CN104231133B - A kind of rare earth catalyst and the method being used for preparing cis conjugated diene polymer thereof - Google Patents
A kind of rare earth catalyst and the method being used for preparing cis conjugated diene polymer thereof Download PDFInfo
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Abstract
The present invention relates to a kind of rare earth catalyst and for preparing the polymerization of cis conjugated diene polymer.Use the homogeneous rare earth catalyst system of binary of major catalyst long-chain carboxylic acid's Rare Earth Complexes and alkyl aluminum composition, after adding optional component conjugated alkene, catalyst system and catalyzing phase also can be made more stable, while ensureing catalysis activity and stable in catalytic performance, reduce the consumption of expensive alkyl aluminum, prepare the conjugated diene polymer of high cis-contents, Narrow Molecular Weight Distribution.
Description
Technical field
The present invention relates to a kind of rare earth catalyst and prepare cis conjugated diene for being catalyzed conjugate diene polymerization
The method of hydrocarbon polymer.
Background technology
Conjugated diene (such as: butadiene or isoprene) at transition-metal catalyst (such as: nickel system, cobalt system or titanium system) and
Polymerization can be oriented under rare earth catalyst (such as: neodymium series), obtain high-cis (cis-Isosorbide-5-Nitrae content > 95%) polybutadiene or poly-different
Pentadiene.This high formula polybutadiene or polyisoprene are particularly well-suited to manufacture tire and other elastic articles.
Cis-1,4 structural contents of polybutadiene rubber or polyisoprene are to its physical and mechanical properties and dynamic mechanical
Performance has a significant effect, when cis-Isosorbide-5-Nitrae structural content ＞ 96% time, its content often increases by 1%, can make the performance of diolefin rubber
Significantly improve, as hot strength can improve 6kg/cm2, see: " rare earth catalyst synthetic rubber collected works ", Science Press, 1980,
250～265；J.Appl.Polym.Sci., 2006,99:88～99.On the other hand, molecular weight distribution is narrow, is conducive to
Build preferable vulcanization crosslinking network and reduce chain free terminal concentration, contributing to improving further rubber performance.Generally, use
Rare-earth catalysis system prepare polybutadiene or polyisoprene product, ratio use cobalt system, titanium system or Nickel salt catalysis
Agent prepare corresponding product there is more preferable green strength and cured properties, as little in hysteresis loss, heat is low, wearability good,
Stress crystallinity is good, autohension is good, the good and warping strength be full of cracks of tear resistance, is suitable for the performance of running at high speed of automobile, meets wheel
The demand of tire high speed meridian.If reach to improve cis-1,4 structures further contain by catalyst or polymerization technique improvement
Amount and reduction molecular weight distribution, then be conducive to obtaining the conjugate diene polymerization product that performance is more excellent.Catalyst
Kind and manner of formulation are cis-1,4 content and the key factors of molecular weight distribution affecting conjugate diene polymerization product.
Ziegler-Natta type rare-earth catalysis system according to component can be divided into binary catalyst system, three-element catalytic system and
Multiple catalyzing system.Binary catalyst system is made up of with alkyl aluminum (Al) neodymium trichloride nL coordination compound (Nd), wherein Al/Nd
Mol ratio is usual > 20, see: Chinese science, B collects, and 2009,39(10): 1006～1027.Binary system component is few, affect because of
Element is few, and preparing process and method are simple.But this kind of catalyst is heterogeneous system mostly, when being catalyzed conjugate diene polymerization
The most difficult control of less stable, catalytic process and polymerization process, polymer molecular weight is relatively big, and molecular weight distribution is wider, polymerization
System viscosity is big, brings difficulty to the production processes such as heat transfer, conveying, glue spraying, cohesion, and increases energy consumption.Above-mentioned non-in order to solve
The deficiency of homogeneous catalyst, it is proposed that improvement by two (trifluoroacetic acid) Neodymium chloride nL coordination compound or alkoxyl Neodymium chloride and alkane
The binary catalyst system of base aluminum composition, such as (CF3COO)2NdCl·(C2H5)2O or (CF3COO)2NdCl·C2H5OH and triethyl group
The binary rare-earth catalyst of aluminum composition in toluene in homogeneous system, but catalyst directionality relative mistake, and toluene is as solvent,
Catalyst activity can be reduced, see: macromolecule communication, 1979,6:367～369；1984,5:358～362.By alkoxyl chlorination
Neodymium Nd (OR)3-nClnWith the binary catalyst system of triethyl aluminum composition, wherein R is butyl or amyl group and isomer thereof, prepared
The cis-content of polybutadiene the most on the low side, see: chemistry journal, 1983,41:490～497.
Three-element catalytic system be by rare earth carboxylate or rare earth phosphonate compounds (Ln), alkyl aluminum (Al), containing halogenated
Compound forms.For rare earth carboxylate system, homogeneous catalyst system can be formed under certain condition, but alkyl aluminum consumption leads to
The biggest, such as: Al/Ln mol ratio > 15, see: Chinese science, B collects, 2009,39:1006～1027.Alkyl aluminum is expensive,
As a example by conventional diisobutylaluminium hydride: the market price of the hexane solution containing 25% diisobutylaluminium hydride is at present: 1778
Unit/800mL.Alkyl aluminum consumption is the highest, and catalyst cost just significantly improves.And, in existing rare earth catalyst system, generally
Need to use increase alkyl aluminum consumption to reduce polymer molecular weight, and make molecular weight distribution broaden.
Additionally, catalyst activity is obviously dependent on preparation condition, cause ternary catalyst systems there may be how activity
Center, catalysis and the most difficult control of polymerization process, cause the molecular weight and molecualr weight distribution of polymerizate to be all difficult to regulate and control, ginseng
See: US5428119 and W09305083.In order to improve catalyst stability and directionality, raising constitutional unit further
Regularity and reduction molecular weight distribution, can add a certain amount of oxygen-containing, phosphorus or sulfur in above-mentioned ternary catalyst systems
Organic compound, forms multiple catalyzing system, sees: CN101927186A and CN102532368A, but catalytic component is many, shadow
The factor of sound is many, complex process, and regulation and control difficulty is the most relatively large.
Summary of the invention
It is an object of the invention to provide a kind of homogeneous rare earth catalyst and for preparing cis conjugate diene polymerization
The method of thing.Use the homogeneous rare earth catalyst of binary of major catalyst long-chain carboxylic acid Rare Earth Complexes A and alkyl aluminum B composition
System, after adding optional component C, also can make catalyst system and catalyzing phase more stable, is ensureing that catalysis activity and catalytic performance are steady
Simultaneously qualitatively, the alkyl aluminum consumption of costliness can be greatly lowered, prepare the conjugation two of high cis-contents, narrow molecular weight distribution
Olefin polymer.
Rare earth catalyst provided by the present invention, it basic composition is:
Component A is chlorination rare earth complex monomer: MCl1(RCOO)2·nL、MCl2(RCOO)1NL or MCl1
(RCOO)2NL and MCl2(RCOO)1The mixture of nL.Wherein, M is rare earth element, preferably neodymium or praseodymium；RCOO-is C6-C10
Straight-chain carboxylic acid's root or branched carboxylic acids root, be selected from: cycloalkanes acid group, 2 ethyl hexanoic acid root, 3-ethyl hexyl acid group, octanoic acid root, 2-second
Base enanthic acid root, 3-ethyl enanthic acid root, n-nonanoic acid root, 2-ethyl octanoic acid root, 3-ethyl octanoic acid root, decanoate, neodecanoic acid root；Preferably
For: cycloalkanes acid group, 2 ethyl hexanoic acid root, octanoic acid root, n-nonanoic acid root or neodecanoic acid root；More preferably: cycloalkanes acid group, 2 ethyl hexanoic acid
Root, octanoic acid root or neodecanoic acid root；N=1-4；L is the organic compound such as alcohol, ether, carboxylic acid or phosphate ester.
Wherein,
Alcohol is C1-C8Alcohol, selected from any one of following material or their mixture: methanol, ethanol, propanol, different
Propanol, butanol, amylalcohol, hexanol, Hexalin, enanthol, benzyl alcohol, phenethanol, capryl alcohol, 2-Ethylhexyl Alcohol；It is preferably: isopropanol,
Hexanol, enanthol, capryl alcohol, 2-Ethylhexyl Alcohol；More preferably: capryl alcohol, 2-Ethylhexyl Alcohol, enanthol.
Carboxylic acid is C6-C10Carboxylic acid, selected from following C6-C10Straight-chain carboxylic acid or any one of branched carboxylic acids material or
Their mixture: 2 ethyl hexanoic acid, 3-thylhexoic acid, enanthic acid, octanoic acid, 2-ethyl enanthic acid, 3-ethyl enanthic acid, n-nonanoic acid, 2-second
Base octanoic acid, 3-ethyl octanoic acid, capric acid, neodecanoic acid；It is preferably: 2 ethyl hexanoic acid, octanoic acid, n-nonanoic acid, neodecanoic acid；More preferably: 2-
Thylhexoic acid, octanoic acid, neodecanoic acid.
Ether is C1-C8Ether, selected from any one of following material or their mixture: ether, ethyl methyl ether, butyl ether,
Oxolane, dioxane；It is preferably: ether, oxolane, dioxane；More preferably: oxolane, dioxane.
Organophosphorus ester is selected from any one of following material or their mixture: trimethyl phosphate, tricresyl phosphate second
Ester, tricresyl phosphate propyl ester, tributyl phosphate, TNPP tri n pentyl phosphate, tri hexyl phosphate, THP triheptylphosphate, triphenyl phosphate, phosphoric acid triphen
Ester, tricresyl phosphate, dimethyl phosphate, diethyl phosphate, di(2-ethylhexyl)phosphate propyl ester, dibutylphosphoric acid ester, di(2-ethylhexyl)phosphate pentyl ester, di(2-ethylhexyl)phosphate
Own ester, di(2-ethylhexyl)phosphate heptyl ester, diphenyl phosphate, diphenyl phosphate, xylenylphosphate, phosphoric acid methyldiphenyl ester, ethyl two
Phenyl ester, phosphoric acid propyl group diphenyl ester or phosphoric acid butyl diphenyl ester.Preferably: tricresyl phosphate propyl ester, tributyl phosphate, TNPP tri n pentyl phosphate, phosphorus
Acid three own esters；More preferably: tricresyl phosphate propyl ester, tributyl phosphate, TNPP tri n pentyl phosphate.
Component B is alkyl aluminum: selected from AlR '3Or AlHR ' (B1)2(B2) or both mixture, wherein R ' is C1-C6's
Alkyl；Selected from any one of following material or their mixture: trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, three isobutyls
Base aluminum, three amyl group aluminum, three hexyl aluminum, diethyl aluminium hydride, diisobutylaluminium hydride；Preferably: triethyl aluminum, triisobutyl aluminium,
Diethyl aluminium hydride, diisobutylaluminium hydride or their mixture；More preferably: triisobutyl aluminium, diisobutylaluminium hydride or
Both mixture.
Optional component C: conjugated alkene.
The mol ratio of each component is A:B:C=1:3～40:0～4, preferably 1:3.5～35:0～3.5, more preferably 1:4
～25:0～3；When use component C time, C/A molar ratio is 0.5～3, the mol ratio of each component be preferably A:B:C=1:4～
25:0.5～3.
Component A is major catalyst, can adopt and prepare with the following method:
Rare earth chloride salt and rare earth carboxylate are mixed to form all according to the molar ratio of 1:2～2:1 in organic ligand L
Phase solution, wherein organic ligand L is 5～20 with the mol ratio of rare earth element, and the lower reaction 4～10h of backflow, by product with having
Machine solvent washs, and filters, and is dried, obtains chlorination rare earth complex monomer.Organic solvent is selected from any one of following material
Or their mixture: hexane, hexamethylene, heptane, octane, hexahydrotoluene or the (C that raffinates oil6～C8Alkane mixed solution).
The rare earth catalyst of the present invention is by major catalyst A rare earth catalyst system homogeneous with the binary that alkyl aluminum B forms,
After adding optional component C, catalyst system and catalyzing phase can be made more stable.The preparation temperature of catalyst is-40～70 DEG C, preferably-
30～65 DEG C, more preferably-20～60 DEG C, can carry out in organic solvent, organic solvent is selected from any in following material
Kind or their mixture: hexane, hexamethylene, heptane, octane, hexahydrotoluene or the (C that raffinates oil6～C8Alkane mixing molten
Liquid).Method for preparing catalyst is fairly simple, component B is joined in component A or in the mixture of component A and component C；Or
The mixture of component A or component A and component C is joined in component B；Or component B2 is joined in component A or component A with
In the mixture of component C, after mixing, add component B1；Or the mixture of component A or component A and component C is joined group
Divide in B2, add component B1.Catalyst depends on Aging Temperature setup time, and temperature is the highest, and the time is the shortest, usually 1 point
Clock～100 hours, preferably: 2 minutes～50 hours, more preferably: 5 minutes～20 hours.
In order to improve catalyst dissolubility in alkane solvent further, it is also possible to add long-chain alcohol, carboxylic acid or phosphoric acid
Ester；Meanwhile, the introducing of a small amount of long-chain alcohol, carboxylic acid or phosphate ester, it is also possible to improve further the molecular weight of polymer and cis contain
Amount, and reduce molecular weight distribution.Introduced long-chain alcohol, carboxylic acid or phosphate ester additive is 0.2 with the mol ratio of major catalyst A
～5, preferably: 0.5～4.8, more preferably: 0.6～4.5.
Present invention also offers and a kind of use above-mentioned rare earth catalyst for preparing cis conjugated diene polymer
Polymerization, in the presence of rare earth catalyst of the present invention, with hydrocarbon compound as polymer solvent, conjugated diene monomer concentration
Be 1.0～6.0mol/L, preferably: 1.2～5.0mol/L, more preferably: 1.5mol/L～4.0mol/L, polymerization temperature be-50～
120 DEG C, preferably :-30～110 DEG C, more preferably :-20～100 DEG C.Catalyst charge makes component A and monomer mole ratio be 0.3
×10-4～1.5 × 10-3, preferably: 0.5 × 10-4～1.3 × 10-3, more preferably: 0.7 × 10-4～1.1 × 10-3。
Polymer solvent described in above-mentioned polymerization is the hydrocarbon compound that conjugate diene polymerization is conventional, preferably is selected from down
Any one of row material or their mixture: hexane, hexamethylene, heptane, octane, hexahydrotoluene or the (C that raffinates oil6
～C8Alkane mixed solution).
The polymerization of the present invention is applicable to polymerization or the combined polymerization of conjugated diene, including 1,3-butadiene, 1,3-is different
Pentadiene, 2,3 dimethyl butadiene, 2,4-hexadiene, 1,3-pentadiene or 2-methyl-1,3-pentylene etc..
Use rare earth catalyst system of the present invention, can reach following effect:
1., without adding chlorine-containing compound as activator, simplify the preparation technology of catalyst, obtain binary the dilutest
Soil catalyst system；
2. halogen and rare earth element are directly with chemical bonds, advantageously form single-activity center, obtain narrow molecular-weight
Distribution polymerization product, and improve the stability of catalyst；
3. alkyl aluminum consumption is greatly lowered, B/A molar ratio even can be down to 4.0 or lower, thus significantly drop
Low catalyst cost；
4. cis-Isosorbide-5-Nitrae the content of the conjugated diene polymer prepared by may be up to more than 99%, and molecular weight distribution is narrower
(profile exponent≤3.0), molecular weight distributing index is up to 1.9.
5., by the ratio of chloride ion in regulation component A with carboxylate radical, can realize regulating the molecular weight of polymerizate, it is not necessary to
Use the alkyl aluminum of costliness.
Detailed description of the invention:
Using Waters1515 type GPC, (oxolane is molten for four root chromatogram columns (HT3, HT4, HT5, HT6) test polymer
Agent system) number-average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (PDI, Mw/Mn).With infrared spectrum (FTIR)
Method measures the microstructure content of polymer.
There is provided following non-limiting example to further illustrate the present invention, but the invention is not restricted to these embodiments.
Embodiment 1
Catalyst preparation and polyreaction are carried out the most under nitrogen protection.
By NdCl3、Nd(C5H10(C2H5)COO)3With oxolane according under the molar ratio of 1:2:10, backflow is lower anti-
Answer 4h, form homogeneous phase solution, obtain product, wash with hexane, filter, be dried, obtain chlorination rare earth complex monomer
NdCl1(C5H10(C2H5)COO)2THF(A1).With hexane as solvent, 0.99mmol A1 is added with 3.95mmol isooctyl acid
In 14.8mmol triisobutyl aluminium, react 1 hour at 45 DEG C, obtain light blue homogeneous catalyst.
In polymer reactor, add 40ml butadiene, raffinate oil and above-mentioned catalyst system, monomer concentration=2.4mol/
L, catalytic component A are 4 × 10 with the mol ratio of monomer-4, polyase 13 hour at 50 DEG C, add 2 containing 1% mass, 6-bis-uncle
The ethanol solution of butyl p-methyl phenol terminates reaction, is dried, is placed in 40 DEG C of vacuum drying ovens being dried to perseverance after washing with water
Weight, polybutadiene yield is 36%, weight average molecular weight (Mw) it is 4.4 × 105, molecular weight distributing index (Mw/Mn) it is 2.7, cis-
1,4 content are 98.0%.
Embodiment 2
Major catalyst is prepared with embodiment 1, simply by Nd (C5H10(C2H5)COO)3Change Nd (C into7H15COO)3, prepare
Catalyst n dCl1(C7H15COO)2THF(A2).0.99mmolA2 is joined in 24.7mmol triisobutyl aluminium, anti-at 45 DEG C
Answer 1 hour, obtain light blue homogeneous catalysis system.
Polymerisation process is with embodiment 1, and simply catalytic component A is 2.4 × 10 with the mol ratio of monomer-4, at 50 DEG C
It is polymerized 2.8 hours.Polybutadiene yield is 31%, MwIt is 3.3 × 105, Mw/MnBeing 2.6, cis-Isosorbide-5-Nitrae content is 98.4%.
Embodiment 3
Major catalyst is prepared with embodiment 2.With hexane as solvent, add in 3.45mmol diisobutyl aluminium hydride
0.99mmol A2, reacts 3 hours at 45 DEG C, obtains light blue homogeneous catalysis system.
Polymerisation process is with embodiment 1, and simply catalytic component A is 8 × 10 with the mol ratio of monomer-4, add polymerization
In system, triisobutyl aluminium is polyase 13 hour at 1,50 DEG C with the mol ratio of A2.Polybutadiene yield is 29%, MwBe 6.14 ×
105, Mw/MnBeing 2.8, cis-Isosorbide-5-Nitrae content is 98.2%.Embodiment 4
Catalyst is prepared with embodiment 3.
With hexane as solvent, 3.455mmol diisobutyl aluminium hydride adds 1.0mmolA1, little 45 DEG C of reactions 3
Time, obtain light blue homogeneous catalysis system.
Polymerisation process is with embodiment 3, and simply adding the mol ratio of triisobutyl aluminium and A2 in polymerization system is 2.Poly-
Butadiene yield is 47%, MwIt is 4.38 × 105, Mw/MnBeing 2.8, cis-Isosorbide-5-Nitrae content is 98.0%.
Embodiment 5
Catalyst preparation and polyreaction are carried out the most under nitrogen protection.Major catalyst preparation method is with embodiment 1, simply
By Nd (C5H10(C2H5)COO)3Change Nd (C into9H19COO)3, prepare catalyst n dCl1(C9H19COO)2THF(A3).Will
0.99mmol A3 and 0.99mmol tributyl phosphate join in 14.8mmol triisobutyl aluminium, react 1 hour at 45 DEG C,
To light blue homogeneous catalysis system.
Polymerization and post-processing approach are with embodiment 1, and simply catalytic component A is 8 × 10 with the mol ratio of monomer-4,
Polyase 13 hour at 50 DEG C.Polybutadiene yield is 48%, MwIt is 4.7 × 105, Mw/MnBeing 2.8, cis-Isosorbide-5-Nitrae content is 98.0%.
Embodiment 6
Major catalyst preparation method, with embodiment 1, simply adds isooctanol (oca), and NdCl in reaction system3: Nd
(C5H10(C2H5)COO)3Mol ratio be 2:1, obtain chlorination rare earth complex monomer NdCl2(C5H10(C2H5)COO)1·4oca
(A4).With hexane as solvent, by 0.99mmol A4 with join in 14.8mmol triisobutyl aluminium, add 1mmol butadiene
React 2 hours at 0 DEG C, obtain catalyst system and catalyzing.
Polymerization and post-processing approach with embodiment 1, simply the mol ratio of catalytic component A4 and monomer be 2.7 ×
10-4, it is polymerized 2.5 hours at 45 DEG C.Polybutadiene yield is 15%, MwIt is 9.63 × 105, Mw/MnIt is 2.6, cis-Isosorbide-5-Nitrae content
It is 99.2%.
Embodiment 7
Major catalyst preparation method is with embodiment 6.With hexane as solvent, by 0.99mmol A4 and 0.99mmol butadiene
Join in 14.8mmol triisobutyl aluminium, react 10min at 40 DEG C, obtain catalyst system and catalyzing.
Polymerization and post-processing approach are with embodiment 1, and simply catalytic component A is 2.7 × 10 with the mol ratio of monomer-4, start at-14 DEG C at latter 45 DEG C of reaction and be polymerized 2.5 hours.Polybutadiene yield is 19%, MwIt is 1.09 × 106, Mw/MnFor
2.2, cis-Isosorbide-5-Nitrae content is 99.0%.
Embodiment 8
Major catalyst preparation method with embodiment 1, simply NdCl3: Nd (C5H10(C2H5)COO)3Mol ratio be 1.2:
1.8, obtain NdCl2(C5H10(C2H5)COO)1THF Yu NdCl (C5H10(C2H5)COO)2The mixture (A5,1:4) of THF.
Method for preparing catalyst, with embodiment 9, simply reacts 2h at 45 DEG C.
Polymerization and post-processing approach are with embodiment 1, and simply catalytic component A is 2.6 × 10 with the mol ratio of monomer-4, polyase 13 hour at 50 DEG C.Polybutadiene yield is 50%, MwIt is 4.49 × 105, Mw/MnBeing 2.8, cis-Isosorbide-5-Nitrae content is
98.2%。
Embodiment 9
Major catalyst preparation method is with embodiment 8.With hexane as solvent, in 8.6mmol triisobutyl aluminium, add
0.99mmol A5, reacts 40min at 45 DEG C, obtains homogeneous catalysis system.
Polymerization and post-processing approach are with embodiment 1, and simply catalytic component A5 is 8 × 10 with the mol ratio of monomer-4,
Polyase 13 hour at 50 DEG C.Polybutadiene yield is 37%, MwIt is 6.94 × 105, Mw/MnBeing 2.9, cis-Isosorbide-5-Nitrae content is
98.3%。
Embodiment 10
Major catalyst preparation method is with embodiment 8.With hexane as solvent, in 6.9mmol triisobutyl aluminium, add
0.99mmol A5, reacts 1h at 45 DEG C, obtains homogeneous catalysis system.
Polymerization and post-processing approach are with embodiment 9, and simply catalytic component A5 is 5 × 10 with the mol ratio of monomer-4,
Add triisobutyl aluminium (Al:A5=2), polyase 13 hour at 50 DEG C.Polybutadiene yield is 47%, MwIt is 4.54 × 105, Mw/Mn
Being 2.2, cis-Isosorbide-5-Nitrae content is 98.3%.
Embodiment 11
Major catalyst preparation method is with embodiment 8.Method for preparing catalyst with embodiment 10, simply Al/A5=15,45 DEG C
Reaction 3h.
Isoprene and butadiene 2/3 are configured to the solution of raffinating oil that concentration is 3.4mol/L, polymerization side in molar ratio
Method and post-processing approach are with embodiment 9, and simply catalytic component A5 is 4 × 10 with the mol ratio of monomer-4, fourth penta copolymer yield
It is 80%, MwIt is 4.19 × 105, Mw/MnBeing 2.9, isoprene unit is cis-Isosorbide-5-Nitrae content is 98.3%, and butadiene unit is cis-
1,4 content are 98.2%.
Embodiment 12
Method for preparing catalyst is with embodiment 11.
Being joined by catalyst in isoprene monomer liquid at 0 DEG C, component A5 is 4 × 10 with the mol ratio of monomer-4, absolutely
Thermal polymerization 3h, post-processing approach is with embodiment 9, and polyisoprene yield is 88%, MwIt is 6.49 × 105, Mw/MnIt is 2.8.
Embodiment 13
Major catalyst preparation method, with embodiment 1, simply adds tributyl phosphate (TBP) in reaction system, and
NdCl3: Nd (C7H15COO)3Mol ratio be 1:2, obtain chlorination rare earth complex monomer NdCl1(C7H15COO)2·TBP
(A6).Method for preparing catalyst with embodiment 10, simply Al/A6=15.
Polymerization and post-processing approach are with embodiment 1, and simply catalytic component A6 is 8 × 10 with the mol ratio of monomer-4,
Polyase 13 hour at 50 DEG C.Polybutadiene yield is 64%, MwIt is 4.81 × 105, Mw/MnBeing 2.8, cis-Isosorbide-5-Nitrae content is
98.0%。
Claims (11)
1. a rare earth catalyst, consisting of:
A: chlorination rare earth complex monomer, for MCl1(RCOO)2·nL、MCl2(RCOO)1NL or MCl1(RCOO)2NL with
MCl2(RCOO)1The mixture of nL；M is rare earth element, and RCOO-is C6-C10Straight-chain carboxylic acid's root or branched carboxylic acids root, n=1-
4；L is organic ligand, selected from alcohol, ether, carboxylic acid or organophosphorus ester；
B: alkyl aluminum compound, selected from AlR '3Or AlHR '2Or both mixture, wherein R ' is C1-C6Alkyl；
C: optional component, for conjugated alkene；
The mol ratio of each component is A:B:C=1:3～40:0～4.
Rare earth catalyst the most according to claim 1, is characterized in that:
Component A is adopted and is prepared with the following method:
Rare earth chloride salt and rare earth carboxylate are mixed to form according to the molar ratio of 1:2～2:1 in organic ligand L and all mix
Liquid, wherein organic ligand L is 5～20 with the mol ratio of rare earth element, and the lower reaction 4～10h of backflow, by product with organic molten
Agent is washed, and filters, and is dried, obtains chlorination rare earth complex monomer；
Component A rare earth elements M is selected from neodymium or praseodymium；RCOO-is selected from: cycloalkanes acid group, 2 ethyl hexanoic acid root, 3-ethyl hexyl acid group,
Octanoic acid root, 2-ethyl enanthic acid root, 3-ethyl enanthic acid root, n-nonanoic acid root, 2-ethyl octanoic acid root, 3-ethyl octanoic acid root, decanoate or new
Decanoate；
B component is selected from any one of following material or their mixture: trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, three
Aluminium isobutyl, three amyl group aluminum, three hexyl aluminum, diethyl aluminium hydride, diisobutylaluminium hydride.
Rare earth catalyst the most according to claim 1, is characterized in that:
In the organic ligand L of component A, alcohol is C1-C8Alcohol, selected from any one of following material or their mixture: first
Alcohol, ethanol, propanol, isopropanol, butanol, amylalcohol, hexanol, Hexalin, enanthol, benzyl alcohol, phenethanol, capryl alcohol, 2-Ethylhexyl Alcohol；
Carboxylic acid is C6-C10Carboxylic acid, selected from following C6-C10Straight-chain carboxylic acid or any one of branched carboxylic acids material or theirs is mixed
Compound: 2 ethyl hexanoic acid, 3-thylhexoic acid, enanthic acid, octanoic acid, 2-ethyl enanthic acid, 3-ethyl enanthic acid, n-nonanoic acid, 2-ethyl octanoic acid, 3-
Ethyl octanoic acid, capric acid, neodecanoic acid；Ether is C1-C8Ether, selected from any one of following material or their mixture: second
Ether, ethyl methyl ether, butyl ether, oxolane, dioxane；Organophosphorus ester is selected from any one of following material or theirs is mixed
Compound: trimethyl phosphate, triethyl phosphate, tricresyl phosphate propyl ester, tributyl phosphate, TNPP tri n pentyl phosphate, tri hexyl phosphate, tricresyl phosphate
Heptyl ester, triphenyl phosphate, tricresyl phosphate, dimethyl phosphate, diethyl phosphate, di(2-ethylhexyl)phosphate propyl ester, dibutylphosphoric acid ester, phosphoric acid
Diamyl ester, phosphoric acid dihexyl, di(2-ethylhexyl)phosphate heptyl ester, diphenyl phosphate, diphenyl phosphate, xylenylphosphate, phosphoric acid methyldiphenyl
Ester, ethyl diphenyl ester, phosphoric acid propyl group diphenyl ester or phosphoric acid butyl diphenyl ester.
4., according to the rare earth catalyst described in Claims 2 or 3, it is characterized in that:
In the organic ligand L of component A, alcohol is selected from: methanol, ethanol, propanol, isopropanol, butanol, amylalcohol, hexanol, Hexalin, heptan
Alcohol, benzyl alcohol, phenethanol, capryl alcohol or 2-Ethylhexyl Alcohol；Ether is selected from: oxolane or dioxane；Carboxylic acid is selected from: 2-ethyl hexyl
Acid, 3-thylhexoic acid, octanoic acid, 2-ethyl enanthic acid, 3-ethyl enanthic acid, n-nonanoic acid, 2-ethyl octanoic acid, 3-ethyl octanoic acid, capric acid or new
Capric acid；Organophosphorus ester is selected from tricresyl phosphate propyl ester, tributyl phosphate, TNPP tri n pentyl phosphate or tri hexyl phosphate；
B component is triethyl aluminum, triisobutyl aluminium, diethyl aluminium hydride, diisobutylaluminium hydride or their mixture.
Rare earth catalyst the most according to claim 4, is characterized in that: in the organic ligand L of component A alcohol be isopropanol, oneself
Alcohol, enanthol, capryl alcohol or 2-Ethylhexyl Alcohol；Carboxylic acid is 2 ethyl hexanoic acid, octanoic acid, n-nonanoic acid or neodecanoic acid；Organophosphorus ester is phosphoric acid
Three propyl ester, tributyl phosphate or TNPP tri n pentyl phosphate.
Rare earth catalyst the most according to claim 2, is characterized in that: in component A, RCOO-is cycloalkanes acid group, 2-ethyl hexyl
Acid group, octanoic acid root, n-nonanoic acid root or decanoate；
B component is triisobutyl aluminium, diisobutylaluminium hydride or both mixture.
Rare earth catalyst the most according to claim 1, is characterized in that: in catalyst, the mol ratio of each component is: A:B:C=
1:3.5～35:0～3.5.
Rare earth catalyst the most according to claim 7, is characterized in that: in catalyst, the mol ratio of each component is: A:B:C=
1:4～25:0～3.
9. the polymerization of a conjugated diene, it is characterised in that: use claim 1-8 any one rare earth catalyst to urge
Change conjugated diene to be all polymerized or copolymerization at hydrocarbon compound solvent, prepare corresponding conjugated alkene homopolymer or be total to
Polymers.
The polymerization of conjugated diene the most according to claim 9, is characterized in that: conjugated diene concentration be 1.0～
6.0mol/L, polymerization temperature is-50～120 DEG C, and catalyst charge is calculated as 0.3 × 10 with component A and monomer mole ratio-4~
1.5×10-3；
Hydrocarbon compound solvent is selected from any one of following material or their mixture: hexane, hexamethylene, heptane, pungent
Alkane, hexahydrotoluene or raffinate oil；
Conjugated diene is selected from 1,3-butadiene, 1,3-isoprene, 2,3 dimethyl butadiene, 2,4-hexadiene, 1,3-penta
Diene or 2-methyl-1,3-pentylene.
The polymerization of 11. conjugated dienes according to claim 10, is characterized in that: conjugated diene monomer concentration is
1.2～5.0mol/L, polymerization temperature is-30～110 DEG C, and catalytic component A and monomer mole ratio are 0.5 × 10-4～1.3 ×
10-3。
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