CN113185672B - Preparation method of waterborne epoxy itaconate resin with high photo-curing activity - Google Patents

Preparation method of waterborne epoxy itaconate resin with high photo-curing activity Download PDF

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CN113185672B
CN113185672B CN202110684611.2A CN202110684611A CN113185672B CN 113185672 B CN113185672 B CN 113185672B CN 202110684611 A CN202110684611 A CN 202110684611A CN 113185672 B CN113185672 B CN 113185672B
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epoxy
resin
itaconate
photo
diisocyanate
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CN113185672A (en
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吴国民
边均娜
孔振武
陈健
杨兆哲
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Institute of Chemical Industry of Forest Products of CAF
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    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
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Abstract

The invention discloses a method for regulating and controlling the photo-curing activity of waterborne epoxy itaconate resin. The first step: reacting a diisocyanate with a hydroxy (meth) acrylate to produce a semi-blocked isocyanate intermediate; and a second step of: and grafting different structures and different amounts of half-blocked isocyanate intermediates into the epoxy itaconate resin structure to prepare the high-activity water-based epoxy itaconate photo-curing resin. The hydroxyl active site generated by the esterification reaction of itaconic acid and epoxy resin is utilized, the half-blocked isocyanate intermediate is quantitatively grafted into the molecular structure of the epoxy itaconate resin under the mild condition, the photo-curing activity of the waterborne epoxy itaconate resin is regulated and controlled, the reaction process is mild and controllable, the manufacturing process is simple and convenient, and the product is environment-friendly.

Description

Preparation method of waterborne epoxy itaconate resin with high photo-curing activity
Technical Field
The invention relates to a preparation method of waterborne epoxy itaconate resin with high photo-curing activity, in particular to a method for regulating the photo-curing activity of waterborne epoxy itaconate resin by grafting half-blocked isocyanate intermediate.
Background
Along with the increasing perfection of environmental regulations and the enhancement of environmental awareness of people, the coating industry is developing towards environmental friendliness such as UV curing, water-based, high solid content and the like. The emerging water-based UV curing coating combines UV curing and water-based technology, and is environment-friendly, high-efficiency, high-safety and environment-friendly without emission of Volatile Organic Compounds (VOC). The traditional epoxy acrylate photo-curing resin has the advantages of high glossiness, good weather resistance and temperature resistance, low cost, easily available raw materials and the like, but also has the defects of large resin smell, high brittleness and poor flexibility of a paint film after curing and the like. Itaconic acid is taken as a biomass resource, and is applied to the development of water-based photo-curing paint, so that the concept of environment-friendly paint is considered, the pressure brought by increasingly deficient petrochemical resources can be effectively relieved, and a new way is provided for the development and utilization of bio-based products instead of petroleum-based compounds.
However, itaconic acid modified resins have the disadvantage of low double bond photo-curing activity. Jinyue Dai et al are respectively different from itaconic acidDiols (ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol) three bio-based unsaturated polyesters were prepared. After the film is coated, the film is dried for 8 hours in a vacuum oven at 80 ℃, and cured for 30 minutes at room temperature by using a high-pressure mercury lamp (500W), so that the film can be crosslinked and formed, and the film has better hardness, water resistance and solvent resistance. Bao Junxiang modified epoxidized soybean oil with itaconate and having a fixed irradiation intensity of 50mW/cm 2 The obtained paint film has good hardness and thermal stability, but the double bond conversion rate is lower. The hydroxyl active site generated by the esterification reaction of itaconic acid and epoxy resin is utilized, the half-blocked isocyanate intermediate is quantitatively grafted into the molecular structure of the epoxy itaconate resin under a mild condition, and the photo-curing activity of the waterborne epoxy itaconate resin can be flexibly regulated and controlled by grafting different amounts of half-blocked isocyanate intermediate.
Disclosure of Invention
The invention aims to provide a method for regulating and controlling the photo-curing activity of waterborne epoxy itaconate resin. The hydroxyl active site generated by the esterification reaction of itaconic acid and epoxy resin is utilized to quantitatively graft the semi-blocked isocyanate intermediate with (methyl) acryloyloxy group at one end into the molecular structure of the epoxy itaconic acid ester resin under the mild condition. The photocuring activity of the waterborne epoxy itaconate resin can be flexibly controlled by changing the intermediate structure and grafting amount of the semi-blocked isocyanate. The water-based epoxy itaconic acid ester resin can obviously improve the photocuring film forming efficiency when being applied to photocuring paint.
The technical scheme of the invention is as follows: a method for regulating and controlling the photo-curing activity of water-based epoxy itaconate resin is realized by the following steps:
the first step: reacting a diisocyanate with a hydroxy (meth) acrylate to produce a semi-blocked isocyanate intermediate;
and a second step of: and grafting different structures and different amounts of half-blocked isocyanate intermediates into the epoxy itaconate resin structure to prepare the high-activity water-based epoxy itaconate photo-curing resin.
The diisocyanate in the first step is any one or more of toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate and hydrogenated diphenylmethane diisocyanate.
The hydroxy (meth) acrylate mentioned in the first step is any one or more of hydroxyethyl methacrylate, hydroxypropyl methacrylate and 4-hydroxybutyl acrylate.
The semi-blocked isocyanate intermediate in the first step refers to a product formed by reacting diisocyanate and hydroxyl (methyl) acrylate according to the mass ratio of 1:1, wherein one end of the product is isocyanate groups, and the other end of the product is (methyl) acryloyloxy groups.
The epoxy itaconate resin in the second step is an esterification product of epoxy resin and itaconic acid, wherein the two ends of the esterification product are carboxyl groups, and the esterification product is formed by reacting the epoxy resin with the itaconic acid according to the mass ratio of 1:2.
The reaction temperature of the first step and the second step is the reflux temperature of the solvent.
The solvent used in the reaction was acetone.
Advantageous effects
The invention quantitatively grafts the semi-blocked isocyanate intermediate with (methyl) acryloyloxy group at one end into the molecular structure of the epoxy itaconate resin by utilizing the hydroxyl active site in the epoxy itaconate resin under mild conditions. The photocuring activity of the waterborne epoxy itaconic acid ester resin is flexibly regulated and controlled by changing the intermediate structure and grafting amount of the semi-blocked isocyanate, so that the film forming efficiency of a photocuring paint film is improved.
Drawings
FIG. 1 is a graph showing the double bond conversion of aqueous epoxy itaconate resins over time after grafting different amounts of half-blocked isocyanate intermediates. With the increase of the grafting amount of the semi-blocked isocyanate, under the same curing time, compared with the modified resin with small grafting amount, the modified resin with large grafting amount has higher double bond conversion rate, and when the double bond conversion rate tends to be stable and basically unchanged, the modified resin with large grafting amount has higher double bond conversion rate and smaller content of residual double bonds. The grafting half-blocked isocyanate intermediate can flexibly regulate and control the photo-curing activity of the water-based epoxy itaconate resin.
FIG. 2 shows three different HDI, TDI, IPDI typesInfrared spectrogram of isocyanate modified epoxy itaconate resin. As shown in the figure, three different modified resins have infrared spectra at 944cm due to the methacrylic double bond contained in the semi-blocked isocyanate -1 And 1634cm -1 The strong C=C characteristic absorption peak appears at the position, the hydroxyl reacts with isocyanate groups to generate carbamate, and the carbamate is formed at 1710cm -1 C=O stretching vibration absorption peaks of urethane bonds appear at the same time, and characteristic absorption peaks of-OH and-NH appear at 3354 cm-1.
Detailed Description
A method for regulating and controlling the photo-curing activity of water-based epoxy itaconate resin is realized by the following steps: the first step:
any one or more of the isotoluene diisocyanate, the hexamethylene diisocyanate, the isophorone diisocyanate, the diphenylmethane diisocyanate and the hydrogenated diphenylmethane diisocyanate and any one or more of the hydroxyethyl methacrylate, the hydroxypropyl methacrylate and the 4-hydroxybutyl acrylate are reacted in an acetone solution for 4-6 hours according to the mass ratio of the diisocyanate to the (methyl) hydroxyl acrylate of 1:1, and the reaction temperature is the acetone reflux temperature, so that the semi-blocked isocyanate intermediates with different structures are obtained.
And a second step of:
slowly dropwise adding a certain amount of acetone solution of the half-blocked isocyanate intermediate into the acetone solution of the epoxy itaconate resin, stirring and heating to the acetone reflux temperature, and reacting for 3-8h to obtain the half-blocked isocyanate modified epoxy itaconate resin. The acid value is measured by sampling, the amount of triethanolamine required to be added as a neutralizing agent is calculated according to the obtained acid value, and neutralization is carried out at the reflux temperature of acetone. And (3) dropwise adding a proper amount of distilled water to adjust the solid content to a proper level, stirring and dispersing for 0.5h, and recovering the solvent from the obtained aqueous dispersion by reduced pressure distillation to obtain the semi-blocked isocyanate modified epoxy itaconic acid ester resin aqueous dispersion.
The first step:
Figure BDA0003124021270000051
and a second step of:
Figure BDA0003124021270000052
comparative example 1
Into a four-necked flask equipped with a thermometer, a stirrer and a condenser, 100.0g of an acetone solution (solid content: 66.7 wt%) of an epoxy itaconate resin was added, the mixture was stirred and heated to an acetone reflux temperature, 15.0g of triethanolamine was added for neutralization, and the reflux reaction was continued for 0.5 hours. Distilled water is slowly added dropwise to stir and disperse to obtain an aqueous dispersion with the solid content of 60wt%, acetone is recovered by reduced pressure distillation to obtain an unmodified (grafting amount of 0%) epoxy itaconic acid ester resin aqueous dispersion. After 30s of illumination of the unmodified resin, the double bond conversion was 62.7%.
Example 1
Into a four-necked flask equipped with a thermometer, a stirrer and a condenser tube, 174.0g of Toluene Diisocyanate (TDI), 130.0g of hydroxyethyl methacrylate and 304.0g of acetone were added, and the mixture was stirred and heated to an acetone reflux temperature to react for 4 hours to obtain an acetone solution (solid content: 50 wt%) of a TDI type semi-blocked isocyanate intermediate.
31.1g of acetone solution (solid content of 50 wt%) of TDI-type semi-blocked isocyanate intermediate is taken, 100.0g of acetone solution (solid content of 66.7 wt%) of epoxy itaconic acid ester resin is slowly added dropwise, and the mixture is stirred and heated to an acetone reflux temperature for reaction for 5 hours, so that the TDI-type semi-blocked isocyanate modified epoxy itaconic acid ester resin is obtained. 24.0g of triethanolamine was added for neutralization, and the reflux reaction was continued for 0.5h. Distilled water is slowly added dropwise to stir and disperse to obtain an aqueous dispersion with the solid content of 60wt%, acetone is recovered by reduced pressure distillation to obtain a modified (grafting amount of 25%) epoxy itaconic acid ester resin aqueous dispersion. After 30s of illumination of the obtained resin, the double bond conversion was 82.0%.
Example 2
Into a four-necked flask equipped with a thermometer, a stirrer and a condenser tube, 168.0g of 1, 6-Hexamethylene Diisocyanate (HDI), 130.0g of hydroxyethyl methacrylate and 298.0g of acetone were added, and the mixture was stirred and heated to an acetone reflux temperature to react for 4 hours to obtain an acetone solution (solid content: 50 wt%) of a half-blocked isocyanate intermediate of the HDI type.
61.0g of acetone solution (solid content of 50 wt%) of the HDI type half-blocked isocyanate intermediate is taken, 100.0g of acetone solution (solid content of 66.7 wt%) of epoxy itaconic acid ester resin is slowly added dropwise, and the mixture is stirred and heated to an acetone reflux temperature for reaction for 6 hours, so that the HDI type half-blocked isocyanate modified epoxy itaconic acid ester resin is obtained. 24.0g of triethanolamine was added for neutralization, and the reflux reaction was continued for 0.5h. Distilled water is slowly added dropwise to stir and disperse to obtain an aqueous dispersion with the solid content of 60wt%, acetone is recovered by reduced pressure distillation to obtain a modified (grafting amount of 50%) epoxy itaconic acid ester resin aqueous dispersion. After 30s of illumination of the resin obtained, the double bond conversion was 84.1%.
Example 3
Into a four-necked flask equipped with a thermometer, a stirrer and a condenser tube, 250.0g of diphenylmethane diisocyanate (MDI), 144.0g of hydroxypropyl methacrylate and 394.0g of acetone were added, and the mixture was stirred and heated to an acetone reflux temperature to react for 6 hours to obtain an acetone solution (solid content: 50% by weight) of an MDI type semi-blocked isocyanate intermediate.
40.3g of acetone solution (solid content of 50 wt%) of the half-blocked isocyanate intermediate of MDI type is taken, 100.0g of acetone solution (solid content of 66.7 wt%) of epoxy itaconic acid ester resin is slowly added dropwise, and the mixture is stirred and heated to an acetone reflux temperature for reaction for 6 hours, so that the MDI type half-blocked isocyanate modified epoxy itaconic acid ester resin is obtained. 24.0g of triethanolamine was added for neutralization, and the reflux reaction was continued for 0.5h. Distilled water is slowly added dropwise to stir and disperse to obtain an aqueous dispersion with the solid content of 60wt%, acetone is recovered by reduced pressure distillation to obtain a modified (grafting amount of 25%) epoxy itaconic acid ester resin aqueous dispersion. After 30s of illumination of the resin obtained, the double bond conversion was 81.6%.
Example 4
Into a four-necked flask equipped with a thermometer, a stirrer and a condenser tube, 222.0g of isophorone diisocyanate (IPDI), 144.0g of 4-hydroxybutyl acrylate and 366.0g of acetone were added, and the mixture was stirred and heated to an acetone reflux temperature and reacted for 6 hours to obtain an acetone solution (solid content: 50 wt%) of a half-blocked isocyanate intermediate of the IPDI type.
112.3g of acetone solution (solid content of 50 wt%) of the half-blocked isocyanate intermediate of the IPDI type is taken, 100.0g of acetone solution (solid content of 66.7 wt%) of the epoxy itaconic acid ester resin is slowly added dropwise, and the mixture is stirred and heated to an acetone reflux temperature for reaction for 6 hours, so as to obtain the IPDI type half-blocked isocyanate modified epoxy itaconic acid ester resin. 24.0g of triethanolamine was added for neutralization, and the reflux reaction was continued for 0.5h. Distilled water is slowly added dropwise to stir and disperse to obtain an aqueous dispersion with the solid content of 60wt%, acetone is recovered by reduced pressure distillation to obtain a modified (grafting amount of 75%) epoxy itaconic acid ester resin aqueous dispersion. After 30s of illumination of the resin obtained, the double bond conversion was 85.2%.
Example 5
Into a four-necked flask equipped with a thermometer, a stirrer and a condenser tube, 174.0g of Toluene Diisocyanate (TDI), 130.0g of hydroxyethyl methacrylate and 304.0g of acetone were added, and the mixture was stirred and heated to an acetone reflux temperature to react for 4 hours to obtain an acetone solution (solid content: 50 wt%) of a TDI type semi-blocked isocyanate intermediate.
124.4g of acetone solution (solid content of 50 wt%) of TDI semi-blocked isocyanate intermediate is taken, 100.0g of acetone solution (solid content of 66.7 wt%) of epoxy itaconic acid ester resin is slowly added dropwise, and the mixture is stirred and heated to an acetone reflux temperature for reaction for 6 hours, so that the TDI semi-blocked isocyanate modified epoxy itaconic acid ester resin is obtained. 24.0g of triethanolamine was added for neutralization, and the reflux reaction was continued for 0.5h. Distilled water is slowly added dropwise to stir and disperse to obtain an aqueous dispersion with the solid content of 60wt%, acetone is recovered by reduced pressure distillation to obtain a modified (grafting amount is 100%) epoxy itaconic acid ester resin aqueous dispersion. After 30s of illumination of the resin obtained, the double bond conversion was 87.9%.

Claims (6)

1. A method for regulating and controlling the photo-curing activity of water-based epoxy itaconate resin is characterized by comprising the following steps:
the first step: reacting a diisocyanate with a hydroxy (meth) acrylate to produce a semi-blocked isocyanate intermediate; the semi-blocked isocyanate intermediate is a product of diisocyanate and (methyl) acrylic acid hydroxyl ester which are reacted according to the mass ratio of 1:1, wherein one end of the product is isocyanate group, and the other end of the product is (methyl) acryloyloxy group;
and a second step of: and grafting different structures and different amounts of half-blocked isocyanate intermediates into the epoxy itaconate resin structure to prepare the high-activity water-based epoxy itaconate photo-curing resin.
2. The method for controlling the photo-curing activity of the waterborne epoxy itaconate resin according to claim 1, wherein the diisocyanate in the first step is any one or more of toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate and hydrogenated diphenylmethane diisocyanate.
3. The method for controlling the photo-curing activity of an aqueous epoxy itaconate resin as claimed in claim 1, wherein the hydroxy (meth) acrylate in the first step is any one or more of hydroxy ethyl methacrylate, hydroxy propyl methacrylate and 4-hydroxybutyl acrylate.
4. The method for controlling the photo-curing activity of an aqueous epoxy itaconate resin according to claim 1, wherein the epoxy itaconate resin in the second step is an esterification product of epoxy resin and itaconic acid in a mass ratio of 1:2, wherein both ends of the esterification product are carboxyl groups.
5. The method for controlling the photo-curing activity of an aqueous epoxy itaconate resin of claim 1 wherein the reaction temperature of the first step and the second step are both reflux temperatures of the solvent.
6. The method for controlling the photo-curing activity of an aqueous epoxy itaconate resin according to claim 1 wherein the solvent used in the reaction is acetone.
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JP4462500B2 (en) * 2003-03-06 2010-05-12 日本化薬株式会社 Photosensitive resin composition and cured product thereof
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