CN107459618B - A kind of preparation method of woodcare paint water-based acrylic resin and the product of acquisition - Google Patents
A kind of preparation method of woodcare paint water-based acrylic resin and the product of acquisition Download PDFInfo
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- CN107459618B CN107459618B CN201710737011.1A CN201710737011A CN107459618B CN 107459618 B CN107459618 B CN 107459618B CN 201710737011 A CN201710737011 A CN 201710737011A CN 107459618 B CN107459618 B CN 107459618B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
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- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
Abstract
The invention belongs to chemistry painting industry fields, and in particular to a kind of preparation method of woodcare paint water-based acrylic resin.The preparation method of woodcare paint provided by the invention water-based acrylic resin is：By the way that methyl methacrylate, hydroxy-ethyl acrylate and Isooctyl acrylate monomer are first carried out polymerisation under given conditions, it is subsequently added into diisocyanate and carries out pre- chain extending reaction under given conditions, be eventually adding dimethylethanolamine and dendritic cation-type water-thinned acrylic resin is obtained by the reaction.The dendritic cation-type water-thinned acrylic resin being prepared can effectively improve the exudative and impervious Huang of hardness, impervious oiliness, anti-pigment of paint film, but also have the advantages that water resistance and corrosion resistance are strong, it is a kind of ideal woodcare paint water-based acrylic resin.
Description
Technical field
The invention belongs to chemistry painting industry fields, and in particular to a kind of preparation method of woodcare paint water-based acrylic resin and
The product of acquisition.
Background technology
With the enhancing of social environment consciousness, tradition is using organic solvent as diluent, the wood containing each type organic such as benzene
Device paint, exists and is detrimental to health, pollute environment, destroy ecology the defects of and gradually by the aqueous woodware paint using water as diluent
Replaced.Acrylic resin is that a kind of have that good weatherability, water resistance be good, ideal woodwork coating tree of strong adhesive force
Fat, but the difference due to acrylic resin in terms of toughness, impact resistance and heat resistance, still cannot for the product of specific use
Requirement is fully met, limits its application.
Modern study finds, the copolymerization of different classes of acrylic monomers, raising acrylic resin that can be in various degree
The performances such as toughness, heat resistance and impact resistance.Therefore, the pre-emulsion application of industrially prepared watersoluble modified acrylic acid is also got at present
Come more extensive.
Patent document CN100588664C discloses a kind of water-based acrylic resin and preparation method thereof, prepares raw material packet
Acrylic monomers, styrene monomer, initiator, cosolvent, active solvent are included, the water-based acrylic resin is by two step method system
It is standby：The first step, prepares aqueous acrylic resin performed polymer, and resin emulsion is made by internal emulsification in second step.The water being prepared
Property acrylic resin have excellent film forming, excellent water resistance, scrub resistance, chemical resistance and stain resistant it is excellent
Point.
Patent document CN102757529B discloses a kind of preparation method of water-based acrylic resin, the preparation method packet
Include the preparation of blocked isocyanate and the synthesis of acrylic resin, the synthesis of the acrylic resin：By methacrylic acid two
Methylamino ethyl ester), butyl acrylate and methyl methacrylate add in azodiisobutyronitrile synthesis.The water-based acrylic resin
Preparation method preparation process it is simple, environmentally protective, excellent storage stability, curing performance is excellent.
Woodenware is generally made of hard herbaceous plant, such as China fir woodenware, broad-leaved wood and shrub timber, due in timber
Wood-fibred in containing lignin, tannic acid and grease, tannic acid and fat content higher especially at node.It is however above-mentioned
Water-based acrylic resin is anionic acrylic resin emulsion, and the grain size and surface tension of this lotion are larger, general to be difficult
It penetrates into the tiny pore inside ground, cation type emulsion surface or polymer itself are positively charged in contrast, tool
There are anion or the incomparable function of non-ionic lotion.
Liu Ren has delivered the paper of one entitled " synthesis of Eudragit RL and its water-soluble Journal of Sex Research ", institute
The Eudragit RL stated is with glycidyl methacrylate, methyl methacrylate, styrene, acrylic acid hydroxypropyl
Ester and butyl acrylate are monomer, pass through radical polymerization and other esters of acrylic acid using glycidyl methacrylate
Monomer tool, introducing group of returning to life from the nether world are made using diethanol amine open loop, the Eudragit RL being prepared with compared with
Good water solubility and stability.But woodcare paint not only requires its feature of environmental protection, tannic acid is prevented to its water paint
With the influence of grease, i.e., to the compactness for improving woodenware water paint, impervious oil, the exudation of anti-pigment and impervious yellow performance also have
Higher requirement.
Therefore, compactness is researched and developed, impervious oil, the exudation of anti-pigment and the good woodcare paint of impervious yellow performance are with aqueous third
Olefin(e) acid resin is still the problem of current urgent need to resolve.
Invention content
In order to overcome impervious oil existing for woodcare paint water-based acrylic resin in the prior art, anti-pigment exudation and impervious
The defects of Huang is poor, hardness is low, poor corrosion resistance.The purpose of the present invention is to provide a kind of woodcare paint water-based acrylic resins
Preparation method and acquisition product, to solve drawbacks described above.
The present invention provides a kind of preparation methods of woodcare paint water-based acrylic resin, include the following steps：
S1 is by 14~16 parts of methyl methacrylates, 14~16 parts of hydroxy-ethyl acrylates, 14~16 parts of Isooctyl acrylate monomers
It is uniformly mixed with 3~5 parts of initiators, obtains monomer mixture, be subsequently added into chain-transferring agent and stir evenly, obtain mixture；
The mixture that S2 obtains 1/2 step S1 adds in stirring in 14~16 parts of n-butanols and, to dissolving, then heats to
110-115 DEG C, after heating 25~35min, the mixing that remaining step S1 obtains is added dropwise with the rate of addition of 0.1~0.3g/min
Object after being added dropwise, is warming up to 120 DEG C of 1~2h of insulation reaction, obtains polymer, and n-butanol is recovered under reduced pressure；
S3 adds in 33~52 parts of diisocyanate in the polymer that step S2 is obtained, and is warming up to 65~112 DEG C, heat preservation is anti-
After answering 2~3h, 50~55 DEG C are cooled to, 30~45 parts of chain extenders is added in, adds 0.05~0.3 part of organotin catalysts, is risen
For temperature to 70~80 DEG C, 2~2.5h of insulation reaction obtains chain extension performed polymer；
When the chain extension performed polymer that step S3 is obtained is cooled to 32~35 DEG C by S4, dimethylethanolamine, the dropwise addition is added dropwise
Speed is 0.04~0.06g/min, and time for adding is 2~3h, is then warming up to 60~65 DEG C, 1.5~2h of insulation reaction must have
Machine amine is modified performed polymer；
S5 is modified addition acetic acid in performed polymer toward the organic amine that step S4 is obtained and is neutralized, and is subsequently added into 300~350 parts
Water carry out emulsion dispersion, solvent removed by vacuum to get.
Further, the initiator in the step S1 was dibenzoyl peroxide.
Further, the additive amount of the chain-transferring agent in the step S1 is the 4-6% of monomer mixture total amount.
Further, the chain-transferring agent in the step S1 presses matter by lauryl mercaptan and ɑ-methyl styrene dimer body
Measure ratio 1:(4~6) it forms.
Further, the chain-transferring agent in the step S1 presses matter by lauryl mercaptan and ɑ-methyl styrene dimer body
Measure ratio 1:5 compositions.
Further, the chain extender in the step S3 is by 1,6- hexylene glycols, pentaerythrite and methyl ethyl ketone in mass ratio (1
~3):(0.08~1.2):(9~12) it forms.
Further, the chain extender in the step S3 is by 1,6- hexylene glycols, pentaerythrite and methyl ethyl ketone in mass ratio 2:
1:10 compositions.
Further, the organotin catalysts in the step S3 are dibutyl tin laurate.
In addition, the wood that is prepared of preparation method the present invention also provides woodcare paint water-based acrylic resin
Device paint water-based acrylic resin.
At present, the water-based acrylic resin of existing cationic is that chain extension hydroxyl is introduced polymer by ring-opening reaction
Then epoxy group in organic amine substance and acrylic resin is reacted and introduces organic amino group by middle formation chain polymer
Group, is subsequently added into case type isocyanates, the catenulate Eudragit RL of shape.The chain being prepared sun from
Subtype acrylic resin is exudative poor to the impervious oiliness and pigment of timber, it is impossible to meet the requirements.Based on above-mentioned discovery, this hair
A person of good sense develops a kind of dendritic Eudragit RL suitable for woodcare paint, has to timber by a large amount of research
There are excellent permeability resistance and impervious Huang.
Dendritic cation-type water-thinned acrylic resin provided by the invention is by first by methyl methacrylate, third
Olefin(e) acid hydroxyl ethyl ester and Isooctyl acrylate monomer carry out polymerisation under given conditions, are subsequently added into diisocyanate specific
Under the conditions of carry out pre- chain extending reaction, be eventually adding dimethylethanolamine reaction be made.The dendritic cation-type water-thinned acrylic acid
The hydroxyl that chain extension is used in resin preparation process is brought directly to by raw material, ensure that the abundant progress of chain extending reaction；It prepares
Diisocyanate is first added in after into polymer to be reacted, and the largely chain extension semi-finished product containing isocyanates is formed, by a small amount of
Two functions, the polyalcohol of tetrafunctional form dendritic chain extension performed polymer, and also there are different for what is further reacted in molecule
Cyanate is reacted for the organic amine containing activity hydroxy.The dendritic cation-type water-thinned acrylic resin being prepared
Effectively to improve the exudative and impervious Huang of the hardness of paint film, impervious oiliness, anti-pigment, but also with water resistance and corrosion resistant
The advantages of corrosion is strong is a kind of ideal woodcare paint water-based acrylic resin.
Further, the present invention is used and is made of lauryl mercaptan and ɑ-methyl styrene dimer body by certain mass ratio
Chain-transferring agent be used to control the degree of polymerization and viscosity of polymer, promote reacting for diisocyanate and polymer, be to form branch
The key factor of shape chain extension performed polymer.The present invention use by 1,6-HD, pentaerythrite and methyl ethyl ketone by certain mass ratio
The chain extender of composition can be effectively promoted the formation of dendritic chain extension performed polymer, while can also effectively improve dendritic chain extension
The stability of performed polymer.
Further, the dendritic sun that the preparation method of woodcare paint provided by the invention water-based acrylic resin is prepared
Ionic water-based acrylic resin has the advantages of hardness is high, and impervious oil, the exudation of anti-pigment and impervious Huang are good, and water resistance is strong.
It is found through experiment that the paint film adhesion of the water-based acrylic resin containing woodcare paint that the present invention is prepared is strong, hardness is high, and
Volatile organic compounds (VOC) content of the paint film is less than 103g/L, tinctorial yield 100%, and flexibility (diameter) is less than
0.86mm, antiseepage Huang performance △ b value are less than 0.35, have preferable absorption of perspiration, resistance to saliva property, alcohol resistance and humidity resistance,
The service life of furniture can effectively be extended.
Further, the diisocyanate that the present invention uses is easily controllable for non-close type isocyanates, solves closing
Type isocyanates is prone to the dimerization or trimerization reaction of diisocyanate, forms the side reactions such as allophanic acid or biuret structure
The defects of influencing acrylic resin modified reaction and quality.
Compared with prior art, the preparation method of woodcare paint water-based acrylic resin provided by the invention has following excellent
Gesture：
(1) the water soluble acrylic acid tree that the preparation method of woodcare paint provided by the invention water-based acrylic resin is prepared
Fat has the advantages that adhesive force is high, coloring is strong, flexibility is good, water resistance and corrosion resistance are strong；
(2) the water soluble acrylic acid tree that the preparation method of woodcare paint provided by the invention water-based acrylic resin is prepared
Fat has the advantages that impervious oil, the exudation of anti-pigment and impervious Huang are good, is a kind of environmental protection, healthy woodcare paint water soluble acrylic acid
Resin；
(3) the water soluble acrylic acid tree that the preparation method of woodcare paint provided by the invention water-based acrylic resin is prepared
There is the transparent light in surface, richness is high, glossy, and the effect do not faded, do not fallen off is used for a long time, is one on fat application woodenware
Kind meets the woodcare paint resin of modern's requirement.
Specific embodiment：
The following describes the present invention further through the description of specific embodiments, but this is not the limit to the present invention
System, those skilled in the art's basic thought according to the present invention can make various modifications or improvements, but without departing from this
The basic thought of invention, is all within the scope of the present invention.Present component is that commercially available routine is divided into, such as：ɑ-methylbenzene second
Alkene dimer is purchased from Wuxi City Heng Hui Chemical Co., Ltd.s, and customs HS is encoded to 29420000.
Embodiment 1, a kind of preparation of woodcare paint water-based acrylic resin
S1 is by 14 parts of methyl methacrylates, 14 parts of hydroxy-ethyl acrylates, 14 parts of Isooctyl acrylate monomers and 3 parts of peroxidating two
Benzoyl is uniformly mixed, and obtains monomer mixture, is subsequently added into chain-transferring agent and is stirred evenly, and the additive amount of the chain-transferring agent is single
The 4% of body amount of the mixture, the chain-transferring agent is by lauryl mercaptan and ɑ-methyl styrene dimer body in mass ratio 1:4 groups
Into obtaining mixture；
The mixture that S2 obtains 1/2 step S1 adds in stirring in 14 parts of n-butanols and, to dissolving, then heats to 110
DEG C, after heating 25min, with the mixture that the rate of addition dropwise addition remaining step S1 of 0.1g/min is obtained, after being added dropwise, heating
To 120 DEG C of insulation reaction 1h, polymer is obtained, and n-butanol is recovered under reduced pressure；
S3 adds in 35 parts of diisocyanate in the polymer that step S2 are obtained, and is warming up to 72 DEG C, after insulation reaction 2h, drop
Temperature adds in 30 parts of chain extenders, the chain extender is by 1,6- hexylene glycols, pentaerythrite and methyl ethyl ketone in mass ratio 3 to 50 DEG C:1.2:
9 compositions, add 0.01 part of dibutyl tin laurate, are warming up to 70 DEG C, insulation reaction 2h obtains chain extension performed polymer；
When the chain extension performed polymer that step S3 is obtained is cooled to 32 DEG C by S4, dimethylethanolamine, the rate of addition is added dropwise
For 0.04g/min, time for adding 2h, 60 DEG C, insulation reaction 1.5h are then warming up to, organic amine is obtained and is modified performed polymer；
S5, which is modified toward organic amine that step S4 is obtained in performed polymer, to be added in acetic acid and is neutralized, be subsequently added into 300 parts of water into
Row emulsion dispersion, solvent removed by vacuum to get.
Embodiment 2, a kind of preparation of woodcare paint water-based acrylic resin
S1 is by 15 parts of methyl methacrylates, 15 parts of hydroxy-ethyl acrylates, 15 parts of Isooctyl acrylate monomers and 4 parts of peroxidating two
Benzoyl is uniformly mixed, and obtains monomer mixture, is subsequently added into chain-transferring agent and is stirred evenly, and the additive amount of the chain-transferring agent is single
The 5% of body amount of the mixture, the chain-transferring agent is by lauryl mercaptan and ɑ-methyl styrene dimer body in mass ratio 1:5 groups
Into obtaining mixture；
The mixture that S2 obtains 1/2 step S1 adds in stirring in 15 parts of n-butanols and, to dissolving, then heats to 113
DEG C, 30min is heated, with the mixture that the rate of addition dropwise addition remaining step S1 of 0.2g/min is obtained, after being added dropwise, is warming up to
120 DEG C of insulation reaction 1.5h, obtain polymer, and n-butanol is recovered under reduced pressure；
S3 adds in 40 parts of diisocyanate in the polymer that step S2 are obtained, and is warming up to 85 DEG C, after insulation reaction 2.5h,
52 DEG C are cooled to, adds in 35 parts of chain extenders, the chain extender is by 1,6- hexylene glycols, pentaerythrite and methyl ethyl ketone in mass ratio 2:1:
10 compositions, add 0.02 part of dibutyl tin laurate, are warming up to 75 DEG C, insulation reaction 2.2h obtains chain extension performed polymer；
When the chain extension performed polymer that step S3 is obtained is cooled to 34 DEG C by S4, dimethylethanolamine, the rate of addition is added dropwise
For 0.05g/min, time for adding is 2~3h, is then warming up to 62 DEG C, insulation reaction 1.8h, obtains organic amine and is modified performed polymer；
S5, which is modified toward organic amine that step S4 is obtained in performed polymer, to be added in acetic acid and is neutralized, be subsequently added into 320 parts of water into
Row emulsion dispersion, solvent removed by vacuum to get.
Embodiment 3, a kind of preparation method of woodcare paint water-based acrylic resin
S1 is by 16 parts of methyl methacrylates, 16 parts of hydroxy-ethyl acrylates, 16 parts of Isooctyl acrylate monomers and 5 parts of peroxidating two
Benzoyl is uniformly mixed, and obtains monomer mixture, is subsequently added into chain-transferring agent and is stirred evenly, and the additive amount of the chain-transferring agent is single
The 6% of body amount of the mixture, the chain-transferring agent is by lauryl mercaptan and ɑ-methyl styrene dimer body in mass ratio 1:6 groups
Into obtaining mixture；
The mixture that S2 obtains 1/2 step S1 adds in stirring in 16 parts of n-butanols and, to dissolving, then heats to 115
DEG C, 35min is heated, with the mixture that the rate of addition dropwise addition remaining step S1 of 0.3g/min is obtained, after being added dropwise, is warming up to
120 DEG C of insulation reaction 2h, obtain polymer, and n-butanol is recovered under reduced pressure；
S3 adds in 50 parts of diisocyanate in the polymer that step S2 are obtained, and is warming up to 100 DEG C, after insulation reaction 3h,
55 DEG C are cooled to, adds in 45 parts of chain extenders, the chain extender is by 1,6- hexylene glycols, pentaerythrite and methyl ethyl ketone in mass ratio 1:
0.08:12 compositions, add 0.05~0.3 part of dibutyl tin laurate, are warming up to 80 DEG C, insulation reaction 2.5h obtains chain extension
Performed polymer；
When the chain extension performed polymer that step S3 is obtained is cooled to 35 DEG C by S4, dimethylethanolamine, the rate of addition is added dropwise
For 0.06g/min, time for adding 3h, 65 DEG C, insulation reaction 2h are then warming up to, organic amine is obtained and is modified performed polymer；
S5, which is modified toward organic amine that step S4 is obtained in performed polymer, to be added in acetic acid and is neutralized, be subsequently added into 350 parts of water into
Row emulsion dispersion, solvent removed by vacuum to get.
Comparative example 1, a kind of preparation of woodcare paint water-based acrylic resin
S1 is by 15 parts of methyl methacrylates, 15 parts of hydroxy-ethyl acrylates, 15 parts of Isooctyl acrylate monomers and 4 parts of peroxidating two
Benzoyl is uniformly mixed, and obtains monomer mixture, is subsequently added into chain-transferring agent and is stirred evenly, and the additive amount of the chain-transferring agent is single
The 5% of body amount of the mixture, the chain-transferring agent is by lauryl mercaptan and ɑ-methyl styrene dimer body in mass ratio 1:5 groups
Into obtaining mixture；
The mixture that S2 obtains 1/2 step S1 adds in stirring in 15 parts of n-butanols and, to dissolving, then heats to 113
DEG C, 30min is heated, with the mixture that the rate of addition dropwise addition remaining step S1 of 0.2g/min is obtained, after being added dropwise, is warming up to
120 DEG C of insulation reaction 1.5h, obtain polymer, and n-butanol is recovered under reduced pressure；
When the obtained polymer of step S2 is cooled to 34 DEG C by S3, dimethylethanolamine is added dropwise, the rate of addition is
0.05g/min, time for adding are 2~3h, are then warming up to 62 DEG C, insulation reaction 1.8h, obtain organic amine modified poly body；
S4 adds in 40 parts of diisocyanate in the organic amine modified poly body that step S3 is obtained, and is warming up to 85 DEG C, heat preservation
After reacting 2.5h, 52 DEG C are cooled to, adds in 35 parts of chain extenders, the chain extender is by 1,6- hexylene glycols, pentaerythrite and methyl ethyl ketone
In mass ratio 2:1:10 compositions, add 0.02 part of dibutyl tin laurate, are warming up to 75 DEG C, insulation reaction 2.2h must have
Machine amine chain-extension polymerization body；
S5 adds in acetic acid into the organic amine chain-extension polymerization body that step S4 is obtained and is neutralized, be subsequently added into 320 parts of water into
Row emulsion dispersion, solvent removed by vacuum to get.
With embodiment 2 difference lies in：It first carries out organic amine reaction and carries out chain extending reaction again.
Comparative example 2, a kind of preparation of woodcare paint water-based acrylic resin
The preparation method of the woodcare paint water-based acrylic resin difference lies in：40 parts of envelopes are added in the step S3
Closed form isocyanates, remaining step such as embodiment 2.
Comparative example 3, a kind of preparation of woodcare paint water-based acrylic resin
The preparation method of the woodcare paint water-based acrylic resin difference lies in：Chain tra nsfer described in the step S1
Agent be ɑ-methyl styrene dimer body, remaining step such as embodiment 2.
Comparative example 4, a kind of preparation of woodcare paint water-based acrylic resin
The preparation method of the woodcare paint water-based acrylic resin difference lies in：Chain-transferring agent in the step S1
By lauryl mercaptan and ɑ-methyl styrene dimer body in mass ratio 1:7 compositions, remaining step such as embodiment 2.
Comparative example 5, a kind of preparation of woodcare paint water-based acrylic resin
The preparation method of the woodcare paint water-based acrylic resin difference lies in：Chain extender in the step S4 by
1,6-HD, pentaerythrite and methyl ethyl ketone in mass ratio 1:1:1 composition, remaining step such as embodiment 2.
Test example one, the experiment of the performance detection of the water-based acrylic resin paint film containing woodcare paint
1st, test material：Embodiment 1, embodiment 2, embodiment 3, comparative example 1, comparative example 2, comparative example 3,4 and of comparative example
The woodcare paint water-based acrylic resin that comparative example 5 is prepared.
2nd, test method：
Embodiment 1, embodiment 2, embodiment 3, comparative example 1, comparative example 2, comparative example 3, comparative example 4 and comparative example 5 are made
Standby obtained water-based acrylic resin adds in the ingredients such as crosslinking agent, antifoaming agent, dispersant, thickener, levelling agent and woodcare paint is made,
And paint film is prepared into according to spray coating method, to the volatile organic compounds (VOC) of paint film, adhesive force, tinctorial yield, flexibility, hard
Degree and antiseepage Huang value are measured,
Wherein：Volatile organic compounds (VOC) is measured with reference to the method for GB/T23986-2009；Adhesive force uses
Cross-hatching is detected；Tinting strength, tinting power is detected with reference to the method for GB/T14624.2-2008, and test condition temperature is 25 ± 1
DEG C, relative humidity is 65 ± 5%, and the calculation formula of tinting strength, tinting power percentage is S=B/A × 100%, wherein：S is tinting strength, tinting power percentage
Than A waters down chalk dosage for standard specimen, and B waters down chalk dosage for sample；Flexibility is examined with reference to the method for GB/T1731-93
It surveys；Hardness is detected with reference to the method for GB/T6739-2006；Antiseepage Huang test condition temperature is 25 ± 1 DEG C, relative humidity
It is 80 ± 5%, △ b values (antiseepage Huang value) is measured after 72 hours dry.
3rd, result of the test：
Result of the test is as shown in table 1.
The performance detection experiment of the water-based acrylic resin paint film containing woodcare paint of table 1
From the performance detection test data containing woodcare paint water-based acrylic resin paint film of table 1：
(1) paint film adhesion for the water-based acrylic resin containing woodcare paint being prepared using the embodiment of the present invention 1~3
By force, hardness is high, and volatile organic compounds (VOC) content of the paint film is less than 103g/L, and tinctorial yield 100% is flexible
Property (diameter) less than 0.86mm, antiseepage Huang performance △ b values are less than 0.35, the wherein volatility for the paint film that embodiment 2 is prepared
Organic compound (VOC) content be 90g/L, tinctorial yield 100%, flexibility (diameter) be 0.78mm, antiseepage Huang performance △ b values
It is 0.18, is most preferred embodiment.
(2) 1 group of comparative example first carries out organic amine reaction and carries out the formation that chain extending reaction affects dendritic acrylic resin again,
So as to reduce the volatile organic compounds of paint film (VOC) content, tinctorial yield, flexibility and antiseepage Huang performance.
(3) 2 groups of chain acrylic resins being prepared using blocked isocyanate of comparative example, greatly reduce paint
Volatile organic compounds (VOC) content of film, tinctorial yield, flexibility and antiseepage Huang performance, substantially without impervious oil, anti-color
Element exudation and the ability of impervious Huang.
(4) variety classes of 3~5 groups of comparative example or the chain-transferring agent and chain extender of different proportion are to acrylic resin modified
Synthesis have large effect.
The corrosion-resistant testing experiment of test example two, the water-based acrylic resin paint film containing woodcare paint
1st, test material：Embodiment 1, embodiment 2, embodiment 3, comparative example 1, comparative example 2, comparative example 3,4 and of comparative example
The woodcare paint water-based acrylic resin that comparative example 5 is prepared.
2nd, test method：
Embodiment 1, embodiment 2, embodiment 3, comparative example 1, comparative example 2, comparative example 3, comparative example 4 and comparative example 5 are made
Standby obtained water-based acrylic resin adds in the ingredients such as crosslinking agent, antifoaming agent, dispersant, thickener, levelling agent and woodcare paint is made,
And paint film is prepared into according to spray coating method, carrying out absorption of perspiration, resistance to saliva property, alcohol resistance and humidity resistance to paint film is measured,
Wherein sweat proof and resistance to saliva property are measured with reference to the method for German Standard 64LFGB.B 82.10-1, and alcohol resistance refers to GB/
The method of T13217.7-2009 is measured, and is wiped using 50% alcohol, and humidity resistance refers to GB/T1740-2007
Method be measured.
3rd, result of the test：
Result of the test is as shown in table 2.
The corrosion-resistant testing experiment of the water-based acrylic resin paint film containing woodcare paint of table 2
As shown in Table 2, using paint film made from the woodcare paint water-based acrylic resin of the preparation of the embodiment of the present invention 1~3
With preferable absorption of perspiration, resistance to saliva property, alcohol resistance and humidity resistance, it can effectively extend the service life of woodenware, and
Absorption of perspiration, resistance to saliva property, the ethanol-tolerant of paint film made from the woodcare paint water-based acrylic resin prepared using comparative example 1~5
Property and humidity resistance are poor, illustrate the water that the preparation method of woodcare paint provided by the invention water-based acrylic resin is prepared
Property acrylic resin better performances, suitable for woodcare paint application.
The stability test of test example three, woodcare paint water-based acrylic resin
1st, high-temperature stability
The woodcare paint that access 10g embodiments 1, embodiment 2, embodiment 3 are prepared is placed in modeling with water-based acrylic resin
Expect in air-tight bottle, constant temperature is placed 1 month in the baking oven of 50 DEG C of temperature, no layering, gel, demulsification, discoloration and curing phenomenon.
2nd, freeze-thaw stability
The woodcare paint that embodiment 1, embodiment 2, embodiment 3 are prepared water-based acrylic resin is packed into air-tight bottle
In, 18h is freezed under conditions of -16 DEG C, 6h, no layering, gel, demulsification, discoloration and curing phenomenon are placed in taking-up at room temperature.
3rd, dilution stability
The woodcare paint water-based acrylic resin that 10g embodiments 1, embodiment 2, embodiment 3 is taken to be prepared, addition go from
Phenomena such as sub- water dilution, no precipitation, demulsification, flocculation, generates.
4th, Calcium ion stability
It is dense that quality is added in the woodcare paint water-based acrylic resin being prepared in embodiment 1, embodiment 2, embodiment 3
The ionic calcium soln for 0.5% is spent, is placed for 24 hours, no phenomena such as demulsification, layering occurs generates.
5th, paint film stability
By embodiment 1, embodiment 2, embodiment 3 prepare water-based acrylic resin add in crosslinking agent, antifoaming agent, dispersant,
Woodcare paint is made in the ingredients such as thickener, levelling agent, and room temperature 36 months is prepared into paint film according to spray coating method, and volatility has
Machine compound (VOC) content, tinctorial yield, flexibility, antiseepage Huang performance and corrosion resistance and test example one and test example diyl
This is consistent.
Claims (7)
1. a kind of preparation method of woodcare paint water-based acrylic resin, which is characterized in that include the following steps：
S1 is by 14 ~ 16 parts of methyl methacrylates, 14 ~ 16 parts of hydroxy-ethyl acrylates, 14 ~ 16 parts of Isooctyl acrylate monomers and 3 ~ 5 parts
Initiator is uniformly mixed, and obtains monomer mixture, is subsequently added into chain-transferring agent and is stirred evenly, obtains mixture；
The mixture that S2 obtains 1/2 step S1 adds in stirring in 14 ~ 16 parts of n-butanols and, to dissolving, then heats to 110-
It 115 DEG C, after heating 25 ~ 35min, with the mixture that the rate of addition dropwise addition remaining step S1 of 0.1 ~ 0.3g/min is obtained, is added dropwise
After, 120 DEG C of 1 ~ 2h of insulation reaction are warming up to, obtain polymer, and n-butanol is recovered under reduced pressure；
S3 adds in 33 ~ 52 parts of diisocyanate in the polymer that step S2 is obtained, and is warming up to 65 ~ 112 DEG C, 2 ~ 3h of insulation reaction
Afterwards, 50 ~ 55 DEG C are cooled to, 30 ~ 45 parts of chain extenders is added in, adds 0.05 ~ 0.3 part of organotin catalysts, be warming up to 70 ~ 80
DEG C, 2 ~ 2.5h of insulation reaction obtains chain extension performed polymer；
When the chain extension performed polymer that step S3 is obtained is cooled to 32 ~ 35 DEG C by S4, dimethylethanolamine is added dropwise, the rate of addition is
0.04 ~ 0.06g/min, time for adding are 2 ~ 3h, are then warming up to 60 ~ 65 DEG C, 1.5 ~ 2h of insulation reaction, obtain organic amine and are modified in advance
Aggressiveness；
S5, which is modified toward organic amine that step S4 is obtained in performed polymer, to be added in acetic acid and is neutralized, be subsequently added into 300 ~ 350 parts of water into
Row emulsion dispersion, solvent removed by vacuum to get；
Chain-transferring agent in the step S1 is by lauryl mercaptan and ɑ-methyl styrene dimer body in mass ratio 1:(4 ~ 6) group
Into；
Chain extender in the step S3 is by 1,6-HD, pentaerythrite and methyl ethyl ketone (1 ~ 3) in mass ratio:(0.08~
1.2):(9 ~ 12) it forms.
2. the preparation method of woodcare paint water-based acrylic resin as described in claim 1, which is characterized in that the step S1
In initiator be dibenzoyl peroxide.
3. the preparation method of woodcare paint water-based acrylic resin as described in claim 1, which is characterized in that the step S1
In the additive amount of chain-transferring agent be the 4 ~ 6% of monomer mixture weight.
4. the preparation method of woodcare paint water-based acrylic resin as described in claim 1, which is characterized in that the step S1
In chain-transferring agent by lauryl mercaptan and ɑ-methyl styrene dimer body in mass ratio 1:5 compositions.
5. the preparation method of woodcare paint water-based acrylic resin as described in claim 1, which is characterized in that the step S3
In chain extender by 1,6-HD, pentaerythrite and methyl ethyl ketone in mass ratio 2:1:10 compositions.
6. the preparation method of woodcare paint water-based acrylic resin as described in claim 1, which is characterized in that the step S3
In organotin catalysts be dibutyl tin laurate.
7. the woodcare paint that the preparation method of the woodcare paint water-based acrylic resin as described in claim 1-6 is any is prepared
Use water-based acrylic resin.
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