CN104140451B - Rare earth compounding and preparation method thereof and catalyst and its application and the preparation method of rare-earth isoprene rubber - Google Patents
Rare earth compounding and preparation method thereof and catalyst and its application and the preparation method of rare-earth isoprene rubber Download PDFInfo
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Abstract
The invention discloses rare earth compounding and preparation method thereof, rare earth catalyst and application, and the preparation method of rare-earth isoprene rubber.Described rare earth compounding has the structure shown in formula (I), wherein, R1、R2、R3, and R4It is each independently hydrogen or C1‑C20Alkyl；Ln is the one in rare earth metal, and THF represents oxolane, and Me represents methyl.Suitable 1,4 structural contents of the rare-earth isoprene rubber that the described rare earth catalyst that the present invention provides prepares are high.
Description
Technical field
The present invention relates to a kind of rare earth compounding and preparation method thereof, the catalyst containing this rare earth compounding, this catalyst
Application in conjugate diene polymerization and the preparation method of rare-earth isoprene rubber.
Background technology
Since China's sixties in last century finds that rare earth compounding can be catalyzed diolefin polymerization, in the world to rare earth metal
The research of organic compound catalytic polymerization has made great progress, and develops series of rare earth catalyst system and catalyzing, such as Neodymium chloride/alkyl
Aluminum binary system, carboxylic acid neodymium/alkyl aluminum/halogenide ternary system and carboxylic acid neodymium/alkyl aluminum/alkyl halide/isoprene
Quaternary catalytic system.The high-cis polybutadiene synthesized with this type of rare earth catalyst and polyisoprene rubber have become industrialization
The important kind produced.
In recent years, some are luxuriant, half luxuriant and non-cyclopentadienyl cationic catalyzing of rare-earth metal system becomes again study hotspot.This kind of urge
Agent, by changing the part of coordination compound, limits its geometric configuration, can improve efficiency and the selectivity of catalyst, it is achieved conjugation
Diene polymerization or the combined polymerization with monoolefine.Rare earth metallocene/alkyl aluminum/organic boron salt such as Riken research worker application
Conjugated alkene is all polymerized and has the highest catalysis activity with the combined polymerization containing halogen alkene by cationic catalysts system, and is polymerized
Reacting the feature of active polymerization, particular content can be found in US2002/0119889, US6,596, and 828, US6,960,631B2,
US6,683,140B2, but these technology are when carrying out the polymerization of isoprene, will obtain the cis-Isosorbide-5-Nitrae higher than more than 95% and select
Property, it is necessary to carrying out under the polymerization temperature less than-20 DEG C, operating condition is harsh.
Chinese Academy of Sciences Changchun should change institute Cui east prunus mume (sieb.) sieb.et zucc. disclose in CN101186663A a kind of NCN clamp type rareearth complexes and
Three component cationic catalyst system and catalyzings of alkyl aluminum, organic boron salt composition, are catalyzed isoprene polymerization in the range of-20 to 80 DEG C
Time, in polymer, cis-Isosorbide-5-Nitrae structural content is 55.0-98.8%；During Butadiene Polymerization, cis-Isosorbide-5-Nitrae structural content in polymer
For 90.1-99.9%.
Summary of the invention
It is an object of the invention on the basis of existing technology, it is provided that a kind of new rare earth compounding and preparation method thereof,
There is the selective rare earth catalyst in high cis-1,4, above-mentioned rare earth catalyst when carrying out isoprene polymerization at common alkadienes
Application during polymerization and the preparation method of a kind of rare-earth isoprene rubber.
The present invention provides a kind of rare earth compounding, and described rare earth compounding has a structure shown in formula (I):
Wherein, R1、R2、R3And R4It is each independently hydrogen or C1-C20Alkyl；Ln is the one in rare earth metal, THF generation
Table oxolane, Me represents methyl.
The present invention also provides for the preparation method of a kind of rare earth compounding, and the method is included in and generates structure shown in formula I
Under conditions of rare earth compounding, it is Ln (CH by there is the compound of structure shown in formula II with formula2SiMe3)3(THF)2Change
Compound contacts in organic solvent,
Wherein, R1、R2、R3And R4It is each independently hydrogen or C1-C20Alkyl；Ln is the one in rare earth metal, THF generation
Table oxolane, Me represents methyl.
Present invention also offers the rare earth compounding prepared by said method.
Present invention also offers a kind of for rare earth catalyst, wherein, described catalyst contain above-mentioned rare earth compounding and
Boride.
Present invention also offers the application in conjugate diene polymerization of the above-mentioned rare earth catalyst.
Present invention also offers the preparation method of a kind of rare-earth isoprene rubber, the method includes: in the existence of organic solvent
Descending and under the conditions of solution polymerization, contacted with rare earth catalyst by isoprene, wherein, described rare earth catalyst is the present invention
The above-mentioned rare earth catalyst provided.
The rare earth catalyst containing described rare earth compounding that the present invention provides, when isoprene polymerization, is preferable to carry out
Cis-1,4 structural contents obtaining rare-earth isoprene rubber in mode may be up to more than 99.6%.
Detailed description of the invention
The rare earth compounding that the present invention provides, described rare earth compounding has a structure shown in formula (I):
Wherein, R1、R2、R3And R4It is each independently hydrogen or C1-C20Alkyl；Ln is the one in rare earth metal, THF generation
Table oxolane, Me represents methyl.
Wherein, described C1-C20Alkyl can be straight or branched, and instantiation can include but not limited to: methyl, second
Base, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, 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-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, n-octadecane base, positive 19
Alkyl and AI3-28404 base.Described C1-C5The instantiation of straight or branched alkyl can include but not limited to: methyl, second
Base, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl and neopentyl.
The present inventor finds under study for action, by specific R1-R4Coordinate the rare earth compounding formed as catalysis
Fabulous catalytic effect can be obtained during the catalytic component of isoprene polymerization, it is therefore preferred that R1、R2、R3And R4The most solely
It is on the spot hydrogen or C1-C4Alkyl；It is further preferred that R1、R2、R3And R4Identical, further preferably R1、R2、R3And R4It is
Methyl or be isopropyl.
The present inventor finds under study for action, and the rare earth compounding being made up of specific rare earth is as catalysis isoamyl
Fabulous catalytic effect can be obtained during the catalyst of diene polymerization, it is therefore preferred that rare earth metal Ln is Sc or Lu or Y, enter one
Walking preferred rare earth metal is Sc or Lu.
The preparation method of the rare earth compounding that the present invention provides is included in and generates the rare earth compounding of structure shown in formula I
Under the conditions of, it is Ln (CH by there is the compound of structure shown in formula II with formula2SiMe3)3(THF)2Compound organic molten
Agent contacts,
Wherein, R1、R2、R3And R4Independently be hydrogen or C1-C20Alkyl；Ln is the one in rare earth metal, and THF represents four
Hydrogen furan, Me represents methyl.
Wherein, as it has been described above, described C1-C20Alkyl can be straight or branched, instantiation can include but not limit
In: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, 1-ethyl propyl, 2-first
Base butyl, 3-methyl butyl, 2,2-dimethyl propyl, n-hexyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, positive heptan
Base, 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, n-octadecane
Base, AI3-36122 base and AI3-28404 base.Described C1-C5The instantiation of straight or branched alkyl can include but not limited to:
Methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl and new
Amyl group.
The present inventor finds under study for action, by specific R1-R4Coordinate the rare earth compounding formed as catalysis
Fabulous catalytic effect can be obtained during the catalyst of isoprene polymerization, it is therefore preferred that R1、R2、R3And R4Independently of one another
For hydrogen or C1-C4Alkyl；It is further preferred that R1、R2、R3And R4Identical, further preferably R1、R2、R3And R4It is methyl
Or it is isopropyl.
According to the present invention, the instantiation of the compound with structure shown in formula II can include but not limited to: 1,8-
(N-2,6-dimethyl) di-imidogen carbazole, 1,8-(N-2,6-diisopropyl) di-imidogen carbazole.Aforementioned substances all can be passed through
It is commercially available.
According to the present invention, formula is Ln (CH2SiMe3)3(THF)2The instantiation of compound can include but do not limit
In: Lu (CH2SiMe3)3(THF)2、Sc(CH2SiMe3)3(THF)2Y(CH2SiMe3)3(THF)2In at least one.Aforementioned substances
All can be commercially available or the method synthesis of common knowledge obtains.Such as, Ln (CH2SiMe3)3(THF)2Can be according to literary composition
Offer Journal of Polymer Science:Part A:Polymer Chemistry DOI10.1002/POLA1376 page public
The method synthesis opened.
According to the present invention, there is compound and the Ln (CH of structure shown in formula II2SiMe3)3(THF)2Compound amount
Can select in wider scope and change, as long as can obtain there is the rare earth compounding of structure shown in formula I i.e.
Can, such as, there is compound and the Ln (CH of structure shown in formula II2SiMe3)3(THF)2The mol ratio of compound can be
1:0.5-1.5, preferably 1:0.75-1.25.
The present inventor finds under study for action, and the rare earth compounding being made up of specific rare earth is as catalysis isoamyl
Fabulous catalytic effect can be obtained during the catalyst of diene polymerization, it is therefore preferred that rare earth metal Ln is Sc or Lu or Y, enter one
Walking preferred rare earth metal is Sc or Lu.
The condition of the rare earth compounding of structure shown in described generation formula I is not particularly limited by the present invention, Ke Yiwei
The conventional selection of this area.As a rule, shown in described generation formula I, the condition of the rare earth compounding of structure includes reaction temperature
And the response time.Wherein, described reaction temperature can select in wider scope and change, in order to be more beneficial for reaction
Carrying out, described reaction temperature can be-20 DEG C to 60 DEG C, be preferably 0-20 DEG C.The prolongation in response time is conducive to reactant
Conversion ratio or the raising of yield of product, but the response time long conversion ratio to reactant or the receipts of product
The increase rate of rate is the most inconspicuous, and therefore, generally, the described response time can be 4-16 hour, it is little to be preferably 8-16
Time.
According to the preparation method of the rare earth compounding that the present invention provides, the described organic solvent for preparing rare earth compounding
Can be existing various can be as the organic substance of reaction media, for example, it is possible to be varsol and/or ether solvent.
Described varsol can be C1-C5Alkane or halogenated alkane, C5-C7Cycloalkane, aromatic hydrocarbons and isoparaffin in one or
Multiple.The instantiation of described varsol can include but not limited to: normal hexane, pentane, normal heptane, pentane, dichloromethane
One or more in alkane, chloroform, hexamethylene, benzene, toluene, 1,4-dioxane and oxolane.Described ether solvent
Can be C4-C15Monoether and/or polyether.The instantiation of described ether solvent can include but not limited to: tert-butoxy second
Epoxide ethane and/or oxolane.Wherein, these solvents can be used alone, can also be used in mixed way.Described organic solvent
Consumption can be Ln (CH according to there is the compound of structure shown in formula II with formula2SiMe3)3(THF)2Compound
Consumption reasonably selects, and such as, the consumption of described solvent is so that have the compound of structure shown in formula II with logical
Formula is Ln (CH2SiMe3)3(THF)2The total concentration of compound be 1-30 weight %, preferably 5-20 weight %.
According to the present invention, the method that the present invention provides is additionally included in after above-mentioned reaction completes, and is gone by described organic solvent
Remove.Wherein, the method removing described organic solvent can use various method well known in the art to carry out, and such as, vacuum line removes
Organic solvent, rotation are evaporated off organic solvent etc., and to this, those skilled in the art all can know, will not be described in great detail at this.
Additionally, in order to obtain sterling, the method that the present invention provides can also include the step of the product purification obtained, institute
The method stating purification can use various purification process well known in the art to carry out, such as recrystallization etc..Solvent used by recrystallization
Can be such as normal hexane and/or hexamethylene.
Present invention also offers the rare earth compounding prepared by said method.
The rare earth catalyst that the present invention provides, this catalyst contains boride and rare earth compounding, and wherein, described rare earth is joined
The above-mentioned rare earth compounding that compound provides for the present invention.
According to the present invention, described rare earth compounding can select with the content of boride in wider scope and become
Dynamic, but so that both materials can play preferably is catalyzed conjugate diene polymerization, under preferable case, described rare earth is joined
Compound can be 1:0.9-1.1, preferably 1:0.95-1.05 with the mol ratio of boride.
According to the present invention, described boride can be the existing various boracic chemical combination that can act as metallocene promoter
Thing, for example, it is possible to selected from [Ph3C][B(C6F5)4]、[PhMe2NH][B(C6F5)4] and B (C6F5)3In one or more.Above
Material all can be commercially available.
According to the present invention, wherein, described catalyst is possibly together with alkyl aluminum and/or alkyl aluminium hydride.
Heretofore described alkyl aluminum and/or alkyl aluminium hydride refer to alkyl aluminum, alkyl aluminium hydride or their mixing
Thing.The most described alkyl aluminum and/or alkyl aluminium hydride are trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, three amyl groups
One or more in aluminum, three hexyl aluminum, diethyl aluminium hydride and hydrogenation dibutyl aluminum；It is preferably tri-butyl aluminum and/or hydrogenation
Dibutyl aluminum.Heretofore described alkyl aluminum and/or alkyl aluminium hydride refer to alkyl aluminum, alkyl aluminium hydride or their mixing
Thing.
Can be in wider scope according to the present invention, described alkyl aluminum and/or alkyl aluminium hydride and rare earth compounding content
Inside select and change, but in order to preferably be catalyzed conjugate diene polymerization, described alkyl aluminum and/or alkyl aluminium hydride are with dilute
The mol ratio of soil coordination compound can be 10-50:1, preferably 15-45::1.Above material all can be commercially available.
The invention provides the rare earth catalyst of the present invention application in conjugate diene polymerization.
When the catalyst of the present invention uses as the catalyst during conjugate diene polymerization, generally relative to every mole
Conjugated diene, usage amount is 1 × 10-6-4×10-4Mol rare earth metal, preferably 1.5 × 10-6-3.5×10-4Mol rare earth gold
Belong to.The excessive cost that not only increases of catalyst amount, but also content of ashes in polymer product may be made to increase.Institute in the present invention
State ash and refer to undecomposable component in polymerizate.
When the catalyst of the present invention is applied to conjugate diene polymerization, the method for described conjugate diene polymerization is referred to
Prior art is carried out, and generally comprises: in the presence of the catalyst of the invention, carries out conjugated diene in inert organic solvents
Polymerisation in solution, or enter under conditions of there is no described inert organic solvents or containing inert organic solvents described in very small amount
The polymerisation in bulk of row conjugated diene, this equal can be known, not repeat them here by those skilled in the art.
In described conjugated diene solution polymerization process, the organic solvent used is not particularly limited, can be selected for this
The normally used aliphatic saturated hydrocarbon inert to reactive component in field and/or alicyclic, such as, can be C5-C10Straight chain alkane
Hydrocarbon and/or C5-C10Cycloalkane, typical organic solvent include but not limited to hexane, hexamethylene, heptane, pentane, isopentane,
One or more in octane, hexahydrotoluene, benzene,toluene,xylene and isopropylbenzene.According to the present invention, described conjugated diene
The organic solvent used in hydrocarbon solution polymerization process can organic molten used in the rare earth compounding preparation process with the present invention
Agent is identical or different.
During described conjugate diene polymerization, described conjugated diene can be conjugated diene commonly used in the art
Hydrocarbon, includes but not limited to C4-C6Conjugated diene, can be such as butadiene, isoprene, 1,3-pentadiene, 1,3-oneself two
Alkene, 2, one or more in 3-dimethyl butadiene, preferably butadiene and/or isoprene.
During described conjugate diene polymerization, the condition of described polymerization is referred to prior art and carries out, preferably feelings
Under condition, the condition of described polymerization includes: the temperature of polymerization is subzero 30 DEG C to 80 DEG C above freezing, the most subzero 20 DEG C extremely above freezing 70
DEG C, the most subzero 10 DEG C to 60 DEG C above freezing；The time of polymerization is 20-300 minute, preferably 30-120 minute.
As it was previously stated, during described conjugate diene polymerization, catalyst amount is generally being total to relative to every mole
Yoke alkadienes, usage amount is 1 × 10-6-4×10-4MolNd, preferably 1.5 × 10-6-3.5×10-4molNd。
During described conjugate diene polymerization, can use terminator commonly used in the art that living polymer is directly entered
Row terminate, described terminator can be such as water and/or alcoholic solvent, preferably water, methanol, ethanol, positive isopropanol, isopropanol and
One or more in 2,6-di-tert-butyl hydroquinone's methanol.
Additionally, present invention also offers the preparation method of a kind of rare-earth isoprene rubber, the method includes: at organic solvent
In the presence of and solution polymerization under the conditions of, isoprene is contacted with rare earth catalyst, wherein, described rare earth catalyst is
The above-mentioned rare earth catalyst that invention provides.
The theing improvement is that of preparation method of institute's rare-earth isoprene rubber that the present invention provides have employed containing above-mentioned rare earth
The rare earth catalyst of coordination compound, and it is used for kind and the solution polymerization condition etc. of the organic solvent of isoprene polymerization
All can be same as the prior art.
According to the present invention, described solution polymerization condition can be the conventional selection of this area, but in order to be had
The content of higher cis-Isosorbide-5-Nitrae, described solution polymerization condition may include that temperature is 10-30 DEG C, and pressure is 0.15-
0.7MPa, the time is 20-300 minute；Isoprene is 1:1 × 10 with the mol ratio of rare earth compounding-6-1×10-4, preferably temperature
Degree is for 15-25 DEG C, and pressure is 0.20-0.65MPa, and the time is 25-250 minute；Isoprene and the mol ratio of rare earth compounding
For 1:1.5 × 10-6-1.5×10-4。
Describe the present invention below by specific embodiment, but the scope of the present invention is not limited to these enforcement
Example.
If not otherwise specified, the chemical reagent used in embodiment is chemically pure reagent.
In the present invention, during the microstructure of the conjugated diene polymer of synthesis uses Germany Bruker Tensor27
Infrared spectrometer and Germany's Bruker400MHz nmr determination, solvent is deuterochloroform；Molecular weight and molecualr weight distribution
Using Shimadzu LC-10AT type chromatograph of gel permeation (GPC) to measure, THF is flowing phase, and Narrow distribution polystyrene is standard specimen, temperature
Degree is 25 DEG C.
In the present invention, the solvent used in preparation process and conjugated diene all process through nitrogen deoxygenation, and aqueous solvent
Value is less than 10ppm.
In the present invention, solvent water number refers to by weight, the water content in solvent.
In the present invention, monomer concentration refers to conjugated diene monomer mass concentration in polymerization system.
In the present invention, monomer conversion is referred to initial monomer and is converted into the percentage ratio of polymer by polyreaction, its
The generally weight of straight polymer and the ratio entering the monomer weight being polymerized workshop section.In the present invention, the weight of straight polymer is poly-
The weight of polymer solution and the product of polymer concentration, wherein, the weight of polymer solution refers to not add the poly-of terminator
The weight of polymer solution, polymer concentration refers to the percentage by weight that straight polymer is shared in a polymer solution.
In following example, the microstructure of polymer uses Germany's Bruker400MHz nuclear magnetic resonance analyser to be measured,
Solvent is deuterochloroform；The weight average molecular weight of polymer and molecular weight distribution use the model purchased from Shimadzu Corporation to be LC-10AT
Chromatograph of gel permeation (GPC) be measured, wherein, with THF for flowing phase, with Narrow distribution polystyrene as standard specimen, test
Temperature is 25 DEG C.
Preparation example 1
Rare earth compounding that this preparation example provides for the present invention is described and preparation method thereof.
At 20 DEG C, will be dissolved with 12.87g(0.03mol) 1,8-(N-2,6-dimethyl) di-imidogen carbazole (Guangzhou in
Science and Technology Ltd. produce) oxolane 150mL be added dropwise to 370mL dissolved with 17.41g (0.03mol) Lu
(CH2SiMe3)3(THF)2Tetrahydrofuran solution, and at 20 DEG C react 12 hours.Vacuum drains oxolane, obtains oily
Residue, adds toluene in oily residue, is filtered to remove insoluble matter, obtains rare earth compounding Q1.
Analysis result shows:
FD-Mass:m/z:919.4 (calcd:919.4)
Elementary analysis: measured value C:60.05%, H:6.81%, N:4.59%
Theoretical value C:60.04%, H:6.79%, N:4.57%
It follows that the structural formula of rare earth compounding Q1 is:
Preparation example 2
Rare earth compounding that this preparation example provides for the present invention is described and preparation method thereof.
At 20 DEG C, will dissolved with (12.87g(0.03mol) 1,8-(N-2,6-dimethyl) di-imidogen carbazole (Guangzhou in
With Science and Technology Ltd. produce) oxolane (150mL) solution be added dropwise to 370mL dissolved with 13.52g (0.03mol)
Sc(CH2SiMe3)3(THF)2Tetrahydrofuran solution, and at 20 DEG C react 12 hours.Vacuum drains oxolane, obtains oil
Shape residue, adds toluene, is filtered to remove insoluble matter, obtains rare earth compounding Q2.
Analysis result shows:
FD-Mass:789.6(calcd:789.4)
Elementary analysis: measured value C:69.93%, H:7.94%, N:5.32
Theoretical value C:69.92%, H:7.91%, N:5.32%
It follows that the structural formula of rare earth compounding Q2 is:
Preparation example 3
Rare earth compounding that this preparation example provides for the present invention is described and preparation method thereof.
At 20 DEG C, will dissolved with 12.87g (0.03mol) 1,8-(N-2,6-dimethyl) di-imidogen carbazole (Guangzhou in
Science and Technology Ltd. produce) oxolane (150mL) solution be added dropwise to 370mL dissolved with 14.82g (0.03mol) Y
(CH2SiMe3)3(THF)2Tetrahydrofuran solution, and at 20 DEG C react 12 hours.Vacuum drains oxolane, obtains oily
Residue, adds toluene, is filtered to remove insoluble matter, obtains rare earth compounding Q3.
Analysis result shows:
FD-Mass:833.2(calcd:833.3)
Elementary analysis: measured value C:66.23%, H:7.47%, N:5.03
Theoretical value C:66.24%, H:7.49%, N:5.04%
The structural formula showing the rare earth compounding Q3 obtained is:
Preparation example 4
Rare earth compounding that this preparation example provides for the present invention is described and preparation method thereof.
At ambient temperature, will dissolved with 16.23g1,8-(N-2,6-diisopropyl) di-imidogen carbazole (Guangzhou in and section
Skill company limited produces) toluene solution (150mL) of (0.03mol) be added dropwise over 370mL dissolved with 8.21g (0.015mol) Lu
(CH2SiMe3)3(THF)2Toluene solution, react after 12h at 20 DEG C, vacuum drains toluene, obtains oily residue, adds
Hexane, is filtered to remove insoluble matter, obtains rare earth compounding Q4；
Analysis result shows:
FD-Mass:1031.6(calcd:1031.5)
Elementary analysis: measured value C:62.85%, H:7.63%, N:4.07
Theoretical value C:62.83%, H:7.62%, N:4.07%.
The structural formula showing the rare earth compounding Q4 obtained is:
Preparation example 5
Rare earth compounding that this preparation example provides for the present invention is described and preparation method thereof.
At 20 DEG C, will dissolved with 16.23g (0.03mol) 1,8-(N-2,6-diisopropyl) di-imidogen carbazole (Guangzhou in
With Science and Technology Ltd. produce) toluene (150mL) solution be added dropwise over 370mL dissolved with 22.23g (0.045mol) Sc
(CH2SiMe3)3(THF)2Toluene (solution, reacts 12h at 20 DEG C, and vacuum drains toluene, obtain oily residue, adds
Hexane, is filtered to remove insoluble matter, obtains rare earth compounding Q5；
Analysis result shows:
FD-Mass:901.5(calcd:901.5)
Elementary analysis: measured value C:71.85%, H:8.73%, N:4.66
Theoretical value C:71.88%, H:8.71%, N:4.66%.
The structural formula showing the rare earth compounding Q5 obtained is:
Preparation example 6
Rare earth compounding that this preparation example provides for the present invention is described and preparation method thereof.
At 20 DEG C, will be dissolved with 16.23g (0.03mol) 1, the toluene of 8-(N-2,6-diisopropyl) di-imidogen carbazole
Solution 150mL be added dropwise over 370mL dissolved with 13.52g (0.03mol) Y (CH2SiMe3)3(THF)2Toluene solution, at 20 DEG C
Lower reaction 1h, vacuum is drained toluene, is obtained oily residue, adds hexane, be filtered to remove insoluble matter, obtain rare earth compounding
Q6；
Analysis result shows:
FD-Mass:945.6(calcd:945.5)
Elementary analysis: measured value C:68.54%, H:9.32%, N:4.41
Theoretical value C:68.54%, H:9.31%, N:4.44%.
The structural formula showing the rare earth compounding Q6 obtained is:
Embodiment 1
This embodiment is for illustrating the preparation using the rare earth compounding Q1 of preparation to carry out rare-earth isoprene rubber:
Be sequentially added in 5L reactor under nitrogen protection 1800g hexane, 300g (4.41mol) isoprene,
0.0406g (44.1 μm ol) rare earth compounding Q1,0.0873g (441 μm ol) triisobutyl aluminium, [Ph3C][B(C6F5)4]
.0407g, (44.1 μm ol), after reacting 2 hours under the conditions of 20 DEG C, polymer solution autoreaction still will be released, and add 2,
6-di-tert-butyl hydroquinone's ethanol solution terminates reaction.Being computed monomer conversion is 92%.Cis-1,4 structural contents of polymer
It is 98.7%, Mn=52 × 104, Mw/Mn=2.55.
Embodiment 2
This embodiment is for illustrating the preparation using the rare earth compounding Q2 of preparation to carry out rare-earth isoprene rubber:
Be sequentially added in 5L reactor under nitrogen protection 1800g hexane, 300g (4.41mol) isoprene,
0.0368g (44.1 μm ol) rare earth compounding Q2,0.0873g (441 μm ol) triisobutyl aluminium, [Ph3C][B(C6F5)4]
.0.0407g, (44.1 μm ol), after reacting 2 hours under the conditions of 20 DEG C, polymer solution autoreaction still will be released, and add
2,6-di-tert-butyl hydroquinone's ethanol solution terminates reaction.Being computed monomer conversion is 96%.Cis-1,4 structures of polymer contain
Amount is 99.0%, Mn=49 × 104, Mw/Mn=2.87.
Embodiment 3
This embodiment is for illustrating the preparation using the rare earth compounding Q3 of preparation to carry out rare-earth isoprene rubber:
Be sequentially added in 5L reactor under nitrogen protection 1800g hexane, 300g (4.41mol) isoprene,
0.0349g (44.1 μm ol) rare earth compounding Q3,0.0873g (441 μm ol) triisobutyl aluminium, [Ph3C][B(C6F5)4]
0.0407g (44.1 μm ol), after reacting 2 hours, will release in polymer solution autoreaction still and adds 2 under the conditions of 20 DEG C,
6-di-tert-butyl hydroquinone's ethanol solution terminates reaction.Being computed monomer conversion is 90%.Cis-1,4 structural contents of polymer
It is 98.8%, Mn=42 × 104, Mw/Mn=2.23.
Embodiment 4
This embodiment is for illustrating the preparation using the rare earth compounding Q4 of preparation to carry out rare-earth isoprene rubber:
Be sequentially added in 5L reactor under nitrogen protection 1800g hexane, 150g (2.21mol) isoprene,
0.0223g (22.1 μm ol) rare earth compounding Q4,0.0873g (441 μm ol) triisobutyl aluminium, [Ph3C][B(C6F5)4]
0.0407g (44.1 μm ol), after reacting 2 hours, will release in polymer solution autoreaction still and adds 2 under the conditions of 20 DEG C,
6-di-tert-butyl hydroquinone's ethanol solution terminates reaction.Being computed monomer conversion is 62%.Cis-1,4 structural contents of polymer
It is 99.0%, Mn=55 × 104, Mw/Mn=2.27.
Embodiment 5
This embodiment is for illustrating the preparation using the rare earth compounding Q5 of preparation to carry out rare-earth isoprene rubber:
Be sequentially added in 5L reactor under nitrogen protection 1800g hexane, 300g (4.41mol) isoprene,
0.0418g (44.1 μm ol) rare earth compounding Q5,0.0873g (441 μm ol) triisobutyl aluminium, [Ph3C][B(C6F5)4]
0.0407g (44.1 μm ol), after reacting 2 hours, will release in polymer solution autoreaction still and adds 2 under the conditions of 20 DEG C,
6-di-tert-butyl hydroquinone's ethanol solution terminates reaction.Being computed monomer conversion is 51%.Cis-1,4 structural contents of polymer
It is 99.3%, Mn=65 × 104, Mw/Mn=2.64.
Embodiment 6
This embodiment is for illustrating the preparation using the rare earth compounding Q6 of preparation to carry out rare-earth isoprene rubber:
Be sequentially added in 5L reactor under nitrogen protection 1800g hexane, 450g (6.61mol) isoprene,
0.0599g (66.2 μm ol) rare earth compounding Q6,0.0873g (441 μm ol) triisobutyl aluminium, [Ph3C][B(C6F5)4]
0.0407g (44.1 μm ol), after reacting 2 hours, will release in polymer solution autoreaction still and adds 2 under the conditions of 20 DEG C,
6-di-tert-butyl hydroquinone's ethanol solution terminates reaction.Being computed monomer conversion is 39%.Cis-1,4 structural contents of polymer
It is 99.1%, Mn=23 × 104, Mw/Mn=1.97.
Embodiment 7
This embodiment is for illustrating the preparation using the rare earth compounding Q2 of preparation to carry out rare-earth isoprene rubber:
Employing is the preparation that the method for embodiment 2 carries out rare-earth isoprene rubber, except for the difference that, reacts 2 under the conditions of-20 DEG C
Hour.Being computed monomer conversion is 17%.Polymer cis-Isosorbide-5-Nitrae structural content is 99.6%, Mn=21 × 104, Mw/Mn=1.52.
Embodiment 8
This embodiment is for illustrating the preparation using the rare earth compounding Q2 of preparation to carry out rare-earth isoprene rubber:
Employing is the preparation that the method for embodiment 2 carries out rare-earth isoprene rubber, except for the difference that, reacts 2 little under the conditions of 0 DEG C
Time.Being computed monomer conversion is 33%.Polymer cis-Isosorbide-5-Nitrae structural content is 99.6%, Mn=30 × 104, Mw/Mn=1.59.
Embodiment 9
This embodiment is for illustrating the preparation using the rare earth compounding Q2 of preparation to carry out rare-earth isoprene rubber:
Employing is the preparation that the method for embodiment carries out rare-earth isoprene rubber, except for the difference that, reacts 30 under the conditions of 40 DEG C
Minute.Being computed monomer conversion is 100%.Polymer cis-Isosorbide-5-Nitrae structural content is 98.6%, Mn=41 × 104, Mw/Mn=
2.91。
Embodiment 10
This embodiment is for illustrating the preparation using the rare earth compounding Q2 of preparation to carry out rare-earth isoprene rubber:
Employing is the preparation that the method for embodiment carries out rare-earth isoprene rubber, except for the difference that, reacts 10 under the conditions of 80 DEG C
Minute.Being computed monomer conversion is 100%.Polymer cis-Isosorbide-5-Nitrae structural content is 98.2%, Mn=37 × 104, Mw/Mn=
3.34。
Data above shows, uses the catalyst of the present invention, by suitably adjusting polymerizing condition, it is also possible to high taking into account
While conversion ratio, the cis-Isosorbide-5-Nitrae structural content of polymer is made to be up to more than 98%.
Claims (15)
1. a rare earth compounding, it is characterised in that described rare earth compounding has a structure shown in formula (I):
Wherein, R1、R2、R3And R4It is each independently hydrogen or C1-C20Alkyl；Ln is Sc, Lu or Y, and THF represents oxolane, Me
Represent methyl.
Rare earth compounding the most according to claim 1, wherein, R1、R2、R3And R4It is each independently hydrogen or C1-C4Alkane
Base.
Rare earth compounding the most according to claim 1 and 2, wherein, R1、R2、R3And R4Identical.
4. a preparation method for rare earth compounding, the method is included in and generates the bar of the rare earth compounding of structure shown in formula I
Under part, it is Ln (CH by there is the compound of structure shown in formula II with formula2SiMe3)3(THF)2Compound at organic solvent
Middle contact,
Wherein, the condition of the rare earth compounding of structure shown in described generation formula I include reaction temperature be-20 DEG C to 60 DEG C, anti-
It is 4-16 hour between Ying Shi；R1、R2、R3, and R4It is each independently hydrogen or C1-C20Alkyl；Ln is Sc, Lu or Y, and THF represents four
Hydrogen furan, Me represents methyl.
Preparation method the most according to claim 4, wherein, has compound and the Ln of structure shown in formula II
(CH2SiMe3)3(THF)2The mol ratio of compound be 1:0.5-1.5.
Preparation method the most according to claim 4, wherein, R1、R2、R3And R4It is each independently hydrogen or C1-C4Alkyl.
Preparation method the most according to claim 6, wherein, R1、R2、R3And R4Identical.
8. a rare earth catalyst, this catalyst contains boride and rare earth compounding, it is characterised in that described rare earth compounding
For the rare earth compounding described in any one in claim 1-3.
Catalyst the most according to claim 8, wherein, described rare earth compounding is 1:0.9-with the mol ratio of boride
1.1。
The most according to claim 8 or claim 9, catalyst, wherein, described boride is selected from [Ph3C][B(C6F5)4]、
[PhMe2NH][B(C6F5)4] and B (C6F5)3In one or more.
11. catalyst according to claim 8 or claim 9, wherein, described catalyst is possibly together with alkyl aluminum and/or alkyl hydrides
Aluminum.
12. catalyst according to claim 11, wherein, the molal quantity of described alkyl aluminum and/or alkyl aluminium hydride is with dilute
The ratio of the molal quantity of soil coordination compound is 10-50:1.
Rare earth catalyst described in any one application in conjugate diene polymerization in 13. claim 8-12.
The preparation method of 14. 1 kinds of rare-earth isoprene rubbers, the method includes: in presence of organic solvent and solution polymerization
Under the conditions of, isoprene is contacted with rare earth catalyst, it is characterised in that described rare earth catalyst is to appoint in claim 8-12
Anticipate a described rare earth catalyst.
15. methods according to claim 14, wherein, described solution polymerization condition includes that temperature is 10-30 DEG C, pressure
Power is 0.15-0.7MPa, and the time is 20-300 minute.
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| CN102174174A (en) * | 2011-01-24 | 2011-09-07 | 吉林大学 | Amine imine rare earth catalyst and preparation methods and application thereof |
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