CN1046125C - Preparation method of dicyclopentadienyl titanium dichloride - Google Patents
Preparation method of dicyclopentadienyl titanium dichloride Download PDFInfo
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- CN1046125C CN1046125C CN97108117A CN97108117A CN1046125C CN 1046125 C CN1046125 C CN 1046125C CN 97108117 A CN97108117 A CN 97108117A CN 97108117 A CN97108117 A CN 97108117A CN 1046125 C CN1046125 C CN 1046125C
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- titanium dichloride
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- dicyclic pentylene
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical compound [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 title abstract 4
- 239000002904 solvent Substances 0.000 claims abstract description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000746 purification Methods 0.000 claims abstract description 20
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 9
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 46
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 23
- 238000000605 extraction Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 15
- 125000002619 bicyclic group Chemical group 0.000 claims description 15
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 claims description 15
- 229960001701 chloroform Drugs 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 10
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 9
- OHUVHDUNQKJDKW-UHFFFAOYSA-N sodium;cyclopenta-1,3-diene Chemical compound [Na+].C=1C=C[CH-]C=1 OHUVHDUNQKJDKW-UHFFFAOYSA-N 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 230000003292 diminished effect Effects 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000004576 sand Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 238000005336 cracking Methods 0.000 claims description 2
- -1 dicyclic pentylene titanium dichlorides Chemical class 0.000 claims description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 7
- 238000007086 side reaction Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 229910003074 TiCl4 Inorganic materials 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000008096 xylene Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 15
- KKDBZWZRJNRBGA-UHFFFAOYSA-L Cl[Ti]Cl.[CH]1C=CC=C1 Chemical compound Cl[Ti]Cl.[CH]1C=CC=C1 KKDBZWZRJNRBGA-UHFFFAOYSA-L 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 238000009835 boiling Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000006837 decompression Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 241000256844 Apis mellifera Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KNQKQKFWNSSXEV-UHFFFAOYSA-N O1CCCC1.C1(C=CC=C1)[Na] Chemical compound O1CCCC1.C1(C=CC=C1)[Na] KNQKQKFWNSSXEV-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011175 product filtration Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The invention discloses a preparation method of dicyclopentadienyl titanium dichloride (namely dicyclopentadienyl titanium dichloride), which uses dicyclopentadiene as a raw material and toluene, xylene or ethylbenzene as a solvent, wherein the adding amount of the dicyclopentadienyl titanium dichloride is 100-1000 ml/100 g TiCl4. The invention solves the problems of low yield, long purification time, environmental pollution and the like, has the advantages of less side reaction, high yield, low production cost, short purification time, less environmental pollution and the like, and is widely suitable for the fields of chemical industry, medicine and the like.
Description
The present invention relates to a kind of dicyclic pentylene titanium dichloride and (be commonly called as cyclopentadienyl titanium dichloride, molecular formula: (C
5H
5)
2TiCl
2) the preparation method.
In the prior art, external " Organometallic Sytheses ", VOl.1, P75, AcademicPress (1965) have reported a kind of synthetic and method of purification.This method be at first dicyclopentadiene at N
2Protection Pintsch process down is the cyclosiloxane monomer pentadiene, the cyclopentadiene of distillation preparation just is added drop-wise in the there-necked flask of tetrahydrofuran (THF) (perhaps glycol dimethyl ether) solvent that sodium sand is housed, at N
2Under the atmosphere sodium sand is fully reacted completely, prepare the cyclopentadienyl sodium tetrahydrofuran (THF) of (being called for short luxuriant sodium) (perhaps ethylene glycol monomethyl ether) solution thus, then, be added drop-wise in the flask that dry benzene and titanium tetrachloride are housed and react, the reaction product filtration under diminished pressure, filter cake is utilized apparatus,Soxhlet's, with trichloromethane is that solvent extracts repeatedly, separates out red crystallization after the extraction liquid cooling, filters and also uses the alkane washing precipitation, air drying gets product, and yield is greater than 50%.For purifying, available trichloromethane recrystallization, 289～291 ℃ of the molten points of product use benzene as solvent when this method is synthetic, and yield is on the low side, and benzene is very harmful to human body.Purification is to use trichloromethane as solvent, and apparatus,Soxhlet's is extracting repeatedly, and a collection of production life cycle of purifying is very long, and trichloromethane is volatile, and loss amount is big, and it is higher to make it cost, and has caused the serious environmental pollution.
Domestic, chemical reagent, 1983,5 (6), 363～379 have reported a kind of synthetic and method of purification, and this method is cracked into the cyclosiloxane monomer pentadiene to dicyclopentadiene and prepares the tetrahydrofuran solution of cyclopentadienyl sodium thus and aforementioned external report the same, and different is at N
2Protection the tetrahydrofuran solution that cyclopentadienyl is received, is added drop-wise to and reacts in the flask that tetrahydrofuran (THF) and titanium tetrachloride are housed down, and reaction product is carried out filtration under diminished pressure, gets filter cake.Be solvent with the filter cake trichloromethane then,, extracting solution at room temperature placed a few hours after-filtration, get red cyclopentadienyl titanium dichloride crystal with apparatus,Soxhlet's extracting repeatedly.Be to improve purity, available chloroform or be that solvent carries out extraction second time with toluene, yield can reach 60%.In this synthetic method, cancelled benzene, all adopted tetrahydrofuran (THF), reduced the pollution of benzene, helped protecting environment environment as solvent as solvent, but because of tetrahydrofuran (THF) as this synthetic solvent, need use LiALH earlier
4Handle, to remove wherein superoxide and moisture, step is more in distillation (collecting 65～66 ℃ of cuts) then.Tetrahydrofuran (THF) is more expensive and the volatilization loss amount is big, has caused synthetic cost higher.Method of purification is the same with external method of purification, utilizes apparatus,Soxhlet's, uses trichloromethane as extraction agent, trichloromethane is volatile, loss amount is big, the cost for purification height, environmental pollution is serious, this method preparation and the product of purifying, detect with abroad the infrared standard spectrogram of Pfaltz Bauer company is consistent through infrared spectrometer, fusing point is 289 ℃, ultimate analysis: C content 47.81%, H content 4.12%, Ti content 19.20%, Cl content 28.45%.
The objective of the invention is to overcome the defective that prior art exists, use new solvent and extraction agent, to improve product yield, reduce cost, shorten the purification time, improve plant capacity, to avoid environmental pollution, the purity of product is reached more than 99% (weight).
In order to achieve the above object; the present invention has adopted following technical scheme: earlier with dicyclopentadiene cracking system cyclopentadiene; in tetrahydrofuran solution, produce cyclopentadienyl sodium then with the sodium sand reaction; the gained mixed solution is handled by the following method: (1) uses toluene; one of dimethylbenzene or ethylbenzene or its mixture as solvent; by 100 100～1000 milliliters of solvents of gram titanium tetrachlorides; solvent and titanium tetrachloride are placed reactor; in nitrogen protection; under stirring and the cooling conditions; slowly add the cyclopentadienyl sodium solution by metering; reacted under the room temperature 1～3 hour; reclaim solvent; adopt low-temperature reduced-pressure to steam to doing to the greatest extent; (2) use N then; dinethylformamide; N; a kind of or its mixed solution of N-N,N-DIMETHYLACETAMIDE is made extraction agent; use 100～300 milliliters of extraction agents by 10 gram dicyclic pentylene titanium dichlorides; extraction agent is added in the reactor; stir, dicyclic pentylene titanium dichloride is fully dissolved, filtration under diminished pressure; again filtrate heating and underpressure distillation are done to most; cooling with alkane or aromatic hydrocarbons washing, is filtered; the trichloromethane crystallization gets red dicyclic pentylene titanium dichloride.
In aforesaid operating process, must add solvent and extraction agent by described measures range, promptly its add-on is not too high or too low.The amount of solvent is very little the time, and its side reaction is many, and heat effect is big, and temperature of reaction is wayward; Solvent adds when too much, and its side reaction also can increase, and the yield of dicyclic pentylene titanium dichloride product is reduced.When the consumption of extraction agent is crossed when low, incomplete to the dissolving of product, yield is reduced; There is no need to use too much extraction agent, consumption too much not only can cause unnecessary waste, also can make the aftertreatment quantitative change big, has increased the load of aftertreatment.
The present invention's technical scheme preferably can be: in preparation dicyclic pentylene titanium dichloride process, the adding mode of cyclopentadienyl sodium solution is slowly to drip, because the thermal discharge of reaction is big, adopt the slow dropping can controls reaction speed, avoid the temperature rise of reaction system too high, adopt slow dropping mode, be aided with water quench (the available where necessary refrigerated water of bigger device) simultaneously, temperature that can the stopping reaction system, and at room temperature reacted 1～3 hour, reach good technical effect.
The present invention's technical scheme preferably also can be: extraction agent gradation used in the purification process adds, generally can divide 2～3 addings as one sees fit, because the dicyclic pentylene titanium dichloride in the extraction agent gradation dissolution reactor of same amount is than once dissolving is more complete, better effects if is beneficial to the yield that improves product.
Compared with prior art, the present invention has following tangible advantage:
1, yield height: replace benzene with toluene, dimethylbenzene or ethylbenzene as solvent when synthetic, than replacing benzene with tetrahydrofuran (THF), energy is controls reaction speed effectively, reduce side reaction, improve the yield of cyclopentadienyl titanium dichloride, its yield is up to more than 70%, and the employing prior art, the yield of cyclopentadienyl titanium dichloride only reaches 50%～60%;
2, cost is low: the toluene boiling point is high 30～40 ℃ than benzene and tetrahydrofuran (THF), and when distillation was reclaimed, loss amount was little, is convenient to recycle, and has reduced synthetic cost, and its cost only is about half of prior art;
3, the purification time is short: use N during purification, dinethylformamide or N, the N-N,N-DIMETHYLACETAMIDE is as extraction agent, because of they are big to the solubleness of cyclopentadienyl titanium dichloride more than trichloromethane to the solubleness of cyclopentadienyl titanium dichloride, and selectivity will be got well, and therefore, does not need to extract repeatedly with apparatus,Soxhlet's, shorten the purification time, reduced purification step.The purification time of product of the present invention is generally in 5 hours, and required purification time of existing technology is all more than 12 hours;
4, environmental pollution is few: N, and dinethylformamide and N,N-dimethylacetamide moderate boiling point, volatilization, loss amount is little, and when having reduced cost for purification, environmental pollution also significantly reduces.
Below the present invention is described in further detail by specific embodiment.
Embodiment 1
100～180ml tetrahydrofuran (THF) and 5.8 gram sodium sands are housed in a 500ml four-hole boiling flask, this four-hole boiling flask is installed in the thermostatic water-circulator bath device, fill with cold water, load onto logical N
2Device, agitator, reflux condensing tube, dropping funnel.At N
2Protection is stirred down, slowly splashes into the 20～30ml cyclopentadiene and the 20～40ml tetrahydrofuran (THF) mixed solution that are newly distilled by Pintsch process; after dripping off, reacted 2～3 hours down, obtain cyclopentadienyl sodium (being commonly called as luxuriant sodium) solution thus at 30～40 ℃; this solution is red; then, under nitrogen protection, in the 1000ml reaction flask; add 25～250ml dry toluene and 25 gram titanium tetrachlorides; the cyclopentadienyl sodium solution for preparing is slowly splashed in this reaction flask, and the cold water cooling is stirred.Add in stirring at room reaction 1～3 hour.Reclaim solvent, adopt low-temperature reduced-pressure to steam to doing to the greatest extent.With 250～750ml N, dinethylformamide joins in the container at twice, fully dissolves contained cyclopentadienyl titanium dichloride, and filtration under diminished pressure is collected filtrate.Utilize the thermostatic water-circulator bath device, heating is under the decompression (condition of high vacuum degree), decompression steams N, dinethylformamide, cooling adds 50～100ml cyclohexane cleaning product, pour B then into, filtration under diminished pressure is used the trichloromethane crystallization then, and vacuum-drying gets product cyclopentadienyl titanium dichloride 22.04 grams, yield is 70.20%, and infrared spectrometer detects its infrared spectrogram and abroad Pfaltz﹠Bauer company infrared spectra standard spectrogram is consistent.DT-30 type differential thermal analyzer carries out differential thermal analysis, absorption peak occurs at 289.5 ℃, and this absorbs honeybee is (C
5H
5)
2TiCl
2Due to the fusion strong endothermic, so fusing point is 289.5 ℃, liquid chromatogram measuring purity is 99.43%, and ultimate analysis C is 47.83%, H is 4.09%, and Ti is 19.21%, Cl be 28.42% and theoretical value C be 48.28%, H is 4.05%, and Ti is 19.24%, and Cl is 28.28% approaching.The purification time of this example is 4.8 hours.
Embodiment 2
With dimethylbenzene (contain the neighbour,, contraposition) make solvent, make extraction agent with N,N-dimethylacetamide, its add-on, working method, operational condition be all with example 1, dicyclic pentylene titanium dichloride product 22.11 grams, yield is 70.42%.By aforementioned analysis determining method, its result: 290.3 ℃ of fusing points, purity 99.47%, ultimate analysis C is 48.02%, and H is 4.07%, and Ti is 19.22%, and Cl is 28.39%.
Embodiment 3
Make solvent with ethylbenzene, use N, dinethylformamide and N,N-dimethylacetamide mixture are made extraction agent, and its add-on, working method and operational condition get dicyclic pentylene titanium dichloride product 22.01 grams all with example 1, and yield is 70.10%.By the analysis determining method of example 1, its result: fusing point is 289.9 ℃, and purity is 99.37%.Ultimate analysis C is 48.19%, and H is 4.04%, and Ti is 19.18%, and Cl is 28.30%.
Embodiment 4
Make solvent with toluene and ethyl benzene mixtures, use N, dinethylformamide is made extraction agent, and its add-on, working method and operational condition get dicyclic pentylene titanium dichloride product 22.17 grams all with example 1, and yield is 70.61%.By the analysis determining method of example 1, its result: 290.1 ℃ of fusing points, purity 99.26%.Ultimate analysis C is 48.13%, and H is 4.06%, and Ti is 19.20%, and Cl is 28.22%.
Embodiment 5 (Comparative Examples)
The preparation of the preparation of cyclopentadienyl titanium dichloride and embodiment 1 is all consistent on raw material input amount and synthetic method.But when purifying, without N, dinethylformamide or N, the N-N,N-DIMETHYLACETAMIDE is divided into four parts to the solid of the solution decompression evaporate to dryness gained in the reactor, each portion that moves into, put into apparatus,Soxhlet's, extract repeatedly with the 500ml trichloromethane, united extraction liquid concentrates extracting solution, separate out red crystals, filter and with alkane wash crystallization thing, vacuum, dry must product, yield is greater than 70%.It is extraction agent extracting repeatedly with the trichloromethane that this embodiment utilizes apparatus,Soxhlet's, and the purification spended time was than long 8 hours of embodiment 1 spended time.Infrared spectrogram and Pfaltz﹠amp; Bauer company standard spectrogram unanimity.DT-30 type differential thermal analyzer test fusing point is 290 ℃, and liquid chromatography test content is 99.15%, and ultimate analysis C is 48.11%, and H is 4.07%, and Ti is 19.21%, and Cl is 28.35%.
Claims (3)
1, a kind of preparation method of dicyclic pentylene titanium dichloride, earlier with dicyclopentadiene cracking system cyclopentadiene, in tetrahydrofuran solution, produce cyclopentadienyl sodium then with the sodium sand reaction, mixed solution in solvent with titanium tetrachloride reaction, through purify dicyclic pentylene titanium dichloride, the invention is characterized in:
(1) with one of toluene, dimethylbenzene or ethylbenzene or its mixture as solvent; by 100 100～1000 milliliters of solvents of gram titanium tetrachlorides; solvent and titanium tetrachloride are placed reactor; under nitrogen protection, stirring and cooling conditions; slowly add the cyclopentadienyl sodium solution by metering, reacted under the room temperature 1～3 hour, reclaim solvent; adopt low-temperature reduced-pressure to steam to doing to the greatest extent, then
(2) use N, a kind of or its mixed solution of dinethylformamide, N,N-dimethylacetamide is made extraction agent, use 100～300 milliliters of extraction agents by 10 gram dicyclic pentylene titanium dichlorides, extraction agent is added in the reactor, stir, dicyclic pentylene titanium dichloride is fully dissolved, filtration under diminished pressure is done cooling with filtrate heating and underpressure distillation again to most, with alkane or aromatic hydrocarbons washing, filter, use the trichloromethane crystallization, get red dicyclic pentylene titanium dichloride.
2, preparation method according to claim 1 is characterized in that preparing in the dicyclic pentylene titanium dichloride process, and the adding mode of cyclopentadienyl sodium solution is slowly to drip.
3, preparation method according to claim 1 and 2 is characterized in that the used extraction agent gradation of purification process adds.
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| CN97108117A CN1046125C (en) | 1997-06-21 | 1997-06-21 | Preparation method of dicyclopentadienyl titanium dichloride |
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|---|---|---|---|
| CN97108117A CN1046125C (en) | 1997-06-21 | 1997-06-21 | Preparation method of dicyclopentadienyl titanium dichloride |
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| CN1046125C true CN1046125C (en) | 1999-11-03 |
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| KR100936349B1 (en) * | 2006-11-23 | 2010-01-12 | 주식회사 엘지화학 | Novel synthesis method of metal cyclopetadienide in bulk |
| CN104262411A (en) * | 2014-10-13 | 2015-01-07 | 岳阳市金茂泰科技有限公司 | Synthesis method of metallocene compound (C5H5)2MCl2 |
| CN108440606B (en) * | 2018-04-02 | 2020-09-29 | 湖北医药学院 | Method for synthesizing titanocene dichloride |
| CN111825728B (en) * | 2020-07-16 | 2022-11-04 | 苏州欣溪源新材料科技有限公司 | Dichlorodicyclopentadienyl tungsten complex and preparation method and application thereof |
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Non-Patent Citations (3)
| Title |
|---|
| ORGANOMETALLIC SYNTHESIS VOL.1 1965.1.1 R.BRUCE KING ACADEMIC PRESS INC * |
| ORGANOMETALLIC SYNTHESIS VOL.1 1965.1.1 R.BRUCE KING ACADEMIC PRESS INC;化学试剂1983，第5卷第6期 P363-366 1983.1.1 李文郁等，"二氯二茂钛的合成及其钛，氯含量的测定" * |
| 化学试剂1983，第5卷第6期 P363-366 1983.1.1 李文郁等，"二氯二茂钛的合成及其钛，氯含量的测定" * |
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| CN1170725A (en) | 1998-01-21 |
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