CN105713174A - Hyperbranched resin pigment dispersant, preparation method and color paste thereof, and applications of color paste - Google Patents
Hyperbranched resin pigment dispersant, preparation method and color paste thereof, and applications of color paste Download PDFInfo
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- CN105713174A CN105713174A CN201410718471.6A CN201410718471A CN105713174A CN 105713174 A CN105713174 A CN 105713174A CN 201410718471 A CN201410718471 A CN 201410718471A CN 105713174 A CN105713174 A CN 105713174A
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Abstract
The invention discloses a hyperbranched resin pigment dispersant. The hyperbranched resin pigment dispersant possesses a hyperbranched structure, and following functional groups: a, hydroxyl; b, oxethyl (-OC2H4-), and c, hydrophobic carbon chains containing 5 to 18 carbon atoms. The hyperbranched resin pigment dispersant is capable of separating and dispersing pigments, strong anchoring effect with pigment can be achieved, compatibility of pigment with main resin is improved, color paste paint forming stability is improved, chromatic aberration is reduced, and the hyperbranched resin pigment dispersant can be applied to aqueous systems.
Description
Technical field
The present invention relates to pigment dispersion and mill base field.Application more particularly, to a kind of hyperbranched resin pigment dispersing agent, preparation method and mill base and mill base.
Background technology
Pigment is as coloring agent, and only uniform and stable is dispersed in film, could well play coloring effect.At present, surface of pigments is modified by general commonly used surfactant and some low molecular coupling agents, changes the polarity of surface of pigments, to reduce reunion and the flocculation of pigment.But, in practical application prepared by pigment dispersion and mill base, however it remains mill base dispersion efficiency is low, the finished product paint aberration of preparation is big, and paint film has floating phenomenon.
Hyper-branched polyester is compared with traditional wire shaped polymer to be had: viscosity is relatively low, intermolecular without advantages such as chain tangle.The patent of invention that publication number is CN101353421A and CN103497319A all discloses a kind of polyester type hyperbranched pigment dispersing agent and preparation method thereof.This pigment dispersing agent is with ByType polyol is core molecule, wherein B representation hydroxy, and its degree of functionality y >=2, with ABxType polyhydroxy acid is for dispersing molecule, wherein A representation carboxy, B representation hydroxy, the degree of functionality of x representation hydroxy and x >=2, the method adopting vacuum fusion polycondensation obtains the polyester type hyperbranched polymer of a kind of thick end strips hydroxyl, carrying out esterification with anhydride at ambient pressure again, the compound of to be finally mono-epoxy-functional's other end again with one end be hydrophobicity long-chain reacts and prepares.This invention is a kind of hyperbranched, dendritic, polyester pigment dispersing agent containing hydroxy functional group and hydrophobicity long-chain Liang Zhong functional group with 3D structure.
The present invention further improves hyperbranched pigment dispersing agent so that it is can be applicable to water-based system.
Summary of the invention
First technical problem that the invention solves the problems that is to provide a kind of hyperbranched resin pigment dispersing agent, this dispersant can effectively separate and disperse pigment, form strong anchor cooperation use with pigment simultaneously, increase the compatibility of pigment and matrix resin, the stability of the lacquering of mill base, reduce aberration, can be applicable to water-based system.
The preparation method that second technical problem that the invention solves the problems that is to provide above-mentioned dispersant.
The 3rd technical problem that the invention solves the problems that is to provide the mill base containing above-mentioned dispersant.
The 4th technical problem that the invention solves the problems that is to provide the application containing above-mentioned dispersant mill base.
For solving above-mentioned first technical problem, the present invention adopts following technical proposals:
A kind of hyperbranched resin pigment dispersing agent, it has dissaving structure, and has following functional group simultaneously:
A. hydroxyl；
B. ethyoxyl (OC2H4-)；
C. the hydrophobic carbon chain of 5-18 carbon is contained.
Preferably, described hyperbranched resin pigment dispersing agent has structure as shown in formula (I),
In formula,For dissaving polymer skeleton, U is the alkyl group of isocyanates, R3For the hydrophobic carbon chain containing 5-18 carbon；Wherein, total functional group number of 12 x+y+k dissaving polymers, x, y, k, q is positive integer；Preferably, 12 x+y+k 80.
Preferably, described hyperbranched resin pigment dispersing agent has structure as shown in formula II,
In formula, R1It is C for carbon chain lengths2-C18The skeleton of anhydride, R2For the hydrophobic carbon chain containing 5-18 carbon, wherein total functional group number of 12 x+y+k+n dissaving polymers, x, y, k, n is positive integer；Preferably, 12 x+y+k+n 80.
Preferably, the number-average molecular weight of described hyperbranched resin pigment dispersing agent is 1500-20000, and solid content is 20%-90%, and its molecular weight distribution is 1-10.
For solving above-mentioned second technical problem, the present invention adopts following technical proposals.
The described hyperbranched resin pigment dispersing agent preparation method with formula (I) structure, including being made by step:
(1) by hyperbranched hydroxyl polyester and C5-C18Satisfied fatty acid, carry out under 60-180 DEG C of stirring condition esterification end capping reaction, the part of hydroxyl obtained is terminated by fatty acid esterification, with the hyperbranched hydroxyl polyester of hydrophobic carbon chain；
(2) poly glycol monomethyl ether and isophorone diisocyanate are reacted under inert gas shielding according to mol ratio 0.8 1.2:1; one isocyanate groups of isophorone diisocyanate is terminated by poly glycol monomethyl ether, forms the IPDI MPEG intermediate containing a reactive isocyanate groups；The hyperbranched hydroxyl polyester with hydrophobic carbon chain that IPDI MPEG intermediate and step (1) prepare is reacted, namely obtaining being provided simultaneously with hydroxyl, hydrophobic carbon chain, three kinds of functional groups of hydrophilic polyglycol monomethyl ether group have the hyperbranched resin pigment dispersing agent of structure as shown in formula (I).
Preferably, hyperbranched hydroxyl polyester described in step (1) is with ByType polyol is core molecule, with ABxType polyhydroxy acid for dispersing molecule, the polyester type hyperbranched polymer of a kind of thick end strips hydroxyl that vacuum fusion polycondensation obtains, the temperature of described vacuum fusion is 100-200 DEG C, wherein, A representation carboxy, B representation hydroxy, degree of functionality x 2, degree of functionality y 2.
Preferably, the solid hydroxyl value 160mgKOH/g of the described hyperbranched hydroxyl polyester of step (1), it is preferable that the solid hydroxyl value of described hyperbranched hydroxyl polyester is 250-550mgKOH/g.
Preferably, step (1) described C5-C18Satisfied fatty acid be linear chain structure.
The preparation method that one has the hyperbranched resin pigment dispersing agent of formula (II) structure, comprises the steps:
In formula, R1It is C for carbon chain lengths2-C18The skeleton of anhydride, R2For the hydrophobic carbon chain containing 5-18 carbon, wherein total functional group number of 12 x+y+k+n dissaving polymers, x, y, k, n is positive integer；Preferably, 12 x+y+k+n 80.
(1) by hyperbranched hydroxyl polyester and C5-C18Satisfied fatty acid, carry out under 60-180 DEG C of stirring condition esterification end capping reaction, the part of hydroxyl obtained is terminated by fatty acid esterification, with the hyperbranched hydroxyl polyester of hydrophobic carbon chain；
(2) hyperbranched hydroxyl polyester part of hydroxyl terminated by fatty acid esterification and anhydride join equipped with, in the reactor of solvent, reacting under 60-180 DEG C of stirring condition；The molal quantity of the anhydride added is the 10%-90% of hydroxy functional group molal quantity in hyperbranched hydroxyl polyester；
(3) the described reaction system acid number of detecting step (1), the ethylene oxidic ester adding the mono-epoxy-functional with hydrophobic carbon chain in backward reactor or (+)-2,3-Epoxy-1-propanol ether compound is stablized to acid number, under 60-180 DEG C of stirring condition, continue reaction stable to acid number, obtain the hyperbranched hydroxyl polyester with hydrophobic carbon chain；The ethylene oxidic ester of the mono-epoxy-functional with hydrophobic carbon chain added or the mole of glycidyl ether are 1-1.2:1 with the ratio of carboxyl functional group mole in step (1) product；
(4) poly glycol monomethyl ether and isophorone diisocyanate are reacted under inert gas shielding according to mol ratio 0.8-1.2:1; one isocyanate groups of isophorone diisocyanate is terminated by poly glycol monomethyl ether, forms the IPDI-MPEG intermediate containing a reactive isocyanate groups；The hyperbranched hydroxyl polyester with hydrophobic carbon chain that IPDI-MPEG intermediate and step (3) prepare is reacted, namely obtaining being provided simultaneously with hydroxyl, hydrophobic carbon chain, three kinds of functional groups of hydrophilic polyglycol monomethyl ether group have the hyperbranched resin pigment dispersing agent of structure as shown in formula (II).
Preferably, hyperbranched hydroxyl polyester described in step (1) is with ByType polyol is core molecule, with ABxType polyhydroxy acid for dispersing molecule, the polyester type hyperbranched polymer of a kind of thick end strips hydroxyl that vacuum fusion polycondensation obtains, the temperature of described vacuum fusion is 100-200 DEG C, wherein, A representation carboxy, B representation hydroxy, degree of functionality x 2, degree of functionality y 2.
Preferably, the solid hydroxyl value 160mgKOH/g of the described hyperbranched hydroxyl polyester of step (1), it is preferable that the solid hydroxyl value of described hyperbranched hydroxyl polyester is 250-550mgKOH/g.
Preferably: step (2) described anhydride is selected from hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrabydrophthalic anhydride, methyl tetrahydro phthalic anhydride, phthalic anhydride, maleic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, dodecenylsuccinic acid acid anhydride or trimellitic anhydride.
Preferably, the ethylene oxidic ester described in step (3) is the ethylene oxidic ester with branched carbon chain structure；Preferably, the ethylene oxidic ester of the described mono-epoxy-functional with hydrophobic carbon chain is selected from tertiary carbonic acid glycidyl ester, 2 ethyl hexanoic acid ethylene oxidic ester, p t butylbenzoic acid ethylene oxidic ester or glycidyl benzoate；The glycidyl ether of the mono-epoxy-functional of hydrophobic carbon chain described in step (3) is selected from C6-C18Alkyl glycidyl ether, epoxy active diluent AGE, cyclohexyl glycidyl ether, phenyl glycidyl ether, substituted-phenyl glycidyl ether, benzyl glycidyl ether or substituted benzyl glycidyl ether.
For solving above-mentioned 3rd technical problem, the present invention adopts following technical proposals.
A kind of mill base containing hyperbranched resin pigment dispersing agent includes:
A. at least one pigment, described pigment accounts for the 5-60wt% of mill base gross weight.
B. at least one hyperbranched resin pigment dispersing agent, described hyperbranched resin pigment dispersing agent accounts for the 5-60wt% of mill base gross weight.
Preferably, described mill base also includes resin, solvent and additive；Described mill base is preferably by the mixing of described hyperbranched resin pigment dispersing agent, pigment, resin, solvent and additive, be uniformly dispersed a kind of pigment dispersion prepared.
Preferably, one or more in titanium dioxide, carbon black, inorganic pigment, organic pigment, inorganic filler and antirust color stuffing of described pigment；
One or more in iron oxides, pucherite class, plumbous chromate class, strontium chromate, barba hispanica, chrome black and chrome green of described inorganic pigment；
One or more in phthalocyanines, diketopyrrolopyrrolecocrystals, quinacridine ketone, azo, benzimidazole ketone, Anthraquinones, 4 formyl-2-imide class and permanent violet of described organic pigment；
One or more in calcium carbonate, Kaolin, barium sulfate and Pulvis Talci of described inorganic filler；
One or more in polymer phosphate aluminum, zinc phosphate, barium metaborate, micaceous iron oxide or glass flake of described antirust color stuffing；
Described mixing, dispersion refer to pearl mill dispersion, concussion dispersion, high-speed stirred dispersion or planet stirring dispersion.
For solving above-mentioned 4th technical problem, the present invention adopts following technical proposals,
The application in heavy-duty antiseptic paint, coiled material paint, automobile coating and general industry and civilian paint of the mill base containing above-mentioned hyperbranched resin pigment dispersing agent,
Preferably, described mill base individually or is used in various paint after allotment.
Preferably, described allotment be add in mill base become owner of resin, crosslinked resin, solvent, additive are formulated as paint；
One or more in acrylic resin, polyester resin, alkyd resin, epoxy resin, vinylite and resins derived therefrom that above-mentioned resin is main body of described main resin；
One or more in amino resins, poly isocyanate and blocked isocyanate of described crosslinked resin.
Beneficial effects of the present invention is as follows:
The hyper-branched polyester pigment dispersing agent that the present invention adopts has a hydroxyl, hydrophobicity branching long-chain, the multiple pigment such as ammonia ester bond (-NH-COO) and ether (EO) epoxy-functional dispersing functional group.These functional groups and pigment form strong anchor cooperation use, and the introducing of hydrophilic poly glycol monomethyl ether (MPEG) simultaneously also can the application extension of hyperbranched resin to water-based system.The framing structure of the 3D of hyperbranched resin, forms interval to pigment, reduces the flocculation once again of dispersion or assembles probability.The remaining hydroxyl of hyperbranched resin can also carry out cross-linking reaction further with cross-linking agent, improves the compactness of overall paint film.The grinding very short time of the mill base containing hyperbranched pigment dispersing resin adopting the present invention can reach fineness requirement, uses it for finished product paint, and hot storage stability is good, can effectively slow down finished product paint precipitation and loose colour.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 illustrates the gas chromatography mass spectrometry collection of illustrative plates of embodiment 1 synthetic product；
Fig. 2 illustrates the gas chromatography mass spectrometry collection of illustrative plates of embodiment 5 synthetic product.
Detailed description of the invention
In order to be illustrated more clearly that the present invention, below in conjunction with preferred embodiment, the present invention is described further.It will be appreciated by those skilled in the art that following specifically described content is illustrative and be not restrictive, should not limit the scope of the invention with this.
Raw materials used:
1.BoltornH40, solid particle, Perstorp company provide, forth generation hyper-branched polyester, hydroxyl value is 470-500mgKOH/g.
2.BoltornH4001,50-55% solid containing light yellow liquid.Being thered is provided by Perstorp company, the derivant of forth generation hyper-branched polyester BoltornH40, its part of hydroxyl is esterified by the satisfied fatty acid of C6-C15.Hydroxyl value is calculated as 300-340mgKOH/g by solid content, and acid number is 2-8mgKOH/g.
3.DesmophenA870, acrylic resin, solid content is 70-75%, and hydroxyl equivalent is 575.Thered is provided by Nuplex company.
4.MPEG750, poly glycol monomethyl ether, the white solid of molecular weight 715-785, buy from Sigma-Aldrich.
5. tertiary carbonic acid glycidyl ester (CarduraE10), is provided by Momentive company.
R1+R2=7 carbon atoms
6. hexahydrophthalic anhydride (HHPA) is provided by new Japan Chemical company.
7.NPSWeatherBond: ippon Singapore WeatherBond exterior wall paint.
8.Tego755W: enlightening height aqueous dispersion.
9. butyl acetate (BA) and dibutyl tin laurate (DBTDL) are provided by Run Jie Reagent Company.
Embodiment 1 (9AH30-12.5%MPEG)
The synthesis of (a) 9AH30
Under nitrogen protection, being heated after 120 degree by 320 grams of H4001, stirring adds 39.59 grams of HHPA.Insulation reaction about 1 hour, the absworption peak of infrared spectrum display anhydride adds 61.63 grams of CarduraE10, is warming up to 140 degree after disappearing, and insulation reaction about 5 hours is until acid number is solid less than 10mgKOH/g. product 9AH30 containing about 67%.
The synthesis of (b) IPDI-MPEG750 adduct
Under nitrogen protection with under room temperature; to 61.75 grams of IPDI; 62.5 the mixture of gram butyl acetate (BA) solvent and 0.312 gram of DBTDL catalyst is slowly added to the mixed solution (weight ratio of MPEG750 and butyl acetate is 4:1) of 312.5 grams of MPEG750 and butyl acetate, within about 1.5 hours, add.Room temperature reaction is about 2-3 hour until the content (NCOwt%) of isocyanate functional group reaches theoretical value 2.14wt%.
The synthesis of (c) 9AH30-12.5%MPEG
Under nitrogen protection, 291 grams of 9AH30 are heated to 80 degree, is subsequently adding 0.291 gram of DBTDL, after stirring 5 minutes, then be slowly stirred the freshly prepd 116.3 grams of IPDI-MPEG750 adducts of addition.Insulation reaction about 2 hours is until NCOwt% is less than 0.1wt%.Products therefrom solid content is about 68%.
The structural formula of products therefrom 9AH30-12.5%MPEG is
In formulaR1For carbon hexatomic ring skeleton；R2Corresponding (III) structure,Wherein R5+R6=7 C；R3For the satisfied fatty acid carbon chain backbone of C6-C15, the meansigma methods of y is the meansigma methods of 22, x+n+k is: 64-22=42, and the relative scale of k, n, x is: 12.5%, 30%, 57.5%.
Fig. 1 is the gas chromatography mass spectrometry collection of illustrative plates of product 9AH30-12.5%MPEG of the present embodiment synthesis, can draw the structure of the product that embodiment 1 synthesizes from figure.
Table 1 is the analysis to peak each in Fig. 1.
Table 19AH30-12.5MPEG
Embodiment 2
The synthesis of (a) 9AH30
With embodiment 1
The synthesis of (b) IPDI-MPEG750 adduct
With embodiment 1
The synthesis of (c) 9AH30-25%MPEG
Under nitrogen protection, 230 grams of 9AH30 are heated to 80 degree, is subsequently adding 0.230 gram of DBTDL, after stirring 5 minutes, then be slowly stirred the freshly prepd 183.8 grams of IPDI-MPEG750 adducts of addition.Insulation reaction about 5 hours is until NCOwt% is less than 0.1wt%.Products therefrom solid content is about 69%.
The structural formula of products therefrom 9AH30-25%MPEG is
In formulaR1For carbon hexatomic ring skeleton；R2Corresponding (III) structure,Wherein R5+R6=7 C；R3For the satisfied fatty acid carbon chain backbone of C6-C15, the meansigma methods of y is the meansigma methods of 22, x+n+k is: 64-22=42, and the relative scale of k, n, x is: 25%, 30%, 45%.
Embodiment 3
The synthesis of (a) 9AH30
With embodiment 1
The synthesis of (b) IPDI-MPEG750 adduct
With embodiment 1
The synthesis of (c) 9AH30-50%MPEG
Under nitrogen protection, 160 grams of 9AH30 are heated to 80 degree, is subsequently adding 0.160 gram of DBTDL, after stirring 5 minutes, then be slowly stirred the freshly prepd 255.8 grams of IPDI-MPEG750 adducts of addition.Insulation reaction about 8 hours is until NCOwt% is less than 0.1wt%.Products therefrom solid content is about 70%.
The structural formula of products therefrom 9AH30-50%MPEG is
In formulaR1For carbon hexatomic ring skeleton；R2Corresponding (III) structure,Wherein R5+R6=7 C；R3For the satisfied fatty acid carbon chain backbone of C6-C15, the meansigma methods of y is the meansigma methods of 22, x+n+k is: 64-22=42, and the relative scale of k, n, x is: 50%, 30%, 20%.
Embodiment 4
The synthesis of (a) 9AH50
Under nitrogen protection, being heated after 120 degree by 240 grams of H4001, stirring adds 49.5 grams of HHPA.Insulation reaction about 2 hours, the absworption peak of infrared spectrum display anhydride adds 77.0 grams of CarduraE10, is warming up to 140 degree after disappearing, and insulation reaction about 5 hours is until acid number is solid less than 10mgKOH/g. product 9AH50 containing about 72%.
The synthesis of (b) IPDI-MPEG750 adduct
With embodiment 1
The synthesis of (c) 9AH50-12.5%MPEG
Under nitrogen protection, 289.5 grams of 9AH50 are heated to 80 degree, is subsequently adding 0.290 gram of DBTDL, after stirring 5 minutes, then be slowly stirred the freshly prepd 100.0 grams of IPDI-MPEG750 adducts of addition.Insulation reaction about 3 hours is until NCOwt% is less than 0.1wt%.Products therefrom solid content is about 72%.
The structural formula of products therefrom 9AH50-12.5%MPEG is
In formulaR1For carbon hexatomic ring skeleton；R2Corresponding (III) structure,Wherein R5+R6=7 C；R3For the satisfied fatty acid carbon chain backbone of C6-C15, the meansigma methods of y is the meansigma methods of 22, x+n+k is: 64-22=42, and the relative scale of k, n, x is: 12.5%, 50%, 37.5%.
Embodiment 5
The synthesis of (a) IPDI-MPEG750 adduct
With embodiment 1
The synthesis of (b) H4001-15%MPEG
Under nitrogen protection, 250.00 grams of H4001 are heated to 80 degree, is subsequently adding 0.142 gram of DBTDL, after stirring 5 minutes, then be slowly stirred the freshly prepd 157.82 grams of IPDI-MPEG750 adducts of addition.Insulation reaction about 2 hours is until NCOwt% is less than 0.1wt%.Products therefrom H4001-15%MPEG solid content is about 62%.
The structural formula of product H4001-15%MPEG is
In formula, R3Satisfied fatty acid carbon chain backbone for C6-C15；The meansigma methods of y is the meansigma methods of 22, x+k: 64-22=42, and the relative scale of k, x is: 15%, 85%.
Fig. 2 is the gas chromatography mass spectrometry collection of illustrative plates of product H4001-15%MPEG of the present embodiment synthesis, can draw the structure of the product that embodiment 5 synthesizes from figure.
Table 2 is the analysis to peak each in Fig. 2
Table 2H4001-15MPEG
Embodiment 6
The synthesis of (a) IPDI-MPEG750 adduct
With embodiment 1
The synthesis of (b) H4001-35%MPEG
Under nitrogen protection, 165.00 grams of H4001 are heated to 80 degree, is subsequently adding 0.094 gram of DBTDL, after stirring 5 minutes, then be slowly stirred the freshly prepd 243.05 grams of IPDI-MPEG750 adducts of addition.Insulation reaction about 3 hours is until NCOwt% is less than 0.1wt%.Products therefrom H4001-35%MPEG solid content is about 65%.
The structural formula of product H4001-35%MPEG is
In formula, R3Satisfied fatty acid carbon chain backbone for C6-C15；The meansigma methods of y is the meansigma methods of 22, x+k: 64-22=42, and the relative scale of k, x is: 35%, 65%.
Embodiment 7,8,9,10,11,12 is the application example at mill base and finished product paint
Mix in the ratio listed by table 1, feed the mixture into after grinder is ground 1-5 hour, carry out fineness test with Hegman fineness grind agent, until fineness is less than 5 μm.After mill base makes finished product paint according to standard recipe, product refers to grind chromatic aberration performance such as table 2.
The mass fraction of each material in table 1 colour paste system
In table 1, mixed solvent is the mixed solution of the arbitrary proportion of one or more in dimethylbenzene, butyl acetate or n-butyl alcohol.Grind the finished product paint that can be seen that aberration containing hyperbranched resin pigment dispersing agent from the finger of finished product paint and aberration is better than contrast sample mostly referring to grind.Particularly embodiment 1 and 4, has branched hydrophobic carbochain and hydrophilic polyglycol group hyperbranched resin dispersant referring to grind on aberration and is significantly better than contrast sample especially.
Finished product paint 1 in table 1, finished product paint 2, finished product paint 3, finished product paint 4, finished product paint 5, finished product paint 6, make finished product paint according to table 2 formula respectively.The classification of dihydroxypropyl resin and melmac and number slightly difference in finished product paint.
The mass fraction of each material in table 2. finished product paint
| Material name | Mass fraction |
| Dihydroxypropyl resin | 40-50 |
| Melmac | 10-20 |
| Mill base | 10 |
| Auxiliary agent | 5 |
| Mixed solvent | 25 |
| Add up to: | 100 |
Embodiment 13,14,15,16,17,18,19 is the application example at aqueous color paste and aqueous finished product paint
Mix in the ratio listed by table 3, feed the mixture into after grinder is ground 2 hours, carry out fineness test with Hegman fineness grind agent.Being joined by 10% mill base after NPSWeatherBond makes finished product paint, mill base and finished product paint refer to grind chromatic aberration performance such as table 3.
Comparing with existing traditional waterborne pigment dispersant Tego755W, under identical grinding condition, hyperbranched resin pigment dispersing agent can help pigment to arrive fineness requirement faster.Grinding aberration from finger, hyperbranched resin pigment dispersing agent can reach the effect suitable with Tego755W.
The mass fraction of each material in table 3 colour paste system
Embodiment 20-29
Repeat embodiment 1, institute is the difference is that CarduraE10 is changed to 2 ethyl hexanoic acid ethylene oxidic ester, p t butylbenzoic acid ethylene oxidic ester, glycidyl benzoate, C5-C18 alkyl glycidyl ether, epoxy active diluent AGE, cyclohexyl glycidyl ether, phenyl glycidyl ether and substituted-phenyl glycidyl ether, benzyl glycidyl ether or substituted benzyl glycidyl ether, and experimental results is similar.
Embodiment 30-39
Repeat embodiment 1, institute is the difference is that hexahydrophthalic anhydride (HHPA) is changed to methylhexahydrophthalic anhydride, tetrabydrophthalic anhydride, methyl tetrahydro phthalic anhydride, phthalic anhydride, maleic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, dodecenylsuccinic acid acid anhydride or trimellitic anhydride, and experimental results is similar.
Obviously; the above embodiment of the present invention is only for clearly demonstrating example of the present invention; and be not the restriction to embodiments of the present invention; for those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; here cannot all of embodiment be given exhaustive, every belong to apparent change that technical scheme extended out or the variation row still in protection scope of the present invention.
Claims (18)
1. a hyperbranched resin pigment dispersing agent, it is characterised in that: described hyperbranched resin pigment dispersing agent has dissaving structure, and has following functional group simultaneously:
A. hydroxyl；
B. ethyoxyl (OC2H4)；
C. the hydrophobic carbon chain of 5-18 carbon is contained.
2. hyperbranched resin pigment dispersing agent according to claim 1, it is characterised in that: described hyperbranched resin pigment dispersing agent has structure as shown in formula (I),
In formula,For dissaving polymer skeleton, U is the alkyl group of isocyanates, R3For the hydrophobic carbon chain containing 5-18 carbon；Wherein, total functional group number of 12 x+y+k dissaving polymers, x, y, k, q is positive integer；Preferably, 12 x+y+k 80.
3. hyperbranched resin pigment dispersing agent according to claim 2, it is characterised in that: described hyperbranched resin pigment dispersing agent has structure as shown in formula II,
In formula, R1It is C for carbon chain lengths2-C18The skeleton of anhydride, R2For the hydrophobic carbon chain containing 5-18 carbon, wherein total functional group number of 12 x+y+k+n dissaving polymers, x, y, k, n is positive integer；Preferably, 12 x+y+k+n 80.
4. according to described hyperbranched resin pigment dispersing agent arbitrary in claim 1-3, it is characterised in that: the number-average molecular weight of described hyperbranched resin pigment dispersing agent is 1500-20000, and solid content is 20%-90%, and its molecular weight distribution is 1-10.
5. the preparation method of a hyperbranched resin pigment dispersing agent as claimed in claim 2, it is characterised in that include being made by step:
(1) by hyperbranched hydroxyl polyester and C5-C18Satisfied fatty acid, carry out under 60-180 DEG C of stirring condition esterification end capping reaction, the part of hydroxyl obtained is terminated by fatty acid esterification, with the hyperbranched hydroxyl polyester of hydrophobic carbon chain；
(2) poly glycol monomethyl ether and isophorone diisocyanate are reacted under inert gas shielding according to mol ratio 0.8 1.2:1; one isocyanate groups of isophorone diisocyanate is terminated by poly glycol monomethyl ether, forms the IPDI MPEG intermediate containing a reactive isocyanate groups；The hyperbranched hydroxyl polyester with hydrophobic carbon chain that IPDI MPEG intermediate and step (1) prepare is reacted, namely obtaining being provided simultaneously with hydroxyl, hydrophobic carbon chain, three kinds of functional groups of hydrophilic polyglycol monomethyl ether group have the hyperbranched resin pigment dispersing agent of structure as shown in formula (I).
6. the preparation method of hyperbranched resin pigment dispersing agent according to claim 5, it is characterised in that: hyperbranched hydroxyl polyester described in step (1) is with ByType polyol is core molecule, with ABxType polyhydroxy acid for dispersing molecule, the polyester type hyperbranched polymer of a kind of thick end strips hydroxyl that vacuum fusion polycondensation obtains, the temperature of described vacuum fusion is 100-200 DEG C, wherein, A representation carboxy, B representation hydroxy, degree of functionality x 2, degree of functionality y 2.
7. the preparation method of hyperbranched resin pigment dispersing agent according to claim 5, it is characterized in that: the solid hydroxyl value 160mgKOH/g of the described hyperbranched hydroxyl polyester of step (1), preferably, the solid hydroxyl value of described hyperbranched hydroxyl polyester is 250-550mgKOH/g.
8. the preparation method of hyperbranched resin pigment dispersing agent according to claim 5, it is characterised in that: step (1) described C5‐C18Satisfied fatty acid be linear chain structure.
9. the preparation method of a hyperbranched resin pigment dispersing agent as claimed in claim 3, it is characterised in that:
(1) by hyperbranched hydroxyl polyester and C5-C18Satisfied fatty acid, carry out under 60-180 DEG C of stirring condition esterification end capping reaction, the part of hydroxyl obtained is terminated by fatty acid esterification, with the hyperbranched hydroxyl polyester of hydrophobic carbon chain；
(2) hyperbranched hydroxyl polyester part of hydroxyl terminated by fatty acid esterification and anhydride join equipped with, in the reactor of solvent, reacting under 60-180 DEG C of stirring condition；The molal quantity of the anhydride added is the 10%-90% of hydroxy functional group molal quantity in hyperbranched hydroxyl polyester；
(3) the described reaction system acid number of detecting step (1), the ethylene oxidic ester adding the mono-epoxy-functional with hydrophobic carbon chain in backward reactor or (+)-2,3-Epoxy-1-propanol ether compound is stablized to acid number, under 60-180 DEG C of stirring condition, continue reaction stable to acid number, obtain the hyperbranched hydroxyl polyester with hydrophobic carbon chain；The ethylene oxidic ester of the mono-epoxy-functional with hydrophobic carbon chain added or the mole of glycidyl ether are 1-1.2:1 with the ratio of carboxyl functional group mole in step (1) product；
(4) poly glycol monomethyl ether and isophorone diisocyanate are reacted under inert gas shielding according to mol ratio 0.8-1.2:1; one isocyanate groups of isophorone diisocyanate is terminated by poly glycol monomethyl ether, forms the IPDI-MPEG intermediate containing a reactive isocyanate groups；The hyperbranched hydroxyl polyester with hydrophobic carbon chain that IPDI-MPEG intermediate and step (3) prepare is reacted, namely obtaining being provided simultaneously with hydroxyl, hydrophobic carbon chain, three kinds of functional groups of hydrophilic polyglycol monomethyl ether group have the hyperbranched resin pigment dispersing agent of structure as shown in formula (II).
10. the preparation method of hyperbranched resin pigment dispersing agent according to claim 9, it is characterised in that: hyperbranched hydroxyl polyester described in step (1) is with ByType polyol is core molecule, with ABxType polyhydroxy acid for dispersing molecule, the polyester type hyperbranched polymer of a kind of thick end strips hydroxyl that vacuum fusion polycondensation obtains, the temperature of described vacuum fusion is 100-200 DEG C, wherein, A representation carboxy, B representation hydroxy, degree of functionality x 2, degree of functionality y 2.
11. the preparation method of hyperbranched resin pigment dispersing agent according to claim 9, it is characterized in that: the solid hydroxyl value 160mgKOH/g of the described hyperbranched hydroxyl polyester of step (1), preferably, the solid hydroxyl value of described hyperbranched hydroxyl polyester is 250-550mgKOH/g.
12. the preparation method of hyperbranched resin pigment dispersing agent according to claim 9, it is characterised in that: step (2) described anhydride is selected from hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrabydrophthalic anhydride, methyl tetrahydro phthalic anhydride, phthalic anhydride, maleic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, dodecenylsuccinic acid acid anhydride or trimellitic anhydride.
13. the preparation method of hyperbranched resin pigment dispersing agent according to claim 9, it is characterised in that: the ethylene oxidic ester of the mono-epoxy-functional with hydrophobic carbon chain described in step (3) is the ethylene oxidic ester with branched carbon chain structure；Preferably, described ethylene oxidic ester is selected from tertiary carbonic acid glycidyl ester, 2 ethyl hexanoic acid ethylene oxidic ester, p t butylbenzoic acid ethylene oxidic ester or glycidyl benzoate；The glycidyl ether of the mono-epoxy-functional of hydrophobic carbon chain described in step (3) is selected from C5-C18Alkyl glycidyl ether, epoxy active diluent AGE, cyclohexyl glycidyl ether, phenyl glycidyl ether, substituted-phenyl glycidyl ether, benzyl glycidyl ether or substituted benzyl glycidyl ether.
14. one kind containing the mill base of arbitrary described hyperbranched resin pigment dispersing agent in claim 1-4, it is characterised in that including:
A. at least one pigment, described pigment accounts for the 5-60wt% of mill base gross weight；
B. at least one hyperbranched resin pigment dispersing agent, described hyperbranched resin pigment dispersing agent accounts for the 5-60wt% of mill base gross weight.
15. mill base according to claim 14, it is characterised in that: described mill base also includes resin, solvent and additive；Described mill base is preferably by the mixing of hyperbranched resin pigment dispersing agent, pigment, resin, solvent and additive, be uniformly dispersed the pigment dispersion obtained.
16. the mill base according to claims 14 or 15, it is characterised in that: one or more in titanium dioxide, carbon black, inorganic pigment, organic pigment, inorganic filler and antirust color stuffing of described pigment；
One or more in iron oxides, pucherite class, plumbous chromate class, strontium chromate, barba hispanica, chrome black and chrome green of described inorganic pigment；
One or more in phthalocyanines, diketopyrrolopyrrolecocrystals, quinacridine ketone, azo, benzimidazole ketone, Anthraquinones, 4 formyl-2-imide class and permanent violet of described organic pigment；
One or more in calcium carbonate, Kaolin, barium sulfate and Pulvis Talci of described inorganic filler；
One or more in polymer phosphate aluminum, zinc phosphate, barium metaborate, micaceous iron oxide or glass flake of described antirust color stuffing；
Described mixing, dispersion refer to pearl mill dispersion, concussion dispersion, high-speed stirred dispersion or planet stirring dispersion.
17. the application that the mill base as described in any one of claim 14-16 is in heavy-duty antiseptic paint, coiled material paint, automobile coating and general industry and civilian paint, it is characterised in that: described mill base individually or is used in various paint after allotment.
18. application according to claim 17, it is characterised in that: described allotment refer to add in mill base become owner of resin, crosslinked resin, solvent, additive are formulated as paint；
One or more in acrylic resin, polyester resin, alkyd resin, epoxy resin, vinylite and resins derived therefrom that above-mentioned resin is main body of described main resin；
One or more in amino resins, poly isocyanate and blocked isocyanate of described crosslinked resin.
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| CN114716871A (en) * | 2022-04-15 | 2022-07-08 | 中国科学院理化技术研究所 | Modified pigment, preparation method and application thereof |
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| CN114621413B (en) * | 2022-04-08 | 2023-08-29 | 维新制漆（江西）有限公司 | Preparation method of aqueous polyurethane for grinding Y-type branched zero-VOC special color paste |
| CN114716871A (en) * | 2022-04-15 | 2022-07-08 | 中国科学院理化技术研究所 | Modified pigment, preparation method and application thereof |
| CN114716871B (en) * | 2022-04-15 | 2023-09-29 | 中国科学院理化技术研究所 | Modified pigment, preparation method and application thereof |
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