CN1153789C - Arene-improved double-olefine polymerizing rare earth catalyst and its preparation - Google Patents
Arene-improved double-olefine polymerizing rare earth catalyst and its preparation Download PDFInfo
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- CN1153789C CN1153789C CNB991212878A CN99121287A CN1153789C CN 1153789 C CN1153789 C CN 1153789C CN B991212878 A CNB991212878 A CN B991212878A CN 99121287 A CN99121287 A CN 99121287A CN 1153789 C CN1153789 C CN 1153789C
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Abstract
The present invention belongs to an arene-improved double-olefin polymerizing rare earth catalyst and a preparing method. The catalyst is composed of rare earth carboxylate, rare earth chloride complexes, organoaluminium compounds, halogen containing compounds and arene. An arene earth catalyst is led in the process of preparing the catalyst; the rare earth catalyst keeps the characteristic of preparing a copolymer of polybutadiene, polyisoprene and butadiene isoprene, and the copolymer has more than 95% of cis-1, 4, high linearity, and no gelatin; the rate earth catalyst also has the characteristics that the catalytic activity is obviously improved, and the molecular weight of polymerisate is effectively regulated by changing the types and the dosage of the arene.
Description
The invention belongs to improved double-olefine polymerizing rare earth catalyst of aromatic hydrocarbons and preparation method.
The catalyzer of being made up of rare earth compound is divinyl, isoprene high cis formula polymeric effective catalyst system, but the molecular weight of its catalytic activity and polymerisate mainly is to regulate by the consumption that changes rare earth compound and aluminum alkyls.For improving the molecular weight of catalytic activity and reduction polymerisate, just must increase the consumption of catalyzer and aluminum alkyls.Document is arranged in monomer solution, to introduce the mode of additive, reported the influence of a series of different structures and polar compound, in the hope of obtaining catalytic activity agent and molecular weight regulator the rare earth catalyst diolefin polymerization.Ren Shoujing etc. are at " rare earth catalyst synthetic rubber collected works, Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences the 4th research department work, Science Press,, 55 pages in 1980; Polymer communication, 1982, the 6 phases, 435 pages " in studied the effect characteristics of heavy addition agent, find to have only some allyl deriv, as 3-iodopropylene, two-α-propylene ether the effect that reduces polymericular weight is arranged when reducing catalytic activity.Throckmorton MC is at United States Patent (USP) U.S.Pat.No.4, disclose a kind of method of regulating the diolefin polymerization molecular weight of product with vinyl chloride, vinyl bromide in 663,405, but mentioned reagent has certain negative interaction to the rare earth catalyst activity.In addition, Japan SYnthetic Rubber Co. Ltd is at patent GB 2,101, disclose among the 616A a kind of in aliphatic solvents BTX aromatics such as toluene to regulate the method for polymer molecular weight, aromatic hydrocarbons in the polymerisation medium has the effect that reduces polymer molecular weight, but also participates in the catalytic activity that obviously reduces rare earth catalyst on the active centre with monomeric competitive coordination effect because of it simultaneously.
The purpose of this invention is to provide improved double-olefine polymerizing rare earth catalyst of a kind of aromatic hydrocarbons and preparation method.In the catalyst preparation process, introduce the rare earth catalyst of aromatic hydrocarbons, remove and keep making Gao Shun-1, outside the characteristics of the polyhutadiene of 4 content＞95%, high linearity gel-free, polyisoprene and butadiene isoprene copolymer, have also that catalytic activity obviously improves and can be by changing the characteristics that aromatic hydrocarbon type and consumption are effectively regulated polymer molecular weight.
Because the aromatic hydrocarbons of in the rare earth catalyst process for preparation, introducing, can improve the solubility property of catalyst component and form title complex with the Lewis acid constituents, participate in alkylated reaction directly and become the part of forming the active centre, therefore help to generate the active centre that quantity is more, thermal stability is higher, improving the active molecular weight that reduces polymerisate simultaneously of rare earth catalyst.
The catalyzer that the present invention proposes is formed LnA
3-AlR
3-X-Ar is the catalysis of rare-earth compound agent system and the LnCl of representative
33L-AlR
3-Ar is that the rare earth chloride catalyst system of representative: Ln is two kinds of elements of neodymium Nd, praseodymium Pr; A is a carboxylate radical, and these carboxylate radicals are cycloalkanes acid group naph, 2 ethyl hexanoic acid root oct, neodecanoic acid root vers; AlR
3Be organo-aluminium compound, they are triethyl aluminum Al (C
2H
5)
3, triisobutyl aluminium Al (i-C
4H
9)
3, diisobutylaluminium hydride Al (i-C
4H
9)
2H; X is chloride compound, and they are aluminium diethyl monochloride Al (C
2H
5)
2Cl, a chloro-di-isobutyl aluminum Al (i-C
4H
9)
2Cl, tertiary butyl chloride t-C
4H
9Cl, trimethylchlorosilane (CH
3)
3SiCl; L is the sub-compound of power supply, and they are Virahol i-C
3H
7OH, tributyl phosphate TBP; Ar is an aromatic hydrocarbons, they be benzene, toluene, ethylbenzene, isopropyl benzene, dimethylbenzene, ortho-xylene ,-dimethylbenzene, right-dimethylbenzene, trimethylbenzene, mellitene, vinyl benzene, Vinylstyrene, naphthalene, dihydronaphthalene, naphthane, anthracene, phenanthrene.
Preparation of catalysts is to carry out ageing under 0～50 ℃ in saturated hydrocarbon solvent, digestion time is 30 minutes～24 hours, can also can in the presence of monomer-free, carry out in the presence of the small amounts of monomer, the mol ratio of each component of catalyzer: the Al/Ln ratio is 20～40, the Cl/Ln ratio is 2.0～4.0, aromatic hydrocarbons/Ln ratio is 1～500, and monomer/Ln ratio is 2～10.This catalyzer is applicable to equal polymerization of the cis of divinyl, isoprene and the cis copolymerization of the two, being aggregated in the solvent existence also can carry out under solvent-free situation down, adopting stable hydrocarbon hexane, hexanaphthene, heptane when carrying out solution polymerization is solvent, monomer concentration is 8～20g/100mL, and catalyst levels Ln/ monomer ratio is 6 * 10
-7～1.0 * 10
-5Mol/g, polymerization temperature are 20～80 ℃, and polymerization time is 1～4 hour; Reaction is containing 1%2, and the ethanolic soln of 6-di-tert-butyl methyl phenol stops, the polymkeric substance that in excess ethyl alcohol, settles out, and after the washing with alcohol extruding, in 40 ℃ of drying under reduced pressure 24 hours, the calculating monomer conversion of weighing; In 30 ℃ of toluene solutions, measure the intrinsic viscosity [η] of polymerisate, and characterize the molecular weight size of polymerisate with [η]; Measure microstructure of product and composition with infrared spectra and nuclear-magnetism spectrum.
The present invention proposes following examples as further instruction:
Embodiment 1:
The Nd (naph) that under nitrogen protection, in exsiccant 15mL catalyst preparation pipe, adds 4.0mL toluene, 1.0mL0.25mol/L successively
3Al (the i-C of hexane solution, 2.5mL0.25mol/L
4H
9)
2Al (the i-C of Cl hexane solution, 2.5mL3.0mol/L
4H
9)
3Hexane solution, [Nd]=2.5 * 10 at this moment
-5Mol/mL, the mol ratio of Nd/Al/Cl/ toluene is 1.0/30/2.5/150, is used for polymerization in 20 ℃ of following ageings after 30 minutes.
Under nitrogen protection, in the polymerization bottle of the dry deoxygenation of about 150mL, add 80mL hexane, 20mL isoprene and 1.0mL catalyst solution.This moment, monomer concentration was 13.6g/100mL, and Nd/ isoprene ratio is 1.8 * 10
-6Mol/g.Reaction is after 4 hours in 50 ℃ of waters bath with thermostatic control, contain 1.0%2 with 2mL, the ethanolic soln of 6-di-tert-butyl methyl phenol stops polymerization, and the polymkeric substance that settles out in excess ethyl alcohol again is after the washing with alcohol extruding, in 40 ℃ of drying under reduced pressure 24 hours, get isoprene polymerization product 12.9g, transformation efficiency 95%, [η] are 6.6dL/g, product is 95.6% through suitable-1, the 4 chain link content of infrared measurement.
Toluene is changed under the situation of hexane when only preparing catalyzer in that other conditionally completes are identical, [η] of monomer conversion and polymerisate is respectively 60%, 8.4dL/g.
Embodiment 2:
As described in embodiment 1, replace under the situation of toluene with benzene when only preparing catalyzer in that other conditionally completes are identical, this moment, Nd/ benzene ratio was 1.0/180, [η] of gained monomer conversion and polymerisate is respectively 75%, 6.4dL/g.
Embodiment 3:
As described in embodiment 1, replace under the situation of toluene with ethylbenzene when only preparing catalyzer in that other conditionally completes are identical, this moment, Nd/ ethylbenzene ratio was 1.0/130, [η] of gained monomer conversion and polymerisate is respectively 80%, 6.9dL/g.
Embodiment 4:
As described in embodiment 1, replace under the situation of toluene with isopropyl benzene when only preparing catalyzer in that other conditionally completes are identical, this moment, Nd/ isopropyl benzene ratio was 1.0/115, [η] of gained monomer conversion and polymerisate is respectively 85%, 6.7dL/g.
Embodiment 5:
As described in embodiment 1, replace under the situation of toluene with ortho-xylene when only preparing catalyzer in that other conditionally completes are identical, this moment, Nd/ ortho-xylene ratio was 1.0/130, [η] of gained monomer conversion and polymerisate is respectively 90%, 6.2dL/g.
Embodiment 6:
As described in embodiment 1, replace under the situation of toluene with sym-trimethylbenzene when only preparing catalyzer in that other conditionally completes are identical, this moment, Nd/ sym-trimethylbenzene ratio was 1.0/115, [η] of gained monomer conversion and polymerisate is respectively 68%, 7.2dL/g.
Embodiment 7:
As described in embodiment 1, replace under the situation of toluene with 4.0mL5.62mol/L vinyl benzene hexane solution when only preparing catalyzer in that other conditionally completes are identical, this moment, Nd/ vinyl benzene ratio was 1.0/90, and [η] of gained monomer conversion and polymerisate is respectively 86%, 7.0dL/g.
Embodiment 8:
As described in embodiment 1, replace under the situation of toluene with 4.0mL3.12mol/L Vinylstyrene hexane solution when only preparing catalyzer in that other conditionally completes are identical, this moment, Nd/ Vinylstyrene ratio was 1.0/50, and [η] of gained monomer conversion and polymerisate is respectively 70%, 6.8dL/g.
Embodiment 9:
Under nitrogen protection, in exsiccant catalyst preparation pipe, add the mellitene hexane solution of 1.0mL0.25mol/L, Nd (naph) 3 hexane solutions of 1.0mL0.25mol/L, the Al (i-C of 2.5mL0.25mol/L successively
4H
9)
2Al (the i-C of Cl hexane solution, 2.5mL3.0mol/L
4H
9)
3Hexane solution, add the 3.0mL hexane, at this moment [Nd]=2.5 * 10
-5Mol/mL, the ratio of Nd/Al/Cl/ mellitene is 1.0/30/2.5/1.0, is used for polymerization in 50 ℃ of following ageings after 60 minutes.
Under nitrogen protection, in the polymerization bottle of the dry deoxygenation of about 150mL, add 70mL hexane, 30mL isoprene and 1.0mL catalyst solution.This moment, monomer concentration was 20g/100mL, and Nd/ isoprene ratio is 1.2 * 10
-6Mol/g.After 2 hours, get isoprene polymerization product 16.3g in 80 ℃ of reactions, transformation efficiency 81%, [η] are 5.0dL/g, and product is 94.8% through suitable-1, the 4 chain link content of infrared analysis.
The mellitene hexane solution is changed under the situation of hexane when only preparing catalyzer in that other conditionally completes are identical, [η] of monomer conversion and polymerisate is respectively 56%, 6.1dL/g.
Embodiment 10:
As described in embodiment 9, hexane solution with the 1.0mL1.0mol/L naphthalene replaces under the situation of mellitene hexane solution in that other conditionally completes are identical when only preparing catalyzer, this moment, the Nd/ naphthalene was than being 1.0/4.0, and [η] of gained monomer conversion and polymerisate is respectively 75%, 3.8dL/g.
Embodiment 11:
As described in embodiment 9, hexane solution with the 1.0mL2.5mol/L dihydronaphthalene replaces under the situation of mellitene hexane solution in that other conditionally completes are identical when only preparing catalyzer, this moment, Nd/ dihydronaphthalene ratio was 1.0/10, and [η] of gained monomer conversion and polymerisate is respectively 70%, 3.5dL/g.
Embodiment 12:
As described in embodiment 9, hexane solution with the 1.0mL5.0mol/L naphthane replaces under the situation of mellitene hexane solution in that other conditionally completes are identical when only preparing catalyzer, this moment, Nd/ naphthane ratio was 1.0/20, and [η] of gained monomer conversion and polymerisate is respectively 72%, 4.0dL/g.
Embodiment 13:
As described in embodiment 9, hexane solution with the 1.0mL0.50mol/L anthracene replaces under the situation of mellitene hexane solution in that other conditionally completes are identical when only preparing catalyzer, this moment, the Nd/ anthracene was than being 1.0/2.0, and [η] of gained monomer conversion and polymerisate is respectively 65%, 4.5dL/g.
Embodiment 14:
As described in embodiment 9, hexane solution with the 1.0mL0.75mol/L phenanthrene replaces under the situation of mellitene hexane solution in that other conditionally completes are identical when only preparing catalyzer, this moment, the ratio of Nd/ phenanthrene was 1.0/3.0, and [η] of gained monomer conversion and polymerisate is respectively 68%, 4.8dL/g.
Embodiment 15:
Al (the C that under nitrogen protection, in the catalyst preparation pipe, adds 2.5mL0.30mol/L successively
2H
5)
2Al (the i-C of Cl cyclohexane solution, 2.5mL3.0mol/L
4H
9)
2The Nd of H cyclohexane solution, 1.0mL0.25mol/L (oct)
3Between cyclohexane solution, 4.0mL-dimethylbenzene, [Nd]=2.5 * 10 at this moment
-5Mol/mL, between Nd/Al/Cl/-ratio of dimethylbenzene is 1.0/30/3.0/130, and is standby after 2 hours in 0 ℃ of following ageing.
Under nitrogen protection, in about 80mL polymerization bottle, add 50mL isoprene, 2.0mL catalyst solution successively, this moment, Nd/ isoprene ratio was 1.5 * 10
-6Mol/g.Reaction gets isoprene polymerization product 21.1g under 20 ℃ after 1 hour, and transformation efficiency 62%, [η] are 3.2dL/g.
Other conditionally completes are identical when only preparing catalyzer will between-dimethylbenzene changes under the situation of hexanaphthene, [η] of monomer conversion and polymerisate is respectively 45%, 5.4dL/g.
Embodiment 16:
As preparation rare earth catalyst agent solution as described in the embodiment 15.Under nitrogen protection, in about 150mL polymerization bottle, add cyclohexane solution, 2g isoprene and a certain amount of hexanaphthene that contains the 8g divinyl successively, make total monomer reach 10g/100mL, add the 0.8mL catalyst solution then, this moment, Nd/ monomer ratio was 2.0 * 10
-6Mol/g.In 50 ℃ of following polymerizations after 2 hours, get butadiene-isoprene copolymer and close product 7.3g, transformation efficiency 73.0%, [η] is 5.2dL/g, product is measured and is indicated as divinyl, isoprene random copolymers through infrared spectra, nuclear-magnetism spectrum, two kinds of suitable-1,4 content of monomer chain link are respectively 97.6%, 95.3%.
Other conditionally completes are identical when only preparing catalyzer will between-dimethylbenzene changes under the situation of hexanaphthene, [η] of monomer conversion and polymerisate is respectively 64%, 7.3dL/g.
Embodiment 17:
The t-C that under nitrogen protection, in the catalyst preparation pipe, adds 4.0mL0.25mol/L successively
4H
9Al (the C of Cl n-heptane solution, 2.5mL3.0mol/L
2H
5)
3The Nd of n-heptane solution, 1.0mL0.25mol/L (vers)
3N-heptane solution, 2.5mL toluene, [Nd]=2.5 * 10 at this moment
-5Mol/mL, the ratio of Nd/Al/Cl/ toluene is 1.0/30/4.0/94, and is standby after 60 minutes in 20 ℃ of following ageings.
Add n-heptane solution and the 0.24mL catalyst solution that 100mL contains the 10g divinyl under nitrogen protection in the polymerization bottle of about 150mL, this moment, monomer concentration was 10g/100mL, and Nd/ divinyl ratio is 6 * 10
-7Mol/g.Reacted 3 hours down in 50 ℃, get polymerizing butadiene product 8.0g, transformation efficiency 80%, [η] are 7.0dL/g, and product records suitable-1,4 chain link content through infrared spectra be 96.8%.
Toluene is changed under the situation of heptane when only preparing catalyzer in that other conditionally completes are identical, [η] of monomer conversion and polymerisate is respectively 62%, 9.4dL/g.
Embodiment 18:
(the CH that under nitrogen protection, in the catalyst preparation pipe, adds 2.5mL0.20mol/L successively
3)
3Al (the i-C of SiCl n-heptane solution, 2.5mL3.0mol/L
4H
9)
2The n-heptane solution of H, the Nd of 1.0mL0.25mol/L (vers)
3N-heptane solution, 4.0mL be right-dimethylbenzene, [Nd]=2.5 * 10 at this moment
-5Mol/mL, Nd/Al/Cl/ is right-and the ratio of dimethylbenzene is 1.0/30/2.0/130, and is standby after 60 minutes in 20 ℃ of following ageings.
Under nitrogen protection, in the polymerization bottle of about 150mL, add the n-heptane solution that 100mL contains the 10g divinyl, the 0.40mL catalyst solution, this moment, monomer concentration was 10g/100mL, Nd/ divinyl ratio is 1.0 * 10
-6Mol/g.Reacted 3 hours down in 50 ℃, get polymerizing butadiene product 8.5g, transformation efficiency 85%, [η] are 2.6dL/g.
Right-dimethylbenzene is changed under the situation of heptane when only preparing catalyzer in that other conditionally completes are identical, [η] of monomer conversion and polymerisate is respectively 70%, 4.4dL/g.
Embodiment 19:
Under nitrogen protection, in the catalyst preparation pipe, add 0.108gPrCl successively
33 (i-C
3H
7OH), the Al (C of 1.7mL1.48mol/L divinyl n-heptane solution, 6.6mL toluene, 1.7mL6.0mol/L
2H
5)
3N-heptane solution is added the 2.5mL heptane, makes [Pr]=2.0 * 10
-5Mol/mL, the ratio of Pr/Al/ divinyl/toluene is 1.0/40/10/250, and is standby after 24 hours in 20 ℃ of following ageings.
Add n-heptane solution, the 0.60mL catalyst solution that 100mL contains the 8.0g divinyl under nitrogen protection in about 150mL polymerization bottle, this moment, Pr/ divinyl ratio was 1.5 * 10
-6Mol/g.50 ℃ of following polymerizations 4 hours, polymerizing butadiene product 6.5g, transformation efficiency 81%, [η] are 9.0dL/g, recording suitable-1,4 chain link content through infrared spectra is 98.0%.
Toluene is changed under the situation of heptane when only preparing catalyzer in that other conditionally completes are identical, [η] of monomer conversion and polymerisate is respectively 60%, 12.4dL/g.
Embodiment 20:
Under nitrogen protection, in the catalyst preparation pipe, add 0.262gPrCl successively
3The divinyl n-heptane solution of 3TBP, 0.34mL1.48mol/L, 11.2mL benzene, the Al (C of 0.84mL6.0mol/L
2H
5)
3N-heptane solution, [Pr]=2.0 * 10 at this moment
-5Mol/mL, the ratio of Pr/Al/ divinyl/benzene is 1.0/20/2/500, and is standby after 24 hours in 20 ℃ of ageings.Carry out the polyreaction of divinyl by embodiment 19 described conditions, polymerizing butadiene product 6.3g, transformation efficiency 79%, [η] are 8.2dL/g.
Benzene is changed under the situation of heptane when only preparing catalyzer in that other conditionally completes are identical, [η] of monomer conversion and polymerisate is respectively 56%, 11.8dL/g.
Claims (2)
1. the improved double-olefine polymerizing rare earth catalyst of aromatic hydrocarbons is characterized in that its composition has LnA
3-AlR
3-X-Ar is the catalysis of rare-earth compound agent system and the LnCl of representative
33L-AlR
3-Ar is that the rare earth chloride catalyst system of representative: Ln is neodymium, two kinds of elements of praseodymium; A is a carboxylate radical, and these carboxylate radicals are cycloalkanes acid group, 2 ethyl hexanoic acid root, neodecanoic acid root; AlR
3Be organo-aluminium compound, they are triethyl aluminum, triisobutyl aluminium, diisobutylaluminium hydride; X is chloride compound, and they are aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, tertiary butyl chloride, trimethylchlorosilane; L is the sub-compound of power supply, and they are Virahols, tributyl phosphate; Ar is an aromatic hydrocarbons, they be benzene, toluene, ethylbenzene, isopropyl benzene, dimethylbenzene, ortho-xylene ,-dimethylbenzene, right-dimethylbenzene, trimethylbenzene, mellitene, vinyl benzene, Vinylstyrene, naphthalene, dihydronaphthalene, naphthane, anthracene, phenanthrene.
2. the preparation method of the improved double-olefine polymerizing rare earth catalyst of aromatic hydrocarbons, it is characterized in that Preparation of catalysts is to carry out ageing under 0～50 ℃ in saturated hydrocarbon solvent, digestion time is 30 minutes～24 hours, can also can in the presence of monomer-free, carry out in the presence of the small amounts of monomer, the mol ratio of each component of catalyzer: the Al/Ln ratio is 20～40, the Cl/Ln ratio is 2.0～4.0, and aromatic hydrocarbons/Ln ratio is 1～500, and monomer/Ln ratio is 2～10.
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| CN101153069B (en) * | 2006-09-25 | 2010-05-12 | 北京化工大学 | Method of producing cis-rich butadiene-styrene block copolymer |
| CN102234356B (en) * | 2010-04-30 | 2013-03-06 | 青岛伊科思新材料股份有限公司 | Method for producing rare-earth isoprene butadiene rubber |
| CN102532355B (en) * | 2010-12-09 | 2014-11-12 | 中国石油化工股份有限公司 | Homogenous neodymium-based rare earth catalyst, and its preparation method and application |
| ITUD20130076A1 (en) | 2012-05-28 | 2013-11-29 | Beijing Res Inst Of Chemical Industry | POLIISOPRENE, ITS METHOD OF PREPARATION, COMPOUNDS IN POLYISOPRENE RUBBER AND ITS VULCANIZED |
| CN103626890B (en) * | 2013-11-26 | 2016-06-01 | 中国科学院长春应用化学研究所 | The preparation method of a kind of rare-earth catalysis system and its preparation method and butadiene isoprene copolymer |
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