CN113150244B - Sulfonate type epoxy acrylate resin and preparation method and application thereof - Google Patents

Sulfonate type epoxy acrylate resin and preparation method and application thereof Download PDF

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CN113150244B
CN113150244B CN202110555401.3A CN202110555401A CN113150244B CN 113150244 B CN113150244 B CN 113150244B CN 202110555401 A CN202110555401 A CN 202110555401A CN 113150244 B CN113150244 B CN 113150244B
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sulfonate
epoxy acrylate
acrylate resin
type epoxy
resin
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CN113150244A (en
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罗青宏
张栋棋
刘晓暄
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Guangdong University of Technology
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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
    • C08G59/1483—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing sulfur
    • 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
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1466—Acrylic or methacrylic 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
    • 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
    • C08G59/1494—Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
    • 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
    • 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 sulfonate type epoxy acrylate resin and a preparation method and application thereof. The sulfonate epoxy acrylate resin has a structure shown in a formula (I): wherein R is1Is one or more of the following structures:
Figure DDA0003076442910000011
R2is H or CH3(ii) a n is a positive integer of 1-3. The sulfonate structure is introduced into the sulfonate type epoxy acrylate resin, and the sulfonate group is a strong hydrophilic group, so that the hydrophilic performance of the epoxy acrylate resin is greatly improved; meanwhile, compared with an ammonium salt system, the sulfonate has lower odor, and does not bring toxic and harmful gases in the synthesis process. The water-based photocureable coating prepared by mixing the sulfonate epoxy acrylate resin, the photoinitiator and water can be rapidly cured under the ultraviolet condition, and the water contact angle of the cured coating is less than or equal to 65 degrees.
Figure DDA0003076442910000012

Description

Sulfonate type epoxy acrylate resin and preparation method and application thereof
Technical Field
The invention relates to the technical field of high polymer material synthesis, and particularly relates to a sulfonate type epoxy acrylate resin and a preparation method and application thereof.
Background
Epoxy resin has good adhesive force to base materials, good chemical resistance, high heat resistance and high electrical insulation, and is widely applied to the fields of buildings, electronic appliances, coatings, adhesives and the like. However, since the conventional epoxy resin is oily, the segment thereof has no hydrophilic group introduced therein or the introduced hydrophilic group has low hydrophilicity, and it is usually necessary to enhance the water solubility thereof by adding an emulsifier or a salt-forming agent at a later stage.
Chinese patent application CN101914171A discloses a sulfonic acid type UV-curable aqueous epoxy emulsion, which is prepared by introducing sulfonic acid groups into two ends of a molecular chain through the reaction of epoxy fumaroyl chloride and sulfamic acid, but hydrogen chloride gas is generated during the reaction process, and in order to avoid the escape of harmful gases, alkali is additionally added into the system for absorption. Chinese patent application CN111961169A discloses a water-based epoxy resin emulsion, which comprises epoxy resin, an emulsifier and water, and improves the hydrophilicity and emulsibility of the epoxy resin. However, the added emulsifier usually needs to be stirred by means of strong machinery to uniformly disperse the epoxy resin, so that on one hand, the process flow is more, and on the other hand, the emulsifier is easily broken by external influence to cause deterioration of hydrophilic performance.
Therefore, it is required to develop an epoxy acrylate resin having good hydrophilicity.
Disclosure of Invention
In order to overcome the defect of poor hydrophilicity in the prior art, the invention provides the sulfonate type epoxy acrylate resin, and the sulfonate type epoxy acrylate resin introduces a sulfonate structure with strong hydrophilicity, so that the hydrophilicity of the epoxy acrylate resin is greatly improved.
The invention also aims to provide a preparation method of the sulfonate epoxy acrylate resin.
The invention also aims to provide the application of the sulfonate epoxy acrylate resin in preparing the aqueous photocuring coating.
In order to solve the technical problems, the invention adopts the technical scheme that:
a sulfonate type epoxy acrylate resin has a structure shown in a formula (I):
Figure BDA0003076442890000021
wherein R is1Is one or more of the following structures:
Figure BDA0003076442890000022
R2is H or CH3(ii) a n is a positive integer of 1-3.
The sulfonate structure is introduced into the sulfonate type epoxy acrylate resin, and the sulfonate group is a strong hydrophilic group, so that the hydrophilic performance of the epoxy acrylate resin is greatly improved; meanwhile, compared with an ammonium salt system, the smell of the sulfonate is lower, and the problem of residual smell of the epoxy resin is avoided.
R in sulfonate type epoxy acrylate resin1The resin is in a chain-shaped or ring-shaped conformation, so that the water solubility of the resin and the hardness of the resin can be improved; wherein
Figure BDA0003076442890000023
Is a chain structure, compared with
Figure BDA0003076442890000024
Figure BDA0003076442890000025
The cyclic structure of (2) is more likely to cause conformational transition of a molecular chain having a chain structure during resin emulsification, thereby having better water solubility.
Preferably, said R is1Is composed of
Figure BDA0003076442890000026
The invention also provides a preparation method of the sulfonate epoxy acrylate resin, which comprises the following steps:
s1, mixing sulfonate dihydric alcohol and an anhydride compound, heating to 100-105 ℃ under a stirring condition, reacting for 1 hour, and monitoring the acid value of a reaction solution;
s2, calculating a theoretical acid value according to the molar ratio of fed reactants, adding epoxy resin and a catalyst into the reaction liquid in the S1 when the titrated acid value reaches the theoretical value, and reacting at the temperature of 110-112 ℃ until the acid value is less than 5 mgKOH/g;
and S3, adding a blocking monomer dissolved with a polymerization inhibitor into the reaction liquid in the S2, and reacting at 115-118 ℃ until the acid value is less than 5mgKOH/g to obtain the sulfonate epoxy acrylic resin.
According to the preparation method, sulfonate diol and anhydride compounds are used as raw materials to introduce sulfonate groups, so that toxic and harmful gases such as hydrogen chloride are not brought in the synthesis process.
In the steps of S1, S2, S3, as the reaction proceeds, the molecular weight of the reactant tends to increase, the entanglement between molecules increases, and the probability of effective collision decreases; therefore, the reaction temperature is increased in a gradient manner to increase the effective collision probability among molecules and promote the reaction degree to be more complete.
However, the reaction temperature is not so high in S1 to S3, and the polymerization of the end-capping monomer and the formation of gel are caused by the too high reaction temperature. Therefore, the reaction temperature is set to 100-105 ℃ in S1, 110-112 ℃ in S2, and 115-118 ℃ in S3.
Preferably, the molecular weight of the sulfonate diol is 500-1000.
In general, the proportion of the hydrophilic segment in the sulfonate diol having a smaller molecular weight is larger, and the proportion of the hydrophobic segment thereof increases as the molecular weight increases, so that the sulfonate diol having a smaller molecular weight has better water solubility.
Preferably, the water content of the sulfonate diol is < 0.1%.
Preferably, the acid anhydride compound is one or more of succinic anhydride, phthalic anhydride or hexahydrophthalic anhydride.
Preferably, the epoxy resin is a bisphenol a type epoxy resin and/or a bisphenol F type epoxy resin.
The epoxy equivalent of the bisphenol A type epoxy resin is 190, and the epoxy equivalent of the bisphenol F type epoxy resin is 170.
Preferably, the catalyst is triphenylphosphine and/or triethylbenzylammonium chloride.
Preferably, the polymerization inhibitor is one or more of tert-butyl hydroquinone, p-hydroxyanisole (MEHQ) and 2-methoxy hydroquinone.
The addition of the polymerization inhibitor can prevent the end-capped monomer from polymerizing at high temperature.
Preferably, the end-capping monomer is acrylic acid and/or methacrylic acid.
Preferably, the mass ratio of the sulfonate dihydric alcohol to the anhydride compound to the epoxy resin to the catalyst to the polymerization inhibitor to the blocked acrylic acid is (25-38) to (5-8) to (28-40) to (0.3-0.5) to (0.05-0.08) to (5-8).
The sulfonate epoxy acrylate resin is dispersible in water.
The invention also protects the application of the sulfonate epoxy acrylate resin in the preparation of the waterborne photocureable coating.
Preferably, the aqueous photocureable coating comprises the following components in parts by weight:
70-80 parts of sulfonate epoxy acrylate resin, 1.5-3 parts of photoinitiator and 20-30 parts of water.
The photoinitiator may be a photoinitiator commonly used in photocurable coatings.
Optionally, the photoinitiator is TPO (2,4, 6-trimethylbenzoyl-diphenylphosphine oxide), TPOL (ethyl 2,4, 6-trimethylbenzoylphenylphosphonate), 1173 (2-hydroxy-2-methyl-1-phenylpropanone).
Compared with the prior art, the invention has the beneficial effects that:
(1) the sulfonate structure is introduced into the sulfonate type epoxy acrylate resin, and the sulfonate group is a strong hydrophilic group, so that the hydrophilic performance of the epoxy acrylate resin is greatly improved, and toxic and harmful gases cannot be brought in the synthesis process.
(2) The water-based photocureable coating prepared by mixing the sulfonate epoxy acrylate resin, the photoinitiator and water can be rapidly cured under the ultraviolet condition, and the water contact angle of the cured coating is less than or equal to 65 degrees.
Drawings
FIG. 1 shows the appearance of epoxy acrylate resins prepared in examples 1 to 2 and comparative example 1.
Detailed Description
The present invention will be further described with reference to the following embodiments.
The raw materials in the examples and comparative examples are all commercially available;
wherein the water content of the sulfonate dihydric alcohol is less than 0.1 percent, and the sulfonate dihydric alcohol is purchased from Beijing Bai Yuan chemical Co., Ltd, BY3306(500 molecular weight), BY3303(1000 molecular weight) and BY3305B (2000 molecular weight);
polyester diol, molecular weight 500, prepared by esterification and dehydration of methyl propylene glycol and succinate.
Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
The embodiment provides a sulfonate type epoxy acrylate resin, which is prepared by the following steps:
s1, mixing sulfonate dihydric alcohol (BY3306, molecular weight 500) and succinic anhydride, heating to 100-105 ℃ under a stirring condition, reacting for 1h, and monitoring the acid value of a reaction solution;
s2, when the acid value of the reaction liquid reaches 160mgKOH/g, adding bisphenol A type epoxy resin (the epoxy equivalent is 190) and triphenylphosphine serving as a catalyst into the reaction liquid in S1, and reacting at the temperature of 110-112 ℃ until the acid value is less than 5 mgKOH/g;
s3, adding acrylic acid dissolved with a polymerization inhibitor (p-hydroxyanisole) into the reaction liquid in S2, and reacting at 115-118 ℃ until the acid value is less than 5mgKOH/g to obtain the sulfonate type epoxy acrylate resin;
wherein the mass ratio of the sulfonate dihydric alcohol (BY3306), the succinic anhydride, the bisphenol A epoxy resin, the catalyst, the polymerization inhibitor and the acrylic acid is 24.81: 9.93: 37.71: 0.3:0.08: 7.15.
The structural formula of the prepared sulfonate type epoxy acrylate resin is as follows:
Figure BDA0003076442890000051
example 2
This example provides a sulfonate epoxy acrylate resin, and the preparation method is different from that of example 1 in that the used sulfonate diol is BY3303, 1000 molecular weight;
wherein the mass ratio of the sulfonate dihydric alcohol (BY3303), the succinic anhydride, the bisphenol A epoxy resin, the catalyst, the polymerization inhibitor and the acrylic acid is 37.83:7.57:28.75:0.3:0.08: 5.45.
Example 3
This example provides a sulfonate type epoxy acrylate resin, which is prepared by a method different from that of example 1 in that methacrylic acid is used in equimolar amounts instead of acrylic acid.
Example 4
This example provides a sulfonate type epoxy acrylate resin, which is prepared by using hexahydrophthalic anhydride instead of succinic anhydride, as a difference from example 2; bisphenol F type epoxy resin (epoxy equivalent: 170) was used in place of bisphenol A type epoxy resin;
wherein the mass ratio of the sulfonate dihydric alcohol (BY3303), the hexahydrophthalic anhydride, the bisphenol F type epoxy resin, the catalyst, the polymerization inhibitor and the acrylic acid is 37.33:11.51:25.38:0.3:0.08: 5.38.
Example 5
This example provides a sulfonate type epoxy acrylate resin, which is prepared by a method different from that of example 1 in that phthalic anhydride is used in equimolar amounts instead of succinic anhydride.
Comparative example 1
This comparison provides a sulfonate type epoxy acrylate resin, which is prepared BY a method different from that of example 1 in that the sulfonate diol used is BY3305B, 2000 molecular weight.
Comparative example 2
This comparative example provides an epoxy acrylate resin, which is prepared by a method different from that of example 1 in that: polyester diol with molecular weight of 500 is used in place of sulfonate diol.
Comparative example 3
This comparative example provides an epoxy acrylate resin, and the preparation method is different from example 1 in that polytetrahydrofuran diol having a molecular weight of 500 and the like are used instead of sulfonate diol.
Performance test
The epoxy acrylate resins prepared in the above examples and comparative examples were used to prepare aqueous photocurable coatings, respectively, by the following methods:
and uniformly mixing 80 parts of epoxy acrylate resin, 20 parts of water or diluted monomer dipropylene glycol triacrylate and 1.5 parts of photoinitiator TPO to obtain the waterborne photocuring coating.
And (3) scraping the waterborne photocuring coating on a glass plate by using a four-side coater to form a film with the thickness of 20 mu m, and irradiating the film for 1-3 s under the wavelength of 365nm by using an ultraviolet lamp of a UV mercury lamp to form the coating.
Respectively carrying out performance tests on the coating film, wherein the specific method comprises the following steps:
water contact angle: the test was performed according to GB/T30693-.
Water absorption of the coating: the test was performed according to HG/T3344-.
The test results of examples 1 to 5 and comparative examples 1 to 3 are shown in Table 1.
TABLE 1 test results of examples 1 to 5 and comparative examples 1 to 3
Water contact angle Water absorption of coating
Example 1 57.7 11.87％
Example 2 62.9 6.13％
Example 3 55.3 9.03％
Example 4 60.4 7.45％
Example 5 56.8 9.67％
Comparative example 1 73.8 5.38％
Comparative example 2 95.7 3.1％
Comparative example 3 90.2 3.56％
According to the test results in Table 1, the water-based photocureable coating prepared from the epoxy acrylate resin in the embodiment 1-5 has a water contact angle of a coating film of less than or equal to 65 degrees after being cured to form a film, which indicates that the coating has good hydrophilic performance. The water resistance of the water-based photo-curing coating with good hydrophilicity is generally poor, but in some occasions, the coating is required to have certain water resistance, and the water absorption rate is not easy to be too high. The water absorption of the coating prepared by the aqueous photocuring coating in each embodiment of the invention is less than or equal to 15 percent, namely the hydrophilicity and the water resistance of the epoxy acrylate resin are well balanced. In comparative example 1, the molecular weight of the sulfonate diol was 2000, the water contact angle of the epoxy acrylate resin with paint was 73.8 °, and the hydrophilicity was slightly poor. In comparative examples 2 and 3, no sulfonic acid group was introduced, and the resulting epoxy acrylate resin had a contact angle of water upon application exceeding 90 °, and had poor hydrophilicity.
The appearance of the epoxy acrylate resin prepared in examples 1-2 and comparative example 1 is shown in FIG. 1. It can be seen that the resin prepared from the sulfonate diol with the molecular weight of 500 is transparent in appearance, which indicates that the water solubility is better; the resin prepared from the sulfonate dihydric alcohol with the molecular weight of 1000 is opaque in appearance and is in an emulsion state with better fluidity; the resin prepared from the sulfonate diol with the molecular weight of 2000 is in a thicker emulsion state in appearance. This appearance state is consistent with the water contact angle test results in table 1, which shows that as the molecular weight of the sulfonate diol increases, the proportion of hydrophilic segments decreases, resulting in a decrease in water solubility and poor hydrophilicity of the resin.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (9)

1. A sulfonate type epoxy acrylate resin is characterized by having a structure shown as a formula (I):
Figure FDA0003626673380000011
wherein R is1Is one or more of the following structures:
Figure FDA0003626673380000012
R2is H or CH3(ii) a n is a positive integer of 1-3.
2. The sulfonate type epoxy acrylate resin according to claim 1 wherein R is1Is composed of
Figure FDA0003626673380000013
3. The method for producing a sulfonate type epoxy acrylate resin according to claim 1 or 2, comprising the steps of:
s1, mixing sulfonate dihydric alcohol and an anhydride compound, heating to 100-105 ℃ under a stirring condition, reacting for 1h, and monitoring the acid value of a reaction solution; the molecular weight of the sulfonate dihydric alcohol is 500-1000;
s2, when the acid value reaches a theoretical value, adding epoxy resin and a catalyst into the reaction liquid in S1, and reacting at 110-112 ℃ until the acid value is less than 5 mgKOH/g;
s3, adding blocked acrylic acid dissolved with a polymerization inhibitor into the reaction liquid in the S2, and reacting at the temperature of 115-118 ℃ until the acid value is less than 5mgKOH/g to obtain the sulfonate type epoxy acrylate resin.
4. The method according to claim 3, wherein the water content of the sulfonate diol is less than 0.1%.
5. The preparation method according to claim 3, wherein the acid anhydride compound is one or more of succinic anhydride, phthalic anhydride or hexahydrophthalic anhydride.
6. The method according to claim 3, wherein the epoxy resin is a bisphenol A type epoxy resin and/or a bisphenol F type epoxy resin.
7. The preparation method according to claim 3, wherein the polymerization inhibitor is one or more of tert-butyl hydroquinone, p-hydroxyanisole or 2-methoxyhydroquinone.
8. The preparation method according to claim 3, wherein the mass ratio of the sulfonate diol, the anhydride compound, the epoxy resin, the catalyst, the polymerization inhibitor and the blocked acrylic acid is (25-55) to (5-12) to (18-40) to (0.3-0.5) to (0.05-0.08) to (3-8).
9. Use of the sulfonate type epoxy acrylate resin according to claim 1 or 2 for the preparation of an aqueous photocurable coating.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4379872A (en) * 1980-08-22 1983-04-12 Nippon Paint Co., Ltd. Amphoteric amino sulfonate derivatives of epoxy resins
EP0098623A1 (en) * 1982-07-06 1984-01-18 Shell Internationale Researchmaatschappij B.V. 2-Hydroxypropane sulphonic acid derivatives; their preparation and curable compositions containing them
US5486580A (en) * 1994-11-02 1996-01-23 The Dow Chemical Company Mesogenic novolacs and resins
WO2004078822A1 (en) * 2003-03-04 2004-09-16 Ebara Corporation Amine-cured type epoxy resin electrolyte having a sulfonic acid group and method for preparation thereof
CN101052919A (en) * 2004-11-01 2007-10-10 日产化学工业株式会社 Sulfonic-ester-containing composition for formation of antireflection film for lithography
CN107936225A (en) * 2017-11-01 2018-04-20 盐城安诺电泳涂料科技有限公司 A kind of thio salt modified epoxy and preparation method and application
CN110066400A (en) * 2019-04-26 2019-07-30 深圳职业技术学院 A kind of highly-water-soluble modified epoxy acrylate resin and preparation method thereof
CN111253547A (en) * 2020-01-21 2020-06-09 武汉工程大学 Sulfonate type ultraviolet-curing waterborne polyurethane and preparation method thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4379872A (en) * 1980-08-22 1983-04-12 Nippon Paint Co., Ltd. Amphoteric amino sulfonate derivatives of epoxy resins
EP0098623A1 (en) * 1982-07-06 1984-01-18 Shell Internationale Researchmaatschappij B.V. 2-Hydroxypropane sulphonic acid derivatives; their preparation and curable compositions containing them
US5486580A (en) * 1994-11-02 1996-01-23 The Dow Chemical Company Mesogenic novolacs and resins
WO2004078822A1 (en) * 2003-03-04 2004-09-16 Ebara Corporation Amine-cured type epoxy resin electrolyte having a sulfonic acid group and method for preparation thereof
CN101052919A (en) * 2004-11-01 2007-10-10 日产化学工业株式会社 Sulfonic-ester-containing composition for formation of antireflection film for lithography
CN107936225A (en) * 2017-11-01 2018-04-20 盐城安诺电泳涂料科技有限公司 A kind of thio salt modified epoxy and preparation method and application
CN110066400A (en) * 2019-04-26 2019-07-30 深圳职业技术学院 A kind of highly-water-soluble modified epoxy acrylate resin and preparation method thereof
CN111253547A (en) * 2020-01-21 2020-06-09 武汉工程大学 Sulfonate type ultraviolet-curing waterborne polyurethane and preparation method thereof

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