CN105330773B - Rare earth catalyst composition and a kind of rare earth catalyst and its preparation method and application - Google Patents
Rare earth catalyst composition and a kind of rare earth catalyst and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of rare earth catalyst composition, wherein, said composition includes：A) neodymium compound, the neodymium compound are with general formula NdL3The neodymium compound of HL, L are branched alkyl carboxylic acid's root or cycloalkanes acid group, and HL is corresponding carboxylic acid；B) methylaluminoxane；C) halide；D) alkyl aluminum compound.The present invention provides a kind of rare earth catalyst.The present invention provides a kind of preparation method of rare earth catalyst.The present invention provides the rare earth catalyst that a kind of preparation method of rare earth catalyst according to the invention is prepared.The present invention provides application of the catalyst of the present invention in conjugate diene polymerization.Neodymium series rare earth catalyst activity height, the catalyst efficiency of the present invention is high, can effectively reduce production cost.
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 rare earth
Application of the catalyst in conjugate diene polymerization.
Technical background
Conjugated diene (such as butadiene and isoprene) can synthesize stereotactic polymer by coordination polymerization process, raw
Produce important synthetic rubber kind (such as cis-1,4-polybutadiene and cis-1,4-polyisoprene).Cis-1,4-poly- isoamyl two
Alkene (polyisoprene rubber), also known as " natural man-made rubber ", has the stretch crystallization performance similar to natural rubber, and thing
Excellent performance is managed, is the kind that natural rubber can be uniquely substituted in synthetic rubber, is widely used in tire, medical, sebific duct glue
The industries such as band.
China's natural rubber resource scarcity, it is to solve China's natural rubber to develop high performance synthetic polyisoprenes rubber
The optimal path of imbalance between supply and demand.Isoprene can synthesize the high poly- isoamyl along Isosorbide-5-Nitrae-structural content under rare earth catalyst effect
Diene, and there is good physical mechanical property.
CN1479754A discloses a kind of catalyst of organic phosphate/alkyl aluminum/alkyl aluminium halide composition, less than 0
Can polyisoprene of the synthesizing cis 1,4- structural contents more than 99% under conditions of DEG C.But the catalyst is for polymerisation
During, it is necessary to carried out under extremely low temperature, and polymerization reaction time is considerably long, therefore is unfavorable for commercial Application.
CN10118663A and CN101260164A discloses a kind of catalyst of clamp type rareearth compound composition, can synthesize
The polyisoprene of high cis-contents, but catalyst preparation process is cumbersome, and cost is high, is unfavorable for commercial Application.
For isoprene product, improve cis-structure content and be conducive to improve its mechanical property, and
Polyisoprene cis-1,4-structural content that method disclosed in CN100448898C, CN101045768A etc. synthesizes is below
98%.
In fact, the polyisoprene product of high molecular weight, Narrow Molecular Weight Distribution has the strain similar to natural rubber
Crystal property is induced, its mechanical property has more advantage.But since carboxylic acid neodymium class rare earth catalyst is there are dynamics model, and as before
Described, the carboxylic acid neodymium class rare earth catalyst obtained according to current formula and preparation method is difficult to obtain narrow molecular-weight for polymerization
The product of distribution.
The content of the invention
High-cis structural content, high molecular weight, Narrow Molecular Weight Distribution can be synthesized the object of the present invention is to provide a kind of
The rare earth catalyst of polymer, thus, the present invention provides a kind of rare earth catalyst composition, rare earth catalyst and its preparation
Method and the application in conjugate diene polymerization.
To realize object defined above, according to the first aspect of the invention, the present invention provides a kind of combination of rare earth catalyst
Thing, wherein, said composition includes：
A) neodymium compound, the neodymium compound are with general formula NdL3The neodymium compound of HL, wherein, L is branched alkyl
Carboxylate radical or cycloalkanes acid group, HL are corresponding carboxylic acid；
B) methylaluminoxane；
C) halide, the halide are with general formula AlR2The aikyl aluminum halide of X, have general formula Al2R3X3Sesquialter alkane
One or more in base aluminium and halogenated hydrocarbons with general formula R X, wherein, R is alkyl, X halogens；
D) alkyl aluminum compound, it with general formula is AlR that the alkyl aluminum compound, which is,3And/or AlHR2Alkyl aluminum chemical combination
Thing, wherein, R is alkyl.
According to the second aspect of the invention, the present invention provides a kind of rare earth catalyst, the catalyst is by of the present invention
Composition under inert gas shielding, contact with each other to obtain in inert organic solvents.
According to the third aspect of the invention we, the present invention provides a kind of preparation method of rare earth catalyst, this method to include：
1) under inert gas shielding, in the presence of an inert organic solvent, by methylaluminoxane and conjugated diene and
Neodymium compound mixes, and obtains the first mixed liquor, wherein, the neodymium compound is with general formula NdL3The neodymium compound of HL, its
In, L is branched alkyl carboxylic acid's root or cycloalkanes acid group, and HL is corresponding carboxylic acid；
2) first mixed liquor is contacted with halide, obtains the second mixed liquor, wherein, the halide is with logical
Formula AlR2The aikyl aluminum halide of X, have general formula Al2R3X3Sesquialkyl aluminium and with general formula R X halogenated hydrocarbons in one kind or
It is a variety of, wherein, R is alkyl, and X is halogen；
3) second mixed liquor is contacted with alkyl aluminum compound, wherein, the alkyl aluminum compound is with general formula
For AlR3And/or AlHR2Alkyl aluminum compound, wherein, R is alkyl.
According to the fourth aspect of the invention, the present invention provides a kind of preparation method of rare earth catalyst according to the invention
The rare earth catalyst being prepared.
According to the fifth aspect of the invention, the present invention provides catalyst of the present invention in conjugate diene polymerization
Application.
Neodymium series rare earth catalyst activity height, the catalyst efficiency of the present invention is high, can effectively reduce production cost；This is sent out
When bright rare earth catalyst is used for conjugated diene such as isoprene polymerization, the polyisoprene product of synthesis have with it is natural
The closely similar microstructure of rubber, it has high along Isosorbide-5-Nitrae-structural content (being more than or equal to 97%), high molecular weight and narrow ditribution
(being less than or equal to 2.5), while there is the strain inducing crystal property similar to natural rubber.Therefore, using the neodymium series of the present invention
The polyisoprene product that rare earth catalyst synthesizes can be used for replacement natural rubber to be widely used in manufacturing industry, in particular for
Tyre industry, in addition, the polyisoprene product synthesized using the neodymium series rare earth catalyst of the present invention is in medical field
Using also there is its advantage.Compared with natural rubber, the polyisoprene that synthesizes of neodymium series rare earth catalyst of the present invention is used
Material of the product without easy allergy of human body such as protein, has been widely used in terms of medical product.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of rare earth catalyst composition, wherein, said composition includes：
A) neodymium compound, the neodymium compound are with general formula NdL3The neodymium compound of HL, wherein, L is branched alkyl
Carboxylate radical or cycloalkanes acid group, HL are corresponding carboxylic acid；
B) methylaluminoxane；
C) halide, the halide are with general formula AlR2The aikyl aluminum halide of X, have general formula Al2R3X3Sesquialter alkane
One or more in base aluminium and halogenated hydrocarbons with general formula R X, wherein, R is alkyl, X halogens；
D) alkyl aluminum compound, it with general formula is AlR that the alkyl aluminum compound, which is,3And/or AlHR2Alkyl aluminum chemical combination
Thing, wherein, R is alkyl.
The purpose of the present invention can be achieved in preceding solution according to the invention, and in order to further improve the present invention's
The activity and catalytic efficiency of rare earth catalyst, for the present invention, further preferred L is branched carboxylic acids root containing 8-12 carbon or contains
The cycloalkanes acid group of 8-12 carbon, such as can be octanoic acid, n-nonanoic acid or capric acid；For the present invention, preferably described neodymium compound is knot
Unify the neodymium naphthenate [Nd (C of molecular naphthenic acid7H9O2)3·(C7H10O2)], with reference to the neodymium iso-octanate [Nd of a molecule isooctyl acid
(C8H15O2)3·(C8H16O2)] or combine a molecule neodecanoic acid neodymium caprate [Nd (C10H19O2)3·(C10H20O2)]。
In the present invention, for the carboxylic acid molecules in preferably described neodymium compound with carboxylic acid neodymium there are bonding action, it can be commercially available
Obtain, can also be prepared, such as can be prepared as follows：Acetic acid neodymium and excessive carboxylic acid atent solvent (such as benzene,
Toluene, chlorobenzene, hexane etc.) in occur metathesis reaction NdL is made3·HR。
The purpose of the present invention can be achieved in preceding solution according to the invention, and in order to further improve the present invention's
The activity and catalytic efficiency of rare earth catalyst, for the present invention, further preferred neodymium compound:Methylaluminoxane:Halide:Alkane
The molar ratio of base aluminium compound is 1:0.5-10:0.5-20:5-20, is preferably 1:2-8:1-10:6-18.
The purpose of the present invention can be achieved in preceding solution according to the invention, for the present invention, in order to urge rare earth
Agent is in homogeneously, and further preferably, composition of the invention further includes：E) conjugated diene；More preferably neodymium compound:Conjugation two
The molar ratio of alkene is 1:1-80, more preferably 1:10-70.
In the present invention, optional wider range of the species of conjugated diene, for the present invention, preferably described conjugated diene
It is preferably butadiene, isoprene, 1,3-pentadiene, 1,3- hexadienes, 2,3- dimethyl butyrates for the conjugated diene of C4-C6
One or more in diene, particularly preferably butadiene or isoprene.
The purpose of the present invention can be achieved in preceding solution according to the invention, and in order to further improve the present invention's
The activity and catalytic efficiency of rare earth catalyst, for the present invention, in the general formula of further preferred halide, R C1-C6Alkyl,
Such as can be ethyl, propyl group, isopropyl, butyl, isobutyl group, the tert-butyl group, benzyl or pi-allyl, X is bromine or chlorine, it is further preferred that
The halide is one in aluminium diethyl monochloride, a chlorine trimethyl silane, sesquialter ethylmercury chloride aluminium and a chloro-di-isobutyl aluminum
Kind is a variety of.
The purpose of the present invention can be achieved in preceding solution according to the invention, and in order to further improve the present invention's
The activity and catalytic efficiency of rare earth catalyst, for the present invention, in the general formula of further preferred alkyl aluminum compound, R C1-C6
Alkyl, more preferably alkyl aluminum compound for trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, triisobutyl aluminium, three
One or more in amyl group aluminium, three hexyl aluminium, diethyl aluminium hydride and hydrogenation dibutyl aluminium, more preferably trimethyl aluminium, three
One or more in aluminium isobutyl, triethyl aluminum and hydrogenation dibutyl aluminium.
The present invention provides a kind of rare earth catalyst, and the catalyst is by composition of the present invention in inert gas shielding
Under, contact with each other to obtain in inert organic solvents.
In the present invention, catalyst by rare earth catalyst composition of the present invention under inert gas shielding, lazy
Property organic solvent in the mode that contacts have it is a variety of, such as can will be in the rare earth catalyst composition of the present invention it is each
Component is dissolved in the inert organic solvents respectively is configured to solution form, is then mixed to obtain, can also send out this
Bright rare earth catalyst directly is mixed to obtain with composition with the inert organic solvents, as long as so that the rare earth of the present invention
Component is contacted in the inert organic solvents and can achieved the object of the present invention in catalyst composition.The present invention's is specific
In embodiment, generally rare earth catalyst is first dissolved in inert organic solvents in advance with the rare earth compound in composition and is configured
Into solution (those skilled in the art's solution is generally referred to as dispersion liquid), then remaining component is added in solution and is contacted
Obtain the catalyst of the present invention.
Heretofore described inert gas can be inert gas commonly used in the art, to this those skilled in the art
It can know, will not enumerate herein.
Rare earth catalyst according to the present invention, the selection of the inert organic solvents are referred to prior art progress, can
Think the aliphatic saturated hydrocarbon or alicyclic hydrocarbon solvents inert to reactive component commonly used in the art, for the present invention, preferably
The inert organic solvents be C5-C10 linear paraffin and/or C5-C10 cycloalkane, particularly preferably pentane, isopentane,
One or more in hexane, hexamethylene, heptane and octane.
The rare earth catalyst being prepared using the foregoing of the present invention, activity is high, catalyst efficiency is high, Neng Gouyou
Effect reduces production cost；When the rare earth catalyst of the present invention is used for conjugated diene such as isoprene polymerization, synthesis gathers
Isoprene product has the microstructure closely similar with natural rubber, and there is high suitable Isosorbide-5-Nitrae-structural content (to be more than or equal to for it
97%), high molecular weight and narrow ditribution (being less than or equal to 2.5), while there is the strain inducing crystal property similar to natural rubber,
Therefore its physical mechanical property is excellent (by taking tensile strength and tearing strength as an example).
A kind of preferred embodiment according to the present invention, the present invention provides a kind of preparation method of rare earth catalyst,
This method includes：
1) under inert gas shielding, in the presence of an inert organic solvent, by methylaluminoxane and conjugated diene and
Neodymium compound mixes, and obtains the first mixed liquor, wherein, the neodymium compound is with general formula NdL3The neodymium compound of HL, its
In, L is branched alkyl carboxylic acid's root or cycloalkanes acid group, and HL is corresponding carboxylic acid；
2) first mixed liquor is contacted with halide, obtains the second mixed liquor, wherein, the halide is with logical
Formula AlR2The aikyl aluminum halide of X, have general formula Al2R3X3Sesquialkyl aluminium and with general formula R X halogenated hydrocarbons in one kind or
It is a variety of, wherein, R is alkyl, and X is halogen；
3) second mixed liquor is contacted with alkyl aluminum compound, wherein, the alkyl aluminum compound is with general formula
For AlR3And/or AlHR2Alkyl aluminum compound, wherein, R is alkyl.
In the present invention, the neodymium compound, conjugated diene, the species of halide and alkyl aluminum compound are in foregoing description
Rare earth catalyst is had been described in in composition, and the present invention does not repeat to repeat herein.
In the present invention, the species of the inert organic solvents has been described in foregoing description rare earth catalyst, this
Invention does not repeat to repeat herein.
A kind of preferred embodiment of preparation in accordance with the present invention, preferably neodymium compound:Methylaluminoxane:Halogenation
Thing:Alkyl aluminum compound:The molar 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 the contact includes：Temperature is subzero 30 DEG C to zero
Upper 50 DEG C, time 1-60min.
Preparation in accordance with the present invention, preferred steps 3) condition of the contact includes：Temperature is subzero 30 DEG C to zero
Upper 80 DEG C, the time is 10min to 24h.
The present invention provides the rare earth catalyst that a kind of preparation method according to the invention is prepared.
The present invention provides application of the rare earth catalyst of the present invention in conjugate diene polymerization.
When the catalyst of the present invention is applied to conjugate diene polymerization, the method for the conjugate diene polymerization is referred to
The prior art carries out, and generally comprises：In the presence of the catalyst of the invention, conjugated diene is carried out in inert organic solvents
Polymerisation in solution, or under the conditions of no inert organic solvents or containing existing for inert organic solvents described in very small amount into
The polymerisation in bulk of row conjugated diene, those skilled in the art can know this details are not described herein.Wherein it is possible to carry out
Continuous polymerization can also carry out batchwise polymerization.
Rare earth catalyst using the present invention is polymerize, and the polymeric articles enabled to, which contain, to be more than or equal to
97% cis Isosorbide-5-Nitrae-structural content, molecular weight distribution are less than or equal to 2.5.
During the conjugate diene polymerization, the inert organic solvents used are not particularly limited, this can be selected
The field usually used aliphatic saturated hydrocarbon and/or alicyclic inert to reactive component, such as can be the straight chain of C5-C10
The cycloalkane of alkane and/or C5-C10, typical solvent include but not limited to hexane, hexamethylene, heptane, pentane, isopentane, pungent
One or more in alkane, hexahydrotoluene, benzene,toluene,xylene and isopropylbenzene, its can with the present invention catalyst described in
Inert organic solvents it is identical or different.
During the conjugate diene polymerization, the conjugated diene can be conjugated diene commonly used in the art
Hydrocarbon, include but not limited to C4-C6 conjugated diene, such as can be butadiene, isoprene, 1,3-pentadiene, 1,3- oneself
One or more in diene, 2,3- dimethyl butadienes, are preferably butadiene and/or isoprene.Special instruction, this
The rare earth catalyst of invention by the use of the conjugated diene in composition and the conjugated diene as polymerized monomer can be identical or not
Together.
During the conjugate diene polymerization, the condition of the polymerization is referred to prior art progress, preferably feelings
Under condition, the condition of the polymerization includes：The temperature of polymerization is subzero 30 DEG C to 80 DEG C above freezing, is preferably subzero 20 DEG C to above freezing 70
DEG C, more preferably subzero 10 DEG C to 60 DEG C above freezing；The time of polymerization is 20-300 minutes, is preferably 30-120 minutes.
As it was previously stated, during the conjugate diene polymerization, catalyst amount is generally to be total to relative to every mole
Yoke alkadienes, usage amount are 1 × 10-6-4×10-4MolNd, preferably 1.5 × 10-6-3.5×10-4molNd。
During the conjugate diene polymerization, can use terminator commonly used in the art to living polymer directly into
Row terminates, and the terminator for example can be water and/or alcoholic solvent, preferably water, methanol, ethanol, positive isopropanol, isopropanol and
One or more in 2,6- di-tert-butyl hydroquinone's methanol.
When the rare earth catalyst of the present invention is used for conjugated diene such as isoprene polymerization, the polyisoprene of synthesis
Product has the microstructure closely similar with natural rubber, it has high along Isosorbide-5-Nitrae-structural content (being more than or equal to 97%), height
Molecular weight (weight average molecular weight is more than or equal to 600,000) and narrow ditribution (being less than or equal to 2.5).
The present invention is described in detail by embodiment and comparative example below, but the scope of the present invention is not limited to these implementations
Example.
If not otherwise specified, the chemical reagent used in embodiment is chemically pure reagent.
In the present invention, the microstructure for the conjugated diene polymer polymerizeing is (such as along Isosorbide-5-Nitrae-structure, head-tail
Bonded unit) using Germany's Bruker400MHz nmr determinations, solvent is deuterochloroform；Molecular weight and molecualr weight distribution
Measured using Shimadzu LC-10AT types gel permeation chromatograph (GPC), THF is mobile phase, and Narrow distribution polystyrene is standard specimen, temperature
Spend for 25 DEG C.
In the present invention, the aging reactor used in preparation process is handled by dry and deoxygenation, is used in preparation process molten
Agent and conjugated diene are handled by nitrogen deoxygenation, and solvent water number is less than 10ppm.
In the present invention, solvent water number refers to by weight, solvent (including the atent solvent in catalyst formulation and polymerization
Used in atent solvent) in water content.
In the present invention, monomer concentration refers to mass concentration of the conjugated diene monomer in polymerization system.
In the present invention, monomer conversion is concept well known to those skilled in the art, and generally referred to as initial monomer passes through
Polymerisation is converted into percentage (weight of its polymer obtained after generally polymerizeing and the initial monomer added of polymer
Weight percentage), in specific implementation process, it is generally the front and rear weight difference of polymer solution drying and polymer is molten
Weight ratio before liquid drying.The weight of polymer solution refers to not adding the weight of the polymer solution of terminator in the present invention
Amount.
Embodiment 1
Catalyst preparation：
Acetic acid neodymium, neodecanoic acid and hexane are mixed, when reaction 6 is small under heated reflux condition, obtain neodymium caprate (Nd
(C10H19O2)3·(C10H20O2)) 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, hydrogen
Change the hexane solution concentration 0.5mol/l, the hexane solution concentration 0.5mol/l of aluminium diethyl monochloride of diisobutyl aluminum.Experiment is used
Hexane solvent water number is less than 15ppm, and deoxygenation processing is carried out with nitrogen using preceding；All operations step is tested in anhydrous and oxygen-free ring
Carried out under border.
By the hexane solution of 4ml neodymium caprates, the hexane solution and 20ml of the butadiene that 180ml concentration is 0.11mol/l
The hexane solution of methylaluminoxane mixes at -30 DEG C, then adds the hexane solution of 8ml aluminium diethyl monochlorides, and contacts
Reaction 60 minutes, then adds the hexane solution of 60ml diisobutylaluminium hydrides, and it is small to continue at haptoreaction 20 at -30 DEG C
When, obtain catalyst.
Butadiene solution polymerization is carried out using the catalyst of preparation：
Under nitrogen protection, above-mentioned catalyst, catalyst and list are added into the hexane solution (1.8mol/l) of butadiene
The ratio of body is 6 × 10-5MolNd/molBD, when reaction 2 is small at 40 DEG C, then adds 2,6-, bis- tertiary fourths into reaction system
The methanol solution of base hydroquinone terminates reaction.A small amount of polymer solution is taken with measuring cup and is weighed, and is subsequently placed in vacuum drying oven
Middle drying calculates monomer conversion by example weight before and after drying, is computed conversion ratio as 98% to constant weight.Polymer along 1,
4- structural contents are 99.1%, weight average molecular weight 487,019, molecular weight distribution 2.0.
Embodiment 2
Acetic acid neodymium, neodecanoic acid and chlorobenzene are mixed, when reaction 5 is small under heated reflux condition, obtain neodymium caprate (NdV
HV chlorobenzene solution).
Triisobutyl aluminium hexane solution concentration is 0.5mol/l, and other reagents and operation are required with embodiment 1.
By 60ml concentration be the hexane solution of isoprene of 5.4mol/l, the hexane solution of 20ml methylaluminoxane and
The chlorobenzene solution mixing of 10ml neodymium caprates (NdVHV), then adds the hexane solution of 30ml aluminium diethyl monochlorides, at 0 DEG C
Under the conditions of haptoreaction 30 minutes, then add the hexane solutions of 180ml triisobutyl aluminiums, the haptoreaction 8 at 20 DEG C of room temperature
Hour.
Isoprene solution polymerization is carried out using the catalyst of preparation.To the hexane solution (1.56mol/l) of isoprene
Middle to add above-mentioned catalyst, the ratio of catalyst and monomer be 4 × 10-5molNd/molIP, and it is small to react 2 at 20 DEG C of room temperature
When, the methanol solution that 2,6- di-tert-butyl hydroquinones are then added into reaction system terminates reaction.Taken on a small quantity with measuring cup
Polymer solution is simultaneously weighed, and is subsequently placed in vacuum drying oven and is dried to constant weight, and calculating monomer by example weight before and after drying turns
Rate, is computed conversion ratio as 92%.Polymer is 98.8% along Isosorbide-5-Nitrae-structural content, and weight average molecular weight is Isosorbide-5-Nitrae 36,903, point
Son amount is distributed as 2.3.
Embodiment 3
Neodymium iso-octanate (Nd (C are prepared with embodiment 1 in agents useful for same and operating method8H15O2)3·(C8H16O2))
Hexane solution.
The isooctyl acid for being 0.5mol/l by the hexane solution of isoprene that 57ml concentration is 1.75mol/l, 10ml concentration
The hexane solution and 80ml concentration of neodymium are the hexane solution mixing of the methylaluminoxane of 0.5mol/l, then add 100ml concentration
For the hexane solution of a chlorine trimethyl silane of 0.5mol/l, and haptoreaction 1 minute at 50 DEG C, adding 60ml concentration is
The hexane solution of the triisobutyl aluminium of 0.5mol/l, continues haptoreaction 10 minutes at 80 DEG C, obtains catalyst.
Butadiene is carried out using the catalyst of preparation and isoprene solution is copolymerized.To butadiene and the hexane of isoprene
(molar ratio of 2mol/l, wherein butadiene and isoprene are 8 to solution：2) the above-mentioned catalyst of addition in, catalyst and monomer
Ratio is 1.1 × 10-4molNd/mol monomers, and when reaction 2.5 is small at 30 DEG C, 2,6-, bis- uncles are then added into reaction system
The methanol solution of butylhydroquinone terminates reaction.A small amount of polymer solution is taken with measuring cup and is weighed, and is subsequently placed in vacuum baking
Dried in case to constant weight, monomer conversion is calculated by example weight before and after drying, be computed conversion ratio as 85%.Copolymer chain
Polybutadiene is 98.9% along Isosorbide-5-Nitrae-structural content in section, and polyisoprene is 98.5% along Isosorbide-5-Nitrae-structural content, copolymer weight
Average molecular weight is 510,312, molecular weight distribution 2.1.
Embodiment 4
Agents useful for same and operating method are the same as embodiment 1.
It is 0.1mol/l's by the hexane solution of neodymium caprate (NdVHV) that 3ml concentration is 0.5mol/l, 75ml concentration
The hexane solution and 30ml concentration of isoprene are the hexane solution mixing of the methylaluminoxane of 0.5mol/l, then add 5ml
Concentration is the hexane solution of the aluminium diethyl monochloride of 0.5mol/l, and when haptoreaction 0.5 is small at 10 DEG C, then adds 60ml
Concentration is the hexane solution of the triisobutyl aluminium of 0.5mol/l, when continuing at that haptoreaction 4 is small at 20 DEG C of room temperature.
Isoprene solution polymerization is carried out using the catalyst of preparation.Into isoprene hexane solution (1.48mol/l)
Add above-mentioned catalyst, the ratio of catalyst and monomer is 1.8 × 10-4molNd/molIP, react at room temperature 1.5 it is small when,
Then the methanol solution that 2,6- di-tert-butyl hydroquinones are added into reaction system terminates reaction.A small amount of polymerization is taken with measuring cup
Thing solution is simultaneously weighed, and is subsequently placed in vacuum drying oven and is dried to constant weight, and monomer conversion is calculated by example weight before and after drying,
Conversion ratio is computed as 97%.Polymer is 98.3% along Isosorbide-5-Nitrae-structural content, weight average molecular weight 1,036,431, molecular weight
It is distributed as 2.5.
Embodiment 5
Agents useful for same and operating method are the same as embodiment 1.
By the hexane solution of 3ml neodymium caprates (NdVHV), the hexane for the isoprene that 240ml concentration is 0.5mol/l
The hexane solution mixing of solution, the methylaluminoxane that 1.5ml concentration is 0.5mol/l, it is 0.5mol/l then to add 12ml concentration
Aluminium diethyl monochloride hexane solution, and when haptoreaction 0.5 is small at 20 DEG C, it is 0.5mol/l then to add 30ml concentration
The hexane solution of triisobutyl aluminium when haptoreaction 6 is small at 20 DEG C, then add and continue at haptoreaction 0.5 at 20 DEG C
Hour.
Isoprene solution polymerization is carried out using the catalyst of preparation.Into isoprene hexane solution (1.48mol/l)
Add above-mentioned catalyst, the ratio of catalyst and monomer is 2.0 × 10-4molNd/molIP, react at room temperature 1.5 it is small when,
Then the methanol solution that 2,6- di-tert-butyl hydroquinones are added into reaction system terminates reaction.A small amount of polymerization is taken with measuring cup
Thing solution is simultaneously weighed, and is subsequently placed in vacuum drying oven and is dried to constant weight, and monomer conversion is calculated by example weight before and after drying,
Conversion ratio is computed as 80%.Polymer is 98.3% along Isosorbide-5-Nitrae-structural content, weight average molecular weight 1,947,865, molecular weight
It is distributed as 2.2.
Embodiment 6
Agents useful for same and operating method are the same as embodiment 5.
Catalyst is prepared as follows：
By the hexane solution of 3ml neodymium caprates (NdVHV), the hexane for the isoprene that 240ml concentration is 0.5mol/l
The hexane solution mixing of solution, the aluminium diethyl monochloride that 12ml concentration is 0.5mol/l, then adding 1.5ml concentration is
The hexane solution of the methylaluminoxane of 0.5mol/l, and when haptoreaction 0.5 is small at 20 DEG C, then adding 30ml concentration is
The hexane solution of the triisobutyl aluminium of 0.5mol/l is when haptoreaction 6 is small at 20 DEG C, then adds to continue at 20 DEG C and connects
Touch reaction 0.5 it is small when.
Isoprene solution polymerization is carried out using the catalyst of preparation.Into isoprene hexane solution (1.48mol/l)
Add above-mentioned catalyst, the ratio of catalyst and monomer is 2.0 × 10-4molNd/molIP, react at room temperature 1.5 it is small when,
Then the methanol solution that 2,6- di-tert-butyl hydroquinones are added into reaction system terminates reaction.A small amount of polymerization is taken with measuring cup
Thing solution is simultaneously weighed, and is subsequently placed in vacuum drying oven and is dried to constant weight, and monomer conversion is calculated by example weight before and after drying,
Conversion ratio is computed as 75%.Polymer is 97.3% along Isosorbide-5-Nitrae-structural content, weight average molecular weight 1,947,865, molecular weight
It is distributed as 2.8.
Comparative example 1
Prepare catalyst：
Method according to embodiment 2 prepares catalyst, the difference is that the neodymium compound used is neodymium caprate (Nd
(C7H9O2)3), obtain catalyst D1.
Isoprene solution polymerization is carried out using the catalyst of preparation：
Method according to embodiment 2 is polymerize, the difference is that the catalyst used is D1, remaining condition all same is single
Transformation rate is 65%；Polymer is 96.4% along Isosorbide-5-Nitrae-structural content, polymer average molecular weight 1,834,791, molecule
Amount is distributed as 3.7.
Comparative example 2
Prepare catalyst：
Method according to embodiment 2 prepares catalyst, the difference is that being urged in preparation process without using methylaluminoxane
Agent D2.
Isoprene solution polymerization is carried out using the catalyst of preparation：
Method according to embodiment 2 is polymerize, the difference is that the catalyst used is D2, remaining condition all same is single
Transformation rate is 75%；Polymer is 97.2% along Isosorbide-5-Nitrae-structural content, polymer average molecular weight 534,791, molecular weight
It is distributed as 3.4.
Comparative example 3
Prepare catalyst：
Method according to embodiment 2 prepares catalyst, the difference is that the neodymium compound used is neodymium caprate (Nd
(C7H9O2)3), and methylaluminoxane is added without, obtain catalyst D3.
Isoprene solution polymerization is carried out using the catalyst of preparation：
Method according to embodiment 2 is polymerize, the difference is that the catalyst used is D3, remaining condition all same is single
Transformation rate is 50%；Polymer is 96.0% along Isosorbide-5-Nitrae-structural content, polymer average molecular weight 1,734,791, molecule
Amount is distributed as 4.0.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (17)
1. a kind of rare earth catalyst composition, it is characterised in that said composition includes：
A) neodymium compound, the neodymium compound are with general formula NdL3The neodymium compound of HL, wherein, L is branched alkyl carboxylic acid's root
Or cycloalkanes acid group, HL are corresponding carboxylic acid；
B) methylaluminoxane；
C) halide, the halide are with general formula AlR2The aikyl aluminum halide of X, have general formula Al2R3X3Sesquialkyl aluminium
With the one or more in the halogenated hydrocarbons with general formula R X, wherein, R is alkyl, X halogens；
D) alkyl aluminum compound, it with general formula is AlR that the alkyl aluminum compound, which is,3And/or AlHR2Alkyl aluminum compound, its
In, R is alkyl；
Neodymium compound:Methylaluminoxane:Halide:The molar ratio of alkyl aluminum compound is 1:0.5-10:0.5-20:5-20.
2. composition according to claim 1, wherein, L is branched carboxylic acids root containing 8-12 carbon or containing 8-12 carbon
Cycloalkanes acid group.
3. composition according to claim 2, wherein, the neodymium compound is Nd (C7H9O2)3·(C7H10O2)、Nd
(C8H15O2)3·(C8H16O2) or Nd (C10H19O2)3·(C10H20O2)。
4. according to the composition described in any one in claim 1-3, wherein, neodymium compound:Methylaluminoxane:Halide:
The molar ratio of alkyl aluminum compound is 1:2-8:1-10:6-18.
5. according to the composition described in any one in claim 1-3, wherein, said composition further includes：E) conjugated diene.
6. composition according to claim 5, wherein, neodymium compound:The molar ratio of conjugated diene is 1:1-80.
7. composition according to claim 6, wherein, the conjugated diene is isoprene and/or butadiene.
8. according to the composition described in any one in claim 1-3, wherein, in the general formula of halide, R C1-C6Alkane
Base, X are bromine or chlorine；In the general formula of alkyl aluminum compound, R C1-C6Alkyl.
9. a kind of rare earth catalyst, which is protected as the composition described in any one in claim 1-8 in inert gas
Under shield, contact with each other to obtain in inert organic solvents.
10. a kind of preparation method of rare earth catalyst, this method include：
1) under inert gas shielding, in the presence of an inert organic solvent, by methylaluminoxane and conjugated diene and neodymium
Compound mixes, and obtains the first mixed liquor, wherein, the neodymium compound is with general formula NdL3The neodymium compound of HL, wherein, L
For branched alkyl carboxylic acid's root or cycloalkanes acid group, HL is corresponding carboxylic acid；
2) first mixed liquor is contacted with halide, obtains the second mixed liquor, wherein, the halide is with general formula
AlR2The aikyl aluminum halide of X, have general formula Al2R3X3Sesquialkyl aluminium and with general formula R X halogenated hydrocarbons in one kind or more
Kind, wherein, R is alkyl, and X is halogen；
3) second mixed liquor is contacted with alkyl aluminum compound, wherein, it with general formula is AlR that the alkyl aluminum compound, which is,3
And/or AlHR2Alkyl aluminum compound, wherein, R is alkyl；
Neodymium compound:Methylaluminoxane:Halide:Alkyl aluminum compound:The molar ratio of conjugated diene is 1:0.5-10:0.5-
20:5-20:1-80。
11. preparation method according to claim 10, wherein, L is the branched carboxylic acids root or a containing 8-12 containing 8-12 carbon
The cycloalkanes acid group of carbon.
12. preparation method according to claim 11, wherein, the neodymium compound is Nd (C7H9O2)3·(C7H10O2)、Nd
(C8H15O2)3·(C8H16O2) or Nd (C10H19O2)3·(C10H20O2)。
13. according to the preparation method described in any one in claim 10-12, wherein, neodymium compound:Methylaluminoxane:Halogen
Compound:Alkyl aluminum compound:The molar ratio of conjugated diene is 1:2-8:1-10:6-18:10-70.
14. according to the preparation method described in any one in claim 10-12, wherein, the conjugated diene is isoamyl two
Alkene and/or butadiene；In the general formula of halide, R C1-C6Alkyl, X is bromine or chlorine；In the general formula of alkyl aluminum compound, R is
C1-C6Alkyl；The inert organic solvents are aliphatic saturated hydrocarbon and/or alicyclic.
15. according to the preparation method described in any one in claim 10-12, wherein, the condition bag of the step 2) contact
Include：Temperature is subzero 30 DEG C to 50 DEG C above freezing, and time 1-60min, the condition of the step 3) contact includes：Temperature is subzero
30 DEG C to 80 DEG C above freezing, the time is 10min to 24h.
16. the rare earth catalyst that the preparation method in claim 10-15 described in any one is prepared.
17. application of the catalyst described in claim 9 or 16 in conjugate diene polymerization.
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| 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 |
| 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 |
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