CN103664469B - Cyclopentadiene-containing star-shaped compound and preparation method thereof - Google Patents
Cyclopentadiene-containing star-shaped compound and preparation method thereof Download PDFInfo
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- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 150000001875 compounds Chemical class 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 150000001555 benzenes Chemical class 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 239000012044 organic layer Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- CLRIMWMVEVYXAK-UHFFFAOYSA-N 5-ethylcyclopenta-1,3-diene Chemical compound CCC1C=CC=C1 CLRIMWMVEVYXAK-UHFFFAOYSA-N 0.000 claims description 4
- PMZBHPUNQNKBOA-UHFFFAOYSA-N 5-methylbenzene-1,3-dicarboxylic acid Chemical group CC1=CC(C(O)=O)=CC(C(O)=O)=C1 PMZBHPUNQNKBOA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- XKEFYDZQGKAQCN-UHFFFAOYSA-N 1,3,5-trichlorobenzene Chemical compound ClC1=CC(Cl)=CC(Cl)=C1 XKEFYDZQGKAQCN-UHFFFAOYSA-N 0.000 claims description 3
- YWDUZLFWHVQCHY-UHFFFAOYSA-N 1,3,5-tribromobenzene Chemical compound BrC1=CC(Br)=CC(Br)=C1 YWDUZLFWHVQCHY-UHFFFAOYSA-N 0.000 claims description 2
- 241001597008 Nomeidae Species 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 31
- 238000006116 polymerization reaction Methods 0.000 abstract description 15
- 229920000642 polymer Polymers 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 6
- 150000002910 rare earth metals Chemical class 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 150000001993 dienes Chemical class 0.000 abstract description 4
- 239000006085 branching agent Substances 0.000 abstract description 2
- 150000004820 halides Chemical class 0.000 abstract 1
- 150000007529 inorganic bases Chemical class 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 18
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- -1 for tackifier Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 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 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000002815 homogeneous catalyst Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 4
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 0 *C1C=CC=C1 Chemical compound *C1C=CC=C1 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910000091 aluminium hydride Inorganic materials 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- SJVNEEBSDQEBOA-UHFFFAOYSA-N [Nd].C(CCCCCCCC)(=O)O Chemical compound [Nd].C(CCCCCCCC)(=O)O SJVNEEBSDQEBOA-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- ACOLQZDYRBEHEV-UHFFFAOYSA-K decanoate;neodymium(3+) Chemical compound [Nd+3].CCCCCCCCCC([O-])=O.CCCCCCCCCC([O-])=O.CCCCCCCCCC([O-])=O ACOLQZDYRBEHEV-UHFFFAOYSA-K 0.000 description 1
- LWSVQEVRIASCOZ-UHFFFAOYSA-N decanoic acid;neodymium Chemical compound [Nd].CCCCCCCCCC(O)=O LWSVQEVRIASCOZ-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N diisobutylaluminium hydride Substances CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- QWUGXIXRFGEYBD-UHFFFAOYSA-M ethylmercuric chloride Chemical compound CC[Hg]Cl QWUGXIXRFGEYBD-UHFFFAOYSA-M 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a star-shaped compound containing cyclopentadiene and a preparation method thereof. Reacting cyclopentadiene and its derivative with star-shaped halide under the action of inorganic base to prepare a cyclopentadiene-containing star-shaped compound. The preparation method of the cyclopentadiene-containing star compound disclosed by the invention is simple in synthesis process, high in yield, easy in obtaining of raw materials and mild in reaction conditions. The cyclopentadiene-containing star compound disclosed by the invention can be used as a branching agent to prepare a star rare earth catalyst in the preparation reaction of the rare earth catalyst for conjugated diene polymerization, so that a star branched polymer is prepared, and the viscosity of a polymer solution is reduced.
Description
Technical field
The present invention relates to class star compound and preparation method thereof, relate in particular to a class and contain star compound of cyclopentadiene and preparation method thereof.
Background technology
Cyclopentadiene contains unsaturated conjugated double bond, chemical property is very active, can carry out being polymerized, hydrogenation, halogenation, addition, the reaction such as condensation and reduction, be mainly used in synthetic rubber and petroleum resin, purposes is as follows: with cyclopentadiene and dicyclopentadiene for Third monomer synthesizes ethylene-propylene rubber(EPR); Cyclopentadiene and dicyclopentadiene thermopolymerization, can obtain petroleum resin, for tackifier, softening agent, coating, sanitas and ink etc.; The synthesis etc. of metallocene catalyst for olefine polymerization is used for as part.
When cyclopentadiene is used for olefinic polymerization metallocene catalyst synthetic ligands, according to the difference of catalyst structure, be divided into monocyclopentadienyl coordination system and bridge-type many cyclopentadienyl ligand system.As CN1461757 discloses a kind of monocyclopentadienyl polyolefin catalyst and preparation method thereof.This catalyzer coordinates with aluminum alkyls or aluminum alkoxide and is used for olefinic polymerization, can obtain the polymkeric substance of high molecular and wide molecular weight distribution.
CN101935366A discloses a kind of for reducing melt index and the biscyclopentadienyl catalyst system increasing polymer-through-out rate, the invention provides the polymerization process of bifunctional catalyst system and these bifunctional catalyst systems of employing.Disclosed polymerization process can be higher productivity produce olefin polymer, and these olefin polymers can have higher molecular weight and/or lower melt index.
CN96101442.3 discloses the preparation method by the Dicyclopentadiene (DCPD) based compound of single carbon atom bridge joint, and it comprises makes carbonyl compound and cyclopentadienyl compounds react under a kind of alkali exists.Can be used for preparing ansa-metallocene with the compound that high yield obtains by the simple single stage method of this invention, it is the active catalyst component in olefin polymerization process.
CN96110141.5 discloses a kind of preparation technology of carbon-bridged dicyclic pentylene compound, this technique uses at least one alkali and a kind of phase-transfer catalyst, one or both cyclopentadiene compounds and a kind of carbonyl compound are reacted, the bridge dicyclopentadiene part that final synthesis obtains, will be used for the preparation of the olefin copolymer with elastic performance.
And bridge-type three cyclopentadienyl compounds seldom adopts in the preparation process of alkene catalyst.Consider the chemically reactive of cyclopentadiene and the star structure of bridge-type three cyclopentadienyl compounds, can predict that this compounds will have good application prospect at non-linear synthetic rubber and petroleum resin field.
Summary of the invention
The object of the invention is proposition one class and contain star compound of cyclopentadiene and preparation method thereof.Such compound synthesis technology is simple, and productive rate is higher, and raw material is easy to get, and reaction conditions is gentle.
Specifically, a class disclosed in this invention is containing the star compound of cyclopentadiene, and its general structure is such as formula shown in I:
(formula I)
Wherein R
1for H, the one in methyl or ethyl;
A class disclosed in this invention is containing the preparation method of the star compound of cyclopentadiene, and its step is as follows:
Under argon shield, cyclopentadiene or derivatives thereof is dissolved in tetrahydrofuran (THF), then adds mineral alkali, heated and stirred backflow 0.5 ~ 2h, then adds trihalogenated benzene, continues backflow 0.5 ~ 3h in reaction system.After cooling, reaction solution is transferred in separating funnel, adds ethyl acetate, organic layer washed with water three times.By organic layer under reduced pressure evaporate to dryness, solid with ethyl acetate recrystallization, obtains clear crystal.The mol ratio of mineral alkali and cyclopentadiene and derivative thereof is (0.3 ~ 1.3): 1, and the mol ratio of trihalogenated benzene and cyclopentadiene and derivative thereof is (0.1 ~ 0.6): 1.
In above-mentioned preparation method, described cyclopentadiene derivant is 5-methyl isophthalic acid, the one in 3-cyclopentadiene or 5-ethyl-1，3-cyclopentadiene.
In above-mentioned preparation method, described mineral alkali is NaH or CaH
2in one.
In above-mentioned preparation method, described trihalogenated benzene is the one in 1,3,5-trichlorobenzene or 1,3,5-tribromo-benzene.
Beneficial effect of the present invention is:
A class disclosed in this invention is containing the preparation method of the star compound of cyclopentadiene, and its synthesis technique is simple, and productive rate is higher, and raw material is easy to get, and reaction conditions is gentle.
A class disclosed in this invention, containing the star compound of cyclopentadiene, at conjugate diene polymerization with in rare earth catalyst preparation feedback, can be used as branching agent and prepares star-like rare earth catalyst (shown in II), wherein
for polyisoprene segments, Nd is catalyst activity point, and in the course of the polymerization process, conjugated diene carries out chainpropagation along this star-like catalyst activity point, finally obtains the polymerisate in star-branched structure; Do not reduce in maintenance rare earth catalyst activity, under the narrow and suitable Isosorbide-5-Nitrae-structural content of molecular weight distribution is greater than the prerequisite of 98%, significantly can reduces the soltion viscosity of polymkeric substance, bring convenience to processes such as the heat transfer in industrial production, conveying, glue spraying and cohesions.
(formula II)
Embodiment
Following examples are further described feature of the present invention, but protection scope of the present invention is not by the restriction of these embodiments.
1, Main Analysis characterizing method
The limiting viscosity of polymkeric substance utilizes dark type viscometer to test at 30 DEG C, and using toluene as solvent, calculation formula is [η]=[2 (η
sp-ln η
r)]
1/2/ c, wherein η
r=t/t
0, η
spη
r-1, t is concentration is the flowing time of the polymkeric substance toluene solution of c, t
0for the flowing time of toluene; Middle average molecular weight (the M of multipolymer
w) and molecular weight distribution (M
w/ M
n) utilize gel permeation chromatography (GPC) to characterize, take polystyrene standards as calibration curve; Suitable Isosorbide-5-Nitrae-the structural content of multipolymer utilizes fourier infrared (FTIR) to characterize.Nucleus magnetic resonance
1h NMR data come from BrukerAC-300 nuclear magnetic resonance analyser, and chemical shift δ unit is ppm, is inside designated as tetramethylsilane.
2, raw material specification and source
Divinyl, isoprene Petrochina Lanzhou Petrochemical Company, polymerization-grade;
High and new technology industrial development zone, carboxylic acid neodymium Ningbo Yu Ling Chemical Industry Science Co., Ltd, 0.5M hexane solution;
Aluminum alkyls and alkyl-al hydride Nanjing communications and liaison Chemical Co., Ltd., purity > 97%;
Alkyl aluminum halide lark prestige Science and Technology Ltd., 0.8M hexane solution;
Other reagent AlfaAesar (Tianjin) Chemical Co., Ltd., SILVER REAGENT.
Embodiment 1
Formula I syntheti c route is as follows:
Its step is as follows:
Work as R
1for methyl: under argon shield; tetrahydrofuran (THF) (150mL) is added successively, 5-methyl isophthalic acid, 3-cyclopentadiene (24g in 250mL round-bottomed bottle; 300mmol); NaH(7.92g, 330mmol) after induction stirring reflux 1h, then add 1; 3; 5-tribromo-benzene (28.3g, 90mmol), continues backflow 2h.After cooling, reaction solution is transferred in separating funnel, and adds ethyl acetate (200mL), organic layer washed with water three times (each 50mL).By organic solvent under reduced pressure evaporate to dryness, solid with ethyl acetate recrystallization, obtains clear crystal (26.7g, yield 95%).Nucleus magnetic resonance:
1h-NMR(300MHz, CDCl
3, ppm): δ 1.56(s, 9H, CH
3), 6.25(d, 6H, CH), 6.35(t, 6H, CH), 6.90(s, 3H, PhH).
Work as R
1for H: step is the same, and now raw material is 1，3-cyclopentadiene, yield 90%.Nucleus magnetic resonance:
1h-NMR(300MHz, CDCl
3, ppm): δ 4.02(d, 3H, CH), 6.21(t, 6H, CH) and, 6.32(t, 6H, CH), 6.82(s, 3H, PhH).
Work as R
1for ethyl: step is the same, and now raw material is 5-ethyl-1，3-cyclopentadiene, yield 93%.Nucleus magnetic resonance:
1h-NMR(300MHz, CDCl
3, ppm): δ 0.82(t, 9H, CH
3), 1.53(q, 6H, CH
2), 6.33(d, 6H, CH), 6.43(t, 6H, CH), 6.96(s, 3H, PhH).
Embodiment 2
Formula I syntheti c route is as follows:
Work as R
1for methyl: under argon shield, add tetrahydrofuran (THF) (20mL) successively in 50mL round-bottomed bottle, 5-methyl isophthalic acid, 3-cyclopentadiene (4g, 50mmol), CaH
2after (1.3g, 30mmol) induction stirring reflux 0.8h, then add 1,3,5-trichlorobenzene (2.7g, 15mmol), continue backflow 1.5h.After cooling, reaction solution is transferred in separating funnel, and adds ethyl acetate (70mL), organic layer washed with water three times (each 50mL).By organic solvent under reduced pressure evaporate to dryness, solid with ethyl acetate recrystallization, obtains clear crystal, obtains clear crystal (4.3g, yield 92%).
Work as R
1for H: step is the same, and now raw material is 1，3-cyclopentadiene, yield 90%.
Work as R
1for ethyl: step is the same, and now raw material is 5-ethyl-1，3-cyclopentadiene, yield 96%.
Embodiment 3
Under argon shield, in the catalyzer configuration bottle of drying, add 0.03mmol neodymium iso-octanate, 0.75mmol triisobutyl aluminium, 0.15mmol diethyl aluminium hydride, 0.09mmol diethylaluminum chloride, 0.3mmol isoprene, 0.02mmol formula I (R
1for methyl) mix after in 25 DEG C of ageing 60min, prepare homogeneous catalyst, for subsequent use.
Under argon shield, add the cyclohexane solution of 0.3mol divinyl in the polymerization reactor of drying, then add the above catalyst solution prepared, catalyst component is a) 1 × 10 with the mol ratio of monomer
-4.Be polymerized after 5 hours at 50 DEG C, add the ethanolic soln termination reaction of the BHT of 1wt%, washing is placed in 45 DEG C of vacuum drying ovens and is dried to constant weight, and polymer yield is 89.0%, weight-average molecular weight (M
w) be 6 × 10
5, molecular weight distributing index (M
w/ M
n) be 1.9, polymkeric substance is 98.3% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 2.4dL/g.
Comparative example 3
In catalyst preparation process, replace formula I with toluene, other condition is with embodiment 3.Polymer yield is 89.7%, weight-average molecular weight (M
w) be 5.7 × 10
5, molecular weight distributing index (M
w/ M
n) be 2.4, polymkeric substance is 98.3% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 3.2dL/g.
Embodiment 4
Under argon shield, in the catalyzer configuration bottle of drying, add 0.036mmol n-nonanoic acid neodymium, 0.6mmol triisobutyl aluminium, 0.4mmol hydrogenation dibutyl aluminium, 0.08mmol di-isobutyl aluminum chloride, 0.8mmol isoprene, 0.06mmol formula I (R
1for ethyl) mix after in 27 DEG C of ageing 50min, prepare homogeneous catalyst, for subsequent use.
Under argon shield, add the cyclohexane solution of 0.6mol divinyl in the polymerization reactor of drying, then add the above catalyst solution prepared, catalyst component is a) 6 × 10 with the mol ratio of monomer
-5.Be polymerized after 4 hours at 55 DEG C, add the ethanolic soln termination reaction of the BHT of 1wt%, washing is placed in 45 DEG C of vacuum drying ovens and is dried to constant weight, and polymer yield is 85.0%, weight-average molecular weight (M
w) be 8.3 × 10
5, molecular weight distributing index (M
w/ M
n) be 1.6, polymkeric substance is 98.7% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 3.3dL/g.
Comparative example 4
In catalyst preparation process, replace formula I with vinyl benzene, other condition is with embodiment 4.Polymer yield is 84.5%, weight-average molecular weight (M
w) be 8.0 × 10
5, molecular weight distributing index (M
w/ M
n) be 1.7, polymkeric substance is 98.8% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 3.7dL/g.
Embodiment 5
Under argon shield, in the catalyzer configuration bottle of drying, add 0.02mmol neodymium caprate, 0.8mmol diisobutylaluminium hydride, 0.03mmol sesquialter ethylmercury chloride aluminium, 0.1mmol isoprene, 0.1mmol formula I (R
1for H) mix after in 35 DEG C of ageing 60min, prepare homogeneous catalyst, for subsequent use.
Under argon shield, add the cyclohexane solution of 1mol isoprene in the polymerization reactor of drying, then add the above catalyst solution prepared, catalyst component is a) 2 × 10 with the mol ratio of monomer
-5.Be polymerized after 5 hours at 70 DEG C, add the ethanolic soln termination reaction of the BHT of 1wt%, washing is placed in 45 DEG C of vacuum drying ovens and is dried to constant weight, and polymer yield is 92.0%, weight-average molecular weight (M
w) be 7.3 × 10
5, molecular weight distributing index (M
w/ M
n) be 1.7, polymkeric substance is 98.9% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 2.2dL/g.
Comparative example 5
In catalyst preparation process, replace formula I with dimethylbenzene, other condition is with embodiment 5.Polymer yield is 91.5%, weight-average molecular weight (M
w) be 9.0 × 10
5, molecular weight distributing index (M
w/ M
n) be 2.8, polymkeric substance is 98.8% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 3.0dL/g.
Embodiment 6
Under argon shield, in the catalyzer configuration bottle of drying, add 0.05mmol capric acid neodymium, 0.25mmol tri-butyl aluminum, 1.5mmol diethyl aluminium hydride, 0.15mmol chlorination dibutyl aluminium, 1.25mmol isoprene, 0.1mmol formula I (R
1for methyl) mix after in 20 DEG C of ageing 30min, prepare homogeneous catalyst, for subsequent use.
Under argon shield, add the cyclohexane solution of 0.25mol divinyl in the polymerization reactor of drying, then add the above catalyst solution prepared, catalyst component is a) 2 × 10 with the mol ratio of monomer
-4.Be polymerized after 4.5 hours at 40 DEG C, add the ethanolic soln termination reaction of the BHT of 1wt%, washing is placed in 45 DEG C of vacuum drying ovens and is dried to constant weight, and polymer yield is 80.0%, weight-average molecular weight (M
w) be 4.5 × 10
5, molecular weight distributing index (M
w/ M
n) be 2.1, polymkeric substance is 99.0% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 2.6dL/g.
Comparative example 6
In catalyst preparation process, replace formula I with Vinylstyrene, other condition is with embodiment 6.Polymer yield is 79.5%, weight-average molecular weight (M
w) be 4.2 × 10
5, molecular weight distributing index (M
w/ M
n) be 2.1, polymkeric substance is 98.9% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 3.3dL/g.
Embodiment 7
Under argon shield, in the catalyzer configuration bottle of drying, add 0.01mmol neodymium iso-octanate, 0.05mmol triethyl aluminum, 0.30mmol hydrogenation dibutyl aluminium, 0.04mmol di-isobutyl aluminum chloride, 0.05mmol isoprene, 0.15mmol formula I (R
1for methyl) mix after in 25 DEG C of ageing 45min, prepare homogeneous catalyst, for subsequent use.
Under argon shield, add the cyclohexane solution of 0.05mol divinyl and 0.05mol isoprene in the polymerization reactor of drying, then add the above catalyst solution prepared, catalyst component is a) 1 × 10 with the mol ratio of monomer
-4.Be polymerized after 5.5 hours at 80 DEG C, add the ethanolic soln termination reaction of the BHT of 1wt%, washing is placed in 45 DEG C of vacuum drying ovens and is dried to constant weight, and polymer yield is 78.0%, weight-average molecular weight (M
w) be 6.5 × 10
5, molecular weight distributing index (M
w/ M
n) be 1.6, polymkeric substance is 98.2% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 3.0dL/g.
Comparative example 7
In catalyst preparation process, replace formula I with naphthalene, other condition is with embodiment 7.Polymer yield is 79.0%, weight-average molecular weight (M
w) be 6.2 × 10
5, molecular weight distributing index (M
w/ M
n) be 2.6, polymkeric substance is 98.1% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 4.0dL/g.
As can be seen from above embodiment and comparative example result, such is containing the preparation method of the star compound of cyclopentadiene, and its synthesis technique is simple, and productive rate is higher, and raw material is easy to get, and reaction conditions is gentle.Relative to prior art, the star-like rare earth catalyst prepared by star compound of the present invention is used in conjugate diene polymerization process, do not reduce at maintenance catalyst activity, molecular weight distribution is narrow and along 1, under 4-structural content is greater than the prerequisite of 98%, significantly can reduce the soltion viscosity of polymkeric substance.
Claims (5)
1. a class is containing the star-like compound of cyclopentadiene, and its general structure is such as formula shown in I:
Wherein R
1for H, the one in methyl or ethyl.
2. the preparation method of a star-like compound according to claim 1, it is characterized in that comprising the following steps: under argon shield, cyclopentadiene or derivatives thereof is dissolved in tetrahydrofuran (THF), then mineral alkali is added, heated and stirred backflow 0.5 ~ 2h, then in reaction system, trihalogenated benzene is added, continue backflow 0.5 ~ 3h, after cooling, reaction solution is transferred in separating funnel, add ethyl acetate, organic layer washed with water three times, by organic layer under reduced pressure evaporate to dryness, solid with ethyl acetate recrystallization, obtain clear crystal, the mol ratio of mineral alkali and cyclopentadiene or derivatives thereof is (0.3 ~ 1.3) ︰ 1, the mol ratio of trihalogenated benzene and cyclopentadiene or derivatives thereof is (0.1 ~ 0.6) ︰ 1.
3. preparation method according to claim 2, is characterized in that described cyclopentadiene derivant is 5-methyl isophthalic acid, the one in 3-cyclopentadiene or 5-ethyl-1，3-cyclopentadiene.
4. preparation method according to claim 2, is characterized in that described mineral alkali is NaH or CaH
2in one.
5. preparation method according to claim 2, is characterized in that described trihalogenated benzene is the one in 1,3,5-trichlorobenzene or 1,3,5-tribromo-benzene.
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| IT1272924B (en) * | 1995-01-23 | 1997-07-01 | Spherilene Srl | PROCEDURE FOR THE PREPARATION OF CYCLOPENTADIENYL COMPOUNDS AND COMPOUNDS SO OBTAINABLE |
| DE19523595A1 (en) * | 1995-06-30 | 1997-01-02 | Hoechst Ag | Process for the preparation of a carbon-bridged biscyclopentadiene compound |
| US6177603B1 (en) * | 1998-06-12 | 2001-01-23 | Bridgestone Corporation | Organo zinc and rare earth catalyst system in the polymerization of conjugated dienes |
| DE19951841A1 (en) * | 1999-10-28 | 2001-05-03 | Bayer Ag | Catalyst based on rare earth compounds |
| CN1182158C (en) * | 2002-05-31 | 2004-12-29 | 中国石油化工股份有限公司 | Single metallocene polyolefine catalyst and its preparation method |
| US8329834B2 (en) * | 2009-06-29 | 2012-12-11 | Chevron Phillips Chemical Company Lp | Dual metallocene catalyst systems for decreasing melt index and increasing polymer production rates |
| CN102115509B (en) * | 2010-12-31 | 2012-07-04 | 大连理工大学 | Starlike branched polybutadiene of rare earth catalyst system and preparation method thereof |
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