Background method.
Ethylene-propylene rubber(EPR) production both at home and abroad is many to be catalyzer with the vanadium sub-group compound, and these vanadium compound are limited to VX
3, VX
4, VOX
3And VO (OR)
3-nX
n, X is a halogen, is mainly the chlorine atom, and R is the alkyl of 6-12 carbon, and n is the integer of 0-2, wherein VOCl
3And VO (OR)
3It is catalyzer the most frequently used in the industrial production.Its main patent is VCl
3(U.S. Pat 5,367,037), VCl
4(U.S. Pat 5,367,037, US4,078,131), VOCl
3(U.S. Pat 5,367,037, US4,078,131) and VO (OR)
3-nCl
n(U.S. Pat 3,173,903, US4,259,468).
VCl
3, VCl
4And VOCl
3Be by V
2O
5High-temp chlorination makes, and uses chlorine not only to damage operator's health in a large number, and causes serious environmental to pollute.On the other hand, VCl
3, VCl
4And VOCl
3Volatile, toxicity is big, meet air decomposes, meets the water blast, thereby brings inconvenience for storage, transportation and use.
VO (OR)
3-nCl
nThough 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.
Contain vanadium organophosphorus monoprotic acid complex compound and still do not have report at present as the ethylene-propylene rubber(EPR) catalyzer.Though contain the synthetic existing report of vanadium organophosphorus monoprotic acid complex compound itself, as " Solvent ExtractionChemistry ", T.Sekine and Y.Hasegawa, Marcel Dekker INC, 1977 reach " non-ferrous extractive metallurgy handbook-rare refractory metal ", metallurgical industry press, 1999.But these work only with the extracting vanadium compound as a kind of separation means in hydrometallurgy and the analytical chemistry, prepare purpose but not be used for vanadium compound, and used organic phase operation capacity is little, vanadium concentration is low, does not possess the industrial preparation meaning.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who is used to produce the ethylene-propylene rubber(EPR) vanadium series catalyst.
The present invention adopts V
2O
5, NaVO
3Intermediates in navajoite product or its sepn process are raw material, organophosphorus monoprotic acid is extraction agent, aliphatic carboxylic acid is for helping the collection agent, saturated alkane is the organic phase solvent, take the cross current solvent extraction method, stable saturated alkane vanadium (IV) or vanadium (V) compound solution of final acquisition directly produced catalyzer as ethylene-propylene rubber(EPR).
The present invention is the aqueous solution with the vanadium compound feedstock production at first, under the given condition of the present invention vanadium atom being extracted to from water with the saturated alkane with the form of organophosphorus monoprotic acid complex compound is the organic phase of solvent, and vanadium atom exists with V (IV) or V (V) valence state in the saturated alkane solvent.
The selected extraction agent organophosphorus monoprotic acid of the present invention is di(2-ethylhexyl)phosphate (2-ethylhexyl) ester ([C
4H
9CH (C
2H
5) CH
2O]
2P (O) OH, commercial disignation P204), 2-ethylhexyl phosphonic acid 2-(ethyl hexyl) ester ([C
4H
9CH (C
2H
5) CH
2] [C
4H
9CH (C
2H
5) CH
2O] P (O) OH, commercial disignation P507) or two (2-ethylhexyl) phosphonic acids ([C
4H
9CH (C
2H
5) CH
2]
2P (O) OH, commercial disignation P229).
The present invention selects for use the aliphatic carboxylic acid that contains 5-13 carbon atom for helping the collection agent, is the best with the aliphatic carboxylic acid that contains 7-9 carbon atom wherein, specifically: enanthic acid, sad, 2 ethyl hexanoic acid or n-nonanoic acid.Helping the effect of collection agent is 1) make inorganic phase and organic phase phase-splitting easy; 2) the vanadium compound saturated alkane solution height of Huo Deing is stable, avoids the vanadium compound precipitation to occur; 3) prepared vanadium series catalyst has good polymerization activity in ethylene-propylene rubber(EPR) production.
It is solvent that the present invention selects saturated alkane for use, and saturated alkane is hexane or heptane.
The present invention reduces the extraction agent unit consumption for improving the loading capacity of vanadium compound, adopts the cross current solvent extraction method.The cross current solvent extraction method is to add new stock liquid to carry out the extraction second time in the organic phase that single extraction obtains, and so can repeatedly extract, and the surplus water of each extraction returns and continues to use.The cross current solvent extraction method can increase substantially the loading capacity of vanadium compound, and the utilization ratio of extraction agent is reached or near 100%, thereby makes this method for preparing catalyst have more industrial significance.
Catalyst preparation process and reaction conditions are as follows:
1) preparation of V (V) organophosphorus monoprotic acid stable hydrocarbon catalyst solution
1. with navajoite product V
2O
5, with NaOH or Na
2CO
3The aqueous solution dissolves, and V (V) compound water solution that forms is adjusted to PH 〉=8;
2. the saturated alkane mixing solutions that above-mentioned V (V) compound water solution is added organophosphorus monoprotic acid and aliphatic carboxylic acid, wherein fatty acid content is the 5-40% molar percentage of total extraction dosage, with mineral acid water is adjusted to PH=0.5-2.0 again, extraction process at room temperature carries out, make water and organic phase thorough mixing with oscillator or agitator, carry out batch or continuous cross current solvent extraction, the concentration KMnO of V (V) in final catalyst prod V (V) the organophosphorus monoprotic acid complex solution
4-Fe
2+The standardized solution redox titration is determined.
2) preparation of V (IV) organophosphorus monoprotic acid saturated hydrocarbon solution
1. with NaVO
3Or V
2O
5Use H
2SO
4Or the HCl dissolving, and add reductive agent.Reductive agent is Na
2SO
3Or H
2C
2O
4, stirred 45-60 minute down at 90-100 ℃, obtain VOSO
4Or VOCl
2V (IV) compound solution.The elimination insolubles is adjusted into about 0.1-1.0mol/L with filter liquor concentration, and pH value is adjusted into 0.5-2.0.As V (IV) stock liquid;
2. the saturated alkane mixing solutions of organophosphorus monoprotic acid that is 5-40% with fatty carboxylic acid molar percentage and aliphatic carboxylic acid adds the NaOH aqueous solution, mixes 1-2 minute, and the add-on of NaOH reaches 6.5-7.0 with the system pH value and is as the criterion.V (IV) stock liquid that adds above-mentioned preparation, the preparation of the same V of extraction process (V) organophosphorus monoprotic acid saturated hydrocarbon solution, the concentration KMnO of V (IV) in final catalyst prod V (IV) the organophosphorus monoprotic acid complex solution
4-Fe
2+The standardized solution oxidation reduction titration is determined.
The prepared novel vanadium series catalyst of the present invention is used for the production of ethylene-propylene-non-conjugated dienes hydrocarbon copolymer (EPDM), and wherein the non-conjugated dienes hydrocarbon is ethylidene norbornene (ENB) or dicyclopentadiene (DCP).
Characteristics of the present invention are: 1) adopt V
2O
5Deng navajoite is raw material, and method for preparing catalyst is easy, and the preparation condition gentleness is fit to the large-scale industry preparation; 2) do not relate to poisonous, the deleterious chlorine of use, do not adopt harsh reaction conditionss such as high-temp chlorination, reduced preparation cost, helped environment protection; 3) prepared catalyzer saturated hydrocarbon solution height homogeneous stability, insensitive to water and air, overcome present commercial catalysts to the extremely sensitive shortcoming of water and air, be convenient to industry and use, reduced the cost in storage, the transportation simultaneously; 4) prepared catalyzer has the catalytic activity higher than commercial catalysts VOC13, and gained ethylene-propylene rubber(EPR) has close molecular chain structure, monomeric unit sequential structure and the 3rd monomer content.
Embodiment
Embodiment 1
Add 200mlH in the 1L beaker
2O, 23.3g solid NaOH stir and make it dissolving, and heating is closely boiled.Other is with the V of 49.5g purity 〉=99%
2O
5Use 100mlH
2O furnishing pulpous state is slowly poured in the NaOH solution, stir about 20 minutes.The a small amount of insolubles of elimination is used 1N H
2SO
4The aqueous solution is adjusted to 8.28 with pH value, uses H
2O is diluted to 1000ml.Sampling is with (NH
4)
2Fe (SO
4)
2Standard solution titration, V (V) concentration is 0.533mol/L.
The hexane mixing solutions that in the 20ml separating funnel, adds di-(2-ethylhexyl)phosphoric acid that the 10ml total concn is 1.034mol/L (hereinafter to be referred as P204) and 2 ethyl hexanoic acid respectively, wherein P204 concentration is 0.8mol/L, 2 ethyl hexanoic acid concentration is 0.234mol/L, the concentration of the above-mentioned preparation of 5ml is V (V) stock liquid of 0.533mol/L, mixes 5 minutes.In separating funnel, add 3ml 1N H
2SO
4The aqueous solution mixed 15 minutes on the earthquake device, and water is emitted in static phase-splitting.Organic phase is V (V) catalyzer hexane solution, and by analysis: V (V) concentration is 0.208mol/L, and extraction agent (P204 and 2 ethyl hexanoic acid) is 5.0: 1 with the mol ratio of V (V).
For increasing loading capacity, reduce the extraction agent consumption, adopt the cross current solvent extraction mode to carry out the second time and extraction for the third time.Above-mentioned organic phase adds the V that concentration is 0.533mol/L (V) stock liquid 3ml again, mixes 15 minutes, and water is emitted in static phase-splitting.Organic phase is by analysis: V (V) concentration is 0.319mol/L, and extraction agent (P204 and 2 ethyl hexanoic acid) is 3.2: 1 with the mol ratio of V (V).Add the V that concentration is 0.533mol/L (V) stock liquid 3ml in the organic phase again, repeat above operation, organic phase by analysis: V (V) concentration is 0.428mol/L, and extraction agent (P204 and 2 ethyl hexanoic acid) is 2.4: 1 with the mol ratio of V (V).
Adding 3L polymerization-grade hexane solvent in 5L stainless steel polymeric kettle, is 40 ℃ by chuck recirculated water controlled polymerization still temperature, and begins to stir.In polymeric kettle, add 5g ethylidene norbornene (ENB), 60mmol aluminium diethyl monochloride hexane solution, 3mmol V (V) catalyzer hexane solution, feeding consists of ethylene content 35mol%, propylene content 63mol%, the ethene of hydrogen content 2%, propylene and hydrogen mixed gas are 8kg/cm by pressurized circulation pump control reactor total pressure
2, and keep gas composition constant.Behind the polyase 13 0 minute, reactor emptying adds small amount of ethanol and stops polyreaction to normal pressure.Polymers soln is emitted at the bottom of by still, through washing, drying, ethylene-propylene-ENB terpolymer EP rubber (EPDM), catalytic efficiency is 1360g EPDM/g V.
Polymkeric substance is by analysis: propylene content is 36.6%, and iodine number is 11.8, is solvent with the perhydronaphthalene, and 135 ℃ are measured intrinsic viscosities down is 1.29dl/g.
Embodiment 2
3.5g solid Na
2CO
3Add 125ml H
2The O heating for dissolving, and be warming up to and boil.Other claims 3.5g V
2O
5Use 30mlH
2O furnishing slurries.Following V (V) method for preparing catalyst obtains the V that concentration is 0.10mol/L (V) catalyzer hexane solution at last with embodiment 1.
Polymerization process is with embodiment 1, polymkeric substance by analysis: propylene content is 37.4%, and iodine number is 9.5, is solvent with the perhydronaphthalene, and 135 ℃ are measured intrinsic viscosities down is 1.29dl/g.
Embodiment 3
With 102.6g V
2O
5Add 100ml H
2O furnishing pulpous state.In addition with 100g oxalic acid H
2C
2O
42H
2O is dissolved in the 200ml hot water.
Add 50mlH in the 1L beaker
2O slowly adds the 62ml vitriol oil, is heated with stirring to and boils.Alternately add V lentamente
2O
5Slurries and H
2C
2O
4Solution stirred 60 minutes down at 95 ℃, and a small amount of insolubles of elimination obtains VOSO
4Solution.Use H
2O is diluted to 1000ml, uses KMnO
4-(NH
4)
2Fe (SO
4)
2The titration of standardized solution oxidation-reduction, V (IV) concentration is 1.0mol/L, PH=0.5.
Adding the 92ml total concn in separating funnel is the di-(2-ethylhexyl)phosphoric acid (hereinafter to be referred as P204) of 1.205mol/L and the hexane mixing solutions of 2 ethyl hexanoic acid, wherein the 2 ethyl hexanoic acid proportion is 25mol%, add the NaOH aqueous solution, PH is adjusted into 7.0 with organic phase.The concentration that adds the above-mentioned preparation of 110ml is V (IV) stock liquid of 0.519mol/L, and by the cross-flow extraction process, working method is with embodiment 1.Obtain V (IV) catalyzer hexane solution at last, by analysis: V (IV) concentration is 0.70mol/L, and extraction agent (P204 and 2 ethyl hexanoic acid) is 2.18: 1 with the mol ratio of V (IV).
V (IV) polymerization catalyst method is with embodiment 1, and catalytic efficiency is 2000g EPDM/g V.
Polymkeric substance is by analysis: propylene content is 37.9%, and iodine number is 10.3, is solvent with the perhydronaphthalene, and 135 ℃ are measured intrinsic viscosities down is 1.29dl/g.
Embodiment 4
With 51.3g V
2O
5Add 100ml H
2O furnishing pulpous state.In addition with 50gNa
2SO
3Be dissolved in the 200ml hot water.
Add 1: 1 hydrochloric acid soln of 180ml in the 1L beaker, be heated with stirring to and boil.Alternately add V lentamente
2O
5Slurries and Na
2SO
3Solution stirred 60 minutes down at 95 ℃, and a small amount of insolubles of elimination obtains VOCl
2Solution.Use H
2O is diluted to 1000ml, uses KMnO
4-(NH
4)
2Fe (SO
4)
2The titration of standardized solution oxidation-reduction, V (IV) concentration is 0.519mol/L, PH=2.0.
Solvent hexane among the embodiment 3 is replaced with heptane, will help collection agent 2 ethyl hexanoic acid to account for ratio in total extraction agent simultaneously and be increased to 40% (mole percentage this), other operational conditions and working method be with embodiment 3, V (IV) catalyzer n-heptane solution.By analysis: V (IV) concentration is 0.72mol/L, and extraction agent (P204 and 2 ethyl hexanoic acid) is 2.12: 1 with the mol ratio of V (IV).
V (IV) polymerization catalyst method is with embodiment 1, and catalytic efficiency is 2020g EPDM/g V.
Polymkeric substance is by analysis: propylene content is 35.4%, and iodine number is 12.2, is solvent with the perhydronaphthalene, and 135 ℃ are measured intrinsic viscosities down is 1.29dl/g.
Embodiment 5
Organophosphorus monoprotic acid P204 among the embodiment 3 is replaced with 2-ethylhexyl phosphonic acid 2-(ethyl hexyl) ester (P507), help collection agent 2 ethyl hexanoic acid to replace with enanthic acid, the ratio that enanthic acid accounts for total extraction agent is 5mol%, other operational conditions and working method get V (IV) catalyzer hexane solution with embodiment 3.By analysis: V (IV) concentration is 0.80mol/L, and extraction agent (P507 and enanthic acid) is 2.32: 1 with the mol ratio of V (IV).
V (IV) polymerization catalyst method is with embodiment 1, and catalytic efficiency is 1820g EPDM/g V.
Polymkeric substance is by analysis: propylene content is 36.9%, and iodine number is 11.8, is solvent with the perhydronaphthalene, and 135 ℃ are measured intrinsic viscosities down is 1.29dl/g.
Embodiment 6
Organophosphorus monoprotic acid P204 among the embodiment 3 is replaced two (2-ethylhexyl) phosphonic acids (P229), and it is sad to help collection agent 2 ethyl hexanoic acid to replace with, and other operational conditions and working method get V (IV) catalyzer hexane solution with embodiment 3.By analysis: V (IV) concentration is 0.65mol/L, and extraction agent (P229 and sad) is 2.22: 1 with the mol ratio of V (IV).
V (IV) polymerization catalyst method is with embodiment 1, and catalytic efficiency is 1910g EPDM/g V.
Polymkeric substance is by analysis: propylene content is 38.7%, and iodine number is 9.9, is solvent with the perhydronaphthalene, and 135 ℃ are measured intrinsic viscosities down is 1.29dl/g.
Embodiment 7
The collection agent 2 ethyl hexanoic acid that helps among the embodiment 3 is replaced with n-nonanoic acid, and other operational conditions and working method get V (IV) catalyzer hexane solution with embodiment 3.By analysis: V (IV) concentration is 0.67mol/L, and extraction agent (P204 and n-nonanoic acid) is 2.17: 1 with the mol ratio of V (IV).
DCP is with embodiment 1 for V (IV) polymerization catalyst method, and catalytic efficiency is 2030g EPDM/g V.
Polymkeric substance is by analysis: propylene content is 40.1%, and iodine number is 10.8, is solvent with the perhydronaphthalene, and 135 ℃ are measured intrinsic viscosities down is 1.29dl/g.
Comparative example 1
Adding 3L polymerization-grade hexane solvent in 5L stainless steel polymeric kettle, is 40 ℃ by chuck recirculated water controlled polymerization still temperature, and begins to stir.In polymeric kettle, add 5g ethylidene norbornene (ENB), 60mmol aluminium diethyl monochloride hexane solution, 3mmol VOCl
3The catalyzer hexane solution feeds and consists of ethylene content 35mol%, propylene content 63mol%, and the ethene of hydrogen content 2%, propylene and hydrogen mixed gas are 8kg/cm by pressurized circulation pump control reactor total pressure
2, and keep gas composition constant.Behind the polyase 13 0 minute, reactor emptying adds small amount of ethanol and stops polyreaction to normal pressure.Polymers soln is emitted at the bottom of by still, through washing, drying, ethylene-propylene-ENB terpolymer EP rubber (EPDM), catalytic efficiency is 1520g EPDM/g V.
Polymkeric substance is by analysis: propylene content is 34.0%, and iodine number is 13.5, is solvent with the perhydronaphthalene, and 135 ℃ are measured intrinsic viscosities down is 1.29dl/g.