CN106905555A - A kind of epoxy resin of surface coating hydrophilic coating and its preparation method and application - Google Patents
A kind of epoxy resin of surface coating hydrophilic coating and its preparation method and application Download PDFInfo
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- CN106905555A CN106905555A CN201710190588.5A CN201710190588A CN106905555A CN 106905555 A CN106905555 A CN 106905555A CN 201710190588 A CN201710190588 A CN 201710190588A CN 106905555 A CN106905555 A CN 106905555A
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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
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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
- 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
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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
- 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
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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
- 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
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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
- 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
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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
- 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
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Abstract
The invention discloses the epoxy resin that a kind of surface coats hydrophilic coating, the bonding mode between the hydrophilic coating and epoxy resin layer is chemical crosslinking, and the epoxy resin layer is the cured epoxy resin of surface grafting hydrophilic polymer, and its structural formula is as follows：In formula, R1~R4It is and other epoxy resin chain structure tie points, R5~R6It is hydrophilic monomer polar group, n1、n2It is natural number, 1≤n1≤ 10,1≤n2≤50000.Method proposed by the present invention does not use surface cleaning treatment or the coating intermediate adhesive layer of harshness, make the cured epoxy resin of surface grafting hydrophilic polymer and the hydrophilic coating secure bond of subsequent coated by crosslinked action, so as to reach the purpose for making hydrophilic coating be adhered strongly to epoxy resin substrate surface；Can select homopolymerization or comonomer of the different ions type monomer as hydrophilic coating.Raw material sources extensively, and can be obtained the homogeneous hydrophilic coating of surface nature.
Description
Technical field
The present invention relates to polymers function surface material technology field.Hydrophilic painting is coated more particularly, to a kind of surface
Epoxy resin of layer and its preparation method and application.
Background technology
Current land oil accumulating relies primarily on pipeline to be carried out, and in extremely frigid zones, accumulating relies primarily on heating and supercharging is real
The flowing of existing crude oil.Because in flow process, temperature can be reduced gradually, the viscosity of crude oil can gradually increase.Meanwhile, with temperature
The reduction of degree, the wax in crude oil etc. are constantly separated out into branch and condense in the protective layer and antirust coat of oil pipeline inwall
On epoxy resin surface, the increase of flow resistance is caused, increase the pressure burden that crude oil is transported in pipeline.There is research table
Bright, in the case where surface is smooth, hydrophilic surface has more preferable Wax proofing effect (Su Jianguo, Li Mingyuan etc.；Glass, ring
Oxygen phenolic aldehyde hot curing varnish Lined Pipeline wax control mechanism, University of Petroleum's journal (natural science edition), 1998,22 (1)).
Oil pipeline inwall scribbles etch-proof epoxy resin layer under normal circumstances, but epoxy resin surface hydrophily compared with
Difference.So can coat hydrophilic coating or epoxy resin surface hydrophilic modifying two ways by epoxy resin surface to improve
Oil pipeline inwall hydrophily.Prior art prepares polymer ultra-hydrophilic surface, the method by constructing nanoporous structure
Manufacturing process is simple, low cost and environmentally friendly, by synthesizing two kinds of polyacrylamides of different ions type, and incite somebody to action the two
It is used in mixed way and has obtained the coating with good hydrophilicity.But, the above method has only focused on coating hydrophily in itself
Can, do not consider for how coating firmly bonds with substrate.And in actual applications, the adhesive strength of coating and substrate
It is very crucial index, determines the practical value of coating.Therefore when considering to increase hydrophilic coating in oil pipeline inwall,
The primary key issue that need to be solved is the adhesion strength of hydrophilic coating and epoxy resin.
, it is necessary to coat one layer of tack coat, such as polyvinyl alcohol therebetween when generally coating is Nian Jie with epoxy resin surface,
Multi-layer film structure is formed, the adhesive force of coating is improved.But when hydrophilic coating is bonded, coating is per se with certain water suction
Property, water may make coating different from the volumetric expansion of tack coat, hydrophilic coating is there may be under long-time use and is come off problem.
Prior art is generally all that grafting modification is carried out to uncured resin, and needs are first carried out at halogen acetylation to resin
Reason, then glycerol polymerization is carried out to resin, manufacture craft is more complicated.
Therefore, the invention provides the epoxy resin that a kind of surface coats hydrophilic coating, glued traditional multilayer is not used
In the case of knot layer, hydrophilic polymer is directly grafted by epoxy resin surface after hardening, then it is made by crosslinked action
With the hydrophilic coating secure bond of subsequent coated, manufacture craft is not only simplify, and cause that hydrophilic coating is adhered strongly to
The surface of epoxy resin substrate.
The content of the invention
It is an object of the present invention to provide the epoxy resin that a kind of surface coats hydrophilic coating.
It is another object of the present invention to provide a kind of preparation method of the epoxy resin of surface coating hydrophilic coating.
Third object of the present invention is to provide a kind of application of the epoxy resin of surface coating hydrophilic coating.
Method proposed by the present invention does not use traditional multi-layered bonded layer, and surface grafting hydrophily is gathered by crosslinked action
The cured epoxy resin of compound and the hydrophilic coating secure bond of subsequent coated, hydrophilic coating is adhered strongly to so as to reach
The purpose of epoxy resin substrate surface.
To reach above-mentioned first purpose, the present invention uses following technical proposals：
A kind of surface coats the epoxy resin of hydrophilic coating, the bonding mode between the hydrophilic coating and epoxy resin layer
It is chemical crosslinking；The epoxy resin layer is the cured epoxy resin of surface grafting hydrophilic polymer, and its structural formula is as follows：
In formula, R1~R4It is and other epoxy resin chain structure tie points, R5~R6It is hydrophilic monomer polar group, n1、
n2It is natural number, 1≤n1≤ 10,1≤n2≤50000。
Epoxy resin surface is directly grafted hydrophilic polymer to the present invention after hardening, is provided in epoxy-surface and can be used to hand over
The chemical group of connection effect, while improve the affinity of the epoxy resin surface after graft curing, beneficial to hydrophilic coating in epoxy
Resin surface is sprawled so that epoxy resin layer is no longer made by crosslinked action and the hydrophilic coating secure bond of subsequent coated
With traditional multi-layered bonded layer, manufacture craft is enormously simplify.
Preferably, the hydrophilic monomer is acrylic acid, acrylamide, 2- propionamido- -2- methyl propane sulfonic acids, pi-allyl
Amine, Methacrylamide, hydroxyethyl methacrylate or hydroxy-ethyl acrylate.The present invention uses above-mentioned hydrophilic monomer, equal band
There is double bond and can be used for the polar group being crosslinked.
Preferably, the cured epoxy resin is grafted hydrophilic polymer by initiator, and graft site is by ehter bond
α-H and β-H.α-H and β-H in epoxy resin by ehter bond are more active, and activated centre is easily formed by the attack of initiator,
And then trigger monomer polymerization, graft in asphalt mixtures modified by epoxy resin fat chain.
Preferably, the hydrophilic coating is hydrophilic homopolymer or hydrophilic copolymers；The hydrophilic homopolymer passes through
Hydrophilic monomer is polymerized；The hydrophilic copolymers are by hydrophilic monomer and other hydrophilic monomer copolymerization or hydrophily
Monomer is prepared with different ions type monomer copolymerization；The molecular weight of the hydrophilic homopolymer or hydrophilic copolymers is
1.0×104~5.0 × 105。
Preferably, the different ions type monomer is anionic, cationic or amphoteric ion type monomer；
Preferably, the cationic monomer is the monomer containing quaternary ammonium salt group；It is highly preferred that the cationic monomer is
Acrylyl oxy-ethyl-trimethyl salmiac, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl benzyl
Ammonium chloride, methylacryoyloxyethyl trimethyl benzyl ammonia chloride, (3- acrylamide propyls) trimethyl ammonium chloride, metering system
Amidopropyltrimonium chloride, p- vinylbenzyltrimethyl ammonium chloride, Methacrylamide-β-Hydroxyproyl Trimethyl chlorine
Change ammonium, acrylamido (2- methyl butyls) trimethyl ammonium chloride or diallyldimethylammonium chloride.
Preferably, the anionic monomer is the monomer containing carboxyl or sulfonic group；It is highly preferred that the anion
Monomer is acrylic acid, methacrylic acid, maleic acid, itaconic acid, 3- acrylamidos -3 Methylbutanoic acid or 2- acrylamides -2-
Methyl propane sulfonic acid and their sodium salt, sylvite or ammonium salt.
To reach above-mentioned second purpose, the present invention uses following technical proposals：
A kind of preparation method of the epoxy resin of surface coating hydrophilic coating, comprises the following steps：
1) to initiator is added in the aqueous solution of hydrophilic monomer, it is made into reaction solution；By the epoxy resin substrate after solidification
It is placed in reaction solution, is reacted under the conditions of inert gas shielding, reaction fluid viscosity stops reaction after there is significant change, obtains table
Face is grafted the cured epoxy resin of hydrophilic polymer.α-H and β-H in epoxy resin by ehter bond are more active, triggered
The attack of agent easily forms activated centre, and then triggers monomer polymerization, grafts in asphalt mixtures modified by epoxy resin fat chain.
2) aqueous solution of hydrophilic homopolymer or hydrophilic copolymers is prepared, crosslinking agent is subsequently adding, and it is 2 to adjust pH value
~6, obtain coating liquid.Treated epoxy resin substrate surface due to substantial amounts of polar group, and selected by hydrophilic coating
Crosslinking agent can also be reacted, and coating is bonded together by way of chemical crosslinking with epoxy layer.
3) by step 2) in the coating liquid for preparing be coated on step 1) in epoxy resin substrate after treatment, after coating
Being put into the baking oven that temperature is 40 DEG C~80 DEG C carries out cross-linking reaction, and the reaction time is 2~5h, finally gives surface and firmly coats
The epoxy resin of hydrophilic coating.
Preferably, step 1) described in initiator be azo-initiator, inorganic or organic peroxide；It is highly preferred that
The initiator is organic peroxide；The azo-initiator is selected from azodiisobutyronitrile, ABVN, azo two
One or more in NSC 18620 hydrochloride, the butyric acid diisobutyl ester of azo two, azo-bis-iso-dimethyl；It is described inorganic or have
Machine peroxide is selected from ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, TBHP, cumyl peroxide, peroxidating
One or more in benzoyl.
Preferably, step 1) described in solidify after epoxy resin substrate be well mixed by by epoxy resin and curing agent
Afterwards, it is coated in substrate, is put into after solidifying in baking oven and prepares；Preferably, the curing agent is m-phenylene diamine (MPD), isophthalic diformazan
Amine, p-phenylenediamine or p dimethylamine；The addition of curing agent depends on epoxy resin epoxy value；The temperature of the baking oven is 80
DEG C, hardening time is 1~2h.
Preferably, step 1) described in hydrophilic monomer addition for solution gross mass 0.5~20wt%, more preferably
Ground, the hydrophilic monomer addition is 1~5wt% of solution gross mass.
Preferably, step 1) described in initiator addition for hydrophilic monomer quality 0.1~5wt%, it is highly preferred that
The initiator addition is 1~3wt% of hydrophilic monomer quality.The present invention is by changing the consumption of initiator to asphalt mixtures modified by epoxy resin
Fat surface grafting degree is regulated and controled.
Preferably, step 1) described in inert gas be nitrogen, the reaction temperature be 50 DEG C, the reaction time be 1~8h,
Preferably, the reaction time is 2~5h.
Preferably, step 2) described in hydrophilic homopolymer or hydrophilic copolymers mass fraction be 5~40wt%；More
Preferably, the mass fraction of the hydrophilic homopolymer or hydrophilic copolymers is 10~30wt%.
Preferably, step 2) described in crosslinking agent mass fraction be 0.01~10wt%；It is highly preferred that the crosslinking agent
Mass fraction be 0.1~5wt%.
Preferably, step 2) described in crosslinking agent be living oligomer, organic crosslinking agent or inorganic crosslinking agent；The activity
Oligomer is Lauxite or phenolic resin；The organic crosslinking agent is formaldehyde, glyoxal, glutaraldehyde, terephthalaldehyde or neighbour
Phthalaldehyde；The inorganic crosslinking agent is chromic salts, zirconates, boron salt, titanium salt or terbium salt.Preferably, when hydrophilic monomer is containing carboxylic
During the hydrophilic monomer of acids, curing reaction is done using inorganic crosslinking agent, when hydrophilic monomer is the hydrophilic monomer containing amine
When, the crosslinking agent can do curing reaction.
Preferably, step 3) described in coating method to rinse painting, blade coating, dip-coating, spraying or rotated with certain rotating speed
Coating.
It is attached between hydrophilic coating and epoxy resin substrate in the epoxy resin of the surface coating hydrophilic coating for finally giving
Ability, the rank of ISO more than 1 is reached (using standard GB/T 9286-1998《The lattice of drawing of paint and varnish paint film are tried
Test》).
To reach above-mentioned 3rd purpose, the present invention uses following technical proposals：
A kind of application of epoxy resin of surface coating hydrophilic coating in oil pipeline.
The present invention makes the solidification of surface grafting hydrophilic polymer in cured epoxy resin surface grafting hydrophilic polymer
The hydrophilic coating secure bond of epoxy resin and subsequent coated, so that hydrophilic coating is at the surface cleaning for not using harshness
Under conditions of reason or coating intermediate adhesive layer, with epoxy resin surface secure bond, production technology is simplified, improve coating
Fastness.
Beneficial effects of the present invention are as follows：
(1) hydrophilic coating can not use harshness surface cleaning treatment or coating intermediate adhesive layer under conditions of, with
Epoxy resin surface is firmly bonded.
(2) different monomers be can select and is grafted on epoxy resin surface, under the conditions of relatively simple process, produced available
In the epoxy resin surface of good bond hydrophilic coating.
(3) homopolymerization or comonomer of the different ions type monomer as hydrophilic coating be can select.Raw material sources are extensive, and
The homogeneous hydrophilic coating of surface nature can be obtained.
Brief description of the drawings
Specific embodiment of the invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 shows the cross-linking reaction process schematic in the embodiment of the present invention 1.
Specific embodiment
In order to illustrate more clearly of the present invention, the present invention is done further with reference to preferred embodiments and drawings
It is bright.Similar part is indicated with identical reference in accompanying drawing.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
Embodiment 1
A kind of preparation of the epoxy resin of surface coating hydrophilic coating, comprises the following steps：
1) cured epoxy resin of surface grafting hydrophilic polymer is prepared
It is standby that reaction solution is prepared first：Take in 3g acrylamides addition 150ml beakers, add water to gross mass up to 100g, fill
Divide stirring and dissolving.Add in 0.03g ammonium persulfates to reaction solution, be sufficiently stirred for dissolving, be configured to reaction solution.
Then epoxy resin is solidified：5g epoxy resin E44 are taken, the ethanol/acetone volume ratio 1 of 2g is dissolved in:1
In epoxide diluent, 1g m-xylene diamines are added, stirred.Glass sheet surface is coated in, 80 DEG C of curing oven 2h are put into,
Taking-up is solidified with the sheet glass of epoxy resin (following be referred to as print) and is put into that to dry place's preservation stand-by.
Finally epoxy resin is grafted：Print is lain in into reaction bulb bottom, reaction solution is added toward reaction bulb, instead
It need to be higher than epoxy resin surface to answer liquid liquid level.3h is reacted under 50 DEG C of nitrogen protective condition, reaction fluid viscosity occurs bright
Stop reaction after aobvious change, take out print.
Print is put into clear water and is soaked 3 days, remove surface non-grafted polymers.It is put into 50 DEG C of vacuum drying ovens
In carry out the drying of 6h, take out stand-by.The group being had using In situ ATR-FTIR method test sample surface, confirms to carry
Amide group, illustrates to be grafted successfully.Put into vacuum drying chamber stand-by.
2) coating liquid is prepared
It is standby that hydrophilic copolymers are prepared first：By gross mass for the acrylamide (AM) of 10g is added with logical nitrogen dress
Put and the 250mL three-neck flasks of agitating device in, add 200mL water, be sufficiently stirred for dissolving.With 5mL water dissolves 0.04g persulfuric acid
Ammonium and 0.5g molecular weight modifier sodium formates, are sufficiently stirred for being allowed to be completely dissolved, and under nitrogen protection warming-in-water to 60 DEG C,
It is formulated as the solution containing initiator.Preparing during the solution containing initiator adds three-neck flask, under nitrogen protection, 60 DEG C of water
3h is reacted in bath.Reaction resulting solution is dropped in the 400mL acetone solns of high-speed stirred, Precipitation white solid particle.
Particle is filtered through suction funnel, places into 50 DEG C of oven drying 2h.Its molecular weight is measured according to GB17514-2008 methods to be about
3.9×105。
Then coating liquid is modulated：Take 0.05g polyacrylamide solid particles to be put into serum bottle, add 1mL water, use small magnetic
Son be sufficiently stirred for dissolving, with solution polymer concentration be 0.05g/mL.Then, add crosslinking agent 0.05g glutaraldehydes (about total
Quality 5%), and adjust coating liquid pH ≈ 2 with hydrochloric acid.
3) coating liquid is coated
Take step 2) in the coating liquid for preparing be paved with 25mm × 25mm in step 1) in the epoxy resin-matrix that treats
On bottom, then start sol evenning machine, initial velocity is about 500r/min, and the duration is 6s；End speed is 1500r/min, when continuing
Between be 20s.Homogeneous face coat is obtained, film thickness is typically about 6 μm or so.The good print of spin coating is removed, is put into baking oven
24h is dried, and obtains the smooth hydrophilic coating of uniform surface, is stored in closed container.Cross-linking reaction process as shown in figure 1,
Firm coating, as tridimensional network, is formed by aldimine condensation.
4) result is tested
Print uses standard GB/T 9286-1998《The cross cut test of paint and varnish paint film》It is poly- to detect sample crosslinking
Adhesive ability between acrilamide layer and acrylamide graft epoxy resin substrate.The use of blade distance is the knife of 2mm, cutting knot
Shu Yihou, is cleared away with banister brush in cutting surfaces, is then bonded at surface using adhesive tape, in stickup after 5min, is taken off,
Observation coating shedding situation.Adhesive force reaches 0 grade of ISO.
Using coating and the static state of water made by Data-physics OCA-20 contact angle measurements measurement embodiment 1
Contact angle is 42.2 °.
Embodiment 2
A kind of surface coats the preparation of the epoxy resin of hydrophilic coating, and method is with embodiment 1, difference：
Step 1) in hydrophilic monomer consumption be 5g, initiator using 0.15g azo-bis-isobutyrate hydrochloride, grafting is anti-
It is 2h between seasonable.
Final experimental result is similar with embodiment 1.
Embodiment 3
A kind of surface coats the preparation of the epoxy resin of hydrophilic coating, and method is with embodiment 1, difference：
Step 1) in hydrophilic monomer using 1g 2- propionamido- -2- methyl propane sulfonic acids, initiator is using 0.01g
Potassium peroxydisulfate, the graft reaction time is 5h.
Step 2) in crosslinking agent use glyoxal, regulation pH ≈ 4.
Final experimental result is similar with embodiment 1.
Embodiment 4
A kind of surface coats the preparation of the epoxy resin of hydrophilic coating, and method is with embodiment 1, difference：
Step 1) in hydrophilic monomer use 5g acrylic acid, the graft reaction time be 4h.
Step 2) in prepare the standby step of hydrophilic copolymers and be changed to：The total matter of 50mL water dissolves is used in 100mL beakers
Measure the acrylic monomers for 4g, in mass ratio 1:7 acrylamide solid and redistillation liquid acrylic mixing, after stirring and dissolving
1g/mL NaOH are added dropwise and adjust pH value of solution to 6~7, the necks of 250mL tri- with logical nitrogen device and agitating device are poured into after preparing
In flask, and under nitrogen protection warming-in-water to 60 DEG C.With 50mL water dissolves 0.016g potassium peroxydisulfates and 0.2g molecular weight
Conditioning agent sodium formate, is sufficiently stirred for being allowed to be completely dissolved, and resulting solution is added in three-neck flask, 60 DEG C of water under nitrogen protection
3h is reacted in bath.Reaction resulting solution is dropped in the 400mL acetone solns of high-speed stirred, Precipitation white solid particle.
Particle is filtered through suction funnel, places into 50 DEG C of oven drying 2h.Its molecular weight is measured according to GB 17514-2008 methods to be about
4.1×105。
Step 2) middle modulation coating liquid：Hydrophilic copolymers are changed makees the present embodiment step 2) the middle copolymer for preparing, crosslinking
Agent uses chromic salts.
The experimental result is similar with embodiment 1.
Embodiment 5
A kind of surface coats the preparation of the epoxy resin of hydrophilic coating, and method is with embodiment 4, difference：
Step 2) in acrylic monomers change and make 2- acrylamide-2-methyl propane sulfonics, initiator uses 0.04g persulfuric acid
Sodium.The hydrophilic copolymers molecular weight obtained according to GB 17514-2008 method measurements is about 3.5 × 105。
Step 2) middle modulation coating liquid：Polyacrylamide is changed makees the present embodiment step 2) the middle copolymer for preparing.
Experimental result is similar with embodiment 1.
Embodiment 6
A kind of surface coats the preparation of the epoxy resin of hydrophilic coating, and method is with embodiment 5, difference：
Step 2) in acrylic monomers change and make dimethyl diallyl ammonium chloride.Measured according to GB 17514-2008 methods
Its molecular weight is about 2.0 × 105。
Step 2) middle modulation coating liquid：Polyacrylamide is changed makees the present embodiment step 2) the middle copolymer for preparing.
Experimental result is similar with embodiment 1.
Embodiment 7
A kind of surface coats the preparation of the epoxy resin of hydrophilic coating, and method is with embodiment 5, difference：
Step 2) in acrylamide monomer, dimethyldiallylammonchloride chloride monomer and sodium acrylate monomers in mass ratio
8:1:1 is configured to reaction solution.Its molecular weight is measured according to GB 17514-2008 methods be about 1.4 × 105。
Step 2) middle modulation coating liquid：Polyacrylamide is changed makees the present embodiment step 2) the middle copolymer for preparing.
Experimental result is similar with embodiment 1.
Embodiment 8
A kind of surface coats the preparation of the epoxy resin of hydrophilic coating, and method is with embodiment 1, difference：
Step 2) middle modulation coating liquid：Take 0.03g polymer beads to be dissolved in 1ml water, crosslinking agent glutaraldehyde is changed makees phenol
Urea formaldehyde, dosage of crosslinking agent is changed and makees 0.03g, pH ≈ 6.
Experimental result is similar with embodiment 1.
Embodiment 9
A kind of surface coats the preparation of the epoxy resin of hydrophilic coating, and method is with embodiment 4, difference：
Step 2) middle modulation coating liquid：Take 0.05g polymer solid particles to be dissolved in 2ml water, crosslinking agent glutaraldehyde is changed
Make zirconates, dosage of crosslinking agent is changed and makees 0.01g.The experimental result is similar with embodiment 1.
Embodiment 10
A kind of surface coats the preparation of the epoxy resin of hydrophilic coating, and method is with embodiment 4, difference：
Step 2) middle modulation coating liquid：Take 0.1g polymer solid particles to be dissolved in 2ml water, crosslinking agent glutaraldehyde changes work
Titanium salt, dosage of crosslinking agent is changed and makees 0.1g.The experimental result is similar with embodiment 1.
Embodiment 11~13
A kind of surface coats the preparation of the epoxy resin of hydrophilic coating, and method is with embodiment 1, difference：Step
1) addition of initiator ammonium persulfate is respectively 0.015g, 0.09g, 0.15g in.
The performance of the epoxy resin of the surface coating hydrophilic coating for preparing is as shown in table 1.
The performance of the epoxy resin of the surface coating hydrophilic coating that the different initiator additions of table 1 are obtained
| Embodiment | Monomer mass fraction wt% | Contact angle | Adhesive force |
| Embodiment 11 | 0.5 | 65° | — |
| Embodiment 12 | 3 | 43° | ISO 0 |
| Embodiment 13 | 5 | 55° | ISO 2 |
| Comparative example 1 | 0.08 | 73° | — |
| Comparative example 2 | 6 | 60° | — |
As it can be seen from table 1 in appropriate scope, the addition of initiator is little on epoxy-surface grafting influence, performance
For contact angle size is close, cross-linked coating adhesive force is good, wherein in the range of 1~3wt% of monomer mass fraction, the contact for obtaining
42 ° or so of angle, it is known that the scope is optimal initiator amount.Initiator amount is too low, and graft reaction degree is very low or nothing
Method is carried out, it is impossible to adhere to hydrophilic coating；Initiator amount is too high, and reaction solution concentration is too high, causes reaction solution viscosity excessive, the later stage
Surface dope is difficult to remove, surface irregularity and hydrophily is not good, it is impossible to coat hydrophilic coating.
Comparative example 1
A kind of surface coats the preparation of the epoxy resin of hydrophilic coating, and method is with embodiment 1, difference：
Step 1) in grafting hydrophilic polymer is not carried out to cured epoxy resin.
The result for finally giving：Adhesive force reaches 4 grades, is measured using Data-physics OCA-20 contact angle measurements
85 ° are learnt, hydrophily declines.
Comparative example 2~3
A kind of surface coats the preparation of the epoxy resin of hydrophilic coating, and method is with embodiment 1, difference：
Step 1) in the consumption of initiator be respectively 0.08wt%, 6wt% of hydrophilic monomer quality.
The result for finally giving：Initiator amount is too low, and reaction can not be carried out；Initiator amount is too high, reaction solution concentration
It is too high, cause reaction solution viscosity excessive, later stage surface dope is difficult to remove.
Comparative example 4
A kind of surface coats the preparation of the epoxy resin of hydrophilic coating, and method is with embodiment 1, difference：
Step 2) in be added without crosslinking agent in coating liquid.
The result for finally giving：Coating liquid cannot solidify, and long-time drying can cause coating volume contraction, and surface is rung,
Form very crisp film.Cannot be Nian Jie with matrix epoxy resin.
Conclusion：The present invention is in cured epoxy resin surface grafting hydrophilic polymer so that epoxy resin layer is by crosslinking
Effect and the hydrophilic coating secure bond of subsequent coated so that hydrophilic coating do not use the surface cleaning treatment of harshness or
Under conditions of coating intermediate adhesive layer, firmly bonded with epoxy resin surface.Grafting hydrophilic polymer and hydrophilic coating with
The crosslinked action of epoxy resin layer cooperates therebetween, synergy, makes the hydrophilic coating of epoxy resin surface more
Firmly, lacking either step can all make the fastness have different degrees of decrease.Products material wide material sources of the invention, can make
Obtain the homogeneous hydrophilic coating of surface nature.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not right
The restriction of embodiments of the present invention, for those of ordinary skill in the field, may be used also on the basis of the above description
To make other changes in different forms, all of implementation method cannot be exhaustive here, it is every to belong to this hair
Obvious change that bright technical scheme is extended out changes row still in protection scope of the present invention.
Claims (10)
1. a kind of surface coats the epoxy resin of hydrophilic coating, it is characterised in that between the hydrophilic coating and epoxy resin layer
Bonding mode for chemical crosslinking；The epoxy resin layer is the cured epoxy resin of surface grafting hydrophilic polymer, its knot
Structure formula is as follows：
In formula, R1~R4It is and other epoxy resin chain structure tie points, R5~R6It is hydrophilic monomer polar group, n1、n2For
Natural number, 1≤n1≤ 10,1≤n2≤50000。
2. a kind of surface according to claim 1 coats the epoxy resin of hydrophilic coating, it is characterised in that the hydrophilic painting
Layer is hydrophilic homopolymer or hydrophilic copolymers, and the hydrophilic homopolymer is prepared by hydrophilic monomer copolymerization, institute
State hydrophilic copolymers to be prepared by hydrophilic monomer and different ions type monomer copolymerization, the hydrophilic homopolymer or parent
The molecular weight of aqueous copolymer is 1.0 × 104~5.0 × 105。
3. a kind of surface according to claim 2 coats the epoxy resin of hydrophilic coating, it is characterised in that the hydrophily
Monomer is acrylic acid, acrylamide, 2- propionamido- -2- methyl propane sulfonic acids, allyl amine, Methacrylamide, metering system
Sour hydroxyl ethyl ester or hydroxy-ethyl acrylate.
4. a kind of surface according to claim 1 coats the epoxy resin of hydrophilic coating, it is characterised in that it is described it is different from
Subtype monomer is anionic, cationic or amphoteric ion type monomer；The cationic monomer is to contain quaternary ammonium salt group
Monomer；The anionic monomer is the monomer containing carboxyl or sulfonic group.
5. a kind of surface according to claim 4 coats the epoxy resin of hydrophilic coating, it is characterised in that the cation
Monomer is acrylyl oxy-ethyl-trimethyl salmiac, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl front three
Base benzyl ammonium chloride, methylacryoyloxyethyl trimethyl benzyl ammonia chloride, (3- acrylamide propyls) trimethyl ammonium chloride, first
Base acrylamido propyl trimethyl ammonium chloride, p- vinylbenzyltrimethyl ammonium chloride, Methacrylamide-β-hydroxypropyl three
Ammonio methacrylate, acrylamido (2- methyl butyls) trimethyl ammonium chloride or diallyldimethylammonium chloride；It is described it is cloudy from
Sub- monomer be acrylic acid, methacrylic acid, maleic acid, itaconic acid, 3- acrylamidos -3 Methylbutanoic acid or 2- acrylamides -
2- methyl propane sulfonic acids and their sodium salt, sylvite or ammonium salt.
6. a kind of surface as described in claim 1-5 is any coats the preparation method of the epoxy resin of hydrophilic coating, its feature
It is to comprise the following steps：
1) to initiator is added in the aqueous solution of hydrophilic monomer, it is made into reaction solution；Epoxy resin substrate after solidification is placed in
In reaction solution, reacted under the conditions of inert gas shielding, reaction fluid viscosity stops reaction after there is significant change, obtains to surface and connects
The cured epoxy resin of branch hydrophilic polymer；
The hydrophilic monomer addition is 0.5~20wt% of solution gross mass, it is preferable that the hydrophilic monomer addition
It is 1~5wt% of solution gross mass；
The initiator addition is 0.1~5wt% of hydrophilic monomer quality, it is preferable that the initiator addition is parent
1~3wt% of aqueous monomers quality；
The inert gas is nitrogen, and the reaction temperature is 50 DEG C, and the reaction time is 1~8h, it is preferable that the reaction time is 2
~5h；
2) aqueous solution of hydrophilic homopolymer or hydrophilic copolymers is prepared, crosslinking agent is subsequently adding, and it is 2~6 to adjust pH value,
Obtain coating liquid；
The mass fraction of the hydrophilic homopolymer or hydrophilic copolymers is 5~40wt%, it is preferable that the hydrophily homopolymerization
The mass fraction of thing or hydrophilic copolymers is 10~30wt%；
The mass fraction of the crosslinking agent be 0.01~10wt%, it is preferable that the mass fraction of the crosslinking agent be 0.1~
5wt%；
3) by step 2) in the coating liquid for preparing be coated on step 1) in epoxy resin substrate after treatment, be put into after coating
Temperature is to carry out cross-linking reaction in 40 DEG C~80 DEG C of baking oven, and the reaction time is 2~5h, finally give surface firmly coat it is hydrophilic
The epoxy resin of coating；The coating method is to rinse painting, blade coating, dip-coating, spraying or carry out rotary coating with certain rotating speed.
7. a kind of surface according to claim 6 coats the preparation method of the epoxy resin of hydrophilic coating, it is characterised in that
Step 1) described in initiator be azo-initiator, inorganic or organic peroxide；The azo-initiator is selected from azo
Bis-isobutyronitrile, ABVN, azo-bis-isobutyrate hydrochloride, the butyric acid diisobutyl ester of azo two, the isobutyric acid diformazan of azo two
One or more in ester；Described inorganic or organic peroxide is selected from ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, the tert-butyl group
One or more in hydrogen peroxide, cumyl peroxide, benzoyl peroxide.
8. a kind of surface according to claim 6 coats the preparation method of the epoxy resin of hydrophilic coating, it is characterised in that
Step 1) described in solidify after epoxy resin substrate by by epoxy resin and curing agent it is well mixed after, be coated in substrate
On, it is put into after solidifying in baking oven and prepares；The curing agent is m-phenylene diamine (MPD), m-xylene diamine, p-phenylenediamine or to benzene two
Methylamine；The temperature of the baking oven is 80 DEG C, and hardening time is 1~2h.
9. a kind of surface according to claim 6 coats the preparation method of the epoxy resin of hydrophilic coating, it is characterised in that
Step 2) described in crosslinking agent be living oligomer, organic crosslinking agent or inorganic crosslinking agent；The living oligomer is ureaformaldehyde tree
Fat or phenolic resin；The organic crosslinking agent is formaldehyde, glyoxal, glutaraldehyde, terephthalaldehyde or OPA；The nothing
Machine crosslinking agent is chromic salts, zirconates, boron salt, titanium salt or terbium salt.
10. a kind of surface as described in claim 1-5 is any coats the epoxy resin of hydrophilic coating answering in oil pipeline
With.
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| CN111635597A (en) * | 2020-06-12 | 2020-09-08 | 中国科学院长春应用化学研究所 | Polystyrene heat-insulating material and preparation method thereof |
| CN112004465A (en) * | 2018-02-26 | 2020-11-27 | T&W工程公司 | Electrode for detecting bioelectric signals |
| CN112142925A (en) * | 2020-10-13 | 2020-12-29 | 湖南平安医械科技有限公司 | Hydrophilic self-lubricating polymer modifier, synthetic method and application thereof |
| CN112827478A (en) * | 2018-07-02 | 2021-05-25 | 旭化成医疗株式会社 | Blood treatment bead |
| CN113694261A (en) * | 2020-05-21 | 2021-11-26 | 江苏百赛飞生物科技有限公司 | Antibacterial composite coating and preparation method and product thereof |
| US11850345B2 (en) | 2018-07-02 | 2023-12-26 | Asahi Kasei Medical Co., Ltd. | Beads for blood processing |
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