Triazinyl compound, polymeric dispersant, color paste and application thereof

Abstract

The invention provides a triazinyl compound, a polymeric dispersant prepared from the triazinyl compound, color paste and application thereof. The triazinyl compound provided by the invention has a structure as shown in formula I, and has a sulfonic acid group and an organic amine group, so that the triazinyl compound can significantly improve the dispersibility and stability of the phthalocyanine pigment in water or an organic solvent, and widens the application of the phthalocyanine pigment in display materials. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the technical field of liquid crystal display materials, and in particular to a triazine-based compound, a polymer dispersant synthesized by using the triazine-based compound, and a color paste containing the polymer dispersant. Background Art

[0002] Phthalocyanine pigments have excellent heat resistance, light resistance, weather resistance and other properties, and bright colors, strong tinting power, and are widely used in printing inks, coatings, plastics, rubber and other fields. However, phthalocyanine pigments have low surface polarity, poor dispersibility, and are very easy to condense in solvents or dispersants, resulting in uneven dispersion. In addition, it has very low solubility in organic solvents, is almost insoluble in water, and is only soluble in a small amount of solvents such as concentrated sulfuric acid, phosphoric acid, chlorosulfonic acid, and trichloroacetic acid (Su Jinli et al., "Dissolution of Copper Phthalocyanine and Preparation of Nano-Copper Phthalocyanine Films"). Therefore, increasing the solubility of phthalocyanine pigments becomes the key to their application.

[0003] At present, the solubilization method of phthalocyanine pigments is mostly to introduce substituents such as sulfonic acid, carboxylic acid, hydroxyl or lipophilic groups into the large benzene ring system of phthalocyanine, or to introduce amphiphilic groups containing both partial lipophilic and partial hydrophilic groups at one time to improve the solubility of phthalocyanine (Liu Chuanren, "Synthesis and Property Research of Soluble Fluorinated Phthalocyanine"). However, the above method has the problems of many reaction steps, complicated post-processing, low product yield and purity, especially low product yield and low purity limit its large-scale application. Patent CN 115124889 discloses a triazine red pigment dispersing synergist, which is a small molecule dispersing synergist obtained by reacting cyanuric chloride with aminobenzenesulfonic acid and p-phenylenediamine, and has the problem of small molecular weight and poor migration resistance. Therefore, it is necessary to develop a more effective dispersant to improve the solubility and stability of phthalocyanine pigments. Summary of the invention

[0004] In order to solve one of the above-mentioned technical problems existing in the prior art, the present invention provides a triazine-based compound, which contains both a sulfonic acid group and an organic amine group. The dispersant obtained after polymerization with other monomers has a particularly good dispersing effect on phthalocyanine pigments, thereby improving the dispersion efficiency and color paste stability.

[0005] The technical solution of the present invention is as follows:

[0006] In a first aspect, the present invention provides a triazine-based compound having a structure shown in Formula I:

[0007]

[0008] wherein R1, R2 and R3 are each independently selected from hydrogen, a C1-C12 alkyl group, a C3-C20 alkyl group inserted by one or more oxygen atoms, or a polyether segment substituted by a hydroxyl group;

[0009] R4 is selected from a free radical polymerizable group containing a carbon-carbon double bond;

[0010] X1 is selected from C1-C12 alkylene, C4-C12 cycloalkylene, C3-C12 heterocycloalkylene, C6-C20 arylene or C3-C20 heteroarylene;

[0011] X2 is selected from a single bond, a C1-C12 alkylene group, a C6-C20 arylene group or a C1-C12 alkylene group containing a polyester / ether group.

[0012] According to some embodiments of the present invention, in Formula I, R1, R2 and R3 are each independently selected from hydrogen and C1-C8 alkyl.

[0013] In some embodiments, R1 is hydrogen, and R2 and R3 are each independently selected from C1-C8 alkyl.

[0014] In some embodiments, R2 and R3 are the same. In some embodiments, R2 and R3 are different.

[0015] According to some embodiments of the present invention, in Formula I, R4 has a structure represented by Formula II:

[0016]

[0017] wherein Y is selected from a single bond, NR7 or O, and R7 is selected from hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl, C3-C12 heterocycloalkyl, C6-C20 aryl or C3-C20 heteroaryl;

[0018] R5 and R6 are each independently selected from hydrogen, carboxyl, C1-C12 alkyl, C3-C12 cycloalkyl, C3-C12 heterocycloalkyl, C6-C20 aryl or C3-C20 heteroaryl;

[0019] n is 0 or 1.

[0020] In some embodiments, in Formula II, R7 is selected from hydrogen, C1-C8 alkyl and C6-C12 aryl.

[0021] In some embodiments, in Formula II, R7 is selected from hydrogen, C1-C4 alkyl and C6-C10 aryl.

[0022] In some preferred embodiments, in Formula II, R7 is selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and phenyl.

[0023] In some specific embodiments, in Formula II, R7 is hydrogen.

[0024] According to some embodiments of the present invention, in Formula II, R5 and R6 are each independently selected from hydrogen, carboxyl, C1-C8 alkyl and C6-C12 aryl.

[0025] According to some preferred embodiments of the present invention, in Formula II, R5 and R6 are each independently selected from hydrogen, carboxyl, C1-C4 alkyl and C6-C10 aryl.

[0026] In some preferred embodiments, in Formula II, R5 and R6 are each independently selected from hydrogen, carboxyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and phenyl.

[0027] In some embodiments, in Formula II, R5 is selected from hydrogen, C1-C8 alkyl, and C6-C12 aryl.

[0028] In some preferred embodiments, in Formula II, R5 is selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and phenyl.

[0029] In some embodiments, in Formula II, R6 is selected from hydrogen, carboxyl, C1-C8 alkyl and C6-C12 aryl.

[0030] In some preferred embodiments, in Formula II, R6 is selected from hydrogen, carboxyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and phenyl.

[0031] In some embodiments, in Formula II, Y is selected from a single bond, NH or O.

[0032] In some preferred embodiments, in Formula II, Y is selected from a single bond or O.

[0033] In some preferred embodiments, in Formula I, R4 is selected from the following structures:

[0034]

[0035] According to some embodiments of the present invention, in Formula I, X1 and X2 are each independently selected from C1-C8 alkylene, C6-C12 arylene.

[0036] According to some embodiments of the present invention, in Formula I, X1 and X2 are each independently selected from C1-C6 alkylene, C6-C10 arylene.

[0037] In some preferred embodiments, in Formula I, X1 and X2 are each independently selected from ethylene, 1,4-butylene and phenylene.

[0038] In some specific embodiments, in Formula I, X1 is phenylene.

[0039] In some specific embodiments, in Formula I, X2 is ethylene.

[0040] In some preferred embodiments, the triazine-based compound has a structure represented by Formula Ia:

[0041]

[0042] In Formula Ia, R2, R3, R4 and X2 are as defined in Formula I.

[0043] In some preferred embodiments, in Formula Ia, R2 and R3 are each independently selected from C1-C8 alkyl, preferably n-butyl.

[0044] In some preferred embodiments, in Formula Ia, X2 is selected from C1-C8 alkylene, preferably C1-C4 alkylene, more preferably ethylene.

[0045] In some preferred embodiments, the triazine-based compound has a structure represented by Formula Ib or Formula Ic:

[0046]

[0047] In Formula Ib and Formula Ic, R1, R2, R3 and X1 are as defined in Formula I.

[0048] In some preferred embodiments, in Formula Ib and Formula Ic, X1 is selected from C6-C10 arylene, and preferably X1 is phenyl.

[0049] In some preferred embodiments, in Formula Ib and Formula Ic, R1 is selected from hydrogen and C1-C6 alkyl, preferably R1 is hydrogen.

[0050] In some preferred embodiments, in Formula Ib and Formula Ic, R2 and R3 are each independently selected from hydrogen and C1-C6 alkyl,

[0051] In some more preferred embodiments, in Formula Ib and Formula Ic, R2 and R3 are the same and are selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.

[0052] According to some preferred embodiments of the present invention, the triazine compound is selected from the following structures:

[0053]

[0054] In a second aspect, the present invention provides a method for preparing the triazine-based compound according to the first aspect, comprising the following steps:

[0055] (1) Mix cyanuric chloride, reagent SM1 and solvent, and react at -10 to 20° C. for 0.5 to 2 hours to obtain intermediate 1;

[0056]

[0057] (2) Mixing the intermediate product 1 with the reagent SM2, and reacting at 50-80° C. for 2-5 h to obtain the intermediate product 2;

[0058]

[0059] (3) adding reagent SM3 to the intermediate product 2, reacting at 100-130° C. for 5-15 h to obtain the compound of formula I;

[0060]

[0061] Wherein, R1, R2, R3, R4, X1 and X2 are defined the same as in Formula I.

[0062] According to some embodiments of the present invention, the solvent in step (1) includes one or more of ethanol, acetone, tetrahydrofuran, toluene, water, and N,N-dimethylformamide.

[0063] In a third aspect, the present invention provides a polymerizable dispersant monomer composition, which includes the triazine-based compound described in the first aspect of the present invention and other compounds, wherein the other compounds include one or more of methacrylate compounds, acrylate compounds, methacrylate compounds containing tertiary amines, and acrylate compounds containing tertiary amines.

[0064] According to some embodiments of the present invention, the methacrylate compound is selected from esters formed by methacrylic acid and one or more selected from C1-C10 monohydric or dihydric fatty alcohols, C1-C10 alicyclic alcohols, C6-C12 aromatic alcohols, and aromatic-substituted C1-C10 monohydric or dihydric fatty alcohols.

[0065] Examples of the methacrylate compounds of the present invention include, but are not limited to, methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, benzyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, and n-octyl methacrylate.

[0066] According to some embodiments of the present invention, the acrylic ester compound is selected from esters formed by acrylic acid and one or more of C1-C10 monohydric or dihydric fatty alcohols, C1-C10 alicyclic alcohols, C6-C12 aromatic alcohols, aromatic-substituted C1-C10 monohydric or dihydric fatty alcohols, tetrahydrofuran-substituted C1-C10 monohydric or dihydric fatty alcohols, and 1,4-oxazahexacyclic alcohols.

[0067] Examples of the acrylic acid ester compounds of the present invention include, but are not limited to, methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, n-butyl acrylate, isobutyl acrylate, benzyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, 2-tetrahydrofuranyl acrylate, and acryloylmorpholine.

[0068] According to some embodiments of the present invention, the tertiary amine-containing methacrylate compound is an adduct of a dialkylamine and a difunctional or multifunctional methacrylate, such as dimethylaminoethyl methacrylate.

[0069] According to some embodiments of the present invention, the tertiary amine-containing acrylate compound is an adduct of a dialkylamine and a difunctional or multifunctional acrylate, such as dimethylaminoethyl acrylate.

[0070] According to some embodiments of the present invention, in the composition, the mass proportion of the triazine-based compound is 2%-40%, and the mass proportion of the other compounds is 60-98%.

[0071] In a fourth aspect, the present invention provides a polymer dispersant, which includes the triazine-based compound described in the first aspect of the present invention, or is prepared from a raw material including the polymerizable dispersant monomer composition described in the third aspect of the present invention.

[0072] The triazine-based compound described in the first aspect of the present invention can be used alone as a polymer dispersant, or can be used as a polymer dispersant after being polymerized with other compounds.

[0073] According to some embodiments of the present invention, the polymer dispersant is obtained by a free radical polymerization reaction between the triazine-based compound and the other compound.

[0074] According to some embodiments of the present invention, in the free radical polymerization reaction, the molar ratio of the triazine compound to the other compound is 1:(1-3).

[0075] According to some embodiments of the present invention, the free radical polymerization reaction is carried out in the presence of an initiator. Examples of the initiator of the present invention include, but are not limited to, ammonium persulfate, potassium persulfate, and the like.

[0076] According to some embodiments of the present invention, the molar ratio of the initiator to the triazine-based compound is (0.01-0.1): 1. In some embodiments, the molar ratio of the initiator to the triazine-based compound is (0.03-0.08): 1.

[0077] According to some embodiments of the present invention, the temperature of the free radical polymerization reaction is 40-60°C.

[0078] In a fifth aspect, the present invention provides a color paste comprising a pigment, a solvent and a dispersant, wherein the dispersant comprises the polymer dispersant described in the fourth aspect of the present invention.

[0079] According to some embodiments of the present invention, the pigment includes one or more of a red pigment, a green pigment, a blue pigment and a black pigment.

[0080] Examples of the red pigment of the present invention include, but are not limited to, PR122 red.

[0081] Examples of the blue pigment of the present invention include, but are not limited to: A4R blue 15:1.

[0082] Examples of the green pigment of the present invention include, but are not limited to, BASF K8730 green.

[0083] Examples of the black pigment of the present invention include, but are not limited to, Mitsubishi Carbon Black MA100.

[0084] According to some embodiments of the present invention, the solvent is selected from water or an organic solvent. Examples of the organic solvent include, but are not limited to, propylene glycol methyl ether acetate. In some embodiments, the solvent is water. In some embodiments, the solvent is propylene glycol methyl ether acetate.

[0085] According to some embodiments of the present invention, in the color paste, the mass of the polymer dispersant is 2-8% of the mass of the pigment.

[0086] According to some embodiments of the present invention, the dispersant further comprises other dispersants. Examples of the other dispersants of the present invention include but are not limited to: dispersant BYK9076, dispersant BYK2012, and the like.

[0087] According to some embodiments of the present invention, the color paste further comprises a resin having an acidic group, and the resin having an acidic group is preferably a polyacrylate or polymethacrylate having a carboxylic acid group.

[0088] Examples of the resin having an acidic group of the present invention include, but are not limited to, copolymers of hydroxyethyl methacrylate, benzyl methacrylate and methacrylic acid, copolymers of methyl methacrylate and methacrylic acid, copolymers of benzyl methacrylate and methacrylic acid, copolymers of methyl methacrylate and butyl methacrylate, and copolymers of methacrylic acid and styrene.

[0089] In a sixth aspect, the present invention provides the use of the triazine compound described in the first aspect, the polymerizable dispersant monomer composition described in the third aspect, the polymer dispersant described in the fourth aspect, or the color paste described in the fifth aspect in printing inks, nail polishes, PCB solder mask inks, photoresists, and coatings.

[0090] Compared with the prior art, the present invention has the following beneficial effects:

[0091] The triazine-based compound provided by the present invention contains both a sulfonic acid group and an organic amine group in its structure, so that it has both pigment affinity and solvent affinity as its interface activity. At the same time, the triazine-based compound also contains a carbon-carbon double bond that can be polymerized by free radicals, so that it can be further polymerized with other monomers and applied to the preparation of color pastes of different colors. The dispersion effect of pigments, especially phthalocyanine pigments, can be greatly improved, the stratification and precipitation phenomena during the storage of the color paste can be significantly improved, and the storage stability of the color paste can be improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0092] Figure 1 The gel permeation chromatogram of the polymer dispersant prepared in Example 3 is shown.

[0093] Figure 2 The gel permeation chromatogram of the polymer dispersant prepared in Example 4 is shown. DETAILED DESCRIPTION

[0094] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments and drawings. The specific embodiments described herein are only used to explain the present invention and are not intended to constitute any limitation to the present invention.

[0095] The term "C1-C12 alkyl" as used herein refers to a linear or branched chain alkyl group having 1 to 12 carbon atoms, including but not limited to methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, n-hexyl and its isomers, n-heptyl and its isomers, n-octyl and its isomers, n-nonyl and its isomers, n-decyl and its isomers, etc. In addition, the alkyl group described in the present invention may be optionally substituted.

[0096] As used herein, the term "C3-C20 alkyl group interrupted by one or more O atoms" refers to a C3-C20 alkyl group that is interrupted by O once or more times, for example, 1-9 times, 1-5 times, 1-3 times, or 2 times or 1 time. If there is more than one spacer group, they are of the same type or different. Two O atoms are separated by at least one methylene group, preferably at least two methylene groups (i.e., ethylene groups). These alkyl groups are linear or branched. For example: -CH2-CH2-O-CH2CH3-, -CH2-CH(CH3)-O-CH2-CH2O-CH3-, etc.

[0097] The term "polyether segment" used herein refers to the smallest unit in the polyether polymer chain that can move independently. The segment length can be used to characterize the flexibility of the chain.

[0098] The term "cycloalkyl" as used herein refers to an alkyl group containing at least one ring, and a C3-C12 cycloalkyl group refers to a cyclic alkyl group having 3 to 12 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like.

[0099] The term "heterocycloalkyl" as used herein includes non-aromatic cyclic groups, including saturated heterocyclic groups having 3-12 ring atoms and unsaturated non-aromatic heterocyclic groups having 3-12 ring atoms, wherein at least one ring atom is selected from the group consisting of nitrogen atom, oxygen atom, sulfur atom, selenium atom, silicon atom, phosphorus atom, germanium atom and boron atom. Examples of heterocycloalkyl include oxirane, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, dioxopentanyl, dioxanyl, aziridinyl, dihydropyrrolyl, tetrahydropyrrolyl, piperidinyl, oxazolidinyl, morpholinyl, piperazinyl, oxepinyl, thiepinyl, azepineyl and tetrahydrothioxyl. In addition, heterocycloalkyl may be optionally substituted.

[0100] The term "aryl or aromatic group" as used herein includes both non-fused and fused systems. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms. Examples of aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, Perylene and azulene, preferably phenyl, biphenyl, biphenyl, triphenylene, fluorene and naphthalene. Examples of non-condensed aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p-(2-phenylpropyl)phenyl, 4'-methylbiphenyl, 4"-tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2,3-xylyl, 3,4-xylyl, 2,5-xylyl, mesityl and m-quadrenyl. In addition, the aryl group may be optionally substituted.

[0101] As used herein, the term "heteroaryl" includes monocyclic or polycyclic ring systems, such as fused ring systems. C3-C20 heteroaryl includes, but is not limited to, thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thianthrenyl, furanyl, dibenzofuranyl, benzopyranyl, xanthene, thioxanthenyl, phenothiazine, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinolyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, perylene, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, phenanthrolinyl, oxazinyl, 7-phenanthrenyl, anthraquinone-2-yl (= 9,10-dioxo-9,10-dihydroanthracen-2-yl), 3-benzo[b]thienyl, 5-benzo[b]thienyl, 2-benzo[b]thienyl, 4-dibenzofuranyl, 4,7-dibenzofuranyl, 4-methyl-7-dibenzofuranyl, 2-xanthenyl, 8-methyl-2-xanthenyl, 3-xanthenyl, 2-phenoxathiol, 2,7-phenothiol, 2-pyrrolyl, 3-pyrrolyl, 5-methyl-3-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2-methyl-4-imidazolyl, 2-ethyl-4-imidazolyl, 2-ethyl- 5-imidazolyl, 1H-tetrazol-5-yl, 3-pyrazolyl, 1-methyl-3-pyrazolyl, 1-propyl-4-pyrazolyl, 2-pyrazinyl, 5,6-dimethyl-2-pyrazinyl, 2-indolizinyl, 2-methyl-3-isoindolyl, 2-methyl-1-isoindolyl, 1-methyl-2-indolyl, 1-methyl-3-indolyl, 1,5-dimethyl-2-indolyl, 1-methyl-3-indazolyl, 2,7-dimethyl-8-purinyl, 2-methoxy-7-methyl-8-purinyl, 2-quinolizinyl, 3-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 3-methoxy-6-isoquinolyl , 2-quinolyl, 6-quinolyl, 7-quinolyl, 2-methoxy-3-quinolyl, 2-methoxy-6-quinolyl, 6-phthalazinyl, 7-phthalazinyl, 1-methoxy-6-phthalazinyl, 1,4-dimethoxy-6-phthalazinyl, 1,8-naphthyridin-2-yl, 2-quinolyl, 6-quinolyl, 2,3-dimethyl-6-quinolyl, 2,3-dimethoxy-6-quinolyl, 2-quinazolinyl, 7-quinazolinyl, 2-dimethylamino-6-quinazolinyl, 3-cinnolinyl, 6-cinnolinyl, 7-cinnolinyl, 3-methoxy-7-cinnolinyl, 2-pteridinyl, 6-pteridinyl, 7-pteridinyl, 6,7-dimethoxy-2-pteridinyl, 2-carbazolyl, 3-carbazolyl, 9-methyl-2-carbazolyl, 9-methyl-3-carbazolyl, β-carbolin-3-yl, 1-methyl-β-carbolin-3-yl, 1-methyl-β-carbolin-6-yl, 3-phenanthridinyl, 2-acridinyl, 3-acridinyl, 2-perylene-1-methyl-5-perylene-1-methyl-5-perylene-1-methyl-6-phenanthridinyl, 1-phenazinyl, 2-phenazinyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-phenothiazinyl, 3-phenothiazinyl, 10-methyl-3-phenothiazinyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 4-methyl-3-furazanyl, 2-phenazinyl, 10-methyl-2-phenazinyl, and the like. Additionally, heteroaryl groups may be optionally substituted.

[0102] The reagent materials and sources used in the present invention are shown in Table 1.

[0103] Table 1

[0104]

[0105]

[0106] The high-speed disperser used in the present invention is model S18-8G, produced by Yangzhou Junrui Machinery Equipment Co., Ltd.; the spectrophotometer used is model UV1800, produced by Shimadzu Instruments.

[0107] Example 1: Preparation of triazine compound I-1

[0108]

[0109] Step 1: Use acetone (40 g) to completely dissolve cyanuric chloride (7.36 g 20 mmol), and use water (1000 g) to completely dissolve sulfanilic acid (6.96 g 20 mmol). The reaction temperature is controlled at 0-5°C. Under stirring, use a constant pressure dropping funnel to drop cyanuric chloride into the sulfanilic acid aqueous solution, and react for 1.5 hours; the filter cake obtained by vacuum filtration is 13 g of the product.

[0110] Step 2: Take the product of the first step (12.84 g 40 mmol) and di-n-butylamine (5.16 g 40 mmol), add triethylamine (8.08 g 80 mmol) as an acid binding agent, react at 80°C for 4 h, and filter under reduced pressure to obtain 14 g of an intermediate product.

[0111] Step 3: Take the product of the second step (8.28 g 20 mmol) and hydroxyethyl methylpropionate (2.6 g 20 mmol) at 120°C and 16 g toluene as solvent, react for 12 hours to obtain 5 g of a yellow-brown viscous liquid.

[0112] Example 2: Preparation of triazine compound I-2

[0113] The second step product in Example 1 (6.2 g, 15 mmol) and ethylene glycol vinyl ether (1.32 g, 15 mmol) were reacted in 32 g of toluene at 120° C. for 12 h, cooled and filtered to obtain 5 g of the product as a yellow-brown solid.

[0114]

[0115] Example 3: Preparation of polymer dispersant 1

[0116] Compound I-1 (1.518 g 3 mmol) prepared in Example 1 was dissolved in 10 g ethanol, ammonium persulfate (0.0342 g 0.15 mmol) 2 g water was dissolved, two equivalents of isooctyl methylpropionate were added, and the reaction was started at 50° C. with nitrogen protection throughout the process; the reaction was continued for 4 h, and the product was cooled and filtered to obtain 1 g of a light yellow, crisp solid. The gel permeation chromatography (GPC) was as follows: Figure 1 shown.

[0117] Example 4: Preparation of polymer dispersant 2

[0118] Compound I-2 (1.398 g 3 mmol) prepared in Example 2 was dissolved in 10 g ethanol, ammonium persulfate (0.0342 g 0.15 mmol) was dissolved in 2 g water, two equivalents of isooctyl methylpropionate were added, and the reaction was started at 50°C with nitrogen protection throughout the process; the reaction was continued for 4 h. The product was cooled and filtered to obtain 1 g of a light yellow solid. The gel permeation chromatography (GPC) was as follows: Figure 2 shown.

[0119] Example 5: Preparation of oily green color paste

[0120] The polymer dispersants in the above-mentioned Examples 3 and 4 are applied to the preparation of phthalocyanine green slurry:

[0121] BASF K8730 green pigment, dispersant BYK9076, polymer dispersant, acidic group-containing resin, PMA (propylene glycol methyl ether acetate) were weighed in sequence, and ultrasonic dispersion was performed for 10 minutes, and high-speed shearing was performed at 5000 r / min, 10 minutes, and 9000 r / min, 10 minutes. The specific contents are shown in Table 2.

[0122] The synthesis method of the acidic group-containing resin is as follows: 6 parts of hydroxyethyl methacrylate, 18 parts of benzyl methacrylate, 6 parts of methacrylic acid, 0.6 parts of dodecanethiol and 200 parts of toluene are weighed in sequence and added into a three-necked flask, and a mixed solution of 1.5 parts of azobisisobutyronitrile and toluene is added dropwise into the flask, and the mixture is added after 1.5 hours, and the reaction is continued for 4 hours, and a white solid product is obtained by cooling and filtering.

[0123] The stability was evaluated by static storage: the mixture was placed for 14 days, the stratification phenomenon was observed, and the stratification ratio (height of the upper liquid layer after stratification / total height) was measured. The results are shown in Table 3.

[0124] Transmittance test: After the prepared color paste was centrifuged at 10000 r / min for 10 min, the supernatant was taken and diluted to three times, and the transmittance was measured at 523 nm using a spectrophotometer. The results are shown in Table 3.

[0125] Table 2 Green color paste formula and test results

[0126]

[0127] Note: “-” means no corresponding ingredient is added.

[0128] Table 3 Delamination and transmittance evaluation

[0129]

[0130] From the results of Table 2 and Table 3, it can be seen that, compared with the comparative color paste a, the addition of the polymer dispersant of the present invention significantly improves the phenomenon of static stratification of the color paste 1-6, and its transmittance after centrifugation is also significantly reduced, which can indicate that the stability of the color paste using the polymer dispersant of the present invention is improved. In particular, when the amount of dispersant is the same, the polymer dispersant 2 of the present invention has a greater degree of improvement in the stability of the phthalocyanine green system. When the amount of the polymer dispersant is 3.33% of the pigment content, the color paste stability effect is the best.

[0131] Example 6: Preparation of blue and red color pastes

[0132] The polymer dispersants in Examples 3 and 4 were applied to the preparation of blue and red color pastes:

[0133] Red or blue pigment, dispersant BYK9076, polymer dispersant, acidic group-containing resin, PMA (propylene glycol methyl ether acetate) were weighed in sequence. Ultrasonic dispersion was performed for 10 min, and high-speed shearing was performed at 5000 r / min, 10 min, and 9000 r / min, 10 min. The specific contents are shown in Table 4. The preparation of the acidic group-containing resin was the same as in Example 5.

[0134] The stability was evaluated by static storage: the solution was stored for 14 days, the precipitation phenomenon was observed, the height of the precipitation layer was measured, and the ratio of the precipitation layer to the total height of the solution was calculated. The results are shown in Table 4.

[0135] Table 4 Blue and red color paste formula and test results

[0136]

[0137] Note: “-” means no corresponding ingredient is added.

[0138] From the test results of color paste 7, color paste 8 and comparative color paste b in Table 4 above, it can be seen that the polymer dispersants in Examples 3 and 4 of the present invention have the effect of increasing the stability of the red pigment system. Color paste 7 did not show precipitation, and color paste 8 showed less precipitation than comparative color paste b.

[0139] From the test results of color paste 9, color paste 10 and comparative color paste c, it can be seen that the polymer dispersants in Examples 3 and 4 of the present invention have the effect of increasing the stability of the blue pigment dispersion system. Color paste 9 is still in a gel state and no precipitation occurs, while the precipitation ratio of color paste 10 is much smaller than that of comparative color paste c.

[0140] Example 7: Preparation of water-based green color paste

[0141] The polymer dispersants in the above-mentioned Examples 3 and 4 are applied to the preparation of phthalocyanine green slurry:

[0142] BASF K8730 green pigment, dispersant BYK9076, polymer dispersant and water were weighed in sequence. Ultrasonic dispersion was performed for 10 min, and high-speed shear was performed at 5000 r / min, 10 min, and 9000 r / min, 10 min. The specific contents are shown in Table 5.

[0143] Transmittance test: After the prepared color paste was centrifuged at 10000 r / min for 20 min, the supernatant was taken and diluted to three times, and the transmittance was measured at 523 nm using a spectrophotometer. The results are shown in Table 5.

[0144] Table 5 Water-based color paste formula and test results

[0145]

[0146] Note: “-” means no corresponding ingredient is added.

[0147] From the results of color paste 11, color paste 12 and comparative color paste d, it can be seen that the color pastes to which the polymer dispersants prepared in Examples 3 and 4 of the present invention are added have significantly reduced transmittance of the dispersed system after centrifugation, indicating that the stability of the dispersed system is improved, especially the effect of the polymer dispersant 2 in Example 4 is more prominent.

[0148] In summary, among the polymer dispersants provided by the present invention, polymer dispersant 1 significantly improves the stability of the red and blue pigment paste systems, and can achieve long-term storage without precipitation. Polymer dispersant 2 significantly improves the stability of the green pigment paste system, and can significantly reduce the stratification ratio of the system and the transmittance after centrifugation.

[0149] The technical solution of the present invention is not limited to the above-mentioned specific embodiments. All technical variations made according to the technical solution of the present invention fall within the protection scope of the present invention.

Claims

1. A triazine compound having a structure shown in Formula I: in, R1, R2 and R3 are each independently selected from hydrogen, C1-C12 alkyl, C3-C20 alkyl inserted by one or more oxygen atoms or a polyether segment substituted by a hydroxyl group; R4 is selected from a free radical polymerizable group containing a carbon-carbon double bond; X1 is selected from C1-C12 alkylene, C4-C12 cycloalkylene, C3-C12 heterocycloalkylene, C6-C20 arylene or C3-C20 heteroarylene; X2 is selected from a single bond, a C1-C12 alkylene group, a C6-C20 arylene group or a C1-C12 alkylene group containing a polyester / ether group.

2. The triazine compound according to claim 1, characterized in that R1, R2 and R3 are each independently selected from hydrogen and C1-C8 alkyl; Preferably, R1 is hydrogen, and R2 and R3 are each independently selected from C1-C8 alkyl.

3. The triazine compound according to claim 1 or 2, characterized in that R4 has a structure represented by formula II: wherein Y is selected from a single bond, NR7 or O, and R7 is selected from hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl, C3-C12 heterocycloalkyl, C6-C20 aryl or C3-C20 heteroaryl, preferably hydrogen, C1-C8 alkyl and C6-C12 aryl, more preferably hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and phenyl; R5 and R6 are each independently selected from hydrogen, carboxyl, C1-C12 alkyl, C3-C12 cycloalkyl, C3-C12 heterocycloalkyl, C6-C20 aryl or C3-C20 heteroaryl, preferably hydrogen, carboxyl, C1-C8 alkyl and C6-C12 aryl, more preferably hydrogen, carboxyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and phenyl; n is 0 or 1; Preferably, R4 is selected from the following structures:

4. The triazine compound according to any one of claims 1 to 3, characterized in that X1 and X2 are each independently selected from C1-C8 alkylene, C6-C12 arylene, preferably ethylene, 1,4-butylene and phenylene.

5. The triazine compound according to any one of claims 1 to 4, characterized in that The triazine compound is selected from the structure shown in Formula Ia, Formula Ib or Formula Ic: In Formula Ia, R2, R3, R4 and X2 are as defined in Formula I; In Formula Ib and Formula Ic, R1, R2, R3 and X1 are as defined in Formula I; Preferably, the triazine-based compound is selected from the structure represented by Formula I-1 or Formula I-2:

6. A method for preparing the triazine compound according to any one of claims 1 to 5, comprising the following steps: (1) Mix cyanuric chloride, reagent SM1 and solvent, and react at -10 to 20° C. for 0.5 to 2 hours to obtain intermediate 1; (2) Mixing the intermediate product 1 with the reagent SM2, and reacting at 50-80° C. for 2-5 h to obtain the intermediate product 2; (3) adding reagent SM3 to the intermediate product 2, reacting at 100-130° C. for 5-15 h to obtain the compound of formula I; in, R1, R2, R3, R4, X1 and X2 are as defined in Formula I; Preferably, the solvent in step (1) comprises one or more of ethanol, acetone, tetrahydrofuran, toluene, water, and N,N-dimethylformamide.

7. A polymerizable dispersant monomer composition, comprising the triazine compound according to any one of claims 1 to 5 and other compounds, wherein the other compounds include one or more of methacrylate compounds, acrylate compounds, methacrylate compounds containing tertiary amines, and acrylate compounds containing tertiary amines; Preferably, the methacrylate compound is selected from esters formed by methacrylic acid and one or more selected from C1-C10 monohydric or dihydric fatty alcohols, C1-C10 alicyclic alcohols, C6-C12 aromatic alcohols, and aromatic substituted C1-C10 monohydric or dihydric fatty alcohols; more preferably, one or more selected from methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, benzyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, and n-octyl methacrylate; Preferably, the acrylic acid ester compound is selected from the ester formed by acrylic acid and one or more of C1-C10 monohydric or dihydric aliphatic alcohols, C1-C10 alicyclic alcohols, C6-C12 aromatic alcohols, aromatic substituted C1-C10 monohydric or dihydric aliphatic alcohols, tetrahydrofuran substituted C1-C10 monohydric or dihydric aliphatic alcohols, and 1,4-oxazine hexacyclic alcohols; more preferably, one or more of methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, n-butyl acrylate, isobutyl acrylate, benzyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, 2-tetrahydrofuran acrylate, and acryloylmorpholine; Preferably, the tertiary amine-containing methacrylate compound and the tertiary amine-containing acrylate compound are selected from the adducts of dialkylamine and difunctional or multifunctional methacrylate, and the adducts of dialkylamine and difunctional or multifunctional acrylate, respectively, preferably dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate; Preferably, in the composition, the mass proportion of the triazine-based compound is 2%-40%, and the mass proportion of the other compounds is 60-98%.

8. A polymer dispersant comprising the triazine-based compound according to any one of claims 1 to 5, or prepared from a raw material comprising the polymerizable dispersant monomer composition according to claim 7.

9. The polymer dispersant according to claim 8, characterized in that The polymer dispersant is obtained by free radical polymerization of the triazine-based compound and the other compounds; Preferably, in the free radical polymerization reaction, the molar ratio of the triazine compound to the other compound is 1:(1-3); Preferably, the free radical polymerization reaction is carried out in the presence of an initiator; more preferably, the initiator comprises ammonium persulfate and / or potassium persulfate; further preferably, the molar ratio of the initiator to the triazine compound is (0.01-0.1):1; Preferably, the temperature of the free radical polymerization reaction is 40-60°C.

10. A color paste comprising a pigment, a solvent and a dispersant, wherein the dispersant comprises the polymer dispersant according to claim 8 or 9.

11. The color paste according to claim 10, characterized in that: The pigment includes one or more of a red pigment, a green pigment, a blue pigment and a black pigment; preferably, the red pigment includes PR122 red, the blue pigment includes A4R blue 15:1, the green pigment includes BASF K8730 green, and the black pigment includes Mitsubishi carbon black MA100; The solvent is selected from water or an organic solvent, preferably water or propylene glycol methyl ether acetate; Preferably, the mass of the polymer dispersant is 2-8% of the mass of the pigment; Optionally, the dispersant further comprises other dispersants, preferably, the other dispersants are selected from BYK9076 and / or BYK2012; Optionally, the color paste also includes a resin having an acidic group, and the resin having an acidic group is preferably a polyacrylate or polymethacrylate having a carboxylic acid group, more preferably hydroxyethyl methacrylate and benzyl methacrylate and methacrylic acid copolymer, methyl methacrylate and methacrylic acid copolymer, benzyl methacrylate and methacrylic acid copolymer, methyl methacrylate and butyl methacrylate, and methacrylic acid and styrene copolymer.

12. Use of the triazine compound according to any one of claims 1 to 5, the polymerizable dispersant monomer composition according to claim 7, the polymer dispersant according to any one of claims 8 to 9, or the color paste according to any one of claims 10 to 11 in printing inks, nail polishes, PCB solder mask inks, photoresists, and coatings.

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