CN105732859B - A kind of polymer of sulfur-bearing end and preparation method thereof - Google Patents
A kind of polymer of sulfur-bearing end and preparation method thereof Download PDFInfo
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- CN105732859B CN105732859B CN201410759001.4A CN201410759001A CN105732859B CN 105732859 B CN105732859 B CN 105732859B CN 201410759001 A CN201410759001 A CN 201410759001A CN 105732859 B CN105732859 B CN 105732859B
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Abstract
The present invention relates to a kind of polymer of sulfur-bearing end and preparation method thereof, and the structure of the polymer is as follows：Wherein R is alkyl, aryl or aralkyl, and M is polymer segments, the polymer or the copolymer by wherein two or more monomer composition for being styrene, butadiene, isoprene and its derivative, n=1~50.The polymer triggers monomer polymerization to prepare using sulfur-bearing functionalized initiators, and sulfur-bearing functionalized initiators are made by organic compounds containing sulfur with hydrocarbyl lithium using advance or reaction in-situ.This method is simple and practicable, raw material is easy to get, side reaction is few, end-functionalization is efficient.
Description
Technical field
The present invention relates to a kind of sulfur-bearing end polymers and preparation method thereof, belong to anionic polymerisation field.
Background technology
The chain end of functionalized polymeric carries specific functional group, can be carried out again greatly using these functionalizing groups
Molecular self-assembling is modified；Can on other oligomer or macromolecular chain can reactive group react；Add in appropriate coupling
Coupling reaction can also occur for agent；Reversible ion association can also be participated in；Other monomer polymerizations even can be triggered.Therefore,
Polymer ends with can reactive functionality largely expanded the application range of material, make it in polymer blending, table
Face is modified, catalysis, drug release and preparing play a significant role in the fields such as block copolymer, but also impart it is unique
Applying value.Through the above it can be seen that chain end functionalization's polymer has become the research hotspot in polymer modification field
Terminal group functional polymer refers to introduce in its end of the chain containing the equiatomic group of N, Si, Sn, O, S and manufactured poly-
Object is closed, the introducing of these groups can effectively expand the application range of material.Active anionic polymerization technology prepares end group at present
Functionalized polymeric mainly has functional initiator to trigger the means such as polymerization and active polymer ends cessation method.Chain termination method
The electrophilic reagent that modified end groups mainly use has oxygenatedchemicals, nitrogenous compound, sn-containing compound, silicon-containing compound, sulfur-bearing
Compound.Triggered using functionalizations such as oxygen-containing organolithium, nitrogenous organolithium, stanniferous organolithium, siliceous organolithium, sulfur-bearing organolithiums
Agent can also realize end-functionalization, and degree of functionalization is higher than the former, it can be achieved that quantification.Such as there is document report to utilize alkane
Oxygroup lithium alkylide [Schwindeman J A, Granger E J, Engel J F, etal.Process for preparing
Functionalized initiators for anionic polymerization.US, US 5621149.1997], 3- bis-
Methylaminopropyl lithium [Pitsikalis M, Hadjichristidis.Model mono-, di-, and tri- ω-
functionalized three-arm star polybutadienes.Macromolecules,1995,28(11):
3904], tri-n-butyl tin lithium (Bu3SnLi)[Hergenrother W L,Bethea T W,Doshak J M.Tin
containing elastomers and products having reduced hysteresis properties.EP
493839A1.1992], 3- (tertiary butyl dimethyl Si base) propyl lithium [Handlin D L, Bening R C, Willis C
L.Preparation of low viscosity terminally functionalized isoprene
Polymers.US, US 5376745.1994] etc. functionalized initiators polymerization is directly triggered to obtain terminally functionalized polymers, official
Degree can be changed as 0.69~1.00.
The research of sulfur-bearing organic lithium initiator is less at present, and patent US2008004386A1 describes a kind of sulfur-bearing end rubber
The preparation method of glue：This method is synthesized at -78 DEG C using tetrahydrofuran, Thioacetal compound and n-BuLi containing sulfanyl
Lithium initiator reacts the mixture of butadiene or butadiene and styrene under the action of sulfur-bearing lithium alkylide；Or in fourth
Thioacetal compound is added in the mixture of diene or butadiene and styrene, n-BuLi fabricated in situ goes out sulfur-bearing end
Rubber.Vulcanization rubber data show that it can promote the useful effect with filler, chain free terminal content are further reduced, so as to drop
Low-rolling-resistance.20080308204 A1 of patent has invented a kind of novel sulfurized functionalized initiators, and structural formula is as follows：What the initiator synthesized in the following ways：Using tetrahydrofuran as solvent, by the miscellaneous butane of sulphur ring
It is stirred to react with n-BuLi at -78 DEG C and synthesizes sulfur-bearing alkyl lithium initiator.Then with the initiator trigger butadiene with
It is styrene copolymerized, and respectively with N, N- methylimidazoles alkanone, ethyl orthosilicate, 2- methyl mercapto thiazole woodss or butter of tin are whole
Only.Vulcanize rubber statistics indicate that Bifunctionalized butadiene-styrene rubber is lower than the tan δ of only monofunctional, chain free terminal is few, further
Reduce rolling resistance.Below -40 DEG C of 20080308204A1 synthesis temperatures, temperature is too low, and big with polymerization temperature difference；It closes
Long into the time, synthesis step is complicated.
Patent US5663398 describes a kind of new protectiveness sulfur-bearing functionalized initiators, and structural formula is as follows：X-Z-T-
[A(R1R2R3)lm, what which synthesized in the following ways：Using hexane with pentane as mixed solvent, by protectiveness function
Change alkyl halide is stirred to react with lithium metal at 60-65 DEG C synthesizes protectiveness sulfur-bearing alkyl lithium initiator.
More than research background is based on, the present invention proposes another new sulfur-bearing end polymer and its preparation side
Method, one step of synthesis step, and it is simple, synthetic method can be previously prepared, can also be prepared in situ and (directly be mixed with monomer instead
Should), generated time is short, 0-100 DEG C of synthesis temperature, consistent with polymerization temperature.It is of the invention mainly using butyl lithium directly with it is specific
The reaction of structure organosulfur compound is prepared in situ functionalized initiators and triggers alkadienes homopolymerization or copolymerization, and this method is simply easy
Row, raw material is easy to get, side reaction is few, end-functionalization is efficient.
The content of the invention
The purpose of the present invention is the organosulfur compound using specific structure and lithium alkylide reaction prepare the functionalization of sulfur-bearing
Initiator, initiation prepares living polymer, then can prepare monofunctional or multiple functionalized polymerization with being coupled to terminate to be combined
Object.
The present invention provides a kind of polymer of sulfur-bearing end, its structural features are as follows：
Wherein R is the alkyl containing 1-20 carbon atom, aryl or aralkyl, and M is polymer segments, is styrene, fourth
Diene, the polymer of isoprene and its derivative or the copolymer by wherein two or more monomer composition, n=1~
50。
Wherein, the R is preferably methyl, ethyl, propyl, butyl, dodecyl, phenyl, benzyl or naphthalene.
Present invention simultaneously provides a kind of preparation method of sulfur-bearing end polymer, including：
1) by organic compounds containing sulfur, solvent under the effect of the catalyst, reaction temperature is 0-100 DEG C of reaction, is obtained molten
Liquid A；
2) it will be added in the solution A in reaction monomers, solvent, conditioning agent, obtain solution B；Or by monomer, solvent,
Conditioning agent, organic compounds containing sulfur are added in reactor, are uniformly mixed, and are added in catalyst reaction, are obtained solution B；
3) coupling agent is added in into solution B to be blocked, obtain solution C
4) terminator is added in into solution B or in C, sulfur-bearing end polymer is obtained after precipitation is dry.
The organic compounds containing sulfur has following structure feature：
Wherein R is preferably alkyl, aryl or aralkyl, contains 1-20 carbon atom.
The organic compounds containing sulfur is preferably benzyl methyl thioether, benzyl ethyl thioether or benzyl phenyl thioether.
The catalyst is preferably n-BuLi, s-butyl lithium, tert-butyl lithium or hexyl lithium.
The dosage molar ratio of the organic compounds containing sulfur and catalyst is preferably 1~1.5.
The solvent is preferably one or more of aromatic hydrocarbon, aliphatic hydrocarbon and cycloalkane.
The solvent is preferably n-hexane, hexamethylene, pentane or pentamethylene.
The reaction monomers are preferably one or more of styrene, butadiene and isoprene.
The conditioning agent is preferably nitrogenous, oxygen heteroatom compound.
The conditioning agent is preferably tetrahydrofuran, dioxane, pentamethyldivinyltriamine or tetrahydrofurfuryl alcohol ethylether.
The molar ratio of the conditioning agent and catalyst is preferably 0.1-4.
The coupling agent is preferably more vinyl-arenes, polydentate compound.
The coupling agent is preferably silicon tetrachloride, butter of tin or divinylbenzene.
The reaction temperature is preferably 20 DEG C -70 DEG C.
The present invention can also be specified as following：
The present invention provides a kind of polymer of sulfur-bearing end and preparation method thereof, and the sulfur-bearing end polymer being related to leads to
Formula is as follows：
Wherein R is that carbon atom is alkyl, aryl or aralkyl, and M is polymer segments, is styrene, butadiene, isoamyl two
The polymer or the copolymer by wherein two or more monomer composition of alkene and its derivative, for example, it is polystyrene (PS), poly-
Butadiene (PB), polyisoprene (PI), polystyrene-polybutadiene random copolymer (SBR), polystyrene-polybutadiene-
Polystyrene triblock copolymer (SBS), styrene-butadiene-isoprene ternary atactic copolymer (SIBR), n 1-50.
Two methods may be employed to prepare in the polymer, first method be by organic compounds containing sulfur and lithium alkylide by
Certain proportion and order are added in varsol, and 10-120min is stirred to react at 0-100 DEG C, and synthesis sulfur-bearing lithium alkylide draws
Send out agent.Conditioning agent is added to by calculation amount in the hydrocarbon-based polymeric solution (concentration is 5~20g/100ml) of diolefinic monomer again,
Sulfur-bearing alkyl lithium initiator solution made from being added in after temperature is risen to 30 DEG C~70 DEG C, reacts 1~2 hour, then terminates
Or terminated after adding in coupling agent, obtain sulfur-bearing end polymer after precipitation is dry.Second method is by monomer, solvent, adjusting
Agent, organic compounds containing sulfur are added in reactor, are uniformly mixed, and lithium alkylide reaction 1 is added in after temperature is risen to 30 DEG C~70 DEG C
Then~2 hours terminate or are terminated after adding in coupling agent, sulfur-bearing end polymer is obtained after precipitation is dry.Specific reaction road
Line is shown below：
The organic compounds containing sulfur that the present invention uses is thioether, including benzyl methyl thioether, benzyl ethyl thioether, benzyl benzene
Base thioether, preferably benzyl methyl thioether.
The catalyst that the present invention uses is preferably normal-butyl for n-BuLi, s-butyl lithium, tert-butyl lithium, hexyl lithium etc.
Lithium, thioether are 1~1.5 with its molar ratio.
The solvent that the present invention uses is preferably ring for the mixed solution of aromatic hydrocarbon, aliphatic hydrocarbon, cycloalkane or the two
Hexane or pentamethylene.
Conditioning agent used in the present invention is nitrogenous, oxygen heteroatom compound, including tetrahydrofuran, dioxane, pentamethyl
Diethylene triamine, tetrahydrofurfuryl alcohol ethylether etc., preferably ethyl tetrahydrofurfuryl ether.The molar ratio of conditioning agent and organolithium is
0.1-4。
Polymeric reaction temperature is 0 DEG C -100 DEG C, preferably 20 DEG C -70 DEG C.
Coupling agent used is more vinyl-arenes, polydentate compound class in the present invention, including silicon tetrachloride, four chlorinations
Tin, divinylbenzene etc., preferably silicon tetrachloride or divinylbenzene.
Use nuclear magnetic resonance1H-NMR carries out analysis and characterization to functionalized polymeric structure and degree of functionalization；It is oozed with gel
Saturating chromatograph (GPC) has carried out analysis and characterization to the number-average molecular weight (Mn) and molecular weight distribution (MWD) of polymer samples.
Invention effect：The present invention provides a kind of polymer containing sulphur end and preparation method thereof, by previously prepared
Go out sulfur-bearing alkyl lithium initiator to trigger synthesis sulfur-bearing end polymer or synthesize by the way that sulfur-bearing alkyl lithium initiator is prepared in situ
Sulfur-bearing end polymer.Synthetic method of the present invention is simple, mild condition, and raw material is easy to get, reaction speed is fast, and side reaction is few, function
Change efficient, be conducive to industrialized production.
Description of the drawings
Fig. 1 ends are the polystyrene of the end containing benzyl methyl thioether1H-NMR spectrum
Fig. 2 ends are the polybutadiene -1 of the end containing benzyl methyl thioether1H-NMR spectrum
Fig. 3 ends are the styrene butadiene random copolymer of the end containing benzyl methyl thioether1H-NMR spectrum
Fig. 4 ends are the GPC spectrograms of the star-like styrene butadiene random copolymer of the end containing benzyl methyl thioether
Specific embodiment
Following example is in order to further illustrate the method for the present invention, but be should not be limited thereto.
Embodiment 1
The preparation of benzyl methyl thioether lithium initiator：Initiator preparation carries out in the there-necked flask of 250ml, and reaction bulb is through taking out
Vacuum, high-temperature baking, inflated with nitrogen displacement repeatedly for three times, are finally filled with nitrogen.Under nitrogen protection, to equipped with magnetic agitation
Tetrahydrofuran, the benzyl methyl thioether (35.8mmol) of 5ml of 150ml is added in the there-necked flask of 250ml, is stirred at room temperature,
The n-BuLi that 15.5ml concentration is 1.425mol/L is added drop-wise in reaction bulb dropwise in 10min, 25 DEG C of reaction temperature,
When reaction 3 is small under magnetic agitation, product is stored in closed container and is placed in refrigerator under nitrogen protection.It is dripped using soda acid
The method of determining measures its concentration as 0.216mol/L.
Embodiment 2
The preparation of benzyl methyl thioether lithium initiator：Initiator preparation carries out in the there-necked flask of 250ml, and reaction bulb is through taking out
Vacuum, high-temperature baking, inflated with nitrogen displacement repeatedly for three times, are finally filled with nitrogen.Under nitrogen protection, to equipped with magnetic agitation
Hexamethylene, the benzyl methyl thioether (143.2mmol) of 20ml of 100ml is added in the there-necked flask of 250ml, is stirred at room temperature,
The n-BuLi that 62ml concentration is 1.425mol/L is added drop-wise in reaction bulb dropwise in 10min, 25 DEG C of reaction temperature,
When reaction 3 is small under magnetic agitation, product is stored in closed container and is placed in refrigerator under nitrogen protection.It is dripped using soda acid
The method of determining measures its concentration as 0.786mol/L.
Embodiment 3
Styrene homopolymers are prepared with benzyl methyl thioether lithium initiation：The there-necked flask of 250ml is evacuated, and high temperature dries
Roasting, inflated with nitrogen displacement repeatedly for three times, then sequentially adds hexamethylene 35ml, styrene in nitrogen environment under room temperature
3.24g, 5ml concentration are the benzyl methyl thioether lithium of 0.216mol/L, when 40 DEG C of reactions 9 are small, finally inject absolute ethyl alcohol and terminate.
Products therefrom agglomerates with ethyl alcohol, wash after when 50 DEG C of vacuum drying chambers dryings 12 are small after characterized.Measuring conversion ratio is
100%, Mn=12700, MWD=1.38.
Embodiment 4
Styrene homopolymers are prepared with benzyl methyl thioether lithium initiation：The there-necked flask of 250ml is evacuated, and high temperature dries
Roasting, inflated with nitrogen displacement repeatedly for three times, then sequentially adds hexamethylene 35ml, styrene in nitrogen environment under room temperature
3.24g, 0.3ml concentration are the benzyl methyl thioether lithium of 0.216mol/L, and when 40 DEG C of reactions 9 are small, it is whole finally to inject absolute ethyl alcohol
Only.Products therefrom agglomerates with ethyl alcohol, wash after when 50 DEG C of vacuum drying chambers dryings 12 are small after characterized.Measuring conversion ratio is
100%, Mn=83900, MWD=1.38.
Embodiment 5
Dienite is prepared with benzyl methyl thioether lithium initiation：The there-necked flask of 250ml is evacuated, and high temperature dries
Roasting, inflated with nitrogen displacement repeatedly for three times, then sequentially adds hexamethylene 26ml, butadiene in nitrogen environment under room temperature
2.73g, 4.2ml concentration are the benzyl methyl thioether lithium of 0.216mol/L, and when 50 DEG C of reactions 4 are small, it is whole finally to inject absolute ethyl alcohol
Only.Products therefrom agglomerates with ethyl alcohol, wash after when 50 DEG C of vacuum drying chambers dryings 12 are small after characterized.Measuring conversion ratio is
100%, Mn=3600, MWD=1.18.
Embodiment 6
Dienite is prepared with benzyl methyl thioether lithium initiation：The there-necked flask of 250ml is evacuated, and high temperature dries
Roasting, inflated with nitrogen displacement repeatedly for three times, then sequentially adds hexamethylene 26ml, butadiene in nitrogen environment under room temperature
2.73g, 0.25ml concentration are the benzyl methyl thioether lithium of 0.216mol/L, and when 50 DEG C of reactions 4 are small, it is whole finally to inject absolute ethyl alcohol
Only.Products therefrom agglomerates with ethyl alcohol, wash after when 50 DEG C of vacuum drying chambers dryings 12 are small after characterized.Measuring conversion ratio is
100%, Mn=50000, MWD=1.20.
Embodiment 7
With the initiation of benzyl methyl thioether lithium and SiCl4Coupling prepares star-like polybutadiene：The there-necked flask of 250ml is true through taking out
Sky, high-temperature baking, inflated with nitrogen displacement repeatedly for three times, then sequentially add hexamethylene 26ml, fourth in nitrogen environment under room temperature
Diene 2.73g, 0.25ml concentration are the benzyl methyl thioether lithium of 0.216mol/L, when 50 DEG C of reactions 1 are small, sampling 1.Then add in
0.73ml concentration is the SiCl of 0.1181mol/L4/ cyclohexane solution when 50 DEG C of reactions 1 are small, finally inject absolute ethyl alcohol and terminates,
Obtain sample 2.Products therefrom 1 and 2 agglomerates with ethyl alcohol, wash after when 50 DEG C of vacuum drying chambers dryings 12 are small after characterized.
It is 100% to measure conversion ratio, the Mn=50000 of sample 1, MWD=1.20；Mn=150000, the MWD=1.64 of sample 2, coupling
Efficiency=85.2%.
Embodiment 8
Triggered with benzyl methyl thioether lithium and DVB couplings prepare star-like polybutadiene：The there-necked flask of 250ml is true through taking out
Sky, high-temperature baking, inflated with nitrogen displacement repeatedly for three times, then sequentially add hexamethylene 26ml, fourth in nitrogen environment under room temperature
The pentamethyldivinyltriamine and 0.25ml concentration that diene 2.73g, 0.5ml concentration is 0.05388mol/L are 0.216mol/L
Benzyl methyl thioether lithium, 50 DEG C reaction 1 it is small when, sampling 1.Then the DVB/ hexamethylenes that 2ml concentration is 0.054mol/L are added in
Solution when 60 DEG C of reactions 1 are small, finally inject absolute ethyl alcohol and terminates, obtain sample 2.Products therefrom 1 and 2 is agglomerated with ethyl alcohol, washed
Afterwards when 50 DEG C of vacuum drying chambers drying 12 is small after characterized.It is 100% to measure conversion ratio, the Mn=50000 of sample 1, MWD
=1.20；The Mn=181000 of sample 2, MWD=1.72, coupling efficiency=76.3%.
Embodiment 9
Atactic butadiene styrene copolymer is prepared with benzyl methyl thioether lithium initiation：The there-necked flask of 250ml is evacuated, and high temperature dries
Roasting, inflated with nitrogen displacement repeatedly for three times, then sequentially adds hexamethylene 40ml, butadiene in nitrogen environment under room temperature
2.73g, the benzyl methyl thioether lithium that styrene 1.17g and 6.0ml concentration are 0.216mol/L, when 60 DEG C of reactions 4 are small, are finally noted
Enter absolute ethyl alcohol termination.Products therefrom agglomerates with ethyl alcohol, wash after when 50 DEG C of vacuum drying chambers dryings 12 are small after characterized.
Conversion ratio is measured as 100%, Mn=3200, MWD=1.24.
Embodiment 10
Atactic butadiene styrene copolymer is prepared with benzyl methyl thioether lithium initiation：The there-necked flask of 250ml is evacuated, and high temperature dries
Roasting, inflated with nitrogen displacement repeatedly for three times, then sequentially adds hexamethylene 40ml, butadiene in nitrogen environment under room temperature
2.73g, the benzyl methyl thioether lithium that styrene 1.17g and 0.36ml concentration are 0.216mol/L, when 60 DEG C of reactions 4 are small, finally
Absolute ethyl alcohol is injected to terminate.Products therefrom agglomerates with ethyl alcohol, wash after when 50 DEG C of vacuum drying chambers dryings 12 are small after carry out table
Sign.Conversion ratio is measured as 100%, Mn=51000, MWD=1.18.
Embodiment 11
With the initiation of benzyl methyl thioether lithium and SiCl4Coupling prepares S-SBR：Evacuated, the high temperature by the there-necked flask of 250ml
Baking, inflated with nitrogen displacement, repeatedly for three times, then sequentially adds hexamethylene 40ml, butadiene in nitrogen environment under room temperature
2.73g, the benzyl methyl thioether lithium that styrene 1.17g and 0.36ml concentration are 0.216mol/L, when 60 DEG C of reactions 1 are small, sampling
1.Then the SiCl that 1.05ml concentration is 0.1181mol/L is added in4/ cyclohexane solution when 70 DEG C of reactions 1 are small, finally injects nothing
Water-ethanol terminates, and obtains sample 2.Products therefrom 1 and 2 agglomerates with ethyl alcohol, wash after when 50 DEG C of vacuum drying chambers dryings 12 are small
After characterized.It is 100% to measure conversion ratio, the Mn=51000 of sample 1, MWD=1.20；The Mn=149000 of sample 2, MWD
=1.63, coupling efficiency=85.6%.
Embodiment 12
S-B-S (SBS) triblock copolymer is prepared with benzyl methyl thioether lithium initiation：By 250ml
There-necked flask it is evacuated, high-temperature baking, inflated with nitrogen displacement, repeatedly for three times, then in nitrogen environment under room temperature successively plus
Enter hexamethylene 40ml, the benzyl methyl thioether lithium that styrene 0.585g and 0.36ml concentration are 0.216mol/L, it is anti-at 30 DEG C
Answer 1 it is small when, then add in butadiene 2.73g, the reaction was continued 1 it is small when after add in styrene 0.585g, and react 1 it is small when, finally
Absolute ethyl alcohol is injected to terminate.Products therefrom agglomerates with ethyl alcohol, wash after when 50 DEG C of vacuum drying chambers dryings 12 are small after carry out table
Sign.Conversion ratio is measured as 100%, Mn=50000, MWD=1.24.
Embodiment 13
Atactic butadiene styrene copolymer is prepared with benzyl methyl thioether lithium initiation：Hexamethylene is sequentially added in 2L reaction kettles
1000ml, styrene 30g, the ethyl tetrahydrofurfuryl ether that butadiene 70g and 3.58ml concentration are 0.2789mol/L, stir 20 points
Clock after polymeric kettle temperature is risen to 40 DEG C, adds in the benzyl methyl thioether lithium that 4.63ml concentration is 0.216mol/L, after 30 minutes
Polymeric kettle temperature is raised to 56 DEG C of peak.It is reacted again half an hour at 50 DEG C, finally injects absolute ethyl alcohol and terminate.Products therefrom second
After alcohol cohesion, washing when 50 DEG C of vacuum drying chambers drying 12 is small after characterized.Conversion ratio is measured as 100%, Mn=
100000, MWD=1.22.
Embodiment 14
With the initiation of benzyl methyl thioether lithium and SiCl4Coupling prepares S-SBR：Hexamethylene is sequentially added in 2L reaction kettles
1000ml, styrene 30g, the ethyl tetrahydrofurfuryl ether that butadiene 70g and 3.58ml concentration are 0.2789mol/L, stir 20 points
Clock after polymeric kettle temperature is risen to 40 DEG C, adds in the benzyl methyl thioether lithium that 4.63ml concentration is 0.216mol/L, after 30 minutes
Polymeric kettle temperature is raised to 62 DEG C of peak.It is reacted again half an hour at 50 DEG C, sampling 1.Then adding in 13.5ml concentration is
The SiCl of 0.1181mol/L4/ cyclohexane solution when 50 DEG C of reactions 1 are small, finally inject absolute ethyl alcohol and terminates, obtain sample 2.Institute
Product 1 and 2 agglomerated with ethyl alcohol, wash after 50 DEG C of vacuum drying chambers dry 12 it is small when after characterized.Measuring conversion ratio is
100%, the Mn=120000 of sample 1, MWD=1.22；The Mn=310000 of sample 2, MWD=1.65, coupling efficiency=
82.2%.
Embodiment 15
Triggered with benzyl methyl thioether lithium and DVB couplings prepare S-SBR：Hexamethylene is sequentially added in 2L reaction kettles
1000ml, styrene 30g, the dioxane that butadiene 70g and 20ml concentration are 2.5mol/L, are stirred 20 minutes, by polymeric kettle
After temperature rises to 40 DEG C, the benzyl methyl thioether lithium that 4.63ml concentration is 0.216mol/L, polymeric kettle temperature after 30 minutes are added in
It is raised to 62 DEG C of peak.It is reacted again half an hour at 50 DEG C, sampling 1.Then the DVB/ rings that 37ml concentration is 0.054mol/L are added in
Hexane solution when 60 DEG C of reactions 1 are small, finally inject absolute ethyl alcohol and terminates, obtain sample 2.Products therefrom 1 and 2 agglomerates with ethyl alcohol,
After washing when 50 DEG C of vacuum drying chambers drying 12 is small after characterized.It is 100% to measure conversion ratio, the Mn=of sample 1
120000, MWD=1.22；The Mn=410000 of sample 2, MWD=1.76, coupling efficiency=73.2%.
Embodiment 16
Atactic butadiene styrene copolymer is prepared with the benzyl methyl thioether lithium initiation being prepared in situ：It is sequentially added in 2L reaction kettles
Hexamethylene 1000ml, styrene 30g, the benzyl methyl thioether of the tetrahydrofuran of butadiene 70g, 4.05ml and 0.14ml
(0.001mol) is stirred 30 minutes, after polymeric kettle temperature is risen to 30 DEG C, adds in the positive fourth that 0.7ml concentration is 1.425mol/L
Base lithium, polymeric kettle temperature is raised to 58 DEG C of peak after 25 minutes.It is reacted again half an hour at 50 DEG C, it is whole finally to inject absolute ethyl alcohol
Only.Products therefrom agglomerates with ethyl alcohol, wash after when 50 DEG C of vacuum drying chambers dryings 12 are small after characterized.Measuring conversion ratio is
100%, Mn=110000, MWD=1.20.
Embodiment 17
Triggered with the benzyl methyl thioether lithium being prepared in situ and DVB couplings prepare S-SBR：It is sequentially added in 2L reaction kettles
Hexamethylene 1000ml, styrene 30g, the benzyl methyl thioether of the tetrahydrofuran of butadiene 70g, 4.05ml and 0.14ml
(0.001mol) is stirred 30 minutes, after polymeric kettle temperature is risen to 30 DEG C, adds in the positive fourth that 0.7ml concentration is 1.425mol/L
Base lithium, polymeric kettle temperature is raised to 58 DEG C of peak after 25 minutes.It is reacted again half an hour at 50 DEG C, sampling 1.Then 37ml is added in
Concentration is the DVB/ cyclohexane solutions of 0.054mol/L, when 60 DEG C of reactions 1 are small, finally inject absolute ethyl alcohol and terminates, obtain sample
2.Products therefrom 1 and 2 agglomerates with ethyl alcohol, wash after when 50 DEG C of vacuum drying chambers dryings 12 are small after characterized.Measure conversion
Rate is 100%, the Mn=110000 of sample 1, MWD=1.20；The Mn=370000 of sample 2, MWD=1.75, coupling efficiency=
78.6%.
Embodiment 18
Butadiene-styrene-isoprene random copolymer is prepared with benzyl methyl thioether lithium initiation：In 2L reaction kettles
It is 0.2789mol/L to sequentially add hexamethylene 1000ml, styrene 20g, butadiene 40g, isoprene 40g and 3.58ml concentration
Ethyl tetrahydrofurfuryl ether, stir 20 minutes, after polymeric kettle temperature is risen to 40 DEG C, it is 0.216mol/L to add in 4.63ml concentration
Benzyl methyl thioether lithium, at 50 DEG C react 2 it is small when, finally inject absolute ethyl alcohol terminate.Products therefrom is agglomerated with ethyl alcohol, washed
After washing when 50 DEG C of vacuum drying chambers drying 12 is small after characterized.Conversion ratio is measured as 100%, Mn=108000, MWD=
1.36。
Embodiment 19
With the initiation of benzyl methyl thioether lithium and SiCl4Coupling prepares star-like SIBR：Hexamethylene is sequentially added in 2L reaction kettles
Alkane 1000ml, styrene 20g, butadiene 40g, the ethyl tetrahydrochysene chaff that isoprene 40g and 3.58ml concentration are 0.2789mol/L
Base ether stirs 20 minutes, after polymeric kettle temperature is risen to 40 DEG C, adds in the benzyl methyl sulphur that 4.63ml concentration is 0.216mol/L
Ether lithium, when reaction 1 is small at 50 DEG C, sampling 1.Then the SiCl that 13.5ml concentration is 0.1181mol/L is added in4/ hexamethylene is molten
Liquid when 50 DEG C of reactions 1 are small, finally inject absolute ethyl alcohol and terminates, obtain sample 2.Products therefrom 1 and 2 agglomerates with ethyl alcohol, wash after
It is characterized after when 50 DEG C of vacuum drying chamber dryings 12 are small.It is 100% to measure conversion ratio, the Mn=105000 of sample 1, MWD
=1.34；The Mn=270000 of sample 2, MWD=1.67, coupling efficiency=78.6%.
Embodiment 20
Butadiene-styrene-isoprene random copolymer is prepared with the benzyl methyl thioether lithium initiation being prepared in situ：
Hexamethylene 1000ml, styrene 20g, butadiene 40g, isoprene 40g, 9.3ml concentration are sequentially added in 2L reaction kettles is
The pentamethyldivinyltriamine of 0.05388mol/L and the benzyl methyl thioether (0.001mol) of 0.14ml stir 30 minutes,
Then the n-BuLi that 0.7ml concentration is 1.425mol/L is added in, when reaction 2 is small at 50 DEG C, it is whole finally to inject absolute ethyl alcohol
Only.Products therefrom agglomerates with ethyl alcohol, wash after when 50 DEG C of vacuum drying chambers dryings 12 are small after characterized.Measuring conversion ratio is
100%, Mn=106000, MWD=1.32.
Embodiment 21
With the benzyl methyl thioether lithium initiation being prepared in situ and SiCl4Coupling prepares star-like SIBR：In 2L reaction kettles according to
Secondary hexamethylene 1000ml, styrene 20g, butadiene 40g, isoprene 40g, 9.3ml concentration of adding in is 0.05388mol/L's
The benzyl methyl thioether of pentamethyldivinyltriamine and 0.14ml (0.001mol) stir 30 minutes, it is dense then to add in 0.7ml
The n-BuLi for 1.425mol/L is spent, when reaction 1 is small at 50 DEG C, sampling 1.Then adding in 13.5ml concentration is
The SiCl of 0.1181mol/L4/ cyclohexane solution when 50 ± 2 DEG C of reactions 1 are small, finally inject absolute ethyl alcohol and terminates, obtain sample
2.Products therefrom 1 and 2 agglomerates with ethyl alcohol, wash after when 50 DEG C of vacuum drying chambers dryings 12 are small after characterized.Measure conversion
Rate is 100%, the Mn=105000 of sample 1, MWD=1.20；The Mn=2880000 of sample 2, MWD=1.53, coupling efficiency=
81.7%.
Embodiment 22
The preparation of benzyl ethyl thioether lithium initiator：Initiator preparation carries out in the there-necked flask of 250ml, and reaction bulb is through taking out
Vacuum, high-temperature baking, inflated with nitrogen displacement repeatedly for three times, finally pour nitrogen.Under nitrogen protection, to equipped with magnetic agitation
Tetrahydrofuran, the benzyl ethyl thioether (35.8mmol) of 5.55g of 150ml is added in the there-necked flask of 250ml, is stirred down at normal temperatures
It mixes, the n-BuLi that 15.5ml concentration is 1.425mol/L is added drop-wise in reaction bulb dropwise in 10min, reaction temperature 25
DEG C, when reaction 3 is small under magnetic stirring, product is stored in closed container and is placed in refrigerator under nitrogen protection.Using
Its concentration of determination of acid-basetitration is 0.215mol/L.
Embodiment 23
Atactic butadiene styrene copolymer is prepared with benzyl ethyl thioether lithium initiation：Hexamethylene is sequentially added in 2L reaction kettles
1000ml, styrene 30g, the ethyl tetrahydrofurfuryl ether that butadiene 70g and 3.58ml concentration are 0.2789mol/L, stir 20 points
Clock after polymeric kettle temperature is risen to 30 DEG C, adds in the benzyl ethyl thioether lithium that 4.65ml concentration is 0.215mol/L, after 30 minutes
Polymeric kettle temperature is raised to 54 DEG C of peak.It is reacted again half an hour at 50 DEG C, finally injects absolute ethyl alcohol and terminate.Products therefrom second
After alcohol cohesion, washing when 50 DEG C of vacuum drying chambers drying 12 is small after characterized.Conversion ratio is measured as 100%, Mn=
106000, MWD=1.25.
Embodiment 24
With the initiation of benzyl ethyl thioether lithium and SiCl4Coupling prepares S-SBR：Hexamethylene is sequentially added in 2L reaction kettles
1000ml, styrene 30g, the ethyl tetrahydrofurfuryl ether that butadiene 70g and 3.58ml concentration are 0.2789mol/L, stir 20 points
Clock after polymeric kettle temperature is risen to 30 DEG C, adds in the benzyl ethyl thioether lithium that 4.65ml concentration is 0.215mol/L, after 30 minutes
Polymeric kettle temperature is raised to 54 DEG C of peak.It is reacted again half an hour at 50 ± 2 DEG C, sampling 1.Then adding in 13.5ml concentration is
The SiCl of 0.1181mol/L4/ cyclohexane solution when 50 DEG C of reactions 1 are small, finally inject absolute ethyl alcohol and terminates, obtain sample 2.Institute
Product 1 and 2 agglomerated with ethyl alcohol, wash after 50 DEG C of vacuum drying chambers dry 12 it is small when after characterized.Measuring conversion ratio is
100%, the Mn=106000 of sample 1, MWD=1.25；The Mn=260000 of sample 2, MWD=1.68, coupling efficiency=
80.7%.
Embodiment 25
Atactic butadiene styrene copolymer is prepared with the benzyl ethyl thioether lithium initiation being prepared in situ：It is sequentially added in 2L reaction kettles
Hexamethylene 1000ml, styrene 30g, the tetrahydrofuran of butadiene 70g, 4.05ml and 12ml concentration are the benzyl of 0.0833mol/L
Base ethyl thioether-cyclohexane solution stirs 30 minutes, and after polymeric kettle temperature is risen to 30 DEG C, adding in 0.7ml concentration is
The n-BuLi of 1.425mol/L, polymeric kettle temperature is raised to 56 DEG C of peak after 25 minutes.It is reacted again half an hour at 50 DEG C, finally
Absolute ethyl alcohol is injected to terminate.Products therefrom agglomerates with ethyl alcohol, wash after when 50 DEG C of vacuum drying chambers dryings 12 are small after carry out table
Sign.Conversion ratio is measured as 100%, Mn=102000, MWD=1.21.
Embodiment 26
With the benzyl ethyl thioether lithium initiation being prepared in situ and SiCl4Coupling prepares S-SBR：Add successively in 2L reaction kettles
It is 0.0833mol/L's to enter hexamethylene 1000ml, styrene 30g, the tetrahydrofuran of butadiene 70g, 4.05ml and 12ml concentration
Benzyl ethyl thioether-cyclohexane solution stirs 30 minutes, and after polymeric kettle temperature is risen to 30 DEG C, adding in 0.7ml concentration is
The n-BuLi of 1.425mol/L, polymeric kettle temperature is raised to 56 DEG C of peak after 25 minutes.It reacts half an hour, samples again at 50 DEG C
1.Then the SiCl that 13.5ml concentration is 0.1181mol/L is added in4/ cyclohexane solution when 60 DEG C of reactions 1 are small, finally injects nothing
Water-ethanol terminates, and obtains sample 2.Products therefrom 1 and 2 agglomerates with ethyl alcohol, wash after when 50 DEG C of vacuum drying chambers dryings 12 are small
After characterized.It is 100% to measure conversion ratio, the Mn=102000 of sample 1, MWD=1.21；The Mn=290000 of sample 2,
MWD=1.54, coupling efficiency=82.9%.
Embodiment 27
Butadiene-styrene-isoprene random copolymer is prepared with benzyl ethyl thioether lithium initiation：In 2L reaction kettles
It is 0.2789mol/L to sequentially add hexamethylene 1000ml, styrene 20g, butadiene 40g, isoprene 40g and 3.58ml concentration
Ethyl tetrahydrofurfuryl ether, stir 20 minutes, after polymeric kettle temperature is risen to 40 DEG C, it is 0.215mol/L to add in 4.65ml concentration
Benzyl ethyl thioether lithium, at 50 DEG C react 2 it is small when, finally inject absolute ethyl alcohol terminate.Products therefrom agglomerates with ethyl alcohol,
After washing when 50 DEG C of vacuum drying chambers drying 12 is small after characterized.Conversion ratio is measured as 100%, Mn=109000, MWD=
1.41。
Embodiment 28
With the initiation of benzyl ethyl thioether lithium and SiCl4Coupling prepares star-like SIBR：Hexamethylene is sequentially added in 2L reaction kettles
Alkane 1000ml, styrene 20g, butadiene 40g, the ethyl tetrahydrochysene chaff that isoprene 40g and 3.58ml concentration are 0.2789mol/L
Base ether stirs 20 minutes, after polymeric kettle temperature is risen to 40 DEG C, adds in the benzyl ethyl sulphur that 4.65ml concentration is 0.215mol/L
Ether lithium, when reaction 1 is small at 50 DEG C, sampling 1.Then the SiCl that 13.5ml concentration is 0.1181mol/L is added in4/ hexamethylene is molten
Liquid when 50 DEG C of reactions 1 are small, finally inject absolute ethyl alcohol and terminates, obtain sample 2.Products therefrom 1 and 2 agglomerates with ethyl alcohol, wash after
It is characterized after when 50 DEG C of vacuum drying chamber dryings 12 are small.It is 100% to measure conversion ratio, the Mn=109000 of sample 1, MWD
=1.41；The Mn=265000 of sample 2, MWD=1.75, coupling efficiency=75.9%.
Embodiment 29
Butadiene-styrene-isoprene random copolymer is prepared with the benzyl ethyl thioether lithium initiation being prepared in situ：
Hexamethylene 1000ml, styrene 20g, butadiene 40g, isoprene 40g, 3.58ml concentration are sequentially added in 2L reaction kettles is
The ethyl tetrahydrofurfuryl ether and 12ml concentration of 0.2789mol/L is benzyl ethyl thioether-cyclohexane solution of 0.0833mol/L,
Then stirring 30 minutes adds in the n-BuLi that 0.7ml concentration is 1.425mol/L, when reaction 2 is small at 50 DEG C, finally injects
Absolute ethyl alcohol terminates.Products therefrom agglomerates with ethyl alcohol, wash after when 50 DEG C of vacuum drying chambers dryings 12 are small after characterized.It surveys
It is 100%, Mn=110000, MWD=1.45 to obtain conversion ratio.
Embodiment 30
With the benzyl ethyl thioether lithium initiation being prepared in situ and SiCl4Coupling prepares star-like SIBR：In 2L reaction kettles according to
Secondary hexamethylene 1000ml, styrene 20g, butadiene 40g, isoprene 40g, 3.58ml concentration of adding in is 0.2789mol/L's
Ethyl tetrahydrofurfuryl ether and benzyl ethyl thioether-cyclohexane solution that 12ml concentration is 0.0833mol/L, stirring 30 minutes, so
The n-BuLi that 0.7ml concentration is 1.425mol/L, when reaction 1 is small at 50 DEG C, sampling 1 are added in afterwards.Then 13.5ml is added in
Concentration is the SiCl of 0.1181mol/L4/ cyclohexane solution when 50 DEG C of reactions 1 are small, finally inject absolute ethyl alcohol and terminates, obtain sample
Product 2.Products therefrom 1 and 2 agglomerates with ethyl alcohol, wash after when 50 DEG C of vacuum drying chambers dryings 12 are small after characterized.It measures and turns
Rate is 100%, the Mn=110000 of sample 1, MWD=1.45；Mn=2860000, the MWD=1.86 of sample 2, coupling effect
Rate=79.4%.
Embodiment 31
The preparation of benzyl phenyl thioether lithium initiator：Initiator preparation carries out in the there-necked flask of 250ml, and reaction bulb is through taking out
Vacuum, high-temperature baking, inflated with nitrogen displacement repeatedly for three times, finally pour nitrogen.Under nitrogen protection, to equipped with magnetic agitation
Tetrahydrofuran, the benzyl ethyl thioether (35.8mmol) of 7.32g of 150ml is added in the there-necked flask of 250ml, is stirred at normal temperatures
It mixes, the n-BuLi that 15.5ml concentration is 1.425mol/L is added drop-wise in reaction bulb dropwise in 10min, reaction temperature 25
DEG C, when reaction 3 is small under magnetic stirring, product is stored in closed container and is placed in refrigerator under nitrogen protection.Using
Its concentration of determination of acid-basetitration is 0.212mol/L.
Embodiment 32
Atactic butadiene styrene copolymer is prepared with benzyl phenyl thioether lithium initiation：Hexamethylene is sequentially added in 2L reaction kettles
1000ml, styrene 30g, the ethyl tetrahydrofurfuryl ether that butadiene 70g and 3.58ml concentration are 0.2789mol/L, by polymeric kettle
After temperature rises to 30 DEG C, the benzyl phenyl thioether lithium that 4.72ml concentration is 0.212mol/L, polymeric kettle temperature after 35 minutes are added in
It is raised to 52 DEG C of peak.It is reacted again half an hour at 50 DEG C, finally injects absolute ethyl alcohol and terminate.Products therefrom is agglomerated with ethyl alcohol, washed
After washing when 50 DEG C of vacuum drying chambers drying 12 is small after characterized.Conversion ratio is measured as 100%, Mn=110000, MWD=
1.28。
Embodiment 33
With the initiation of benzyl phenyl thioether lithium and SiCl4Coupling prepares S-SBR：Hexamethylene is sequentially added in 2L reaction kettles
1000ml, styrene 30g, the ethyl tetrahydrofurfuryl ether that butadiene 70g and 3.58ml concentration are 0.2789mol/L, by polymeric kettle
After temperature rises to 30 DEG C, the benzyl phenyl thioether lithium that 4.72ml concentration is 0.212mol/L, polymeric kettle temperature after 35 minutes are added in
It is raised to 52 DEG C of peak.It is reacted again half an hour at 50 DEG C, sampling 1.Then it is 0.1181mol/L's to add in 13.5ml concentration
SiCl4/ cyclohexane solution when 50 DEG C of reactions 1 are small, finally inject absolute ethyl alcohol and terminates, obtain sample 2.Products therefrom 1 and 2 is used
After ethyl alcohol cohesion, washing when 50 DEG C of vacuum drying chambers drying 12 is small after characterized.It is 100% to measure conversion ratio, sample 1
Mn=110000, MWD=1.28；The Mn=276000 of sample 2, MWD=1.82, coupling efficiency=76.5%.
Embodiment 34
Atactic butadiene styrene copolymer is prepared with the benzyl phenyl thioether lithium initiation being prepared in situ：It is sequentially added in 2L reaction kettles
Hexamethylene 1000ml, styrene 30g, butadiene 70g, 3.58ml concentration be 0.2789mol/L ethyl tetrahydrofurfuryl ether and
15ml concentration is benzyl phenyl thioether-cyclohexane solution of 0.0667mol/L, after polymeric kettle temperature is risen to 30 DEG C, is added in
0.7ml concentration is the n-BuLi of 1.425mol/L, and polymeric kettle temperature is raised to 53 DEG C of peak after 32 minutes.It is reacted again at 50 DEG C
Half an hour finally injects absolute ethyl alcohol and terminates.Products therefrom agglomerates with ethyl alcohol, wash after it is small in 50 DEG C of vacuum drying chambers dryings 12
When after characterized.Conversion ratio is measured as 100%, Mn=108000, MWD=1.26.
Embodiment 35
With the benzyl phenyl thioether lithium initiation being prepared in situ and SiCl4Coupling prepares S-SBR：Add successively in 2L reaction kettles
Enter hexamethylene 1000ml, styrene 30g, butadiene 70g, 3.58ml concentration be 0.2789mol/L ethyl tetrahydrofurfuryl ether and
15ml concentration is benzyl phenyl thioether-cyclohexane solution of 0.0667mol/L, after polymeric kettle temperature is risen to 30 DEG C, is added in
0.7ml concentration is the n-BuLi of 1.425mol/L, and polymeric kettle temperature is raised to 53 DEG C of peak after 32 minutes.It is reacted again at 50 DEG C
Half an hour, sampling 1.Then the SiCl that 13.5ml concentration is 0.1181mol/L is added in4/ cyclohexane solution, when 50 DEG C of reactions 1 are small,
It finally injects absolute ethyl alcohol to terminate, obtains sample 2.Products therefrom 1 and 2 agglomerates with ethyl alcohol, wash after in 50 DEG C of vacuum drying chambers
It is characterized after when drying 12 is small.It is 100% to measure conversion ratio, the Mn=108000 of sample 1, MWD=1.26；The Mn of sample 2
=286000, MWD=1.80, coupling efficiency=80.4%.
Embodiment 36
Butadiene-styrene-isoprene random copolymer is prepared with benzyl phenyl thioether lithium initiation：In 2L reaction kettles
It is 0.2789mol/L to sequentially add hexamethylene 1000ml, styrene 20g, butadiene 40g, isoprene 40g and 3.58ml concentration
Ethyl tetrahydrofurfuryl ether, stir 20 minutes, after polymeric kettle temperature is risen to 40 DEG C, it is 0.212mol/L to add in 4.72ml concentration
Benzyl phenyl thioether lithium, at 50 DEG C react 2 it is small when, finally inject absolute ethyl alcohol terminate.Products therefrom is agglomerated with ethyl alcohol, washed
After washing when 50 DEG C of vacuum drying chambers drying 12 is small after characterized.Conversion ratio is measured as 100%, Mn=112000, MWD=
1.48。
Embodiment 37
With the initiation of benzyl phenyl thioether lithium and SiCl4Coupling prepares star-like SIBR：Hexamethylene is sequentially added in 2L reaction kettles
Alkane 1000ml, styrene 20g, butadiene 40g, the ethyl tetrahydrochysene chaff that isoprene 40g and 3.58ml concentration are 0.2789mol/L
Base ether stirs 20 minutes, after polymeric kettle temperature is risen to 40 DEG C, adds in the benzyl phenyl sulphur that 4.72ml concentration is 0.212mol/L
Ether lithium, when reaction 1 is small at 50 DEG C, sampling 1.Then the SiCl that 13.5ml concentration is 0.1181mol/L is added in4/ hexamethylene is molten
Liquid when 60 DEG C of reactions 1 are small, finally inject absolute ethyl alcohol and terminates, obtain sample 2.Products therefrom 1 and 2 agglomerates with ethyl alcohol, wash after
It is characterized after when 50 DEG C of vacuum drying chamber dryings 12 are small.It is 100% to measure conversion ratio, the Mn=112000 of sample 1, MWD
=1.48；The Mn=297000 of sample 2, MWD=1.94, coupling efficiency=74.8%.
Embodiment 38
Butadiene-styrene-isoprene random copolymer is prepared with the benzyl phenyl thioether lithium initiation being prepared in situ：
Hexamethylene 1000ml, styrene 20g, butadiene 40g, isoprene 40g, 3.58ml concentration are sequentially added in 2L reaction kettles is
The ethyl tetrahydrofurfuryl ether and 15ml concentration of 0.2789mol/L is benzyl phenyl thioether-cyclohexane solution of 0.0667mol/L,
Then stirring 30 minutes adds in the n-BuLi that 0.7ml concentration is 1.425mol/L, when reaction 3 is small at 50 DEG C, finally injects
Absolute ethyl alcohol terminates.Products therefrom agglomerates with ethyl alcohol, wash after when 50 DEG C of vacuum drying chambers dryings 12 are small after characterized.It surveys
It is 100%, Mn=107000, MWD=1.42 to obtain conversion ratio.
Embodiment 39
With the benzyl phenyl thioether lithium initiation being prepared in situ and SiCl4Coupling prepares star-like SIBR：In 2L reaction kettles according to
Secondary hexamethylene 1000ml, styrene 20g, butadiene 40g, isoprene 40g, 3.58ml concentration of adding in is 0.2789mol/L's
Ethyl tetrahydrofurfuryl ether and benzyl phenyl thioether-cyclohexane solution that 15ml concentration is 0.0667mol/L, stirring 30 minutes, so
The n-BuLi that 0.7ml concentration is 1.425mol/L, when reaction 1 is small at 50 DEG C, sampling 1 are added in afterwards.Then 13.5ml is added in
Concentration is the SiCl of 0.1181mol/L4/ cyclohexane solution when 60 DEG C of reactions 1 are small, finally inject absolute ethyl alcohol and terminates, obtain sample
Product 2.Products therefrom 1 and 2 agglomerates with ethyl alcohol, wash after when 50 DEG C of vacuum drying chambers dryings 12 are small after characterized.It measures and turns
Rate is 100%, the Mn=107000 of sample 1, MWD=1.42；The Mn=299000 of sample 2, MWD=1.91, coupling efficiency
=81.6%.
Claims (13)
1. a kind of polymer of sulfur-bearing end, its structural features are as follows：
Wherein R be the alkyl containing 1-20 carbon atom, aryl or aralkyl, M is polymer segments, for styrene, butadiene,
The polymer or the copolymer by wherein two or more monomer composition of isoprene and its derivative, n=1~4；
The R is methyl, ethyl, propyl, butyl, phenyl, benzyl or naphthalene.
2. a kind of preparation method of sulfur-bearing end polymer, which is characterized in that including：
1) by organic compounds containing sulfur, solvent under the effect of the catalyst, reaction temperature is 0-100 DEG C of reaction, obtains solution A；
2) it will be added in the solution A in reaction monomers, solvent, conditioning agent, obtain solution B；Or by monomer, solvent, adjusting
Agent, organic compounds containing sulfur are added in reactor, are uniformly mixed, and are added in catalyst reaction, are obtained solution B；
3) coupling agent is added in into solution B to be blocked, obtain solution C
4) terminator is added in into solution B or in C, sulfur-bearing end polymer is obtained after precipitation is dry；
The organic compounds containing sulfur has following structure feature：
Wherein R is alkyl, aryl or aralkyl, contains 1-20 carbon atom；
The R is methyl, ethyl, propyl, butyl, phenyl, benzyl or naphthalene；
The reaction monomers are one or more of styrene, butadiene and isoprene.
3. the preparation method of sulfur-bearing end polymer according to claim 2, it is characterised in that：The sulfur-bearing organic compound
Object is benzyl methyl thioether, benzyl ethyl thioether or benzyl phenyl thioether.
4. the preparation method of sulfur-bearing end polymer according to claim 2, it is characterised in that：The catalyst is positive fourth
Base lithium, s-butyl lithium, tert-butyl lithium or hexyl lithium.
5. the preparation method of the sulfur-bearing end polymer according to any one of claim 2~4, it is characterised in that：It is described
The dosage molar ratio of organic compounds containing sulfur and catalyst is 1~1.5.
6. the preparation method of the sulfur-bearing end polymer according to any one of claim 2~4, it is characterised in that：It is described
Solvent is one or more of aromatic hydrocarbon, aliphatic hydrocarbon and cycloalkane.
7. the preparation method of sulfur-bearing end polymer according to claim 6, it is characterised in that：The solvent for just oneself
Alkane, hexamethylene, pentane or pentamethylene.
8. the preparation method of sulfur-bearing end polymer according to claim 2, it is characterised in that：The conditioning agent be containing
Nitrogen, oxygen heteroatom compound.
9. the preparation method of sulfur-bearing end polymer according to claim 8, it is characterised in that：The conditioning agent is tetrahydrochysene
Furans, dioxane, pentamethyldivinyltriamine or tetrahydrofurfuryl alcohol ethylether.
10. the preparation method of sulfur-bearing end polymer according to claim 2, it is characterised in that：The conditioning agent is with urging
The molar ratio of agent is 0.1-4.
11. the preparation method of sulfur-bearing end polymer according to claim 2, it is characterised in that：The coupling agent is more
Vinyl-arene, polydentate compound.
12. the preparation method of sulfur-bearing end polymer according to claim 11, it is characterised in that：The coupling agent is four
Silicon chloride, butter of tin or divinylbenzene.
13. the preparation method of sulfur-bearing end polymer according to claim 2, it is characterised in that：The reaction temperature is
20℃-70℃。
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| CN103030784A (en) * | 2012-12-24 | 2013-04-10 | 中南民族大学 | Sulfur-containing hyperbranched epoxy resin and preparation method thereof |
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| Title |
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| A Giant Surfactant of Polystyrene-(Carboxylic Acid-Functionalized Polyhedral Oligomeric Silsesquioxane)Amphiphile with Highly Stretched Polystyrene Tails in Micellar Assemblies;Xinfei Yu，等;《Journal of American chemistry society》;20101104;第132卷;第16741-16744页 * |
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