CN104231263B - A kind of multistage continuous polyaniline synthesis technique - Google Patents
A kind of multistage continuous polyaniline synthesis technique Download PDFInfo
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- CN104231263B CN104231263B CN201310242287.4A CN201310242287A CN104231263B CN 104231263 B CN104231263 B CN 104231263B CN 201310242287 A CN201310242287 A CN 201310242287A CN 104231263 B CN104231263 B CN 104231263B
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Abstract
The invention discloses a kind of multistage contact polyaniline synthesis technique, under conditions of 20 ~ 50 DEG C, aniline monomer, oxidant and medium aqueous acid are continuously added in the tubular reactor of plural serial stage, generate polyaniline.This technique can use the raw material of higher concentration under cryogenic, reduce discharging of waste liquid, the polyaniline prepared with this technique has high yield, gained polyaniline relative molecular weight distribution is more concentrated, and the tubular reactor used by synthesized polyaniline is affected without the ratio by heat transfer area with reaction volume.
Description
Technical field
The invention belongs to conducting polymer technical field, relate to a kind of polyaniline continuous synthesis technique.
Background technology
Polyaniline is a kind of new functional macromolecule material, is commonly called as conductive plastics, is a kind of special type function material, has and mould
The density of material, has again the electric conductivity of metal and the machinability of plastics, also has a metal and chemistry that plastics are short of and electricity
Chemical property, is the chemical material winning the Nobel Prize, because of its have uniqueness chemistry, electrochemistry and optical property, the energy,
There is wide prospect in the field such as electromagnetic shielding and electrochromism, and related industry relates to electronic chemical product, shipping industry, oil
Many aspects such as chemical industry, military stealth material, become countries in the world and fall over each other research, the active material of exploitation.
Conducting polymer achieves from insulator to semiconductor, then the change to conductor, is leap amplitude in all substances
A maximum class, is that the most any material is incomparable.Through the research of more than 20 years, people gradually recognized conduction
Polymer has the structure of uniqueness and excellent physical and chemical performance, makes it in the energy, information, opto-electronic device, chemistry and life
The fields such as thing sensor, electromagnetic shielding, stealth technology and metal erosion protection have broad application prospects.2000 10
Month, the Nobel chemistry Prize of 2000 is authorized Japan University of tsukuba Shirakawa professor by Royal Swedish Academy of Sciences, the U.S. adds profit
University Santa Barbara, welfare Asia branch school Heeger professor and Univ Pennsylvania USA MacDiarmid teach, to reward them
Successfully develop conducting polymer composite, fully indicate scientific circles to the great attention of this area research and encouragement.
The synthesis of polyaniline has chemical oxidative polymerization, condensation polymerization method and electrochemical polymerization method, chemical oxidative polymerization
Most having industrial prospect, it is to make aniline monomer oxidation polymerization with oxidant in acid condition, the oxygen that aniline polymerization is conventional
Agent has (NH4)2S2O8, K2Cr2O7, H2O2, FeCl3Deng, gained polyaniline character is essentially identical.At present it is known that polyaniline close
Technique is become to be mainly intermittent reaction.Both at home and abroad manufacturer's synthesized polyaniline mainly be chemical oxidative polymerization, processing
On then use after doping method.Such as United States Patent (USP) 5,436,317 provide a kind of polyaniline synthesis technique, by aniline and oxide by
Gradually joining in watery hydrochloric acid, reaction generates the polyaniline of doping, then goes doping with alkali neutralization, obtains polyaniline in eigenstate product,
Applicable acid doping can be added in polyaniline in eigenstate again and possess certain electric conductivity, by selecting dopant acid again to adjust
The electric conductivity of joint polyaniline.
Owing to the synthesis of polyaniline belongs to exothermic reaction, the temperature being likely to result in local in building-up process is too high so that
Aniline and oxidant react and acutely occur that over oxidation causes polyaniline chain rupture, thus affect dividing of the molecular weight of polyaniline
Cloth, over oxidation also can reduce the yield of polyaniline.
HUANG J, KANER R B.(The intrinsic nanofibrillar morphology of
Polyaniline [J] .Chem Commun, 2006 (4): 367-376.) provide a kind of polyaniline synthesis technique: by aniline list
Body and oxidant mix rapidly, obtain polyaniline nano fiber.But each polymeric monomer concentration of the method can not be the highest, Er Qieju
The substantial amounts of reaction heat produced during conjunction cannot move away rapidly and be difficult to large-scale production.
CN1432033A provides a kind of polyaniline synthesis technique continuously, uses the technique that multiple tubular reactor is in parallel,
Realize polyaniline in building-up process the ratio of heat transfer surface area and reaction volume not less than 10m-1, preferably 20m-1, thus obtain
Polymerization temperature stable and controlled as far as possible.But heat transfer surface area limits the big of tubular reactor with the ratio of reaction volume
Little, in the reactor of less internal diameter, the polyaniline particle that reaction generates brings certain can to the mass transfer of whole reaction system
, even there is the generation of adhesion condition in impact.
In at present polyaniline synthesis, there is following point:Substantial amounts of oxidant is simultaneously introduced with aniline monomer, it is impossible to
Mix rapidly, cause local excessive oxidation in polymerization process to cause polyaniline chain rupture, which results in polyaniline yield fall
Low；Because in reactor, heat of reaction can not be removed in time, local temperature is too high, and causes polyaniline molecule amount wider distribution.
Above-mentioned both sides problem directly affects performance and the yield of polyaniline.
Summary of the invention
For solving the problems referred to above, the present invention provides a kind of multistage continuous polyaniline synthesis technique, uses the multistage of oxidant
The method added so that in course of reaction, will not affect polyaniline because selective oxidation agent excess is too high with local temperature
Yield and performance, to improve yield and the product quality of polyaniline.
Technique of the present invention is as follows: under conditions of-20 ~ 50 DEG C, by aniline monomer, oxidant and medium acid water-soluble
Liquid adds the tubular reactor of plural serial stage, generates polyaniline.
Usually, in present invention process, reaction temperature preferably-10 DEG C ~ 20 DEG C.
The progression of the tubular reactor series connection of described plural serial stage is not less than 3 grades, preferably 3 ~ 6 grades.
The total amount of the oxidant entered added by described each stage reactor and the molar ratio of aniline monomer are 0.2 ~ 3.0, preferably
0.1~2.0。
Heretofore described aniline monomer has a following molecular structure:,
Wherein R1, R2, R3, R4, R5 can be H, NO respectively2、—SO3H、—OH、—CH3、—CH2CH3、—O
CH3, any one in F, Cl, Br, I.
Oxidant used is ammonium persulfate, hydrogen peroxide, ferric trichloride, potassium bichromate, potassium permanganate, Potassiumiodate, chloric acid
The mixture of one or more in potassium, manganese dioxide, carbonates peroxide.
In described medium acid, hydrogen ion is 0.1 ~ 2.0 with the molar ratio of aniline monomer.
The synthesis technique of the present invention, adding of oxidant uses the multistage method being continuously added to, owing to oxidant is multistage
Adding, this would not occur that, because adding while a large amount of oxidants, selective oxidation agent is excessive and causes the situation of over oxidation to be sent out
Raw, multistage being continuously added to of oxidant can also solve to cause temperature not because the heat produced in oxidizing process can not remove rapidly
Controlled situation occurs.Every grade of oxidant adds all use static mixers and is mixed by reactant.Meanwhile, static mixer
Also serving as the tubular reactor of polymerization, material realizes the process of mass transfer and heat transfer in static mixer, it is ensured that polymerisation exists
One uniformly, stable under conditions of carry out, solve mass transfer and the problem of heat transfer that polyaniline runs in the industrial production.
Accompanying drawing explanation
Accompanying drawing 1 is the block flowsheet schematic diagram of embodiment of the present invention synthesis technique.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in detail in.
The technological process of following example is as shown in Figure 1.
Embodiment 1
With constant flow pump, sulfuric acid and aniline are persistently added drop-wise in the reactor of plural serial stage, the flow 0.547L/h of aniline,
15% ammonium persulfate solution constant flow pump divides three grades to join in reactor, flow be followed successively by 4.564L/h, 2.7384L/h,
1.825.6L/min, reaction temperature controls at about 0 DEG C.Product is washed through washing, acetone, after the operation such as vacuum drying, poly-
The yield of aniline is 80%, number-average molecular weight 1.8 × 104, molecular weight distribution value 1.8, polyaniline particles diameter is not more than 25 μm.
After sulfuric acid adulterates, electrical conductivity is 10S cm-1。
Embodiment 2
With constant flow pump, beta-naphthalenesulfonic-acid and aniline are persistently added drop-wise in the reactor of plural serial stage, the flow of aniline
0.547L/h, 25% ammonium persulfate solution constant flow pump point level Four joins in reactor, flow be followed successively by 2.1907L/h,
1.643L/h, 1.0954L/h, 0.5477L/h, reaction temperature controls at about 5 DEG C.Product through washing, acetone wash, vacuum
Being dried etc. after operation, the yield of polyaniline is 82%, and electrical conductivity is 10S cm-1, number-average molecular weight 2.3 × 104, molecular weight distribution
Value 2.1, polyaniline particles diameter is not more than 25 μm.
Embodiment 3
With constant flow pump, DBSA and 2-chloroaniline are persistently added drop-wise in the reactor of plural serial stage, 2-chlorobenzene
The flow 0.750L/h of amine, 30% ammonium persulfate solution constant flow pump point Pyatyi joins in reactor, and flow is followed successively by
1.369L/h, 1.369L/h, 1.369L/h, 0.958L/h, 0.411 L/h, reaction temperature controls at about 5 DEG C.Product
Wash through washing, acetone, after the operation such as vacuum drying, the yield of polyaniline is 75%, and electrical conductivity is 2.0S cm-1, number-average molecular weight
3.8×104, molecular weight distribution value 3.1, polyaniline particles diameter is not more than 25 μm.
Embodiment 4
With constant flow pump, sodium methanedisulfonate and aniline are persistently added drop-wise in the reactor of plural serial stage, the flow of aniline
0.547L/h, 30% hydrogen peroxide constant flow pump point level Four joins in reactor, flow be followed successively by 0.182L/h, 0.182L/h,
0.182L/h, 0.182L/h, reaction temperature controls at about 15 DEG C.Product is washed through washing, acetone, the operation such as vacuum drying
After, the yield of polyaniline is 55%, and electrical conductivity is 2.0S cm-1, number-average molecular weight 1.5 × 104, molecular weight distribution value 3.1, poly-
Aniline particle diameter is not more than 25 μm.
Embodiment 5
With constant flow pump, dodecyl sulphate and o-toluidine are persistently added drop-wise in the reactor of plural serial stage, adjacent methyl
The flow 0.605L/h of aniline, 30% ammonium persulfate solution constant flow pump point level Four joins in reactor, and flow is followed successively by
0.182L/h, 0.182L/h, 0.182L/h, 0.182L/h, reaction temperature controls at about 25 DEG C.Product through washing, third
After the operations such as ketone is washed, vacuum drying, the yield of polyaniline is 55%, and electrical conductivity is 1.0S cm-1, number-average molecular weight 1.0 × 104,
Molecular weight distribution value 4.2, polyaniline particles diameter is not more than 25 μm.
Embodiment 6
With constant flow pump, sodium methanedisulfonate, solution of ferrous chloride and o-aminoanisole are persistently added drop-wise to the anti-of plural serial stage
Answering in device, the flow 0.620L/h of o-aminoanisole, 30% hydrogen peroxide constant flow pump point Pyatyi joins in reactor, flow
Being followed successively by 0.160L/h, 0.160L/h, 0.160L/h, 0.160L/h, 0.080 L/h, reaction temperature controls at about 25 DEG C.Instead
Answer product to wash through washing, acetone, after the operation such as vacuum drying, the yield of polyaniline is 50%, and electrical conductivity is 1.0S cm-1, number is all
Molecular weight 1.0 × 104, molecular weight distribution value 3.4, polyaniline particles diameter is not more than 25 μm.
Embodiment 7
With constant flow pump, adjacent aniline sulfonic acid is persistently added drop-wise in the reactor of plural serial stage, the flow of adjacent aniline sulfonic acid
0.547L/h, 10% ammonium persulfate constant flow pump point level Four joins in reactor, flow be followed successively by 0.720L/h, 0.720L/h,
0.720L/h, 0.180L/h, reaction temperature controls at about 15 DEG C.Product is washed through washing, acetone, the operation such as vacuum drying
After, obtaining the poly-aniline sulfonic acid of auto-dope, its yield is 70%, and electrical conductivity is 10.0S cm-1, number-average molecular weight 3.2 × 104,
Molecular weight distribution value 3.1, polyaniline particles diameter is not more than 25 μm.
Claims (2)
1. a multistage continuous polyaniline synthesis technique, it is characterised in that: with constant flow pump, sulfuric acid and aniline are persistently added drop-wise to many
In the reactor of level series connection, the flow 0.547L/h of aniline, 15% ammonium persulfate solution constant flow pump divides three grades to join reactor
In, flow is followed successively by 4.564L/h, 2.7384L/h, 1.825.6L/min, and reaction temperature controls at 0 DEG C, and product is through water
Wash, acetone is washed, after Vacuum Drying Step, the yield of polyaniline is 80%, number-average molecular weight 1.8 × 104, molecular weight distribution value
1.8, polyaniline particles diameter is not more than 25 μm, and after sulfuric acid adulterates, electrical conductivity is 10S cm-1。
2. a multistage continuous polyaniline synthesis technique, it is characterised in that: with constant flow pump, beta-naphthalenesulfonic-acid and aniline are persistently dripped
In the reactor of plural serial stage, the flow 0.547L/h of aniline, 25% ammonium persulfate solution constant flow pump point level Four joins instead
Answering in device, flow is followed successively by 2.1907L/h, 1.643L/h, 1.0954L/h, 0.5477L/h, and reaction temperature controls at 5 DEG C, instead
Answer product to wash through washing, acetone, after Vacuum Drying Step, the yield of polyaniline is 82%, and electrical conductivity is 10S cm-1, number is divided equally
Son amount 2.3 × 104, molecular weight distribution value 2.1, polyaniline particles diameter is not more than 25 μm.
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| WO2022210825A1 (en) * | 2021-03-31 | 2022-10-06 | 出光興産株式会社 | Polyaniline composite body, solution composition, rust inhibitor, rust preventive coating material, rust preventive coating film, method for producing rust preventive coating film, and structure |
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Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee after: China Petroleum & Chemical Corp. Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee before: China Petroleum & Chemical Corp. Patentee before: Nanhua Group Research Institute |
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