CN101817911A - Star block copolymer prepared from isoprene, butadiene and styrene, and preparation method and application thereof - Google Patents
Star block copolymer prepared from isoprene, butadiene and styrene, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a star block copolymer prepared from isoprene, butadiene and styrene, which contains a structure of the following formula (1): (pI-pSB)n-X, and optionally contains a structure of the following formula (2): pI- pSB, wherein pI is an isoprene homopolymerized block; pSB is an irregular polymerized block of the styrene and the butadiene; X is a residue of a coupling agent; and n is an average number of arms connected with the X and is a figure more than 2 and less than or equal to 4. In addition, the invention also relates to a method for preparing the star block copolymer, which comprises the following steps of: (a) initiating polymerization of the isoprene by utilizing lithium alkyl to obtain an active polyisoprene block; (b) initiating the polymerization of the styrene and the butadiene by utilizing the polyisoprene block to obtain a block copolymer; and (c) adding the coupling agent into the block copolymer for coupling to obtain the star block copolymer. The star block copolymer has low rolling resistance and acceptable slippery resistance and can be applied to the fields of high-performance tread rubber of automobile tires and other rubber products. Finally, the invention also relates to the application of the star block copolymer as the tread rubber of automobile tires.
Description
Technical field
The present invention relates to star block copolymer that forms by isoprene, divinyl and vinylbenzene and its production and use.Particularly, the present invention relates to the star block copolymer formed by isoprene homopolymerization section and divinyl and cinnamic random copolymerization section and the preparation method of this star block copolymer and purposes.
Background technology
The present rubber various commonly used that uses, as cis-1,4-polybutadiene rubber (BR), natural rubber (NR), emulsion polymerized styrene butadiene rubber (ESBR), solution polymerization styrene-butadiene rubber (SSBR) etc., they have own special advantages, but also deficiency are arranged.Flexible best as BR, rolling resistance is little, but wet-sliding resistant performance is relatively poor; NR is flexible placed in the middle, the rolling resistance better performances, but wet-sliding resistant performance is general; The higher SBR wet-sliding resistant performance of styrene-butadiene rubber(SBR) (SBR), especially styrene content is superior, but the rolling resistance performance is relatively poor.In various conventional rubbers, any all various performance demands of balance preferably.From present data, the wet-sliding resistant performance of rubber generally characterizes indirectly with rubber tan δ value during in 0 ℃ in dynamic properties test, and common this value is showing more than 0.20 that wet-sliding resistant performance is better; And the rolling resistance performance is generally represented with the tan δ value of rubber 60 ℃ the time, and this value is showing the rolling resistance better performances below 0.12 usually.
For the over-all properties of balance rubber preferably, Nordsiek has proposed the notion of integrated rubber (referring to K H Nordsiek, The " integral rubber " concept-an approach to an ideal tire tread rubber, Kautschuk, Gummi Kunststoffe, 1985,38 (3): 178-185), this rubber is the terpolymer of a kind of vinylbenzene, divinyl and isoprene, better the over-all properties of balance rubber.United States Patent (USP) 4,843,120 have reported the synthetic integrated rubber with a plurality of second-order transition temperatures of the two-step approach that adopts two reactor successive polymerizations, wherein in first still, add styrene monomer, isoprene monomer, divinylic monomer, n-butyl lithium initiator, inert organic solvents and polar modifier in 85 ℃ of following polyase 13s 0 minute, and after transformation efficiency reaches 60%, reaction mixture is transferred in second still, further reacts down and reached 100% transformation efficiency in 1 hour in 88 ℃ to 91 ℃.Products therefrom has a plurality of second-order transition temperatures, and its tan δ value of 60 ℃ is 0.091.As seen styrene butadiene-isoprene terpolymer (integrated rubber) is in the distinctive feature that oneself is arranged aspect the reduction rolling resistance.In addition, it is initiator that EP 438967A1 has set forth with the lithium alkylide, adopt the substep feed way to prepare a kind of linear polymer, this linear polymer has following structure: I-SB, wherein: I is a polyisoprene blocks, 1, and the 4-structural content is 75%～98%, 3, the 4-structural content is 2%-25%; SB is 1,3-butadiene and cinnamic copolymerization section, and wherein in the divinyl repeating unit 1, the 2-structure is 50-92%.The polymkeric substance that obtains according to this patent working example has 60 ℃ lower tan δ (0.130) and 0 ℃ higher tan δ value (0.306), describes the butadiene-styrene-isoprene block copolymer for preparing with this method as can be known according to it and has comprehensive performance than the product that SBR/NR blend obtains.
Summary of the invention
Based on above-mentioned prior art situation, the present inventor has carried out research extensively and profoundly aspect the wet-sliding resistant performance of rubber and rolling resistance performance well balanced, discover, a kind of specific isoprene-butadiene-styrol copolymer rubber has excellent rolling resistance performance, rolling resistance is low, its wet-sliding resistant performance is not significantly weakened simultaneously, still is within the acceptable scope, thereby can be used for high-performance tread rubber of automobile tires and other rubber item fields.The star block copolymer (also claim radiation segmented copolymer) of this multipolymer for forming by isoprene, divinyl and vinylbenzene, the star block copolymer that it is made up of isoprene homopolymerization section and divinyl and cinnamic random copolymerization section.
Thereby, the object of the present invention is to provide a kind of new isoprene-butadiene-cinnamic star block copolymer, this multipolymer has excellent rolling resistance performance, rolling resistance is low, its wet-sliding resistant performance is not significantly weakened simultaneously, still be within the acceptable scope, thereby can be used for high-performance tread rubber of automobile tires and other rubber item fields.
Above-mentioned purpose is achieved by a kind of star block copolymer that is formed by isoprene, divinyl and vinylbenzene, and this star block copolymer comprises following formula (1) structure:
(pI-pSB)
n-X????(1)
And randomly comprise following formula (2) structure:
pI-pSB????(2)
Wherein:
PI is the homopolymerization section of isoprene, and pSB is the random copolymerization section of vinylbenzene and divinyl, and X is the residue of coupling agent, the average quantity of the arm that is connected with X with n representative and be smaller or equal to 4 number greater than 2;
The basic number-average molecular weight of this star block copolymer, promptly the number-average molecular weight of polymkeric substance in the polymerization system before coupling agent adds is 50000-500000; Based on the weight sum of pI section in this star block copolymer and pSB section, the content of pI section is 5-50 weight %, and the isoprene 1 in this pI section, 4-structural content are 60-98%, and isoprene 3,4-structural content are 2-40%; And in the pSB section, the content of divinyl repeating unit is that the content of 50-95 weight % and vinylbenzene repeating unit is 5-50 weight %.
The invention is characterized in: polyisoprene IR and Butadiene random copolymer rubber SBR in-situ accomplishes chemistry in polymerization reactor are composite, make the isoprene-butadiene-cinnamic star block copolymer rubber that obtains according to the present invention have the advantage of IR and SBR concurrently.
Star block copolymer of the present invention is before the use coupling agent carries out coupling, and its number-average molecular weight is generally 50000-500000, also can have higher or lower number-average molecular weight certainly, but is preferably 100000-300000.
After coupling, the number-average molecular weight of star block copolymer of the present invention is generally greater than 100000 to 2000000, is preferably 200000-2000000, more preferably 400000-800000; Molecular weight distributing index is generally 1.0-3.0.
In star block copolymer of the present invention, weight sum based on pI section in this star block copolymer and pSB section, the content of pI section (that is, the weight content of isoprene repeating unit) is generally 5-50 weight %, be preferably 15-25 weight %, that is to say, all repeating units of the content of pSB section or pSB section (promptly, divinyl repeating unit and vinylbenzene repeating unit) content be 50-95 weight %, be preferably 75-85 weight %.The microstructure that this pI section has is normally: isoprene 1,4-structural content are 60-98%, and 3, the 4-structural content is 2-40%; Preferably, in the pI section, isoprene 1,4-structural content are 80-90%, and 3, the 4-structural content is 10-20%.
In a preferred embodiment of the invention, the number-average molecular weight of the pI section in the star block copolymer is generally 10000-200000, is preferably 20000-100000.
In the pSB of star block copolymer of the present invention section, usually, the content of divinyl repeating unit is 50-95 weight %, and the content of vinylbenzene repeating unit is 5-50 weight %; Preferably, the content of divinyl repeating unit is 60-80 weight %, and the content of vinylbenzene repeating unit is 20-40 weight %.
In another preferred embodiment of the present invention, in the pSB of star block copolymer section, based on all divinyl repeating units, divinyl 1,2-structural content are 15-45%, and 1, the 4-structural content is 55-85%; Preferably, divinyl 1,2-structural content are 30-45%, and 1, the 4-structural content is 55-70%.
In another preferred embodiment of the present invention, the number-average molecular weight of the pSB section of star block copolymer is generally 40000-300000, is preferably 80000-200000, more preferably 100000-200000.
In star block copolymer of the present invention, X is the residue of coupling agent.The concrete coupling agent of this residue and use is closely related, and those skilled in the art can determine the structure of residue fully according to the coupling agent that uses.
In addition, for the purpose of the present invention, the average quantity of the arm that n in the formula (1) representative is connected with the residue X of coupling agent, and these are several greater than 2 smaller or equal to 4, preferably n is smaller or equal to 3.8 number more than or equal to 2.5.
In addition, the present invention also provides a kind of method for preparing star block copolymer of the present invention, and it comprises:
(a) make the isoprene monomer polymerization in the non-polar hydrocarbon kind solvent in the presence of alkyl lithium initiator, obtain active polyisoprene section, in this polyisoprene section, isoprene 1,4-structural content are 60-98% and 3, and the 4-structural content is 2-40%;
(b) utilize the active polyisoprene section that obtains in the step (a) to cause divinyl and cinnamic copolymerization, this copolyreaction is carried out in the presence of polar modifier, obtains the segmented copolymer that polyisoprene homopolymerization section is connected with the random copolymerization section of vinylbenzene and divinyl; And
(c) add coupling agent, make the middle segmented copolymer coupling that obtains of step (b) to obtain star block copolymer, this star block copolymer comprises following formula (1) structure:
(pI-pSB)
n-X????(1)
And randomly comprise following formula (2) structure:
pI-pSB????(2)
Wherein:
PI is the homopolymerization section of isoprene, and pSB is the random copolymerization section of vinylbenzene and divinyl, and X is the residue of coupling agent, the average quantity of the arm that is connected with X with n representative and be smaller or equal to 4 number greater than 2; And
The basic number-average molecular weight of this star block copolymer, promptly the number-average molecular weight of polymkeric substance in the polymerization system before coupling agent adds is 50000-500000; Based on the weight sum of pI section in this star block copolymer and pSB section, the content of pI section is 5-50 weight %, and the isoprene 1 in this pI section, 4-structural content are 60-98% and isoprene 3, and the 4-structural content is 2-40%; And in the pSB section, the content of divinyl repeating unit is that the content of 50-95 weight % and vinylbenzene repeating unit is 5-50 weight %.
This it is pointed out that all related in preparation method of the present invention technical characterictics all have with above about the described identical or corresponding implication of star block copolymer of the present invention.
In preparation method of the present invention, in step (a), used the non-polar hydrocarbon kind solvent.At this, those skilled in the art should be appreciated that obviously this solvent should be in a liquid state under the polymeric reaction condition of step (a), and can not participate in polyreaction, also can not react with the polymkeric substance that reaction obtains, and promptly this solvent is an inert.This kind solvent is conspicuous for the those of ordinary skill in isoprene polymerization field, and can easily make one's options.However, for the purpose of the present invention, this non-polar hydrocarbon kind solvent is preferably benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, Mixed XYLENE, raffinate oil or aforementioned solvents in two or more arbitrary combination.For the polymerization of step (a), the consumption of non-polar hydrocarbon kind solvent is conventional.
In the step (a) of the inventive method, isoprene generation homopolymerization obtains active polyisoprene.In order to cause this polyreaction, the present invention has adopted alkyl lithium initiator.This alkyl lithium initiator can be lithium methide, lithium ethide, sec.-propyl lithium, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, hexyllithium, uncle's octyl group lithium, positive decyl lithium or the like, and the preferred alkyl lithium initiator that uses comprises n-Butyl Lithium, s-butyl lithium and tert-butyl lithium.In the methods of the invention, also can use two or more alkyl lithium initiator, for example use the arbitrary combination of the cited alkyl lithium catalyst in front.Particularly preferably be, the inventive method is used the initiator of n-Butyl Lithium as step (a).
The consumption of alkyl lithium initiator depend on for the purpose of the present invention the catalytic activity wanting the molecular weight of synthetic polyisoprene and depend on initiator itself.For using specific alkyl lithium initiator to synthesize the polyisoprene with specified molecular weight, those skilled in the art can determine the consumption of this alkyl lithium initiator according to its common practise.
In the methods of the invention, the temperature of using lithium alkylide to cause isoprene polymerization can change in wide region, and usually, this kick off temperature is 20-150 ℃, is preferably 60-100 ℃.
In step (a), allow the polymerization of isoprene carry out always, till all isoprene monomers exhaust substantially, that is to say that this polymerization will continue until that the isoprene transformation efficiency is greater than 99%.Owing to adopted lithium alkylide to cause the polymerization of isoprene, so polymerization obtains active polyisoprene section.
In step (a) step (b) afterwards, need utilize the active polyisoprene section that obtains in the step (a) to cause divinyl and cinnamic copolymerization, this copolyreaction is carried out in the presence of polar modifier.For the present invention, operable polar modifier comprises ether, dibutyl ether, tetrahydrofuran (THF), glycol dimethyl ether, diglyme, tetrahydrofurfuryl alcohol ether, dioxane, crown ether, triethylamine, Tetramethyl Ethylene Diamine, HMPA, potassium tert.-butoxide, tertiary amyl alcohol potassium, potassium lauryl, alkyl benzene sulphonate (ABS) potassium, sodium alkyl benzene sulfonate, the arbitrary combination of two or more in the perhaps aforementioned polar modifier.
In the step (b) of the inventive method, vinylbenzene and divinyl carry out random copolymerization under the condition that active polyisoprene causes, obtain the segmented copolymer that polyisoprene homopolymerization section is connected with the random copolymerization section of vinylbenzene and divinyl.This copolymerization is usually by carrying out in the reaction mixture that contains active polyisoprene section that polar modifier and monomer (being vinylbenzene and divinyl) is added to acquisition in the step (a).This is to add polar modifier by elder generation, and back interpolation vinylbenzene and divinylic monomer are realized.At this moment, if necessary, can additionally add solvent, to keep the proper concn of monomer and polymkeric substance, so that monomeric random copolymerization.
When adding divinyl and styrene monomer, the temperature of polymerization reaction mixture is 10-80 ℃, preferred 20-60 ℃.
In the random copolymerization section of vinylbenzene that step (b) produces and divinyl, this copolymerization section is usually by the repeating unit of derived from butadiene and the constituting derived from cinnamic repeating unit of 5-50 weight % of 50-95 weight %.Preferably, the random copolymerization section of this vinylbenzene and divinyl is by the repeating unit of the derived from butadiene of 60-80 weight % and constituting derived from cinnamic repeating unit of 20-40 weight %.In a further preferred embodiment, in the random copolymerization section of this vinylbenzene and divinyl, based on all divinyl repeating units, divinyl 1,2-structural content are 15-70%, and 1, the 4-structural content is 30-85%; Preferably, divinyl 1,2-structural content are 30-50%, and 1, the 4-structural content is 50-70%.
Till copolymerization in the step (b) continues until that usually all comonomers (that is, vinylbenzene and divinylic monomer) exhaust substantially.That is to say that this copolymerization will be carried out always, till the total conversion rate of vinylbenzene and divinylic monomer is greater than 99%.
After the copolymerization of step (b) is finished, in the gained reaction mixture, add coupling agent, make polyisoprene homopolymerization section wherein carry out coupling with the segmented copolymer that the random copolymerization section of vinylbenzene and divinyl is connected.To this, can use any coupling agent that described segmented copolymer coupling can be obtained star block copolymer.For example, this coupling agent can for be selected from down the group in one or more: many vinyl aromatic (co)s hydro carbons (as Vinylstyrene), polyfunctional epoxies (as epoxy oleum lini, epoxy soybean oil), imines class, aldehydes, ketone, acid anhydride class, ester class (as ethyl acetate), isocyanates and halogenide.The preferred coupling agent that uses is tin tetrachloride, silicon tetrachloride or its combination.Coupling efficiency is generally 20-100%, preferred 40-80%.
After the linked reaction of step (c), if necessary, can also use terminator to stop polyreaction.The terminator that is used for this is conventional to those skilled in the art.Common operable terminator comprises deionized water, alcohol, acid etc.For pure terminator, it normally contains the lower alcohol of 1-4 carbon atom, and the example comprises methyl alcohol, ethanol, Virahol, n-propyl alcohol and the trimethyl carbinol.The use of terminator stops reactive polymer.
After coupling or after stopping, can also in reaction mixture (that is polymkeric substance glue), add anti-aging agent.For the present invention, conventional anti-aging agent can use.Preferably, operable anti-aging agent comprises according to the present invention: 2,6-ditertbutylparacresol (264), Irganox 1520 (Switzerland vapour Bagong department), four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (promptly 1010)/tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) compound anti-aging agent (wherein 168 content is not higher than 50 weight %) ester (promptly 168)), and 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl (promptly 1076)/tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester (promptly 168) compound anti-aging agent (wherein 168 content is not higher than 50 weight %).After adding anti-aging agent such as Irganox 1520 and be two keys of preventing in the conjugated diene polymer molecular chain and oxygen etc. and contacting under certain condition, produce adverse consequences down such as heat effect, as reactions such as crosslinked, degradeds, increase the gel content of rubber in toluene solution.According to the present invention, the consumption of anti-aging agent is 0.05-2 weight % based on dried glue weight (being polymer weight).
Afterwards, from the polymkeric substance glue, reclaim star block copolymer of the present invention.This processing is conventional to those skilled in the art.For example, the measure that can take comprises modes such as alcoholization precipitation, centrifugation, filtration, decant, hot water cohesion, required polymkeric substance is precipitated from solvent separate out.After multipolymer is separated from solution, can also adopt the steam stripped mode that the volatile organic solvent in the multipolymer is separated, thereby realize the purifying of multipolymer, the star block copolymer that obtains purifying.
Star block copolymer of the present invention or star block copolymer prepared according to the methods of the invention have extremely low rolling resistance, and have acceptable anti-slippery and a good physical and mechanical properties, be highly suitable for high-performance tread rubber of automobile tires, and can be applicable to other rubber item fields.
Therefore, last aspect of the present invention relates to the purposes of star block copolymer of the present invention as tread rubber of automobile tires.
Enumerate some embodiments of the present invention below, so as to further specifying characteristics of the present invention, but do not limit the scope of the invention with this.
Embodiment
In the present invention, the basic number-average molecular weight of synthetic star block copolymer rubber, coupling efficiency adopt U.S. WATERS company 2690 type gel permeation chromatographs (GPC) to measure, and wherein THF is a moving phase, and narrow distribution polystyrene is a standard specimen, and temperature is 25 ℃.
The microtexture of synthetic star block copolymer rubber is characterized by the Bruker400 nuclear magnetic resonance spectrometer.
The dynamic properties of synthetic star block copolymer rubber adopts the U.S. DMA-2980 of TA company type viscoelastic spectrometer to measure, and its medium frequency is 2Hz, and temperature rise rate is 5 ℃/min, rises to 100 ℃ by-120 ℃, and sample size is 40mm * 5mm * 1mm.
Rubber adopts mill mixing, the roller temperature be carry out under 50 ± 5 ℃ mixing, mixing after, park after 4 hours and carry out back mixing, back mixing finishes, and parks half an hour.With the vulcanizing press sulfuration, cure conditions: 145 ℃ of temperature, more than the pressure 10MPa, sulfuration 35min cools off film then from mould, be used for performance test.The sulfuration basic components, rubber: 100g; Aromatic hydrocarbon oil (oil company, Kelamayi, Xinjiang): 5g; Carbon black (Haitun Carbon Black Co., Ltd. Tianjin): 45g; Sulphur (Yangquan, Shanxi mineral factory): 1g; Promotor (N-cyclohexyl-2-[4-morpholinodithio base sulphenamide, the new biochemical plant in Shenyang): 1g; Stearic acid (Shunyi, Beijing Lee satisfies the chemical plant): 2g; Anti-aging agent (N-Phenyl beta naphthylamine, organic factory of Lanzhou chemical industrial company): 1g; Zinc oxide (auxiliary reagent factory, Shenyang): 5g.Vulcanizating glue physical performance adopts XLL250 type rubber puller system (day island proper Tianjin company) to press GB/T528-1998 and measures; Mooney viscosity is pressed GB/T1232-92 with Japanese SHIMADZU mooney viscosity and is measured.
Embodiment 1
In 5 liters of stainless steel stirring tanks, add 3000 milliliters of hexanaphthenes and 180 gram isoprene and add the 20mmol n-butyl lithium initiator down at 65 ℃, react 60 minutes (this moment, the transformation efficiency of isoprene monomer was 99.6%).Add the 0.12mol tetrahydrofuran (THF) then, treat to add when system temperature is reduced to 40 ℃ 135 gram divinyl and 45 gram vinylbenzene, react (this moment, the total conversion rate of divinyl and styrene monomer was 99.8%) after 90 minutes, add the SnCl of 0.31mmol
46 milliliters of Virahol terminators of adding after 20 minutes are reacted in reaction.The glue that obtains adds antioxidant 264, and add-on is 0.6% of a dried glue weight, with hot water cohesion, hot-rolling drying treatment.Sample is carried out the physicals test, and the result is as shown in table 1 below.
Embodiment 2
Polymerization technique and condition are with embodiment 1, and the quality that just adds isoprene is 144 grams, divinyl 162 grams, vinylbenzene 54 grams.Sample is carried out the physicals test, and the result is as shown in table 1 below.
Embodiment 3
Polymerization technique and condition are with embodiment 1, and the quality that just adds isoprene is 108 grams, divinyl 189 grams, vinylbenzene 63 grams.Sample is carried out the physicals test, and the result is as shown in table 1 below.
Embodiment 4
Polymerization technique and condition are with embodiment 1, and the quality that just adds isoprene is 72 grams, divinyl 216 grams, vinylbenzene 72 grams.Sample is carried out the physicals test, and the result is as shown in table 1 below.
Embodiment 5
Polymerization technique and condition are with embodiment 1, and the quality that just adds isoprene is 36 grams, divinyl 243 grams, vinylbenzene 81 grams.Sample is carried out the physicals test, and the result is as shown in table 1 below.
Table 1 polymerization process condition and product rerum natura
| Embodiment | ?1 | ??2 | ??3 | ??4 | ??5 |
| Isoprene repeating unit (weight %) | ?50 | ??40 | ??30 | ??20 | ??10 |
| The isoprene kick off temperature (℃) | ?65 | ??65 | ??65 | ??65 | ??65 |
| Divinyl repeating unit (weight %) | ?37.5 | ??45 | ??52.5 | ??60 | ??67.5 |
| Vinylbenzene repeating unit (weight %) | ?12.5 | ??15 | ??17.5 | ??20 | ??22.5 |
| System temperature when adding SB (℃) | ?40 | ??40 | ??40 | ??40 | ??40 |
| Embodiment | ?1 | ??2 | ??3 | ??4 | ??5 |
| Segmented copolymer basis number-average molecular weight, the i.e. number-average molecular weight (ten thousand) before the coupling not | ?18.5 | ??18.8 | ??18.7 | ??19.0 | ??19.5 |
| Average arm is counted n | ?3.19 | ??3.15 | ??2.82 | ??3.02 | ??3.40 |
| Coupling efficiency (%) | ?62 | ??66 | ??64 | ??60 | ??61 |
| Shao Er hardness | ?66 | ??56 | ??60 | ??60 | ??66 |
| Tear strength (MPa) | ?37 | ??40 | ??34 | ??35 | ??40 |
| Tension set (%) | ?5 | ??4 | ??4 | ??7 | ??14 |
| Mooney point | ?33 | ??36 | ??53 | ??66 | ??99 |
| 300% tensile modulus (MPa) | ?11.2 | ??9.6 | ??10.8 | ??11.2 | ??10.5 |
| Tensile strength (MPa) | ?17.7 | ??15.2 | ??17.3 | ??20.5 | ??15.2 |
| Elongation at break (%) | ?414 | ??401 | ??392 | ??447 | ??403 |
| 1,2-Bd% (mass ratio is based on all Bd that introduce polymkeric substance) | ?38.9 | ??40.8 | ??38.0 | ??38.5 | ??37.0 |
| 1,4-Bd% (mass ratio is based on all Bd that introduce polymkeric substance) | ?61.1 | ??59.2 | ??62.0 | ??61.5 | ??63.0 |
| 1,4-Ip% (mass ratio is based on all Ip that introduce polymkeric substance) | ?88.1 | ??87.1 | ??89.8 | ??84 | ??82.7 |
| 3,4-Ip% (mass ratio is based on all Ip that introduce polymkeric substance) | ?11.9 | ??12.9 | ??10.2 | ??16 | ??17.2 |
| ??tanδ(0℃) | ?0.1757 | ??0.1740 | ??0.1722 | ??0.2244 | ??0.2156 |
| ??tanδ(60℃) | ?0.07235 | ??0.06357 | ??0.04799 | ??0.05566 | ??0.05455 |
Claims (18)
1. star block copolymer that forms by isoprene, divinyl and vinylbenzene, described star block copolymer comprises following formula (1) structure:
(pI-pSB)
n-X????(1)
And randomly comprise following formula (2) structure:
pI-pSB????(2)
Wherein:
PI is the homopolymerization section of isoprene, and pSB is the random copolymerization section of vinylbenzene and divinyl, and X is the residue of coupling agent, and the average quantity of the arm that is connected with X with n representative and be greater than 2 smaller or equal to 4 number is preferably the number of 2.5-3.8;
The basic number-average molecular weight of described star block copolymer, promptly the number-average molecular weight of polymkeric substance in the polymerization system before coupling agent adds is 50000-500000; Based on the weight sum of pI section in the described star block copolymer and pSB section, the content of pI section is 5-50 weight %, and the isoprene 1 in the described pI section, 4-structural content are 60-98% and isoprene 3, and the 4-structural content is 2-40%; And in the pSB section, the content of divinyl repeating unit is that the content of 50-95 weight % and vinylbenzene repeating unit is 5-50 weight %.
2. according to the star block copolymer of claim 1, its basic number-average molecular weight is 100000-300000.
3. according to the star block copolymer of claim 1 or 2, wherein based on the weight sum of pI section in the described star block copolymer and pSB section, the content of pI section is 15-25 weight %.
4. according to each star block copolymer among the claim 1-3, the isoprene 1 in the pI section wherein, the 4-structural content is 80-90%, and isoprene 3, the 4-structural content is 10-20%.
5. according to each star block copolymer among the claim 1-4, wherein the number-average molecular weight of pI section is 10000-200000, is preferably 20000-100000.
6. according to each star block copolymer among the claim 1-5, wherein in the pSB section, the content of divinyl repeating unit is that the content of 60-80 weight % and vinylbenzene repeating unit is 20-40 weight %.
7. according to each star block copolymer among the claim 1-6, wherein in the pSB section, based on all divinyl repeating units, divinyl 1, the 2-structural content is 15-45%, with divinyl 1, the 4-structural content is 55-85%, preferably, divinyl 1, the 2-structural content is 30-45% and divinyl 1, and the 4-structural content is 55-70%.
8. according to each star block copolymer among the claim 1-7, wherein the number-average molecular weight of pSB section is 40000-300000, is preferably 100000-200000.
9. method for preparing as each desired star block copolymer among the claim 1-8, it comprises:
(a) make the isoprene monomer polymerization in the non-polar hydrocarbon kind solvent in the presence of alkyl lithium initiator, obtain active polyisoprene section, in described polyisoprene section, isoprene 1,4-structural content are 60-98% and 3, and the 4-structural content is 2-40%;
(b) utilize the active polyisoprene section that obtains in the step (a) to cause divinyl and cinnamic copolymerization, described copolyreaction is carried out in the presence of polar modifier, obtains the segmented copolymer that polyisoprene homopolymerization section is connected with the random copolymerization section of vinylbenzene and divinyl; And
(c) add coupling agent, make the middle segmented copolymer coupling that obtains of step (b) to obtain star block copolymer, described star block copolymer comprises following formula (1) structure:
(pI-pSB)
n-X????(1)
And randomly comprise following formula (2) structure:
pI-pSB????(2)
Wherein:
PI is the homopolymerization section of isoprene, and pSB is the random copolymerization section of vinylbenzene and divinyl, and X is the residue of coupling agent, and the average quantity of the arm that is connected with X with n representative and be greater than 2 smaller or equal to 4 number is preferably the number of 2.5-3.8; And
The basic number-average molecular weight of described star block copolymer, promptly the number-average molecular weight of polymkeric substance in the polymerization system before coupling agent adds is 50000-500000; Based on the weight sum of pI section in the described star block copolymer and pSB section, the content of pI section is 5-50 weight %, and the isoprene 1 in the described pI section, 4-structural content are 60-98% and isoprene 3, and the 4-structural content is 2-40%; And in the pSB section, the content of divinyl repeating unit is that the content of 50-95 weight % and vinylbenzene repeating unit is 5-50 weight %.
10. according to the method for claim 9, wherein said non-polar hydrocarbon kind solvent is benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, Mixed XYLENE, raffinate oil or aforementioned solvents in two or more arbitrary combination.
11. according to the method for claim 9 or 10, wherein said alkyl lithium initiator is n-Butyl Lithium, s-butyl lithium, tert-butyl lithium or their arbitrary combination, preferred n-Butyl Lithium.
12. according to each method among the claim 9-11, the polymeric temperature that wherein causes isoprene is 20-150 ℃, preferred 60-100 ℃.
13. according to each method among the claim 9-12, wherein said polar modifier is an ether, dibutyl ether, tetrahydrofuran (THF), glycol dimethyl ether, diglyme, tetrahydrofurfuryl alcohol ether, dioxane, crown ether, triethylamine, Tetramethyl Ethylene Diamine, HMPA, potassium tert.-butoxide, tertiary amyl alcohol potassium, potassium lauryl, alkyl benzene sulphonate (ABS) potassium, sodium alkyl benzene sulfonate, the arbitrary combination of two or more in the perhaps aforementioned polar modifier.
14. according to each method among the claim 9-13, wherein when adding divinyl and styrene monomer, the temperature of reaction mixture is 10-80 ℃, preferred 20-60 ℃.
15. according to each method among the claim 9-14, use therein coupling agent is to be selected from down in the group one or more: many vinyl aromatic (co)s hydro carbons, polyfunctional epoxies, imines class, aldehydes, ketone, acid anhydride class, ester class, isocyanates and halogenide, the coupling agent that preferably uses is tin tetrachloride, silicon tetrachloride or its combination.
16. according to each method among the claim 9-15, wherein coupling efficiency is 20-100%, preferred 40-80%.
17., wherein after the linked reaction of step (c), use terminator to stop polyreaction according to each method among the claim 9-16.
18. as each desired star block copolymer among the claim 1-8 as the purposes of tread rubber of automobile tires.
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