CN106397656B - A kind of preparation and application of water-based hydrophobic modified polymethyl hydrochlorate dispersant - Google Patents
A kind of preparation and application of water-based hydrophobic modified polymethyl hydrochlorate dispersant Download PDFInfo
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- CN106397656B CN106397656B CN201610914804.1A CN201610914804A CN106397656B CN 106397656 B CN106397656 B CN 106397656B CN 201610914804 A CN201610914804 A CN 201610914804A CN 106397656 B CN106397656 B CN 106397656B
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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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
Abstract
The present invention provides a kind of preparation and application of solvent-free water-based hydrophobic modified polymethyl hydrochlorate dispersant, using with the reactive hydrophobic compound of carboxyl as polymeric carrier, polymer hydrophobic group of the polymerization after reaction was completed is formed, generating has solvent-free hydrophobically modified dispersant.The hydrophobically modified dispersant has preferable peptizaiton, excellent color developing and water resistance to inorganic and organic pigment and powder, is particularly suitable for that excellent water resistance and resistance to washmarking effect can be obtained in coating and ink system.
Description
Technical field
The present invention relates to a kind of preparation of solvent-free water-based hydrophobic modified high-molecular dispersant and applications more particularly to one
The water-based hydrophobic of pigment and filler for coating and ink system of the kind with high dispersive efficiency and water resistance is modified poly- (first
Base) acrylate polymer dispersant.
Background technology
In the application of water paint and water-based ink, aqueous pigment dispersions, also referred to as aqueous color paste have in beauty
With very important effect is embodied in required performance.And acting on for aqueous dispersant is prepared in aqueous color paste, especially
The crucial effect of comparison is all played in the application of water paint and water-based ink.
Dispersant is also referred to as wetting dispersing agent, the wetting and dispersing effect of pigment and filler is widely used in, to break face
The cohesion of material and filler itself, disperses to be formed the uniform fine grained with application effect, and can keep by coarse granule
Enough stability.Its usual active group one end having can be adsorbed on the surface of pigments of the fine particle of crushing, another
Holding has solvation to form the adsorption layer for playing stabilization, makes to generate repulsion (charge repulsion between pigment particles
Or steric hindrance repulsion), it avoids flocculating again, to ensure that the colour paste system generated has relatively good storage stability, and it is good
Good peptizaiton can make scattered pigment particles have relatively high gloss and excellent exhibition in the application in later stage
Color acts on, the application being especially embodied in coating and ink system.
The pigment of water-based system disperses, and is generally divided into wetting, dispersion, stablizes three phases.Wetting refers to playing wetting to make
Resin replaces the air of surface of pigments, formed by empty gas/solid interface transformation at liquid/solid interface when dispersion resin and face
The surface of material forms certain combination；Dispersion refers to that secondary agglomeration particle agglomerated together is smashed shape using the strength of machinery
At the small particles close to primary particle, the suspended particles of pigment in water are formed；Stabilization refers to the aqueous suspended particles to be formed
What can be stablized under conditions of no external force is suspended in water-based system, is not in flocculate again.For being used for coating and oil
The stability of the dispersion of the aqueous color paste of ink, the size of the particle of dispersion and the pigment of formation is most important.
Low molecular weight sodium polyacrylate has been widely used in the wetting and dispersing system of inorganic pigment and powder, is had
Relatively high peptizaiton and stability, it mainly keeps the stability of dispersion by the repulsion of charge.But by
Stronger in the Sodium Polyacrylate water solubility of low molecular weight, the mill base of prepared aqueous dispersion is applied in coating and ink
When, since the film-forming resin in Sodium Polyacrylate and coating and ink does not have interaction force, often cause coating and ink
Water resistance it is poor, meet water and will appear Sodium Polyacrylate and cause the damage of paint film from paint film exudation, or paint film is caused to occur
The defects of gloss decline, floating.And for most organic pigment, the surface polarity of organic pigment is smaller so that polypropylene
Wetting action of the sour sodium on organic pigment surface is bad, and organic pigment surface can not be formed with Sodium Polyacrylate it is relatively steady
Fixed surface " anchoring " effect, causes dispersion effect poor.So in the dispersion process of organic pigment, if it is desired that with being modified
Dispersant, hydrophobically modified usually is carried out to dispersant, changes the polarity of dispersant, or introduces parent in the molecule of dispersant
The group of organic pigment improves the peptizaiton to organic pigment.
For modified dispersant, hydrophobic polymerized monomer is often required to use, but these hydrophobic polymerizations are single
Body is insoluble in water or is slightly soluble in water, and no image of Buddha polyacrylic acid directly carries out polymerization preparation in water like that.It generally requires
Hydrophobic monomer is dissolved using a large amount of solvent and reduces the viscosity in reaction process, can introduce more solvent in this way,
Cause the pollution to environment.Patent US6683121 disclose prepare a kind of styrene, the dilute modification of Alpha-Methyl benzene second polyacrylic acid
Then copolymer is arranged in pairs or groups dispersant as pigment with the block copolymer containing polyoxyethylene polyoxypropylene ether；In aqueous oil
In the application of ink, prepared dispersant has relatively high gloss and relatively good color developing.It is prepared in the invention to change
Property the molecular weight of acrylic copolymer be 4000-16000, have higher than 70 DEG C of Tg.Although the hydrophobically modified of gained
Sodium Polyacrylate can all obtain good dispersion effect to organic pigment and inorganic pigment, but prepare modified polyacrylate sodium
It needs to carry out in special reactor at high temperature under high pressure during or, causes the difficulty of production and high cost in this way；
It needing to be reacted at high temperature using solvent, the solvent introduced in this way can form VOC (" organic volatilizable compound "),
Cause the harm to environment and construction personnel；And the temperature of polymerization process reaches 180 DEG C, the boiling of the monomer used higher than polymerization
Point can cause the safety of production bigger influence.Therefore, exploitation one kind not containing solvent and can be to organic and nothing
Machine pigment all dispersants with relatively good peptizaiton are to have important meaning to the development of this field.
Invention content
In view of the drawbacks described above of the prior art, technical problem to be solved by the invention is to provide a kind of solvent-free bodies
System does not contribute VOC, and with the water-based hydrophobic modifiers dispersants to the preferable peptizaiton of inorganic and organic pigment.
To achieve the above object, on the one hand, the present invention provides a kind of solvent-free water-based hydrophobic modifiers dispersants, by making
Use the compound (hydrophobic compound) containing the group that can be reacted with carboxyl as the carrier of polymerisation, the carrier was both
The influence that system viscosity is excessively high in polymerization process can be overcome, and can be with polymer chain after the completion of polymerization process and polymerization
On carboxylic group reacted, to form a part for solventless polymer.The height for the hydrophobically modified that the present invention is generated
Dispersal agent molecule greatly improves the water resistance of pigment dispersion, and with the comparison of the low polar pigment with organic pigment etc.
Good interaction, improves dispersion and stabilization.The solvent-free water-based hydrophobic modifiers dispersants are used for water paint and water
Property ink system can preferably improve its stability and water resistance, especially coating application in, can greatly improve paint
The washmarking defect of film.
Specifically, solvent-free water-based hydrophobic modified high-molecular dispersant of the present invention is the poly- of hydrophobic grouping modification
(methyl) acrylate polymer dispersant, wherein the hydrophobic grouping includes component (A) and component (B) two parts, component
(A) it is the hydrophobic monomer of the aromatic group containing double bond, be copolymerized to polymerizeing with (methyl) acrylic acid as comonomer
Owner's chain；Component (B) be the compound containing the group that can be reacted with the carboxyl on (methyl) acrylic acid, polymerization after with
(methyl) acrylic acid carries out reactive grafting to the main chain of polymer.
Preferably, the hydrophobic monomer component (A) of the aromatic group containing double bond is selected from styrene, 4- methylbenzene second
It is one or more in alkene, 2- vinyl naphthalenes, α-methylstyrene.It is described containing can with the carboxyl on (methyl) acrylic acid into
The compound component (B) of the group of row reaction is the compound containing single terminal epoxy groups, and it is sweet to be preferably selected from propyl shrink
Oily ether, butyl glycidyl ether, tertiary butyl glycidyl ether, hexyl glycidyl ether, octyl glycidyl ether, lauryl alcohol shrink
Glycerin ether, polyoxyethylene monoglycidyl ether (polyoxyethylene ether segment contains 3-50 repetitive unit), polyoxypropylene list shrink
One kind in glycerin ether (polyoxyethylene ether segment contains 3-20 repetitive unit), polyoxyethylene polyoxypropylene monoglycidyl ether
Or it is several.
In the specific implementation mode of the present invention, based on polymeric dispersant weight, hydrophobic monomer component (A) is in poly- (first
Base) content in acrylate polymer is 10-50wt%, preferably 10-40wt%, more preferable 20-40wt%.In the present invention
In, dosage of the hydrophobic monomer component (A) less than 10wt% can lead to scattered dispersible pigment color paste bad stability, be susceptible to and return
Thick phenomenon；Dosage higher than 60wt% can cause dispersion efficiency to be lower.Component (B) is in poly- (methyl) acrylate polymer
Content is 8-30wt%, preferably 8-25wt%, more preferable 8-20wt%.(methyl) acrylic acid polymerize in poly- (methyl) acrylates
Content in object is 20-82wt%, preferably 20-60wt%, more preferably 30-60wt%.
In the better embodiment of the present invention, by weight, the solvent-free water-based hydrophobic modifiers dispersants include 10-
The hydrophobic monomer component (A) of the aromatic group containing double bond of 50wt%, 8-30wt% contain can be with carboxylic on (methyl) acrylic acid
The compound component (B) for the group that base is reacted, 20-82wt% (methyl) acrylic acid.
On the other hand, the present invention also provides a kind of poly- (methyl) acrylate polymers point preparing hydrophobic grouping modification
The method of powder, specifically includes：
1) a certain proportion of component (A), (methyl) acrylic acid and chain-transferring agent are uniformly mixed；
2) a certain amount of component (B) is added into reactor, is then heated to 80-110 DEG C；
3) start the mixed liquor that uniformly mixed component (A)/(methyl) acrylic acid is added dropwise into above compound, add simultaneously
Enter a certain amount of radical initiator, it is 2-6 hours that the time, which is added,；
4) after completion of dropwise addition, 2 hours is kept the temperature, is then slowly added into the aqueous solution of neutralization reagent, temperature is maintained at when addition
It 80 DEG C or more, adjusts and arrives suitable pH and solid content；
5) it and then is warming up to 90-95 DEG C, the N of 0.1-1% is added, N- dimethylethanolamines, the reaction was continued to infrared detection
Component (B) is reacted completely, is cooled to room temperature, suitable deionized water is added and is diluted, required hydrophobically modified is obtained by filtration
Poly- (methyl) acrylates dispersant.
Preferably, initiator used in preparation method of the invention is oil-soluble radical initiator, by dispersant
The dosage of total weight, radical initiator is 0.5-8wt%.It is highly preferred that radical initiator is selected from t-butyl peroxy
Change hydrogen, benzoyl peroxide, dilauroyl peroxide, azodiisobutyronitrile, the peroxidating isooctyl acid tert-butyl ester, perbenzoic acid
One or more of tert-butyl ester.
In another better embodiment of the present invention, poly- (methyl) acrylate polymer of hydrophobic grouping modification is prepared
Chain-transferring agent is also used during dispersant, and the molecule for generating product is controlled by chain-transferring agent and radical initiator
Amount；The molecular weight for poly- (methyl) acrylate polymer that the hydrophobic grouping of the present invention is modified is 1500-6000；It is preferred that 1500-
5000；More preferable 1500-4500.In the present invention, poly- (methyl) acrylates that those skilled in the art can be according to demand is poly-
The molecular weight of object dispersant is closed to determine the dosage of chain-transferring agent.Preferably, used chain-transferring agent be selected from mercaptopropionic acid,
One or several kinds in mercapto-propionate, mercaptopropionic acid butyl ester, lauryl mercaptan.
In poly- (methyl) the acrylate polymer method for preparing hydrophobic grouping modification of the present invention, neutralization is used to try
Agent is preferably selected from ammonium hydroxide, ethanol amine, diethanol amine, triethanolamine, AMP-95, triethylamine, N, N- dimethylethanolamines, two different
It is one or several kinds of in Propanolamine, sodium hydroxide, potassium hydroxide.Preferably, using neutralization reagent ammonium hydroxide, ethanol amine, three ethyl alcohol
Amine, N, N- dimethylethanolamines adjust pH value to 6.0-8.0.
On the other hand, the present invention also provides a kind of poly- (methyl) acrylate polymers being modified the hydrophobic grouping
Application of the dispersant in coating, the especially application in the coating such as aqueous building coating, industrial coating and water-based ink.
Technique effect
The macromolecule dispersing agent of the hydrophobically modified of the present invention has to the preferable peptizaiton of inorganic and organic pigment, greatly
The water resistance of pigment dispersion, and the relatively good interaction with polar pigment low with organic pigment etc. are improved, is carried
High dispersive and stabilization.It, which is used for water paint and water-based ink system, can improve relatively good stability and water resistance,
Especially in coating application, it can greatly improve the washmarking defect of paint film.Specifically, hydrophobically modified dispersant of the invention
Can have to a variety of inorganic pigments and filler such as titanium dioxide, iron oxide red, iron oxide yellow, ultramarine, lithopone, calcium carbonate relatively good dispersion and
Storage stability；Have simultaneously to for example organic red, phthalocyanine blue of the carbon black and organic pigment of more difficult dispersion, organic yellow etc. relatively good
Dispersion and stabilization, and there is relatively good color developing and high glaze；Aqueous building coating, industry can be widely used in
The fields such as coating and water-based ink.The hydrophobically modified dispersant of the present invention can shorten the milling time of pigment, stabilising dispersions
System prevents from flocculating and precipitate, and reduces loose colour and floating tendency in pigments system.If having been used in preparation process and having contained polyoxy
The epoxide of vinethene or polyethenoxy ether can greatly improve the stability of heat storage.
The technique effect of the design of the present invention, concrete structure and generation is made furtherly below with reference to specific embodiment
It is bright, it is fully understood from the purpose of the present invention, feature and effect to help those skilled in the art.But the present invention is not limited to these
Example.
Specific implementation mode
The raw material used in each embodiment in the present invention is all commercial goods, specific as follows：
Embodiment 1：
Under nitrogen protection, in 2 liters of reaction bulb be added 120 grams of butyl glycidyl ethers, be heated to 85 DEG C, then start to
The mixed liquor being made of 180 grams of styrene, 300 grams of acrylic acid and 12 grams of MPA is added dropwise in reaction bulb, while 28 are added dropwise to reaction bulb
Gram TBPEH.Time for adding is 2.5 hours, and maintaining reaction temperature is at 85-90 DEG C.After completion of dropwise addition, heat preservation is small in 85-90 degree 2
When.Then 80 degree are cooled to, slowly into reaction bulb be added dropwise 220 gram 25% ammonia solvent 650 grams of deionized waters solution,
It is 30 minutes that the time, which is added,.During dropwise addition, reaction solution is become cloudy by clarifying, and then becomes clarification again.Then 95 degree are warming up to, to
1.5 grams of N are added in reaction bulb, N- dimethylethanolamines stir 4 hours, then gas-chromatography (GC) used to detect at this temperature
The content of butyl glycidyl ether, later every detection in 1 hour once until butyl glycidyl ether reacts completely.It is cooled to room
Temperature, is added 100 grams of deionized water dilutions, and colourless to lurid transparency liquid is arrived in filtering.Solid content is 38%, and pH value is
7.2.
Embodiment 2：
Under nitrogen protection, in 2 liters of reaction bulb be added 180 grams of butyl glycidyl ethers, be heated to 85 DEG C, then start to
The mixed liquor being made of 60 grams of styrene, 360 grams of methacrylic acids and 15 grams of MMP is added dropwise in reaction bulb, while being dripped to reaction bulb
Add 28 grams of TBPEH.Time for adding is 2.5 hours, and maintaining reaction temperature is at 85-90 DEG C.After completion of dropwise addition, keep the temperature in 85-90 degree 2
Hour.Then 80 degree are cooled to, 250 gram 25% of ammonia solvent is slowly added dropwise into reaction bulb in the molten of 620 grams of deionized waters
Liquid, it is 30 minutes that the time, which is added,.During dropwise addition, reaction solution is become cloudy by clarifying, and then becomes clarification again.Then 95 are warming up to
Degree, 1.5 grams of N are added into reaction bulb, and N- dimethylethanolamines stir 4 hours, then use gas-chromatography (GC) at this temperature
The content of butyl glycidyl ether is detected, later every detection in 1 hour once until reaction completely.It is cooled to room temperature, is added 100
The colourless liquid to light yellow clear is arrived in the dilution of gram deionized water, filtering.Solid content is 38.2%, pH value 7.8.
Embodiment 3：
Under nitrogen protection, 80 grams of butyl glycidyl ethers, 100 grams of polyethylene glycol (Mw=800) are added in 2 liters of reaction bulb
Monoglycidyl ether, is heated to 85 DEG C, then starts to be added dropwise by 120 grams of styrene, 300 grams of acrylic acid and 15 grams into reaction bulb
The mixed liquor of MPA compositions, while 28 grams of TBPEH are added dropwise to reaction bulb.Time for adding is 2.5 hours, and maintaining reaction temperature is in 85-
90℃.After completion of dropwise addition, heat preservation was in 85-90 degree 2 hours.Then 80 degree are cooled to, 230 gram 25% is slowly added dropwise into reaction bulb
Ammonia solvent 640 grams of deionized waters solution, be added the time be 30 minutes.During dropwise addition, reaction solution becomes muddy by clarification
It is turbid, then become clarification again.Then 95 degree are warming up to, 1.5 grams of N of addition into reaction bulb, N- dimethylethanolamines, at this temperature
Stirring 4 hours detects butyl glycidyl ether using infrared (FTIR) and polyethylene glycol (Mw=800) monoglycidyl ether contains
Amount, later every detection in 1 hour once until reaction completely.It is cooled to room temperature, 100 grams of deionized water dilutions is added, filtering
To colourless to lurid transparency liquid.Solid content is 38%, pH value 7.5.
Embodiment 4：
Under nitrogen protection, in 2 liters of reaction bulb be added 60 grams of butyl glycidyl ethers, be heated to 85 DEG C, then start to
The mixed liquor being made of 300 grams of styrene, 240 grams of acrylic acid and 15 grams of MPA is added dropwise in reaction bulb, while 28 are added dropwise to reaction bulb
Gram TBPEH.Time for adding is 2.5 hours, and maintaining reaction temperature is at 85-90 DEG C.After completion of dropwise addition, heat preservation is small in 85-90 degree 2
When.Then 80 degree are cooled to, 290 grams of N are slowly added dropwise into reaction bulb, N- dimethylethanolamines are dissolved in 600 grams of deionized waters
Solution, be added the time be 30 minutes.During dropwise addition, reaction solution is become cloudy by clarifying, and then becomes clarification again.Then it is warming up to
It 95 degree, stirs at this temperature 4 hours, the content of gas-chromatography (GC) detection butyl glycidyl ether is then used, later every 1
Hour detection once until react completely.It is cooled to room temperature, 100 grams of deionized water dilutions is added, arriving for filtering is colourless to pale yellow
The transparency liquid of color.Solid content is 39%, pH value 8.0.
Embodiment 5：
Under nitrogen protection, in 2 liters of reaction bulb be added 60 grams of butyl glycidyl ethers, be heated to 85 DEG C, then start to
The mixed liquor being made of 180 grams of styrene, 200 grams of acrylic acid, 100 grams of methacrylic acids and 18 grams of n-DDM is added dropwise in reaction bulb,
30 grams of BPO are added dropwise to reaction bulb simultaneously and are dissolved in the solution in 60 grams of butyl glycidyl ethers.Time for adding is 4.5 hours, dimension
Reaction temperature is held at 85-90 DEG C.After completion of dropwise addition, heat preservation was in 85-90 degree 2 hours.Then 80 degree are cooled to, slowly to reaction bulb
240 grams of N of middle dropwise addition, N- dimethylethanolamines are dissolved in the solution of 600 grams of deionized waters, and it is 30 minutes that the time, which is added,.It was added dropwise
Cheng Zhong, reaction solution are become cloudy by clarifying, and then become clarification again.Then 95 degree are warming up to, at this temperature stirring 4 hours, then
The content of butyl glycidyl ether is detected with gas-chromatography (GC), later every detection in 1 hour once until reaction completely.It is cooling
To room temperature, 100 grams of deionized water dilutions are added, colourless to lurid transparency liquid is arrived in filtering.Solid content is 40%, pH
Value is 6.5.
Embodiment 6-10 and comparative example 1-2：
The preparation of pigment dispersion：
*For the mixed liquor of 1 gram of wetting agent 810,997.5 grams of deionized water of 104E, 1.5 grams of antifoaming agent Tego.
The storage stability of pigment dispersion is tested：
Test condition：It is stored 10 days at 50 DEG C
By upper table it can be seen that there is relatively good storage stability using the dispersant prepared by the present invention.
Embodiment 11-13 and the comparison of comparative example 3-4 color developings：
The preferred embodiment of the present invention has been described in detail above.It should be appreciated that the ordinary skill of this field is without wound
The property made labour, which according to the present invention can conceive, makes many modifications and variations.Therefore, all technician in the art
Pass through the available technology of logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Scheme, all should be in the protection domain being defined in the patent claims.
Claims (8)
1. a kind of water-based hydrophobic modified polymethyl hydrochlorate dispersant, by weight, including：10-50 wt%'s contains double bond
The hydrophobic monomer A of aromatic group, 8-30 wt% compound B, the 20-82 wt% containing terminal epoxy groups (methyl) third
Olefin(e) acid；
The hydrophobic monomer A of the wherein described aromatic group containing double bond is selected from styrene, 4- methyl styrenes, 2- vinyl
It is one or more in naphthalene, α-methylstyrene；
The compound B containing terminal epoxy groups is selected from propyl glycidyl ether, butyl glycidyl ether, tertiary butyl contracting
Water glycerin ether, hexyl glycidyl ether, octyl glycidyl ether, lauryl alcohol glycidol ether, polyoxyethylene monoglycidyl ether,
One or several kinds in polyoxypropylene monoglycidyl ether, polyoxyethylene polyoxypropylene monoglycidyl ether；
It is characterized in that, the preparation method of the dispersant includes：
1）The component A, (methyl) acrylic acid and chain-transferring agent are uniformly mixed；
2）Component B is heated to 80-110oC；
3）Start the mixed liquor that component A/ (methyl) acrylic acid/chain-transferring agent is added dropwise into component B, while free radical initiation is added
Agent, it is 2-6 hours that the time, which is added,；
4）After completion of dropwise addition, 2 hours are kept the temperature, is then slowly added into the aqueous solution of neutralization reagent, temperature is maintained at 80 when additionoC with
On, adjust pH and solid content；
5）It is warming up to 90-95oThe N of 0.1-1% is added in C, and N- dimethylethanolamines to reaction terminate, and are cooled to room temperature, and addition is gone
Ionized water is diluted, and required water-based hydrophobic modified polymethyl hydrochlorate dispersant is obtained by filtration；
Wherein, the chain-transferring agent is in mercaptopropionic acid, mercapto-propionate, mercaptopropionic acid butyl ester, lauryl mercaptan
One or several kinds.
2. water-based hydrophobic modified polymethyl hydrochlorate dispersant as described in claim 1, wherein the virtue containing double bond
The content of the hydrophobic monomer A of perfume base group is 10-40 wt%.
3. water-based hydrophobic modified polymethyl hydrochlorate dispersant as claimed in claim 2, wherein the virtue containing double bond
The content of the hydrophobic monomer A of perfume base group is 20-40 wt%.
4. water-based hydrophobic modified polymethyl hydrochlorate dispersant as described in claim 1, wherein described contain terminal epoxy
The content of the compound B of group is 8-25 wt%.
5. water-based hydrophobic modified polymethyl hydrochlorate dispersant as claimed in claim 4, wherein described contain terminal epoxy
The content of the compound B of group is 8-20 wt%.
6. water-based hydrophobic modified polymethyl hydrochlorate dispersant as described in claim 1, wherein the radical initiator
To be selected from tert-butyl hydroperoxide, benzoyl peroxide, dilauroyl peroxide, azodiisobutyronitrile, peroxidating isooctyl acid uncle
Butyl ester, peroxidized t-butyl perbenzoate are one such or several, and dosage is 0.5-8 wt%.
7. water-based hydrophobic modified polymethyl hydrochlorate dispersant as described in claim 1, wherein the neutralization reagent is choosing
From ammonium hydroxide, ethanol amine, diethanol amine, triethanolamine, AMP-95, triethylamine, N, N- dimethylethanolamines, diisopropanolamine (DIPA), hydrogen
It is one or several kinds of in sodium oxide molybdena, potassium hydroxide；In step 4 pH to 6.0-8.5 is adjusted using the neutralization reagent.
8. as described in claim 1-7 is any water-based hydrophobic modified polymethyl hydrochlorate dispersant aqueous building coating,
Application in industrial coating or water-based ink.
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| CN201610914804.1A CN106397656B (en) | 2016-10-20 | 2016-10-20 | A kind of preparation and application of water-based hydrophobic modified polymethyl hydrochlorate dispersant |
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| CN1473889A (en) * | 1996-09-13 | 2004-02-11 | 大日本油墨化学工业株式会社 | Method for producing ink jet ink |
| CN1771280A (en) * | 2003-04-02 | 2006-05-10 | 瓦尔斯帕供应公司 | Aqueous dispersions and coatings |
| CN101575397A (en) * | 2009-06-02 | 2009-11-11 | 中山大学 | Method for preparing water-soluble solid styrene/acrylic resin and application thereof |
| WO2015116916A1 (en) * | 2014-01-30 | 2015-08-06 | Basf Se | Resin-support emulsion polymerication of hydrophobic monomers |
| CN105601785A (en) * | 2015-11-06 | 2016-05-25 | 武汉工程大学 | Epoxy active diluent modified acrylic acid resin aqueous dispersion |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1473889A (en) * | 1996-09-13 | 2004-02-11 | 大日本油墨化学工业株式会社 | Method for producing ink jet ink |
| CN1771280A (en) * | 2003-04-02 | 2006-05-10 | 瓦尔斯帕供应公司 | Aqueous dispersions and coatings |
| CN101575397A (en) * | 2009-06-02 | 2009-11-11 | 中山大学 | Method for preparing water-soluble solid styrene/acrylic resin and application thereof |
| WO2015116916A1 (en) * | 2014-01-30 | 2015-08-06 | Basf Se | Resin-support emulsion polymerication of hydrophobic monomers |
| CN105601785A (en) * | 2015-11-06 | 2016-05-25 | 武汉工程大学 | Epoxy active diluent modified acrylic acid resin aqueous dispersion |
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