CN110357996B - Polymer used as leveling agent and preparation method and application thereof - Google Patents
Polymer used as leveling agent and preparation method and application thereof Download PDFInfo
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- CN110357996B CN110357996B CN201910702088.4A CN201910702088A CN110357996B CN 110357996 B CN110357996 B CN 110357996B CN 201910702088 A CN201910702088 A CN 201910702088A CN 110357996 B CN110357996 B CN 110357996B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F130/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F130/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F130/08—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/47—Levelling agents
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
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Abstract
The invention relates to a polymer used as a leveling agent, a preparation method and application thereof, wherein hexafluoropropylene oxide is reacted with an acrylic monomer to obtain an intermediate; reacting the intermediate with an alkoxy silane monomer to obtain an alkoxy silane fluorine-containing acrylate monomer; under the action of an initiator, the alkoxy silane fluorine-containing acrylate monomer adopts an atom transfer radical polymerization method to further obtain the polyalkoxy silane fluorine-containing acrylate. The siloxane-based polymer has smooth property and can be used as a leveling agent of paint and ink.
Description
Technical Field
The invention belongs to the technical field of preparation of high polymer materials, and particularly relates to a polymer used as a leveling agent, and a preparation method and application thereof.
Background
The leveling agent is a common coating and printing ink auxiliary agent, can reduce the surface tension of the coating, promotes the stability and the uniformity of the surface tension in the wet film drying process, and is used for improving the leveling and the smoothness degree of a coated film, so that most of the leveling agents need to have the functions of shrinkage cavity prevention, smoothness, leveling and the like.
The existing leveling agents are roughly divided into two categories, one category is acted by adjusting the viscosity of a paint film and the leveling time, and most of the leveling agents are organic solvents with high boiling points or mixtures thereof, such as isophorone, diacetone alcohol, Solvesso150 and the like; the other is acted by adjusting the surface property of the paint film, and the leveling agent migrates to the surface of the paint film through limited compatibility to influence the surface properties such as the interfacial tension of the paint film and the like, so that the paint film obtains good leveling. Depending on the chemical structure, there are three main classes of such levelling agents: acrylics, silicones, and fluorocarbons. Wherein, the organic silicon flatting agent has no surface state control capability, so the organic silicon flatting agent is basically used in the flatting agent and is mostly used for the 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.
The application number 201510592088.5 discloses a preparation method of a fluorine-containing acrylate copolymer leveling agent, under the action of a rare earth metal coordination catalyst or a transition metal coordination catalyst, an acrylate monomer and a fluorine-containing acrylate monomer are subjected to coordination polymerization reaction in a solvent, the reaction solvent is removed under reduced pressure, and the fluorine-containing acrylate leveling agent and an auxiliary agent are prepared into an environment-friendly water-soluble paint according to a ratio, so that the surface tension of a paint system can be effectively reduced, and the paint has the characteristics of high leveling speed, strong anti-cratering capability and the like.
Chinese patent application nos. 200810020505.9, 201110059353.5 and 201110059479.2 report preparation methods of a series of fluorine-containing acrylate leveling agents, but these patents all adopt a traditional free radical polymerization method, and because a free radical polymerization reaction is initiated by heating, the free radical is initiated quickly, grows quickly, and emits a large amount of heat, implosion is easy to occur in the production process, the controllability is poor, and certain danger exists.
Disclosure of Invention
The invention aims to provide a polymer used as a leveling agent and a preparation method thereof, which can be used as the leveling agent and an anti-shrinkage agent in paint and printing ink.
A polymer for use as a leveling agent, having the structure shown below:
wherein R is1～R3、R5All are alkyl groups, and n is 10 to 200.
A preparation method of a polymer used as a leveling agent specifically comprises the following steps:
s1, reacting hexafluoropropylene oxide with an acrylic monomer to obtain an intermediate;
s2, reacting the intermediate obtained in the step S1 with an alkoxy silane monomer to obtain an alkoxy silane fluorine-containing acrylate monomer;
s3, under the action of an initiator, the alkoxy silane fluorine-containing acrylate monomer obtained in the step S2 is subjected to atom transfer radical polymerization to further obtain the polyalkoxysilane fluorine-containing acrylate.
Further, in the step S1, the acrylic monomer is acrylic acid or methacrylic acid.
Further, the mole ratio of the hexafluoropropylene oxide to the acrylic monomer is 1: 1-1.2, and the reaction is carried out in a nitrogen atmosphere, wherein the reaction temperature is 60-80 ℃.
Further, the alkoxy silane monomer in step S2 is one or more of trimethyl oxysilane, trifluoro propane trimethoxy silane, and dimethyl siloxane.
Furthermore, in the step S3, the reaction ratio of the alkoxysilane fluoroacrylate monomer and the initiator is adjusted according to the requirement of the molecular weight of the target polyalkylsilane fluoroacrylate polymer, and the temperature of the polymerization reaction is 40-70 ℃.
A polymer used as a leveling agent is applied to paint or ink and can be used as the leveling agent and the anti-shrinkage agent at the same time.
The invention has the following beneficial effects:
1. the invention adopts hexafluoropropylene oxide to react with acrylic monomer to obtain intermediate, R of the intermediate5For alkyl, the reaction mechanism is as follows:
the intermediate reacts with alkoxy silane monomer to obtain alkoxy silane fluorine-containing acrylate monomer, wherein R in the alkoxy silane monomer1～R4All of which are the same or different alkyl groups, the reaction mechanism is as follows:
the alkoxy silane fluorine-containing acrylate monomer is prepared into the polyalkoxy silane fluorine-containing acrylate by adopting an atom transfer radical polymerization method, wherein the reaction mechanism is as follows:
2. the polyalkoxysilane fluorine-containing acrylate prepared by the method has excellent smoothness and anti-shrinkage performance, the leveling agent or the anti-shrinkage agent prepared by the polyalkoxysilane fluorine-containing acrylate has excellent leveling property and gloss, the fluorine-containing acrylic glycol ester is prepared by the reaction of the fluorine-containing monomer and the acrylic monomer, so that the polymer has extremely low surface tension and is suitable for the leveling agent, the fluorine-containing acrylic glycol ester is reacted with the alkyl siloxane, and the atom transfer radical polymerization is adopted to obtain the target polymer, so that the target polymer has the lubricity and the spreadability of the alkyl siloxane.
Drawings
FIG. 1 shows nuclear magnetic fluorine spectrum of polyalkoxysilane fluorine-containing acrylate prepared by the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
The preparation method of the alkoxy silane fluorine-containing acrylate specifically comprises the following steps:
s1, reacting hexafluoropropylene oxide with acrylic acid in the atmosphere of nitrogen, wherein the molar ratio of hexafluoropropylene oxide to acrylic acid is 1:1, and the reaction temperature is 60 ℃, so as to obtain an intermediate;
s2, reacting the intermediate obtained in the step S1 with trimethylsiloxy to obtain an alkoxysilane fluorine-containing acrylate monomer;
s3, adopting an atom transfer radical polymerization method to obtain the polyalkoxysilane fluorine-containing acrylate by the alkoxysilane fluorine-containing acrylate monomer obtained in the step S2 under the action of an initiator, wherein the polymerization reaction temperature is 40 ℃.
Furthermore, according to the requirement of the molecular weight of the target polymer of the polyalkylsilane fluoroacrylate, the reaction ratio of the alkoxysilane fluoroacrylate monomer and the initiator in the polymerization reaction is adjusted, one initiator corresponds to the formation of one macromolecule, if the monomers are more, the initiator is less, the molecular weight of the obtained polymer is larger, and conversely, if the monomers are less, the initiator is more, and the molecular weight is smaller.
Example 2
The preparation method of the alkoxy silane fluorine-containing acrylate specifically comprises the following steps:
s1, reacting hexafluoropropylene oxide with methacrylic acid in the nitrogen atmosphere, wherein the molar ratio of hexafluoropropylene oxide to methacrylic acid is 1:1.1, and the reaction temperature is 80 ℃, so as to obtain an intermediate;
s2, reacting the intermediate obtained in the step S1 with a mixture of trifluoropropyltrimethoxysilane or dimethyl siloxane to obtain an alkoxy silane fluorine-containing acrylate monomer;
s3, adopting an atom transfer radical polymerization method to obtain the polyalkoxysilane fluorine-containing acrylate by the alkoxysilane fluorine-containing acrylate monomer obtained in the step S2 under the action of an initiator, wherein the polymerization reaction temperature is 70 ℃.
Example 3
The preparation method of the alkoxy silane fluorine-containing acrylate specifically comprises the following steps:
s1, reacting hexafluoropropylene oxide with methacrylic acid in the nitrogen atmosphere, wherein the molar ratio of hexafluoropropylene oxide to methacrylic acid is 1:1.2, and the reaction temperature is 70 ℃, so as to obtain an intermediate;
s2, reacting the intermediate obtained in the step S1 with trifluoropropane trimethoxy silane to obtain an alkoxy silane fluorine-containing acrylate monomer;
s3, adopting an atom transfer radical polymerization method to obtain the polyalkoxysilane fluorine-containing acrylate by the alkoxysilane fluorine-containing acrylate monomer obtained in the step S2 under the action of an initiator, wherein the polymerization reaction temperature is 60 ℃.
In conclusion, the alkoxysilane fluoroacrylate prepared by the preparation methods of examples 1-3 can be used as a leveling agent and an anti-cratering agent for coatings and inks.
And (3) performance testing:
the samples prepared in examples 1-3 are used as leveling agents for oily coatings, and then influence on product performance is caused, wherein compatibility is measured according to national standard GB/T21782.12-2010, leveling property is measured according to national standard GB1750-89(79), smoothness is represented by a friction coefficient value, surface smoothness of MXS-05A tin can coatings is detected by an MXS-05A tin can coating surface smoothness tester, foam stability is measured by a Roche foam tester, and glossiness is measured by an XD-1050 glossiness tester.
TABLE 1 Properties measurements of Polyalkoxy silane fluoroacrylates
TABLE 2 Effect of Polyalkoxy silane fluoroacrylates on coating Properties
| Test sample | Compatibility | Leveling property | Degree of shrinkage | Foam stability |
| Example 1 | Is transparent | Good taste | Without shrinkage cavity | Defoaming |
| Example 2 | Is transparent | Good taste | Without shrinkage cavity | Defoaming |
| Example 3 | Is transparent | Good taste | Without shrinkage cavity | Defoaming |
As can be seen from tables 1 and 2, the polyalkoxysilane fluorine-containing acrylate prepared by the invention is used as a leveling agent in an oil paint, so that the surface tension, the surface viscosity and the friction coefficient of the paint are reduced, the glossiness of the paint is improved, and the finally prepared paint has good compatibility, leveling property and foam stability and can prevent shrinkage cavity.
Referring to FIG. 1, the nuclear magnetic fluorine spectrum of the polyalkoxysilane fluorine-containing acrylate is shown, different groups existing in the prepared polymer are judged mainly through chemical shift values in the spectrum, and in a low field region, the peak value of the polymer meets-CF3、-CF2And the chemical shift value of the-OCF-group, wherein-CF3Has a chemical shift value of-52 to-87 ppm and-CF2The chemical shift of-OCF-is in the range of-80 to-120 ppm and the chemical shift of-OCF-is in the range of-125 to-150 ppm.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (7)
1. A polymer for use as a leveling agent, characterized by: has the following structure:
wherein R is1～R3Is alkyl, R5Is a hydrogen atom or a methyl group, and n is 10 to 200.
2. The polymer as a leveling agent according to claim 1, which is applied to a coating or ink, and can serve as both a leveling agent and an anti-cratering agent.
3. The method for preparing a polymer used as a leveling agent according to claim 1, comprising the steps of:
s1, reacting hexafluoropropylene oxide with an acrylic monomer to obtain an intermediate;
s2, reacting the intermediate obtained in the step S1 with an alkoxy silane monomer to obtain an alkoxy silane fluorine-containing acrylate monomer;
s3, under the action of an initiator, the alkoxy silane fluorine-containing acrylate monomer obtained in the step S2 is subjected to atom transfer radical polymerization to further obtain the polyalkoxysilane fluorine-containing acrylate.
4. A method of preparing a polymer for use as a leveling agent according to claim 3, wherein: the acrylic monomer in step S1 is acrylic acid or methacrylic acid.
5. A method of preparing a polymer for use as a leveling agent according to claim 3, wherein: the mole ratio of the hexafluoropropylene oxide to the acrylic monomer is 1: 1-1.2, and the reaction is carried out in a nitrogen atmosphere at the reaction temperature of 60-80 ℃.
6. A method of preparing a polymer for use as a leveling agent according to claim 3, wherein: the alkoxy silane monomer in the step S2 is trimethyl oxysilane.
7. A method of preparing a polymer for use as a leveling agent according to claim 3, wherein: the temperature of the polymerization reaction in the step S3 is 40-70 ℃.
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| JPS60190727A (en) * | 1984-03-09 | 1985-09-28 | Daikin Ind Ltd | Fluorine-containing organic silane compound, preparation and use thereof |
| ATE434023T1 (en) * | 2001-10-17 | 2009-07-15 | Ciba Holding Inc | FLOWING AND ANTI-CRATER AGENTS |
| EP2247678B1 (en) * | 2008-02-22 | 2011-11-30 | Basf Se | Fluoro levelling agents |
| CN103524651B (en) * | 2013-10-12 | 2016-03-16 | 三明学院 | A kind of flow agent and anticrater agent |
| CN107964063B (en) * | 2017-09-29 | 2020-02-11 | 三明学院 | PFOA-free polymer and preparation method and application thereof |
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