Method of preparing of catalyst solid component for $$$-olefins (co)polymerization

专利摘要:
A solid titanium catalyst component (A) of a catalyst system useful in the polymerization of olefins or copolymerization of two or more olefins or one or more olefins and a diene is prepared by contacting a liquid hydrocarbon solution of (i) a magnesium compound, such as magnesium chloride, with (ii) a liquid titanium compound, such as TiCl4, or a solution of a titanium compound in a hydrocarbon solvent, to form a solid product. The solid product is formed in the presence of (D) an electron donor, e.g. methyl formate, acetic acid, acetic anhydride, acetone, methyl ether, butyl Cellosolve, dimethyl carbonate, methyl silicate. The solid product is also contacted with a polycarboxylic acid ester, e.g. diethyl methylsuccinate. The polymerization or copolymerization of the olefin is carried out in the presence of the solid titanium catalyst (A) and (B) an organometallic compound of a Group I to III metal and (C) an organic silicon compound having an Si-O-C bond. Granular or spherical polyethylene, polypropylene, poly(butene-1), poly(4-methylpentene-1), etc. are produced in high yield, with good flowability, high bulk density, and narrow particle size distribution. The polymers can be produced over a wide range of melt index values without reduction in stereospecificity. Catalyst activity is retained with passage of time.
公开号:SU1826972A3
申请号:SU823514794
申请日:1982-11-12
公开日:1993-07-07
发明作者:Kioka Mamoru；Kasiva Norio
申请人:Mitsui Petrochemical Ind；
IPC主号:

专利说明:

The invention relates to the plastics industry, and in particular to the production of stereospecific (co) polymerization catalysts of a-olefins.
The aim of the invention is to increase the activity of the catalyst during polymerization. especially in the presence of hydrogen.
This goal is achieved by the fact that in the method for producing a solid component (copolymerization of alpha-olefins by the interaction of a hydrocarbon solution of a magnesium compound selected from the group consisting of magnesium chloride, Cr-Cbc-Dialkoximagnesium and Ci-Ci-alkoxymagnesium chloride, a liquid titanium compound of the general formula
Ti (OR) gCU-g, where R = Ci-Csu-alkyl:
g = 0.1 or 4, and an electron-donating compound selected from the group consisting of esters of C2-C20 monocarboxylic acids, aliphatic MF-MFO-carboxylic acids, anhydrides of MFMF-carboxylic acids, and C3-MF5 ketones. aliphatic C3-Cch5 ethers, aliphatic C3-Cc5-carbonates, C3-Cc0-monoesters of ethylene glycol and Cc-Cchioorganic phosphates, C8 ~ C3-dicarboxylic acid ester is introduced during or after the formation of the solid product and the process carry out at a molar ratio of ester of Sv-Szo-dicarboxylic acid: magnesium compounds from 0.05: 1 to 0.5: 1; electron-donating compound: magnesium compound from 0.05: 1 to 0.5: 1; and titanium compound: magnesium compound from 2: 1 to 200: 1.
1826972 AZ
Example 1, Preparation of a solid titanium catalyst component (A).
At a temperature of 130 ° C, a reaction between 4.76 g (50 mmol) of anhydrous magnesium chloride, 25 ml of decane and 23.4 ml (150 mmol) of 2-ethylhexyl alcohol is carried out for 2 hours, resulting in a uniform solution. 1.11 g (7.5 mmol) of phthalic anhydride was added to this solution, and the mixture was stirred at 130 ° C. for 1 h, which allowed phthalic anhydride to be dissolved in a uniform solution. Thus prepared, a new homogeneous solution is cooled to room temperature and completely added dropwise over 1 h in 200 ml (1.8 mol) of titanium tetrachloride, the temperature of which is maintained at -20 ° C. After completion of the addition operation within 4 hours, the temperature of the mixture was raised to 110 ° C, and when the temperature reached 110 ° C, 2.68 ml (12.5 mmol) of diisobutyl phthalate was added to it. Then the mixture was kept at this temperature for 2 hours with stirring. After completion of the reaction, the reaction mixture was subjected to hot filtration, collecting a solid fraction. This solid fraction was resuspended in 200 ml of titanium tetrachloride and a reaction was carried out at 110 ° C. for 2 hours. After completion of the reaction, a solid portion is collected by hot filtration and washed with decane, which is maintained at 110 ° C, and hexane until no free titanium compound is detected in the wash liquids.
The solid titanium catalyst component (A) synthesized by the above method is stored as a suspension in hexane. Part of this suspension is dried to verify the composition of the catalyst. As a result, it was found that the obtained solid titanium catalytic component (A) consists of 3.1 wt.% Titanium, 56.0 wt.% Chlorine, 17.0 wt.% Magnesium and 20; 9 wt.% Diisobutyl phthalate.
Polymerization.
750 ml of purified hexane are charged into a two-liter autoclave and 2.51 mmol of triethylaluminium, 0.125 mmol of phenyltriethoxysilane and 0.015 mmol, calculated on the atomic amount of titanium of the catalytic component (A) prepared as described above, are introduced into the autoclave in the propylene sphere at room temperature. After adding 200 ml of hydrogen, the temperature was raised to 70 ° C and propylene was polymerized for 2 hours. During the polymerization, the pressure was maintained at 7 kg / cm ² (gauge pressure).
Upon completion of the polymerization, the sludge containing the obtained polymer is filtered off, resulting in a white powdery polymer and a liquid layer. After drying, the amount of white powdery polymer is 379.2 g. After extraction with boiling n-heptane, the remainder of this polymer is 98.9%, the melt index (IR) of the polymer is 7.5 g / 10 min, and its apparent density is 0.44 g / ml The particle size distribution of such a white powder polymer is shown in table. 1. As a result of concentration of the liquid layer, 1.9 g of solvent-soluble polymer are obtained. Thus, the activity is 25,400 g of polypropylene / mmol of titanium, and the stereoregularity index (PS) of the polymer as a whole is 98.4%.
Examples 2-6. The experiment of Example 1 is repeated, except that in this case, the amount of hydrogen used in the polymerization process is changed to 100.400, 800, 1000 and 2000 ml, respectively. The results are summarized in table. 2.
EXAMPLES 7 and 8. The experiment of example 1 is repeated completely, except that the polymerization process is carried out at a temperature of 80 and 90 ° C, respectively. The results are summarized in table. 3.
Example 9. 500 g of propylene are charged into a two-liter autoclave and 0.25 mmol of triethylaluminium, 0.025 mmol of diphenyldimethoxysilane and 0.005 mmol, calculated on the atomic amount of titanium of the catalytic component (A) described in Example 1, are introduced into this autoclave at room temperature. 750 ml of hydrogen The temperature was raised to 80 ° C and propylene was polymerized for 1 h. After drying, the amount of the obtained polymer as a whole is 192.3 g. After extraction of the polymer with boiling n-heptane, the residue is 98.6%, its TS is 3.2 g / 10 min, and the apparent density is 0.48 g / ml. Thus, the activity over this period of time is 38500 g of polypropylene / mmol of titanium.
Examples 10-14. The process according to example 9 is completely repeated, except that 0.375 mmol of triethylaluminium, 0.0188 mmol, phenyltriethoxysilane and 0.0025 mmol are calculated on the basis of the atomic amount of titanium of the catalyst component (A) described in example 1, and the duration the polymerization process in these cases is changed respectively to 15 minutes, 30 minutes, 1 hour, 2 hours and 3 hours.
The results are summarized in table. 4,
Example 15, 750 ml of purified hexane are charged into a two-liter autoclave and 2.51 mmol of triethylaluminium, 0.125 mmol of diphenyldimethoxysilane and 0.015 mmol, calculated on the atomic amount of titanium of the catalytic component (A) described in Example 1, are introduced into the autoclave at room temperature in a propylene atmosphere. After the introduction of 200 ml of hydrogen, the temperature was raised to 70 ° C and the propylene was polymerized for 2 hours. During the polymerization, the overpressure was maintained at 7 kg / cm ² . The reaction mixture was processed according to the same procedure as described in example 1.
The results are summarized in table. 5.
Example 16. 750 ml of purified hexane are charged into a two-liter autoclave and 2.51 mmol of triethyl aluminum are added to the autoclave in a propylene atmosphere at room temperature. 0.225 mmol of phenyltrimethoxysilane and U, 015 mmol (in terms of the atomic amount of titanium) of the catalytic component (A) described in Example 1. After 200 ml of hydrogen was introduced, the temperature was raised to 70 ° C and the polymerization of propylene was carried out for 2 hours. During this process, the overpressure is maintained at 7 kg / cm ² . The reaction mixture is then subjected to processing similarly to the above in example 1. The results obtained are summarized in table. 5.
Example 17. 750 ml of purified hexane are charged into a two-liter autoclave and 2.51 mmol of triethyl aluminum, 0.30 mmol of vinyltrimethoxysilane and 0.015 mmol (in terms of atomic amount of titanium) of the catalytic component (A) are added to the autoclave at room temperature in a propylene atmosphere. ), described in example 1. After the introduction of 200 ml of hydrogen, the temperature is increased to 70 ° C and the polymerization of propylene is carried out for 4 hours. During the polymerization, the overpressure is maintained at 7 kg / cm ² , then the reaction mixture is treated similarly to the above in example 1.
The results are summarized in table. 5.
Example 18. In a two-liter autoclave, 750 ml of purified hexane was charged and, in a propylene atmosphere at room temperature, 2.51 mmol of triethyl aluminum per atomic amount of titanium) of the catalyst component (A) described in Example 1 was added to the autoclave. After adding 200 ml of hydrogen to it, the temperature increase to 70 ° C and for 2 hours the polymerization of propylene is carried out. During this polymerization, the excess pressure is maintained at 7 kg / cm ² . Next, the reaction mixture is subjected to processing similarly to the above in example 1. The results obtained are summarized in table. 5.
Example 19. In a two-liter autoclave, 750 ml of purified hexane are charged and in the propylene atmosphere at room temperature 2.51 mmol of triethylaluminium, 0.30 mmol of tetraethoxysilane and 0.015 mmol (in terms of atomic amount of titanium) of the catalyst component (A) are added described in example 1. After introducing 200 ml of hydrogen into the autoclave, the temperature was raised to 70 ° C and the propylene polymerization was carried out for 4 hours. During the polymerization, the overpressure is maintained at 7 kg / cm ² . This reaction mixture is subjected to processing similarly to the above in example 1. The results obtained are summarized in table. 5.
Example 20. In a two-liter autoclave, 750 ml of purified hexane are charged and in the propylene atmosphere at room temperature 2.51 mmol, triethylaluminium, 0.225 mmol ethyltriethoxysilane and 0.015 mmol (in terms of atomic amount of titanium) of the catalytic component (A) described in example 1. After introducing 200 ml of hydrogen into the autoclave, the temperature was raised to 70 ° C and for 4 hours the propylene polymerization was carried out. During this polymerization, the overpressure is maintained at 7 kg / cm ² . Next, the reaction mixture is subjected to processing similarly to the above in example 1. The results obtained are summarized in table. 5.
Example 21. 750 ml of purified hexane are charged into a two-liter autoclave and 2.51 mmol of triethylaluminium, 0.225 mmol of vinyltriethoxysilane and 0.015 mmol (in terms of atomic amount of titanium) of the catalytic component are added to the autoclave at room temperature in a propylene atmosphere. A) described in example 1. After the introduction of 200 ml of hydrogen, the temperature was raised to 70 ° C for 4 hours, the polymerization of propylene was carried out. Next, the reaction mixture is subjected to processing similarly to the above in example 1. The results obtained are summarized in table. 5.
Example 22. In a two-liter autoclave, 750 ml of purified hexane was charged and in the propylene atmosphere at room temperature 2.51 mmol of triethyl aluminum, 0.225 mmol of methylphenyldimethoxysilane and 0.015 mmol (in terms of atomic amount of titanium) of the catalyst component (A) described in Example 1. After introducing 200 ml of hydrogen into the autoclave, the temperature is increased to 70 ° C and the propylene polymerization is carried out for 2 hours. During this polymerization, the overpressure is maintained at 7 kg / cm. Next, the reaction mixture is subjected to processing similarly to the above in example 1. The results are summarized in table. 5.
Example 23. In a two-liter autoclave, 750 ml of purified hexane are charged and 1.8 mmol of triethylaluminium, 0.45 mmol of monochlorodiethylaluminum, 0.12 mmol of phenyltriethoxysilane and 0.015 mmol (in terms of atomic amount of titanium) are added to this autoclave at room temperature in a propylene atmosphere. ) of the catalytic component (A) described in example 1. After introducing 200 ml of hydrogen into the autoclave, the temperature was raised to 70 ° C and propylene was polymerized for 2 hours. During this polymerization, the overpressure is maintained at 7 kg / cm ² . Next, the reaction mixture is subjected to processing similarly to the above in example 1. The results obtained are summarized in table. 5.
Example 24. Preparation of a titanium catalyst component (A).
4.76 g (50 mmol) of anhydrous magnesium chloride are reacted with 25 ml of decane and
23.4 ml (150 mmol) of 2-ethylhexyl alcohol at a temperature of 130 ° C for 2 hours to obtain a homogeneous solution. Then, 1.11 g (7.5 mmol) of phthalic anhydride is added to this solution. To dissolve phthalic anhydride, the mixture is stirred at a temperature of 130 ° C for 1 h. The prepared homogeneous solution is cooled to room temperature and completely for! h is added to 200 ml (1.8 mmol) of titanium tetrachloride, the temperature of which is maintained at -20 ° C. After completion of this operation, the temperature of the mixed solution is increased to 110 ° C over 4 hours. When the temperature reaches 110 ° C, 3.5 g (12.5 mmol) of di-n-butyl phthalate are added to the mixture, and then the mixture is kept at the same temperature for 2 hours. After these 2 hours, a solid fraction is isolated from the mixture. which is collected by hot filtration of the reaction mixture. The solid fraction is then resuspended in 200 ml of titanium tetrachloride and again kept at a temperature of 120 ° C for 2
h. After completion of the reaction, the solid fraction is collected by hot filtration and washed completely with decane, the temperature of which is maintained at 120 ° C, and hexane, until any free titanium compound is no longer detected in the washing liquid.
The resulting catalyst component (A) is stored in hexane as a slurry. Part of this slurry is dried in order to verify the composition of the catalyst. The resulting catalytic component (A) contains, as it was found, 2.1 wt.% Titanium.
Using the obtained solid titanium catalytic component, the propylene polymerization operation is carried out similarly to the above in Example 1. The results are summarized in table. 5.
Example 25. Preparation of a solid titanium catalyst component (A).
4.76 g (50 mmol) of anhydrous magnesium chloride are reacted with 25 ml of decane and
23.4 ml (150 mmol) of 2-ethylhexyl alcohol for 2 hours at a temperature of 130 ° C, resulting in a homogeneous solution. Then, 1.11 g (7.5 mmol) of phthalic anhydride is added to this solution, and at a temperature of 130 ° C., the solution is stirred for 1 hour in order to dissolve the phthalic anhydride. The resulting homogeneous solution was cooled to room temperature, and titanium tetrachloride was added dropwise in 200 ml (1.8 mol) of titanium tetrachloride at a temperature of -20 ° C over 1 h. After completion of the addition operation, the mixture was heated to 110 ° C for 4 hours. When the temperature reached 110 ° C, 2.6 ml (13.0 mmol) of diethyl phthalate were added. At this temperature, the mixture was kept for 2 hours. After completion of the two-hour reaction, the solid fraction was isolated from the reaction mixture by hot filtration. The solid fraction was resuspended in 200 ml of titanium tetrachloride and the reaction was again carried out at a temperature of 120 ° C for 2 hours. After completion of the reaction, the solid fraction was again collected by hot filtration and washed with decane, the temperature of which was maintained at 120 ° C, and hexane until complete disappearance in the wash liquid of any freely detectable titanium compounds.
The prepared solid titanium catalytic component (A) described above is stored in the form of its slurry in hexane. Part of this sludge is dried in order to verify the composition of the catalyst. The obtained solid titanium catalytic component (A) contains, as was established 5, 4.0 wt.% Titanium.
Using the final solid catalytic titanium component (A), the polymerization of propylene is carried out in the same manner as in Example 1 above. The results are summarized in table. 5.
Example 26. Preparation of solid titanium catalyst component (A).
A reaction of 4.76 g (50 mmol) of anhydrous 15 mg of magnesium chloride is carried out. 25 ml Dean ° and
23.4 ml (150 mmol) of 2-ethylhexyl alcohol at a temperature of 130 ° C for 2 hours resulting in a homogeneous solution. Next, 1.11 g of 20 (7.5 mmol) phthalic anhydride was added to this solution, and the mixture was stirred at 130 ° C for 1 h to dissolve phthalic anhydride. The resulting homogeneous solution was cooled to room temperature and, over a period of 1 h, titanium tetrachloride was added dropwise in 200 ml (1.8 mmol), the temperature of which was maintained at -20 ° C. After completion of this addition operation 30, the mixture is heated to 110 ° C for 4 hours. When the temperature of the mixture reaches 110 ° C, 2.9 ml (12.5 mmol) of diisopropyl phthalate is added to it and then the mixture is kept at this temperature for 35 hours. After completion of the 2-hour reaction, the solid fraction is isolated from the reaction mixture by hot filtration . This solid fraction was resuspended in 200 ml of titanium tetrachloride 40 and the reaction was again carried out at a temperature of 120 ° C. for 2 hours. After completion of the reaction, the solid fraction was again collected by hot filtration and washed with decane, the temperature of which was maintained at 120 ° C., and with hexane to until they no longer detect any free titanium compounds in the wash liquid.
The solid titanium catalytic component (A) prepared as described above is stored as sludge in hexane. A portion of this slurry is dried to verify the composition of the catalyst. Ready solid titanium catalytic component (A) contains, as it was found, 2.9 wt.% Titanium.
G using this finished solid titanium catalyst component (A), the polymerization of propylene is carried out similarly to the above in example 1. The results obtained are summarized in table. 5.
Example 27. Preparation of the catalytic component (A).
5.25 g of C2H5OM CI, 23.2 ml of 2-ethylhexyl alcohol and 50 ml of decane are stirred at room temperature for about 1 hour. 1.11 g of phthalic anhydride is added to the prepared homogeneous solution and the reaction is carried out at a temperature of 130 ° C. for 1 h, as a result of which the phthalic anhydride is dissolved in this homogeneous solution. Then the solution is cooled to room temperature. Thus prepared a homogeneous solution is added dropwise with stirring for 1 h in 200 ml of titanium tetrachloride, the temperature of which is maintained at -20 ° C. Next, the mixture is subjected to processing similarly to the above in example 1, whereby the catalyst component (A) is prepared.
Polymerization.
Propylene is polymerized similarly to the above in Example 15, except that in this case the catalytic component (A) prepared according to the foregoing is used. The polymerization activity is 23700 g of polypropylene / mmol of titanium, and the PS of the polymer as a whole is 96.0%. The apparent density of the polymer is 0.42 g / ml.
PRI me R 28. Preparation of the catalytic component (A).
150 ml of a decane solution containing 50 mmol of ethylbutylmagnesium and 17.0 ml of 2-ethylhexanol are reacted at a temperature of 80 ° C. for 2 hours, resulting in a uniform solution. To this solution, 1.11 g (7.5 mmol) of ft- is then added. left anhydride, resulting in a completely homogeneous solution. Then, this homogeneous solution was added dropwise with stirring in 1 ml in 200 ml of titanium tetrachloride, whose temperature was maintained at 20 ° С. Then, the same process is carried out as described in Example 1, whereby the catalyst component (A) is obtained.
Polymerization.
Propylene is polymerized in the same way as in Example 15 using the prepared catalyst component 55 (A). The results are summarized in table. 5.
Example 29. Preparation of the catalytic component (A).
A reaction is carried out between 4.76 g (50 mmol) of anhydrous magnesium chloride. 25 ml of decane, 3.4 ml (10 mmol) of tetrabutoxy titanium
1826972 12 and 17.9 ml (115 mmol) of 2-ethylhexyl alcohol at 13 ° C for 2 hours, resulting in a uniform solution. 1.11 g (7.5 mmol) of phthalic anhydride was added to this solution, and the mixture was stirred at 130 ° C. for 1 hour to dissolve the phthalic anhydride. The prepared homogeneous solution is cooled to room temperature and, over a period of 1 h, is completely added dropwise to 200 ml (1.8 mmol) of titanium tetrachloride, the temperature of which is maintained at 20 ° C. Then, the same operation as described in Example 1 is carried out, whereby a solid titanium catalyst component (A) is obtained.
Polymerization.
Propylene is polymerized in the same way as in Example 15 using the obtained solid titanium catalyst component (A). The results are summarized in table. 5.
Example p 30. Preparation of solid titanium catalyst component (A).
The solid catalyst component (A) was prepared in the same way as in Example 1, except that in this case, instead of 1.11 g (7.5 mmol) of phthalic anhydride, 1.43 910 mmol) of ethyl benzoate was used. Such a catalytic component (A) contains 2.4 wt.% Titanium.
Polymerization.
Propylene is polymerized in the same way as in Example 1 using the prepared solid catalyst component (A). The results are summarized in table. 5.
Example 31. Preparation of solid titanium catalyst component (A).
The solid catalyst component (A) is synthesized in the same way as in Example 1 except that 1.80 ml (15.6 mmol) of benzoyl chloride are used in place of 1.11 g (7.5 mmol) of phthalic anhydride, as a result which in the process of preparing the catalyst receive 2-ethylhexylbenzoate. The finished solid catalyst component (A) contains 3.1 wt.% Titanium.
Polymerization.
Propylene is polymerized in the same way as in Example 1 using the prepared solid, catalytic component (A). The results are summarized in table. 5.
PRI me R 32. Preparation of solid titanium catalytic component (A).
The solid catalyst component (A) is prepared in the same way as in Example 1, except that in this case, 1.47 ml (15 mmol) of methyl acetate are used instead of 1.11 g (7.5 mmol) of phthalic anhydride. The finished solid catalyst component (A) contains 4.7 wt.% Titanium. 5 Polymerization.
Polypropylene is polymerized in the same way as in Example 15 using the prepared solid titanium catalyst component (A). The 10 results obtained are summarized in table. 5.
Example 33. Preparation of a solid titanium catalyst component (A).
The solid catalyst component (A) is prepared in the same manner as in Example 15 above, except that in this case, instead of 1.11 g (7.5 mmol) of phthalic anhydride, 1.12 ml of 915 mmol) of propionic acid is used. The finished solid catalytic component (A) contains 3.1 to 20 wt.% Titanium.
Polymerization.
Propylene is polymerized in the same manner as in Example 15 above using the solid catalyst component (A). 25 The results are summarized in table. 5.
Example 34. Preparation of solid titanium catalyst component (A).
The solid catalyst component (A) was prepared analogously to the above 30 in Example 1, except that in this case, instead of 1.11 g (7.5 mmol) of phthalic anhydride, 7.5 mmol of diphenylketone was used. The resulting solid catalyst component (A) contains 2.5 to 35 wt.% Titanium.
Polymerization.
Propylene is polymerized in the same way as in Example 15 using the prepared solid titanium 40 catalyst component (A). The results are summarized in table. 5.
Example 35. Preparation of solid titanium catalyst component (A).
The solid catalyst component (A) 45 was synthesized in the same manner as in Example 1 except that 1.82 ml (15 mmol) of diethyl carbonate were used instead of 1.11 g (7.5 mmol) of phthalic anhydride. The resulting solid catalytic 50 component (A) contains 4.3 wt.% Titanium.
Polymerization.
Propylene is polymerized in the same way as in Example 15 using the prepared solid catalytic 55 component (A). The results are summarized in table. 5.
Example 36. Preparation of solid titanium catalyst component (A).
The solid catalyst component (A) is prepared in the same manner as in Example 1 except that 0.88 ml (7.5 mmol) of tetramethyl silicate are used in place of 1.11 g (7.5 mmol) of phthalic anhydride. The finished solid catalyst component (A) contains 5.1 wt.% Titanium,
Polymerization.
Propylene is polymerized in the same way as in Example 15 using the prepared solid titanium catalyst component (A). The results obtained are summarized in table 5.
Example 37. Preparation of solid titanium catalyst component (A).
The solid catalyst component (A) is prepared in the same way as in Example 1, except that in this case, instead of 1.11 g (7.5 mmol) of phthalic anhydride, 0.99 ml (7.5 mmol) of n-butyl cellosolve is used. The finished solid catalyst component (A) contains 3.5 wt.% TiUana.
Polymerization.
Propylene is polymerized in the same way as in Example 15 using the finished solid catalyst component.
(A) The results obtained are summarized in table 5.
Example 38. Preparation of solid titanium catalyst component (A).
The solid catalyst component (A) was prepared in the same way as in Example 1, except that in this case, 4.86 ml (20 mmol) of 2-ethylhexyl benzoate was used instead of 1.1 g (7.5 mmol) of phthalic anhydride. The finished catalyst component (A) contains 3.1 wt.% Titanium.
Polymerization.'
Propylene is polymerized in the same way as in Example 15 using the finished titanium catalyst component (A). The results are summarized in table. 5.
Example 39. 750 ml of purified hexane are charged into a two-liter autoclave and 2.51 mmol of triethyl aluminum are introduced into the autoclave at room temperature in a propylene atmosphere. 0.15 mmol of phenyltriethoxysilane and 0.015 mmol (in terms of the atomic amount of titanium) of the catalyst component A. described in example 1. After introducing 100 ml of hydrogen into the autoclave, its temperature was raised to 60 ° C. When the temperature of the polymerization system reaches 60 ° C, a gas mixture of propylene and ethylene containing 8.1 mol% of ethylene is introduced into the autoclave, and an excess polymerization pressure of 2 kg / cm ^{2 is} maintained in the autoclave for 2 hours. After completion of the polymerization, the sludge that contained the obtained polymer is filtered off, as a result of which the reaction mixture is separated into a white powder and a liquid layer. After drying, it was found that the amount of the obtained white powdery polymer is 273.2 g. The IR of this polymer is 6.9, and the pro apparent density is 0.37 g / ml. By measuring the infrared spectrogram of this white powdery polymer, it was found to contain 5.0 mol% of isolated ethylene. According to the method of differential scanning calorimetry, it was found that the melting temperature (Tm) of this polymer is 135 ° C. As a result of concentration of the liquid layer, 14.8 g of polymer dissolved in a solvent are obtained. Thus, the catalytic activity is 19,200 g of polypropylene / mmol of titanium, and the polymer yield is 94.9%.
Examples 40 to 47
Preparation of the catalytic component (A).
The catalytic component (A) was obtained similarly to the above in example 1, except that in this case, instead of 2.68 ml of diisobutyl phthalate, 12.5 mmol of each of the compounds shown in table are used. 5.
Polymerization.
Propylene is polymerized in the same way as in Example 15. except that in this case the catalytic component (A) prepared according to the above is used. The results are summarized in table. 5.
PRI me R 48. Preparation of the catalytic component (A).
mmol of a solid obtained by the reaction of butyl magnesium chloride with silicon tetrachloride, 25 ml of decane and 23.4 ml of 2-ethyl-hexyl alcohol was incubated at 130 ° C for 2 hours, resulting in a uniform solution. Then, 1.11 g of phthalic anhydride is added and a reaction is carried out for 1 h at the same temperature, as a result of which a homogeneous solution is again formed. Next, this solution is subjected to processing similarly to the above in example 1. as a result of which the catalytic component (A) is obtained.
Polymerization.
Propylene is polymerized similarly to the above in Example 15, except that in this case the catalytic component (A) prepared according to the foregoing is used. The results are summarized in table. 5.
Example 49. Preparation of the catalytic component (A).
At a temperature of 130 ° C for 3 hours in the presence of hydrogen chloride, a reaction is carried out between 5.73 g of diethoxymagnesium, 23.4 ml of 2-ethylhexyl alcohol and 50 ml of decane. 1.11 g of phthalic anhydride is added to the prepared homogeneous solution and the reaction is carried out for 1 h at the same temperature. The newly prepared homogeneous solution is subjected to processing similarly to the above in example 1, resulting in the formation of a catalytic component (A).
Polymerization.
Propylene is polymerized similarly to the above in Example 15, except that in this case the catalytic component (A) prepared according to the foregoing is used. The results are summarized in table. 5.
PRI me R s 50 and 51,
Preparation of the catalytic component (A),
Catalytic component (A) was prepared in the same way as in Example 1, except that oleyl alcohol (Example 50) or n-butyl cellosolve (Example 51) was used instead of 2-ethylhexyl alcohol.
Polymerization.
Propylene is polymerized similarly to the above in Example 15, except that in this case the catalytic component (A) prepared according to the foregoing is used. The results obtained are summarized in table 5.
PRI me R 52.
1000 ml of purified hexane are charged into a two-liter autoclave, and further 1.0 mmol of triisobutylaluminium, 0.05 mmol of phenyltriethoxysilane and 0.02 mmol (in terms of atomic amount of titanium) of the catalyst component prepared in Example 1 are introduced into this autoclave. The autoclave is hermetically closed after which the temperature is raised to 80 ° C. At a temperature of 80 ° C, the overpressure is increased to 3 kg / cm ² by hydrogen addition, after which ethylene is introduced into the autoclave to a total overpressure of 8 kg / cm ² . The temperature is maintained at 90 ° C for 2 hours. After 2 hours after the introduction of ethylene, the supply of this latter to the autoclave is stopped and the contents of the autoclave are rapidly cooled.
At the end of the polymerization, the sludge containing the resulting polymer is filtered, and as a result a white powdery polymer is collected. The amount of white powdery polymer after drying is 316 g. The apparent density of this polymer is 0.39 g / ml, and its IR was 5.1. The resulting polymer is characterized by a very good particle size distribution, 5 as shown in the table. 6. The molecular weight distribution of the white powder polymer is measured by gel permeation chromatographic analysis, and as a result, it was found that the value of the molecular weight / M ratio is 3.9.
PRI me R 53. In a two-liter autoclave after being purged with nitrogen, 1000 ml of 4-methylpentene-1, 1.0 mmol of triethylaluminium 15, 0.7 mmol of diphenyldimethoxysilane and 0.02 mmol (in terms of atomic amount of titanium) of the catalytic component ( A) obtained by the above in example 1, after its opening for supplying the catalyst 20 to the autoclave is closed. Next, 50 ml of hydrogen are introduced into the autoclave. The contents of the autoclave are heated to a temperature of 60 ° C and then kept at this temperature for 2 hours. After 2 hours, the contents of the autoclave are rapidly cooled.
After polymerization, the sludge, which included the obtained polymer, is filtered, as a result of which it is separated into a white powdery polymer and a liquid 30 phase. The amount of the obtained white powdery polymer after drying is 213.2 g. The apparent density of this polymer is 0.31 g / ml, and its intrinsic viscosity is (¾) 5.5. By concentrating the liquid phase, 3.1 g of a solvent-soluble polymer are obtained. Thus, the activity of the catalyst is 10,800 g of polymer / mmol of titanium: polymer yield of 98.6 wt.%.
Example 54. After purging with nitrogen in a two-liter autoclave, 1 l (580 g) of purified butene-1 was charged with it and at a temperature of 0 ° C, 1.0 mmol of triethylaluminium, 0.7 mmol of diphenyldimethoxy 45 lan and 0.02 were introduced into this autoclave mmol (in terms of the atomic amount of titanium) of the catalytic component (A) prepared in accordance with the above in Example 1. The hole for feeding the catalyst into the autoclave was closed and then 300 ml of hydrogen were introduced into the autoclave. The contents of the autoclave are further heated to 35 ° C and maintained at this temperature for 2 hours. After 2 hours, 10 ml of methanol is added to stop the polymerization. Unreacted butene-1 is removed from the autoclave by purging. The obtained white powdery polymer is dried and its amount is determined. It is 263 g. The residue after extraction of the polymer with boiling n-heptane 96.5%.
The conditions and results of examples 55-135 are presented in tables 7 and 8.

权利要求:
Claims (1)
[1]
Claim
A method of obtaining a solid component of the catalyst for (co) polymerization of a-olefins by reacting a hydrocarbon solution of a magnesium compound selected from the group consisting of magnesium chloride, Cr ~ Cbc-dialkoximagnesium and Cc ~ Cigalkoxymagnesium chloride, a liquid titanium compound of the general formula
Ti (OR) gCU-g, where R is Cч-Cоо alkyl;
g = 0.1 or 4,. and at least one electron-donating compound selected from the group consisting of esters of Cg-Cg-monocarboxylic acids, aliphatic Cg-Cch-carboxylic acids, anhydrides of Cg-Cch-carboxylic acids, C3-C- | 5-ketones, aliphatic simple C3 MF-esters, aliphatic C3-C15 carbonates, simple C3-Ci-monoesters of ethylene glycol, and C-Ci-organic phosphates, until a solid product is formed, it must be so that in order to increase the activity of the catalyst during polymerization, especially in the presence of hydrogen, during or after formation the solid product is introduced ester Sv ~ C3-dicarboxylic acid and the process is carried out at a molar ratio of the ester of St-C3-dicarboxylic acid: magnesium compound from 0.05: 1 to 0.50: 1, electron-donating compound: magnesium compound from 0.05 : 1 to 0.50: 1 and titanium compound: magnesium compound from 2: 1 to 200: 1.
Table 1
Over Over Over Over Over Over Over Less 190 mk 840 mk 420 mk 250 mk 177 mk 105 mk 44 mk 44 mk 0 0 4.1 95.7 0.2 0 0 0
That! 5 liters 2 Example Amount of hydrogen IR Activity, g polypropylene / mmol titanium PS (%) white powder polymer PS (%) of the polymer as a whole 2 100 ml 2.7 20,000 98.9 98.4 1 200 ml 7.5 25,400 98.9 98.4 3 400 ml 20 30 900 98.6 98.0 4 800 ml 69 32 100 98.3 97.7 5 1000 ml 145 34 00 97.7 97.0 6 2000 ml 280 29,600 97.4 96.6
Table 3
Example Temperature, g polypropylene / mmol titanium Activity, g polypropylene / mmol titanium PS (%) white polymer powder PS (%) of the polymer as a whole Bulk weight g / ml IR. g 1 70 ° C 25,400 98.9 98.4 0.44 7.4 7 80 ° C 25 300 99,2 98.6 0.43 10.1 8 90 ° C 22,600 98.7 98.1 0.41 21.3
Table 4
Example Polymerization time, min Activity, g polypropylene / mmol titanium PS (%) of the polymer as a whole Bulk weight, g / ml 10 fifteen 10 400 97.0 0.47 eleven thirty 25,200 98.2 0.48 12 60 32 800 98.3 0.49 thirteen 120 72,400 97.9 0.48 14 180 88,400 97.9 0.49
19 1826972
Table β
"Example Magnesium compound Titanium compound Electron donor ether (0 Siloxane (C) Asset. polymorph / nmrl-Ti L% PURE polymer Bulk weight g / ml Vffc molar ratio The molar ratio of D / lfg Tirtfc molar ratio The molar ratio C / B 1 2 3 I " 5 6 7 8 9 10 eleven 12 thirteen 1 Chloride T1S1 Phthalic Diyeobu- Fennltrietoksi- 15,400 98.4 0.44 0.25 0.15 36,4 0,050 magnesiumanhydride tilphthalate silane2 -and- , ti. 20,000 98.4 0.42-AND- -eleven- .... 3 · ”· »··.30,800 98, " 0.44- • I. -AND- .... 4 -AND. .eleven.32,100- 57.7 0.44-AND-- ¹ · - 5 -"1. 34,000 97.0 0.45 -n- -1*. -1"- -AND· 6 .and. 29,600 96.6 0.42 -H- -Ί- 7.4.-II " • l »· 25,300 98.6 0.43 .... b22, $ 00 98.1 «, 4 |-Ί- ... " 9 - ¹ * - -*1" .. Dnephenyldiethoxysilane. 38,500 98.6 0.48.N. -IN- 0.10 10 .... "··". -I- .and. Feiltrietoxyslnaya 10,400 97.0 0.47 - "m..... 0,050 AND25.200 98.2 0.48-eleven · -eleven- -I. 1232,800 98.3 0.49 -eleven-—41 - -eleven- 13 n ·· 72.400 97.9 o.4e-1·- -IN- -eleven- Chlorinated Tici ftlevlevy Diyeobutyal- Fenmltrietoksisi- 86,400 97.9 0.49 οχ 0.15 36,4 0,050 rotted.anhydride phthalate Dan fifteen Life> "<Plmmetoksisi-31,600 98.9 ", 45 L. - - ·· -0,050 barking16 - “·.AND. •> and Fvnltrietoksisi- 23,700 98.6 0.45 .'1. -1 " _and"AND- 0,090 llamas1.7.... .1·" -and- Oinltrimethoxysilane 19,200 97.6 0.44 ....· 0.12 ie -P_ Nettrmtmehsisi · 23,300 96.9 0.44.1". -eleven- 0.18 barking ia• n. -n- Tetraethoxysilane 22.300 96.8 0, * 3 .and. -.4-0.12 20 Ethnltrnethoxysilane 22,200 98.0 0.44-AND- -AND- 0,090 21 -II. ...." Oinyltrimethoxysilane .8,700 98.8 0.43 ·. .... - · -. 22 .... „H" 1 Ιβ tmlfe nildime toksisilen 26,700 98.6 0.45 .... 23 -and- Fenmltrietohsnsi- 23,100 97.6 0.44.'1-0,053 barking2kTiCl _v Dn-yzo-bu-. tmlphthalate .and. 23,000 97.8 0.41 0.25 - ··· i »N- 0,050 25 ... Diethphthalate "and. 18.300. 97.5 0.44 -"1. .... 26 - “.eleven. Dnisopro * Pylphthalate ji. · 20,100 97.3 0.44 -'•I.... .... 27 C ^ jOligCl.eleven. Diisobutml Difenzldimethoxy 23.70 " 96.0 0.42 -1"--eleven- -•1- phthalate silane· .- 28 < Tici ₄Phthalic Diyvo6yt "n- Diphenyldimethoxy 23.200 97.6 0.43 0.25 0.15 36, " 0,050 anhydride Phthalate silane 29th Chloride Tetrabu- . . 24,300 98.1 0.43 magnesium Toxins - ’Tan / T SCthirtyT1STs Ethylben *Fenmltrietoksisi- 13.14 " 97, b 0.43 -L- 0.20 howlslan 31 ....I-ethylhexyl benzoate.and. 15,400 97.4 0.40 - * ύ 0.3132 Methyl-Difenmldimethoxy-17,700 97.8 0.35.0.30 .and acetateLEN 33 Propio no-.... 25,100 97.3 0.43 -n- 0.30 ,, -U shaft kitty ”lot * 34 -AND. -N. Diphenylketo n.... 31,100 97.3 0.370.15 - ·> -
132 ......... 1 6. ) 7 'τ 9 1 ^{, 0}n [ 12 35 Magnesium chloride T1C1 | Lietipkaronat Liisobutndcarjenate Life ached dyne penny lan, -> 6.30 in 98.1 8.350.3036 ....Tetramethylsilicate.and. B, 400 97.5 0.110.15.... 37· ”· n-Sutml- ·: ", celloeol 17.JU0 96.0 0.36 .eleven. 38 Chlormd magnesium2-ethylhexylbenzoate Liaobutylphthalate Yaiphenyldnietoxysilane 22,100 97.7 0.11 0.25 0.10 36.4 0.050 39 - ·· -Phthalic anhydrideFemiltrietokemsilan 19.200 91.9 0.37 0.25 0.15 36.4 0,060 10 Dia> entmphthalate Dmphenyldimethokemenpan 25,900 S6.4- 0.13 0,050 111 - · -- * ’· Momoethyl phthalate19 ¢ 00 93.1 0.12 12 .... Diphenylphthalzt23,900 95.1 0.12 43 Dm-2-ETM | 1hexylphthalate .... 21,200 96J 0.12.'L .... - · - *4 Diethyl phenyl malonate20,700 92.9 0.11 --- fifteen - ··· Di-2-ethylhexnylcamate19,500 95.1 0.11 - ^u - 16 Liethnl-1,2tsnkhloheksan dikarboxmlat23,100 93.1 0.10 17 1,2-diacetoxymbenzene .... 21,300 92.8 0.11 - ·· - 18 L- * Tici * Phthalic anhydride Dmizobutnp phthalate Life Shldmmethoxysilane 21,300 91.9 0.11 0.25 0.15 36,4 0,050 19 Diethoxymagnet »L · ”· -1·. IB,> 00 95.1 0.12 -i "- fifty Magnesium chloride• ^m 19,300 96.1 o.M• - “·.5> - ^and - - · - 24,300 96.1 0.13 ---. - ·· --..- 52 -1·- Feyltrietoksi-silane > 5.800 R / L 3.9 0.39 --- 53 • .4. nn Diphenyldimetokem Ifl.fiCO 98Λ 0.31 0.70 54 · 1), 000 38.5 --H-
The magnesium compound is obtained according to the specified text of Example 28. * The magnesium compound is prepared according to the text * Example 18,
Table 6
More than 1190 mk More than 840MK More than 420MK Over 250MK More than 177MK More than 105MK More than 44MK Less than 44MK 0 0.3 6.8 90.5 2,3 0.1 0 0.
Example
Compound! magnesium I
55 Magnesium Chloride
5&
S7
6 '|
Table 7
Compound! titanium i
Electron donor
Ether (C)
Siloxane (C)
Activity (-polmed imol-TT)
L PURE polymer
Bulk Weight (g / ml)
Molar;
from cache i
E / tfc | Zero ratio | O / »g
The molar ratio T> Alg
Molar I about r ngmve in
C / B
T1sts n-Ohtanraic acid
Acetic anhydride Dm-p-butylketone
Li-p-hexyl. ether
Di-p-hexnpkaro'nat
1 I
tilphthalate Liphenylmetho-. silane 21,0040.41 0.25 0.15 36.6 0,050 .... .... 25,000 92.6 0.38 .... -'•and -in. -in- .... 7,800 92.5 0.60 -. · - .... .... ....26,600 97.4 0.35.... - · _ -AND. ....21,400 97.1 0.40. .and. _P 23,500 57.0 0.60.... .... .... ....13,500 97.5 0.33,,
Iethylcelloaleols
Magnesium chloride
PSC m-Hexyl-Diyeobutylcellosolve phthalate phenylcellosolve p (cnr, pfoepipy.
F (OPh)
68 Phthalic anhydride Di-p-butyl Ita * Conat 69Ti (OEt) Cl, Tici _A ^JDimethyl * Ketone Dioeobutyl phthalate 70 N "" - Tlclj phthalic anhydride Di-2-ethylhexylphenium 71 ιίΜαιΡϊ Diisothylphthalate ' 72 Yves (0-IEO- 73 Mg (οαι pci -and. 74 llg (0 “H3o- - · -
& 3 VC
9 's “n,) _t
Chloride • Magnesium
Chloride • Magnesium
TTsOSP.k '
TiCl „
Ti (0-2etilgem · forces «T1STs
TtCU ’
Ti "" - 2ZTIPheksip) C1. t> ss ^TiC, 4
T1STs
Phthalic ant idr "1d .11.
Dodecylbenzoate
Diisobutyl phthalate
Diespropyl carbamate
Lngheptyl carbonate
Phthalic ZN hydride
Ftapeev ENGIDOID
Lisobutylphthalate
-93 y'i 6
3
100 {Cpip ^ HUCpiPj (μ-αι ^ ιρ, οι.ωαφ ,:. (E-ayytppitoay *: (ο-αι, φφ ^ Ηοαιρρ (ρ-αι, φρρίωε, Η ^: "^ rPfSitoaipi: и-С, and ₇ ЗК0С,! 1Д cpi „(afp solution: c ₄ u _f / aipsi (o (yip ₄ ; c ₆ H _<e 3i (oaiy>,;
cp » _H si (<jcpip _a cy ^ siwatpjCi ¹ (nc ^ pitociip *: si (oai _r ) _t : (i8O-C | K,), Si (GCHp ₄ : nc ^ n ^ sHwpipj '
12,100
56.5
0.36
Diefeikpme Tokensilan
Liphenyldimethoxysilane sitocnp, Cjllj-SHOCUPj. n-cpij.siUatpjCi
12,500 96 f oh 3b 0.25 0.15 36Λ 0.050 11.00 95.5 0.35 0.25 0.15 36.1. 0,050 16,500 06.5 9.36 - · »»-IN. .... 16,700 96.7 0.37-in. .... 14,500 55.5 0.35 22.600 04.9 0.42 .... .... 23,500 98.2 0.39 .... .... .... 20,500 97.8 0.42.... .... 19, eoo .97.3 0.38 .... .... .... ... 21,000 97.1 '0.40 ’ -IN- .IN. 20,100 57.9 0.30 ....-IN- .... 21,200 97.1 0.60 .... -IN- .... .... 26,000 00.3 0.43 0.25 0.15 36,4 0,050 25,500 00.1, 0.61 · - .... .... .... 23,300 98.0 0.40 .... -in- -IN. .... .21,300 97.9 0.63 - * · - 18,500 96.5 0.38 -AND. -in- -in- -IN 15,200 97.4 0.35 .... •AND..... v.zos 07.3 ozz .... ....u zso 06.7 0.64.IN. .... 0,090 10,200 97.6 0.44 .1·.-AND- 13,300 97.2 0.44 0.25 0.15 36.6 0,090 18,900 96.5 0.43 .... - ¹ '. 31,700 98.8 0.44 _H_ - 0.10 24,000 98.0 0.45 -in. .20,600 58.1 0.46 - ·· - .IN., 22,200 56.2 0.42-IN- .... _ | _ 24,300 08.5 0.42 -in. -IN- 1.9,300 97.6 0.44 0.25 0.15 36,4 0.10 18,900 38.8 0.44· '»<, 20,200 96.8 0.42 -M_ 31.700 98.7 0.44 -N. -in- .IN. 20,200 96.8 0.43 -N.-in. _ | 1_ 20,000 00.6 ' 0.46-IN--IN. 10.300 97.2 0.64 - · - 1b, CC0. 97.1 0.44 0.25 0.15 36,4 0.10 33,100 98.7 $ 0.4 -in. 33,500 99.1 0.65•TOJ1.10C 99.0 0.45-IN. .... .... 15.800 97.0 0.43-in- -in. 1,0
182’6972
’[ ·; .......: 1 ::::: 1 g ._________ L · .............. „IG ..... 1 ³1 " 1 ..... 1 ^{, g}G ’’ ·· 103 Magnesium chloride TiCl * F1 left anhydride Liieobutil ’(OCH,) * 28,300phthalate 96.1 0.43 0.25 0.15 36.4 0, 10 104 ** '* cf: „(a: p si (acute, 14,100 98.5 0.40 - ·· --about. 0.10 105 Proliono’s acid Dmphenyldmmetoxm ”silane 28, "100 96.8 0.39 0.11 0.060.050 106- ”* * * ’’17,900 37.6 0.41 0.45 0.45 -IN. - ··. 107 19,700 97.7 0.40 0.45 0.06 -AND. 10V ’*16, zoo 96.5 0.43 0.11 0.45109w ’. Ztilben-'aoat31,200 9B.0 0.42 0.14 0.30 3.64 0.10 110 ··Phthalic anhydride30,700 58.2 0.4)0.15 | 80 111 30.500 39,2 0.44 - ·· --and- 0.5 112 - · - ⁿ * 25,000 99.5 0.44 -and. 2.0
The polymerization conditions corresponds to example 15
At- Bring- Connected Electron donor Ether (£) ABOUT Siloxane Assets* AND% The bulk Polar Polar Polar Molar measures nenke some (FROM) bone PURE my weight otnom- OTHOW4 * again otnom- naked titanium -polymer/ half a kilo (g / mp) to me nie to me not iol * -T1 raB / HB D / Μβ s / h C / B
113H4I5 T1 chloride. SC magnesium Phthalic Anhydride (lSO ~ Btl) C-C00Et----. COOEi P-BuCH-COOEtCoolC-COOElc-coon Diphenyl * 14,200. methoxy * silane19, U09,900 91.891.192.1 0.350.320.34 0.25 0.15 36,4. ··· 0,050 116 -P. .... CjHfCH-COOEH ____ cootH - ’· * 16.700 31.9 0.3 * .... .... .... .... 117 - · -GNG ^C00EN '^ COOtH 17,300 92.1 0.35 - · - .... .... .... 118 ^^ - COOMe Dineobutnphthalate 20,800 96.9 0.40 .... .... P9.... <g) -coo-nc ₃ H ₇22,800 96.0 0.42 U'--''IN 120 .... .... <^ - C0tMeo-C ₃ H, - '* * 24,100 96.0 0.4 0.25 0.15 > 8.8 0,050 121 .... .... {(5> -coo-nc ₃ n ₃* · '* 20,900 98.9 0.43 * ’ 122.... <5 ^ COO-HJO-C * H ₉ „ 21,800 97.1 0.40 Ji. ....123 .... .... ^ C ^ “COO-U30AMMA„ 26,000 96.2 0.45 .and. .,1..... 124 .... .... <§Bcoo- 20,900 94.7 0.38 .... -it.125 "P_Me- <§) -COOMe * 23,000 97.2 0.83 .... 126 »'·· 23,100 96.9 0.38 .... 127 .... .... COOEl 28, too 96.6 0.41 .....*8- -ABOUT. 128 .... .... MeO - @ - COOEi * · ’* 24,100 96.7 0.40 .... .... .... .... 129 .... .... CHjCH _a COOH * “* 25,100 97.3 0.48 ί ,, 130 .V.CHjCOOH ’ * · ’* 26,100 * 94.7 0.4l -Η- .μ. 131 Triethyl anhydride ** 9.100 90.7 0.36 _n. Ji.132 Maleic anhydride 7,500 91.6 0.38 0.25 0.15 036.4 0,050 133 **Dimethylketone 20,400 93.3 0.43 .and. 134 * *Dioeamyl ether 12,100 92.2 0.38 .eleven. 135 96.0 0.35 ..... .... ....
. (

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同族专利:

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公开号 | 公开日

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DK164284C|1992-11-30|

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BR8206573A|1983-09-27|

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GB2111066B|1985-05-09|

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BE895019A|1983-03-16|

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GB2111066A|1983-06-29|

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PL239001A1|1983-10-10|

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JPH069722A|1994-01-18|

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NO161178B|1989-04-03|

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FR2516520A1|1983-05-20|

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SE458278B|1989-03-13|

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DE3241999A1|1983-05-26|

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DE3241999C2|1988-12-01|

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PH18781A|1985-09-25|

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SE8206460L|1983-06-28|

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KR860001806B1|1986-10-23|

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RU2091393C1|1997-09-27|

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ATA406682A|1990-10-15|

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FI71325C|1986-12-19|

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RO85779B|1985-01-30|

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HU196612B|1988-12-28|

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DK504982A|1983-05-14|

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RU2024303C1|1994-12-15|

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NL186245C|1990-10-16|

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DK164284B|1992-06-01|

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JPH0356245B2|1991-08-27|

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FI71325B|1986-09-09|

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KR840002415A|1984-07-02|

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PL146395B1|1989-01-31|

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SE8206460D0|1982-11-12|

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FI823892L|1983-05-14|

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AU554187B2|1986-08-14|

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FI823892A0|1982-11-12|

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AT392645B|1991-05-10|

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US4952649A|1990-08-28|

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NL8204385A|1983-06-01|

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JPH0686491B2|1994-11-02|

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NO161178C|1989-07-12|

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JPS5883006A|1983-05-18|

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RO85779A|1985-01-24|

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AU8982182A|1983-05-19|

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FR2516520B1|1985-05-03|

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NO823798L|1983-05-16|

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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JP56181019A|JPH0356245B2|1981-11-13|1981-11-13|

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JP4192798A|JPH0686491B2|1981-11-13|1992-06-29|Solid titanium catalyst component for olefin polymerization|

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