CN109439142A - Acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion and preparation method thereof and curing method - Google Patents
Acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion and preparation method thereof and curing method Download PDFInfo
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- CN109439142A CN109439142A CN201811283807.5A CN201811283807A CN109439142A CN 109439142 A CN109439142 A CN 109439142A CN 201811283807 A CN201811283807 A CN 201811283807A CN 109439142 A CN109439142 A CN 109439142A
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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
- 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
- C09D5/03—Powdery paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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Abstract
The invention discloses a kind of acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion and preparation method thereof and curing methods, are calculated in mass percent, which is made up of following raw material of emulsion polymerization in situ: emulsifier 0.5~10%；Initiator 0.1~0.5%；Stabilizer 0.01~0.4%；Acrylic ester monomer 15~40%；Functional monomer 0.5~15%；Other auxiliary agents 0~2%；Active Low-Temperature Curable Epoxy Powder Paint 15~40%；Surplus is water.Aqueous dispersion of the invention has excellent decorative effect and performance, overcomes the defect that powdery paints is difficult to realize high glaze, high transparency, high sense of fullness decorative effect.
Description
Technical field
The present invention relates to coating and field of coating more particularly to a kind of acrylate modified nanometer powder coating interpenetrating networks
Aqueous dispersion and preparation method thereof and curing method.
Background technique
Compared with traditional liquid coating (paint), " 4E type " that powdery paints is approved as everybody (high production efficiency,
Excellent film performance, ecological, environmental protective, economy) coating, the mankind more pay attention to environmental protection, various countries launch respectively limitation atmosphere
Under the situation of organic gas discharge, development space is increasing.However, powdery paints also has clearly disadvantageous place, it is most main
What is wanted is exactly not full enough the beauty of the film coated surface to be formed, and the requirement of high decoration is not achieved.Be in particular in coating layer thickness it is too thick,
The aspects such as poor flatness, gloss is low；The coating layer thickness of powdery paints is usually at 60~100 μm, considerably beyond common paint paint film
Thickness, so thick coating not only influences coating quality, but also brings unnecessary waste.Spraying temperature excessively high (180 simultaneously
~230 DEG C) limitation of × (10~20min) and the requirement to substrate conductivity etc. considerably increases the popularization resistance of powdery paints
Power.
Application No. is the Chinese patents of CN200780025825.7 to disclose a kind of water dispersion of the particle of polymer overmold
Body and preparation method thereof.The purpose that aqueous dispersion is prepared in the patent is to improve pigments and fillers dispersion efficiency in powdery paints.
Application No. is the Chinese patent literatures of CN01804808.0 to disclose a kind of powder painting prepared comprising component A and B
Expect the method for aqueous dispersion, wherein component A is binder resin or binder resin mixture, and component B is that crosslinking agent or crosslinking agent are mixed
Close that object or component A are crosslinking agent or crosslinker mixture and component B is binder resin or binder resin mixture, wherein the party
Method is the following steps are included: a) by the way that the composition that dispersion in water solution includes component A, b are added in Phase inversion emulsification method) it is being added
The composition that component B is added while aqueous medium or later and c) is optionally mixed to get, to obtain point comprising component A and B
Granular media.This method can prepare the stable powdery paints slurry of the particle with 50~800nm range.
Patent WO96/37561 discloses a kind of wet milling process of aqueous powder coating dispersion, by solid powder paint group
At wet-milling in an aqueous medium.But the particle diameter distribution of obtained water dispersion powdery paints is wider (3~20 μm), and partial size shape is not advised
Then, and it is larger.
Patent WO97/45476 provides a kind of method for preparing aqueous powder coating dispersion, wherein by under melting condition
Resin and crosslinking agent etc. are scattered in liquid medium under extrusion condition.It is first that binder resin and crosslinking agent etc. is molten in this method
Melt, then add water in system, obtains aqueous dispersion.The method is not suitable for resin and the fusing point or softening point of crosslinking agent connect
System close or lower than reaction temperature.
Interpenetrating net polymer (IPN) is a kind of unique polyblend, it is poly- by cross-linked polymer I and crosslinking
Made of resulting network continuously mutually interts after conjunction each self-crosslinking of object II.IPN is different from graft copolymer, because in IPN
Chemical bonds do not occur between middle polymer I and II.According to synthetic method difference, IPN can be divided into different type, IPN
Synchronous IPN (SIN), substep IPN (SIPN), interpenetrating networks elastomer (IEN), latex ipn (LIPN) can be divided into.Wherein LIPN is
A kind of emerging IPN composite material.LIPN refers generally to the latex interpenetratingpolymernetworks of broad sense, and this interpenetrating is poly- from composition
Whether the polymer for closing object is crosslinked, and LIPN can be divided into two kinds: i.e. half IPN of LIPN and latex.The former refers to form interpenetrating net
The two kinds of polymer of network crosslinks, and the latter then refers to that only having one kind in two kinds of polymer crosslinks and another kind is
Linear.IPN technology carries out the molecular level of multiple polymers or the physical blending of supermolecule grade in the method for chemistry, it is utilized
The advantages of " forcing compatible " and " synergistic effect " have taken into account both physical blending and chemical copolymerization, it is many that it assigns polymer material
Valuable performance.LIPN is one of most active field in IPN technology, it can be used as paint binder and directly uses, and
It is also beneficial to the post-production molding of polymer.
Summary of the invention
The present invention provides a kind of acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion, aqueous dispersion tools
There are excellent decorative effect and performance, overcomes powdery paints and be difficult to realize high glaze, high transparency, high sense of fullness decorative effect
Defect.
Specific technical solution is as follows:
A kind of acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion, is calculated in mass percent, by following original
Material is made up of emulsion polymerization in situ:
Preferably, a kind of acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion, is calculated in mass percent, by
Following raw material is made up of emulsion polymerization in situ:
The invention also discloses the preparation method of the acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion,
The following steps are included:
(1) swelling of active Low-Temperature Curable Epoxy Powder Paint is cut in cooling bath in acrylic ester monomer
Cutting dissipates, and functional monomer is added later and is dissolved into oil-soluble initiator, obtains oil phase part point；
Other auxiliary agents and the emulsifier of part formulation amount are added in the water of part formulation amount, emulsified water is prepared；
The emulsifier of stabilizer and remaining formula ratio is added in the water of remaining formula ratio, bottoming liquid is prepared；
(2) oil phase part point is added in emulsified water, emulsification pretreatment is prepared into pre-emulsion of the partial size less than 1 μm；
(3) pre-emulsion is added drop-wise in bottoming liquid, emulsion polymerization is carried out using hungry dripping method, pre-emulsion drips
60~90 DEG C are warming up to after complete to be kept the temperature；
Add water soluble starter again later, 60~90 DEG C are kept the temperature, and cooling, filtering, filtrate is that acrylate changes
Property nanometer powder coating interpenetrating networks aqueous dispersion.
The present invention passes through acrylic ester monomer to the swelling action of active Low-Temperature Curable Epoxy Powder Paint resin, in height
Under the mechanical shearing dispersion and emulsion effect of speed shearing dispersion machine, Low-Temperature Curable Epoxy Powder Paint particle is distributed to nano particle size
Pre-emulsification drop in, then by oil-soluble initiator cause pre-emulsification drop Central Plains position polymerization method prepare acrylate
Class micro-crosslinked polymer fetters active Low-Temperature Curable Epoxy Powder Paint and forms lotion, and active temperature curing epoxy low powder is prevented to apply
Material occurs mutually separating in the course of the polymerization process；Emulsion polymerization finally is carried out with intermittent hungry dripping method, it is low that preparation is wrapped in activity
The acrylate aqueous dispersion of the nano-scale particle of warm cured epoxy powdery paints.
Added into the acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion being prepared a small amount of levelling agent,
After the auxiliary agents such as defoaming agent, film forming accelerating, the nanometer aqueous dispersion coating material that can contain 50% or more powdery paints can be produced
Material, which can be with the coating process coating of water paint.
In acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion of the invention, active temperature curing epoxy low powder
Last coating is to be dispersed in acrylic ester monomer with nanoscale, and pass through emulsion polymerization, the micro- cross-linked polymeric of acrylate
Object fetters active Low-Temperature Curable Epoxy Powder Paint, and prevents two kinds of resin systems from mutually separating, and forms microcosmic doped structure；Simultaneously
Because acrylate polymer and epoxide resin polymer have different polymerizations, curing mode and different crosslinking conditions and work
Property point, epoxy resin and acrylate generate respective crosslinking section after aqueous dispersion dried coating film, form different crosslinkings
The resinous coat of network (LIPN structure).
The emulsifier is yin nonionic emulsifier and the reactive emulsifier containing reactivity.
The initiator is radical polymerization initiator；Including oil-soluble initiator and water soluble starter.
The stabilizer be one of sodium pyrophosphate, sodium dihydrogen phosphate, sodium bicarbonate, ferrous sulfate and sodium chloride or
It is a variety of.
The acrylic ester monomer be (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate,
One of (methyl) butyl acrylate, Process Conditions of Cetane Acrylate, Isooctyl acrylate monomer, propylene cyanogen, styrene and itaconic acid are more
Kind.
The functional monomer is N hydroxymethyl acrylamide (NMA), hydroxyethyl acrylamide (NHEMAA), diacetone
Acrylamide (DAAM), acetoacetoxyethyl methacrylate (AAEMA), acetoacetoxyethyl methacrylate
(AAEM), acrylic acid shrinks glycerin ether (GMA), hydroxyethyl methacrylate (HEMA), hydroxy-ethyl acrylate (HEA), acrylic acid
One of hydroxypropyl acrylate (HPA) and N- (N- butoxymethyl) acrylamide (IBMA) are a variety of.
Other described auxiliary agents be crosslinking accelerator, solubilizer, chain-transferring agent, suspension dispersive agent, nano inorganic colloidal sol and
One of nano inorganic particle is a variety of.
It is calculated in mass percent, the active Low-Temperature Curable Epoxy Powder Paint is prepared from the following raw materials:
The low temperature curing agent is the modified glyoxaline compound of liquid-state epoxy resin, and active secondary amino group is by liquid ring
The epoxy group of oxygen resin is protected, and the molar ratio of the epoxy group of the active secondary amino group and liquid-state epoxy resin of glyoxaline compound is
1: 1~1.4.
When using the low temperature curing agent, the epoxy group in active Low-Temperature Curable Epoxy Powder Paint is solidified using imidazoles
Agent solidifies under ionic polymerization mechanism, and general condition of cure is 100~130 DEG C, 3~10min.
The preparation method of the active Low-Temperature Curable Epoxy Powder Paint the following steps are included:
(i) each raw material, melting extrusion after mixing, melting extrusion parameter are weighed by formula ratio are as follows: the area I temperature is 85 DEG C, II
Area's temperature is 75 DEG C, and extruder revolving speed is 80rpm；
(ii) tabletting after melting extrusion, crushing, separation to get.
The curing method of acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion of the invention, comprising: by institute
The acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion stated is sprayed into film, and film is dried at 50~75 DEG C
Afterwards, 100~180 DEG C of 3~10min of crosslinking are warming up to.
Compared with prior art, the invention has the benefit that
(1) in acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion of the invention, active low-temperature setting ring
The solidification temperature of oxygen powdery paints is 100~130 DEG C；And the groups such as hydroxyl, carboxyl or-N hydroxyl (methyl) ethyl of acrylate
It is difficult at 130 DEG C and the epoxy group of powdery paints crosslinks reaction, and acrylate is by Hydrogen Proton item
The polycondensations such as-N hydroxyl (methyl) ethyl crosslinking is taken off under part.The distribution of powdery paints nanoscale and Acrylic emulsion partial size connect
Closely, the mutual doping efficiency of the two is promoted, so high performance IPN polymer can be formed.IPN in any solvent can only be molten
It is swollen, it cannot dissolve, IPN will not be crept and flowed, so that IPN has better bonding force, therefore of the invention
After acrylate modified nanometer powder coating intercrossed network water dispersion cured film forming, adhesive force and solvent resistance are than common ring
Oxygen powdery paints is more preferable；Due to the glass transition temperature (Tg) of the various polymer of IPN be it is selectable, can choose wherein
One phase has lower Tg, so that coating has higher toughness, wear-resisting and adhesion strength；IPN polymer phase region simultaneously
Generally 10~100nm, the far smaller than wavelength of visible light, therefore its coating transparency is not influenced.
Therefore acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion of the invention has excellent decorative effect
And performance, overcome the defect that powdery paints is difficult to realize high glaze, high transparency, high sense of fullness decorative effect.
(2) acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion of the invention combines powdery paints and water
Property coating technical advantage, reduce demand to coalescing agent in water paint coating, realize aqueous dispersion Diamond Search s row
The coating process put.
(3) resin and auxiliary agent fusing point or softening point are wanted when technical solution of the present invention overcomes powder coating formulation design
The limitation asked increases cost advantage when material selection.
(4) acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion of the invention overcomes cryogenic curing
The shorter defect of (100~120 DEG C) powdery paints Storage period.
(5) acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion of the invention can be improved powdery paints face and fill out
Expect dispersion efficiency, increases coating layer decorative colour vividness.
(6) acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion of the invention can be applied with the powder that water dusts
The shortcomings that filling new process spraying, traditional powder coating is overcome to require coated base high conductivity, extends the market of powdery paints
The fields such as range, such as solid wood furniture spraying.
Detailed description of the invention
Fig. 1 is the emulsion particle diameter of acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion prepared by embodiment 1
Distribution map；
Fig. 2 is the aqueous of the acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion prepared containing embodiment 1
The DSC of lacquer coat schemes；
Fig. 3 is the aqueous of the acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion prepared containing embodiment 1
The glass transition temperature figure of lacquer coat；
Fig. 4 is the SEM figure after the aqueous dispersion coating metal spraying prepared containing embodiment 2 and comparative example 1, wherein (a) is pair
Ratio 1 (b) is embodiment 2.
Specific embodiment
Present invention is further described in detail with reference to the accompanying drawings and examples, it should be pointed out that reality as described below
It applies example to be intended to convenient for the understanding of the present invention, and does not play any restriction effect to it.
Raw material and source in embodiment is as shown in table 1:
1 raw material of table and source
Embodiment 1
A kind of emulsion polymerization in situ prepares the side of acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion
Method, comprising the following steps:
1. the preparation of active Low-Temperature Curable Epoxy Powder Paint
(1) it is formulated (kilogram):
(2) technique:
Machine mixing (10min) → melting extrusion (85 DEG C of the area I temperature, the area II of raw material → in mixing pot is weighed by formula
75 DEG C, extruder revolving speed is 80rpm) → tabletting material → ACM crushing → cyclonic separation → powder coating product detection packaging → half
Finished product.
2. preparing acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion
(1) it is formulated (kilogram):
A. pre-emulsion:
B. bottoming liquid:
C. initiator is added:
10 parts of water；
0.2 part of APS.
(2) polymerization technique
1) formula ratio of pre-emulsion is pressed, active Low-Temperature Curable Epoxy Powder Paint is molten in acrylic ester monomer
It is swollen, and (ice bath) with high shear homogeneous emulsifying machine carries out shearing dispersion in sub-cooled bath, by powder coating particles shearing point
Be scattered to it is translucent, the dispersing and dissolving time be 4~5min, add functional monomer and be dissolved into oil-soluble initiator AIBN, obtain
To active Low-Temperature Curable Epoxy Powder Paint monomer solution (oil phase part point)；Simultaneously by pre-emulsion be formulated in other components dissolve
It is dispersed in water, forms aqueous portion；
2) aqueous portion is slowly added to oil phase part point with high shear homogeneous emulsifying machine while stirring and carries out emulsification pretreatment, emulsifies
Time is 3min, is prepared into pre-emulsion of the partial size less than 1 μm, the pre-emulsion after emulsification must be homogeneous, long-time storage not
Layering；
3) bottoming liquid is added in 500 liters of reaction kettles, this pre-emulsion is added dropwise to (time for adding is and reaction temperature control
Matched, general 500 liters of reaction kettles are made, time for adding is 3 hours) into reaction kettle, lotion is carried out with effects of hunger dripping method
Polymerization, reaction temperature are 80 DEG C, and lotion is warming up to 85 DEG C and keeps the temperature 1 hour after dripping entirely, initiator are added, after adding initiator
It keeps the temperature 1.5 hours for 85 DEG C again, is finally cooled to 45 DEG C hereinafter, with 120 mesh filter-cloth filterings, discharging packages spare.
Embodiment 2
A kind of emulsion polymerization in situ prepares the side of acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion
Method, comprising the following steps:
1. the preparation of active Low-Temperature Curable Epoxy Powder Paint
(1) it is formulated (kilogram):
(2) technique:
Machine mixing (10min) → melting extrusion (85 DEG C of the area I temperature, the area II of raw material → in mixing pot is weighed by formula
75 DEG C, extruder revolving speed is 80rpm) → tabletting material → ACM crushing → cyclonic separation → powder coating product detection packaging → half
Finished product.
2. preparing acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion
(1) it is formulated (kilogram):
A. pre-emulsion:
B. bottoming liquid:
C. initiator is added:
10 parts of water；
0.2 part of APS.
(2) polymerization technique
1) formula ratio of pre-emulsion is pressed, active Low-Temperature Curable Epoxy Powder Paint is molten in acrylic ester monomer
It is swollen, and shearing dispersion is carried out with high shear homogeneous emulsifying machine in sub-cooled bath, powder coating particles shearing is distributed to half
Transparent, the dispersing and dissolving time is 4~5min, adds functional monomer and is dissolved into oil-soluble initiator AIBN, obtains activity
Low-Temperature Curable Epoxy Powder Paint monomer solution (oil phase part point)；Simultaneously by pre-emulsion be formulated in the dissolution of other components be dispersed in
In water, aqueous portion is formed；
2) aqueous portion is slowly added to oil phase part point with high shear homogeneous emulsifying machine while stirring and carries out emulsification pretreatment, emulsifies
Time is 3min, is prepared into pre-emulsion of the partial size less than 1 μm, the pre-emulsion after emulsification must be homogeneous, long-time storage not
Layering；
3) bottoming liquid is added in 500 liters of reaction kettles, this pre-emulsion is added drop-wise in reaction kettle, is dripped with effects of hunger
Addition carries out emulsion polymerization, and reaction temperature is 80 DEG C, and lotion is warming up to 85 DEG C and keeps the temperature 1 hour after dripping entirely, adds initiator,
It adds after initiator and to keep the temperature 1.5 hours for 85 DEG C again, be finally cooled to 45 DEG C hereinafter, with 120 mesh filter-cloth filterings, spout bag equipment
With.
Embodiment 3
A kind of emulsion polymerization in situ prepares the side of acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion
Method, comprising the following steps:
1. the preparation of active Low-Temperature Curable Epoxy Powder Paint
(1) it is formulated (kilogram):
(2) technique:
Machine mixing (10min) → melting extrusion (85 DEG C of the area I temperature, the area II of raw material → in mixing pot is weighed by formula
75 DEG C, extruder revolving speed is 80rpm) → tabletting material → ACM crushing → cyclonic separation → powder coating product detection packaging → half
Finished product.
2. preparing acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion
(1) it is formulated (kilogram):
A. pre-emulsion:
B. bottoming liquid:
C. initiator is added:
10 parts of water；
0.2 part of KPS；
0.08 part of sodium hydrogensulfite.
(2) polymerization technique
1) formula ratio of pre-emulsion is pressed, active Low-Temperature Curable Epoxy Powder Paint is molten in acrylic ester monomer
It is swollen, and shearing dispersion is carried out with high shear homogeneous emulsifying machine in sub-cooled bath, powder coating particles shearing is distributed to half
Transparent, the dispersing and dissolving time is 4~5min, adds functional monomer and is dissolved into oil-soluble initiator BPO and triethylamine, obtains
To active Low-Temperature Curable Epoxy Powder Paint monomer solution (oil phase part point)；Simultaneously by pre-emulsion be formulated in other components dissolve
It is dispersed in water, forms aqueous portion；
2) aqueous portion is slowly added to oil phase part point with high shear homogeneous emulsifying machine while stirring and carries out emulsification pretreatment, emulsifies
Time is 3min, is prepared into pre-emulsion of the partial size less than 1 μm, the pre-emulsion after emulsification must be homogeneous, long-time storage not
Layering；
3) in 500 liters of reaction kettles, first lead to nitrogen and catch up with hydrogen, heat up in bottoming, when temperature reaches 60 DEG C, by above-mentioned pre-emulsification
Drop is added in reaction kettle, carries out emulsion polymerization with effects of hunger dripping method, reaction temperature is 60 DEG C, and lotion drips Quan Housheng
Temperature keeps the temperature 1 hour to 75 DEG C, adds initiator, adds after initiator and to keep the temperature 1.5 hours for 75 DEG C again, be finally cooled to 45 DEG C with
Under, appropriate ammonium hydroxide and adipic dihydrazide aqueous solution is added with 120 mesh filter-cloth filterings, discharging packages spare.
Comparative example 1
Formula does not add active low temperature cured powder coating and carries out in-situ polymerization with embodiment 2, but by active low temperature
Cured powder paint is blended with acrylic acid ester emulsion.Its specific embodiment and proportion are as follows:
1. the preparation of active Low-Temperature Curable Epoxy Powder Paint
(1) it is formulated (kilogram):
(2) technique:
Machine mixing (10min) → melting extrusion (85 DEG C of the area I temperature, the area II of raw material → in mixing pot is weighed by formula
75 DEG C, extruder revolving speed is 80rpm) → tabletting material → ACM crushing → cyclonic separation → powder coating product detection packaging → half
Finished product.
2. powdery paints modified acrylate emulsion system
(1) it is formulated (kilogram):
A. pre-emulsion:
B. bottoming liquid:
C. initiator is added:
10 parts of water；
0.2 part of APS.
(2) polymerization technique
1) according to pre-emulsion recipe configuration and pre-emulsification, acrylate pre-emulsion is obtained；
2) bottoming liquid is added in 500 liters of reaction kettles, this pre-emulsion is added drop-wise in reaction kettle, is dripped with effects of hunger
Addition carries out emulsion polymerization, and reaction temperature is 80 DEG C, and lotion is warming up to 85 DEG C and keeps the temperature 1 hour after dripping entirely, adds initiator,
It adds after initiator and to keep the temperature 1.5 hours for 85 DEG C again, be finally cooled to 45 DEG C hereinafter, a small amount of ammonium hydroxide is added, with 120 mesh filter cloth mistakes
Filter, discharging package spare；
3) active 100 parts of Low-Temperature Curable Epoxy Powder Paint (kilogram) is added in above-mentioned emulsion, appropriate increase then is added
Thick dose is thickened to 1500~2000cP of viscosity, prevents powdery paints from precipitating.
Test case
1. emulsion polymer obtained in pair embodiment 1 is tested for the property
As shown in Figure 1, being analyzed using the Zetasizer Nano-ZS nano particle size of Malvern company, Britain, Zeta potential
Instrument is analyzed lotion, average grain diameter 135.4nm, and emulsion particle is in multi-modal.
Emulsion polymer coating (is spontaneously dried 24 hours, room temperature with the Q200 differential scanning calorimeter of TA company, the U.S.
Vacuum dehydration 30min) differential scanning is carried out, DSC figure is as shown in Fig. 2, as can be seen from the figure there are two put emulsion polymer
Thermal spike shows that there are two crosslinking temperature sections for emulsion polymer tool, with the crosslinking temperature of two kinds of interpenetrating net polymers of design
It is almost the same.
Coating is 1.5 hours dry at 60 DEG C, after 120 DEG C of solidification 20min, emulsion polymerization is tested using DSC thermal analysis system
It can be seen that only one wider Tg (as shown in Figure 3) of two kinds of interpenetrating net polymers when the glass transition of object, illustrate poly-
Closing object does not have split-phase, meets the property of interpenetrating net polymer.
2. with acrylate modified nanometer powder coating intercrossed network water dispersion preparation Aqueous paint, to the aqueous lacquer coat
It is tested for the property
Acrylate modified 100 parts of nanometer powder coating interpenetrating networks aqueous dispersion of the preparation of Example 1, are added film forming
5 parts of auxiliary agent propandiol butyl ether, 0.2 part of defoaming agent, 0.2 part of levelling agent, triethanolamine prepares aqueous powder paint in right amount；Coating
Substrate: solid wood；Coating method: spraying；Condition of cure: 50~65 DEG C × 10min, 120 DEG C × 5min.
Test result is shown in Table 2.
2 water paint coating performance test result of table
3. the film performance of pair embodiment 2 and comparative example 1 is compared
After after the lotion of the lotion of comparative example 1 and embodiment 2 is diluted 1 times, it is small to be applied to 60 DEG C of dryings 1.5 on glass slide
When, after 120 DEG C solidify simultaneously vacuum dehydration 30min, surface metal spraying, in scanning electron microscope (the desk-top scanning of Hitachi, Japan SU-3500
Electronic Speculum) under observe its configuration of surface, see Fig. 4.
From Fig. 4 this it appears that emulsion polymerization in situ prepared by embodiment 2 prepares acrylate modified nanometer powder
Coating interpenetrating net polymer film (b) has than the powdery paints of comparative example 1 with emulsion blending polymer coating film (a) higher
Consistency and lustrous surface, it was demonstrated that the technology of the present invention can make powdery paints in acrylate with the microcosmic total of nanoscale
Mixed effect without mutually separating, and uses the blend method of comparative example 1 that cannot reach the effect.
Technical solution of the present invention and beneficial effect is described in detail in embodiment described above, it should be understood that
Above is only a specific embodiment of the present invention, it is not intended to restrict the invention, it is all to be done in spirit of the invention
Any modification, supplementary, and equivalent replacement etc., should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion, which is characterized in that it is calculated in mass percent,
It is made up of following raw material of emulsion polymerization in situ:
2. acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion according to claim 1, which is characterized in that
It is calculated in mass percent, is made up of following raw material of emulsion polymerization in situ:
3. acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion according to claim 1, which is characterized in that
The acrylic ester monomer is (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) third
One of olefin(e) acid butyl ester, Process Conditions of Cetane Acrylate, Isooctyl acrylate monomer, propylene cyanogen, styrene and itaconic acid are a variety of.
4. acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion according to claim 1, which is characterized in that
The functional monomer is N hydroxymethyl acrylamide, hydroxyethyl acrylamide, Diacetone Acrylamide, acetoacetyl first
Base ethyl acrylate, acetoacetoxyethyl methacrylate, acrylic acid shrink glycerin ether (GMA), hydroxyethyl methacrylate second
Ester (HEMA), hydroxy-ethyl acrylate (HEA), hydroxypropyl acrylate (HPA) and N- (N- butoxymethyl) acrylamide (IBMA)
One of or it is a variety of.
5. acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion according to claim 1, which is characterized in that
It is calculated in mass percent, the active Low-Temperature Curable Epoxy Powder Paint is prepared from the following raw materials:
6. acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion according to claim 5, which is characterized in that
The low temperature curing agent is the modified glyoxaline compound of liquid-state epoxy resin, and active secondary amino group is by liquid-state epoxy resin
Epoxy group protection, the molar ratio of the epoxy group of the active secondary amino group and liquid-state epoxy resin of glyoxaline compound is 1: 1~
1.4。
7. acrylate modified nanometer powder coating interpenetrating networks aqueous dispersion according to claim 5, which is characterized in that
The preparation method of the active Low-Temperature Curable Epoxy Powder Paint the following steps are included:
(i) each raw material, melting extrusion after mixing, melting extrusion parameter are weighed by formula ratio are as follows: the area I temperature is 85 DEG C, the area II temperature
Degree is 75 DEG C, and extruder revolving speed is 80rpm；
(ii) tabletting after melting extrusion, crushing, separation to get.
8. a kind of acrylate modified nanometer powder coating interpenetrating networks moisture according to any one of claims 1 to 7
The preparation method of granular media, which comprises the following steps:
(1) swelling of active Low-Temperature Curable Epoxy Powder Paint is subjected to shearing point in acrylic ester monomer in cooling bath
It dissipates, functional monomer is added later and is dissolved into oil-soluble initiator, obtain oil phase part point；
Other auxiliary agents and the emulsifier of part formulation amount are added in the water of part formulation amount, emulsified water is prepared；
The emulsifier of stabilizer and remaining formula ratio is added in the water of remaining formula ratio, bottoming liquid is prepared；
(2) oil phase part point is added in emulsified water, emulsification pretreatment is prepared into pre-emulsion of the partial size less than 1 μm；
(3) pre-emulsion is added drop-wise in bottoming liquid, emulsion polymerization is carried out using hungry dripping method, after pre-emulsion is added dropwise completely
60~90 DEG C are warming up to be kept the temperature；
Add water soluble starter again later, 60~90 DEG C are kept the temperature, and cooling, filtering, filtrate is acrylate modified receive
Rice powdery paints interpenetrating networks aqueous dispersion.
9. a kind of acrylate modified nanometer powder coating interpenetrating networks moisture according to any one of claims 1 to 7
The curing method of granular media characterized by comprising by the acrylate modified nanometer powder coating interpenetrating networks water dispersion
Body spraying film forming, after film is dried at 50~75 DEG C, is warming up to 100~180 DEG C of 3~10min of crosslinking.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113771439A (en) * | 2021-09-17 | 2021-12-10 | 佛山市嘉信盈科技有限公司 | Non-woven fabric toughened water-absorbing acrylate high polymer material and preparation method thereof |
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| CN1400992A (en) * | 2000-02-11 | 2003-03-05 | 阿克佐诺贝尔股份有限公司 | Process for preparing an aqueous powder coating dispersion |
| CN102690588A (en) * | 2012-06-13 | 2012-09-26 | 天长市银狐漆业有限公司 | Powder coating compound for coating thermal sensitive substrate and coating method |
| CN103755890A (en) * | 2014-01-21 | 2014-04-30 | 山东圣光化工集团有限公司 | Method for preparing special epoxy modified polyacrylate emulsion for waterborne industrial paints |
| CN107674540A (en) * | 2017-09-18 | 2018-02-09 | 江苏锐康新材料科技有限公司 | A kind of low temperature curing type powdery paints and its preparation method and application |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1400992A (en) * | 2000-02-11 | 2003-03-05 | 阿克佐诺贝尔股份有限公司 | Process for preparing an aqueous powder coating dispersion |
| CN102690588A (en) * | 2012-06-13 | 2012-09-26 | 天长市银狐漆业有限公司 | Powder coating compound for coating thermal sensitive substrate and coating method |
| CN103755890A (en) * | 2014-01-21 | 2014-04-30 | 山东圣光化工集团有限公司 | Method for preparing special epoxy modified polyacrylate emulsion for waterborne industrial paints |
| CN107674540A (en) * | 2017-09-18 | 2018-02-09 | 江苏锐康新材料科技有限公司 | A kind of low temperature curing type powdery paints and its preparation method and application |
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| CN113771439A (en) * | 2021-09-17 | 2021-12-10 | 佛山市嘉信盈科技有限公司 | Non-woven fabric toughened water-absorbing acrylate high polymer material and preparation method thereof |
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