CN104059196A - Structure adjusting agent for olefin anionic polymerization, ternary copolymerized rubber, preparation method and application thereof - Google Patents
Structure adjusting agent for olefin anionic polymerization, ternary copolymerized rubber, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a structure adjusting agent for olefin anionic polymerization, ternary copolymerized rubber, a preparation method and an application thereof. The structure adjusting agent comprises bis(tetrahydrofuran) compound and alkylbenzene sulfonate, wherein the bis(tetrahydrofuran) compound is a compound with a structure as shown in formula I. The preparation method of ternary copolymerized rubber comprises contacting a monomer mixture containing vinyl aromatic hydrocarbons, first conjugated diene, and second conjugated diene with an organic lithium initiator and the structure adjusting agent in a solvent in inert atmosphere under an anionic polymerization reaction condition. The invention also provides the ternary copolymerized rubber and an application thereof. The structure adjusting agent provided in the invention can high-efficiently adjust the microstructure of olefin copolymer at a high polymerization temperature, and has no undesirable smell; the ternary copolymerized rubber has excellent wet-slipping resistance and low rolling resistance. The formula I is as shown in the description.
Description
Technical field
The present invention relates to a kind of structure regulator for alkene anionoid polymerization, adopt described structure regulator to prepare the method for terpolymer rubber, the terpolymer rubber of preparing according to described method, and the terpolymer rubber of preparation is thus in the application of preparing in tire.
Background technology
At present, the polymerization of conjugated diene and the monovinylarene sequences that add structure regulator to control multipolymer that adopt distribute and microtexture more.The structures shape of olefin copolymer they different purposes.Olefin copolymer microtexture mainly refers to suitable, the trans-Isosorbide-5-Nitrae-structure, 1 of multipolymer, 2-structure or 3,4-structure, and the sequence of multipolymer distributes.Affect a lot of because have of multipolymer microtexture, the kind of for example initiator, the impact of concentration, impact, the temperature etc. of solvent and structure regulator.In many factors, adding structure regulator, to synthesize the multipolymer with diverse microcosmic structure be most important method, and therefore structure regulator is research emphasis on the impact of Olefins Product Streams structure always.Along with people's researchdevelopment, novel structure regulator constantly occurs.
In US5448003, disclose a kind of method that adopts anionoid polymerization synthesis of ternary copolymer rubber, the method is to adopt alkyl tetrahydro furfuryl group ether as structure regulator, thereby obtains the multipolymer of high-vinyl-content.But this structure regulator has strong impulse smell, Shortcomings aspect environmental protection and operation environment safety.
In US5137998, disclose a kind of method that adopts anionoid polymerization synthesis of ternary copolymer rubber, the method adopts three piperidines phosphine oxides (TPPO) or alkali metal alcoholates (preferably potassium alcoholate) as structure regulator.But this structure regulator only just can obtain good structure regulating power under lower polymerization temperature (as-10 DEG C to 40 DEG C).
In US5300599, disclose a kind of method that adopts anionoid polymerization synthesis of ternary copolymer rubber, the method adopts the composite structure regulation system of tetrahydrofurfuryl alcohol salt and Tetramethyl Ethylene Diamine (TMEDA) or tetrahydrofurfuryl alcohol salt and alkoxyl group potassium as structure regulator.Although this composite structure regulation system can reduce side contents of ethylene, the structure regulating power that can show still need to cause under lower polymerization temperature.
Therefore the structure regulator that, exploitation has a good structure regulating power under higher conditions of polymerization temperature vary just becomes one of hot issue of current alkene anionoid polymerization area research.
Summary of the invention
One object of the present invention, in order to overcome the existing structure regulator for alkene anionoid polymerization poor defect of structure regulating power under higher conditions of polymerization temperature vary, provides a kind of new structure regulator for alkene anionoid polymerization.
Another object of the present invention is to provide the method that uses above-mentioned new structure regulator to prepare terpolymer rubber, and the terpolymer rubber of being prepared by the method and application thereof.
To achieve these goals, the invention provides a kind of structure regulator for alkene anionoid polymerization, wherein, this structure regulator contains double tetrahydrofuran compound and alkylbenzene sulfonate, described double tetrahydrofuran compound is the compound with structure shown in formula I
formula I,
Wherein, R
1and R
2be the alkyl of C1-C10 independently of one another.
The present invention also provides a kind of preparation method of terpolymer rubber, the method comprises: under inert atmosphere, under anionic polymerisation condition, the monomer mixture that contains monovinylarene, the first conjugated diene and the second conjugated diene is contacted with structure regulator with organic lithium initiator in solvent, wherein, described structure regulator is the above-mentioned structure regulator for alkene anionoid polymerization.
The present invention also provides the terpolymer rubber of preparing according to aforesaid method.
In addition, the present invention also provides above-mentioned terpolymer rubber in the application of preparing in tire.
At the described structure regulator for alkene anionoid polymerization of the present invention, by by composite to double tetrahydrofuran compound and alkylbenzene sulfonate, make this structure regulator under higher polymerization temperature, still can show good structure regulating power.Particularly, in the process of preparing terpolymer rubber, adopt the described structure regulator for alkene anionoid polymerization of the present invention, under higher polymerization temperature, can effectively the structural content of the structural content of olefin copolymer medium vinyl and propenyl be controlled to higher level, and the structural content of the micro-block of monovinylarene is controlled to a lower level, makes the terpolymer rubber of preparation there is good anti-slippery and low-rolling-resistance performance.
In addition, double tetrahydrofuran compound and alkylbenzene sulfonate in structure regulator provided by the invention all do not have undesirable smell, and therefore structure regulator provided by the invention has the good feature of environmental protection.
In the present invention, it should be noted that, the structure regulating power of structure regulator in alkene anionic polymerisation process refers to that the repeated structural unit number of controlling the structural content of olefin copolymer medium vinyl and the structural content of propenyl and exist with micro-block is greater than the ability of the structural content of 5 monovinylarene structural unit.Structure regulating power is better, and the structural content of olefin copolymer medium vinyl and the structural content of propenyl are higher, and the structural content that the repeated structural unit number existing with micro-block is greater than 5 monovinylarene structural unit is lower.
Wherein, the structural content of vinyl refers to the ratio of weight and the olefin copolymer gross weight of the vinyl that participates in polymerization in olefin copolymer.The nuclear magnetic resonance spectrometer that it is AVANCE DRX400MHz that the structural content of described vinyl for example can adopt purchased from the model of Bruker company of Switzerland is measured, and wherein, solvent is deuterochloroform.Equally, the structural content of propenyl refers to the ratio of weight and the olefin copolymer gross weight of the propenyl that participates in polymerization in olefin copolymer, and the instrument of mensuration can be identical with instrument and the method for said determination " structural content of vinyl " with method.
The structural content of the side group of olefin copolymer refers to the summation of the structural content of the vinyl in olefin copolymer and the structural content of propenyl.
In this article, 1, the structural content of 2-BD represents that divinyl is with 1, the content of the structural unit that the mode of 2-polymerization forms, 3, the structural content of 4-IP represents the content of the structural unit that isoprene forms in the mode of 3,4-polymerization, and the structural content of St block represents that the number of repeat unit existing with micro-block in multipolymer is greater than the content of 5 cinnamic structural unit.The structural content of side group represents structural unit and isoprene that divinyl forms with 1, the 2-polymerization methods total content with the structural unit of 3,4-polymerization methods formation.
Other features and advantages of the present invention are described in detail the embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of structure regulator for alkene anionoid polymerization, wherein, this structure regulator contains double tetrahydrofuran compound and alkylbenzene sulfonate, and described double tetrahydrofuran compound is the compound with structure shown in formula I,
formula I,
Wherein, R
1and R
2be the alkyl of C1-C10 independently of one another.
In the present invention, described alkyl can be straight chain, can be also side chain.The example of the alkyl of described C1-C10 can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 2-methyl butyl, 3-methyl butyl, 2,2-dimethyl propyl, n-hexyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, n-heptyl, 2-methyl hexyl, 3-methyl hexyl, 4-methyl hexyl, 5-methyl hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl and 3,7-dimethyl octyl group.
According to the present invention, described structure regulator contains double tetrahydrofuran compound and alkylbenzene sulfonate.Described double tetrahydrofuran compound is the compound with structure shown in formula I, wherein, and R
1and R
2be the alkyl of C1-C10 independently of one another.Under preferable case, R
1and R
2for the alkyl of C1-C5.The example of described double tetrahydrofuran compound includes but not limited to: two tetrahydrochysene chaff propane, two tetrahydrochysene chaff butane, two tetrahydrochysene chaff pentane, two tetrahydrochysene chaff hexane and two tetrahydrochysene chaff heptane.Under further preferable case, R
1and R
2for the alkyl of C1-C2, most preferably be methyl, described double tetrahydrofuran compound is two tetrahydrochysene chaff propane (DTHFP).
According to the present invention, the mol ratio of described double tetrahydrofuran compound and alkylbenzene sulfonate is not particularly limited, can in wider scope, change.But, described in making, can show better adjustment structure ability for the structure regulator of alkene anionoid polymerization in alkene anionic polymerisation process, the mol ratio of described double tetrahydrofuran compound and alkylbenzene sulfonate is preferably 1:0.0125-10, more preferably 1:0.033-1.25.
According to the present invention, adopt double tetrahydrofuran compound and alkylbenzene sulfonate compound as structure regulator, can effectively regulate the microtexture of olefin copolymer.Described alkylbenzene sulfonate is the compound with structure shown in formula II, wherein, and R
3for the alkyl of C4-C20.Under preferable case, R
3for the alkyl of C12-C16, most preferably be the alkyl of C12,
formula II,
Wherein, R
3for the alkyl of C4-C20, M is Na or K.
The example of the alkyl of described C4-C20 can include but not limited to: normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 2-methyl butyl, 3-methyl butyl, 2, 2-dimethyl propyl, n-hexyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, n-heptyl, 2-methyl hexyl, 3-methyl hexyl, 4-methyl hexyl, 5-methyl hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, 3, 7-dimethyl octyl group, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, Octadecane base, NSC 77136 base and NSC 62789 base.
In most preferred embodiments, described pair of tetrahydro-compound is two tetrahydrochysene chaff propane, and described alkylbenzene sulfonate is Sodium dodecylbenzene sulfonate.In this case, by the structure regulator that two tetrahydrochysene chaff propane and Sodium dodecylbenzene sulfonate are composited, in alkene anionic polymerisation process, can show excellent structure regulating power, the structural content of the structural content of olefin copolymer medium vinyl and propenyl can be controlled to higher level and the structural content of the micro-block of monovinylarene is controlled to lower level.
The present invention also provides a kind of preparation method of terpolymer rubber, the method comprises: under inert atmosphere, under anionic polymerisation condition, the monomer mixture that contains monovinylarene, the first conjugated diene and the second conjugated diene is contacted with structure regulator with organic lithium initiator in solvent, wherein, this structure regulator is the above-mentioned structure regulator for alkene anionoid polymerization.
In the present invention, " second " in " first " and the second conjugated diene in term the first conjugated diene do not have special implication, just in order to illustrate that the first conjugated diene and the second conjugated diene are different conjugated dienes.
According to the present invention, the double tetrahydrofuran compound in described structure regulator and the mol ratio of organic lithium initiator are not particularly limited, can in wider scope, change.Under preferable case, the double tetrahydrofuran compound in described structure regulator and the mol ratio of organic lithium initiator are 0.1-4:1, more preferably 0.4-3:1.
In addition, structure regulator of the present invention is that the composite structure conditioning agent of described double tetrahydrofuran compound and alkylbenzene sulfonate can join in reaction system in the mode of various routines, for example, described structure regulator can join in polymerization system together with organic lithium initiator or respectively.
According to the present invention, described inert atmosphere all refers to not any one gas or the gaseous mixture with reactant and product generation chemical reaction, as one or more in nitrogen and periodic table of elements zero group gas.Keep inert atmosphere method can for to pass in reaction system above-mentioned not with any one gas or the gaseous mixture of reactant and product generation chemical reaction.
The method according to this invention, is not particularly limited for total consumption of described solvent and described monomer mixture, can be the conventional amount used of this area.Preferably, with respect to the described solvent of 100 weight parts and total consumption of monomer mixture, the consumption of described monomer mixture is 8-20 weight part, and the consumption of described solvent is 80-92 weight part.More preferably, with respect to the described solvent of 100 weight parts and total consumption of described monomer mixture, the consumption of described monomer mixture is 10-16 weight part, and the consumption of described solvent is 84-90 weight part.
The method according to this invention, the ratio between described the first conjugated diene, the second conjugated diene and described monovinylarene can be carried out appropriate selection according to the application scenario of final multipolymer.Under preferable case, with respect to total consumption of the described monomer mixture of 100 weight parts, the consumption of described the first conjugated diene is 10-80 weight part, and the consumption of described the second conjugated diene is 10-80 weight part, and the consumption of described monovinylarene is 10-40 weight part.Further under preferable case, with respect to total consumption of the described monomer mixture of 100 weight parts, the consumption of described the first conjugated diene is 20-60 weight part, and the consumption of described the second conjugated diene is 20-50 weight part, and the consumption of described monovinylarene is 20-30 weight part.
Generally, in described monomer mixture, the content of described the first conjugated diene, described the second conjugated diene and monovinylarene can be more than 90 % by weight.
According to the present invention, various monovinylarenes and conjugated diene that described monovinylarene, the first conjugated diene and the second conjugated diene can be well known to those skilled in the art.For example, described monovinylarene can be the various aromatic monomers with a vinyl substituted base on the conventional aromatic ring in this area.As a rule, described monovinylarene can be the monovinylarene with the structure shown in formula III:
formula III,
Wherein, R
5can be replacement or the unsubstituted aryl of C6-C20, the phenyl that is preferably phenyl and is replaced by the alkyl of one or more C1-C5.
In the present invention, the replacement of described C6-C20 or the example of unsubstituted aryl can for but be not limited to: phenyl, tolyl, ethylbenzene, tert-butyl-phenyl, dodecylphenyl, di-n-butyl phenyl (comprise adjacent di-n-butyl phenyl, a di-n-butyl phenyl and to di-n-butyl phenyl), n-propyl phenyl and diethyl phenyl (comprise adjacent two positive ethylphenyls, a two positive ethylphenyl and to two positive ethylphenyls).
In the present invention, described monovinylarene can be for example vinylbenzene, Vinyl toluene, alpha-methyl styrene, 4-t-butyl styrene, 4-vinyl toluene, 3,5-diethylbenzene ethene, 3, one or more in 5-di-n-butyl vinylbenzene, 4-n-propylbenzene ethene and 4-dodecyl vinylbenzene.From obtaining complexity and industrialization reality, be preferably one or more in vinylbenzene, Vinyl toluene and alpha-methyl styrene, more preferably vinylbenzene.
According to the present invention, conjugated diene refers to the various unsaturated acyclic hydrocarbons that contain conjugated double bond (,-C=C-C=C-) in molecular structure.Described the first conjugated diene and described the second conjugated diene can be the conventional various conjugated dienes in this area, and can carry out choose reasonable according to the application scenario of the olefin copolymer finally obtaining, for example, described the first conjugated diene and described the second conjugated diene separately can be for being selected from divinyl, isoprene, 1,3-pentadiene, 1, one or more in 3-hexadiene and 2,3-dimethylbutadiene.Under preferable case, described the first conjugated diene and described the second conjugated diene are respectively divinyl and isoprene.
In addition, can select first to add monovinylarene to carry out polymerization, add again described the first conjugated diene and described the second conjugated diene to carry out polymerization, also can first add described the first conjugated diene and described the second conjugated diene to carry out polymerization, add again monovinylarene to carry out polymerization, can also be simultaneously by monovinylarene, described the first conjugated diene and described the second conjugated diene add and in reaction system, carry out polyreaction, all can know these those skilled in the art, and can reasonably select according to practical situation, to repeat no more at this.
According to the present invention, in the preparation process of olefin copolymer, described initiator can be the existing various organic lithium initiators that can cause described monovinylarene and conjugate diene polymerization, and for example, described organic lithium initiator can be that molecular formula is R conventionally
4the compound of Li, wherein, R
4for the alkyl of the straight or branched of C1-C6, cycloalkyl, the aralkyl of C7-C14 or the aryl of C6-C12 of C3-C12.Particularly, described organic lithium initiator can be selected from one or more in lithium ethide, propyl lithium, isopropyl lithium, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, phenyl lithium, 2-naphthyl lithium, 4-butyl phenyl lithium, 4-tolyl lithium, cyclohexyl lithium and 4-butyl cyclohexyl lithium, be preferably n-Butyl Lithium and/or s-butyl lithium, more preferably n-Butyl Lithium.
The present invention is not particularly limited the consumption of described organic lithium initiator, and can reasonably select according to the microtexture of the size of the molecular weight of target product and target product.Those skilled in the art should hold intelligible, in the time need to preparing the larger olefin copolymer of molecular weight, can reduce the consumption of organic lithium initiator, but now rate of polymerization also can correspondingly reduce; In the time need to preparing the olefin copolymer of molecular weight, can increase the consumption of organic lithium initiator, but now rate of polymerization also can correspondingly increase.Therefore, consider rate of polymerization and the molecular size range of the olefin copolymer that obtains, under preferable case, the weight of monomer mixture described in 100g relatively, the consumption of described initiator can be 0.01-10mmol, is preferably 0.25-2.5mmol.
According to the present invention, described solvent can be the various organic substances that can serve as reaction media, for example, can be varsol, described varsol can be selected from hexanaphthene, normal hexane, Skellysolve A, normal heptane, benzene and raffinate oil in one or more.In the present invention, described in to raffinate oil be in petroleum refining process, be rich in catalytic reformate remaining distillate after extraction aromatic hydrocarbons of aromatic hydrocarbons.In addition, these solvents can be used alone, but also also mix together.Under preferable case, described solvent can be the mixture of hexanaphthene and normal hexane, and wherein, the weight ratio of hexanaphthene and normal hexane can be 80:20 to 90:10.
The present invention is not particularly limited described anionic polymerisation condition, can be that the routine of this area is selected.As a rule, described anionic polymerisation condition comprises temperature of reaction, reaction pressure and reaction times.Wherein, described temperature of reaction and reaction pressure all can be selected and change in wider scope, and in order to be more conducive to the carrying out of polyreaction, described temperature of reaction is preferably 40-100 DEG C, more preferably 40-90 DEG C; Described reaction pressure is preferably 0.005-1.1MPa, more preferably 0.1-0.3MPa.As a rule, the prolongation in described reaction times is conducive to the raising of the transformation efficiency of reactant and the yield of reaction product, but the amplitude that long transformation efficiency to reactant of reaction times and reaction product yield improve not obvious.Therefore, consider polymerization efficiency and effect, the described reaction times is preferably 10-120min, more preferably 30-90min.In addition, as mentioned above, the method that makes monovinylarene and conjugated diene carry out polyreaction in solvent is preferably under anionic polymerisation condition, under the existence of organic lithium initiator and structure regulator, first add monovinylarene in solvent, to carry out polymerization, then add conjugated diene to carry out polymerization.The condition of these two sections of polyreactions can be that those skilled in the art are known, will repeat no more at this.
In the present invention, described pressure all refers to gauge pressure.
As a rule, anionic polymerisation system does not have obvious termination reaction and shift reaction, and when ruing out of after whole monomers, active centre still exists.Therefore, preparation method of the present invention contacts the reaction product obtaining after can also being included in polyreaction with terminator, so that polyreaction termination, even active centre inactivation.Described terminator can be the various terminators that can stop active copolymer chain in anionoid polymerization field.Can be for example one or more in water, methyl alcohol, ethanol, n-propyl alcohol and Virahol.Under preferable case, described terminator can be Virahol.
The present invention is not particularly limited the consumption of terminator, as long as can make active centre inactivation.Under preferable case, it is 0.1-2:1, more preferably 0.2-1.5:1 that the consumption of described terminator makes the mol ratio of described terminator and organic lithium initiator.
According to the present invention, under preferable case, after polyreaction completes, before terminator adds, can also add coupling agent, so that the active copolymer chain generating in polymerization process carries out coupling.It is coupled that the consumption of coupling agent makes to ensure the active copolymer chain of 20%-100%.The kind of described coupling agent is known to the skilled person, can be for example one or more in Vinylstyrene, four vinyl silanes, tetrachloromethane, silicon tetrachloride, tin tetrachloride and dimethyl terephthalate (DMT), be preferably one or more in Vinylstyrene, silicon tetrachloride and tin tetrachloride.
The present invention is not particularly limited the consumption of described coupling agent, as long as realize the coupled object of active copolymer segment.Under preferable case, it is 0.1-2:1, more preferably 0.15-1.8:1 that the consumption of described coupling agent makes the mol ratio of described coupling agent and organic lithium initiator.
According to the present invention, under preferable case, after polyreaction completes, can also in the terpolymer rubber obtaining, add various additives, to give described terpolymer rubber various performances.Described additive can be for example anti-aging agent, so that the terpolymer rubber obtaining has good ageing resistance.
The present invention is not particularly limited for the kind of described anti-aging agent, can be the various anti-aging agent of this area routine.For example, described anti-aging agent can be phenols and/or amines antioxidants.Particularly, described anti-aging agent can be the anti-aging agent that to be purchased from the trade mark of Switzerland's vapour Bagong department be Irganox1520, four [3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (trade mark is 1010), tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester (trade mark is 168), 3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl (trade mark is 1076), 2, 6-ditertbutylparacresol (trade mark is 264), tert-butyl catechol and 2, one or more in 2 '-methylene radical-bis-(4-methyl-6-tert-butylphenol) (trade mark is 2246).By four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester mix use time, the content of tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester is not preferably higher than 50 % by weight; By 3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl and tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester is while being used in combination, and the content of tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester is not preferably higher than 50 % by weight.
According to the present invention, the consumption of described anti-aging agent can be also the conventional amount used of this area.For example, with respect to total consumption of the described monomer mixture of 100 weight parts, the consumption of described anti-aging agent can be 0.005-2 weight part, is preferably 0.1-1 weight part.
According to the present invention, adding after anti-aging agent, described terpolymer rubber can be precipitated out by methods such as purifying precipitation, centrifugation, filtration, decant, hot water cohesions from solution, also can adopt air lift method by the removal of solvents in reaction system, all can know these those skilled in the art, will repeat no more at this.In addition, polymerization process of the present invention can be implemented by batchwise polymerization mode, also can implement by successive polymerization mode.
One of the present invention preferred embodiment in, described the first conjugated diene is divinyl, described the second conjugated diene is isoprene, described monovinylarene is vinylbenzene, described organic lithium initiator is n-Butyl Lithium, described coupling agent is tin tetrachloride, and described double tetrahydrofuran compound is two tetrahydrochysene chaff propane (DTHFP), and described alkylbenzene sulfonate is that Sodium dodecylbenzene sulfonate (SDBS) adopts DTHFP/SDBS binary composite structure conditioning agent.Preferred embodiment can be realized under higher polymerization temperature by this, can effectively the structural content of the vinyl structure content in olefin copolymer and propenyl be controlled to higher level, and the structural content of the micro-block of styryl is controlled to a lower level, makes the terpolymer rubber of preparation there is good anti-slippery and low-rolling-resistance performance.
According to the present invention, the adjusting of the microtexture of terpolymer rubber so that the microtexture of terpolymer rubber there is following characteristics: taking the gross weight of terpolymer rubber as benchmark, the structural content of 3,4-IP can be 10-38 % by weight, is preferably 12-33 % by weight; The structural content of 1,2-BD can be 10-35 % by weight, is preferably 14-27 % by weight; The structural content of side group can be 20-73 % by weight, is preferably 27-60 % by weight; The content that the number of repeat unit existing with micro-block is greater than 5 cinnamic structural unit (St block) can be less than 1 % by weight.
In addition, the present invention also provides the terpolymer rubber of being prepared by aforesaid method.In described terpolymer rubber, taking the gross weight of terpolymer rubber as benchmark, the structural content of 3,4-IP can be 10-38 % by weight, is preferably 12-33 % by weight; The structural content of 1,2-BD can be 10-35 % by weight, is preferably 14-27 % by weight; The structural content of side group can be 20-73 % by weight, is preferably 27-60 % by weight; The content that the number of repeat unit existing with micro-block is greater than 5 cinnamic structural unit (St block) can be less than 1 % by weight.
Terpolymer rubber provided by the invention has good low-rolling-resistance performance and excellent wet-sliding resistant performance, thereby is particularly suitable for preparing high performance tire, particularly tire tread.
The present invention also provides above-mentioned terpolymer rubber in the application of preparing in tire.
Below will describe the present invention by embodiment.
In following examples and comparative example, the number-average molecular weight of the terpolymer rubber that contains monovinylarene structural unit and conjugated diene structural unit and molecular weight distribution adopt the gel permeation chromatograph (GPC) that the model of WATERS company of the U.S. is ALLIANCE2690 to measure, wherein, THF is moving phase, Narrow distribution polystyrene is standard specimen, and temperature is 25 DEG C.
The microtexture of terpolymer rubber adopt the Switzerland AVANCE DRX 400MHz of Bruker company nuclear magnetic resonance spectrometer (
1h-NMR) measure, non-polar hydrocarbon kind solvent is deuterochloroform; Wherein, 1,2-BD% represents the content of the structural unit that divinyl forms in the mode of 1,2-polymerization, 3,4-IP% represents that isoprene is with 3, the content of the structural unit that the mode of 4-polymerization forms, side group % represent divinyl with 1,2-polymerization methods form structural unit and isoprene with 3, the total content of structural unit that 4-polymerization methods forms, St block% represents that repeating unit of copolymer number is greater than the content of 5 the cinnamic structural unit existing with micro-block.
Dissipation factor adopts the U.S. DMA-2980 of TA company type viscoelastic spectrometer to measure, frequency 2Hz, and 5 DEG C/min of temperature rise rate, Range of measuring temp is-120 DEG C to 100 DEG C, sample size 40mm × 5mm × 1mm.
Vulcanizating glue physical performance adopts Japanese SHIMADZU AG-20KNG type puller system, measures according to GB/T528-1998;
Vulcanize and prepare according to the A series formula of GB/T8656-1998 for the sample of measuring dissipation factor and mechanical property, cure conditions comprises: rubber adopts mill mixing, roller temperature be at 50 ± 5 DEG C, carry out mixing; The temperature of sulfuration is 145 DEG C, and pressure is more than 10MPa, and curing time is 35 minutes.
Unless stated otherwise, compound and the reagent in following examples and comparative example, used are commercially available product.
Embodiment 1
This embodiment is for illustrating the preparation method of terpolymer rubber provided by the invention.
In 5 liters of stainless steel stirred autoclaves, under high pure nitrogen protection, add 2288g mixed solvent (mixed solution of hexanaphthene and normal hexane: 82/18, mass ratio), 62.4g vinylbenzene, 62.4g isoprene and 187.2g divinyl.Use the binary composite structure conditioning agent of DTHFP/SDBS, wherein the consumption of two tetrahydrochysene chaff propane (DTHFP) is 0.756mmol, the consumption of Sodium dodecylbenzene sulfonate (SDBS) is 0.945mmol(DTHFP/Li=0.4, SDBS/Li=0.5, DTHFP/SDBS=0.8), taking n-Butyl Lithium as initiator, first kill assorted by n-butyl lithium initiator, add again the n-Butyl Lithium of 1.89mmol, it is 90 DEG C at polymeric reaction temperature, polymerization pressure is controlled under the condition of 0.1MPa and reacts 40 minutes, again to the tin tetrachloride that adds 0.42mmol in still, after 70 minutes, add the Virahol termination reaction of 2.27mmol, add afterwards 2 of 2.5g, 6-ditertbutylparacresol is (purchased from Switzerland's vapour Bagong department, the trade mark 264), glue obtains star-like terpolymer rubber after water vapor cohesion, the molecular weight of product, microtexture, physical and mechanical properties and dynamic properties data are in table 1.
Embodiment 2
This embodiment is for illustrating the preparation method of terpolymer rubber provided by the invention.
In 5 liters of stainless steel stirred autoclaves, under high pure nitrogen protection, add 2288g mixed solvent (mixed solution of hexanaphthene and normal hexane: 82/18, mass ratio), 68.7g vinylbenzene, 124.8g isoprene and 118.6g divinyl.Use the binary composite structure conditioning agent of DTHFP/SDBS, wherein the consumption of two tetrahydrochysene chaff propane (DTHFP) is 1.66mmol, the consumption of Sodium dodecylbenzene sulfonate (SDBS) is 0.5mmol(DTHFP/Li=1.0, SDBS/Li=0.3, DTHFP/SDBS=3.33), taking n-Butyl Lithium as initiator, first kill assorted by n-butyl lithium initiator, add again the n-Butyl Lithium of 1.66mmol, it is 85 DEG C at polymeric reaction temperature, polymerization pressure is controlled under the condition of 0.3MPa and reacts 40 minutes, again to the tin tetrachloride that adds 0.37mmol in still, after 70 minutes, add the Virahol termination reaction of 1.99mmol, add afterwards 2 of 2.5g, 6-ditertbutylparacresol is (purchased from Switzerland's vapour Bagong department, the trade mark 264), glue obtains star-like terpolymer rubber product after water vapor cohesion, the molecular weight of product, microtexture, physical and mechanical properties and dynamic properties data are in table 1.
Comparative example 1
This comparative example is used for illustrating contrast terpolymer rubber and preparation method thereof.
Prepare reference terpolymer rubber according to the method for comparative example 2, difference is, in structure regulator, containing SDBS, adopts DTHFP to replace the binary composite structure conditioning agent of DTHFP/SDBS as structure regulator, and the consumption of DTHFP is 1.66mmol.Molecular weight, microtexture, physical and mechanical properties and the dynamic properties data of product are in table 1.
Comparative example 2
This comparative example is used for illustrating contrast terpolymer rubber and preparation method thereof.
Prepare reference terpolymer rubber according to the method for comparative example 2, difference is, adopt the binary composite structure conditioning agent of tetrahydrofurfuryl alcohol butyl ether/SDBS to replace the binary composite structure conditioning agent of DTHFP/SDBS, wherein the consumption of tetrahydrofurfuryl alcohol butyl ether is 1.66mmol, the consumption of Sodium dodecylbenzene sulfonate (SDBS) is 0.5mmol(tetrahydrofurfuryl alcohol butyl ether/Li=1.0, SDBS/Li=0.3, DTHFP/SDBS=3.33).Molecular weight, microtexture, physical and mechanical properties and the dynamic properties data of product are in table 1.
Embodiment 3
This embodiment is for illustrating the preparation method of terpolymer rubber provided by the invention.
In 5 liters of stainless steel stirred autoclaves, under high pure nitrogen protection, add 2288g mixed solvent (mixed solution of hexanaphthene and normal hexane: 82/18, mass ratio), 93.6g vinylbenzene, 156g isoprene and 62.4g divinyl.Use the binary composite structure conditioning agent of DTHFP/SDBS, wherein the consumption of two tetrahydrochysene chaff propane (DTHFP) is 5.22mmol, the consumption of Sodium dodecylbenzene sulfonate (SDBS) is 0.174mmol(DTHFP/Li=3, SDBS/Li=0.1, DTHFP/SDBS=30), taking n-Butyl Lithium as initiator, first kill assorted by n-butyl lithium initiator, add again the n-Butyl Lithium of 1.74mmol, it is 40 DEG C at polymeric reaction temperature, polymerization pressure is controlled under the condition of 0.2MPa and reacts 40 minutes, again to the tin tetrachloride that adds 0.38mmol in still, after 70 minutes, add the Virahol termination reaction of 2.09mmol, add afterwards 2 of 2.5g, 6-ditertbutylparacresol is (purchased from Switzerland's vapour Bagong department, the trade mark 264), glue obtains star-like terpolymer rubber product after water vapor cohesion, the molecular weight of product, microtexture, physical and mechanical properties and dynamic properties data are in table 1.
Embodiment 4
This embodiment is for illustrating the preparation method of terpolymer rubber provided by the invention.
In 5 liters of stainless steel stirred autoclaves, under high pure nitrogen protection, add 2288g mixed solvent (mixed solution of hexanaphthene and normal hexane: 82/18, mass ratio), 62.4g vinylbenzene, 124.8g isoprene and 124.8g divinyl.Use the binary composite structure conditioning agent of two tetrahydrochysene chaff propane/Sodium dodecylbenzene sulfonatees (DTHFP/SDBS), wherein the consumption of two tetrahydrochysene chaff propane (DTHFP) is 0.173mmol, the consumption of Sodium dodecylbenzene sulfonate (SDBS) is 1.73mmol(DTHFP/Li=0.1, SDBS/Li=1, DTHFP/SDBS=0.1), taking n-Butyl Lithium as initiator, first kill assorted by n-butyl lithium initiator, add again the n-Butyl Lithium of 1.73mmol, it is 70 DEG C at polymeric reaction temperature, polymerization pressure is controlled under the condition of 0.1MPa and reacts 40 minutes, again to the tin tetrachloride that adds 0.38mmol in still, after 70 minutes, add the Virahol termination reaction of 2.076mmol, add afterwards 2 of 2.5g, 6-ditertbutylparacresol is (purchased from Switzerland's vapour Bagong department, the trade mark 264), glue obtains star-like terpolymer rubber product after water vapor cohesion, the molecular weight of product, microtexture, physical and mechanical properties and dynamic properties are in table 1.
Embodiment 5
This embodiment is for illustrating the preparation method of terpolymer rubber provided by the invention.
In 5 liters of stainless steel stirred autoclaves, under high pure nitrogen protection, add 2288g mixed solvent (mixed solution of hexanaphthene and normal hexane: 82/18, mass ratio), 62.4g vinylbenzene, 124.8g isoprene and 124.8g divinyl.Use the compound regulation system of binary of DTHFP/SDBS, wherein the consumption of two tetrahydrochysene chaff propane (DTHFP) is 0.28mmol, the consumption of Sodium dodecylbenzene sulfonate (SDBS) is 0.14mmol(DTHFP/Li=0.2, SDBS/Li=0.4, DTHFP/SDBS=0.5), taking n-Butyl Lithium as initiator, first kill assorted by n-butyl lithium initiator, add again the n-Butyl Lithium of 1.39mmol, it is 100 DEG C at polymeric reaction temperature, polymerization pressure is controlled under the condition of 0.1MPa and reacts 40 minutes, again to the tin tetrachloride that adds 0.31mmol in still, after 70 minutes, add the Virahol termination reaction of 1.67mmol, add afterwards 2 of 2.5g, 6-ditertbutylparacresol is (purchased from Switzerland's vapour Bagong department, the trade mark 264), glue obtains star-like terpolymer rubber product after water vapor cohesion, the molecular weight of product, microtexture, physical and mechanical properties and dynamic properties are in table 1.
Embodiment 6
This embodiment is for illustrating the preparation method of terpolymer rubber provided by the invention.
In 5 liters of stainless steel stirred autoclaves, under high pure nitrogen protection, add 2288g mixed solvent (mixed solution of hexanaphthene and normal hexane: 82/18, mass ratio), 62.4g vinylbenzene, 124.8g isoprene and 124.8g divinyl.Use the compound regulation system of binary of DTHFP/SDBS, wherein the consumption of two tetrahydrochysene chaff propane (DTHFP) is 8.68mmol, the consumption of Sodium dodecylbenzene sulfonate (SDBS) is 0.11mmol(DTHFP/Li=4, SDBS/Li=0.05, DTHFP/SDBS=80), taking n-Butyl Lithium as initiator, first kill assorted by n-butyl lithium initiator, add again the n-Butyl Lithium of 2.17mmol, it is 40 DEG C at polymeric reaction temperature, polymerization pressure is controlled under the condition of 0.1MPa and reacts 40 minutes, again to the tin tetrachloride that adds 0.38mmol in still, after 70 minutes, add the Virahol termination reaction of 2.08mmol, add afterwards 2 of 2.5g, 6-ditertbutylparacresol is (purchased from Switzerland's vapour Bagong department, the trade mark 264), glue obtains star-like terpolymer rubber product after water vapor cohesion, the molecular weight of product, microtexture, physical and mechanical properties and dynamic properties the results are shown in Table 1.
Table 1
Can find out from the data of embodiment 2 and comparative example 1, in the situation that other conditions are all identical, in the time not adding SDBS, the content that in synthetic terpolymer rubber, number of repeat unit is greater than 5 the cinnamic structural unit existing with micro-block exceedes 1 % by weight, and adding after SDBS, the content that in terpolymer rubber, number of repeat unit is greater than 5 the cinnamic structural unit existing with micro-block has obtained effective control (being less than 1 % by weight); Can find out from the data of embodiment 2 and comparative example 2: composite structure conditioning agent of the present invention can effectively be controlled at higher level by the content of the content of olefin copolymer medium vinyl, propenyl under higher conditions of polymerization temperature vary, and micro-monovinylarene block content is controlled to a lower level; In addition, can find out from Mechanical Data, the terpolymer rubber that adopts composite structure conditioning agent of the present invention to make has good mechanical property; Can find out from the test data (Tan (0 DEG C) and Tan (60 DEG C)) of dynamic mechanical, the terpolymer rubber that adopts composite structure conditioning agent of the present invention to make has good anti-slippery and low-rolling-resistance performance.
Claims (13)
1. for a structure regulator for alkene anionoid polymerization, it is characterized in that, this structure regulator contains double tetrahydrofuran compound and alkylbenzene sulfonate, and described double tetrahydrofuran compound is the compound with structure shown in formula I,
formula I,
Wherein, R
1and R
2be the alkyl of C1-C10 independently of one another.
2. structure regulator according to claim 1, wherein, the mol ratio of described double tetrahydrofuran compound and alkylbenzene sulfonate is 1:0.0125-10, is preferably 1:0.033-1.25.
3. structure regulator according to claim 1 and 2, wherein, described alkylbenzene sulfonate is the compound with structure shown in formula II,
formula II,
Wherein, R
3for the alkyl of C4-C20, M is Na or K.
4. structure regulator according to claim 1 and 2, wherein, described double tetrahydrofuran compound is two tetrahydrochysene chaff propane, described alkylbenzene sulfonate is Sodium dodecylbenzene sulfonate.
5. the preparation method of a terpolymer rubber, the method comprises: under inert atmosphere, under anionic polymerisation condition, the monomer mixture that contains monovinylarene, the first conjugated diene and the second conjugated diene is contacted with structure regulator with organic lithium initiator in solvent, it is characterized in that, described structure regulator is the structure regulator for alkene anionoid polymerization described in any one in claim 1-4.
6. preparation method according to claim 5, wherein, the double tetrahydrofuran compound in described structure regulator and the mol ratio of organic lithium initiator are 0.1-4:1, are preferably 0.4-3:1.
7. preparation method according to claim 5, wherein, with respect to the described solvent of 100 weight parts and total consumption of described monomer mixture, the consumption of described monomer mixture is 8-20 weight part, the consumption of described solvent is 80-92 weight part.
8. preparation method according to claim 5, wherein, with respect to total consumption of the described monomer mixture of 100 weight parts, the consumption of described the first conjugated diene is 10-80 weight part, the consumption of described the second conjugated diene is 10-80 weight part, and the consumption of described monovinylarene is 10-40 weight part.
9. according to the preparation method described in any one in claim 5,7 and 8, wherein, described the first conjugated diene and described the second conjugated diene are respectively done for oneself and are selected from divinyl, isoprene, 1,3-pentadiene, 1,3-hexadiene and 2, one or more in 3-dimethylbutadiene, are preferably respectively divinyl and isoprene; Described monovinylarene is for being selected from vinylbenzene, Vinyl toluene, alpha-methyl styrene, 4-t-butyl styrene, 4-vinyl toluene, 3,5-diethylbenzene ethene, 3, one or more in 5-di-n-butyl vinylbenzene, 4-n-propylbenzene ethene and 4-dodecyl vinylbenzene, are preferably vinylbenzene.
10. according to the preparation method described in claim 5 or 6, wherein, described solvent is varsol, be preferably hexanaphthene, normal hexane, Skellysolve A, normal heptane, benzene and raffinate oil in one or more; Described organic lithium initiator is that molecular formula is R
4the compound of Li, wherein, R
4for the alkyl of the straight or branched of C1-C6, cycloalkyl, the aralkyl of C7-C14 or the aryl of C6-C12 of C3-C12, preferably, described organic lithium initiator is one or more in lithium ethide, propyl lithium, isopropyl lithium, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, phenyl lithium, 2-naphthyl lithium, 4-butyl phenyl lithium, 4-tolyl lithium, cyclohexyl lithium and 4-butyl cyclohexyl lithium.
11. preparation methods according to claim 5, wherein, the condition of described anionic polymerisation comprises: temperature of reaction is 40-100 DEG C, is preferably 40-90 DEG C; Reaction pressure is 0.005-1.1MPa, is preferably 0.1-0.3MPa; Reaction times is 10-120min, is preferably 30-90min.
12. terpolymer rubbers of preparing according to the method described in any one in claim 5-11.
Terpolymer rubber described in 13. claims 12 is in the application of preparing in tire.
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| EP3532515A4 (en) * | 2016-10-31 | 2020-06-03 | Bridgestone Corporation | Methods for producing polydienes |
| CN113956383A (en) * | 2020-07-20 | 2022-01-21 | 中国石油天然气股份有限公司 | Binary composite regulating system for conjugated diene anion homopolymerization or copolymerization |
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| CN101962423A (en) * | 2009-07-22 | 2011-02-02 | 中国石油化工股份有限公司 | Method for preparing ternarypolymerization rubber and application thereof |
| CN102372823A (en) * | 2010-08-26 | 2012-03-14 | 中国石油化工股份有限公司 | Terpolymer rubber with medium/high side group content and preparation method and applications thereof |
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| EP3532515A4 (en) * | 2016-10-31 | 2020-06-03 | Bridgestone Corporation | Methods for producing polydienes |
| US11084892B2 (en) | 2016-10-31 | 2021-08-10 | Bridgestone Corporation | Methods for producing polydienes |
| CN108017866A (en) * | 2016-11-01 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of polymer composition |
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