CA1326733C - Ethylene-.alpha.-olefin copolymer and process for producing the same - Google Patents
Ethylene-.alpha.-olefin copolymer and process for producing the sameInfo
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- CA1326733C CA1326733C CA000601918A CA601918A CA1326733C CA 1326733 C CA1326733 C CA 1326733C CA 000601918 A CA000601918 A CA 000601918A CA 601918 A CA601918 A CA 601918A CA 1326733 C CA1326733 C CA 1326733C
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- ethylene
- alpha
- olefin
- molecular weight
- average molecular
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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
Abstract
ABSTRACT OF THE DISCLOSURE
An ethylene-.alpha.-olefin copolymer is disclosed, which comprises ethylene and an .alpha.-olefin having from 3 to 10 carbon atoms, has an ethylene/.alpha.-olefin molar ratio of from 88/12 to 98/2, and which has a number average molecular weight of from 35,000 to 80,000 and a weight average molecular weight/number average molecular weight ratio of from 1.8/1 to 3.0/1 as determined by gas permeation chromatography. A process for producing the ethylene-.alpha.-olefin copolymer is also disclosed. The ethylene-.alpha.-olefin copolymer exhibits excellent trans-parency and excellent low-temperature heat-sealing properties. The process is advantageous from the stand-point of equipment, energy and cost.
An ethylene-.alpha.-olefin copolymer is disclosed, which comprises ethylene and an .alpha.-olefin having from 3 to 10 carbon atoms, has an ethylene/.alpha.-olefin molar ratio of from 88/12 to 98/2, and which has a number average molecular weight of from 35,000 to 80,000 and a weight average molecular weight/number average molecular weight ratio of from 1.8/1 to 3.0/1 as determined by gas permeation chromatography. A process for producing the ethylene-.alpha.-olefin copolymer is also disclosed. The ethylene-.alpha.-olefin copolymer exhibits excellent trans-parency and excellent low-temperature heat-sealing properties. The process is advantageous from the stand-point of equipment, energy and cost.
Description
1 ET~YLENE-a-OLEFIN COPOLYMER AND
PROCESS FOR PRODUCING T~E SAME
FIELD OF THE INVENTION
This invention relates to an ethylene-a-olefin copolymer and a process for producing the same. More particularly, it relates to an ethylene-~-olefin co-polymer excellent in transparency and low-temperature heat~sealing properties and to a process for producing such an ethylene--olefin copolymer.
BACKGROUND OF THE INVENTION
E~hylene~-oleEin copolymers exhibit excellent characteristics such as heat resistance, weather resis-tance and ozone resistance and have therefore found broad applications as automobile materials, cons~ruc-tional materials, industrial materials and resin modifiers. In particular, ethylene-~-olefin copolymers having a high ethylene content are soft resins having propertieq midway between rubbers and crystalline pla8tic8 and ar~ now in growing demand as packaging ~ film, etc. Inter al;a, copolymers obtained by copoly-merizinq ethylene and an -olefin in the presence of a titanium-based polymeriza~ion catalyst are known as linear low density polye~hylene (hereinater abbreviated a~ LLDPE) and are widely employed~ ~owever, Eilms ~5 produced from LLDP~ do not al~ays sati~fy reguirement~
1 of low-temperature hea~-sealing properties and transparency. The insufficient ~ransparency or heat-sealing properties of the LLDPE are considered attributed to non-uniform composition of ethylene and ~-olefin in the copolymer and broad molecular weight di.stribution.
~n the other hand, several processes for producing ethylene-~-olefin copolymers using a vanadium-based catalyst have been proposed. For example, JP-B-46-21212 (the tPrm "~P-B" as used herein means an "examined published Japanese patent application") discloses a process of solution polymerization of ethylene and an ~-olefin using a catalyst system compri~ed of a vanadium compound and an organoaluminum sompound. According to this process, a copolymer is obtained in the form of a uniform solution, i.e., as dissolved in a polymerization solven~. However, the : vanadium compound uqed ~reatly reduces in catalytic : ac~ivi~y as ~he polymerization temperature increases.
For example, as ~hown in the working examples o~ this patent publication, the polymeri ation activity becomes too low to be suited for practical use in a high temperature range, e.g., at 100C, only to produce a copolymer having broad molecular weight di~trihution and having a high solvent ~tractable content. 3P-B-47-1 26185 discloses a process for producing an ethylene--olefin copolymer by using a halogenated lower aliphatic hydrocarbon or a hydrocarbon having f rom 3 to 5 carbon atoms as a polymerization solvent and a combination of a VOX3 compound and an organoaluminum compound as a catalyst system. Polymerization in a halogenated hydro-carbon produces a polymer as a precipitate insoluble in the polymerization solvent, forming a slurry having a low viscosity as a whole. This is economically advantageGus in stirring or transporting the system but, in turn, there are problems arising from decomposition of the halogenated hydrocarbon, such a~ corrosion of apparatus and storage stability of the polymer. In the case of slurry polymerization in a hydrocarbon solvent having 3 to 5 carbon atoms, closeness of the boilin~
point of this solvent to that of the ethylene-copolymer-izable ~-olefin, particularly propylene or l-bu~ene, gives rise to a great problem in ~eparating the unreacted monomer and the p~l~merization solvent in the purifica~ion ~tep. Further/ from an economical view-point, this proceæ~ is not always reoognized advan-tageous since hydrocarbon~ havîng 3 to 5 carbon atoms have low boiling points and ~erefore require a freezing apparatus ~or liquefication and a pressure-resi~tant apparatus as well a~ a cooliDg medi~m~ Furthermore, the 1 process requires large-sized equipment for an ashing step for removing the catalyst components incorporated into the produced polymer particles.
JP-B-55-24447 discloses a process for producing an ethylene-l-butene copolymer having an ethylene content of from 85 to 95 mol~, in Which copolymerization is effected at a temperature of from -20 to 30C in an aliphatic hydrocarbon having from 6 to 15 carbon atoms as a polymerization solvent in the presence of a cataly~t system composed of a ~oluble vanadium compound and an organoaluminum halide. Similarly, JP-A~63-17912 (the term "JP-A" as used herein means an "unexamined published Japanese patent application") describes a process for copolymerizing ethylene and an ~-olefin at from -20 ~o 30C using a catalyst syste~ composed of a soluble vanadium compound and a chlorinated or~ano-aluminum compound. Both of these processes relate to slurry polymerization with a differen¢e lying in that the Al/V atomic molar ratio is from 2/1 to 50/1 i~ the former proce3s and from S5/1 to 17~/1 in the latter proce~s. According to either pxocess, since poly~eri-zation i~ carried out at a relatively low temperature ~from -20 to 30C), a large quantity of a c~oling medium and an enersy for driving a freezing device are neces~ary. In addit;on, the reaction rate attainea is 1 so low that the retention time in the reaction vessel becomes long, increasing the overall volume of the reaction vessel, which results in large consumption of stirring power in the reaction vessel.
In shortr when ethylene-~-olefin copolymers having a high ethylene content are produced by sluxry polymerization, that is, in a system in which a part of the copolymer produced is insoluble in a polymerization solvent so that the reaction proceeds while the insoluble copolymer being in a precipitated state, by the conventional processes, it is necessary to make a proper choice of a solvent, and the reaction should be conducted at low temperatures, which is disadvantageous from the standpoint of equipment and energy. On the other hand, in the case of solution polymerization in a system in which copolymerization proceeds while the whole copolymer being di~solved in the solvent, the conven~ional processes require relatively high temper-atures a~d sufer from reduction of ca~alyst efficiency, resulting in economical disadvantage.
From all these considerations, it hAs been keenly demanded to develop a ~lurry polymerization techni~ue which can be effected at a midway temperature~
more specifically at around 40 to 65C at which vanadium-based catalyst exerts the pos~ible highest 1 activity, which would be of advantage from the standpoint of equipment, energy, and cost. The most relevant process so far proposed in this connection is found, e.g., in JP-B-46-11028. According to the S disclosed technique, however, the resultin~ copolymer has a much non-uniform composition and a broad molecular weight distribution, thereby possessing poor strength and poor transparency.
SUMMARY OF THE INVENTION
One object of this invention is to eliminate the disadvantages associated with the conventional processes and to provide a process for producing an ethylene-~-olefin copolymer having a narrow molecular weight distribution and a uniform composition by slurry poly-merization with industrial advantages from the stand-point of equipment, energy, and cost.
Another object of this invention is to provide an ethylene--olefin copolymer having a narrow molecular weight di~tribu~ion~ a uniform composition, and a low ~ solvent extractable content, thereby exhibiting sat,~s-factory tran~parency and excellent low-temperature heat-sealing properties.
The inventors have conducted e~tensive investigations on a process for producin~ an ethylene-~-olefin copolymer having a narrow molecular weight 1 distribution and a uniform composition. As a resultf it has now been found that slurry polymerization can be carried out at a low viscosity by using a three-component catalyst system comprising a specific vanadium compound, a specific organoaluminum compound and a specific halogenated ester compound at a specific mixing ratio and by property selecting a copolymerization temperature, a molar ratio of ethylene and an ~-olefin, and a copolymeri~ation solvent to be used. It has also been found that an ethylenP-~-olefin copolymer having the above-described properties can be obtained by slightly elevating the temperature of the system after completion of the copolymerization thereby making it possible to handle the reaction system as a uniform solution and facilitating ashing of the copolymer. ~he present invention has been completed based on these findings.
That is t in one embodiment ~he present invention provides an ethylene-a-olefin copol~mer wh;ch co~priæes ethylene and an ~-olefin having from 3 to 10 carbon atoms, ha~ an ethylene~-olefin molar ratio of from 88/12 to 98/2, and which has a number average molecular weight of from ~5r000 to 80,000 and a weight avera~e molecular weight~numb~r average molecular weight ratio 1 of from 1.8/1 to 3.0/1 as determined by gas permeation chromatography IGPC).
Further, in another embodi~ent the present invention provides a process for producing an ethylene-~-olefin copolymer having an ethylene/ olefin molar ratio of from 88/12 to 98/2 and having a number average molecular~ weight of from 35,000 to 80,000 and a weight average molecular we;ght/number average molecular weight ratio of from 1.8/1 to 3.0/1 as determined by GPCt which comprises copolymerizing ethylene and an a-ole~in havin~
from 3 to 10 carbon atoms at an ethylene/ olefin molar ratio of from 35/65 to 60/40 a~d at a temperature of from 40 to 80C using a oatalyst system composed of a vanadium compound represented by formula:
`15 , wherein R represents a hydrocarbon group; X represents a halogen~atom; and n is a number of from 0 to 3, an organoaluminum compound represented ~y formula:
~U
R'~A~X3_~
wherein R' repre~ent~ a hydrocarbon group; X represents a halogen atom; and m represents a nu~b*r of from 1 to 3, and a halogenated e~ter compound represented by formula:
C - OR"' wherein R" represent~ an organic group derived from a hydrocarbon group having from 1 to 20 carbon atoms by substituting a part or all of the hydrogen atoms thereof with a halogen atom; and R"' represents a hydrocarbon group having from 1 to 20 carbon atoms, at an or~anoaluminum compound/vanadium compound molar ratio of 2.5/1 or more and at a halogenated ester compound/vanadium compound molar ratio of 1.5/1 or more, in a system in ~hich a polymer insoluble in a hydro-carbon solvent and a polymer soluble in a hydrocarbon solvent coexist.
The process of the present invention is characterized in that ~he copolymeriza~ion is oaxried out in a system where a hydroearbon solvent-soluble polymer and a hydrocarbon solvent-insoluble polymer coex~st, more specifically, in a mixed system comprising a di~solved state polymer and insoluble fine poly~er par~icles having a particle size of not more tha~ 0.5 mm. Such a mixed polymeri%ation ~y5t8m, when set at 40~C, contains 95~ by weight or more of the hydrocarbon solvent-insoluble polymer based on the total polymer.
In ~his ca~e, the ~ystem ha~ a low visco~ity ~5 _ 9 _ 1 eharacteristic of a slurry polymerization system. When the system is set at 70C or higher, the system becomes a uniform solution.
DETAILED_DESCRIPTION OF T~E INVENTION
Important in the present invention are choices of a combination of catalyst components, a copolymeriza-tion sol~ent, and a copolymerization temperature.
Specific examples of the vanadium compo~nd represented by formula VO(OR)nX3_n, wherein R, X, and n are as defined above r include WOC13, VO(OCH3)Cl2, VO(OCH3~2Cl, VO(OCH3)3, VOl~C2~5~C12, VO(OC2~5)2C~
Vo(oc2H5)3~ Vo(oc3~7)cl2~ VO~OC3H7)2Cl, vo(oc3 7)3r iso C3~7)C12~ V(~-iSO-~3~7)2Cl, Vo(o-iso-c3~7)3~ and mixtures thereof. These vanadium compounds except for VOC13 can easily be prepared by reacting VOC13 with an alcohol or by reacting VOC13 with VO(OR)3. PreEerred of them are those wherein O~n~l, i.e.~ VOC13~ VO(OC~3)Cl2, VO~OC2~s)Cl2, V1C3~7)C12, and VO(O-iso-C3~7)~l2, ~rom the vie~point of obtaining copol~mers having a narrow molecular weight distribution and a uniform composition.
In particular, VOC13 (n-O~ is the mo~t preferred.
The copolymerization sys.e~ in ~he co-presence of a hydrocarbon ~olvent-insoluble polymer and a hydrocarbon solver.t-soluble polymer may al~o be achieYed by the use of the vanadium compound~ wherein l<n~3, 1 e.g., VO(OC~3)2Cl, VO(OC~3)3, VO(OC~3s)2~l, VO(OC2H5~3 Vo~oc3H7)2cl, VO(OC3H7)3, VO(O-iS-C3H7)2Cl~ a~d VO(O
C3H7)3- However, the ethylene-~-olefin copolymers obtained from such a system have tw~ endothermic peaks in differential thermal analysis (DrA) by ~eans of a differential sCanning calorimeter lDSC), o~e in the region between 80C a~d 105C and the other in the region exceeding lQ5C. Some of s~ch copolymers may suffer from reduction of heat-sealing properties or transparency.
The organoaluminum compound represented by formula R'mAlX3_m, wherein R', X, an~ m are as defined above, which can be used in the catalyst system includes (C~5)2AlCl, tC4H9)2Alcl~ (C6~l3)2AlCl~ ~C2~5)1.~AlCl1.5' ~C4~9)l.~AlC1l.5, (C6~l3)l.5AlC1l.5, C2~5AlCl2, C4~9AlCl2, and C6~l3AlCl2. From the standpoint Oc reaction rate and yield, preferred of them are those wherein 15~52, with (C2~5)1.5AlC1l.5 being more preferred.
The halogenated ester compound represe~ted by formula R"-C-OR"', wherein R" and R"' are as defined above, which can be used a~ a cataly~t component preferably includes those wherei~ R" is a group in which all the hydrogen atoms thereof are substituted with a halogen atom, more preferably perohlorocrotonic acid 1 esters. Specific example~ of the halo~enated ester compound are ethyl dichloroacetate, methyl trichloro-acetate, ethyl trichloroacetate, methyl dichlorophenyl-acetate, ethyl dichlorophenylacet~te, methyl perchloro-erotonate, ethyl perchlorocrotonate, propyl perchloro-crotonate, isopropyl perchlorocrotonate, butyl per-chlorocrQtonate, cyclopropyl perchlorocrotonate, and phenyl perchlorocrotonate.
In the copolymerization system, the vanadium compound concentration ranges from 0.00005 mmol/~ to 5 mmols/~, preferably from 0.0001 mmol/~ to 1 mmol/e. The molar ratio of the organoaluminum compound to the vanadium compound should be 2.5/1 or more, preerably from 2.5/1 to 30/1, and the molar ratio of the halogenated ester compound to the vanadium compound shQuld be 1.5/1 or more. If the organoaluminum compound/vanadium compound molar ratio is le~s than 2.5/1, the copolymerization reaction becomes extremely unstable, resulting in stopping or failing to obtain a desired copolymer having a narrow molecular weight distribution. If the halogenated ester compound/
vanadium compound molar ratio is less than 1.5/1, the resulting copolymer has a broad molecular weî~ht di~tribution.
1The copolymerization according to the present invention is carried out in a hydrocarbon solvent. The hydrocarbon solvent to be used includes aliphatic hydro-carbons, e.g., hexane, heptane, octane, decane, 5dodecane, and kerosine; alicyclic hydrocarbons, e.~., cyclohexane, methylcyclopentane, and methylcyclohexane;
and aromatic hydrocarbons, e.g., benzene, toluene, and xylene. Preferred of them are hexane, heptane, octane, and cyclohexane. The solvent may be partly or wholly 10replaced with an -olefin, e.g., propylene, l-butene~ 1-pentene, and l-hexene.
The copolymeri2ation temperature ranges from 40 to 80~C, preferably from 40 to 65C. If it is lower than 40C, the reaction rate is seriously reduced and, 15in addition, a specific equipment of cooling or freezing would be necessary to remove the reaction heat. On the other hand, at temperatures hi~her than 80 , the whole copolymer produced becomes soluble in the solvent throughout the copolymerization ~ystem to increase the 20viscosi~y of the sy~em, thus so much increasing the po~er required for ~tirring and mixing. At even higher temperatur2s, the polymerization activity of the catalyst is lost, failing to produce a copoly~er.
The copolymerization is carried out under 25atmospheric pressure or under an eleYated pressure, l preferably at a pressure of from l to 30 kg/cm2, more preferably from l to 20 kg/cm2.
The retention time of the copolymerization reaction mixture in the copolymerization vessel ranges from lO to 180 minutes, preferably from 20 to 120 minutes, in average. In order to assure good reproduci-bility i~ obtaining an ethylene-~-olein copolymer with satisfactory physical properties, the total polymer concentration in the copolymerization ~ystem is adjusted not to exceed 15% by weight, preferably not to exceed 12% by weight.
The copolymerization is effected in a system where a hydrocarbon solvent-insoluble polymer and a hydrocarbon solvent-soluble polymer coexist while lS tirring. It is preferable to control the molar ratio of ethylene and ~-olefin to be charged in such a manner :that the hydrocarbon solvent-insoluble polymer content may amount ~o 95~ by weight or more at 40C or the total polymer may solely comprise the hydrocarbon solvent~
soluble polymer at 70C. In such a copol~merization system, the copolymeriza~ion temperature is preferably set at from 40 ~o ~5C, more preferably at from 40 ~o 55C. In this particular system, since the reactio~
proceed with the hydrocarbon solvent-insoluble polymer bein~ suspended in the form of fine particles of 0.5 m~
1 or smaller in diameter, the viscosity of the system can be kept low, the stirring power energy can be minimized, and the reaction heat can easily be removed. Moreover, a satisfactory mixing state of the catalyst and the monomers can be obtained, as is advantageous for obtaining a polymer having a narrow molecular weight distribution and a uniform composition. The temperature in the downstream side of the reaction vessel, on the other hand, is controlled ~t 7DC or higher, whereby the total polymer in this side becomes soluble in the solvent. Such temperature control can thus eliminate the problem due to precipitated polymer particles generally encountered in slurry polymerization systems effected on an industrial scale, i.e., sedimentation and deposition of the polymer particles in areas of insufficient flow in the plant or obstruction of piping.
The weight ratio of the hydrocarbon solvent-insoluble polymer and the hydrocarbon solvent-soluble polymer can be determined by filtering the reaction mixture sampled from the copolymerization system through a metallic net of 300 mesh to separate into a hydrocarbon solvent-soluble matter and a hydrocarbon ~olvent-insoluble matter, removing the hydrocarbon solvent from each matter by drying, and weighing each of the resulting solids.
1 The ethylene-~-olefin copolymer according to the present invention has an ethylene/-olefin molar ratio of from 88/12 to 98/2 and a ratio of weight average molecular weight ~Mw~ to number avera~e molecular weight (Mn), Mw/Mn (hereinafter referred to as a Q value), of from l~R/l to 3.0/1 as determined by GPC. The ethylene-~-olefin.copolymer satisfying these conditions exhibits excellent performance properties in terms of strength at break, elongation, and surfaee hardness as measured according to JIS K-6301. Preferred ethylene--olefin copolymers which are particularly e~cellent in heat-sealing properties and transparency have an ethylene/~-olefin molar ratio of from 92~8 to 96/4 and a Q value o~ from 1.8~1 to 2.6/1, and shows only one endothermic peak as determined with DSC, said peak being between 80C and 105~C.
The ethylene--olefin copolymer according to the present invention has a number average molecular weight of from 35,000 to 80,000 as determined by GPC~ If it is less than 35,000~ the copolymer produced has an insufficient strength. On the other hand, if i~ exceeds 80r300~ the molding processability is poor.
GPC a~ used herein was conducted under the ollowing measurement conditions:
1 GP Chromatograph: 150 C Model, manufactured by Waters Corp.
Column: Shodex~ AC-80M, manufactured by Shoda Denko K.K.
Sample Volume: 300 ~e ~polymer conc.: 0.2~ by weight) Flow Rate: 1 ml/min Temp.: 135C
Solvent 1,2,4-trichlorobenzene A calibration curv~ was prepared in a usual manner by using a standard polystyrene produced by Tosoh lo Corporation. Data were processed by the use o~ Data Proces~or CP-8 Model III, manufactured by Tosoh Corporation.
Molecular weight control of the ethylene/~-olefin copolymer can be done with ~2~ diethylamine, allyl chloride, pyridine-N-oxide, etc., with ~2 being . particularly preferred.
The present invention is now illustrated in greater detail by way of the following Examples~
Comparative Examples, Reference Examples, and Compara-tive ~eference Example~, but it shculd be understood that the present inven~ion is not dee~ed to be limited thereto.
Ethylene and l-butene were continuously co-polymerized by usin~ a 5 e-volume SUS-made polymeriza-tion vessel equipped with a stirrin~ blade.
Hexane as a polymerization solvent was continu-ously fPd into the lower part of the vessel at a rate of 5 e/hr~ while a polymerization mixturP was continuously withdrawn from the upper part of the vessel so as to maintain the volume of the polymerization mixture in the vessel at 5 ~. As a catalyst system, vanadium oxytri chloride, ethylaluminum sesquichloride, and n-butyl per-chlorocrotonate were continuously fed to the upper part of the vessel at a rate of 0.050 mmol/hr, 1.2 mmols/hr, and 0.12 mmol/hr, respectiv~ly. Ethylene and l-~utene as monomers were continuously fed to the lower part of the vessel at a feed rate of 230 g/hr and 360 y/hr, respectively. Molecular weight control was effected with hydrogen. The copolymerization temperature was controlled at 55C by circulatin~ cooling water through a ~acket provided around the ves~el.
The copolymerization reaction was carried out under the above-recited conditions to thereby produce an ethylene-l-butene copolymer in the form of a mixture of a polymerization solven~-insoluble matter and a polymerization solvent-soluble mat~er. A small amount 1 of methanol was added to the polymerization mixture withdrawn from the reaction vessel to ~top the reaction.
Any unreacted monomers were removed from the mixture, the mixture was washed with water, and the solvent was removed by stripping with steam in a large quantity of water. The collected copolymer was dried at 80C under reduced pressure for one day. There was thus obtained an ethylene-l-butene copolymer at an output rate of 170 9/hr.
The ethylene content of the resulting copolymer was found to be 96.1 mol% by infrared absorption analysis. GPS analysis revealed that the copolymer had an Mw of 112,000 and an Mn of 55,000, givin~ a Q value of 2.2/1. The DTA curve of the copolymer o~tained by the use of DSC had a single fusion peak, showing a melting point (Tm~ at 99C and a heat of fusion (~m~ of 19 cal/g.
The polymeriza~ion mixture withdrawn ~rom the reaction vessel was filtered through a metallic net of ~ 30-0 mesh to separate into a solvent-insoluble mat~er and a solvent-soluble matter, and ea¢h of them was weighed to give an insoluble matter/soluble matter weight ratio o~ 61/39.
When the copolymer was press molded, the result.-ing molded article exhibi~ed highly satisfactcry trans-1 parency and had a strength at break of 330 kg~/cm2, an elongation at break of 710~, and a surface hardness of 93, each measured in accordance with JIS K-6301.
Ethylene and l-butene were copolymeriæed in the same manner as in Example 1, except for altering the conditiQn~ as shown in Table 1. Each of the rPsulting copolymers was analyzed and evaluated in the same manner as in Example 1, and ~he results obtained are shown in Table ~. .
EXAMPL~ES 6 AND ?
. Copolymerization was carried out in the same manner as in Example 1, except for replacing l-butene with propylene and altering the polymerization conditions as shown in Table 1. Each of the resulting ethylene-~-olef;n copolymers was analyzed and evaluated : in the same manner as in Example 1, and the resul~s obtalned are shown in Table 2.
COMP RATIVE EXhMPLES l_AND 2 Copolymerization was carried out in the same manner as in Example 1, except for using, as catalyst components, vanadium oxytrichloride and ethylaluminum sesquichloride only but using no n butyl perchloro-crotona~e and altering the reaction conditions as shown in Table 1. Each o~ the resulting copolymers was - 2~
1 ~26733 1 analyzed and evaluated in the same manner as in Example 1, and the results obtained are shown in Table 2.
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~, . ~. ~ ~ ~, .. ~, 3 z E , 1~ e ~ ~ O x COMPARATIVE EXAMPLE_ 3 Copolymerization was carried out in the same manner as in Example 1, except for changing the ethylene feed rate to 100 g/hr and the l-butene feed rate to 500 g/hr. ~he copolymer produced was totally soluble in the h~xane solvent, and the system became a vis~ous solutio~.~ The copolymer recovered was rubber-like and had a low strength at break as 140 kgf/cm2.
0 Copolymerization was carried out in the same manner as in Example 1, except for chanying the ethylene feed rate to 300 g/hr, the l-butene feed ra~e to 300 g/hr~ and the polymerization temperature to 25C. As a result, the copolymerization system became a slurry in which most of the copolymer produced was suspending in the hexane solvent as insoluble fine particles, a part of the copolymer particles being found deposited onto the inner wall of the piping in the downstream side of the outlet of the ves~el. The recovered copolymer had a low elongation at break as 420%.
Ethylene and l-butene were continuously co-polymerized by using the same polymerization vessel as used in Example 1 to which was connected a 10 e-volume SUS-made pressure-resistant stirring tank equipped with - 24 ~
1 a stirrin~ blade, a jacket, and an outlet for with-drawing gasified components at the top thereof ~here-inafter referred to as degassing apparatus).
~exane as a polymeriza~ion solvent was continu-ously fed to the lower part of the vessel at a feed rate o~ 5 ~/hr/ ~hile the polymeriza~ion mixture was continu-ously withdrawn from the upper part of the vessel so as to maintain the volume of the pol~merization mixture in the v~ssel at 5 e and introduced into the degassing apparatus~ The polymerization mixture was further continuously withdrawn from the side of the degassing apparatus so as to control the volume of the polymeriza-tion mixture in the apparatus at 5 e. As a catalyst system, vanadium oxytrichloride, ethylaluminum sesqui-chloride, and ethyl dichlorophenylacetate were continu-ously fed to the lower part of the vessel at a rate of 0.020 mmol/hr, 0~55 mmol/hr, and 0~0~0 mmol/hr, respectively. Ethylene and l-butene were continuously ed to the lower part of the vessel at a rate of 155 g/hr and 175 g/hr, respectively. Molecular weight control was effected with hydro~en, The copolymeriza-tion temperature was controlled at 55C by circulatin~
cooling water through a jacket provided around the vessel.
2~
^` 1 326733 1 The copolymerization reaction was carried out under the above-recited conditions to thereby produce an ethylene-l-butene copolymer in the form of a mixture of a polymerization solvent-insoluble matter and a polymerization solvent-soluble matter. The polymeriza-tion mixture was continuously withdrawn from the vessel and intro~duced into the degassing apparatus. A small amount of methanol was added to the polymerization mixture in the degassing apparatus to stop the reaction.
The inner temperature of the apparatus was controlled at 40C while removing the unreacted monomers. The mixture withdrawn fr~m the degassing apparatus assumed a slurry condition in which copolymer particles having a particle size of from about 0.01 to 0.1 mm wPre suspending in thP
hexane solvent.
The polymerization mi~ture sampled from the degassing apparatus was filtered through a metallic net of 300 mesh to separate into a polymerization solvent-insoluble matter and a polymerization solvent-soluble matter, and each of them was wPighed to give an insoluble matter/soluble matter weight ratio of 98/2.
On the other hand, the polymerization mixture sampled from the polymerization vessel was found to have an insoluble matter/soluble matter weight ratio of 44/56.
1 While continuing the polymerization, warm water was then circulated through the jacket of the degassing apparatus to control the inner temperature at 70C. The polymerization mixture withdrawn from the apparatus contained no solid particles and, instead, the copolymer produced was found to be in a dissolved ~tate in the hexane so.lvent.
Polymerization was further continued, and the inner temperature of the degassing apparatus was cooled to 40C. Then, the polymerization mixture returned to the slurry state oomprising suspending copolymer particles.
The structural values of the copolymer sampled from the polymerization mixture kept at 70C were consistent with those of the copolymer sampled from the mixture cooled to 40C within measurement errors. The resulting copolymer was found to have an ethylene content of 94 mol% by infrared absorption analysis; an Mw of 9R,OOO~ an Mn of 49r000 by GPC analysis, giving a Q value of 2.0/l; a single fusion peak showing a Tm of 95C and a ~m of 23 cal/g by DSC. Transparency and m~chanical properties of the copolymer were evaluated in the same manner as in Example 1. The polymerization conditions used are shown in Table 3, and ~he results of analyses and evaluations are ~hown in Table 4.
~ - \
1 EXAMPLES 9 ~ND 10 AND COMPA~ATIV~ EXAMPLES 5 AND 6 Copolymerization was carried out in the same manner as in Example 8, except for changing the feed .rates of the polymerization solvent, organoaluminum compound, halogenated ester compound, ethylene, and 1-butene or changing the kind or amount of the vanadium compound~as shown in Table 3.
Each of the resulting copolymers was analyzed and evaluated in the same manner as in Example 1, and the results obtained are shown in Table 4.
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1 3267~3 Each of the copolymers obtained in Examples 8, 9, and 10 was mixed with 0.1% by weight of calcium stearate, 0.2% by weight of octadecyl-3-~3',5'-di-t-S butyl-4-hydroxyphenyl)propionate ("IRGANOX~ 1076"
produced by Chiba-Geigy AG), and 0.05% by weight of trisnonylphenyl phosphite ("ANTIGENE~ TNP" produced by Sumitomo Chemical Co., Ltd.). The resulting compound was pelletized and molded into a film having a thickness of 30 ~m. Physical properties of the film are shown in Table 5.
COMPARATIVE REFERENCE EXA~LES 1 TO 3 Each of the copolymers obtained in Comparative Examples 5 and 5 and an ~LDP2 was compounded with additives and molded into a film in the same manner as in Reference Examples 1 to 3. Physical properties of each of the resulting films are shown in Table 5.
2~
Reference ~xample No. C~mp. Ref. Ex. No.
1 2 3 _ 1 2 3 Copolymer Ex. 8 Ex. 9 Ex. 10 CG~P. Comp. LLDPE
Ex. 5 Ex. 6 *5 Density~l 0.9064 0.9081 0.9012 0.9018 0.90~0 0.9120 ~g/cm3) ~aze*2 (%? 2.8 3~2 2.2 6.9 25.3 10.4 CXS*3 (~) 1.6 1.5 2.1 3.6 5.7 10.3 Heat-Sealable 92 95 90 ~3 98 110 Temp *4 ( C) Note: *1: Measured at 25C
*2: Measured according to ASTM D-1003 *3: A weight loss of a test specimen on immersion in xylene at 30C for 24 hours was determined.
*4: Two sheets of a sample film (width: 1.5 om) were fused together under a pressure of 2 kg/cm2 for a sealin~ time of 1 second by : means of a heat sealer, and the sealed area was subjected to peel test. The minimum heat sealing temperature which provided such a sealing ~trength that the sealed area was divided into two layers through breaking without involving peeling at the sealed 1 surface was taken as a heat-sealable temperature.
*5: A trial product of SUMIKAT~ENE~ L prod~ced by Sumitomo Chemical Co., Ltd., having a melt flow index ~MFI) of l.9 at 190C, which is confirmed to be an ethylene-l-butene copolymer by infrared absorption analysis.
As described above, the present invention provides an ethylene-a-olefin copolymer having a narrow molecular weight, a uniform ~omposition, and a s~all solvent extractable content and thereby exhibiting excellent ~ransparency and low-temperature heat-sealing properties. The pro.cess according to the present invention for producing such an ethylene-~-olefin copolymer, in which copolymerization is carried out in such a system that a hydrocarbon solvent-insoluble : polymer and a hydrocarbon solvent-soluble polymer coexist, is advantagPous from the standpoint of equipment, energy, and cost.
While the invention has been described in detail and with reference ~o specific embodiments thereof, it will be apparent to one skilled in the art tha~ various : changes and modifications can be made therein without departing from the spirit and scope thereof.
PROCESS FOR PRODUCING T~E SAME
FIELD OF THE INVENTION
This invention relates to an ethylene-a-olefin copolymer and a process for producing the same. More particularly, it relates to an ethylene-~-olefin co-polymer excellent in transparency and low-temperature heat~sealing properties and to a process for producing such an ethylene--olefin copolymer.
BACKGROUND OF THE INVENTION
E~hylene~-oleEin copolymers exhibit excellent characteristics such as heat resistance, weather resis-tance and ozone resistance and have therefore found broad applications as automobile materials, cons~ruc-tional materials, industrial materials and resin modifiers. In particular, ethylene-~-olefin copolymers having a high ethylene content are soft resins having propertieq midway between rubbers and crystalline pla8tic8 and ar~ now in growing demand as packaging ~ film, etc. Inter al;a, copolymers obtained by copoly-merizinq ethylene and an -olefin in the presence of a titanium-based polymeriza~ion catalyst are known as linear low density polye~hylene (hereinater abbreviated a~ LLDPE) and are widely employed~ ~owever, Eilms ~5 produced from LLDP~ do not al~ays sati~fy reguirement~
1 of low-temperature hea~-sealing properties and transparency. The insufficient ~ransparency or heat-sealing properties of the LLDPE are considered attributed to non-uniform composition of ethylene and ~-olefin in the copolymer and broad molecular weight di.stribution.
~n the other hand, several processes for producing ethylene-~-olefin copolymers using a vanadium-based catalyst have been proposed. For example, JP-B-46-21212 (the tPrm "~P-B" as used herein means an "examined published Japanese patent application") discloses a process of solution polymerization of ethylene and an ~-olefin using a catalyst system compri~ed of a vanadium compound and an organoaluminum sompound. According to this process, a copolymer is obtained in the form of a uniform solution, i.e., as dissolved in a polymerization solven~. However, the : vanadium compound uqed ~reatly reduces in catalytic : ac~ivi~y as ~he polymerization temperature increases.
For example, as ~hown in the working examples o~ this patent publication, the polymeri ation activity becomes too low to be suited for practical use in a high temperature range, e.g., at 100C, only to produce a copolymer having broad molecular weight di~trihution and having a high solvent ~tractable content. 3P-B-47-1 26185 discloses a process for producing an ethylene--olefin copolymer by using a halogenated lower aliphatic hydrocarbon or a hydrocarbon having f rom 3 to 5 carbon atoms as a polymerization solvent and a combination of a VOX3 compound and an organoaluminum compound as a catalyst system. Polymerization in a halogenated hydro-carbon produces a polymer as a precipitate insoluble in the polymerization solvent, forming a slurry having a low viscosity as a whole. This is economically advantageGus in stirring or transporting the system but, in turn, there are problems arising from decomposition of the halogenated hydrocarbon, such a~ corrosion of apparatus and storage stability of the polymer. In the case of slurry polymerization in a hydrocarbon solvent having 3 to 5 carbon atoms, closeness of the boilin~
point of this solvent to that of the ethylene-copolymer-izable ~-olefin, particularly propylene or l-bu~ene, gives rise to a great problem in ~eparating the unreacted monomer and the p~l~merization solvent in the purifica~ion ~tep. Further/ from an economical view-point, this proceæ~ is not always reoognized advan-tageous since hydrocarbon~ havîng 3 to 5 carbon atoms have low boiling points and ~erefore require a freezing apparatus ~or liquefication and a pressure-resi~tant apparatus as well a~ a cooliDg medi~m~ Furthermore, the 1 process requires large-sized equipment for an ashing step for removing the catalyst components incorporated into the produced polymer particles.
JP-B-55-24447 discloses a process for producing an ethylene-l-butene copolymer having an ethylene content of from 85 to 95 mol~, in Which copolymerization is effected at a temperature of from -20 to 30C in an aliphatic hydrocarbon having from 6 to 15 carbon atoms as a polymerization solvent in the presence of a cataly~t system composed of a ~oluble vanadium compound and an organoaluminum halide. Similarly, JP-A~63-17912 (the term "JP-A" as used herein means an "unexamined published Japanese patent application") describes a process for copolymerizing ethylene and an ~-olefin at from -20 ~o 30C using a catalyst syste~ composed of a soluble vanadium compound and a chlorinated or~ano-aluminum compound. Both of these processes relate to slurry polymerization with a differen¢e lying in that the Al/V atomic molar ratio is from 2/1 to 50/1 i~ the former proce3s and from S5/1 to 17~/1 in the latter proce~s. According to either pxocess, since poly~eri-zation i~ carried out at a relatively low temperature ~from -20 to 30C), a large quantity of a c~oling medium and an enersy for driving a freezing device are neces~ary. In addit;on, the reaction rate attainea is 1 so low that the retention time in the reaction vessel becomes long, increasing the overall volume of the reaction vessel, which results in large consumption of stirring power in the reaction vessel.
In shortr when ethylene-~-olefin copolymers having a high ethylene content are produced by sluxry polymerization, that is, in a system in which a part of the copolymer produced is insoluble in a polymerization solvent so that the reaction proceeds while the insoluble copolymer being in a precipitated state, by the conventional processes, it is necessary to make a proper choice of a solvent, and the reaction should be conducted at low temperatures, which is disadvantageous from the standpoint of equipment and energy. On the other hand, in the case of solution polymerization in a system in which copolymerization proceeds while the whole copolymer being di~solved in the solvent, the conven~ional processes require relatively high temper-atures a~d sufer from reduction of ca~alyst efficiency, resulting in economical disadvantage.
From all these considerations, it hAs been keenly demanded to develop a ~lurry polymerization techni~ue which can be effected at a midway temperature~
more specifically at around 40 to 65C at which vanadium-based catalyst exerts the pos~ible highest 1 activity, which would be of advantage from the standpoint of equipment, energy, and cost. The most relevant process so far proposed in this connection is found, e.g., in JP-B-46-11028. According to the S disclosed technique, however, the resultin~ copolymer has a much non-uniform composition and a broad molecular weight distribution, thereby possessing poor strength and poor transparency.
SUMMARY OF THE INVENTION
One object of this invention is to eliminate the disadvantages associated with the conventional processes and to provide a process for producing an ethylene-~-olefin copolymer having a narrow molecular weight distribution and a uniform composition by slurry poly-merization with industrial advantages from the stand-point of equipment, energy, and cost.
Another object of this invention is to provide an ethylene--olefin copolymer having a narrow molecular weight di~tribu~ion~ a uniform composition, and a low ~ solvent extractable content, thereby exhibiting sat,~s-factory tran~parency and excellent low-temperature heat-sealing properties.
The inventors have conducted e~tensive investigations on a process for producin~ an ethylene-~-olefin copolymer having a narrow molecular weight 1 distribution and a uniform composition. As a resultf it has now been found that slurry polymerization can be carried out at a low viscosity by using a three-component catalyst system comprising a specific vanadium compound, a specific organoaluminum compound and a specific halogenated ester compound at a specific mixing ratio and by property selecting a copolymerization temperature, a molar ratio of ethylene and an ~-olefin, and a copolymeri~ation solvent to be used. It has also been found that an ethylenP-~-olefin copolymer having the above-described properties can be obtained by slightly elevating the temperature of the system after completion of the copolymerization thereby making it possible to handle the reaction system as a uniform solution and facilitating ashing of the copolymer. ~he present invention has been completed based on these findings.
That is t in one embodiment ~he present invention provides an ethylene-a-olefin copol~mer wh;ch co~priæes ethylene and an ~-olefin having from 3 to 10 carbon atoms, ha~ an ethylene~-olefin molar ratio of from 88/12 to 98/2, and which has a number average molecular weight of from ~5r000 to 80,000 and a weight avera~e molecular weight~numb~r average molecular weight ratio 1 of from 1.8/1 to 3.0/1 as determined by gas permeation chromatography IGPC).
Further, in another embodi~ent the present invention provides a process for producing an ethylene-~-olefin copolymer having an ethylene/ olefin molar ratio of from 88/12 to 98/2 and having a number average molecular~ weight of from 35,000 to 80,000 and a weight average molecular we;ght/number average molecular weight ratio of from 1.8/1 to 3.0/1 as determined by GPCt which comprises copolymerizing ethylene and an a-ole~in havin~
from 3 to 10 carbon atoms at an ethylene/ olefin molar ratio of from 35/65 to 60/40 a~d at a temperature of from 40 to 80C using a oatalyst system composed of a vanadium compound represented by formula:
`15 , wherein R represents a hydrocarbon group; X represents a halogen~atom; and n is a number of from 0 to 3, an organoaluminum compound represented ~y formula:
~U
R'~A~X3_~
wherein R' repre~ent~ a hydrocarbon group; X represents a halogen atom; and m represents a nu~b*r of from 1 to 3, and a halogenated e~ter compound represented by formula:
C - OR"' wherein R" represent~ an organic group derived from a hydrocarbon group having from 1 to 20 carbon atoms by substituting a part or all of the hydrogen atoms thereof with a halogen atom; and R"' represents a hydrocarbon group having from 1 to 20 carbon atoms, at an or~anoaluminum compound/vanadium compound molar ratio of 2.5/1 or more and at a halogenated ester compound/vanadium compound molar ratio of 1.5/1 or more, in a system in ~hich a polymer insoluble in a hydro-carbon solvent and a polymer soluble in a hydrocarbon solvent coexist.
The process of the present invention is characterized in that ~he copolymeriza~ion is oaxried out in a system where a hydroearbon solvent-soluble polymer and a hydrocarbon solvent-insoluble polymer coex~st, more specifically, in a mixed system comprising a di~solved state polymer and insoluble fine poly~er par~icles having a particle size of not more tha~ 0.5 mm. Such a mixed polymeri%ation ~y5t8m, when set at 40~C, contains 95~ by weight or more of the hydrocarbon solvent-insoluble polymer based on the total polymer.
In ~his ca~e, the ~ystem ha~ a low visco~ity ~5 _ 9 _ 1 eharacteristic of a slurry polymerization system. When the system is set at 70C or higher, the system becomes a uniform solution.
DETAILED_DESCRIPTION OF T~E INVENTION
Important in the present invention are choices of a combination of catalyst components, a copolymeriza-tion sol~ent, and a copolymerization temperature.
Specific examples of the vanadium compo~nd represented by formula VO(OR)nX3_n, wherein R, X, and n are as defined above r include WOC13, VO(OCH3)Cl2, VO(OCH3~2Cl, VO(OCH3)3, VOl~C2~5~C12, VO(OC2~5)2C~
Vo(oc2H5)3~ Vo(oc3~7)cl2~ VO~OC3H7)2Cl, vo(oc3 7)3r iso C3~7)C12~ V(~-iSO-~3~7)2Cl, Vo(o-iso-c3~7)3~ and mixtures thereof. These vanadium compounds except for VOC13 can easily be prepared by reacting VOC13 with an alcohol or by reacting VOC13 with VO(OR)3. PreEerred of them are those wherein O~n~l, i.e.~ VOC13~ VO(OC~3)Cl2, VO~OC2~s)Cl2, V1C3~7)C12, and VO(O-iso-C3~7)~l2, ~rom the vie~point of obtaining copol~mers having a narrow molecular weight distribution and a uniform composition.
In particular, VOC13 (n-O~ is the mo~t preferred.
The copolymerization sys.e~ in ~he co-presence of a hydrocarbon ~olvent-insoluble polymer and a hydrocarbon solver.t-soluble polymer may al~o be achieYed by the use of the vanadium compound~ wherein l<n~3, 1 e.g., VO(OC~3)2Cl, VO(OC~3)3, VO(OC~3s)2~l, VO(OC2H5~3 Vo~oc3H7)2cl, VO(OC3H7)3, VO(O-iS-C3H7)2Cl~ a~d VO(O
C3H7)3- However, the ethylene-~-olefin copolymers obtained from such a system have tw~ endothermic peaks in differential thermal analysis (DrA) by ~eans of a differential sCanning calorimeter lDSC), o~e in the region between 80C a~d 105C and the other in the region exceeding lQ5C. Some of s~ch copolymers may suffer from reduction of heat-sealing properties or transparency.
The organoaluminum compound represented by formula R'mAlX3_m, wherein R', X, an~ m are as defined above, which can be used in the catalyst system includes (C~5)2AlCl, tC4H9)2Alcl~ (C6~l3)2AlCl~ ~C2~5)1.~AlCl1.5' ~C4~9)l.~AlC1l.5, (C6~l3)l.5AlC1l.5, C2~5AlCl2, C4~9AlCl2, and C6~l3AlCl2. From the standpoint Oc reaction rate and yield, preferred of them are those wherein 15~52, with (C2~5)1.5AlC1l.5 being more preferred.
The halogenated ester compound represe~ted by formula R"-C-OR"', wherein R" and R"' are as defined above, which can be used a~ a cataly~t component preferably includes those wherei~ R" is a group in which all the hydrogen atoms thereof are substituted with a halogen atom, more preferably perohlorocrotonic acid 1 esters. Specific example~ of the halo~enated ester compound are ethyl dichloroacetate, methyl trichloro-acetate, ethyl trichloroacetate, methyl dichlorophenyl-acetate, ethyl dichlorophenylacet~te, methyl perchloro-erotonate, ethyl perchlorocrotonate, propyl perchloro-crotonate, isopropyl perchlorocrotonate, butyl per-chlorocrQtonate, cyclopropyl perchlorocrotonate, and phenyl perchlorocrotonate.
In the copolymerization system, the vanadium compound concentration ranges from 0.00005 mmol/~ to 5 mmols/~, preferably from 0.0001 mmol/~ to 1 mmol/e. The molar ratio of the organoaluminum compound to the vanadium compound should be 2.5/1 or more, preerably from 2.5/1 to 30/1, and the molar ratio of the halogenated ester compound to the vanadium compound shQuld be 1.5/1 or more. If the organoaluminum compound/vanadium compound molar ratio is le~s than 2.5/1, the copolymerization reaction becomes extremely unstable, resulting in stopping or failing to obtain a desired copolymer having a narrow molecular weight distribution. If the halogenated ester compound/
vanadium compound molar ratio is less than 1.5/1, the resulting copolymer has a broad molecular weî~ht di~tribution.
1The copolymerization according to the present invention is carried out in a hydrocarbon solvent. The hydrocarbon solvent to be used includes aliphatic hydro-carbons, e.g., hexane, heptane, octane, decane, 5dodecane, and kerosine; alicyclic hydrocarbons, e.~., cyclohexane, methylcyclopentane, and methylcyclohexane;
and aromatic hydrocarbons, e.g., benzene, toluene, and xylene. Preferred of them are hexane, heptane, octane, and cyclohexane. The solvent may be partly or wholly 10replaced with an -olefin, e.g., propylene, l-butene~ 1-pentene, and l-hexene.
The copolymeri2ation temperature ranges from 40 to 80~C, preferably from 40 to 65C. If it is lower than 40C, the reaction rate is seriously reduced and, 15in addition, a specific equipment of cooling or freezing would be necessary to remove the reaction heat. On the other hand, at temperatures hi~her than 80 , the whole copolymer produced becomes soluble in the solvent throughout the copolymerization ~ystem to increase the 20viscosi~y of the sy~em, thus so much increasing the po~er required for ~tirring and mixing. At even higher temperatur2s, the polymerization activity of the catalyst is lost, failing to produce a copoly~er.
The copolymerization is carried out under 25atmospheric pressure or under an eleYated pressure, l preferably at a pressure of from l to 30 kg/cm2, more preferably from l to 20 kg/cm2.
The retention time of the copolymerization reaction mixture in the copolymerization vessel ranges from lO to 180 minutes, preferably from 20 to 120 minutes, in average. In order to assure good reproduci-bility i~ obtaining an ethylene-~-olein copolymer with satisfactory physical properties, the total polymer concentration in the copolymerization ~ystem is adjusted not to exceed 15% by weight, preferably not to exceed 12% by weight.
The copolymerization is effected in a system where a hydrocarbon solvent-insoluble polymer and a hydrocarbon solvent-soluble polymer coexist while lS tirring. It is preferable to control the molar ratio of ethylene and ~-olefin to be charged in such a manner :that the hydrocarbon solvent-insoluble polymer content may amount ~o 95~ by weight or more at 40C or the total polymer may solely comprise the hydrocarbon solvent~
soluble polymer at 70C. In such a copol~merization system, the copolymeriza~ion temperature is preferably set at from 40 ~o ~5C, more preferably at from 40 ~o 55C. In this particular system, since the reactio~
proceed with the hydrocarbon solvent-insoluble polymer bein~ suspended in the form of fine particles of 0.5 m~
1 or smaller in diameter, the viscosity of the system can be kept low, the stirring power energy can be minimized, and the reaction heat can easily be removed. Moreover, a satisfactory mixing state of the catalyst and the monomers can be obtained, as is advantageous for obtaining a polymer having a narrow molecular weight distribution and a uniform composition. The temperature in the downstream side of the reaction vessel, on the other hand, is controlled ~t 7DC or higher, whereby the total polymer in this side becomes soluble in the solvent. Such temperature control can thus eliminate the problem due to precipitated polymer particles generally encountered in slurry polymerization systems effected on an industrial scale, i.e., sedimentation and deposition of the polymer particles in areas of insufficient flow in the plant or obstruction of piping.
The weight ratio of the hydrocarbon solvent-insoluble polymer and the hydrocarbon solvent-soluble polymer can be determined by filtering the reaction mixture sampled from the copolymerization system through a metallic net of 300 mesh to separate into a hydrocarbon solvent-soluble matter and a hydrocarbon ~olvent-insoluble matter, removing the hydrocarbon solvent from each matter by drying, and weighing each of the resulting solids.
1 The ethylene-~-olefin copolymer according to the present invention has an ethylene/-olefin molar ratio of from 88/12 to 98/2 and a ratio of weight average molecular weight ~Mw~ to number avera~e molecular weight (Mn), Mw/Mn (hereinafter referred to as a Q value), of from l~R/l to 3.0/1 as determined by GPC. The ethylene-~-olefin.copolymer satisfying these conditions exhibits excellent performance properties in terms of strength at break, elongation, and surfaee hardness as measured according to JIS K-6301. Preferred ethylene--olefin copolymers which are particularly e~cellent in heat-sealing properties and transparency have an ethylene/~-olefin molar ratio of from 92~8 to 96/4 and a Q value o~ from 1.8~1 to 2.6/1, and shows only one endothermic peak as determined with DSC, said peak being between 80C and 105~C.
The ethylene--olefin copolymer according to the present invention has a number average molecular weight of from 35,000 to 80,000 as determined by GPC~ If it is less than 35,000~ the copolymer produced has an insufficient strength. On the other hand, if i~ exceeds 80r300~ the molding processability is poor.
GPC a~ used herein was conducted under the ollowing measurement conditions:
1 GP Chromatograph: 150 C Model, manufactured by Waters Corp.
Column: Shodex~ AC-80M, manufactured by Shoda Denko K.K.
Sample Volume: 300 ~e ~polymer conc.: 0.2~ by weight) Flow Rate: 1 ml/min Temp.: 135C
Solvent 1,2,4-trichlorobenzene A calibration curv~ was prepared in a usual manner by using a standard polystyrene produced by Tosoh lo Corporation. Data were processed by the use o~ Data Proces~or CP-8 Model III, manufactured by Tosoh Corporation.
Molecular weight control of the ethylene/~-olefin copolymer can be done with ~2~ diethylamine, allyl chloride, pyridine-N-oxide, etc., with ~2 being . particularly preferred.
The present invention is now illustrated in greater detail by way of the following Examples~
Comparative Examples, Reference Examples, and Compara-tive ~eference Example~, but it shculd be understood that the present inven~ion is not dee~ed to be limited thereto.
Ethylene and l-butene were continuously co-polymerized by usin~ a 5 e-volume SUS-made polymeriza-tion vessel equipped with a stirrin~ blade.
Hexane as a polymerization solvent was continu-ously fPd into the lower part of the vessel at a rate of 5 e/hr~ while a polymerization mixturP was continuously withdrawn from the upper part of the vessel so as to maintain the volume of the polymerization mixture in the vessel at 5 ~. As a catalyst system, vanadium oxytri chloride, ethylaluminum sesquichloride, and n-butyl per-chlorocrotonate were continuously fed to the upper part of the vessel at a rate of 0.050 mmol/hr, 1.2 mmols/hr, and 0.12 mmol/hr, respectiv~ly. Ethylene and l-~utene as monomers were continuously fed to the lower part of the vessel at a feed rate of 230 g/hr and 360 y/hr, respectively. Molecular weight control was effected with hydrogen. The copolymerization temperature was controlled at 55C by circulatin~ cooling water through a ~acket provided around the ves~el.
The copolymerization reaction was carried out under the above-recited conditions to thereby produce an ethylene-l-butene copolymer in the form of a mixture of a polymerization solven~-insoluble matter and a polymerization solvent-soluble mat~er. A small amount 1 of methanol was added to the polymerization mixture withdrawn from the reaction vessel to ~top the reaction.
Any unreacted monomers were removed from the mixture, the mixture was washed with water, and the solvent was removed by stripping with steam in a large quantity of water. The collected copolymer was dried at 80C under reduced pressure for one day. There was thus obtained an ethylene-l-butene copolymer at an output rate of 170 9/hr.
The ethylene content of the resulting copolymer was found to be 96.1 mol% by infrared absorption analysis. GPS analysis revealed that the copolymer had an Mw of 112,000 and an Mn of 55,000, givin~ a Q value of 2.2/1. The DTA curve of the copolymer o~tained by the use of DSC had a single fusion peak, showing a melting point (Tm~ at 99C and a heat of fusion (~m~ of 19 cal/g.
The polymeriza~ion mixture withdrawn ~rom the reaction vessel was filtered through a metallic net of ~ 30-0 mesh to separate into a solvent-insoluble mat~er and a solvent-soluble matter, and ea¢h of them was weighed to give an insoluble matter/soluble matter weight ratio o~ 61/39.
When the copolymer was press molded, the result.-ing molded article exhibi~ed highly satisfactcry trans-1 parency and had a strength at break of 330 kg~/cm2, an elongation at break of 710~, and a surface hardness of 93, each measured in accordance with JIS K-6301.
Ethylene and l-butene were copolymeriæed in the same manner as in Example 1, except for altering the conditiQn~ as shown in Table 1. Each of the rPsulting copolymers was analyzed and evaluated in the same manner as in Example 1, and ~he results obtained are shown in Table ~. .
EXAMPL~ES 6 AND ?
. Copolymerization was carried out in the same manner as in Example 1, except for replacing l-butene with propylene and altering the polymerization conditions as shown in Table 1. Each of the resulting ethylene-~-olef;n copolymers was analyzed and evaluated : in the same manner as in Example 1, and the resul~s obtalned are shown in Table 2.
COMP RATIVE EXhMPLES l_AND 2 Copolymerization was carried out in the same manner as in Example 1, except for using, as catalyst components, vanadium oxytrichloride and ethylaluminum sesquichloride only but using no n butyl perchloro-crotona~e and altering the reaction conditions as shown in Table 1. Each o~ the resulting copolymers was - 2~
1 ~26733 1 analyzed and evaluated in the same manner as in Example 1, and the results obtained are shown in Table 2.
'10 o 3 K ~ N O Cl~ ~r a~ ~ U a OU~
Ul . .
~ O E S u~ o u~ o o o u~
D. ~ _, ~ ` w ~ ~ Nl D~ O tn ~ ~ ~I ~ ~I ~ I N N
E ~ ^ o ~ Z
~ O
E ~1 o ~ ~ N O t~ 10 X li~ 8 o ~ o ~ w ~o o ~ u~
O ~ .0 . 1 ~ z S 1~ N O
''~ .C O O u~ In M~ e W tn ~ ~ ~
~O ~ ~
v ~ 0 :: ~ N N r~ J N
C tn E ~ ~
0 E ~
c ~ n O
P4 ~ t ~ E ~ N
U E3 ~:1 L~ C _i n N
la ~ "~ N ,~ o O
~ C~ O O O O O O O
P-~ ~ ol~
~1 N ~ ~r ~n ' ,1 ~ 1~ . ' N
Cl o. c' '' ~0 Cl, O- a a ~ E ~ fi 111 X t~ XX O ~t ~ P~
-- ~2 -- .
1 32673~
10 ~ ~ ~ O ~ r~
1 ~ ~ o~
C
P. ~ ~ _ o o o o o o o o ~ m OP,~ o O
I c 1~ w C .C
C L~ ~ O O C:l O O O O O O
h ~ ~ i ~ N ~ _I N r1 rl ~ I O~
U~ I _ 10 ~ ~ ` 'O ~ ~ L' ~ I O _ S ~ ~ g ~ $
h c IDI ~ t~l p~
^ ~ O _l m ~
I El U ~ ~0 U7 ~ o ~n ~ ~
~ a E~
W
: 5 . ~, ~d r O ~ - ~ N ~
r~
æ ~ O O o O O O 0 O 0 O ~:3 0 0 0 0 0 0 0 ~ O O O O O O O C~ O
.~ O O O O O O O O O
In ~ ~ O ~ ~ U~
u~ o ~ W ~ ~ ~ ~r C ~ 13 . O ~ O . , O
O ~ ~ ~ ~ W
w ~ r~ ~ ~ o 01 ~ ~ ~ ~ ~n 0 al .
~, . ~. ~ ~ ~, .. ~, 3 z E , 1~ e ~ ~ O x COMPARATIVE EXAMPLE_ 3 Copolymerization was carried out in the same manner as in Example 1, except for changing the ethylene feed rate to 100 g/hr and the l-butene feed rate to 500 g/hr. ~he copolymer produced was totally soluble in the h~xane solvent, and the system became a vis~ous solutio~.~ The copolymer recovered was rubber-like and had a low strength at break as 140 kgf/cm2.
0 Copolymerization was carried out in the same manner as in Example 1, except for chanying the ethylene feed rate to 300 g/hr, the l-butene feed ra~e to 300 g/hr~ and the polymerization temperature to 25C. As a result, the copolymerization system became a slurry in which most of the copolymer produced was suspending in the hexane solvent as insoluble fine particles, a part of the copolymer particles being found deposited onto the inner wall of the piping in the downstream side of the outlet of the ves~el. The recovered copolymer had a low elongation at break as 420%.
Ethylene and l-butene were continuously co-polymerized by using the same polymerization vessel as used in Example 1 to which was connected a 10 e-volume SUS-made pressure-resistant stirring tank equipped with - 24 ~
1 a stirrin~ blade, a jacket, and an outlet for with-drawing gasified components at the top thereof ~here-inafter referred to as degassing apparatus).
~exane as a polymeriza~ion solvent was continu-ously fed to the lower part of the vessel at a feed rate o~ 5 ~/hr/ ~hile the polymeriza~ion mixture was continu-ously withdrawn from the upper part of the vessel so as to maintain the volume of the pol~merization mixture in the v~ssel at 5 e and introduced into the degassing apparatus~ The polymerization mixture was further continuously withdrawn from the side of the degassing apparatus so as to control the volume of the polymeriza-tion mixture in the apparatus at 5 e. As a catalyst system, vanadium oxytrichloride, ethylaluminum sesqui-chloride, and ethyl dichlorophenylacetate were continu-ously fed to the lower part of the vessel at a rate of 0.020 mmol/hr, 0~55 mmol/hr, and 0~0~0 mmol/hr, respectively. Ethylene and l-butene were continuously ed to the lower part of the vessel at a rate of 155 g/hr and 175 g/hr, respectively. Molecular weight control was effected with hydro~en, The copolymeriza-tion temperature was controlled at 55C by circulatin~
cooling water through a jacket provided around the vessel.
2~
^` 1 326733 1 The copolymerization reaction was carried out under the above-recited conditions to thereby produce an ethylene-l-butene copolymer in the form of a mixture of a polymerization solvent-insoluble matter and a polymerization solvent-soluble matter. The polymeriza-tion mixture was continuously withdrawn from the vessel and intro~duced into the degassing apparatus. A small amount of methanol was added to the polymerization mixture in the degassing apparatus to stop the reaction.
The inner temperature of the apparatus was controlled at 40C while removing the unreacted monomers. The mixture withdrawn fr~m the degassing apparatus assumed a slurry condition in which copolymer particles having a particle size of from about 0.01 to 0.1 mm wPre suspending in thP
hexane solvent.
The polymerization mi~ture sampled from the degassing apparatus was filtered through a metallic net of 300 mesh to separate into a polymerization solvent-insoluble matter and a polymerization solvent-soluble matter, and each of them was wPighed to give an insoluble matter/soluble matter weight ratio of 98/2.
On the other hand, the polymerization mixture sampled from the polymerization vessel was found to have an insoluble matter/soluble matter weight ratio of 44/56.
1 While continuing the polymerization, warm water was then circulated through the jacket of the degassing apparatus to control the inner temperature at 70C. The polymerization mixture withdrawn from the apparatus contained no solid particles and, instead, the copolymer produced was found to be in a dissolved ~tate in the hexane so.lvent.
Polymerization was further continued, and the inner temperature of the degassing apparatus was cooled to 40C. Then, the polymerization mixture returned to the slurry state oomprising suspending copolymer particles.
The structural values of the copolymer sampled from the polymerization mixture kept at 70C were consistent with those of the copolymer sampled from the mixture cooled to 40C within measurement errors. The resulting copolymer was found to have an ethylene content of 94 mol% by infrared absorption analysis; an Mw of 9R,OOO~ an Mn of 49r000 by GPC analysis, giving a Q value of 2.0/l; a single fusion peak showing a Tm of 95C and a ~m of 23 cal/g by DSC. Transparency and m~chanical properties of the copolymer were evaluated in the same manner as in Example 1. The polymerization conditions used are shown in Table 3, and ~he results of analyses and evaluations are ~hown in Table 4.
~ - \
1 EXAMPLES 9 ~ND 10 AND COMPA~ATIV~ EXAMPLES 5 AND 6 Copolymerization was carried out in the same manner as in Example 8, except for changing the feed .rates of the polymerization solvent, organoaluminum compound, halogenated ester compound, ethylene, and 1-butene or changing the kind or amount of the vanadium compound~as shown in Table 3.
Each of the resulting copolymers was analyzed and evaluated in the same manner as in Example 1, and the results obtained are shown in Table 4.
- 2~ -o ~ 1 326733 o ~ a ul o _l ~ l l l o P~ ' ~ O E ~
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.- c ~ o ~ ~OD 0 o I I ~ ~I v ::1 c V ~ E o v ~ I ~ L ~~ ,~ o r tl ~J C: C ~ U~ O '~
~ o 3 ~ O O o ~ ~ e O ~ I~
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_ ~: ~ ~ ~ ~ O a~
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~ ~ ~ ~
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~ v ~ ~
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~ ~ m~
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tn ~ .x ~3 = = ~ o ~ t~ N
E _IN ~ or _~
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~ o ~ ~ ~ ,r S~ O O o O
~ r l ~ O trl O O O O O
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~ O ~ a u~
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1 3267~3 Each of the copolymers obtained in Examples 8, 9, and 10 was mixed with 0.1% by weight of calcium stearate, 0.2% by weight of octadecyl-3-~3',5'-di-t-S butyl-4-hydroxyphenyl)propionate ("IRGANOX~ 1076"
produced by Chiba-Geigy AG), and 0.05% by weight of trisnonylphenyl phosphite ("ANTIGENE~ TNP" produced by Sumitomo Chemical Co., Ltd.). The resulting compound was pelletized and molded into a film having a thickness of 30 ~m. Physical properties of the film are shown in Table 5.
COMPARATIVE REFERENCE EXA~LES 1 TO 3 Each of the copolymers obtained in Comparative Examples 5 and 5 and an ~LDP2 was compounded with additives and molded into a film in the same manner as in Reference Examples 1 to 3. Physical properties of each of the resulting films are shown in Table 5.
2~
Reference ~xample No. C~mp. Ref. Ex. No.
1 2 3 _ 1 2 3 Copolymer Ex. 8 Ex. 9 Ex. 10 CG~P. Comp. LLDPE
Ex. 5 Ex. 6 *5 Density~l 0.9064 0.9081 0.9012 0.9018 0.90~0 0.9120 ~g/cm3) ~aze*2 (%? 2.8 3~2 2.2 6.9 25.3 10.4 CXS*3 (~) 1.6 1.5 2.1 3.6 5.7 10.3 Heat-Sealable 92 95 90 ~3 98 110 Temp *4 ( C) Note: *1: Measured at 25C
*2: Measured according to ASTM D-1003 *3: A weight loss of a test specimen on immersion in xylene at 30C for 24 hours was determined.
*4: Two sheets of a sample film (width: 1.5 om) were fused together under a pressure of 2 kg/cm2 for a sealin~ time of 1 second by : means of a heat sealer, and the sealed area was subjected to peel test. The minimum heat sealing temperature which provided such a sealing ~trength that the sealed area was divided into two layers through breaking without involving peeling at the sealed 1 surface was taken as a heat-sealable temperature.
*5: A trial product of SUMIKAT~ENE~ L prod~ced by Sumitomo Chemical Co., Ltd., having a melt flow index ~MFI) of l.9 at 190C, which is confirmed to be an ethylene-l-butene copolymer by infrared absorption analysis.
As described above, the present invention provides an ethylene-a-olefin copolymer having a narrow molecular weight, a uniform ~omposition, and a s~all solvent extractable content and thereby exhibiting excellent ~ransparency and low-temperature heat-sealing properties. The pro.cess according to the present invention for producing such an ethylene-~-olefin copolymer, in which copolymerization is carried out in such a system that a hydrocarbon solvent-insoluble : polymer and a hydrocarbon solvent-soluble polymer coexist, is advantagPous from the standpoint of equipment, energy, and cost.
While the invention has been described in detail and with reference ~o specific embodiments thereof, it will be apparent to one skilled in the art tha~ various : changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (13)
1. An ethylene-.alpha.-olefin copolymer which comprises ethylene and an .alpha.-olefin having from 3 to 10 carbon atoms, has an ethylene/.alpha.-olefin molar ratio of from 88/12 to 98/2, and which has a number average molecular weight of from 35,000 to 80,000 and a weight average molecular weight/number average molecular weight ratio of from 1.8/1 to 3.0/1 as determined by gas permeation chromatography.
2. An ethylene-.alpha.-olefin copolymer which comprises ethylene and an .alpha.-olefin having from 3 to 10 carbon atoms, has an ethylene/.alpha.-olefin molar ratio of from 92/8 to 96/4, has a number average molecular weight of from 35,000 to 80,000 and a weight average molecular weiqht/number average molecular weight ratio of from 1.8/1 to 2.6/1 as determined by gas permeation chromato-graphy, and which shows a single endothermic peak as determined by means of a differential scanning calori-meter, said endothermic peak being in the range of from 80°C to 105°C,
3. A process for producing an ethylene-.alpha.-olefin copolymer having an ethylene/.alpha.-olefin molar ratio of from 88/12 to 98/2 and having a number average molecular weight of from 35,000 to 80,000 and a weight average molecular weight/number average molecular weight ratio of from 1.8/1 to 3.0/1 as determined by gas permeation chromatography, which comprises copolymerizing ethylene and an .alpha.-olefin having from 3 to 10 carbon atoms at an ethylene/.alpha.-olefin molar ratio of from 35/65 to 60/40 at a temperature of from 40 to 80°C using a catalyst system composed of a vanadium compound represented by formula:
VO(OR)nX3-n wherein R represents a hydrocarbon group; X represents a halogen atom; and n is a number of from 0 to 3, an organoaluminum compound represented by formula:
R'mA?X3-m wherein R' represents a hydrocarbon group; X represents a halogen atom; and m represents a number of from 1 to 3, and a halogenated ester compound represented by formula:
wherein R" represents an organic group derived from a hydrocarbon group having from 1 to 20 carbon atoms by substituting a part or all of the hydrogen atoms thereof with a halogen atom; and R"' represents a hydrocarbon group having from 1 to 20 carbon atoms, at an organoaluminum compound/vanadium compound molar ratio of 2.5/1 or more and at a halogenated ester compound/vanadium compound molar ratio of 1.5/1 or more, in a system in which a polymer insoluble in a hydrocarbon solvent and a polymer soluble in a hydrocarbon solvent coexist.
VO(OR)nX3-n wherein R represents a hydrocarbon group; X represents a halogen atom; and n is a number of from 0 to 3, an organoaluminum compound represented by formula:
R'mA?X3-m wherein R' represents a hydrocarbon group; X represents a halogen atom; and m represents a number of from 1 to 3, and a halogenated ester compound represented by formula:
wherein R" represents an organic group derived from a hydrocarbon group having from 1 to 20 carbon atoms by substituting a part or all of the hydrogen atoms thereof with a halogen atom; and R"' represents a hydrocarbon group having from 1 to 20 carbon atoms, at an organoaluminum compound/vanadium compound molar ratio of 2.5/1 or more and at a halogenated ester compound/vanadium compound molar ratio of 1.5/1 or more, in a system in which a polymer insoluble in a hydrocarbon solvent and a polymer soluble in a hydrocarbon solvent coexist.
4. A process for producing an ethylene-.alpha.-olefin copolymer having an ethylene/.alpha.-olefin molar ratio of from 92/8 to 96/4 and having a number average molecular weight of from 35,000 to 80,000 and a weight average molecular weight/number average molecular weight ratio of from 1.8/1 to 2.6/1 as determined by gas permeation chromatography, and showing a single endothermic peak as determined by means of a differential scanning calorimeter, said endothermic peak being in the range of from 80°C to 105°C, which comprises copolymerizing ethylene and an .alpha.-olefin having from 4 to 8 carbon atoms at an ethylene/.alpha.-olefin molar ratio of from 40/60 to 58/42 at a temperature of from 40 to 65°C using a catalyst system composed of a vanadium compound represented by formula:
VO(OR)nX3-n wherein R represents a hydrocarbon group; X represents a halogen atom; and n is a number of from 0 to 1, an organoaluminum compound represented by formula:
R'mA?X3-m wherein R' represents a hydrocarbon group; X represents a halogen atom; and m represents a number of from 1 to 2, and a halogenated ester compound represented by formula:
wherein R" represents an organic group derived from a hydrocarbon group having from 1 to 20 carbon atoms by substituting a part or all of the hydrogen atoms thereof with a halogen atom; and R''' represents a hydrocarbon group having from 1 to 20 carbon atoms, at an organoaluminum compound/vanadium compound molar ratio of from 2.5/1 to 30/1 and at a halogenated ester compound/vanadium compound molar ratio of 1.5/1 or more, in a system in which a polymer insoluble in a hydrocarbon solvent and a polymer soluble in a hydrocarbon solvent coexist, said hydrocarbon solvent-insoluble polymer is 95% by weight or more based on the total polymer at 40°C and 100% by weight based on the total polymer at 70°C.
VO(OR)nX3-n wherein R represents a hydrocarbon group; X represents a halogen atom; and n is a number of from 0 to 1, an organoaluminum compound represented by formula:
R'mA?X3-m wherein R' represents a hydrocarbon group; X represents a halogen atom; and m represents a number of from 1 to 2, and a halogenated ester compound represented by formula:
wherein R" represents an organic group derived from a hydrocarbon group having from 1 to 20 carbon atoms by substituting a part or all of the hydrogen atoms thereof with a halogen atom; and R''' represents a hydrocarbon group having from 1 to 20 carbon atoms, at an organoaluminum compound/vanadium compound molar ratio of from 2.5/1 to 30/1 and at a halogenated ester compound/vanadium compound molar ratio of 1.5/1 or more, in a system in which a polymer insoluble in a hydrocarbon solvent and a polymer soluble in a hydrocarbon solvent coexist, said hydrocarbon solvent-insoluble polymer is 95% by weight or more based on the total polymer at 40°C and 100% by weight based on the total polymer at 70°C.
5. A process as claimed in claim 3, wherein n in the formula representing the vanadium compound is 0.
6. A process as claimed in claim 4, wherein n in the formula representing the vanadium compound is 0.
7. A process as claimed in claim 3, wherein m in the formula representing the organoaluminum compound is 1.5.
8. A process as claimed in claim 4, wherein m in the formula representing the organoaluminum compound is 1.5.
9. A process as claimed in claim 3, wherein said halogenated ester compound is a perchlorocrotonic acid ester.
10. A process as claimed in claim 4, wherein said halogenated ester compound is a perchlorocrotonic acid ester.
11. A process as claimed in claim 3, wherein said .alpha.-olefin is 1-butene.
12. A process as claimed in claim 4, wherein said .alpha. -olefin is 1-butene.
13. An ethylene-.alpha.-olefin copolymer produced by a process as claimed in any of claims 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14252288 | 1988-06-08 | ||
| JP142522/88 | 1988-06-08 | ||
| JP141854/89 | 1989-06-01 | ||
| JP1141854A JP2805841B2 (en) | 1988-06-08 | 1989-06-01 | Ethylene-α-olefin copolymer and method for producing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1326733C true CA1326733C (en) | 1994-02-01 |
Family
ID=26474018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000601918A Expired - Fee Related CA1326733C (en) | 1988-06-08 | 1989-06-06 | Ethylene-.alpha.-olefin copolymer and process for producing the same |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5082908A (en) |
| EP (1) | EP0346098B1 (en) |
| CA (1) | CA1326733C (en) |
| DE (1) | DE68910589T2 (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6025448A (en) | 1989-08-31 | 2000-02-15 | The Dow Chemical Company | Gas phase polymerization of olefins |
| US6538080B1 (en) | 1990-07-03 | 2003-03-25 | Bp Chemicals Limited | Gas phase polymerization of olefins |
| US5674342A (en) | 1991-10-15 | 1997-10-07 | The Dow Chemical Company | High drawdown extrusion composition and process |
| US5278272A (en) | 1991-10-15 | 1994-01-11 | The Dow Chemical Company | Elastic substantialy linear olefin polymers |
| US5582923A (en) | 1991-10-15 | 1996-12-10 | The Dow Chemical Company | Extrusion compositions having high drawdown and substantially reduced neck-in |
| US5783638A (en) | 1991-10-15 | 1998-07-21 | The Dow Chemical Company | Elastic substantially linear ethylene polymers |
| US5395471A (en) | 1991-10-15 | 1995-03-07 | The Dow Chemical Company | High drawdown extrusion process with greater resistance to draw resonance |
| US5525695A (en) * | 1991-10-15 | 1996-06-11 | The Dow Chemical Company | Elastic linear interpolymers |
| JPH09502464A (en) * | 1993-06-21 | 1997-03-11 | デーエスエム ナムローゼ フェンノートシャップ | Process for the preparation of low molecular weight copolymers of ethylene with at least one other 1-alkene |
| US5332793A (en) * | 1993-06-28 | 1994-07-26 | Union Carbide Chemicals & Plastics Technology Corporation | Ethylene/propylene copolymer rubbers |
| US5480850A (en) * | 1993-06-28 | 1996-01-02 | Union Carbide Chemical & Plastics Technology Corporation | Ethylene/propylene copolymer rubbers |
| US5342907A (en) * | 1993-06-28 | 1994-08-30 | Union Carbide Chemicals & Plastics Technology Corporation | Ethylene/propylene copolymer rubbers |
| US5416053A (en) * | 1993-06-28 | 1995-05-16 | Union Carbide Chemicals & Plastics Technology Corporation | Homogenous polyethylenes and ethylene/propylene copolymers rubbers |
| US5502127A (en) * | 1994-03-31 | 1996-03-26 | Union Carbide Chemicals & Plastics Technology Corporation | Process for production of homogeneous polyethylene |
| US5410003A (en) * | 1994-03-31 | 1995-04-25 | Union Carbide Chemicals & Plastics Technology Corporation | Process for production of homogeneous polyethylenes |
| US5492986A (en) * | 1994-03-31 | 1996-02-20 | Union Carbide Chemicals & Plastics Technology Corporation | Process for producing homogeneous polyethylenes |
| US5773106A (en) | 1994-10-21 | 1998-06-30 | The Dow Chemical Company | Polyolefin compositions exhibiting heat resistivity, low hexane-extractives and controlled modulus |
| US5569516A (en) * | 1995-03-03 | 1996-10-29 | Union Carbide Chem Plastic | Membrane and mixture comprising a thermoplastic elastomer |
| IT1283587B1 (en) * | 1996-04-11 | 1998-04-22 | Enichem Elastomers | PROCEDURE FOR THE PREPARATION OF POLYMER MIXTURES BASED ON ELASTOMERIC COPOLYMERS EP (D) M |
| EP0967230B1 (en) * | 1998-06-24 | 2003-01-02 | Bayer Aktiengesellschaft | Catalyst system for the preparation of olefin (co)polymers |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3301834A (en) * | 1963-09-11 | 1967-01-31 | Hercules Inc | Polymerization of olefins |
| US3622548A (en) * | 1966-09-02 | 1971-11-23 | Huels Chemische Werke Ag | Polymers and catalyst compositions |
| CA849081A (en) * | 1967-03-02 | 1970-08-11 | Du Pont Of Canada Limited | PRODUCTION OF ETHYLENE/.alpha.-OLEFIN COPOLYMERS OF IMPROVED PHYSICAL PROPERTIES |
| DE1720643A1 (en) * | 1967-04-05 | 1971-06-16 | Bunawerke Huels Gmbh | Process for the production of amorphous copolymers from ethylene and higher alpha-olefins in suspensions with modified organometallic mixed catalysts |
| GB1403372A (en) * | 1972-01-13 | 1975-08-28 | Int Synthetic Rubber | Alpha monoolefin polymerisation process |
| DE2532115A1 (en) * | 1975-07-18 | 1977-02-03 | Huels Chemische Werke Ag | HIGH MOLECULAR SEMI-CRYSTALLINE SATURATED TERPOLYMERS WITH IMPROVED RAW PROPERTIES |
| JPS5524447A (en) * | 1978-08-09 | 1980-02-21 | Fujitsu Ltd | Method of testing ceramic circuit board |
| JPS57105411A (en) * | 1980-12-23 | 1982-06-30 | Mitsubishi Petrochem Co Ltd | Ethylenic copolymer |
| JPH0714981B2 (en) * | 1986-07-10 | 1995-02-22 | 日本合成ゴム株式会社 | Method for producing ethylene-α-olefin copolymer |
| JPH072812B2 (en) * | 1986-07-11 | 1995-01-18 | 日本合成ゴム株式会社 | Ethylene copolymer and method for producing the same |
-
1989
- 1989-06-06 CA CA000601918A patent/CA1326733C/en not_active Expired - Fee Related
- 1989-06-07 DE DE89305752T patent/DE68910589T2/en not_active Expired - Fee Related
- 1989-06-07 EP EP89305752A patent/EP0346098B1/en not_active Expired - Lifetime
- 1989-06-08 US US07/363,654 patent/US5082908A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US5082908A (en) | 1992-01-21 |
| EP0346098A3 (en) | 1991-04-17 |
| DE68910589D1 (en) | 1993-12-16 |
| DE68910589T2 (en) | 1994-03-24 |
| EP0346098A2 (en) | 1989-12-13 |
| EP0346098B1 (en) | 1993-11-10 |
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