CN104059177B - A kind of load single metallocene catalyst for vinyl polymerization - Google Patents
A kind of load single metallocene catalyst for vinyl polymerization Download PDFInfo
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Abstract
The present invention relates to a kind of supported single metallocene catalyst for vinyl polymerization and preparation method, this catalyst includes (a) mono-metallocene compound；(b) chlorination alkyl silica modifier；(c) alkylaluminoxane；The product of (d) silica-gel carrier；Its preparation method includes: the preparation of (1) chlorination alkyl Si modification silica-gel carrier, the preparation of (2) alkylaluminoxane modified silica gel carrier, the preparation of (3) modified silica-gel load single metallocene catalyst, obtained single metallocene catalyst catalyzed ethylene polymerization or combined polymerization have the highest polymerization activity.Used silica gel support preparation method is simple, and the carried catalyst particle shape of gained is good, and size is adjustable.
Description
Technical field
The present invention relates to the preparation method of a kind of modified silica-gel load single metallocene catalyst, and gained catalyst
Application in terms of olefinic polymerization.
Background technology
The exploitation application of metallocene catalyst is after traditional Ziegler-Natta catalyst, and alkene gathers
Close the another important breakthrough of catalyst field, the particularly eighties, Kaminsky and Sinn et al. (Angew.
Chem., 1980,19,390;Adv.Organoment.Chem., 1980,18,99) develop efficiently
Promoter MAO (MAO) so that the research of metallocene catalyst entered into one fast-developing
Stage.In the last few years, in the research of olefin polymerization catalysis, urge with to the mono-metallocene of electron donor ligand
Agent increasingly comes into one's own, and document reports the catalyst of many this kind of unique energy, as with virtue
Epoxide (Organometallics, 1998,17 (11): 2152-2154), amino (Organometallics,
1996,15 (14): 3176-3181), amidino groups (J.Am.Chem.Soc., 2000,122 (5): 958-959),
Imino group (J.Am.Chem.Soc., 2000,122 (23): 5499-5509), phosphine amino
(Organometallics, 2003,22 (9): 1937-1947) etc. are to the luxuriant titanium of the list of electron donor ligand or Dan Mao
Zirconium.Owing to the MAO consumption needed for homogeneous single metallocene catalyst high activity to be reached is big, production cost is high,
And the polymer obtained is amorphous, it is impossible to make on widely used slurry process or gas phase polymerization technique
With, the effective way overcoming the problems referred to above is exactly supported for solubility single metallocene catalyst process.
At present, relevant supported metallocene research report is the most, wherein uses spherical magnesium chloride (containing alcohol)
The catalyst of load metallocene has good particle shape, such as PCT Int.Appl.99/21898；US
6,455,647；J.Mol.Catal.A2002,188,123；PCT Int.APP1.2004/078804；
CN 101817892；CN 101172988, but containing the components such as alcohol, water, alkoxyl, carrier system in carrier
Standby complicated；And with Si02Report for carrier is studied also a lot, such as WO2012044063；CN 102286114；
CN 1174848；CN 1174849；CN 1356343；US 4,808,561；US 5,026,797；US
5,763,543；US 5,661,098, but carrier preparation needs to use substantial amounts of alkyl aluminum, and catalyst
Load efficiency is relatively low, is still in the course of the polymerization process introduce substantial amounts of MAO, and disadvantage mentioned above limits silicon
The commercial Application of glue load single metallocene catalyst.
Also document is had to use the carrier loaded mono-metallocene (Polymer containing magnesium chloride, silica gel etc.
International, 2002,51,417-423;US5962360), but activity is the lowest, and in polymerization
Time need to add substantial amounts of MAO.
Summary of the invention
One of the object of the invention is to provide the Dan Mao of a kind of alkylaluminoxane/chlorination silicon alkyl/silica gel load
Metallic catalyst and preparation method thereof.
The two of the object of the invention are above-mentioned load single metallocene catalyst is used for vinyl polymerization or combined polymerization,
There is high polymerization activity.
A kind of supported single metallocene catalyst for vinyl polymerization of the present invention, this catalyst includes following group
The product divided:
A kind of supported single metallocene catalyst for vinyl polymerization of the present invention, this catalyst includes following group
The product divided:
(1) mono-metallocene compound；
(2) chlorination silicon alkyl；
(3) alkylaluminoxane；
(4) silica-gel carrier；
Component (1) described mono-metallocene compound, refers to the mono-metallocene coordination compound shown in formula 1,
Formula 1
In formula 1: M is the transition metal of the 4th race in the periodic table of elements；X1And X2Selected from halogen or unsubstituted
Aliphatic, aromatics or cyclic group, or a combination thereof；X3It is substituted or unsubstituted cyclopentadienyl group, indenes
Base or fluorenyl, at X3On any substituent group selected from hydrogen atom, substituted or unsubstituted aliphatic, aromatics or
Cyclic group, or a combination thereof；
X4For-O-RA、-NH-RA、-PH-RA、-N=RA、-S-RA、-O-Si-RB 3Or-O-C-RB 3, wherein:
RASelected from substituted or unsubstituted aliphatic, aromatics, cyclic group or a combination thereof；RBFor hydrogen atom, take
Generation or unsubstituted aliphatic, aromatics, cyclic group or a combination thereof；
Component (2) described chlorination alkyl silica modifier refers to compound described in below general formula: ClnSi(R1)4-n
Wherein R1Represent C1-C20Alkyl, n represents the integer of 1-4；
Component (3) described alkylaluminoxane formula is:
Wherein R represents C1-C12Alkyl, a represents the integer of 4-30.
In formula 1, X1And X2Preferably methyl, phenyl, benzyl or halogen.
X3The most substituted or unsubstituted cyclopentadiene, X3On the preferred hydrogen atom of each substituent group, methyl, second
Base, propyl group, normal-butyl, the tert-butyl group or hexyl.
X4Preferably-O-RAOr-N=RA；And X4It is-O-RATime, RAIt is 2, the dibasic aryl of 6-, RAUpper institute
State substituent group be methyl, ethyl, propyl group, normal-butyl, the tert-butyl group, cyclopenta, cyclohexyl, methoxyl group,
Ethyoxyl, propoxyl group or butoxy；X4It is-N=RATime, RAIt it is alkyl.
Component (2) described chlorination silicon alkyl R1Preferably methyl, ethyl, propyl group or phenyl；Concrete such as trimethyl
Chlorosilane, chlorotriethyl silane, tri isopropyl chlorosilane, dimethyl ethyl chlorosilane, diethylpropyl chlorine
Silane, dipropyl methylchlorosilane, dichloro-dimethyl silicon, Dichlorodiethyl silicon, dichlorophenyl silicon, two
Chloromethyl n-pro-pyl silane, dichloromethyl phenyl silane, trichloromethyl silane, trichloroethyl silane, phenyl
Trichlorosilane or Silicon chloride. etc., preferably trim,ethylchlorosilane, chlorotriethyl silane, dichloro-dimethyl silicon,
Dichlorodiethyl silicon, dichlorophenyl silicon, trichloromethyl silane, trichloroethyl silane and Silicon chloride..
For the load single metallocene catalyst of ethylene polymerization, the ratio between each reactant is with every gram of silicon
Glue carrier meter, chloric ether SiClx addition is 0.01-3mmol；The addition of mono-metallocene compound is
1-1000μmol。
The preferred titanium of central metal M or zirconium.
Described chlorination silicon alkyl, wherein R1Preferably methyl, ethyl, propyl group, n represents the integer of 1-4；
The preferred methyl of described alkylaluminoxane wherein R, a represents the integer of 10-30；Described alkyl aluminum
The preferred MAO of oxygen alkane (MAO), the MAO (MMAO) improved.
The preparation method of a kind of supported single metallocene catalyst for vinyl polymerization of the present invention, including as follows
Step:
(1) preparation of the silica-gel carrier of chlorination alkyl Si modification: under noble gas such as nitrogen is protected, by silicon
Glue carrier adds in reactor, adds solvent, is dispersed into suspension, adds chlorination alkyl silicon, is warming up to 0-90
DEG C, stirring reaction 3-24 hour；Preferably 30-80 DEG C, stirring reaction 3-6 hour, with 30-60 DEG C
Good.Then with solvent wash for several times, vacuum drying, obtain good fluidity containing chlorination alkyl Si modification
Silica supports, described solvent is toluene, benzene, dimethylbenzene, hexane, heptane, hexamethylene；Excellent
Select toluene, saturated alkane.
(2) preparation of the silica-gel carrier of alkylaluminoxane: under noble gas such as nitrogen is protected, by (1st)
The silica-gel carrier obtained in step adds in reactor, adds solvent, is dispersed into suspension, adds alkyl alumina
Alkane, is warming up to 30-90 DEG C, preferably 40-90 DEG C, stirring reaction 3-24 hour, preferably 3-8 hour,
Then washing for several times with solvent, vacuum drying, the silica gel containing alkylaluminoxane obtaining good fluidity carries
Body, described solvent is toluene, benzene, dimethylbenzene, hexane, heptane, hexamethylene；The preferred toluene of solvent.
(3) preparation of modified silica-gel load single metallocene catalyst: under noble gas such as nitrogen is protected, will
At the silica-gel carrier containing alkylaluminoxane that (2nd) step prepares, join in solvent and make serosity, will
The solution of single metallocene catalyst precursor is slowly dropped in this serosity, at 0-80 DEG C, reacts 1-120
Minute, obtain loading single metallocene catalyst, serosity can be directly used in polyreaction, or gained is reacted
Thing removes solvent, washs the solid supported single metallocene catalyst obtaining good fluidity after drying, described
Solvent is toluene, benzene, dimethylbenzene, hexane, heptane, hexamethylene；The preferred toluene of solvent, hexane or both
Mixture.
Load single metallocene catalyst for ethylene polymerization of the present invention can be used in different gathering
In conjunction method, such as gas-phase polymerization and slurry polymerization etc..Can be used for all polymerizations or the copolymerization of alkene, special
Be not applicable to ethylene homo close or the copolymerization of ethylene and other alpha-olefin, wherein alpha-olefin use propylene,
Butylene, amylene, hexene, octene, 4-methylpentene-1 etc..
In supported single metallocene catalyst method of the present invention, the catalyst of preparation is used directly for alkene
Polymerized hydrocarbon, as in gas-phase polymerization process;Olefinic polymerization can also be used for by additional aluminum alkyl catalyst, special
Be not add in slurry process alkyl aluminum can impurity in removing system, improve polymerization to a certain extent
Activity, and expensive MAO need not be added and make promoter.
The solvent that wherein polymerization is used is selected from alkane, aromatic hydrocarbon or halogenated hydrocarbons.Preferably hexane, pentane, heptan
A kind of in alkane, benzene, toluene, dichloromethane, chloroform, dichloroethanes or their mixture, most preferably
For a kind of in hexane, toluene, heptane or their mixture.
The load single metallocene catalyst concentration when polymerization is 1 × 10-8Mol/L～1 × 10-3Mol/L,
Preferred concentration range is 1 × 10-8Mol/L～1 × 10-5Mol/L.
Polymerization temperature is-78 DEG C-100 DEG C, preferably 20 DEG C-90 DEG C.
Polymerization pressure is 0.01-10.0MPa, preferably 0.01-2.0MPa.
The present invention compared with prior art has the following advantages:
1, modified silica gel carrier preparation method of the present invention is simple, and the catalyst granules form obtained is good,
Catalyst particle size is adjustable.
2, in load single metallocene catalyst method of the present invention, the catalyst of preparation has the highest ethylene
Polymerization catalytic activity.
3, in load single metallocene catalyst method of the present invention, the catalyst of preparation has good catalysis
Ethylene and the copolymerization of high alpha-olefin, Copolymerization activity is high.
4, load single metallocene catalyst of the present invention obtains resin powder have well for olefinic polymerization
Particle shape, bulk density is high, goes for slurry process and vapor phase method polymerization technique.
Analysis and characterization instrument used in the present invention is as follows:
1, ICP (plasma emission spectrum) characterizes: the weight percent of metal in quantitative determination carried catalyst
Ratio.The P1000 type ICP-AES plasma emission spectrometer that PE company of the instrument selection U.S. produces.
2, polymer molecular weight and the sign of molecular weight distribution: molecular weight and distribution thereof are by gel permeation chromatography
(GPC) measuring, instrument uses Waters Alliance GPCV 2000, and solvent is 1,2,4-trichloro-benzenes,
Sample concentration is lmg/ml, and solvent flow rate is 1.0ml/min;Measuring temperature is 150 DEG C.Each sample is measured
Secondary.
3, in polymer, co-monomer content characterizes: in polymer, hexene monomers content is by nuclear-magnetism13C-NMR surveys
Fixed, instrument uses Bruker AVANCE400, rate of scanning l00.6MHz, and temperature is 398K.Sampling time
For 5sec, time delay is 10sec, scanning times 5000 times.Sample concentration is 10-20mg/ml.
Embodiment
Embodiment 1
(1) preparation of chlorination silicon alkyl/silica-gel carrier
Under nitrogen protection, take dry silica-gel carrier 10.0 grams and add in glass reactor, add 100 millis
Rise dried hexane, be dispersed into suspension, add 1 milliliter of SiCl2(n-Bu)2, start stirring, be warming up to
30 DEG C, react 4 hours, vacuum drying, obtain the pressed powder of good fluidity.
(2) preparation of alkylaluminoxane/chlorination silicon alkyl/silica-gel carrier
Under nitrogen protection, take modified silica gel carrier obtained above 5.0 grams and add in glass reactor, add
60 milliliters of dried toluene, are dispersed into suspension, add the MAO (MAO) of 18 milliliters of 10wt%
Toluene solution, is warming up to 50 DEG C, stirring reaction 4 hours, then washs three times with 50 milliliters × 3 toluene,
Then wash with hexane, vacuum drying, obtain the pressed powder of good fluidity, i.e. contain MAO
Silica-gel carrier.
(3) preparation of supported single metallocene catalyst A
Under nitrogen protection, the silica-gel carrier 2.50 grams containing MAO that will be previously obtained, join
In glass reactor, add 35 milliliters of dried toluene and make serosity, be dissolved in 20 milliliters of toluene
0.108 gram of Cp*TiCl2(O-2,6-iPr2C6H3) solution be added drop-wise in reactor, 30 DEG C react 30 points
Clock, then with 35 milliliters of toluene washings, vacuum drying, obtains loading single metallocene catalyst A.Through ICP
Characterizing, in catalyst A, Ti weight content is 0.32%, and Al weight content is 10.21%.
Comparing embodiment 1
(1) preparation of alkylaluminoxane/silica-gel carrier
Under nitrogen protection, take the magnesium chloride support spraying prepared in 7.01 grams of embodiments 1 and add glass reaction
In device, add 90 milliliters of dried toluene, be dispersed into suspension, add the MAO of 40 milliliters of 10wt%
(MAO) toluene solution, is warming up to 50 DEG C, and stirring reaction 4 hours, then with 50 milliliters × 3
Toluene washs three times, then washs with hexane, vacuum drying, obtains the pressed powder of good fluidity, i.e.
Alkylaluminoxane/silica-gel carrier.
(2) preparation of supported single metallocene catalyst A*
Under nitrogen protection, the above-mentioned alkylaluminoxane/silica-gel carrier prepared 2.50 grams is joined glass anti-
Answer in device, add 25 milliliters of dried toluene and make serosity, be dissolved in 20 milliliters of toluene 0.108
Gram Cp*TiCl2(O-2,6-iPr2C6H3) solution droplets be added in reactor, 30 DEG C react 30 minutes,
Then with 30 milliliters of toluene washings, vacuum drying, supported non-metallocene single site catalysts A* is obtained.
Characterizing through ICP, in catalyst A*, Ti weight content is 0.34%, and Al weight content is 14.28%.
Embodiment 2
(1) preparation of chlorination silicon alkyl/silica-gel carrier
With embodiment 1 step (1), only by SiCl in embodiment 12(n-Bu)2It is changed to SiCl4。
(2) preparation of alkylaluminoxane/chlorination silicon alkyl/silica-gel carrier
With embodiment 1 step (2).
(3) preparation of supported metallocene catalyst B
With embodiment 1 step (3), obtain load metallocene catalyst B.Characterize through ICP, in catalyst B,
Ti weight content is 0.30%, and Al weight content is 11.18%.
Embodiment 3
(1) preparation of chlorination silicon alkyl/silica-gel carrier
With embodiment 1 step (1), only by SiCl in embodiment 12(n-Bu)2It is changed to CH3SiCl3。
(2) preparation of alkylaluminoxane/chlorination silicon alkyl/silica-gel carrier
With embodiment 1 step (2).
(3) preparation of supported metallocene catalyst C
With embodiment 1 step (3), obtain load metallocene catalyst C.Characterize through ICP, in catalyst C,
Ti weight content is 0.31%, and Al weight content is 11.22%.
Embodiment 4
(1), (2) are with (1), (2) preparation method in embodiment 1.
(3) preparation of supported metallocene catalyst D
With embodiment 1 step (3), only by 0.108 gram of Cp*TiCl in embodiment 12(O-2,6-iPr2C6H3)
Replace with 0..081 gram of CpTiCl2(N=CtBu2), obtain load metallocene catalyst D.Characterize through ICP,
In catalyst D, Ti weight content is 0.27%, and Al weight content is 10.16%.
High pressure ethylene polymerization is tested
High pressure ethylene polymerization experimentation is as follows:
In the rustless steel polymerization autoclave of 2 liters, respectively replace three times with nitrogen and ethylene, be subsequently adding 1000
Milliliter hexane solvent, along with the addition of hexane, by molten for triethyl aluminum (TEA) hexane of 5 milliliter of 1 mol/L
The 1-hexene of liquid and requirement adds, and is subsequently added into the load single metallocene catalyst that above-described embodiment prepares
50-100 milligram, is warming up to 60 DEG C, and pressure rises to and maintains 1.0MPa, reacts 1 hour.Polymerization is anti-
After should terminating, cooling, collect polyethylene particle powder, weigh.
Concrete polymerization result is shown in Table 1.
Table 1, supported single metallocene catalyst polymerization result
Table 1, supported single metallocene catalyst polymerization result
Claims (10)
1. the supported single metallocene catalyst for vinyl polymerization, it is characterised in that under this catalyst includes
The product of row component:
(1) mono-metallocene compound；
(2) chlorination silicon alkyl；
(3) alkylaluminoxane；
(4) silica-gel carrier；
Component (1) described mono-metallocene compound, refers to the mono-metallocene coordination compound shown in formula 1,
In formula 1: M is the transition metal of the 4th race in the periodic table of elements；X1And X2Selected from halogen or unsubstituted
Aliphatic, aromatics or cyclic group, or a combination thereof；X3It is substituted or unsubstituted cyclopentadienyl group, indenes
Base or fluorenyl, at X3On any substituent group selected from hydrogen atom, substituted or unsubstituted aliphatic, aromatics or
Cyclic group, or a combination thereof；
X4For-O-RA、-NH-RA、-PH-RA,-N=RA、-S-RA、-O-Si-RB 3Or-O-C-RB 3, wherein:
RASelected from substituted or unsubstituted aliphatic, aromatics, cyclic group or a combination thereof；RBFor hydrogen atom, take
Generation or unsubstituted aliphatic, aromatics, cyclic group or a combination thereof；
Component (2) described chlorination alkyl silica modifier refers to compound described in below general formula: ClnSi(R1)4-n
Wherein R1Represent C1-C20Alkyl, n represents the integer of 1-4；
Component (3) described alkylaluminoxane formula is:
Wherein R represents C1-C12Alkyl, a represents the integer of 4-30.
Supported single metallocene catalyst for vinyl polymerization the most according to claim 1, it is characterised in that
Described mono-metallocene coordination compound, central metal M is titanium or zirconium；X1And X2Selected from methyl, phenyl, benzyl
Or halogen；X3It is substituted or unsubstituted cyclopentadiene, X3On each substituent group selected from hydrogen atom, methyl,
Ethyl, propyl group, normal-butyl, the tert-butyl group or hexyl.
Supported single metallocene catalyst for vinyl polymerization the most according to claim 1, it is characterised in that
Described mono-metallocene coordination compound, wherein X4It is-O-RAOr-N=RA；And X4It is-O-RATime, RAIt is 2,6-
Dibasic aryl；X4It is-N=RATime, RAIt it is alkyl.
Supported single metallocene catalyst for vinyl polymerization the most according to claim 1, it is characterised in that
RAUpper described substituent group is methyl, ethyl, propyl group, normal-butyl, the tert-butyl group, cyclopenta, cyclohexyl, methoxy
Base, ethyoxyl, propoxyl group or butoxy.
Supported single metallocene catalyst for vinyl polymerization the most according to claim 1, it is characterised in that
Described chlorination silicon alkyl, wherein R1For methyl, ethyl, propyl group or phenyl；Described alkylaluminoxane,
For MAO (MAO), the MAO (MMAO) of improvement.
Load single metallocene catalyst for vinyl polymerization the most according to claim 1, it is characterised in that
Ratio between each reactant is in terms of every gram of silica-gel carrier, and chlorination silicon alkyl addition is 0.01-3mmol, alkane
Addition 0.01-30mmol of base aikyiaiurnirsoxan beta, the addition of mono-metallocene compound is 1-1000 μm ol.
Supported single metallocene catalyst for vinyl polymerization the most according to claim 1, it is characterised in that
In supported single metallocene catalyst, the weight content of aluminum is 1-15%；The weight content of central metal M is
0.05-2%.
8. the system of the supported single metallocene catalyst for vinyl polymerization described in any one in claim 1-7
Preparation Method, it is characterised in that comprise the following steps:
The first step: under inert gas shielding, silica-gel carrier reacts 3-24 with chlorination silicon alkyl at 0-90 DEG C
Hour；
Second step: under inert gas shielding, by the first step gained chlorination alkyl same alkyl aluminum of Si modification silica gel
Oxygen alkane reacts 3-24 hour at 0-90 DEG C；
3rd step: under inert gas shielding, by the second step gained same Dan Maojin of alkylaluminoxane modified silica-gel
Belong to compound to react 0.5-24 hour at 0-90 DEG C；
Solvent described in above three steps is toluene, benzene, dimethylbenzene, hexane, heptane or hexamethylene.
The preparation method of the supported single metallocene catalyst for vinyl polymerization the most according to claim 8,
It is characterized in that, be 30-60 DEG C in first step reaction temperature, dispersant used is toluene or saturated alkane；
It is 40-90 DEG C in second step reaction temperature；Dispersant used is toluene；It is first at dispersant used by the 3rd step
Benzene, hexane or both mixture.
10. in claim 1-7, the supported single metallocene catalyst for vinyl polymerization described in any one exists
Application in olefinic polymerization.
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| CN1539855A (en) * | 2003-10-29 | 2004-10-27 | 扬子石油化工股份有限公司 | Loaded method of load type Non-metallocene catalyst-and polymerizing application |
| CN101077879A (en) * | 2006-05-23 | 2007-11-28 | 中国石油天然气股份有限公司 | Monodentate compound containing phenoxy, preparation method and application thereof |
| CN101786019A (en) * | 2010-02-26 | 2010-07-28 | 中国石油天然气股份有限公司 | Transition metal catalyst containing cyclopentadienyl and preparation and application thereof |
| CN102453124A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Supported metallocene catalyst and olefin polymer, and preparation methods thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1539855A (en) * | 2003-10-29 | 2004-10-27 | 扬子石油化工股份有限公司 | Loaded method of load type Non-metallocene catalyst-and polymerizing application |
| CN101077879A (en) * | 2006-05-23 | 2007-11-28 | 中国石油天然气股份有限公司 | Monodentate compound containing phenoxy, preparation method and application thereof |
| CN101786019A (en) * | 2010-02-26 | 2010-07-28 | 中国石油天然气股份有限公司 | Transition metal catalyst containing cyclopentadienyl and preparation and application thereof |
| CN102453124A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Supported metallocene catalyst and olefin polymer, and preparation methods thereof |
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