CN106700028B - A kind of cathode electrophoresis dope sulfosalt type dispersion resin and preparation method thereof - Google Patents
A kind of cathode electrophoresis dope sulfosalt type dispersion resin and preparation method thereof Download PDFInfo
- Publication number
- CN106700028B CN106700028B CN201611069027.1A CN201611069027A CN106700028B CN 106700028 B CN106700028 B CN 106700028B CN 201611069027 A CN201611069027 A CN 201611069027A CN 106700028 B CN106700028 B CN 106700028B
- Authority
- CN
- China
- Prior art keywords
- compound
- alcohol
- preparation
- added
- semi
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
-
- 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
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0809—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic 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
- C08G18/58—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
- C09D17/005—Carbon black
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/4465—Polyurethanes
-
- 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
- C08G2150/00—Compositions for coatings
- C08G2150/90—Compositions for anticorrosive coatings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Molecular Biology (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
本发明属于涂料技术领域，涉及一种阴极电泳涂料用硫鎓盐型分散树脂及其制备方法。该分散树脂的制备方法包括如下步骤：1)制备小分子增稠剂半封闭的异氰酸酯；2)制备含活泼氢的硫醚类化合物半封闭的异氰酸酯；3)制备醇类化合物或醇醚类化合物半封闭的异氰酸酯；4)制备分散树脂。该分散树脂侧链上硫醚键中的硫原子可以和铁系基材形成铁硫键，进而提高涂层与金属基材的结合力，提高涂层的耐腐蚀能力和抗再溶性能力；同时，该分散树脂拥有较好的流平性，可以提高涂层的光泽；另外，该分散树脂属于水性分散树脂，较少使用有机溶剂，具有低VOC环保特性。相比于季铵盐型分散树脂拥有诸多优点，具有广阔的应用前景。The invention belongs to the technical field of coatings, and relates to a sulfonium salt type dispersing resin for cathodic electrophoretic coatings and a preparation method thereof. The preparation method of the dispersing resin comprises the following steps: 1) preparing a semi-blocked isocyanate of a small molecular thickener; 2) preparing a semi-blocked isocyanate containing an active hydrogen-containing thioether compound; 3) preparing an alcohol compound or an alcohol ether compound Semi-blocked isocyanate; 4) Preparation of dispersion resin. The sulfur atoms in the sulfide bond on the side chain of the dispersed resin can form an iron-sulfur bond with the iron-based substrate, thereby improving the bonding force between the coating and the metal substrate, and improving the corrosion resistance and resolubility of the coating; at the same time; , the dispersion resin has good leveling, which can improve the gloss of the coating; in addition, the dispersion resin is a water-based dispersion resin, less use of organic solvents, and has low VOC environmental protection characteristics. Compared with quaternary ammonium salt type dispersing resin, it has many advantages and has broad application prospects.
Description
Technical field
The invention belongs to technical field of coatings, it is related to a kind of corrosion resistance that can be improved cathode electrophoresis dope, paint film table
The sulfosalt type dispersion resin and preparation method thereof of face gloss and anti-dissolubility ability again.
Background technique
Electrophoretic coating typically refers under electric field action, and the main substance in coating is finally baked into deposited on substrates
A kind of water paint of film.After decades of development, status of the electrophoretic coating in coating industry is more and more important, this is main
Being attributed to electrophoretic coating has the characteristics that utilization efficiency of coatings is high, corrosion resistance is strong, good environmental protection.
Auto industry is one of most important application field of cathode electrophoresis dope, and the cathode electrophoresis dope for the field is logical
Frequently with epoxy resin as matrix resin, mill base is prepared using the dispersion resin containing quaternary ammonium salt structure.This cathode electricity
Swimming coating possesses good corrosion resistance when handling before Zinc phosphating, and it is small to can reach 1000 under the conditions of neutral salt spray test
When.But the higher cost of Zinc phosphating pre-treatment, through frequently with iron series phosphorus in the work progress in some low-end applications fields
Change pre-treatment to be substituted, have the characteristics that construction is simple, low in cost, but the salt spray resistance ability of gained paint film significantly under
Drop, is unfavorable for the protection of substrate.Using ferric solid-acid as preceding processing when, traditional quaternary dispersion resin it is corrosion-resistant
Scarce capacity.Since there are a large amount of ammonium salts in dispersion resin, in high-temperature baking, paint film is easy loss of gloss, xanthochromia.Quaternary
Mill base prepared by dispersion resin is easy to return slightly, affects the stability of construction to a certain extent after precipitating.
In terms of the corrosion resistance for improving electrophoretic coating, forefathers are made that a large amount of work.Li Xiangtao uses zirconium film
Technology is as pre-treatment, and the binding force and corrosion resistance for improving paint film and substrate are (referring to Li Xiangtao, before cathode electro-coating
The research [D] of processing, Dalian Polytechnic University's master thesis, 2013), but zirconium pre-treatment is still than ferric solid-acid cost
It is high.The epoxy resin of high equivalent weight was once added in Nie Ren state in using electrodeposited paint film of the ferric solid-acid as preceding processing, improved paint
The degree of cross linking of film improves corrosion resistance of the electrodeposited paint film in ferric solid-acid (referring to Nie Ren state, SGMW to a certain extent
Vehicle corrosion resistance and vehicle body Anti-corrosive process for oil [D], Jilin University's master thesis, 2011), but the asphalt mixtures modified by epoxy resin of high equivalent weight
Rouge brings the problem of levelling aspect again, and the appearance of paint film is caused to be deteriorated.
Summary of the invention
For above situation, the purpose of the present invention is to provide a kind of cathode electrophoresis dope sulfosalt type dispersion resin and
Preparation method.The dispersion resin is a kind of cation dispersion resin, by the semi-enclosed isocyanates of small molecule thickener, containing work
Sprinkle hydrogen the semi-enclosed isocyanates of thio-ether type compounds, alcohol compound or the semi-enclosed isocyanates of alcohol ethers compound and
Epoxy resin reaction prepares matrix resin, then using the thio-ether type compounds and aforementioned body resin reaction being acidified through Bronsted acid
It is made, in which: alcohol compound or the semi-enclosed isocyanates of alcohol ethers compound are by alcohol compound or alcohol ethers compound
It reacts and is made with isocyanate ester compound；The semi-enclosed isocyanates of thio-ether type compounds containing active hydrogen is by containing active hydrogen
Thio-ether type compounds are reacted with isocyanate ester compound to be made；The semi-enclosed isocyanates of small molecule thickener is by polyethers
Object or polyethylene glycols compound is closed to react with isocyanate ester compound, then again with alcohol compound and alcohol ethers compound
Reaction is made.
In order to achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method of cathode electrophoresis dope sulfosalt type dispersion resin comprising following steps:
1) isocyanic acid under inert gas protection, is added into the reaction vessel with agitating device and cooling back installation
Ester type compound, the revolving speed for controlling agitating device is 300~600rpm；Polyethers (also known as polyether polyol) class compound is added dropwise,
Cooling back installation is opened simultaneously, keeps the temperature 1~4 hour in 20~40 DEG C；Alcohol compound or alcohol ethers compound is added dropwise, in 20
~40 DEG C keep the temperature 1~4 hour；Methyl iso-butyl ketone (MIBK) is added and obtains the semi-enclosed isocyanic acid of small molecule thickener after mixing evenly
Ester, it is spare；
Wherein: the molar ratio between the isocyanate ester compound and the polyethers chemical combination is 2~3:1；It is described different
Molar ratio between cyanate compound and the alcohol compound or alcohol ethers compound is 1.5~2:1；
2) isocyanic acid under inert gas protection, is added into the reaction vessel with agitating device and cooling back installation
Ester type compound, the revolving speed for controlling agitating device is 300~600rpm；The thio-ether type compounds containing active hydrogen are added dropwise, in 20~
40 DEG C keep the temperature 1~4 hour；Methyl iso-butyl ketone (MIBK) is added, it is semiclosed to obtain the thio-ether type compounds containing active hydrogen after mixing evenly
Isocyanates, it is spare；
Wherein: the molar ratio between the isocyanate ester compound and the thio-ether type compounds containing active hydrogen is
0.5~1:1；
3) isocyanic acid under inert gas protection, is added into the reaction vessel with agitating device and cooling back installation
Ester type compound, the revolving speed for controlling agitating device is 300~600rpm；Alcohol compound or alcohol ethers compound is added dropwise, in 20
~40 DEG C keep the temperature 1~4 hour；Methyl iso-butyl ketone (MIBK) is added, after mixing evenly, obtains alcohol compound or alcohol ethers compound half
Closed isocyanates, it is spare；
Wherein: the molar ratio between the isocyanate ester compound and the alcohol compound or alcohol ethers compound is
0.5~1:1；
4) under inert gas protection, be added into the reaction vessel with heating device and agitating device epoxy resin,
Bisphenol-A, nonyl phenol and dimethylbenzene are heated to 100~110 DEG C, and the revolving speed for controlling agitating device is 300~600rpm；First is added
Base triphenyl phosphonium iodide catalyst keeps the temperature 1~4 hour in 130~140 DEG C, is cooled to 100~110 DEG C, keeps the temperature 1~2 hour；
A dropping step 1) obtained in the semi-enclosed isocyanates of small molecule thickener, the thioether class containing active hydrogen obtained in step 2)
Alcohol compound obtained in the semi-enclosed isocyanates of compound and step 3) or the semi-enclosed isocyanic acid of alcohol ethers compound
Ester is cooled to 60~65 DEG C after keeping the temperature 1~3 hour in 100~110 DEG C；Thio-ether type compounds, Bronsted acid and water is added, in 65
~75 DEG C keep the temperature 4~8 hours, and water dilution is added, after mixing, obtains cathode electrophoresis dope sulfosalt type dispersion resin；
Wherein: between the semi-enclosed isocyanates of small molecule thickener and the epoxy resin obtained in the step 1)
Mass ratio be 5~15:100；The semi-enclosed isocyanates of thio-ether type compounds obtained in the step 2) containing active hydrogen
Mass ratio between the epoxy resin is 10~20:100；Alcohol compound obtained in the step 3) or alcohol ethers
Closing the mass ratio between the semi-enclosed isocyanates of object and the epoxy resin is 20~30:100.
Preferably, in the above preparation method, the inert gas includes nitrogen, helium, neon and argon gas, preferably nitrogen
Gas.
Preferably, in the above preparation method, the isocyanate ester compound include toluene di-isocyanate(TDI) (including 2,
4- toluene di-isocyanate(TDI) and 2,6- toluene di-isocyanate(TDI), preferably 2,4- toluene di-isocyanate(TDI)), two isocyanide of diphenyl methane
Acid esters (including 4,4 '-methyl diphenylene diisocyanates, 2,4 '-methyl diphenylene diisocyanates and 2,2 '-diphenyl methanes
Diisocyanate, preferably 4,4 '-methyl diphenylene diisocyanates), (including 1,3- benzene two is sub- for benzene dimethylene diisocyanate
Methyl diisocyanate and Isosorbide-5-Nitrae-benzene dimethylene diisocyanate, preferably 1,3- benzene dimethylene diisocyanate), six methylenes
Group diisocyanate, isophorone diisocyanate and dicyclohexyl methyl hydride diisocyanate (including 4,4 '-dicyclohexyl methyl hydrides
Diisocyanate, 2,4 '-dicyclohexyl methyl hydride diisocyanates and 2,2 '-dicyclohexyl methyl hydride diisocyanates, preferably 4,4 '-
Dicyclohexyl methyl hydride diisocyanate), preferred toluene di-isocyanate(TDI).
Preferably, in the above preparation method, the average molecular weight of the polyether compound is 200~2000.
Preferably, in the above preparation method, the alcohol compound includes isopropanol, n-butanol, the tert-butyl alcohol, Zhong Ding
Alcohol, n-amyl alcohol, tert-pentyl alcohol and isooctanol, preferably isooctanol.
Preferably, in the above preparation method, the alcohol ethers compound (is passed through by glycol compound and alcohol compound
Compound made from etherification reaction) it include ethylene glycol ethyl ether, butyl glycol ether, propylene glycol monomethyl ether, propandiol butyl ether and diethyl two
Alcohol butyl ether, preferably propandiol butyl ether.
Preferably, in the above preparation method, the thio-ether type compounds containing active hydrogen include methylthio phenyl methanol (packet
Include 4- methylthio phenyl methanol, 3- methylthio phenyl methanol and 2- methylthio phenyl methanol, preferably 4- methylthio phenyl methanol), methylthio phenyl
Phenol (including 4- methylthiophenol, 3- methylthiophenol and 2- methylthiophenol, preferably 4- methylthiophenol), 3- methyl mercapto -1-
Hexanol, 2- ethylthioethanol, 3- ethylmercapto group propyl alcohol, thiodiglycol, 4,4'- dihydroxy diphenyl sulfide and 2- Mercaptoethyl,
It is preferred that 2- ethylthioethanol.
Preferably, in the above preparation method, the epoxy resin includes bisphenol A type epoxy resin and bisphenol F type epoxy
Resin, preferably bisphenol A type epoxy resin；The epoxide equivalent (EEW) of the epoxy resin be 200~5000, preferably 500~
2000。
Preferably, in the above preparation method, the thio-ether type compounds include diethyl thioether, dipropyl thioether, two
Butyl thioether, diphenyl sulfide, thiodiglycol, methylthio phenyl methanol (including 4- methylthio phenyl methanol, 3- methylthio phenyl methanol and 2-
Methylthio phenyl methanol, preferably 4- methylthio phenyl methanol), methylthiophenol (including 4- methylthiophenol, 3- methylthiophenol and 2-
Methylthiophenol, preferably 4- methylthiophenol), methylthio-benzoic acid (including 4- methylthio-benzoic acid, 3- methylthio-benzoic acid and
2- methylthio-benzoic acid, preferably 4- methylthio-benzoic acid), methylthio phenyl acetic acid (including 4- methylthio phenyl acetic acid, 3- methylthio phenyl
Acetic acid and 2- methylthio phenyl acetic acid, preferably 4- methylthio phenyl acetic acid), 3 methyl mercapto 1 hexanol, 2- ethylthioethanol, 3- second sulphur
Base propyl alcohol, 4,4'- dihydroxy diphenyl sulfide and 2- Mercaptoethyl, preferably thiodiglycol.
Preferably, the Bronsted acid includes formic acid, glacial acetic acid, sulfamic acid, nitric acid, lactic acid and 2,2- dihydroxymethyl third
Acid, preferably glacial acetic acid.
Preferably, the water is deionized water.
The cathode electrophoresis dope sulfosalt type dispersion resin prepared by above-mentioned preparation method.In the dispersion resin structure
Sulphur atom can with iron ion formed iron sulfide linkage, improve the active force between coating and substrate, and then improve coating
Corrosion resistance and anti-dissolubility ability again；Meanwhile the dispersion resin has better levelability, improves the gloss of coating surface
And appearance.
Compared with prior art, by adopting the above technical scheme the present invention has the advantage that
(1) sulfosalt type dispersion resin of the invention forms iron sulphur using the sulphur atom and iron ion of the thioether bond in structure
Key, improves the binding force of coating and substrate, and then improves the corrosion resistance of coating and resist dissolubility ability again；
(2) solution viscosity of the lesser sulfosalt type resin of average molecular weight is lower, and sedimentation is also easy to produce when preparing mill base,
The present invention enables the resistance to settling of sulfosalt type dispersion resin to obtain greatly using the method for grafting small molecule association thickener
It is big to be promoted；
(3) average molecular weight of sulfosalt type dispersion resin of the invention is less than common quaternary ammonium salt dispersion resin, possesses more
Low glass transition temperature, levelability is more preferable, and the gloss of coating surface can be improved, and improves appearance attribute；
(4) the thioether key section in sulfosalt type dispersion resin structure of the invention is instead of quaternary dispersion resin knot
Ether-oxygen bond in structure improves the ability of high temperature resistant and color-changing；
(5) sulfosalt type dispersion resin of the invention is water-base resin, less to use organic solvent, low with VOC content,
The features such as good environmental protection；
(6) preparation method of the invention have simple process, reaction temperature is low, processing cost is low, is easy to operate in large scale
The advantages that.
Detailed description of the invention
Fig. 1 is the synthetic route chart of the 2 semi-enclosed isocyanates of small molecular thickener of embodiment.
Fig. 2 is the synthetic route chart of the semi-enclosed isocyanates of thio-ether type compounds containing active hydrogen in embodiment 2.
Fig. 3 is the synthetic route chart of alcohol compound or the semi-enclosed isocyanates of alcohol ethers compound in embodiment 2.
Fig. 4 is the synthetic route chart of cathode electrophoresis dope sulfosalt type dispersion resin in embodiment 2.
Specific embodiment
Further description is made to technical solution of the present invention below with reference to the drawings and specific embodiments.It should be understood that
, the following example is merely to illustrate the present invention, and is not the protection scope that present invention is limited in any form.In addition, removing
No special explanation, instrument, material, reagent used in the following example etc. can be obtained by routine business means.
Embodiment 1: cathode electrophoresis dope component A is prepared --- lotion.
Preparation method can refer to the method recorded in US8486538B2, US4419467, US3984299.
Prepare following each components in parts by weight: 816 parts of epoxy resin, 828,2 parts of methyl triphenyl phosphonium iodide catalysis
Agent, 384 parts of bisphenol-As, 60 parts of dimethylbenzene, 847 parts of blocked isocyanate crosslinking agents are (by toluene di-isocyanate(TDI) and isooctanol and three
Hydroxymethyl-propane reaction is made, and the molar ratio of isooctanol and trimethylolpropane is 7:3, solid point 85%), 45 parts of N- methyl lists
Ethanol amine, 144 parts of ketimides (be made by diethylenetriamines and methyl iso-butyl ketone (MIBK) through dehydration, solid point 85%), 120
Part propylene glycol n-butyl ether, 60 parts of propylene glycol phenylates, 24 parts of glacial acetic acid, 3500 parts of deionized waters.
Under nitrogen protection, epoxy resin 828, bisphenol-A are put into the reaction kettle with heating device and agitating device
And dimethylbenzene, control revolving speed are 400rpm, are heated to 100 DEG C or so；To all melt and after mixing, methyl triphen is added
Base phosphonium iodide catalyst keeps the temperature 2 hours in 140 DEG C；When test epoxide equivalent is 1100~1150, it is cooled to 100 DEG C or so；Add
Enter propylene glycol n-butyl ether and propylene glycol phenylate, (2-hydroxyethyl)methylamine) is then added, keeps the temperature 1 hour in 100 DEG C；It is sub- that ketone is added
Amine keeps the temperature 2 hours in 110 DEG C；Blocked isocyanate crosslinking agent is added, is stirred 0.5 hour in 120 DEG C of constant temperature；It is cooled to 90 DEG C
Hereinafter, glacial acetic acid is added, 0.5 hour is kept the temperature in 80 DEG C, obtains pre-dispersed resin；Deionization is added into another reaction vessel
Above-mentioned pre-dispersed resin is added in water under stirring, and control revolving speed is 1200rpm, after being uniformly dispersed, obtains lotion, spare.
Embodiment 2: sulfosalt type dispersion resin is prepared.
(1) prepare following each components in parts by weight: 174 parts of 2,4 toluene diisocyanate (molecular weight 174g/
Mol), 200 parts of polyethers 204 (average molecular weight 400g/mol), 90 parts of methyl iso-butyl ketone (MIBK)s, 130 parts of isooctanol (molecular weight
130g/mol)；
As shown in Figure 1, under nitrogen protection, being added into the four-hole bottle with blender, recirculated cooling water and head tank
2,4- toluene di-isocyanate(TDI)s, control revolving speed are 400rpm；Polyethers 204 is added dropwise, while opening cooling circulating water, is added dropwise within 3 hours
It finishes, keeps the temperature 2 hours in 30 DEG C；Isooctanol is added dropwise, is added dropwise within 2 hours, keeps the temperature 3 hours in 30 DEG C；Methyl-isobutyl is added
Ketone obtains the semi-enclosed isocyanates of small molecule thickener (component X in Fig. 1 and Fig. 4) after mixing evenly, spare.
(2) prepare following each components in parts by weight: 174 parts of 2,4 toluene diisocyanate (molecular weight 174g/
Mol), 107 parts of 2- ethylthioethanols (molecular weight 107g/mol), 15 parts of methyl iso-butyl ketone (MIBK)s；
As shown in Fig. 2, under nitrogen protection, being added into the four-hole bottle with blender, recirculated cooling water and head tank
2,4- toluene di-isocyanate(TDI)s, control revolving speed are 400rpm；2- ethylthioethanol is added dropwise and (originates from Maoming City Maoming Yunlong
Industrial development Co., Ltd, purity 99wt%), while cooling circulating water is opened, it is added dropwise within 2 hours, it is small in 30 DEG C of heat preservations 2
When；Methyl iso-butyl ketone (MIBK) is added and obtains semi-enclosed isocyanates (Fig. 2 of thio-ether type compounds containing active hydrogen after mixing evenly
With the Y component in Fig. 4), it is spare.
(3) prepare following each components in parts by weight: 174 parts of 2,4 toluene diisocyanate (molecular weight 174g/
Mol), 130 parts of isooctanol (molecular weight 130g/mol), 38 parts of methyl iso-butyl ketone (MIBK)s；
As shown in figure 3, under nitrogen protection, being added into the four-hole bottle with blender, recirculated cooling water and head tank
2,4- toluene di-isocyanate(TDI)s, control revolving speed are 400rpm；Isooctanol is added dropwise, while opening cooling circulating water, drips within 2 hours
Finish, keeps the temperature 2 hours in 30 DEG C；Methyl iso-butyl ketone (MIBK) is added, after mixing evenly, obtains alcohol compound or alcohol ethers compound half
Closed isocyanates (Z component in Fig. 3 and Fig. 4) is spare.
(4) prepare following each components in parts by weight: 443 parts of epoxy resin, 828,2 parts of methyl triphenyl phosphonium iodides
Catalyst, 157 parts of bisphenol-As, 44 parts of nonyl phenols, 20 parts of dimethylbenzene, the middle semiclosed isocyanates prepared of 35 parts of steps (1), 68
Semiclosed isocyanates, the middle semiclosed isocyanates prepared of 100 parts of steps (3), 147 parts of sulphur two prepared in part step (2)
Glycol, 48 parts of glacial acetic acid, 20 parts of deionized waters (1), 344 parts of propandiol butyl ethers, 200 parts of deionized waters (2)；
As shown in figure 4, being added into the four-hole bottle with vacuum evacuation device, agitating device, recirculated cooling water and head tank
Epoxy resin 828, bisphenol-A, nonyl phenol and dimethylbenzene are heated to 100 DEG C or so, and control revolving speed is 400rpm；To whole thawings
And after mixing, methyl triphenyl phosphonium iodide catalyst is added, keeps the temperature 2 hours in 140 DEG C, is cooled to 100 DEG C or so, heat preservation
1 hour；The three kinds of semi-enclosed isocyanates (component X, Y component and Z component) prepared in step (1) to (3) are added, in 110
DEG C heat preservation 2 hours after be cooled to 65 DEG C or so；The nco value in reaction product is measured less than 5 ‰, determines that grafting is complete；Sulphur is added
Diethylene glycol (DEG) (originating from Maoming City Maoming Yunlong Industrial Development Co., Ltd., purity 99wt%), glacial acetic acid and deionization
Water (1) keeps the temperature 4 hours in 70 DEG C, and deionized water (2) dilution is added, after mixing, obtains cathode electrophoresis dope sulfosalt
Type dispersion resin.The acid value for measuring final product is 1~3mgKOH/g, judges fully reacting, obtains expected product.
Embodiment 3: cathode electrophoresis dope B component is prepared --- mill base.
Prepare following each components in parts by weight: the sulfosalt type dispersion resin for preparing in 314 parts of embodiments 2,460
Part deionized water, 260 parts of china clay, 40 parts of carbon blacks, 8 parts of bismuth oxides and 1 part of Surfynol104E type wetting agent (originate from U.S.'s air
Chemical products Co., Ltd)；
Deionized water is added into the reaction vessel with high-speed stirring apparatus, control revolving speed is 1200rpm or so；It is added
Sulfosalt type dispersion resin is simultaneously uniformly dispersed；China clay, carbon black, bismuth oxide and Surfynol 104E type wetting agent is added and mixes
Uniformly；It is ground using high-speed grinder, control revolving speed is 3000rpm or so, is ground 2 hours, until fineness less than 20 microns, obtains
It is spare to mill base.
Embodiment 4: cathode electrophoresis dope working solution is prepared.
Prepare following each components in parts by weight: being made in the lotion that is prepared in 400 parts of embodiments 1,67 parts of embodiments 3
Standby mill base, 500 parts of deionized waters；
Deionized water is added in lotion, mill base is stirring evenly and then adding into, is uniformly mixed post curing 4 hours, then carries out
Electrophoresis operation, design parameter are as follows: construction voltage is 140V, and electrophoresis time is 2 minutes, and baking temperature is 140 DEG C.
Embodiment 5: the performance test of cathode electrophoresis dope.
Under identical operating conditions, the cathode that will be prepared respectively by sulfosalt type dispersion resin and quaternary dispersion resin
Electrophoretic coating carries out the performance comparison in terms of salt spray resistance, anti-dissolubility ability again and gloss, and wherein salt spray resistance test is pressed
It is carried out according to the method recorded in " measurement of the resistance to neutral salt spray performance of GB/T1771-2007 paint and varnish ", resists dissolubility ability again
Test is carried out according to the method recorded in " HG/T 3952-2007 cathode electrophoresis dope ", and measurement of luster is according to " GB/T 9754-
2007 paint and varnish without metallic pigments colored paint paint film 20 °, 60 ° and 85 ° bright lusters measurement " in record method
It carries out, the results are shown in Table 1.
The performance test results for the cathode electrophoresis dope that table 1. is prepared by different dispersion resins
As shown in Table 1, using sulfosalt type dispersion resin of the invention, it can be improved the corrosion resistance of coating and resist again
Dissolubility ability；In addition, sulfosalt type dispersion resin of the invention possesses lower glass transition temperature, levelability is more preferable, energy
The gloss for enough improving coating surface, improves appearance attribute.
Claims (9)
1. a kind of cathode electrophoresis dope preparation method of sulfosalt type dispersion resin comprising following steps:
1) isocyanates under inert gas protection, is added into the reaction vessel with agitating device and cooling back installation
Compound, the revolving speed for controlling agitating device is 300~600rpm；Polyether compound is added dropwise, while opening cooling back installation,
1~4 hour is kept the temperature in 20~40 DEG C；Alcohol compound or alcohol ethers compound is added dropwise, keeps the temperature 1~4 hour in 20~40 DEG C；Add
Enter methyl iso-butyl ketone (MIBK), after mixing evenly, obtains the semi-enclosed isocyanates of small molecule thickener, it is spare；
Wherein: the molar ratio between the isocyanate ester compound and the polyether compound is 2~3:1；The isocyanide
Molar ratio between acid esters compound and the alcohol compound or alcohol ethers compound is 1.5~2:1；
2) isocyanates under inert gas protection, is added into the reaction vessel with agitating device and cooling back installation
Compound, the revolving speed for controlling agitating device is 300~600rpm；The thio-ether type compounds containing active hydrogen are added dropwise, in 20~40 DEG C
Heat preservation 1~4 hour；Methyl iso-butyl ketone (MIBK) is added, it is semi-enclosed different to obtain the thio-ether type compounds containing active hydrogen after mixing evenly
Cyanate, it is spare；
Wherein: molar ratio between the isocyanate ester compound and the thio-ether type compounds containing active hydrogen is 0.5~
1:1；
3) isocyanates under inert gas protection, is added into the reaction vessel with agitating device and cooling back installation
Compound, the revolving speed for controlling agitating device is 300~600rpm；Alcohol compound or alcohol ethers compound is added dropwise, in 20~40
DEG C heat preservation 1~4 hour；Methyl iso-butyl ketone (MIBK) is added to obtain alcohol compound after mixing evenly or alcohol ethers compound is semiclosed
Isocyanates, it is spare；
Wherein: the molar ratio between the isocyanate ester compound and the alcohol compound or alcohol ethers compound is 0.5
~1:1；
4) epoxy resin, bis-phenol under inert gas protection, are added into the reaction vessel with heating device and agitating device
A, nonyl phenol and dimethylbenzene are heated to 100~110 DEG C, and the revolving speed for controlling agitating device is 300~600rpm；Methyl three is added
Phenyl phosphonium iodide catalyst keeps the temperature 1~4 hour in 130~140 DEG C, is cooled to 100~110 DEG C, keeps the temperature 1~2 hour；It is added dropwise
Thioether class chemical combination obtained in the semi-enclosed isocyanates of small molecule thickener, step 2) obtained in step 1) containing active hydrogen
Alcohol compound obtained in the semi-enclosed isocyanates of object and step 3) or the semi-enclosed isocyanates of alcohol ethers compound, in
100~110 DEG C heat preservation 1~3 hour after be cooled to 60~65 DEG C；Thio-ether type compounds, Bronsted acid and water is added, in 65~75 DEG C
Heat preservation 4~8 hours is added water dilution, after mixing, obtains cathode electrophoresis dope sulfosalt type dispersion resin；
Wherein: the matter between the semi-enclosed isocyanates of small molecule thickener and the epoxy resin obtained in the step 1)
Amount is than being 5~15:100；The semi-enclosed isocyanates of thio-ether type compounds and institute obtained in the step 2) containing active hydrogen
Stating the mass ratio between epoxy resin is 10~20:100；Alcohol compound obtained in the step 3) or alcohol ethers compound
Mass ratio between semi-enclosed isocyanates and the epoxy resin is 20~30:100.
2. preparation method according to claim 1, it is characterised in that:
The inert gas includes nitrogen, helium, neon and argon gas.
3. preparation method according to claim 1, it is characterised in that:
The isocyanate ester compound includes toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, phenylenedimethylidyne two
Isocyanates, hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexyl methyl hydride diisocyanate.
4. preparation method according to claim 1, it is characterised in that:
The average molecular weight of the polyether compound is 200~2000.
5. preparation method according to claim 1, it is characterised in that:
The alcohol compound includes isopropanol, n-butanol, the tert-butyl alcohol, sec-butyl alcohol, n-amyl alcohol, tert-pentyl alcohol and isooctanol；
The alcohol ethers compound includes ethylene glycol ethyl ether, butyl glycol ether, propylene glycol monomethyl ether, propandiol butyl ether and diethylene glycol
Butyl ether.
6. preparation method according to claim 1, it is characterised in that:
The thio-ether type compounds containing active hydrogen include methylthio phenyl methanol, methylthiophenol, 3 methyl mercapto 1 hexanol, 2-
Ethylthioethanol, 3- ethylmercapto group propyl alcohol, thiodiglycol, 4,4'- dihydroxy diphenyl sulfide and 2- Mercaptoethyl.
7. preparation method according to claim 1, it is characterised in that:
The epoxy resin includes bisphenol A type epoxy resin and bisphenol f type epoxy resin, and epoxide equivalent is 200~5000.
8. preparation method according to claim 1, it is characterised in that:
The thio-ether type compounds include diethyl thioether, dipropyl thioether, butyl sulfide, diphenyl sulfide, thiodiglycol, first
Sulfenyl benzyl alcohol, methylthiophenol, methylthio-benzoic acid, methylthio phenyl acetic acid, 3 methyl mercapto 1 hexanol, 2- ethylthioethanol,
3- ethylmercapto group propyl alcohol, 4,4'- dihydroxy diphenyl sulfide and 2- Mercaptoethyl；
The Bronsted acid includes formic acid, glacial acetic acid, sulfamic acid, nitric acid, lactic acid and 2,2- dihydromethyl propionic acid；
The water is deionized water.
9. a kind of cathode electrophoresis dope sulfosalt type dispersion resin, by according to any one of claim 1 to 8
Preparation method preparation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611069027.1A CN106700028B (en) | 2016-11-28 | 2016-11-28 | A kind of cathode electrophoresis dope sulfosalt type dispersion resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611069027.1A CN106700028B (en) | 2016-11-28 | 2016-11-28 | A kind of cathode electrophoresis dope sulfosalt type dispersion resin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106700028A CN106700028A (en) | 2017-05-24 |
| CN106700028B true CN106700028B (en) | 2019-03-22 |
Family
ID=58935018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611069027.1A Active CN106700028B (en) | 2016-11-28 | 2016-11-28 | A kind of cathode electrophoresis dope sulfosalt type dispersion resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106700028B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108690460A (en) * | 2018-04-03 | 2018-10-23 | 河北晨阳工贸集团有限公司 | A kind of cathode electrophoresis dope and preparation method thereof |
| CN108976981B (en) * | 2018-06-11 | 2021-09-03 | 中海油常州涂料化工研究院有限公司 | Emulsion for cathode electrophoretic coating, preparation method of emulsion, cathode electrophoretic coating and preparation method of cathode electrophoretic coating |
| CN111393683B (en) * | 2020-04-20 | 2023-05-23 | 广东科德环保科技股份有限公司 | Modified cationic microgel and preparation method and application thereof |
| CN114874413B (en) * | 2022-02-25 | 2024-03-01 | 上海金力泰化工股份有限公司 | Dispersing resin for cathode electrophoretic coating matched with film pretreatment and preparation method and application thereof |
| CN115716907B (en) * | 2022-11-22 | 2024-12-13 | 江苏富琪森新材料有限公司 | A zwitterionic waterborne epoxy resin and preparation method thereof, and a dispersion, preparation method thereof and application thereof |
| CN117551381B (en) * | 2023-11-10 | 2024-08-27 | 珠海东胜科技有限公司 | Heat-insulating glass coating and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06231444A (en) * | 1993-02-03 | 1994-08-19 | Nippon Polyurethane Ind Co Ltd | Polyurethane resin binder for magnetic recording medium |
| CN1111651A (en) * | 1994-03-22 | 1995-11-15 | 日本油漆株式会社 | Modified epoxy resins containing blocked isocyanate moieties and cationic groups and their use in cathodic electrodeposition coatings |
| CN1128275A (en) * | 1994-01-10 | 1996-08-07 | 日本油漆株式会社 | Pigment grinding resin for electrodeposition paint and pigment slurry containing the same |
| JP2002356645A (en) * | 2001-05-31 | 2002-12-13 | Nippon Paint Co Ltd | Lead-free cationic electrodeposition coating composition |
| CN1493627A (en) * | 2003-09-10 | 2004-05-05 | 江苏鸿业涂料科技产业有限公司 | Pigment dispersion resin for cathode electrophoresis paint and its pigment paste |
| CN105885662A (en) * | 2016-06-22 | 2016-08-24 | 广德瑞邦涂料有限公司 | Environment-friendly compound cathode electrophoretic paint |
| CN106118347A (en) * | 2016-06-22 | 2016-11-16 | 广德瑞邦涂料有限公司 | A kind of color inhibition cathode electrodip painting of environment-friendly and green |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4060620B2 (en) * | 2002-03-26 | 2008-03-12 | 日本ペイント株式会社 | Electrodeposition coating method using lead-free cationic electrodeposition paint |
-
2016
- 2016-11-28 CN CN201611069027.1A patent/CN106700028B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06231444A (en) * | 1993-02-03 | 1994-08-19 | Nippon Polyurethane Ind Co Ltd | Polyurethane resin binder for magnetic recording medium |
| CN1128275A (en) * | 1994-01-10 | 1996-08-07 | 日本油漆株式会社 | Pigment grinding resin for electrodeposition paint and pigment slurry containing the same |
| CN1111651A (en) * | 1994-03-22 | 1995-11-15 | 日本油漆株式会社 | Modified epoxy resins containing blocked isocyanate moieties and cationic groups and their use in cathodic electrodeposition coatings |
| JP2002356645A (en) * | 2001-05-31 | 2002-12-13 | Nippon Paint Co Ltd | Lead-free cationic electrodeposition coating composition |
| CN1493627A (en) * | 2003-09-10 | 2004-05-05 | 江苏鸿业涂料科技产业有限公司 | Pigment dispersion resin for cathode electrophoresis paint and its pigment paste |
| CN105885662A (en) * | 2016-06-22 | 2016-08-24 | 广德瑞邦涂料有限公司 | Environment-friendly compound cathode electrophoretic paint |
| CN106118347A (en) * | 2016-06-22 | 2016-11-16 | 广德瑞邦涂料有限公司 | A kind of color inhibition cathode electrodip painting of environment-friendly and green |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106700028A (en) | 2017-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106700028B (en) | A kind of cathode electrophoresis dope sulfosalt type dispersion resin and preparation method thereof | |
| RU2692788C1 (en) | Flexible non-chromate anticorrosive primer | |
| CN106232750B (en) | Electrodeposition coating composition, electrodeposition coating composition catalyst | |
| CN103635547A (en) | Cationic electrodeposition paint composition capable even of coating sections having narrow clearance, and electrodeposition paint-film formation method using same | |
| CN109504264B (en) | Edge anti-corrosion electrophoretic coating composition, preparation method and application | |
| KR20100112573A (en) | Organic solvent free pigment dispersant for waterborne electrocoating | |
| EP3904454B1 (en) | Preparation method for emulsifier, emulsifier, aqueous epoxy resin dispersion and formulation method | |
| CN1310212A (en) | Cation electro-deposition coating composition | |
| CN109111793A (en) | A kind of electrophoretic coating mill base improving wearability | |
| CN114621648A (en) | Water-based single-component anticorrosive primer and preparation method thereof | |
| CA3222684A1 (en) | Electrodepositable coating compositions | |
| JP2013064069A (en) | Rust-prevention coating composition | |
| CN102898884B (en) | Environment-friendly cashew amine epoxy curing agent for low volatile organic compound (VOC) anticorrosive coating and preparation method for curing agent | |
| CN116179064A (en) | Water-based low-temperature baking material for bicycles and preparation method thereof | |
| US7790802B2 (en) | Coating material, method for production and use thereof for the production of adhesive tone and/or effect-generating coatings | |
| CN113563561B (en) | Resin for cathode electrophoretic coating color paste, preparation method of resin and coating color paste | |
| CN114874413B (en) | Dispersing resin for cathode electrophoretic coating matched with film pretreatment and preparation method and application thereof | |
| JP2015193684A (en) | cationic electrodeposition coating composition | |
| JP5595131B2 (en) | Cationic electrodeposition coating composition | |
| WO2017187900A1 (en) | Electrodeposition coating composition and method for producing same | |
| WO2025193641A1 (en) | Emulsifiable resins | |
| CN120758133A (en) | A kind of water-based dip coating for mining chain and preparation method thereof | |
| CN115725224A (en) | Solvent-free pure water anticorrosive paint and preparation method thereof | |
| CN119286374A (en) | A vegetable oil-based polyurethane anticorrosive coating | |
| CN115124918A (en) | Production process of cathode two-component electrophoretic paint with high throwing power |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |