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    • 专利摘要:
    A method is disclosed for preparing a catalyst system for polymerizing alpha -olefins. This method comprises admixing with at least an organoaluminum compound an activated titanium component which is prepared by first reacting a titanium compound of the general formula, TiXn(OR)4-n (in which X is a halogen atom, R is an alkyl group or a phenyl group, and n is 2 to 4), with a metal of Group II or III of the Periodic Table and a halide of a metal of Group II or III of the Periodic Table in the presence of an aromatic compound, then treating the resulting reaction product with an oxygen-containing organic compound, and further treating with a tetrahalide of titanium, vanadium or both at a temperature of from -80 DEG C. to 80 DEG C., and finally aging at a temperature above 30 DEG C. for from 30 minutes to 24 hours.
    公开号:SU1014465A3
    申请号:SU772447301
    申请日:1977-02-04
    公开日:1983-04-23
    发明作者:Такамура Есинори；Хамада Хакусеи；Китамура Киеюки；Инада Тецуро；Кодама Кунио；Юсами Котуюки
    申请人:Мицуи Тоацу Кемикалз,Инкорпорейтед (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to methods for producing the titanium component of a catalytic system for the polymerization of propylene.
    A method is known for producing the titanium component of a catalytic system for the polymerization of propylene by reducing titanium tetrachloride with hydrogen or titanium at kOO ° C lj.
    The closest to the proposed technical essence and the achieved effect is a method of obtaining the titanium component of a catalytic system for the polymerization of propylene containing an organoaluminum compound, consisting in the chemical interaction of titanium tetrachloride dissolved in an inert solvent, with aluminum diethyl monochloride or with aluminum ethyl ethyl chloride dissolved in an inert solvent, inert inert inert solvent, or aluminum ethyl ethyl chloride dissolved in an inert solvent dissolved in an inert solvent, or dissolved aluminum inert solvent, or dissolved in inert solvent and in an inert solvent dissolved in an inert solvent. , and in the subsequent heat treatment at after washing 2j,
    However, the known catalytic system is practically inapplicable due to its low activity. Thus, the activity of the catalytic system | containing the titanium component obtained in a known manner used to polymerize propylene, is 160-220 g of polymer / g h.
    The purpose of the invention is to obtain a component that increases the activity of the catalytic system,
    The goal is achieved in that according to the method of producing the titanium component of the catalytic system for the polymerization of propylene by reacting titanium tetrachloride, aluminum metal and aluminum trichloride at 50-200 ° C in the presence of benzene or benzene with heptane in a volume ratio of 1: 1, first processing the resulting product with an oxygen-containing organic compound at minus 50, plus IfjO C, then titanium tetrachloride or vanadium pentachloride at minus 5, plus followed by aging at 30-90 C.
    Aluminum is used; in an amount of 1 mol per 1 mol of titanium compound, benzene in an amount of 19 mol per mol of titanium compound, as the oxygen-containing organic compound, a compound selected from the group comprising n-propyl ether, butyl ether, isoamyl ether, anisole , diethyl ketone and butyl acetate, in an amount of 1.0-3.2 mol per J mol of the reaction product.
    The method for producing the titanium component of the catalytic system for the polymerization of propylene provides a component that enhances the activity of the catalytic system. Thus, the activity of the catalytic system containing the titanium component obtained according to the invention used in the polymerization of propylene is 623-893 polypropylene / g-h
    A catalytic system for the polymerization of propylene consists of a mixture of an organoaluminum compound and an enhanced titanium component, which is obtained by reacting titanium tetrachloride, aluminum metal and aluminum trichloride in the presence of benzene or benzene with heptane to obtain the reaction product (complex A); Complex A is treated with an oxygen-containing organic compound with a minus 50-plus liJOCs further treated with titanium or vanadium tetrachloride and brought to its natural state (kept) at a temperature above 30-90 C.
    Polymerization of propylene in the presence of a catalytic system proceeds at a very high rate and flow rate; -: to obtain polymers with a small amount of fine fractions and the same size of crystalline particles.
    Metallic aluminum and aluminum trichloride are used in quantities; the molar ratio of which is 0, preferably 0.5–20, due to a conflict with the titanium compound, respectively. The aromatic compound serves both as a reagent and as a solvent, and it is usually used in an amount whose molar ratio is 11-10 (/, preferably 20 O in comparison with the titanium compound.
    The reaction temperature for the preparation of complex A is usually in the range of 50-200 ° C. The reaction time is usually h, although this number is not critical.
    The resulting complex is then treated with an oxygen-containing organic compound.  Typical predatic compounds are esters, ketones,.  complex zfira and similar compounds.  Of these, n-propyl ether, n-butyl ether, isoamyl ether, anisole diethyl ketone and butyl acetate are preferred.  The treatment of the complex with an A-oxygen-containing organic compound can be carried out in the presence of an aromatic compound such as benzene used in the preparation of complex A with or without the addition of a fresh solvent such as n-heptec, or can be carried out after the primary removal of the aromatic compound from.  complex A and the addition of a fresh solvent, such as n-heptane for replacement.  It is desirable that the treatment temperatures be within minus 50 - plus 150. WITH.  The reaction time, although not standardized, usually ranges from a few minutes to 24 hours, during which time the reaction mixture is preferably stirred.  The amount of oxygen-containing compound is in the range of 0.1-20 mol, preferably 0.5-5 mol per 1 mol of complex A.  Complex A treated with an oxygen-containing organic compound is then treated with titanium tetrachloride with vanadium or both in the presence or absence of a solvent such as n-heptane.  Such processing can be carried out in the presence of a VII of a mixture of an oxygen-containing organic compound and a solvent such. as n-heptane from the preceding step, or it can be prozode after replacing this medium with an inert solvent, such as n-heptane, by separating the treated complex A from the hkydka medium by means of decanting or filtration.  The treatment is preferably carried out under mixing at minus 80-Gluse 80 ° С, preferably minus 50-plus 30 ° С.  Temperatures higher not only lower the activity of the catalytic system obtained here during polymerization, even, sCP: -1 the titanium component is activated by treatment (aging, aging), but also lowers the stereoregularity of the polyosphins obtained in the polymerization stage.  The processing time is usually within 5 minutes to 24 hours, although it is not critical.  in the range of 0.1–20 mol, preferably 0.5i mol per mole in the beginning of the complex A used.  After completion of the treatment, the titanium component undergoes aging (aging), the titanium component obtained. before aging (aging), it is brown or black brown and does not show.  almost no activity when used either directly, either during the polymerization of propylene, or in combination with an organoaluminum compound during the polymerization of propylene.  Such a titanium component cannot be used in the polymerization of propylene.  When a titanium component is used in the catalytic system, which is obtained from the reduction of titanium tetrachloride using an organoaluminum compound and aging (aging), the activity in the polymerization of olefins and the sterility of polymers, sex. scientists on their ocHCiv-s may improve.  However, the activity during polymerization and the ability of the titanium component of the pp to give stereo regulation is still very high. stoicap even if titanoBZ compo. nzntg undergoes aging 1 cut; .  When the titanium component rolled. , the classical system undergoes aging (aging), then the activity of the catalytic system, ---; mean feno uelpchiaget ;.  its ability to increase and the ability to receive the polyegulrnost, temperature measures with T: aging (dy. romanil) in practice, you need: c-hold above 30 ° C iron; ; :.  t: areas.  Time-old chip  depending on the temperature, it finds: cv ----- ex ZS mi- (24 c, although it is not a critical time for FP 3 fip, the sting should be carried out under such conditions of temperature and pressure; the color of the titanium component should turn from brown 3 black -purple.  The obtained ciKTHBHpoBaHHvio titanose component of the catalytic system can be used in the state of suspension, or after removing a solvent such as n-heptav used before aging, it can be dried.  The activated titanium component in combination with an organoaluminum compound is used as a catalytic system for the polymerization of propylene.  The organo-aluminum compound that is used in combination with the activated titanium component can be any of the known organo-aluminum compounds that are commonly used as catalysts for the polymerization of olefins together with transition metal halides, such as titanium trichloride.  The catalytic system of the invention can be added to the well-known third component of the system, as this is done in the practical use for the polymerization of olefins in the catalytic system of the gatgoid transition metal — the organo-aluminum compound — the third component.  Preferred organoaluminium compounds are those that meet the general formula or AIR. wherein R is an alkyl group or aryl group, and X is a halogen atom.  Examples of preferred organo-aluminum compounds are diethyl aluminum monochloride, aluminum triethyl, di-n-propyl aluminum monochloride, tri-n-butyl aluminum, di-isobuty aluminum monochloride, tri-isobutyl aluminum or mixtures of them.  The molar ratio of the organoaluminum compound to the activated titanium component is usually in the range of 1: 0.1-1; 100, preferably 1: 0.5-1: 50.  In addition to propylene, various types of monomers, such as ethylene, butenpentene-1, hexene-1, -methylpentene-1, and their mixture can polymerize or copolymerize.  The polymerization reaction can be carried out under conditions that are commonly used in polymerization.  That is, the reaction temperature is in the region of 20 ° C, preferably SO-IOO C, and the reaction pressure ranges from atmospheric to 200 atm, preferably to 100 atm.  Aliphatic alloys may be used as the solvent for the polymerization reaction.  alicyclic and aromatic hydrocarbons or mixtures thereof.  For example, it is desirable to use propane, butane, hexane, heptane, benzene, toluene and similar solvents. Olefins can be polymerized or copolymerized under conditions that are free of solvent, for example in the gas phase, in a block or by liquid-phase polymerization.  The molecular sec of the polymers varies depending on the reaction method, type of catalyst system and polymerization conditions, but it can also be controlled by adding hydrogen, alkyl halide, dialkyl zinc or other additives. All activated titanium components obtained in the examples are colored black-purple. .  PRI me R 1, 1).  Preparation of the complex A.  300 ml of benzene, 3 g of titanium tetrachloride, 32 g of aluminum trichloride and fj g of powdered metallic aluminum are loaded into a four-necked flask with a capacity of 500 t-in, with a stirrer, nitrogen atmosphere.  The temperature of the contents of the flask is gradually increased with stirring until the boiling of the reaction system begins, followed by maintaining the boiling point of temperature using a reflux condenser for approximately 15 hours.  After completion of the reaction, unreacted mpxxJ, the treated aluminum and aluminum metal are removed from the reaction system, and the resulting liquid phase (t. e.  the solution of complex A) is introduced into the flask for the liquid catalyst and stored.  The concentration of complex A is 0.2 g / ml.  2 c) Treatment with an oxygen-containing organic compound.  77 ml of complex A, prepared according to  1), loaded into a 300-ml four-necked distillation flask equipped with a stirrerJ in a nitrogen atmosphere.  Then 22 ml of n-butyl ether was added to this flask with stirring.  After completion of the addition operation, the temperature of the flask is gradually increased from to with the next;; stirring at this temperature for about 1 hour.  After this, 50 L of fresh are added to the flask. - {- heptane.  7iQ 3c).  Treatment with titanium tetrachloride.  The reaction system, which is described in paragraph  2), is continuously stirred at 3i) C and then cooled to, maintaining this temperature, and a mixture of 10 ml of titanium tetrachloride and 50 ml of n-heptane is added dropwise over about 30 minutes to obtain a precipitate of the titanium component.  4d).  Aging (aging) After completing the operation of adding titanium tetrachloride dropwise, the flask is heated with increasing temperature from 10 to. Stirring is continued for another 2 hours. Thus, the operation is completed with aging with the reaction product washed once with 100 ml each time. -heptane, as a result of which an activated titanium component is obtained.  five).  Polymerization of propylene using activated titanium components.  1 liter of heptane, 200 mg of the activated titanium component and 0.3 ml of diethyl aluminum monochloride are introduced into an autoclave with a capacity of 2. l in the atmosphere of nitrogen.  The autoclave with nitrogen is purged with propylene, and then propylene is fed until the pressure reaches 0.2 kg / cm and hydrogen until the pressure reaches 0.8 kg / cm.  The contents of the autoclave are heated so that the internal temperature rises to 70 ° C for 5 minutes.  Polymerization is continued at.  In the polymerization process, propylene is continuously fed in, so that the pressure of the reaction system is maintained at 5 kg / cm.  After 2 hours from the start of the polymerization, the supply of propylene is stopped and the contents of the autoclave are rapidly cooled to 25 seconds.  The unreacted propylene is discharged from the autoclave.  To the contents was added 290 ml of methanol and heated. up to 90s for deactivation of polymerization.  After cooling the autoclave, its contents are removed from the autoclave, to which 500 ml of heptane is added.  Next, 500 ml of water is added to the reaction solution and heated to 60 ° C with stirring to wash the polymer and the liquid. the phase is separated by decantation.  This procedure is repeated three times, then the solution is filtered and dried under reduced pressure to obtain g of white powdered crystalline polypropylene.  The resulting polypropylene has a characteristic viscosity of 1.6, which is measured in a tetramine at 135 ° C, the bulk density being 0.42 g / ml.  The ratio of the weight of the polymer that remained after extraction of the white powdered crystalline polypropylene with n-heptane to the weight of the white powdered crystalline polypropylene is 98.1%.  The amount of fine fractions with a particle size of less than 200 mesh in crystalline polypropylene is only 1.6 wt.  t. e.  92.9 weight.  powdered crystalline polypropylene is comprised of particles of 20-48 mesh, which exhibit a very clear size distribution (the size distribution is quite narrow).  After evaporation of the filtrate, 5 g of amorphous polypropylene are obtained.  Thus, all the polymer produced is a sum of white powdered crystalline polypropylene and amorphous polypropylene. The weight ratio of crystalline polypropylene to the entire polymer product, t. e.  output-  The powder is 98.0 wt. %  The product consisting of the yield of the powder and the residue after extraction with n-heptane, t. e.  the ratio of aesa of crystalline polypropylene to the weight of the whole polymer is 96.1%; the ACTIVITY of the catalytic system during polymerization is 868 g / g-h.  Example 2, Example 1 is repeated to prepare complex A, except that 150 ml of benzo is used; ash, 159 m, p n-heptane (solvents), 17 g of titanium tetrachloride, 16 g of aluminum trichloride and 2.5 g of aluminum metal powder, instead of 300 ml of benzene, 3 g of titanium tetrachloride 32 g of aluminum trichloride and 5 g of aluminum metal powder .  15 g of the obtained complex A are loaded into a 500 ml four-necked flask, which is equipped with a stirrer for distillation, in a nitrogen atmosphere.  An activated titanium component is then prepared in the same manner as in Example 1.  The activated titanium component is used in combination with an organoaluminum compound to polymerize propylene in the same manner as in Example 1.  The results of the experiment are given in table.  one.  PRI me R 3.  Example 1 is repeated except that 25 ml of isoamyl ether is used instead of 22 ml of n-butyl ether and 8 ml of titanium tetrachloride instead of 10 ml, then the polymerization of propylene is carried out.  The results of the experiment are also given in table.  one.  PRI me R.  Example 1 is repeated using 16. ml of butyl acetate and 22 ml of n-butyl ether as the oxygen-containing organic compound.  Then the polymerization of propylene is carried out.  The results of the experiment are given in Table.  one.  Froze  Example 1 is repeated to obtain the activated titanium component except that instead of 22 ml of n-butyl ether, 4.5 ml of anisole is used as the oxygen-containing organic compound.  The activated titanium component thus obtained is used for poly-.  mercury ethylene.  1 liter of heptane, 1UO mg of activated titanium components and 0.3 ml of aluminum triisobutyl are introduced into a 2 l autoclave under a nitrogen atmosphere.  The autoclave is purged with hydrogen to displace nitrogen, then under.  give hydrogen at pressures up to 3 kg / cm, ethylene under pressure of 5 kg / cm.  The contents of the autoclave are heated until the internal temperature rises to 85 ° C for 5 minutes and the polymerization reaction is continued at this temperature.  In the polymerization process, ethylene is continuously fed under pressure, despite the fact that the internal pressure is maintained at 8 kg / cm.  3 hours after the start of the reaction, the supply of ethylene is stopped, and the contents of the autoclave are rapidly cooled to 2 ° C.  Unprotected ethylene is quickly discharged from the autoclave.  Then, 290 ml of methanol is added to the contents, which are then heated and maintained at 90 for 30 minutes to deactivate the polymerization.  After cooling, the contents are discharged from the autoclave and 50 ml of heptane are added.  To the mixture is added 500 ml of water, which is heated to, and stirred for washing.  The aqueous phase is then removed from the mixture.  The procedure is repeated three times, filtered, and dried under reduced pressure to obtain 376 g of white powdery crystalline polyethylene.  The powdered polyethylene thus obtained has an intrinsic viscosity of 1.86, a bulk density Q, kk g / ml and a residue from extraction into n-heptane of 99.3 wt. .  G Polymerization activity of the catalytic system is 1257 g / g. h  The content of fine fractions in powdered polyethylene (particle size less than 200 mesh) 0.7 weight. .  PRI me R 6.  Example 1 is repeated to obtain an activated titanium component.  However, instead of 22 ml of n-butyl ether, 13 ml of diethyl ketone are used as the oxygen-containing organic compound.  The polymerization procedure of Example 5 is then repeated to polymerize ethylene using the resulting activated titanium component. The results of the experiment are given in table.  2  Example 7-9.  Example 1 is repeated using temperatures ranging from minus (example 7), (example 8) and 70 ° C (example 9) instead of adding titanium tetrachloride, as in step 3) of example 1, resulting in the resultant activated titanium components.  These activated titanium components are used in the polymerization of propylene in the same manner as in Example 1.  The results of the experiment are given in table. 3  Comparative example 1.  Example 1 is repeated, however, instead of the temperature used to add titanium tetrachloride, the temperature is used in the same manner as in step 5.  of an example, as a result of which, the titanium component of black-brown is activated.  Then, using the thus prepared activated titanium component, propylene was polymerised in the same manner as in Example 1.  The results of the experiment are given in table. 3  I'll try it on.  Example 1 is repeated using instead vanadium tetrachloride in titanium tetrachloride in stage 3 of example 1 to obtain an activated titanium component.  Then Example 5 is repeated using the titanium component thus prepared to polymerize ethylene.  The results of the experiment are given in you, k.  Example T1-13.  Example 1 is repeated using aging (aging) temperatures (Example 11),.  (example 12) and 90. C (Example 13) instead of preparing three & IDA activated titanium components, respectively.  Propylene was polymerized in the same manner as in Example 1, using the above three types of activated titanium components, respectively.  The results of the experiment are given in table. 6  Comparative example 2.  Example 1 is repeated using instead of the aging temperature and the aging time of 2 hours, the aging temperature and the time of 3 hours, with the result that an activated titanium component (brown) is obtained.  The activated titanium component thus prepared is used to polymerize propylene in such a manner as in Example 1. The results of the experiment are shown in Table.  five.  Comparative examples 3- i and example 15.  To ensure effective aging, (aging), which is the last step in obtaining the activated titanium component, is prepared in accordance with methods A and B described in examples 1 and 2 of known solution 2, two.  kind of titanium component.  Method A.  30 ml of titanium tetrachloride and 120 ml of n-heptane are loaded into a 500 ml four-neck distillation flask equipped with a stirrer under a nitrogen atmosphere.  The contents are cooled to 5 ° C, despite the fact that the mixing is carried out at a speed of J50 rev. / min  Then, a solution of 35 ml of diethyl aluminum monochloride dissolved in 30 ml of n-heptane is added to the flask at a constant rate for 4 hours, keeping the temperature at 5 ° C.  After the addition is complete, stirring is continued for a further 2 hours to complete the reaction.  The obtained brown precipitate I 512 titanium components are washed, five times with, each time with a portion of 100 ml of n-heptane without aging (aging J. The resulting titanium component is an unceremonized (undifferentiated) titanium component N.   Method B.  Method A was repeated until the washing step, resulting in a precipitate of the titanium component.  The precipitate is gradually heated to without stirring and maintained with no stirring for, then washed five times with 100 ml portions of n-heptane at 25 ° C.  The resulting activated titanium component in magenta is the aged titanium component H. Next, two kinds of activated titanium components are prepared (methods C and D).  Method C.  The procedure of Example 1 is repeated until the aging step, as a result of which a precipitate of the titanium component is formed.  The titanium component thus obtained is washed five times with 100 ml portions of n-heptane without curing, the obtained brown titanium component is an unsupported titanium component M.  Method D.  The procedure of Example 1 is repeated until the aging step to form a precipitate of the titanium component.  The precipitate thus obtained is gradually heated to with stirring and kept under stirring for more than 4 hours.  After that, the titanium component is washed at 25 ° C with five times portions of 100 ml of n-heptane to obtain the purple activated titanium component — the aged titanium component M.  Four named titanium components of the type are used instead of the activated titanium component of the example for the polymerization of propylene in the same way as in example 1.  The results of the experiment are given in table.  7  Example 16  Using the activated titanium component prepared in Example 1, propylene block polymerization is carried out, i. e.  100 mg of activated titanium components and 0. 3 ml of dimethyl aluminum monochloride dispersed in 30 ml of heptane are loaded into a 6 l autoclave under a nitrogen atmosphere.  Nitrogen from the autoclave is removed (pumped out) by means of a vacuum pump, and then 2 liters of hydrogen and 2.5 kg of propylene are supplied to the autoclave. The contents of the asocle are heated until the temperature inside it has risen to 10 minutes, at which temperature polymerization.  20 ml of methanol are added after 1 hour after polymerization, and the contents are stirred for another 10 minutes to decompose the catalyst.  After cooling the autoclave, its contents are discharged and dried under reduced pressure to obtain 1120 g of white powdered crystalline lippropylene.  The white crystalline polypropylene thus obtained has an intrinsic viscosity of 2.10, a bulk density of 0.3 g / cm, an index of 9.1%.  The fines content (less than 200 mesh) is 1.5%.  The polymerization activity of the catalytic system is 2,240 g / g. h  PRI me R 17.  Example 1 is repeated to obtain an activated titanium component, however, 25 ml of isoamyl ether is used as an oxygen-containing organic compound instead of 20 ml of n-butyl ether, and instead of being treated in this case using an oxygen-containing compound.  In the polymerization, an activated titanium compound is used instead of the activated titanium compound used in the experiment of Example 1.  The results of the experiment are summarized in table.  eight.  P r and m el 8. In example 17, an activated titanium compound is obtained, however, instead of 25 ml of isoamyl ether, 22 ml of n-butyl ether are used, and in the process of polymerization of propylene, example 17 is repeated, and the treatment is carried out at.  The results of the experiment are given in table.  eight.  Examples 19 and 2C.  In Example 1, an activated titanium component is obtained, but instead the boiling point is maintained under reflux for Example 19 and for Example 20, the polymerization process of Example 1 is repeated to polymerize propylene, however, activated titanium components are used instead of the activated titanium component.  The results of the experiments are given in table.  9,
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    权利要求:
    Claims (5)
    [1]
    1. METHOD FOR PRODUCING A TITANIUM COMPONENT OF THE CATALYTIC SYSTEM FOR POLYMERIZATION OF PROPYLENE, comprising the interaction of titanium tetrachloride with an aluminum-containing compound, characterized in that, in order to obtain a component that increases the activity of the catalytic system, aluminum tetrachloride and aluminum chloride 50 are reacted with aluminum chloride 50 -200 C in the presence of benzene or benzene with heptane in a volume ratio of 1: 1, the product obtained is treated first with an oxygen-containing organic compound at minus 50 °, plus 150 ° C, then titanium tetrachloride or vanadium pentachloride at minus 5 ° plus 70 ° C, followed by exposure at 30-90 ° C.
    [2]
    2. The way pop, ^ characterized in that they use aluminum in an amount of 1 mol per mol of titanium compound.
    [3]
    3. The method of pop. 1, about l and h and ίου; and with the fact that they use benzene in an amount of 19 mol 'per 1 mol of titanium compound.
    [4]
    4. The method according to p. Characterized in that as an oxygen-containing organic compound, a compound selected from the group consisting of n-propyl ether, n-butyl ether, isoamyl ether, anisole, diethyl ketone and butyl acetate is used.
    [5]
    5. The way to pop, 1, the fact that the oxygen-containing organic compound is used in an amount of 1.0-3.2 mol per 1 "ol of the reaction product.
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    CA1106099A|1981-07-28|Process for producing copolymers of ethylene and higher alpha-olefins
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    CA2040598A1|1991-10-21|Process for producing polyolefins
    CA1132129A|1982-09-21|Polymerization catalyst and process
    US4175171A|1979-11-20|Catalyst for polymerizing α-olefins
    CA2055140C|2002-09-17|Stereoselective catalyst for the polymerization of olefins
    EP0004789B1|1982-06-30|Catalyst component for alpha-olefin polymerization and use thereof
    US4083802A|1978-04-11|Polymerization of olefins and catalysts therefor
    CA1160202A|1984-01-10|Magnesium containing solid
    SU654175A3|1979-03-25|Method of obtaining catalyst of polymerization and copolymerization of c3-c8-alpha-olefins
    US4110248A|1978-08-29|Manufacture of catalysts for polymerization of olefins
    SU1014465A3|1983-04-23|Process for preparing titanium component of catalytic system for polymerization of propylene
    EP0201647B1|1990-12-27|Process for polymerization of butene-1
    KR100330059B1|2002-08-08|Elastomer Ethylene-Propylene Copolymer Production Catalyst
    US4446288A|1984-05-01|Polymerization method
    US4208304A|1980-06-17|Catalyst system for producing ethylene polymers
    US4304892A|1981-12-08|Olefin polymerization catalyst
    US4199475A|1980-04-22|Catalyst for producing polymers of ethylene
    NL8400441A|1984-09-17|SOLID CATALYST COMPONENT FOR THE POLYMERIZATION OF OLEFINS AND METHOD FOR THE PREPARATION THEREOF.
    US4892852A|1990-01-09|Transition metal composition
    US4273905A|1981-06-16|Process for producing propylene polymer or copolymer
    US3944529A|1976-03-16|Process for the preparation of polybutene-1
    同族专利:
    公开号 | 公开日
    PT66092B|1978-06-27|
    FR2340329A1|1977-09-02|
    FR2340329B1|1982-11-12|
    US4190555A|1980-02-26|
    JPS591286B2|1984-01-11|
    PT66092A|1977-02-01|
    JPS5294391A|1977-08-08|
    NL184276B|1989-01-02|
    NL7700687A|1977-08-09|
    NL184276C|1989-06-01|
    IT1085060B|1985-05-28|
    MX143057A|1981-03-06|
    GB1541195A|1979-02-21|
    CS198216B2|1980-05-30|
    DE2704271A1|1977-08-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3492281A|1967-06-29|1970-01-27|Goodyear Tire & Rubber|Process for the polymerization of diolefins with beta titanium trichloride and organoaluminum compounds|
    IE35231B1|1970-03-26|1975-12-24|Solvay|Process for the preparation of a ziegler-natta type catalyst|
    US3984350A|1974-05-09|1976-10-05|Standard Oil Company |Catalyst component comprising brown titanium trichloride|
    JP3920501B2|1999-04-02|2007-05-30|株式会社東芝|Nonvolatile semiconductor memory device and data erase control method thereof|
    JP5115187B2|2007-12-27|2013-01-09|セイコーエプソン株式会社|Liquid ejector|EP0019312B1|1979-04-30|1983-08-17|Shell Internationale Researchmaatschappij B.V.|Olefin polymerization catalyst compositions and a process for the polymerization of olefins employing such compositions|
    US4363746A|1979-05-29|1982-12-14|Phillips Petroleum Company|Composition of matter and method of preparing same, catalyst, method of producing the catalyst and polymerization process employing the catalyst|
    IT1132230B|1980-07-24|1986-06-25|Anic Spa|PROCEDURE FOR THE PRODUCTION OF THE CHOLESTEROL-ESTERASE ENZYME AND FOR HYDROLYSIS OF ESTERS WITH FATTY ACIDS OF CHOLESTEROL BY USING THE ENZYME ITSELF|
    US4406818A|1982-01-28|1983-09-27|Phillips Petroleum Company|Olefin polymerization|
    US6046126A|1998-05-12|2000-04-04|Kelly; Mark|Titanium process for making catalyst|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP1080576A|JPS591286B2|1976-02-05|1976-02-05|
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