CN110305251A - Polyisoprene oligomer, branched modification agent and branching type rare-earth isoprene rubber preparation method - Google Patents
Polyisoprene oligomer, branched modification agent and branching type rare-earth isoprene rubber preparation method Download PDFInfo
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- CN110305251A CN110305251A CN201810231313.6A CN201810231313A CN110305251A CN 110305251 A CN110305251 A CN 110305251A CN 201810231313 A CN201810231313 A CN 201810231313A CN 110305251 A CN110305251 A CN 110305251A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
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- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/46—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals
- C08F4/461—Catalysts containing at least two different components covered by the same or by different subgroups of group C08F4/46, e.g. butyllithium + propylrubidium
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Abstract
The present invention relates to polyisoprene branching agent fields, disclose the preparation method of polyisoprene oligomer, branched modification agent and branching type rare-earth isoprene rubber.The polyisoprene oligomer, wherein the number-average molecular weight of the oligomer is 3000~30000, it along the content of Isosorbide-5-Nitrae structural unit is 65~75 weight % in the structure of the oligomer, anti-1, the content of 4 structural units is 18~28 weight %, and the content of 3,4 structural units is 6~12 weight %.The method that polyisoprene oligomer provided by the invention can provide through the invention is prepared as branched modification agent, and preparation process is simply and without using water or ethyl alcohol as terminator；It is further used for preparing branching type rare-earth isoprene rubber and polymer kinetics viscosity can be effectively reduced, is conducive to polymer post-production.
Description
Technical field
The present invention relates to polyisoprene branching agent fields, and in particular, to polyisoprene oligomer, branched modification agent
With the preparation method of branching type rare-earth isoprene rubber.
Background technique
The structure and performance of isoprene rubber are similar to natural rubber, are a kind of general synthesis rubbers with Good All-around Property
Glue, mainly for the production of tire.In recent years, since there is rare-earth isoprene rubber good anti-slippery and lower rolling to hinder
Power, and wearability is still able to maintain good level, in the world, tire enterprise is concerned.
But the isoprene rubber molecular weight of rare earth catalyst isoprene polymerization preparation is high, and linear degree is high, narrow molecular weight distribution,
The problems such as solution viscosity is big during polymerization process, poor in processability limits its industrialized popularization.It synthetic rubber branching and connects
The chemistry " cutting out " of branch structure is the effective ways for controlling Polymer Solution Viscosity and Polymer Processing viscoelastic effect power, simultaneously
The compatibility with other glue kinds and used time can also be improved.
Mooney cis-butadiene cement new varieties 1280 (BR) have a series of excellent processing in the branching that Goodyear company releases
Characteristic also has and the comparable physico-mechanical properties of other cis-butadiene cements.Jin Hu company, South Korea is using dialkyl group zinc as a kind of tune
Agent is saved, is realized on the basis of not influencing Isosorbide-5-Nitrae-structural content to nickel system along the control of Isosorbide-5-Nitrae-polybutadiene degree of branching, product
With good processing performance and physical property.Polymerization reaction of the company, Michelin in rare earth neodymium series catalyzed preparation of poly isoprene
Later period is added lewis acid and prepares branching polyisoprene.Branched modification which reflects rubber is current rubber new varieties
A hot spot.
Liquid polybutadiene is prepared using molybdenum system or lithium-based catalyst in CN200610083360.8, then urges in molybdenum system
Butadiene and liquid polybutadiene carry out the high vinyl polybutadiene rubber that copolymerization is prepared under change system.Due to polybutadiene
The presence of its end of the chain or the double bond in chain in alkene macromonomer, can be copolymerized with other vinyl monomers can prepare setting
Graft copolymer.This method is compared with for the graft polymers of other existing preparations, and the length of branch can be in preparation solution
It is just controlled when state polymer, distribution is relatively uniform, and homopolymer content is few, and product quality is high.But the standby liquid of the patent system
Polybutadiene needs to terminate through ethyl alcohol, precipitates, washs and drying and other steps obtain, then by the rear of liquid polybutadiene dissolution
It can be used.Route is lengthy and cumbersome.Furthermore it is molten that water, oxygen and remaining polarity can be inevitably introduced in above-mentioned sequence of operations
Agent influences subsequent polymerization activity.
Summary of the invention
The purpose of the present invention is to solve existing isoprene rubber branching agent preparation process there are the problem of, provide
Polyisoprene oligomer, branched modification agent and branching type rare-earth isoprene rubber preparation method, the polyisoprene oligomer
Branching agent as rare-earth type isoprene rubber, preparation process is simpler and does not bring isoprene rubber polymerization such as water, ethyl alcohol impurity into,
The branching type rare-earth isoprene rubber of acquisition has better viscosity reducing effect.
To achieve the goals above, first aspect present invention provides a kind of polyisoprene oligomer, wherein described oligomeric
The number-average molecular weight of object is 3000~30000, and the content in the structure of the oligomer along Isosorbide-5-Nitrae structural unit is 65~75 weights
% is measured, the content of anti-Isosorbide-5-Nitrae structural unit is 18~28 weight %, and the content of 3,4 structural units is 6~12 weight %.
Preferably, the number-average molecular weight of the oligomer is 4500~28000, along Isosorbide-5-Nitrae knot in the structure of the oligomer
The content of structure unit is 67~71 weight %, and the content of anti-Isosorbide-5-Nitrae structural unit is 19~26 weight %, and 3,4 structural units contain
Amount is 7~11 weight %.
Second aspect of the present invention provides a kind of branched modification agent, which is made in accordance with the following methods:
In the presence of inert atmosphere and alkyl lithium initiator, the isoprene in oligomeric solvent is subjected to oligomerization, is obtained
To polyisoprene oligomer of the invention；
The polyisoprene oligomer is mixed with alkyl aluminum, obtains the branched modification agent.
Preferably, the lithium alkylide is general formula R1Li compound represented, wherein R1For C1~C6Alkyl；It is preferred that described
Lithium alkylide is n-BuLi.
Preferably, the lithium alkylide is (2 × 10 with the molar ratio of isoprene in terms of Li-3~2 × 10-2): 1, preferably
(2.5×10-3~1.5 × 10-2): 1.
Preferably, the alkyl aluminum is general formula AlR2 3Compound represented, wherein R2For C1~C6Alkyl, it is preferably described
Alkyl aluminum is triisobutyl aluminium.
Preferably, the alkyl aluminum is in terms of Al, and the lithium alkylide is in terms of Li, mole of the alkyl aluminum and the lithium alkylide
Than for (1~2): 1, preferably (1.05~1.5): 1.
Preferably, the oligomeric solvent is C5~C10Saturated alkane, oligomerization temperature is 10~70 DEG C, and oligomeric pressure is
0.1~0.4MPa, oligomerization times are 1~10h；It is preferred that oligomerization temperature is 25~65 DEG C, oligomeric pressure is 0.15~0.35MPa,
Oligomerization times are 3~7h.
Third aspect present invention provides a kind of preparation method of branching type rare-earth isoprene rubber, comprising:
In the presence of inert atmosphere and rare earth polymerization catalyst, by isoprene monomer in polymer solvent and of the invention
Branched modification agent carries out polymerization reaction.
Preferably, concentration of the isoprene monomer in the polymer solvent is 8~20 weight %；The branched modification agent
Containing polyisoprene oligomer, the polyisoprene oligomer is 0.5~7 weight % of the isoprene monomer；Institute
It states rare earth polymerization catalyst and contains neodymium element, molar ratio of the rare earth polymerization catalyst in terms of Nd with the isoprene monomer
It is (0.6 × 10-4~5 × 10-4): 1.
Preferably, polymeric reaction temperature is 0~70 DEG C, and polymerization pressure is 0.1~0.4MPa, and polymerization reaction time is
1~10h.
Preferably, the rare earth polymerization catalyst contains carboxylic acid neodymium, alkyl aluminum compound and halide；The alkyl calorize
It is (10~80) with molar ratio of the carboxylic acid neodymium in terms of Nd that object, which is closed, in terms of Al: 1；The halide in terms of halogen with the carboxylic acid
Molar ratio of the neodymium in terms of Nd is (1~6): 1.
Preferably, the carboxylic acid neodymium is the carboxylic acid neodymium of carbon atom number 7-14, and the alkyl aluminum compound is general formula AlR3 3With/
Or AlHR4 2The compound of expression, R3、R4It is respectively C1~C6Alkyl；The halide is general formula AlR5 2The change that Cl is indicated
Close object, R5For C1~C6Alkyl.
Through the above technical solutions, the method that polyisoprene oligomer provided by the invention can provide through the invention
It is prepared as branched modification agent, preparation process is simply and without using water or ethyl alcohol as terminator；The branched modification agent is further
It is used to prepare branching type rare-earth isoprene rubber, the dynamic viscosity of polymer obtained can be effectively reduced, be conducive to polymer
Post-production.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
First aspect present invention provides a kind of polyisoprene oligomer, wherein the number-average molecular weight of the oligomer is
3000~30000, it along the content of Isosorbide-5-Nitrae structural unit is 65~75 weight %, anti-Isosorbide-5-Nitrae structural unit in the structure of the oligomer
Content be 18~28 weight %, the contents of 3,4 structural units is 6~12 weight %.
Preferably, the number-average molecular weight of the oligomer is 4500~28000, along Isosorbide-5-Nitrae knot in the structure of the oligomer
The content of structure unit is 67~71 weight %, and the content of anti-Isosorbide-5-Nitrae structural unit is 19~26 weight %, and 3,4 structural units contain
Amount is 7~11 weight %.
In the present invention, the number-average molecular weight of the oligomer can be characterized by gel permeation chromatography (GPC).It is described low
The structural unit of polymers passes through1H NMR characterization is tested using the AVANCE II 400 of Brooker,Switzerland company production.Along 1,4
Content in each leisure oligomer of structural unit, anti-1,4 structural unit and 3,4 structural units passes through acquisition1H NMR
Spectrogram measures the area of characteristic peak, is computed determination.
Second aspect of the present invention provides a kind of branched modification agent, which is made in accordance with the following methods:
In the presence of inert atmosphere and alkyl lithium initiator, the isoprene in oligomeric solvent is subjected to oligomerization, is obtained
To polyisoprene oligomer of the invention；
The polyisoprene oligomer is mixed with alkyl aluminum, obtains the branched modification agent.
In the present invention, the optional wider range of the type of the lithium alkylide, lithium alkylide commonly used in the art is realized of the invention
Purpose.Preferably, the lithium alkylide is general formula R1Li compound represented, wherein R1For C1~C6Alkyl.Specifically,
The lithium alkylide can be selected from one of lithium methide, isopropyl lithium, n-BuLi, s-butyl lithium, tert-butyl lithium or a variety of, excellent
Selecting the lithium alkylide is n-BuLi.
In the present invention, the dosage of the lithium alkylide can be not particularly limited, can be according to point of expected oligomer
Son amount is suitably selected.Preferably, the lithium alkylide is (2 × 10 with the molar ratio of isoprene in terms of Li-3~2 × 10-2): 1, preferably (2.5 × 10-3~1.5 × 10-2): 1.
In the present invention, the optional wider range of the type of the alkyl aluminum is achieved the object of the present invention.Preferably, institute
Stating alkyl aluminum is general formula AlR2 3Compound represented, wherein R2For C1~C6Alkyl, the preferably described alkyl aluminum be triisobutyl
Aluminium.
In the present invention, the alkyl aluminum is added after the oligomerization, for oligomeric with the polyisoprene
Object mixing.With the increase of alkyl aluminum dosage, a large amount of inactive co-ordination complexs can be formed, lithium system can be greatly reduced and urge
The rate for changing polymerization reaction finally makes it lose polymerization activity.Preferably, the alkyl aluminum is in terms of Al, and the lithium alkylide is with Li
The molar ratio of meter, the alkyl aluminum and the lithium alkylide is (1~2): 1, preferably (1.05~1.5): 1.
In the present invention, the oligomerization achievees the purpose that obtain polyisoprene oligomer of the invention.It is preferred that
Ground, the oligomeric solvent are C5~C10Saturated alkane, oligomerization temperature be 10~70 DEG C, oligomeric pressure be 0.1~0.4MPa, it is low
The poly- time is 1~10h；It is preferred that oligomerization temperature be 25~65 DEG C, oligomeric pressure be 0.15~0.35MPa, oligomerization times be 3~
7h。
In the present invention, the oligomeric solvent can be selected from hexane, hexamethylene, methyl cyclopentane, normal heptane and normal octane extremely
Few one kind.In the oligomeric solvent, the concentration of isoprene can be 8~20 weight %.
In the present invention, the inert atmosphere can be oxygen free condition, such as nitrogen atmosphere.
In the present invention, the preparation process of the branched modification agent can be with specifically:
Multiple polymerization bottles are vacuumized, High Purity Nitrogen is filled with after high-temperature baking repeatedly three times；By oligomeric solvent, isoamyl two
Alkene is added in multiple polymerization bottles with identical additional amount.
It takes a wherein polymerization bottle conduct to kill miscellaneous bottle, 4-vinylpridine is added as indicator, (referred to as using lithium alkylide
Li the amount of impurity in oligomeric solvent and isoprene) is demarcated.
The initiator lithium alkylide for deducting the metering for accordingly killing miscellaneous amount is added in other polymerization bottles, then above-mentioned oligomeric anti-
The oligomerization of isoprene is carried out under conditions of answering.
Alkyl aluminum (abbreviation Al) is added into polymerization bottle after reaction, obtains the branching containing polyisoprene oligomer
Modifying agent.
The branched modification agent provided by the invention such as above method is made, comprising having limiting structure polyisoprene of the present invention
The alkyl aluminum of oligomer and limited amount can be used for preparing branching type rare-earth isoprene rubber with reduced dynamic viscosity, have
Conducive to the post-production of polymer.
A kind of preparation method of polyisoprene oligomer of the invention can also be provided in the present invention, comprising: in inertia
In the presence of atmosphere and alkyl lithium initiator, the isoprene in oligomeric solvent is subjected to oligomerization.Condition institute as above therein
It states.
Third aspect present invention provides a kind of preparation method of branching type rare-earth isoprene rubber, comprising:
In the presence of inert atmosphere and rare earth polymerization catalyst, by isoprene monomer in polymer solvent and of the invention
Branched modification agent carries out polymerization reaction.
In the present invention, it is preferable that concentration of the isoprene monomer in the polymer solvent be can be 8~20 weights
Measure %.
In the present invention, it is preferable that the branched modification agent contains present invention polyisoprene oligomer above-mentioned, described poly-
Isoprene oligomer is 0.5~7 weight % of the isoprene monomer；Preferably 3~5 weight %.
In the present invention, it is preferable that polymeric reaction temperature is 0~70 DEG C, and polymerization pressure is 0.1~0.4MPa, polymerization
Reaction time is 1~10h.It is preferred that polymeric reaction temperature is 5~65 DEG C, polymerization pressure is 0.15~0.35MPa, polymerization
Reaction time is 2~6h.
In the present invention, the polymer solvent can be C5~C10Alkane and/or C5~C10Cycloalkane, it is highly preferred that
The polymer solvent is selected from one of pentane, isopentane, n-hexane, hexamethylene, normal heptane and normal octane or a variety of.
In the present invention, in order to overcome oxygen inhibition, the polymerization reaction can carry out in an inert atmosphere.Keep inert atmosphere
Method can be to be passed through inert gas into polymerization reaction system.The inert atmosphere for example can be nitrogen.
In the present invention, after polymerization reaction completion, the method for terminating reaction can be carried out using addition terminator
So that living polymer chains is lost activity, achievees the purpose that terminate the polymerization reaction.The type and dosage of the terminator do not have
It is particularly limited to, as long as the terminator can be such that polymer active chain inactivates.Generally, the terminator can for water,
C1~C6Aliphatic alcohol, C4~C12Aliphatic carboxylic acid and one of aryl polyol or a variety of, the aryl is more
Hydroxy compounds refers to that at least there are two be optionally substituted by a hydroxyl group compound generated to the hydrogen atom on phenyl ring.Preferably, the end
Only agent is one of water, methanol, ethyl alcohol, isopropanol and 2,6- di-tert-butyl hydroquinone or a variety of.
In the present invention, the dosage of the terminator is not particularly limited, as long as the dosage of the terminator can incite somebody to action
Active specy inactivation in polymerizate, repeats no more herein.
In the present invention, complete after terminating reaction, polymer solution obtains branching type rare earth isoamyl through precipitating, washing, drying
Rubber.
In the present invention, the type for carrying out the rare earth polymerization catalyst used when the polymerization reaction is not limited especially
System, can be in the prior art for the various rare earth catalysts in isoprene rubber.For example, rare earth polymerization catalyst can contain
It organic carboxylate, alkyl aluminum and/or the alkyl-al hydride of rare earth, halogen contained compound and is obtained by conjugate diene polymerization
Polymer.For another example, rare earth polymerization catalyst can contain carboxylic acid neodymium, alkyl aluminum compound and halide.Preferably, described dilute
Native polymerization catalyst contains carboxylic acid neodymium, alkyl aluminum compound and halide.
In the present invention, it is preferable that the alkyl aluminum compound is (10 with molar ratio of the carboxylic acid neodymium in terms of Nd in terms of Al
~80): 1, preferably (20~50): 1；The halide be with molar ratio of the carboxylic acid neodymium in terms of Nd in terms of halogen (1~
6): 1, preferably (2~4): 1.
In the present invention, the optional wider range of the type of the carboxylic acid neodymium, carboxylic acid neodymium commonly used in the art is realized of the invention
Purpose.Preferably, the carboxylic acid neodymium is the carboxylic acid neodymium of carbon atom number 7-14, it is preferable that the carboxylic acid neodymium can be selected from cycloalkanes
One of sour neodymium, caprylic acid neodymium, neodymium iso-octanate, neodymium caprate and n-capric acid neodymium are a variety of.
In the present invention, the optional wider range of the type of the alkyl aluminum compound, alkyl aluminum commonly used in the art realizes this
The purpose of invention.The alkyl aluminum compound is general formula AlR3 3And/or AlHR4 2The compound of expression, R3、R4Respectively
For C1~C6Alkyl；It is preferred that the alkyl aluminum compound is triisobutyl aluminium and/or diisobutylaluminium hydride.
In the present invention, the optional wider range of the type of the halide, halide commonly used in the art is realized of the invention
Purpose.The halide is general formula AlR5 2The compound that Cl is indicated, R5For C1~C6Alkyl.It is preferred that the halide is
One of aluminium diethyl monochloride, ethyl aluminium sesquichloride and a chloro-di-isobutyl aluminum are a variety of.
In the present invention, the usage amount of the rare earth polymerization catalyst can be according to expected branching type rare-earth isoprene rubber
Molecular weight is suitably selected.Preferably, the rare earth polymerization catalyst contains neodymium element, and the rare earth polymerization catalyst is with Nd
The molar ratio of meter and the isoprene monomer is (0.6 × 10-4~5 × 10-4): 1, preferably (1 × 10-4~4 × 10-4): 1.
In the present invention, the ageing liquid of the rare earth polymerization catalyst can be used.It can be made by the following method:
Any two component in carboxylic acid neodymium, alkyl aluminum compound and halide is contacted in organic solvent and carries out first
Remaining another component, is then added and carries out the second ageing by ageing.
In the present invention, described optional wider range of organic solvent, such as aliphatic saturated hydrocarbon and alicyclic can be selected from；It is preferred that
Selected from C5~C10Linear paraffin and C5~C10Cycloalkane；It is more preferably selected from pentane, isopentane, n-hexane, hexamethylene, just
One of heptane and normal octane are a variety of.
In the present invention, first ageing, the second condition being aged are known to the skilled person, as long as enabling to
Each component in rare earth catalyst is sufficiently mixed, reacts, and then is catalyzed isoprene polymerization and obtains having gathering for the above property different
Pentadiene, but in order to eliminate or reduce the influence caused by ageing process of each component in air, it is described under preferable case
First ageing and the second ageing carry out in an inert atmosphere.The inert atmosphere, which refers to, does not occur chemistry with reactants and products
Any one gas or admixture of gas of effect, such as one or more of nitrogen and periodic table of elements zero group gas.It is described
First ageing condition generally include temperature can for 30~60 DEG C, the time can be 10~60min, it is described second ageing item
Part generally include temperature can for 10~30 DEG C, the time can be 1~48h.
The present invention will be described in detail by way of examples below.
The following are the test characterizing methods in embodiment and comparative example.
Glue dynamic viscosity measuring method: making solvent with hexamethylene, and polymerizate is made into the solution of 2g/100ml,
Torque α of the rotary viscosity measuring solution at different rotating speeds (γ) is used at 25 ± 0.2 DEG C.Glue sample is dynamic according to the following formula
Mechanics viscosities il: τ=α × Z, η=τ/Ds, Z are corner constant, and τ is shear stress, and Ds is shear rate；
Utilize the weight average molecular weight (Mw) and molecular weight distribution (Mw/ of gel permeation chromatography (GPC) characterization polyisoprene
Mn), standard curve is formulated with polystyrene standards；
The microstructure of polymer uses1H NMR characterization, the AVANCE II 400 produced using Brooker,Switzerland company
Test.
Selecting chemical shift δ is the formant of 1.61ppm as the-CH in trans-1,4-polyisoprene3Peak and 3 is analyzed,
- CH in 4- polyisoprene3Peak is analyzed, peak area is denoted as Q；
Chemical shift δ is selected to be used as the formant of 1.68ppm along-CH in 1,4- polyisoprene3, peak area is denoted as P；
Select chemical shift δ for 4.68-4.76ppm formant as in 3,4- polyisoprene=CH2Analysis
Peak, peak area are denoted as N；
Chemical shift δ is selected to be used as the formant of 5.12ppm along 1,4- polyisoprene and trans-1,4-polyisoprene
In isoprene rubber=and CH- analysis peak, peak area M.Then:
Along 1,4- structure %=P/ (P+Q) × 100%
Anti- 1,4- structure %=2M/ (2M+N) × 100%-P/ (P+Q) × 100%
3,4- structure %=N/ (2M+N) × 100%.
Embodiment A1-A3
4 polymerization bottles are labeled as A0, A1, A2, A3, vacuumizes and is filled with High Purity Nitrogen after high-temperature baking, repeatedly
Three times；
In each polymerization bottle be added same amount hexane and isoprene (content of isoprene be 0.10g isoprene/
ML hexane, abbreviation Ip).It takes polymerization bottle A0 as miscellaneous bottle is killed, 4-vinylpridine is added as indicator, nBuLi volumetric solution
The amount of middle impurity obtains killing miscellaneous amount.
It is added in polymerization bottle A1, A2 and A3 and has deducted the initiator nBuLi (abbreviation Li) for killing miscellaneous amount, initiator nBuLi
Metering according to Li/Ip in table 1 data.The isoprene in polymerization bottle A1, A2, A3 is carried out according to Oligomerization conditions in table 1
Oligomerization, is added the triisobutyl aluminium (abbreviation Al) of metering into polymerization bottle A1, A2, A3 after reaction, the metering of Al with
The molar ratio of the additional amount of Li for killing miscellaneous amount has been deducted according to as listed in table 1, obtaining branched modification agent PIP.
The molecular weight and microstructure content of gained PIP is shown in Table 1.
Embodiment A1, embodiment A2, the respective method of embodiment A3, which correspond to polymerization bottle A1, A2, A3 and respectively obtain branching, to be changed
Property agent PIP method, the branched modification agent number accordingly obtained is PIP-1, PIP-2, PIP-3.
Comparative example A 1
According to the method for embodiment A2, unlike, the additional amount of triisobutyl aluminium meets that " metering of Al is killed with having deducted
The molar ratio of the additional amount of the Li of miscellaneous amount be 0.8 " substitution " Al metering with deducted the molar ratio for killing the additional amount of Li of miscellaneous amount
It is 1.05.Prepare branched modification agent PIP, number PIP-D1.
The molecular weight and microstructure content of gained PIP is shown in Table 1.
Comparative example A 2
According to the method for embodiment A2, the difference is that, " second containing hydrogen chloride is added into polymerization bottle A2 after reaction
Alcoholic solution (metering of HCl is 6 with the molar ratio for having deducted the additional amount of Li for killing miscellaneous amount) " substitution is " after reaction to polymerizeing
The triisobutyl aluminium of metering is added in bottle A2, the metering of Al is 1.05 " with the molar ratio for having deducted the additional amount of Li for killing miscellaneous amount.
Be made liquid polyisoprene by Rotary Evaporators removal major part solvent, then it is vacuum dried after obtain branching
Modifying agent PIP, number PIP-D2.
The molecular weight and microstructure content of resulting liquid PIP is shown in Table 1.
Preparation example 1
Prepare rare earth polymerization catalyst.
A certain amount of neodymium caprate (referred to as: Nd) and triisobutyl is added into catalyst preparation device under nitrogen protection
Aluminium (referred to as: Al), Al/Nd (mol)=30:1；It is aged 0.5h at 30 DEG C, (the letter of a certain amount of aluminium diethyl monochloride is then added
Claim: Cl), Cl/Nd (mol)=2.5:1 continues at 30 DEG C to be aged 1h.
Catalyst aging liquid is made and is denoted as Cat-1.
Preparation example 2
Prepare rare earth polymerization catalyst.
A certain amount of neodymium caprate (referred to as: Nd) and triisobutyl is added into catalyst preparation device under nitrogen protection
Aluminium (referred to as: Al), Al/Nd (mol)=20:1；It is aged 10min at 40 DEG C, a certain amount of aluminium diethyl monochloride is then added
(referred to as: Cl), Cl/Nd (mol)=4:1 continue to be aged 48h at 20 DEG C.
Catalyst aging liquid is made and is denoted as Cat-2.
Preparation example 3
Prepare rare earth polymerization catalyst.
A certain amount of neodymium caprate (referred to as: Nd) and triisobutyl is added into catalyst preparation device under nitrogen protection
Aluminium (referred to as: Al), Al/Nd (mol)=50:1；It is aged 1h at 60 DEG C, (the letter of a certain amount of aluminium diethyl monochloride is then added
Claim: Cl), Cl/Nd (mol)=2:1 continues at 10 DEG C to be aged 35h.
Catalyst aging liquid is made and is denoted as Cat-3.
Embodiment B1
It is replaced in stainless steel cauldron three times through vacuum pump drainage and high pure nitrogen, is then respectively adding hexane and isoamyl
The branched modification agent PIP-1 (institute that embodiment A1 is obtained is added in diene (concentration of isoprene in hexane is about 13 weight %)
Containing polyisoprene (WPIP) it is isoprene (WIp) 3 weight %).Cat-1 (Nd/Ip (mol)=3.0 × 10 is added-4: 1)
Afterwards, 6h is reacted at 50 DEG C, 0.25MPa, it is whole with the ethyl alcohol containing 2,6- di-tert-butyl hydroquinone (264) after polymerization
It only reacts, obtains polymer glue.Polymer solution is through precipitating, washing, dry polymer.
Polymer test result is shown in Table 2.Rotational viscometer measures γ=49.81s-1When dynamic viscosity be 0.165Pa
It is 35.4 ten thousand that s, GPC, which measure polymer number-average molecular weight, molecular weight distributing index 3.87, and polymerizate Isosorbide-5-Nitrae-structural content is
98.0%.
Embodiment B2
It is replaced in stainless steel cauldron three times through vacuum pump drainage and high pure nitrogen, is then respectively adding hexane and isoamyl
The branched modification agent PIP-2 (institute that embodiment A2 is obtained is added in diene (concentration of isoprene in hexane is about 13 weight %)
Containing polyisoprene (WPIP) it is isoprene (WIp) 5 weight %).Cat-1 (Nd/Ip (mol)=3.0 × 10 is added-4: 1)
Afterwards, 5h is reacted at 55 DEG C, 0.20MPa, it is whole with the ethyl alcohol containing 2,6- di-tert-butyl hydroquinone (264) after polymerization
It only reacts, polymer solution is through precipitating, washing, dry polymer.
Polymer analysis test is carried out, table 2 is as a result listed in.
Embodiment B3
It is replaced in stainless steel cauldron three times through vacuum pump drainage and high pure nitrogen, is then respectively adding hexane and isoamyl
The branched modification agent PIP-3 (institute that embodiment A3 is obtained is added in diene (concentration of isoprene in hexane is about 13 weight %)
Containing polyisoprene (WPIP) it is isoprene (WIp) 4 weight %).Cat-1 (Nd/Ip (mol)=3.0 × 10 is added-4: 1)
Afterwards, 6h is reacted at 60 DEG C, 0.30MPa, it is whole with the ethyl alcohol containing 2,6- di-tert-butyl hydroquinone (264) after polymerization
It only reacts, polymer solution is through precipitating, washing, dry polymer.
Polymer analysis test is carried out, table 2 is as a result listed in.
Embodiment B4
According to the method for embodiment B1, the difference is that, " it is (contained that the branched modification agent PIP-1 that embodiment A1 is obtained is added
Polyisoprene (WPIP) it is isoprene (WIp) 0.5 weight %) " " the obtained branched modification agent of embodiment A1 is added in substitution
PIP-1 (contained polyisoprene (WPIP) it is isoprene (WIp) 3 weight %) ".Prepare polymer.
Polymer analysis test, is as a result listed in table 2.
Embodiment B5
According to the method for embodiment B1, the difference is that, " it is (contained that the branched modification agent PIP-1 that embodiment A1 is obtained is added
Polyisoprene (WPIP) it is isoprene (WIp) 1.5 weight %) " " the obtained branched modification agent of embodiment A1 is added in substitution
PIP-1 (contained polyisoprene (WPIP) it is isoprene (WIp) 3 weight %) ".Prepare polymer.
Polymer analysis test, is as a result listed in table 2.
Embodiment B6
It is replaced in stainless steel cauldron three times through vacuum pump drainage and high pure nitrogen, is then respectively adding hexane and isoamyl
The branched modification agent PIP-2 (institute that embodiment A2 is obtained is added in diene (concentration of isoprene in hexane is about 13 weight %)
Containing polyisoprene (WPIP) it is isoprene (WIp) 1 weight %).Cat-1 (Nd/Ip (mol)=3.0 × 10 is added-4: 1)
Afterwards, 4h is reacted at 50 DEG C, after polymerization, terminates reaction with the ethyl alcohol containing 2,6- di-tert-butyl hydroquinone (264), obtain
To polymer glue.Polymer solution is through precipitating, washing, dry polymer.
Polymer analysis test is carried out, table 2 is as a result listed in.
Embodiment B7
According to the method for embodiment B6, the difference is that, " it is (contained that the branched modification agent PIP-2 that embodiment A2 is obtained is added
Polyisoprene (WPIP) it is isoprene (WIp) 3 weight %) " " the obtained branched modification agent PIP- of embodiment A2 is added in substitution
2 (contained polyisoprene (WPIP) it is isoprene (WIp) 1 weight %) ".Prepare polymer.
Polymer analysis test, is as a result listed in table 2.
Embodiment B8
According to the method for embodiment B6, the difference is that, " it is (contained that the branched modification agent PIP-2 that embodiment A2 is obtained is added
Polyisoprene (WPIP) it is isoprene (WIp) 7 weight %) " " the obtained branched modification agent PIP- of embodiment A2 is added in substitution
2 (contained polyisoprene (WPIP) it is isoprene (WIp) 1 weight %) ".Prepare polymer.
Polymer analysis test, is as a result listed in table 2.
Embodiment B9
It is replaced in stainless steel cauldron three times through vacuum pump drainage and high pure nitrogen, is then respectively adding hexane and isoamyl
The branched modification agent PIP-3 (institute that embodiment A3 is obtained is added in diene (concentration of isoprene in hexane is about 13 weight %)
Containing polyisoprene (WPIP) it is isoprene (WIp) 1 weight %).Cat-1 (Nd/Ip (mol)=3.0 × 10 is added-4: 1)
Afterwards, 4h is reacted at 50 DEG C, after polymerization, terminates reaction with the ethyl alcohol containing 2,6- di-tert-butyl hydroquinone (264), obtain
To polymer glue.Polymer solution is through precipitating, washing, dry polymer.
Polymer analysis test is carried out, table 2 is as a result listed in.
Embodiment B10
According to the method for embodiment B9, the difference is that, " it is (contained that the branched modification agent PIP-3 that embodiment A3 is obtained is added
Polyisoprene (WPIP) it is isoprene (WIp) 2 weight %) " " the obtained branched modification agent PIP- of embodiment A3 is added in substitution
3 (contained polyisoprene (WPIP) it is isoprene (WIp) 1 weight %) ".Prepare polymer.
Polymer analysis test, is as a result listed in table 2.
Embodiment B11
It is replaced in stainless steel cauldron three times through vacuum pump drainage and high pure nitrogen, is then respectively adding hexane and isoamyl
The branched modification agent PIP-2 (institute that embodiment A2 is obtained is added in diene (concentration of isoprene in hexane is about 20 weight %)
Containing polyisoprene (WPIP) it is isoprene (WIp) 5 weight %).Cat-2 (Nd/Ip (mol)=5.0 × 10 is added-4: 1)
Afterwards, 2h is reacted at 10 DEG C, 0.15MPa, it is whole with the ethyl alcohol containing 2,6- di-tert-butyl hydroquinone (264) after polymerization
It only reacts, polymer solution is through precipitating, washing, dry polymer.
Polymer analysis test is carried out, table 2 is as a result listed in.
Embodiment B12
It is replaced in stainless steel cauldron three times through vacuum pump drainage and high pure nitrogen, is then respectively adding hexane and isoamyl
The branched modification agent PIP-3 (institute that embodiment A3 is obtained is added in diene (concentration of isoprene in hexane is about 8 weight %)
Containing polyisoprene (WPIP) it is isoprene (WIp) 4 weight %).Cat-3 (Nd/Ip (mol)=0.6 × 10 is added-4: 1),
8h is reacted at 60 DEG C, 0.35MPa, after polymerization, is terminated with the ethyl alcohol containing 2,6- di-tert-butyl hydroquinone (264) anti-
It answers, polymer solution is through precipitating, washing, dry polymer.
Polymer analysis test is carried out, table 2 is as a result listed in.
Embodiment B13
According to the method for embodiment B11, the difference is that, with " the branched modification agent PIP-2 (institute that addition embodiment A2 is obtained
Containing polyisoprene (WPIP) it is isoprene (WIp) 3 weight %) " " the obtained branched modification agent of embodiment A2 is added in substitution
PIP-2 (contained polyisoprene (WPIP) it is isoprene (WIp) 5 weight %) ".Prepare polymer.
Polymer analysis test, is as a result listed in table 2.
Embodiment B14
According to the method for embodiment B12, the difference is that, with " the branched modification agent PIP-3 (institute that addition embodiment A3 is obtained
Containing polyisoprene (WPIP) it is isoprene (WIp) 2 weight %) " " the obtained branched modification agent of embodiment A3 is added in substitution
PIP-3 (contained polyisoprene (WPIP) it is isoprene (WIp) 4 weight %) ".Prepare polymer.
Polymer analysis test, is as a result listed in table 2.
Comparative example B1
It is replaced in stainless steel cauldron three times through vacuum pump drainage and high pure nitrogen, is then respectively adding hexane and isoamyl
Cat-1 (Nd/Ip (mol)=3.0 × 10 is added in diene (concentration of isoprene in hexane is about 13 weight %)-4: 1) after,
It is reacted 4 hours at 50 DEG C, after polymerization, terminates reaction with the ethyl alcohol containing 2,6- di-tert-butyl hydroquinone (264), gather
Polymer solution is through precipitating, washing, dry polymer.
Polymer analysis test is carried out, table 2 is as a result listed in.
Comparative example B2
It is replaced in stainless steel cauldron three times through vacuum pump drainage and high pure nitrogen, is then respectively adding hexane and isoamyl
The branched modification agent PIP-D1 that comparative example A 1 obtains is added in diene (concentration of isoprene in hexane is about 13 weight %)
(contained polyisoprene (WPIP) it is isoprene (WIp) 3 weight %).Cat-1 (Nd/Ip (mol)=3.0 × 10 is added-4:
1) it after, reacts 4 hours at 50 DEG C, after polymerization, is terminated with the ethyl alcohol containing 2,6- di-tert-butyl hydroquinone (264) anti-
It answers, polymer solution is through precipitating, washing, dry polymer.
Polymer analysis test is carried out, table 2 is as a result listed in.
Comparative example B3
It is replaced in stainless steel cauldron three times through vacuum pump drainage and high pure nitrogen, is then respectively adding hexane and isoamyl
The branched modification agent PIP-D2 that comparative example A 2 obtains is added in diene (concentration of isoprene in hexane is about 13 weight %)
(contained polyisoprene (WPIP) it is isoprene (WIp) 3 weight %).Cat-1 (Nd/Ip (mol)=3.0 × 10 is added-4:
1) it after, reacts 4 hours at 50 DEG C, after polymerization, is terminated with the ethyl alcohol containing 2,6- di-tert-butyl hydroquinone (264) anti-
It answers, polymer solution is through precipitating, washing, dry polymer.
Polymer analysis test is carried out, table 2 is as a result listed in.
Comparative example B4
It is replaced in stainless steel cauldron three times through vacuum pump drainage and high pure nitrogen, is then respectively adding hexane and isoamyl
Diene (concentration of isoprene in hexane is about 20 weight %).Cat-2 (Nd/Ip (mol)=5.0 × 10 is added-4: 1) after,
2h is reacted at 10 DEG C, 0.15MPa, after polymerization, is terminated with the ethyl alcohol containing 2,6- di-tert-butyl hydroquinone (264) anti-
It answers, polymer solution is through precipitating, washing, dry polymer.
Polymer analysis test is carried out, table 2 is as a result listed in.
Comparative example B5
It is replaced in stainless steel cauldron three times through vacuum pump drainage and high pure nitrogen, is then respectively adding hexane and isoamyl
Diene (concentration of isoprene in hexane is about 8 weight %).Cat-3 (Nd/Ip (mol)=0.6 × 10 is added-4: 1),
60 DEG C, react 8h under 0.35MPa, after polymerization, terminated with the ethyl alcohol containing 2,6- di-tert-butyl hydroquinone (264) anti-
It answers, polymer solution is through precipitating, washing, dry polymer.
Polymer analysis test is carried out, table 2 is as a result listed in.
Table 1
Table 2
It can be seen that in embodiment B1-B3, B7 from embodiment, comparative example and 2 result of table, using identical catalyst
Branching type rare-earth isoprene rubber is prepared in the case where Cat-1 and dosage, is added in polymerization reaction provided by the invention different containing gathering
The branched modification agent (the branched modification agent PIP of embodiment A1- embodiment A3) of pentadiene oligomer and dosage meets poly- isoamyl two
When alkene oligomer is 3~5 weight % of isoprene monomer, (same catalyst Cat-1 is used compared to comparative example B1-B3
And dosage, but without addition branched modification agent (B1), and use branched modification agent (PIP-D1, PIP-D2)), it can synthesize to obtain
When the branching type rare-earth isoprene rubber of suitable number-average molecular weight, it is effectively reduced the dynamics of rare-earth isoprene rubber glue obtained
Viscosity, and it is little to the influence of polymerization activity simultaneously, and conversion ratio can reach 95% or more.
Embodiment B4-B6, B8-B10 similarly when preparing branching type rare-earth isoprene rubber, is added branching of the invention and changes
Property agent (PIP-1, PIP-2, PIP-3), compared to comparative example B1-B3 use identical catalyst Cat-1 and dosage when, can obtain
To suitable number-average molecular weight branching type rare-earth isoprene rubber when, be effectively reduced the power of rare-earth isoprene rubber glue obtained
Learn viscosity.
Cat-2 or Cat-3 is used in embodiment B11-B14, and is limited to the dosage in the present invention and is carried out isoprene rubber conjunction
Cheng Shi is using same catalyst and dosage (but branched modification agent is not added) compared to comparative example B4, B5, is quite being counted
The branching type rare-earth isoprene rubber of average molecular weight can equally be effectively reduced the dynamics of rare-earth isoprene rubber glue obtained
Viscosity.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of polyisoprene oligomer, which is characterized in that the number-average molecular weight of the oligomer is 3000~30000, institute
The content for stating suitable Isosorbide-5-Nitrae structural unit in the structure of oligomer is 65~75 weight %, and the content of anti-Isosorbide-5-Nitrae structural unit is 18~28
Weight %, the content of 3,4 structural units are 6~12 weight %.
2. oligomer according to claim 1, wherein the number-average molecular weight of the oligomer is 4500~28000, described
The content of suitable Isosorbide-5-Nitrae structural unit is 67~71 weight % in the structure of oligomer, and the content of anti-Isosorbide-5-Nitrae structural unit is 19~26 weights
% is measured, the content of 3,4 structural units is 7~11 weight %.
3. a kind of branched modification agent, which is made in accordance with the following methods:
In the presence of inert atmosphere and alkyl lithium initiator, the isoprene in oligomeric solvent is subjected to oligomerization, is weighed
Benefit require 1 or 2 described in polyisoprene oligomer；
The polyisoprene oligomer is mixed with alkyl aluminum, obtains the branched modification agent.
4. branched modification agent according to claim 3, wherein the lithium alkylide is general formula R1Li compound represented, wherein
R1For C1~C6Alkyl；It is preferred that the lithium alkylide is n-BuLi；
Preferably, the lithium alkylide is (2 × 10 with the molar ratio of isoprene in terms of Li-3~2 × 10-2): 1, preferably (2.5
×10-3~1.5 × 10-2): 1.
5. branched modification agent according to claim 3, wherein the alkyl aluminum is general formula AlR2 3Compound represented,
Middle R2For C1~C6Alkyl, the preferably described alkyl aluminum be triisobutyl aluminium；
Preferably, the alkyl aluminum is in terms of Al, and in terms of Li, the molar ratio of the alkyl aluminum and the lithium alkylide is the lithium alkylide
(1~2): 1, preferably (1.05~1.5): 1.
6. branched modification agent according to claim 3, wherein the oligomeric solvent is C5~C10Saturated alkane, it is oligomeric
Temperature is 10~70 DEG C, and oligomeric pressure is 0.1~0.4MPa, and oligomerization times are 1~10h；
It is preferred that oligomerization temperature is 25~65 DEG C, oligomeric pressure is 0.15~0.35MPa, and oligomerization times are 3~7h.
7. a kind of preparation method of branching type rare-earth isoprene rubber, comprising:
In the presence of inert atmosphere and rare earth polymerization catalyst, by the isoprene monomer and claim 3-6 in polymer solvent
Any one of described in branched modification agent carry out polymerization reaction.
8. preparation method according to claim 7, wherein concentration of the isoprene monomer in the polymer solvent is 8
~20 weight %；The branched modification agent contains polyisoprene oligomer, and the polyisoprene oligomer is the isoamyl
0.5~7 weight % of diene monomers；The rare earth polymerization catalyst contains neodymium element, and the rare earth polymerization catalyst is in terms of Nd
Molar ratio with the isoprene monomer is (0.6 × 10-4~5 × 10-4): 1；
Preferably, polymeric reaction temperature be 0~70 DEG C, polymerization pressure be 0.1~0.4MPa, polymerization reaction time be 1~
10h。
9. preparation method according to claim 7 or 8, wherein the rare earth polymerization catalyst contains carboxylic acid neodymium, alkyl aluminum
Compound and halide；The alkyl aluminum compound is (10~80) with molar ratio of the carboxylic acid neodymium in terms of Nd in terms of Al: 1；
The halide is (1~6) with molar ratio of the carboxylic acid neodymium in terms of Nd in terms of halogen: 1.
10. preparation method according to claim 9, wherein the carboxylic acid neodymium is the carboxylic acid neodymium of carbon atom number 7-14, described
Alkyl aluminum compound is general formula AlR3 3And/or AlHR4 2The compound of expression, R3、R4It is respectively C1~C6Alkyl；It is described
Halide is general formula AlR5 2The compound that Cl is indicated, R5For C1~C6Alkyl.
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