CN106916240B - A method of preparing rare-earth isoprene rubber catalyst - Google Patents
A method of preparing rare-earth isoprene rubber catalyst Download PDFInfo
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- CN106916240B CN106916240B CN201510993721.1A CN201510993721A CN106916240B CN 106916240 B CN106916240 B CN 106916240B CN 201510993721 A CN201510993721 A CN 201510993721A CN 106916240 B CN106916240 B CN 106916240B
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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
- C08F136/08—Isoprene
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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
- 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
- C08F4/52—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 selected from boron, aluminium, gallium, indium, thallium or rare earths
Abstract
The invention discloses a kind of methods for preparing rare-earth isoprene rubber catalyst, comprising the following steps: (1) prepares triisobutylaluminum toluene solution；(2) triisobutylaluminum toluene solution and pentadiene mixture are prepared；(3) it prepares a water neodymium chloride isopropanol complex: progress complexation reaction in toluene is added in a water neodymium chloride and isopropanol and obtains a water neodymium chloride isopropanol complex；(4) it prepares catalyst: a water neodymium chloride isopropanol complex being added in triisobutylaluminum toluene solution and pentadiene mixture, is reacted to obtain catalyst, reaction temperature is -5 DEG C hereinafter, the time is 5~10min, and should be carried out under stiring；(5) catalyst aging: catalyst aging 16h or more prepared by step (4), the Aging Temperature are 20~40 DEG C.Preparation rare-earth rubber catalyst technical matters provided by the present invention is simple and easy, raw material is easy to get, side reaction is few, catalyst activity is high.
Description
Technical field
The present invention relates to a kind of catalysis, specifically a kind of to be applied to isoprene solution polymerization rare earth isoamyl rubber
The preparation method of the rare earth catalyst of glue.
Background technique
The development for developing all its corresponding catalyst always of rubber industry is inseparable, Ziegler-Natta catalysis
The appearance of agent is that synthesis butadiene rubber and isoprene rubber bring revolutionary breakthrough, is laid a good foundation for modern rubber industry.
The further development of rubber industry is greatly facilitated in the appearance of the catalyst such as lithium system, iron series, titanium system, cobalt system, nickel system.Eighties of last century
China begins one's study Rare Earth rubber catalyst from the sixties, and achieves important breakthrough.Compared with traditional rubber catalyst,
Rare earth catalyst has the following characteristics that in rubber polymerization reaction using saturated hydrocarbons as solvent, is conducive to environmental protection；Monomer conversion is high；No
Reaction is easily crosslinked, gel is generated；Dimer generating rate is low, it is possible to reduce dimer pollution on the environment；Temperature
The structure of polymerizate and performance are influenced little.
With the active highest of Nd-based catalyst in rare earth series catalysts, mostly uses the ternary of organic acid neodymium to be aged greatly now and urge
Change system.Changchun Institute of Applied Chemistry had studied the neodymium series such as P204, P507, P229 catalyst system in 1975 and is catalyzed to isoprene polymerization
Active research (Science Press's " rare earth catalyst synthetic rubber collected works " in 1980).
Ziegler-Natta type rare earth catalyst can be divided into binary rare-earth catalyst system, three-element catalytic body according to component
System and multicomponent catalyst system.Binary catalyst system is made of neodymium trichloride nL complex (Nd) and alkyl aluminum (Al),
Wherein Al/Nd molar ratio it is usual > 20, referring to Chinese science, B volumes, 2009,39 (10): 1006~1027.Binary system component
It reduces, influence factor is few, and preparing process and method are simple.But this kind of catalyst is heterogeneous system mostly, in catalysis conjugation two
Stability is poor when olefinic polymerization, and catalytic process and polymerization process are more difficult to control, and polymer molecular weight is larger, molecular weight distribution compared with
Width, polymerization system viscosity is big, brings difficulty to production processes such as heat transfer, conveying, glue spraying, cohesions and increases energy consumption.In order to solve
The deficiency of above-mentioned heterogeneous catalysis proposes improved by two (trifluoroacetic acid) neodymium chloride nL complexs or alkoxy chlorination
The binary catalyst system of neodymium and alkyl aluminum composition, such as (CF3COO)2NdCl·(C2H5)2O or (CF3COO)2NdCl·C2H5OH
Binary rare-earth catalyst with triethyl aluminum composition is in homogeneous system in toluene, but catalysis directionality is relatively poor, referring to: it is high
Molecule communication, 1979,6:367-369；1984,5:358~362.By alkoxy neodymium chloride Nd (OR)3-nClnWith triethyl aluminum group
At binary catalyst system, wherein R is that butyl or amyl and its isomers, the cis-content of prepared polybutadiene are opposite
It is relatively low, referring to: chemical journal, 1983,41:490~497.
In using research of the neodymium chloride as catalyst in the past, neodymium chloride uses anhydrous neodymium chloride, anhydrous neodymium chloride at
This height, preparation difficulty are big.
Summary of the invention
The main purpose of the present invention is to provide a kind of methods for preparing rare-earth isoprene rubber catalyst, to overcome existing skill
The preparation process of rare-earth isoprene rubber catalyst is complicated in art, defect at high cost.
The object of the present invention is achieved like this, a method of rare-earth isoprene rubber catalyst being prepared, this method includes
Following steps:
(1) it prepares triisobutylaluminum toluene solution: triisobutyl aluminium and toluene is hybridly prepared into triisobutyl aluminium toluene
Solution；
(2) triisobutylaluminum toluene solution and pentadiene mixture are prepared: the triisobutyl aluminium first that step (1) is prepared
Benzole soln and pentadiene are mixed to get triisobutylaluminum toluene solution and pentadiene mixture；
(3) it prepares a water neodymium chloride isopropanol complex: a water neodymium chloride and isopropanol being added in toluene and are coordinated
Reaction obtains a water neodymium chloride isopropanol complex, and the temperature of complexation reaction is 20~40 DEG C, and the time is 6~16h, and should stirred
Mix lower progress；
(4) it prepares catalyst: a water neodymium chloride isopropanol complex prepared by step (3) being added to step (2) and is prepared
Triisobutylaluminum toluene solution and pentadiene mixture in, reacted to obtain catalyst, reaction temperature be -5 DEG C hereinafter,
Time is 5~10min, and should be carried out under stiring；And
(5) catalyst aging: catalyst aging 16h or more prepared by step (4), Aging Temperature are 20~40 DEG C, and
It should carry out under stiring, rare-earth isoprene rubber catalyst can be obtained.
The method of the present invention for preparing rare-earth isoprene rubber catalyst, wherein in step (1), the triisobutyl
The mass content of triisobutyl aluminium is preferably 13~18% in aluminium toluene solution.
The method of the present invention for preparing rare-earth isoprene rubber catalyst, wherein in step (2), the triisobutyl
In aluminium toluene solution and pentadiene mixture, the molar ratio of triisobutyl aluminium and pentadiene is preferably 9~18:2~4.
The method of the present invention for preparing rare-earth isoprene rubber catalyst, wherein in step (3), the water chlorination
In neodymium isopropanol complex, the molar ratio of a water neodymium chloride and isopropanol is preferably 1:2~4.
The method of the present invention for preparing rare-earth isoprene rubber catalyst, wherein in step (4), the water chlorination
Neodymium isopropanol complex is in terms of a water neodymium chloride, and the triisobutylaluminum toluene solution and pentadiene mixture are with triisobutyl
Aluminium meter, a water neodymium chloride isopropanol complex and triisobutylaluminum toluene solution and the molar ratio of pentadiene mixture are preferably
1:9~18.
The method of the present invention for preparing rare-earth isoprene rubber catalyst, wherein complexation reaction in the step (3)
Temperature is preferably 25~38 DEG C, and the time is preferably 8~14h.
The method of the present invention for preparing rare-earth isoprene rubber catalyst, wherein reaction temperature is excellent in the step (4)
- 5 DEG C~-18 DEG C are selected as, the time is preferably 6~10min.
The method of the present invention for preparing rare-earth isoprene rubber catalyst, wherein digestion time is excellent in the step (5)
It is selected as 16h~98h, Aging Temperature is preferably 24~38 DEG C.
Beneficial effects of the present invention:
Preparation rare-earth rubber catalyst technical matters provided by the present invention is simple and easy, raw material is easy to get, side reaction is few, urges
Agent activity is high.In addition, carrying out reacting in toluene solution with isopropanol in one Neodymium chloride hydrate of preparation process reducing reaction
The viscosity of solution improves industrial production operability afterwards, indirectly reduces production cost.
Specific embodiment
Elaborate below to the embodiment of the present invention: the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
Embodiment 1
The preparation of rare-earth isoprene rubber catalyst: catalyst preparation is in the screw socket polymerization bottle and 50ml two-mouth bottle of 100ml
It carries out, reaction flask and two-mouth bottle are evacuated, high-temperature baking, and inflated with nitrogen displacement repeatedly for three times, is finally filled with nitrogen.In nitrogen
Under protection, the toluene of 18ml, the mono- water chlorine of isopropanol and 2g of 1.57ml are added into the two-mouth bottle of the 50ml equipped with magnetic agitation
Change neodymium, 6h is stirred at room temperature, forms a water neodymium chloride isopropanol complex.The pentadiene of 0.44ml is added to 21ml matter
It measures in the triisobutylaluminum toluene solution that content is 16.5%, is cooled to -15 DEG C, mono- water neodymium chloride isopropanol of 4ml is then added
Complex, after mixing, reaction temperature are mentioned to 25 DEG C, are aged 16 hours under magnetic stirring, are obtained rare-earth isoprene rubber and urge
9ml isoprene, 34ml n-hexane and above-mentioned catalyst 0.3ml are added into 100ml screw socket polymerization bottle for agent.Gather at 50 DEG C
Half an hour is closed, the ethanol solution that 2, the 6- toluene di-tert-butyl phenol containing 1% mass is added terminates reaction, does after being washed with water
It is dry, it is placed in 60 DEG C of vacuum ovens and dries to constant weight, polyisoprene yield is 73%.
Embodiment 2
The preparation of rare-earth isoprene rubber catalyst: catalyst preparation is in the screw socket polymerization bottle and 50ml two-mouth bottle of 100ml
It carries out, reaction flask and two-mouth bottle are evacuated, high-temperature baking, and inflated with nitrogen displacement repeatedly for three times, is finally filled with nitrogen.In nitrogen
Under protection, the toluene of 18ml, the isopropanol of 1.57ml and 2g mono- are added into the two-mouth bottle of the 50ml equipped with magnetic agitation and is hydrated
6h is stirred at room temperature in neodymium chloride, forms a water neodymium chloride isopropanol complex.The pentadiene of 0.44ml is added to 14ml
In the triisobutylaluminum toluene solution that mass content is 16.5%, -15 DEG C are cooled to, mono- water neodymium chloride isopropyl of 4ml is then added
Alcohol complex, after mixing, reaction temperature are mentioned to 25 DEG C, are aged 30 hours under magnetic stirring, are obtained rare-earth isoprene rubber
9ml isoprene, 34ml n-hexane and above-mentioned catalyst 0.2ml are added into 100ml screw socket polymerization bottle for catalyst.At 50 DEG C
It polymerize half an hour, the ethanol solution that 2, the 6- toluene di-tert-butyl phenol containing 1% mass is added terminates reaction, after being washed with water
It is dry, it is placed in 60 DEG C of vacuum ovens and dries to constant weight, polyisoprene yield is 62%.
Embodiment 3
The preparation of rare-earth isoprene rubber catalyst: catalyst preparation is in the screw socket polymerization bottle and 50ml two-mouth bottle of 100ml
It carries out, reaction flask and two-mouth bottle are evacuated, high-temperature baking, and inflated with nitrogen displacement repeatedly for three times, is finally filled with nitrogen.In nitrogen
Under protection, the toluene of 18ml, the isopropanol of 1.57ml and 2g mono- are added into the two-mouth bottle of the 50ml equipped with magnetic agitation and is hydrated
6h is stirred at room temperature in neodymium chloride, forms a water neodymium chloride isopropanol complex.The pentadiene of 0.44ml is added to 25ml
In the triisobutylaluminum toluene solution that mass content is 16.5%, -15 DEG C are cooled to, mono- water neodymium chloride isopropyl of 4ml is then added
Alcohol complex, after mixing, reaction temperature are mentioned to 25 DEG C, are aged 20 hours under magnetic stirring, are obtained rare-earth isoprene rubber
9ml isoprene, 34ml n-hexane and above-mentioned catalyst 0.35ml are added into 100ml screw socket polymerization bottle for catalyst.At 50 DEG C
It polymerize half an hour, the ethanol solution that 2, the 6- toluene di-tert-butyl phenol containing 1% mass is added terminates reaction, after being washed with water
It is dry, it is placed in 60 DEG C of vacuum ovens and dries to constant weight, polyisoprene yield is 78%.
Embodiment 4
The preparation of rare-earth isoprene rubber catalyst: catalyst preparation is in the screw socket polymerization bottle and 50ml two-mouth bottle of 100ml
It carries out, reaction flask and two-mouth bottle are evacuated, high-temperature baking, and inflated with nitrogen displacement repeatedly for three times, is finally filled with nitrogen.In nitrogen
Under protection, the toluene of 18ml, the isopropanol of 1.57ml and 2g mono- are added into the two-mouth bottle of the 50ml equipped with magnetic agitation and is hydrated
6h is stirred at room temperature in neodymium chloride, forms a water neodymium chloride isopropanol complex.The pentadiene of 0.21ml is added to 21ml
In the triisobutylaluminum toluene solution that mass content is 16.5%, -15 DEG C are cooled to, mono- water neodymium chloride isopropyl of 4ml is then added
Alcohol complex, after mixing, reaction temperature are mentioned to 25 DEG C, are aged 20 hours under magnetic stirring, are obtained rare-earth isoprene rubber
9ml isoprene, 34ml n-hexane and above-mentioned catalyst 0.3ml are added into 100ml screw socket polymerization bottle for catalyst.At 50 DEG C
It polymerize half an hour, the ethanol solution that 2, the 6- toluene di-tert-butyl phenol containing 1% mass is added terminates reaction, after being washed with water
It is dry, it is placed in 60 DEG C of vacuum ovens and dries to constant weight, polyisoprene yield is 70%.
Embodiment 5
The preparation of rare-earth isoprene rubber catalyst: catalyst preparation is in the screw socket polymerization bottle and 50ml two-mouth bottle of 100ml
It carries out, reaction flask and two-mouth bottle are evacuated, high-temperature baking, and inflated with nitrogen displacement repeatedly for three times, is finally filled with nitrogen.In nitrogen
Under protection, the toluene of 18ml, the isopropanol of 1.2ml and 2g mono- are added into the two-mouth bottle of the 50ml equipped with magnetic agitation and is hydrated chlorine
Change neodymium, 16h is stirred at room temperature, forms a water neodymium chloride isopropanol complex.The pentadiene of 0.4ml is added to 21ml matter
It measures in the triisobutylaluminum toluene solution that content is 16.5%, is cooled to -15 DEG C, mono- water neodymium chloride isopropanol of 4ml is then added
Complex, after mixing, reaction temperature are mentioned to 25 DEG C, are aged 20 hours under magnetic stirring, are obtained rare-earth isoprene rubber and urge
9ml isoprene, 34ml n-hexane and above-mentioned catalyst 0.3ml are added into 100ml screw socket polymerization bottle for agent.Gather at 50 DEG C
Half an hour is closed, the ethanol solution that 2, the 6- toluene di-tert-butyl phenol containing 1% mass is added terminates reaction, does after being washed with water
It is dry, it is placed in 60 DEG C of vacuum ovens and dries to constant weight, polyisoprene yield is 72%.
Embodiment 6
The preparation of rare-earth isoprene rubber catalyst: catalyst preparation is in the screw socket polymerization bottle and 50ml two-mouth bottle of 100ml
It carries out, reaction flask and two-mouth bottle are evacuated, high-temperature baking, and inflated with nitrogen displacement repeatedly for three times, is finally filled with nitrogen.In nitrogen
Under protection, the toluene of 18ml, the isopropanol of 2.4ml and 2g mono- are added into the two-mouth bottle of the 50ml equipped with magnetic agitation and is hydrated chlorine
Change neodymium, 6h is stirred at room temperature, forms a water neodymium chloride isopropanol complex.The pentadiene of 0.4ml is added to 21ml matter
It measures in the triisobutylaluminum toluene solution that content is 16.5%, is cooled to -15 DEG C, mono- water neodymium chloride isopropanol of 4ml is then added
Complex, after mixing, reaction temperature are mentioned to 25 DEG C, are aged 20 hours under magnetic stirring, are obtained rare-earth isoprene rubber and urge
9ml isoprene, 34ml n-hexane and above-mentioned catalyst 0.3ml are added into 100ml screw socket polymerization bottle for agent.Gather at 50 DEG C
Half an hour is closed, the ethanol solution that 2, the 6- toluene di-tert-butyl phenol containing 1% mass is added terminates reaction, does after being washed with water
It is dry, it is placed in 60 DEG C of vacuum ovens and dries to constant weight, polyisoprene yield is 80%.
Embodiment 7
The preparation of rare-earth isoprene rubber catalyst: catalyst preparation is in the screw socket polymerization bottle and 50ml two-mouth bottle of 100ml
It carries out, reaction flask and two-mouth bottle are evacuated, high-temperature baking, and inflated with nitrogen displacement repeatedly for three times, is finally filled with nitrogen.In nitrogen
Under protection, the toluene of 18ml, the isopropanol of 2.0ml and 2g mono- are added into the two-mouth bottle of the 50ml equipped with magnetic agitation and is hydrated chlorine
Change neodymium, 6h is stirred at room temperature, forms a water neodymium chloride isopropanol complex.The pentadiene of 0.4ml is added to 33ml matter
It measures in the triisobutylaluminum toluene solution that content is 13.2%, is cooled to -15 DEG C, mono- water neodymium chloride isopropanol of 4ml is then added
Complex, after mixing, reaction temperature are mentioned to 25 DEG C, are aged 30 hours under magnetic stirring, are obtained rare-earth isoprene rubber and urge
9ml isoprene, 34ml n-hexane and above-mentioned catalyst 0.45ml are added into 100ml screw socket polymerization bottle for agent.Gather at 50 DEG C
Half an hour is closed, the ethanol solution that 2, the 6- toluene di-tert-butyl phenol containing 1% mass is added terminates reaction, does after being washed with water
It is dry, it is placed in 60 DEG C of vacuum ovens and dries to constant weight, polyisoprene yield is 75%.
Embodiment 8
The preparation of rare-earth isoprene rubber catalyst: catalyst preparation is in the screw socket polymerization bottle and 50ml two-mouth bottle of 100ml
It carries out, reaction flask and two-mouth bottle are evacuated, high-temperature baking, and inflated with nitrogen displacement repeatedly for three times, is finally filled with nitrogen.In nitrogen
Under protection, the toluene of 18ml, the isopropanol of 2.0ml and 2g mono- are added into the two-mouth bottle of the 50ml equipped with magnetic agitation and is hydrated chlorine
Change neodymium, 6h is stirred at room temperature, forms a water neodymium chloride isopropanol complex.The pentadiene of 0.4ml is added to 17ml matter
It measures in the triisobutylaluminum toluene solution that content is 17.8%, is cooled to -15 DEG C, mono- water neodymium chloride isopropanol of 4ml is then added
Complex, after mixing, reaction temperature are mentioned to 25 DEG C, are aged 30 hours under magnetic stirring, are obtained rare-earth isoprene rubber and urge
9ml isoprene, 34ml n-hexane and above-mentioned catalyst 0.3ml are added into 100ml screw socket polymerization bottle for agent.Gather at 50 DEG C
Half an hour is closed, the ethanol solution that 2, the 6- toluene di-tert-butyl phenol containing 1% mass is added terminates reaction, does after being washed with water
It is dry, it is placed in 60 DEG C of vacuum ovens and dries to constant weight, polyisoprene yield is 83%.
Embodiment 9
The preparation of rare-earth isoprene rubber catalyst: catalyst preparation is in the screw socket polymerization bottle and 50ml two-mouth bottle of 100ml
It carries out, reaction flask and two-mouth bottle are evacuated, high-temperature baking, and inflated with nitrogen displacement repeatedly for three times, is finally filled with nitrogen.In nitrogen
Under protection, the toluene of 18ml, the isopropanol of 2.0ml and 2g mono- are added into the two-mouth bottle of the 50ml equipped with magnetic agitation and is hydrated chlorine
Change neodymium, 6h is stirred at room temperature, forms a water neodymium chloride isopropanol complex.The pentadiene of 0.4ml is added to 17ml matter
It measures in the triisobutylaluminum toluene solution that content is 17.8%, is cooled to -18 DEG C, mono- water neodymium chloride isopropanol of 4ml is then added
Complex, after mixing, reaction temperature are mentioned to 25 DEG C, are aged 98 hours under magnetic stirring, are obtained rare-earth isoprene rubber and urge
9ml isoprene, 34ml n-hexane and above-mentioned catalyst 0.3ml are added into 100ml screw socket polymerization bottle for agent.Gather at 50 DEG C
Half an hour is closed, the ethanol solution that 2, the 6- toluene di-tert-butyl phenol containing 1% mass is added terminates reaction, does after being washed with water
It is dry, it is placed in 60 DEG C of vacuum ovens and dries to constant weight, polyisoprene yield is 85%.
Embodiment 10
The preparation of rare-earth isoprene rubber catalyst: catalyst preparation is in the screw socket polymerization bottle and 50ml two-mouth bottle of 100ml
It carries out, reaction flask and two-mouth bottle are evacuated, high-temperature baking, and inflated with nitrogen displacement repeatedly for three times, is finally filled with nitrogen.In nitrogen
Under protection, the toluene of 18ml, the isopropanol of 2.0ml and 2g mono- are added into the two-mouth bottle of the 50ml equipped with magnetic agitation and is hydrated chlorine
Change neodymium, 16h is stirred at room temperature, forms a water neodymium chloride isopropanol complex.The pentadiene of 0.4ml is added to 17ml matter
It measures in the triisobutylaluminum toluene solution that content is 17.8%, is cooled to -5 DEG C, mono- water neodymium chloride isopropanol of 4ml is then added and matches
Object is closed, after mixing, reaction temperature is mentioned to 25 DEG C, is aged 20 hours under magnetic stirring, and rare-earth isoprene rubber catalysis is obtained
9ml isoprene, 34ml n-hexane and above-mentioned catalyst 0.3ml are added into 100ml screw socket polymerization bottle for agent.It polymerize at 50 DEG C
Half an hour, the ethanol solution that 2, the 6- toluene di-tert-butyl phenol containing 1% mass is added terminate reaction, do after being washed with water
It is dry, it is placed in 60 DEG C of vacuum ovens and dries to constant weight, polyisoprene yield is 75%.
Embodiment 11
The preparation of rare-earth isoprene rubber catalyst: catalyst preparation is in the screw socket polymerization bottle and 50ml two-mouth bottle of 100ml
It carries out, reaction flask and two-mouth bottle are evacuated, high-temperature baking, and inflated with nitrogen displacement repeatedly for three times, is finally filled with nitrogen.In nitrogen
Under protection, the toluene of 18ml, the isopropanol of 2.0ml and 2g mono- are added into the two-mouth bottle of the 50ml equipped with magnetic agitation and is hydrated chlorine
Change neodymium, 12h is stirred at room temperature, forms a water neodymium chloride isopropanol complex.The pentadiene of 0.4ml is added to 17ml matter
It measures in the triisobutylaluminum toluene solution that content is 17.8%, is cooled to -15 DEG C, mono- water neodymium chloride isopropanol of 4ml is then added
Complex, after mixing, reaction temperature are mentioned to 25 DEG C, are aged 16 hours under magnetic stirring, are obtained rare-earth isoprene rubber and urge
9ml isoprene, 34ml n-hexane and above-mentioned catalyst 0.3ml are added into 100ml screw socket polymerization bottle for agent.Gather at 50 DEG C
Half an hour is closed, the ethanol solution that 2, the 6- toluene di-tert-butyl phenol containing 1% mass is added terminates reaction, does after being washed with water
It is dry, it is placed in 60 DEG C of vacuum ovens and dries to constant weight, polyisoprene yield is 70%.
Beneficial effects of the present invention:
Preparation rare-earth rubber catalyst technical matters provided by the present invention is simple and easy, raw material is easy to get, side reaction is few, urges
Agent activity is high.In addition, carrying out reacting in toluene solution with isopropanol in one Neodymium chloride hydrate of preparation process reducing reaction
The viscosity of solution improves industrial production operability afterwards, indirectly reduces production cost.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to the protection scope of the claims in the present invention.
Claims (7)
1. a kind of method for preparing rare-earth isoprene rubber catalyst, which is characterized in that method includes the following steps:
(1) it prepares triisobutylaluminum toluene solution: triisobutyl aluminium and toluene is hybridly prepared into triisobutylaluminum toluene solution；
(2) prepare triisobutylaluminum toluene solution and pentadiene mixture: the triisobutyl aluminium toluene that step (1) is prepared is molten
Liquid and pentadiene are mixed to get triisobutylaluminum toluene solution and pentadiene mixture；
(3) it prepares a water neodymium chloride isopropanol complex: a water neodymium chloride and isopropanol being added in toluene and carry out complexation reaction
A water neodymium chloride isopropanol complex is obtained, the temperature of complexation reaction is 20~40 DEG C, and the time is 6~16h, and should be under stiring
It carries out；
(4) it prepares catalyst: a water neodymium chloride isopropanol complex prepared by step (3) is added to the three of step (2) preparation
In aluminium isobutyl toluene solution and pentadiene mixture, reacted to obtain catalyst, reaction temperature is -5 DEG C hereinafter, the time
For 5~10min, and should carry out under stiring；And
(5) catalyst aging: catalyst aging 16h or more prepared by step (4), Aging Temperature are 20~40 DEG C, and should be
Stirring is lower to be carried out, and rare-earth isoprene rubber catalyst can be obtained；
In step (1), the mass content of triisobutyl aluminium is 13~18% in the triisobutylaluminum toluene solution.
2. the method according to claim 1 for preparing rare-earth isoprene rubber catalyst, which is characterized in that in step (2), institute
It states in triisobutylaluminum toluene solution and pentadiene mixture, the molar ratio of triisobutyl aluminium and pentadiene is 9~18:2
~4.
3. the method according to claim 1 for preparing rare-earth isoprene rubber catalyst, which is characterized in that in step (3), institute
It states in a water neodymium chloride isopropanol complex, the molar ratio of a water neodymium chloride and isopropanol is 1:2~4.
4. the method according to claim 1 for preparing rare-earth isoprene rubber catalyst, which is characterized in that in step (4), institute
A water neodymium chloride isopropanol complex is stated in terms of a water neodymium chloride, the triisobutylaluminum toluene solution and pentadiene mixture
In terms of triisobutyl aluminium, a water neodymium chloride isopropanol complex and triisobutylaluminum toluene solution are rubbed with pentadiene mixture
You are than being 1:9~18.
5. the method according to claim 1 for preparing rare-earth isoprene rubber catalyst, which is characterized in that the step (3)
The temperature of middle complexation reaction is 25~38 DEG C, and the time is 8~14h.
6. the method according to claim 1 for preparing rare-earth isoprene rubber catalyst, which is characterized in that the step (4)
Middle reaction temperature is -5 DEG C~-18 DEG C, and the time is 6~10min.
7. the method according to claim 1 for preparing rare-earth isoprene rubber catalyst, which is characterized in that the step (5)
Middle digestion time is 16h~98h, and Aging Temperature is 24~38 DEG C.
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