CN101407562A - Wide / bimodal molecular weight distribution polyolefin catalyst and preparation thereof - Google Patents
Wide / bimodal molecular weight distribution polyolefin catalyst and preparation thereof Download PDFInfo
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Abstract
The invention disclose a catalyst with wide/bimodality molecular weight distribution polyolefin and a preparation method thereof, belonging the field of catalysts, wherein the major catalyst comprises the following constituents: an inorganic substance carrier after activation treatment by an alkyl metal compound, the carrier loads at least one type of dialkyl magnesium compound, at least one type of polyfunctional compound and at least one type of titanium compound. The proportion among each constituent is calculated by each mol alkyl metal compound: 0.05-10 mol of carrier, 0.05-30mol of dialkyl magnesium compound, and 0.1-50mol of polyfunctional compound; and the amount of cocatalyst is calculated by titanium in the major catalyst being 1mol, and the cocatalyst is 10-300mol. The invention also discloses a preparation method of the catalyst, the catalyst is high in activity and the preparation method is simple, low requirement on equipment, little pollution to the environment, and has good hydrogen harmonic copolymerization performance. The catalyst is applicable to slurry process and gas phase polymerization technology and single reactor technology.
Description
Technical field
The present invention relates to a kind of be used for alkene particularly ethylene homo close or the Ziegle-Natta supported catalysts of copolymerization and with the preparation method of the synthetic wide molecular weight distribution polyolefin resin of this catalyzer.
Background technology
China's ethylene yield is big at present, guarantees for polyethylene industry provides reliable raw material.But because China and being becoming tight world petroleum resource day, back petroleum times, close on, an urgent demand develop consumption few, easily process and don't lose the rosin products of original performance.Wide molecular weight distribution/multimodal polyethylene can make the film attenuate, also can make the further thin-walled property of blow molded bottle, extruding pipe material and section bar, reduces the resin demand of single-piece commodity, and has better environmental stress cracking resistance; Wide molecular weight distribution/multimodal polyethylene resin returnability is good, the unimodal polyvinyl resin that the mechanical property of the resin that secondary uses is better than using first; Wide molecular weight distribution/multimodal polyethylene resin can obviously improve the processing characteristics of PE under the condition of the physicals of not losing PE substantially.Therefore, exploitation wide molecular weight distribution/multimodal polyethylene resin product has important and practical meanings.
Oneself method for preparing bimodal polyethylene of report mainly contains in the document at present: simple melt blending method, step reaction method and one section reaction method.Because one section reaction method only need be by regulating the kind and the distribution in active centre in the catalyst system, just can effectively regulate the molecular weight and the molecular weight distribution of polymerisate, and the steady quality of polymerisate, less investment, so the research of this respect is subjected to the attention of business circles and academia day by day.At present, adopt the wide branch of " one-stage process " preparation to mainly contain " compound primary catalysts method ", " complex carrier method " etc. in the method for weight distribution polyethylene.And the rare report of the poly patent of single preparing carriers broad peak.In existing efficient Mg-Ti catalyst system, recent development is to add the electron donor compound in the catalyst component preparation process, and evidence, the introducing of electron donor compound can improve the polymerization activity of catalyzer and the hydrogen regulation performance of catalyzer.
CN 1158136A discloses and used the long carbochain fat alcohol compound with α-side chain in the process of catalyst composition preparation, and the introducing of this compounds has improved the polymerization activity and the hydrogen regulation performance of catalyzer.But this system viscosity higher (can see the catalyst component that obtains good fluidity among the embodiment) brings difficulty to preparation process.
Summary of the invention
The purpose of this invention is to provide a kind of catalyzer that olefinic polymerization in the single reactor prepares wide molecular weight distribution or bimodal distribution polyvinyl resin that is suitable for.Provide a kind of single carried catalyst to prepare the preparation method of wide molecular weight distribution or bimodal distribution polyvinyl resin.This catalyst activity height, the preparation method is simple, and is low for equipment requirements, and environmental pollution is little.
The invention provides a kind of catalyzer that is used for the wide/double peak molecular weight distribution polyolefin of vinyl polymerization; Described catalyzer is made up of Primary Catalysts and promotor, it is characterized in that:
Primary Catalysts comprises following component: a kind of is MeR through general formula
1R
2R
3Alkyl metal cpd (b) activation treatment after inorganic oxide carrier (a), R in the formula
1, R
2, R
3Be C
1～C
30Alkyl; At least a general formula of load is MgR on this carrier
4R
5Dialkyl magnesium compound (c), R in the formula
4, R
5Be C
1～C
20Alkyl,
At least a general formula of load is
In R6, R7 in the general formula (d), R8, R9, six functional groups of R10, R11, wherein at least one functional group is a halogen group, and halogen comprises: F, C1, Br or I when halogen group during more than two, can be identical or different halogen groups; Wherein at least one functional group is hydroxyl, acyl group, amido or ester group, and they can be identical or different; Wherein at least one group is alkyl, the aromatic base of C1～C20, the derivative that contains heteroatomic substituted radical and replaced by described halogen group or functional group.
At least a general formula of load is Ti (OR
12)
4-mX
mTitanium compound (e), R
12Be C
1～C
20Aliphatic group, aryl radical, COR` or COOR`, wherein R` has C
1～C
10Fatty group or aromatic base;
Ratio between the each component is with every mole of MeR
1R
2R
3The alkyl metal cpd meter: carrier is 0.05～10mol, dialkyl magnesium compound MgR
4R
5Be 0.05～30mol, polyfunctional compound is 0.05～10mol, and titanium compound is: 0.1～50mol;
The promotor general formula is AlR
nX
3-n, R is C in the formula
1～C
15Aliphatic group, X is a halogen atom, n is 0 to 3 positive integer; The add-on of promotor is 1mol in the titanium content in the Primary Catalysts, and promotor is 10～300mol.
The Primary Catalysts preparation may further comprise the steps:
(1) will be MeR through general formula
1R
2R
3The alkyl metal cpd activation treatment after inorganic oxide carrier dissolving or be dispersed in the inert solvent;
(2) add dialkyl magnesium compound MgR
4R
5
(3) add polyfunctional compound
Product in inert solvent after dissolving or the dispersion;
(4) add titanium compound Ti (OR
12)
4-mX
m,-50 ℃～150 ℃ reactions were removed unreacted reactant and solvent after 0.5～24 hour, and adopted toluene and hexane wash, obtained Primary Catalysts.
Be used for carrier of the present invention and be mainly used in load active component.Carrier (a) is selected from silicon-dioxide, silicon carbide, magnesium dihalide, aluminum oxide, aluminum halide, oxidation sial, magnesium oxide, titanium oxide, vanadium oxide, gac, diatomite, chromic oxide and zirconium white or the like.Preferred silicon-dioxide, magnesium chloride.
Described alkyl metal cpd such as general formula (b) MeR
1R
2R
3Shown in, R in the formula
1, R
2, R
3Be identical or different C
1～C
30Alkyl is with C
1～C
30Straight chain, side chain or cyclic alkyl are good, Me is an IIIA family element in the periodic table of elements, preferred aluminium, relatively exemplary compounds as, trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, trioctylaluminum etc. are good with triethyl aluminum, triisobutyl aluminium especially wherein.
Described dialkyl magnesium compound such as general formula (c) MgR
4R
5Shown in, R in the formula
4, R
5Be identical or different C
1～C
20Alkyl, preferred identical or different C
2～C
15Alkyl, for example: ethyl, propyl group, butyl, amyl group, hexyl, octyl group etc.Concrete example includes but not limited to: di-n-butyl magnesium, normal-butyl sec-butyl magnesium, di-isopropyl magnesium, di-n-hexyl magnesium, sec.-propyl normal-butyl magnesium, ethyl n-hexyl magnesium, ethyl normal-butyl magnesium, di-n-octyl magnesium, butyl octyl magnesium, the dialkyl magnesium compound that is suitable in the reaction is preferably dibutylmagnesium, butyl ethyl magnesium or butyl octyl magnesium etc.
Described polyfunctional compound such as general formula (d)
Shown in.
In R6, R7 in the general formula (d), R8, R9, six functional groups of R10, R11, wherein at least one functional group is a halogen group, and halogen comprises: F, Cl, Br or I when halogen group during more than two, can be identical or different halogen groups; Wherein at least one functional group is functional groups such as hydroxyl, acyl group, amido or ester group, when functional group during more than two, can be identical or different functional groups; All the other groups are C
1～C
20Alkyl, aromatic base, the derivative that contains heteroatomic substituted radical and replaced by described halogen group or functional group.The polyfunctional compound specific examples includes but not limited to:
Preferably
Described titanium compound such as general formula (e) Ti (OR
12)
4-mX
m, X is a halogen atom in the formula, m is 0 to 4 integer, R
12Be C
1～C
20Aliphatic group, or aryl radical or COR`, or COOR` (R` has C
1～C
10Fatty group or aromatic base), each R
12Can be identical, also can be different.R
12Be preferably: methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, isobutyl-, the tertiary butyl, isopentyl, tert-pentyl, 2-ethylhexyl, phenyl, naphthyl, neighbour-aminomethyl phenyl ,-aminomethyl phenyl, right-aminomethyl phenyl, neighbour-sulfonic group phenyl, formyl radical, ethanoyl, benzoyl or the like.Specifically can select a kind of in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium, tetrabutyl titanate, isopropyl titanate, methoxyl group titanous chloride, dibutoxy titanium dichloride, three butoxy titanium chlorides, four phenoxide titaniums, a chlorine triple phenoxyl titanium, two chlorodiphenyl oxygen base titaniums, trichlorine one phenoxide titanium or their mixture for use, described titanium compound should be a completely soluble liquefied compound under application of temperature, in the non-polar solvent, preferred titanium tetrachloride.
Inert solvent described in the Primary Catalysts component of the present invention can adopt hexane, heptane, octane, appoint alkane, decane, undecane, dodecane, benzene,toluene,xylene, tetrahydrofuran (THF), 1,2-ethylene dichloride, chlorobenzene, 1,4-dioxane and other hydro carbons or halogenated hydrocarbon compound, above-mentioned inert solvent can be suitable for separately, use also capable of being combined.
In the preparation process of Primary Catalysts component of the present invention, the ratio between the each component is in every mole of general formula (b) compound: carrier is 0.05～10mol, preferred 0.1～5mol; Dialkyl magnesium compound MgR
4R
5(c) be 0.05～30mol, preferred 0.1～10mol; Polyfunctional compound (d) is 0.05～10mol, preferred 0.1～5mol; Titanium compound such as general formula (e) are: 0.1～50mol, preferred 1～30mol.
Reaction process among the present invention is generally at-50 ℃～150 ℃.Reaction times also can change in relative broad range, is generally 0.5～24 hour, should make the sufficiently long time of reaction between the component under desired reaction temperature.For further improving the particle form of catalyzer and the tap density of polymerisate, can use slight vacuum, means such as elevated temperature or nitrogen purging in intermediate steps.
The general formula of promotor of the present invention is AlR
nX
3-n, R is that hydrogen or carbonatoms are that 1～20 alkyl, X are halogen in the formula, n is the number of 0＜n≤3; Relatively exemplary compounds as: trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-tert aluminium, trioctylaluminum, aluminium diethyl monochloride, ethyl aluminum dichloride, sesquialter ethyl aluminum chloride etc. are good with triethyl aluminum, triisobutyl aluminium especially wherein; Can use separately, also can several mixing use.
The ratio of promotor and catalyst component is in the titanium content in the resulting catalyst component (1mol) among the present invention, and promotor is 10～300mol, preferred 50～200mol.
The catalyzer that the present invention relates to is applicable to the equal polymerization of ethene or the copolymerization of ethene and alpha-olefin, the wherein preferred propylene of alpha-olefin, 1-butylene, 1-hexene, 1-octene, 4-methyl-1-pentene, 1,3-dibutene, isoprene, vinylbenzene etc.
Can adopt following reaction conditions to carry out the equal polymerization of ethene or the copolymerization of ethene and alpha-olefin:
Polymerization temperature: 10～130 ℃, preferred 60～100 ℃
Polymerization pressure: 0.1～10.0MPa, preferred 0.1～2.0MPa
The invention provides a kind of wide molecular weight distribution polyolefin catalyst that is used to prepare.The catalyst activity height, the preparation method is simple, and is low for equipment requirements, and environmental pollution is little, has good hydrogen mediation copolymerization performance.This catalyzer is applicable to slurry process and gas-phase polymerization process.Be applicable to single reactor technology.
Embodiment
Embodiment is at preference of the present invention, but is not limited to following embodiment when practical application.
The Ti assay of catalyzer: claim 0.5g catalyzer concentrated sulfuric acid dissolution, adopt its content of spectrophotometric determination.
The relative molecular mass of PE and measure of spread thereof: adopt the Polymer Laboratoties PL-GPC220 of company type gel permeation chromatography (GPC) to measure the average weight-molecular mass (M of bimodal HDPE
w), number average relative molecular mass (M
n) and (M that distributes
w/ M
n), solvent is 1,2, the 4-trichlorobenzene, and the mass concentration of sample is 1mg/mL, and solution flow is 1.0mL/min, and probe temperature is 150 ℃.
Melt index (MI)) measures: adopt ASTM D1238-99 to measure.
Embodiment 1
(1) preparation of catalyst component: in the reactor of fully replacing, add 1g silicon-dioxide successively, newly steam hexane 30ml, AlEt through nitrogen
3Be 0.6ml (2.0M), be warming up to 50 ℃ of reaction 1h, add dibutylmagnesium (being mixed with concentration is the 1.0M n-heptane solution) 4.8ml, tetrahydrofuran (THF) 20ml, 2,2 '-methylene-bis (4-chlorophenol) 0.646g, be warming up to 60 ℃ of reaction 1h, be cooled to-25 ℃ and be added dropwise to TiCl
4Be 1.3ml, be warming up to 70 ℃ of reaction 2h, stop to stir, leave standstill, extract supernatant liquid, toluene, hexane respectively wash twice, and nitrogen dries up, and obtains the ingredient of solid catalyst of good fluidity, narrow diameter distribution.
(2) vinyl polymerization
At 0.5 liter of stainless steel autoclave, after nitrogen is fully replaced, in still, add above-mentioned synthetic catalyst component (1) 20mg successively, dehydration hexane 200ml, AlEt
3Solution 0.46ml (2mmol/ml) charges into hydrogen 0.28MPa after being warming up to 80 ℃, charges into ethene 0.45MPa, constant voltage isothermal reaction 2h.Experimental result sees Table 1.
Embodiment 2
(1) preparation of catalyst component: in the reactor of fully replacing, add 1g silicon-dioxide successively, newly steam hexane 30ml, AlEt through nitrogen
3Be 0.1ml (2.0M), be warming up to 50 ℃ of reaction 1h, be added dropwise to n-heptane solution (1.0M) 0.1ml of dibutylmagnesium, tetrahydrofuran (THF) 20ml, 2,2 '-methylene-bis (4-chlorophenol) 0.03g, be warming up to 60 ℃ of reaction 1h, be cooled to-25 ℃ and be added dropwise to TiCl
4Be 0.13ml, be warming up to 70 ℃ of reaction 2h, stop to stir, leave standstill, extract supernatant liquid, toluene, hexane respectively wash twice, and nitrogen dries up, and obtains the ingredient of solid catalyst of good fluidity, narrow diameter distribution.
Be AlEt in the vinyl polymerization
3The amount of solution changes into outside the 0.32ml, and other conditions are with embodiment 1
Embodiment 3
(1) preparation of catalyst component: in the reactor of fully replacing, add 1g silicon-dioxide successively, newly steam hexane 30ml, AlEt through nitrogen
3Be 6ml (2.0M), be warming up to 50 ℃ of reaction 1h, be added dropwise to n-heptane solution (1.0M) 12ml of dibutylmagnesium, tetrahydrofuran (THF) 50ml, 2,2 '-methylene-bis (4-chlorophenol) 0.03g, be warming up to 60 ℃ of reaction 1h, be cooled to-25 ℃ and be added dropwise to TiCl
4Be 4.0ml, be warming up to 70 ℃ of reaction 2h, stop to stir, leave standstill, extract supernatant liquid, toluene, hexane respectively wash twice, and nitrogen dries up, and obtains the ingredient of solid catalyst of good fluidity, narrow diameter distribution.
Be AlEt in the vinyl polymerization
3The amount of solution changes into outside the 0.43ml, and other conditions are with embodiment 1
Embodiment 4
Remove with 2,2 in the catalyst preparation process '-methylene-bis (4-chlorophenol) makes 1 into, 4-two chloro-2, outside the 5-dihydroxy-benzene 0.430g, other are identical with embodiment 1;
Be AlEt in the vinyl polymerization
3The amount of solution changes into outside the 0.41ml, and other conditions are with embodiment 1.
Embodiment 5
Remove with 2,2 in the catalyst preparation process '-methylene-bis (4-chlorophenol) makes 2-amine-4 into, outside the 6-two chloro-5-cresols 0.461g, other are identical with embodiment 1;
Be AlEt in the vinyl polymerization
3The amount of solution changes into outside the 0.37ml, and other conditions are with embodiment 1.
Embodiment 6
Remove with 2,2 in the catalyst preparation process '-methylene-bis (4-chlorophenol) makes 4-amine-2 into, outside the 6-dichloro cresols 0.427g, other are identical with embodiment 1;
Be AlEt in the vinyl polymerization
3The amount of solution changes into outside the 0.44ml, and other conditions are with embodiment 1.
Embodiment 7
Remove the TiCl in the catalyst preparation process
4Amount change into outside the 0.7ml, other are identical with embodiment 1;
Be AlEt in the vinyl polymerization
3The amount of solution changes into outside the 0.41ml, and other conditions are with embodiment 1.
Embodiment 8
Remove the TiCl in the catalyst preparation process
4Amount change into outside the 2.6ml, other are identical with embodiment 1;
Be AlEt in the vinyl polymerization
3The amount of solution changes into outside the 0.46ml, and other conditions are with embodiment 1.
Embodiment 9
Remove with in the catalyst preparation process do not add 2,2 '-methylene-bis (4-chlorophenol) outside, other are identical with embodiment 1;
Be AlEt in the vinyl polymerization
3The amount of solution changes into outside the 0.29ml, and other conditions are with embodiment 1.
Embodiment 10
The preparation of catalyst component: in the reactor of fully replacing through nitrogen, add the 1g magnesium dichloride successively, the new THF 30ml that steams, be added dropwise to n-heptane solution (1.0M) 2.8ml of dibutylmagnesium, 2,2 '-methylene-bis (4-chlorophenol) 0.33g, be warming up to 60 ℃ of reaction 1h, be cooled to-25 ℃ and be added dropwise to TiCl
4Be 8ml, be warming up to 70 ℃ of reaction 2h, be added dropwise to new steaming hexane 40ml, stop to stir, leave standstill, extract supernatant liquid, toluene, hexane respectively wash twice, and nitrogen dries up, and obtains the ingredient of solid catalyst of good fluidity, narrow diameter distribution.
Be AlEt in the vinyl polymerization
3The amount of solution changes into outside the 1.48ml, and other conditions are with embodiment 1.
Embodiment 11
Remove with 2,2 in the catalyst preparation process '-methylene-bis (4-chlorophenol) makes 1 into, 4-two chloro-2, outside the 5-dihydroxy-benzene 0.28g, other are identical with embodiment 10;
Be AlEt in the vinyl polymerization
3The amount of solution changes into outside the 1.31ml, and other conditions are with embodiment 1.
Embodiment 12
Remove with 2,2 in the catalyst preparation process '-methylene-bis (4-chlorophenol) makes 2-amine-4 into, outside the 6-two chloro-5-cresols 0.31g, other are identical with embodiment 10;
Be AlEt in the vinyl polymerization
3The amount of solution changes into outside the 1.21ml, and other conditions are with embodiment 1.
Embodiment 13
Remove with 2,2 in the catalyst preparation process '-methylene-bis (4-chlorophenol) makes 4-amine-2 into, outside the 6-dichloro cresols 0.30g, other are identical with embodiment 10;
Be AlEt in the vinyl polymerization
3The amount of solution changes into outside the 1.27ml, and other conditions are with embodiment 1.
Embodiment 14
Remove the TiCl in the catalyst preparation process
4Change into outside the titanium tetrabromide 2.0ml, other are identical with embodiment 1.
Be AlEt in the vinyl polymerization
3The amount of solution changes into outside the 0.41ml, and other conditions are with embodiment 1.
Embodiment 15
Except that the TiCl4 in the catalyst preparation process is changed into the purity titanium tetraethoxide 2.3, other are identical with embodiment 1.
Be AlEt in the vinyl polymerization
3The amount of solution changes into outside the 0.29ml, and other conditions are with embodiment 1.
Copolymerization embodiment
Embodiment 16
Preparation of catalysts is with embodiment 1;
The evaluating catalyst condition just after adding catalyzer, adds the 1-hexene of 15ml, carries out the copolymerization of ethene and hexene.Other are identical with embodiment 1.Experimental result sees Table 1.
Embodiment 17
Preparation of catalysts is with embodiment 3;
The evaluating catalyst condition just after adding catalyzer, adds the 1-hexene of 15ml, carries out the copolymerization of ethene and hexene.Other are identical with embodiment 3.Experimental result sees Table 1.
Embodiment 18
Preparation of catalysts is with embodiment 4;
The evaluating catalyst condition just after adding catalyzer, adds the 1-hexene of 15ml, carries out the copolymerization of ethene and hexene.Other are identical with embodiment 4.Experimental result sees Table 1.
Embodiment 19
Preparation of catalysts is with embodiment 5;
The evaluating catalyst condition just after adding catalyzer, adds the 1-hexene of 15ml, carries out the copolymerization of ethene and hexene.Other are identical with embodiment 5.Experimental result sees Table 1.
Embodiment 20
Preparation of catalysts is with embodiment 6;
The evaluating catalyst condition just after adding catalyzer, adds the 1-hexene of 15ml, carries out the copolymerization of ethene and hexene.Other are identical with embodiment 6.Experimental result sees Table 1.
Embodiment 21
Preparation of catalysts is with embodiment 7;
The evaluating catalyst condition just after adding catalyzer, adds the 1-hexene of 15ml, carries out the copolymerization of ethene and hexene.Other are identical with embodiment 7.Experimental result sees Table 1.
Embodiment 22
Preparation of catalysts is with embodiment 8;
The evaluating catalyst condition just after adding catalyzer, adds the 1-hexene of 15ml, carries out the copolymerization of ethene and hexene.Other are identical with embodiment 8.Experimental result sees Table 1.
Embodiment 23
Preparation of catalysts is with embodiment 9;
The evaluating catalyst condition just after adding catalyzer, adds the 1-hexene of 15ml, carries out the copolymerization of ethene and hexene.Other are identical with embodiment 9.Experimental result sees Table 1.
Embodiment 24
Preparation of catalysts is with embodiment 10;
The evaluating catalyst condition just after adding catalyzer, adds the 1-hexene of 15ml, carries out the copolymerization of ethene and hexene.Other are identical with embodiment 10.Experimental result sees Table 1.
Embodiment 25
Preparation of catalysts is with embodiment 11;
The evaluating catalyst condition just after adding catalyzer, adds the 1-hexene of 15ml, carries out the copolymerization of ethene and hexene.Other are identical with embodiment 11.Experimental result sees Table 1.
Embodiment 26
Preparation of catalysts is with embodiment 12;
The evaluating catalyst condition just after adding catalyzer, adds the 1-hexene of 15ml, carries out the copolymerization of ethene and hexene.Other are identical with embodiment 12.Experimental result sees Table 1.
Embodiment 27
Preparation of catalysts is with embodiment 13;
The evaluating catalyst condition just after adding catalyzer, adds the 1-hexene of 15ml, carries out the copolymerization of ethene and hexene.Other are identical with embodiment 13.Experimental result sees Table 1.
Embodiment 28
Preparation of catalysts is with embodiment 14;
The evaluating catalyst condition just after adding catalyzer, adds the 1-hexene of 15ml, carries out the copolymerization of ethene and hexene.Other are identical with embodiment 13.Experimental result sees Table 1.
Embodiment 29
Preparation of catalysts is with embodiment 15;
The evaluating catalyst condition just after adding catalyzer, adds the 1-hexene of 15ml, carries out the copolymerization of ethene and hexene.Other are identical with embodiment 13.Experimental result sees Table 1.
Table 1
| Ti content (quality %) | Catalytic efficiency (KgPE/gc at) | MW D | Tap density (g/ml) | MI 2.16 (g/10min) | |
| Embodiment 1 | 2.21 | 3.6 | 13.7 | 0.39 | 0.45 |
| Embodiment 2 | 1.53 | 1.0 | 8.7 | 0.37 | 0.33 |
| Embodiment 3 | 2.07 | 3.4 | 13.2 | 0.38 | 0.42 |
| Embodiment 4 | 1.94 | 3.0 | 11.1 | 0.37 | 0.37 |
| Embodiment 5 | 1.76 | 2.1 | 9.9 | 0.38 | 0.33 |
| Embodiment 6 | 2.10 | 2.4 | 12.3 | 0.38 | 0.41 |
| Embodiment 7 | 1.98 | 2.7 | 11.4 | 0.38 | 0.40 |
| Embodiment 8 | 2.18 | 3.6 | 13.6 | 0.39 | 0.44 |
| Embodiment 9 | 1.41 | 1.9 | 3.7 | 0.37 | 0.30 |
| Embodiment 10 | 7.11 | 44.3 | 27.5 | 0.32 | 0.38 |
| Embodiment 11 | 6.32 | 42.2 | 23.7 | 0.32 | 0.31 |
| Embodiment 12 | 5.83 | 39.9 | 24.0 | 0.30 | 0.29 |
| Embodiment 13 | 6.14 | 42.2 | 25.2 | 0.31 | 0.36 |
| Embodiment 14 | 1.50 | 2.3 | 10.7 | 0.38 | 0.34 |
| Embodiment 15 | 1.42 | 2.1 | 9.8 | 0.39 | 0.37 |
| Embodiment 16 | 2.21 | 3.9 | 14.4 | 0.38 | 0.72 |
| Embodiment 17 | 2.07 | 3.6 | 14.2 | 0.38 | 0.68 |
| Embodiment 18 | 1.94 | 3.5 | 13.4 | 0.39 | 0.65 |
| Embodiment 19 | 1.76 | 2.5 | 10.7 | 0.39 | 0.59 |
| Embodiment 20 | 2.10 | 3.4 | 12.9 | 0.38 | 0.66 |
| Embodiment 21 | 1.98 | 2.4 | 12.6 | 0.39 | 0.61 |
| Embodiment 22 | 2.18 | 3.3 | 14.1 | 0.39 | 0.67 |
| Embodiment 23 | 1.41 | 1.9 | 4.3 | 0.38 | 0.53 |
| Embodiment 24 | 7.11 | 44.0 | 28.1 | 0.32 | 0.73 |
| Embodiment 25 | 6.32 | 43.4 | 24.4 | 0.31 | 0.69 |
| Embodiment 26 | 5.83 | 41.1 | 24.8 | 0.30 | 0.66 |
| Embodiment 27 | 6.14 | 43.3 | 26.6 | 0.32 | 0.71 |
| Embodiment 28 | 1.50 | 2.7 | 11.7 | 0.39 | 0.67 |
| Embodiment 29 | 1.42 | 2.4 | 10.3 | 0.39 | 0.61 |
Claims (2)
1, a kind of catalyzer of wide/double peak molecular weight distribution polyolefin, described catalyzer is made up of Primary Catalysts and promotor, it is characterized in that:
Primary Catalysts comprises following component: a kind of is MeR through general formula
1R
2R
3The alkyl metal cpd activation treatment after inorganic matter carrier, R in the formula
1, R
2, R
3Be C
1～C
30Alkyl, Me are IIIA family elements in the periodic table of elements;
At least a general formula of load is MgR on this carrier
4R
5The dialkyl magnesium compound, R in the formula
4, R
5Be C
1～C
20Alkyl;
At least a general formula of load is
In R6 in the formula, R7, R8, R9, six functional groups of R10, R11, wherein at least one is a halogen group, at least one is a functional group, and this functional group is hydroxyl, acyl group, amido or ester group, and at least one is for the alkyl of C1～C20, aromatic base or contain heteroatomic substituted radical;
With at least a general formula of load be Ti (OR
12)
4-mX
mTitanium compound, R
12Be C
1～C
20Aliphatic group, aryl radical, COR` or COOR`, wherein R` has C
1～C
10Fatty group or aromatic base;
Ratio between the each component is with every mole of MeR
1R
2R
3The alkyl metal cpd meter: carrier is 0.05～10mol, dialkyl magnesium compound MgR
4R
5Be 0.05～30mol, polyfunctional compound is 0.05～10mol, and titanium compound is: 0.1～50mol;
The promotor general formula is AlR
nX
3-n, R is C in the formula
1～C
15Aliphatic group, X is a halogen atom, n is 0 to 3 positive integer; The add-on of promotor is 1mol in the titanium content in the Primary Catalysts, and promotor is 10～300mol.
According to the Preparation of catalysts method of the described wide/double peak molecular weight distribution polyolefin of claim 1, it is characterized in that 2, the Primary Catalysts preparation may further comprise the steps:
(1) will or be dispersed in the inert solvent through the dissolving of the inorganic matter carrier after the activation treatment;
(2) add dialkyl magnesium compound MgR
4R
5
(3) add polyfunctional compound
Product in inert solvent after dissolving or the dispersion;
(4) add titanium compound Ti (OR
12)
4-mX
m,-50 ℃～150 ℃ reactions were removed unreacted reactant and solvent after 0.5～24 hour, and adopted toluene and hexane wash, obtained Primary Catalysts.
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| CN2008102273703A CN101407562B (en) | 2008-11-28 | 2008-11-28 | Wide / bimodal molecular weight distribution polyolefin catalyst and preparation thereof |
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| CN101407562B CN101407562B (en) | 2011-06-01 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103380154A (en) * | 2010-11-22 | 2013-10-30 | 阿尔比马尔公司 | Activator compositions, their preparation, and their use in catalysis |
| CN105732852A (en) * | 2014-12-10 | 2016-07-06 | 中国石油天然气股份有限公司 | A Z-N catalyst |
-
2008
- 2008-11-28 CN CN2008102273703A patent/CN101407562B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103380154A (en) * | 2010-11-22 | 2013-10-30 | 阿尔比马尔公司 | Activator compositions, their preparation, and their use in catalysis |
| CN105732852A (en) * | 2014-12-10 | 2016-07-06 | 中国石油天然气股份有限公司 | A Z-N catalyst |
| CN105732852B (en) * | 2014-12-10 | 2018-08-10 | 中国石油天然气股份有限公司 | Z-N catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101407562B (en) | 2011-06-01 |
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