CN106047068A - VOC-free (volatile organic compounds free) epoxy resin and HNT (halloysite nanotube) composite self-repair coating and preparation method thereof - Google Patents
VOC-free (volatile organic compounds free) epoxy resin and HNT (halloysite nanotube) composite self-repair coating and preparation method thereof Download PDFInfo
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- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
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Abstract
A VOC-free (volatile organic compounds free) epoxy resin and HNT (halloysite nanotube) composite self-repair coating comprises the following components: waterborne epoxy resin and HNT composite emulsion, a curing agent, 0.1-0.8 part of a leveling agent, a wetting agent and a defoaming agent; a preparation method includes the steps: first, weighing 69.5-145 parts of waterborne epoxy resin emulsion in a three-port flask, weighing 0.5-5 parts of HNT loading a corrosion inhibitor, adding to the three-port flask, and electrically and chemically stirring; second, ultrasonically dispersing, moving to an electric stirring device, stirring, repeating three times to form disperse, stable and homogeneous waterborne epoxy resin and HNT composite emulsion; third, mixing well the waterborne epoxy resin and HNT composite emulsion, the curing agent, the leveling agent, the wetting agent and the defoaming agent to required fineness; the coating has antiseptic and self-repair functions; the coating is green, nontoxic and harmless, good in adhesion, high in hardness, simple to prepare and low in production cost.
Description
Technical field
The present invention relates to nano hybridization self-healing coatings and field of compound material, particularly to a kind of VOC free epoxy resin/
HNTs is combined self-healing coatings and preparation method thereof.
Background technology
Halloysite nanotubes (HNTs) is a kind of natural inorganic aluminosilicate, is naturally to be rolled up by under aluminosilicate lamella air slaking
The hollow tubular structure of curved one-tenth, has big draw ratio.Internal diameter is about 5 ~ 20 nm, and external diameter is about 10 ~ 50 nm, and length is about
100~400 nm.Outer tube layer is silicon-oxy tetrahedron layer, and internal layer is alumina octahedral sheet.HNTs has that heat stability is strong, specific surface
The advantage such as long-pending big, in addition the hollow nano tubular structure of its uniqueness and surface texture, be widely used in composite, pottery,
The field such as nano-form, catalyst carrier.As filler, can effectively strengthen the performance of high molecular polymer.Due to galapectite
Nanotube has polar surfaces, thus modifies without any surface and just can preferably be distributed to epoxy resin (EP) isopolarity
In polymer.
Traditional epoxy coating volatile organic matter (VOC) content is high, has penetrating odor, is unfavorable for environmental protection
With health.And aqueous epoxide resin paint is compared with traditional, have again hardness deficiency, mechanical property not and poor water resistance etc. lacks
Point.Being combined with aqueous epoxy resins by HNTs, can give full play to the nano effect of HNTs, the hardness of reinforced epoxy, heat are steady
Qualitative and mechanical property.It addition, at present polymer base selfreparing nano material is usually: nano silicon, nano metal from
Son, nano-metal-oxide etc., but need autonomous preparation, cost is high, uneconomical environmental protection.
The most also there is not adding the product of the aqueous epoxy resins class self-repair material of halloysite nanotubes, yet
Have no report.
Summary of the invention
For overcoming above-mentioned the deficiencies in the prior art, it is an object of the invention to provide the self-repair function that has of a kind of VOC free
Aqueous epoxy resins/HNTs composite coating and preparation method thereof, the present invention it is critical only that inorganic nano material and aqueous ring
Epoxy resins is combined, and combines the characteristic of the two, has obtained having the composite coating that combination property is higher.Utilize HNTs from
The cavity structure that body is regular, loads corrosion inhibiter wherein so that it is have the function of slow release.And use polyelectrolyte self assembly layer by layer
Method, it is packaged according to predetermined needs, with strengthen inorganic material slow release effect and extend slow-release time.Originally ring
Protect the compound rear prepared coating of HNTs of non-toxic water epoxy resin latex pure natural in addition, more safe and harmless, have good
Good economic benefit and social benefit, environmental protection.And due to the effect that nano material is unique, primary resin film also can be improved
Storage modulu, hardness, pliability and heat stability etc..When film is the most impaired, corrosion inhibiter will be had to release
Release and carry out self-repair function.
For reaching above-mentioned purpose, the technical solution used in the present invention is:
A kind of VOC free epoxy resin/HNTs is combined self-healing coatings, it is characterised in that include following components: water-base epoxy tree
Fat/HNTs complex emulsions 70 ~ 150 parts, 12 ~ 35 parts of firming agent, levelling agent 0.1 ~ 0.8 part, wetting agent 0.1 ~ 1 part, defoamer 0.1
~ 0.6 part.
Described aqueous epoxy resins/HNTs complex emulsions includes: aqueous epoxy resin emulsion 69.5 ~ 145 parts, has
Load the HNTs filler 0.5 ~ 5 part of corrosion inhibiter；Described corrosion inhibiter be BTA (BTA), methyl benzotriazazole (TTA),
A kind of or the most several in water solublity mercapto benzothiazole (CAS), mercaptobenzothiazoler (MBT), 8-hydroxyquinoline.
Described firming agent is the ERC2602 of Guangzhou Ou Peng Chemical Co., Ltd., ERC2606, ERC2608, ERC2609,
One or more in ERC2635；
Described wetting agent is BD-3245, TEGO245 of Hangzhou Bao Er get organosilicon company limited, the Guangzhou limited public affairs of Ou Peng chemical industry
One in the O-level X1840 of department；
Described levelling agent is the Modarez PSL2000 of Guangzhou Ou Peng Chemical Co., Ltd., Modarez PW336, Modarez
One or more in X080 levelling agent；
The EL-2600 of described defoamer Dongguan City Yi Lian Chemical Industry Science Co., Ltd, EL-2601, EL-2602, EL-2603,
One or more in EL-2607, EL-2638 defoamer.
A kind of VOC free epoxy resin/HNTs is combined the preparation method of self-healing coatings, comprises the following steps:
By aqueous epoxy resins/HNTs complex emulsions 70 ~ 150 parts, 12 ~ 35 parts of firming agent, levelling agent 0.1 ~ 0.8 part, wetting agent
0.1 ~ 1 part, defoamer 0.1 ~ 0.6 part is sufficiently mixed, and is sufficiently stirred for, and reaches the fineness needed.
Described is to use ultrasonic disperse and machinery by the method that aqueous epoxy resin emulsion and HNTs filler carry out being combined
Stirring alternately mixing so that it is be dispersed in emulsion.
The preparation technology of described HNTs filler includes: use the method for vacuum loading that corrosion inhibiter is loaded into the sky of HNTs
In chamber, utilize the adsorption mechanism of polyelectrolyte, the method using LBL self-assembly, the HNTs equipped with corrosion inhibiter is packaged place
Reason.
The preparation process of described aqueous epoxy resins/HNTs complex emulsions includes:
First, the aqueous epoxy resin emulsion weighing 69.5 ~ 145 parts is placed in the there-necked flask of 100 ml, then weighs 0.5 ~ 5 part
Equipped with the HNTs of corrosion inhibiter, it is slowly added in there-necked flask, at 20 DEG C ~ 35 DEG C, motor machine stirring 10 ~ 20 min；
Secondly, carried out ultrasonic disperse, after ultrasonic 10 ~ 30 min, then moved under electric mixing device, stirred 5 ~ 10 min,
So circulation three times, forms the emulsion that stably dispersing is homogeneous.
Described HNTs filler loads the preparation technology of corrosion inhibiter and comprises the following steps:
A, weighs the HNTs of 0.5 ~ 5 part, is slowly added to fill in the beaker of deionized water, stirs 3 ~ 5h, so at 20 DEG C ~ 35 DEG C
After in centrifuge, separate 3 ~ 5 min with the rotating speed of 1000 ~ 2000 rad/min, be divided into from three times, and sucking filtration, steaming be repeated
Distilled water is washed, and is dried 18 ~ 30h, is ground after drying in 40 DEG C ~ 50 DEG C vacuum tanks；
B, weighs the corrosion inhibiter of 0.1 ~ 0.5 part, is placed in beaker, adds 1 ~ 5 part of deionized water and 1 ~ 5 part of dehydrated alcohol mixing
Liquid, at 20 ~ 25 DEG C, magnetic agitation 10 ~ 20 min, then weigh the HNTs of 0.2 ~ 2 part, it is slowly added in beaker, 20 ~ 25
At DEG C, magnetic agitation 15 ~ 30min so that it is be sufficiently mixed uniformly；
C. the solution in the beaker of step b is transferred in the Dewar bottle being dried, carries out vacuum loading, make the true of vacuum equipment
Reciprocal of duty cycle is 0.1 ~ 1MPa, and the persistent period is 20 ~ 40min, for proof load effect, can repeatedly circulate and load, after load
On centrifuge, the rotating speed of 1000 ~ 2000 rad/min separates 5 ~ 15 min, is washed with deionized 2 ~ 6 times, and 40 ~ 55 DEG C are dried
24 ~ 72 h, grind into powder is standby.
The method for packing of described HNTs filler is as follows:
A., polyelectrolyte is configured to solution for standby, and concentration is 2 ~ 15g/L；
B. weighing the HNTs loading corrosion inhibiter of 0.1 ~ 1 part, join in deionized water, being made into concentration is 0.05 ~ 0.5 g/L
Solution, be placed at 20 ~ 35 DEG C stirring 20 ~ 30 min so that it is formed stable homogeneous suspension；
C. take 2 ~ 10 parts of polyelectrolyte solutions to be placed in there-necked flask, the HNTs solution that 0.4 ~ 1 part loads corrosion inhibiter is slowly fallen
Enter in flask, at a temperature of 20 ~ 30 DEG C, stir 10 ~ 30 min, be then centrifuged 5 ~ 10 min with the rotating speed of 800 ~ 2000rad/min,
Deionized water fully washs 2 ~ 5 times, and once encapsulation terminates；
D. according to predetermined needs, zwitterion polyelectrolyte alternately, is circulated and repeatedly encapsulates.
Described polyelectrolyte is polyacrylic acid (PAA), polyvinyl sulfonic acid (PVS), polystyrolsulfon acid (PSS), polyphenyl
Vinyl sulfonic acid sodium-maleic acid (PSSMA), polymine (PEI) and polypropylene amine (PAH), chitosan (CS), Sargassum
A kind of or the most several in acid sodium (ALG).
The invention has the beneficial effects as follows:
Product of the present invention has the advantages such as VOC free, safety and environmental protection, high rigidity, high adhesion force, environmental protection, and has slow release
Self-repair function and protective effect, can be applicable to metal surface.The present invention is with HNTs as carrier, is loaded wherein by corrosion inhibiter
Forming filler, then it be combined with aqueous epoxy resin emulsion, the auxiliary agent being equipped with asepsis environment-protecting forms coating.The preparation of the present invention
Method is the most easily implemented, and has good dispersibility；The HNTs used is natural mineral raw, aboundresources, the easiest
?；After being equipped with the HNTs filler of corrosion inhibiter, aqueous epoxide resin paint can not only be made to have anticorrosion, selfreparing merit
Can, also can strengthen the mechanical properties such as the hardness of aqueous epoxy resins matrix, toughness, improve the heat stability such as its heat decomposition temperature
Can, improve the film performances such as the resistance to water of film, chemical-resistant.
Present invention elder generation as filler, is centrifuged purification processes, the HNTs after process with halloysite nanotubes (HNTs)
Dry, grind standby.Use the mode of vacuum loading, with HNTs as carrier, corrosion inhibiter is sufficiently mixed in solvent,
Under conditions of the vacuum equipments such as vacuum pump, BTA (BTA) and two kinds of corrosion inhibiter of 8-hydroxyquinoline are loaded in HNTs,
It is centrifuged processing, fully washs with deionized water, obtain the composite equipped with corrosion inhibiter；Then polyelectrolyte is used layer by layer
The mode of self assembly is packaged, and takes a small amount of composite equipped with corrosion inhibiter, is distributed in deionized water, by certain ratio
It is sufficiently mixed by example from different polyelectrolyte solutions, is gradually packaged, and is centrifuged processing, fully washes with deionized water
Wash, dry, grind into powder standby；Last according to certain ratio, packaged composite is evenly spread to aqueous ring
In epoxy resins emulsion, prepare good aqueous self-healing coatings.The self-healing coatings of the present invention is applicable to metal primer or gold
Belong to material, the external coating of paper products.There is the function of anticorrosion, protection, selfreparing.This coating environmental protection, nontoxic, have good
Good adhesive force, higher hardness, simple preparation technology and production cost.
Coating prepared by the present invention is the aqueous self-repair function coating of environmental protection.
Accompanying drawing explanation
Fig. 1 is the TEM figure that the present invention loads the HNTs of corrosion inhibiter.
Fig. 2 is the SEM figure that the present invention loads the HNTs/ aqueous epoxy resins of corrosion inhibiter.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1:
A kind of VOC free epoxy resin/HNTs is combined self-healing coatings, including following components: aqueous epoxy resins/HNTs Composite Milk
Liquid 103 parts (wherein: aqueous epoxy resin emulsion 100.5 parts, there is the HNTs filler 2.5 parts loading corrosion inhibiter), firming agent
ERC2602 13 parts, levelling agent Modarez PSL2000 0.2 part, wetting agent BD-3245 0.25 part, defoamer EL-2600
0.15 part.By said components, it mixes, and is sufficiently stirred for reaching the fineness of requirement, thus prepares VOC free asphalt mixtures modified by epoxy resin
Fat/HNTs is combined self-healing coatings.(before application, it is slowly added to 20 parts of firming agent, stirs 5 min, the works such as film can be carried out
Skill.)
Embodiment 2:
A kind of VOC free epoxy resin/HNTs is combined self-healing coatings, including following components: aqueous epoxy resins/HNTs Composite Milk
Liquid 73 parts, firming agent ERC2606 12 parts, levelling agent Modarez PW336 0.5 part, wetting agent TEGO245 0.65 part, froth breaking
Agent EL-2601 0.35 part；Aqueous epoxy resin emulsion 70 parts；There is the HNTs filler 3 parts loading corrosion inhibiter.
By said components, it mixes, and is sufficiently stirred for reaching the fineness of requirement, thus prepares VOC free asphalt mixtures modified by epoxy resin
Fat/HNTs is combined self-healing coatings.
Embodiment 3:
A kind of VOC free epoxy resin/HNTs is combined self-healing coatings, including following components: aqueous epoxy resins/HNTs Composite Milk
Liquid 150 parts, firming agent ERC2608 12 parts, levelling agent Modarez X080 0.5 part, wetting agent O-level X1840 0.65
Part, defoamer EL-2603 0.35 part；Aqueous epoxy resin emulsion 145 parts；There is the HNTs filler 5 parts loading corrosion inhibiter.
By said components, it mixes, and is sufficiently stirred for reaching the fineness of requirement, thus prepares VOC free asphalt mixtures modified by epoxy resin
Fat/HNTs is combined self-healing coatings.
Embodiment 4
A kind of VOC free epoxy resin/HNTs is combined self-healing coatings, including following components: aqueous epoxy resins/HNTs Composite Milk
Liquid 86 parts (aqueous epoxy resin emulsion 78 parts has the HNTs filler 8 parts loading corrosion inhibiter), levelling agent 0.2 part, wetting agent
0.25 part, defoamer 0.15 part.It is blended together, is sufficiently stirred for reaching the fineness of requirement, thus prepares VOC free ring
Epoxy resins/HNTs is combined self-healing coatings.(before application, it is slowly added to 20 parts of firming agent, stirs 5 min, film etc. can be carried out
Technique.)
Embodiment 5
(aqueous epoxy resin emulsion 82 parts has the HNTs loading corrosion inhibiter to aqueous epoxy resins/HNTs complex emulsions 86 parts
Filler 4 parts), levelling agent 0.4 part, wetting agent 0.5 part, defoamer 0.38 part.It is blended together, is sufficiently stirred for reaching to want
The fineness asked, thus prepare VOC free epoxy resin/HNTs and be combined self-healing coatings.(before application, it is slowly added to firming agent 10
Part, stir 6 min, the techniques such as film can be carried out.)
Embodiment 6
The preparation process of described aqueous epoxy resins/HNTs complex emulsions includes:
First, the aqueous epoxy resin emulsion weighing 50 parts is placed in the there-necked flask of 100ml, then weighs 0.5 part equipped with inhibition
The HNTs of agent, is slowly added in there-necked flask, and at 27 DEG C, motor machine stirs 15 min；
Secondly, carried out ultrasonic disperse, after ultrasonic 20min, then move under electric mixing device, stir 5 min, so circulate
Three times, form the emulsion that stably dispersing is homogeneous.
Embodiment 7
The preparation process of described aqueous epoxy resins/HNTs complex emulsions includes:
First, the aqueous epoxy resin emulsion weighing 100 parts is placed in the there-necked flask of 100ml, then weighs 5 parts equipped with corrosion inhibiter
HNTs, be slowly added in there-necked flask, at 35 DEG C, motor machine stirs 20 min；
Secondly, carried out ultrasonic disperse, after ultrasonic 30min, then move under electric mixing device, stir 10 min, so follow
Ring three times, forms the emulsion that stably dispersing is homogeneous.
Embodiment 8
The preparation process of described aqueous epoxy resins/HNTs complex emulsions includes:
First, the aqueous epoxy resin emulsion weighing 75 parts is placed in the there-necked flask of 100ml, then weighs 3 parts equipped with corrosion inhibiter
HNTs, be slowly added in there-necked flask, under the conditions of 20 DEG C, motor machine stirs 10 min；
Secondly, carried out ultrasonic disperse, after ultrasonic 10 ~ 30min, then moved under electric mixing device, stirred 8 min, so
Circulate three times, form the emulsion that stably dispersing is homogeneous.
Embodiment 9
The preparation process of described aqueous epoxy resins/HNTs complex emulsions includes:
The aqueous epoxy resin emulsion weighing 78 parts is placed in the there-necked flask of 100 ml, then weighs 8 parts equipped with corrosion inhibiter
HNTs, is slowly added in there-necked flask, and at 25 DEG C, motor machine stirs 15 min；
Carried out ultrasonic disperse again, after ultrasonic 15 min, then moved under electric mixing device, stir 6 min, so circulate three
Secondary, form the emulsion that stably dispersing is homogeneous.I.e. can get the aqueous epoxy resins in the present invention/HNTs complex emulsions.
Embodiment 10
First, the aqueous epoxy resin emulsion weighing 82 parts is placed in the there-necked flask of 100 ml, then weighs 4 parts equipped with corrosion inhibiter
HNTs, be slowly added in there-necked flask, at 25 DEG C, motor machine stirs 15 min；
Secondly, carried out ultrasonic disperse, after ultrasonic 15 min, then move under electric mixing device, stir 6 min, so follow
Ring three times, forms the emulsion that stably dispersing is homogeneous.I.e. can get the aqueous epoxy resins in the present invention/HNTs complex emulsions.
Embodiment 11
Described HNTs filler loads the preparation technology of corrosion inhibiter and comprises the following steps:
A, weighs the HNTs of 1.5 parts, is slowly added to fill in the beaker of deionized water, stirs 3h, then centrifugal at 20 DEG C
In machine, the rotating speed with 1000rad/min separates 3min, is divided into from three times, and sucking filtration, distilled water wash are repeated, 40 DEG C of vacuum
Case is dried 18h, is ground after drying；
B, weighs the corrosion inhibiter of 0.15 part, is placed in beaker, adds 1 part of deionized water and 1 portion of dehydrated alcohol mixed liquor, 20 DEG C
Under, magnetic agitation 10min, then weigh the HNTs of 0.22 part, it is slowly added in beaker, at 20 DEG C, magnetic agitation
15min so that it is be sufficiently mixed uniformly；
C. the solution in the beaker of step b is transferred in the Dewar bottle being dried, carries out vacuum loading, make the true of vacuum equipment
Reciprocal of duty cycle is 0.12MPa, and the persistent period is 20min, for proof load effect, can repeatedly circulate and load, centrifugal after load
On machine, the rotating speed of 1000rad/min separates 6min, is washed with deionized 2 times, and 41 DEG C of dry 24h, grind into powder is standby.
Embodiment 12
Described HNTs filler loads the preparation technology of corrosion inhibiter and comprises the following steps:
A, weighs the HNTs of 4 parts, is slowly added to fill in the beaker of deionized water, stirs 5h, then at centrifuge at 35 DEG C
In separate 5 min with the rotating speed of 2000 rad/min, be divided into from three times, and sucking filtration, distilled water wash be repeated, 50 DEG C of vacuum
Case is dried 30h, is ground after drying；
B, weighs the corrosion inhibiter of 0.5 part, is placed in beaker, adds 5 parts of deionized waters and 5 portions of dehydrated alcohol mixed liquors, at 25 DEG C,
Magnetic agitation 20 min, then weigh the HNTs of 2 parts, it is slowly added in beaker, at 25 DEG C, magnetic agitation 30min so that it is
It is sufficiently mixed uniformly；
C. the solution in the beaker of step b is transferred in the Dewar bottle being dried, carries out vacuum loading, make the true of vacuum equipment
Reciprocal of duty cycle is 1MPa, and the persistent period is 40min, for proof load effect, can repeatedly circulate and load, at centrifuge after load
On, the rotating speed of 2000 rad/min separates 15 min, is washed with deionized 6 times, and 55 DEG C are dried 72 h, and grind into powder is standby
With.
Embodiment 13
Described HNTs filler loads the preparation technology of corrosion inhibiter and comprises the following steps:
A, weighs the HNTs of 2.1 parts, is slowly added to fill in the beaker of deionized water, stirs 4h, then centrifugal at 30 DEG C
Separating 4 min with the rotating speed of 1500 rad/min in machine, be divided into from three times, and sucking filtration, distilled water wash are repeated, 45 DEG C true
Empty van is dried 24h, is ground after drying；
B, weighs the corrosion inhibiter of 0.3 part, is placed in beaker, adds 3 parts of deionized waters and 3 portions of dehydrated alcohol mixed liquors, at 23 DEG C,
Magnetic agitation 15min, then weigh the HNTs of 1.2 parts, it is slowly added in beaker, at 23 DEG C, magnetic agitation 22min, make
It is sufficiently mixed uniformly；
C. the solution in the beaker of step b is transferred in the Dewar bottle being dried, carries out vacuum loading, make the true of vacuum equipment
Reciprocal of duty cycle is 5.6MPa, and the persistent period is 30min, for proof load effect, can repeatedly circulate and load, at centrifuge after load
On, the rotating speed of 1500 rad/min separates 11 min, is washed with deionized 4 times, and 48 DEG C of dry 48h, grind into powder is standby.
Embodiment 14
Described HNTs filler loads the preparation technology of corrosion inhibiter and comprises the following steps:
First, weigh the HNTs of 1.2 parts, be slowly added to fill in the beaker of deionized water, at 25 DEG C, stir 3h, then from
Scheming separates 4 min with the rotating speed of 2000 rad/min, is divided into from three times, and sucking filtration, distilled water wash are repeated, 45 DEG C
Vacuum tank is dried 20 h, is ground standby after drying；
Secondly, then weigh the corrosion inhibiter of 0.2 part, be placed in beaker, add 4 parts of deionized waters and 3 portions of dehydrated alcohol mixed liquors, 25
At DEG C, magnetic agitation 10min, then weigh the HNTs of 0.4 part, and it is slowly added in beaker, at 25 DEG C, magnetic agitation
15min so that it is be sufficiently mixed uniformly；
Finally, the solution in above-mentioned beaker is transferred in the Dewar bottle being dried, carries out vacuum loading.Make the vacuum of vacuum equipment
Degree is 0.1MPa, and the persistent period is 20 min, and after load on centrifuge, the rotating speed of 2000 rad/min separates 10 min, uses
Deionized water wash 3 times, 50 DEG C are dried 48 h, and grind into powder is standby；
Embodiment 15
Described HNTs filler loads the preparation technology of corrosion inhibiter and comprises the following steps:
First, weigh the HNTs of 2 parts, be slowly added to fill in the beaker of deionized water, at 25 DEG C, stir 3h, then centrifugal
In machine, the rotating speed with 2000 rad/min separates 4min, is divided into from three times, and sucking filtration, distilled water wash are repeated, and 45 DEG C true
Empty van is dried 20h, is ground standby after drying；
Secondly, then weigh the corrosion inhibiter of 0.4 part, be placed in beaker, add 6 parts of deionized waters and 4 portions of dehydrated alcohol mixed liquors,
At 25 DEG C, magnetic agitation 10min, then weigh the HNTs of 0.9 part, and it is slowly added in beaker, at 25 DEG C, magnetic agitation
15min so that it is be sufficiently mixed uniformly；
Finally, the solution in above-mentioned beaker is transferred in the Dewar bottle being dried, carries out vacuum loading, make the vacuum of vacuum equipment
Degree is 0.1MPa, and the persistent period is 20 min, and vacuum is reduced to zero, keeps 5min, the again vacuum loading before repetition,
The vacuum of vacuum equipment is 0.1MPa, and the persistent period is 20 min, after load on centrifuge, and the rotating speed of 2000rad/min
Separating 10min, be washed with deionized 3 times, 50 DEG C of dry 60h, grind into powder is standby.
Embodiment 16:
The preparation technology that described HNTs filler loads corrosion inhibiter is as follows:
First, weigh the HNTs of 1 part, be slowly added to fill in the beaker of deionized water, at 25 DEG C, stir 3h, then centrifugal
In machine, the rotating speed with 2000 rad/min separates 4min, is divided into from three times, and sucking filtration, distilled water wash are repeated, and 45 DEG C true
Empty van is dried 20h, is ground standby after drying；
Secondly, then weigh the corrosion inhibiter of 0.2 part, be placed in beaker, add 4 parts of deionized waters and 3 portions of dehydrated alcohol mixed liquors,
At 25 DEG C, magnetic agitation 10 min.Weigh the HNTs of 0.4 part again, be slowly added in beaker, at 25 DEG C, magnetic agitation
15min so that it is be sufficiently mixed uniformly；
Finally, the solution in upper step beaker is transferred in the Dewar bottle being dried, carries out vacuum loading, make the true of vacuum equipment
Reciprocal of duty cycle is 0.1MPa, and the persistent period is 20min, and after load on centrifuge, the rotating speed of 2000 rad/min separates 10min, uses
Deionized water wash 3 times, 50 DEG C of dry 48h, grind into powder is standby；
Embodiment 17
The method for packing of described HNTs filler is as follows:
Polyelectrolyte is configured to solution for standby (concentration is 8 g/L) according to certain concentration, weighs the loading corrosion inhibiter of 0.4 part
HNTs, join in deionized water, be made into the solution that concentration is 0.1g/L, be placed at 35 DEG C and stir 25 min so that it is
Form the suspension of stable homogeneous；Take 6 parts of polyelectrolyte solutions again to be placed in there-necked flask, load corrosion inhibiter by 0.5 part
HNTs solution is poured slowly in flask, at a temperature of 25 DEG C, stirs 20 min, is then centrifuged 6 with the rotating speed of 1500 rad/min
Min, deionized water fully washs 3 times, and once encapsulation terminates；According to predetermined needs, zwitterion polyelectrolyte alternately, can enter
Row circulation repeatedly encapsulates.
Embodiment 18:
A kind of VOC free epoxy resin/HNTs is combined self-healing coatings, including following components: aqueous epoxy resins/HNTs Composite Milk
Liquid 103 parts (aqueous epoxy resin emulsion 100.5 parts has the HNTs filler 2.5 parts loading corrosion inhibiter), levelling agent 0.2 part,
Wetting agent 0.25 part, defoamer 0.15 part.It is blended together, is sufficiently stirred for reaching the fineness of requirement, thus prepares
VOC free epoxy resin/HNTs is combined self-healing coatings.(before application, it is slowly added to 20 parts of firming agent, stirs 5 min, Ji Kejin
The techniques such as row film.)
Wherein, the preparation technology of aqueous epoxy resins/HNTs complex emulsions is as follows:
First, weigh certain mass HNTs, be slowly added to fill in the beaker of deionized water, at 25 DEG C, stir 3h, so
After in centrifuge, separate 4min with the rotating speed of 2000rad/min, be divided into from three times, and sucking filtration, distilled water wash be repeated,
45 DEG C of vacuum tanks are dried 20h, are ground standby after drying；Weigh the corrosion inhibiter of 0.2 part again, be placed in beaker, add 4 parts
Deionized water and 3 portions of dehydrated alcohol mixed liquors, at 25 DEG C, magnetic agitation 10min, then weigh the HNTs of 0.4 part, it is slow
Join in beaker, at 25 DEG C, magnetic agitation 15min so that it is be sufficiently mixed uniformly.It is transferred to do by the solution in above-mentioned beaker
In dry Dewar bottle, carry out vacuum loading.The vacuum making vacuum equipment is 0.1MPa, and the persistent period is 20 min, after load
On centrifuge, the rotating speed of 2000 rad/min separates 10 min, is washed with deionized 3 times, and 50 DEG C are dried 48 h, grind to form
Powder is standby；
Secondly, polyelectrolyte is configured to solution for standby (concentration is 8 g/L) according to certain concentration, weighs the loading of 0.4 part
The HNTs of corrosion inhibiter, joins in deionized water, is made into the solution that concentration is 0.1 g/L, is placed at 35 DEG C stirring
25min so that it is form the suspension of stable homogeneous.Take 6 parts of polyelectrolyte solutions again to be placed in there-necked flask, by 0.5 part of loading
The HNTs solution of corrosion inhibiter is poured slowly in flask, at a temperature of 25 DEG C, stirs 20min, then with the rotating speed of 1500rad/min from
Heart 6min, deionized water fully washs 3 times, and once encapsulation terminates.According to predetermined needs, zwitterion polyelectrolyte replaces,
Can be circulated and repeatedly encapsulate；
Finally, use the method that ultrasonic disperse is combined with mechanical agitation by aqueous epoxy resin emulsion and the HNTs loading corrosion inhibiter
Filler is combined；The aqueous epoxy resin emulsion weighing 80 parts is placed in the there-necked flask of 100 ml, then weigh 1.9 parts equipped with
The HNTs of corrosion inhibiter, is slowly added in there-necked flask, and at 25 DEG C, motor machine stirs 15 min.Carried out ultrasonic point again
Dissipating, after ultrasonic 15 min, then move under electric mixing device, stir 6 min, so circulation three times, forms stably dispersing homogeneous
Emulsion.I.e. can get the aqueous epoxy resins in the present invention/HNTs complex emulsions.
Described corrosion inhibiter is BTA (BTA) with 8-hydroxyquinoline according to the mixture of 1:1.Described polyelectrolyte material
Material is polystyrolsulfon acid (PSS) and chitosan (CS) two kinds.
Described firming agent is the ERC2602 of Guangzhou Ou Peng Chemical Co., Ltd.；Described wetting agent is that Hangzhou Bao Er get is organic
The BD-3245 of silicon company limited；Described levelling agent is the Modarez PSL2000 of Guangzhou Ou Peng Chemical Co., Ltd.；Described disappear
Infusion is the EL-2600 of Dongguan City Yi Lian Chemical Industry Science Co., Ltd.
Fig. 1 is the TEM figure after HNTs load corrosion inhibiter.As shown in Figure 1, corrosion inhibiter the most successfully loads in HNTs.
Embodiment 19: contrast experiment
A kind of VOC free epoxy resin/HNTs is combined self-healing coatings, including following components: aqueous epoxy resins/HNTs Composite Milk
Liquid 86 parts (aqueous epoxy resin emulsion 78 parts has the HNTs filler 8 parts loading corrosion inhibiter), levelling agent 0.2 part, wetting agent
0.25 part, defoamer 0.15 part.It is blended together, is sufficiently stirred for reaching the fineness of requirement, thus prepares VOC free ring
Epoxy resins/HNTs is combined self-healing coatings.(before application, it is slowly added to 20 parts of firming agent, stirs 5 min, film etc. can be carried out
Technique.)
Wherein, the preparation technology of aqueous epoxy resins/HNTs complex emulsions is as follows:
First, weigh certain mass HNTs, be slowly added to fill in the beaker of deionized water, at 25 DEG C, stir 3h, so
After in centrifuge, separate 4 min with the rotating speed of 2000 rad/min, be divided into from three times, and be repeated sucking filtration, distillation washing
Wash, 45 DEG C of vacuum tanks are dried 20 h, are ground standby after drying.Weigh the corrosion inhibiter of 0.2 part again, be placed in beaker, add
Enter 4 parts of deionized waters and 3 portions of dehydrated alcohol mixed liquors, at 25 DEG C, magnetic agitation 10 min.Weigh the HNTs of 0.4 part again, will
It is slowly added in beaker, at 25 DEG C, and magnetic agitation 15 min so that it is be sufficiently mixed uniformly.By the solution in above-mentioned beaker
It is transferred in the Dewar bottle being dried, carries out vacuum loading.The vacuum making vacuum equipment is 0.1MPa, and the persistent period is 20
min.After load on centrifuge, the rotating speed of 2000 rad/min separates 10 min, is washed with deionized 3 times.50 DEG C are dried
48 h, grind into powder is standby；
Secondly, polyelectrolyte is configured to solution for standby (concentration is 8 g/L) according to certain concentration.Weigh the loading of 0.4 part
The HNTs of corrosion inhibiter, joins in deionized water, is made into the solution that concentration is 0.1 g/L, is placed at 35 DEG C stirring 25
Min so that it is form the suspension of stable homogeneous.Take 6 parts of polyelectrolyte solutions again to be placed in there-necked flask, 0.5 part is loaded slow
The HNTs solution of erosion agent is poured slowly in flask, at a temperature of 25 DEG C, stirs 20 min.Then with the rotating speed of 1500 rad/min from
The heart 6 min.Deionized water fully washs 3 times.Once encapsulation terminates.According to predetermined needs, zwitterion polyelectrolyte replaces,
Can be circulated and repeatedly encapsulate；
Finally, use the method that ultrasonic disperse is combined with mechanical agitation by aqueous epoxy resin emulsion and the HNTs loading corrosion inhibiter
Filler is combined.The aqueous epoxy resin emulsion weighing 78 parts is placed in the there-necked flask of 100 ml, then weighs 8 parts equipped with slow
The HNTs of erosion agent, is slowly added in there-necked flask, and at 25 DEG C, motor machine stirs 15 min.Carried out ultrasonic disperse again,
After ultrasonic 15 min, then moving under electric mixing device, stir 6 min, so circulation three times, forms the breast that stably dispersing is homogeneous
Liquid.I.e. can get the aqueous epoxy resins in the present invention/HNTs complex emulsions.
Described corrosion inhibiter is BTA (BTA) with 8-hydroxyquinoline according to the mixture of 1:1.Described polyelectrolyte material
Material is polystyrolsulfon acid (PSS) and chitosan (CS) two kinds.
Described firming agent is the ERC2602 of Guangzhou Ou Peng Chemical Co., Ltd.；Described wetting agent is that Hangzhou Bao Er get is organic
The BD-3245 of silicon company limited；Described levelling agent is the Modarez PSL2000 of Guangzhou Ou Peng Chemical Co., Ltd.；Described disappear
Infusion is the EL-2600 of Dongguan City Yi Lian Chemical Industry Science Co., Ltd.
Fig. 2 is to load the SEM figure that the HNTs of corrosion inhibiter is distributed in aqueous epoxy resins.As shown in Figure 2, excess is higher
HNTs adds in aqueous epoxy resins, it may occur that agglomeration, and substantial amounts of nanoparticle agglomerates will affect the performance of coating.
Embodiment 20:
A kind of VOC free epoxy resin/HNTs is combined self-healing coatings, including following components: aqueous epoxy resins/HNTs Composite Milk
Liquid 86 parts (aqueous epoxy resin emulsion 82 parts has the HNTs filler 4 parts loading corrosion inhibiter), levelling agent 0.4 part, wetting agent
0.5 part, defoamer 0.38 part.It is blended together, is sufficiently stirred for reaching the fineness of requirement, thus prepares VOC free ring
Epoxy resins/HNTs is combined self-healing coatings.(before application, it is slowly added to 10 parts of firming agent, stirs 6 min, film etc. can be carried out
Technique.)
Wherein, the preparation technology of aqueous epoxy resins/HNTs complex emulsions is as follows:
First, weigh certain mass HNTs, be slowly added to fill in the beaker of deionized water, at 25 DEG C, stir 3h, so
After in centrifuge, separate 4 min with the rotating speed of 2000 rad/min, be divided into from three times, and be repeated sucking filtration, distillation washing
Wash, 45 DEG C of vacuum tanks are dried 20 h, are ground standby after drying.Weigh the corrosion inhibiter of 0.4 part again, be placed in beaker, add
Enter 6 parts of deionized waters and 4 portions of dehydrated alcohol mixed liquors, at 25 DEG C, magnetic agitation 10 min.Weigh the HNTs of 0.9 part again, will
It is slowly added in beaker, at 25 DEG C, and magnetic agitation 15 min so that it is be sufficiently mixed uniformly.By the solution in above-mentioned beaker
It is transferred in the Dewar bottle being dried, carries out vacuum loading.The vacuum making vacuum equipment is 0.1MPa, and the persistent period is 20
min.Vacuum being reduced to zero, keeps 5 min, the vacuum loading before repeating again, the vacuum of vacuum equipment is
0.1MPa, the persistent period is 20 min.After load on centrifuge, the rotating speed of 2000 rad/min separates 10 min, spend from
Sub-water washs 3 times, and 50 DEG C of dry 60h, grind into powder is standby；
Secondly, polyelectrolyte is configured to solution for standby (concentration is 8 g/L) according to certain concentration；Weigh the loading of 0.4 part
The HNTs of corrosion inhibiter, joins in deionized water, is made into the solution that concentration is 0.1 g/L, is placed at 35 DEG C stirring 25
Min so that it is form the suspension of stable homogeneous.Take 6 parts of polyelectrolyte solutions again to be placed in there-necked flask, 0.5 part is loaded slow
The HNTs solution of erosion agent is poured slowly in flask, at a temperature of 25 DEG C, stirs 20 min.Then with the rotating speed of 1500 rad/min from
The heart 6 min, deionized water fully washs 3 times, and once encapsulation terminates, and encapsulates four times；
Finally, use the method that ultrasonic disperse is combined with mechanical agitation by aqueous epoxy resin emulsion and the HNTs loading corrosion inhibiter
Filler is combined；The aqueous epoxy resin emulsion weighing 82 parts is placed in the there-necked flask of 100 ml, then weighs 4 parts equipped with slow
The HNTs of erosion agent, is slowly added in there-necked flask, and at 25 DEG C, motor machine stirs 15 min.Carried out ultrasonic disperse again,
After ultrasonic 15 min, then moving under electric mixing device, stir 6 min, so circulation three times, forms the breast that stably dispersing is homogeneous
Liquid.I.e. can get the aqueous epoxy resins in the present invention/HNTs complex emulsions.
Described corrosion inhibiter is BTA (BTA) with mercaptobenzothiazoler (MBT) according to the mixture of 1:2.Described poly-
Electrolyte is polystyrolsulfon acid (PSS), polyacrylic acid (PAA), polypropylene amine (PAH) and chitosan (CS) four kinds.
Described firming agent is the ERC2606 of Guangzhou Ou Peng Chemical Co., Ltd.；Described wetting agent is that Hangzhou Bao Er get is organic
The TEGO245 of silicon company limited；Described levelling agent is the Modarez PW336 of Guangzhou Ou Peng Chemical Co., Ltd.；Described froth breaking
Agent is the EL-2638 of Dongguan City Yi Lian Chemical Industry Science Co., Ltd.
Three kinds of VOC free epoxy resin/HNTs that embodiment 18-20 prepares are combined self-healing coatings and are coated onto the most equably
Tinplate surface forms paint film, and detects the main performance of paint film, the results are shown in Table 1.
。
Claims (9)
1. VOC free epoxy resin/HNTs is combined self-healing coatings, it is characterised in that include following components: water-base epoxy tree
Fat/HNTs complex emulsions 70 ~ 150 parts, 12 ~ 35 parts of firming agent, levelling agent 0.1 ~ 0.8 part, wetting agent 0.1 ~ 1 part, defoamer 0.1
~ 0.6 part.
A kind of VOC free epoxy resin/HNTs the most according to claim 1 is combined self-healing coatings, it is characterised in that institute
The aqueous epoxy resins stated/HNTs complex emulsions includes: aqueous epoxy resin emulsion 69.5 ~ 145 parts, has loading corrosion inhibiter
HNTs filler 0.5 ~ 5 part；Described corrosion inhibiter is BTA (BTA), methyl benzotriazazole (TTA), water solublity sulfydryl
A kind of or the most several in benzothiazole (CAS), mercaptobenzothiazoler (MBT), 8-hydroxyquinoline.
A kind of VOC free epoxy resin/HNTs the most according to claim 1 is combined self-healing coatings, it is characterised in that described
Firming agent is the one in ERC2602, ERC2606, ERC2608, ERC2609, ERC2635 of Guangzhou Ou Peng Chemical Co., Ltd.
Or it is several；
Described wetting agent is BD-3245, TEGO245 of Hangzhou Bao Er get organosilicon company limited, the Guangzhou limited public affairs of Ou Peng chemical industry
One in the O-level X1840 of department；
Described levelling agent is the Modarez PSL2000 of Guangzhou Ou Peng Chemical Co., Ltd., Modarez PW336, Modarez
One or more in X080 levelling agent；
The EL-2600 of described defoamer Dongguan City Yi Lian Chemical Industry Science Co., Ltd, EL-2601, EL-2602, EL-2603,
One or more in EL-2607, EL-2638 defoamer.
4. VOC free epoxy resin/HNTs is combined the preparation method of self-healing coatings, it is characterised in that comprise the following steps:
First, the aqueous epoxy resin emulsion weighing 69.5 ~ 145 parts is placed in the there-necked flask of 100ml, then weighs 0.5 ~ 5 part
Equipped with the HNTs of corrosion inhibiter, it is slowly added in there-necked flask, at 20 ~ 35 DEG C, motor machine stirring 10 ~ 20 min；
Secondly, carried out ultrasonic disperse, after ultrasonic 10 ~ 30min, then moved under electric mixing device, stirred 5 ~ 10 min, as
This circulation three times, forms aqueous epoxy resins/HNTs complex emulsions that stably dispersing is homogeneous；
Finally, by aqueous epoxy resins/HNTs complex emulsions 70 ~ 150 parts, 12 ~ 35 parts of firming agent, levelling agent 0.1 ~ 0.8 part, profit
Humectant 0.1 ~ 1 part, defoamer 0.1 ~ 0.6 part is sufficiently mixed, and is sufficiently stirred for, and reaches the fineness needed.
A kind of VOC free epoxy resin/HNTs the most according to claim 2 is combined the preparation method of self-healing coatings, and it is special
Levying and be, described is to use ultrasonic disperse and machinery by the step that aqueous epoxy resin emulsion and HNTs filler carry out being combined
Stirring alternately mixing so that it is be dispersed in aqueous epoxy resin emulsion.
A kind of VOC free epoxy resin/HNTs the most according to claim 1 is combined the preparation method of self-healing coatings, and it is special
Levying and be, the preparation technology of described HNTs filler includes: use the method for vacuum loading that corrosion inhibiter is loaded into the sky of HNTs
In chamber, utilize the adsorption mechanism of polyelectrolyte, the method using LBL self-assembly, the HNTs equipped with corrosion inhibiter is packaged place
Reason.
A kind of VOC free epoxy resin/HNTs the most according to claim 4 is combined the preparation method of self-healing coatings, and it is special
Levying and be, described HNTs filler loads the preparation technology of corrosion inhibiter and comprises the following steps:
A. weigh the HNTs of 0.5 ~ 5 part, be slowly added to fill in the beaker of deionized water, at 20 DEG C ~ 35 DEG C, stir 3 ~ 5h,
Then in centrifuge, separate 3 ~ 5 min with the rotating speed of 1000 ~ 2000 rad/min, be divided into from three times, and be repeated sucking filtration,
Distilled water wash, is dried 18 ~ 30h, is ground after drying in 40 DEG C ~ 50 DEG C vacuum tanks；
B. weigh the corrosion inhibiter of 0.1 ~ 0.5 part, be placed in beaker, add 1 ~ 5 part of deionized water and 1 ~ 5 part of dehydrated alcohol mixing
Liquid, at 20 ~ 25 DEG C, magnetic agitation 10 ~ 20 min, then weigh the HNTs of 0.2 ~ 2 part, it is slowly added in beaker, 20 ~ 25
At DEG C, magnetic agitation 15 ~ 30min so that it is be sufficiently mixed uniformly；
C. the solution in the beaker of step b is transferred in the Dewar bottle being dried, carries out vacuum loading, make the true of vacuum equipment
Reciprocal of duty cycle is 0.1 ~ 1MPa, and the persistent period is 20 ~ 40min, for proof load effect, can repeatedly circulate and load, after load
On centrifuge, the rotating speed of 1000 ~ 2000 rad/min separates 5 ~ 15 min, is washed with deionized 2 ~ 6 times, and 40 ~ 55 DEG C are dried
24 ~ 72 h, grind into powder is standby.
A kind of VOC free epoxy resin/HNTs the most according to claim 6 is combined the preparation method of self-healing coatings, and it is special
Levying and be, the described method for packing equipped with the HNTs filler of corrosion inhibiter is as follows:
A., polyelectrolyte is configured to solution for standby, and concentration is 2 ~ 15g/L；
B. weighing the HNTs loading corrosion inhibiter of 0.1 ~ 1 part, join in deionized water, being made into concentration is 0.05 ~ 0.5 g/L
Solution, be placed at 20 ~ 35 DEG C stirring 20 ~ 30 min so that it is formed stable homogeneous suspension；
C. take 2 ~ 10 parts of polyelectrolyte solutions to be placed in there-necked flask, the HNTs solution that 0.4 ~ 1 part loads corrosion inhibiter is slowly fallen
Enter in flask, at a temperature of 20 ~ 30 DEG C, stir 10 ~ 30 min, be then centrifuged 5 ~ 10 min with the rotating speed of 800 ~ 2000rad/min,
Deionized water fully washs 2 ~ 5 times, and once encapsulation terminates；
D. according to predetermined needs, zwitterion polyelectrolyte alternately, is circulated and repeatedly encapsulates.
A kind of VOC free epoxy resin/HNTs the most according to claim 8 is combined the preparation method of self-healing coatings, and it is special
Levying and be, described polyelectrolyte is polyacrylic acid (PAA), polyvinyl sulfonic acid (PVS), polystyrolsulfon acid (PSS), polyphenyl second
Alkene sodium sulfonate-maleic acid (PSSMA), polymine (PEI) and polypropylene amine (PAH), chitosan (CS), alginic acid
A kind of or the most several in sodium (ALG).
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| CN112280419A (en) * | 2019-07-25 | 2021-01-29 | 天津大学 | Intelligent epoxy coating containing halloysite nanotube loaded 8-hydroxyquinoline and preparation method and application thereof |
| CN110305565A (en) * | 2019-08-05 | 2019-10-08 | 大洋电力科技集团有限公司 | A kind of anticorrosive paint and preparation method thereof of defecation just pipeline |
| CN113249008A (en) * | 2021-03-24 | 2021-08-13 | 吉林大学 | Bionic intelligent repeatable self-repairing epoxy resin coating and electrostatic spraying process method thereof |
| CN113245166A (en) * | 2021-03-24 | 2021-08-13 | 吉林大学 | Bionic intelligent repeatable self-repairing coating and drop coating process method thereof |
| CN113637391A (en) * | 2021-08-20 | 2021-11-12 | 西安石油大学 | Graphene self-repairing solvent-free epoxy anticorrosive paint and preparation method and use method thereof |
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| CN115612066A (en) * | 2022-11-03 | 2023-01-17 | 华南理工大学 | Micromolecular corrosion inhibitor modified waterborne epoxy curing agent and preparation method thereof |
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