• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    There are disclosed catalyst components for polymerizing olefins, consisting of the product obtained by successively reacting (A) a Mg compound (halide, alcoholate, haloalcoholate, carboxylate, oxyde, hydroxyde, salt of an inorganic oxygen containing acid, Grignard reagent or reaction product of a Grignard reagent with a silicon compound), optionally in the form of a complex with an electron-donor compound, with (B) a compound having general formula [MOx(OR)y]n, wherein M=Ti, V or Zr, R=an alkyl, an aryl or a cycloalkyl containing 1 to 20 carbon atoms, x may be zero, y is an integer not lower than 2, 2x+y=a valence of M, and n=an integer from 1 to 6 (inclusive), and with (C) a compound, other than the aluminium halides, exerting on component (B) a halogenating action and a reducing action, or a mixture of a halogenating compound with a reducing substance. These components, used to prepare the final catalysts by mixing them with organometallic compounds of metals belonging to Groups I, II and III of the Mendelyeev Periodic Table, provide catalysts which are particularly active in the polymerization of ethylene, alpha-olefins having at least three carbon atoms, and mixtures of ethylene with alpha-olefins and/or with diolefins or multiolefins.
    公开号:SU812185A3
    申请号:SU782620109
    申请日:1978-05-24
    公开日:1981-03-07
    发明作者:Цуккини Умберто；Куффиани Илларо
    申请人:Монтэдисон С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    one
    A known method of producing polyethylene by polymerizing ethylene in an inert hydrocarbon solvent at 50-75 ° C and a pressure of about 10 atm in the presence of Ziegler catalysts, consisting of aluminum triisobutyl and titanium tetrachloride.
    The closest to the invention to the technical essence and the achieved effect is a method of producing polyethylene by polymerization of ethylene into an inert hydrocarbon solvent medium at SO-ISO C and a pressure of 1-50 atm in the presence of a catalyst consisting of triisobutyl aluminum and a component including the product of the interaction of titanium with magnesium compound , used as a magnesium dihalide, pretreated with an electron donor compound, for example, carboxylic acid ester 2.
    The disadvantage of the known method is the broad molecular weight distribution of the polymer, the polyethylene obtained is difficult to process by pressure casting, as evidenced by the relatively high ratio of the melting index measured according to the conditions of standard A5TMD-1238 (MIN) and conditions E that standard. (MtE). This ratio is 9.8. The 1 CRI melting index is 5 g / 10 ml as determined by ASTM D-1238 (condition E), the particle size distribution of polymer particles by size is 30% 100 µm, 70% between 100 and 1000 microns, -j polymer bulk density 0.35 g / cm
    In order to obtain a polyethylene with a narrow molecular weight distribution that can be processed by the injection molding method, a method of producing polyethylene by the polymerization of ethylene in an inert hydrocarbon solvent at 50-150 ° C and a pressure of 1-50 atm in the presence of a catalyst consisting of from triisobutylaluminum and the component comprising the product obtained at a temperature of 45-98 ° C by the interaction of a magnesium compound () selected from the group including anhydrous MgCl2., MgC
    Mg (OC,;, H5-) 2, (CH COOaMg. MgC Pj. H dO, Cn.HjHgCl, the product of the interaction of polymethylsiloxane with MDO, the product
    interaction, MgCI with diphenylsilanediol, titanium (II) compounds of general formula Ti (OnR) Ci, where R C4-C9, m, n 0 or n 1, m 3, and silicon compound (ill) selected from the group including a compound of the formula (-Si-CI -H, | where m 1-2, n 1-3, with m + n 3, mixtures: SiС 1d with polymethylhydroxyloxane, SiCl4 with CaHgMgCI „SiCI with S1 (OC2H5) 5H, SiHCI with a polymethylhydrosiloxane. A distinctive feature of the invention is the use of a catalyst comprising, as a component, a product obtained at a temperature of 45-98 ° C by reacting. A III of a magnesium compound (I) selected from The compounds of the compound of titanium (II) of the above formula and the compound of silicon (III) selected by the listed group of compounds. The proposed method of producing polyethylene as compared to the known method allows to obtain polyethylene with a narrow molecular-mass distribution, which can be processed by casting Thus, the value of the ratio Ml N / MI E of polyethylene obtained by the proposed method is 7.6 and the particle size distribution of polyethylene particles is as follows: 0% 100 µm, 90% between 177-500 µm, 10% between 500 IUOO microns. Higher polymer bulk density 0, 40 g / cm. These characteristics of the ethylene homopolymers prepared according to the invention suggest that such polymers can be used for injection molding. Example 1. 2.4 g (0.025 mol) of MgCli and 17 g (0.05 mol) of Ti (O-n-C Hg) j are stirred in a flask at 160 ° C and under a nitrogen atmosphere, after 4 hours the MgCl4 completely dissolves. The resulting solution, cooled to, is diluted with 80 cm of anhydrous n-heptane. A solution of 5.8 cm (0.05 moles) S i C 1 in 20 cm n-heptane is added to this solution, which is maintained at 60 ° C with stirring for 1 h. Upon completion of the introduction of this solution, the reaction mixture is heated at 1.5 hours. - The temperature of the resulting suspension is reduced to. and 19.4 cm (20.6 polymethylhydrosiloxane (PMHS) of the formula (CH3) e, 510 1 cN3), Si- (CH5) 3, where n is a value of about 35, are introduced dropwise over 2 hours to it. According to after the introduction of the reagent, the mixture is stirred for 1 h at. After the temperature of the mixture decreases to room temperature, a precipitate is formed, which is washed several times with anhydrous n-hexane and finally dried at 70 ° C under vacuum to constant weight. As a result, 11.2 g of a reddish-orange powder containing 16.95% of Ti are obtained. To carry out the polymerization process, a 2.5-liter stainless steel autoclave is used, which is filled in the following manner under a nitrogen atmosphere: 1000 cm anhydrous -heptane, 1.5 g A1 (izo-CfN) -as a cocatalyst and finally 0.014 g of the catalytic powder obtained in accordance with the procedure described above. The autoclave is immediately heated to, after which 5, 2 atmospheres of hydrogen and 7.8 atmospheres of ethylene are introduced into it, the latter being introduced continuously for 4 hours. Then the suspension is discharged from the autoclave, it is filtered and the polyethylene is dried in a thermostat to a constant weight. As a result, 170 g of polyethylene is obtained, which corresponds to a yield of 71,700 g / g of Ti, a melt index of the obtained polymer E (M1) is 3.5 g / 10 min, and the ratio MIN / MIE is 8.6. Pr 2. 2. 2.4 g (0.025 mol) MDS l-i is dissolved in 17 g (O., 05 mol) Ti ()}. as described in example 1. After cooling, the solution is diluted with 50 cm of anhydrous n-heptane. In this solution, maintained at 45 ° C, with constant stirring, a solution consisting of 30 cm of dry n-heptane, 8 cm of PMHS (the same type used in Example 1) and 17.4 cm (0.15 mol) S i C 14. After the introduction of the reagent is complete, the suspension is stirred for another 1 hour at and then for 1 hour at the boiling point of hexane. After cooling to room temperature, the precipitated precipitate was collected as described in Example 1. Thus, 4.4 g of a light brown powder containing 4.75% of Ti was obtained. To carry out the process of polymerization of ethylene, the same procedure is used as in example 1, but 0.01646 g of the powder obtained in this example is loaded into an autoclave. As a result, 400 g of polyethylene was obtained, which corresponds to a conclusion of 577,200 g / g Ti. The polymer melt index is 4.85 g / 10 min and the MIN / MlE ratio is 8.2. Example 3. 2.4 g MdCl (0.025 mol) is dissolved in 17 g (0.05 mol) Ti (, Hi)) as described in Example 1. After the solution temperature drops to 45 ° C, it is diluted with 50 see dehydrated n-hexane. A solution of 10.65 cm PMGS (of the same type as in Example 3) and 20 cm of dehydrated n-hexane are introduced into this solution, maintained at 4 ° C, while stirring. After the introduction of the reagent, the mixture is heated for another 1 h at the boiling point of hexane. Then the temperature of the mixture is reduced to and a solution consisting of 25.5 g (0.15 mol) of S i C 14 and 20 cm of anhydrous n-hexane is introduced into the resulting suspension within 90 minutes. After the introduction of the solution is complete, the reaction mixture is heated for another 90 minutes at the boiling point of hexane. Upon cooling the solution to room temperature, the precipitated precipitate is separated as described in Example 1. As a result, 5 g of brown powder containing 12.65% Ti is obtained. The process of ethylene polymerization was carried out as described in Example 1, but 0.0136 g of the obtained catalytic powder was loaded into the autoclave. 328 g of polyethylene was obtained, which corresponds to a yield of 190,700 g / g Ti Melt Index E of the polymer is 4.55 g / 10 min, and the MIN / MIE ratio is 8.5. Example 4. 1.35 g of MgCl (0.014 mol) is dissolved in 8.5 g of Ti (0-p-CuNd) 4 (0.025 mol) as described in Example 1. The resulting 90P is cooled to room temperature, diluted with 50 see n-heptane and for 2 hours, inject into a flask containing 17 cm of 2.93 M Cj HjMgCIB diethyl ether (stirred), which is at a temperature. Then, the resulting suspension is gradually heated to and introduced into 34 g (0.2 mol) S C for 1 hour. After the introduction of S i C 1, the reaction mixture is stirred for another 90 minutes after heating it to. As soon as the temperature of the mixture drops to room temperature, the precipitated precipitate is separated as described in Example 1. As a result, 9.0 g of gray powder containing 5.3% Ti is obtained. The polymerization of ethylene was carried out as described in Example 1, but 0.016 g of the obtained catalytic powder was charged into the autoclave. 320 g of polyethylene were obtained, which corresponds to a yield of 377,300 r / r-Ti. The polymer melt index was 9.7 g / 10 min, and the H1N / MIE ratio was 8.6. Example 5, 2.4 g MDS l (0.025 mol) is dissolved in 17 g Ti (O-p-C H) (0.05 mol) as described in Example 1. Then the solution is cooled to and diluted, 80 cm of dehydrated n-heptane. 15.7 cm (0.15 mol) of dichloromethylsilane are introduced into this solution, maintained with stirring at 40 ° C, for 3 hours. After the introduction of the reagent is completed, the suspension is heated for 2 more hours. 98C. After cooling the reaction mixture to room temperature, the precipitated precipitate was separated as described in Example 1. As a result, 4.5 bright red powders containing 8.05% Ti were obtained. The process of polymerization of ethylene is carried out as described in [11], except for that. That in the autoclave load 0,0107 g of the obtained catalytic powder. 317 g of polyethylene was obtained, which corresponds to a yield of 368,600 g / g T1. The melt index E of the polymer is 3.2.r / dO min, and the ratio of the melt index N to the melt index E is 8.2. Example 6. 2.4 g (0.025 mol) are dissolved in 17 g (0.05 mol) T i (O-p-C H) j as described in Example 1. The resulting solution is cooled to room temperature and diluted 49 see dehydrated n-hexane. A solution of 40.9 g (0.3 mol) of SiHCU and 10 cm of dehydrated hexane is introduced into this solution, cooled with stirring for 4 hours. After the introduction of this solution, the temperature of the mixture is raised to 60 ° C and maintained for an additional hour. After cooling the mixture to room temperature, the precipitated precipitate is separated as described in Example 1. In a result, 3.6 g of gray powder are obtained 6.4% Ti. The process of polymerization of ethylene is pro-water, as described in Example 1, but 0.0088 g of the obtained catalytic powder is charged to an autoclave. 330 g of polyethylene were obtained, which corresponds to an output of 586 100 g / g Ti. The melt index E of the polymer is 2.3 g / 10 min, and the ratio of the melt index N. to the melt index is E 9, 0. Example 7. 4.8 g (0.05 mol) MgCJa is dissolved in a mixture of 17 g (0.05 mol) Ti (O-p-C H) 4 and 4.5 cm (0.05 mol) p-butanol . After drying, 20 cm of dehydrated n-hexane, 12.7 cm (0.11 mol) SiCl4 and 24.3 cm PMHS were added to the solution. 8.1 g of a catalytic compound containing 8.5% Ti are obtained. The process of ethylene polymerization was carried out as described in Example 1, but 0.012 g of the obtained catalytic compound was charged into the autoclave. 170 g of polyethylene was obtained, which corresponds to a yield of 167,000 g / g Ti -. The melt index E of the polymer is 4.3 g / 10 min, and the ratio of the melt index N to the melt index is E 8, 8.
    Example 8. 4.8 g (0.05 mol) MgCl is dissolved in 34 g (0.1 mol) T F (0-p-C Nl) 4. After dissolving, 50 cm of p-hex. HAf is added to the solution, after which the resulting hexane solution, heated to 45 ° C, is introduced into a solution for 3 hours, consisting 1CT of 20 cm of n-hexane, 17.3 cm | (0 , 15 mole) Si C14 and 16.8 cm / cm. 11.1 g of a catalytic compound containing 11.0% of Ti was obtained. The polymerization of ethylene was carried out as described in Example 1, except that 0.016 g of the obtained catalytic compound was charged to the autoclave. 320 g of polyethylene was obtained, which corresponds to a yield of 178,000 g / g T i. The melt index E of the polymer was 5.4 g / 10 min and the ratio of the melt index N to the melt index E was 8.0.
    Example 9. 2.4 g (0.025 mol) MDS l. dissolved in 31 g (0.05 ml) of T i (0-n-CftH g) 4. After dissolution, 50 cm of n-hexane is added to the solution, followed by 8.6 cm (0.075 mol) of 6.8 cm of PMHS and the entire reaction is carried out for 3 hours. 4.1 g of a catalytic compound containing 7.7% Tm was obtained. The polymerization of ethylene is carried out as in Example 1, but 0.016 g of the obtained catalytic compound is charged to the autoclave.
    130 g of polyethylene was obtained, which corresponds to a yield of 102,000 g / g Ti. The melt index E of the polymer is 2.7 g / 10 min, and the ratio of the melt index N to the melt index E is 9.1.
    Example 10. The sequence of operations of Example 5 is repeated, using the same amounts of MDS 1, T i (Nd) and n-heptane, but with the difference that instead of CI CHjSIN, 33 cm (0.3 mol) is used (C.ISIH Received 7.8 g of a catalytic compound containing 14.1% Ti.
    The process of polymerizing ethylene is carried out as described in Example 1, using 0.01-76 g of the obtained catalytic compound. 265 g of polyethylene was obtained, which is equivalent to a yield of 106,000 g / g Ti. The melt index E of the polymer is 5.9 g / 10 min, and the ratio of melt index N to melt index E is 7.9.
    Example 11. The sequence of operations of Example 8 is repeated with the only difference that S i C 1 and PMGS solution is added to the other reagents immediately, and not in 3 hours. 9.3 g of a catalytic compound containing 5.0% T are obtained i.
    The ethylene polymerization process was carried out as in Example 1, except that 0.015 g was used.
    the resulting catalytic compound.
    360 grams of polyethylene is poured, which corresponds to a yield of 480,000 g / g Ti. The melt index E of the polymer is 5.3 g / 10 min, and the ratio of the melt index H and the melt index is E 7, 9.
    Approximately 12. Example 2 is repeated, using 13.9 g (0.04 mol) Ti 0 4) (0.019 mol) MgGI / j. and instead of 7.1 cm (0.06 mol) of PMHS, 7.5 g (0.04 mol) of Si are used (Thus 3.2 g of the catalytic compound containing 13.65% of T1 is obtained.
    The polymerization of ethylene was carried out.
    as in Example 1, in the presence of 0.020 g of the catalytic compound described. Received 195 g of polyethylene, which corresponds to the output
    0 7050.0 g / g TI. The melt index of Epo, limer is 3.0 / 10 min, and the ratio of the melt index N to the melt index E is 8.4.
    Example 13. Repeat example.
    5 2, using 17 g (0.05 mol)
    Ti. (0-p-C H) 4, 2.2 g (0.023 mol) MgCl, 9.1 cm Dy-PMGS and 10 cm (0, i mol) Si HC C instead of 510 (4. Light 9.1 g of a catalytic compound containing 13.0% of Ti. By polymerizing ethylene in the same manner as pn-isan in Example 1, in the presence of 0.015 g of the resulting catalytic compound, 129 g
    C polyethylene, which corresponds to a native of 65,000 g / g Ti. The melt index E of the polymer was 4.2 g / 10 min, and the ratio of the melt index N to the melt index E was 8; .0.
    Example 14: Repeat Example
    0 2, using 34 g (0.1 mol) T (OnC Hg);}, 4.8 g (0.05 mol) MgCtj, 17.3 cm (0.15 mol) SiCi and instead of PMHS - 28 g partially methylated polymethylhydrosilane containing 0.9 wt.% of hydrogen (Tegloxane PTF 16, produced by Golschmidt). 12.2 g of a catalytic compound containing 9.1% of Ti were obtained.
    Ethylene polymerization is carried out
    0 as described in example 1, in the presence of 0.016 g of the described catalytic compound, 125 g of polyethylene are obtained, which corresponds to a yield of 85–500 g / g Ti. Melt Index
    e E polymer - 1.1 g / 10 min, and the ratio of the melt index P to the melt index E - 7.75.
    Example 15. Example 2 is repeated, except that instead of Ti (0-p-C4Hl) 4, 15.9 g (0.052 mol U Ti (Oh-CxHg) 3 C I, are used. 5.8 g instead of MgCl1). (0.0176 mol) MDS 1,2. SCgHyOH. According to the procedure described in Example 2,
    5 17.3 cm (0.15 mol) SiCl4 and 20.2 cm PMHS. 2.9 g of a catalytic compound containing 9.4% T-t was obtained. Polymerization of ethylene was carried out as in Example 1, in the presence of 0.16 of the described catalytic compound, 296 g of polyethylene was obtained, which corresponds to a yield of 197,000 g / T1. The melt index E of the polymer is 6, 8 g / 10 min, and the ratio of the melt index N to the melt index is E., 5. Example 16. In a 250 ml flask, 0.925 g (0.038 l) of magnesium shavings, 6.7 g of absolute ethanol and 25 g (0.0725 mol) of T1 (0-P-C4 Nd) are placed, the temperature is gradually increased to 130 C and is maintained at this level for 2 hours, then unreacted ethanol is distilled off. After cooling down, 50 cm of n-hexane is added to the obtained solution, followed by 43 cm (0.375 mol) of StCf4 and 27 PMHS for 4 hours to enter this diluted solution, maintained at 50 ° C. After all the reactants are injected, the whole mixture is heated at the boiling point of hexane for 1 hour. After cooling to room temperature, the precipitate of the catalytic compound is washed with hexanes to a negative reaction with CE-ions. After drying, 9.4 g of a catalytic compound containing 6.3% TG was obtained. ; . . The polymerization of ethylene is carried out as in Example 1, in the presence of 0.0144 g of the described catalytic compound, 411 g of polyethylene is obtained, which corresponds to the yield. 466,000 g / g T1, Melt Index E of the polymer — 3.5 g / 10 min, and the ratio of the M melt index to the melt index E — 8.7. Example 17. Reaction between 2.4 g (0.0167 mol) anhydrous magnesium acetate and 17 g (0.05 mol) 11 (0-0-041-19) 4. carried out at 135 G for 3 hours. The reagents are partially dissolved, the reaction mixture is diluted with 35 cm of n-hexane, and 31 cm (0.31 mol) SiHCl is added dropwise to it at. The precipitate obtained is washed and dried, as shown in the preceding examples, 1/8 g of the catalytic compound containing 3.3% T is obtained. The polymerization of ethylene is carried out as in Example 1, but 0.01223 g of the described catalytic compound is used. 160 g of polyethylene are obtained, which corresponds to a yield of 395,000 g / g T1. The melt index E of the polymer is 3.2 g / 10 min, and the ratio of the melt index N to the melt index E is 8.4. Example 18. The sequence of operations of Example 6 is repeated with the only difference that 2 are used; 0 g (0, .016 mol) - HdCl / g1.2 HoO and 17 g- (0.05 mol) T1 (0-n -CdH9T4. The subsequent reaction with S1HCL is carried out at 50 Pc in the presence of 31 cm (0/31 mol) SiHCI, 2.8 g of a metal-containing compound containing 10.9% TI is obtained. The melt index E of the polymer is 3.8 g / 10 min ,, and the ratio of the melt index N to the melt index E 9, 0. Example 19. 17 g (o, 05 mol) T (0-p-CuHQ) 4 are placed in a 250-cm flask and diluted with 17 cm of ethyl ether; in this solution maintained at 0 ° C, rfo drops for 1 hour, 17 cm of an ethereal 0.05 mol solution of CtMgC are introduced. After the introduction of the reagent, the temperature of the mixture is gradually raised to simultaneously distilling off diethyl ether. The solid residue is suspended in 100 cm5 l-hexane and added at 50 ° C for 1 hour 26, 266 mole) S i e 1 then the reaction mixtures are heated at the boiling point of n-hexane for another 1 hour. The resulting solid. This product was washed with n-hexane and, dried as described in the preceding examples, 10.7 g of a reddish-brown powder containing 6.95% T were obtained. The polymerization of ethylene was carried out as described in example 1, but using 0.0122 g catalytic powder obtained in accordance with the above method. 318 g of polyethylene was obtained, which corresponds to a yield of 375,000 g / g T i. The melt index E of the polymer is 6.6 g / 10 min / and the ratio of the melt index N to the melt index E is 8.8. Example 20, 35 g (0.1 mol) of Ti (0-n-Cj tc)} is diluted with 35 cm of toluene in a flask with a capacity of 500 cm and to this solution 66 cm of toluene solution is added to the solution at room temperature for 1 h, containing a product obtained by reacting 0.75 moles of C HgMgCI and 0.75 moles (calculated as silicon) of PMGS. at 70 ° C in tetrahydrofuran medium, after removing the tetrahydrofuran by evaporation and using toluene instead. After the addition of this toluene solution, the resulting reddish-brown solution is heated at 2 hours, after cooling the reaction mixture to room temperature, 33.3 cm (0.31 mol) are introduced into it. in 30 minutes Then, the resulting suspension is heated for 1 hour at the boiling point of SiC C. The resulting carbon is washed with a n-hexane bath and dried, as is the catalytic
    权利要求:
    Claims (1)
    [1]
    Claim
    A method of producing polyethylene by polymerization of ethylene in an inert hydrocarbon solvent at 50-150 ° C and a pressure of 1-50 atm in the presence of a catalyst consisting of trieobutylaluminium and a component comprising the product of the interaction of titanium with a magnesium compound, characterized in that, with In order to obtain polyethylene with a narrow molecular weight distribution, capable of being processed by injection molding, a catalyst is used that contains as a component a product obtained at a temperature of 45-98 ° С by interaction the effect of a magnesium compound (i) selected from the group including anhydrous MDS, MDS1 2 , BSOH ^ OH, MD (0CH) % , (CH dCOO ^ MD, MDC12'N 2 0, C 2 H MDS I, product the interaction of polymethyl or hydrosiloxane with MdO, the reaction product of ~ C 4 HgMgCI with diphenylsilanediol, titanium compounds ((I) of the general formula T i (On = R) w C ί Μ ·, where R = С ^ -. С 9 , m = 4, π = 0. or η = 1, m = 3, and a silicon compound (IG) selected from the group comprising compounds of the formula (CH ^) ^ - Si - Cl „- H, where 'm = 1-2, η = 1–3, for 'm + n = 3 mixtures of SiSC with polymethylhydrosiloxane, SiC with C 2 H 5 MgCI, S1CI 4 t Si (OC 2 tp „H, SiHClj with polymethylhydrosiloxane.
    类似技术:
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    同族专利:
    公开号 | 公开日
    GR72907B|1984-01-04|
    ES470120A1|1979-01-01|
    DK219578A|1978-11-25|
    NO781728L|1978-11-27|
    BE867400A|1978-11-24|
    DE2822809A1|1978-11-30|
    AU522013B2|1982-05-13|
    NL186701B|1990-09-03|
    AT362931B|1981-06-25|
    MX150091A|1984-03-15|
    DE2822809C2|1991-07-11|
    NO153575C|1986-04-16|
    DK151891C|1988-07-18|
    SE440224B|1985-07-22|
    SE7805739L|1978-11-25|
    BR7803292A|1978-12-19|
    IT1078995B|1985-05-08|
    CA1120910A|1982-03-30|
    AU3628178A|1979-11-22|
    US4218339A|1980-08-19|
    JPS5416393A|1979-02-06|
    NL7805410A|1978-11-28|
    GB1601426A|1981-10-28|
    FR2392037A1|1978-12-22|
    DK151891B|1988-01-11|
    FR2392037B1|1980-04-11|
    PT68068B|1979-10-26|
    PT68068A|1978-06-01|
    NL186701C|1991-02-01|
    ZA782971B|1979-05-30|
    NO153575B|1986-01-06|
    ATA364978A|1980-11-15|
    JPS6366842B2|1988-12-22|
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    申请号 | 申请日 | 专利标题
    IT23942/77A|IT1078995B|1977-05-24|1977-05-24|CATALYSTS FOR THE POLYMERIZATION OF OLEFINE|
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