CN102532355A - Homogenous neodymium-based rare earth catalyst, and its preparation method and application - Google Patents
Homogenous neodymium-based rare earth catalyst, and its preparation method and application Download PDFInfo
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- CN102532355A CN102532355A CN2010105949541A CN201010594954A CN102532355A CN 102532355 A CN102532355 A CN 102532355A CN 2010105949541 A CN2010105949541 A CN 2010105949541A CN 201010594954 A CN201010594954 A CN 201010594954A CN 102532355 A CN102532355 A CN 102532355A
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Abstract
The invention relates to a novel homogenous neodymium-based rare earth catalyst, and a preparation method of the catalyst and application in polymerization of conjugated diene. The synthesis method of the catalyst is simple and easy to control, thus the obtained catalyst has high activity and good stability. By using the inventive homogenous neodymium-based rare earth catalyst for catalyzing polymerization of isoprene, the polymerization process is stable, easy to control, and suitable for continuous operation, and polyisoprene with a cis structure content higher than 98% and adjustable Mooney viscosity range within 60-100 can be synthesized.
Description
Technical field
The present invention relates to a kind of rare earth catalyst, is homogeneous phase rare earth catalyst and preparation method thereof in particular to a kind of novel neodymium.Neodymium of the present invention is the catalyzer that the homogeneous phase rare earth catalyst is particularly suited for being used as conjugate diene polymerization, with synthetic polymkeric substance with high-cis structural content.
Technical background
Conjugated diene (like divinyl and isoprene) can be produced important viton kind (like cis 1 and cis 1,4-TR 301) through the synthetic tactic polymer of coordination polymerization process.The polyisoprene rubber of high-cis structural content has the stretch crystallization performance similar with tree elastomer; And physical and mechanical property is excellent; Be unique kind that can substitute tree elastomer in the viton, be widely used in industries such as tire, medical, glue tube belt.Wherein, tyre industry has the call to polyisoprene rubber.Polyisoprene rubber can partly substitute tree elastomer and be used for each position of tire, and is high along 1, and 4-structural content and suitable mooney viscosity are the important factors that guarantees polyisoprene rubber physical and mechanical property and processing characteristics.And rare earth catalyst synthetic polybutadiene rubber is compared with the polybutadiene rubber polyhutadiene that traditional titanium system, cobalt system, nickel catalyst catalysis obtains; Have better green strength and cured properties; Adapt to the requirement of galloping, can be used for making high-performance tire.
Isoprene adopts solution polymerization process can synthesize along 1 the 4-TR 301 under the rare earth catalyst effect.Rare earth catalyst viton collected works (1980; Science Press, 72-82 page or leaf) mentions the heterogeneous catalyst of forming by neodymium naphthenate/triisobutyl aluminium/aluminium diethyl monochloride in, can synthesize along 1; The 4-structural content all is lower than 95% TR 301; But because along 1, the 4-structural content is on the low side, makes polymer performance undesirable.In addition, there are problems such as the difficult control of less stable, catalytic process and polymerization process in heterogeneous catalysis system owing to possibly there be many active site.Catalyzer is formed and preparation condition can obtain the homogeneous phase rare earth catalyst to address the above problem through changing.
CN 100448898C discloses a kind of homogeneous catalyst of being made up of carboxylic acid neodymium/aluminum alkyls/halogenated organic hydrocarbon/conjugated alkene or carboxylic acid; Be under 1: 1～30: 1～50: 0～17/6 the condition in the catalyst component ratio; Can synthesize along 1, the 4-structural content is 95.32%, and molecular weight is 5.75 * 10
5TR 301.Because along 1, the 4-structural content is on the low side, molecular weight is lower, gained TR 301 product is not suitable for tire product.
US 2005/0137338A1 proposes in the catalyzer ageing process, to add a small amount of diolefinic monomer, helps improving catalyst activity.Catalyzer is made up of carboxylic acid neodymium/aluminum alkyls (triisobutyl aluminium or diisobutylaluminium hydride)/halogen, and carboxylic acid neodymium and aluminum alkyls reaction generate Nd-A l title complex, with the halogen reaction, obtains homogeneous catalyst again.According to embodiment, can synthesize the polyisoprene rubber of high Mooney viscosity, along 1, the 4-structural content is greater than 95.0, and MWD is between 1.0～2.5.But owing to used halogen (like chlorine) in the catalyst preparation process, big to equipment corrosion, and be prone to cause environmental pollution.
CN101045768A discloses a kind of by carboxylic acid neodymium or the phosphor/phosphine acid homogeneous catalyst that neodymium/aluminum alkyls/muriate/conjugated diene is formed; It adopts the mixing solutions that forms carboxylic acid neodymium or phosphor/phosphine acid neodymium, conjugated diene and aluminum alkyls earlier; Reacted 1～10 minute down in 30 ℃～80 ℃, obtain coloured solution; Add muriate then in 10 ℃～80 ℃ down reactions 5 minutes～24 hours, method prepare catalyzer, can synthesize along 1, the 4-structural content is greater than 96%, MWD is less than 3 TR 301.But it is along 1, and it is synthetic polyisoprene and tree elastomer (＞98%) that the 4-structural content still is lower than titanium.
CN1153790C proposes by rare earth compound/halogenated organic hydrocarbon/mixture of alkyl aluminum preparation catalyzer; Each component mol ratio is 1.0～5.0: 1: 20～100; Its activity is higher than the catalyzer that uses single aluminum alkyls preparation; Change the molecular weight of the blending ratio adjustable polymerisate of aluminum alkyls, the synthetic TR 301 is along 1, and the 4-structural content is greater than 95%.Because along 1, the 4-structural content is on the low side, is used for the tire product poor-performing, and aluminum alkyls large usage quantity in the catalyzer, the catalyzer cost is higher.
Summary of the invention
The present invention is fully studying on the basis of relevant conjugate diene polymerization with the prior art of rare earth catalyst; Through optimizing catalyst formulation, be surprised to find that a kind of high reactivity neodymium that synthesizes the conjugated diene polymer of high-cis structural content, especially high cis-1,4-polyisoprene is the homogeneous phase rare earth catalyst.The simple control easily of this process for synthetic catalyst, active high, stablize.Use neodymium of the present invention be rare earth catalyst can the synthesizing cis structural content greater than 98%, mooney viscosity adjustable TR 301 in 60～100 scopes, and polymerization process steadily is easy to control, is fit to the continuous processing operation.
The purpose of this invention is to provide a kind of novel neodymium is the homogeneous phase rare earth catalyst;
Another object of the present invention provides the preparation method that said neodymium is the homogeneous phase rare earth catalyst;
It is the application of homogeneous phase rare earth catalyst aspect conjugate diene polymerization that another purpose of the present invention provides said neodymium, and especially along 1, the 4-structural content is synthetic greater than 98% TR 301.
Particularly, it is the homogeneous phase rare earth catalyst that one aspect of the present invention provides a kind of neodymium, and it mainly consists of:
A) carboxylic acid neodymium compound;
B) having general formula is AlR
3Or AlHR
2Aluminum alkyls or alkyl aluminium hydride, or the mixture of the two, wherein R is C
1-C
6Straight or branched alkane;
C) halogen contained compound;
D) conjugated diene;
Wherein the mol ratio of each component is: a: b: c: d=1: 5～30: 1～10: 35～100.
At neodymium of the present invention is in the homogeneous phase rare earth catalyst, and said carboxylic acid neodymium compound is C a)
1-C
20The carboxylic acid neodymium is preferably C
6-C
10The carboxylic acid neodymium, it can be neodymium naphthenate or branched alkyl carboxylic acid's neodymium.The instance of said carboxylic acid neodymium compound includes but not limited to: neodymium naphthenate, neodymium octoate, isocaprylic acid neodymium, n-nonanoic acid neodymium, neodecanoic acid neodymium or capric acid neodymium.
At neodymium of the present invention is in the homogeneous phase rare earth catalyst, said components b) for having general formula AlR
3Or AlHR
2Aluminum alkyls or alkyl aluminium hydride; Or the mixture of the two, it can be any in the following material or their mixture: trimethylaluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, three amyl group aluminium, three hexyl aluminium, diethyl aluminium hydride and hydrogenation dibutyl aluminium.Preferred said amount of component b) is tri-butyl aluminum, hydrogenation dibutyl aluminium and composition thereof, more preferably triisobutyl aluminium, diisobutylaluminium hydride and composition thereof.
At neodymium of the present invention is in the homogeneous phase rare earth catalyst, said halogen contained compound c) can be and have general formula AlR
2The aikyl aluminum halide of X or have general formula Al
2R
3X
3Sesquialkyl aluminium, wherein R can be ethyl, propyl group, sec.-propyl, butyl, isobutyl-or the tertiary butyl, X is bromine or chlorine; In addition, said halogen contained compound also can be halogen-containing organic cpds or organic clement compound, like liquid bromine, chlorine, benzyl chloride, bromotoluene, tertiary butyl chloride, methyl chloride silane or silicon tetrachloride.Preferred said halogen contained compound is aluminium diethyl monochloride, sesquialter aluminium triethyl or a chloro-di-isobutyl aluminum.
At neodymium of the present invention is in the homogeneous phase rare earth catalyst, said conjugated diene d) be meant any monomer that in its molecule, has conjugated double bond, the example includes but not limited to C
4-C
6Conjugated diene monomer is like divinyl, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethylbutadiene and composition thereof.Said conjugated diene is preferably divinyl or isoprene, most preferably is isoprene.
At neodymium of the present invention is in the homogeneous phase rare earth catalyst, and the ratio between each component can change in wide region, is benchmark a) with component wherein, components b) and mol ratio a) be about 5～about 30, be preferably about 10～about 25; Amount of component b) and mol ratio a) be about 1～about 10, preferred about 2～about 4; Component d) and mol ratio a) be about 35～about 100, preferred about 35～about 80.
In another aspect of this invention, it is the preparation method of homogeneous phase rare earth catalyst that a kind of neodymium also is provided, and prepared neodymium is that homogeneous catalyst has that active high (with the isoprene is example, and catalyst levels is 1 * 10 when being used for conjugate diene polymerization
-5～6 * 10
-4MolNd/molIP), the characteristics of good stability, be particularly useful for synthetic along 1, the 4-structural content more than 98%, mooney viscosity adjustable TR 301 between 60～90.
Neodymium of the present invention is that the preparation method of homogeneous phase rare earth catalyst comprises: in organic solvent, each component is mixed with random order, and experience ageing reaction obtains the homogeneous phase rare earth catalyst.Preferably at first with component a), b), d) mix with random order, add amount of component b then) experience ageing reaction; Perhaps at first with component a) with component d) mix, then with components b) join in the aforementioned mixed solution, add amount of component b at last), make mixture experience ageing reaction a)-d) of the component that obtains.
To neodymium of the present invention is that the organic solvent that uses among the preparation method of homogeneous phase rare earth catalyst has no particular limits, and can select that this area is normally used to be inert aliphatic saturated hydrocarbon or cycloaliphates solvent to reactive component for use, often selects C for use
5-C
10Alkane or naphthenic hydrocarbon are like pentane, iso-pentane, hexane, hexanaphthene, heptane, octane etc. or its mixture.
At neodymium of the present invention is among the preparation method of homogeneous phase rare earth catalyst, and ageing is reflected under-60 ℃～30 ℃ to be carried out 0.5～24 hour.Preferably in organic solvent, component a), b), d) mixed solution contact afterreaction 10～120 minutes, this reactions step can-60 ℃～30 ℃, preferably under-30 ℃～30 ℃, carry out; Add amount of component b again) reaction 0.5～24 hour, this reactions step can-60 ℃～30 ℃, preferably under-40 ℃～20 ℃, carry out.
At neodymium of the present invention is in homogeneous catalyst and the method for preparing catalyst; According to actual needs; Arbitrary or various ingredients below can adding; Be used to change catalyst activity and regulate polymer molecular weight and MWD, as: aromatic hydroxy compounds such as benzene, toluene, ethylbenzene, YLENE, isopropyl benzene, ether compounds such as ether, phenyl ether.This component can add in arbitrary step of Preparation of Catalyst, and this component and mol ratio a) are about 1～about 500.
In one side more of the present invention; It is the application of homogeneous phase rare earth catalyst aspect conjugated diene, especially isoprene polymerization that said neodymium also is provided; It is included in the inert hydrocarbon solvent, and adopting neodymium of the present invention is that the homogeneous phase rare earth catalyst carries out the conjugated diene solution polymerization.
Adopting neodymium of the present invention is that rare earth catalyst carries out the isoprene solution polymerization, and the synthetic TR 301 is along 1, and the 4-structural content is greater than 98%, and mooney viscosity is adjustable in 60～100 scopes, and physical and mechanical property and processing characteristics are excellent.
In conjugate diene polymerization technology of the present invention, being used for the polymeric catalytic amount can change in wide region.Is example with isoprene as polymerization single polymerization monomer, and catalyst levels is controlled at 1 * 10 usually
-5～6 * 10
-4MolNd/molIP, preferred 1.5 * 10
-5～4 * 10
-4In the scope of molNd/molIP.Catalyst levels is crossed too not only increases cost, and ash oontent increases in the polymer product but also possibly make.
In conjugate diene polymerization technology of the present invention, described conjugated diene includes but not limited to C
4-C
6Conjugated diene monomer is like divinyl, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethylbutadiene and composition thereof.Said conjugated diene is preferably isoprene or divinyl, most preferably is isoprene.
In isoprene polymerization technology of the present invention; To the not special restriction of the inert hydrocarbon solvent that uses, typical solvent include but not limited to hexane, hexanaphthene, heptane, pentane, iso-pentane or, octane, methylcyclohexane, benzene,toluene,xylene and isopropyl benzene etc.
In isoprene polymerization technology of the present invention; Can adopt this area mode commonly used that reactive polymer is directly stopped; Mostly available terminator is water or alcohols, for example water, methyl alcohol, ethanol, positive Virahol, Virahol, 2,6-di-tert-butyl hydroquinone methyl alcohol etc.
Neodymium of the present invention is that the optimal conditions of homogeneous phase rare earth catalyst when carrying out the catalysis isoprene polymerization is: the temperature of polyreaction is-30 ℃～80 ℃, is preferably-10 ℃～70 ℃, more preferably 0 ℃～60 ℃; Time is 20～360 minutes, is preferably 30～120 minutes.
Major advantage of the present invention and effect:
Through the preferred catalytic agent prescription; Be surprised to find that a kind of high reactivity neodymium that synthesizes the conjugated diene polymer of high-cis structural content, especially high cis-1,4-polyisoprene is the homogeneous phase rare earth catalyst, use this catalyzer can the synthesizing cis structural content greater than 98%, mooney viscosity adjustable TR 301 in 60～100 scopes.The simple control easily of the compound method of catalyzer of the present invention, catalyst activity is high, good stability is convenient to storage.Adopt this catalyzer to carry out the conjugated diene solution polymerization, polymerization process steadily is easy to control, is fit to the continuous processing operation.Physical and mechanical propertiess such as synthetic polymer processing performance, autohension, wear resistance, subduing property, aging resistance are excellent, can partly replace tree elastomer to be used for tire product.
Embodiment
Describe the present invention in detail by embodiment and Comparative Examples below, but scope of the present invention is not limited to these embodiment.
In the present invention, the microtexture of synthetic conjugated diene polymer adopts German Bruker Tensor 27 mid-infrared light spectrometers and German Bruker 400MHz nmr determination, and solvent is a deuterochloroform; The mooney viscosity of polymkeric substance adopts day automatic Mooney viscometer determining of island proper Tianjin SMV-300 type according to GB/T 1232.1_2000 regulation.
Embodiment 1
The cyclohexane solution concentration of neodymium naphthenate is 0.2mol/l.The cyclohexane solution concentration of diisobutylaluminium hydride and aluminium diethyl monochloride is 1mol/l.The solvent water number is lower than 15ppm, carries out deoxygenation with nitrogen before using and handles; Aging reactor is handled through dry and deoxygenation.
Under nitrogen protection, in 2L catalyzer aging reactor, add the 580g cyclohexane solution, then 54ml isoprene, 60ml neodymium naphthenate solution and 192ml diisobutylaluminium hydride solution are added in the aging reactor, contact reacts is 15 minutes under 20 ℃ and agitation condition.Then 42ml aluminium diethyl monochloride solution is added in the aging reactor, in 10 ℃ of following ageings 30 minutes.Catalyst concn is 1.0 * 10
-5Mol/ml.
Under nitrogen protection, in the 5L polymeric kettle, add 400g isoprene, 1541g hexanaphthene and 88ml catalyzer successively, monomer concentration is 20%., after 60 minutes polymers soln is emitted in still and added 2,6-di-tert-butyl hydroquinone methanol solution termination reaction in reaction under 20 ℃ of conditions.Before emitting polymers soln, with take a morsel polymers soln and weighing of weighing bottle, placing vacuum drying oven to be dried to constant weight then, calculate monomer conversion through example weight before and after dry, is 85% through calculating transformation efficiency.Polymkeric substance is along 1, and the 4-structural content is 98.3%, and mooney viscosity is 76.
Embodiment 2
The hexane solution that triisobutyl aluminium and sesquialter aluminium triethyl is mixed with 0.5mol/l concentration respectively is subsequent use.It is subsequent use that neodymium naphthenate is mixed with the hexane solution of 0.2mol/l concentration.The processing mode of solvent and aging reactor is identical with embodiment 1.
Under nitrogen protection, in 5L catalyzer aging reactor, add 195ml isoprene, 130ml neodymium naphthenate solution, 936ml triisobutyl aluminum solutions, 104ml sesquialter aluminium triethyl solution and 1278g hexane solution, 10 ℃ with agitation condition under ageing 2 hours.Catalyst concn is 0.8 * 10
-5Mol/ml.
Under nitrogen protection, in the 5L polymeric kettle, add 350g isoprene, 1800g hexane and 103ml catalyzer successively, monomer concentration is 15%., after 1.5 hours polymers soln is emitted in still and added 2,6-di-tert-butyl hydroquinone methanol solution termination reaction in reaction under 15 ℃ of conditions.Monomer conversion is 87%.Polymkeric substance is along 1, and the 4-structural content is 98.2%, mooney viscosity 75.
Embodiment 3
The hexane solution that triisobutyl aluminium and aluminium diethyl monochloride is mixed with 0.5mol/l concentration respectively is subsequent use.It is subsequent use that the neodecanoic acid neodymium is mixed with the hexane solution of 0.2mol/l concentration.The processing mode of solvent and aging reactor is identical with embodiment 1.
Under nitrogen protection; In 1L catalyzer aging reactor, add 158g hexane solution, 20ml divinyl, 30ml neodymium naphthenate solution and 180ml triisobutyl aluminum solutions; In 25 ℃ with agitation condition under contact reacts 10 minutes, add 30ml aluminium diethyl monochloride solution then and continue at 25 ℃ of following ageings 1 hour.Catalyst concn is 1.2 * 10
-5Mol/ml.
Under nitrogen protection, in the 5L polymeric kettle, add 350g isoprene, 1800g hexane and 56ml catalyzer successively, monomer concentration is 15.4%.10 ℃ of down reactions after 3 hours, polymers soln is emitted in still and added 2,6-di-tert-butyl hydroquinone methanol solution termination reaction.Monomer conversion is 90%; Polymkeric substance is along 1, and the 4-structural content is 98.6%, mooney viscosity 80.
Embodiment 4
The hexane solution that the neodecanoic acid neodymium is mixed with 0.4mol/l concentration is subsequent use.Triisobutyl aluminium and tertiary butyl chloride are mixed with the hexane solution of 1mol/l concentration respectively.The processing mode of solvent and aging reactor is identical with embodiment 1.
Under nitrogen protection; In 10L catalyzer aging reactor, add 100ml neodecanoic acid neodymium solution, 192ml isoprene, 3544g hexane solution; Add 600ml triisobutyl aluminum solutions then; In-10 ℃ with agitation condition under contact reacts 40 minutes, add 400ml tertiary butyl chloride solution then and continue ageing 5 hours.Catalyst concn is 0.6 * 10
-5Mol/ml.
Under nitrogen protection, in the 5L polymeric kettle, add 250g isoprene, 2150g hexane and 80ml catalyzer successively, monomer concentration is 10%, polymeric reaction temperature is 50 ℃.React after 40 minutes, polymers soln is emitted in still and added 2,6-di-tert-butyl hydroquinone methanol solution termination reaction.Monomer conversion is 92%; Polymkeric substance is along 1, and the 4-structural content is 98.0%, mooney viscosity 78.
Embodiment 5
The hexane solution that the neodecanoic acid neodymium is mixed with 0.5mol/l concentration is subsequent use.Triisobutyl aluminium and aluminium diethyl monochloride are mixed with the hexane solution of 0.5mol/l concentration respectively.The processing mode of solvent and aging reactor is identical with embodiment 1.
Under nitrogen protection; In 10L catalyzer aging reactor, add 240ml isoprene, 1L triisobutyl aluminum solutions, 100ml neodecanoic acid neodymium solution and 3043g hexane solution; In 15 ℃ with agitation condition under contact reacts after 20 minutes; Add 300ml aluminium diethyl monochloride solution, continue ageing 4 hours down in 0 ℃.Catalyst concn is 0.8 * 10
-5Mol/ml.
Under nitrogen protection, in the 5L polymeric kettle, add 390g isoprene, 1845g hexane and 150ml catalyzer successively, monomer concentration is 17%.0 ℃ of down reaction after 5 hours, polymers soln is emitted in still and added 2,6-di-tert-butyl hydroquinone methanol solution termination reaction.Monomer conversion is 81%; Polymkeric substance is along 1, and the 4-structural content is 98.9%; Mooney viscosity 96.
Embodiment 6
Described in embodiment 5, prefabricated agents useful for same.The processing mode of solvent and aging reactor is identical with embodiment 1
Under nitrogen protection; In 10L catalyzer aging reactor, add 1.2L triisobutyl aluminum solutions and 100ml neodecanoic acid neodymium solution; Add 240ml isoprene and 2910g hexane solution then; In 20 ℃ with agitation condition under contact reacts after 20 minutes, add 300ml aluminium diethyl monochloride solution, continue ageings 2 hours down in 10 ℃.Catalyst concn is 0.8 * 10
-5Mol/ml.
Under nitrogen protection, in the 5L polymeric kettle, add 350g isoprene, 1845g hexane and 105ml catalyzer successively, monomer concentration is 15%.15 ℃ of down reactions after 2 hours, polymers soln is emitted in still and added 2,6-di-tert-butyl hydroquinone methanol solution termination reaction.Monomer conversion is 90%; Polymkeric substance is along 1, and the 4-structural content is 98.6%; Mooney viscosity 87.
Embodiment 7
Described in embodiment 5, prefabricated agents useful for same.The processing mode of solvent and aging reactor is identical with embodiment 1.
Under nitrogen protection; In 20L catalyzer aging reactor, add 136g isoprene, 80ml neodecanoic acid acid neodymium solution and 4409g hexane solution; Add 240ml aluminium diethyl monochloride solution in 0 ℃ down with agitation condition again; Contact reacts adds 800ml triisobutyl aluminum solutions after 15 minutes, continue ageing 18 hours.Catalyst concn is 0.5 * 10
-5Mol/ml.
Under nitrogen protection, in the 5L polymeric kettle, add 350g isoprene, 1860g hexane and 134ml catalyzer successively, monomer concentration is 15%.20 ℃ of down reactions after 1.5 hours, polymers soln is emitted in still and added 2,6-di-tert-butyl hydroquinone methanol solution termination reaction.Monomer conversion is 92%; Polymkeric substance is along 1, and the 4-structural content is 98.7%, mooney viscosity 90.
Embodiment 8 (Comparative Examples)
Described in embodiment 5, prefabricated agents useful for same.The processing mode of solvent and aging reactor is identical with embodiment 1
Under nitrogen protection; In 10L catalyzer aging reactor, add 50ml isoprene, 3.5L triisobutyl aluminum solutions, 100ml neodecanoic acid neodymium solution and 1848g hexane solution; In 50 ℃ with agitation condition under contact reacts after 10 minutes; Add 300ml aluminium diethyl monochloride solution, continue ageing 30 minutes.Catalyst concn is 1.0 * 10
-5Mol/ml.
Under nitrogen protection, in the 5L polymeric kettle, add 350g isoprene, 1845g hexanaphthene and 130ml catalyzer successively, monomer concentration is 15%.40 ℃ of down reactions after 3 hours, polymers soln is emitted in still and added 2,6-di-tert-butyl hydroquinone methanol solution termination reaction.Monomer conversion is 85%; Polymkeric substance is along 1, and the 4-structural content is 96.7%, mooney viscosity 62.
Claims (13)
1. a neodymium is the homogeneous phase rare earth catalyst, and it mainly consists of:
A) carboxylic acid neodymium compound;
B) having general formula is AlR
3Or AlHR
2Aluminum alkyls or alkyl aluminium hydride, or the mixture of the two, wherein R is C
1-C
6Straight or branched alkane;
C) halogen contained compound;
D) conjugated diene;
Wherein the mol ratio of each component is: a: b: c: d=1: 5～30: 1～10: 35～100.
2. according to the catalyzer of claim 1, wherein said carboxylic acid neodymium compound is C
1-C
20The carboxylic acid neodymium; Preferred said carboxylic acid neodymium compound is C
6-C
10The carboxylic acid neodymium; More preferably said carboxylic acid neodymium compound is neodymium naphthenate, neodymium octoate, isocaprylic acid neodymium, n-nonanoic acid neodymium, neodecanoic acid neodymium or capric acid neodymium.
3. according to the catalyzer of claim 1, wherein said aluminum alkyls or alkyl aluminium hydride are selected from trimethylaluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, three amyl group aluminium, three hexyl aluminium, diethyl aluminium hydride, hydrogenation dibutyl aluminium and composition thereof; Preferred said aluminum alkyls or alkyl aluminium hydride are selected from tri-butyl aluminum, hydrogenation dibutyl aluminium and composition thereof; More preferably aluminum alkyls or alkyl aluminium hydride are selected from triisobutyl aluminium, diisobutylaluminium hydride and composition thereof.
4. according to the catalyzer of claim 1, wherein said halogen contained compound is for having general formula AlR
2The aikyl aluminum halide of X or have general formula Al
2R
3X
3Sesquialkyl aluminium, wherein R is ethyl, propyl group, sec.-propyl, butyl, isobutyl-or the tertiary butyl, X is bromine or chlorine; Preferred said aluminium diethyl monochloride, sesquialter aluminium triethyl or a chloro-di-isobutyl aluminum.
5. according to the catalyzer of claim 1, wherein said halogen contained compound is halogen-containing organic cpds or organic clement compound, is preferably liquid bromine, chlorine, benzyl chloride, bromotoluene, tertiary butyl chloride, methyl chloride silane or silicon tetrachloride.
6. according to the catalyzer of claim 1, wherein said conjugated diene is C
4-C
6The conjugated diene list; Preferred said conjugated diene is selected from divinyl, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethylbutadiene and composition thereof; More preferably said conjugated diene is divinyl or isoprene; Most preferably said conjugated diene is an isoprene.
7. according to each catalyzer among the claim 1-6, be benchmark a) wherein, components b) with component and mol ratio a) be 10～25; Amount of component b) and mol ratio a) be 2～4; Component d) and mol ratio a) be 35～80.
8. according to each catalyzer among the claim 1-7, it further comprises one or more components that are selected from benzene, toluene, ethylbenzene, YLENE, isopropyl benzene, ether and phenyl ether, and these one or more components and component mol ratio a) are 1～500.
9. according to each method for preparing catalyst among the claim 1-8, it comprises:
In inert organic solvents, each component is mixed with random order, and experience ageing reaction; Preferably at first with component a), b), c) mix; Add component d then) experience ageing reaction, perhaps at first with component a) with component d) mix, then with components b) join in the aforementioned mixed solution; Add amount of component b at last), make component mixture experience ageing reaction a)-d) that obtains.
10. according to the preparation method of claim 9, wherein said inert organic solvents is saturated fatty or cycloaliphates solvent, is preferably C
5-C
10Alkane or naphthenic hydrocarbon are like pentane, iso-pentane, hexane, hexanaphthene, heptane, octane etc. or its mixture.
11. according to the preparation method of claim 9 or 10, wherein said ageing is reflected under-60 ℃～30 ℃ to be carried out 0.5～24 hour; Preferably make component a), b), c) mixed solution contact afterreaction 10～120 minutes, this reactions step-60 ℃～30 ℃, preferably under-30 ℃～30 ℃, carry out; Add component d again) reaction 0.5～24 hour, this reactions step-60 ℃～30 ℃, preferably under-40 ℃～20 ℃, carry out.
12. according among the claim 1-8 each catalyzer or by the catalyzer of each method preparation among the claim 9-11 in the application aspect the conjugate diene polymerization.
13. according to the application of claim 12, wherein said conjugated diene is an isoprene.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231139A (en) * | 2013-06-08 | 2014-12-24 | 中国石油化工股份有限公司 | Polyisoprene rubber and continuous polymerization method thereof |
| CN106589195A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Method for preparing polyisoprene |
| CN106749780A (en) * | 2015-11-20 | 2017-05-31 | 中国石油天然气股份有限公司 | A kind of preparation method of rare earth polymer |
| CN107207654A (en) * | 2014-11-17 | 2017-09-26 | 株式会社普利司通 | The polymerisation in bulk of polyisoprene with preform catalyst |
| JP2020530511A (en) * | 2017-10-30 | 2020-10-22 | エルジー・ケム・リミテッド | A method for producing a catalyst for conjugated diene polymerization, a catalyst, and a method for producing a conjugated diene-based polymer using the catalyst. |
| CN112142893A (en) * | 2019-06-27 | 2020-12-29 | 中国石油化工股份有限公司 | Polyisoprene and preparation method thereof |
| CN112409520A (en) * | 2019-08-21 | 2021-02-26 | 中国石油化工股份有限公司 | Polybutadiene prepared by homogeneous rare earth catalyst and catalyst thereof |
| CN112409539A (en) * | 2019-08-21 | 2021-02-26 | 中国石油化工股份有限公司 | Butadiene-isoprene copolymer and preparation method thereof |
| CN112552441A (en) * | 2020-12-09 | 2021-03-26 | 浙江传化合成材料有限公司 | Preparation method of neodymium rare earth rubber |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5686371A (en) * | 1991-09-09 | 1997-11-11 | Enichem Elastomers Ltd. | Conjugated diene polymerisation |
| CN1295087A (en) * | 1999-11-05 | 2001-05-16 | 中国科学院长春应用化学研究所 | Arene-improved double-olefine polymerizing rare earth catalyst and its preparation |
| CN1813010A (en) * | 2003-06-25 | 2006-08-02 | 株式会社普利司通 | Butadiene polymer and process for producing the same, and rubber composition and tire comprising or made from the same |
| CN101045768A (en) * | 2007-04-12 | 2007-10-03 | 中国科学院长春应用化学研究所 | Rare earth catalyst for preparing polyisoprene and preparation method and method for preparing polyisoprene |
-
2010
- 2010-12-09 CN CN201010594954.1A patent/CN102532355B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5686371A (en) * | 1991-09-09 | 1997-11-11 | Enichem Elastomers Ltd. | Conjugated diene polymerisation |
| CN1295087A (en) * | 1999-11-05 | 2001-05-16 | 中国科学院长春应用化学研究所 | Arene-improved double-olefine polymerizing rare earth catalyst and its preparation |
| CN1813010A (en) * | 2003-06-25 | 2006-08-02 | 株式会社普利司通 | Butadiene polymer and process for producing the same, and rubber composition and tire comprising or made from the same |
| CN101045768A (en) * | 2007-04-12 | 2007-10-03 | 中国科学院长春应用化学研究所 | Rare earth catalyst for preparing polyisoprene and preparation method and method for preparing polyisoprene |
Cited By (15)
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|---|---|---|---|---|
| CN104231139A (en) * | 2013-06-08 | 2014-12-24 | 中国石油化工股份有限公司 | Polyisoprene rubber and continuous polymerization method thereof |
| CN104231139B (en) * | 2013-06-08 | 2017-02-15 | 中国石油化工股份有限公司 | Polyisoprene rubber and continuous polymerization method thereof |
| CN107207654A (en) * | 2014-11-17 | 2017-09-26 | 株式会社普利司通 | The polymerisation in bulk of polyisoprene with preform catalyst |
| CN106589195A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Method for preparing polyisoprene |
| CN106589195B (en) * | 2015-10-19 | 2018-11-02 | 中国石油化工股份有限公司 | A method of preparing polyisoprene |
| CN106749780A (en) * | 2015-11-20 | 2017-05-31 | 中国石油天然气股份有限公司 | A kind of preparation method of rare earth polymer |
| JP2020530511A (en) * | 2017-10-30 | 2020-10-22 | エルジー・ケム・リミテッド | A method for producing a catalyst for conjugated diene polymerization, a catalyst, and a method for producing a conjugated diene-based polymer using the catalyst. |
| US11655315B2 (en) | 2017-10-30 | 2023-05-23 | Lg Chem, Ltd. | Method for preparing catalyst for polymerizing conjugated diene, catalyst and method for preparing conjugated diene-based polymer using the same |
| CN112142893A (en) * | 2019-06-27 | 2020-12-29 | 中国石油化工股份有限公司 | Polyisoprene and preparation method thereof |
| CN112142893B (en) * | 2019-06-27 | 2022-07-12 | 中国石油化工股份有限公司 | Polyisoprene and preparation method thereof |
| CN112409520A (en) * | 2019-08-21 | 2021-02-26 | 中国石油化工股份有限公司 | Polybutadiene prepared by homogeneous rare earth catalyst and catalyst thereof |
| CN112409539A (en) * | 2019-08-21 | 2021-02-26 | 中国石油化工股份有限公司 | Butadiene-isoprene copolymer and preparation method thereof |
| CN112409539B (en) * | 2019-08-21 | 2023-07-21 | 中国石油化工股份有限公司 | Butadiene-isoprene copolymer and preparation method thereof |
| CN112409520B (en) * | 2019-08-21 | 2023-07-21 | 中国石油化工股份有限公司 | Preparation of polybutadiene and catalyst thereof by homogeneous rare earth catalyst |
| CN112552441A (en) * | 2020-12-09 | 2021-03-26 | 浙江传化合成材料有限公司 | Preparation method of neodymium rare earth rubber |
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