CN1292389A - Compounded catalyst for olefinic polymerization - Google Patents
Compounded catalyst for olefinic polymerization Download PDFInfo
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- CN1292389A CN1292389A CN 99109944 CN99109944A CN1292389A CN 1292389 A CN1292389 A CN 1292389A CN 99109944 CN99109944 CN 99109944 CN 99109944 A CN99109944 A CN 99109944A CN 1292389 A CN1292389 A CN 1292389A
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Abstract
The compounded type catalyst containing metallocene for synthesizing polyolefine resin with molecular weight wide/double distribution is characterized by that its bimetal active center is formed from metallocene catalyst and traditional titanium series catalyst, and the cocatalyst for forming metallocene catalyst is mixed type alkylaluminiumoxyalkane. By regulating mole ratio of two kinds of metals and regulating dosage of two kinds or more than two kinds of alkylaluminiums when the mixed alkylaluminiumoxyalkane is prepared it can regulate molecular weight of polymer and molecular weight distribution in large range so as to obtain the polyolefine resin with wide molecular weight distribution. Said invented polyolefine resin possesses good workability and extensive application range.
Description
The present invention relates to a kind of compounded catalyst for olefinic polymerization, particularly synthetic molecular weight wide/pair distribution polyolefin resin is with the compounded catalyst that contains metallocene.
The catalyzer that metallocene compound and aikyiaiurnirsoxan beta are formed is used for olefinic polymerization, and its molecular weight product is low, narrow molecular weight distribution, and Mw/Mn=2-3[J.Polym.Sci.Pol.chem.Ed.23 (1985) 2117; EP-A-302424].Injection molding and general fiber product require narrow molecular weight, but the resin of a large amount of thermoformings, extrusion moulding, blow molding, foamex, film product requirement molecular weight distribution broad.
US-A-4461873 has reported two kinds of resin physics blending under molten state that molecular weight is different, and this kind method energy consumption, material consumption are higher, and it is many to mix the back gel content, and the apparent property of resin is poor.WO 92/15619, US-A-4307209 reported the two-stage polymerization reaction generate molecular weight wide/method of pair distribution resin.This method is used the successive polymerization in two or more reactors of a kind of catalyzer, requires catalyst life long, and by processing condition such as comonomer, temperature of reaction in the change different reactor, the schedule of operation complexity, facility investment is big, production cost is high.
Patent reports such as DE-A 3640924, EP-A 387691, US-A-5539066 in single reaction vessel, generate the technology of wide/pair distribution polyolefin resin with two kinds of metallocene catalysts, metallocene compound is that zirconium is luxuriant, hafnium is luxuriant or its mixture.But metallocene catalyst cost height, polymericular weight is low.
WO 96/09328,95/11264 has reported the technology with the titanium wide/pair distribution polyolefin resin that is that Ziegler-Natta catalyst and metallocene catalyst mixed system generate in single reaction vessel, metallocene catalyst adds aikyiaiurnirsoxan beta with metallocene and makes, at first aikyiaiurnirsoxan beta must be synthetic separately, the cost height, secondly the variable range of molecular weight distribution is very limited, often will be with a large amount of expensive metallocene catalysts.
The object of the present invention is to provide a kind of synthetic wide/pair distribution polyolefin resin catalyzer cheaply, increase the variable range of polyolefin resin molecular weight and distribution thereof.
For realizing purpose of the present invention, catalyzer of the present invention is that to be that Ziegler-Natta catalyst is composite make for metallocene catalyst and titanium, wherein the promotor of metallocene catalyst adopts mixed type alkylaluminoxane more than two kinds, in the mixed type alkylaluminoxane in aluminium and the metallocene compound mol ratio of metal generally be controlled at 1000: 1-1: between 1, be preferably in 250: 1-30: between 1; Titanium is that the promotor of Ziegler-Natta catalyst adopts aluminum alkyls, and the mol ratio of titanium metal is generally 2 in aluminum alkyls and the Ziegler-Natta catalyst: 1-200: between 1; The mol ratio of titanium metal can be 10 in metallocene and the Ziegler-Natta catalyst: 1-1: regulate between 50.
The metallocene compound of metallocene catalyst has following structure formation: Cp in the compounded catalyst of the present invention
mMR
nX
q, wherein Cp is luxuriant ring or substituent luxuriant ring is arranged, and also can be indenyl or fluorenyl, but between two Cp, indenyl or the fluorenyls also the bridge chain link; M is Zr, Ti or Hf, and R is C
1-C
8Alkyl or hydrogen atom, X is halogen F, Cl, Br, I or methyl.As Cp
2ZrCl
2, Cp
2ZrMe
2, Cp
2HfCl
2, Cp
2HfMe
2, Cp
2ZrHCl, Cp
2HfHCl, (CpMe
5)
2ZrCl
2, (CpMe
5)
2HfCl
2, CpZrCl
3, Ind
2ZrCl
2Deng, the alkyl of its promotor mixed type alkylaluminoxane can be two or more alkyl in methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, hexyl, octyl group, decyl, cyclohexyl, ring octyl group, the ring decyl etc., preferably contains methyl; As the aluminum alkyls of Ziegler-Natta catalyst promotor, can be trimethyl aluminium, triethyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-octylaluminium, three iso-octyl aluminium etc.
The preparation of metallocene catalyst is preferably adopted and is no less than two kinds of aluminum alkylss and water-containing column direct reaction generation mixed type alkylaluminoxane in the compounded catalyst of the present invention, be loaded with the silica gel and the metallocene compound reaction of mixed alkyl alumina alkane then, thereby formed the metallocene catalyst active centre on the silica gel surface.Aluminum alkyls comprises trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisopropylaluminiuand, three n-butylaluminum, triisobutyl aluminium, three sec-butyl aluminium, tri-tert aluminium, three amyl group aluminium, three hexyl aluminium, trioctylaluminum, three decyl aluminium, thricyclohexyl aluminium, three ring octyl group aluminium, three ring decyl aluminium etc., but more than listed aluminum alkyls two or more mix to use, preferably wherein contain trimethyl aluminium.
Water-containing column is as carrier for olefin polymerization catalyst the time, the introducing agent of water during again as synthetic aikyiaiurnirsoxan beta, the less water of introducing be no less than two kinds of aluminum alkyls direct reaction and generate the mixed type alkylaluminoxanes.The employing of water-containing column is finished synthetic and catalyst cupportization step in a reaction flask of aikyiaiurnirsoxan beta, has simplified Preparation of catalysts technology.
The specific surface of used silica gel is usually at 10-700m
2Between/the g, 200-400m preferably
2/ g; Pore volume between 3-0.5cc/g, 2-1cc/g preferably; The carrier water content between weight fraction 1-30%, 6-20% preferably; Average particle size particle size is between 0.3-100 μ m, and gas fluidised bed polymerisation used silica gel carrier average particle size particle size is preferably between the 30-60 μ m, and liquid polymerization used silica gel carrier average particle size particle size is preferably between the 0.3-10 μ m.Concrete preparation method is, water-containing column is added in mixed alkyl aluminum solutions whipped state under lentamente, always in aluminum alkyls and the water-containing column mol ratio of water generally 3: 1-1: between 2, preferably 1.2: 1-0.8: 1.Solvent alkane is as butane, pentane, hexane, heptane, octane, hexanaphthene; Aromatic hydrocarbons is as toluene, dimethylbenzene, trimethylbenzene etc.After water-containing column slowly added in the mixed alkyl aluminum solutions, temperature of reaction was controlled at-50-100 ℃ between, the reaction times added metallocene compound then between 1-20 hour.In the mixture of alkyl aluminum in aluminium and the metallocene compound mol ratio of metal generally be controlled at 1000: 1-1: between 1, be preferably in 250: 1-30: between 1.
After adding metallocene compound, in room temperature or slightly under the high-temperature behind the reaction 30min-4h, extract solution out, with the non-polar solvent washing for several times, non-polar solvent such as butane, pentane, hexane, heptane, octane, hexanaphthene, after generally washing static 30min, solvent does not have till the yellow substantially, purpose is to remove the component of not load, improves the flowability of catalyzer, reduces the content of low-molecular weight polymer in the polymkeric substance, as in vinyl polymerization, reducing the content of polyethylene wax, help improving the form of polymkeric substance in the copolyreaction, remove solvent then, obtain mobile well carried metallocene catalyst.
The gained carried metallocene catalyst again with a kind of be that the titanium of promotor is that Ziegler-Natta catalyst mixes with the aluminum alkyls, make bimetal of the present invention active centre compounded catalyst, metallocene and titanium are that the mol ratio of titanium metal in the Ziegler-Natta catalyst can be 10: 1-1: regulate between 50.This catalyzer is used for the homopolymerization or the copolymerization of alkene, just can obtain the wide polyolefin resin of molecular weight distribution.As the homopolymerization of ethene or the copolymerization of ethene and alpha-olefin, regulate molecular weight with hydrogen, the ratio of hydrogen dividing potential drop and stagnation pressure is regulated between 0.1%-20%.Alpha-olefin can be propylene, 1-butylene, 1-hexene, 1-octene etc.The multipolymer density range is at 0.880-0.965g/cm
3, the comonomer molar content is between 1%-25% in the co-polymer.Molecular weight distribution mw/mn=the 2.0-20 of resin, MFR is between 28-200.The consumption of two or more aluminum alkyls can in very large range be adjusted the molecular weight and the molecular weight distribution of polymkeric substance, thereby obtain the wide polyolefin resin of molecular weight distribution when when adjusting preparation mixed alkyl alumina alkane by the mole of adjusting two kinds of metals.
Compounded catalyst of the present invention can be used for the gas-phase fluidized-bed or slurry polymerization of alkene.Have the advantages that the catalyzer cost is low, activity is high, easy to operate, the high/low molecular weight component of resulting polymers is easy to adjust, molecular weight distribution is wide.The resin treatment that makes with compounded catalyst of the present invention is good, and apparent property is good, and the product application scope is wide.
Embodiment 1
1 liter of reactor that nitrogen replacement is good adds 200 milliliters of toluene, concentration is 80 milliliters of the triisobutylaluminum toluene solution of 1.0 mol, concentration is 150 milliliters of the trimethyl aluminium toluene solutions of 1. mol, induction stirring slowly adds water content and is 12.8% silica gel (Davison 948) 50 grams.After adding silica gel, stirred 1 hour down, progressively be warming up to 30 ℃ in 1 hour when continuing to stir, stirred 4 hours down at 30 ℃ then at-5 ℃.Add then and contain 1.0 gram bis cyclopentadienyl zirconium dichloride toluene solutions, stirred 30 minutes under the room temperature.Stop to stir, static 15 minutes, the sucking-off upper solution.Add 100 milliliters of hexanes, stirred 15 minutes, stop to stir, static 15 minutes, the sucking-off upper solution.So washing is three times, drain solvent, obtain mobile well special metallocene catalyst powder, with this catalyzer 0.5 gram and model of Beijing Chemical Research Institute's development is that the titanium of BCH is that Ziegler-Natta catalyst (this catalyzer titaniferous amount is 1.4 mmoles/gram catalyzer) powder 0.1 restrains to mix and promptly obtains compounded catalyst of the present invention, and this compounded catalyst is used for the copolyreaction of ethene and hexene-1.Detailed process is as follows:
Use 2 liters of reactors, add 1 liter of hexane behind the nitrogen replacement, 10 ml concns are the triethyl aluminum hexane solution of 0.5 mol.20 milliliters of hexenes, hydrogen dividing potential drop 0.015MP, ethylene partial pressure 0.985MPa.80 ℃ of temperature of reaction, 1 hour time, the polymerization resulting polymers makes the active ingredient inactivation with hydrochloric acid/methanol solution, and polymkeric substance dries weighs, and polymer quality is 298 grams, and molecular weight distribution is 12.2.
Embodiment 2
Triisobutyl aluminium is different with the consumption of trimethyl aluminium when removing the preparation metallocene catalyst, triisobutyl aluminium is with 120 milliliters, trimethyl aluminium is with outside 125 milliliters, other is with embodiment 1, obtain special metallocene catalyst powder, with this catalyzer 0.5 gram and Beijing Chemical Research Institute's system model is that the titanium of BCH is that Ziegler-Natta catalyst powder 0.1 restrains to mix and promptly obtains compounded catalyst of the present invention, and this compounded catalyst is used for the copolyreaction of ethene and hexene-1.Detailed process is with embodiment 1, and obtaining polymer quality is 243 grams, and molecular weight distribution is 10.7.
Embodiment 3
The triisobutyl aluminium during except that the preparation metallocene catalyst in 80 milliliters of alternative embodiments 1 of triethyl aluminum toluene solution of usefulness concentration 1.0 mol, other is with embodiment 1, obtain special metallocene catalyst powder, with this catalyzer 0.5 gram and Beijing Chemical Research Institute's system model is that the titanium of BCH is that Ziegler-Natta catalyst powder 0.1 restrains to mix and promptly obtains compounded catalyst of the present invention, and this compounded catalyst is used for the copolyreaction of ethene and hexene-1.Detailed process is with embodiment 1, and obtaining polymer quality is 190 grams, and molecular weight distribution is 8.1.
Embodiment 4
Use 200 milliliters of triisobutyl aluminiums when removing the preparation metallocene catalyst, trimethyl aluminium is with outside 65 milliliters, other is with embodiment 1, obtain special metallocene catalyst powder, with this catalyzer 0.5 gram and Beijing Chemical Research Institute's system model is that the titanium of BCH is that Ziegler-Natta catalyst powder 0.1 restrains to mix and promptly obtains compounded catalyst of the present invention, and this compounded catalyst is used for the copolyreaction of ethene and hexene-1.Detailed process is with embodiment 1, and obtaining polymer quality is 182 grams, and molecular weight distribution is 9.2.
Embodiment 5
What mixture of alkyl aluminum used when removing the preparation metallocene catalyst is 100 milliliters of triisobutyl aluminiums, 100 milliliters of trimethyl aluminiums, 60 milliliters (concentration is triethyl aluminum: 1.0 mol), other is with embodiment 1, obtain special metallocene catalyst powder, with this catalyzer 0.5 gram and Beijing Chemical Research Institute's system model is that the titanium of BCH is that Ziegler-Natta catalyst powder 0.1 restrains to mix and promptly obtains compounded catalyst of the present invention, and this compounded catalyst is used for the copolyreaction of ethene and hexene-1.Detailed process is with embodiment 1, and obtaining polymer quality is 266 grams, and molecular weight distribution is 13.8.
Embodiment 6
Except that preparation during metallocene catalyst with 1.0 bis cyclopentadienyl zirconium dichlorides that restrain in the dichloro hafnocene alternative embodiments 1, other is with embodiment 1, obtain special metallocene catalyst powder, with this catalyzer 0.3 gram and Beijing Chemical Research Institute's system model is that the titanium of BCH is that Ziegler-Natta catalyst powder 0.3 restrains to mix and promptly obtains compounded catalyst of the present invention, and this compounded catalyst is used for the copolyreaction of ethene and hexene-1.Detailed process is with embodiment 1, and obtaining polymer quality is 320 grams, and molecular weight distribution is 11.8.
Embodiment 7
In 1000 milliliters there-necked flask, add 15.8 gram AL through crushing screening
2(SO
4)
318H
2O, and add 200 milliliters of dry toluene, after nitrogen is fully put reaction flask, in this there-necked flask, slowly drip 80 milliliters of the triisobutylaluminum toluene solution of 1.0 mol and the mixed solution of 150 milliliters of compositions of trimethyl aluminium toluene solution of 1.5 mol by constant pressure funnel down and under the induction stirring at-5 ℃.In 2 hours, all add above-mentioned mixed solution in the reaction flask; and under-5 ℃, continue to stir 2 hours; in 1 hour, temperature of reaction is slowly risen to 30 ℃ then; stir to stop after 4 hours stirring and stop to heat; after question response bottle temperature is chilled to room temperature, solid matter such as elimination Tai-Ace S 150 under protection of nitrogen gas, filtrate is under 10mmHg pressure; steam and remove a large amount of solvents, remaining about 50 ml solns are the toluene solution that mixes aikyiaiurnirsoxan beta.
In above-mentioned aluminum mixture oxygen alkane toluene solution (50 milliliters), add silica gel (Davison 955) 5 grams; under nitrogen protection, stirred 1 hour down at 40 ℃, add 0.1 gram bis cyclopentadienyl zirconium dichloride (adding) then with toluene dissolving back; continuing stirring down at 40 ℃ stops after 2 hours stirring; static 15 minutes, the sucking-off upper solution added 50 milliliters of hexanes; stirred 15 minutes; stop to stir, static 15 minutes, the sucking-off upper solution.So washing is three times, drain solvent, obtain mobile well special metallocene catalyst powder, with this catalyzer 0.5 gram and Beijing Chemical Research Institute's system model is that the titanium of BCH is that Ziegler-Natta catalyst powder 0.1 restrains to mix and promptly obtains compounded catalyst of the present invention, and this compounded catalyst is used for the copolyreaction of ethene and hexene-1.Detailed process is with embodiment 1, and obtaining polymer quality is 300 grams, and molecular weight distribution is 12.0.
Comparative example 1
Do not contain triisobutyl aluminium when removing the preparation metallocene catalyst, outside 205 milliliters of trimethyl aluminiums, other is with embodiment 1, obtain coventional type metallocene catalyst powder, with this catalyzer 0.5 gram and Beijing Chemical Research Institute's system model is that the titanium of BCH is that Ziegler-Natta catalyst powder 0.1 restrains to mix and promptly obtains compounded catalyst of the present invention, and this compounded catalyst is used for the copolyreaction of ethene and hexene-1.Detailed process is with embodiment 1, and obtaining polymer quality is 267 grams, and molecular weight distribution is 5.5.
Comparative example 2
The titanium of getting Beijing Chemical Research Institute system model and be BCH is the copolyreaction that Ziegler-Natta catalyst powder 0.6 gram is directly used in ethene and hexene-1.Detailed process is with embodiment 1, and obtaining polymer quality is 150 grams, and molecular weight distribution is 3.4.
Comparative example 3
Do not contain triisobutyl aluminium when removing the preparation metallocene catalyst, outside 205 milliliters of trimethyl aluminiums, other obtains coventional type metallocene catalyst powder with embodiment 1, this catalyzer 0.5 gram is directly used in the copolyreaction of ethene and hexene-1.Detailed process is with embodiment 1, and obtaining polymer quality is 156 grams, and molecular weight distribution is 2.8.
Claims (9)
- A synthetic molecular weight wide/pair distribution polyolefin resin is with the compounded catalyst that contains metallocene, it is characterized in that metallocene catalyst and titanium are that Ziegler-Natta catalyst is composite, wherein the promotor of metallocene catalyst adopts two or more mixed type alkylaluminoxane; The mol ratio of titanium metal can be 10 in metallocene and the Ziegler-Natta catalyst: 1-1: regulate between 50.
- 2. compounded catalyst according to claim 1 is characterized in that in the used mixture of alkyl aluminum of promotor of metallocene catalyst wherein that the mol ratio of metal is 1000 in the aluminium and metallocene compound: 1-1: between 1.
- 3. compounded catalyst according to claim 1 is characterized in that in the used mixture of alkyl aluminum of promotor of metallocene catalyst wherein that the mol ratio of metal is 250 in the aluminium and metallocene compound: 1-30: between 1.
- 4. compounded catalyst according to claim 1 is characterized in that the metallocene compound of metallocene catalyst has following structure formation, Cp in the compounded catalyst mMR nX q, Cp is luxuriant ring or substituent luxuriant ring is arranged, and also can be indenyl or fluorenyl, but between two Cp, indenyl or the fluorenyls also the bridge chain link; M is Zr, Ti or Hf, and R is C 1-C 8Alkyl or hydrogen atom, X is halogen F, Cl, Br, I or methyl.
- 5. compounded catalyst according to claim 1, it is characterized in that metallocene catalyst is to generate the mixed type alkylaluminoxane by moisture 1-30wt% silica gel and two or more aluminum alkyls mixing solutions direct reaction in the compounded catalyst, reaction makes the mixed type alkylaluminoxane with metallocene compound again.
- 6. according to claim 1 or 2 or 3 or 5 described compounded catalysts, the alkyl that it is characterized in that the promotor-mixed type alkylaluminoxane of metallocene catalyst in the compounded catalyst can be two or more alkyl in methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, hexyl, octyl group, decyl, cyclohexyl, ring octyl group, the ring decyl.
- 7. according to claim 1 or 2 or 3 or 5 described compounded catalysts, it is characterized in that alkyl includes methyl in metallocene catalyst in the compounded catalyst-promotor mixed type alkylaluminoxane.
- 8. compounded catalyst according to claim 1, it is characterized in that the titanium in the compounded catalyst is the promotor employing aluminum alkyls of Ziegler-Natta catalyst, the mol ratio of titanium metal is 2 in aluminum alkyls and the Ziegler-Natta catalyst: 1-200: between 1.
- 9. according to claim 1 or 8 described compounded catalysts, it is characterized in that the titanium in the compounded catalyst is the aluminum alkyls of Ziegler-Natta catalyst promotor, can be trimethyl aluminium, triethyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-octylaluminium, three iso-octyl aluminium.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99109944 CN1207313C (en) | 1999-06-23 | 1999-06-23 | Compounded catalyst for olefinic polymerization |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99109944 CN1207313C (en) | 1999-06-23 | 1999-06-23 | Compounded catalyst for olefinic polymerization |
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| Publication Number | Publication Date |
|---|---|
| CN1292389A true CN1292389A (en) | 2001-04-25 |
| CN1207313C CN1207313C (en) | 2005-06-22 |
Family
ID=5274264
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99109944 Expired - Fee Related CN1207313C (en) | 1999-06-23 | 1999-06-23 | Compounded catalyst for olefinic polymerization |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006047913A1 (en) * | 2004-11-05 | 2006-05-11 | Institute Of Chemistry, Chinese Academy Of Sciences | Polyolefin composite material and method for producing the same |
| CN100363391C (en) * | 2005-02-28 | 2008-01-23 | 中国石油化工股份有限公司 | Supported bimetal polyvinyl catalyst and preparation method thereof |
| CN102887967A (en) * | 2012-10-17 | 2013-01-23 | 上海化工研究院 | Composite catalyst for producing polyethylene with wide molecular weight distribution as well as production method and application thereof |
-
1999
- 1999-06-23 CN CN 99109944 patent/CN1207313C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006047913A1 (en) * | 2004-11-05 | 2006-05-11 | Institute Of Chemistry, Chinese Academy Of Sciences | Polyolefin composite material and method for producing the same |
| CN100363391C (en) * | 2005-02-28 | 2008-01-23 | 中国石油化工股份有限公司 | Supported bimetal polyvinyl catalyst and preparation method thereof |
| CN102887967A (en) * | 2012-10-17 | 2013-01-23 | 上海化工研究院 | Composite catalyst for producing polyethylene with wide molecular weight distribution as well as production method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1207313C (en) | 2005-06-22 |
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