CN101029106A - Use of ethene-polymerized catalyst - Google Patents
Use of ethene-polymerized catalyst Download PDFInfo
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- CN101029106A CN101029106A CN 200710085106 CN200710085106A CN101029106A CN 101029106 A CN101029106 A CN 101029106A CN 200710085106 CN200710085106 CN 200710085106 CN 200710085106 A CN200710085106 A CN 200710085106A CN 101029106 A CN101029106 A CN 101029106A
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Abstract
A catalyst for polymerizing ethane and its use are disclosed. It adopts toluene as solvent and modified methyl alundumne as catalytic auxiliaries, complex catalytic activity reaches to 7.68X106g/molTi.h under normal pressure. It's simple and cheap and has higher linear density.
Description
The present invention is that denomination of invention is ' ethylene rolymerization catalyst, preparation method and use ', the applying date to be that 2005.07.29 and application number are dividing an application of 200510028280.8 patent of invention.
Technical field
The present invention relates to a kind of purposes of ethylene rolymerization catalyst.This ethylene rolymerization catalyst is a kind of title complex of β-diimine class early transition metal titanium of halogen substituent, and this title complex is by the β-diimine of halogen substituent and the early transition metal titanium is synthetic forms.This title complex can be used for the polymerization of ethene.
Background technology
With the polyolefine is the macromolecular material of representative, occupies in national economy and consequence.Olefin polymerization catalysis such as ethene have been developed into the non-luxuriant transition-metal catalyst of the third generation through semicentennial development by the Qi Ge-Natta catalyst of the first-generation.Non-luxuriant transition-metal catalyst is just to begin in nearly ten years to occur, and has become the focus of olefin polymerization catalysis research at present.
The transition metal complex that contains N-N class polydentate ligand is modal non-metallocene olefin polymerization catalyst.But people such as Brookhart find the olefinic polymerization of diimine late transition metal complex highly active catalytic (JohnsonL.K., Killian C.M., Brookhart M.J.Am.Chem.Soc.1995,117,6414. first; Johnson L.K., Ecking S.M., Brookhart M.J.Am.Chem.Soc.1996,118,267.) since, people have produced keen interest to the research of Nonmetallocene organic coordination compound.People such as McConville are early transition metal title complex (Scollard J.D. that contain N-N class polydentate ligand of the first routine highly active catalytic olefinic polymerization in Ti, the Zr title complex (I) of a class chelating β-diamines of 1996 annual reports, McConville D.H., Payne N.C., Vittal J.J.Macromolecules 1996,29,5241.Scollard J.D., McConville D.H.J.Am.Chem.Soc.1996,118,10008.).
Beta-diimine class title complex (II) also is the important non-metallocene olefin polymerization catalyst that contains N-N class part of a class.Because the sterically hindered and electrocharge effect of beta-diimine part is easy to regulate and control by the substituent change on the arylamine; According to the character of metal and the change of coordination environment, all right different one-tenth key mode and the metal-complexings of beta-diimine part not only can be with two nitrogen-atoms with η as beta-diimine
2Mode and metal Cheng Jian can also be with five atoms with η
5Coordination mode and metal form the structure (shown in III) of similar metallocene; Therefore make synthetic, the structure of transition metal organic coordination compound of part with beta-diimine and the research of reaction property has caused chemist's extensive concern (Bourget-Merle, L.; Lappert, M.F.; Severn, J.R.Chem.Rev.2002,102,3031.), and find that this class title complex has some special reaction properties.The title complex that beta-diimine and many transition metal form is as Sc (Hayes, P.G.; Piers, W.E.; Lee, L.W.M.; Knight, L.K.; Parvez, M.; Elsegood, M.R.J.; Clegg, W.Organometallics 2001,20,2533.Hayes, P.G.; Piers, W.E.; McDonald, R.J.Am.Chem.Soc.2002,124,2132.), Ti (Kim, W.K.; Fevola, M.J.; Liable-Sands, L.M.; Rheingold, A.L.; Theopold, K.H.Organometallics 1998,17,4541.Budzelaar, P.H.M.; Van Oort, A.B.; Orpen, A.G.Eur.J.Inorg.Chem.1998,1485.), Zr (Jin, X.; Novak, B.M.Macromolecules 2000,33,6205.Vollmerhaus, R.; Rahim, M.; Tomaszewski, R.; Xin, S.X.; Taylor, N.J.; Collins, S.Organometallics 2000,19,2161.), V (Kim, W.K.; Fevola, M.J.; Liable-Sands, L.M.; Rheingold, A.L.; Theopold, K.H.Organometallics 1998,17,4541.), Cr (Gibson, V.C.; Newton, C.; Redshaw, C.; Solan, G.A.; White, A.J.P.; Williams, D.J.Eur.J.Inorg.Chem.2001,1895.MacAdams, L.A.; Kim, W.-K.; Liable-Sands, L.M.; Guzei, I.A.; Rheingold, A.L.; Theopold, K.H.Organometallics 2002,21,952.), Mn etc., can both be used as olefin polymerization catalysis.Activity was generally lower or medium when these title complexs were used for vinyl polymerization.
Because the beta-diimine title complex is synthetic simple, coordination mode is flexible, and coordination environment is easy to regulation and control, thereby its catalytic performance also can regulate by substituent change, is the title complex of a kind of comparatively ideal research structure and catalytic performance relation.In the former bibliographical information, substituent space steric effect is studied morely to the influence of the catalytic performance of various title complexs, and few applying electronic effect is regulated and control catalytic performance.The inventor is once at late transition metal catalyst---and pyridine diimine iron is to introduce halogen in the title complex, uses different electronic effect and the steric effects of halogen, has realized selectivity of ethylene polymerization and oligomerisation (Yaofeng Chen high reactivity, Changtao Qian, Jie Sun.Organometallics 2003,22,1231.Yaofeng Chen, Ruifang Chen, ChangtaoQian, Xicheng Dong, Jie Sun.Organometallics 2003,22,4312.).The inventor introduces halogen in the beta-diimine title complex, with the electronic effect and the steric effect of halogen the coordination environment of title complex is regulated and control, thereby is regulated the catalytic performance of title complex, develops the ethylene rolymerization catalyst system of application prospect.
Goal of the invention
The purpose of this invention is to provide a kind of new ethylene rolymerization catalyst, it be a kind of halogen substituent β-diimine class titanium complex purposes it can be used for catalyzed ethylene polymerization.
Summary of the invention
The purposes of ethylene rolymerization catalyst provided by the invention, ethylene rolymerization catalyst of the present invention are the β-diimine class organic titanium title complexs of the following halogen substituent of a kind of structure.
In the said structure formula, R
a-R
cBe hydrogen, C
1-30Alkyl, aryl or halo C
1-4Alkyl; R
a-R
cCan be the same or different R
aWith R
cAnd/or R
bWith R
cBetween can distinguish or become simultaneously aromatic ring again; Described virtue is bad to be phenyl ring, naphthalene nucleus or anthracene nucleus;
R
1-R
10In have one at least for halogen or halogen-containing group, all the other are hydrogen, halogen, C
1-6Alkyl, aryl or trihalomethyl group; R
1-R
10Can be the same or different, can be between them each other in key Cheng Huan;
X comprises halogen, C
1-C
30Alkyl, aryl, oxy radical, nitrogen-containing group at interior negatively charged ion or coordinating group; The halogen here comprises fluorine, chlorine, bromine or iodine; Described oxy radical can be propylene oxide base, butylene oxide ring base, epoxy pentyl or methyl ethyl diketone; Described nitrogen-containing group can be a secondary amine, especially two (C
1-16Alkyl) amine;
M=1 or 2, the number of expression and metal titanium coordinate part;
N=1,2,3 or 4;
Above-mentioned halo C
1-4Alkyl, preferably from trihalomethyl group, trifluoromethyl especially.Described aryl can be the C that phenyl or phenyl replace
1-4Alkyl;
Negatively charged ion negative charge sum should be identical with the burning attitude in the structural formula.
Ethylene rolymerization catalyst of the present invention can be the following organic titanium title complex of a kind of structural formula:
In the said structure formula, R
1-R
10, X as previously mentioned.
Ethylene rolymerization catalyst of the present invention, the organic titanium title complex that especially a kind of structural formula is following:
In the said structure formula, R
1 'And/or R
5 'And/or R
6 'And/or R
10 '=F, Cl, Br or I; R
3 'And/or R
8 '=H, CH
3Or CH
2(CH
3)
2
Synthesizing of catalyzer of the present invention:
The synthetic method of catalyzer of the present invention is by the negative ion of the β of halogen substituent-diimine class part or part and the compound TiX of early transition metal titanium
nIn organic solvent, mix, obtained the compound TiX of the negative ion of part or part and titanium in 0.1～48 hour to the temperature range internal reaction that refluxes at-78 ℃
nMol ratio be 1: 0.1-10; X is halogen, C
1-C
30Alkyl, aryl, oxy radical, nitrogen-containing group at interior negatively charged ion or coordinating group; Described aryl can be the C that phenyl or phenyl replace
1-4Alkyl.The halogen here comprises fluorine, chlorine, bromine or iodine; N=1,2,3 or 4; Organic solvent can be tetrahydrofuran (THF), ether, sherwood oil, pentane, hexane, hexanaphthene, heptane, benzene,toluene,xylene, chlorobenzene, dichlorobenzene, methylene dichloride, trichloromethane, CCl
4, 2,4-dioxane or 1,2-ethylene dichloride etc.Reacting general yield is 30～100%.
The structural formula of the β of described halogen substituent-diimine class part can for:
Wherein, R
a-R
cBe hydrogen, C
1-30Alkyl, aryl or halo C
1-4Alkyl; R
a-R
cCan be the same or different R
aWith R
cAnd/or R
bWith R
cBetween can distinguish or aromatic ring more simultaneously; Described aromatic ring is phenyl ring, naphthalene nucleus or anthracene nucleus;
R
1-R
10In have one at least for halogen or halogen-containing group, all the other are hydrogen, halogen, C
1-6Alkyl, aryl or halo C
1-4Alkyl; R
1-R
10Can be the same or different, can be between them each other in key Cheng Huan;
Above-mentioned halo C
1-4Alkyl, preferably from trihalomethyl group, trifluoromethyl especially.Described aryl can be the C that phenyl or phenyl replace
1-4Alkyl.
Part part of the present invention is as follows:
A kind of synthetic method of described β-diimine class part can be a raw material by beta-diketon and aryl amine derivatives, is catalyzer with the complex oxide of organic acid, mineral acid, Lewis acid or silicon, aluminium, and reaction obtained in 1-50 hour in organic solvent.Can add in the reaction or do not add molecular sieve as dewatering agent.Wherein the mol ratio of beta-diketon, aryl amine derivatives, catalyzer and molecular sieve is 1: 1-10: 0.001-3: 0-100 is recommended as 1: 1-5: 0.001-2: 0-50; Organic solvent can be tetrahydrofuran (THF), ether, sherwood oil, C
5-8Alkane, C
5-8Naphthenic hydrocarbon, benzene,toluene,xylene, chlorobenzene, dichlorobenzene, methylene dichloride, trichloromethane, CCl
4, 2,4-dioxane or 1,2-ethylene dichloride etc.; The yield of part is 20%～98%.
Described organic acid can be glacial acetic acid, tosic acid, trifluoromethane sulfonic acid etc.; Described mineral acid can be phosphoric acid, sulfuric acid, hydrochloric acid etc.; Described Lewis acid can be TiCl
4, AlCl
3, BF
3, BCl
3, rare earth muriate etc.
The purposes of the β of halogen substituent of the present invention-diimine class organic titanium title complex is to be used for catalyzed ethylene polymerization.
Ethylene polymerization carries out in round-bottomed flask or autoclave, and ethylene pressure is 0.1～100 * 10
5Pa, polymerization temperature are-30～300 ℃, are solvent with alkane, naphthenic hydrocarbon, aromatic hydrocarbons etc., with MAO (methylaluminoxane), and MMAO (methylaluminoxane of modification), EAO (ethyl aikyiaiurnirsoxan beta), BAO (butyl aikyiaiurnirsoxan beta), LiR
11(R
11=C
1-4Alkyl), AR
12 M 'Cl
N '(R
12=C
1-3Alkyl, m '=1-3, n '=0-2), Lewis acid (Lewis acid), LiR/Lewis acid (R
11=C
1-4Alkyl), AlR
M 'Cl
N '/ Lewis acid (R
12=C
1-3Alkyl, m '=1-3, n '=0-2), borine such as B (C
6F
5)
3Deng making promotor.The mol ratio of described ethylene rolymerization catalyst and promotor is 1: 1-200; Behind the reaction certain hour, centrifugal or filter with containing the methyl alcohol or the ethanol termination reaction of 5% hydrochloric acid as 5-100 minute, solid is with methyl alcohol or washing with alcohol, and is centrifugal again or filter, solid in 30～70 ℃ of vacuum-dryings to constant weight, the calculating productive rate of weighing.
Ethylene rolymerization catalyst provided by the invention not only synthetic method is simple, and the catalyzer cost is lower, and the catalyzed ethylene polymerization reactive activity is high.Find that first electronic effect plays very large effect to complex-catalyzed performance in this type of early transition metal title complex.Halogen-containing catalyzer is compared with not halogen-containing catalyzer in the part in the part part, and catalyzed ethylene polymerization is active significantly to be increased.With toluene is solvent, and MMAO is a promotor, and under the normal temperature and pressure, the catalytic activity of title complex is up to 7.68 * 10
6G/molTihatm, and the activity of corresponding methyl substituted title complex has only 8.8 * 10
3G/molTih, the catalytic activity of the title complex of halogen substituent is active nearly 1000 times of the title complex of methyl substituents.Product is a linear high-density polyethylene.
Description of drawings
Fig. 1 has provided the single crystal structure of title complex 3a.
Embodiment
The present invention will be helped further to understand by following embodiment, but content of the present invention can not be limited.
Following example has shown not ipsilateral of the present invention, and given data comprise synthetic, metal complexes synthetic of synthetic, the part of compound, polyreaction operation.Unless dated especially, the synthetic and polyreaction of metal complexes is all carried out under argon gas or nitrogen atmosphere.Raw material and solvent are all used the standard method purification process.Institute responds and all uses thin layer silica gel chromatogram tracking, the efficient tlc silica gel plate that uses the Yantai chemical institute to produce, and ultraviolet, iodine cylinder or potassium permanganate colour developing, rapid column chromatography carries out on silica gel H, and eluent is sherwood oil and ethyl acetate.The thermometer that uses in the experiment is not calibrated.1H NMR measures on the BrukerAMX-300 type nuclear magnetic resonance spectrometer at Varian EM-390.Ultimate analysis is measured by analytic centre of Shanghai organic chemistry institute of the Chinese Academy of Sciences.
Embodiment 1
Ligand 1 a's is synthetic
In having the 100ml there-necked flask of water trap and reflux condensing tube, (2.0g, 0.020mol), 2, (5.3g 0.041mol) and glacial acetic acid (0.02ml), adds 60ml toluene, reflux water-dividing 24 hours to the 6-difluoroaniline then to add beta-diketon successively.Stopped reaction, vacuum is spin-dried for toluene solvant, adds 40ml water and small amount of N a
2CO
3Be alkaline to solution, add the 50ml ether again, tell ether layer, water layer extracts at twice with the 60ml ether, and combined ether layer is used anhydrous Na
2SO
4Dry; Be spin-dried for ether, get the yellow-green colour solid, add about 10ml normal heptane recrystallization, get light yellow solid 5.575g, yield is 86.6%.
1H NMR (300MHz, CDCl
3): δ 12.23 (s, 1H, N-H), 7.09-6.87 (m, 6H, Ph-H), 5.11 (s, 1H ,=CH), 1.94 (s, 6H ,-CH
3). ultimate analysis: C
17H
14F
4N
2Calculated value: C, 63.35; H, 4.38; N, 8.69. measured value: C, 63.47; H, 4.33; N, 8.69.
Embodiment 2
Ligand 1 b's is synthetic
In the 100ml there-necked flask, add 1.0g beta-diketon, 3.7g penta fluoro benzene amine, 3g molecular sieve and 0.6gSi-Al oxide catalyst carrier (grade 135) successively, add 60ml toluene then, normal temperature stirred 48 hours down.Stopped reaction is spin-dried for toluene solvant after the filtration, add about 6ml normal hexane recrystallization in the head product, and product yield is 66.5%.
1H NMR (300MHz, CDCl
3): δ 12.08 (s, 1H, N-H), 5.20 (s, 1H ,=CH), 1.95 (s, 6H ,-CH
3). ultimate analysis: C
17H
8F
10N
2Calculated value: C, 47.46; H, 1.87; N, 6.51. measured value: C, 47.54; H, 2.15; N, 6.39.
Embodiment 3
Ligand 1 c's is synthetic
In having the 250ml there-necked flask of water trap and reflux condensing tube, add 2.0g beta-diketon, 6.5g2 successively, 6-dichlorphenamide bulk powder and 3.6g tosic acid add 100ml toluene then, reflux water-dividing 24 hours.Stopped reaction goes out supernatant liquid just after leaving standstill, add 50ml ether, 40ml water and 3.3g Na in lower floor's solid
2CO
3, stir and solid was dissolved fully in 10 minutes, tell ether layer, water layer extracts at twice with the 60ml ether, and combined ether layer is used anhydrous Na
2SO
4Dry; Be spin-dried for ether, add about 10ml normal heptane recrystallization, get light yellow solid, yield is 77%.
1H NMR (300MHz, CDCl
3): δ 12.15 (s, 1H, N-H), 7.34-7.31 (d, 4H, Ph-H), 7.03-6.98 (t, 2H, Ph-H), 5.07 (s, 1H ,=CH), 1.84 (s, 6H ,-CH
3). ultimate analysis C
17H
14Cl
4N
2Calculated value: C, 52.61; H, 3.64; N, 7.22. measured value: C, 52.50; H, 3.63; N, 7.18.
Embodiment 4
Ligand 1 d's is synthetic
In the 100ml there-necked flask, add 5.02g 2 successively, the hexane of 6-dibromo aniline, 1.0g beta-diketon and 50ml, nitrogen protection slowly drips the TiCl of 2ml down
4, normal temperature stirred 2 hours down.Decompression is spin-dried for hexane solvent, adds washing, extracted with diethyl ether, and head product carries out recrystallization with heptane, obtains ligand 1 d, and yield is 80.6%.
1H NMR (300MHz, CDCl
3): δ 12.20 (s, 1H, N-H), 7.57-7.53 (d, 4H, Ph-H), 6.90-6.81 (t, 2H, Ph-H), 5.06 (s, 1H ,=CH), 1.84 (s, 6H ,-CH
3). ultimate analysis: C
17H
14Br
4N
2Calculated value: C, 36.08; H, 2.49; N, 4.95. measured value: C, 35.86; H, 2.62; N, 4.82.
Embodiment 5
Ligand 1 e's is synthetic
In having the 250ml there-necked flask of water trap and reflux condensing tube, add 1.1g beta-diketon, 1.4g2-naphthylamines and 0.02g tosic acid successively, add 100ml toluene then, reflux water-dividing 18 hours, add 1.6g 4-5-trifluoromethylaniline again, continue to reflux stopped reaction 24 hours, drain solvent, product Na
2CO
3The aqueous solution wash, use extracted with diethyl ether then, the head product that obtains is used ethyl alcohol recrystallization again, obtains ligand 1 e, yield is 67.4%.
1H NMR (300MHz, CDCl
3): δ 7.7-7.2 (m, 11H, Ph-H), 1.90 (s, 2H, CH
2), 0.9 (d, 6H ,-CH
3). ultimate analysis: C
22H
19F
3N
2Calculated value: C, 71.73; H, 5.20; N, 7.60. measured value: C, 71.98; H, 5.34; N, 7.64.
Embodiment 6
Ligand 1 f's is synthetic
In the 250ml there-necked flask, add 1.11g beta-diketon, 2.2g 2-Iodoaniline and the 0.1ml vitriol oil successively, add 100ml toluene then, refluxed 25 hours, stopped reaction is drained solvent, and product anhydrous methanol recrystallization obtains ligand 1 f, and yield is 58.1%.
1H NMR (300MHz, CDCl
3): δ 7.6-7.0 (m, 11H, Ph-H), 1.45 (s, 2H, CH
2). ultimate analysis: C
20H
13F
3I
2N
2S calculated value: C, 38.48; H, 2.10; N, 4.49. measured value: C, 38.58; H, 2.14; N, 4.54.
Embodiment 7
Ligand 1 g's is synthetic
In the 250ml there-necked flask, add 2.40g raw material 1g-1,2.65g 2 successively, 6-two bromo-4-monomethylanilines and 0.1ml glacial acetic acid add the 100ml dehydrated alcohol then, refluxed 20 hours, stopped reaction is drained solvent, product obtains ligand 1 g by column chromatography, and yield is 83.1%.
1H NMR (300MHz, CDCl
3): δ 12.10 (s, 1H, N-H), 7.2-6.6 (m, 9H, Ph-H), 2.35 (s, 9H, CH
3), 1.05 (s, 3H, CH
3). ultimate analysis: C
23H
22Br
2N
2Calculated value: C, 56.81; H, 4.56; N, 5.76. measured value: C, 56.68; H, 4.54; N, 5.64.
Ligand 1 h's is synthetic
In the 100ml there-necked flask, add 1.60g 1 successively, 8-bisnaphthol, 2.55g p-Chlorobenzoic acid amide, 3g molecular sieve and 0.6g Si-Al oxide catalyst carrier (grade 135) add 60ml toluene then, and normal temperature stirred 48 hours down.Stopped reaction is spin-dried for toluene solvant after the filtration, head product obtains ligand 1 h by column chromatography, and yield is 71.6%.
1H NMR (300MHz, CDCl
3): δ 11.90 (s, 2H, N-H), 7.13-6.40 (m, 6H, Ph-H). ultimate analysis: C
22H
16Cl
2N
2Calculated value: C, 69.67; H, 4.25; N, 7.39. measured value: C, 69.68; H, 4.25; N, 7.34.
Embodiment 9
Title complex 3a's is synthetic
Ligand 1 a 0.8g (2.48mmol) is dissolved in the 20ml toluene, and-78 ℃ slowly drip 1.6M n-Butyl Lithium 1.55ml (2.48mmol) down, add in 10 minutes, rise to stirring at room 4 hours; 0.272ml (2.48mmol) titanium tetrachloride is dissolved in the 20ml toluene, the toluene solution of titanium tetrachloride slowly adds among the above-mentioned lithium salt solution 2a down in-78 ℃, rises to room temperature, and stirring is spent the night; Centrifugal, derive upper strata dark red solution, the toluene extracting at twice of 40ml heat of lower floor's brownish black solid, combining methylbenzene solution, vacuum concentration ,-30 ℃ of recrystallizations obtain brownish black solid 0.768g, yield 65%.Crystalline structure as shown in Figure 1.
1H NMR (300MHz, CDCl
3): δ 7.32-7.04 (m, 6H, Ph-H), 6.26 (s, 1H ,=CH), 2.20 (s, 6H ,-CH
3). ultimate analysis C
17H
13Cl
3F
4N
2Ti:C, 42.94; H, 2.76; N, 5.89. measured value: C, 42.85; H, 2.82; N, 5.98.
Embodiment 10
Title complex 3b's is synthetic
1.07g ligand 1 b is dissolved in the 20ml hexane ,-78 ℃ of slow down droppings are dissolved with 0.56g Ti (NMe
2)
4The 10ml hexane solution, added in 10 minutes, slowly rise to room temperature, be heated to 50 ℃, stirred 12 hours.The decompressing and extracting solvent, vacuum-drying 3 hours, head product toluene recrystallization gets title complex 3b, and yield is 66%.
1H NMR (300MHz, CDCl
3): δ 6.29 (s, 1H ,=CH), 2.47 (s, 18H ,-CH
3), 2.23 (s, 6H ,-CH
3). ultimate analysis: C
23H
25F
10N
5Ti calculated value: C, 45.34; H, 4.14; N, 11.49. measured value: C, 45.00; H, 4.32; N, 11.34.
Embodiment 11
Title complex 3c's is synthetic
1.366g ligand 1 c is dissolved in the 20ml toluene ,-78 ℃ slowly drip 1.6M n-Butyl Lithium 3.5ml down, add in 10 minutes, slowly rise to room temperature, and restir 4 hours obtains the xanchromatic lithium salt solution.Slowly add in this lithium salt solution while stirring and be dissolved with 0.62ml TiCl
4The orange-yellow toluene solution of 10ml, solution becomes dark red immediately, stirs under the room temperature 24 hours.Solution filters, and solid extracts at twice with the 60ml hot toluene, merging filtrate, and vacuum concentration is to half of liquor capacity, and-30 ℃ are freezing down, have the atropurpureus solid to separate out, and filter the final vacuum drying, get title complex 3c, and yield is 84.7%.
1H NMR (300MHz, CDCl
3): δ 7.42-7.45 (d, 4H, Ph-H), 7.24-7.19 (t, 2H, Ph-H), 6.48 (s, 1H ,=CH), 2.15 (s, 6H ,-CH
3). ultimate analysis C
17H
13Cl
7N
2Ti calculated value: C, 37.72; H, 2.42; N, 5.17. measured value: C, 37.60; H, 2.32; N, 5.34.
Embodiment 12
Title complex 3d's is synthetic
0.932g ligand 1 d is dissolved in the 20ml toluene ,-78 ℃ slowly drip 1.6M n-Butyl Lithium 1.75ml down, add in 10 minutes, slowly rise to room temperature, and restir 4 hours obtains the xanchromatic lithium salt solution.Slowly add in this lithium salt solution while stirring and be dissolved with 0.61g TiBr
4Toluene solution, solution becomes dark red immediately, stirs under the room temperature 24 hours.Solution filters, and solid extracts at twice with 50ml toluene, merging filtrate, and vacuum concentration is to half of liquor capacity, and-30 ℃ are freezing down, have the atropurpureus solid to separate out, and filter the final vacuum drying, get title complex 3d, and the yield of title complex 3d is 72%.
1H NMR (300MHz, CDCl
3): δ 7.66-7.63 (d, 4H, Ph-H), 7.09-7.03 (t, 2H, Ph-H), 6.48 (s, 1H ,=CH), 2.19 (s, 6H ,-CH
3). ultimate analysis C
17H
13Br
7N
2Ti calculated value: C, 23.95; H, 1.54; N, 3.29. measured value: C, 24.10; H, 1.32; N, 3.34.
Embodiment 13
Title complex 3e's is synthetic
1.23g ligand 1 e is dissolved in the 20ml methylene dichloride, slowly is added drop-wise in the dichloromethane solution of the 10ml that is dissolved with 0.08g NaH, adds in 10 minutes, stirs 10 hours, centrifugal, filter after, while stirring in this sodium salt solution slowly adding be dissolved with 1.10g TiCl
4(THF) 2 10ml dichloromethane solution, solution becomes dark red immediately, stirs 24 hours under the room temperature.Solution filters, and solid extracts at twice with the 20ml methylene dichloride, and merging filtrate is drained solvent, uses the toluene recrystallization, gets title complex 3e, and yield is 53%.
1H NMR (300MHz, CDCl
3): δ 7.7-7.2 (m, 11H, Ph-H), 5.90 (s, 1H ,=CH), 3.75 (t, 4H ,-CH
2), 2.19 (d, 6H ,-CH
3), 1.85 (m, 4H ,-CH
2). ultimate analysis C
26H
25Cl
3F
3N
2OTi calculated value: C, 52.69; H, 4.25; N, 4.73. measured value: C, 52.09; H, 4.39; N, 4.90.
Embodiment 14
Title complex 3f's is synthetic
1.04g ligand 1 f is dissolved in the 20ml ether ,-78 ℃ of slow down droppings are dissolved with 0.18g Ti (CH
3)
4The 10ml diethyl ether solution, added in 10 minutes, slowly rise to room temperature, be heated to 40 ℃, stirred 12 hours.The decompressing and extracting solvent, vacuum-drying 3 hours, head product hexane recrystallization gets title complex 3f, and yield is 77%.
1H NMR (300MHz, CDCl
3): δ 7.52-6.86 (m, 11H, Ph-H), 5.45 (s, 1H ,=CH), 1.3 (s, 9H, CH
3). ultimate analysis: C
23H
21F
3I
2N
2STi calculated value: C, 38.57; H, 2.96; N, 3.91. measured value: C, 38.06; H, 2.52; N, 3.64.
Embodiment 15
Title complex 3g's is synthetic
1.21g ligand 1 g is dissolved in the 20ml toluene ,-78 ℃ slowly drip 1.6M n-Butyl Lithium 1.56ml down, add in 10 minutes, slowly rise to room temperature, and restir 4 hours obtains the xanchromatic lithium salt solution.Slowly add the orange-yellow toluene solution of 10ml that is dissolved with 0.32ml TiCl4 while stirring in this lithium salt solution, solution becomes red-brown immediately, stirs 24 hours under the room temperature.Solution filters, and solid extracts at twice with 60ml toluene, merging filtrate, and vacuum concentration is to half of liquor capacity, and-30 ℃ are freezing down, have the red-brown solid to separate out, and filter the final vacuum drying, get title complex 3g, and yield is 63.7%.
1H NMR (300MHz, CDCl
3): δ 7.15-6.46 (m, 9H, Ph-H), 2.35 (s, 9H, CH
3), 1.05 (s, 3H, CH
3). ultimate analysis C
46H
42Br
4Cl
2N
4Ti calculated value: C, 50.72; H, 3.89; N, 5.14. measured value: C, 50.30; H, 4.32; N, 5.34.
Embodiment 16
Title complex 3h's is synthetic
0.95g ligand 1 h is dissolved in the 20ml toluene ,-78 ℃ of slow down droppings are dissolved with 1.03g Ti (CH
2Ph)
4The 10ml toluene solution, be warming up to 50 ℃ and stirred 24 hours.Solution for vacuum concentration is to half of original volume, and-30 ℃ freezing down, obtains 3h, yield 68.1%.
1H NMR (300MHz, CDCl
3): δ 7.13-6.20 (m, 24H, Ph-H), 2.60 (s, 4H ,-CH
2). ultimate analysis: C
36H
28Cl
2N
2Ti calculated value: C, 71.19; H, 4.65; N, 4.61. measured value: C, 71.25; H, 5.22; N, 4.38.
Embodiment 17
The polymerization bottle of 100ml is taken out roasting three times, with high pure nitrogen displacement twice, replaces with ethylene gas for the last time.Under 1atm ethene atmosphere, add 28.4ml toluene, temperature is controlled at 0 ℃, adds the MMAO toluene solution of 0.6ml (1mmol) while stirring, continues to stir ten minutes, and adding 1ml contains the toluene solution of 1 μ mol title complex 3a and picks up counting.React after 5 minutes, also with a large amount of acidifying washing with alcohol, polymer filtration, washing with alcohol, are weighed and calculated activity to constant weight in 50 ℃ of vacuum-dryings with the ethanol stopped reaction that contains 5% hydrochloric acid.The result is as shown in table 1.
Embodiment 18
The polymerization bottle of 100ml is taken out roasting three times, with high pure nitrogen displacement twice, replaces with ethylene gas for the last time.Under 1atm ethene atmosphere, add 28.4ml toluene, temperature is controlled at 15 ℃, adds the MMAO toluene solution of 0.6ml (1mmol) while stirring, continues to stir ten minutes, and adding 1ml contains the toluene solution of 1 μ mol title complex 3a and picks up counting.React after 5 minutes, also with a large amount of acidifying washing with alcohol, polymer filtration, washing with alcohol, are weighed and calculated activity to constant weight in 50 ℃ of vacuum-dryings with the ethanol stopped reaction that contains 5% hydrochloric acid.The result is as shown in table 1.
Embodiment 19
The polymerization bottle of 100ml is taken out roasting three times, with high pure nitrogen displacement twice, replaces with ethylene gas for the last time.Under 1atm ethene atmosphere, add 28.4ml toluene, be warming up to 30 ℃, add the MMAO toluene solution of 0.6ml (1mmol) while stirring, continue to stir ten minutes, adding 1ml contains the toluene solution of 1 μ mol title complex 3a and picks up counting.React after 5 minutes, also with a large amount of acidifying washing with alcohol, polymer filtration, washing with alcohol, are weighed and calculated activity to constant weight in 50 ℃ of vacuum-dryings with the ethanol stopped reaction that contains 5% hydrochloric acid.The result is as shown in table 1.
Embodiment 20
The polymerization bottle of 100ml is taken out roasting three times, with high pure nitrogen displacement twice, replaces with ethylene gas for the last time.Under 1atm ethene atmosphere, add 22ml toluene, be warming up to 50 ℃, add the MMAO toluene solution of 3ml (5mmol) while stirring, continue to stir ten minutes, adding 5ml contains the toluene solution of 5 μ mol title complex 3a and picks up counting.React after 20 minutes, also with a large amount of acidifying washing with alcohol, polymer filtration, washing with alcohol, are weighed and calculated activity to constant weight in 50 ℃ of vacuum-dryings with the ethanol stopped reaction that contains 5% hydrochloric acid.The result is as shown in table 1.
Embodiment 21
The polymerization bottle of 100ml is taken out roasting three times, with high pure nitrogen displacement twice, replaces with ethylene gas for the last time.Under 1atm ethene atmosphere, add 22ml toluene, be warming up to 70 ℃, add the MMAO toluene solution of 3ml (5mmol) while stirring, continue to stir ten minutes, adding 5ml contains the toluene solution of 5 μ mol title complex 3a and picks up counting.React after 20 minutes, also with a large amount of acidifying washing with alcohol, polymer filtration, washing with alcohol, are weighed and calculated activity to constant weight in 50 ℃ of vacuum-dryings with the ethanol stopped reaction that contains 5% hydrochloric acid.The result is as shown in table 1.
Embodiment 22
The polymerization bottle of 100ml is taken out roasting three times, with high pure nitrogen displacement twice, replaces with ethylene gas for the last time.Under 1atm ethene atmosphere, add 28.7ml toluene, be warming up to 30 ℃, add the MMAO toluene solution of 0.3ml (0.5mmol) while stirring, continue to stir ten minutes, adding 1ml contains the toluene solution of 1 μ mol title complex 3a and picks up counting.React after 5 minutes, also with a large amount of acidifying washing with alcohol, polymer filtration, washing with alcohol, are weighed and calculated activity to constant weight in 50 ℃ of vacuum-dryings with the ethanol stopped reaction that contains 5% hydrochloric acid.The result is as shown in table 1.
Embodiment 23
The polymerization bottle of 100ml is taken out roasting three times, with high pure nitrogen displacement twice, replaces with ethylene gas for the last time.Under 1atm ethene atmosphere, add 28.1ml toluene, be warming up to 30 ℃, add the MMAO toluene solution of 0.9ml (1.5mmol) while stirring, continue to stir ten minutes, adding 1ml contains the toluene solution of 1 μ mol title complex 3a and picks up counting.React after 5 minutes, also with a large amount of acidifying washing with alcohol, polymer filtration, washing with alcohol, are weighed and calculated activity to constant weight in 50 ℃ of vacuum-dryings with the ethanol stopped reaction that contains 5% hydrochloric acid.The result is as shown in table 1.
Embodiment 24
The polymerization bottle of 100ml is taken out roasting three times, with high pure nitrogen displacement twice, replaces with ethylene gas for the last time.Under 1atm ethene atmosphere, add 27.8ml toluene, be warming up to 30 ℃, add the MMAO toluene solution of 1.2ml (2mmol) while stirring, continue to stir ten minutes, adding 1ml contains the toluene solution of 1 μ mol title complex 3a and picks up counting.React after 5 minutes, also with a large amount of acidifying washing with alcohol, polymer filtration, washing with alcohol, are weighed and calculated activity to constant weight in 50 ℃ of vacuum-dryings with the ethanol stopped reaction that contains 5% hydrochloric acid.The result is as shown in table 1.
Embodiment 25
The polymerization bottle of 100ml is taken out roasting three times, with high pure nitrogen displacement twice, replaces with ethylene gas for the last time.Under 1atm ethene atmosphere, add 27.5ml toluene, be warming up to 30 ℃, add the MMAO toluene solution of 1.5ml (2.5mmol) while stirring, continue to stir ten minutes, adding 1ml contains the toluene solution of 1 μ mol title complex 3a and picks up counting.React after 5 minutes, also with a large amount of acidifying washing with alcohol, polymer filtration, washing with alcohol, are weighed and calculated activity to constant weight in 50 ℃ of vacuum-dryings with the ethanol stopped reaction that contains 5% hydrochloric acid.The result is as shown in table 1.
Embodiment 26
The polymerization bottle of 100ml is taken out roasting three times, with high pure nitrogen displacement twice, replaces with ethylene gas for the last time.Under 1atm ethene atmosphere, add 27.2ml toluene, be warming up to 30 ℃, add the MMAO toluene solution of 1.8ml (3mmol) while stirring, continue to stir ten minutes, adding 1ml contains the toluene solution of 1 μ mol title complex 3a and picks up counting.React after 5 minutes, also with a large amount of acidifying washing with alcohol, polymer filtration, washing with alcohol, are weighed and calculated activity to constant weight in 50 ℃ of vacuum-dryings with the ethanol stopped reaction that contains 5% hydrochloric acid.The result is as shown in table 1.
Embodiment 27
The polymerization bottle of 100ml is taken out roasting three times, with high pure nitrogen displacement twice, replaces with ethylene gas for the last time.Under 1atm ethene atmosphere, add 28.9ml toluene, be warming up to 30 ℃, add the MMAO toluene solution of 0.6ml (1mmol) while stirring, continue to stir ten minutes, adding 0.5ml contains the toluene solution of 0.5 μ mol title complex 3a and picks up counting.React after 10 minutes, also with a large amount of acidifying washing with alcohol, polymer filtration, washing with alcohol, are weighed and calculated activity to constant weight in 50 ℃ of vacuum-dryings with the ethanol stopped reaction that contains 5% hydrochloric acid.The result is as shown in table 1.
Embodiment 28
The polymerization bottle of 100ml is taken out roasting three times, with high pure nitrogen displacement twice, replaces with ethylene gas for the last time.Under 1atm ethene atmosphere, add 28.9ml toluene, be warming up to 30 ℃, add the MMAO toluene solution of 0.6ml (1mmol) while stirring, continue to stir ten minutes, adding 0.5ml contains the toluene solution of 0.5 μ mol title complex 3a and picks up counting.React after 20 minutes, also with a large amount of acidifying washing with alcohol, polymer filtration, washing with alcohol, are weighed and calculated activity to constant weight in 50 ℃ of vacuum-dryings with the ethanol stopped reaction that contains 5% hydrochloric acid.The result is as shown in table 1.
Embodiment 29
The polymerization bottle of 100ml is taken out roasting three times, with high pure nitrogen displacement twice, replaces with ethylene gas for the last time.Under 1atm ethene atmosphere, add 25.2ml toluene, be warming up to 30 ℃, add the MMAO toluene solution of 1.8ml (3mmol) while stirring, continue to stir ten minutes, adding 3ml contains the toluene solution of 3 μ mol title complex 3b and picks up counting.React after 20 minutes, also with a large amount of acidifying washing with alcohol, polymer filtration, washing with alcohol, are weighed and calculated activity to constant weight in 50 ℃ of vacuum-dryings with the ethanol stopped reaction that contains 5% hydrochloric acid.The result is as shown in table 1.
Embodiment 30
The polymerization bottle of 100ml is taken out roasting three times, with high pure nitrogen displacement twice, replaces with ethylene gas for the last time.Under 1atm ethene atmosphere, add 23.4ml toluene, be warming up to 30 ℃, add the MMAO toluene solution of 3.6ml (6mmol) while stirring, continue to stir ten minutes, adding 3ml contains the toluene solution of 3 μ mol title complex 3b and picks up counting.React after 15 minutes, also with a large amount of acidifying washing with alcohol, polymer filtration, washing with alcohol, are weighed and calculated activity to constant weight in 50 ℃ of vacuum-dryings with the ethanol stopped reaction that contains 5% hydrochloric acid.The result is as shown in table 1.
Embodiment 31
The polymerization bottle of 100ml is taken out roasting three times, with high pure nitrogen displacement twice, replaces with ethylene gas for the last time.Under 1atm ethene atmosphere, add 19ml toluene, be warming up to 30 ℃, add the MMAO toluene solution of 6ml (10mmol) while stirring, continue to stir ten minutes, adding 5ml contains the toluene solution of 5 μ mol title complex 3c and picks up counting.React after 60 minutes, also with a large amount of acidifying washing with alcohol, polymer filtration, washing with alcohol, are weighed and calculated activity to constant weight in 50 ℃ of vacuum-dryings with the ethanol stopped reaction that contains 5% hydrochloric acid.The result is as shown in table 1.
Embodiment 32
The polymerization bottle of 100ml is taken out roasting three times, with high pure nitrogen displacement twice, replaces with ethylene gas for the last time.Under 1atm ethene atmosphere, add 19ml toluene, be warming up to 30 ℃, add the MMAO toluene solution of 6ml (10mmol) while stirring, continue to stir ten minutes, adding 5ml contains the toluene solution of 5 μ mol title complex 3d and picks up counting.React after 60 minutes, also with a large amount of acidifying washing with alcohol, polymer filtration, washing with alcohol, are weighed and calculated activity to constant weight in 50 ℃ of vacuum-dryings with the ethanol stopped reaction that contains 5% hydrochloric acid.The result is as shown in table 1.
Embodiment 33
The polymerization bottle of 100ml is taken out roasting three times, with high pure nitrogen displacement twice, replaces with ethylene gas for the last time.Under 1atm ethene atmosphere, add 19ml toluene, be warming up to 30 ℃, add the MMAO toluene solution of 6ml (10mmol) while stirring, continue to stir ten minutes, adding 5ml contains the toluene solution of 5 μ mol title complex 3e and picks up counting.React after 60 minutes, also with a large amount of acidifying washing with alcohol, polymer filtration, washing with alcohol, are weighed and calculated activity to constant weight in 50 ℃ of vacuum-dryings with the ethanol stopped reaction that contains 5% hydrochloric acid.The result is as shown in table 1.
Embodiment 34
The polymerization bottle of 100ml is taken out roasting three times, with high pure nitrogen displacement twice, replaces with ethylene gas for the last time.Under 1atm ethene atmosphere, add 19ml toluene, be warming up to 30 ℃, add the MMAO toluene solution of 6ml (10mmol) while stirring, continue to stir ten minutes, adding 5ml contains the toluene solution of 5 μ mol title complex 3f and picks up counting.React after 60 minutes, also with a large amount of acidifying washing with alcohol, polymer filtration, washing with alcohol, are weighed and calculated activity to constant weight in 50 ℃ of vacuum-dryings with the ethanol stopped reaction that contains 5% hydrochloric acid.The result is as shown in table 1.
Embodiment 35
The polymerization bottle of 100ml is taken out roasting three times, with high pure nitrogen displacement twice, replaces with ethylene gas for the last time.Under 1atm ethene atmosphere, add 19ml toluene, be warming up to 30 ℃, add the MMAO toluene solution of 6ml (10mmol) while stirring, continue to stir ten minutes, adding 5ml contains the toluene solution of 5 μ mol title complex 3g and picks up counting.React after 60 minutes, also with a large amount of acidifying washing with alcohol, polymer filtration, washing with alcohol, are weighed and calculated activity to constant weight in 50 ℃ of vacuum-dryings with the ethanol stopped reaction that contains 5% hydrochloric acid.The result is as shown in table 1.
Embodiment 36
The polymerization bottle of 100ml is taken out roasting three times, with high pure nitrogen displacement twice, replaces with ethylene gas for the last time.Under 1atm ethene atmosphere, add 19ml toluene, be warming up to 30 ℃, add the MMAO toluene solution of 6ml (10mmol) while stirring, continue to stir ten minutes, adding 5ml contains the toluene solution of 5 μ mol title complex 3h and picks up counting.React after 60 minutes, also with a large amount of acidifying washing with alcohol, polymer filtration, washing with alcohol, are weighed and calculated activity to constant weight in 50 ℃ of vacuum-dryings with the ethanol stopped reaction that contains 5% hydrochloric acid.The result is as shown in table 1.
Table 1 β-diimine titanium complex catalyzed ethylene polymerization activity
a
| entry | complex(μmol) | temp(℃) | Al/Ti | time(min) | Polymer(g) | Activity b |
| 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 | 3a(1) 3a(1) 3a(1) 3a(5) 3a(5) 3a(1) 3a(1) 3a(1) 3a(1) 3a(1) 3a(0.5) 3a(0.5) 3b(3) 3b(3) 3c(5) 3d(5) 3e(5) 3f(5) 3g(5) 3h(5) 3i(5)c | 0 15 30 50 70 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 | 1000 1000 1000 1000 1000 500 1500 2000 2500 3000 2000 2000 1000 2000 2000 2000 2000 2000 2000 2000 2000 | 5 5 5 20 20 5 5 5 5 5 10 20 20 15 60 60 60 60 60 60 60 | 0.164 0.22 0.337 2.56 1.053 0.32 0.433 0.593 0.64 0.63 0.43 0.848 1.212 1.277 1.203 0.595 0.144 0.367 1.355 1.569 0.044 | 1968 2640 4044 1536 632 3840 5196 7116 7680 7560 5160 5088 1212 1702.8 240.6 119 28.8 73.4 271 313.8 8.8 |
A: toluene 30ml, 1atm; B:kg/molTi.h.atm; C: title complex 3i is that fluorine among the title complex 3a is by methyl substituted, in order to contrast with halogen-containing title complex.
Note: entry represents sequence number, and complex represents title complex, and temp represents temperature, and Al/Ti represents al-ti ratio, and time represents the time, and Polymer represents polymer weight, and Activity represents catalytic activity.
Claims (10)
1. the purposes of an ethylene rolymerization catalyst is characterized in that at ethylene pressure be 0.1～100 * 10
5Pa, polymerization temperature are-30～300 ℃, are solvent with alkane, naphthenic hydrocarbon or aromatic hydrocarbons, with methylaluminoxane, ethyl aikyiaiurnirsoxan beta, butyl aikyiaiurnirsoxan beta, the LiR of methylaluminoxane, modification
11, AlR
12 M 'Cl
N ', Lewis acid, LiR
11/ Lewis acid, AR
12 M 'Cl
N '/ Lewis acid or borine are made promotor; The mol ratio of described ethylene rolymerization catalyst and promotor is 1: 1-200; Reacted 5-100 minute; Wherein, R
11=C
1-4Alkyl; R
12=C
1-3Alkyl, m '=1-3, n '=0-2; Described ethylene rolymerization catalyst is the organic coordination compound of the β-diimine class early transition metal titanium of the following halogen substituent of a kind of structural formula:
R
a-R
cBe hydrogen, C
1-30Alkyl, aryl or halo (C
1-4) alkyl; R
a-R
cIdentical or different, perhaps R
aWith R
cAnd/or R
bWith R
cBetween become aromatic ring respectively or simultaneously again; Described aromatic ring is phenyl ring, naphthalene nucleus or anthracene nucleus;
R
1-R
10In have one at least for halogen or halogen-containing group, all the other are hydrogen, halogen, C
1-6Alkyl, aryl or halo (C
1-4) alkyl; R
1-R
10Identical or different, or between them each other in key Cheng Huan;
X comprises halogen, C
1-C
30Alkyl, aryl, oxy radical, nitrogen-containing group at interior negatively charged ion or coordinating group; The halogen here is fluorine, chlorine, bromine or iodine;
Above-mentioned aryl is the C that phenyl or phenyl replace
1-4Alkyl;
M=1 or 2, the number of expression and metal titanium coordinate part;
N=1,2,3 or 4;
Negatively charged ion negative charge sum should be identical with the burning attitude in the structural formula.
2. the purposes of a kind of ethylene rolymerization catalyst as claimed in claim 1 is characterized in that described oxy radical is propylene oxide base, butylene oxide ring base, epoxy pentyl or methyl ethyl diketone.
3. the purposes of a kind of ethylene rolymerization catalyst as claimed in claim 1 is characterized in that described nitrogen-containing group is a secondary amine;
4. the purposes of a kind of ethylene rolymerization catalyst as claimed in claim 1 is characterized in that described halo (C
1-4) alkyl is trifluoromethyl.
5. the purposes of a kind of ethylene rolymerization catalyst as claimed in claim 1 is characterized in that the organic titanium title complex that a kind of structural formula is following:
In the said structure formula, R
1-R
10, X as mentioned above.
6. the purposes of a kind of ethylene rolymerization catalyst as claimed in claim 5 is characterized in that the organic titanium title complex that a kind of structural formula is following:
In the said structure formula, R
1 'And/or R
5 'And/or R
6 'And/or R
10 '=F, Cl, Br or I; R
3 'And/or R
8 '=H, CH
3Or CH
2(CH
3)
2
7. the purposes of ethylene rolymerization catalyst as claimed in claim 1 is characterized in that this catalyzer obtains high molecular weight polymers or linear high-density polyethylene with the promotor catalyzed ethylene polymerization.
8. the purposes of ethylene rolymerization catalyst as claimed in claim 1 is characterized in that described promotor is a methylaluminoxane, the methylaluminoxane of modification, ethyl aikyiaiurnirsoxan beta, butyl aikyiaiurnirsoxan beta, C
1-4Alkyl Li, C
1-3Alkyl Al
1-3Cl
0-2, Lewis acid, C
1-4Alkyl Li/ Lewis acid, C
1-3Alkyl Al
1-3Cl
0-2/ Lewis acid or borine.
9. the purposes of ethylene rolymerization catalyst as claimed in claim 1 is characterized in that described product with the methyl alcohol or the ethanol termination reaction that contain 5% hydrochloric acid, and is centrifugal or filter, and solid is with methyl alcohol or washing with alcohol, centrifugal again or filter, and solid is in 30～70 ℃ of vacuum-dryings.
10. the purposes of ethylene rolymerization catalyst as claimed in claim 1 is characterized in that described catalyzed ethylene polymerization in toluene solvant, and the methylaluminoxane of modification is a promotor, and under the normal temperature and pressure, the catalytic activity of title complex reaches 7.68 * 10
6G/molTihatm.
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| CN102020741B (en) * | 2010-10-20 | 2012-11-14 | 中南民族大学 | Method for preparing linear low-density polyethylene and bifunctional catalyst system |
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