CN117603604A - Preparation method of printing gloss oil with amino-terminated hyperbranched self-assembled polyamide as main component - Google Patents

Preparation method of printing gloss oil with amino-terminated hyperbranched self-assembled polyamide as main component Download PDF

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CN117603604A
CN117603604A CN202311535388.0A CN202311535388A CN117603604A CN 117603604 A CN117603604 A CN 117603604A CN 202311535388 A CN202311535388 A CN 202311535388A CN 117603604 A CN117603604 A CN 117603604A
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solvent
acid
amino
hyperbranched
temperature
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张斯乔
唐丘
宋之太
李颂国
宋子轩
张晨曦
吴帅男
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Jiangsu Zhonglisheng Package Technology Co ltd
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    • 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
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4054—Mixtures of compounds of group C08G18/60 with other macromolecular compounds
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    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/60—Polyamides or polyester-amides
    • C08G18/603—Polyamides
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203

Abstract

The invention belongs to the technical field of high polymer materials, and relates to a preparation method of printing gloss oil with terminal amino hyperbranched self-assembled polyamide as a main component, which comprises the following steps of preparing halogenated tert-butyl dimethyl ester; then adding hexamethylenetetramine/NaHCO to the prepared halogenated tert-butyl dimethyl ester 3 Obtaining amino tertiary butyl dimethyl ester; then adding the carboxylic acid or adding K 2 CO 3 Methanol solution to obtain hyperbranched pre-polymerized monomer AB n The method comprises the steps of carrying out a first treatment on the surface of the Adding a catalyst to obtain amino-terminated hyperbranched polyamide; adding the polyatomic alcohol, the polyisocyanate and the chain extender into the solvent, stirring and dissolving, and continuously adding the acrylic diluent, the photoinitiator, the flatting agent and the wax slurry to obtain the printing gloss oil. The printing gloss oil prepared by the invention has excellent drying and curing efficiency, and the coating obtained after curing has higher glossiness and good leveling effect, and has outstanding advantages in aspects such as hardness, adhesive force and water resistance.

Description

Preparation method of printing gloss oil with amino-terminated hyperbranched self-assembled polyamide as main component
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to printing varnish, in particular to a preparation method of printing varnish taking amino-terminated hyperbranched self-assembled polyamide as a main component.
Background
After the start of the application of synthetic polymers to commercial products, researchers in the field of material science have been striving to improve polymer properties by new methods. At that time, the most common techniques have not simply been to develop a new monomer or to synthesize a new polymer, or to modify existing polymers by chemical routes, often by changing the catalyst or using different monomers. For example, short chain branches and long chain branches are used for modifying the original molecular structure of the polymer, and the crystallinity and viscosity of the polymer are adjusted.
In 1952, the famous polymer scientist Flory, in his "principle of polymer chemistry", indicated another method of synthesizing polymers, and established the theory of preparing polymers by condensing a plurality of functional monomers. He predicts that such polymers have a broad molecular mass distribution and are not easily entangled and crystallized between the molecules due to their highly branched structure. However, flory at the time considered that such polymers have not been of great research value because of the poor mechanical strength of such polymers. Until thirty years later, the first paper on synthetic dendrimers was published, and in 1985, the Tomalia doctor and the Newkome doctor respectively published an article on dendrimers. Dendrimers have many very unique properties compared to linear polymers. For example, in the case of sufficiently high molecular weights, dendrimers exhibit a spherical structure, and dendrimers behave more like molecular micelles than linear polymers.
Researchers have found that dendritic polymers, while having some unique properties, are too complex to synthesize perfect dendrimers, are costly to synthesize and require significant time and effort. Following this, dupont technicians Kim and Webster developed a one-step synthesis of branched polyphenyl during the study of dendrons as rheology modifiers and spherical polyfunctional initiators. Such polymers are highly branched dendrimers with polydispersity, which have defects in the formation of the linear segments of the molecule, not perfectly monodisperse dendrimers, which Kim and Webster name hyperbranched polymers (Hyperbaranched polymer).
Hyperbranched polymers are widely noted for their unique properties and find application in agriculture, medicine, liquid crystals, functional materials, life sciences, cosmetics, xu Liao, paints and other fields.
(1) Application of hyperbranched polymer in functional conjugated material
The hyperbranched conjugated polymer can be synthesized due to the good solubility, excellent processability and three-dimensional stereomorphology of the hyperbranched polymer. Currently, hyperbranched polymers are favored by many researchers as novel optical, electrical and magnetic materials. The three-dimensional structure of the hyperbranched conjugated polymer can reduce interactions between molecules under the aggregation state condition compared with the linear conjugated polymer, thereby reducing the reduction in luminous efficiency caused by the aggregation of the molecules.
(2) Hyperbranched electrolytes
The solid polymer electrolyte should meet four requirements: 1. not easy to crystallize, 2 has strong solvation property for proper ions, 3 has good ion conductivity, and 4 has electrochemical stability. It is known that the oligosaccharide (ethylene glycol) segment satisfies the latter three conditions of the four conditions required for the solid polymer electrolyte, while the hyperbranched polymer has a property of being not easily crystallized, so that the hyperbranched polymer and the ethylene glycol segment are combined in molecular design to form the hyperbranched polymer with the hexanediol segment, so that the hyperbranched polymer has the function of the polymer electrolyte.
(3) Application of hyperbranched polymer in nano material
Hyperbranched polymers and their alternatives can be used as nanomaterials in encapsulation reactions and in the manufacture of organic-inorganic mixtures, even directly as nanoreactors in certain reactions. The esterification reaction of the hyperbranched polymer and the fatty acid can synthesize a nano structure which has an amphiphilic core-shell structure. The nanostructure was found to be a reverse single-molecule micelle without aggregation in the diluent by light scattering.
(4) Application of hyperbranched polymer in biological material
Hyperbranched polymers are of increasing interest for use in the field of biological materials, as they have more defined multifunctional groups, a narrower polydispersity structure and a low viscosity by improving the synthesis methods and techniques. Hyperbranched polymers have two roles in the field of biological materials: 1. the biological carrier material, the hyperbranched polymer can be covalently bound with the selected target object through the functional group of the molecule, or the hyperbranched polymer can chelate the guest molecule by utilizing the core-shell structure of the molecule; 2. biodegradable materials.
(5) Application of hyperbranched polymer in coating
Due to the high solubility, dendritic macromolecular structure, low viscosity and functional groups of various functions of the hyperbranched polymer, the hyperbranched polymer can be applied to various coating resins, such as powder coating, high-solid coating, flame-retardant coating, isolation coating for flexible packaging and the like. The low viscosity makes the hyperbranched polymer suitable for application in high solid component coating, and can be blended with linear polymer coating to reduce the viscosity of the system and change the fluidity of the system; the high solubility can increase the solid content of the finished product, reduce the application of the solvent, and effectively reduce the cost and the pollution to the environment; the dendritic macromolecular structure enables the hyperbranched polymer coating to have good film forming property; the plurality of end group functional groups can lead the hyperbranched polymer coating to have strong modifiable property, and can prepare coatings with different purposes. Hyperbranched polymers are widely studied in the coating field and commercial products exist. Currently, hyperbranched polymers are mostly studied as hyperbranched polyesters, hyperbranched polyethers, hyperbranched polyamines/esters, hyperbranched polyamides/esters and the like.
Disclosure of Invention
The invention aims to overcome the defects of poor gloss effect, low mechanical strength, weak water resistance and the like of the traditional printing gloss oil, and discloses a preparation method of the printing gloss oil taking amino-terminated hyperbranched self-assembled polyamide as a main component and a necessary preparation process for obtaining the amino-terminated hyperbranched self-assembled polyamide.
Technical proposal
A preparation method of printing varnish with amino-terminated hyperbranched self-assembled polyamide as a main component comprises the following steps:
(1) Adding a polyhalogenated carboxylic acid into a solvent, stirring and dissolving, and controlling the temperature to be 10-50 ℃, preferably 22 ℃; adding tert-butyl dimethyl chloropropane/imidazole and then preserving heat for 4-20 hours, or adding tert-butyl dimethyl chloropropane/morpholine and then preserving heat for 10-50 minutes, preferably adding tert-butyl dimethyl chloropropane/morpholine and then preserving heat for 27 minutes; removing the solvent to obtain halogenated tert-butyl dimethyl ester; wherein the polyhalocarboxylic acid is 2, 3-dibromopropionic acid, 2, 3-dibromobutyric acid, 2, 3-dichloropropionic acid, 2, 3-dichloroisobutyric acid, 3, 5-dibromobenzoic acid, 3, 5-dibromo-4-methylbenzoic acid, 2, 6-dichlorobenzoic acid, 2,4, 6-trichlorobenzoic acid, 2, 4-dichlorobenzoic acid, pyridine-2-acetamide, 3, 5-dichloro-4-methylbenzoic acid, etc., preferably 2, 3-dibromobutyric acid; the solvent is dimethylformamide, tetrahydrofuran, dioxane, diethyl ether, toluene and the like, preferably tetrahydrofuran; the mass ratio of the tert-butyl dimethyl chloropropane to the imidazole is 1:0.5; the mass ratio of the tert-butyl dimethyl chloropropane to the morpholine is 1:3; the material ratio of the polyhalogenated carboxylic acid, the solvent, the tert-butyl dimethyl chloropropane/imidazole or the tert-butyl dimethyl chloropropane/morpholine is
1.0mol:20 to 120mL:0.92 to 1.22mol, preferably 1.0mol:90mL:1.08mol;
(2) Adding the prepared halogenated tert-butyl dimethyl ester into a solvent, stirring and dissolving, and controlling the temperature to be 50-140 ℃, preferably 82 ℃; addition of hexamethylenetetramine/NaHCO 3 Preserving heat for 5-20 h, preferably 12h; adding acid to adjust the pH to 3.8-6.7, preferably pH 5.0; removing the solvent to obtain amino tertiary butyl dimethyl ester; wherein, the hexamine/NaHCO 3 The ratio of the amounts of the substances is 1:1; the solvent is methanol, ethanol, tertiary butanol, isopropanol, etc., preferably ethanol; the acid is dilute hydrochloric acid, dilute nitric acid, dilute sulfuric acid, etc., preferably dilute hydrochloric acid; the halogenated tert-butyl dimethyl ester, solvent and hexamethylenetetramine/NaHCO 3 The material ratio of (2) is
1.0mol:25 to 70mL:0.2 to 0.6mol, preferably 1.0mol:68mL:0.3mol;
(3) Adding the prepared amino tertiary butyl dimethyl ester into a solvent, stirring and dissolving, and controlling the temperature to be 12-48 ℃, preferably 25 ℃; adding carboxylic acid and then preserving heat for 7-40 h, or adding K 2 CO 3 After the methanol solution is subjected to heat preservation for 1 to 6 hours, K is preferably added 2 CO 3 Keeping the temperature for 2 hours after the methanol solution is prepared; removing the solvent to obtain hyperbranched pre-polymerized monomer (AB n ) The method comprises the steps of carrying out a first treatment on the surface of the Wherein the K is 2 CO 3 The mass ratio of the methanol is 3:1; the solvent is tetrahydrofuran, dimethylformamide, toluene, dioxane, diethyl ether, chloroform, etc., preferably tetrahydrofuran; the carboxylic acid is acetic acid, propionic acid, n-butyric acid, etc., preferably acetic acid; said amino-tert-butyldimethyl ester, solvent, carboxylic acid or K 2 CO 3 The material ratio of the methanol solution is 1.0 mol:10-60 mL:2-4 mol, preferably 1.0mol:48mL:3mol;
(4) The hyperbranched pre-polymerized monomer (AB) n ) Adding solvent, stirring and dissolving, controlling the temperature to be 80-140 ℃, preferably 116 ℃, adding catalyst, and preserving the heat for 1-7 h, preferably 5h; removing the solvent to obtain amino-terminated hyperbranched polyamide; wherein the solvent is dioxane, methyl tertiary butyl ether, toluene, dimethylformamide, acetone, butanone, N-methylpyrrolidone, etc., preferably methyl tertiary butyl ether; the catalyst is AlCl 3 、BF 3 、ZnCl 2 、SO 3 、FeBr 2 Etc., preferably ZnCl 2 The method comprises the steps of carrying out a first treatment on the surface of the The material proportion of the hyperbranched pre-polymerization monomer, the solvent and the catalyst is 1.0-8.0 mol:80 mL:10-60 mg, preferably 6.0mol:80mL:24mg;
(5) Adding the polyatomic alcohol, the polyisocyanate and the chain extender into the solvent, stirring and dissolving, and controlling the temperature to be 80-220 ℃, preferably 165 ℃; adding a catalyst and preserving heat for 3-17 hours, preferably 8 hours after the prepared amino-terminated hyperbranched polyamide is added; regulating the temperature to 20-60 ℃, preferably 48 ℃, adding an acrylic diluent, a photoinitiator, a leveling agent and wax slurry, and then preserving the temperature for 20-60 min, preferably 50min; adding solvent to regulate the solid content to 30-45% to obtain printing varnish; wherein the polyhydric alcohol is polyether glycol (PPG-1000, PPG-2000, NJ210, NJ220, NJ 230), polytetrahydrofuran glycol (PTMG 1000, PTMG 2000), poly epsilon-caprolactone glycol (PCL 1000, PCL 2000) or the like, preferably NJ220; the polyisocyanate is dimethylbiphenyl diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4' -triphenylmethane triisocyanate, etc., preferably isophorone diisocyanate; the chain extender is 1, 4-butanediol, carbodiimide, 3-dichloro-4, 4-diaminodiphenylmethane, 4-methylenebis (di-chloroaniline), triisopropanolamine, uretonimine, isobutyl 3, 5-diaminop-chlorobenzoate, etc., preferably 1, 4-butanediol; the solvent is dioxane, acetone, butanone, toluene, cyclohexanone, dimethylformamide and the like, preferably acetone; the catalyst is a tertiary amine catalyst, an organotin compound, a non-tin organometallic compound, etc., preferably an organotin compound such as dibutyltin dilaurate; the acrylic acid diluent is BA-St, BA-TPGDA, BA-TMPTA and the like, the mass ratio of the BA-St to the BA-TPGDA is 1:0.1-10, and the mass ratio of the BA-TPGDA to the BA-TPGDA is preferably 1:0.5; the photoinitiator is 2-hydroxy-2-methyl-1-phenylpropion (Darocur 1173), 1-hydroxycyclohexylphenyl ketone, 2-methyl-2- (4-morpholino) -1- [4- (methylthio) phenyl ] -1-propanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoyl-phenylphosphonate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholino) phenyl ] -1-butanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, methyl benzoylformate or the like, preferably 2-hydroxy-2-methyl-1-phenylpropion; the leveling agent is H-633, H-850, H-810, LAG-450, etc., preferably H-850; the wax slurry is OP wax, paraffin oil, montana wax, methyl silicone oil and the like, preferably methyl silicone oil; the material proportion of the polyatomic alcohol, the polyisocyanate, the chain extender, the solvent added for the first time, the catalyst, the acrylic acid diluent, the photoinitiator, the flatting agent, the wax slurry and the amino-terminated hyperbranched polyamide is
1 mol:1.2-3.0 mol:0.2-0.5 mol:20-90 mL:3-10 mg:0.1-2.0 g:3-12 mg:0.6-20 mg:0.1-4 mg:9-18 mg, preferably 1mol:2.8mol:0.3mol:85mL:4mg:1.6g:7mg:13mg:0.8mg:16mg.
Experimental method
(1) Leveling effect test
Uniformly coating printing gloss oil on the surface of white cardboard, and controlling the wet coating amount to be 6.0+/-0.5 g/m 2 And standing the white cardboard after surface drying at room temperature in the dark, keeping the coating vertical to the horizontal plane for 20min, irradiating ultraviolet light for 30s, and observing and recording the rheological effect of the printing gloss oil.
(2) Field emission Scanning Electron Microscope (SEM)
Microstructural characterization of the printed gloss oil cured coating surface using a field emission scanning electron microscope (Hitachi S4800 model, japanese Hitachi Co.). Fixing the cured printing gloss oil obtained in the step (1) under a viewing mirror, and recording the structure and the morphology of the printing gloss oil under the size of 5 mu mm.
(3) X-ray diffraction test (XRD)
The XRD spectrum of the printed varnish coating was obtained by filtering the reflected scans of the copper nickel K alpha radiation using an energy spectrometer element analyzer (D8, karl-Ruher, germany) and recording part of the examples, the X-ray generator was operated at a voltage of 50kV and a current of 70m, and all XRD tests were carried out over a range of 5-80 °.
(4) Printing gloss oil combination property characterization
1. Drying performance test, according to GB/T1728-1979 paint film and putty film drying time determination method, measuring surface drying time by a finger touch method and measuring real drying time by a filter pressing paper method;
2. Gloss testing, namely testing the 60-degree gloss effect of the coating by adopting a gloss tester (BXl 568S type, sichuan Pick technology Co., ltd.) according to the method provided by GB1743-1979 paint film gloss measurement method, and taking 3 points in two mutually perpendicular directions for testing and averaging;
3. hardness test, namely, a film coating pencil scratch hardness tester (QHQ, tianjin, seisakusho Material testing machine) is adopted to measure the hardness of a film coating according to GB/T6739-2006 (color paint and varnish pencil method), 3 points are respectively taken in two directions which are perpendicular to each other for testing and averaging;
4. adhesive force test, namely, a paint film cross-cut tester (QFH type, tianjin, department of fine materials testing machine) is adopted to test 3 points in two mutually perpendicular directions and average according to GB/T9286-1998 'cross-cut test of paint films of color paint and varnish';
5. and (3) water resistance test, namely testing the water resistance of the printing varnish by adopting a water immersion experiment method provided by GB/T1733-1993 paint film water resistance measurement method, sealing edges by using a 1:1 mixture of paraffin and rosin, wherein the edge sealing width is about 2mm, adding deionized water into a water tank, adjusting the water temperature to be 23+/-2 ℃, and putting 2/3 of the lengths of three parallel experiment templates into the water tank. Every lh, observing whether phenomena such as light loss, color change, foaming, wrinkling, falling and rusting exist;
6. Impact resistance test, the same samples were measured 3 times and averaged using a simple beam impact tester (LSDJZ-50J, xiamen Lai St. Scientific instruments Co., ltd.) according to GB/T1732-1993 "paint film impact resistance test".
(5) Anti-rub protection test for printing gloss oil
The sample was uniformly applied to the surface of a paper printed with dark ink at a rate of about 1.6.+ -. 0.05g/m 2 The coating was tested for 1 minute and then observed for post-rub conditions using an ink tribometer (model 2000, sutherland, USA) set at a pressure of 4 lbs. at 85 rpm.
Advantageous effects
The invention discloses a preparation method of printing gloss oil with terminal amino hyperbranched self-assembled polyamide as a main component, the obtained printing gloss oil shows excellent drying and curing efficiency, a coating obtained after curing has higher glossiness and good leveling effect, and has outstanding advantages in aspects such as hardness, adhesive force and water resistance, the coating is mainly attributed to a hyperbranched structure, so that a polymer molecular chain shows three-dimensional spherical arrangement, the arrangement among chain segments is tidy and compact, compatibility effects of leveling agents, wax slurry and the like are good, and the terminal amino hyperbranched polyamide contains a large amount of active amino groups and provides more covalent bonding and hydrogen bonding sites, so that the cured film has better mechanical property and adhesion fastness, and the coating can be used as a protective layer of the printing gloss oil to effectively prevent the peeling and transfer of ink; in addition, the printing gloss oil adopts an ultraviolet curing mode, has simple construction operation, low energy consumption and other auxiliary materials during construction, and has wide application prospect.
Drawings
FIG. 1 shows a schematic diagram of the leveling effect of the printing varnish, wherein (a) is the printing varnish of comparative example 1, (b) is the printing varnish of comparative example 2, and (c) is the printing varnish of example 1;
FIG. 2 is a SEM image of a printing varnish, wherein (I) is a printing varnish of comparative example 1 and (II) is a printing varnish of example 1;
FIG. 3 XRD spectra of some examples of printing gloss oils;
FIG. 4 shows the anti-friction protective effect of the varnish, wherein (A) is the varnish for comparative example 1 and (B) is the varnish for example 1.
Detailed Description
The invention will now be described in detail with reference to specific examples which will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by those skilled in the art without departing from the spirit of the invention, which falls within the scope of the invention.
Comparative example 1
1mol of NJ220, 2.8mol of isophorone diisocyanate and 0.3mol of 1, 4-butanediol are added into 85mL of acetone, and then stirred for dissolution, and the temperature is controlled at 165 ℃; adding 4mg of dibutyltin dilaurate, and preserving heat for 8 hours; the temperature is adjusted to 48 ℃, 1.6g of BA-TPGDA (1:0.5), 72mg of 2-hydroxy-2-methyl-1-phenylpropionic acid, 13mg of H-850 and 0.8mg of methyl silicone oil are added, and then the mixture is kept for 50 minutes; adding solvent to regulate the solid content to 30-45% to obtain the printing varnish.
Comparative example 2
Adding 90mL of tetrahydrofuran into 1.0mol of 2, 3-dibromobutyric acid, stirring for dissolution, and controlling the temperature to 22 ℃; adding 1.08mol of tert-butyl dimethyl chloropropane/morpholine (1/3), and preserving the heat for 27min; removing the solvent to obtain halogenated tert-butyl dimethyl ester;
adding 68mL of ethanol into 1.0mol of halogenated tert-butyl dimethyl ester, stirring for dissolution, and controlling the temperature to 82 ℃; 0.3mol of hexamethylenetetramine/NaHCO is added 3 (1/1) and then preserving heat for 12h; adding dilute hydrochloric acid to adjust the pH to 5.0; removing the solvent to obtain amino tertiary butyl dimethyl ester;
adding 48mL of tetrahydrofuran into 1.0mol of the amino tertiary butyl dimethyl ester, stirring and dissolving, and controlling the temperature to 25 ℃; adding 3mol of K 2 CO 3 Keeping the temperature for 2h after the methanol solution (3/1); removing the solvent to obtain hyperbranched pre-polymerized monomer (ABn);
adding 80mL of methyl tertiary butyl ether into 6.0mol of the hyperbranched pre-polymerization monomer, stirring and dissolving, controlling the temperature to 116 ℃, and adding 24mg of ZnCl 2 Preserving heat for 5 hours; removing the solvent to obtain amino-terminated hyperbranched polyamide;
1mol of NJ220, 2.8mol of isophorone diisocyanate and 0.3mol of 1, 4-butanediol are added into 85mL of acetone, and then stirred for dissolution, and the temperature is controlled at 165 ℃; adding 4mg of dibutyl tin dilaurate and 16mg of the amino-terminated hyperbranched polyamide, and then preserving heat for 8 hours; regulating the temperature to 48 ℃, adding 72mg of 2-hydroxy-2-methyl-1-phenylpropionic acid, and preserving the heat for 50min; adding solvent to regulate the solid content to 30-45% to obtain the printing varnish.
Example 1
A preparation method of printing varnish with amino-terminated hyperbranched self-assembled polyamide as a main component comprises the following steps:
adding 90mL of tetrahydrofuran into 1.0mol of 2, 3-dibromobutyric acid, stirring for dissolution, and controlling the temperature to 22 ℃; adding 1.08mol of tert-butyl dimethyl chloropropane/morpholine (1/3), and preserving the heat for 27min; removing the solvent to obtain halogenated tert-butyl dimethyl ester;
adding 68mL of ethanol into 1.0mol of halogenated tert-butyl dimethyl ester, stirring for dissolution, and controlling the temperature to 82 ℃; 0.3mol of hexamethylenetetramine/NaHCO is added 3 (1/1) and then preserving heat for 12h; adding dilute hydrochloric acid to adjust the pH to 5.0; removing the solvent to obtain amino tertiary butyl dimethyl ester;
adding 48mL of tetrahydrofuran into 1.0mol of the amino tertiary butyl dimethyl ester, stirring and dissolving, and controlling the temperature to 25 ℃; adding 3mol of K 2 CO 3 Keeping the temperature for 2h after the methanol solution (3/1); removing the solvent to obtain hyperbranched pre-polymerized monomer (AB n )；
Adding 80mL of methyl tertiary butyl ether into 6.0mol of the hyperbranched pre-polymerization monomer, stirring and dissolving, controlling the temperature to 116 ℃, and adding 24mg of ZnCl 2 Preserving heat for 5 hours; removing the solvent to obtain amino-terminated hyperbranched polyamide;
1mol of NJ220, 2.8mol of isophorone diisocyanate and 0.3mol of 1, 4-butanediol are added into 85mL of acetone, and then stirred for dissolution, and the temperature is controlled at 165 ℃; adding 4mg of dibutyl tin dilaurate and 16mg of the amino-terminated hyperbranched polyamide, and then preserving heat for 8 hours; the temperature is adjusted to 48 ℃, 1.6g of BA-TPGDA (1:0.5), 72mg of 2-hydroxy-2-methyl-1-phenylpropionic acid, 13mg of H-850 and 0.8mg of methyl silicone oil are added, and then the mixture is kept for 50 minutes; adding solvent to regulate the solid content to 30-45% to obtain the printing varnish.
The preparation route pattern of this example is as follows:
example 2
A preparation method of printing varnish with amino-terminated hyperbranched self-assembled polyamide as a main component comprises the following steps:
adding 20mL of tetrahydrofuran into 1.0mol of 2, 3-dibromobutyric acid, stirring for dissolution, and controlling the temperature to be 10 ℃; adding 0.92mol of tert-butyldimethyl chloropropane/morpholine (1/3), and preserving the heat for 10min; removing the solvent to obtain halogenated tert-butyl dimethyl ester;
adding 25mL of ethanol into 1.0mol of halogenated tert-butyl dimethyl ester, stirring for dissolution, and controlling the temperature to be 50 ℃; adding 0.2mol of hexamethylenetetramine/NaHCO 3 (1/1) and then preserving heat for 5 hours; adding dilute hydrochloric acid to regulate the pH to 3.8; removing the solvent to obtain amino tertiary butyl dimethyl ester;
1.0mol of the above amino tert-butyl dimethyl ester is addedAdding 10mL of tetrahydrofuran, stirring and dissolving, and controlling the temperature to be 12 ℃; adding 2mol of acetic acid, and preserving heat for 7 hours; removing the solvent to obtain hyperbranched pre-polymerized monomer (AB n )；
Adding 80mL of methyl tertiary butyl ether into 1.0mol of the hyperbranched pre-polymerization monomer, stirring and dissolving, controlling the temperature to 80 ℃, and adding 10mg of ZnCl 2 Preserving heat for 1h; removing the solvent to obtain amino-terminated hyperbranched polyamide;
1mol of NJ220, 1.2mol of isophorone diisocyanate and 0.2mol of 1, 4-butanediol are added into 20mL of acetone, and then stirred for dissolution, and the temperature is controlled to be 80 ℃; 3mg of dibutyltin dilaurate and 9mg of the amino-terminated hyperbranched polyamide are added, and the temperature is kept for 3 hours; temperature was adjusted to 20℃and after adding 0.1g of BA-TPGDA (1:0.1), 3mg of 2-hydroxy-2-methyl-1-phenylpropionic acid, 0.6mg of H-850 and 0.1mg of methyl silicone oil, the mixture was kept for 20 minutes; adding solvent to regulate the solid content to 30-45% to obtain the printing varnish.
Example 3
A preparation method of printing varnish with amino-terminated hyperbranched self-assembled polyamide as a main component comprises the following steps:
adding 120mL of tetrahydrofuran into 1.0mol of 2, 3-dibromobutyric acid, stirring and dissolving, and controlling the temperature to be 50 ℃; adding 1.22mol of tert-butyl dimethyl chloropropane/morpholine (1/3), and preserving the heat for 50min; removing the solvent to obtain halogenated tert-butyl dimethyl ester;
adding 70mL of ethanol into 1.0mol of halogenated tert-butyl dimethyl ester, stirring for dissolution, and controlling the temperature to 140 ℃; adding 0.6mol of hexamethylenetetramine/NaHCO 3 (1/1) and then preserving heat for 20h; adding dilute hydrochloric acid to adjust the pH to 6.7; removing the solvent to obtain amino tertiary butyl dimethyl ester;
adding 60mL of tetrahydrofuran into 1.0mol of the amino tertiary butyl dimethyl ester, stirring and dissolving, and controlling the temperature to be 48 ℃; or 4mol of K 2 CO 3 Keeping the temperature for 6 hours after the methanol solution (3/1); removing the solvent to obtain hyperbranched pre-polymerized monomer (AB n )；
Adding 80mL of methyl tertiary butyl ether into 8.0mol of the hyperbranched pre-polymerization monomer, stirring and dissolving, controlling the temperature to 140 ℃, and adding 60mg of ZnCl 2 Preserving heat for 7 hours; removing the solvent to obtain amino-terminated hyperbranched polyamide;
1mol of NJ220, 3.0mol of isophorone diisocyanate and 0.5mol of 1, 4-butanediol are added into 90mL of acetone, and then are stirred and dissolved, and the temperature is controlled to be 220 ℃; adding 10mg of dibutyltin dilaurate and 18mg of the amino-terminated hyperbranched polyamide, and then preserving heat for 17 hours; temperature was adjusted to 60℃and after adding 2.0g of BA-TPGDA (1:10), 12mg of 2-hydroxy-2-methyl-1-phenylpropionic acid, 20mg of H-850, 4mg of methyl silicone oil, the mixture was kept for 60 minutes; adding solvent to regulate the solid content to 30-45% to obtain the printing varnish.
Example 4
A preparation method of printing varnish with amino-terminated hyperbranched self-assembled polyamide as a main component comprises the following steps:
adding 23mL of dimethylformamide into 1.0mol of 2, 3-dibromopropionic acid, stirring for dissolution, and controlling the temperature to 47 ℃; adding 0.95mol of tert-butyl dimethyl chloropropane/imidazole (1/0.5), and preserving heat for 7h; removing the solvent to obtain halogenated tert-butyl dimethyl ester;
adding 35mL of methanol into 1.0mol of halogenated tert-butyl dimethyl ester, stirring for dissolution, and controlling the temperature to be 56 ℃; adding 0.4mol of hexamethylenetetramine/NaHCO 3 (1/1) and then preserving heat for 6 hours; adding dilute nitric acid to adjust the pH to 3.9; removing the solvent to obtain amino tertiary butyl dimethyl ester;
adding 12mL of dimethylformamide into 1.0mol of the amino tertiary butyl dimethyl ester, stirring and dissolving, and controlling the temperature to 13 ℃; adding 4mol of propionic acid, and preserving heat for 8 hours; removing the solvent to obtain hyperbranched pre-polymerized monomer (AB n )；
Adding 80mL of dioxane into 2.3mol of the hyperbranched pre-polymerization monomer, stirring for dissolution, controlling the temperature to 82 ℃, and adding 11mg of AlCl 3 Preserving heat for 2h; removing the solvent to obtain amino-terminated hyperbranched polyamide;
1mol of PPG-1000, 1.3mol of dimethylbiphenyl diisocyanate and 0.4mol of carbodiimide are added into 21mL of dioxane, and then stirred for dissolution, and the temperature is controlled at 81 ℃; adding 5mg of dibutyl tin dilaurate and 10mg of the amino-terminated hyperbranched polyamide, and then preserving the heat for 4 hours; temperature was adjusted to 26℃and after adding 0.3g of BA-St (1:0.1), 4mg of 1-hydroxycyclohexyl phenyl ketone, 7.2mg of H-633, 0.2mg of OP wax, the mixture was incubated for 21min; adding solvent to regulate the solid content to 30-45% to obtain the printing varnish.
Example 5
A preparation method of printing varnish with amino-terminated hyperbranched self-assembled polyamide as a main component comprises the following steps:
adding 1.0mol of 2, 3-dichloropropionic acid into 42mL of dioxane, stirring for dissolution, and controlling the temperature to 17 ℃; 1.21mol of tert-butyldimethyl chloropropane/imidazole (1/0.5) is added and then the mixture is kept for 12 hours; removing the solvent to obtain halogenated tert-butyl dimethyl ester;
adding 33mL of tertiary butyl alcohol into 1.0mol of halogenated tertiary butyl dimethyl ester, stirring and dissolving, and controlling the temperature to be 75 ℃; adding 0.5mol of hexamethylenetetramine/NaHCO 3 (1/1) and then preserving heat for 7h; adding dilute sulfuric acid to adjust the pH to 5.8; removing the solvent to obtain amino tertiary butyl dimethyl ester;
adding 14mL of toluene into 1.0mol of the amino tertiary butyl dimethyl ester, stirring and dissolving, and controlling the temperature to be 31 ℃; adding 4mol of n-butyric acid, and preserving heat for 32h; removing the solvent to obtain hyperbranched pre-polymerized monomer (AB n )；
Adding 80mL of dimethylformamide into 5.2mol of the hyperbranched pre-polymerization monomer, stirring for dissolution, controlling the temperature to 110 ℃, and adding 36mg of SO 3 Preserving heat for 6 hours; removing the solvent to obtain amino-terminated hyperbranched polyamide;
1mol of PTMG1000, 2.5mol of p-phenylene diisocyanate and 0.3mol of 3, 3-dichloro-4, 4-diaminodiphenylmethane are added into 50mL of butanone, and then stirred and dissolved, and the temperature is controlled at 174 ℃; adding 5mg of dibutyltin dilaurate and 12mg of the amino-terminated hyperbranched polyamide, and then preserving heat for 14h; adjusting the temperature to 48 ℃, adding 1.7g of BA-TMPTA (1:3), 6mg of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 7.3mg of LAG-450 and 2.3mg of Montana wax, and preserving the temperature for 48min; adding solvent to regulate the solid content to 30-45% to obtain the printing varnish.
Example 6
A preparation method of printing varnish with amino-terminated hyperbranched self-assembled polyamide as a main component comprises the following steps:
adding 58mL of diethyl ether into 1.0mol of 2, 3-dichloroisobutyric acid, stirring and dissolving, and controlling the temperature to 38 ℃; adding 1.03mol of tert-butyl dimethyl chloropropane/morpholine (1/3), and preserving the heat for 31min; removing the solvent to obtain halogenated tert-butyl dimethyl ester;
1.0mol of the halogenated tert-butyl dimethyl ester is added into 49mL of isopropanol, stirred and dissolved, and the temperature is controlled71 ℃; adding 0.6mol of hexamethylenetetramine/NaHCO 3 (1/1) then preserving heat for 17h; adding dilute sulfuric acid to regulate the pH value to 4.0; removing the solvent to obtain amino tertiary butyl dimethyl ester;
adding 38mL of chloroform into 1.0mol of the amino tertiary butyl dimethyl ester, stirring and dissolving, and controlling the temperature to 15 ℃; adding 2mol of K 2 CO 3 Keeping the temperature for 5h after the methanol solution (3/1); removing the solvent to obtain hyperbranched pre-polymerized monomer (AB n )；
Adding 80mL of N-methylpyrrolidone into 2.3mol of the hyperbranched pre-polymerization monomer, stirring for dissolution, controlling the temperature to 124 ℃, and adding 13mg of FeBr 2 Preserving heat for 5 hours; removing the solvent to obtain amino-terminated hyperbranched polyamide;
1mol of PCL1000, 2.5mol of 4, 4' -triphenylmethane triisocyanate and 0.4mol of triisopropanolamine are added into 21mL of dimethylformamide, and then stirred for dissolution, and the temperature is controlled at 96 ℃; adding 10mg of dibutyltin dilaurate and 14mg of the amino-terminated hyperbranched polyamide, and then preserving heat for 8 hours; temperature was adjusted to 54℃and 1.5g of BA-St (1:4), 11mg of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 12mg of H-810, 3.5mg of Montana wax were added and then the mixture was kept for 27 minutes; adding solvent to regulate the solid content to 30-45% to obtain the printing varnish.
Example 7
A preparation method of printing varnish with amino-terminated hyperbranched self-assembled polyamide as a main component comprises the following steps:
adding 1.0mol of 2, 6-dichlorobenzoic acid into 100mL of toluene, stirring for dissolution, and controlling the temperature to be 12 ℃; adding 0.97mol of tert-butyl dimethyl chloropropane/morpholine (1/3), and preserving the heat for 47min; removing the solvent to obtain halogenated tert-butyl dimethyl ester;
adding 38mL of isopropanol into 1.0mol of halogenated tert-butyl dimethyl ester, stirring for dissolution, and controlling the temperature to be 64 ℃; adding 0.6mol of hexamethylenetetramine/NaHCO 3 (1/1) and then preserving heat for 12h; adding dilute hydrochloric acid to adjust the pH to 3.8-6.7, preferably pH 4.0; removing the solvent to obtain amino tertiary butyl dimethyl ester;
adding 1.0mol of the amino tertiary butyl dimethyl ester into 13mL of dioxane, stirring and dissolving, and controlling the temperature to be 35 ℃; adding 4mol of n-butyric acid, and preserving heat for 12 hours; removing the solvent to obtain hyperbranched pre-polymerized monomer (AB n )；
Adding 80mL of butanone into 7.3mol of the hyperbranched pre-polymerization monomer, stirring for dissolution, controlling the temperature to 106 ℃, and adding 30mg of AlCl 3 Preserving heat for 2h; removing the solvent to obtain amino-terminated hyperbranched polyamide;
1mol of PPG-2000, 2.1mol of hexamethylene diisocyanate and 0.4mol of triisopropanolamine are added into 50mL of dimethylformamide, and then stirred for dissolution, and the temperature is controlled to be 144 ℃; 7mg of dibutyltin dilaurate and 12mg of the amino-terminated hyperbranched polyamide are added, and the temperature is kept for 8 hours; temperature was adjusted to 38deg.C, and after adding 2.0g BA-St (1:2), 8mg 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone, 14mg LAG-450, 1.2mg OP wax, the mixture was incubated for 25min; adding solvent to regulate the solid content to 30-45% to obtain the printing varnish.
Example 8
A preparation method of printing varnish with amino-terminated hyperbranched self-assembled polyamide as a main component comprises the following steps:
adding 1.0mol of 2, 4-dichlorobenzoic acid into 55mL of toluene, stirring for dissolution, and controlling the temperature to 39 ℃; adding 1.22mol of tert-butyldimethyl chloropropane/imidazole (1/0.5), and preserving the heat for 14 hours; removing the solvent to obtain halogenated tert-butyl dimethyl ester;
adding 62mL of tert-butyl alcohol into 1.0mol of halogenated tert-butyl dimethyl ester, stirring for dissolution, and controlling the temperature to 67 ℃; adding 0.5mol of hexamethylenetetramine/NaHCO 3 (1/1) and then preserving heat for 13h; adding dilute sulfuric acid to adjust the pH to 4.7; removing the solvent to obtain amino tertiary butyl dimethyl ester;
adding 12mL of tetrahydrofuran into 1.0mol of the amino tertiary butyl dimethyl ester, stirring and dissolving, and controlling the temperature to 17 ℃; adding 4mol of acetic acid, and preserving heat for 9 hours; removing the solvent to obtain hyperbranched pre-polymerized monomer (AB n )；
Adding 80mL of toluene into 5.3mol of the hyperbranched pre-polymerization monomer, stirring for dissolution, controlling the temperature to 92 ℃, and adding 33mg of FeBr 2 Preserving heat for 2h; removing the solvent to obtain amino-terminated hyperbranched polyamide;
1mol PTMG2000, 2.2mol p-phenylene diisocyanate and 0.4mol uretonimine are added into 78mL cyclohexanone, and then stirred for dissolution, and the temperature is controlled at 85 ℃; adding 10mg of dibutyltin dilaurate and 18mg of the amino-terminated hyperbranched polyamide, and then preserving heat for 17 hours; temperature was adjusted to 20℃and 2.0g of BA-TMPTA (1:9), 10mg of 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone, 12mg of LAG-450, 3mg of a montan wax were added and incubated for 30min; adding solvent to regulate the solid content to 30-45% to obtain the printing varnish.
Example 9
A preparation method of printing varnish with amino-terminated hyperbranched self-assembled polyamide as a main component comprises the following steps:
adding 1.0mol of pyridine-2-acetamide into 30mL of diethyl ether, stirring for dissolution, and controlling the temperature to 42 ℃; adding 0.92mol of tert-butyldimethyl chloropropane/imidazole (1/0.5), and preserving the heat for 14 hours; removing the solvent to obtain halogenated tert-butyl dimethyl ester;
adding 55mL of tert-butyl alcohol into 1.0mol of halogenated tert-butyl dimethyl ester, stirring for dissolution, and controlling the temperature to 63 ℃; adding 0.6mol of hexamethylenetetramine/NaHCO 3 (1/1) and then preserving heat for 12h; adding dilute hydrochloric acid to regulate the pH to 5.2; removing the solvent to obtain amino tertiary butyl dimethyl ester;
adding 20mL of chloroform into 1.0mol of the amino tertiary butyl dimethyl ester, stirring and dissolving, and controlling the temperature to 33 ℃; 4mol of K2CO are added 3 Keeping the temperature for 2h after the methanol solution (3/1); removing the solvent to obtain hyperbranched pre-polymerized monomer (AB n )；
Adding 80mL of dimethylformamide into 7.4mol of the hyperbranched pre-polymerization monomer, stirring for dissolution, controlling the temperature to 87 ℃, and adding 22mg of FeBr 2 Preserving heat for 5 hours; removing the solvent to obtain amino-terminated hyperbranched polyamide;
1mol of PCL1000, 2.4mol of 4, 4' -triphenylmethane triisocyanate and 0.4mol of 3, 5-diamino-p-chlorobenzoic acid isobutyl ester are added into 90mL of dimethylformamide, and then stirred and dissolved, and the temperature is controlled to be 161 ℃; adding 5mg of dibutyl tin dilaurate and 10mg of the amino-terminated hyperbranched polyamide, and then preserving heat for 8 hours; temperature was adjusted to 49℃and after adding 2.0g of BA-St (1:3.3), 9mg of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, 10mg of LAG-450, 3mg of OP wax, the mixture was incubated for 43min; adding solvent to regulate the solid content to 30-45% to obtain the printing varnish.
Example 10
A preparation method of printing varnish with amino-terminated hyperbranched self-assembled polyamide as a main component comprises the following steps:
1.0mol of 3, 5-dichloro-4-methylbenzoic acid is added into 70mL of toluene, stirred and dissolved, and the temperature is controlled at 28 ℃; 1.22mol of tert-butyldimethyl chloropropane/imidazole (1/0.5) is added and then the mixture is kept for 8 hours; removing the solvent to obtain halogenated tert-butyl dimethyl ester;
adding 70mL of isopropanol into 1.0mol of halogenated tert-butyl dimethyl ester, stirring for dissolution, and controlling the temperature to be 53 ℃; adding 0.4mol of hexamethylenetetramine/NaHCO 3 (1/1) and then preserving heat for 9 hours; adding dilute sulfuric acid to regulate the pH value to 4.0; removing the solvent to obtain amino tertiary butyl dimethyl ester;
adding 13mL of chloroform into 1.0mol of the amino tertiary butyl dimethyl ester, stirring and dissolving, and controlling the temperature to be 13 ℃; adding 4mol of acetic acid, and preserving heat for 32 hours; removing the solvent to obtain hyperbranched pre-polymerized monomer (AB n )；
Adding 80mL of N-methylpyrrolidone into 8.0mol of the hyperbranched pre-polymerization monomer, stirring for dissolution, controlling the temperature to 112 ℃, and adding 60mg of ZnCl 2 Preserving heat for 2h; removing the solvent to obtain amino-terminated hyperbranched polyamide;
1mol of PCL2000, 2.5mol of hexamethylene diisocyanate and 0.4mol of uretonimine are added into 21mL of dioxane, and then stirred for dissolution, and the temperature is controlled to be 89 ℃; adding 10mg of dibutyltin dilaurate and 12mg of the amino-terminated hyperbranched polyamide, and then preserving heat for 8 hours; the temperature is regulated to 48 ℃, 1.7g of BA-St (1:6), 4mg of 1-hydroxycyclohexyl phenyl ketone, 14mg of H-633 and 3mg of methyl silicone oil are added, and then the mixture is kept for 23min; adding solvent to regulate the solid content to 30-45% to obtain the printing varnish.
Test results and data analysis
The results of the leveling effect test of the printing gloss oil obtained in comparative example 1, comparative example 2 and example 1 are shown in fig. 1. It can be seen that the photograph (a) shows obvious sagging phenomenon, mainly due to poor surface drying performance of the printing gloss oil, and the coating still generates rheology after the white cardboard stands upright; the photo (b) shows a prickly heat phenomenon, mainly because the printing gloss oil can finish surface drying and curing in the same time, but the components lack leveling agents, wax slurry and other auxiliary agents which are helpful for coating leveling, and the gloss oil lacks due surface flatness after curing; the photo (c) shows excellent surface drying and leveling effects, and fully illustrates that the surface drying time can be remarkably shortened after the hyperbranched structure is introduced into the gloss oil system, and meanwhile, leveling agents, wax slurry and the like can participate in and optimize the leveling effect of the coating.
The SEM test of the coating film surface after curing the printing varnish of comparative example 1 and the printing varnish of example 1 are shown in fig. 2. It can be seen that the surface of the former has larger particles, and the brightness is alternate, which may be that the main chain, side chain and the like of the polymer molecule are related to the mutual repulsion phenomenon of the flatting agent and the wax slurry; compared with the prior art, the surface of the polymer is smoother and smoother, almost has no cracks, has better continuity and compactness, and is mainly characterized in that hyperbranched structures are introduced into the polymer system, the inner molecular chain segments are more tightly and regularly arranged along the hyperbranched spheroids, the compatibility among the components is good, and the cured film has excellent continuity and compactness from the SEM view.
XRD patterns of the printed varnish coatings of comparative example 1 and examples 1, 3, and 5 were respectively measured, and the results are shown in fig. 3. It can be seen that each sample produced an amorphous diffraction peak around 2θ=20°, which is mainly a crystalline diffraction peak from aggregation of soft segments of polyurethane in the molecular structure of the polymer; the samples of examples 1, 3 and 5 generate obvious absorption peaks at two positions near 2θ= 26.50 ° and 29.50 °, because the cured system contains a large number of hyperbranched structures, the internal three-dimensional network arrangement and crosslinking are more compact, free rotation of chain segments and crystal growth are limited, and the hyperbranched polyamide plays a substantial role in the modification of polyurethane-acrylic ester.
The combination properties of the printed varnish coatings of the comparative examples and part of examples were respectively tested, and the results of the gloss, water resistance and drying properties are shown in table 1. It can be seen that the comparative example 2 and examples 1, 3, 5, 7 and 9 have better water resistance and drying efficiency than the comparative example 1, because the polymer molecular structure is hyperbranched modified, the chain segments are arranged more flexibly and compactly, the removal of internal solvents is facilitated in the curing process, and water molecules are difficult to penetrate after curing and film forming; it is noted that examples 1, 3, 5, 7, 9 are optimal in terms of gloss, comparative example 1 is the worst, and comparative example 2 is mainly because comparative example 2 contains hyperbranched structures but lacks leveling agents, wax slurries, and the like, so that the continuity of the coating after curing is limited, and the appearance of the coating shows a 'prickly heat' phenomenon; the comparative example 1 was more glossy centered than the other two cases, and the surface polymer molecular segments were guided by leveling agents, wax slurries, etc., each of which exhibited a somewhat regular arrangement, but the curing system lacked quick-drying properties, thus appearing as sagging.
TABLE 1 characterization of gloss, water resistance and drying Property of printing gloss oil and its coating
The combination properties of the printed varnish coatings of comparative example 1, comparative example 2 and some examples were respectively tested, and pencil hardness, adhesion and impact resistance were measured as shown in table 2. It can be seen that the hyperbranched structures are introduced into the systems of comparative example 2 and examples 1, 3, 5, 7 and 9, and the coating layer shows excellent hardness and impact resistance, which is mainly attributed to the fact that the polymer molecules are modified by hyperbranched, and the molecular chains are in a stretched and compact arrangement along the hyperbranched radial shape, so that the system has better rigidity; on the other hand, the amino-terminated hyperbranched polyamide contains a plurality of amino structures, and can form stronger acting force with polyurethane segments or acrylic ester segments during the period, so that the strength of the cured film is further enhanced; in addition, the coating adhesion after hyperbranched modification is enhanced mainly because a plurality of active amino groups in the hyperbranched structure can form a stable covalent structure with nucleophilic groups in the base material, so that the coating material is firmly attached to the surface of the white cardboard.
TABLE 2 printing gloss oil and coating mechanical characterization results thereof
The results of the anti-abrasion protection effect of the printing gloss oil obtained in comparative example 1 and example 1 were each measured, and are shown in fig. 4. The latter has better protection effect on the printed pattern, and the printed ink layer is not obviously peeled off and transferred after the friction test, which is mainly attributed to the regular and compact arrangement of the molecular chain segments of the system after the hyperbranched modification of the printing gloss oil, and the coating has better continuity and higher strength after being cured into a film, thus the printed ink layer for protecting the covered area can be played, and the printed ink layer is also verified with the microscopic image observed by SEM.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related technical fields are included in the scope of the present invention.

Claims (10)

1. The preparation method of the printing varnish taking the amino-terminated hyperbranched self-assembled polyamide as a main component is characterized by comprising the following steps of:
(1) Adding a solvent into polyhalogenated carboxylic acid, stirring and dissolving, controlling the temperature to be 10-50 ℃, adding tertiary butyl dimethyl chloropropane/imidazole, then preserving the heat for 4-20 hours, or adding tertiary butyl dimethyl chloropropane/morpholine, then preserving the heat for 10-50 minutes, and removing the solvent to obtain halogenated tertiary butyl dimethyl ester; wherein the polyhalogenated carboxylic acid is 2, 3-dibromopropionic acid, 2, 3-dibromobutyric acid, 2, 3-dichloropropionic acid, 2, 3-dichloroisobutyric acid, 3, 5-dibromobenzoic acid, 3, 5-dibromo-4-methylbenzoic acid, 2, 6-dichlorobenzoic acid, 2,4, 6-trichlorobenzoic acid, 2, 4-dichlorobenzoic acid, pyridine-2-acetamide or 3, 5-dichloro-4-methylbenzoic acid; the solvent is dimethylformamide, tetrahydrofuran, dioxane, diethyl ether or toluene; the mass ratio of the tert-butyl dimethyl chloropropane to the imidazole is 1:0.5; the mass ratio of the tert-butyl dimethyl chloropropane to the morpholine is 1:3; the material ratio of the polyhalogenated carboxylic acid to the solvent to the tert-butyldimethyl chloropropane/imidazole or tert-butyldimethyl chloropropane/morpholine is 1.0 mol:20-120 mL:0.92-1.22 mol;
(2) Adding the prepared halogenated tert-butyl dimethyl ester into a solvent, stirring and dissolving, and controlling the temperature to be 50-to-50 DEG140 ℃, add hexamethylenetetramine/NaHCO 3 Then preserving heat for 5-20 h, adding acid to adjust pH to 3.8-6.7, and removing the solvent to obtain amino tertiary butyl dimethyl ester; wherein, the hexamine/NaHCO 3 The ratio of the amounts of the substances is 1:1; the solvent is methanol, ethanol, tertiary butanol or isopropanol, and the acid is dilute hydrochloric acid, dilute nitric acid or dilute sulfuric acid; the halogenated tert-butyl dimethyl ester, solvent and hexamethylenetetramine/NaHCO 3 The material ratio of (2) is
1.0mol:25～70mL:0.2～0.6mol；
(3) Adding the prepared amino tertiary butyl dimethyl ester into a solvent, stirring and dissolving, controlling the temperature to be 12-48 ℃, adding carboxylic acid, and then preserving the temperature for 7-40 h, or adding K 2 CO 3 Keeping the temperature for 1 to 6 hours after the methanol solution is treated, and removing the solvent to obtain the hyperbranched pre-polymerization monomer AB n The method comprises the steps of carrying out a first treatment on the surface of the Wherein the K is 2 CO 3 The mass ratio of the methanol is 3:1; the solvent is tetrahydrofuran, dimethylformamide, toluene, dioxane, diethyl ether or chloroform, preferably tetrahydrofuran; the carboxylic acid is acetic acid, propionic acid or n-butyric acid, preferably acetic acid; said amino-tert-butyldimethyl ester, solvent, carboxylic acid or K 2 CO 3 The material ratio of the methanol solution is 1.0 mol:10-60 mL:2-4 mol, preferably 1.0mol:48mL:3mol;
(4) The hyperbranched pre-polymerized monomer AB prepared n Adding a solvent, stirring and dissolving, controlling the temperature to be 80-140 ℃, adding a catalyst, and then preserving the heat for 1-7 hours to remove the solvent to obtain the amino-terminated hyperbranched polyamide; wherein the solvent is dioxane, methyl tertiary butyl ether, toluene, dimethylformamide, acetone, butanone or N-methylpyrrolidone, preferably methyl tertiary butyl ether; the catalyst is AlCl 3 、BF 3 、ZnCl 2 、SO 3 Or FeBr 2 Preferably ZnCl 2 The method comprises the steps of carrying out a first treatment on the surface of the The material proportion of the hyperbranched pre-polymerization monomer, the solvent and the catalyst is 1.0-8.0 mol:80 mL:10-60 mg, preferably 6.0mol:80mL:24mg;
(5) Adding a solvent into the poly polyol, the polyisocyanate and the chain extender, stirring and dissolving, controlling the temperature to be 80-220 ℃, adding a catalyst, preserving heat for 3-17 hours after adding the prepared amino-terminated hyperbranched polyamide, regulating the temperature to be 20-60 ℃, adding an acrylic acid diluent, a photoinitiator, a leveling agent and wax slurry, preserving heat for 20-60 minutes, and adding the solvent to regulate the solid content to be 30-45% to obtain printing gloss oil; wherein the polyol is a polyether glycol (PPG-1000, PPG-2000),
NJ210, NJ220, NJ 230), polytetrahydrofuran glycol (PTMG 1000, PTMG 2000), polyepsilon caprolactone diol (PCL 1000, PCL 2000), and the like, with NJ220 being preferred; the polyisocyanate is dimethylbiphenyl diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4', 4 "
Triphenylmethane triisocyanate and the like, preferably isophorone diisocyanate; the chain extender is 1, 4-butanediol, carbodiimide, 3-dichloro-4, 4-diaminodiphenylmethane, 4-methylenebis (di-chloroaniline), triisopropanolamine, uretonimine, isobutyl 3, 5-diaminop-chlorobenzoate, etc., preferably 1, 4-butanediol; the solvent is dioxane, acetone, butanone, toluene, cyclohexanone, dimethylformamide and the like, preferably acetone; the catalyst is a tertiary amine catalyst, an organotin compound, a non-tin organometallic compound, etc., preferably an organotin compound such as dibutyltin dilaurate; the acrylic acid diluent is BA-St, BA-TPGDA, BA-TMPTA and the like, the mass ratio of the BA-St to the BA-TPGDA is 1:0.1-10, and the mass ratio of the BA-TPGDA to the BA-TPGDA is preferably 1:0.5; the photoinitiator is 2-hydroxy-2-methyl-1-phenylpropion (Darocur 1173), 1-hydroxycyclohexylphenyl ketone, 2-methyl-2- (4-morpholino) -1- [4- (methylthio) phenyl ] -1-propanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoyl-phenylphosphonate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholino) phenyl ] -1-butanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, methyl benzoylformate or the like, preferably 2-hydroxy-2-methyl-1-phenylpropion; the leveling agent is H-633, H-850, H-810, LAG-450, etc., preferably H-850; the wax slurry is OP wax, paraffin oil, montana wax, methyl silicone oil and the like, preferably methyl silicone oil; the material proportion of the polyatomic alcohol, the polyisocyanate, the chain extender, the solvent added for the first time, the catalyst, the acrylic acid diluent, the photoinitiator, the flatting agent, the wax slurry and the amino-terminated hyperbranched polyamide is
1 mol:1.2-3.0 mol:0.2-0.5 mol:20-90 mL:3-10 mg:0.1-2.0 g:3-12 mg:0.6-20 mg:0.1-4 mg:9-18 mg, preferably 1mol:2.8mol:0.3mol:85mL:4mg:1.6g:7mg:13mg:0.8mg:16mg.
2. The process for producing a varnish for printing comprising an amino-terminated hyperbranched self-assembled polyamide as a main component according to claim 1, wherein: in the step (1), the polyhalogenated carboxylic acid is added into a solvent, stirred and dissolved, the temperature is controlled at 22 ℃, the temperature is kept for 27min after the tertiary butyl dimethyl chloropropane/morpholine is added, and the solvent is removed to obtain halogenated tertiary butyl dimethyl ester.
3. The process for producing a varnish for printing comprising an amino-terminated hyperbranched self-assembled polyamide as a main component according to claim 1, wherein: the polyhalogenated carboxylic acid in step (1) is 2, 3-dibromobutyric acid, the solvent is tetrahydrofuran, the mass ratio of t-butyldimethylphloropropane/imidazole is 1:0.5, and the mass ratio of t-butyldimethylphloropropane/morpholine is 1:3.
4. The process for producing a varnish for printing comprising an amino-terminated hyperbranched self-assembled polyamide as a main component according to claim 1, wherein: the ratio of the polyhalogenated carboxylic acid, solvent, t-butyldimethylphloropropane/imidazole or t-butyldimethylphloropropane/morpholine in step (1) was 1.0mol:90mL:1.08mol.
5. The process for producing a varnish for printing comprising an amino-terminated hyperbranched self-assembled polyamide as a main component according to claim 1, wherein: in the step (2), the prepared halogenated tert-butyl dimethyl ester is added into a solvent and then stirred for dissolution, the temperature is controlled at 82 ℃, and hexamethylenetetramine/NaHCO is added 3 And then preserving the heat for 12 hours, adding acid to adjust the pH value to 5.0, and removing the solvent to obtain the amino tertiary butyl dimethyl ester.
6. The process for producing a varnish for printing comprising an amino-terminated hyperbranched self-assembled polyamide as a main component according to claim 1, wherein: the solvent in step (2) is ethanol and the acid is dilute hydrochloric acid.
7. The process for producing a varnish for printing comprising an amino-terminated hyperbranched self-assembled polyamide as a main component according to claim 1, wherein: the halogenated tert-butyl dimethyl ester, solvent and hexamethylenetetramine/NaHCO in the step (2) 3 The ratio of the materials was 1.0mol:68mL:0.3mol.
8. The process for producing a varnish for printing comprising an amino-terminated hyperbranched self-assembled polyamide as a main component according to claim 1, wherein: adding the prepared amino tertiary butyl dimethyl ester into a solvent in the step (3), stirring and dissolving, controlling the temperature to 25 ℃, and adding K 2 CO 3 Keeping the temperature for 2 hours after the methanol solution is treated, and removing the solvent to obtain the hyperbranched pre-polymerized monomer AB n 。
9. The process for producing a varnish for printing comprising an amino-terminated hyperbranched self-assembled polyamide as a main component according to claim 1, wherein: the hyperbranched pre-polymerized monomer AB prepared in the step (4) n Adding a solvent, stirring and dissolving, controlling the temperature to 116 ℃, adding a catalyst, preserving the heat for 5 hours, and removing the solvent to obtain the amino-terminated hyperbranched polyamide.
10. The process for producing a varnish for printing comprising an amino-terminated hyperbranched self-assembled polyamide as a main component according to claim 1, wherein: adding the polyalcohol, the polyisocyanate and the chain extender into a solvent, stirring and dissolving, controlling the temperature to 165 ℃, adding a catalyst, preserving the heat for 8 hours after adding the catalyst, and preserving the heat for 50 minutes after adding the acrylic acid diluent, the photoinitiator, the flatting agent and the wax slurry, wherein the temperature is adjusted to 48 ℃; adding solvent to regulate the solid content to 30-45% to obtain the printing varnish.
CN202311535388.0A 2023-11-16 2023-11-16 Preparation method of printing gloss oil with amino-terminated hyperbranched self-assembled polyamide as main component Pending CN117603604A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998026028A1 (en) * 1996-12-09 1998-06-18 Orr William C Fuel compositions exhibiting improved fuel stability
CN101023057A (en) * 2004-05-06 2007-08-22 赛特凯恩蒂克公司 Certain chemical entities, compositions, and methods
CN104945565A (en) * 2015-07-14 2015-09-30 扬州市祥华新材料科技有限公司 Electrical aluminum gilding foil glue layer resin and preparing method thereof
US20220315761A1 (en) * 2019-01-25 2022-10-06 Isp Investments Llc Dihydroxy lactam based polymers, compositions and applications thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998026028A1 (en) * 1996-12-09 1998-06-18 Orr William C Fuel compositions exhibiting improved fuel stability
CN101023057A (en) * 2004-05-06 2007-08-22 赛特凯恩蒂克公司 Certain chemical entities, compositions, and methods
CN104945565A (en) * 2015-07-14 2015-09-30 扬州市祥华新材料科技有限公司 Electrical aluminum gilding foil glue layer resin and preparing method thereof
US20220315761A1 (en) * 2019-01-25 2022-10-06 Isp Investments Llc Dihydroxy lactam based polymers, compositions and applications thereof

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