• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 引用文献
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  • 优先权
    • 专利摘要:
    Catalyst system, suitable for the (co)polymerization of ethylene and optionally minor amounts of 1-alkenes and/or dienes at such temperatures that the copolymer formed goes into solution, to be prepared by combining at least two components A and B, which components comprise: A : one or more magnesium compounds, one or more aluminium compounds, one or more transition metal compounds and optionally one or more halogen compounds, in such amounts that the atomic ratio of halogen to magnesium is at least 2, the atomic ratio of aluminium to transition metal is at least 3, the atomic ratio of aluminium to magnesium is at least 1, and the atomic ratio of magnesium to transition metal is at least 0.5, B : one or more organoaluminium. compounds of the general formula Rm<1>Al X<1>3-m, where the symbols R<1> are equal or different and represent a hydrocarbon residue with 1-20 carbon atoms and the symbols X<1> are equal or different and represent a hydrogen atom, a group of the general formula -NR<2>2 (where R<2> is a hydrocarbon residue with 1-10 carbon atoms), a group of the general formula -OR<3> (where R<3> is a hydrocarbon residue with 1-20 carbon atoms or a group of the general formula -Si(R<4>)3, where the symbols R<4> are equal or different and represent a hydrogen atom and/or a hydrocarbon residue with 1-20 carbon atoms), and 0 < m < 3, or a group of the general formula -[OAlR<5>)]n-OAlR2<5>, where the symbols R<5> are equal or different and represent a hydrocarbon residue with 1-10 carbon atoms, and n >/= 0, which two components are, separately or in combination, supplied direct to the polymerization vessel in such amounts that the atomic ratio of the aluminium from component B to the aluminium from component A is at least 0.1.
    公开号:SU1706377A3
    申请号:SU884355187
    申请日:1988-02-10
    公开日:1992-01-15
    发明作者:Мария Констант Косеманс Люк；Йозеф Паулус Герардус Ван Ден Бош Франс
    申请人:Стамикарбон Б.В.(Лайсенсинг Сабсидиари Ов Дсм) (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a catalytic system for the copolymerization of ethylene and 1-octene, to the preparation of this catalytic system and to a method for producing an ethylene-1-octene copolymer. The purpose of the invention is to increase the catalytic activity of the system due to the content in the component A as a magnesium compound butyl magnesium, as the halogen-containing compound is isopropyl chloride, and additionally sesquiethyl aluminum chloride at a certain atomic ratio of halogen to magnesium, aluminum to titanium, aluminum to magnesium , magnesium to titanium, due to the content in
     s
    ten
    15
    component B as alkyl aluminum alkoxide of diethyl aluminum ethoxide or as alkyl aluminum siloxide - diethyl aluminum dimethylethyl- oxide, at a certain atomic ratio of aluminum of component B to aluminum of component A.
    The purpose of the method for producing a catalytic system is to simplify the technology by using components A and B containing the above-mentioned compounds as starting components in a certain atomic ratio, due to their interaction at a certain temperature and a certain supply of components when mixed.
    The purpose of the method of obtaining a copolymer of ethylene and 1-octene is to obtain a copolymer with a high molecular weight and a good processability of bridges by using the aforementioned catalytic system and carrying out the copolymerization under certain conditions.
    The following examples illustrate the invention.
    PRI me R 1 and comparative example 1. Ethylene and hydrogen are metered into the reactor in quantities of 1325 and 9 mg / h, respectively, and octene-1 in the amount of / 60 g / h. The gasoline feed rate is 8.3 l / h. Isopropyl chloride (JPC1) is metered into the gasoline stream in an amount of 0.10 mmol / l. Component A is prepared by sequentially dosed with sesquiethyl aluminum chloride (SEAX, EI, i5AlCl, s), ethylbutylmagnesium
    20
    (COMPUTER) and tetrabutoxytitanium (TBT) along a separate supply line to the reactor in the amount indicated in Table 1. In this case, the catalyst ingredients are pre-mixed at -10 ° C during their residence in the feed lines, before the components are separately pumped into the reactor.
    The residence time in the feed lines of the catalyst components of the invention is usually sufficient to produce an active catalyst system. In most cases, this time should not exceed, for example, 5 minutes; more often, it is a smaller value, for example, less than 3 minutes and a minimum of 1 minute.
    In addition, diethyl aluminum ethoxide (LELGOX) is metered in as a component B in the gasoline supply line,
    17063774
    The polymer is recovered, if necessary, stabilized, dried and weighed. The activity of the catalytic system (a) is expressed in g PE / min / mol ethylene / l. The melt index (I.P.), expressed in g / min, is determined according to ASTM D1238, cf. The melt flow ratio (OTP) is calculated as a quotient of the melt index according to ASTM D 1238, conv. F, and the melt index according to ASTM D 1238, sm. E. Density d (kg / dm3) is measured according to ASTM D 1505. The effect of the presence of component B is visible from the results in Table 1 (examples 1 -3); Examples C-6 are given for comparison.
    Tables 8–14 give the values of atomic ratios of halogen to magnesium, aluminum to titanium, aluminum to magnesium, -magnesium to titanium, aluminum, aluminum, component A, and components A and B of the examples.
    Example 2 (comparative).
    To the final volume of 5U ml of pentamethylheptane (PMN) 0.6 mmol / l ethylbutylmagnesium solution (computer) and 3.0 mmol / l sesquiethylaluminium chloride solution (SEAX) are added, stirred for 2 hours at 7 ° C. Tetrabutoxytitanium is then added to a final concentration of 0.3 mmol / l and stirring is continued for 2 hours at 12f: ° C.
    The result is a precipitate in the form of a brown-black piece, which cannot be used for polymerization.
    PRI me R 3 (comparative). Example 1 is repeated, but in the absence of component B.
    The results are presented in table 2 (experiments 1, 2 and 3).
    PR and meer k (comparative).
    component B to isopropylchloro- according to prie30
    35
    40
    50
    Example 1 is repeated, but using Ј sesquiethyl aluminum chloride (SEAX) as component B (see Table 2, experiment k).
    PrimerZ (comparative). Example 1 is repeated, but triethyl aluminum (TEA) is used as component B (see Table 2, examples 5, 6 and 7).
    Example 2 and comparative example 6. 55 1975 g / h of ethylene, 16 mg / h of hydrogen, 1100 g / h of 1-octene and 12.2 l / h of gasoline are loaded into the reactor. The ethylene stream contains 0.10 mmol / l isopropyl chloride. AT
    Tables 8–14 give the values of atomic ratios of halogen to magnesium, aluminum to titanium, aluminum to magnesium, -magnesium to titanium, aluminum, aluminum, component A, and components A and B of the examples.
    component B to isopropylchloro- according to
    Example 1 is repeated, but using Ј sesquiethyl aluminum chloride (SEAX) as component B (see Table 2, experiment k).
    PrimerZ (comparative). Example 1 is repeated, but triethyl aluminum (TEA) is used as component B (see Table 2, examples 5, 6 and 7).
    Example 2 and comparative example 6. 5 1975 g / h of ethylene, 16 mg / h of hydrogen, 1100 g / h of 1-octene and 12.2 l / h of gasoline are loaded into the reactor. The ethylene stream contains 0.10 mmol / l isopropyl chloride. AT
    five
    Table 3, in which Example 1 is included for comparison, shows the effect of increasing amounts of component B with a low TBT content.
    Example (comparative). Example 2 is repeated, but in the absence of component B,
    The data are summarized in Table.
    Example 3. This example illustrates the effect of component B on increasing activity with an increase in the TBTB content of the polymerization conditions given in example 2. From this example (see table 5) in comparison with comparative example 7, it is clear that the amount of transition compound The metal required to achieve a certain activity decreases markedly.
    An example is comparative example 8. 1325 g / h of ethylene, 760 g / h of 1-octene, 9 mg / h of hydrogen and 8.3 l / h of gasoline are fed to the reactor. The ethylene stream contains 0.10 mmol / l isopropyl / loride. A mixture is used as the transition metal compound (see table 6, example 1 included, for comparison).
    Example 3 and comparative example 9. 1731 g / h of ethylene, 2 OC with g / h of 1-octene, 5 mg / h of hydrogen and 9 L / m of gasoline are fed to the reactor; ethylene flow is 0.10 mmol / l isopropyl chloride. As component B, use is made (see Table 7) of diethyl aluminum - dimethylethylsiloxide (LADS).
    Experiment 1 is included in Table 7 for the purpose of comparison.
    As follows from the presented data, the catalyst according to the invention is not only very active, but also very fast, so that its residence time is very short (about 5 minutes). A short residence time is of great importance, since it makes it possible to use a small reactor. Thus, in a reactor with a capacity of 5 m3, using catalysts according to the invention, annual production of more than 500 ppm can be achieved. According to the known method, the total preparation time of component A is from b to 16 hours .
    Another advantage is that components A and B are fed directly into the reaction vessel, i.e. without additional heating, holding
    ten
    15
    20
     7 (
    ki, sediment recovery and / or other treatments. This is a significant advantage for polymerization on an industrial scale, where all efforts are aimed at improving the process. The polymers produced by the catalysts of this invention have properties that are commercially desirable, for example, a sufficiently high molecular weight (low melting index) and good processability. They can be used to produce injection-molded films and blown-half films with good mechanical and optical properties, while their rheological properties and ability to swell meet the usual requirements. Polymers are also suitable for many other applications, for example injection molding or by shading.
    权利要求:
    Claims (3)
    [1]
    1. Catalytic system for the copolymerization of ethylene and 1-octene in solution, containing component A, including Magiir compound, titanium compound - tetraabutoxytitanium and / or titanium tetrachloride, hydrogen oxide compound, and -. B, representing itself. lh: mini-alkoxide or 1 alkyl-aluminum / y-, xyd, it is noted that, with the aim of increasing the catalytic activity of the system, component A contains ethylbutyl magnesium as the magnesium compound, and isopropyl chloro as the magnesium compound - read and additionally sesquiethyl aluminum chloride at the following atomic ratio: halogen to magnesium from 2.08. to 17, aluminum to titanium from, 75 to M, I 4, aluminum to magnesium from 2.72 to 5.02, magnesium to titanium from 1.25 to 10.0 and component B contains diethyl aluminum ethoxide as alkyl aluminum alkoxide or as an alkylaluminum sulfoxide, it is dimethyl aluminum dimethyl ethylsiloxide with an atomic ratio of aluminum of component B to aluminum of component A equal to 0.13-1.58.
    [2]
    2. A method for preparing a catalytic system for the copolymerization of ethylene and 1-octene in solution, comprising reacting component A containing a magnesium compound, compound
    0
    0
    five
    0
    five
    eleven
    titanium - tetrabutoxytitanium and / or titanal tetrachloride, a halogen-containing compound, and component B, which is an alkyl aluminum-alkoxide or alkyl aluminum siloxide, characterized in that, to simplify the technology, use component A, containing ethylbutyl magnesium as the magnesium compound the halogen-containing compound is isopropyl chloride and additionally containing sesqui-ethyl aluminum chloride at the following atomic ratio: halogen to magnesium from 2.08 to 17, aluminum to titanium from 75 to 1.04, aluminum to magnesium from 2.7 2 to 5.02, magnesium to titanium from 1.25 to 10.00, and component B, containing diethyl aluminum ethoxide as the alkyl aluminum alkoxide or diethyl aluminum dimethyl ethyl siloxide as the alkyl aluminum siloxane, and the reaction is carried out by sequential mixing at 10 C first with magnesium compounds with sesquiethyl aluminum chloride, then with isopropyl chloride and titanium compound, followed by feeding component B with an atomic ratio of aluminum of component B to aluminum of component A equal to 0.13-1.58.
    063778
    [3]
    3. A method of producing a copolymer of ethylene and 1-octene by copolymerizing ethylene and 1-octene in solution at elevated temperature in the presence of a catalytic system containing component A, including a magnesium compound, a titanium compound — tetrabutoxytitanium, and / or tetrachloride
    Yu titanium, and component B, which is an alkylaluminium alkoxide or an alkylaluminium aluminum oxide, characterized in that, in order to obtain a copolymer with a low melt index,
    J5 uses a catalytic system comprising component A, containing magnesium butyl magnesium in the achestate compound, and isopropyl chloride as the halogen-containing compound
    20 and additionally contains sesquiatyl aluminum chloride with the following atomic ratio: halogen to magnesium from 2.08 to 1.17, aluminum to titanium from 4.75 to 1, aluminum to magnesium from 2.72
    25 to 5.0., Magnesium to titanium from 1.25 to 10.00, and component B, containing diethyl aluminum ethoxide as the alkylominylminoalkyl oxide or minidimethylethylsiloxide as the alkylaluminum siloxane, with an atomic ratio of the aluminum component. B to the aluminum component A, equal to 0.13-1.58, and the copolymerization is carried out at 185 ° C.
    Table 1
    one
    2
    3 C S
    TEA (triethyl aluminum) 0,300,06 0,03
    0.10
    925
    5С
    Table 2
    Table5
    and
    u
    Table
    Table 10
    15
    17P6377
     sixteen
    Continuation of table 10
    Table 13
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    同族专利:
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    NL8700322A|NL8700322A|1987-02-11|1987-02-11|CATALYST SYSTEM FORPOLYMERIZATION OF ETHENE IN SOLUTION.|
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