A kind of dispersing agent and preparation method thereof based on rosin derivativeTechnical field
The present invention relates to a kind of dispersing agents and preparation method thereof, more particularly to point of the coating and printing ink system containing solid particlePowder and preparation method thereof, the in particular to dispersing agent and preparation method thereof based on rosin derivative.
Background technique
Be widely applied in the industries such as coating, adhesive, ink, paint vehicle, colorant solid particle as coloring orFiller material.Particularly, granular solids (such as pigment and filler) are the important components of coating.They can not only assign paintingThe good covering power of layer, color abundant can also additionally provide improved physical property and chemically for coating compositionCan, including improve chemical resistance and thermal stability.In order to make being mixed into liquid medium of Pickering, higher machinery is neededPower.Thus it is common to use dispersing agent reduces these dispersion forces, to not only make the gross energy for needing to enter in system minimumChange, and jitter time also minimizes.Known dispersing agent is usually surface reactive material, these substances are added with seldom amountInto liquid medium, play the role of dispersion solid particle.
Patent CN105295500A discloses a kind of coating dispersant, and the coating dispersant is by acrylic acid, methacrylic acidMethyl esters, ethylene glycol, modification infusorial earth, initiator, sodium sulfite and neutralizer are prepared, and the dispersing agent being prepared into can reduceThe surface tension of water paint enhances the wetting effect to granules of pigments, makes the dispersion that granules of pigments is always stable in liquid phase, andCan firmly be combined rapidly with coating surface group, make pigment particles are stable to be suspended in aqueous solvent, make pigment obtain compared withGood dispersion, reaches optimal dispersion effect, by adding modification infusorial earth, improves dispersion effect and thinning effect, improvesIts stability.But the dispersing agent reacts complicated during the preparation process, and needs advanced processing diatomite, and to certain solid particlesDispersibility is poor.That is in the environment of existing heavy industrialization application, the narrow model of existing wetting dispersing agentIt encloses and has become obstacle, be applied in the system of coating and printing ink containing solid particle that dispersion effect is bad, lead to the viscosity of coating and printing inkExcessively high, glossiness is too low and turbidity is too high, reduces product quality.
Thus, the wetting dispersing agent of high compatibility can be shown with common resin and dicyandiamide solution by being badly in need of invention.
Summary of the invention
To solve the above-mentioned problems, the object of the present invention is to provide a kind of dispersing agent based on rosin derivative and its preparationsMethod especially shows the wetting dispersing agent of high compatibility with common resin and dicyandiamide solution, and the dispersing agent is for droppingLow viscosity and the glossiness and mist shadow of the coating and printing ink system comprising the wetting dispersing agent are not adversely affected.
There is provided a kind of to be suitable as wetting dispersing agent, institute based on rosin derivative for a technical solution of the inventionStating wetting dispersing agent is additive compound, and the additive compound has following general formula:
Wherein R1It is independently indicated in skeleton at each occurrence containing the polyether residue for repeating-C-O- structure or containing weightThe polyester residue of multiple-COO- structure；R2The amino residue for containing-NH- structure in skeleton is independently indicated when occurring every time.
Wherein, the residue R1When for polyethers, there is structure represented by following formula:
Wherein R1C is independently indicated at each occurrence1-C18Alkyl, C2-C18Alkenylene, C6-C18Aralkyl；-(CH2CH2O)m, wherein m is in the range of 0 to 100；-(CH2CH2CH2O)n, wherein n is in the range of 0 to 100；P is everyIt is secondary independently to indicate hydroxyl, methylol, primary amine groups, the group containing active hydrogen such as secondary amine when occurring.
The residue R1When for polyester, there is structure represented by following formula:
Wherein R2C is independently indicated at each occurrence1-C18Alkyl, C2-C18Alkenylene, C6-C18Aralkyl；Wherein R3?C is independently indicated when occurring every time1-C18Alkyl, C2-C18Alkenylene, C6-C18Aralkyl；Wherein, m is in the range of 0 to 100.
Another aspect provides a kind of methods for being used to prepare the wetting dispersing agent, pass through polyethers or polyesterFirst carry out esterification with rosin derivative, generate the compound containing double carboxyls, then with the compound containing amine active hydrogen withIts amidation process, this polymer can be used as pigment and filler.
Specifically, described method includes following steps:
(i) polyethers containing active hydrogen represented by least one following formula is provided
Wherein R1C is independently indicated at each occurrence1-C18Alkyl, C2-C18Alkenylene, C6-C18Aralkyl；-(CH2CH2O)m, wherein m is in the range of 0 to 100；-(CH2CH2CH2O)n, wherein n is in the range of 0 to 100；P is everyIt is secondary independently to indicate hydroxyl, methylol, primary amine groups, the group containing active hydrogen such as secondary amine when occurring；
(ii) or the polyester containing active hydrogen represented by least one following formula is provided
Wherein R2C is independently indicated at each occurrence1-C18Alkyl, C2-C18Alkenylene, C6-C18Aralkyl；
Wherein R3C is independently indicated at each occurrence1-C18Alkyl, C2-C18Alkenylene, C6-C18Aralkyl；
Wherein, m is in the range of 0 to 100；
(iii) at least one compound containing amine active hydrogen is provided；
(iV) so that above-mentioned polyethers or polyester and rosin derivative is first carried out esterification, generate the chemical combination containing double carboxylsObject, then with the compound containing amine active hydrogen and its amidation process, to form the dispersing agent.
In embodiments of the present invention, the esterification reaction process of polyethers or polyester and rosin derivative needs catalyst, rightThe catalyst such as toluenesulfonic acid, dibutyltin dilaurate, tetrabutyl titanate ester, four isobutyl group titanate esters.
In embodiments of the present invention, such as R1For polyethers, wherein polyether residue R1Selected from number-average molecular weight between 200The poly glycol monomethyl ether of~3000g/mol, one of polyethyleneglycol ether or polyethylene glycol monobutyl ether, also can be selected fromNumber-average molecular weight between 200~3000g/mol polypropylene glycol monomethyl ether, in polypropylene glycol list ether or polypropylene glycol monobutyl etherOne kind, perhaps selected from number-average molecular weight between 200~3000g/mol atactic polyether or selected from number-average molecular weight between 200The monoalkyl polyetheramine of~2000g/mol.
In embodiments of the present invention, such as R1For polyester, wherein polyester residue R1Preparation use pure and mild lactone as startingRaw material, the polyester number-average molecular weight synthesized is between 200~3000g/mol.
As the example of alcohol, normal propyl alcohol, isopropanol, n-butanol, n-amyl alcohol, n-hexyl alcohol, isohexyl alcohol, positive heptan can be usedOne of alcohol, n-octyl alcohol, isooctanol, n-nonyl alcohol or lauryl alcohol are a variety of.Preferably, using n-octyl alcohol or lauryl alcohol.
As the example of lactone, propiolactone, butyrolactone, δ-valerolactone, 6-caprolactone or C can be used1-8Alkyl replacesOne of 6-caprolactone or a variety of.Preferably, use 6-caprolactone as lactone.
Implement under the reaction condition that the esterification of pure and mild lactone can be known in the art, such as can be to toluene sulphurIn the presence of acid, dibutyltin dilaurate or tetrabutyl titanate ester catalyst about 80 DEG C to 180 DEG C at a temperature of implement.
In embodiments of the present invention, wherein the compound containing amine active hydrogen be selected from monoethanolamine, diethanol amine, threeEthanol amine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, polyethylene polyamine, polyethyleneimine, N- pyrrolidones, 1-(2- ethoxy) piperazine, 2-aminopyridine, 4-aminopyridine, 2- aminooimidazole, 4- aminooimidazole, 1- (3- aminopropyl) miaowAzoles, 1,3 hexamethylene dimethylamine are one or more in diamino-dicyclohexyl methane or isophorone diamine.
In embodiments of the present invention, wherein rosin derivative refers to maleic rosin or fumaric acid colophonium.
In embodiments of the present invention, the ratio between molar equivalent of the polyethers or polyester and rosin derivative is 1~1.2: 1In the range of.
In embodiments of the present invention, the ratio between molar equivalent of the compound of the amine active hydrogen and rosin derivative is 1~1.2: 1 range.
Compared with the prior art, the advantages of the present invention are as follows:
Polymer synthesized by the present invention utilizes excellent compatible of rosin derivative using rosin derivative as intermediateProperty, long-chain polyether or polyester segment are as wetting and steric hindrance segment in grafting, while double carboxyls and amine on rosin derivativeActive hydrogen compounds reaction combines solid particles surface using amino residue after reaction and carboxyl itself and anchors, of the inventionBranched polymer dispersing aid can provide excellent synthesis dispersion performance when dispersed particulate solids for resulting dispersion.
Specific embodiment
The present invention provides a kind of monomer mixtures to pass through polymer prepared by esterification and amidation process, this polymerIt can be used as the wetting dispersing agent preparation method for pigment and filler, to facilitate the understanding of the present invention, below with reference to embodimentTo invention is more fully described, following present presently preferred embodiments of the present invention.But the present invention can be with many notWith form realize, however it is not limited to embodiment described herein.On the contrary, the purpose for improving these embodiments is made to thisThe understanding of the disclosure of invention is more preferably thorough and comprehensive.
It is described as including in composition or in the case where comprising specific components, it is contemplated that this hair is not precluded in the compositionThe bright optional components being not directed to, and it is expected that the composition can be constituted or be formed by related component, or retouched in methodState be include or comprising specific process step in the case where, it is contemplated that the optional technique that is not directed to of the present invention is not precluded in this methodStep, and it is expected that this method can be constituted or be formed by related processing step.
Term " preferred " and " preferably " refer to, can provide the embodiment party of the present invention of certain benefits in some casesFormula.However, in the case that it is identical or other, other embodiments are also likely to be preferred.In addition, one or more preferred realThe narration for applying mode does not mean that other embodiments are disabled, and is not intended to and excludes other embodiments in the present inventionOutside range.
As used herein, "an", "the", "at least one" and " one or more " are used interchangeably.Therefore, exampleSuch as dispersion comprising "an" granular solids can be interpreted to indicate that the dispersion includes " one or more " granular solids.
For simplicity, some numberical ranges are only expressly disclosed herein.However, any lower limit can be with any upper limit groupClose the range for being formed and being not known and recording；And any lower limit can form the range for being not known and recording with other lower values, togetherAny upper limit of sample can combine the range to be formed and not yet explicitly be recorded with any other upper limit.In addition, recorded although being not known,Each point or single number between endpoints of ranges are included within the scope of this.Thus, each point or single number can be used as certainlyThe lower limit or the upper limit of body, which combine with any other point or single number or combine to be formed with other lower limits or the upper limit, not yet explicitly to be recordedRange.
Foregoing invention content of the invention is not intended to each disclosed embodiment or every kind of reality in the description present inventionExisting mode.Illustrative embodiments are more particularly exemplified described below.Many places in entire chapter application pass through a series of realitiesIt applies example and provides guidance, these embodiments can use in a variety of combinations.In various embodiments, described to enumerate only as generationTable group should not be construed as exhaustion.
Embodiment
Following embodiments more particularly describe present disclosure, these being only intended to illustrate property of embodiment are saidIt is bright, because carrying out various amendments in scope of the present disclosure and changing to be obvious for a person skilled in the art's.Unless otherwise stated, all parts, percentage and the ratio reported in following embodiment are by weight meter, Er QieshiApply that all reagents are all commercially available used in example and can be used directly without being further processed.
Embodiment 1
The synthesis of polyester segment
Petchem 1
Under nitrogen protection, by 186.33 parts of lauryl alcohol, 1710 parts of 6-caprolactone monomer, 1.9 parts of tetrabutyl titaniumAcid esters is added at room temperature in the four-hole boiling flask for being equipped with thermometer, overhead, gas access and condenser pipe, and is allowed toIt homogenizes.Heat riser is opened, is arranged 160 DEG C of reaction temperature, while opening stirring, mixing speed 100rpm is set, when reaction is mixedWhen conjunction object reaches about 160 DEG C, after maintaining thermotonus 18h, reaction is terminated, to obtain petchem 1.It is computed, countsAverage molecular weight is about 1896g/mol.
Petchem 2
Under nitrogen protection, by 130 parts of isooctanol, 1710 parts of 6-caprolactone monomer, 1.7 parts of tetrabutyl titanate esterIt is added in the four-hole boiling flask for being equipped with thermometer, overhead, gas access and condenser pipe at room temperature, and is allowed to evenChange.Heat riser is opened, is arranged 160 DEG C of reaction temperature, while opening stirring, mixing speed 100rpm is set, when reaction mixesWhen object reaches about 160 DEG C, after maintaining thermotonus 18h, reaction is terminated, to obtain petchem 2.It is computed, number is equalMolecular weight is about 1840g/mol.
Petchem 3
Under nitrogen protection, by 130 parts of isooctanol, 2850 parts of 6-caprolactone monomer, 3 parts of tetrabutyl titanate ester existsIt is added in the four-hole boiling flask for being equipped with thermometer, overhead, gas access and condenser pipe at room temperature, and is allowed to homogenize.Heat riser is opened, is arranged 160 DEG C of reaction temperature, while opening stirring, mixing speed 100rpm is set, when reaction mixture reachesWhen to about 160 DEG C, after maintaining thermotonus 18h, reaction is terminated, to obtain petchem 3.It is computed, counts equal moleculeAmount is about 2980g/mol.
The synthesis of rosin derivative-polyether/polyester segment
Rosin derivative-polyether/polyester segment 1
Under nitrogen protection, by 400 parts of maleic rosin, 1991 parts of .8 parts of petchem Isosorbide-5-Nitrae of dibutyl tinCinnamic acid tin is added at room temperature in the four-hole boiling flask for being equipped with thermometer, overhead, gas access and condenser pipe, and makesHomogenize.Heat riser is opened, is arranged 120 DEG C of reaction temperature, while opening stirring, mixing speed 100rpm is set, reaction is worked asWhen mixture reaches about 120 DEG C, after maintaining thermotonus 6h, reaction is terminated, to obtain rosin derivative-polyether/polyester chainSection 1.It is computed, number-average molecular weight is about 2296g/mol.
Rosin derivative-polyether/polyester segment 2
The synthesis of rosin derivative-polyether/polyester segment 2 is similar with rosin derivative-synthesis of polyether/polyester segment 1,The difference is that the petchem 3 using 3129 parts replaces petchem 1, it is computed, number-average molecular weight is about3380g/mol。
Rosin derivative-polyether/polyester segment 3
The synthesis of rosin derivative-polyether/polyester segment 3 is similar with rosin derivative-synthesis of polyether/polyester segment 1,The difference is that the poly glycol monomethyl ether (Mn=1000) using 1050 parts replaces petchem 1, it is computed, countsAverage molecular weight is about 1400g/mol.
Rosin derivative-polyether/polyester segment 4
The synthesis of rosin derivative-polyether/polyester segment 4 is similar with rosin derivative-synthesis of polyether/polyester segment 1,The difference is that the polyetheramine M2070 (Mn=2000) using 2100 parts replaces petchem 1, it is computed, number is divided equallySon amount is about 2470g/mol.
Rosin derivative-polyether/polyester segment 5
The synthesis of rosin derivative-polyether/polyester segment 5 is similar with rosin derivative-synthesis of polyether/polyester segment 1,The difference is that the polypropylene glycol monomethyl ether (Mn=400) using 420 parts replaces petchem 1, it is computed, number is equalMolecular weight is about 800g/mol.
The synthesis of dispersing agent
Dispersing agent 1
Under nitrogen protection, by 1,146 part of 2296 parts of rosin derivative-polyether/polyester segment of triethylene tetramine, addIt is added in the four-hole boiling flask for being equipped with thermometer, overhead, gas access and the condenser pipe with fractionating device, and is allowed toIt homogenizes.Heat riser is opened, is arranged 150 DEG C of reaction temperature, while opening stirring, mixing speed 100rpm is set, when reaction is mixedWhen conjunction object reaches about 150 DEG C, stop after maintaining reaction temperature reaction 4h, to obtain dispersing agent 1.
Dispersing agent 2-9
The preparation process of dispersing agent 2-9 is similar with the preparation process of dispersing agent 1, the difference is that polyethers-silicic acid usedEthyl ester branching is different with the type of amine-containing active hydrogen compounds and dosage is different, as shown in table 1 below.
Table 1
Embodiment 2: the dispersion and its thixotropic property of granular solids
By the dispersing aid 1,6,8 (solid content 30%) or commercially available dispersing aid of the invention of dosage shown in the following table 2BYK161 (solid content 30%) respectively with short oil-ity alcohol acid resin (solid content 60%), the coloring carbon black FW200 of powder type, thirdGlycol methyl ether acetate is mixed, and is dispersed 1 hour in Dispermat with 40 DEG C of bead, so that it is solid to obtain particleThe dispersion 1,2,3 and control dispersion of body.
Table 2
Note: the viscosity of the dispersion of granular solids uses No. 3 spindles using Brookfield LVDV-I Prime viscosimeterMeasurement
The result shows that the granules of pigments solid dispersions comprising inventive dispersant are shown compared with low viscosity and thixotropy,Show more excellent dispersibility.
Embodiment 3: the dispersion and its stably dispersing performance of granular solids
By 1 in embodiment 2,2,3 dispersions and NC resin are according to dispersion: NC=1: 10 ratio is uniformly mixed, with100 μm of wet-film thickness is applied in the comparison recording sheet of BYK-Gardner.After coating material is dried at room temperature for, useThe gloss of BYK-Gardner-turbidity tester is with the gloss of 60 ° of test angular measurement film and the turbidity of measurement film.
| Product source | Glossiness | Turbidity |
| Control | 89 | 124 |
| Dispersion 1 | 92 | 85 |
| Dispersion 2 | 93 | 89 |
| Dispersion 3 | 95 | 56 |
The result shows that the granules of pigments solid dispersions comprising inventive dispersant show higher gloss and lowerTurbidity shows more excellent dispersibility.