CN110627966A - Low-surface-tension rare-earth functionalized water-based acrylic resin and preparation method thereof - Google Patents
Low-surface-tension rare-earth functionalized water-based acrylic resin and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a low surface tension rare earth functionalized water-based acrylic resin which is composed of an acrylic soft monomer, an acrylic hard monomer, hydroxyethyl acrylate, polyisocyanate, a fluorine alkene monomer, a hydroxyl Schiff base monomer, a rare earth solution, a sodium ethoxide ethanol solution, absolute ethyl alcohol, acrylic acid, azodiisobutyronitrile, an emulsifier, a neutralizer and deionized water; the adopted acrylate monomers have no methyl at one end of a double bond, so that the steric hindrance of polymerization reaction is reduced, and the influence of the methyl on the coordination of rare earth ions is reduced; the low surface tension rare earth functionalized water-based acrylic resin prepared by the invention has good adhesive force, good electromagnetic shielding performance, wear resistance, long luminescence afterglow time and the like; high cost performance and wide application, and may be used in inner and outer wall paint, luminous paint, electromagnetic shielding paint, etc.
Description
Technical Field
The invention relates to a modified water-based acrylic resin, in particular to a low-surface-tension rare-earth functionalized water-based acrylic resin and a preparation method thereof, belonging to the technical field of functional resins.
Background
For years, the development of the acrylic resin industry in China is rapid, the product output is continuously expanded, the development of the acrylic resin industry to high-technology products is encouraged by national industry policies, and the investment of newly-increased investment projects of domestic enterprises is gradually increased. The attention of investors to the acrylic resin industry is becoming more and more intense, which increases the need for developing research in the acrylic resin industry. At present, the variety of acrylic resin in China is relatively perfect, but compared with the advanced operation in foreign countries, products with certain production scale, process control and part of special performance requirements have certain gaps, along with increasingly fierce market competition, the profit of the general acrylic resin continuously falls, under the condition, the profit of the acrylic product is required to be enlarged, and no one has but has the advantages of people and self only by researching and developing high-performance special products. Only in this way, the competitive power of the product participating in the market can be really improved, and the comprehensive benefit of the enterprise can be improved.
With the development of science and technology, materials with single property can not meet the needs of people, and the combination, low-dimensional and intelligentization are the trend of modern material development and the urgent needs of information technology development. By the function composition, performance complementation and optimization of two or more materials, the hybrid material with excellent performance can be prepared. Therefore, organic-inorganic polymer resin hybrid materials having the advantages of both inorganic and organic materials are gradually being regarded as important. The structure of the polymer material determines the performance, the control and modification of the structure, the availability of materials with different performances, the unique structure and easy modification of the polymer, the easy processing and other characteristics, so that the polymer material has incomparable superiority and irreplaceability compared with other materials, and is widely applied to various scientific fields.
The rare earth ions are directly connected with the high polymer material by coordination bonds, the rare earth complex is widely applied to the fields of luminescence and display by the unique fluorescence characteristic, and particularly the development prospect of preparing the functional polymer material by compounding the rare earth complex in a polymer matrix is more remarkable. However, the use of the light emitting material in which the rare earth complex is simply doped into the polymer matrix is limited due to its inherent disadvantages.
Chinese patent CN102304201A discloses a preparation method of rare earth functionalized polymer composite luminescent resin, and particularly relates to a preparation method of rare earth functionalized polymer composite luminescent resin. The method comprises the steps of firstly synthesizing high molecular resin by adopting an organic synthesis method, designing and constructing a functional organic connector on a molecular level, introducing a luminous rare earth complex into the high molecular resin by the functional organic connector in a covalent bond mode, then bonding and assembling the luminous rare earth complex into a rare earth functional high molecular resin compound, and finally forming the obtained complex into xerogel by adopting a hydrolysis-copolycondensation sol method, so that an organic ligand containing amino is embedded into a high molecular resin matrix under the action of a coordination bond, and thus the high molecular resin composite material with stable chemical and thermodynamic properties, regular surface appearance and characteristic fluorescence emission is obtained. The invention adopts rare earth complex to graft in the polymer resin, the reaction process is more complex, and the rare earth ions are easy to be coated, thus influencing the energy transfer between the polymer resin and the rare earth ions, and simultaneously the surface tension of the polymer resin is larger, thus being easy to be polluted by pollutants, thus influencing the performance of the polymer resin.
Therefore, the invention develops an organic-inorganic water-based resin which has low surface tension and good energy transfer efficiency between rare earth ions and high polymer resin, and the rare earth ions are directly matched on the high polymer resin to form the organic-inorganic water-based resin, thereby having good economic value and meeting the development requirement of environmental protection.
Disclosure of Invention
The rare earth element has abundant fluorescence characteristics due to the unique electronic structure, so that the rare earth material is determined to show unique properties in the aspects of electricity, magnetism and the like. However, since the 4f transition of the rare earth metal ion belongs to forbidden transition, the absorption coefficient in the ultraviolet region is small, and the capability of exciting energy is weak, the luminous intensity is generally low, and then the research on various rare earth organic complexes finds that: the organic ligand can realize effective energy transfer to the rare earth ions by absorbing energy, excite the rare earth ions to emit characteristic fluorescence, and have good monochromaticity of luminescence.
Besides the application significance of general compounds, the Schiff base also has unique biological activity different from other structures, and meanwhile, the Schiff base compound can form a stable complex with rare earth ions due to the fact that the Schiff base compound contains C = N double bonds.
Therefore, the technical problem to be solved by the invention is to overcome the defects of poor durability, easy elution, easy coating and the like of physically adding rare earth ions and grafting the rare earth ions on the high polymer resin.
In order to solve the technical problems, the invention firstly synthesizes the aqueous acrylic resin containing Schiff base structure, then the rare earth ions are directly introduced into the aqueous acrylic resin, and the Schiff base structure is positioned at the two ends of the acrylic resin, thereby effectively solving the defect that the rare earth ions are coated by the high polymer resin; in order to solve the problems that the energy transfer between the polymer resin and the rare earth ions is influenced because the coating is easily polluted by pollutants, and the like, the fluorine element with low surface tension is introduced, so that the surface tension of the coating is effectively reduced, and the pollutants are difficult to attach to the surface.
The invention aims to provide a low-surface tension rare earth functionalized water-based acrylic resin.
The invention also provides a preparation method of the low surface tension rare earth functionalized water-based acrylic resin.
In order to solve the technical problems, the invention adopts the following technical scheme: the invention relates to a low surface tension rare earth functionalized water-based acrylic resin which comprises the following components in parts by weight: 5.0-8.0 parts of acrylic acid soft monomer, 8.0-15.0 parts of acrylic acid hard monomer, 2.0-5.5 parts of hydroxyethyl acrylate, 3.0-6.0 parts of polyisocyanate, 2.0-5.0 parts of vinyl monomer, 2.5-5.0 parts of hydroxyl Schiff base monomer, 0.4-1.5 parts of rare earth solution, 0.5-2.0 parts of sodium ethoxide ethanol solution, 0.5-3.0 parts of absolute ethyl alcohol, 2.5-4.5 parts of acrylic acid, 0.4-1.0 part of azodiisobutyronitrile, 1.5-3.0 parts of emulsifier, 1.0-4.0 parts of neutralizer and 42.0-65.0 parts of deionized water.
The adopted acrylate monomers do not contain methyl at one end of a double bond, so that the steric hindrance of polymerization reaction is reduced, and the influence of methyl on the coordination of rare earth ions is reduced.
The acrylic acid hard monomer is one or the combination of two of methyl acrylate and isobornyl acrylate.
The fluorine-containing alkene monomer is one or a combination of more of perfluorohexyl ethyl acrylate, perfluorohexyl ethyl methacrylate, perfluorooctyl ethyl acrylate, perfluorooctyl ethyl methacrylate, perfluoroalkyl ethyl acrylate and perfluoroalkyl ethyl methacrylate.
The acrylic acid soft monomer is one or a combination of butyl acrylate, isooctyl acrylate, cyclohexyl acrylate, lauryl acrylate and stearyl acrylate.
The polyisocyanate is one or a combination of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate and tetramethyl xylylene diisocyanate.
The rare earth solution is 0.1 mol.L-1Eu (NO)3)3Ethanol solution, Tb (NO)3)3Ethanol solution, Sm (NO)3)3Ethanol solution, Ho (NO)3)3One or more of ethanol solution.
The molar concentration of the sodium ethoxide ethanol solution is 0.5 mol.L-1Sodium ethoxide ethanol solution.
The neutralizing agent is at least one of triethylamine, ammonia water and dimethylethanolamine.
The invention provides a preparation method of a low-surface-tension rare earth functionalized water-based acrylic resin, which comprises the following steps:
a) adding part of acrylic acid soft monomers and acrylic acid hard monomers as solvents into a reaction kettle, heating to 78-80 ℃, adding hydroxyl Schiff base monomers, uniformly stirring, slowly adding polyisocyanate, stirring for reaction for 1.0-1.5 h, slowly dropwise adding hydroxyethyl acrylate, heating to 82-85 ℃, stirring for reaction for 2.5-2.5 h, detecting the NCO value, measuring the NCO value and the designed value, and cooling to 72-75 ℃. Adding absolute ethyl alcohol for reaction, consuming the residual NCO, cooling to room temperature, adding azobisisobutyronitrile, uniformly stirring, and placing in a metering tank G1 to obtain a reaction mixed solution I;
b) weighing the components according to the formula proportion, sequentially adding the rest acrylic acid soft monomer, the acrylic acid, the rest acrylic acid hard monomer, the fluorine alkene monomer and the azodiisobutyronitrile into a metering tank G2, and uniformly stirring to obtain a mixed solution II;
c) adding part of deionized water and an emulsifier into a reaction kettle, heating to 78-80 ℃ at a stirring speed of 100r/min, slowly adding 1/4 mixed solution II, reacting for 0.5h, then dropwise adding the rest mixed solution II at a constant speed, controlling the dropwise adding time to be 3.0-3.5 h, and controlling the temperature to be 76-80 ℃ in the dropwise adding process;
d) after the dropwise addition of the mixed solution II is finished, dropwise adding the mixed solution I at a constant speed, controlling the dropwise adding time to be 2.0-3.0 h, keeping the reaction at 80-82 ℃ for 2h after the dropwise addition is finished, cooling to 35-45 ℃ after the reaction is finished, adding a neutralizing agent and the rest deionized water, and stirring for 0.5h to obtain an intermediate III;
e) adding the intermediate III into a reaction kettle, heating to 60-65 ℃, then dropwise adding a rare earth solution, and adding 0.5 mol.L-1And slowly adjusting the pH value of the solution to 7.0-7.5 by using the sodium ethoxide ethanol solution, continuously reacting for 2 hours, stopping the reaction, and filtering to obtain the low-surface-tension rare earth functionalized water-based acrylic resin.
The low surface tension rare earth functionalized water-based acrylic resin prepared by the invention has good adhesive force, good electromagnetic shielding performance, good radiation resistance, long luminescence afterglow time and the like; high cost performance and wide application, and may be used in inner and outer wall paint, luminous paint, electromagnetic shielding paint, etc.
Detailed Description
The preparation of the low surface tension rare earth functionalized aqueous acrylic resin is further described with reference to the following examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
Example 1
A low surface tension rare earth functionalized water-based acrylic resin comprises the following steps:
a) adding 1.5 parts of butyl acrylate, 1.0 part of isooctyl acrylate and 2.0 parts of methyl acrylate as solvents into a reaction kettle, heating to 78-80 ℃, adding 3.8 parts of hydroxyl Schiff base monomer, uniformly stirring, slowly adding 5.4 parts of isophorone diisocyanate, stirring, reacting for 1.0-1.5 h, slowly dropwise adding 3.2 parts of hydroxyethyl acrylate, heating to 82-85 ℃, stirring, reacting for 2.5-2.5 h, detecting the NCO value, measuring the NCO value and the designed value, and cooling to 72-75 ℃. Adding 1.1 parts of absolute ethyl alcohol for reaction, consuming the residual NCO, cooling to room temperature, adding 0.3 part of azobisisobutyronitrile, uniformly stirring, and placing in a metering tank G1 to obtain a reaction mixed solution I;
b) weighing 2.5 parts of butyl acrylate, 2.0 parts of isooctyl acrylate, 8.5 parts of methyl acrylate, 3.2 parts of acrylic acid, 3.0 parts of perfluorohexyl ethyl methacrylate and 0.5 part of azobisisobutyronitrile according to the proportion of the formula, sequentially adding into a metering tank G2, and uniformly stirring to obtain a mixed solution II;
c) adding 20.0 parts of deionized water and 2.0 parts of emulsifier into a reaction kettle, heating to 78-80 ℃ at a stirring speed of 100r/min, slowly adding 1/4 mixed solution II, reacting for 0.5h, then dropwise adding the rest mixed solution II at a constant speed, controlling the dropwise adding time to be 3.0-3.5 h, and controlling the temperature to be 76-80 ℃ in the dropwise adding process;
d) after the dropwise addition of the mixed solution II is finished, dropwise adding the mixed solution I at a constant speed, controlling the dropwise adding time to be 2.0-3.0 h, keeping the reaction at 80-82 ℃ for 2h after the dropwise addition is finished, cooling to 35-45 ℃, adding 2.2 parts of a neutralizing agent and 35.9 parts of deionized water, and stirring for 0.5h to obtain an intermediate III;
e) adding the intermediate III intoHeating to 60-65 ℃ in a reaction kettle, and then dropwise adding Tb (NO)3)30.9 part of ethanol solution, 0.5 mol.L-1And slowly adjusting the pH value of the solution to 7.0-7.5 by 1.0 part of the sodium ethoxide ethanol solution, continuously reacting for 2 hours, stopping the reaction, and filtering to obtain the low-surface-tension rare earth functionalized water-based acrylic resin.
Example 2
A low surface tension rare earth functionalized water-based acrylic resin comprises the following steps:
a) adding 1.0 part of butyl acrylate, 1.0 part of lauryl acrylate and 2.5 parts of isobornyl acrylate as solvents into a reaction kettle, heating to 78-80 ℃, adding 3.6 parts of hydroxyl Schiff base monomer, uniformly stirring, slowly adding 5.2 parts of toluene diisocyanate, stirring, reacting for 1.0-1.5 h, slowly dropwise adding 3.1 parts of hydroxyethyl acrylate, heating to 82-85 ℃, stirring, reacting for 2.5-2.5 h, detecting the NCO value, measuring the NCO value and the designed value, and cooling to 72-75 ℃. Adding 1.4 parts of absolute ethyl alcohol for reaction, consuming the residual NCO, cooling to room temperature, adding 0.3 part of azobisisobutyronitrile, uniformly stirring, and placing in a metering tank G1 to obtain a reaction mixed solution I;
b) weighing 2.8 parts of butyl acrylate, 2.0 parts of lauryl acrylate, 9.0 parts of isobornyl acrylate, 3.8 parts of acrylic acid, 3.2 parts of perfluoroalkyl ethyl acrylate and 0.5 part of azobisisobutyronitrile according to the proportion of the formula, sequentially adding into a metering tank G2, and uniformly stirring to obtain a mixed solution II;
c) adding 20.0 parts of deionized water and 2.0 parts of emulsifier into a reaction kettle, heating to 78-80 ℃ at a stirring speed of 100r/min, slowly adding 1/4 mixed solution II, reacting for 0.5h, then dropwise adding the rest mixed solution II at a constant speed, controlling the dropwise adding time to be 3.0-3.5 h, and controlling the temperature to be 76-80 ℃ in the dropwise adding process;
d) after the dropwise addition of the mixed solution II is finished, dropwise adding the mixed solution I at a constant speed, controlling the dropwise adding time to be 2.0-3.0 h, keeping the reaction at 80-82 ℃ for 2h after the dropwise addition is finished, cooling to 35-45 ℃, adding 2.8 parts of neutralizing agent and 34.1 parts of deionized water, and stirring for 0.5h to obtain an intermediate III;
e) will be provided withAdding the intermediate III into a reaction kettle, heating to 60-65 ℃, and then dropwise adding Ho (NO)3)30.8 part of ethanol solution, 0.5 mol.L-1And slowly adjusting the pH value of the solution to 7.0-7.5 by 0.9 part of sodium ethoxide ethanol solution, continuously reacting for 2 hours, stopping the reaction, and filtering to obtain the low-surface-tension rare earth functionalized water-based acrylic resin.
Example 3
A low surface tension rare earth functionalized water-based acrylic resin comprises the following steps:
a) adding 1.2 parts of butyl acrylate, 1.3 parts of octadecyl acrylate and 2.5 parts of isobornyl acrylate into a reaction kettle as solvents, heating to 78-80 ℃, adding 4.0 parts of hydroxyl Schiff base monomer, uniformly stirring, slowly adding 5.4 parts of hexamethylene diisocyanate, stirring, reacting for 1.0-1.5 hours, slowly dropwise adding 3.6 parts of hydroxyethyl acrylate, heating to 82-85 ℃, stirring, reacting for 2.5-2.5 hours, detecting the NCO value, measuring the NCO value and the designed value, and cooling to 72-75 ℃. Adding 2.0 parts of absolute ethyl alcohol for reaction, consuming the residual NCO, cooling to room temperature, adding 0.3 part of azobisisobutyronitrile, uniformly stirring, and placing in a metering tank G1 to obtain a reaction mixed solution I;
b) weighing 3.0 parts of butyl acrylate, 1.5 parts of octadecyl acrylate, 10.0 parts of isobornyl acrylate, 4.0 parts of acrylic acid, 3.8 parts of perfluoroalkyl ethyl methacrylate and 0.5 part of azobisisobutyronitrile according to the proportion of the formula, adding into a metering tank G2, and uniformly stirring to obtain a mixed solution II;
c) adding 20.0 parts of deionized water and 2.0 parts of emulsifier into a reaction kettle, heating to 78-80 ℃ at a stirring speed of 100r/min, slowly adding 1/4 mixed solution II, reacting for 0.5h, then dropwise adding the rest mixed solution II at a constant speed, controlling the dropwise adding time to be 3.0-3.5 h, and controlling the temperature to be 76-80 ℃ in the dropwise adding process;
d) after the dropwise addition of the mixed solution II is finished, dropwise adding the mixed solution I at a constant speed, controlling the dropwise adding time to be 2.0-3.0 h, keeping the reaction at 80-82 ℃ for 2h after the dropwise addition is finished, cooling to 35-45 ℃, adding 3.4 parts of neutralizing agent and 28.9 parts of deionized water, and stirring for 0.5h to obtain an intermediate III;
e) adding the intermediate III into a reaction kettle, heating to 60-65 ℃, and then dropwise adding Eu (NO)3)3Ethanol solution 1.2 parts, 0.5 mol.L-1And slowly adjusting the pH value of the solution to 7.0-7.5 by 1.4 parts of sodium ethoxide ethanol solution, continuously reacting for 2 hours, stopping the reaction, and filtering to obtain the low-surface-tension rare earth functionalized water-based acrylic resin.
The examples of the invention are compared with the water-based acrylic resin (comparative examples) according to relevant standards of water resistance (GB/T1733-1993), adhesion (GB/T9286-1998), neutral salt fog resistance (GB/T1771-2007), contact angle (GB/T30693-2014), wear resistance (GB/T1768-2006), filiform corrosion (GB/T13452.4-92), radiation resistance (GB/T30142-2013) and the like, and the detected performance indexes are shown in Table 1.
Table 1: example comparison with aqueous acrylic resin Properties
Although the present invention has been described in detail and with reference to exemplary embodiments thereof, it will be apparent to one skilled in the art that various changes, modifications and variations can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (9)
1. A low surface tension rare earth functionalized water-based acrylic resin is characterized in that: the composition comprises the following components in parts by weight: 5.0-8.0 parts of acrylic acid soft monomer, 8.0-15.0 parts of acrylic acid hard monomer, 2.0-5.5 parts of hydroxyethyl acrylate, 3.0-6.0 parts of polyisocyanate, 2.0-5.0 parts of vinyl monomer, 2.5-5.0 parts of hydroxyl Schiff base monomer, 0.4-1.5 parts of rare earth solution, 0.5-2.0 parts of sodium ethoxide ethanol solution, 0.5-3.0 parts of absolute ethyl alcohol, 2.5-4.5 parts of acrylic acid, 0.4-1.0 part of azodiisobutyronitrile, 1.5-3.0 parts of emulsifier, 1.0-4.0 parts of neutralizer and 42.0-65.0 parts of deionized water;
the adopted acrylate monomers do not contain methyl at one end of a double bond, so that the steric hindrance of polymerization reaction is reduced, and the influence of methyl on the coordination of rare earth ions is reduced.
2. The low surface tension rare earth functionalized aqueous acrylic resin of claim 1, wherein: the acrylic acid hard monomer is one or the combination of two of methyl acrylate and isobornyl acrylate.
3. The low surface tension rare earth functionalized aqueous acrylic resin of claim 1, wherein: the fluorine-containing alkene monomer is one or a combination of more of perfluorohexyl ethyl acrylate, perfluorohexyl ethyl methacrylate, perfluorooctyl ethyl acrylate, perfluorooctyl ethyl methacrylate, perfluoroalkyl ethyl acrylate and perfluoroalkyl ethyl methacrylate.
4. The low surface tension rare earth functionalized aqueous acrylic resin of claim 1, wherein: the acrylic acid soft monomer is one or a combination of butyl acrylate, isooctyl acrylate, cyclohexyl acrylate, lauryl acrylate and stearyl acrylate.
5. The low surface tension rare earth functionalized aqueous acrylic resin of claim 1, wherein: the polyisocyanate is one or a combination of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate and tetramethyl xylylene diisocyanate.
6. The low surface tension rare earth functionalized aqueous acrylic resin of claim 1, wherein: the rare earth solution is 0.1 mol.L-1Eu (NO)3)3Ethanol solution, Tb (NO)3)3Ethanol solution, Sm (NO)3)3Ethanol solution, Ho (NO)3)3One or more of ethanol solution.
7. The low surface tension rare earth functionalized aqueous acrylic resin of claim 1, wherein: the molar concentration of the sodium ethoxide ethanol solution is 0.5 mol.L-1Sodium ethoxide ethanol solution.
8. The low surface tension rare earth functionalized aqueous acrylic resin of claim 1, wherein: the neutralizing agent is at least one of triethylamine, ammonia water and dimethylethanolamine.
9. The method for preparing the low surface tension rare earth functionalized aqueous acrylic resin according to claim 1, wherein the method comprises the following steps: the preparation process comprises the following steps:
a) adding part of acrylic acid soft monomers and acrylic acid hard monomers serving as solvents into a reaction kettle, heating to 78-80 ℃, adding hydroxyl Schiff base monomers, uniformly stirring, slowly adding polyisocyanate, stirring for reaction for 1.0-1.5 h, slowly dropwise adding hydroxyethyl acrylate, heating to 82-85 ℃, stirring for reaction for 2.5-2.5 h, detecting an NCO value, measuring the NCO value and a design value, cooling to 72-75 ℃, adding absolute ethyl alcohol for reaction, consuming the rest NCO, cooling to room temperature, adding azobisisobutyronitrile, uniformly stirring, placing in a metering tank G1, and obtaining a reaction mixed solution I;
b) weighing the components according to the formula proportion, sequentially adding the rest acrylic acid soft monomer, the acrylic acid, the rest acrylic acid hard monomer, the fluorine alkene monomer and the azodiisobutyronitrile into a metering tank G2, and uniformly stirring to obtain a mixed solution II;
c) adding part of deionized water and an emulsifier into a reaction kettle, heating to 78-80 ℃ at a stirring speed of 100r/min, slowly adding 1/4 mixed solution II, reacting for 0.5h, then dropwise adding the rest mixed solution II at a constant speed, controlling the dropwise adding time to be 3.0-3.5 h, and controlling the temperature to be 76-80 ℃ in the dropwise adding process;
d) after the dropwise addition of the mixed solution II is finished, dropwise adding the mixed solution I at a constant speed, controlling the dropwise adding time to be 2.0-3.0 h, keeping the reaction at 80-82 ℃ for 2h after the dropwise addition is finished, cooling to 35-45 ℃ after the reaction is finished, adding a neutralizing agent and the rest deionized water, and stirring for 0.5h to obtain an intermediate III;
e) adding the intermediate III into a reaction kettle, heating to 60-65 ℃, then dropwise adding a rare earth solution, and adding 0.5 mol.L-1And slowly adjusting the pH value of the solution to 7.0-7.5 by using the sodium ethoxide ethanol solution, continuously reacting for 2 hours, stopping the reaction, and filtering to obtain the low-surface-tension rare earth functionalized water-based acrylic resin.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112646084A (en) * | 2020-12-18 | 2021-04-13 | 合众（佛山）化工有限公司 | Tripolyindenone derivative modified waterborne acrylic resin and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432756A (en) * | 2011-09-09 | 2012-05-02 | 中科院广州化学有限公司 | Linear polymer rare-earth complex capable of emitting near infrared light, and preparation method and application |
| CN105461849A (en) * | 2015-12-28 | 2016-04-06 | 重庆市环境科学研究院 | Preparation method of hydrophobic oleophilic resin and application of hydrophobic oleophilic resin in oil-water separation material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432756A (en) * | 2011-09-09 | 2012-05-02 | 中科院广州化学有限公司 | Linear polymer rare-earth complex capable of emitting near infrared light, and preparation method and application |
| CN105461849A (en) * | 2015-12-28 | 2016-04-06 | 重庆市环境科学研究院 | Preparation method of hydrophobic oleophilic resin and application of hydrophobic oleophilic resin in oil-water separation material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112646084A (en) * | 2020-12-18 | 2021-04-13 | 合众（佛山）化工有限公司 | Tripolyindenone derivative modified waterborne acrylic resin and preparation method thereof |
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Application publication date: 20191231 |