CN104098608B - The preparation method of a kind of luxuriant scandium metal catalysts precursors and its preparation method and application and multipolymer - Google Patents
The preparation method of a kind of luxuriant scandium metal catalysts precursors and its preparation method and application and multipolymer Download PDFInfo
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Abstract
The invention provides the preparation method of a kind of luxuriant scandium metal catalysts precursors and its preparation method and application and a kind of ethene and cyclic olefine copolymer.Described luxuriant scandium metal catalysts precursors has the structure shown in formula (I), wherein, and 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.Catalyzer containing described luxuriant scandium metal catalysts precursors provided by the invention has higher catalytic activity.
formula (I).
Description
Technical field
The present invention relates to a kind of luxuriant scandium metal catalysts precursors based on two indenyl ligand, a kind of preparation method of the luxuriant scandium metal catalysts precursors based on two indenyl ligand, the luxuriant scandium metal catalysts precursors based on two indenyl ligand prepared by the method, the application of above-mentioned luxuriant scandium metal catalysts precursors in catalyzed ethylene and cycloolefin copolymer react and the preparation method of a kind of ethene and cyclic olefine copolymer.
Background technology
Cyclic olefine copolymer (COC) is the polymkeric substance that ethene and cycloolefin copolymer 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, transparency good non-crystalline state amorphous macromolecule polymkeric substance, can be used for engineering thermoplastic material.
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 makes it can compare favourably with glass aspheric lenses, 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 adopting existing method to prepare exists the very high problem of snappiness difference, second-order transition temperature, it is not easy to be processed to goods.In order to improve these shortcomings, and obtaining cheap, that performance is more excellent cyclic olefine copolymer, realizing its large-scale application as engineering materials, deep research must be carried out to the synthesis of cyclic olefine copolymer and application art.Wherein, the catalyzer preparing described cyclic olefine copolymer has become the focus of a research.
Research shows, adopts metallocene catalyst can not only obtain multipolymer (Angew.Chem.Int.Ed.2005,44 with higher ring-type monomer content; 962); but also range of choice (J.Organomet.Chem.2006,691,3114 of cyclic monomer can be expanded; Macromolecules, 2012,45,5397).In addition, research shows, compared with single-metal reforming catalyst, has synergistic bimetallic catalyst and not only can improve polymerization activity, can also improve comonomer ratio in the polymer (PNAS.2006,103,15295).Along with the reach of science, research and develop the prior development direction that the novel catalyzer for cycloolefin copolymer has become 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 ligand, a kind of preparation method of the luxuriant scandium metal catalysts precursors based on two indenyl ligand, the luxuriant scandium metal catalysts precursors based on two indenyl ligand prepared by the method, the application of above-mentioned luxuriant scandium metal catalysts precursors in catalyzed ethylene and cycloolefin copolymer react 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 ligand, 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.
Present invention also offers a kind of preparation method of the luxuriant scandium metal catalysts precursors based on two indenyl ligand, under the method is included in 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 react in organic solvent, obtain having the luxuriant scandium metal catalysts precursors based on two indenyl ligand 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.
Present invention also offers the luxuriant scandium metal catalysts precursors based on two indenyl ligand prepared by aforesaid method.
Present invention also offers the application of above-mentioned catalyzer in catalyzed ethylene and cycloolefin copolymer react.
In addition, present invention also offers the preparation method of a kind of ethene and cyclic olefine copolymer, the method is included in above-mentioned based under the luxuriant scandium metal catalysts precursors of two indenyl ligand and the existence of boride, under olefinic polyreaction condition, make ethene and cycloolefin carry out copolyreaction in organic solvent.
Catalyzer containing the described luxuriant scandium metal catalysts precursors based on two indenyl ligand provided by the invention has higher catalytic activity.This catalyzer is used for catalyzed ethylene and cycloolefin copolymer when reacting, catalytic activity can up to 2.6 × 10
6gmol
-1(cat) h
-1.In addition, simple based on the method for the luxuriant scandium metal catalysts precursors of two indenyl ligand described in preparation provided by the invention, cost is lower.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is 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 described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
Luxuriant scandium metal catalysts precursors based on two indenyl ligand 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-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 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
5coordinate during catalyzer as catalyzed ethylene and cycloolefin copolymer of the luxuriant scandium metal catalysts precursors based on two indenyl ligand that forms and 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.
Under the preparation method of the luxuriant scandium metal catalysts precursors based on two indenyl ligand provided by the invention is included in coordination reaction condition, be Sc (R by compound and the general formula with structure shown in formula II
4si (R
5)
3)
3(THF)
2compound react in organic solvent, obtain having the luxuriant scandium metal catalysts precursors based on two indenyl ligand 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-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 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, two (the 2-tertiary butyl-1-methyl isophthalic acid H-indenes-3-replaces) hexane, 1 of 6-, 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 two (the 2-tertiary butyl-1-methyl isophthalic acid H-indenes-3-replaces) hexane of 1,6-.
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 carry out selecting and changing in wider scope, as long as the luxuriant scandium metal catalysts precursors based on two indenyl ligand with structure shown in formula I can be obtained, such as, 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 can be 1:1.8-2.2.
The present invention is not particularly limited described coordination reaction condition, and such as, described coordination reaction condition can comprise temperature of reaction and be-20 DEG C to 60 DEG C, and the reaction times is 4-16 hour.Under preferable case, it is 0-20 DEG C that described coordination reaction condition comprises temperature of reaction, and the reaction times is 8-16 hour, more can be conducive to the carrying out reacted like this, and improve the yield of product.
According to the present invention, described organic solvent can be existing various can, as the organic substance of reaction media, such as, can be varsol and/or ether solvent.Described varsol can be C
1-C
5alkane or halogenated alkane, C
5-C
7naphthenic hydrocarbon, one or more in aromatic hydrocarbons and isoparaffin.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-butoxyethoxy ethane and/or tetrahydrofuran (THF).Wherein, these solvents can be used alone, also can be used in combination.The consumption of described organic solvent can according to having the compound of structure shown in formula II and general formula is Sc (R
4si (R
5)
3)
3(THF)
2the consumption of compound reasonably select, such as, the consumption of described solvent can make to have the compound of structure shown in formula II and general formula is 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 is removed by described organic solvent.Wherein, the method removing described organic solvent can adopt various method well known in the art to carry out, and such as, vacuum line removes organic solvent, revolves and steam except organic solvent etc., all can know, will repeat no more at this these those skilled in the art.
In addition, in order to obtain sterling, method provided by the invention can also comprise the step of the product purification obtained, 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 such as normal hexane and/or hexanaphthene.
Present invention also offers the luxuriant scandium metal catalysts precursors based on two indenyl ligand prepared by aforesaid method.
Present invention also offers the application of above-mentioned catalyzer in catalyzed ethylene and cycloolefin copolymer react.
In addition, present invention also offers the preparation method of a kind of ethene and cyclic olefine copolymer, the method is included in above-mentioned based under the luxuriant scandium metal catalysts precursors of two indenyl ligand and the existence of boride, under olefinic polyreaction condition, make ethene and cycloolefin carry out copolyreaction in organic solvent.
According to the present invention, the content of the described luxuriant scandium metal catalysts precursors based on two indenyl ligand and boride can carry out selecting and changing in wider scope, but in order to the effect making these two kinds of materials can play concerted catalysis ethene and cycloolefin copolymer better, under preferable case, described is 1:0.9-1.1 based on the luxuriant scandium metal catalysts precursors of two indenyl ligand and the mol ratio of boride.
According to the present invention, described boride can be the existing various boron-containing compound that can be used as metallocene promotor, such as, 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 improvements of the preparation method of described ethene provided by the invention and cyclic olefine copolymer are to have employed containing above-mentioned based on the luxuriant scandium metal catalysts precursors of two indenyl ligand 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 the existing various organic substance that can be used as reaction medium, such as, 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 an inert atmosphere.Described inert atmosphere refer to not with any one gas or the gaseous mixture of reactant and product generation chemical reaction, as one or more in nitrogen and periodic table of elements zero group gas.Keep the method for inert atmosphere can for 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, and such as, described temperature of reaction can be-30 DEG C to 80 DEG C, is 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 completion of the polymerization reaction, the polymers soln obtained should be contacted with terminator make active centre inactivation.The consumption of described terminator can reasonably select according to the consumption of described catalyzer, and as a rule, described in described terminator and catalyzer, the mol ratio of luxuriant scandium metal catalysts precursors can be 0.1-1:1.Described terminator can be the existing various reagent that can make active centre inactivation, such as, can be selected from one or more in water, methyl alcohol, ethanol and Virahol.
Below will be described the present invention by embodiment.
In following examples, the fusing point of polymkeric substance adopts the model of purchased from American PE company to be that the differential scanning calorimeter (DSC) of PEDSC-7 measures, and wherein, it is 10 DEG C/min that test condition comprises temperature rise rate.The weight-average molecular weight of polymkeric substance and molecular weight distribution adopt the model purchased from Shimadzu Corporation to be that the gel permeation chromatograph (GPC) of LC-10AT measures, and wherein, being moving phase with THF, take Narrow distribution polystyrene as standard specimen, and probe temperature is 25 DEG C.
Preparation example 1
This preparation example is for illustration of luxuriant scandium metal catalysts precursors based on two indenyl ligand provided by the invention and preparation method thereof.
By 1,2-bis-(1H-indenyl-3-replaces) ethane (wherein, R of 5.17g (20mmol)
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 react 8 hours at 20 DEG C.After reaction terminates, removed by solvent with vacuum line, thick product normal hexane recrystallization, obtain the luxuriant scandium metal catalysts precursors Q1 of 8.12g based on two indenyl ligand, productive rate is 56%.
Results of elemental analyses shows, Anal.Calc.forC
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 illustration of luxuriant scandium metal catalysts precursors based on two indenyl ligand provided by the invention and preparation method thereof.
1,2-bis-(1H-indenyl-3-replaces) ethane of 0.21g (0.81mmol) 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 react 16 hours at 0 DEG C.After reaction terminates, removed by solvent with vacuum line, thick product normal hexane recrystallization, obtain the luxuriant scandium metal catalysts precursors Q2 of 0.36g based on two indenyl ligand, productive rate is 62%.Characterization result is identical with preparation example 1.
Preparation example 3
This preparation example is for illustration of luxuriant scandium metal catalysts precursors based on two indenyl ligand provided by the invention and preparation method thereof.
1,2-bis-(1H-indenyl-3-replaces) ethane of 0.25g (0.96mmol) 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 react 8 hours at 20 DEG C.After reaction terminates, removed by solvent with vacuum line, thick product normal hexane recrystallization, obtain the luxuriant scandium metal catalysts precursors Q3 of 0.38g based on two indenyl ligand, productive rate is 54%.Characterization result is identical with preparation example 1.
Preparation example 4
This preparation example is for illustration of luxuriant scandium metal catalysts precursors based on two indenyl ligand 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 react 8 hours at 20 DEG C.After reaction terminates, removed by solvent with vacuum line, thick product normal hexane recrystallization, obtain the luxuriant scandium metal catalysts precursors Q4 of 0.48g based on two indenyl ligand, productive rate is 47%.
Results of elemental analyses shows, Anal.Calc.forC
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 illustration of the preparation method of ethene provided by the invention and cyclic olefine copolymer.
500mL polymeric kettle after heat drying is vacuumized logical nitrogen twice, ethylene gas is passed into after vacuumizing again, then add the toluene solution that toluene solution that 2mL concentration is the luxuriant scandium metal catalysts precursors Q1 based on two indenyl ligand of 1 μm of ol/mL, 70mL are the norbornylene of 2mmol/mL through the toluene of anhydrous and oxygen-free process, 20mL concentration successively, finally add [the Ph that 3mL concentration is 1 μm of ol/mL
3c] [B (C
6f
5)
4] toluene solution, and pass into the ethene that pressure is 1atm under mechanical stirring, and at this pressure in 20 DEG C of reaction 10min, add ethanol termination reaction afterwards, obtain 0.39g polymkeric substance G1, polymerization activity is 1.2 × 10
6gmol
-1(cat) h
-1.
The fusing point adopting DSC to record polymkeric substance G1 is 103.1 DEG C, and the number-average molecular weight adopting GPC to record polymkeric substance G1 is 2.9 × 10
5, molecular weight distribution is 2.46.
Embodiment 2
This embodiment is for illustration of the preparation method of ethene provided by the invention and cyclic olefine copolymer.
500mL polymeric kettle after heat drying is vacuumized logical nitrogen twice, ethylene gas is passed into after vacuumizing again, then add the toluene solution that toluene solution that 2mL concentration is the luxuriant scandium metal catalysts precursors Q2 based on two indenyl ligand of 1 μm of ol/mL, 70mL are the norbornylene of 2mmol/mL through the toluene of anhydrous and oxygen-free process, 20mL concentration successively, finally add [the Ph that 2mL concentration is 1 μm of ol/mL
3c] [B (C
6f
5)
4] toluene solution, and pass into the ethene that pressure is 1atm under mechanical stirring, and at this pressure in 20 DEG C of reaction 10min, add ethanol termination reaction afterwards, obtain 0.54g polymkeric substance G2, polymerization activity is 1.6 × 10
6gmol
-1(cat) h
-1.
The fusing point adopting DSC to record polymkeric substance G2 is 108.1 DEG C, and the number-average molecular weight adopting GPC to record polymkeric substance G1 is 3.6 × 10
5, molecular weight distribution is 2.55.
Embodiment 3
This embodiment is for illustration of the preparation method of ethene provided by the invention and cyclic olefine copolymer.
500mL polymeric kettle after heat drying is vacuumized logical nitrogen twice, ethylene gas is passed into after vacuumizing again, then add the toluene solution that toluene solution that 4mL concentration is the luxuriant scandium metal catalysts precursors Q3 based on two indenyl ligand of 1 μm of ol/mL, 70mL are the norbornylene of 2mmol/mL through the toluene of anhydrous and oxygen-free process, 20mL concentration successively, finally add [the Ph that 4mL concentration is 1 μm of ol/mL
3c] [B (C
6f
5)
4] toluene solution, and pass into the ethene that pressure is 1atm under mechanical stirring, and at this pressure in 20 DEG C of reaction 10min, add ethanol termination reaction afterwards, obtain 0.87g polymkeric substance G3, polymerization activity is 1.3 × 10
6gmol
-1(cat) h
-1.
The fusing point adopting DSC to record polymkeric substance G3 is 102.7 DEG C, and the number-average molecular weight adopting GPC to record polymkeric substance G3 is 2.8 × 10
5, molecular weight distribution is 2.11.
Embodiment 4
This embodiment is for illustration of the preparation method of ethene provided by the invention and cyclic olefine copolymer.
500mL polymeric kettle after heat drying is vacuumized logical nitrogen twice, ethylene gas is passed into after vacuumizing again, then add the toluene solution that toluene solution that 2mL concentration is the luxuriant scandium metal catalysts precursors Q2 based on two indenyl ligand of 1 μm of ol/mL, 70mL are the norbornylene of 2mmol/mL through the toluene of anhydrous and oxygen-free process, 20mL concentration successively, finally add [the Ph that 2mL concentration is 1 μm of ol/mL
3c] [B (C
6f
5)
4] toluene solution, and pass into the ethene that pressure is 1atm under mechanical stirring, and at this pressure in 20 DEG C of reaction 30min, add ethanol termination reaction afterwards, obtain 1.04g polymkeric substance G4, polymerization activity is 1.0 × 10
6gmol
-1(cat) h
-1.
The fusing point adopting DSC to record polymkeric substance G4 is 110.3 DEG C, and the number-average molecular weight adopting GPC to record polymkeric substance G4 is 4.7 × 10
5, molecular weight distribution is 2.63.
Embodiment 5
This embodiment is for illustration of the preparation method of ethene provided by the invention and cyclic olefine copolymer.
500mL polymeric kettle after heat drying is vacuumized logical nitrogen twice, ethylene gas is passed into after vacuumizing again, then add the toluene solution that toluene solution that 2mL concentration is the luxuriant scandium metal catalysts precursors Q2 based on two indenyl ligand of 1 μm of ol/mL, 70mL are the norbornylene of 2mmol/mL through the toluene of anhydrous and oxygen-free process, 20mL concentration successively, finally add [the PhMe that 2mL concentration is 1 μm of ol/mL
2nH] [B (C
6f
5)
4] toluene solution, and pass into the ethene that pressure is 1atm under mechanical stirring, and at this pressure in 20 DEG C of reaction 10min, add ethanol termination reaction afterwards, obtain 0.28g polymkeric substance G5, polymerization activity is 8.4 × 10
5gmol
-1(Sc) h
-1.
The fusing point adopting DSC to record polymkeric substance G5 is 105.5 DEG C, and the number-average molecular weight adopting GPC to record polymkeric substance G5 is 3.8 × 10
5, molecular weight distribution is 2.24.
Embodiment 6
This embodiment is for illustration of the preparation method of ethene provided by the invention and cyclic olefine copolymer.
500mL polymeric kettle after heat drying is vacuumized logical nitrogen twice, ethylene gas is passed into after vacuumizing again, then add the toluene solution that toluene solution that 2mL concentration is the luxuriant scandium metal catalysts precursors Q2 based on two indenyl ligand of 1 μm of ol/mL, 70mL are the norbornylene of 2mmol/mL through the toluene of anhydrous and oxygen-free process, 20mL concentration successively, finally add [the Ph that 2mL concentration is 1 μm of ol/mL
3c] [B (C
6f
5)
4] toluene solution, and pass into the ethene that pressure is 2atm under mechanical stirring, and at this pressure in 20 DEG C of reaction 10min, add ethanol termination reaction afterwards, obtain 0.75g polymkeric substance G6, polymerization activity is 2.2 × 10
6gmol
-1(cat) h
-1.
The fusing point adopting DSC to record polymkeric substance G6 is 113.8 DEG C, and the number-average molecular weight adopting GPC to record polymkeric substance G6 is 5.2 × 10
5, molecular weight distribution is 2.85.
Embodiment 7
This embodiment is for illustration of the preparation method of ethene provided by the invention and cyclic olefine copolymer.
500mL polymeric kettle after heat drying is vacuumized logical nitrogen twice, ethylene gas is passed into after vacuumizing again, then add the toluene solution that toluene solution that 2mL concentration is the luxuriant scandium metal catalysts precursors Q2 based on two indenyl ligand of 1 μm of ol/mL, 70mL are the norbornylene of 2mmol/mL through the toluene of anhydrous and oxygen-free process, 20mL concentration successively, finally add [the Ph that 2mL concentration is 1 μm of ol/mL
3c] [B (C
6f
5)
4] toluene solution, and pass into the ethene that pressure is 1atm under mechanical stirring, and at this pressure in 40 DEG C of reaction 10min, add ethanol termination reaction afterwards, obtain 0.61g polymkeric substance G7, polymerization activity is 1.8 × 10
6gmol
-1(cat) h
-1.
The fusing point adopting DSC to record polymkeric substance G7 is 100.2 DEG C, and the number-average molecular weight adopting GPC to record polymkeric substance G7 is 2.6 × 10
5, molecular weight distribution is 2.33.
Embodiment 8
This embodiment is for illustration of the preparation method of ethene provided by the invention and cyclic olefine copolymer.
500mL polymeric kettle after heat drying is vacuumized logical nitrogen twice, ethylene gas is passed into after vacuumizing again, then add the toluene solution that toluene solution that 2mL concentration is the luxuriant scandium metal catalysts precursors Q2 based on two indenyl ligand of 1 μm of ol/mL, 60mL are the norbornylene of 2mmol/mL through the toluene of anhydrous and oxygen-free process, 30mL concentration successively, finally add [the Ph that 2mL concentration is 1 μm of ol/mL
3c] [B (C
6f
5)
4] toluene solution, and pass into the ethene that pressure is 1atm under mechanical stirring, and at this pressure in 20 DEG C of reaction 10min, add ethanol termination reaction afterwards, obtain 0.40g polymkeric substance G8, polymerization activity is 1.2 × 10
6gmol
-1(cat) h
-1.
The fusing point adopting DSC to record polymkeric substance G8 is 99.5 DEG C, and the number-average molecular weight adopting GPC to record polymkeric substance G8 is 2.2 × 10
5, molecular weight distribution is 2.68.
Embodiment 9
This embodiment is for illustration of the preparation method of ethene provided by the invention and cyclic olefine copolymer.
500mL polymeric kettle after heat drying is vacuumized logical nitrogen twice, ethylene gas is passed into after vacuumizing again, then add the hexane solution that toluene solution that 2mL concentration is the luxuriant scandium metal catalysts precursors Q2 based on two indenyl ligand of 1 μm of ol/mL, 60mL are the norbornylene of 2mmol/mL through the normal hexane of anhydrous and oxygen-free process, 20mL concentration successively, finally add [the Ph that 2mL concentration is 1 μm of ol/mL
3c] [B (C
6f
5)
4] toluene solution 2mL(1 μm ol/mL), and pass into the ethene that pressure is 1atm under mechanical stirring, and at this pressure in 20 DEG C of reaction 10min, add ethanol termination reaction afterwards, obtain 0.44g polymkeric substance G9, polymerization activity is 1.3 × 10
6gmol
-1(cat) h
-1.
The fusing point adopting DSC to record polymkeric substance G9 is 105.8 DEG C, and the number-average molecular weight adopting GPC to record polymkeric substance G9 is 5.9 × 10
5, molecular weight distribution is 2.99.
Embodiment 10
This embodiment is for illustration of the preparation method of ethene provided by the invention and cyclic olefine copolymer.
500mL polymeric kettle after heat drying is vacuumized logical nitrogen twice, ethylene gas is passed into after vacuumizing again, then add the toluene solution that toluene solution that 2mL concentration is the luxuriant scandium metal catalysts precursors Q4 based on two indenyl ligand of 1 μm of ol/mL, 60mL are the dicyclopentadiene of 2mmol/mL through the toluene of anhydrous and oxygen-free process, 20mL concentration successively, finally add [the Ph that 2mL concentration is 1 μm of ol/mL
3c] [B (C
6f
5)
4] toluene solution, and pass into the ethene that pressure is 1atm under mechanical stirring, and at this pressure in 20 DEG C of reaction 10min, add ethanol termination reaction afterwards, obtain 0.85g polymkeric substance G10, polymerization activity is 2.6 × 10
6gmol
-1(cat) h
-1.
The fusing point adopting DSC to record polymkeric substance G10 is 124.2 DEG C, and the number-average molecular weight adopting GPC to record polymkeric substance G10 is 5.2 × 10
5, molecular weight distribution is 2.39.
As can be seen from the result of above embodiment, the catalyzer containing the described luxuriant scandium metal catalysts precursors based on two indenyl ligand provided by the invention has higher catalytic activity.In addition, simple based on the method for the luxuriant scandium metal catalysts precursors of two indenyl ligand described in preparation provided by the invention, 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 characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different 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. based on a luxuriant scandium metal catalysts precursors for two indenyl ligand, it is characterized in that, described luxuriant scandium metal catalysts precursors has the structure shown in 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., based on a preparation method for the luxuriant scandium metal catalysts precursors of two indenyl ligand, under the method is included in coordination reaction condition, be Sc (R by compound and the general formula with structure shown in formula II
4si (R
5)
3)
3(THF)
2compound react in organic solvent, be there is the luxuriant scandium metal catalysts precursors based on two indenyl ligand of structure shown in formula I as claimed in claim 1;
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 with structure shown in formula II is 1,2-bis-(1H-indenyl-3-replaces) ethane and/or 1, two (the 2-tertiary butyl-1-methyl isophthalic acid H-indenes-3-replaces) hexane of 6-, general formula is Sc (R
4si (R
5)
3)
3(THF)
2compound be Sc (CH
2siMe
3)
3(THF)
2.
5. the preparation method according to 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. the preparation method according to claim 3 or 4, wherein, described coordination reaction condition comprises temperature of reaction and is-20 DEG C to 60 DEG C, and the reaction times is 4-16 hour.
7. preparation method according to claim 6, wherein, it is 0-20 DEG C that described coordination reaction condition comprises temperature of reaction, and the reaction times is 8-16 hour.
8. the application of luxuriant scandium metal catalysts precursors in catalyzed ethylene and cycloolefin copolymer react based on two indenyl ligand described in claim 1 or 2.
9. the preparation method of an ethene and cyclic olefine copolymer, the method be included in described in claim 1 or 2 based under the luxuriant scandium metal catalysts precursors of two indenyl ligand and the existence of boride, under olefinic polyreaction condition, make ethene and cycloolefin carry out copolyreaction in organic solvent.
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. preparation methods according to claim 9 or 10, 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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| JP2008266523A (en) * | 2007-04-24 | 2008-11-06 | Institute Of Physical & Chemical Research | Method for producing cyclic olefin addition polymer using metallocene complex |
| CN101443343A (en) * | 2006-05-09 | 2009-05-27 | 独立行政法人理化学研究所 | Metallocene complex and polymerization catalyst composition containing the same |
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| JP2008266523A (en) * | 2007-04-24 | 2008-11-06 | Institute Of Physical & Chemical Research | Method for producing cyclic olefin addition polymer using metallocene complex |
| CN101220060A (en) * | 2008-01-23 | 2008-07-16 | 中国科学院上海有机化学研究所 | Single-indenyl rareearth complexes, synthesizing method and application thereof |
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