CN1229409C - Preparation method of poly(2,5-dialkoxy-1,4-benzene) - Google Patents
Preparation method of poly(2,5-dialkoxy-1,4-benzene) Download PDFInfo
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- CN1229409C CN1229409C CN 200410013287 CN200410013287A CN1229409C CN 1229409 C CN1229409 C CN 1229409C CN 200410013287 CN200410013287 CN 200410013287 CN 200410013287 A CN200410013287 A CN 200410013287A CN 1229409 C CN1229409 C CN 1229409C
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- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000000926 separation method Methods 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 238000000746 purification Methods 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 93
- 239000000047 product Substances 0.000 claims description 73
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 62
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 42
- 238000001035 drying Methods 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 150000002910 rare earth metals Chemical group 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 31
- 239000000463 material Substances 0.000 abstract description 13
- 238000006116 polymerization reaction Methods 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 10
- 238000005691 oxidative coupling reaction Methods 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000010409 thin film Substances 0.000 abstract description 3
- 229920000547 conjugated polymer Polymers 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 235000005811 Viola adunca Nutrition 0.000 abstract 1
- 240000009038 Viola odorata Species 0.000 abstract 1
- 235000013487 Viola odorata Nutrition 0.000 abstract 1
- 235000002254 Viola papilionacea Nutrition 0.000 abstract 1
- -1 alkoxy carbon Chemical compound 0.000 abstract 1
- 239000012043 crude product Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 31
- 239000007787 solid Substances 0.000 description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 26
- 239000004570 mortar (masonry) Substances 0.000 description 24
- 238000004458 analytical method Methods 0.000 description 23
- 239000007788 liquid Substances 0.000 description 20
- 238000005481 NMR spectroscopy Methods 0.000 description 16
- 238000000710 polymer precipitation Methods 0.000 description 14
- 238000005303 weighing Methods 0.000 description 14
- 229910052742 iron Inorganic materials 0.000 description 13
- 150000001805 chlorine compounds Chemical class 0.000 description 10
- 238000001542 size-exclusion chromatography Methods 0.000 description 9
- GHKFGRVGAQYZNT-UHFFFAOYSA-N 1,2-dibutoxybenzene Chemical compound CCCCOC1=CC=CC=C1OCCCC GHKFGRVGAQYZNT-UHFFFAOYSA-N 0.000 description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- QZYDOKBVZJLQCK-UHFFFAOYSA-N 1,2-diethoxybenzene Chemical compound CCOC1=CC=CC=C1OCC QZYDOKBVZJLQCK-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000006887 Ullmann reaction Methods 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000005224 alkoxybenzenes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- KNRQFACTBMDELK-UHFFFAOYSA-N hexoxybenzene Chemical compound CCCCCCOC1=CC=CC=C1 KNRQFACTBMDELK-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical class O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
本发明公开了一种固态氧化偶联聚合制备聚(2，5-二烷氧基-1，4-苯)的方法。该方法以烷氧基碳原子数为1至18的对二烷氧基苯为单体，以金属氯化物为催化剂，在5～65℃、混合研磨下反应10至30分钟得粗产品；分离、纯化即得聚(2，5-二烷氧基-1，4-苯)。本发明由于在聚合反应时不用溶剂，减少了环境的污染；降低了生产成本；聚合反应时间短，仅需10-30分钟，使生产效率提高；提高了聚合产率，可达90%；得到的聚合物具有良好的结构区位规整性，苯环之间全部以对位链接。所得到的聚合物的荧光发射峰值约405纳米，属于蓝紫光发射材料。这种共轭聚合物可以用于制造电致发光器件、有机薄膜晶体管和其它光电转换器件。The invention discloses a method for preparing poly(2,5-dialkoxy-1,4-benzene) by solid-state oxidative coupling polymerization. The method uses p-dialkoxybenzene with an alkoxy carbon number of 1 to 18 as a monomer, uses metal chloride as a catalyst, and reacts for 10 to 30 minutes at 5 to 65 ° C under mixing and grinding to obtain a crude product; separation , and purification to obtain poly(2,5-dialkoxy-1,4-benzene). Since the present invention does not use a solvent during the polymerization reaction, the pollution of the environment is reduced; the production cost is reduced; the polymerization reaction time is short, only needing 10-30 minutes, so that the production efficiency is improved; the polymerization yield is improved, which can reach 90%; The polymer has good structural regioregularity, and all the benzene rings are linked in the para position. The fluorescence emission peak of the obtained polymer is about 405 nanometers, which belongs to the blue-violet light emission material. This conjugated polymer can be used in the manufacture of electroluminescent devices, organic thin film transistors and other photoelectric conversion devices.
Description
Technical field
The present invention relates to a class main chain by poly-preparation method to benzene is formed, side chain has alkoxyl group poly-(2,5-dialkoxy-1,4-benzene).
Background technology
Poly-to benzene (PPP) and derivative thereof, be the main chain conjugated type polymkeric substance that main chain is made up of with the contraposition link phenyl, have broad application prospects at aspects such as organic semiconductor thin film transistor, organic elctroluminescent device and information technologies.Particularly in organic elctroluminescent device, make the polymeric film luminescent layer, have advantages such as low-voltage dc voltage drives, ultra-thin, full curing.Synthetic main chain is by the poly-conjugated polymers that benzene is formed, must on phenyl ring, introduce halogen atom, by ullmann reaction (Ullmann Reaction) or Suzuki reaction [Synthetic Communications, 11 (7), 513-519,1981.] condensation is removed halogen atom and is formed polymkeric substance; The latter also will use precious metal to make catalyzer, thereby these compound cost height, produces relatively difficulty in batches.In order to satisfy the processing requirement of making device, polymkeric substance must be dissolved in organic solvent, therefore introduces the hydrotropy group usually on phenyl ring, as alkyl, alkoxyl group etc.The oxidative coupling method is synthetic poly-the simplest to the method for benzene and derivative thereof, and K.Mukai. etc. have reported CuCl in oil of mirbane
2And AlCl
3Have poly-(2,5-dimethoxy-1,4-benzene) [K.Mukai, Teshirogi etc.: J.Polym.Sci.Polym.Chem.Ed., 1985,23,1259.] of preparation down, the oil of mirbane price is expensive, toxicity is big, AlCl
3The moisture absorption in air is emitted hydrogenchloride, is difficult for storage and processing.U.Mitsuru. with A.Tetsuya. FeCl in oil of mirbane
3Prepared under existing poly-(2,5-n-butoxy-1,4-benzene), used FeCl
3Replace AlCl
3, make preparation process simpler and easy, but still used oil of mirbane [M.Ueda, T.Abe, and H.Awano:Macromolecules, 1992,25,5125.].After, Li Jianke etc. replace oil of mirbane with chloroform, make solvent price and toxicity reduce (Li Jianke, positive bright book etc.: polymer journal, 1998,4,487).All aforesaid methods all use poisonous and volatile solvent, and expensive.Main problem is that the poly-dialkoxy of oxidative coupling method synthetic is bad to the position regularity (regioregularity) of benzene, is forming phenyl ring 1, generates 1 in the time of the link of 4-position, and the 3-position connects, and influences the performance of material.The present invention has overcome the shortcoming of traditional method, does not use solvent during polymerization; And resulting polymkeric substance has good position regularity, and is promptly poly-completely to the benzene structure.
Summary of the invention
The purpose of this invention is to provide the preparation method of poly-(2,5-dialkoxy-1,4-benzene), this method is simple and direct, easily mass-produced, and also the polymkeric substance that makes has good position regularity structure and better material performance.
For achieving the above object, the technical solution used in the present invention is as follows:
Directly form poly-(2,5-dialkoxy-1,4-benzene) by the reaction of solid oxide coupling polymerization, general formula is:
In the formula, R represents the alkyl of 1 to 10 carbon, n=30 to 200.
The preparation method of above-mentioned poly-(2,5-dialkoxy-1,4-benzene) is as follows: with the alkoxyl group carbonatoms be 1 to 18 be monomer to dialkoxy benzene, be catalyzer with the metal chloride, under 5～65 ℃, mixed grinding reaction 10 to 30 minutes thick product; Separation, purifying promptly get and gather (2,5-dialkoxy-1,4-benzene).
Above-mentioned catalyst levels is monomeric 1 to 4 times (mol ratio).
Above-mentioned catalyzer is rare-earth metal chloride, FeCl
36H
2O, anhydrous CuCl
2, anhydrous FeCl
3Or their mixture.Preferred anhydrous FeCl
3
Above-mentioned separation, purification step are: catalyzer and the intact monomer of unreacted are removed in the dilute hydrochloric acid washing of thick product water, methyl alcohol, ethanol or 1-2M/L, and centrifugation or filtration are gathered (2,5-dialkoxy-1,4-benzene).Perhaps,, in alcoholic solvent such as methyl alcohol or ethanol, precipitate dissolving with chloroform behind the thick product drying, collecting precipitation, drying is gathered (2,5-dialkoxy-1,4-benzene).
According to technical scheme of the present invention, described reaction conditions is a solid phase, participates in the direct and catalyst action by monomer without any need for solvent.
Provided by the present invention poly-(2,5-dialkoxy-1,4-benzene) can be dissolved in usual vehicle, absorbing wavelength is 350 nanometers, the emission wavelength peak value is about 410 nanometers, decomposition temperature＞250 ℃ can be used for making electroluminescent device, photo luminescent devices, organic semiconductor thin film transistor and other electrooptical device and product.
The present invention is a reactive functionality with the active hydrogen on the aromatic ring in polyreaction, need not the general polymerization reaction introduce bifunctional like that on monomer, has saved the monomeric complex reaction step of preparation, makes the preparation process of material simplify; The more important thing is under solid-state situation and realize oxidative coupling polymerization, make technology of preparing and further raising has all been arranged with quality product.Compare with traditional oxidative coupling technology, the present invention has following beneficial effect:
1, the present invention resulting poly-(2,5-dialkoxy-1,4-benzene) has good position regularity, and is promptly poly-completely to the benzene structure; Usually bad by oxidative coupling method synthetic poly-(dialkoxy) to the position regularity (regioregularity) of benzene, forming phenyl ring 1, generate 1 in the time of the link of 4-position, the 3-position connects, generated poly-between the benzene structure, influence the performance of material.
2, because the method for having invented the solid oxide coupling polymerization, avoided that general oxidative coupling polymerization adopts as oil of mirbane, poisonous and expensive organic solvent such as chloroform has reduced cost.
3, not using solvent, reduced environmental pollution, is an eco-friendly Green Chemical Technology.
4, the present invention shortens the reaction times greatly, only needs 10-30 minute, and production efficiency is improved greatly.The time of traditional solution reaction generally needs 10-40 hour.
5, the present invention improves polymerization yield rate, and the solid state polymerization productive rate is generally at 70-80%, and high reaches 90%; The polymerization yield rate of traditional solution reaction is generally below 60%.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is further described:
Embodiment 1: take by weighing 0,61 grams dibutoxy benzene and 1.00 gram Anhydrous Ferric Chlorides are put into mortar, grind under the room temperature.Grind after 30 minutes stopped reaction.With the product in ethanol or the methanol wash mortar, use the centrifugal mode with solid-liquid separation, to remove iron(ic) chloride and unreacted monomer.Separate the solid that obtains with ethanol or methanol wash, it is dry to put into constant temperature oven (50 ℃) then.After the oven dry, with a spot of chloroform product is dissolved fully, adding four to methyl alcohol that is five times in the chloroform amount or ethanol gets off polymer precipitation, carry out centrifugal once more with solid-liquid separation, after putting constant temperature oven (50 ℃) drying, obtain product poly-(2,5-dialkoxy-1,4-benzene) 0.44 gram, productive rate reaches 72%.The number-average molecular weight that size exclusion chromatography is measured polymkeric substance is 30,000.Through 300,000,000 nuclear magnetic resonance spectroscopies, hydrogen spectrum resonance absorbing peak appears at 7.075,3.915,1.663,1.385, and 0.894ppm belongs on the phenyl ring 2,5 respectively, the methylene radical that links to each other with oxygen, intermediate sub methyl, the hydrogen of methylene radical; Between phenyl ring hydrogen vibrating area, only occur unimodally, illustrate that the phenyl ring on-link mode (OLM) is 1,4 link; If 1,3 connection should occur 4.05,7.49, the 7.62ppm absorption peak does not occur at this.The carbon-13 nmr spectra analytical results: resonance absorbing peak appears at 150.143,127.669, and 117.456ppm belongs to the carbon that links to each other with-oxyl on the phenyl ring respectively; The carbon that links to each other with adjacent phenyl rings, and 2,5 carbon.If 1,3 connection should absorption peak occur at the 153ppm place.The fourier infrared collection of illustrative plates has the vibration peak that is positioned at wave number 860, is phenyl ring 1,2, and 4,5 signs that replace prove that the phenyl ring on-link mode (OLM) is 1,4 connection.This polymkeric substance has good position regularity structure.About 404 nanometers of its emission peak of fluorometric analysis are the royal purple light-emitting material.
Embodiment 2: take by weighing 0,61 grams to dibutoxy benzene mix with 2.00 grams anhydrous rare-earth chlorination (product industrial goods in packet header contain La27% in the rare earth, Ce51%, Nd15% Pr5%) puts into mortar and grinds.Grind after 20 minutes, put into constant temperature oven (60 ℃) 0.5 hour.Continue to grind after 10 minutes stopped reaction.Wash the product in the mortar with water, with filtering mode with solid-liquid separation, to remove rare earth.With ethanol or methanol wash solid secondary, it is dry to put into constant temperature oven (50 ℃) then.After the oven dry, use the washing with alcohol product, make solid-liquid separation with the centrifugal mode then, inclining supernatant liquor, stays precipitation.Then precipitation is put into oven drying, promptly obtain product poly-(2,5-dialkoxy-1,4-benzene).After product adding chloroform dissolves fully, under the irradiation of ultraviolet lamp, can see blue-fluorescence.Product is through 3000 nuclear magnetic resonance spectroscopies, and the fourier infrared atlas analysis proves that the phenyl ring on-link mode (OLM) is 1,4 connection, and this polymkeric substance has good position regularity structure.
Embodiment 3: take by weighing 0,61 grams and dibutoxy benzene and 0.81 is restrained anhydrous cupric chloride put into mortar and grind.Grind after 10 minutes, put into constant temperature oven (50 ℃) 1 hour.Continue to grind after 10 minutes stopped reaction.With the product in ethanol or the methanol wash mortar, use the centrifugal mode with solid-liquid separation, to remove cupric chloride and unreacted monomer.With ethanol or methanol wash solid three times, it is dry to put into constant temperature oven (50 ℃) then.After the oven dry, obtain product poly-(2,5-dialkoxy-1,4-benzene).With chloroform it is dissolved fully, under the irradiation of ultraviolet lamp, can see blue-fluorescence.Product is through 300,000,000 nuclear magnetic resonance spectroscopies, and the fourier infrared atlas analysis proves that the phenyl ring on-link mode (OLM) is 1,4 connection, and this polymkeric substance has good position regularity structure.
Embodiment 4: take by weighing 0,61 grams and dibutoxy benzene and 2.44 is restrained Iron trichloride hexahydrates put into mortar and grind.Grind after 20 minutes, put into constant temperature oven (50 ℃) 3 hours.Continue to grind after 10 minutes stopped reaction.With the product in ethanol or the methanol wash mortar, use the centrifugal mode with solid-liquid separation, to remove iron(ic) chloride and unreacted monomer.Separate the solid that obtains with ethanol or methanol wash, it is dry to put into constant temperature oven (50 ℃) then.After the oven dry, with a spot of chloroform product is dissolved fully, adding four to methyl alcohol that is five times in the chloroform amount or ethanol gets off polymer precipitation, carry out centrifugal once more with solid-liquid separation, after anti-constant temperature oven (50 ℃) drying, obtain product poly-(2,5-dialkoxy-1,4-benzene) 0.37 gram, productive rate reaches 60%.Through about 404 nanometers of its emission peak of fluorometric analysis, be blue light emitting material.Product is through 300,000,000 nuclear magnetic resonance spectroscopies, and the fourier infrared atlas analysis proves that the phenyl ring on-link mode (OLM) is 1,4 connection, and this polymkeric substance has good position regularity structure.
Embodiment 5: take by weighing 0,61 grams and dibutoxy benzene and 1.45 is restrained Anhydrous Ferric Chlorides put into mortar and grind.Grind after 30 minutes stopped reaction under the room temperature.With the product in ethanol or the methanol wash mortar, use the centrifugal mode with solid-liquid separation, to remove iron(ic) chloride and unreacted monomer.With ethanol or methanol wash solid three times, it is dry to put into constant temperature oven (50 ℃) then.After the oven dry, with a spot of chloroform product is dissolved fully, adding four to methyl alcohol that is five times in the chloroform amount or ethanol gets off polymer precipitation, carry out centrifugal once more with solid-liquid separation, after putting constant temperature oven (50 ℃) drying, obtain product poly-(2,5-dialkoxy-1,4-benzene) 0.50 gram, productive rate reaches 83%.The number-average molecular weight that size exclusion chromatography is measured polymkeric substance is 3.1 ten thousand.Product is through 300,000,000 nuclear magnetic resonance spectroscopies, and the fourier infrared atlas analysis proves that the phenyl ring on-link mode (OLM) is 1,4 connection, and this polymkeric substance has good position regularity structure.Through about 404 nanometers of its emission peak of fluorometric analysis, be blue light emitting material.
Embodiment 6: take by weighing 0,61 grams and dibutoxy benzene and 1.99 is restrained Iron trichloride hexahydrates put under the mortar room temperature and grind.Grind after 25 minutes stopped reaction.With the product in ethanol or the methanol wash mortar, use the centrifugal mode with solid-liquid separation, to remove iron(ic) chloride and unreacted monomer.With ethanol or methanol wash solid secondary, it is dry to put into constant temperature oven (50 ℃) then.After the oven dry, chloroform with 12 milliliters dissolves product fully, adding four to methyl alcohol that is five times in the chloroform amount or ethanol gets off polymer precipitation, carry out centrifugal once more with solid-liquid separation, after solid put into constant temperature oven (50 ℃) drying, obtain product poly-(2,5-dialkoxy-1,4-benzene) 0.50 gram, productive rate reaches 83%.The number-average molecular weight that size exclusion chromatography is measured polymkeric substance is 2.8 ten thousand.Through about 404 nanometers of its emission peak of fluorometric analysis, be blue light emitting material.Product is through 300,000,000 nuclear magnetic resonance spectroscopies, and the fourier infrared atlas analysis proves that the phenyl ring on-link mode (OLM) is 1,4 connection, and this polymkeric substance has good position regularity structure.
Embodiment 7: take by weighing 0,61 grams and dibutoxy benzene and 1.45 is restrained Anhydrous Ferric Chlorides put under the mortar room temperature and grind.Grind after 30 minutes stopped reaction.With the product in the dilute hydrochloric acid of the 1M washing mortar, with filter type with solid-liquid separation, to remove iron(ic) chloride.Repeatedly washed product is to neutrality for water again, and it is middle dry that product is put constant temperature oven (50 ℃).After the oven dry, with about 10 milliliters of chloroforms product is dissolved fully, adding four to methyl alcohol that is five times in the chloroform amount or ethanol gets off polymer precipitation, carry out centrifugal once more with solid-liquid separation, after solid put into constant temperature oven (50 ℃) drying, obtain product poly-(2,5-dialkoxy-1,4-benzene) 0.50 gram, productive rate reaches 83%.The number-average molecular weight that size exclusion chromatography is measured polymkeric substance is 30,000.Through about 404 nanometers of its emission peak of fluorometric analysis, be blue light emitting material.Product is through 300,000,000 nuclear magnetic resonance spectroscopies, and the fourier infrared atlas analysis proves that the phenyl ring on-link mode (OLM) is 1,4 connection, and this polymkeric substance has good position regularity structure.
Embodiment 8: take by weighing 6,1 gram dibutoxy benzene, 14.5 is restrained Anhydrous Ferric Chlorides, puts into the bottle that agate ball (or glass sphere) is housed, vial is placed on the bobbing machine vibrates, make agate ball (or glass sphere) griding reaction thing, grind after 30 minutes stopped reaction under the room temperature.With the product in the dilute hydrochloric acid washing bottle of 1M, with filter type with solids constituent from, to remove iron(ic) chloride.Water repeatedly washs to neutrality again, puts in the constant temperature oven (50 ℃) product dry.After the oven dry, product is dissolved fully, and join in 400 milliliters the ethanol, stir with 100 milliliters of chloroforms, after treating that polymer precipitation gets off, refilter to isolate solid, put into constant temperature oven (50 ℃) drying after, obtain product poly-(2,5-dialkoxy-1,4-benzene) 5.0 grams, productive rate reaches 81%.The number-average molecular weight that size exclusion chromatography is measured polymkeric substance is 2.8 ten thousand.Through about 404 nanometers of its emission peak of fluorometric analysis, be blue light emitting material.Product is through 300,000,000 nuclear magnetic resonance spectroscopies, and the fourier infrared atlas analysis proves that the phenyl ring on-link mode (OLM) is 1,4 connection, and this polymkeric substance has good position regularity structure.
Embodiment 9: take by weighing 0.55 gram and two hexyloxy benzene and 1.00 are restrained Anhydrous Ferric Chlorides put under the mortar room temperature and grind.Grind after 30 minutes stopped reaction.Isolate solid with filter type, with 20 milliliters of washings of dilute hydrochloric acid solid of 1M, to remove iron(ic) chloride.Water repeatedly washs to neutrality again, puts in the constant temperature oven (50 ℃) product dry.After the oven dry, 10 milliliters chloroform dissolves product fully, joins in 40 milliliters the methyl alcohol, stirs, polymer precipitation is got off, carry out again centrifugal with separate solid, put into constant temperature oven (50 ℃) drying after, obtain product poly-(2,5-dialkoxy-1,4-benzene) 0.50 gram, productive rate 90%.The number-average molecular weight that size exclusion chromatography is measured polymkeric substance is 2.85 ten thousand.Through about 404 nanometers of its emission peak of fluorometric analysis, be blue light emitting material.Product is through 300,000,000 nuclear magnetic resonance spectroscopies, and the fourier infrared atlas analysis proves that the phenyl ring on-link mode (OLM) is 1,4 connection, and this polymkeric substance has good position regularity structure.
Embodiment 10: take by weighing 0.55 gram and two hexyloxy benzene and 0.64 are restrained Anhydrous Ferric Chloride put under the mortar room temperature and grind.Grind after 30 minutes stopped reaction.With the product in ethanol or the methanol wash mortar, use the centrifugal mode with solid-liquid separation, to remove iron(ic) chloride and unreacted monomer.With ethanol or methanol wash solid three times, it is dry to put into constant temperature oven (50 ℃) then.After the oven dry, product is dissolved fully, add in 40 milliliters of ethanol, stir with 10 milliliters of chloroforms, polymer precipitation gets off, and carries out centrifugally with solid-liquid separation once more, after anti-constant temperature oven (50 ℃) drying, obtains product poly-(2,5-dialkoxy-1,4-benzene) 0.50 gram, productive rate reaches 90%.The number-average molecular weight that size exclusion chromatography is measured polymkeric substance is 3.2 ten thousand.Through about 404 nanometers of its emission peak of fluorometric analysis, be blue light emitting material.Product is through 300,000,000 nuclear magnetic resonance spectroscopies, and the fourier infrared atlas analysis proves that the phenyl ring on-link mode (OLM) is 1,4 connection, and this polymkeric substance has good position regularity structure.
Embodiment 11: claim 0.5 gram that diethoxybenzene and 1.46 is restrained Anhydrous Ferric Chlorides and put under the mortar room temperature and grind.Grind after 30 minutes stopped reaction.With the product in ethanol or the methanol wash mortar, use the centrifugal mode with solid-liquid separation, to remove iron(ic) chloride and unreacted monomer.With ethanol or methanol wash solid secondary, it is dry to put into constant temperature oven (50 ℃) then.After the oven dry, product is dissolved, join in 40 milliliters the methyl alcohol, stir with 8 milliliters chloroforms, after polymer precipitation gets off, carry out centrifugally separating solid once more, after constant temperature oven (50 ℃) drying, obtain product poly-(2,5-dialkoxy-1,4-benzene) 0.36 gram, productive rate 73%.The number-average molecular weight that size exclusion chromatography is measured polymkeric substance is 30,000.Product is through 300,000,000 nuclear magnetic resonance spectroscopies, and the fourier infrared atlas analysis proves that the phenyl ring on-link mode (OLM) is 1,4 connection, and this polymkeric substance has good position regularity structure.
Embodiment 12: claim 0.5 gram that diethoxybenzene and 1.2 Anhydrous Ferric Chlorides are put under the mortar room temperature and grind.Grind after 25 minutes stopped reaction.With 30 milliliters of washing bottle reactants of dilute hydrochloric acid of 2M,, isolate solid with filter type to remove iron(ic) chloride and unreacted monomer.Water repeatedly washs to neutrality again, puts in the constant temperature oven (50 ℃) product dry.After the oven dry, with 10 milliliters chloroforms product is dissolved, adding four to methyl alcohol that is five times in the chloroform amount or ethanol gets off polymer precipitation, carry out centrifugally once more, after anti-constant temperature oven (50 ℃) drying, obtain product poly-(2 with solid-liquid separation, 5-dialkoxy-1,4-benzene) 0.35 gram, productive rate 71%.Product is through 300,000,000 nuclear magnetic resonance spectroscopies, and the fourier infrared atlas analysis proves that the phenyl ring on-link mode (OLM) is 1,4 connection, and this polymkeric substance has good position regularity structure.
Embodiment 13: take by weighing 0.41 gram p-dimethyoxy benzene and 1.46 and restrain Anhydrous Ferric Chlorides and put under the mortar room temperature and grind.Grind after 30 minutes, stopped reaction is isolated solid with filter type, and with the dilute hydrochloric acid washing solid of 2M, to remove iron(ic) chloride, water repeatedly washs to neutrality again, puts in the constant temperature oven (50 ℃) product dry.After the oven dry, with the least possible chloroform product is dissolved fully, adding four to methyl alcohol that is five times in the chloroform amount or ethanol gets off polymer precipitation, carry out centrifugal once more with solid-liquid separation, after anti-constant temperature oven (50 ℃) drying, obtain product 0.3 gram, productive rate reaches 73,5%.The number-average molecular weight that size exclusion chromatography is measured polymkeric substance is 3.3 ten thousand.Product is through 300,000,000 nuclear magnetic resonance spectroscopies, and the fourier infrared atlas analysis proves that the phenyl ring on-link mode (OLM) is 1,4 connection, and this polymkeric substance has good position regularity structure.
Embodiment 14: take by weighing 0.67 pair two octyloxy benzene and 0,98 the gram Anhydrous Ferric Chlorides put into mortar, grind under the room temperature.Grind after 20 minutes stopped reaction.Filter to isolate solid, with 20 milliliters of washings of dilute hydrochloric acid solid of 2M, to remove iron(ic) chloride and unreacted monomer.Water repeatedly washs again, and to neutrality, it is dry to put into constant temperature oven (50 ℃).After the oven dry, with 10 milliliters chloroforms product is dissolved, join in 40 ml methanol, stir, after polymer precipitation gets off, carry out centrifugally once more, isolate solid, after constant temperature oven (50 ℃) drying, obtain product 0.53 gram, productive rate reaches 80%.Product is through 300,000,000 nuclear magnetic resonance spectroscopies, and the fourier infrared atlas analysis proves that the phenyl ring on-link mode (OLM) is 1,4 connection, and this polymkeric substance has good position regularity structure.
Embodiment 15: take by weighing 0.56 gram and 2 16 alkoxy benzenes and 0.49 are restrained Anhydrous Ferric Chloride put under the mortar room temperature and grind.Grind after 30 minutes stopped reaction.Filter, isolate solid, with 15 milliliters of washing with alcohol.It is dry then solid to be put into constant temperature oven (50 ℃).After the oven dry, with 8 milliliters chloroforms product is dissolved fully, the methyl alcohol or the ethanol that add 40 milliliters get off polymer precipitation, carry out centrifugally with solid-liquid separation once more, after anti-constant temperature oven (50 ℃) drying, obtain product 0.43 gram, and productive rate reaches 77%.Product is through 300,000,000 nuclear magnetic resonance spectroscopies, and the fourier infrared atlas analysis proves that the phenyl ring on-link mode (OLM) is 1,4 connection, and this polymkeric substance has good position regularity structure.
Embodiment 16: take by weighing 0,61 grams 2 18 alkoxy benzenes and 0,49 gram Anhydrous Ferric Chlorides are put under the mortar room temperature and ground.Grind after 25 minutes stopped reaction.With 15 milliliters of washing reaction things of dilute hydrochloric acid of 2M, isolate solid with filter type, to remove iron(ic) chloride and unreacted monomer.Water repeatedly washs to neutrality again, puts in the constant temperature oven (50 ℃) product dry.After the oven dry, with the least possible chloroform product is dissolved fully, adding four to methyl alcohol that is five times in the chloroform amount or ethanol gets off polymer precipitation, carry out centrifugal once more with solid-liquid separation, after anti-constant temperature oven (50 ℃) drying, obtain product 0,36 grams, productive rate reaches 60%.Product is through 300,000,000 nuclear magnetic resonance spectroscopies, and the fourier infrared atlas analysis proves that the phenyl ring on-link mode (OLM) is 1,4 connection, and this polymkeric substance has good position regularity structure.
Claims (6)
1. the preparation method of poly-(2,5-dialkoxy-1,4-benzene) is characterized in that: with the alkoxyl group carbonatoms be 1 to 18 be monomer to dialkoxy benzene, be catalyzer with the metal chloride, under 5～65 ℃, mixed grinding reaction 10 to 30 minutes thick product; Separation, purifying promptly get and gather (2,5-dialkoxy-1,4-benzene); Wherein catalyst consumption is 1 to 4 times of monomer molar amount.
2. preparation method according to claim 1 is characterized in that: catalyzer is rare-earth metal chloride, FeCl
36H
2O, anhydrous CuCl
2, anhydrous FeCl
3Or their mixture.
3. preparation method according to claim 1 is characterized in that: catalyzer is anhydrous FeCl
3
4. preparation method according to claim 1, it is characterized in that: catalyzer and the intact monomer of unreacted are removed in the dilute hydrochloric acid washing that separate, purification step is thick product water, methyl alcohol, ethanol or 1-2M/L, centrifugation or filtration are gathered (2,5-dialkoxy-1,4-benzene).
5. preparation method according to claim 1 is characterized in that: separates, purification step is, with the chloroform dissolving, in alcoholic solvent, precipitates behind the thick product drying, and collecting precipitation, drying is gathered (2,5-dialkoxy-1,4-benzene).
6. preparation method according to claim 5 is characterized in that: alcoholic solvent is methyl alcohol or ethanol.
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