CN1340551A - Metallocene titanium compound and its preparing process - Google Patents

Metallocene titanium compound and its preparing process Download PDF

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CN1340551A
CN1340551A CN 00119775 CN00119775A CN1340551A CN 1340551 A CN1340551 A CN 1340551A CN 00119775 CN00119775 CN 00119775 CN 00119775 A CN00119775 A CN 00119775A CN 1340551 A CN1340551 A CN 1340551A
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titanium compound
metallocene titanium
compound according
cpticl
preparation
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CN1116310C (en
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钱延龙
马海燕
张越
黄吉玲
周文乐
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East China University of Science and Technology
Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
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East China University of Science and Technology
Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
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Abstract

A metallocene titanium compound and its preparing process are disclosed. Its general formula is CpTiCl2(OR1OR2), where Cp is cyclopentadienyl, R1 is alkyl with 2-6 carbon atoms or aryl with 6-10 carbon atoms, and R2 is the alkyl with 1-4 carbon atoms. It can be used for polymerizing styrene with the advantages of high catalytic activity and high content of syndiotactic polystyrene.

Description

Metallocene titanium compound and preparation method thereof
The present invention relates to metallocene titanium compound and preparation method thereof.
(Polystyrene is a kind of unregulated polymer PS) to the polystyrene that obtains by radical polymerization, and matter is hard, transparent, rigidity, electrical insulating property, cheap, dyeing has become one of current four big general-purpose plastics easily, be widely used in packing, building, medicine, electronics, automobile, industries such as daily necessities.But because the randomness of structure causes it frangible, thermo-labile, not resistance to chemical attack.
European patent EP 210615 obtains a kind of polystyrene of high tacticity, and wherein the syndiotactic structure arrangement is pressed in the phenyl ring replacement.This crystalline material no longer has the shortcoming of unregulated polymer, is dissolved in any organic solvent hardly, and has high melting range (250～280 ℃), heat-resisting, resistance to chemical attack, its performance can with polyester, polyurethane, poly-imines etc. compares favourably.
The catalyst system that is generally used for syndiotactic polymerization of phenylethylene is made up of two portions, i.e. transition metal organometallic compound, especially Ti, and the compound of Zr, and with methylaluminoxane (MAO) and B (C 6F 5) 3Promotor for representative.
Common catalyzer comprises the various halogenide of titanium in the document, four alkoxy compounds (methoxyl group, oxyethyl group, propoxy-, isopropoxy etc.), titanic acid ester, a metallocene compound (luxuriant trichlorine titanium, one luxuriant trialkyl titanium, one luxuriant tri-alkoxy titanium, and replace luxuriant all cpds), tetraalkyl titanium and corresponding zirconium compounds.
Metallocene catalyst is since the fifties, it is the research focus of catalysis in olefine polymerization always, the beginning of the eighties, the discovery catalyzed polymerization that promotes alkene especially of Kaminsky promotor methylaluminoxane entered new research climax, and wherein the catalyst system of compositions such as half sandwich compound and methylaluminoxane has the catalytic activity of stipulating tropism and Gao between significant to the catalyzed polymerization of styrene monomer.After this, the patent that relates to various half-sandwich compounds occurs in succession.
U.S. Pat 4978730 (nineteen ninety) (Process for producing styrene-based polymers andcatalysts foruse therein) discloses a structural formula class metallocene-titanium catalyst as follows:
R 1TiR 2R 3R 4
Typical compound is CpTiCl 3, Cp *TiCl 3,
CpTi(OR) 3，Cp *Ti(OR) 3，(R＝Me，Et，Pr，Bu，Ph)，
CpTiR 3，Cp *TiR 3，(R＝Me，Et，Pr，Bu)
In the embodiment, such compound for catalysis activity is up to 2.9 * 10 6Gram PS/ (mole Ti mole S hour), normality reaches 98% between the gained polystyrene.The compound that wherein adopts trialkyl, tri-alkoxy to replace, catalytic activity reaches 3.59 * 10 5Gram PS/ (mole Ti mole S hour), visible in the polymerization process that it adopted, the catalytic effect of this compounds is not high; And according to document, the compound of this type is owing to three alkyl or alkoxyl group replacement, and the polarity of compound is very low, and raw alcohol easily mixes mutually with product, is difficult to separate purification.
One of purpose of the present invention is in order to overcome the metallocene compound of introducing in the document in the past and to be used for the syndiotactic polymerization of phenylethylene process, has the not high shortcoming of catalytic effect, and a kind of new metallocene titanium compound is provided.When this metallocene titanium compound is used for the syndiotactic polymerization of phenylethylene process, has the catalytic activity height, excellent catalytic effect, the high characteristics of syndiotactic polystyrene content of acquisition.
Two of purpose of the present invention provides the preparation method of the metallocene titanium compound that one of a kind of and purpose adapt.
One of purpose of the present invention is to realize by following technical scheme: a kind of metallocene titanium compound, and its structure has following general formula:
CpTiCl 2(OR 1OR 2)
Cp is a cyclopentadienyl in the formula;
R 1Be the alkyl of 2～6 carbon atoms or the aryl of 6～10 carbon atoms;
R 2It is the alkyl of 1～4 carbon atom.
R in the technique scheme 1Preferred version is ethyl, sec.-propyl or phenyl; R 2Preferred version is a methyl.
Two of purpose of the present invention is to realize by following technical scheme: a kind of metallocene titanium compound CpTiCl 2(OR 1OR 2), Cp is a cyclopentadienyl in the formula; R 1Be the alkyl of 2～6 carbon atoms or the aryl of 6～10 carbon atoms; R 2It is the alkyl of 1～4 carbon atom.Its preparation method is as follows: the aryloxy alcohol that at first will contain the alkoxyl alcohol of 2～6 carbon atoms or contain 6～10 carbon atoms joins CpTiCl with the solution that contains the low-grade aliphatic amine of 1～6 carbon atom 3Solution in, CpTiCl wherein 3With the mol ratio of alkoxyl alcohol or aryloxy alcohol be 1: 1～1.5, CpTiCl 3With the mol ratio of low-grade aliphatic amine be 1: 1～2, under inert atmosphere protection, be 10～100 ℃ in temperature of reaction, the reaction times is to react under the condition in 1～24 hour, then after filtration, concentrate, use the organic solvent recrystallization, must the product metallocene titanium compound.
CpTiCl in the technique scheme 3With the mol ratio preferable range of alkoxyl alcohol or aryloxy alcohol be 1: 1～1.2, CpTiCl 3With the mol ratio preferable range of low-grade aliphatic amine be 1: 1～1.5, the temperature of reaction preferable range is 25～35 ℃, the reaction times preferable range is 4～8 hours, the low-grade aliphatic amine preferred version is a triethylamine, organic solvent is selected from ether, benzene, toluene, normal hexane or sherwood oil and composition thereof, and the used gas of inert atmosphere can be with argon gas or nitrogen.
The catalyst system that metallocene titanium compound of the present invention and alkylaluminoxane are formed, when being used for syndiotactic polymerization of phenylethylene, activity of such catalysts reaches as high as 1.92 * 10 7Gram PS/ mole Ti mole S hour, rule content is up to 99.5% between catalysis gained polystyrene, and melting point polymer is 259.7～262.5 ℃, has obtained effect preferably.It is simple that the preparation method of this metallocene titanium compound also has process, and separate and purify easily, characteristics with low cost, and more easily obtained required metallocene titanium compound.
The invention will be further elaborated below by embodiment: [embodiment 1]
(preparation of compd A): under argon shield, with 1: 1.2 alkoxyl alcohol of mol ratio (R wherein 1=ethyl, R 2=methyl) and the diethyl ether solution of said low-grade aliphatic amine (triethylamine), slowly join and pure equimolar CpTiCl 3Diethyl ether solution in, under 35 ℃ condition, stirring reaction 4 hours filters, clear liquid is drained, the oily matter of gained obtains limpid yellow oil with toluene and normal hexane recrystallization.The analytical test result is as follows:
Molecular formula: C 8H 12Cl 2O 2Ti; Mass spectrum demonstration molecular ion peak 258 (4, M +).
Ir data (cm -1): 3106m, 2920m, 2886m, 1436m, 1354w, 1088w, 1131s, 1100s, 1017s, 821s, 792s.
Nuclear magnetic data ( 1H NMR, ppm): 6.74～6.60 (m, 5H), 4.67 (t, 2H, J=4.2Hz), 3.56 (t, 2H, J=4.2Hz), 3.40 (s, 3H).
Ultimate analysis data: actual measurement, C:37.13% H:4.51%
Calculate C:37.10% H:4.68%[embodiment 2]
(preparation of compd B): under argon shield, with 1: 1.2 said alkoxyl alcohol (R of mol ratio 1=CH (CH 3) CH 2, R 2=methyl) and the diethyl ether solution of said low-grade aliphatic amine (triethylamine), slowly joining with pure mol ratio is 1: 1.5 CpTiCl 3Diethyl ether solution in, under 25 ℃ condition, stirring reaction 8 hours filters, clear liquid is drained, the oily matter of gained obtains limpid yellow oil with toluene and normal hexane recrystallization.The analytical test result is as follows:
Molecular formula: C 9H 14Cl 2O 2Ti mass spectrum demonstration molecular ion peak 272 (4, M +).
Ir data (cm -1): 3107m, 2932m, 2890m, 1441m, 1373w, 1147m, 1110s, 1093s, 1014s, 822s, 790s.
Nuclear magnetic data ( 1H NMR, ppm): 6.94～6.72 (m, 5H), 4.99 (m, 1H), 3.49～3.45 (m, 2H), 3.45 (s, 3H), 1.35 (d, 3H, J=6.6Hz).
Ultimate analysis data: actual measurement, C:38.41% H:4.64%
Calculate C:39.59% H:5.18%[embodiment 3]
(preparation of Compound C): under argon shield, with 1: 1.2 said aryloxy alcohol of mol ratio ( R 2=methyl) and the benzole soln of said low-grade aliphatic amine (triethylamine), slowly joining with pure mol ratio is 1: 1.2 CpTiCl 3Benzole soln in, under 10 ℃ condition, stirring reaction 24 hours filters, clear liquid is drained, the oily matter of gained obtains limpid dark red oily matter with toluene and normal hexane recrystallization.The analytical test result is as follows:
Molecular formula: C 12H 12Cl 2O 2Ti; Mass spectrum demonstration molecular ion peak 306 (7, M +).
Ir data (cm -1): 3108m, 1612w, 1596m, 1501s, 1484m, 1361w, 1263s, 1225s, 1100s, 1022m, 824s, 794s, 750s.
Nuclear magnetic data ( 1H NMR, ppm): 6.93～6.85 (m, 4H), 6.62～6.45 (m, 5H), 3.88 (s, 3H).
Ultimate analysis data: actual measurement, C:47.08% H:4.07%
Calculate C:46.94% H:3.95%[embodiment 4]
(preparation of Compound D): under argon shield, the diethyl ether solution with 1: 1.2 said alkoxyl alcohol (tetrahydrofurfuryl alcohol) of mol ratio and said low-grade aliphatic amine (triethylamine) slowly joins and pure equimolar CpTiCl 3Diethyl ether solution in, under 25 ℃ condition, stirring reaction 8 hours filters, clear liquid is drained, the oily matter of gained obtains limpid yellow oil with toluene and normal hexane recrystallization.The analytical test result is as follows:
Molecular formula: C 10H 14Cl 2O 2Ti; Mass spectrum demonstration molecular ion peak 284 (0.2, M +).
Ir data (cm -1): 3107w, 2950m, 2870m, 1440m, 1367w, 1118s, 1077s, 1025m, 826s, 793m.
Nuclear magnetic data ( 1H NMR, ppm): 6.82～6.59 (m, 5H), 4.73～4.52 (m, 2H), 4.03～3.98 (m, 1H), 3.88～3.84 (t, 1H, J=6.8H), 3.83～3.78 (t, 1H, J=6.8H), 2.01～1.72 (m, 4H).
Ultimate analysis data: actual measurement, C:42.48% H:5.09%
Calculate C:42.13% H:4.96%[embodiment 5]
Polyreaction is carried out in the ampere bottle of a baking argon filling three times.2 milliliters of vinylbenzene, 3.4 milliliter toluene, 6.6 the methylaluminoxane toluene solution of ml concn 1.53 mol, and the toluene solution of 0.1 milliliter 0.05 mol compd A is injected in the ampere bottle successively was positioned in the oil bath of constant temperature to 50 in advance ℃ polymerization 1.5 hours.Stop polyreaction with the ethanol that contains 10%HCl, after filtration, after the carrying out washing treatment, resulting polymers in 80 ℃ of following vacuum-dryings 24 hours to constant weight, 0.4565 gram polystyrene, catalytic activity is 3.50 * 10 6Gram PS/ (mole Ti mole S hour).Refluxed 2 hours in butanone, remove random polystyrene, recording syndiotactic polystyrene content is 95.1%, 259.7 ℃ of the fusing points of polymkeric substance.[embodiment 6]
2 milliliters of vinylbenzene, 3.4 milliliter toluene, 6.6 the methylaluminoxane toluene solution of ml concn 1.53 mol, and the toluene solution of 0.1 milliliter 0.05 mol Compound C is injected in the ampere bottle successively, be positioned in the oil bath of constant temperature to 50 in advance ℃ polymerization 1 hour, get 0.3845 gram polystyrene, catalytic activity is 4.42 * 10 6Gram PS/ (mole Ti mole S hour), recording syndiotactic polystyrene content is 96.7%, the fusing point of polymkeric substance is 262.5 ℃.[embodiment 7]
11 milliliters of vinylbenzene, 0.5 ml concn is the methylaluminoxane toluene solution of 1.53 mol, and the toluene solution of 0.05 milliliter 0.05 mol Compound C is injected in the ampere bottle successively, be positioned in the oil bath of constant temperature to 50 in advance ℃ polymerase 10 .5 hour, get 2.3008 gram polystyrene, catalytic activity is 1.92 * 10 7Gram PS/ (mole Ti mole S hour), recording syndiotactic polystyrene content is 86.2%.[comparative example 1]
11 milliliters of vinylbenzene, 0.5 ml concn are the methylaluminoxane toluene solution of 1.53 mol, and 0.05 milliliter 0.05 mol CpTiCl 3Toluene solution be injected into successively in the ampere bottle, be positioned in the oil bath of constant temperature to 50 in advance ℃ polymerase 10 .5 hour, 0.6102 gram polystyrene, catalytic activity is 5.1 * 10 6Gram PS/ (mole Ti mole S hour), recording syndiotactic polystyrene content is 60.0%.[embodiment 8]
11 milliliters of vinylbenzene, 1 ml concn is the methylaluminoxane toluene solution of 1.53 mol, and the toluene solution of 0.1 milliliter 0.05 mol Compound C is injected in the ampere bottle successively, be positioned in the oil bath of constant temperature to 90 in advance ℃ polymerization 2 hours, get 3.1504 gram polystyrene, catalytic activity is 3.29 * 10 6Gram PS/ (the little mole of mole Ti S hour), recording syndiotactic polystyrene content is 79.6%.[embodiment 9]
11 milliliters of vinylbenzene, 1 ml concn is the methylaluminoxane toluene solution of 1.53 mol, and the toluene solution of 0.1 milliliter 0.05 mol Compound C is injected in the ampere bottle successively, be positioned in the oil bath of constant temperature to 70 in advance ℃ polymerization 1 hour, get 3.0240 gram polystyrene, catalytic activity is 6.32 * 10 6Gram PS/ (mole Ti mole S hour) records and asks that stereospecific polymerized styrene content is 94.7%.[comparative example 2]
11 milliliters of vinylbenzene, 1 ml concn are the methylaluminoxane toluene solution of 1.53 mol, and 0.1 milliliter 0.05 mol CpTiCl 3Toluene solution be injected into successively in the ampere bottle, be positioned in the oil bath of constant temperature to 70 in advance ℃ polymerization 1 hour, 1.5727 gram polystyrene, catalytic activity is 3.29 * 10 6Gram PS/ (mole Ti mole S hour), recording syndiotactic polystyrene content is 73.1%.[embodiment 10]
2 milliliters of vinylbenzene, 3.4 milliliter toluene, 6.6 the methylaluminoxane toluene solution of ml concn 1.53 mol, and the toluene solution of 0.05 milliliter 0.05 mol Compound D is injected in the ampere bottle successively, be positioned in the oil bath of constant temperature to 50 in advance ℃ polymerase 10 .7 hour, get 0.4023 gram polystyrene, catalytic activity is 1.32 * 10 7Gram PS/ (mole Ti mole S hour), recording syndiotactic polystyrene content is 99.5%.[embodiment 11]
11 milliliters of vinylbenzene, 1 ml concn is the methylaluminoxane toluene solution of 1.53 mol, and the toluene solution of 0.1 milliliter 0.05 mol Compound D is injected in the ampere bottle successively, be positioned in the oil bath of constant temperature to 25 in advance ℃ polymerase 10 .5 hour, get 0.5167 gram polystyrene, catalytic activity is 2.16 * 10 6Gram PS/ (mole Ti mole S hour), recording syndiotactic polystyrene content is 48.9%.[embodiment 12]
11 milliliters of vinylbenzene, 1 ml concn is the methylaluminoxane toluene solution of 1.53 mol, and the toluene solution of 0.1 milliliter 0.05 mol Compound D is injected in the ampere bottle successively, be positioned in the oil bath of constant temperature to 70 in advance ℃ polymerization 1 hour, get 3.3322 gram polystyrene, catalytic activity is 6.96 * 10 6Gram PS/ (mole Ti mole S hour), recording syndiotactic polystyrene content is 90.1%.

Claims (10)

1, a kind of metallocene titanium compound, its structure has following general formula:
CpTiCl 2(OR 1OR 2)
Cp is a cyclopentadienyl in the formula;
R 1Be the alkyl of 2～6 carbon atoms or the aryl of 6～10 carbon atoms;
R 2It is the alkyl of 1～4 carbon atom.
2, metallocene titanium compound according to claim 1 is characterized in that R 1Be ethyl, sec.-propyl or phenyl.
3, metallocene titanium compound according to claim 1 is characterized in that R 2Be methyl.
4, the preparation method of metallocene titanium compound according to claim 1, the aryloxy alcohol that at first will contain the alkoxyl alcohol of 2～6 carbon atoms or contain 6～10 carbon atoms joins CpTiCl with the lower aliphatic amine aqueous solution that contains 1～6 carbon atom 3Solution in, Cp is cyclopentadienyl, wherein CpTiCl 3With the mol ratio of alkoxyl alcohol or aryloxy alcohol be 1: 1～1.5, CpTiCl 3With the mol ratio of low-grade aliphatic amine be 1: 1～2, under inert atmosphere protection, be 10～100 ℃ in temperature of reaction, the reaction times is to react under the condition in 1～24 hour, then after filtration, concentrate, use the organic solvent recrystallization, must the product metallocene titanium compound.
5, the preparation method of metallocene titanium compound according to claim 4 is characterized in that CpTiCl 3With the mol ratio of alkoxyl alcohol or aryloxy alcohol be 1: 1～1.2.
6, the preparation method of metallocene titanium compound according to claim 4 is characterized in that CpTiCl 3With the mol ratio of low-grade aliphatic amine be 1: 1～1.5.
7, the preparation method of metallocene titanium compound according to claim 4 is characterized in that temperature of reaction is 25～35 ℃.
8, the preparation method of metallocene titanium compound according to claim 4 is characterized in that the reaction times is 4～8 hours.
9, the preparation method of metallocene titanium compound according to claim 4 is characterized in that low-grade aliphatic amine is a triethylamine.
10, the preparation method of metallocene titanium compound according to claim 4 is characterized in that organic solvent is selected from ether, benzene, toluene, normal hexane or sherwood oil and composition thereof.
CN 00119775 2000-08-29 2000-08-29 Metallocene titanium compound and its preparing process Expired - Fee Related CN1116310C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101250238B (en) * 2008-03-28 2010-06-02 中国石油天然气股份有限公司 Boroxol titanocene metal catalyzer and preparation method and application thereof
JP2011507974A (en) * 2007-12-31 2011-03-10 エスケー エナジー カンパニー リミテッド Transition metal compound, catalyst composition containing the same, and olefin homopolymerization or copolymer production method using the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011507974A (en) * 2007-12-31 2011-03-10 エスケー エナジー カンパニー リミテッド Transition metal compound, catalyst composition containing the same, and olefin homopolymerization or copolymer production method using the same
CN101250238B (en) * 2008-03-28 2010-06-02 中国石油天然气股份有限公司 Boroxol titanocene metal catalyzer and preparation method and application thereof

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