CN1459443A - Gamma-alkyl heteroatom substituted ether and its synthesis method - Google Patents
Gamma-alkyl heteroatom substituted ether and its synthesis method Download PDFInfo
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Abstract
A gamma-heteroatom substituted alkyl ether compound containnig fluorene structure, its synthesizing process, and its application to preparing the catalyst for olefin polymerization are disclosed. As shown in the ganeral formula, R1 and R2 may be the same or not the same, representing 1-20 C atom-contained straight chain or branching alkyl, cycloalkyl, aryl, alkaryl or aralkyl group; A represents S or Z-R3 groups, where Z is N or P and R3 represents H or 1-10 C atom-contained straight chain or branching alkyl, cycloalkyl, aryl, alkaryl or aralkyl group.
Description
Technical field
The present invention relates to a class novel contain fluorene structured gamma-alkyl heteroatom substituted ether compounds, specifically, relate to a class 9-(-oxyl methyl)-9-(sulfenyl methyl) fluorene compound, the application in the preparation olefin polymerization catalysis of the preparation method of this compound and this compound.
Background technology
1, it is known that the 3-diether compounds uses as the electron donor in the olefin polymerization catalyst, for example document CN1298887, CN1143651 disclosed contain fluorene structured 1,3-third diether compounds and contain heteroatomic ring polyenoid 1,3-the third two ether derivants etc.
At present, bibliographical information two kinds of synthetic methods of β--oxyl thio-ether type compounds:
First method is by β--oxyl haloalkane and sodium mercaptides prepared in reaction β--oxyl thioether, as bibliographical information the reaction of 1-chloro-2-Ethoxyethane and sodium methyl mercaptide, generate 1-methylthio group-2-Ethoxyethane (referring to J.Am.Chem.Soc.1955,77,514).
Second method is with beta-hydroxy thioether and haloalkane, under alkaline condition, etherification reaction takes place, and generates corresponding β--oxyl thioether (referring to Bull.Chem.Soc.Jpn.1984,57 (7), 1863).Used beta-hydroxy thioether generally is to be reacted by beta-hydroxy haloalkane and sodium mercaptides to prepare (referring to J.Am.Chem.Soc., 1928,50,2446), or prepares (referring to J.Org.Chem.1967,32,1717) by methyl thioether and aldehyde reaction.
But γ--oxyl thio-ether type compounds and synthetic method thereof are not appeared in the newspapers.The inventor has proposed novel 9-(-oxyl methyl)-9-(sulfenyl methyl) fluorene compound of a class, and this compound is the special γ of a class--oxyl thio-ether type compounds.
If prepare γ--oxyl thioether, then need at first to prepare intermediate γ--oxyl haloalkane with first method.The synthetic needed intermediate γ of 9-(-oxyl methyl) 9-(hydrocarbon thiomethyl) fluorene compound--oxyl haloalkane is 9-(-oxyl methyl)-9-(halogenated methyl) fluorenes.This intermediate need be synthesized through monoetherization and halogenation two-step reaction by dibasic alcohol, but the inventor recognizes through repetition test, dibasic alcohol 9, single etherate (as 9-(methoxymethyl)-9-(methylol) fluorenes) of two (methylol) fluorenes of 9-is difficult to generate 9-(-oxyl methyl)-9-(halogenated methyl) fluorenes with the halide reagent reaction.
If prepare γ--oxyl thioether, then need at first to prepare intermediate γ-hydroxyl thioether with second method.Synthetic 9-(-oxyl the methyl)-needed intermediate γ of 9-(sulfenyl methyl) fluorene compound-hydroxyl thioether, be 9-(hydroxymethyl)-9-(sulfenyl methyl) fluorenes, it need be reacted by 9-(hydroxymethyl)-9-(halogenated methyl) fluorenes and sodium mercaptides and prepare.But 9-(hydroxymethyl)-9-(halogenated methyl) fluorenes is difficult to synthetic.
Because there is above-mentioned shortcoming in the synthetic method of prior art, therefore the inventor has proposed a kind of easier, practical synthetic method, by 1, the ammediol compounds synthesizes γ--oxyl thio-ether type compounds, and this compound is applied to olefin polymerization catalysis as electron donor.
Summary of the invention
Ether compound with following general formula (I):
Wherein, R
1, R
2Can be identical or different, represent straight chain or branched-alkyl, cycloalkyl, aryl, alkaryl or the aralkyl of 1～20 carbon atom; Preferred R
1, R
2Representative has the alkyl of 1-4 carbon atom, as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-etc.; More preferably R
1, R
2Be methyl;
A represents S or Z-R
3Group, wherein Z is N or P, R
3Represent hydrogen or straight chain or branched-alkyl, cycloalkyl, aryl, alkaryl or the aralkyl of 1-10 carbon atom arranged, and can with R
2Be keyed to ring; Preferred R
3Represent hydrogen or the alkyl of 1-4 carbon atom arranged, and can with R
2Be keyed to ring; More preferably R
3Represent hydrogen or methyl.
Preferred compound is that A represents Z-R
3Group, wherein Z is N or P, R
1Be methyl, R
3With R
2Be keyed to five-ring or six-ring.
Ether compound of the present invention can specifically be selected from following example:
9-(methoxyl methyl)-9-(methyl thiomethyl) fluorenes;
9-(methoxyl methyl)-9-(ethyl thiomethyl) fluorenes;
9-(methoxyl methyl)-9-(n-propyl thiomethyl) fluorenes;
9-(methoxyl methyl)-9-(sec.-propyl thiomethyl) fluorenes;
9-(methoxyl methyl)-9-(normal-butyl thiomethyl) fluorenes;
9-(methoxyl methyl)-9-(isobutyl-thiomethyl) fluorenes;
9-(methoxyl methyl)-9-(tertiary butyl thiomethyl) fluorenes;
9-(methoxyl methyl)-9-(cyclopentyl thiomethyl) fluorenes;
9-(methoxyl methyl)-9-(cyclohexyl thiomethyl) fluorenes;
9-(methoxyl methyl)-9-(phenyl thiomethyl) fluorenes;
9-(methoxyl methyl)-9-(p-methylphenyl thiomethyl) fluorenes;
9-(methoxyl methyl)-9-(phenmethyl thiomethyl) fluorenes;
9-(methoxyl methyl)-9-[(dimethyl) amino methyl] fluorenes;
9-(methoxyl methyl)-9-[(1-hexahydropyridine base) methyl] fluorenes;
9-(methoxyl methyl)-9-[(1-Pyrrolidine base) methyl] fluorenes;
9-(methoxyl methyl)-9-[(1-phosphorus heterocycle amyl group) methyl] fluorenes;
9-(methoxyl methyl)-9-[(1-phosphorus heterocycle cyclohexyl) methyl] fluorenes etc.
Compound 9-of the present invention (-oxyl methyl)-9-(sulfenyl methyl) fluorenes is by 9, two (methylol) fluorenes of 9-carry out the monohydroxy etherification reaction with haloalkane earlier, 9-(-oxyl methyl)-9-(methylol) fluorenes that generates again with the sulphonic acid chloride reaction, the last and mercaptan of product 9-(-oxyl methyl)-9-(sulphonyl oxygen methyl) fluorenes carries out nucleophilic substitution reaction and obtains.
Other gamma-alkyl heteroatom substituted ethers of the present invention can use similar method synthetic.
9, two (methylol) fluorenes of 9-can prepare according to various known synthetic methods, can be referring to ActaChemica Scandinavia 1967,21,718-720.
Method of the present invention may further comprise the steps: the monoether reaction of (1) dibasic alcohol
In anhydrous and inert atmosphere, with solvent, with the corresponding dibasic alcohol of general formula (I), halohydrocarbon R
1X and alkali add reactor, react, and obtain corresponding monoether 9-(-oxyl methyl)-9-(methylol) fluorenes, wherein, and R
1Representative and the identical group of general formula (I) definition,
X represents Cl, Br and I,
The mol ratio of halohydrocarbon and dibasic alcohol is 1～10: 1, is preferably 2～5: 1,
The mol ratio of alkali and dibasic alcohol is 0.5～1.5: 1, is preferably 0.8～1.2: 1,
Used alkali is the hydride or the oxyhydroxide of basic metal or alkaline-earth metal, as sodium hydride, hydrolith, sodium hydroxide, calcium hydroxide etc., is preferably sodium hydride and sodium hydroxide, and preferably adds gradually after dibasic alcohol, haloalkane and solvent add again,
Preferred used solvent is selected from tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), ether, dimethyl formamide, aliphatic hydrocarbon such as pentane, hexane, heptane or aromatic hydrocarbons such as benzene, toluene etc. or their mixture; (2) sulfonylation with the monoether of step (1) gained and SULPHURYL CHLORIDE in the presence of solvent and alkali; in temperature of reaction is-20～100 ℃; preferably-5 ℃～react under the room temperature; obtain 9-(-oxyl methyl)-9-(sulphonyl oxygen methyl) fluorenes; wherein, alkali is mineral alkali or organic bases, as sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, triethylamine, Trimethylamine, tributylamine or pyridine etc.; be preferably triethylamine
The solvent that uses can be selected from halohydrocarbon, hydrocarbon, ether or their mixture, as methylene dichloride, trichloromethane, tetracol phenixin, benzene, toluene, tetrahydrofuran (THF) or their mixture, is preferably ethylene dichloride,
The mol ratio of monoether and SULPHURYL CHLORIDE is 1: 1～2, and preferred monoether: alkali: the mol ratio of SULPHURYL CHLORIDE is 1: 1～1.3: 1～1.3; (3) nucleophilic substitution reaction
With 9-(-oxyl methyl)-9-(sulphonyl oxygen methyl) fluorenes of step (2) gained, in the presence of alkali, be under 0～200 ℃ in temperature, under preferred 0～100 ℃, react with mercaptan, obtain 9-(-oxyl methyl)-9-(sulfenyl methyl) fluorenes,
Wherein, alkali is basic metal M, alkalimetal hydride MH, alkali-metal oxyhydroxide MOH, alkali-metal alkoxide MOR (R represents the alkyl of C1-C5) or alkaline carbonate M
2CO
3, be preferably basic metal M or/and its carbonate M
2CO
3,
The solvent that uses can be selected from dimethyl sulfoxide (DMSO), dimethyl formamide, hexamethylphosphoramide, acetonitrile, acetone, ethanol, toluene, benzene or their mixture,
The mol ratio of 9-(-oxyl methyl)-9-(sulphonyl oxygen methyl) fluorenes and mercaptan is 1: 1～5, and preferred mol ratio is 9-(-oxyl methyl)-9-(sulphonyl oxygen methyl) fluorenes: mercaptan: alkali=1: 2.5～5: 2.5～5.
The invention discloses novel cpd 9-(-oxyl methyl)-9-(sulfenyl methyl) fluorenes and intermediate 9-(-oxyl methyl)-9-(sulphonyl oxygen methyl) fluorenes thereof, its structure can be confirmed by mass spectroscopy, 1H nuclear magnetic resonance spectroscopy, results of IR.Compound of the present invention be can be applicable to prepare polypropylene catalyst as internal electron donor, aspect improving activity of such catalysts and controlling polyacrylic degree of isotacticity, have good performance; Also can be extended to part is used in other catalyzer.
Embodiment
The preparation of embodiment 19-(methoxymethyl)-9-(methylol) fluorenes
In anhydrous and nitrogen atmosphere, add 80ml tetrahydrofuran (THF) (THF), 22.6g 9 successively, two (methylol) fluorenes of 9-and 57g methyl iodide, stirring makes fully and mixes.At room temperature, during 2 hours in, add 4.6g content in batches and be 52% sodium hydride, add the back and stirred 2 hours continuing.
Reclaim unreacted methyl iodide by distillation, dilute remaining material with 100ml water, with extracted with diethyl ether twice, each consumption 100ml.Merge ether extraction liquid, add anhydrous sodium sulfate drying.Behind the dried diethyl ether solution evaporate to dryness, obtain the thick product of 22.8g.Behind column chromatographic isolation and purification, obtain 14.9g 9-(methoxymethyl)-9-(methylol) fluorenes, yield 62%.
1H-NMR(CDCl
3/TMS)δ(ppm)：3.40(s，3H，-OCH
3)，3.71(s，2H，-CH
2O-)，3.96(s，2H，-CH
2O-)，7.31(t，2H，2ArH)，7.41(t，2H，2ArH)，7.65(d，2H，2ArH)，7.75(d，2H，2ArH)。
The preparation of embodiment 29-(methoxymethyl)-9-(sulphonyl oxygen methyl) fluorenes
5.45g 9-(methoxymethyl)-9-(methylol) fluorenes is dissolved in the 50ml methylene dichloride.Solution is cooled to-5～0 ℃, adds 4ml triethylamine and 2.2ml methylsulfonyl chloride successively, stirring reaction 6 hours.Then, reaction solution water, saturated aqueous solution of sodium bicarbonate washing respectively.The organic layer of telling is used anhydrous sodium sulfate drying again after washing, concentrate, and obtains 14.2g 9-(methoxymethyl)-9-(sulphonyl oxygen methyl) fluorenes (yield 96%), mp70～72 ℃.
1H-NMR(CDCl
3/TMS)δ(ppm)：2.85(s，3H，-OSO
2CH
3)，3.40(s，3H，-OCH
3)，3.60(s，2H，-CH
2O-)，4.50(s，2H，-CH
2OSO
2-)，7.32(t，2H，J＝7.6Hz，2ArH)，7.43(t，2H，J＝7.2，7.6Hz，2ArH)，7.64(d，2H，J＝7.6Hz，2ArH)，7.75(d，2H，J＝7.2Hz，2ArH)。
The preparation of embodiment 39-(methoxymethyl)-9-(ethyl thiomethyl) fluorenes
Under nitrogen protection, 18ml exsiccant toluene and 1g sodium Metal 99.5 are added in the reaction flask, add the 6.8ml sulfur alcohol again.Be stirred to the sodium Metal 99.5 loss for reaction under the room temperature.Dropwise 5 .8g 9-(methoxymethyl)-9-(sulphonyl oxygen methyl) fluorenes is dissolved in the solution of 58ml dimethyl formamide (DMF).Reaction solution reacted 24 hours down for 40 ℃ in oil bath, again in 60～72 ℃ of reactions 7 hours.Be chilled to room temperature, add 120ml toluene and 120ml deionized water, jolting divides water-yielding stratum.Water layer is again with the extraction of 76ml toluene.The combining methylbenzene layer washes with water, uses anhydrous sodium sulfate drying then, concentrates, and gets 4.6g 9-(methoxymethyl)-9-(ethyl thiomethyl) fluorenes (yield 88.6%), mp80～81.Mass spectroscopy (EI) m/e:284 (M
+).
1H-NMR(CDCl
3/TMS)δ(ppm)：1.10(t，3H，J＝7.4Hz，-CH
3)，2.30(q，2H，J＝7.4Hz，-CH
2-)，3.22(s，2H，-CH
2Ar)，3.34(s，3H，-OCH
3)，3.58(s，2H，-CH
2O-)，7.30(t，2H，J＝1.0，7.5Hz，2ArH)，7.37(t，2H，J＝1.1，7.6Hz，2ArH)，7.65(d，2H，J＝7.6Hz，2ArH)，7.73(d，2H，J＝7.5Hz，2ArH)。
Embodiment 4
1. the preparation of solid ingredient in the catalyst system
In through the abundant metathetical reactor of high pure nitrogen, add magnesium chloride 4.8g successively, toluene 95ml, epoxy chloropropane 4ml, tributyl phosphate 12.5ml is warming up to 50 ℃ under stirring, and kept 2.5 hours, solid dissolves fully, adds Tetra hydro Phthalic anhydride 1.4g, continues to keep 1 hour.Solution is cooled to below-25 ℃, drips TiCl in 1 hour
456ml, slowly be warming up to 80 ℃, in temperature-rise period, separate out solids gradually, 9-(methoxymethyl)-9-(ethyl thiomethyl) fluorenes 1.7g that adding embodiment 3 prepares is as the internal electron donor compound, holding temperature 1 hour after the filtration, adds toluene 70ml, the washing secondary obtains solid sediment.Add toluene 60ml then, TiCl
440ml is warmed up to 100 ℃ and handled 2 hours, after the venting filtrate, adds toluene 60ml again, TiCl
440ml is warmed up to 100 ℃ and handled venting filtrate 2 hours.Add toluene 60ml boiling attitude washing 5 minutes, triplicate adds hexane 60ml again, and boiling attitude washed twice adds hexane 60ml, after the washed twice, obtains the 5.9g solid ingredient under the normal temperature.
2. polymerization experiment
Volume is the stainless steel cauldron of 5L, after gaseous propylene is fully replaced, adds AlEt32.5mmol, methylcyclohexyl dimethoxy silane (CHMMS) 0.1mmol, add 1 solid ingredient 10mg that obtains and 0.18MPa hydrogen again, feed liquid propene 2.3L, be warming up to 70 ℃, kept this temperature 1 hour, pressure is put in cooling, obtains the PP resin, catalyst activity is 12500gPP/gCat., the polyacrylic degree of isotacticity 94.0% of gained.
Embodiment 5
1. the preparation of solid ingredient in the catalyst system
Only 100 ℃ of titaniums among the embodiment 4 are handled in Preparation of Catalyst and changed into 0.5 hour in 2 hours, all the other conditions are identical with embodiment 4, obtain the 6.4g solid ingredient.
2. polymerization experiment
Add the 1 solid ingredient 10mg that obtains, all the other conditions are with embodiment 4, and catalyst activity is 18800gPP/gCat., the degree of isotacticity 95.4% of resulting polymers.
Claims (12)
1. ether compound with following formula:
Wherein: R
1, R
2Can be identical or different, representative has straight chain or branched-alkyl, cycloalkyl, aryl, alkaryl or the aralkyl of 1-20 carbon atom; A represents S or Z-R
3Group, wherein Z is N or P, R
3Represent hydrogen or straight chain or branched-alkyl, cycloalkyl, aryl, alkaryl or the aralkyl of 1-10 carbon atom arranged, and can with R
2Be keyed to ring.
2. according to the ether compound of claim 1, R wherein
1, R
2Representative has the alkyl of 1-4 carbon atom; A is Z-R
3, wherein Z is N or P, R
3Represent hydrogen or the alkyl of 1-4 carbon atom arranged, and can with R
2Be keyed to ring.
3. according to the ether compound of claim 2, R wherein
1, R
2Be methyl, R
3Represent hydrogen or methyl.
4. according to the ether compound of claim 2, R wherein
1Be methyl, R
3With R
2Be keyed to five-ring or six-ring.
5. according to the ether compound of claim 1, R wherein
1, R
2Representative has the alkyl of 1-4 carbon atom, and A is S.
6. according to the ether compound of claim 1, can be selected from following compounds:
9-(methoxyl methyl)-9-(methyl thiomethyl) fluorenes,
9-(methoxyl methyl)-9-(ethyl thiomethyl) fluorenes,
9-(methoxyl methyl)-9-(n-propyl thiomethyl) fluorenes,
9-(methoxyl methyl)-9-(sec.-propyl thiomethyl) fluorenes,
9-(methoxyl methyl)-9-(normal-butyl thiomethyl) fluorenes,
9-(methoxyl methyl)-9-(isobutyl-thiomethyl) fluorenes,
9-(methoxyl methyl)-9-(tertiary butyl thiomethyl) fluorenes,
9-(methoxyl methyl)-9-(cyclopentyl thiomethyl) fluorenes,
9-(methoxyl methyl)-9-(cyclohexyl thiomethyl) fluorenes,
9-(methoxyl methyl)-9-(phenyl thiomethyl) fluorenes,
9-(methoxyl methyl)-9-(p-methylphenyl thiomethyl) fluorenes,
9-(methoxyl methyl)-9-(phenmethyl thiomethyl) fluorenes,
9-(methoxyl methyl)-9-[(dimethyl) amino methyl] fluorenes,
9-(methoxyl methyl)-9-[(1-hexahydropyridine base) methyl] fluorenes,
9-(methoxyl methyl)-9-[(1-Pyrrolidine base) methyl] fluorenes,
9-(methoxyl methyl)-9-[(1-phosphorus heterocycle amyl group) methyl] fluorenes,
9-(methoxyl methyl)-9-[(1-phosphorus heterocycle cyclohexyl) methyl] fluorenes.
7. according to the preparation method of the ether compound of claim 1, may further comprise the steps: the monoether reaction of (1) dibasic alcohol
In anhydrous and inert atmosphere, with solvent, with the corresponding dibasic alcohol of general formula (I), halohydrocarbon R
1X and alkali add reactor, react, and obtain corresponding monoether 9-(-oxyl methyl)-9-(methylol) fluorenes, wherein, and R
1Representative and the identical group of general formula (I) definition,
X represents Cl, Br and I,
Alkali is the hydride or the oxyhydroxide of basic metal or alkaline-earth metal,
The mol ratio of halohydrocarbon and dibasic alcohol is 1～10: 1,
The mol ratio of alkali and dibasic alcohol is 0.5～1.5: 1; (2) sulfonylation
The monoether of step (1) gained and SULPHURYL CHLORIDE in the presence of solvent and alkali, are reacted under for-20～100 ℃ in temperature of reaction, obtain 9-(-oxyl methyl)-9-(sulphonyl oxygen methyl) fluorenes,
Wherein, alkali is mineral alkali or organic bases,
The solvent that uses can be selected from halohydrocarbon, hydrocarbon, ether or their mixture,
The mol ratio of monoether and SULPHURYL CHLORIDE is 1: 1～2; (3) substitution reaction
With 9-(-oxyl methyl)-9-(sulphonyl oxygen methyl) fluorenes of step (2) gained, in the presence of alkali, be under 0～200 ℃ in temperature, react with mercaptan, obtain 9-(-oxyl methyl)-9-(sulfenyl methyl) fluorenes,
Wherein, alkali is basic metal M, alkalimetal hydride MH, alkali-metal oxyhydroxide MOH, (R represents C to alkali-metal alkoxide MOR
1-C
5Alkyl) or alkaline carbonate M
2CO
3,
The solvent that uses can be selected from dimethyl sulfoxide (DMSO), dimethyl formamide, hexamethylphosphoramide, acetonitrile, acetone, ethanol, toluene, benzene or their mixture,
The mol ratio of 9-(-oxyl methyl)-9-(sulphonyl oxygen methyl) fluorenes and mercaptan is 1: 1～5.
8. R among the preparation method according to claim 7, wherein said step (1)
1The mol ratio of X and dibasic alcohol is 2～5: 1; The mol ratio of alkali and dibasic alcohol is 0.8～1.2: 1; Used alkali is sodium hydride or sodium hydroxide, and adds gradually after dibasic alcohol, halohydrocarbon and solvent add again; Used solvent is selected from tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), ether, dimethyl formamide, aromatic hydrocarbons or C
5-C
10Aliphatic hydrocarbon or their mixture.
9. the mol ratio of monoether and alkali is 1: 1～1.3 among the preparation method according to claim 7, wherein said step (2); The mol ratio of monoether and SULPHURYL CHLORIDE is 1: 1～1.3; Used alkali is sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, triethylamine, Trimethylamine, tributylamine or pyridine; Used solvent is selected from methylene dichloride, trichloromethane, tetracol phenixin, benzene, toluene, tetrahydrofuran (THF) or their mixture; Temperature of reaction is-5 a ℃～room temperature.
10. preparation method according to claim 9, wherein used alkali is triethylamine in the step (2), used solvent is an ethylene dichloride.
11. the mol ratio of 9-(-oxyl methyl) among the preparation method according to claim 7, wherein said step (3)-9-(sulphonyl oxygen methyl) fluorenes and mercaptan is 1: 2.5～5; The mol ratio of 9-(-oxyl methyl)-9-(sulphonyl oxygen methyl) fluorenes and alkali is 1: 2.5～5; Used alkali is that basic metal M is or/and its carbonate M
2CO
3Temperature of reaction is 0～100 ℃.
12. according to the application of the described compound of one of claim 1-6 in the preparation olefin polymerization catalysis.
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100389112C (en) * | 2004-12-16 | 2008-05-21 | 中国石油化工股份有限公司 | cyclic acetal and ketal compound and application thereof |
| CN109382135A (en) * | 2018-11-05 | 2019-02-26 | 大连理工大学 | A method of the polycyclic hydro carbons jet fuel of high density is prepared by fluorenes |
-
2002
- 2002-05-24 CN CNB021179379A patent/CN1189440C/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100389112C (en) * | 2004-12-16 | 2008-05-21 | 中国石油化工股份有限公司 | cyclic acetal and ketal compound and application thereof |
| CN109382135A (en) * | 2018-11-05 | 2019-02-26 | 大连理工大学 | A method of the polycyclic hydro carbons jet fuel of high density is prepared by fluorenes |
| CN109382135B (en) * | 2018-11-05 | 2020-12-11 | 大连理工大学 | Method for preparing high-density polycyclic hydrocarbon jet fuel from fluorene |
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