CN103374137B - A kind of Synthesis and applications of the styrene-conjugated diene multipolymer containing active combined sulfur - Google Patents
A kind of Synthesis and applications of the styrene-conjugated diene multipolymer containing active combined sulfur Download PDFInfo
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Abstract
A kind of Synthesis and applications of the styrene-conjugated diene multipolymer containing active combined sulfur.Must following characteristics be had: A in sulfuric silane molecular structure) end of sulphur atom is connected with carbon atom, B) poly-sulphur is with-S
n-occur in the molecule, wherein n=2 ~ 5, C) in molecule containing silicon key, as-Si-R
3, wherein R is alkoxy or halogen.The molecular ratio of polymer ends active lithium and sulfuric silane is 1 ~ 6: 1, the molecular-weight average of polymkeric substance is 8-40 ten thousand, molecular weight distribution presents unimodal distribution, molecular weight distributing index is 1 ~ 2.8, the active sulphur mass content of the combination of multipolymer is 0.030-0.062%, copolymer resin or elastomerics intensity high, multipolymer rubber cold flow properties is low, good processability, cross-linked rubber do not revert.
Description
Technical field
The present invention relates to the methods for making and using same of the styrene-conjugated diene multipolymer containing active combined sulfur.
Background technology
Vinylbenzene and conjugated diolefine orientable polymerization synthesize random or segmented copolymer in a solvent under the initiation of butyllithium, but molecular chain line style or star-like, and this material is specially adapted to thermoplastic elastomer or for the manufacture of tire or other plastic material.It should be noted especially and inevitably produce some oligopolymer in preparation line style styrene-conjugated diene polymkeric substance, these oligopolymer present the high plastic state of liquid state or easy-cold flow at normal temperatures, oligopolymer to be mingled in granular SBS, SIS adhesion caking in storage, makes troubles to following process; If the solution polymerized butadiene styrene rubber of synthesis can produce unwanted cold flow in storage, show cold flow excessive (namely very property is not good, and after preferably very the usual rubber of property parks 3 months, height conservation rate is greater than 96%).
That prepares wide distribution to interrupter method in addition contains intermingle with styrene-conjugated diene rubber; usually there will be some oligomers; the number-average molecular weight of polymkeric substance then affects larger by small-molecular-weight fraction; its numerical value also relatively contained small molecules fraction molecular weight; and the critical molecular weight that the more crosslinked polymer of small-molecular-weight tangles can be larger; the crosslinked entanglement of rubber can be less, and the intensity embodying cross-linked rubber can decline.
The anionic copolymer such as star-shaped sbs, SIS preparation principle prepares type SBS with process to coupling method, SIS is similar, the key distinction is that coupling agent used is different, and polyfunctional group coupler has ethylene dichloride, ethylene dibromide, dichlorodimethylsilane, trichlorosilane, tetrachloro silicane, tetramethoxy-silicane etc. for the synthesis of star-shaped sbs, SIS; Epoxidised soybean oil class is used for the coupling of transparent butadiene-styrene impact resin; Tin tetrachloride is used for the coupling of solution polymerized butadiene styrene rubber.The coupling degree of the polymkeric substance that these coupling agents obtain is at 2-4.Elastomerics after coupling is heat-resisting, breaking tenacity is improved, and oil-filled rate also improves simultaneously, expands the range of application of material.
US P4194154 provides a kind of active SB by Styrene-Butadiene block copolymerization, then obtains a kind of four arm SBS with silicon tetrachloride coupling, coupling degree 3.6, number-average molecular weight 280,000, the shoemaking of this polymkeric substance optimum; EP386671 discloses a kind of styrene-isoprene and prepares star-like SIS, and the coupler of employing is trichlorosilane, coupling degree 2.8, and molecular weight contains part linear structure, and this SIS is suitable for the material making non-setting adhesive; K-Resin series product commercially available at present under butyllithium causes, carry out random copolymerization by styrene butadiene, finally carrying out by epoxidised soybean oil the GPC spectrogram that coupling obtains is 3 peaks distributions, molecular weight distributing index is the resin of 32, melting index 6-8g/min, this material is mainly used in transparent container product.JP61-231013 provides a kind of method that solution polymerization styrene-butadiene rubber is prepared in styrene-butadiene random copolymerization, the coupling agent that the method uses is tin tetrachloride, the styrene-butadiene rubber(SBR) of coupling synthesis improves with the linear solution polymerized butadiene styrene rubber phase specific tensile strength of non-tin coupling, and rolling resistance reduces; In addition, Wang Nini etc., the synthesis [J] of the oil-filled styrene-isoprene-butadiene terpolymer of tin coupling type, China Synthetic Rubber Industry, 2010, describe the method adopting tin tetrachloride coupling styrene-isoprene-butadiene copolymer in 33 (6).Liang Aimin etc., the research [J] of tire low cis polybutadiene rubber, elastomerics, 2004.14 (5). describing the coupler used in Anionic Polymerization of Butadiene in a literary composition is tin tetrachloride, and obtained polymkeric substance GPC spectrogram is bimodal distribution; Li Ximei etc., structure regulator is on the impact [J] of lithium system soluble polybutaamyl-rubber microtexture, and elastomerics, the coupling agent that in 2004.14 (1), the poly-butadiene-isoprene rubber of preparation uses is silicon tetrachloride.
Above-mentioned technology, in polymer molecule except activity double key, without other active group, use the powerful physical crosslinking by itself to produce because of elastomeric, and contain intermingle with styrene-conjugated diene rubber need add when sulfuration quantitative simple substance sulphur sulfuration produce micro-crosslinked after just have use value.The vulcanization process of this additional elemental sulfur belongs to heterogeneous vulcanization reaction, is difficult to the phenomenon of reverting controlling sulphur in sulfidation, does not ensure that the best of vulcanizing material and goods is powerful.
To at present, the multipolymer of the silicoorganic compound coupling styrene-conjugated diene containing active many sulphur is adopted to yet there are no report.
Summary of the invention
The object of this invention is to provide a kind of multi-sulfur silane coupling butadiene-styrene copolymer and obtained a kind of styrene-conjugated diene multipolymer containing active combined sulfur; This material can improve the intensity of vulcanized rubber, reduces the phenomenon of reverting of sulfuration.
Another object of the present invention aims to provide the simple preparation method efficiently of above-mentioned materials.
Of the present inventionly also provide a kind of organic multi-sulfur silane in the application of above-mentioned preparation method.
A kind of styrene-conjugated diene multipolymer containing active combined sulfur of the present invention, being organic multi-sulfur silane coupling styrene-conjugated diene active copolymer, is formed through coupling polymerization by the component of following A, B raw material;
The organic multi-sulfur silane of A, coupling agent, must have following characteristics in its structure: a) end of sulphur atom is connected with carbon atom; B) poly-sulphur occurs in the molecule with-Sn-, wherein n=2 ~ 5; C) silicon key-Si-R is contained in molecule
3, wherein R is the alkoxy or halogen of C1-C4;
B, make initiator with butyllithium, conjugated diene and vinylbenzene are the polymer that random copolymerization or block polymerization obtain that molecular end is active lithium;
Vinylbenzene and conjugated diolefine mass ratio be=25-75: 25-75, and butyllithium is 1 ~ 6: 1 with the amount of substance ratio of organic multi-sulfur silane.
Described conjugated diene is divinyl or isoprene or their mixture.
Described organic multi-sulfur silane is preferably two-[γ-(tri-alkoxy silicon) propyl group] polysulfide, and wherein alkoxyl group is methoxy or ethoxy; In molecule, poly-sulphur is with-S
n-occur, wherein n=2 ~ 5.
The particularly preferred organic multi-sulfur silane of the present invention comprises: organic multi-sulfur silane is two-[γ-(trimethoxy silicon) propyl group] disulphide, two-[γ-(trimethoxy silicon) propyl group] tetrasulfide, two-[γ-(triethoxysilicane) propyl group] disulphide, two-[γ-(tri-alkoxy) propyl group] pentasulfide, may also be two-[γ-(three chloro silicon) propyl group] disulphide, two-[γ-(three chloro silicon) propyl group] tetrasulfide, a kind of in two-[γ-(three chloro silicon) propyl group] pentasulfide or the mixture in them.
Two-[γ-(three chloro silicon) propyl group] pentasulfide can be formed by 3-trichlorosilane base-n-propyl chloride and sodium pentosulfide condensation; Equally, other organic multi-sulfur silane can be prepared by similar approach.
Described butyllithium is n-Butyl Lithium or isobutyl-lithium.
Preparation method of the present invention is, described vinylbenzene and conjugated diolefine cause with butyllithium in hexane-hexanaphthene mixed solvent, carry out random or block polymerization, after polymerization, form active lithium polymer PSBLi, then add organic multi-sulfur silane solution and carry out linked reaction.
In the present invention, organic multi-sulfur silane is 1: 1-6 with the polymeric amount of substance ratio of active lithium.
Linked reaction temperature 30-120 DEG C of the present invention.
Solvent in organic multi-sulfur silane solution used is hexane, hexanaphthene or octane.
Vinylbenzene and conjugated diolefine are at butyllithium-initiated polymerization temperature of reaction 30-120 DEG C, and polymerization reaction time is 20-120min, and the linked reaction time is 20-60min.
Present invention also offers the application of above-mentioned organic multi-sulfur silane, described organic multi-sulfur silane is used as coupling agent and is applied in the polyreaction that vinylbenzene and conjugated diene cause at butyllithium.
Styrene-butadiene rubber(SBR) particularly containing active combined sulfur in the product of the styrene-conjugated diene multipolymer containing active combined sulfur of the present invention's synthesis is making the tire tread glue processing characteristics, the anti-cold flow of rubber, bending resistance, the reduction tire crackle extensibility that have had, and even more important is can the reverting of sulfur resistive in sulfidation.And synthesize the sizing material that this styrene-butadiene rubber(SBR) containing active combined sulfur can be used as green, environmental protection, high-performance tire, many sulphur that activity in this sizing material combines are energy self-crosslinking in sulfidation, belong to homogeneous phase sulfuration addition, thus improve the physical and mechanical properties of vulcanizing material.
The molecular-weight average of multipolymer of the present invention is 8-40 ten thousand, and molecular weight distribution presents unimodal distribution, and molecular weight distributing index is 1 ~ 2.8, and the active sulphur mass content of the combination of multipolymer is 0.030-0.062%,
The application of multipolymer of the present invention be also using by conjugated diene and vinylbenzene the obtained styrene-butadiene rubber(SBR) containing active combined sulfur after random copolymerization and linked reaction complete apply the material as tire tread glue.
After linked reaction completes, add extending oil in styrene-butadiene rubber(SBR) solution, adding weight part is add 35-40 part in 100 parts of dry glue amounts of styrene-butadiene rubber(SBR).
Styrene-butadiene rubber(SBR) containing active combined sulfur of the present invention, belongs to homogeneous solution polymerization coupling system, comprises following component and obtains.
A. organic multi-sulfur silane is as coupling agent, two-[γ-(tri-alkoxy silicon) propyl group] polysulfide, and wherein alkoxyl group is methoxy or ethoxy; In its molecule, many sulphur is with-S
n-occur, wherein n=2 ~ 5; Or two-[γ-(three halogen silicon) propyl group] polysulfide, in its molecule, many sulphur is with-S
n-occurring, wherein n=2 ~ 5, halogeno-group can be-Cl or-Br.
B. cause conjugated diene with butyllithium in a solvent, conjugated diene can be divinyl (B), isoprene (Ip) and their mixture; Conjugated diene and vinylbenzene can be random copolymerization or block polymerization, and polymer molecule chain end is active lithium.
C. vinylbenzene (S) and conjugated diolefine mass ratio are 25-75/25-75, and butyllithium is 1 ~ 6: 1 with the amount of substance ratio of organic multi-sulfur silane.
D. add environment-protection filling oil (as being environment-friendly type RAE oil, being produced by SHELL company) in the styrene-butadiene rubber(SBR) solution after coupling, add-on is 35-40 part of 100 parts of styrene-butadiene rubber(SBR) dry glue amount quality.
The present invention is polystyrene-conjugated diene block or random copolymers with the active lithium multipolymer of organic multi-sulfur silane coupling, as SBS elastomerics, SIS elastomerics, styrene-butadiene transparent impact resins, SSBR solution polymerization styrene-butadiene rubber, SIBR soluble polybutaamyl benzene rubber.
The present invention is in the preparation of solution polymerized butadiene styrene rubber, the molecular ratio of active lithium and coupling agent is can 1-6: 1, the molecular ratio of preferred active lithium and coupling agent is 1-2: 1, in conjunction with the mass content of active sulphur be 0.03-0.062%, molecular weight distribution is 1.4-2.8, rubber excellent storage stability, without obvious cold flow.
Feature of the present invention is that styrene butadiene or isoprene are caused composite reactive with butyllithium is in a solvent lithium integrated, then carries out coupling with organic multi-sulfur silane, obtains containing the rubber of many sulphur silicon structure or resin or elastomerics.Active sulphur is combined in polymer macromolecule with covalent linkage form, if with in sulfurizing formula, separately need add more elemental sulfur during conventional rubber sulfuration could compared with sulfuration, this traditional vulcanization substantially belong to heterogeneous or half homogeneous phase micro-crosslinked.Obtained polymkeric substance can be single armed linear, may also be both arms linear, may also be three arms, four arms, five arms, six arm star structures.As contained-S-S-key or-S-S-S-S-S-key in obtained solution polymerized butadiene styrene rubber molecular structure, because many sulphur-sulfide linkages are more active than single thioether bond, in certain hour at high temperature, easily and-C=C-double bond generation addition reaction in rubber (may also be SBS, butadiene styrene resin), its process is as follows for sulphur atom in polysulfidic bond:
Many sulphur in this rubber molecule participate in sulfuration formed micro-crosslinked after, the intensity of vulcanized rubber (as SBS, butadiene styrene resin) can be improved on the one hand, as wear resistance, endurance of cutting, resistance to pressure.They are two years old, polysulfidic bond is converted into more stable single thioether, and all form the sizing material that reverts of sulfuration resistant, serve the effect that sulfuration/promotion is active, break the balance of conventional vulcanized mode, reduce the phenomenon of reverting of sulfuration, which enhance the resistance to bending of elastomeric material, hysteresis quality when reducing tire rolling, reduce heat-dissipating and crack growth.In addition, do not have the silane group of coupling also can with the hydroxyl coupling (shrink and react) in White Carbon black in elastomeric material, like this White Carbon black molecule is introduced in the vulcanized network body of rubber molecule, further increase the intensity of cross-linked rubber, in vulcanization system, enhance the resistance to deterioration of material, its three, in polymkeric substance, after oligopolymer coupling, molecular weight obtains increase, reduce the cold flow properties of rubber, improve the intensity of cross-linked rubber.Its four, adopt this law synthesis styrene-butadiene rubber(SBR) molecule medium vinyl content can control arbitrarily between 13-72% (wt).
The preparation method of the styrene-conjugated diene multipolymer containing active combined sulfur of the present invention is:
Described vinylbenzene and conjugated diolefine cause with butyllithium in hexane-hexanaphthene mixed solvent, carry out random or block polymerization, after polymerization, form active lithium polymer PSBLi, then add organic multi-sulfur silane solution and carry out linked reaction and obtain.
The general formula of linked reaction of the present invention is:
PSBLi+R
3-Si-(CH
2)
3-Sn-(CH
2)
3-Si-R
3→(PSB)
3-x-SiR
3-Y-(CH
2)
3-(S)
n-(CH
2)
3-SiR
3-Y-(PSB)
3-x+RLi
Wherein, n=2-5, X=0-3, Y=3-0; R can be the alkoxyl group of C1-C4, and (as methoxyl group, oxyethyl group) also can be halogen as-Cl ,-Br.
SB randomly may also be block structure.
The concrete embodiment of the present invention is:
Be solvent with hydrocarbon compound in polymeric kettle, with vinylbenzene, divinyl or isoprene or their mixture are monomer, at 30-120 DEG C, make initiator with butyllithium start polyreaction, butyllithium add-on is 0.25-2mmol/100g monomer, vinylbenzene can first cause with butyllithium, add diene monomers to be again polymerized, also can by vinylbenzene, add butyllithium again after diene monomers mixing and carry out initiated polymerization, also the styrenic-diene monomer of mixing and butyllithium can be added in polymeric kettle simultaneously, polymerization reaction time is 20-120min, after monomer polymerization, add organic multi-sulfur silane in time and carry out coupling, coupling agent add-on is n (butyllithium)/n (coupler)=(1-6)/1, linked reaction time 20-30min.
By adding the RAE extending oil of the 27.2-28.5% of dry glue total mass, last discharging, cohesion, drying.
In polymerization process of the present invention, polymer solvent is the common solvent of anionoid polymerization, is preferably hexane, hexanaphthene.
Polymerization process of the present invention is not only suitable for the copolymerization of butadiene-styrene, also can be suitable for the copolymerization of styrene-isoprene.
Polymerization process of the present invention is not only suitable for solution polymerized butadiene styrene rubber, also can be suitable for preparation SBS, SIS, SIBS and transparent butadiene-styrene impact resin.
Method of the present invention can use the multiple stage reactor polymerization technique of separate unit intermittent polyreaction device or successive polymerization.
The present invention's organic multi-sulfur silane coupling agent used is easy to get, and belongs to homogeneous phase coupled reaction, easy to use, and reaction is easy to control.
When the present invention is prepared for solution polymerization styrene-butadiene rubber, guarantee initiator non-inactivation and coupler stable while, polymerization process is steadily easily controlled, in system, monomer concentration is 20% time, still polyreaction can be made to be well controlled, and can synthesize and obtain not containing gel, monomer conversion is close to 100%, in polymkeric substance, polyhutadiene section vinyl mass content is 13-72%, and can arbitrarily control.Linked reaction can efficiently be carried out, without low molecular weight polycaprolactone zoarium (Fig. 1 is the gel permeation chromatography figure containing active combined sulfur solution polymerized butadiene styrene rubber HVSBR) in coupling post-consumer polymer, that usually can prepare contains intermingle with this rubber of fourth molecular-weight average 20-45 ten thousand, molecular weight distributing index is 1.4-2.8, polymer gel permeation chromatography figure is unimodal wide distribution, crude rubber Mooney viscosity is 40-65, and the active sulphur mass content of the combination in rubber is 0.03-0.062%.
The present invention is used for the sulfurizing formula (mass parts) of tire tread glue: BR 60, mutation rubber 140, White Carbon black Z115GR 105, carbon black N3307.5, Si-693, stearic acid 3, zinc oxide 4.5, antioxidant 4020 2.5, accelerant CZ 2, TBBS1.5, RAE oil 10, sulphur 1.6.
Accompanying drawing explanation
Fig. 1 is embodiment 4 solution polymerized butadiene styrene rubber gel permeation chromatography figure, and its middle-molecular-weihydroxyethyl 290,000, molecular weight distributing index is 1.73, and crude rubber Mooney viscosity is 48, and the active sulphur mass content combined in rubber Middle molecule is 0.061%.
Embodiment
The present invention's following examples are described, and do not form the restriction to the scope of the invention or implementation method.
Measure number-average molecular weight, weight-average molecular weight and the molecular weight distributing index of polymkeric substance (taking tetrahydrofuran (THF) as solvent and moving phase) with gel permeation chromatograph (GPC) in the following example.H-NMR is adopted to compose the microtexture content of quantitative assay polymkeric substance.Mooney viscosity determinator is adopted to measure the crude rubber Mooney viscosity of polymkeric substance; The tan δ value of dynamic visco-elasticity analyser when 0 DEG C and 60 DEG C is adopted to characterize anti-slippery and the rolling resistance of tire tread glue.
Embodiment 1
Under nitrogen protection; the mixture of the hexane-hexanaphthene mixed solvent of 2.2L and vinylbenzene (the S)-divinyl (B) of 360g is added in the polymerization reactor of 5 liters at 60-120 DEG C; wherein quality S/B=75/25; open and stir and add 0.4mol/L butyllithium 12ml; after polyreaction 30min; then add two-[γ-(triethoxysilicane) propyl group] tetrasulfide 1.6mmol and carry out coupled reaction 20min; add the BHT of 1.2g afterwards.After last polymer with water devaporation removes solution and moisture, then drying, survey the number-average molecular weight 8.3 × 10 of product
4, coupling degree 2.47, molecular weight distributing index 2.38, the melting index 8.5g/10min of resin, in conjunction with active sulphur mass content 0.056%.Table 1 is for preparing the physicals of butadiene styrene resin.
The physicals of table 1 combined sulfur butadiene styrene resin
Embodiment 2
Under nitrogen protection; at 50-90 DEG C; hexane-hexanaphthene and the 70g vinylbenzene (S) of 2.5L is added in the polymerization reactors of 5 liters; then add to open and stir and add 0.4mol/L butyllithium 11mol; after polyreaction 30min; add 163.3g divinyl (S/B=3/7) again and continue reaction 25min; then add 0.678mmol two-[γ-(trimethoxy silicon) propyl group] trisulphide carries out coupled reaction 20min; the BHT of 1.5g is added after discharging.Finally by after polymer with water devaporation, drying, record the number-average molecular weight 32 × 10 of product
4, coupling degree 5.63, molecular weight distributing index 1.06, the sulphur mass content 0.032% combined in the star-shaped sbs of synthesis.Table 2 is the physicals of preparation SBS.
Table 2 is containing the physicals of combined sulfur SBS
Embodiment 3
Under nitrogen protection; at 50-90 DEG C; hexanaphthene/hexane mixed solvent and the 30g vinylbenzene (S) of 3.5L is added in the polymerization reactors of 5 liters; then add to open and stir and add 0.4mol/L butyllithium 8ml; after polyreaction 30min; add 146.4g isoprene (S/Ip=17/83) again and continue reaction 25min; then add 1.60mmol two-[γ-(three chloro silicon) propyl group] tetrasulfide carries out coupled reaction 20min; the BHT of 0.8g is added after discharging.Finally by after polymer with water devaporation, drying, record the number-average molecular weight 10.3 × 10 of product
4, coupling degree 1.82, molecular weight distributing index 1.08, the sulphur mass content 0.062% combined in the amphitene type SIS of synthesis.The physicals containing the even type SIS of active sulphur line that table 3 is preparation.
Table 3 is containing the physicals of combined sulfur SIS
Embodiment 4
Under nitrogen protection; at 30-70 DEG C; the mixed solvent of the hexanaphthene/hexane of 2.6L is added in the polymerization reactors of 5 liters; add 0.6ml conditioning agent-T simultaneously; add 70g vinylbenzene (S) and 210 divinyl (B) afterwards; open and stir and add 0.4mol/L butyllithium 5ml; after polyreaction 90min; then add 1.07mmol two-[γ-(three chloro silicon) propyl group] pentasulfide carries out coupled reaction 20min; the BHT of 1.5g and the RAE oil of 105g is added after discharging.Finally by after polymer with water devaporation, drying, record the number-average molecular weight 29 × 10 of product
4, coupling degree 1.46, molecular weight distributing index 1.73, vinyl mass content 72%, GPC spectrogram presents unimodal wide distribution, and the sulphur mass content 0.061% combined in the solution polymerized butadiene styrene rubber (dry glue) of synthesis, crude rubber Mooney viscosity ML100 DEG C 1+4 is 40.The physicals containing active sulphur solution polymerized butadiene styrene rubber that table 4 is preparation.
Table 4 is used for the physicals of high-performance tread rubber containing active sulphur solution polymerized butadiene styrene rubber
Embodiment 5
As implemented polymerization in 4 and oil-filled condition, only adding 0.05ml tetrahydrofuran (THF) and saving coupled processes.The result of the solution polymerized butadiene styrene rubber now synthesized is the number-average molecular weight 28 × 10 of product
4, molecular weight distributing index 1.75, mooney viscosity ML100 DEG C 1+4 is 45, and vinyl mass content 13%, GPC spectrogram presents unimodal wide distribution, not containing active sulphur in the oil-filled rate 27.2% in rubber, rubber molecule.
Embodiment 6
As implemented polymerization in 4 and oil-filled condition, only just two-[γ-(triethoxysilicane) propyl group] pentasulfide add-on is 0.8mmol, solution polymerized butadiene styrene rubber mooney viscosity when finally obtaining is 56, coupling degree 1.91, GPC spectrogram presents unimodal distribution, and molecular weight distributing index is 1.83, the vinyl quality 68% in styrene-butadiene rubber(SBR) in polybutadiene unit; styrene-butadiene rubber(SBR) (dry glue) active sulphur content 0.037%, mooney viscosity ML100 DEG C 1+4 is 58.Table 5 is for styrene-butadiene rubber(SBR) is for the physical and mechanical properties of tire tread glue.
Table 5 styrene-butadiene rubber(SBR) is used for the physical and mechanical properties of tread rubber
Embodiment 7
Under nitrogen protection, at 30-80 DEG C, the mixed solvent of the hexanaphthene/hexane of 2.3L is added in the polymerization reactors of 5 liters, add the structure regulator-T of 0.4ml simultaneously, add 90g vinylbenzene (S) afterwards, the mix monomer of the divinyl (B) of 60g isoprene and 130g, open and stir and add 0.4mol/L butyllithium 6ml, after polyreaction 30min, then add 1.07mmol two-[γ-(triethoxysilicane) propyl group] tetrasulfide carries out coupled reaction 20min, 2 of 1.5g are added after discharging, the RAE oil of 6-di-tert-butyl methyl phenol and 105g.Finally by after polymer with water devaporation, drying, record the number-average molecular weight 29 × 10 of product
4coupling degree 1.57, molecular weight distributing index 2.81, GPC spectrogram presents unimodal wide distribution, the sulphur mass content 0.062% combined in the solution polymerized butadiene styrene rubber (dry glue) of synthesis, crude rubber Mooney viscosity ML100 DEG C 1+4 is 52, and the vinyl mass content in polyhutadiene section is 42,3,4-structures 72% in polyisoprene section.The physicals containing intermingle with butadiene-isoprene-styrenerubber (SIBR) containing active sulphur that table 6 is preparation.
Table 6 is used for the physical and mechanical properties of high-performance tire face glue containing active combined sulfur SIBR
Embodiment 8
Under nitrogen protection; at 30-70 DEG C; the mixed solvent of the hexanaphthene/hexane of 2.6L is added in the polymerization reactors of 5 liters; add 0.2ml conditioning agent-T simultaneously; add 75g vinylbenzene (S) and 205g divinyl (B) afterwards; open and stir and add 0.4mol/L butyllithium 4ml; after polyreaction 30min; add again then add 1.20mmol two-[γ-(trimethoxy silicon) propyl group] pentasulfide carries out coupled reaction 30min; the BHT of 1.5g and the RAE oil of 105g is added after discharging.Finally by after polymer with water devaporation, drying, record the number-average molecular weight 29 × 10 of product
4, coupling degree 1.15, molecular weight distributing index 2.63, vinyl mass content 34%, GPC spectrogram presents unimodal wide distribution, and the sulphur mass content 0.060% combined in the solution polymerized butadiene styrene rubber (dry glue) of synthesis, crude rubber Mooney viscosity ML100 DEG C 1+4 is 47.The physicals containing active combined sulfur solution polymerized butadiene styrene rubber that table 7 is preparation.
Table 7 is used for the physical and mechanical properties of high-performance tread rubber containing active combined sulfur styrene-butadiene rubber(SBR)
Embodiment 9
Under nitrogen protection, at 30-70 DEG C, the mixed solvent of the hexanaphthene/hexane of 2.6L is added in the polymerization reactors of 5 liters, add 0.45ml conditioning agent-T simultaneously, add 90g vinylbenzene (S) and 190g divinyl (B) afterwards, open and stir and add 0.4mol/L butyllithium 16ml, after polyreaction 120min, add again 0.9mmol two-[γ-(triethoxysilicane) propyl group] pentasulfide and 0.2mmol two-[γ-(three chloro silicon) propyl group] disulphide carries out coupled reaction 60min, 2 of 1.5g are added after discharging, 6-di-tert-butyl methyl phenol and RAE oil.Finally by after polymer with water devaporation, drying, record the number-average molecular weight 45 × 10 of product
4, coupling degree 5.56, molecular weight distributing index 1.73, vinyl mass content 73%, GPC spectrogram presents unimodal wide distribution, and the sulphur mass content 0.045% combined in the solution polymerized butadiene styrene rubber (dry glue) of synthesis, crude rubber Mooney viscosity ML100 DEG C 1+4 is 62.The physicals containing active combined sulfur solution polymerized butadiene styrene rubber that table 8 is preparation.
Table 8 is used for the physical and mechanical properties of high-performance tread rubber containing active combined sulfur styrene-butadiene rubber(SBR)
Claims (2)
1., containing a styrene-conjugated diene multipolymer for active combined sulfur, it is characterized in that, being organic multi-sulfur silane coupling styrene-conjugated diene active copolymer, is formed through coupling polymerization by the component of following A, B raw material;
A. the organic multi-sulfur silane of coupling agent, wherein organic multi-sulfur silane is two-[γ-(tri-alkoxy silicon) propyl group] polysulfide, and wherein alkoxyl group is methoxy or ethoxy; In molecule, poly-sulphur is with-S
n-occur, wherein n=2 ~ 5; Or organic multi-sulfur silane is a kind of in two-[γ-(three chloro silicon) propyl group] disulphide, two-[γ-(three chloro silicon) propyl group] tetrasulfide, two-[γ-(three chloro silicon) propyl group] pentasulfide or the mixture in them;
B. make initiator with butyllithium, conjugated diene and vinylbenzene are the polymer that random copolymerization or block polymerization obtain that molecular end is active lithium;
Vinylbenzene and conjugated diolefine mass ratio are=25-75:75-25, and butyllithium is 1 ~ 6:1 with the amount of substance ratio of organic multi-sulfur silane.
2. the styrene-conjugated diene multipolymer containing active combined sulfur as claimed in claim 1, it is characterized in that, the molecular-weight average of described multipolymer is 8-40 ten thousand, molecular weight distribution presents unimodal distribution, molecular weight distributing index is 1 ~ 2.8, and the active sulphur mass content of the combination of this multipolymer is 0.030-0.062%.
3. the styrene-conjugated diene multipolymer containing active combined sulfur as claimed in claim 1, is characterized in that, described conjugated diene is divinyl or isoprene or their mixture.
4. the styrene-conjugated diene multipolymer containing active combined sulfur as claimed in claim 1, it is characterized in that, described two-[γ-(tri-alkoxy silicon) propyl group] polysulfide be pair a kind of in-[γ-(trimethoxy silicon) propyl group] disulphide, two-[γ-(trimethoxy silicon) propyl group] tetrasulfide, two-[γ-(triethoxysilicane) propyl group] disulphide, two-[γ-(tri-alkoxy silicon) propyl group] pentasulfide or the mixture in them.
5. the styrene-conjugated diene multipolymer containing active combined sulfur as claimed in claim 1, it is characterized in that, butyllithium is n-Butyl Lithium or isobutyl-lithium.
6. an application for organic multi-sulfur silane, is characterized in that, described organic multi-sulfur silane is two-[γ-(tri-alkoxy silicon) propyl group] polysulfide, and wherein alkoxyl group is methoxy or ethoxy; In molecule, poly-sulphur is with-S
n-occur, wherein n=2 ~ 5; Or two-[γ-(three chloro silicon) propyl group] disulphide, two-[γ-(three chloro silicon) propyl group] tetrasulfide, a kind of in two-[γ-(three chloro silicon) propyl group] pentasulfide or the mixture in them; Organic multi-sulfur silane is used as coupling agent to be applied in the polyreaction that vinylbenzene and conjugated diene cause at butyllithium.
7. application according to claim 6, it is characterized in that, described two-[γ-(tri-alkoxy silicon) propyl group] polysulfide be pair a kind of in-[γ-(trimethoxy silicon) propyl group] disulphide, two-[γ-(trimethoxy silicon) propyl group] tetrasulfide, two-[γ-(triethoxysilicane) propyl group] disulphide, two-[γ-(tri-alkoxy silicon) propyl group] pentasulfide or the mixture in them.
8. the application of the styrene-conjugated diene multipolymer containing active combined sulfur described in any one of claim 1-5, it is characterized in that, using conjugated diene and vinylbenzene, the obtained styrene-butadiene rubber(SBR) containing active combined sulfur after random copolymerization and linked reaction complete applies the material as tire tread glue.
9. the application of the styrene-conjugated diene multipolymer containing active combined sulfur according to claim 8, after linked reaction completes, add extending oil in styrene-butadiene rubber(SBR) solution, adding weight part is add 35-40 part in 100 parts of dry glue amounts of styrene-butadiene rubber(SBR).
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| 佟园园等."用γ-氯丙基三甲氧基硅烷端基改性星形溶聚丁苯橡胶".《合成橡胶工业》.2011,第34卷(第2期), * |
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