CN103897101A - Acrylic polyester-type hyperdispersant and preparation method and application thereof - Google Patents
Acrylic polyester-type hyperdispersant and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of a dispersant, and particularly relates to an acrylic polyester-type hyperdispersant and a preparation method thereof. The acrylic polyester-type hyperdispersant is a polymer obtained from a monomer A, a monomer B and a monomer C by free radicals atactic polymerization, wherein the monomer A is the monomer containing phenyl m-pentadecyl acrylate or derivatives thereof; the monomer B is the monomer containing carboxyl or sulfonic acid or phosphonic acid group; the monomer C is an alkyl (meth)acrylate monomer. The hyperdispersant disclosed by the invention is excellent in dissolving property in an organic medium, the viscosity of a dispersion system can be reduced, the mobility of the dispersion system is improved, and the storage and use performances under a low-temperature condition are good.
Description
Technical field
The invention belongs to dispersion agent technical field, particularly a kind of acrylic polyester type hyper-dispersant and its preparation method and application.
Background technology
In ink and coating industry, mineral dye and nano-powder, in dispersion application process, inevitably there will be agglomeration, and then finally affect the properties of product.Tradition dispersion agent is better at the dispersion effect of water-based system, and the dispersion effect in solvent is poor.For solving this difficult problem, the eighties in last century JamesS.HamPton proposed this completely new concept of hyper-dispersant (J.S.HamPton.A review of hyperdispersant technology[J] .American Chemical Society, 1986,192:9～12; J.S.Hampton et al.Extending the boundaries of dispersant technology[J] .Progress in Organic Coating, 2002,45 (2): 249～257).Hyper-dispersant is the efficient polymer dispersant of a class, in Molecular Structure Design, has broken away from the limitation of conventional dispersion agent, all has good dispersion effect in water-based and non-aqueous media.Hyper-dispersant has many good qualities in application, can be fast fully wetting granules of pigments, can improve solid content in dispersion system, can make that system is uniformly dispersed, good stability, significantly improve dispersion product performance.
Hyper-dispersant has similitude compared with dispersion agent, also has difference.Resemblance is that the molecular structure of hyper-dispersant is also divided into two parts, and wherein hydrophilic segment is called anchoring group, common are-NR
3 +,-COOH ,-COO
-,-SO
3h ,-SO
3 -,-PO
4 2-, polyamine, polyvalent alcohol and polyethers; Lipophilic group is called solvation segment, common are polyethers, polyester, polyacrylic ester and polyolefine etc.Different, the Length Ratio tradition dispersion agent of solvation segment is long, and general requirement is greater than 80 carbon atoms.Anchoring group in dispersion process with surface of pigments effect, make hyper-dispersant absorption or act on granules of pigments.Because solvation segment has enough length and snappiness; it and dispersion medium have good consistency; in solvent medium, can take the conformation relatively stretching, can form with solid particles surface the protective layer of adequate thickness, to improve the stability of dispersion system.
In coating and printing-ink and pesticide industry, conventionally pigment need be dispersed in and in solvent, form pigment dispersion.Pigment dispersion is generally by mechanical means, by broken the aggregate of granules of pigments and reduce the method preparation of average particle size particle size, grinds the normally best method of dispersion solid particle.Generally dispersion process is divided into three phases, soaks, break, decentralized stabilization, in fact this three phases is overlapping, is simultaneous sometimes.In industrial production, an important indicator investigating dispersing agent performance is to reduce milling time.The ability that pigment reaches ideal dispersion grade has at short notice become generally acknowledged most important index.
Acrylic polyester type hyper-dispersant is as the type being most widely used in hyper-dispersant, because the range of choice of acrylate monomer is very extensive, the polarity of its solvent chain and solubility parameter can regulate easily by the feed ratio that changes comonomer, and therefore the scope of application is wider.In order to obtain single-ended functionalized solvent chain, generally select the material such as mercaptan acid, mercaptoalcohol as chain-transfer agent.The molecular weight of solvent chain can be controlled by the consumption that changes initiator and chain-transfer agent, obtains holding carboxyl or hydroxy terminated polypropylene acid esters hyper-dispersant.In recent years, esters of acrylic acid application of dispersant is comparatively extensive, but its low-temperature construction performance and dispersion stabilization Shortcomings, the viscosity aspect effect that is mainly manifested in reduction dispersion system is undesirable, and dispersion system is stored and uses limited larger under cold condition simultaneously.
Summary of the invention
The object of this invention is to provide a kind of acrylic polyester type hyper-dispersant and its preparation method and application, described dispersion agent has good performance reducing aspect the viscosity of dispersion system and raising dispersion system mobility, and is conducive to dispersion system and under cold condition, stores and use.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of acrylic polyester type hyper-dispersant, described polyester type ultra-dispersant agent is to carry out by monomer A, monomers B and monomer C the polymkeric substance that free radical random polymerization obtains, described monomer A is to contain a monomer for pentadecyl phenyl acrylate or derivatives thereof, described monomers B is the monomer that contains carboxyl or sulfonic acid or phosphonyl group, and described monomer C is (methyl) alkyl-acrylates monomer.
The weight-average molecular weight of described hyper-dispersant is at 1000-80000, and preferable weight-average molecular weight is at 3000-50000, more preferably 3000-10000.
In the gross weight of three kinds of monomers, monomer A content is 2-30%, and monomers B content is 2-40%, and monomer C content is 50-90%.Preferred: monomer A content is 5-20%, monomers B content is 5-20%, and monomer C content is 60-85%.
Monomer A preferably between pentadecyl phenyl acrylate or a pentadecyl phenyl methacrylate, more preferably between pentadecyl phenyl acrylate.
Between pentadecyl phenyl acrylate and derivative thereof be a kind of novel monomer, can react and obtain with acrylate chloride or methacrylic chloride by a pentadecyl phenol, concrete grammar can be with reference to Process Variables of the Esterification Reaction of 3-Pentadecylphenol and Acryloyl Chloride Catalyzed by an Ionic Liquid, chemical engineering and technology, 36,2013,559-566.
Monomers B can be selected vinylformic acid, methacrylic acid, ethylacrylic acid, α-chloroacrylic acid, alpha-cyanoacrylate, Beta-methyl vinylformic acid (β-crotonic acid), α-phenylacrylic acid, β-acryloxy propionic, Sorbic Acid, α-chlorine Sorbic Acid, styracin, to chloro-cinnamic acid, β-styrene acrylic (1-carboxyl-4-phenyl-1, 3-divinyl), methylene-succinic acid, toxilic acid, citraconic acid, propene dicarboxylic acid, equisetic acid, fumaric acid, three carboxyl ethene (tricarboxy ethylene), muconic acid, 2-acryloxy propionic and styrene sulfonic acid, 2-acrylamido-2-methyl propane sulfonic acid, 1-allyloxy-2-hydroxypropanesulfonic acid, allyloxy Phenylsulfonic acid, vinyl sulfonic acid, methallyl sulfonic acid, allyloxy Phenylsulfonic acid or vinyl phosphonate, preferably vinylformic acid, methacrylic acid.
Monomer C can select (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid 2-methyl pentyl ester, (methyl) vinylformic acid 2-propyl group heptyl ester, (methyl) vinylformic acid 2-butyl monooctyl ester, (methyl) 2-EHA, (methyl) Octyl acrylate, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) vinylformic acid 2-tertiary butyl heptyl ester, (methyl) vinylformic acid 3-sec.-propyl heptyl ester, (methyl) decyl acrylate, (methyl) vinylformic acid undecane ester, (methyl) vinylformic acid 5-methyl undecane ester, (methyl) vinylformic acid dodecane ester, (methyl) vinylformic acid 2-methyl dodecane ester, (methyl) vinylformic acid tridecane ester, (methyl) vinylformic acid 5-methyl tridecane ester, (methyl) vinylformic acid tetradecane ester, (methyl) vinylformic acid pentadecane ester, (methyl) vinylformic acid n-Hexadecane ester, (methyl) vinylformic acid 2-methyl n-Hexadecane ester, (methyl) vinylformic acid heptadecane ester, (methyl) vinylformic acid octadecane ester, (methyl) vinylformic acid nonadecane ester, (methyl) vinylformic acid eicosane ester, wherein preferred butyl acrylate.
The preparation method of described acrylic polyester type hyper-dispersant, use ordinary method, can carry out: will under the condition that monomer A, monomers B and monomer C exist at polymerization starter, solvent exists or do not exist, use or do not use chain-transfer agent, carry out free radical random polymerization as follows.
Preferably, under the condition that monomer A, monomers B and monomer C are existed at polymerization starter, chain-transfer agent and solvent, carry out polyreaction, temperature of reaction is not higher than 90 ℃.
This binary polymerization reaction, is preferably solution polymerization.In this situation, be effective in order to make the molecular weight of the acrylic acid polymer after polymerization in preferable range, be combined with chain-transfer agent in the time of polymerization.As chain-transfer agent, for example, can use thio-alcohol or the Thiovanic acids etc. such as normal-butyl mercaptan, lauryl mercaptan, stearyl-mercaptan, cyclohexyl mercaptan, preferably Thiovanic acid.
As polymerization starter, can use the known thermal polymerizations such as superoxide such as azo-compound, peroxidized t-butyl perbenzoate, peroxide-2-ethyl hexanoic acid tert-butyl such as AIBN (Diisopropyl azodicarboxylate).
For polymerization temperature, for the better polymerization of controlling acrylic monomer, preferably not too high temperature, as made below its polymerization at 90 ℃.
Can use polar solvent or the non-polar solvent solvent as solution polymerization.As polar organic solvent, can use the mixed solvent of ester series solvent, alcohol series solvent, ketone series solvent, ether series solvent or above solvent.
Described polar solvent is selected from one of following or more than one mixture: ethyl acetate, methyl acetate, methyl propionate, ethyl propionate, isopropyl acetate, butylacetate, acetic acid methoxyl group propyl ester, ethyl butyrate, Wickenol 116, Wickenol 117, ethyl sebacate, single capric acid propylene glycol ester, trimethylolpropane tris 2-ethylhexyl, three 2 ethyl hexanoic acid glyceryl ester, acetone, butanone, methyl isoamyl ketone, metacetone, diisopropyl ketone, methyl isopropyl Ketone, diisobutyl ketone, pimelinketone, methyl alcohol, ethanol, propyl alcohol, butanols, Virahol, different tetradecyl alcohol, different palmityl alcohol, isooctadecanol, oleyl alcohol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol dibutyl ether.
As non-polar organic solvent, can use aromatic hydrocarbons, aliphatic hydrocarbon or hydrochloric ether.Nonpolar aromatic hydrocarbons can be selected toluene or dimethylbenzene.Aliphatic hydrocarbon is as hexane, heptane, octane, decane or petroleum distillate (petroleum naphtha and mineral oil).Hydrochloric ether can be selected trieline, methylene dichloride, trichloromethane, tetracol phenixin, tetrachloroethylene or chlorobenzene.
The application of described acrylic polyester type hyper-dispersant, can be used for disperseing mineral dye, pigment dyestuff, or as dispersion, the abrasive of granular solids, liquid medium.Be mainly used in coating, ink, pesticide industry.
The example of mineral dye comprises metal oxide, for example, as the titanium oxide of the titanium dioxide of titanium dioxide, rutile titanium dioxide and surface-coated, different colours (yellow and black), the ferriferous oxide of different colours, for example yellow, redness, brown and black, zinc oxide, zirconium white, aluminum oxide; Oxygen metallic compound, for example, in pucherite, Leyden blue, cobaltous stannate, Rinmann's green, zinc chromate and manganese, nickel, titanium, chromium, antimony, magnesium, cobalt, iron or the aluminium mixed metal oxide of two or more; Molybdate and the chromic salt of Prussian blue, cinnabar, ultramarine, zinc phosphate, zinc sulphide, calcium and zinc; Metallic effect pigments, for example aluminum slice, copper and copper/zinc alloy; Pearly-lustre thin slice, for example lead carbonate and pearl white.
Pigment dyestuff comprises azo, tetrazo, condensation azo, indanthrone, different Yin Dan ketone, naphthoquinones, isodibenzanthrone, triphendioxazine, quinacridone and phthalocyanine series dyes, especially copper phthalocyanine and halo derivatives dyestuff thereof, and the color lake of matching stain, basic dyestuff and mordant dye.Pigment dyestuff is phthalocyanine, copper phthalocyanine, monoazo, tetrazo, indanthrone, quinacridone preferably.
Hyper-dispersant of the present invention is specially adapted to make a kind of particulate solid thing to be scattered in a kind of organic medium.As particulate solid thing, hyper-dispersant and organic medium are prepared into dispersion liquid.
Described solids can be to be insoluble in this organic medium at low temperature and normal temperature, and wishes that it is stable at any inorganic or organic solid material of organic medium with fine form.
Be suitable for the example of solid as pigment, paint and pigment, weighting agent and filler for plastics for solvent ink; Dyestuff, dispersed dye; Granular ceramic material; Magneticsubstance and magnetic pipe recording material, fire retardant etc.
Particulate solid thing comprises enriching substance and filler, the calcium carbonate that for example grinds and precipitate, calcium sulfate, calcium oxide, caoxalate, calcium phosphate, phosphonic acids calcium, barium sulfate, barium carbonate, magnesium oxide, magnesium hydroxide, brucite or brucite, precipitated magnesium hydroxide, magnesiumcarbonate, rhombspar, three aluminium hydroxides, peroxidation aluminium or boehmite, the silicate of calcium and magnesium, silico-aluminate (comprises nanoclay, kaolin), montmorillonite (comprises wilkinite, hectorite and saponite), mica, talcum (comprises white mica, phlogopite, lithionite and chlorite), chalk, synthesize and precipitated silica, calcination silicon-dioxide, steel fiber and powder, zinc, aluminium, glass fibre, refractory fibre, carbon black (comprises single wall and multi-walled carbon nano-tubes, the carbon black that strengthens and do not strengthen), graphite.
Granular ceramic material is as aluminum oxide, zirconium white, titanium oxide, cerium oxide, silicon nitride, aluminium nitride, boron nitride, silicon carbide, norbide, silicon-aluminium mixed nitride thing and metal titanium hydrochlorate; Magneticsubstance for example, as the magnetic oxide of transition metal (being generally iron and chromium), γ-Fe
2o
3, Fe
3o
4, cobalt doping ferriferous oxide, wustite (for example barium ferrite) and metallic particles (for example metallic aluminium, iron, nickel, cobalt, copper, silver, gold, palladium and platinum and alloy thereof).
Organic medium for particulate solid thing of the present invention or pigment dispersion is non-aqueous liquid.Be preferably the nonpolar in fact aromatic hydrocarbons of a kind of polar organic media or one, aliphatic hydrocarbon or hydrochloric ether.
Polar organic media can be selected especially low alkyl group ethers, ester class, ketone or amides equal solvent of ethers.Ketone is as acetone, methylethylketone, metacetone, diisopropyl ketone, methyl isopropyl Ketone, diisobutyl ketone, methyl isoamyl ketone or pimelinketone.Ester class can be selected methyl acetate, ethyl acetate, isopropyl acetate, butylacetate, ethyl formate, methyl propionate, acetic acid methoxyl group propyl ester or ethyl butyrate.Nonpolar aromatic hydrocarbons can be selected toluene or dimethylbenzene.Aliphatic hydrocarbon is as hexane, heptane, octane, decane or petroleum distillate (petroleum naphtha and mineral oil).Hydrochloric ether can be selected trieline, methylene dichloride, trichloromethane, tetracol phenixin, tetrachloroethylene or chlorobenzene.
In dispersion liquid, solids content is 5-95wt%, specifically depends on the character of this solid and the relative density of this solid and this organic medium and its application.This dispersion liquid can make for the preparation of any common method of dispersion liquid with known.So particulate solid thing, hyper-dispersant and dispersion organic medium can mix in any order, then use the mechanical treatment of high-speed shearing emulsion machine, ball milling, pearl mill or colloidal mill to make the microparticulate of solid to suitable granularity, until form dispersion liquid.Particulate solid thing also can first mix with hyper-dispersant, makes in a suitable manner solid particulate be distributed to suitable particle size, and then mixes with other additives such as resins, finally makes dispersion liquid.
Hyper-dispersant of the present invention is specially adapted to high speed shear emulsification and prepares dispersion system.Particulate solid thing is neutralized to one or more film-forming resins and other additive makes dispersion liquid simultaneously at one or more organic dispersion mediums.Preferably, take the gross weight of this dispersion liquid as benchmark, the particulate solid that this dispersion system contains 10-70%, better, the weight percentage of the particulate solid thing that dispersion liquid contains is not less than 30%, not higher than 60%; The consumption of hyper-dispersant is the 0.1-10% of particulate solid thing.In this dispersion liquid, resin demand is not less than 10% of dispersion liquid gross weight, not higher than 40% of dispersion liquid total amount.The dispersion liquid that contains hyper-dispersant of the present invention is particularly useful for paint, height admittedly containing industries such as paint, ink, flexographic ink, gravure printing ink, screen printing ink, agricultural chemicals and non-ceramic water techniques.
Hyper-dispersant of the present invention demonstrates the advantage that is better than general acrylic polyester type dispersion agent, particularly demonstrate solubility property excellent in the organic mediums such as polar organic media or a kind of nonpolar in fact aromatic hydrocarbons, aliphatic hydrocarbon or hydrochloric ether, and microphase-separated or crystallization do not occur when 4 ℃ of standing storages.When in low temperature storage, can there is microphase-separated phenomenon at-10 ℃, but when temperature recovery during to 4-10 ℃ this hyper-dispersant easily dissolve again.When for paint and ink, hyper-dispersant of the present invention can produce lower viscosity, higher gloss, lower photographic fog, improves the flocculating property of dispersion liquid.
The present invention, with respect to prior art, has following advantage:
The superior solubility of hyper-dispersant of the present invention in organic medium, can reduce the viscosity of dispersion system, improves the mobility of dispersion system, and under cold condition storage and use properties good.
Accompanying drawing explanation
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of 11 pentadecyl phenyl acrylate/methacrylic acid/butyl acrylate terpolymers of embodiment;
Fig. 2 is the infrared spectrum of 11 pentadecyl phenyl acrylate/methacrylic acid/butyl acrylate terpolymers of embodiment.
Embodiment
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not limited to this:
In following examples, all umbers are unless otherwise noted all in weight part.
Between the preparation of pentadecyl phenyl acrylate
In 250mL four-hole boiling flask, add appropriate solvent and a pentadecyl phenol and cuprous chloride (500PPM), then add acrylate chloride and ionic liquid, under agitation slowly drip acid binding agent triethylamine with constant pressure funnel, reflux condensing tube top seals with balloon.The mol ratio of an acyl chlorides/pentadecyl phenol is 1.15, is warming up to 57 ℃, and after reaction 8.25h finishes, filtered while hot is removed the triethylamine hydrochloride generating.Get filtrate and dilute with hplc grade methanol, carry out liquid phase analysis, to determine reaction yield.Filtrate is after washing, and rotary evaporation is removed solvent and obtained a pentadecyl phenyl acrylate crude product, obtains sterling through recrystallization.
Embodiment 1
Take 1 part of methacrylic acid, 8.5 parts of butyl acrylates, 0.1 part of pentadecyl phenyl acrylate and chain-transfer agent Thiovanic acid between 0.5 part (lower same), 0.1 part of AIBN of initiator, 25 parts of acetone and Virahol (both mass ratio 1:1, lower with) solvent is pre-mixed, a part is (without strictly restriction, can first add half) join in the four-hole boiling flask with thermometer, pass into nitrogen and be placed in the oil bath pan that is heated in advance 70 ℃, turn on agitator.After question response 2h, add remaining mixture with constant pressure funnel.Then make reaction solution be incubated 4h at 70 ℃, after cooling, add tetrahydrofuran (THF) dilution.Finally reaction solution is poured into Precipitation polymkeric substance in the mixing solutions of first alcohol and water, will precipitate vacuum-drying, get final product to obtain acrylic polyester type hyper-dispersant.It is 20000 that GPC detects weight-average molecular weight.
Embodiment 2
Take 1 part of methacrylic acid, 8.5 parts of butyl acrylates, pentadecyl phenyl acrylate and chain-transfer agent between 0.5 part, 0.15 part of AIBN of initiator, 25 parts of acetone and isopropanol solvent are pre-mixed, a part joins in the four-hole boiling flask with thermometer, passes into nitrogen and is placed in the oil bath pan that is heated in advance 80 ℃, turn on agitator.After question response 2h, add remaining mixture with constant pressure funnel.Then make reaction solution be incubated 4h at 80 ℃, after cooling, add tetrahydrofuran (THF) dilution.Finally reaction solution is poured into Precipitation polymkeric substance in the mixing solutions of first alcohol and water, will precipitate vacuum-drying, get final product to obtain acrylic polyester type hyper-dispersant.It is 10000 that GPC detects weight-average molecular weight.
Embodiment 3
Take 1 part of methacrylic acid, 8.5 parts of butyl acrylates, pentadecyl phenyl acrylate between 0.5 part, 0.08 part of AIBN of initiator, 10 parts of acetone and isopropanol solvent are pre-mixed, a part joins in the four-hole boiling flask with thermometer, passes into nitrogen and is placed in the oil bath pan that is heated in advance 60 ℃, turn on agitator.After question response 2h, add remaining mixture with constant pressure funnel.Then make reaction solution be incubated 4h at 60 ℃, after cooling, add tetrahydrofuran (THF) dilution.Finally reaction solution is poured into Precipitation polymkeric substance in the mixing solutions of first alcohol and water, will precipitate vacuum-drying, get final product to obtain acrylic polyester type hyper-dispersant.It is 80000 that GPC detects weight-average molecular weight.
Embodiment 4
Take 2 parts of methacrylic acids, 7 parts of butyl acrylates, pentadecyl phenyl acrylate and chain-transfer agent between 1 part, 0.15 part of AIBN of initiator, 25 parts of acetone and isopropanol solvent are pre-mixed, a part joins in the four-hole boiling flask with thermometer, passes into nitrogen and is placed in the oil bath pan that is heated in advance 70 ℃, turn on agitator.After question response 2h, add remaining mixture with constant pressure funnel.Then make reaction solution be incubated 4h at 70 ℃, after cooling, add tetrahydrofuran (THF) dilution.Finally reaction solution is poured into Precipitation polymkeric substance in the mixing solutions of first alcohol and water, will precipitate vacuum-drying, get final product to obtain acrylic polyester type hyper-dispersant.It is 12000 that GPC detects weight-average molecular weight.
Embodiment 5
Take 4 parts of methacrylic acids, 5 parts of butyl acrylates, pentadecyl phenyl acrylate and chain-transfer agent between 1 part, 0.1 part of AIBN of initiator, 15 parts of acetone and isopropanol solvent are pre-mixed, a part joins in the four-hole boiling flask with thermometer, passes into nitrogen and is placed in the oil bath pan that is heated in advance 60 ℃, turn on agitator.After question response 2h, add remaining mixture with constant pressure funnel.Then make reaction solution be incubated 4h at 60 ℃, after cooling, add tetrahydrofuran (THF) dilution.Finally reaction solution is poured into Precipitation polymkeric substance in the mixing solutions of first alcohol and water, will precipitate vacuum-drying, get final product to obtain acrylic polyester type hyper-dispersant.It is 50000 that GPC detects weight-average molecular weight.
Embodiment 6
Take 1 part of methacrylic acid, 6 parts of butyl acrylates, pentadecyl phenyl acrylate and chain-transfer agent between 3 parts, 0.1 part of AIBN of initiator, 20 parts of acetone and isopropanol solvent are pre-mixed, a part joins in the four-hole boiling flask with thermometer, passes into nitrogen and is placed in the oil bath pan that is heated in advance 60 ℃, turn on agitator.After question response 2h, add remaining mixture with constant pressure funnel.Then make reaction solution be incubated 4h at 60 ℃, after cooling, add tetrahydrofuran (THF) dilution.Finally reaction solution is poured into Precipitation polymkeric substance in the mixing solutions of first alcohol and water, will precipitate vacuum-drying, get final product to obtain acrylic polyester type hyper-dispersant.It is 30000 that GPC detects weight-average molecular weight.
Embodiment 7
Take 0.2 part of methacrylic acid, 9 parts of butyl acrylates, pentadecyl phenyl acrylate and chain-transfer agent between 0.8 part, 0.2 part of AIBN of initiator, 25 parts of acetone and isopropanol solvent are pre-mixed, a part joins in the four-hole boiling flask with thermometer, passes into nitrogen and is placed in the oil bath pan that is heated in advance 70 ℃, turn on agitator.After question response 2h, add remaining mixture with constant pressure funnel.Then make reaction solution be incubated 4h at 70 ℃, after cooling, add tetrahydrofuran (THF) dilution.Finally reaction solution is poured into Precipitation polymkeric substance in the mixing solutions of first alcohol and water, will precipitate vacuum-drying, get final product to obtain acrylic polyester type hyper-dispersant.It is 15000 that GPC detects weight-average molecular weight.
Embodiment 8
Take 0.8 part of methacrylic acid, 9 parts of butyl acrylates, pentadecyl phenyl acrylate and chain-transfer agent between 0.2 part, 0.1 part of AIBN of initiator, 25 parts of acetone and isopropanol solvent are pre-mixed, a part joins in the four-hole boiling flask with thermometer, passes into nitrogen and is placed in the oil bath pan that is heated in advance 70 ℃, turn on agitator.After question response 2h, add remaining mixture with constant pressure funnel.Then make reaction solution be incubated 4h at 70 ℃, after cooling, add tetrahydrofuran (THF) dilution.Finally reaction solution is poured into Precipitation polymkeric substance in the mixing solutions of first alcohol and water, will precipitate vacuum-drying, get final product to obtain acrylic polyester type hyper-dispersant.It is 22000 that GPC detects weight-average molecular weight.
Embodiment 9
Take 1 part of methacrylic acid, 8.3 parts of butyl acrylates, pentadecyl phenyl acrylate and chain-transfer agent between 0.7 part, 0.3 part of AIBN of initiator, 30 parts of acetone and isopropanol solvent are pre-mixed, a part joins in the four-hole boiling flask with thermometer, passes into nitrogen and is placed in the oil bath pan that is heated in advance 90 ℃, turn on agitator.After question response 2h, add remaining mixture with constant pressure funnel.Then make reaction solution be incubated 4h at 80 ℃, after cooling, add tetrahydrofuran (THF) dilution.Finally reaction solution is poured into Precipitation polymkeric substance in the mixing solutions of first alcohol and water, will precipitate vacuum-drying, get final product to obtain acrylic polyester type hyper-dispersant.It is 3000 that GPC detects weight-average molecular weight.
Embodiment 10
Take 1 part of methacrylic acid, 8.3 parts of butyl acrylates, pentadecyl phenyl acrylate and chain-transfer agent between 0.7 part, 0.2 part of AIBN of initiator, 30 parts of acetone and isopropanol solvent are pre-mixed, a part joins in the four-hole boiling flask with thermometer, passes into nitrogen and is placed in the oil bath pan that is heated in advance 80 ℃, turn on agitator.After question response 2h, add remaining mixture with constant pressure funnel.Then make reaction solution be incubated 4h at 80 ℃, after cooling, add tetrahydrofuran (THF) dilution.Finally reaction solution is poured into Precipitation polymkeric substance in the mixing solutions of first alcohol and water, will precipitate vacuum-drying, get final product to obtain acrylic polyester type hyper-dispersant.It is 5000 that GPC detects weight-average molecular weight.
Take 1 part of methacrylic acid, 8.3 parts of butyl acrylates, pentadecyl phenyl acrylate and chain-transfer agent between 0.7 part, 0.2 part of AIBN of initiator, 30 parts of acetone and isopropanol solvent are pre-mixed, a part joins in the four-hole boiling flask with thermometer, passes into nitrogen and is placed in the oil bath pan that is heated in advance 75 ℃, turn on agitator.After question response 2h, add remaining mixture with constant pressure funnel.Then make reaction solution be incubated 4h at 70 ℃, after cooling, add tetrahydrofuran (THF) dilution.Finally reaction solution is poured into Precipitation polymkeric substance in the mixing solutions of first alcohol and water, will precipitate vacuum-drying, get final product to obtain acrylic polyester type hyper-dispersant.It is 6000 that GPC detects weight-average molecular weight.
The nucleus magnetic hydrogen spectrum that obtains terpolymer refers to Fig. 1.
Concrete parsing seen the following form:
GPC lining average molecular weight can and nuclear-magnetism have deviation because every kind of testing method has its limitation and the scope of application.It is that the little meeting of molecular weight is more accurate based on functional group's terminal hydrogen analysis that nuclear-magnetism is surveyed molecular weight.In the time that molecular weight distribution is wider, the end group ratio of small molecules amount is large, and the stronger molecular weight of signal is less than normal.What GPC surveyed is that 3 powers of ultraviolet light intensity and size are directly proportional, and the signal that molecular weight is large is stronger.So wanting that the molecular weight ratio nuclear-magnetism that GPC records calculates is large.As can be seen from the above table, between each group of terpolymer, proportioning is: pentadecyl phenyl acrylate/methacrylic acid/butyl acrylate=1:7:36, the molecular weight of inferring thus acrylic polyester type hyper-dispersant is 5568, and the weight-average molecular weight of GPC test is 6000.
The infared spectrum that obtains terpolymer refers to Fig. 2.Can find out from infared spectrum: 1730cm
-1place, for C=O stretching vibration absorption peak, illustrates that product contains ester group; 3450cm
-1place is the hydroxyl absorption peak in carboxyl; And 2950cm
-1place is the absorption peak of methyl methylene radical; 1630cm
-1place is the characteristic peak of phenyl ring; Prove thus to contain in polymkeric substance phenyl ring, ester group, hydroxyl and methyl, methylene radical.
Embodiment 12
Take 1 part of methacrylic acid, 8.3 parts of butyl acrylates, pentadecyl phenyl acrylate and chain-transfer agent between 0.7 part, 0.2 part of AIBN of initiator, 30 parts of acetone and isopropanol solvent are pre-mixed, a part joins in the four-hole boiling flask with thermometer, passes into nitrogen and is placed in the oil bath pan that is heated in advance 70 ℃, turn on agitator.After question response 2h, add remaining mixture with constant pressure funnel.Then make reaction solution be incubated 4h at 60 ℃, after cooling, add tetrahydrofuran (THF) dilution.Finally reaction solution is poured into Precipitation polymkeric substance in the mixing solutions of first alcohol and water, will precipitate vacuum-drying, get final product to obtain acrylic polyester type hyper-dispersant.It is 8000 that GPC detects weight-average molecular weight.
Embodiment 13
Take 1 part of vinylformic acid, 8.3 parts of butyl acrylates, pentadecyl phenyl methacrylate and chain-transfer agent between 0.7 part, 0.2 part of AIBN of initiator, 30 parts of acetone and isopropanol solvent are pre-mixed, a part joins in the four-hole boiling flask with thermometer, passes into nitrogen and is placed in the oil bath pan that is heated in advance 80 ℃, turn on agitator.After question response 2h, add remaining mixture with constant pressure funnel.Then make reaction solution be incubated 4h at 80 ℃, after cooling, add tetrahydrofuran (THF) dilution.Finally reaction solution is poured into Precipitation polymkeric substance in the mixing solutions of first alcohol and water, will precipitate vacuum-drying, get final product to obtain acrylic polyester type hyper-dispersant.It is 5000 that GPC detects weight-average molecular weight.
Contrast sample 1
Take 1 part of methacrylic acid, 8.3 parts of butyl acrylates, 0.7 part of vinylbenzene and chain-transfer agent, 0.3 part of AIBN of initiator, 30 parts of acetone and isopropanol solvent are pre-mixed, a part joins in the four-hole boiling flask with thermometer, passes into nitrogen and is placed in the oil bath pan that is heated in advance 70 ℃, turn on agitator.After question response 2h, add remaining mixture with constant pressure funnel.Then make reaction solution be incubated 4h at 70 ℃, after cooling, add tetrahydrofuran (THF) dilution.Finally reaction solution is poured into Precipitation polymkeric substance in the mixing solutions of first alcohol and water, will precipitate vacuum-drying, get final product and to obtain contrast sample 1 dispersion agent.It is 8000 that GPC detects weight-average molecular weight.
The intermiscibility of dispersion agent
2 parts of dispersion agents are dissolved in after toluene 10ml, add 10 parts of ETERSET2327 resins (Changxing, Jiangsu company) to stir, be stored in respectively 25 ℃, 4 ℃ ,-10 ℃, different condition, whether different time is observed dispersion system as clear as crystal, the results are shown in table 1.
Table 1
The test of pigment flowability properties
White pigment preparation
0.5 part of dispersion agent is dissolved in 8 parts, 4:1 (weight ratio) mixture of dimethylbenzene and propyl carbinol.8 parts of titanium dioxide white pigment (R920) are added in mixture, after using high-speed shearing emulsion machine 8000r/min emulsify at a high speed 30min, use rotary viscosity instrumentation dispersion system viscosity, (viscosity <20mpas is excellent to the mobility of the dispersion system that evaluation obtains; 20mpas≤viscosity <35mpas is for well; 35mpas≤viscosity≤50mpas is that general, viscosity >50mpas is for poor), the results are shown in table 2.
Red iron oxide pigment preparation
0.5 part of dispersion agent is dissolved in 8 parts, the mixture of dimethylbenzene and propyl carbinol 4:1 (weight ratio).Red ferric oxide pigment (120M) 8 parts added in mixture, after using high-speed shearing emulsion machine 8000r/min emulsify at a high speed 30min, use rotary viscosity instrumentation dispersion system viscosity, the mobility of the dispersion system that evaluation obtains is (excellent, good, general, poor, the same white pigment of standard)
The results are shown in table 2.
Carbon black pigment preparation
1 part of dispersion agent is dissolved in 8 parts, the dimethylbenzene of 4:1 (weight ratio) and the mixture of propyl carbinol.10 parts of carbon blacks are added in mixture, after using high-speed shearing emulsion machine 8000r/min emulsify at a high speed 30min, use rotary viscosity instrumentation dispersion system viscosity, the mobility (excellent, good, general, poor, the same white pigment of standard) of the dispersion system that evaluation obtains, the results are shown in table 2.
Above-described embodiment is the preferred embodiment of the present invention, but embodiments of the present invention are not restricted to the described embodiments, and the change that other any the present invention of not deviating from does all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. an acrylic polyester type hyper-dispersant, it is characterized in that, described polyester type ultra-dispersant agent is to carry out by monomer A, monomers B and monomer C the polymkeric substance that free radical random polymerization obtains, described monomer A is to contain a monomer for pentadecyl phenyl acrylate or derivatives thereof, described monomers B is the monomer that contains carboxyl or sulfonic acid or phosphonyl group, and described monomer C is (methyl) alkyl-acrylates monomer.
2. acrylic polyester type hyper-dispersant as claimed in claim 1, is characterized in that, the weight-average molecular weight of described hyper-dispersant is at 1000-80000.
3. acrylic polyester type hyper-dispersant as claimed in claim 2, is characterized in that, in the gross weight of three kinds of monomers, monomer A content is 2-30%, and monomers B content is 2-40%, and monomer C content is 50-90%
.
4. acrylic polyester type hyper-dispersant as claimed in claim 3, is characterized in that, monomer A content is 5-20%, and monomers B content is 5-20%, and monomer C content is 60-85%
.
5. the acrylic polyester type hyper-dispersant as described in as arbitrary in claim 1-4, is characterized in that, monomer A be between pentadecyl phenyl acrylate or a pentadecyl phenyl methacrylate.
6. acrylic polyester type hyper-dispersant as claimed in claim 5, it is characterized in that, monomers B is vinylformic acid, methacrylic acid, ethylacrylic acid, α-chloroacrylic acid, alpha-cyanoacrylate, Beta-methyl vinylformic acid, α-phenylacrylic acid, β-acryloxy propionic, Sorbic Acid, α-chlorine Sorbic Acid, styracin, to chloro-cinnamic acid, β-styrene acrylic (1-carboxyl-4-phenyl-1, 3-divinyl), methylene-succinic acid, toxilic acid, citraconic acid, propene dicarboxylic acid, equisetic acid, fumaric acid, three carboxyl ethene, muconic acid, 2-acryloxy propionic and styrene sulfonic acid, 2-acrylamido-2-methyl propane sulfonic acid, 1-allyloxy-2-hydroxypropanesulfonic acid, allyloxy Phenylsulfonic acid, vinyl sulfonic acid, methallyl sulfonic acid, allyloxy Phenylsulfonic acid or vinyl phosphonate, monomer C is (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid 2-methyl pentyl ester, (methyl) vinylformic acid 2-propyl group heptyl ester, (methyl) vinylformic acid 2-butyl monooctyl ester, (methyl) 2-EHA, (methyl) Octyl acrylate, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) vinylformic acid 2-tertiary butyl heptyl ester, (methyl) vinylformic acid 3-sec.-propyl heptyl ester, (methyl) decyl acrylate, (methyl) vinylformic acid undecane ester, (methyl) vinylformic acid 5-methyl undecane ester, (methyl) vinylformic acid dodecane ester, (methyl) vinylformic acid 2-methyl dodecane ester, (methyl) vinylformic acid tridecane ester, (methyl) vinylformic acid 5-methyl tridecane ester, (methyl) vinylformic acid tetradecane ester, (methyl) vinylformic acid pentadecane ester, (methyl) vinylformic acid n-Hexadecane ester, (methyl) vinylformic acid 2-methyl n-Hexadecane ester, (methyl) vinylformic acid heptadecane ester, (methyl) vinylformic acid octadecane ester, (methyl) vinylformic acid nonadecane ester, (methyl) vinylformic acid eicosane ester.
7. the preparation method of acrylic polyester type hyper-dispersant described in claim 1-6, it is characterized in that, will under the condition that monomer A, monomers B and monomer C exist at polymerization starter, solvent exists or do not exist, use or do not use chain-transfer agent, carry out free radical random polymerization.
8. the preparation method of acrylic polyester type hyper-dispersant as claimed in claim 7, is characterized in that, under the condition that monomer A, monomers B and monomer C are existed at polymerization starter, chain-transfer agent and solvent, carries out polyreaction, and temperature of reaction is not higher than 90 ℃.
9. the preparation method of acrylic polyester type hyper-dispersant as claimed in claim 8, is characterized in that, described chain-transfer agent is normal-butyl mercaptan, lauryl mercaptan, stearyl-mercaptan, cyclohexyl mercaptan or Thiovanic acid.
10. the application of acrylic polyester type hyper-dispersant described in claim 1-6, is characterized in that, described acrylic polyester type hyper-dispersant is used for disperseing mineral dye, organic dye, or as dispersion, the abrasive of granular solids, liquid medium.
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