CN115677997A - Low-viscosity UV (ultraviolet) photocuring hyperbranched polyester acrylate resin as well as preparation method and application thereof - Google Patents
Low-viscosity UV (ultraviolet) photocuring hyperbranched polyester acrylate resin as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a low-viscosity UV (ultraviolet) photocuring hyperbranched polyester acrylate resin as well as a preparation method and application thereof; the low-viscosity UV photocuring hyperbranched polyester acrylate resin is obtained by reacting hydroxyl-terminated hyperbranched polyester with acrylic acid and then terminating the rest of hydroxyl groups with small molecular acid; the mass ratio of the acrylic acid reacted with the hydroxyl groups to the hydroxyl groups of the hydroxyl-terminated hyperbranched polyester is 3-6. The resin disclosed by the invention not only has 100% solid content and smaller viscosity, but also can be formed into a film only by extremely low UV LED curing energy, and the film has good adhesion, flexibility, high gloss and high hardness, is simple in preparation process, can be produced in a large scale, is easy to adjust the double bond content of the resin, and can be widely applied to the fields of UV curing coatings, 3D printing, metal decorative ink and coatings, packaging printing and the like.
Description
Technical Field
The invention belongs to the technical field of light-cured resin, and particularly relates to low-viscosity UV light-cured hyperbranched polyester acrylate resin as well as a preparation method and application thereof.
Technical Field
In recent years, the problem of environmental pollution is a key problem restricting the high-speed development of economy in China, and the protection of the environment is as important as the development of the economy. In the chemical field, the coating plays a significant role. However, the hazards posed when using traditional solvent-based coatings containing Volatile Organic Compounds (VOCs) are not insignificant, both polluting the environment and threatening life health. Therefore, such solvent-based coatings will gradually exit the historical arena, and environmentally friendly coatings such as UV light curable coatings will gradually take over. The UV photocuring coating system is taken as a representative of environment-friendly coatings, basically has no or very little Volatile Organic Compound (VOC), and has the advantages of fast curing, energy conservation, excellent coating performance and the like, so that the UV photocuring coating system is widely researched and applied.
In the light curing system, the resin plays a more key role in curing, construction and final performance of the material. Epoxy acrylates, urethane acrylates and polyester acrylates are the three most widely used types of resins in photocuring systems today. These photocurable resins have advantages but also unavoidable disadvantages, which limit their further use. The polyester acrylate resin is one of the most widely used UV light-cured resins, has the advantages of low viscosity and low price, and also has the defects of poor flexibility, unstable adhesion, low curing speed and the like; in particular, the low curing rate limits their use in many fields.
Due to the highly branched three-dimensional space structure, the hyperbranched polyester has the characteristics of less intermolecular entanglement, good solubility, low viscosity, good film forming property, high reactivity and the like, and is receiving more and more attention recently. Wangchen (hyperbranched modified ultraviolet curing urethane acrylate, materials science and engineering report, 2021,39 (02), 277-281) adopts diphenylmethane diisocyanate, polypropylene glycol 400 and hydroxyethyl methacrylate as raw materials to prepare urethane acrylate Prepolymer (PUA), andthen, preparing hyperbranched polyurethane by modifying PUA with autonomous hyperbranched polyester in a laboratory; compared with unmodified PUA, the viscosity of the hyperbranched modified PUA is obviously reduced, the mechanical property and the glass transition temperature of the resin after curing are also improved, but the resin has too high viscosity in the aspect of industrial application, needs to be added with a large amount of diluents, has high molecular weight and low content of double bonds, and causes the curing rate to be not ideal; in addition, the price of the isocyanate is high in recent years, and the cost is high. The polyester acrylate has the outstanding advantages of simple synthesis, good material compatibility, lower viscosity and higher curing rate compared with epoxy acrylate and polyurethane acrylate. End group modification or direct synthesis is the main method for preparing hyperbranched polyester acrylate. For example, organic acids containing double bonds such as acrylic acid can be esterified directly with the hydroxyl-terminated hyperbranched polyester or unsaturated groups can be introduced using the reactive agent anhydride or acid chloride. However, the use of acid anhydride or acid chloride leads to higher synthesis cost, and the modification of acrylic acid also faces the problem that gel is easily generated under the condition of high substitution degree. Synthesis of Ningchunhua (Ningchunhui, chenyouyue, yonghanyu, yi's UV curable hyperbranched polyester acrylate and curing property paint industry 2018,48 (03), 23-27) pentaerythritol and 2, 2-dimethylolpropionic acid are used as raw materials to synthesize hyperbranched polyester polyol, the hyperbranched polyester polyol is reacted with succinic anhydride to obtain hyperbranched polyester polybasic acid, finally hydroxyethyl methacrylate is used for modification to synthesize the hyperbranched polyester acrylate, and the complete curing energy of the hyperbranched polyester acrylate is 600J/m 2 And the viscosity is high, a large amount of diluent is added, the synthesis cost is high, and the industrialization is not facilitated.
The hyperbranched polyester acrylate in the existing market has the defects of slow curing, incapability of meeting the requirements of curing under low energy, high viscosity and poor flexibility.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a low-viscosity UV light-cured hyperbranched polyester acrylate resin with a novel structure, and a preparation method and application thereof. The preparation method is characterized in that flexible chain polyol and micromolecular acid are introduced into hyperbranched polyester acrylate, and a reaction intermediate capable of being cured by UV is introduced, so that the polymer simultaneously contains alkyl chains, ether bonds, ester bonds and acrylic double bonds; and the acrylated hyperbranched polyester is synthesized with high conversion rate through process optimization. In addition, the number of terminal acrylic double bonds of the hyperbranched polyester acrylate UV photocuring resin prepared by the invention is adjustable, and the crosslinking density of the resin can be adjusted within a certain range, so that the physical properties of the cured coating are changed, and the performance requirements of different application fields can be better met.
The purpose of the invention is realized by the following technical scheme:
a low-viscosity UV light-cured hyperbranched polyester acrylate resin is prepared by reacting hydroxyl-terminated hyperbranched polyester with acrylic acid, and then terminating the residual hydroxyl groups with small molecular acid; the mass ratio of the acrylic acid reacted with the hydroxyl groups to the hydroxyl groups of the hydroxyl-terminated hyperbranched polyester is 3-6.
Preferably, the mass ratio of the acrylic acid reacted with hydroxyl groups to the hydroxyl groups of the hydroxyl-terminated hyperbranched polyester is 4-6.
Preferably, the hydroxyl-terminated hyperbranched polyester has a hydroxyl-terminated number of 6 to 8 (determined by the number of hydroxyl groups of the polyol used and the number of reaction generations).
Preferably, the hydroxyl-terminated hyperbranched polyester consists of polyol and AB 2 The multifunctional monomer is obtained by reaction; the AB 2 The type multifunctional monomer is one or more of acid compounds with two hydroxyl groups at the end; the polyol is one or more of compounds containing two or three hydroxyl groups.
Further preferably, the polyol and AB 2 A catalyst is added into the type polyfunctional monomer reaction system; more preferably, the catalyst is p-toluenesulfonic acid;
further preferably, the AB is 2 The type polyfunctional monomer is one or two of dimethylolbutyric acid and dimethylolpropionic acid; the polyalcohol is trimethylolpropane, diethylene glycol, 1, 6-hexanediol, polyethylene glycol 200. One or more of polycaprolactone triol 300.
Preferably, the small molecule acid is a small molecule compound containing one carboxyl group.
Further preferably, the small molecular acid is one or more of propionic acid, butyric acid, n-caprylic acid and oleic acid.
The preparation method of the low-viscosity UV photocuring hyperbranched polyester acrylate resin comprises the following steps:
adding acrylic acid, a polymerization inhibitor, an antioxidant and a catalyst into the hydroxyl-terminated hyperbranched polyester, and reacting to obtain hyperbranched polyester acrylate HBPA-OH containing partial hydroxyl; adding small molecular acid to continue reacting until the residual hydroxyl is completely terminated, separating and purifying to obtain the low-viscosity UV photocuring hyperbranched polyester acrylate resin.
Preferably, the antioxidant is one or more of dibutyl hydroxy toluene, tris (2, 4-di-tert-butylphenyl) phosphite, trinonylphenol phosphite and triphenyl phosphite.
Preferably, the polymerization inhibitor is one or more of hydroquinone, methyl hydroquinone and 4-methoxyphenol.
Preferably, the esterification reaction process is subjected to water diversion treatment; the aqueous solvent is toluene.
The low-viscosity UV photocuring hyperbranched polyester acrylate resin is applied to the fields of UV curing coatings, 3D printing, metal decorative ink, coatings, packaging printing and the like.
The invention has the beneficial effects that:
the invention not only has 100 percent of solid content and lower viscosity, but also only needs extremely low UV LED curing energy, namely 117.5J/m 2 The paint can be formed into a film, has 1-grade adhesive force, good flexibility, high gloss and high hardness after film forming, and is simple in preparation process, mass in production and easy to adjust the double bond content of the resin.
Drawings
Fig. 1 is an infrared curve before and after the low-viscosity UV light-cured hyperbranched polyester acrylate resin of example 1 is modified.
FIG. 2 is a graph showing the change of acid value with time in the reaction system for synthesizing hyperbranched polyester in the first step of example 1.
FIG. 3 is the NMR spectrum of the low viscosity UV light-cured hyperbranched polyester acrylate resin of example 1.
FIG. 4 is a UV spectrum of the low viscosity UV light-cured hyperbranched polyester acrylate resin of example 1,2,3, 4.
FIG. 5 is a thermogram of the low viscosity UV light-cured hyperbranched polyester acrylate resin of example 1.
FIG. 6 is a differential thermal scanning calorimetry thermogram of the low viscosity UV light cured hyperbranched polyester acrylate resin of example 1.
FIG. 7 is an infrared curve of the low viscosity UV light-cured hyperbranched polyester acrylate resin of example 1 without being terminated with a small molecular acid after being acrylic-modified.
Detailed Description
The following examples are given in detail in connection with specific experimental procedures and are presented herein for the purpose of illustration only and not for the purpose of limitation. This is described here.
The invention provides a low-viscosity UV (ultraviolet) photocuring hyperbranched polyester acrylate resin and a preparation method thereof 2 Adding a catalyst into a multifunctional monomer according to a certain proportion to react to obtain hydroxyl-terminated hyperbranched polyester (HBP) with different generations; adding certain acrylic acid, polymerization inhibitor and antioxidant into the synthesized hyperbranched polyester, and reacting to obtain hyperbranched polyester acrylate (HBPA-OH) containing partial hydroxyl; completely blocking the residual hydroxyl of the HBPA-OH by using small molecular acid to prepare UV (ultraviolet) light-curable hyperbranched polyurethane acrylate resin (HBPA) containing 3-6 terminal acrylic double bonds on average; and separating and purifying to obtain the colorless or light yellow transparent low-viscosity hyperbranched polyester acrylate UV curing resin.
The AB 2 The type multifunctional monomer is an acid compound with two hydroxyl groups at the end or a mixture thereof, wherein the acid compound is selected from dimethylol butyric acid or dimethylol propionic acid.
As a preferred technical scheme, the polyalcohol core is a compound containing two or three hydroxyl groups-OH or a mixture thereof, wherein the polyalcohol core is selected from one or more of trimethylolpropane, diethylene glycol, 1, 6-hexanediol, polyethylene glycol 200 and polycaprolactone triol 300.
As a preferred technical scheme, the small molecule acid is a small molecule compound containing a carboxyl, wherein the small molecule compound is selected from one or more of propionic acid, butyric acid, n-caprylic acid and oleic acid.
As a preferred technical scheme, the antioxidant is one or more of dibutyl hydroxy toluene, tris (2, 4-di-tert-butylphenyl) phosphite, trinonylphenol phosphite and triphenyl phosphite.
As a preferable technical scheme, the polymerization inhibitor is one or more of hydroquinone, methyl hydroquinone, 4-methoxyphenol and the like.
As a preferred technical scheme, the catalyst is p-toluenesulfonic acid.
Example 1
A preparation method of a low-viscosity UV light-cured hyperbranched polyester acrylate resin specifically comprises the following steps:
1) Adding 24g of dimethylolbutyric acid (DMBA) into a mixture of 8.6g of diethylene glycol (DEG) and 0.3g of p-toluenesulfonic acid under stirring at 90 ℃, heating to 130 ℃, continuously adding 48g of dimethylolbutyric acid (DMBA) after reacting for 1h, reacting for 2h, and vacuumizing for 0.5h to obtain the colorless or light yellow molten hydroxyl-terminated hyperbranched polyester.
2) And (2) in a reaction vessel provided with a water separator, a thermometer and a stirrer, when the temperature of the synthesized hyperbranched polyester is reduced to 90 ℃, adding 50ml of toluene (as a solvent with water), 0.15g of hydroquinone, 0.05g of methyl hydroquinone and 0.05g of tris (2, 4-di-tert-butylphenyl) phosphite, mixing and stirring for 5min, adding 40.88g of acrylic acid for reaction for 2h, heating to 125 ℃, and continuing the reaction until the water content in the water separator is 8.75g, thereby obtaining the non-terminated hyperbranched polyester acrylate resin.
3) 19.16g of propionic acid was added to the above reaction system, and the reaction was continued until the amount of water in the trap was 11.7g in total. After the reaction is finished, separation and purification are carried out to obtain light yellow or colorless transparent liquid.
The prepared hyperbranched polyester molecule contains 8 terminal functional group hydroxyl groups on average, double bonds and alkyl chains are introduced to prepare the hyperbranched polyester acrylate, the terminal groups contain 4-6 acrylic double bonds on average, the viscosity is low, and the curing rate is high.
FIG. 1 is an infrared curve before and after modification of the low-viscosity UV light-cured hyperbranched polyester acrylate resin of example 1. FT-IR (American Nicolet Fourier Infrared spectrometer) 3400cm －1 Substantially disappeared-OH peaks at 1640 and 810cm －1 The characteristic peak of C = C double bond appears obviously, the surface hydroxyl has reacted completely, the double bond is connected in a large amount, and the target resin is synthesized successfully.
FIG. 2 is a graph showing the change of acid value with time in the reaction system for synthesizing hyperbranched polyester in the first step of example 1, which demonstrates that as the reaction proceeds, the esterification reaction between hydroxyl and carboxyl groups results in a decrease of acid value, and the reaction becomes stable after 4h, indicating that the reaction is almost complete.
FIG. 3 is a NMR chart of the low viscosity UV light-cured hyperbranched polyester acrylate resin of example 1. The peak at delta = 5.7-6.7 ppm belongs to the hydrogen peak on the carbon-carbon double bond in the product, further proves the synthesis of standard ester and can calculate the average double bond content of the resin according to the peak area.
FIG. 5 is a thermogram of the low viscosity UV light-cured hyperbranched polyester acrylate resin of example 1. Almost no weight loss is generated before 100 ℃, and the weight loss is less than 5% at 200 ℃, which indicates that the photo-curing of the coating is relatively complete and basically no residual micromolecular substance exists; it can be seen that at 300 c, the weight loss is significant, at which point the chemical bonds within the coating begin to break down. When the mass loss is 10 percent, the temperature is higher than 300 ℃, and when the temperature reaches about 500 ℃, the residual mass is about 0 percent. Indicating that the paint film has excellent thermal stability.
FIG. 6 is a differential thermal scanning calorimetry thermogram of the low viscosity UV light cured hyperbranched polyester acrylate resin of example 1. The degree of terminal acrylation increases and the content of soft segments in the molecule increases, so that the glass transition temperature of HBPA is reduced to-57 ℃.
FIG. 7 is a low viscosity UV light cure of example 1And the infrared curve of the hyperbranched polyester acrylate resin which is not terminated by micromolecular acid after being modified by acrylic acid. FT-IR (American Nicolet Fourier Infrared Spectroscopy) 3400cm －1 Peaks at (D) indicate that residual-OH remained unreacted, 1640 and 810cm －1 The characteristic peak of C = C double bond clearly appears indicating successful introduction of the double bond.
Example 2
A preparation method of a low-viscosity UV light-cured hyperbranched polyester acrylate resin specifically comprises the following steps:
1) Adding 24g of dimethylolbutyric acid (DMBA) into a mixture of 21.7g of Trimethylolpropane (TMP) and 0.3g of p-toluenesulfonic acid under stirring at 90 ℃, heating to 130 ℃, continuously adding 48g of dimethylolbutyric acid (DMBA) after reacting for 1h, reacting for 2h, and vacuumizing for 0.5h to obtain the colorless or light yellow molten hydroxyl-terminated hyperbranched polyester.
2) In a reaction vessel provided with a water separator, a thermometer and a stirrer, 50ml of toluene, 0.15g of hydroquinone, 0.05g of methyl hydroquinone and 0.05g of tris (2, 4-di-tert-butylphenyl) phosphite are added when the temperature of the synthesized hyperbranched polyester is reduced to 90 ℃, mixed and stirred for 5min, 58.21g of acrylic acid is added for reaction for 2h, and the reaction is continued after the temperature is raised to 125 ℃ until the water content in the water separator is 8.16g.
3) 19.16g of propionic acid was added to the above reaction system, and the reaction was continued until the amount of water in the trap was 11.7g in total. After the reaction is finished, separation and purification are carried out to obtain light yellow or colorless transparent liquid.
The prepared hyperbranched polyester molecule contains 6 terminal functional group hydroxyl groups on average, double bonds and alkyl chains are introduced to prepare the hyperbranched polyester acrylate, the terminal groups contain 3-5 acrylic double bonds on average, the viscosity is low, and the curing rate is high.
FT-IR (American Nicolet Fourier Infrared Spectroscopy) 3400cm －1 At which-OH peaks substantially disappeared, 1640 and 810cm －1 The characteristic peak of C = C double bond appears clearly.
NMR (bruker AVANCE NEO nuclear magnetic resonance spectrometer).
Example 3
A preparation method of a low-viscosity UV light-cured hyperbranched polyester acrylate resin specifically comprises the following steps:
1) Adding 24g of dimethylolbutyric acid (DMBA) into a mixture of 9.57g of 1, 6-Hexanediol (HDO) and 0.3g of p-toluenesulfonic acid under stirring at 90 ℃, heating to 130 ℃, continuously adding 48g of dimethylolbutyric acid (DMBA) after reacting for 1h, reacting for 2h, and then vacuumizing for reacting for 0.5h to obtain the colorless or light yellow molten hydroxyl-terminated hyperbranched polyester.
2) In a reaction vessel provided with a water separator, a thermometer and a stirrer, 50ml of toluene, 0.15g of hydroquinone, 0.05g of methylhydroquinone and 0.05g of tris (2, 4-di-tert-butylphenyl) phosphite are added when the temperature of the synthesized hyperbranched polyester is reduced to 90 ℃, mixed and stirred for 5min, 58.21g of acrylic acid is added for reaction for 2h, and the reaction is continued after the temperature is raised to 125 ℃ until the water content in the water separator is 8.16g.
3) 19.16g of propionic acid was added to the above reaction system, and the reaction was continued until the amount of water in the water trap was 11.7g in total. After the reaction is finished, separation and purification are carried out to obtain light yellow or colorless transparent liquid.
The prepared hyperbranched polyester molecule contains 8 terminal functional group hydroxyl groups on average, double bonds and alkyl chains are introduced to prepare the hyperbranched polyester acrylate, the terminal groups contain 5-6 acrylic double bonds on average, the viscosity is low, and the curing rate is high.
FT-IR (American Nicolet Fourier Infrared spectrometer) 3400cm －1 At which-OH peaks substantially disappeared, 1640 and 810cm －1 The characteristic peak of C = C double bond appears clearly.
NMR (bruker AVANCE NEO nuclear magnetic resonance spectrometer).
Example 4
A preparation method of a low-viscosity UV (ultraviolet) light-cured hyperbranched polyester acrylate resin specifically comprises the following steps:
1) Adding 24g of dimethylol butyric acid (DMBA) into a mixture of 48.5g of polycaprolactone triol 300 (PCL 300) and 0.3g of p-toluenesulfonic acid under stirring at 90 ℃, heating to 130 ℃, continuously adding 48g of dimethylol butyric acid (DMBA) after reacting for 1h, reacting for 2h, and vacuumizing for 0.5h to obtain the colorless or light yellow molten hydroxyl-terminated hyperbranched polyester.
2) In a reaction vessel provided with a water separator, a thermometer and a stirrer, 50ml of toluene, 0.15g of hydroquinone, 0.05g of methyl hydroquinone and 0.05g of tris (2, 4-di-tert-butylphenyl) phosphite are added when the temperature of the synthesized hyperbranched polyester is reduced to 90 ℃, mixed and stirred for 5min, 58.21g of acrylic acid is added for reaction for 2h, and the reaction is continued after the temperature is raised to 125 ℃ until the water content in the water separator is 8.16g.
3) 19.16g of propionic acid was added to the above reaction system, and the reaction was continued until the amount of water in the water trap was 11.7g in total. After the reaction is finished, separation and purification are carried out to obtain light yellow or colorless transparent liquid.
The prepared hyperbranched polyester molecule contains 6 terminal functional group hydroxyl groups on average, double bonds and alkyl chains are introduced to prepare the hyperbranched polyester acrylate, the terminal groups contain 3-5 acrylic double bonds on average, the viscosity is low, and the curing rate is high.
FT-IR (American Nicolet Fourier Infrared Spectroscopy) 3400cm －1 Substantially disappeared-OH peaks at 1640 and 810cm －1 The characteristic peak of C = C double bond appears clearly.
NMR (bruker AVANCE NEO nuclear magnetic resonance spectrometer).
The paint preparation method comprises the following steps: the UV curable hyperbranched polyester synthesized in the previous experiment was formulated with TPO as photoinitiator according to resin HDDA: photoinitiator = 65. The coating was applied to glass and cured under a UV curing machine (117.5J/m) 2 ). The adhesive force, pencil hardness, glossiness, impact resistance and other properties of the resin paint film are tested according to a national standard test method. And compared with 6316 type resin (multifunctional polyester acrylate) of taiwan chang corporation.
Viscosity is determined as GBT 22235-2008;
the pencil hardness is measured according to GB/6739-1996;
flexibility was determined according to GB/T1731-1993;
gloss was measured according to GB/T1743-1993.
The test results are given in table 1 below:
TABLE 1
FIG. 4 is a UV spectrum of the low viscosity UV light-cured hyperbranched polyester acrylate resin of example 1,2,3, 4. The hyperbranched polyester modified by the ether bond, the long carbon chain and the micromolecule acid has the advantages of high solid content, good flexibility, low viscosity, high gloss and high hardness, high curing rate, simple and cheap raw materials, and the hyperbranched polyester is worthy of large-scale industrial popularization, and the overall level of the hyperbranched polyester achieves the effect expected by experiments.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any simple changes, substitutions, combinations and simplifications made by those skilled in the art according to the disclosure of the present invention should be considered as equivalent substitutions and alterations all included in the scope of the present invention.
Claims (10)
1. A low-viscosity UV light-cured hyperbranched polyester acrylate resin is characterized in that hydroxyl-terminated hyperbranched polyester reacts with acrylic acid, and then the remaining hydroxyl is terminated by micromolecular acid; the mass ratio of the acrylic acid reacted with the hydroxyl groups to the hydroxyl groups of the hydroxyl-terminated hyperbranched polyester is 3-6.
2. The low viscosity UV light-curable hyperbranched polyester acrylate resin according to claim 1 wherein the hydroxyl-terminated hyperbranched polyester has a number of terminal hydroxyl groups of 6-8.
3. The low viscosity UV light curable hyperbranched polyester acrylate resin of claim 1 wherein the hydroxyl terminated hyperbranched polyester is composed of a polyol and AB 2 The multifunctional monomer is obtained by reaction;
the AB 2 The type multifunctional monomer is one or more of acid compounds with two hydroxyl groups at the end;
the polyol is one or more of compounds containing two or three hydroxyl groups.
4. The low viscosity UV light-curable hyperbranched polyester acrylate resin of claim 3, wherein the polyol and AB are 2 A catalyst is added into the multifunctional monomer reaction system; the catalyst is p-toluenesulfonic acid;
the AB is 2 The type polyfunctional monomer is one or two of dimethylolbutyric acid and dimethylolpropionic acid; the polyalcohol is one or more of trimethylolpropane, diethylene glycol, 1, 6-hexanediol, polyethylene glycol 200 and polycaprolactone triol 300.
5. The low viscosity UV light-curable hyperbranched polyester acrylate resin of claim 1, wherein the small molecule acid is a small molecule compound containing one carboxyl group.
6. The low viscosity UV curable hyperbranched polyester acrylate resin of claim 5 wherein the small molecule acid is one or more of propionic acid, butyric acid, n-octanoic acid, and oleic acid.
7. The method for preparing the low viscosity UV light-curable hyperbranched polyester acrylate resin of any one of claims 1 to 6, comprising the steps of:
adding acrylic acid, a polymerization inhibitor, an antioxidant and a catalyst into the hydroxyl-terminated hyperbranched polyester, and reacting to obtain hyperbranched polyester acrylate HBPA-OH containing partial hydroxyl; adding small molecular acid to continue reacting until residual hydroxyl groups are completely terminated, and separating and purifying to obtain the low-viscosity UV photocuring hyperbranched polyester acrylate resin.
8. The method according to claim 7, wherein the antioxidant is one or more of dibutylhydroxytoluene, tris (2, 4-di-tert-butylphenyl) phosphite, trinonylphenol phosphite, and triphenyl phosphite.
9. The preparation method of claim 7, wherein the polymerization inhibitor is one or more of hydroquinone, methylhydroquinone and 4-methoxyphenol;
the catalyst is p-toluenesulfonic acid.
10. The low viscosity UV light curable hyperbranched polyester acrylate resin of any one of claims 1 to 6 for use in UV curable coatings, 3D printing, metallic decorative inks and coatings, and packaging printing.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5834118A (en) * | 1994-09-08 | 1998-11-10 | Neste Oy Of Keilaniemi | Radiation curable resins comprising hyperbranched polyesters |
| CN102911349A (en) * | 2012-10-11 | 2013-02-06 | 华南理工大学 | Caprolactone modified hyperbranched polyester and preparation method and application thereof |
| CN103242627A (en) * | 2013-03-27 | 2013-08-14 | 宋雪晶 | Application of fatty acid ester end group hyperbranched polyester as high polymer material viscosity reducing and toughening agent |
| CN105461933A (en) * | 2015-12-02 | 2016-04-06 | 威海晨源分子新材料有限公司 | Hyperbranched UV (ultraviolet) resin as well as preparation method and application of hyperbranched UV resin in coating |
| CN106565965A (en) * | 2016-11-07 | 2017-04-19 | 华南理工大学 | Hyperbranched hydroxyl polyester resin, and preparation method and application of hyperbranched hydroxyl polyester resin |
| CN108840999A (en) * | 2018-05-31 | 2018-11-20 | 肇庆福田化学工业有限公司 | A kind of synthetic method of hyper-branched polyester |
| CN109265663A (en) * | 2018-09-25 | 2019-01-25 | 厦门大学 | A kind of preparation method of hyperbranched unsaturated polyester (UP) |
-
2022
- 2022-11-02 CN CN202211363707.XA patent/CN115677997A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5834118A (en) * | 1994-09-08 | 1998-11-10 | Neste Oy Of Keilaniemi | Radiation curable resins comprising hyperbranched polyesters |
| CN102911349A (en) * | 2012-10-11 | 2013-02-06 | 华南理工大学 | Caprolactone modified hyperbranched polyester and preparation method and application thereof |
| CN103242627A (en) * | 2013-03-27 | 2013-08-14 | 宋雪晶 | Application of fatty acid ester end group hyperbranched polyester as high polymer material viscosity reducing and toughening agent |
| CN105461933A (en) * | 2015-12-02 | 2016-04-06 | 威海晨源分子新材料有限公司 | Hyperbranched UV (ultraviolet) resin as well as preparation method and application of hyperbranched UV resin in coating |
| CN106565965A (en) * | 2016-11-07 | 2017-04-19 | 华南理工大学 | Hyperbranched hydroxyl polyester resin, and preparation method and application of hyperbranched hydroxyl polyester resin |
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| CN109265663A (en) * | 2018-09-25 | 2019-01-25 | 厦门大学 | A kind of preparation method of hyperbranched unsaturated polyester (UP) |
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