CN107459597A - Load typed iron catalyst and preparation method thereof and Iron catalyst system - Google Patents
Load typed iron catalyst and preparation method thereof and Iron catalyst system Download PDFInfo
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Abstract
The invention belongs to olefin polymerization catalysis field, specifically, there is provided a kind of load typed iron catalyst and preparation method thereof and Iron catalyst system.The load typed iron catalyst includes zinc chloride/silica-gel carrier and the iron single active center component being supported on carrier；Wherein, the precursor of the iron single active center component is complex for the pyridine diimine Fe (II) of structure shown in formula 1, wherein, R1~R10It is identical or different, it each is selected from H, halogen or C1~C4Straight or branched alkyl, the load typed iron catalyst of the present invention is when for olefinic polymerization, compared to without zinc chloride modified pyridine diimine Fe (II) series catalysts, not only there is higher polymerization activity, and can also be basically unchanged the molecular weight distribution of polymer.
Description
Technical field
The invention belongs to olefin polymerization catalysis field, in particular it relates to a kind of load typed iron catalyst
And preparation method thereof, and a kind of Iron catalyst system for olefinic polymerization.
Background technology
In the evolution of olefin polymerization catalysis, the 1990s, the single active center of exploitation urged
Agent has obtained great development and concern.Particularly the iron of the part containing pyridine diimine, cobalt metal are matched somebody with somebody
Compound, there is very high catalyzed alkene oligomerisation and polymerization activity, and the features such as functionalization can be obtained
Vistanex, have a good application prospect.But this kind of catalyst without load when, obtain
Polymer be in amorphous state, can not make on wide variety of slurry process or gas phase polymerization technique
With.
At present, the supported research report of relevant single site catalysts is very more, wherein using silica gel as
Carrier report most study (CN1174848A, CN1174849A, CN1356343A,
US4,808,561, US5,026,797, US5,763,543, US5,661,098), this kind of support type is urged
Agent can use in partially polymerized technique, but use condition is more harsh, and usually require with valency
The expensive MAO (MAO) of lattice is co-catalyst, and this makes the cost of olefinic polymerization higher.
Also there is document report (such as macromolecule journal, 2004 (3), 406-409), urged in Z-N
Agent system using zinc dichloride and MAO processing silica gel, compared to not plus zinc dichloride catalyst,
Its activity improves, but the molecular weight of polymer and its distribution produce large change, can not effectively control
The processing characteristics of polymer.
The content of the invention
In order to solve above mentioned problem existing for prior art, the invention provides a kind of catalysis of loading type iron
Agent and preparation method thereof, and a kind of Iron catalyst system for olefinic polymerization.
The present inventor is had found under study for action, and zinc chloride is introduced into silica-gel carrier, and with containing pyrrole
The iron complex of pyridine diimide ligand is load typed iron catalyst prepared by precursor, for vinyl polymerization
When, the activity of catalytic reaction can be significantly improved, and original iron catalyst (not adding zinc chloride) can be kept
The molecular weight distribution of the polymer of gained is basically unchanged.Found based on more than, so as to propose the present invention.
According to the first aspect of the invention, the invention provides a kind of load typed iron catalyst, this is negative
Carrying sections catalyst includes zinc chloride/silica-gel carrier and the iron single active center group being supported on carrier
Point；Wherein, the precursor of the iron single active center component is the pyridine diimine Fe (II) of structure shown in formula 1
It is complex：
Wherein, R1~R10It is identical or different, it each is selected from H, halogen or C1~C4Straight chain or branch
Alkyl group.
According to the second aspect of the invention, the invention provides one kind to prepare the loading type iron catalysis
The method of agent, this method include：
(1) zinc chloride/silica-gel carrier is prepared
In the presence of the first solvent, silica gel is contacted with zinc chloride, obtain mixed solution；Then,
The first solvent in the mixed solution is removed, so as to which the zinc chloride/silica-gel carrier be made；
(2) load
In the presence of the second solvent, make the zinc chloride/silica-gel carrier and iron single active center component
Precursor reacted.
According to the third aspect of the present invention, the invention provides a kind of iron catalysis for olefinic polymerization
Agent system, the Iron catalyst system include：Major catalyst and co-catalyst, the major catalyst are upper
The load typed iron catalyst stated.
The load typed iron catalyst particle shape of the present invention is good, when for olefinic polymerization, not only has
There is higher polymerization activity, and can also be held essentially constant the molecular weight distribution of polymer.In addition,
The present invention Iron catalyst system applicability it is wide, and can preferably using alkyl aluminum as co-catalyst, compared to
The usually used MAO of olefinic polymerization (MAO), there is the characteristics of cost is low.
Brief description of the drawings
Fig. 1 a- Fig. 1 b are the load typed iron catalyst of the preparation of the embodiment of the present invention 1 in different amplification
Under SEM figure.
Embodiment
The embodiment of the present invention is described in detail below.It should be appreciated that this place
The embodiment of description is merely to illustrate and explain the present invention, and is not intended to limit the invention.
According to the first aspect of the invention, the invention provides a kind of load typed iron catalyst, this is negative
Carrying sections catalyst includes zinc chloride/silica-gel carrier and the iron single active center group being supported on carrier
Point；Wherein, the precursor of the iron single active center component is the pyridine diimine Fe (II) of structure shown in formula 1
It is complex：
Wherein, R1~R10It is identical or different, it each is selected from H, halogen or C1~C4Straight chain or branch
Alkyl group.
According to the present invention, the halogen can be selected from Cl, Br or F.
The C1~C4The instantiation of straight or branched alkyl include：Methyl (Me), ethyl (Et),
N-propyl, isopropyl (iPr), normal-butyl, isobutyl group and the tert-butyl group, preferably methyl, ethyl and
Isopropyl.
Preferably, in formula 1, R1、R3、R4And R6It is identical, R2And R5It is identical, R7~R10It is identical.
In one embodiment, R7~R10It is H.
It is highly preferred that the precursor of iron single active center component in following complex at least one
Kind：
Complex 1：R1=R3=R4=R6=Me, R2=R5=H, R7=R8=R9=R10=H；
Complex 2：R1=R3=R4=R6=Et, R2=R5=H, R7=R8=R9=R10=H；
Complex 3：R1=R3=R4=R6=iPr, R2=R5=H, R7=R8=R9=R10=H；
Complex 4：R1=R2=R3=R4=R5=R6=Me, R7=R8=R9=R10=H；
Complex 5：R1=R3=R4=R6=Me, R2=R5=Br, R7=R8=R9=R10=H；
Complex 6：R1=R3=R4=R6=Me, R2=R5=Et, R7=R8=R9=R10=H；
Complex 7：R1=R3=R4=R6=Et, R2=R5=Me, R7=R8=R9=R10=H；
Complex 8：R1=R3=R4=R6=Et, R2=R5=Br, R7=R8=R9=R10=H；
Complex 9：R1=R3=R4=R6=F, R2=R5=H, R7=R8=R9=R10=H；
Complex 10：R1=R3=R4=R6=Cl, R2=R5=H, R7=R8=R9=R10=H；
Complex 11：R1=R3=R4=R6=Br, R2=R5=H, R7=R8=R9=R10=H.
The pyridine diimine Fe (II) is that complex can be by commercially available, can also be according to ability
The conventional method in domain is made, and specifically, is referred to document J.Am.Chem.Soc.1998, and 120,
4049-4050 and WO9902472A1, will not be repeated here.
According to the present invention, on the basis of the gross weight of the load typed iron catalyst, Zn content can be with
Content for 0.5~7.0 weight %, Fe can be 0.01~5 weight %.
Preferably, on the basis of the gross weight of the load typed iron catalyst, Zn content is 0.5~4.0
Weight %, Fe content are 0.2~0.5 weight %；It is highly preferred that Zn content is 0.5~2.5 weight %.
In the present invention, the zinc chloride/silica-gel carrier refers to through zinc chloride modified silica-gel carrier, described
The granular size of load typed iron catalyst can be regulated and controled by carrier.
According to the second aspect of the invention, the invention provides one kind to prepare the loading type iron catalysis
The method of agent, this method include：
(1) zinc chloride/silica-gel carrier is prepared
In the presence of the first solvent, silica gel is contacted with zinc chloride, obtain mixed solution；Then,
The first solvent in the mixed solution is removed, so as to which the zinc chloride/silica-gel carrier be made；
(2) load
In the presence of the second solvent, make the zinc chloride/silica-gel carrier and iron single active center component
Precursor reacted.
In step (1), conventional selection when first solvent can be this area modified silica gel carrier,
As long as the silica gel and zinc chloride can be dissolved.For example, first solvent may be selected from tetrahydrofuran,
At least one of ethanol, methanol, propyl alcohol, butanol, 2-Ethylhexyl Alcohol, ethylene glycol and glycerine.It is excellent
Selection of land, first solvent are tetrahydrofuran.
The contact is generally carried out under inert gas (for example, nitrogen) protection, the process of the contact
It can include：Zinc chloride is dissolved in the first solvent, then at a temperature of 50~80 DEG C, adds silicon
Glue, stirring and dissolving 0.5~3 hour.
Removing the detailed process of the first solvent can include：First, solvent is steamed by heating；Then,
Heating vacuumizes, so as to obtain the zinc chloride/silica-gel carrier of solid powdery.Wherein, in order to enter
One step obtains the carrier of good fluidity, and preferably described heating is vacuumized and can carried out in two stages, the
The condition in one stage includes：Temperature is 80~150 DEG C, and the time is 0.5~3 hour；The bar of second stage
Part includes：Temperature is 200~400 DEG C, and the time is 6~15 hours.Furthermore it is possible to pass through gas-chromatography
Analyze whether first solvent eliminates.
In step (2), the reaction is generally carried out under inert gas (for example, nitrogen) protection,
The method that the actual conditions of reaction is referred to conventional load catalyst is carried out.The condition of the reaction can be with
Including：Temperature is 0~80 DEG C, preferably 15~40 DEG C；Time is 1~8 hour, and preferably 3~6 is small
When.
Second solvent can be in toluene, benzene, dimethylbenzene, hexane, heptane and hexamethylene
At least one, preferably toluene.
In addition, after reaction terminates, methods described can also include：Using the second solvent to the reaction
Obtained slurries are washed, and are then dried in vacuo, so as to which the loading type iron of solid be made
Catalyst.
In the present invention, the dosage of first solvent and the second solvent is referred to prior art progress
Selection, will not be repeated here.
Described load typed iron catalyst is used directly for olefinic polymerization, such as in gas-phase polymerization process,
Can also additional co-catalyst (such as MAO, alkyl aluminum) be used for olefinic polymerization.
According to the third aspect of the present invention, the invention provides a kind of iron catalysis for olefinic polymerization
Agent system, the Iron catalyst system include：Major catalyst and co-catalyst, the major catalyst are upper
The load typed iron catalyst stated.
The co-catalyst is preferably alkyl aluminum.In the present invention, adding alkyl aluminum in the polymerization can be with
The impurity in polymerization system is removed, improves polymerization activity to a certain extent, and is held high without adding price
Expensive MAO makees co-catalyst.
Preferably, the alkyl aluminum is selected from trimethyl aluminium, triethyl aluminum (TEA), tri-propyl aluminum, three
Butyl aluminium, triisopropylaluminiuand, triisobutyl aluminium, tri-tert aluminium, three amyl group aluminium, three hexyl aluminium,
At least one of trioctylaluminum, aluminium diethyl monochloride and ethyl aluminum dichloride.It is highly preferred that the alkane
Base aluminium is triethyl aluminum.
In the case of using alkyl aluminum as co-catalyst, in the catalyst system, Fe/Al's mole can
With than for 1：1.0×104~1.0 × 105。
Described Iron catalyst system can be with different polymerizations, such as gas-phase polymerization and slurry
Polymerization etc..Homopolymerization or copolymerization available for alkene, especially suitable for ethylene homo conjunction or second
The copolymerization of alkene and other alpha-olefins, the wherein non-limiting examples of alpha-olefin can include third
Alkene, butylene, amylene, hexene, octene and 4- methylpentenes -1 etc..
In polymerization, the alkyl aluminum can add simultaneously with the load typed iron catalyst, can also
Successively it is added in polymer reactor.
Solvent used in polymerization can be selected from alkane, aromatic hydrocarbon or halogenated hydrocarbons, preferably hexane, penta
One kind or their mixing in alkane, heptane, benzene, toluene, dichloromethane, chloroform, dichloroethanes
Thing, more preferably hexane.
In terms of Fe elements, the load typed iron catalyst polymerization when concentration can be 1 ×
10-8Mol/L~1 × 10-2mol/L。
The temperature of polymerization can be 0~80 DEG C；The pressure of polymerization can be 1~40MPa.
The present invention will be described in detail by way of examples below.
In following examples and comparative example, used silica gel model 2485, purchased from Regus-Dai Wei
Processing is being dried using preceding in this company, various solvents.
The percentage by weight of metal determines by the following method in load typed iron catalyst：Using plasma
Emission spectrometry (ICP), the P1000 types ICP-AES etc. of PE companies of instrument selection U.S. production from
Sub- emission spectrometer.
Polymer molecular weight determines by the following method with molecular weight distribution：Using gel permeation chromatography
(GPC), instrument uses Waters Alliance GPCV 2000, and solvent is 1,2,4- trichloro-benzenes, sample
Product concentration is 1mg/mL, solvent flow rate 1.0mL/min；Measurement temperature is 150 DEG C.
Embodiment 1
The present embodiment is used to illustrate load typed iron catalyst of the present invention and preparation method thereof.
1) preparation of zinc chloride/silica-gel carrier
Under nitrogen protection, in glass reactor, 0.54 gram of zinc chloride is added in room temperature, is then added
500 milliliters of tetrahydrofurans, start stirring, and 13.16 grams of silica gel are added in reactor, are warming up to 65 DEG C,
Stirring and dissolving 2 hours, then the evaporation of solvent at 80 DEG C, obtains white solid powder.Will be white
Color solid powder is dried in vacuo 2 hours at 100 DEG C, then is dried in vacuo 10 hours at 300 DEG C,
Zinc chloride solid/silica-gel carrier of good fluidity is obtained, through gas chromatographic analysis, fails to detect four
Hydrogen furans.
2) load of iron single site catalysts
Under nitrogen protection, that above-mentioned 1.4 grams of the zinc chloride/silica-gel carrier prepared is added into glass is anti-
Answer in device, add 20 milliliters of toluene and slurries are made, by 0.056g Fe catalyst precarsors 2, the double [1- (2,4,6- of 6-
Trimethylbenzene imines) methyl] pyridyl iron dichloride (that is, complex 4) is added in reactor, at 25 DEG C
Reaction 4 hours, is then washed with 15 milliliters of toluene, is dried in vacuo, is obtained load typed iron catalyst A
Product.The microscopic appearance of the load typed iron catalyst as illustrated in figs. 1A and ib, as seen from the figure, is urged
The particle shape of agent is good.In addition, the content of metal is as shown in table 1 in the product.
Embodiment 2
The present embodiment is used to illustrate load typed iron catalyst of the present invention and preparation method thereof.
1) preparation of zinc chloride/silica-gel carrier
Under nitrogen protection, in glass reactor, 0.67 gram of zinc chloride is added in room temperature, is then added
500 milliliters of tetrahydrofurans, start stirring, and 10.5 grams of silica gel are added in reactor, are warming up to 65 DEG C,
Stirring and dissolving 2 hours, then the evaporation of solvent at 80 DEG C, obtains white solid powder.Will be white
Color solid powder is dried in vacuo 2 hours at 100 DEG C, then is dried in vacuo 10 hours at 300 DEG C,
Zinc chloride solid/silica-gel carrier of good fluidity is obtained, through gas chromatographic analysis, fails to detect four
Hydrogen furans.
2) load of iron single site catalysts
Under nitrogen protection, that above-mentioned 1.1 grams of the zinc chloride/silica-gel carrier prepared is added into glass is anti-
Answer in device, add 20 milliliters of toluene and slurries are made, by 0.042g Fe catalyst precarsors 2, the double [1- (2,4,6- of 6-
Trimethylbenzene imines) methyl] pyridyl iron dichloride is added in reactor, react 4 hours at 25 DEG C, so
Washed afterwards with 15 milliliters of toluene, be dried in vacuo, obtain load typed iron catalyst B products.In the product
The content of metal is as shown in table 1.
Embodiment 3
The present embodiment is used to illustrate load typed iron catalyst of the present invention and preparation method thereof.
1) preparation of zinc chloride/silica-gel carrier
Under nitrogen protection, in glass reactor, 1.2 grams of zinc chloride are added in room temperature, are then added
500 milliliters of tetrahydrofurans, after starting stirring, 13.08 grams of silica gel are added in reactor, are warming up to
65 DEG C, stirring and dissolving 2 hours, then the evaporation of solvent at 80 DEG C, obtains white solid powder.
White solid powder is dried in vacuo 2 hours at 100 DEG C, then vacuum drying 10 is small at 300 DEG C
When, Zinc chloride solid/silica-gel carrier of good fluidity is obtained, through gas chromatographic analysis, fails to detect
To tetrahydrofuran.
2) load of iron single site catalysts
Under nitrogen protection, that above-mentioned 1.1 grams of the zinc chloride/silica-gel carrier prepared is added into glass is anti-
Answer in device, add 20 milliliters of toluene and slurries are made, by 0.048g Fe catalyst precarsors 2, the double [1- (2,4,6- of 6-
Trimethylbenzene imines) methyl] pyridyl iron dichloride is added in reactor, react 4 hours at 25 DEG C, so
Washed afterwards with 15 milliliters of toluene, be dried in vacuo, obtain load typed iron catalyst C products.In the product
The content of metal is as shown in table 1.
Comparative example 1
Under nitrogen protection, by silica-gel carrier 1.0 grams be added in glass reactor, add 20 milliliters
Slurries are made in toluene, by 0.037g Fe catalyst 2, double [1- (2,4, the 6- trimethylbenzene imines) methyl] pyridines of 6-
Ferrous chloride is added in reactor, is reacted 4 hours, is then washed with 15 milliliters of toluene, very at 25 DEG C
Sky is dried, and obtains support type Fe catalyst D1 products.The content of metal is as shown in table 1 in the product.
Test case 1~4
High pressure ethylene polymerization is tested
In 1 liter of stainless steel polymerization autoclave, with nitrogen and ethene, respectively displacement three times, then adds
The hexane solution of 500 milliliters of hexane solvents and the triethyl aluminum (TEA) of 1 milliliter of 1 mol/L,
Then above-described embodiment and 20 milligrams of the loaded catalyst A-C and D1 of comparative example preparation are separately added into,
30 DEG C are warming up to, pressure is risen into 10MPa, and react 1 hour at this pressure.Polymerisation knot
Shu Hou, cooling, polyethylene particle powder is collected, is weighed.Polymerization activity and polymerization in the experiment
Physical performance is as shown in table 2.
Table 1
| Numbering | Load typed iron catalyst | Zn contents/%wt | Fe contents/%wt |
| Embodiment 1 | A | 1.40 | 0.32 |
| Embodiment 2 | B | 1.92 | 0.33 |
| Embodiment 3 | C | 2.31 | 0.34 |
| Comparative example 1 | D1 | - | 0.30 |
Table 2
Embodiment 1-3 is understood compared with the result of comparative example 1, ZnCl2Addition can improve
The polymerization activity of iron catalyst；Can also the molecular weight distribution of basic guarantee polymer be basically unchanged.
The preferred embodiment of the present invention described in detail above, still, the present invention is not limited to above-mentioned
Detail in embodiment, can be to the skill of the present invention in the range of the technology design of the present invention
Art scheme carries out a variety of simple variants, and these simple variants belong to protection scope of the present invention.This
Outside, various embodiments of the present invention can be combined randomly, as long as it is not disobeyed
The thought of the present invention is carried on the back, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of load typed iron catalyst, it is characterised in that the load typed iron catalyst includes zinc chloride
/ silica-gel carrier and the iron single active center component being supported on carrier；Wherein, the iron single active center
The precursor of component is complex for the pyridine diimine Fe (II) of structure shown in formula 1：
Wherein, R1~R10It is identical or different, it each is selected from H, halogen or C1~C4Straight chain or branch
Alkyl group.
2. load typed iron catalyst according to claim 1, wherein, in formula 1, R1、R3、
R4And R6It is identical, R2And R5It is identical, R7~R10It is identical.
3. load typed iron catalyst according to claim 1, wherein, the iron single active center
The precursor of component is selected from least one of following complex：
Complex 1：R1=R3=R4=R6=Me, R2=R5=H, R7=R8=R9=R10=H；
Complex 2：R1=R3=R4=R6=Et, R2=R5=H, R7=R8=R9=R10=H；
Complex 3：R1=R3=R4=R6=iPr, R2=R5=H, R7=R8=R9=R10=H；
Complex 4：R1=R2=R3=R4=R5=R6=Me, R7=R8=R9=R10=H；
Complex 5：R1=R3=R4=R6=Me, R2=R5=Br, R7=R8=R9=R10=H；
Complex 6：R1=R3=R4=R6=Me, R2=R5=Et, R7=R8=R9=R10=H；
Complex 7：R1=R3=R4=R6=Et, R2=R5=Me, R7=R8=R9=R10=H；
Complex 8：R1=R3=R4=R6=Et, R2=R5=Br, R7=R8=R9=R10=H；
Complex 9：R1=R3=R4=R6=F, R2=R5=H, R7=R8=R9=R10=H；
Complex 10：R1=R3=R4=R6=Cl, R2=R5=H, R7=R8=R9=R10=H；
Complex 11：R1=R3=R4=R6=Br, R2=R5=H, R7=R8=R9=R10=H.
4. according to the load typed iron catalyst described in any one in claim 1-3, wherein, with institute
On the basis of the gross weight for stating load typed iron catalyst, Zn content is containing for 0.5~7.0 weight %, Fe
Measure as 0.01~5 weight %.
5. a kind of method for preparing load typed iron catalyst described in any one in claim 1-4, its
It is characterised by, this method includes：
(1) zinc chloride/silica-gel carrier is prepared
In the presence of the first solvent, silica gel is contacted with zinc chloride, obtain mixed solution；Then,
The first solvent in the mixed solution is removed, so as to which the zinc chloride/silica-gel carrier be made；
(2) load
In the presence of the second solvent, make the zinc chloride/silica-gel carrier and iron single active center component
Precursor reacted.
6. load typed iron catalyst according to claim 5, wherein, in step (1), institute
State the first solvent and be selected from tetrahydrofuran, ethanol, methanol, propyl alcohol, butanol, 2-Ethylhexyl Alcohol, ethylene glycol
At least one of with glycerine, preferably tetrahydrofuran；
In step (2), second solvent is selected from toluene, benzene, dimethylbenzene, hexane, heptane and ring
At least one of hexane, preferably toluene.
7. the method according to claim 11, wherein, in step (2), the bar of the reaction
Part includes：Temperature is 0~80 DEG C, and the time is 1~8 hour.
A kind of 8. Iron catalyst system for olefinic polymerization, it is characterised in that the Iron catalyst system
Including：Major catalyst and co-catalyst, the major catalyst is described in any one in claim 1-4
Load typed iron catalyst.
9. Iron catalyst system according to claim 8, wherein, the co-catalyst is alkyl
Aluminium；Preferably, the alkyl aluminum be selected from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum,
Triisopropylaluminiuand, triisobutyl aluminium, tri-tert aluminium, three amyl group aluminium, three hexyl aluminium, trioctylaluminum,
At least one of aluminium diethyl monochloride and ethyl aluminum dichloride.
10. Iron catalyst system according to claim 9, wherein, Fe/Al mol ratio is 1：
1.0×104~1.0 × 105。
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| CN107459597B (en) | 2020-02-18 |
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