CN103159882B - A kind for the treatment of process of the polyisoprene solution containing catalyzer - Google Patents
A kind for the treatment of process of the polyisoprene solution containing catalyzer Download PDFInfo
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- CN103159882B CN103159882B CN201110408169.7A CN201110408169A CN103159882B CN 103159882 B CN103159882 B CN 103159882B CN 201110408169 A CN201110408169 A CN 201110408169A CN 103159882 B CN103159882 B CN 103159882B
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Abstract
The invention provides a kind for the treatment of process of the polyisoprene solution containing catalyzer, described catalyzer is halogenated titanium and aluminum alkyls and the interactional product of electron donor, wherein, under the method is included in hyperacoustic acting in conjunction of multiple frequency, the described polyisoprene solution containing catalyzer is contacted with aqueous sodium hydroxide solution, makes described catalyst deactivation.Adopt method of the present invention to process the polyisoprene solution containing catalyzer, can not to environment, technique is simple and the Inactivation Effect of catalyzer is good.
Description
Technical field
The present invention relates to a kind for the treatment of process of the polyisoprene solution containing catalyzer.
Background technology
Polyisoprene can be divided into cis-Isosorbide-5-Nitrae-polyisoprene, anti-form-1,4-polyisoprene, 3,4-polyisoprene and 1,2-polyisoprene.Wherein, cis-Isosorbide-5-Nitrae-polyisoprene is commonly called as polyisoprene rubber, and its microtexture is similar to natural rubber (as hevea, guayule).At present, polyisoprene rubber has been widely used in manufacturing tire and other rubber items, is the main substitute of natural rubber.
Because cis-Isosorbide-5-Nitrae-polyisoprene has high degree of unsaturation, in some physics and chemistry factors as under the effect of oxygen, ozone, light, high temperature and ultraviolet etc., its molecular chain easily ruptures and degrades.At present, usually adopt Ziegler-Natta catalyst to carry out synthesizing cis-Isosorbide-5-Nitrae-polyisoprene, more representational is TiCl
4-AlR
3and TiCl
4-poly-this two classes catalyzer of imido grpup aluminium alkane.Research shows, the active ingredient TiCl in this type of catalyzer
3at room temperature can generate such as Cl with oxygen reaction
3ti-O-O-TiCl
3superoxide, this superoxide easily decomposes free radical (the such as Cl that generation can cause the degraded of cis-Isosorbide-5-Nitrae-polyisoprene
3tiO).As can be seen here, in polymkeric substance, the degraded of existence to polymkeric substance of active catalyst has a significant impact.Therefore, in order to prevent the degraded of cis-Isosorbide-5-Nitrae-polyisoprene, the traces of catalyst removed in cis-Isosorbide-5-Nitrae-polyisoprene is very important.
Mentioning in " isoprene tactic polymerization " (Science Press, 1984) book that this storehouse of neat Olympic Competition is shown to adopt methyl alcohol, ethanol or acetone as catalyst deactivation agent.In industrial production in early days, these deactivators are all widely used.But these reagent itself are poisonous, a large amount of use Water purification and environment protection can bring very large pressure undoubtedly.
Disclose in SU689212 and use maleic acid derivatives as catalyst deactivation agent.But in order to make Inactivation Effect better, also need to add methyl alcohol or ethanol, and complex treatment process.
Disclose in GB1317507 and aliphatic diamine or polyamines can be used as deactivator, but research shows, adopt the effect of metal titanium in this deactivator removal polymkeric substance unsatisfactory.
Summary of the invention
When the method that the object of the invention is to overcome employing prior art removes the catalyzer in polyisoprene solution, existing may the undesirable defect of the Inactivation Effect of contaminate environment, complex process and catalyzer, provide a kind of can not to environment, technique the simple and treatment process of the polyisoprene solution that the Inactivation Effect of catalyzer is good.
The invention provides a kind for the treatment of process of the polyisoprene solution containing catalyzer, described catalyzer is halogenated titanium and aluminum alkyls and the interactional product of electron donor, wherein, under the method is included in hyperacoustic acting in conjunction of multiple frequency, the described polyisoprene solution containing catalyzer is contacted with aqueous sodium hydroxide solution, makes described catalyst deactivation.
The present inventor stumbles on, described sodium hydroxide can with catalyzer, that is, halogenated titanium and aluminum alkyls and the interactional product of electron donor react, thus reach the object removed by described catalyzer.Describedly to carry out under hyperacoustic acting in conjunction of multiple frequency containing the polyisoprene solution of catalyzer and the contact of aqueous sodium hydroxide solution, when the ultrasonic wave of different frequency acts on mixture simultaneously, its sound field is wider, and " mixing sound field " effect can be produced, strengthen hyperacoustic action effect further.In the preferred embodiment of the present invention, as shown in Figure 2, described cavity 3 is right cylinder, and multiple ultrasonic transducer 5 is positioned at same plane, and ultrasonic emitting 6 is staggered, ultrasonic wave to be sent to mixture in ultrasonic mixer by by stretching into ultrasonic emitting in ultrasonic mixer 6 by each ultrasonic generator 4, the polyisoprene solution containing catalyzer so not only can be made with aqueous sodium hydroxide solution to mix more even, hyperacoustic " cavitation effect " can also be utilized to accelerate catalyst activity component residual in polyisoprene solution and the speed of response of sodium hydroxide, improve mixing efficiency, decrease the consumption of sodium hydroxide simultaneously.In addition, in another kind of preferred implementation of the present invention, when cavity 3 be rectangular parallelepiped or square time, described ultrasonic emitting 6 length stretched in ultrasonic mixer are described cavity 3 height or the 1/4-3/4 of width; Or when described cavity 3 is right cylinder, described ultrasonic emitting 6 length stretched in ultrasonic mixer are the 1/4-3/4 of described cavity 3 diameter; Then described ultrasonic emitting 6 can also play good barrier effect to material, material is formed in ultrasonic emitting 6 surrounding stream, to further ensure in polyisoprene solution fully contacting of residual catalyst activity component and sodium hydroxide, effect is more excellent.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Fig. 1 is the sectional view of ultrasonic mixer provided by the invention;
Fig. 2 is the left view of ultrasonic mixer provided by the invention.
Description of reference numerals:
1-entrance; 2-exports; 3-cavity; 4-ultrasonic generator; Described ultrasonic generator comprises: 5-ultrasonic transducer; 6-ultrasonic emitting head.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
According to the treatment process of the polyisoprene solution containing catalyzer provided by the invention, described catalyzer is halogenated titanium and aluminum alkyls and the interactional product of electron donor, wherein, under the method is included in hyperacoustic acting in conjunction of multiple frequency, the described polyisoprene solution containing catalyzer is contacted with aqueous sodium hydroxide solution, makes described catalyst deactivation.
According to method provided by the invention, described halogenated titanium can be such as one or more in titanium tetrachloride, titanium tetrafluoride, titanium tetrabromide and titanium tetra iodide, is preferably titanium tetrachloride.The aluminum alkyls that described aluminum alkyls can be commonly used for field of olefin polymerisation such as, can be AlR for general formula
3organo-aluminium compound, wherein, R can be the straight or branched of 1-6 carbon atom; Be preferably in trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand, three n-butylaluminum and triisobutyl aluminium one or more; More preferably triisobutyl aluminium.Described electron donor can be the conventional electron donor of field of olefin polymerisation, such as, can be one or more in aliphatic ether, aromatic oxide, aliphatic amine and aromatic amine, preferably phenyl ether.
The present inventor is through in depth studying discovery, described aqueous sodium hydroxide solution can interact with the titanium in polyisoprene solution, aluminium and generate water-fast titanium oxide, aluminum oxide, described titanium oxide, aluminum oxide can be separated from polyisoprene solution by solid-liquid separation.The method of described solid-liquid separation can be selected from the method for existing various solid-liquid separation, such as, filter, centrifugal etc., and those skilled in the art can reasonably select, and will repeat no more at this.
The quantity of the present invention to hyperacoustic frequency is not particularly limited, but in order to reduce different frequency ultrasonic wave between mutual interference and improve contact effect, under preferable case, the quantity of described hyperacoustic frequency is 2-6, more preferably 3-4; Hyperacoustic difference on the frequency of any two different frequencies is at least 5KHz, and under preferable case, hyperacoustic difference on the frequency of any two different frequencies is 10KHz-20KHz.
In treatment process according to polyisoprene solution provided by the invention, the selectable range of described hyperacoustic frequency is wider, such as, described hyperacoustic frequency can be 15KHz-1MHz, under hyperacoustic effect of this frequency, the object of the polyisoprene solution and sodium hydroxide that contain catalyzer being carried out good contact can be realized.As a rule, ultrasonic frequency is higher, and its penetrativity is stronger, and contact effect is better, but frequency more highly energy-consuming is larger, therefore, combined factors is considered from every side, more preferably, in situation, described hyperacoustic frequency is 20KHz-600KHz, more preferably 20KHz-60KHz.
The concentration of the present invention to described aqueous sodium hydroxide solution is not particularly limited, can with the catalyst reaction in described polyisoprene solution as long as meet, thus reach the object removing described catalyzer well, such as, with the total weight of described aqueous sodium hydroxide solution, the content of described sodium hydroxide is 0.1-1 % by weight.In order to less impurity introducing, obtain the higher polyisoprene of purity, under preferable case, the water in described aqueous sodium hydroxide solution is deionized water.
According to the present invention, the consumption of sodium hydroxide can in very large range change, but, the catalyzer in polyisoprene solution is also effectively removed in waste in order to avoid sodium hydroxide, under preferable case, in the metal titanium in catalyzer described in 1mol, the consumption of described sodium hydroxide is 1-100mol, more preferably 8-50mol.
According to the present invention, although the temperature and time of contact can not produce obvious impact to the effect removing described catalyzer, but, in order to avoid there is the degraded of polyisoprene and improving the efficiency removing described catalyzer, under preferable case, described Contact Temperature is 0-80 DEG C, and the time of contact is 5-60min; More preferably, described duration of contact is 5-60min, and the time of contact is 10-20min.
According to the present invention, the mode that the described polyisoprene solution containing catalyzer contacts with aqueous sodium hydroxide solution can be various mode known in the field, such as, the described polyisoprene solution containing catalyzer can be mixed mutually with aqueous sodium hydroxide solution.
According to the present invention, under preferable case, the treatment process of the polyisoprene solution containing catalyzer provided by the invention is included in ultrasonic mixer 1, the described polyisoprene solution containing catalyzer is contacted with aqueous sodium hydroxide solution; Described ultrasonic mixer 1 comprises the cavity 3 with entrance 1 and outlet 2 and the multiple ultrasonic generators 4 be arranged on cavity 3 wall, described ultrasonic generator 4 comprises ultrasonic transducer 5, and the ultrasonic emitting of described ultrasonic transducer 56 probes in cavity 3; The ultrasonic frequency having at least two ultrasonic generators 4 to launch is different.
The number of the present invention to the ultrasonic generator 4 in described ultrasonic mixer is not particularly limited, but consider from the effect and cost removing described catalyzer, under preferable case, the number of described ultrasonic generator 4 is 2-6, more preferably 3-4; Adopt ultrasonic mixer provided by the invention by means of only the shorter time and consume small amount aqueous sodium hydroxide solution just can by the catalyzer in described polyisoprene solution abundant inactivation.
According to the present invention, the ultrasonic frequency that described ultrasonic generator 4 is launched can change in a big way, as long as ensure that the ultrasonic frequency having at least two ultrasonic generators 4 to launch is different, is preferably multiple all not identical.Described ultrasonic frequency is preferably 15KHz-1MHz, more preferably 20-600KHz, is more preferably 20-60KHz.
According to the present invention, described ultrasonic generator 4 can be fixed on the wall of described ultrasonic mixer in any way, such as, can by being fixedly connected with, as riveted joint, bolt connection etc.
The shape of the present invention to described cavity 3 is not particularly limited, as long as the polyisoprene solution can held containing catalyzer and aqueous sodium hydroxide solution, and ultrasonic wave can be made to act on its generation.Such as, according to one of the present invention preferred embodiment, described cavity 3 is rectangular parallelepiped or square, multiple ultrasonic transducer 5 can be arranged on the same wall of cavity 3, also can be separately positioned on multiple walls of cavity 3, but sound field, the raising contact effect in order to strengthen described ultrasonic mixer further.Under preferable case, as shown in Figure 1, described multiple ultrasonic transducer 5 is separately positioned on two relative walls of cavity 3, and further preferably not coaxial the and multiple ultrasonic emitting of the ultrasonic emitting 6 of any two ultrasonic transducers 56 be staggered.
According to the present invention, described entrance 1 and outlet 2 also can be arranged on the optional position of described cavity 3, there is no and distinguishingly limit, as long as the polyisoprene solution containing catalyzer and aqueous sodium hydroxide solution can be made to introduce in cavity 3, can draw in cavity after contact.But in order to improve the effect of contact, under preferable case, described entrance 1 lays respectively on two relative walls of cavity 3 with outlet 2.As mentioned above, under preferable case, when described cavity 3 be rectangular parallelepiped or square time, multiple ultrasonic transducer 5 is arranged on two relative walls of cavity 3 (as described in cavity there is four sidewalls, a diapire, and have uncovered, two relative sidewalls can be arranged on; As described in cavity there are four sidewalls, diapire and roofs, two relative sidewalls can be arranged on and also can be arranged on relative roof and diapire), when then described entrance 1 and outlet 2 are preferably separately positioned on two other wall of rectangular parallelepiped or square cavity 3, described catalyst deactivation effect can be made even more ideal.
According to another preferred embodiment of the present invention, as shown in Figure 2, described cavity 3 is right cylinder, under preferable case, described multiple ultrasonic transducer 5 is all positioned at same plane, and the ultrasonic emitting of ultrasonic transducer 56 is staggered, and the ultrasonic emitting of any two ultrasonic transducers 56 is not coaxial; Described entrance 1 and outlet 2 can lay respectively at the two ends of cavity 3.
According to the present invention, described polyisoprene solution containing catalyzer and the contact of aqueous sodium hydroxide solution in ultrasonic mixer can continous way also can intermittent type.Described continous way is and is passed into described ultrasonic mixer from the entrance 1 of ultrasonic mixer with certain liquid hourly space velocity by the mixed solution of the polyisoprene solution containing catalyzer and aqueous sodium hydroxide solution, make catalyst deactivation under hyperacoustic acting in conjunction of multiple frequency after, draw from outlet with above-mentioned liquid hourly space velocity, then carry out the process of subsequent step.Described intermittent type is and adds a certain amount of in ultrasonic mixer containing the polyisoprene solution of catalyzer and the mixed solution of aqueous sodium hydroxide solution simultaneously, make catalyst deactivation under hyperacoustic acting in conjunction of multiple frequency after, draw from outlet, then carry out the process of subsequent step.
According to the present invention, the ultrasonic emitting of described ultrasonic transducer 56 stretches in cavity 3, then extend into ultrasonic emitting in described cavity 36 and can not only launch ultrasonic wave, also serve baffle effect simultaneously, be conducive to fully mixing of described polyisoprene solution and aqueous sodium hydroxide solution.The present inventor studies discovery, and when described ultrasonic emitting 6 length stretched in ultrasonic mixer are the 1/4-3/4 of the height of described cavity 3 or width or diameter, speed and the effect of removing described catalyzer are all fabulous.
According to the present invention, the ultrasonic emitting of any one ultrasonic transducer 56 frequency of launching and different from the frequency of this ultrasonic emitting other adjacent ultrasonic emitting heads, the difference on the frequency of the two is at least 5KHz, is preferably 10-20KHz.
According to the present invention, described ultrasonic transducer 5 can be various ultrasonic transducer well known in the art, as long as ultrasonic wave can be passed to the material in cavity through ultrasonic emitting head, such as, described ultrasonic transducer 5 can be piezoelectric type, magnetostriction type, electromagnetic type and hydrokinetic type etc., is more preferably piezoelectric-type ultrasonic wave transducer.
As a rule, ultrasonic transducer 5 can be connected with the ultrasonic power of exterior arrangement by cable by terminal box, ultrasonic wave to be sent to material in ultrasonic mixer by by stretching into ultrasonic emitting in ultrasonic mixer 6 by described ultrasonic transducer 5, polyisoprene solution so not only can be made to mix with aqueous sodium hydroxide solution more even, hyperacoustic " cavitation effect " can also be utilized to accelerate catalyst activity component residual in polyisoprene solution and the speed of response of sodium hydroxide.
According to the present invention, the treatment process of described polyisoprene solution also comprises the mixed solution after the polyisoprene solution containing catalyzer being contacted with aqueous sodium hydroxide solution and carries out oily water separation, and removes the step of the organic solvent in the oil phase obtained.The method of described oily water separation and the method for removal organic solvent can be the method for existing various oily water separation and the method for removal organic solvent, such as, polyisoprene solution after contacting with aqueous sodium hydroxide solution can be introduced stratification in layering tank, and isolate oil phase; Again oil phase is introduced air lift still removing organic solvent.
Also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
By the following examples the present invention is described in further detail, but these embodiments should not think limitation of the scope of the invention.
In embodiment and comparative example, in the polyisoprene obtained, the content of titanium and aluminium is by inductively coupled plasma atomic emission spectrometer (IRIS/AP type; Be purchased from company of Thermo Electron Corp.) measure; Wherein, the correlation parameter of this instrument is as follows: high frequency power: 1150W; Assisted gas flow velocity: 0.5L/min; Wriggling pump speed: 100 turns/min; Integral time: 10s; Nebulizer gas pressure: 32.06psi; Sample size: 1.85mL/min.
Ash content in embodiment and comparative example measures by the following method: take 2g sample in porcelain crucible, and be placed in cascade raising temperature to 450 DEG C in high temperature resistance furnace, ashing was taken out after 1 hour, add 5mL hydrochloric acid, on hot plate, slowly solution, until ash content dissolves completely, steams to dry to the greatest extent, adds 3mL hydrochloric acid by heating, proceed in 50mL volumetric flask, and carry out constant volume with water.
Mooney viscosity in embodiment and comparative example is measured by automatic mooney's viscosimeter (SMV-300 type, is purchased from Shimadzu Corporation), and probe temperature is 100 DEG C.
Embodiment 1
The present embodiment is for illustration of the treatment process of polyisoprene solution provided by the invention.
(1) preparation of polyisoprene solution:
Under nitrogen protection, in the reactor of 5L, add 1490g hexane, 350g isoprene (IP), and add catalyzer TiCl
4(relative to 1mol isoprene, the add-on of three is respectively 1.0 × 10 to/triisobutyl aluminium/phenyl ether
-3mol, 1.0 × 10
-3mol, 0.5 × 10
-3mol) hexane solution 104g, is uniformly mixed.React 2 hours at 20 DEG C, obtain 1944g polyisoprene solution, wherein, with the gross weight of the polyisoprene solution containing catalyzer for benchmark, the content of polyisoprene is 16 % by weight.
(2) process of polyisoprene solution:
At 20 DEG C, in ultrasonic mixer as shown in Figure 1, the aqueous sodium hydroxide solution being 0.5 % by weight by the polyisoprene solution containing catalyzer and the 2000g concentration of step (1) gained contacts 10min.Wherein, the ultrasonic generator 4 that described ultrasonic mixer is respectively 20KHz, 60KHz, 600KHz by three frequencies forms, described ultrasonic generator 4 is arranged on the wall of cavity 3 of rectangular parallelepiped, and these three ultrasonic transducers 5 are staggered respectively on two relative walls of cavity 3; Ultrasonic emitting 6 length probeed in cavity 3 are 1/2 of cavity 3 height.Solution after contacting with sodium hydroxide is introduced layering tank after standing 30 minutes, and by oil phase and aqueous phase separation, then the oil phase that will obtain introduces air lift still removal organic solvent, and vacuum drying, obtains removing traces of catalyst and stable polyisoprene.
The content measuring metal titanium in isolated polymkeric substance is 184ppm, and the content of aluminium is 95ppm, and ash content is 0.35 % by weight, and mooney viscosity is 75.
Embodiment 2
The present embodiment is for illustration of the treatment process of polyisoprene solution provided by the invention.
(1) preparation of polyisoprene solution: under nitrogen protection, adds 1880g hexane in the reactor of 5L, 350g isoprene (IP), and adds catalyzer TiCl
4(relative to 1mol isoprene, the add-on of three is respectively 1.0 × 10 to/triisobutyl aluminium/phenyl ether
-3mol, 1.0 × 10
-3mol, 0.5 × 10
-3mol) hexane solution 103.3g, is uniformly mixed.React 2 hours at 20 DEG C, obtain 2333.3g polyisoprene solution, wherein, with the gross weight of the polyisoprene solution containing catalyzer for benchmark, the content of polyisoprene is 12 % by weight.
(2) process of polyisoprene solution:
At 10 DEG C, in ultrasonic mixer, the aqueous sodium hydroxide solution being 0.8 % by weight by the polyisoprene solution containing catalyzer and the 2500g concentration of step (1) gained contacts 20min.Wherein, the ultrasonic generator 4 that the transducer group of described ultrasonic mixer is respectively 20KHz, 40KHz, 60KHz by three operating frequencies forms, described ultrasonic generator 4 is arranged on the wall of cavity 3 of square, and these three ultrasonic transducers 5 are staggered respectively on two relative walls of cavity 3; Ultrasonic emitting 6 length probeed in cavity 3 are 3/4 of cavity 3 height.Solution after contacting with sodium hydroxide is introduced layering tank after standing 30 minutes, and by oil phase and aqueous phase separation, then the oil phase that will obtain introduces air lift still removal organic solvent, and vacuum drying, obtains removing traces of catalyst and stable polyisoprene.
The content measuring metal titanium in isolated polymkeric substance is 96ppm, and the content of aluminium is 54ppm, and ash content is 0.24 % by weight, and mooney viscosity is 83.
Embodiment 3
The present embodiment is for illustration of the treatment process of polyisoprene solution provided by the invention.
(1) preparation of polyisoprene solution: under nitrogen protection, adds 2240g hexane in the reactor of 5L, 350g isoprene (IP), and adds catalyzer TiCl
4(relative to 1mol isoprene, the add-on of three is respectively 1.0 × 10 to/triisobutyl aluminium/phenyl ether
-3mol, 1.0 × 10
-3mol, 0.5 × 10
-3mol) hexane solution 102.3g, is uniformly mixed.React 2 hours at 20 DEG C, obtain 2692.3g polyisoprene solution, wherein, with the gross weight of the polyisoprene solution containing catalyzer for benchmark, the content of polyisoprene is 10 % by weight.
(2) process of polyisoprene solution:
At 50 DEG C, in ultrasonic mixer, the aqueous sodium hydroxide solution being 0.54 % by weight by the polyisoprene solution containing catalyzer and the 2800g concentration of step (1) gained contacts 30min.Wherein, the ultrasonic generator 4 that the transducer group of described ultrasonic mixer is respectively 20KHz, 30KHz, 50KHz by three operating frequencies forms, described ultrasonic generator 4 is arranged on the wall of cylindrical cavity 3, and these three ultrasonic transducers 5 are all positioned at same plane, and ultrasonic emitting 6 is staggered; Ultrasonic emitting 6 length probeed in cavity 3 are 2/3 of cavity 3 diameter.Solution after contacting with sodium hydroxide is introduced layering tank after standing 30 minutes, and by oil phase and aqueous phase separation, then the oil phase that will obtain introduces air lift still removal organic solvent, and vacuum drying, obtains removing traces of catalyst and stable polyisoprene.
The content measuring metal titanium in isolated polymkeric substance is 65ppm, and the content of aluminium is 46ppm, and ash content is 0.21 % by weight, and mooney viscosity is 85.
Embodiment 4
The present embodiment is for illustration of the treatment process that the invention provides polyisoprene solution.
(1) preparation of polyisoprene solution: under nitrogen protection, adds 1600g hexane in the reactor of 5L, 350g isoprene (IP), and adds catalyzer TiCl
4(relative to 1mol isoprene, the add-on of three is respectively 1.0 × 10 to/triisobutyl aluminium/phenyl ether
-3mol, 1.0 × 10
-3mol, 0.5 × 10
-3mol) hexane solution 108.8g, is uniformly mixed.React 2 hours at 20 DEG C, obtain 2058.8g polyisoprene solution, wherein, with the gross weight of the polyisoprene solution containing catalyzer for benchmark, the content of polyisoprene is 15 % by weight.
(2) process of polyisoprene solution:
At 60 DEG C, in ultrasonic mixer, the aqueous sodium hydroxide solution being 0.17 % by weight by the polyisoprene solution containing catalyzer and the 1800g concentration of step (1) gained contacts 60min.Wherein, the ultrasonic generator 4 that the transducer group of described ultrasonic mixer is respectively 30KHz, 50KHz, 80KHz, 100KHz, 200KHz by five operating frequencies forms, described ultrasonic generator 4 is arranged on the wall of cavity 3 of rectangular parallelepiped, and these five ultrasonic transducers 5 are staggered respectively on two relative walls of cavity 3; Ultrasonic emitting 6 length probeed in cavity 3 are 3/4 of cavity 3 height.Solution after contacting with sodium hydroxide is introduced layering tank after standing 30 minutes, and by oil phase and aqueous phase separation, then the oil phase that will obtain introduces air lift still removal organic solvent, and vacuum drying, obtains removing traces of catalyst and stable polyisoprene.
The content measuring metal titanium in isolated polymkeric substance is 156ppm, and the content of aluminium is 87ppm, and ash content is 0.21 % by weight, and mooney viscosity is 81.
Embodiment 5
The present embodiment is for illustration of the treatment process that the invention provides polyisoprene solution.
(1) preparation of polyisoprene solution: under nitrogen protection, adds 1838g hexane in the reactor of 5L, 350g isoprene (IP), and adds catalyzer TiCl
4(relative to 1mol isoprene, the add-on of three is respectively 1.0 × 10 to/triisobutyl aluminium/phenyl ether
-3mol, 1.0 × 10
-3mol, 0.5 × 10
-3mol) hexane solution 312g, is uniformly mixed.React 2 hours at 20 DEG C, obtain 2500g polyisoprene solution, wherein, with the gross weight of the polyisoprene solution containing catalyzer for benchmark, the content of polyisoprene is 10 % by weight.
(2) process of polyisoprene solution:
At 80 DEG C, in ultrasonic mixer, the aqueous sodium hydroxide solution being 0.1 % by weight by the polyisoprene solution containing catalyzer and the 500g concentration of step (1) gained contacts 30min.Wherein, the ultrasonic generator 4 that the transducer group of described ultrasonic mixer is respectively 20KHz, 35KHz, 60KHz, 100KHz, 200KHz, 500KHz by six operating frequencies forms, described ultrasonic generator 4 is arranged on the wall of cavity 3 of rectangular parallelepiped, and these six ultrasonic transducers 5 are staggered respectively on two relative walls of cavity 3; Ultrasonic emitting 6 length probeed in cavity 3 are 2/3 of cavity 3 height.Solution after contacting with sodium hydroxide is introduced layering tank after standing 30 minutes, and by oil phase and aqueous phase separation, then the oil phase that will obtain introduces air lift still removal organic solvent, and vacuum drying, obtains removing traces of catalyst and stable polyisoprene.
The content measuring metal titanium in isolated polymkeric substance is 285ppm, and the content of aluminium is 145ppm, and ash content is 0.33 % by weight, and mooney viscosity is 69.
Embodiment 6
The present embodiment is for illustration of the treatment process that the invention provides polyisoprene solution.
(1) preparation of polyisoprene solution: under nitrogen protection, adds 1250g hexane in the reactor of 5L, 350g isoprene (IP), and adds catalyzer TiCl
4(relative to 1mol isoprene, the add-on of three is respectively 1.0 × 10 to/triisobutyl aluminium/phenyl ether
-3mol, 1.0 × 10
-3mol, 0.5 × 10
-3mol) hexane solution 150g, is uniformly mixed.React 2 hours at 20 DEG C, obtain 1750g polyisoprene solution, wherein, with the gross weight of the polyisoprene solution containing catalyzer for benchmark, the content of polyisoprene is 17 % by weight.
(2) process of polyisoprene solution:
At 30 DEG C, in ultrasonic mixer, the aqueous sodium hydroxide solution being 0.41 % by weight by the polyisoprene solution containing catalyzer and the 2500g concentration of step (1) gained contacts 30min.Wherein, the ultrasonic generator 4 that the transducer group of described ultrasonic mixer is respectively 20KHz, 30KHz, 45KHz, 60KHz by four operating frequencies forms, described ultrasonic generator 4 is arranged on the wall of cavity 3 of rectangular parallelepiped, and these four ultrasonic transducers 5 are staggered respectively on two relative walls of cavity 3; Ultrasonic emitting 6 length probeed in cavity 3 are 2/3 of cavity 3 height.Solution after contacting with sodium hydroxide is introduced layering tank after standing 30 minutes, and by oil phase and aqueous phase separation, then the oil phase that will obtain introduces air lift still removal organic solvent, and vacuum drying, obtains removing traces of catalyst and stable polyisoprene.
The content measuring metal titanium in isolated polymkeric substance is 105ppm, and the content of aluminium is 78ppm, and ash content is 0.23 % by weight, and mooney viscosity is 84.
Embodiment 7
The present embodiment is for illustration of the treatment process that the invention provides polyisoprene solution.
According to the method process polyisoprene solution of embodiment 2, unlike, the ultrasonic generator 4 that the transducer group of ultrasonic mixer used is respectively 20KHz, 40KHz, 200KHz by three operating frequencies forms.The content measuring metal titanium in isolated polymkeric substance is 132ppm, and the content of aluminium is 82ppm, and ash content is 0.22 % by weight, and mooney viscosity is 82.
Embodiment 8
The present embodiment is for illustration of the treatment process that the invention provides polyisoprene solution.
According to the method process polyisoprene solution of embodiment 2, unlike, the ultrasonic generator 4 that the transducer group of ultrasonic mixer used is respectively 20KHz, 40KHz by two operating frequencies forms.The content measuring metal titanium in isolated polymkeric substance is 286ppm, and the content of aluminium is 151ppm, and ash content is 0.35 % by weight, and mooney viscosity is 68.
Comparative example 1
This comparative example is for illustration of the treatment process of reference polyisoprene solution.
Prepare polyisoprene solution according to the method for embodiment 4 and described polyisoprene solution is processed, unlike, when processing described polyisoprene solution, the contact of polyisoprene solution and aqueous sodium hydroxide solution is carry out under the mechanical stirring of 300r/min at rotating speed.
The content measuring metal titanium in isolated polymkeric substance is 1282ppm, and the content of aluminium is 887ppm, and ash content is 0.98 % by weight, and mooney viscosity is 46.
Comparative example 2
This comparative example is for illustration of the treatment process of reference polyisoprene solution.
Prepare polyisoprene solution according to the method for embodiment 4 and described polyisoprene solution is processed, unlike, the ultrasonic frequency of described ultrasonic generator 4 is 100KHz.
The content measuring metal titanium in isolated polymkeric substance is 713ppm, and the content of aluminium is 524ppm, and ash content is 0.71 % by weight, and mooney viscosity is 58.
Table 1
Result as can be seen from table, method of the present invention is adopted to process the polyisoprene solution containing catalyzer, metal titanium in the polymkeric substance obtained, the content of metallic aluminium are all lower, ash content is also lower, mooney viscosity is higher, as can be seen here, treatment process of the present invention described catalyzer can be carried out well inactivation and remove, respond well, and the ageing-resistant performance of polymkeric substance can not be affected.
Claims (22)
1. the treatment process of the polyisoprene solution containing catalyzer, described catalyzer is halogenated titanium and aluminum alkyls and the interactional product of electron donor, it is characterized in that, under the method is included in hyperacoustic acting in conjunction of multiple frequency, the described polyisoprene solution containing catalyzer is contacted with aqueous sodium hydroxide solution, makes described catalyst deactivation.
2. treatment process according to claim 1, wherein, described hyperacoustic number of frequencies is 2-6; Hyperacoustic difference on the frequency of any two different frequencies is at least 5KHz.
3. treatment process according to claim 2, wherein, described hyperacoustic number of frequencies is 3-4.
4. treatment process according to claim 2, wherein, hyperacoustic difference on the frequency of any two different frequencies is 10KHz-20KHz.
5. according to the treatment process in claim 1-4 described in any one, wherein, described hyperacoustic frequency is 15KHz-1MHz.
6. treatment process according to claim 5, wherein, described hyperacoustic frequency is 20KHz-600KHz.
7. treatment process according to claim 1, wherein, the concentration of described aqueous sodium hydroxide solution is 0.1-1 % by weight.
8. treatment process according to claim 1, wherein, the condition of described contact comprises: in the metal titanium in catalyzer described in 1mol, and the consumption of described sodium hydroxide is 1-100mol; The temperature of contact is 0-80 DEG C; The time of contact is 5-60min.
9. treatment process according to claim 8, wherein, in the metal titanium in catalyzer described in 1mol, the consumption of described sodium hydroxide is 8-50mol.
10. treatment process according to claim 8, wherein, the temperature of contact is 30-60 DEG C.
11. treatment processs according to claim 8, wherein, the time of contact is 10-20min.
12. treatment processs according to claim 1, wherein, the method is included in ultrasonic mixer, the described polyisoprene solution containing catalyzer is contacted with aqueous sodium hydroxide solution; Described ultrasonic mixer comprises the cavity (3) with entrance (1) and outlet (2) and the multiple ultrasonic generators (4) be arranged on cavity (3) wall, described ultrasonic generator (4) comprises ultrasonic transducer (5), and the ultrasonic emitting head (6) of described ultrasonic transducer (5) probes in cavity (3); The ultrasonic frequency having at least two ultrasonic generators (4) to launch is different.
13. treatment processs according to claim 12, wherein, the number of described ultrasonic generator (4) is 2-6; The ultrasonic frequency that described ultrasonic generator (4) is launched is 15KHz-1MHz.
14. treatment processs according to claim 13, wherein, the number of described ultrasonic generator (4) is 3-4.
15. treatment processs according to claim 13, wherein, the ultrasonic frequency that described ultrasonic generator (4) is launched is 20KHz-600KHz.
16. according to the treatment process in claim 13-15 described in any one, wherein, described cavity (3) is rectangular parallelepiped or square, and multiple ultrasonic transducer (5) is separately positioned on two relative walls of cavity (3), and the ultrasonic emitting head (6) of ultrasonic transducer (5) is staggered, and the ultrasonic emitting head (6) of any two ultrasonic transducers (5) is not coaxial; Described entrance (1) lays respectively on two relative walls of cavity (3) with outlet (2).
17. treatment processs according to claim 16, wherein, ultrasonic emitting head (6) length probeed in cavity (3) of described ultrasonic transducer (5) is the 1/4-3/4 of cavity (3) height or width.
18. according to the treatment process in claim 13-15 described in any one, wherein, described cavity (3) is right cylinder, and multiple ultrasonic transducer (5) is all positioned at same plane, and the ultrasonic emitting head (6) of ultrasonic transducer (5) is staggered, and the ultrasonic emitting head (6) of any two ultrasonic transducers (5) is not coaxial; Described entrance (1) and outlet (2) lay respectively at the two ends of cavity (3).
19. treatment processs according to claim 18, wherein, ultrasonic emitting head (6) length probeed in cavity (3) of described ultrasonic transducer (5) is the 1/4-3/4 of cavity (3) diameter.
20. according to the treatment process in claim 13-15 described in any one, wherein, the frequency that the ultrasonic emitting head (6) of any one ultrasonic transducer (5) is launched and different from the frequency of this ultrasonic emitting other adjacent ultrasonic emitting heads, the difference on the frequency of the two is at least 5KHz.
21. treatment processs according to claim 20, wherein, the frequency that the ultrasonic emitting head (6) of any one ultrasonic transducer (5) is launched and different from the frequency of this ultrasonic emitting other adjacent ultrasonic emitting heads, the difference on the frequency of the two is 10KHz-20KHz.
22. treatment processs according to claim 1 or 12, wherein, the method also comprise the polyisoprene solution containing catalyzer is contacted with aqueous sodium hydroxide solution after the mixed solution that obtains carry out oily water separation, and remove the step of the organic solvent in the oil phase obtained.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1317507A (en) * | 1970-08-08 | 1973-05-23 | Bayer Ag | Processing catalyst-containing polyisoprene solutions |
| SU689212A1 (en) * | 1976-09-01 | 1992-02-28 | V P Alekseenko | Method of obtaining cis-1,4-polyisoprene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1317507A (en) * | 1970-08-08 | 1973-05-23 | Bayer Ag | Processing catalyst-containing polyisoprene solutions |
| SU689212A1 (en) * | 1976-09-01 | 1992-02-28 | V P Alekseenko | Method of obtaining cis-1,4-polyisoprene |
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