CN106905555B - Epoxy resin with hydrophilic coating coated on surface and preparation method and application thereof - Google Patents

Epoxy resin with hydrophilic coating coated on surface and preparation method and application thereof Download PDF

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CN106905555B
CN106905555B CN201710190588.5A CN201710190588A CN106905555B CN 106905555 B CN106905555 B CN 106905555B CN 201710190588 A CN201710190588 A CN 201710190588A CN 106905555 B CN106905555 B CN 106905555B
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epoxy resin
hydrophilic
coating
coated
monomer
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CN106905555A (en
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张玉玺
刘宇鹏
王晨夕
赵榆霞
戴玉华
吴飞鹏
施盟泉
张云龙
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Technical Institute of Physics and Chemistry of CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/24—Homopolymers or copolymers of amides or imides
    • C08J2433/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2439/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers

Abstract

The invention discloses an epoxy resin with a hydrophilic coating coated on the surface, wherein the hydrophilic coating and the epoxy resin layer are chemically crosslinked in an adhesion mode, the epoxy resin layer is a cured epoxy resin with a hydrophilic polymer grafted on the surface, and the structural formula of the epoxy resin is as follows:
Figure DDA0001256039660000011
in the formula, R 1～R 4For the structural connection point with other epoxy resin chains, R 5～R 6Is a hydrophilic monomeric polar group, n 1、n 2Is a natural number, n is more than or equal to 1 1≤10，1≤n 2Less than or equal to 50000. The method provided by the invention does not use harsh surface cleaning treatment or coat an intermediate bonding layer, and the cured epoxy resin with the surface grafted with the hydrophilic polymer is firmly bonded with the hydrophilic coating which is coated subsequently through the crosslinking action, so that the aim of firmly adhering the hydrophilic coating to the surface of the epoxy resin substrate is fulfilled; different ionic monomers can be selected as the homo-or co-monomers of the hydrophilic coating. The raw material source is wide, and the hydrophilic coating with uniform surface property can be prepared.

Description

Epoxy resin with hydrophilic coating coated on surface and preparation method and application thereof
Technical Field
The invention relates to the technical field of polymer functional surface materials. More particularly, it relates to an epoxy resin with hydrophilic coating on its surface, its preparation method and application.
Background
At present, onshore petroleum storage and transportation are mainly carried out by pipelines, and in alpine regions, the storage and transportation mainly depend on heating and pressurization to realize the flow of crude oil. Since the temperature is gradually decreased during the flowing process, the viscosity of the crude oil is gradually increased. Meanwhile, along with the reduction of the temperature, compositions such as wax in the crude oil can be continuously separated out and condensed on the surfaces of the protective layer and the epoxy resin of the antirust layer on the inner wall of the oil pipeline, so that the flow resistance is increased, and the pressure burden of the crude oil in the pipeline is increased. It has been found that hydrophilic surfaces have a better anti-waxing effect in the case of smooth surfaces (Soviet, Li Ming et al; glass, epoxy phenolic stoving varnish-lined pipe anti-waxing mechanism, proceedings of the university of Petroleum (Nature science edition), 1998, 22 (1)).
The inner wall of an oil pipeline is coated with an anti-corrosion epoxy resin layer in general, but the surface of the epoxy resin layer is poor in hydrophilicity. Therefore, the hydrophilicity of the inner wall of the oil pipeline can be improved by coating a hydrophilic coating on the surface of the epoxy resin or performing hydrophilic modification on the surface of the epoxy resin. In the prior art, a polymer super-hydrophilic surface is prepared by constructing a nano-microporous structure, the method is simple in preparation process, low in cost and environment-friendly, and a coating with good hydrophilic performance is obtained by synthesizing two polyacrylamide with different ion types and mixing the two polyacrylamide. However, the above method only focuses on the hydrophilic property of the coating itself, and does not consider how the coating can be firmly bonded to the substrate. In practical application, the bonding strength of the coating and the substrate is a very critical index, and the practical value of the coating is determined. Therefore, when a hydrophilic coating is added on the inner wall of an oil pipeline, the first key problem to be solved is the bonding strength between the hydrophilic coating and the epoxy resin.
When the coating is adhered to the surface of the epoxy resin, a bonding layer, such as polyvinyl alcohol, needs to be coated between the coating and the epoxy resin to form a multi-layer film structure, so that the adhesion of the coating is improved. However, when the hydrophilic coating is bonded, the coating has certain water absorption, the volume expansion of the coating and the volume expansion of the bonding layer are different due to water, and the hydrophilic coating can fall off after long-term use. In the prior art, the uncured resin is generally subjected to chemical grafting modification, and the resin needs to be subjected to halogen acetylation treatment and then to graft polymerization, so that the preparation process is complex.
Therefore, the invention provides the epoxy resin with the surface coated with the hydrophilic coating, under the condition of not using the traditional multilayer bonding layer, the hydrophilic polymer is directly grafted on the surface of the cured epoxy resin, and then the cured epoxy resin is firmly bonded with the hydrophilic coating coated subsequently through the crosslinking action, so that the manufacturing process is simplified, and the hydrophilic coating is firmly adhered to the surface of the epoxy resin substrate.
Disclosure of Invention
An object of the present invention is to provide an epoxy resin coated with a hydrophilic coating layer on the surface thereof.
The invention also aims to provide a preparation method of the epoxy resin with the hydrophilic coating coated on the surface.
The third purpose of the invention is to provide the application of the epoxy resin with the hydrophilic coating on the surface.
The method provided by the invention does not use the traditional multilayer bonding layer, and the cured epoxy resin with the surface grafted with the hydrophilic polymer is firmly bonded with the hydrophilic coating which is coated subsequently through the crosslinking action, so that the aim of firmly adhering the hydrophilic coating to the surface of the epoxy resin substrate is fulfilled.
In order to achieve the first purpose, the invention adopts the following technical scheme:
the epoxy resin with the hydrophilic coating coated on the surface is bonded with the epoxy resin layer in a chemical crosslinking mode; the epoxy resin layer is a cured epoxy resin with a surface grafted with a hydrophilic polymer, and the structural formula of the cured epoxy resin is as follows:
Figure BDA0001256039640000021
in the formula, R 1～R 4For the structural connection point with other epoxy resin chains, R 5～R 6Is a hydrophilic monomeric polar group, n 1、n 2Is a natural number, n is more than or equal to 1 1≤10，1≤n 2≤50000。
According to the invention, the hydrophilic polymer is directly grafted on the surface of the cured epoxy resin, a chemical group for crosslinking is provided on the epoxy surface, the hydrophilicity of the surface of the epoxy resin after grafting and curing is improved, the hydrophilic coating is favorably spread on the surface of the epoxy resin, so that the epoxy resin layer is firmly bonded with the hydrophilic coating coated subsequently through crosslinking, the traditional multilayer bonding layer is not used, and the manufacturing process is greatly simplified.
Preferably, the hydrophilic monomer is acrylic acid, acrylamide, 2-propionamido-2-methylpropanesulfonic acid, allylamine, methacrylamide, hydroxyethyl methacrylate or hydroxyethyl acrylate. The hydrophilic monomers are adopted in the invention, and both have double bonds and polar groups which can be used for crosslinking.
Preferably, the hydrophilic polymer is grafted on the cured epoxy resin through an initiator, the grafting sites are α -H and β -H beside an ether bond, α -H and β -H beside the ether bond in the epoxy resin are more active and are easily attacked by the initiator to form an active center, so that monomer polymerization is initiated and the monomer is grafted to an epoxy resin chain.
Preferably, the hydrophilic coating is a hydrophilic homopolymer or a hydrophilic copolymer; the hydrophilic homopolymer is formed by polymerizing hydrophilic monomers; the hydrophilic copolymer is prepared by copolymerization of hydrophilic monomers and other hydrophilic monomers or copolymerization of hydrophilic monomers and different ionic monomers; the molecular weight of the hydrophilic homopolymer or the hydrophilic copolymer is 1.0 multiplied by 10 4～5.0×10 5。
Preferably, the different ionic monomers are anionic, cationic or zwitterionic monomers;
preferably, the cationic monomer is a monomer containing a quaternary ammonium salt group, more preferably, the cationic monomer is acryloyloxyethyltrimethyl ammonium chloride, methacryloyloxyethyltrimethylbenzyl ammonium chloride, (3-acrylamidopropyl) trimethylammonium chloride, methacrylamidopropyltrimethylammonium chloride, p-vinylbenzyltrimethylammonium chloride, methacrylamide- β -hydroxypropyltrimethylammonium chloride, acrylamido (2-methylbutyl) trimethylammonium chloride or diallyldimethylammonium chloride.
Preferably, the anionic monomer is a monomer containing a carboxyl group or a sulfonic group; more preferably, the anionic monomer is acrylic acid, methacrylic acid, maleic acid, itaconic acid, 3-acrylamido-3-methylbutyric acid or 2-acrylamido-2-methylpropanesulfonic acid and their sodium, potassium or ammonium salts.
In order to achieve the second purpose, the invention adopts the following technical scheme:
a preparation method of epoxy resin with a hydrophilic coating coated on the surface comprises the following steps:
1) the method comprises the steps of adding an initiator into an aqueous solution of a hydrophilic monomer to prepare a reaction solution, placing a cured epoxy resin substrate into the reaction solution, reacting under the protection of inert gas, stopping the reaction after the viscosity of the reaction solution is obviously changed, and obtaining the cured epoxy resin with the surface grafted with the hydrophilic polymer, wherein α -H and β -H beside an ether bond in the epoxy resin are more active and are easy to form an active center under the attack of the initiator, so that the monomer is initiated to polymerize and grafted to an epoxy resin chain.
2) Preparing an aqueous solution of a hydrophilic homopolymer or a hydrophilic copolymer, adding a cross-linking agent, and adjusting the pH value to 2-6 to obtain a coating liquid. The treated surface of the epoxy resin substrate is provided with a plurality of polar groups, and the crosslinking agent selected for the hydrophilic coating can also react with the polar groups, so that the coating and the epoxy layer are bonded together by means of chemical crosslinking.
3) Coating the coating liquid prepared in the step 2) on the epoxy resin substrate treated in the step 1), and putting the coated epoxy resin substrate into a drying oven at the temperature of 40-80 ℃ for cross-linking reaction for 2-5 h to finally obtain the epoxy resin with the surface firmly coated with the hydrophilic coating.
Preferably, the initiator in step 1) is an azo initiator, an inorganic or organic peroxide; more preferably, the initiator is an organic peroxide; the azo initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile, azobisisobutyramidine hydrochloride, diisobutyl azobisbutyrate and dimethyl azobisisobutyrate; the inorganic or organic peroxide is selected from one or more of ammonium persulfate, sodium persulfate, potassium persulfate, tert-butyl hydroperoxide, dicumyl peroxide and benzoyl peroxide.
Preferably, the cured epoxy resin substrate in the step 1) is prepared by uniformly mixing epoxy resin and a curing agent, coating the mixture on a substrate, and curing the mixture in an oven; preferably, the curing agent is m-phenylenediamine, m-xylylenediamine, p-phenylenediamine or p-xylylenediamine; the amount of the curing agent added depends on the epoxy value of the epoxy resin; the temperature of the oven is 80 ℃, and the curing time is 1-2 h.
Preferably, the adding amount of the hydrophilic monomer in the step 1) is 0.5-20 wt% of the total mass of the solution, and more preferably, the adding amount of the hydrophilic monomer is 1-5 wt% of the total mass of the solution.
Preferably, the adding amount of the initiator in the step 1) is 0.1-5 wt% of the mass of the hydrophilic monomer, and more preferably, the adding amount of the initiator is 1-3 wt% of the mass of the hydrophilic monomer. The method regulates and controls the surface grafting degree of the epoxy resin by changing the using amount of the initiator.
Preferably, the inert gas in the step 1) is nitrogen, the reaction temperature is 50 ℃, the reaction time is 1-8 hours, and preferably, the reaction time is 2-5 hours.
Preferably, the mass fraction of the hydrophilic homopolymer or the hydrophilic copolymer in the step 2) is 5-40 wt%; more preferably, the mass fraction of the hydrophilic homopolymer or the hydrophilic copolymer is 10 to 30 wt%.
Preferably, the mass fraction of the cross-linking agent in the step 2) is 0.01-10 wt%; more preferably, the mass fraction of the cross-linking agent is 0.1-5 wt%.
Preferably, the crosslinking agent in step 2) is a reactive oligomer, an organic crosslinking agent or an inorganic crosslinking agent; the active oligomer is urea-formaldehyde resin or phenolic resin; the organic cross-linking agent is formaldehyde, glyoxal, glutaraldehyde, terephthalaldehyde or o-phthalaldehyde; the inorganic cross-linking agent is chromium salt, zirconium salt, boron salt, titanium salt or terbium salt. Preferably, when the hydrophilic monomer is a hydrophilic monomer containing carboxylic acids, an inorganic cross-linking agent is used for the curing reaction, and when the hydrophilic monomer is a hydrophilic monomer containing amines, the cross-linking agent can be used for the curing reaction.
Preferably, the coating manner in step 3) is rinsing, blade coating, dip coating, spray coating or spin coating at a certain rotation speed.
The final epoxy resin with hydrophilic coating on the surface has a level of adhesion between the hydrophilic coating and the epoxy resin substrate above ISO 1 (Standard GB/T9286-1998 test of marking the paint film of colored paint and varnish).
In order to achieve the third purpose, the invention adopts the following technical scheme:
the application of epoxy resin with hydrophilic coating on the surface in oil pipeline.
According to the invention, the hydrophilic polymer is grafted on the surface of the cured epoxy resin, so that the cured epoxy resin with the hydrophilic polymer grafted on the surface is firmly bonded with the hydrophilic coating which is coated subsequently, and the hydrophilic coating is firmly bonded with the surface of the epoxy resin under the condition of not using harsh surface cleaning treatment or coating an intermediate bonding layer, so that the production process is simplified, and the firmness of the coating is improved.
The invention has the following beneficial effects:
(1) the hydrophilic coating can be firmly bonded with the surface of the epoxy resin without using harsh surface cleaning treatment or coating an intermediate bonding layer.
(2) Different monomers can be selected to be grafted on the surface of the epoxy resin, and the surface of the epoxy resin which can be used for firmly adhering the hydrophilic coating can be manufactured under relatively simple process conditions.
(3) Different ionic monomers can be selected as the homo-or co-monomers of the hydrophilic coating. The raw material source is wide, and the hydrophilic coating with uniform surface property can be prepared.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 shows a schematic diagram of the crosslinking reaction process in example 1 of the present invention.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
The preparation of epoxy resin with hydrophilic coating on its surface includes the following steps:
1) preparation of cured epoxy resin with surface grafted with hydrophilic polymer
Firstly, preparing a reaction solution for later use: 3g of acrylamide is added into a 150ml beaker, water is added until the total mass reaches 100g, and the acrylamide solution is fully stirred and dissolved. 0.03g of ammonium persulfate was added to the reaction solution, and the mixture was sufficiently stirred and dissolved to prepare a reaction solution.
The epoxy resin is then cured: 5g of epoxy resin E44 is dissolved in 2g of epoxy diluent with the volume ratio of ethanol to acetone being 1:1, 1g of m-xylylenediamine is added, and the mixture is stirred uniformly. Coating on the surface of the glass sheet, putting the glass sheet into an oven at 80 ℃ for curing for 2h, taking out the glass sheet (hereinafter referred to as a sample sheet) cured with the epoxy resin, and storing the glass sheet in a dry place for later use.
And finally, grafting the epoxy resin: and (3) flatly placing the sample wafer at the bottom of the reaction bottle, and adding reaction liquid into the reaction bottle, wherein the liquid level of the reaction liquid needs to be higher than the surface of the epoxy resin. Reacting for 3 hours under the protection of nitrogen at 50 ℃, stopping the reaction after the viscosity of the reaction solution is obviously changed, and taking out the sample.
And (3) soaking the sample piece in clear water for 3 days to remove the polymer which is not grafted on the surface. Drying in a constant temperature vacuum drying oven at 50 deg.C for 6 hr, and taking out for use. And testing the groups on the surface of the sample wafer by using a total reflection infrared spectroscopy, and confirming that the sample wafer has amide groups, thereby indicating that the grafting is successful. Placing the mixture into a vacuum drying oven for standby.
2) Preparation of coating solution
First, a hydrophilic copolymer is prepared for use: acrylamide (AM) in an amount of 10g in total mass was charged into a 250mL three-necked flask equipped with a nitrogen introduction device and a stirring device, and 200mL of water was added thereto and dissolved by stirring sufficiently. Dissolving 0.04g ammonium persulfate and 0.5g sodium formate as molecular weight regulator in 5mL water, stirring to dissolve completely, heating the water bath to 60 deg.C under the protection of nitrogen gas, and making into initiator-containing solution. Adding the prepared solution containing the initiator into a three-neck flask, and reacting in a water bath at 60 ℃ for 3 hours under the protection of nitrogen. The solution obtained by the reaction was added dropwise to 400mL of acetone solution stirred at a high speed, and white solid particles were precipitated. The particles were filtered through a suction filter funnel and then dried in a 50 ℃ oven for 2 h. Its molecular weight is about 3.9X 10 as measured according to GB17514-2008 5。
Then preparing coating liquid: 0.05g of polyacrylamide solid particles are put into a serum bottle, 1mL of water is added, and the solution is fully stirred and dissolved by small magnetons to obtain a solution with the polymer concentration of 0.05 g/mL. Then, 0.05g of glutaraldehyde (about 5% by mass) as a crosslinking agent was added, and the pH of the dope solution was adjusted with hydrochloric acid by ca.2.
3) Coating film liquid
Spreading the coating solution prepared in the step 2) on the epoxy resin substrate which is processed in the step 1) and is 25mm multiplied by 25mm, and then starting a spin coater, wherein the initial speed is about 500r/min, and the duration is 6 s; the final speed is 1500r/min and the duration is 20 s. A uniform surface coating is obtained, the film thickness generally being about 6 μm. And taking down the sample wafer which is subjected to spin coating, putting the sample wafer into a drying oven for drying for 24 hours to obtain a smooth hydrophilic coating with a uniform surface, and storing the hydrophilic coating in a closed container. The crosslinking reaction process is shown in fig. 1, and the aldehyde amine is condensed to form a three-dimensional network structure, so that a firm coating is formed.
4) Checking the result
The sample is tested for the adhesion between the crosslinked polyacrylamide layer and the acrylamide grafted epoxy resin substrate using the standard GB/T9286-1998 test for marking out the paint film of the color paint and the varnish. And (3) using a knife with the blade distance of 2mm, after cutting, cleaning the cut surface by using a soft brush, then adhering the surface by using an adhesive tape, after adhering for 5min, removing the adhesive tape, and observing the falling condition of the coating. The adhesive force reaches ISO 0 grade.
The static contact angle of the coating produced in example 1 with water was measured to be 42.2 ° using a Data-physics OCA-20 contact angle measuring instrument.
Example 2
The preparation method of the epoxy resin with the hydrophilic coating coated on the surface is the same as the method of the example 1, except that:
in the step 1), the using amount of the hydrophilic monomer is 5g, 0.15g of azo-bis-isobutyramidine hydrochloride is adopted as an initiator, and the grafting reaction time is 2 hours.
The final experimental results were similar to those in example 1.
Example 3
The preparation method of the epoxy resin with the hydrophilic coating coated on the surface is the same as the method of the example 1, except that:
in the step 1), 1g of 2-propionamido-2-methylpropanesulfonic acid is adopted as the hydrophilic monomer, 0.01g of potassium persulfate is adopted as the initiator, and the grafting reaction time is 5 hours.
In the step 2), glyoxal is adopted as a crosslinking agent, and the pH is adjusted to be approximately equal to 4.
The final experimental results were similar to those in example 1.
Example 4
The preparation method of the epoxy resin with the hydrophilic coating coated on the surface is the same as the method of the example 1, except that:
in the step 1), 5g of acrylic acid is adopted as the hydrophilic monomer, and the grafting reaction time is 4 h.
The step of preparing the hydrophilic copolymer in the step 2) for later use is changed into the following steps: in thatDissolving 4g of acrylic acid monomer in 50mL of water in a 100mL beaker, mixing acrylamide solid and redistilled acrylic acid liquid according to the mass ratio of 1:7, dropwise adding 1g/mL of NaOH to adjust the pH value of the solution to 6-7 after stirring and dissolving, pouring the solution into a 250mL three-neck flask with a nitrogen introducing device and a stirring device after preparation, and heating the water bath to 60 ℃ under the protection of nitrogen. Dissolving 0.016g of potassium persulfate and 0.2g of sodium formate serving as a molecular weight regulator in 50mL of water, fully stirring to completely dissolve the potassium persulfate and the sodium formate, adding the obtained solution into a three-neck flask, and reacting in a water bath at 60 ℃ for 3 hours under the protection of nitrogen. The solution obtained by the reaction was added dropwise to 400mL of acetone solution stirred at a high speed, and white solid particles were precipitated. The particles were filtered through a suction filter funnel and then dried in a 50 ℃ oven for 2 h. The molecular weight is about 4.1 × 10 measured according to GB17514-2008 method 5。
Preparing coating liquid in step 2): the hydrophilic copolymer was replaced with the copolymer prepared in step 2) of this example, and chromium salt was used as the crosslinking agent.
The experimental results were similar to those in example 1.
Example 5
The preparation of an epoxy resin coated with a hydrophilic coating on the surface is the same as that of example 4, except that:
in the step 2), the acrylic acid monomer is replaced by 2-acrylamide-2-methylpropanesulfonic acid, and 0.04g of sodium persulfate is adopted as the initiator. The molecular weight of the hydrophilic copolymer measured according to GB17514-2008 method is about 3.5X 10 5。
Preparing coating liquid in step 2): the polyacrylamide was replaced by the copolymer prepared in step 2) of this example.
The experimental results were similar to those in example 1.
Example 6
The preparation of an epoxy resin coated with a hydrophilic coating on the surface is the same as that of example 5, except that:
in the step 2), the acrylic acid monomer is replaced by dimethyl diallyl ammonium chloride. The molecular weight of the molecular weight is about 2.0 multiplied by 10 measured according to the GB17514-2008 method 5。
Preparing coating liquid in step 2): the polyacrylamide was replaced by the copolymer prepared in step 2) of this example.
The experimental results were similar to those in example 1.
Example 7
The preparation of an epoxy resin coated with a hydrophilic coating on the surface is the same as that of example 5, except that:
in the step 2), the acrylamide monomer, the dimethyl diallyl ammonium chloride monomer and the sodium acrylate monomer are prepared into reaction liquid according to the mass ratio of 8:1: 1. Its molecular weight is about 1.4X 10 measured according to GB17514-2008 method 5。
Preparing coating liquid in step 2): the polyacrylamide was replaced by the copolymer prepared in step 2) of this example.
The experimental results were similar to those in example 1.
Example 8
The preparation method of the epoxy resin with the hydrophilic coating coated on the surface is the same as the method of the example 1, except that:
preparing coating liquid in step 2): 0.03g of polymer particles are dissolved in 1ml of water, the crosslinking agent glutaraldehyde is replaced by phenolic resin, the amount of the crosslinking agent is replaced by 0.03g, and the pH is approximately equal to 6.
The experimental results were similar to those in example 1.
Example 9
The preparation of an epoxy resin coated with a hydrophilic coating on the surface is the same as that of example 4, except that:
preparing coating liquid in step 2): 0.05g of the polymer solid particles were dissolved in 2ml of water, the crosslinking agent glutaraldehyde was replaced by zirconium salt and the amount of crosslinking agent was replaced by 0.01 g. The experimental results were similar to those in example 1.
Example 10
The preparation of an epoxy resin coated with a hydrophilic coating on the surface is the same as that of example 4, except that:
preparing coating liquid in step 2): 0.1g of the polymer solid particles were dissolved in 2ml of water, and the crosslinking agent glutaraldehyde was replaced by titanium salt, and the amount of the crosslinking agent was replaced by 0.1 g. The experimental results were similar to those in example 1.
Examples 11 to 13
The preparation method of the epoxy resin with the hydrophilic coating coated on the surface is the same as the method of the example 1, except that: the addition amount of the initiator ammonium persulfate in the step 1) is 0.015g, 0.09g and 0.15g respectively.
The properties of the prepared epoxy resin having a hydrophilic coating layer coated on the surface thereof are shown in table 1.
TABLE 1 Properties of epoxy resins with hydrophilic coating applied to the surface, obtained with different initiator additions
Examples Mass fraction wt% of monomer Contact angle Adhesion force
Example 11 0.5 65° —
Example 12 3 43° ISO 0
Example 13 5 55° ISO 2
Comparative example 1 0.08 73° —
Comparative example 2 6 60° —
As can be seen from Table 1, in a proper range, the addition amount of the initiator has little influence on the grafting of the epoxy surface, and the contact angle is similar, the adhesion of the crosslinked coating is good, wherein the contact angle is about 42 degrees within the range of 1-3 wt% of the mass fraction of the monomer, and the range is the best initiator dosage. The initiator dosage is too low, the grafting reaction degree is very low or the grafting reaction can not be carried out, and the hydrophilic coating can not be adhered; the initiator dosage is too high, the concentration of the reaction liquid is too high, so that the viscosity of the reaction liquid is too high, sticky substances on the surface in the later period are difficult to remove, the surface is uneven, the hydrophilicity is not good, and a hydrophilic coating cannot be coated.
Comparative example 1
The preparation method of the epoxy resin with the hydrophilic coating coated on the surface is the same as the method of the example 1, except that:
the step 1) does not graft a hydrophilic polymer to the cured epoxy resin.
The final results obtained were: the adhesive force reaches 4 grades, and 85 degrees and the hydrophilicity is reduced by measuring with a Data-physics OCA-20 contact angle measuring instrument.
Comparative examples 2 to 3
The preparation method of the epoxy resin with the hydrophilic coating coated on the surface is the same as the method of the example 1, except that:
the dosage of the initiator in the step 1) is 0.08 wt% and 6 wt% of the mass of the hydrophilic monomer respectively.
The final results obtained were: the initiator dosage is too low, and the reaction can not be carried out; the initiator dosage is too high, the concentration of the reaction liquid is too high, the viscosity of the reaction liquid is too high, and the sticky substances on the surface at the later stage are difficult to remove.
Comparative example 4
The preparation method of the epoxy resin with the hydrophilic coating coated on the surface is the same as the method of the example 1, except that:
and 2), adding no cross-linking agent into the coating liquid in the step 2).
The final results obtained were: the coating liquid can not be solidified, and the long-time drying can cause the volume shrinkage of the coating and the surface knock-up of the coating, thus forming a very brittle film. And cannot be bonded to the base epoxy.
And (4) conclusion: according to the invention, the hydrophilic polymer is grafted on the surface of the cured epoxy resin, so that the epoxy resin layer is firmly bonded with the hydrophilic coating which is coated subsequently through the crosslinking action, and the hydrophilic coating is firmly bonded with the surface of the epoxy resin under the condition of not using harsh surface cleaning treatment or coating an intermediate bonding layer. The hydrophilic polymer is grafted, the hydrophilic coating and the epoxy resin layer are mutually matched in cross-linking effect, the hydrophilic coating on the surface of the epoxy resin is firmer under the synergistic effect, and the firmness is weakened to different degrees due to the lack of any step. The product of the invention has wide raw material sources, and can prepare the hydrophilic coating with uniform surface properties.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims (10)

1. The epoxy resin with the hydrophilic coating coated on the surface is characterized in that the hydrophilic coating and the epoxy resin layer are bonded in a chemical crosslinking mode; the epoxy resin layer is a cured epoxy resin with a surface grafted with a hydrophilic polymer, and the structural formula of the cured epoxy resin is as follows:
Figure FDA0002187884390000011
in the formula, R 1～R 4For the structural connection point with other epoxy resin chains, R 5～R 6Is a hydrophilic monomeric polar group, n 1、n 2Is a natural number, n is more than or equal to 1 1≤10，1≤n 2≤50000；
The preparation process of the epoxy resin with the hydrophilic coating coated on the surface comprises the following steps:
1) adding an initiator into an aqueous solution of a hydrophilic monomer to prepare a reaction solution; placing the cured epoxy resin substrate in a reaction solution, reacting under the protection of inert gas, and stopping the reaction after the viscosity of the reaction solution is obviously changed to obtain the cured epoxy resin with the surface grafted with the hydrophilic polymer;
the adding amount of the hydrophilic monomer is 0.5-20 wt% of the total mass of the solution, the adding amount of the initiator is 0.1-5 wt% of the mass of the hydrophilic monomer, the inert gas is nitrogen, the reaction temperature is 50 ℃, and the reaction time is 1-8 hours;
2) preparing an aqueous solution of a hydrophilic homopolymer or a hydrophilic copolymer, adding a cross-linking agent, and adjusting the pH value to 2-6 to obtain a coating liquid;
the mass fraction of the hydrophilic homopolymer or the hydrophilic copolymer is 5-40 wt%, and the mass fraction of the cross-linking agent is 0.01-10 wt%;
3) coating the coating liquid prepared in the step 2) on the epoxy resin substrate treated in the step 1), and putting the coated epoxy resin substrate into a drying oven at the temperature of 40-80 ℃ for crosslinking reaction for 2-5 h to finally obtain epoxy resin with a hydrophilic coating firmly coated on the surface; the coating mode is rinsing coating, blade coating, dip coating, spray coating or rotary coating at a certain rotating speed.
2. The epoxy resin with the hydrophilic coating coated on the surface of the epoxy resin as claimed in claim 1, wherein the hydrophilic coating is a hydrophilic homopolymer or a hydrophilic copolymer, the hydrophilic homopolymer is prepared by copolymerizing hydrophilic monomers, and the hydrophilic copolymer is prepared by copolymerizing hydrophilic monomers and different monomersThe molecular weight of the hydrophilic homopolymer or the hydrophilic copolymer is 1.0 multiplied by 10 4～5.0×10 5。
3. The epoxy resin with a hydrophilic coating applied on the surface thereof as claimed in claim 2, wherein the hydrophilic monomer is acrylic acid, acrylamide, 2-propionamido-2-methylpropanesulfonic acid, allylamine, methacrylamide, hydroxyethyl methacrylate or hydroxyethyl acrylate.
4. The epoxy resin with a hydrophilic coating coated on the surface of the epoxy resin according to claim 2, wherein the different ionic monomers are anionic, cationic or zwitterionic monomers; the cationic monomer is a monomer containing a quaternary ammonium salt group; the anionic monomer is a monomer containing carboxyl or sulfonic group.
5. The epoxy resin coated with a hydrophilic coating according to claim 4, wherein the cationic monomer is acryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyltrimethylbenzylammonium chloride, (3-acrylamidopropyl) trimethylammonium chloride, methacrylamidopropyltrimethylammonium chloride, p-vinylbenzyltrimethylammonium chloride, methacrylamide- β -hydroxypropyltrimethylammonium chloride, acrylamido (2-methylbutyl) trimethylammonium chloride or diallyldimethylammonium chloride, and the anionic monomer is acrylic acid, methacrylic acid, maleic acid, itaconic acid, 3-acrylamido-3-methylbutyric acid or 2-acrylamido-2-methylpropanesulfonic acid, or a sodium salt, a potassium salt or an ammonium salt thereof.
6. The method for preparing the epoxy resin with the hydrophilic coating coated on the surface according to any one of claims 1 to 5, comprising the steps of:
1) adding an initiator into an aqueous solution of a hydrophilic monomer to prepare a reaction solution; placing the cured epoxy resin substrate in a reaction solution, reacting under the protection of inert gas, and stopping the reaction after the viscosity of the reaction solution is obviously changed to obtain the cured epoxy resin with the surface grafted with the hydrophilic polymer;
the adding amount of the hydrophilic monomer is 1-5 wt% of the total mass of the solution;
the addition amount of the initiator is 1-3 wt% of the mass of the hydrophilic monomer;
the inert gas is nitrogen, the reaction temperature is 50 ℃, and the reaction time is 2-5 h;
2) preparing an aqueous solution of a hydrophilic homopolymer or a hydrophilic copolymer, adding a cross-linking agent, and adjusting the pH value to 2-6 to obtain a coating liquid;
the mass fraction of the hydrophilic homopolymer or the hydrophilic copolymer is 10-30 wt%;
the mass fraction of the cross-linking agent is 0.1-5 wt%;
3) coating the coating liquid prepared in the step 2) on the epoxy resin substrate treated in the step 1), and putting the coated epoxy resin substrate into a drying oven at the temperature of 40-80 ℃ for crosslinking reaction for 2-5 h to finally obtain epoxy resin with a hydrophilic coating firmly coated on the surface; the coating mode is rinsing coating, blade coating, dip coating, spray coating or rotary coating at a certain rotating speed.
7. The method for preparing the epoxy resin with the hydrophilic coating coated on the surface according to claim 6, wherein the initiator in the step 1) is an azo initiator, an inorganic or organic peroxide; the azo initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile, azobisisobutyramidine hydrochloride, diisobutyl azobisbutyrate and dimethyl azobisisobutyrate; the inorganic or organic peroxide is selected from one or more of ammonium persulfate, sodium persulfate, potassium persulfate, tert-butyl hydroperoxide, dicumyl peroxide and benzoyl peroxide.
8. The preparation method of the epoxy resin with the hydrophilic coating coated on the surface, according to claim 6, is characterized in that the cured epoxy resin substrate in the step 1) is prepared by uniformly mixing the epoxy resin and the curing agent, coating the mixture on the substrate, and curing the mixture in an oven; the curing agent is m-phenylenediamine, m-xylylenediamine, p-phenylenediamine or p-xylylenediamine; the temperature of the oven is 80 ℃, and the curing time is 1-2 h.
9. The method for preparing the epoxy resin with the hydrophilic coating coated on the surface according to claim 6, wherein the crosslinking agent in the step 2) is a reactive oligomer, an organic crosslinking agent or an inorganic crosslinking agent; the active oligomer is urea-formaldehyde resin or phenolic resin; the organic cross-linking agent is formaldehyde, glyoxal, glutaraldehyde, terephthalaldehyde or o-phthalaldehyde; the inorganic cross-linking agent is chromium salt, zirconium salt, boron salt, titanium salt or terbium salt.
10. Use of an epoxy resin coated with a hydrophilic coating according to any one of claims 1 to 5 in oil pipelines.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4082884A (en) * 1975-09-19 1978-04-04 United States Trading International, Inc. Method of reducing fouling of marine structures and coated structure thereof
CN102083897A (en) * 2008-05-30 2011-06-01 3M创新有限公司 Method of making ligand functionalized substrates
CN102307955A (en) * 2008-12-05 2012-01-04 森普鲁斯生物科学公司 Non-fouling, anti-microbial, anti-thrombogenic graft-from compositions
CN104857572A (en) * 2014-12-05 2015-08-26 美昕医疗器械（上海）有限公司 Method for preparing hydrophilic lubrication coating layer on surface of inert high-molecular material and medical instrument

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4082884A (en) * 1975-09-19 1978-04-04 United States Trading International, Inc. Method of reducing fouling of marine structures and coated structure thereof
CN102083897A (en) * 2008-05-30 2011-06-01 3M创新有限公司 Method of making ligand functionalized substrates
CN102307955A (en) * 2008-12-05 2012-01-04 森普鲁斯生物科学公司 Non-fouling, anti-microbial, anti-thrombogenic graft-from compositions
CN104857572A (en) * 2014-12-05 2015-08-26 美昕医疗器械（上海）有限公司 Method for preparing hydrophilic lubrication coating layer on surface of inert high-molecular material and medical instrument

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