CN106905458A - Rare earth catalyst containing mixed ligand and its preparation method and application - Google Patents
Rare earth catalyst containing mixed ligand and its preparation method and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/06—Butadiene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/54—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof
- C08F4/545—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof rare earths being present, e.g. triethylaluminium + neodymium octanoate
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Abstract
The invention discloses a kind of rare earth catalyst containing mixed ligand, the catalyst is solid powdery, and the catalyst is made up of rear earth element nd with two kinds of parts, and the part is acid organo phosphates class compound and organic acid compound.The invention also discloses the preparation method and application of the rare earth catalyst containing mixed ligand.Rare earth catalyst of the invention can not only improve its dissolubility in organic solvent (aliphatic and aromatic hydrocarbons), and the optimization to the molecular parameter of resulting polymers is realized by the structure control of part, the characteristics of resulting polymers have cis superelevation, Narrow Molecular Weight Distribution index.
Description
Technical field
The present invention relates to a kind of mixed ligand rare earth catalyst solid powder and preparation method thereof, the catalyst can
It is applied to the polymerization of butadiene.
Background technology
Rare earth catalyst is used for polymerizing butadiene, can obtain the polybutadiene of high-cis structure.Rare earth catalyst
The polybutadiene rubber phase that the polybutadiene rubber of synthesis is prepared with traditional titanium system, cobalt system and nickel catalyst
Than with more preferable green strength and cured properties, therefore can be used to manufacture high-performance tire.And rare earth
The quality control of catalyst is one of key factor of synthesis high-quality rare-earth rubber.Come for rare earth catalyst
Say, the phase and phase stability of rare earth catalyst are to evaluate the important indicator of rare earth catalyst quality, not only
Influence catalyst activity, the molecular weight of gained polybutadiene and molecular weight distribution, and influence entirely to produce
The stability of journey and the stability of product quality.Catalyst fines is easy to transport and stores simultaneously.
《Rare earth catalyst synthetic rubber collected works》In " different coordinating group rare earth compounds are poly- in isoprene
Catalysis activity in conjunction " (Science Press, Changchun applied chemistry institute of the Chinese Academy of Sciences the 4th in 1980
Research department) in sketched the preparation method of phosphate neodymium catalyst, its product is solid phosphate ester neodymium catalyst.
The method that the method is used is simple, but the solid catalyst is insoluble in alkane, aromatic solvent, upper in application
With certain limitation.Carried respectively in United States Patent (USP) US6838534, US7157533, US7056998
A kind of preparation method of neodymium phosphate has been supplied, it is essentially identical with above-mentioned method, it is using neodymia and hydrochloric acid
Reaction prepares neodymium chloride solution, then using di-(2-ethylhexyl)phosphoric acid ester and acetone, two (2- ethyls
Hexyl) phosphate and acetone, di-(2-ethylhexyl)phosphoric acid ester and acetone reacts, and prepares phosphate
Neodymium solid catalyst, the catalyst equally exists the problem of the dissolubility difference in alkane, aromatic solvent.
As can be seen here, rare earth catalyst solidification is possible to replace traditional liquid catalyst in industrializing from now on
The status of agent.But the current preparation method on neodymium phosphate solid catalyst cannot all solve solid catalyst institute
The shortcoming of the dissolubility difference of presence.
The content of the invention
It is an object of the invention to provide a kind of rare earth catalyst containing mixed ligand and its preparation method and application.
To achieve the above object, the present invention provides a kind of rare earth catalyst containing mixed ligand, the catalyst
It is solid powdery, the catalyst is made up of rear earth element nd with two kinds of parts, described two parts are acid
Property organophosphorus ester compound and organic acid compound.
Wherein, the rear earth element nd and the mol ratio of described two parts are 1：3, the acidity is organic
Phosphate compounds are 1 with the mol ratio of the organic acid compound:5~5:1.
Wherein, the acid organo phosphates class compound is di-(2-ethylhexyl)phosphoric acid ester, 2- ethyls
One or more in hexyl phosphoric acid 2- ethylhexyls and methyl acid phosphate diformazan fat in heptan；The organic acid
Compound is the one kind or several in diethyl caproic acid, 2- ethyl -2,5- dimethylhexanoic acids, aphthenic acids and neodecanoic acid
Kind.
To achieve the above object, the present invention also provides a kind of preparation side of the rare earth catalyst containing mixed ligand
Method, comprises the following steps：
Step one：The saturated salt solution of rare earth element is prepared with the oxide and hydrochloric acid of rear earth element nd；
Step 2：Add acid organo phosphates class compound and have in saturated salt solution prepared by step one
Machine acid compounds, add alcohols or ketone, have product to separate out, and pH is adjusted with reagent；
Step 3：Product to separating out is filtered, dried.
Wherein, rear earth element nd and the acid organo phosphates class compound and the organic acid compound
Mol ratio be 1:3, the acid organo phosphates class compound and the organic acid compound mole
Than being 1:5~5:1.
Wherein, the acid organo phosphates class compound is di-(2-ethylhexyl)phosphoric acid ester, 2- ethyls
One or more in hexyl phosphoric acid 2- ethylhexyls and methyl acid phosphate diformazan fat in heptan；The organic acid
Compound is the one kind or several in diethyl caproic acid, 2- ethyl -2,5- dimethylhexanoic acids, aphthenic acids and neodecanoic acid
Kind.
Wherein, pH value is 5~7 in step 2.
Wherein, regulation pH agents useful for same is ammoniacal liquor or sodium hydroxide solution.
Wherein, the alcohols is methyl alcohol, ethanol or propyl alcohol；The ketone is acetone.
Wherein, drying using the drying that heated up under natural drying or vacuum in the step 3.
To achieve the above object, the present invention also provides a kind of polymerization of butadiene, and the polymerization should
With the rare earth catalyst containing mixed ligand.
Wherein, co-catalyst is alkyl aluminum compound and alkyl chloride aluminium compound, and reaction medium is hexane or first
Benzene, 0~120 DEG C of polymerization temperature, polymerization reaction time is 0.5~4.5h.
Wherein, the alkyl aluminum compound is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, diisobutyl
Hydrogen aluminium or diethylhydroaluminum；The alkyl chloride aluminium compound is aluminium diethyl monochloride, ethyl aluminum dichloride, sesquialter
Ethylmercury chloride aluminium, a chloro-di-isobutyl aluminum, dichloro aluminium isobutyl or sesquialter isobutyl group aluminium chloride, it is preferred that
The alkyl aluminum compound is diisobutyl hydrogen aluminium.
Wherein, the polymerization temperature is 30~80 DEG C.
The beneficial effects of the invention are as follows：
Catalyst of the present invention have polymerization activity high, simple production process, low production cost, be easy to fortune
Defeated the features such as, catalyst of the present invention not only has higher molten in organic solvent (aliphatic and aromatic hydrocarbons)
Xie Xing, and can be by the control realization to ligand structure to the molecular parameter of resulting polymers optimization,
The characteristics of resulting polymers have cis superelevation, Narrow Molecular Weight Distribution index.
Brief description of the drawings
Fig. 1 is the gained polybutadiene of embodiment 1313C-NMR spectrograms.
Specific embodiment
The present invention provides a kind of rare earth catalyst containing mixed ligand, and the catalyst is solid powdery, institute
State catalyst to be made up of with two kinds of parts rear earth element nd, described two parts are acid organo phosphates class
Compound and organic acid compound.
Wherein, the rear earth element nd and the mol ratio of described two parts are 1：3, the acidity is organic
Phosphate compounds are 1 with the mol ratio of the organic acid compound:5~5:1.
Wherein, the acid organo phosphates class compound is di-(2-ethylhexyl)phosphoric acid ester, 2- ethyls
One or more in hexyl phosphoric acid 2- ethylhexyls and methyl acid phosphate diformazan fat in heptan；The organic acid
Compound is the one kind or several in diethyl caproic acid, 2- ethyl -2,5- dimethylhexanoic acids, aphthenic acids and neodecanoic acid
Kind.
The present invention also provides a kind of preparation method of the rare earth catalyst containing mixed ligand, comprises the following steps：
Step one：The saturated salt solution of rare earth element is prepared with the oxide and hydrochloric acid of rear earth element nd；
Step 2：Add acid organo phosphates class compound and have in saturated salt solution prepared by step one
Machine acid compounds, add alcohols or ketone, have product to separate out, and pH is adjusted with reagent；
Step 3：Product to separating out is filtered, dried.
Wherein, rear earth element nd and the acid organo phosphates class compound and the organic acid compound
Mol ratio be 1:3, the acid organo phosphates class compound and the organic acid compound mole
Than being 1:5~5:1.
Wherein, the acid organo phosphates class compound is di-(2-ethylhexyl)phosphoric acid ester, 2- ethyls
One or more in hexyl phosphoric acid 2- ethylhexyls and methyl acid phosphate diformazan fat in heptan；The organic acid
Compound is the one kind or several in diethyl caproic acid, 2- ethyl -2,5- dimethylhexanoic acids, aphthenic acids and neodecanoic acid
Kind.
Wherein, pH value is 5~7 in step 2.
Wherein, regulation pH agents useful for same is ammoniacal liquor or sodium hydroxide solution.
Wherein, the alcohols is methyl alcohol, ethanol or propyl alcohol；The ketone is acetone.
Wherein, drying using the drying that heated up under natural drying or vacuum in the step 3.
The present invention also provides a kind of polymerization of butadiene, and the polymerization application is dilute containing mixed ligand
Native catalyst.
Wherein, co-catalyst is alkyl aluminum compound and alkyl chloride aluminium compound, and reaction medium is hexane or first
Benzene, 0~120 DEG C of polymerization temperature, polymerization reaction time is 0.5~4.5h.
Wherein, the alkyl aluminum compound is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, diisobutyl
Hydrogen aluminium or diethylhydroaluminum；The alkyl chloride aluminium compound is aluminium diethyl monochloride, ethyl aluminum dichloride, sesquialter
Ethylmercury chloride aluminium, a chloro-di-isobutyl aluminum, dichloro aluminium isobutyl or sesquialter isobutyl group aluminium chloride, it is preferred that
The alkyl aluminum compound is diisobutyl hydrogen aluminium.
Wherein, the polymerization temperature is 30~80 DEG C.
The preparation method of the rare earth catalyst containing mixed ligand provided by the present invention, using mixed ligand technology
Traditional single phosphate part is instead of, the method accurately controls two kinds of ratios of part, can obtain height
Activity, the rare earth catalyst solid powder of highly-solid selectively.Control is conducive to be polymerized in polymerizing butadiene
The quality of course of reaction and polymeric articles, polymerization process is steady and easily controllable, is adapted to continuous chemical industry life
Produce；This catalyst saves production cost to a certain extent, and can improve the fineness of product；It is relative in addition
In liquid catalyst, solid powder has greater advantage, this method solve solid at aspects such as transport, storages
The problem of rare earth catalyst system dissolubility difference in hexane, toluene, improves industrial operability.
Specific embodiment of the invention is described in detail below, it should be appreciated that described herein
Specific embodiment be merely to illustrate and explain the present invention, be not intended to limit the invention.
In the present invention, the microstructure of the polybutadiene of synthesis is using Bruker companies of Germany Vertex-70
FTIR types infrared spectrometer and Germany's Bruker companies AVANCE400 types NMR spectrometer with superconducting magnet are determined.
Molecular weight and molecualr weight distribution uses the TDA302 type gel permeation chromatographs of Viscotek companies of the U.S.
(GPC) determine, tetrahydrofuran is mobile phase, and Narrow distribution polystyrene is standard specimen, and flow velocity is 1.0ml/min,
Test temperature is 30 DEG C.
The invention provides a kind of preparation method of the rare earth catalyst containing mixed ligand, it is with rear earth element nd
Example, the method is comprised the following steps：
The aqueous solution of neodymium trichloride is obtained using neodymium oxide and hydrochloric acid solution reaction, heating makes three oxidations two
Neodymium all dissolve, and be evaporated to solution supersaturation untill；
Distilled water is added, phosphate and organic carboxyl acid are added by different ratio；
Adding ethanol has solid precipitate, and ammoniacal liquor stabilization pH value=6 are added dropwise；
Stirring, placement make the precipitated and separated of solution and generation, filtering of coming down in torrents, then are washed three times with ethanol；
Treat that ethanol volatilizees completely, rare earth catalyst is put into vacuum drying oven, 40 DEG C of dryings 4 hours obtain white powder
Last shape product.
In order to further illustrate technical scheme, with reference to embodiment to the present invention side of being preferable to carry out
Case is described, but it is to be understood that these descriptions are simply to further illustrate the features and advantages of the present invention,
Rather than limiting to the claimed invention.
Embodiment 1
By Nd2O33.361g is put into 500m1 beakers, adds 30m1 distilled water, adds 5.5m1
Concentrated hydrochloric acid and Nd2O3Reaction untill being evaporated to when crystallization will be separated out, adds 6.4481g to solution clarification
Di-(2-ethylhexyl)phosphoric acid ester (P204), 5.8285g diethyl caproic acid (EHA) and industrial alcohol
100m1, produces White Flocculus, dropwise addition ammoniacal liquor stabilization to pH=6 or so, and white is now produced in solution
Powdered precipitation, stirring, placement make solution and precipitated and separated, filtering of coming down in torrents, then are washed three times with ethanol, treat
Ethanol volatilizees completely, is dried 4 hours under 40 DEG C of vacuum, obtains white powder product for Nd (EHA)2P204。
Embodiment 2
By Nd2O33.361g is put into 500m1 beakers, adds 30m1 distilled water, then add 5.5m1
Concentrated hydrochloric acid, with Nd2O3Reaction adds 12.8968 to solution clarification, and untill being evaporated to when crystallization will be separated out
g P204, 2.8841g EHA and industrial alcohol 100m1, produce White Flocculus, be added dropwise ammoniacal liquor stabilization extremely
PH=6 or so, now produces white powder precipitation in solution, stirring, placement make solution and precipitated and separated,
Come down in torrents filtering, then washed three times with ethanol, treat that ethanol volatilizees completely, dried 4 hours under 40 DEG C of vacuum,
It is Nd (P to obtain white powder product204)2EHA。
Embodiment 3
By Nd2O33.361g is put into 500m1 beakers, adds 30m1 distilled water, then add 5.5m1
Concentrated hydrochloric acid, with Nd2O3Reaction adds 16.1241 to solution clarification, and untill being evaporated to when crystallization will be separated out
g P204, 1.4421g EHA and industrial alcohol 100m1, produce White Flocculus, be added dropwise ammoniacal liquor stabilization extremely
PH=6 or so, now produces white powder precipitation in solution, stirring, placement make solution and precipitated and separated,
Come down in torrents filtering, then washed three times with ethanol, treat that ethanol volatilizees completely, dried 4 hours under 40 DEG C of vacuum,
It is Nd (P to obtain white powder product204)2.5EHA0.5。
Embodiment 4
By Nd2O33.361g is put into 500m1 beakers, adds 30m1 distilled water, then add 5.5m1
Concentrated hydrochloric acid and Nd2O3Reaction adds 2- ethyls to solution clarification, and untill being evaporated to when crystallization will be separated out
Hexyl phosphoric acid 2- ethylhexyl 6.128g (P507), 5.8285g diethyl caproic acid (EHA), industrial second
Alcohol 100m1, produces White Flocculus, dropwise addition ammoniacal liquor stabilization to pH=6 or so, is now produced in solution
White powder is precipitated, and stirring, placement make solution and precipitated and separated, filtering of coming down in torrents, then are washed three times with ethanol,
Treat that ethanol volatilizees completely, dried 4 hours under 40 DEG C of vacuum, obtaining white powder product is
Nd(EHA)2P507。
Embodiment 5
By Nd2O33.361g is put into 500m1 beakers, adds 30m1 distilled water, then add 5.5m1
Concentrated hydrochloric acid and Nd2O3Reaction adds 2- ethyls to solution clarification, and untill being evaporated to when crystallization will be separated out
Hexyl phosphoric acid 2- ethylhexyl 3.064g (P507), 7.2103g diethyl caproic acid (EHA), industrial second
Alcohol 100m1, produces White Flocculus, dropwise addition ammoniacal liquor stabilization to pH=6 or so, is now produced in solution
White powder is precipitated, and stirring, placement make solution and precipitated and separated, filtering of coming down in torrents, then are washed three times with ethanol,
Treat that ethanol volatilizees completely, dried 4 hours under 40 DEG C of vacuum, obtain white powder product for Nd (EHA)2.5
(P507)0.5。
Embodiment 6
By Nd2O33.361g is put into 500m1 beakers, adds 30m1 distilled water, then add 5.5m1
Concentrated hydrochloric acid and Nd2O3Reaction adds 19.3443g to solution clarification, and untill being evaporated to when crystallization will be separated out
P204, industrial alcohol 100m1, generation White Flocculus, dropwise addition ammoniacal liquor stabilization to pH=6 or so, now
White powder precipitation is produced in solution, stirring, placement make solution and precipitated and separated, filtering of coming down in torrents, then use
Ethanol is washed three times, treats that ethanol volatilizees completely, is dried 4 hours under 40 DEG C of vacuum, obtains white powder product
Thing is Nd (P204)3。
Embodiment 7
By Nd2O33.361g is put into 500m1 beakers, adds 30m1 distilled water, then add 5.5m1
Concentrated hydrochloric acid and Nd2O3Reaction adds 2- ethyls to solution clarification, and untill being evaporated to when crystallization will be separated out
Hexyl phosphoric acid 2- ethylhexyl 6.128g (P507), 3.6856g 2- ethyl -2,5- dimethylhexanoic acids (Vers),
Industrial alcohol 100m1, produces White Flocculus, dropwise addition ammoniacal liquor stabilization to pH=6 or so, now solution
Middle generation white powder precipitation, stirring, placement make solution and precipitated and separated, filtering of coming down in torrents, then use ethanol
Wash three times, treat that ethanol volatilizees completely, dried 4 hours under 40 DEG C of vacuum, obtaining white powder product is
(P507)2Nd(Vers)。
Embodiment 8
By Nd2O33.361g is put into 500m1 beakers, adds 30m1 distilled water, then add 5.5m1
Concentrated hydrochloric acid and Nd2O3Reaction adds 2- ethyls to solution clarification, and untill being evaporated to when crystallization will be separated out
Hexyl phosphoric acid 2- ethylhexyl 3.064g (P507), 1.2615g aphthenic acids (Naph), industrial alcohol 100
M1, produces White Flocculus, dropwise addition ammoniacal liquor stabilization to pH=6 or so, and white powder is now produced in solution
Last shape precipitation, stirring, placement make solution and precipitated and separated, filtering of coming down in torrents, then are washed three times with ethanol, treat second
Alcohol volatilizees completely, is dried 4 hours under 40 DEG C of vacuum, obtains white powder product for (P507)2Nd(Naph)。
Embodiment 9
By Nd2O33.361g is put into 500m1 beakers, adds 30m1 distilled water, then add 5.5m1
Concentrated hydrochloric acid and Nd2O3Reaction to solution clarification, and untill being evaporated to when crystallization will be separated out, methylate di(2-ethylhexyl)phosphate
First fat in heptan 6.406g (P350), 1.2615g aphthenic acids (Naph), industrial alcohol 100m1 produces white wadding
Shape thing, dropwise addition ammoniacal liquor stabilization to pH=6 or so, now produce white powder precipitation in solution, stir,
Placement makes solution and precipitated and separated, filtering of coming down in torrents, then is washed three times with ethanol, treats that ethanol volatilizees completely,
Dried 4 hours under 40 DEG C of vacuum, obtain white powder product for (P350)2Nd(Naph)。
Embodiment 10
By Nd2O33.361g is put into 500m1 beakers, adds 30m1 distilled water, then add 5.5m1
Concentrated hydrochloric acid and Nd2O3Reaction to solution clarification, and untill being evaporated to when crystallization will be separated out, plus 2- ethyl hexyls
Base phosphoric acid 2- ethylhexyl 3.064g (P507), 7.3712g 2- ethyl -2,5- dimethylhexanoic acids (Vers), work
Industry ethanol 100m1, produces White Flocculus, dropwise addition ammoniacal liquor stabilization to pH=6 or so, now in solution
White powder precipitation is produced, stirring, placement make solution and precipitated and separated, filtering of coming down in torrents, then are washed with ethanol
Three times, treat that ethanol volatilizees completely, dried 4 hours under 40 DEG C of vacuum, obtaining white powder product is
(P507)Nd(Vers)2。
Embodiment 11
Activity rating is carried out to solid catalyst prepared by embodiment 1,
Catalyst activity evaluation method：Commented using batch solution polymerization technique synthesizing rare-earth butadiene rubber
Valency, specific method is：To adding the oil of 2000mL carbon six in polymeric kettle, then to adding 5.74mol in polymeric kettle
Butadiene, stirs, and temperature of charge in polymeric kettle is maintained at 30 DEG C, and the oil of carbon six, butadiene add
Entered range request to be protected using nitrogen；To addition 3.44 × 10 in catalyst addition tube-4mol
Nd(EHA)2P204、6.88×10-3mol AlH(i-Bu)2、0.4×10-3mol Al2Et3Cl3Will using nitrogen
Catalyst in catalyst addition tube is pressed into reactor；Discharges material after reacting 4 hours；Material in kettle
Boiled in boiling water 30 minutes, take out material and pressed dry in mill (mill temperature control is 120 DEG C)
Afterwards, rare earth polybutadiene rubber is obtained, dry glue 254g is obtained.
Embodiment 12
The same solid catalyst prepared using embodiment 1
Catalyst activity evaluation method：Commented using batch solution polymerization technique synthesizing rare-earth butadiene rubber
Valency, specific method is：To adding the oil of 2000mL carbon six in polymeric kettle, then to adding 5.74mol in polymeric kettle
Butadiene, is stirred, and temperature of charge in polymeric kettle is maintained at 0 DEG C, and the oil of carbon six, butadiene are added
Range request is crossed to be protected using nitrogen；To addition 3.44 × 10 in catalyst addition tube-4mol Nd(EHA)2P204、
6.88×10-3mol AlH(i-Bu)2、1.20×10-3mol AlEt2Cl；Using nitrogen by catalyst addition tube
In catalyst be pressed into reactor；Discharges material after reacting 4 hours；Material is boiled in boiling water in kettle
30 minutes, after taking-up material is pressed dry in mill (mill temperature control is 120 DEG C), obtain rare earth
Butadiene rubber, obtains dry glue 35g.
Embodiment 13
The same solid catalyst prepared using embodiment 1
Catalyst activity evaluation method：Commented using batch solution polymerization technique synthesizing rare-earth butadiene rubber
Valency, specific method is：To adding the oil of 2000mL carbon six in polymeric kettle, then to adding 5.74mol in polymeric kettle
Butadiene, stirs, and temperature of charge in polymeric kettle is maintained at 50 DEG C, and the oil of carbon six, butadiene add
Entered range request to be protected using nitrogen；To addition 3.44 × 10 in catalyst addition tube-4mol
Nd(EHA)2P204、6.88×10-3mol AlH(i-Bu)2、1.20×10-3mol AlEt2Cl；Will using nitrogen
Catalyst in catalyst addition tube is pressed into reactor；Discharges material after reacting 4 hours；Material in kettle
Boiled in boiling water 30 minutes, take out material and pressed dry in mill (mill temperature control is 120 DEG C)
Afterwards, rare earth polybutadiene rubber is obtained, is weighed.Obtain dry glue 304g.
Embodiment 14
The same solid catalyst prepared using embodiment 2
Catalyst activity evaluation method：Commented using batch solution polymerization technique synthesizing rare-earth butadiene rubber
Valency, specific method is：To adding the oil of 2000mL carbon six in polymeric kettle, then to adding 5.74mol in polymeric kettle
Butadiene, stirs, and temperature of charge in polymeric kettle is maintained at 50 DEG C, and the oil of carbon six, butadiene add
Entered range request to be protected using nitrogen；To addition 3.44 × 10 in catalyst addition tube-4mol
Nd(P204)2EHA、6.88×10-3mol AlH(i-Bu)2、1.20×10-3mol AlEt2Cl；Will using nitrogen
Catalyst in catalyst addition tube is pressed into reactor；Discharges material after reacting 4 hours；Material in kettle
Boiled in boiling water 30 minutes, take out material and pressed dry in mill (mill temperature control is 120 DEG C)
Afterwards, rare earth polybutadiene rubber is obtained, is weighed.Obtain dry glue 300g.
Embodiment 15
The same solid catalyst prepared using embodiment 4
Catalyst activity evaluation method：Commented using batch solution polymerization technique synthesizing rare-earth butadiene rubber
Valency, specific method is：To adding the oil of 2000mL carbon six in polymeric kettle, then to adding 5.74mol in polymeric kettle
Butadiene, stirs, and temperature of charge in polymeric kettle is maintained at 50 DEG C, and the oil of carbon six, butadiene add
Entered range request to be protected using nitrogen；To addition 3.44 × 10 in catalyst addition tube-4mol
Nd(EHA)2P507、6.88×10-3mol Al(i-Bu)3、1.20×10-3mol Al(i-Bu)2Cl；Use nitrogen
Be pressed into catalyst in catalyst addition tube in reactor by gas；Discharges material after reacting 4 hours；In kettle
Material is boiled 30 minutes in boiling water, and taking-up material is in mill (mill temperature control is 120 DEG C)
After pressing dry, rare earth polybutadiene rubber is obtained, weighed.Obtain dry glue 295g.
Embodiment 16
The same solid catalyst prepared using embodiment 3
Catalyst activity evaluation method：Commented using batch solution polymerization technique synthesizing rare-earth butadiene rubber
Valency, specific method is：To adding the oil of 2000mL carbon six in polymeric kettle, then to adding 5.74mol in polymeric kettle
Butadiene, stirs, and temperature of charge in polymeric kettle is maintained at 80 DEG C, and the oil of carbon six, butadiene add
Entered range request to be protected using nitrogen；To addition 3.44 × 10 in catalyst addition tube-4mol Nd(P507)2.5
EHA0.5、6.88×10-3mol AlH(i-Bu)2、0.4×10-3mol Al2(i-Bu)3Cl3；Will using nitrogen
Catalyst in catalyst addition tube is pressed into reactor；Discharges material after reacting 4 hours；Material in kettle
Boiled in boiling water 30 minutes, take out material and pressed dry in mill (mill temperature control is 120 DEG C)
Afterwards, rare earth polybutadiene rubber is obtained, is weighed.Obtain dry glue 290g.
Embodiment 17-22
Respectively using the catalyst prepared by embodiment 5-10, with embodiment 13, it lives other polymerizing conditions
Property and cis-content result see the table below.
Certainly, the present invention can also have other various embodiments, without departing substantially from spirit of the invention and its essence
In the case of, those of ordinary skill in the art can make various corresponding changes and change according to the present invention
Shape, but these corresponding changes and deformation should all belong to the protection domain of the claims in the present invention.
Claims (14)
1. a kind of rare earth catalyst containing mixed ligand, it is characterised in that the catalyst is solid powder
Shape, the catalyst is made up of rear earth element nd with two kinds of parts, and described two parts are acidic organo phosphorus acid
Ester type compound and organic acid compound.
2. the rare earth catalyst containing mixed ligand according to claim 1, it is characterised in that described
Rear earth element nd is 1 with the mol ratio of described two parts：3, the acid organo phosphates class compound
It is 1 with the mol ratio of the organic acid compound:5~5:1.
3. the rare earth catalyst containing mixed ligand according to claim 1, it is characterised in that described
Acid organo phosphates class compound is di-(2-ethylhexyl)phosphoric acid ester, 2- ethylhexyl phosphoric acid 2- ethyls
One or more in hexyl ester and methyl acid phosphate diformazan fat in heptan；The organic acid compound be diethyl oneself
One or more in acid, 2- ethyl -2,5- dimethylhexanoic acids, aphthenic acids and neodecanoic acid.
4. the preparation method of the rare earth catalyst containing mixed ligand described in claim 1, it is characterised in that
Comprise the following steps：
Step one：The saturated salt solution of rare earth element is prepared with the oxide and hydrochloric acid of rear earth element nd；
Step 2：Add acid organo phosphates class compound and have in saturated salt solution prepared by step one
Machine acid compounds, add alcohols or ketone, have product to separate out, and pH is adjusted with reagent；
Step 3：Product to separating out is filtered, dried.
5. the preparation method of the rare earth catalyst containing mixed ligand according to claim 4, its feature
It is that rear earth element nd and the acid organo phosphates class compound and the organic acid compound rub
You are than being 1:3, the acid organo phosphates class compound is with the mol ratio of the organic acid compound
1:5~5:1.
6. the preparation method of the rare earth catalyst containing mixed ligand according to claim 4, its feature
It is that the acid organo phosphates class compound is di-(2-ethylhexyl)phosphoric acid ester, 2- ethylhexyls
One or more in phosphoric acid 2- ethylhexyls and methyl acid phosphate diformazan fat in heptan；The organic acid chemical combination
Thing is one or more in diethyl caproic acid, 2- ethyl -2,5- dimethylhexanoic acids, aphthenic acids and neodecanoic acid.
7. the preparation method of the rare earth catalyst containing mixed ligand according to claim 4, its feature
It is that pH value is 5~7 in step 2.
8. the preparation method of the rare earth catalyst containing mixed ligand according to claim 4, its feature
It is that regulation pH agents useful for same is ammoniacal liquor or sodium hydroxide solution.
9. the preparation method of the rare earth catalyst containing mixed ligand according to claim 4, its feature
It is that the alcohols is methyl alcohol, ethanol or propyl alcohol；The ketone is acetone.
10. the preparation method of the rare earth catalyst containing mixed ligand according to claim 4, its feature
It is, drying using the drying that heated up under natural drying or vacuum in the step 3.
A kind of 11. polymerizations of butadiene, it is characterised in that the polymerization application claim
The rare earth catalyst containing mixed ligand described in 1~3 any one.
The polymerization of 12. butadiene according to claim 11, it is characterised in that co-catalyst
It is alkyl aluminum compound and alkyl chloride aluminium compound, reaction medium is hexane or toluene, polymerization temperature 0~120
DEG C, polymerization reaction time is 0.5~4.5h.
The polymerization of 13. butadiene according to claim 12, it is characterised in that the alkyl
Aluminium compound is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, diisobutyl hydrogen aluminium or diethylhydroaluminum；
The alkyl chloride aluminium compound is aluminium diethyl monochloride, ethyl aluminum dichloride, sesquialter aluminium ethide, the isobutyl of a chlorine two
Base aluminium, dichloro aluminium isobutyl or sesquialter aluminium isobutyl.
The polymerization of 14. butadiene according to claim 12, it is characterised in that the polymerization
Temperature is 30~80 DEG C.
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