CN104098608A - Scandium metallocene catalyst precursor, preparation method and application thereof, and preparation method for copolymer - Google Patents
Scandium metallocene catalyst precursor, preparation method and application thereof, and preparation method for copolymer Download PDFInfo
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- CN104098608A CN104098608A CN201310115914.8A CN201310115914A CN104098608A CN 104098608 A CN104098608 A CN 104098608A CN 201310115914 A CN201310115914 A CN 201310115914A CN 104098608 A CN104098608 A CN 104098608A
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Abstract
The invention provides a scandium metallocene catalyst precursor, a preparation method and application thereof, and a preparation method for a copolymer of ethylene and a cycloolefine. The scandium metallocene catalyst precursor has the structure shown as the formula (I), R1 is a C1-C20 linear or branched alkylidene, R2 and R3 are independently H or a C1-C20 linear or branched alkyl, R4 is methylene, and R5 is a C1-C5 linear or branched alkyl. A catalyst containing the scandium metallocene catalyst precursor has relatively high catalytic activity.
Description
Technical field
The present invention relates to a kind of luxuriant scandium metal catalysts precursors, a kind of preparation method of the luxuriant scandium metal catalysts precursors based on two indenyl ligands, the luxuriant scandium metal catalysts precursors based on two indenyl ligands being prepared by the method, the application of above-mentioned luxuriant scandium metal catalysts precursors in catalyzed ethylene and cycloolefin copolyreaction and preparation method of a kind of ethene and cyclic olefine copolymer based on two indenyl ligands.
Background technology
Cyclic olefine copolymer (COC) is the polymkeric substance that ethene and cycloolefin copolymerization obtain, and comprises cyclic olefin monomers structural unit in its skeleton structure.For polypropylene and polyethylene, cyclic olefine copolymer is that a kind of modulus is higher, water-intake rate is lower, the good non-crystalline state amorphous macromolecule of transparency polymkeric substance, can be used for engineering thermoplastic materials.
Research shows, the optical property of cyclic olefine copolymer is similar to polymethylmethacrylate (PMMA), has low birefringence and water-absorbent and has higher rigidity.Common ethene has the transparency good as glass and humidity resistance with the multipolymer of cycloolefin, and ultralow complex refractivity index can compare favourably with glass aspheric lenses it, can be used to the field such as CD, optical lens.Meanwhile, cyclic olefine copolymer also has good chemical resistant properties and thermostability, also may become the desirable substitute products of polycarbonate, polymethylmethacrylate (synthetic glass), polystyrene and polyvinyl chloride.At present, cyclic olefine copolymer has been used to consumer goods market and medical field, comprises food and pharmaceutical packing.
But because the cyclic olefine copolymer that adopts existing method to prepare exists the problem that snappiness is poor, second-order transition temperature is very high, it is not easy to be processed to goods.In order to improve these shortcomings, and obtain cyclic olefine copolymer cheap, that performance is more excellent, realize its large-scale application as engineering materials, must carry out deep research to the synthetic and application art of cyclic olefine copolymer.Wherein, the catalyzer of preparing described cyclic olefine copolymer has become the focus of a research.
Research shows, adopts metallocene catalyst not only can obtain having multipolymer (Angew.Chem.Int.Ed.2005,44 of higher ring-type monomer content; 962); but also can expand range of choice (J.Organomet.Chem.2006,691,3114 of cyclic monomer; Macromolecules, 2012,45,5397).In addition, research shows, compared with single-metal reforming catalyst, to have synergistic bimetallic catalyst and not only can improve polymerization activity, can also improve the ratio (PNAS.2006,103,15295) of comonomer in polymkeric substance.Along with the reach of science, researching and developing the novel catalyzer for cycloolefin copolymerization has become the prior development direction in this field.
Summary of the invention
The object of this invention is to provide a kind of new luxuriant scandium metal catalysts precursors based on two indenyl ligands, a kind of preparation method of the luxuriant scandium metal catalysts precursors based on two indenyl ligands, the luxuriant scandium metal catalysts precursors based on two indenyl ligands being prepared by the method, the application of above-mentioned luxuriant scandium metal catalysts precursors in catalyzed ethylene and cycloolefin copolyreaction and the preparation method of a kind of ethene and cyclic olefine copolymer.
The invention provides a kind of luxuriant scandium metal catalysts precursors based on two indenyl ligands, wherein, described luxuriant scandium metal catalysts precursors has the structure shown in formula (I):
formula (I),
Wherein, R
1for C
1-C
20straight or branched alkylidene group, R
2and R
3be hydrogen or C independently of one another
1-C
20straight or branched alkyl, R
4for methylene radical, R
5for C
1-C
5straight or branched alkyl.
The present invention also provides a kind of preparation method of the luxuriant scandium metal catalysts precursors based on two indenyl ligands, and the method is included under coordination reaction condition, is Sc (R by compound and the general formula with structure shown in formula II
4si (R
5)
3)
3(THF)
2compound in organic solvent, react, obtain having the luxuriant scandium metal catalysts precursors based on two indenyl ligands of structure shown in formula I;
formula II,
Wherein, R
1for C
1-C
20straight or branched alkylidene group, R
2and R
3be hydrogen or C independently of one another
1-C
20straight or branched alkyl, R
4for methylene radical, R
5for C
1-C
5straight or branched alkyl.
The present invention also provides the luxuriant scandium metal catalysts precursors based on two indenyl ligands being prepared by aforesaid method.
The present invention also provides the application of above-mentioned catalyzer in catalyzed ethylene and cycloolefin copolyreaction.
In addition, the present invention also provides the preparation method of a kind of ethene and cyclic olefine copolymer, the method is included under the existence of above-mentioned luxuriant scandium metal catalysts precursors based on two indenyl ligands and boride, under olefinic polyreaction condition, makes ethene and cycloolefin in organic solvent, carry out copolyreaction.
The catalyzer that contains the described luxuriant scandium metal catalysts precursors based on two indenyl ligands provided by the invention has higher catalytic activity.When this catalyzer is used for to catalyzed ethylene and cycloolefin copolyreaction, catalytic activity can be up to 2.6 × 10
6gmol
-1(cat) h
-1.In addition, the method for the luxuriant scandium metal catalysts precursors based on two indenyl ligands described in preparation provided by the invention is simple, and cost is lower.
Other features and advantages of the present invention are described in detail the embodiment part subsequently.
Brief description of the drawings
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the preparation flow schematic diagram of luxuriant scandium metal catalysts precursors provided by the invention.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
Luxuriant scandium metal catalysts precursors based on two indenyl ligands provided by the invention has the structure shown in formula (I):
formula (I),
Wherein, R
1for C
1-C
20straight or branched alkylidene group, R
2and R
3be hydrogen or C independently of one another
1-C
20straight or branched alkyl, R
4for methylene radical, R
5for C
1-C
5straight or branched alkyl.
Wherein, described C
1-C
20the specific examples of straight or branched alkyl can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 1-ethyl propyl, 2-methyl butyl, 3-methyl butyl, 2, 2-dimethyl propyl, n-hexyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, n-heptyl, 2-methyl hexyl, 3-methyl hexyl, 4-methyl hexyl, 5-methyl hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, 3, 7-dimethyl octyl group, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, Octadecane base, NSC 77136 base and NSC 62789 base.
The present inventor finds under study for action, by specific R
1-R
5while coordinating the luxuriant scandium metal catalysts precursors based on two indenyl ligands that forms as the catalyzer of catalyzed ethylene and cycloolefin copolymerization, can obtain fabulous catalytic effect, therefore, preferably, R
1for ethylidene, R
2and R
3for hydrogen, R
4for methylene radical, R
5for methyl, corresponding luxuriant scandium metal catalysts precursors has the structure shown in formula III; Or, R
1for hexylidene, R
2for the tertiary butyl, R
3for methyl, R
4for methylene radical, R
5for methyl, corresponding luxuriant scandium metal catalysts precursors has the structure shown in formula IV.
The preparation method of the luxuriant scandium metal catalysts precursors based on two indenyl ligands provided by the invention is included under coordination reaction condition, is Sc (R by compound and the general formula with structure shown in formula II
4si (R
5)
3)
3(THF)
2compound in organic solvent, react, obtain having the luxuriant scandium metal catalysts precursors based on two indenyl ligands of structure shown in formula I;
formula II,
Wherein, R
1for C
1-C
20straight or branched alkylidene group, R
2and R
3be hydrogen or C independently of one another
1-C
20straight or branched alkyl, R
4for methylene radical, R
5for C
1-C
5straight or branched alkyl.Detailed process as shown in Figure 1.
Wherein, as mentioned above, described C
1-C
20the specific examples of straight or branched alkyl can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 1-ethyl propyl, 2-methyl butyl, 3-methyl butyl, 2, 2-dimethyl propyl, n-hexyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, n-heptyl, 2-methyl hexyl, 3-methyl hexyl, 4-methyl hexyl, 5-methyl hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, 3, 7-dimethyl octyl group, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, Octadecane base, NSC 77136 base and NSC 62789 base.
According to the present invention, the specific examples with the compound of structure shown in formula II can include but not limited to 1,2-bis-(1H-indenyl-3-replaces) ethane, 1,6-two (the 2-tertiary butyl-1-methyl isophthalic acid H-indenes-3-replaces) hexane, 1,4-bis-(1,2-dimethyl-1H-indenyl-3-replaces) butane and 1, one or more in 4-bis-(1-methyl isophthalic acid H-indenyl-3-replaces) butane, be particularly preferably 1,2-bis-(1H-indenyl-3-replaces) ethane and/or 1,6-two (the 2-tertiary butyl-1-methyl isophthalic acid H-indenes-3-replaces) hexane.
According to the present invention, general formula is Sc (R
4si (R
5)
3)
3(THF)
2the specific examples of compound can include but not limited to Sc (CH
2siMe
3)
3(THF)
2, Sc (CH
2siEt
3)
3(THF)
2, Sc (CH
2siPr
3)
3(THF)
2, Sc (CH
2siBu
3)
3(THF)
2in one or more, be particularly preferably Sc (CH
2siMe
3)
3(THF)
2.
According to the present invention, compound and the general formula with structure shown in formula II are Sc (R
4si (R
5)
3)
3(THF)
2the consumption of compound can in wider scope, select and change, as long as can obtain having the luxuriant scandium metal catalysts precursors based on two indenyl ligands of structure shown in formula I, for example, the compound and the general formula that have a structure shown in formula II are Sc (R
4si (R
5)
3)
3(THF)
2the mol ratio of compound can be 1:1.8-2.2.
The present invention is not particularly limited described coordination reaction condition, and for example, described coordination reaction condition can comprise that temperature of reaction is-20 DEG C to 60 DEG C, and the reaction times is 4-16 hour.Under preferable case, described coordination reaction condition comprises that temperature of reaction is 0-20 DEG C, and the reaction times is 8-16 hour, can more be conducive to like this carrying out of reaction, and improves the yield of product.
According to the present invention, described organic solvent can be the existing various organic substance that can serve as reaction media, for example, can be varsol and/or ether solvent.Described varsol can be C
1-C
5alkane or halogenated alkane, C
5-C
7naphthenic hydrocarbon, aromatic hydrocarbons and isoparaffin in one or more.The specific examples of described varsol can include but not limited to: one or more in normal hexane, Skellysolve A, normal heptane, pentane, methylene dichloride, trichloromethane, hexanaphthene, benzene, toluene, Isosorbide-5-Nitrae-dioxane and tetrahydrofuran (THF).Described ether solvent can be C
4-C
15monoether and/or polyether.The specific examples of described ether solvent can include but not limited to: tert.-butoxy Ethoxyethane and/or tetrahydrofuran (THF).Wherein, these solvents can use separately, also can mix use.The consumption of described organic solvent can be Sc (R according to compound and the general formula with structure shown in formula II
4si (R
5)
3)
3(THF)
2the consumption of compound reasonably select, for example, compound and general formula that the consumption of described solvent can make to have structure shown in formula II are Sc (R
4si (R
5)
3)
3(THF)
2the total concn of compound be 1-30 % by weight, be preferably 5-20 % by weight.
According to the present invention, method provided by the invention is also included in after coordination reaction completes, and described organic solvent is removed.Wherein, the method for removing described organic solvent can adopt the whole bag of tricks well known in the art to carry out, and for example, vacuum line removes organic solvent, revolves to steam and remove organic solvent etc., all can know these those skilled in the art, will repeat no more at this.
In addition, in order to obtain sterling, method provided by the invention can also comprise the step of the product purification obtaining, and the method for described purifying can adopt various purification process well known in the art to carry out, as recrystallization etc.Recrystallization solvent used can be for example normal hexane and/or hexanaphthene.
The present invention also provides the luxuriant scandium metal catalysts precursors based on two indenyl ligands being prepared by aforesaid method.
The present invention also provides the application of above-mentioned catalyzer in catalyzed ethylene and cycloolefin copolyreaction.
In addition, the present invention also provides the preparation method of a kind of ethene and cyclic olefine copolymer, the method is included under the existence of above-mentioned luxuriant scandium metal catalysts precursors based on two indenyl ligands and boride, under olefinic polyreaction condition, makes ethene and cycloolefin in organic solvent, carry out copolyreaction.
According to the present invention, described luxuriant scandium metal catalysts precursors based on two indenyl ligands and the content of boride can be selected and change in wider scope, but in order to make these two kinds of materials can play the effect of concerted catalysis ethene and cycloolefin copolymerization better, under preferable case, described luxuriant scandium metal catalysts precursors based on two indenyl ligands and the mol ratio of boride are 1:0.9-1.1.
According to the present invention, described boride can be the existing various boron-containing compound that can be used as metallocene promotor, for example, can be selected from [Ph
3c] [B (C
6f
5)
4], [PhMe
2nH] [B (C
6f
5)
4] and B (C
6f
5)
3in one or more.Above-mentioned boride can be commercially available, and also can prepare according to existing method, will repeat no more at this.
The preparation method's of described ethene provided by the invention and cyclic olefine copolymer improvements have been to adopt and have contained above-mentioned luxuriant scandium metal catalysts precursors based on two indenyl ligands and the catalyzer of boride, and the kind of described cyclic olefine copolymer and organic solvent and olefinic polyreaction condition etc. all can be same as the prior art.
Particularly, described cyclic olefine copolymer can be existing various C
5-C
20cycloolefin, be particularly preferably norbornylene and/or dicyclopentadiene.
According to the present invention, in preparation method's process of described ethene and cyclic olefine copolymer, described organic solvent can be existing various can be as the organic substance of reaction medium, for example, can be aromatic hydrocarbons, also can be aliphatic hydrocarbon.Particularly, described organic solvent can be selected from one or more in benzene, toluene, normal hexane, hexanaphthene and normal heptane.
According to the present invention, described olefinic polyreaction condition can be that the routine of this area is selected, but in order to overcome oxygen inhibition, obtain having the copolymerization product of larger molecular weight, described olefinic polyreaction preferably carries out in inert atmosphere.Described inert atmosphere refers to not any one gas or the gaseous mixture with reactant and product generation chemical reaction, as one or more in nitrogen and periodic table of elements zero group gas.Keep inert atmosphere method can for to pass in reaction system above-mentioned not with any one gas or the gaseous mixture of reactant and product generation chemical reaction.Described olefinic polyreaction condition also comprises temperature of reaction and reaction times, for example, described temperature of reaction can be-30 DEG C to 80 DEG C, be preferably 0-40 DEG C; The described reaction times can be 5-60 minute, is preferably 10-30 minute.
According to the present invention, after polyreaction completes, the polymers soln obtaining should be contacted with terminator so that active centre inactivation.The consumption of described terminator can reasonably be selected according to the consumption of described catalyzer, and as a rule, the mol ratio of luxuriant scandium metal catalysts precursors described in described terminator and catalyzer can be 0.1-1:1.Described terminator can be the existing various reagent that can make active centre inactivation, for example, can be selected from one or more in water, methyl alcohol, ethanol and Virahol.
Below will describe the present invention by embodiment.
In following examples, the differential scanning calorimeter (DSC) that it is PE DSC-7 purchased from the model of PE company of the U.S. that the fusing point of polymkeric substance adopts is measured, and wherein, test condition comprises that temperature rise rate is 10 DEG C/min.The gel permeation chromatograph (GPC) that it is LC-10AT purchased from the model of Shimadzu company that the weight-average molecular weight of polymkeric substance and molecular weight distribution adopt is measured, and wherein, taking THF as moving phase, taking Narrow distribution polystyrene as standard specimen, probe temperature is 25 DEG C.
Preparation example 1
This preparation example is for illustrating luxuriant scandium metal catalysts precursors based on two indenyl ligands provided by the invention and preparation method thereof.
By 1 of 5.17g (20mmol), 2-bis-(1H-indenyl-3-replaces) ethane (wherein, R
1for ethylidene, R
2and R
3for hydrogen, purchased from Alfa company, lower same) be dissolved in normal hexane solvent, at 20 DEG C, this solution is added to Sc (CH
2siMe
3)
3(THF)
2in the hexane solution of (17.9g, 41mmol), and at 20 DEG C, react 8 hours.After reaction finishes, with vacuum line, solvent is removed, thick product normal hexane recrystallization, obtains the luxuriant scandium metal catalysts precursors Q1 of 8.12g based on two indenyl ligands, and productive rate is 56%.
Results of elemental analyses shows, Anal.Calc.for C
38h
66sc
2si
4: C, 62.94; H, 9.71.Found:C, 62.86; H, 9.69.FD-MS:m/z692.5(calcd692.3)。
Preparation example 2
This preparation example is for illustrating luxuriant scandium metal catalysts precursors based on two indenyl ligands provided by the invention and preparation method thereof.
By 1 of 0.21g (0.81mmol), 2-bis-(1H-indenyl-3-replaces) ethane is dissolved in normal hexane solvent, at 0 DEG C, this solution is added to Sc (CH
2siMe
3)
3(THF)
2in the hexane solution of (0.73g, 1.62mmol), and at 0 DEG C, react 16 hours.After reaction finishes, with vacuum line, solvent is removed, thick product normal hexane recrystallization, obtains the luxuriant scandium metal catalysts precursors Q2 of 0.36g based on two indenyl ligands, and productive rate is 62%.Characterization result is identical with preparation example 1.
Preparation example 3
This preparation example is for illustrating luxuriant scandium metal catalysts precursors based on two indenyl ligands provided by the invention and preparation method thereof.
By 1 of 0.25g (0.96mmol), 2-bis-(1H-indenyl-3-replaces) ethane is dissolved in dichloromethane solvent, at 20 DEG C, this solution is added to Sc (CH
2siMe
3)
3(THF)
2in the dichloromethane solution of (0.86g, 1.92mmol), and at 20 DEG C, react 8 hours.After reaction finishes, with vacuum line, solvent is removed, thick product normal hexane recrystallization, obtains the luxuriant scandium metal catalysts precursors Q3 of 0.38g based on two indenyl ligands, and productive rate is 54%.Characterization result is identical with preparation example 1.
Preparation example 4
This preparation example is for illustrating luxuriant scandium metal catalysts precursors based on two indenyl ligands provided by the invention and preparation method thereof.
By 0.51g(1.12mmol) 1,6-two (the 2-tertiary butyl-1-methyl isophthalic acid H-indenes-3-replaces) hexane (R
1for hexylidene, R
2for the tertiary butyl, R
3for methyl, purchased from Alfa company) be dissolved in normal hexane solvent, at 20 DEG C, this solution is added to Sc (CH
2siMe
3)
3(THF)
2in the hexane solution of (1.01g, 2.24mmol), and at 20 DEG C, react 8 hours.After reaction finishes, with vacuum line, solvent is removed, thick product normal hexane recrystallization, obtains the luxuriant scandium metal catalysts precursors Q4 of 0.48g based on two indenyl ligands, and productive rate is 47%.
Results of elemental analyses shows, Anal.Calc.for C
52h
94sc
2si
4: C, 67.77; H, 10.28.Found:C, 67.57; H, 10.18.FD-MS:920.64。
Embodiment 1
This embodiment is for illustrating the preparation method of ethene provided by the invention and cyclic olefine copolymer.
500mL polymeric kettle after heat drying is vacuumized to twice of logical nitrogen, after vacuumizing again, pass into ethylene gas, then to add successively 2mL concentration be the toluene solution, 70mL of the luxuriant scandium metal catalysts precursors Q1 based on two indenyl ligands of 1 μ mol/mL through the toluene solution of the toluene of anhydrous and oxygen-free processing, norbornylene that 20mL concentration is 2mmol/mL, and finally adding 3mL concentration is the [Ph of 1 μ mol/mL
3c] [B (C
6f
5)
4] toluene solution, and under mechanical stirring, pass into the ethene that pressure is 1atm, and under this pressure in 20 DEG C of reaction 10min, add afterwards ethanol termination reaction, obtain 0.39g polymkeric substance G1, polymerization activity is 1.2 × 10
6gmol
-1(cat) h
-1.
The fusing point that adopts DSC to record polymkeric substance G1 is 103.1 DEG C, and the number-average molecular weight that adopts GPC to record polymkeric substance G1 is 2.9 × 10
5, molecular weight distribution is 2.46.
Embodiment 2
This embodiment is for illustrating the preparation method of ethene provided by the invention and cyclic olefine copolymer.
500mL polymeric kettle after heat drying is vacuumized to twice of logical nitrogen, after vacuumizing again, pass into ethylene gas, then to add successively 2mL concentration be the toluene solution, 70mL of the luxuriant scandium metal catalysts precursors Q2 based on two indenyl ligands of 1 μ mol/mL through the toluene solution of the toluene of anhydrous and oxygen-free processing, norbornylene that 20mL concentration is 2mmol/mL, and finally adding 2mL concentration is the [Ph of 1 μ mol/mL
3c] [B (C
6f
5)
4] toluene solution, and under mechanical stirring, pass into the ethene that pressure is 1atm, and under this pressure in 20 DEG C of reaction 10min, add afterwards ethanol termination reaction, obtain 0.54g polymkeric substance G2, polymerization activity is 1.6 × 10
6gmol
-1(cat) h
-1.
The fusing point that adopts DSC to record polymkeric substance G2 is 108.1 DEG C, and the number-average molecular weight that adopts GPC to record polymkeric substance G1 is 3.6 × 10
5, molecular weight distribution is 2.55.
Embodiment 3
This embodiment is for illustrating the preparation method of ethene provided by the invention and cyclic olefine copolymer.
500mL polymeric kettle after heat drying is vacuumized to twice of logical nitrogen, after vacuumizing again, pass into ethylene gas, then to add successively 4mL concentration be the toluene solution, 70mL of the luxuriant scandium metal catalysts precursors Q3 based on two indenyl ligands of 1 μ mol/mL through the toluene solution of the toluene of anhydrous and oxygen-free processing, norbornylene that 20mL concentration is 2mmol/mL, and finally adding 4mL concentration is the [Ph of 1 μ mol/mL
3c] [B (C
6f
5)
4] toluene solution, and under mechanical stirring, pass into the ethene that pressure is 1atm, and under this pressure in 20 DEG C of reaction 10min, add afterwards ethanol termination reaction, obtain 0.87g polymkeric substance G3, polymerization activity is 1.3 × 10
6gmol
-1(cat) h
-1.
The fusing point that adopts DSC to record polymkeric substance G3 is 102.7 DEG C, and the number-average molecular weight that adopts GPC to record polymkeric substance G3 is 2.8 × 10
5, molecular weight distribution is 2.11.
Embodiment 4
This embodiment is for illustrating the preparation method of ethene provided by the invention and cyclic olefine copolymer.
500mL polymeric kettle after heat drying is vacuumized to twice of logical nitrogen, after vacuumizing again, pass into ethylene gas, then to add successively 2mL concentration be the toluene solution, 70mL of the luxuriant scandium metal catalysts precursors Q2 based on two indenyl ligands of 1 μ mol/mL through the toluene solution of the toluene of anhydrous and oxygen-free processing, norbornylene that 20mL concentration is 2mmol/mL, and finally adding 2mL concentration is the [Ph of 1 μ mol/mL
3c] [B (C
6f
5)
4] toluene solution, and under mechanical stirring, pass into the ethene that pressure is 1atm, and under this pressure in 20 DEG C of reaction 30min, add afterwards ethanol termination reaction, obtain 1.04g polymkeric substance G4, polymerization activity is 1.0 × 10
6gmol
-1(cat) h
-1.
The fusing point that adopts DSC to record polymkeric substance G4 is 110.3 DEG C, and the number-average molecular weight that adopts GPC to record polymkeric substance G4 is 4.7 × 10
5, molecular weight distribution is 2.63.
Embodiment 5
This embodiment is for illustrating the preparation method of ethene provided by the invention and cyclic olefine copolymer.
500mL polymeric kettle after heat drying is vacuumized to twice of logical nitrogen, after vacuumizing again, pass into ethylene gas, then to add successively 2mL concentration be the toluene solution, 70mL of the luxuriant scandium metal catalysts precursors Q2 based on two indenyl ligands of 1 μ mol/mL through the toluene solution of the toluene of anhydrous and oxygen-free processing, norbornylene that 20mL concentration is 2mmol/mL, and finally adding 2mL concentration is the [PhMe of 1 μ mol/mL
2nH] [B (C
6f
5)
4] toluene solution, and under mechanical stirring, pass into the ethene that pressure is 1atm, and under this pressure in 20 DEG C of reaction 10min, add afterwards ethanol termination reaction, obtain 0.28g polymkeric substance G5, polymerization activity is 8.4 × 10
5gmol
-1(Sc) h
-1.
The fusing point that adopts DSC to record polymkeric substance G5 is 105.5 DEG C, and the number-average molecular weight that adopts GPC to record polymkeric substance G5 is 3.8 × 10
5, molecular weight distribution is 2.24.
Embodiment 6
This embodiment is for illustrating the preparation method of ethene provided by the invention and cyclic olefine copolymer.
500mL polymeric kettle after heat drying is vacuumized to twice of logical nitrogen, after vacuumizing again, pass into ethylene gas, then to add successively 2mL concentration be the toluene solution, 70mL of the luxuriant scandium metal catalysts precursors Q2 based on two indenyl ligands of 1 μ mol/mL through the toluene solution of the toluene of anhydrous and oxygen-free processing, norbornylene that 20mL concentration is 2mmol/mL, and finally adding 2mL concentration is the [Ph of 1 μ mol/mL
3c] [B (C
6f
5)
4] toluene solution, and under mechanical stirring, pass into the ethene that pressure is 2atm, and under this pressure in 20 DEG C of reaction 10min, add afterwards ethanol termination reaction, obtain 0.75g polymkeric substance G6, polymerization activity is 2.2 × 10
6gmol
-1(cat) h
-1.
The fusing point that adopts DSC to record polymkeric substance G6 is 113.8 DEG C, and the number-average molecular weight that adopts GPC to record polymkeric substance G6 is 5.2 × 10
5, molecular weight distribution is 2.85.
Embodiment 7
This embodiment is for illustrating the preparation method of ethene provided by the invention and cyclic olefine copolymer.
500mL polymeric kettle after heat drying is vacuumized to twice of logical nitrogen, after vacuumizing again, pass into ethylene gas, then to add successively 2mL concentration be the toluene solution, 70mL of the luxuriant scandium metal catalysts precursors Q2 based on two indenyl ligands of 1 μ mol/mL through the toluene solution of the toluene of anhydrous and oxygen-free processing, norbornylene that 20mL concentration is 2mmol/mL, and finally adding 2mL concentration is the [Ph of 1 μ mol/mL
3c] [B (C
6f
5)
4] toluene solution, and under mechanical stirring, pass into the ethene that pressure is 1atm, and under this pressure in 40 DEG C of reaction 10min, add afterwards ethanol termination reaction, obtain 0.61g polymkeric substance G7, polymerization activity is 1.8 × 10
6gmol
-1(cat) h
-1.
The fusing point that adopts DSC to record polymkeric substance G7 is 100.2 DEG C, and the number-average molecular weight that adopts GPC to record polymkeric substance G7 is 2.6 × 10
5, molecular weight distribution is 2.33.
Embodiment 8
This embodiment is for illustrating the preparation method of ethene provided by the invention and cyclic olefine copolymer.
500mL polymeric kettle after heat drying is vacuumized to twice of logical nitrogen, after vacuumizing again, pass into ethylene gas, then to add successively 2mL concentration be the toluene solution, 60mL of the luxuriant scandium metal catalysts precursors Q2 based on two indenyl ligands of 1 μ mol/mL through the toluene solution of the toluene of anhydrous and oxygen-free processing, norbornylene that 30mL concentration is 2mmol/mL, and finally adding 2mL concentration is the [Ph of 1 μ mol/mL
3c] [B (C
6f
5)
4] toluene solution, and under mechanical stirring, pass into the ethene that pressure is 1atm, and under this pressure in 20 DEG C of reaction 10min, add afterwards ethanol termination reaction, obtain 0.40g polymkeric substance G8, polymerization activity is 1.2 × 10
6gmol
-1(cat) h
-1.
The fusing point that adopts DSC to record polymkeric substance G8 is 99.5 DEG C, and the number-average molecular weight that adopts GPC to record polymkeric substance G8 is 2.2 × 10
5, molecular weight distribution is 2.68.
Embodiment 9
This embodiment is for illustrating the preparation method of ethene provided by the invention and cyclic olefine copolymer.
500mL polymeric kettle after heat drying is vacuumized to twice of logical nitrogen, after vacuumizing again, pass into ethylene gas, then to add successively 2mL concentration be the toluene solution, 60mL of the luxuriant scandium metal catalysts precursors Q2 based on two indenyl ligands of 1 μ mol/mL through the hexane solution of the normal hexane of anhydrous and oxygen-free processing, norbornylene that 20mL concentration is 2mmol/mL, and finally adding 2mL concentration is the [Ph of 1 μ mol/mL
3c] [B (C
6f
5)
4] toluene solution 2mL(1 μ mol/mL), and under mechanical stirring, pass into the ethene that pressure is 1atm, and under this pressure in 20 DEG C of reaction 10min, add afterwards ethanol termination reaction, obtain 0.44g polymkeric substance G9, polymerization activity is 1.3 × 10
6gmol
-1(cat) h
-1.
The fusing point that adopts DSC to record polymkeric substance G9 is 105.8 DEG C, and the number-average molecular weight that adopts GPC to record polymkeric substance G9 is 5.9 × 10
5, molecular weight distribution is 2.99.
Embodiment 10
This embodiment is for illustrating the preparation method of ethene provided by the invention and cyclic olefine copolymer.
500mL polymeric kettle after heat drying is vacuumized to twice of logical nitrogen, after vacuumizing again, pass into ethylene gas, then to add successively 2mL concentration be the toluene solution, 60mL of the luxuriant scandium metal catalysts precursors Q4 based on two indenyl ligands of 1 μ mol/mL through the toluene solution of the toluene of anhydrous and oxygen-free processing, dicyclopentadiene that 20mL concentration is 2mmol/mL, and finally adding 2mL concentration is the [Ph of 1 μ mol/mL
3c] [B (C
6f
5)
4] toluene solution, and under mechanical stirring, pass into the ethene that pressure is 1atm, and under this pressure in 20 DEG C of reaction 10min, add afterwards ethanol termination reaction, obtain 0.85g polymkeric substance G10, polymerization activity is 2.6 × 10
6gmol
-1(cat) h
-1.
The fusing point that adopts DSC to record polymkeric substance G10 is 124.2 DEG C, and the number-average molecular weight that adopts GPC to record polymkeric substance G10 is 5.2 × 10
5, molecular weight distribution is 2.39.
Can find out from the result of above embodiment, the catalyzer that contains the described luxuriant scandium metal catalysts precursors based on two indenyl ligands provided by the invention has higher catalytic activity.In addition, the method for the luxuriant scandium metal catalysts precursors based on two indenyl ligands described in preparation provided by the invention is simple, and cost is lower.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition each the concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode.For fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, also can carry out arbitrary combination between various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (11)
1. the luxuriant scandium metal catalysts precursors based on two indenyl ligands, is characterized in that, described luxuriant scandium metal catalysts precursors has the structure shown in formula (I):
formula (I),
Wherein, R
1for C
1-C
20straight or branched alkylidene group, R
2and R
3be hydrogen or C independently of one another
1-C
20straight or branched alkyl, R
4for methylene radical, R
5for C
1-C
5straight or branched alkyl.
2. luxuriant scandium metal catalysts precursors according to claim 1, wherein,
R
1for ethylidene, R
2and R
3for hydrogen, R
4for methylene radical, R
5for methyl, or,
R
1for hexylidene, R
2for the tertiary butyl, R
3for methyl, R
4for methylene radical, R
5for methyl.
3. a preparation method for the luxuriant scandium metal catalysts precursors based on two indenyl ligands, the method is included under coordination reaction condition, is Sc (R by compound and the general formula with structure shown in formula II
4si (R
5)
3)
3(THF)
2compound in organic solvent, react, obtain having the luxuriant scandium metal catalysts precursors based on two indenyl ligands of structure shown in formula I;
formula II,
Wherein, R
1for C
1-C
20straight or branched alkylidene group, R
2and R
3be hydrogen or C independently of one another
1-C
20straight or branched alkyl, R
4for methylene radical, R
5for C
1-C
5straight or branched alkyl.
4. preparation method according to claim 3, wherein, the compound that has a structure shown in formula II is 1,2-bis-(1H-indenyl-3-replaces) ethane and/or 1,6-two (the 2-tertiary butyl-1-methyl isophthalic acid H-indenes-3-replaces) hexane, general formula is Sc (R
4si (R
5)
3)
3(THF)
2compound be Sc (CH
2siMe
3)
3(THF)
2.
5. according to the preparation method described in claim 3 or 4, wherein, compound and the general formula with structure shown in formula II are Sc (R
4si (R
5)
3)
3(THF)
2the mol ratio of compound be 1:1.8-2.2.
6. according to the preparation method described in claim 3 or 4, wherein, described coordination reaction condition comprises that temperature of reaction is-20 DEG C to 60 DEG C, and the reaction times is 4-16 hour; Preferably, described coordination reaction condition comprises that temperature of reaction is 0-20 DEG C, and the reaction times is 8-16 hour.
7. the luxuriant scandium metal catalysts precursors based on two indenyl ligands being prepared by the method described in any one in claim 3-6.
8. the application of the luxuriant scandium metal catalysts precursors based on two indenyl ligands described in claim 1,2 or 7 in catalyzed ethylene and cycloolefin copolyreaction.
9. the preparation method of an ethene and cyclic olefine copolymer, the method is included under the existence of the luxuriant scandium metal catalysts precursors based on two indenyl ligands described in claim 1,2 or 7 and boride, under olefinic polyreaction condition, makes ethene and cycloolefin in organic solvent, carry out copolyreaction.
10. preparation method according to claim 9, wherein, the mol ratio of described luxuriant scandium metal catalysts precursors and boride is 1:0.9-1.1.
11. according to the preparation method described in claim 9 or 10, and wherein, described boride is selected from [Ph
3c] [B (C
6f
5)
4], [PhMe
2nH] [B (C
6f
5)
4] and B (C
6f
5)
3in one or more.
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| CN109081882A (en) * | 2017-06-13 | 2018-12-25 | 中国石油化工股份有限公司 | Cyclic olefine copolymer and preparation method thereof |
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| CN114891137A (en) * | 2022-06-06 | 2022-08-12 | 中国科学院长春应用化学研究所 | Binuclear four-group metal catalyst for olefin polymerization, and preparation method, composition and application thereof |
| CN115850548A (en) * | 2022-11-30 | 2023-03-28 | 中国化学赛鼎宁波工程有限公司 | Preparation method of cycloolefin copolymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109081882A (en) * | 2017-06-13 | 2018-12-25 | 中国石油化工股份有限公司 | Cyclic olefine copolymer and preparation method thereof |
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| CN113307896A (en) * | 2021-06-09 | 2021-08-27 | 中国科学院长春应用化学研究所 | Binuclear rare earth catalyst and preparation method and application thereof |
| CN114891137A (en) * | 2022-06-06 | 2022-08-12 | 中国科学院长春应用化学研究所 | Binuclear four-group metal catalyst for olefin polymerization, and preparation method, composition and application thereof |
| CN114891137B (en) * | 2022-06-06 | 2024-04-09 | 中国科学院长春应用化学研究所 | Binuclear group IV metal catalyst for olefin polymerization, and preparation method, composition and application thereof |
| CN115850548A (en) * | 2022-11-30 | 2023-03-28 | 中国化学赛鼎宁波工程有限公司 | Preparation method of cycloolefin copolymer |
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