CN104231133A - Rare-earth catalyst and method of using same to prepare high cis conjugated diene polymer - Google Patents
Rare-earth catalyst and method of using same to prepare high cis conjugated diene polymer Download PDFInfo
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Abstract
The invention relates to a rare-earth catalyst and a polymerization method of using the same to prepare a high cis conjugated diene polymer. A two-composition rare-earth catalyst system composed of a main catalyst long-chain carboxylic acid chlorinated rare earth complex and aluminium alkyl is employed, after an optional composition conjugated alkene is added, the phase state of the catalyst system is relatively stable, when the catalytic activity and the catalytic-performance stability are guaranteed, the usage amount of expensive aluminium alkyl is reduced, so that the conjugated diene polymer with high cis content and narrow molecular weight distribution is prepared.
Description
Technical field
The present invention relates to a kind of rare earth catalyst and prepare the method for high-cis conjugated diene polymer for catalysis conjugate diene polymerization.
Background technology
Conjugated diene (as: divinyl or isoprene) can carry out tactic polymerization under transition-metal catalyst (as: nickel system, cobalt system or titanium system) and rare earth catalyst (as: neodymium system), obtain high-cis (cis-Isosorbide-5-Nitrae content >95%) polyhutadiene or polyisoprene.This high Cis formula polyhutadiene or polyisoprene are specially adapted to manufacture tire and other elastomeric articles.
The cis-1 of polybutadiene rubber or polyisoprene, 4 structural contents have a significant effect to its physical and mechanical properties and dynamic properties, when cis-1, during 4 structural content > 96%, its content often increases by 1%, the performance of diolefin rubber can be made to significantly improve, as tensile strength can improve 6kg/cm
2, 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 building desirable vulcanization crosslinking network and reducing chain free terminal concentration, contributes to improving rubber performance further.Usually, the polyhutadiene adopting rare-earth catalysis system obtained or polyisoprene product, than adopting the obtained corresponding product of cobalt system, titanium system or Nickel salt catalyzer, there is better green strength and cured properties, as little in hysteresis loss, heat-dissipating is low, wear resistance good, stress crystallinity is good, autohension is good, the good and warping strength be full of cracks of tear strength, the performance of running at high speed of automobile can be adapted to, meet the demand of tire high speed meridian.Improve cis-Isosorbide-5-Nitrae structural content further if improve to reach by catalyzer or polymerization technique and reduce molecular weight distribution, being then conducive to obtaining the more excellent conjugate diene polymerization product of performance.The kind of catalyzer and manner of formulation affect the cis-Isosorbide-5-Nitrae content of conjugate diene polymerization product and the important factor of molecular weight distribution.
Ziegler-Natta type rare-earth catalysis system can be divided into binary catalyst system, three-element catalytic system and multiple catalyzing system according to component.Binary catalyst system is made up of neodymium trichloride nL title complex (Nd) and aluminum alkyls (Al), the wherein usual >20 of Al/Nd mol ratio, see: Chinese science, B collects, 2009,39(10): 1006 ~ 1027.Binary system component is few, and influence factor is few, blending process and method simple.But this kind of catalyzer is nonhomogeneous system mostly, the less stable when catalysis conjugate diene polymerization, the all more difficult control of catalytic process and polymerization process, polymericular weight is larger, molecular weight distribution is wider, polymerization system viscosity is large, brings difficulty to the production processes such as heat transfer, conveying, glue spraying, cohesion, and increases energy consumption.In order to solve the deficiency of above-mentioned heterogeneous catalyst, propose the binary catalyst system be made up of two (trifluoroacetic acid) Neodymium trichloride nL title complex or alkoxyl group Neodymium trichloride and aluminum alkyls of improvement, as (CF
3cOO)
2ndCl (C
2h
5)
2o or (CF
3cOO)
2ndClC
2h
5the binary rare-earth catalyzer that OH and triethyl aluminum form is homogeneous system in toluene, but catalyzer directional property relative mistake, and toluene is as solvent, can reduce catalyst activity, and see: polymer communication, 1979,6:367 ~ 369; 1984,5:358 ~ 362.By alkoxyl group Neodymium trichloride Nd (OR)
3-ncl
nthe binary catalyst system formed with triethyl aluminum, wherein R is butyl or amyl group and isomer thereof, and the cis-content of prepared polyhutadiene is relatively on the low side, see: chemical journal, 1983,41:490 ~ 497.
Three-element catalytic system is made up of rare earth carboxylate or rare earth phosphonate compounds (Ln), aluminum alkyls (Al), halogen contained compound.For rare earth carboxylate system, can homogeneous catalyst system be formed under certain condition, but aluminum alkyls consumption is usually comparatively large, as: Al/Ln mol ratio >15, see: Chinese science, B collects, 2009,39:1006 ~ 1027.Aluminum alkyls is expensive, the diisobutylaluminium hydride for conventional: the market value at present containing the hexane solution of 25% diisobutylaluminium hydride is: 1778 yuan/800mL.Aluminum alkyls consumption is higher, and catalyzer cost just significantly improves.And, in existing rare earth catalyst system, usually need to adopt increase aluminum alkyls consumption to reduce polymericular weight, and molecular weight distribution is broadened.
In addition, catalyst activity obviously depends on preparation condition, causes may there is dynamics model in ternary catalyst systems, all more difficult control of catalysis and polymerization process, the molecular weight and molecualr weight distribution of polymerisate is caused all to be difficult to regulation and control, see: US5428119 and W09305083.In order to improve catalyst stability and directional property further, improve constitutional unit regularity and reduce molecular weight distribution, can add a certain amount of containing oxygen, phosphorus or sulphur organic compound in above-mentioned ternary catalyst systems, form multiple catalyzing system, see: CN101927186A and CN102532368A, but catalyst component is many, influence factor is many, complex process, and regulation and control difficulty is also relatively large.
Summary of the invention
The object of this invention is to provide a kind of homogeneous phase rare earth catalyst and the method for the preparation of high-cis conjugated diene polymer thereof.Adopt the binary homogeneous phase rare earth catalyst system that Primary Catalysts long-chain carboxylic acid Rare Earth Complexes A and aluminum alkyls B forms, after adding selectable components C, catalyst system phase also can be made more stable, while guarantee catalytic activity and stable in catalytic performance, significantly can reduce expensive aluminum alkyls consumption, prepare the conjugated diene polymer of high cis-contents, narrow molecular weight distribution.
Rare earth catalyst provided by the present invention, it basic composition is:
Component A is chlorination rare earth complex monomer: MCl
1(RCOO)
2nL, MCl
2(RCOO)
1nL or MCl
1(RCOO)
2nL and MCl
2(RCOO)
1the mixture of nL.Wherein, M is rare earth element, preferred neodymium or praseodymium; RCOO-is C
6-C
10straight-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, sad, 2-ethyl enanthic acid root, 3-ethyl enanthic acid root, n-nonanoic acid root, sad of 2-ethyl, sad of 3-ethyl, decanoate, neodecanoic acid root; Be preferably: cycloalkanes acid group, 2 ethyl hexanoic acid root, sad, n-nonanoic acid root or neodecanoic acid root; Be more preferably: cycloalkanes acid group, 2 ethyl hexanoic acid root, sad or neodecanoic acid root; N=1-4; L is the organic compound such as alcohol, ether, carboxylic acid or phosphoric acid ester.
Wherein,
Alcohol is C
1-C
8alcohol, be selected from any one in following material or their mixture: methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, amylalcohol, hexanol, hexalin, enanthol, phenylcarbinol, phenylethyl alcohol, octanol, 2-Ethylhexyl Alcohol; Be preferably: Virahol, hexanol, enanthol, octanol, 2-Ethylhexyl Alcohol; Be more preferably: octanol, 2-Ethylhexyl Alcohol, enanthol.
Carboxylic acid is C
6-C
10carboxylic acid, be selected from following C
6-C
10straight-chain carboxylic acid or branched carboxylic acids material in any one or their mixture: 2 ethyl hexanoic acid, 3-thylhexoic acid, enanthic acid, sad, 2-ethyl enanthic acid, 3-ethyl enanthic acid, n-nonanoic acid, 2-ethyl is sad, 3-ethyl is sad, capric acid, neodecanoic acid; Be preferably: 2 ethyl hexanoic acid, sad, n-nonanoic acid, neodecanoic acid; Be more preferably: 2 ethyl hexanoic acid, sad, neodecanoic acid.
Ether is C
1-C
8ether, be selected from any one in following material or their mixture: ether, methyl ethyl ether, butyl ether, tetrahydrofuran (THF), dioxane; Be preferably: ether, tetrahydrofuran (THF), dioxane; More preferably: tetrahydrofuran (THF), dioxane.
Organophosphate is selected from any one in following material or their mixture: trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate propyl ester, tributyl phosphate, TNPP tri n pentyl phosphate, tri hexyl phosphate, THP triheptylphosphate, triphenylphosphate, triphenylphosphate, Tritolyl Phosphate, dimethyl phosphate, diethyl phosphoric acid, di(2-ethylhexyl)phosphate propyl ester, dibutyl phosphate, di(2-ethylhexyl)phosphate pentyl 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.Preferred: tricresyl phosphate propyl ester, tributyl phosphate, TNPP tri n pentyl phosphate, tri hexyl phosphate; More preferably: tricresyl phosphate propyl ester, tributyl phosphate, TNPP tri n pentyl phosphate.
B component is aluminum alkyls: be selected from AlR '
3or AlHR ' (B1)
2(B2) or both mixtures, wherein R ' is C
1-C
6alkyl; Be selected from any one in following material or their mixture: trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three amyl group aluminium, three hexyl aluminium, diethyl aluminium hydride, diisobutylaluminium hydride; Preferred: triethyl aluminum, triisobutyl aluminium, diethyl aluminium hydride, diisobutylaluminium hydride or their mixture; More preferably: triisobutyl aluminium, diisobutylaluminium hydride or both mixtures.
Selectable components C: conjugated alkene.
The mol ratio of each component is A:B:C=1:3 ~ 40:0 ~ 4, is preferably 1:3.5 ~ 35:0 ~ 3.5, is more preferably 1:4 ~ 25:0 ~ 3; When using component C, C/A molar ratio is 0.5 ~ 3, and the mol ratio of each component is preferably A:B:C=1:4 ~ 25:0.5 ~ 3.
Component A is Primary Catalysts, can adopt and prepare with the following method:
Rare earth chloride salt and rare earth carboxylate are mixed to form homogeneous phase solution according to the molar ratio of 1:2 ~ 2:1 in organic ligand L, wherein the mol ratio of organic ligand L and rare earth element is 5 ~ 20, the lower reaction 4 ~ 10h of backflow, by reaction product organic solvent washing, filter, drying, obtains chlorination rare earth complex monomer.Organic solvent is selected from any one in following material or their mixture: hexane, hexanaphthene, heptane, octane, methylcyclohexane or the (C that raffinates oil
6~ C
8alkane mixing solutions).
Rare earth catalyst of the present invention is the binary homogeneous phase rare earth catalyst system be made up of Primary Catalysts A and aluminum alkyls B, after adding optional component C, catalyst system phase can be made more stable.The preparation temperature of catalyzer 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 one in following material or their mixture: hexane, hexanaphthene, heptane, octane, methylcyclohexane or the (C that raffinates oil
6~ C
8alkane mixing solutions).Method for preparing catalyst is fairly simple, B component 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 B component; Or B component 2 is joined in component A or component A and component C mixture in, add B component 1 again after mixing; Or the mixture of component A or component A and component C is joined in B component 2, then adds B component 1.Catalyzer depends on Aging Temperature setup time, and temperature is higher, and the time is shorter, is generally 1 minute ~ 100 hours, preferably: 2 minutes ~ 50 hours, more preferably: 5 minutes ~ 20 hours.
In order to improve the solvability of catalyzer in alkane solvent further, long-chain alcohol, carboxylic acid or phosphoric acid ester can also be added; Meanwhile, the introducing of a small amount of long-chain alcohol, carboxylic acid or phosphoric acid ester, can also improve molecular weight and the cis-content of polymkeric substance further, and reduce molecular weight distribution.The mol ratio of the long-chain alcohol introduced, carboxylic acid or phosphate ester additive and Primary Catalysts A is 0.2 ~ 5, preferably: 0.5 ~ 4.8, more preferably: 0.6 ~ 4.5.
Present invention also offers and a kind ofly adopt above-mentioned rare earth catalyst for the preparation of the polymerization process of high-cis conjugated diene polymer, under the existence of rare earth catalyst of the present invention, take hydrocarbon compound as polymer solvent, conjugated diene monomer concentration is 1.0 ~ 6.0mol/L, preferred: 1.2 ~ 5.0mol/L, more preferably: 1.5mol/L ~ 4.0mol/L, polymerization temperature is-50 ~ 120 DEG C, preferred :-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 process is the hydrocarbon compound that conjugate diene polymerization is conventional, any one preferably in following material or their mixture: hexane, hexanaphthene, heptane, octane, methylcyclohexane or the (C that raffinates oil
6~ C
8alkane mixing solutions).
Polymerization process of the present invention is applicable to polymerization or the copolymerization of conjugated diene, comprises 1,3-butadiene, 1,3-isoprene, 2,3-dimethylbutadienes, 2,4-hexadienes, 1,3-pentadiene or 2-methyl isophthalic acid, 3-pentadiene etc.
Adopt rare earth catalyst system of the present invention, following effect can be reached:
1. without the need to adding chlorine-containing compound as activator, simplifying the preparation technology of catalyzer, obtaining binary homogeneous phase rare earth catalyst system;
2. halogen and rare earth element are directly with chemical bonds, are conducive to forming single-activity center, obtain narrow molecular weight distributions polymerisate, and improve the stability of catalyzer;
3. significantly reduce aluminum alkyls consumption, even B/A molar ratio can be down to 4.0 or lower, thus significantly reduce catalyzer cost;
4. cis-Isosorbide-5-Nitrae the content of the conjugated diene polymer prepared by can up to more than 99%, and molecular weight distribution narrower (dispersion index≤3.0), molecular weight distributing index can reach 1.9.
5. by regulating the ratio of chlorion and carboxylate radical in component A, the molecular weight regulating polymerisate can be realized, without the need to using expensive aluminum alkyls.
Embodiment:
Adopt Waters1515 type GPC, the number-average molecular weight (M of four root chromatogram columns (HT3, HT4, HT5, HT6) test polymer (tetrahydrofuran solvent system)
n), weight-average molecular weight (M
w) and molecular weight distribution (PDI, M
w/ M
n).The microtexture content of polymkeric substance is measured by infrared spectra (FTIR) method.
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 preparing and polyreaction are carried out all under nitrogen protection.
By NdCl
3, Nd (C
5h
10(C
2h
5) COO)
3with tetrahydrofuran (THF) according under the molar ratio of 1:2:10, under backflow, react 4h, form homogeneous phase solution, obtain reaction product, with hexanes wash, filter, dry, obtain chlorination rare earth complex monomer NdCl
1(C
5h
10(C
2h
5) COO)
2tHF(A1).Take hexane as solvent, 0.99mmol A1 and 3.95mmol isocaprylic acid are joined in 14.8mmol triisobutyl aluminium, 45 DEG C of reactions 1 hour, obtain light blue homogeneous catalyst.
In polymerization reactor, add 40ml divinyl, raffinate oil and above-mentioned catalyst system, monomer concentration=2.4mol/L, the mol ratio of catalyst component A and monomer is 4 × 10
-4, polyase 13 hour at 50 DEG C, adds the ethanolic soln termination reaction of the BHT containing 1% quality, washes rear drying with water, and is placed in 40 DEG C of vacuum drying ovens and is dried to constant weight, and polyhutadiene yield is 36%, weight-average molecular weight (M
w) be 4.4 × 10
5, molecular weight distributing index (M
w/ M
n) be 2.7, cis-Isosorbide-5-Nitrae content is 98.0%.
Embodiment 2
Primary Catalysts preparation, with embodiment 1, is by Nd (C
5h
10(C
2h
5) COO)
3change Nd (C into
7h
15cOO)
3, prepare catalyst n dCl
1(C
7h
15cOO)
2tHF(A2).0.99mmolA2 is joined in 24.7mmol triisobutyl aluminium, 45 DEG C of reactions 1 hour, obtain light blue homogeneous catalysis system.
Polymerisation process is with embodiment 1, and just the mol ratio of catalyst component A and monomer is 2.4 × 10
-4, be polymerized 2.8 hours at 50 DEG C.Polyhutadiene yield is 31%, M
wbe 3.3 × 10
5, M
w/ M
nbe 2.6, cis-Isosorbide-5-Nitrae content is 98.4%.
Embodiment 3
Primary Catalysts preparation is with embodiment 2.Take hexane as solvent, in 3.45mmol diisobutyl aluminium hydride, add 0.99mmol A2,45 DEG C of reactions 3 hours, obtain light blue homogeneous catalysis system.
Polymerisation process is with embodiment 1, and just the mol ratio of catalyst component A and monomer is 8 × 10
-4, the mol ratio adding triisobutyl aluminium and A2 in polymerization system is polyase 13 hour at 1,50 DEG C.Polyhutadiene yield is 29%, M
wbe 6.14 × 10
5, M
w/ M
nbe 2.8, cis-Isosorbide-5-Nitrae content is 98.2%.Embodiment 4
Catalyst preparing is with embodiment 3.
Take hexane as solvent, in 3.455mmol diisobutyl aluminium hydride, add 1.0mmolA1,45 DEG C of reactions 3 hours, obtain light blue homogeneous catalysis system.
Polymerisation process is with embodiment 3, and the mol ratio just adding triisobutyl aluminium and A2 in polymerization system is 2.Polyhutadiene yield is 47%, M
wbe 4.38 × 10
5, M
w/ M
nbe 2.8, cis-Isosorbide-5-Nitrae content is 98.0%.
Embodiment 5
Catalyst preparing and polyreaction are carried out all under nitrogen protection.Primary Catalysts preparation method, with embodiment 1, is by Nd (C
5h
10(C
2h
5) COO)
3change Nd (C into
9h
19cOO)
3, prepare catalyst n dCl
1(C
9h
19cOO)
2tHF(A3).0.99mmol A3 and 0.99mmol tributyl phosphate are joined in 14.8mmol triisobutyl aluminium, 45 DEG C of reactions 1 hour, obtains light blue homogeneous catalysis system.
Polymerization process and post-treating method are with embodiment 1, and just the mol ratio of catalyst component A and monomer is 8 × 10
-4, polyase 13 hour at 50 DEG C.Polyhutadiene yield is 48%, M
wbe 4.7 × 10
5, M
w/ M
nbe 2.8, cis-Isosorbide-5-Nitrae content is 98.0%.
Embodiment 6
Primary Catalysts preparation method, with embodiment 1, just adds isooctyl alcohol (oca) in reaction system, and NdCl
3: Nd (C
5h
10(C
2h
5) COO)
3mol ratio be 2:1, obtain chlorination rare earth complex monomer NdCl
2(C
5h
10(C
2h
5) COO)
14oca (A4).Take hexane as solvent, by 0.99mmol A4 with join in 14.8mmol triisobutyl aluminium, then add 1mmol divinyl 0 DEG C reaction 2 hours, obtain catalyst system.
Polymerization process and post-treating method are with embodiment 1, and just the mol ratio of catalyst component A4 and monomer is 2.7 × 10
-4, be polymerized 2.5 hours at 45 DEG C.Polyhutadiene yield is 15%, M
wbe 9.63 × 10
5, M
w/ M
nbe 2.6, cis-Isosorbide-5-Nitrae content is 99.2%.
Embodiment 7
Primary Catalysts preparation method is with embodiment 6.Take hexane as solvent, 0.99mmol A4 and 0.99mmol divinyl are joined in 14.8mmol triisobutyl aluminium, at 40 DEG C of reaction 10min, obtain catalyst system.
Polymerization process and post-treating method are with embodiment 1, and just the mol ratio of catalyst component A and monomer is 2.7 × 10
-4, be polymerized 2.5 hours start latter 45 DEG C of reaction at-14 DEG C at.Polyhutadiene yield is 19%, M
wbe 1.09 × 10
6, M
w/ M
nbe 2.2, cis-Isosorbide-5-Nitrae content is 99.0%.
Embodiment 8
Primary Catalysts preparation method, with embodiment 1, is NdCl
3: Nd (C
5h
10(C
2h
5) COO)
3mol ratio be 1.2:1.8, obtain NdCl
2(C
5h
10(C
2h
5) COO)
1tHF and NdCl (C
5h
10(C
2h
5) COO)
2the mixture (A5,1:4) of THF.Method for preparing catalyst, with embodiment 9, just reacts 2h at 45 DEG C.
Polymerization process and post-treating method are with embodiment 1, and just the mol ratio of catalyst component A and monomer is 2.6 × 10
-4, polyase 13 hour at 50 DEG C.Polyhutadiene yield is 50%, M
wbe 4.49 × 10
5, M
w/ M
nbe 2.8, cis-Isosorbide-5-Nitrae content is 98.2%.
Embodiment 9
Primary Catalysts preparation method is with embodiment 8.Take hexane as solvent, in 8.6mmol triisobutyl aluminium, add 0.99mmol A5, at 45 DEG C of reaction 40min, obtain homogeneous catalysis system.
Polymerization process and post-treating method are with embodiment 1, and just the mol ratio of catalyst component A5 and monomer is 8 × 10
-4, polyase 13 hour at 50 DEG C.Polyhutadiene yield is 37%, M
wbe 6.94 × 10
5, M
w/ M
nbe 2.9, cis-Isosorbide-5-Nitrae content is 98.3%.
Embodiment 10
Primary Catalysts preparation method is with embodiment 8.Take hexane as solvent, in 6.9mmol triisobutyl aluminium, add 0.99mmol A5, at 45 DEG C of reaction 1h, obtain homogeneous catalysis system.
Polymerization process and post-treating method are with embodiment 9, and just the mol ratio of catalyst component A5 and monomer is 5 × 10
-4, add triisobutyl aluminium (Al:A5=2), polyase 13 hour at 50 DEG C.Polyhutadiene yield is 47%, M
wbe 4.54 × 10
5, M
w/ M
nbe 2.2, cis-Isosorbide-5-Nitrae content is 98.3%.
Embodiment 11
Primary Catalysts preparation method is with embodiment 8.Method for preparing catalyst is with embodiment 10, and just Al/A5=15,45 DEG C are reacted 3h.
Isoprene and divinyl 2/3 are configured to the solution of raffinating oil that concentration is 3.4mol/L in molar ratio, and polymerization process and post-treating method are with embodiment 9, and just the mol ratio of catalyst component A5 and monomer is 4 × 10
-4, fourth penta copolymer yield is 80%, M
wbe 4.19 × 10
5, M
w/ M
nbe 2.9, isoprene unit cis-Isosorbide-5-Nitrae content is 98.3%, and butadiene unit cis-Isosorbide-5-Nitrae content is 98.2%.
Embodiment 12
Method for preparing catalyst is with embodiment 11.
Joined by catalyzer in isoprene monomer liquid at 0 DEG C, the mol ratio of component A5 and monomer is 4 × 10
-4, adiabatic polymerisation 3h, post-treating method is with embodiment 9, and polyisoprene yield is 88%, M
wbe 6.49 × 10
5, M
w/ M
nbe 2.8.
Embodiment 13
Primary Catalysts preparation method, with embodiment 1, just adds tributyl phosphate (TBP) in reaction system, and NdCl
3: Nd (C
7h
15cOO)
3mol ratio be 1:2, obtain chlorination rare earth complex monomer NdCl
1(C
7h
15cOO)
2tBP (A6).Method for preparing catalyst, with embodiment 10, is Al/A6=15.
Polymerization process and post-treating method are with embodiment 1, and just the mol ratio of catalyst component A6 and monomer is 8 × 10
-4, polyase 13 hour at 50 DEG C.Polyhutadiene yield is 64%, M
wbe 4.81 × 10
5, M
w/ M
nbe 2.8, cis-Isosorbide-5-Nitrae content is 98.0%.
Claims (10)
1. a rare earth catalyst, it basic composition is:
A: chlorination rare earth complex monomer is MCl
1(RCOO)
2nL, MCl
2(RCOO)
1nL or MCl
1(RCOO)
2nL and MCl
2(RCOO)
1the mixture of nL; M is rare earth element, and RCOO-is C
6-C
10straight-chain carboxylic acid's root or branched carboxylic acids root, n=1-4; L is organic ligand, is selected from alcohol, ether, carboxylic acid or organophosphate;
B: alkylaluminium cpd, is selected from AlR '
3or AlHR '
2or both mixtures, wherein R ' is C
1-C
6alkyl;
C: selectable components is conjugated alkene;
The mol ratio of each component is A:B:C=1:3 ~ 40:0 ~ 4.
2. rare earth catalyst 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 homogeneous phase solution according to the molar ratio of 1:2 ~ 2:1 in organic ligand L, wherein the mol ratio of organic ligand L and rare earth element is 5 ~ 20, the lower reaction 4 ~ 10h of backflow, by reaction product organic solvent washing, filter, drying, 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, sad, 2-ethyl enanthic acid root, 3-ethyl enanthic acid root, n-nonanoic acid root, sad of 2-ethyl, sad of 3-ethyl, decanoate or neodecanoic acid root;
B component is selected from any one in following material or their mixture: trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three amyl group aluminium, three hexyl aluminium, diethyl aluminium hydride, diisobutylaluminium hydride.
3. rare earth catalyst according to claim 1, is characterized in that:
In the organic ligand L of component A, alcohol is C
1-C
8alcohol, be selected from any one in following material or their mixture: methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, amylalcohol, hexanol, hexalin, enanthol, phenylcarbinol, phenylethyl alcohol, octanol, 2-Ethylhexyl Alcohol, carboxylic acid is C
6-C
10carboxylic acid, be selected from following C
6-C
10straight-chain carboxylic acid or branched carboxylic acids material in any one or their mixture: 2 ethyl hexanoic acid, 3-thylhexoic acid, enanthic acid, sad, 2-ethyl enanthic acid, 3-ethyl enanthic acid, n-nonanoic acid, 2-ethyl is sad, 3-ethyl is sad, capric acid, neodecanoic acid, ether is C
1-C
8ether, be selected from any one in following material or their mixture: ether, methyl ethyl ether, butyl ether, tetrahydrofuran (THF), dioxane, organophosphate is selected from any one in following material or their mixture: trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate propyl ester, tributyl phosphate, TNPP tri n pentyl phosphate, tri hexyl phosphate, THP triheptylphosphate, triphenylphosphate, triphenylphosphate, Tritolyl Phosphate, dimethyl phosphate, diethyl phosphoric acid, di(2-ethylhexyl)phosphate propyl ester, dibutyl phosphate, di(2-ethylhexyl)phosphate pentyl 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 of claim 2 and 3, it is characterized in that:
In the organic ligand L of component A, alcohol is selected from: methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, amylalcohol, hexanol, hexalin, enanthol, phenylcarbinol, phenylethyl alcohol, n-Octanol or 2-Ethylhexyl Alcohol; Ether is selected from: tetrahydrofuran (THF) or Isosorbide-5-Nitrae-dioxane; Carboxylic acid is selected from: 2 ethyl hexanoic acid, 3-thylhexoic acid, n-caprylic acid, 2-ethyl enanthic acid, 3-ethyl enanthic acid, n-nonanoic acid, 2-ethyl is sad, 3-ethyl is sad, n-capric acid or neodecanoic acid; Organophosphate 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.
5. rare earth catalyst according to claim 4, is characterized in that: in the organic ligand L of component A, alcohol is Virahol, hexanol, enanthol, octanol or 2-Ethylhexyl Alcohol; Carboxylic acid is 2 ethyl hexanoic acid, sad, n-nonanoic acid or neodecanoic acid; Organophosphate is tricresyl phosphate propyl ester, tributyl phosphate or TNPP tri n pentyl phosphate.
6. rare earth catalyst according to claim 2, is characterized in that: in component A, RCOO-is cycloalkanes acid group, 2 ethyl hexanoic acid root, sad, n-nonanoic acid root or decanoate;
B component is triisobutyl aluminium, diisobutylaluminium hydride or both mixtures.
7. rare earth catalyst according to claim 1, is characterized in that: in catalyzer, the mol ratio of each component is: A:B:C=1:3.5 ~ 35:0 ~ 3.5, are more preferably 1:4 ~ 25:0 ~ 3.
8. a polymerization process for conjugated diene, is characterized in that: adopt claim 1-7 any one rare earth catalyst catalysis conjugated diene to be all polymerized or copolymerization at hydrocarbon compound solvent, prepare corresponding conjugated alkene homopolymer or multipolymer.
9. the polymerization process of conjugated diene according to claim 8, is characterized in that: conjugated diene concentration is 1.0 ~ 6.0mol/L, and polymerization temperature is-50 ~ 120 DEG C, and catalyst charge counts 0.3 × 10 with component A and monomer mole ratio
-4~ 1.5 × 10
-3;
Hydrocarbon compound solvent is selected from any one in following material or their mixture: hexane, hexanaphthene, heptane, octane, methylcyclohexane or raffinate oil;
Conjugated diene is selected from 1,3-butadiene, 1,3-isoprene, 2,3-dimethylbutadienes, 2,4-hexadienes, 1,3-pentadiene or 2-methyl isophthalic acid, 3-pentadiene.
10. the polymerization process of conjugated alkene according to claim 9, is characterized in that: conjugated diene monomer concentration is 1.2 ~ 5.0mol/L, and polymerization temperature is-30 ~ 110 DEG C, and catalyst component A and monomer mole ratio are 0.5 × 10
-4~ 1.3 × 10
-3.
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