CN107602747A - A kind of synthetic method of high-cis polydiene hydrocarbon - Google Patents
A kind of synthetic method of high-cis polydiene hydrocarbon Download PDFInfo
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Abstract
The present invention provides a kind of synthetic method of high-cis polydiene hydrocarbon, including：In the closed container of anhydrous and oxygen-free, the reaction solution including diolefinic monomer, liquid isobutene and rare earth composite catalyst is subjected to polymerisation, obtains high-cis polydiene hydrocarbon；The diolefinic monomer is liquid butadiene and/or isoprene；Compactedness of the reaction solution in closed container is 30~70%.The present invention is using liquid butadiene and/or isoprene as raw material, using the isobutene of low boiling point as solvent, in anhydrous and oxygen-free under confined conditions, catalysis through rare earth composite catalyst carries out polymerisation, reaction terminates that rear isobutene is i.e. volatilizable at room temperature, reduces the dissolvent residual in product, obtained product easily reclaims, be easily separated, product postprocessing temperature is reduced, saves the energy.
Description
Technical field
The present invention relates to polymer synthesis techniques field, more particularly to a kind of synthetic method of high-cis polydiene hydrocarbon.
Background technology
It is more and more stronger for the demand of excellent properties rubber in the world with the fast development of auto industry.Rare earth gathers
Butadiene rubber has the characteristics that high intensity, resistance to flexion, low-heat-generation, anti-slippery and rolling resistance are low, is development high-performance tire
With the preferred glue kind of energy-saving tire；Rare earth polyisoprene rubber, structure is similar with performance with natural rubber, is a kind of comprehensive
The good general purpose rubber of energy, and water resistance, insulating properties exceed natural rubber；Rare earth butadiene-isoprene copolymer glue (fourth penta
Rubber) because of its excellent resistance to low temperature, wearability and low temperature rolling resistance every performance for meeting contemporary standard such as low, can
It is used as and prepares various high-performance tires, will there is wide development potentiality in future, by butadiene-isoamyl two of Rare Earth Metal Catalyzed in Polymerization
Alkene (Bd-Ip) copolymer rubber, reachable -104 DEG C of its Tg, and generation crystallization, cryogenic property and silicon rubber phase are not easy at low temperature
Seemingly, and mechanical property is better than silicon rubber, but vulcanizate is in -55 DEG C of long-term uses, can also be formed crystallization (China Synthetic Rubber Industry,
1986,9(5):354-357)。
The preparation method of a variety of butadiene, isoprene homopolymer and copolymer is reported in the prior art, but is adopted mostly
Organic solvent is used as by the use of high boiling solvents such as hexane, hexamethylene or heptane.For example, Publication No. CN101831032B China is specially
Profit reports a kind of preparation method of butadiene isoprene copolymer, and this method is by controlling reaction monomers and catalyst
Mol ratio controls the molecular weight and molecualr weight distribution of butadiene isoprene copolymer, and is terminated by the hydroxyl in ethanol
Polymerisation, preparing has low molecule amount, the butadiene isoprene copolymer of Narrow Molecular Weight Distribution, and organic solvent used is
Hexane, hexamethylene or heptane.Publication No. CN103724378A Chinese patent reports a kind of isoprene-butadiene binary
Copolymer and preparation method thereof, this method is using butadiene-isoprene monomer, rare earth compounding, alkyl aluminum and contains alkyl halide
The halogen donor of base aluminium is as catalyst system and catalyzing, there is provided a kind of to have higher Isosorbide-5-Nitrae-structure polybutadiene segments 3,4- structures are gathered
The preparation method of the Isoprene-butadiene bipolymer of isoprene segment.
Above-mentioned technical proposal is mostly using high boiling solvents such as hexane, hexamethylene or heptane as organic solvent, due to boiling
Point is higher, and if the boiling point of hexane is 69 DEG C, the boiling point of hexamethylene is 80.7 DEG C, and the boiling point of heptane is 98.42 DEG C, is easily made in product
Into dissolvent residual, increase volatile matter content, and product postprocessing need to reach certain temperature, cause energy waste.
The content of the invention
It is an object of the invention to provide a kind of synthetic method of high-cis polydiene hydrocarbon.High-cis provided by the invention gathers
The synthetic method solvent boiling point of alkadienes is low, reduces the dissolvent residual in product.
The invention provides a kind of synthetic method of high-cis polydiene hydrocarbon, including：
In the closed container of anhydrous and oxygen-free, by including diolefinic monomer, liquid isobutene and rare earth composite catalyst
Reaction solution carries out polymerisation, obtains high-cis polydiene hydrocarbon；The diolefinic monomer is liquid butadiene and/or isoamyl two
Alkene；Compactedness of the reaction solution in closed container is 30~70%.
Preferably, the reaction solution is mixed to get by diolefinic monomer, liquid isobutene and rare earth composite catalyst, institute
The temperature for stating mixing is less than -100 DEG C.
Preferably, the rare earth composite catalyst includes rare earth compound, alkyl aluminum and halide-containing.
Preferably, the mol ratio of the rare earth compound, alkyl aluminum and halide-containing is 1:(1~100):(1~50).
Preferably, the mol ratio of the rare earth compound and diolefinic monomer is (1~200) × 10-4:1。
Preferably, the rare earth compound includes rare earth-beta-diketon class complex.
Preferably, the alkyl aluminum includes one kind or more in triethyl aluminum, diisobutylaluminium hydride and triisobutyl aluminium
Kind.
Preferably, the halide-containing includes the one or more in alkyl aluminium halide, halosilanes and inorganic halides.
Preferably, the temperature of the polymerisation is 0~50 DEG C, and the time of polymerisation is 0.5~6h.
Preferably, the polymerisation is terminated by adding terminator into the closed container.
The invention provides a kind of synthetic method of high-cis polydiene hydrocarbon, including：In the closed container of anhydrous and oxygen-free,
Reaction solution including diolefinic monomer, liquid isobutene and rare earth composite catalyst is subjected to polymerisation, obtains high-cis
Polydiene；The diolefinic monomer is liquid butadiene and/or isoprene；The reaction solution filling out in closed container
Degree of filling is 30~70%.The present invention is using liquid butadiene and/or isoprene as raw material, using the isobutene of low boiling point as solvent,
In anhydrous and oxygen-free under confined conditions, the catalysis through rare earth composite catalyst carries out polymerisation, and reaction terminates rear isobutene in room
It is i.e. volatilizable under temperature, the dissolvent residual in product is reduced, obtained product easily reclaims, be easily separated, reduces product postprocessing
Temperature, save the energy.Test result indicates that synthetic method provided by the invention turns without carrying out extra process, product to solvent
Rate is 90.4%, and up to 98.8%, the cis-structure of polyisoprene segments reaches the cis-structure of polybutadiene segments in product
97.6%.
Embodiment
The invention provides a kind of synthetic method of high-cis polydiene hydrocarbon, including：
In the closed container of anhydrous and oxygen-free, by including diolefinic monomer, liquid isobutene and rare earth composite catalyst
Reaction solution carries out polymerisation, obtains high-cis polydiene hydrocarbon；The diolefinic monomer is liquid butadiene and/or isoamyl two
Alkene；Compactedness of the reaction solution in closed container is 30~70%.
In the present invention, the diolefinic monomer is liquid butadiene and/or isoprene.In the present invention, when described
When diolefinic monomer is liquid butadiene, the polydiene is polybutadiene；When the diolefinic monomer is isoprene,
The polydiene is polyisoprene；When the diolefinic monomer is liquid butadiene and isoprene, the polydiene
Hydrocarbon is butadiene isoprene copolymer.It is special that the present invention does not have to the mol ratio of the liquid butadiene and isoprene
Limit, be adjusted according to required product.
In the present invention, the boiling point of the liquid isobutene is -6.9 DEG C, i.e. volatilizable at room temperature, greatly reduces product
In dissolvent residual, obtained product easily reclaims, is easily separated, can substantially reduce product postprocessing temperature, saves the energy.
In the present invention, the rare earth composite catalyst preferably includes rare earth compound, alkyl aluminum and halide-containing.
In the present invention, the mol ratio of the rare earth compound, alkyl aluminum and halide-containing is preferably 1:(1~100):(1~50), more
Preferably 1:(10~80):(2~30), most preferably 1:(15~40):(3~15).In the present invention, the rare earth compound
Mol ratio with diolefinic monomer is preferably (1~200) × 10-4:1, more preferably (2~100) × 10-4:1, it is most preferably (3
~50) × 10-4:1.The present invention does not have special restriction to the dosage of the liquid isobutene, ripe using those skilled in the art
The solvent load known.
In the present invention, the rare earth compound preferably includes rare earth-beta-diketon class complex, more preferably including aphthenic acids
One or more in rare earth, neodecanoic acid rare earth and phosphate rare earth.In the present invention, the rare earth member in the rare earth compound
Plain preferably Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, more preferably Nd.The present invention's
In embodiment, the rare earth compound is preferably neodymium naphthenate, neodymium caprate, phosphate neodymium and one kind or more in neodymium iso-octanate
Kind.
In the present invention, the alkyl aluminum is preferably included in triethyl aluminum, diisobutylaluminium hydride and triisobutyl aluminium
It is one or more.In the present invention, the halide-containing is preferably included in alkyl aluminium halide, halosilanes and inorganic halides
One or more, more preferably including the one or more in chlorination alkyl aluminum, chlorosilane and butter.In the reality of the present invention
Apply in example, the halide-containing is preferably diethylaluminum chloride, di-isobutyl aluminum chloride, chloroform, SiCl4、SnCl4、
MgCl2And ZnCl2In one or more.
The present invention does not have special restriction to the preparation method of the rare earth composite catalyst, using those skilled in the art
The technical scheme of the preparation of well known rare earth composite catalyst.In the present invention, the preparation of the rare earth composite catalyst
It is preferred that with reference to the B of Chinese patent CN 101831032.In the present invention, the rare earth compound in the rare earth composite catalyst with
Alkylated reaction occurs for alkyl aluminum, and halogen exchange reaction occurs with halide-containing, ultimately generates the complexing of bimetallic binuclear active
Thing, or multinuclear activated complex.
In the present invention, the environment of the anhydrous and oxygen-free is preferably vacuum or inert atmosphere, more preferably High Purity Nitrogen atmosphere.
In the present invention, the closed container of the anhydrous and oxygen-free preferably obtains in the following way：In a heated condition by clean dried
Closed container carry out vacuumize process, when the pressure of closed container reaches negative pressure, be filled with high pure nitrogen；Treat closed container perseverance
Wen Hou, repeat the above steps 3~5 times.In the present invention, the purity of the High Purity Nitrogen is preferably more than 99.999%.In this hair
In bright, the anhydrous and oxygen-free can avoid losing with stronger chemically active catalyst chance water and oxygen generation vigorous reaction
It is living.
The present invention does not have special restriction to the species of the closed container, using it is well known to those skilled in the art can
Sealing and high voltage bearing container.In the present invention, the closed container is preferably polymerization bottle.
In the present invention, the reaction solution is preferably mixed by diolefinic monomer, liquid isobutene and rare earth composite catalyst
Conjunction obtains；The temperature of the mixing is preferably less than -100 DEG C, more preferably less than -150 DEG C.The present invention is preferably in liquid nitrogen frozen
Under conditions of by diolefinic monomer, liquid isobutene and rare earth composite catalyst mix.In the present invention, the alkadienes list
The mixing of body, liquid isobutene and rare earth composite catalyst is preferably：By the closed container of diolefinic monomer access anhydrous and oxygen-free
In, then under conditions of liquid nitrogen frozen, liquid isobutene is added, is eventually adding rare earth composite catalyst.
In the present invention, compactedness of the reaction solution in closed container is 30~70%, preferably 40~60%,
More preferably 45~55%.In the present invention, the compactedness can ensure the fourth in closed container under polymeric reaction temperature
Diene and isobutene can exist with liquid phase.
After obtaining reaction solution, the reaction solution is carried out polymerisation by the present invention in the closed container, is obtained
High-cis polydiene hydrocarbon.In the present invention, the temperature of the polymerisation is preferably 0~50 DEG C, more preferably 10~40 DEG C, most
Preferably 20~30 DEG C；The time of the polymerisation is preferably 0.5~6h, more preferably 1~5h, most preferably 2~4h.
In the present invention, the polymerisation is preferably carried out under water bath condition.In the present invention, the diolefinic monomer is compound in rare earth
Under the catalytic action of catalyst, polymerization obtains high-cis polydiene hydrocarbon.
In the present invention, the polymerisation is preferably terminated by adding terminator into the closed container.The present invention
There is no special restriction to the species of the terminator, using the terminator well known to those skilled in the art for polymerisation
.In the present invention, the terminator is preferably the ethanol solution of 2,6- di-tert-butyl-4-methy phenols (antioxidant 264)；
The mass content of 2,6 di tert butyl 4 methyl phenol is preferably 1~2% in the terminator.
After polymerisation terminates, the present invention preferably opens the closed container, makes environment restoration in the closed container
To normal temperature and pressure.In the present invention, the isobutylene solvent is i.e. volatilizable at normal temperatures, obtains polymeric reaction product.
After obtaining polymeric reaction product, the polymeric reaction product is preferably washed and dried successively by the present invention, is obtained
To high-cis polydiene hydrocarbon.The present invention is to the washing and the no special restriction of operation dried, using people in the art
Washing known to member and the operation dried.In the present invention, the detergent of the washing is preferably absolute ethyl alcohol；It is described to wash
The number washed is preferably 3~5 times.In the present invention, the drying is preferably air drying；The time of the drying is preferably 8
~10h.
It is i.e. volatilizable at room temperature that synthetic method provided by the invention reaction terminates rear isobutylene solvent, reduces in product
Dissolvent residual, obtained product easily reclaims, is easily separated, reduces product postprocessing temperature, saves the energy.
In order to further illustrate the present invention, with reference to synthesis of the embodiment to high-cis polydiene hydrocarbon provided by the invention
Method is described in detail, but they can not be interpreted as into limiting the scope of the present invention.
Embodiment 1:
Under vacuum state, into the 100ml polymerization bottles of clean dried, 7mL isoprene monomers and 6mL fourths two are sequentially added
Alkene monomer, under the conditions of liquid nitrogen frozen, 20mL isobutenes are accessed in polymerization bottle, form monomer solution, butadiene and isoamyl two
The mol ratio of alkene is 1: 1, then adds the catalyst solution that about 6mL is prepared, catalyst molar ratio [Nd]/[Al]/[Cl] /=
1/15/2, Rare Earths in Catalyst compound and monomer mole ratio [Nd]/[M]=10.0 × 10-4:1；Catalyst is matched somebody with somebody with solvent hexane
Solution is set to, rare earth compound is configured to 0.1mol/L solution, alkyl aluminum 1.0mol/L solution, halide-containing
0.1mol/L solution, it is configured to the convenient metering addition of solution.
Rare Earths in Catalyst compound is neodymium caprate, and alkyl aluminum is triisobutyl aluminium, and halide-containing is that chlorination two is different
Butyl aluminium.
Polymerization bottle is put into water bath with thermostatic control, under the conditions of 30 DEG C of constant temperature, after reacting 5 hours, adds quality containing antioxidant 264
The ethanol solution that fraction is 1% carries out terminating reaction.
Product is shredded after the washing of absolute ethyl alcohol repeatedly for three times and is put in normal temperature on culture dish and does by gained copolymerization product
Dry 8 hours, it was 84.1% to measure product yield, and suitable Isosorbide-5-Nitrae-structural content of polybutadiene segments is 97.6%, poly- isoamyl two
The suitable 1,4- structural contents of alkene segment are 95.8%.
Embodiment 2:
Under vacuum state, into the 100ml polymerization bottles of clean dried, 17.5ml isoprene monomers and 15mL are sequentially added
Divinylic monomer, under the conditions of liquid nitrogen frozen, will 25mL isobutenes access polymerization bottle in, formed monomer solution, butadiene with it is different
The mol ratio of pentadiene is 1: 1, then adds the catalyst solution that about 6ml is prepared, catalyst molar ratio [Nd]/[Al]/
[Cl] /=1/15/2, Rare Earths in Catalyst compound and monomer mole ratio [Nd]/[M]=4.2 × 10-4:1；
Rare Earths in Catalyst compound is neodymium caprate, and alkyl aluminum is triisobutyl aluminium, and halide-containing is that chlorination two is different
Butyl aluminium.
Polymerization bottle is put into water bath with thermostatic control, under the conditions of 30 DEG C of constant temperature, after reacting 5 hours, adds quality containing antioxidant 264
The ethanol solution that fraction is 1% carries out terminating reaction.
Product is shredded after the washing of absolute ethyl alcohol repeatedly for three times and is put in normal temperature on culture dish and does by gained copolymerization product
Dry 8 hours, product yield was measured as 86.7%；Suitable Isosorbide-5-Nitrae-the structural content for measuring polybutadiene segments is 98.1%, is gathered different
The suitable 1,4- structural contents of pentadiene segment are 97.2%.
Embodiment 3:
Under vacuum state, into the 100ml polymerization bottles of clean dried, 17.5ml isoprene monomers and 15mL are sequentially added
Divinylic monomer, under the conditions of liquid nitrogen frozen, will 25mL isobutenes access polymerization bottle in, formed monomer solution, butadiene with it is different
The mol ratio of pentadiene is 1: 1, then adds the catalyst solution that about 3ml is prepared, catalyst molar ratio [Nd]/[Al]/
[Cl] /=1/15/2, Rare Earths in Catalyst compound and monomer mole ratio [Nd]/[M]=2.1 × 10-4:1；
Rare Earths in Catalyst compound is neodymium caprate, and alkyl aluminum is triisobutyl aluminium, and halide-containing is that chlorination two is different
Butyl aluminium.
Polymerization bottle is put into water bath with thermostatic control, under the conditions of 30 DEG C of constant temperature, after reacting 5 hours, adds quality containing antioxidant 264
The ethanol solution that fraction is 1% carries out terminating reaction.
Product is shredded after the washing of absolute ethyl alcohol repeatedly for three times and is put in normal temperature on culture dish and does by gained copolymerization product
Dry 8 hours, it was 88.2% to measure product yield, and the suitable Isosorbide-5-Nitrae-structural content for measuring polybutadiene segments is 98.8%, is gathered different
The suitable 1,4- structural contents of pentadiene segment are 97.6%.
Embodiment 4:
Under vacuum state, into the 100ml polymerization bottles of clean dried, 7ml isoprene monomers and 6mL fourths two are sequentially added
Alkene monomer, under the conditions of liquid nitrogen frozen, 20mL isobutenes are accessed in polymerization bottle, form monomer solution, butadiene and isoamyl two
The mol ratio of alkene is 1: 1, then adds the catalyst solution that about 6ml is prepared, catalyst molar ratio [Nd]/[Al]/[Cl] /=
1/15/2, Rare Earths in Catalyst compound and monomer mole ratio [Nd]/[M]=10.0 × 10-4:1；
Rare Earths in Catalyst compound is neodymium caprate, and alkyl aluminum is triisobutyl aluminium, and halide-containing is that chlorination two is different
Butyl aluminium.
Polymerization bottle is put into water bath with thermostatic control, under the conditions of 40 DEG C of constant temperature, after reacting 5 hours, adds quality containing antioxidant 264
The ethanol solution that fraction is 1% carries out terminating reaction.
Product is shredded after the washing of absolute ethyl alcohol repeatedly for three times and is put in normal temperature on culture dish and does by gained copolymerization product
Dry 8 hours, it was 83.9% to measure product yield, and suitable Isosorbide-5-Nitrae-structural content of polybutadiene segments is 98.1%, poly- isoamyl two
The suitable 1,4- structural contents of alkene segment are 96.9%.
Embodiment 5:
Under vacuum state, into the 100ml polymerization bottles of clean dried, 17.5ml isoprene monomers and 15mL are sequentially added
Divinylic monomer, under the conditions of liquid nitrogen frozen, will 25mL isobutenes access polymerization bottle in, formed monomer solution, butadiene with it is different
The mol ratio of pentadiene is 1: 1, then adds the catalyst solution that about 6ml is prepared, catalyst molar ratio [Nd]/[Al]/
[Cl] /=1/15/2, Rare Earths in Catalyst compound and monomer mole ratio [Nd]/[M]=4.2 × 10-4:1；
Rare Earths in Catalyst compound is neodymium caprate, and alkyl aluminum is triisobutyl aluminium, and halide-containing is that chlorination two is different
Butyl aluminium.
Polymerization bottle is put into water bath with thermostatic control, under the conditions of 40 DEG C of constant temperature, after reacting 5 hours, adds quality containing antioxidant 264
The ethanol solution that fraction is 1% carries out terminating reaction.
Product is shredded after the washing of absolute ethyl alcohol repeatedly for three times and is put in normal temperature on culture dish and does by gained copolymerization product
Dry 8 hours, product yield was measured as 89.8%；Suitable Isosorbide-5-Nitrae-the structural content for measuring polybutadiene segments is 98.2%, is gathered different
The suitable 1,4- structural contents of pentadiene segment are 97.1%.
Embodiment 6:
Under vacuum state, into the 100ml polymerization bottles of clean dried, 17.5ml isoprene monomers and 15mL are sequentially added
Divinylic monomer, under the conditions of liquid nitrogen frozen, will 25mL isobutenes access polymerization bottle in, formed monomer solution, butadiene with it is different
The mol ratio of pentadiene is 1: 1, then adds the catalyst solution that about 3ml is prepared, catalyst molar ratio [Nd]/[Al]/
[Cl] /=1/15/2, Rare Earths in Catalyst compound and monomer mole ratio [Nd]/[M]=2.1 × 10-4:1；
Rare Earths in Catalyst compound is neodymium caprate, and alkyl aluminum is triisobutyl aluminium, and halide-containing is that chlorination two is different
Butyl aluminium.
Polymerization bottle is put into water bath with thermostatic control, under the conditions of 40 DEG C of constant temperature, after reacting 5 hours, adds quality containing antioxidant 264
The ethanol solution that fraction is 1% carries out terminating reaction.
Product is shredded after the washing of absolute ethyl alcohol repeatedly for three times and is put in normal temperature on culture dish and does by gained copolymerization product
Dry 8 hours, it was 90.1% to measure product yield, and the suitable Isosorbide-5-Nitrae-structural content for measuring polybutadiene segments is 98.1%, is gathered different
The suitable 1,4- structural contents of pentadiene segment are 96.9%.
Embodiment 7:
Under vacuum state, into the 100ml polymerization bottles of clean dried, 7ml isoprene monomers and 6mL fourths two are sequentially added
Alkene monomer, under the conditions of liquid nitrogen frozen, 20mL isobutenes are accessed in polymerization bottle, form monomer solution, butadiene and isoamyl two
The mol ratio of alkene is 1: 1, then adds the catalyst solution that about 6ml is prepared, catalyst molar ratio [Nd]/[Al]/[Cl] /=
1/15/2, Rare Earths in Catalyst compound and monomer mole ratio [Nd]/[M]=10.0 × 10-4:1；
Rare Earths in Catalyst compound is neodymium caprate, and alkyl aluminum is triisobutyl aluminium, and halide-containing is that chlorination two is different
Butyl aluminium.
Polymerization bottle is put into water bath with thermostatic control, under the conditions of 50 DEG C of constant temperature, after reacting 5 hours, adds quality containing antioxidant 264
The ethanol solution that fraction is 1% carries out terminating reaction.
Product is shredded after the washing of absolute ethyl alcohol repeatedly for three times and is put in normal temperature on culture dish and does by gained copolymerization product
Dry 8 hours, it was 84.6% to measure product yield, and suitable Isosorbide-5-Nitrae-structural content of polybutadiene segments is 98.5%, poly- isoamyl two
The suitable 1,4- structural contents of alkene segment are 97.4%.
Embodiment 8
Under vacuum state, into the 100ml polymerization bottles of clean dried, 17.5ml isoprene monomers and 15mL are sequentially added
Divinylic monomer, under the conditions of liquid nitrogen frozen, will 25mL isobutenes access polymerization bottle in, formed monomer solution, butadiene with it is different
The mol ratio of pentadiene is 1: 1, then adds the catalyst solution that about 6ml is prepared, catalyst molar ratio [Nd]/[Al]/
[Cl] /=1/15/2, Rare Earths in Catalyst compound and monomer mole ratio [Nd]/[M]=4.2 × 10-4:1；
Rare Earths in Catalyst compound is neodymium caprate, and alkyl aluminum is triisobutyl aluminium, and halide-containing is diethyl
Base aluminium.
Polymerization bottle is put into water bath with thermostatic control, under the conditions of 50 DEG C of constant temperature, after reacting 5 hours, adds quality containing antioxidant 264
The ethanol solution that fraction is 1% carries out terminating reaction.
Product is shredded after the washing of absolute ethyl alcohol repeatedly for three times and is put in normal temperature on culture dish and does by gained copolymerization product
Dry 8 hours, product yield was measured as 89.3%；Suitable Isosorbide-5-Nitrae-the structural content for measuring polybutadiene segments is 98.1%, is gathered different
The suitable 1,4- structural contents of pentadiene segment are 96.9%.
Embodiment 9
Under vacuum state, into the 100ml polymerization bottles of clean dried, 17.5ml isoprene monomers and 15mL are sequentially added
Divinylic monomer, under the conditions of liquid nitrogen frozen, will 25mL isobutenes access polymerization bottle in, formed monomer solution, butadiene with it is different
The mol ratio of pentadiene is 1: 1, then adds the catalyst solution that about 3ml is prepared, catalyst molar ratio [Nd]/[Al]/
[Cl] /=1/15/2, Rare Earths in Catalyst compound and monomer mole ratio [Nd]/[M]=2.1 × 10-4:1；
Rare Earths in Catalyst compound is neodymium caprate, and alkyl aluminum is triisobutyl aluminium, and halide-containing is diethyl
Base aluminium.
Polymerization bottle is put into water bath with thermostatic control, under the conditions of 50 DEG C of constant temperature, after reacting 5 hours, adds quality containing antioxidant 264
The ethanol solution that fraction is 1% carries out terminating reaction.
Product is shredded after the washing of absolute ethyl alcohol repeatedly for three times and is put in normal temperature on culture dish and does by gained copolymerization product
Dry 8 hours, it was 90.4% to measure product yield, and the suitable Isosorbide-5-Nitrae-structural content for measuring polybutadiene segments is 97.4%, is gathered different
The suitable 1,4- structural contents of pentadiene segment are 96.5%.
Embodiment 10
Under vacuum state, into the 100ml polymerization bottles of clean dried, 12mL divinylic monomers are added, in liquid nitrogen frozen bar
Under part, 25mL isobutenes are accessed in polymerization bottle, monomer solution is formed, then adds the catalyst solution that about 2.5ml is prepared,
Catalyst molar ratio [Nd]/[BD]/[Al]/[Cl] /=1/15/2, Rare Earths in Catalyst compound and monomer mole ratio [Nd]/
[M]=4.0 × 10-4:1；
Rare Earths in Catalyst compound is neodymium caprate, and alkyl aluminum is triisobutyl aluminium, and halide-containing is diethyl
Base aluminium.
Polymerization bottle is put into water bath with thermostatic control, under the conditions of 30 DEG C of constant temperature, after reacting 5 hours, adds quality containing antioxidant 264
The ethanol solution that fraction is 1% carries out terminating reaction.
Product is shredded after the washing of absolute ethyl alcohol repeatedly for three times and is put in air drying 8 on culture dish by products therefrom
Hour, it is 86.1% to measure product yield, and suitable Isosorbide-5-Nitrae-structural content of polybutadiene segments is 97.1%.
Embodiment 11
Under vacuum state, into the 100ml polymerization bottles of clean dried, 14ml isoprene is added, in liquid nitrogen frozen condition
Under, 25mL isobutenes are accessed in polymerization bottle, monomer solution is formed, then adds the catalyst solution that about 2.5ml is prepared, urge
Agent mol ratio [Nd]/[Al]/[Cl] /=1/15/2, Rare Earths in Catalyst compound and monomer mole ratio [Nd]/[M]=4.0
×10-4:1；
Rare Earths in Catalyst compound is neodymium caprate, and alkyl aluminum is triisobutyl aluminium, and halide-containing is diethyl
Base aluminium.
Polymerization bottle is put into water bath with thermostatic control, under the conditions of 30 DEG C of constant temperature, after reacting 5 hours, adds quality containing antioxidant 264
The ethanol solution that fraction is 1% carries out terminating reaction.
Product is shredded after the washing of absolute ethyl alcohol repeatedly for three times and is put in air drying 8 on culture dish by products therefrom
Hour, it is 84.2% to measure product yield, and suitable Isosorbide-5-Nitrae-structural content of polyisoprene segments is 96.4%.
As can be seen from the above embodiments, synthetic method reaction provided by the invention terminates rear solvent can wave at room temperature
Hair, reduces the dissolvent residual in product, and obtained product easily reclaims, be easily separated, reduces product postprocessing temperature, saves energy
Source, and product yield is high, product is high-cis structure.
Described above is only the preferred embodiment of the present invention, not makees any formal limitation to the present invention.Should
Point out, for those skilled in the art, under the premise without departing from the principles of the invention, if can also make
Dry improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of synthetic method of high-cis polydiene hydrocarbon, including：
In the closed container of anhydrous and oxygen-free, the reaction of diolefinic monomer, liquid isobutene and rare earth composite catalyst will be included
Solution carries out polymerisation, obtains high-cis polydiene hydrocarbon；The diolefinic monomer is liquid butadiene and/or isoprene；
Compactedness of the reaction solution in closed container is 30~70%.
2. synthetic method according to claim 1, it is characterised in that the reaction solution is different by diolefinic monomer, liquid
Butylene and rare earth composite catalyst are mixed to get, and the temperature of the mixing is less than -100 DEG C.
3. synthetic method according to claim 1, it is characterised in that the rare earth composite catalyst includes rare earth chemical combination
Thing, alkyl aluminum and halide-containing.
4. synthetic method according to claim 3, it is characterised in that the rare earth compound, alkyl aluminum and halogen chemical combination
The mol ratio of thing is 1:(1~100):(1~50).
5. the synthetic method according to claim 3 or 4, it is characterised in that the rare earth compound and diolefinic monomer
Mol ratio is (1~200) × 10-4:1。
6. the synthetic method according to claim 3 or 4, it is characterised in that the rare earth compound includes rare earth-beta-diketon
Class complex.
7. the synthetic method according to claim 3 or 4, it is characterised in that the alkyl aluminum includes triethyl aluminum, hydrogenation two
One or more in aluminium isobutyl and triisobutyl aluminium.
8. the synthetic method according to claim 3 or 4, it is characterised in that the halide-containing include alkyl aluminium halide,
One or more in halosilanes and inorganic halides.
9. synthetic method according to claim 1, it is characterised in that the temperature of the polymerisation is 0~50 DEG C, polymerization
The time of reaction is 0.5~6h.
10. the synthetic method according to claim 1 or 9, it is characterised in that the polymerisation is by the closed appearance
Terminator is added in device to terminate.
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| CN104136470A (en) * | 2012-02-17 | 2014-11-05 | 巴斯夫欧洲公司 | Method for producing high-molecular-weight polyisobutylene |
| CN104725564A (en) * | 2013-12-24 | 2015-06-24 | 青岛伊科思新材料股份有限公司 | Polymerization method of isoprene and butadiene |
| CN105087168A (en) * | 2015-07-30 | 2015-11-25 | 仲恺农业工程学院 | Method for fast making crude fat from brewed soya residues |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104136470A (en) * | 2012-02-17 | 2014-11-05 | 巴斯夫欧洲公司 | Method for producing high-molecular-weight polyisobutylene |
| CN104725564A (en) * | 2013-12-24 | 2015-06-24 | 青岛伊科思新材料股份有限公司 | Polymerization method of isoprene and butadiene |
| CN105087168A (en) * | 2015-07-30 | 2015-11-25 | 仲恺农业工程学院 | Method for fast making crude fat from brewed soya residues |
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