CN109293839A - Chlorinated polypropylene modified water-based acrylic resin with excellent water boiling resistance performance and preparation method thereof, coating - Google Patents
Chlorinated polypropylene modified water-based acrylic resin with excellent water boiling resistance performance and preparation method thereof, coating Download PDFInfo
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- CN109293839A CN109293839A CN201811039286.9A CN201811039286A CN109293839A CN 109293839 A CN109293839 A CN 109293839A CN 201811039286 A CN201811039286 A CN 201811039286A CN 109293839 A CN109293839 A CN 109293839A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/023—On to modified polymers, e.g. chlorinated polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D151/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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Abstract
The present invention relates to chlorinated polypropylene modified water-based acrylic resins with excellent water boiling resistance performance and preparation method thereof, coating.Chlorinated polypropylene modified water-based acrylic resin of the invention, is made of the raw material of following mass percent: cosolvent 5~20%；Chlorinated polypropylene 2.5~15%；Hydrophilic monomer 4.5~10%；Function monomer 5~20%；Initiator a 0.05~3%；Vinyl monomer 5~30%；Initiator b 0.05~3%；Neutralizer 3~12%；Deionized water 25~45.45%.The present invention is combined chlorinated polypropylene component and acrylic resin component by graft copolymerization, the adhesive force of resin Yu nonpolar polyolefin base material can be promoted, using two step dripping methods, it flocks together by hydrophilic monomer and with the functional monomer compared with strong-hydrophobicity and larger space steric hindrance, guarantees resin while with good adhesion with excellent water boiling resistance performance.
Description
Technical field
The present invention relates to a kind of modified aqueous acrylic acid resins, and in particular to the chlorination poly- third with excellent water boiling resistance performance
Alkene modified aqueous acrylic acid resin and preparation method thereof, coating.
Background technique
Component one of of the bumper as outside vehicle, it has certain decoration function not only for automobile appearance, heavier
What is wanted is to assume responsibility for absorbing and mitigating foreign impacts power, protection vehicle body and the important task for protecting occupant safety.Bumper at present
Plastic bumper is mainly used, this is because the elasticity of plastics itself will effectively absorb the impact force with pedestrian impact, to the greatest extent
The possible injured degree for allowing pedestrian reaches minimum.
Bumper mainly chooses polypropylene as material, in order to promote the appearance of plastic bumper and vehicle, needs moulding
Coat a coating in material surface.Since polypropylene material is non-polar substrate, to not affine with polar coating composition, cause
Coating adhesive force on polypropylene base is poor.Polypropylene material is solved usually using chlorinated polypropylene modified water-based acrylic resin
The adhesion problem of material.In recent years, for the pressure of environmental regulation, in order to reduce solvent of the bumper in coating process
Volatilization, research institution gradually develops chlorinated polypropylene modified water-based acrylic resin, significantly reduces the discharge of solvent.Chlorination is poly-
The synthesis path of propylene modified aqueous acrylic acid resin mainly introduces hydrophilic radical in chlorinated polypropylene, has resin
There is hydrophily, since chlorinated polypropylene hydrophobicity is stronger, it is therefore desirable to prepared chlorinated polypropylene modified aqueous acrylic acid
The hydrophilic radical content of resin is higher to can be only achieved Water-borne modification, this will be substantially reduced the water resistance of resin or even final coating.
But bumper coating industry requires coating to have preferable patience (it is required that coating is in 40 DEG C of hot water in the hot water
In water-fast 10 days not blistering non-whitenings).Polypropylene currently on the market is wanted with the performance that water paint is not possible to meet water boiling resistance
It asks, developing a kind of water-base resin for being able to satisfy the water boiling resistance that bumper field uses becomes an urgent demand in the field.
Summary of the invention
The purpose of the present invention is to provide a kind of chlorinated polypropylene modified water soluble acrylic acids with excellent water boiling resistance performance
Coating is made while with good adhesion with excellent using the chlorinated polypropylene modified water-based acrylic resin in resin
Water boiling resistance.
Second object of the present invention is to provide the chlorinated polypropylene modified aqueous acrylamide with excellent water boiling resistance performance
The preparation method of acid resin.
Third object of the present invention is to provide a kind of coating have excellent water boiling resistance performance containing above-mentioned in the coating
Chlorinated polypropylene modified water-based acrylic resin.
To achieve the above object, the technical scheme is that
Chlorinated polypropylene modified water-based acrylic resin with excellent water boiling resistance performance, by the original of following mass percent
Material is made:
Cosolvent: 5~20%；
Chlorinated polypropylene: 2.5~15%；
Hydrophilic monomer: 4.5~10%；
Function monomer: 5~20%；
Initiator a:0.05~3%；
Vinyl monomer: 5~30%；
Initiator b:0.05~3%；
Neutralizer: 3~12%；
Deionized water: 25~45.45%.
The function monomer is isobornyl methacrylate, isobornyl acrylate, 4- tert-butylcyclohexyl methyl-prop
Olefin(e) acid ester, 4- tert-butylcyclohexyl acrylate, cyclohexyl methacrylate, in cyclohexyl acrylate any one or it is several
Kind.
The chlorinty of the chlorinated polypropylene is 15~55%.
The preparation method of the above-mentioned chlorinated polypropylene modified water-based acrylic resin with excellent water boiling resistance performance, including with
Lower step:
1) hydrophilic monomer, function monomer and initiator a are uniformly mixed, obtain mix monomer A；By vinyl monomer and
Initiator b is uniformly mixed to obtain mix monomer B；
2) will cosolvent and chlorinated polypropylene mix after be warming up to 70~80 DEG C and gradually dissolve, be continuously heating to 80 later~
90 DEG C, mix monomer A is added dropwise, after completion of dropwise addition, in 80~90 DEG C of 0.5~1h of heat preservation, is warming up to 100~120 DEG C later, continues
Mix monomer B is added dropwise, after completion of dropwise addition, 2~4h is kept the temperature at 100~120 DEG C, neutralizer is added after cooling and is neutralized, side
It stirs side and deionized water is added, obtain chlorinated polypropylene modified water-based acrylic resin.
Mix monomer A and mix monomer B in step 2) in 2~3h in being added dropwise.
40~60 DEG C are cooled in step 2).
The hydrophilic monomer is acrylic acid, methacrylic acid, any one or a few in maleic anhydride.
The vinyl monomer methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate,
Propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, acrylic acid-2-ethyl caproite, acrylic acid
N-octyl, n octyl methacrylate, benzyl acrylate, any one or a few in styrene.
The initiator a is azo-initiator, and the azo-initiator is azodiisobutyronitrile, azo diisoamyl
Nitrile, azobisisoheptonitrile any one or a few；The initiator b is peroxide type initiators, the peroxide
Initiator is dibenzoyl peroxide, in peroxide di-t-butyl, two tertiary pentyl of peroxide, peroxidized t-butyl perbenzoate
Any one or a few.
The neutralizer is N, N- dimethylethanolamine, triethylamine, any one or a few in ammonium hydroxide.Alkali is added, makes
It, at salt, forms water-based system in water conducive to resin dispersion with carboxyl.If not using alkali to be neutralized, due in strand
The number of active center for shortening anion is few, so that strand is not easy to that aquation occurs with water, shows poor water dispersible；
If it is excessive that alkali is added, dispersion stability variation may cause, therefore the additional amount of neutralizer of the invention need to carry out strictly
Control.
The cosolvent is dimethylbenzene, trimethylbenzene, butanone, hexahydrotoluene, butyl glycol ether, propylene glycol monomethyl ether, the third two
Any one or a few in alcohol butyl ether.
A kind of coating, using the above-mentioned chlorinated polypropylene modified water-based acrylic resin system with excellent water boiling resistance performance
?.
The present invention has the chlorinated polypropylene modified water-based acrylic resin of excellent water boiling resistance performance, is a kind of aqueous tree
Rouge, raw material is simple, and using the functional monomer having compared with strong-hydrophobicity and larger space steric hindrance, which is nonpolarity knot
Structure is able to ascend the adhesive force of resin of the present invention Yu nonpolar polyolefin base material, meanwhile, to guarantee the aqueous of resin of the present invention
Change, resin raw material of the present invention also containing 4.5~10% hydrophilic monomer, by two step dripping methods, by hydrophilic monomer and tool
Have compared with strong-hydrophobicity together with the functional monomer " binding " of larger space steric hindrance, therefore, chlorinated polypropylene of the invention changes
Property water-based acrylic resin, with excellent water boiling resistance while with good adhesion.
The present invention has the preparation method of the chlorinated polypropylene modified water-based acrylic resin of excellent water boiling resistance performance, will mix
It closes monomer and is divided into two components dropwise additions, be added dropwise using the method that two steps are added dropwise.Wherein, the mix monomer A that the first step is added dropwise
Comprising hydrophilic monomer and function monomer, function monomer is with (methyl) acrylic acid compared with strong-hydrophobicity and larger space steric hindrance
The two components are added dropwise naphthenic base monomer simultaneously, and in synthesized polymer, hydrophilic monomer and function monomer " binding " exist
Together, a large amount of acrylate base function with stronger hydrophobic property and larger space steric hindrance is assembled around hydrophilic radical
Group, realizes the MOLECULE DESIGN that two kinds of functional group components bundle, to realize function monomer to the " protection of hydrophilic monomer
The effect of umbrella " can be obviously improved the water resistance of prepared resin, especially the water boiling resistance performance of final coating, without addition
Existing resin and the bad technical problem of coating water boiling resistance performance can be solved in other function monomers.
Preparation method of the invention, during two steps are added dropwise, first step initiator a uses azo-initiator, such
The initiation reaction of initiator is first order reaction, only forms a kind of free radical, and no induction is decomposed, and initiation reaction is to solvent and polymer
Insensitive, chain transfer reaction is relatively fewer, and polymerization process middle-molecular-weihydroxyethyl narrow distribution facilitates hydrophilic monomer and function monomer
" binding " is aggregated in the same polymer chain, and function monomer is made to play a protective role hydrophilic monomer, promotes prepared tree
The water resistance of rouge；Second step initiator b uses peroxide type initiators, generally causes at relatively high temperatures, the freedom of generation
Base energy is high, is also easy to produce hydrogen abstraction reaction, so that resin is generated branching crosslinking in the graft polymerization reaction later period, and crosslink density increases, point
Son amount distribution broadens, and two kinds of initiator collocation of the present invention use, and can further promote the water resistance of resin and coating, especially
Water boiling resistance performance.
Specific embodiment
Embodiment and comparative example raw materials are unless otherwise stated commercially available industrial goods, can be purchased by commercial channel
?.
Involved raw material include: in embodiment and comparative example
Chlorinated polypropylene 16-LP (solid content: 100%, chlorinity: 29%), technical grade, Japanese Japan's weaving；
Chlorinated polypropylene PP 803MWS (solid content: 100%, chlorinity: 29.5%), technical grade, Nippon Paper；
Methyl methacrylate, styrene, acrylic acid, methacrylic acid, isobornyl methacrylate, 4- tert-butyl ring
Hexyl methacrylate, 4- tert-butylcyclohexyl acrylate, butyl acrylate, hexahydrotoluene: technical grade, South Korea's SKization
It learns；
Dipropylene (DPnB), technical grade, DOW Chemical；
Dimethylethanolamine (DMEA) analyzes pure, BASF；
Azodiisobutyronitrile, dibenzoyl peroxide, peroxide di-t-butyl, peroxidized t-butyl perbenzoate: analysis
It is pure, Shanghai Ling Feng chemical reagent Co., Ltd；
Deionized water, self-control；Defoaming agent TEGO 902W, technical grade, Degussa Digao；
Wetting agent TEGO 270, technical grade, Degussa Digao；
Thickener RHEOLATE 299, technical grade, extra large name Si De are modest；
Aqueous color paste (ash): CTW-6086, aqueous finish paint (white): CTW-6090, double-component waterborne polyurethane coating varnish:
CTW-6096, technical grade, CNOOC Changzhou EP Coating Co., Ltd.；
The standard PP plate that PP plastic basis material is provided using Jiangyin City Rong Xin plasticizing Co., Ltd.
Embodiment 1
The present embodiment has the chlorinated polypropylene modified water-based acrylic resin of excellent water boiling resistance performance, by following raw material system
:
4.5g acrylic acid, 20g 4- tert-butylcyclohexyl acrylate, 0.2g azodiisobutyronitrile, 0.1 gram of peroxidating two
Benzoyl, 5g methyl methacrylate, 5.2g butyl acrylate, 5g dimethylbenzene, 5g propylene glycol monomethyl ether, 5g chlorinated polypropylene
16-LP, 5g neutralizer N, N- dimethylethanolamine, 45g deionized water.
The present embodiment has the preparation method of the chlorinated polypropylene modified water-and acrylate of excellent water boiling resistance performance, including
Following steps:
1) 4.5g acrylic acid, 20g 4- tert-butylcyclohexyl acrylate and 0.2g azodiisobutyronitrile are uniformly mixed,
Obtain mix monomer A；5g methyl methacrylate, 5.2g butyl acrylate and 0.1 gram of dibenzoyl peroxide are stirred
It is even, obtain mix monomer B；
2) equipped with dropping funel, thermometer, condenser and agitating device flask in, 5g dimethylbenzene and 5g the third two is added
Alcohol methyl ether adds 5g chlorinated polypropylene 16-LP as bottom material as cosolvent, be to slowly warm up to 75 DEG C it is gradually molten
Solution, is continuously heating to 85 DEG C, and mix monomer A then is added dropwise using dropping funel, drips off in 3h, after completion of dropwise addition, at 85 DEG C
1h is kept the temperature, after heat preservation, 110 DEG C is continuously heating to and mix monomer B is added dropwise using dropping funel, dripped off in 3h, completion of dropwise addition
Afterwards, 2h is kept the temperature at 110 DEG C, after heat preservation, is cooled to 40 DEG C, is added in neutralizer N, the N- dimethylethanolamine progress of 5g
With adjustment mixing speed to 1000rpm, 45g deionized water is added while stirring, obtains chlorinated polypropylene modified water soluble acrylic acid
Resin CM-WPA-1 (solid content: 40%).
Embodiment 2
The present embodiment has the chlorinated polypropylene modified water-based acrylic resin of excellent water boiling resistance performance, by following raw material system
:
10g methacrylic acid, 12g 4- t-butylcyclohexyl methyl acrylate, 0.15g azodiisobutyronitrile, 0.15g
Peroxide di-t-butyl, 3g methyl methacrylate, 8.2g butyl acrylate, 10g dimethylbenzene, 10g propylene glycol monomethyl ether, 15g
Chlorinated polypropylene PP 803MWS, 6.5g neutralizer N, N- dimethylethanolamine, 25g deionized water.
The present embodiment has the preparation method of the chlorinated polypropylene modified water-based acrylic resin of excellent water boiling resistance performance, packet
Include following steps:
1) 10g methacrylic acid, 12g4- t-butylcyclohexyl methyl acrylate, 0.15g azodiisobutyronitrile are stirred
It is uniformly mixed, obtains mix monomer A；By 3g methyl methacrylate, 8.2g butyl acrylate and 0.15g peroxide di-t-butyl
It is uniformly mixed, obtains mix monomer B；
2) in the flask equipped with dropping funel, thermometer, condenser and agitating device, 10g dimethylbenzene and 10g third is added
Glycol methyl ether adds 15g chlorinated polypropylene PP 803MWS as bottom material as cosolvent, is to slowly warm up to 75 DEG C
It gradually dissolves, is continuously heating to 85 DEG C, mix monomer A then is added dropwise using dropping funel, is dripped off in 2h, after completion of dropwise addition,
0.5h is kept the temperature at 85 DEG C, is continuously heating to 115 DEG C later, and mix monomer B is added dropwise using dropping funel, drips off in 2h, in 115 DEG C
Lower heat preservation 3h after heat preservation, is cooled to 40 DEG C, and neutralizer N, the N- dimethylethanolamine that 6.5g is added is neutralized, adjusted
25g deionized water is added while stirring, obtains chlorinated polypropylene modified water-based acrylic resin CM- to 500rpm for mixing speed
WPA-2 (solid content: 48.5%).
Embodiment 3
The present embodiment has the chlorinated polypropylene modified water-based acrylic resin of excellent water boiling resistance performance, by following raw material system
:
6g acrylic acid, 5g isobornyl methacrylate, 0.05g azodiisobutyronitrile, 15g methyl methacrylate, 15g
Butyl acrylate, 3g dibenzoyl peroxide, 5g dimethylbenzene, 2.5g chlorinated polypropylene 16-LP, 3g neutralizer triethylamine,
45.45g deionized water.
The present embodiment has the preparation method of the chlorinated polypropylene modified water-based acrylic resin of excellent water boiling resistance performance, packet
Include following steps:
1) 6g acrylic acid, 5g isobornyl methacrylate and 0.05g azodiisobutyronitrile are uniformly mixed, are obtained mixed
Close monomer A；15g methyl methacrylate, 15g butyl acrylate and 3g dibenzoyl peroxide are uniformly mixed, obtained mixed
Close monomer B；
2) in the flask equipped with dropping funel, thermometer, condenser and agitating device, 5g dimethylbenzene is added as hydrotropy
Agent, while 2.5g chlorinated polypropylene 16-LP is added as bottom material, it is to slowly warm up to 80 DEG C and gradually dissolves, be continuously heating to
90 DEG C, crylic acid ester mixture monomer A then is added dropwise using dropping funel, is dripped off in 3h, keeps the temperature 0.5h at 90 DEG C later, then
120 DEG C are continuously heating to, mix monomer B is added dropwise using dropping funel, drips off in 3h, after completion of dropwise addition, is kept the temperature at 120 DEG C
2h after heat preservation, is cooled to 50 DEG C, and the neutralizer triethylamine that 3g is added is neutralized, adjusts mixing speed to 800rpm, side
Stir side be added 45.45g deionized water, obtain chlorinated polypropylene modified water-based acrylic resin CM-WPA-3 (solid content:
46.55%).
Embodiment 4
The present embodiment has the chlorinated polypropylene modified water-based acrylic resin of excellent water boiling resistance performance, by following raw material system
:
9g acrylic acid, 15g isobornyl methacrylate, 3g azobisisoheptonitrile, 2g styrene, 3.95g acrylic acid fourth
Ester, 0.05g peroxidized t-butyl perbenzoate, 15g dimethylbenzene, 10g chlorinated polypropylene 16-LP, 12g neutralizer N, N- bis-
Methylethanolamine, 30g deionized water.
The present embodiment has the preparation method of the chlorinated polypropylene modified water-based acrylic resin of excellent water boiling resistance performance, packet
Include following steps；
1) 9g acrylic acid, 15g isobornyl methacrylate and 3g azobisisoheptonitrile are stirred, must be mixed single
Body A；2g styrene, 3.95g butyl acrylate and 0.05g peroxidized t-butyl perbenzoate are uniformly mixed, must be mixed single
Body B；
2) in the flask equipped with dropping funel, thermometer, condenser and agitating device, addition 15g dimethylbenzene, which is used as, to be helped
Solvent, while 10g chlorinated polypropylene 16-LP is added as bottom material, it is to slowly warm up to 70 DEG C and gradually dissolves, be continuously heating to
80 DEG C, mix monomer A then is added dropwise using dropping funel, is dripped off in 2h, after completion of dropwise addition, 1h, heat preservation knot are kept the temperature at 80 DEG C
Shu Hou is continuously heating to 100 DEG C, and mix monomer B is added dropwise using dropping funel, drips off in 2h, after completion of dropwise addition, at 100 DEG C
4h is kept the temperature, after heat preservation, is cooled to 45 DEG C, neutralizer N, the N- dimethylethanolamine that 12g is added is neutralized, adjusts stirring
30g deionized water is added while stirring, obtains chlorinated polypropylene modified water-based acrylic resin CM-WPA- to 1000rpm for speed
4 (solid contents: 43%).
Comparative example 1
It is in place of comparative example 1 and the difference of embodiment 1, the 5g chlorinated polypropylene 16-LP in embodiment 1 is gone
Fall, and methyl methacrylate increases to 10g by 5g and (is equivalent to 5g chlorination poly- third in the mix monomer B that second step is added dropwise
Olefine resin 16-LP changes 5g methyl methacrylate into, and is placed in mix monomer B and is added), other are identical with embodiment 1,
Standard aqueous acrylic resin C-CM-WPA-1 (solid content 40%) is finally prepared.Pass through pair of embodiment 1 and comparative example 1
Than investigating chlorinated polypropylene component influences the performance of prepared water-base resin and corresponding aqueous priming paint.
Comparative example 2
It is in place of comparative example 2 and the difference of embodiment 1, by function monomer (the 20g 4- t-butylcyclohexyl in embodiment 1
Base acrylate) remove, 20g methyl methacrylate is replaced with, other are identical with embodiment 1, are finally prepared and change
Property watersoluble chlorinated polypropylerie resin C-CM-WPA-2 (solid content 40%).By the comparison of embodiment 1 and comparative example 2, function is investigated
Energy monomer influences the performance of prepared water-base resin and corresponding aqueous priming paint.
Comparative example 3
The raw material of comparative example 3 and embodiment 1 are completely the same, and difference is, it is in comparative example 3 the preparation method is as follows:
1) by 4.5g acrylic acid, 20g 4- tert-butylcyclohexyl acrylate, 5g methyl methacrylate, 5.2g acrylic acid
Butyl ester, 0.2g azodiisobutyronitrile mix 0.1g dibenzoyl peroxide and mix after mixing, obtain mix monomer；
2) equipped with dropping funel, thermometer, condenser and agitating device flask in, 5g dimethylbenzene and 5g the third two is added
Alcohol methyl ether adds 5g chlorinated polypropylene 16-LP as bottom material as cosolvent, be to slowly warm up to 75 DEG C it is gradually molten
Solution, is continuously heating to 85 DEG C, then uses dropping funel a dropping step 1) in mix monomer, drip off in 6h, after completion of dropwise addition,
3h is kept the temperature at 110 DEG C, after heat preservation, is cooled to 40 DEG C, neutralizer N, the N- dimethylethanolamine for being added 5g neutralized,
Mixing speed is adjusted to 1000rpm, 45g deionized water is added while stirring, obtains chlorinated polypropylene modified water soluble acrylic acid tree
Rouge C-CM-WPA-3 (solid content: 40%).By the comparison of embodiment 1 and comparative example 3, investigates one step of mix monomer and be added dropwise and divide
Two steps, which are added dropwise, influences the performance of prepared water-base resin and corresponding aqueous priming paint.
Experimental example
1) preparation of coating
According to being formulated in table 1, polypropylene plastics aqueous priming paint is prepared.
To test prepared chlorinated polypropylene modified water-based acrylic resin water resistance and water boiling resistance performance, by embodiment 1-
Water-base resin CM-WPA-1, CM-WPA-2, CM-WPA-3, the CM-WPA-4 prepared in 4 is formulated as film-forming resin according to table 1
Prepare aqueous priming paint.The specific process is as follows: being first uniformly mixed film-forming resin in table 1 (serial number 1~3), sequentially add all kinds of
Coating additive (serial number 4~7) is added deionized water and adjusts viscosity, obtain aqueous priming paint after mixing evenly.
The mono-component aqueous base paint formulation of 1 Polypropylene Plastic Coatings of table
Wherein, using chlorinated polypropylene modified water-based acrylic resin CM-WPA-1, the CM- prepared in embodiment 1-4
The aqueous priming paint that WPA-2, CM-WPA-3, CM-WPA-4 are prepared is denoted as respectively: P-CM-1, P-CM-2, P-CM-3, P-CM-4 are adopted
Chlorinated polypropylene modified water-based acrylic resin C-CM-WPA-1, C-CM-WPA-2, the C-CM-WPA-3 prepared with comparative example 1-3
The aqueous priming paint as a comparison prepared is denoted as respectively: CP-CM-1, CP-CM-2, CP-CM-3.
2) template is prepared
Polypropylene plastics workpiece surface is cleaned up with solvent first, then applies aqueous priming paint made from step 1).According to
Deionized water is added in primers and adjusts viscosity to 40~50s for construction requirement, sprays 15~20min of surface drying, and then 80~90 DEG C
15~20min is toasted, base coat thickness is controlled at 10~15 μm.Prepared template places test performance after 7 days under room temperature.Bottom
Paint template, which is mainly tested, investigates adhesive force.
3) composite coating template is prepared
Polypropylene plastics workpiece surface is cleaned up with solvent first, then successively sprays bottom made from aqueous step 1)
Paint, aqueous finish paint and double-component waterborne polyurethane coating varnish.Spray-applied primer first is added in primers according to construction requirement and goes
Ionized water adjusts viscosity, sprays 15~20min of surface drying, then 80~90 DEG C of 15~20min of baking, and base coat thickness controls 10~
15μm；Spray aqueous finish paint CTW-6090 again, finishing coat thickness control is at 15~25 μm, 15~20min of surface drying；Two-component is sprayed again
Aqueous polyurethane coating varnish CTW-6096, coating varnish thickness control is between 35~45 μm, 10~15min of drying at room temperature
Afterwards, 30min solidification is toasted at 80 DEG C.Prepared template places test performance after 7 days under room temperature.
Composite coating template mainly investigates adhesive force, water resistance and water boiling resistance performance.
4) performance test
Adhesive force: coating adhesion is tested according to GB/T 9286-1998, is divided into 0~5 grade, 0 grade preferably, and 5 grades most
Difference.
Water resistance: water resistance and water boiling resistance performance are for composite coating.Wherein, water resistance is according to GB/T1733-
1993 " paint film water resistance measuring method " methods are measured, and are tested 10 days under room temperature (25 DEG C)；It is always divided into 1~4 grade, 1 grade most
Good, 4 grades worst, and 1 grade: paint film is unchanged；2 grades: paint film slightly blisters, and nothing falls off 3 grades: paint film wrinkles and falls off on a small quantity, part
It gets rusty；4 grades of paint blisters wrinkle, fall off and get rusty.
Water boiling resistance performance: water boiling resistance performance is tested according to GB/T 1733-1993 method, wherein hot water temperature 40
DEG C, the testing time 10 days.It is always divided into 1~4 grade, 1 grade preferably, and 4 grades worst, and 1 grade: paint film is unchanged；2 grades: paint film slightly rises
Bubble, nothing fall off 3 grades: paint film wrinkles and falls off on a small quantity, partially gets rusty；4 grades of paint blisters wrinkle, fall off and get rusty.
Coating property test result is shown in Table 2.
2 polypropylene aqueous priming paint of table and composite coating test result
By the performance test results in table 2 it is found that using the chlorinated polypropylene modified water soluble acrylic acid prepared in embodiment 1-4
The aqueous priming paint that resin CM-WPA-1, CM-WPA-2, CM-WPA-3, CM-WPA-4 are prepared is denoted as respectively: P-CM-1, P-CM-2,
P-CM-3, P-CM-4, this 4 aqueous priming paints have preferable adhesive force to substrate, and prepared composite coating equally has more
The ply adhesion of excellent adhesive force, i.e. coating is preferable.
Compared with the priming paint and aqueous composite coating that embodiment 1-4 is prepared, water-base resin used in priming paint is free of in comparative example 1
Chlorinated polypropylene component, prepared priming paint and composite coating adhesive force are worst, are 5 grades, and water resistance and water boiling resistance performance are also poor,
It is 4 grades.
Comparative example 2 is free of function monomer, prepared priming paint and compound painting in the acrylic acid mix monomer that the first step is added dropwise
The adhesive force of layer is 1 grade, is only second to embodiment 1-4, but the water resistance of coating is reduced to 3 grades, water boiling resistance is down to 4 grades, illustrates function
Energy monomer is obviously improved effect to coating water boiling resistance performance.
Monomer, therefore synthesized resin function monomer and hydrophilic monomer are added dropwise using a step dripping method in comparative example 3
Not Assembled distribution, by data in table 2 it is found that the adhesive force of priming paint and composite coating is slightly inferior to embodiment 1-4, composite coating
Water resistance is reduced to 2 grades, and water boiling resistance is reduced to 4 grades.It can be seen that first hydrophilic monomer and function monomer are added dropwise by the present invention
It polymerize into acrylic resin bottom material, hydrophilic monomer is assembled around hydrophilic radical together with function monomer " binding "
The a large amount of acrylate base functional group with stronger hydrophobic property and larger space steric hindrance, can be obviously improved prepared
The water boiling resistance performance of the water resistance of resin, especially final coating, to solve existing resin and coating water boiling resistance performance is bad
Technical problem.
It will be apparent to those skilled in the art that can make various other according to the above description of the technical scheme and ideas
Corresponding change and deformation, and all these changes and deformation all should belong to the protection scope of the claims in the present invention
Within.
Claims (10)
1. the chlorinated polypropylene modified water-based acrylic resin with excellent water boiling resistance performance, which is characterized in that by following quality
The raw material of percentage is made:
Cosolvent: 5~20%；
Chlorinated polypropylene: 2.5~15%；
Hydrophilic monomer: 4.5~10%；
Function monomer: 5~20%；
Initiator a:0.05~3%；
Vinyl monomer: 5~30%；
Initiator b:0.05~3%；
Neutralizer: 3~12%；
Deionized water: 25~45.45%.
2. the chlorinated polypropylene modified water-based acrylic resin according to claim 1 with excellent water boiling resistance performance,
It is characterized in that, the function monomer is isobornyl methacrylate, isobornyl acrylate, 4- tert-butylcyclohexyl methyl-prop
Olefin(e) acid ester, 4- tert-butylcyclohexyl acrylate, cyclohexyl methacrylate, in cyclohexyl acrylate any one or it is several
Kind.
3. the chlorinated polypropylene modified water-based acrylic resin according to claim 1 with excellent water boiling resistance performance,
It is characterized in that, the chlorinty of the chlorinated polypropylene is 15~55%.
4. a kind of chlorinated polypropylene modified water-based acrylic resin with excellent water boiling resistance performance as described in claim 1
Preparation method, which comprises the following steps:
1) hydrophilic monomer, function monomer and initiator a are uniformly mixed, obtain mix monomer A；By vinyl monomer and initiation
Agent b is uniformly mixed to obtain mix monomer B；
2) 70~80 DEG C are warming up to after mixing cosolvent and chlorinated polypropylene gradually to dissolve, is continuously heating to 80~90 later
DEG C, mix monomer A is added dropwise, after completion of dropwise addition, in 80~90 DEG C of 0.5~1h of heat preservation, is warming up to 100~120 DEG C later, continues to drip
Add mix monomer B, after completion of dropwise addition, 2~4h is kept the temperature at 100~120 DEG C, neutralizer is added after cooling and is neutralized, while stirring
It mixes side and deionized water is added, obtain the chlorinated polypropylene modified water-based acrylic resin with excellent water boiling resistance performance.
5. the system of the chlorinated polypropylene modified water-based acrylic resin according to claim 4 with excellent water boiling resistance performance
Preparation Method, which is characterized in that mix monomer A and mix monomer B in step 2) in 2~3h in being added dropwise.
6. the system of the chlorinated polypropylene modified water-based acrylic resin according to claim 4 with excellent water boiling resistance performance
Preparation Method, which is characterized in that 40~60 DEG C are cooled in step 2).
7. the system of the chlorinated polypropylene modified water-based acrylic resin according to claim 4 with excellent water boiling resistance performance
Preparation Method, which is characterized in that the hydrophilic monomer be acrylic acid, methacrylic acid, in maleic anhydride any one or it is several
Kind.
8. the system of the chlorinated polypropylene modified water-based acrylic resin according to claim 4 with excellent water boiling resistance performance
Preparation Method, which is characterized in that the vinyl monomer methyl acrylate, methyl methacrylate, ethyl acrylate, methyl-prop
Olefin(e) acid ethyl ester, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, acrylic acid-2-ethyl oneself
Ester, n-octyl, n octyl methacrylate, benzyl acrylate, any one or a few in styrene.
9. the system of the chlorinated polypropylene modified water-based acrylic resin according to claim 4 with excellent water boiling resistance performance
Preparation Method, which is characterized in that the initiator a is azo-initiator, and the azo-initiator is azodiisobutyronitrile, idol
Nitrogen diisoamyl nitrile, azobisisoheptonitrile any one or a few；The initiator b is peroxide type initiators, the mistake
Oxide-based initiator is dibenzoyl peroxide, peroxide di-t-butyl, two tertiary pentyl of peroxide, perbenzoic acid
Any one or a few in the tert-butyl ester.
10. a kind of coating, which is characterized in that use the chlorinated polypropylene described in claim 1 with excellent water boiling resistance performance
Modified aqueous acrylic acid resin is made.
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| CN111534215A (en) * | 2020-05-22 | 2020-08-14 | 中国科学院长春应用化学研究所 | Water-based paint for automobile bumpers and preparation method thereof |
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| CN101260178A (en) * | 2008-02-22 | 2008-09-10 | 常州南京大学高新技术研究院 | Modified chlorinated polyolefin resin and preparing method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111534215A (en) * | 2020-05-22 | 2020-08-14 | 中国科学院长春应用化学研究所 | Water-based paint for automobile bumpers and preparation method thereof |
| CN111534215B (en) * | 2020-05-22 | 2021-07-02 | 中国科学院长春应用化学研究所 | Water-based paint for automobile bumpers and preparation method thereof |
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