CN104231139B - Polyisoprene rubber and continuous polymerization method thereof - Google Patents
Polyisoprene rubber and continuous polymerization method thereof Download PDFInfo
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- CN104231139B CN104231139B CN201310226356.2A CN201310226356A CN104231139B CN 104231139 B CN104231139 B CN 104231139B CN 201310226356 A CN201310226356 A CN 201310226356A CN 104231139 B CN104231139 B CN 104231139B
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Abstract
The invention relates to polyisoprene rubber and a continuous polymerization method thereof. The continuous polymerization method includes the steps: in the presence of an organic solvent and a catalyst, isoprene monomers are subjected to a polymerization reaction in a continuous polymerization device comprising a plurality of series-connection reaction kettles; the catalyst is obtained through mutual contact of a component A, a component B, a component C and a component D in an inert organic solvent, the component A is neodymium carboxylate, the component B is aluminum alkyl, the component C is a halide, the component D is a conjugated diene, and the aluminum alkyl in the component B is aluminum alkyl having the general formula of AlR3, wherein R is a C5-C10 alkyl; the content of cyclohexane in the organic solvent is not less than 50 wt%; the method also includes the aluminum alkyl is added into a first reaction kettle, wherein the molar ratio of the added aluminum alkyl to neodymium carboxylate in the first reaction kettle is 1-15:1. The method can obtain the polyisoprene rubber having the content of a cis-1,4- structure in the structure unit of greater than 98.5 mol%, and the per-pass conversion rate of the continuous polymerization reaction is 95.3% or more.
Description
Technical field
The present invention relates to a kind of isoprene rubber and its continuous polymerization method.
Background technology
Currently, domestic natural gum production capacity is limited, leads to the import volume of natural gum to increase year by year.Research has confirmed, performance
Excellent isoprene rubber can partly replace natural gum, the therefore production of the isoprene rubber of research and development excellent performance in actual applications
Method becomes the main path solving China's natural gum deficiency contradiction.The isoprene rubber that rare earth catalyst isoprene polymerization obtains with
The isoprene rubber that other catalyst systems obtain is compared, closer to natural rubber in terms of microstructure and physical and mechanical properties
（NR）, it is the preferable substitute products of natural gum.Although rare earth catalyst isoprene interstitial polymerization can obtain high cis-1,4-knot
Structure（>=96 moles of %）, the isoprene rubber of HMW, but take continuous polymerization method produce when then be relatively inaccessible to obtain Gao Shun
Formula 1,4- structure（>=96 moles of %）, HMW isoprene rubber effect.
CN101880344A disclose rare-earth isoprene rubber solution polymerization insulation method it is characterised in that：By isoamyl two
Alkene monomer and solvent together enter polyplant with rare earth catalyst after mixing to be polymerized, and isoprene monomer is in solvent
Middle concentration is 9-15%, and rare earth catalyst agent concentration is 1-8 × 10-6Mol Nd/g isoprene monomer, after polymerization glue reaction terminating
Plus age resistor, then after condensing, be dehydrated, be dried, packing, obtain rare-earth isoprene rubber product, above-mentioned rare earth catalyst is by rare earth
The ternary system of compound, alkyl aluminum and halide composition, wherein, rare earth compound is rare earth carboxylate or rare earth acid phosphatase
Salt, rare earth carboxylate is specially neodymium caprate, neodymium naphthenate or neodymium iso-octanate, and rare earth superphosphate is specially Nd (P204)3Or
Nd(P507)3；Abovementioned alkyl aluminium compound is triisobutyl aluminium, diisobutyl aluminium hydride or ADEH；Above-mentioned halide
For a chloro-di-isobutyl aluminum, aluminium diethyl monochloride, sesquialter aluminium ethide, tertiary butyl chloride, benzyl chloride or chlorine.This invention is used for solving
Thermo Isolation Technique produces high energy consumption, the problem of high cost that rare-earth isoprene rubber exists, using rare earth three component catalyst system, can
To carry out one-pot interval or multi-floating bodies adiabatic polymerisation.But the content of cis-structure can not be true in the polymerizate of the method preparation
Fixed.
CN101045768A discloses the rare earth catalyst preparing polyisoprene it is characterised in that this rare earth catalyst
Component and proportioning are A. rare earth organic compounds, select rare earth carboxylate or rare earth acidic phosphor/phosphine hydrochlorate；B. trialkylaluminium or hydrogen
Change alkyl aluminum；C. chloride is：One chloro-di-isobutyl aluminum, aluminium diethyl monochloride, sesquialter aluminium ethide, tertiary butyl chloride, benzyl chloride, alkene
Propyl chloride, silicon tetrachloride or Me4-nSiClnWherein n is 1,2 or 3；D. conjugated diolefin；The mol ratio of each component is：B：A=5-
30：1, C：A=1.0-4.0：1, D：A=5-20：1.This invention is used for obtaining the rare earth catalyst of homogeneous stability, in higher polymerization
At a temperature of cause isoprene polymerization, obtain high cis- Isosorbide-5-Nitrae structural content（>=mole 96%）And narrow molecular weight distribution（＜ 3.0）And
There is the polyisoprene of stretch crystallization performance characteristics.This invention can only obtain along 1,4- structure under one-pot batch polymerization conditions
Content is 96.0-97.2%, and molecular weight distribution is the polyisoprene of 2.02-2.88.
RU2263121 and RU2109753C1 discloses and carries out diolefin polymerization using toluene for solvent, and catalyst system makes
With rare earth element, diisobutyl sesquichloride aluminium, pentadiene and triisobutyl aluminium, the diolefin mixing and toluene
It is separately added into first three reactor, on the device of 5 or 6 reactor series connection, the conversion ratio of last reactor reaches
92%.In polymerization product, cis-1,4-content is 95.0%.
As can be seen here, improve the conversion per pass of isoprene rubber continuous polymerization, and it is high to obtain cis Isosorbide-5-Nitrae-structural content
Isoprene rubber remains technical issues that need to address.
Content of the invention
The purpose of the present invention is low for solving conversion per pass during isoprene rubber continuous polymerization, and the isoprene rubber obtaining
The low problem of cis Isosorbide-5-Nitrae-structural content, provides a kind of isoprene rubber and its continuous polymerization method.
To achieve these goals, the invention provides a kind of method of isoprene rubber continuous polymerization, the method includes：?
In the presence of organic solvent and catalyst, isoprene monomer is carried out in continuous polymerization reaction unit polymerisation, described company
Continuous polymerizing reactor includes the reactor of multiple series connection；Described catalyst passes through component A, component B, component C and component D exist
Contact with each other in inert organic solvents and obtain, component A is carboxylic acid neodymium, component B is alkyl aluminum, component C is halide, component D is
Conjugated diene, the described alkyl aluminum in component B is AlR for formula3Alkyl aluminum, wherein R be C5-C10Alkyl；Described have
The content of machine solvent cyclohexane is not less than 50 weight %；Wherein, the method also includes adding alkyl aluminum in the first reactor,
And the mol ratio of the carboxylic acid neodymium in the described alkyl aluminum and described first reactor adding is 1-15：1.
Present invention also offers a kind of isoprene rubber being prepared by the method that the invention described above provides, wherein, described
The content of the cis-1,4-structure in isoprene rubber is more than 98.5 moles of %.
By the method for the present invention, the conversion per pass of the isoprene rubber continuous polymerization not only carrying out is high, and obtain
Cis-1,4-structural content in isoprene rubber is up to 98.5-99 mole of %.For example in embodiment 1, using three positive decyl aluminium, gather
The organic solvent closing reaction is n-hexane and cyclohexane mixtures, and its cyclohexane is 80 weight %, adds in the first reactor
Three positive decyl aluminium are 10 with the mol ratio of neodymium caprate:When 1, the content of the cis Isosorbide-5-Nitrae-structure in the isoprene rubber of acquisition is 99
Mole %, the conversion per pass that isoprene carries out continuous polymerization reaction is 95.2%.
Suitable 1,4- structural content in the isoprene rubber that the method that the present invention provides is obtained reaches as high as 99 moles of %.Study carefully it
Reason it may be possible in catalyst system adopt alkyl aluminum and polymerisation organic solvent used in hexamethylene structure institute
The space steric effect having, have impact on the polymerization process of isoprene, and passes through in polymerization to the first reactor
A certain amount of alkyl aluminum of middle addition, the chelation structure that can play rugged catalyst, the effect removing impurity in polymerization system, has
Beneficial to avoiding catalyst to inactivate, also help obtain the high isoprene rubber product of cis Isosorbide-5-Nitrae-structural content.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that it is described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of method of isoprene rubber continuous polymerization, the method includes：In organic solvent and catalyst
In the presence of, isoprene monomer is carried out in continuous polymerization reaction unit polymerisation, described continuous polymerization reaction unit bag
Include the reactor of multiple series connection；Described catalyst passes through component A, component B, component C and component D is mutual in inert organic solvents
Contact and obtain, component A is carboxylic acid neodymium, component B is alkyl aluminum, component C is halide, component D is conjugated diene, component B
In described alkyl aluminum for formula be AlR3Alkyl aluminum, wherein R be C5-C10Alkyl；Described organic solvent cyclohexane
Content is not less than 50 weight %；Wherein, the method also includes adding alkyl aluminum in the first reactor, and the described alkyl adding
The mol ratio of the carboxylic acid neodymium in aluminium and described first reactor is 1-15：1；The described alkyl aluminum being preferably added to is anti-with described first
The mol ratio answering the carboxylic acid neodymium in kettle is 1-10：1.
Although prepare being used for alkyl aluminum during catalyst, it was found by the inventors of the present invention that passing through in polymerization again
Extra addition alkyl aluminum, it is possible to obtain the higher isoprene rubber product of cis Isosorbide-5-Nitrae-structural content.According to the present invention, in isoamyl rubber
In glue continuous polymerization course of reaction, to the species of alkyl aluminum adding in the first reactor, there is no particular limitation, as long as energy
Enough play the chelation structure removing impurity and rugged catalyst in polymerization system, under preferable case, the described alkyl of addition
Aluminium is AlR ' for formula3Alkyl aluminum, wherein R ' be C1-C10Alkyl；The described alkyl aluminum being preferably added to is AlR ' for formula3
Alkyl aluminum, wherein R ' be C5-C10Alkyl；More preferably addition described alkyl aluminum be tri-n-hexyl aluminum, tri-n-octylaluminium and
One or more of three positive decyl aluminium.In the preferred embodiment of the present invention, the described alkyl aluminum of addition is three just
Decyl aluminium.The extra alkyl aluminum adding can be preferably identical with to prepare alkyl aluminum used during catalyst identical or different.
According to the present invention, although as long as adding extra alkyl aluminum to can achieve the mesh of the present invention in the first reactor
, the opportunity of addition can select in relative broad range, can add after being mixed together with organic solvent and catalyst it is also possible to
Be individually added into simultaneously but each it is also possible to be initially charged organic solvent and catalyst, polymerisation start a period of time after but go out
Extra alkyl aluminum is added before expecting the second reactor, but in order to obtain more preferable polymerisation effect, under preferable case,
The opportunity adding alkyl aluminum meets t1：t2=1：1.1-5, wherein t1 represent the time starting to addition alkyl aluminum from polymerisation
Section, t2 represents that isoprene monomer carries out the time of staying of polymerisation in the first reactor.This mode carries out polymerisation
The content of the cis Isosorbide-5-Nitrae-structure in the isoprene rubber obtaining can be higher, and conversion ratio is also higher.
According to the present invention, the described alkyl aluminum in component B is co-catalyst in the catalyst, acts primarily as alkyl and is turned into
With generating rare earth carbon activity center, also there is the effect removing impurity, stabilizing active center and chain tra nsfer simultaneously.In order to
Obtain the isoprene rubber product with high-cis Isosorbide-5-Nitrae-structural content in isoprene rubber continuous polymerization, in the present invention, adopt molecule to tie
The alkyl aluminum of larger space steric hindrance, the active sites of guard catalyst are had on structure.Described alkyl aluminum in preferred ingredient B is for three just
One or more of hexyl aluminium, tri-n-octylaluminium and three positive decyl aluminium；Described alkyl aluminum more preferably in component B was the three positive last of the ten Heavenly stems
Base aluminium.
According to the present invention, described carboxylic acid neodymium is the major catalyst of described catalyst, and wherein element neodymium is central metal atom,
Coordinate with Carboxylic Acid Ions and play catalytic action.Carboxylic Acid Ions are by empty ligancy and the cloud density distribution of change element neodymium
Change bond polarity and intensity etc., thus affecting activity and the directionality of described rare earth catalyst.In the present invention, preferable case
Under, described carboxylic acid neodymium is neodymium naphthenate and/or C1-C20Carboxylic acid neodymium；Preferably described carboxylic acid neodymium be neodymium naphthenate, caprylic acid neodymium,
One or more of neodymium iso-octanate, neodymium caprate and n-capric acid neodymium.Wherein, described neodymium naphthenate can adopt known in this field
Method, is synthesized with neodymium chloride by aphthenic acids, and aphthenic acids can be the aphthenic acids that acid number is 200-500mgKOH.
In the present invention, described halide makes described catalyst have high activity, and under preferable case, described halide is to have
Formula AlR "2The aikyl aluminum halide of X, there is formula Al2R″3X3Sesquialkyl aluminium and there is general formula R " in the halogenated hydrocarbons of X
Plant or multiple, wherein R " is alkyl or aryl, X is bromine or chlorine；Preferably described halide is aluminium diethyl monochloride, sesquialter ethyl chloride
Change one or more of aluminium and a chloro-di-isobutyl aluminum.
In the present invention, described conjugated diene plays the effect stablizing described rare earth catalyst activated centre, preferable case
Under, described conjugated diene is C4-C6Conjugated diene；Preferably described conjugated diene is butadiene and/or isoprene.
According to the present invention, there is no particular limitation for the composition content of each component in described catalyst, under preferable case, institute
The mol ratio stating component A, component B, component C and component D is A：B：C：D=1：5-10：1-3：10-20.
According to the present invention, the mode of described contact does not have special restriction, as long as can prepare that continuous polymerization of the present invention is met
The required homogeneous catalyst of reaction, under preferable case, the mode of described contact is：（1）By component C be added to component A and
In the mixture of component D, obtain mixture ADC；（2）Component B is added in described mixture ADC.
According to the present invention, in the mode of described contact, described component C can be -30 after being added to described mixture AD
It is aged 5-250 minute at DEG C -60 DEG C, obtain mixture ADC.Described component B can be -30 after being added to described mixture ADC
Continue ageing 0.5-48 hour at DEG C -60 DEG C, obtain described catalyst.
According to the present invention, used in the mode of described contact inert organic solvents can be selected for inert to reactive component
Aliphatic saturated hydrocarbon or alicyclic, often select C5-C10Alkane and/or cycloalkane, such as pentane, isopentane, n-hexane, hexamethylene, heptan
One or more of alkane and octane.
In the present invention, in the mode of described contact, can be according to the mode of above-mentioned contact by component A, component B, component C
It is added in inert organic solvents with component D；Can also be that component A, component B and component C are first dissolved separately in inertia is organic
In solvent, form multiple organic solutions containing different component, then contact in the way of above-mentioned contact again.Preferably by component A,
Component B and component C are first dissolved separately in described inert organic solvents, form multiple organic solutions containing different component；Many
The individual organic solution containing different component can be using different described inert organic solvents it is also possible to all using described in identical
Inert organic solvents, preferably use identical inert organic solvents；Then according to the mode of above-mentioned contact contacts.
In the present invention, to the concentration of multiple organic solutions containing different component being formed, there is no particular limitation, as long as
Disclosure satisfy that and obtain described catalyst, the such as concentration of component solution A can be 0.1-0.5mol/L, component B solution
Concentration can be 0.1-2mol/L, and the concentration of component C solution can be 0.1-2mol/L.
According to the present invention, the mode of described contact can be carried out in an inert atmosphere.Described inert atmosphere can be for example
Nitrogen.
According to the present invention, the organic solvent carrying out described polymerisation use also contains C5-C10Alkane and/or remove hexamethylene
Outer C5-C10Cycloalkane, more preferably described organic solvent is also containing in pentane, isopentane, n-hexane, heptane and octane
One or more.
According to the invention it is preferred in the case of, described organic solvent is hexamethylene and above-mentioned C5-C10Alkane and/or remove hexamethylene
C outside alkane5-C10Cycloalkane mixing mixed organic solvents.In described organic solvent, with the gross weight of described organic solvent
On the basis of, the content of hexamethylene can be not less than 50 weight %, and the preferably content of hexamethylene is 60-95 weight %.Isoprene list
Body polymerization using sterically hindered larger organic solvent on molecular structure, can help to improve cis Isosorbide-5-Nitrae in isoprene rubber product-
The content of structure.
According to the present invention, in continuous polymerization unit, the addition of isoprene monomer and catalyst can particularly not advised
Fixed, the addition of catalyst has enough catalytic action, and the addition of isoprene monomer meets polymerisation production
Require.Under preferable case, concentration in described organic solvent for the described isoprene monomer is 9-40 weight %, described urges
Carboxylic acid neodymium in agent is 0.6-5 × 10 with the mol ratio of described isoprene monomer-4：1.
According to the invention it is preferred in the case of, the water content of described isoprene monomer is below 20ppm, oxide content
For below 10ppm.
According to the present invention, described continuous polymerization reaction unit can include the reactor of multiple series connection.Under preferable case, institute
State the reactor that continuous polymerization reaction unit includes three series connection；Further preferred second reactor and the 3rd reactor are
Adiabatic reaction kettle.In the present invention, the reactor that continuous polymerization reaction unit includes can be equal-volume reactor.
According to the present invention, it is anti-that described isoprene monomer carries out polymerization in multiple reactors of continuous polymerization reaction unit
The time of staying answered, there is no particular limitation and the time of staying in each reactor can be the same.Under preferable case,
The time of staying of multiple reaction kettle for reaction in continuous polymerization reaction unit for the described isoprene monomer is 35min-50min.
In the method for the present invention, carry out polymerisation in multiple reactors of described continuous polymerization reaction unit, wherein
The polymeric reaction temperature in the first reactor can be made to be 0-10 DEG C because of the temperature of charging.Second and the 3rd polymerization in reactor
Reaction temperature can carry out produced temperature for adiabatic polymerisation.
In the present invention, add described isoprene monomer, described organic solvent and described catalyst in the first reactor,
Under preferable case, the temperature of the described isoprene monomer, described organic solvent and described catalyst of addition is -40 DEG C to 0 DEG C.
According to the present invention, after described isoprene rubber continuous polymerization completes, can be made using the method adding terminator
Living polymer chains lose activity, and reach the purpose terminating described polymerisation.The species of described terminator and consumption do not have spy
Do not limit, as long as described terminator can make polymer active chain inactivate.Usually, described terminator can be water, C1-
C6Aliphatic alcohol, C4-C12Aliphatic carboxylic acid and one or more of aryl polyol, described aryl polyhydroxy
Compound refers to that the hydrogen atom at least two on phenyl ring is optionally substituted by a hydroxyl group generated compound.Preferably, described terminator
For one or more of water, methyl alcohol, ethanol, isopropanol 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 can will be polymerized
Active specy in product inactivates, and repeats no more herein.
In the present invention, after described isoprene rubber continuous polymerization is terminated, then through condensing, being dehydrated, be dried to obtain isoamyl rubber
Glue product.
In the preferred embodiment of the present invention, the organic solvent cyclohexane of multi-floating bodies continuous polymerization reaction contains
Amount is not less than 50 weight %, and adds alkyl aluminum in the first reactor, and the described alkyl aluminum adding and described first reaction
The mol ratio of the carboxylic acid neodymium in kettle is 1-15：1, the conversion per pass of isoprene rubber continuous polymerization can be improved, and help obtain
Obtain the higher isoprene rubber product of cis-1,4-structural content.
In another kind of preferred embodiment of the present invention, using containing component A be carboxylic acid neodymium, component B be alkyl aluminum, group
Point C is halide and component D is the catalyst of conjugated diene, and wherein said alkyl aluminum is formula is AlR3Alkyl aluminum, its
Middle R is C5-C10Alkyl, and A：B：C：The mol ratio of D is 1：5-10：1-3：10-20；Multi-floating bodies continuous polymerization reaction
Organic solvent cyclohexane content is not less than 50 weight %, and adds alkyl aluminum in the first reactor, and the described alkane adding
The mol ratio of the carboxylic acid neodymium in base aluminium and described first reactor is 1-15：1, it is possible to obtain preferably isoprene rubber continuous polymerization
Conversion per pass, and be more beneficial for obtaining the high isoprene rubber product of cis Isosorbide-5-Nitrae-structural content.
Present invention also offers a kind of isoprene rubber being prepared by the method that the invention described above is passed through, wherein, described
The content of the cis-1,4-structure in isoprene rubber is more than 98.5 moles of %；Cis-1,4-structure in preferably described isoprene rubber
Content be 98.5-99 mole of %.
Hereinafter will be described the present invention by embodiment.
In the present invention, in isoprene rubber, the assay of cis Isosorbide-5-Nitrae-structure is using red in German Bruker Tensor27
External spectrum instrument or German Bruker400MHz NMR, solvent is deuterochloroform.Conversion per pass be determined as gravimetric method,
The i.e. percentage of dry glue and the weight ratio of isoprene in glue；Described glue is the isoprene list adding in the first reactor
The polymeric reaction solution that body and organic solvent and catalyst are formed, described dry glue is the final isoprene rubber product obtaining.
Embodiment 1
The method that the present embodiment is used for the isoprene rubber continuous polymerization of the present invention is described.
（1）The preparation of catalyst.Under nitrogen protection, in the catalyst aging kettle of 20L add 200ml isoprene,
185ml concentration is neodymium caprate hexane solution and the 10L hexane solution of 0.36mol/L, then adds 200ml in 0 DEG C of stirring
Concentration is 1mol/L aluminium diethyl monochloride hexane solution, continues to be aged 30 minutes at 0 DEG C.Being subsequently adding 890ml concentration is
The three positive decyl aluminium hexane solutions of 0.74mol/L, continue to be aged 10 hours at 0 DEG C, obtain catalyst C1, wherein neodecanoic acid
Neodymium：Three positive decyl aluminium：Aluminium diethyl monochloride：Isoprene=1:8:3:20（Mol ratio）.
（2）Rubber is polymerized.Using three reactors connected as polymerizing reactor, the wherein second reactor and the 3rd
Reactor is adiabatic reaction kettle.Each reactor volume is 5L.Under nitrogen protection, add temperature successively in the first reactor
The organic solvent of the 350kg isoprene for -40 DEG C, 2000g n-hexane and hexamethylene mixing and 180ml catalyst C1.Wherein,
The water content of isoprene monomer is 20ppm, and oxide content is 10ppm；The content of organic solvent cyclohexane is 80 weights
Amount %；Neodymium caprate is 1.6 × 10 with the monomer mole ratio of isoprene monomer-4:1, the concentration of isoprene monomer is 14 weights
Amount %.
When polymerisation proceeds to 10 minutes in the first reactor, in the first reactor, add three positive decyl aluminium,
The amount of three positive decyl aluminium adding is 10 with the mol ratio of neodymium caprate:1.Polymer material is in first, second, and third reactor
In the time of staying be respectively 50 minutes, and first, second, and third temperature of reaction kettle is respectively：7 DEG C, 25 and 31 DEG C.
Processed with the material that 2,6- di-tert-butyl hydroquinone's methanol solution is discharged to the 3rd reactor, terminate polymerization
Reaction, then condenses through ethanol, is vacuum dried 48 hours.Obtain isoprene rubber product, after measured cis Isosorbide-5-Nitrae-knot in this product
The content of structure is 99 moles of %.Be computed isoprene monomer carry out continuous polymerization conversion per pass be 95.2%.
Embodiment 2
The method that the present embodiment is used for the isoprene rubber continuous polymerization of the present invention is described.
（1）The preparation of catalyst.Under nitrogen protection, in the catalyst aging kettle of 20L add 200ml isoprene,
185ml concentration is the neodymium naphthenate of 0.36mol/L（It is obtained with the aphthenic acids that acid number is 230）Hexane solution and 10L n-hexane
Solution, then add 200ml concentration for 1mol/L aluminium diethyl monochloride hexane solution in 0 DEG C of stirring, continue to be aged 30 at 0 DEG C
Minute.It is subsequently adding the three positive decyl aluminium hexane solutions that 890ml concentration is 0.74mol/L, continue ageing 10 at 0 DEG C little
When, obtain catalyst C2, wherein for neodymium naphthenate：Three positive decyl aluminium：Aluminium diethyl monochloride：Isoprene=1:8:3:20（Mole
Than）.
（2）Rubber is polymerized.Using three reactors connected as polymerizing reactor, the wherein second reactor and the 3rd
Reactor is adiabatic reaction kettle.Each reactor volume is 5L.Under nitrogen protection, add temperature successively in the first reactor
The organic solvent of the 350kg isoprene for -40 DEG C, 2000g n-hexane and hexamethylene mixing and 180ml catalyst C2.Wherein,
The water content of isoprene monomer is 20ppm, and oxide content is 10ppm；The content of organic solvent cyclohexane is 60 weights
Amount %；Neodymium naphthenate is 1.7 × 10 with the mol ratio of isoprene monomer-4:1, the concentration of isoprene monomer is 14 weight %.
When polymerisation proceeds to 20 minutes in the first reactor, in the first reactor, add three positive decyl aluminium,
The amount of three positive decyl aluminium adding is 5 with the mol ratio of neodymium naphthenate:1.The time of staying in first, second, and third reactor
It is respectively 50 minutes, and the first temperature of reaction kettle is respectively：8 DEG C, 26 DEG C and 32 DEG C.
Processed with the material that 2,6- di-tert-butyl hydroquinone's methanol solution is discharged to the 3rd reactor, terminate polymerization
Reaction, then condenses through ethanol, is vacuum dried 48 hours.Obtain isoprene rubber product, after measured cis Isosorbide-5-Nitrae-knot in this product
The content of structure is 98.8 moles of %.Be computed isoprene monomer carry out continuous polymerization conversion per pass be 95.3%.
Embodiment 3
The method that the present embodiment is used for the isoprene rubber continuous polymerization of the present invention is described.
（1）The preparation of catalyst.Under nitrogen protection, in the catalyst aging kettle of 20L add 200ml isoprene,
185ml concentration is neodymium caprate hexane solution and the 10L hexane solution of 0.36mol/L, then adds 200ml in 0 DEG C of stirring
Concentration is 1mol/L aluminium diethyl monochloride hexane solution, continues to be aged 30 minutes at 0 DEG C.Being subsequently adding 890ml concentration is
The three positive decyl aluminium hexane solutions of 0.74mol/L, continue to be aged 10 hours at 0 DEG C, obtain catalyst C3, wherein for the new last of the ten Heavenly stems
Sour neodymium：Three positive decyl aluminium：Aluminium diethyl monochloride：Isoprene=1:8:3:20（Mol ratio）.
（2）Rubber is polymerized.Using three reactors connected as polymerizing reactor, the wherein second reactor and the 3rd
Reactor is adiabatic reaction kettle.Each reactor volume is 5L.Under nitrogen protection, add temperature successively in the first reactor
The organic solvent of the 350kg isoprene for -40 DEG C, 2000g n-hexane and hexamethylene mixing and 180ml catalyst C3.Wherein,
The water content of isoprene monomer is 20ppm, and oxide content is 10ppm；The content of organic solvent cyclohexane is 60 weights
Amount %；Neodymium caprate is 1.5 × 10 with the monomer mole ratio of isoprene monomer-4:1, the concentration of isoprene monomer is 14 weights
Amount %.
When polymerisation proceeds to 40 minutes in the first reactor, in the first reactor, add three positive decyl aluminium,
The amount of three positive decyl aluminium adding is 1 with the mol ratio of neodymium caprate:1.The time of staying in first, second, and third reactor
It is respectively 45 minutes, and the first temperature of reaction kettle is respectively：8 DEG C, 27 DEG C and 34 DEG C.
Processed with the material that 2,6- di-tert-butyl hydroquinone's methanol solution is discharged to the 3rd reactor, terminate polymerization
Reaction, then condenses through ethanol, is vacuum dried 48 hours.Obtain isoprene rubber product, after measured cis Isosorbide-5-Nitrae-knot in this product
The content of structure is 98.7 moles of %.Be computed isoprene monomer carry out continuous polymerization conversion per pass be 96.5%.
Embodiment 4
The method that the present embodiment is used for the isoprene rubber continuous polymerization of the present invention is described.
（1）The preparation of catalyst.Under nitrogen protection, in the catalyst aging kettle of 20L add 200ml isoprene,
185ml concentration is the neodymium naphthenate of 0.36mol/L（It is obtained with the aphthenic acids that acid number is 230）Hexane solution and 10L n-hexane
Solution, then add 200ml concentration for 1mol/L aluminium diethyl monochloride hexane solution in 0 DEG C of stirring, continue to be aged 30 at 0 DEG C
Minute.It is subsequently adding the tri-n-hexyl aluminum hexane solution that 890ml concentration is 0.74mol/L, continue ageing 10 at 0 DEG C little
When, obtain catalyst C1, wherein neodymium naphthenate：Tri-n-hexyl aluminum：Aluminium diethyl monochloride：Isoprene=1:8:3:20（Mole
Than）.
（2）Rubber is polymerized.Using three reactors connected as polymerizing reactor, the wherein second reactor and the 3rd
Reactor is adiabatic reaction kettle.Each reactor volume is 5L.Under nitrogen protection, add temperature successively in the first reactor
The organic solvent of the 350kg isoprene for -40 DEG C, 2000g n-hexane and hexamethylene mixing and 180ml catalyst C1.Wherein,
The water content of isoprene monomer is 20ppm, and oxide content is 10ppm；The content of organic solvent cyclohexane is 60 weights
Amount %；Neodymium naphthenate is 1.6 × 10 with the mol ratio of isoprene monomer-4:1；The concentration of isoprene monomer is 15 weight %.
When polymerisation proceeds to 10 minutes in the first reactor, in the first reactor, add three positive decyl aluminium,
The amount of tri-n-hexyl aluminum adding is 5 with the mol ratio of neodymium naphthenate:1.The time of staying in first, second, and third reactor
For 48 minutes, and second and the 3rd temperature of reaction kettle be respectively：10 DEG C, 26 DEG C and 33 DEG C.
Processed with the material that 2,6- di-tert-butyl hydroquinone's methanol solution is discharged to the 3rd reactor, terminate polymerization
Reaction, then condenses through ethanol, is vacuum dried 48 hours.Obtain isoprene rubber product, after measured cis Isosorbide-5-Nitrae-knot in this product
The content of structure is 98.6 moles of %.Be computed isoprene monomer carry out continuous polymerization conversion per pass be 95.5%.
Embodiment 5
Method according to embodiment 1 carries out the continuous polymerization of isoprene rubber, except for the difference that, step（2）Rubber polymerization procedure
In, three positive decyl aluminium are simultaneously introduced in the first polymeric kettle with organic solvent, catalyst and isoprene.Obtain isoprene rubber to produce
Product, in this product, the content of cis Isosorbide-5-Nitrae-structure is 98.5 moles of % after measured.It is computed isoprene monomer and carry out continuous polymerization
Conversion per pass be 95.3%.
Comparative example 1
According to the method for embodiment 1, except for the difference that, in the first reactor, do not add three positive decyls in the course of the polymerization process
Aluminium.
Continuously aggregated reaction obtains isoprene rubber product, and in this product, the content of cis Isosorbide-5-Nitrae-structure is 98.2 after measured
Mole %.Be computed isoprene monomer carry out continuous polymerization conversion per pass be 90%.
Comparative example 2
According to the method for embodiment 1, except for the difference that,（1）In catalyst, substitute three positive decyl aluminium with triisobutyl aluminium.
Continuously aggregated reaction obtains isoprene rubber product, and in this product, the content of cis Isosorbide-5-Nitrae-structure is 97.9 after measured
Mole %.Be computed isoprene monomer carry out continuous polymerization conversion per pass be 95.1%.
Comparative example 3
According to the method for embodiment 1, except for the difference that,（2）In isoprene rubber continuous polymerization, with n-hexane substitute n-hexane and
The organic solvent of hexamethylene mixing.
Continuously aggregated reaction obtains isoprene rubber product, and in this product, the content of cis Isosorbide-5-Nitrae-structure is rubbed for 98 after measured
You are %.Be computed isoprene monomer carry out continuous polymerization conversion per pass be 95%.
Be can be seen that by the data result of above-described embodiment and contain the alkyl with greater room steric hindrance employing
A certain amount of alkyl aluminum is added in the first reactor when the catalyst of al composition, the organic solvent containing hexamethylene and polymerization
In the case of, in the isoprene rubber product that isoprene rubber continuous polymerization obtains, the content of cis Isosorbide-5-Nitrae-structure is improved, and reaches
98.5-99 mole of %, highest can reach 99 moles of %.And the conversion per pass of continuous polymerization reaction reaches more than 95.3%.
And do not take above-mentioned three kind corrective measure, the isoprene rubber product of acquisition in comparative example 1-3 completely simultaneously
In cis Isosorbide-5-Nitrae-structure highest be only capable of as 98.2 moles of %, the conversion per pass of continuous polymerization reaction only up to have 95.1%, no
The isoprene rubber continuous polymerization effect that can have obtained.
Therefore, take the aluminum alkyl component comprising in the catalyst there is greater room steric hindrance, in continuous polymerization reaction
Using the mixed organic solvents containing a certain amount of hexamethylene with the method that adds a certain amount of alkyl aluminum in the first reactor
It is to implement the preferred embodiment of the present invention.
Claims (27)
1. a kind of method of isoprene rubber continuous polymerization, the method includes：In the presence of organic solvent and catalyst, by isoamyl two
Alkene monomer carries out polymerisation in continuous polymerization reaction unit, and described continuous polymerization reaction unit includes the reaction of multiple series connection
Kettle；
Described catalyst passes through to contact with each other component A, component B, component C and component D in inert organic solvents to obtain, component
A is carboxylic acid neodymium, and component B is alkyl aluminum, and component C is halide, and component D is conjugated diene, and the described alkyl aluminum in component B is
Formula is AlR3Alkyl aluminum, wherein R be C5-C10Alkyl；
The content of the organic solvent cyclohexane that polymerisation uses is not less than 50 weight %；
Wherein, the method also includes adding extra alkyl aluminum, and the extra alkyl aluminum of addition and institute in the first reactor
The mol ratio stating the carboxylic acid neodymium in the first reactor is 1-15：1；Described alkyl aluminum in component B is tri-n-hexyl aluminum, three just pungent
One or more of base aluminium and three positive decyl aluminium.
2. method according to claim 1, wherein, carboxylic acid in the extra alkyl aluminum of addition and described first reactor
The mol ratio of neodymium is 1-10：1.
3. method according to claim 1 and 2, wherein, adds the opportunity of extra alkyl aluminum to meet t1：T2=1：1.1-
5, wherein t1 represent and start to the time period adding extra alkyl aluminum from polymerisation, and t2 represents isoprene monomer first
Carry out the time of staying of polymerisation in reactor.
4. method according to claim 1, wherein, the described alkyl aluminum in component B is three positive decyl aluminium.
5. method according to claim 1 and 2, wherein, the content of the organic solvent cyclohexane that polymerisation uses is
60-95 weight %.
6. method according to claim 3, wherein, the content of the organic solvent cyclohexane that polymerisation uses is 60-
95 weight %.
7. method according to claim 1 and 2, wherein, the organic solvent that polymerisation uses also contains C5-C10Alkane
And/or the C in addition to hexamethylene5-C10Cycloalkane.
8. method according to claim 7, wherein, polymerisation use organic solvent also contain pentane, isopentane,
One or more of n-hexane, heptane and octane.
9. method according to claim 3, wherein, the organic solvent that polymerisation uses also contains C5-C10Alkane and/or
C in addition to hexamethylene5-C10Cycloalkane.
10. method according to claim 9, wherein, the organic solvent that polymerisation uses also contains pentane, isoamyl
One or more of alkane, n-hexane, heptane and octane.
11. methods according to claim 1 and 2, wherein, described carboxylic acid neodymium is neodymium naphthenate and/or C1-C20Carboxylic acid
Neodymium；
Described halide is to have formula AlR "2The alkyl or aryl aluminum halide of X, there is formula Al2R″3X3Sesquialkyl aluminium or
" one or more of halogenated hydrocarbons of X, wherein R " is alkyl or aryl to sesquialter aryl aluminium with having general formula R, and X is bromine or chlorine；
Described conjugated diene is C4-C6Conjugated diene.
12. methods according to claim 11, wherein, described carboxylic acid neodymium be neodymium naphthenate, caprylic acid neodymium, neodymium iso-octanate,
One or more of neodymium caprate and n-capric acid neodymium；Described halide is aluminium diethyl monochloride, sesquialter ethylmercury chloride aluminium and one
One or more of chloro-di-isobutyl aluminum；Described conjugated diene is butadiene and/or isoprene.
13. methods according to claim 3, wherein, described carboxylic acid neodymium is neodymium naphthenate and/or C1-C20Carboxylic acid neodymium；
Described halide is to have formula AlR "2The alkyl or aryl aluminum halide of X, there is formula Al2R″3X3Sesquialkyl aluminium or
" one or more of halogenated hydrocarbons of X, wherein R " is alkyl or aryl to sesquialter aryl aluminium with having general formula R, and X is bromine or chlorine；
Described conjugated diene is C4-C6Conjugated diene.
14. methods according to claim 13, wherein, described carboxylic acid neodymium be neodymium naphthenate, caprylic acid neodymium, neodymium iso-octanate,
One or more of neodymium caprate and n-capric acid neodymium；Described halide is aluminium diethyl monochloride, sesquialter ethylmercury chloride aluminium and one
One or more of chloro-di-isobutyl aluminum；Described conjugated diene is butadiene and/or isoprene.
15. methods according to claim 1 and 2, wherein, the mol ratio of described component A, component B, component C and component D is
A：B：C：D=1：5-10：1-3：10-20.
16. methods according to claim 3, wherein, the mol ratio of described component A, component B, component C and component D is A：
B：C：D=1：5-10：1-3：10-20.
17. methods according to claim 1 and 2, wherein, the mode of described contact is：
(1) component C is added in component A and the mixture of component D, obtains mixture ADC；
(2) component B is added in described mixture ADC.
18. methods according to claim 3, wherein, the mode of described contact is：
(1) component C is added in component A and the mixture of component D, obtains mixture ADC；
(2) component B is added in described mixture ADC.
19. methods according to claim 1 and 2, wherein, described continuous polymerization reaction unit includes the reaction of three series connection
Kettle.
20. methods according to claim 19, wherein, second reactor and the 3rd reactor are adiabatic reaction kettle.
21. methods according to claim 3, wherein, described continuous polymerization reaction unit includes the reactor of three series connection.
22. methods according to claim 21, wherein, second reactor and the 3rd reactor are adiabatic reaction kettle.
23. methods according to claim 1 and 2, wherein, the extra alkyl aluminum of addition is AlR ' for formula3Alkyl
Aluminium, wherein R ' are C1-C10Alkyl.
24. methods according to claim 23, wherein, the extra alkyl aluminum of addition is AlR ' for formula3Alkyl aluminum,
Wherein R ' is C5-C10Alkyl.
25. methods according to claim 3, wherein, the extra alkyl aluminum of addition is AlR ' for formula3Alkyl aluminum, its
Middle R ' is C1-C10Alkyl.
26. methods according to claim 25, wherein, the extra alkyl aluminum of addition is AlR ' for formula3Alkyl aluminum,
Wherein R ' is C5-C10Alkyl.
Isoprene rubber that a kind of 27. methods described in any one in claim 1-26 prepare is it is characterised in that institute
The content stating the cis-1,4-structure in isoprene rubber is more than 98.5 moles of %.
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| CN102532379A (en) * | 2010-12-09 | 2012-07-04 | 中国石油化工股份有限公司 | Polymerization method for preparing rare earth isoprene rubber |
| CN102532355A (en) * | 2010-12-09 | 2012-07-04 | 中国石油化工股份有限公司 | Homogenous neodymium-based rare earth catalyst, and its preparation method and application |
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| CN102532379A (en) * | 2010-12-09 | 2012-07-04 | 中国石油化工股份有限公司 | Polymerization method for preparing rare earth isoprene rubber |
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