CN105732699B - Vanadium alkoxy compound and its preparation method and application - Google Patents
Vanadium alkoxy compound and its preparation method and application Download PDFInfo
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- CN105732699B CN105732699B CN201410757952.8A CN201410757952A CN105732699B CN 105732699 B CN105732699 B CN 105732699B CN 201410757952 A CN201410757952 A CN 201410757952A CN 105732699 B CN105732699 B CN 105732699B
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Abstract
The present invention relates to a kind of vanadium alkoxy compound and preparation method thereof, this method the specific steps are：Reactor is placed in low temperature cold hydrazine, temperature range is maintained at 40~10 DEG C；First vfanadium compound is added in reactor, is then slowly added into alcohol compound, while being passed through high pure nitrogen and being bubbled；After waiting for that alcohol compound is added, continue to be passed through the fixed gas generated in high pure nitrogen to complete blowout reaction, up to vanadium alkoxy compound, clean vanadium alkoxy compound products can be made using the preparation method, use the vanadium alkoxy compound as major catalyst, alkyl aluminium halide is the ethylene-alpha-olefin non-conjugated dialkene random copolymer that co-catalyst can synthesize narrow ditribution.
Description
Technical field
The present invention relates to EP rubbers to synthesize field, more particularly to a kind of vanadium alkoxy compound and preparation method thereof should
Vanadium alkoxy compound can be used for the random copolymerization of ethylene-alpha-olefin-nonconjugated alkadienes.
Background technology
Random copolymerization process of the vanadium alkoxy compound in ethene-alpha-olefin, ethylene-alpha-olefin-nonconjugated alkadienes
In be used for major catalyst, although the catalyst of the random copolymerization of ethene-alpha-olefin, ethene-alpha-olefin-alkadienes has developed to
Metallocene technology, but vfanadium compound is still the mainstream catalyst of ethene-alpha-olefin combined polymerization now, and this vfanadium compound is solvable
Property (being dissolved in inertia long chain alkane) it is good, the obtained random elastomeric body function admirable of ethene-alpha-olefin combined polymerization, thus still extensively
Applied in ethene-alpha-olefin combined polymerization field, it is especially modified vfanadium compound, polymer molecular weight distribution obtained due to it
It is narrow, it is widely used in fields such as resin modifieds, so vanadium alkoxy compound is non-total as narrow ditribution ethene-alpha-olefin-
The important catalyst of the random copolymerization object of yoke alkadienes.The synthesis of vanadium alkoxy compound is divided into the synthesis of pure material and has molten
Agent synthesizes, and has solvent synthetic technology more ripe, and the low concentration vanadium alkoxy compound of synthesis is as clear as crystal, does not precipitate generation,
Charge pump is not blocked when feeding in industrialization, since effective concentration is low, needs the flow of charge pump big, high energy consumption is relevant
Equipment investment is big.The synthesis of pure material, effective concentration is high, can be fed with low-capacity pump, and low energy consumption, and equipment investment is few, but closes
At when side reaction generate clogging deposits pump, the cleaning of pump is frequent, if can obtain side reaction almost without pure material synthesis
Vanadium alkoxy compound be more satisfactory state and spirit of the invention where.
Invention content
The purpose of the present invention is to provide a kind of vanadium alkoxy compounds and preparation method thereof, and non-in ethene-alpha-olefin-
Application in the random copolymerization of conjugated diene.To synthesize the vanadium alkoxy chemical combination almost without precipitation in preparation process
Object.
To achieve the goals above, the present invention provides a kind of vanadium alkoxy compound, general structure is：
VAmLnX
Wherein 2≤m≤4,1≤n≤3,1≤w≤3；A is oxygen, and L is the linear paraffin or branched paraffin of 1-12 carbon, and X is
Any one in fluorine, chlorine, bromo element.
The present invention also provides a kind of preparation methods of vanadium alkoxy compound, include the following steps：
A. reactor is placed in low temperature cold hydrazine, temperature range is maintained at -40~10 DEG C；
B. first vfanadium compound is added in step A, is then slowly added into alcohol compound, at the same be passed through high pure nitrogen into
Row is bubbled；
C. after waiting for that alcohol compound is added, continue to be passed through not coagulating of being generated in high pure nitrogen to complete blowout reaction
Gas is to get vanadium alkoxy compound；
Wherein, the molar ratio of the alcohol compound and vfanadium compound is 1~3：1.
The preparation method of vanadium alkoxy compound of the present invention, wherein the preferred vanadium oxytrichloride of the vfanadium compound, four
Vanadium chloride or vanadium trichloride.
The preparation method of vanadium alkoxy compound of the present invention, wherein the preferred methanol of the alcohol compound, ethyl alcohol,
Isopropanol, n-butanol, n-octyl alcohol, isooctanol or lauryl alcohol.
The preparation method of vanadium alkoxy compound of the present invention, wherein the alcohol compound and vfanadium compound rub
That ratio preferably 1~1.5：1.
The preparation method of vanadium alkoxy compound of the present invention, wherein the temperature range preferably -20 in the step A
~8 DEG C.
The preparation method of vanadium alkoxy compound of the present invention, wherein the temperature range preferably -10 in the step A
~5 DEG C.
During vfanadium compound reacts with alcohol compound and prepares vanadium alkoxy compound, there are many selectable condition,
It is found in many preparation conditions by studying, when reaction temperature is in -40~10 DEG C of ranges, the vanadium alkoxy compound of generation is
Brown color, it is as clear as crystal, it the by-products such as does not precipitate and generates, preferable temperature condition is -20~8 DEG C, better temperature condition
It is -10~5 DEG C, and the vanadium alkoxy compound appearance prepared at normal temperatures is in brownish black, it is opaque, illustrate have side reaction heavy
It forms sediment and generates.
Vanadium alkoxy compound of the present invention can be in the random copolymerization of ethylene-alpha-olefin-nonconjugated alkadienes
Middle use.
Vanadium alkoxy compound of the present invention is used in the random copolymerization of ethylene-alpha-olefin-nonconjugated alkadienes
Make major catalyst, the preferred alkyl aluminium halide of co-catalyst of the present invention, more preferable chlorine diethyl chlorine, one ethyl of dichloro
Chlorine, two aluminium of ethylaluminum, further preferably two aluminium of ethylaluminum (sesquialter aluminium), Al and V in major catalyst wherein in co-catalyst
Molar ratio preferably 1~100, more preferable 5~50, further preferably 6~20.
The present invention is used makees major catalyst with vanadium alkoxy compound, and synthesizing ethylene-alpha-olefin, ethene-alpha-olefin-are non-total
When yoke dialkene random copolymer, the aliphatic olefins such as the preferred propylene of alpha-olefin, 1- butylene, 1- hexenes, 1- octenes；It is non-conjugated
The preferred 1,4- hexadienes of alkadienes, 1,6- octadienes, 5- methyl-1s, 4- hexadienes, 3,7- dimethyl -1,6- octadienes, 3,7 2
Methyl-1,7- octadienes, the diene containing monocycle such as 1,4- cyclohexadiene, 1,5- cyclo-octadiene, 12 carbon diene of 1,5- rings；Containing bridge
The diene of ring such as methyl tetrahydroquinone, cyclopentadiene, dicyclopentadiene, 5- methyl -2- norbornene, 5- ethylidene -2- norborneols
Alkene (ethylidene norbornene ENB), 5- vinyl -2- norbornene.
In being usually used in preparing the non-conjugated diene of these copolymers, it is preferred that the diene of a double bond is at least contained in ring
, more preferable 5- ethylidene -2- norbornene (ethylidene norbornene ENB).
In polymerization process of the present invention, polymerisation carries out under molecular weight regulator, selected molecular weight regulator
It is preferred that diethyl zinc or hydrogen, more preferable hydrogen.
The wherein preferred 0.5%-20% of hydrogen proportion in mixed air, more preferable 1%-10%, further preferably 2%-
8%.
Polymerization of the present invention is ethylene, propylene, the common homogeneous polymerization of alkadienes ternary polymerization, is used
Polymer solvent preferred aliphat alkane, cycloalkane or aromatic compound, more preferable aliphatic alkane, further preferably hexane.
In polymerization process of the present invention, polymerization reaction time is generally 10-180 minutes, preferably 20-60 minutes.
In ethylene, propylene mixed air, propylene/ethylene (molar ratio) 1 to 6, preferably 2 to 4.
Polymerization temperature is generally 15 DEG C -60 DEG C, preferably 25 DEG C -45 DEG C.
Polymerization pressure is generally 0.01MPa-2MPa, preferably 0.1MPa-1MPa.
The vanadium alkoxy compound that the present invention synthesizes, it is as clear as crystal, there is no side reaction, is applied to ethylene-α-alkene
The random copolymerization of hydrocarbon-non-conjugated diene hydrocarbon, can be obtained the ethylene-propylene terpolymer of narrow ditribution.
Specific implementation mode
The present invention is described in further detail with reference to specific embodiment, but the present invention is not by following embodiments
Limitation.The change of any design and scope without departing from the present invention, is within the scope of the present invention.
The type of vfanadium compound：
In the present invention, the type of vfanadium compound is not particularly limited, such as can enumerated：Vanadium oxytrichloride, four chlorinations
Vanadium or vanadium trichloride.
The type of alcohol compound：
In the present invention, the type of alcohol compound is not particularly limited, such as can enumerated：Methanol, ethyl alcohol, isopropyl
Alcohol, n-butanol, n-octyl alcohol, isooctanol or lauryl alcohol.
The molar ratio of alcohol compound and vfanadium compound：
In the present invention, the molar ratio of alcohol compound and vfanadium compound is not particularly limited, usually：1~3：1,
It is preferred that 1~1.5：1.If the molar ratio of alcohol compound and vfanadium compound is less than 1：When 1, then there is synthesized vanadium alkoxy
There is free vfanadium compound in compound, causes in application polymerization process, the possibility that polymer architecture is had an impact.And
If the molar ratio of alcohol compound and vfanadium compound is more than 3：When 1, then exists and exist in synthesized vanadium alkoxy compound
Free alcohol compound causes in application polymerization process, and free alcohol can consume co-catalyst and activated centre is made to be poisoned,
Prevent polymerization from the possibility that is normally carried out.
Temperature range in step A：
In the present invention, the temperature range in step A is not particularly limited, usually：- 40~10 DEG C, preferably -20~
8 DEG C, further preferably -10~5 DEG C.If the temperature range in step A is less than -40 DEG C, there are vanadium alkoxy compound synthesis
Reaction speed is slow and leads to the possibility of industrialization difficulty since synthesis temperature is too low.And if the temperature range in step A is more than
At 10 DEG C, then the vanadium alkoxy compound side reaction that there is synthesis is excessive, and these side reactions are deposited during industrial applications
In the possibility for blocking charge pump.
Embodiment 1：
The synthesizer of catalyst is glass reactors of the 200ml with bottom insert canal, feed pipe, exhaust pipe, before reacting in advance
Anhydrous, anaerobic processing is carried out to reactor, high pure nitrogen is used in combination to protect.Reactor is placed in low temperature cold hydrazine by reaction in advance before starting
It is interior, it is constant after -5 DEG C after temperature, the medical needle tubing of the vanadium oxytrichloride of 20ml is added in reactor, 18ml is then slowly added into
Ethyl alcohol (alcohol/vanadium molar ratio be 1.5/1), while being passed through high pure nitrogen and being bubbled, after alcohols is added, continue with high-purity
Nitrogen is bubbled 2 hours, and obtained vanadium alkoxy compound is as clear as crystal brown yellow solution, specific data such as table 1.
Embodiment 2：
Ethyl alcohol in embodiment 1 is replaced with n-butanol, remaining condition and operation are same as Example 1, as a result such as table 1.
Embodiment 3：
Ethyl alcohol in embodiment 1 is replaced with n-octyl alcohol, remaining condition and operation are same as Example 1, as a result such as table 1.
Embodiment 4：
Vanadium oxytrichloride in embodiment 1 is replaced with vanadium tetrachloride, ethyl alcohol is replaced with lauryl alcohol, and -5 DEG C are replaced with 10 DEG C,
Alcohol/vanadium molar ratio is 1/1, remaining operation and embodiment 1 are same, as a result such as table 1.
Embodiment 5：
Vanadium oxytrichloride in embodiment 1 is replaced with vanadium trichloride, ethyl alcohol is replaced with isopropanol, and -5 DEG C are replaced with -40 DEG C,
Alcohol/vanadium molar ratio is 3/1, remaining operation and embodiment 1 are same, as a result such as table 1.
Comparative example 1：
The synthesis of vanadium alkoxy compound, in addition to reaction temperature is room temperature, remaining condition and operation are same as Example 1,
As a result such as table 1.
Comparative example 2：
Vanadium oxytrichloride is substituted with vanadium tetrachloride, it is 1/1 that alcohols, which uses n-butanol, alcohol/vanadium molar ratio, remaining condition and operation
It is identical as comparative example 1, as a result such as table 1.
Comparative example 3：
Vanadium oxytrichloride is substituted with vanadium trichloride, it is 3/1 that alcohols, which uses lauryl alcohol, alcohol/vanadium molar ratio, remaining condition and operation
It is identical as comparative example 1, as a result such as table 1.
Application examples：
It chooses embodiment 1-3 and 1 obtained vanadium alkoxy compound of comparative example carries out ethylene, propylene, ethylidene norborneol
Alkene binary polymerization reacts：
Ethylene, propylene, hydrogen are pressed 1 by mixing arrangement：2：0.15 is prepared, and is then carried out by recycle compressor
It is sufficiently mixed uniformly, polymerization carries out in 5L polymeric kettles, and 5L polymeric kettles are carried out to anhydrous and oxygen-free processing 1 under vacuum conditions
Hour, used inert gas be high pure nitrogen, then thereto be added 2000ml drying hexane (aqueous≤10ppm) its
In contain norbornene (ENB) 4ml, ON cycle compressor is passed through gaseous mixture, mixed gas flow 150L/ into polymeric kettle
Hour, so that the mixed gas that hexane dissolves is reached saturation, is then added sequentially in above-described embodiment of 2ml (0.4mmol) and obtains
Vanadium alkoxy compound hexane dilution, be added sesquialter aluminium, make Al/V ratios be 10/1, polymerization temperature be 30 DEG C, polymerization pressure
Power is 0.5MPa, and polymerization reaction time is 1 hour, after polymerisation, by glue by pressure in kettle from polymeric kettle lower bottom pipe
It releases, is used in combination ethyl alcohol to terminate, quantitative anti-aging agent is added, obtained glue is subjected to steam distillation, obtained wet glue is 60
It is 24 hours dry under DEG C vacuum.As a result and analysis 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 normal-temperature reaction
Vanadium alkoxy compound does not have difference in indices, but in the industry cycle a undisputable fact is the alkoxylate more than side reaction
Charge pump can often be blocked in the industrial production by closing object, be to have byproduct precipitate life because of in opaque alkoxide compound
At, and then generated without precipitation in as clear as crystal alkoxide compound, this is also present invention purpose to be achieved.
Claims (6)
1. a kind of preparation method of vanadium alkoxy compound, which is characterized in that include the following steps：
A. reactor is placed in low temperature cold hydrazine, temperature range is maintained at -40~10 DEG C；
B. first vfanadium compound is added in step A, is then slowly added into alcohol compound, while be passed through high pure nitrogen and being roused
Bubble；
C. after waiting for that alcohol compound is added, continue to be passed through the fixed gas generated in high pure nitrogen to complete blowout reaction, i.e.,
Obtain vanadium alkoxy compound；
Wherein, the molar ratio of the alcohol compound and vfanadium compound is 1~3：1；
The general structure of the vanadium alkoxy compound is：
VAmLnXw
Wherein 2≤m≤4,1≤n≤3,1≤w≤3；A is oxygen, and L is the linear paraffin or branched paraffin of 1-12 carbon, X be fluorine,
Any one in chlorine, bromo element.
2. the preparation method of vanadium alkoxy compound according to claim 1, it is characterised in that the vfanadium compound is three
Chlorine vanadyl, vanadium tetrachloride or vanadium trichloride.
3. the preparation method of vanadium alkoxy compound according to claim 1, it is characterised in that the alcohol compound is
Methanol, ethyl alcohol, isopropanol, n-butanol, n-octyl alcohol, isooctanol or lauryl alcohol.
4. the preparation method of vanadium alkoxy compound according to claim 1, it is characterised in that the alcohol compound with
The molar ratio of vfanadium compound is 1~1.5：1.
5. the preparation method of vanadium alkoxy compound according to claim 1, it is characterised in that the temperature in the step A
Ranging from -20~8 DEG C.
6. the preparation method of vanadium alkoxy compound according to claim 5, it is characterised in that the temperature in the step A
Ranging from -10~5 DEG C.
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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 |
-
2014
- 2014-12-10 CN CN201410757952.8A patent/CN105732699B/en active Active
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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