CN110437711A - A kind of low temperature curing type B68 extinction powder epoxy resin and the preparation method and application thereof - Google Patents
A kind of low temperature curing type B68 extinction powder epoxy resin and the preparation method and application thereof Download PDFInfo
- Publication number
- CN110437711A CN110437711A CN201910770042.6A CN201910770042A CN110437711A CN 110437711 A CN110437711 A CN 110437711A CN 201910770042 A CN201910770042 A CN 201910770042A CN 110437711 A CN110437711 A CN 110437711A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- low temperature
- curing type
- temperature curing
- extinction powder
- 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.)
- Granted
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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/066—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with chain extension or advancing agents
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery 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
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/42—Gloss-reducing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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)
- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
Abstract
The invention belongs to powder coating technology fields, and in particular to a kind of low temperature curing type B68 extinction powder epoxy resin and the preparation method and application thereof.Low temperature curing type B68 extinction powder epoxy resin of the present invention, with bisphenol-A, epoxychloropropane, sodium hydroxide, 2, 2- dimethyl malonic acid, terephthalic acid (TPA), toluene, and E-44 epoxy resin of high epoxy-reactive etc. is that raw material is polymerize, the monomer diethylene glycol diglycidyl glycerin ether of high activity is used to be blocked for end-capping reagent, and the mode mixed again after epoxy resin I and epoxy resin II is prepared respectively by using double formulas, it obtains finally dispersing compatibility relatively poor, and segment is softer, the higher epoxy resin product of activity, be conducive to obtain the film of more low gloss, and due to molecule segment difference, so that activity difference is obvious, softening point relative reduction, 150 DEG C/20min may be implemented sufficiently to solidify, not only largely reduce energy consumption, and coating film gloss can be with It is even lower to reach 5%.
Description
Technical field
The invention belongs to powder coating technology fields, and in particular to a kind of low temperature curing type B68 extinction powder asphalt mixtures modified by epoxy resin
Rouge and the preparation method and application thereof.
Background technique
Powdery paints is a kind of 100% solid powder without organic solvent, it is different from oil paint and water paint,
Not using solvent or water as decentralized medium when coating, but using air as decentralized medium, it is uniformly coated on workpiece surface, is passed through
A kind of new type environment friendly coating of one layer of film with specific use is formed after heating.Powdery paints has VOC free, environmental protection, section
Can, the advantages that construction efficiency height and application range is wide, and the advantages that, environmental protection economic with it, brilliant efficient and performance, just gradually replace
For organic solvent type coatings, become the important development direction in coating industry, is always maintained at faster growth rate.Polyesters
Powdery paints more with its excellent durability, dicoration and processing forming the features such as, be widely used in field of coating.
Epoxy powder coating is a kind of thermosetting powder coating with corrosion resistance and toughness, is not only applied
Earliest, and development is also the quickest.Epoxy powder coating system is mostly by epoxy resin, pigments and fillers, additive and curing agent
Composition.The preparation of epoxy powder coating is also mostly to be wrapped using the method for international production thermosetting powder coating
Including melting mixing extrusion molding -- mixing, melting mixing squeeze out, are finely divided and etc..Under normal conditions, epoxy powder coating
Preparation process in require to select hard resin of the epoxide equivalent between 700-1000 as film forming matter, curing agent is main
Including dicyandiamide, cyanoguanidine derivative, acid anhydrides, imidazoles, cyclic ethers, phenolic resin polyester resin, boron trifluoride amine complex etc., work
In industry, dicyandiamide, imidazoles and cyclic ethers are mostly used, and the most common dulling and curing agent in low gloss epoxide powder coating field is
B68 dulling and curing agent.B68 dulling and curing agent is the complex compound of Pyromellitic Acid Yu 2- benzylimidazoline, can be with E-12 epoxy
Resin is solidified to obtain the film of low gloss (< 10%), to obtain decorative outstanding film coated surface.
Common E-12 epoxy resin is that directly reaction obtains in the presence of alkali using bisphenol-A and epoxychloropropane, is produced
The molecular structure of product is single, and the activity of terminal epoxy is influenced by bisphenol-A steric hindrance, and activity is slightly lower, and softening point is high, usually exists
It is difficult sufficiently to solidify lower than 180 DEG C, even if being solidified with B68 dulling and curing agent, being generally also required to 185 DEG C/20min could be real
Now sufficiently solidification, the energy consumption for not only resulting in curing process is higher, and causes film impact property poor, and due to asphalt mixtures modified by epoxy resin
Rouge strand is more uniform, also cause normal additive amount B68 dulling and curing agent can not effectively delustring to 5% and its less.
Have great importance as it can be seen that developing a kind of achievable low temperature curing type B68 extinction powder with epoxy resin.
Summary of the invention
For this purpose, technical problem to be solved by the present invention lies in provide a kind of low temperature curing type B68 extinction powder epoxy
Resin, to solve that E-12 epoxy resin cure temperature in the prior art is higher, to lead to solidify energy consumption high and influence product glossiness
The problem of；
Second technical problem that the present invention solves is to provide above-mentioned low temperature curing type B68 extinction powder epoxy resin
Preparation method and its purposes for being used to prepare epoxy-resin systems powdery paints.
In order to solve the above technical problems, a kind of low temperature curing type B68 extinction powder epoxy resin of the present invention, with
It prepares raw material total amount meter, the raw material components including following molar content:
Preferably, the raw material for preparing further includes catalyst.
Specifically, the mole dosage of the catalyst accounts for the 0.1-0.2% of the raw material components integral molar quantity.
Specifically, the catalyst includes benzyltrimethylammonium chloride and/or triphenylmethylphosphonium bromide phosphorus.
The invention also discloses a kind of methods for preparing the low temperature curing type B68 extinction powder epoxy resin, including
Following steps:
(1) it takes the sodium hydroxide of formula ratio to prepare to obtain sodium hydroxide solution, and the bisphenol-A of formula ratio is added, in
30-40 DEG C is reacted；The epoxychloropropane of formula ratio is then added, is reacted in 80-100 DEG C, to reaction system
PH < 9.5 when, stop reaction, obtain bisphenol-A sealing end epoxy resin；
(2) diethylene glycol of formula ratio is added in the epoxy resin composition material blocked to bisphenol-A obtained above
Diglycidyl ether when the epoxide equivalent of resin reaches 750-800eq/100g, stops in 80-90 DEG C of progress end capping reaction
Reaction, obtains epoxy resin I, spare；
(3) toluene of formula ratio, E-44 epoxy resin, 2,2- dimethyl malonic acid, terephthalic acid (TPA) are separately taken and is urged
Agent mixes, and in 90-105 DEG C of progress chain extending reaction, when the epoxide equivalent of resin reaches 800-850eq/100g, stops anti-
It answers, obtains epoxy resin II, it is spare；
(4) above-mentioned epoxy resin I and epoxy resin II is mixed, is reacted in 80-90 DEG C, is reached to epoxide equivalent
When 830-860eq/100g, vacuum decompression removes toluene solvant, and high temperature discharging while hot, through cooling, broken, granulation to get institute
Need low temperature curing type B68 extinction powder epoxy resin.
Specifically, the mass concentration for controlling the sodium hydroxide solution is 30-50wt% in the step (1).
Specifically, further including after the completion of reaction, the epoxy resin I being added water washing and is carried out in the step (2)
The step of decompression dehydration.
The invention also discloses the low temperature curing type B68 extinction powders to be used to prepare the use of powdery paints with epoxy resin
On the way.
Specifically, the powdery paints is B68 curing system epoxy powder coating.
The invention also discloses the powdery paints prepared by the low temperature curing type B68 extinction powder with epoxy resin.
Low temperature curing type B68 extinction powder epoxy resin of the present invention, with bisphenol-A, epoxychloropropane, hydroxide
Sodium, 2,2- dimethyl malonic acid, terephthalic acid (TPA), toluene and E-44 epoxy resin of high epoxy-reactive etc. carry out for raw material
Polymerization, uses the monomer diethylene glycol diglycidyl glycerin ether of high activity to be blocked for end-capping reagent, and by using double formulas point
The mode mixed again after epoxy resin I and epoxy resin II is not prepared, obtains finally dispersing that compatibility is relatively poor and chain
Section is softer, the higher epoxy resin product of activity, is conducive to obtain the film of more low gloss, and due to molecule segment difference, make
Activity difference it is obvious, softening point relative reduction may be implemented 150 DEG C/20min and sufficiently solidify, not only largely reduces
Energy consumption, and to can achieve 5% even lower for coating film gloss.
The activity of low temperature curing type B68 extinction powder epoxy resin of the present invention, product is higher, and softening point is opposite
It is lower, it is ensured that good low temperature levelability, low-temperature setting reactivity, extinction performance and impact property, resistance to boiling water
It boils, the performances such as gloss and adhesive force reach the application requirement of powdery paints, film performance and at present common E-12 epoxy resin
The cured film of normal temperature is suitable, and extinction effect is better than the cured film of ordinary temp, and various aspects of performance can reach E-
12 epoxy resin and the normal cured application requirement of 185 DEG C/20min of B68 dulling and curing agent, can be used for condition of cure be 150 DEG C/
Excellent comprehensive performance is achieved in the low temperature cured powder coating of 20min, can meet client to 5% and more low-luster product
Effect requirements.
Specific embodiment
Embodiment 1
Low temperature curing type B68 extinction powder epoxy resin described in the present embodiment, preparing raw material includes following mole hundred
Divide the raw material components of ratio:
The preparation method of low temperature curing type B68 extinction powder epoxy resin, includes the following steps: described in the present embodiment
(1) add water to prepare to obtain the sodium hydroxide solution of 30% solid content the sodium hydroxide of formula ratio, and be pumped into reaction
In kettle I, 30 DEG C are warming up to, the bisphenol-A of formula ratio is added, carries out insulation reaction 1-2h；The epoxy of formula ratio is then then added
Chloropropane, in 80 DEG C of progress insulation reaction 2-4h, the pH of solution stops reaction, obtains when pH reaches 9.5 or less after tested
The epoxy resin of bisphenol-A sealing end；
(2) the diethylene glycol diglycidyl glycerol of formula ratio is added in the epoxy resin composition material of Xiang Shangshu bisphenol-A sealing end
Ether, in 80 DEG C of progress end capping reaction 1-2h, then the epoxide equivalent of sampling and testing epoxy resin, is 750- to epoxide equivalent
When 800eq/100g, stops reaction, separate water phase and asphalt mixtures modified by epoxy resin lipid phase, epoxy resin washing is washed 5-8 times, use water quality every time
It is finally spare to epoxy resin I is obtained after epoxy resin progress decompression dehydration for the one third of resin quality；
(3) separately take reaction kettle II, be added the toluene of formula ratio, E-44 epoxy resin, 2,2- dimethyl malonic acid, to benzene two
Formic acid and catalyst are warming up to 90 DEG C of progress chain extending reaction 2-4h, when the epoxide equivalent of resin is 800-850eq/100g, stop
It only reacts, obtains epoxy resin II；
(4) epoxy resin I spare in reaction kettle I is added in reaction kettle II, is carried out with epoxy resin II at 80 DEG C
Hybrid reaction 1-2h, when epoxide equivalent is 830-860eq/100g, starting vacuum carries out removed under reduced pressure toluene solvant, then takes advantage of
Hot high temperature discharging, and with the cooling epoxy resin of the steel band with condensed water, be then crushed be granulated to get.
After tested, it is colorless and transparent particle that epoxy resin, which is prepared, in the present embodiment, and epoxide equivalent 845eq/100g is soft
Change 84 DEG C of point.
Embodiment 2
Low temperature curing type B68 extinction powder epoxy resin described in the present embodiment, preparing raw material includes following mole hundred
Divide the raw material components of ratio:
The preparation method of low temperature curing type B68 extinction powder epoxy resin, includes the following steps: described in the present embodiment
(1) add water to prepare to obtain the sodium hydroxide solution of 40% solid content the sodium hydroxide of formula ratio, and be pumped into reaction
In kettle I, 35 DEG C are warming up to, the bisphenol-A of formula ratio is added, carries out insulation reaction 1-2h；The epoxy of formula ratio is then then added
Chloropropane, in 90 DEG C of progress insulation reaction 2-4h, the pH of solution stops reaction, obtains when pH reaches 9.5 or less after tested
The epoxy resin of bisphenol-A sealing end；
(2) the diethylene glycol diglycidyl glycerol of formula ratio is added in the epoxy resin composition material of Xiang Shangshu bisphenol-A sealing end
Ether, in 85 DEG C of progress end capping reaction 1-2h, then the epoxide equivalent of sampling and testing epoxy resin, is 750- to epoxide equivalent
When 800eq/100g, stops reaction, separate water phase and asphalt mixtures modified by epoxy resin lipid phase, epoxy resin washing is washed 5-8 times, use water quality every time
It is finally spare to epoxy resin I is obtained after epoxy resin progress decompression dehydration for the one third of resin quality；
(3) separately take reaction kettle II, be added the toluene of formula ratio, E-44 epoxy resin, 2,2- dimethyl malonic acid, to benzene two
Formic acid and catalyst are warming up to 100 DEG C of progress chain extending reaction 2-4h, when the epoxide equivalent of resin is 800-850eq/100g,
Stop reaction, obtains epoxy resin II；
(4) epoxy resin I spare in reaction kettle I is added in reaction kettle II, is carried out with epoxy resin II at 85 DEG C
Hybrid reaction 1-2h, when epoxide equivalent is 830-860eq/100g, starting vacuum carries out removed under reduced pressure toluene solvant, then takes advantage of
Hot high temperature discharging, and with the cooling epoxy resin of the steel band with condensed water, be then crushed be granulated to get.
After tested, it is colorless and transparent particle that epoxy resin, which is prepared, in the present embodiment, and epoxide equivalent 858eq/100g is soft
Change 86 DEG C of point.
Embodiment 3
Low temperature curing type B68 extinction powder epoxy resin described in the present embodiment, preparing raw material includes following mole hundred
Divide the raw material components of ratio:
The preparation method of low temperature curing type B68 extinction powder epoxy resin, includes the following steps: described in the present embodiment
(1) add water to prepare to obtain the sodium hydroxide solution of 50% solid content the sodium hydroxide of formula ratio, and be pumped into reaction
In kettle I, 40 DEG C are warming up to, the bisphenol-A of formula ratio is added, carries out insulation reaction 1-2h；The epoxy of formula ratio is then then added
Chloropropane, in 100 DEG C of progress insulation reaction 2-4h, the pH of solution stops reaction, obtains when pH reaches 9.5 or less after tested
The epoxy resin of bisphenol-A sealing end；
(2) the diethylene glycol diglycidyl glycerol of formula ratio is added in the epoxy resin composition material of Xiang Shangshu bisphenol-A sealing end
Ether, in 90 DEG C of progress end capping reaction 1-2h, then the epoxide equivalent of sampling and testing epoxy resin, is 750- to epoxide equivalent
When 800eq/100g, stops reaction, separate water phase and asphalt mixtures modified by epoxy resin lipid phase, epoxy resin washing is washed 5-8 times, use water quality every time
It is finally spare to epoxy resin I is obtained after epoxy resin progress decompression dehydration for the one third of resin quality；
(3) separately take reaction kettle II, be added the toluene of formula ratio, E-44 epoxy resin, 2,2- dimethyl malonic acid, to benzene two
Formic acid and catalyst are warming up to 105 DEG C of progress chain extending reaction 2-4h, when the epoxide equivalent of resin is 800-850eq/100g,
Stop reaction, obtains epoxy resin II；
(4) epoxy resin I spare in reaction kettle I is added in reaction kettle II, is carried out with epoxy resin II at 90 DEG C
Hybrid reaction 1-2h, when epoxide equivalent is 830-860eq/100g, starting vacuum carries out removed under reduced pressure toluene solvant, then takes advantage of
Hot high temperature discharging, and with the cooling epoxy resin of the steel band with condensed water, be then crushed be granulated to get.
After tested, it is colorless and transparent particle that epoxy resin, which is prepared, in the present embodiment, and epoxide equivalent 834eq/100g is soft
Change 88 DEG C of point.
Embodiment 4
Low temperature curing type B68 extinction powder epoxy resin described in the present embodiment, preparing raw material includes following mole hundred
Divide the raw material components of ratio:
The preparation method of low temperature curing type B68 extinction powder epoxy resin, includes the following steps: described in the present embodiment
(1) add water to prepare to obtain the sodium hydroxide solution of 40% solid content the sodium hydroxide of formula ratio, and be pumped into reaction
In kettle I, 35 DEG C are warming up to, the bisphenol-A of formula ratio is added, carries out insulation reaction 1-2h；The epoxy of formula ratio is then then added
Chloropropane, in 90 DEG C of progress insulation reaction 2-4h, the pH of solution stops reaction, obtains when pH reaches 9.5 or less after tested
The epoxy resin of bisphenol-A sealing end；
(2) the diethylene glycol diglycidyl glycerol of formula ratio is added in the epoxy resin composition material of Xiang Shangshu bisphenol-A sealing end
Ether, in 85 DEG C of progress end capping reaction 1-2h, then the epoxide equivalent of sampling and testing epoxy resin, is 750- to epoxide equivalent
When 800eq/100g, stops reaction, separate water phase and asphalt mixtures modified by epoxy resin lipid phase, epoxy resin washing is washed 5-8 times, use water quality every time
It is finally spare to epoxy resin I is obtained after epoxy resin progress decompression dehydration for the one third of resin quality；
(3) separately take reaction kettle II, be added the toluene of formula ratio, E-44 epoxy resin, 2,2- dimethyl malonic acid, to benzene two
Formic acid and catalyst are warming up to 95 DEG C of progress chain extending reaction 2-4h, when the epoxide equivalent of resin is 800-850eq/100g, stop
It only reacts, obtains epoxy resin II；
(4) epoxy resin I spare in reaction kettle I is added in reaction kettle II, is carried out with epoxy resin II at 85 DEG C
Hybrid reaction 1-2h, when epoxide equivalent is 830-860eq/100g, starting vacuum carries out removed under reduced pressure toluene solvant, then takes advantage of
Hot high temperature discharging, and with the cooling epoxy resin of the steel band with condensed water, be then crushed be granulated to get.
After tested, it is colorless and transparent particle that epoxy resin, which is prepared, in the present embodiment, and epoxide equivalent 852eq/100g is soft
Change 85 DEG C of point.
Comparative example 1
The raw material composition of epoxy resin described in this comparative example is same as Example 2, and difference is only that without containing diethyl two
Alcohol diglycidyl ether.
After tested, this comparative example be prepared epoxy resin epoxide equivalent be 1130eq/100g, 95 DEG C of softening point.
Comparative example 2
The raw material composition of epoxy resin described in this comparative example is same as Example 2, and difference is only that without containing 2,2- bis-
Methylmalonic acid.
After tested, this comparative example be prepared epoxy resin epoxide equivalent be 720eq/100g, 92 DEG C of softening point.
Comparative example 3
The raw material composition of epoxy resin described in this comparative example is same as Example 2, and difference is only that without containing to benzene two
Formic acid.
After tested, this comparative example be prepared epoxy resin epoxide equivalent be 760eq/100g, 80 DEG C of softening point.
Experimental example
Epoxy resin made from 1-4 of the embodiment of the present invention and comparative example 1-3 is taken respectively, is grouped as progress according to following group
The preparation of B68 extinction powder coating, specific formula are as follows:
Raw material is commercially available common material in formula, and wherein B68 dulling and curing agent is purchased from Huangshan Huahui Technology Co., Ltd.,
Trade mark HC68, levelling agent and optical brightener are purchased from Ningbo South-sea Chemical Co., Ltd., and the trade mark is respectively GLP388, BLC701.
With the intermediate product-epoxy resin I (epoxide equivalent 780eq/100g, 83 DEG C of softening point) prepared in embodiment 2
Instead of low temperature curing type epoxy resin of the present invention as a comparison case 4.
With the intermediate product-epoxy resin II (epoxide equivalent 820eq/100g, 88 DEG C of softening point) prepared in embodiment 2
Instead of low temperature curing type epoxy resin of the present invention as a comparison case 5.
The present invention is replaced with existing commercially available common E-12 epoxy resin (epoxide equivalent 870eq/100g, 93 DEG C of softening point)
The low temperature curing type epoxy resin as a comparison case 6.
The present invention is replaced with existing commercially available common E-12 epoxy resin (epoxide equivalent 870eq/100g, 93 DEG C of softening point)
The low temperature curing type epoxy resin, and being solidified under the conditions of 185 DEG C/20min, as a comparison case 7.
The preparation of powdery paints coating: each material is mixed according to the formula of B68 extinction powder coating, uses double screw extruder
Extrusion, is crushed tabletting, then sheet stock pulverizes and sieves, powdery paints (180 mesh) is made；Powdery paints is sprayed using electrostatic gun
On tinplate substrate after surface treated, solidify through 150 DEG C/20min to get paint coatings.
Coating Indexs measure is according to GB/T 21776-2008 " the examination criteria guide of powdery paints and its coating ", attachment
Power level estimate establishing criteria GB/T 9286-1998 " cross cut test of paint and varnish paint film ".
Above-described embodiment and comparative example are made after coating is made according to above-mentioned coating formula of the present invention in epoxy resin and test it
Coating performance result is as shown in Table 1 below.
1 performance powder coating detection data of table
Made from data in upper table 1 it is found that epoxy resin is made in 1-4 of the embodiment of the present invention by the collaboration between each component
With obtained epoxy resin is used in B68 delustring cured powder paint, low-temperature setting reactivity, extinction performance etc. such as punching
The application requirement that performance, resistance to boiling water boiling, gloss and adhesive force etc. reach powdery paints is hit, makes epoxy resin obtained for solid
Excellent comprehensive performance is achieved in the low temperature cured powder coating that change condition is 150 DEG C/20min.
And the scheme of epoxy resin is prepared in comparative example 1-3, due to lacking individual related components, obtained epoxy resin exists
Film is apparent, consolidate gloss, defect occurs in solidification situation and impact property.Such as, diethylene glycol diglycidyl glycerin ether is scarce
The epoxy resin I terminal epoxy activity that will lead to less is low, and 150 DEG C/20min, which cannot achieve, to be fully cured, and impact property becomes
Difference, and the adhesive force of film and resistance to boiling water boiling performance do not reach requirement (see comparative example 1)；Lack in comparative example 2 and comparative example 3
The components such as 2,2- dimethyl malonic acids and terephthalic acid (TPA), the shock resistance that will lead to the epoxy resin II to be formed are deteriorated, shadow
The adhesive force of the final epoxy resin of sound and resistance to boiling water boiling performance.
Such as data in comparative example 4-5, epoxy resin I or epoxy resin II is used alone, due to the work of epoxy-functional
Property it is more single, activity it is higher, although may be implemented with the solidification of B68 dulling and curing agent be crosslinked, extinction effect is general, gloss
It is slightly higher；After needing to mix both its epoxy resin I and epoxy resin II the blending epoxy system that is formed due to and meanwhile have
Active different epoxy functionalized figure, when solidifying with B68, speed is variant, causes extinction effect obvious.
Such as data in comparative example 6-7, using commercially available common E-12 epoxy resin, due to the segment and steric hindrance of bisphenol-A,
The low temperature active of epoxy-functional is not high, and 150 DEG C/20min, which cannot achieve, to be fully cured, and film performance is very poor (see comparative example 6),
And good cured coating film may be implemented in 185 DEG C/20min of normal cure condition in it (see comparative example 7).
To sum up, the low temperature curing type B68 extinction powder epoxy resin of this programme preparation can exist with B68 dulling and curing agent
150 DEG C/20min realizes sufficiently solidification, and film performance is suitable with the current common E-12 cured film of epoxy resin normal temperature,
Simultaneously as the particularity of formula and technique, extinction effect is better than the common cured film of E-12 epoxy resin normal temperature.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of low temperature curing type B68 extinction powder epoxy resin, which is characterized in that in terms of preparing raw material total amount by it, including
The raw material components of following molar content:
2. low temperature curing type B68 extinction powder epoxy resin according to claim 1, which is characterized in that the preparation is former
Material further includes catalyst.
3. low temperature curing type B68 extinction powder epoxy resin according to claim 2, which is characterized in that the catalyst
Mole dosage account for the 0.1-0.2% of the raw material components integral molar quantity.
4. the low temperature curing type B68 extinction powder epoxy resin according to Claims 2 or 3, which is characterized in that the catalysis
Agent includes benzyltrimethylammonium chloride and/or triphenylmethylphosphonium bromide phosphorus.
5. a kind of method for preparing any one of claim 1-4 low temperature curing type B68 extinction powder epoxy resin, special
Sign is, includes the following steps:
(1) it takes the sodium hydroxide of formula ratio to prepare to obtain sodium hydroxide solution, and the bisphenol-A of formula ratio is added, in 30-40
It DEG C is reacted；Then be added formula ratio the epoxychloropropane, reacted in 80-100 DEG C, to reaction system pH <
When 9.5, stop reaction, obtains the epoxy resin of bisphenol-A sealing end；
(2) diethylene glycol two that formula ratio is added in the epoxy resin composition material blocked to bisphenol-A obtained above contracts
Water glycerin ether when the epoxide equivalent of resin reaches 750-800eq/100g, stops reaction in 80-90 DEG C of progress end capping reaction,
Epoxy resin I is obtained, it is spare；
(3) toluene, E-44 epoxy resin, 2,2- dimethyl malonic acid, terephthalic acid (TPA) and the catalyst of formula ratio are separately taken
It mixes, in 90-105 DEG C of progress chain extending reaction, when the epoxide equivalent of resin reaches 800-850eq/100g, stops reaction, obtain
It is spare to epoxy resin II；
(4) above-mentioned epoxy resin I and epoxy resin II is mixed, is reacted in 80-90 DEG C, reaches 830- to epoxide equivalent
When 860eq/100g, vacuum decompression removes toluene solvant, and high temperature discharging while hot, through cooling, broken, granulation to get required low
Warm curing type B68 extinction powder epoxy resin.
6. the preparation method of low temperature curing type B68 extinction powder epoxy resin according to claim 5, which is characterized in that
In the step (1), the mass concentration for controlling the sodium hydroxide solution is 30-50wt%.
7. according to the preparation method of the low temperature curing type B68 extinction powder epoxy resin of claim 5 or 6, feature exists
In further including after the completion of reaction, the epoxy resin I being added water washing and carries out the step of decompression dehydration in the step (2)
Suddenly.
8. any one of the claim 1-4 low temperature curing type B68 extinction powder is used to prepare powdery paints with epoxy resin
Purposes.
9. purposes according to claim 8, which is characterized in that the powdery paints is B68 curing system epoxy resin powder
Last coating.
10. the powdery paints prepared by any one of the claim 1-4 low temperature curing type B68 extinction powder with epoxy resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910770042.6A CN110437711B (en) | 2019-08-20 | 2019-08-20 | Epoxy resin for low-temperature curing type B68 extinction powder and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910770042.6A CN110437711B (en) | 2019-08-20 | 2019-08-20 | Epoxy resin for low-temperature curing type B68 extinction powder and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110437711A true CN110437711A (en) | 2019-11-12 |
| CN110437711B CN110437711B (en) | 2021-07-13 |
Family
ID=68436687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910770042.6A Active CN110437711B (en) | 2019-08-20 | 2019-08-20 | Epoxy resin for low-temperature curing type B68 extinction powder and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110437711B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110835403A (en) * | 2019-11-18 | 2020-02-25 | 黄山学院 | Epoxy resin for low-temperature curable flame-retardant powder coating and preparation method thereof |
| CN112048057A (en) * | 2020-09-11 | 2020-12-08 | 安徽鑫友高分子新材料科技有限公司 | Epoxy resin, application and high-leveling ultralow-temperature curing type pure powder coating |
| CN112321799A (en) * | 2020-11-04 | 2021-02-05 | 黄山新佳精细材料有限公司 | Epoxy resin for high-hardness and low-temperature curing type powder coating and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050288450A1 (en) * | 2003-05-23 | 2005-12-29 | Tim Fletcher | Coating matting agent comprising amide condensation product |
| CN104693150A (en) * | 2015-02-17 | 2015-06-10 | 南通职业大学 | Flexible epoxy resin and preparation method thereof |
| CN109749054A (en) * | 2018-12-13 | 2019-05-14 | 珠海宏昌电子材料有限公司 | A kind of extinction powder coating epoxy resin and its preparation method and application |
-
2019
- 2019-08-20 CN CN201910770042.6A patent/CN110437711B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050288450A1 (en) * | 2003-05-23 | 2005-12-29 | Tim Fletcher | Coating matting agent comprising amide condensation product |
| CN104693150A (en) * | 2015-02-17 | 2015-06-10 | 南通职业大学 | Flexible epoxy resin and preparation method thereof |
| CN109749054A (en) * | 2018-12-13 | 2019-05-14 | 珠海宏昌电子材料有限公司 | A kind of extinction powder coating epoxy resin and its preparation method and application |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110835403A (en) * | 2019-11-18 | 2020-02-25 | 黄山学院 | Epoxy resin for low-temperature curable flame-retardant powder coating and preparation method thereof |
| CN110835403B (en) * | 2019-11-18 | 2022-07-22 | 黄山学院 | Epoxy resin for low-temperature-curable flame-retardant powder coating and preparation method thereof |
| CN112048057A (en) * | 2020-09-11 | 2020-12-08 | 安徽鑫友高分子新材料科技有限公司 | Epoxy resin, application and high-leveling ultralow-temperature curing type pure powder coating |
| CN112321799A (en) * | 2020-11-04 | 2021-02-05 | 黄山新佳精细材料有限公司 | Epoxy resin for high-hardness and low-temperature curing type powder coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110437711B (en) | 2021-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105925130B (en) | A kind of hyperbranched polyether type epoxy resin/epoxy resin composite anticorrosion coating and preparation method thereof | |
| CN110437711A (en) | A kind of low temperature curing type B68 extinction powder epoxy resin and the preparation method and application thereof | |
| CN105925145A (en) | High-performance anti-corrosion epoxy powder coating | |
| CN100396748C (en) | Epoxy resin type high strength structure adhesive | |
| CN102250321A (en) | Quick-drying room temperature curing waterborne epoxy resin curing agent and preparation method thereof | |
| CN110343443A (en) | A kind of graphene coating and preparation method thereof | |
| CN110423539A (en) | A kind of high indoor epoxy resin used for powder coating of levelling 50:50 and preparation method thereof | |
| CN103113809B (en) | High-bonding strength base paint for wet concrete interface and preparation method thereof | |
| JP4906049B2 (en) | Epoxy resin powder coating composition | |
| CN109294402A (en) | A kind of wet structure solidifies solvent-free anticorrosive paint and preparation process | |
| JPH02227470A (en) | Epoxy resin powder coating composition | |
| CN109134825A (en) | Modified epoxy and its preparation and application | |
| CN109181480A (en) | A kind of epoxy zinc-enriched paint comprising modifying titanium dioxide and preparation method and purposes | |
| CN110358403B (en) | Anticorrosive paint based on cyclic carbonate active solvent and preparation method and application thereof | |
| CN105754451A (en) | Konjac fly powder based epoxy resin, preparation method thereof and coating prepared from konjac fly powder based epoxy resin | |
| CN110194924A (en) | A kind of anti-corrosive powder paint and preparation method thereof | |
| CN110078894A (en) | A kind of naphthalenediol type hyperbranched epoxy resin and its preparation method and application | |
| CN109181483A (en) | A kind of epoxy powder coating dulling and curing agent and the preparation method and application thereof | |
| CN109370389A (en) | Band wet bands rust type large arch dam wet-heat resisting salt spray resistance anticorrosive coating and preparation process | |
| CN108929618A (en) | A kind of coating and its preparation method suitable for decorating coating | |
| CN107936477B (en) | Graphene/epoxy resin composite high polymer material | |
| CN107974043B (en) | Preparation method of graphene/epoxy resin composite high polymer material | |
| CN107955134B (en) | Application of graphene in epoxy resin composite material | |
| CN116023837B (en) | Anti-scaling coating for civil heating heat exchanger and preparation method thereof | |
| CN114957709A (en) | Water-based epoxy emulsion and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |