CN106589195A - Method for preparing polyisoprene - Google Patents
Method for preparing polyisoprene Download PDFInfo
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- CN106589195A CN106589195A CN201510680000.5A CN201510680000A CN106589195A CN 106589195 A CN106589195 A CN 106589195A CN 201510680000 A CN201510680000 A CN 201510680000A CN 106589195 A CN106589195 A CN 106589195A
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- 0 CC(C)(C1C=CCC#CC1)[Cn][NH2+]C Chemical compound CC(C)(C1C=CCC#CC1)[Cn][NH2+]C 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/08—Isoprene
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Abstract
The invention relates to the field of catalytic polymerization and discloses a method for preparing polyisoprene. The method comprises steps as follows: an isoprene monomer and rare earth catalyst composition are subjected to a contact reaction under the polymerization condition, the rare earth catalyst composition contains a rare earth metal organic compound, an aluminum-containing compound and a halogen source, the aluminum-containing compound is alkyl aluminum and/or alkyl aluminum hydride, and the rare earth metal organic compound has the structure shown in the formula (I) in the specification. Polyisoprene prepared with the method contains relatively rich cis-1,4 bonds with narrow molecular weight distribution; besides, the mass of the product prepared with the method is little influenced by fluctuation of the polymerization condition and industrial production is facilitated.
Description
Technical field
The present invention relates to catalytic polymerization field, in particular it relates to a kind of method for preparing polyisoprene.
Background technology
With the development of auto industry, the demand of tire tread glue is also gradually increasing.As China is sub-
Tropic countries, it is not easy to which estate rubber tree is come natural rubber of receiving, so needing to develop the different of synthetic
Penta rubber is substituting.High cis- 1,4 linkage content of isoprene copolymer and narrow molecular weight distribution can be improved
The performance of the isoprene rubber for synthesizing.
CN102464745A describes a kind of rare earth catalyst composition for conjugate diene polymerization,
Said composition includes：
- as the neodymium caprate or neodymium naphthenate of rare earth catalyst,
- diethyl aluminium hydride, the triethyl aluminum mixture of one or two or more kinds therein,
- one chloro-di-isobutyl aluminum or aluminium diethyl monochloride.
In this carbon monoxide-olefin polymeric, the cis-Isosorbide-5-Nitrae linkage content of resulting polyisoprene is 96.6 weights
Amount weight % of % to 97.2.
CN1479754A describes a kind of side for preparing high cis-1,4 chaining isoprene copolymer
Method, methods described are reacted with carbon monoxide-olefin polymeric in the presence of being included in isoprene, the catalyst group
Compound includes：
A kind of-diene monomers of conjugation
- as the organic phosphoric acid neodymium of rare earth catalyst,
- molecular formula is included for AlR3Or HAlR2Alkyl aluminum alkylating reagent,
- the halogen donor comprising alkyl aluminum chloride.
In this preparation method, the preparation method of carbon monoxide-olefin polymeric is relatively complicated, and be polymerized all zero degree with
Under, it has not been convenient to large-scale industrial application.
Document Macromol.Chem.Phys.200,1163-1166 (1999) describes a kind of for preparing
The preparation method of butadiene polymer, wherein the carbon monoxide-olefin polymeric for using includes：
A kind of-conjugated diene monomer,
- rare earth compound,
- formula is AlR3Alkyl aluminum,
- the halogen donor that is made up of alkyl aluminium halide.
In this carbon monoxide-olefin polymeric, the Nd { N (SiMe for having used nitrogen to be coordinated3)2}3It is organic as rare earth metal
Compound, but the preparation method of the carbon monoxide-olefin polymeric is excessively simple, is simply simply mixed.This catalysis
Agent compositionss are only used for the polymerization of butadiene, when the polymerization for isoprene, will to reaction condition
Ask harsh, and affected larger by condition, the cis-content of the product of acquisition is not high and molecular weight distribution is wider.
The content of the invention
The purpose of the present invention is the defect for overcoming prior art, there is provided a kind of new cis- Isosorbide-5-Nitrae key of preparation height contains
The method of the polyisoprene of amount.
To achieve these goals, the present invention provides a kind of method for preparing polyisoprene, the method bag
Include：Under the polymerization conditions, isoprene monomer and rare earth catalyst composition are carried out into haptoreaction,
In the rare earth catalyst composition containing Rare-earth chemicals, the compound containing aluminium element and
Halogen source, the compound containing aluminium element are alkyl aluminum and/or alkyl aluminium hydride, and the rare earth metal is organic
Compound has the structure shown in formula (I)：
Wherein, M is any one in lanthanide rare metallic element；
R1、R2、R3、R4、R5And R6It is identical or different, it is each independently selected from hydrogen, C1-8Alkyl,
C6-12Aryl, and the R1、R2、R3、R4、R5And R6It is asynchronously in hydrogen and methyl
It is at least one；
L is-OR7Or-NR8, wherein, the R7Formed together with oxygen atom containing 2-10 carbon atom
Heterocycle, the R8The heterocycle containing 2-10 carbon atom or the R are formed together with nitrogen-atoms8
For C1-4Alkyl；
X is 1,2 or 3, and y=3-x.
By cis- 1,4 linkage content in the polyisoprene for preparing of said method of the present invention it is higher and point
Son amount narrowly distributing, and, the quality of the product obtained by the method for the present invention receives the ripple of polymeric reaction condition
It is dynamic to affect little, that is to say, that the method for the present invention can avoid carrying out under severe conditions, be conducive to
Commercial production.
In addition, the present inventor is found that the novel rare-earth based on rare earth metal salt is catalyzed under study for action
Agent compositionss, the novel rare-earth carbon monoxide-olefin polymeric include the rare earth metal organic compound as catalyst
Thing, the Rare-earth chemicals are based on No. 57 elements in the periodic table of elements between No. 71 elements
Element, the novel rare-earth carbon monoxide-olefin polymeric form coordinate bond by nitrogen and rare earth element, carry out isoprene
The polymerization of polymerization, in realizing resulting polymers, cis- Isosorbide-5-Nitrae linkage content is all higher than or is equal to 99 weight %,
Molecular weight distribution is less than or equal to 2.1.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of method for preparing polyisoprene, the method includes：In polyreaction bar
Under part, isoprene monomer and rare earth catalyst composition are carried out into haptoreaction, the rare earth catalyst
It is containing Rare-earth chemicals, the compound containing aluminium element and halogen source in compositionss, described containing aluminum
The compound of element is alkyl aluminum and/or alkyl aluminium hydride, and the Rare-earth chemicals have formula
(I) structure shown in：
Wherein, M is any one in lanthanide rare metallic element；
R1、R2、R3、R4、R5And R6It is identical or different, it is each independently selected from hydrogen, C1-8Alkyl,
C6-12Aryl, and the R1、R2、R3、R4、R5And R6It is asynchronously in hydrogen and methyl
It is at least one；
L is-OR7Or-NR8, wherein, the R7Formed together with oxygen atom containing 2-10 carbon atom
Heterocycle, the R8The heterocycle containing 2-10 carbon atom or the R are formed together with nitrogen-atoms8
For C1-4Alkyl；
X is 1,2 or 3, and y=3-x.
Under preferable case, in the structure shown in formula (I), M is neodymium or cerium；R1、R2、R3、R4、
R5And R6It is identical or different, it is each independently selected from hydrogen, C1-6Alkyl, C6-10Aryl, it is and described
R1、R2、R3、R4、R5And R6It is asynchronously at least one in hydrogen and methyl；L is-OR7
Or-NR8, wherein, the R7The heterocycle containing 2-7 carbon atom is formed together with oxygen atom, it is described
R8The heterocycle containing 2-7 carbon atom or the R are formed together with nitrogen-atoms8For C1-4Alkyl；x
For 1,2 or 3, and y=3-x.
In the case of more preferably, in the structure shown in formula (I), M is neodymium or cerium；R1、R2、R3、
R4、R5And R6It is identical or different, it is each independently selected from hydrogen, methyl, ethyl, n-pro-pyl, isopropyl
Base, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, n-hexyl, cyclopropyl, methyl ring
Propyl group, ethyl cyclopropyl, cyclopenta, methylcyclopentyl, cyclohexyl, phenyl, aminomethyl phenyl, ethyl
Phenyl, 3,5-dimethylphenyl, trimethylphenyl, Methylethyl phenyl, diethyl phenyl and triethyl group phenyl,
And the R1、R2、R3、R4、R5And R6It is asynchronously at least one in hydrogen and methyl；L
For-OR7Or-NR8, wherein, the R7The heterocycle containing 2-4 carbon atom is formed together with oxygen atom,
The R8The heterocycle containing 2-5 carbon atom or the R are formed together with nitrogen-atoms8For C1-4Hydrocarbon
Base；X is 1,2 or 3, and y=3-x.
Under preferable case, in the structure shown in formula (I), the L and M is bonded by coordination
Connect.
According to a kind of preferred embodiment, in the structure shown in formula (I) in the present invention, M
For neodymium or cerium；R1、R2、R3、R4、R5And R6It is identical or different, it is each independently selected from hydrogen, first
Base, ethyl, n-pro-pyl, isopropyl, normal-butyl, phenyl, aminomethyl phenyl, 3,5-dimethylphenyl, front three
Base phenyl, Methylethyl phenyl, ethylphenyl, diethyl phenyl and triethyl group phenyl, and the R1、
R2、R3、R4、R5And R6It is asynchronously at least one in hydrogen and methyl；L is selected from tetrahydrochysene furan
Mutter, pyridine and acetonitrile；X is 1,2 or 3, and y=3-x.
According to another kind of preferred embodiment, in the structure shown in formula (I) in the present invention, M
For neodymium or cerium；R1、R2、R3、R4、R5And R6It is identical or different, it is each independently selected from hydrogen, first
Base, ethyl, n-pro-pyl, isopropyl, normal-butyl, phenyl, aminomethyl phenyl, 3,5-dimethylphenyl, front three
Base phenyl, Methylethyl phenyl, ethylphenyl, diethyl phenyl and triethyl group phenyl, and the R1、
R2、R3、R4、R5And R6It is asynchronously at least one in hydrogen and methyl；X is 3, and y is
0。
According to the third preferred embodiment, in the structure shown in formula (I) in the present invention, M
For neodymium or cerium；R1、R2、R3、R4、R5And R6It is identical or different, be each independently selected from methyl,
N-pro-pyl, normal-butyl, phenyl and cyclohexyl, and the R1、R2、R3、R4、R5And R6When different
For methyl；L is selected from tetrahydrofuran, pyridine and acetonitrile；X is 1 or 2, and y=3-x.
According to the 4th kind of preferred embodiment, in the structure shown in formula (I) in the present invention, M
For neodymium or cerium；R1、R2、R3、R4、R5And R6It is identical or different, be each independently selected from methyl,
Normal-butyl and phenyl, and the R1、R2、R3、R4、R5And R6It is asynchronously methyl；X is 3, and
Y is 0.
The present invention does not have spy to the method for preparing the Rare-earth chemicals of the structure shown in formula (I)
Other restriction.Those skilled in the art can take the synthesis coordinationization of routine in the art according to structural formula
The method of compound is prepared.
Under preferable case, the invention provides a kind of method for preparing Rare-earth chemicals, this is dilute
Earth metal organic compound has the structure shown in formula (I), and the method includes：In protective gas and
In the presence of organic solvent, rare earth metal source is contacted with the compound of structure shown in formula (II), institute
It is the compound containing the element shown in M to state rare earth metal source, the organic solvent selected from halogenated hydrocarbons,
Alcohols, aromatic hydrocarbons, halogenated aryl hydrocarbon, formula OR7Shown Oxygenic heterocyclic compounds and formula NR8Shown chemical combination
At least one in thing,
Wherein, M, R1、R2、R3、R4、R5、R6、L、R7、R8, x and y definition as this
It is bright aforementioned to be defined.
Each in structure and the compound of structure shown in formula (II) shown in wherein involved formula (I)
The definition of group is identical with the foregoing teachings of the present invention, and the present invention will not be described here, art technology
Personnel should not be construed as limiting the invention.
Preferably, the rare earth metal source can be the salt containing the element shown in M, for example, can be
Any one in chloride containing the element shown in M, nitrate, sulfate.
Preferably, the consumption mole in the compound of structure shown in the formula (II) and the rare earth metal source
Than for 0.5-10：1；Preferably 1-4：1.
The species of the organic solvent is not particularly limited, as long as enabling to the rare earth metal
Wherein just, preferably the organic solvent is polarity to the compound dissolution of source and structure shown in formula (II)
Organic solvent, the more preferably organic solvent are the chemical combination that coordinate bond can be formed with the M element
Thing.
The consumption of the organic solvent is had no particular limits, those skilled in the art can be according to ability
The conventional amount used in domain is selected.Preferably, those skilled in the art can also prepare as needed
Target compound in x and y ratio determining the consumption of organic solvent.
The protective gas can be the noble gases for being not involved in reacting, for example, can be nitrogen, argon
Deng.
Preferably, the condition for being contacted includes：Temperature is 0-80 DEG C, and the time is 5-500 minutes.
The product that above-mentioned contact is obtained can also be concentrated by the present invention, and preferably, by dense
The crystal for adding appropriate non-polar solven such as ether higher to obtain purity in the product of contracting.
The halogen source be refer to provide halogen element compound, the halogen element include fluorine, chlorine, bromine,
Iodine.
In the rare earth catalyst composition, the Rare-earth chemicals, the change containing aluminium element
The content mol ratio of compound and halogen source is 1：2-10：1-30；More preferably 1：4-8：1-15.
It should be strongly noted that can also contain aluminium element in the halogen source, the present invention is especially defined
Compound containing halogen element and aluminium element falls within halogen source of the present invention；And contain aluminium element and not
Compound containing halogen element belongs to the compound containing aluminium element of the present invention.
Alkyl in the alkyl aluminum can be C2-C8Alkyl, specifically, the alkyl aluminum can be
In trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, triisobutyl aluminium and three amyl group aluminum one
Plant or various；At least one preferably in triethyl aluminum, triisobutyl aluminium and triethyl aluminum；More preferably
For triisobutyl aluminium or triethyl aluminum.
Alkyl in the alkyl aluminium hydride can be C2-C4Alkyl, specifically, the alkyl hydrides
Aluminum can be diethyl aluminium hydride and/or hydrogenation dibutyl aluminum；Dibutyl aluminum is hydrogenated preferably.
Preferably, when the M in Rare-earth chemicals is neodymium, the alkyl aluminum is preferably hydrogen
Change diisobutyl aluminum or triisobutyl aluminium.
The halogen source can be aikyl aluminum halide；It is preferred that the aikyl aluminum halide be diethyl aluminum chloride and/
Or diisobutyl aluminum chloride.
The haptoreaction can be carried out in the presence of an organic；It is preferred that the organic solvent selected from just oneself
At least one in alkane, pentane, hexane, heptane, hexamethylene, toluene, dimethylbenzene and chlorobenzene；More
Preferably normal hexane.
The catalytic condition can include：Temperature is 0-100 DEG C, and the time is 0.1-24h；It is preferred that
Ground, the catalytic condition include：Temperature is 5-80 DEG C, and the time is 0.2-12h.Especially,
The catalytic time zero is present in same system to participate in catalytic whole key elements
When middle.
Preferably, the isoprene monomer and the rare earth catalyst composition in terms of rare earth metal
The mol ratio of consumption is 1000-10000：1；More preferably 2000-9000：1；Particularly preferably
3500-9000：1.
Can also contain in the rare earth catalyst composition and be ready to use in the monomer for carrying out polyreaction (as
Isoprene monomer).In the rare earth catalyst composition, described being ready to use in carries out polyreaction
Monomer is 1-120 with the mol ratio of the Rare-earth chemicals：1；Preferably 10-80：1.
Under the conditions of being somebody's turn to do, more preferable catalysis activity can be obtained.
The rare earth catalyst composition can be generated in the course of reaction situ of polyreaction, it is also possible to
Using the method production for preparing in advance.Specifically, the preparation method of the carbon monoxide-olefin polymeric can include：
By Rare-earth chemicals, the compound containing aluminium element and halogen source and it is optional be ready to use in into
The monomer of row polyreaction is mixed in inert hydrocarbon solvent.
In the present invention, it is described " by Rare-earth chemicals, the compound containing aluminium element and halogen source
And optional being ready to use in carries out the monomer of polyreaction and is mixed in inert hydrocarbon solvent " refer to,
The mixing can presence or absence of it is described be ready to use in carry out the monomer of polyreaction in the case of enter
OK, that is to say, that carry out mixing needs or described need not being ready to use in described in aforesaid carrying out being polymerized instead
The monomer answered.
According to a kind of preferred embodiment, by Rare-earth chemicals, the change containing aluminium element
Compound and halogen source and the optional monomer for carrying out polyreaction that is ready to use in are carried out in inert hydrocarbon solvent
The step of mixing, includes：
(1) by the Rare-earth chemicals and the compound containing aluminium element and it is optional described in
Being ready to use in the conjugated diene for carrying out polyreaction carries out hybrid reaction in inert hydrocarbon solvent；
(2) introduce the halogen source in mixture system to be aged.
Under preferable case, in the present invention, in step (1), the condition of the hybrid reaction includes：
Temperature is 5-40 DEG C；Time is 0.01-2h.
Under preferable case, in the present invention, in step (2), the condition of the ageing includes：Temperature
Spend for 45-85 DEG C；Time is 0.02-5h.
The inert hydrocarbon solvent includes but is not limited to arsol (such as toluene) or aliphatic or alicyclic
Solvent is (such as pentane, pentane, isopentane, hexanes mixtures, normal hexane, hexamethylene, methyl cyclohexane
Alkane, heptane mixture or normal heptane).
The consumption of the inert hydrocarbon solvent is caused in the rare earth catalyst composition, preferably described dilute
Concentration >=the 0.0002mol/L of earth metal organic compound.
The whole polymerization process of the present invention is steadily easily controllable, is very suitable for serialization commercial production, institute
In the polymeric articles for obtaining, cis- Isosorbide-5-Nitrae linkage content is high, and molecular weight distribution is less than or equal to 2.1.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Hereinafter will be described the present invention by embodiment.
In following examples, the cis- Isosorbide-5-Nitrae linkage content in the polymeric articles uses C13 nuclear magnetic resonance methods
Or the measurement of near-infrared analysis method；The molecular weight distribution of the polyisoprene product is by gpc measurement；System
Standby metal-organic raw material is obtained by commercial sources, especially, in Sigma-Aldrich medicaments
Company buys.
Preparation example 1-9 is used to prepare Rare-earth chemicals.
Embodiment 1-9 is used for the method for preparing polyisoprene for illustrating the present invention.
Preparation example 1
The preparation of three (1,3- diphenyl -1,1,3,3- tetramethyl, two silicon substrate amine) neodymium, structural formula are as follows：
In the presence of nitrogen, NdCl is introduced in flask3(2.1 mMs) and 1,3- diphenyl -1,1,3,3-
Two silicon substrate amine of tetramethyl (6.5 mMs), and 25 milliliters of THF is added thereto, at 25 DEG C
Stirring 30 minutes, subsequently at 50 DEG C carries out vacuum distillation to solution and is condensed into 1-2 milliliters, subsequently adds
Enter 0.5 milliliter of ether.Clear crystal is obtained in the solution.
Preparation example 2
The preparation of three (1,3- dibutyl -1,1,3,3- tetramethyl, two silicon substrate amine) neodymium, structural formula are as follows：
In the presence of nitrogen, NdCl is introduced in flask3(2.0 mMs) and 1,3- dibutyl -1,1,3,3-
Two silicon substrate amine of tetramethyl (7.5 mMs)；And 25 milliliters of pyridine is added thereto, stir at 20 DEG C
Mix 60 minutes, subsequently vacuum distillation to solution is carried out at 50 DEG C and be condensed into 1-2 milliliters, be subsequently added
0.5 milliliter of ether.Clear crystal is obtained in the solution.
Preparation example 3
The preparation of three (1,3- diphenyl -1,1,3,3- tetramethyl, two silicon substrate amine) cerium, structural formula are as follows：
In the presence of nitrogen, CeCl is introduced in flask3(2.0 mMs) and 1,3- diphenyl -1,1,3,3-
Two silicon substrate amine of tetramethyl (7.0 mMs)；And 25 milliliters of acetonitrile is added thereto, at 40 DEG C
Stirring 20 minutes, subsequently at 50 DEG C carries out vacuum distillation to solution and is condensed into 1-2 milliliters, subsequently adds
Enter 0.5 milliliter of ether.Clear crystal is obtained in the solution.
Preparation example 4
The preparation of two (1,3- diphenyl -1,1,3,3- tetramethyl, two silicon substrate amine) tetrahydrofuran neodymium, structural formula are as follows
It is shown：
In the presence of nitrogen, NdCl is introduced in flask3(2.1 mMs) and 1,3- diphenyl -1,1,3,3-
Two silicon substrate amine of tetramethyl (4.0 mMs)；And 25 milliliters of THF is added thereto, at 30 DEG C
Stirring 30 minutes, subsequently at 50 DEG C carries out vacuum distillation to solution and is condensed into 1-2 milliliters, subsequently adds
Enter 0.5 milliliter of ether.Clear crystal is obtained in the solution.
Preparation example 5
The preparation of two (1,3- diphenyl -1,1,3,3- tetramethyl, two silicon substrate amine) pyridine neodymium, structural formula are as follows：
In the presence of nitrogen, NdCl is introduced in flask3(2.1 mMs) and 1,3- diphenyl -1,1,3,3-
Two silicon substrate amine of tetramethyl (4.0 mMs)；And 25 milliliters of pyridine is added thereto, at 40 DEG C
Stirring 20 minutes, subsequently at 50 DEG C carries out vacuum distillation to solution and is condensed into 1-2 milliliters, subsequently adds
Enter 0.5 milliliter of ether.Clear crystal is obtained in the solution.
Preparation example 6
The preparation of two (1,3- diphenyl -1,1,3,3- tetrapropyl, two silicon substrate amine) tetrahydrofuran cerium, structural formula are as follows
It is shown：
In the presence of nitrogen, CeCl is introduced in flask3(2.1 mMs) and 1,3- diphenyl -1,1,3,3-
Two silicon substrate amine of tetrapropyl (4.0 mMs)；And 25 milliliters of THF is added thereto, at 45 DEG C
Stirring 20 minutes, subsequently at 50 DEG C carries out vacuum distillation to solution and is condensed into 1-2 milliliters, subsequently adds
Enter 0.5 milliliter of ether.Clear crystal is obtained in the solution.
Preparation example 7
The preparation of (1,3- dipropyl -1,1,3, the 3- tetrabutyl, two silicon substrate amine)-two tetrahydrofuran ceriums, structural formula is such as
Shown in lower：
In the presence of nitrogen, CeCl is introduced in flask3(2.1 mMs) and 1,3- dipropyl -1,1,3,3-
Two silicon substrate amine of the tetrabutyl (2.0 mMs)；And 25 milliliters of THF is added thereto, at 30 DEG C
Stirring 25 minutes, subsequently at 50 DEG C carries out vacuum distillation to solution and is condensed into 1-2 milliliters, subsequently adds
Enter 0.5 milliliter of ether.Clear crystal is obtained in the solution.
Preparation example 8
The preparation of (1,3- dicyclohexyl -1,1,3,3- tetramethyl, two silicon substrate amine)-two pyridine neodymiums, structural formula are as follows
It is shown：
In the presence of nitrogen, NdCl is introduced in flask3(2.1 mMs) and 1,3- dicyclohexyl -1,1,3,3-
Two silicon substrate amine of tetramethyl (2.0 mMs)；And 25 milliliters of pyridine is added thereto, at 50 DEG C
Stirring 20 minutes, subsequently at 50 DEG C carries out vacuum distillation to solution and is condensed into 1-2 milliliters, subsequently adds
Enter 0.5 milliliter of ether.Clear crystal is obtained in the solution.
Preparation example 9
The preparation of two (1,3- Hexaethyl, two silicon nitrogen amine) acetonitrile neodymium, structural formula are as follows：
Under a nitrogen, NdCl is introduced in flask3(1.1 mMs) and hexaethyl disilazine (2.1
MM)；And 25 milliliters of acetonitrile is added thereto, stir 30 minutes at 35 DEG C, subsequently exist
Vacuum distillation to solution is carried out at 50 DEG C and is condensed into 1-2 milliliters, be subsequently added 0.5 milliliter of ether.
Clear crystal is obtained in solution.
Embodiment 1
In the presence of nitrogen, the normal hexane of 50mL is introduced in flask, 0.24mmol preparation examples 1 are obtained
Rare-earth chemicals and 4.1mmol isoprene, temperature be 30 DEG C at contact 5 minutes；
1.0mmol triisobutyl aluminiums are subsequently introduced, are to contact 30 minutes at 30 DEG C in temperature；It is subsequently introduced
0.72mmol diethyl aluminum chlorides, are to be aged 2h at 60 DEG C in temperature；It is subsequently introduced 0.96mol isoamyls
Diene is polymerized, and is to react 3h at 30 DEG C in temperature, is subsequently made reaction terminating by adding methanol,
Obtain polymeric articles.
As a result：In polymeric articles, cis- Isosorbide-5-Nitrae linkage content is 99.7 weight %, and molecular weight distribution is 1.8.
Embodiment 2
In the presence of nitrogen, the normal hexane of 50mL is introduced in flask, 0.24mmol preparation examples 2 are obtained
Rare-earth chemicals and 7.2mmol isoprene, temperature be 35 DEG C at contact 7 minutes；
1.44mmol diisobutylaluminium hydrides are subsequently introduced, are to contact 20 minutes at 35 DEG C in temperature；Subsequently
0.72mmol diisobutyl aluminum chlorides are introduced, and are 2.5h to be aged at 60 DEG C in temperature；It is subsequently introduced 1mol
Isoprene is polymerized, and is to react 4h at 35 DEG C in temperature, is subsequently made reaction end by adding methanol
Only, polymeric articles are obtained.
As a result：In polymeric articles, cis- Isosorbide-5-Nitrae linkage content is 99.5 weight %, and molecular weight distribution is 1.8.
Embodiment 3
In the presence of nitrogen, the normal hexane of 50mL is introduced in flask, 0.24mmol preparation examples 3 are obtained
Rare-earth chemicals and 7.2mmol isoprene, temperature be 20 DEG C at contact 15 minutes；
1.44mmol triethyl aluminums are subsequently introduced, are to contact 30 minutes at 20 DEG C in temperature；It is subsequently introduced
0.72mmol diisobutyl aluminum chlorides, are to be aged 3h at 50 DEG C in temperature；It is subsequently introduced 1.2mol isoamyls
Diene is polymerized, and is to react 3h at 60 DEG C in temperature, is subsequently made reaction terminating by adding methanol,
Obtain polymeric articles.
As a result：In polymeric articles, cis- Isosorbide-5-Nitrae linkage content is 99.5 weight %, and molecular weight distribution is 1.9.
Embodiment 4-5
Embodiment 4-5 is carried out using method similar to Example 1, except that, in embodiment 4
Made using the preparation example 1 in the Rare-earth chemicals alternative embodiment 1 that preparation example 4 is prepared
The standby Rare-earth chemicals for obtaining；The rare earth gold prepared using preparation example 5 in embodiment 5
The Rare-earth chemicals that preparation example 1 in category organic compound alternative embodiment 1 is prepared.
Remaining is in the same manner as in Example 1.
As a result：In the polymeric articles that embodiment 4 is obtained cis- Isosorbide-5-Nitrae linkage content be 99.6 weight %, molecule
Amount is distributed as 1.7；
In the polymeric articles that embodiment 5 is obtained cis- Isosorbide-5-Nitrae linkage content be 99.6 weight %, molecular weight distribution
For 1.8.
Embodiment 6-7
Embodiment 6-7 is carried out using method similar to Example 3, except that, in embodiment 6
Made using the preparation example 3 in the Rare-earth chemicals alternative embodiment 3 that preparation example 6 is prepared
The standby Rare-earth chemicals for obtaining；The rare earth gold prepared using preparation example 7 in embodiment 7
The Rare-earth chemicals that preparation example 3 in category organic compound alternative embodiment 3 is prepared.
Remaining is in the same manner as in Example 3.
As a result：In the polymeric articles that embodiment 6 is obtained cis- Isosorbide-5-Nitrae linkage content be 99.4 weight %, molecule
Amount is distributed as 1.8；
In the polymeric articles that embodiment 7 is obtained cis- Isosorbide-5-Nitrae linkage content be 99.5 weight %, molecular weight distribution
For 1.9.
Embodiment 8-9
Embodiment 8-9 is carried out using method similar to Example 2, except that, in embodiment 8
Made using the preparation example 2 in the Rare-earth chemicals alternative embodiment 2 that preparation example 8 is prepared
The standby Rare-earth chemicals for obtaining；The rare earth gold prepared using preparation example 9 in embodiment 9
The Rare-earth chemicals that preparation example 2 in category organic compound alternative embodiment 2 is prepared.
Remaining is in the same manner as in Example 2.
As a result：In the polymeric articles that embodiment 8 is obtained cis- Isosorbide-5-Nitrae linkage content be 99.5 weight %, molecule
Amount is distributed as 1.9；
In the polymeric articles that embodiment 9 is obtained cis- Isosorbide-5-Nitrae linkage content be 99.3 weight %, molecular weight distribution
For 1.7.
Comparative example 1
Polymeric articles are prepared according to the method described in embodiment 1, except that, adopt in this comparative example
The Rare-earth chemicals prepared with the preparation example 1 in Neodymium chloride alternative embodiment 1.
Remaining is in the same manner as in Example 1.
As a result：Polymeric articles cannot be detected.
Comparative example 2
Polymeric articles are prepared according to the method described in embodiment 2, except that, adopt in this comparative example
The Rare-earth chemicals prepared with the preparation example 2 in neodymium oxalate alternative embodiment 2.
Remaining is in the same manner as in Example 2.
As a result：Polymeric articles cannot be detected.
Comparative example 3
Polymeric articles are prepared according to the method described in embodiment 3, except that, adopt in this comparative example
With the Nd (N (SiMe in Macro.Chem.Phys. (200,1163)3)2)3Preparation example in alternative embodiment 3
3 Rare-earth chemicals for preparing.
Remaining is in the same manner as in Example 3, obtains polymeric articles.
As a result：In polymeric articles, cis- Isosorbide-5-Nitrae linkage content is 93.6 weight %, and molecular weight distribution is 2.7.
Comparative example 4
Polymeric articles are prepared according to the method described in embodiment 2, except that, adopt in this comparative example
With the Nd (N (SiMe in Macro.Chem.Phys. (200,1163)3)2)3Preparation example in alternative embodiment 2
2 Rare-earth chemicals for preparing.
Remaining is in the same manner as in Example 2, obtains polymeric articles.
As a result：In polymeric articles, cis- Isosorbide-5-Nitrae linkage content is 87.6 weight %, and molecular weight distribution is 3.4.
Comparative example 5
Polymeric articles are prepared according to the method described in embodiment 1, except that, adopt in this comparative example
With the Nd (N (SiMe in Macro.Chem.Phys. (200,1163)3)2)3Preparation example in alternative embodiment 1
1 Rare-earth chemicals for preparing.
Remaining is in the same manner as in Example 1, obtains polymeric articles.
As a result：In polymeric articles, cis- Isosorbide-5-Nitrae linkage content is 80.7 weight %, and molecular weight distribution is 3.2.
By the result of embodiment 1-9 and comparative example 1-5 it is recognised that being prepared into using the method for the present invention
The cis- Isosorbide-5-Nitrae linkage content of the polyisoprene for arriving is higher, and the product molecular weight distribution for obtaining is narrower,
Suitable industrialized production.
And, can also be seen that from the result of embodiment 1-9：The polymerization produce that the method for the present invention is obtained
The cis-content of product is little with the change fluctuation of reaction condition, and molecular weight distribution is also narrower.However, comparative example
The result of 3-5 shows, using containing Nd (N (SiMe3)2)3Catalyst polyreaction when, obtain
Polymeric articles in cis-content it is big with the change fluctuation of reaction condition, and the molecular weight of the product for obtaining
Distribution is also wider.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, the present invention are no longer separately illustrated to various possible compound modes.
Additionally, combination in any between a variety of embodiments of the present invention, can also be carried out, as long as its
Without prejudice to the thought of the present invention, which should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of method for preparing polyisoprene, the method include：Under the polymerization conditions, will
Isoprene monomer carries out haptoreaction with rare earth catalyst composition, in the rare earth catalyst composition
Containing Rare-earth chemicals, the compound containing aluminium element and halogen source, the change containing aluminium element
Compound is alkyl aluminum and/or alkyl aluminium hydride, it is characterised in that the Rare-earth chemicals have
Structure shown in formula (I)：
Wherein, M is any one in lanthanide rare metallic element；
R1、R2、R3、R4、R5And R6It is identical or different, it is each independently selected from hydrogen, C1-8Alkyl,
C6-12Aryl, and the R1、R2、R3、R4、R5And R6It is asynchronously in hydrogen and methyl
It is at least one；
L is-OR7Or-NR8, wherein, the R7Formed together with oxygen atom containing 2-10 carbon atom
Heterocycle, the R8The heterocycle containing 2-10 carbon atom or the R are formed together with nitrogen-atoms8
For C1-4Alkyl；
X is 1,2 or 3, and y=3-x.
2. method according to claim 1, wherein, in the structure shown in formula (I), M is
Neodymium or cerium；
R1、R2、R3、R4、R5And R6It is identical or different, it is each independently selected from hydrogen, C1-6Alkyl,
C6-10Aryl, and the R1、R2、R3、R4、R5And R6It is asynchronously in hydrogen and methyl
It is at least one；
L is-OR7Or-NR8, wherein, the R7Formed together with oxygen atom containing 2-7 carbon atom
Heterocycle, the R8The heterocycle containing 2-7 carbon atom or the R are formed together with nitrogen-atoms8For
C1-4Alkyl；
X is 1,2 or 3, and y=3-x.
3. method according to claim 2, wherein, in the structure shown in formula (I), M is
Neodymium or cerium；
R1、R2、R3、R4、R5And R6It is identical or different, it is each independently selected from hydrogen, methyl, second
Base, n-pro-pyl, isopropyl, normal-butyl, phenyl, aminomethyl phenyl, 3,5-dimethylphenyl, trimethylphenyl,
Methylethyl phenyl, ethylphenyl, diethyl phenyl and triethyl group phenyl, and the R1、R2、R3、
R4、R5And R6It is asynchronously at least one in hydrogen and methyl；
L is selected from tetrahydrofuran, pyridine and acetonitrile；
X is 1 or 2, and y=3-x.
4. method according to claim 2, wherein, in the structure shown in formula (I), M is
Neodymium or cerium；
R1、R2、R3、R4、R5And R6It is identical or different, it is each independently selected from hydrogen, methyl, second
Base, n-pro-pyl, isopropyl, normal-butyl, phenyl, aminomethyl phenyl, 3,5-dimethylphenyl, trimethylphenyl,
Methylethyl phenyl, ethylphenyl, diethyl phenyl and triethyl group phenyl, and the R1、R2、R3、
R4、R5And R6It is asynchronously at least one in hydrogen and methyl；
X is 3, and y is 0.
5. the method according to any one in claim 1-4, wherein, in the rare earth catalyst
In agent compositionss, the content of the Rare-earth chemicals, the compound containing aluminium element and halogen source
Mol ratio is 1：2-10：1-30；Preferably 1：4-8：1-15.
6. the method according to any one in claim 1-4, wherein, the alkyl aluminum is three
One kind in aluminium methyl, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, triisobutyl aluminium and three amyl group aluminum
Or it is various；It is preferred that the alkyl aluminum is triisobutyl aluminium and/or triethyl aluminum；
The alkyl aluminium hydride is diethyl aluminium hydride and/or hydrogenation dibutyl aluminum；It is preferred that the hydrogenation alkane
Base aluminum is hydrogenation dibutyl aluminum.
7. the method according to any one in claim 1-4, wherein, the halogen source is alkyl
Aluminum halide；It is preferred that
The aikyl aluminum halide is diethyl aluminum chloride and/or diisobutyl aluminum chloride.
8. method according to claim 1, wherein, the haptoreaction is present in organic solvent
Under carry out, the organic solvent selected from normal hexane, pentane, hexane, heptane, hexamethylene, toluene, two
At least one in toluene and chlorobenzene；It is preferred that
The organic solvent is normal hexane.
9. method according to claim 1, wherein, the catalytic condition includes：Temperature
Spend for 0-100 DEG C, the time is 0.1-24h；It is preferred that
The isoprene monomer and the consumption of the rare earth catalyst composition in terms of rare earth metal
Mol ratio is 1000-10000：1.
10. method according to claim 1, wherein, also contain in the rare earth catalyst composition
Have and be ready to use in the isoprene monomer for carrying out polyreaction；It is preferred that
It is described to be ready to use in the isoprene monomer and the Rare-earth chemicals for carrying out polyreaction
Content mol ratio be 1-120：1.
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