CN104140435A - Rare earth complex and preparation method thereof, catalyst and application thereof, and preparation method of rare earth isoprene rubber - Google Patents
Rare earth complex and preparation method thereof, catalyst and application thereof, and preparation method of rare earth isoprene rubber Download PDFInfo
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Abstract
The invention discloses a rare earth complex and a preparation method thereof, a rare earth catalyst and application thereof, and a preparation method of rare earth isoprene rubber. The rare earth complex has a structure as shown in formula (I), R1, R2, and R3 are independently hydrogen or C1-C20 alkyl; Ln is one of rare earth metals, THF is tetrahydrofuran, and Me represents methyl. The content of cis-1, 4 structure rare earth isoprene rubber prepared by the e rare earth catalyst is high.
Description
Technical field
The present invention relates to a kind of rare earth compounding and preparation method thereof, containing catalyzer, the application of this catalyzer in conjugate diene polymerization and the preparation method of rare-earth isoprene rubber of this rare earth compounding.
Technical background
Since the sixties in last century, China found rare earth compounding energy catalysis diolefin polymerization, in the world the research of rare earth metal organic compound catalyzed polymerization is had made great progress, develop series of rare earth catalyst system, as Neodymium trichloride/aluminum alkyls binary system, carboxylic acid neodymium/aluminum alkyls/halogenide ternary system and carboxylic acid neodymium/aluminum alkyls/alkyl halide/isoprene quaternary catalytic system, with the synthetic high-cis polybutadiene of this type of rare earth catalyst and polyisoprene rubber, become the important kind of suitability for industrialized production.
In recent years, some are luxuriant, half luxuriant and non-luxuriant cationic catalyzing of rare-earth metal system becomes again study hotspot.This class catalyzer, by changing the part of title complex, limits its geometric configuration, can improve efficiency and the selectivity of catalyzer, realize conjugate diene polymerization or with the copolymerization of monoolefine.As rare earth metallocene/aluminum alkyls/organic boron salt cation catalyst system of Riken researchist's application has very high catalytic activity to the equal polymerization of conjugated alkene and with the copolymerization of vinyl aromatic compounds, and polyreaction has the feature of living polymerization, specifically can be referring to US2002/0119889, US6,596,828, US6,960,631B2, and US6,683,140B2, but these technology, when carrying out the polymerization of isoprene, obtain higher than cis-Isosorbide-5-Nitrae selectivity more than 95 % by weight, must under the polymerization temperature lower than-20 ℃, carry out, operational condition is harsh.
Chinese Academy of Sciences Changchun should be changed Cui of institute east plum and in CN101186663A, disclose the cationic catalyst system of three components that a kind of NCN clamp type rareearth complexes and aluminum alkyls, organic boron salt form, within the scope of-20 to 80 ℃ during catalysis isoprene polymerization, in polymkeric substance, cis-Isosorbide-5-Nitrae structural content is 55.0-98.8%; During Butadiene Polymerization, in polymkeric substance, cis-Isosorbide-5-Nitrae structural content is 90.1-99.9%.
Summary of the invention
The object of the invention is on the basis of existing technology, a kind of new rare earth compounding and preparation method thereof is provided, when carrying out isoprene polymerization, there is high cis-Isosorbide-5-Nitrae optionally rare earth catalyst, the application of above-mentioned rare earth catalyst when conjugate diene polymerization and a kind of preparation method of rare-earth isoprene rubber.
The invention provides a kind of rare earth compounding, wherein, described rare earth compounding has the structure shown in formula (I):
Wherein, R
1, R
2and R
3be hydrogen or C independently of one another
1-C
20alkyl; Ln is a kind of in rare earth metal, and THF represents tetrahydrofuran (THF), Me represent methylidene.
The present invention also provides a kind of preparation method of rare earth compounding, and the method is included under the condition that generates the rare earth compounding of structure shown in formula I, by compound and the general formula with structure shown in formula II, is Ln (CH
2siMe
3)
3(THF)
2compound in organic solvent, contact,
Wherein, R
1, R
2and R
3be hydrogen or C independently of one another
1-C
20alkyl; Ln is a kind of in rare earth metal, and THF represents tetrahydrofuran (THF), Me represent methylidene.
The present invention also provides the rare earth compounding being prepared by aforesaid method.
It is a kind of for rare earth catalyst that the present invention also provides, and wherein, described catalyzer contains above-mentioned rare earth compounding and boride.
The present invention also provides the application of above-mentioned rare earth catalyst in conjugate diene polymerization.
The present invention also provides a kind of preparation method of rare-earth isoprene rubber, the method comprises: under the existence of organic solvent and under solution polymerization condition, isoprene is contacted with rare earth catalyst, and wherein, described rare earth catalyst is above-mentioned rare earth catalyst provided by the invention.
The rare earth catalyst that contains described rare earth compounding provided by the invention is during for isoprene polymerization, and the cis-Isosorbide-5-Nitrae structural content that obtains rare-earth isoprene rubber in preferred implementation can be up to 99 % by weight.
Embodiment
Rare earth compounding provided by the invention, described rare earth compounding has the structure shown in formula (I):
Wherein, R
1, R
2and R
3be hydrogen or C independently of one another
1-C
20alkyl; Ln is a kind of in rare earth metal, and THF represents tetrahydrofuran (THF), Me represent methylidene.
Wherein, described C
1-C
20alkyl can be straight or branched, specific examples 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.Described C
1-C
5the 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, isopentyl, tert-pentyl and neo-pentyl.
The present inventor finds under study for action, by specific R
1-R
3while coordinating the rare earth compounding form as the component of the catalyzer of catalysis isoprene polymerization, can obtain fabulous catalytic effect, therefore, preferably, R
1, R
2and R
3be hydrogen or C independently of one another
1-C
4alkyl; Further preferably, R
1, R
2and R
3identical, more further preferred R
1, R
2and R
3be methyl or be sec.-propyl.
The present inventor finds under study for action, the rare earth compounding being comprised of specific rare earth can be obtained fabulous catalytic effect during as the catalyzer of catalysis isoprene polymerization, therefore, and preferably, rare earth metal Ln is Sc or Lu or Y, and further preferably rare earth metal is Sc or Lu.
The preparation method of rare earth compounding provided by the invention, the method is included under the condition that generates the rare earth compounding of structure shown in formula I, by compound and the general formula with structure shown in formula II, is Ln (CH
2siMe
3)
3(THF)
2compound in organic solvent, contact,
Wherein, R
1, R
2and R
3be hydrogen or C independently of one another
1-C
20alkyl; Ln is a kind of in rare earth metal, and THF represents tetrahydrofuran (THF), Me represent methylidene.
Wherein, as mentioned above, described C
1-C
20alkyl can be straight or branched, specific examples 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.Described C
1-C
5the 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, isopentyl, tert-pentyl and neo-pentyl.
The present inventor finds under study for action, by specific R
1-R
3while coordinating the rare earth compounding form as the catalyzer of catalysis isoprene polymerization, can obtain fabulous catalytic effect, therefore, preferably, R
1, R
2, and R
3be hydrogen or C independently of one another
1-C
3alkyl; Further preferably, R
1, R
2and R
3identical, more further preferred R
1, R
2and R
3be methyl or be sec.-propyl.
According to the present invention, the specific examples with the compound of structure shown in formula II can include but not limited to: 8-(N-2,6-dimethyl) imido grpup 1,2,3,4-tetrahydroquinoline, 8-(N-2,6-di-isopropyl) imido grpup 1,2,3,4-tetrahydroquinoline.Aforementioned substances all can be commercially available.
According to the present invention, general formula is Ln (CH
2siMe
3)
3(THF)
2the specific examples of compound can include but not limited to: Lu (CH
2siMe
3)
3(THF)
2, Sc (CH
2siMe
3)
3(THF)
2y (CH
2siMe
3)
3(THF)
2.Aforementioned substances all can be by being purchased or common practise is synthetic obtains.For example, Ln (CH
2siMe
3)
3(THF)
2can be synthetic according to the disclosed method of document Journal of Polymer Science:Part A:Polymer Chemistry DOI10.1002/POLA1376 page.
According to the present invention, there is compound and the Ln (CH of structure shown in formula II
2siMe
3)
3(THF)
2compound amount can in wider scope, select and change, as long as can access the rare earth compounding with structure shown in formula I, for example, there is compound and the Ln (CH of structure shown in formula II
2siMe
3)
3(THF)
2the mol ratio of compound can be 1:0.5-1.5, be preferably 1:0.75-1.25.
The present inventor finds under study for action, the rare earth compounding being comprised of specific rare earth can be obtained fabulous catalytic effect during as the catalyzer of catalysis isoprene polymerization, therefore, and preferably, rare earth metal Ln is Sc or Lu or Y, and further preferably rare earth metal is Sc or Lu.
The present invention is not particularly limited the condition of the rare earth compounding of structure shown in described generation formula I, can select for the routine of this area.As a rule, shown in described generation formula I, the condition of the rare earth compounding of structure comprises temperature of reaction and reaction times.Wherein, described temperature of reaction can be selected and change in wider scope, in order to be more conducive to the carrying out of reaction, described temperature of reaction can for-20 ℃ to 60 ℃, be preferably 0-20 ℃.The prolongation in reaction times is conducive to the raising of the transformation efficiency of reactant or the yield of reaction product, but the reaction times is long to the increase rate of the yield of the transformation efficiency of reactant or reaction product not obvious, therefore, generally, the described reaction times can for 4-16 hour, be preferably 8-16 hour.
According to the preparation method of rare earth compounding provided by the invention, the described organic solvent for the preparation of rare earth compounding can for existing various can, as the organic substance of 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 be used separately, also can mix use.The consumption of described organic solvent can be Ln (CH according to compound and the general formula with structure shown in formula II
2siMe
3)
3(THF)
2the consumption of compound reasonably select, for example, the consumption of described solvent can be Ln (CH so that have compound and the general formula of structure shown in formula II
2siMe
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 above-mentioned 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., and to this, those skilled in the art all can know, at this, will repeat no more.
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 rare earth compounding being prepared by aforesaid method.
Rare earth catalyst provided by the invention, this catalyzer contains boride and rare earth compounding, and wherein, described rare earth compounding is above-mentioned rare earth compounding provided by the invention.
According to the present invention, the content of described rare earth compounding and boride can be selected and change in wider scope, but in order to make these two kinds of materials can play catalysis conjugate diene polymerization better, under preferable case, the mol ratio of described rare earth compounding and boride can be 1:0.9-1.1, is preferably 1:0.95-1.
According to the present invention, described boride can, for the existing various boron-containing compounds 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 material all can be commercially available.
According to the present invention, wherein, described catalyzer also contains aluminum alkyls and/or alkyl aluminium hydride.
Aluminum alkyls described in the present invention and/or alkyl aluminium hydride refer to aluminum alkyls, alkyl aluminium hydride or their mixture.Preferred described aluminum alkyls and/or alkyl aluminium hydride are one or more in trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, three amyl group aluminium, three hexyl aluminium, diethyl aluminium hydride and hydrogenation dibutyl aluminium; Be preferably tri-butyl aluminum and/or hydrogenation dibutyl aluminium.Aluminum alkyls described in the present invention and/or alkyl aluminium hydride refer to aluminum alkyls, alkyl aluminium hydride or their mixture.
According to the present invention, described aluminum alkyls and/or alkyl aluminium hydride and rare earth compounding content can be selected and change in wider scope, but for catalysis conjugate diene polymerization better, the ratio of the total mole number of described aluminum alkyls and/or alkyl aluminium hydride and the mole number of rare earth compounding can be 10-50:1.Above material all can be commercially available.
The invention provides the application of rare earth catalyst of the present invention in conjugate diene polymerization.
When catalyzer of the present invention is used as the catalyzer in conjugate diene polymerization process, the general conjugated diene with respect to every mole, usage quantity is 1 * 10
-6-4 * 10
-4mol rare earth metal, preferably 1.5 * 10
-6-3.5 * 10
-4mol rare earth metal.The excessive cost that not only increases of catalyst levels, but also may make ash oontent in polymer product increase.Ash content described in the present invention refers to undecomposable component in polymerisate.
When catalyzer of the present invention is applied to conjugate diene polymerization, the method of described conjugate diene polymerization can be carried out with reference to prior art, generally comprise: under the existence of catalyzer of the present invention, in inert organic solvents, carry out conjugated diene solution polymerization, or under the condition that there is no described inert organic solvents or contain inert organic solvents described in minute quantity, carry out the mass polymerization of conjugated diene, those skilled in the art all can know this, not repeat them here.
In described conjugated diene solution polymerization process, the organic solvent using is not particularly limited, can select normally used aliphatic saturated hydrocarbon and/or the alicyclic hydrocarbon that reactive component is to inertia in this area, can be for example C
5-C
10straight-chain paraffin and/or C
5-C
10naphthenic hydrocarbon, typical organic solvent includes but not limited to one or more in hexane, hexanaphthene, heptane, pentane, iso-pentane, octane, methylcyclohexane, benzene,toluene,xylene and isopropyl benzene.According to the present invention, the organic solvent using in described conjugated diene solution polymerization process can be identical or different with the organic solvent that uses in rare earth compounding preparation process of the present invention.
In described conjugate diene polymerization process, described conjugated diene can, for the conventional conjugated diene in this area, include but not limited to C
4-C
6conjugated diene, can be for example divinyl, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2, one or more in 3-dimethylbutadiene, are preferably divinyl and/or isoprene.
In described conjugate diene polymerization process, the condition of described polymerization can be carried out with reference to prior art, and under preferable case, the condition of described polymerization comprises: the temperature of polymerization is subzero 30 ℃ to 80 ℃ above freezing, be preferably subzero 20 ℃ to 70 ℃ above freezing, more preferably subzero 10 ℃ to 60 ℃ above freezing; The time of polymerization is 20-300 minute, is preferably 30-120 minute.
As previously mentioned, in described conjugate diene polymerization process, catalyst levels is generally the conjugated diene with respect to every mole, and usage quantity is 1 * 10
-6-4 * 10
-4mol rare earth metal, preferably 1.5 * 10
-6-3.5 * 10
-4mol rare earth metal.
In described conjugate diene polymerization process, can adopt the conventional terminator in this area directly to stop reactive polymer, described terminator can be for example water and/or alcoholic solvent, be preferably one or more in water, methyl alcohol, ethanol, positive Virahol, Virahol and 2,6-di-tert-butyl hydroquinone methyl alcohol.
In addition, the present invention also provides a kind of preparation method of rare-earth isoprene rubber, and the method comprises: under the existence of organic solvent and under solution polymerization condition, isoprene is contacted with rare earth catalyst, wherein, described rare earth catalyst is above-mentioned rare earth catalyst provided by the invention.
The preparation method's of institute provided by the invention rare-earth isoprene rubber improvements have been to adopt the rare earth catalyst that contains above-mentioned rare earth compounding, and all can be same as the prior art for the kind of the organic solvent of isoprene polymerization and solution polymerization condition etc.
According to the present invention, described solution polymerization condition can be that the routine of this area selects, but higher by cis-1 in order to obtain having, 4 content, described solution polymerization condition can comprise: temperature is 10-30 ℃, and pressure is 0.15-0.7MPa, and the time is 20-300 minute; The mol ratio of isoprene and rare earth compounding is 1:1 * 10
-6-1 * 10
-4.
Below by specific embodiment, describe the present invention, but scope of the present invention is not limited to these embodiment.
If not otherwise specified, the chemical reagent using in embodiment is chemically pure reagent.
In the present invention, the microtexture of synthetic conjugated diene polymer adopts German Bruker Tensor27 mid-infrared light spectrometer and German Bruker400MHz nmr determination, and solvent is deuterochloroform; Molecular weight and molecualr weight distribution adopts Shimadzu LC-10AT type gel permeation chromatograph (GPC) to measure, and THF is moving phase, and Narrow distribution polystyrene is standard specimen, and temperature is 25 ℃.
In the present invention, the solvent using in preparation process and conjugated diene are all processed through nitrogen deoxygenation, and solvent water number is lower 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 the mass concentration of conjugated diene monomer in polymerization system.
In the present invention, monomer conversion is concept well known to those skilled in the art, in the present invention, monomer conversion refers to monomer and by polyreaction, is converted into the per-cent of polymkeric substance, and it is generally the weight and the ratio that enters the monomer weight of polymerization workshop section of straight polymer.The weight that in the present invention, the weight of straight polymer is polymers soln and the product of polymer concentration, wherein, the weight of polymers soln refers to the weight of the polymers soln that does not add terminator, and polymer concentration refers to straight polymer shared weight percent in polymers soln.
In following examples, in polymkeric substance, cis-Isosorbide-5-Nitrae structural content adopts German Bruker400MHz nuclear magnetic resonance analyser to measure, and solvent is deuterochloroform; The weight-average molecular weight of polymkeric substance and molecular weight distribution adopt the gel permeation chromatograph (GPC) that the model purchased from Shimadzu company is LC-10AT to measure, wherein, with
THF is moving phase, take Narrow distribution polystyrene as standard specimen, and probe temperature is 25 ℃.
Preparation example 1
This preparation example is used for illustrating rare earth compounding provided by the invention and preparation method thereof.
At 20 ℃, by Lu (CH
2siMe
3)
3(THF)
217.41g (0.03mol) joins in the toluene of 370mL, then dropwise will be dissolved with 8-(N-2,6-dimethyl) imido grpup 1,2,3, toluene (150mL) solution of 4-tetrahydroquinoline (Guangzhou Cheng He Science and Technology Ltd. produces, 7.92g, 0.03mol) joins the aforementioned 370mL making and is dissolved with Lu (CH
2siMe
3)
3(THF)
2in the toluene solution of 17.41g (0.03mol), at 20 ℃, react after 1h, vacuum is drained toluene, obtains oily resistates, adds hexane, removes by filter insolubles, in oily resistates, adds toluene, obtains rare earth compounding Q1;
Analytical results shows:
FD-Mass:697.3（calcd:697.3）
Ultimate analysis: measured value C:53.36%, H:7.23%, N:4.01
Theoretical value C:53.35%, H:7.22%, N:4.01%.Hence one can see that, and the structural formula of rare earth compounding Q1 is:
Preparation example 2
This preparation example is used for illustrating rare earth compounding provided by the invention and preparation method thereof.
At 20 ℃, by Sc (CH
2siMe
3)
3(THF)
213.52g (0.03mol) joins in the toluene of 370mL, then dropwise will be dissolved with 8-(N-2,6-dimethyl) imido grpup 1,2,3, toluene (150mL) solution of 4-tetrahydroquinoline (Guangzhou Cheng He Science and Technology Ltd. produces, 7.92g, 0.03mol) joins the aforementioned 370mL obtaining and is dissolved with Sc (CH
2siMe
3)
3(THF)
2the toluene solution of 13.52g (0.03mol), reaction solution reacts after 1h at 20 ℃, and vacuum is drained toluene, obtains oily resistates, adds hexane, removes by filter insolubles, obtains rare earth compounding Q2;
Analytical results shows:
FD-Mass:567.4（calcd:567.3）
Ultimate analysis: measured value C:65.57%, H:8.85%, N:4.92
Theoretical value C:65.57%, H:8.87%, N:4.93%.
Hence one can see that, and the structural formula of rare earth compounding Q2 is:
Preparation example 3
This preparation example is used for illustrating rare earth compounding provided by the invention and preparation method thereof.
At 20 ℃, by Lu (CH
2siMe
3)
3(THF)
28.71g (0.015mol) joins in the toluene of 370mL, then dropwise will be dissolved with 8-(N-2,6-di-isopropyl) imido grpup 1,2,3, the toluene solution (150mL) of 4-tetrahydroquinoline (Guangzhou Cheng He Science and Technology Ltd. produce, 9.66g, 0.03mol) join the aforementioned 370mL obtaining containing Lu (CH
2siMe
3)
3(THF)
2in the toluene solution of 17.41g (0.03mol), reaction solution reacts after 1h at 20 ℃, and vacuum is drained toluene, obtains oily resistates, adds hexane, removes by filter insolubles, obtains rare earth compounding Q3;
Analytical results shows:
FD-Mass:753.4（calcd:753.4）
Ultimate analysis: measured value C:55.76%, H:7.77%, N:3.73
Theoretical value C:55.75%, H:7.75%, N:3.72%.
Hence one can see that, and the structural formula of rare earth compounding Q3 is:
Preparation example 4
This preparation example is used for illustrating rare earth compounding provided by the invention and preparation method thereof.
At 20 ℃, by Sc (CH
2siMe
3)
3(THF)
220.28g (0.045mol) joins 370mL toluene, dropwise will be dissolved with 8-(N-2,6-di-isopropyl) imido grpup 1,2,3, the toluene solution 150mL of 4-tetrahydroquinoline (Guangzhou Cheng He Science and Technology Ltd. produces, 9.66g, 0.03mol) joins the aforementioned 370mL making containing Sc (CH
2siMe
3)
3(THF)
2in the toluene solution of 13.52g (0.03mol), at 20 ℃, react after 1h, vacuum is drained toluene, obtains oily resistates, adds hexane, removes by filter insolubles, obtains rare earth compounding Q4;
Analytical results shows:
FD-Mass:623.5（calcd:623.4）
Ultimate analysis: measured value C:67.38%, H:9.39%, N:4.48%
Theoretical value C:67.37%, H:9.37%, N:4.49%.
Hence one can see that, and the structural formula of rare earth compounding Q4 is:
Embodiment 1
This embodiment is used for illustrating and uses the rare earth compounding Q1 of preparation to carry out the preparation of rare-earth isoprene rubber:
Under nitrogen protection, in 5L reactor, add successively 1800g hexane, 300g (4.41mol) isoprene, 0.0302g (44.1 μ mol) rare earth compounding Q1,0.0873g (441 μ mol) triisobutyl aluminium, [Ph
3c] [B (C
6f
5)
4] 0.0407g (44.1 μ mol), under 20 ℃ of conditions, react after 2 hours, polymers soln is emitted in still and add 2,6-di-tert-butyl hydroquinone ethanolic soln termination reaction.Transformation efficiency is 64% as calculated.The cis-Isosorbide-5-Nitrae structural content of polymkeric substance is 97.3%, Mn=62 * 10
4, Mw/Mn=1.17.
Embodiment 2
This embodiment is used for illustrating and uses the rare earth compounding Q2 of preparation to carry out the preparation of rare-earth isoprene rubber:
Under nitrogen protection, in 5L reactor, add successively 1800g hexane, 300g (4.41mol) isoprene, 0.0244g (44.1 μ mol) rare earth compounding Q2,0.0873g (441 μ mol) triisobutyl aluminium, [Ph
3c] [B (C
6f
5)
4] 0.0407g (44.1 μ mol), under 20 ℃ of conditions, react after 2 hours, polymers soln is emitted in still and add 2,6-di-tert-butyl hydroquinone ethanolic soln termination reaction.Transformation efficiency is 81% as calculated.The cis-Isosorbide-5-Nitrae structural content of polymkeric substance is 98.1%, Mn=76 * 10
4, Mw/Mn=1.12.
Embodiment 3
This embodiment is used for illustrating and uses the rare earth compounding Q3 of preparation to carry out the preparation of rare-earth isoprene rubber:
Under nitrogen protection, in 5L reactor, add successively 1800g hexane, 300g (4.41mol) isoprene, 0.0327g (44.1 μ mol) rare earth compounding Q3,0.0873g (441 μ mol) triisobutyl aluminium, [Ph
3c] [B (C
6f
5)
4] 0.0407g (44.1 μ mol), under 20 ℃ of conditions, react after 2 hours, polymers soln is emitted in still and add 2,6-di-tert-butyl hydroquinone ethanolic soln termination reaction.Transformation efficiency is 55% as calculated.The cis-Isosorbide-5-Nitrae structural content of polymkeric substance is 98.0%, Mn=81 * 10
4, Mw/Mn=1.23.
Embodiment 4
This embodiment is used for illustrating and uses the rare earth compounding Q4 of preparation to carry out the preparation of rare-earth isoprene rubber:
Under nitrogen protection, in 5L reactor, add successively 1800g hexane, 150g (2.21mol) isoprene, 0.0135g (22.1 μ mol) rare earth compounding Q4,0.0873g (441 μ mol) triisobutyl aluminium, [Ph
3c] [B (C
6f
5)
4] 0.0407g (44.1 μ mol), under 20 ℃ of conditions, react after 2 hours, polymers soln is emitted in still and add 2,6-di-tert-butyl hydroquinone ethanolic soln termination reaction.Transformation efficiency is 37% as calculated.The cis-Isosorbide-5-Nitrae structural content of polymkeric substance is 98.1%, Mn=52 * 10
4, Mw/Mn=1.27.
Embodiment 5
This embodiment is used for illustrating and uses the rare earth compounding Q2 of preparation to carry out the preparation of rare-earth isoprene rubber:
Employing is that the method for embodiment 2 is carried out the preparation of rare-earth isoprene rubber, different, under-20 ℃ of conditions, reacts 2 hours.Transformation efficiency is 10% as calculated.The cis-Isosorbide-5-Nitrae structural content of polymkeric substance is 99%, Mn=91 * 10
4, Mw/Mn=1.13.
Embodiment 6
This embodiment is used for illustrating and uses the rare earth compounding Q2 of preparation to carry out the preparation of rare-earth isoprene rubber:
Employing is that the method for embodiment 2 is carried out the preparation of rare-earth isoprene rubber, different, under 0 ℃ of condition, reacts 2 hours.Transformation efficiency is 22% as calculated.The cis-Isosorbide-5-Nitrae structural content of polymkeric substance is 98.4%, Mn=84 * 10
4, Mw/Mn=1.16.
Embodiment 7
This embodiment is used for illustrating and uses the rare earth compounding Q2 of preparation to carry out the preparation of rare-earth isoprene rubber:
Employing is that the method for embodiment 2 is carried out the preparation of rare-earth isoprene rubber, different, under 40 ℃ of conditions, reacts 30 minutes.Transformation efficiency is 100% as calculated.The cis-Isosorbide-5-Nitrae structural content of polymkeric substance is 96.1%, Mn=53 * 10
4, Mw/Mn=2.22.
Embodiment 8
This embodiment is used for illustrating and uses the rare earth compounding Q2 of preparation to carry out the preparation of rare-earth isoprene rubber:
Employing is that the method for embodiment 2 is carried out the preparation of rare-earth isoprene rubber, different, under 80 ℃ of conditions, reacts 10 minutes.Transformation efficiency is 100% as calculated.The cis-Isosorbide-5-Nitrae structural content of polymkeric substance is 93.2%, Mn=47 * 10
4, Mw/Mn=2.56.
Embodiment 9
This embodiment is used for illustrating and uses the rare earth compounding Q2 of preparation to carry out the preparation of rare-earth isoprene rubber:
Employing is that the method for embodiment 2 is carried out the preparation of rare-earth isoprene rubber, different, under nitrogen protection, in 5L reactor, adds successively 1800g hexane, 450g (6.61mol) isoprene, 0.357g (661 μ mol) rare earth compounding 2, [Ph
3c] [BC
6f
5]
4] 0.407g (441 μ mol), under 20 ℃ of conditions, react after 2 hours, polymers soln is emitted in still and add 2,6-di-tert-butyl hydroquinone ethanolic soln termination reaction.Emit polymers soln, by Ethanol Treatment, obtain solid polymer, then polymkeric substance is placed in to vacuum drying oven and is dried to constant weight.Transformation efficiency is 29% as calculated.The cis-Isosorbide-5-Nitrae structural content of polymkeric substance is 98.0%, Mn=66 * 10
4, Mw/Mn=1.18.
Above data show, adopt catalyzer of the present invention, by suitable adjustment polymerizing condition, can also, when taking into account high transformation efficiency, make the cis-Isosorbide-5-Nitrae structural content of polymkeric substance up to more than 98%.
Claims (18)
1. a rare earth compounding, is characterized in that, described rare earth compounding has the structure shown in formula (I):
Wherein, R
1, R
2and R
3be hydrogen or C independently of one another
1-C
20alkyl; Ln is a kind of in rare earth metal, and THF represents tetrahydrofuran (THF), Me represent methylidene.
2. rare earth compounding according to claim 1, wherein, R
1, R
2and R
3be hydrogen or C independently of one another
1-C
4alkyl.
3. rare earth compounding according to claim 1 and 2, wherein, R
1, R
2and R
3identical.
4. rare earth compounding according to claim 1, wherein, Ln is Sc or Lu or Y.
5. a preparation method for rare earth compounding, the method is included under the condition that generates the rare earth compounding of structure shown in formula I, by compound and the general formula with structure shown in formula II, is Ln (CH
2siMe
3)
3(THF)
2compound in organic solvent, contact,
Wherein, R
1, R
2and R
3be hydrogen or C independently of one another
1-C
20alkyl; Ln is a kind of in rare earth metal, and THF represents tetrahydrofuran (THF), Me represent methylidene.
6. preparation method according to claim 5, wherein, has compound and the Ln (CH of structure shown in formula II
2siMe
3)
3(THF)
2the mol ratio of compound be 1:0.5-1.5.
7. according to the preparation method described in claim 5 or 6, wherein, Ln is Sc or Lu or Y.
8. preparation method according to claim 5, wherein, the condition of the rare earth compounding of structure shown in described generation formula I comprises that temperature of reaction is that-20 ℃ to 60 ℃, reaction times are 4-16 hour.
9. preparation method according to claim 5, wherein, R
1, R
2and R
3be hydrogen or C independently of one another
1-C
4alkyl.
10. preparation method according to claim 9, wherein, R
1, R
2and R
3identical.
11. 1 kinds of rare earth catalysts, this catalyzer contains boride and rare earth compounding, it is characterized in that described rare earth compounding is the rare earth compounding described in any one in claim 1-4.
12. catalyzer according to claim 11, wherein, the mol ratio of described rare earth compounding and boride is 1:0.9-1.1.
13. according to the catalyzer described in claim 11 or 12, 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.
14. according to the catalyzer described in claim 11 or 12, and wherein, described catalyzer also contains aluminum alkyls and/or alkyl aluminium hydride.
15. catalyzer according to claim 14, wherein, the ratio of the mole number of described aluminum alkyls and/or alkyl aluminium hydride and the mole number of rare earth compounding is 10-50:1.
The application of rare earth catalyst in 16. claim 11-15 described in any one in conjugate diene polymerization.
The preparation method of 17. 1 kinds of rare-earth isoprene rubbers, the method comprises: under the existence of organic solvent and under solution polymerization condition, isoprene is contacted with rare earth catalyst, it is characterized in that, described rare earth catalyst is the rare earth catalyst described in any one in claim 11-15.
18. methods according to claim 17, wherein, described solution polymerization condition comprises that temperature is 10-30 ℃, and pressure is 0.15-0.7MPa, and the time is 20-300 minute.
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|---|---|---|---|---|
| CN101186617A (en) * | 2007-11-23 | 2008-05-28 | 中国科学院上海有机化学研究所 | Nitrogen-containing ligand rare earth catalyst and application thereof in polyester synthesis |
| KR101189194B1 (en) * | 2009-03-18 | 2012-10-09 | 주식회사 엘지화학 | Novel transition metal complexes |
-
2013
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186617A (en) * | 2007-11-23 | 2008-05-28 | 中国科学院上海有机化学研究所 | Nitrogen-containing ligand rare earth catalyst and application thereof in polyester synthesis |
| KR101189194B1 (en) * | 2009-03-18 | 2012-10-09 | 주식회사 엘지화학 | Novel transition metal complexes |
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| Title |
|---|
| GEORGE J.P. BRITOVSEK ET AL.: "The role of bulky substituents in the polymerization of ethylene using late transition metal catalysts: a comparative study of nickel and iron catalyst systems", 《INORGANICA CHIMICA ACTA》 * |
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