JPS6337826B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is an improved method for producing crystalline polypropylene compositions having a β-type crystal structure. It has been known that there are three crystal modifications of crystalline polypropylene: α, β, and γ. However, 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 having a hexagonal crystal structure has a lower melting point and a lower force required for deformation under heating than α-type polypropylene. As a method for obtaining β-type polypropylene, quinacridone and its derivatives, quinacridonequinone,
A method in which derivatives and their metal chelate compounds are mixed with ordinary polymerization catalysts to produce crystalline polypropylene (catalyst mixing method), or a method in which these compounds are mixed with ordinary crystalline polypropylene and pelletized (polymer Mixed method) etc. are known from Japanese Patent Publications No. 47-30297, No. 31930, and No. 48890. Of these methods, the former involves adding and mixing the various compounds mentioned above directly to the catalyst.In actual continuous production of various brands on site, when switching to another grade, the above-mentioned compounds are added and mixed directly to the catalyst. Contamination is a problem and is not desirable. In other words, polypropylene containing the above-mentioned compounds accumulates or adheres to polymerization tanks, post-treatment tanks, drying equipment, storage equipment, and even various types of piping, but these may have an adverse effect on other grades and must be thoroughly inspected for quality control purposes. need to be removed. However, in order to completely remove it, it is necessary to clean the manufacturing equipment with other polypropylene for a very long time, which is almost impossible in practice in a factory. In addition, we have another patent application for a method for continuously producing polypropylene on-site using a solid catalyst containing a titanium compound, which includes a step of co-pulverizing with the compound specified in the present invention in the manufacturing process. However, this does not necessarily completely eliminate the same problems as above. Furthermore, since the various compounds mentioned above are usually colored in various ways, the latter method (polymer mixing method) requires a larger amount of these compounds added than the former method, and the resulting β-type polypropylene composition is quite deeply colored. Therefore, its practical use is limited. 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. Using a new solid catalyst 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, Polypropylene (which is also crystalline) obtained by polymerizing propylene in the range of 0.3 to 500 g per 1 g of the solid catalyst component is synthesized in advance by a batch polymerization method and then converted into conventional crystalline polypropylene. It has been discovered that by addition and mixing, a β-type crystalline polypropylene composition that does not contaminate the on-site continuous polymerization apparatus and is hardly colored can be obtained, and the present invention has been achieved. That is, the present invention provides: (A) titanium trichloride, a titanium trichloride composition, or a titanium compound whose manufacturing process includes a step of co-pulverizing with one or more compounds represented by the following formulas () to (); Propylene or propylene and other α-olefins are polymerized in an amount of 0.3 to 500 g per 1 g of component (A) using a catalyst system consisting of one or more supported catalysts bound or supported and (B) an organoaluminum compound. This is a method for producing a β-type crystalline polypropylene composition, which is characterized by adding and mixing the polypropylene obtained in the conventional crystalline 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, and M'' is a divalent metal.) In the present invention, titanium trichloride and titanium trichloride compositions refer to titanium tetrachloride. Titanium trichloride obtained by reducing titanium tetrachloride with hydrogen, a eutectic of titanium trichloride and a metal halide obtained by reducing titanium tetrachloride with a metal, and titanium tetrachloride as a compound with a Si-H bond or an organic aluminum It means all titanium trichloride compositions containing titanium trichloride or titanium trichloride as a main component, such as titanium trichloride compositions obtained by reduction with compounds. These titanium trichloride and titanium trichloride compositions have the formula ( Before or after being co-pulverized with one or more of the compounds shown in ) to (), it may be subjected to treatments such as pulverization, reaction, or washing with various other compounds, if necessary.This invention A wide range of solid supports are used, including silica, alumina, silica alumina, boron oxide, and magnesium compounds.However, among magnesium compounds such as magnesium halides, magnesium hydroxyhalides, and magnesium oxides, Magnesium halide is particularly suitable. There are no particular limitations on the method of binding or supporting the titanium compound on these solid carriers. For example, (1) co-pulverizing the solid carrier with the titanium compound. In this case, the solid carrier, In addition to titanium compounds, various metal compounds, electron-donating compounds, silicon tetrachloride,
A method of grinding in the coexistence of polysiloxane, aluminum halide, and an organic acid ester complex; (2) heat treatment of a solid support and titanium tetrachloride in the presence or absence of a solvent; In this case,
After reacting the aforementioned solid support with titanium tetrachloride or preparing a composition consisting of a complex of the solid support and an electron donating compound or an electron donating compound and various metal compounds, etc., the solid support is heat-treated with titanium tetrachloride. There are other ways to do this. Here, the titanium compound refers to the aforementioned titanium trichloride, titanium trichloride composition, and titanium tetrachloride. The operation of adding and co-pulverizing the compounds represented by formulas () to () may be carried out either before or after the step of bonding 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 any crystal modification is equally effective for the purpose of the present invention. 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[a·e]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[a,e]quinacridonequinone, and the like. Among the compounds represented by formula (), preferred are 6,13-dihydroquinacridone, 2,9-dichloro-6,13-dihydroquinacridone, and 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.
These include 11-dibenz-6,13-dihydroquinacridone. 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 () used for a normal solid catalyst component, its intermediate, or its raw material (a)
The ratio of compound (b) shown in ~() is b/(a+
b) = 0.005 to 0.70, preferably 0.05 to 0.20
It is. Even if b/(a+b) is smaller than 0.005,
β-type PP can be obtained, but in the case of the method of the present invention, in which the obtained crystalline polypropylene is added to and mixed with ordinary crystalline polypropylene, a large amount of the former crystalline polypropylene is required, which is technically important. lose. When b/(a+b) exceeds 0.70, the polymerization activity of the catalyst decreases, which is not preferable. The time for co-pulverizing a and b is not particularly limited, but is usually 1 to 100 hours, usually 5 to 40 hours. In the present invention, the amount of polypropylene obtained by reacting the solid catalyst component (A) containing (a) and the organoaluminum compound (B) with propylene or propylene with another α-olefin is (A) for the purpose of the present invention.
It is 0.3 to 500 g per 1 g of component. Particularly preferably 1.0 to 50 g. If the amount is less than 0.3 g, decomposition after polymerization, washing with water, etc. will be considerably difficult, which is not preferable. Although β-type crystalline polypropylene can be obtained even if the amount is more than 500 g, in the case of the method of obtaining a β-type crystalline polypropylene composition by adding and mixing the polypropylene obtained in the present invention to ordinary conventional crystalline polypropylene, the former A large amount of polypropylene is required, which is not preferable. Other α-olefins that can be used with propylene in the present invention include ethylene, butene-1, isobutylene, pentene-1, hexene-1, 4-methylpentene-1, heptene-1,
These include octene-1, styrene, etc., and these can be used even if mixed. When polymerizing propylene and other α-olefins, there is no need to particularly limit the propylene content in the resulting polypropylene, but it is usually sufficient as long as it is 50 wt% or more. The organoaluminum compound used in the present invention may be any compound commonly used to obtain crystalline polypropylene. For example, triethylaluminum, triisobutylaluminum, tri-n-propylaluminum,
triisoprenylaluminum, diethylaluminium monochloride, diisobutylaluminum monochloride, diethylaluminium monobromide, diethylaluminium monoiodide, diethylaluminium monoethoxide, diisobutylaluminum monoisobutoxide,
In addition to ethylaluminum chloride monoethoxide, ethylaluminum sesquichloride, diethylaluminum monohydride, diisobutylaluminum monohydride, etc., it also includes complex compounds or reaction products of these organoaluminum compounds and electron-donating compounds, etc.
These can be used alone or in combination. 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 may be carried out under conditions commonly used in the art. The polymerization temperature at that time is in the range of 20 to 200°C, preferably 50 to 100°C, and the polymerization pressure is in the range of normal pressure to
It is preferable to carry out the reaction at a pressure of 200 atm, generally in the range of normal pressure to 100 atm. As a medium for carrying out the polymerization, aliphatic,
Alicyclic, aromatic hydrocarbons or mixtures thereof are used. Examples include propane, butane, hexane, heptane, benzene, toluene, etc. Also, liquefied propylene and other α-
The polypropylene of the present invention may be obtained by bulk polymerization using an olefin as a medium or by gas phase polymerization in which propylene and other α-olefins are polymerized in the gas phase under conditions substantially free of a medium. The molecular weight of the polypropylene obtained in the present invention varies depending on the reaction mode, catalyst system, polymerization conditions, etc., but can be controlled, for example, by adding hydrogen, alkyl halide, dialkylzinc, etc., as necessary. The polypropylene used in the present invention is effective when used in small amounts, so it can be synthesized in advance by a batch polymerization method and then used as needed. This is extremely advantageous. The conventional crystalline polypropylene used in the present invention refers to a crystalline polypropylene homopolymer or a crystalline propylene-α-olefin copolymer having a propylene content of 50 wt% or more.
Here, α-olefin means ethylene, butene-
1, isobutylene, pentene-1, hexene-
These include 1,4-methylpentene-1, heptene-1, octene-1, styrene, etc., and are composed of one or more of these. There is no particular restriction on the ratio of polypropylene (d) obtained by solid catalyst (A) and organoaluminum compound (B) in the present invention to conventional crystalline polypropylene (e), but usually d/(d+e)= 1/10～
It is 1/10 ⁸ , preferably 1/10 ³ to 1/10 ⁶ . The β-type crystalline polypropylene composition (f) obtained by mixing (d) and (e) contains one or more of the compounds represented by formulas () to () (b). Contains approximately 1×10 ^-3 to 1×10 ^-9 wt%. 1×
Even if the content is 10 ^-3 wt% or more, the composition becomes β-type crystals, but the degree of coloring is no longer negligible and no special effect is observed. The β-type crystalline polypropylene composition obtained by the present invention contains conventionally used antioxidants, hydrochloric acid catch agents, slip agents, ultraviolet absorbers, antistatic agents, pigments, inorganic additives, etc. There is no particular problem in including various additives. The β-type crystalline polypropylene composition obtained by the method of the present invention always has a stable β-type crystal structure even after repeated melting, cooling, and solidification. Furthermore, it can be processed by methods such as injection molding, extrusion molding, and compression molding, and has a wide range of uses such as containers, sheets, films, and filaments. The low deformation forces required at high temperatures (100°C to 140°C) make it particularly useful in the production of stretched films, tapes, bands, and filaments. The effects of the present invention will be clarified in the following Comparative Examples and Examples, and the β-crystal polypropylene content in the β-crystalline polypropylene compositions shown in each table 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 20-B model), and the temperature was raised at a heating rate of 10°C/min in a nitrogen atmosphere. The β-crystal content (area %) is determined from the peak area of the crystals. ” Examples 1 to 4: Approximately 600 ml of internal volume containing approximately 80 steel balls with a diameter of 12 mm
Prepare a vibrating mill equipped with a grinding pot.
In the pot, a titanium trichloride/aluminum chloride eutectic (composition is approximately
_TiCl3・1/ _3AlCl3 . ) 60g was charged, and after pulverizing for 40 hours, 6.6g of γ-quinacridone was charged, and further 17
Continued time grinding. In a SUS-32 autoclave having an internal volume of 2, 1 part of n-heptane, 50 g of the above pulverized product (solid catalyst), and 6 ml of diethylaluminium monochloride were charged under a nitrogen atmosphere. After evacuating the nitrogen in the autoclave using a vacuum pump, hydrogen was charged at a gas phase partial pressure of 1.5 kg/cm ² , and then propylene was charged to reduce the pressure in the gas phase to 2 kg/cm 2 .
cm ² gauge. The contents of the autoclave were heated and after 10 minutes the internal temperature was raised to 70°C and the polymerization continued at this temperature. During the polymerization, propylene was continuously fed under pressure to maintain the internal pressure at 5 kg/cm ² gauge. After polymerizing 225g of propylene, stop introducing propylene, release unreacted gas, and methanol
350 ml was added and stirred at 90°C for 30 minutes to decompose the catalyst. Take out the contents, wash thoroughly with water at 60℃, filter,
After drying, 230 g of polypropylene was obtained. This product contains γ-quinacridone and is crystalline. A predetermined amount of the above polypropylene is added to 3,5-di-t
-A predetermined amount of butyl-4-hydroxytoluene (0.10wt% based on the total polypropylene) [η]
Add and mix 500g of normal conventional crystalline polypropylene homopolymer powder of 1.81 to 20mmφ.
It was extruded and granulated using an extruder at 250°C. The β-crystal content of the obtained samples is shown in Table 1 and the drawings. The β-type crystalline polypropylene composition obtained by the method of the present invention is obtained by directly pelletizing the polypropylene obtained by the catalyst mixing method described at the beginning (Comparative Examples 1 to 5) (Table 2, Figure 1). Its performance is second to none. In the method of the present invention, it is only necessary to add a small amount of polypropylene (for addition) that has been synthesized batchwise in advance, so even if it is applied on-site, it will not contaminate the equipment as would occur when the methods of Comparative Examples 1 to 8 were applied on-site. This is extremely advantageous in practice.

[Table] Comparative Examples 1 to 5 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
30 g of TiCl ₃ 1/3 AlCl ₃ ) (hereinafter abbreviated as titanium trichloride) was charged, and after grinding for 40 hours, a predetermined amount of γ-quinacridone shown in Table 2 was added, and grinding was continued for an additional 17 hours. . In an autoclave with an internal volume of 2, under a nitrogen atmosphere, 1 part of n-heptane, about 0.45 g of the above solid catalyst,
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 polymerization, propylene is continuously fed under pressure to maintain an internal pressure of 7.
Kg/cm ² gauge was maintained. After reacting about 450g of propylene, unreacted gas is released and methanol is
350 ml was added and 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 a control crystalline polypropylene containing γ-quinacridone. After adding and mixing 0.1 wt% of 3,5-di-t-butyl-4-hydroxytoluene to the control polypropylene, the mixture was extruded into granules at 250°C using a 20 mmφ extruder. The β-crystal content (area %) of the obtained samples is shown in Table 2 and FIG.

[Table] Comparative Examples 6 to 8 Catalysts were prepared in the same manner as in Comparative Examples 1 to 5, and propylene was polymerized, except that γ-quinacridone was not added when grinding titanium trichloride, but was added in a predetermined amount when polymerizing propylene. . A specific method for adding γ-quinacridone was to charge approximately 0.45 g of titanium trichloride catalyst and 1 ml of diethylaluminium monochloride, and then add a predetermined amount of γ-quinacridone. The results are shown in Table 3 and Figure 1. From Table 3 and FIG. 1, it is clear that Comparative Examples 6 to 8 require a significantly larger amount of γ-quinacridone when producing polypropylene with the same β-crystal content compared to the method of the present invention. .

[Table] Examples 5 to 9 4,11-dimethoxyquinacridone, quinacridonequinone, 6,13 instead of γ-quinacridone
- After co-pulverizing dihydroquinacridone, quinacridone quinone potassium salt, and quinacridone quinone copper chelate compound with titanium trichloride/aluminum chloride eutectic in the proportions shown in Table 4, propylene is polymerized at the working height shown in the table, and methanol decomposition is carried out. ,
After washing with water and drying, a quinacridone-containing polypropylene powder (d) was obtained. A product polypropylene composition (f) was prepared in the same manner as in Examples 1 to 4, except that the obtained polypropylene powder was mixed with the conventional crystalline polypropylene used in Example 1 in the amounts shown in Table 4. Obtained. The β-crystal content is also shown in the same table, and all of them show a high and satisfactory β-crystal content.

【table】 [Brief explanation of the drawing]

The drawing shows the γ-quinacridone content (wt%) in the β-type crystalline polypropylene according to the present invention or the crystalline polypropylene shown in the comparative example and the β-crystal content (area %) in these crystalline polypropylenes. It shows the relationship.

Claims (1)

[Claims] 1 (A) Titanium trichloride, a titanium trichloride composition, or a titanium compound whose manufacturing process includes a step of co-pulverizing one or more of the compounds represented by formulas () to (). Propylene or propylene and other α-olefins are polymerized in an amount of 0.3 to 500 g per 1 g of component (A) using a catalyst system consisting of one or more supported catalysts bound or supported and (B) an organoaluminum compound. 1. A method for producing a β-type crystalline polypropylene composition, which comprises adding and mixing the polypropylene obtained by adding the obtained polypropylene to conventional crystalline polypropylene. (Here, R is a hydrogen atom, an alkyl group, an aromatic nucleus, a halogen atom, or an 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 (Indicates a divalent metal.)