CN106831629B - A kind of derivative of Pyromellitic Acid and preparation method thereof - Google Patents
A kind of derivative of Pyromellitic Acid and preparation method thereof Download PDFInfo
- Publication number
- CN106831629B CN106831629B CN201710097148.5A CN201710097148A CN106831629B CN 106831629 B CN106831629 B CN 106831629B CN 201710097148 A CN201710097148 A CN 201710097148A CN 106831629 B CN106831629 B CN 106831629B
- Authority
- CN
- China
- Prior art keywords
- pyromellitic acid
- derivative
- preparation
- products
- catalyst
- 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
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole 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, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D263/14—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole 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, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with radicals substituted by oxygen atoms
-
- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of derivative of Pyromellitic Acid, structural formula (I) is as follows:The method for preparing the derivative of Pyromellitic Acid includes the following steps: (1) using pyromellitic acid anhydride and methanol as starting material, carries out complete esterification under the effect of the catalyst and esterification products are made；(2) esterification products are reacted with amino alcohol, ammonia products is made；(3) ammonia products are reacted with thionyl chloride, in NaCO3The derivative (I) of Pyromellitic Acid of the invention is made under effect.The defects of curing agent that the derivative of prepared Pyromellitic Acid can be used as outdoor polyester powder coating uses, and made film coated surface is pin-free, and there is excellent weatherability.
Description
Technical field
It is the present invention relates to a kind of derivative of Pyromellitic Acid and its manufacturing method, in particular to a kind of for outdoor polyester
The derivative and its manufacturing method of the Pyromellitic Acid of type powder paint solidifying agent.
Background technique
Triglycidyl isocyanurate (TGIC) is earliest exploitation for the most important solid of the resin containing carboxyl functional group
Agent, the comprehensive performance that TGIC has other type curing agent incomparable, such as good weatherability, excellent resistance to overbaking
Xanthochromia etc..But since it also has many defects, such as with irritation, cell mutation and environmental contamination etc., people
The use to it is gradually decreased, starts many substitutes occur.
Hydroxyalkyl amide (HAA) is the most important one kind of numerous substitute species, it is the use developed by u s company earliest
For the Novel curing agent of powdery paints, trade names are PrimidXL 552.HAA does not have irritation and cell mutation, because
This is valued by people quickly, and usage amount also increases year by year.Since 552 curing mechanism of PrimidXL is hydroxyl and polyester
Esterification between carboxyl, the water for reacting generation is by-product.Exactly because also esterification has hydrone releasing, made film
Unavoidably there is the defects of pin hole.
Therefore, develop it is functional be similar to HAA, but the defects of film coated surface is not in pin hole again is people's institute's phase
It hopes.
Summary of the invention
In order to solve the above technical problems, structure formula (I) is such as the present invention provides a kind of derivative of Pyromellitic Acid
Under:
In structure formula (I), R1For H, CH3Or C2H5, R2For H, CH3Or C2H5。
The present invention also provides a kind of preparation methods of the derivative of Pyromellitic Acid, the following steps are included:
Prepare complete esterification products:
Using pyromellitic acid anhydride and lower alcohol as starting material, temperature be 50-80 DEG C under conditions of by catalyst into
Row catalysis 2~8h of reaction, after reaction to generation anhydrous in oil water separator, the NaOH solution for being 0.5% by concentration is to product
It is neutralized, isolates organic layer, be washed with water and wash organic layer, obtain being esterified production completely after filtering, drying, decompression filter
Object；Wherein the molar ratio of pyromellitic acid anhydride and lower alcohol is 1:10~12, and catalyst amount is 2~7wt%；
Prepare ammonia products:
The complete esterification products of preparation and amino alcohol are reacted into 12~17h under the conditions of temperature is 150~210 DEG C, then
Suction filtration obtains the solid ammonia products of white after 4 times of amount methanol eddy 1h are added；Wherein amino alcohol and complete esterification products rub
1:3~6 Er Biyue；
Prepare final product Pyromellitic Acid derivative:
The white solid product of the ammonolysis of preparation is dissolved in solvent, by thionyl chloride 0~8 DEG C at a temperature of be added drop-wise to
In ammonia products, after being added dropwise, it is heated to 30-80 DEG C of progress 9~15h of back flow reaction, after the reaction was completed, cools down, is added
10% NaCO3Solution, to there is sediment precipitation, it is Pyromellitic Acid derivative that suction filtration, which obtains product, for stirring；Wherein protochloride
The molar ratio of sulfone and ammonia products is about 1:5~9.
Preferably, the lower alcohol chemical formula is CnH(2n+2)O (II), wherein n is 1,2 or 3.
Preferably, the catalyst can be liquid acid catalyst, non-acid catalyst, solid super-strong acid.
Preferably, the catalyst be non-acid catalyst, the non-acid catalyst include butyl titanate, hydroxide,
Organo metallic oxide.
Preferably, the esterification products include four methyl esters of Pyromellitic Acid, Pyromellitic Acid tetra-ethyl ester and equal benzene tetramethyl
Sour orthocarbonate.
Preferably, amino alcohol described in step (2) can be indicated with structural formula (III), wherein R1For H, CH3Or C2H5,R2
For H, CH3Or C2H5。
Preferably, solvent described in step (3) can be methylene chloride, dichloroethanes or chloroform, preferably dichloroethanes.
Preferably, it is described prepare complete esterification products during, the molar ratio of pyromellitic acid anhydride and lower alcohol is preferred
For 1:10~11, catalyst amount is preferably 3~5wt%；The reaction temperature is preferably 60-70 DEG C, and the reaction time is preferably 3
~5h；
During the white solid product for preparing ammonolysis, the molar ratio of amino alcohol and complete esterification products is 1:4~5, instead
Answering temperature is preferably 170~190 DEG C, and the reaction time is preferably 13~16h；
During preparing final product Pyromellitic Acid derivative, the molar ratio of thionyl chloride and ammonia products is preferably 1:
6~8；Dropping temperature is preferably 2~5 DEG C；Reaction temperature is preferably 40~70 DEG C；Reflux time is preferably 10~13h.
The invention has the following advantages:
The curing agent that the derivative of Pyromellitic Acid prepared by the present invention can be used as outdoor polyester powder coating uses, institute
The defects of film coated surface processed is pin-free, and there is excellent weatherability.
Certainly, it implements any of the products of the present invention and does not necessarily require achieving all the advantages described above at the same time.
Specific embodiment
The technical solution in the present invention is clearly and completely described below in conjunction with the embodiment of the present invention, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
All other embodiment obtained by those of ordinary skill in the art without making creative efforts, belongs to this hair
The range of bright protection.
A preferred embodiment of the invention is first to prepare Pyromellitic Acid methyl esters, then manufacture 1,2 with Pyromellitic Acid methyl esters,
4,5- tetra- (2- oxazoline group) benzene (referred to as TOB).Detailed implementation steps and reaction equation are as follows:
(1) prepare the three neck round bottoms equipped with mechanical stirring device, condensing unit, oil water separator and temperature control equipment to burn
1 mole of pyromellitic acid anhydride and 10 moles of methanol are added into flask, while 7g butyl titanate is added for bottle.It is heated to
Reflux, after reacting 3h, the anhydrous generation of oil water separator separates organic layer with 0.5% NaOH solution neutralized reaction product.It is washed with water
It washs organic layer 3 times, filters, anhydrous magnesium sulfate is dry.Vacuum distillation, finally obtains the complete esterification of pale yellow transparent semifluid shape
Product.Reaction equation is as follows:
(2) 1 mole of complete esterification products is taken, 4.5 moles of ethanol amine is added, temperature is increased to 170 DEG C, reacts 16h, instead
It should stop.4 times of amount methanol are added, after the 1h that flows back, decompression filters and obtains the white solid object of ammonolysis.Reaction equation is as follows:
(3) 1 mole of ammonia products is taken, is dissolved in dichloroethanes, 7 moles of thionyl chloride is added drop-wise to ammonolysis at 3 DEG C and is produced
In object, after thionyl chloride is added dropwise, heating reflux reaction 12h, reaction stops, and temperature drops to 20 DEG C, and 10% bicarbonate is added
Sodium solution stirs 2 hours, there is sediment precipitation, and suction filtration obtains solids, is rinsed with water filter cake, finally obtains white solid production
Object 1,2,4,5- tetra- (2- oxazoline group) benzene (referred to as TOB).Reaction equation is as follows:
(2) powder coating solidification evaluates embodiment
TOB synthesized by the present invention and reference substance HAA is subjected to powdery paints ingredient, then passes through the mixture prepared
High-speed mixer is mixed, and mixed material squeezes out tabletting by double screw extruder, and extruder extrusion temperature is set as 100
DEG C, after tabletting material is crushed by pulverizer, after the sieving of 180 mesh screens, powder coating formulation 1 and 2, tool are made respectively
Body is shown in Table 1.The method that formulation for coating material 1 and 2 is electrostatically sprayed respectively is sprayed on stainless steel respectively, toasts 10 at 200 DEG C
Minute, finally obtaining dried film thickness is 90-95um, carries out the performance test of film to each formula respectively, is specifically shown in Table 1.
The performance test methods and evaluation criterion of film are as follows:
The appearance of film: whether smooth specimen surface is visually observed, if having the defects of tangerine peel and pin hole.
The levelability evaluation criterion of film carries out levelling grading according to the levelling effect rating scale plate of U.S. PCI, and 1 is
Difference, 10 be excellent.
The glossiness of film is tested and evaluation is referring to GB/T 9754-2007.
The impact resistance of film is tested and evaluation is referring to GB/T 1732-1993.
The weatherability of the weatherable films of film is tested using artificial accelerated aging instrument, and test item is QUV-B test,
Test condition be 50 DEG C UV illumination 4 hours, then 40 DEG C of Water, steam circulations are tested 4 hours, are so recycled, and total testing time is
480h.Finally by the gloss of coating before and after measurement experiment, light-protection rate is calculated.
The outdoor polyester powder coating formula of table 1 and the performance test results
1. polyester resin, Anhui Shenjian New Material Co., Ltd.'s production.
2. hydroxyalkyl amide, the production of Anhui Liuan Jietongda Chemical Co., Ltd..
3. polyacrylate levelling agent, German Worlee company production.
4. ultra-fine barium sulfate, Guizhou China adds fine mining industry Co., Ltd to produce.
5. carbon black, Mitsubishi Corporation of Japan production.
It can be seen that from the film performance test result in table 1 and use institute produced compounds TOB of the present invention as curing agent and make
With the mechanical performance and ageing-resistant performance of made film are substantially identical as HAA cured coating film, but institute's produced compounds of the present invention
The cured film of TOB does not have pin hole, and compactness is substantially better than the cured film of HAA.
Present invention disclosed above preferred embodiment is only intended to help to illustrate the present invention.There is no detailed for preferred embodiment
All details are described, are not limited the invention to the specific embodiments described.Obviously, according to the content of this specification,
It can make many modifications and variations.These embodiments are chosen and specifically described to this specification, is in order to better explain the present invention
Principle and practical application, so that skilled artisan be enable to better understand and utilize the present invention.The present invention is only
It is limited by claims and its full scope and equivalent.
Claims (9)
1. a kind of derivative of Pyromellitic Acid, which is characterized in that its structure formula (I) is as follows:
In structure formula (I), R1For CH3Or C2H5, R2For H, CH3Or C2H5。
2. a kind of preparation method of the derivative of Pyromellitic Acid according to claim 1, it is characterised in that, including it is following
Step:
Prepare complete esterification products:
Using pyromellitic acid anhydride and lower alcohol as starting material, urged under conditions of temperature is 50-80 DEG C by catalyst
Change reaction 2-8h, after reaction to generation anhydrous in oil water separator, the NaOH solution for being 0.5% by concentration is in product progress
With, isolate organic layer, be washed with water and wash organic layer, by filtering, drying, decompression filter after obtain complete esterification products；Its
The molar ratio of middle pyromellitic acid anhydride and lower alcohol is 1:10-12, catalyst amount 2-7wt%；
Prepare ammonia products:
The complete esterification products of preparation and amino alcohol are reacted into 12-17h under the conditions of temperature is 150-210 DEG C, are then added 4 times
It is filtered after amount methanol eddy 1h and obtains the solid ammonia products of white；The wherein molar ratio about 1 of amino alcohol and complete esterification products:
3-6；
Prepare final product Pyromellitic Acid derivative:
The white solid product of the ammonolysis of preparation is dissolved in solvent, by thionyl chloride 0-8 DEG C at a temperature of be added drop-wise to ammonolysis
In product, after being added dropwise, it is heated to 30-80 DEG C of progress back flow reaction 9-15h, after the reaction was completed, room temperature is down to, is added 10%
NaCO3Solution, to there is sediment precipitation, it is Pyromellitic Acid derivative that suction filtration, which obtains product, for stirring；Wherein thionyl chloride with
The molar ratio of ammonia products is about 1:5-9.
3. the preparation method of the derivative of Pyromellitic Acid according to claim 2, which is characterized in that the lower alcohol
Chemical formula is CnH(2n+2)O (II), wherein n is 1,2 or 3.
4. the preparation method of the derivative of Pyromellitic Acid according to claim 2, it is characterised in that, the catalyst
For liquid acid catalyst, non-acid catalyst, solid super-strong acid.
5. the preparation method of the derivative of Pyromellitic Acid according to claim 2, the catalyst is non-acid catalysis
Agent, the non-acid catalyst are butyl titanate, hydroxide, organo metallic oxide.
6. the preparation method of the derivative of Pyromellitic Acid according to claim 2, it is characterised in that, the esterification produces
Object is four methyl esters of Pyromellitic Acid, Pyromellitic Acid tetra-ethyl ester and Pyromellitic Acid orthocarbonate.
7. the preparation method of the derivative of Pyromellitic Acid according to claim 2, it is characterised in that, institute in step (2)
The amino alcohol stated indicates with structural formula (III), wherein R1For CH3Or C2H5,R2For H, CH3Or C2H5
。
8. the preparation method of the derivative of Pyromellitic Acid according to claim 2, which is characterized in that institute in step (3)
The solvent stated is dichloroethanes.
9. the preparation method of the derivative of Pyromellitic Acid according to claim 2, which is characterized in that the preparation is complete
During esterification products, the molar ratio of pyromellitic acid anhydride and lower alcohol is 1:10-11, catalyst amount 3-5wt%；Institute
Stating reaction temperature is 60-70 DEG C, reaction time 3-5h；
During preparing ammonia products, the molar ratio of amino alcohol and complete esterification products is 1:4-5, reaction temperature 170-190
DEG C, reaction time 13-16h；
During preparing final product Pyromellitic Acid derivative, the molar ratio of thionyl chloride and ammonia products is 1:6-8；It is added dropwise
Temperature is 2-5 DEG C；Reaction temperature is 40-70 DEG C；Reflux time is 10-13h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710097148.5A CN106831629B (en) | 2017-02-22 | 2017-02-22 | A kind of derivative of Pyromellitic Acid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710097148.5A CN106831629B (en) | 2017-02-22 | 2017-02-22 | A kind of derivative of Pyromellitic Acid and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106831629A CN106831629A (en) | 2017-06-13 |
| CN106831629B true CN106831629B (en) | 2019-10-08 |
Family
ID=59134813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710097148.5A Active CN106831629B (en) | 2017-02-22 | 2017-02-22 | A kind of derivative of Pyromellitic Acid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106831629B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5366572A (en) * | 1993-05-20 | 1994-11-22 | Thiokol Corporation | Oxazoline bonding agents in composite propellants |
| JP2001288437A (en) * | 2000-04-07 | 2001-10-16 | Hitachi Kasei Polymer Co Ltd | Adhesive composition for cover lay film and cover lay film for flexible printed circuit board using its adhesive composition |
| CN104151257A (en) * | 2013-05-13 | 2014-11-19 | 上海药合生化科技有限公司 | 1,3,5-benzenetricarboxylic acid derivative and making method thereof |
-
2017
- 2017-02-22 CN CN201710097148.5A patent/CN106831629B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5366572A (en) * | 1993-05-20 | 1994-11-22 | Thiokol Corporation | Oxazoline bonding agents in composite propellants |
| JP2001288437A (en) * | 2000-04-07 | 2001-10-16 | Hitachi Kasei Polymer Co Ltd | Adhesive composition for cover lay film and cover lay film for flexible printed circuit board using its adhesive composition |
| CN104151257A (en) * | 2013-05-13 | 2014-11-19 | 上海药合生化科技有限公司 | 1,3,5-benzenetricarboxylic acid derivative and making method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis of chiral benzene-based tetraoxazolines and their application in asymmetric Friedel-Crafts alkylation of indole derivatives with nitroalkenes;Wei-Jie Li，等;《Catalysis Communications》;20140705;第52卷;第54页Fig. 1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106831629A (en) | 2017-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102140179B (en) | Method for preparing styrene grafted silicon dioxide superhydrophobic thin film | |
| CN102807807B (en) | Paint used for coiled metal material | |
| CN103333314B (en) | A kind of cationic photo-cured fluorine-containing urethane resin and preparation method thereof | |
| CN105368150B (en) | A kind of water-based weather-proof glass ink | |
| CN103571294B (en) | Pollution-free environmental protection wrinkle varnish and preparation method thereof | |
| CN109852127A (en) | A kind of polyester type powder paint composite curing agent and the preparation method and application thereof | |
| CN102746768A (en) | Water-borne colorful glass paint and preparation method and application thereof | |
| CN106831629B (en) | A kind of derivative of Pyromellitic Acid and preparation method thereof | |
| CN105038533A (en) | Aqueous baking varnish coating specially used for antitheft doors, and preparation method thereof | |
| CN109486297A (en) | A kind of white fluorine carbon finishing paint and its preparation process | |
| CN109054463B (en) | Preparation method of high-dispersibility pigment for PVC (polyvinyl chloride) film structural material | |
| CN101935448A (en) | polyurethane curing agent and two-component polyurethane coating not containing benzene, methylbenzene or dimethylbenzene and TDI | |
| CN103740241A (en) | Automobile plate spring anticorrosive priming paint and preparation method thereof | |
| CN102101956B (en) | Preparation method of low-carbon light reflecting energy-saving coating | |
| CN109957046A (en) | Fluorine-containing fluorenes oxime ester lightlike initiating agent, the Photocurable composition comprising it and its application | |
| CN104945603B (en) | A kind of low cost alkyd resin and its preparation process | |
| CN103555155A (en) | High-performance high-decoration environment-friendly automobile baking finish coat and preparation method thereof | |
| TW201823392A (en) | Coating composition and method of manufacturing the same | |
| CN107365547B (en) | Bright water-based epoxy floor paint and preparation method thereof | |
| JPS6259147B2 (en) | ||
| CN101967326A (en) | Exterior-wall reflectorized soluble paint | |
| CN108641020A (en) | A kind of preparation method of the degradation-resistant polyvinyl butyral of low acid value | |
| CN104151257B (en) | All derivative and manufacture methods thereof of benzene tricarbonic acid | |
| CN107629616B (en) | A kind of elastic building paint | |
| CN110358346A (en) | A kind of environmental-protection flame-retardant additive 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 |