JPS6150085B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a propylene-ethylene block copolymer which has extremely good powder properties, namely particle size distribution and adhesion, and has improved properties. Crystalline polyolefins have been produced industrially since the invention of stereoregular catalysts by Ziegler and Natsuta et al. In particular, crystalline polypropylene is attracting attention as a general-purpose resin having excellent rigidity and heat resistance. However, crystalline polypropylene has the disadvantage of being brittle at low temperatures, so it is difficult to use in applications that require impact resistance at low temperatures. Various studies have been made to overcome this drawback, and many improved methods have already been proposed, but one of the most industrially useful methods is the block copolymerization of propylene and other olefins, especially ethylene. method is known. In other words, Tokko Akira
As shown in Japanese Patent Publication No. 38-14834, Japanese Patent Publication No. 39-1836, Japanese Patent Publication No. 39-15535, etc., propylene is first added in an inert solvent in the presence of a composite catalyst to polymerize a crystalline propylene homopolymer block, Then, ethylene or ethylene and propylene are added to polymerize a statistical copolymer block of ethylene-propylene, or as shown in Japanese Patent Publications No. 44-20621, No. 49-24593, and No. 48-25781. Furthermore, in the block copolymerization, a method is known in which a statistical copolymer block of ethylene-propylene is further divided into two stages and polymerized, and is widely practiced industrially. However, in such a method, after the completion of polymerization, it is necessary to decompose the catalyst or further extract the catalyst residue, and then separate the inert solvent and the polymer. The polymer is further dried to obtain a product polymer. On the other hand, the separated inert solvent is usually industrially separated from dissolved low-molecular-weight, low-crystalline polymers and catalyst residues, purified, and reused, which requires complicated steps. In order to solve this problem,
17488, JP 43-13049, JP 47-26113, JP 49-120986, JP 51-107387, JP 51-
135987, JP-A-52-3684, etc., propylene is homopolymerized in the first step in liquefied propylene or in the gas phase in the absence of an inert solvent using a composite catalyst, and then in the second step A block copolymerization method has been proposed in which ethylene and propylene are statistically copolymerized in liquefied propylene or in the gas phase. Since these methods do not substantially use an inert solvent, the solvent purification process is omitted, and furthermore, the drying of the polymer can also be omitted or greatly simplified. However, in liquefied propylene, the solubility of low-molecular-weight, low-crystalline polymers is lower than that in inert solvents, and therefore, when polymerization is carried out in liquefied propylene, a large amount of polymer particles are formed inside and on the surface of the resulting polymer particles. A low molecular weight, low crystalline polymer remains. If the polymerization is carried out in the gas phase, even larger amounts of low molecular weight, low crystallinity polymer remain. When polymer particles contain a large amount of low-molecular-weight, low-crystalline polymers, many serious problems occur as shown below. In other words, since low molecular weight, low crystalline polymers have high stickiness, the adhesion force between polymer particles increases, and therefore adhesion to the inner wall of the polymerization tank is likely to occur.
The efficiency of removing polymerization heat is greatly reduced. Furthermore, during the transfer of polymer slurry or polymer powder, blockages occur frequently in piping, and also in silos and hoppers for polymer powder, making stable production difficult. In addition, when carrying out polymerization in the gas phase,
Special Publication No. 41-597, No. 47-13962, Special Publication No. 13962, No. 51-
145589, it is an effective means to use a fluidized bed reactor that circulates polymerization gas or a stirred fluidized bed reactor for the purpose of removing polymerization heat or preventing polymer solidification and melting. However, when the adhesive force between polymer particles is large, a very large circulating gas flow rate or stirring power is required to fluidize the polymer particles. Furthermore, if the adhesion force is significantly large, it will no longer be possible to maintain a uniform fluid state, and uniform heat removal will not be possible, resulting in solidification and melting of the polymer, making production difficult. Furthermore, if the polymer particles contain a large amount of low-molecular-weight, low-crystalline polymer, the rigidity and heat resistance, which are characteristics of polypropylene, are significantly impaired. For this reason, when propylene-ethylene block copolymerization is carried out in liquefied propylene or in the gas phase in the substantial absence of an inert solvent, the side effects of low molecular weight, low crystalline polymers are reduced; Furthermore, it is necessary to use a catalyst system that does not increase the adhesive force between polymer particles even if it has some side effects. Furthermore, as mentioned above, when conducting polymerization in the gas phase, circulating the monomer gas is an effective means, but in places where the particle size distribution of the produced polymer particles is wide, scattering of fine particles may occur. happens, heat exchanger,
Alternatively, a great deal of effort is required to separate and remove fine particles because they may clog the circulation pump. Therefore, it is preferable that the particle size distribution of the produced polymer particles be as narrow as possible. In producing the propylene-ethylene block copolymer of the present invention, there is little by-product of low-molecular-weight, low-crystalline polymer, and even if some by-product is produced, the adhesion of the polymer particles is small. Furthermore, a catalyst system that allows the produced polymer particles to have a narrow particle size distribution is essential. However, when carrying out the polymerization of the present invention using a conventional catalyst system in the absence of an inert solvent, the polymer particles contain a large amount of low-molecular-weight, low-crystalline polymer. A problem occurs.
In addition, by reducing titanium tetrachloride with an organoaluminum compound and further heat-treating it in JP-A No. 39-20501, JP-A No. 46-10415, JP-A No. 46-1046, etc.
A method has been proposed for producing a titanium trichloride composition that provides a polymer with few fine particles and a narrow particle size distribution. However, when the present invention is carried out using such a catalyst, although the particle size distribution is narrow, the adhesion of the polymer particles is extremely large due to the presence of a large amount of low molecular weight, low crystallinity polymer. Therefore, it is actually very difficult to stably produce the propylene-ethylene block copolymer of the present invention. As a result of intensive studies, the present inventors have discovered a method for stably and economically producing a propylene-ethylene block copolymer having improved properties by overcoming such problems, and have achieved the present invention. Ivy. That is, the present invention uses a catalyst system consisting of an activated titanium trichloride solid catalyst and an organoaluminum compound, or in addition, a stereoregularity modifier.
In a method for producing a propylene-ethylene block copolymer in liquefied propylene or in the gas phase in the substantial absence of an inert solvent, a titanium trichloride composition is mixed with a mixture of a halogen compound and an ether compound. The present invention relates to a method for producing a propylene-ethylene block copolymer, which is characterized by using an activated titanium trichloride solid catalyst produced by reaction. The titanium trichloride composition used here is obtained by the following method. (1) Titanium tetrachloride has the general formula R′ _o AlX′ _3-o (R′ is a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group, an alicyclic hydrocarbon group, or an aromatic X' represents a halogen or hydrogen; n is a number represented by 1≦n≦3. A titanium trichloride composition obtained by heat-treating a reduction product, or further the reduction product, at a temperature of 50 to 120°C in the presence or absence of an inert hydrocarbon. (2) Titanium tetrachloride has the general formula R′ _o AlX′ _3-o (R′ is a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group, an alicyclic hydrocarbon group, or an aromatic group) represents a hydrocarbon group. X' represents halogen or hydrogen; n is a number represented by 1≦n≦3. general formula
R″ _p AlX _3-p (R″ represents a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. X represents a halogen and p is a number represented by 1≦p≦1.5), or further reacted with an ether compound. (3) Titanium tetrachloride has the general formula R′ _o AlX′ _3-o (R′ is a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group, an alicyclic hydrocarbon group, or an aromatic carbonized represents a hydrogen group. X' represents a halogen or hydrogen. Also, n is a number represented by 1≦n≦3. The ether-treated solid thus prepared is then reacted with the general formula R″ _p AlX _3-p (R″ is a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group, or an alicyclic hydrocarbon). or an aromatic hydrocarbon group; X represents a halogen; p is a number expressed as 1≦p<1.5); A titanium trichloride composition obtained by reaction. (4) Titanium tetrachloride has the general formula R′ _o AlX′ _3-o (R′ is a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group, an alicyclic hydrocarbon group, or an aromatic carbonized represents a hydrogen group. X' represents a halogen or hydrogen. Also, n is a number represented by 1≦n≦3. A titanium trichloride composition prepared by treating the ether treated solid with titanium tetrachloride. The method for producing the activated titanium trichloride solid catalyst in the present invention is a novel method by the present inventors, and is disclosed in Japanese Patent Application No. 108276/1983;
This has already been proposed in 127705 etc. The method of the present invention will be explained in more detail. In the above items (1), (2), (3) and (4), the general formula R' _o AlX' _3-o (R' has 1 to 18 carbon atoms) is used for the production of the reduction product. represents a straight-chain alkyl group, a branched alkyl group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. X' represents a halogen or hydrogen.
Further, n is a number expressed as 1≦n≦3. ) Examples of organoaluminum compounds represented by methylaluminum dichloride, ethylaluminum dichloride, n-propylaluminum dichloride, ethylaluminum sesquichloride, dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, trimethylaluminum, triethylaluminum , tri-isobutylaluminum, ethyldicyclohexylaluminum, triphenylaluminum, diethylaluminium hydride, di-isobutylaluminum hydride, diethylaluminum bromide, diethylaluminum iodide, and the like. Among these, diethylaluminum chloride and ethylaluminum sesquichloride give particularly preferable results. Reduction reaction at -60 to 60℃, preferably -30 to 30℃
Perform at a temperature between . Further, the reduction reaction is preferably carried out in an inert solvent such as pentane, hexane, heptane, octane or decane. When heat treatment is carried out in the above item (1), it can be carried out either in the presence or absence of an inert solvent. Specifically, inert solvents include hexane, heptane,
Examples include compounds such as octane and decane. The heat treatment temperature is 30 to 150℃, preferably
Temperatures between 50 and 120°C are preferably used. The heating time from the reduction reaction temperature to the heat treatment temperature is within 2 hours. There are no particular restrictions on the heat treatment time, but usually
Time periods between 30 minutes and 5 hours are preferably used. In addition, in the above items (3) and (4), the ether compound used when reacting the reduction product with the ether compound has the general formula R ₁ -O-R ₂ (R ₁ and R ₂
represents a linear alkyl group or a branched alkyl group having 1 to 8 carbon atoms, and R ₁ and R ₂ may be the same group or different groups. ) is a compound represented by Specifically, diethyl ether, di-n-propyl ether, di-isopropyl ether, di-
n-butyl ether, di-isoamyl ether,
Dineopentyl ether, di-n-hexyl ether, methyl-n-butyl ether, methyl-
Examples include compounds such as isoamyl ether and ethyl-isobutyl ether. Among these, di-n-butyl ether and diisoamyl ether give particularly preferable results. The reaction between the ether compound and the reduction product is advantageously carried out in the presence of a diluent. As the diluent, inert hydrocarbon compounds such as hexane, heptane, octane, decane, decalin, benzene, and toluene are preferably used. The amount of ether compound to be used is from 0.05 to 3.0 mol, preferably from 0.5 to 1.5 mol, per mole of titanium trichloride. The treatment temperature is preferably 0 to 100°C. There are no particular limitations on the treatment time, but a time between 20 minutes and 5 hours is preferably used. In addition, in paragraphs (2) and (3) above, the reduction product and the ether-treated solid are expressed by the general formula R″ _p AlX _3-p
(R'' represents a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. X represents a halogen. Also, p is 1≦ (This is a number expressed by p<1.5.)
As the compound used when reacting with the aluminum compound represented by, an alkyl aluminum dihalogenide is preferable. Alkylaluminum dichlorides give particularly favorable results. Specifically, methylaluminum dichloride, ethylaluminum dichloride,
n-propylaluminum dichloride, n-butylaluminum dichloride, n-hexylaluminum dichloride, n-octylaluminum dichloride, phenylaluminum dichloride, o
-Tolylaluminum dichloride, cyclohexylaluminum dichloride, methylaluminum dibromide, ethylaluminum dibromide, phenylaluminum dibromide, methylaluminum diiodide and the like. Among these, ethylaluminum dichloride gives particularly favorable results. Further, the above aluminum compound may be used alone or in a mixed system consisting of two or more types of organoaluminum compounds. There are no particular restrictions on the treatment temperature, but the temperature is from room temperature to 200°C, preferably from 50 to 180°C. Although there is no particular restriction on the processing time, a time between 30 minutes and 5 hours is usually preferably used. In addition, in the above paragraphs (2) and (3), the reduction product is reacted with an aluminum compound,
The ether compound used when the ether-treated solid is further reacted with an ether compound can be arbitrarily selected from those used when reacting the reduction product with the ether compound. . The amount of ether compound to be used is 0.05 per mole of titanium trichloride.
~3.0 mol. The treatment temperature is preferably from 0 to 100°C. Although there is no particular restriction on the treatment time, a time between 20 minutes and 5 hours is preferably used. In the above item (4), when the titanium tetrachloride treatment is carried out in producing the titanium trichloride composition, it is advantageous to carry out the treatment in the presence of a diluent. Diluents include hexane, heptane, benzene,
Examples include compounds such as toluene and xylene. The concentration of titanium tetrachloride used is usually preferably in the range of 10% by volume to 70% by volume. The processing temperature is preferably from room temperature to 100°C, preferably from 50°C to 80°C. The treatment time is preferably between 30 minutes and 4 hours. Next, the titanium trichloride composition obtained in this way is mixed with (a) a halogen represented by the general formula X ₂ (X represents Cl, Br or I), (b) _a halogen represented by the general formula represents Cl, Br or I, and a is a number represented by 1 or 3.) (c) Interhalogen compound represented by the general formula R ³ -X (R ³ has 3 to 18 carbon atoms) represents a straight-chain alkyl group, a branched alkyl group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group.
X represents halogen. ⁾ and at least one ^{halogen or halogen} compound selected from the following: a halogenated hydrocarbon compound represented by (Representing a linear alkyl group or a branched alkyl group, and R ¹ and R ² may be the same group or different groups.) Reaction with a mixture with an ether compound represented by let Halogens used in this case include chlorine, bromine, iodine, etc., and interhalogen compounds include bromine chloride, iodine chloride, iodine trichloride,
Examples include iodine bromide. Further, as halogenated hydrocarbon compounds, there are compounds such as linear or branched alkyl halides, alicyclic halides, aromatic halides, and aralkyl halides, but among these, linear or branched alkyl halides give preferable results. bring. Furthermore, among these, linear and branched primary alkyl iodides and linear and branched secondary iodides give preferable results. Particularly preferred is n-butyl iodide. Furthermore, among halogen compounds, iodine gives the most favorable results. Further, as the ether compound used together with the above halogen compound, diethyl ether, di-n
-propyl ether, di-isopropyl ether, di-n-butyl ether, di-isoamyl ether, di-neopentyl ether, di-n-hexyl ether, methyl-n-butyl ether,
Examples include compounds such as methyl-isoamyl ether and ethyl-isobutyl ether. Among these, di-n-butyl ether and di-isoamyl ether give particularly preferable results. The reaction methods include (1) adding a titanium trichloride composition to a mixed system of a halogen compound and an ether compound, (2) bringing the titanium trichloride composition and an ether compound into contact in advance, and then adding a halogen compound. It can be carried out in various forms, such as a method in which the reaction is carried out. The above reaction is preferably carried out in a hydrocarbon solvent such as hesane, heptane, octane, decane, benzene, toluene, xylene. The amount of halogen compound to be used varies depending on the nature of the halogen compound, the nature of the titanium trichloride composition, and the reaction conditions, but is usually 0.001 to 2.0 mol per mol of titanium trichloride in the titanium trichloride composition. , preferably 0.005 to 1.0 mol. In addition, the amount of the ether compound to be used is per mole of titanium trichloride in the titanium trichloride composition,
The amount is 0.001 to 5.0 mol, preferably 0.005 to 3.0 mol. The temperature at which the titanium trichloride composition is reacted with the mixture of the halogen compound and the ether compound can be arbitrarily selected depending on the properties of the reactants, but -
The temperature is 30-200°C, preferably 0-150°C. The processing time is preferably from 5 minutes to 5 hours. Next, the organoaluminum compound used in the block copolymerization of propylene-ethylene in the present invention has the general formula R _l AlY _3-l (R represents a linear alkyl group or a branched alkyl group having 1 to 8 carbon atoms). Y represents a halogen, hydrogen, or an alkoxy group; l is a number represented by 2≦l≦3). Specifically, dimethylaluminum chloride,
Diethylaluminium chloride, diisobutylaluminum chloride, diethylaluminium bromide, diethylaluminium iodide, trimethylaluminum, triethylaluminum,
Examples include diethylaluminum hydride and diethylaluminum ethoxide, and among these, diethylaluminium chloride is particularly preferred. Furthermore, when using stereoregularity modifiers, amines, ethers, esters, sulfur, halogens,
Known compounds such as benzene, azulene derivatives, organic and inorganic nitrogen, and phosphorus can be used. Specifically, triethylamine, tri-n-butylamine, diethyl ether, ethyl vinyl ether, methyl acrylate, methyl methacrylate, ethyl benzoate, p-ethyl anisate, n-
Methyl butyrate, γ-butyrolactone, ε-caprolactone, di-n-butyl sulfide, thiophenol, benzoyl chloride, methyl-p-methylbenzoate, tri-n-butyl phosphite, triphenyl phosphite, tri-n-butyl Phosphine, triphenylphosphine, tri-
Examples include n-butyl phosphate and hexamethylphosphoric acid amide. The amounts of the catalyst components, (A) the activated titanium trichloride solid catalyst, (B) the organoaluminum compound, and (C) the stereoregularity improver, do not need to be particularly limited, but (C)/(A ) = 0.1-10 molar ratio, preferably 0.5-5
It is a molar ratio, and component (B) has a concentration of 1 to 1 in the polymerization tank.
A range of 100 mmol/((B)/(A)>1 molar ratio or more) is preferably used. There is no particular limitation on the order in which the catalyst components are added to the polymerization tank, but if component (A) comes into direct contact with component (C) at a high concentration in the absence of component (B), a decrease in activity may occur. In such cases, it may be necessary to consider the order of addition. By carrying out propylene-ethylene block copolymerization using the composite catalyst system of the present invention, it is possible to obtain a polymer with less by-product of low molecular weight and low crystallinity and low adhesion. That is, in the present invention, the process of reacting the titanium trichloride composition with the mixture of a halogen compound and an ether compound is essential if it is desired to improve the adhesive strength of the resulting polymer particles, and the process of reacting the titanium trichloride composition with a mixture of a halogen compound and an ether compound is essential, and the process of reacting the titanium trichloride composition with a mixture of a halogen compound and an ether compound is essential if it is desired to improve the adhesion of the resulting polymer particles. The adhesion improvement effect is unique to the composite catalyst system according to the present invention. Since the adhesive force of the polymer particles is small, the method of the present invention prevents the polymer from adhering to the inner wall of the reaction tank during polymerization, or from clogging pipes during the transfer of polymer slurry or powder, or from powder hoppers, Also, various difficulties in powder handling such as agglomeration and clogging in the silo are eliminated. Furthermore, in terms of quality, since the formation of low molecular weight, low crystalline polymers is small, a propylene-ethylene block copolymer having extremely well-balanced physical properties of impact resistance, rigidity and heat resistance can be obtained. Furthermore, since the propylene-ethylene block copolymer obtained in the present invention has a particle size distribution in a very narrow range, polymerization in the gas phase can be carried out in a fluidized bed reactor or in a stirred fluidized bed reactor. When carried out in this way, troubles such as particle scattering loss are avoided and steady operation is possible. In addition, serious problems such as polymer agglomeration in the polymerization zone due to powder adhesion and wide particle size distribution, increased stirring power, and polymer adhesion to the reactor wall are eliminated, making the polymerization tank easier to use. Stirring and heat removal or fluidization becomes extremely easy. Furthermore, another feature of the present invention is that, as a unique feature of the composite catalyst system of the present invention, the polymerization activity is extremely high compared to conventional catalyst systems. That is, the amount of polymer produced per catalyst is dramatically increased, and it becomes possible to omit or greatly simplify the step of removing catalyst residues that is carried out subsequent to polymerization. The polymerization method carried out in the present invention involves dividing the polymerization into two stages in the presence of the above-mentioned composite catalyst and substantially in the absence of an inert solvent. Then, by polymerizing propylene alone or by adding a small amount of ethylene so that the ethylene content in the polymer produced in the first step is 4% by weight or less, crystals of 60 to 95% by weight of the final polymer can be obtained. in liquefied propylene, followed by a second step in liquefied propylene.
Alternatively, statistical copolymerization of propylene and ethylene in the gas phase or homopolymerization of ethylene in the gas phase is performed so that the ethylene content in the polymer produced in the second step is 10% by weight or more. A method for producing a statistical copolymer of ethylene-propylene or a homopolymer of ethylene in an amount of 5 to 40% by weight of the final polymer, or a second stage of polymerization, and a stepwise adjustment of the mixing ratio of ethylene and propylene. These methods include polymerizing in two or more stages instead of the above, or polymerizing by continuously changing the mixing ratio, or repeating the steps from the first stage multiple times. When homopolymerizing propylene in the first step, a polymer with a good balance of impact resistance, heat resistance, and rigidity can be obtained by performing the second step polymerization following the first step. However, if it is desired to further improve surface gloss, impact strength, and degree of whitening upon impact, even at the cost of some rigidity, a small amount of ethylene may be added in the first step. It is also possible to carry out copolymerization. Specific embodiments of propylene-ethylene block copolymerization include (1) a method in which all polymerization steps are carried out in liquefied propylene; (2) a method in which the first stage polymerization is started in liquefied propylene and then Examples include a method in which the polymerization is continued in liquefied propylene or in the gas phase, and then the second and subsequent stages of polymerization are performed in the gas phase; (3) a method in which all polymerization steps are performed in the gas phase; The composite catalyst system in the present invention can be applied to any of the above polymerization embodiments,
Its effects are fully demonstrated. When polymerization is carried out in liquefied propylene, the polymerization is carried out at a temperature of 0 to 90°C, preferably 40 to 80°C, under a pressure capable of keeping the propylene in a liquid state, preferably 15 to 40°C.
Performed at Kg/cm ² (gauge pressure). In addition, when polymerization is carried out in the gas phase, the polymerization is carried out at a temperature below the temperature at which the resulting polymer softens, preferably at a temperature of 40°C to
The temperature is 100° C. and the pressure is normal pressure to 60 kg/cm ² (gauge pressure), preferably 5 to 50 kg/cm ² (gauge pressure). In addition, at each stage of polymerization, it is preferable to add a known molecular weight regulator such as hydrogen in order to adjust the melt fluidity of the polymer, but statistical copolymerization of ethylene-propylene It may also be carried out in the absence of a regulator. Regarding the type of polymerization, each stage of polymerization can be carried out batchwise using one or more polymerization tanks, or it can be carried out continuously using two or more polymerization tanks. When polymerizing in liquefied propylene, a commonly used tank reactor or loop reactor is preferably used, and when polymerizing in a gas phase, a stirred mixing tank reactor is preferably used. , a fluidized bed reactor, or a stirred fluidized bed reactor. In order to explain the present invention more clearly, Examples and Comparative Examples are described below, but the present invention is not limited only by these Examples. The results are shown in Tables 1 and 2, and the physical property values and characteristic values in the tables were measured according to the following criteria. Melt index: ASTM D1238−57T Vikatsu softening point: ASTM D1525 Brittle temperature: ASTM D746 Bending stiffness: ASTM D747−58T Izot impact strength: Based on ASTM D256, 20
℃, measured at -20℃. The ethylene content in all polymers was determined by a known infrared spectroscopy method. The intrinsic viscosity [η] was measured at 135°C in tetralin. The powder adhesion force was determined from the shear stress when the normal stress was extrapolated to 0 using the one-plane shear test method. According to the findings of the present inventors, powder adhesion is 2
When it exceeds g/cm ² , handling of the powder becomes extremely difficult. In addition, the polymerization rate <R _p > is the amount of propylene-ethylene block copolymer produced per gram of titanium trichloride solid catalyst using the amount of propylene-ethylene block copolymer produced by polymerization per hour.
Number (g of polymer/g of titanium trichloride solid catalyst.hours)
Expressed as a value converted to Example 1 Catalyst Preparation Method 1 After purging the reaction vessel in 1 with argon, 200 c.c. of dry hexane and 50 c.c. of titanium tetrachloride were added, and the solution was kept at -5°C. Then, a solution consisting of 150 c.c. of dry hexane and 58 c.c. of diethylaluminum chloride was added dropwise to the reaction system so as to maintain the temperature at -3°C. After the addition is complete, continue stirring for another 30 minutes, then
The temperature was raised to 70°C in minutes, and stirring was continued for an additional hour. Then, the reduction product is separated into solid and liquid by leaving it still.
It was further washed with 200 c.c. of hexane to obtain 74.0 g of reduced product. Catalyst preparation method 2 Reduction product obtained in catalyst preparation method 1 of Example 1
31.0 g was suspended in 110 c.c. of dry hexane, then di-isoamyl ether was added in a molar ratio of 1.2 to titanium trichloride, and the mixture was stirred at 40°C for 1 hour. After the reaction is complete, remove the supernatant and add another 100
Washed three times with cc hexane and dried. Catalyst Preparation Method 3 13.0 g of the ether-treated solid obtained in Catalyst Preparation Method 2 of Example 1 was charged into a solution consisting of 40 c.c. of n-decane and 25 c.c. of ethylaluminum dichloride.
Treatment was carried out for 2 hours at °C. After the reaction, the supernatant was taken out, washed three times with 40 c.c. of hexane, and dried. The titanium trichloride composition thus obtained is referred to as a titanium trichloride composition (A). Catalyst preparation method 4 11.0g of titanium trichloride composition (A) and 55.0cc of toluene
The mixture was slurried, and iodine and di-isoamyl ether were added so that the molar ratio of titanium trichloride composition (A)/iodine/di-isoamyl ether was 1/0.10/1.0, and the mixture was reacted at 80°C for 1 hour. The titanium trichloride solid catalyst thus obtained is referred to as a titanium trichloride solid catalyst (). Propylene-ethylene block copolymerization 200
After evacuating the autoclave with a stirrer, propylene was pressurized to 300 mmHg (gauge pressure) and -500
The operation of reducing the pressure to mmHg (gauge pressure) was repeated three times. Next, 1.9 g of titanium trichloride solid catalyst (2) and 20 g of diethylaluminium chloride were added. First, in the first stage, 51 kg of liquefied propylene was supplied, and the polymerization proceeded in the liquefied propylene at a polymerization temperature of 70°C and in the presence of hydrogen. When the polymerization amount reached 17.0 kg, a small amount of the polymer was immediately sampled in order to measure [η] of the produced polymer. Furthermore, in the second stage, after the temperature inside the tank was set to 55°C, ethylene gas was supplied, and ethylene-propylene was statistically converted in the liquefied propylene until the polymerization amount at this stage reached 4.5 kg in the presence of hydrogen. Copolymerization was carried out. During polymerization, the ethylene concentration in the gas phase in the tank is
8.9–11.3 mol%, with an average gas phase ethylene concentration of
It was 10.2 mol%. After the completion of the second stage, the polymer slurry is introduced into the upper part of the 200 mm countercurrent washing tank, and 100 mm liquefied propylene is supplied from the lower part to wash the soluble catalyst and soluble by-product polymer in the polymer slurry. The polymer was extracted from the bottom of the tank. The obtained polymer was dried to obtain a white powdery polymer. Furthermore, the obtained polymer was granulated by adding known additives. No particular problems occurred throughout the entire process of the experiment. The structure of the obtained polymer is shown in Table 1, and the physical properties etc. are shown in Table 2. Comparative Example 1 The same operation as in Example 1 was repeated except that 6.7 g of pulverized activated titanium trichloride (grade name: TAC) manufactured by Toho Titanium Co., Ltd. was used instead of the titanium trichloride solid catalyst (). The ethylene concentration in the gas phase in the second stage is 8.7
~11.0 mol%, with an average gas phase concentration of 10.0 mol%. The obtained polymer was treated in exactly the same manner as in Example 1, but since there was a large amount of catalyst residue in the polymer and the pellets were colored yellow during granulation, alcohol and heptane were further added to decompose the catalyst and extract the catalyst residue. After this, the mixture was dried to obtain a white powdery polymer. The obtained polymer was granulated by adding known additives. The structure of the obtained polymer is shown in Table 1, and the physical properties etc. are shown in Table 2. In Comparative Example 1, a blockage occurred in the piping when the polymer slurry was extracted from the polymerization tank, making it difficult to transfer the polymer slurry. Heat removal became difficult and the polymerization temperature became extremely unstable. Table 2 also shows that by using the composite catalyst system of the present invention, propylene powder has good powder properties and has an extremely well-balanced physical property of impact resistance, rigidity, and heat resistance. It can be seen that an ethylene block copolymer can be obtained. Example 2 Catalyst Preparation Method 1 After purging a 500 c.c. reaction vessel with argon, 80 c.c. of heptane and 20 c.c. of titanium tetrachloride were charged. Then, a solution consisting of 100 cc of heptane and 41.2 cc of ethylaluminum sesquichloride was added dropwise over 3 hours with stirring so that the temperature of the reaction system was maintained at -10°C. After the dropwise addition was completed, the temperature was raised to 95°C in 35 minutes, and stirring was continued for an additional 2 hours. Then, the reduction product is separated into solid and liquid by leaving it still.
After further washing with 100 c.c. of heptane four times, the obtained reduced solid is used as a titanium trichloride composition (B). Catalyst preparation method 2 Titanium trichloride composition (B) is suspended in 250 c.c. of toluene, and iodine and di-n-butyl ether are each mol. Add so that the ratio is 0.1 and 1.0,
The reaction was carried out at 95°C for 1 hour. After the reaction, the supernatant was taken out and washed three times with 30 c.c. of toluene and twice with 30 c.c. of heptane. After drying, 28.0 g of titanium trichloride solid catalyst was obtained. The titanium trichloride solid catalyst thus obtained is referred to as a titanium trichloride solid catalyst (). Propylene-ethylene block copolymerization 200
After evacuating the autoclave with a stirrer, propylene was pressurized to 300 mmHg (gauge pressure), and the temperature was reduced to −500 mmHg.
The operation of reducing the pressure to mmHg (gauge pressure) was repeated three times. Next, 2.6 g of titanium trichloride solid catalyst (2) and 51 g of diethylaluminium chloride were added. First, in the first step, 51 kg of liquefied propylene was injected under pressure, and polymerization proceeded in the liquefied propylene at a polymerization temperature of 70°C and in the presence of hydrogen. When the polymerization amount reached 23.2Kg, a small amount of polymer was immediately sampled to measure [η] of the produced polymer, and unreacted monomer in the polymerization tank was purged to 2Kg/cm ² (gauge pressure). . Furthermore, in the second stage, ethylene gas and propylene gas were supplied, and after increasing the pressure to 10 kg/cm ² (gauge pressure), polymerization was carried out in the gas phase at a polymerization temperature of 60°C in the presence of hydrogen. Ta. When the amount of polymerization reaches 1.4Kg, in order to measure [η] of the produced polymer, immediately sample a small amount of the polymer and reduce the unreacted monomer in the polymerization tank to 6.5Kg/cm ² (gauge pressure). I purged it. The ethylene concentration in the tank during the second stage polymerization was 18.0 to 30.5 mol%, and the average ethylene concentration was
It was 24.0 mol%. Subsequently, in the third stage, ethylene gas and propylene gas were supplied to continue polymerization in the gas phase at a polymerization temperature of 70° C. in the presence of hydrogen. During polymerization, in order to remove the polymerization reaction heat, the monomer mixed gas in the polymerization tank is extracted at a flow rate of 18.4 ^m3 per hour, and after the mixed gas is heated to 50°C in a heat exchanger, it is pumped to the lower part of the polymerization tank by a circulation compressor. I blew it again. When the polymerization amount reached 6.3 kg, the circulation of the monomer mixed gas was stopped, and the unreacted monomer in the polymerization tank was purged. The ethylene concentration in the polymerization tank in the third stage is 54.0~
The average ethylene concentration was 55.0 mol%. The obtained polymer was transferred to a 200°C autoclave equipped with a stirrer, 180g of propylene oxide was added, and stirred at 60°C for 30 minutes to render the catalyst residue contained in the polymer harmless, and then dried. A white powdery polymer was obtained. The obtained polymer was granulated by adding known additives, but the pellets were not colored and had no particular problems. There were no problems such as blockage of pipes throughout the entire process of the experiment, and when the interior of the polymerization tank was inspected after the experiment, no polymer adhesion to the walls or polymer agglomeration was observed. The structure of the obtained polymer is shown in Table 1, and the physical properties etc. are shown in Table 2. Furthermore, the particle size distribution of the produced polymer is shown in FIG. Comparative Example 2 Example 2 except that 8.5 g of crushed activated titanium trichloride (grade name TAC) manufactured by Toho Titanium Co., Ltd. was used instead of the titanium trichloride solid catalyst (2).
I repeated the exact same operation. Ethylene concentration in the second stage is 18.2-27.5 mol%
The average ethylene concentration was 22.9 mol%. Also, the ethylene concentration in the third stage is 52.5 to 59.5
In mole percent, the average ethylene concentration was 55.7 mole percent. When the obtained polymer is treated with propylene oxide in the same manner as in Example 2, there is a large amount of catalyst residue in the polymer, and the pellets are colored yellow during granulation. Therefore, alcohol and heptane were added to decompose the catalyst and extract the catalyst residue, followed by drying to obtain a white powdery polymer. Furthermore, granulation was performed by adding known additives. Furthermore, during the circulation blowing of the monomer mixed gas in the third stage, polymers with fine particle diameters were scattered in the polymerization tank, clogging the mixed gas extraction line, making it impossible to operate satisfactorily. Furthermore, it was extremely difficult to control the polymerization temperature during polymerization, and when the polymer was removed from the polymerization tank after polymerization, clogging occurred in the piping, making it difficult to transfer the polymer. When the inside of the polymerization tank was inspected after the experiment, a large amount of polymer was found to have adhered to the walls of the polymerization tank and the stirrer. The structure of the obtained polymer is shown in Table 1, and the physical properties etc. are shown in Table 2. Further, the particle size distribution of the produced polymer is shown in FIG. 2a. Comparative Example 3 Catalyst Preparation Method After replacing the 500 c.c. reaction vessel with argon, the n-
Decane 200c.c., diethylaluminum chloride 15
I added cc. Next, n-degan 120 c.c. and titanium tetrachloride 25 c.c.
A solution consisting of the following was added dropwise over 3 hours with stirring so that the temperature of the reaction system was maintained at -30 to -35°C. After completing the dropwise addition, the temperature was raised to 40°C for 1 hour while continuing to stir.
The temperature was raised to 40°C and kept at 40°C for 2 hours. Furthermore, the reaction mixture was heated from 40 °C to 160 °C for 1.5 h.
The temperature was raised to 160°C, and stirring was continued for 1 hour. Then, the reduced product is separated into solid and liquid by standing still, and after washing with 100 cc of n-decane four times, the obtained titanium trichloride solid catalyst is referred to as a titanium trichloride solid catalyst (). Propylene-ethylene block copolymerization The same procedure as in Example 2 was repeated except that 5.0 g of titanium trichloride solid catalyst (2) was used instead of titanium trichloride solid catalyst (2). Ethylene concentration in the second stage is 18.5-28.4 mol%
The average ethylene concentration was 23.4 mol%. Further, the ethylene concentration in the third stage was 52.4 to 58.9 mol%, and the average ethylene concentration was 55.6 mol%. The obtained polymer was granulated by adding known additives, but there were no particular problems during granulation. Also, during the circulation blowing of the monomer mixed gas in the third stage, no troubles such as clogging of pipes due to scattering of fine particles occurred. However, it was extremely difficult to control the polymerization temperature during the second and third stages, and when extracting the polymer powder after the polymerization, there were often
It was clogged and it was difficult to transfer the polymer. After the experiment, when the inside of the polymerization tank was inspected, a large amount of polymer was found to have adhered to the walls of the polymerization tank and the stirrer. The structure of the obtained polymer is shown in Table 1, and the physical properties etc. are shown in Table 2. The particle size distribution of the produced polymer is shown in FIG. 2b. By using the composite catalyst system according to the present invention,
It can be seen that a propylene-ethylene block copolymer with excellent powder properties and an extremely well-balanced physical property of impact resistance, rigidity and heat resistance can be obtained. Example 3 After purging an autoclave with a stirrer sufficiently with nitrogen, 200 g of common salt was charged for catalyst dispersion. Then titanium trichloride solid catalyst ()0.263
g, and 4.0 g of diethylaluminum chloride were charged, and hydrogen corresponding to a partial pressure of 0.20 Kg/cm ² was added. After raising the temperature inside the autoclave to 80℃,
Press in propylene to 15Kg/cm ² (gauge pressure),
Polymerization was continued in the gas phase while replenishing propylene to maintain this pressure. After 2 hours, the introduction of propylene was stopped and the unreacted propylene gas was removed until the pressure inside the autoclave was 10
It was purged until it reached Kg/cm ² (gauge pressure). Calculating the mass balance from the amount of propylene gas replenished into the autoclave during polymerization shows that 230 g of propylene homopolymer has been produced by this stage. Furthermore, after raising the temperature to 80° C., ethylene gas was pressurized until the pressure inside the autoclave reached 15 Kg/cm ² (gauge pressure). The statistical copolymerization of ethylene-propylene was continued in the gas phase while replenishing propylene and ethylene to maintain this pressure. At this time, the ethylene concentration in the autoclave was adjusted to be constantly maintained at 35 mol%. After 1 hour, the introduction of propylene and ethylene was stopped, unreacted monomers were purged, and butanol 100%
cc was added to decompose the catalyst. The resulting polymer was filtered using a Buchner filter and treated with heptane.
After washing with 500 c.c. three times and drying under reduced pressure at 60° C., 532 g of white powder was obtained. Excluding 200 g of salt for catalyst dispersion, 332 g of propylene-ethylene block copolymer was obtained. The polymerization activity of titanium trichloride solid catalyst () is g-
The polymer yield per TiCl ₃ hour <R _p > (g.polymer/g-TiCl ₃ .hr) was 421. The ethylene content in the total polymer was 21% by weight. Furthermore, the powder adhesion of the resulting polymer was measured and found to be 1.58 g/cm ² . Comparative Example 4 The same operation as in Example 3 was repeated except that 0.512 g of pulverized activated titanium trichloride (grade name: TAC) manufactured by Toho Titanium Co., Ltd. was used instead of the titanium trichloride solid catalyst (2007). 256 g of ethylene copolymer was obtained. The polymerization activity of titanium trichloride is determined by the polymer yield per g- _TiCl3 /hour <R _p > (g.polymer/g-
It was 167 expressed in TiCl ₃ .hr). Also, the ethylene content in the total polymer is 19% by weight
It was hot. Furthermore, the powder adhesion of the resulting polymer was measured and found to be 3.35 g/cm ² . It can be seen that by using the composite catalyst system according to the present invention, powder adhesion is reduced and the polymerization activity is dramatically increased.

【table】

【table】 [Brief explanation of the drawing]

Figures 1 and 2 show the mass percentage of particles smaller than a certain particle size, based on all particles;
In other words, it represents the particle size distribution.

Claims (1)

[Scope of Claims] 1. Liquefied propylene in substantially the absence of an inert solvent using a catalyst system consisting of an activated titanium trichloride solid catalyst and an organoaluminium compound, or additionally a stereoregularity improver. Activated trichloride prepared by reacting a titanium trichloride composition with a mixture of a halogen compound and an ether compound in a method for producing a propylene-ethylene block copolymer in the medium or gas phase. A method for producing a propylene-ethylene block copolymer, characterized by using a titanium chloride solid catalyst. 2. The manufacturing method according to claim 1, wherein the halogen compound is iodine. 3. The manufacturing method according to claim 1, wherein the ether compound is diisoamyl ether or di-n-butyl ether. 4 The titanium trichloride composition is composed of titanium tetrachloride with the general formula R' _o AlX' _3-o (R' is a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. A patent which is a titanium trichloride composition obtained by heat-treating the obtained reduction product or further the reduction product at a temperature of 50 to 120°C in the presence or absence of an inert solvent. The manufacturing method according to claim 1. 5 The titanium trichloride composition is composed of titanium tetrachloride with the general formula R' _o AlX' _3-o (R' is a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group. X' represents a halogen or hydrogen. Also, n is a number represented by 1≦n≦3.) The resulting reduction product is expressed by the general formula
R″ _p AlX _3-p (R″ represents a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. X is a halogen (in addition, p is a number expressed by 1≦p<1.5), or further, a titanium trichloride composition obtained by reacting with an ether compound. The method according to claim 1. 6 The titanium trichloride composition is composed of titanium tetrachloride with the general formula R′ _o AlX′ _3-o (R′ is a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group.X' represents a halogen or hydrogen.In addition, n is 1≦n≦3.
It is a number expressed as . ), the resulting reduction product is reacted with an ether compound, and the ether-treated solid thus prepared has the general formula R″ _p AlX _3-p.
(R" represents a linear alkyl group, branched alkyl group, alicyclic hydrocarbon group, or aromatic hydrocarbon group having 1 to 18 carbon atoms. X represents a halogen. Also, p is 1≦ Claim 1 is a titanium trichloride composition obtained by reacting with an aluminum compound represented by p<1.5 or further reacting with an ether compound. The manufacturing method described in 7. The titanium trichloride composition is made of titanium tetrachloride with the general formula R' _o AlX' _3-o (R' is a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group, It represents an alicyclic hydrocarbon group or an aromatic hydrocarbon group. X' represents a halogen or hydrogen. Also, n is 1≦n≦3.
It is a number expressed as . ) A titanium trichloride composition produced by reducing the obtained reduction product with an organoaluminum compound represented by The manufacturing method according to claim 1.