CN1280991A - Process for preparing carried catalyst for polymerization of olefin - Google Patents
Process for preparing carried catalyst for polymerization of olefin Download PDFInfo
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- CN1280991A CN1280991A CN 99109825 CN99109825A CN1280991A CN 1280991 A CN1280991 A CN 1280991A CN 99109825 CN99109825 CN 99109825 CN 99109825 A CN99109825 A CN 99109825A CN 1280991 A CN1280991 A CN 1280991A
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- polymerization
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- catalyst
- carried catalyst
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Abstract
A carried metallocene catalyst for olefin polymerization is prepared through mixing metallocene with alkylaluminoxyane in mole ratio of 1:(1-100) and carrying reaction of obtained solution on carrier at 70-250 deg.c for 2-48 hr and under normal pressure. Its advantages include high productivity and catalytic activity of catalyst and no sticking to reactor. When it is used for olefin polymerization, a cheap alkylaluminium other than expensive alkylaluminoxyane is added, and the resultant homopolymer has a specific weight not much different from that of the copolymer and a high apparent specific weight.
Description
The present invention relates to a kind of carried catalyst for polymerization of olefin and preparation method thereof.
Existing many reports that are used for olefinic polymerization about transistion metal compound, for example be used for USP 4 aspect the olefinic polymerization at relevant metallocene, 542,199 have reported the method that adopts metallocene catalyst and methylaluminoxane catalysis in olefine polymerization, and JP-A-01-502036 (1989) has introduced the method with metallocene catalyst and boron compound catalysis in olefine polymerization.Yet the polymer morphology with the preparation of the homogeneous phase metallocene compound of above-mentioned bibliographical information is poor, apparent specific gravity is low and can seriously be bonded in and make industrial production be difficult to carry out on the reactor wall.
In order to address the above problem, people's employing loads on metallocene makes carried catalyst on the carrier.W.Kaminskyl has introduced preparation method (the Makromol.Chem.Rapid Commun.14 of some known load metallocene catalysts, 239-243,1993), but the activity that the catalyzer of these method preparations has is not high, and the sticking still phenomenon of serious polymkeric substance takes place in the meeting that has.USP5,240,894 reports be a kind of method at the lesser temps load metallocene catalyst, as being lower than 66 ℃ of load metallocene catalysts, but serious sticking still phenomenon can take place in this catalyzer when being applied to olefinic polymerization.Patent WO 97/26285 has reported the preparation method of a kind of carried catalyst component and carried catalyst system; Be characterized in load need high pressure (＞10psig) carry out.
The objective of the invention is to overcome low, the sticking still of polymerisate poor morphology in the background technology, apparent specific gravity, shortcoming that catalytic activity is low, provide a kind of method of normal pressure load metallocene-alkylaluminoxane, the carried catalyst for polymerization of olefin of preparation high comprehensive performance.Prepare the catalyst production height with method of the present invention, and improved the apparent specific gravity of homopolymer, the apparent specific gravity difference of itself and multipolymer is dwindled.
The raw material metallocene compound that relates among the preparation method of the present invention has following structure:
Cp
ⅠMR
1R
2R
3???????(Ⅰ)????Cp
Ⅰ-A-R
1MR
2R
3???????(Ⅱ)
Cp
ICp
IIMR
1R
2(III) Cp
I-A-Cp
IIMR
1R
2(IV) wherein M is Ti, Zr or Hf; Cp
IAnd Cp
IIBe the monocycle of band conjugated pi electron such as cyclopentadienyl, indenyl, fluorenyl or the ligand of polynuclear plane, they can have substituting group or not have substituting group.R
1, R
2, R
3Be H
-, alkyl, haloid element or alkoxyl group, silylation, amido, phosphino-etc. contain the ligand compound of O, Si, N, P.A is-(CY
2) n-,-(SiY
2) n-,-(GeY
2) n-,-(Y)
2Si-O-Si (Y)
2-, wherein Y is H, alkyl, haloid element or alkoxyl group, silylation, amido, phosphino-, A also can be the ring texture group, n=1,2,3; A also can be doube bridge or many bridge constructions, promptly with plural bridge two parts is coupled together.
The raw material alkylaluminoxane that relates among the preparation method of the present invention has following structure: linear structure R-(AlR-O) n-AlR
2, ring texture (AlR-O) wherein n=1-40, preferably 10-20 of m; M=3-40,3-20 preferably, R is a kind of C
1-C
8Alkyl, methyl preferably.
The raw material carrier that relates among the preparation method of the present invention can be the organic or inorganic carrier, generally is cavernous carrier.The example of non-limiting scope such as MgCl
2, talcum, zeolite, inorganic oxide Al
2O
3, SiO
2, resin carrier such as polyethylene, polystyrene can be complex carrier such as MgCl
2/ SiO
2, also can use variety carrier such as MgCl simultaneously
2+ SiO
2, Al
2O
3+ SiO
2+ MgCl
2
The carrier granule size is 0.1-600mm, specific surface 50-1000m
2/ g, the aperture is the 50-500 dust, pore volume is 0.3-5.0cc/g.
Preparation of catalysts method of the present invention, carry out in the following order:
1, be 1 in molar ratio with metallocene and alkylaluminoxane: 100-1: 1, be preferably 1: 50-1: 5 are mixed into solution.Alkylaluminoxane concentration is the 0.01-10 mol in the solution, and solvent is the inert solvent of dryings such as hexane, certain herbaceous plants with big flowers alkane, ethylene dichloride, toluene, dimethylbenzene, ethylbenzene, Benzene Chloride, available mixed solvent, aromatic hydrocarbon solvent commonly used, the most frequently used toluene.
2, the weight ratio by carrier and alkylaluminoxane is 100: 1-1: 100, preferably 10: 1-1: 10, will carry out load-reaction under above-mentioned solution and the carrier normal pressure, and make supported metallocene-alkylaluminoxane olefin polymerization catalysis.Temperature of reaction is 70-250 ℃, and preferably 100-130 ℃, the reaction times is 2-48 hour, and preferably 8-16 hour can be above-mentioned solution to be added in the carrier or with carrier add in the solution.Above-mentioned carrier need dewater earlier or dehydroxylation is handled, and availablely vacuumizes, heats, method or other known methods of chemistry.The method of heating commonly used, temperature 100-600 ℃, preferably 200-300 ℃, can there be very big variation range in the treatment time, is generally 2-10 hour.
3, the carried catalyst that filtration, washing, drying make.
Carried catalyst of the present invention is applicable to gas phase, solution or slurry olefin polymerization.Olefinic monomer can be ethene or other high alpha-olefins, as propylene, vinylbenzene, hexene, octene, 4-methyl-amylene-1 etc., also can be that two or more alkene carries out copolymerization.Carried catalyst of the present invention is best suited for the copolymerization of ethylene homo or ethene and other alpha-olefins.
Need not add expensive alkylaluminoxane in the polymerization process again and do promotor, added promotor is corresponding inexpensive aluminum alkyls, trimethyl aluminium commonly used, triethyl aluminum, triisobutyl aluminium or its mixture.
Preparation method of the present invention and the catalyzer that makes thus have following characteristics:
1. the present invention adopts the long load-reaction time, is 2-48 hour, is generally 8-16 hour;
2. the present invention adopts high load-reaction temperature, is 70-250 ℃, is generally 100-130 ℃;
3. catalyst preparation process productive rate of the present invention is 90-99.9%;
4. catalyzer of the present invention is used for the polymkeric substance apparent specific gravity height that olefinic polymerization makes, and has particularly dwindled the apparent specific gravity difference with multipolymer owing to the apparent specific gravity of homopolymer is also higher, and when modulation altogether during amount of monomer, apparent specific gravity changes little like this;
5. catalyzer of the present invention is used for the polymkeric substance that olefinic polymerization makes, and serious sticking still phenomenon, catalytic activity height can not take place;
6. when catalyzer of the present invention was used for olefinic polymerization, promotor can expensive alkylaluminoxane and with corresponding inexpensive aluminum alkyls.
Prepare catalyzer and use institute's controlling catalyst by method of the present invention and the results are shown in table one in ethylene homo, copolymerization gained.
Table one, Preparation of Catalyst and ethylene homo and copolymerization result
Annotate: h: hour; PE: polymkeric substance; BD: apparent density
| Embodiment metallocene BD (g/ml) | Preparation of Catalyst load time (h) | Ethylene homo and copolymerization | ||||
| Productive rate (%) | Hexene (ml) | PE(g) | ||||
| 1?Et(Ind) 2ZrCl 2 | ?12 | ????95 | ????0 ????55 | ?298 ?394 | 0.37 0.40 | |
| 2?Et(Ind) 2ZrCl 2 | ?12 | ????99 | ????0 ????55 | ?308 ?420 | 0.378 0.415 | |
| 3(CH 3) 2Si(Ind) 2ZrCl 2 | ?12 | ????96 | ????0 | ?288 | ?0.34 | |
| 4?Et(Ind) 2ZrCl 2 | ?10 | ????94 | ????0 ????55 | ?270 ?354 | 0.34 0.38 | |
| 5?Et(Ind) 2ZrCl 2 | ?16 | ????98 | ????0 ????55 | ?280 ?360 | 0.36 0.39 | |
| 6?Et(Ind) 2ZrCl 2 | ?8 | ????92 | ????0 ????55 | ?279 ?372 | 0.345 0.37 | |
| 7?Et(Ind) 2ZrCl 2 | ?6 | |||||
| 8?Et(Ind) 2ZrCl 2 | ?2 | |||||
| 9?Et(Ind) 2ZrCl 2 | ?20 | |||||
| 10?Et(Ind) 2ZrCl 2 | ?48 | |||||
Embodiment
Embodiment 1:
Vehicle treated: SiO
2Carrier is handled after 6 hours at dry N under 250 ℃ in muffle furnace
2Protection is standby down.
Preparation of Catalyst: get above-mentioned SiO
2Carrier 3.12g puts into the two mouthfuls of flasks of 100ml round bottom that are connected to prolong, vacuumizes the dry N of displacement
2Protection.Get 199mg ethyl bridge two indenyl zirconium dichlorides [Et (Ind)
2ZrCl
2] after metallocene catalyst and 48ml methylaluminoxane (10%MAO toluene solution) stir and mix down, SiO is equipped with in the mixing solutions adding
2In two mouthfuls of flasks of the 100ml round bottom of carrier, after intensification begins to reflux, back flow reaction 12 hours; After the time, be cooled to 40 ℃, filter,, add under the 60ml hexane room temperature as above method after so repeating 4 times and wash twice, vacuumized dry catalyst then 4 hours with 5 minutes after-filtration of 40 ℃ of following agitator treatings of 60ml toluene.Get the pulverulent solids catalyst A
16.85g productive rate is 95%.
Olefinic polymerization: polymerization is to carry out in 2 liters autoclave.Autoclave is replaced 3 times with ethene after high temperature (more than 100 ℃) vacuumizes 2 hours, after being cooled to room temperature, add 25ml hexene (during copolymerization) at normal temperatures and pressures successively, 0.4ml triisobutyl aluminium (3.3M), 85mg carried catalyst, 1 liter of hexane, vinyl polymerization pressure is 1.4MPa, and 84 ℃ of polymerization temperatures rise to 84 ℃ of post polymerization 2 hours in temperature, added the 10ml hexene every 30 minutes in the polymerization process, the total add-on of hexene is 55ml.As above operate during ethylene homo, just do not add hexene.Get Alathon 298 grams, apparent specific gravity 0.37; Get multipolymer 394 grams, apparent specific gravity 0.40.
Embodiment 2:
Preparation of Catalyst: get 3.71g SiO
2Carrier, 229mg ethyl bridge two indenyl zirconium dichlorides [Et (Ind)
2ZrCl
2] metallocene catalyst and 55.6ml methylaluminoxane (10%MAO toluene solution), toluene or hexane are 80ml/ time during washing, make the pulverulent solids catalyst A by the method for example one
28.41g productive rate is 99.5%.
Olefinic polymerization: get Alathon 308 grams, apparent specific gravity 0.378 by embodiment one method; Get multipolymer 420 grams, apparent specific gravity 0.415.
Embodiment 3:
Preparation of Catalyst: get 3.0g SiO
2Carrier, 190mg dimethyl silicon bridge two indenyl zirconium dichloride [(CH
3)
2Si (Ind)
2ZrCl
2] metallocene catalyst and 45ml methylaluminoxane (10%MAO toluene solution), toluene or hexane are 60ml/ time during washing, make the pulverulent solids catalyst A by the method for example one
36.67g productive rate is 96%.
Olefinic polymerization: get Alathon 288 grams, apparent specific gravity 0.34 by embodiment one method.
Embodiment 4:
Preparation of Catalyst: get 3.0g SiO
2Carrier, 190mg ethyl bridge two indenyl zirconium dichlorides [Et (Ind)
2ZrCl
2] metallocene catalyst and 45ml methylaluminoxane (10%MAO toluene solution), back flow reaction 10 hours, toluene or hexane are 60ml/ time during washing, make the pulverulent solids catalyst A by the method for example one
46.52g productive rate is 94%.
Olefinic polymerization: get Alathon 270 grams, apparent specific gravity 0.34 by embodiment one method; Get multipolymer 354 grams, apparent specific gravity 0.38.Embodiment 5:
Preparation of Catalyst: get 3.0g SiO
2Carrier, 190mg ethyl bridge two indenyl zirconium dichlorides [Et (Ind)
2ZrCl
2] metallocene catalyst and 45ml methylaluminoxane (10%MAO toluene solution), back flow reaction 16 hours, toluene or hexane are 60ml/ time during washing, make the pulverulent solids catalyst A by the method for example one
56.80g productive rate is 98%.
Olefinic polymerization: get Alathon 280 grams, apparent specific gravity 0.36 by embodiment one method; Get multipolymer 360 grams, apparent specific gravity 0.39.
Embodiment 6:
Preparation of Catalyst: get 3.0g SiO
2Carrier, 190mg ethyl bridge two indenyl zirconium dichlorides [Et (Ind)
2ZrCl
2] metallocene catalyst and 45ml methylaluminoxane (10%MAO toluene solution), back flow reaction 8 hours, toluene or hexane are 60ml/ time during washing, make the pulverulent solids catalyst A by the method for example one
66.36g productive rate is 92%.
Olefinic polymerization: get Alathon 279 grams, apparent specific gravity 0.345 by embodiment one method; Get multipolymer 372 grams, apparent specific gravity 0.37.
Claims (10)
1, a kind of preparation method of carried catalyst for polymerization of olefin is characterized in that following these steps to carrying out:
(1) metallocene and alkylalumoxane solution are mixed, metallocene and alkylaluminoxane mol ratio are 1: 100-1: 1;
(2) will press the weight ratio 100 of carrier and alkylaluminoxane: 1-1 through carrier that dehydration or dehydroxylation are handled and above-mentioned solution: 100 mix mutually after, carried out load-reaction 2-48 hour at 70-250 ℃;
(3) after filtration, washing, drying makes.
2, the preparation method of a kind of carried catalyst for polymerization of olefin according to claim 1 is characterized in that metallocene and alkylaluminoxane are 1 in molar ratio: 50-1: 5.
3, the preparation method of a kind of carried catalyst for polymerization of olefin according to claim 1, the weight ratio that it is characterized in that carrier and carrier and alkylaluminoxane is 10: 1-1: 10.
4, the preparation method of a kind of carried catalyst for polymerization of olefin according to claim 1 is characterized in that the metal in the described metallocene is Ti, Zr or Hf.
5, the preparation method of a kind of carried catalyst for polymerization of olefin according to claim 1 is characterized in that described alkylalumoxane solution concentration is the 0.1-10 mol.
6, the preparation method of a kind of carried catalyst for polymerization of olefin according to claim 1 is characterized in that described alkylaluminoxane is a methylaluminoxane.
7, the preparation method of a kind of carried catalyst for polymerization of olefin according to claim 1 is characterized in that described carrier is a porous carrier.
8, the preparation method of a kind of carried catalyst for polymerization of olefin according to claim 1 is characterized in that described load-reaction 8-16 hour.
9, the preparation method of a kind of carried catalyst for polymerization of olefin according to claim 1 is characterized in that it is 200-300 ℃ that described dehydration or dehydroxylation are handled the temperature of carrier, and the treatment time is 2-10 hour.
10, porous carrier according to claim 7 is SiO
2
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991098250A CN1176112C (en) | 1999-07-16 | 1999-07-16 | Process for preparing carried catalyst for polymerization of olefin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991098250A CN1176112C (en) | 1999-07-16 | 1999-07-16 | Process for preparing carried catalyst for polymerization of olefin |
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| Publication Number | Publication Date |
|---|---|
| CN1280991A true CN1280991A (en) | 2001-01-24 |
| CN1176112C CN1176112C (en) | 2004-11-17 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464732A (en) * | 2010-11-16 | 2012-05-23 | 中国石油化工股份有限公司 | Olefin polymerization method and olefin polymer prepared with same |
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1999
- 1999-07-16 CN CNB991098250A patent/CN1176112C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464732A (en) * | 2010-11-16 | 2012-05-23 | 中国石油化工股份有限公司 | Olefin polymerization method and olefin polymer prepared with same |
| CN102464732B (en) * | 2010-11-16 | 2013-06-05 | 中国石油化工股份有限公司 | Olefin polymerization method and olefin polymer prepared with same |
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| CN1176112C (en) | 2004-11-17 |
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