due to rainwater after being transported outdoors, and has high practical application value.
Drawings
FIG. 1 is a graph comparing the contact angle to water after 2 hours of surface drying for coating sample 1 based on the waterborne alkyd resin composite of example 1 of the present invention and coating sample 4 based on the waterborne alkyd resin composite of comparative example 2, wherein A is a graph measuring the contact angle to water after 2 hours of surface drying for coating sample 1 based on the waterborne alkyd resin composite of example 1; b is a contact angle test chart for water after 2 hours of surface drying based on the waterborne alkyd resin composite coating sample 4 of comparative example 2.
Detailed Description
The following will further illustrate the waterborne alkyd resin composite material provided by the present invention, and its preparation method and application.
The preparation method of the waterborne alkyd resin composite material provided by the invention comprises the following steps:
s1, mixing vegetable oleic acid, polybasic acid, polyhydric alcohol, an esterification catalyst and an organic solvent under a protective atmosphere, and carrying out an esterification reaction to obtain an esterification product;
s2, reacting the esterification product with a half-capping reagent to obtain a half-capped esterification product, wherein the half-capping reagent is selected from at least one of o-hydroxybenzoic acid and o-hydroxynaphthoic acid;
s3, removing the solvent in the half-end-capped esterification product, and reacting with acid anhydride to obtain the product with the acid value of 35mgKOH g-1-55mgKOH·g-1The end-capped esterification product of (a);
s4, diluting the end-capped esterification product, and reacting with a neutralizer to obtain an alkyd resin polyol prepolymer; and
and S5, mixing the alkyd resin polyol prepolymer with the amino modified halloysite nanotube, and reacting with a diisocyanate solution to obtain the water-based alkyd resin composite material.
In order to prepare a waterborne alkyd resin with excellent quality, the types and the amounts of the vegetable oil acid, the polybasic acid and the polyhydric alcohol in the step S1 can be regulated.
Specifically, the mass ratio of the vegetable oleic acid to the polybasic acid to the polyhydric alcohol is (23-33): 16-24): 20-30; the molar ratio of the polyol to the vegetable oil acid is 1:1-1.5: 1; the molar ratio of the hydroxyl content in the polyol to the carboxyl content in the vegetable oleic acid is 2:1-3: 1; the molar ratio of the hydroxyl content in the polyol to the carboxyl content in the polyacid is 1:1-1.7: 1.
Wherein the vegetable oil acid is at least one selected from dehydrated ricinoleic acid, linoleic acid, tall oil acid and soybean oil acid; the polybasic acid is selected from at least one of maleic anhydride, isophthalic acid, terephthalic acid, adipic acid and phthalic anhydride; the polyalcohol is at least one of glycerol, neopentyl glycol, trimethylolpropane and ethylene glycol.
In one embodiment, the protective atmosphere is selected from nitrogen.
In one embodiment, the mass ratio of the organic solvent to the polyol is 1:2.5 to 1: 4; the organic solvent is at least one selected from toluene, xylene and propylene glycol methyl ether.
In one embodiment, the mass ratio of the esterification catalyst to the polyol is from 1:40 to 1: 50; the esterification catalyst is selected from at least one of dibutyltin dilaurate, di-n-butyltin oxide and antimony trioxide.
In actual preparation, in order to remove water generated in the reaction, the reaction is carried out at 150-190 ℃ for 1-2 h, preferably at 180 ℃ for 1h by using a reflux solvent in step S1; after partial reflux solvent is removed, the mixture is reacted for 1.5 to 3 hours at the temperature of 210 to 240 ℃ and preferably for 2 hours at the temperature of 230 ℃ to obtain an esterification product.
Wherein the reflux solvent is at least one of dimethylbenzene and methylbenzene, the mass ratio of the reflux solvent to the polyhydric alcohol is 1:2-1:5, and the mass of the removed reflux solvent accounts for 15-50% of the mass of the total reflux solvent.
In step S2, at least one of o-hydroxybenzoic acid and o-hydroxynaphthoic acid is used as a half-capping reagent to perform a half-capping reaction with the esterification product, and o-hydroxyl is introduced into the alkyd resin, so that the construction of the water-based alkyd resin composite material with a certain space structure is facilitated, and the anisotropy of the molecular chain of the water-based alkyd resin composite material is enhanced.
Specifically, the o-hydroxybenzoic acid is at least one selected from the group consisting of 2, 3-dihydroxybenzoic acid, 2, 3-dihydroxy-5-methylbenzoic acid, 3, 4-dihydroxybenzoic acid, 2,3, 4-trihydroxybenzoic acid, and 3,4, 5-trihydroxybenzoic acid.
Specifically, the o-hydroxynaphthoic acid is at least one selected from the group consisting of 2, 3-dihydroxynaphthoic acid, 6, 7-dihydroxynaphthoic acid, 7, 8-dihydroxynaphthoic acid, 5, 6-dihydroxy-2-naphthoic acid, 6, 7-dihydroxy-2-naphthoic acid, and 4,6, 7-dihydroxy-2-naphthoic acid.
In one embodiment, the mass ratio of the half-capping reagent to the polyol is from 1:2 to 1:6, and the temperature of the reaction of the esterification product with the half-capping reagent is from 190 ℃ to 220 ℃, preferably 210 ℃.
In order to quantify the degree of reaction between the esterification product and the half-capping agent, it is necessary to measure the acid value of the half-capped esterification product obtained by reacting the esterification product with the half-capping agent.
In one embodiment, when the acid value of the half-blocked esterified product is 10mgKOH g-1-20mgKOH·g-1The half-capping reaction of the esterification product is completed.
In step S3, by reacting the half-capped esterified product with an acid anhydride, it is possible to ensure that the esterified product is fully capped and to improve the hydrophilicity of the alkyd resin. In the reaction process, the hydroxyl in the half-end-capped esterification product causes the ring opening of the anhydride to generate carboxyl and ester bond.
Specifically, the mass ratio of the acid anhydride to the polyhydric alcohol is 1:1.1-1:3, and the acid anhydride is selected from at least one of trimellitic anhydride, maleic anhydride and phthalic anhydride.
In one embodiment, the solvent is removed from the half-capped esterified product and then reacted with an acid anhydride at a temperature of 150 ℃ to 180 ℃ until the acid value of the system reaches 35mgKOH g-1-55mgKOH·g-1. Wherein, the solvent in the half-end-capped esterification product can be removed by evaporation, and the reaction temperature is preferably 170 ℃.
In step S4, in order to reduce the viscosity of the end-capped esterified product, the diluent is preferably added to the end-capped esterified product at a temperature of 80 ℃ to 120 ℃ and mixed for 30min to 60min, further, the reaction temperature is preferably 120 ℃ and the mixing time is preferably 30 min.
Specifically, the mass ratio of the diluent to the polyhydric alcohol is 1:1-1:3, and the diluent is selected from at least one of propylene glycol methyl ether, propylene glycol butyl ether, tert-butyl alcohol and ethylene glycol butyl ether.
The carboxyl in the blocked esterification product can be neutralized by using a neutralizing agent, the hydrophilicity of a molecular chain segment is improved, the neutralizing agent is preferably added to the blocked esterification product at the temperature of 40-70 ℃, the mixture is mixed for 30-60 min, and the reaction temperature is further preferably 50 ℃.
Specifically, the mass ratio of the neutralizing agent to the polyhydric alcohol is 1:2.5-1:10, and the neutralizing agent is selected from at least one of N, N-dimethylethanolamine, triethylamine and ammonia water.
In step S5, the chain extension of the alkyd resin is performed by using diisocyanate, so that not only the alkyd resin with a certain molecular weight can be generated, but also urethane bonds and urea bonds can be introduced into the alkyd resin, which is beneficial to further improving the drying property of the aqueous alkyd resin composite material.
Specifically, the diisocyanate solution comprises diisocyanate and a solvent without a nucleophilic functional group, the mass ratio of the diisocyanate to the polyol is 1:2-1:15, and the mass ratio of the diisocyanate to the solvent without the nucleophilic functional group is 1:1-1.5: 1.
The diisocyanate is at least one selected from toluene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate, and is preferably toluene diisocyanate; the solvent without nucleophilic functional group is selected from at least one of xylene and toluene, and is preferably xylene.
In order to further extend the chain of the alkyd resin, amino modified halloysite nanotubes can be used to graft with an alkyd resin containing isocyanate linkages.
Specifically, the mass ratio of the amino modified halloysite nanotubes to the polyol is 1:5.5-1: 20.
In order to enhance the dispersion stability of the halloysite nanotube in alkyd resin, the invention modifies the halloysite nanotube with organic amine, and the preparation steps comprise: acid washing is carried out on the halloysite nanotube to obtain an acidified halloysite nanotube; reacting the acidified halloysite nanotube with sodium bromide saturated solution until the water content is not lower than 5.5% to obtain a hydrated halloysite nanotube; and mixing the mixed solution of the hydrated halloysite nanotube and the organic solvent with the organic amine solution for not less than 24 hours, filtering, washing and drying to obtain the amino modified halloysite nanotube.
The organic amine solution is selected from a mixed solution of ammonia water and 3-aminopropyltrimethoxysiloxane, and the mass ratio of the ammonia water to the 3-aminopropyltrimethoxysiloxane is 1:1.5-1: 2; the mass ratio of the hydrated halloysite nanotube to the organic solvent is 1:2-1: 5; the mass ratio of the hydrated halloysite nanotube to the organic amine solution is 1:5-1: 25.
To further illustrate the amino modification process of halloysite nanotubes, the reaction formula of the amino modification of the halloysite nanotubes is shown in the following formula (1), taking hydrated halloysite nanotubes and 3-aminopropyltrimethoxysiloxane as an example:
Figure BDA0003586436620000081
in one embodiment, the diisocyanate solution is added to the mixed solution of the alkyd resin polyol prepolymer and the amino modified halloysite nanotube in batches for reaction, the batch addition mode is preferably dropwise addition, the reaction temperature is 50-80 ℃, and the reaction time is 2-3 h. When the content of the isocyanate in the reaction solution is less than 0.5 percent, the preparation of the waterborne alkyd resin composite material is finished.
To further illustrate the reaction process of step S5, taking the amino-modified halloysite nanotubes obtained by formula (1) above, toluene diisocyanate, and 3, 4-dihydroxybenzoic acid-terminated alkyd polyol prepolymer as an example, the reaction equation of step S5 is shown in formula (2) below:
Figure BDA0003586436620000091
the invention also provides a waterborne alkyd resin composite material prepared by the preparation method of the waterborne alkyd resin composite material.
The invention also provides application of the water-based alkyd resin composite material in paint.
In one embodiment, the mass fraction of the waterborne alkyd resin composite in the coating is 15-30%.
In one embodiment, the paint further comprises 35% -50% of pigment and filler, 20% -25% of water, 1% -3% of cosolvent, 0.1% -1% of drier and 0.05% -0.2% of defoaming agent.
Specifically, the pigment and filler is selected from at least one of superfine barium sulfate, ultrawhite heavy calcium carbonate 800 meshes and iron oxide red 168; the cosolvent is at least one selected from propylene glycol butyl ether, ethylene glycol butyl ether and n-butyl alcohol, and is preferably ethylene glycol butyl ether; the drier is selected from at least one of VOK-6533, CM001 and WX-1440, preferably CM 001; the defoaming agent is selected from at least one of the group consisting of Xiaometer AFE 1410, MO 2190 and BYK-024, and is preferably BYK-024.
The invention provides a water-based alkyd resin composite material with a certain space structure, which has good drying property, can be used in a coating, can improve the surface drying speed of the coating, enhances the roughness of the coating, further improves the initial water resistance of the coating, effectively avoids the problem that a coated steel structure is rusted due to rainwater after being transported outdoors, and has high practical application value.
The water-borne alkyd resin composite material, its preparation and use will now be further illustrated by the following specific examples.
Example 1
Heating 57g of linoleic acid, 171g of soybean oil acid, 128g of phthalic anhydride, 25.6g of isophthalic acid, 80g of trimethylolpropane, 60g of glycerol, 3g of antimony trioxide and 40g of xylene to 140 ℃ under the protection of nitrogen, starting stirring after melting, heating to 180 ℃, taking 35g of xylene as a reflux solvent, carrying out heat preservation reaction for 1h, removing water generated by esterification and 18g of xylene, heating to 230 ℃ at the speed of 0.5 ℃/min, and carrying out heat preservation reaction until the acid value of the system is 20mgKOH g-1And then, evaporating xylene to obtain an esterification product.
Adding 30g of 3, 4-dihydroxybenzoic acid into the esterification product, and reacting at 210 ℃ until the acid value of the system is 12mgKOH g-1And obtaining a semi-terminated esterification product.
Evaporating the solvent in the semi-terminated esterification product, adding 50g of trimellitic anhydride, and reacting at 170 ℃ until the acid value of the system is 48mgKOH g-1To obtain the end-capped esterified product.
Adding 130g of propylene glycol methyl ether into the end-capped esterified product, stirring for 30min at 120 ℃, then cooling to 50 ℃, adding 50g of triethylamine, stirring for 30min at the heat preservation condition, and cooling to room temperature to obtain the alkyd resin polyol prepolymer.
Adding 25g of amino modified halloysite nanotube into an alkyd resin polyol prepolymer, then dropwise adding a mixed solution of 32g of toluene diisocyanate and 30g of xylene into the alkyd resin polyol prepolymer, wherein the dropwise adding time is 1h, reacting for 2h at 65 ℃ after the dropwise adding is finished, and obtaining the water-based alkyd resin composite material when the content of isocyanic acid radical in reactants is 0.45%.
Example 2
90g of dehydrated ricinoleic acid, 115g of linoleic acid, 121g of phthalic anhydride, 24g of terephthalic acid, 75g of trimethylolHeating propane, 65g of glycerol, 3g of antimony trioxide and 40g of xylene to 140 ℃ under the protection of nitrogen, starting stirring after the materials are molten, heating to 180 ℃, taking 35g of xylene as a reflux solvent, carrying out heat preservation reaction for 1 hour, removing water generated by esterification and 18g of xylene, heating to 230 ℃ at the speed of 0.5 ℃/min, and carrying out heat preservation reaction until the acid value of a system is 20 mgKOH/g-1And then, evaporating xylene to obtain an esterification product.
Adding 35g of 2, 3-dihydroxy naphthoic acid into the esterification product, and reacting at 210 ℃ until the acid value of the system is 12.5mgKOH g-1To obtain a semi-blocked esterification product.
Evaporating the solvent in the semi-terminated esterification product, adding 50g of trimellitic anhydride, and reacting at 170 ℃ until the acid value of the system is 45mgKOH g-1To obtain the end-capped esterified product.
Adding 130g of propylene glycol methyl ether into the end-capped esterified product, stirring for 30min at 120 ℃, then cooling to 50 ℃, adding 45g of triethylamine, stirring for 30min at the heat preservation condition, and cooling to room temperature to obtain the alkyd resin polyol prepolymer.
Adding 20g of amino modified halloysite nanotube into an alkyd resin polyol prepolymer, dropwise adding a mixed solution of 30g of toluene diisocyanate and 30g of xylene into the alkyd resin polyol prepolymer for 1h, reacting at 65 ℃ for 2h after dropwise adding is completed, and obtaining the waterborne alkyd resin composite material when the content of isocyanato in reactants is 0.45%.
Comparative example 1
Comparative example 1 differs from example 1 in that the aqueous alkyd resin composite was prepared without the addition of amino-modified halloysite nanotubes.
Comparative example 2
Comparative example 2 differs from example 1 in that the esterification product after removal of the solvent is reacted directly with trimellitic anhydride and no longer with 3, 4-dihydroxybenzoic acid.
Comparative example 3
Comparative example 3 is different from example 1 in that 30g of 3, 5-dihydroxybenzoic acid is used instead of 30g of 3, 4-dihydroxybenzoic acid.
Comparative example 4
Comparative example 4 differs from example 1 in that the half-blocked esterified product after the solvent was removed was reacted with trimellitic anhydride to a system acid value of 65 mgKOH. g-1The reaction was terminated.
The waterborne alkyd resin composites prepared in examples 1-2 and comparative examples 1-4 were used to prepare paint samples 1-6, respectively, having the formulation shown in Table 1, and the water contact angle tests were performed on paint sample 1 and paint sample 4, the results of which are shown in FIG. 1, and the performance tests were performed on paint samples 1-6, the results of which are shown in Table 2.
TABLE 1
Figure BDA0003586436620000121
Figure BDA0003586436620000131
TABLE 2
Figure BDA0003586436620000132
As can be seen from fig. 1 and table 2, the solid dry time of sample 2 is extended compared to sample 1 because sample 2 uses partially dehydrated ricinoleic acid instead of linoleic acid, dehydrated ricinoleic acid has a lower iodine value than linoleic acid, and the time required for oxidative crosslinking is relatively extended; the modified halloysite nanotube is not added in the sample 3, and the longer surface drying time is caused by the lower hydrogen bond content in the molecule; samples 4 and 5 have poor initial water resistance and salt water resistance, because the structure is not introduced with a half-end-capped structure of an ortho-hydroxyl group, the halloysite nanotube in the molecule cannot be effectively stretched; the acid value of sample 6 was raised to 65 mgKOH. g-1The residual amount of hydroxyl is reduced, so that the grafting reaction of diisocyanate and halloysite is not facilitated, and the partially modified halloysite is directly dispersed in the coating, so that the storage stability and the coating resistance of the coating are influenced.
The parameters described in the present invention are based on the following test criteria:
(1) the skinning property and the storage stability are measured according to the national standard GB-T6753.3-1986;
(2) the freeze-thaw stability is determined according to the GB-T9268-2008A method;
(3) the drying time is measured according to the national standard GB/T1728-79;
(4) the bending test is determined according to the national standard GB 6742-1986;
(5) the impact resistance is measured according to the national standard GBT 1732-93;
(6) the cross-check experiment is measured according to the national standard GB-T9286-1998;
(7) the initial water resistance and the water resistance are measured according to the national standard GB/T1733-93;
(8) the salt water resistance is measured according to the national standard GB/T9274-88.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.

Claims (10)

1. The preparation method of the water-based alkyd resin composite material is characterized by comprising the following steps:
under the protective atmosphere, mixing vegetable oleic acid, polybasic acid, polyalcohol, an esterification catalyst and an organic solvent, and carrying out esterification reaction to obtain an esterification product;
reacting the esterification product with a half-end-capping reagent to obtain a half-end-capped esterification product, wherein the half-end-capping reagent is selected from at least one of o-hydroxybenzoic acid and o-hydroxynaphthoic acid;
removing the solvent in the semi-end-capping esterification product, and then reacting with acid anhydride to obtain the product with the acid value of 35mgKOH g-1-55mgKOH·g-1The end-capped esterification product of (a);
diluting the end-capped esterification product, and reacting with a neutralizer to obtain an alkyd resin polyol prepolymer; and
and mixing the alkyd resin polyol prepolymer with the amino modified halloysite nanotube, and then reacting with a diisocyanate solution to obtain the water-based alkyd resin composite material.
2. The method of claim 1, wherein the ortho-hydroxybenzoic acid is selected from at least one of 2, 3-dihydroxybenzoic acid, 2, 3-dihydroxy-5-methylbenzoic acid, 3, 4-dihydroxybenzoic acid, 2,3, 4-trihydroxybenzoic acid, 3,4, 5-trihydroxybenzoic acid; the o-hydroxynaphthoic acid is at least one selected from the group consisting of 2, 3-dihydroxynaphthoic acid, 6, 7-dihydroxynaphthoic acid, 7, 8-dihydroxynaphthoic acid, 5, 6-dihydroxy-2-naphthoic acid, 6, 7-dihydroxy-2-naphthoic acid, and 4,6, 7-dihydroxy-2-naphthoic acid.
3. The method of claim 1, wherein the half-blocked esterification product has an acid number of 10 mgKOH-g-1-20mgKOH·g-1。
4. The method of claim 1, wherein in the step of mixing vegetable oleic acid, a polybasic acid, a polyhydric alcohol, an esterification catalyst, and a solvent, the mass ratio of the vegetable oleic acid, the polybasic acid, and the polyhydric alcohol is (23-33): 16-24): 20-30;
and/or in the step of reacting the esterification product with a half-end capping agent, the mass ratio of the half-end capping agent to the polyol is 1:2-1: 6;
and/or removing the solvent in the half-end-capped esterification product, and reacting with anhydride, wherein the mass ratio of the anhydride to the polyol is 1:1.1-1: 3;
and/or diluting the end-capped esterification product, and reacting with a neutralizing agent, wherein the mass ratio of the neutralizing agent to the polyhydric alcohol is 1:2.5-1: 10;
and/or in the step of mixing the alkyd resin polyol prepolymer and the amino-modified halloysite nanotubes, the mass ratio of the amino-modified halloysite nanotubes to the polyol is 1:5.5-1: 20.
5. The method of claim 1, wherein the molar ratio of the hydroxyl content of the polyol to the carboxyl content of the vegetable oil acid is from 2:1 to 3:1, and the molar ratio of the hydroxyl content of the polyol to the carboxyl content of the polyacid is from 1:1 to 1.7: 1.
6. The method of preparing the waterborne alkyd resin composite of claim 1, wherein the diisocyanate solution comprises a diisocyanate and a solvent that does not contain nucleophilic functional groups, and wherein the mass ratio of the diisocyanate to the polyol is from 1:2 to 1:15, and the mass ratio of the diisocyanate to the solvent that does not contain nucleophilic functional groups is from 1:1 to 1.5: 1.
7. The method of claim 1, wherein the step of reacting the esterification product with a half-capping agent is carried out at a temperature of 190 ℃ to 220 ℃.
8. A waterborne alkyd resin composite obtained by the method of any one of claims 1-7.
9. Use of the aqueous alkyd resin composite of claim 8 in a coating.
10. The use of the aqueous alkyd resin composite of claim 9 in a paint, wherein the mass fraction of the aqueous alkyd resin composite in the paint is 15% to 30%.
CN202210364412.8A 2022-04-08 2022-04-08 Water-based alkyd resin composite material and preparation method and application thereof Active CN114752043B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210364412.8A CN114752043B (en) 2022-04-08 2022-04-08 Water-based alkyd resin composite material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210364412.8A CN114752043B (en) 2022-04-08 2022-04-08 Water-based alkyd resin composite material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114752043A true CN114752043A (en) 2022-07-15
CN114752043B CN114752043B (en) 2023-08-15

Family

ID=82328576

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210364412.8A Active CN114752043B (en) 2022-04-08 2022-04-08 Water-based alkyd resin composite material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114752043B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4298658A (en) * 1979-09-19 1981-11-03 J.G.L. Chemicals Ltd. Vapor permeation curable coatings based on alkyd resins
CN1306056A (en) * 1999-12-23 2001-08-01 索鲁蒂奥地利有限公司 Water paint compsns.
CN1668664A (en) * 2002-05-23 2005-09-14 拜尔材料科学股份公司 Polyisocyanates and polyurethanes containing polymer modifiers and their use

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4298658A (en) * 1979-09-19 1981-11-03 J.G.L. Chemicals Ltd. Vapor permeation curable coatings based on alkyd resins
CN1306056A (en) * 1999-12-23 2001-08-01 索鲁蒂奥地利有限公司 Water paint compsns.
CN1668664A (en) * 2002-05-23 2005-09-14 拜尔材料科学股份公司 Polyisocyanates and polyurethanes containing polymer modifiers and their use

Also Published As

Publication number Publication date
CN114752043B (en) 2023-08-15

Similar Documents

Publication Publication Date Title
CN108727952B (en) Self-emulsifying water-based alkyd resin, self-emulsifying water-based alkyd paint and preparation methods
CN109575195B (en) Modified alkyd resin and preparation method thereof
JPS5839871B2 (en) Suiseitoriyoso Seibutuno Seihou
US7129278B2 (en) Aqueous polymer dispersions
CN107513340A (en) A kind of self-drying aqueous alkyd paint of high rigidity and preparation method thereof
CN108976981B (en) Emulsion for cathode electrophoretic coating, preparation method of emulsion, cathode electrophoretic coating and preparation method of cathode electrophoretic coating
AU2001238537A1 (en) Aqueous polymer dispersions
CN114752043B (en) Water-based alkyd resin composite material and preparation method and application thereof
CN114773970A (en) Water-based high-volume solid-content steel structure normal-temperature anticorrosive paint and preparation method thereof
CN111393627B (en) Non-isocyanate polyurethane modified waterborne alkyd resin and preparation method thereof
CN116102942B (en) Anticorrosive high-temperature-resistant waterborne polyurethane coating and preparation method thereof
CN113717325B (en) Modified aqueous alkyd resin, preparation method thereof and aqueous dispersion containing modified aqueous alkyd resin
DE19715695A1 (en) Low-emission curable paint or printing ink binders
EP0668305B1 (en) Environmentally friendly autoxidisable alkyd coating composition
CN114057980A (en) Self-dispersible ester-soluble polyurethane ink resin, preparation method and ink
CN115044013B (en) Bio-based air-curing type water-based polyurethane urea resin and preparation method thereof
CN115386053B (en) Modified epoxy resin and preparation method and application thereof
CN115490864B (en) POSS hybridized waterborne polyurethane emulsion and preparation method and application thereof
CN116355145A (en) Epoxy acrylate hybrid dispersion and preparation method and application thereof
CN112646158B (en) Modification method and modification intermediate of waterborne alkyd resin and preparation method of modified waterborne alkyd resin
CN112625227B (en) Curing agent modified waterborne alkyd resin and modified intermediate
JPH0139456B2 (en)
KR20180089663A (en) internal emulsified polyurethane alkyd emulsion resin and manufacturing method of the same and water-borne enamel paint including the same
CN118546342A (en) Fumaric acid alkyd resin with excellent impact resistance and adhesive force and preparation method thereof
JPH0726202A (en) Resin composition for water-based coating

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant