CN1209387C - Catalyst for preparing polyethylene possessing distribution of molecular weight with doublet and/or broad peak - Google Patents

Catalyst for preparing polyethylene possessing distribution of molecular weight with doublet and/or broad peak Download PDF

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CN1209387C
CN1209387C CN 03115181 CN03115181A CN1209387C CN 1209387 C CN1209387 C CN 1209387C CN 03115181 CN03115181 CN 03115181 CN 03115181 A CN03115181 A CN 03115181A CN 1209387 C CN1209387 C CN 1209387C
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molecular weight
aluminium
boron
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weight distribution
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王齐
李利东
杨华祥
范志强
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Zhejiang University ZJU
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Abstract

The present invention discloses a catalyst for preparing polyethylene having molecular weight distribution with double and/or broad peaks. The catalyst comprises (a) a transitional metal compound using imine as ligand and (b) one kind of the following substances: (1) a boron-aluminoxane whose chemical formula is R1-[Al(R1)-O]1-[B(R2)-O]m-[Al(R3)-O]n-R3 or (2) carried boron-aluminoxane which is formed by carrying the boron-aluminoxane on the surface of an inert solid carrier, wherein R1, R2 and R3 in the chemical formula are hydrocarbyl. The catalysts in the class are adopted to catalyze the polymerization of ethylene; obtained polymers have molecular-weight distribution with doublet and/or broad peaks. The proportion of the low molecular weight part of ethene polymers prepared by the catalyst of the present invention is much less than the proportion of the high molecular weight part within a range of molecular weight distribution with double peaks, namely that the polymers with high molecular weight has advantages. The catalyst having the molecular weight distribution with double peaks has the advantages of good processing performance and strong mechanical performance.

Description

Preparation has catalyst of polyethylene bimodal and/or the broad peak molecular weight distribution
Technical field
The present invention relates to a kind of preparation and have catalyst of polyethylene bimodal and/or the broad peak molecular weight distribution.
Background technology
Poly toughness, intensity and rupture strength are important properties very, and these character can strengthen along with the increase of poly molecular weight.But polymericular weight increases, and its processing characteristics generally will variation.If polymkeric substance has wide or bimodal molecular weight distribution, then both can make polymkeric substance have high mechanical strength, good processing properties, particularly extrudability are arranged again.The method of producing the polyvinyl resin with bimodal molecular weight distribution at present mainly contains three kinds.First kind is that resin with different molecular weight carries out blend under molten state, and this method cost is than higher, and the homogeneity of resin is not good, so that influence the performance of resin.Second method is to carry out stage feeding polymerization by a plurality of reactors, prepares the different polymkeric substance of molecular weight respectively.This method can obtain to form resin comparatively uniformly, the handiness that can regulate is arranged, but on efficient and cost problem is arranged all.The third method is to adopt the polyethylene of single catalyst or mixed catalyst direct production wide molecular weight or bimodal molecular weight distribution in single reaction vessel.In this method, mixed catalyst has more report, discloses a kind of catalyzer of many active centre as Chinese patent CN1342716, and this catalyzer comprises Ti component and V component.
It is title complex part, that contain transition metal with the diimine that U.S. Pat 5955555 discloses multiple, under the activation of aluminum alkyls or aikyiaiurnirsoxan beta, can prepare linear polyethylene.But this patent does not relate to the preparation of double peak weight distributing polyethylene.
Summary of the invention
The purpose of this invention is to provide a kind of preparation and have catalyst of polyethylene bimodal and/or the broad peak molecular weight distribution.
Catalyzer of the present invention comprises following component a and b:
A) a kind of diimine ligand compound that contains transition metal has following structure:
Figure C0311518100041
R wherein a, R b, R c, R d, R eAnd R fBe alkyl; Mt is Fe or Co; X is a halogen atom.The substituent R in the part imines specifically aAnd R bBe methyl; R c, R d, R eAnd R fIdentical or different, be selected from a kind of in hydrogen, methyl, the sec.-propyl; X is fluorine, chlorine, bromine or iodine atom;
B) a kind of in the following material: (1) a kind of boron-aluminium-oxygen alkane consists of R 1-[Al (R 1)-O] l-[B (R 2)-O] m-[Al (R 3)-O] n-R 3, R in the formula 1, R 2, R 3Be alkyl, wherein 3≤l+m+n≤20,0.01≤l/n≤99,0.01≤m/ (l+n)≤1; L, m and n are positive integer; Or (2) load on above-mentioned boron-aluminium-oxygen alkane the loading type aikyiaiurnirsoxan beta that obtains on the inert solid carrier.Wherein inert solid carrier is silica gel or clay.When carrier is clay, can be inorganic polynite or through the fatty quaternary amine montmorillonite modified.
What particularly point out is, the b1 in the components b is loaded on the components b 2 that obtains on the inert solid carrier cooperate with component a, can prepare the polyethylene of bimodal and/or wide molecular weight distribution equally.
Components b in the catalyzer described in the present invention prepares by method described below.With alkane or aromatic hydrocarbon is solvent, with alkylboronic acids RB (OH) 2, after reacting with a kind of aluminum alkyls earlier, add same or another kind of aluminum alkyls then.Said mixture reacts with water at low temperatures, except that after desolvating, can obtain components b 1 and be white powder.Also can not remove and desolvate, the solution that contains components b 1 that makes is directly used.
When the components b 1 of preparation catalyzer, the substituting group on the selected aluminum alkyls is selected from C 1-C 20Straight or branched alkane substituting group, as methyl, ethyl, isobutyl-, butyl, hexyl or 2-ethylhexyl etc.Substituting group on the selected alkylboronic acids is selected from the alkyl of straight or branched, or contains the fragrant substituting group of phenyl ring, as methyl, ethyl, butyl, isobutyl-, phenyl or 4-fluoro phenyl.
When the components b 1 of preparation catalyzer, can adopt a kind of, two or more aluminum alkyls.When adopting two kinds of aluminum alkylss, the molar ratio of the aluminum alkyls that aluminum alkyls that elder generation adds and back add is 1/99-99/1, wherein is the best with 1/5-5/1.The molar ratio of alkylboronic acids and aluminum alkyls is 1/99-1/1, wherein is best with 1/50-1/3.
When the components b 1 of preparation catalyzer, the temperature when dripping water is the best with-10 ℃ to 10 ℃ wherein at-170 ℃ to-20 ℃.The amount that adds entry, relevant with the amount of used aluminum alkyls and boric acid.(H 2O+B)/the Al mol ratio is 0.51-0.99, wherein is best with 0.75-0.95.The water that drips above-mentioned amount can be finished in 0.5-2 hour.
When the components b 2 of preparation catalyzer, in the toluene solution that contains b1, add carriers such as an amount of silica gel or laminated clay, at 20-80 ℃, be preferably 30-60 ℃ of reaction 0.5-6 hour, be preferably 1-2 hour, can obtain components b 2 except that after desolvating.The solid weight that adds is the solution of the boron-aluminium-oxygen alkane of 1M in aluminium content, is 0.2-4g, and preferred add-on is at 0.4-1g.
When the components b 2 of preparation catalyzer, the silica gel of employing is the inorganic carrier of common load Ziegler-Natta catalyst or metallocene catalyst, and adoptable silica gel model is 952,955 etc.The clay that adopts also can be done the carrier of olefin polymerization catalysis, can be inorganic polynite or through the fatty quaternary amine montmorillonite modified.
With component a and b1 or b2, cooperate according to certain stoichiometry, can in organic solvents such as toluene, carry out the homogeneous phase or the slurry polymerization of ethene.Polyreaction can be to carry out under the 0.1-2.0MPa at 0-60 ℃, ethylene pressure.Preferred polymerization temperature is 20-50 ℃.The molecular weight distribution of prepared polymkeric substance and can be observed significantly bimodally on the graph of molecular weight distribution (GPC figure) of polymkeric substance between 2.5-9.0, and two peaks compare, and preponderates in the peak of high molecular part.
Characteristics of the present invention are to adopt single catalyst system, in single reaction vessel, by adopting boron-aluminium-oxygen alkane of the present invention is molecular weight and the molecular weight distribution that stoichiometry between promotor, the two kinds of components of regulating catalyzer is come controlling polymers, can obtain a series of molecular weight distribution forms from unimodal to bimodal.Particularly, adopt the ethene polymers of Preparation of Catalyst involved in the present invention, in its bimodal molecular weight distribution, the shared ratio of low-molecular-weight part will be significantly less than the shared ratio of high molecular part; That is to say to have high molecular weight polymers and preponderate.Such bimodal molecular weight distribution could well can embody good processing properties, can keep more intense mechanical property again.
Description of drawings
Fig. 1 is the molecular weight of polyethylene distribution plan (GPC figure) among the embodiment 2-4, a) embodiment 2, b among the figure) embodiment 3, c) embodiment 4;
Fig. 2 is the molecular weight of polyethylene distribution plan (GPC figure) in embodiment 5 and 6, a) embodiment 5, b among the figure) embodiment 6;
Fig. 3 is the molecular weight of polyethylene distribution plan (GPC figure) in embodiment 10 and 11, a) embodiment 10, b among the figure) embodiment 11;
Fig. 4 is the molecular weight of polyethylene distribution plan (GPC figure) among the embodiment 13-15, a) embodiment 13, b among the figure) embodiment 14, c) embodiment 15.
Embodiment
The present invention illustrates with the following examples, but scope of the present invention is not limited to these embodiment.
All synthetic and polyreactions are to carry out under the reaction conditions of anhydrous and oxygen-free.
The component a that is used for the catalyzer of embodiment is to prepare according to the method described in the US5955555.Concrete method is as follows.In the flask of 200ml, add 50ml methyl alcohol respectively, 2.0 gram 2,6 diacetyl pyridines and 4.32 grams, 2,6 diisopropyl anilines.Add several formic acid again and make catalyzer.Above-mentioned solution at room temperature stirs and spends the night, and has the faint yellow solid precipitation to generate.The solid that obtains after filtration obtains 3.6 gram faint yellow solid, i.e. two (2,6 diisopropyl phenyls)-2,6 diacetyl pyridine imines or { [(ArN=C (Me)) with cold methanol wash several after drying 2C 5H 3N] FeCl 2(Ar=2,6-diisopropyl aniline), productive rate 61%.In 10ml exsiccant tetrahydrofuran (THF), add the anhydrous FeCl of 0.1 gram 2, and dispersed with stirring.Add 0.38 gram, two (2,6 diisopropyl phenyls)-2,6 diacetyl pyridine imines again.The color of solution deepens gradually, and has blue precipitation to generate.Above-mentioned reactant at room temperature stirred 3 days, filtered then.The solid of gained washs after drying with pentane, obtains 0.4 gram blue solid, is { [(ArN=C (Me)) 2C 5H 3N] FeCl 2(Ar=2,6-diisopropyl aniline).
Adopt and use the same method, replace 2,6 diisopropyl anilines can prepare the title complex of another kind of part and iron with 2,6 xylidines.The component a that is used for the catalyzer of embodiment, its concrete example is: in following general formula,
Figure C0311518100071
Work as R aAnd R bBe methyl; R c, R d, R eAnd R fBe all sec.-propyl; Mt is Fe (II), and when X was Cl, this compound number was Fe-1.Work as R aAnd R bBe methyl; R c, R d, R eAnd R fBe all methyl; Mt is Fe (II), and when X was Cl, this compound number was Fe-2.
The components b 1 that is used for the catalyzer of embodiment is according to following method preparation.In 500 milliliters reaction flask, add 200 milliliters of toluene successively, 0.16 mole of triethyl aluminum.Reacted 1 hour with 0.004 mole of phenyl-boron dihydroxide at 0 ℃, at room temperature add 0.04 mole of triisobutyl aluminium then, and at room temperature stirred 30 minutes.The solution that obtains is cooled to-78 ℃, under fully stirring, slowly drips 3.0 gram water.After water adds, return to room temperature naturally, continue reaction 3 hours, obtain the toluene solution of water white boron-aluminium-oxygen alkane.The concentration of the aluminium of this solution is 1M.Under reduced pressure remove and desolvate, can obtain the solid boron-aluminium-oxygen alkane of white.Change the ratio of aluminum alkyls, the kind of alkylboronic acids can prepare other various boron-aluminium-oxygen alkanes.Proportioning during the components b 1 of concrete preparation catalyzer sees Table 1.
The components b 2 that is used for the catalyzer of embodiment is according to following method preparation.To 200 ml aluminium concentration is in the toluene solution of boron-aluminium-oxygen alkane of 1M, adds the silica gel of 0.08g, continues 50 ℃ of reactions after 3 hours, and decompression removes down and desolvates, and can obtain the boron-aluminium-oxygen alkane of white powder.The weight of the silica gel that is added can be between 0.04g-0.8g.Proportioning during the components b 2 of concrete preparation catalyzer sees Table 1.
The slurry polymerization of ethene carries out according to method described below.Polyreaction is to carry out in the polymerization reaction kettle of 500ml.The exsiccant reactor with ethylene gas displacement three times, is added 200ml toluene, components b 1 or b2 then successively.Stirring allows ethene reach capacity in toluene.Add Fe catalyzer initiated polymerization then.The constant pressure that in polymerization process, keeps ethene.After the polymerization 1 hour, with acidifying ethanol termination reaction, polymkeric substance behind washing, suction filtration 60 ℃ of following vacuum-dryings to constant weight, polymerization activity is calculated in weighing.Polyreaction can be carried out at 20-60 ℃, and the pressure of ethene is respectively 0.1 and 0.5MPa during polymerization.The consumption of catalyzer a, b component and other reaction conditions see Table 2 during polymerization.
The molecular weight of polymkeric substance and molecular weight distribution are measured on PL GPC-220 gel chromatograph.(with 1,2,4 trichlorobenzene are moving phase, and 150 ℃ of detected temperatures are done pervasive correction with polystyrene standards, K=59.1, α=0.69).
Each embodiment the results are shown in Table 2.
Embodiment 1
Adopt Fe-1 and do not add the ethyl-isobutyl aluminium alkoxide that boric acid prepares and make catalyzer, the result of catalyzed ethylene polymerization, as a comparison case.
Embodiment 2-7
Adopt Fe-1 and by the result of boron-aluminium-oxygen alkane catalyzed ethylene polymerization under differing temps of triethyl aluminum, triisobutyl aluminium and phenyl-boron dihydroxide preparation.
Embodiment 8
Adopt Fe-1 and by the result of the boron-aluminium-oxygen alkane catalyzed ethylene polymerization of triethyl aluminum, triisobutyl aluminium and the preparation of 4-fluorobenzene ylboronic acid.
Embodiment 9
Adopt Fe-1 and by the result of the boron-aluminium-oxygen alkane catalyzed ethylene polymerization of triethyl aluminum, triisobutyl aluminium and the preparation of normal-butyl boric acid.
Embodiment 10-12
Adopt Fe-1 and by the result of the load boron-aluminium-oxygen alkane catalyzed ethylene polymerization of triethyl aluminum, triisobutyl aluminium and phenyl-boron dihydroxide preparation.
Embodiment 13-15
Adopt Fe-2 and by the result of the boron-aluminium-oxygen alkane catalyzed ethylene polymerization of triethyl aluminum, triisobutyl aluminium and the preparation of 4-fluorobenzene ylboronic acid.
Table 1 catalyst component b1 and b2 prepare proportioning A, b
Numbering Boric acid The B/Al mol ratio H 2O/[B+Al] mol ratio Carrier consumption gram
EB - 0/100 0.9 0
BB5 nC 4H 9B(OH) 2 5/95 0.9 0
PB2 C 6H 5B(OH) 2 2/98 0.9 0
PB10 C 6H 5B(OH) 2 10/90 0.9 0
FB2 p-FC 6H 4B(OH) 2 2/98 0.9 0
FB5 p-FC 6H 4B(OH) 2 5/95 0.9 0
SPB2a C 6H 5B(OH) 2 2/98 0.9 0.02 c
SPB2b C 6H 5B(OH) 2 2/98 0.9 0.10 d
SPB5a C 6H 5B(OH) 2 5/95 0.85 0.10 c
So a) for building-up reactions is made solvent with 200ml toluene, keep concentration [Al+B]=1.0M.
When b) preparing boron-aluminium-oxygen alkane, used aluminum alkyls is triethyl aluminum and triisobutyl aluminium, and both mol ratios are 4: 1.
C) carrier was a silica gel 952,400 ℃ of following vacuum-dryings 6 hours.
D) carrier was a sodium-based montmorillonite, 200 ℃ of following vacuum-dryings 6 hours.
Table 2 vinyl polymerization result a
Embodiment catalyst system (Al+B)/Mt polymerization temperature ethylene pressure polymerization activity Log (molecular weight) bMw/Mn c
Component a components b 1 or b2 mol ratio ℃ MPa 10 7GPE/ (MolMt *H *MPa) 1 peak 2, peak
1 Fe-1 EB 2000 30 0.1 1.52 5.12 - 2.3
2 Fe-1 PB2 1000 30 0.1 0.81 4.84 4.08 6.1
3 Fe-1 PB2 2000 30 0.1 1.42 5.10 4.01 6.1
4 Fe-1 PB2 3000 30 0.1 2.01 5.03 3.97 4.6
5 Fe-1 PB2 2000 40 0.1 2.05 4.11 - 3.2
6 Fe-1 PB2 2000 50 0.1 1.85 5.17 4.11 5.6
7 Fe-1 PB10 3000 30 0.1 2.76 4.65 - 3.1
8 Fe-1 FB5 2000 30 0.1 0.97 5.16 - 6.3
9 Fe-1 BB5 2000 30 0.1 1.83 5.07 - 3.0
10 Fe-1 SPB2a 1000 50 0.1 1.40 2.77 5.10 8.1
11 Fe-1 SPB2b 1000 50 0.5 1.01 2.83 5.07 9.8
12 Fe-1 SPB5a 1000 50 0.1 1.20 2.89 5.25 7.8
13 Fe-2 FB2 800 30 0.1 0.6 4.16 5.08 6.7
14 Fe-2 FB2 1000 30 0.1 0.7 4.12 5.02 5.2
15 Fe-2 FB2 1200 30 0.1 1.0 4.11 5.06 4.8
A) polymerizing condition: 200ml toluene, [Fe]=1 * 10 -5M, 1 hour;
B) listed data are the molecular weight of each summit in the table;
C) be the molecular weight distributing index of whole polymkeric substance.Relevant graph of molecular weight distribution is seen accompanying drawing 1,2 and 3.

Claims (10)

1. one kind prepares and has catalyst of polyethylene bimodal and/or the broad peak molecular weight distribution, it is characterized in that being made up of following component a and components b:
The a component is a kind of title complex that contains the diimine of transition metal, has following structure:
Figure C031151810002C1
R wherein a, R b, R c, R d, R eAnd R fIt respectively is identical or different alkyl; Mt is transition-metal Fe or Co; X is a halogen;
The b component is a kind of in the following material: (1) a kind of boron-aluminium-oxygen alkane, it consists of R 1-[Al (R 1)-O] 1-[B (R 2)-O] m-[Al (R 3)-O] n-R 3, R in the formula 1, R 2, R 3Be alkyl, 3≤l+m+n≤20,0.01≤l/n≤99,0.01≤m/ (l+n)≤1 wherein, l, m and n are positive integer; Or (2) load on above-mentioned boron-aluminium-oxygen alkane the loading type boron-aluminium-oxygen alkane that obtains on the inert solid carrier;
Wherein the ratio between b component and a component with (aluminium+boron) and transition metal molar ratio computing, is 50～4000.
2. a kind of preparation according to claim 1 has catalyst of polyethylene bimodal and/or the broad peak molecular weight distribution, it is characterized in that, the composition correlation proportion of said boron-aluminium-oxygen alkane is 5≤l+m+n≤15,0.2≤l/n≤5,0.02≤m/ (l+n)≤0.25.
3. a kind of preparation according to claim 1 and 2 has catalyst of polyethylene bimodal and/or the broad peak molecular weight distribution, it is characterized in that, said boron-aluminium-oxygen alkane is under the condition of standard anhydrous and oxygen-free, with alkane or aromatic hydrocarbon is solvent, at-50 ℃ under 20 ℃, with alkylboronic acids R ' B (OH), R ' is an alkyl, earlier with a kind of aluminum alkyls reaction, reaction times is 0.5 to 8 hour, at room temperature add identical or different aluminum alkyls then again, under-170 ℃ to-20 ℃, slowly drip water, water droplet add finish after, naturally return to room temperature, and at room temperature reacted 1-6 hour, remove then or be not prepared from except that desolvating.
4. a kind of preparation according to claim 3 has catalyst of polyethylene bimodal and/or the broad peak molecular weight distribution, it is characterized in that, the temperature of said alkylboronic acids and aluminum alkyls reaction is at-10 ℃ to 10 ℃, time is 1-2 hour, temperature when dripping water is-100 ℃ to-50 ℃, water was added dropwise to complete at 0.5-2 hour, and the amount that adds entry is relevant with the amount of used aluminum alkyls and boric acid, (H 2O+B)/the Al mol ratio is 0.51-0.99.
5. a kind of preparation according to claim 3 has catalyst of polyethylene bimodal and/or the broad peak molecular weight distribution, it is characterized in that, in the preparation process of said boron-aluminium-oxygen alkane, when using different aluminum alkylss, successively the mol ratio of two kinds of aluminum alkylss that add is 1/20～20/1, and the alkylboronic acids of use and the mol ratio of aluminum alkyls are 1/99～1/1.
6. a kind of preparation according to claim 3 has catalyst of polyethylene bimodal and/or the broad peak molecular weight distribution, it is characterized in that, the mol ratio of said two kinds of aluminum alkylss is 1/5～5/1, and the alkylboronic acids of use and the mol ratio of aluminum alkyls are 1/50～1/3.
7. a kind of preparation according to claim 3 has catalyst of polyethylene bimodal and/or the broad peak molecular weight distribution, it is characterized in that the alkyl substituent on the said aluminum alkyls is selected from C 1-C 20Straight or branched alkane substituting group, the alkyl substituent on the alkylboronic acids is selected from the alkyl of straight or branched or contains the fragrant substituting group of phenyl ring.
8. a kind of preparation according to claim 1 has catalyst of polyethylene bimodal and/or the broad peak molecular weight distribution, it is characterized in that, said load boron-aluminium-oxygen alkane is to prepare by following steps: in the toluene solution of 0.02-2M boron-aluminium-oxygen alkane, add inert solid carrier, in aluminium content is the solution of the boron-aluminium-oxygen alkane of 1M, and quality is 0.2-4g, continues 20-80 ℃ of reaction after 0.5-4 hour, decompression removes down and desolvates, and can obtain the load boron-aluminium-oxygen alkane of white powder.
9. a kind of preparation according to claim 8 has catalyst of polyethylene bimodal and/or the broad peak molecular weight distribution, it is characterized in that, the add-on of said inert solid carrier is the solution of the boron-aluminium-oxygen alkane of 1M in aluminium content, is 0.4-1g.
10. a kind of preparation according to claim 8 has catalyst of polyethylene bimodal and/or the broad peak molecular weight distribution, it is characterized in that, said inert solid carrier is porous silica gel, lamellated clay; Clay is inorganic polynite or through the polynite of fatty quaternary amine modification.
CN 03115181 2003-01-23 2003-01-23 Catalyst for preparing polyethylene possessing distribution of molecular weight with doublet and/or broad peak Expired - Fee Related CN1209387C (en)

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