CN105566542B - Prepare the catalyst system and catalyzing of polar functionalities polyolefin and the preparation method of the polyolefin - Google Patents
Prepare the catalyst system and catalyzing of polar functionalities polyolefin and the preparation method of the polyolefin Download PDFInfo
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Abstract
The present invention relates to a kind of catalyst system and catalyzing for preparing polar functionalities polyolefin, including：A) transistion metal compound having shown in formula I as major catalyst, wherein, X is selected from halogen；B) co-catalyst；C) ethene；And d) carry the alhpa olefin of polar group.The invention further relates to a kind of method for preparing the polyolefine material containing polar group, in the presence of major catalyst and co-catalyst shown in formula I, the copolyreaction of ethene and the alkene with polar group is carried out.
Description
Technical field
The invention belongs to be catalyzed and field of olefin polymerisation, it is related to a kind of transistion metal compound and alkane with specific structure
The catalyst system and catalyzing of the olefinic polymerization of base aikyiaiurnirsoxan beta composition, the catalyst system can be catalyzed ethene and carry polar group (such as hydroxyl)
Olefin-copolymerization, obtain the polyolefine material containing polar group.
Background technology
The single centre transition-metal catalyst of olefin polymerization recent decades be always Organometallic Chemistry, catalysis learn,
The study hotspot of polymer chemistry and materialogy.Using this kind of catalyst, molecular weight distribution and chemical composition distribution can be obtained
All well-proportioned olefin polymer, while the molecular structure of polymer and molecular weight can by adjusting catalyst structure height
Control.By single-site catalysts, the not getable olefin polymer of traditional Ziegler-Natta catalyst can be obtained.
Polyolefin has good mechanical property, electric property, chemical property and processing characteristics, and cheap, extensively
It is general to be applied to the fields such as daily life, industrial and agricultural production.Polyolefin chain presentation is nonpolar, surface energy is low, and molecule is in chemical inertness,
These characteristics greatly influence their applications in many aspects, it is difficult to meet the needs of society is growing.To poly-
Alkene carry out functional modification all multi-methods in, by polar monomer by copolymerization process be introduced into polyolefin chain always just by
The great attention of people.Introduce polar group, be not only able to efficiently control many critical natures of polyolefin, as cohesive,
Dyeability, printing, solvent resistance, compatibility and rheological characteristic etc., and the original characteristic of polyolefin is kept well.
After polar group introduces polymerization system, coordination that can be to polymerization process, increase generation and have a strong impact on, it is poly- so as to reduce
Activity is closed, serious meeting causes system to inactivate.Due to the characteristic of post transition metal elements, this influence is catalyzed to late transition metal
Agent influence is small a lot, so most of research on polar monomer copolymerization all uses late transition metal catalyst (Science
2000,287,460；Chem.Rev.2000,100,1479；Chem.Rev.2000,100,1169), and early transition metal is used,
The research of particularly IVB metallic catalysts is relatively fewer.
Using Ziegler-Natta catalyst system and catalyzings, the homopolymerization of straight chain-ω alkene esters can be catalyzed.Typically first use R2AlCl is (such as
Et2AlCl monomer) is handled, sterically hindered bigger ester has higher conversion ratio
(J.Polym.Sci.Polym.Chem.1988,26,677).Use same catalyst system and catalyzing, it is possible to achieve one including ethene
The copolymerization (J.Polym.Sci.Polym.Chem.1989,27,2051) of serial alpha-olefin and ω-alkene ester.
It can realize that ω-allyl ester monomer is copolymerized with ethene and propylene using metallocene catalysis system.When use (n-BuCp)2ZrCl2/ MAO is that catalyst ethene is copolymerized with the alkene methyl esters of 9- ten and with Et (Ind)2ZrCl2/ MAO is catalyzed propylene and 9-
When ten alkene methyl esters, the copolymerization of 10- hendecenes isobutyl, significantly reducing for activity can be observed
(Eur.Polym.J.1997,33,1187；1998,34,1093).The chloro- 1- of 11- can be prepared using means of special bridged metallocene catalysts
The random copolymer of hendecene and 1- heptene and it and ethene, the terpolymer of propylene
(Macromol.Chem.Phys.1997,198,291).M ü lhaupt can realize N, (the front three silicon of N- bis- using zirconocene catalyst
Base) -1- amido -10- hendecenes and ethene copolymerization (Polymer, 1997,38,2455).Novak is urged with non-bridged combined metal
Agent, ethene is set to be copolymerized (Polym.Mater.Sci.Eng.1999,80,45) with acrylate monomer.
Using non-luxuriant zirconium-based catalyst, it is catalyzed ethene and undecylenic alcohol is copolymerized, activity is substantially suitable with ethylene homo,
Polar monomer in the polymer molar fraction more than 8% (J.Polym.Sci.Polym.Chem.2005,43,5944).Three wells are public
" the FI catalyst " of department can be used for the copolymerization of ethene and polar monomer.Using this kind of catalyst, successfully make 5- hexenyls -1-
Acetate is copolymerized with ethene, with the increase of co-monomer dosage, polar monomer content increase in the polymer, is reached as high as
3.2%, but polymerization activity and polymer molecular weight are all decreased obviously (J.Am.Chem.Soc.2008,130,17636).
Patent CN 200410088511 discloses the titanium catalyst being coordinated using Schiff, can be catalyzed-alkene and polarity
Monomer copolymerization.The titanium catalyst that CN 200610028958 is coordinated using tridentate ligand, the copolymerization of ethene and polar monomer is carried out,
Monomer is applied widely, and activity is higher, and co-monomer insertion rate can be more than 8%.
Alpha-olefin and polar monomer copolymerization, it is critically important research direction.From document as can be seen that this direction is deposited at present
In following Railway Project：1) because the coordination with activated centre easily occurs for the polar group nearer apart from double bond, cause to be catalyzed
Agent inactivates, so in most research and development, it is long-chain co-monomer, i.e. alkene to polymerize with the co-monomer with polar group
The carbon atom being spaced between hydrocarbon double bond and polar group is more, to ensure that loss of activity is carried out in the not excessive area of polar group；2) to the greatest extent
Pipe employs the polar monomer of longer chain length, but the effect in polar group and activated centre is still inevitable, with alpha-olefin
Homopolymerization compare, the Copolymerization activity of alpha-olefin and polar monomer will reduce a lot；3) compared with the homopolymerization of alpha-olefin, alpha-olefin with
The polymer molecular weight that the copolymerization of polar monomer obtains is also much lower.So polymerization catalyst system that research and development are new, it is ensured that good
Good polymerization behavior and polymer architecture performance, are still an important problem so as to obtain new polyolefine material.
The content of the invention
It is used to prepare the catalyst system and catalyzing containing polar group polyolefine material it is an object of the invention to provide a kind of.The catalysis
System can be catalyzed ethene and the monomer copolymerization with polar group, while high polymerization activity is ensured, obtain having higher pole
The polyolefine material of property group content.
First embodiment of the present invention is related to a kind of catalyst system and catalyzing for being used to prepare polar functionalities polyolefin, bag
Include：
A) transistion metal compound having shown in formula I as major catalyst；
Wherein, X is selected from halogen；
B) co-catalyst；
C) ethene；And
D) alpha-olefin of polar group is carried.
In a preferred embodiment of the present invention, the halogen is selected from fluorine, chlorine and bromine, preferably chlorine.
In a preferred embodiment of the present invention, the co-catalyst is alkylaluminoxane.
In further preferred embodiment, the alkylaluminoxane is selected from structure such as formula (II) and/or formula (III)
Alkylaluminoxane：
Wherein R1-R7It is identical or different, alkyl, cycloalkyl or aryl are each independently selected from, n is 4~30 integer, excellent
Select 10~30 integer.
In a preferred embodiment of the present invention, the alkyl is C1~C20Straight chain or branched saturated alkyl, preferably
For C1~C10Straight chain or branched saturated alkyl, more preferably C1~C6Straight chain or branched saturated alkyl；It is it is further preferred that described
Alkyl is selected from following compound：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, positive penta
Base, sec-amyl, isopentyl, n-hexyl, Sec-Hexyl, isohesyl, n-heptyl and its isomers；Still more preferably methyl, ethyl,
N-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, sec-amyl, isopentyl, n-hexyl or dissident
Base；Most preferable.
In a preferred embodiment of the present invention, the cycloalkyl is C3~C20Saturated cyclic alkyl, preferably C3
~C10Saturated cyclic alkyl, more preferably C3~C6Saturated cyclic alkyl；Most preferably, the cycloalkyl is selected from following chemical combination
Thing：Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl；Most preferably cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl.
In a preferred embodiment of the present invention, the aryl is selected from phenyl, substituted-phenyl, naphthyl or pyridine radicals,
More preferably phenyl or substituted-phenyl.
In a preferred embodiment of the present invention, the alpha-olefin with polar group is α-alkene with hydroxyl
Hydrocarbon, preferably 9- decen-1-ols.
Second embodiment of the present invention is related to a kind of method for the polyolefin for preparing polar functionalities, is included in such as formula
In the presence of major catalyst and co-catalyst shown in I, the copolyreaction of ethene and the alkene with polar group is carried out；
Wherein, X is selected from halogen.
In a preferred embodiment of the present invention, the halogen is selected from fluorine, chlorine and bromine, preferably chlorine.
In a preferred embodiment of the present invention, the co-catalyst is alkylaluminoxane.
In a preferred embodiment of the present invention, the alkylaluminoxane is selected from structure such as formula (II) and/or formula
(III) alkylaluminoxane：
Wherein R1-R7It is identical or different, alkyl, cycloalkyl or aryl are each independently selected from, n is 4~30 integer, excellent
Select 10~30 integer.
In a preferred embodiment of the present invention, the alkyl is C1~C20Straight chain or branched saturated alkyl, preferably
For C1~C10Straight chain or branched saturated alkyl, more preferably C1~C6Straight chain or branched saturated alkyl；It is it is further preferred that described
Alkyl is selected from following compound：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, positive penta
Base, sec-amyl, isopentyl, n-hexyl, Sec-Hexyl, isohesyl, n-heptyl and its isomers；Still more preferably methyl, ethyl,
N-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, sec-amyl, isopentyl, n-hexyl or dissident
Base；Most preferable.
In a preferred embodiment of the present invention, the cycloalkyl is C3~C20 saturated cyclic alkyl, preferably C3
~C10 saturated cyclic alkyl, more preferably C3~C6 saturated cyclics alkyl；Most preferably, the cycloalkyl is selected from following chemical combination
Thing：Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl；Most preferably cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl.
In a preferred embodiment of the present invention, the aryl is selected from phenyl, substituted-phenyl, naphthyl or pyridine radicals,
More preferably phenyl or substituted-phenyl.
In a preferred embodiment of the present invention, the alkene with polar group is the alkene with hydroxyl,
It is preferred that 9- decen-1-ols.
In a preferred embodiment of the present invention, the reaction temperature for stating copolyreaction is -20 DEG C to 200 DEG C, preferably
20 DEG C to 180 DEG C, reacting ethylene pressure is 1 to 80atm.
The carbon monoxide-olefin polymeric that the present invention is formed using catalyst and the MAO of the structure carry out ethene with
During the copolymerization of the alkene (such as 9- decen-1-ols) with polar group.Polar group wherein can be carried using as co-monomer
Alkene in advance with co-catalyst (such as triisobutyl aluminium) handle, protected.It is polymerize under different polymerization temperatures, is polymerize
The content of polar monomer is different and different according to polar monomer inlet amount in thing, while polymerization temperature is to the insertion of polar monomer
Also have an impact.
Brief description of the drawings
Fig. 1 is the GPC curves of the polymer of embodiment 1.
Fig. 2 is the DSC curve of the polymer of embodiment 1.
Fig. 3 is the polymer of embodiment 113C-NMR spectrograms.
Fig. 4 is the GPC curves of the polymer of embodiment 4.
Fig. 5 is the DSC curve of the polymer of embodiment 4.
Fig. 6 is the polymer of embodiment 413C-NMR spectrograms.
Fig. 7 is the GPC curves of the polymer of embodiment 9.
Fig. 8 is the DSC curve of the polymer of embodiment 9.
Fig. 9 is the polymer of embodiment 913C-NMR spectrograms.
Embodiment
The following example is only used for that the present invention is described in detail, it will be appreciated that the scope of the present invention is not limited to
These embodiments.
In an embodiment of the present invention：
Polymer molecular weight is determined using GPC, wherein PDI=Mw/Mn (the ratio between weight average molecular weight and number-average molecular weight)；
Polar monomer content uses in polymer13C-NMR is determined；
Melting point polymer is determined using DSC；
Activity is calculated in the following manner, by the quality (kg) of polymer divided by the molal weight of catalyst (with Ti
Molal weight meter) again divided by the reaction time.
Embodiment 1
The polyplant fully dried, is then vacuumized to it, and is purged with nitrogen, repeatedly for three times.Again to poly-
Attach together to put and vacuumized, solenoid valve control, be filled with ethene, 25.8 milliliters of toluene are added at 25 DEG C, add 0.1 milliliter of 9- last of the ten Heavenly stems
Alkene -1- alcohol, 0.6 milliliter of triisobutylaluminum toluene solution (1.1 mole/milliliter), stir 10 minutes.It is molten to add 3mL MAO toluene
Transistion metal compound (X=Cl) solution (10 micromoles/milliliter), starts to count described in liquid (1.67 mole/milliliter), 1 milliliter of Formulas I
When.After 20 minutes, ethene is closed, acidic ethanol is added in reaction solution, is stirred more than 6 hours, is filtrated to get polymer, will
The polymer arrived is dried in vacuo 24 hours at 60 DEG C, weighs to obtain 0.49 gram of polymer.Specific reaction condition and result are listed in
In table 1.The CPC test curves of compound made from the present embodiment, DSC curve and13C-NMR test results are respectively such as Fig. 1-3 institutes
Show.
Embodiment 2
The polyplant fully dried, is then vacuumized to it, and is purged with nitrogen, repeatedly for three times.Again to poly-
Attach together to put and vacuumized, solenoid valve control, be filled with ethene, 25.1 milliliters of toluene are added at 25 DEG C, add 0.2 milliliter of 9- last of the ten Heavenly stems
Alkene -1- alcohol, 1.2 milliliters of triisobutylaluminum toluene solutions (1.1 mole/milliliter), stir 10 minutes.It is molten to add 3mL MAO toluene
Transistion metal compound (X=Cl) liquid (10 micromoles/milliliter), starts to count described in liquid (1.67 mole/milliliter), 1 milliliter of Formulas I
When.After 20 minutes, ethene is closed, adds acidic ethanol in reaction solution, stirred more than 6 hours, be filtrated to get polymer, 60 DEG C
Lower vacuum drying 24 hours, weighs to obtain 0.61 gram of polymer.Specific reaction condition and result are listed in Table 1.
Embodiment 3
The polyplant fully dried, is then vacuumized to it, and is purged with nitrogen, repeatedly for three times.Again to poly-
Attach together to put and vacuumized, solenoid valve control, be filled with ethene, 24.4 milliliters of toluene are added at 25 DEG C, add 0.3 milliliter of 9- last of the ten Heavenly stems
Alkene -1- alcohol, 1.8 milliliters of triisobutylaluminum toluene solutions (1.1 mole/milliliter), stir 10 minutes.It is molten to add 3mL MAO toluene
Transistion metal compound (X=Cl) solution (10 micromoles/milliliter), starts to count described in liquid (1.67 mole/milliliter), 1 milliliter of Formulas I
When.After 20 minutes, ethene is closed, adds acidic ethanol in reaction solution, stirred more than 6 hours, be filtrated to get polymer, 60 DEG C
Lower vacuum drying 24 hours, weighs to obtain 0.43 gram of polymer.Specific reaction condition and result are listed in Table 1.
Embodiment 4
The polyplant fully dried, is then vacuumized to it, and is purged with nitrogen, repeatedly for three times.Again to poly-
Attach together to put and vacuumized, solenoid valve control, be filled with ethene, 23.0 milliliters of toluene are added at 25 DEG C, add 0.5 milliliter of 9- last of the ten Heavenly stems
Alkene -1- alcohol, 3.0 milliliters of triisobutylaluminum toluene solutions (1.1 mole/milliliter), stir 10 minutes.It is molten to add 3mL MAO toluene
Transistion metal compound (X=Cl) solution (10 micromoles/milliliter), starts to count described in liquid (1.67 mole/milliliter), 1 milliliter of Formulas I
When.After 20 minutes, ethene is closed, adds acidic ethanol in reaction solution, stirred more than 6 hours, be filtrated to get polymer, 60 DEG C
Lower vacuum drying 24 hours, obtains the polymeric articles.Specific reaction condition and result are listed in Table 1.The present embodiment is made
The CPC test curves of compound, DSC curve and13C-NMR test results difference is as Figure 4-Figure 6.
Embodiment 5
The polyplant fully dried, is then vacuumized to it, and is purged with nitrogen, repeatedly for three times.Again to poly-
Attach together to put and vacuumized, solenoid valve control, be filled with ethene, 25.8 milliliters of toluene are added at 50 DEG C, add 0.1 milliliter of 9- last of the ten Heavenly stems
Alkene -1- alcohol, 0.6 milliliter of triisobutylaluminum toluene solution (1.1 mole/milliliter), stir 10 minutes.It is molten to add 3mL MAO toluene
Transistion metal compound (X=Cl) solution (10 micromoles/milliliter), starts to count described in liquid (1.67 mole/milliliter), 1 milliliter of Formulas I
When.After 20 minutes, ethene is closed, adds acidic ethanol in reaction solution, stirred more than 6 hours, be filtrated to get polymer, 60 DEG C
Lower vacuum drying 24 hours, weighs to obtain 0.73 gram of polymer.Specific reaction condition and result are listed in Table 1.
Embodiment 6
The polyplant fully dried, is then vacuumized to it, and is purged with nitrogen, repeatedly for three times.Again to poly-
Attach together to put and vacuumized, solenoid valve control, be filled with ethene, 25.1 milliliters of toluene are added at 25 DEG C, add 0.2 milliliter of 9- last of the ten Heavenly stems
Alkene -1- alcohol, 1.2 milliliters of triisobutylaluminum toluene solutions (1.1 mole/milliliter), stir 10 minutes.It is molten to add 3mL MAO toluene
Transistion metal compound (X=Cl) solution (10 micromoles/milliliter), starts to count described in liquid (1.67 mole/milliliter), 1 milliliter of Formulas I
When.After 20 minutes, ethene is closed, adds acidic ethanol in reaction solution, stirred more than 6 hours, be filtrated to get polymer, 60 DEG C
Lower vacuum drying 24 hours, weighs to obtain 0.56 gram of polymer.Specific reaction condition and result are listed in Table 1.
Embodiment 7
The polyplant fully dried, is then vacuumized to it, and is purged with nitrogen, repeatedly for three times.Again to poly-
Attach together to put and vacuumized, solenoid valve control, be filled with ethene, 24.4 milliliters of toluene are added at 25 DEG C, add 0.3 milliliter of 9- last of the ten Heavenly stems
Alkene -1- alcohol, 1.8 milliliters of triisobutylaluminum toluene solutions (1.1 mole/milliliter), stir 10 minutes.It is molten to add 3mL MAO toluene
Transistion metal compound (X=Cl) solution (10 micromoles/milliliter), starts to count described in liquid (1.67 mole/milliliter), 1 milliliter of Formulas I
When.After 20 minutes, ethene is closed, adds acidic ethanol in reaction solution, stirred more than 6 hours, be filtrated to get polymer, 60 DEG C
Lower vacuum drying 24 hours, weighs to obtain 0.87 gram of polymer.Specific reaction condition and result are listed in Table 1.
Embodiment 8
The polyplant fully dried, is then vacuumized to it, and is purged with nitrogen, repeatedly for three times.Again to poly-
Attach together to put and vacuumized, solenoid valve control, be filled with ethene, 23.0 milliliters of toluene are added at 25 DEG C, add 0.5 milliliter of 9- last of the ten Heavenly stems
Alkene -1- alcohol, 3.0 milliliters of triisobutylaluminum toluene solutions (1.1 mole/milliliter), stir 10 minutes.It is molten to add 3mL MAO toluene
Transistion metal compound (X=Cl) solution (10 micromoles/milliliter), starts to count described in liquid (1.67 mole/milliliter), 1 milliliter of Formulas I
When.After 20 minutes, ethene is closed, adds acidic ethanol in reaction solution, stirred more than 6 hours, be filtrated to get polymer, 60 DEG C
Lower vacuum drying 24 hours, weighs to obtain 0.74 gram of polymer.Specific reaction condition and result are listed in Table 1.
Embodiment 9
The polyplant fully dried, is then vacuumized to it, and is purged with nitrogen, repeatedly for three times.Again to poly-
Attach together to put and vacuumized, solenoid valve control, be filled with ethene, add 25.8 milliliters of toluene at 80 DEG C, add 0.1 milliliter of 9- last of the ten Heavenly stems
Alkene -1- alcohol, 0.6 milliliter of triisobutylaluminum toluene solution (1.1 mole/milliliter), stir 10 minutes.It is molten to add 3mL MAO toluene
Transistion metal compound (X=Cl) solution (10 micromoles/milliliter), starts to count described in liquid (1.67 mole/milliliter), 1 milliliter of Formulas I
When.After 20 minutes, ethene is closed, adds acidic ethanol in reaction solution, stirred more than 6 hours, be filtrated to get polymer, 60 DEG C
Lower vacuum drying 24 hours, weighs to obtain 1.08 grams of polymer.Specific reaction condition and result are listed in Table 1.The present embodiment system
The CPC test curves of compound, DSC curve and13C-NMR test results difference is as Figure 7-9.
Embodiment 10
The polyplant fully dried, is then vacuumized to it, and is purged with nitrogen, repeatedly for three times.Again to poly-
Attach together to put and vacuumized, solenoid valve control, be filled with ethene, 25.1 milliliters of toluene are added at 80 DEG C, add 0.2 milliliter of 9- last of the ten Heavenly stems
Alkene -1- alcohol, 1.2 milliliters of triisobutylaluminum toluene solutions (1.1 mole/milliliter), stir 10 minutes.It is molten to add 3mL MAO toluene
Transistion metal compound (X=Cl) solution (10 micromoles/milliliter), starts to count described in liquid (1.67 mole/milliliter), 1 milliliter of Formulas I
When.After 20 minutes, ethene is closed, adds acidic ethanol in reaction solution, stirred more than 6 hours, be filtrated to get polymer, 60 DEG C
Lower vacuum drying 24 hours, weighs to obtain 0.96 gram of polymer.Specific reaction condition and result are listed in Table 1.
Embodiment 11
The polyplant fully dried, is then vacuumized to it, and is purged with nitrogen, repeatedly for three times.Again to poly-
Attach together to put and vacuumized, solenoid valve control, be filled with ethene, 24.4 milliliters of toluene are added at 80 DEG C, add 0.3 milliliter of 9- last of the ten Heavenly stems
Alkene -1- alcohol, 1.8 milliliters of triisobutylaluminum toluene solutions (1.1 mole/milliliter), stir 10 minutes.It is molten to add 3mL MAO toluene
Transistion metal compound (X=Cl) solution (10 micromoles/milliliter), starts to count described in liquid (1.67 mole/milliliter), 1 milliliter of Formulas I
When.After 20 minutes, ethene is closed, adds acidic ethanol in reaction solution, stirred more than 6 hours, be filtrated to get polymer, 60 DEG C
Lower vacuum drying 24 hours, weighs to obtain 1.18 grams of polymer.Specific reaction condition and result are listed in Table 1.
Embodiment 12
The polyplant fully dried, is then vacuumized to it, and is purged with nitrogen, repeatedly for three times.Again to poly-
Attach together to put and vacuumized, solenoid valve control, be filled with ethene, 23.0 milliliters of toluene are added at 80 DEG C, add 0.5 milliliter of 9- last of the ten Heavenly stems
Alkene -1- alcohol, 3.0 milliliters of triisobutylaluminum toluene solutions (1.1 mole/milliliter), stir 10 minutes.It is molten to add 3mL MAO toluene
Transistion metal compound (X=Cl) solution (10 micromoles/milliliter), starts to count described in liquid (1.67 mole/milliliter), 1 milliliter of Formulas I
When.After 20 minutes, ethene is closed, adds acidic ethanol in reaction solution, stirred more than 6 hours, be filtrated to get polymer, 60 DEG C
Lower vacuum drying 24 hours, weighs to obtain 0.50 gram of polymer.Specific reaction condition and result are listed in Table 1.
The preferred embodiment of the present invention is the foregoing is only, but the scope of the present invention is not limited thereto, Ren Heben
The technical staff in field easily can be changed or change in technical scope disclosed by the invention, and this change or change
Change should be all included within the scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Enclose and be defined.
Table 1
It should be noted that embodiment described above is only used for explaining the present invention, do not form to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, on the contrary, this hair
It is bright to can be extended to other all methods and applications with identical function.
Claims (38)
1. a kind of catalyst system and catalyzing for preparing polar functionalities polyolefin, including：
A) transistion metal compound having shown in formula I as major catalyst；
Wherein, X is selected from halogen；
B) co-catalyst；
C) ethene；And
D) alpha-olefin of polar group is carried；Wherein, the alpha-olefin with polar group is 9- decen-1-ols.
2. catalyst system and catalyzing according to claim 1, it is characterised in that the halogen is selected from fluorine, chlorine and bromine.
3. catalyst system and catalyzing according to claim 2, it is characterised in that the halogen is chlorine.
4. catalyst system and catalyzing according to claim 1, it is characterised in that the co-catalyst is alkylaluminoxane.
5. catalyst system and catalyzing according to claim 4, it is characterised in that the alkylaluminoxane is selected from structure such as formula (II)
And/or the alkylaluminoxane of formula (III)：
Wherein R1-R7 is identical or different, is each independently selected from alkyl, cycloalkyl or aryl, and n is 4~30 integer.
6. catalyst system and catalyzing according to claim 5, it is characterised in that n is 10~30 integer.
7. catalyst system and catalyzing according to claim 5, it is characterised in that the alkyl is C1~C20 straight chains or branched saturation
Alkyl.
8. catalyst system and catalyzing according to claim 7, it is characterised in that the alkyl is C1~C10 straight chains or branched saturation
Alkyl.
9. catalyst system and catalyzing according to claim 8, it is characterised in that the alkyl is C1~C6 straight chains or branched saturation alkane
Base.
10. catalyst system and catalyzing according to claim 9, it is characterised in that the alkyl is selected from following compound：Methyl, second
Base, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, sec-amyl, isopentyl, n-hexyl, it is secondary oneself
Base, isohesyl and its isomers.
11. catalyst system and catalyzing according to claim 10, it is characterised in that the alkyl is selected from following compound：Methyl, second
Base, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, sec-amyl, isopentyl, n-hexyl or different
Hexyl.
12. catalyst system and catalyzing according to claim 11, it is characterised in that the alkyl is methyl.
13. according to the catalyst system and catalyzing any one of claim 5-12, it is characterised in that the cycloalkyl is C3~C20
Saturated cyclic alkyl.
14. catalyst system and catalyzing according to claim 13, it is characterised in that the cycloalkyl is C3~C10 saturated cyclic hydrocarbon
Base.
15. catalyst system and catalyzing according to claim 14, it is characterised in that the cycloalkyl is C3~C6 saturated cyclic hydrocarbon
Base.
16. catalyst system and catalyzing according to claim 15, it is characterised in that the cycloalkyl is cyclopropyl, cyclobutyl, ring penta
Base or cyclohexyl.
17. according to the catalyst system and catalyzing any one of claim 5-12, it is characterised in that the aryl is selected from phenyl, taken
For phenyl, naphthyl or pyridine radicals.
18. catalyst system and catalyzing according to claim 17, it is characterised in that the aryl is phenyl or substituted-phenyl.
19. a kind of method for preparing polar functionalities polyolefin, it is included in depositing for major catalyst shown in formula I and co-catalyst
Under, the copolyreaction of ethene and the alkene with polar group is carried out；
Wherein, X is selected from halogen；The alkene with polar group is 9- decen-1-ols.
20. according to the method for claim 19, it is characterised in that the halogen is selected from fluorine, chlorine and bromine.
21. according to the method for claim 20, it is characterised in that the halogen is chlorine.
22. according to the method any one of claim 19-21, it is characterised in that the co-catalyst is alkyl alumina
Alkane.
23. according to the method for claim 22, it is characterised in that the alkylaluminoxane be selected from structure such as formula (II) and/
Or the alkylaluminoxane of formula (III)：
Wherein R1-R7 is identical or different, is each independently selected from alkyl, cycloalkyl or aryl, and n is 4~30 integer.
24. according to the method for claim 23, it is characterised in that n is 10~30 integer.
25. according to the method for claim 23, it is characterised in that the alkyl is C1~C20 straight chains or branched saturation alkane
Base.
26. according to the method for claim 25, it is characterised in that the alkyl is C1~C10 straight chains or branched saturation alkane
Base.
27. according to the method for claim 26, it is characterised in that the alkyl is C1~C6 straight chains or branched saturation alkane
Base.
28. according to the method for claim 27, it is characterised in that the alkyl is selected from following compound：Methyl, ethyl,
N-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, sec-amyl, isopentyl, n-hexyl, Sec-Hexyl,
Isohesyl and its isomers.
29. according to the method for claim 28, it is characterised in that the alkyl is selected from following compound：Methyl, ethyl,
N-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, sec-amyl, isopentyl, n-hexyl or dissident
Base.
30. according to the method for claim 29, it is characterised in that the alkyl is methyl.
31. according to the method any one of claim 23-30, it is characterised in that the cycloalkyl is C3~C20 saturations
Cyclic hydrocarbon group.
32. according to the method for claim 31, it is characterised in that the cycloalkyl is C3~C10 saturated cyclic alkyl.
33. according to the method for claim 32, it is characterised in that the cycloalkyl is C3~C6 saturated cyclic alkyl.
34. according to the method for claim 33, it is characterised in that the cycloalkyl be cyclopropyl, cyclobutyl, cyclopenta or
Cyclohexyl.
35. according to the method any one of claim 23-30, it is characterised in that the aryl is selected from phenyl, substituted benzene
Base, naphthyl or pyridine radicals.
36. according to the method for claim 35, it is characterised in that the aryl is phenyl or substituted-phenyl.
37. according to the method any one of claim 19-21, it is characterised in that the reaction temperature of the copolyreaction
For -20 DEG C to 200 DEG C, reacting ethylene pressure is 1atm to 80atm.
38. according to the method for claim 37, it is characterised in that the reaction temperature of the copolyreaction is 20 to 180 DEG C.
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| US5777050A (en) * | 1993-09-27 | 1998-07-07 | Dsm N.V. | Process for polymerizing ethylene in the presence of a catalyst composition |
| CN1472230A (en) * | 2000-07-04 | 2004-02-04 | 三井化学株式会社 | Method for preparing polar olefin copolymer and polar olefin copolymer therefrom |
| CN101910187A (en) * | 2007-12-31 | 2010-12-08 | Sk能源株式会社 | Transition metal complexes, catalysts composition containing the same, and process for preparing ethylene homopolymers or copolymers of ethylene and alpha-olefins using the same |
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|---|---|---|---|---|
| US5777050A (en) * | 1993-09-27 | 1998-07-07 | Dsm N.V. | Process for polymerizing ethylene in the presence of a catalyst composition |
| CN1472230A (en) * | 2000-07-04 | 2004-02-04 | 三井化学株式会社 | Method for preparing polar olefin copolymer and polar olefin copolymer therefrom |
| CN101910187A (en) * | 2007-12-31 | 2010-12-08 | Sk能源株式会社 | Transition metal complexes, catalysts composition containing the same, and process for preparing ethylene homopolymers or copolymers of ethylene and alpha-olefins using the same |
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