CN111234202B - Solvent-free high-nitrogen-content polycarboxyl type hyperdispersant as well as preparation method and application thereof - Google Patents

Solvent-free high-nitrogen-content polycarboxyl type hyperdispersant as well as preparation method and application thereof Download PDF

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CN111234202B
CN111234202B CN202010123502.9A CN202010123502A CN111234202B CN 111234202 B CN111234202 B CN 111234202B CN 202010123502 A CN202010123502 A CN 202010123502A CN 111234202 B CN111234202 B CN 111234202B
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diglycidyl ether
ether
hyperdispersant
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solvent
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CN111234202A (en
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黄月文
王斌
宋斌
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Guoke Guanghua Fine Chemical Incubator Nanxiong Co ltd
Guoke Guanghua Nanxiong New Materials Research Institute Co ltd
Guangzhou Chemical Co Ltd of CAS
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Guoke Guanghua Nanxiong New Materials Research Institute Co ltd
Nanxiong Cas Incubator Operation Co ltd
Guangzhou Chemical Co Ltd of CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C08G65/3324—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof cyclic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/001—Pigment pastes, e.g. for mixing in paints in aqueous medium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/003—Pigment pastes, e.g. for mixing in paints containing an organic pigment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular

Abstract

The invention discloses a solvent-free high-nitrogen-content polycarboxyl hyperdispersant, and a preparation method and application thereof. The hyperdispersant is prepared by carrying out local end capping and primary chain extension on 2 molar parts of polyamine containing 2-6 nitrogen atoms, 0.5-1 molar part of monoepoxy compound and 1 molar part of polyether polyol diglycidyl ether at room temperature and in a heating environment, carrying out secondary and tertiary chain extension on the polyether polyol diglycidyl ether or micromolecule polyglycidyl ether, and then carrying out ring opening reaction on the polyether polyol diglycidyl ether or micromolecule polyglycidyl ether or carrying out addition reaction on the polyether polyol diglycidyl ether or micromolecule polyglycidyl ether and cyclic anhydride to form a solvent-free polycarboxylic compound type polyether-based hyperdispersant. The hyper-dispersant contains a large amount of strongly coordinated N atoms, carboxyl, hydroxyl, carbonyl, acylamino, amino and the like to form a multidentate ligand, has strong stabilizing and dispersing effects on metal atoms or ions, and has wide application prospects in the fields of printing ink, pigments, coatings, ceramics, medicines and the like.

Description

Solvent-free high-nitrogen-content polycarboxyl type hyperdispersant as well as preparation method and application thereof
Technical Field
The invention belongs to the field of fine chemical engineering, and particularly relates to a solvent-free high-nitrogen-content polycarboxyl type hyperdispersant, and a preparation method and application thereof.
Background
Pigment color paste is one of indispensable components of ink or paint, pigment particles are required to be dispersed in a medium by a dispersing agent when various color pastes are prepared, the traditional dispersing agent such as polyacrylate plays a certain dispersion stabilizing role on inorganic pigment particles due to adsorption and interparticle charge repulsion, but the interaction of dispersing agent molecules on the surfaces of the pigment particles, particularly organic pigments, is not firm, and further dispersed particles are aggregated or precipitated again. The hyper-dispersant is a special polymer type multifunctional wetting dispersing auxiliary agent, overcomes the limitation of the traditional dispersant on the molecular structure, and simultaneously contains a solvation group and an anchoring group. At present, the application of the hyper-dispersant is very wide, and the hyper-dispersant comprises a water-based type, an oil-based type and a water-oil universal type, and is mainly used for color paste, printing ink, coating, ceramics, cement concrete, medicines, magnetic powder, biological materials, filling plastics and the like.
The polycarboxylic acid type hyperdispersants are the most commonly used ones, in which the solvating groups are polyether groups and a large number of carboxyl groups are anchoring groups. However, these single carboxyl groups have limited complexing stabilizing effects on metal ions on the surface of many solid particles. In addition, the common methods for preparing the hyperdispersant all use a solvent as a medium, particularly when an organic solvent is used as a reaction medium, the solvent has adverse effects on human health and environment, does not accord with the development trend of environmental protection, and limits the application of the hyperdispersant in an aqueous system. The solvent-free oil-water universal type hyperdispersant is an important development direction. Meanwhile, the polycarboxylic acid type hyperdispersant containing only oxyhydrogen elements only contains electron-rich groups COOH and COO - And atom O provides coordination to electron-deficient metal ions, the resulting coordination complexes are not sufficiently stable, and thus they have poor dispersion stability to pigments or inks containing metal ions.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention mainly aims to provide the solvent-free high-nitrogen-content polycarboxyl type hyperdispersant with high dispersion stability and the preparation method thereof.
The invention also aims to provide the solvent-free high-nitrogen-content polycarboxyl hyperdispersant and application thereof in water-based or oil-based color pastes, colored coatings and colored ink containing metal pigments.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a solvent-free high-nitrogen-content polycarboxyl type hyperdispersant comprises the following steps:
(1) Slowly adding 0.5-1 molar part of monoepoxy compound and 1 molar part of polyether polyol diglycidyl ether into 2 molar parts of polyamine containing 2-6 nitrogen atoms under stirring, keeping the temperature of the mixed solution at 15-40 ℃, continuing to react for 3-24 hours after the addition is finished, then heating to 50-70 ℃ for 2-6 hours, and cooling;
(2) Slowly adding 0.25-0.5 molar part of glycidyl ether into the solution obtained in the step (1) while stirring, keeping the temperature of the mixed solution at 15-50 ℃, continuing to react for 4-24 hours after the addition is finished, then heating to 50-60 ℃, reacting for 0-6 hours, and cooling; the reaction in the step (2) can be repeated twice, and the mole fraction of the total epoxy groups in the glycidyl ether is 1-1.5;
(3) Slowly adding 4-12 molar parts of one of cyclic anhydride or acrylic acid into the solution obtained in the step (2) under stirring, then reacting for 3-8 hours at 50-100 ℃, and cooling to obtain a solvent-free high-nitrogen-content polycarboxylic super-dispersant;
the total amount of the polyether glycol diglycidyl ether in the step (1) and the polyethylene glycol group in the glycidyl ether in the step (2) is 50 to 85wt percent of the total amount of the polyethylene glycol group and the polypropylene glycol group.
Preferably, the cyclic anhydride in step (3) is at least one of maleic anhydride, succinic anhydride, methylhexahydrophthalic anhydride and methyltetrahydrophthalic anhydride, and the molar fraction of all cyclic anhydrides in step (3) does not exceed the molar fraction of active hydrogen of the polyamine.
Preferably, the glycidyl ether in the step (2) is one or more of polyether polyol diglycidyl ether, micromolecular diglycidyl ether and micromolecular triglycidyl ether; when the reaction in the step (2) is repeated twice, the mole number of epoxy groups in the glycidyl ether is decreased progressively; the molecular weight of the polyether glycol diglycidyl ether in the step (1) is 300-2000.
Preferably, the polyether polyol diglycidyl ether described in step (2) has a molecular weight of 300 to 2000.
Preferably, the total amount of the polyethylene glycol groups in the polyether polyol diglycidyl ether in the step (1) and the glycidyl ether in the step (2) is 60 to 80wt% of the total amount of the polyethylene glycol groups and the polypropylene glycol groups.
Preferably, the dropping time of the slow addition in the step (1) is 3 to 5 hours; the dropping speed of the slow adding in the step (2) is 0.3 to 1 g/min; the dripping time of the slow addition in the step (3) is 0.5 to 1 hour.
Preferably, the monoepoxy compound in step (1) is at least one of benzyl glycidyl ether, phenyl glycidyl ether, alkyl phenyl glycidyl ether and alkyl glycidyl ether;
the polyether polyol diglycidyl ether in the step (1) and the step (2) is one of polyethylene glycol-polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether;
the polyamine in the step (1) is one of ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine;
the micromolecule diglycidyl ether in the step (2) is one of ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether and cyclohexanediol diglycidyl ether;
the micromolecular triglycidyl ether in the step (2) is one of trimethylolpropane triglycidyl ether and glycerol triglycidyl ether.
The hyperdispersant prepared by any method is applied to a color paste dispersion system. Color pastes are one component of paints or inks. The application is to directly apply the obtained solvent-free high-nitrogen-content polycarboxyl type hyperdispersant to an aqueous or oily dispersion system without neutralization; or the solvent-free high-nitrogen-content polycarboxylic type hyperdispersant is dispersed in water in advance, and an appropriate amount of alkali is added to partially or completely neutralize the carboxylic acid in the water-based dispersion system.
The application of the hyperdispersant is in water-based or oil-based paint or ink.
The hyper-dispersant prepared by the invention has a remarkably different dispersion stabilizing effect compared with the traditional dispersant polyacrylic acid or polyacrylate on pigments, printing ink or coatings containing metal ions. The traditional polyacrylic acid or polyacrylate dispersant is quickly separated out in an oily system due to the compatibility problem, is quickly separated out and separated out in an aqueous system, has only a charge stabilizing effect on metal ions in the pigment, and has extremely limited stability. The hyperdispersant prepared by the invention is prepared by carrying out local end capping and primary chain extension reaction on polyamine containing 2-6 nitrogen atoms, monoepoxy compound and polyether polyol diglycidyl ether at room temperature and in a heating environment, then carrying out secondary and tertiary chain extension on the polyether polyol diglycidyl ether or micromolecule polyglycidyl ether, wherein hydroxyl generated by ring opening of residual N-H and epoxy groups further carries out ring opening reaction on cyclic anhydride, or the residual N-H carries out addition reaction on acrylic acid to form a solvent-free high-nitrogen-content polycarboxylic hyperdispersant which takes polyether as a solvating group and carbonyl (C = O), COO, OH and N atoms as anchoring groups or atoms, and the anchoring groups and atoms construct a stable cyclic multidentate coordination compound for metal ions, so that the pigment containing the metal ions presents high dispersibility and stability in an aqueous or oily medium under the stabilizing action of the solvating groups in the dispersant. The long carbon chain, benzene ring, polypropylene glycol (PPO) and carbonyl in the hyperdispersant are helpful for oleophylicity, and the polyoxyethylene ether (polyethylene glycol, PEO) group and COO group - OH and N are beneficial to hydrophilicity, so that dual purposes of oil and water are realized. In addition, the hyperdispersant disclosed by the invention does not need an organic solvent and water as media in the preparation process, is free of VOC, and has the remarkable characteristics of environmental protection, energy conservation and emission reduction.
Compared with the prior art, the invention has the following outstanding characteristics:
(1) The paint does not contain any solvent, does not contain VOC, is environment-friendly, energy-saving and emission-reducing;
(2) Can be used for both oily systems and aqueous dispersion systems;
(3) Has high dispersion stability to pigment with metal ion, especially transition metal ion, on the surface.
Drawings
FIG. 1 is an IR spectrum of a hyperdispersant SD1 prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1
A solvent-free high-nitrogen-content polycarboxyl hyperdispersant is prepared by the following method:
(1) 1 molar part of benzyl glycidyl ether XY692 and 1 molar part of polyethylene glycol-polypropylene glycol diglycidyl ether (average molecular weight is 1000, structure is CH) are stirred 2 (O)CHCH 2 O-(PPO)1-PEO-(PPO)2-CH 2 CH(O)CH 2 Wherein PEO =609, (PPO) 1+ (PPO) 2= 261) is slowly dripped into 2 molar parts of Ethylenediamine (EDA) cooled by a water bath, the dripping time is 4 hours, the reaction is exothermic, the temperature of the mixed solution is kept between 15 ℃ and 40 ℃, the reaction is continued for 24 hours after the dripping is finished, then the temperature is increased to 50 ℃ for reaction for 6 hours, and the reaction is cooled to room temperature, so that polyether which is mainly subjected to chain extension once and contains a plurality of active N-H bonds and is shown as the following formula is obtained:
(XY692)NH-CH 2 CH 2 NH-CH 2 CH(OH)CH 2 O-(PPO)1-PEO-(PPO)2-CH 2 CH(OH)CH 2 -NHCH 2 CH 2 NH 2 。
(2) Then slowly dropwise adding 0.33 molar parts of trimethylolpropane triglycidyl ether XY636 under stirring, wherein the dropping speed is 0.3 g/min, keeping the temperature of the mixed solution at 15-40 ℃, continuing to react for 24 hours after the dropwise adding is finished, and cooling to room temperature to obtain the secondary chain-extended polyether mainly containing multiple active N-H bonds shown as the following formula:
[(XY692)NH-CH 2 CH 2 NH-CH 2 CH(OH)CH 2 O-(PPO)1-PEO-(PPO)2-CH 2 CH(OH)CH 2 -NHCH 2 CH 2 NH-] 3 XY636。
(3) Finally, 8 molar parts of maleic anhydride is slowly added under stirring for 1 hour, and then the mixture reacts for 3 hours at 80 ℃ and is cooled to obtain the solvent-free high-nitrogen-containing polycarboxyl hyper-dispersant SD1. The SD1 infrared spectrogram is shown in figure 1.
As can be seen from FIG. 1, at 3462cm -1 The broad absorption peak at (A) is the stretching vibration peak of the O-H bond in the carboxyl group, 3278cm -1 Is the stretching vibration peak of the N-H bond, 2871cm -1 Is the stretching vibration peak of the C-H bond, 1726cm -1 Is the stretching vibration peak of carbonyl in ester group, 1631.5cm -1 Is the absorption peak of carbonyl stretching vibration in the compound of amide, carboxylic acid and amine, 1576cm -1 Is the bending vibration peak of N-H on amide, and shows that the hyperdispersant contains rich groups with coordination and complexation stabilizing effects on metal ions, particularly transition metal ions, such as O-H, N-H, COOH, COO-, CONH and the like, and the groups (COO) are rich in electrons - ) And atom (N, O) containing lone pair of electrons jointly act on the electron-deficient metal ions to form a multidentate coordination complex with stable ring shape; 1107cm -1 The nearby strong absorption peak is a characteristic absorption peak of polyether C-O-C, is a solvation chain and plays a role in stable dispersion in a medium; 3051cm -1 Is a C-H stretching vibration absorption peak of C = C-H.
Example 2
A solvent-free high-nitrogen-content polycarboxyl type hyperdispersant is prepared by the following method:
(1) And (2) the steps are the same as example 1;
(3) And finally, slowly adding 4 molar parts of maleic anhydride under stirring, completing the addition within 0.5 hour, then reacting for 3 hours at 80 ℃, and cooling to obtain the solvent-free high-nitrogen-content polycarboxyl type hyperdispersant SD1-2.
Example 3
A solvent-free high-nitrogen-content polycarboxyl hyperdispersant is prepared by the following method:
(1) 0.5 molar part of o-tolyl glycidyl ether and 1 molar part of polyethylene glycol-polypropylene glycol diglycidyl ether (average molecular weight 2000, structure CH) were added under stirring 2 (O)CHCH 2 O-(PEO)1-PPO-(PEO)2-CH 2 CH(O)CH 2 Wherein PPO =748, (PEO) 1+ (PEO) 2= 1122) slowly dripping into 2 molar parts of triethylene tetramine cooled by a water bath for 4 hours, reacting to release heat at the moment, keeping the temperature of a mixed solution at 15-40 ℃, continuing to react for 12 hours after dripping is finished, then heating to 70 ℃, reacting for 2 hours, and cooling to room temperature;
(2) Then, slowly adding 0.5 molar part of polyethylene glycol diglycidyl ether (with the average molecular weight of 350 and PEO = 220) while stirring for secondary chain extension reaction, wherein the dropping speed is 0.5 g/min, keeping the temperature of the mixed solution at 15-50 ℃, continuing the reaction for 12 hours after the dropping is finished, then heating to 50 ℃ for reaction for 2 hours, and cooling to room temperature;
slowly adding 0.25 molar part of propylene glycol diglycidyl ether under stirring for three chain extension reactions, wherein the dropping speed is 1 g/min, keeping the temperature of the mixed solution at 15-40 ℃, and continuing to react for 24 hours after the dropping is finished;
(3) And finally, slowly adding 7 molar parts of succinic anhydride and 1 molar part of methyltetrahydrophthalic anhydride under stirring, finishing the addition for 1 hour, then reacting for 7 hours at 55 ℃, and cooling to obtain the solvent-free high-nitrogen-containing polycarboxyl hyper-dispersant SD2.
Example 4
A solvent-free high-nitrogen-content polycarboxyl type hyperdispersant is prepared by the following method:
(1) And (2) the same procedure as in example 3;
(3) And finally, slowly adding 3 molar parts of succinic anhydride and 1 molar part of methyltetrahydrophthalic anhydride under stirring, finishing the addition within 0.5 hour, then reacting for 7 hours at 55 ℃, and cooling to obtain the solvent-free high-nitrogen-containing polycarboxyl type hyperdispersant SD2-2.
Example 5
A solvent-free high-nitrogen-content polycarboxyl hyperdispersant is prepared by the following method:
(1) Slowly dropwise adding 1 mol part of phenyl glycidyl ether and 1 mol part of polypropylene glycol diglycidyl ether (average molecular weight is 500,PPO = 370) into 2 mol parts of tetraethylenepentamine cooled by water bath under stirring, wherein the dropwise adding time is 4 hours, the reaction releases heat, the temperature of the mixed solution is kept between 15 and 40 ℃, the reaction is continued for 4 hours after the dropwise adding is finished, then the temperature is increased to 50 ℃, the reaction is continued for 4 hours, and the mixed solution is cooled to room temperature;
(2) Then, slowly adding 0.5 molar part of polyethylene glycol diglycidyl ether (with average molecular weight of 1500, PEO = 1370) while stirring for secondary chain extension reaction, wherein the dropping speed is 1 g/min, keeping the temperature of the mixed solution at 15-50 ℃, continuing to react for 12 hours after the dropping is finished, then heating to 50 ℃ for reaction for 2 hours, and cooling to room temperature;
slowly adding 0.25 molar part of ethylene glycol diglycidyl ether under stirring for three times of chain extension reaction, wherein the dropping speed is 0.5 g/min, keeping the temperature of the mixed solution at 15-40 ℃, and continuing to react for 16 hours after the dropping is finished;
(3) Finally, slowly adding 8 molar parts of acrylic acid under stirring, finishing the addition for 1 hour, then reacting for 7 hours at 70 ℃, reacting for 1 hour at 100 ℃, and cooling to obtain the solvent-free high-nitrogen-containing polycarboxyl type hyperdispersant SD3.
Example 6
A solvent-free high-nitrogen-content polycarboxyl hyperdispersant is prepared by the following method:
(1) And (2) the same procedure as in example 5;
(3) And finally, slowly adding 4 molar parts of acrylic acid under stirring, completing the addition within 0.5 hour, then reacting at 70 ℃ for 7 hours, reacting at 100 ℃ for 1 hour, and cooling to obtain the solvent-free high-nitrogen-content polycarboxyl type hyperdispersant SD3-2.
Example 7
A solvent-free high-nitrogen-content polycarboxyl hyperdispersant is prepared by the following method:
(1) Slowly adding 0.5 molar part of octyl glycidyl ether, 0.5 molar part of benzyl glycidyl ether and 1 molar part of polyethylene glycol diglycidyl ether (average molecular weight is 660, PEO = 530) into 2 molar parts of pentaethylenehexamine cooled by a water bath under stirring, dropwise adding for 4 hours, keeping the temperature of the mixed solution at 15-40 ℃, continuing to react for 12 hours after dropwise adding is finished, then heating to 50 ℃, reacting for 5 hours, and cooling to room temperature;
(2) Then, slowly adding 0.5 molar part of polypropylene glycol diglycidyl ether (the average molecular weight is 450, PPO = 320) while stirring for secondary chain extension reaction, wherein the dropping speed is 1 g/min, keeping the temperature of the mixed solution at 15-50 ℃, continuing to react for 4 hours after the dropping is finished, then heating to 50 ℃ for reaction for 5 hours, and cooling to room temperature;
(3) And finally, slowly adding 10 molar parts of maleic anhydride and 2 molar parts of methylhexahydrophthalic anhydride under stirring, finishing the addition for 1 hour, then reacting for 3 hours at 80 ℃, and cooling to obtain the solvent-free high-nitrogen-containing polycarboxyl hyper-dispersant SD4.
Example 8
A solvent-free high-nitrogen-content polycarboxyl hyperdispersant is prepared by the following method:
(1) And (2) the same procedure as in example 7;
(3) And finally, slowly adding 2 molar parts of maleic anhydride and 2 molar parts of methylhexahydrophthalic anhydride under stirring, finishing the addition within 0.5 hour, reacting at 80 ℃ for 3 hours, and cooling to obtain the solvent-free high-nitrogen-containing polycarboxyl hyperdispersant SD4-2.
Application example 1:
(1) Taking 35 g of copper phthalocyanine, adding 63 g of water, stirring at a high speed, and quickly standing to show a layering phenomenon; then 2 g of SD3 is added, high-speed stirring is carried out for 3 minutes, and the mixture is kept stand for 30 days and 60 days to observe the stability of the mixture respectively;
(2) Taking 35 g of copper phthalocyanine, adding 63 g of water, stirring at a high speed, and quickly showing a layering phenomenon after standing; then 2 g of SD3-2 is added, high-speed stirring is carried out for 3 minutes, and the mixture is kept stand for 30 days and 60 days to observe the stability of the mixture respectively;
(3) Taking 35 g of copper phthalocyanine, adding 63 g of water, stirring at a high speed, and quickly standing to show a layering phenomenon; then adding 2 g of SD1, stirring at high speed for 3 minutes, standing for 30 days and 60 days, and observing the stability of the mixture respectively;
(4) Taking 35 g of copper phthalocyanine, adding 63 g of water, stirring at a high speed, and quickly showing a layering phenomenon after standing; then adding 2 g of SD1-2, stirring at high speed for 3 minutes, standing for 30 and 60 days, and observing the stability of the mixture respectively;
(5) Taking 35 g of copper phthalocyanine, adding 63 g of water, stirring at a high speed, and quickly standing to show a layering phenomenon; then adding 2 g of SD4-2, stirring at high speed for 3 minutes, standing for 30 and 60 days, and observing the stability of the mixture respectively;
(6) Taking 35 g of copper phthalocyanine, adding 60 g of water, stirring at a high speed, and quickly standing to show a layering phenomenon; then, mixing and stirring 2 g of SD4-2, 3 g of water and 0.12 g of NaOH to dissolve to form 5.12 g of partially neutralized SD4-2 solution, adding the partially neutralized SD4-2 solution into the mixture of the copper phthalocyanine and the water, stirring at a high speed for 3 minutes, standing for 30 and 60 days, and observing the stability of the mixture respectively;
(7) Taking 35 g of copper phthalocyanine, adding 60 g of water, stirring at a high speed, and quickly standing to show a layering phenomenon; then 5 g of 40wt% sodium polyacrylate SPA1 (average molecular weight is 3000, all carboxyl groups in polyacrylic acid are converted into sodium carboxylate) aqueous solution is added, high-speed stirring is carried out for 3 minutes, and the stability is observed after standing for 30 days and 60 days respectively;
(8) Taking 35 g of copper phthalocyanine, adding 60 g of water, stirring at a high speed, and quickly standing to show a layering phenomenon; then 5 g of 40wt% sodium polyacrylate SPA2 (average molecular weight is 3000, half of carboxyl in polyacrylic acid is converted into sodium carboxylate) aqueous solution is added, high-speed stirring is carried out for 3 minutes, and the stability is observed after standing for 30 days and 60 days respectively;
the results of the experiments in (1) to (8) are shown in Table 1.
Application example 2:
(1) Taking 30 g of cobalt acetate, adding 70 g of water, heating to 70 ℃ to dissolve the cobalt acetate to prepare a saturated solution, and cooling to separate out a large amount of crystals; then heating until re-dissolving, adding 3 g SD1, stirring at high speed for 3 min, standing for 30 and 60 days, and observing the stability of the mixture respectively;
(2) Taking 30 g of cobalt acetate, adding 70 g of water, heating to 70 ℃ to dissolve the cobalt acetate to prepare a saturated solution, and cooling to separate out a large amount of crystals; then heating until re-dissolving, adding 3 g SD1-2, stirring at high speed for 3 min, standing for 30 and 60 days, and observing the stability;
(3) 30 g of cobalt acetate, 70 g of water are added, the mixture is heated to 70 ℃ to be dissolved to prepare saturated solution, and a large amount of crystals are separated out after the saturated solution is cooled; then heating until re-dissolving, adding 3 g SD4, stirring at high speed for 3 min, standing for 30 and 60 days, and observing the stability of the mixture;
(4) 30 g of cobalt acetate, 70 g of water are added, the mixture is heated to 70 ℃ to be dissolved to prepare a saturated solution, and a large amount of crystals are separated out after cooling; then heating until re-dissolving, adding 3 g SD4-2, stirring at high speed for 3 min, standing for 30 and 60 days, and observing the stability;
(5) Taking 30 g of cobalt acetate, adding 65.5 g of water, heating to 70 ℃ to dissolve the cobalt acetate to prepare a saturated solution, and cooling to separate out a large amount of crystals; then heating until re-dissolving, adding 7.5 g of 40wt% sodium polyacrylate SPA1 aqueous solution, stirring at high speed for 3 minutes, standing for 30 and 60 days, and observing the stability of the mixture respectively;
(6) Taking 30 g of cobalt acetate, adding 65.5 g of water, heating to 70 ℃ to dissolve the cobalt acetate to prepare a saturated solution, and cooling to separate out a large amount of crystals; then heating until re-dissolving, adding 7.5 g of 40wt% sodium polyacrylate SPA2 aqueous solution, stirring at high speed for 3 minutes, standing for 30 and 60 days, and observing the stability of the mixture respectively;
the results of the experiments in (1) to (6) are shown in Table 1.
Application example 3:
(1) Taking 10 g of cobalt acetate, adding 70 g of isododecane, refluxing and heating to 100 ℃, keeping the temperature for 2 hours, obviously showing that the suspension is not transparent, and separating out a large amount of solids after standing; then adding 20 g of SD2, heating to 100 ℃, stirring for 0.5 hour, cooling, standing for 30 days, and observing the stability of the mixture for 60 days;
(2) Taking 10 g of cobalt acetate, adding 70 g of isododecane, refluxing and heating to 100 ℃, keeping the temperature for 2 hours, obviously showing that the suspension is not transparent, and separating out a large amount of solids after standing; then 20 g of SD2-2 is added, the mixture is heated to 100 ℃ and stirred for 0.5 hour, and the mixture is cooled and then stands for 30 days and 60 days to respectively observe the stability of the mixture;
(3) Taking 10 g of cobalt acetate, adding 70 g of isododecane, refluxing and heating to 100 ℃, keeping the temperature for 2 hours, obviously showing that the suspension is not transparent, and separating out a large amount of solids after standing; then adding 20 g of polyacrylic acid PAA (with the average molecular weight of 3000), heating to 100 ℃, stirring for 0.5 hour, cooling, standing for 30 days, and observing the stability of the mixture for 60 days;
(4) Taking 10 g of cobalt acetate, adding 70 g of isododecane, refluxing and heating to 100 ℃, keeping the temperature for 2 hours, obviously showing that the suspension is not transparent, and separating out a large amount of solids after standing; then adding 20 g of sodium polyacrylate SPA2, heating to 100 ℃, stirring for 0.5 hour, cooling, standing for 30 days, and observing the stability of the mixture for 60 days;
the results of the experiments in (1) to (4) are shown in Table 1.
Table 1: experimental result on dispersibility and stability of super-dispersant SD and polyacrylic acid PAA or sodium polyacrylate SPA dispersant in color paste
Figure BDA0002393710360000121
From the above examples and application examples, it can be seen that, compared with the conventional polyacrylic acid or polyacrylate dispersant containing no complex nitrogen atoms and having a high content of carboxyl groups, the polyacrylic acid or polyacrylate dispersant has poor compatibility with oily systems and is precipitated quickly, the dispersant has poor dispersibility for organic pigments in aqueous systems, the pigments are precipitated and delaminated quickly, and the dispersant molecules have only COO in carboxyl groups - The metal ion with positive charges has a charge adsorption effect, and the coordination stability of a single O atom to a plurality of metal ions is poor; the solvent-free high-nitrogen-content polycarboxylic hyper-dispersant prepared by the invention can be conveniently and directly added into metal ion color paste or can be used in metal ion color paste or ink after aqueous solution formed by alkali neutralization (SD 4-2 (neutralization) in application example 1), the dispersant can be rapidly dispersed into the whole system without layering and separation, has good compatibility, has high dispersibility on the color paste, ensures that the whole system is uniformly dispersed, has no color difference and flooding, can be stable for a long time, and has certain weak coordination stabilizing effect on metal ions except O or double bonds in carbonyl (C = O) in dispersant molecules - Has charge stabilizing effect on metal cations in the pigment, and also has carboxyl groupOH. Alcoholic hydroxyl C-OH and ester group COOWeak coordination stabilization of O atom in R to metal ion, especially lone pair electron in N atomThe strong coordination function formed by the interaction of the empty tracks of the metal ions of the pigment, namely, the dispersant molecules and the metal ions form a multi-tooth ring-shaped complex, so that the stability of the complex formed between the metal ions and the dispersant molecules is greatly improved, and the solvation groups (polyether PPO and PEO) in the dispersant ensure the dispersion and stability of the complex in a medium, thereby greatly improving the stability of the pigment color paste containing the metal ions. As can be seen from Table 1, in the same application example 1, the dispersant was added with the carbonyl group, the N element and the nitrogen content (2 wt% or more) at a given valueO(comprisingOH,COOR,COONa) and stability of the color paste (for example, SD3 (total content 24.04%), SD4-2 (total content 25.67%) or SD4-2 (neutralization) (total content 24.87%) in application example 1 respectively for SD3-2 (total content 18.8%), SD1 (total content 32.65%) and SD1-2 (total content 23.41%)); when the total content is close to each other, the stability of the color paste with high N element content is increased (such as SD3 (total content 24.04%, N content 5.84%)) vs. SD1-2 (total content 23.41%, N content 3.15%) in application example 1).
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A preparation method of a solvent-free high-nitrogen-content polycarboxyl hyperdispersant is characterized by comprising the following steps:
(1) Slowly adding 0.5-1 molar part of monoepoxy compound and 1 molar part of polyether polyol diglycidyl ether into 2 molar parts of polyamine containing 2-6 nitrogen atoms under stirring, keeping the temperature of the mixed solution at 15-40 ℃, continuing to react for 3-24 hours after the addition is finished, then heating to 50-70 ℃ for 2-6 hours, and cooling;
(2) Slowly adding 0.25-0.5 mol part of glycidyl ether into the solution obtained in the step (1) while stirring, keeping the temperature of the mixed solution at 15-50 ℃, continuing to react for 4-24 hours after the addition is finished, then heating to 50-60 ℃ for reacting for 0-6 hours, and cooling; the reaction in the step (2) is repeated twice, and the mole fraction of the total epoxy groups in the glycidyl ether is 1-1.5;
(3) Slowly adding 4-12 molar parts of one of cyclic anhydride or acrylic acid into the solution obtained in the step (2) under stirring, then reacting for 3-8 hours at 50-100 ℃, and cooling to obtain a solvent-free high-nitrogen-content polycarboxyl type hyperdispersant;
the total amount of the polyether glycol diglycidyl ether in the step (1) and the polyethylene glycol radical in the glycidyl ether in the step (2) is 50 to 85 weight percent of the total amount of the polyethylene glycol radical and the polypropylene glycol radical;
the glycidyl ether in the step (2) is one or more of polyether polyol diglycidyl ether, micromolecular diglycidyl ether and micromolecular triglycidyl ether.
2. The method according to claim 1, wherein the cyclic anhydride in step (3) is at least one of maleic anhydride, succinic anhydride, methylhexahydrophthalic anhydride and methyltetrahydrophthalic anhydride, and the molar fraction of all cyclic anhydrides in step (3) does not exceed the molar fraction of active hydrogen of the polyamine.
3. The production method according to claim 1, wherein the reaction of step (2) is repeated twice, the number of moles of epoxy groups in the glycidyl ether decreases; the molecular weight of the polyether polyol diglycidyl ether in the step (1) is 300-2000.
4. The method according to claim 3, wherein the molecular weight of the polyether polyol diglycidyl ether in the step (2) is 300 to 2000.
5. The production method according to claim 1 or 2 or 3 or 4, characterized in that the total amount of the polyethylene glycol groups in the polyether polyol diglycidyl ether in the step (1) and the glycidyl ether in the step (2) is 60 to 80wt% of the total amount of the polyethylene glycol groups and the polypropylene glycol groups.
6. The production method according to claim 1 or 2 or 3 or 4, wherein the dropping time of the slow addition in the step (1) is 3 to 5 hours; the dropping speed of the slow addition in the step (2) is 0.3 to 1 g/min; the dropping time of the slow addition in the step (3) is 0.5 to 1 hour.
7. The method according to claim 1 or 2 or 3 or 4, wherein the monoepoxy compound in step (1) is at least one of benzyl glycidyl ether, phenyl glycidyl ether, alkylphenyl glycidyl ether, and alkyl glycidyl ether;
the polyether polyol diglycidyl ether in the step (1) and the step (2) is one of polyethylene glycol-polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether;
the polyamine in the step (1) is one of ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine;
the micromolecule diglycidyl ether in the step (2) is one of ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether and cyclohexanediol diglycidyl ether;
the micromolecular triglycidyl ether in the step (2) is one of trimethylolpropane triglycidyl ether and glycerol triglycidyl ether.
8. A solvent-free high nitrogen-containing polycarboxy-type hyperdispersant prepared by the method of any one of claims 1 to 7.
9. Use of the hyperdispersant of claim 8 in mill base dispersions.
10. Use according to claim 9, wherein said hyperdispersant is used in aqueous or oily coatings, aqueous or oily inks.
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