CA1104117A - Catalysts for polymerizing ethylene - Google Patents
Catalysts for polymerizing ethyleneInfo
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- CA1104117A CA1104117A CA279,611A CA279611A CA1104117A CA 1104117 A CA1104117 A CA 1104117A CA 279611 A CA279611 A CA 279611A CA 1104117 A CA1104117 A CA 1104117A
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- catalysts
- compound
- grignard
- carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
Abstract
ABSTRACT OF THE DISCLOSURE
Catalysts for polymerizing ethylene to high yields of polyethylene having a controlled particle size are disclosed.
The catalysts are prepared from new catalyst-forming components which are the reaction products of solid halogenated titanium compounds, Grignard compounds and halogenating agents. Said components, on mixing with organometallic compounds of metals belonging to Groups I-III of the Mendelyeev Periodic Table result in the catalysts capable of polymerizing ethylene to polyethylene having a controlled particle size.
Catalysts for polymerizing ethylene to high yields of polyethylene having a controlled particle size are disclosed.
The catalysts are prepared from new catalyst-forming components which are the reaction products of solid halogenated titanium compounds, Grignard compounds and halogenating agents. Said components, on mixing with organometallic compounds of metals belonging to Groups I-III of the Mendelyeev Periodic Table result in the catalysts capable of polymerizing ethylene to polyethylene having a controlled particle size.
Description
~ 7 THE PRIOR ART
It is known to polymerize ethylene to polyethylene with the aid of catalysts of various types, in particular with the aid of catalysts consisting of the products o~tained by mixing titanium compounds with organometalIic compounds of metals belonging to Groups I to III of the Mendelyeev Periodic Table r such as the products obtained by mixing TiC14 or TiC13 with an aluminum trialkyl or a dialkyl aluminum monohalida. However, such catalysts do not exhibit an activity which is suEEiciently high for the production of polyethylene on a commercial scale.
Catalysts which are much more highly active in the polymerization Gf ethylene to polyethylene and in which the titanium compound is supported on a magnesium dihalide, especially MgC12, in an activated state characterized by a very large surface area and/or by a modified X-rays powder spectrum which does not show the most in~ense diffraction lines as they appear in the spectrum of the normal, non-activated Mg dihalide, are now known.
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: Exceptionallyhigh yields of polyethylene in g~s/gm of Ti used are obtained when ethylene is polymerized in contact with said catalysts one component of which is prepared by supporting the Ti compound on a support comprising the activated Mg dihalide.
- ~ 5 However, the polymer thus obtainPd exhibits a dispersed granulometry. That is to say the polymer particles are not of uniform or substantially uniform size.
THE PRESENT INVENTION
An object of this invention was to provide a process for polymeri~ing ethylene in contact with a catalyst one component of which comprises a Ti compound supported on a Mg dihalide in the active state but which, in addition to result-ing in high yields of polyethylene in gmsfgm of Ti used, also results in a particulate polyethylene having a controlled particle size.
That and other objects are achieved by the present invention in accordance with which ethylene, or a mixture thereof with alpha-olefins of the formula CH2 -- CRR in which R
is an alkyl radical containing 1 to 6 carbon atomsr e.g., propylene or butene-l, is polymerized in contact with a catalyst one component of which is the reaction product of a solid halogenated Ti compound, a Grignard compolmd and a haloge~ating agent.
The solid halogenated Ti compound used to prepare the aforesaid catalyst component is a TiC13 obtained by the reduction o~ TiC14 by different techniques or a solid Ti-halogen-alcoholate such as, e.q., C13TiOC~3.
The Grignard compounds used in preparing said catalyst component are those of the formula RMgX, in which X is Cl or sr ,,.` '
It is known to polymerize ethylene to polyethylene with the aid of catalysts of various types, in particular with the aid of catalysts consisting of the products o~tained by mixing titanium compounds with organometalIic compounds of metals belonging to Groups I to III of the Mendelyeev Periodic Table r such as the products obtained by mixing TiC14 or TiC13 with an aluminum trialkyl or a dialkyl aluminum monohalida. However, such catalysts do not exhibit an activity which is suEEiciently high for the production of polyethylene on a commercial scale.
Catalysts which are much more highly active in the polymerization Gf ethylene to polyethylene and in which the titanium compound is supported on a magnesium dihalide, especially MgC12, in an activated state characterized by a very large surface area and/or by a modified X-rays powder spectrum which does not show the most in~ense diffraction lines as they appear in the spectrum of the normal, non-activated Mg dihalide, are now known.
.
.
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: Exceptionallyhigh yields of polyethylene in g~s/gm of Ti used are obtained when ethylene is polymerized in contact with said catalysts one component of which is prepared by supporting the Ti compound on a support comprising the activated Mg dihalide.
- ~ 5 However, the polymer thus obtainPd exhibits a dispersed granulometry. That is to say the polymer particles are not of uniform or substantially uniform size.
THE PRESENT INVENTION
An object of this invention was to provide a process for polymeri~ing ethylene in contact with a catalyst one component of which comprises a Ti compound supported on a Mg dihalide in the active state but which, in addition to result-ing in high yields of polyethylene in gmsfgm of Ti used, also results in a particulate polyethylene having a controlled particle size.
That and other objects are achieved by the present invention in accordance with which ethylene, or a mixture thereof with alpha-olefins of the formula CH2 -- CRR in which R
is an alkyl radical containing 1 to 6 carbon atomsr e.g., propylene or butene-l, is polymerized in contact with a catalyst one component of which is the reaction product of a solid halogenated Ti compound, a Grignard compolmd and a haloge~ating agent.
The solid halogenated Ti compound used to prepare the aforesaid catalyst component is a TiC13 obtained by the reduction o~ TiC14 by different techniques or a solid Ti-halogen-alcoholate such as, e.q., C13TiOC~3.
The Grignard compounds used in preparing said catalyst component are those of the formula RMgX, in which X is Cl or sr ,,.` '
-2-., . ' 11~ 1~
and R is an alkyl, a cycloalkyl, or an aryl radical containing from 2 to 16 carbon atoms.
The halogenating agents used to prepare the catalyst component are those which react with the Griynard compound, decomposing it to Mg halide. Examples of such halogenating agents include TiC14, SiC14 and PC13.
The useful TiC13 can be obtained by reducing TiC14 with Al-alkyls, such as, for example, A12Et3C13 or AlEt2Cl (B-TiC13), or by reduction of TiC14 with Al metal. In the latter case, the TiC13 is successively activated by dry-grinding.
The TiC13 obtained by reduction of TiC14 with Al-alkyls can be used, also, in an activated state attainable by heat treatment.
Furthermore, the TiC13 used may be obtained by reduc-tion of TiC14 with hydrogen, followed by activation thereof by grinding.
In a presently preferred embodiment of the invention, the Grignard compounds used are the Mg-alkyl chlorides in which the alkyl contain~ from 2 to 12 carbon atoms. Good results have also been obtained using the Mg-alkyl bromides in which the alkyl contains from 4 to 8 carbon atoms.
Also, in the presently preferred embodiment, the halogenating agent used is TiCl~ or SiC14. PCI3 gives a polymer having a narrow particle-si~e distribution but the particles are very small (mean diameter - 155~), which is of par~icular advantage in some uses to which the polymer is put in practice.
The new catalyst components of the invention are pre-pared by reacting the solid halogenated Ti compound with the Grignard compound in an aliphatic hydrocarbon, such as n-he~ane or n-heptane, at a temperature between 35 and 40~C, according to a molar ratio Grignard compound/Ti-compound of at least 7.
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In practice, for reasons of economy, it is not advisable to employ ratios higher than 12. Such ~eaction generally takes 2 to 4 hours.
The reaction product, separated by filtration, is raacted with the halogenating agent at a temperature ranging from 0 to 150C, preferably at 100-110C, according to a halogenating agent/Grignard compound molar ratio higher than 0.5 and in particular comprised between 0.5 and 5. In practice, the preferred ratio is equal to 2 or a little higher, e.g., up to 2.5. The reaction can be conducted in the presence of an inert hydrocarbon, such as n-hexane or n-heptane.
The catalytic components prepared as described are use~ in combination with organometallic compounds of metals belonging to Groups I to II~ of the lMendelyeev] Periodic Table, preferably an Al-trialkyl, such as A1-triethyl or Al-triisobutyl, according to an Al/Ti ratio higher than 1 and generally com-prised between 1 and 1000, in particular between 5 and 200.
The particle size distribution of the polymer is measured by the set of AST~-E 11 screens according to method ASTM D 1921-63.
The analytical results are determined in conformity ~ith a calculus program by a computer that provides the parameters of the particle size distribution and the distribution diagram.
The mean diameter of the polymer particles is calcu-lated by the Reboux formula:
mean diameter = ~1/0 ) in which 0i indicates the geometrical mean diameter of the per-centage. by weight xi of polymer retained between two consecu~ive screens.
The dispersion, which defines the width of the particle-size distribution, is given by the formula:
p - p dispersion = 84 16 in which P84 and P16 represent the so-called "percentile diameters", which can be calculated on the basis of the cumula-tive curve of the particle-size distribution.
Such curve is drawn by plotting on the abscissa the diameter x of the particles and on the ordinate the percentage y of polymer having x as maximum diameter of its particles, i.e., the percentage of polymer in particles having a diameter ~x.
Using the distribution cumulative curve it is possible to find, on the abscissa, the "percentile diameter" Py corres-ponding to a given percentage y of polymer: so, in correspon-dence of 16~ and of 8q% of the polymer it is possible to find, on the abscissa, the values of P16 and P84 expressed, for example, in micron.
Satisfactory particle-size distributions are those corresponding to dispersion values not higher than ~.2.
The polymerization of ethylene and of mixtures thereof with lesser amounts of alpha-olefins in the presence of the above-described catalysts is conducted according to known methods, at a temperature ranging from 0 to 150C, preferably from 50 to ~0C, by operating in a liquid phase either in the presence or in the absence of an aliphatic hydrocarbon, such as n-hexane or n-heptane, or in the gas phase. The Al-organic compound is employed in an amount corresponding to 2 g/liter of the reaction medium.
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l ~ l In the following examples, given to illustrate the invention, and not intended as limiting, ~he polymerization of ethylene was carried out at 85C in n-hexane, at an ethylene and hydrogen pressure of 6 and 7 atm~ gauge respectively.
(a) Preparation of the catalyst component of the invention.
N-octyl-magnesium chloride (n-C8H17MgCl) was prepared by introducing into a 2-liter flask equipped with a stirrer, 500 ml of anhydrous diethyl ether and 22.3 g of magnesium in powder form and activated with Li-butyl.
The mixture was heated at re~lux and 20 ml of a solution obtained from 153 ml of n-octyl chloride and from S0 ml of anhydrous diethyl ether were quickly added dropwise. The remaining portion of such solution was added in 2 hours and 30 minutes, and the whole was allowed to stand at reflux fox 12 hours. Successively, the unreacted magnesium was removed by filtration on a fritted bottom G 3, thus obtaining a limpid solution of the Grignard compound in ether, from which the ether was removed by substitutive distillation with anhydrous n-hexane, until a temperature of 67-68C was reached at the top of the column.
At the conclusion of the operation, 1000 ml of a sus-pension containing 0.85 moles of n C8H17MgCl were obtained, the yield being about 95% calculated on the octyl chloride employed.
The residual ether in the suspension was egual to about 2% by weight.
TiC13 type TR was prepared by reducing TiC14 with A12Et3C13 at 10C in n-heptane, with an Al/Ti atomic ratio equal to 1.26, and operating as ~ollows: a solutio~ of 45% by weight I
-of TiC14 in n-heptane was gradually added, in 90 minutes and _ undcr stirring, to the amount of A12Et3C13 necessary to arrive at an Al/Ti ratio equal to 1.26. The whole was kept under o stirring for 3 hours at 10C and then was allowed to stand for 8-10 hours. After 2 washings with n-heptane the product was .
thermally activated for 2 hours at 130DC, to obtain a violet - ~r compound consisting of TiC13.nAlC13 of type ~ and havin~ the following composition: total Ti-= 20.40%, Ti3 = 20.4%;
Al = 5.55~: Cl = 68.75~. ,-~
2.65 g of the TiC13TR ~11.3 m/moles) and 100 ml of a suspension of n-C8H17MgCl (85 m/moles) were introduced into a 250 ml flask equipped with a stirrer. The mass was heated to 35~C and kept at such temperature for 4 hours. After filtra-tion, 5 washings with anhydrous n-heptane were carried out, i;
whereupon the product was dried under vacuum. A solution of 30 ml of TiC14 in 30 ml of n-heptane was then added, and the whole ¦
was heated to 65C and kept under stirring for 2 hours. After filtration, 5 washings with n-heptane were effected and, l finally, the product was dried under vacuum.
¦ A violet powder having the following composition was thus obtained: total Ti = 10%; Ti3 = 7.05%; Mg = 12.3~;
¦ Al = 0.8~; Cl = 68.2~. Surface area = 31.7 m2/g.
¦ (b) Polymerization of ethylene.
The polymerization was conducted in a stainless steel autoclave having a capacity of 1.8 1, equipped with a stirring device and with a thermoregulating circuit. After degassing with hot W2, the following materials were introduced:
- 750 ml of anhydrous n-hexane free from aromatic compounds;
1.6 g of Al-triisobutyl;
- 0.015 g of the catalyst component described in (a).
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l rhe temperature was rapidly brought to 85C, H2 was ¦ introduced up to a pressure of 7 kg~cm gauge followed by the introduction of ethylene up to a pressure of 13 kg/cm2 gauge.
The polymerization was carried out for 4 hours, keeping the S ¦ pressure constant by introducing ethylene~ Polymerization was stopped, the polymer was separated by filtration, and dried at 70C in a nitrogen flow. 200 g of polyethylene were thus obtained, containing 4 ppm of residual titanium and having a l melt index of 9.9 g/10 min. The mean diameter of the polymer ¦ particles was 0.343 mm and the dispersion was 0.12.
_XAMPLE 2 ¦ (a) Preparation of a catalyst component according to the invention.
l Example l(a) was repeated but, using, instead of l TiC13TR, a ~-TiC13 prepared as follows: a solution of TiC14 in n-hexane was added, in 4 hours and under stirring, to an amount of AlEt2C1 such as to attain an Al/Ti atomic ratio = 1, taking care to keep the temperature at 0C. Once the introduc-l tion of AlEt2Cl was concluded, the mixture was kept at 0~C for ¦ a further 30 minutes, then brought to 65C for 1 hour, and allowed to stand overnight. The reaction mass was filtered and l the solid reaction product was washed five times with n-hexane, ¦ whereupon the product was dried under vacuum at 50C.
¦ On analysis, the brown powder obtained had the follow-l ing composition: total Ti = 21.85%; Ti = 21.80%; Al = 4.25%;
Cl ~ 66%. On X-ray analysis the product was shown to be a ¦ ~-TiC13.nA1~13.
l After reaction with n-C~H17MgCl and TiClg as in Example ¦ l(a), a powder having the following composition was obtained:
¦ ~ ~ L~al41LiL'7 total Ti - 10.3%; Ti = 7.75%; Mg = 13.9%; Al = 0.2~;
Cl = 63.05%.
(b) Polymerization of ethylen_ The polymerization was carried out as in ~xample l(b), using 0.020 g of the catalytic component, (a). 198 g of polymer containing 9 ppm of residual Ti were obtained.
The melt index was 15.6 g/10 min.
Mean diameter = 0.420 mm.
Dispersion = 0.123.
(a) Preparation of a catalytic component of the invention The TiC13 used was prepared by reduction of TiClq with metal Al at 150-160C and thereafter acti~ated by dry-grinding in a ball mill~ to obtain a ~-TiC13Ø33 AlC13 having the fol-lS lowing composition: total Ti = 23.75%; Ti = 23.45%;
Al = 4.60%; Cl = 70.35%. After reaction with n-C8H17MgC1 and TiC14 as in Example l(a), a product having the following composition was obtained: total Ti = 6.6%; Ti3 = 6.6~;
Mg = 14.85%; Al = 0.9%; C1 = 65.05%.
(b) Polymerization o~ eth ~
By operating as in Example l(b), and using 0.016 g of catalytic component (a) there were obtained 175 g of polymer having a residual Ti content of 5 ppm, a melt index of 8.6 g/10 min., a mean diameter of 0.342 mm and a dispersion o~ 0.133.
By employing 0.037 g of TiC13 prepared as above, 188 g oi polymer ha~lng the llowing ch~rtcteristics were obtainedl _g_ i j ~l~4~4 residual Ti = 39 ppm melt index - 0.49 gJ10 min.
mean diameter = 0.397 mm dispersion = 0.484.
An ~-TiC13 of type XR, obtained by reduction of TiC14 with H2 under conventional conditions, was used. The catalyst component obtained after reaction of the ~-TiC13 with n-C8H17MgCl and TiC14, as in the preceding examples, exhibited the following composition: total Ti = 10.15~; Mg = 13.0%;
Ti3~ = 9.4%; Cl = 68.75~.
The polymerization of e~hylene in contact with a catalyst as in Example l~b) and using 0.015 g of the catalytic l component described in the foregoing paragraph yielded 126 g of 5 ¦ polymer containing 7 ppm of residual Ti, and having a melt index of 11.3 g/10 min., a mean diameter of 0.321 mm, and a dispersion of 0.140.
The polymer obtained by using ~-TiC13 (202 g from l 0.037 g of catalytic component) contained 90 ppm of Ti, had a 1 melt index of 0.54, a mean diameter of 0.841 mm and a dispersion o~ 0.946.
EXAMæLE 5 (a) Preparation of a_ catalyst component of the invention The compound n-C12H25MgCl was prepare~ from ~g and n-C12H25Cl by operating according to the modalities described in E~ample l(a) fox the compound n-C8X17MgCl.
A suspension of the Grignard compound in n-hexane, wi~h a yield of 92.5~ and a ~esidual content of ether equal to 0.8~, . I
s~4~
¦ was obtain~d. It was reacted with TiC13TR in the same molar ¦ ratio as in Examplc l~a). After reaction with TiC14 a product ¦ exhibiting the following composition was obtai~ed:
¦ total Ti = 9.7%; Ti = 7.3%; Mg = 13.95%; Al = 0.45~;
Cl = 63.75%.
(b) Polymeriæation of ethylene Ethylene was polymerized under the same conditions as specified in th2 previous examples, ~sing 0.023 g of the catalyst component (a). 231 g of polyethylene containing 8 ppm of residual Ti were obtained. The melt index was 4 . 45 g/10 min., the mean diameter 0.389 mm, the dispersion 0.117.
ta) Preparation of a catalyst component of the invention The compound n-C4HgMgCl, obtained by the method described in Example l(a) and with a yield of 87% and a residual ether content equal to 2.65%, was used. After reaction thereof with TiC13TR and then with TiC14, a product exhibiting the following composition was obtained: total Ti = 11.2~;
Ti3 = 7.75%; Mg = 11.5%, Al = 1.1% Cl = 66.1~.
~b) Polymerization of ethylene By polymeriæing ethylene as in the previous examples, and using a catalyst prepared from 0.024 g of catalytic com-ponent ta) and the organometallic compound, there were obtained 215 g of polymer having the following characteristics:
residual Ti = 7 ppm melt index = 7.3 g/10 min.
mean diameter = 0.3~30 mm d ersion = 0.110.
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EXA~PLE 7 (a) Preparation of a catalytic component of the invention In this example, TiC13TR was reacted with n-C4HgMgBr prepared according to the usual modalities (yield = 71%, residual ether = 3.8%), and then with TiC14 as in Example l~a).
The resulting.catalyst component had the following composition: total Ti = 12.15~; Ti3 = 7.05~; Mg = 10.15%;
Al = 0.35%; (Cl ~ Br~ = 57.60% (thoroughly expressed as Cl).
(b) Polymerization of ethylene Following the modalities of previous examples and employing 0.0195 g.of catalytic component (a) in admixture with the organometallic compound of Example l(b), there were obtained 230 g of polyethylene which had the following characteristics:
residual Ti = 7 ppm melt index = 6.35 g/10 min.
mean diameter = 0.353 mm dispersion = 0.119.
~a) Preparation of a catalyst component of the invention Example l(a) was repeated, employing TiC13 TR and n-C8H17MgCl, with the exception that, as halogenating agent, SiC14 was utilized instead of TiC14. A product having the following composition was obtained: total Ti = 2.1%;
Ti = 1. 25%; Mg - 7.95%; Al = 0.25Q; Cl = 27.1%;
Si: not determined.
tb) Polymerization of_ thylene By using 0.030 g of the aforesaid catalyst component (a) and operating as in Example l(b), there were obtained 297 g ~ 7 of a polyethylene having a residual Ti < 4 ppm, a melt index =
19.2 g~l0 min., a mean diameter = 0.347 mm, and a dispersion =
0.122.
¦ ~a) Preparation of a catalyst component of the invention Example l(a) was repeated but using PC13 as the halo-genating agent instead of TiC14. The resulting product had the following composition: total Ti = 2.4~; Ti = 0.95~;
Mg = 13.95~; Al = 0.25%; Cl = 64;35% P = 6.3%.
tb) Polymerization of ethylene By operating as in Example l(b) and employing 0.36 g ¦ of the catalyst component, (a) described in this example, there were obtained 224 g of polyethylene having a residual Ti content < 4 ppm. The melt index was 24 g~l0 min., the mean diameter 0.155 mm and the dispersion 0.123.
EXAMPLE 10 (comparative test) (a) Preparation of a catal~st component without using a solid halogenated titanium compound __ Only 50 ml of a suspension of n-C8H17MgCl in n-hexane tequal to 44 m/moles) and 15 ml of TiC14 (136 m/~oles) were reacted at 65C for 2 hours under stirring. The mass was filtered, and the reaction product washed 5 times with n-heptane, then dried under vacuum. The resulting powder had the following composition: total Ti = 13%; Ti = 5.6%; Mg = 12.55~;
Cl = 62.15%.
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, -- l~ 4~17 ¦ ~b) Polymerization of ethylene ¦ By operating as in Example l(b) and employing 0.02S g ¦ of the abo~e catalyst component, 163 g of polymer were obtained.
¦ The residual Ti was 22 ppm, the melt index 9.0 g/10 min., the ¦ mean diameter 0.524 mm and the dispersion 0.530.
This comparative test establishes that a catalyst as in Example l(b) but prepared from a component obtained by simple reaction between the Mg compound and TiC14 does not yield, l when mi~ed with the organometallic compound, a catalyst capable ¦ of polymerizing ethylene to polyethylene having a narrow partlcle- ~e distribut1on.
.~. . , . - ........... , ,.,_.................. .
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and R is an alkyl, a cycloalkyl, or an aryl radical containing from 2 to 16 carbon atoms.
The halogenating agents used to prepare the catalyst component are those which react with the Griynard compound, decomposing it to Mg halide. Examples of such halogenating agents include TiC14, SiC14 and PC13.
The useful TiC13 can be obtained by reducing TiC14 with Al-alkyls, such as, for example, A12Et3C13 or AlEt2Cl (B-TiC13), or by reduction of TiC14 with Al metal. In the latter case, the TiC13 is successively activated by dry-grinding.
The TiC13 obtained by reduction of TiC14 with Al-alkyls can be used, also, in an activated state attainable by heat treatment.
Furthermore, the TiC13 used may be obtained by reduc-tion of TiC14 with hydrogen, followed by activation thereof by grinding.
In a presently preferred embodiment of the invention, the Grignard compounds used are the Mg-alkyl chlorides in which the alkyl contain~ from 2 to 12 carbon atoms. Good results have also been obtained using the Mg-alkyl bromides in which the alkyl contains from 4 to 8 carbon atoms.
Also, in the presently preferred embodiment, the halogenating agent used is TiCl~ or SiC14. PCI3 gives a polymer having a narrow particle-si~e distribution but the particles are very small (mean diameter - 155~), which is of par~icular advantage in some uses to which the polymer is put in practice.
The new catalyst components of the invention are pre-pared by reacting the solid halogenated Ti compound with the Grignard compound in an aliphatic hydrocarbon, such as n-he~ane or n-heptane, at a temperature between 35 and 40~C, according to a molar ratio Grignard compound/Ti-compound of at least 7.
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In practice, for reasons of economy, it is not advisable to employ ratios higher than 12. Such ~eaction generally takes 2 to 4 hours.
The reaction product, separated by filtration, is raacted with the halogenating agent at a temperature ranging from 0 to 150C, preferably at 100-110C, according to a halogenating agent/Grignard compound molar ratio higher than 0.5 and in particular comprised between 0.5 and 5. In practice, the preferred ratio is equal to 2 or a little higher, e.g., up to 2.5. The reaction can be conducted in the presence of an inert hydrocarbon, such as n-hexane or n-heptane.
The catalytic components prepared as described are use~ in combination with organometallic compounds of metals belonging to Groups I to II~ of the lMendelyeev] Periodic Table, preferably an Al-trialkyl, such as A1-triethyl or Al-triisobutyl, according to an Al/Ti ratio higher than 1 and generally com-prised between 1 and 1000, in particular between 5 and 200.
The particle size distribution of the polymer is measured by the set of AST~-E 11 screens according to method ASTM D 1921-63.
The analytical results are determined in conformity ~ith a calculus program by a computer that provides the parameters of the particle size distribution and the distribution diagram.
The mean diameter of the polymer particles is calcu-lated by the Reboux formula:
mean diameter = ~1/0 ) in which 0i indicates the geometrical mean diameter of the per-centage. by weight xi of polymer retained between two consecu~ive screens.
The dispersion, which defines the width of the particle-size distribution, is given by the formula:
p - p dispersion = 84 16 in which P84 and P16 represent the so-called "percentile diameters", which can be calculated on the basis of the cumula-tive curve of the particle-size distribution.
Such curve is drawn by plotting on the abscissa the diameter x of the particles and on the ordinate the percentage y of polymer having x as maximum diameter of its particles, i.e., the percentage of polymer in particles having a diameter ~x.
Using the distribution cumulative curve it is possible to find, on the abscissa, the "percentile diameter" Py corres-ponding to a given percentage y of polymer: so, in correspon-dence of 16~ and of 8q% of the polymer it is possible to find, on the abscissa, the values of P16 and P84 expressed, for example, in micron.
Satisfactory particle-size distributions are those corresponding to dispersion values not higher than ~.2.
The polymerization of ethylene and of mixtures thereof with lesser amounts of alpha-olefins in the presence of the above-described catalysts is conducted according to known methods, at a temperature ranging from 0 to 150C, preferably from 50 to ~0C, by operating in a liquid phase either in the presence or in the absence of an aliphatic hydrocarbon, such as n-hexane or n-heptane, or in the gas phase. The Al-organic compound is employed in an amount corresponding to 2 g/liter of the reaction medium.
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l ~ l In the following examples, given to illustrate the invention, and not intended as limiting, ~he polymerization of ethylene was carried out at 85C in n-hexane, at an ethylene and hydrogen pressure of 6 and 7 atm~ gauge respectively.
(a) Preparation of the catalyst component of the invention.
N-octyl-magnesium chloride (n-C8H17MgCl) was prepared by introducing into a 2-liter flask equipped with a stirrer, 500 ml of anhydrous diethyl ether and 22.3 g of magnesium in powder form and activated with Li-butyl.
The mixture was heated at re~lux and 20 ml of a solution obtained from 153 ml of n-octyl chloride and from S0 ml of anhydrous diethyl ether were quickly added dropwise. The remaining portion of such solution was added in 2 hours and 30 minutes, and the whole was allowed to stand at reflux fox 12 hours. Successively, the unreacted magnesium was removed by filtration on a fritted bottom G 3, thus obtaining a limpid solution of the Grignard compound in ether, from which the ether was removed by substitutive distillation with anhydrous n-hexane, until a temperature of 67-68C was reached at the top of the column.
At the conclusion of the operation, 1000 ml of a sus-pension containing 0.85 moles of n C8H17MgCl were obtained, the yield being about 95% calculated on the octyl chloride employed.
The residual ether in the suspension was egual to about 2% by weight.
TiC13 type TR was prepared by reducing TiC14 with A12Et3C13 at 10C in n-heptane, with an Al/Ti atomic ratio equal to 1.26, and operating as ~ollows: a solutio~ of 45% by weight I
-of TiC14 in n-heptane was gradually added, in 90 minutes and _ undcr stirring, to the amount of A12Et3C13 necessary to arrive at an Al/Ti ratio equal to 1.26. The whole was kept under o stirring for 3 hours at 10C and then was allowed to stand for 8-10 hours. After 2 washings with n-heptane the product was .
thermally activated for 2 hours at 130DC, to obtain a violet - ~r compound consisting of TiC13.nAlC13 of type ~ and havin~ the following composition: total Ti-= 20.40%, Ti3 = 20.4%;
Al = 5.55~: Cl = 68.75~. ,-~
2.65 g of the TiC13TR ~11.3 m/moles) and 100 ml of a suspension of n-C8H17MgCl (85 m/moles) were introduced into a 250 ml flask equipped with a stirrer. The mass was heated to 35~C and kept at such temperature for 4 hours. After filtra-tion, 5 washings with anhydrous n-heptane were carried out, i;
whereupon the product was dried under vacuum. A solution of 30 ml of TiC14 in 30 ml of n-heptane was then added, and the whole ¦
was heated to 65C and kept under stirring for 2 hours. After filtration, 5 washings with n-heptane were effected and, l finally, the product was dried under vacuum.
¦ A violet powder having the following composition was thus obtained: total Ti = 10%; Ti3 = 7.05%; Mg = 12.3~;
¦ Al = 0.8~; Cl = 68.2~. Surface area = 31.7 m2/g.
¦ (b) Polymerization of ethylene.
The polymerization was conducted in a stainless steel autoclave having a capacity of 1.8 1, equipped with a stirring device and with a thermoregulating circuit. After degassing with hot W2, the following materials were introduced:
- 750 ml of anhydrous n-hexane free from aromatic compounds;
1.6 g of Al-triisobutyl;
- 0.015 g of the catalyst component described in (a).
, , ~ ~.
o7 ~ j, . .
.
. ~ ~4~
l rhe temperature was rapidly brought to 85C, H2 was ¦ introduced up to a pressure of 7 kg~cm gauge followed by the introduction of ethylene up to a pressure of 13 kg/cm2 gauge.
The polymerization was carried out for 4 hours, keeping the S ¦ pressure constant by introducing ethylene~ Polymerization was stopped, the polymer was separated by filtration, and dried at 70C in a nitrogen flow. 200 g of polyethylene were thus obtained, containing 4 ppm of residual titanium and having a l melt index of 9.9 g/10 min. The mean diameter of the polymer ¦ particles was 0.343 mm and the dispersion was 0.12.
_XAMPLE 2 ¦ (a) Preparation of a catalyst component according to the invention.
l Example l(a) was repeated but, using, instead of l TiC13TR, a ~-TiC13 prepared as follows: a solution of TiC14 in n-hexane was added, in 4 hours and under stirring, to an amount of AlEt2C1 such as to attain an Al/Ti atomic ratio = 1, taking care to keep the temperature at 0C. Once the introduc-l tion of AlEt2Cl was concluded, the mixture was kept at 0~C for ¦ a further 30 minutes, then brought to 65C for 1 hour, and allowed to stand overnight. The reaction mass was filtered and l the solid reaction product was washed five times with n-hexane, ¦ whereupon the product was dried under vacuum at 50C.
¦ On analysis, the brown powder obtained had the follow-l ing composition: total Ti = 21.85%; Ti = 21.80%; Al = 4.25%;
Cl ~ 66%. On X-ray analysis the product was shown to be a ¦ ~-TiC13.nA1~13.
l After reaction with n-C~H17MgCl and TiClg as in Example ¦ l(a), a powder having the following composition was obtained:
¦ ~ ~ L~al41LiL'7 total Ti - 10.3%; Ti = 7.75%; Mg = 13.9%; Al = 0.2~;
Cl = 63.05%.
(b) Polymerization of ethylen_ The polymerization was carried out as in ~xample l(b), using 0.020 g of the catalytic component, (a). 198 g of polymer containing 9 ppm of residual Ti were obtained.
The melt index was 15.6 g/10 min.
Mean diameter = 0.420 mm.
Dispersion = 0.123.
(a) Preparation of a catalytic component of the invention The TiC13 used was prepared by reduction of TiClq with metal Al at 150-160C and thereafter acti~ated by dry-grinding in a ball mill~ to obtain a ~-TiC13Ø33 AlC13 having the fol-lS lowing composition: total Ti = 23.75%; Ti = 23.45%;
Al = 4.60%; Cl = 70.35%. After reaction with n-C8H17MgC1 and TiC14 as in Example l(a), a product having the following composition was obtained: total Ti = 6.6%; Ti3 = 6.6~;
Mg = 14.85%; Al = 0.9%; C1 = 65.05%.
(b) Polymerization o~ eth ~
By operating as in Example l(b), and using 0.016 g of catalytic component (a) there were obtained 175 g of polymer having a residual Ti content of 5 ppm, a melt index of 8.6 g/10 min., a mean diameter of 0.342 mm and a dispersion o~ 0.133.
By employing 0.037 g of TiC13 prepared as above, 188 g oi polymer ha~lng the llowing ch~rtcteristics were obtainedl _g_ i j ~l~4~4 residual Ti = 39 ppm melt index - 0.49 gJ10 min.
mean diameter = 0.397 mm dispersion = 0.484.
An ~-TiC13 of type XR, obtained by reduction of TiC14 with H2 under conventional conditions, was used. The catalyst component obtained after reaction of the ~-TiC13 with n-C8H17MgCl and TiC14, as in the preceding examples, exhibited the following composition: total Ti = 10.15~; Mg = 13.0%;
Ti3~ = 9.4%; Cl = 68.75~.
The polymerization of e~hylene in contact with a catalyst as in Example l~b) and using 0.015 g of the catalytic l component described in the foregoing paragraph yielded 126 g of 5 ¦ polymer containing 7 ppm of residual Ti, and having a melt index of 11.3 g/10 min., a mean diameter of 0.321 mm, and a dispersion of 0.140.
The polymer obtained by using ~-TiC13 (202 g from l 0.037 g of catalytic component) contained 90 ppm of Ti, had a 1 melt index of 0.54, a mean diameter of 0.841 mm and a dispersion o~ 0.946.
EXAMæLE 5 (a) Preparation of a_ catalyst component of the invention The compound n-C12H25MgCl was prepare~ from ~g and n-C12H25Cl by operating according to the modalities described in E~ample l(a) fox the compound n-C8X17MgCl.
A suspension of the Grignard compound in n-hexane, wi~h a yield of 92.5~ and a ~esidual content of ether equal to 0.8~, . I
s~4~
¦ was obtain~d. It was reacted with TiC13TR in the same molar ¦ ratio as in Examplc l~a). After reaction with TiC14 a product ¦ exhibiting the following composition was obtai~ed:
¦ total Ti = 9.7%; Ti = 7.3%; Mg = 13.95%; Al = 0.45~;
Cl = 63.75%.
(b) Polymeriæation of ethylene Ethylene was polymerized under the same conditions as specified in th2 previous examples, ~sing 0.023 g of the catalyst component (a). 231 g of polyethylene containing 8 ppm of residual Ti were obtained. The melt index was 4 . 45 g/10 min., the mean diameter 0.389 mm, the dispersion 0.117.
ta) Preparation of a catalyst component of the invention The compound n-C4HgMgCl, obtained by the method described in Example l(a) and with a yield of 87% and a residual ether content equal to 2.65%, was used. After reaction thereof with TiC13TR and then with TiC14, a product exhibiting the following composition was obtained: total Ti = 11.2~;
Ti3 = 7.75%; Mg = 11.5%, Al = 1.1% Cl = 66.1~.
~b) Polymerization of ethylene By polymeriæing ethylene as in the previous examples, and using a catalyst prepared from 0.024 g of catalytic com-ponent ta) and the organometallic compound, there were obtained 215 g of polymer having the following characteristics:
residual Ti = 7 ppm melt index = 7.3 g/10 min.
mean diameter = 0.3~30 mm d ersion = 0.110.
,,'' . .
, 41:1'i' ~
EXA~PLE 7 (a) Preparation of a catalytic component of the invention In this example, TiC13TR was reacted with n-C4HgMgBr prepared according to the usual modalities (yield = 71%, residual ether = 3.8%), and then with TiC14 as in Example l~a).
The resulting.catalyst component had the following composition: total Ti = 12.15~; Ti3 = 7.05~; Mg = 10.15%;
Al = 0.35%; (Cl ~ Br~ = 57.60% (thoroughly expressed as Cl).
(b) Polymerization of ethylene Following the modalities of previous examples and employing 0.0195 g.of catalytic component (a) in admixture with the organometallic compound of Example l(b), there were obtained 230 g of polyethylene which had the following characteristics:
residual Ti = 7 ppm melt index = 6.35 g/10 min.
mean diameter = 0.353 mm dispersion = 0.119.
~a) Preparation of a catalyst component of the invention Example l(a) was repeated, employing TiC13 TR and n-C8H17MgCl, with the exception that, as halogenating agent, SiC14 was utilized instead of TiC14. A product having the following composition was obtained: total Ti = 2.1%;
Ti = 1. 25%; Mg - 7.95%; Al = 0.25Q; Cl = 27.1%;
Si: not determined.
tb) Polymerization of_ thylene By using 0.030 g of the aforesaid catalyst component (a) and operating as in Example l(b), there were obtained 297 g ~ 7 of a polyethylene having a residual Ti < 4 ppm, a melt index =
19.2 g~l0 min., a mean diameter = 0.347 mm, and a dispersion =
0.122.
¦ ~a) Preparation of a catalyst component of the invention Example l(a) was repeated but using PC13 as the halo-genating agent instead of TiC14. The resulting product had the following composition: total Ti = 2.4~; Ti = 0.95~;
Mg = 13.95~; Al = 0.25%; Cl = 64;35% P = 6.3%.
tb) Polymerization of ethylene By operating as in Example l(b) and employing 0.36 g ¦ of the catalyst component, (a) described in this example, there were obtained 224 g of polyethylene having a residual Ti content < 4 ppm. The melt index was 24 g~l0 min., the mean diameter 0.155 mm and the dispersion 0.123.
EXAMPLE 10 (comparative test) (a) Preparation of a catal~st component without using a solid halogenated titanium compound __ Only 50 ml of a suspension of n-C8H17MgCl in n-hexane tequal to 44 m/moles) and 15 ml of TiC14 (136 m/~oles) were reacted at 65C for 2 hours under stirring. The mass was filtered, and the reaction product washed 5 times with n-heptane, then dried under vacuum. The resulting powder had the following composition: total Ti = 13%; Ti = 5.6%; Mg = 12.55~;
Cl = 62.15%.
.
- -13- . I
, -- l~ 4~17 ¦ ~b) Polymerization of ethylene ¦ By operating as in Example l(b) and employing 0.02S g ¦ of the abo~e catalyst component, 163 g of polymer were obtained.
¦ The residual Ti was 22 ppm, the melt index 9.0 g/10 min., the ¦ mean diameter 0.524 mm and the dispersion 0.530.
This comparative test establishes that a catalyst as in Example l(b) but prepared from a component obtained by simple reaction between the Mg compound and TiC14 does not yield, l when mi~ed with the organometallic compound, a catalyst capable ¦ of polymerizing ethylene to polyethylene having a narrow partlcle- ~e distribut1on.
.~. . , . - ........... , ,.,_.................. .
, , ., " . -I
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Components of catalysts for polymerizing ethylene or mixtures thereof with minor amounts of alpha-olefins of formula CH2=CHR, in which R is an alkyl radical containing from 1 to 6 carbon atoms, to polymers having a narrow particle-size distribution corresponding to a dispersion value not higher than 0.2, said components comprising the product obtained by reacting a titanium compound selected from the group consisting of TiCl3 and solid Ti-halogen-alcoholates with a Grignard compound having the formula R Mg X, in which R is an alkyl, cycloalkyl or aryl radical con-taining from 2 to 16 carbon atoms and X is Cl or Br, isolating the solid reaction product and reacting it with a halogenating agent capable or decomposing the Grignard compound to magnesium halide.
2. The process for preparing catalyst components according to claim 1, which process comprises reacting a titanium compound selected from the group consisting of TiCl3 and solid Ti-halogen-alcoholates with a Grignard compound of the formula RMgX, in which X is Cl or Br and R is an alkyl, a cycloalkyl or an aryl containing from 2 to 16 carbon atoms, in an aliphatic hydrocarbon, at a temperature comprised between 35° and 40°C and a Grignard com-pound/titanium compound molar ratio equal to at least 7, isolating the solid reaction product and reacting it with a halogenating agent at a temperature comprised between 0° to 150°C and a halo-genating agent/Grignard compound molar ratio higher than 0.5.
3. The process of claim 2, in which the halogenating agent/Grignard compound molar ratio is higher than 0.5 and up to 5Ø
4. The process of claim 2, in which the solid halo-genated titanium compound is TiCl3.
5. The process of claim 2, in which the Grignard compound is selected from the group consisting of n-C8H17MgCl, n-C12H25MgCl, n-C4H9MgCl and n-C4H9MgBr.
6. The process of claim 2, in which the halogenating agent is selected from the group consisting of TiCl4, SiCl4 and PCl3.
7: Catalysts for polymerizing ethylene or mixtures thereof with minor amounts of alpha-olefins having the formula CH2 = CHR in which R is an alkyl containing from 1 to 6 carbon atoms, said catalysts being obtained by mixing the catalyst components of claim 1 with organometallic compounds of metals belonging to Groups I to III of the Mendelyeev Periodic Table.
8. The catalysts of claim 7 in which the organometallic compound is an aluminum trialkyl.
9. The process for polymerizing ethylene or mixtures thereof with minor amounts of alpha-olefins of the formula CH2 = CHR in which is an alkyl containing from 1 to 6 carbon atoms, in which the polymerization is conducted in the presence of the catalysts of claim 7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT23903A/76 | 1976-06-03 | ||
| IT23903/76A IT1062072B (en) | 1976-06-03 | 1976-06-03 | CATALYSTS FOR THE POLYMERIZATION OF ETHYLENE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1104117A true CA1104117A (en) | 1981-06-30 |
Family
ID=11210762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA279,611A Expired CA1104117A (en) | 1976-06-03 | 1977-06-01 | Catalysts for polymerizing ethylene |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US4380507A (en) |
| JP (1) | JPS6234045B2 (en) |
| BE (1) | BE855312A (en) |
| CA (1) | CA1104117A (en) |
| DE (1) | DE2724974A1 (en) |
| ES (1) | ES459442A1 (en) |
| FR (1) | FR2353572A1 (en) |
| GB (1) | GB1550980A (en) |
| IT (1) | IT1062072B (en) |
| NL (1) | NL191120C (en) |
| SE (1) | SE435931B (en) |
| ZA (1) | ZA773321B (en) |
Families Citing this family (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1099805B (en) * | 1978-10-26 | 1985-09-28 | Montedison Spa | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINS |
| JPS5846202B2 (en) * | 1979-01-31 | 1983-10-14 | 住友化学工業株式会社 | Production method of olefin polymer |
| DE2929325A1 (en) * | 1979-07-19 | 1981-02-05 | Wacker Chemie Gmbh | METHOD FOR POLYMERIZING AT LEAST ONE ALPHA -OLEFIN |
| EP0026655A1 (en) * | 1979-10-01 | 1981-04-08 | Imperial Chemical Industries Plc | Titanium halide material and production thereof |
| JPS5718707A (en) * | 1980-07-09 | 1982-01-30 | Toa Nenryo Kogyo Kk | Catalyst component for polymerizing alpha-olefin and its using method |
| US4707530A (en) * | 1983-01-31 | 1987-11-17 | Exxon Research & Engineering Co. | Polymerization catalyst |
| JPS62193033U (en) * | 1986-05-29 | 1987-12-08 | ||
| US5231119A (en) * | 1990-04-27 | 1993-07-27 | Himont Incorporated | Crystalline olefin polymers and copolymers in the form of spherical particles at high porosity |
| EP0878484B1 (en) * | 1997-03-27 | 2004-12-15 | Council of Scientific and Industrial Research | A process for the preparation of a megnesium halide supported metallocene catalyst |
| KR100240519B1 (en) * | 1997-09-11 | 2000-01-15 | 유현식 | Chealate catalyst for polymerising olefin |
| KR100524293B1 (en) | 1999-05-27 | 2005-10-26 | 삼성토탈 주식회사 | A catalyst for ethylene homo- and co-polymerization |
| ATE276281T1 (en) | 1999-10-23 | 2004-10-15 | Samsung General Chemicals Co | IMPROVED CATALYST FOR OLEFIN HOMO- AND CO-POLYMERIZATION |
| KR100361224B1 (en) * | 1999-12-01 | 2002-11-29 | 삼성종합화학주식회사 | Method for preparing catalyst for ethylene homo- and co-polymerization |
| KR100359932B1 (en) | 2000-06-15 | 2002-11-07 | 삼성종합화학주식회사 | A catalyst for ethylene homo- and copolymerization |
| KR100387734B1 (en) * | 2000-06-17 | 2003-06-18 | 삼성종합화학주식회사 | Catalyst and process for polymerization of olefin |
| KR100389476B1 (en) * | 2000-11-09 | 2003-06-27 | 삼성종합화학주식회사 | A method for producing ethylene homo- and co-polymer |
| KR100389477B1 (en) * | 2000-11-09 | 2003-06-27 | 삼성종합화학주식회사 | A method for producing ethylene homo- and co-polymer |
| KR100389475B1 (en) * | 2000-11-09 | 2003-06-27 | 삼성종합화학주식회사 | Preparation method of catalyst for ethylene polymeration or copolymeration |
| KR100389962B1 (en) * | 2000-11-10 | 2003-07-02 | 삼성종합화학주식회사 | Preparation method of catalyst for ethylene polymeration or copolymeration |
| KR100421551B1 (en) * | 2000-12-16 | 2004-03-09 | 삼성아토피나주식회사 | Catalyst obtained by prepolymerization of polyolefin and olefin polymerization method using the same |
| EP1358223A4 (en) * | 2000-12-22 | 2005-01-05 | Samsung General Chemicals Co | Chelate catalyst for olefin polymerization and olefin polymerization method using the same |
| JP2004516379A (en) * | 2000-12-22 | 2004-06-03 | サムソン ジェネラル ケミカルズ カンパニー リミテッド | Polypropylene resin composition with improved surface hardness and scratch resistance |
| CN1220789C (en) * | 2000-12-22 | 2005-09-28 | 三星综合化学株式会社 | Flame retardant polypropylene resin composition |
| ATE305490T1 (en) * | 2000-12-22 | 2005-10-15 | Samsung General Chemicals Co | POLYOLEFIN RESIN COMPOSITION |
| KR100530794B1 (en) * | 2001-06-21 | 2005-11-23 | 삼성토탈 주식회사 | Catalyst for polymerization and copolymerization of ethylene |
| KR100496776B1 (en) * | 2001-06-21 | 2005-06-22 | 삼성토탈 주식회사 | Catalyst for polymerization and copolymerization of ethylene |
| KR100530795B1 (en) * | 2001-12-26 | 2005-11-23 | 삼성토탈 주식회사 | A method for ethylene homo- and copolymerization |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK133012C (en) * | 1968-11-21 | 1976-08-09 | Montedison Spa | CATALYST FOR POLYMERIZATION OF ALKENES |
| YU35844B (en) * | 1968-11-25 | 1981-08-31 | Montedison Spa | Process for obtaining catalysts for the polymerization of olefines |
| JPS4911269B1 (en) * | 1970-06-06 | 1974-03-15 | ||
| NL165757C (en) * | 1971-04-20 | 1983-11-16 | Montedison Spa | METHOD FOR PREPARING A CATALYST ON THE BASIS OF A GRIGNARD COMPOUND AND METHOD FOR POLYMERIZING THEREFOR. |
| DE2124591C3 (en) * | 1971-05-18 | 1980-06-19 | Basf Ag, 6700 Ludwigshafen | Process for the manufacture of polyethylene |
| DE2126249A1 (en) * | 1971-05-26 | 1972-12-07 | Wacker Chemie Gmbh | Process for the production of high density, high vibrating weight polyethylene in powder form |
| US4022958A (en) * | 1973-03-26 | 1977-05-10 | Nippon Oil Company Ltd. | Process for preparing polyolefins |
| DE2331103C2 (en) * | 1973-06-19 | 1983-12-08 | Basf Ag, 6700 Ludwigshafen | Process for the production of small homo- or copolymers of ethylene |
-
1976
- 1976-06-03 IT IT23903/76A patent/IT1062072B/en active
-
1977
- 1977-05-27 GB GB22412/77A patent/GB1550980A/en not_active Expired
- 1977-05-31 NL NL7705957A patent/NL191120C/en not_active IP Right Cessation
- 1977-05-31 SE SE7706339A patent/SE435931B/en not_active IP Right Cessation
- 1977-06-01 CA CA279,611A patent/CA1104117A/en not_active Expired
- 1977-06-01 FR FR7716754A patent/FR2353572A1/en active Granted
- 1977-06-02 BE BE178127A patent/BE855312A/en not_active IP Right Cessation
- 1977-06-02 ZA ZA00773321A patent/ZA773321B/en unknown
- 1977-06-02 ES ES459442A patent/ES459442A1/en not_active Expired
- 1977-06-02 DE DE19772724974 patent/DE2724974A1/en active Granted
- 1977-06-03 JP JP52064946A patent/JPS6234045B2/ja not_active Expired
-
1981
- 1981-11-24 US US06/324,419 patent/US4380507A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE2724974C2 (en) | 1992-04-23 |
| JPS6234045B2 (en) | 1987-07-24 |
| US4380507A (en) | 1983-04-19 |
| DE2724974A1 (en) | 1977-12-15 |
| FR2353572A1 (en) | 1977-12-30 |
| FR2353572B1 (en) | 1980-07-18 |
| NL191120B (en) | 1994-09-01 |
| ZA773321B (en) | 1978-04-26 |
| ES459442A1 (en) | 1978-04-01 |
| JPS52147592A (en) | 1977-12-08 |
| NL7705957A (en) | 1977-12-06 |
| BE855312A (en) | 1977-12-02 |
| NL191120C (en) | 1995-02-01 |
| IT1062072B (en) | 1983-06-25 |
| SE435931B (en) | 1984-10-29 |
| GB1550980A (en) | 1979-08-22 |
| SE7706339L (en) | 1977-12-04 |
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