CN1283675C - Supported catalytic system for preparing double-peak polythenes and preparation process thereof - Google Patents
Supported catalytic system for preparing double-peak polythenes and preparation process thereof Download PDFInfo
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- CN1283675C CN1283675C CN 03137600 CN03137600A CN1283675C CN 1283675 C CN1283675 C CN 1283675C CN 03137600 CN03137600 CN 03137600 CN 03137600 A CN03137600 A CN 03137600A CN 1283675 C CN1283675 C CN 1283675C
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- catalyst system
- transition metal
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- metallocene compound
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Abstract
The invention discloses a supported catalytic system for preparing bimodal polyethylene, which is mainly composed of a main catalyst, alkylaluminium oxane and a SiO2 carrier, wherein the main catalyst is a mixture of metallocene compounds and late transition metal compounds with the general formula of C25H27X2MN3. The catalytic system is obtained through the mixing reaction of alkylaluminium oxane supported on SiO2 and the alkylated main catalyst at the temperature of 20 DEG C to-20 DEG C.
Description
Technical field
The present invention relates to a kind of supported catalyst system and preparation method thereof, specifically is a kind of supported catalyst system of being made up of metallocene compound and rear transition metal compound and preparation method thereof, is specially adapted to olefinic polymerization and prepares bimodal polyethylene.
Prior art
For many application, it is crucial that polyethylene has high tenacity, high strength and good performances such as resisting environmental stress and cracking, adopts High molecular weight polyethylene can easily reach these high-performance.Yet, when polymericular weight increases, the processing characteristics of this resin is descended.Have polymkeric substance wide or bimodal molecular weight distribution by providing, not only can keep the characteristic performance of high molecular weight resin, and can also improve the processing characteristics of resin, so the research and development of Bi-modal polyethylene resin have become question of common concern.
Producing the effective way of bimodal polyethylene in the prior art is to adopt bimetal or many metal active constituents catalyzer in single reaction vessel, utilizes their different separately polymerization behavior direct production bimodal polyethylenes.Many active centre can by two kinds and two or more ziegler-natta catalyzer be composite, metallocene catalyst and the ziegler-natta catalyzer is composite, two kinds of metallocene catalysts are composite etc. that mode obtains.As CN88101779 utilize the catalyst system in Ti, V bimetal active centre produce in the resin of molecular weight distribution, and adopted before the polyreaction technology with two kinds of catalyst mix; CN1058601A discloses the reduction vanadium compound and the organic oxygen-containing zirconium compounds passes through the catalyst composition of immersion deposition on active carrier material altogether; US6051525 employing metallocene catalyst such as zirconium cyclopentadinyl compound and non-luxuriant transistion metal compound such as titanium catalyst carry out composite, the luxuriant polyvinyl resin that preparation has bimodal or wide molecular weight distribution; EP0676418 employing metallocene catalyst and ziegler-natta catalyzer are composite, prepare the polyvinyl resin with bimodal or wide molecular weight distribution; CN1250058 provides a kind of mixed catalyst of being made up of carried metallocene catalyst and carrying transition metal Nonmetallocene type catalyzer, the polyolefine that is used for synthetic wide or bimodal distribution, this mixed catalyst are mixed getting after adding the another kind of loaded catalyst for preparing in advance by two kinds of loaded catalysts through blending or in a kind of catalyzer process of preparation.
Late transition metal catalyst is the new focus of the research of olefin polymerization catalysis in recent years, successfully is applied to prepare branched polyethylene (CN1358772) and ethylene oligomer (CN1323766).Transistion metal compound is as catalyst for oligomerization after the people such as Liu Zhongyang, metallocene compound is formed bifunctional catalysis system as catalyst for copolymerization, successfully use a kind of polymerization single polymerization monomer ethene, a kind of promotor to prepare long-chain branched polyethylene (Science Bulletin with in-situ polymerization, the 46th the 15th phase of volume, August calendar year 2001), adopt during its polymerization to add back transition compound earlier, the back adds the mode of cyclopentadinyl compound.US6114483 has also proposed the composite catalyst system of late transition metal catalyst and metallocene catalyst and has been used for polymerization in homogeneous phase.US6194341B1 has required by at least a late transition metal catalyst and at least a rear transition metal, metallocene, the ziegler-natta catalyzer of being selected from, and the catalyst system that at least a promotor is formed is used for olefinic polymerization.Late transition metal catalyst wherein should satisfy general formula LMX
r, the compound of this general formula is with ketone and 2, the 6-Diethyl Aniline is a synthesis material.The process of this catalyst cupportization is disclosed in an embodiment.: catalyzer and promotor form precursor liquid in the presence of solvent; Adding porous support again stirs; After desolventizing, vacuum put to the room temperature 12～16 hours.This carrying method load efficiency is low, and simple aftertreatment makes the form of polymer particles bad.
Summary of the invention
One of purpose of the present invention is to propose a kind of loaded metallocene-rear transition metal double activity center catalyst system, is used to prepare the polyvinyl resin with bimodal distribution.
Another object of the present invention provides the preparation method of above-mentioned catalyst system.
Catalyst system of the present invention is by Primary Catalysts, alkylaluminoxane promotor, SiO
2Carrier is formed, and wherein Primary Catalysts is the mixture of metallocene compound and rear transition metal compound.Concrete composition is:
A: general formula is C
25H
27X
2MN
3The rear transition metal compound, wherein X:Cl, Br, I; M:Fe, Co, Ni.
Concrete structure is as follows:
C
25H
27X
2MN
3
B: structural formula is Cp
mThe MXn metallocene compound, wherein Cp is cyclopentadienyl, indenyl or fluorenyl, also can be to be with substituent cyclopentadienyl, indenyl or fluorenyl, but between two luxuriant rings also the bridge chain link; M is Ti, Zr, Hf; X is halogen or C
1～C
8Alkyl; M and n are between 1～2.The metallocene compound that is suitable for has Cp
2ZrCl
2, (n-BuCp)
2ZrCl
2, IndCpZrCl
2, Cp
2ZrMe
2, Ind
2ZrCl
2, Cp
2HfCl
2, Si (CH
3)
2Cp
2ZrCl
2, [(CH
3)
4Cp]
2ZrCl
2, optimum compound is IndCpZrCl
2
C: promoter aluminium alkyl oxygen alkane, can generate by aluminum alkyls and water reaction, suitable alkylaluminoxane comprises methylaluminoxane, ethyl aikyiaiurnirsoxan beta, isobutyl aluminium alkoxide etc., is preferably methylaluminoxane (MAO);
D:SiO
2Carrier, SiO among the present invention
2Specific surface area usually at 100～700m
2/ g is preferably in 200～400m
2/ g; Pore volume is at 0.5～3cm
3/ g is preferably in 1～2cm
3/ g; Median size is preferably in 40～60 μ m. at 20～100 μ m.
More than in each catalyst component, c and (a+b) between molar ratio between 50～1000, be preferably between 400～600.The mol ratio of metallocene compound and rear transition metal compound can be adjusted according to product needed, does not do special qualification among the present invention.
The catalyst system of above-mentioned composition is reaction medium with the hexane, and under certain ethylene pressure, polymerizable generates the polyvinyl resin with bimodal distribution.
With preload at SiO
2On alkylaluminoxane mix with alkylating metallic compound, under 20 ℃～-20 ℃ (being preferably 0～-20 ℃) temperature the reaction can obtain catalyst system of the present invention.Concrete preparation method is:
1) toluene solution of alkylaluminoxane and SiO
2Carrier was 60～200 ℃ of following stirring reactions 4～6 hours, and cooling obtains suspending liquid A, wherein, and the toluene solution of alkylaluminoxane and SiO
2The amount ratio of carrier is 10～50ml/g SiO
2(be preferably 15～30ml/g SiO
2);
2) with in the toluene solution of metallocene compound and rear transition metal compound adding alkylaluminoxane (consumption of metallocene compound, rear transition metal compound and carrier is controlled at 0.15～0.5mmol metal ion/g carrier), under 20～60 ℃, reacted 0.5～4 hour, and obtained solution B;
3) suspending liquid A and solution B are mixed, under 20 ℃～-20 ℃ temperature, (be preferably 0～-20 ℃) and reacted 1～5 hour, with obtaining catalyst fines after hexane wash, the vacuum-drying.
The polyvinyl resin that supported catalyst system of the present invention, catalyzed polymerization obtain has two fusing points, the characteristic of bimodal distribution, and MFR is 10～50.
Description of drawings
The DSC spectrogram of the polymkeric substance that Fig. 1 embodiment 1 obtains
The DSC spectrogram of the polymkeric substance that Fig. 2 embodiment 2 obtains
Following embodiment helps to strengthen the understanding of the present invention, but is not limitation of the invention.
Embodiment
Embodiment 1:
A. extract the toluene solution of MAO, press 15ml/g SiO
2Feed ratio is added to carrier S iO
2In.Reaction is after 5 hours down at 90 ℃, and cooling obtains suspending liquid A;
B. with (Ind) of 0.026g
2ZrCl
2C with 0.12g
25H
27Cl
2FeN
3Press Zr: Fe=1: 5 composite after, add in the toluene solution of MAO, 25 ℃ of reactions 4 hours down, obtain solution B;
C. A and B are mixed, after 4 hours, use hexane wash 4 times in reaction under-15 ℃, dry under vacuum state, obtain solid catalyst 1.
Vinyl polymerization and evaluation
5 liters of autoclave nitrogen replacement three times add 2 liters of hexanes, and the 2ml triethyl aluminum stirs removal of impurities and heats up.When still temperature to 50 ℃, add catalyzer 0.2 gram, feed ethene to 1.0MPa, 80 ℃ of following polymerizations.After 1 hour, add hydrochloric acid and alcohol mixeding liquid termination reaction, the polymkeric substance oven dry is weighed.
After tested: polymerization activity is 3500gPE/gcat, and the polymer particle form is good, and bulk density is 0.35.MFR is 35, and the DSC test polymer has two fusing points, and molecular weight is bimodal distribution.
Embodiment 2:
Choose C
25H
27Br
2CoN
30.2 gram, (BuCp)
2ZrCl
20.2 gram mixes, and forms the Co-Zr catalyst system.Prepare catalyzer by the carrying method described in the embodiment 1, obtain the solid catalyst 2 of loading type.
Press embodiment 1 identical vinyl polymerization and evaluation method, the polymkeric substance that obtains polymerization activity after tested is 4200gPE/gcat, and the polymer particle form is good, and bulk density is 0.38.MFR is 28, the DSC test shows, and this polymkeric substance has two fusing points, and molecular weight is bimodal distribution.
Comparative Examples 1:
A is with 0.026g metallocene compound (Ind)
2ZrCl
2With 0.12g rear transition metal C
25H
27Cl
2FeN
3Press Zr: Fe=1: 5 composite after, add in the toluene solution of 15ml alkylaluminoxane, stir solution A.
B is transferred to solution A in another container, simultaneously 1g silica gel is added to stir in this container slurries B.
C extracted solvent 12～16 hours under room temperature and vacuum state, obtain the solid catalyst powder of good fluidity.
Vinyl polymerization and evaluation
Press embodiment 1 identical vinyl polymerization and evaluation method, the polymkeric substance that obtains polymerization activity after tested is 560gPE/gcat.The particle shape of polymkeric substance is bad, and bulk density is 0.16, sticking still, discharging difficulty.
Comparative Examples 2:
Taking by weighing Co is late transition metal catalyst C
25H
27Br
2CoN
30.2 gram, metallocene catalyst (Ind)
2ZrCl
20.2 gram mixes, and forms the Co-Zr catalyst system.Prepare catalyzer by the carrying method of narrating in the Comparative Examples 1, obtain the solid catalyst of loading type.
Press embodiment 1 identical vinyl polymerization and evaluation method, the polymkeric substance that obtains polymerization activity after tested is 800gPE/gcat.The particle shape of polymkeric substance is bad, and bulk density is 0.16, sticking still, discharging difficulty.
Claims (8)
1. supported catalyst system that is used to prepare bimodal polyethylene is by the mixture of metallocene compound and rear transition metal compound, alkylaluminoxane, SiO
2Carrier is formed, and it is characterized in that the rear transition metal compound satisfies general formula: C
25H
27X
2MN
3, wherein X:Cl, Br or I; M:Fe, Co or Ni, concrete structural formula is:
C
25H
27X
2MN
3。
2. catalyst system according to claim 1 is characterized in that metallocene compound satisfies general formula Cp
mMXn, wherein Cp is cyclopentadienyl, indenyl or fluorenyl, also can be to be with substituent cyclopentadienyl, indenyl or fluorenyl, but between two luxuriant rings also the bridge chain link; M is Ti, Zr or Hf; X is halogen or C
1～C
8Alkyl; M and n are between 1～2.
3. catalyst system according to claim 2 is characterized in that metallocene compound is Cp
2ZrCl
2, (n-BuCp)
2ZrCl
2, IndCpZrCl
2, Cp
2ZrMe
2, Ind
2ZrCl
2, Cp
2HfCl
2, Si (CH
3)
2Cp
2ZrCl
2Or [(CH
3)
4Cp]
2ZrCl
2
4. catalyst system according to claim 3 is characterized in that metallocene compound is IndCpZrCl
2
5. the catalyst system one of described according to claim 1 to 4 is characterized in that alkylaluminoxane is a methylaluminoxane.
6. a method for preparing the described catalyst system of claim 1 is characterized in that catalyst system is to load on SiO
2Last alkylaluminoxane and alkylating Primary Catalysts obtain 20 ℃～-20 ℃ temperature hybrid reactions, alkylation Primary Catalysts wherein be metallocene compound and rear transition metal compound 20～60 ℃ down with the reactants of alkylaluminoxane, the consumption of metallic compound and carrier is controlled at 0.15～0.5mmol metal ion/g carrier; The rear transition metal compound satisfies general formula C
25H
27X
2MN
3, wherein X:Cl, Br or I; M:Fe, Co or Ni; The structural formula of metallocene compound is Cp
mMXn, wherein Cp is cyclopentadienyl, indenyl or fluorenyl, also can be to be with substituent cyclopentadienyl, indenyl or fluorenyl, but between two luxuriant rings also the bridge chain link; M is Ti, Zr or Hf; X is halogen or C
1～C
8Alkyl; M and n are between 1～2.
7. the preparation method of catalyst system according to claim 6 is characterized in that the preparation method of catalyst system is as follows:
1) by 15～30ml/g SiO
2Amount ratio the toluene solution of methylaluminoxane is added to SiO
2, stirring is after 4～6 hours down at 60～200 ℃, and cooling obtains suspending liquid A;
2) metallocene compound and rear transition metal compound are added in the toluene solution of methylaluminoxane, under 20～60 ℃, reacted 0.5～4 hour, obtain solution B, wherein, the consumption of metallocene compound, rear transition metal compound and carrier is controlled at 0.15～0.5mmol metal ion/g carrier;
3) A and B are mixed, under 0 ℃～-20 ℃ temperature, reacted 1～5 hour, with obtaining catalyst fines after hexane wash, the drying.
8. according to the preparation method of the described catalyst system of claim 7, it is characterized in that metallocene compound is IndCpZrCl
2
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03137600 CN1283675C (en) | 2003-06-18 | 2003-06-18 | Supported catalytic system for preparing double-peak polythenes and preparation process thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03137600 CN1283675C (en) | 2003-06-18 | 2003-06-18 | Supported catalytic system for preparing double-peak polythenes and preparation process thereof |
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|---|---|
| CN1566163A CN1566163A (en) | 2005-01-19 |
| CN1283675C true CN1283675C (en) | 2006-11-08 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613425B (en) * | 2009-07-21 | 2011-05-04 | 浙江大学 | Catalyst of polyethylene with double peak and/or broad peak molecular weight distribution |
| CN101928360B (en) * | 2010-08-20 | 2013-12-04 | 中国石油天然气股份有限公司 | Wide molecular weight distribution polyolefin catalyst and preparation and application thereof |
| WO2014149360A1 (en) | 2013-03-15 | 2014-09-25 | Univation Technologies, Llc | Multiple catalyst system comprising metallocenes and tridentate nitrogen based ligand complexes for olefin polymerisation |
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