CN100429239C - Vanadium catalyst and preparation method thereof - Google Patents
Vanadium catalyst and preparation method thereof Download PDFInfo
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- CN100429239C CN100429239C CNB2004100704491A CN200410070449A CN100429239C CN 100429239 C CN100429239 C CN 100429239C CN B2004100704491 A CNB2004100704491 A CN B2004100704491A CN 200410070449 A CN200410070449 A CN 200410070449A CN 100429239 C CN100429239 C CN 100429239C
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- vanadium
- organophosphate
- vanadyl
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- 239000003054 catalyst Substances 0.000 title claims abstract description 24
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 17
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 239000004711 α-olefin Substances 0.000 claims abstract description 11
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 54
- 125000005287 vanadyl group Chemical group 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 10
- -1 alcohol compound Chemical class 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- 150000003682 vanadium compounds Chemical class 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- JRPHGDYSKGJTKZ-UHFFFAOYSA-N selenophosphoric acid Chemical compound OP(O)([SeH])=O JRPHGDYSKGJTKZ-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000003513 alkali Substances 0.000 abstract description 5
- 239000005977 Ethylene Substances 0.000 abstract description 4
- 239000003570 air Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 150000001993 dienes Chemical class 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000002585 base Substances 0.000 description 18
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 12
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 230000002194 synthesizing effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 241000790917 Dioxys <bee> Species 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- NAGJZTKCGNOGPW-UHFFFAOYSA-K dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [O-]P([O-])([S-])=S NAGJZTKCGNOGPW-UHFFFAOYSA-K 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- SNAMIIGIIUQQSP-UHFFFAOYSA-N bis(6-methylheptyl) hydrogen phosphate Chemical compound CC(C)CCCCCOP(O)(=O)OCCCCCC(C)C SNAMIIGIIUQQSP-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 3
- CTIFNEKNJNIQMG-UHFFFAOYSA-N OP1CCC2=CC=CC=C12 Chemical compound OP1CCC2=CC=CC=C12 CTIFNEKNJNIQMG-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 125000002270 phosphoric acid ester group Chemical group 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 2
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 125000005340 bisphosphate group Chemical group 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 150000003681 vanadium Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- JREQABAVGPIXJB-UHFFFAOYSA-N 1-hydroxyphosphinane Chemical compound OP1CCCCC1 JREQABAVGPIXJB-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical group C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- RQINQJTUMGQYOB-UHFFFAOYSA-N 6-methylheptyl dihydrogen phosphate Chemical compound CC(C)CCCCCOP(O)(O)=O RQINQJTUMGQYOB-UHFFFAOYSA-N 0.000 description 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
- PKUWKAXTAVNIJR-UHFFFAOYSA-N O,O-diethyl hydrogen thiophosphate Chemical compound CCOP(O)(=S)OCC PKUWKAXTAVNIJR-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- PYKHKJJMHQLJOH-UHFFFAOYSA-N bis(3-methylbutyl) hydrogen phosphate Chemical compound CC(C)CCOP(O)(=O)OCCC(C)C PYKHKJJMHQLJOH-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a novel vanadium catalyst, a preparation method thereof and application of the catalyst in copolymerization of ethylene, alpha-olefin and diene. The catalyst is soluble in a nonpolar solvent, is insensitive to air, water, acid and alkali, has a simple synthesis method, is easy to industrialize, and shows high activity in the ternary polymerization of ethylene, alpha-olefin and diene.
Description
Technical field
The present invention relates to a kind of new vanadium catalyst and easy, the application of preparation method, and this catalyzer efficiently in ethene, alpha-olefin, diolefine copolymerization thereof that alkene is had greater activity.
Background technology
Often vanadium system Ziegler-Natta catalyst is used for ethene, alpha-olefin, diolefine terpolymerization in the industrial production and prepares rubber elastomer.Representative Primary Catalysts has VOCl
3, VCl
3, VCl
4, V (acac)
3Deng, promotor is an I-III family organometallic compound (as aluminum alkyls), these V-alkyl aluminum systems have been brought into play vital role on synthetic EPDM elastomerics.But this type of catalyzer also exists many shortcomings simultaneously, the first, lower to the unexpectedly poly-rate of propylene, diolefine than ethene, therefore in industrial production, must make propylene etc. excessive greatly, if obtain ideal diene and propylene insertion rate, will recycle excessive propylene and diolefine; The second, the terpolymer activity is not high enough; The 3rd, therefore these compounds are being produced storage and are being used and can bring many problems sensitivities such as air, water, acid, alkali; The 4th, the building-up reactions once through yield is low.
US5086023 is by change center surrounding environment, promptly with group (imino-) substituted oxy with different characteristic electrons, solved the insertion problem of propylene, diolefine, its polymerization activity is better, but employed complex compound is still to sensitivities such as air, water, acid, alkali.US4598132 discloses a kind of vanadium catalyst system that contains the ester group polymkeric substance, can only improve the gel problem with the system that this catalyzer and aluminum alkyls form in synthetic EPDM process; As vulcanize problem.What solved among the US5122493 is the molecular weight distribution problem, by using branching dihydroxyl hydrocarbon, makes polymericular weight form narrow distribution, employed VO (acac)
2Though catalyzer is insensitive to air, water etc.,, have difficulties when therefore using because it is insoluble to inert solvent (as hexane).
Summary of the invention
The object of the present invention is to provide a kind of stable, active height of copolymerization, new vanadium catalyst easy to use and preparation method thereof, and the application of this catalyzer in ethene, alpha-olefin, diolefine terpolymer.
A kind of vanadium catalyst provided by the present invention, its structural formula is:
VALL′
Wherein: V is vanadium 4 valency ions;
A is oxygen, sulphur, selenium;
L, L ' are part, and L, L ' are organophosphate, and L, L ' can be identical, also can be inequality.
Organophosphate in the catalyzer that invention is provided can be dialkyl phosphate, dialkyl group thiophosphatephosphorothioate, dialkyl dithiophosphate, seleno phosphoric acid ester, two seleno phosphoric acid ester, annular phosphate, ring-type thiophosphatephosphorothioate, heterocycle Hypophosporous Acid, 50, heterocycle sulfo-Hypophosporous Acid, 50, condensed ring phosphoric acid ester, condensed ring thiophosphatephosphorothioate, preferred dialkyl phosphate.
Because the phosphoryl in the organophosphate wherein has the sub-property of power supply, exactly the oxygen of phosphoryl has the sub-property of power supply, thereby easily forms hydrogen bond and extremely strong metal complex ability is arranged at vanadium catalyst provided by the present invention; Easy and the Cl of hydrogen in the while bisphosphate hydroxyl
-And SO
4 2-Form acid (forming salt), and make bisphosphate become covalent linkage with the central atom V-arrangement, make bisphosphate and halogenation vanadium or halogenation vanadyl can form stable complex compound if add alkali.
Preparation of catalysts step provided by the present invention is as follows:
(A) under the condition that alcohol compound, carboxylic acid or carbonyl compound exist, pentavalent vanadium compound and inorganic acid reaction, obtain intermediate product 4 valency vanadyl compounds, pentavalent vanadium compound: mineral acid: alcohol compound, carboxylic acid or carbonyl compound (mol ratio)=1: 2～100: 1～20;
(B) after the cooling, 4 valency vanadyl compounds and organophosphate react pentavalent vanadium compound in non-polar solvent: organophosphate (mol ratio)=1: 1～3, stir, and drip alkaline inorganics, obtain catalyzer.
Or rather, the pentavalent vanadium compound in the Preparation of catalysts method provided by the present invention can Vanadium Pentoxide in FLAKES; Mineral acid can be hydrochloric acid or sulfuric acid; Nonmetallic reduction agent is as using alcohol compound, preferred alcohol, as be the carboxylic acid preferable formic acid, as be the preferred acetone of carbonyl compound; The alkalescence inorganics can be sodium carbonate solution; Non-polar solvent can be straight-chain paraffin or naphthenic hydrocarbon, preferred hexane.
New vanadium catalyst preferably provided by the invention is as follows:
(two (di (isooctyl) phosphate base)) vanadyl, (two O-(2-ethylhexyl)-ethylhexyl dihydrogen phosphate base) vanadyl, (O-di (isooctyl) phosphate O-(2-ethylhexyl)-ethylhexyl dihydrogen phosphate base) vanadyl, (two (diisoamyl phosphate base)) vanadyl, (two (O, O-diethyl phosphorothioate base)) vanadyl, (two (dibutyl phosphate base)) vanadyl, (two (p diethylaminobenzoic acid ester group)) vanadyl, (oxidation hydroxyl-1,3,2-benzo dioxy phospha five rings base) vanadyl, (two (O, O-encircles third phosphorodithioate)) vanadyl, (two (O, S-diisooctyl phosphoric acid ester group)) vanadyl, (oxidation hydroxyl phospha cyclohexane base) vanadyl, (two (oxidation hydroxy benzo phospholane base)) vanadyl, (two (dimethyl phosphate base)) vanadyl, (two (dibutyl phosphate base)) vanadyl, (two (p diethylaminobenzoic acid ester group)) vanadyl, (two (O, O-Methyl disulfide substituted phosphate base)) vanadyl.
The present invention also provides the application of described catalyzer in the terpolymerization of ethene, alpha-olefin, diolefine.In the terpolymerization of ethene, alpha-olefin, diolefine, can use catalyzer provided by the present invention to be Primary Catalysts, promotor is an aluminum alkyls.Aluminum alkyls can be triisobutyl aluminium, a chloro-di-isobutyl aluminum, aluminium diethyl monochloride, trichlorine triethyl two aluminium, dichloro one aluminium triethyl or triethyl aluminum; Preferred trichlorine triethyl two aluminium; Solvent is a non-polar solvent, can be straight-chain paraffin or naphthenic hydrocarbon, preferred hexane.
Alpha-olefin can be C
3～C
8Alkene, preferred propylene; Diolefine can be cyclopentadiene, dicyclopentadiene, ethylidene norbornene, 1,4-hexadiene, 5-vinyl-2-norbornylene etc., preferred ethylidene norbornene.
Polymerization temperature is 10～50 ℃, and polymerization pressure is 0.1～4.0Mpa, polymerization time 0.5～3.0 hour.
The application concrete operations of described catalyzer in the terpolymerization of ethene, alpha-olefin, diolefine are as follows:
Adopt the solution polymerization process polymerization.Reactor is a 5L Stainless Steel Band jacket reactor.The effect of chuck is a control reaction temperature.Unstripped gas is the mixed gas of ethene, propylene, hydrogen, ethene: propylene: hydrogen (mol ratio) is 1: 1.5～4.5: 0.15～0.45.In reactor, add solvent in proportion.Feed unstripped gas by certain speed in reactor, control unstripped gas air inlet speed prevents the excessive hexane of carrying secretly of tolerance.Emptying adds a certain amount of Primary Catalysts, promotor after 10 minutes, temperature of reaction is remained between 10～50 ℃, control reaction pressure 0.3～0.6Mpa, the middle interruption adds diolefine, use the cooling water control temperature of reaction, polymerization 1 hour adds ethanol and makes reaction terminating.Add 20%NaOH solution then and carry out repetitive scrubbing several times, the product static layering with obtaining bleeds off water layer, and remaining upper strata glue obtains terpolymer EPDM 50 ℃ of following vacuum-dryings 48 hours.
The present invention adopts two-step approach synthesizing new vanadium Ziegler-Natta catalyst, and total yield reaches 90%～100%, and synthetic method is simple, and is workable, is easy to industrialization.Advantage of the present invention is that the new vanadium catalyst that is provided contains heteroatom phosphate, be dissolved in non-polar solvent (for example hexane)-better solvent of the second third glue industrialization, and this catalyzer is all insensitive to air, water, acid, alkali, therefore gives and uses and the synthetic great convenience of bringing.This catalyzer demonstrates high reactivity in ethene, alpha-olefin, diolefine terpolymerization.
Embodiment
The invention will be further described below by embodiment.
Embodiment 1
Synthesizing of dichloro vanadyl
Get the 250ml there-necked flask and reinstall flow condenser, electromagnetism heated and stirred (Gong Yi of Henan Province city).Accurately take by weighing 5g V
2O
5(27.5mmol), pack in the there-necked flask, measure 18ml (18.5mmol) concentrated hydrochloric acid (36%) then, add 15ml water, 5ml reagent alcohol, heated sealed stirring and refluxing, half hour internal reaction liquid by brick red to yellowish green, become mazarine at last, react half an hour again, get mazarine dichloro vanadyl solution.
B.[two (diisooctyl phosphoric acid ester group)] vanadyl synthetic
Get that 1000ml there-necked flask installation tool stirs, minim pipette, above-mentioned synthetic dichloro vanadyl is packed in the there-necked flask, add the 300ml industrial hexane, stirring adds 95.5% industrial diisooctyl phosphoric acid ester 38ml down again, stir 10% the sodium carbonate solution of slowly dripping, restir 10 minutes, stop to stir and pour the quantizer layering into, get oil phase, it is inferior to give a baby a bath on the third day after its birth with 1000ml distilled water again, gets the blue vanadium complexes of 325ml at last, concentration is 17.6% by analysis, and yield is 99%.
Embodiment 2
Synthesizing of vanadylic sulfate
Get the 250ml there-necked flask, reinstall flow condenser, the electromagnetism heated and stirred.Accurately take by weighing 5gV
2O
5(27.5mmol) pack in the there-necked flask, measure the vitriol oil of 8ml98% then, slowly add 12.5ml distilled water again, add the 10ml dehydrated alcohol again, sealed reactor, heated and stirred refluxes, half an hour internal reaction liquid by brick red to blackish green, be mazarine at last.React half an hour again, get mazarine vanadylic sulfate solution.
B.[two (diisooctyl phosphoric acid ester group)] vanadyl synthetic
Get the 1000ml there-necked flask, installation tool stirring, minim pipette, above-mentioned synthetic vanadylic sulfate is packed in the there-necked flask, add the 300ml industrial hexane and stir and add 95.5% industrial diisooctyl phosphoric acid ester 38ml down, stir, slowly drip 10% sodium carbonate solution, when reaction solution water PH=6～7, stop to drip sodium carbonate solution, restir 10 minutes, stop to stir, pour quantizer into, get oil phase, it is inferior to give a baby a bath on the third day after its birth with 1000ml distilled water again, get the blue vanadium complexes of 305ml at last, yield 92%.
Embodiment 2
Elementary operation is with embodiment 1.The diisooctyl phosphoric acid ester is replaced with O-(2-ethylhexyl)-ethylhexyl dihydrogen phosphate, get 310 blue solution, yield 96%.
Ultimate analysis: C theoretical value 56.65, measured value 55.66; H theoretical value 10.03, measured value 9.56; P theoretical value 14.17, measured value 14.00; V theoretical value 11.66, measured value 9.65.
Synthesizing of embodiment 3 (two O-(2-ethylhexyl)-ethylhexyl dihydrogen phosphate base) vanadyl
Elementary operation is with embodiment 1.The diisooctyl phosphoric acid ester is replaced with the different ester of defending of di(2-ethylhexyl)phosphate, get the blue hexane solution of 295ml, yield 90%.
Ultimate analysis: C theoretical value 44.31, measured value 44.60; H theoretical value 8.12, measured value 8.19; P theoretical value 7.58, measured value 7.33; V theoretical value 9.42, measured value 9.00.
Synthesizing of embodiment 4 (oxidation hydroxyl-1,3,2-benzo dioxy phospha five rings base) vanadyl
Elementary operation is with embodiment 1.The diisooctyl phosphoric acid ester is replaced with oxidation hydroxyl-1,3,2-benzo dioxy phospha five rings, get the blue hexane solution of 300ml, yield 91%.
Ultimate analysis: C theoretical value 17.60, measured value 16.95; H theoretical value 1.22, measured value 1.23; P theoretical value 7.58, measured value 7.33; V theoretical value 12.47, measured value 10.69.
Synthesizing of embodiment 5 (oxidation hydroxyl-1,3,2-benzo dioxy phospha five rings base) vanadyl
Elementary operation is with embodiment 2.The diisooctyl phosphoric acid ester is replaced with oxidation hydroxyl-1,2,2-benzo dioxy phospha five rings, get the blue hexane solution of 310ml, yield 98%.
Ultimate analysis: C theoretical value 17.60, measured value 16.80; H theoretical value 1.22, measured value 1.20; P theoretical value 7.58, measured value 7.37; V theoretical value 12.47, measured value 11.69.
Embodiment 6 (two (O, O-encircle third phosphorodithioate)) vanadyl
Elementary operation is with embodiment 1.Different is with two different hot phosphoric acid ester with O, and O '-ring third phosphorodithioate substitutes, final the blue hexane solution of 280ml, yield 85%.
Ultimate analysis: C theoretical value 8.89, measured value 8.70; H theoretical value 1.73, measured value 1.56; P theoretical value 7.65, measured value 7.63; V theoretical value 12.59, measured value 11.76.
Embodiment 7 (two (O, O-encircle third phosphorodithioate)) vanadyl
Elementary operation is with embodiment 2.Different is with two different hot phosphoric acid ester with O, and O '-ring third phosphorodithioate substitutes, final the blue hexane solution of 290ml, yield 88%.
Ultimate analysis: C theoretical value 8.89, measured value 8.77; H theoretical value 1.73, measured value 1.68; P theoretical value 7.65, measured value 7.56; V theoretical value 12.59, measured value 11.87.
Synthesizing of embodiment 8 (two (oxidation hydroxy benzo phospholane base)) vanadyl
Elementary operation is with embodiment 1.Different is that di (isooctyl) phosphate is substituted the blue hexane solution of the final 290ml of getting, yield 90% with oxidation hydroxy benzo phospha five rings.
Ultimate analysis: C theoretical value 23.94, measured value 23.65; H theoretical value 2.24, measured value 2.31; P theoretical value 7.73, measured value 7.68; V theoretical value 12.72, measured value 12.13.
Synthesizing of embodiment 9 (two (oxidation hydroxy benzo phospholane base)) vanadyl
Elementary operation is with embodiment 2.Different is that di (isooctyl) phosphate is substituted the blue hexane solution of the final 295ml of getting, yield 92% with oxidation hydroxy benzo phospha five rings.
Ultimate analysis: C theoretical value 23.94, measured value 23.90; H theoretical value 2.24, measured value 2.26; P theoretical value 7.73, measured value 7.23; V theoretical value 12.72, measured value 11.89.
Embodiment 10
Adding the 2000ml hexane in the 5L polymeric kettle stirs, in polymeric kettle, feed ethene under the normal temperature, propylene, hydrogen mixed gas, [two (di (isooctyl) phosphate the base)] vanadyl that adds 0.04mmol, and the alkyl aluminum halide of 0.8mmol, ethene: propylene: hydrogen=1: 2.5: 0.2, polymerization pressure 0.5Mpa, polymerization 1 hour, stop to stir, add the ethanol termination reaction, use the 20%NaOH solution washing for several times then, static layering, get the glue layer, reclaim solvent, product got product 85.2g, molecular weight 47500 in 24 hours 50 ℃ of following vacuum-dryings, molecular weight distribution 2.5, ethylene content 52%.
Embodiment 11
In the 5L polymeric kettle, add the 2000ml hexane, stir, in polymeric kettle, feed ethene under the normal temperature; propylene; hydrogen mixed gas; [the titanium dioxide hydroxyl-1 that adds 0.02mmol; 3,2-benzo dioxy phospha five rings)] alkyl aluminum halide of vanadyl and 1mmol, ethene: propylene: hydrogen=1: 2.5: 0.2; polymerization pressure 0.6Mpa; polymerization 1 hour stops gas mixture, stops to stir; add the ethanol termination reaction; use the 20%NaOH solution washing then three times, static layering is got the glue layer; reclaim hexane; product gets product 46g, molecular weight 56000 at 60 ℃ of following vacuum-drying 24h; molecular weight distribution 2.8, ethylene content 62%.
Claims (8)
1. vanadium catalyst, its structural formula is:
VALL′
Wherein: V is vanadium 4 valency ions;
A is an oxygen;
L, L ' are organophosphate part identical or inequality.
2. vanadium catalyst according to claim 1 is characterized in that organophosphate is dialkyl phosphate, dialkyl group thiophosphatephosphorothioate, dialkyl dithiophosphate, seleno phosphoric acid ester, two seleno phosphoric acid ester, annular phosphate, ring-type thiophosphatephosphorothioate, heterocycle Hypophosporous Acid, 50, heterocycle sulfo-Hypophosporous Acid, 50, condensed ring phosphoric acid ester or condensed ring thiophosphatephosphorothioate.
3. the described Preparation of catalysts method of claim 1, step is as follows:
(A) under alcohol compound, carboxylic acid or carbonyl compound existence condition, pentavalent vanadium compound and inorganic acid reaction, obtain intermediate product 4 valency vanadyl compounds, pentavalent vanadium compound: mineral acid: alcohol compound, carboxylic acid or carbonyl compound (mol ratio)=1: 2～100: 1～20;
(B) after the cooling, 4 valency vanadyl compounds and organophosphate react pentavalent vanadium compound in non-polar solvent: organophosphate (mol ratio)=1: 1～3, stir, and drip alkaline inorganics, obtain catalyzer.
4. Preparation of catalysts method according to claim 3, it is characterized in that pentavalent vanadium compound wherein is a Vanadium Pentoxide in FLAKES, mineral acid is hydrochloric acid or sulfuric acid, and organophosphate is a dialkyl phosphate, the alkalescence inorganics is a sodium carbonate solution, and non-polar solvent is a hexane.
5. Preparation of catalysts method according to claim 3 is characterized in that wherein alcohol compound, carboxylic acid or carbonyl compound can be ethanol, formic acid or acetone.
6. the application of the catalyzer of a claim 1 in the terpolymerization of ethene, alpha-olefin, diolefine is characterized in that adding aluminum alkyls as promotor.
7. Application of Catalyst according to claim 6 is characterized in that aluminum alkyls is triisobutyl aluminium, a chloro-di-isobutyl aluminum, aluminium diethyl monochloride, trichlorine triethyl two aluminium, dichloro one aluminium triethyl or triethyl aluminum.
8. Application of Catalyst according to claim 6 is characterized in that terpolymerization temperature wherein is 10～50 ℃, and polymerization pressure is 0.1～1.0Mpa, polymerization time 0.5～3.0 hour.
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| CN108889319B (en) * | 2018-07-23 | 2021-05-07 | 贵州大学 | Efficient H2O2/Se composite modified vanadium catalyst and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0518415A2 (en) * | 1991-06-13 | 1992-12-16 | Akzo N.V. | Catalyst for EPDM polymerization |
| EP1002800A1 (en) * | 1998-11-19 | 2000-05-24 | Enichem S.p.A. | Catalysts based on vanadium, their preparation and use in the (co)polymerization of alpha-olefins. |
| JP2001064316A (en) * | 1999-08-27 | 2001-03-13 | Ube Ind Ltd | Production of conjugated diene polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0518415A2 (en) * | 1991-06-13 | 1992-12-16 | Akzo N.V. | Catalyst for EPDM polymerization |
| EP1002800A1 (en) * | 1998-11-19 | 2000-05-24 | Enichem S.p.A. | Catalysts based on vanadium, their preparation and use in the (co)polymerization of alpha-olefins. |
| JP2001064316A (en) * | 1999-08-27 | 2001-03-13 | Ube Ind Ltd | Production of conjugated diene polymer |
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