CN105524197B - A kind of preparation method of rare earth polybutadiene rubber - Google Patents
A kind of preparation method of rare earth polybutadiene rubber Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of rare earth polybutadiene rubber, this method includes：In presence of organic solvent with the conditions of solution polymerization, butadiene is contacted with rare earth catalyst, it is characterised in that contain the rare earth compounding of structure shown in formula (I) in the rare earth catalyst：Wherein, R1、R2And R3It is each independently hydrogen or C1‑C20Alkyl；R4And R5It is each independently hydrogen or C1‑C6Alkyl；Ln is one kind in rare earth metal；THF represents tetrahydrofuran.The suitable Isosorbide-5-Nitrae structural content that the preparation method provided by the invention enables to obtained rare earth polybutadiene rubber is high, and the high conversion rate of substrate.
Description
Technical field
The present invention relates to a kind of preparation method of rare earth polybutadiene rubber.
Background technology
Since the sixties in last century, China found that rare earth compounding can be catalyzed diolefin polymerization, in the world to rare earth metal
The research of organic compound catalytic polymerization has made great progress, and develops series of rare earth catalyst system and catalyzing, such as neodymium chloride/alkyl
Aluminum binary system, carboxylic acid neodymium/alkyl aluminum/halide ternary system and carboxylic acid neodymium/alkyl aluminum/alkyl halide/isoprene
Quaternary catalytic system, industrialization is turned into the high-cis polybutadiene and polyisoprene rubber of such rare earth catalyst synthesis
The important kind of production.
In recent years, some luxuriant, half luxuriant and non-luxuriant cationic catalyzing of rare-earth metal systems turn into study hotspot again.It is this kind of to urge
Agent limits its geometric configuration, can improve the efficiency and selectivity of catalyst, realize conjugation by changing the part of complex
Diene polymerization or the combined polymerization with monoolefine.Rare earth metallocene/alkyl aluminum/organic the boron salt applied such as Riken researcher
Cationic catalysts system has very high catalytic activity to combined polymerization and with the combined polymerization of vinyl aromatic compounds,
And the characteristics of polymerisation active polymerization, it for details, reference can be made to US2002/0119889, US6,596,828, US6,960,
631B2, and US6,683,140B2, but to be obtained higher than 95 weight % using these technologies when carrying out the polymerization along butadiene
During the cis- Isosorbide-5-Nitrae selectivity of the above, it is necessary to carried out under the polymerization temperature less than subzero 30 DEG C, operating condition is very harsh.
Changchun Institute of Applied Chemistry of Chinese Academy of Sciences Cui east plum disclosed in CN101186663A a kind of NCN clamp type rareearth complexes and
Three component cationic catalyst system and catalyzings of alkyl aluminum, organic boron salt composition, are catalyzed isoamyl two in the range of subzero 20 DEG C to 80 DEG C
When alkene polymerize, cis- Isosorbide-5-Nitrae structural content is 55.0-98.8% in polymer；During Butadiene Polymerization, cis- Isosorbide-5-Nitrae in polymer
Structural content is 90.1-99.9%.
The content of the invention
The purpose of the present invention is on the basis of existing technology, there is provided a kind of new method for preparing rare earth polybutadiene rubber,
By using the present invention this method prepare rare earth polybutadiene rubber when can improve simultaneously rare earth polybutadiene rubber selectivity and
The conversion ratio of reaction substrate, and the method for the present invention is relative to the method reaction condition milder of prior art.
To achieve these goals, the present invention provides a kind of preparation method of rare earth polybutadiene rubber, and this method includes：Having
In the presence of solvent and under the conditions of solution polymerization, butadiene is contacted with rare earth catalyst, in the rare earth catalyst
Rare earth compounding containing structure shown in formula (I)：
Wherein, R1、R2And R3It is each independently hydrogen or C1-C20Alkyl；R4And R5It is each independently hydrogen or C1-C6's
Alkyl；Ln is one kind in rare earth metal；THF represents tetrahydrofuran.
When preparing rare earth polybutadiene rubber by using the above method of the present invention, rare earth polybutadiene rubber can be improved simultaneously
The conversion ratio of selectivity and reaction substrate.Such as it can be seen that being prepared using the method for the present invention from embodiments of the invention
During butadiene rubber, the cis- Isosorbide-5-Nitrae structural content of polymer while high conversion ratio is taken into account, can be made to be up to more than 97%, very
It can reach 99.6% to highest.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
In the present invention, in the case where not making opposite explanation, " the C1-C20Alkyl " can be straight chain or branched chain
Formula, instantiation can include but is not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tertiary fourth
Base, n-pentyl, 1- ethyl propyls, 2- methyl butyls, 3- methyl butyls, 2,2- dimethyl propyls, n-hexyl, 2- methyl amyls,
3- methyl amyls, 4- methyl amyls, n-heptyl, 2- methylhexyls, 3- methylhexyls, 4- methylhexyls, 5- methylhexyls, positive heptan
Base, n-octyl, n-nonyl, positive decyl, 3,7- dimethyl octyl group, dodecyl, n-tridecane base, n-tetradecane base, positive ten
Five alkyl, n-hexadecyl, n-octadecane base, NSC 77136 base and n-eicosane base.The C1-C5Straight or branched alkyl
Instantiation can include but is not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tertiary fourth
Base, n-pentyl, isopentyl, tertiary pentyl and neopentyl.
" the C1-C12Alkyl " can be straight chain or branched chain formula, instantiation can include but is not limited to：Methyl,
Ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, 1- ethyl propyls, 2- methyl butyls,
3- methyl butyls, 2,2- dimethyl propyls, n-hexyl, 2- methyl amyls, 3- methyl amyls, 4- methyl amyls, n-heptyl, 2- first
Base hexyl, 3- methylhexyls, 4- methylhexyls, 5- methylhexyls, n-heptyl, n-octyl, n-nonyl, positive decyl, 3,7- diformazans
Base octyl group and dodecyl.
" the C1-C6Alkyl " can be straight chain or branched chain formula, instantiation can include but is not limited to：Methyl, second
Base, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, 1- ethyl propyls, 2- methyl butyls, 3-
Methyl butyl, 2,2- dimethyl propyls, n-hexyl, 2- methyl amyls, 3- methyl amyls and 4- methyl amyls.
" the C1-C4Alkyl " can be straight chain or branched chain formula, instantiation can include but is not limited to：Methyl, second
Base, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group and the tert-butyl group.
" the C1-C3Alkyl " can be straight chain or branched chain formula, instantiation can include but is not limited to：Methyl, second
Base, n-propyl and isopropyl.
The invention provides a kind of preparation method of rare earth polybutadiene rubber, this method includes：In presence of organic solvent
Under the conditions of solution polymerization, butadiene is contacted with rare earth catalyst, knot shown in formula (I) is contained in the rare earth catalyst
The rare earth compounding of structure：
Wherein, R1、R2And R3It is each independently hydrogen or C1-C20Alkyl；R4And R5It is each independently hydrogen or C1-C6's
Alkyl；Ln is one kind in rare earth metal；THF represents tetrahydrofuran.
The present inventor has found under study for action, by specific, R1、R2、R3、R4And R5Formed rare earth is coordinated to coordinate
Fabulous catalytic effect can be obtained during component of the thing as the catalyst of Butadiene Polymerization.It is therefore preferred that in the present invention
In, R1、R2And R3It is each independently hydrogen or C1-C12Alkyl, R4And R5It is each independently hydrogen or C1-C3Alkyl；It is more excellent
Selection of land, in the present invention, R1、R2And R3It is identical, and be hydrogen or C1-C4Alkyl, R4And R5It is identical, and be methyl.
The present inventor has found under study for action, contains the rare earth compounding of specific rare earth element as catalysis fourth two
Good catalytic effect can be obtained during the catalyst of alkene polymerization.It is therefore preferred that Ln is Y, Lu, La, Nd, Sm, Eu, Sc and Tm
In one kind；It is highly preferred that Ln is Lu or Sc.
In the present invention, it is preferred to the rare earth compounding can be prepared with the following method：Shown in generation formula (I)
Under conditions of the rare earth compounding of structure, the compound of the compound of structure and structure shown in formula (III) shown in formula (II) is entered
Row reaction,
Ln(CH2Si(R4)3)2(CH2Si(R5)3)(THF)2Formula (III),
Wherein, the R in formula (II)1、R2And R3It is each independently hydrogen or C1-C20Alkyl；
R in formula (III)4And R5It is each independently hydrogen or C1-C6Alkyl；
Ln in formula (III) is one kind in rare earth metal；
THF in formula (III) represents tetrahydrofuran.
Wherein, as described above, R1、R2、R3、R4、R5, structure shown in the alternative groups of Ln and above-mentioned formula (I) rare earth
Corresponding group is identical respectively in complex, and the present invention will not be repeated here.
According to the present invention, there is the instantiation of the compound of structure shown in formula (II) can include but is not limited to：8-(N-
2,6- dimethyl) imido grpup 1,2- EEDQs, 8- (N-2,6- diisopropyls) imido grpup 1,2- EEDQs.Aforementioned substances are equal
It can be commercially available.
According to the present invention, the instantiation of the compound of structure can include but is not limited to shown in formula (III)：Lu
(CH2SiMe3)3(THF)2、Sc(CH2SiMe3)3(THF)2、Y(CH2SiMe3)3(THF)2.Aforementioned substances can by commercially available or
Common knowledge synthesizes to obtain.For example, Ln (CH2SiMe3)3(THF)2Can be according to document Journal of Polymer
Science:Part A:Method disclosed in Polymer Chemistry DOI10.1002/POLA pages 1376 synthesizes.
According to the present invention, the dosage with the compound of structure shown in formula (II) with the compound of structure shown in formula (III)
It can be selected and be changed in wider scope, as long as the rare earth compounding of structure shown in formula (I) can be obtained having i.e.
Can, for example, the mol ratio with the compound of structure shown in formula (II) and the compound of structure shown in formula (III) can be 1：
0.5-1.5, preferably 1:0.75-1.25.
The present invention is not particularly limited to the condition of the rare earth compounding of structure shown in the generation formula (I), Ke Yiwei
The conventional selection of this area.As a rule, the condition of the rare earth compounding of structure includes reaction temperature shown in the generation formula (I)
And the reaction time.Wherein, the reaction temperature can be selected and changed in wider scope, in order to be more beneficial for reacting
Progress, the reaction temperature can be subzero 20 DEG C to 60 DEG C, be preferably 0-20 DEG C.The extension in reaction time is advantageous to react
The raising of the conversion ratio of thing or the yield of reaction product, but reaction time long conversion ratio or reaction product to reactant
The increase rate of yield and unobvious, therefore, generally, the reaction time can be 4-16 hours, preferably 8-16
Hour.
In the present invention, the organic solvent for preparing rare earth compounding can be that existing various can be used as reacts matchmaker
The organic substance of Jie, for example, can be varsol and/or ether solvent.The varsol can be C1-C5Alkane or
Halogenated alkane, C5-C7Cycloalkane, the one or more in aromatic hydrocarbons and isoparaffin.The instantiation of the varsol can be with
Including but not limited to：N-hexane, pentane, normal heptane, pentane, dichloromethane, chloroform, hexamethylene, benzene, toluene, 1,4-
One or more in dioxane and tetrahydrofuran.The ether solvent can be C4-C15Monoether and/or polyether.It is described
The instantiation of ether solvent can include but is not limited to：Tert-butoxyethoxy ethane and/or tetrahydrofuran.Wherein, these
Solvent can be used alone, can also be used in mixed way.The dosage of the organic solvent can be tied according to formula (II)
The dosage of the compound of structure and the compound of structure shown in formula (III) is reasonably selected, for example, the dosage of the solvent can
To have the total concentration of the compound of structure shown in formula (II) and the compound of structure shown in formula (III) heavy as 1-30
Measure %, preferably 5-20 weight %.
According to the invention, it is further possible to structure shown in the compound of structure shown in formula (II) and formula (III) compound it
Between reaction after the completion of, organic solvent therein is removed.Wherein, this area can be used by removing the method for the organic solvent
Known various methods are carried out, for example, vacuum removal organic solvent, revolving removing organic solvent etc., on the other hand, people in the art
Member can know, will not be described in great detail herein.
In addition, in order to obtain sterling, the step of can also including product purification obtained above, the method for the purifying
Various purification process well known in the art can be used to carry out, such as recrystallized.Recrystallization solvent used for example can be just
Hexane and/or hexamethylene.
Under preferable case, in method of the present invention, also contain boride in the rare earth catalyst.
According to the present invention, the content of the rare earth compounding and boride can be selected and become in wider scope
It is dynamic, but in order that both materials can play preferably Butadiene Polymerization, under preferable case, the rare earth catalyst
In rare earth compounding and boride mol ratio be 1：0.9-1.1.
According to the present invention, the boride can be the existing various boracic chemical combination that can act as metallocene co-catalyst
Thing, for example, [Ph can be selected from3C][B(C6F5)4]、[PhMe2NH][B(C6F5)4] and B (C6F5)3In one or more.More than
Material can be commercially available.
According to the present invention, wherein, alkyl aluminum and/or alkyl aluminium hydride are also contained in the rare earth catalyst.
Heretofore described alkyl aluminum and/or alkyl aluminium hydride refer to alkyl aluminum, alkyl aluminium hydride or their mixing
Thing.It is preferred that the alkyl aluminum and/or alkyl aluminium hydride are trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, three amyl groups
One or more in aluminium, three hexyl aluminium, diethyl aluminium hydride and hydrogenation dibutyl aluminium；Preferably tri-butyl aluminum and/or hydrogenation
Dibutyl aluminium.Heretofore described alkyl aluminum and/or alkyl aluminium hydride refer to alkyl aluminum, alkyl aluminium hydride or their mixing
Thing.
According to the present invention, the content of the alkyl aluminum and/or alkyl aluminium hydride and rare earth compounding can be in wider model
Enclose it is interior selected and changed, but in order to which preferably Butadiene Polymerization, the alkyl aluminum and/or alkyl aluminium hydride always rubs
The ratio of the molal quantity of that number and rare earth compounding can be 10-50：1.Above material can be commercially available.
According to a kind of preferred embodiment of the present invention, above-mentioned formula (I) can be contained in the rare earth catalyst
Rare earth compounding, boride and the alkyl aluminum and/or alkyl aluminium hydride of shown structure.
Under preferable case, in above-mentioned embodiment, the rare earth compounding, boride and alkyl aluminum and/or hydrogen
The ratio for changing the molal quantity of alkyl aluminum can be 1：0.9-1.1：10-50.
In the present invention, it is preferred to relative to every mole of butadiene, the rare earth catalyst in terms of rare earth element therein,
The rare earth catalyst usage amount is 1 × 10-6-4×10-4Mol, preferably 1.5 × 10-6-3.5×10-4mol.Catalyst amount mistake
It is big to be not only added to this, but also may increase content of ashes in polymer product.Heretofore described ash content refers to gathering
Close undecomposable component in product.
Organic solvent in the polymerization of the present invention can be various organic solvents commonly used in the art, art technology
Personnel to this it is equal can know, for example, can be selected the aliphatic saturated hydrocarbon inert to reactive component commonly used in the art and/or
Alicyclic, such as can be C5-C10Linear paraffin and/or C5-C10Cycloalkane, typical organic solvent includes but is not limited to
One kind in hexane, hexamethylene, heptane, pentane, isopentane, octane, hexahydrotoluene, benzene,toluene,xylene and isopropylbenzene or
It is a variety of.
In method of the present invention, in order that the conversion ratio for obtaining butadiene is higher, and the choosing of product butadiene rubber
Selecting property is higher, and the present invention preferably solution polymerization condition includes：Temperature is subzero 20 DEG C to 100 DEG C above freezing, more preferably
For subzero 10 DEG C to 80 DEG C above freezing；Time is 20-300 minutes, more preferably 30-250 minutes.
In the preparation process of the butadiene rubber, living polymer can directly be entered using terminator commonly used in the art
Row terminates, and the terminator for example can be water and/or alcoholic solvent, preferably water, methanol, ethanol, positive isopropanol, isopropanol and
One or more in 2,6- di-tert-butyl hydroquinone's methanol.
The present invention will be described in detail by way of examples below.But the scope of the present invention is not limited to these implementations
Example.
If not otherwise specified, the chemical reagent used in embodiment is chemically pure reagent.
In the present invention, the microstructure (including along Isosorbide-5-Nitrae structural content etc.) of the butadiene rubber polymer of synthesis uses moral
State's Bruker 400MHz nmr determinations, solvent is deuterochloroform；Molecular weight and molecualr weight distribution uses Shimadzu LC-
10AT types gel permeation chromatograph (GPC) determines, and THF is mobile phase, and Narrow distribution polystyrene is standard specimen, and temperature is 25 DEG C.
In the present invention, monomer conversion is concept well known to those skilled in the art, in the present invention, what monomer conversion referred to
It is the percentage that divinylic monomer is converted into butadiene rubber by polymerisation.The weight of straight polymer is polymer in the present invention
The weight of solution and the product of polymer concentration, wherein, the weight of polymer solution refers to not adding the polymer of terminator
The weight of solution, polymer concentration refer to straight polymer shared percentage by weight in a polymer solution.The list of the present invention
The conversion ratio of body is calculated by equation below：
Preparation example 1
The preparation example is used to prepare rare earth compounding of the present invention.
At 20 DEG C, by Lu (CH2SiMe3)3(THF)2(17.41g, 0.03mol) is added in 370mL toluene, then
It is added dropwise molten dissolved with 8- (N-2,6- dimethyl) imido grpup 1, the toluene (150mL) of 2- EEDQs (8.28g, 0.03mol)
Liquid, after reacting 8h at 20 DEG C, vacuum drains toluene, obtains oily residue, adds hexane, is filtered to remove insoluble matter, toward oil
Toluene is added in shape residue, obtains rare earth compounding Q1；
Analysis result is shown：
FD-Mass:696.3(calcd:696.3)
Elementary analysis:Measured value C:53.44 weight %, H:7.04 weight %, N:4.01 weight %
Theoretical value C:53.43%, H:7.04%, N:4.02%.It follows that rare earth compounding Q1 structural formula is：
Preparation example 2
The preparation example is used to prepare rare earth compounding of the present invention.
At 20 DEG C, by Sc (CH2SiMe3)3(THF)2(13.51g, 0.03mol) is added in 370mL toluene, then
It is added dropwise molten dissolved with 8- (N-2,6- dimethyl) imido grpup 1, the toluene (150mL) of 2- EEDQs (8.28g, 0.03mol)
Liquid, after reaction solution reacts 8h at 20 DEG C, vacuum drains toluene, obtains oily residue, adds hexane, is filtered to remove insoluble
Thing, obtain rare earth compounding Q2；
Analysis result is shown：
FD-Mass:566.4(calcd:566.3)
Elementary analysis:Measured value C:65.69 weight %, H:8.66 weight %, N:4.92 weight %
Theoretical value C:65.69 weight %, H:8.65 weight %, N:4.94 weight %.
It follows that rare earth compounding Q2 structural formula is：
Preparation example 3
The preparation example is used to prepare rare earth compounding provided by the invention.
At 20 DEG C, by Lu (CH2SiMe3)3(THF)28.71g (0.015mol) is added in 370mL toluene, then
It is added dropwise dissolved with 8- (N-2,6- diisopropyl) imido grpup 1, the toluene solution of 2- EEDQs (9.96g, 0.03mol)
(150mL), after reaction solution reacts 8h at 20 DEG C, vacuum drains toluene, obtains oily residue, adds hexane, is filtered to remove
Insoluble matter, obtain rare earth compounding Q3；
Analysis result is shown：
FD-Mass:751.4(calcd:751.4)
Elementary analysis:Measured value C:55.90 weight %, H:7.58 weight %, N:3.73 weight %
Theoretical value C:55.90 weight %, H:7.59 weight %, N:3.73 weight %.
It follows that rare earth compounding Q3 structural formula is：
Preparation example 4
The preparation example is used to prepare rare earth compounding provided by the invention.
At 20 DEG C, by Sc (CH2SiMe3)3(THF)2(20.28g, 0.045mol) is added to 370mL toluene, adds dropwise
Enter dissolved with 8- (N-2,6- diisopropyl) imido grpup 1, the toluene solution (150mL) of 2- EEDQs (9.96g, 0.03mol),
After reacting 8h at 20 DEG C, vacuum drains toluene, obtains oily residue, adds hexane, is filtered to remove insoluble matter, obtains rare earth and match somebody with somebody
Compound Q4；
Analysis result is shown：
FD-Mass:621.5(calcd:621.4)
Elementary analysis:Measured value C:67.58 weight %, H:9.19 weight %, N:4.51 weight %
Theoretical value C:67.59 weight %, H:9.17 weight %, N:4.51 weight %.
It follows that rare earth compounding Q4 structural formula is：
Embodiment 1
The present embodiment is used for illustrating the preparation for carrying out rare earth polybutadiene rubber using the rare earth compounding Q1 prepared：
1800g hexanes, 300g (4.41mol) butadiene, 0.0307g are sequentially added into 5L reactors under nitrogen protection
(44.1 μm of ol) rare earth compounding Q1,0.0873g (441 μm of ol) triisobutyl aluminium, 0.0407g (44.1 μm of ol) [Ph3C][B
(C6F5)4], after being reacted 2 hours under the conditions of 20 DEG C, polymer solution is released from kettle and adds 2,6- di-t-butyls to benzene
Diphenol ethanol solution terminating reaction.Conversion ratio is computed as 81%.The cis- Isosorbide-5-Nitrae structural content of polymer be 98.0%, Mn=12 ×
104, Mw/Mn=1.21.
Embodiment 2
The embodiment is used for illustrating the preparation for carrying out rare earth polybutadiene rubber using the rare earth compounding Q2 prepared：
1800g hexanes, 300g (4.41mol) butadiene, 0.0249g are sequentially added into 5L reactors under nitrogen protection
(44.1 μm of ol) rare earth compounding Q2,0.0873g (441 μm of ol) triisobutyl aluminium, 0.0407g (44.1 μm of ol) [Ph3C][B
(C6F5)4], after being reacted 2 hours under the conditions of 20 DEG C, polymer solution is released from kettle and adds 2,6- di-t-butyls to benzene
Diphenol ethanol solution terminating reaction.Conversion ratio is computed as 89%.The cis- Isosorbide-5-Nitrae structural content of polymer be 98.7%, Mn=14 ×
104, Mw/Mn=1.65.
Embodiment 3
The embodiment is used for illustrating the preparation for carrying out rare earth polybutadiene rubber using the rare earth compounding Q3 prepared：
1800g hexanes, 300g (4.41mol) butadiene, 0.0331g are sequentially added into 5L reactors under nitrogen protection
(44.1 μm of ol) rare earth compounding Q3,0.0873g (441 μm of ol) triisobutyl aluminium, 0.0407g (44.1 μm of ol) [Ph3C][B
(C6F5)4], after being reacted 2 hours under the conditions of 20 DEG C, polymer solution is released from kettle and adds 2,6- di-t-butyls to benzene
Diphenol ethanol solution terminating reaction.Conversion ratio is computed as 55%.The cis- Isosorbide-5-Nitrae structural content of polymer is 97.1%, Mn=8.3
×104, Mw/Mn=1.41.
Embodiment 4
The embodiment is used for illustrating the preparation for carrying out rare earth polybutadiene rubber using the rare earth compounding Q4 prepared：
1800g hexanes, 150g (2.21mol) butadiene, 0.0137g are sequentially added into 5L reactors under nitrogen protection
(22.1 μm of ol) rare earth compounding Q4,0.0873g (441 μm of ol) triisobutyl aluminium, 0.0407g (44.1 μm of ol) [Ph3C][B
(C6F5)4], after being reacted 2 hours under the conditions of 20 DEG C, polymer solution is released from kettle and adds 2,6- di-t-butyls to benzene
Diphenol ethanol solution terminating reaction.Conversion ratio is computed as 41%.The cis- Isosorbide-5-Nitrae structural content of polymer is 97.4%, Mn=7.9
×104, Mw/Mn=1.37.
Embodiment 5
The embodiment is used for illustrating the preparation for carrying out rare earth polybutadiene rubber using the rare earth compounding Q2 prepared：
Using the preparation for the method progress rare earth polybutadiene rubber for being embodiment 2, the difference is that, it is anti-under the conditions of subzero 20 DEG C
Answer 2 hours.Conversion ratio is computed as 22%.The cis- Isosorbide-5-Nitrae structural content of polymer is 99.6%, Mn=6.1 × 104, Mw/Mn=
1.57。
Embodiment 6
The embodiment is used for illustrating the preparation for carrying out rare earth polybutadiene rubber using the rare earth compounding Q2 prepared：
Using the preparation for the method progress rare earth polybutadiene rubber for being embodiment 2, the difference is that, it is small that 2 are reacted under the conditions of 0 DEG C
When.Conversion ratio is computed as 34%.The cis- Isosorbide-5-Nitrae structural content of polymer is 99.3%, Mn=6.4 × 104, Mw/Mn=1.45.
Embodiment 7
The embodiment is used for illustrating the preparation for carrying out rare earth polybutadiene rubber using the rare earth compounding Q2 prepared：
Using the preparation for the method progress rare earth polybutadiene rubber for being embodiment 2, the difference is that, react 90 under the conditions of 40 DEG C
Minute.Conversion ratio is computed as 100%.The cis- Isosorbide-5-Nitrae structural content of polymer is 98.5%, Mn=17 × 104, Mw/Mn=
2.31。
Embodiment 8
The embodiment is used for illustrating the preparation for carrying out rare earth polybutadiene rubber using the rare earth compounding Q2 prepared：
Using the preparation for the method progress rare earth polybutadiene rubber for being embodiment 2, the difference is that, react 60 under the conditions of 80 DEG C
Minute.Conversion ratio is computed as 100%.The cis- Isosorbide-5-Nitrae structural content of polymer is 98.1%, Mn=15 × 104, Mw/Mn=
2.77。
Embodiment 9
The embodiment is used for illustrating the preparation for carrying out rare earth polybutadiene rubber using the rare earth compounding Q1 prepared：
Using the preparation for the method progress rare earth polybutadiene rubber for being embodiment 1, the difference is that, it is added without in rare earth catalyst
[Ph3C][B(C6F5)4].Conversion ratio is computed as 70%.The cis- Isosorbide-5-Nitrae structural content of polymer is 97.2%, Mn=14 × 104,
Mw/Mn=1.43.
Embodiment 10
The embodiment is used for illustrating the preparation for carrying out rare earth polybutadiene rubber using the rare earth compounding Q1 prepared：
Using the preparation for the method progress rare earth polybutadiene rubber for being embodiment 1, the difference is that, it is added without in rare earth catalyst
Triisobutyl aluminium.Conversion ratio is computed as 62%.The cis- Isosorbide-5-Nitrae structural content of polymer is 97.0%, Mn=14 × 104, Mw/Mn
=1.41.
From embodiment 9-10 result：When the method according to the invention prepares butadiene rubber, even if being added without existing
The alkyl aluminum and/or alkyl aluminium hydride commonly used in technology or when being added without boride, can also be prepared cis- Isosorbide-5-Nitrae structure
The higher rare earth polybutadiene rubber of content.
Embodiment 11
The embodiment is used for illustrating the preparation for carrying out rare earth polybutadiene rubber using the rare earth compounding Q3 prepared：
Using the preparation for the method progress rare earth polybutadiene rubber for being embodiment 3, the difference is that, the dosage of triisobutyl aluminium is
441 μm of ol, and [Ph3C][B(C6F5)4] dosage be 8.02 μm of ol.Conversion ratio is computed as 45%.Cis- 1,4 structure of polymer
Content is 96.5%, Mn=10 × 104, Mw/Mn=1.40.
Data above shows, anti-by reasonably adjusting polymerisation in solution when preparing butadiene rubber using the method for the present invention
The condition answered, the cis- Isosorbide-5-Nitrae structural content of polymer while high conversion ratio is taken into account, can be made to be up to more than 97%, even
Highest can reach 99.6%.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (14)
1. a kind of preparation method of rare earth polybutadiene rubber, this method include：In presence of organic solvent and solution polymerization
Under the conditions of, butadiene is contacted with rare earth catalyst, it is characterised in that contain structure shown in formula (I) in the rare earth catalyst
Rare earth compounding：
Wherein, R1、R2And R3It is each independently hydrogen or C1-C20Alkyl；R4And R5It is each independently hydrogen or C1-C6Alkyl；
Ln is one kind in rare earth metal；THF represents tetrahydrofuran.
2. the method according to claim 11, wherein, in the rare earth compounding of structure shown in formula (I), R1、R2And R3Each
It independently is hydrogen or C1-C12Alkyl；R4And R5It is each independently hydrogen or C1-C3Alkyl；Ln be Y, Lu, La, Nd, Sm,
One kind in Eu, Sc and Tm.
3. the method according to claim 11, wherein, in the rare earth compounding of structure shown in formula (I), R1、R2And R3Phase
Together, and it is hydrogen or C1-C4Alkyl；R4And R5It is identical, and be methyl；Ln is Lu or Sc.
4. according to the method described in any one in claim 1-3, wherein, also contain boride in the rare earth catalyst.
5. the method according to claim 11, wherein, mole of rare earth compounding and boride in the rare earth catalyst
Than for 1：0.9-1.1.
6. according to the method for claim 4, wherein, the boride is [Ph3C][B(C6F5)4]、[PhMe2NH][B
(C6F5)4] and B (C6F5)3In one or more.
7. according to the method described in any one in claim 1-3, wherein, also contain alkyl aluminum in the rare earth catalyst
And/or alkyl aluminium hydride.
8. according to the method for claim 7, wherein, alkyl aluminum and/or alkyl aluminium hydride in the rare earth catalyst
The ratio of the molal quantity of molal quantity and rare earth compounding is 10-50：1.
9. according to the method described in any one in claim 1-3, wherein, in the rare earth catalyst also containing boride with
And alkyl aluminum and/or alkyl aluminium hydride.
10. the method according to claim 11, wherein, rare earth catalyst middle rare earth complex, boride and the alkyl aluminum
And/or the ratio of the molal quantity of alkyl aluminium hydride is 1：0.9-1.1：10-50.
11. according to the method described in any one in claim 1-3, wherein, the rare earth catalyst is with rare earth therein member
Element meter, the dosage mol ratio of the rare earth catalyst and butadiene is 1 × 10-6-4×10-4：1.
12. according to the method for claim 11, wherein, the dosage mol ratio of the rare earth catalyst and butadiene is 1.5
×10-6-3.5×10-4：1.
13. according to the method described in any one in claim 1-3, wherein, the solution polymerization condition includes：Temperature
For subzero 20 DEG C to 100 DEG C above freezing；Time is 20-300 minutes.
14. according to the method for claim 13, wherein, the solution polymerization condition includes：Temperature is subzero 10 DEG C
To 80 DEG C above freezing.
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| Title |
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| Highly trans-1,4 selective (co-)polymerization of butadiene and isoprene with quinolyl anilido rare earth metal bis(alkyl) precursors;Dongtao Liu;《Dalton Transactions》;20111231(第40期);7756-7757，7760 * |
| Isoprene Polymerization with Indolide-Imine Supported Rare-Earth Metal Alkyl and Amidinate complexes;Yi Yang;《Journal of Polymer Science Part A: Polymer Chemistry》;20080618;第46卷(第15期);5255-5256,5258 * |
| 稀土催化剂及其用于合成橡胶／弹性体的研究进展;朱寒;《高分子通报》;20140531(第5期);65-87 * |
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