WO1997021746A1 - Processus de production de copolymeres de propylene bimodal - Google Patents

Processus de production de copolymeres de propylene bimodal Download PDF

Info

Publication number
WO1997021746A1
WO1997021746A1 PCT/US1996/019304 US9619304W WO9721746A1 WO 1997021746 A1 WO1997021746 A1 WO 1997021746A1 US 9619304 W US9619304 W US 9619304W WO 9721746 A1 WO9721746 A1 WO 9721746A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrocarbon
propylene
copolymer
weight
reactor
Prior art date
Application number
PCT/US1996/019304
Other languages
English (en)
Inventor
Mahmoud R. Rifi
Carlo F. Martino
Original Assignee
Union Carbide Chemicals & Plastics Technology Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Union Carbide Chemicals & Plastics Technology Corporation filed Critical Union Carbide Chemicals & Plastics Technology Corporation
Priority to AU11290/97A priority Critical patent/AU1129097A/en
Publication of WO1997021746A1 publication Critical patent/WO1997021746A1/fr

Links

Classifications

    • 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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
    • C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
    • C08F297/083—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene

Definitions

  • This invention relates to a process for the production of polypropylene copolymers, both random and impact.
  • Random copolymers of propylene and one or more alpha-olefins generally exhibit good clarity, low temperature impact strength, and melt sealing characteristics. It would be advantageous, however, for certain applications such as food containers if these random copolymers could be provided with further improvements in clarity and impact strength as well as processability.
  • impact polypropylene copolymers Polypropylene homopolymers are widely used for many consumer and industrial applications where high impact strength at low temperatures is not required. For applications requiring a high level of low temperature impact strength, so-called “impact polypropylene copolymers” are used. These polypropylene copolymers are usually manufactured by the incorporation of an elastomeric impact modifier, e.g., an ethylene/propylene copolymer rubber (EPR), into a homopolymer matrix either by blending the homopolymer with the EPR or by producing the copolymer in situ.
  • EPR ethylene/propylene copolymer rubber
  • Impact copolymers generally have excellent low temperature properties, but suffer from a deficiency known as "stress whitening" or "blushing".
  • An object of this invention is to provide a process for the production of a random and impact copolymers of propylene and one or more alpha-olefins, which exhibit improved impact strength and processability.
  • a catalyst system comprising (i) a catalyst precursor, which includes titanium, magnesium and an electron donor; (ii) a hydrocarbylaluminum cocatalyst; and (iii) a selectivity control agent in one or more reactors, under polymerization conditions; and
  • a second embodiment of the invention is represented by (i) a copolymer of propylene and one or more alpha-olefins, and blended therewith (ii) one or more saturated alicyclic hydrocarbon(s), said hydrocarbon(s) being liquid at blending temperature, non-polar, essentially amorphous, and containing less than about 15 percent by weight paraffin wax, in an amount of about 0.1 to about 20 parts by weight of hydrocarbon(s) per 100 parts by weight of component (i), said copolymer, after blending, exhibiting bimodality.
  • a third embodiment is an in situ process for the production of bimodal impact polypropylene copolymers comprising an ethylene/propylene or 1-butene copolymer incorporated into a matrix of propylene homopolymer or copolymer comprising the following steps:
  • a catalyst system comprising (i) a catalyst precursor, which includes titanium, magnesium and an electron donor; (ii) a hydrocarbylaluminum cocatalyst; and (iii) a selectivity control agent in a first reactor, under polymerization conditions, such that a matrix of homopolymer of propylene or copolymer of propylene and alpha olefin(s), which includes active catalyst, is produced;
  • step (b) passing the matrix from step (a) into a second reactor;
  • a fourth embodiment of the invention is represented by an impact polypropylene copolymer comprising (i) an ethylene/propylene or 1-butene copolymer incorporated into a matrix of propylene homopolymer or copolymer and blended therewith (ii) one or more saturated alicyclic hydrocarbon(s), said hydrocarbon(s) being liquid at blending temperature, non-polar, essentially amorphous, and containing less than about 15 percent by weight paraffin wax, in an amount of about 0.1 to about 20 parts by weight of hydrocarbon(s) per 100 parts by weight of component (i), said impact copolymer exhibiting bimodality after blending.
  • the process steps and conditions and the catalyst system used in the reactor(s) are exemplified in United States Patent 4,414,132; 4,882,380; and 5,093,415, and the reactors are preferably gas phase reactors such as the fluidized bed reactor described in United States Patent 4,482,687.
  • Other transition metal catalyst systems useful in the preparation of polypropylene can also be used including, for example, metallocene catalyst systems such as those described in United States Patents 4,937,299 and 5,317,036. Many of the transition metal catalyst systems are referred to as Ziegler-Natta catalyst systems.
  • a typical catalyst system is made up of a catalyst precursor, which includes magnesium, titanium, chlorine, and an electron donor; an organoaluminum compound, which can be referred to as a cocatalyst; and a selectivity control agent.
  • the selectivity control agent is defined as an additive, which modifies the catalyst precursor in such a manner as to increase the overall percentage of isotactic crystalline polymer produced.
  • the catalyst precursor can be obtained by halogenating a magnesium compound having the formula MgR2-nXn wherein each R is independently an alkoxide, aryloxide, or carboxylate group, X is a halogen, and n is 0 or 1 with a tetravalent titanium halide in the presence of a halohydrocarbon and an electron donor; contacting the halogenated product with a tetravalent titanium halide, optionally treating the resulting solid with an aromatic acid halide; washing the halogenated product to remove unreacted titanium compounds; and recovering the solid product.
  • the atomic or mole ratios of catalyst components are generally as follows:
  • Suitable halogen containing magnesium compounds that can be used to prepare the catalyst precursor are alkoxy and aryloxy magnesium halides such as isobutoxy magnesium chloride, ethoxy magnesium bromide, phenoxy magnesium iodide, cumyloxy magnesium bromide, and naphthenoxy magnesium chloride.
  • Magnesium compounds which can be used are magnesium dialkoxides, diaryloxides, and carboxylates having 2 to 24 carbon atoms such as magnesium di-isopropoxide, magnesium diethoxide, magnesium dibutoxide, magnesium diphenoxide, magnesium dinaphthenoxide, and ethoxy magnesium isobutoxide, magnesium dioctanoate, and magnesium dipropionate.
  • Magnesium compounds having one alkoxide and aryloxide group can also be employed. Examples of such compounds are ethoxy magnesium phenoxide and napthenoxide magnesium isoamyloxide. Also suitable are compounds having one carboxylate group and one alkoxide, aryloxide, or halide group such as ethoxy magnesium octanoate, phenoxy magnesium propionate, and chloromagnesium dodecanoate.
  • Suitable halides of tetravalent titanium include arloxy- or alkoxy di- and tri-halides, such as dihexoxy titanium dibromide, isopropoxy titanium triiodide, and phenoxy titanium trichloride, are preferred.
  • the halohydrocarbons employed can be aromatic or aliphatic. Each aliphatic halohydrocarbon preferably contains from 1 to 12 carbon atoms and at least 2 halogen atoms.
  • the aliphatic halohydrocarbons include carbon tetrachloride, dibromomethane, trichloromethane, 1,2-dichloroethane, dichlorobutane, 1,1,3- trichloroethane, trichlorocyclohexane, dichlorofluoroethane, trichloropropane, trichlorofluorooctane, dibromodifuluorodecane, hexachloroethane, and tetrachloroisooctane.
  • Carbon tetrachloride and 1,1,3-trichloroethane are preferred.
  • Aliphatic halohydrocarbons containing only one halogen atom per molecule such as butyl chloride and amyl chloride, can also be employed.
  • Suitable aromatic halohydrocarbons include chlorobenzene, bromobenzene, dichlorobenzene, dichloride bromobenzene, naphthyl chloride, clorotoluene, and dichlorotoluene.
  • Chlorobenzene is the most preferred aromatic halohydrocarbon.
  • Suitable electron donors which can be used in the Mg/Ti complex (as an inside electron donor) separately or complexed with the organoaluminum compound, are ethers, mono- or polycarboxyhc acid esters, ketones, phenols, amines, amides, imines, nitriles, silanes, - phosphines, phosphites, stilbenes, arsines, phosphoramides, and alcoholates.
  • the selectivity control agent (the outside electron donor) is generally different from the inside electron donor.
  • esters of carboxylic acids such as ethyl and methyl benzoate, p-methoxy ethyl benzoate, ethylacrylate, methyl methacrylate, ethyl acetate, p-chloroethyl benzoate, p-amino hexyl benzoate, isopropyl naphthenate, n-amyl toluate, ethyl cyclohexanoate, and propyl pivalate.
  • amines are N,N,N',N' - tetramethylethylene diamine, 1,24-trimethyl piperazine, and 2,2,6,6- tetramethyl piperidine.
  • the preferred electron donor for use in preparing the catalyst precursor is ethyl benzoate.
  • the preferred electron donor for use as a selectivity control agent is para-ethoxy ethyl benzoate.
  • outside electron donor a silicon compound containing a silicon oxygen carbon linkage wherein the atomic ratio of aluminum in the hydrocarbyl aluminum cocatalyst to silicon in the silicon compound is in the range of about 0.5:1 to about 100:1 and the atomic ratio of said aluminum to the titanium in the catalyst precursor is in the range of about 5:1 to about 300:1.
  • the polycarboxyhc acid ester is characterized by a molecularly rigid structure wherein two ester groups are attached to adjacent carbon atoms of the molecule and lie in a single plane.
  • Such esters include: (a) polycarboxyhc acid esters containing two ester groups which are attached to ortho carbon atoms of a monocyclic or polycyclic aromatic ring, each of said ester groups being further linked to a branched or unbranched chain hydrocarbon radical; (b) polycarboxyhc acid esters containing two ester groups which are attached to vicinal carbon atoms of a non-aromatic monocyclic or polycyclic ring and which lie in a syn configuration with respect to each other, each of said ester groups being further linked to a branched or unbranched chain hydrocarbon radical; and (c) polycarboxyhc acid esters containing two ester groups which are attached to vicinal double bonded carbon atoms of an unsaturated aliphatic compound and which lie in a syn
  • polycarboxyhc acid esters which can be employed as inside electron donors are dimethyl phthalate, diethyl phthalate, di-n- propyl phthalate, diisobutyl phthalate, di-tert-butyl phthalate, diisoamyl phthalate, di-tertamyl phthalate, dineopent l phthalate, di- e-ethylhexyl phthalate, di-2-ethyldecyl phthalate, diethyl-1,2- fluorenedicarboxylate, diisoprophyl-l,2-ferrocenedicarboxylate, cis- diisobutyl-cyclobutane-l,2-dicarboxylate, endo-diisobutyl-5- norbornene-2,3-dicarboxylate and endo-diisobutyl-bicyclo [2.2.2]oct-5- ene-2,3-dicarboxylate, di
  • the silicon compounds employed as selectivity control agents (outside electron donors) in the catalyst system employed in the process of the invention contain at least one silicon-oxygen-carbon linkage.
  • Suitable silicon compounds include compounds having the formula
  • R is a hydrocarbon radical having 1 to 20 carbon atoms
  • Y is -OR' or -OCOR' wherein R' is a hydrocarbon radical having 1 to 20 carbon atoms
  • X is hydrogen or halogen
  • m is an integer having a value of 0 to 3
  • n is an integer having a value of 1 to 4
  • p is an integer having a value of 0 or 1
  • m + n + p is equal to 4.
  • R and R' can be the same or different, and, if desired, substituted with any substituent which is inert under the reaction conditions employed during polymerization.
  • R and R' contain from 1 to 10 carbon atoms when they are aliphatic or cycloaliphatic, and from 6 to 10 carbon atoms when they are aromatic.
  • Silicon compounds in which two or more silicon atoms are linked to each other by an oxygen atom may also be employed, provided that the requisite silicon-oxygen-carbon linkage is also present.
  • the hydrocarbyl aluminum cocatalyst can be represented by the formula R3AI wherein each R is an alkyl, cycloalkyl, aryl, or hydride radical; at least one R is a hydrocarbyl radical; two or three R radicals can be joined in a cyclic radical forming a heterocyclic structure; each R can be alike or different; and each R, which is a hydrocarbyl radical, has 1 to 20 carbon atoms, and preferably 1 to 10 carbon atoms.
  • each alkyl radical can be straight or branched chain and such hydrocarbyl radical can be a mixed radical, i.e., the radical can contain alkyl, aryl, and/or cycloalkyl groups.
  • radicals are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, 2-methylpentyl, heptyl, octyl, isoctyl, 2-ethylhexyl, 5,5-dimethylhexyl, nonyl, decyl, isodecyl, undecyl, dodecyl, phenyl, phenethyl, methoxyphenyl, benzyl, tolyl, xylyl, naphthyl, naphthal, methylnaphthyl, cyclohexyl, cycloheptyl, and cyclooctyl.
  • hydrocarbyl aluminum compounds are as follows: triisobutyl aluminum, trihexylaluminum, di- isobutylaluminum dihydride, hexylaluminum dihydride, di- isobutylhexylaluminum, isobutyl dihexylaluminum, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, trioctylaluminum, tridecylaluminum, tridodecylaluminum, tribenzylaluminum, triphenylaluminum, trinaphthylaluminum, and tritoylaluminum.
  • the preferred hydrocarbyl aluminums are triethylaluminum, triisobutylaluminum, trihexylaluminum, di-isobutylaluminum hydride, and dihexylaluminum hydride.
  • the acid halide mentioned above as optional is the derivative of the ester compound used as an inside electron donor.
  • the halide is a chloride or bromide.
  • the acid halide can contain 7 to 22 carbon atoms and one or more aromatic rings.
  • the polymerization can be conducted in one or more reactors using gas phase, slurry, or solution processes; however, the polymerization is preferably carried out in one reactor and in the gas phase.
  • gas phase polymerizations fluidized bed reactors are the reactors of choice.
  • impact copolymers the same applies except that two or more reactors are used, preferably two reactors, and the second reactor, in particular, is preferably operated in the gas phase.
  • a typical fluidized bed reactor can be described as follows:
  • the bed is usually made up of the same granular resin that is to be produced in the reactor.
  • the bed comprises formed polymer particles, growing polymer particles, and catalyst particles fluidized by polymerizable and modifying gaseous components introduced at a flow rate or velocity sufficient to cause the particles to separate and act as a fluid.
  • the fluidizing gas is made up of the initial feed, feed, and cycle (recycle) gas, i.e., monomers and, if desired, modifiers and/or an inert carrier gas.
  • the essential parts of the reaction system are the vessel, the bed, the gas distribution plate, inlet and outlet piping, a compressor, a cycle gas cooler, and a product discharge system. In the vessel, above the bed, there is a velocity reduction zone, and in the bed a reaction zone. Both are above the gas distribution plate.
  • Each fluidized bed reactor is, generally, operated at a temperature in the range of about 40° C. to about 150°C. and preferably about 60°C. to about 120°C. and a pressure of about 50 psig to about 700 psig and preferably about 250 psig to about 550 psig.
  • the velocity of the fluidizing gas is in the range of about 0.1 to about 3.0 feet per second and preferably about 0.5 to about 2.0 feet per second.
  • the weight flow ratio of monomer to catalyst in the first reactor is about 1000:1 to about 100,000:1 and is preferably about 10,000:1 to about 100,000:1.
  • a mixture of propylene and one or more alpha-olefin(s) is introduced together with hydrogen and catalyst into a reactor.
  • the alpha-olefin comonomers can each have 2 or 4 to 12 carbon atoms, and preferably have 2 or 4 to 8 carbon atoms, which can be, for example, ethylene, 1-butene, or 1-hexene, or various mixtures of alpha-olefins.
  • the mole ratio of alpha-olefin to propylene is about 0.01 to about 0.06 and, preferably, is about 0.015 to about 0.04.
  • the mole ratio of hydrogen to propylene alone or combined propylene and alpha-olefin is in the range of about 0.001 to about 0.45 and is preferably about 0.004 to about 0.1.
  • Hydrogen can be introduced into the reactor as a chain control agent.
  • the mole ratio of hydrogen to combined propylene and alpha-olefin is about 0.1 to about 1.0 and is preferably about 0.1 to about 0.4.
  • the process of the invention calls for the addition of a hydrocarbon or mixture of hydrocarbons. On addition of the hydrocarbon(s), the random propylene copolymer increases its modality from monomodal to bimodal. Thus, the post-blend propylene copolymers can be characterized as bimodal.
  • Propylene or a mixture of propylene and one or more alpha- olefin(s) is introduced together with hydrogen and catalyst into the first reactor.
  • the alpha-olefins can each have 2 or 3 to 12 carbon atoms, and preferably have 2 or 4 to 8 carbon atoms.
  • Examples of alpha-olefin comonomers are ethylene, 1-butene, or 1-hexene, or various mixtures of alpha-olefins.
  • the mole ratio of alpha-olefin to propylene is about 0.01 to about 0.06 and, preferably, is about 0.015 to about 0.04.
  • the mole ratio of hydrogen to propylene alone or combined propylene and alpha-olefin is in the range of about 0.001 to about 0.45 and is preferably about 0.004 to about 0.1.
  • ethylene and propylene or 1-butene are introduced in a mole ratio of about 10 to about 100 moles of ethylene per mole of propylene or 1-butene, and preferably about 10 to about 50 moles of ethylene per mole of propylene or 1-butene.
  • the combined ethylene/propylene or 1-butene addition is sufficient to provide a copolymer fraction of about 20 to about 45 percent by weight of copolymer based on the weight of the product, and preferably a copolymer fraction of about 25 to about 30 percent by weight.
  • the product i.e., the final product
  • Hydrogen is also introduced into the second reactor together with the ethylene and propylene or 1-butene.
  • the mole ratio of hydrogen to combined ethylene and propylene or 1- butene is about 0.1 to about 1.0 and is preferably about 0.1 to about 0.4. It should be noted that some or all of the propylene or 1-butene in the second reactor can come from the first reactor.
  • the two reactors are operated continuously, in series.
  • the process of the invention calls for the addition of a hydrocarbon or mixture of hydrocarbons.
  • the impact polypropylene copolymer increases its modality from monomodal to bimodal.
  • the post-blend impact polypropylene copolymers can be characterized as bimodal.
  • the hydrocarbon(s) are saturated alicyclic hydrocarbon. They are unsubstituted. Alicyclic hydrocarbons are mixtures of aliphatic and cycloaliphatic hydrocarbons.
  • the hydrocarbon(s) are generally liquid at ambient temperatures; are liquid at process temperature, non-polar, essentially amorphous, and contain less than 15 percent by weight paraffin wax, preferably less than one percent by weight paraffin wax. No paraffin wax would be most preferable, but this is not considered practical or necessary for the composition applications.
  • the liquid hydrocarbons can have a viscosity in the range of about 200 to about 1000 SUS (Saybolt Universal Seconds) at 100°F (37.8°C) and preferably have a viscosity in the range of about 250 to about 800 SUS at 100°F.
  • these hydrocarbons are Kaydol® 350, 380, and 550 hydrocarbons.
  • Other examples are Tufflo® 6056 and 6026 hydrocarbons. It is noted that these Tufflo® hydrocarbons do not comply with the FDA regulations for food contact. Kaydol® 350 is reported to contain 11.8 percent by weight paraffin wax and Kaydol® 550 is reported to contain less than one percent by weight paraffin wax.
  • the molecular weight of these hydrocarbons is in the range of about 200 to about 5000.
  • the hydrocarbon(s) can be present in the mixture of polypropylene copolymer and hydrocarbon(s) in an amount of about 0.1 to about 20 parts by weight of hydrocarbon(s) per 100 parts by weight of polypropylene copolymer, and are preferably present in an amount of about 1 to about 15 parts by weight. These values refer to total hydrocarbons and total polypropylene copolymer. In any case, the amount of hydrocarbon(s) should be such that the surface of each particle of propylene copolymer resin is essentially free of these hydrocarbon(s).
  • the hydrocarbon(s) are also miscible with the propylene copolymer at process temperatures, and, in the suggested proportions, reside in the amorphous phase of the propylene copolymer.
  • extrusion processes shall be considered to include conventional extrusion processes such as blown tubular film extrusion (see discussion in United States Patent 4,814,135), and pipe and sheet extrusion, and blow molding, injection molding, rotational molding, and slot casting.
  • the hydrocarbon(s) are usually dry blended with the propylene copolymer post-polymerization and prior to extrusion (preblending), but the hydrocarbon(s) and resin can be blended in the extruder itself under melt processing conditions, if desired. Preblending is preferable, however, since it shortens the mixing time and is a key factor in achieving uniform distribution of the hydrocarbon in the resin.
  • the propylene copolymer is in the molten state when the blending is initiated. The propylene copolymer mixes readily with the hydrocarbon(s) without the use of heat except, as noted, when it is in pelletized form.
  • Preblending can be carried out at ambient or elevated temperatures, however.
  • Useful mixers and extruders are conventional off-the-shelf equipment.
  • Mixers, which can be used to blend the resin and the liquid hydrocarbon are, for example, BanburyTM or other internal mixers, two roll mills, Baker PerkinsTM or similar sigma blade mixers, ribbon blenders, and HenschelTM mixers.
  • extruders can also be used to mix the resin and the hydrocarbon(s). Blending can also be effected by injecting the hydrocarbon(s) into fluidized propylene copolymer.
  • the preferred blending technique is to add the hydrocarbon(s) to the polymerization reactor.
  • the advantage of this technique is improved homogeneity of the blend with an attendant improvement in many of the improved properties achieved in dry or melt blending. It will be understood that sufficient hydrocarbon(s) have to be added to the reactor to provide the amount set forth above for the blend. In the case of impact copolymers, it is preferred to add the hydrocarbon(s) to the first reactor or prior to the second reactor.
  • Extruders and processes for extrusion are described in United States patents 4,169,679; 4,814,135; 4,857,600; 5,076,988; and 5,153,382.
  • Examples of various extruders are a single screw type such as one modified with a blown film die and air ring and continuous take off equipment; a blown film extruder; and a slot cast extruder.
  • Twin screw extruders can also be considered.
  • a typical single screw type extruder can be described as one having a hopper at its upstream end and a die at its downstream end. The hopper feeds into a barrel, which contains a screw. At the downstream end, between the end of the screw and the die, is a screen pack and a breaker plate.
  • the screw portion of the extruder is considered to be divided up into three sections, the feed section, the compression section, and the metering section, and multiple heating zones from the rear heating zone to the front heating zone, the multiple sections and zones running from upstream to downstream. If it has more than one barrel, the barrels are connected in series.
  • the length to diameter ratio of each barrel is in the range of about 16:1 to about 30:1.
  • the extrusion can take place at temperatures in the range of about 160 to about 270 degrees C, and is preferably carried out at temperatures in the range of about 180 to about 240 degrees C.
  • the die of the crosshead feeds directly into a heating zone, and this zone can be maintained at a temperature in the range of about 130°C to about 260°C, and preferably in the range of about 170°C to about 220°C.
  • An important advantage of this invention is the improvement in the Notched Izod Impact Strength at 23 degrees C and 0 degrees C as measured under ASTM D-256. Further, there is an improvement in clarity.
  • the hydrocarbon(s) are introduced into the reactor(s), it is noted that the product is not sticky and does not foul the reactor; and the static is reduced.
  • the copolymers exhibit bimodality.
  • additives can be added to the hydrocarbon modified propylene copolymer during the preblending step and/or the extrusion step, and, in some cases, directly to the polymerization reactor.
  • One method for addition involves first blending the desired additive(s) with the hydrocarbon(s) and then blending the mixture with the propylene copolymer .
  • Stabilization packages are advantageously added in this way.
  • the amount of additive is usually in the range of about 0.01 to about 5 percent by weight based on the weight of the resin.
  • the amount of filler can reach 60 percent or higher.
  • Useful additives are antioxidants, ultraviolet absorbers, antistatic agents, pigments, dyes, fillers, slip agents, fire retardants, plasticizers, processing aids, lubricants, stabilizers, smoke inhibitors, viscosity control agents, vulcanizing agents, crosslinking agents, crosslinking catalysts, and crosslinking boosters.
  • the product produced by the process of this invention can be a propylene copolymer blend comprising:
  • component (b) one or more saturated alicyclic hydrocarbon(s), said hydrocarbon(s) being liquid at process temperature, non-polar, essentially amorphous, and containing less than about 15 percent by weight paraffin wax, in an amount of about 0.1 to about 20 parts by weight of hydrocarbon(s) per 100 parts by weight of component (a), defined above, and preferably in an amount of about 0.5 to about 15 parts by weight, said copolymer exhibiting bimodality after blending.
  • the bimodal random propylene copolymer of this invention preferably has the following physical properties:
  • melt flow in the range of about 0.5 to about 50 grams per 10 minutes, and preferably about 1 to about 30 grams per 10 minutes (melt flow is determined under ASTM D-1238 at 230 degrees C and at 2.16 kilograms);
  • a density is in the range of 0.890 to 0.905 gram per cubic centimeter, and is preferably in the range of 0.895 to 0.903 gram per cubic centimeter;
  • DSC Melting Point (m.p.) for polyethylene crystalline fraction (PE) and polypropylene crystalline fraction (PP) is given in degrees Centigrade (°C).
  • the delta H (Heat of Fusion) for polyethylene can be measured in calories per gram (cal/g).
  • the tests used are ASTM 3417 and 3418.
  • the PE value stands for the endotherm peak associated with the melting of the polyethylene crystalline fraction.
  • the PP value stands for the endotherm peak associated with the melting of the polypropylene crystalline fraction.
  • the delta H PE represents the energy required to melt the polyethylene crystalline fraction.
  • liquid propylene and the comonomer ethylene in a mole ratio of about 7:1, and a prepared catalyst precursor having the following approximate composition: TiCl4 » 12 MgCl2 ⁇ 2 C6H5COOC2H5.
  • the weight ratio of liquid propylene to catalyst precursor is 10 kilograms of propylene per gram of catalyst precursor.
  • a cocatalyst, triethylaluminum, and a selectivity control agent, para-ethoxy ethyl benzoate, in a mole ratio of about 2:1, are fed into the reactor at the same time as the catalyst precursor.
  • the atomic ratio of aluminum to titanium is about 60.
  • a hydrocarbon, as defined above, is also added to the fluidized bed in an amount sufficient to provide 10 parts by weight of hydrocarbon per 100 parts by weight of resin product.
  • Conditions under which the fluidized bed reactor is operated are approximately as follows: temperature: 65 degrees C; pressure: 40 pounds per square inch absolute (psia); and fluidizing gas velocity: 1.0 foot per second.
  • the product produced by the invention can also be an impact polypropylene copolymer blend comprising:
  • a polymer matrix selected from the group consisting of a homopolymer of propylene and a random copolymer of propylene and at least one alpha-olefin having 2 or 4 to 8 carbon atoms wherein (i) the polymer is present in an amount of about 55 to about 90 percent by weight based on the weight of the impact polypropylene copolymer, and is preferably present in an amount of about 60 to about 75 percent by weight; and (ii) the portion of the random copolymer based on alpha-olefins other than propylene is not greater than about 7 percent by weight based on the weight of the random copolymer and is preferably about 1 to about 3 percent by weight;
  • a copolymer of ethylene and propylene or 1-butene within the matrix wherein (i) the copolymer is present in an amount of about 10 to about 45 percent by weight based on the weight of the impact polypropylene copolymer, and is preferably present in an amount of about 25 to about 40 percent by weight; and (ii) the portion of the copolymer based on ethylene is at least about 90 percent be weight based on the weight of the copolymer and is preferably at least about 95 percent by weight; and, blended therewith,
  • Copolymer Fraction is the percent by weight of ethylene/propylene copolymer based on the weight of total polymer produced, i.e., product. This refers to the copolymer produced in the second reactor. The amount of copolymer is determined by conventional infrared spectrophotometric techniques.
  • the bimodal impact polypropylene copolymer of this invention preferably has the following physical properties:
  • melt flow in the range of about 0.5 to about 50 grams per 10 minutes, and preferably about 1 to about 30 grams per 10 minutes (melt flow is determined under ASTM D-1238 at 230 degrees C and at 2.16 kilograms);
  • a density is in the range of 0.890 to 0.905 gram per cubic centimeter, and is preferably in the range of 0.895 to 0.903 gram per cubic centimeter;
  • DSC Melting Point (m.p.) for polyethylene crystalline fraction (PE) and polypropylene crystalline fraction (PP) is given in degrees Centigrade (jC).
  • the delta H (Heat of Fusion) for polyethylene can be determined in calories per gram (cal/g).
  • the tests used are ASTM 3417 and 3418.
  • the PE value stands for the endotherm peak associated with the melting of the polyethylene crystalline fraction.
  • the PP value stands for the endotherm peak associated with the melting of the polypropylene crystalline fraction.
  • the delta H PE represents the energy required to melt the polyethylene crystalline fraction.
  • a typical in situ process is carried out as follows: To the first fluidized bed is charged liquid polypropylene and a prepared catalyst precursor having the following approximate composition: TiCl4* 12 MgCl2 # 2 C6H5COOC2H5. The weight ratio of liquid polypropylene to catalyst precursor is 10 kilograms of propylene per gram of catalyst precursor. A cocatalyst, triethylaluminum, and a selectivity control agent, para-ethoxy ethyl benzoate, in a mole ratio of about 2:1, are fed into the reactor at the same time as the catalyst precursor. The atomic ratio of aluminum to titanium is about 60.
  • Conditions under which the first fluidized bed reactor is operated are approximately as follows: temperature: 65 degrees C; pressure: 40 pounds per square inch absolute(psia); and fluidizing gas velocity: 1.0 foot per second.
  • the mixture from the first reactor is transferred to the second reactor and ethylene, propylene, and hydrogen are introduced into the second reactor.
  • Conditions under which the second fluidized bed reactor is operated are approximately as follows: temperature: 70jC; pressure: 165 psia (except 240 psia in examples 1 and 5); and fluidizing gas velocity: 1.2 foot per second.
  • a hydrocarbon, as defined above, is added to either fluidized bed, but preferably the first reactor or prior to the second reactor, in an amount sufficient to provide 10 parts by weight of hydrocarbon per 100 parts by weight of resin product.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

L'invention porte sur processus de production de copolymères de propylène aléatoires ou d'impact à caractère bimodal comportant les étapes suivantes: (a) mise en contact du propylène et d'une ou plusieurs alpha-oléfines avec un système de catalyseurs comprenant: (i) un précurseur de catalyse comportant du titane, du magnésium et un donneur d'électrons, (ii) un cocatalyseur d'hydrocarbylaluminium, et (iii) un agent de contrôle sélectif placé dans un ou plusieurs des réacteurs dans des conditions de polymérisation; et (b) introduction dans le ou les réacteurs, ou après réaction dans le copolymère de propylène d'un ou plusieurs hydrocarbures alicycliques saturés liquides à la température de traitement, non polaires, essentiellement amorphes, et contenant moins de 15 % en poids de cire de paraffine, et de 0,1 à 20 parties en poids d'hydrocarbures pour 100 parties en poids de copolymère de propylène.
PCT/US1996/019304 1995-12-08 1996-12-04 Processus de production de copolymeres de propylene bimodal WO1997021746A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU11290/97A AU1129097A (en) 1995-12-08 1996-12-04 Process for the production of bimodalpropylene copolymers

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US836795P 1995-12-08 1995-12-08
US841795P 1995-12-08 1995-12-08
US008,367 1995-12-08
US008,417 1995-12-08

Publications (1)

Publication Number Publication Date
WO1997021746A1 true WO1997021746A1 (fr) 1997-06-19

Family

ID=26678117

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/019304 WO1997021746A1 (fr) 1995-12-08 1996-12-04 Processus de production de copolymeres de propylene bimodal

Country Status (2)

Country Link
AU (1) AU1129097A (fr)
WO (1) WO1997021746A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1270651A1 (fr) * 2001-06-27 2003-01-02 Borealis Technology Oy Film polymère comprenant un copolymère statistique de propylène
WO2005035597A1 (fr) * 2003-09-23 2005-04-21 Dow Global Technologies Inc. Composition catalytique pour la polymerization de l'ethylene

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3639515A (en) * 1956-10-15 1972-02-01 Eastman Kodak Co Preparation of alpha-olefin block copolymers
JPS5645932A (en) * 1979-09-20 1981-04-25 Adeka Argus Chem Co Ltd Polyolefin pesin composition
EP0067525A2 (fr) * 1981-05-13 1982-12-22 UNIROYAL CHEMICAL COMPANY, Inc. Un procédé pour la préparation d'un elastomère thermoplastique
JPS5968340A (ja) * 1982-10-14 1984-04-18 Asahi Chem Ind Co Ltd 発泡用ポリプロピレン系樹脂組成物
EP0384264A1 (fr) * 1989-02-15 1990-08-29 Hoechst Aktiengesellschaft Cire de polypropylène et procédé pour la préparer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3639515A (en) * 1956-10-15 1972-02-01 Eastman Kodak Co Preparation of alpha-olefin block copolymers
JPS5645932A (en) * 1979-09-20 1981-04-25 Adeka Argus Chem Co Ltd Polyolefin pesin composition
EP0067525A2 (fr) * 1981-05-13 1982-12-22 UNIROYAL CHEMICAL COMPANY, Inc. Un procédé pour la préparation d'un elastomère thermoplastique
JPS5968340A (ja) * 1982-10-14 1984-04-18 Asahi Chem Ind Co Ltd 発泡用ポリプロピレン系樹脂組成物
EP0384264A1 (fr) * 1989-02-15 1990-08-29 Hoechst Aktiengesellschaft Cire de polypropylène et procédé pour la préparer

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 005, no. 106 (C - 062) 10 July 1981 (1981-07-10) *
PATENT ABSTRACTS OF JAPAN vol. 008, no. 168 (C - 236) 3 August 1984 (1984-08-03) *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1270651A1 (fr) * 2001-06-27 2003-01-02 Borealis Technology Oy Film polymère comprenant un copolymère statistique de propylène
WO2003002639A1 (fr) * 2001-06-27 2003-01-09 Borealis Technology Oy Film polymere comprenant un copolymere de propylene aleatoire
EP1607433A1 (fr) * 2001-06-27 2005-12-21 Borealis Technology Oy Film polymère comprenant un copolymère statistique de propylène
US7683141B2 (en) 2001-06-27 2010-03-23 Borealis Technology Oy Polymer film comprising a propylene random copolymer
WO2005035597A1 (fr) * 2003-09-23 2005-04-21 Dow Global Technologies Inc. Composition catalytique pour la polymerization de l'ethylene
AU2004280327B2 (en) * 2003-09-23 2009-11-05 Dow Global Technologies Inc. Catalyst composition for ethylene polymerization
CN1856516B (zh) * 2003-09-23 2010-07-07 陶氏环球技术公司 用于乙烯聚合的催化剂组合物
EP2261268A1 (fr) * 2003-09-23 2010-12-15 Dow Global Technologies Inc. Polymerization de l'ethylene utilisant des compositions catalytiques de type ziegler-natta

Also Published As

Publication number Publication date
AU1129097A (en) 1997-07-03

Similar Documents

Publication Publication Date Title
AU604935B2 (en) Process for the production of impact polypropylene copolymers
KR100602310B1 (ko) 고강성 프로필렌 중합체 및 그것의 제조방법
AU744410B2 (en) Process for preparing polypropylene
EP2157104B1 (fr) Compositions des polymères à base d'éthylène
SK646389A3 (en) Process for the in situ blending of polymers
EP1818365A1 (fr) Compositions de polypropylène
AU609294B2 (en) Process for the preparation of random copolymers
US20180273661A1 (en) Synthesis of substituted amidobenzoate compounds, the compounds obtained and the use thereof as phthalate free internal electron donor for polymerization of olefins
JPS5953508A (ja) オレフイン重合体物品の製造方法
KR100323784B1 (ko) 프로필렌-에틸렌블럭공중합체의연속제조법
CN103403087B (zh) 具有改进的流动性和冲击强度的杂相聚烯烃组合物
WO1997021746A1 (fr) Processus de production de copolymeres de propylene bimodal
JP2607099B2 (ja) 高剛性エチレン−プロピレンブロック共重合体組成物
EP0461883B1 (fr) Compositions de polymères
EP0509169B1 (fr) Procédé de production de polyoléfine
EP1355954B1 (fr) Procede de preparation de polymeres de propylene
JP2855459B2 (ja) エチレン重合体組成物
JP2562915B2 (ja) 高剛性高溶融粘弾性エチレン−プロピレンブロック共重合体組成物
EP0390382B1 (fr) Composition thermoplastique
KR20230111390A (ko) 투명성, 강성 및 열안정성이 개선된 호모 폴리프로필렌 및 이의 제조방법
JPH11130922A (ja) 低結晶性ポリプロピレン樹脂組成物
JPH08325414A (ja) 安定化されたポリオレフィン組成物
JP2021025015A (ja) 射出成形体
JPH0768538A (ja) ポリプロピレンの連続製造方法
JPH09302052A (ja) プロピレンのブロック共重合体の製造方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR CA CN JP MX US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE DE ES FI FR GB GR IE IT NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: JP

Ref document number: 97522096

Format of ref document f/p: F

122 Ep: pct application non-entry in european phase