CN103923246A - Preparation method of catalyst containing trivalent vanadium, vanadium catalyst composition and application thereof - Google Patents
Preparation method of catalyst containing trivalent vanadium, vanadium catalyst composition and application thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a catalyst containing trivalent vanadium. The preparation method comprises the steps of dissolving vanadium pentoxide or sodium metavanadate with concentration sulfuric acid or concentrated hydrochloric acid, reacting under the action of oxalic acid, and controlling the pH value to be 2-4; then adding sodium sulfite or sodium hydrosulfite to react, and controlling the pH value to be 5.5-7, thus obtaining a water solution containing a trivalent vanadium compound; mixing the water solution containing the trivalent vanadium compound, a saturated alkane solution containing an extraction agent and an extraction aid and 0.5-2mol/L of sodium hydroxide solution and stirring the materials, and discharging the water phase after oscillating and layering, thus obtaining the catalyst containing trivalent vanadium, wherein the extraction agent is organic carboxylic acid; the extraction aid is organic monobasic phosphoric acid or organophosphate. The preparation method is simple. The obtained catalyst has good stability and safety; when the catalyst is used for preparing ethylene propylene rubber (EPR), the cost can be reduced, and EPR with excellent properties can be obtained.
Description
Technical field
The present invention relates to ethylene-propylene rubber(EPR) catalyst field, particularly contain preparation method, vanadium catalyst composition and the application thereof of the catalyzer of trivalent vanadium.
Background technology
Ethylene-propylene rubber(EPR) production is both at home and abroad catalyzer mainly with vanadium sub-group compound, and in these vanadium sub-group compounds, the valence state of vanadium is generally trivalent, tetravalence or pentavalent.Wherein trivalent vanadium compound is less for the preparation of the research of ethylene-propylene rubber(EPR), mainly contains at present VCl
3, V (acac)
3, V
5-9acid compound and V
5-9-Et
3al
2cl
3system.
In the mechanism research to vanadium series catalyst catalyzed ethylene and copolymerization of propylene, (C.Lorber, B.Dommadieu and E.Choukroun Organometallic, 2000,19,1963.), about the vanadium valence state in active centre, think that active substance is V-Al complex compound, V
3+become V
2+just lost activity.G.Natta (Natta, G.; Paquon, I.and A., Z.J.Am.Chem.Soc.1962,84,1488-1490.) etc., according to paramagnetic resonance research, also think that active centre is RVCl
2the V of type
3+, thermolysis forms V
2+vCl
2, lose activity.Therefore, from above-mentioned Copolymerization Mechanism, with V
3+compound, as the Primary Catalysts of producing ethylene-propylene rubber(EPR), can reach raising polymerization activity, saves the object of the consumption of alkylaluminium cpd, but due to V
3+the valence state of compound is difficult for stable, and existing several V
3+the preparation of compound and use exist a large amount of problems.
For example, VCl
3, be by V equally
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, volatile, toxicity is large, meet air decomposes, meets water blast, thereby brings inconvenience to storage, transportation and use.Five or nine acid, as paraffin oxidation by product, are originated at that time abundant, low price, and five or nine sour vanadium (are write a Chinese character in simplified form V
5-9) dissolve in again fat hydrocarbon solvent, but in its building-up process, need to under high temperature, reduce vanadium+5 valency oxide compound (V
2o
5) and synthesize V
3+oxide compound (the V of vanadium
2o
3), complex process, high to equipment requirements, and there is no now five or nine acid products, cannot be applied in industrial production.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of preparation method, vanadium catalyst composition and application thereof of the catalyzer that contains trivalent vanadium, and the method for preparing catalyst that the present invention contains trivalent vanadium is simple, safety and environmental protection, and catalytic activity is high.
The preparation method who the invention discloses a kind of catalyzer that contains trivalent vanadium, comprises the following steps:
(A) Vanadium Pentoxide in FLAKES or sodium metavanadate are dissolved with the vitriol oil or concentrated hydrochloric acid, under oxalic acid effect, react, controlling pH value is 2～4;
And then add S-WAT or V-Brite B reaction, controlling pH value is 5.5～7, obtains the aqueous solution that contains trivalent vanadium compound;
(B) by the described aqueous solution that contains trivalent vanadium compound, contain extraction agent and help the extraction saturated alkane solution of agent and the sodium hydroxide solution mix and blend of 0.5～2mol/L, after concussion layering, discharge water, obtain the catalyzer that contains trivalent vanadium;
Described extraction agent is organic carboxyl acid; Described help extraction agent be organic monobasic phosphoric acid or organophosphate.
Preferably, described step (A) is specially:
By Vanadium Pentoxide in FLAKES concentrated sulfuric acid dissolution, under oxalic acid effect, react, controlling pH value is 2～4;
Then add S-WAT reaction, controlling pH value is 5.5～7, obtains the aqueous solution that contains trivalent vanadium compound.
Preferably, described step (A) is specially:
Sodium metavanadate is dissolved with concentrated hydrochloric acid, under oxalic acid effect, react, controlling pH value is 2～4;
Then add V-Brite B reaction, controlling pH value is 5.5～7, obtains the aqueous solution that contains trivalent vanadium compound.
Preferably, in described step (B), the described quality percentage composition containing helping extraction agent in the saturated alkane solution that extracts agent and extraction agent is greater than 50%.
Preferably, in described step (B), described in contain trivalent vanadium compound the aqueous solution be 1:1～3:1 with containing extraction agent and helping the volume ratio of saturated alkane solution of extraction agent.
Preferably, in described step (B), the mol ratio of described extraction agent and vanadium is 3:1～18:1.
Preferably, in described step (B), the mol ratio of described extraction agent and sodium hydroxide is 0.75～1.05:1.
The invention provides a kind of vanadium catalyst composition, comprise the catalyzer that contains trivalent vanadium that prepared by method described in technique scheme, activation promotor and organo-aluminium compound.
Preferably, described in contain trivalent vanadium catalyzer in the ratio of the mole number of vanadium and the mole number of organo-aluminium compound be 1:20～100, described in contain trivalent vanadium catalyzer in the mole number of vanadium be 1:2～20 with the ratio of the mole number of activation promotor.
The present invention also provides the application in preparing ethylene-propylene rubber(EPR) of vanadium catalyst composition described in a kind of technique scheme.
Compared with prior art, the preparation method of the catalyzer that the present invention contains trivalent vanadium is: Vanadium Pentoxide in FLAKES or sodium metavanadate are dissolved with the vitriol oil or concentrated hydrochloric acid, under oxalic acid effect, react, controlling pH value is 2～4; And then add S-WAT or V-Brite B reaction, controlling pH value is 5.5～7, obtains the aqueous solution that contains trivalent vanadium compound; By the described aqueous solution that contains trivalent vanadium compound, contain extraction agent and help the extraction saturated alkane solution of agent and the sodium hydroxide solution mix and blend of 0.5～2mol/L, after concussion layering, discharge water, obtain the catalyzer that contains trivalent vanadium; Described extraction agent is organic carboxyl acid; Described help extraction agent be organic monobasic phosphoric acid or organophosphate.
The present invention adopts water synthetic, then through extraction, obtains the catalyzer that contains trivalent vanadium.In described preparation method, trivalent vanadium compound water solution preparation is simple, usings that it can directly synthesize as intermediate the organic compound that contains trivalent vanadium in extraction, thereby obtains the catalyzer that contains trivalent vanadium.Preparation method of the present invention is simple, and the catalyzer obtaining all has satisfactory stability in water and air.In the catalyzer that contains trivalent vanadium prepared by the present invention, trivalent vanadium is the active centre of catalyzed ethylene and propylene polymerization, can be directly and alkylaluminium cpd react, compare with the vanadium compound of other tetravalences or pentavalent, can reach minimizing aluminum alkyls and use, reduce the effect of ethylene-propylene rubber(EPR) cost.Experimental result shows, the catalyst activity that contains trivalent vanadium prepared by the present invention is higher than VOCl
3, it is wide that its catalysis prepares ethylene-propylene rubber(EPR) molecular weight distribution, and physical and mechanical properties is good, is conducive to following process.
Accompanying drawing explanation
Fig. 1 is that the catalyzer that contains vanadium (III) of embodiment 1 preparation carries out ultra-violet absorption spectrum.
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 are described is for further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention.
The preparation method who the embodiment of the invention discloses a kind of catalyzer that contains trivalent vanadium, comprises the following steps:
(A) Vanadium Pentoxide in FLAKES or sodium metavanadate are dissolved with the vitriol oil or concentrated hydrochloric acid, under oxalic acid aqueous solution effect, react, controlling pH value is 2～4;
And then add S-WAT or V-Brite B reaction, controlling pH value is 5.5～7, obtains the aqueous solution that contains trivalent vanadium compound;
(B) by the described aqueous solution that contains trivalent vanadium compound, contain extraction agent and help the extraction saturated alkane solution of agent and the sodium hydroxide solution mix and blend of 0.5～2mol/L, after concussion layering, discharge water, obtain the catalyzer that contains trivalent vanadium;
Described extraction agent is organic carboxyl acid; Described help extraction agent be organic monobasic phosphoric acid or organophosphate.
In the present invention, take Vanadium Pentoxide in FLAKES or sodium metavanadate as raw material, first described Vanadium Pentoxide in FLAKES or sodium metavanadate are dissolved with the vitriol oil or concentrated hydrochloric acid, under oxalic acid aqueous solution effect, react.The mass percentage concentration of described oxalic acid aqueous solution is preferably 5～12%.Described oxalic acid provides hydrogen ion for reaction on the one hand, on the one hand as reductive agent, Vanadium Pentoxide in FLAKES or sodium metavanadate is reduced.It is 2～4 that pH is controlled in described reaction, more preferably 2.1～3.8.After described reaction, then add S-WAT or V-Brite B reaction, control pH5.5～7, obtain the aqueous solution that contains trivalent vanadium compound.Described S-WAT or V-Brite B are reductive agent, and the product after oxalic acid reduction is carried out to secondary reduction, by controlling pH value, finally obtain the aqueous solution that contains trivalent vanadium compound.
Described step is preferably: by Vanadium Pentoxide in FLAKES concentrated sulfuric acid dissolution, under oxalic acid effect, react, controlling pH value is 2～4; Then add S-WAT reaction, controlling pH value is 5.5～7, obtains the aqueous solution that contains trivalent vanadium compound.
The mol ratio of described oxalic acid and Vanadium Pentoxide in FLAKES is preferably 1.05～1.5:1.The mass ratio of the described vitriol oil and oxalic acid is preferably 1.05～1.5:1.The mol ratio of described Vanadium Pentoxide in FLAKES and S-WAT is preferably 1:3～1:8.
Or be preferably:
Sodium metavanadate is dissolved with concentrated hydrochloric acid, under oxalic acid effect, react, controlling pH value is 2～4; Then add V-Brite B reaction, controlling pH value is 5.5～7, obtains the aqueous solution that contains trivalent vanadium compound.
The mol ratio of described oxalic acid and sodium metavanadate is preferably 1.05～1.5:1.The mass ratio of described concentrated hydrochloric acid and oxalic acid is 2.1:1～3:1.The mol ratio of described sodium metavanadate and V-Brite B is 2:1.5～2:3.
Described in obtaining, contain after the aqueous solution of trivalent vanadium compound, preferably through titration, obtain the mole number of trivalent vanadium in the described aqueous solution, so that subsequent reactions.
In the present invention, by the described aqueous solution containing trivalent vanadium compound, containing helping extraction agent and the saturated alkane solution of extraction agent and the sodium hydroxide solution mix and blend of 0.5～2mol/L, after concussion layering, discharge water, obtain the catalyzer that contains trivalent vanadium;
Described extraction agent is organic carboxyl acid, is preferably the aliphatic carboxylic acid of C5～C10, more preferably sad or isocaprylic acid; Described help extraction agent be organic monobasic phosphoric acid or organophosphate, be preferably P
204or P
507.Described saturated alkane is preferably the aliphatics saturated alkane of C5～C10, more preferably hexane, hexanaphthene or octane.The present invention is by extraction agent and the mating reaction that helps extraction agent, and vanadium is extracted to and is take the organic phase that saturated alkane is solvent from water with the form of organic carboxyl acid vanadium compound, and vanadium atom exists with trivalent form in saturated alkane solvent.The described quality percentage composition containing helping extraction agent in the saturated alkane solution of extraction agent and extraction agent is preferably greater than 50%, and more preferably 60%～90%.The mol ratio of described extraction agent and vanadium is preferably 3:1～18:1.The described aqueous solution that contains trivalent vanadium compound is preferably 1:1～3:1 with the volume ratio containing helping the saturated alkane solution of extraction agent and extraction agent, more preferably 1.05:1～2:1.The mol ratio of described extraction agent and sodium hydroxide is preferably 0.75～1.05:1.
The invention discloses a kind of vanadium catalyst composition, comprise the catalyzer that contains trivalent vanadium that prepared by method described in technique scheme, activation promotor and organo-aluminium compound.
In vanadium catalyst composition of the present invention, comprise described activation promotor, its effect is to make deactivated bivalent vanadium compound oxidation become activated trivalent vanadium compound, increases the number in active centre, the active lifetime that activation promotor can extend growing chain, makes active centre stable.Described activation promotor is preferably halogenated alkane or ester class, ethyl trichloroacetate more preferably, CH
3cl, CH
2cl
2or CHCl
3.
In vanadium catalyst composition of the present invention, include machine aluminium compound, there is auxiliary catalysis effect.Described organo-aluminium compound is preferably one or more in trichlorine triethyl two aluminium, ethyl aluminum dichloride, aluminium diethyl monochloride and dichloro aluminium isobutyl, more preferably one or both in ethyl aluminum dichloride and aluminium diethyl monochloride.The present invention is also not particularly limited the source of described alkylaluminium cpd, can be bought by market.
In the described catalyzer that contains trivalent vanadium, the ratio of the mole number of vanadium and the mole number of organo-aluminium compound is preferably 1:20～100, more preferably 1:30～80; In the described catalyzer that contains trivalent vanadium, the mole number of vanadium is preferably 1:2～20, more preferably 1:3～15 with the ratio of the mole number of activation promotor.
The invention also discloses the application in preparing ethylene-propylene rubber(EPR) of vanadium catalyst composition described in technique scheme.
Vanadium catalyst composition described in technique scheme can, for the preparation of ethylene propylene rubber, also can be prepared terpolymer EP rubber.
The method of utilizing vanadium catalyst composition described in technique scheme to prepare ethylene propylene rubber is:
In organic solvent, ethene and propylene are under the catalyst composition effect described in technique scheme, and polymerization reaction take place, obtains ethylene propylene rubber.
In the present invention, the concentration of organic vanadium (III) compound in organic solvent shown in 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 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.
After described polyreaction finishes, preferably pass through aftertreatment, obtain ethylene propylene rubber.Described last handling process is preferably the product of polyreaction is joined in hydrochloric acid-ethanolic soln, and the mass percent of described hydrochloric acid is 5%, and after filtration, by washing with alcohol precipitation, then vacuum-drying, obtains final ethylene propylene rubber.
The method of utilizing vanadium catalyst composition described in technique scheme to prepare terpolymer EP rubber is:
In organic solvent, ethene, propylene and non-conjugated diene are under the catalyst composition effect described in technique scheme, and polymerization reaction take place, obtains terpolymer EP rubber.
In the present invention, in described catalyst composition, the concentration of organic vanadium (III) compound in organic solvent 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 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.
After described polyreaction finishes, preferably pass through aftertreatment, obtain terpolymer EP rubber.Described last handling process is preferably the product of polyreaction is joined in hydrochloric acid-ethanolic soln, and the mass percent of described hydrochloric acid is 5%, and after filtration, by washing with alcohol precipitation, then vacuum-drying, obtains final terpolymer EP rubber.
Ethylene-propylene rubber(EPR) prepared by the present invention is analyzed through DSC, NMR, IR and high temperature GPC, and result shows, ethylene-propylene rubber(EPR) molecular weight distribution prepared by the present invention is wide, is conducive to post-treatment.
In order further to understand the present invention, below in conjunction with embodiment, the preparation method of the catalyzer that contains trivalent vanadium provided by the invention, vanadium catalyst composition and application thereof are described, protection scope of the present invention is not limited by the following examples.
Embodiment 1
(1) by 5g V
2o
5(Vanadium Pentoxide in FLAKES) adds 50mL to contain the dense H of 3.5mL
2sO
4acidic aqueous solution in, be heated to 70 ℃, then 3.7g oxalic acid slowly added wherein, controlling pH value is 2.2.At 70 ℃, stir, treat V
2o
5after (Vanadium Pentoxide in FLAKES) dissolves completely, more slowly add 21.2g Na in batches
2sO
3, after it all dissolves, at 70 ℃, stir 2h, green vanadium (III) compound water solution, controlling pH value is 6, as the intermediate of synthetic vanadium catalyst.Described vanadium (III) compound water solution is carried out to titration, obtain the content of trivalent vanadium.
(2) molar content of the vanadium of obtaining is vanadium oxalate (III) the solution 35ml of 4mmol;
(3) preparation is containing 2.5mL extraction agent isocaprylic acid, and the P507 of 12mL1.0mol/L helps the organic phase cyclohexane solution 20mL of extraction agent;
(4) preparation is containing the aqueous solution 5mL of 1.0gNaOH;
By the solution mix and blend 5min of above-mentioned (3) and (4), the solution of acquisition adds in the vanadium oxalate solution in (2), through vibration layering, gets rid of water, and organic phase is the catalyzer that contains vanadium (III).
Through analyzing purity, the concentration of the catalyzer that vanadium (III) is contained in Yi Fanwei unit is 0.1mol/L.
The catalyzer that contains vanadium (III) obtaining is carried out to ultraviolet absorption spectroscopy, and referring to Fig. 1, Fig. 1 is that the catalyzer that contains vanadium (III) of embodiment 1 preparation carries out ultra-violet absorption spectrum.By Fig. 1, can qualitatively be illustrated, in catalyzer prepared by the present invention, contain trivalent vanadium.In Fig. 1, A curve is that the catalyst dilution that contains vanadium (III) prepared by embodiment 1 is the ultra-violet absorption spectrum after 0.04mol/L; B curve is that the catalyst dilution that contains vanadium (III) prepared by embodiment 1 is the ultra-violet absorption spectrum after 0.02mol/L; C curve is that the catalyst dilution that contains vanadium (III) prepared by embodiment 1 is the ultra-violet absorption spectrum after 0.005mol/L.
Embodiment 2
(1) first that 3.0g oxalic acid is soluble in water, the oxalic acid aqueous solution of preparation 60mL, stirs and adds 4.0g sodium metavanadate thereupon, is warming up to 65 ℃, then 11.5mL concentrated hydrochloric acid is slowly added wherein, and controlling pH value is 3, forms oxalic acid tetravalence vanadium solution;
With stirring, in gained solution, add 8.2g V-Brite B to react, controlling pH value is 6.4 again, forms trivalent vanadium mixture solution;
Adopt analyzing purity concentration stand-by above-mentioned+3 valency vanadium oxalate solution, as the intermediate that synthesizes vanadium catalyst.
(2) molar content of the vanadium of obtaining is vanadium oxalate (III) the solution 15ml of 4mmol;
(3) preparation is containing 0.65mL extraction agent isocaprylic acid, and the P507 of 12mL1.0mol/L helps the organic phase cyclohexane solution 20mL of extraction agent;
(4) preparation is containing the aqueous solution 5mL of 0.6gNaOH;
By the solution mix and blend 5min of above-mentioned (3) and (4), the solution of acquisition adds in the vanadium oxalate solution in (2), through vibration layering, gets rid of water, and organic phase is the catalyzer that contains vanadium (III).
Through analyzing purity, the concentration of the catalyzer that vanadium (III) is contained in Yi Fanwei unit is 0.2mol/L.
Embodiment 3
Install polymerization reactor used, keep stopping property, use nitrogen replacement 2-3 time; The catalyzer that contains vanadium (III), 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; The mixed gas that to pass into ethene, propylene mol ratio be 1:2, control polymerization pressure at 0.4MPa, stir, at 20 ℃, react 30min, after polymerization finishes, in polymerisate, add the hydrochloric acid-ethanolic soln of mass percent 5%, and by washing with alcohol, and then under vacuum in dry, obtain terpolymer EP rubber 16.7g.
Through differential calorimetry (DSC), analyze, the second-order transition temperature of resulting polymers is 57.4 ℃; Warp
13c NMR spectroscopic analysis, the combination propylene molar content (C of resulting polymers
3mol%) be: 34.5%; Through gpc analysis, the number-average molecular weight of resulting polymers is that the two key molar content of 11.4 ten thousand, C=C are: 3.9%, and molecular weight distributing index is 2.7.
Embodiment 4
Install polymerization reactor used, keep stopping property, use nitrogen replacement 2-3 time; The catalyzer 0.1mmol that contains vanadium (III) that adds successively embodiment 2 preparations by proportioning, 4.0mmol aluminium diethyl monochloride (Al (C
2h
5)
2cl), 0.6mmol ethyl trichloroacetate (ETCA), 300ml normal hexane; The mixed gas that to pass into ethene, propylene mol ratio be 1:2, control certain polymerization pressure, stir, at 20 ℃, react 30min, after polymerization finishes, in polymerisate, add the hydrochloric acid-ethanolic soln of mass percent 5%, and by washing with alcohol, and then under vacuum in dry, obtain ethylene propylene rubber 14.8g.
Through differential calorimetry (DSC), analyze, the second-order transition temperature of resulting polymers is 56.5 ℃; Warp
13c NMR spectroscopic analysis, the combination propylene molar content (C of resulting polymers
3mol%) be: 32.5%; Through gpc analysis, the number-average molecular weight of resulting polymers is 10.4 ten thousand, and molecular weight distributing index is 3.4.
Embodiment 5～8
The preparation of the catalyzer that contains vanadium (III), selects extraction agent isocaprylic acid to use 1.3ml, helps the P of extraction agent 1mol/L
507use 16ml, other preparation conditions and step are with embodiment 1.
Install polymerization reactor used, keep stopping property, use nitrogen replacement 2-3 time; The catalyzer that contains vanadium (III), the 4.0mmol ethyl aluminum dichloride (AlC that add successively 0.1mmol aforesaid method to obtain
2h
5cl
2), 0.6mmol activation promotor, 2ml ENB, hexane 300ml; The mixed gas that to pass into ethene, propylene mol ratio be 1:2, control polymerization pressure at 0.4MPa, stir, at 20 ℃, react 30min, after polymerization finishes, in polymerisate, add the hydrochloric acid-ethanolic soln of mass percent 5%, and by washing with alcohol, and then under vacuum in dry, obtain terpolymer EP rubber.Character to described terpolymer EP rubber is measured, and result is referring to table 1.Table 1 is the performance of the terpolymer EP rubber of embodiment 5～8 preparations.
The described activation promotor of using in embodiment 5～8 is respectively ethyl trichloroacetate (ETCA), CH
3cl, CH
2cl
2and CHCl
3.
The structural parameter of the terpolymer EP rubber of table 1 embodiment 5～8 preparations
Embodiment 9～13
The preparation of the catalyzer that contains vanadium (III), selects extraction agent isocaprylic acid to use 2.5ml, helps the P of extraction agent 1mol/L
507use 12ml, other preparation conditions and step are with embodiment 1.
Install polymerization reactor used, keep stopping property, use nitrogen replacement 2-3 time; The catalyzer that contains vanadium (III), the dichloro aluminium isobutyl (AlC that by proportioning, add successively 0.1mmol aforesaid method to prepare
4h
9c
l2), 0.6mmol ethyl trichloroacetate (ETCA), 2ml ENB, hexane 300ml; The mixed gas that to pass into ethene, propylene mol ratio be 1:2, control polymerization pressure at 0.4MPa, stir, at 20 ℃, react 30min, after polymerization finishes, in polymerisate, add the hydrochloric acid-ethanolic soln of mass percent 5%, and by washing with alcohol, and then under vacuum in dry, obtain terpolymer EP rubber.
In embodiment 9～13, 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 result is referring to table 2.Table 2 is the performance of the terpolymer EP rubber of embodiment 9～13 preparations.
The structural parameter of the terpolymer EP rubber of table 2 embodiment 9～13 preparations
Embodiment 14～18
The preparation of the catalyzer that contains vanadium (III), selects extraction agent isocaprylic acid to use 2.5ml, helps the P of extraction agent 1mol/L
507use 8ml, other preparation conditions and step are with embodiment 1.
Install polymerization reactor used, keep stopping property, use nitrogen replacement 2-3 time; By proportioning, add successively 150ml normal hexane, the catalyzer that contains vanadium (III) prepared by 0.1mmol aforesaid method, 4.0mmol dichloro aluminium isobutyl (AlC
4h
9c
l2), ethyl trichloroacetate (ETCA), 2ml ENB, 150ml hexanaphthene; The mixed gas that to pass into ethene, propylene mol ratio be 1:2, control polymerization pressure at 0.4MPa, stir, at 20 ℃, react 30min, after polymerization finishes, in polymerisate, add the hydrochloric acid-ethanolic soln of mass percent 5%, and by washing with alcohol, and then under vacuum in dry, obtain terpolymer EP rubber.
In embodiment 14～18, 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 result is referring to table 3.Table 3 is the performance of the terpolymer EP rubber of embodiment 14～18 preparations.
The structural parameter of the terpolymer EP rubber of table 3 embodiment 14～18 preparations
Embodiment 19～23
The preparation of the catalyzer that contains vanadium (III), selects extraction agent isocaprylic acid to use 3.2ml, helps the P of extraction agent 1mol/L
507use 4ml, other preparation conditions and step are with embodiment 2.
Install polymerization reactor used, keep stopping property, use nitrogen replacement 2-3 time; The catalyzer that contains vanadium (III) that adds 0.1mmol aforesaid method to prepare by proportioning successively, 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; The mixed gas that to pass into ethene, propylene mol ratio be 1:2, control polymerization pressure 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 by washing with alcohol, and then under vacuum in dry, obtain terpolymer EP rubber.
The temperature of reaction of embodiment 19～23 is respectively 0 ℃, 30 ℃, 40 ℃, 50 ℃ and 70 ℃.
Character to described terpolymer EP rubber is measured, and result is referring to table 4.Table 4 is the performance of the terpolymer EP rubber of embodiment 19～23 preparations.
The structural parameter of the terpolymer EP rubber of table 4 embodiment 19～23 preparations
Embodiment 24～26
The preparation of the catalyzer that contains vanadium (III), selects extraction agent isocaprylic acid to use 0.6ml, helps the P of extraction agent 1mol/L
507use 20ml, other preparation conditions and step are with embodiment 2.
Install polymerization reactor used, keep stopping property, use nitrogen replacement 2-3 time; The catalyzer that contains vanadium (III) that adds successively 0.1mmol aforesaid method to prepare by proportioning, 4.0mmol aluminium diethyl monochloride (Al (C
2h
5)
2cl), 0.6mmol ethyl trichloroacetate (ETCA), 2ml1,4-hexadiene, 300ml normal hexane; The mixed gas that to pass into ethene, propylene mol ratio be 1:2, control certain polymerization pressure, stir, at 20 ℃, react 30min, after polymerization finishes, in polymerisate, add the hydrochloric acid-ethanolic soln of mass percent 5%, and by washing with alcohol, and then under vacuum in dry, obtain terpolymer EP rubber.
In embodiment 24～26, polymerization pressure is respectively 0.1MPa, 0.2MPa and 0.6MPa.
Character to described terpolymer EP rubber is measured, and result is referring to table 5.Table 5 is the performance of the terpolymer EP rubber of embodiment 24～26 preparations.
The structural parameter of the terpolymer EP rubber of table 5 embodiment 24～26 preparations
Embodiment 27～31
The preparation of the catalyzer that contains vanadium (III), selects extraction agent isocaprylic acid to use 0.7ml, helps the P of extraction agent 1.0mol/L
204help extraction agent 12ml, other preparation conditions and step are with embodiment 2.
Install polymerization reactor used, keep stopping property, use nitrogen replacement 2-3 time; The catalyzer that contains vanadium (III) that adds successively aforesaid method to prepare by proportioning, 4.0mmol aluminium diethyl monochloride (Al (C
2h
5)
2cl), 0.6mmol ethyl trichloroacetate (ETCA), 300ml normal hexane; The mixed gas that to pass into ethene, propylene mol ratio be 1:2, control certain polymerization pressure, stir, at 20 ℃, react 30min, after polymerization finishes, in polymerisate, add the hydrochloric acid-ethanolic soln of mass percent 5%, and by washing with alcohol, and then under vacuum in dry, obtain ethylene propylene rubber.
In embodiment 27～31, the addition of organic vanadium (III) compound is respectively 0.03mmol, 0.15mmol, 0.3mmol, 0.45mmol, 0.6mmol.
Character to described ethylene propylene rubber is measured, and result is referring to table 6.Table 6 is the performance of the ethylene propylene rubber of embodiment 27～31 preparations.
The structural parameter of the ethylene propylene rubber of table 6 embodiment 27～31 preparations
Comparative example 1
Install polymerization reactor used, keep stopping property, use nitrogen replacement 2-3 time; By proportioning, add successively 0.15mmol VOCl
3, 4.0mmol aluminium diethyl monochloride (Al (C
2h
5)
2cl), 0.6mmol ethyl trichloroacetate (ETCA), 300ml normal hexane; The mixed gas that to pass into ethene, propylene mol ratio be 1:2, control certain polymerization pressure, stir, at 20 ℃, react 30min, after polymerization finishes, in polymerisate, add the hydrochloric acid-ethanolic soln of mass percent 5%, and by washing with alcohol, and then under vacuum in dry, obtain ethylene propylene rubber.
The method of preparing ethylene-propylene rubber(EPR) of use as shown in embodiment 28, the catalyzer that application contains vanadium (III) and the VOCl of industrial production ethylene-propylene rubber(EPR)
3vanadium series catalyst is prepared ethylene-propylene rubber(EPR) and contrasts, and the results are shown in following table:
In table 7 embodiment 28 and comparative example 1, adopt different catalysts to prepare the structural parameter comparison of ethylene-propylene rubber(EPR)
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles 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 the claims in the present invention.
Above-mentioned explanation to the disclosed embodiments, makes professional and technical personnel in the field can realize or use the present invention.To the multiple modification of these embodiment, will be apparent for those skilled in the art, General Principle as defined herein can, in the situation that not departing 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. a preparation method who contains the catalyzer of trivalent vanadium, comprises the following steps:
(A) Vanadium Pentoxide in FLAKES or sodium metavanadate are dissolved with the vitriol oil or concentrated hydrochloric acid, under oxalic acid effect, react, controlling pH value is 2～4;
And then add S-WAT or V-Brite B reaction, controlling pH value is 5.5～7, obtains the aqueous solution that contains trivalent vanadium compound;
(B) by the described aqueous solution that contains trivalent vanadium compound, contain extraction agent and help the extraction saturated alkane solution of agent and the sodium hydroxide solution mix and blend of 0.5～2mol/L, after concussion layering, discharge water, obtain the catalyzer that contains trivalent vanadium;
Described extraction agent is organic carboxyl acid; Described help extraction agent be organic monobasic phosphoric acid or organophosphate.
2. preparation method according to claim 1, is characterized in that, described step (A) is specially:
By Vanadium Pentoxide in FLAKES concentrated sulfuric acid dissolution, under oxalic acid effect, react, controlling pH value is 2～4;
Then add S-WAT reaction, controlling pH value is 5.5～7, obtains the aqueous solution that contains trivalent vanadium compound.
3. preparation method according to claim 1, is characterized in that, described step (A) is specially:
Sodium metavanadate is dissolved with concentrated hydrochloric acid, under oxalic acid effect, react, controlling pH value is 2～4;
Then add V-Brite B reaction, controlling pH value is 5.5～7, obtains the aqueous solution that contains trivalent vanadium compound.
4. according to the preparation method described in claim 2 or 3 any one, it is characterized in that, in described step (B), the described quality percentage composition containing helping extraction agent in the saturated alkane solution that extracts agent and extraction agent is greater than 50%.
5. preparation method according to claim 4, is characterized in that, in described step (B), described in contain trivalent vanadium compound the aqueous solution be 1:1～3:1 with containing extraction agent and helping the volume ratio of saturated alkane solution of extraction agent.
6. preparation method according to claim 4, is characterized in that, in described step (B), the mol ratio of described extraction agent and vanadium is 3:1～18:1.
7. preparation method according to claim 4, is characterized in that, in described step (B), the mol ratio of described extraction agent and sodium hydroxide is 0.75～1.05:1.
8. a vanadium catalyst composition, comprises the catalyzer that contains trivalent vanadium that prepared by method described in claim 1～7 any one, activation promotor and organo-aluminium compound.
9. catalyst composition according to claim 8, it is characterized in that, in the described catalyzer that contains trivalent vanadium, the ratio of the mole number of vanadium and the mole number of organo-aluminium compound is 1:20～100, described in contain trivalent vanadium catalyzer in the mole number of vanadium be 1:2～20 with the ratio of mole number of activation promotor.
10. the application of vanadium catalyst composition claimed in claim 8 in preparing ethylene-propylene rubber(EPR).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105413589A (en) * | 2015-11-13 | 2016-03-23 | 中国石油集团东北炼化工程有限公司吉林设计院 | Method for discharging catalysts for ethylene propylene rubber production |
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| CN1583810A (en) * | 2004-06-03 | 2005-02-23 | 中国科学院长春应用化学研究所 | Preparing technology for production of EPT rubber vanadium catalyst |
| CN101362684A (en) * | 2008-07-23 | 2009-02-11 | 郑德龙 | Solution containing vanadium oxalate and preparation method thereof |
| CN102964375A (en) * | 2012-11-28 | 2013-03-13 | 中国科学院长春应用化学研究所 | Vanadium catalyst, vanadium catalyst composition and preparation method of ethylene propylene rubber |
| CN103319326A (en) * | 2012-03-23 | 2013-09-25 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method for vanadyl oxalate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1583810A (en) * | 2004-06-03 | 2005-02-23 | 中国科学院长春应用化学研究所 | Preparing technology for production of EPT rubber vanadium catalyst |
| CN101362684A (en) * | 2008-07-23 | 2009-02-11 | 郑德龙 | Solution containing vanadium oxalate and preparation method thereof |
| CN103319326A (en) * | 2012-03-23 | 2013-09-25 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method for vanadyl oxalate |
| CN102964375A (en) * | 2012-11-28 | 2013-03-13 | 中国科学院长春应用化学研究所 | Vanadium catalyst, vanadium catalyst composition and preparation method of ethylene propylene rubber |
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| CN105413589A (en) * | 2015-11-13 | 2016-03-23 | 中国石油集团东北炼化工程有限公司吉林设计院 | Method for discharging catalysts for ethylene propylene rubber production |
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