CN101962481B - Macromolecular compound suitable for being used as solvent-based pigment dispersant - Google Patents
Macromolecular compound suitable for being used as solvent-based pigment dispersant Download PDFInfo
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Abstract
The invention discloses a macromoleclar composite sutable of being used as the solvent-based pigment dispersant. The macromoleclar composite contains grafted macromolecule copolymer. The graft macromolecule copolymer contains the following structures: (1) a main chain, wherein the main chain is acrylic copolymer with epoxy groups; (2) grafting side chains, wherein the grafting side chains are straight chain polyester with terminal amino groups; and (3) polar groups with the function of anchoring pigment, wherein the polar groups are selected from aromatic compounds or heterocyclic amine compounds and connected with the side groups of the main chain through the grafting reactions of the side chains. The macromoleclar composite can be widely used in the solvent-based coating system, have excellent wetting and dispersing functions on most of inorganic and organic pigments, and increase the grinding distribution efficiency of pigment and the stability during storage.
Description
Technical field
The macromolecular compound that to the present invention relates to a kind of grafting main chain be PEMULEN TR2, this macromolecular compound all have excellent wetting divergent function as pigment dispersing agent to various pigment.
Background technology
Pigment dispersing agent is effectively to realize pigment particles homodisperse and analog assistant in paint vehicle steady in a long-term in process of lapping.In coating manufacture process, pigment is dispersed in by in the middle of the paint vehicle of resin, auxiliary agent and solvent composition with the form of molecule under the grinding shearing action of external force.Since poor without consistency between wetting pigment and the base-material, there is the phase repulsive interaction, therefore, in such dispersion system, pigment particles has the tendency of reunion, and it is thick finally to show as returning of paint vehicle, and disadvantages such as sedimentation influence the paint vehicle quality.The adding of wetting dispersing agent can not only reduce the surface tension of pigment particles between paint vehicle to greatest extent, improves dispersing of pigments efficient and stability, can also reduce paint vehicle viscosity simultaneously, improves the workability of paint vehicle.
The specific function of wetting dispersing agent comes from the specific molecule structure, requires to contain simultaneously in the molecule structural unit of close pigment and close resin.Main coating is the polymkeric substance with certain geometry with pigment dispersing agent at present, and main class comprises polyurethanes (US 4,032,689, and US 4,647647) and polyacrylic.Wherein acrylic polymers is numerous in variety, is applicable to different systems, therefore uses comparatively extensive.
Acrylic dispersants early generally obtains through the copolyreaction of macromonomer and small molecules Acrylic Acid Monomer; For example world patent WO 9; 518; 170 have introduced and have a kind ofly caused the method that caprolactone polymerization prepares the polyester acrylic macromonomer through Hydroxyethyl acrylate, and through with the free-radical polymerized vinylformic acid dispersion agent that obtains having pectination of other Acrylic Acid Monomers; Other has patent WO 9,903,937, and WO 2; 005,105; 855, US 6,521; 715 grades introduced a kind of with cobalt class title complex as catalyzer, contain the macromole Acrylic Acid Monomer of unsaturated double-bond through the synthetic end group of catalysis chain transfer reaction (CCTP), and the dispersion agent with pectination synthesized in macromonomer that obtains and the copolymerization of small molecules Acrylic Acid Monomer.Though this type can synthesize the product with wetting divergent function through the method for the synthetic pectination vinylformic acid dispersion agent of unit molecule monomer copolymerization; But still there is an important defective in this method: the polymerization activity of macromonomer is far below the small molecules Acrylic Acid Monomer, therefore; Be difficult to realize the desirable copolymerization of macromonomer and small molecule monomer through conventional radical polymerization; In real reaction, have only less a part of macromonomer to participate in copolyreaction, so residual more macromonomer and the XPA of macromonomer in the grafting not in the product; The effective constituent that finally can play wetting dissemination is not high, influences last product performance.
In order to improve the content of effective of product, researchers have proposed two kinds of new synthesis paths, and a kind of is the controllable free-radical polymerisation method, and related patent U.S. Patent No. comprises US 7,317,062, and US 20; 040,143,035, US 6,306, and 521; US 6,413,306, and CN 1,378, and 564 etc.These methods can be controlled the molecular structure of PEMULEN TR2 under severe condition, improve the product content of effective, but the present applicable surface of these methods is narrow, and technology is amplified difficulty, and therefore, its achievement still rests on the experimental phase.
Two outer a kind of route of synthesis effectively are polymer graft methods, and this also is the most effective at present, the most a kind of method of technology controlling and process.For example authorized the U.S. Pat 5,852,123 of Huybrechts on December 22nd, 1998.This patent has been introduced the agent structure of a kind of polymkeric substance with polyester grafting epoxy acrylic resin as dispersion agent; And in grafting on the main polymer chain polar group as pigment anchoring component; This product shows good wetting dispersion effect when mill base grinds; Yet the mode of this single anchoring remains on stability in some problems, and these single polar groups that act on surface of pigments are substituted easily under the condition of polar solvent or other strong polar group existence and split away off from the pigment particles surface, lose the stable provide protection to pigment particles; And finally cause pigment to flocculate, even return thick.
Therefore, guarantee dispersion agent to the long-term dispersing property of pigment just must on the pigment anchoring unit of dispersion agent, introduce with the stronger group of pigment avidity.Main pigment anchoring group is divided into two types at present: pigment anchoring group the earliest is an acidic-group, like carboxyl, and sulfonate radical, phosphate radical etc.; See patent CN 1,242,794A, US 5; 130,463, GB 2,001; 083 etc., such anchoring group has stronger wetting dissemination to the mineral-type color stuffing, and therefore range of application is very wide in early days.Along with the appearance of pigment dyestuff with popularize, as comprise the phthalocyanine serial pigment of ICI company, the azo class pigment of CIBA company, the benzimidazolone pigment that the quinacridone pigment of E.I.Du Pont Company and Clariant company produce all contains the heterocyclic chromophore; With the avidity of acidic-group a little less than, therefore develop second type of dispersion agent, contain the dispersion agent of amine group, main amine anchoring group tertiary amine, quaternary ammonium salt; Carbamate, urea groups, imide is seen patent EP 1,837; 355, US 7,312,260, and US 5; 424,364, CN 1,339, and 533 etc.Simultaneously, US 6,596,816, and CN 101,234, and patents such as 313 can further improve the pigment anchorage effect to a certain extent with the introducing anchoring unit of polyamine.
The present invention introduces multiple pigment anchoring group on this basis, especially contains the heterocyclic anchoring group, strengthens the pigment anchorage effect greatly through synergy, obtains a kind of excellent performance, the pigment dispersing agent that steady time is longer.
Summary of the invention
The objective of the invention is to provide a kind of macromolecular compound that is applicable to as the solvent-borne type pigment dispersing agent; This compound has the branch sub-frame structures of straight chain amido polyester grafting epoxy acrylic resin, and in the grafting simultaneously of the different positions on the propenoic acid main chain one or more polar groups.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of macromolecular compound that is applicable to as the solvent-borne type pigment dispersing agent; It is characterized in that this macromolecular compound is a kind of graft type high-molecular copolymer; This graft type high-molecular copolymer has: (1), main chain, this main chain are the PEMULEN TR2 that contains epoxide group; (2) graft side chain, this graft side chain are the straight chain type polyester that end group has amido; And (3) have the polar group of pigment anchorage effect, and this polar group is from aromatic ring or heterocyclic amine compound, and are connected on the main chain side group through the side chain graft reaction.
The number-average molecular weight of macromolecular compound is 3000-30000g/mol; Wherein main chain PEMULEN TR2 molecular weight is 2000-20000g/mol; Be preferably 3000-10000g/mol, the molecular weight of graft side chain is 500-10000g/mol, is preferably 1000-5000g/mol.
The PEMULEN TR2 main chain accounts for the 20%-80% of graft type high-molecular copolymer gross weight, preferably approximately 30-70%, and the straight chain type polyester accounts for the 80%-20% of graft type high-molecular copolymer gross weight, preferably approximately 70%-30%.The graft type high-molecular copolymer further comprises and accounts at least 3% of its total amount, and the polar group of preferred 5-20% is as the pigment conjugated group, and the hydroxyl that comprises about 2%-5% simultaneously is as reactive group.
The building-up process of pigment dispersing agent comprises three parts: the preparation of straight chain type polyester, the molecule assembling of synthesizing and passing through graft reaction realization anchoring group and amido polyester and XPA main chain of main chain PEMULEN TR2.The dispersion agent that obtains can the inorganic and pigment dyestuff of efficient wetting dispersion, comprise being difficult to dispersive charcoal blacks and the blue or green pigment of phthalein, and the coating compound storage stability that obtains is good, even in intensive polar solvent, still can keep excellent stability.
PEMULEN TR2 as main chain can form through the free radicals copolymerization reaction approach of Acrylic Acid Monomer, and the used raw material of synthesizing propylene acid copolymer mainly contains technical grade Acrylic Acid Monomer and methacrylic acid monomer, like methyl acrylate; Ethyl propenoate, Bing Xisuandingzhi, TEB 3K; Jia Jibingxisuanyizhi; NSC 20956 etc., in addition, but the also vinylbenzene of copolymerization part; Another significant element was an epoxy acrylate during monomer was formed, and like SY-Monomer G (GMA), the PEMULEN TR2 epoxy group content is not less than 0.1mol/100g.The synthetic used initiator of this polymkeric substance can be the solvent-borne type initiator of using always, like the azo class: Diisopropyl azodicarboxylate, AMBN, ABVN; Peroxide: peroxide tertiary butyl, dicumyl peroxide, di-isopropyl peroxydicarbonate etc.Main chain PEMULEN TR2 synthesis technique is conventional solvent method synthesis technique, and common solvent is the mixed solvent that benzene kind solvent and esters solvent are formed, and benzene kind solvent commonly used mainly contains toluene; YLENE; Trimethylbenzene, esters solvent mainly contains ETHYLE ACETATE, butylacetate etc.
Straight chain type polyester as graft side chain can obtain through the ring-opening polymerization of amido monohydroxy-alcohol initiation lactone cpd, and the synthesis material of straight chain type polyester is mainly amido monohydroxy-alcohol and lactone cpd.Wherein, the amido monohydroxy-alcohol comprises thanomin, Propanolamine, para hydroxybenzene amine etc.Lactone cpd mainly contains caprolactone, GBL.This reaction is a ring-opening polymerization, and initiator is the amido monohydroxy-alcohol, and lactone cpd is the ring-opening polymerization monomer.Accomplish this reaction and also need add catalyzer, catalyzer commonly used is the organo-metallic class, like organotin, and organo-bismuth, catalyzer commonly used has stannous octoate, dibutyl tin laurate etc.
The polar group as the pigment anchoring group that grafts on propenoic acid main chain among the present invention comes from the aminated compounds that has reactive hydrogen, like primary amine, and secondary amine, imide; Preferably have phenyl ring, the secondary-amine compound of heterocycle equiconjugate ring is like pentanoic; Hexahydropyridine, imidazoles, triazole; Pyrazoles, methylamino benzoglyoxaline, phthalic imidine etc.Behind the epoxide group generation graft reaction of this compounds and main chain, produce hydroxyl and the amido that contains reactive hydrogen, when the paint curing film forming, can react, be attached in the paint film network structure, pigment is played fixed action with solidifying agent in the consecutive position.In order to improve the pigment anchorage effect of dispersion agent, can increase the aminated compounds that contains unsaturated double-bond and improve anchorage effect, like vinyl aniline, allyl imidazole etc.Unsaturated double-bond and nitrogen-containing group produce synergy, can improve anchoring efficient greatly.
The invention has the beneficial effects as follows: this compound has the branch sub-frame structures of straight chain amido polyester grafting epoxy acrylic resin, and in the grafting simultaneously of the different positions on the propenoic acid main chain one or more polar groups.Polar group on the propenoic acid main chain side group has stronger wetting affinity interaction to surface of pigments; And a plurality of polar groups of same position can also further be strengthened the anchorage effect to surface of pigments through synergy, and dispersion agent can steady in a long-termly not replaced by other polar materials with the pigment particles surface; Straight chain polyester-polyurethane and general organic solvent and coating all have good consistency with matrix resin, realize the stability to pigment particles through the steric exclusion effect.Remain with a spot of reactive group on the compound dispersing agent; Like hydroxyl; Dispersion agent can be fixed to through the crosslinking reaction of reactive group and solidifying agent in the network structure of paint film in the thermoset film process; Improve the stability of paint film form and aspect, this advantage shows more outstanding when using as finish paint.This compound of the present invention not only has regular Grafting Structure, and contains and comprise aromatic nucleus, tertiary amine; Carbamate, imide, polynary pigment anchoring group such as unsaturated double-bond; Various pigment are all had excellent wetting divergent function, with mineral dye outstanding dispersion and stabilization are arranged all organic, and adaptable across vibrin; Vinyl resin, various resin systems such as epoxy resin.
Below in conjunction with embodiment the present invention is further specified.
Embodiment
In following examples; Embodiment 1-5 introduces straight chain type polyester compound method; Embodiment 6-12 introduces the polar group graft reaction that the main chain PEMULEN TR2 synthesizes and have anchorage effect; Embodiment 13-17 introduces the synthetic graft type high-molecular copolymer product of straight chain type polyester side chains location grafting, and embodiment 18 introduces graft type high-molecular copolymer dispersing agent performance evaluation method and result.
Embodiment 1
Take by weighing thanomin 61.1g, 6-caprolactone 938.9g, the isocaprylic acid tin 0.1g volume of packing into is in the four neck round-bottomed flasks of 2000ml, and behind 120 ℃ of reactions of insulation 7h, the caprolactone transformation efficiency is greater than 99% down in nitrogen protection.Replenish the 1000 back dischargings of adding N-BUTYL ACETATE, obtain the straight chain type polyester, it is 50% that testing product contains admittedly, and hydroxy radical content is 0.85wt%, and the amine value is 28.1mgKOH/g.The theoretical molecular of product is 1000g/mol.
Embodiment 2
Take by weighing thanomin 40.7g, 6-caprolactone 959.3g, the isocaprylic acid tin 0.15g volume of packing into is in the four neck round-bottomed flasks of 2000ml, and behind 120 ℃ of reactions of insulation 7h, the caprolactone transformation efficiency is greater than 99% down in nitrogen protection.Replenish the 1000 back dischargings of adding N-BUTYL ACETATE, obtain the straight chain type polyester, it is 50% that testing product contains admittedly, and hydroxy radical content is 0.58wt%, and the amine value is 18.8mgKOH/g.The theoretical molecular of product is 1500g/mol.
Embodiment 3
Take by weighing thanomin 20.4g, 6-caprolactone 979.6g, the dibutyl tin laurate 0.1g volume of packing into is in the four neck round-bottomed flasks of 2000ml, and behind 130 ℃ of reactions of insulation 7h, the caprolactone transformation efficiency is greater than 99% down in nitrogen protection.Discharging behind the additional adding N-BUTYL ACETATE 1000g obtains the straight chain type polyester, and it is 50% that testing product contains admittedly, and hydroxy radical content is 0.28wt%, and the amine value is 9.3mgKOH/g.The theoretical molecular of product is 3000g/mol.
Embodiment 4
Take by weighing PARA AMINOPHENOL 109.1g, GBL 890.9g, the dibutyl tin laurate 0.1g volume of packing into is in the four neck round-bottomed flasks of 2000ml, and behind 130 ℃ of reactions of insulation 7h, the caprolactone transformation efficiency is greater than 99% down in nitrogen protection.Discharging behind the additional adding N-BUTYL ACETATE 1000g obtains the straight chain type polyester, and it is 50% that testing product contains admittedly, and hydroxy radical content is 1.02wt%, and the amine value is 33.6mgKOH/g.The theoretical molecular of product is 1000g/mol.
Embodiment 5
Take by weighing PARA AMINOPHENOL 36.4g, GBL 963.6g, the dibutyl tin laurate 0.1g volume of packing into is in the four neck round-bottomed flasks of 2000ml, and behind 130 ℃ of reactions of insulation 7h, the caprolactone transformation efficiency is greater than 99% down in nitrogen protection.Replenish the 667 back dischargings of adding N-BUTYL ACETATE, obtain the straight chain type polyester, it is 60% that testing product contains admittedly, and hydroxy radical content is 0.28wt%, and the amine value is 9.3mgKOH/g.The theoretical molecular of product is 3000g/mol.
Embodiment 6
In the four neck round-bottomed flasks that the 2000ml that condensation manages admittedly is housed, add trimethylbenzene 350g, N-BUTYL ACETATE 100g feeds nitrogen and also is warming up to 120 ℃; Take by weighing NSC 20956 (BMA) 500g; SY-Monomer G (GMA) 100g, AMBN 18g, the back insulation that stirs at the uniform velocity drops in the four neck round-bottomed flasks for 120 ℃; Dropwise in 2 hours, dropwise the back and add the solution of forming by 3g AMBN and 50g N-BUTYL ACETATE.Be incubated 120 ℃ of reactions and add Powdered phthalic imidine 60g after 3 hours, be warming up to 150 ℃ of insulation reaction after 3 hours, the solid particulate reaction finishes, and adds N-BUTYL ACETATE 180g, stopped reaction.
The product yellow transparent is thick, and the test sample solid content is 50%, and number-average molecular weight is 8000g/mol, and hydroxy radical content is 0.51%.
Embodiment 7
In the four neck round-bottomed flasks that the 2000ml that condensation manages admittedly is housed, add trimethylbenzene 350g, N-BUTYL ACETATE 100g feeds nitrogen and also is warming up to 130 ℃; Take by weighing methyl methacrylate butyl ester (MMA) 400g; SY-Monomer G (GMA) 200g, peroxide tertiary butyl 25g, the back insulation that stirs at the uniform velocity drops in the four neck round-bottomed flasks for 130 ℃; Dropwise in 2 hours, dropwise the back and add the solution of forming by 2g peroxide tertiary butyl and 50g N-BUTYL ACETATE.Be incubated 130 ℃ of reactions and add Powdered phthalic imidine 100g after 3 hours, be warming up to 150 ℃ of insulation reaction after 3 hours, the solid particulate reaction finishes, and adds N-BUTYL ACETATE 220g, stopped reaction.
Product is the yellow transparent liquid viscous liquid, and the test sample solid content is 50%, and number-average molecular weight is 5000g/mol, and hydroxy radical content is 0.85%.
Embodiment 8
In the four neck round-bottomed flasks that the 2000ml that condensation manages admittedly is housed, add trimethylbenzene 400g, N-BUTYL ACETATE 50g feeds nitrogen and also is warming up to 150 ℃; Take by weighing NSC 20956 (BMA) 300g; SY-Monomer G (GMA) 300g, peroxide tertiary butyl 28g, the back insulation that stirs at the uniform velocity drops in the four neck round-bottomed flasks for 150 ℃; Dropwise in 2 hours, dropwise the back and add the solution of forming by 3g peroxide tertiary butyl and 50g N-BUTYL ACETATE.Be incubated 150 ℃ of reactions and add Powdered phthalic imidine 120g after 3 hours, insulation reaction is after 3 hours, and the solid particulate reaction finishes, and adds termination reaction behind the N-BUTYL ACETATE 240g after being cooled to 130 ℃.
Product is a deep yellow transparent liquid viscous liquid, and the test sample solid content is 50%, and number-average molecular weight is 4000g/mol, and hydroxy radical content is 1.0%.
Embodiment 9
In the four neck round-bottomed flasks that the 2000ml that condensation manages admittedly is housed, add trimethylbenzene 350g, N-BUTYL ACETATE 100g feeds nitrogen and also is warming up to 130 ℃; Take by weighing NSC 20956 (BMA) 500g; SY-Monomer G (GMA) 100g, AMBN 18g, the back insulation that stirs at the uniform velocity drops in the four neck round-bottomed flasks for 120 ℃; Dropwise in 2 hours, dropwise the back and add the solution of forming by 3g AMBN and 50g N-BUTYL ACETATE.Be incubated 120 ℃ of reactions and add Powdered imidazoles 47.8g after 3 hours, insulation reaction is after 3 hours, and the solid particulate reaction finishes, and adds N-BUTYL ACETATE 168g, stopped reaction.
Product is the yellow transparent liquid viscous liquid, and the test sample solid content is 50%, and number-average molecular weight is 8000g/mol, and hydroxy radical content is 0.9wt%.
Embodiment 10
In the four neck round-bottomed flasks that the 2000ml that condensation manages admittedly is housed, add trimethylbenzene 350g, N-BUTYL ACETATE 100g feeds nitrogen and also is warming up to 130 ℃; Take by weighing NSC 20956 (BMA) 400g; SY-Monomer G (GMA) 200g, peroxide tertiary butyl 25g, the back insulation that stirs at the uniform velocity drops in the four neck round-bottomed flasks for 130 ℃; Dropwise in 2 hours, dropwise the back and add the solution of forming by 3g peroxide tertiary butyl and 50g N-BUTYL ACETATE.Be incubated 130 ℃ of reactions and add Powdered imidazoles 95g after 3 hours, be warming up to 150 ℃ of insulation reaction after 3 hours, the solid particulate reaction finishes, termination reaction behind the adding N-BUTYL ACETATE 225g.
Product is the yellow transparent liquid viscous liquid, and the test sample solid content is 50%, and number-average molecular weight is 5000g/mol, and hydroxy radical content is 1.6wt%.
Embodiment 11
In the four neck round-bottomed flasks that the 2000ml that condensation manages admittedly is housed, add trimethylbenzene 350g, N-BUTYL ACETATE 100g feeds nitrogen and also is warming up to 130 ℃; Take by weighing NSC 20956 (BMA) 400g; SY-Monomer G (GMA) 200g, peroxide tertiary butyl 25g, the back insulation that stirs at the uniform velocity drops in the four neck round-bottomed flasks for 130 ℃; Dropwise in 2 hours, dropwise the back and add the solution of forming by 3g peroxide tertiary butyl and 50g N-BUTYL ACETATE.Be incubated 130 ℃ of reactions and add hexahydropyridine 85g after 3 hours, insulation reaction is after 3 hours, and the solid particulate reaction finishes, and adds N-BUTYL ACETATE 213 back termination reaction g.
Product is light yellow transparent liquid viscous liquid, and the test sample solid content is 50%, and number-average molecular weight is 5000g/mol, and hydroxy radical content is 1.2wt%.
Embodiment 12
In the four neck round-bottomed flasks that the 2000ml that condensation manages admittedly is housed, add trimethylbenzene 350g, N-BUTYL ACETATE 100g feeds nitrogen and also is warming up to 130 ℃; Take by weighing NSC 20956 (BMA) 400g; SY-Monomer G (GMA) 200g, peroxide tertiary butyl 25g, the back insulation that stirs at the uniform velocity drops in the four neck round-bottomed flasks for 130 ℃; Dropwise in 2 hours, dropwise the back and add the solution of forming by 3g peroxide tertiary butyl and 50g N-BUTYL ACETATE.Be incubated 130 ℃ of reactions and add hexahydropyridine 45g after 3 hours, insulation reaction was cooled to 60 ℃ and adds Resorcinol 0.1g after 3 hours, vinyl aniline 40g, insulation reaction 2h, termination reaction behind the adding N-BUTYL ACETATE 263g.
Product is light yellow transparent liquid viscous liquid, and the test sample solid content is 50%, and number-average molecular weight is 5000g/mol, and hydroxy radical content is 1.2wt%.
Embodiment 13
Take by weighing embodiment 1 products therefrom 800g, embodiment 6 products therefrom 800g add in the four neck round-bottomed flasks that the 2000ml that condensation manages admittedly is housed, and are warming up to 80 ℃ of insulation reaction, and system viscosity increases.Stopped reaction after 3 hours.Cooling discharging, product are yellow thick transparent liquid, and solid content is 50%, and number-average molecular weight is 16000g/mol.
Embodiment 14
Take by weighing embodiment 1 products therefrom 800g, embodiment 7 products therefrom 800g add in the four neck round-bottomed flasks that the 2000ml that condensation manages admittedly is housed, and are warming up to 80 ℃ of insulation reaction, and system viscosity increases.Stopped reaction after 3 hours.Cooling discharging, product are yellow thick transparent liquid, and solid content is 50%, and number-average molecular weight is 10000g/mol.
Embodiment 15
Take by weighing embodiment 3 products therefrom 800g, embodiment 6 products therefrom 800g add in the four neck round-bottomed flasks that the 2000ml that condensation manages admittedly is housed, and are warming up to 80 ℃ of insulation reaction, and system viscosity increases.Stopped reaction after 3 hours.Cooling discharging, product are yellow thick transparent liquid, and solid content is 50%, and number-average molecular weight is 16000g/mol.
Embodiment 16
Take by weighing embodiment 5 products therefrom 800g, embodiment 11 products therefrom 800g add in the four neck round-bottomed flasks that the 2000ml that condensation manages admittedly is housed, and are warming up to 80 ℃ of insulation reaction, and system viscosity increases.Stopped reaction after 3 hours.Cooling discharging, product are yellow thick transparent liquid, and solid content is 50%, and number-average molecular weight is 10000g/mol.
Embodiment 17
Take by weighing embodiment 5 products therefrom 1600g, embodiment 10 products therefrom 800g add in the four neck round-bottomed flasks that the 2000ml that condensation manages admittedly is housed, and are warming up to 80 ℃ of insulation reaction, and system viscosity increases.Stopped reaction after 3 hours.Cooling discharging, product are yellow thick transparent liquid, and solid content is 50%, and number-average molecular weight is 15000g/mol.
Embodiment 18
Experimental design is estimated different dispersing agent performances; And with market on sophisticated commodity dispersant A compare; Method of evaluating performance is following: reference formulation (table 1) configuration abrasive is a hone with the basket type sand mill, grinds 4 hours; Weigh the moisture dispersibility ability of dispersion agent through detecting fineness pace of change (table 2) to pigment, and through the stability (table 3) of high temperature (65 ℃) storage The effects dispersion agent to pigment.
Table 1 abrasive material prescription:
| Numbering | The material name | Charging capacity (part) |
| 1 | Hydroxylated acrylic resin | 500 |
| 2 | Charcoal blacks | 50 |
| 3 | Dispersion agent | 30 |
| 4 | Mixed solvent (butylacetate/YLENE=1:1) | 100 |
Table 2 fineness detected result
Table 3 fineness detected result
Based on above experimental result,, realize the synergistic effect of polynary anchoring group, thereby make the dispersion agent product that obtains have the performance that surmounts the existing goods dispersion agent fully through this patent location crosslinking technology.Through adjustment dispersion agent structure and composition, can also do further to improve to dispersing agent performance.
Claims (3)
1. one kind is applicable to the macromolecular compound as the solvent-borne type pigment dispersing agent; It is characterized in that this macromolecular compound is a kind of graft type high-molecular copolymer, this graft type high-molecular copolymer has: (1), main chain, this main chain are the PEMULEN TR2 that contains epoxide group; Its number-average molecular weight is 2000-20000g/mol; Wherein, be that free radicals copolymerization reaction approach through Acrylic Acid Monomer forms as the PEMULEN TR2 of main chain, wherein Acrylic Acid Monomer comprises epoxy acrylate; And methyl acrylate, ethyl propenoate, Bing Xisuandingzhi, TEB 3K, one or more in Jia Jibingxisuanyizhi, the NSC 20956; (2) graft side chain; This graft side chain is that end group has amino straight chain type polyester, and the polar group with pigment anchorage effect, and this polar group is from aromatic ring or heterocyclic amine compound; And be connected on the main chain side group through side chain graft reaction; Wherein, aromatic ring or heterocyclic amine compound are one or more in pentanoic, hexahydropyridine, imidazoles, triazole, pyrazoles, methylamino benzoglyoxaline, the phthalic imidine, and the number-average molecular weight of graft side chain is 500-10000g/mol; Wherein polar group content is the 3%-20% of multipolymer gross weight, comprise simultaneously account for multipolymer gross weight 2%-5% hydroxyl as reactive group.
2. a kind of macromolecular compound that is applicable to as the solvent-borne type pigment dispersing agent according to claim 1 is characterized in that said epoxy acrylate is a SY-Monomer G, and the epoxy group content of PEMULEN TR2 is not less than 0.1mol/100g.
3. a kind of macromolecular compound that is applicable to as the solvent-borne type pigment dispersing agent according to claim 1; It is characterized in that the straight chain type polyester as graft side chain is to cause the lactone cpd ring-opening polymerization through the amido monohydroxy-alcohol to obtain; Wherein the amido monohydroxy-alcohol is one or more in thanomin, Propanolamine, the para hydroxybenzene amine, and lactone cpd is caprolactone or GBL.
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| US10604665B2 (en) * | 2015-01-27 | 2020-03-31 | Sumitomo Metal Mining Co., Ltd. | Near infrared absorbing fine particle dispersion liquid and method for producing the same, anti-counterfeit ink composition using near infrared absorbing fine particle dispersion liquid, and anti-counterfeit printed matter using near infrared absorbing fine particles |
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| CN106750342B (en) * | 2016-12-07 | 2020-11-27 | 华东理工大学 | Comb type hyperdispersant, preparation method and application |
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