Method of producing polyolefins

专利摘要:
A method for producing crystalline copolymers of propylene (major component), ethylene and an alpha -olefin having 4 to 12 carbon atoms, superior in any of various practical physical properties such as cold-resistance, transparency, heat-seal temperature, percentage shrinkage, etc. is provided, wherein a catalyst solution obtained by mixing together a titanium trichloride composition (obtained by mixing and milling a titanium trichloride with a mixed reaction product of TiCl4 with an ether), a dialkylaluminum halide, an electron-donor compound and an inert solvent, is activated in advance of copolymerization, by feeding propylene into the solution under specified feeding conditions, and copolymerization is carried out by feeding propylene and said alpha -olefin simultaneously and continuously, while feeding ethylene intermittently into the gas phase part of the polymerization zone containing the solution.
公开号:SU784785A3
申请号:SU772470316
申请日:1977-04-19
公开日:1980-11-30
发明作者:Сузуки Такеси；Чиба Хиромаса
申请人:Чиссо Корпорейшн (Фирма)；
IPC主号:

专利说明:

one
The invention relates to the plastics plastics and can be used to produce frost-resistant films, for example packaging films, used in the winter season or for storing frozen products, films that can be sealed at low temperatures, films that shrink during heating, films highly transparent sheets used in laminates for blow molding, etc.
A known method for producing polyolefins by copolymerizing propylene, ethylene with α-olefin in the presence of a Ziegler-HaTTatl type catalyst.
Ethylene is fed into the system in an amount of 2-40% of C4-C i-i-olefin pulsed at intervals of 60 minutes. Titanium trichloride is altered as a catalyst component.
The product obtained in a known manner has poor transparency, insufficiently high physicomechanical characteristics: like impact strength, rigidity, and Young's modulus. In addition, a large amount is formed during the copolymerization process.
soluble copolymer, which is a byproduct.
The aim of the invention is to improve the physico-chemical properties and 5 ug; the yield of the final product.
This goal is achieved by using a catalyst as catalyst.
10 mixture of titanium trichloride co-milling product with titanium tetrachloride and ether, a dialkyl aluminum halide, an electron donor compound selected from the group including methyl methacrylate, triethylphosphite, n-butylamine, pyridine, carbon disulfide, dimethyl ether, diethylene glycol and dimethyl ether, and n-butylamine;
20 tetraethylene glycol, and an inert hydrocarbon solvent, activated at 10-50 ° C with propylene with a weight ratio of propylene to a mixture of 0.02 to 1.00, and copolymerization process is carried out with a continuous supply of propylene and α-α-olefin and pulsed ethylene at intervals of 5-60 minutes.
The method involves the implementation of the copolymerization of 72-97 wt.%
propylene, 1-10 wt.% ethylene and 2 18 wt.% C „, - C i-olefin.
Example. 100 g of titanium trichloride (AA) are loaded into a stainless steel ball mill with a volume of 1 l (cylindrical, centrifugal type - 120 rpm in 1 min and containing 30 steel balls with a diameter of 10 mm), after which the reaction product, previously obtained by mixing and reacting, is fed there 5.0 g diethyl ether with 1.0 g T | SVD at room temperature. The grinding operation is carried out at room temperature for 15 hours.
Preparation of the catalyst.
Into a reactor with a capacity of 1 l, add g of 0.5 l of n-hexane and add 6.0 g of diethyl aluminum chloride, 5.0 g of the triclortitic compound prepared in accordance with the indicated procedure, and 0.05 ml of diethylene glycol dimethyl ether. Further, while the prepared mixture was kept at 30 ° C with propylene, propylene was fed for 2 h and its absorption was carried out at a rate of 3.0 g / h.
Polymerization reaction.
25 liters of hexane are poured into a 50-liter reactor and then the full amount of this catalyst is introduced and 25 liters of hydrogen are fed. A mixture of propylene and butene-1 in a ratio of 9: 1 is continuously fed to the reactor to maintain the pressure inside the reactor 10 kg / cm. The temperature inside the reactor is maintained equal.
On the other hand, ethylene is periodically introduced into the gas part of the reactor, with the duration of the intervals between the ethylene feed being equal to 3 D of such intervals at the long run, the flow of ethylene is 5 minutes and each feed of ethylene is 16.0 g.
After 300 minutes from the start of polymerization, 5 liters of methyl alcohol are added to the contents of the reactor and the monomer residue is extracted. Then povy; temperature up to 75 ° C and stirred for 30 minutes, after which 10 liters of purified water are added and the mass is additionally stirred for another 30 minutes. The product obtained is settled and the lower layer of methanol-water is poured. To the upper layer is added 10 L of an aqueous solution containing 5 g of sodium hydroxide in dissolved form. After stirring for 30 minutes, the aqueous layer is discarded. The washing and draining of the aqueous layer is repeated using 10 liters of purified water and, finally, using a centrifugal separator, the powdered polymer is recovered and dried.
The result is 5.1 kg of powdered copolymer.
Further, a portion of the n-hexane liquid obtained by centrifugation is taken to measure the amount of soluble alumina present in it. It has been found that 0.11 kg of soluble polymer is formed.
Polymerization conditions, results and test results for determining the physical properties are shown in Table. 1-5.
Examples 2-4. Example 1 is repeated with the only difference being that the ratio of ethylene to butene 1 is changed, the time intervals in the supply of ethylene, the time of feeding of ethylene and the polymerization temperature.
The polymerization conditions and the results are shown in Table. 1-6.
Examples 5-7. Example 1 is repeated with the difference that pentene-1, hexene 1, octene-1 are used as α-olefin instead of butene-1.
The conditions of polymerization and the result is given in table. 1-6.
Comparative Example 1. Example 1 is repeated, with the difference that the specified trichlorotitanate (DA) is used without mixing and grinding with the reaction product of TiCP with ether.
Comparative example 2. Repeat example 1 with the difference that diethylene glycol dimethyl ether is not used as the third component.
The conditions of polymerization and the results are shown in table 1.
Comparative Example 3. Example 1 is repeated, with the difference that before copolymerization, the propylene solution is not treated with the specified catalyst solution containing the specified trichlorotitanium composition, diethyl aluminum chloride, n-hexane and diethylene glycol dimethyl ether.
The conditions of the polymerization reaction and the results are shown in Table 1.
Comparative Example 4. Example 1 is repeated with the difference that no diethylene glycol dimethyl ether is added as the third component, and the catalyst solution is not treated with propylene.
The conditions of polymerization and the result are presented in table. one.
Comparative example 5. Repeat example 1 with the difference that ethylene is fed to the part of the reactor filled with the liquid phase.
The conditions of polymerization and the results are presented in table. one.
Comparative example 6. Repeat example 1 with the difference that ethylene is fed continuously, not in portions.
The polymerization conditions and the results are shown in Table. 1-6.
Comparative example 7. Repeat example 1 with the difference that the time intervals of ethylene feeds are increased. The results of the polymerization and the conditions are presented in table. 1. Comparative examples 8-11. The polymerization reaction is carried out under the conditions listed in the table, using two monomers, ethylene and propylene without a L-olefin with a carbon number of 4-12. The results are presented in table. 1-6. EXAMPLE 8 An example is repeated with the difference that, together with 100 g of the decree: 1 trichlorotitane (AA), the reaction product obtained by reacting 10 g of diethyl ether with 2 g is used. The results are summarized in tab. Examples 9-11. Example 1 is repeated, with the difference that, together with 100 g of the indicated trichloro-titanium (AA), the reaction products obtained by reacting 12 g of n-butyl ether with 1.2 g of T1064 or reacting 4 g of n-propyl ether with 0 are used. , 6 g of T i se. , or by the interaction of 14 g of isoamyl ether with 1.3 g of TiCEA. The results are summarized in table. b. Example12. Example 1 is repeated with the difference that 0.025 ml of tetraethylene glycol diethyl ether is added instead of 0.05 m diethylene glycol dimethyl ether. The results are summarized in table 5. Examples 13-17. Example 1 is repeated, with the difference that instead of 0.05 ml of diethylene glycol dimethyl ether, 0.05 ml of methyl methacrylate, 0.01 g of trisyl phosphite, 0.01 ml of n-butylamine, 0.03 ml of pyridine or 0.05 ml are added respectively. ml of carbon disulfide. The results are summarized in tab. EXAMPLE 18 Example 1 is repeated, with the difference that, when the catalyst is prepared, propylene is fed at a rate of 0.058 g / h for 20 hours. We obtain the soluble trichl obtained and soluble + weld temperature: contact joint Tying at a given temperature under a load of 1 kg / cm for 1 s using a pa lnik and peeling using a T-type device with a peeling angle of 180 ° and at a peeling speed of 200 mm, min. The temperature at 0.50 kg / 15 mm is the temperature of the weld. Relative shrinkage: the percentage of shrinkage of the sample heated in a glycerol bath at 150 ° C for 30 s,%. The strength of the termination: The results are summarized in table. 6. Examples 19 and 20. Example 1 is repeated, with the difference that the treatment of the catalyst solution with propylene is carried out at a propylene feed rate of 0.02 g (per 1 g of the trichlorotitanium composition per hour; feed time is 30 h (the amount of O, 6 g / h of TiCCj composition (Example 19), or at a propylene feed rate of 1.0 and a feed time of 5 hours (amount fed: 5.0 g (Example 20). Examples 21 and 22. Example 1 is repeated with the difference that the temperature during the treatment of the catalytic solution with propylene (Example 21) or 50 ° C (Example 22). Examples 23 and 24. Example 1 is repeated. the difference that propylene is supplied in the amount of 0.5 g of TiCfj composition, feed rate 0.1 g per 1 g of T i C 5 - compositions per 1 h. Feed time 5 h (Example 23) or 5 g, feed rate 0, 5, the delivery time is 10 hours (Example 24). EXAMPLE 25. The copolymerization is carried out as in Example 1, except that the total amount of ethylene fed is 30 g, the ratio of 1-butene to propylene in the gas mixture is em 1/5. Example 26: The copolymerization is carried out analogously to Example 1, except that the total amount of ethylene fed is 500 g, the ratio of butene is 1. propylene in the gas mixture is 1/50, the polymerization temperature is 40 ° C, the polymerization time is 12 hours, ethylene is fed for 5 minutes, followed by an interval of 60 minutes. EXAMPLE 27 The copolymerization is carried out analogously to example 1 with the difference that 1-dodecene is used instead of butene-1. The results of examples 19-27 are shown in table 2. Expressions and measurement methods used in the tables. Oshok. The new composition, g mer, g x 100% ca, g imer, g corresponds to the load at which the area from 1 cm peels off under the action of a shear tester. Note. With the exception of examples 4 and 5, the polymerization is carried out at 60 ° C. In these examples, the temperature is 70 ° C. In the case of comparative examples 5 and 6, ethylene is fed to the liquid phase. In case of comparative example 7, the feed spacing is too long and the transparency is degraded.
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权利要求:
Claims (2)
[1]
Claim
D. A method for producing polyolefins by copolymerization of propylene, ethylene and C4. — C _1X - ά. -olefin in the presence of a Ziegler-Natta type catalyst, characterized in that * in order to improve the physicochemical properties and increase the yield of the final * product, a mixture of the product of joint grinding of titanium trichloride with the reaction product of titanium tetrachloride and simple ester, dialkylaluminium halides !, electron-donating compound selected from the group consisting of methyl methacrylate, triethyl phosphite, n-butyl__ amine, pyridine, carbon disulfide, dimethyl ** diethylene glycol ether dimethyl tetraethylene glycol ether, and an inert hydrocarbon solvent activated at 10-50 ° C with propylene at a weight ratio of 40 propylene to the mixture from 0.02 to 1.00, and the copolymerization process is carried out with continuous feeding of pro. pylene and C ₄ -C ^ x-4-olefin and pulsed ethylene supply at intervals of 45 to 5-60 minutes.
[2]
2. The method according to claim 1, characterized in that they carry out the copolymerization of 72-97 wt.% Propylene, 1-10 wt.% Ethylene and 2-18 wt.%
50 Cd-Ci <O-olefin.

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同族专利:

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JPS607645B2|1985-02-26|

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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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JP51044315A|JPS607645B2|1976-04-19|1976-04-19|

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