CN104693440A - Preparation method of doped poly(2,3-dimethylaniline) and use of doped poly(2,3-dimethylaniline) in anticorrosion paint - Google Patents
Preparation method of doped poly(2,3-dimethylaniline) and use of doped poly(2,3-dimethylaniline) in anticorrosion paint Download PDFInfo
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- CN104693440A CN104693440A CN201310654268.2A CN201310654268A CN104693440A CN 104693440 A CN104693440 A CN 104693440A CN 201310654268 A CN201310654268 A CN 201310654268A CN 104693440 A CN104693440 A CN 104693440A
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Abstract
The invention provides a preparation method of a polyaniline derivative of which the phenyl ring contains an electron donating substituent, relates to a preparation method of an electron donating group-substituted doped poly(2,3-dimethylaniline) and provides a preparation method of a protonic acid-doped poly(2,3-dimethylaniline) and a use of the protonic acid-doped poly(2,3-dimethylaniline) in anticorrosion paint. The poly(2,3-dimethylaniline) is synthesized by a solution in-situ polymerization method, and the method comprises the following steps of adding distilled water, protonic acid and 2,3-dimethylaniline into a container, dissolving ammonium persulfate or sodium persulfate as an oxidizing agent in distilled water, slowly and dropwisely adding the solution into a reaction system, and after the reaction, carrying out pumping filtration, washing, drying and grinding to obtain doped poly(2,3-dimethylaniline) powder. The doped poly(2,3-dimethylaniline) improves polyaniline dissolvability and dispersibility and has anti-corrosive properties better that that of intrinsic polyaniline.
Description
Technical field
The present invention relates to preparation phenyl ring gathering 23 dimethyl aniline containing the polyaniline derivative of electron donating group, particularly relate to the preparation that doping state gathers 23 dimethyl aniline, and as the application of anticorrosive additive in protective system.
Background technology
In the past in decades, conductive polymers application in the electronics industry causes showing great attention to of people, such as: anti electromagnetic wave interference shielding, electrostatic protection etc.Electrically conductive polyaniline is as a kind of novel functional high molecule material, due to it, to have electroconductibility better, the features such as raw material is cheap and easy to get, synthesis technique is easy, good stability, have a wide range of applications in the fields such as secondary cell, electric driven color-changing part, photorectifier and protection against corrosion.
At corrosion-resistant field, polyaniline (PANI) carrys out supercoat mainly as sustained release dosage.Owing to there is C=N functional group in PANI molecule, therefore can be easier to be adsorbed to metallic surface, thus play corrosion inhibition.1984, DeBerry electrochemically prepared PANI, and its result of study shows, in medium of oxides, PANI, by anodic protection, can protect soft steel effectively.Although PANI improves the Corrosion Protection of material, the feature of its molten (melting) poor in processability, significantly limit its application in material antiseptic.In order to improve the workability of PANI, current adoptable method has: finishing, introduce functional protonic acid and carry out adulterating, carry out compound with soluble high-molecular and prepare lactam microballoon etc.In recent years, investigator, by introducing electron donating group on phenyl ring, to reducing intermolecular interaction force, does not improve the solvability of PANI.Wang Qingwu etc. with aniline and ORTHO ANISIDINE for monomer, PANI, Polyanisidine and aniline are synthesized, find that above three kinds of polymkeric substance all show excellent erosion resistance to tinplate, aniline then comparatively significantly improve polyaniline solvability (research [J] of aniline/epoxy altogether tear system protection against corrosion behavior. electrochemistry, 2004,10:222-228).In addition, cyclosubstituted polyaniline derivative also has potential application in other field, as Chinese patent CN1667020 provides the synthetic method of poly-2, the 5-dimethoxyaniline of a kind of electron donor substituted polyaniline derivatives, to being applied on modified electrode; External Anjali etc. have prepared doped polyaniline and derivative thereof, have studied their sensing effects to fatty alcohol.
But, adopt protonic acid to adulterate the still rarely seen report of method of synthesizing blender state P2,3-DMA, and, also have no report about doping state p2,3-DMA in the research in metal corrosion and protection field.
Summary of the invention
The object of this invention is to provide a kind of each method of system of polyaniline derivative, state of especially adulterating gathers each method of system of 23 dimethyl aniline, and it is more excellent than polyaniline in solvability and preservative property.
Monomer 23 dimethyl aniline for the preparation of poly-23 dimethyl aniline is the derivative of aniline, has following molecular formula:
According to the first embodiment of the present invention, each method of the system providing protonic acid doping state to gather 2.3 xylidines, the method comprises:
1) distilled water, protonic acid and 23 dimethyl aniline are added reactor, stir and make it mix, wherein the mol ratio of protonic acid and 23 dimethyl aniline is 1 ~ 5.5:1;
2), after oxygenant being dissolved in distilled water, be slowly added drop-wise in reactor;
3) reaction 1 ~ 30 hour at the temperature of 10 ~ 100 DEG C, preferably 20 ~ 80 DEG C, more preferably 30 ~ 70 DEG C, preferably 3 ~ 20 hours, more preferably 5 ~ 17 hours, preferably 7 ~ 14 hours further;
4) filter and wash, obtaining protonic acid doping state and gather 23 dimethyl aniline filter cake.Preferably: carry out suction filtration, and be washed with distilled water to filtrate colourless till.
In more preferably situation, the method is further comprising the steps of:
5) gained filter cake carry out drying (such as 2 ~ 18 hours, 12 hours, preferred ore deposit; Drying temperature is preferably 40 ~ 80 DEG C, more preferably 50 ~ 70 DEG C, such as 60 DEG C), and then grind, obtain the poly-2.3 xylidine powder of protonic acid doping.This drying can be carried out in baking oven or other drying plant.
Preferably, in step, the mol ratio of distilled water and 23 dimethyl aniline is 20 ~ 200:1, preferably 30 ~ 150:1, and preferably 50 ~ 100:10 is preferred further, in step.In, the mol ratio of protonic acid and 23 dimethyl aniline is 1 ~ 4.5:1, preferably 1 ~ 3.5:1, more preferably 1 ~ 2.5:10
In step, protonic acid be organic acid (such as C1-C50 organic acid, C2-C50 organic dibasic acid, C3-C50 organic ternary acid) or mineral acid (such as hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid) in one or two or more.Preferably, organic acid is selected from organic carboxyl acid, organic radical sulfonic acid, organic radical phosphoric acid, or organic radical-sulfinic acid.Organic acid generally has the short base of C1 (or C2 or C3 or C4) to C50, preferably there is the short base of C1 (or C2 or C3 or C4) to C40, more preferably there is the short base of C1 (or C2 or C3 or C4) to C30, preferably there is the short base of C1 (or C2 or C3 or C4) to C20 further.As protonic acid, such as organic carboxyl acid is the organic mono carboxylic acid of the short base with C1 (or C2 or C3 or C4) to C50 (or C40 or C30 or C20) or Dicarboxylic Acids or organic ternary carboxylic acid, i.e. C1 to C50 (or C40 or C30 or C20) machine monocarboxylic acid or C2 (or C3 or C4) to C50 (or C40 or C30 or C20) Dicarboxylic Acids or C3 (or C4) to C50 (or C40 or C30 or C20) organic ternary carboxylic acid, organic radical sulfonic acid is the organic mono sulfonic acid of the short base with C1 (or C2 or C3 or C4) to C50 (or C40 or C30 or C20) or organic dibasic sulfoacid or organic ternary sulfonic acid, i.e. C1 to C50 (or C40 or C30 or C20) organic mono sulfonic acid or C2 (or C3) to C50 (or C40 or C30 or C20) organic dibasic sulfoacid or C3 (or C4) to C50 (or C40 or C30 or C20) organic ternary sulfonic acid: organic phosphoric acid is the organic mono phosphoric acid of the short base with C1 (or C2 or C3 or C4) to C50 (or C40 or C30 or C20) or organic binary phosphoric acid or organic ternary phosphoric acid, i.e. C1 to C50 (or C40 or C30 or C20) organic mono phosphoric acid or C2 (or C3) to C50 (or C40 or C30 or C20) organic binary phosphoric acid or C3 (or C4) to C50 (or C40 or C30 or C20) organic ternary phosphoric acid, organic radical-sulfinic acid is the organic mono-sulfinic acid of the short base with C1 (or C2 or C3 or C4) to C50 (or C40 or C3 or C20) or organic binary-sulfinic acid or organic ternary-sulfinic acid, i.e. C1 to C50 (or C40 or C30 or C20) organic mono-sulfinic acid or C2 (or C3) to C50 (or C40 or C30 or C20) organic binary-sulfinic acid or C3 (or C4) to C50 (or C40 or C30 or C20) organic ternary-sulfinic acid.
Preferably, in step 2) in, the mol ratio of oxygenant and 23 dimethyl aniline is 5:1;
Generally, in step 2) in, the mol ratio of oxygenant and distilled water is 1:5 ~ 10, preferred 1:6 ~ 9, more preferably 1:6.5 ~ 8.
Preferably, in step 2) in, oxygenant is that persulfuric acid connects or Sodium Persulfate.
According to the second embodiment of the present invention, the protonic acid doping state prepared by aforesaid method is provided to gather 23 dimethyl aniline.
According to the third embodiment the present invention, provide and gather 23 dimethyl aniline as the application of anticorrosive additive in anticorrosive paint composition by the made each protonic acid doping state of aforesaid method.Base coating composition is selected from conventional epoxy-resin coating composite, polyurethane coating composition, resol coating compositions, Synolac coating compositions, polyacrylic ester coating compositions, lacquer composition and oil-based paint composition.It is 1000-100000 scope that protonic acid doping state gathers the molecular-weight average (weight average) that 23 dimethyl aniline has, preferably in 5000-50000 scope.
The solubleness of the doping state P2.3-DMA that the present invention obtains in organic solvent (such as dehydrated alcohol or ethyl acetate) than the solubleness height 2-10 of eigenstate PANI in same organic solvent (such as dehydrated alcohol or ethyl acetate) doubly, doubly, more preferably high 4-8 doubly for preferred high 3-9.
The doping state that the present invention obtains, 3-DMA solubleness is in organic solvent equal to or higher than 2mg/ml, preferably be equal to or higher than 2.5mg/ml, more preferably 2.8mg/ml is equal to or higher than, be equal to or higher than 3mg/ml further, most preferably be equal to or higher than 3.5mg/ml such as, the solubleness in dehydrated alcohol is higher than 6mg/ml, and the solubleness in ethyl acetate is higher than 3mg/ml.
Protonic acid doping state of the present invention, 3-DMA joins in base coating composition, thus obtains composite coating.This composite coating (i.e. anticorrosive paint composition) is especially used as anti-corrosive metal coating, is namely coated in and needs on rot-resistant metallic surface.Wherein base coating composition is selected from epoxy-resin coating composite, polyurethane coating composition, resol coating compositions, Synolac coating compositions, polyacrylic ester coating compositions, lacquer composition and oil-based paint composition.
Adopt and prepare protonic acid doping state with the present invention, the method that the method for 3-DMA is similar prepare eigenstate PANI or
Adopt the eigenstate PANI of prior art, join in base coating composition, preparation contrast composite coating.
Base epoxy resin coating composition described here is the coating composition be purchased, such as, and Yongfu, Tianjin board epoxy resin varnish.Base polyurethane coating composition is Zhejiang heavenly maiden's board polyurethane paint.
Embodiment
Embodiment 1:
Under water-bath 10 DEG C of conditions, in three-necked flask, add 50ml distilled water, 8.2*10
-3mol sulfuric acid and 1.6*10
-2mol2,3-xylidine, stirs and makes it mix; Being connect by 7.5g persulfuric acid is dissolved in 25ml distilled water, slowly in instillation reaction system, stirs lower reaction 9 hours; After reaction terminates, suction filtration, colourless to filtrate with distilled water wash filter cake; Filter cake after dry 6 hours, takes out grinding in 60 DEG C of baking ovens, obtains the P2 of sulfuric acid doping, 3-DMA powder.The measuring method of molecular weight adopts high performance liquid chromatography.Molecular-weight average (weight-average molecular weight) is 35428.
Embodiment 2:
Under water-bath 40 DEG C of conditions, in three-necked flask, add 50ml distilled water, 2.5*10
-3mol Witco 1298 Soft Acid and 1.6*10
-2m0l 23 dimethyl aniline, stirs and makes it mix; Being connect by 7.5g persulfuric acid is dissolved in 25ml distilled water,
In slow instillation reaction system, stir lower reaction 9 hours; Reaction terminate after, suction filtration, with distilled water wash filter cake to filtrate without
Look; Filter cake after dry 8 hours, takes out grinding in 60 DEG C of baking ovens, obtains the P2 of Witco 1298 Soft Acid doping, 3-DMA powder.
Embodiment 3:
Under water-bath 70 DEG C of conditions, in three-necked flask, add 50ml distilled water, 4*10
-2mol camphorsulfonic acid and 1.6*10
-2mol 23 dimethyl aniline, stirs and makes it mix; Skim over sulfuric acid to connect be dissolved in 25ml distilled water by 1, slowly in instillation reaction system, stir lower reaction 12 hours; After reaction terminates, suction filtration, colourless to filtrate with distilled water wash filter cake; Filter cake after dry 10 hours, takes out grinding in 60 DEG C of baking ovens, obtains the P2 of camphorsulfonic acid doping, 3-DMA powder.
Claims (10)
1. protonic acid doping state gathers each method of system of 23 dimethyl aniline, and the method comprises:
1) distilled water, protonic acid and 23 dimethyl aniline are added reactor, stir and make it mix, wherein the mol ratio of protonic acid and 23 dimethyl aniline is 1 ~ 5.5:1;
2), after oxygenant being dissolved in distilled water, be slowly added drop-wise in reactor;
3) react 1 ~ 30 hour at the temperature of 10 ~ 100 DEG C;
4) filter and wash; Obtain protonic acid doping state and gather 23 dimethyl aniline filter cake.
2. method according to claim 1, further comprising the steps of:
5) gained filter cake carries out drying and then grinds, and obtains the poly-23 dimethyl aniline powder of protonic acid doping, preferably: carry out suction filtration, and it is colourless to be washed till filtrate with distilled water.
3. state of adulterating preparing according to claims 1 gathers the method for 23 dimethyl aniline, it is characterized in that: step 1) in, the mol ratio of distilled water and 23 dimethyl aniline is 20 ~ 200:1, preferably 30 ~ 150:1, more preferably 50 ~ 100:10.
4. state of adulterating preparing according to claims 1 gathers the method for 2.3 xylidines, it is characterized in that: step 1) in, the mol ratio of protonic acid and 23 dimethyl aniline is 1 ~ 4.5:1, preferably 1 ~ 3.5:1, more preferably 1 ~ 2.5:10.
5. state of adulterating preparing according to claims 1 or 4 gathers the method for 23 dimethyl aniline, it is characterized in that: step 2) in, the mol ratio of oxygenant and 23 dimethyl aniline is 1 ~ 5:1, preferably 1 ~ 4:1, more preferably 1 ~ 3:10.
6. state of adulterating preparing according to claims 1 or 4 gathers the method for 23 dimethyl aniline, it is characterized in that: step 2) in, the mol ratio of oxygenant and distilled water is 1:5 ~ 10.
7. state of adulterating preparing according to claims 1 gathers the method for 23 dimethyl aniline, it is characterized in that: step 2) in, oxygenant is ammonium persulphate or Sodium Persulfate.
8. the protonic acid doping state prepared by any one method in claim 1-7 gathers 23 dimethyl aniline.
9. prepared by any one method in claim 1-7 or protonic acid doping state according to claim 8 poly-2,3-xylidine is as the application of anticorrosive additive in anticorrosive paint composition, wherein this doping state poly-2,3-xylidine joins in base coating composition as a kind of anticorrosive additive with the consumption of 0.1 ~ 50wt% of the weight based on base coating composition, obtains anticorrosive paint composition.
10. application according to claim 9, wherein base coating composition is selected from epoxy-resin coating composite, polyurethane coating composition, resol coating compositions, Synolac coating compositions, polyacrylic ester coating compositions, lacquer composition and oil-based paint composition.
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| CN201310654268.2A CN104693440A (en) | 2013-12-05 | 2013-12-05 | Preparation method of doped poly(2,3-dimethylaniline) and use of doped poly(2,3-dimethylaniline) in anticorrosion paint |
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| CN201310654268.2A CN104693440A (en) | 2013-12-05 | 2013-12-05 | Preparation method of doped poly(2,3-dimethylaniline) and use of doped poly(2,3-dimethylaniline) in anticorrosion paint |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105295708A (en) * | 2015-10-28 | 2016-02-03 | 天长市润达金属防锈助剂有限公司 | Anticorrosive rare earth aluminum alloy pulling sol and preparation method thereof |
| CN105400416A (en) * | 2015-10-28 | 2016-03-16 | 天长市润达金属防锈助剂有限公司 | Titanium dioxide-modified aluminum alloy anticorrosion dipping sol and preparation method thereof |
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- 2013-12-05 CN CN201310654268.2A patent/CN104693440A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105295708A (en) * | 2015-10-28 | 2016-02-03 | 天长市润达金属防锈助剂有限公司 | Anticorrosive rare earth aluminum alloy pulling sol and preparation method thereof |
| CN105400416A (en) * | 2015-10-28 | 2016-03-16 | 天长市润达金属防锈助剂有限公司 | Titanium dioxide-modified aluminum alloy anticorrosion dipping sol and preparation method thereof |
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Application publication date: 20150610 |