CA1203949A - Ethylene polymers having a linear structure and method for preparing - Google Patents
Ethylene polymers having a linear structure and method for preparingInfo
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- CA1203949A CA1203949A CA000421142A CA421142A CA1203949A CA 1203949 A CA1203949 A CA 1203949A CA 000421142 A CA000421142 A CA 000421142A CA 421142 A CA421142 A CA 421142A CA 1203949 A CA1203949 A CA 1203949A
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Materials For Medical Uses (AREA)
Abstract
"Ethylene polymers having a linear structure and method for preparing"
Abstract of the disclosure Particular ethylene polymers are described having a linear structure, that is a structure which is essentially devoid of lengthy branching offs and having a density less than 0.9450 g/cm.3. They are crystalline ethylene copolymers with at least another alpha olefin having a density com-prised between 0.9150 and 0.9450 g/cm3, in which the con-tents of comonomer varies from 1 molar % to 7 molar %.
Such copolymers are further characterized by a melting point comprised between 115°C and 130°C and an X-ray crystalli-nity variable between 39% and 55% as a function of the quantity of comonomer, and a Melt Flow Index (according to the ASTM D-1238 test method) comprised between 0.1 and 50 g/10 min.
Abstract of the disclosure Particular ethylene polymers are described having a linear structure, that is a structure which is essentially devoid of lengthy branching offs and having a density less than 0.9450 g/cm.3. They are crystalline ethylene copolymers with at least another alpha olefin having a density com-prised between 0.9150 and 0.9450 g/cm3, in which the con-tents of comonomer varies from 1 molar % to 7 molar %.
Such copolymers are further characterized by a melting point comprised between 115°C and 130°C and an X-ray crystalli-nity variable between 39% and 55% as a function of the quantity of comonomer, and a Melt Flow Index (according to the ASTM D-1238 test method) comprised between 0.1 and 50 g/10 min.
Description
3~4~ .
1.
This invention relates to particular polymers of ethylene having a linear structure (-that is substantially devoid of legthy brancing oils having a density lower than 0.9450 g/cm . More particularly, the invention relates to copolymers of ethylene with at least another alpha-olefin having densities comprised in the range from 0.9150 and 0.9450 g/cm3 and also relates to the methods for preparing such polymers.
It is already known (for example, Brit. Patent N
1 131 528 and US Patent N 4 067 882), that it is possible to obtain linear polyethylene having a low or a medium density by low pressure polymerization processes, during progress of which ethylene is copolymerized with another : alpha-olefin, butene-l or octene-l preferably, in the presence : of Ziegler type catalysts or, at any rate, in the presence of ; catalytic systems of the kind conventionally employed for the preparation of poly-alpha-olefines.
; Such linear low-density copolymers differ from the conventional low-density polyethylene (as obtained with :~ 20 radicalic high-pressure procedures) not only for their linear : structure rather than branched off, but, above all, for the considerable improvement of a few properties such as the modulus and the elongation-at break as illustrated by the Table reported hereunder:
Density Melt Flexural Elonga- Tensile Flow Modulus tion at Strength Index break g/cm g/10 min MPa % MPa , = , _ Linear LDPE 0.9213 2.0 278 617 14.9 30 Conventional 0.9230 2.0 214 545 10.0 LDPE
LDPE = Low Density Polyethylene I
3~9
1.
This invention relates to particular polymers of ethylene having a linear structure (-that is substantially devoid of legthy brancing oils having a density lower than 0.9450 g/cm . More particularly, the invention relates to copolymers of ethylene with at least another alpha-olefin having densities comprised in the range from 0.9150 and 0.9450 g/cm3 and also relates to the methods for preparing such polymers.
It is already known (for example, Brit. Patent N
1 131 528 and US Patent N 4 067 882), that it is possible to obtain linear polyethylene having a low or a medium density by low pressure polymerization processes, during progress of which ethylene is copolymerized with another : alpha-olefin, butene-l or octene-l preferably, in the presence : of Ziegler type catalysts or, at any rate, in the presence of ; catalytic systems of the kind conventionally employed for the preparation of poly-alpha-olefines.
; Such linear low-density copolymers differ from the conventional low-density polyethylene (as obtained with :~ 20 radicalic high-pressure procedures) not only for their linear : structure rather than branched off, but, above all, for the considerable improvement of a few properties such as the modulus and the elongation-at break as illustrated by the Table reported hereunder:
Density Melt Flexural Elonga- Tensile Flow Modulus tion at Strength Index break g/cm g/10 min MPa % MPa , = , _ Linear LDPE 0.9213 2.0 278 617 14.9 30 Conventional 0.9230 2.0 214 545 10.0 LDPE
LDPE = Low Density Polyethylene I
3~9
2.
The linear low density polyethylene has a higher mechanical resistance than the conventional low density poly-ethylene and this property, for example in the processing runs for obtaining films, may make it possible to save up to 30% of the product and appreciable advantages are achieved in injection moulding and in the manufacture of filaments and cables by virtue of the improved mechanical properties at the low temperatures, such as shock resistance and the properties of the copolymers are a function of the distribution of the comonomer in the polymeric chain.
The present invention, in particular, provides ethylene copolymers with at least one other alpha olefin comonomer having, as a function of the quantity of comonomer which is present, densities comprised in the range from 0.9150 g/cm3 to 0.9450 g/cm3, a melting point comprised between 115C and 130C, an X-ray crystallinity variable between 39% and 55%, a Melt Flow Index according to the ASTM D-1238 method comprised between 0.1 and 50 g/10 min., and a contents of comonomer variable from 1% to 7% molar.
In accordance with the present invention the other alpha olefin may be selected from the group consisting of butene-l, hexene~l and octene-l.
The present invention, in anothex aspect, provides a process for preparing copolymers of ethylene as defined above characterized in contacting ethylene with at least one other alpha olefin in the presence of a catalytic system comprising an organic metallic compound of aluminium and a composition selected from the product of the reaction of metallic vapours with a titanium compound and a halogen donor or the product obtained from the preceding reaction previously modified by an organic metallic compound of aluminium or an alcohol.
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In accordance with the present invention, it is pos-- /
/
/
.
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sible to prepare polymers having a differential distribution of the comonomer by using catalytic systems of the high--yield class which are already known for the preparation of high-density and medium-density polyethylene as disclosed in the Canadian Patent N1.118.748 granted on February 23, 1982, Canadian Patent Nl.108.110 granted on September 1, 1981, Canadian Pat. Appln. N407.655 filed on July 20, 1982 and Canadian Patent Appln. N368.250-1 filed on January 9, 1981, by modifying the production process or introducing variations in the process itself.
The catalytic systems in question comprise constituents which are basically composed of an organic metallic compound of alumlnium and a second compound which may be the product of the reaction of metallic vapours with a compound of titanium and a halogen donor or such compound as modified by a subsequent reaction with an organic me-tallic compound of aluminium or with an alcohol.
In the first case, the catalyst can be represented by a formula such as TiX3.m'MXn, wherein X is a halogen, M
a metal selected from among Mg, Al, Ti, V, Mn, Cr, Mo, Ca, Zn, n is the valency of M an m' is equal to or higher than l:n.
Such a formulation is obtained by a process which provides for the vaporization under vacuum of at least one of the metals enumerated above and the reaction of the vapours thus obtained with the titanium compound in the presence of a compound capable of delivering halogen atoms. As outlined above, such a composition can be used as such or it can be modified by reacting it with an organic metallic compound of aluminium, whereby a formulation is obtained which is of the type TiX3.mM'Yn.qM 'Y'p.cAlY 3_sR 5 wherein X is a halogen, M' and M" are metals different from one ; another and selected from among those enumerated above, Y, Y' and Y", equal or different from each other are halo-gens and, in their turn, can be equal to or different from ~Z~:I 399~9 X, _ and can be 0 or different from 0 but cannot be zero simultaneously, c is always other than zero, n and are ; the valencies of M' and Ml',respectively, s can take any value between 0 and 3, R' is a hydrocarbon radical, preferably having a number of carbon atoms lower than or equal to 10.
As an alternative, the catalyst can be the product of the reaction between a titanium compound, selected from among the halides and the alcoholates, vapours of an electrically positive metal having reducing properties condensed at a low temperature, an organic halogen compound or an inorganic halogen compound and an alcohol.
As a co-catalyst, at any rate, a derivative of aluminium having the formula Al R"p,X3_p,is always employed, wherein R" is a hydrocarbon radical, X is a halogen and p' is a number variable from 1 to 3. In addition to the com-positions aforementioned, the catalyst system can be ob-tained starting from (a) the product of the reaction bet-ween a compound of titanium selected from among the ha-lides and the alcoholates, vapours of magnesium condensed at low temperatures, an organic or an inorganic halogen compound and an alcohol, (b) an aluminium trialkyl and an aluminium halide corresponding to the formula AlR'''SX3 s wherein X is C1 or Br, and s is comprised between 0 and 2.
The adoption of the catalytic compositions outlined above permits to obtain low-density polyethylene, and more particularly linear low density polyethylene by having the polymerization of ethylene taking place in the presence of at least another alpha olefin having a number of carbon atoms from 3 to 10. It has been observed that the alpha olefins, particularly butene-l improves the efficiency of the catalytic systems employed.
Quite particular advantages have been achieved by using butene-l, hexene 1 and octene-l: the final crystalline copolymers have a comonomer contents ranging ,, .
~Z~ 4~
from 1% molar to 7% molar, a melting point comprised between 115C and 130C, a crystallinity (X-ray) variable from 39%
and 55% as a function of the amount of comonomer which is present, and a Melt Flow Index (according to the ASTM D-1238 method) comprised between 0.1 and 50 grams per 10 minutes (g/10 min.), the density being always below 0.9450 g/cm3 and preferably comprised between 0.9150 and 0.9450 g/cm3.
The distribution of the comonomer in the polymeric chain is differentiated as a function of the process adopted for its preparation and this fact is evidenced by the different contents of substances which can be extracted by boiling heptane if the density is the same and the Melt Flow Index is the same.
The polymerization can be carried out, indifferently, in suspension, in solution, and in the gaseous phase, and, ; whenever necessary, the reaction medium can be composed of linear or branched C4-C10 hydrocarbons, cyclic hydrocarbons, halogenated hydrocarbons, or a C4-cut from reforming, con-sistently with the procedure to be adopted.
; 20 obviously, also the procedures vary consistently with the method which is adopted: thus the polymerization in the gaseous phase is carried out by feeding the cataly-tic system aforementioned into a gaseous mixture consisting of ethylene, one alpha-olefin, preferably propylene or butene-l, and hydrogen as a molecular weight adjuster in variable proportions consistently with the product to be obtained, at a temperature which can be selected between 10C and 100C, preferably between 60C and 90C under a pressure comprised between 5 and 50 bar, preferably from 10 to 30 bar. The products thus obtained are characterized by a density comprised between 0.9150 and 0.9450 g/cm3 and by a content of substances extractable by boiling heptane which range, for products having the same Melt Flow Index, from 65% to 5.9%.
,
The linear low density polyethylene has a higher mechanical resistance than the conventional low density poly-ethylene and this property, for example in the processing runs for obtaining films, may make it possible to save up to 30% of the product and appreciable advantages are achieved in injection moulding and in the manufacture of filaments and cables by virtue of the improved mechanical properties at the low temperatures, such as shock resistance and the properties of the copolymers are a function of the distribution of the comonomer in the polymeric chain.
The present invention, in particular, provides ethylene copolymers with at least one other alpha olefin comonomer having, as a function of the quantity of comonomer which is present, densities comprised in the range from 0.9150 g/cm3 to 0.9450 g/cm3, a melting point comprised between 115C and 130C, an X-ray crystallinity variable between 39% and 55%, a Melt Flow Index according to the ASTM D-1238 method comprised between 0.1 and 50 g/10 min., and a contents of comonomer variable from 1% to 7% molar.
In accordance with the present invention the other alpha olefin may be selected from the group consisting of butene-l, hexene~l and octene-l.
The present invention, in anothex aspect, provides a process for preparing copolymers of ethylene as defined above characterized in contacting ethylene with at least one other alpha olefin in the presence of a catalytic system comprising an organic metallic compound of aluminium and a composition selected from the product of the reaction of metallic vapours with a titanium compound and a halogen donor or the product obtained from the preceding reaction previously modified by an organic metallic compound of aluminium or an alcohol.
~Z~35~
2a .
In accordance with the present invention, it is pos-- /
/
/
.
~L~C~3~
sible to prepare polymers having a differential distribution of the comonomer by using catalytic systems of the high--yield class which are already known for the preparation of high-density and medium-density polyethylene as disclosed in the Canadian Patent N1.118.748 granted on February 23, 1982, Canadian Patent Nl.108.110 granted on September 1, 1981, Canadian Pat. Appln. N407.655 filed on July 20, 1982 and Canadian Patent Appln. N368.250-1 filed on January 9, 1981, by modifying the production process or introducing variations in the process itself.
The catalytic systems in question comprise constituents which are basically composed of an organic metallic compound of alumlnium and a second compound which may be the product of the reaction of metallic vapours with a compound of titanium and a halogen donor or such compound as modified by a subsequent reaction with an organic me-tallic compound of aluminium or with an alcohol.
In the first case, the catalyst can be represented by a formula such as TiX3.m'MXn, wherein X is a halogen, M
a metal selected from among Mg, Al, Ti, V, Mn, Cr, Mo, Ca, Zn, n is the valency of M an m' is equal to or higher than l:n.
Such a formulation is obtained by a process which provides for the vaporization under vacuum of at least one of the metals enumerated above and the reaction of the vapours thus obtained with the titanium compound in the presence of a compound capable of delivering halogen atoms. As outlined above, such a composition can be used as such or it can be modified by reacting it with an organic metallic compound of aluminium, whereby a formulation is obtained which is of the type TiX3.mM'Yn.qM 'Y'p.cAlY 3_sR 5 wherein X is a halogen, M' and M" are metals different from one ; another and selected from among those enumerated above, Y, Y' and Y", equal or different from each other are halo-gens and, in their turn, can be equal to or different from ~Z~:I 399~9 X, _ and can be 0 or different from 0 but cannot be zero simultaneously, c is always other than zero, n and are ; the valencies of M' and Ml',respectively, s can take any value between 0 and 3, R' is a hydrocarbon radical, preferably having a number of carbon atoms lower than or equal to 10.
As an alternative, the catalyst can be the product of the reaction between a titanium compound, selected from among the halides and the alcoholates, vapours of an electrically positive metal having reducing properties condensed at a low temperature, an organic halogen compound or an inorganic halogen compound and an alcohol.
As a co-catalyst, at any rate, a derivative of aluminium having the formula Al R"p,X3_p,is always employed, wherein R" is a hydrocarbon radical, X is a halogen and p' is a number variable from 1 to 3. In addition to the com-positions aforementioned, the catalyst system can be ob-tained starting from (a) the product of the reaction bet-ween a compound of titanium selected from among the ha-lides and the alcoholates, vapours of magnesium condensed at low temperatures, an organic or an inorganic halogen compound and an alcohol, (b) an aluminium trialkyl and an aluminium halide corresponding to the formula AlR'''SX3 s wherein X is C1 or Br, and s is comprised between 0 and 2.
The adoption of the catalytic compositions outlined above permits to obtain low-density polyethylene, and more particularly linear low density polyethylene by having the polymerization of ethylene taking place in the presence of at least another alpha olefin having a number of carbon atoms from 3 to 10. It has been observed that the alpha olefins, particularly butene-l improves the efficiency of the catalytic systems employed.
Quite particular advantages have been achieved by using butene-l, hexene 1 and octene-l: the final crystalline copolymers have a comonomer contents ranging ,, .
~Z~ 4~
from 1% molar to 7% molar, a melting point comprised between 115C and 130C, a crystallinity (X-ray) variable from 39%
and 55% as a function of the amount of comonomer which is present, and a Melt Flow Index (according to the ASTM D-1238 method) comprised between 0.1 and 50 grams per 10 minutes (g/10 min.), the density being always below 0.9450 g/cm3 and preferably comprised between 0.9150 and 0.9450 g/cm3.
The distribution of the comonomer in the polymeric chain is differentiated as a function of the process adopted for its preparation and this fact is evidenced by the different contents of substances which can be extracted by boiling heptane if the density is the same and the Melt Flow Index is the same.
The polymerization can be carried out, indifferently, in suspension, in solution, and in the gaseous phase, and, ; whenever necessary, the reaction medium can be composed of linear or branched C4-C10 hydrocarbons, cyclic hydrocarbons, halogenated hydrocarbons, or a C4-cut from reforming, con-sistently with the procedure to be adopted.
; 20 obviously, also the procedures vary consistently with the method which is adopted: thus the polymerization in the gaseous phase is carried out by feeding the cataly-tic system aforementioned into a gaseous mixture consisting of ethylene, one alpha-olefin, preferably propylene or butene-l, and hydrogen as a molecular weight adjuster in variable proportions consistently with the product to be obtained, at a temperature which can be selected between 10C and 100C, preferably between 60C and 90C under a pressure comprised between 5 and 50 bar, preferably from 10 to 30 bar. The products thus obtained are characterized by a density comprised between 0.9150 and 0.9450 g/cm3 and by a content of substances extractable by boiling heptane which range, for products having the same Melt Flow Index, from 65% to 5.9%.
,
3~
The suspension polymerization is carried out in aliphatic C4-C10 hydrocarbonaceous solvents, straight line or bxanched, preferably butane or isobutane, or halogen-sub-stituted hydrocarbons, using as the comonomer alpha olefins of the C3-C10 range, those from C3 to C6 being preferred, and any of the catalytic system described hereinabove.
The polymerization is carried out at a temperature which can be selected between 20C and 90C, preferably between 50C and 80C under a pressure comprised between 1 and 60 bar, preferably between 13 and 30 bar. The poly-merization can be carried out as a single-step run or in a plural stage run with serially arranged reactors and by feeding the gaseous phase with different composition.
The finishing of the product can be carried out lS either by evaporation of the solvent in the case of low-boiling solvents, or by centrifugation and drying of the powder, or by stripping.
The products which are obtained from a single-step process and having a density comprised between 0.9150 and 0.9450 g/cm3 have a fraction of substances extractable by boiling heptane comprised between 43% and 3%, whereas the samples obtained from a two-step process have a fraction of extractable subtances comprised between 50~ and 3.5%.
For the polymerization process in solution, it is necessary to work with solvents the critical temperature of which is above the temperature of polymerization, the latter being selected within the range 130C - 250C; particularly advantageous have proven to be the cyclic hydrocarbons such as cyclohexane and methylcyclohexane and mixture of normal and isohydrocarbons the boiling point of which is comprised between 120C and 180C, inasmuch as they have a fair dissolving power towards the copolymers to be produced, the best results being obtained by maintaining the concentration of the polymer in the reaction mixture not above 40~ by I: s ~lzl~39~9 weight relative to the solvent.
The adjustment of the molecular weight of the copolymers as produced is carried out in a conventional way by using hydrogen in an amount comprised between 0.003 and 0.5 mol per mol of ethylene.
The polymerization can be carried out by intro-ducing in the reaction environment ethylene, hydrogen, an alpha-olefin (C3-C10l preferably C6-C10, straight line of branched) and any or the catalytic systems described above, while maintaining the reaction mixture stirred so as to encourage the dissipation of the polymerization heat and to achieve an improved homogeneousness of the system. The stay times of the polymeric solution may vary consistently with the polymerization conditions Erom 1 minute to 24 hours, the preferred range being between 5 minutes and 4 hours, the polymerization pressures are comparatively low and are comprised between 5 and 100 bar.
The copolymers are recovered by removing the un- -reacted monomers and the solvent from the polymerization mixture and by deactivating the catalytic system with appropriate reagents.
The products thus obtained, having a density comprised between 0.9150 and 0.9450 g/cm3 have a fraction of substances extractable by boiling heptane comprised between 56% and 5%.
In order to give an evidence of the differentiation of the products which can be obtained with the different procedures,Table 1 reports data as to the substances which can be extracted by nC7 (normal heptane) at the boiling point temperature, as well as a few technological proper-ties of the films obtained correspondingly.
f ' 3~
T A B L E _l Example Process reaction Density Polymer. Melt Extracta- Ccmonomer No. Medium Temper. Flow ble nC7 contents Index at 98C
g/cm3 C g/lOmin % % by wt 2 l-step isobutane 0.9210 122 1.2 33.8 6.8 slurry 2-step isobutane 0.9204 122 1.1 39 7.0 slurry 6 l-step nor.hexane 0.9213 122.5 0.9 50.1 6.2 slurry 9 gaseous --------- 0.9198 121.5 1.3 58 6.9 phase solution cyclohe~neO.9210 124 1.0 44 6.0 The foregoing and other modes of operation will become still more conspicuous from the scrutiny of the following examples, to which a mere function of illustration is to be attributed, without however construing them as being limitations whatsoever to the scope of the present invention.
Preparation of the catalyst A rotary evaporator is used, in the flask of which, centrally a tungsten filament is arranged, which is spiralled and connected to a source of electricity Beneath the flask a cooling bath is horizontally arranged.
',~` ', I, 3~
g The apparatus is connected, via a 3-way cock to the vacuum and the nitrogen-feed lines.
Around the tungsten resistor, which is appropriately protected, a magnesium wire of 1 gram is coiled and the 500-ml flask is charged under a nitrogen blanket with 250 mls of anhydrous and de-aerated heptane, 15 mls of l-chlorohexane, corresponding to 105 millimols (mM) and 0.23 ml of TiC14 corresponding to 2.1 mM. The flask is cooled to -70C, a vacuum of 10 2 Torr is produced and the tungsten spiral is heated so as to vaporize the metal coiled thereon. On ; completion of the vaporization step nitrogen is fed into the apparatus and the flask is restored to room temperature while keeping the mixture stirred, whereafter the flask is heated during 1 hour to 80C (Catalyst A).
A 500-ml flask is charged with 70 g of polyethylene powder having a controlled particle-size, drying under vacuum -I is carried out for 30 minutes whereafter the flask is filled with nitrogen and, still in such an inert atmosphere, the suspension previously obtained is charged in the flask. The solvent is driven off under vacuum with vigorous stirring by heating the flask to 50C-60C.
On completion of the solvent evaporation, the flask is filled with nitrogen again. The catalyst thus obtained (catalyst B) is a free-flowing powder having a hazelnut colour.
The analysis gives:
Ti= 0.029 milligramatom/g - Mg= 0.532 milligramatom/g and Cl =1.12 milligramatom/g.
A 5-litre autoclave fitted with an anchor-shaped stirrer is de-aerated under vacuum and charged with 1.3 litres of isobutane, the temperature is raised to 60C
whereafter there are added 120 g of butene-l, 7mM of aluminium triisobutyl, hydrogen to a pressure of 1.55 bar, I' ~Q3~9 ethylene to a total pressure of 13 bar and 0.5 g of the catalyst (B) equivalent to 0.0145 milligramatom of Ti.
The temperature is maintained at 60C and ethylene is fed by weeping the total pressure constant.
After polymerization for 2 hours, the reaction is stopped with 20 mls of ethanol, whereafter the solvent is evaporated off. There are obtained 310 g of polymer corresponding to a yield of 430 ~g of polymer per g of Ti, the polymer having the following specifications:
Density 0.9210 g/cm3 Butene contents (NMR) 6.8~ by wt CH3/100 C (number) 1.70 Melt Flow Index (MFI) at 2.16 kg 1.2 g/10 mins.
Melting point 122C
X-ray cristallinity 42%
Apparent density 0.33 g/cm Ave.diameter of the powder 350 microns Extract from boiling C7 33.8%
The same apparatus and procedure as in Example 2 are adopted but with different quantity of butene, that is, 80 g. There are obtained 260 g of polymer, corresponding to a yield of 360 kg of polymer per g of titanium, the 25 polymer having the following specifications:
Density 0.9284 g/cm3 Butene contents 4.8% by wt CH3/100 C (number) 1.1 MFI (Melt Flow Index) 0.4 g/10 min.
Apparent density 0.30 g/cm Melting point 124.5C
The same apparatus and procedure as in Example 2 I
~3~
are adopted but with a quantity of butene-l equal to 140 g.
There are obtained 350 g of polymer corresponding to a yield of 480 kg of polymer per g of Ti, the polymer having the following specifications:
Density 0.9152 g/cm3 Butene contents 10.3% by wt CH3/100 C 2.5 MFI (2.16 kg) 1.2 g/10 min.
Apparent density 0.25 g/cm3 Melting point 120C
Heptane extract (boiling) 52%
The same apparatus as in Example 2 is used, but by varying the mode of operation as follows: there is charged 1.3 litre of isobutene, which is brought to 60~C, whereafter there are added 40 g of butene-l, 6 mM (millimols) of aluminium triisobutyl, hydrogen to a pressure of 1.70 bar, ethylene up to a pressure (total) of 14 bar and 0.5 g of catalyst (B) of Example 1, which is equivalent to 0.0145 milligramatom of Ti. The temperature is maintained at 60C
and ethylene is introduced by keeping the total pressure constant. After a 15-minute polymerization (about 30% of the total polymer is produced), there are charged 140 g of butene and polymerization is continued while the total pressure is maintained at 14 bar by feeding ethylene again.
After a overall polymerization time of 2 hours, the polyme-rization is halted with 19 cm3 of ethanol, whereafter the solvent is evaporated off. There are obtained 320 g of po-lymer, which correspond to a yield of 445 kg of polymer per g of Ti, the polymer having the following properties:
Density 0.9204 g/cm3 Butene contents 7.0% by wt Melt Flow Index 1.1 g/10 min.
Apparent density 0.33 g/cm3 .,, =.
,;
~35~
Melting point 122C
Extract from boiling C7 39 A 5-litre autoclave equipped with an anchor-shaped stirrer is de-aerated under vacuum and is charged with 2 litres of anhydrous and de-aerated hexane and brought to 60C, whereafter there are added 130 g of butene-l, 6mM
(millimol) of aluminium triisobutyl, hydrogen to a partial pressure of 2.2 bar, ethylene to a total gauge pressure of 6 bar and 0.5 g of the catalyst (B) of Example 1, corre-sponding to 0.0145 milligramatom of Ti.
The temperature is maintained at 60C and ethylene is fed by keeping the total pressure constant. After two hours of polymerization, the reaction is stopped with 10 cm3 of ethanol, whereafter the autoclave is allowed to cool, the gases are vented and the polymer suspension is stripped of the solvents.
; The dried polymer, 250 g, corresponding to a yield of 350 ky of polymer per g of Ti is a free-flowing powder 20 and exhibits the following specifications:
Density 0.9213 g/cm Butene-l contents 6.2% by wt Melt Flow Index 0.9 g/10 min.
Apparent density 0.23 g/cm3 Extract from boiling C7 50.1 The apparatus and the procedure of Example 2 are adopted but using anhydrous nor.butane as the reaction medium and all the same components for the polymerization 30 in the same amounts so that the overall gauge pressure is ; 11.5 bar.
The polymer is obtained in an amount of 280 g, corresponding to a yield of 385 kg of polymer per g of Ti, and has the following properties:
3~9 Density 0.9215 g/cm3 Butene contents 6.5% by wt C~13/100 C (number) 1.65 Melt Flow Index 0.90 g/10 min.
X-ray crystallinity 41%
Apparent density 0.34 g/cm The same apparatus and procedure as in Example 6 are adopted using 300 g of anhydrous and de-aerated hexene.
10 There are obtained 240 g of a polymer having the following specifications:
Density 0.9290 g/cm3 C~3/100 C (number) 0.90 Hexene contents 5.4% by wt Melt Flow Index 1.1 g/10 min.
Apparent density 0.25 g/cm In a test tube having a tail portion which has been previously dried and placed in an inert atmosphere, there are charged 2 g of catalyst (B) and 6 milligramatoms of A1-iso-Bu3 dissolved in 15 mls hexane: stirring is effected with a magnetic stirrer whereafter hexane is evaporated off, with stirring, until the sample is thoroughly dry.
1 g of catalyst, equivalent to 0.013 milligramatoms of Ti, is charged under a nitrogen blanket in a 2-litre autoclave fitted with a stirrer, dried and maintained in an inert atmosphere. The autoclave is evacuated to drive the nitrogen off, is heated to 70C whereafter there are introduced with a gas stream having the following compo-sition: ethylene 80% by volume, butene 15%, hydrogen 5%
to a pressure of 10 bar.
; After one hour of polymerization there are obtained 100 g of powdered polymer having the following properties:
Density 0.9198 g/cm3 ~3~35~9 Butene-l contents 6.9% by wt MFI 1.30 g/10 mint Melting point 121.5C
Extract from boiling C7 58%
A 5-litre autoclave having a stirrer is charged with 2 litres of anydrous and de-aerated cyclohexane con-taining 1 millimol of Al(nor. Oct)3, the temperature is raised to 150C whereafter there are added 100 g of octene-l, hydrogen to a pressure of 0.5 bar, ethylene to ; a total gauge pressure of 10 bar and 1.5 cm3 of catalyst of the type (A) of Example 1 corresponding to 0.012 mil-ligramatoms of titanium. The pressure is maintamed constant by feeding ethylene for 30 minutes. On completion of the polymerization, the reaction is halted, the autoclave is allowed to cool and the gases are vented. The product thus ;~ obtained consists of 140 g of polymer, corresponding to a yield of 230 kg of polymer per g of titanium.
The polymer thus obtained has the following properties: -Density 0.9210 g/cm3 Octene contents 7.2~ by wt CH3/100 C 0.96 Melting point 122C
Melt Flow Index 1.0 g/10 min.
C7 extract (boiling) 44.5~
:
,; .
The suspension polymerization is carried out in aliphatic C4-C10 hydrocarbonaceous solvents, straight line or bxanched, preferably butane or isobutane, or halogen-sub-stituted hydrocarbons, using as the comonomer alpha olefins of the C3-C10 range, those from C3 to C6 being preferred, and any of the catalytic system described hereinabove.
The polymerization is carried out at a temperature which can be selected between 20C and 90C, preferably between 50C and 80C under a pressure comprised between 1 and 60 bar, preferably between 13 and 30 bar. The poly-merization can be carried out as a single-step run or in a plural stage run with serially arranged reactors and by feeding the gaseous phase with different composition.
The finishing of the product can be carried out lS either by evaporation of the solvent in the case of low-boiling solvents, or by centrifugation and drying of the powder, or by stripping.
The products which are obtained from a single-step process and having a density comprised between 0.9150 and 0.9450 g/cm3 have a fraction of substances extractable by boiling heptane comprised between 43% and 3%, whereas the samples obtained from a two-step process have a fraction of extractable subtances comprised between 50~ and 3.5%.
For the polymerization process in solution, it is necessary to work with solvents the critical temperature of which is above the temperature of polymerization, the latter being selected within the range 130C - 250C; particularly advantageous have proven to be the cyclic hydrocarbons such as cyclohexane and methylcyclohexane and mixture of normal and isohydrocarbons the boiling point of which is comprised between 120C and 180C, inasmuch as they have a fair dissolving power towards the copolymers to be produced, the best results being obtained by maintaining the concentration of the polymer in the reaction mixture not above 40~ by I: s ~lzl~39~9 weight relative to the solvent.
The adjustment of the molecular weight of the copolymers as produced is carried out in a conventional way by using hydrogen in an amount comprised between 0.003 and 0.5 mol per mol of ethylene.
The polymerization can be carried out by intro-ducing in the reaction environment ethylene, hydrogen, an alpha-olefin (C3-C10l preferably C6-C10, straight line of branched) and any or the catalytic systems described above, while maintaining the reaction mixture stirred so as to encourage the dissipation of the polymerization heat and to achieve an improved homogeneousness of the system. The stay times of the polymeric solution may vary consistently with the polymerization conditions Erom 1 minute to 24 hours, the preferred range being between 5 minutes and 4 hours, the polymerization pressures are comparatively low and are comprised between 5 and 100 bar.
The copolymers are recovered by removing the un- -reacted monomers and the solvent from the polymerization mixture and by deactivating the catalytic system with appropriate reagents.
The products thus obtained, having a density comprised between 0.9150 and 0.9450 g/cm3 have a fraction of substances extractable by boiling heptane comprised between 56% and 5%.
In order to give an evidence of the differentiation of the products which can be obtained with the different procedures,Table 1 reports data as to the substances which can be extracted by nC7 (normal heptane) at the boiling point temperature, as well as a few technological proper-ties of the films obtained correspondingly.
f ' 3~
T A B L E _l Example Process reaction Density Polymer. Melt Extracta- Ccmonomer No. Medium Temper. Flow ble nC7 contents Index at 98C
g/cm3 C g/lOmin % % by wt 2 l-step isobutane 0.9210 122 1.2 33.8 6.8 slurry 2-step isobutane 0.9204 122 1.1 39 7.0 slurry 6 l-step nor.hexane 0.9213 122.5 0.9 50.1 6.2 slurry 9 gaseous --------- 0.9198 121.5 1.3 58 6.9 phase solution cyclohe~neO.9210 124 1.0 44 6.0 The foregoing and other modes of operation will become still more conspicuous from the scrutiny of the following examples, to which a mere function of illustration is to be attributed, without however construing them as being limitations whatsoever to the scope of the present invention.
Preparation of the catalyst A rotary evaporator is used, in the flask of which, centrally a tungsten filament is arranged, which is spiralled and connected to a source of electricity Beneath the flask a cooling bath is horizontally arranged.
',~` ', I, 3~
g The apparatus is connected, via a 3-way cock to the vacuum and the nitrogen-feed lines.
Around the tungsten resistor, which is appropriately protected, a magnesium wire of 1 gram is coiled and the 500-ml flask is charged under a nitrogen blanket with 250 mls of anhydrous and de-aerated heptane, 15 mls of l-chlorohexane, corresponding to 105 millimols (mM) and 0.23 ml of TiC14 corresponding to 2.1 mM. The flask is cooled to -70C, a vacuum of 10 2 Torr is produced and the tungsten spiral is heated so as to vaporize the metal coiled thereon. On ; completion of the vaporization step nitrogen is fed into the apparatus and the flask is restored to room temperature while keeping the mixture stirred, whereafter the flask is heated during 1 hour to 80C (Catalyst A).
A 500-ml flask is charged with 70 g of polyethylene powder having a controlled particle-size, drying under vacuum -I is carried out for 30 minutes whereafter the flask is filled with nitrogen and, still in such an inert atmosphere, the suspension previously obtained is charged in the flask. The solvent is driven off under vacuum with vigorous stirring by heating the flask to 50C-60C.
On completion of the solvent evaporation, the flask is filled with nitrogen again. The catalyst thus obtained (catalyst B) is a free-flowing powder having a hazelnut colour.
The analysis gives:
Ti= 0.029 milligramatom/g - Mg= 0.532 milligramatom/g and Cl =1.12 milligramatom/g.
A 5-litre autoclave fitted with an anchor-shaped stirrer is de-aerated under vacuum and charged with 1.3 litres of isobutane, the temperature is raised to 60C
whereafter there are added 120 g of butene-l, 7mM of aluminium triisobutyl, hydrogen to a pressure of 1.55 bar, I' ~Q3~9 ethylene to a total pressure of 13 bar and 0.5 g of the catalyst (B) equivalent to 0.0145 milligramatom of Ti.
The temperature is maintained at 60C and ethylene is fed by weeping the total pressure constant.
After polymerization for 2 hours, the reaction is stopped with 20 mls of ethanol, whereafter the solvent is evaporated off. There are obtained 310 g of polymer corresponding to a yield of 430 ~g of polymer per g of Ti, the polymer having the following specifications:
Density 0.9210 g/cm3 Butene contents (NMR) 6.8~ by wt CH3/100 C (number) 1.70 Melt Flow Index (MFI) at 2.16 kg 1.2 g/10 mins.
Melting point 122C
X-ray cristallinity 42%
Apparent density 0.33 g/cm Ave.diameter of the powder 350 microns Extract from boiling C7 33.8%
The same apparatus and procedure as in Example 2 are adopted but with different quantity of butene, that is, 80 g. There are obtained 260 g of polymer, corresponding to a yield of 360 kg of polymer per g of titanium, the 25 polymer having the following specifications:
Density 0.9284 g/cm3 Butene contents 4.8% by wt CH3/100 C (number) 1.1 MFI (Melt Flow Index) 0.4 g/10 min.
Apparent density 0.30 g/cm Melting point 124.5C
The same apparatus and procedure as in Example 2 I
~3~
are adopted but with a quantity of butene-l equal to 140 g.
There are obtained 350 g of polymer corresponding to a yield of 480 kg of polymer per g of Ti, the polymer having the following specifications:
Density 0.9152 g/cm3 Butene contents 10.3% by wt CH3/100 C 2.5 MFI (2.16 kg) 1.2 g/10 min.
Apparent density 0.25 g/cm3 Melting point 120C
Heptane extract (boiling) 52%
The same apparatus as in Example 2 is used, but by varying the mode of operation as follows: there is charged 1.3 litre of isobutene, which is brought to 60~C, whereafter there are added 40 g of butene-l, 6 mM (millimols) of aluminium triisobutyl, hydrogen to a pressure of 1.70 bar, ethylene up to a pressure (total) of 14 bar and 0.5 g of catalyst (B) of Example 1, which is equivalent to 0.0145 milligramatom of Ti. The temperature is maintained at 60C
and ethylene is introduced by keeping the total pressure constant. After a 15-minute polymerization (about 30% of the total polymer is produced), there are charged 140 g of butene and polymerization is continued while the total pressure is maintained at 14 bar by feeding ethylene again.
After a overall polymerization time of 2 hours, the polyme-rization is halted with 19 cm3 of ethanol, whereafter the solvent is evaporated off. There are obtained 320 g of po-lymer, which correspond to a yield of 445 kg of polymer per g of Ti, the polymer having the following properties:
Density 0.9204 g/cm3 Butene contents 7.0% by wt Melt Flow Index 1.1 g/10 min.
Apparent density 0.33 g/cm3 .,, =.
,;
~35~
Melting point 122C
Extract from boiling C7 39 A 5-litre autoclave equipped with an anchor-shaped stirrer is de-aerated under vacuum and is charged with 2 litres of anhydrous and de-aerated hexane and brought to 60C, whereafter there are added 130 g of butene-l, 6mM
(millimol) of aluminium triisobutyl, hydrogen to a partial pressure of 2.2 bar, ethylene to a total gauge pressure of 6 bar and 0.5 g of the catalyst (B) of Example 1, corre-sponding to 0.0145 milligramatom of Ti.
The temperature is maintained at 60C and ethylene is fed by keeping the total pressure constant. After two hours of polymerization, the reaction is stopped with 10 cm3 of ethanol, whereafter the autoclave is allowed to cool, the gases are vented and the polymer suspension is stripped of the solvents.
; The dried polymer, 250 g, corresponding to a yield of 350 ky of polymer per g of Ti is a free-flowing powder 20 and exhibits the following specifications:
Density 0.9213 g/cm Butene-l contents 6.2% by wt Melt Flow Index 0.9 g/10 min.
Apparent density 0.23 g/cm3 Extract from boiling C7 50.1 The apparatus and the procedure of Example 2 are adopted but using anhydrous nor.butane as the reaction medium and all the same components for the polymerization 30 in the same amounts so that the overall gauge pressure is ; 11.5 bar.
The polymer is obtained in an amount of 280 g, corresponding to a yield of 385 kg of polymer per g of Ti, and has the following properties:
3~9 Density 0.9215 g/cm3 Butene contents 6.5% by wt C~13/100 C (number) 1.65 Melt Flow Index 0.90 g/10 min.
X-ray crystallinity 41%
Apparent density 0.34 g/cm The same apparatus and procedure as in Example 6 are adopted using 300 g of anhydrous and de-aerated hexene.
10 There are obtained 240 g of a polymer having the following specifications:
Density 0.9290 g/cm3 C~3/100 C (number) 0.90 Hexene contents 5.4% by wt Melt Flow Index 1.1 g/10 min.
Apparent density 0.25 g/cm In a test tube having a tail portion which has been previously dried and placed in an inert atmosphere, there are charged 2 g of catalyst (B) and 6 milligramatoms of A1-iso-Bu3 dissolved in 15 mls hexane: stirring is effected with a magnetic stirrer whereafter hexane is evaporated off, with stirring, until the sample is thoroughly dry.
1 g of catalyst, equivalent to 0.013 milligramatoms of Ti, is charged under a nitrogen blanket in a 2-litre autoclave fitted with a stirrer, dried and maintained in an inert atmosphere. The autoclave is evacuated to drive the nitrogen off, is heated to 70C whereafter there are introduced with a gas stream having the following compo-sition: ethylene 80% by volume, butene 15%, hydrogen 5%
to a pressure of 10 bar.
; After one hour of polymerization there are obtained 100 g of powdered polymer having the following properties:
Density 0.9198 g/cm3 ~3~35~9 Butene-l contents 6.9% by wt MFI 1.30 g/10 mint Melting point 121.5C
Extract from boiling C7 58%
A 5-litre autoclave having a stirrer is charged with 2 litres of anydrous and de-aerated cyclohexane con-taining 1 millimol of Al(nor. Oct)3, the temperature is raised to 150C whereafter there are added 100 g of octene-l, hydrogen to a pressure of 0.5 bar, ethylene to ; a total gauge pressure of 10 bar and 1.5 cm3 of catalyst of the type (A) of Example 1 corresponding to 0.012 mil-ligramatoms of titanium. The pressure is maintamed constant by feeding ethylene for 30 minutes. On completion of the polymerization, the reaction is halted, the autoclave is allowed to cool and the gases are vented. The product thus ;~ obtained consists of 140 g of polymer, corresponding to a yield of 230 kg of polymer per g of titanium.
The polymer thus obtained has the following properties: -Density 0.9210 g/cm3 Octene contents 7.2~ by wt CH3/100 C 0.96 Melting point 122C
Melt Flow Index 1.0 g/10 min.
C7 extract (boiling) 44.5~
:
,; .
Claims (20)
1. Ethylene copolymers with at least one other alpha olefin comonomer having, as a function of the quantity of comonomer which is present, densities comprised in the range from 0.9150 g/cm3 to 0.9450 g/cm3, a melting point comprised between 115°C and 130°C, an X-ray crystallinity variable between 39% and 55%, a Melt Flow Index according to the ASTM D-1238 method comprised between 0.1 and 50 g/10 min., and a contents of comonomer variable from 1% to 7% molar.
2. Copolymers according to claim 1, wherein the other alpha olefin is selected from the group consisting of butene-2, hexene-1 and octene-1.
3. A process for preparing copolymers of ethylene according to claim 1, characterized in contacting ethylene with at least one other alpha olefin in the presence of a catalytic system comprising an organic metallic compound of aluminium and a composition selected from the product of the reaction of metallic vapours with a titanium compound and a halogen donor or the product obtained from the preceding reaction previously modified by an organic metallic compound of aluminium or an alcohol.
4. A process for the preparation of copolymers of ethylene according to claim 3, wherein the catalyst system consists of a compound having the formula TiX3.m'MXn wherein X is a halogen, M a metal selected from among Mg, Al, Ti, V, MN, CR, Mo, Ca and Zn, n is the valency of M and m' is equal to l/n or greater.
5. A process for the preparation of copolymers of ethylene according to claim 3, wherein the catalyst system consists of a compound having the formula TiX3.mM'Yn.qM''Y'p.
cAlY" 3-sR's wherein X is a halogen, M' and M" are metals different from one another and selected from among those enumerated in claim 4, Y, Y', and Y" equal to each other or different from each other are halogens and can be equal to or different from X, m and q can be 0 or other than zero, but not both simultaneously equal to zero, c is always different from zero, n and p are the valencies of M' and M'', respectively, s can take any value from 0 to 3, R' is a hydrocarbon radical having a number of carbon atoms equal to 10 or lower.
cAlY" 3-sR's wherein X is a halogen, M' and M" are metals different from one another and selected from among those enumerated in claim 4, Y, Y', and Y" equal to each other or different from each other are halogens and can be equal to or different from X, m and q can be 0 or other than zero, but not both simultaneously equal to zero, c is always different from zero, n and p are the valencies of M' and M'', respectively, s can take any value from 0 to 3, R' is a hydrocarbon radical having a number of carbon atoms equal to 10 or lower.
6. A process for the preparation of copolymers of ethylene according to claim 3, characterized in that the polymerization is carried out by contacting a gaseous mixture comprising ethylene, at least one other alpha olefin and hydrogen with said catalyst system.
7. A process for the preparation of ethylene copolymers according to claim 6, characterized in that the reaction is carried out at a temperature comprised between 20°C and 100°C and under pressures comprised between 5 and 50 bar.
8. A process for the preparation of ethylene copolymers according to claim 6, characterized in that the reaction is carried out at a temperature comprised between 60°C and 90°C and under a pressure comprised between 10 and 30 bar.
9. process for the preparation of ethylene copolymers according to claim 3, characterized in that the polymerization reaction is carried out in suspension.
10. A process for the preparation of copolymers of ethylene according to claim 9, characterized in that the reaction is carried out in the presence of a solvent selected from among the aliphatic C4-C10 hydrocarbons or from among the halogen substituted hydrocarbons.
11. A process for the preparation of ethylene copolymers according to claim 9 or claim 10, characterized in that the reaction is carried out at a temperature comprised between 20°C and 90°C and under a pressure comprised between 1 and 60 bar.
12. A process for the preparation of ethylene copolymers according to claim 10, characterized in that the reaction is carried out at a temperature comprised between 50°C and 80°C and under a pressure comprised between 13 and 30 bar.
13. A process for the preparation of ethylene copolymers according to claim 3, characterized in that the polymerization is carried out in solution.
14. A process for the preparation of ethylene copolymers according to claim 13, characterized in that the reaction is carried out at a temperature comprised between 130°C and 250°C.
15. A process for the preparation of ethylene copolymers according to claim 13, characterized in that the reaction is carried out in the presence of a solvent having a critical temperature which is higher than the polymeriza-tion temperature.
16. A process for the preparation of ethylene copolymers according to claim 14, characterized in that the reaction is carried out in the presence of a solvent having a critical temperature which is higher than the polymerization temperature.
17. A process for the preparation of ethylene copolymers according to claim 15, characterized in that the solvent is selected from among cyclical hydrocarbons and hydrocarbon mixtures.
18. A process for the preparation of ethylene copolymers according to claim 16, characterized in that the solvent is selected from among cyclical hydrocarbons and hydrocarbon mixtures.
19. A process for the preparation of copolymers of ethylene according to claim 3, 4 or 5, wherein the other alpha olefin is selected from the group consisting of butene-1, hexene-1 and octene-1.
20. A process for the preparation of copolymers of ethylene according to claim 8, 12 or 18, wherein the other alpha olefin is selected from the group consisting of hutene-1, hexene-1 and octene-1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT8219614A IT1210855B (en) | 1982-02-12 | 1982-02-12 | LINEAR STRUCTURE ETHYLENE POLYMERS AND PROCESSES FOR THEIR PREPARATION. |
| IT19614A/82 | 1982-02-12 |
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| CA1203949A true CA1203949A (en) | 1986-04-29 |
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| CA000421142A Expired CA1203949A (en) | 1982-02-12 | 1983-02-08 | Ethylene polymers having a linear structure and method for preparing |
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| JP (1) | JPS58171409A (en) |
| BE (1) | BE895878A (en) |
| CA (1) | CA1203949A (en) |
| CH (1) | CH659076A5 (en) |
| DD (1) | DD207546A5 (en) |
| DE (1) | DE3304758A1 (en) |
| DK (1) | DK59783A (en) |
| ES (1) | ES519970A0 (en) |
| FR (1) | FR2521570B1 (en) |
| GB (1) | GB2114584B (en) |
| GR (1) | GR78079B (en) |
| IE (1) | IE830281L (en) |
| IL (1) | IL67871A (en) |
| IT (1) | IT1210855B (en) |
| LU (1) | LU84641A1 (en) |
| NL (1) | NL8300457A (en) |
| NO (1) | NO830405L (en) |
| PL (1) | PL240435A1 (en) |
| PT (1) | PT76232B (en) |
| RO (1) | RO86175B (en) |
| SE (1) | SE8300602L (en) |
| TR (1) | TR21950A (en) |
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| JPS5975910A (en) * | 1982-10-25 | 1984-04-28 | Mitsui Petrochem Ind Ltd | Ethylene copolymer |
| FI68632C (en) * | 1983-06-22 | 1985-10-10 | Neste Oy | FOER FARING FRAMSTAELLNING AV SAMPOLYMER AV ETEN OCH LANGKEDJADE ALFA-OLEFINER |
| JPS6088016A (en) * | 1983-10-21 | 1985-05-17 | Mitsui Petrochem Ind Ltd | Ethylene copolymer |
| IT1176299B (en) * | 1984-06-22 | 1987-08-18 | Anic Spa | METHOD FOR THE PREPARATION OF A ZIRCONIUM OR AFHNIUM CATALYST AND PROCESS OF POLYMERIZATION OR COPOLYMERIZATION OF UNSATURATE COMPOUNDS USING THE SAME |
| EP3059261B1 (en) * | 2015-02-23 | 2018-10-03 | Indian Oil Corporation Limited | Process for preparing a catalyst for olefin polymerization and polymerization |
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| US4076698A (en) * | 1956-03-01 | 1978-02-28 | E. I. Du Pont De Nemours And Company | Hydrocarbon interpolymer compositions |
| DE1420399B2 (en) * | 1956-10-19 | 1972-12-07 | Farbwerke Hoechst AG, vormals Mei ster Lucius & Bruning, 6000 Frankfurt | METHOD FOR MANUFACTURING MODIFIED POLYAETHYLENE |
| GB847706A (en) * | 1957-04-17 | 1960-09-14 | Exxon Research Engineering Co | Process for making plastic ethylene-butene copolymers, and products thereof |
| GB1131528A (en) * | 1966-08-01 | 1968-10-23 | Du Pont | Ethylene polymerisation process and apparatus |
| US3666736A (en) * | 1969-03-24 | 1972-05-30 | Phillips Petroleum Co | Low density ethylene-butene copolymers |
| AR206852A1 (en) * | 1975-03-10 | 1976-08-23 | Union Carbide Corp | PROCEDURE FOR PREPARING LOW AND MEDIUM DENSITY ETHYLENE POLYMERS IN A FLUID BED REACTOR |
| GR60862B (en) * | 1976-01-30 | 1978-09-01 | Snam Progetti | Process for olephines polymerization and compositions suitable for the polymerization |
| JPS5952643B2 (en) * | 1977-01-27 | 1984-12-20 | 三井化学株式会社 | ethylene copolymer |
| IT1080687B (en) * | 1977-06-30 | 1985-05-16 | Snam Progetti | TRIALHYGEN TITANIUM-BASED CHEMICAL COMPOSITIONS, PROCEDURE FOR THEIR PREPARATION AND USE |
| FR2405961A1 (en) * | 1977-10-12 | 1979-05-11 | Naphtachimie Sa | PROCESS FOR THE COPOLYMERIZATION OF OLEFINS IN A GAS PHASE IN THE PRESENCE OF A FLUIDIZED COPOLYMER BED AND A CATALYST CONTAINING TITANIUM AND MAGNESIUM |
| IT1110494B (en) * | 1978-08-02 | 1985-12-23 | Montedison Spa | ETHYLENE POLYMERS AND PROCEDURE FOR THEIR PREPARATION |
| JPS5558210A (en) * | 1978-10-26 | 1980-04-30 | Nippon Oil Co Ltd | Production of copolymer |
| JPS5573712A (en) * | 1978-11-29 | 1980-06-03 | Nippon Oil Co Ltd | Preparation of copolymer |
| IT1130243B (en) * | 1980-02-01 | 1986-06-11 | Anic Spa | CHEMICAL COMPOSITION BASED ON TRIALHYGEN TITANIUM, METHOD FOR ITS PREPARATION AND PROCESS OF POLYMERIZATION OR COPOLYMERISATION OF UNSATURATED COMPOUNDS USING THE SAME |
| JPS57105411A (en) * | 1980-12-23 | 1982-06-30 | Mitsubishi Petrochem Co Ltd | Ethylenic copolymer |
-
1982
- 1982-02-12 IT IT8219614A patent/IT1210855B/en active
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- 1983-01-28 GR GR70357A patent/GR78079B/el unknown
- 1983-01-28 GB GB08302384A patent/GB2114584B/en not_active Expired
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- 1983-02-04 SE SE8300602A patent/SE8300602L/en not_active Application Discontinuation
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- 1983-02-08 CH CH708/83A patent/CH659076A5/en not_active IP Right Cessation
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- 1983-02-08 CA CA000421142A patent/CA1203949A/en not_active Expired
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- 1983-02-10 FR FR8302158A patent/FR2521570B1/en not_active Expired
- 1983-02-10 RO RO109969A patent/RO86175B/en unknown
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Also Published As
| Publication number | Publication date |
|---|---|
| TR21950A (en) | 1985-12-04 |
| FR2521570B1 (en) | 1987-02-20 |
| BE895878A (en) | 1983-08-10 |
| GB2114584B (en) | 1985-08-14 |
| PL240435A1 (en) | 1983-08-15 |
| DD207546A5 (en) | 1984-03-07 |
| IE830281L (en) | 1983-08-12 |
| NO830405L (en) | 1983-08-15 |
| DK59783A (en) | 1983-08-13 |
| RO86175A (en) | 1985-03-15 |
| IT8219614A0 (en) | 1982-02-12 |
| LU84641A1 (en) | 1983-09-08 |
| GR78079B (en) | 1984-09-26 |
| ES8403931A1 (en) | 1984-04-01 |
| FR2521570A1 (en) | 1983-08-19 |
| PT76232A (en) | 1983-03-01 |
| PT76232B (en) | 1986-01-27 |
| DE3304758A1 (en) | 1983-08-25 |
| GB2114584A (en) | 1983-08-24 |
| ES519970A0 (en) | 1984-04-01 |
| YU27083A (en) | 1985-10-31 |
| RO86175B (en) | 1985-03-31 |
| IL67871A (en) | 1986-12-31 |
| GB8302384D0 (en) | 1983-03-02 |
| JPS58171409A (en) | 1983-10-08 |
| IL67871A0 (en) | 1983-06-15 |
| DK59783D0 (en) | 1983-02-11 |
| IT1210855B (en) | 1989-09-29 |
| CH659076A5 (en) | 1986-12-31 |
| SE8300602L (en) | 1983-08-13 |
| SE8300602D0 (en) | 1983-02-04 |
| ZA83602B (en) | 1983-12-28 |
| NL8300457A (en) | 1983-09-01 |
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