CN1176115C - Synthesis process of oleine polymerizing metallocene catalyst - Google Patents
Synthesis process of oleine polymerizing metallocene catalyst Download PDFInfo
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- CN1176115C CN1176115C CNB021039089A CN02103908A CN1176115C CN 1176115 C CN1176115 C CN 1176115C CN B021039089 A CNB021039089 A CN B021039089A CN 02103908 A CN02103908 A CN 02103908A CN 1176115 C CN1176115 C CN 1176115C
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Abstract
The present invention relates to a synthesis process of a main metallocene catalyst for oleine polymerization. In the late preparation period of a metallocene compound, at least two metallocene reaction liquids are mixed and react for 2 to 4 hours, so that each metallocene component exists in a compound state, and a compound proportion is stable and controllable. When the catalyst is used for catalyzing oleine polymerization together with a cocatalyst, the component compound is uniformly loaded on a carrier according to a set proportion; the catalyst has high catalytic polymerization activity, and metallocene polyolefine resin produced by the reaction has obvious double peak (or broad peak) distribution.
Description
Technical field
The present invention relates to the synthetic method of metallocene compound in the polyolefin catalyst.
The metallocene compound Chang Zuowei Primary Catalysts that is used for olefinic polymerization uses, and it mainly is divided into three kinds of non-bridged combined metal compound, bridged combined metal compound and single cyclopentadienyl metallocene compounds.When metallocene compound was used for olefinic polymerization, the molecular resin amount that obtains distributed narrow, causes the poor processability of resin itself, and makes metallocene catalyst can not get considerable breakthrough in application facet.At present, bimodal (broad peak) polyolefinic exploitation all is devoted in countries in the world, and one of main path is with traditional ziegler-natta catalyzer and the composite use of various metallocene catalyst, represents patent that US5539076, US5529965, US6001766 etc. are arranged.Two kinds of catalyzer are when catalysis in olefine polymerization but most of researchist thinks, the uncooperativeness to hydrogen is transferred causes the synthetic resin not achieve the desired result.The another kind of selection is the metallocene that two kinds of structures and catalytic performance differ greatly to be mixed use, and as disclosed at least two kinds of different chiralitys of CN1032343A and inflexible, general formula is R " [C
5(R ')
4]
2MQ
pThe catalyst system formed of metallocene, in the formula: [C
5(R ')
4]
2Be the cyclopentadiene of cyclopentadiene or replacement, also optional from containing indenyl atomic group group; R " is a methylene radical; Q is hydrocarbon radical or halogen, and 0＜p＜3 are mainly used in the polyolefin resin of propylene polymerization production wide molecular weight distribution; CN1247875A also adopts two kinds of composite vinyl polymerizations that are used for of metallocene compound, produces the polyethylene of branching and wide distribution.Because two kinds of different cyclopentadinyl compounds load factor difference in the load process, do not reach both certainty ratios between two kinds of main catalyst component of actual loading to the carrier, when producing the resin of bimodal distribution, can not realize controlledly well, the catalyzed polymerization activity is on the low side.
Summary of the invention
The synthetic method that the purpose of this invention is to provide a kind of compound metallocene compound.When being used to prepare carried metallocene catalyst, the ratio that metallocene compound can be set is carried on the carrier equably, has improved the uneven shortcoming of load.
The present invention comes the stable compound metallocene compound of synthetic ratio with two or more different cyclopentadienyl part.Concrete preparation process is as follows:
A. the preparation of part negative ion: both the part of certainty ratio was used dissolution with solvents respectively, under the nitrogen protection of strictness, in 1.4～1.1: the ratio of 1 (mol) adds proton acceptor, its temperature of reaction is at-35～20 ℃, be preferably in-10～5 ℃, behind reinforced the finishing, continue reaction 4～20 hours, be preferably 6～10 hours, reaction has obtained the part negative ion after finishing;
B. react with the central atom metallic compound: in temperature of reaction is-20～20 ℃, be preferably under-15～5 ℃ of conditions, by the metallizing thing reaction separately in certain proportion of above two kinds of part mole numbers, 8～36 hours reaction times was preferably 12～24 hours, then above two kinds of reaction solutions was mixed, continue reaction 2～4 hours, reaction finishes, and drains solvent, get final product metallocene compound of the present invention.
The alternative part of the present invention comprises all cyclopentadienyl ligand compounds, mainly comprises: the ligand compound of the cyclopentadienyl type of the cyclopentadiene of indenes, fluorenes, cyclopentadiene, replacement and bridging.
Proton acceptor is an organometallic compound, is generally lithium alkylide, is preferably butyllithium.
Reaction solvent can be selected polar solvent or non-polar solvent for use.Polar solvent refers to aromatic hydrocarbon solvent and ether solvent, is mainly tetrahydrofuran (THF) (THF); Non-polar solvent refers to alkane solvents, mainly uses hexane and pentane.Select different solvents, different to the post-treating method of negative ion, if what use is non-polar solvent such as saturated alkane, then after reaction finishes, to filter, washing (washing with reaction solvent) obtains the negative ion solid; If usefulness is polar solvent, then after reaction finishes, also can directly carry out next step reaction without handling.
The central atom metallic compound is selected from ZrCl at least
4, TiCl
4, HfCl
4Wherein a kind of.
The compound metallocene compound component of being made by this method exists with a kind of stable chemical combination attitude, and cooperate the ratio stable and controllable, during with promotor effect catalysis in olefine polymerization, the component compound can be carried on the carrier according to both certainty ratios very equably, the catalytic activity height, the metallocene-polyolefin resin that reaction generates has significantly bimodal
(or broad peak) distributes.
Embodiment
The preparation of embodiment 1 composite metallocene compound-1
A. take by weighing indenes 29g (purity is 96.4%) and cyclopentadiene 16.5g (purity is 97%) respectively, it is positioned over respectively in three mouthfuls of reaction flasks of two 500ml, add exsiccant normal hexane 200ml respectively, in the time of-5 ℃, drip the cyclohexane solution of 130ml butyllithium respectively, after dropwising, continued low-temp reaction 8 hours, to the reaction end;
B. take by weighing zirconium tetrachloride 29g and titanium tetrachloride 27.5g respectively, be modulated into complex compound, at normal temperatures, add in above two reaction flasks with THF, reaction is 12 hours in the time of 0 ℃, mixes, and continues reaction 4 hours, stopped reaction, filtration is drained, and obtains 104g composite metallocene-1.
The aggregation test of embodiment 2 composite metallocenes-1 reaches the contrast with compounded catalyst
Get 0.04g metallocene-1 and load to and make cyclopentadienyl catalyst-1 (aluminium zirconium ratio is 50: 1) on the 2.4g silica gel, at 60 ℃, under the 0.8Mpa, with ethylene homo 1 hour, obtain the 1443g polymkeric substance, every test result sees Table 1.
Get two kinds of metallocene compounds (two indenyl zirconium dichlorides (purity is 94%) and cyclopentadienyl titanium dichloride (purity is 93%) by 1: 1 molar ratio,) common 0.04g, load to and obtain comparative catalyst-1 (aluminium zirconium ratio is 50: 1) on 2.4 silica gel, get the identical consumption of cyclopentadienyl catalyst-1 (the component molar ratio is 1: 1) and under identical condition, carry out vinyl polymerization, polymerization result and product performance such as table 1.
Table 1 aggregation test and product performance
| Metallocene compound amount (g) | Polymerization activity (gPE/molZr h) | MI | The Mw/Mn of polymkeric substance | GPC | Film (25 μ m) dart impact strength (Mpa) * | |
| Metallocene catalyst-1 | 0.04g | 1.47×10 7 | 9.4 | 5.4 | Have obviously bimodal | 120 |
| Comparative catalyst-1 | 0.04g | 1.34×10 6 | 9.1 | 4.1 | Bimodal not obvious | 90 |
*The sheet blowing temperature is 170～190 ℃.
Dart impact strength is according to the GB-T9639 standard testing
The preparation of embodiment 3 composite metallocene compounds-2
A. take by weighing part normal-butyl cyclopentadiene 32g (purity is 96.8%) and methyl cyclopentadiene 10.5g (purity is 99%) respectively, it is positioned over respectively in three mouthfuls of reaction flasks of two 500ml, add exsiccant THF100ml and 150ml dissolving respectively, in the time of-5 ℃, drip the cyclohexane solution of 137ml and 69ml butyllithium respectively, after dropwising, continued low-temp reaction 6 hours, to the reaction end;
B. take by weighing zirconium tetrachloride 44.9g and 30.6g respectively, be modulated into complex compound, under ice bath, drip above two kinds of negative ions respectively with THF, reaction is 12 hours in the time of 0 ℃, mixes, and continues reaction 2 hours, stopped reaction, filtration is drained, and obtains 117.4g metallocene compound-2.
The aggregation test of embodiment 4 metallocene compounds-2 reaches the contrast with compounded catalyst
Get 0.04g cyclopentadinyl compound-2 and load to and make cyclopentadienyl catalyst-2 (aluminium zirconium ratio is 50: 1) on the 2.4g silica gel, at 60 ℃, under the 0.8Mpa, with ethylene homo 1 hour, obtain the 1623g polymkeric substance, its coalescent fruit sees Table 2 with product performance.
Get two n-butyl cyclopentadienyl zirconium dichlorides (purity is 96%) and two methyl cyclopentadienyl zirconium dichloride (purity is 94%) by 2: 1 molar ratio, its) common 0.04g, mix back loading and obtain comparative catalyst-2 to silica gel, its polymerization result and product performance see Table 2.
Table 2 polymerization result and product performance
| The amount of cyclopentadinyl compound (g) | Polymerization activity (gPE/molZrh) | MI | The Mw/Mn of polymkeric substance | GPC | Film (25 μ m) dart impact strength (Mpa) * | |
| Metallocene catalyst-2 | 0.04g | 1.02×10 7 | 8.7 | 7.6 | Have obviously bimodal | 120 |
| Comparative catalyst-2 | 0.04g | 1.34×10 6 | 9.2 | 4.1 | Bimodal not obvious | 100Mpa |
*The sheet blowing temperature is 170～190 ℃.
Dart impact strength is according to the GB-T9639 standard testing
Embodiment 5,6
Adopt the method identical with embodiment 1 to make metallocene compound, concrete reaction raw materials and consumption see Table 3, and aggregation test the results are shown in Table 4.
The reaction raw materials of table 3 cyclopentadinyl compound and proportioning
| Embodiment | Part negative ion (pairs of anion) | The kind of central atom metallic compound and consumption (g) | ||||
| The kind of part and consumption (g) | Solvent | Proton acceptor | ||||
| Ligand 1 | Part 2 | Consumption with respect to ligand 1 | Consumption with respect to part 2 | |||
Table 4 aggregation test and result
| Embodiment | Polymerization activity (gPE/molZr.h) | The MFR of polymkeric substance (g/10min) | The Mw/Mn of polymkeric substance |
| 1 | 1.47×10 7 | 7.6 | 5.4 |
| 3 | 1.02×10 7 | 3.1 | 7.6 |
| 5 | 1.55×10 7 | 9.4 | 6.3 |
| 6 | 1.27×10 7 | 4.4 | 5.6 |
Polymerizing condition: 60 ℃, vinyl polymerization is 1 hour under the 0.8Mpa
Claims (6)
1. the synthetic method of oleine polymerizing metallocene catalyst is characterized in that preparing as follows:
A. the preparation of part negative ion: both at least two kinds of cyclopentadienyl parts of certainty ratio were used dissolution with solvents respectively, under the nitrogen protection of strictness, mol ratio by 1.4～1.1: 1 adds proton acceptor, its temperature of reaction is at-35～20 ℃, behind reinforced the finishing, continue reaction 4～20 hours, reaction has obtained the part negative ion after finishing;
B. react with the central atom metallic compound: be under-20～20 ℃ the condition in temperature of reaction, above-mentioned at least two kinds of part negative ions react with the central atom metallic compound according to a certain percentage separately, 8～36 hours reaction times, then reaction solution is mixed, continue reaction 2～4 hours, reaction finishes, and drains solvent, get final product metallocene compound;
Wherein, the central atom metallic compound is selected from least wherein a kind of of titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride.
2. the synthetic method of oleine polymerizing metallocene catalyst is characterized in that preparing as follows:
A. the preparation of part negative ion: both at least two kinds of cyclopentadienyl parts of certainty ratio were used dissolution with solvents respectively, under the nitrogen protection of strictness, mol ratio by 1.4～1.1: 1 adds proton acceptor, its temperature of reaction is at-10～5 ℃, behind reinforced the finishing, continue reaction 6～10 hours, reaction has obtained the part negative ion after finishing;
B. react with the central atom metallic compound: in temperature of reaction is under-15～5 ℃ of conditions, above-mentioned at least two kinds of part negative ions are in 1～2: 1 ratio is reacted with the central atom metallic compound separately, reaction times is 12～24 hours, then reaction solution is mixed, continue reaction 2～4 hours, reaction finishes, and drains solvent, get final product metallocene compound;
Wherein, the central atom metallic compound is selected from least wherein a kind of of titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride.
3. synthetic method according to claim 1 and 2 is characterized in that proton acceptor is a butyllithium.
4. synthetic method according to claim 1 and 2 is characterized in that solvent is polarity or non-polar solvent.
5. synthetic method according to claim 1 and 2 is characterized in that solvent is a tetrahydrofuran (THF).
6. synthetic method according to claim 1 and 2 is characterized in that solvent is a normal hexane.
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| CN102085337B (en) * | 2009-12-07 | 2012-10-24 | 罗谦 | Patch for treating bronchial asthma of children |
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