CN105732699A - Alkyloxy vanadium compounds, preparing method thereof and applications of the compounds - Google Patents
Alkyloxy vanadium compounds, preparing method thereof and applications of the compounds Download PDFInfo
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- CN105732699A CN105732699A CN201410757952.8A CN201410757952A CN105732699A CN 105732699 A CN105732699 A CN 105732699A CN 201410757952 A CN201410757952 A CN 201410757952A CN 105732699 A CN105732699 A CN 105732699A
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Abstract
The invention relate to alkyloxy vanadium compounds and a preparing method thereof. The method includes putting a reactor into a low-temperature cold trap, maintaining the temperature in a range from -40 DEG C to 10 DEG C, adding a vanadium compound into the reactor, slowly adding an alcohol compound, bubbling in high-purity nitrogen, and continuously feeding the high-purity nitrogen after the addition of the alcohol compound is finished until noncondensable gas produced in a reaction is fully blew out, thus preparing an alkyloxy vanadium compound. Clean alkyloxy vanadium compound products can be prepared through the method. Ethylene-alpha-olefin-conjugated diene random copolymers narrow in distribution can be synthesized through adopting the alkyloxy vanadium compounds as main catalysts and adopting alkyl aluminium halide as a cocatalyst.
Description
Technical field
The present invention relates to EP rubbers synthesis field, particularly to a kind of vanadium alkoxy compound and preparation method thereof, this vanadium alkoxy compound can be used for the random copolymerization of ethylene-alpha-olefin-nonconjugated alkadienes.
Background technology
nullVanadium alkoxy compound is at ethene-alpha-olefin、For major catalyst in the random copolymerization process of ethylene-alpha-olefin-nonconjugated alkadienes，Although ethene-alpha-olefin、The catalyst of the random copolymerization of ethene-alpha-olefin-alkadienes has evolved to Metallocene technology，But vfanadium compound is still the main flow catalyst of ethene-alpha-olefin combined polymerization now，It is good that this vfanadium compound solubility (is dissolved in inertia long chain alkane)，The random elastomeric body function admirable that ethene-alpha-olefin combined polymerization is obtained，So being still widely used in ethene-alpha-olefin combined polymerization field，Especially modified vfanadium compound，Owing to its molecular weight distribution obtained is narrow，It is widely used in fields such as resin modifieds，So vanadium alkoxy compound becomes the important catalyst of the random copolymerization compound of the ethylene-alpha-olefin-nonconjugated alkadienes of narrow ditribution.The synthesis of vanadium alkoxy compound is divided into the synthesis of pure material and has solvent to synthesize, there is solvent synthetic technology more ripe, the low concentration vanadium alkoxy compound of synthesis is as clear as crystal, do not precipitate generation, industrialization when feeding in raw material do not block charge pump, owing to valid density is low, it is necessary to the flow of charge pump is big, energy consumption is high, and relevant equipment investment is big.The synthesis of pure material, valid density is high, can feed in raw material with low-capacity pump, energy consumption is low, equipment investment is few, but the clogging deposits pump that during synthesis, side reaction produces, the cleaning of pump is frequent, if can obtain side reaction almost without the vanadium alkoxy compound of pure material synthesis be more satisfactory state, be also the objective place of the present invention.
Summary of the invention
It is an object of the invention to provide a kind of vanadium alkoxy compound and preparation method thereof and the application in the random copolymerization of ethylene-alpha-olefin-nonconjugated alkadienes.To synthesizing the vanadium alkoxy compound almost without precipitation in preparation process.
To achieve these goals, the invention provides a kind of vanadium alkoxy compound, its general structure is:
VAmLnX
Wherein 2≤m≤4,1≤n≤3,1≤w≤3；A is oxygen, and L is linear paraffin or the branched paraffin of 1-12 carbon, and X is any one in fluorine, chlorine, bromo element.
The preparation method that present invention also offers a kind of vanadium alkoxy compound, comprises the steps:
A. being placed in by reactor in low temperature cold hydrazine, temperature range is maintained at-40～10 DEG C；
B. first vfanadium compound is joined in step A, be then slowly added into alcohol compound, pass into high pure nitrogen simultaneously and carry out bubbling；
C., after treating that alcohol compound adds, continue to pass into the fixed gas that high pure nitrogen produces to blowout reaction completely, obtain vanadium alkoxy compound；
Wherein, described alcohol compound is 1～3:1 with the mol ratio of vfanadium compound.
The preparation method of vanadium alkoxy compound of the present invention, the preferred vanadium oxytrichloride of wherein said vfanadium compound, vanadium tetrachloride or vanadium trichloride.
The preparation method of vanadium alkoxy compound of the present invention, the preferred methanol of wherein said alcohol compound, ethanol, isopropanol, n-butyl alcohol, n-octyl alcohol, isooctanol or lauryl alcohol.
The mol ratio preferably 1～1.5:1 of the preparation method of vanadium alkoxy compound of the present invention, wherein said alcohol compound and vfanadium compound.
The preparation method of vanadium alkoxy compound of the present invention, the temperature range in wherein said step A preferably-20～8 DEG C.
The preparation method of vanadium alkoxy compound of the present invention, the temperature range in wherein said step A preferably-10～5 DEG C.
React in preparation vanadium alkoxy compound process at vfanadium compound and alcohol compound, selectable condition is a lot, find in many preparation conditions by studying, when reaction temperature is when-40～10 DEG C of scopes, the vanadium alkoxy compound generated is brown color, as clear as crystal, the by-product such as precipitation does not generate, good temperature conditions is-20～8 DEG C, better temperature conditions is-10～5 DEG C, and the vanadium alkoxy compound outward appearance prepared at normal temperatures is brownish black, opaque, illustrate that side reaction precipitation produces.
Vanadium alkoxy compound of the present invention can use in the random copolymerization of ethylene-alpha-olefin-nonconjugated alkadienes.
Vanadium alkoxy compound of the present invention is used as major catalyst in the random copolymerization of ethylene-alpha-olefin-nonconjugated alkadienes, the preferred alkyl aluminium halide of promoter of the present invention, more preferably a chlorine diethyl chlorine, dichloro one ethyl chloride, ethylaluminum two aluminum, further preferably ethylaluminum two aluminum (sesquialter aluminum), the wherein mol ratio of V preferably 1～100 in Al and major catalyst in promoter, more preferably 5～50, further preferably 6～20.
Employing vanadium alkoxy compound of the present invention makes major catalyst, when synthesizing ethylene-alpha-olefin, ethylene-alpha-olefin-nonconjugated dialkene random copolymer, and the aliphatic alkene such as the preferred propylene of alpha-olefin, 1-butylene, 1-hexene, 1-octene；The preferred 1,4-hexadiene of non-conjugated diene hydrocarbon, 1,6-octadiene, 5-methyl isophthalic acid, 4-hexadiene, 3,7-dimethyl-1,6-octadiene, 3,7 dimethyl-1,7-octadienes, diene such as 1 containing monocycle, 4-cyclohexadiene, 1,5-cyclo-octadiene, 1,5-ring 12 carbon diene；Diene containing bridged ring such as methyl tetrahydroindene, cyclopentadiene, dicyclopentadiene, 5-methyl-2-norborene, 5-ethylidene-2-norbornene (ethylidene norbornene ENB), 5-vinyl-2-norborene.
In the non-conjugated diene being usually used in preparing these copolymers, in ring, at least diene containing a double bond is preferred, more preferably 5-ethylidene-2-norbornene (ethylidene norbornene ENB).
In polymerization process of the present invention, polyreaction carries out under molecular weight regulator, the preferred diethyl zinc of selected molecular weight regulator or hydrogen, more preferably hydrogen.
The wherein preferred 0.5%-20% of hydrogen proportion in mixed air, more preferably 1%-10%, further preferably 2%-8%.
Polymerization of the present invention is the homogeneous polymerization that ethylene, propylene, alkadienes ternary polymerization are conventional, polymer solvent preferred aliphat alkane, cycloalkane or the aromatic compound adopted, more preferably aliphatic alkane, further preferably hexane.
In polymerization process of the present invention, polymerization reaction time is generally 10-180 minute, it is preferable that 20-60 minute.
In ethylene, propylene mixed air, propylene/ethylene (mol ratio) 1 to 6, it is preferable that 2 to 4.
Polymerization temperature is generally 15 DEG C-60 DEG C, it is preferable that 25 DEG C-45 DEG C.
Polymerization pressure is generally 0.01MPa-2MPa, it is preferable that 0.1MPa-1MPa.
The vanadium alkoxy compound of present invention synthesis, as clear as crystal, it does not have side reaction occurs, and is applied to the random copolymerization of ethylene-alpha-olefin-nonconjugated alkadienes, can obtain the ethylene-propylene terpolymer of narrow ditribution.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, but the present invention is not by the restriction of following embodiment.The change of any design without departing from the present invention and category, is within the scope of the present invention.
The kind of vfanadium compound:
In the present invention, the kind of vfanadium compound is not particularly limited, for instance can enumerate: vanadium oxytrichloride, vanadium tetrachloride or vanadium trichloride.
The kind of alcohol compound:
In the present invention, the kind of alcohol compound is not particularly limited, for instance can enumerate: methanol, ethanol, isopropanol, n-butyl alcohol, n-octyl alcohol, isooctanol or lauryl alcohol.
The mol ratio of alcohol compound and vfanadium compound:
In the present invention, the mol ratio of alcohol compound Yu vfanadium compound is not particularly limited, is generally: 1～3:1, it is preferable that 1～1.5:1.If the mol ratio of alcohol compound and vfanadium compound is less than 1:1, then exists in synthesized vanadium alkoxy compound and there is free vfanadium compound, cause, in application polymerization process, polymer architecture producing the possibility of impact.And if the mol ratio of alcohol compound and vfanadium compound more than 3:1 time, then exist in synthesized vanadium alkoxy compound and there is free alcohol compound, cause in application polymerization process, free alcohol can consume promoter and make active center poisoning, makes the possibility that polymerization can not be normally carried out.
Temperature range in step A:
In the present invention, the temperature range in step A is not particularly limited, is generally :-40～10 DEG C, it is preferable that-20～8 DEG C, further preferably-10～5 DEG C.If the temperature range in step A is less than-40 DEG C, then there is vanadium alkoxy compou nd synthesis response speed and slowly and cause the possibility that industrialization is difficult owing to synthesis temperature is too low.And if the temperature range in step A more than 10 DEG C time, then the vanadium alkoxy compound side reaction that there is synthesis is too much, and these side reactions exist the possibility blocking charge pump in industrial applications process.
Embodiment 1:
The synthesizer of catalyst be 200ml with bottom insert canal, feed pipe, exhaustor glass reactor, in advance reactor is carried out before reaction anhydrous, anaerobic and processes, and protect with high pure nitrogen.Reactor is placed in low temperature cold hydrazine before starting by reaction in advance, until temperature constant after-5 DEG C, the vanadium oxytrichloride of 20ml is added in reactor with medical needle tubing, it is then slowly added into the ethanol (alcohol/vanadium mol ratio is 1.5/1) of 18ml, pass into high pure nitrogen simultaneously and carry out bubbling, after alcohols adds, continue to use high pure nitrogen bubbling 2 hours, the vanadium alkoxy compound obtained is as clear as crystal brown yellow solution, concrete data such as table 1.
Embodiment 2:
By identical to the n-butyl alcohol replacement of the ethanol in embodiment 1, all the other conditions and operation and embodiment 1, result is table 1. such as
Embodiment 3:
By identical to the n-octyl alcohol replacement of the ethanol in embodiment 1, all the other conditions and operation and embodiment 1, result is table 1. such as
Embodiment 4:
Being replaced by vanadium oxytrichloride in embodiment 1 vanadium tetrachloride, ethanol lauryl alcohol replaces ,-5 DEG C with 10 DEG C of replacement, alcohol/vanadium mol ratio is 1/1, and all the other operations are same with embodiment 1, and result is table 1 such as.
Embodiment 5:
Being replaced by vanadium oxytrichloride in embodiment 1 vanadium trichloride, ethanol isopropanol replaces ,-5 DEG C with-40 DEG C of replacement, alcohol/vanadium mol ratio is 3/1, and all the other operations are same with embodiment 1, and result is table 1 such as.
Comparative example 1:
The synthesis of vanadium alkoxy compound, except being room temperature except reaction temperature, all the other conditions and operation and embodiment 1 identical, result is table 1 such as.
Comparative example 2:
With vanadium tetrachloride substitute vanadium oxytrichloride, alcohols adopt n-butyl alcohol, alcohol/vanadium mol ratio is 1/1, all the other conditions and operation and comparative example 1 identical, result is table 1 such as.
Comparative example 3:
With vanadium trichloride substitute vanadium oxytrichloride, alcohols adopt lauryl alcohol, alcohol/vanadium mol ratio is 3/1, all the other conditions and operation and comparative example 1 identical, result is table 1 such as.
Application examples:
Choose embodiment 1-3 and the obtained vanadium alkoxy compound of comparative example 1 carry out ethylene, propylene, the reaction of ethylidene norbornene binary polymerization:
nullBy ethylene、Propylene、Hydrogen is prepared by 1:2:0.15 by mixing arrangement，Then pass through recycle compressor to carry out being sufficiently mixed uniformly，Polymerization carries out in 5L polymeric kettle，5L polymeric kettle carries out anhydrous and oxygen-free under vacuum conditions process 1 hour，The noble gas used is high pure nitrogen，Then the 2000ml hexane (moisture≤10ppm) dried it is added thereto to wherein containing norborene (ENB) 4ml，ON cycle compressor，Gaseous mixture is passed in polymeric kettle，Mixed gas flow is 150L/ hour，The mixing gas that hexane dissolves is made to reach capacity，Then the hexane diluent of the vanadium alkoxy compound obtained it is added sequentially in above-described embodiment of 2ml (0.4mmol)，Add sesquialter aluminum，Making Al/V ratio is 10/1，Polymerization temperature is 30 DEG C，Polymerization pressure is 0.5MPa，Polymerization reaction time is 1 hour，After polyreaction，Glue is released from polymeric kettle lower bottom pipe by pressure in still，And terminate with ethanol，Add quantitative age resistor，The glue obtained is carried out steam distillation，The wet glue obtained dries 24 hours under 60 DEG C of vacuum.Result and analytical data such as table 2.
Table 1
Table 2
Find out from embodiment, although in the course of the polymerization process, the vanadium alkoxy compound of low-temp reaction and the vanadium alkoxy compound of normal-temperature reaction do not have difference at indices, but in the industry cycle a undisputable fact is, the many alkoxide compound of side reaction often can block charge pump in the industrial production, being because in opaque alkoxide compound has byproduct precipitate to generate, and does not then precipitate generation in as clear as crystal alkoxide compound, and this is also the purpose that the present invention to reach.
Claims (8)
1. a vanadium alkoxy compound, it is characterised in that the general structure of described vanadium alkoxy compound is:
VAmLnXw
Wherein 2≤m≤4,1≤n≤3,1≤w≤3；A is oxygen, and L is linear paraffin or the branched paraffin of 1-12 carbon, and X is any one in fluorine, chlorine, bromo element.
2. a preparation method for vanadium alkoxy compound, it is the preparation method of the vanadium alkoxy compound described in claim 1, comprises the steps:
A. being placed in by reactor in low temperature cold hydrazine, temperature range is maintained at-40～10 DEG C；
B. first vfanadium compound is joined in step A, be then slowly added into alcohol compound, pass into high pure nitrogen simultaneously and carry out bubbling；
C., after treating that alcohol compound adds, continue to pass into the fixed gas that high pure nitrogen produces to blowout reaction completely, obtain vanadium alkoxy compound；
Wherein, described alcohol compound is 1～3:1 with the mol ratio of vfanadium compound.
3. the preparation method of vanadium alkoxy compound according to claim 2, it is characterised in that described vfanadium compound is vanadium oxytrichloride, vanadium tetrachloride or vanadium trichloride.
4. the preparation method of vanadium alkoxy compound according to claim 2, it is characterised in that described alcohol compound is methanol, ethanol, isopropanol, n-butyl alcohol, n-octyl alcohol, isooctanol or lauryl alcohol.
5. the preparation method of vanadium alkoxy compound according to claim 2, it is characterised in that the mol ratio of described alcohol compound and vfanadium compound is 1～1.5:1.
6. the preparation method of vanadium alkoxy compound according to claim 2, it is characterised in that the temperature range in described step A is-20～8 DEG C.
7. the preparation method of vanadium alkoxy compound according to claim 6, it is characterised in that the temperature range in described step A is-10～5 DEG C.
8. the application in the random copolymerization of ethylene-alpha-olefin-nonconjugated alkadienes of the vanadium alkoxy compound described in claim 1.
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| US3457244A (en) * | 1964-04-28 | 1969-07-22 | Mitsubishi Petrochemical Co | Process for preparing a polymer |
| CN1049850A (en) * | 1989-08-08 | 1991-03-13 | 英国石油化学品有限公司 | Preparation is applicable to the method for the catalytic component based on vanadium of olefinic polymerization |
| CN1053242A (en) * | 1990-01-03 | 1991-07-24 | 英国石油化学品有限公司 | The preparation method of ziegler-natta type catalyst |
| CN1055367A (en) * | 1990-03-30 | 1991-10-16 | 英国石油化学品有限公司 | Ethene gas phase (being total to) polymeric carrier model polyolefin catalyst |
| CN1489603A (en) * | 2001-02-07 | 2004-04-14 | 沙特基础工业公司 | Catalyst composition for polymerization of olefins and method for preparing same |
| 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 |
| CN103665206A (en) * | 2013-12-10 | 2014-03-26 | 上海化工研究院 | Preparation method of multi-active-centre catalyst for olefin polymerization |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3457244A (en) * | 1964-04-28 | 1969-07-22 | Mitsubishi Petrochemical Co | Process for preparing a polymer |
| CN1049850A (en) * | 1989-08-08 | 1991-03-13 | 英国石油化学品有限公司 | Preparation is applicable to the method for the catalytic component based on vanadium of olefinic polymerization |
| CN1053242A (en) * | 1990-01-03 | 1991-07-24 | 英国石油化学品有限公司 | The preparation method of ziegler-natta type catalyst |
| CN1055367A (en) * | 1990-03-30 | 1991-10-16 | 英国石油化学品有限公司 | Ethene gas phase (being total to) polymeric carrier model polyolefin catalyst |
| CN1489603A (en) * | 2001-02-07 | 2004-04-14 | 沙特基础工业公司 | Catalyst composition for polymerization of olefins and method for preparing same |
| 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 |
| CN103665206A (en) * | 2013-12-10 | 2014-03-26 | 上海化工研究院 | Preparation method of multi-active-centre catalyst for olefin polymerization |
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