CN102532160A - Catalytic synthesis method of conductive polymer monomer - Google Patents
Catalytic synthesis method of conductive polymer monomer Download PDFInfo
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- CN102532160A CN102532160A CN2011103839359A CN201110383935A CN102532160A CN 102532160 A CN102532160 A CN 102532160A CN 2011103839359 A CN2011103839359 A CN 2011103839359A CN 201110383935 A CN201110383935 A CN 201110383935A CN 102532160 A CN102532160 A CN 102532160A
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Abstract
The invention discloses a catalytic synthesis method of a conductive polymer monomer 3,4-ethylenedioxythiophene, which is characterized by comprising the following steps that: 3,4-dibromo-thiophene and a Cu-based nano-porous catalyst {[Cu (HTCPZ) 0.5 ]} infinity, in which HTCPZ is 3-(4-tetrazole phenyl)amine, are reacted with sodium methoxide in a methanol solvent to obtain 3,4-dimethoxy-thiophene; and then the 3,4-dimethoxy thiophene is reacted with ethylene glycol in the presence of p-toluenesulfonic acid as a catalyst and toluene as a solvent to obtain a low-boiling-point alcohol ROH by rectification, and the alcohol ROH is washed, dried and distilled in a vacuum to obtain the 3,4-ethylenedioxythiophene. The catalytic synthesis method provided by the invention has the advantages of high yield and small quantity of used catalyst.
Description
Technical field
The invention belongs to the compound method of conductive high polymer monomer, be specifically related to high purity 3, the process for catalytic synthesis of 4-ethene dioxythiophene (EDOT) conductive high polymer monomer.
Background technology
Japanization scholar Bai Chuanying sets (H.Shirakawa), and Americanized scholar Mike wears close (A.G.MacDiarmid) and U.S. physicist Xi Ge (A.J.Heeger) has obtained Nobel chemistry Prize in 2000 jointly because the initiative of in the conductive polymers field, making is contributed.Also changed the impression that people are regarded as polymer (plastics) isolator thus.In recent years, because the fast development of conducting polymer composite makes the electronics of general using metallic substance and information products further to develop to light, thin, short, little direction.The constitutional features of conductive polymers is to contain a long π-electron conjugated main chain, has in light weight, easy processing, anticorrosive and metallic conductivity and inorganic semiconductor characteristic etc., thereby has huge commercial application value.Consider the factors such as intensity of the air stability and the material of conductive polymers; At present the more conductive polymers of research comprises polyacetylene series, polyaniline is serial, polypyrrole is serial, Polythiophene series etc., and wherein the series of the polyaniline in the aromatic series relies on its outstanding conductive stability and lower cost mass production in industry.But,, be a kind of strong carcinogen because p-diaminodiphenyl is poisonous because of the existence that in the process of synthesized polyaniline, has p-diaminodiphenyl has limited the research of people to it.Therefore polypyrrole and the Polythiophene in the aromatic series just becomes the conductive polymers that development potentiality is more arranged, and is that monomeric conductive polymers has electrochemical behavior and excellent stability preferably with thiophene and verivate thereof wherein, and extremely people's favor.
Thiophene is the monomer of Polythiophene, but its solubleness is low, and color is dark deeply, is unfavorable for processing and uses.In the later stage in the 1980's, Bayer A.G's successful development goes out a kind of novel conductive polymer poly enedioxy thiophene (PEDOT), because 3,4 of its thiphene ring by electron donating group-substituted, make PEDOT have the performance more excellent than general polythiofuran derivative.Monomer enedioxy thiophene (EDOT) more is prone to form linear unsaturated long-chain than other thiophene derivant; And its thiphene ring 3; 4 have been reduced monomeric oxidation potential after the electron donating group-substituted, increased the solubleness in water, have expanded the polymerization of thiophene in the aqueous solution.The molecular structure that gathers enedioxy thiophene (PEDOT) and monomer whose enedioxy thiophene (EDOT) is following:
At present synthetic EDOT mainly adopts two kinds of methods.A kind of is that employing sulfo-two sweet acid esters are the synthetic schemes of raw material.This respect has Chinese patent CN101104619A, CN101429205, CN101591345, CN101519409A, CN101570541 and CN101062927, U.S. Pat 2002/0002287A1, US2001/0034453A1, US6169238 and US6528662, and " Hangzhou chemical industry " (2007; 37; 31-35), " New Chemical Materials " (2007,35,19-21) with " Henan chemical industry " (2008; 25,12-14) did relevant report.This synthetic schemes mainly is to be raw material with sulfo-two sweet acid, obtains EDOT through esterification, cyclisation, closed loop, acidifying and decarboxylation five steps reaction:
But the total recovery of this synthetic schemes is on the low side, and side reaction is on the high side; And use sulfo-two sweet acid expensive, raw material is difficult to obtain; Particularly last decarboxylation temperature is high, makes cost increase severely with dangerous, thereby has limited its industrial mass production.
Another kind is that the employing thiophene is the synthetic schemes of raw material.Existing Chinese patent CN101570542 of this respect and CN101220038A, and " tetrahedron wall bulletin " (Tetra.Lett.2004,45, relevant report 6049-6050).This synthetic schemes mainly is to be raw material with the thiophene that is easy to obtain, and obtains EDOT through bromination, reduction, etherificate and cyclisation four-step reaction:
But its total recovery is also on the low side, and side reaction is on the high side.Major cause is 3, and the yield of 4-dibromo thiophene when etherificate is on the low side, only can reach 50-70%, and temperature drift, and the reaction times is long; Owing to do not find appropriate catalyst, the general at present copper salt catalyst consumption that uses is very many, and is suitable with the mole materials ratio of raw material; Make cost very high, and be not suitable for the carrying out of big charging capacity reaction, thereby limited its suitability for industrialized production.
Summary of the invention
The purpose of this invention is to provide a kind of conductive polymers monomer 3, the process for catalytic synthesis of 4-ethene dioxythiophene (EDOT) is to solve the long reaction time of synthetic EDOT committed step in the prior art, poor selectivity, the problem that productive rate is low.
Conductive polymers monomer 3 of the present invention, the process for catalytic synthesis of 4-ethene dioxythiophene is characterized in that:
Press 3 earlier, 4-dibromo thiophene: pure alkali ROM: catalyzer { [Cu (HTCPZ)
0.5]
∞Mol ratio be 1: 2～10: 0.001～0.1, make 3, the 4-dibromo thiophene in alcoholic solvent, Cu-Quito pore catalyst { [Cu (HTCPZ)
0.5]
∞Effect reacts with pure alkali at 60-100 ℃ down, filters, and distillation promptly obtains 3, the 4-dialkoxythiophene; Said Cu-Quito pore catalyst { [Cu (HTCPZ)
0.5]
∞HTCPZ in the formula is three-(4-tetrazole base phenyl) amine;
By 3,4-dimethoxy-thiophene: terepthaloyl moietie: the mol ratio of p-methyl benzenesulfonic acid is 1: 1～1.2: 0.01～0.1, with 3 again; The 4-dialkoxythiophene is a catalyzer with the strong acid p-methyl benzenesulfonic acid in arene or polarity high boiling solvent, under 50-160 ℃ of temperature condition, with terepthaloyl moietie pure permutoid reaction takes place; Rectifying goes out the lower boiling alcohol roh, washing, drying; Underpressure distillation promptly obtains product 3, the 4-ethene dioxythiophene.
Said alcoholic solvent is the lower boiling alcohol roh, and wherein R is methyl or ethyl, preferable methyl;
Said pure alkali is ROM, and M is Li, and Na or K are preferably Na. Wherein R is methyl or ethyl, preferable methyl;
Said aromatic hydrocarbon or strong polar reaction solvent are benzene,toluene,xylene, trimethylbenzene, N, dinethylformamide, N, N-DEF, DMAC N,N, dioxane or methyl-sulphoxide; Preferred toluene.
Said pure permutoid reaction temperature is preferably 100～120 ℃;
Said 3,4-dimethoxy-thiophene: terepthaloyl moietie: the mol ratio of p-methyl benzenesulfonic acid is preferably 1: 1～and 1.1: 0.01～0.05.
The above-mentioned technological line of the inventive method can be represented as follows:
3,4-dibromo thiophene 3,4-dialkoxythiophene 3,4-ethene dioxythiophene.
{ [the Cu (HTCPZ) of employed catalyzer among the present invention
0.5]
∞Adopt following method to prepare: the CuCl that presses 0.1023g (0.6mmol)
22H
2O, the part three of 0.0449g (0.1mmol)-(4-tetrazole base phenyl) amine (H
3TCPZ) and 6mL N, dinethylformamide (DMF) joins in the autoclave of 15mL, airtightly is heated to 170 ℃ and kept 72 hours; Cool to room temperature by the speed that is not higher than 10 ℃/h then, filter water washing; Dry under the condition of room temperature, obtain glassy yellow hexa-prism crystal.The analysis of monocrystalline X-ray has confirmed that its structure is a hexagonal system, and molecular formula is { [Cu (HTCPZ)
0.5]
∞, in the formula, HTCPZ is three-(4-tetrazole base phenyl) amine, is that a molecular structure does
Three parts; This porous crystalline material is the hexagonal system crystalline material; Spacer is P6122; The duct size range is 1～1.2nm.
Because the inventive method adopts the immobilized interior inorganic-organic hybridization nano porous material of vesicular structure that arrives of metal center as catalyzer, has the following advantages:
(1) catalyst levels is few;
(2) metal center homodisperse, contact area is big, and the catalysis capacity is big;
(3) the hybrid inorganic-organic crystalline material is insoluble to common solvent, and after reacting completely, direct filtration is recyclable catalyzer, is easy to handle, and reclaims.
(4) catalyzer can be reused through behind the simple dry precipitation, and this has more realistic meaning in industrial application.
(5) excellent catalytic effect, product yield is high, and yield is high, and side reaction is few.
(6) operational safety, can not produce a large amount of stills residual with solid-liquid rubbish mutually, more environmental protection is fit to commercialization production.
Description of drawings
Fig. 1 is employed catalyzer { [Cu (HTCPZ) among the present invention
0.5]
∞The crystalline structure synoptic diagram.
Embodiment
Embodiment 1:3, the preparation of 4-dimethoxy-thiophene
Under nitrogen protection, in the 250ml four-hole boiling flask, add the MeOH solution that 150mL contains 16.2g (0.3mol) MeONa, add 0.5g catalyzer { [Cu (HTCPZ) again
0.5]
∞, drip 24.2g (0.1mol) 3 then, the 4-dibromo thiophene, after dropwising, temperature rising reflux 24h.Normal pressure reclaims methyl alcohol, in flask, adds PhMe extraction, filtering recovering catalyst 0.498g once more.The organic phase washing, drying, colourless transparent liquid 12.96g (GC＞99%) is collected in underpressure distillation, and nuclear-magnetism is confirmed as product 3,4-dimethoxy-thiophene, yield 90%.H NMR (400M, CDCl
3): 3.9ppm (s, 6H (methylene radical)); (6.2ppm s, 2H (thiphene ring)).
{ [the Cu (HTCPZ) of employed catalyzer among the present invention
0.5]
∞The following method that adopts prepare: with the CuCl of 0.1023g (0.6mmol)
22H
2O, the part three of 0.0449g (0.1mmol)-(4-tetrazole base phenyl) amine (H
3TCPZ) and 6mL N, dinethylformamide (DMF) joins in the autoclave of 15mL, airtightly is heated to 170 ℃ and kept 72 hours, cools to room temperature by the speed that is not higher than 10 ℃/h then.Filter, water washing, dry under the condition of room temperature, obtain glassy yellow hexa-prism crystal 0.0404g, productive rate is 70%.The analysis of monocrystalline X-ray confirms that the crystalline structure of products therefrom is a hexagonal system, and its molecular formula is { [Cu (HTCPZ)
0.5]
∞, in the formula, HTCPZ is three-(4-tetrazole base phenyl) amine, is that a molecular structure does
Three parts; This porous crystalline material is the hexagonal system crystalline material; Spacer is P6122; The duct size range is 1～1.2nm.
Fig. 1 is the { [Cu (HTCPZ) of employed catalyzer among the present invention
0.5]
∞The crystalline structure synoptic diagram.This porous crystal has the duct that size reaches 1.2nm, possesses the catalytic size in duct.
Porous the crystalline material { [Cu (HTCPZ) as catalyzer use of following table 1 for preparing among measured the present invention
0.5]
∞Crystal parameter:
Table 1
The preparation of embodiment 2:EDOT
Get 250 milliliter of four neck flask, under nitrogen protection, with 3; 4-dimethoxy-thiophene 28.84 grams (0.2mol), and terepthaloyl moietie (13.67 grams, 0.22mmol); 150 milliliters of toluene, tosic acid (PTSA) 2 grams add in the four neck flasks magnetic agitation successively; Intensification rectifying 12 hours, limit backflow limit rectifying goes out methyl alcohol.Reaction finishes, and adds 50 ml waters, stirs, and tells organic layer, with the saturated common salt water washing, uses anhydrous Na
2SO
4Carry out drying, toluene is reclaimed in underpressure distillation, obtains colourless transparent liquid 21.3g (GC＞99%), and nuclear-magnetism confirms to be product EDOT, yield 75%.H NMR (300M, CDCl
3): 4.22ppm (s, 4H (methylene radical)); (6.34ppm s, 2H (thiphene ring)).
Claims (6)
1. conductive polymers monomer 3, the process for catalytic synthesis of 4-ethene dioxythiophene is characterized in that:
Press 3 earlier, 4-dibromo thiophene: pure alkali ROM: catalyzer { [Cu (HTCPZ)
0.5]
∞Mol ratio be 1: 2～10: 0.001～0.1, make 3, the 4-dibromo thiophene in alcoholic solvent, Cu-Quito pore catalyst { [Cu (HTCPZ)
0.5]
∞Effect reacts with pure alkali at 60-100 ℃ down, filters, and distillation promptly obtains 3, the 4-dialkoxythiophene; Said Cu-Quito pore catalyst { [Cu (HTCPZ)
0.5]
∞HTCPZ in the formula is three-(4-tetrazole base phenyl) amine;
By 3,4-dimethoxy-thiophene: terepthaloyl moietie: the mol ratio of p-methyl benzenesulfonic acid is 1: 1～1.2: 0.01～0.1, with 3 again; The 4-dialkoxythiophene is a catalyzer with the strong acid p-methyl benzenesulfonic acid in arene or polarity high boiling solvent, under 50-160 ℃ of temperature condition, with terepthaloyl moietie pure permutoid reaction takes place; Rectifying goes out the lower boiling alcohol roh, washing, drying; Underpressure distillation promptly obtains product 3, the 4-ethene dioxythiophene;
Said alcoholic solvent is the lower boiling alcohol roh, and wherein R is methyl or ethyl;
Said pure alkali is ROM, and M is Li, Na or K; Wherein R is methyl or ethyl;
Said aromatic hydrocarbon or strong polar reaction solvent are benzene,toluene,xylene, trimethylbenzene, N, dinethylformamide, N, N-DEF, DMAC N,N, dioxane or methyl-sulphoxide.
2. according to the said conductive polymers monomer 3 of claim 1, the process for catalytic synthesis of 4-ethene dioxythiophene is characterised in that said catalyzer { [Cu (HTCPZ)
0.5]
∞Adopt following method to prepare: the CuCl that presses 0.1023g
22H
2O, the part three of 0.0449g-(4-tetrazole base phenyl) amine (H
3TCPZ) and 6mL N, dinethylformamide joins in the autoclave of 15mL, airtightly is heated to 170 ℃ and kept 72 hours; Cool to room temperature by the speed that is not higher than 10 ℃/h then, filter water washing; Dry under the condition of room temperature, obtain glassy yellow hexa-prism crystal; In the formula, HTCPZ is three-(4-tetrazole base phenyl) amine, is that a molecular structure does
Three parts; This porous crystalline material is the hexagonal system crystalline material; Spacer is P6122; The duct size range is 1～1.2nm.
3. according to the said conductive polymers monomer 3 of claim 1, the process for catalytic synthesis of 4-ethene dioxythiophene is characterised in that the M among the said pure alkali ROM is Na.
4. according to the said conductive polymers monomer 3 of claim 1, the process for catalytic synthesis of 4-ethene dioxythiophene is characterised in that R is a methyl among the said pure alkali ROM.
5. according to the said conductive polymers monomer 3 of claim 1, the process for catalytic synthesis of 4-ethene dioxythiophene is characterised in that said pure permutoid reaction temperature is 100～120 ℃.
6. according to the said conductive polymers monomer 3 of claim 1, the process for catalytic synthesis of 4-ethene dioxythiophene is characterised in that saidly 3, and the mol ratio of 4-dimethoxy-thiophene: terepthaloyl moietie: catalyst P TSA is 1: 1～1.1: 0.01～0.05.
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| CN109054044A (en) * | 2018-09-26 | 2018-12-21 | 中国科学技术大学苏州研究院 | A kind of porous crystalline material and its preparation method and application |
| CN113929893A (en) * | 2020-07-13 | 2022-01-14 | 万华化学集团股份有限公司 | Copolycarbonate with high refractive index and low birefringence |
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| CN113929893A (en) * | 2020-07-13 | 2022-01-14 | 万华化学集团股份有限公司 | Copolycarbonate with high refractive index and low birefringence |
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Application publication date: 20120704 |