CN104628896B - Method for improving coupling efficiency of solution polymerized styrene-butadiene rubber - Google Patents
Method for improving coupling efficiency of solution polymerized styrene-butadiene rubber Download PDFInfo
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Abstract
The invention discloses a method for improving the coupling efficiency of solution polymerized styrene-butadiene rubber. The method includes: under anionic polymerization conditions, in the presence of an organic lithium initiator and a structure regulator, polymerizing styrene and butadiene in a solvent, and within 2-15min after the polymerization reaction reaches a peak temperature, adding a coupling agent to conduct coupling. Specifically, the structure regulator is a compound with a structure shown as formula (I), and in the formula (I), R1 is alkyl of C1-C10. The method provided by the invention can regulate the coupling efficiency of the solution polymerized styrene-butadiene rubber and improve the coupling efficiency of the dissolved styrene butadiene rubber. (formula I).
Description
Technical field
The present invention relates to a kind of method for improving solution polymerized butadiene styrene rubber coupling efficiency.
Background technology
The synthetic reaction of existing solution polymerized butadiene styrene rubber mainly adopts anionic solution polymerization method.With hexamethylene as molten
Agent, lithium alkylide or rare earth are catalyst, and by anionic solution polymerization method solution polymerized butadiene styrene rubber is synthesized.Solution polymerized butadiene styrene rubber
Main purposes be used as tire product.Tire product develops into radial from cross-ply, and then to high-performance
Radial tire and green radial, higher and higher requirement is it is also proposed to performance, both required low rolling resistance with
Beneficial to energy-conservation, require there is very high wet-sliding resistant performance to ensure vehicle driving safety again, while also requiring to have good wearability
Can be with other combination properties.Require for the specific performance of tire solution polymerized butadiene styrene rubber, the use of more method is at present to adopt
Synthesize star-like solution polymerized butadiene styrene rubber with coupling method, the coupling agent for generally using is stanniferous or silicon atom halogenide, adopts these
The GPC spectrograms of the star-type polymer of method synthesis are usually bimodal distribution curve.
It is anti-using being coupled more than the batch-type solution polymerized butadiene styrene rubber of styrene random copolyreaction synthesis with butadiene at present
Molecular weight distribution should be widened, molecular weight is changed into bimodal wide distribution, to reaching the effect for improving processing characteristics from unimodal narrow ditribution
Really, the main coupling agent for adopting has Silicon chloride., butter of tin etc..At present, in solution polymerized butadiene styrene rubber building-up process, it is coupled effect
Rate need to be improved, and needs a kind of method for improving solution polymerized butadiene styrene rubber coupling efficiency.
The content of the invention
It is an object of the invention to provide a kind of method for simply increasing solution polymerized butadiene styrene rubber coupling efficiency, by using
The method can regulate and control to solution polymerized butadiene styrene rubber coupling efficiency, improve solution polymerized butadiene styrene rubber coupling efficiency.
To achieve these goals, the present invention provides a kind of method for improving solution polymerized butadiene styrene rubber coupling efficiency, the method
Including：
Under anionic polymerization conditions, in the presence of organic lithium initiator and structure regulator, styrene and fourth two are made
Alkene is polymerized in a solvent, and adds coupling agent to be coupled in 2-15 minutes after polyreaction reaches peak temperature；
Wherein, the structure regulator is with formula（I）The compound of shown structure,
Formula（I）In, R1For C1-C10Alkyl.
By above-mentioned technical proposal, solution polymerized butadiene styrene rubber coupling efficiency can be regulated and controled, improve solution polymerized butadiene styrene rubber
Coupling efficiency.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It should be appreciated that described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The present invention provides a kind of method for improving solution polymerized butadiene styrene rubber coupling efficiency, and the method includes：
Under anionic polymerization conditions, in the presence of organic lithium initiator and structure regulator, styrene and fourth two are made
Alkene is polymerized in a solvent, and adds coupling agent to be coupled in 2-15 minutes after polyreaction reaches peak temperature；
Wherein, the structure regulator is with formula（I）The compound of shown structure,
Formula（I）In, R1For C1-C10Alkyl.
According to the present invention, the structure regulator is with formula（I）The compound of shown structure,
Formula（I）In, R1For C1-C10Alkyl, including C1-C10Straight chained alkyl and C3-C10Branched alkyl, its concrete reality
Example can be including but not limited to：Methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, positive penta
Base, isopentyl, tertiary pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and positive decyl.
Formula（I）In, R1Preferably C1-C6Alkyl, more preferably C1-C4Alkyl, more preferably ethyl or butyl,
The butyl can be normal-butyl, sec-butyl, isobutyl group or the tert-butyl group.
The alkyl tetrahydro furfuryl group ether is specifically as follows but is not limited to：Ethyl tetrahydrofury ether, tetrahydrofurfuryl propyl ether, four
Tetrahydrofurfuryl butyl ether, tetrahydrofurfuryl amyl ether, tetrahydrofurfuryl hexyl ether, tetrahydrofurfuryl heptyl ether, tetrahydrofurfuryl Octyl Ether, tetrahydrochysene
One or more in furfuryl group nonyl ethers and tetrahydrofurfuryl decyl ethers, preferably ethyl tetrahydrofury ether and/or tetrahydrofurfuryl fourth
Base ether, more preferably ethyl tetrahydrofury ether.
According to the present invention, the consumption of the structure regulator can carry out appropriate selection according to specific polymerizing condition.
Usually, relative to the weight portion of total amount 100 of styrene and butadiene, the consumption of the structure regulator is 0.1-0.5 weights
Amount part, preferably 0.2-0.3 weight portions.
The structure regulator can be added in polymerization system in various conventional modes.For example, the structure is adjusted
Agent can together or separately be added in polymerization system with organic lithium initiator.
The organic lithium initiator can be anionic polymerisation field commonly use various can cause the organic of olefinic polymerization
Single lithium compound, organic two-lithium compound or organic many lithium compounds, are not particularly limited.The organic lithium initiator is preferably
Organo monolithium compounds, more preferably formula（II）The compound of shown structure,
R2Li formulas（II）,
Formula（II）In, R2For C1-C6Alkyl, C3-C12Cycloalkyl, C7-C14Aralkyl or C6-C12Aryl.
The C1-C6Alkyl include C1-C6Straight chained alkyl and C3-C6Branched alkyl, its instantiation can include
But it is not limited to：Methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, uncle
Amyl group, neopentyl and n-hexyl.
The C3-C12The instantiation of cycloalkyl can including but not limited to：Cyclopropyl, cyclopenta, cyclohexyl, 4- first
Butylcyclohexyl, 4- ethylcyclohexyls, 4- n-pro-pyls cyclohexyl and 4- normal-butyl cyclohexyl.
The C7-C14The instantiation of aralkyl can including but not limited to：Phenyl methyl, phenylethyl, phenyl are just
Propyl group, phenyl normal-butyl, phenyl t-butyl, propyloxy phenyl base, phenyl n-pentyl and phenyl normal-butyl.
The C6-C12The instantiation of aryl can including but not limited to：Phenyl, naphthyl, 4- aminomethyl phenyls and 4- second
Base phenyl.
The organic lithium initiator is specifically as follows but is not limited to：Ethyl-lithium, n-pro-pyl lithium, isopropyl lithium, n-BuLi,
S-butyl lithium, tert-butyl lithium, phenyl lithium, 2- naphthyl lithiums, 4- butyl phenyl lithiums, 4- tolyl lithiums, cyclohexyl lithium and 4- butyl rings
One or more in hexyl lithium, preferably n-BuLi and/or s-butyl lithium, more preferably n-BuLi.
The present invention is not particularly limited to the consumption of the organic lithium initiator, can prepare solution polymerized butylbenzene rubber for this area
Conventional consumption during glue.Under preferable case, relative to 100g polymerized monomers（Styrene and butadiene）, the organic lithium initiator
Consumption can be 0.5-2mmol, preferably 0.5-1mmol.
According to the present invention, the relative scale between the styrene and butadiene can prepare solution polymerized butylbenzene rubber for this area
Conventional ratio during glue.Under normal circumstances, the styrene and the weight ratio of butadiene can be 0.17-0.43：1.
The present invention is not particularly limited to the anionic polymerisation condition, can be the conventional selection of this area.
As a rule, the anionic polymerisation condition includes temperature, pressure and time.Wherein, the temperature and pressure can be with
Selected and changed in wider scope, in order to be more beneficial for the carrying out of polyreaction, the temperature is preferably 10-160
DEG C, more preferably 40-70 DEG C, the pressure is preferably 0.05-0.5MPa, more preferably 0.1-0.3MPa.
In the present invention, the pressure refers both to gauge pressure.
According to the present invention, the solvent can for it is various can be able to be hydrocarbon for example as the organic substance of reaction media
Class solvent and/or ether solvent.The varsol can be C5-C7Cycloalkane, aromatic hydrocarbons and isoparaffin in one kind or many
Kind.The instantiation of the varsol can be including but not limited to：Benzene, toluene, hexane, hexamethylene, pentane, heptane, hexane
With one or more in hexamethylene.The ether solvent can be C4-C15Monoether and/or polyether.The ether solvent
Instantiation can be including but not limited to：Tert-butoxyethoxy ethane and/or tetrahydrofuran.Wherein, these solvents can
It is used alone, can also be used in mixed way.The consumption of the solvent can reasonably be selected according to the consumption of monomer, for example,
It is 1-30 weight %, preferably 5-20 weight % that the consumption of the solvent can cause the total concentration of the styrene and butadiene.
Additionally, it is as well known to those skilled in the art, micro water is there may be in the solvent.But water is anionic polymerisation
Terminator, it can terminate chain propagation reaction by proton translocation, therefore, in order that the anionic polymerisation can
It is smoothed out, solvent is preferably carried out eliminating water by the present invention.The mode of the eliminating water can be to add deicer toward the solvent.
The species of the deicer is known to the skilled person, for example, can be 5A point purchased from Dalian Kang Yu Chemical Co., Ltd.s
Son sieve.
According to the present invention, described being aggregated in the atmosphere formed by non-active gas is carried out.The non-active gas are referred to
There is no chemically interactive gas with reactant, reaction product and solvent under polymerization conditions, for example：Nitrogen
And/or group 0 element gas（Such as argon）.
According to the present invention, also include mixture and the coupling agent haptoreaction for obtaining polymerization, so that polymerization process
The living chain of middle generation is coupled.The coupling agent preferably has formula（III）The compound of shown structure
RaSiYbFormula（III）,
Formula（III）In, each R is independently of one another C1-C8Alkyl, C3-C8Cycloalkyl, C3-C8Cycloalkyl-C1-C8Alkyl, C1-
C8Alkyl-C3-C8Cycloalkyl, C6-C10Aryl, C6-C10Aryl-C1-C8Alkyl or C1-C8Alkyl-C6-C10Aryl, preferred C1-C6
Alkyl, cyclopenta, cyclohexyl, phenyl, naphthyl, tolyl, benzyl or phenethyl；A is 0-3, preferential 0-2；Y is halogen, preferably
Chlorine or bromine, more preferably chlorine；Subscript b is 1-4, preferential 2-4.
In order in the conditions of the invention, further improve the coupling efficiency of the coupling agent, the coupling agent is more preferably
For methyl trichlorosilane and/or Silicon chloride..
The consumption of the coupling agent is so that the polymer after being coupled disclosure satisfy that specifically used requirement is defined.Usually, institute
Organic lithium initiator is stated in terms of lithium, the coupling agent is 0.1-0.25 with the mol ratio of the organic lithium initiator：1, preferably
0.13-0.22, more preferably 0.15-0.2：1.
According to the present invention, in order to control the coupling efficiency of the coupling agent, the addition opportunity of the coupling agent is extremely important.
The present inventor has found through in-depth study, adds the idol in 2-15 minutes after reach peak temperature in polyreaction
Connection agent, it is possible to increase the coupling efficiency of the coupling agent.In order to further improve the coupling efficiency of the coupling agent, preferably poly-
Close reaction and reach and add in 5-8 minutes after peak temperature the coupling agent.
According to the present invention, coupling condition is not particularly limited, can be the conventional selection of this area.Normal conditions
Under, coupling condition includes temperature, pressure and time, and under preferable case, the temperature can be for example 50-120 DEG C, be preferably
60-100 DEG C, the pressure can be for example 0.01-0.5MPa, and preferably 0.1-0.3MPa, the time for example can be 1-
100 minutes, preferably 5-60 minutes.
According to the invention, it is further possible to be included in after coupling reaction terminates, the reactant mixture for obtaining is contacted with terminator,
So that polyreaction terminates.The terminator can be that commonly use in anionic polymerisation field various can make active chain termination
Material, for example, can be preferably C for water and/or alcohol, the alcohol1-C5Alcohol, in methanol, ethanol, normal propyl alcohol and isopropanol
One or more.Under preferable case, the terminator can be water.
The present invention is not particularly limited to the consumption of the terminator, can be the conventional amount used of this area.Usually, institute
State terminator and organic lithium initiator（In terms of lithium）Mol ratio can be 0.2-2：1, preferably 0.5-1：1.
Complete in polyreaction（Generally terminate polymerization）Afterwards, the method according to the invention can also be included to being polymerized
To mixture in add various additives, obtain polymer with various performances or function to give, for example, add age resistor,
So that the polymer for obtaining has good ageing resistace.
The present invention is not particularly limited for the type of the age resistor, can be the conventional various age resistor in this area.
For example, the age resistor can be phenols and/or amines antioxidants.Specifically, the age resistor can be 4,6- dioctyl sulfur
Acute pyogenic infection of nails base orthoresol, four [3- (3,5- di-tert-butyl-hydroxy phenyls) propanoic acid] pentaerythritol esters, (uncles of 2,4- bis- of phosphorous acid three
Butyl phenyl) ester, 3- (3,5- di-tert-butyl-hydroxy phenyls) propanoic acid stearyl, DBPC 2,6 ditertiary butyl p cresol, tertiary fourth
One or more in base catechol and 2,2 '-methylene-bis- (4- methyl-6-tert-butylphenols).By four [3- (3,5-
Di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester and phosphorous acid three (2,4- di-tert-butyl-phenyl) ester be when being used in mixed way,
The content of phosphorous acid three (2,4- di-tert-butyl-phenyls) ester is preferably no greater than 50 weight %；By 3- (3,5- di-t-butyl -4- hydroxyls
Base phenyl) propanoic acid stearyl and phosphorous acid three (2,4- di-tert-butyl-phenyl) ester be when being applied in combination, phosphorous acid three (2,4- bis-
Tert-butyl-phenyl) content of ester is preferably no greater than 50 weight %.
According to the present invention, the consumption of the age resistor can be the conventional amount used of this area.For example, relative to styrene and
The weight portion of total amount 100 of butadiene, the consumption of the age resistor can be 0.5-2 weight portions, preferably 0.1-1 weight portions.
The method according to the invention, after age resistor is added, the solution polymerized butadiene styrene rubber can be by purification precipitation, centrifugation
The methods such as separation, filtration, decantation, hot water cohesion are precipitated out from solution, it would however also be possible to employ air- extraction is by reaction system
Solvent is removed, and can know that here will not be described in great detail to this those skilled in the art.
Hereinafter will be described the present invention by embodiment, but the present invention is not limited in following embodiments.
In following examples and comparative example, coupling efficiency carries out gpc analysis by will be coupled the mixture for obtaining, and corresponds to
The peak of remaining copolymer after being coupled the peak area of the polymer for being formed and being coupled the peak area of the polymer for being formed and be coupled
The ratio of area sum is coupling efficiency.
In following examples and comparative example, number-average molecular weight and coupling efficiency are by using the model purchased from Shimadzu Corporation
The chromatograph of gel permeation of LC-10AT（GPC）Measure is obtained, wherein, with THF as mobile phase, with Narrow distribution polystyrene as mark
Sample, test temperature is 25 DEG C.
Embodiment 1
Before the polymerization, by mixed solvent, (hexamethylene and normal hexane, weight ratio is 88：12) with 5A molecular sieves (φ 3 × 5,
Purchased from Dalian Kang Yu Chemical Co., Ltd.s, dry 5 hours at 500 DEG C in advance) soak 1 week.High pure nitrogen protection under, successively to
Mixed solvent 195Kg, styrene 7.83Kg, regulator ethyl tetrahydrofury ether are added in 300 liters of polymeric kettles（ETE）78.4g, gather
Syzygy system Jing high-purity Ns2After displacement deoxidation, butadiene 21.17Kg is added, after stirring 10 minutes, add n-butyllithium solution 350ml
(concentration of n-BuLi is 0.6mol/L) carries out polyreaction.Polymerization initiating temperature is 50 DEG C, and reaction pressure is 0.1MPa.Instead
90 DEG C of peak temperature is reached when answering 10 minutes, reaction pressure is 0.28MPa.116ml methyl three is added in 8 minutes backward reactors of peak temperature
(concentration is 0.25mol/L to chlorosilane solution, and it is 88 that solvent is weight ratio：12 hexamethylene and the mixture of normal hexane) carry out idol
Connection, after being coupled 15 minutes, deionized water 4.8g is added in polymeric kettle, carries out terminating reaction.Stirring adds age resistor after 5 minutes
DBPC 2,6 ditertiary butyl p cresol 232g.
Glue obtains solution polymerized butadiene styrene rubber after water vapor accumulation Jing after mill is dried.Its number-average molecular weight and its
Coupling efficiency is shown in Table 1.
Embodiment 2
Before the polymerization, by mixed solvent, (hexamethylene and normal hexane, weight ratio is 88：12) with 5A molecular sieves (3 × 5,
Purchased from Dalian Kang Yu Chemical Co., Ltd.s, dry 5 hours at 500 DEG C in advance) soak 1 week.High pure nitrogen protection under, successively to
Mixed solvent 195Kg, styrene 7.83Kg, regulator ethyl tetrahydrofury ether are added in 300 liters of polymeric kettles（ETE）58g, polymerization
System Jing high-purity N2After displacement deoxidation, butadiene 21.17Kg is added, after stirring 10 minutes, add n-butyllithium solution 420ml
(concentration of n-BuLi is 0.6mol/L) carries out polyreaction.Polymerization initiating temperature is 50 DEG C, and reaction pressure is 0.1MPa.Instead
90 DEG C of peak temperature is reached when answering 10 minutes, reaction pressure is 0.28MPa.The chlorinations of 170ml tetra- are added in 5 minutes backward reactors of peak temperature
(concentration is 0.33mol/L to silicon solution, and it is 88 that solvent is weight ratio：12 hexamethylene and the mixture of normal hexane) it is coupled,
After being coupled 15 minutes, deionized water 6.0g is added in polymeric kettle, carry out terminating reaction.Stirring adds age resistor 2 after 5 minutes,
6- ditertbutylparacresol 232g.
Glue obtains solution polymerized butadiene styrene rubber after water vapor accumulation Jing after mill is dried.Its number-average molecular weight and its
Coupling efficiency is shown in Table 1.
Embodiment 3
Method according to embodiment 1 is carried out, and 116ml methyl three is except for the difference that added into reactor after peak temperature 15 minutes
(concentration is 0.25mol/L to chlorosilane solution, and it is 88 that solvent is weight ratio：12 hexamethylene and the mixture of normal hexane) carry out idol
Connection, obtains solution polymerized butadiene styrene rubber, and its number-average molecular weight and its coupling efficiency are shown in Table 1.
Embodiment 4
Method according to embodiment 1 is carried out, and 116ml methyl three is except for the difference that added into reactor after peak temperature 10 minutes
(concentration is 0.25mol/L to chlorosilane solution, and it is 88 that solvent is weight ratio：12 hexamethylene and the mixture of normal hexane) carry out idol
Connection, obtains solution polymerized butadiene styrene rubber, and its number-average molecular weight and its coupling efficiency are shown in Table 1.
Comparative example 1
Method according to embodiment 1 is carried out, and 116ml methyl three is except for the difference that added into reactor after peak temperature 20 minutes
(concentration is 0.25mol/L to chlorosilane solution, and it is 88 that solvent is weight ratio：12 hexamethylene and the mixture of normal hexane) carry out idol
Connection, obtains solution polymerized butadiene styrene rubber, and its number-average molecular weight and its coupling efficiency are shown in Table 1.
Comparative example 2
Method according to embodiment 2 is carried out, and 116ml methyl three is except for the difference that added into reactor after peak temperature 30 minutes
(concentration is 0.25mol/L to chlorosilane solution, and it is 88 that solvent is weight ratio：12 hexamethylene and the mixture of normal hexane) carry out idol
Connection, obtains solution polymerized butadiene styrene rubber, and its number-average molecular weight and its coupling efficiency are shown in Table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | |
| Mn (ten thousand) | 16 | 13 | 16 | 17 | 16 | 13 |
| CE（%） | 50 | 54 | 46 | 49 | 10 | 7.5 |
By table 1, it is applied in the synthesis of solution polymerized butadiene styrene rubber by the method for the present invention, raising can be reached even
The purpose of connection efficiency.And by adding coupling agent within peak temperature 5-8 minute, can further improve coupling efficiency.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, the present invention range of the technology design in, various simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
Claims (8)
1. it is a kind of improve solution polymerized butadiene styrene rubber coupling efficiency method, it is characterised in that the method includes：
Under anionic polymerization conditions, in the presence of organic lithium initiator and structure regulator, styrene is set to exist with butadiene
It is polymerized in solvent, and adds coupling agent to be coupled in 5-8 minutes after polyreaction reaches peak temperature；
Wherein, the structure regulator is the compound with structure shown in formula (I),
In formula (I), R1For C1-C10Alkyl；
The coupling agent is methyl trichlorosilane and/or Silicon chloride..
2. method according to claim 1, wherein, in the formula (I), R1For C1-C6Alkyl.
3. method according to claim 1, wherein, it is described relative to the weight portion of total amount 100 of styrene and butadiene
The consumption of structure regulator is 0.1-0.5 weight portions.
4. method according to claim 1, wherein, the organic lithium initiator for structure shown in formula (II) compound,
R2Li formulas (II),
In formula (II), R2For C1-C6Alkyl, C3-C12Cycloalkyl, C7-C14Aralkyl or C6-C12Aryl.
5. method according to claim 4, wherein, the organic lithium initiator is n-BuLi.
6. the method according to claim 1,4 or 5, wherein, the organic lithium initiator in terms of lithium, the coupling agent with
The mol ratio of the organic lithium initiator is 0.1-0.25：1.
7. method according to claim 6, wherein, in terms of lithium, the coupling agent has the organic lithium initiator with described
The mol ratio of machine lithium initiator is 0.13-0.22：1.
8. method according to claim 1, wherein, the anionic polymerization conditions include：Temperature is 10-160 DEG C, with table
Pressure meter, pressure is 0.05-0.5MPa.
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