CN102964375A - Vanadium catalyst, vanadium catalyst composition and preparation method of ethylene propylene rubber - Google Patents
Vanadium catalyst, vanadium catalyst composition and preparation method of ethylene propylene rubber Download PDFInfo
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Abstract
The invention provides a vanadium complex shown as a formula (I) and a preparation method thereof. The invention further provides a vanadium catalyst composition comprising the vanadium complex shown as the formula (I), an organic aluminium compound and an activating accelerator. The catalyst composition can be used for preparation of a binary ethylene propylene rubber and a ternary ethylene propylene rubber. The vanadium complex shown as the formula (I) is a solid substance, so the catalyst composition has good stability and long preservation time in water and air; and in addition, the catalyst composition with high catalytic activity is used, so that the production cost of the ethylene propylene rubber is reduced. An experimental result shows that the productivity of the ethylene propylene rubber obtained by catalyzing via the catalyst composition is 70-80%; and in addition, the ethylene propylene rubber prepared and obtained by the vanadium catalyst composition has the advantages of wide molecular weight distribution and good physical and mechanical properties, and is beneficial to the subsequent process.
Description
Technical field
The present invention relates to field of rubber materials, particularly vanadium catalyst, vanadium catalyst composition and ethylene-propylene rubber(EPR) preparation method.
Background technology
Ethylene-propylene rubber(EPR) is a kind of copolymer rubber take ethene and propylene as basic monomer.It specifically can be divided into ethylene propylene rubber and terpolymer EP rubber.Compare with other rubber clones, ethylene-propylene rubber(EPR) has the following advantages: one, do not contain two keys in the main chain, and fully saturated, anti-ozone, ageing-resistant, chemicals-resistant and high temperature resistant; Two, light specific gravity; Three, excellent insulation performance; Four, being can highly oil-filled rubber clone.Ethylene-propylene rubber(EPR) is one of at present the most rising rubber kind, since it is commercially produced, its Application Areas is constantly expanded, and has been widely used in trolley part, building materials, electric wire, heat-resistant rubber hose, senior sealing material, lubricating oil additive and the aspect such as polyolefin modified.
Producing ethylene-propylene rubber(EPR) both at home and abroad is Primary Catalysts mainly with vanadium sub-group compound.These vanadium compound are VX
3, VX
4, VOX
3And VO (OR)
3-nX
n, X is halogen, is mainly the chlorine atom, and R is the alkyl of 6-12 carbon, and n is the integer of 0-2.But all there are various shortcomings in numerous vanadium sub-group compounds.VCl
3, VCl
4And VOCl
3By V
2O
5High-temp chlorination makes, and uses in a large number chlorine not only to damage operator's health, and causes serious environmental pollution.On the other hand, VCl
3, VCl
4And VOCl
3Volatile, toxicity is large, meet air decomposes, meets the water blast, thereby brings inconvenience for storage, transportation and use.VO (OR)
3-nCl
nAlthough comparatively stable, it is by VOCl
3And Fatty Alcohol(C12-C14 and C12-C18) (ROH) direct reaction makes, and can not avoid VOCl equally
3The shortcoming of preparation process.
In order to solve above-mentioned technical problem, the researchist is devoted to research and develop alternative VOCl
3Vanadium series catalyst, application number is that the Chinese patent of CN1310981C and CN101108885B adopts respectively the vanadium compound of extraction process preparation as vanadium series catalyst take acid organic phosphine, Fatty Alcohol(C12-C14 and C12-C18) as part.This class catalyzer is stable, the preparation method is simple, use safety, and reaction conditions is gentle, has overcome existing commercial catalysts VOCl
3Many disadvantages in preparation and use procedure.But use VOCl
3When catalyzed ethylene and copolymerization of propylene or ethene, propylene and the copolymerization of non-conjugated dienes hydrocarbon, catalytic activity is lower, and production cost is very high, causes the ethylene-propylene rubber(EPR) cost value high.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of vanadium series catalyst composition, and catalytic activity is high, good stability.
The invention discloses a kind of vanadium complex as shown in the formula (I),
VOCl
2·nROH（I）；
Wherein, R is the alkyl of C5 ~ C10,1≤n≤3.
The invention discloses a kind of preparation method of vanadium complex, may further comprise the steps:
Fatty Alcohol(C12-C14 and C12-C18) and mixing diluents with C5 ~ C10 obtain diluent; Described thinner is the saturated alkane of C6 ~ C8;
After described diluent, the sodium metavanadate aqueous solution and concentrated hydrochloric acid hybrid reaction, extract, obtain vanadium complex saturated alkane solution;
After the ratio of Fatty Alcohol(C12-C14 and C12-C18) volumetric molar concentration and vanadium volumetric molar concentration in the described vanadium complex saturated alkane solution is adjusted to 2.5 ~ 3.5, carry out air distillation, obtain intermediate product;
Described intermediate product is carried out underpressure distillation process under the stablizer protection, obtain vanadium complex as shown in the formula (I) after the drying; Described stablizer is mass concentration less than the lipid acid of C2 ~ C4 of 1%
VOCl
2·nROH（I）；
Wherein, R is the alkyl of C5 ~ C10,1≤n≤3.
Preferably, the temperature of described underpressure distillation is 0 ~ 30 ℃, and the time of described underpressure distillation is 1 ~ 4 hour.
Preferably, the temperature of described drying is 20 ~ 40 ℃.
Preferably, described Fatty Alcohol(C12-C14 and C12-C18) is the saturated fatty alcohol of C6 ~ C8.
The invention discloses a kind of vanadium catalyst composition, comprise as shown in the formula (I) vanadium complex, organo-aluminium compound and activation promotor;
Described activation promotor is haloalkane or ester class;
The mol ratio of described organo-aluminium compound and vanadium complex is 20 ~ 100:1;
The mol ratio of described activation promotor and vanadium complex is 1 ~ 20:1;
VOCl
2·nROH（I）；
Wherein, R is the alkyl of C5 ~ C10,1≤n≤3.
Preferably, described activation promotor is ethyl trichloroacetate, CH
3Cl, CH
2Cl
2Or CHCl
3
Preferably, described organo-aluminium compound is one or more in trichlorine triethyl two aluminium, ethyl aluminum dichloride, aluminium diethyl monochloride and the dichloro aluminium isobutyl.
The invention discloses a kind of preparation method of ethylene propylene rubber, may further comprise the steps:
In organic solvent, ethene and propylene are under catalyst composition effect claimed in claim 8, and polymerization reaction take place obtains ethylene propylene rubber.
The invention also discloses a kind of preparation method of terpolymer EP rubber, may further comprise the steps:
In organic solvent, ethene, propylene and non-conjugated diene are under catalyst composition effect claimed in claim 8, and polymerization reaction take place obtains terpolymer EP rubber.
Compared with prior art, vanadium catalyst composition of the present invention comprises vanadium complex, organo-aluminium compound and activation promotor as shown in the formula (I), and wherein as shown in the formula (I) vanadium complex plays main katalysis.Vanadium complex as shown in the formula (I) is solid matter, and therefore described catalyst composition has good stability in water and air, and the shelf time is long.Secondly, use catalyst composition catalytic activity of the present invention high, reduced the production cost of ethylene-propylene rubber(EPR); Experimental result shows that the ethylene-propylene rubber(EPR) productive rate that is obtained by its catalysis is 70% ~ 80%.In addition, by the ethylene-propylene rubber(EPR) that described long catalyst composition prepares, molecular weight distribution is wide, and physical and mechanical properties is good, is conducive to following process.
Description of drawings
Fig. 1 is the mass spectrum of the vanadium complex of embodiment 1 preparation.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, but should be appreciated that these describe just as further specifying the features and advantages of the present invention, rather than to the restriction of claim of the present invention.
The embodiment of the invention discloses a kind of vanadium complex as shown in the formula (I),
VOCl
2·nROH（I）；
Wherein, R is the alkyl of C5 ~ C10, is preferably the alkyl of C6 ~ C8; 1≤n≤3, preferred n is 2 or 3.
The invention discloses a kind of preparation method of vanadium complex, may further comprise the steps:
Fatty Alcohol(C12-C14 and C12-C18) and mixing diluents with C5 ~ C10 obtain diluent; Described thinner is the saturated alkane of C6 ~ C8;
After described diluent, the sodium metavanadate aqueous solution and concentrated hydrochloric acid hybrid reaction, extract, obtain vanadium complex saturated alkane solution;
After the ratio of Fatty Alcohol(C12-C14 and C12-C18) volumetric molar concentration and vanadium volumetric molar concentration in the described vanadium complex saturated alkane solution is adjusted to 2.5 ~ 3.5, carry out air distillation, obtain intermediate product;
Described intermediate product is carried out underpressure distillation process under the stablizer protection, obtain vanadium complex as shown in the formula (I) after the drying; Described stablizer is mass concentration less than the lipid acid of C2 ~ C4 of 1%;
VOCl
2·nROH（I）；
Wherein, R is the alkyl of C5 ~ C10,1≤n≤3.
According to the present invention, at first prepare diluent and the sodium metavanadate aqueous solution.When the preparation diluent, Fatty Alcohol(C12-C14 and C12-C18) and mixing diluents with C5 ~ C10 obtain diluent.Described Fatty Alcohol(C12-C14 and C12-C18) is preferably the Fatty Alcohol(C12-C14 and C12-C18) of C6 ~ C8, more preferably n-Octanol, isooctyl alcohol, secondary octanol or n-hexyl alcohol.Described thinner is the saturated alkane of C6 ~ C8, is preferably in hexane and the heptane one or both.The concentration of described diluent is Fatty Alcohol(C12-C14 and C12-C18) concentration in the diluent, is preferably 0.3 ~ 4mol/L, and more preferably 1 ~ 3.5mol/L most preferably is 1.5 ~ 3mol/L.
Behind the described diluent, with after itself and sodium metavanadate and the concentrated hydrochloric acid hybrid reaction, extract, obtain vanadium complex saturated alkane solution.Described sodium metavanadate can add with the form of pressed powder, also can be configured to solution and add.When the preparation sodium metavanadate aqueous solution, the present invention does not have particular restriction to its preparation method, can be according to method configuration well known to those skilled in the art.
Fatty Alcohol(C12-C14 and C12-C18) in the described diluent and the mol ratio Q of sodium metavanadate
ROH/ Q
VBe preferably 2.5 ~ 3.02, more preferably 2.7 ~ 3.02.The concentration of described concentrated hydrochloric acid is preferably 11.9mol/L, its not only with the reaction of sodium metavanadate and diluent, but also the concentration of hydrochloric acid to 0.2 of initial water ~ 9mol/L will regulate extraction the time; The add-on of described concentrated hydrochloric acid is for reacting acid consumption (with QHCl
(1)Expression) with the acid consumption of regulating initial aqueous-phase concentration of hydrochloric acid (with QHCl
(2)Expression) sum.The time of described reaction is preferably 5 ~ 20 minutes, and the temperature of described reaction does not have particular restriction, and room temperature gets final product.Described reaction extracts after finishing, and the concentration of hydrochloric acid of initial water is 0.2 ~ 9mol/L during extraction, is preferably 1 ~ 5mol/L, more preferably 1.5 ~ 3.5mol/L.
After the extraction, obtain organic phase and be vanadium complex saturated alkane solution.After the ratio of Fatty Alcohol(C12-C14 and C12-C18) volumetric molar concentration and vanadium volumetric molar concentration in the described vanadium complex saturated alkane solution is adjusted to 2.5 ~ 3.5, carry out air distillation, obtain intermediate product.The measuring method of described vanadium volumetric molar concentration is preferably: get vanadium complex saturated alkane solution and strip with the sodium hydroxide solution of 1mol/L, then utilize Oxidation-Reduction Volumetric Analysis Method to obtain the vanadium volumetric molar concentration.After obtaining the vanadium volumetric molar concentration, the ratio of Fatty Alcohol(C12-C14 and C12-C18) volumetric molar concentration and vanadium volumetric molar concentration if be lower than 2.5, preferably add an amount of Fatty Alcohol(C12-C14 and C12-C18) described ratio is adjusted to 2.5 ~ 3.5 in the calculating vanadium complex saturated alkane solution.The Heating temperature of described air distillation is preferably 60 ~ 80 ℃, more preferably 65 ~ 75 ℃.Described intermediate product is VOCl
3NROH, wherein, R is the alkyl of C5 ~ C10,1≤n≤3.
After obtaining intermediate product, it is carried out underpressure distillation process under the stablizer protection, obtain vanadium complex as shown in the formula (I) after the drying; Described stablizer is mass concentration less than the lipid acid of C2 ~ C4 of 1%;
VOCl
2·nROH（I）；
Wherein, R is the alkyl of C5 ~ C10,1≤n≤3.
The temperature that described underpressure distillation is processed is preferably 0 ~ 30 ℃, more preferably 10 ~ 20 ℃; The time of described underpressure distillation is preferably 1 ~ 4 hour, more preferably 2 ~ 3 hours.The temperature of described drying is preferably 20 ~ 40 ℃, more preferably 25 ~ 30 ℃.Described stablizer is mass concentration less than the lipid acid of C2 ~ C4 of 1%; The mass concentration of the lipid acid of described C2 ~ C4 is preferably 0.3% ~ 0.5%.The lipid acid of described C2 ~ C4 is preferably propionic acid or acetic acid.。
The invention discloses a kind of vanadium catalyst composition, comprise as shown in the formula (I) vanadium complex, organo-aluminium compound and activation promotor;
Described activation promotor is haloalkane or ester class;
The mol ratio of described organo-aluminium compound and vanadium complex is 20 ~ 100:1;
The mol ratio of described activation promotor and vanadium complex is 1 ~ 20:1;
VOCl
2·nROH（I）；
Wherein, R is the alkyl of C5 ~ C10,1≤n≤3.
According to the present invention, vanadium catalyst composition comprises vanadium complex, organo-aluminium compound and activation promotor as shown in the formula (I).
Described organo-aluminium compound has the auxiliary catalysis effect as the component of vanadium catalyst composition to vanadium complex.Described organo-aluminium compound is preferably one or more in trichlorine triethyl two aluminium, ethyl aluminum dichloride, aluminium diethyl monochloride and the dichloro aluminium isobutyl, more preferably one or both in ethyl aluminum dichloride and the aluminium diethyl monochloride.The present invention does not have particular restriction to the source of described alkylaluminium cpd yet, can be bought by market.
In described vanadium catalyst composition, also comprise activation promotor, the effect of described activation promotor is to make deactivated V
2+Compound oxidation becomes activated V
3+Compound has increased the number in active centre, and accelerative activator can prolong the active lifetime of growing chain, makes the active centre stable.Described activation promotor is haloalkane or ester class, is preferably ethyl trichloroacetate, CH
3Cl, CH
2Cl
2Or CHCl
3
The mol ratio of described organo-aluminium compound and vanadium complex is 20 ~ 100:1, is preferably 30 ~ 80:1; The mol ratio of described activation promotor and vanadium complex is 1 ~ 20:1, is preferably 3 ~ 12:1.
The invention discloses a kind of preparation method of ethylene propylene rubber, may further comprise the steps:
In organic solvent, ethene and propylene are under the described catalyst composition effect of technique scheme, and polymerization reaction take place obtains ethylene propylene rubber.
Among the present invention, the concentration of vanadium complex in organic solvent shown in the described catalyst composition Chinese style (I) is preferably 1 * 10
-4Mol/L ~ 2 * 10
-3Mol/L; More preferably 3 * 10
-4Mol/L ~ 1.5 * 10
-3Mol/L.The mol ratio of described ethene and propylene is preferably (1:7) ~ (4:5).Described organic solvent is preferably one or more in normal hexane, hexanaphthene and the heptane.The temperature of described polyreaction is preferably 0 ~ 70 ℃, more preferably 20 ~ 50 ℃; The pressure of described polyreaction is preferably 0.1 ~ 0.6MPa, more preferably 0.3 ~ 0.5MPa; The time of described polyreaction is preferably 10 ~ 90 minutes, more preferably 20 ~ 70 minutes.
Described polyreaction is preferably passed through aftertreatment after finishing, and obtains ethylene propylene rubber.The product that described last handling process is preferably polyreaction joins in hydrochloric acid-ethanolic soln, and the mass percent of described hydrochloric acid is 5%, and after the filtration, with the washing with alcohol precipitation, then vacuum-drying obtains final ethylene propylene rubber.
Originally issuing a statement also discloses a kind of preparation method of terpolymer EP rubber, may further comprise the steps:
In organic solvent, ethene, propylene and non-conjugated diene are under the described catalyst composition effect of technique scheme, and polymerization reaction take place obtains terpolymer EP rubber.
In the present invention, the concentration of vanadium complex in organic solvent shown in the described catalyst composition Chinese style (I) is preferably 1 * 10
-4Mol/L ~ 2 * 10
-3Mol/L; More preferably 3 * 10
-4Mol/L ~ 1.5 * 10
-3Mol/L.The mol ratio of described ethene and propylene is preferably (1:7) ~ (4:5).Described non-conjugated diene is preferably dicyclopentadiene (DCPD), ethylidene norbornene (ENB) or Isosorbide-5-Nitrae-hexadiene.The add-on of described non-conjugated diene is preferably 1 ~ 38% of end product terpolymer EP rubber massfraction.Described organic solvent is preferably one or more in normal hexane, hexanaphthene and the heptane.The temperature of described polyreaction is preferably 0 ~ 70 ℃, more preferably 20 ~ 50 ℃; The pressure of described polyreaction is preferably 0.1 ~ 0.6MPa, more preferably 0.3 ~ 0.5MPa; The time of described polyreaction is preferably 10 ~ 90 minutes, more preferably 20 ~ 70 minutes.
Described polyreaction is preferably passed through aftertreatment after finishing, and obtains terpolymer EP rubber.The product that described last handling process is preferably polyreaction joins in hydrochloric acid-ethanolic soln, and the mass percent of described hydrochloric acid is 5%, and after the filtration, with the washing with alcohol precipitation, then vacuum-drying obtains final terpolymer EP rubber.
Ethylene-propylene rubber(EPR) to the present invention's preparation is analyzed through DSC, NMR, IR and high temperature GPC, and the result shows that the ethylene-propylene rubber(EPR) molecular weight distribution of the present invention's preparation is wide, is conducive to post-treatment.
In order further to understand the present invention, below in conjunction with embodiment the preparation method of vanadium series catalyst composition provided by the invention and ethylene-propylene rubber(EPR) is described, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Add 50g V in the 200mL beaker
2O
5With 100mL pure water furnishing thin pulp.Adding 100mL pure water and 24.2gNaOH stir and make it dissolving in the 1000mL beaker, and heating is closely boiled, and slowly adds V
2O
5Slurries stirred 20 minutes, got faint yellow NaVO
3Solution, then the elimination insolubles is diluted to 325mL with pure water, obtains NaVO
3Solution.Sampling analysis, NaVO
3The concentration of solution is 1.679mol/L.
Get the 20mL isooctyl alcohol and be diluted to 100mL with hexane, obtaining isooctyl alcohol concentration is the isooctyl alcohol diluent of 1.280mol/L.
In the 250mL separating funnel, add isooctyl alcohol saturated alkane solution 60mL(ROH/V=2.5), press vanadic acid sodium add-on and [HCl]
f=9mol/L requires to calculate and adds dense HCl102.6mL, adds NaVO again
3Solution 18.3mL places on the Kang Shi vibrator vibration two-phase fully to be mixed in 20 minutes separating funnel.Then leave standstill and got final product phase-splitting in 15 minutes, lower floor is that the raffinate water is emitted from end opening, and upper organic phase is the saturated alkane solution of the vanadium compound take isooctyl alcohol as part.Sampling analysis vanadium total concn ∑ [V]=0.4579mol/L.Calculate ∑ [ROH]/∑ [V]=2.8, obtain the vanadium compound saturated alkane solution take isooctyl alcohol as part.
With above-mentioned vanadium compound saturated alkane solution take isooctyl alcohol as part, put into flask, add the 1.0mL propionic acid, hexane is removed in the heating air distillation between 70 ℃ under nitrogen protection, obtains blackish green viscous liquid.
Blackish green viscous liquid uses Rotary Evaporators to adopt under 30 ℃ of the underpressure distillation modes, is transferred to behind the reaction 2h in the vacuum drying oven 30 ℃ vacuum-drying to constant weight, obtains blackish green amorphous solid, is vanadium complex of the present invention.Chemical formula is VOCl
2NROH.
Fig. 1 is the mass spectrum of the vanadium complex of embodiment 1 preparation, and the result shows that its chemical formula is VOCl
2NROH.
Embodiment 2 ~ 6
Use successively that isooctyl alcohol is extraction agent in secondary octanol, n-Octanol, nonylcarbinol, n-hexyl alcohol or the primary isoamyl alcohol alternate embodiment 1, carry out the catalyzer preparation with embodiment 1 same procedure, detailed process condition and preparation the results are shown in table 1.
Table 1 embodiment 1 ~ 6 detailed process condition and preparation result
Symbol in the table: [ROH]
0, [NaVO
3], [HCl] represents respectively the Fatty Alcohol(C12-C14 and C12-C18) of adding, NaVO
3The concentration of solution and dense HCl.
Embodiment 7
Install the used reactor of polymerization, keep stopping property, use nitrogen replacement 2-3 time; The vanadium complex, the 4.0mmol aluminium diethyl monochloride (Al (C that add successively 0.1mmol embodiment 1 preparation
2H
5)
2Cl), 0.6mmol ethyl trichloroacetate (ETCA), 2mL ENB, hexane 300mL; Pass into ethene, the propylene mol ratio is the mixed gas of 1:2, the control polymerization pressure is at 0.4MPa, stir, at 20 ℃ of lower reaction 30min, after polymerization finishes, in polymerisate, add the hydrochloric acid-ethanolic soln of mass percent 5%, and use washing with alcohol, and then under vacuum in drying, obtain terpolymer EP rubber 6.6g.
Analyze through differential calorimetry (DSC), the second-order transition temperature of resulting polymers is 57.4 ℃; Warp
13C NMR spectroscopic analysis, resulting polymers in conjunction with propylene molar content (C
3Mol%) be: 44.8%; Through gpc analysis, the number-average molecular weight of resulting polymers is that the two key molar content of 10.4 ten thousand, C=C are: 3.9%, and molecular weight distributing index is 3.7.
Embodiment 8 ~ 13
Install the used reactor of polymerization, keep stopping property, use nitrogen replacement 2-3 time; Add successively 0.1mmol vanadium complex, 4.0mmol organo-aluminium compound, 0.6mmol activation promotor, 2mL ENB, hexane 300mL; Pass into ethene, the propylene mol ratio is the mixed gas of 1:2, the control polymerization pressure is at 0.4MPa, stir, at 20 ℃ of lower reaction 30min, after polymerization finishes, in polymerisate, add the hydrochloric acid-ethanolic soln of mass percent 5%, and use washing with alcohol, and then under vacuum in drying, obtain terpolymer EP rubber.Character to described terpolymer EP rubber is measured, and the result is referring to table 2.Table 2 is the performance of the terpolymer EP rubber of embodiment 8 ~ 13 preparations.
Embodiment 8 ~ 13 used vanadium complexes are respectively the vanadium complex of embodiment 1 ~ 6 preparation, and described organo-aluminium compound is aluminium diethyl monochloride (Al (C
2H
5)
2Cl), described activation promotor is ethyl trichloroacetate (ETCA).
The performance of the terpolymer EP rubber of table 2 embodiment 8 ~ 13 preparations
Embodiment 14 ~ 17
Install the used reactor of polymerization, keep stopping property, use nitrogen replacement 2-3 time; Add successively many vanadium complex, the 4.0mmol ethyl aluminum dichloride (AlC of 0.1mmol embodiment 1 preparation
2H
5Cl
2), 0.6mmol activation promotor, 2mL ENB, hexane 300mL; Pass into ethene, the propylene mol ratio is the mixed gas of 1:2, the control polymerization pressure is at 0.4MPa, stir, at 20 ℃ of lower reaction 30min, after polymerization finishes, in polymerisate, add the hydrochloric acid-ethanolic soln of mass percent 5%, and use washing with alcohol, and then under vacuum in drying, obtain terpolymer EP rubber.Character to described terpolymer EP rubber is measured, and the result is referring to table 3.Table 3 is the performance of the terpolymer EP rubber of embodiment 14 ~ 17 preparations.
The described activation promotor of using among the embodiment 14 ~ 17 is respectively ethyl trichloroacetate (ETCA), CH
3Cl, CH
2Cl
2And CHCl
3
The performance of the terpolymer EP rubber of table 3 embodiment 14 ~ 17 preparations
Embodiment 18 ~ 22
Install the used reactor of polymerization, keep stopping property, use nitrogen replacement 2-3 time; The vanadium complex, the dichloro aluminium isobutyl (AlC that add successively 0.1mmol embodiment 1 preparation by proportioning
4H
9Cl
2), 0.6mmol ethyl trichloroacetate (ETCA), 2mL ENB, hexane 300mL; Pass into ethene, the propylene mol ratio is the mixed gas of 1:2, the control polymerization pressure is at 0.4MPa, stir, at 20 ℃ of lower reaction 30min, after polymerization finishes, in polymerisate, add the hydrochloric acid-ethanolic soln of mass percent 5%, and use washing with alcohol, and then under vacuum in drying, obtain terpolymer EP rubber.
Among the embodiment 18 ~ 22, dichloro aluminium isobutyl (AlC
4H
9Cl
2) add-on be respectively 2.0mmol, 5.0mmol, 6.0mmol, 8.0mmol, 10.0mmol.
Character to described terpolymer EP rubber is measured, and the result is referring to table 4.Table 4 is the performance of the terpolymer EP rubber of embodiment 18 ~ 22 preparations.
The performance of the terpolymer EP rubber of table 4 embodiment 18 ~ 22 preparations
Embodiment 23 ~ 27
Install the used reactor of polymerization, keep stopping property, use nitrogen replacement 2-3 time; Add successively the 150mL normal hexane by proportioning, the vanadium complex of 0.1mmol embodiment 1 preparation, 4.0mmol dichloro aluminium isobutyl (AlC
4H
9Cl
2), ethyl trichloroacetate (ETCA), 2mLENB, 150mL hexanaphthene; Pass into ethene, the propylene mol ratio is the mixed gas of 1:2, the control polymerization pressure is at 0.4MPa, stir, at 20 ℃ of lower reaction 30min, after polymerization finishes, in polymerisate, add the hydrochloric acid-ethanolic soln of mass percent 5%, and use washing with alcohol, and then under vacuum in drying, obtain terpolymer EP rubber.
Among the embodiment 23 ~ 27, the add-on of ethyl trichloroacetate is 0.1mmol, 0.4mmol, 0.8mmol, 1.0mmol, 1.2mmol respectively.
Character to described terpolymer EP rubber is measured, and the result is referring to table 5.Table 5 is the performance of the terpolymer EP rubber of embodiment 23 ~ 27 preparations.
The performance of the terpolymer EP rubber of table 5 embodiment 23 ~ 27 preparations
Embodiment 28 ~ 32
Install the used reactor of polymerization, keep stopping property, use nitrogen replacement 2-3 time; The vanadium complex that adds successively 0.1mmol embodiment 1 preparation by proportioning, 2.0mmol aluminium diethyl monochloride (Al (C
2H
5)
2Cl), 2.0mmol AlC
2H
5Cl
2, 0.6mmol ethyl trichloroacetate (ETCA), 2mL DCPD, hexane 300mL; Pass into ethene, the propylene mol ratio is the mixed gas of 1:2, the control polymerization pressure is at 0.4MPa, stir, react at a certain temperature 30min, after polymerization finishes, in polymerisate, add the hydrochloric acid-ethanolic soln of mass percent 5%, and use washing with alcohol, and then under vacuum in drying, obtain terpolymer EP rubber.
The temperature of reaction of embodiment 28 ~ 32 is respectively 0 ℃, 30 ℃, 40 ℃, 50 ℃ and 70 ℃.
Character to described terpolymer EP rubber is measured, and the result is referring to table 6.Table 6 is the performance of the terpolymer EP rubber of embodiment 28 ~ 32 preparations.
The performance of the terpolymer EP rubber of table 6 embodiment 28 ~ 32 preparations
Embodiment 33 ~ 35
Install the used reactor of polymerization, keep stopping property, use nitrogen replacement 2-3 time; Add successively the vanadium complex that 0.1mmol embodiment 1 prepares, 4.0mmol aluminium diethyl monochloride (Al (C by proportioning
2H
5)
2Cl), ethyl trichloroacetate (ETCA), 2mL1,4-hexadiene, 300mL normal hexane; Pass into ethene, the propylene mol ratio is the mixed gas of 1:2, control certain polymerization pressure, stir, at 20 ℃ of lower reaction 30min, after polymerization finishes, in polymerisate, add the hydrochloric acid-ethanolic soln of mass percent 5%, and use washing with alcohol, and then under vacuum in drying, obtain terpolymer EP rubber.
Among the embodiment 33 ~ 35, polymerization pressure is respectively 0.1MPa, 0.2MPa and 0.6MPa.
Character to described terpolymer EP rubber is measured, and the result is referring to table 7.Table 7 is the performance of the terpolymer EP rubber of embodiment 33 ~ 35 preparations.
The performance of the terpolymer EP rubber of table 7 embodiment 33 ~ 35 preparations
Embodiment 36 ~ 40
Install the used reactor of polymerization, keep stopping property, use nitrogen replacement 2-3 time; Add successively the vanadium complex that embodiment 1 prepares, 4.0mmol aluminium diethyl monochloride (Al (C by proportioning
2H
5)
2Cl), ethyl trichloroacetate (ETCA), 300mL normal hexane; Pass into ethene, the propylene mol ratio is the mixed gas of 1:2, control certain polymerization pressure, stir, at 20 ℃ of lower reaction 30min, after polymerization finishes, in polymerisate, add the hydrochloric acid-ethanolic soln of mass percent 5%, and use washing with alcohol, and then under vacuum in drying, obtain ethylene propylene rubber.
Among the embodiment 36 ~ 40, the addition of the vanadium complex of embodiment 1 preparation is respectively 0.03mmol, 0.15mmol, 0.3mmol, 0.45mmol, 0.6mmol.
Character to described ethylene propylene rubber is measured, and the result is referring to table 8.Table 8 is the performance of the ethylene propylene rubber of embodiment 36 ~ 40 preparations.
The performance of the ethylene propylene rubber of table 8 embodiment 36 ~ 40 preparations
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be apparent concerning those skilled in the art, and General Principle as defined herein can in the situation that does not break away from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. vanadium complex as shown in the formula (I),
VOCl
2·nROH（I）；
Wherein, R is the alkyl of C5 ~ C10,1≤n≤3.
2. the preparation method of a vanadium complex may further comprise the steps:
Fatty Alcohol(C12-C14 and C12-C18) and mixing diluents with C5 ~ C10 obtain diluent; Described thinner is the saturated alkane of C6 ~ C8;
After described diluent, the sodium metavanadate aqueous solution and concentrated hydrochloric acid hybrid reaction, extract, obtain vanadium complex saturated alkane solution;
After the ratio of Fatty Alcohol(C12-C14 and C12-C18) volumetric molar concentration and vanadium volumetric molar concentration in the described vanadium complex saturated alkane solution is adjusted to 2.5 ~ 3.5, carry out air distillation, obtain intermediate product;
Described intermediate product is carried out underpressure distillation process under the stablizer protection, obtain vanadium complex as shown in the formula (I) after the drying; Described stablizer is mass concentration less than the lipid acid of C2 ~ C4 of 1%;
VOCl
2·nROH（I）；
Wherein, R is the alkyl of C5 ~ C10,1≤n≤3.
3. preparation method according to claim 2 is characterized in that, the temperature of described underpressure distillation is 0 ~ 30 ℃, and the time of described underpressure distillation is 1 ~ 4 hour.
4. preparation method according to claim 2 is characterized in that, the temperature of described drying is 20 ~ 40 ℃.
5. preparation method according to claim 2 is characterized in that, described Fatty Alcohol(C12-C14 and C12-C18) is the saturated fatty alcohol of C6 ~ C8.
6. a vanadium catalyst composition comprises as shown in the formula (I) vanadium complex, organo-aluminium compound and activation promotor;
Described activation promotor is haloalkane or ester class;
The mol ratio of described organo-aluminium compound and vanadium complex is 20 ~ 100:1;
The mol ratio of described activation promotor and vanadium complex is 1 ~ 20:1;
VOCl
2·nROH（I）；
Wherein, R is the alkyl of C5 ~ C10,1≤n≤3.
7. catalyst composition according to claim 1 is characterized in that, described activation promotor is ethyl trichloroacetate, CH
3Cl, CH
2Cl
2Or CHCl
3
8. catalyst composition according to claim 1 is characterized in that, described organo-aluminium compound is one or more in trichlorine triethyl two aluminium, ethyl aluminum dichloride, aluminium diethyl monochloride and the dichloro aluminium isobutyl.
9. the preparation method of an ethylene propylene rubber may further comprise the steps:
In organic solvent, ethene and propylene are under catalyst composition effect claimed in claim 8, and polymerization reaction take place obtains ethylene propylene rubber.
10. the preparation method of a terpolymer EP rubber may further comprise the steps:
In organic solvent, ethene, propylene and non-conjugated diene are under catalyst composition effect claimed in claim 8, and polymerization reaction take place obtains terpolymer EP rubber.
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