United States Patent (19) 11) 4,180,636 Hirota et al. 45) Dec. 25, 1979 54 PROCESS FOR POLYMERIZING OR CO-POLYMERIZING PROPYLENE FOREIGN PATENT DOCUMENTS 2230672 12/1972 Fed. Rep. of Germany ........... 526/125 (75. Inventors: Kiwami Hirota; Hideki Tamano; 2504036 8/1975 Fed. Rep. of Germany ........... 526/125 Shintaro Inazawa, all of Oita, Japan Primary Examiner-Edward J. Smith 73 Assignee: Showa Denko Kabushiki Kaisha, Attorney, Agent, or Firm-Sughrue, Rothwell, Mion, Tokyo, Japan Zinn and Macpeak (21) Appl. No.: 809,873 57 ABSTRACT A process for polymerizing or co-polymerizing propy (22 Filed: Jun, 24, 1977 lene in the presence of a catalyst consisting essentially 30 Foreign Application Priority Data of (A) a solid catalyst component which is prepared by Jun. 24, 1976 JP Japan ... ... 51-7383O contacting Jun. 28, 1976 JP Japan ... ... 5175427 (1) a copulverized material obtained by copulverizing Jun. 30, 1976 JP Japan ... 51-76533 a magnesium dihalide compound together with an Jul. 6, 1976 JP Japan ... ... 51-7945.5 acyl halide with Jul. 27, 1976 JP Japan ............................. ... 51-88708 (2) a mixture or addition-reaction product of a tetra Aug. 9, 1976 JP Japan .................................. 51-93948 valent titanium compound containing at least one halogen atom with at least one electron donor Aug. 10, 1976 JP Japan .................................. S1944-40 compound selected from the group consisting of 51) Int. Cl........................... C08F 4/02; C08F 10/06 organic compounds containing a P-O bond, or 52 U.S. C. ............................... 526/125; 252/429 B; ganic compounds containing an Si-O bond, ether 252/429 C; 526/143; 526/351; 526/906 compounds, nitrite ester compounds, sulfite ester 58) Field of Search ....................... 252/429 B, 429 C; compounds, alcohol compounds, phenol com 526/125, 143 pounds and naphthol compounds, (56) References Cited (B) a trialkyl aluminum compound, and (C) a carboxylic acid ester compound. U.S. PATENT DOCUMENTS 3,642,746 2/1972 Kashiwa et al. ..................... 526/125 30 Claims, 8 Drawing Figures U.S. Patent Dec. 25, 1979 Sheet 1 of 4 4,180,636 S ss S U.S. Patent Dec. 25, 1979 Sheet 2 of 4 4,180,636 S act / S2 7 C O // S 33 SR 3 S U.S. Patent Dec. 25, 1979 Sheet 3 of 4 4 9 180,636 |0 06 98 U.S. Patent Dec. 25, 1979 Sheet 4 of 4 4,180,636 02 ? ZO |0 06 G8 |0IH ZO |0 06 98 4,180,636 2 (D) a method which comprises pre-treating MX2 PROCESS FOR POLYMEREZING OR with an electron donor compound and then treating CO-POLYMERIZING PROPYLENE with a transition metal compound (with or without an Sior Sn halide compound) (Japanese Laid-Open Patent BACKGROUND OF THE INVENTION Publications Nos. 88983/74, 51378/74, 72383/74, 21989/75, and 13492/77), 1. Field of the Invention (E) a method which comprises copulverizing MX2, a This invention relates to a process for polymerizing transition metal compound and a silicon-containing or co-polymerizing propylene in the presence of a novel organic compound (Japanese Laid-Open Patent Publi catalyst system. 10 cations Nos. 86482/74, 55385/76, 55386/76, 55387/76, 2. Description of the Prior Art and 28889/76), It is well known that catalyst systems obtained from (F) a method which comprises copulverizing MX2, a halide compounds of transition metals (generally tita transition metal compound and an alcohol, ester, ke nium trichloride) and organometallic compounds (gen tone, aldehyde or the like (Japanese Laid-Open Patent erally organoaluminum compounds) are suitable as pol 5 Publication No. 55388/76), ymerization catalysts for preparing polymers of olefins (G) a method which comprises preparing a catalyst (especially propylene). Polymers prepared with such made from MX2 and a transition metal compound catalysts, however, do not have entirely satisfactory which has a surface of more than 3 m/g or whose stereoregularity. Hence, the resulting polymers have X-ray diffraction spectrum is broader than that of non relatively high amorphous contents, and their mechani 20 activated MX2 and a transition metal compound (Japa cal properties are inferior. Therefore, a step of remov nese laid-open patent publication) Nos. 9342/72 and ing the amorphous portion is required after polymeriza 16986-8/73), and tion, and in this case the degree of effective utilization of (H) a method which comprises supporting a titanium the starting olefins is reduced. Furthermore, these cata compound on MX2 pretreated with an electron donor lysts have low polymerization activities, and the poly 25 compound, and then treating the product with an or mers obtained with the catalyst contain so much cata ganic acid ester (Japanese Laid-Open Patent Publica lyst residue that, it is necessary to remove it from the tion No. 57789/76). iresulting polymer. The catalyst systems obtained in these known meth Many suggestions have therefore been made for cata ods are mainly a combination of an organo aluminum lysts which can afford highly stereoregular polymers. 30 compound (with or without an electron donor com One of the coinventors of the present invention already pound) and a complex compound in which either a suggested a catalyst system prepared from titanium magnesium compound or a titanium compound is trichloride or an eutectic mixture of it with aluminum treated with an electron donor compound. But, any of chloride treated by contact with an acyl halide, and an these catalyst systems (particularly, in polymerization organoaluminum compound (Japanese Laid-Open Pa 35 of propylene) are quite unsatisfactory in crystallinity of tent Publication No. 26487/72). This catalyst system has polymer. That is, the crystallinity (H.R.) as seen in the greatly improved polymerization activity and stereo examples of these prior arts is in the range of 87 to 93% specificity, but the activity is still not sufficient as to in terms of H.R. value taking into consideration the permit the omission of a step of removing the catalyst amount of non-crystalline polymers dissolved in the residue from the polymer. 40 polymerization solvent. Further, in the prior art, hydro On the other hand, various methods have been sug gen (as a chain transfer agent) is not used in the poly gested for supporting a transition metal compound merization. When it is used in order to obtain a polymer (mainly a titanium compound) on halide compound of a which has a practical M.F.I. value (i.e., 1 to 20 g/10 divalent metal, Mg and Mn, (to be referred to as "MX2'). min.), the H.R. value is reduced by 2 to 5%. Thus, when In recent years, it has been suggested to perform this 45 polypropylene is produced by the catalyst as proposed supporting by first treating MX2 with an electron donor above, and non-crystalline polymers are not removed at compound (e.g., by copulverization) and then treating it all their practical mechanical properties of the resulting with a transition metal compound (with or without polymer are quite unsatisfactory. another electron donor compound), or by simulta In addition, these known methods do not at all sug neously treating MX2, a transition metal compound and 50 gest a method as in the present invention in which a an electron donor compound. mixture or a reaction product of a titanium compound Typical examples of these methods include: and an electron donor compound is supported on a (A) a method which comprises pre-treating MX2 with magnesium dihalide compound copulverized with an an organic acid ester and a halogenated silicate were a acyl halide, and the resultant is then activated with an polysiloxane, and then with a transition metal com 55 organoaluminum compound an electron donor com pound and an organic acid ester (Japanese Laid-Open pound. It is an unexpected and excellent effect that in Patent Publication Nos. 108385/75, 20297/76, the practical MFI range, the H.R. value of the polymer 28189/76,92885/76, and 24293/77), produced with the thus obtained catalyst exhibits 94 to (B) a method which comprises pre-treating MX2 with 98%. It is therefore not too much to say that the pro a ketone, an aldehyde, an alcohol or the like, and then duction of polypropylene having the same practical reacting the product with a titanium compound (Japa properties as in commercially available polypropylene nese Laid-Open Patent Publications Nos. 90687/74, has first become possible by the process of the present 1 19980/74, and 8238/76), invention without removing its catalyst residue and (C) a method which comprises reacting an organo amorphous portion. magnesium compound with an Si-containing com 65 It is believed that a catalyst system prepared from a pound, and then treating the pre-treated product with a solid component resulting from the supporting of a transition metal compound (Japanese Laid-Open Patent titanium compound on a magnesium halide and an or Publication No. 133489/74), ganoaluminum compound (to be referred to as "catalyst 4,180,636 3 4. system A') has higher polymerization activity than the parative Examples 8, 16 and 42 and Reference Example conventional catalyst systems, and can possibly omit a 1 (shown in Table 13); , process to remove the catalyst residue from the result FIG. 7 is a diagram showing the relation between the ing polymer. However, the resulting polymer has a MFI values (g/10 min, on the axis of the abscissas) and relatively low crystallinity, and without removing an the HR values (%, on the axis of ordinates) of polypro amorphous polymer, it does not exhibit satisfactory pylene powders prepared in Examples 30 and 35. Con properties in practical use. Furthermore, since the poly parative Examples 43 and 42 and Reference Example 1 merization activity of this catalyst system per unit shown (in Table 14); amount of the carrier is not high enough, a relatively FIG.