CN115850715A - Fluorine-containing hyperbranched polymer without PFOA (perfluorooctanoic acid), and preparation method and application thereof - Google Patents
Fluorine-containing hyperbranched polymer without PFOA (perfluorooctanoic acid), and preparation method and application thereof Download PDFInfo
- Publication number
- CN115850715A CN115850715A CN202211476592.5A CN202211476592A CN115850715A CN 115850715 A CN115850715 A CN 115850715A CN 202211476592 A CN202211476592 A CN 202211476592A CN 115850715 A CN115850715 A CN 115850715A
- Authority
- CN
- China
- Prior art keywords
- pfoa
- acid
- hyperbranched polymer
- fluorine
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Paints Or Removers (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a fluorine-containing hyperbranched polymer without PFOA (perfluorooctanoic acid), a preparation method and application thereof, which are mainly obtained by the reaction of the following components: (a) at least one hyperbranched polyester; (b) at least one hexafluoropropylene oxide polymer; (c) At least one saturated or unsaturated carboxylic acid containing from 6 to 22 carbon atoms; the PFOA-free fluorine-containing hyperbranched polymer has the number average molecular weight of 1000-18000, the acid value of less than 10mg KOH/g and the solid content of 20-100 percent. The polymer can enable the coating to have excellent wettability, shrinkage cavity and pinhole prevention performance on a substrate, enable the coating to be smooth and attractive, and simultaneously effectively prevent the formation of Bernedy vortex in the drying process of the coating, thereby avoiding the generation of surface defects such as orange peel and the like.
Description
Technical Field
The invention belongs to the technical field of fluorine modified leveling agents, and particularly relates to a fluorine-containing hyperbranched polymer without PFOA (perfluorooctanoic acid), and a preparation method and application thereof.
Background
The main functions of the coating are protection and decoration, and the surface state of the coating film has great influence on the two functions. The surface of the coating film often suffers from defects such as orange peel, cratering, waviness, floating color, brush marks, roll marks, sagging, and the like, which are related to the surface tension of the coating system, which is a major driving force for the flow and leveling of the coating film, so that it is necessary to control and adjust the surface tension of the coating film in order to control the surface state of the coating film.
The leveling agent is also called a surface state control agent, is a surface active substance capable of being directionally arranged on a liquid/air interface, is a substance with limited compatibility with a coating system, is easy to migrate to the surface of a coating film to form a low-surface-energy interface in the coating process, thereby controlling the surface state of the coating film, can promote the coating to form a flat, smooth and uniform coating film in the drying film-forming process, can effectively reduce the surface tension of the coating liquid, improve the leveling property and uniformity of the coating liquid, improve the permeability of the coating liquid, reduce the possibility of generating spots and marks in the brushing process, increase the coverage property, and enable the film-forming to be uniform and natural.
The existing leveling agent mainly comprises acrylate polymer, organic modified polysiloxane and fluorocarbon, wherein the organic silicon leveling agent does not have the surface state control capability, so the organic silicon leveling agent is basically not used in the leveling agent and is mostly used in the aspect of high temperature resistance; the acrylic leveling agent has strong leveling property and defoaming capability, does not influence interlayer adhesion, but has poor wettability of a base material and can not eliminate shrinkage cavity; the fluorine leveling agent has good substrate wettability and strong anti-shrinkage capability, but has poor defoaming capability and interlayer adhesion, so that the acrylic leveling agent modified by fluorine can complement the advantages and disadvantages of fluorine and acrylic acid.
It is known that the introduction of long-chain alkyl fluoride (C8) into a leveling agent can significantly improve the surface activity of a coating, reduce the surface tension of a liquid coating and its curing stage, and improve its leveling property. Since the typical long-chain perfluoroalkyl C8 compound gives ammonium Perfluorooctanoate (PFOA) under the environment, the compound is very difficult to degrade in the environment and has persistence, bioaccumulation and possibility of long-distance environmental migration, animal experiments have proved that the compound has reproductive toxicity and carcinogenicity and has been limited by the world's multi-national legislation. Therefore, the development of the leveling agent without PFOA is of great significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a fluorine-containing hyperbranched polymer without PFOA, the polymer does not contain PFOA and derivatives thereof, is more environment-friendly, has enough length of fluorocarbon chains, can be used as a leveling agent and a shrinkage-proof agent in coating and printing ink, and has good slip property, shrinkage-proof property and substrate wetting effect.
In order to achieve the purpose, the invention provides the following technical scheme:
a fluorine-containing hyperbranched polymer without PFOA is obtained by the reaction of the following components:
(a) At least one hyperbranched polyester;
(b) At least one hexafluoropropylene oxide polymer;
(c) At least one saturated or unsaturated carboxylic acid containing from 6 to 22 carbon atoms;
the PFOA-free fluorine-containing hyperbranched polymer has the number average molecular weight of 1000-18000, the acid value of less than 10mg KOH/g and the solid content of 20-100 percent.
Preferably, the molecular chain of the hyperbranched polyester has at least 6 hydroxyl functional groups, and the hydroxyl value of the molecular chain is more than 180mg KOH/g.
Preferably, the hydroxyl functional groups comprise primary and secondary hydroxyl groups.
Preferably, the structural formula of the component (b) is as follows:
wherein n is an integer between 1 and 5.
More preferably, the component (b) is one or more of hexafluoropropylene oxide dimer, hexafluoropropylene oxide trimer and hexafluoropropylene oxide tetramer.
Preferably, the component (c) is one or more of saturated fatty acid or unsaturated fatty acid.
More preferably, the component (c) is one or more of coconut oil acid, soya oil acid, palmitoleic acid, linoleic acid and stearic acid.
Preferably, the component (a) is 40-90 parts, the component (b) is 1-30 parts, and the component (c) is 10-30 parts by weight.
The invention also discloses a preparation method of the fluorine-containing hyperbranched polymer without PFOA, which comprises the following steps:
s1, dissolving the component (a) in a solvent, and adding an acid-binding agent to obtain a solution A; then, dropwise adding the component (B) into the solution A, after dropwise adding, carrying out chromatographic tracking on hexafluoropropylene oxide polymer to completely react, and filtering to remove salt to obtain a product B;
s2, adding the component (c) and a catalyst into the product B obtained in the step S1, carrying out esterification reaction until the acid value is less than 10mg KOH/g, thus obtaining the fluorine-containing hyperbranched polymer without PFOA, and finally adding butyl acetate to obtain a product with 20-100% of solid content.
Preferably, the acid-binding agent in step S1 is one or more of triethylamine, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
Preferably, the catalyst in step S2 is one or more of concentrated sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, and o-cresolsulfonic acid.
The invention also protects the application of the fluorine-containing hyperbranched polymer without PFOA as a leveling agent in coating, printing ink or plastics.
Compared with the prior art, the invention has the following beneficial effects:
(1) The fluorine-containing hyperbranched polymer without PFOA prepared by the invention has a hyperbranched structure, so that the fluidity and the dispersibility of the leveling agent can be improved, the prepared leveling agent can be uniformly dispersed in the coating, the high dispersion performance of the coating is realized, and the coating is more uniformly dispersed; meanwhile, fluorine atoms also have the characteristic of low polarizability, electron clouds can be tightly close to the peripheries of the fluorine atoms, the binding force between electrostatic acting forces is reduced, so that the cohesive force between C and F is small, the fluorine atoms are easy to migrate from the inside to the outside under the action of temperature and the like, the surface tension of a polymer is small, the leveling performance of a coating fluid is improved, the surface tension of a coating is uniform, a uniform interface is formed on the coating, and shrinkage cavities on the surface of the coating are reduced. In addition, the hexafluoropropylene oxide polymer contains more trifluoromethyl, the capability of reducing the surface tension of the hexafluoropropylene oxide polymer is higher than that of difluoroethyl, the hexafluoropropylene oxide polymer has excellent leveling property and shrinkage-proof performance, and the generated hyperbranched product has stable and uniform structure, so that the thermal stability and the aging resistance of the surface of the prepared coating are uniform.
(2) The fluorine-containing hyperbranched polymer without PFOA prepared by the invention can enable the coating to have excellent wettability, anti-shrinkage and anti-pinhole performances on a substrate, enable the coating to be smooth and attractive, and simultaneously can effectively prevent the formation of Benard vortex in the drying process of the coating, thereby avoiding the generation of surface defects such as orange peel and the like.
(3) The fluorine-containing hyperbranched polymer without PFOA prepared by the invention can be in a solid form, can also be dissolved in an organic solvent or water, and can also be dissolved in water after neutralization. The polymer is added into an organic solvent type coating system and a water-based coating system, and can also be prepared into a powder leveling agent together with an inorganic carrier, such as carbon dioxide, diatomite or alumina, and the like, and the powder leveling agent is added into a powder coating to play a role in leveling, shrinkage cavity prevention or (and) substrate wetting.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The hyperbranched polyester is purchased from an Oncuan novel carbon material Changzhou limited company, the average hydroxyl number is 6-24, and the hydroxyl value is 400-700mg KOH/g; the hexafluoropropylene oxide dimer, the hexafluoropropylene oxide trimer and the hexafluoropropylene oxide tetramer are all purchased from Guangdong Wengjiang chemical reagent, inc., wherein, the hexafluoropropylene oxide dimer CAS 2062-98-8; hexafluoropropylene oxide trimer CAS 2641-34-1; hexafluoropropylene oxide tetramer CAS 27639-98-1;
all commodities are purchased through market channels unless specially stated.
Example 1
A preparation method of the fluorine-containing hyperbranched polymer without PFOA comprises the following steps:
s1, dissolving 70g of hyperbranched polyester (the average hydroxyl number is 11, and the hydroxyl value is 520mg KOH/g) in 300mL of acetone, adding 30mL of triethylamine, and uniformly stirring to obtain a solution A; then, 20g of hexafluoropropylene oxide dimer is dripped into the solution A, after the dripping is finished, the reaction is carried out at 50 ℃, the hexafluoropropylene oxide dimer is tracked by a chromatograph and completely reacted, the salt is removed by filtration, and the solvent is removed by vacuumizing to obtain a product B;
s2, adding 20g of coconut oleic acid and 3g of p-toluenesulfonic acid into the product B obtained in the step S1, carrying out esterification reaction at 80 ℃, reacting until the acid value is less than 10mg KOH/g to obtain the PFOA-free fluorine-containing hyperbranched polymer, and finally adding butyl acetate to obtain a product with 70% of solid content.
The prepared fluorine-containing hyperbranched polymer without PFOA has the number average molecular weight of 13000 and the acid value of 8mg KOH/g.
Example 2
A preparation method of the fluorine-containing hyperbranched polymer without PFOA comprises the following steps:
s1, dissolving 60g of hyperbranched polyester (the average hydroxyl number is 6, and the hydroxyl value is 240mg KOH/g) in 300mL of butanone, adding 20g of sodium carbonate, and uniformly stirring to obtain a solution A; then dropwise adding 15g of hexafluoropropylene oxide trimer into the solution A, reacting at 75 ℃ after dropwise adding, tracking the hexafluoropropylene oxide trimer by a chromatograph to completely react, filtering to remove salt, and vacuumizing to remove the solvent to obtain a product B;
s2, adding 15g of soya-bean oil acid and 2g of methanesulfonic acid into the product B obtained in the step S1, carrying out esterification reaction at 90 ℃, reacting until the acid value is less than 10mg KOH/g to obtain the PFOA-free fluorine-containing hyperbranched polymer, and finally adding butyl acetate to obtain a product with a solid content of 60%.
The prepared fluorine-containing hyperbranched polymer without PFOA has the number average molecular weight of 10000 and the acid value of 5mg KOH/g.
Example 3
A preparation method of the fluorine-containing hyperbranched polymer without PFOA comprises the following steps:
s1, dissolving 40g of hyperbranched polyester (the average hydroxyl number is 22, and the hydroxyl value is 670mg KOH/g) in 300mL of acetone, adding 25g of sodium bicarbonate, and uniformly stirring to obtain a solution A; then dripping 1g of hexafluoropropylene oxide tetramer into the solution A, reacting at 50 ℃ after dripping, tracking the hexafluoropropylene oxide tetramer by a chromatograph to react completely, filtering to remove salt, and vacuumizing to remove the solvent to obtain a product B;
s2, adding 10g of linoleic acid and 1g of concentrated sulfuric acid into the product B obtained in the step S1, carrying out esterification reaction at 70 ℃, reacting until the acid value is less than 10mg KOH/g to obtain the PFOA-free fluorine-containing hyperbranched polymer, and finally adding butyl acetate to obtain a product with a solid content of 50%.
The prepared fluorine-containing hyperbranched polymer without PFOA has the number average molecular weight of 6000 and the acid value of 7mg KOH/g.
Example 4
A preparation method of the fluorine-containing hyperbranched polymer without PFOA comprises the following steps:
s1, dissolving 80g of hyperbranched polyester (the average hydroxyl number is 11, and the hydroxyl value is 520mg KOH/g) in 300mL of butanone, adding 25g of potassium carbonate, and uniformly stirring to obtain a solution A; dropwise adding 25g of hexafluoropropylene oxide trimer into the solution A, reacting at 75 ℃ after dropwise adding, tracking by a chromatograph that the hexafluoropropylene oxide trimer is completely reacted, filtering to remove salt, and vacuumizing to remove the solvent to obtain a product B;
s2, adding 25g of palmitoleic acid and 4g of p-toluenesulfonic acid into the product B obtained in the step S1, performing esterification reaction at 90 ℃, reacting until the acid value is less than 10mg KOH/g to obtain the PFOA-free fluorine-containing hyperbranched polymer, and finally adding butyl acetate to obtain a product with 70% of solid content.
The prepared PFOA-free fluorine-containing hyperbranched polymer has the number average molecular weight of 9000 and the acid value of 6mg KOH/g.
Example 5
A preparation method of the fluorine-containing hyperbranched polymer without PFOA comprises the following steps:
s1, dissolving 90g of hyperbranched polyester (the average hydroxyl number is 6, and the hydroxyl value is 240mg KOH/g) in 300mL of butanone, adding 20g of potassium bicarbonate, and uniformly stirring to obtain a solution A; then dripping 30g of hexafluoropropylene oxide dimer into the solution A, reacting at 75 ℃ after dripping, tracking the hexafluoropropylene oxide dimer by a chromatograph to completely react, filtering to remove salt, and vacuumizing to remove the solvent to obtain a product B;
s2, adding 30g of stearic acid and 5g of o-cresol sulfonic acid into the product B obtained in the step S1, carrying out esterification reaction at 100 ℃, reacting until the acid value is less than 10mg KOH/g to obtain the PFOA-free fluorine-containing hyperbranched polymer, and finally adding butyl acetate to obtain a product with the solid content of 80%.
The prepared PFOA-free fluorine-containing hyperbranched polymer has the number average molecular weight of 15000 and the acid value of 8mg KOH/g.
Application example: the polymer products prepared in examples 1-5 were used as leveling agents in paints, respectively, and the specific steps were as follows:
60g of hydroxyl acrylic resin (trade name is Hypomer FS-2050), 6g of xylene, 6g of propylene glycol monomethyl ether acetate (PMA) and 0.2g of a leveling agent (prepared in examples 1-5) are put into a clamping and oscillating oil mixer to oscillate for 15min, then 80g of diisocyanate (trade name is HDI HT 100) is added to prepare a curable varnish, the prepared varnish is coated on the surface of steel and iron, baked and cured for 15min at 50-60 ℃, and the leveling effect of the leveling agent is evaluated in terms of leveling speed of the coating, flatness of a coating plane and the like in each brushing process, and the leveling agent is evaluated for 1-5 grades, wherein the leveling property of 1 grade is the worst, and the leveling property of 5 grades is the best. Meanwhile, observing the affinity and the binding power of the coating on the surface of the first coating when painting for the second time, evaluating the re-painting effect of the coating according to whether an obvious interface exists between the two coatings, the strength of the binding power between the coatings and the like, and rating 1-5, wherein the 1 is the worst re-painting effect, and the 5 is the best re-painting effect, the result of which is shown in the table 1, meanwhile, a blank group without a leveling agent is arranged, the slip performance is represented by the friction coefficient value and is detected by an MXS-05A tin can coating surface slip performance tester, the gloss is tested by an XD-1050 gloss tester, and the test result is shown in the following table 1:
TABLE 1
| Leveling property | Overcoatability | Smoothness (coefficient of friction) | 60 ° gloss/%) | Degree of shrinkage | |
| Example 1 | 5 | 5 | 0.49 | 87 | 1 |
| Example 2 | 4 | 4 | 0.48 | 86 | 2 |
| Example 3 | 5 | 3 | 0.52 | 82 | 1 |
| Example 4 | 4 | 4 | 0.54 | 85 | 2 |
| Example 5 | 3 | 4 | 0.51 | 84 | 1 |
| Blank group | 2 | 2 | 0.66 | 74 | 7 |
The degree of shrinkage in Table 1 is rated on a scale of 1 to 10, with smaller numbers indicating better shrinkage resistance and correspondingly larger numbers indicating poor performance. As can be seen from the above table 1, the fluorine-containing hyperbranched polymer without PFOA prepared by the invention is used as a leveling agent in an oily coating, and the coating has good leveling property, recoatability and anti-shrinkage-cavity performance by adding a small amount of the fluorine-containing hyperbranched polymer, and the fluorine-containing chain segment of the hexafluoropropylene oxide polymer has a plurality of trifluoromethyl units, so that the fluorine-containing hyperbranched polymer has more excellent surface tension reducing capability, and further has more excellent anti-shrinkage-cavity performance. The finally prepared coating has good compatibility, leveling property and shrinkage prevention property, and has good application prospect.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A fluorine-containing hyperbranched polymer without PFOA is characterized by being obtained by the reaction of the following components:
(a) At least one hyperbranched polyester;
(b) At least one hexafluoropropylene oxide polymer;
(c) At least one saturated or unsaturated carboxylic acid containing from 6 to 22 carbon atoms;
the PFOA-free fluorine-containing hyperbranched polymer has the number average molecular weight of 1000-18000, the acid value of less than 10mg KOH/g and the solid content of 20-100 percent.
2. The PFOA-free fluorinated hyperbranched polymer according to claim 1, wherein the molecular chain of the hyperbranched polyester has at least 6 hydroxyl functional groups and a hydroxyl value of more than 180mg KOH/g.
3. The PFOA-free fluorinated hyperbranched polymer according to claim 2 wherein the hydroxyl functional groups comprise primary and secondary hydroxyl groups.
4. The PFOA-free fluorinated hyperbranched polymer according to claim 1, wherein the structural formula of the component (b) is as follows:
wherein n is an integer between 1 and 5.
5. The PFOA-free fluorinated hyperbranched polymer as claimed in claim 1, wherein the component (c) is one or more of coconut oleic acid, soya oleic acid, palmitoleic acid, linoleic acid and stearic acid.
6. The PFOA-free fluorinated hyperbranched polymer according to claim 1, wherein the component (a) is 40-90 parts, the component (b) is 1-30 parts, and the component (c) is 10-30 parts by weight.
7. A process for the preparation of fluorinated hyperbranched polymers free of PFOA according to any one of claims 1 to 6, characterized in that it comprises the following steps:
s1, dissolving the component (a) in a solvent, and adding an acid-binding agent to obtain a solution A; then, dropwise adding the component (B) into the solution A, after dropwise adding, carrying out chromatographic tracking on hexafluoropropylene oxide polymer to completely react, and filtering to remove salt to obtain a product B;
s2, adding the component (c) and a catalyst into the product B obtained in the step S1, carrying out esterification reaction until the acid value is less than 10mg KOH/g, thus obtaining the fluorine-containing hyperbranched polymer without PFOA, and finally adding butyl acetate to obtain a product with 20-100% of solid content.
8. The preparation method of claim 7, wherein the acid-binding agent in step S1 is one or more of triethylamine, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
9. The preparation method according to claim 7, wherein the catalyst in step S2 is one or more of concentrated sulfuric acid and sulfonic acid.
10. Use of a PFOA-free fluorinated hyperbranched polymer as defined in any one of claims 1 to 6 as a levelling agent in coatings, inks or plastics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211476592.5A CN115850715B (en) | 2022-11-23 | 2022-11-23 | Fluorine-containing hyperbranched polymer without PFOA (PFOA), and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211476592.5A CN115850715B (en) | 2022-11-23 | 2022-11-23 | Fluorine-containing hyperbranched polymer without PFOA (PFOA), and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115850715A true CN115850715A (en) | 2023-03-28 |
| CN115850715B CN115850715B (en) | 2023-09-22 |
Family
ID=85665523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211476592.5A Active CN115850715B (en) | 2022-11-23 | 2022-11-23 | Fluorine-containing hyperbranched polymer without PFOA (PFOA), and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115850715B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002249706A (en) * | 2001-02-27 | 2002-09-06 | Dainippon Ink & Chem Inc | Coating composition |
| CN1687180A (en) * | 2005-03-18 | 2005-10-26 | 上海瀛正科技有限公司 | Method for preparing super branched polyacrylate fluorine and application in finishing agent for textile |
| CN105482680A (en) * | 2016-01-06 | 2016-04-13 | 天津科技大学 | Ultraviolet light polymerization hyperbranched perfluoropolyether urethane acrylate coating |
| CN107964063A (en) * | 2017-09-29 | 2018-04-27 | 三明学院 | A kind of polymer without PFOA and preparation method thereof, purposes |
| CN108531061A (en) * | 2018-04-12 | 2018-09-14 | 太仓中化环保化工有限公司 | A kind of powdery paints and its preparation method and application |
| US20220204760A1 (en) * | 2020-12-31 | 2022-06-30 | Rohm And Haas Electronic Materials Llc | Polymers useful as surface leveling agents |
-
2022
- 2022-11-23 CN CN202211476592.5A patent/CN115850715B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002249706A (en) * | 2001-02-27 | 2002-09-06 | Dainippon Ink & Chem Inc | Coating composition |
| CN1687180A (en) * | 2005-03-18 | 2005-10-26 | 上海瀛正科技有限公司 | Method for preparing super branched polyacrylate fluorine and application in finishing agent for textile |
| CN105482680A (en) * | 2016-01-06 | 2016-04-13 | 天津科技大学 | Ultraviolet light polymerization hyperbranched perfluoropolyether urethane acrylate coating |
| CN107964063A (en) * | 2017-09-29 | 2018-04-27 | 三明学院 | A kind of polymer without PFOA and preparation method thereof, purposes |
| CN108531061A (en) * | 2018-04-12 | 2018-09-14 | 太仓中化环保化工有限公司 | A kind of powdery paints and its preparation method and application |
| US20220204760A1 (en) * | 2020-12-31 | 2022-06-30 | Rohm And Haas Electronic Materials Llc | Polymers useful as surface leveling agents |
Non-Patent Citations (2)
| Title |
|---|
| ZILIN MENG，等: "Perfluoro octanoic acid–modified magnetic hyperbranched polyamideamine as a sorbent for the extraction of fluorine-containing pesticides from water samples", 《JOURNAL OF SEPARATION SCIENCE》, vol. 44, no. 20, pages 3830 - 3839 * |
| 史雅娜，等: "具有"树枝状"结构的短氟碳链含氟单体的合成与表征", 《高分子材料科学与工程》, vol. 34, no. 12, pages 25 - 30 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115850715B (en) | 2023-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108624197B (en) | Water-based finishing oil for coiled materials and preparation method thereof | |
| CN110982371A (en) | Environment-friendly water-based high-gloss high-fullness high-temperature baking varnish | |
| CN102585667B (en) | Hydrophilic ultraviolet light curing coating and preparation method thereof | |
| CN110698963A (en) | High-wear-resistance water-based acrylic acid-polyurethane two-component finish paint | |
| CN111303741A (en) | High-film-thickness waterborne polyurethane long-acting anticorrosive paint for wind power and petrochemical equipment and preparation method thereof | |
| CN110760223A (en) | Water-based single-color paint and preparation method thereof | |
| CN106479295A (en) | A kind of high-performance environment protection type aqueouss bicycle coating and preparation method thereof | |
| CN113234368A (en) | Water-based acrylic coating composition and preparation method thereof | |
| CN112940203A (en) | Organosilicon modified acrylic acid secondary dispersion and preparation method thereof | |
| CN112457764A (en) | Ultraviolet curing coating without thickening and preparation method thereof | |
| CN111019038A (en) | Water-based acrylic resin with high acid and alkali resistance and preparation method thereof | |
| CN110746870A (en) | High-performance water-based acrylic polyurethane two-component coating | |
| CN115850715A (en) | Fluorine-containing hyperbranched polymer without PFOA (perfluorooctanoic acid), and preparation method and application thereof | |
| CN113512325A (en) | Water-based fluorocarbon matte coating and preparation method thereof | |
| CA2281433C (en) | Polyacrylates and their use as degassing agents for paints and coatings | |
| CN1106406C (en) | Acrylic polymer composition | |
| CN111574915A (en) | Water-dispersible alkyd resin coating and preparation method thereof | |
| CN114106648B (en) | Water-based single-component primer surfacer and preparation method and application thereof | |
| CN113930152B (en) | Water-based organic silicon high-temperature-resistant coating and preparation method thereof | |
| CN111925677B (en) | Ultraviolet-curable high-temperature-resistant coating for reflecting cover of illumination metal plate and preparation method thereof | |
| CN114686069B (en) | Polyacrylate resin modified waterborne epoxy emulsion and preparation method thereof | |
| CN114940724A (en) | Modified hydroxyl acrylic acid dispersion and preparation method thereof | |
| CN109280154B (en) | Self-emulsifying water-based low-temperature epoxy resin curing agent based on heterocyclic compound | |
| CN115537089A (en) | Reflective film UV printing primer, preparation method thereof and reflective film | |
| CN114853982B (en) | Water-based UV (ultraviolet) curing epoxy acrylate resin as well as preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |