CN103665217B - A kind of continuous polymerization method - Google Patents
A kind of continuous polymerization method Download PDFInfo
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Abstract
The invention provides a kind of continuous polymerization method, the method comprises: (1) in the presence of an inert organic solvent, by carboxylic acid neodymium, alkylaluminium cpd and conjugated diene Continuous Contact in the first reactor, obtain product of contact, and by described product of contact and halogen contained compound Continuous Contact in the second reactor, obtain mixture, the more continuous ageing in tubular reactor of described mixture is obtained rare earth catalyst; (2) rare earth catalyst under the polymerization conditions, conjugated diene, step (1) obtained is sent in polymerized unit continuously with inert organic solvents and is contacted.Adopt the method for successive polymerization provided by the invention, the molecular weight of the polymkeric substance obtained can be made and distribution is comparatively stable, fluctuation is less and performance is comparatively stable.In addition, this continuous polymerization method is integrated continuously with polyreaction by Kaolinite Preparation of Catalyst, improves production efficiency, reduces labour intensity and production cost, have prospects for commercial application.
Description
Technical field
The present invention relates to a kind of continuous polymerization method.
Background technology
Compared with lithium system, nickel system, titanium system, cobalt system cis-1,4-polybutadiene rubber, the cis-1,4-polybutadiene rubber adopting rare earth catalyst to prepare has the highest cis-structure and minimum vinyl units, the degree of branching is very little, macromolecular chain is made to have very high regularity and perfect linear structure, give rare earth polybutadiene rubber high strength, high abrasion with good dynamic properties, with ensure by its obtained tire at a high speed, energy-conservation, safety, development in environmental protection etc. needs, be specially adapted to tread rubber and sidewall rubber.Therefore, rare earth polybutadiene rubber is considered to the best a kind of cis-1,4-polybutadiene rubber of development prospect, achieves suitability for industrialized production in the country such as Italian, German, Russian.
At present, the method preparing rare earth catalyst is all the mode adopting interval ageing without exception.Such as, CN101045768A discloses a kind of rare earth catalyst and preparation method thereof, and the preparation method specifically disclosing described catalyzer is included in ageing container and adds rare earth organic compounds, conjugated diolefin and aluminum alkyls successively, react after 1-10 minute, then add muriate continue reaction be 5 minutes to 24 hours.Company of Michelin discloses a kind of Synthetic polyisoprene and its preparation method in CN1479754A; Wherein, rare earth catalyst used is made up of conjugated diolefin/RE phosphate/aluminum alkyls/halogenide, and its preparation method is comparatively complicated, is divided into seven stages, the temperature and time that each stage will be strict with, and catalyzer needs storage at-15 DEG C that final preparation is intact.But, adopt the mode Kaolinite Preparation of Catalyst of interval ageing that polymerisate performance will be made to produce fluctuation, this be due to: although the catalyzer of every batch all according to certain condition go preparation, but be difficult to control identical, thus the performance of the catalyzer obtained also be there are differences, and the performance of the polymkeric substance finally obtained is caused to produce larger fluctuation.
Summary of the invention
The object of this invention is to provide a kind of new continuous polymerization method.
The invention provides a kind of continuous polymerization method, the method comprises:
(1) in the presence of an inert organic solvent, by carboxylic acid neodymium, alkylaluminium cpd and conjugated diene Continuous Contact in the first tank reactor, obtain product of contact, and by described product of contact and halogen contained compound Continuous Contact in the second tank reactor, obtain mixture, the more continuous ageing in tubular reactor of described mixture is obtained rare earth catalyst;
(2) rare earth catalyst under the polymerization conditions, conjugated diene, step (1) obtained is sent in polymerized unit continuously with inert organic solvents and is contacted.
The present inventor finds, in the suitability for industrialized production of conjugated diene polymer, adopts the technique Kaolinite Preparation of Catalyst of interval, and prepares complete catalyzer and need to be stored in catalyzer storage tank, just can be finished after using for some time.During this period of time, still can react between catalyst components, its character is changed, thus cause producing in the process of conjugated diene polymer in successive polymerization, molecular weight and the distribution thereof of the polymeric articles that different time is produced change always, the polymkeric substance of these different molecular weights and distribution thereof mixes in glue tank or condensing field, and the product finally obtained is actual is a kind of mixture, shows as wider molecular weight distribution.But the wider molecular weight distribution of polymkeric substance can cause the vulcanized network of cross-linked rubber laxer, the density of network Elastic significant part declines, thus makes the reduction of the physical and mechanical properties of cross-linked rubber, limits its application.In addition, adopt the mode Kaolinite Preparation of Catalyst of interval ageing to bring inconvenience to production, as need be repeatedly carried out, catalyst preparation work, labour intensity are comparatively large, the loss that is very long, material of regulate expenditure higher, nonproductive operating time is larger.
Tank reactor and tubular reactor combine with continuous production rare earth catalyst by the present invention dexterously, described carboxylic acid neodymium can not only be ensured, alkylaluminium cpd, conjugated diene and halogen contained compound fully mix in tank reactor, reaction, obtain homogeneous system, and because tubular reactor is for being bulldozed flow reactor, in this tubular reactor, the mixture obtained after the first tank reactor fully contacts with the second tank reactor flows in tubular reactor with regime flow, parallelly to move forward, back-mixing is there is hardly on the direction of material movement, thus can ensure that reaction mass particle is equal to the time (i.e. the particle residence time in the reactor) leaving reactor from entering reactor.Therefore, four kinds of components of described rare earth catalyst can fully ageing, reaction, obtain the catalyzer of stable in properties.The catalyzer of the stable in properties obtained by continuous production is again sent in polymerization reaction system, and the performance inconsistency of the polymkeric substance obtained is less.A preferred embodiment of the invention, when the length-to-diameter ratio of described tubular reactor is 20-50:1, the performance of the polymkeric substance obtained is more stable.In addition, continuous polymerization method of the present invention by catalyst preparation process and polymerization technique integrated continuously, thus not only increase production efficiency, reduce labour intensity, decrease process cost, but also easily realize automatic production, obtain the polymerisate of stable performance, have prospects for commercial application.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.
Fig. 1 is the schematic flow sheet of continuous polymerization method provided by the invention.
Description of reference numerals
1-first tank reactor; 2-second tank reactor; 3-tubular reactor.
Embodiment
Below 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.
Continuous polymerization method provided by the invention comprises:
(1) in the presence of an inert organic solvent, by carboxylic acid neodymium, alkylaluminium cpd and conjugated diene Continuous Contact in the first tank reactor, obtain product of contact, and by described product of contact and halogen contained compound Continuous Contact in the second tank reactor, obtain mixture, the more continuous ageing in tubular reactor of described mixture is obtained rare earth catalyst;
(2) rare earth catalyst under the polymerization conditions, conjugated diene, step (1) obtained is sent in polymerized unit continuously with inert organic solvents and is contacted.
According to the present invention, from the angle being convenient to describe, call " the first tank reactor " by the tank reactor of carboxylic acid neodymium, alkylaluminium cpd and conjugated diene Continuous Contact, call " the second tank reactor " by the tank reactor of described product of contact and halogen contained compound Continuous Contact.The kind of described tank reactor is known to the skilled person, and can be the tank reactor that existing various band stirs, will repeat no more at this.
In the present invention, described first tank reactor and the second tank reactor can take external jacket to carry out temperature control operation, such as, the temperature in tank reactor can be controlled in required scope by the circulatory mediator in chuck.Described circulatory mediator comprises heating medium and heat-eliminating medium, and the kind of described heating medium and heat-eliminating medium is known to the skilled person, and such as, the specific examples of described heating medium includes but not limited to hot water; The specific examples of described heat-eliminating medium includes but not limited to mixture of ice and water and chilled brine, is preferably chilled brine.
According to the present invention, the kind of described tubular reactor is known to the skilled person, the present inventor finds through further investigation, when the length-to-diameter ratio of described tubular reactor is 20-50:1, when being preferably 30-45:1, material flow pattern is in the reactor closer to piston flow, and the activity of the rare earth catalyst obtained is higher.Further preferably, described tubular reactor is adiabatic reactor, is so not only more conducive to the abundant ageing between above-mentioned four kinds of components, reaction, forms the catalyzer that character is more stable, can also save energy.
According to the present invention, in step (1), as long as although by four of catalyzer kinds of components Continuous Contact in the first tank reactor and the second tank reactor according to the method described above, and rare earth catalyst of the present invention can be obtained by contacting the mixture continuous ageing in tubular reactor obtained, and the condition of contact and ageing is all not particularly limited.But in order to eliminate or reduce the impact that each component in air causes catalyst preparing, under preferable case, described contact and ageing are carried out all in an inert atmosphere.Described inert atmosphere refer to not with any one gas or the gaseous mixture of reactant and product generation chemical action, as one or more in nitrogen and periodic table of elements zero group gas.The condition of carboxylic acid neodymium, alkylaluminium cpd and conjugated diene Continuous Contact in the first tank reactor is also comprised temperature and time usually; described temperature can be selected in wider scope; under normal circumstances; in order to be beneficial to Homogeneous phase mixing between each component, reaction further; described temperature can be 30-80 DEG C, is preferably 40-60 DEG C.The prolongation of duration of contact is conducive to the dispersion that each component realizes molecular level, but considers effect and efficiency, and the described time can be 5-60min usually, is preferably 20-45min.
In like manner, by described product of contact and halogen contained compound, the condition of Continuous Contact in the second tank reactor also comprises temperature can be 0-40 DEG C, preferably 10-30 DEG C, and the time can be 5-120min, be preferably 20-45min.The condition of described mixture continuous ageing in tubular reactor also being comprised temperature can be 0-40 DEG C, preferably 10-30 DEG C, and the time can be 1-48 hour, be preferably 2-5 hour.
According to the present invention, in step (1), the range of choices of the consumption of carboxylic acid neodymium, alkylaluminium cpd, halogen contained compound and conjugated diene is wider, in order to optimize continuous polymerization method of the present invention further, for the present invention, the mol ratio of described carboxylic acid neodymium, alkylaluminium cpd, halogen contained compound and conjugated diene is preferably 1:15-30:2-4:8-30.
According to the present invention, the range of choices of the kind of described carboxylic acid neodymium is wider, and the carboxylic acid neodymium that this area is commonly used all can realize object of the present invention.For the present invention, in step (1), described carboxylic acid neodymium is preferably C
1-C
20carboxylic acid neodymium, be more preferably C
6-C
10carboxylic acid neodymium, be particularly preferably in neodymium naphthenate, neodymium octoate, neodymium iso-octanate, n-nonanoic acid neodymium, neodymium caprate and n-capric acid neodymium one or more.
According to the present invention, the range of choices of the kind of described alkylaluminium cpd is wider, and the alkylaluminium cpd that this area is commonly used all can realize object of the present invention.For the present invention, in step (1), described alkylaluminium cpd preferably has general formula AlR
3and/or AlHR
2alkylaluminium cpd, wherein, R is C
1-C
6alkyl; One or more more preferably in trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, triisobutyl aluminium, three amyl group aluminium, three hexyl aluminium, ADEH, dibutyl aluminum hydride and diisobutyl aluminium hydride of described alkylaluminium cpd, be more preferably in tri-butyl aluminum, triisobutyl aluminium, dibutyl aluminum hydride and diisobutyl aluminium hydride one or more, be particularly preferably triisobutyl aluminium and/or diisobutyl aluminium hydride.
According to the present invention, the range of choices of the kind of described halogen contained compound is wider, and the halogen contained compound that this area is commonly used all can realize object of the present invention.For the present invention, in step (1), described halogen contained compound preferably has general formula AlR
2the aikyl aluminum halide of X, there is general formula Al
2r
3x
3sesquialter aikyl aluminum halide, have general formula R X halohydrocarbon, there is general formula H
4-asi [(CH
2)
ny]
asilane in one or more.Wherein, R described in each general formula is ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, benzyl or allyl group independently of one another, X and Y is bromine or chlorine independently of one another, and n is the integer of 0-6,4 >=a >=1; Be more preferably in benzyl chloride, bromotoluene, tertiary butyl chloride, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium, sesquialter isobutyl-aluminum chloride, chloromethyl silane and tetrachloro silicane one or more.
According to the present invention, the range of choices of the kind of described conjugated diene is wider, and the conjugated diene that this area is commonly used all can realize object of the present invention.For the present invention, in step (1) and step (2), described conjugated diene is preferably C independently of one another
4-C
6conjugated diene, one or more more preferably in divinyl, isoprene, 1,3-pentadiene, 1,3-hexadiene and 2,3-dimethylbutadiene, are more preferably divinyl and/or isoprene, are particularly preferably divinyl.
According to the present invention, all object of the present invention can be realized according to preceding solution, consider the transformation efficiency of conjugated diene and the performance of resulting polymers, for the present invention, under preferable case, in step (2), described polymerized unit comprises the polymerization reaction kettle of at least 2 series connection, preferably include the polymerization reaction kettle of 3-10 series connection further, more preferably comprise the polymerization reaction kettle of 3-5 series connection.
Wherein, polymerization reaction kettle can take external jacket to carry out temperature control operation, such as, the temperature in polymerization reaction kettle can be controlled in required scope by the circulatory mediator (heating medium or heat-eliminating medium) in chuck.The heating medium used and the kind of heat-eliminating medium are known to the skilled person, and such as, the specific examples of described heating medium includes but not limited to hot water; The specific examples of described heat-eliminating medium includes but not limited to mixture of ice and water and chilled brine, is preferably chilled brine.
Those skilled in the art it is easily understood that, in order to rare earth catalyst step (1) obtained is continuously for the production of polymkeric substance in step (2), namely, the preparation realizing catalyzer is integrated continuously with the polymerization of conjugated diene, according to the flow direction of material, described tubular reactor and first polymerization reaction kettle are connected in series, thus step (1) is contacted the rare earth catalyst obtained directly send into polymerized unit.
According to the present invention, under preferable case, method of the present invention also comprises: under the polymerization conditions, before conjugated diene, rare earth catalyst and inert organic solvents are sent into continuously in polymerized unit and contacted, described conjugated diene, rare earth catalyst and inert organic solvents are carried out premix.The range of choices of the condition of described premix is wider, can according to the temperature and time of the flow choose reasonable premix of conjugated diene, rare earth catalyst and inert organic solvents, (5-40 DEG C) carries out premix 5-20min above-mentioned three kinds of components can be made to mix generally at normal temperatures.Described premix can carry out in traditional autoclave premixed device.In this case, according to the flow direction of material, described tubular reactor and autoclave premixed device are connected in series, and described autoclave premixed device is connected in series with first polymerization reaction kettle again, thus the preparation realizing catalyzer is integrated continuously with the polymerization of conjugated diene.Be known to the skilled person in specific implementation process, will no longer repeat at this.
According to the present invention, all object of the present invention can be realized according to preceding solution, in order to optimize continuous polymerization method of the present invention further, for the present invention, in preferred steps (2), described polymeric reaction condition comprises: the temperature in each polymerization reaction kettle is-30 DEG C to 80 DEG C independently of one another, is preferably 0-70 DEG C, is more preferably 10-60 DEG C; The time contacted in each polymerization reaction kettle is 10-90min independently of one another, is preferably 20-80min, is more preferably 30-60min; The total time contacted in each polymerization reaction kettle is no more than 300min, is preferably 90-180min, is more preferably 110-150min.
According to the present invention, the consumption of described rare earth catalyst suitably can be selected based on the principle of industrial economy, and as a rule, catalyst levels is less, then the molecular weight of the polymerisate obtained is larger, but rate of polymerization is slower; Catalyst levels is larger, then rate of polymerization is faster, but can increase cost, ash oontent in the polymerisate obtained also may be made to increase, be unfavorable for subsequent disposal or the application of described product.Therefore, combined factors is from every side considered, in every mole of conjugated diene for benchmark, the consumption of described rare earth catalyst is preferably 1 × 10
-5-4 × 10
-4molNd, is more preferably 1.5 × 10
-5-2.5 × 10
-4molNd.
According to the present invention, described inert organic solvents can be existing various not with the organic solvent of reactant and reaction product generation chemical action.Usually, the inert organic solvents in step (1) and step (2) can be identical or different, and be selected from one or more in aromatic hydrocarbons, saturated alkane and naphthenic hydrocarbon independently of one another; Particularly, benzene, toluene, ethylbenzene, dimethylbenzene (comprising o-Xylol, m-xylene and p-Xylol), pentane and isomer (such as: Skellysolve A, iso-pentane, methylcyclopentane, 2-methylpentane and 3-methylpentane) thereof, hexane and isomer (such as: normal hexane, hexanaphthene), heptane and isomer (such as: normal heptane) thereof, octane and isomer (such as: octane) thereof, hexanaphthene and one or more in raffinating oil can be selected from independently of one another.The consumption of described inert organic solvents can be the routine selection of this area, is not particularly limited.In general, in step (1), the consumption of described inert organic solvents can make in carboxylic acid neodymium, and the concentration of described rare earth catalyst is 1 × 10
-4-1 × 10
-2mol/L, to ensure to mix, steadily the carrying out and obtain the higher rare earth catalyst of activity of ageing process.In step (2), with the conjugated diene of 100 weight parts for benchmark, the consumption of inert organic solvents can be 400-900 weight part, so not only makes polyreaction steadily to carry out, but also can obtain higher productive rate.
According to the present invention, after polymerization was complete, the conventional various methods in this area can be adopted to make reactive polymer inactivation.Such as, living polymer chains can be lost activity by adding terminator in polymerization reaction system.The kind of described terminator and consumption can be that the routine of this area is selected, and are not particularly limited, as long as described terminator can make the polymer chain inactivation with active end group.Usually, described terminator can for being selected from water, C
1-C
6fatty alcohol, C
4-C
12aliphatic carboxylic acid, one or more in aryl polyol.Described aryl polyol refers to that the hydrogen atom on phenyl ring has at least two to be optionally substituted by a hydroxyl group generated compound.Preferably, described terminator is one or more in water, methyl alcohol, ethanol, Virahol and 2,6-di-tert-butyl hydroquinone.The present invention is not particularly limited for the consumption of described terminator, as long as the consumption of described terminator by the active specy inactivation in polymerisate, will be able to repeat no more at this.
Below in conjunction with accompanying drawing, brief description is carried out to continuous polymerization method of the present invention.As shown in Figure 1, first in the presence of an inert organic solvent, by carboxylic acid neodymium, alkylaluminium cpd and conjugated diene Continuous Contact in the first tank reactor 1, obtain product of contact, and by described product of contact and halogen contained compound Continuous Contact in the second tank reactor 2, obtain mixture, the more continuous ageing in tubular reactor 3 of described mixture is obtained rare earth catalyst; The described rare earth catalyst obtained is sent into polymerized unit continuously.Wherein, in described first tank reactor 1, second tank reactor 2 and polymerized unit, polymerization reaction kettle used is all taked in external jacket, pass into circulatory mediator and is carried out temperature control, realizes the preparation of catalyzer and the continuous prodution of conjugate diene polymerization thus.
Below will be described the present invention by embodiment.
In following examples and comparative example, the microtexture of synthesized polymerisate adopts the mid-infrared light spectrometer of German BrukerTensor27 and the nmr determination of German Bruker400MHz, and solvent is deuterochloroform; Mooney viscosity is measured by automatic mooney's viscosimeter (SMV-300 type, is purchased from Shimadzu Corporation), and probe temperature is 100 DEG C.
In following examples and comparative example, monomer conversion refers to the per-cent that conversion of monomer is polymkeric substance, is obtained, that is, by the weight of polymkeric substance with the ratio calculation entering the monomer weight being polymerized workshop section
Embodiment 1
This embodiment is for illustration of continuous polymerization method provided by the invention.
Be polymerized by the schema shown in Fig. 1:
(1) preparation of rare earth catalyst:
Under nitrogen protection; volume pump adds neodymium caprate/hexane solution that concentration is 0.01mol/L continuously in the first tank reactor 1, concentration is 0.1mol/L a hydrogen diisobutyl aluminum/hexane solution and concentration is adopted to be the divinyl/hexane solution of 0.05mol/L; control flow and be respectively 244mL/h, 366mL/h and 500mL/h; service temperature is 40 DEG C, and the residence time is 45min.After the first tank reactor 1 is full of material, adopt volume pump to start in the second tank reactor 2, add aluminium diethyl monochloride/hexane solution that concentration is 0.02mol/L continuously, flow is 280mL/h, and service temperature is 30 DEG C, and the residence time is 20min.Material enters adiabatic tubular reactor 3(length-to-diameter ratio after being full of the second tank reactor 2 be 30:1) in, the residence time is 5 hours, obtains the rare earth catalyst of pistac;
(2) preparation of cis-1,4-polybutadiene rubber:
Tubular reactor 3 is exported the described rare earth catalyst obtained, divinyl and hexane are (wherein, the flow of divinyl and hexane is respectively 16.2kg/h, 120kg/h) under normal temperature, carry out premix in continuous feeding autoclave premixed device and obtain reaction raw material, reaction raw material is sent into continuously four polymerization reaction kettles of series connection, in four polymerization reaction kettles, the residence time of material is 40min, logical circulatory mediator in each reactor jacket, by the first polymerization reaction kettle, second polymerization reaction kettle, trimerization reactor, the still temperature of the 4th polymerization reaction kettle controls at 30 DEG C respectively, 40 DEG C, 50 DEG C, 55 DEG C.After continuous seepage operates steadily, got a certain amount of glue every 4 hours from the 4th reactor outlet, after stopping, removing solvent, drying treatment, carry out analytical test.Continuous 24 sampling results are: monomer conversion is 89-92%, and the content of the suitable Isosorbide-5-Nitrae-structure of product is 98.6-98.8%, and weight-average molecular weight is 5.94 × 10
5-6.15 × 10
5, molecular weight distributing index is 2.61-2.67.In final mixing prod, the content along Isosorbide-5-Nitrae-structure is 98.7%, and weight-average molecular weight is 6.08 × 10
5, molecular weight distributing index is 2.66.
Embodiment 2
This embodiment is for illustration of continuous polymerization method provided by the invention.
Be polymerized by the schema shown in Fig. 1:
(1) preparation of rare earth catalyst:
Under nitrogen protection; volume pump adds neodymium caprate/hexane solution that concentration is 0.01mol/L continuously in the first tank reactor 1, concentration is 0.1mol/L a hydrogen diisobutyl aluminum/hexane solution and concentration is adopted to be the divinyl/hexane solution of 0.05mol/L; control flow and be respectively 366mL/h, 900mL/h and 2050mL/h; service temperature is 60 DEG C, and the residence time is 20min.After the first tank reactor 1 is full of material, adopt volume pump to start in the second tank reactor 2, add aluminium diethyl monochloride/hexane solution that concentration is 0.02mol/L continuously, flow is 680mL/h, and service temperature is 10 DEG C, and the residence time is 45min.Material enters adiabatic tubular reactor 3(length-to-diameter ratio after being full of the second tank reactor 2 be 45:1) in, the residence time is 2 hours, obtains the rare earth catalyst of pistac;
(2) preparation of cis-1,4-polybutadiene rubber:
Tubular reactor 3 is exported the described rare earth catalyst, divinyl and the hexane that obtain (wherein, the flow of divinyl and hexane is respectively 16.2kg/h, 120kg/h) send in autoclave premixed device continuously and under normal temperature, carry out premix obtain reaction raw material, reaction raw material is sent into continuously three polymerization reaction kettles of series connection, in three polymerization reaction kettles, the residence time of material is 40min, in each reactor jacket, logical circulatory mediator, controls at 30 DEG C, 50 DEG C, 60 DEG C respectively by the still temperature of the first polymerization reaction kettle, the second polymerization reaction kettle, trimerization reactor.After continuous seepage operates steadily, got a certain amount of glue every 4 hours from the 3rd reactor outlet, after stopping, removing solvent, drying treatment, carry out analytical test.Continuous 24 sampling results are: monomer conversion is 93-97%, and the content of the suitable Isosorbide-5-Nitrae-structure of product is 98.0-98.3%, and weight-average molecular weight is 5.04 × 10
5-5.22 × 10
5, molecular weight distributing index is 2.77-2.82.In final mixing prod, the content along Isosorbide-5-Nitrae-structure is 98.1%, and weight-average molecular weight is 5.09 × 10
5, molecular weight distributing index is 2.81.
Embodiment 3
This embodiment is for illustration of continuous polymerization method provided by the invention.
Be polymerized by the schema shown in Fig. 1:
(1) preparation of rare earth catalyst:
Under nitrogen protection; volume pump adds neodymium caprate/hexane solution that concentration is 0.01mol/L continuously in the first tank reactor 1, concentration is 0.1mol/L a hydrogen diisobutyl aluminum/hexane solution and concentration is adopted to be the divinyl/hexane solution of 0.05mol/L; control flow and be respectively 270mL/h, 400mL/h and 850mL/h; service temperature is 30 DEG C, and the residence time is 56min.After the first tank reactor 1 is full of material, adopt volume pump to start in the second tank reactor 2, add aluminium diethyl monochloride/hexane solution that concentration is 0.02mol/L continuously, flow is 400mL/h, and service temperature is 40 DEG C, and the residence time is 30min.Material enters adiabatic tubular reactor 3(length-to-diameter ratio after being full of the second tank reactor 2 be 20:1) in, the residence time is 12 hours, obtains the rare earth catalyst of pistac;
(2) preparation of cis-1,4-polybutadiene rubber:
Tubular reactor 3 is exported the described rare earth catalyst obtained, divinyl and hexane are (wherein, the flow of divinyl and hexane is respectively 14.5kg/h, 100kg/h) under normal temperature, carry out premix in continuous feeding autoclave premixed device and obtain reaction raw material, reaction raw material is sent into continuously four polymerization reaction kettles of series connection, in four polymerization reaction kettles, the residence time of material is 40min, logical circulatory mediator in each reactor jacket, by the first polymerization reaction kettle, second polymerization reaction kettle, trimerization reactor, the still temperature of the 4th polymerization reaction kettle controls at 30 DEG C respectively, 40 DEG C, 50 DEG C, 60 DEG C.After continuous seepage operates steadily, got a certain amount of glue every 4 hours from the 4th reactor outlet, after stopping, removing solvent, drying treatment, carry out analytical test.Continuous 24 sampling results are: monomer conversion is 85-88%, and the content of the suitable Isosorbide-5-Nitrae-structure of product is 98.1-98.3%, and weight-average molecular weight is 5.24 × 10
5-5.49 × 10
5, molecular weight distributing index is 2.71-2.80.In final mixing prod, the content along Isosorbide-5-Nitrae-structure is 98.1%, and weight-average molecular weight is 5.26 × 10
5, molecular weight distributing index is 2.82.
Embodiment 4
This embodiment is for illustration of continuous polymerization method provided by the invention.
Be polymerized by the schema shown in Fig. 1:
(1) preparation of rare earth catalyst:
Under nitrogen protection; volume pump adds neodymium naphthenate/hexane solution that concentration is 0.01mol/L continuously in the first tank reactor 1, concentration is 0.1mol/L a hydrogen diisobutyl aluminum/hexane solution and concentration is adopted to be the divinyl/hexane solution of 0.05mol/L; control flow and be respectively 270mL/h, 400mL/h and 850mL/h; service temperature is 80 DEG C, and the residence time is 7min.After the first tank reactor 1 is full of material, adopt volume pump to start in the second tank reactor 2, add aluminium diethyl monochloride/hexane solution that concentration is 0.02mol/L continuously, flow is 350mL/h, and service temperature is 5 DEG C, and the residence time is 120min.Material enters adiabatic tubular reactor 3(length-to-diameter ratio after being full of the second tank reactor 2 be 30:1) in, the residence time is 7 hours, obtains the rare earth catalyst of pistac;
(2) preparation of cis-1,4-polybutadiene rubber:
Tubular reactor 3 is exported the described rare earth catalyst obtained, divinyl and hexane are (wherein, the flow of divinyl and hexane is respectively 14.5kg/h, 100kg/h) under normal temperature, carry out premix in continuous feeding autoclave premixed device and obtain reaction raw material, reaction raw material is sent into continuously four polymerization reaction kettles of series connection, in four polymerization reaction kettles, the residence time of material is 40min, logical circulatory mediator in each reactor jacket, by the first polymerization reaction kettle, second polymerization reaction kettle, trimerization reactor, the still temperature of the 4th polymerization reaction kettle controls at 30 DEG C respectively, 40 DEG C, 50 DEG C, 60 DEG C.After continuous seepage operates steadily, got a certain amount of glue every 4 hours from the 4th reactor outlet, after stopping, removing solvent, drying treatment, carry out analytical test.Continuous 24 sampling results are: monomer conversion is 82-87%, and the content of the suitable Isosorbide-5-Nitrae-structure of product is 98.2-98.5%, and weight-average molecular weight is 5.01 × 10
5-5.27 × 10
5, molecular weight distributing index is 2.50-2.62.In final mixing prod, the content along Isosorbide-5-Nitrae-structure is 98.3%, and weight-average molecular weight is 5.08 × 10
5, molecular weight distributing index is 2.77.
Embodiment 5
This embodiment is for illustration of continuous polymerization method provided by the invention.
Successive polymerization reaction is carried out according to the method for embodiment 1, unlike, the length-to-diameter ratio of described tubular reactor 3 is 10:1.After continuous seepage operates steadily, got a certain amount of glue every 4 hours from the 4th reactor outlet, after stopping, removing solvent, drying treatment, carry out analytical test.Continuous 24 sampling results are: monomer conversion is 80-91%, and the content of the suitable Isosorbide-5-Nitrae-structure of product is 98.3-98.7%, and weight-average molecular weight is 5.66 × 10
5-6.17 × 10
5, molecular weight distributing index is 2.63-2.69.In final mixing prod, the content along Isosorbide-5-Nitrae-structure is 98.5%, and weight-average molecular weight is 5.97 × 10
5, molecular weight distributing index is 2.71.
Comparative example 1
This embodiment is for illustration of reference continuous polymerization method.
Cis-1,4-polybutadiene rubber is prepared according to the method for embodiment 1, unlike, described tubular reactor tank reactor substitutes.After continuous seepage operates steadily, got a certain amount of glue every 4 hours from the 4th reactor outlet, after stopping, removing solvent, drying treatment, carry out analytical test.Continuous 24 sampling results are: monomer conversion is 79-90%, and the content of the suitable Isosorbide-5-Nitrae-structure of product is 98.2-98.7%, and weight-average molecular weight is 4.86 × 10
5-6.74 × 10
5, molecular weight distributing index is 2.63-3.14.In final mixing prod, the content along Isosorbide-5-Nitrae-structure is 98.4%, and weight-average molecular weight is 5.41 × 10
5, molecular weight distributing index is 3.92.
Comparative example 2
This embodiment is for illustration of reference polymerization process.
(1) preparation of rare earth catalyst:
Rare earth catalyst is prepared according to the mol ratio between the order of addition(of ingredients) in embodiment 1, each component, temperature of reaction and reaction times, unlike, adopt the preparation method of interval.Be specially: under nitrogen protection; be the neodymium caprate/hexane solution of 0.01mol/L by 12.2L concentration, to add volume be in the tank reactor of 100L to the divinyl/hexane solution of 18.3L concentration to be the hydrogen diisobutyl aluminum/hexane solution of 0.1mol/L and 25L concentration be 0.05mol/L, at 40 DEG C, react 45min.Then after temperature of reactor being down to 30 DEG C, be that the aluminium diethyl monochloride/hexane solution of 0.02mol/L joins in this tank reactor by 14L concentration, react 5 hours 20 minutes, obtained homogeneous phase rare earth catalyst.
(2) preparation of cis-1,4-polybutadiene rubber:
The rare earth catalyst (flow is 1.39L/h) adopting the discontinuous method of step (1) to obtain, divinylic monomer (flow is 16.2kg/h) are sent into hexane (120kg/h) and be polymerized workshop section, continuous polymerization method is identical with embodiment 1.After continuous seepage operates steadily, got a certain amount of glue every 4 hours from the 4th reactor outlet, after stopping, removing solvent, drying treatment, carry out analytical test.Continuous 24 sampling results are: monomer conversion is 72-88%, and the content of the suitable Isosorbide-5-Nitrae-structure of product is 98.0-98.7%, and weight-average molecular weight is 4.12 × 10
5-7.28 × 10
5, molecular weight distributing index is 2.84-3.67.The content of the suitable Isosorbide-5-Nitrae-structure of final mixing prod is 98.2%, and weight-average molecular weight is 5.65 × 10
5, molecular weight distributing index is 4.52.
As can be seen from the contrast of embodiment 1-5 and comparative example 1-2, the molecular weight of the polymkeric substance obtained and distribution thereof are comparatively stable, fluctuation is less and performance is comparatively stable to adopt the method for successive polymerization provided by the invention to make.As can be seen from the contrast of embodiment 1 and embodiment 5, when the length-to-diameter ratio of described tubular reactor is in preferable range of the present invention, the performance of the polymkeric substance obtained is more stable.In addition, continuous polymerization method of the present invention by by catalyst preparation process and polymerization technique integrated continuously, not only increase production efficiency, reduce labour intensity, decrease process cost, and rise also easily realize automatic production, have prospects for commercial application.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, 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.
Claims (26)
1. a continuous polymerization method, the method comprises:
(1) in the presence of an inert organic solvent, by carboxylic acid neodymium, alkylaluminium cpd and the first conjugated diene Continuous Contact in the first tank reactor, obtain product of contact, and by described product of contact and halogen contained compound Continuous Contact in the second tank reactor, obtain mixture, the more continuous ageing in tubular reactor of described mixture is obtained rare earth catalyst;
(2) rare earth catalyst under the polymerization conditions, the second conjugated diene, step (1) obtained is sent in polymerized unit continuously with inert organic solvents and is contacted.
2. method according to claim 1, wherein, in step (1), it is 30-80 DEG C that the condition of carboxylic acid neodymium, alkylaluminium cpd and the first conjugated diene Continuous Contact in the first tank reactor is comprised temperature, and the time is 5-60min.
3. method according to claim 2, wherein, in step (1), it is 40-60 DEG C that the condition of carboxylic acid neodymium, alkylaluminium cpd and the first conjugated diene Continuous Contact in the first tank reactor is comprised temperature, and the time is 20-45min.
4. method according to claim 1, wherein, in step (1), by described product of contact and halogen contained compound, the condition of Continuous Contact in the second tank reactor comprises temperature is 0-40 DEG C, and the time is 5-120min.
5. method according to claim 4, wherein, in step (1), by described product of contact and halogen contained compound, the condition of Continuous Contact in the second tank reactor comprises temperature is 10-30 DEG C, and the time is 20-45min.
6. method according to claim 1, wherein, in step (1), it is 0-40 DEG C that the condition of described mixture continuous ageing in tubular reactor is comprised temperature, and the time is 1-48 hour.
7. method according to claim 6, wherein, in step (1), it is 10-30 DEG C that the condition of described mixture continuous ageing in tubular reactor is comprised temperature, and the time is 2-5 hour.
8. method according to claim 1, wherein, the length-to-diameter ratio of described tubular reactor is 20-50:1.
9. method according to claim 8, wherein, the length-to-diameter ratio of described tubular reactor is 30-45:1.
10. method according to claim 1, wherein, described tubular flow reactor is adiabatic reactor.
11. methods according to claim 1, wherein, in step (1), the mol ratio of carboxylic acid neodymium, alkylaluminium cpd, halogen contained compound and the first conjugated diene is 1:15-30:2-4:8-30.
12. methods according to claim 1, wherein, in step (1), described carboxylic acid neodymium is C
1-C
20carboxylic acid neodymium;
Described alkylaluminium cpd is for having general formula Al (R
1)
3and/or AlH (R
2)
2alkylaluminium cpd, wherein, R
1and R
2be respectively C
1-C
6alkyl;
Described halogen contained compound is for having general formula Al (R
3)
2the aikyl aluminum halide of X, there is general formula Al
2(R
4)
3x
3sesquialter aikyl aluminum halide, there is general formula R
5the halohydrocarbon of X, there is general formula H
4-asi [(CH
2)
ny]
asilane in one or more, wherein, R described in general formula
3-R
5be ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, benzyl or allyl group independently of one another, X and Y is bromine or chlorine independently of one another, and n is the integer of 0-6,4>=a>=1.
13. methods according to claim 12, wherein, in step (1), described carboxylic acid neodymium is C
6-C
10carboxylic acid neodymium.
14. methods according to claim 13, wherein, in step (1), described carboxylic acid neodymium is one or more in neodymium naphthenate, neodymium octoate, neodymium iso-octanate, n-nonanoic acid neodymium, neodymium caprate and n-capric acid neodymium.
15. methods according to claim 12, wherein, in step (1), described alkylaluminium cpd is one or more in trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, triisobutyl aluminium, three amyl group aluminium, three hexyl aluminium, ADEH, dibutyl aluminum hydride and diisobutyl aluminium hydride.
16. methods according to claim 12, wherein, in step (1), described halogen contained compound is one or more in benzyl chloride, bromotoluene, tertiary butyl chloride, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium, sesquialter isobutyl-aluminum chloride, chloromethyl silane and tetrachloro silicane.
17. according to the method described in claim 1, and wherein, in step (1) and step (2), described first conjugated diene and the second conjugated diene are C independently of one another
4-C
6conjugated diene.
18. according to the method described in claim 17, wherein, in step (1) and step (2), described first conjugated diene and the second conjugated diene are divinyl, isoprene, 1,3-pentadiene, 1, one or more in 3-hexadiene and 2,3-dimethylbutadiene.
19. according to the method described in claim 18, and wherein, in step (1) and step (2), described first conjugated diene and the second conjugated diene are divinyl and/or isoprene.
20. methods according to claim 1, wherein, in step (2), described polymerized unit comprises the polymerization reaction kettle of at least 2 series connection.
21. methods according to claim 20, wherein, in step (2), described polymerized unit comprises the polymerization reaction kettle of 3-10 series connection.
22. methods according to claim 21, wherein, in step (2), described polymerized unit comprises the polymerization reaction kettle of 3-5 series connection.
23. methods according to claim 20, wherein, according to the flow direction of material, described tubular reactor and first polymerization reaction kettle are connected in series, thus step (1) is contacted the rare earth catalyst obtained directly send into polymerized unit.
24. methods according to claim 20, wherein, in step (2), described polymeric reaction condition comprises: the temperature in each polymerization reaction kettle is-30 DEG C to 80 DEG C independently of one another; The time contacted in each polymerization reaction kettle is 10-90min independently of one another; The total time contacted in each polymerization reaction kettle is no more than 300min.
25. methods according to claim 24, wherein, in step (2), described polymeric reaction condition comprises: the temperature in each polymerization reaction kettle is 0-70 DEG C independently of one another; The time contacted in each polymerization reaction kettle is 20-80min independently of one another; The total time contacted in each polymerization reaction kettle is 90-180min.
26. methods according to claim 25, wherein, in step (2), described polymeric reaction condition comprises: the temperature in each polymerization reaction kettle is 10-60 DEG C independently of one another; The time contacted in each polymerization reaction kettle is 30-60min independently of one another; The total time contacted in each polymerization reaction kettle is 110-150min.
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| CN107537408A (en) * | 2016-06-23 | 2018-01-05 | 中国石油化工股份有限公司 | A kind of method of catalyst pre-contact device and catalyst pre-contact for alkene continuous polymerization |
| PL3710510T3 (en) | 2017-11-13 | 2021-12-27 | Eni S.P.A. | Process for preparing polycarbonate and catalytic system used |
| IT201800006303A1 (en) | 2018-06-14 | 2019-12-14 | CONFIGURATION OF REACTION AND PROCEDURE FOR THE PRODUCTION OF POLYMERS | |
| WO2023158211A1 (en) * | 2022-02-17 | 2023-08-24 | 주식회사 엘지화학 | Method for preparing catalyst composition and method for preparing conjugated diene-based polymer |
| KR20230123816A (en) * | 2022-02-17 | 2023-08-24 | 주식회사 엘지화학 | Method for preparing catalyst composition and method for preparing conjugated-diene polymer |
| KR20230123815A (en) * | 2022-02-17 | 2023-08-24 | 주식회사 엘지화학 | Method for preparing catalyst composition and method for preparing conjugated-diene polymer |
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| CN101010705A (en) * | 2004-07-08 | 2007-08-01 | 埃克森美孚化学专利公司 | Polymer production at supercritical conditions |
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