CN103665218B - A kind of polyisoprene and preparation method thereof and rubber combination - Google Patents
A kind of polyisoprene and preparation method thereof and rubber combination Download PDFInfo
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- CN103665218B CN103665218B CN201210336365.2A CN201210336365A CN103665218B CN 103665218 B CN103665218 B CN 103665218B CN 201210336365 A CN201210336365 A CN 201210336365A CN 103665218 B CN103665218 B CN 103665218B
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Abstract
The invention provides a kind of polyisoprene and preparation method, in this polyisoprene, the content of cis Isosorbide-5-Nitrae-structures alone unit is more than 98%, and the content of trans Isosorbide-5-Nitrae-structures alone unit is that the monomeric unit of less than 2%, at least 99.8% is with head-tail mode keyed jointing.Under method of the present invention is included in rare earth catalyst existence, isoprene is polymerized, described rare earth catalyst is that the oil solution containing at least one carboxylic acid neodymium, halogen source and at least one conjugated diene are carried out the first contact in inert organic solvents, and the mixture obtained and at least one alkylating reagent are carried out second and contact and make, with the gross weight of oil solution for benchmark, its water-content is below 300wppm.Present invention also offers a kind of rubber combination containing above-mentioned polyisoprene.Polyisoprene of the present invention has the stretch crystallization performance similar to natural rubber and physical and mechanical properties.The corrodibility of method of the present invention to equipment is little.
Description
Technical field
The present invention relates to a kind of polyisoprene and preparation method thereof, the invention still further relates to a kind of rubber combination.
Background technology
Conjugated diene (as divinyl and isoprene), by coordination polymerization process synthesis tactic polymer, produces important synthetic rubber kind (as cis 1，4-polybutadiene and cis Isosorbide-5-Nitrae-polyisoprene).Cis 1,4-polyisoprene (namely, polyisoprene rubber), also known as " natural synthetic rubber ", there is the stretch crystallization performance similar to natural rubber, and excellent physical properties is the kind that uniquely can substitute natural rubber in synthetic rubber, be widely used in the industries such as tire, medical, glue tube belt.
Although polyisoprene rubber in main physical and mechanical properties close to natural rubber, but in microtexture, molecular parameter and polar group etc., there is different with natural rubber, thus cause both in physical and mechanical properties and chemical conduct, show certain difference.Wherein, outstanding is that the green strength of polyisoprene rubber is lower than natural rubber.From microtexture, in natural rubber, the content of cis Isosorbide-5-Nitrae-structure is 98%, not containing trans 1,4-structure, and the monomeric unit 100% of cis Isosorbide-5-Nitrae-structure is that head-(Zhao Xutao, Liu great Hua edit, " China Synthetic Rubber Industry handbook " in tail arrangement, the second edition, Chemical Industry Press, the 515th page).In polyisoprene rubber, not only have trans 1,4-structures alone unit, but also exist with the monomeric unit of head-head and tail-tail mode keyed jointing, this have impact on arrangement compactness and the regularity of polymer segment, cause the stretch crystallization speed of polyisoprene rubber lower than natural rubber, and then make its physical and mechanical properties not as good as natural rubber.
Therefore, to reduce in polyisoprene rubber trans Isosorbide-5-Nitrae-structures alone unit content and be the key improving polyisoprene rubber physical and mechanical properties with the content of the monomeric unit of head-head and tail-tail mode keyed jointing.
US2005/0137338A1 discloses a kind of rare earth catalyst containing carboxylic acid neodymium, aluminum alkyls and halogen, in the polyisoprene using this catalyzer to synthesize, cis 1, the content of 4-structures alone unit is between 98.0-99.5%, trans 1, the content of 4-structures alone unit can be within the scope of 0-0.5%, with the content of the monomeric unit of head-head and tail-tail mode keyed jointing for less than 1%.But, from embodiment disclosed in US2005/0137338A1 specification sheets, in the polyisoprene rubber of preparation, with the content of the monomeric unit of head-head and tail-tail mode keyed jointing for 0.4%, still higher, and find in practice: adopting method disclosed in US2005/0137338A1 cannot obtain with the content of the monomeric unit of head-head and tail-tail mode keyed jointing is polyisoprene lower than 0.4%.In addition, in the preparation process of the catalyzer that method disclosed in US2005/0137338A1 uses, use halogen (as chlorine) as halogen source, large to equipment corrosion, and easily cause environmental pollution.
To sum up, preparation not only has high cis Isosorbide-5-Nitrae-structural content and low trans Isosorbide-5-Nitrae-structural content, and the polyisoprene of monomer unit content with higher head-tail keyed jointing remains a technical problem urgently to be resolved hurrily.
Summary of the invention
The object of the present invention is to provide a kind of polyisoprene and preparation method thereof, this polyisoprene not only has high cis 1,4-structures alone unit content and low trans Isosorbide-5-Nitrae-structures alone unit content, and there is the monomer unit content of high head-tail keyed jointing; When this polyisoprene is used as rubber, there is the stretch crystallization performance similar to natural rubber and physical and mechanical properties.
The invention provides a kind of polyisoprene, in this polyisoprene, the content of cis Isosorbide-5-Nitrae-structures alone unit is more than 98%, and the content of trans Isosorbide-5-Nitrae-structures alone unit is that the monomeric unit of less than 2%, at least 99.8% is with head-tail mode keyed jointing.
Present invention also offers a kind of method preparing polyisoprene, under the method is included in rare earth catalyst existence, isoprene is polymerized, described rare earth catalyst is that the oil solution containing at least one carboxylic acid neodymium, at least one halogen source and at least one conjugated diene are carried out the first contact at least one inert organic solvents, and the mixture obtained and at least one alkylating reagent are carried out second and contact and make, wherein, with the gross weight of described oil solution for benchmark, the water-content of described oil solution is below 300wppm.
Invention further provides a kind of polyisoprene prepared by method of the present invention.
Invention further provides a kind of rubber combination, this rubber combination is containing with good grounds polyisoprene of the present invention and at least one vulcanizing agent.
Polyisoprene according to the present invention has high cis 1,4-structures alone unit content, low trans 1,4-structures alone unit content and high with the content of the monomeric unit of head-tail mode keyed jointing, polyisoprene according to the present invention is when being used as natural synthetic rubber, there is the same or analogous stretch crystallization performance with natural rubber, and then there is the physical and mechanical properties that can compare favourably with natural rubber.
Further, the corrodibility of method according to the present invention to equipment is little, environmental friendliness.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
The one that Fig. 1 is the coalescing separator for providing the catalyzer used in method of the present invention preferred embodiment; And
Fig. 2 is for illustration of the single segmental baffle used in coalescing separator of the present invention.
Embodiment
The invention provides a kind of polyisoprene.
According to polyisoprene of the present invention, the content of cis Isosorbide-5-Nitrae-structures alone unit is more than 98%, can be generally that 98-99.6%(such as can for 98-99%).
According to polyisoprene of the present invention, the content of trans Isosorbide-5-Nitrae-structures alone unit is less than 2%, is preferably less than 1%, is more preferably less than 0.5%, more preferably less than 0.2%, most preferably be 0.
According to polyisoprene of the present invention, the monomeric unit of at least 99.8% is with head-tail mode keyed jointing, and preferably the monomeric unit of 100% is with head-tail mode keyed jointing (that is, according in polyisoprene of the present invention, monomeric unit is with head-tail mode keyed jointing).
In the present invention, cis Isosorbide-5-Nitrae-structures alone unit refer to isoprene with Isosorbide-5-Nitrae-polymerization methods formed and be configured as the monomeric unit of cis, the monomeric unit namely shown in formula I:
In the present invention, trans Isosorbide-5-Nitrae-structures alone unit refer to isoprene with Isosorbide-5-Nitrae-polymerization methods formed and be configured as trans monomeric unit, the monomeric unit namely shown in formula II:
One of the present invention preferred embodiment in, in described polyisoprene, the content of cis Isosorbide-5-Nitrae-structures alone unit is more than 98%, and the content of trans Isosorbide-5-Nitrae-structures alone unit is that the monomeric unit of less than 0.2%, 100% is with head-tail mode keyed jointing.
Molecular weight and molecualr weight distribution according to polyisoprene of the present invention can carry out appropriate selection according to its embody rule occasion.When polyisoprene according to the present invention is used as natural synthetic rubber, the weight-average molecular weight of described polyisoprene can be 600,000-3,000,000, be preferably 800,000-2,600,000; Molecular weight distributing index (that is, M
w/ M
n) can be 2.5-5, be preferably 3-4.Described weight-average molecular weight and molecular weight distributing index are by gel permeation chromatography (that is, GPC), measure using monodisperse polystyrene as standard substance.
Present invention also offers a kind of method preparing polyisoprene, under the method is included in rare earth catalyst existence, isoprene is polymerized, described rare earth catalyst is that the oil solution containing at least one carboxylic acid neodymium, at least one halogen source and at least one conjugated diene are carried out the first contact at least one inert organic solvents, and the mixture obtained and at least one alkylating reagent is carried out second and contact and make.
According to method of the present invention, with the gross weight of the described oil solution containing at least one carboxylic acid neodymium for benchmark, the water-content of the described oil solution containing at least one carboxylic acid neodymium is below 300wppm.With the angle of the content of the monomeric unit of head-tail mode keyed jointing from the polyisoprene of the transformation efficiency and preparation that improve monomer further, the water-content of the described oil solution containing at least one carboxylic acid neodymium is preferably lower than 300wppm, is more preferably 20-298wppm.From the angle reducing the energy consumption needed for Kaolinite Preparation of Catalyst further, the water-content of the described oil solution containing at least one carboxylic acid neodymium is more preferably 50-298wppm, is further preferably 200-298wppm.Water-content in carboxylic acid neodymium oil solution is recorded by Karl-Fischer method.In the present invention, wppm refers to PPM by weight.
According to method of the present invention, the mol ratio of the carboxylic acid neodymium in described oil solution, described alkylating reagent, described halogen source and described conjugated diene can be 0.01-0.05:0.02-1.25:0.01-0.5:1, is preferably 0.01-0.04:0.1-1:0.02-0.35:1.
According to method of the present invention, the described oil solution containing at least one carboxylic acid neodymium can be undertaken being isolated by being sent in coalescing separator by the oil solution of at least one carboxylic acid neodymium containing water.Described coalescing separator can be common various coalescing separators.
In order to reduce the water-content of the oil solution containing at least one carboxylic acid neodymium obtained further, preferably as shown in Figure 1, described coalescing separator comprises tank body 2 and is successively set on valve plate 3, Coalescence filter core 4 and the traverse baffle 5 in tank body 2 along flow direction of material, described tank body 2 offers profit material inlet 1, water port 6 and oil discharge outlet 7, after valve plate 3, Coalescence filter core 4 and traverse baffle 5 are positioned at profit material inlet 1, and before being positioned at oil discharge outlet 7 and water port 6.When being separated the oil solution of at least one carboxylic acid neodymium containing water in aforementioned coalescing separator, comprise the following steps: the oil solution of the described at least one carboxylic acid neodymium containing water is sent into the tank body 2 of coalescing separator from the profit material inlet 1 of described coalescing separator, then entered in Coalescence filter core 4 by valve plate 3 and carry out oily water separation, material after separation is divided into aqueous phase and carboxylic acid neodymium oil solution phase through traverse baffle 5, wherein, aqueous phase is discharged from water port 6, and carboxylic acid neodymium oil solution is discharged from oil discharge outlet 7.
Be separated by adopting the aforementioned oil solution of coalescing separator at least one carboxylic acid neodymium containing water being provided with traverse baffle, the water-content contained in the oil solution of at least one carboxylic acid neodymium being separated and obtaining can be reduced further, and in actual application, can according to the specific requirement of the water-content of the oil solution containing at least one carboxylic acid neodymium, the quantity of traverse baffle is adjusted, such as: obtain the alap oil solution containing at least one carboxylic acid neodymium of water-content for requiring, more traverse baffle can be set.Usually, the quantity of described traverse baffle can be 1-5 block, is preferably 2-4 block.
Described traverse baffle can play the flow direction changing material or the parts playing throttling action (that is, can increase the residence time of material in tank body 2) for various.Such as: can be conventional segmental baffle (comprising single segmental baffle, double segmental baffle and triple segmental baffle) or disc and doughnut baffle.Be preferably segmental baffle, be more preferably the multiple segmental baffles be crisscross arranged.The form of traverse baffle has a variety of, the traverse baffle that those skilled in the art can predict various variation according to overall technical architecture of the present invention all can be used for the present invention, and reasonably can select traverse baffle according to the size and shape of coalescing separator in actual application.
When multiple segmental baffle is crisscross arranged, the spacing between traverse baffle can be conventional selection.
In order to ensure the streams separated from Coalescence filter core after traverse baffle, export from water port and oil discharge outlet respectively, preferably, described Coalescence filter core axially can be projected on the traverse baffle adjacent with this Coalescence filter core along tank body.Such as: when described traverse baffle is single segmental baffle, the minor increment of the on-fixed end of this single segmental baffle and the sidewall of tank body is d
1, be d with this on-fixed end apart from minimum sidewall to the minor increment of the outer wall of Coalescence filter core
2, wherein, d
1< d
2.
When the quantity of traverse baffle is two or more and the tank body of coalescing separator is horizontal positioned, preferably adjacent with Coalescence filter core traverse baffle is fixed on the lower wall in tank body; More preferably adjacent with described Coalescence filter core traverse baffle is fixed on the lower wall in tank body, and offers water out near the inboardend of the traverse baffle adjacent with this Coalescence filter core, and (water out 8 as shown in Figure 1), discharges with the water that will be deposited in tank body.The position of described water out on this traverse baffle is as the criterion the water be deposited in tank body can be discharged.Preferably, the minor increment of the upper limb of described water out and the inboardend of traverse baffle is d
3, the minor increment of the inboardend of the projection on traverse baffle of the lower edge of the Coalescence filter core adjacent with this traverse baffle and this traverse baffle is d
4, preferred d
3< d
4.
The structure of described Coalescence filter core is known to those skilled in the art to be known, and is generally made up of filtering layer and coalescing layer, does not repeat them here herein.
Carboxylic acid neodymium in the oil solution of the described at least one carboxylic acid neodymium containing water can be that the routine of this area is selected.Preferably, described carboxylic acid neodymium is selected from neodymium naphthenate, neodymium caprate, n-capric acid neodymium, n-caprylic acid neodymium and neodymium iso-octanate.
The oil solution of at least one carboxylic acid neodymium containing water in the various sources that the described oil solution containing at least one carboxylic acid neodymium of water can be commonly used for this area.Preferably, the oil solution of the described at least one carboxylic acid neodymium containing water adopts the method preparation comprised the steps:
Under neodymium compound and carboxylate salt are carried out the condition reacting to prepare carboxylic acid neodymium, the aqueous solution of at least one neodymium compound is contacted with the oil solution containing at least one carboxylate salt, to obtain the product containing at least one carboxylic acid neodymium; Described product is left standstill, separates oil phase and aqueous phase; Described oil phase is washed, thus obtains the oil solution of the described at least one carboxylic acid neodymium containing water.
What described neodymium compound can be commonly used for this area can react with carboxylate salt the compound forming carboxylic acid neodymium, and the example includes but not limited to Neodymium trichloride or neodymium nitrate.
The aqueous solution of described neodymium compound can adopt the ordinary method of this area to prepare.Such as, by being contacted with hydrochloric acid or nitric acid by neodymium sesquioxide pressed powder, and the product deionized water obtained can be diluted to suitable concentration, thus obtain the aqueous solution of described neodymium compound.
The various methods that this area can be adopted to commonly use prepare the described oil solution containing at least one carboxylate salt.Such as: the oil solution containing at least one carboxylic acid can be contacted with alkali and prepare, not repeat them here.
Described carboxylic acid and carboxylate salt can carry out appropriate selection according to the kind of the carboxylic acid neodymium of expection according to the Conventional wisdom of this area.Described carboxylic acid can be such as C
6-C
10straight or branched saturated carboxylic acid or C
6-C
10naphthenic acid, its specific examples includes but not limited to C
6-C
10naphthenic acid, neodecanoic acid, n-capric acid, n-caprylic acid and isocaprylic acid.The specific examples of described carboxylate salt can include but not limited to the sodium salt of carboxylic acid or the sylvite of carboxylic acid.
The range of choices of the organic solvent in the oil solution of the described at least one carboxylic acid neodymium containing water is wider, such as, can be selected from aliphatic saturated hydrocarbon and alicyclic hydrocarbon; Be preferably selected from C
5-C
10straight-chain paraffin and C
5-C
10naphthenic hydrocarbon; More preferably Skellysolve A, iso-pentane, normal hexane, hexanaphthene, normal heptane and octane is selected from.
According to method of the present invention, described halogen source and alkylating reagent can be that the routine of this area is selected.Usually, described halogen source can be selected from benzyl chloride, bromotoluene, tertiary butyl chloride, methyl chloride silane, tetrachloro silicane, aluminium diethyl monochloride, sesquialter ethylmercury chloride aluminium and a chloro-di-isobutyl aluminum.Described alkylating reagent can be selected from aluminum alkyls and alkyl-al hydride, is preferably selected from triisobutyl aluminium and diisobutylaluminium hydride.
Described first contact can be selected for the routine of this area with the second condition contacted.Usually, the condition of described first contact comprises: temperature can for-30 DEG C to 80 DEG C, and the time can be 5-120 minute; The condition of described second contact comprises: temperature can for-30 DEG C to 60 DEG C, and the time can be 0.5-48 hour.
According to method of the present invention, carry out in the inert organic solvents that described polymerization can be commonly used in this area.Particularly, the inert organic solvents as the medium of polyreaction can be selected from C
5-C
10straight or branched alkane and C
5-C
10substituted or unsubstituted naphthenic hydrocarbon, its specific examples can include but not limited to: Skellysolve A, iso-pentane, normal hexane, hexanaphthene, normal heptane, octane, methylcyclohexane, benzene,toluene,xylene and isopropyl benzene.Inert organic solvents as polymerisation medium is preferably refined before use, and described refining condition is known in the field, repeats no more herein.The consumption of the present invention to the inert organic solvents of the medium as polyreaction is not particularly limited, and can be that the routine of this area is selected.Usually, the consumption as the inert organic solvents of the medium of polyreaction makes the concentration of isoprene be 5-40 % by weight.
According to method of the present invention, the various methods that this area can be adopted to commonly use regulate the molecular weight of the polyisoprene finally obtained, to meet service requirements.Such as: the polyisoprene with different molecular weight can be prepared by regulating the relative proportion between isoprene and described alkylating reagent.When prepared according to the methods of the invention polyisoprene is used as natural synthetic rubber, the mol ratio of described isoprene and described alkylating reagent can be 1:0.0075-0.045, is preferably 1:0.009-0.042.
According to method of the present invention, the condition that isoprene carries out being polymerized is not particularly limited, can is that the routine of this area is selected, specific requirement can be met with the transformation efficiency of the molecular weight of the polyisoprene finally prepared and isoprene and be as the criterion.Usually, described polymerization can be carried out at the temperature of-30 DEG C to 80 DEG C, preferably carries out at the temperature of-10 DEG C to 70 DEG C.The time of described polymerization can carry out appropriate selection according to the temperature of polymerization, and usually, the time of described polymerization can be 0.1-5 hour.
According to method of the present invention, after being polymerized, polymerization can be stopped by adding polymerization terminator in the mixture that obtains to polymerization.The kind of described polymerization terminator and consumption can be that the routine of this area is selected, and are not particularly limited, as long as described polymerization terminator can make the polymer chain deactivation with active end group.Particularly, described polymerization terminator can be 2,6-di-tert-butyl hydroquinone.
Present invention also offers a kind of polyisoprene prepared by method of the present invention.
In prepared according to the methods of the invention polyisoprene, the content of cis Isosorbide-5-Nitrae-structures alone unit and high with the content of the Isosorbide-5-Nitrae-structures alone unit of head-tail mode keyed jointing, and the content of trans Isosorbide-5-Nitrae-structures alone unit is low.Particularly, in the polyisoprene prepared by method of the present invention, the content of cis Isosorbide-5-Nitrae-structures alone unit is more than 98%, and being preferably 98-99.6%(can be such as 98-99%); The content of trans Isosorbide-5-Nitrae-structures alone unit is less than 2%, is preferably less than 1%, is more preferably less than 0.5%, more preferably less than 0.2%, most preferably be 0; The monomeric unit of at least 99.8% is with head-tail mode keyed jointing, and preferably the monomeric unit of 100% is with head-tail mode keyed jointing.
The molecular weight of prepared according to the methods of the invention polyisoprene can carry out appropriate selection according to its embody rule occasion.When polyisoprene prepared by method of the present invention is used as natural synthetic rubber, the weight-average molecular weight of the polyisoprene prepared by method of the present invention can be 600,000-3,000,000, be preferably 800,000-2,600,000; Molecular weight distributing index can be 2.5-5, is preferably 3-4.
Invention further provides a kind of rubber combination, said composition contains polyisoprene provided by the invention and at least one vulcanizing agent, and the weight-average molecular weight of described polyisoprene is 600,000-3, and 000,000, be preferably 800,000-2,600,000; Molecular weight distributing index is 2.5-5, is preferably 3-4.
The present invention is that the polyisoprene that provides of the application of the invention is to realize object of the present invention, the kind of vulcanizing agent and consumption are not particularly limited, appropriate selection can be carried out according to the embody rule occasion of described rubber combination according to the Conventional wisdom of this area.Such as, when rubber combination according to the present invention is used for field of automobile tires, relative to polyisoprene described in 100 weight parts, the total amount of described vulcanizing agent can be 0.5-3 weight part, is preferably 0.6-2.5 weight part.Described vulcanizing agent can for being selected from one or more vulcanizing agents in sulphur, selenium, tellurium, benzoyl peroxide, urethanum and 2,5-2，5-dimethyl-2，5-di(t-butyl peroxy)2，5-hexane.
According to rubber combination of the present invention, at least one vulcanization accelerator can also be contained.The various vulcanization accelerators that described vulcanization accelerator can be commonly used for this area, are not particularly limited.Such as: described vulcanization accelerator can be selected from zinc oxide, magnesium oxide and stearic acid.The consumption of described vulcanization accelerator can carry out appropriate selection according to the kind of vulcanizing agent, repeats no more herein.
According to the various additives that rubber combination of the present invention can also be commonly used containing rubber materials according to specific needs, as anti-aging agent, filler, to improve elastomeric performance or to give synthetic rubber with various performance or function.Such as, anti-aging agent can be added in the product of contact being added with described polymerization terminator, to make the synthetic rubber obtained, there is good ageing resistance.The kind of described additive and consumption can be that the routine of this area is selected, and repeat no more herein.
The present invention is described in detail below in conjunction with embodiment and comparative example.
In following examples and comparative example, the microtexture of the polyisoprene of synthesis adopts German Bruker400MHz nmr determination, and solvent is deuterochloroform; The mooney viscosity of the polyisoprene of synthesis, according to the method specified in GB/T1232.12000, adopts the automatic Mooney viscometer determining of Japanese Shimadzu SMV-300 type; The molecular weight and molecualr weight distribution index of the polyisoprene of synthesis adopts the ALLIANCE2690 type gel permeation chromatograph of WATERS company of the U.S. to measure, adopt the PLgelMixed-C type gel chromatographic columns be purchased from Agilent company, take THF as moving phase, take Narrow distribution polystyrene as standard specimen, temperature is 25 DEG C.
In following examples and comparative example, the tensile strength of rubber is according to the method specified in ASTMD6746-03, and adopt the INSTRON5567 material pull-test machine test of INSTRON company, wherein, ASTMD412-06ADieC dumbbell shape test die made by sample.
In following examples and comparative example, rubber adopts mill to carry out mixing at roller temperature is 70 ± 5 DEG C; Cure conditions comprises: temperature is 145 DEG C, and curing time is 20min; Sulfuration basic components is: 100g rubber; 45g carbon black; 2g sulphur; 0.9g accelerant CZ; 4g stearic acid; 5g zinc oxide.Vulcanizating glue physical performance is the method according to specifying in GB/T528-1998, sample made 1 pattern sample test and obtains.
In following examples and comparative example, the water-content in carboxylic acid neodymium oil solution, by Karl-Fischer method, adopts to be purchased and records from the C21 type micro-water analyzer of MIT.
In following examples and comparative example, monomer conversion be the isoprene added weight be polymerized after the per-cent of the weight of polyisoprene that obtains.
In following examples and comparative example, the solvent of use adopts the ordinary method of this area to refine; Reaction unit before use, adopts the method for this area routine to carry out drying and deoxygenation.
In following examples and comparative example, if not otherwise specified, following coalescing separator is used to be separated: the tank body 2(internal diameter that described coalescing separator (as shown in Figure 1) comprises horizontal positioned is 500mm) and the valve plate 3 that is successively set on along flow direction of material in tank body 2, the quantity of Coalescence filter core 4(Coalescence filter core is 3, the spacing of adjacent Coalescence filter core is 50mm, the external diameter of each Coalescence filter core is 100mm, the middle axis of Coalescence filter core and the dead in line of tank body is positioned in three Coalescence filter cores) and traverse baffle 5, described tank body 2 offers profit material inlet 1, water port 6 and oil discharge outlet 7, valve plate 3, Coalescence filter core 4 and traverse baffle 5 are positioned at profit material inlet 1, between oil discharge outlet 7 and water port 6.
Wherein, described traverse baffle is single segmental baffle (as shown in Figure 2), and namely, the center of circle of traverse baffle is to the vertical range of the on-fixed end of this traverse baffle for breach action H() be 0.1 with the ratio of the internal diameter of tank body 2; The quantity of traverse baffle is 1-4; When the quantity of traverse baffle is more than 2, spacing between traverse baffle is 200mm, for being staggered between traverse baffle, the traverse baffle adjacent with Coalescence filter core is fixed on the lower wall of tank body, and offering water out 8 near the inboardend of the traverse baffle adjacent with Coalescence filter core, this water out 8 is 25mm with the minor increment of the inwall of tank body.
The concrete operations adopting the oil solution of this coalescing separator to the carboxylic acid neodymium containing water to be separated the oil solution prepared containing carboxylic acid neodymium are: send into the tank body 2 of coalescing separator by the oil solution of at least one carboxylic acid neodymium containing water from the profit material inlet 1 of coalescing separator, then entered in Coalescence filter core 4 by valve plate 3 and be separated, material after separation is divided into aqueous phase and the oil solution phase containing at least one carboxylic acid neodymium through traverse baffle 5, wherein, aqueous phase is discharged from described water port 6, oil solution containing at least one carboxylic acid neodymium is discharged from described oil discharge outlet 7.
Embodiment 1-8 is for illustration of polyisoprene of the present invention and preparation method thereof and rubber combination.
Embodiment 1
(1) 3.6kg neodymium oxide powder, 6.37kg concentrated hydrochloric acid (concentration is 37 % by weight) and deionized water are mixed, under condition of heating and stirring, neodymium sesquioxide is dissolved completely, the obtained Neodymium trichloride aqueous solution, then adding deionized water, to be diluted to concentration be 7.6 % by weight.
(2) at the temperature of 50 DEG C, with stirring, in the cyclohexane solution (concentration is 24 % by weight) of 72.46kg naphthenic acid (acid number is 230), add the aqueous sodium hydroxide solution that the Neodymium trichloride aqueous solution prepared by step (1) and 62.8kg concentration are 5 % by weight, and continue stirring 30 minutes at such a temperature.Stop heating and stir, after mixed solution is left standstill 30 minutes, separating aqueous phase.Then with deionized water, the oil phase obtained is washed, then stratification, isolate oil phase, repeat this step twice, obtain the oil solution of the neodymium naphthenate containing water, wherein, water-content is 0.98 % by weight.
(3) oil solution step (2) obtained is sent into (be staggered in coalescing separator 3 pieces of traverse baffles) in coalescing separator and is separated, obtain the oil solution containing neodymium naphthenate, and by obtain to be diluted to concentration containing the oil solution hexanaphthene of neodymium naphthenate be 0.2mol/L; With the gross weight of this oil solution for benchmark, water-content is 280wppm.
(4) triisobutyl aluminium and aluminium diethyl monochloride are mixed with the cyclohexane solution that concentration is 2mol/L respectively.
Under nitrogen protection, 535g cyclohexane solution is added in the catalyst aging still of 2L, then neodymium naphthenate solution prepared by 34g isoprene and 83mL step (3) is added in aging reactor, again at the temperature of 10 DEG C, with stirring, 21mL aluminium diethyl monochloride solution is added in aging reactor, make isoprene, neodymium naphthenate and aluminium diethyl monochloride contact reacts 15 minutes at the temperature of 10 DEG C, add 166mL triisobutyl aluminum solutions subsequently, ageing 2 hours is continued at the temperature of 10 DEG C, thus obtain catalyzer, wherein, the concentration of triisobutyl aluminium is 0.33mol/L.
(5) in the polymeric kettle of 5L, under nitrogen protection, add catalyzer prepared by 258.4g isoprene, 2309g hexanaphthene and 25mL step (4) successively.Off-response still, and 40 DEG C of reactions 50 minutes.Then release in the reaction mixture auto-polymerization still obtained, and add the methanol solution termination reaction of 2,6-di-tert-butyl hydroquinone.After the solvent in vapor removal polymers soln and unreacted isoprene, obtain polyisoprene.
After reaction terminates, release before polymers soln, to take a morsel polymers soln weighing with weighing bottle, be then placed in vacuum drying oven and be dried to constant weight, calculating monomer conversion is 90%.
After measured, in the polyisoprene obtained, the content of cis Isosorbide-5-Nitrae-structures alone unit is 98.0%, and the content of trans Isosorbide-5-Nitrae-structures alone unit is 0.2%, and the content of the monomeric unit of head-tail keyed jointing is 100%; Weight-average molecular weight is Isosorbide-5-Nitrae 49,633, and molecular weight distributing index is 3.6; The tensile strength of rubber is 0.60MPa; The tensile strength of the rubber after sulfuration is 25.4MPa, and tear strength is 53MPa.
Embodiment 2
(1) 2.6kg neodymium oxide powder, 4.54kg concentrated hydrochloric acid (concentration is 37 % by weight) and deionized water are mixed, under condition of heating and stirring, neodymium sesquioxide is dissolved completely, the obtained Neodymium trichloride aqueous solution, then adding deionized water, to be diluted to concentration be 6.2 % by weight.
(2) at the temperature of 50 DEG C, with stirring, in the hexane solution (concentration is 39 % by weight) of 22.01kg neodecanoic acid, add the aqueous solution that the Neodymium trichloride aqueous solution prepared by step (1) and 20kg concentration are the sodium hydroxide of 10 % by weight, and continue stirring 30 minutes at such a temperature.Stop heating and stir, after mixed solution is left standstill 40 minutes, separating aqueous phase.Then wash the oil phase obtained with deionized water, then stratification isolates oil phase, repeats this step twice, obtain the oil solution of the neodymium caprate containing water, wherein, water-content is 0.91 % by weight.
(3) oil solution that step (2) obtained is sent in coalescing separator (be staggered in coalescing separator 2 pieces of traverse baffles) and is separated, and obtains the oil solution containing the sour neodymium of neodecanoic acid, and oil solution normal hexane to be diluted to concentration be 0.5mol/L; With the gross weight of this oil solution for benchmark, water-content is 296wppm.
(4) triisobutyl aluminium and sesquialter ethylmercury chloride aluminium are mixed with the hexane solution that concentration is 0.5mol/L respectively.
Under nitrogen protection; in the catalyst aging still of 5L, add 82g isoprene, oil solution prepared by 80mL step (3) and 700g normal hexane; again at the temperature of 20 DEG C; add 96mL sesquialter ethylmercury chloride aluminum solutions with stirring, at the temperature of 20 DEG C, contact reacts is after 10 minutes, adds 1600mL triisobutyl aluminum solutions; and at the temperature of 10 DEG C, continue ageing 1.5 hours; thus obtain catalyzer, wherein, the concentration of triisobutyl aluminium is 0.27mol/L.
(5) in the polymeric kettle of 1L, under nitrogen protection, add catalyzer prepared by 400g isoprene, 2266g normal hexane and 62mL step (4) successively.Off-response still, and react 60 minutes at the temperature of 10 DEG C.Then release in the reaction mixture auto-polymerization still obtained, and add the methanol solution termination reaction of 2,6-di-tert-butyl hydroquinone.After the solvent in vapor removal polymers soln and unreacted isoprene, obtain polyisoprene.
After reaction terminates, release before polymers soln, to take a morsel polymers soln weighing with weighing bottle, be then placed in vacuum drying oven and be dried to constant weight, calculating monomer conversion is 92%.
After measured, in the polyisoprene obtained, the content of cis Isosorbide-5-Nitrae-structures alone unit is 98.2%, and the content of trans Isosorbide-5-Nitrae-structures alone unit is 0%, and the content of the monomeric unit of head-tail keyed jointing is 100%; Weight-average molecular weight is 1,534,791, and molecular weight distributing index is 3.7; The tensile strength of rubber is 0.61MPa; The tensile strength of the rubber after sulfuration is 26.0MPa, and tear strength is 54MPa.
Embodiment 3
(1) 1.9kg neodymium oxide powder, 3.45kg concentrated hydrochloric acid (concentration is 37 % by weight) and deionized water are mixed, under condition of heating and stirring, neodymium sesquioxide is dissolved completely, the obtained Neodymium trichloride aqueous solution, then adding deionized water, to be diluted to concentration be 8 % by weight.
(2) at the temperature of 50 DEG C, with stirring, in the hexane solution (concentration is 18 % by weight) of 30kg isocaprylic acid, add the aqueous sodium hydroxide solution that the Neodymium trichloride aqueous solution prepared by step (1) and 15.5kg concentration are 10 % by weight, and continue stirring 30 minutes at such a temperature.Stop heating and stir, after mixed solution is left standstill 60 minutes, removing lower floor's aqueous phase.Then wash the oil phase obtained with deionized water, then stratification isolates oil phase, repeats this step twice, obtain the oil solution of moisture neodymium iso-octanate, wherein, water-content is 0.83 % by weight.
(3) oil solution that step (2) obtained is sent in coalescing separator (be staggered in coalescing separator 4 pieces of traverse baffles) and is separated, and obtains the oil solution containing neodymium iso-octanate, and this oil solution normal hexane is diluted to concentration is 0.2mol/L; With the gross weight of this oil solution for benchmark, water-content is 217wppm.
(4) diisobutylaluminium hydride and tertiary butyl chloride are mixed with the hexane solution that concentration is 0.5mol/L respectively.
Under nitrogen protection; oil solution prepared by 33g isoprene and 80mL step (3) is added in the catalyst aging still of 2L; again at the temperature of 30 DEG C; add 320mL tertiary butyl chloride solution with stirring, at the temperature of 30 DEG C, contact reacts is after 5 minutes, adds 800mL diisobutylaluminium hydride solution; and at the temperature of 10 DEG C, continue ageing 2 hours; thus obtain catalyzer, wherein, the concentration of diisobutylaluminium hydride is 0.32mol/L.
(5) in the polymeric kettle of 5L, under nitrogen protection, add catalyzer prepared by 350g isoprene, 1860g normal hexane and 40mL step (4) successively.Off-response still, and react 90 minutes at the temperature of 30 DEG C.Then release in the reaction mixture auto-polymerization still obtained, and add the methanol solution termination reaction of 2,6-di-tert-butyl hydroquinone.After the solvent in vapor removal polymers soln and unreacted isoprene, obtain polyisoprene.
After reaction terminates, release before polymers soln, to take a morsel polymers soln weighing with weighing bottle, be then placed in vacuum drying oven and be dried to constant weight, calculating monomer conversion is 95%.
After measured, in the polyisoprene obtained, the content of cis Isosorbide-5-Nitrae-structures alone unit is 98.6%, and the content of trans Isosorbide-5-Nitrae-structures alone unit is 0.1%, and the content of the monomeric unit of head-tail keyed jointing is 100%; Weight-average molecular weight is 1,367,906; Molecular weight distribution is 3.7; The tensile strength of rubber is 0.66MPa; The tensile strength of the rubber after sulfuration is 25.2MPa, and tear strength is 53MPa.
Embodiment 4
(1) method identical with embodiment 1 is adopted to prepare the oil solution containing neodymium naphthenate, unlike, it is 0.15mol/L that the oil solution hexanaphthene containing neodymium naphthenate obtained is diluted to concentration.
(2) diisobutylaluminium hydride and a chlorine trimethyl silane are mixed with the hexane solution that concentration is 0.5mol/L respectively.
Under nitrogen protection; 78mL mono-chlorine trimethyl silane solution is added in the catalyst aging still of 1L; and at the temperature of 50 DEG C; with stirring the oil solution adding 29g isoprene and 86mL and contain neodymium naphthenate, at the temperature of 50 DEG C, contact reacts is after 5 minutes, adds 464mL diisobutylaluminium hydride solution; and at the temperature of 5 DEG C, continue ageing 1.5 hours; thus obtain catalyzer, wherein, the concentration of diisobutylaluminium hydride is 0.34mol/L.
(3) in the polymeric kettle of 5L, under nitrogen protection, add catalyzer prepared by 350g isoprene, 1927g normal hexane and 235mL step (2) successively.Off-response still, and react 80 minutes at the temperature of 10 DEG C.Then release in the reaction mixture auto-polymerization still obtained, and add the methanol solution termination reaction of 2,6-di-tert-butyl hydroquinone.After the solvent in vapor removal polymers soln and unreacted isoprene, obtain polyisoprene.
After reaction terminates, release before polymers soln, to take a morsel polymers soln weighing with weighing bottle, be then placed in vacuum drying oven and be dried to constant weight, calculating monomer conversion is 96%.
After measured, in the polyisoprene obtained, the content of cis Isosorbide-5-Nitrae-structures alone unit is 98.1%, and the content of trans Isosorbide-5-Nitrae-structures alone unit is 0.2%, and the content of the monomeric unit of head-tail keyed jointing is 100%; Weight-average molecular weight is 1,340,531; Molecular weight distributing index is 3.5; The tensile strength of rubber is 0.60MPa; The tensile strength of the rubber after sulfuration is 25.2MPa, and tear strength is 53MPa.
Embodiment 5
(1) method identical with embodiment 2 is adopted to prepare the oil solution containing neodymium caprate.
(2) triisobutyl aluminium and aluminium diethyl monochloride are mixed with the hexane solution that concentration is 0.5mol/L respectively.
Under nitrogen protection; in the catalyst aging still of 10L, add 80mL contain the oil solution of neodymium caprate, 185g isoprene and 3475g normal hexane; again at the temperature of 0 DEG C; add 240mL aluminium diethyl monochloride solution with stirring, at the temperature of 0 DEG C, contact reacts is after 20 minutes, adds 800mL triisobutyl aluminum solutions; ageing 16 hours is continued at the temperature of 0 DEG C; thus obtain catalyzer, wherein, the concentration of triisobutyl aluminium is 0.06mol/L.
(3) in the polymeric kettle of 5L, under nitrogen protection, add catalyzer prepared by 300g isoprene, 1933g normal hexane and 110mL step (2) successively.Off-response still, and react 60 minutes at the temperature of 20 DEG C.Then release in the reaction mixture auto-polymerization still obtained, and add the methanol solution termination reaction of 2,6-di-tert-butyl hydroquinone.After the solvent in vapor removal polymers soln and unreacted isoprene, obtain polyisoprene.
After reaction terminates, release before polymers soln, to take a morsel polymers soln weighing with weighing bottle, be then placed in vacuum drying oven and be dried to constant weight, calculating monomer conversion is 89%.
After measured, in the polyisoprene obtained, the content of cis Isosorbide-5-Nitrae-structures alone unit is 98.4%, and the content of trans Isosorbide-5-Nitrae-structures alone unit is 0.1%, and the content of the monomeric unit of head-tail keyed jointing is 100%; Weight-average molecular weight is 2,301,570; Molecular weight distributing index is 3.3; The tensile strength of rubber is 0.63MPa; The tensile strength of the rubber after sulfuration is 26.9MPa, and tear strength is 56MPa.
Embodiment 6
(1) method identical with embodiment 2 is adopted to prepare the oil solution containing neodymium caprate.
(2) triisobutyl aluminium and diisobutyl aluminum chloride are mixed with the hexane solution that concentration is 0.5mol/L respectively.
Under nitrogen protection; the oil solution containing neodymium caprate prepared by 231g isoprene, 7557g normal hexane and 80mL step (2) is added in the catalyst aging still of 20L; again at the temperature of-10 DEG C; adding 200mL diisobutyl aluminum chloride solution with stirring ,-10 DEG C of contact reactss after 15 minutes, adding 1600mL triisobutyl aluminum solutions; and at the temperature of 0 DEG C, continue ageing 6 hours; thus obtain catalyzer, wherein, the concentration of triisobutyl aluminium is 0.058mol/L.
(3) in the polymeric kettle of 5L, under nitrogen protection, add catalyzer prepared by 280g isoprene, 2437g hexanaphthene and 123mL step (2) successively.Close polymeric kettle, and react 100 minutes at the temperature of-10 DEG C.Then release in the reaction mixture auto-polymerization still obtained, and add the methanol solution termination reaction of 2,6-di-tert-butyl hydroquinone.After the solvent in vapor removal polymers soln and unreacted isoprene, obtain polyisoprene.
After reaction terminates, release before polymers soln, to take a morsel polymers soln weighing, be then placed in vacuum drying oven and be dried to constant weight with weighing bottle, calculate monomer conversion by example weight before and after dry, transformation efficiency is 85% as calculated.
After measured, in the polyisoprene obtained, the content of cis Isosorbide-5-Nitrae-structures alone unit is 98.8%, and the content of trans Isosorbide-5-Nitrae-structures alone unit is 0%, and the content of the monomeric unit of head-tail keyed jointing is 100%; Weight-average molecular weight is 1,891,969; Molecular weight distributing index is 3.0; The tensile strength of rubber is 0.68MPa; The tensile strength of the rubber after sulfuration is 26.6MPa, and tear strength is 55MPa.
Embodiment 7
(1) oil solution containing neodymium naphthenate is prepared according to the method identical with embodiment 1, unlike, in the coalescing separator of use, the quantity of traverse baffle is 1, and all the other structures are identical, with the total amount of the oil solution containing neodymium naphthenate finally obtained for benchmark, water-content is 300wppm.
(2) method identical with embodiment 1 is adopted to prepare polyisoprene, unlike, catalyzer is catalyzer prepared by embodiment 7 step (1).
After reaction terminates, release before polymers soln, to take a morsel polymers soln weighing with weighing bottle, be then placed in vacuum drying oven and be dried to constant weight, calculating monomer conversion is 85%.
After measured, in the polyisoprene obtained, the content of cis Isosorbide-5-Nitrae-structures alone unit is 98.1%, and the content of trans Isosorbide-5-Nitrae-structures alone unit is 0.5%, and the content of the monomeric unit of head-tail keyed jointing is 99.8%; Weight-average molecular weight is 1,687,403; Molecular weight distributing index is 3.9; The tensile strength of rubber is 0.54MPa; The tensile strength of the rubber after sulfuration is 24.9MPa, and tear strength is 53MPa.
Comparative example 1
(1) oil solution containing neodymium naphthenate is prepared according to the method identical with embodiment 1, unlike, do not arrange traverse baffle in the coalescing separator of use, all the other structures are identical, with the total amount of the oil solution containing neodymium naphthenate finally obtained for benchmark, water-content is 500wppm.
(2) method identical with embodiment 1 is adopted to prepare polyisoprene, unlike, catalyzer is catalyzer prepared by comparative example 1 step (1).
After reaction terminates, release before polymers soln, to take a morsel polymers soln weighing, be then placed in vacuum drying oven and be dried to constant weight with weighing bottle, calculate monomer conversion by example weight before and after dry, transformation efficiency is 78% as calculated.
After measured, in the polyisoprene obtained, the content of cis Isosorbide-5-Nitrae-structures alone unit is 98.0%, and the content of trans Isosorbide-5-Nitrae-structures alone unit is 0.8%, and the content of the monomeric unit of head-tail keyed jointing is 99.1%; Weight-average molecular weight is 1,790,457; Molecular weight distributing index is 4.2; The tensile strength of rubber is 0.50MPa; The tensile strength of the rubber after sulfuration is 24.2MPa, and tear strength is 51MPa.
Comparative example 2
The method identical with embodiment 1 is adopted to prepare polyisoprene, unlike, do not carry out step (3), but the oil solution of the neodymium naphthenate containing water step (2) obtained distills at ambient pressure, collect the cut that boiling range is 76-80 DEG C, thus obtain the oil solution containing neodymium naphthenate.With the total amount of this oil solution for benchmark, water-content is 600wppm.
As calculated, monomer conversion is 68%.
After measured, in the polyisoprene obtained, the content of cis Isosorbide-5-Nitrae-structures alone unit is 97.6%, and the content of trans Isosorbide-5-Nitrae-structures alone unit is 1.0%, and the content of the monomeric unit of head-tail keyed jointing is 99.0%; Weight-average molecular weight is 1,844,132; Molecular weight distributing index is 4.5; The tensile strength of rubber is 0.38MPa; The tensile strength of the rubber after sulfuration is 24.1MPa, and tear strength is 49MPa.
Embodiment 8
(1) oil solution containing neodymium naphthenate is prepared according to the method identical with embodiment 1, unlike, in the coalescing separator of use, the quantity of traverse baffle is 4, and all the other structures are identical, with the total amount of the oil solution containing neodymium naphthenate finally obtained for benchmark, water-content is 50wppm.
(2) method identical with embodiment 1 is adopted to prepare polyisoprene, unlike, catalyzer is catalyzer prepared by embodiment 9 step (1).
After reaction terminates, release before polymers soln, to take a morsel polymers soln weighing with weighing bottle, be then placed in vacuum drying oven and be dried to constant weight, calculating monomer conversion is 99%.
After measured, in the polyisoprene obtained, the content of cis Isosorbide-5-Nitrae-structures alone unit is 98.6%, and the content of trans Isosorbide-5-Nitrae-structures alone unit is 0%, and the content of the monomeric unit of head-tail keyed jointing is 100%; Weight-average molecular weight is 185,412; Molecular weight distributing index is 3.0; The tensile strength of rubber is 0.64MPa; The tensile strength of the rubber after sulfuration is 26.0MPa, and tear strength is 55MPa.
Claims (20)
1. a polyisoprene, in this polyisoprene, the content of cis Isosorbide-5-Nitrae-structures alone unit is more than 98%, trans 1, the content of 4-structures alone unit be the monomeric unit of less than 0.2%, at least 99.8% with head-tail mode keyed jointing, the weight-average molecular weight of this polyisoprene is 600,000-3,000,000, molecular weight distributing index is 2.5-5.
2. polyisoprene according to claim 1, wherein, in this polyisoprene, the content of trans Isosorbide-5-Nitrae-structures alone unit is 0.
3. polyisoprene according to claim 1, wherein, in this polyisoprene, the monomeric unit of 100% is with head-tail mode keyed jointing.
4. according to the polyisoprene in claim 1-3 described in any one, wherein, the weight-average molecular weight of this polyisoprene is 800,000-2,600,000, and molecular weight distributing index is 3-4.
5. prepare a method for polyisoprene, in described polyisoprene, the content of cis Isosorbide-5-Nitrae-structures alone unit is more than 98%, the content of trans Isosorbide-5-Nitrae-structures alone unit is less than 0.2%, the monomeric unit of at least 99.8% is with head-tail mode keyed jointing, the weight-average molecular weight of this polyisoprene is 600, 000-3, 000, 000, molecular weight distributing index is 2.5-5, under the method is included in rare earth catalyst existence, isoprene is polymerized, described rare earth catalyst is by the oil solution containing at least one carboxylic acid neodymium, at least one halogen source and at least one conjugated diene carry out the first contact at least one inert organic solvents, and the mixture obtained and at least one alkylating reagent are carried out second and contact and make, wherein, with the gross weight of described oil solution for benchmark, the water-content of described oil solution is lower than 300wppm.
6. method according to claim 5, wherein, the mol ratio of the carboxylic acid neodymium in described oil solution, described alkylating reagent, described halogen source and described conjugated diene is 0.01-0.05:0.02-1.25:0.01-0.5:1.
7. method according to claim 5, wherein, the mol ratio of the carboxylic acid neodymium in described oil solution, described alkylating reagent, described halogen source and described conjugated diene is 0.01-0.04:0.1-1:0.02-0.35:1.
8., according to the method in claim 5-7 described in any one, wherein, with the gross weight of described oil solution for benchmark, the water-content of described oil solution is 20-298wppm.
9., according to the method in claim 5-7 described in any one, wherein, with the gross weight of described oil solution for benchmark, the water-content of described oil solution is 200-298wppm.
10. according to the method in claim 5-7 described in any one, wherein, described carboxylic acid neodymium is selected from neodymium naphthenate, neodymium caprate, n-capric acid neodymium, n-caprylic acid neodymium and neodymium iso-octanate.
11. according to the method in claim 5-7 described in any one, and wherein, described halogen source is selected from benzyl chloride, bromotoluene, tertiary butyl chloride, methyl chloride silane, tetrachloro silicane, aluminium diethyl monochloride, sesquialter ethylmercury chloride aluminium and a chloro-di-isobutyl aluminum;
Described alkylating reagent is selected from aluminum alkyls and alkyl-al hydride;
Described inert organic solvents is selected from C
5-C
10alkane and C
5-C
10naphthenic hydrocarbon.
12. methods according to claim 11, wherein, described alkylating reagent is selected from triisobutyl aluminium and diisobutylaluminium hydride.
13. methods according to claim 11, wherein, described inert organic solvents is selected from Skellysolve A, iso-pentane, normal hexane, hexanaphthene, normal heptane and octane.
14. methods according to claim 5, wherein, the mol ratio of described isoprene and described alkylating reagent is 1:0.0075-0.045.
15. methods according to claim 5, wherein, the condition of described first contact comprises: temperature is-30 DEG C to 80 DEG C, and the time is 5-120 minute; The condition of described second contact comprises: temperature is-30 DEG C to 60 DEG C, and the time is 0.5-48 hour.
16. methods according to claim 5, wherein, in described polyisoprene, the content of trans Isosorbide-5-Nitrae-structures alone unit is 0.
17. methods according to claim 5, wherein, in described polyisoprene, the monomeric unit of 100% is with head-tail mode keyed jointing.
18. according to the method in claim 5,16 and 17 described in any one, and wherein, the weight-average molecular weight of described polyisoprene is 800,000-2, and 600,000, molecular weight distributing index is 3-4.
19. 1 kinds of rubber combinations, this rubber combination contains polyisoprene in claim 1-4 described in any one or the polyisoprene prepared by the method in claim 5-18 described in any one and at least one vulcanizing agent.
20. rubber combinations according to claim 19, wherein, relative to polyisoprene described in 100 weight parts, the content of described vulcanizing agent is 0.5-3 weight part.
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