CN105968050A - Extinction curing agent for epoxy powder coating and preparation thereof - Google Patents
Extinction curing agent for epoxy powder coating and preparation thereof Download PDFInfo
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- CN105968050A CN105968050A CN201610272349.XA CN201610272349A CN105968050A CN 105968050 A CN105968050 A CN 105968050A CN 201610272349 A CN201610272349 A CN 201610272349A CN 105968050 A CN105968050 A CN 105968050A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/06—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses an extinction curing agent for an epoxy powder coating and preparation thereof; the extinction curing agent is excellent in curing effect and has popularization value. The extinction curing agent is a salt of polycarboxylic acid represented by the formula 1 and imidazoline represented by the formula 2, wherein R1 represents C2-C10 straight or branched chain alkyl, C2-C10 branched or straight chain halogen mono-substituted or mulit-substituted alkyl, C2-C10 branched or straight chain aryl substituted alkyl, or O or S hetero atom-containing C2-C10 branched or straight chain alkyl, and R2 represents aryl, preferably phenyl, and C1-C10 branched or straight chain aryl substituted alkyl; the compound represented by the formula 2 is preferably 2-phenylimidazoline.
Description
Technical field
The present invention relates to salt formed by polybasic carboxylic acid and imidazoline amine compound, its answering in epoxide powder coating
With, and manufacture method.
Background technology
It is known that epoxy resin can be with such as dicyandiamide, polyprotic acid, hydrazides, boron trifluoride compounds, subotituted dicyardiamide
Solidify etc. multiple firming agent, but during for the occasion of some particular/special requirements such as low-luster, dumb light etc., it is necessary to it is special to use
Firming agent or additive method obtain.Industry generally uses following four kinds of means:
(1) powder systems increases inorganic filler or adds polymer powders such as calcium carbonate, Pulvis Talci or politef
Powder etc.；
(2) powder of differential responses activity is dry mixed；
(3) resin is modified；
(4) the special firming agent containing amido and carboxyl specific functional groups is used to realize.
In above-mentioned four kinds of methods, method (1) can affect spraying property, and mechanical performance is also difficult to be guaranteed.Method (2)
The gloss repeatability of floating coat is the best, it is difficult to ensure the film of uniform and stable gloss.In method (3), the modification of resin likely increases
Add cost or make the mobile performance of resin impacted.Method (4) is a kind of conventional, method of effectively reducing gloss.
Deutsche Bundespatent Offenlegungss Chrift 2324696 describes and is made solidification by polyprotic acid and organic amine
The method of agent.It is a kind of mono-salt or salty generated with cyclic amidines by Pyromellitic Acid or trimellitic acid.Use this firming agent
The features such as the resin of solidification has good fluidity, and gloss is stable, are therefore widely applied.But the shortcoming of such firming agent is also
It will be evident that as in baking process easy xanthochromia, bad mechanical property, therefore with such firming agent prepare white or light-colored powder painting
Material is restricted.Additionally, this firming agent is in hybrid system, gloss is more sensitive to the dependence of polyester.
Summary of the invention
The invention provides a kind of dulling and curing agent for powdery paints and preparation method thereof, it is a kind of containing polynary
Acid and the Novel curing agent of organic amine structure, solve easy xanthochromia in baking process, bad mechanical property, gloss the quickest to polyester
The problems such as sense.
The invention provides a kind of dulling and curing agent for epoxide powder coating, it is polybasic carboxylic acid and the formula 2 of formula 1
The salt of imidazoline；
Formula 1:
Wherein,
R1 represents the straight or branched alkyl of C2-C10；The side chain of C2-C10 or straight chain halogen is monosubstituted or polysubstituted alkane
Base；The side chain of C2-C10 or straight chain aryl substituted alkyl；Or the branched-chain or straight-chain alkyl containing the heteroatomic C2-C10 of O or S；
Formula 2:
Wherein:
R2 represents aryl, preferably phenyl；The side chain of C1-C10 or straight chain aryl substituted alkyl；
The compound of formula 2 is preferably 2-benzylimidazoline.
In one embodiment, the compound of formula 1 is the trimellitic anhydride of formula 3 with the diol compound of formula 4 through esterification
With hydrolysis preparation；
Formula 3:
Formula 4:
Wherein,
R3 represents the straight or branched alkyl of C2-C10；The side chain of C2-C10 or straight chain halogen is monosubstituted or polysubstituted alkane
Base；Or the branched-chain or straight-chain alkyl containing the heteroatomic C2-C10 of O, S；
Described diol compound is preferably ethylene glycol.
In one embodiment, the polybasic carboxylic acid of formula 1 is 1: 1-2 with the mol ratio of the imidazoline of formula 2.
Provide the manufacture method of dulling and curing agent in one embodiment, the polybasic carboxylic acid of its Chinese style 1 and the miaow of formula 2
Oxazoline becomes salt in aqueous according to mol ratio 1: 1-2, is then passed through filter, is dried preparation.
In one embodiment, solvent is water or other polar organic solvent.
Provide the dulling and curing agent purposes for epoxide powder coating of the present invention in one embodiment.
The present invention has following compared with the firming agent that Deutsche Bundespatent Offenlegungss Chrift 2324696 describes
Advantage:
(1) good extinction effect, stable mechanical performance；
(2) good heat-resisting quantity, easily preparation white or light-coloured coating；
(3) in mixed type extinction coefficient, gloss is less to the sensitivity of polyester, and extinction effect is stable.
The object of the present invention is achieved like this: dulling and curing agent is by the trimellitic acid contracting diol ester polyprotic acid of formula 1 and formula 2
Imidazoline amido thing formed by salt.
The polyprotic acid of the present invention has a structure that
Formula 1:
Wherein,
R1 represents the straight or branched alkyl of C2-C10；The side chain of C2-C10 or straight chain halogen is monosubstituted or polysubstituted alkane
Base；The side chain of C2-C10 or straight chain aryl substituted alkyl；Or the branched-chain or straight-chain alkyl containing the heteroatomic C2-C10 of O, S；
Formula 1 compound is preferably trimellitic acid condensed ethandiol ester, trimellitic acid contracting propylene glycol ester, trimellitic acid contracting butanediol
Ester.
Imidazoline used in the present invention such as following formula:
Formula 2:
Wherein:
R2 represents aromatic radical, preferably phenyl；The side chain of C1-C10 or straight chain aryl substituted alkyl；
Formula 2 compound is preferably 2-benzylimidazoline, 2-methylimidazole quinoline, 2-ethyl imidazol(e) quinoline.
In one embodiment, dulling and curing agent is the salt that the polyprotic acid of formula 1 generates with the imidazoline amido thing of formula 2,
Solidification temperature is between 160-240 DEG C, and polybasic carboxylic acid is trimellitic acid contracting diol ester；
In one embodiment, the imidazoline amido thing of dulling and curing agent has a following structure:
Wherein:
R2 represents aromatic radical, preferably phenyl；The side chain of C1-C10 or straight chain aryl substituted alkyl；
Representation compound is 2-benzylimidazoline.
In one embodiment, formula 1 compound is prepared by the following method: by 2.0-2.5mol trimellitic anhydride with
1.0-1.3mol diol compound mixes, nitrogen purge.Under nitrogen sustainable protection, it is warming up to 220-240 DEG C, during this period of time can
Constantly there is water to distillate, after distillating close to the water (2mol) of theoretical amount, be warming up to 260 DEG C under vacuum 10-15mmHg and keep 2 hours,
Cooling, with 4 times of quality acetone refinings, obtains intermediate, off-white powder, yield 85%.Obtain intermediate 5% sodium hydroxide water
Solution hydrolyzes, acidifying, filters, and is dried to obtain final products, yield 95%.
In one embodiment, dulling and curing agent is by the imidazoline amido thing 1-2mol of the polyprotic acid 1mol of formula 1 Yu formula 2
The salt generated, concrete grammar is: by the imidazoline amido thing 1-2mol of formula 1 polyprotic acid 1mol and formula 2 in polar solvent or water
Heating, carries out reaction and obtains, and described polar solvent includes methanol, ethanol, DMF and water.Response time regards solvent and determines, under backflow
Generally 2-4 hour, as in room temperature reaction, ten a few to tens of hours of possibility.The solvent that reaction is used must be polarity
, so can add fast response.This solvent also needs to possess following characteristics: first it can promote reaction to complete, the most after the cooling period
Reactant must be made to be precipitated out.According to the present invention, determine that solvent is methanol, ethanol, DMF and water.These solution react,
Reacting at a reflux temperature and completed at about 2 hours, product precipitation degree is relatively big at room temperature, and mother solution can be applied mechanically, circulation
Use, decrease the discharge of waste water and waste liquid.
The salt generated can be with 1, and 2-epoxide curing generation photoextinction, this epoxide is by 2,2-bis-(4-hydroxyl
Phenyl) addition compound product of propane and epichlorohydrin reaction, its softening point at least ＞ 40 DEG C.Must be at room temperature solid, 1,
2-diepoxide can be saturated, it is also possible to is undersaturated, and they can be aliphatic, alicyclic, aromatic series or miscellaneous
Cycle compound, it is also possible to containing other substituent groups such as hydroxyl, aryl, ether, but pair must not occur
Reaction.Bromine group also will not cause side reaction, therefore can include wherein.In solid epoxy molecule, it is necessary to containing big
In the epoxide group of, epoxide equivalent is between 700-1400, and softening point is at 85-110 DEG C.It is used as solid epoxy
Mixture, in order to obtain uniformity film must levelling agent be added to improve apparent condition, they can be one
Plant or the polymer of multiple acrylate.Such as methyl methacrylate, ethyl acrylate, butyl acrylate, Isobutyl 2-propenoate
Copolymerization or homopolymer, it is also possible to be silane-modified acrylate polymer.The consumption of levelling agent is generally powder total amount
0.5-1.5%, generally 1%.The component of powder can also add other components, such as pigment and filler, available color stuffing
Having titanium dioxide, barium sulfate, calcium carbonate, Pulvis Talci, lithopone etc., filler is preferably used ultra-fine or particle type, so contributes to
Improve mobility.During the salt cured epoxy resin of the present invention, when consumption is the 9-12% of amount of resin, firming agent in hybrid system
Consumption should deduct the amount needed for the epoxy resin consumed by polyester.
The method of the present invention is: during preparing powder, first by relevant resin, firming agent, levelling agent, filling material
Carry out sufficient physical mixed, then homogenized by extruder extrusion.Outlet of extruder temperature should control between 90-115 DEG C, squeezes
Going out that the material after cooling is broken to sieve, the powder after sieving can be uniformly applied on metal surface by electrostatic spraying, then
Baking-curing at a proper temperature, general baking temperature between 160-240 DEG C, 10-30 minute time.This firming agent
Under same baking condition, baking more resistance to than the salt prepared by PMDA and 2-benzylimidazoline is good.
Detailed description of the invention
Further illustrate below by embodiment
Embodiment 1 (synthesis of trimellitic acid glycol ester)
Trimellitic anhydride (1.0mol) 192 grams is mixed with ethylene glycol (0.55mol) 34 grams, nitrogen purge.Hold at nitrogen
Continuation of insurance is protected down and is warming up to 230-240 DEG C, can constantly have water to distillate during this period of time, after distillating close to the water (18 grams) of theoretical amount, very
It is warming up to 260 DEG C under empty 10-15mmHg keep 2 hours, cooling, with 900-1200 gram of acetone refining, obtains intermediate trimellitic acid
Acid anhydride glycol ester, off-white powder 176 grams, yield 86%.Obtain intermediate to hydrolyze with 5% sodium hydrate aqueous solution, dilute hydrochloric acid
It is acidified to PH=1-3, filters, be dried to obtain final products trimellitic acid glycol ester, white powder 211.8 grams, yield 95%.
Embodiment 2 (firming agent of the present invention)
The trimellitic acid glycol ester (1mol) 446 grams embodiment 1 obtained is dissolved in 1800 milliliters of dehydrated alcohol, heating
To backflow, the most molten, it is slowly added to 2-benzylimidazoline (1mol) 146 grams, insulation reaction 3 hours, is concentrated into original volume one
Half, it is cooled to room temperature, the salt Precipitation of generation, filter, mother solution can be applied mechanically.Filter cake 80 DEG C vacuum drying, obtains white powder 580
Gram, yield 98%.
Comparative example 3 (Germany Degussa dulling and curing agent B68)
Embodiment 2 and comparative example 3 are done application test, and proportioning see table with result:
Note: E-12 epoxy resin is that Fenghua Nanhai Pharmaceutical Chemistry Group Corp., Ltd. produces, and epoxide number is 0.11-0.125；
Titanium dioxide is the R902 of Do Pont company
402 polyacrylate flow agents produced for Fenghua Nanhai Pharmaceutical Chemistry Group Corp., Ltd.；
Polyester resin be Anhui Hua Jia company produce acid value be 35mgKaOH/g carboxyl polyester；
Gloss measures GB1743-79；
Impact strength experiment GB1732-79；
Flexible strength GB6742-86
To sum up embodiment explanation, embodiment 2 yellowing is slight, and yellowing performance is better than comparative example 3, and therefore the present invention has replacement
The level of import like product, has promotion and application to be worth.
Claims (6)
1., for a dulling and curing agent for epoxide powder coating, it is the polybasic carboxylic acid salt with the imidazoline of formula 2 of formula 1；
Formula 1:
Wherein,
R1 represents the straight or branched alkyl of C2-C10；The side chain of C2-C10 or straight chain halogen is monosubstituted or polysubstituted alkyl；C2-
The side chain of C10 or straight chain aryl substituted alkyl；Or the branched-chain or straight-chain alkyl containing the heteroatomic C2-C10 of O or S；
Formula 2:
Wherein:
R2 represents aryl, preferably phenyl；The side chain of C1-C10 or straight chain aryl substituted alkyl；
The compound of formula 2 is preferably 2-benzylimidazoline.
2. the dulling and curing agent in claim 1, the compound of its Chinese style 1 is the trimellitic anhydride glycol chemical combination with formula 4 of formula 3
Thing is through esterification and hydrolysis preparation；
Formula 3:
Formula 4:
Wherein,
R3 represents the straight or branched alkyl of C2-C10；The side chain of C2-C10 or straight chain halogen is monosubstituted or polysubstituted alkyl；Or
Person contains the branched-chain or straight-chain alkyl of the heteroatomic C2-C10 of O, S；
Described diol compound is preferably ethylene glycol.
3. the dulling and curing agent in claim 1, the polybasic carboxylic acid of its Chinese style 1 is 1: 1-2 with the mol ratio of the imidazoline of formula 2.
4. the manufacture method of the dulling and curing agent in claim 1, the imidazoline of the polybasic carboxylic acid of its Chinese style 1 and formula 2 is according to rubbing
You become salt in aqueous than 1: 1-2, are then passed through filter, are dried preparation.
5. the dulling and curing agent in claim 1, wherein solvent is water or other polar organic solvent.
6. the dulling and curing agent in claim 1 is for the purposes of epoxide powder coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610272349.XA CN105968050A (en) | 2016-04-29 | 2016-04-29 | Extinction curing agent for epoxy powder coating and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610272349.XA CN105968050A (en) | 2016-04-29 | 2016-04-29 | Extinction curing agent for epoxy powder coating and preparation thereof |
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| CN105968050A true CN105968050A (en) | 2016-09-28 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109181483A (en) * | 2018-09-05 | 2019-01-11 | 安徽泰达新材料股份有限公司 | A kind of epoxy powder coating dulling and curing agent and the preparation method and application thereof |
| CN109824500A (en) * | 2018-08-09 | 2019-05-31 | 阜阳市诗雅涤新材料科技有限公司 | A kind of preparation method and application of 2- benzylimidazoline and Pyromellitic Acid anhydride adduct |
| CN110229553A (en) * | 2019-06-13 | 2019-09-13 | 安庆精益精化工有限公司 | The dulling and curing agent for epoxy powder paint prepared based on cyclobutane tetracid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1247714C (en) * | 1999-12-29 | 2006-03-29 | 奉化南海药化集团有限公司 | Dulling and curing agent for epoxy powder paint and its producing method |
-
2016
- 2016-04-29 CN CN201610272349.XA patent/CN105968050A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1247714C (en) * | 1999-12-29 | 2006-03-29 | 奉化南海药化集团有限公司 | Dulling and curing agent for epoxy powder paint and its producing method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109824500A (en) * | 2018-08-09 | 2019-05-31 | 阜阳市诗雅涤新材料科技有限公司 | A kind of preparation method and application of 2- benzylimidazoline and Pyromellitic Acid anhydride adduct |
| CN109181483A (en) * | 2018-09-05 | 2019-01-11 | 安徽泰达新材料股份有限公司 | A kind of epoxy powder coating dulling and curing agent and the preparation method and application thereof |
| CN110229553A (en) * | 2019-06-13 | 2019-09-13 | 安庆精益精化工有限公司 | The dulling and curing agent for epoxy powder paint prepared based on cyclobutane tetracid |
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Application publication date: 20160928 |