CN106589239A - Butadiene/isoprene copolymer preparation method - Google Patents
Butadiene/isoprene copolymer preparation method Download PDFInfo
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- CN106589239A CN106589239A CN201510679313.9A CN201510679313A CN106589239A CN 106589239 A CN106589239 A CN 106589239A CN 201510679313 A CN201510679313 A CN 201510679313A CN 106589239 A CN106589239 A CN 106589239A
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Abstract
The present invention relates to the field of catalytic polymerization, and discloses a butadiene/isoprene copolymer preparation method, wherein the copolymer contains a butadiene chain segment unit and an isoprene chain segment unit, the cis-1,4 bond content in the butadiene chain segment unit is more than or equal to 98.0%, the cis-1,4 bond content in the isoprene chain segment unit is more than or equal to 98.0%, and the molecular weight distribution of the copolymer is 1.2-2.1. The preparation method comprises that under a polymerization reaction condition, a butadiene monomer, an isoprene monomer and a rare earth catalyst composition are subjected to a contact reaction, wherein the rare earth catalyst composition contains a rare earth metal organic compound, an aluminum-containing compound and a halogen source, and the rare earth metal organic compound has a structure represented by a formula (I). According to the present invention, the cis-1,4 bond contents in the butadiene chain segment unit and the isoprene chain segment unit of the butadiene/isoprene copolymer are high, and the molecular weight distribution is narrow. The formula (I) is defined in the specification.
Description
Technical field
The present invention relates to catalytic polymerization field, in particular it relates to one kind to prepare butadiene/isoprene common
The method of polymers.
Background technology
For catalytic polymerization conjugated diene rare earth catalyst composition it is general all by rare earth catalyst, help
Catalyst and halogen source are constituted.Conjugated diene can be catalyzed becomes the polymer with high-cis structure.It is special
Not, these polymer can be widely used on manufacture automobile tire.In rare earth catalyst, neodymium series
The low price of catalyst, expression activitiy is high.
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.
CN1484657A describes a kind of rare earth catalyst composition for conjugate diene polymerization, should
Compositionss include：
A kind of-conjugated diene monomer,
The rare earth metal salt of-organic phosphoric acid,
- formula is AlR3Or HAlR2Alkyl aluminum,
- the halogen donor being made up of alkyl aluminium halide.
In this carbon monoxide-olefin polymeric, the cis-Isosorbide-5-Nitrae linkage content of resulting polyisoprene is 95.7 weights
Amount weight % of % to 98.7.
Conventional Nd-based catalyst includes alkyl carboxylic acid neodymium, alkoxyl neodymium and phosphate ester neodymium, and these parts are all
It is that coordinate bond is formed with oxygen and neodymium.Up to now, polyreaction is carried out with what nitrogen and neodymium formed coordinate bond
It is Catalyzed by Organometallic Compounds agent research and few.
Boisson has used Nd (N (SiMe on Macro.Chem.Phys. (200,1163)3)2)3As urging
Agent is polymerized to butadiene, and in addition to neodymium catalyst, the carbon monoxide-olefin polymeric also includes：
- as the butadiene of conjugated diene monomer,
- as the triisobutyl aluminium of alkylating reagent,
- as the diethylaluminum chloride of aikyl aluminum halide.
In this carbon monoxide-olefin polymeric, nitrogen and neodymium define coordinate bond in rare earth catalyst, and resulting is poly-
The cis-1,4 chaining of butadiene is 93.1 weight % to 99.0 weight %.But the carbon monoxide-olefin polymeric
Preparation method it is excessively simple, be simply simply mixed.This carbon monoxide-olefin polymeric is only used for the poly- of butadiene
Close, when the copolymerization for butadiene and isoprene, harshness is required to reaction condition, and by condition shadow
Sound is larger, and the cis-content of the product of acquisition is not high and molecular weight distribution is wider, and this is unfavorable for industrial metaplasia
Optimum catalyst compositing formula carries out the preparation of polymer used in product.
The content of the invention
The purpose of the present invention is the defect for overcoming prior art, there is provided a kind of cis- Isosorbide-5-Nitrae linkage content is in butadiene
Higher and narrow molecular weight distribution butadiene/isoprene in chain segment unit and isoprene segment unit
Copolymer and preparation method thereof.
To achieve these goals, the present invention provides a kind of side for preparing butadiene/isoprene copolymer
Method, the method includes：Under the polymerization conditions, by divinylic monomer and isoprene monomer and rare earth
Carbon monoxide-olefin polymeric carries out haptoreaction, organises containing rare earth metal in the rare earth catalyst composition
Compound, the compound containing aluminium element and halogen source, the compound containing aluminium element is alkyl aluminum and/or hydrogen
Change alkyl aluminum, the Rare-earth chemicals have 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.
The butadiene segment unit and isoprene chain of butadiene/isoprene copolymer that the present invention is provided
Cis- 1,4 linkage content is higher in segment unit and narrow molecular weight distribution.
In addition, the present inventor is found that under study for action the novel rare-earth based on rare earth metal salt is catalyzed
Agent compositionss, the novel rare-earth carbon monoxide-olefin polymeric includes 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 forms coordinate bond by nitrogen and rare earth element, carry out butadiene/
The polymerization of isoprene copolymer, realizes butadiene segment unit and isoprene chain in copolymer
Cis-content in segment unit is all higher than or equal to 98 weight %, preferably greater than or equal to 99 weight %,
Molecular weight distribution is less than or equal to 2.1.
Butadiene/isoprene copolymer that the present invention is provided also has good resistance to low temperature, wear-resisting
The performance such as property and low temperature rolling resistance.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
The specific embodiment of the present invention is described in detail below.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 butadiene/isoprene copolymer, the method includes：
Under the polymerization conditions, divinylic monomer and isoprene monomer are carried out with rare earth catalyst composition
Haptoreaction, in the rare earth catalyst composition containing Rare-earth chemicals, containing aluminium element
Compound and halogen source, the compound containing aluminium element is alkyl aluminum and/or alkyl aluminium hydride, described dilute
Earth metal 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.
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 is bonded with the M 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 is no special 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 present invention can also be concentrated the product that above-mentioned contact is obtained, 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；Preferably hydrogenate dibutyl aluminum.
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 includes：Temperature is 5-80 DEG C, and the time is 0.2-12h.Especially,
The catalytic time zero exists in same system to participate in catalytic whole key elements
When middle.
Preferably, the total amount of the divinylic monomer and the isoprene monomer with terms of rare earth metal
The mol ratio of the consumption of the rare earth catalyst composition is 1000-10000：1；More preferably
2000-9000：1；Particularly preferably 3500-9000：1.
Preferably, the consumption mol ratio of the divinylic monomer and the isoprene monomer is 1-10：1；
More preferably 1-5：1.
Can also contain in the rare earth catalyst composition and be ready to use in the monomer for carrying out polyreaction.Institute
In stating rare earth catalyst composition, the monomer that carries out polyreaction and the rare earth metal of being ready to use in has
The mol ratio of machine compound is 1-120：1；Preferably 10-80：1.Under this condition, can obtain more
Good catalysis activity.
It is divinylic monomer and/or the isoprene list to be ready to use in and carry out the monomer of polyreaction
Body.
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 the monomer for carrying out 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 compound containing aluminium element and it is optional described in
Be ready to use in the conjugated diene for carrying out polyreaction carries out hybrid reaction in inert hydrocarbon solvent；
(2) halogen source is introduced 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
Containing butadiene segment unit and isoprene segment unit, the butadiene in the copolymer product for obtaining
Cis- Isosorbide-5-Nitrae linkage content >=98.0% in chain segment unit, the cis- Isosorbide-5-Nitrae key in the isoprene segment unit contains
Amount >=98.0%, the molecular weight distribution of the copolymer is 1.2-2.1.Under preferable case, the butadiene
Cis- Isosorbide-5-Nitrae linkage content >=98.5% in chain segment unit, the cis- Isosorbide-5-Nitrae key in the isoprene segment unit contains
Amount >=98.5%, the molecular weight distribution of the copolymer is 1.4-1.9.
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, butadiene segment unit and isoprene segment unit in the copolymer product
In cis- 1,4 linkage content measured using C13 nuclear magnetic resonance methods or near-infrared analysis method；The butadiene/
The molecular weight distribution of isoprene copolymer is by gpc measurement；Prepare metal-organic raw material by
Commercial sources are obtained, especially, in the purchase of Sigma-Aldrich medicaments company.
Preparation example 1-9 is used to prepare Rare-earth chemicals.
Embodiment 1-9 is used to illustrate the method for preparing butadiene/isoprene copolymer of the present invention.
Preparation example 1
The preparation of three (1,3- diphenyl -1, the silicon substrate amine of 1,3,3- tetramethyl two) neodymiums, structural formula is as follows：
In the presence of nitrogen, NdCl is introduced in flask3(2.1 mMs) and 1,3- diphenyl -1,1,3,3-
The silicon substrate amine of tetramethyl two (6.5 mMs), and 25 milliliters of THF is added thereto, at 25 DEG C
Stirring 30 minutes, subsequently carries out vacuum distillation to solution at 50 DEG C 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, the silicon substrate amine of 1,3,3- tetramethyl two) neodymiums, structural formula is as follows：
In the presence of nitrogen, NdCl is introduced in flask3(2.0 mMs) and 1,3- dibutyl -1,1,3,3-
The silicon substrate amine of tetramethyl two (7.5 mMs)；And be added thereto 25 milliliters of pyridine, 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, the silicon substrate amine of 1,3,3- tetramethyl two) ceriums, structural formula is as follows：
In the presence of nitrogen, CeCl is introduced in flask3(2.0 mMs) and 1,3- diphenyl -1,1,3,3-
The silicon substrate amine of tetramethyl two (7.0 mMs)；And be added thereto 25 milliliters of acetonitrile, at 40 DEG C
Stirring 20 minutes, subsequently carries out vacuum distillation to solution at 50 DEG C 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, the silicon substrate amine of 1,3,3- tetramethyl two) tetrahydrofuran neodymiums, structural formula is 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-
The silicon substrate amine of tetramethyl two (4.0 mMs)；And be added thereto 25 milliliters of THF, at 30 DEG C
Stirring 30 minutes, subsequently carries out vacuum distillation to solution at 50 DEG C 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, the silicon substrate amine of 1,3,3- tetramethyl two) pyridine neodymiums, structural formula is as follows：
In the presence of nitrogen, NdCl is introduced in flask3(2.1 mMs) and 1,3- diphenyl -1,1,3,3-
The silicon substrate amine of tetramethyl two (4.0 mMs)；And be added thereto 25 milliliters of pyridine, at 40 DEG C
Stirring 20 minutes, subsequently carries out vacuum distillation to solution at 50 DEG C 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, the silicon substrate amine of 1,3,3- tetrapropyl two) tetrahydrofuran ceriums, structural formula is 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-
The silicon substrate amine of tetrapropyl two (4.0 mMs)；And be added thereto 25 milliliters of THF, at 45 DEG C
Stirring 20 minutes, subsequently carries out vacuum distillation to solution at 50 DEG C 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, the silicon substrate amine of 1,3, the 3- tetrabutyl two)-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-
The silicon substrate amine of the tetrabutyl two (2.0 mMs)；And be added thereto 25 milliliters of THF, at 30 DEG C
Stirring 25 minutes, subsequently carries out vacuum distillation to solution at 50 DEG C 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, the silicon substrate amine of 1,3,3- tetramethyl two)-two pyridine neodymiums, structural formula is 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-
The silicon substrate amine of tetramethyl two (2.0 mMs)；And be added thereto 25 milliliters of pyridine, at 50 DEG C
Stirring 20 minutes, subsequently carries out vacuum distillation to solution at 50 DEG C 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 (the silicon nitrogen amine of 1,3- Hexaethyl two) acetonitrile neodymiums, structural formula is as follows：
Under a nitrogen, NdCl is introduced in flask3(1.1 mMs) and hexaethyl disilazine (2.1
MM)；And be added thereto 25 milliliters of acetonitrile, 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 butadiene, temperature be 30 DEG C at contact 5 minutes；
1.0mmol triisobutyl aluminiums are subsequently introduced, are contacted 30 minutes in the case where temperature is for 30 DEG C；It is subsequently introduced
0.72mmol diethyl aluminum chlorides, in the case where temperature is for 60 DEG C 2h is aged；It is subsequently introduced 0.48mol fourths two
Alkene and 0.48mol isoprene are polymerized, and 3h are reacted in the case where temperature is for 30 DEG C, subsequently by adding
Methanol makes reaction terminating, obtains polymeric articles.
As a result：In polymer the cis- Isosorbide-5-Nitrae linkage content of butadiene segment unit be 99.2 weight %, isoamyl two
The cis- Isosorbide-5-Nitrae linkage content of alkene chain segment unit is 99.0 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 contacted 20 minutes in the case where temperature is for 35 DEG C；Subsequently
0.72mmol diisobutyl aluminum chlorides are introduced, in the case where temperature is for 60 DEG C 2.5h is aged；It is subsequently introduced 0.4mol
Butadiene and 0.6mol isoprene are polymerized, and 4h are reacted in the case where temperature is for 35 DEG C, subsequently by adding
Entering methanol makes reaction terminating, obtains polymeric articles.
As a result：In polymer the cis- Isosorbide-5-Nitrae linkage content of butadiene segment unit be 99.5 weight %, isoamyl two
The cis- Isosorbide-5-Nitrae linkage content of alkene chain segment unit is 98.9 weight %, and molecular weight distribution is 1.5.
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 butadiene, temperature be 20 DEG C at contact 15 minutes；
1.44mmol triethyl aluminums are subsequently introduced, are contacted 30 minutes in the case where temperature is for 20 DEG C；It is subsequently introduced
0.72mmol diisobutyl aluminum chlorides, in the case where temperature is for 50 DEG C 3h is aged；It is subsequently introduced 0.8mol fourths two
Alkene and 0.2mol isoprene are polymerized, and 3h are reacted in the case where temperature is for 60 DEG C, subsequently by adding first
Alcohol makes reaction terminating, obtains polymeric articles.
As a result：In polymer the cis- Isosorbide-5-Nitrae linkage content of butadiene segment unit be 99.2 weight %, isoamyl two
The cis- Isosorbide-5-Nitrae linkage content of alkene chain segment unit is 99.0 weight %, and molecular weight distribution is 1.7.
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：Cis- 1,4 linkage content of butadiene segment unit is 99.0 in the polymer that embodiment 4 is obtained
Weight %, the cis- Isosorbide-5-Nitrae linkage content of isoprene segment unit is 99.0 weight %, and molecular weight distribution is 1.7；
The cis- Isosorbide-5-Nitrae linkage content of butadiene segment unit is 99.1 weight % in the polymer that embodiment 5 is obtained,
The cis- Isosorbide-5-Nitrae linkage content of isoprene segment unit is 99.0 weight %, and molecular weight distribution is 1.7.
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：Cis- 1,4 linkage content of butadiene segment unit is 99.3 in the polymer that embodiment 6 is obtained
Weight %, the cis- Isosorbide-5-Nitrae linkage content of isoprene segment unit is 99.0 weight %, and molecular weight distribution is 1.6；
The cis- Isosorbide-5-Nitrae linkage content of butadiene segment unit is 99.2 weight % in the polymer that embodiment 7 is obtained,
The cis- Isosorbide-5-Nitrae linkage content of isoprene segment unit is 99.1 weight %, and molecular weight distribution is 1.7.
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：Cis- 1,4 linkage content of butadiene segment unit is 99.5 in the polymer that embodiment 8 is obtained
Weight %, the cis- Isosorbide-5-Nitrae linkage content of isoprene segment unit is 99.1 weight %, and molecular weight distribution is 1.6；
The cis- Isosorbide-5-Nitrae linkage content of butadiene segment unit is 99.4 weight % in the polymer that embodiment 9 is obtained,
The cis- Isosorbide-5-Nitrae linkage content of isoprene segment unit is 98.9 weight %, and molecular weight distribution is 1.5.
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, obtains polymeric articles.
As a result：In polymer the cis- Isosorbide-5-Nitrae linkage content of butadiene segment unit be 68.2 weight %, isoamyl two
The cis- Isosorbide-5-Nitrae linkage content of alkene chain segment unit is 64.0 weight %, and molecular weight distribution is 3.7.
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, obtains polymeric articles.
As a result：In polymer the cis- Isosorbide-5-Nitrae linkage content of butadiene segment unit be 74.5 weight %, isoamyl two
The cis- Isosorbide-5-Nitrae linkage content of alkene chain segment unit is 85.7 weight %, and molecular weight distribution is 2.4.
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 polymer the cis- Isosorbide-5-Nitrae linkage content of butadiene segment unit be 86.3 weight %, isoamyl two
The cis- Isosorbide-5-Nitrae linkage content of alkene chain segment unit is 94.2 weight %, and molecular weight distribution is 2.6.
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 polymer the cis- Isosorbide-5-Nitrae linkage content of butadiene segment unit be 79.8 weight %, isoamyl two
The cis- Isosorbide-5-Nitrae linkage content of alkene chain segment unit is 89.3 weight %, and molecular weight distribution is 3.5.
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 polymer the cis- Isosorbide-5-Nitrae linkage content of butadiene segment unit be 8.3 weight %, isoamyl two
The cis- Isosorbide-5-Nitrae linkage content of alkene chain segment unit is 89.2 weight %, and molecular weight distribution is 3.7.
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
To butadiene/isoprene copolymer butadiene segment unit and isoprene segment unit in it is suitable
- Isosorbide-5-Nitrae linkage content is higher, and the product molecular weight distribution for obtaining is narrower, is adapted to industrialized production.
And, can also be seen that from the result of embodiment 1-9：The copolymerization 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
Copolymer product 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 is no longer separately illustrated to various possible compound modes.
Additionally, combination in any can also be carried out between a variety of embodiments of the present invention, as long as its
Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of method for preparing butadiene/isoprene copolymer, the method includes：In polyreaction
Under the conditions of, divinylic monomer and isoprene monomer are carried out into 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 compound containing aluminium element is alkyl aluminum and/or alkyl aluminium hydride, it is characterised in that described
Rare-earth chemicals have 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.
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 exists 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 total amount of the divinylic monomer and the isoprene monomer with it is described dilute in terms of rare earth metal
The mol ratio of the consumption of native carbon monoxide-olefin polymeric is 1000-10000：1.
10. method according to claim 1, wherein, the divinylic monomer and the isoamyl two
The consumption mol ratio of alkene monomer is 1-10：1；Preferably 1-5：1.
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