CN105330773A - Composition for rare earth catalyst, rare earth catalyst, and preparation method and application thereof - Google Patents
Composition for rare earth catalyst, rare earth catalyst, and preparation method and application thereof Download PDFInfo
- Publication number
- CN105330773A CN105330773A CN201410326913.2A CN201410326913A CN105330773A CN 105330773 A CN105330773 A CN 105330773A CN 201410326913 A CN201410326913 A CN 201410326913A CN 105330773 A CN105330773 A CN 105330773A
- Authority
- CN
- China
- Prior art keywords
- general formula
- rare earth
- earth catalyst
- preparation
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Polymerization Catalysts (AREA)
Abstract
The invention provides a composition for a rare earth catalyst. The composition includes: a) a neodymium compound with a general formula NdL3.HL, wherein L represents branched alkyl carboxylate radical or naphthenic acid radical, and HL represents the corresponding carboxylic acid; b) methyl aluminoxane; c) halide; and d) an aluminum alkyl compound. The invention provides a rare earth catalyst. The invention provides a preparation method of the rare earth catalyst. The invention provides a rare earth catalyst prepared by the preparation method provided by the invention. The invention provides the application of the catalyst to conjugated diene polymerization. The neodymium rare earth catalyst has high activity and high catalyst efficiency, and can effectively reduce production costs.
Description
Technical field
The present invention relates to a kind of rare earth catalyst composition, and a kind of rare earth catalyst and preparation method thereof and the application of rare earth catalyst in conjugate diene polymerization.
Technical background
Conjugated diene (as divinyl and isoprene), by coordination polymerization process synthesis tactic polymer, produces important synthetic rubber kind (as cis 1，4-polybutadiene and cis Isosorbide-5-Nitrae-polyisoprene).Cis 1,4-polyisoprene (polyisoprene rubber), also known as " natural synthetic rubber ", there is the stretch crystallization performance similar to natural rubber, and excellent physical properties, be the kind that uniquely can substitute natural rubber in synthetic rubber, be widely used in the industries such as tire, medical, glue tube belt.
China's natural rubber resource scarcity, developing high performance synthetic polyisoprenes rubber is the optimal path solving China's natural rubber imbalance between supply and demand.Isoprene, under rare earth catalyst effect, can synthesize the high polyisoprene along Isosorbide-5-Nitrae-structural content, and have good physical and mechanical properties.
CN1479754A discloses the catalyzer of a kind of organophosphate/aluminum alkyls/alkyl aluminum halide composition, can synthesizing cis Isosorbide-5-Nitrae-structural content polyisoprene of being greater than 99% under lower than the condition of 0 DEG C.But this catalyzer is in polymerization process, carrying out under extremely low temperature of needs, and polymerization reaction time is quite long, is therefore unfavorable for industrial application.
CN10118663A and CN101260164A discloses the catalyzer of a kind of clamp type rareearth compound composition, and can synthesize the polyisoprene of high cis-contents, but catalyst preparation process is loaded down with trivial details, cost is high, is unfavorable for industrial application.
For isoprene product, improve cis-structure content and be conducive to improving its mechanical property, and the polyisoprene cis Isosorbide-5-Nitrae-structural content of the disclosed method synthesis such as CN100448898C, CN101045768A is all lower than 98%.
In fact, the polyisoprene product of high molecular, narrow molecular weight distributions has the strain-crystallization performance similar to natural rubber, and its mechanical property has more advantage.But because carboxylic acid neodymium class rare earth catalyst exists dynamics model, and as previously mentioned, the carboxylic acid neodymium class rare earth catalyst obtained according to current formula and preparation method is difficult to obtain the product of narrow molecular weight distributions for being polymerized.
Summary of the invention
The object of this invention is to provide a kind of rare earth catalyst of polymkeric substance that can synthesize high-cis structural content, high molecular, narrow molecular weight distributions, thus, the invention provides a kind of rare earth catalyst composition, rare earth catalyst and preparation method thereof and the application in conjugate diene polymerization.
For realizing aforementioned object, according to a first aspect of the invention, the invention provides a kind of rare earth catalyst composition, wherein, said composition comprises:
A) neodymium compound, described neodymium compound is for having general formula NdL
3the neodymium compound of HL, wherein, L is branched alkyl carboxylic acid's root or cycloalkanes acid group, and HL is corresponding carboxylic acid;
B) methylaluminoxane;
C) halogenide, described halogenide is for having general formula AlR
2the aikyl aluminum halide of X, there is general formula Al
2r
3x
3sesquialkyl aluminium and have in the halohydrocarbon of general formula R X one or more, wherein, R is alkyl, X halogen;
D) alkylaluminium cpd, described alkylaluminium cpd is AlR for having general formula
3and/or AlHR
2alkylaluminium cpd, wherein, R is alkyl.
According to a second aspect of the invention, the invention provides a kind of rare earth catalyst, this catalyzer by composition of the present invention, is contacted with each other and obtains under protection of inert gas in inert organic solvents.
According to a third aspect of the invention we, the invention provides a kind of preparation method of rare earth catalyst, the method comprises:
1) under protection of inert gas, in the presence of an inert organic solvent, methylaluminoxane mixed with conjugated diene and neodymium compound, obtain the first mixed solution, wherein, described neodymium compound is for having general formula NdL
3the neodymium compound of HL, wherein, L is branched alkyl carboxylic acid's root or cycloalkanes acid group, and HL is corresponding carboxylic acid;
2) contacted with halogenide by described first mixed solution, obtain the second mixed solution, wherein, described halogenide is for having general formula AlR
2the aikyl aluminum halide of X, there is general formula Al
2r
3x
3sesquialkyl aluminium and have in the halohydrocarbon of general formula R X one or more, wherein, R is alkyl, and X is halogen;
3) contacted with alkylaluminium cpd by described second mixed solution, wherein, described alkylaluminium cpd is AlR for having general formula
3and/or AlHR
2alkylaluminium cpd, wherein, R is alkyl.
According to a forth aspect of the invention, the invention provides a kind of rare earth catalyst prepared according to the preparation method of rare earth catalyst of the present invention.
According to a fifth aspect of the invention, the invention provides the application of catalyzer of the present invention in conjugate diene polymerization.
Neodymium system of the present invention rare earth catalyst activity is high, catalyst efficiency is high, effectively can reduce production cost; When rare earth catalyst of the present invention being used for conjugated diene such as isoprene polymerization, the polyisoprene product of synthesis has the microtexture closely similar with natural rubber, it has high along 1,4-structural content (being more than or equal to 97%), high molecular and narrow ditribution (being less than or equal to 2.5), have the strain-crystallization performance similar to natural rubber simultaneously.Therefore, use neodymium system of the present invention rare earth catalyst to synthesize the polyisoprene product obtained to can be used for alternative natural rubber and be widely used in production, in particular for tyre industry, in addition, use neodymium system of the present invention rare earth catalyst to synthesize the polyisoprene product obtained and also have its advantage in the application of medical field.Compared with natural rubber, the polyisoprene product using neodymium system of the present invention rare earth catalyst to synthesize to obtain containing the material that the human bodies such as protein are easily irritated, does not have been widely used in medical product.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of rare earth catalyst composition, wherein, said composition comprises:
A) neodymium compound, described neodymium compound is for having general formula NdL
3the neodymium compound of HL, wherein, L is branched alkyl carboxylic acid's root or cycloalkanes acid group, and HL is corresponding carboxylic acid;
B) methylaluminoxane;
C) halogenide, described halogenide is for having general formula AlR
2the aikyl aluminum halide of X, there is general formula Al
2r
3x
3sesquialkyl aluminium and have in the halohydrocarbon of general formula R X one or more, wherein, R is alkyl, X halogen;
D) alkylaluminium cpd, described alkylaluminium cpd is AlR for having general formula
3and/or AlHR
2alkylaluminium cpd, wherein, R is alkyl.
All object of the present invention can be realized according to preceding solution of the present invention, and in order to the activity that improves rare earth catalyst of the present invention further and catalytic efficiency, for the present invention, further preferably L be containing 8-12 carbon branched carboxylic acids root or contain the cycloalkanes acid group of 8-12 carbon, can be such as sad, n-nonanoic acid or capric acid; For the present invention, preferred described neodymium compound is the neodymium naphthenate [Nd (C in conjunction with a part naphthenic acid
7h
9o
2)
3(C
7h
10o
2)], in conjunction with the neodymium iso-octanate [Nd (C of a part isocaprylic acid
8h
15o
2)
3(C
8h
16o
2)] or in conjunction with the neodymium caprate [Nd (C of a part neodecanoic acid
10h
19o
2)
3(C
10h
20o
2)].
In the present invention, there is bonding action in the carboxylic acid molecules in preferred described neodymium compound and carboxylic acid neodymium, it can be commercially available, also can prepare, such as, can prepare as follows: acetic acid neodymium and excessive carboxylic acid in inert solvent (as benzene, toluene, chlorobenzene, hexane etc.), replacement(metathesis)reaction occur and obtain NdL
3hR.
All object of the present invention can be realized according to preceding solution of the present invention, and in order to the activity that improves rare earth catalyst of the present invention further and catalytic efficiency, for the present invention, preferred neodymium compound further: methylaluminoxane: halogenide: the mol ratio of alkylaluminium cpd is 1:0.5-10:0.5-20:5-20, is preferably 1:2-8:1-10:6-18.
All can realize object of the present invention according to preceding solution of the present invention, for the present invention, in order to make rare earth catalyst be homogeneous phase, further preferably, composition of the present invention also comprises: e) conjugated diene; More preferably neodymium compound: the mol ratio of conjugated diene is 1:1-80, more preferably 1:10-70.
In the present invention, the range of choices of the kind of conjugated diene is wider, for the present invention, preferred described conjugated diene is the conjugated diene of C4-C6, be preferably divinyl, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2, one or more in 3-dimethylbutadiene, are particularly preferably divinyl or isoprene.
All can realize object of the present invention according to preceding solution of the present invention, and in order to the activity that improves rare earth catalyst of the present invention further and catalytic efficiency, for the present invention, in further preferred halid general formula, R is C
1-C
6alkyl, can be such as ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, benzyl or allyl group, X is bromine or chlorine, and more preferably, described halogenide is one or more in aluminium diethyl monochloride, a chlorine trimethyl silane, sesquialter ethylmercury chloride aluminium and a chloro-di-isobutyl aluminum.
All can realize object of the present invention according to preceding solution of the present invention, and in order to the activity that improves rare earth catalyst of the present invention further and catalytic efficiency, for the present invention, in the general formula of further preferred alkyl aluminum compound, R is C
1-C
6alkyl, more preferably alkylaluminium cpd is one or more in trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, triisobutyl aluminium, three amyl group aluminium, three hexyl aluminium, diethyl aluminium hydride and hydrogenation dibutyl aluminium, is more preferably one or more in trimethyl aluminium, triisobutyl aluminium, triethyl aluminum and hydrogenation dibutyl aluminium.
The invention provides a kind of rare earth catalyst, this catalyzer by composition of the present invention, is contacted with each other and obtains under protection of inert gas in inert organic solvents.
In the present invention, catalyzer by rare earth catalyst composition of the present invention under protection of inert gas, in inert organic solvents, contact the mode obtained has multiple, such as each component in rare earth catalyst composition of the present invention can be dissolved in described inert organic solvents respectively and be configured to solution form, then mix contact to obtain, also rare earth catalyst composition of the present invention directly can be mixed to contact with described inert organic solvents and obtain, as long as make component in rare earth catalyst composition of the present invention contact in described inert organic solvents can realize object of the present invention.In the specific embodiment of the present invention, general being dissolved in advance in inert organic solvents by rare earth compound in rare earth catalyst composition is configured to solution (those skilled in the art generally claim this solution to be dispersion liquid), then all the other components is joined in solution to carry out contact and obtain catalyzer of the present invention.
Rare gas element described in the present invention can be the rare gas element that this area routine uses, and all can know, will not enumerate at this these those skilled in the art.
According to rare earth catalyst of the present invention, the selection of described inert organic solvents can be carried out with reference to prior art, can be this area normally used be aliphatic saturated hydrocarbon or the alicyclic hydrocarbon solvents of inertia to reactive component, for the present invention, preferred described inert organic solvents is the straight-chain paraffin of C5-C10 and/or the naphthenic hydrocarbon of C5-C10, is particularly preferably one or more in pentane, iso-pentane, hexane, hexanaphthene, heptane and octane.
Use the rare earth catalyst that foregoing of the present invention prepares, activity is high, catalyst efficiency is high, effectively can reduce production cost; When rare earth catalyst of the present invention being used for conjugated diene such as isoprene polymerization, the polyisoprene product of synthesis has the microtexture closely similar with natural rubber, it has high along 1,4-structural content (being more than or equal to 97%), high molecular and narrow ditribution (being less than or equal to 2.5), there is the strain-crystallization performance similar to natural rubber simultaneously, therefore its physical and mechanical properties excellence (for tensile strength and tear strength).
According to one of the present invention preferred embodiment, the invention provides a kind of preparation method of rare earth catalyst, the method comprises:
1) under protection of inert gas, in the presence of an inert organic solvent, methylaluminoxane mixed with conjugated diene and neodymium compound, obtain the first mixed solution, wherein, described neodymium compound is for having general formula NdL
3the neodymium compound of HL, wherein, L is branched alkyl carboxylic acid's root or cycloalkanes acid group, and HL is corresponding carboxylic acid;
2) contacted with halogenide by described first mixed solution, obtain the second mixed solution, wherein, described halogenide is for having general formula AlR
2the aikyl aluminum halide of X, there is general formula Al
2r
3x
3sesquialkyl aluminium and have in the halohydrocarbon of general formula R X one or more, wherein, R is alkyl, and X is halogen;
3) contacted with alkylaluminium cpd by described second mixed solution, wherein, described alkylaluminium cpd is AlR for having general formula
3and/or AlHR
2alkylaluminium cpd, wherein, R is alkyl.
In the present invention, the kind of described neodymium compound, conjugated diene, halogenide and alkylaluminium cpd is described in detail in foregoing description rare earth catalyst composition, and the present invention does not repeat to repeat at this.
In the present invention, the kind of described inert organic solvents is described in detail in foregoing description rare earth catalyst, and the present invention does not repeat to repeat at this.
A kind of preferred implementation of preparation in accordance with the present invention, preferred neodymium compound: methylaluminoxane: halogenide: alkylaluminium cpd: the mol ratio of conjugated diene is 1:0.5-10:0.5-20:5-20:1-80, is preferably 1:2-8:1-10:6-18:10-70.
Preparation in accordance with the present invention, preferred steps 2) condition of described contact comprises: temperature is subzero 30 DEG C to 50 DEG C above freezing, and the time is 1-60min.
Preparation in accordance with the present invention, preferred steps 3) condition of described contact comprises: temperature is subzero 30 DEG C to 80 DEG C above freezing, and the time is 10min to 24h.
The invention provides a kind of rare earth catalyst prepared according to preparation method of the present invention.
The invention provides the application of rare earth catalyst of the present invention in conjugate diene polymerization.
Catalyst application of the present invention is when conjugate diene polymerization, the method of described conjugate diene polymerization can be carried out with reference to prior art, generally comprise: in the presence of the catalyst of the invention, conjugated diene solution polymerization is carried out in inert organic solvents, or there is no described inert organic solvents or containing inert organic solvents existent condition described in minute quantity under carry out the mass polymerization of conjugated diene, those skilled in the art all can know this, do not repeat them here.Wherein, successive polymerization can be carried out and also can carry out batchwise polymerization.
Use rare earth catalyst of the present invention to be polymerized, the polymeric articles obtained can be made to contain be more than or equal to the cis Isosorbide-5-Nitrae-structural content of 97%, molecular weight distribution is less than or equal to 2.5.
In described conjugate diene polymerization process, the inert organic solvents used is not particularly limited, it is aliphatic saturated hydrocarbon and/or the alicyclic hydrocarbon of inertia to reactive component that this area can be selected normally used, can be such as the straight-chain paraffin of C5-C10 and/or the naphthenic hydrocarbon of C5-C10, typical solvent include but not limited in hexane, hexanaphthene, heptane, pentane, iso-pentane, octane, methylcyclohexane, benzene,toluene,xylene and isopropyl benzene one or more, it can be identical or different with the inert organic solvents described in catalyzer of the present invention.
In described conjugate diene polymerization process, the conjugated diene that described conjugated diene can be commonly used for this area, include but not limited to the conjugated diene of C4-C6, can be such as divinyl, isoprene, 1,3-pentadiene, 1, one or more in 3-hexadiene, 2,3-dimethylbutadienes, are preferably divinyl and/or isoprene.Special instruction, the conjugated diene in rare earth catalyst composition of the present invention can be identical or different with the conjugated diene as polymerization single polymerization monomer.
In described conjugate diene polymerization process, the condition of described polymerization can be carried out with reference to prior art, and under preferable case, the condition of described polymerization comprises: the temperature of polymerization is subzero 30 DEG C to 80 DEG C above freezing, be preferably subzero 20 DEG C to 70 DEG C above freezing, be more preferably subzero 10 DEG C to 60 DEG C above freezing; The time of polymerization is 20-300 minute, is preferably 30-120 minute.
As previously mentioned, in described conjugate diene polymerization process, catalyst levels is generally the conjugated diene relative to every mole, and usage quantity is 1 × 10
-6-4 × 10
-4molNd, preferably 1.5 × 10
-6-3.5 × 10
-4molNd.
In described conjugate diene polymerization process, the conventional terminator in this area can be adopted directly to stop reactive polymer, described terminator can be such as water and/or alcoholic solvent, be preferably in water, methyl alcohol, ethanol, positive Virahol, Virahol and 2,6-di-tert-butyl hydroquinone methyl alcohol one or more.
When rare earth catalyst of the present invention being used for conjugated diene such as isoprene polymerization, the polyisoprene product of synthesis has the microtexture closely similar with natural rubber, it has high along 1,4-structural content (being more than or equal to 97%), high molecular (weight-average molecular weight is more than or equal to 600,000) and narrow ditribution (being less than or equal to 2.5).
Describe the present invention in detail by embodiment and comparative example below, but scope of the present invention is not limited to these embodiments.
If not otherwise specified, the chemical reagent used in embodiment is chemically pure reagent.
In the present invention, the microtexture (such as along Isosorbide-5-Nitrae-structure, head-tail keyed jointing unit) of being polymerized the conjugated diene polymer obtained adopts German Bruker400MHz nmr determination, and solvent is deuterochloroform; Molecular weight and molecualr weight distribution adopts Shimadzu LC-10AT type gel permeation chromatograph (GPC) to measure, and THF is moving phase, and Narrow distribution polystyrene is standard specimen, and temperature is 25 DEG C.
In the present invention, the aging reactor used in preparation process is through super-dry and deoxygenation process, and the solvent used in preparation process and conjugated diene are all through the process of nitrogen deoxygenation, and solvent water number is lower than 10ppm.
In the present invention, solvent water number refers to by weight, the water-content in solvent (inert solvent comprising the inert solvent in catalyst formulation and use in being polymerized).
In the present invention, monomer concentration refers to the mass concentration of conjugated diene monomer in polymerization system.
In the present invention, monomer conversion is concept well known to those skilled in the art, generally refer to initial monomer is converted into polymkeric substance per-cent (weight of its polymkeric substance obtained after being generally polymerization and the per-cent of the weight of the initial monomer added) by polyreaction, in specific implementation process, it is generally the weight difference before and after polymers soln drying and the weight ratio before polymers soln drying.In the present invention, the weight of polymers soln refers to the weight of the polymers soln not adding terminator.
Embodiment 1
Catalyst preparing:
Acetic acid neodymium, neodecanoic acid and hexane are mixed, reacts 6 hours under heated reflux condition, obtain neodymium caprate (Nd (C
10h
19o
2)
3(C
10h
20o
2)) hexane solution, concentration 0.5mol/l.
The hexane solution concentration of neodymium caprate is 0.5mol/l, the hexane solution concentration 0.5mol/l of methylaluminoxane, the hexane solution concentration 0.5mol/l of diisobutylaluminium hydride, the hexane solution concentration 0.5mol/l of aluminium diethyl monochloride.Experiment lower than 15ppm, uses front nitrogen to carry out deoxygenation process with hexane solvent water number; Experiment all operations step is all carried out under anhydrous and oxygen-free environment.
Be that the hexane solution of the divinyl of 0.11mol/l and the hexane solution of 20ml methylaluminoxane mix at-30 DEG C by the hexane solution of 4ml neodymium caprate, 180ml concentration, and then add the hexane solution of 8ml aluminium diethyl monochloride, and contact reacts 60 minutes, then the hexane solution of 60ml diisobutylaluminium hydride is added, and contact reacts 20 hours at continuing at-30 DEG C, obtain catalyzer.
The catalyzer of preparation is used to carry out butadiene solution polymerization:
Under nitrogen protection, in the hexane solution (1.8mol/l) of divinyl, add above-mentioned catalyzer, the ratio of catalyzer and monomer is 6 × 10
-5molNd/molBD, reacts 2 hours, in reaction system, then adds the methanol solution termination reaction of 2,6-di-tert-butyl hydroquinone at 40 DEG C.To take a morsel polymers soln weighing with weighing bottle, be then placed in vacuum drying oven and be dried to constant weight, calculate monomer conversion by example weight before and after dry, transformation efficiency is 98% as calculated.Polymkeric substance is 99.1% along Isosorbide-5-Nitrae-structural content, and weight-average molecular weight is 487,019, and molecular weight distribution is 2.0.
Embodiment 2
Acetic acid neodymium, neodecanoic acid and chlorobenzene are mixed, reacts 5 hours under heated reflux condition, obtain the chlorobenzene solution of neodymium caprate (NdVHV).
Triisobutyl aluminium hexane solution concentration is 0.5mol/l, and other reagent and operational requirement are with embodiment 1.
It is the chlorobenzene solution mixing of the hexane solution of the isoprene of 5.4mol/l, the hexane solution of 20ml methylaluminoxane and 10ml neodymium caprate (NdVHV) by 60ml concentration, then the hexane solution of 30ml aluminium diethyl monochloride is added, contact reacts 30 minutes under 0 DEG C of condition, then the hexane solution of 180ml triisobutyl aluminium is added, contact reacts 8 hours at room temperature 20 DEG C.
The catalyzer of preparation is used to carry out isoprene solution polymerization.Above-mentioned catalyzer is added in the hexane solution (1.56mol/l) of isoprene, the ratio of catalyzer and monomer is 4 × 10-5molNd/molIP, react 2 hours at room temperature 20 DEG C, in reaction system, then add the methanol solution termination reaction of 2,6-di-tert-butyl hydroquinone.To take a morsel polymers soln weighing with weighing bottle, be then placed in vacuum drying oven and be dried to constant weight, calculate monomer conversion by example weight before and after dry, transformation efficiency is 92% as calculated.Polymkeric substance is 98.8% along Isosorbide-5-Nitrae-structural content, and weight-average molecular weight is Isosorbide-5-Nitrae 36,903, and molecular weight distribution is 2.3.
Embodiment 3
Agents useful for same and working method, with embodiment 1, prepare neodymium iso-octanate (Nd (C
8h
15o
2)
3(C
8h
16o
2)) hexane solution.
Be the hexane solution of the isoprene of 1.75mol/l by 57ml concentration, the hexane solution mixing of 10ml concentration to be the hexane solution of the neodymium iso-octanate of 0.5mol/l and 80ml concentration the be methylaluminoxane of 0.5mol/l, then the hexane solution that 100ml concentration is a chlorine trimethyl silane of 0.5mol/l is added, and at 50 DEG C contact reacts 1 minute, add the hexane solution that 60ml concentration is the triisobutyl aluminium of 0.5mol/l again, continue contact reacts 10 minutes at 80 DEG C, obtain catalyzer.
The catalyzer of preparation is used to carry out divinyl and isoprene solution copolymerization.To the hexane solution (2mol/l of divinyl and isoprene, wherein the mol ratio of divinyl and isoprene is 8:2) in add above-mentioned catalyzer, the ratio of catalyzer and monomer is 1.1 × 10-4molNd/mol monomer, react 2.5 hours at 30 DEG C, then in reaction system, add the methanol solution termination reaction of 2,6-di-tert-butyl hydroquinone.To take a morsel polymers soln weighing with weighing bottle, be then placed in vacuum drying oven and be dried to constant weight, calculate monomer conversion by example weight before and after dry, transformation efficiency is 85% as calculated.In multipolymer segment, polyhutadiene is 98.9% along Isosorbide-5-Nitrae-structural content, and polyisoprene is 98.5% along Isosorbide-5-Nitrae-structural content, and multipolymer weight-average molecular weight is 510,312, and molecular weight distribution is 2.1.
Embodiment 4
Agents useful for same and working method are with embodiment 1.
Be the hexane solution of the neodymium caprate (NdVHV) of 0.5mol/l by 3ml concentration, the hexane solution mixing of 75ml concentration to be the hexane solution of the isoprene of 0.1mol/l and 30ml concentration the be methylaluminoxane of 0.5mol/l, then the hexane solution that 5ml concentration is the aluminium diethyl monochloride of 0.5mol/l is added, and at 10 DEG C contact reacts 0.5 hour, then add the hexane solution that 60ml concentration is the triisobutyl aluminium of 0.5mol/l, to continue at room temperature 20 DEG C contact reacts 4 hours.
The catalyzer of preparation is used to carry out isoprene solution polymerization.Above-mentioned catalyzer is added in isoprene hexane solution (1.48mol/l), the ratio of catalyzer and monomer is 1.8 × 10-4molNd/molIP, react 1.5 hours under room temperature, in reaction system, then add the methanol solution termination reaction of 2,6-di-tert-butyl hydroquinone.To take a morsel polymers soln weighing with weighing bottle, be then placed in vacuum drying oven and be dried to constant weight, calculate monomer conversion by example weight before and after dry, transformation efficiency is 97% as calculated.Polymkeric substance is 98.3% along Isosorbide-5-Nitrae-structural content, and weight-average molecular weight is 1,036,431, and molecular weight distribution is 2.5.
Embodiment 5
Agents useful for same and working method are with embodiment 1.
The hexane solution mixing that the hexane solution being the isoprene of 0.5mol/l by the hexane solution of 3ml neodymium caprate (NdVHV), 240ml concentration, 1.5ml concentration are the methylaluminoxane of 0.5mol/l, then the hexane solution that 12ml concentration is the aluminium diethyl monochloride of 0.5mol/l is added, and at 20 DEG C contact reacts 0.5 hour, then adding 30ml concentration is the hexane solution of the triisobutyl aluminium of 0.5mol/l contact reacts 6 hours at 20 DEG C, and then add continue at 20 DEG C at contact reacts 0.5 hour.
The catalyzer of preparation is used to carry out isoprene solution polymerization.Above-mentioned catalyzer is added in isoprene hexane solution (1.48mol/l), the ratio of catalyzer and monomer is 2.0 × 10-4molNd/molIP, react 1.5 hours under room temperature, in reaction system, then add the methanol solution termination reaction of 2,6-di-tert-butyl hydroquinone.To take a morsel polymers soln weighing with weighing bottle, be then placed in vacuum drying oven and be dried to constant weight, calculate monomer conversion by example weight before and after dry, transformation efficiency is 80% as calculated.Polymkeric substance is 98.3% along Isosorbide-5-Nitrae-structural content, and weight-average molecular weight is 1,947,865, and molecular weight distribution is 2.2.
Embodiment 6
Agents useful for same and working method are with embodiment 5.
Kaolinite Preparation of Catalyst as follows:
The hexane solution mixing that the hexane solution being the isoprene of 0.5mol/l by the hexane solution of 3ml neodymium caprate (NdVHV), 240ml concentration, 12ml concentration are the aluminium diethyl monochloride of 0.5mol/l, then the hexane solution that 1.5ml concentration is the methylaluminoxane of 0.5mol/l is added, and at 20 DEG C contact reacts 0.5 hour, then adding 30ml concentration is the hexane solution of the triisobutyl aluminium of 0.5mol/l contact reacts 6 hours at 20 DEG C, and then add continue at 20 DEG C at contact reacts 0.5 hour.
The catalyzer of preparation is used to carry out isoprene solution polymerization.Above-mentioned catalyzer is added in isoprene hexane solution (1.48mol/l), the ratio of catalyzer and monomer is 2.0 × 10-4molNd/molIP, react 1.5 hours under room temperature, in reaction system, then add the methanol solution termination reaction of 2,6-di-tert-butyl hydroquinone.To take a morsel polymers soln weighing with weighing bottle, be then placed in vacuum drying oven and be dried to constant weight, calculate monomer conversion by example weight before and after dry, transformation efficiency is 75% as calculated.Polymkeric substance is 97.3% along Isosorbide-5-Nitrae-structural content, and weight-average molecular weight is 1,947,865, and molecular weight distribution is 2.8.
Comparative example 1
Kaolinite Preparation of Catalyst:
According to the method Kaolinite Preparation of Catalyst of embodiment 2, unlike the use of neodymium compound be neodymium caprate (Nd (C
7h
9o
2)
3), obtain catalyzer D1.
The catalyzer of preparation is used to carry out isoprene solution polymerization:
Be polymerized according to the method for embodiment 2, unlike the use of catalyzer be D1, all the other conditions are all identical, and monomer conversion is 65%; Polymkeric substance is 96.4% along Isosorbide-5-Nitrae-structural content, and polymer average molecular weight is 1,834,791, and molecular weight distribution is 3.7.
Comparative example 2
Kaolinite Preparation of Catalyst:
According to the method Kaolinite Preparation of Catalyst of embodiment 2, do not use methylaluminoxane unlike in preparation process, obtain catalyzer D2.
The catalyzer of preparation is used to carry out isoprene solution polymerization:
Be polymerized according to the method for embodiment 2, unlike the use of catalyzer be D2, all the other conditions are all identical, and monomer conversion is 75%; Polymkeric substance is 97.2% along Isosorbide-5-Nitrae-structural content, and polymer average molecular weight is 534,791, and molecular weight distribution is 3.4.
Comparative example 3
Kaolinite Preparation of Catalyst:
According to the method Kaolinite Preparation of Catalyst of embodiment 2, unlike the use of neodymium compound be neodymium caprate (Nd (C
7h
9o
2)
3), and do not add methylaluminoxane, obtain catalyzer D3.
The catalyzer of preparation is used to carry out isoprene solution polymerization:
Be polymerized according to the method for embodiment 2, unlike the use of catalyzer be D3, all the other conditions are all identical, and monomer conversion is 50%; Polymkeric substance is 96.0% along Isosorbide-5-Nitrae-structural content, and polymer average molecular weight is 1,734,791, and molecular weight distribution is 4.0.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (13)
1. a rare earth catalyst composition, is characterized in that, said composition comprises:
A) neodymium compound, described neodymium compound is for having general formula NdL
3the neodymium compound of HL, wherein, L is branched alkyl carboxylic acid's root or cycloalkanes acid group, and HL is corresponding carboxylic acid;
B) methylaluminoxane;
C) halogenide, described halogenide is for having general formula AlR
2the aikyl aluminum halide of X, there is general formula Al
2r
3x
3sesquialkyl aluminium and have in the halohydrocarbon of general formula R X one or more, wherein, R is alkyl, X halogen;
D) alkylaluminium cpd, described alkylaluminium cpd is AlR for having general formula
3and/or AlHR
2alkylaluminium cpd, wherein, R is alkyl.
2. composition according to claim 1, wherein, L is the branched carboxylic acids root containing 8-12 carbon or the cycloalkanes acid group containing 8-12 carbon; Preferred described neodymium compound is Nd (C
7h
9o
2)
3(C
7h
10o
2), Nd (C
8h
15o
2)
3(C
8h
16o
2) or Nd (C
10h
19o
2)
3(C
10h
20o
2).
3. composition according to claim 1 and 2, wherein, neodymium compound: methylaluminoxane: halogenide: the mol ratio of alkylaluminium cpd is 1:0.5-10:0.5-20:5-20, is preferably 1:2-8:1-10:6-18.
4. according to the composition in claim 1-3 described in any one, wherein, said composition also comprises: e) conjugated diene; Preferred neodymium compound: the mol ratio of conjugated diene is 1:1-80, and more preferably described conjugated diene is isoprene and/or divinyl.
5., according to the composition in claim 1-4 described in any one, wherein, in halid general formula, R is C
1-C
6alkyl, X is bromine or chlorine; In the general formula of alkylaluminium cpd, R is C
1-C
6alkyl.
6. a rare earth catalyst, this catalyzer by the composition in claim 1-5 described in any one, is contacted with each other and obtains under protection of inert gas in inert organic solvents.
7. a preparation method for rare earth catalyst, the method comprises:
1) under protection of inert gas, in the presence of an inert organic solvent, methylaluminoxane mixed with conjugated diene and neodymium compound, obtain the first mixed solution, wherein, described neodymium compound is for having general formula NdL
3the neodymium compound of HL, wherein, L is branched alkyl carboxylic acid's root or cycloalkanes acid group, and HL is corresponding carboxylic acid;
2) contacted with halogenide by described first mixed solution, obtain the second mixed solution, wherein, described halogenide is for having general formula AlR
2the aikyl aluminum halide of X, there is general formula Al
2r
3x
3sesquialkyl aluminium and have in the halohydrocarbon of general formula R X one or more, wherein, R is alkyl, and X is halogen;
3) contacted with alkylaluminium cpd by described second mixed solution, wherein, described alkylaluminium cpd is AlR for having general formula
3and/or AlHR
2alkylaluminium cpd, wherein, R is alkyl.
8. preparation method according to claim 7, wherein, L is the branched carboxylic acids root containing 8-12 carbon or the cycloalkanes acid group containing 8-12 carbon, and preferred described neodymium compound is Nd (C
7h
9o
2)
3(C
7h
10o
2), Nd (C
8h
15o
2)
3(C
8h
16o
2) or Nd (C
10h
19o
2)
3(C
10h
20o
2).
9. the preparation method according to claim 7 or 8, wherein, neodymium compound: methylaluminoxane: halogenide: alkylaluminium cpd: the mol ratio of conjugated diene is 1:0.5-10:0.5-20:5-20:1-80, is preferably 1:2-8:1-10:6-18:10-70.
10. according to the preparation method in claim 7-9 described in any one, wherein, described conjugated diene is isoprene and/or divinyl; In halid general formula, R is C
1-C
6alkyl, X is bromine or chlorine; In the general formula of alkylaluminium cpd, R is C
1-C
6alkyl; Described inert organic solvents is aliphatic saturated hydrocarbon and/or alicyclic hydrocarbon.
11. preparation methods according to any one of claims of claim 7-10, wherein, step 2) condition of described contact comprises: temperature is subzero 30 DEG C to 50 DEG C above freezing, time is 1-60min, step 3) condition of described contact comprises: temperature is subzero 30 DEG C to 80 DEG C above freezing, and the time is 10min to 24h.
The rare earth catalyst that preparation method in 12. claim 7-11 described in any one prepares.
The application of catalyzer described in 13. claims 6 or 12 in conjugate diene polymerization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410326913.2A CN105330773B (en) | 2014-07-10 | 2014-07-10 | Rare earth catalyst composition and a kind of rare earth catalyst and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410326913.2A CN105330773B (en) | 2014-07-10 | 2014-07-10 | Rare earth catalyst composition and a kind of rare earth catalyst and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105330773A true CN105330773A (en) | 2016-02-17 |
| CN105330773B CN105330773B (en) | 2018-04-13 |
Family
ID=55281556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410326913.2A Active CN105330773B (en) | 2014-07-10 | 2014-07-10 | Rare earth catalyst composition and a kind of rare earth catalyst and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105330773B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106631994A (en) * | 2017-01-04 | 2017-05-10 | 安徽国星生物化学有限公司 | Method for preparing 3-methylpyridine |
| JP2019522100A (en) * | 2016-07-29 | 2019-08-08 | 株式会社ブリヂストン | Process for producing high cis-1,4-polydienes with lanthanide-based catalyst compositions |
| CN110903423A (en) * | 2018-09-18 | 2020-03-24 | 中国石油天然气股份有限公司 | Rare earth catalyst, preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0873515A (en) * | 1994-07-08 | 1996-03-19 | Ube Ind Ltd | Process for polymerizing conjugated diolefin |
| US20020173606A1 (en) * | 2000-03-16 | 2002-11-21 | Kwag Gwang Hoon | Novel monomeric neodymium carboxylate and its use in polymerization of conjugated diene |
| 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 |
| CN102532365A (en) * | 2010-12-09 | 2012-07-04 | 中国石油化工股份有限公司 | Neodymium-based homogeneous phase rare earth catalyst and preparation method and application thereof |
| CN102532353A (en) * | 2010-12-09 | 2012-07-04 | 中国石油化工股份有限公司 | Homogenous neodymium-based rare earth catalyst, and its preparation method and application |
-
2014
- 2014-07-10 CN CN201410326913.2A patent/CN105330773B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0873515A (en) * | 1994-07-08 | 1996-03-19 | Ube Ind Ltd | Process for polymerizing conjugated diolefin |
| US20020173606A1 (en) * | 2000-03-16 | 2002-11-21 | Kwag Gwang Hoon | Novel monomeric neodymium carboxylate and its use in polymerization of conjugated diene |
| 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 |
| CN102532365A (en) * | 2010-12-09 | 2012-07-04 | 中国石油化工股份有限公司 | Neodymium-based homogeneous phase rare earth catalyst and preparation method and application thereof |
| CN102532353A (en) * | 2010-12-09 | 2012-07-04 | 中国石油化工股份有限公司 | Homogenous neodymium-based rare earth catalyst, and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| GWANGHOON KWAG: "A Highly Reactive and Monomeric Neodymium Catalyst", 《MACROMOLECULES》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019522100A (en) * | 2016-07-29 | 2019-08-08 | 株式会社ブリヂストン | Process for producing high cis-1,4-polydienes with lanthanide-based catalyst compositions |
| CN106631994A (en) * | 2017-01-04 | 2017-05-10 | 安徽国星生物化学有限公司 | Method for preparing 3-methylpyridine |
| CN106631994B (en) * | 2017-01-04 | 2019-05-21 | 安徽国星生物化学有限公司 | A kind of preparation method of 3- picoline |
| CN110903423A (en) * | 2018-09-18 | 2020-03-24 | 中国石油天然气股份有限公司 | Rare earth catalyst, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105330773B (en) | 2018-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102532355B (en) | Homogenous neodymium-based rare earth catalyst, and its preparation method and application | |
| CN102786621B (en) | Rare earth catalytic system based high-cis styrene/isoprene/butadiene ternary polymer and its preparation method | |
| CN102108105B (en) | Neodymium (Nd)-based homogeneous rare earth catalyst as well as preparation method and application thereof | |
| CN105985472B (en) | A kind of preparation method of rare earth catalyst and preparation method thereof and polyisoprene | |
| Martins et al. | Highly efficient cis-1, 4 polymerisation of isoprene using simple homoleptic amido rare earth-based catalysts | |
| CN103450373B (en) | Rare earth catalyst composition and rare earth catalyst and application thereof | |
| CN102532365B (en) | Neodymium-based homogeneous phase rare earth catalyst and preparation method and application thereof | |
| CN101927186B (en) | Rare earth catalyst system and method for preparing high cis-1,4-polyisoprene | |
| CN105330773A (en) | Composition for rare earth catalyst, rare earth catalyst, and preparation method and application thereof | |
| CN103360516A (en) | Neodymium homogeneous phase rare earth catalyst composition and neodymium homogeneous phase rare earth catalyst as well as preparation method and application of neodymium homogeneous phase rare earth catalyst | |
| CN102532354B (en) | The homogeneous rare earth catalyst of neodymium series, its preparation method and application thereof | |
| CN102532353B (en) | Homogenous neodymium-based rare earth catalyst, and its preparation method and application | |
| JPS63179908A (en) | Myrcene polymer and production thereof | |
| CN106188356A (en) | A kind of Tetraheteropoly rare earth catalyst system and catalyzing and its preparation method and application | |
| CN102558400B (en) | Neodymium-based homogeneous phase rare earth catalyst and preparation method and application thereof | |
| CN108659182B (en) | Conjugated diene-polar monomer block copolymer and preparation method thereof | |
| TWI432470B (en) | Modified high cis conjugated diene copolymer and manufacturing method of the same | |
| CN116333199A (en) | Preparation method of polybutadiene | |
| CN104558451A (en) | High cis-butadiene-isoprene block copolymer and preparation method thereof | |
| CN101845111B (en) | Method for preparing conjugated diene polymer | |
| CN105330763A (en) | Composition for rare earth catalyst, rare earth catalyst, preparation method and application thereof, and olefin polymerization method | |
| CN103709282A (en) | Rare earth catalyst, and preparation method and application thereof | |
| CN105085720A (en) | Composition for rare earth catalyst, rare earth catalyst, preparation method and application of rare earth catalyst and isoprene polymerization method | |
| CN113754805A (en) | Rare earth catalyst and preparation and application thereof | |
| CN106916240B (en) | A method of preparing rare-earth isoprene rubber catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |