CN108752532A - One kind having gradient damping structure styrene-acrylic emulsion and can toast heavy sizing aqueous damping paint and preparation - Google Patents
One kind having gradient damping structure styrene-acrylic emulsion and can toast heavy sizing aqueous damping paint and preparation Download PDFInfo
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- CN108752532A CN108752532A CN201810477508.9A CN201810477508A CN108752532A CN 108752532 A CN108752532 A CN 108752532A CN 201810477508 A CN201810477508 A CN 201810477508A CN 108752532 A CN108752532 A CN 108752532A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
One kind having gradient damping structure styrene-acrylic emulsion and can toast heavy sizing aqueous damping paint and preparation, belongs to water paint field.Heavy sizing aqueous damping paint can be toasted and formed by having the styrene-acrylic emulsion of gradient damping structure, water, wetting dispersing agent, coalescents, thickener, levelling agent, mica powder, calcium carbonate, graphite and functional filler.With gradient damping structure styrene-acrylic emulsion, latex particle intramolecule structure is prepared by power level charging method, consecutive variations are presented, latex particle is distributed from inside to outer layer styrene is presented graded.The phenomenon that the defects of invention overcomes existing aqueous damping coating and toasted in the short open hour under thick painting state, and surface generates blistering, skinning, cracking.The aqueous damping coating of the invention is by disposable blade coating and spraying, it can be achieved that wet-film thickness reaches 3mm or more.Coating has outstanding rheological property, and shear shinning is apparent, has good sag resistance, good damping capacity to can be applied to automobile making etc. and need the quick-drying field of aqueous damping coating.
Description
Technical field
The invention belongs to water paint fields, and providing one kind having gradient damping structure styrene-acrylic emulsion and can toast quick-drying thickness
Sizing aqueous damping paint preparation method.Aqueous damping coating provided by the invention can be used as automobile, high ferro, big machinery and fly
Damping material in the industries such as machine.
Background technology
Gradual stringent with national environmental protection policy, coating industry makes the transition in terms of facing hydrotropismization coating, aqueous damping
Coating can effectively reduce generated vibration in mechanized equipment operational process, reach vibration and noise reducing as a kind of environment-friendly type coating
Effect.Film forming matter of the resin aqueous emulsion as aqueous damping coating is coating damping capacity main provider, resin
The quality of fine or not decision maker's coating.High-performance water-based damping coating material lotion should have excellent damping capacity, good resistance to
Chemical mediator stability, excellent mechanical stability and higher storage stability.
In quick-drying water-based damping paint development process at this stage, seldom it is related to the fast dry system of baking of thick painting system.
Patent " aqueous paint composition of baking-drying type " disclosed in 101405353 A of patent publication No. CN uses styrene-
The matrix of butadiene copolymer emulsions, acrylate copolymer emulsion and ethane-acetic acid ethyenyl ester copolymer emulsion as coating
Resin selects calcium carbonate, talcum powder, diatomite, barium sulfate, zeolite, mica etc. as filler, and developed can toast quick-drying
Aqueous damping coating.But the aqueous damping coating thickness that developed applies performance (2-3mm) and does not specify, coating under thick painting state
Sag resistance does not specify simultaneously.
Patent disclosed in 105602371 A of patent publication No. CN be " a kind of automobile high-temperature baking type aqueous damping coating
The emulsion acrylic resin of preparation method " using different glass transition temperature be blended after as coating matrix resin, choosing
It is filler to select wollastonite in powder, mica powder, coarse whiting, and 15-20min paint films can be toasted at 140 DEG C by, which being prepared for, is completely dried zero defect
Aqueous damping coating product.But baking quick-drying performance of the coating under thick painting state is not referred in its patent.
Patent " automobile aqueous damping coating " is with styrene-acrylic emulsion, pure third disclosed in 105907192 A of patent publication No. CN
Matrix resin of the blending emulsion of lotion and acetate emulsion as coating selects carbon nanotube, rubber powder, mica powder, stone
Ink powder is filler, is prepared for the aqueous damping coating product of damping temp field width.It is fast under aqueous damping coating product thickness painting state
It is dry functional, but coating emulsion dosage is more than 50%, and select carbon nanotube, rubber powder as filler, the two content is
Through 10% more than coating total mass fraction, application cost is high, is unfavorable for commercialization and promotes.
Patent " high temperature resistant quick-drying water-based damping paint and its preparation side disclosed in 106147419 A of patent publication No. CN
Method " selects short glass fiber, mica powder, talcum powder as filler systems, prepares using styrene-acrylic emulsion as the matrix resin of coating
Wide damping temperature domain and can heat drying aqueous damping coating product.But coating is not mentioned in patent in thick painting state
The sag resistance and baking quick-drying performance of lower paint film.
" a kind of zero defect automobile suitable for high-temperature baking is aqueous for patent disclosed in 106554686 A of patent publication No. CN
Matrix tree of the damping paint and preparation method thereof " using the mixed emulsion of pure-acrylic emulsion, styrene-acrylic emulsion and styrene-butadiene emulsion as coating
Fat selects calcium carbonate, mica powder, talcum powder, wollastonite for filler, is prepared for automobile water-based suitable for the zero defect of high-temperature baking
Property damping paint.It solves the quick-drying performance of coating under thick painting state and is realized by the way that proper amount of surfactant is added, but
That the addition of surfactant can adversely affect paint film property during the use of paint film later stage, paint film resistance to medium and
Endurance quality needs to be investigated.
It carries out toasting fast dry-cure under standard aqueous damping paint thickness painting state, it may appear that surface skining, blistering, crackle etc.
Phenomenon seriously affects coating use.In automobile manufacture industry, manufacturing process is continuous production, aqueous damping coating to
Baking is sprayed to, the open hour only less than 10 minutes, just enter high temperature drying tunnel (140 DEG C -160 DEG C of temperature) later, aqueous
Damping paint surface is dried rapidly, rapid skinning, is caused moisture in thick painting film that can not be precipitated, is caused paint film defect, therefore mesh
Preceding heavy sizing aqueous damping paint can not be used widely in automobile manufacturing field.
Invention content
The present invention solves the technical problem of the aqueous damping coatings (wet-film thickness 2-3mm) of thickness painting in short opening
The defects of time (in half an hour) just directly carries out 120 DEG C of -160 DEG C of high-temperature bakings, and surface generates skinning, bubbling, cracking is asked
Topic.Present invention aims at provide one kind thick to apply the aqueous damping that (wet-film thickness 2-3mm) directly carries out high-temperature baking afterwards
Coating.The coating resin content is low, but comprehensive performance reaches TB-T 2932-1998 B class damping paint performance requirements, have compared with
High commercial application value, especially suitable for automobile manufacture industry and other quick continuous manufacturings.
The present invention provides one kind having gradient damping structure styrene-acrylic emulsion and synthetic method, can be synthesized by this method
Go out suitable for the resin aqueous emulsion for preparing large arch dam, quick-drying water-based damping paint.
One kind having gradient damping structure styrene-acrylic emulsion, which is characterized in for preparing latex particle by power level charging method, breast
Consecutive variations are presented in the sub- internal structure of micelle, and latex particle is distributed from inside to outer layer styrene is presented graded；It is preferred that benzene
Ethylene contents gradient increases.
Emulsion formulations raw material include as follows according to parts by weight ingredient：
5 parts -30 parts of styrene monomer
10 parts -30 parts of methyl methacrylate monomer
10 parts -40 parts of n-butyl acrylate monomer
1 part -8 parts of functional monomer
0.1 part -1 part of sodium bicarbonate
1 part -4 parts of emulsifier
30 parts -60 parts of deionized water
0.01 part -0.1 part of initiator
Wherein preferred function monomer is by acrylic acid, methacrylic acid, Methacrylamide, methyl propenoic acid glycidyl
One or more of compositions of ester.Emulsifier is using nonionic emulsifier and anionic emulsifier compounding composition.Initiator is adopted
Use redox system initiator.
Preferred emulsifier is the mixture of TX-21, the mixture of neopelex or TX-30, SR-10,
Weight ratio is 1-6: 1-10.
Redox system is built using ammonium persulfate and sodium hydrogensulfite, according to weight ratio ammonium persulfate: bisulfite
Sodium is 1: 1-3: 1.
Synthesis technology is included the following steps using power level charging method：
1. the preparation of seed emulsion
Part styrene, part methyl methyl acrylate, part acrylic acid N-butyl, partial function are added in a kettle
Property monomer, emulsifier, pH adjusting agent and portions of de-ionized water prepare bottoming liquid, under nitrogen atmosphere, stir deoxygenation；It is separately added into
Initiator solution, heat preservation obtain seed emulsion in 0.5-1 hours；
2. the preparation of monomer mixed solution
Part styrene, part methyl methyl acrylate, part acrylic acid N-butyl, part functionalities monomer are mixed simultaneously
Monomer mixed solution I is prepared, monomer mixed solution is kept to be in stirring, such as using mechanical agitation with 100rpm speed.
3. the preparation of pre-emulsion
By residual styrene, remaining methyl methacrylate, residual acrylic acid N-butyl, remaining functional monomer, residue
Emulsifier, portions of de-ionized water mixing composition pre-emulsion II, are kept pre-emulsion II to be in stirring, are such as stirred using machinery
It mixes with 100rpm speed；
4. the preparation of initiator solution
Remaining initiator is dissolved in remaining deionized water and prepares initiator solution；
5. polymerization procedure
Using power level charging method, monomer mixed solution I and pre-emulsion II is added dropwise into seed emulsion；It will using metering pump I
Monomer mixed solution I is added dropwise to reaction kettle, and pre-emulsion is added dropwise in mix monomer liquid I by metering pump II, is counted by controlling
The velocity ratio of amount pump I and metering pump II, realize that the composition of mix monomer liquid constantly changes, it is 4 hours that total duration, which is added dropwise, is dripped
3 hours are kept the temperature afterwards, cools to obtain final products.
Styrene accounts for that styrene in the mole percent of monomer, pre-emulsion II accounts for monomer in monomer mixed solution moles hundred
Score is different, the final latex particle for preparing the distribution from inside to outer layer styrene and graded being presented.
It is preferred that making benzene in dropping liquid by adjusting the rate of addition of monomer mixed solution and the rate of addition of pre-emulsion II
Ethylene is more than the mole percent that styrene in seed emulsion accounts for monomer by the mole percent of monomer.
The present invention on the basis of above to have the styrene-acrylic emulsion of gradient damping structure as main film forming substance, with cloud
Mother, calcium carbonate, graphite are main stuffing, and part functionalities filler, chopped polypropylene fibre are added on this basis, are prepared for
The heavy sizing aqueous damping paint of quick-drying can be toasted.
Coating composition is as follows according to parts by weight ingredient：
Has 20-40 parts of the styrene-acrylic emulsion of gradient damping structure
20-50 parts of mica powder
0-20 parts of calcium carbonate
0-10 parts of graphite
Be chopped 0-3 parts of polypropylene fibre
10-30 parts of functional filler
2-10 parts of auxiliary agent
5-20 parts of deionized water
Mica powder is muscovite, by 200 mesh, one or more of groups of 325 mesh, 800 mesh, 1000 mesh, four kinds of different meshes
At.
Calcium carbonate selects powdered whiting, by 200 mesh, 325 mesh, 800 mesh, one kind of 1250 mesh, four kinds of different meshes or several
Kind composition.
Graphite is flaky graphite, is made of the one or more of 32 mesh, 100 mesh, 325 three kinds of different meshes of mesh.
Be chopped polypropylene fibre by 3mm be chopped polypropylene fibre, 6mm be chopped polypropylene fibre, 9mm be chopped polypropylene fibre
One or more of compositions.
Functional filler is talcum powder, bentonite, vermiculite, diatomite, flyash, expanded graphite, expanded perlite, hollow
One or several kinds of compositions of ceramic, Procedure of Polymerized Micro-Particles with Hollow.
Auxiliary agent includes：The common aqueous promoter such as wetting dispersing agent, antifoaming agent, coalescents, thickener, levelling agent.Into one
It is 1~5 part to walk preferred wetting dispersing agent dosage, and antifoaming agent dosage is 0.5~3 part, and coalescents dosage is 0.5~2 part, thickening
Agent dosage is 0.1~2 part, and levelling agent dosage is 0.1-1 parts.Wherein wetting dispersing agent is polyether-type modified siloxane, has face
One or several kinds of compositions of filler affinity groups copolymer, polyester and polyether polymer；Antifoaming agent is type siloxane antifoaming agent
It is one or several kinds of；Coalescents are alcohol ethers, the one or several kinds of alcohol ether esters coalescents；Thickener is urea-modified
One or more of compositions of polyurethane solutions, hyperbranched structure polyurethane solution；Levelling agent is polyether-modified organosilicon.It is excellent
Choosing wherein wetting dispersing agent is one or several kinds of compositions of BYK-180, BYK-181, BYK-2012, BYK-307；Antifoaming agent is
The one or several kinds of BYK-011, BYK-012, BYK-024, BYK-035；Coalescents are dipropylene；Thickener is
BYK-425, BYK-420 are formed；Levelling agent is BYK-333.
The above-mentioned modulation process for toasting the heavy sizing aqueous damping paint of quick-drying：Homogenizer 1000-1400r/min
Under, deionized water is added into the styrene-acrylic emulsion for having gradient damping structure, then be added pH adjusting agent adjust pH to 8.8~
9.0, addition wetting dispersing agent, coalescents and antifoaming agent turn speed as 1400-1800r/min after stirring 10-30min, stir
30-60min.Then functional filler, calcium carbonate, graphite and mica powder is added, thickening is added after 30-60min is stirred after adding
Agent and levelling agent obtain baking quick-drying water-based damping paint after stirring 15-30min, and paint process whole process leads to condensed water drop
Temperature.
The present invention is by having gradient-structure styrene-acrylic resin lotion and special color stuffing system, prepared aqueous resistance
Damping paint can disposably scratch 2-3mm not saggings, and be immediately placed in 120 DEG C of -160 DEG C of baking ovens after scratching and toasted,
Paint film is completely dried in 20min, coating surface zero defect.Paint film comprehensive performance meets TB-T 2932-1998 B class damping paints
Performance requirement is suitble to serialization quickly performance requirement of the production to aqueous damping coating.
Compared with prior art, the beneficial effects of the invention are as follows：
The method of the present invention selects styrene as the principal monomer for improving lotion damping capacity, real by power level charging method
Consecutive variations are presented in existing intramolecule structure, and latex particle is distributed from inside to outer layer styrene is presented graded, synthesis
Have the styrene-acrylic emulsion of gradient damping structure, has effectively widened the effective damping temperature range of lotion.
Selection has the functional filler of special microstructure, is baking paint in coating internal build hydrophobic channel
The spilling of moisture provides path in the process, solves to carry out toasting dry coating under aqueous damping coating thickness painting state and gas occurs
The problem of bubble, cracking.
Description of the drawings
Fig. 1 is the schematic device that the styrene-acrylic emulsion for having gradient damping structure is prepared using power level charging method.
Specific implementation mode
With reference to embodiment, the invention will be further described, but the present invention is not limited to following embodiments.
(1) power level charging method synthesis has gradient damping structure styrene-acrylic emulsion
The principle and feature of the synthetic resin method of the present invention are described below in conjunction with example, example is served only for
It explains the present invention, is not intended to limit the scope of the present invention.
Raw material sources：
Styrene, methyl methacrylate, n-butyl acrylate：SINOPEC Qilu Petro-Chemical Corp
(methyl) acrylic acid：Shanghai Mike's woods biochemical technology Co., Ltd
Methacrylamide：Mitsui Chemicals, Inc
Glycidyl methacrylate：Ningbo Hua Jia Chemical Co., Ltd.s
TX-21/TX-30：Jiangsu Hai'an Petrochemical Plant
SR-10：Asahi Denka Kogyo K. K
Neopelex, sodium bicarbonate, ammonium persulfate, sodium hydrogensulfite：Three factory of Beijing chemical reagent
Deionized water：It makes by oneself in laboratory
One kind having gradient-structure styrene-acrylic emulsion synthetic method, includes the following steps：
According to a certain ratio by monomer mixing compositing monomer mixed liquor I, according to a certain ratio by emulsifier, deionized water,
Monomer is made pre-emulsion II, wherein I and II and contains monomer styrene, methyl methacrylate, n-butyl acrylate, methyl-prop
Acrylamide, (methyl) acrylic acid, glycidyl methacrylate.
Monomer, emulsifier, PH conditioning agents and deionized water is added according to a certain percentage in a kettle and prepares bottoming liquid, in
Under nitrogen atmosphere, deoxygenation is stirred at a certain temperature.
It is separately added into ammonium persulfate and sodium hydrogensulfite initiator solution, heat preservation obtains seed emulsion in 0.5-1 hours.
Using power level charging method, monomer mixed solution I and pre-emulsion II is added dropwise.By controlling metering pump I and metering pump II
Velocity ratio, realize that the composition of monomer constantly changes, be added dropwise total duration be 4 hours.3 hours are kept the temperature after dripping, is cooled
Obtain final products.Reaction unit figure is shown in attached drawing 1.
Embodiment 1
First by 4.52 parts of styrene, 4.52 parts of methyl methacrylates, 9.71 parts of n-butyl acrylates, 0.12 part of propylene
Acid, 0.25 part of Methacrylamide, 0.36 part of glycidyl methacrylate, 2.53 parts of TX-21,5.06 parts of detergent alkylates
Sodium sulfonate, 0.98 part of sodium bicarbonate, 365 parts of deionized waters are added in reaction kettle after mixing, open agitating device adjusting and turn
Speed is 340r/min and heating device to 80 DEG C, and 30min is stirred under nitrogen atmosphere.By 0.0281 part of ammonium persulfate and 0.0281
Part sodium hydrogensulfite is directly added into reaction kettle after being dissolved in respectively in 5 parts of water, and seed emulsion is obtained after curing 30min.
By 85.86 parts of styrene, 85.86 parts of methyl methacrylates, 184.54 parts of n-butyl acrylates, 2.31 parts of propylene
Acid, 6.95 parts of glycidyl acrylates utilize Methacrylamide (4.63 parts of first that 4.63 parts are added after mechanical agitation mixing
Base acrylamide is dissolved in 9.75 parts of deionized waters) monomer mixed solution I is made, it keeps monomer mixture to be in using mechanical agitation and stirs
Mix state, rotating speed 100rpm.
By 135 parts of styrene, 135 parts of methyl methacrylates, 105 parts of n-butyl acrylates, 2.44 parts of acrylic acid, 7.31
Part glycidyl methacrylate, 1.46 parts of TX-21,2.92 parts of neopelexes, 240 parts of deionized waters utilize machine
Tool is added 4.88 parts of Methacrylamides (4.88 parts of Methacrylamides are dissolved in 9.75 parts of deionized waters) after being stirred and is made
Pre-emulsion II keeps pre-emulsion to be in stirring, rotating speed 100rpm using mechanical agitation.
1.0969 parts of ammonium persulfates and 1.0969 parts of sodium hydrogensulfites are separately added into 50 parts of deionized waters, initiation is made
Agent aqueous solution.
Initiator solution is added dropwise respectively to the reaction kettle equipped with seed emulsion, while monomer is added dropwise using metering pump I and mixes
Liquid I is closed, pre-emulsion II is added dropwise into monomer mixed solution I using metering pump II.It is 265 parts mixed to control flow pump I rate of addition
Close monomer per hour, control flow pump II rate of addition be 165.6 parts of pre-emulsions per hour, initiator solution be added dropwise it is total when
A length of 4 hours.
3 hours are kept the temperature after dripping all monomers and initiator solution, final products are obtained after cooling.
Embodiment 2
First by 4.52 parts of styrene, 4.52 parts of methyl methacrylates, 9.71 parts of n-butyl acrylates, 0.12 part of propylene
Acid, 0.25 part of Methacrylamide, 0.24 part of glycidyl methacrylate, 2.53 parts of TX-21,5.06 parts of detergent alkylates
Sodium sulfonate, 0.98 part of sodium bicarbonate, 365 parts of deionized waters are added in reaction kettle after mixing, open agitating device adjusting and turn
Speed is 340r/min and heating device to 80 DEG C, and 30min is stirred under nitrogen atmosphere.By 0.0281 part of ammonium persulfate and 0.0281
Part sodium hydrogensulfite is directly added into reaction kettle after being dissolved in respectively in 5 parts of water, and seed emulsion is obtained after curing 30min.
By 85.86 parts of styrene, 85.86 parts of methyl methacrylates, 184.54 parts of n-butyl acrylates, 2.31 parts of propylene
Acid, 4.63 parts of glycidyl acrylates utilize Methacrylamide (4.63 parts of first that 4.63 parts are added after mechanical agitation mixing
Base acrylamide is dissolved in 9.75 parts of deionized waters) monomer mixed solution I is made, it keeps monomer mixture to be in using mechanical agitation and stirs
Mix state, rotating speed 100rpm.
By 135 parts of styrene, 135 parts of methyl methacrylates, 105 parts of n-butyl acrylates, 2.44 parts of acrylic acid, 4.87
Part glycidyl methacrylate, 1.46 parts of TX-21,2.92 parts of neopelexes, 240 parts of deionized waters utilize machine
Tool is added 4.88 parts of Methacrylamides (4.88 parts of Methacrylamides are dissolved in 9.75 parts of deionized waters) after being stirred and is made
Pre-emulsion II keeps pre-emulsion to be in stirring, rotating speed 100rpm using mechanical agitation.
1.0969 parts of ammonium persulfates and 1.0969 parts of sodium hydrogensulfites are separately added into 50 parts of deionized waters, initiation is made
Agent aqueous solution.
Initiator solution is added dropwise respectively to the reaction kettle equipped with seed emulsion, while monomer is added dropwise using metering pump I and mixes
Liquid I is closed, pre-emulsion II is added dropwise into monomer mixed solution I using metering pump II.It is 265 parts mixed to control flow pump I rate of addition
Close monomer per hour, control flow pump II rate of addition be 165.6 parts of pre-emulsions per hour, initiator solution be added dropwise it is total when
A length of 4 hours.
3 hours are kept the temperature after dripping all monomers and initiator solution, final products are obtained after cooling.
Embodiment 3
First by 4.52 parts of styrene, 4.52 parts of methyl methacrylates, 9.71 parts of n-butyl acrylates, 0.12 part of propylene
Acid, 0.25 part of Methacrylamide, 0.12 part of glycidyl methacrylate, 2.53 parts of TX-21,5.06 parts of detergent alkylates
Sodium sulfonate, 0.98 part of sodium bicarbonate, 365 parts of deionized waters are added in reaction kettle after mixing, open agitating device adjusting and turn
Speed is 340r/min and heating device to 80 DEG C, and 30min is stirred under nitrogen atmosphere.By 0.0281 part of ammonium persulfate and 0.0281
Part sodium hydrogensulfite is directly added into reaction kettle after being dissolved in respectively in 5 parts of water, and seed emulsion is obtained after curing 30min.
By 85.86 parts of styrene, 85.86 parts of methyl methacrylates, 184.54 parts of n-butyl acrylates, 2.31 parts of propylene
Acid, 2.32 parts of glycidyl acrylates utilize Methacrylamide (4.63 parts of first that 4.63 parts are added after mechanical agitation mixing
Base acrylamide is dissolved in 9.75 parts of deionized waters) monomer mixed solution I is made, it keeps monomer mixture to be in using mechanical agitation and stirs
Mix state, rotating speed 100rpm.
By 135 parts of styrene, 135 parts of methyl methacrylates, 105 parts of n-butyl acrylates, 2.44 parts of acrylic acid, 2.44
Part glycidyl methacrylate, 1.46 parts of TX-21,2.92 parts of neopelexes, 240 parts of deionized waters utilize machine
Tool is added 4.88 parts of Methacrylamides (4.88 parts of Methacrylamides are dissolved in 9.75 parts of deionized waters) after being stirred and is made
Pre-emulsion II keeps pre-emulsion to be in stirring, rotating speed 100rpm using mechanical agitation.
1.0969 parts of ammonium persulfates and 1.0969 parts of sodium hydrogensulfites are separately added into 50 parts of deionized waters, initiation is made
Agent aqueous solution.
Initiator solution is added dropwise respectively to the reaction kettle equipped with seed emulsion, while monomer is added dropwise using metering pump I and mixes
Liquid I is closed, pre-emulsion II is added dropwise into monomer mixed solution I using metering pump II.It is 265 parts mixed to control flow pump I rate of addition
Close monomer per hour, control flow pump II rate of addition be 165.6 parts of pre-emulsions per hour, initiator solution be added dropwise it is total when
A length of 4 hours.
3 hours are kept the temperature after dripping all monomers and initiator solution, final products are obtained after cooling.
Embodiment 4
First by 4.52 parts of styrene, 4.52 parts of methyl methacrylates, 9.71 parts of n-butyl acrylates, 0.12 part of methyl-prop
Olefin(e) acid, 0.25 part of Methacrylamide, 0.36 part of glycidyl methacrylate, 2.53 parts of TX-30,5.06 parts of SR-10,
0.98 part of sodium bicarbonate, 365 parts of deionized waters are added in reaction kettle after mixing, open agitating device adjusting rotating speed and are
340r/min and heating device stir 30min to 80 DEG C under nitrogen atmosphere.By 0.0281 part of ammonium persulfate and 0.0281 part of Asia
Niter cake is directly added into reaction kettle after being dissolved in respectively in 5 parts of water, seed emulsion is obtained after curing 30min.
By 85.86 parts of styrene, 85.86 parts of methyl methacrylates, 184.54 parts of n-butyl acrylates, 2.31 parts of methyl
Acrylic acid, 6.95 parts of glycidyl acrylates utilize the Methacrylamide (4.63 that 4.63 parts are added after mechanical agitation mixing
Part Methacrylamide is dissolved in 9.75 parts of deionized waters) monomer mixed solution I is made, it is kept at monomer mixture using mechanical agitation
In stirring, rotating speed 100rpm.
By 135 parts of styrene, 135 parts of methyl methacrylates, 105 parts of n-butyl acrylates, 2.44 parts of methacrylic acids,
7.31 parts of glycidyl methacrylate, 1.46 parts of TX-30,2.92 parts of SR-10,240 parts of deionized waters utilize mechanical agitation
4.88 parts of Methacrylamides (4.88 parts of Methacrylamides are dissolved in 9.75 parts of deionized waters) are added after mixing, pre-emulsification is made
Liquid II keeps pre-emulsion to be in stirring, rotating speed 100rpm using mechanical agitation.
1.0969 parts of ammonium persulfates and 1.0969 parts of sodium hydrogensulfites are separately added into 50 parts of deionized waters, initiation is made
Agent aqueous solution.
Initiator solution is added dropwise respectively to the reaction kettle equipped with seed emulsion, while monomer is added dropwise using metering pump I and mixes
Liquid I is closed, pre-emulsion II is added dropwise into monomer mixed solution I using metering pump II.It is 265 parts mixed to control flow pump I rate of addition
Close monomer per hour, control flow pump II rate of addition be 165.6 parts of pre-emulsions per hour, initiator solution be added dropwise it is total when
A length of 4 hours.
3 hours are kept the temperature after dripping all monomers and initiator solution, final products are obtained after cooling.
Embodiment 5
First by 4.52 parts of styrene, 4.52 parts of methyl methacrylates, 9.71 parts of n-butyl acrylates, 0.12 part of methyl-prop
Olefin(e) acid, 0.25 part of Methacrylamide, 0.24 part of glycidyl methacrylate, 2.53 parts of TX-30,5.06 parts of SR-10,
0.98 part of sodium bicarbonate, 365 parts of deionized waters are added in reaction kettle after mixing, open agitating device adjusting rotating speed and are
340r/min and heating device stir 30min to 80 DEG C under nitrogen atmosphere.By 0.0281 part of ammonium persulfate and 0.0281 part of Asia
Niter cake is directly added into reaction kettle after being dissolved in respectively in 5 parts of water, seed emulsion is obtained after curing 30min.
By 85.86 parts of styrene, 85.86 parts of methyl methacrylates, 184.54 parts of n-butyl acrylates, 2.31 parts of methyl
Acrylic acid, 4.63 parts of glycidyl acrylates utilize the Methacrylamide (4.63 that 4.63 parts are added after mechanical agitation mixing
Part Methacrylamide is dissolved in 9.75 parts of deionized waters) monomer mixed solution I is made, it is kept at monomer mixture using mechanical agitation
In stirring, rotating speed 100rpm.
By 135 parts of styrene, 135 parts of methyl methacrylates, 105 parts of n-butyl acrylates, 2.44 parts of methacrylic acids,
4.87 parts of glycidyl methacrylate, 1.46 parts of TX-30,2.92 parts of SR-10,240 parts of deionized waters utilize mechanical agitation
4.88 parts of Methacrylamides (4.88 parts of Methacrylamides are dissolved in 9.75 parts of deionized waters) are added after mixing, pre-emulsification is made
Liquid II keeps pre-emulsion to be in stirring, rotating speed 100rpm using mechanical agitation.
1.0969 parts of ammonium persulfates and 1.0969 parts of sodium hydrogensulfites are separately added into 50 parts of deionized waters, initiation is made
Agent aqueous solution.
Initiator solution is added dropwise respectively to the reaction kettle equipped with seed emulsion, while monomer is added dropwise using metering pump I and mixes
Liquid I is closed, pre-emulsion II is added dropwise into monomer mixed solution I using metering pump II.It is 265 parts mixed to control flow pump I rate of addition
Close monomer per hour, control flow pump II rate of addition be 165.6 parts of pre-emulsions per hour, initiator solution be added dropwise it is total when
A length of 4 hours.
3 hours are kept the temperature after dripping all monomers and initiator solution, final products are obtained after cooling.
Embodiment 6
First by 4.52 parts of styrene, 4.52 parts of methyl methacrylates, 9.71 parts of n-butyl acrylates, 0.12 part of methyl-prop
Olefin(e) acid, 0.25 part of Methacrylamide, 0.12 part of glycidyl methacrylate 2.53 parts of TX-30,5.06 parts of SR-10,
0.98 part of sodium bicarbonate, 365 parts of deionized waters are added in reaction kettle after mixing, open agitating device adjusting rotating speed and are
340r/min and heating device stir 30min to 80 DEG C under nitrogen atmosphere.By 0.0281 part of ammonium persulfate and 0.0281 part of Asia
Niter cake is directly added into reaction kettle after being dissolved in respectively in 5 parts of water, seed emulsion is obtained after curing 30min.
By 85.86 parts of styrene, 85.86 parts of methyl methacrylates, 184.54 parts of n-butyl acrylates, 2.31 parts of methyl
Acrylic acid, 2.32 parts of glycidyl acrylates utilize the Methacrylamide (4.63 that 4.63 parts are added after mechanical agitation mixing
Part Methacrylamide is dissolved in 9.75 parts of deionized waters) monomer mixed solution I is made, it is kept at monomer mixture using mechanical agitation
In stirring, rotating speed 100rpm.
By 135 parts of styrene, 135 parts of methyl methacrylates, 105 parts of n-butyl acrylates, 2.44 parts of methacrylic acids,
2.44 parts of glycidyl methacrylate, 1.46 parts of TX-30,2.92 parts of SR-10,240 parts of deionized waters utilize mechanical agitation
4.88 parts of Methacrylamides (4.88 parts of Methacrylamides are dissolved in 9.75 parts of deionized waters) are added after mixing, pre-emulsification is made
Liquid II keeps pre-emulsion to be in stirring, rotating speed 100rpm using mechanical agitation.
1.0969 parts of ammonium persulfates and 1.0969 parts of sodium hydrogensulfites are separately added into 50 parts of deionized waters, initiation is made
Agent aqueous solution.
Initiator solution is added dropwise respectively to the reaction kettle equipped with seed emulsion, while monomer is added dropwise using metering pump I and mixes
Liquid I is closed, pre-emulsion II is added dropwise into monomer mixed solution I using metering pump II.It is 265 parts mixed to control flow pump I rate of addition
Close monomer per hour, control flow pump II rate of addition be 165.6 parts of pre-emulsions per hour, initiator solution be added dropwise it is total when
A length of 4 hours.
3 hours are kept the temperature after dripping all monomers and initiator solution, final products are obtained after cooling.
Lotion prepared by embodiment 1-6, comprehensive performance see the table below 1.
1 lotion comprehensive performance of table
(2) preparation of quick-drying water-based damping paint can be toasted
Resin aqueous emulsion used by during paint is the lotion synthesized by embodiment 1 in above-mentioned emulsion synthesis.
Raw material sources：
Lotion：Lotion prepared by embodiment 1
Talcum powder, flaky graphite, expanded graphite, dicalcium powder, mica powder：Kai Jie Mineral Products Trades company
Diatomite：Tianjin good fortune morning chemical reagent factory
Flyash：Lingshou County perseverance stone ore product processing factory
Procedure of Polymerized Micro-Particles with Hollow：Akzo Nobel N.V.
Aminomethyl propanol, dipropylene：DOW Chemical
BYK-2012,BYK-307,BYK-024,BYK-425,BYK-420：Bi Ke auxiliary agents Co., Ltd
Embodiment 7
Under homogenizer 1200r/min, 25 parts of deionized waters are added into 75 parts of lotions, 0.6 part of ammonia first is then added
Base propyl alcohol adjusts pH to 8.8~9.0, and 7.2 parts of byk-2012,0.82 part of byk-333,3 parts of dipropylene glycol are added after stirring 10min
It is 1600r/min that butyl ether and 3 parts of byk-024, which turn speed, stirs 30min.Then 12.5 parts of talcum powder of addition, 8 parts of flaky graphites,
4.5 parts of expanded graphites, the chopped polypropylene fibres of 2 parts of 3mm, 10 parts of diatomite, 15 parts of dicalcium powders and 75 parts of mica powders, are stirred after adding
0.66 part of byk-425 is added after mixing 30min, 1.96 parts of byk-420 are added after stirring 10min, 0.66 part is added after stirring 10min
Byk-425 obtains baking quick-drying water-based damping paint after stirring 15min.Paint process whole process leads to condensed water cooling.
Embodiment 8
Under homogenizer 1200r/min, 25 parts of deionized waters are added into 75 parts of lotions, 0.6 part of ammonia first is then added
Base propyl alcohol adjusts pH to 8.8~9.0, and 7.2 parts of byk-2012,0.82 part of byk-333,3 parts of dipropylene glycol are added after stirring 10min
It is 1600r/min that butyl ether and 3 parts of byk-024, which turn speed, stirs 30min.Then 12.5 parts of talcum powder of addition, 8 parts of flaky graphites,
4.5 parts of expanded graphites, the chopped polypropylene fibres of 2 parts of 3mm, 10 parts of diatomite, 15 parts of dicalcium powders and 75 parts of mica powders, are stirred after adding
0.88 part of byk-425 is added after mixing 30min, 1.96 parts of byk-420 are added after stirring 10min, 0.88 part is added after stirring 10min
Byk-425 obtains baking quick-drying water-based damping paint after stirring 15min.Paint process whole process leads to condensed water cooling.
Embodiment 9
Under homogenizer 1200r/min, 25 parts of deionized waters are added into 75 parts of lotions, 0.6 part of ammonia first is then added
Base propyl alcohol adjusts pH to 8.8~9.0, and 7.2 parts of byk-2012,0.82 part of byk-333,3 parts of dipropylene glycol are added after stirring 10min
It is 1600r/min that butyl ether and 3 parts of byk-024, which turn speed, stirs 30min.Then 12.5 parts of talcum powder of addition, 8 parts of flaky graphites,
4.5 parts of flyash, the chopped polypropylene fibres of 2 parts of 3mm, 10 parts of diatomite, 15 parts of dicalcium powders and 75 parts of mica powders, are stirred after adding
0.66 part of byk-425 is added after 30min, 1.96 parts of byk-420 are added after stirring 10min, 0.66 part is added after stirring 10min
Byk-425 obtains baking quick-drying water-based damping paint after stirring 15min.Paint process whole process leads to condensed water cooling.
Embodiment 10
Under homogenizer 1200r/min, 25 parts of deionized waters are added into 75 parts of lotions, 0.6 part of ammonia first is then added
Base propyl alcohol adjusts pH to 8.8~9.0, and 7.2 parts of byk-2012,0.82 part of byk-333,3 parts of dipropylene glycol are added after stirring 10min
It is 1600r/min that butyl ether and 3 parts of byk-024, which turn speed, stirs 30min.Then 12.5 parts of talcum powder of addition, 8 parts of flaky graphites,
4.5 parts of flyash, the chopped polypropylene fibres of 2 parts of 3mm, 10 parts of diatomite, 15 parts of dicalcium powders and 75 parts of mica powders, are stirred after adding
0.88 part of byk-425 is added after 30min, 1.96 parts of byk-420 are added after stirring 10min, 0.88 part is added after stirring 10min
Byk-425 obtains baking quick-drying water-based damping paint after stirring 15min.Paint process whole process leads to condensed water cooling.
Embodiment 11
Under homogenizer 1200r/min, 25 parts of deionized waters are added into 75 parts of lotions, 0.6 part of ammonia first is then added
Base propyl alcohol adjusts pH to 8.8~9.0, and 7.2 parts of byk-2012,0.82 part of byk-333,3 parts of dipropylene glycol are added after stirring 10min
It is 1600r/min that butyl ether and 3 parts of byk-024, which turn speed, stirs 30min.Then 12.5 parts of talcum powder of addition, 8 parts of flaky graphites,
4.5 parts of Procedure of Polymerized Micro-Particles with Hollow, the chopped polypropylene fibres of 2 parts of 3mm, 10 parts of diatomite, 15 parts of dicalcium powders and 75 parts of mica powders, add
0.66 part of byk-425 is added after stirring 30min after complete, 1.96 parts of byk-420 are added after stirring 10min, are added after stirring 10min
0.66 part of byk-425 obtains baking quick-drying water-based damping paint after stirring 15min.Paint process whole process leads to condensed water drop
Temperature.
Embodiment 12
Under homogenizer 1200r/min, 25 parts of deionized waters are added into 75 parts of lotions, 0.6 part of ammonia first is then added
Base propyl alcohol adjusts pH to 8.8~9.0, and 7.2 parts of byk-2012,0.82 part of byk-333,3 parts of dipropylene glycol are added after stirring 10min
It is 1600r/min that butyl ether and 3 parts of byk-024, which turn speed, stirs 30min.Then 12.5 parts of talcum powder of addition, 8 parts of flaky graphites,
4.5 parts of Procedure of Polymerized Micro-Particles with Hollow, the chopped polypropylene fibres of 2 parts of 3mm, 10 parts of diatomite, 15 parts of dicalcium powders and 75 parts of mica powders, add
0.88 part of byk-425 is added after stirring 30min after complete, 1.96 parts of byk-420 are added after stirring 10min, are added after stirring 10min
0.88 part of byk-425 obtains baking quick-drying water-based damping paint after stirring 15min.Paint process whole process leads to condensed water drop
Temperature.
Comparative example 7~12 toasts the comprehensive performance of quick-drying water-based damping paint, and wherein wet-film thickness is 2.2mm, is applied
120 DEG C of high-temperature bakings are directly carried out after film, performance is shown in Table 2：
2 aqueous damping coating comprehensive performance of table
Above example is some examples in the present invention, not does other any type of limitations to the present invention, any
Those skilled in the art are changed or are modified as the example of equivalent variations possibly also with the technology contents of the disclosure above,
In every case it is invented without departing from this technology and generates conflict, made any simple modification etc. according to the technical essence of the invention, still fall within this
The protection category of inventive technique scheme.
Claims (10)
1. one kind having gradient damping structure styrene-acrylic emulsion, which is characterized in that prepare latex particle, particle by power level charging method
Consecutive variations are presented in internal structure, and latex particle is distributed from inside to outer layer styrene is presented graded；
Emulsion formulations raw material include as follows according to parts by weight ingredient：
5 parts -30 parts of styrene monomer
10 parts -30 parts of methyl methacrylate monomer
10 parts -40 parts of n-butyl acrylate monomer
1 part -8 parts of functional monomer
0.1 part -1 part of sodium bicarbonate
1 part -4 parts of emulsifier
30 parts -60 parts of deionized water
0.01 part -0.1 part of initiator
Wherein functional monomer by acrylic acid, methacrylic acid, Methacrylamide, glycidyl methacrylate one kind
Or several compositions；Emulsifier is using nonionic emulsifier and anionic emulsifier compounding composition；Initiator is gone back using oxidation
Substance series initiators.
A kind of there is gradient damping structure styrene-acrylic emulsion 2. described in accordance with the claim 1, which is characterized in that latex particle is from interior
When portion is distributed presentation graded to outer layer styrene, styrene-content gradient increases.
3. described in accordance with the claim 1 a kind of with gradient damping structure styrene-acrylic emulsion, which is characterized in that wherein functional single
Body is made of the one or more of acrylic acid, methacrylic acid, Methacrylamide, glycidyl methacrylate；Emulsification
Agent is using nonionic emulsifier and anionic emulsifier compounding composition；Initiator uses redox system initiator.
4. described in accordance with the claim 1 a kind of with gradient damping structure styrene-acrylic emulsion, which is characterized in that emulsifier TX-
21, the mixture of the mixture of neopelex or TX-30, SR-10, weight ratio 1-6:1-10；Using
Ammonium sulfate builds redox system with sodium hydrogensulfite, according to weight ratio ammonium persulfate：Sodium hydrogensulfite is 1:1-3:1.
5. preparing claim 1-4 any one of them has the method for gradient damping structure styrene-acrylic emulsion, which is characterized in that packet
Include following steps：
1. the preparation of seed emulsion
Part styrene, part methyl methyl acrylate, part acrylic acid N-butyl, part functionalities list are added in a kettle
Body, emulsifier, pH adjusting agent and portions of de-ionized water prepare bottoming liquid, under nitrogen atmosphere, stir deoxygenation；It is separately added into initiation
Agent aqueous solution, heat preservation obtain seed emulsion in 0.5-1 hours；
2. the preparation of monomer mixed solution
Part styrene, part methyl methyl acrylate, part acrylic acid N-butyl, part functionalities monomer are mixed and prepared
Go out monomer mixed solution I, monomer mixed solution is kept to be in stirring, such as using mechanical agitation with 100rpm speed.
3. the preparation of pre-emulsion
By residual styrene, remaining methyl methacrylate, residual acrylic acid N-butyl, remaining functional monomer, remaining emulsification
Agent, portions of de-ionized water mixing composition pre-emulsion II, keep pre-emulsion II be in stirring, such as use mechanical agitation with
100rpm speed；
4. the preparation of initiator solution
Remaining initiator is dissolved in remaining deionized water and prepares initiator solution；
5. polymerization procedure
Using power level charging method, monomer mixed solution I and pre-emulsion II are added dropwise into seed emulsion；Using metering pump I by monomer
Mixed liquor I is added dropwise to reaction kettle, and pre-emulsion is added dropwise in mix monomer liquid I by metering pump II, by controlling metering pump I
With the velocity ratio of metering pump II, realize that the composition of mix monomer liquid constantly changes, it is 4 hours that total duration, which is added dropwise, is protected after dripping
Temperature 3 hours, cools to obtain final products；
Styrene accounts for the mole percent that styrene in the mole percent of monomer, pre-emulsion II accounts for monomer in monomer mixed solution
Difference, the final latex particle for preparing the distribution from inside to outer layer styrene and graded being presented.
6. according to the method for claim 5, which is characterized in that by adjusting the rate of addition and pre-emulsification of monomer mixed solution
The rate of addition of liquid II to be added dropwise styrene in night and accounts for monomer more than styrene in seed emulsion by the mole percent of monomer
Mole percent.
7. a kind of comprising claim 1-4 any one of them there is the quick-drying thickness of toasting of gradient damping structure styrene-acrylic emulsion to starch
Type aqueous damping coating, which is characterized in that coating composition is as follows according to parts by weight ingredient：
Has 20-40 parts of the styrene-acrylic emulsion of gradient damping structure
20-50 parts of mica powder
0-20 parts of calcium carbonate
0-10 parts of graphite
Be chopped 0-3 parts of polypropylene fibre
10-30 parts of functional filler
2-10 parts of auxiliary agent
5-20 parts of deionized water.
8. the heavy sizing aqueous damping paint of quick-drying can be toasted according to claim 7, which is characterized in that mica powder is white
Mica is made of the one or more of 200 mesh, 325 mesh, 800 mesh, 1,000 four kinds of different meshes of mesh；
Calcium carbonate selects powdered whiting, by 200 mesh, one or more of groups of 325 mesh, 800 mesh, 1250 mesh, four kinds of different meshes
At；
Graphite is flaky graphite, is made of the one or more of 32 mesh, 100 mesh, 325 three kinds of different meshes of mesh；
Be chopped polypropylene fibre by 3mm be chopped polypropylene fibre, 6mm be chopped polypropylene fibre, 9mm be chopped polypropylene fibre one
Kind or several compositions；
Functional filler is talcum powder, bentonite, vermiculite, diatomite, flyash, expanded graphite, expanded perlite, hollow ceramic
One or several kinds of compositions of micro mist, Procedure of Polymerized Micro-Particles with Hollow；
Auxiliary agent includes：The common aqueous promoter of wetting dispersing agent, antifoaming agent, coalescents, thickener, levelling agent.
9. the heavy sizing aqueous damping paint of quick-drying can be toasted according to claim 8, which is characterized in that wetting dispersing agent is used
Amount is 1~5 part, and antifoaming agent dosage is 0.5~3 part, and coalescents dosage is 0.5~2 part, and thickener dosage is 0.1~2 part,
Levelling agent dosage is 0.1-1 parts；Wherein wetting dispersing agent is polyether-type modified siloxane, has the copolymerization of color stuffing affinity groups
One or several kinds of compositions of object, polyester and polyether polymer；Antifoaming agent is the one or several kinds of type siloxane antifoaming agent；At
Film auxiliary agent is alcohol ethers, the one or several kinds of alcohol ether esters coalescents；Thickener is the polyurethane solutions of urea-modified, height
One or more of compositions of branched structure polyurethane solutions；Levelling agent is polyether-modified organosilicon.Wetting and dispersing preferably wherein
Agent is one or several kinds of compositions of BYK-180, BYK-181, BYK-2012, BYK-307；Antifoaming agent is BYK-011, BYK-
012, the one or several kinds of BYK-024, BYK-035；Coalescents are dipropylene；Thickener is BYK-425, BYK-
420 compositions；Levelling agent is BYK-333.
10. the modulation process of the heavy sizing aqueous damping paint of quick-drying can be toasted by preparing claim 6-9 any one of them, special
Sign is, under homogenizer 1000-1400r/min, deionized water is added into the styrene-acrylic emulsion for having gradient damping structure,
Then pH adjusting agent is added and adjusts pH to 8.8~9.0, stir be added after 10-30min auxiliary agent wetting dispersing agent, coalescents and
It is 1400-1800r/min that antifoaming agent, which turns speed, stirs 30-60min；Then functional filler, calcium carbonate, graphite and cloud is added
Auxiliary agent thickener and levelling agent is added after stirring 30-60min after adding in female powder, and baking quick-drying is obtained after stirring 15-30min
Type aqueous damping coating, paint process whole process lead to condensed water cooling.
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| CN201910337953.XA CN109942756B (en) | 2018-05-17 | 2019-04-24 | Styrene-acrylic emulsion with gradient damping structure and bakeable thick-paste type water-based damping coating and preparation |
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| CN201910337953.XA Active CN109942756B (en) | 2018-05-17 | 2019-04-24 | Styrene-acrylic emulsion with gradient damping structure and bakeable thick-paste type water-based damping coating and preparation |
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| CN109679426A (en) * | 2018-12-17 | 2019-04-26 | 万华化学集团股份有限公司 | A kind of aqueous damping coating and preparation method thereof |
| CN112680047A (en) * | 2020-12-29 | 2021-04-20 | 重庆德天汽车新材料研究院有限公司 | Automotive bakeable thick paste type water-based damping coating and preparation method thereof |
| CN116217786A (en) * | 2021-12-02 | 2023-06-06 | 万华化学集团股份有限公司 | Water-based styrene-acrylic JS waterproof emulsion and preparation method thereof |
| CN114316860A (en) * | 2022-01-20 | 2022-04-12 | 安徽衡光新材料科技有限公司 | Preparation method of gradient-structure high-peel-strength high-water-resistance pressure-sensitive adhesive |
| CN114316860B (en) * | 2022-01-20 | 2023-09-19 | 安徽衡光新材料科技有限公司 | Preparation method of pressure-sensitive adhesive with gradient structure and high peel strength and water resistance |
| CN116120800A (en) * | 2023-02-21 | 2023-05-16 | 中国人民解放军陆军工程大学 | Low-temperature-resistant water-based damping coating and preparation method thereof |
| CN116120800B (en) * | 2023-02-21 | 2023-10-20 | 中国人民解放军陆军工程大学 | Low-temperature-resistant water-based damping coating and preparation method thereof |
| CN116640487A (en) * | 2023-06-21 | 2023-08-25 | 沈阳帕卡濑精有限总公司 | High-temperature baking type water-based protective coating and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN109942756B (en) | 2021-06-08 |
| CN109942756A (en) | 2019-06-28 |
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