JPS6337804B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention primarily relates to an improved method for producing crystalline polypropylene having a β-type crystal structure. It has been known that there are three crystal modifications of crystalline polypropylene: α, β, and γ. Polypropylene produced by conventional methods mainly has an α-type (monoclinic) crystal structure, and most commercially available natural polypropylene pellets belong to this type. On the other hand, β-type polypropylene, which has a hexagonal crystal structure, has a lower melting point than α-type polypropylene, and is characterized by a lower force required for deformation during heating. As a method for obtaining β-type polypropylene, quinacridone and its derivatives, quinacridonequinone,
Japanese Patent Publication No. 47-30297 describes a method of producing crystalline polypropylene by mixing derivatives thereof and their metal chelate compounds with ordinary polymerization catalysts, or a method of mixing these compounds with ordinary crystalline polypropylene and pelletizing it. , 31930, same
Known as 48890. In all of these methods, large amounts of the various compounds described above are added, resulting in high production costs. Moreover, since all of them are colored compounds, if the amount added is large, the obtained β-type polypropylene will also be colored considerably, which is not preferable. Therefore, as a result of intensive studies to solve these problems, the present inventors found that quinacridone and quinacridone were used as a solid catalyst for polymerizing propylene or propylene and other α-olefins during the synthesis process of the catalyst. By using a product obtained by co-pulverizing one or more selected from derivatives, quinacridonequinone, derivatives thereof, and metal chelate compounds thereof, and the solid catalyst component, its intermediate, or its raw material, It has been discovered that even if the amount of the above compound added is very small, a sufficient effect can be achieved, and the present invention has been achieved. That is, the present invention provides titanium trichloride, a titanium trichloride composition, or a titanium compound that includes a step of co-pulverizing one or more of the compounds represented by formulas () to () in the manufacturing process. Crystalline polypropylene characterized in that propylene or propylene and other α-olefins are polymerized using a catalyst system consisting of one or more supported catalysts bound or supported and (B) an organoaluminum compound. This is the manufacturing method. (Here, R is a hydrogen atom, an alkyl group, an aromatic nucleus,
Halogen atom or alkoxy group, n is 0, 1
or 2, M is a monovalent metal, M' is the same as M or a hydrogen atom, and M'' is a divalent metal.) In the present invention, titanium trichloride is co-pulverized with the compounds represented by the above formulas. Alternatively, the titanium trichloride composition refers to titanium trichloride obtained by reducing titanium tetrachloride with hydrogen, a eutectic of titanium trichloride and metal halide obtained by reducing titanium tetrachloride with a metal,
or all titanium trichloride compositions containing titanium trichloride or titanium trichloride as a main component, such as titanium trichloride compositions obtained by reducing titanium tetrachloride with a compound having a Si-H bond or an organoaluminum compound. do. Before or after these titanium trichloride and titanium trichloride compositions are co-pulverized with the compounds represented by the above formulas, if necessary,
It may be subjected to treatments such as pulverization, reaction, or washing with various compounds. In the present invention, a wide variety of solid supports are used to support the supported catalyst, including silica, alumina, silica alumina, boron oxide, and magnesium compounds. Among magnesium compounds such as halides and magnesium oxide, magnesium halides are particularly preferred. There are no particular limitations on the method of binding or supporting the titanium compound on these solid carriers, but for example, (1) the solid is co-pulverized with the titanium compound. In this case, in addition to the solid carrier and the titanium compound, various metal compounds, electron-donating compounds, silicon tetrachloride, polysiloxane, aluminum halides, and organic acid ester complexes are present in the coexistence of pulverization (2). Titanium tetrachloride is heat treated in the presence or absence of a solvent. In this case, after reacting the solid carrier described above with titanium tetrachloride or preparing a composition consisting of a complex of the solid carrier and an electron-donating compound or an electron-donating compound and various metal compounds, There are methods such as heat treatment with titanium. The titanium compound here refers to the aforementioned titanium trichloride, titanium trichloride composition, or titanium tetrachloride. The operation of co-pulverizing with one or more of the compounds represented by the above formulas may be carried out either before or after the step of binding or supporting the solid carrier and the titanium compound. The compounds represented by formulas () to () used in the present invention exist in a number of crystal modifications, but the objects of the present invention are equally effective in all crystal modifications. Among the compounds represented by formula (), preferred are quinacridone, 2,9- or 4,11-dimethylquinacridone, 2,4,9,11-tetrachloroquinacridone, 2,9-dibromoquinacridone, 2. These include 9-dichloroquinacridone, 2,9- or 4,11 dimethoxyquinacridone, dibenzo[ae]quinacridone, and the like. Among the compounds represented by formula (), preferred are quinacridonequinone, 2,9-dimethylquinacridonequinone, 2,9-dichloroquinacridonequinone, 4,11-dibromoquinacridonequinone,
These include 1,8-dimethoxyquinacridonequinone, dibenzo[ae]quinacridonequinone, and the like. Among the compounds represented by formula (), preferred are 6,13-dihydroquinacridone, 2,9-dichloro-6,13-dihydroquinacridone, 4,11
-dimethoxy-6,13-dihydroquinacridone,
2,4,9,11-tetrachlor-6,13-dihydroquinacridone, 2,3-,9,10-dibenz-
6,13-dihydroquinacridone, 3,4-,
10.11-dibenz-6,13-dihydroquinacridone, etc. Among the compounds represented by the formula (), preferred are a combination of the above-mentioned compound represented by the formula () and potassium as a metal. Among the compounds represented by the formula (), preferred are compounds represented by the above-mentioned formula () in combination with copper, zinc, or nickel as a divalent metal. In the present invention, the formula () is co-pulverized with a normal solid catalyst component, its intermediate, or its raw material (a).
The ratio of compound (b) shown in ~() is not particularly limited, but usually b/(a+b) = 5 to 1 x 10 ^-6 wt%
and preferably 1 to 1×10 ⁻⁵ wt%. There is no particular restriction on the time for co-pulverization, but it is usually 1 to 100 hours, preferably 5 to 40 hours. The amount of crystalline polypropylene obtained in the present invention usually reaches 500 to 10,000 g per gram of component (A). Other α-olefins that may be used with propylene in this invention include ethylene, butene-
1, isobutylene, pentene-1, hexene-
These include 1,4-methylpentene-1, heptene-1, octene-1, styrene, etc., and these may be used in combination. When polymerizing propylene and other α-olefins, the propylene content in the obtained crystalline polypropylene is not particularly limited, but is usually 50 wt% or more. The organoaluminum compound used in the present invention may be any one commonly used in obtaining crystalline polypropylene. For example, triethylaluminum, triisobutylaluminum, tri-n-propylaluminum,
triisoprenylaluminum, diethylaluminium monochloride, diisobutylaluminum monochloride, diethylaluminium monobromide, diethylaluminium monoiodide, diethylaluminium monoethoxide, diisobutylaluminum monoisobutoxide,
These include ethylaluminum chloride monoethoxide, ethylaluminum sesquichloride, diethylaluminum monohydride, diisobutylaluminum monohydride, etc., and complex compounds or reaction products of these organoaluminum compounds and electron-donating compounds, etc. More than one species is used. Electron-donating compounds and the like added as necessary may be used by being mixed with a solid catalyst and an organoaluminum compound in advance, or may be added directly to the polymerization system. The polymerization reaction in the method of the present invention is carried out under conditions commonly practiced in the art.
The polymerization temperature at that time is in the range of 20 to 200℃, preferably 50 to 100℃, and the polymerization pressure is in the range of normal pressure to 200℃.
It is preferable to carry out the reaction under atmospheric pressure, generally in the range of normal pressure to 100 atmospheres. As a medium for carrying out the polymerization, aliphatic,
Alicyclic, aromatic hydrocarbons or mixtures thereof are used. Examples include propane, butane, hexane, heptane, benzene, and toluene. In addition, bulk polymerization using liquefied propylene and other α-olefins as a medium, or propylene and α-olefin polymerization in substantially no medium.
- The invention can also be carried out by gas phase polymerization, in which the olefin is polymerized in the gas phase. The molecular weight of the polymer obtained by the method of the present invention varies depending on the reaction mode, catalyst system, polymerization conditions, etc., but can be controlled as necessary by adding hydrogen, alkyl halides, dialkylzinc, etc. can do. The crystalline polypropylene obtained in the present invention includes a crystalline polypropylene homopolymer and a crystalline propylene-α-olefin copolymer having a propylene content of 50 wt% or more. Here α−
Olefins include ethylene, butene-1, isobutylene, pentene-1, hexene-1, 4-methylpentene-1, heptene-1, octene-1, styrene, and mixtures thereof. The crystalline polypropylene obtained by the present invention may contain various commonly used additives such as antioxidants, hydrochloric acid catch agents, slip agents, ultraviolet absorbers, antistatic agents, pigments, and inorganic additives. . The crystalline polypropylene obtained by the method of the present invention always has a stable β-type crystal structure even after repeated melting, cooling, and solidification. The crystalline polypropylene obtained by the method of the present invention can be processed by methods such as injection molding, extrusion molding, and compression molding, and has a wide range of applications such as containers, sheets, films, and filaments. Because it requires less force to deform at high temperatures (100℃ to 140℃),
It is particularly useful in the production of stretched films, tapes, bands and filaments. This will be explained using the following comparative examples and examples. Note that the β-crystal PP content of β-type polypropylene was measured as follows. ``Crimp 5 to 10 mg of the sample with an aluminum plate, melt it at 220℃ for 15 minutes in a nitrogen atmosphere, and then
The temperature is lowered to near room temperature in min. The sample prepared by the above method was set in the sample holder of DSC (Shimadzu Model 20B), and the temperature was raised at a rate of 10°C/min in a nitrogen atmosphere. Determine the β-crystal content (area %) from the peak area. ” Examples 1 to 4 Inner volume approximately 600 containing approximately 80 steel balls with a diameter of 12 mmφ
Prepare a vibrating mill equipped with a ml grinding pot. In the pot, titanium trichloride/aluminum chloride eutectic (composition is approximately
30g of TiCl ₃ 1/3 AlCl ₃ (hereinafter abbreviated as titanium trichloride) was charged, and after pulverizing for 40 hours, the prescribed amount of γ-quinacridone shown in Table 1 was added, and pulverization was continued for an additional 17 hours. Ta. In an autoclave with an internal volume of 2, 1 part of n-heptane and about 0.45 g of the above solid pulverized material were added under a nitrogen atmosphere.
and 1 ml of diethylaluminum monochloride
was loaded. After replacing the nitrogen in the autoclave with propylene, hydrogen was charged at a hydrogen partial pressure of 0.4 Kg/cm ^{for 2} minutes.
The contents of the autoclave were heated to an internal temperature of 70°C after 10 minutes, and polymerization was continued at 70°C. During the polymerization, propylene was continuously fed under pressure to maintain the internal pressure at 7 kg/cm ² gauge. Propylene about 450
After the reaction, unreacted gas was released, 350 ml of methanol was added, and the mixture was stirred at 90°C for 30 minutes to decompose the catalyst. The contents were taken out, thoroughly washed with water at 60°C, filtered, and dried to obtain crystalline polypropylene. 3,5-di-t-
After adding and mixing 0.1 wt% of butyl-4-hydroxytoluene, the mixture was extruded at 250°C using a 20 mmφ extruder to form granules. The β-crystal content (area %) of the obtained Sample is shown in Table 1 and the drawings. Further, since quinacridone had migrated to the crystalline polypropylene obtained by implementing the present invention, the amount thereof was also measured and the values are also listed in Table 1. Comparative Examples 1 to 3 The same procedures as Examples 1 to 4 were carried out, except that γ-quinacridone was not added at the time of grinding titanium trichloride, and a predetermined amount was added at the time of polymerizing propylene. A specific method for adding γ-quinacridone was to charge approximately 0.45 g of titanium trichloride catalyst and 1 ml of diethylaluminum monochloride, and then add a predetermined amount of γ-quinacridone. The results are shown in Table 2 and the drawings. From Table 2 and the drawings, it can be seen that Comparative Examples 1 to 3 require a significantly larger amount of γ-quinacridone when producing PP with the same β crystal content compared to the method of the present invention. On the other hand, compared to the addition method during polymerization of Comparative Examples 1 to 3 (Table 2, drawings), the method of the present invention has a very small amount of γ-
It can be seen that PP with a high β-crystal content can be obtained depending on the amount of quinacridone. Comparative Example 4 Comparative Examples 1 to 3 were repeated except that propylene was polymerized without using γ-quinacridone at all. The results are shown in Table 2, and no β crystals were obtained. Examples 5 to 9 Instead of γ-quinacridone, 4,11-dimethoxyquinacridone, quinacridonequinone, 6,13
- The same procedures as Examples 1 to 4 were carried out except that dihydroquinacridone, quinacridone quinone potassium salt, and quinacridone quinone copper chelate compound were used in the proportions shown in Table 3. The results are shown in Table 1, and it is clear that PP with a high β-crystal content can be obtained by adding very small amounts.

【table】

【table】

【table】 [Brief explanation of the drawing]

FIG. 1 is a flow diagram showing the catalyst preparation process to aid understanding of the present invention, and FIG. 2 is a flowchart showing the γ-quinacridone content (wt
%) and the β-crystal content (area %) in these polypropylenes.

Claims (1)

[Scope of Claims] 1 (A) Titanium trichloride, a titanium trichloride composition, which includes a step of co-pulverizing with one or more compounds represented by the following formulas () to () in the manufacturing process, or A crystal characterized in that it polymerizes propylene or propylene and other α-olefins using a catalyst system consisting of one or more supported catalysts on which a titanium compound is bound or supported and (B) an organoaluminium compound. method for producing polypropylene. (Here, R is a hydrogen atom, an alkyl group, an aromatic nucleus,
(Halogen atom or alkoxy group, n is 0.1 or 2, M is a monovalent metal, M' is the same as M or a hydrogen atom, M'' is a divalent metal)