CN1286861C - Binuclear titanium series polyolefin catalyst, and its preparing method and use - Google Patents

Binuclear titanium series polyolefin catalyst, and its preparing method and use Download PDF

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CN1286861C
CN1286861C CN 03149936 CN03149936A CN1286861C CN 1286861 C CN1286861 C CN 1286861C CN 03149936 CN03149936 CN 03149936 CN 03149936 A CN03149936 A CN 03149936A CN 1286861 C CN1286861 C CN 1286861C
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hydrogen
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pyrrole
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纪洪波
许学翔
赵伟
孙敏
景振华
时晓岚
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Department Of Petrochemical Engineering China Petroleum Chemical Co
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Abstract

The present invention relates to a binuclear titanium serial polyolefin catalyst which has a structure expression of a formula (I), wherein R1 and R2 are respectively substituted groups on a benzene ring, and the quantity of the substituted groups on each benzene ring is from 1 to 4; R1 and R2 are respectively selected from hydrogen or an alkyl group of C1 to C8; R3 is selected from the hydrogen or an alkyl group of C1 to C3; R4 is substituted groups on a pyrrole ring, and the quantity of the substituted groups is from 1 to 3; R4 is selected from the hydrogen or an alkyl group of C1 to C6; Y is selected from-O-,-S-or-CH2-; M is selected from IV group metal; X is the same or different groups and is selected from a halogen or pyrrole compound and a condensation compound of pyrrole methanal condensed aniline, and pyrrole methanal condensed cyclohexylamine or the alkyl substitution thereof; the alkyl group is selected from C1 to C4. The compound is matched with alkylaluminium oxyalkyl or alkylaluminium to be used as the olefin polymerization catalyst, and a polyolefin product with high molecular weight can be obtained.

Description

Double-core titanium polyolefin catalyzer and preparation method and application
Technical field
The present invention relates to a kind of olefin polymerization catalysis and preparation method thereof and application, specifically, is that a kind of double-core titanium is non-luxuriant class polyolefin catalyst and preparation method thereof and application.
Background technology
After metallocene catalyst successfully was used for polyolefin industry production, a kind of was the transition metal complex of part with the heteroatomic compound, and promptly Nonmetallocene polyolefine catalyst is developed rapidly.On metallocene 99 years can (MetCon ' 99), T.Fujita etc. have reported a kind of new olefine polymerization catalyst series (FI Catalysts) that is better than metallocene catalyst, this catalyst series uses salicylic alidehyde imine as the concentricity atom titanium of part, zirconium or hafnium coordination, catalytic activity to vinyl polymerization is very high, and can be by changing ligand structure and the promotor polymkeric substance of production from the low-molecular weight polymer to the ultra-high molecular weight arbitrarily.
USP5,539,124 disclose a kind of transition metal compound catalizer that contains pyrrole ring, this catalyzer uses pyrroles, indoles, carbazole or their alkyl substituent as part, with central atom titanium or zirconium coordination, under promotor methylaluminoxane (MAO) effect, make alpha-olefin, carry out homopolymerization or copolymerization as ethene.
CN1317500A discloses the polyolefin catalyst that contains pyrrole ring in a kind of part, and the condensation product that this catalyzer generates with the amino benzenes compounds reaction with the carbonyl derivative of pyroles heterogeneous ring compound is as part, again with the halogenide such as the TiCl of IVB family metal 4, ZrCl 4Deng reacting, generate catalyzer, under promotor MAO effect, can be used for the catalyzer of ethylene polymerization, have high reaction activity and high, but the molecular weight of polymerisate is lower.
Summary of the invention
The purpose of this invention is to provide a kind of double-core titanium is non-luxuriant class polyolefin catalyst and preparation method, and this catalyzer has high polymerization activity, and the polymericular weight that makes is higher.
It is Primary Catalysts that another object of the present invention provides with above-mentioned catalyzer, the method for carrying out olefinic polymerization.
Double-core titanium polyolefin catalyzer provided by the invention has following structural formula:
Figure C0314993600041
In the formula (I), R 1And R 2Be respectively the substituting group on the phenyl ring, the substituting group on each phenyl ring is 1～4, R 1And R 2Be selected from hydrogen or C respectively 1～C 8Alkyl; R 3Be selected from hydrogen or C 1～C 3Alkyl; R 4Be the substituting group on the pyrrole ring, replacing radix is 1～3, R 4Be selected from hydrogen or C 1～C 6Alkyl; Y is selected from-O-,-S-or-CH 2-; M is selected from IV family metal; X is identical or different group, is selected from the condenses of halogen or carbonyl pyrrolidine compound and aniline, hexahydroaniline or their alkyl substituent, and described alkyl is selected from C 1～C 4Alkyl.
The present invention adopts the diphenylamine compound of bridging and carbonyl pyrrolidine compounds to carry out condensation reaction to prepare ligand compound, and this part has two coordination structures, can make the catalyzer of dual-core architecture with the transistion metal compound reaction.In this structure, pyrrole ring and atoms metal form the structure that is similar to metallocene, and in the side chain lone-pair electron on the imido grpup also with the atoms metal effect, play the effect of constrained geometry configuration, the substituting group that connects on the imido grpup also can influence to some extent to the sterie configuration and the electron distributions of catalyzer.This catalyzer is compared with the similar catalyst at monometallic center, and the polymer molecular weight that makes is bigger.
Embodiment
R in the catalyzer of the present invention 1And R 2Be respectively the substituting group on the phenyl ring, the substituting group number is 1～4, and preferred replacement position is 2,4 of phenyl ring, and number is respectively two, R 1And R 2Preferred hydrogen of difference or C 1～C 4Alkyl, more preferably hydrogen, methyl, ethyl, propyl group or sec.-propyl.
R 3For with carbon atom that imines links to each other on substituting group, preferred hydrogen, methyl or ethyl, more preferably hydrogen or methyl.
R 4Be the substituting group on the pyrrole ring, can be positioned at any position on the pyrrole ring, be preferably placed at 5, R 4Preferred hydrogen or C 1～C 3Alkyl, as methyl, ethyl, propyl group or sec.-propyl, more preferably hydrogen, methyl or ethyl.
Y is a bridged group, preferred-O-or-CH 2-; Preferred titanium of M or zirconium.
X is identical or different group, when X is identical group, and preferred chlorine or bromine.When X is a group inequality, wherein two groups are selected from chlorine or bromine, another group is selected from the condenses of carbonyl pyrrolidine compound and aniline, hexahydroaniline or their alkyl substituent, on described aniline ring or the cyclohexane ring one or more substituting group can be arranged, and substituting group is selected from C 1～C 4Alkyl; Preferred pyrrole aldehyde anil of described condenses or the pyrrole aldehyde hexahydroaniline that contracts.
Preparation of catalysts method of the present invention comprises:
(1) in non-polar organic solvent, with the organic acid is catalyzer, make the bridging phenylenediamine compound shown in carbonyl pyrrolidine compounds shown in the formula (II) and the formula (III), carry out condensation reaction 20～150 ℃ of mol ratios by 2: 1, remove and desolvate, the gained solid drying is promptly got two coordinate ligand compounds, in the formula (II), R 3Be selected from hydrogen or C 1～C 3Alkyl; R 4Be the substituting group on the pyrrole ring, replacing radix is 1～3, R 4Be selected from hydrogen or C 1～C 6Alkyl; R in the formula (III) 1And R 2Be respectively the substituting group on the phenyl ring, the substituting group on each phenyl ring is 1～4, R 1And R 2Be selected from hydrogen or C respectively 1～C 8Alkyl; Y is selected from-O-,-S-or-CH 2-;
Figure C0314993600051
(2) in the presence of ether solvents, make the above-mentioned ligand compound that makes and basic metal, alkali metal compound or alkaline earth metal compound by 1: 2 mol ratio-20～100 ℃ of reactions, make the basic metal or the alkaline earth salt of part.
(3) in ether solvents, be MX with the basic metal of the part that makes or alkaline earth salt and general formula 4Transition metal halide by 1: 2 mol ratio-20～100 ℃ of reactions, remove ether solvents, the resistates organic substance extraction is removed the insolubles after drying, described formula M X 4Middle M is selected from IV family metal; X is a halogen.
Aforesaid method (1) step is the preparation of part of the present invention, and used organic acid catalyst is formic acid or acetate, and described non-polar organic solvent is selected from hexane, benzene, toluene, preferred benzene, toluene, and its consumption is 2～20 times of reactant.
Described (2) step be the preparation of part salt, part can be directly and basic metal react the sodium salt of making part, also can react and make corresponding salt with alkali metal compound or alkaline earth metal compound.Preferred sodium of basic metal or potassium, preferred butyllithium of alkali metal compound or sodium hydride, alkaline earth metal compound preferable methyl magnesium chloride or ethylmagnesium chloride.Ether solvents consumption described in this step is 10～40 times of reactant.
Described (3) step is Preparation of catalysts, used transition metal halide MX 4Preferred titanium tetrachloride or zirconium tetrachloride.The ether solvents consumption is 20～200 times of reactant during preparation.Reaction finishes, remove ether solvents after, resistates will be used organic substance extraction, preferred organism is a toluene.Described extraction promptly be with organism with the catalyst dissolution in the resistates, the salt that reaction generates is insoluble to organism, is solid and separates out, the solids removed by filtration thing is drying to obtain catalyzer with filtrate.The liquid-solid volume ratio of extraction liquid and resistates is 50～100: 1 during extraction.
Preferred 60～80 ℃ of the temperature of (1) step condensation reaction in the aforesaid method, preferred 1～8 hour of time.(2) and preferred-10～40 ℃ of (3) step temperature of reaction, preferred 1～10 hour of the time.(2) and described ether solvents of (3) step be ether or tetrahydrofuran (THF), preferred tetrahydrofuran (THF).
The catalyzer that aforesaid method makes is the transition metal trihalid of ligand compound, and just 3 X are halogen in the catalyzer, preferred chlorine.An alkali metal salt of this compound and other part reacts, and also can make the transistion metal compound of two parts.In this compound, the part of an X for introducing, two other X is a halogen.Described introducing part is the condenses of carbonyl pyrrolidine compound and aniline, hexahydroaniline or their alkyl substituent, the preferred pyrrole aldehyde of carbonyl pyrrolidine compound wherein, the preferred C of the alkyl on aniline or the hexahydroaniline 1～C 4Alkyl.Concrete preparation method is: with the catalyzer that makes of (3) step in the presence of tetrahydrofuran (THF) with the sodium salt of the condenses of carbonyl pyrrolidine compound and aniline, hexahydroaniline or their alkyl substituent by 1: 2 mol ratio at-20～100 ℃, preferably-10～40 ℃ reaction, the contract sodium salt of hexahydroaniline of preferred pyrrole aldehyde anil of described sodium salt or pyrrole aldehyde, the reaction times is 1～24 hour.Be heated to the reflux temperature of tetrahydrofuran (THF), remove tetrahydrofuran (THF), resistates extracts with toluene, removes the insolubles after drying.The tetrahydrofuran (THF) that adds during reaction is 20～100 times of reaction-ure mixture.
When using catalyzer of the present invention to carry out olefinic polymerization, needing with alkylaluminoxane or aluminum alkyls be promotor, makes alkene at 0～110 ℃, 0.1～1.0MPa, preferred 10～120 ℃, carries out polyreaction under more preferably 30～80 ℃, 0.1～0.8MPa condition.During reaction in the promotor in Al and the Primary Catalysts mol ratio of metal be 25～2000: 1, preferred 150～1500: 1.
The polyreaction of carrying out with catalyzer of the present invention can be alkene homopolymerization or with the copolymerization of alpha-olefin.Suitable olefinic monomer is ethene, propylene, butylene, hexene or vinylbenzene, the preferred butylene of comonomer, hexene or octene.
Described promoter aluminium alkyl oxygen alkane preferable methyl aikyiaiurnirsoxan beta, the preferred trimethyl aluminium of aluminum alkyls, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, aluminium diethyl monochloride or their mixture.
Further specify the present invention below by example, but the present invention is not limited to this.
Example 1
Preparation [two (pyrrole aldehydes) contract 4,4 '-methylene radical-two (2, the 6-Diethyl Aniline)] titanous chloride.
(1) preparation part: two (pyrrole aldehydes) contract 4,4 '-methylene radical-two (2, the 6-ethylaniline).
In having the there-necked flask of reflux exchanger, add 4 of 10 milliliters of toluene and 0.005 mole, 4 '-methylene radical-two (2, the 6-Diethyl Aniline) and 0.01 mole of 2-pyrrole aldehyde (Sweden, ACR  S company), splash into 2 formic acid, 60 ℃ were reacted 4 hours, reactant was left standstill under-10 ℃ 48 hours, add 10 milliliters hexane, filter, solid is distinguished washed twice with 10 milliliters of hexanes, the following 60 ℃ of dryings that reduce pressure 1 hour, part a: two (pyrrole aldehydes) contract 4,4 '-methylene radical-two (2, the 6-Diethyl Aniline), yield 96 quality %.
Ultimate analysis actual measurement (calculating), quality %:C 80.11 (80.13); H 7.72 (7.81); N 12.35 (12.06).
H 1 NMR：δ4.00；δ8.27；δ10.32。
(2) preparation part salt
Under the high pure nitrogen protection, in the Schelenk bottle, add 0.002 mole of part a, with 30 milliliters of tetrahydrofuran (THF) dissolvings, be cooled to 0 ℃, and under this temperature, slowly add 0.004 mole NaH, rise to 40 ℃ of reactions 4 hours then, form the sodium salt slurries of part.
(3) preparation catalyzer
TiCl with 0.004 mole 4Be dissolved in 20 milliliters of tetrahydrofuran (THF)s and make solution, this solution is cooled to 0 ℃, slowly splash in the sodium salt slurries of part a, and reacted 1 hour under this temperature, be heated to the reflux temperature of tetrahydrofuran (THF), the reaction system color becomes brown by yellow.Remove tetrahydrofuran (THF) under the decompression, resistates stirs extraction 6 hours with 50 milliliters of toluene, remove by filter insoluble white solid, gained filtrate is under reduced pressure steamed except that toluene, under 60 ℃ of decompressions dry 1 hour then, the deep yellow solid, be the following catalyst A of structural formula: [two (pyrrole aldehydes) contract 4,4 '-methylene radical-two (2, the 6-Diethyl Aniline)] titanous chloride, yield 76 quality %.
Ultimate analysis actual measurement (calculating), quality %:C 48.31 (48.28); H 4.56 (4.44); N 7.15 (7.27).
Figure C0314993600081
Example 2
Preparation [two (pyrrole aldehydes) contract 4,4 '-methylene radical-two (2, the 6-Diethyl Aniline)] tri-chlorination zirconium.
Method by example 1 prepares catalyzer, in different is (3) step with 0.004 mole ZrCl 4Carry out with part a, the following catalyst B of structural formula: [two (pyrrole aldehydes) contract 4,4 '-methylene radical-two (2, the 6-Diethyl Aniline)] tri-chlorination zirconium, yield 87 quality %.
Ultimate analysis actual measurement (calculating), quality: C 43.58 (43.40); H 4.59 (4.00); N 6.24 (6.58).
Figure C0314993600082
Example 3
Preparation [two (pyrrole aldehydes) contract 4,4 '-methylene radical-two (2, the 6-diisopropyl aniline)] titanous chloride.
(1) preparation part: two (pyrrole aldehydes) contract 4,4 '-methylene radical-two (2, the 6-diisopropyl aniline).
Method by example 1 (1) step prepares part, and different is with 4,4 '-methylene radical-two (2, the 6-diisopropyl aniline) carry out condensation reaction with the 2-pyrrole aldehyde, part b: two (pyrrole aldehydes) contract 4,4 '-methylene radical-two (2, the 6-diisopropyl aniline), yield 98 quality %.
Ultimate analysis actual measurement (calculating), quality %:C 76.83 (76.42); H 8.98 (8.55); N 10.63 (10.85).
H 1 NMR：δ8.26；δ10.21。
(2) preparation catalyzer
Prepare catalyzer by example 1 (2), the method in (3) step, different is replaces part a to react with part b, the following catalyzer C:[two (pyrrole aldehyde) of structural formula contract 4,4 '-methylene radical-two (2, the 6-diisopropyl aniline)] titanous chloride, yield 75 quality %.
Ultimate analysis actual measurement (calculating), quality %:C 48.23 (47.80); H 5.64 (5.11); N 6.34 (6.76).
Figure C0314993600091
Example 4
Preparation [two (pyrrole aldehydes) contract 4,4 '-methylene radical-two (2, the 6-diisopropyl aniline)] tri-chlorination zirconium.
Method by example 3 prepares catalyzer, and different is to use ZrCl 4Reacting with part salt, the catalyzer D:[two (pyrrole aldehyde) that must have a following structural formula contracts 4,4 '-methylene radical-two (2, the 6-diisopropyl aniline)] the tri-chlorination zirconium, yield 91 quality %.
Ultimate analysis actual measurement (calculating), quality %:C 43.75 (43.46); H 4.87 (4.64): N 6.09 (6.15).
Figure C0314993600092
Example 5
Preparation [two (pyrrole aldehydes) contract 4,4 '-oxydianiline] titanous chloride.
(1) preparation part: two (pyrrole aldehydes) contract 4,4 '-oxydianiline.
Method by example 1 (1) step prepares part, and different is with 4,4 '-oxydianiline and 2-pyrrole aldehyde carry out condensation reaction, and replaces toluene with benzene, and must part c: two (pyrrole aldehydes) contract 4,4 '-oxydianiline, yield 98 quality %.
Ultimate analysis actual measurement (calculating), quality %:C 74.41 (74.55); H 5.16 (5.12); N 15.72 (15.81).
H 1 NMR：δ8.29；δ10.40。
(2) preparation catalyzer
Method by example 1 (2), (3) step prepares catalyzer, and different is to replace part a to react with part c, must the following catalyzer E:[two (pyrrole aldehyde) of structural formula contract 4,4 '-oxydianiline] titanous chloride, yield 95 quality %.
Ultimate analysis actual measurement (calculating), quality %:C 40.12 (39.98); H 2.56 (2.44); N 8.32 (8.48).
Figure C0314993600101
Example 6
Preparation [two (pyrrole aldehydes) contract 4,4 '-methylene dianiline (MDA)] titanous chloride.
(1) preparation part: two (pyrrole aldehydes) contract 4,4 '-methylene dianiline (MDA).
Method by example 1 (1) step prepares part, and different is with 4,4 '-methylene dianiline (MDA) and 2-pyrrole aldehyde carry out condensation reaction, and must part d: two (pyrrole aldehydes) contract 4,4 '-methylene dianiline (MDA), yield 97 quality %.
Ultimate analysis actual measurement (calculating), quality %:C 78.46 (78.37); H 5.78 (5.72); N 15.77 (15.90).
H 1 NMR：δ4.00；δ8.25；δ10.18。
(2) preparation catalyzer
Method by example 1 (2), (3) step prepares catalyzer, and different is to replace part a to react with part d, must the following catalyzer F:[two (pyrrole aldehyde) of structural formula contract 4,4 '-methylene dianiline (MDA)] titanous chloride, yield 93 quality %.
Ultimate analysis actual measurement (calculating), quality %:C 42.08 (41.92); H 2.93 (2.75); N 8.32 (8.51).
Figure C0314993600102
Example 7
Preparation [two (pyrrole aldehydes) contract 4,4 '-methylene dianiline (MDA)] (pyrrole aldehyde anil) titanium dichloride.
(1) preparation part: pyrrole aldehyde anil.
Method by 1 (1) step of example prepares part, and different is to carry out condensation reaction with 0.01 mole aniline and 0.01 mole 2-pyrrole aldehyde, gets part e: pyrrole aldehyde anil, yield 97 quality %.
Ultimate analysis actual measurement (calculating), quality %:C 77.77 (77.61); H 5.95 (5.92); N 16.43 (16.46).
H 1 NMR：δ8.26；δ10.22。
(2) salt of preparation part e
Under the high pure nitrogen protection, in the Schelenk bottle, add 0.004 mole of part e, with 30 milliliters of tetrahydrofuran (THF) dissolvings; be cooled to 0 ℃; and under this temperature, slowly add 0.004 mole NaH, and be warming up to 40 ℃ of reactions 4 hours then, form the sodium salt slurries of part e.
(3) preparation catalyzer
The catalyzer F that 0.002 mole of example 6 is made is dissolved in 20 milliliters of tetrahydrofuran (THF)s and makes solution, this solution is cooled to 0 ℃, slowly splashes in the sodium salt slurries of part e, and under this temperature, reacted 1 hour, be heated to the reflux temperature of tetrahydrofuran (THF), the reaction system color becomes brown by yellow.Decompression is steamed down and is removed tetrahydrofuran (THF), resistates stirs extraction 6 hours with 50 milliliters of toluene, remove by filter insoluble white solid, filtrate is under reduced pressure steamed except that toluene, with product under 60 ℃ of decompressions dry 1 hour, the following catalyzer G:[two (pyrrole aldehyde) of aterrimus structural formula contract 4,4 '-methylene dianiline (MDA)] (pyrrole aldehyde anil) titanium dichloride, yield 89 quality %.
Ultimate analysis actual measurement (calculating), quality %:C 58.56 (58.34); H 4.13 (3.92); N 11.94 (12.12).
Example 8
Preparation [two (pyrrole aldehydes) contract 4,4 '-methylene dianiline (MDA)] (pyrrole aldehyde contract hexahydroaniline) titanium dichloride.
(1) preparation part: the pyrrole aldehyde hexahydroaniline that contracts.
Method by 1 (1) step of example prepares part, and different is to carry out condensation reaction with 0.01 mole hexahydroaniline and 0.01 mole 2-pyrrole aldehyde, gets part f, yield 94 quality %.
Ultimate analysis actual measurement (calculating), quality %:C75.03 (74.96); H 9.23 (9.15); N 15.67 (15.93).
H 1NMR：δ8.14；δ8.38。
(2) preparation catalyzer
Prepare catalyzer by example 7 (2), the method in (3) step, different is to change part e into part f to react, the following catalyzer H:[two (pyrrole aldehyde) of structural formula contracts 4,4 '-methylene dianiline (MDA)] (pyrrole aldehyde contract hexahydroaniline) titanium dichloride, yield 92 quality %.
Ultimate analysis actual measurement (calculating), quality %:C 57.80 (57.59); H 5.37 (5.16); N 11.61 (11.94).
Figure C0314993600121
Example 9
Method by example 6 prepares part d, presses example 1 (2), (3) step preparation catalyzer again, and different is (2) step to react the sodium salt slurries that make part d with part d and NaH, and (3) use ZrCl in the step 4React with the sodium salt of part d, the following catalyzer K:[two (pyrrole aldehyde) of structural formula contract 4,4 '-methylene dianiline (MDA)] the tri-chlorination zirconium, yield 71 quality %.
Ultimate analysis actual measurement (calculating), quality %:C, 37.11 (37.05); H, 2.56 (2.43); N, 7.51 (7.52).
Figure C0314993600122
Example 10
Prepare catalyzer by example 7 (2), the method in (3) step, different is the sodium salt that (2) step makes part f with part f and NaH reaction, (3) step reacts with sodium salt and the catalyzer K of part f, get the following catalyst I of structural formula: [two (pyrrole aldehydes) contract 4,4 '-methylene dianiline (MDA)] (pyrrole aldehyde contract hexahydroaniline) } zirconium dichloride, yield 96 quality %.
Ultimate analysis actual measurement (calculating), quality %:C 53.01 (52.72); H 4.86 (4.72); N 10.78 (10.93).
Comparative Examples
Method by example 1 (1) step prepares part g, different is with 0.01 mole 2, the 2-pyrrole aldehyde of 6-diisopropyl aniline and 0.01 mole carries out condensation reaction, must part g: pyrrole aldehyde contracts 2,6-diisopropyl aniline, yield 84 quality %.
Method by 1 (2) step of example makes 0.004 mole part g and 0.004 mole NaH reaction, makes the sodium salt slurries of part g, and then will contain 0.004 mole of TiCl by (3) one step process 4Tetrahydrofuran solution splash into wherein and react, with toluene extraction recrystallization again after the drying, comparative catalyst M:(pyrrole aldehyde contracts 2, the 6-diisopropyl aniline) titanous chloride.
Example 11～21
With 250 milliliters of reaction flasks that have an agitator with nitrogen replacement after, feed ethylene gas, control pressure is 0.1MPa.Add 50 milliliters of exsiccant toluene and concentration and be the toluene solution (production of U.S. Albemarle company) of 10 methylaluminoxane (MAO), wherein contain MAO 7.5 * 10 -3Mol, the mol ratio that makes aluminium and transition metal is 2000: 1, stirs 5 minutes, adds and contains 1.0 * 10 -5The toluene solution of mol catalyzer, 80 ℃ were reacted 0.5 hour, added 10 milliliters of acidifying ethanol that contain 30%HCl and stopped polyreactions.Reactant was continued to stir in excess ethyl alcohol 1 hour, filter, use washing with alcohol, 70 ℃ of vacuum-drying 4 hours must polymkeric substance.Each example catalyst system therefor and polymer property see Table 1, and wherein polymericular weight is measured with gel chromatography (GPC).
Table 1
Instance number The catalyzer numbering Catalyst activity, (gPE/molMhr) Polymericular weight Mw (* 10 4)
11 12 13 14 15 16 17 18 19 20 21 A B C D E F G H K I M 1.3×10 5 1.0×10 5 1.6×10 5 1.2×10 5 3.5×10 5 2.1×10 5 1.1×10 7 2.02×10 7 1.8×10 5 1.6×10 4 1.3×10 5 17.0 16.8 16.4 17.2 15.2 14.7 13.2 19.5 13.6 25.9 5.9
Annotate: M is titanium or zirconium

Claims (12)

1, a kind of double-core titanium polyolefin catalyzer has following structural formula:
In the formula (I), R 1And R 2Be respectively the substituting group on the phenyl ring, the substituting group on each phenyl ring is 1～4, R 1And R 2Be selected from hydrogen or C respectively 1～C 8Alkyl; R 3Be selected from hydrogen or C 1～C 3Alkyl; R 4Be the substituting group on the pyrrole ring, replacing radix is 1～3, R 4Be selected from hydrogen or C 1～C 6Alkyl; Y is selected from-O-,-S-or-CH 2-; M is selected from IV family metal; X is identical or different group, is selected from the condenses of halogen or carbonyl pyrrolidine compound and aniline, hexahydroaniline or their alkyl substituent, and described alkyl is selected from C 1～C 4Alkyl.
2, according to the described catalyzer of claim 1, it is characterized in that R 1And R 2Be selected from hydrogen or C respectively 1～C 4Alkyl, R 3Be selected from hydrogen, methyl or ethyl, R 4Be selected from hydrogen or C 1～C 3Alkyl, Y is selected from-O-or-CH 2-; M is titanium or zirconium, and X is chlorine, bromine, pyrrole aldehyde anil or the pyrrole aldehyde hexahydroaniline that contracts.
3, according to the described catalyzer of claim 1, it is characterized in that the substituent R on the phenyl ring 1And R 2Number be respectively two, be positioned at 2,4 of phenyl ring, R 1And R 2Be selected from hydrogen, methyl, ethyl, propyl group or sec.-propyl respectively.
4, according to described any one catalyzer of claim 1～3, it is characterized in that described R 3Be selected from hydrogen or methyl, R 4The replacement position be 5, R 4Be selected from hydrogen, methyl or ethyl.
5, the described Preparation of catalysts method of a kind of claim 1 comprises:
(1) in non-polar organic solvent, with the organic acid is catalyzer, make the bridging phenylenediamine compound shown in carbonyl pyrrolidine compounds shown in the formula (II) and the formula (III), carry out condensation reaction 20～150 ℃ of mol ratios by 2: 1, remove and desolvate, the gained solid drying is promptly got the ligand compound with two coordination abilities, in the formula (II), R 3Be selected from hydrogen or C 1～C 3Alkyl; R 4Be the substituting group on the pyrrole ring, replacing radix is 1～3, R 4Be selected from hydrogen or C 1～C 6Alkyl; R in the formula (III) 1And R 2Be respectively the substituting group on the phenyl ring, the substituting group on each phenyl ring is 1～4, R 1And R 2Be selected from hydrogen or C respectively 1～C 8Alkyl; Y is selected from-O-,-S-or-CH 2-;
(2) in the presence of ether solvents, make the above-mentioned ligand compound that makes and basic metal, alkali metal compound or alkaline earth metal compound by 1: 2 mol ratio-20～100 ℃ of reactions, make the basic metal or the alkaline earth salt of part.
(3) in ether solvents, be MX with the basic metal of the part that makes or alkaline earth salt and general formula 4Transition metal halide is pressed 1: 2 mol ratio-20～100 ℃ of reactions, removes ether solvents, and the resistates organic substance extraction is removed the insolubles after drying, described formula M X 4Middle M is selected from IV family metal; X is the condenses of halogen or carbonyl pyrrolidine compound and aniline, hexahydroaniline or their alkyl substituent, and described alkyl is selected from C 1～C 4Alkyl.
6, in accordance with the method for claim 5, it is characterized in that with the catalyzer that makes of (3) step in the presence of tetrahydrofuran (THF) with the sodium salt of the condenses of carbonyl pyrrolidine compound and aniline, hexahydroaniline or their alkyl substituent by 1: 2 mol ratio-20～100 ℃ of reactions, be heated to the reflux temperature of tetrahydrofuran (THF), remove tetrahydrofuran (THF), resistates extracts with toluene, removes the insolubles after drying.
7, in accordance with the method for claim 6, the sodium salt that it is characterized in that the condenses of described carbonyl pyrrolidine compound and aniline, hexahydroaniline or their alkyl substituent is selected from the contract sodium salt of hexahydroaniline of pyrrole aldehyde anil or pyrrole aldehyde.
8, in accordance with the method for claim 5, it is characterized in that the temperature of reaction in (1) step is 60～80 ℃, described organic acid is formic acid or acetate, and non-polar organic solvent is hexane, benzene or toluene.
9, in accordance with the method for claim 5, it is characterized in that described basic metal of (2) step is sodium or potassium, alkali metal compound is butyllithium or sodium hydride, and alkaline earth metal compound is methylmagnesium-chloride or ethylmagnesium chloride, and (3) go on foot described MX 4Be selected from titanium tetrachloride or zirconium tetrachloride, the organism that is used for extracted residues is a toluene.
10, in accordance with the method for claim 5, it is characterized in that the temperature of reaction in (2) and (3) step is-10～40 ℃, described ether solvents is ether or tetrahydrofuran (THF),
11, a kind of olefine polymerizing process, comprise that with the described catalyzer of claim 1 be Primary Catalysts, with aikyiaiurnirsoxan beta or aluminum alkyls is promotor, make alkene under 0～110 ℃, 0.1～1.0MPa condition, carry out polyreaction, during reaction in the promotor in Al and the Primary Catalysts mol ratio of metal be 25～2000: 1.
12, in accordance with the method for claim 11, it is characterized in that described aikyiaiurnirsoxan beta is a methylaluminoxane, aluminum alkyls is selected from trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, aluminium diethyl monochloride or their mixture, during reaction in the promotor in Al and the Primary Catalysts mol ratio of metal be 150～1500: 1.
CN 03149936 2003-07-31 2003-07-31 Binuclear titanium series polyolefin catalyst, and its preparing method and use Expired - Lifetime CN1286861C (en)

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