CN113896862A - Polymer epoxy resin, preparation method and application thereof - Google Patents
Polymer epoxy resin, preparation method and application thereof Download PDFInfo
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- CN113896862A CN113896862A CN202111434926.8A CN202111434926A CN113896862A CN 113896862 A CN113896862 A CN 113896862A CN 202111434926 A CN202111434926 A CN 202111434926A CN 113896862 A CN113896862 A CN 113896862A
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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
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
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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
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
- C08G59/4261—Macromolecular compounds obtained by reactions involving only unsaturated carbon-to-carbon bindings
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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Abstract
The invention provides a preparation method of polymer epoxy resin, which comprises the following steps: preparing an oleophylic-hydrophilic polymer, preparing an oleophylic-hydrophilic polymer epoxy resin, sequentially adding the oleophylic-hydrophilic polymer, the epoxy resin and a chain initiator into a solvent, uniformly mixing, and stirring in an oxygen-free reaction container to obtain the oleophylic-hydrophilic polymer epoxy resin. The invention also provides the polymer epoxy resin prepared by the method and application thereof. The lipophilic-hydrophilic polymer epoxy resin prepared by the invention can control the polymerization degree of the polymer by regulating and controlling the proportion and the dosage of the lipophilic monomer, the hydrophilic monomer and the chain transfer agent, and fully exerts the excellent performances of the lipophilic polymer and the hydrophilic polymer. The epoxy resin obtained by the invention is used for preparing the high-solid anticorrosive paint, can improve the film forming property of the paint, and effectively promotes the preparation of the later high-solid anticorrosive paint.
Description
Technical Field
The invention relates to the technical field of polymer epoxy resin synthesis, in particular to a polymer epoxy resin, a preparation method and application thereof.
Background
The core problem for preparing the high-solid anticorrosive paint is to reduce the molecular weight of a film forming material (epoxy resin), improve the solubility of the resin and reduce the viscosity of the paint, so that the selected base material should meet the requirements of low molecular weight, few polar chemical bonds and groups in a paint film, high crosslinking density, low viscosity, high solubility and the like.
At present, liquid epoxy resin E51 or E44 with low molecular weight is generally selected as a base material for main resin of the high-solid anticorrosive paint, but the dry film forming property of the obtained high-solid anticorrosive paint is poor.
Disclosure of Invention
The invention provides a polymer epoxy resin, a preparation method and application thereof, and solves the problem of poor film forming property of a dry film of a high-solid anticorrosive coating in the prior art.
The technical scheme of the invention is realized as follows:
according to a first aspect of embodiments of the present invention, a method of preparing a polymeric epoxy resin is presented.
In one embodiment, the method for preparing the polymer epoxy resin comprises the following steps:
step one, preparing lipophilic-hydrophilic polymer
Adding a lipophilic monomer, a solvent, a chain transfer agent and a chain initiator into an oxygen-free reaction container and stirring, wherein the temperature of the reaction container is 60-80 ℃, obtaining a lipophilic polymer solution, and purifying the lipophilic polymer solution to obtain a lipophilic polymer; sequentially adding a lipophilic polymer, a hydrophilic monomer, a chain initiator and a solvent into an oxygen-free reaction vessel and stirring, wherein the temperature of the reaction vessel is 60-80 ℃, so as to obtain a lipophilic-hydrophilic polymer mixed solution, and purifying the mixed solution to obtain a lipophilic-hydrophilic polymer;
step two, preparing polymer epoxy resin
Sequentially adding the oleophilic-hydrophilic polymer, the epoxy resin and the chain initiator into a solvent, uniformly mixing, and stirring in an oxygen-free reaction vessel at the temperature of 60-80 ℃ to obtain the polymer epoxy resin.
Optionally, the lipophilic monomer is a styrene monomer, a vinyl monomer, or an acrylate monomer.
Optionally, the hydrophilic monomer is an acrylic acid or methacrylic acid.
Optionally, the solvent is a polar solvent.
Optionally, the solvent is 1, 4-dioxane or absolute ethanol.
Optionally, the chain transfer agent is a trithiocarbonate chain transfer agent or a dithioester chain transfer agent.
Optionally, the chain initiator is benzoyl peroxide or azobisisobutyronitrile.
Optionally, the epoxy resin is a bisphenol a type epoxy resin.
Optionally, in the first step, the mass ratio of the lipophilic monomer, the chain transfer agent, the chain initiator and the solvent is 3-5: 0.5-0.8: 1-1.5: 3-5.
Optionally, in the first step, the mass ratio of the lipophilic polymer, the hydrophilic monomer, the chain initiator and the solvent is 3-5: 1-1.5: 3-5.
Optionally, in the step one, in the step of adding the lipophilic monomer, the solvent, the chain transfer agent and the chain initiator into an anaerobic reaction vessel and stirring, the stirring speed is 700-900 rpm, and the stirring time is 6-10 hours; in the step of sequentially adding the lipophilic polymer, the hydrophilic monomer, the chain initiator and the solvent into an anaerobic reaction container and stirring, the stirring speed is 700-900 rpm, and the stirring time is 6-10 hours.
Optionally, in the second step, the lipophilic-hydrophilic polymer, the epoxy resin and the chain initiator are sequentially added into the solvent, the mixture is uniformly mixed, and in the stirring step in the anaerobic reaction vessel, the stirring speed is 700-900 rpm, and the stirring time is 6-10 hours.
Optionally, in the second step, the mass ratio of the lipophilic-hydrophilic polymer to the epoxy resin to the chain initiator to the solvent is 3-5: 1-1.5: 3-5.
According to a second aspect of embodiments of the present invention, there is provided a polymeric epoxy resin prepared by the above method.
In one embodiment, the viscosity of the polymer epoxy resin is 700 to 11000 mPa.S.
According to a third aspect of embodiments of the present invention, there is provided a use of the above-mentioned polymer epoxy resin.
In one embodiment, the polymeric epoxy resin is used to prepare a high-solids anticorrosion coating.
The invention has the beneficial effects that:
the lipophilic-hydrophilic polymer epoxy resin prepared by the invention has simple preparation process, the polymerization degree of the polymer can be controlled by regulating and controlling the proportion and the dosage of the reagent monomer and the chain transfer agent, and the excellent performances of the lipophilic polymer and the hydrophilic polymer are fully exerted. The epoxy resin is used for preparing the high-solid anticorrosive paint, can improve the film forming property of the paint, and effectively promotes the preparation of the later high-solid anticorrosive paint and the engineering applicability thereof.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a graph showing the effect of film formation after brushing of a coating prepared from an oleophilic-hydrophilic polymer epoxy resin according to the present invention as shown in example 1;
FIG. 2 is a graph showing the effect of film formation after brushing of a coating prepared from the oleophilic-hydrophilic polymer epoxy resin according to example 2;
FIG. 3 is a diagram showing the film forming effect of a coating brushed without using the paint prepared from the oleophilic-hydrophilic polymer epoxy resin of the invention.
Detailed Description
To make the features and effects of the present invention comprehensible to those having ordinary knowledge in the art, general description and definitions are made with respect to terms and phrases mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In this document, the terms "comprising," "including," "having," "containing," or any other similar term, are intended to be open-ended transitionalphase, which is intended to cover non-exclusive inclusions. For example, a composition or article comprising a plurality of elements is not limited to only those elements recited herein, but may include other elements not expressly listed but generally inherent to such composition or article. In addition, unless expressly stated to the contrary, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or". For example, the condition "a or B" is satisfied in any of the following cases: a is true (or present) and B is false (or not present), a is false (or not present) and B is true (or present), both a and B are true (or present). Furthermore, in this document, the terms "comprising," including, "" having, "" containing, "and" containing "are to be construed as specifically disclosed and to cover both closed and semi-closed conjunctions, such as" consisting of … "and" consisting essentially of ….
All features or conditions defined herein as numerical ranges or percentage ranges are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to have covered and specifically disclosed all possible subranges and individual numerical values within the ranges, particularly integer numerical values. For example, a description of a range of "1 to 8" should be considered to have specifically disclosed all subranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, and so on, particularly subranges bounded by all integer values, and should be considered to have specifically disclosed individual values such as 1, 2, 3, 4, 5, 6, 7, 8, and so on, within the range. Unless otherwise indicated, the foregoing explanatory methods apply to all matters contained in the entire disclosure, whether broad or not.
If an amount or other value or parameter is expressed as a range, preferred range, or a list of upper and lower limits, it is to be understood that all ranges subsumed therein for any pair of that range's upper or preferred value and that range's lower or preferred value, whether or not such ranges are separately disclosed, are specifically disclosed herein. Further, when a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.
In this context, numerical values should be understood to have the precision of the number of significant digits of the value, provided that the object of the invention is achieved. For example, the number 40.0 should be understood to cover a range from 39.50 to 40.49. In this document, where Markush group (Markush group) or Option language is used to describe features or examples of the invention, those skilled in the art will recognize that a sub-group of all elements or any individual element within a Markush group or list of options may also be used to describe the invention. For example, if X is described as "selected from the group consisting of1、X2And X3The group consisting ofX has been fully described as X1Is claimed with X1And/or X2Claim (5). Furthermore, where Markush group or option terms are used to describe features or examples of the invention, those skilled in the art will recognize that any combination of sub-groups of all elements or individual elements within the Markush group or option list can also be used to describe the invention. Accordingly, for example, if X is described as "selected from the group consisting of1、X2And X3Group consisting of "and Y is described as" selected from Y1、Y2And Y3The group "formed indicates that X has been fully described as X1Or X2Or X3And Y is Y1Or Y2Or Y3Claim (5).
The following detailed description is merely exemplary in nature and is not intended to limit the invention or the application thereof. Furthermore, there is no intention to be bound by any theory presented in the preceding prior art or the summary of the invention or the following detailed description or examples.
Example 1
A preparation method of polymer epoxy resin comprises the following steps:
step one, preparing lipophilic-hydrophilic polymer
Adding a styrene monomer, 1, 4-dioxane, trithiocarbonate and benzoyl peroxide into an oxygen-free reaction container, stirring, wherein the temperature of the reaction container is 60 ℃, the stirring speed is 700rpm, and the stirring time is 10 hours, wherein the mass ratio of the styrene monomer, the trithiocarbonate, the benzoyl peroxide to the 1, 4-dioxane is 3:0.5:1:3, obtaining a polystyrene solution, and purifying the polystyrene solution to obtain polystyrene; sequentially adding polystyrene, methacrylic acid, benzoyl peroxide and 1, 4-dioxane into an oxygen-free reaction container, stirring, wherein the temperature of the reaction container is 60 ℃, the stirring speed is 700rpm, and the stirring time is 6 hours, wherein the mass ratio of the polystyrene, the methacrylic acid, the benzoyl peroxide and the 1, 4-dioxane is 3:3:1:3, so as to obtain a polystyrene-polymethacrylic acid mixed solution, and purifying the polystyrene-polymethacrylic acid mixed solution to obtain polystyrene-polymethacrylic acid;
step two, preparing oleophylic-hydrophilic polymer epoxy resin
Adding polystyrene-polymethacrylic acid, epoxy resin E44 and benzoyl peroxide into 1, 4-dioxane in sequence, wherein the mass ratio of the polystyrene-polymethacrylic acid to the epoxy resin E44 to the benzoyl peroxide to the 1, 4-dioxane is 3:3:1:3, uniformly mixing, stirring in an oxygen-free reaction vessel at the temperature of 60 ℃, the stirring speed of 700rpm and the stirring time of 10 hours to obtain the polystyrene-polymethacrylic acid epoxy resin.
Optionally, the polymeric epoxy resin has a viscosity of 800mPa · S.
Example 2
A preparation method of polymer epoxy resin comprises the following steps:
step one, preparing lipophilic-hydrophilic polymer
Adding a styrene monomer, 1, 4-dioxane, trithiocarbonate and benzoyl peroxide into an oxygen-free reaction container, stirring, wherein the temperature of the reaction container is 80 ℃, the stirring speed is 900rpm, and the stirring time is 6 hours, wherein the mass ratio of the styrene monomer, the trithiocarbonate, the benzoyl peroxide and the 1, 4-dioxane is 5:0.8:1.5:5, the stirring speed is 900rpm, and the stirring time is 6 hours, so as to obtain a polystyrene solution, and purifying the polystyrene solution to obtain polystyrene; sequentially adding polystyrene, methacrylic acid, benzoyl peroxide and 1, 4-dioxane into an oxygen-free reaction container, stirring, wherein the temperature of the reaction container is 80 ℃, the stirring speed is 900rpm, and the stirring time is 6 hours, wherein the mass ratio of the polystyrene to the methacrylic acid to the benzoyl peroxide to the 1, 4-dioxane is 4:3:1:3, obtaining a polystyrene-polymethacrylic acid mixed solution, and purifying the polystyrene-polymethacrylic acid mixed solution to obtain polystyrene-polymethacrylic acid;
step two, preparing oleophylic-hydrophilic polymer epoxy resin
Adding polystyrene-polymethacrylic acid, epoxy resin E44 and benzoyl peroxide into 1, 4-dioxane in sequence, wherein the mass ratio of the polystyrene-polymethacrylic acid to the epoxy resin E44 to the benzoyl peroxide to the 1, 4-dioxane is 5:5:1.5:5, uniformly mixing, stirring in an oxygen-free reaction container at the temperature of 80 ℃, the stirring speed of 900rpm and the stirring time of 6 hours to obtain the polystyrene-polymethacrylic acid epoxy resin.
Optionally, the polymeric epoxy resin has a viscosity of 3000mPa · S.
Example 3
A preparation method of polymer epoxy resin comprises the following steps:
step one, preparing lipophilic-hydrophilic polymer
Adding ethylene, absolute ethyl alcohol, alkyl dithioester and azobisisobutyronitrile into an anaerobic reaction vessel and stirring, wherein the temperature of the reaction vessel is 70 ℃, the stirring speed is 600rpm, and the stirring time is 8 hours, wherein the mass ratio of the ethylene to the alkyl dithioester to the azobisisobutyronitrile to the absolute ethyl alcohol is 4:0.6:1.2:4, so as to obtain a polyethylene solution, and purifying the polyethylene solution so as to obtain polyethylene; sequentially adding polyethylene, acrylic acid, azobisisobutyronitrile and absolute ethyl alcohol into an anaerobic reaction container and stirring, wherein the temperature of the reaction container is 70 ℃, the stirring speed is 800rpm, and the stirring time is 8 hours, wherein the mass ratio of the polyethylene to the acrylic acid to the azobisisobutyronitrile to the absolute ethyl alcohol is 4:4:1:3, so as to obtain a polyethylene-polyacrylic acid mixed solution, and purifying the mixed solution to obtain polyethylene-polyacrylic acid;
step two, preparing oleophylic-hydrophilic polymer epoxy resin
Sequentially adding polyethylene-polyacrylic acid, epoxy resin E51 and azobisisobutyronitrile into absolute ethyl alcohol, wherein the mass ratio of the polyethylene-polyacrylic acid to the epoxy resin E51 to the azobisisobutyronitrile to the absolute ethyl alcohol is 4:4:1.2:4, uniformly mixing, and stirring in an oxygen-free reaction vessel at the temperature of 70 ℃, the stirring speed of 800rpm and the stirring time of 8 hours to obtain the polyethylene-polyacrylic acid epoxy resin.
Optionally, the polymeric epoxy resin has a viscosity of 5000mPa · S.
Example 4
A preparation method of polymer epoxy resin comprises the following steps:
step one, preparing lipophilic-hydrophilic polymer
Adding ethylene, absolute ethyl alcohol, alkyl dithioester and benzoyl peroxide into an anaerobic reaction vessel and stirring, wherein the temperature of the reaction vessel is 60 ℃, the stirring speed is 700rpm, and the stirring time is 8 hours, wherein the mass ratio of the ethylene to the alkyl dithioester to the benzoyl peroxide to the absolute ethyl alcohol is 3:0.8:1.5:3, so as to obtain a polyethylene solution, and purifying the polyethylene solution to obtain polyethylene; sequentially adding polyethylene, methacrylic acid, benzoyl peroxide and absolute ethyl alcohol into an oxygen-free reaction container, stirring, wherein the temperature of the reaction container is 60 ℃, the stirring speed is 700rpm, and the stirring time is 8 hours, wherein the mass ratio of the polyethylene to the methacrylic acid to the benzoyl peroxide to the absolute ethyl alcohol is 5:4:1.2:4, so as to obtain a polyethylene-polymethacrylic acid mixed solution, and purifying the mixed solution to obtain polyethylene-polymethacrylic acid;
step two, preparing oleophylic-hydrophilic polymer epoxy resin
Adding polyethylene-polymethacrylic acid, epoxy resin E44 and benzoyl peroxide into absolute ethyl alcohol in sequence, wherein the mass ratio of the polyethylene-polymethacrylic acid to the epoxy resin E44 to the benzoyl peroxide to the absolute ethyl alcohol is 3:5:1.5:3, uniformly mixing, stirring in an oxygen-free reaction vessel, wherein the temperature of the reaction vessel is 60 ℃, the stirring speed is 700rpm, and the stirring time is 8 hours, so as to obtain the polyethylene-polymethacrylic acid epoxy resin.
Optionally, the polymeric epoxy resin has a viscosity of 8000 mPa-S.
Example 5
A preparation method of polymer epoxy resin comprises the following steps:
step one, preparing lipophilic-hydrophilic polymer
Adding a methyl acrylate monomer, 1, 4-dioxane, trithiocarbonate and azobisisobutyronitrile into an oxygen-free reaction vessel and stirring, wherein the temperature of the reaction vessel is 80 ℃, the stirring speed is 800rpm, and the stirring time is 10 hours, wherein the mass ratio of the methyl acrylate monomer, the trithiocarbonate, the azobisisobutyronitrile to the 1, 4-dioxane is 5:0.8:1.5:3, so as to obtain a polymethyl acrylate solution, and purifying the polymethyl acrylate solution to obtain polymethyl acrylate; sequentially adding polymethyl acrylate, acrylic acid, azodiisobutyronitrile and 1, 4-dioxane into an oxygen-free reaction container, and stirring, wherein the temperature of the reaction container is 80 ℃, the stirring speed is 800rpm, and the stirring time is 10 hours, wherein the mass ratio of the polymethyl acrylate, the acrylic acid, the azodiisobutyronitrile to the 1, 4-dioxane is 5:5:1.2:5, so as to obtain a polymethyl acrylate-polyacrylic acid mixed solution, and purifying the mixed solution so as to obtain the polymethyl acrylate-polyacrylic acid;
step two, preparing oleophylic-hydrophilic polymer epoxy resin
Adding polymethyl acrylate-polyacrylic acid, epoxy resin E51 and azodiisobutyronitrile into 1, 4-dioxane in sequence, wherein the mass ratio of the polymethyl acrylate-polyacrylic acid to the epoxy resin E51 to the azodiisobutyronitrile to the 1, 4-dioxane is 5:5:1.5:3, uniformly mixing, stirring in an oxygen-free reaction vessel at the temperature of 80 ℃, the stirring speed of 800rpm and the stirring time of 10 hours to obtain the polymethyl acrylate-polyacrylic acid epoxy resin.
Optionally, the polymeric epoxy resin has a viscosity of 10000mPa · S.
Fig. 1 and 2 show the paint-coated coatings prepared from the oleophilic-hydrophilic polymer epoxy resins of examples 1 and 2 of the invention, respectively, and fig. 3 shows the paint-coated coatings prepared from the oleophilic-hydrophilic polymer epoxy resins of the invention, by comparison, it is obvious that the paint-coated coatings prepared from the oleophilic-hydrophilic polymer epoxy resins of examples 1 and 2 of the invention, after the coatings are dried, effectively improve the film-forming property of the coatings.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (16)
1. A preparation method of polymer epoxy resin is characterized by comprising the following steps:
step one, preparing lipophilic-hydrophilic polymer
Adding a lipophilic monomer, a solvent, a chain transfer agent and a chain initiator into an oxygen-free reaction container and stirring, wherein the temperature of the reaction container is 60-80 ℃, obtaining a lipophilic polymer solution, and purifying the lipophilic polymer solution to obtain a lipophilic polymer; sequentially adding a lipophilic polymer, a hydrophilic monomer, a chain initiator and a solvent into an oxygen-free reaction vessel and stirring, wherein the temperature of the reaction vessel is 60-80 ℃, so as to obtain a lipophilic-hydrophilic polymer mixed solution, and purifying the mixed solution to obtain a lipophilic-hydrophilic polymer;
step two, preparing polymer epoxy resin
Sequentially adding the oleophilic-hydrophilic polymer, the epoxy resin and the chain initiator into a solvent, uniformly mixing, and stirring in an oxygen-free reaction vessel at the temperature of 60-80 ℃ to obtain the polymer epoxy resin.
2. The method of claim 1, wherein the lipophilic monomer is a styrene monomer, a vinyl monomer, or an acrylate monomer.
3. The method of claim 1, wherein the hydrophilic monomer is an acrylic acid or a methacrylic acid.
4. The method of claim 1, wherein the solvent is a polar solvent.
5. The method of claim 4, wherein the solvent is 1, 4-dioxane or absolute ethanol.
6. The method of claim 1, wherein the chain transfer agent is a trithiocarbonate chain transfer agent or a dithioester chain transfer agent.
7. The method of claim 1, wherein the chain initiator is benzoyl peroxide or azobisisobutyronitrile.
8. The method of claim 1, wherein the epoxy resin is a bisphenol a epoxy resin.
9. The method for preparing a polymer epoxy resin according to claim 1, wherein in the first step, the mass ratio of the lipophilic monomer, the chain transfer agent, the chain initiator and the solvent is 3-5: 0.5-0.8: 1-1.5: 3-5.
10. The method for preparing a polymer epoxy resin according to claim 1, wherein in the first step, the mass ratio of the lipophilic polymer, the hydrophilic monomer, the chain initiator and the solvent is 3-5: 1-1.5: 3-5.
11. The method for preparing a polymer epoxy resin according to claim 1, wherein in the step one, the lipophilic monomer, the solvent, the chain transfer agent and the chain initiator are added into an oxygen-free reaction vessel and stirred, the stirring speed is 700-900 rpm, and the stirring time is 6-10 h; in the step of sequentially adding the lipophilic polymer, the hydrophilic monomer, the chain initiator and the solvent into an anaerobic reaction container and stirring, the stirring speed is 700-900 rpm, and the stirring time is 6-10 hours.
12. The method for preparing polymer epoxy resin according to claim 1, wherein in the second step, the lipophilic-hydrophilic polymer, the epoxy resin and the chain initiator are sequentially added into the solvent and uniformly mixed, and in the step of stirring in an oxygen-free reaction vessel, the stirring speed is 700-900 rpm, and the stirring time is 6-10 h.
13. The method for preparing the polymer epoxy resin according to claim 1, wherein in the second step, the mass ratio of the lipophilic-hydrophilic polymer to the epoxy resin to the chain initiator to the solvent is 3-5: 1-1.5: 3-5.
14. A polymeric epoxy resin prepared by the process of any one of claims 1 to 13.
15. A polymeric epoxy resin according to claim 14,
the viscosity of the polymer epoxy resin is 700-11000 mPa & S.
16. Use of the polymeric epoxy resin according to claim 14 for the preparation of high-solids corrosion protection coatings.
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| CN109294394A (en) * | 2018-09-21 | 2019-02-01 | 华东理工大学 | A kind of superhydrophilic self-cleaning epoxy coating and the preparation method and application thereof |
| CN111019071A (en) * | 2019-11-22 | 2020-04-17 | 济宁明升新材料有限公司 | Block-type dispersant based on RAFT polymerization and preparation method thereof |
| CN112375451A (en) * | 2020-12-10 | 2021-02-19 | 无锡市太湖防腐材料有限公司 | Low-film-thickness high-performance water-based single-component anticorrosive paint and preparation method thereof |
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| CN109180877A (en) * | 2018-09-19 | 2019-01-11 | 江苏三木化工股份有限公司 | Plastic paint waterborne epoxy modified acrylic resin and preparation method thereof |
| CN109294394A (en) * | 2018-09-21 | 2019-02-01 | 华东理工大学 | A kind of superhydrophilic self-cleaning epoxy coating and the preparation method and application thereof |
| CN111019071A (en) * | 2019-11-22 | 2020-04-17 | 济宁明升新材料有限公司 | Block-type dispersant based on RAFT polymerization and preparation method thereof |
| CN112375451A (en) * | 2020-12-10 | 2021-02-19 | 无锡市太湖防腐材料有限公司 | Low-film-thickness high-performance water-based single-component anticorrosive paint and preparation method thereof |
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