CN1467232A - Catalyst for preparing syndiotactic polystyrene - Google Patents
Catalyst for preparing syndiotactic polystyrene Download PDFInfo
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- CN1467232A CN1467232A CNA021124493A CN02112449A CN1467232A CN 1467232 A CN1467232 A CN 1467232A CN A021124493 A CNA021124493 A CN A021124493A CN 02112449 A CN02112449 A CN 02112449A CN 1467232 A CN1467232 A CN 1467232A
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- Prior art keywords
- catalyzer
- syndiotactic polystyrene
- cyclopentadienyl
- alkylaluminoxane
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- 229920010524 Syndiotactic polystyrene Polymers 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 title abstract description 15
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 12
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 8
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical group CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 10
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 claims description 8
- 150000003609 titanium compounds Chemical class 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 125000005234 alkyl aluminium group Chemical group 0.000 abstract 1
- SRKKQWSERFMTOX-UHFFFAOYSA-N cyclopentane;titanium Chemical compound [Ti].[CH]1C=CC=C1 SRKKQWSERFMTOX-UHFFFAOYSA-N 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 46
- 238000006243 chemical reaction Methods 0.000 description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 description 7
- 230000006698 induction Effects 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- -1 organo-metallic titanium compound Chemical class 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- LZQHZOIDAMYHSS-UHFFFAOYSA-N [F].[Ti] Chemical compound [F].[Ti] LZQHZOIDAMYHSS-UHFFFAOYSA-N 0.000 description 2
- HQRTUZASZSPFOU-UHFFFAOYSA-N [Ti].[Br] Chemical compound [Ti].[Br] HQRTUZASZSPFOU-UHFFFAOYSA-N 0.000 description 2
- IAYXVNDWLLVXOK-UHFFFAOYSA-N [Ti].[I] Chemical compound [Ti].[I] IAYXVNDWLLVXOK-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- KQDJTBPASNJQFQ-UHFFFAOYSA-N 2-iodophenol Chemical compound OC1=CC=CC=C1I KQDJTBPASNJQFQ-UHFFFAOYSA-N 0.000 description 1
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 1
- RHMPLDJJXGPMEX-UHFFFAOYSA-N 4-fluorophenol Chemical compound OC1=CC=C(F)C=C1 RHMPLDJJXGPMEX-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- MCJUWBUSIQXMPY-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1 MCJUWBUSIQXMPY-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A catalyst for preparing the syndiotactic polystyrene features use of cyclopentadienyl titanium compound R1Ti(OR2R3)3, alkyl aluminoxyane and alkylaluminium, where R1 is cyclopentadienyl or the substituted cyclopentadienyl whose ring contains 1-5 substituents, R2 is phenyl, and R3 is F, Br or I. Its advantages are high catalytic activity and high catalytic efficiency.
Description
Technical field
The present invention relates to prepare the catalyzer of syndiotactic polystyrene.
Background technology
Styrene polymer can be divided into random polystyrene (aPS), isotactic polyphenylacetylene (iPS) and syndiotactic polystyrene (sPS).The catalyst system that synthesis of syndiotactic polystyrene adopts organo-metallic titanium compound and poly-methylaluminoxane (MAO) to form usually, wherein organometallic compound mainly is a cyclopentadiene titanium compound.It is CpTiCl that document EP 210615, US5252693, JP0291104 and EP389981 etc. have reported structure
3/ MAO, Cp
*TiCl
3/ MAO catalyst system is used for the situation of syndiotactic polymerization of phenylethylene, but its catalytic activity and catalytic efficiency are not high, and industrial application is undesirable.
Summary of the invention
Technical problem to be solved by this invention is to overcome catalytic activity and the not high problem of catalytic efficiency that exists in the above-mentioned document, and a kind of catalyzer of new preparation syndiotactic polystyrene is provided, and this catalyzer has advantages of high catalytic activity and catalytic efficiency.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyzer for preparing syndiotactic polystyrene comprises metallocene titanium compound I and alkylaluminoxane II:
R
1Ti(OR
2R
3)
3 I
R in the formula
1For containing 1～5 C on cyclopentadienyl or the ring
1～C
4The cyclopentadienyl of alkyl substituent;
R
2For containing the aryl of 6～10 carbon atoms;
R
3Be fluorine, bromine or iodine;
R
4For containing the alkyl of 1～4 carbon atom;
N is the oligomerisation degree of alkylaluminoxane, and its value is 6～40;
Wherein the aluminium among the alkylaluminoxane II is 50～2000 to the mole ratio of metallocene titanium compound I, Ti and R
2Between have Sauerstoffatom to link to each other.
The preferred value of oligomerisation degree n is 10～30 in the technique scheme, and the catalyzer preferred version is also to contain aluminum alkyls component III in the catalyzer, is AlX
3, X is the alkyl of 1～4 carbon atom, and preferred version is the triisobutyl aluminium component, and with the molar ratio computing aluminum alkyls: alkylaluminoxane is 0.1～3, R
1Preferred version be cyclopentadienyl or pentamethyl-cyclopentadienyl, more preferably scheme is the pentamethyl-cyclopentadienyl.R
2Preferred version be phenyl.R
3Preferred version be that the position that is selected from fluorine, bromine or iodine is contraposition.
Poly-alkylaluminoxane is prepared by control hydrolysis by aluminum alkyls.Reactants water can be the water that contains in the inorganic salt of crystal water, and the inorganic salt that contain crystal water can be CaCl
26H
2O, MgCl
26H
2O, CuSO
45H
2O, CaSO
42H
2O, Al
2(SO
4)
318H
2O, MgSO
47H
2O, FeSO
47H
2O, Ti (SO
4)
24H
2O, Ti
2(SO
4)
38H
2O and ZnSO
47H
2O etc.Trimethyl aluminium (TMA) is 1: 1～1: 3 with the mole ratio of water, and temperature of reaction is-20～100 ℃, and the reaction times is 10～40 hours.Aluminum alkyls commonly used has trimethyl aluminium, triethyl aluminum, triisobutyl aluminium etc.Concrete steps are: aluminum alkyls is pressed Al/H
2The O mole ratio is slowly to be added dropwise to Al in 1: 1～1: 2 under-20～0 ℃
2(SO
4)
318H
2In the toluene mixture liquid of O, the dropping time is 0.5～4 hour.Reaction 5～40 hours is continued in elevated temperature to 20～100 ℃ gradually under this temperature then.Reaction mixture is solids removed by filtration under nitrogen protection, and solvent evaporated under reduced pressure gets white solid product, promptly obtains the alkylaluminoxane that structure is II.
The preparation method of metallocene titanium compound I is as follows: is that solvent reaction make with the hydrocarbon polymer by corresponding cyclopentadienyl titanous chloride and corresponding substituent phenolic compound in the presence of chlorine hydride absorbent.Chlorine hydride absorbent can be various aminated compoundss, wherein is advisable with trialkylamine, for example triethylamine.Hydrocarbon polymer can be aliphatic hydrocarbon or aromatic hydrocarbon, uses aromatic hydrocarbon better, for example benzene, toluene etc.Concrete steps are: the mixing solutions of triethylamine and corresponding substituent phenolic compound is slowly dropped in the benzole soln of corresponding cyclopentadienyl titanous chloride, the mole ratio of corresponding cyclopentadienyl titanous chloride and corresponding substituent phenolic compound is 1.0: 3.0, the mole ratio of corresponding cyclopentadienyl titanous chloride and triethylamine is 1.0: 3.0～4.0, temperature of reaction is 1～130 ℃, 2～48 hours reaction times.Solids removed by filtration under protection of inert gas, underpressure distillation are removed and to be desolvated, and the crude product that obtains is with toluene/hexane double solvents recrystallization, remove volatile matter after, the xanchromatic crystal.
Its data are as follows:
Work as R
1Be pentamethyl-cyclopentadienyl, R
2Be phenyl, R
3Structural formula of compound is during for the contraposition fluorine:
Learn that through hydrogen nuclear magnetic resonance spectrogram and infrared spectra map analysis structure is the said structure formula.
Its data are as follows:
Ultimate analysis (element analysis)
C
28H
27O
3F
3Ti：
Calcd.For (calculated value)
C 65.11％
H 5.23％
F 11.04％
Found (measured value)
C 65.06％
H 5.30％
F 10.97％
The proton nmr spectrum
[HNMR CDCl
3TMS intern (interior mark)]
δ6.55～7.00(m，12H，-(OPhHF)
3)
δ2.0～2.15(s，15H，Cp-CH
3)
(m/e, %intensity), intensity is an abundance to mass spectroscopy MS
516(36.99，M)
517(43.13，M+1)
406 (100, M-OPhF) work as R
1Be pentamethyl-cyclopentadienyl, R
2Be phenyl, R
3Structural formula of compound is during for the contraposition bromine:
Learn that through hydrogen nuclear magnetic resonance spectrogram and infrared spectra map analysis structure is the said structure formula.Its data are as follows:
Ultimate analysis (element analysis)
C
28H
27O
3Br
3Ti：
Calcd.For (calculated value)
C?48.07％
H 3.86％
Br?18.83％
Found (measured value)
C 48.16％
H 4.13％
Br?17.71％
The proton nmr spectrum
[HNMR CDCl
3TMS intern (interior mark)]
δ6.55～7.35(m，12H，-(OPhHBr)
3)
δ1.9～2.15(s，15H，Cp-CH
3)
(m/e, %intensity), intensity is an abundance to mass spectroscopy MS
699(37.75，M)
700(34.15，M+1)
527 (100, M-OPhBr) work as R
1Be pentamethyl-cyclopentadienyl, R
2Be phenyl, R
3Structural formula of compound is during for contraposition iodine:
Learn that through hydrogen nuclear magnetic resonance spectrogram and infrared spectra map analysis structure is the said structure formula.Its data are as follows:
Ultimate analysis (element analysis)
C
28H
27O
3I
3Ti：
Calcd.For (calculated value)
C?40.00％
H?3.21％
I?45.36％
Found (measured value)
C 40.12％
H 3.47％
I 44.10％
The proton nmr spectrum
[HNMR CDCl
3TMS intern (interior mark)]
δ6.55～7.50(m，12H，-(OPhHI)
3)
δ2.0～2.15(s，15H，Cp-CH
3)
(m/e, %intensity), intensity is an abundance to mass spectroscopy MS
840(8.92，M)
841(3.72，M+1)
220(100，-OPhI)
621(24.44％，M-OphI)
This metallocene titanium compound I and alkylaluminoxane II add the aluminum alkyls component again by the simple catalyzer that promptly can be used as syndiotactic polymerization of phenylethylene that mixes in the catalyzer, effect is better.
Catalyst component III and vinylbenzene can be under protection of inert gas (for example nitrogen, argon gas etc.) under 0～50 ℃, preferably 30 ℃ are mixed earlier.
Polyreaction is preferably carried out between 50～90 ℃ under 30～1100 ℃.In order to obtain the polymkeric substance of ideal performance, polymerization needs the regular hour, and by several hours, preferably 0.1～3 hour, the ideal polymerization time depended on polymerization temperature, solvent and other polymerizing condition from several minutes.The polyreaction mode can adopt solution polymerization, slurry polymerization and mass polymerization.For solution polymerization and slurry polymerization, the solvent of employing is aliphatic hydrocarbon or aromatic hydrocarbon, as hexane, heptane, hexanaphthene, benzene, toluene etc.The concentration of vinylbenzene in solvent is in 5～100% scopes.
The present invention adopts the Primary Catalysts of a kind of new metallocene titanium compound as the preparation syndiotactic polystyrene, make the catalytic activity of catalyzer reach 523 kg of polymer/gram titanium/hour, obtained effect preferably.
The invention will be further elaborated below by embodiment.
Embodiment [embodiment 1]
Preparation of Catalyst
In the there-necked flask of 250 milliliters of exsiccant, N
2Pump drainage 3 times adds the 1.317 single luxuriant titanium of gram pentamethyl-trichlorine and 90 milliliters of benzene, from 30 milliliters of benzene of top dropping, 1.53 the mixture of gram p-fluorophenol and 1.38 gram triethylamines dripped off after 30 minutes, normal-temperature reaction is after 1 hour, reheat reacts after 2 hours to the benzene reflux temperature, stops heating, normal-temperature reaction 16 hours is filtered, and filtrate is drained, with toluene, hexane mixing solutions (1: 10) recrystallization three times, drain, get yellow crystals 1.97 grams, yield 84%.[embodiment 2]
Preparation of Catalyst
In the there-necked flask of 250 milliliters of exsiccant, N
2Pump drainage 3 times adds the 1.66 single luxuriant titanium of gram pentamethyl-trichlorine and 95 milliliters of benzene, from 45 milliliters of benzene of top dropping, 2.97 the mixture of gram p bromophenol and 1.76 gram triethylamines dripped off after 40 minutes, normal-temperature reaction is after 2 hours, reheat reacts after 3 hours to the benzene reflux temperature, stops heating, normal-temperature reaction 18 hours is filtered, and filtrate is drained, with toluene, hexane mixing solutions (1: 6) recrystallization three times, drain, get yellow crystals 3.28 grams, yield 82%.[embodiment 3]
Preparation of Catalyst
In the there-necked flask of 250 milliliters of exsiccant, N
2Pump drainage 3 times adds the 0.78 single luxuriant titanium of gram pentamethyl-trichlorine and 80 milliliters of benzene, from 30 milliliters of benzene of top dropping, 1.79 gram drips off reacting by heating 4 hours to the mixture of iodophenol and 0.83 gram triethylamine after 40 minutes, normal-temperature reaction is 16 hours again, reacting by heating 3 hours is once more filtered at last, and filtrate is drained, with toluene, hexane mixing solutions (1: 4) recrystallization three times, drain, get yellow crystals 2.26 grams, productive rate 75%.[embodiment 4]
On in baking, 50 milliliters of two mouthfuls of bottles of exsiccant, use high-purity N
2Pump drainage 3 times, add 10 milliliters of commercial benzene vinyl monomers, induction stirring was injected triisobutyl aluminium 0.2 mmole with syringe after 20 minutes in 60 ℃ of oil baths, MAO 0.6 mmole, the luxuriant titanium fluorine catalyst 0.001 mmole reaction of embodiment 2 with ethanol-hydrochloric acid soln stopped reaction, was washed after 10 minutes, dry that powder solid 3.84 restrains, catalytic activity 481 kg of polymer/(the gram titanium. hour), a normality 97%, Mw=46 * 10
4, 272 ℃ of fusing points.[embodiment 5]
On in baking, 50 milliliters of two mouthfuls of bottles of exsiccant, use high-purity N
2Pump drainage 3 times, add 10 milliliters of commercial benzene vinyl monomers, induction stirring was injected triisobutyl aluminium 0.4 mmole with syringe after 20 minutes in 60 ℃ of oil baths, MAO 0.4 mmole, the luxuriant titanium fluorine catalyst 0.001 mmole reaction of embodiment 2 with ethanol-hydrochloric acid soln stopped reaction, was washed after 10 minutes, dry that powder solid 4.17 restrains, catalytic activity 523 kg of polymer/(the gram titanium. hour), a normality 97%, Mw=30 * 10
4, 272 ℃ of fusing points.[embodiment 6]
On in baking, 50 milliliters of two mouthfuls of bottles of exsiccant, use high-purity N
2Pump drainage 3 times, add 10 milliliters of commercial benzene vinyl monomers, induction stirring was injected triisobutyl aluminium 0.2 mmole with syringe after 20 minutes in 60 ℃ of oil baths, MAO 0.6 mmole, the luxuriant titanium bromine catalyst 0.001 mmole reaction of embodiment 2 with ethanol-hydrochloric acid soln stopped reaction, was washed after 10 minutes, dry that powder solid 3.68 restrains, catalytic activity 461 kg of polymer/(the gram titanium. hour), a normality 97%, Mw=49 * 10
4, 272 ℃ of fusing points.[embodiment 7]
On in baking, 50 milliliters of two mouthfuls of bottles of exsiccant, use high-purity N
2Pump drainage 3 times, add 10 milliliters of commercial benzene vinyl monomers, induction stirring was injected triisobutyl aluminium 0.4 mmole with syringe after 20 minutes in 60 ℃ of oil baths, MAO 0.4 mmole, the luxuriant titanium bromine catalyst 0.001 mmole reaction of embodiment 2 with ethanol-hydrochloric acid soln stopped reaction, was washed after 10 minutes, dry that powder solid 3.91 restrains, catalytic activity 491 kg of polymer/(the gram titanium. hour), a normality 96%, Mw=34 * 10
4, 270 ℃ of fusing points.[embodiment 8]
On in baking, 50 milliliters of two mouthfuls of bottles of exsiccant, use high-purity N
2Pump drainage 3 times, add 10 milliliters of commercial benzene vinyl monomers, induction stirring was injected triisobutyl aluminium 0.2 mmole with syringe after 20 minutes in 60 ℃ of oil baths, MAO 0.6 mmole, the luxuriant titanium iodine catalyst 0.001 mmole reaction of embodiment 2 with ethanol-hydrochloric acid soln stopped reaction, was washed after 10 minutes, dry that powder solid 3.68 restrains, catalytic activity 461 kg of polymer/(the gram titanium. hour), a normality 97%, Mw=49 * 10
4, 272 ℃ of fusing points.[embodiment 9]
On in baking, 50 milliliters of two mouthfuls of bottles of exsiccant, use high-purity N
2Pump drainage 3 times, add 10 milliliters of commercial benzene vinyl monomers, induction stirring was injected triisobutyl aluminium 0.4 mmole with syringe after 20 minutes in 60 ℃ of oil baths, MAO 0.4 mmole, the luxuriant titanium iodine catalyst 0.001 mmole reaction of embodiment 2 with ethanol-hydrochloric acid soln stopped reaction, was washed after 10 minutes, dry that powder solid 3.91 restrains, catalytic activity 491 kg of polymer/(the gram titanium. hour), a normality 96%, Mw=34 * 10
4, 270 ℃ of fusing points.[comparative example 1]
On in baking, 50 milliliters of two mouthfuls of bottles of exsiccant, use high-purity N
2Pump drainage 3 times adds 10 milliliters of commercial benzene vinyl monomers, and induction stirring was injected triisobutyl aluminium 0.4 mmole, MAO 0.4 mmole, Cp with syringe after 20 minutes in 60 ℃ of oil baths
*TiCl
30.001 mmole reaction (Cp after 10 minutes
*Be the pentamethyl-cyclopentadienyl), with ethanol-hydrochloric acid soln stopped reaction, washing, dry that powder solid 0.41 restrains, catalytic activity 51 kg of polymer/(the gram titanium. hour), a normality 94%, Mw=15 * 10
4
Claims (8)
1, a kind of catalyzer for preparing syndiotactic polystyrene comprises metallocene titanium compound I and alkylaluminoxane II:
R
1Ti(OR
2R
3)
3 I
R in the formula
1For containing 1～5 C on cyclopentadienyl or the ring
1～C
4The cyclopentadienyl of alkyl substituent;
R
2For containing the aryl of 6～10 carbon atoms;
R
3Be fluorine, bromine or iodine;
R
4For containing the alkyl of 1～4 carbon atom;
N is the oligomerisation degree of alkylaluminoxane, and its value is 6～40;
Wherein the aluminium among the alkylaluminoxane II is 50～2000 to the mole ratio of metallocene titanium compound I, Ti and R
2Between have Sauerstoffatom to link to each other.
2, the catalyzer of preparation syndiotactic polystyrene according to claim 1 is characterized in that R
1Be cyclopentadienyl or pentamethyl-cyclopentadienyl.
3, the catalyzer of preparation syndiotactic polystyrene according to claim 2 is characterized in that R
1Be the pentamethyl-cyclopentadienyl.
4, the catalyzer of preparation syndiotactic polystyrene according to claim 1 is characterized in that R
2Be phenyl.
5, the catalyzer of preparation syndiotactic polystyrene according to claim 1 is characterized in that R
3The position that is selected from fluorine, bromine or iodine is contraposition.
6, the catalyzer of preparation syndiotactic polystyrene according to claim 1 is characterized in that the value of the oligomerisation degree n of alkylaluminoxane is 10～30.
7, the catalyzer of preparation syndiotactic polystyrene according to claim 1, it is characterized in that also containing in the catalyzer aluminum alkyls component III is AlX
3, X is the alkyl that contains 1～4 carbon atom, with the molar ratio computing aluminum alkyls: alkylaluminoxane is 0.1～3.
8, the catalyzer of preparation syndiotactic polystyrene according to claim 7 is characterized in that the aluminum alkyls component is a triisobutyl aluminium.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA021124493A CN1467232A (en) | 2002-07-10 | 2002-07-10 | Catalyst for preparing syndiotactic polystyrene |
| US10/410,036 US6921734B2 (en) | 2002-04-10 | 2003-04-09 | Titanocene complexes and its catalyst for preparing syndiotactic polystyrene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA021124493A CN1467232A (en) | 2002-07-10 | 2002-07-10 | Catalyst for preparing syndiotactic polystyrene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1467232A true CN1467232A (en) | 2004-01-14 |
Family
ID=34141928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA021124493A Pending CN1467232A (en) | 2002-04-10 | 2002-07-10 | Catalyst for preparing syndiotactic polystyrene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1467232A (en) |
-
2002
- 2002-07-10 CN CNA021124493A patent/CN1467232A/en active Pending
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