CN102718908B - Catalyst system of ethylene-propylene copolymerization and application thereof - Google Patents
Catalyst system of ethylene-propylene copolymerization and application thereof Download PDFInfo
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- CN102718908B CN102718908B CN201110079725.0A CN201110079725A CN102718908B CN 102718908 B CN102718908 B CN 102718908B CN 201110079725 A CN201110079725 A CN 201110079725A CN 102718908 B CN102718908 B CN 102718908B
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Abstract
The invention discloses a catalyst system of ethylene-propylene copolymerization, comprising vanadium compound, organo-aluminum compound and activating accelerator, wherein the molar ratio of Al in the organo-aluminum compound to V in the vanadium compound is 10-200:1, the molar ratio of the activating accelerator to V in the vanadium compound is 1-50:1, the activating accelerator is selected from alkyltrihalosilane of R'X3Si or boric acid ester of B(OR'')3, the R' and R'' are respectively selected from C1-C4 alkyl or C6-C8 alkaryl, and X is halogen. The catalyst system can effectively raise the activity of vanadium catalyst.
Description
Technical field
The present invention is a kind of second the third copolymerization catalyst system and application, specifically, is a kind of catalyst system take vanadium compound as Primary Catalysts and the application in second the third copolymerization.
Background technology
Ethylene-propylene rubber(EPR) is the very important starting material of a class in rubber item industry, there is highly ageing-resistant, heat-resisting, cold-resistant, chemical resistance and electrical insulating property, also there is low, the high fillibility of relative density simultaneously and have the advantages such as good intermiscibility with multiple superpolymer, being widely used in trolley part, building water-proof material, polymer modifiers, oil dope, wire cable insulating layer and other numerous rubber items.
Ethylene-propylene rubber(EPR) can be divided into binary, ternary, modification and thermoplasticity ethylene-propylene rubber(EPR).Ethylene propylene rubber forms with ethene, copolymerization of propylene, and make take ethene, propylene and a small amount of non-conjugated dienes as monomer copolymerization as terpolymer EP rubber.Can adopt bromination, chlorination, sulfonation, cis-butenedioic anhydride, maleation, organosilicon etc. to carry out modification to binary or terpolymer EP rubber, can also adopt the methods such as blend, copolymerization, grafting to carry out modification, thereby improve the performance of multipolymer, obtain the better macromolecular material of over-all properties.
CN1427016A discloses a kind of preparation method of ethylene-propylene copolymer, adopting vanadium acetylacetonate, alkyl aluminum halide is the synthetic ethylene-propylene copolymer of catalyzer, production can be applied to the ethylene-propylene copolymer of lubricating oil viscosity index improver, the low and narrowly distributing of the ethylene-propylene copolymer relative molecular mass of preparation, without degree of crystallinity.
CN1593763A discloses a kind of containing furfuran metal catalyst and preparation method and application, described catalyzer comprises containing furfuran metal, this catalyzer coordinates methylaluminoxane promotor to can be used for alpha-olefin copolymer production ethylene-propylene copolymer, also can be used for production second the third glue, the Lewis acid in the stable cationic active centre of its use is tritane base four (pentafluorophenyl group boron), liquid second the third adhesive tape of producing has α-terminal double link of 95%, average molecular mass Mn is 6440, and molecular weight distribution is 1.87.
CN101092466A discloses vanadium catalysis system and the application thereof of a kind of ethene, propylene, diolefine copolymerization, take vanadium complexes as Primary Catalysts, by introduce activation promotor in vanadium catalysis system, form new active catalytic system, make it to ethene, propylene, the active obviously raising of diolefine terpolymerization, the add-on of vanadium catalyst significantly reduces, and make removing easily of aftertreatment vanadium, the activation promotor of its use is a kind of phenyl derivatives of saturated or undersaturated ester family's hydrochloric ether or the ester family chloro with 2～5 chlorine atoms.
A shortcoming that is used for the vanadium catalyst of second the third copolymerization is that catalyst life is short, and catalytic efficiency is low.So just cause the content of vanadium in product excessive, thereby make the color of product excessively dark, electrical property, ageing-resistant performance and poor processability, just need in vanadium catalysis system, add activation promotor in order to obtain rational output, improve the catalytic efficiency of vanadium, regulate polymer molecular weight distributes, and reduces the consumption of catalyzer.Activation promotor is generally the compound of the electron-donating group of lone-pair electron such as containing oxygen, sulphur, phosphorus and nitrogen that many halogen replaces, as trichoroacetic acid(TCA) alkyl ester, perchloro-crotonate or acyl chlorides, replacement sulfonyl chloride, chloro vanadic acid ester, alkyl titanate etc.
Summary of the invention
The object of this invention is to provide a kind of second the third copolymerization catalyst system and application, it is activator that this catalyst system uses special alkyl halosilane or boric acid ester, can effectively improve catalyst activity.
Second the third copolymerization catalyst system provided by the invention, comprise vanadium compound, organo-aluminium compound and activation promotor, the mol ratio of V in Al and vanadium compound in described organo-aluminium compound is 10～200: 1, the mol ratio of V in activation promotor and vanadium compound is 1～50: 1, and it is R ' X that described activation promotor is selected from general formula
3alkyl three halosilanes of Si or general formula are B (OR ")
3boric acid ester, in described general formula, R ' and R " are selected from respectively C
1～C
4alkyl or C
6～C
8alkaryl, X is halogen.
Second the third copolymerization catalyst system of the present invention, use alkyl three halosilanes or not halogen-containing boric acid ester for activation promotor, can obviously improve the polymerization catalyzed efficiency of second third of vanadium catalyst, during particularly take alkyl three halosilanes as activation promotor, also can make praseodynium vanadyl [VO (acac)
3] under identical polymerization pressure, obtain the ethylene-propylene copolymer that relative molecular mass is higher, and use boric acid ester for activation promotor, can avoid introducing halogen in polymerization system, with the corrosion of halogen to equipment and the pollution to environment that prevent from using halogen-containing activation promotor to discharge in reaction process.
Embodiment
Vanadium catalysis system provided by the invention comprises Primary Catalysts, promotor and activation promotor, described Primary Catalysts is vanadium compound, promotor is organo-aluminium compound, activation promotor is alkyl three halosilanes or boric acid ester, the activation promotor of selecting due to the present invention has special structure, compared with traditional activation promotor ethyl trichloroacetate (ETCA), second third Copolymerization activity of Primary Catalysts vanadium compound obviously improves.
The preferred vanadium oxytrichloride of Primary Catalysts vanadium compound of the present invention, praseodynium vanadyl [VO (acac)
3], vanadium trichloride or vanadium tetrachloride.
Described promotor organo-aluminium compound preferred alkyl aikyiaiurnirsoxan beta, aluminum alkyls or chlorination aluminum alkyls.The preferred triethyl aluminum of described aluminum alkyls or triisobutyl aluminium, the described preferred aluminium diethyl monochloride of chlorination aluminum alkyls or trichlorine triethyl two aluminium (sesquialter aluminium triethyl).
The preferred chlorine of halogen in described alkyl three halosilanes general formulas, R ' is C preferably
1～C
3alkyl or C
6～C
8alkaryl, described alkaryl comprises phenyl, tolyl or xylyl.Alkyl three halosilanes preferable methyl trichlorosilanes, ethyl trichlorosilane or phenyl-trichloro-silicane, more preferably METHYL TRICHLORO SILANE or phenyl-trichloro-silicane.
R in described boric acid ester general formula " preferably C
1～C
4alkyl, as methyl, ethyl, propyl group or butyl, described propyl group is n-propyl or sec.-propyl, butyl is normal-butyl, isobutyl-or the tertiary butyl.Described boric acid ester preferred boric acid trimethyl, triethyl borate, tripropoxy-boron or tributyl borate, more preferably tributyl borate.
In catalyst system provided by the invention, the mol ratio of V in Al and vanadium compound in described organo-aluminium compound preferably 10～100: 1, more preferably 20～80: 1, the mol ratio of the V in activation promotor and vanadium compound preferably 1～30: 1, more preferably 2～10: 1.
Vanadium catalysis system provided by the invention can be used for the binary copolymerization of ethene, propylene.
Second the third copolymerization process provided by the invention, is included under organic solvent existence, makes ethene contact and carry out copolyreaction with catalyst system provided by the invention with propylene.
The present invention preferably adopts solution polymerization in homogeneous phase method, the preferred hexane of organic solvent used, heptane or hexanaphthene.In the time of polymerization, preferably use hydrogen for relative molecular mass conditioning agent.
While carrying out polyreaction by the inventive method, first in polymeric kettle, add organic solvent, add again Primary Catalysts of the present invention, promotor aluminum alkyls and activation promotor, stir ageing, the gas mixture that passes into ethene and propylene carries out polymerization, and the mol ratio of propylene and ethene is 1～6: 1, preferably 2～4: 1.Preferably in reaction system, add hydrogen, add the gas mixture of hydrogen, ethene and propylene, propylene in the hierarchy of control: ethene: the mol ratio of hydrogen is 1.0～6.0: 1.0: 0.1～1.0, preferably 2.0～4.0: 1.0: 0.1～1.0, controlling temperature of reaction is 10～70 ℃, preferably 20～50 ℃, and polymerization pressure is 0.1～1.0MPa, more preferably 0.3～0.8MPa preferably.Polymerization time preferably 0.1～3.0 hour, more preferably 0.3～2.0 hour, after reaction, add ethanol termination reaction, add again the NaOH solution washing of 10～20 quality % to remove the vanadium in system, and then fully wash with deionized water, by upper strata glue dry ethylene-propylene copolymer that obtains for 24～48 hours under 40～65 ℃ of decompressions.
Further describe the present invention below by example, but the present invention is not limited to this.
In example, the relative molecular mass (Mw) of polymkeric substance and relative molecular mass distribution (Mw/Mn) are measured with gel permeation chromatography (GPC), and instrument is the Alliance GPC2000 type gel permeation chromatograph of Waters company of the U.S..
In ethylene-propylene copolymer, the measuring method of propylene content is: take orthodichlorobenzene as solvent, according to multipolymer
13c-NMR spectrogram (recording with VARIAN INOVA 500M nuclear magnetic resonance spectrometer) calculates.
Example 1
The third copolyreaction of high pressure second.
1 liter of autoclave is fully replaced with nitrogen, then with hydrogen exchange once, then add successively hexane solution (containing Al 12mmol) and the 0.03mL VOCl of hexane that 500mL is dry, trichlorine triethyl two aluminium that 6mL concentration is 2mol/L
3(0.32mmol), add again the METHYL TRICHLORO SILANE of 0.15mL (1.29mmol), stir 15 minutes, be warming up to 30 ℃, pass into the gas mixture of ethene and propylene, boost to 0.55MPa, propylene in system: ethene: the mol ratio of hydrogen is 3: 1.5: 1, stirring reaction 1 hour, is depressurized to 0.1MPa, add ethanol termination reaction, reactant is the NaOH solution washing 2 times of 20 quality % by concentration, deionized water wash 3 times, by second the third sol solution obtaining after washing 55 ℃ of drying under reduced pressure 24 hours, obtain ethylene-propylene copolymer A, reaction result is in table 1.
Example 2
Prepare ethylene-propylene copolymer B by the method for example 1, that different is the VO (acac) with 40mg (0.16mmol)
3replace VOCl
3, by the phenyl-trichloro-silicane replacement METHYL TRICHLORO SILANE of 0.2mL (1.25mmol), reaction result is in table 1.
Example 3
Prepare ethylene-propylene copolymer C by the method for example 1, that different is the VCl with 0.03mL (0.28mmol)
4replace VOCl
3, the dosage of METHYL TRICHLORO SILANE is 0.15mL (1.29mmol), reaction result is in table 1.
Example 4
Prepare ethylene-propylene copolymer D by the method for example 1, difference is the VO (acac) with 40mg (0.16mmol)
3replace VOCl
3, control propylene in reaction system: ethene: the mol ratio of hydrogen is 4: 2: 1, and reaction pressure is 0.7MPa, and reaction result is in table 1.
Example 5
Prepare ethylene-propylene copolymer E by the method for example 1, difference is the tri-n-butyl borate [B (OBu) with 0.3mL (1.26mmol)
3] replacing METHYL TRICHLORO SILANE, reaction result is in table 1.
Example 6
Prepare ethylene-propylene copolymer F by the method for example 1, difference is the VO (acac) with 40mg (0.16mmol)
3replace VOCl
3, with the tri-n-butyl borate [B (OBu) of 0.2mL (0.84mmol)
3] replacing METHYL TRICHLORO SILANE, reaction result is in table 1.
Comparative example 1
Prepare ethylene-propylene copolymer G by the method for example 1, different is to replace METHYL TRICHLORO SILANE with a chlorine trimethyl silane of 0.15mL (1.19mmol), and reaction result is in table 1.
Comparative example 2
Prepare ethylene-propylene copolymer H by the method for example 1, difference is the VO (acac) with 40mg (0.16mmol)
3replace VOCl
3, by the dichlorodimethylsilane replacement METHYL TRICHLORO SILANE of 0.2mL (0.17mmol), reaction result is in table 1.
Comparative example 3
1 liter of autoclave is fully replaced with nitrogen, again with hydrogen exchange once, add successively the hexane solution (containing Al 12mmol) of hexane that 500mL is dry, trichlorine triethyl two aluminium that 6mL concentration is 2mol/L and the VO (acac) of 40mg (0.16mmol)
3, stir 15 minutes, be warming up to 30 ℃, the gas mixture that passes into ethene and propylene, boosts to 0.55MPa, propylene in system: ethene: the mol ratio of hydrogen is 3: 1.5: 1, stirring reaction 1 hour, be depressurized to 0.1MPa, add ethanol termination reaction, reactant is the NaOH solution washing 2 times of 20 quality % by concentration, deionized water wash 3 times, second the third sol solution of obtaining after washing, 55 ℃ of drying under reduced pressure 24 hours, is obtained to ethylene-propylene copolymer O, and reaction result is in table 1.
Comparative example 4
Prepare ethylene-propylene copolymer P by the method for comparative example 1, that different is the VOCl with 0.03mL (0.32mmol)
3replace VO (acac)
3, reaction result is in table 1.
Comparative example 5
Prepare ethylene-propylene copolymer Q by the method for comparative example 1, different is the activation promotor ethyl trichloroacetate (ECTA) that adds 0.2mL (1.44mmol) in reaction system, and reaction result is in table 1.
From table 1 data, use alkyl trichlorosilane of the present invention, than the reaction that uses other alkyl chlorinated silane as activation promotor, catalyst activity obtains raising by a relatively large margin, and in the ethylene-propylene copolymer making, propylene content is higher.In addition, when the present invention uses boric acid ester for activation promotor, catalyst activity is also improved significantly, and in the ethylene-propylene copolymer making, propylene content also increases.
Table 1
Claims (10)
1. a second third copolymerization catalyst system, comprise vanadium compound, organo-aluminium compound and activation promotor, the mol ratio of V in Al and vanadium compound in described organo-aluminium compound is 10～200: 1, the mol ratio of V in activation promotor and vanadium compound is 1～50: 1, and it is R ' X that described activation promotor is selected from general formula
3alkyl three halosilanes of Si or general formula are B (OR ")
3boric acid ester, in described general formula, R ' and R " are selected from respectively C
1～C
4alkyl or C
6～C
8alkaryl, X is halogen, described vanadium compound is vanadium oxytrichloride or praseodynium vanadyl.
2. according to catalyst system claimed in claim 1, it is characterized in that described organo-aluminium compound is alkylaluminoxane, aluminum alkyls or chlorination aluminum alkyls.
3. according to catalyst system claimed in claim 2, it is characterized in that described aluminum alkyls is selected from triethyl aluminum or triisobutyl aluminium, described chlorination aluminum alkyls is selected from aluminium diethyl monochloride or trichlorine triethyl two aluminium.
4. according to catalyst system claimed in claim 1, it is characterized in that described alkyl three halosilanes are selected from METHYL TRICHLORO SILANE, ethyl trichlorosilane or phenyl-trichloro-silicane.
5. according to catalyst system claimed in claim 1, it is characterized in that described boric acid ester is selected from trimethyl borate, triethyl borate, tripropoxy-boron or tributyl borate.
6. according to catalyst system claimed in claim 1, it is characterized in that the mol ratio of the Al in described organo-aluminium compound and the V in vanadium compound is 10～100: 1, the mol ratio of the V in activation promotor and vanadium compound is 2～10: 1.
7. second third copolymerization process, is included under organic solvent existence, makes ethene contact and carry out copolyreaction with catalyst system claimed in claim 1 with propylene.
8. in accordance with the method for claim 7, it is characterized in that described organic solvent is hexane, heptane or hexanaphthene.
9. the mol ratio that in accordance with the method for claim 7, it is characterized in that propylene and ethene is 1～6: 1.
10. in accordance with the method for claim 7, it is characterized in that copolyreaction temperature is 10～70 ℃.
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| CN112940165B (en) * | 2019-12-11 | 2022-10-04 | 中国石油天然气股份有限公司 | Preparation method of ethylene propylene rubber |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044282A (en) * | 1988-12-30 | 1990-08-01 | 联合碳化化学品及塑料有限公司 | Regulate the catalyzer that molecular weight ethylene polymer distributes |
| CN101092466A (en) * | 2006-06-23 | 2007-12-26 | 中国石油天然气股份有限公司 | Vanadium catalysis system for combined polymerization of ethylene, propylene, and diolefin, and application |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044282A (en) * | 1988-12-30 | 1990-08-01 | 联合碳化化学品及塑料有限公司 | Regulate the catalyzer that molecular weight ethylene polymer distributes |
| CN101092466A (en) * | 2006-06-23 | 2007-12-26 | 中国石油天然气股份有限公司 | Vanadium catalysis system for combined polymerization of ethylene, propylene, and diolefin, and application |
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