This invention relates to certain polymer compositions having an excellent balance of mechanical properties, such as low hexane extractables content, low heat seal initiation temperatures, and optical properties, such as good clarity, low yellowing, and low haze. More particularly, the invention relates to random copolymers of propylene and butene-1 of particular compositions. Background Art

Polyolefin polymers compositions have gained wide acceptance and usage in numerous commercial applications because of the relatively low cost of the polymers and the desirable properties they exhibit. Such commercial applications include plastic film, such as mono-oriented cast film and biaxially oriented films, for food packaging, containers for food and medical devices such as syringes.

It is very important for materials used as containers for foods and medical devices, that the presence or absence of impurities or foreign substances such as refuse or the like in the contents of a container can be externally confirmed. It is not desirable that the color tint of the contents be changed when it is observed through the container. For this reason, it is desired to use a polymer composition of good transparency or clarity, in these fields.

There has widely been used a method for improving the clarity or transparency of polymer composition, in particular polypropylene resins, which comprises incorporating a sorbitol derivative into the resins. Yokote et al, U.S. 5,153,249 discloses a polypropylene resin composition which incorporates an additive package of 1-3, 2-4 di-benzylidene sorbitol and talc which are well-known nucleating additives. Although the reference cited above teaches a copolymer composition exhibiting some improvement in optical

properties, it would be of advantage to provide improved random copolymer compositions including a process for producing the improved copolymer compositions, having an improved balance of low haze (i.e., good transparency), low blooming, low yellowing, low hexane extractables content, and low heat seal initiation temperature.

In recent years, the film industry is requesting polymer compositions with lower heat seal initiation temperature in order to facilitate the film converting process. Polypropylene random copolymers containing ethylene as the comonomer are typically used for this application. These ethylene-containing polymers typically require high heat seal initiation temperatures. Further, as ethylene random film ages, a "grease" or "bloom" layer develops on the surface of the film which adversely effects the clarity of the film.

In an attempt to provide polymer compositions suitable for making films, various polymer blends for packaging film are known. Isaka et al, U.S. 4,230,767 discloses a packaging material with heat seal packaging properties composed of blends of a polypropylene/ethylene copolymer with a variety of other propylene olefins and copolymers. Hwo, U.S. 4,618,804, discloses polybutylene/ propylene polymer film having low heat sealing temperatures as well as good hot tack and clarity. The film comprises a polypropylene copolymer as a core layer and a polymer blend as a surface layer which is a butene-1 propylene copolymer having a propylene content of from about 10% to about 25% by weight. European Patent Application 246369 discloses butene copolymer blends comprising (a) copolymer of butene-1 and propylene wherein the propylene content is 12 to 30% by weight, and (b) a copolymer of propylene and ethylene.

Oda et al, U.S. 4,168,361, disclose random copolymers comprising 40 to 90 mole% of propylene and 60 to 10 mole% of 1-butene, which are produced in the presence of a magnesium, titanium-containing catalyst. The patent states that the elongation at break, as measured by JIS K6301, of

its copolymers must be at least 300%. Fakui et al, U.S. 4, 600,762, discloses a random copolymer of 60 to 99 moles of 1-butene and less than 40 to 1 moles of polypropylene. Balloni et al, 5,110,671 disclosed an oriented, multilayer polymer film.

Low hexane extractables content copolymers is very desirable because the U.S. Food and Drug Administration ("FDA") has specific solubles requirements that polyolefin copolymers must satisfy in order to be used for food or medical packaging. In particular, FDA regulations require that the polyolefin copolymer have a hexane extractable content (at 50°C) of less than 2.6% for holding food during cooking and less than 5.5% for general food packaging applications. As noted previously, polypropylene random copolymers containing ethylene are typically used for food and medical packaging. However, some ethylene containing randoms require an additional washing step during manufacture to meet the FDA hexane extractables limits. Disclosure of the Invention The present invention relates to polymer compositions having an excellent balance of improved mechanical and optical properties.

More particularly, according to one embodiment of the present invention relates to a polymer composition of (1) a random copolymer comprising from about 0.8% to about 20% by weight of butene-1 and 80% to 99.2% by weight of propylene. The resulting polymer product has one or more of the following:

(a) an elongation at break in the range from 600% to 2000%,

(b) heat seal initiation temperature in the range from about 105°C to about 140°C,

(c) a haze of up to 6%, as measured according to ASTM D- 1003, and (d) hexane extractables at 50°C of up to about 5.5%.

According to another embodiment of the invention the polymer compositions of this invention, optionally includes

(1) at least one additive, and (2) at least one non-nucleating, clarifying agent which is calcium montanate, at least one polyolefin wax or combinations thereof. The invention also relates to a process for producing the random copolymer of the polymer composition and therefore the polymer composition, in the presence of a high activity stereoregular catalyst system obtained by contacting (i) an olefin polymerization procatalyst with (ii) an organoaluminum cocatalyst and (iii) a selectivity control agent. Best Mode for Carrying Out the Invention

The present invention comprises certain polymer compositions which, because of the particular composition thereof, exhibit an improved balance of mechanical properties and optical properties. These compositions are characterized as propylene/butene-1 random copolymer resins.

The resulting polymer compositions have low hexane extractables content, low heat seal initiation temperature and excellent optical properties, such as low haze, low blooming, and low yellowing. According to an embodiment of the invention, the polymer resin compositions are characterized as comprising (1) a propylene/butene-1 random copolymer resin, (2) at least one additive and (3) at least one haze-reducing, non-nucleating, clarifying agent which is calcium montanate, at least one polyolefin wax or combinations thereof.

The polymer resin composition of the present invention are obtained by polymerizing propylene and butene- 1 under polymerization conditions in the presence of a titanium-based, olefin polymerization catalyst system, such as a magnesium, titanium-containing polymerization catalyst system. Such polymerization catalyst systems are typically obtained by the combination of a titanium halide-based

catalyst component, an organoaluminum compound and one or more electron donors. For convenience of reference, the solid titanium-containing catalyst component is referred to herein as "procatalyst", the organoaluminum compound, as "cocatalyst", and an electron donor compound, which is typically used separately or partially or totally complexed with the organoaluminum compound, as "selectivity control agent" (SCA) .

Although a variety of chemical compounds are useful for the production of the procatalyst, a typical procatalyst of the invention is prepared by halogenating a magnesium compound of the formula MgR'R", wherein R' is an alkoxide or aryloxide group and R" is an alkoxide, hydrocarbyl carbonate, aryloxide group or halogen, with a halogenated tetravalent titanium compound in the presence of a halohydrocarbon and an electron donor.

The magnesium compound employed in the preparation of the solid catalyst component contains alkoxide, aryloxide, hydrocarbyl carbonate or halogen. The alkoxide, when present, contain from 1 to 10 carbon atoms. Alkoxide containing from 1 to 8 carbon atoms is preferable, with alkoxides of 2 to 4 carbon atoms being more preferable. The aryloxide, when present, contains from 6 to 10 carbon atoms, with 6 to 8 carbon atoms being preferred. The hydrocarbyl carbonate, when present, contains 1 to 10 carbon atoms. When halogen is present, it is preferably present as bromine, fluorine, iodine or chlorine, with chlorine being more preferred.

Suitable magnesium compounds are magnesium chloride, ethoxy magnesium bromide, isobutoxy magnesium chloride, phenoxy magnesium iodide, magnesium fluoride, cumyloxy magnesium bromide, magnesium diethoxide, magnesium isopropoxide, magnesium stearate, magnesium ethyl carbonate and naphthoxy magnesium chloride. The preferred magnesium compound is magnesium diethoxide.

Halogenation of the magnesium compound with the halogenated tetravalent titanium compound is effected by

using an excess of the titanium compound. At least 2 moles of the titanium compound should ordinarily be used per mole of the magnesium compound. Preferably from 4 moles to 100 moles of the titanium compound are used per mole of the magnesium compound, and most preferably from 8 moles to 20 moles of the titanium compound are used per mole of the magnesium compound.

Halogenation of the magnesium compound with the halogenated tetravalent titanium compound can be effected by contacting the compounds at an elevated temperature in the range from about 60°C to about 150°C, preferably from about 70°C to about 120°C. Usually the reaction is allowed to proceed over a period of 0.1 to 6 hours, preferably from about 0.5 to about 3.5 hours. The halogenated product is a solid material which can be isolated from the liquid reaction medium by filtration, decantation or a suitable method.

The halogenated tetravalent titanium compound employed to halogenate the magnesium compound contains at least two halogen atoms, and preferably contains four halogen atoms. The halogen atoms are chlorine atoms, bromine atoms, iodine atoms or fluorine atoms. The halogenated tetravalent titanium compounds has up to two alkoxy or aryloxy groups. Examples of suitably halogenated tetravalent titanium compounds include alkoxy titanium halides, diethoxytitanium dibromide, isopropoxytitanium triiodide, dihexoxytitanium dichloride, and phenoxytitanium trichloride, titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide. The preferred halogenated tetravalent titanium compound is titanium tetrachloride.

Suitable halohydrocarbons include aromatic or aliphatic, including cyclic and alicyclic compounds. Preferably the halohydrocarbon contains 1 or 2 halogen atoms, although more may be present if desired. It is preferred that the halogen is, independently, chlorine, bromine or fluorine. Exemplary of suitable aromatic

halohydrocarbons are chlorobenzene, bromobenzene, dichloro¬ benzene, dichlorodibromobenzene, chlorotoluene, dichloro- toluene, chloronaphthalene. Chlorobenzene, chlorotoluene and dichlorobenzene are the preferred halohydrocarbons, with chlorobenzene and chlorotoluene being more pre erred.

The aliphatic halohydrocarbons which can be employed suitably of 1 to 12 carbon atoms. Preferably such halohydrocarbons have 1 to 9 carbon atoms and at least 2 halogen atoms. Most preferably, the halogen is present as chlorine. Suitable aliphatic halohydrocarbons include dibromo ethane, trichloromethane, 1,2-dichloroethane, trichloroethane, dichlorofluoroethane, hexachloroethane, trichloropropane, chlorobutane, dichlorobutane, chloro- pentane, trichlorofluorooctane, tetrachloroisooctane, dibromodifluorodecane. The preferred aliphatic halo¬ hydrocarbons are carbon tetrachloride and trichloroethane. Aromatic halohydrocarbons are preferred, particularly those of 6 to 12 carbon atoms, and especially those of 6 to 10 carbon atoms. Suitable inert hydrocarbon diluents include aromatic hydrocarbons such as toluene, o-xylene, m-xylene, p-xylene, benzene, ethylbenzene, propylbenzene such as isopropylbenzene or cumene, trimethylbenzene and the like which are liquid at normal temperature. The electron donors which are suitably included within the procatalyst are the generally conventional electron donors employed in titanium-based olefin polymerization procatalysts including ethers, esters, ketones, amines, imines, nitriles, phosphines, stibines, arsines and alcoholates. The preferred electron donors are esters and particularly aliphatic esters of aromatic monocarboxylic or dicarboxylic acids. Examples of such preferred electron donors are methyl benzoate, ethyl benzoate, ethyl p-ethoxybenzoate, ethyl p-methylbenzoate, diethyl phthalate, dibutylphthalate, diisobutyl phthalate, diisopropyl terephthalate and dimethyl naphthalenedi- carboxylate. The electron donor is a single compound or a

mixture of two or more compounds but preferably the electron donor is provided as a single compound. Of the preferred ester electron donors, ethyl benzoate and diisobutyl phthalate are particularly preferred. Sufficient electron donor is provided so that the molar ratio of electron donor to magnesium in the procatalyst is from about 0.002 to about 0.3. It is preferred that the molar ratio of electron donor to magnesium in the procatalyst is from about 0.03 to about 0.2, with a ratio from about 0.03 to 0.16 being more preferred.

After the solid halogenated product has been separated from the liquid reaction medium, it is treated one or more times with additional halogenated tetravalent titanium compound. Preferably, the halogenated product is treated multiple times with separate portions of the halogenated tetravalent titanium compound. Better results are obtained if the halogenated product is treated twice with separate portions of the halogenated tetravalent titanium compound. As in the initial halogenation, at least 2 moles of the titanium compound should ordinarily be employed per mole of the magnesium compound, and preferably from 4 moles to 100 moles of the titanium compound are employed per mole of the magnesium compound, most preferably from 4 moles to 20 moles of the titanium compound per mole of the magnesium compound.

The reaction conditions employed to treat the solid halogenated product with the titanium compound are the same as those employed during the initial halogenation of the magnesium compound. Optionally, the solid halogenated product is treated at least once with one or more acid chlorides after washing the solid halogenated product at least once with additional amounts of the halogenated tetravalent titanium compound. Suitable acid chlorides include benzoyl chloride and phthaloyl chloride. The preferred acid chloride is phthaloyl chloride.

After the solid halogenated product has been treated one or more times with additional halogenated tetravalent titanium compound, it is separated from the liquid reaction medium, washed at least once with an inert hydrocarbon of up to 10 carbon atoms to remove unreacted titanium compounds, and dried. Exemplary of the inert hydrocarbons that are suitable for the washing are isopentane, isooctane, hexane, heptane and cyclohexane.

The final washed product has a titanium content of from 1.5 percent by weight to 6.0 percent by weight, preferably from 2.0 percent by weight to 4.0 percent by weight. The atomic ratio of titanium to magnesium in the final product is between 0.01:1 and 0.2:1, preferably between 0.02:1 and 0.1:1. The cocatalyst is an organoaluminum compound which is selected from the aluminum-based cocatalysts conven¬ tionally employed with titanium-based procatalysts. Illustrative organoaluminum compounds are trialkylaluminum compounds, alkylaluminum alkoxide compounds and alkyl- aluminum halide compounds wherein each alkyl independently has from 2 to 6 carbon atoms inclusive. The preferred organoaluminum compounds are halide free and particularly preferred are the trialkylaluminum compounds such as triethylaluminum, triisobutylaluminum, triisopropylaluminum and diethylhexylaluminum. Triethylaluminum is the preferred member of the class of trialkylaluminum compounds. The cocatalyst is employed in a sufficient quantity to provide a ratio of aluminum atoms to titanium atoms in the procatalyst from about 1:1 to about 300:1 but preferably from about 10:1 to about 100:1.

The organoaluminum cocatalyst is employed in sufficient quantity to provide from 1 mole to about 150 moles of aluminum per mole of titanium in the procatalyst. It is preferred that the cocatalyst is present in sufficient quantities to provide from 10 moles to about 100 moles of aluminum per mole of titanium in the procatalyst.

The selectivity control agents which are employed in the production of the olefin polymerization catalyst are those conventionally employed in conjunction with titanium- based procatalysts and organoaluminum cocatalysts. Suitable selectivity control agents include those electron donors as listed above for use in procatalyst production but also include organosilane compounds such as alkylalkoxysilanes and arylalkoxysilanes of the formula

R' _r Si(OR) ₄ _ _r wherein R ¹ is alkyl or aryl of up to 32 carbon atoms inclusive, R is lower alkyl of up to 4 carbon atoms and r is 0 to 3.

Illustrative of the suitable selectivity control agents are esters such as ethyl p-ethoxybenzoate, diisobutyl phthalate, ethyl benzoate and ethyl p-methylbenzoate, and organosilanes such as diisobutyldimethoxysilane, n-propyl- trimethoxysilane, isopropyltrimethoxysilane, ethyltriethoxy- silane, octadecyltriethoxysilane, octadecyltrimethoxysilane, andcyclohexylmethyldimethoxysilane. The selectivitycontrol agent is provided in a quantity sufficient to provide from about 0.01 mole to about 100 moles per mole of titanium in the procatalyst. It is preferred that the selectivity control agent is provided in a quantity sufficient to provide from about 0.5 mole to about 70 moles per mole of titanium in the procatalyst, with about 8 moles to about 50 moles being more preferred.

The manner by which the solid procatalyst precursor, tetravalent titanium halide, the optional inert diluent and the electron donor are contacted is material but not critical and is generally conventional. In one embodiment the procatalyst precursor and the tetravalent titanium halide are mixed and the electron donor is subsequently added to the resulting mixture. In another embodiment, the electron donor and procatalyst precursor are mixed with the tetravalent titanium halide or a mixture of tetravalent titanium halide and optional inert diluent and the resulting solid is contacted one or more additional

times with tetravalent titanium halide or the mixture of tetravale ⁿ t titanium halide and optional inert diluent. The inrtial contacting of electron donor, procatalyst precursor and tetravalent titanium halide or the tetravalent titanium halide/optional inert diluent mixture is suitably conducted at a temperature from about ambient to about 150°C. Better interaction of these materials is obtained if they are heated and initial contacting temperatures from about 70°C to about 130°C are preferred, with temperatures from about 75°C to about 110°C being more preferred.

During each contacting with tetravalent titanium halide a portion of the inert diluent is optionally present and the reaction is facilitated on some occasions by the additional presence of an acid halide such as benzoyl chloride or phthaloyl chloride. The solid procatalyst is typically finished by a final sh with an inert hydrocarbon of up to 10 carbon atoms _^ nd drying under nitrogen. Exemplary of the inert hydrocarbons that are suitable for the washing are isopentane, isooctane, hexane, heptane and cylohexane.

The components of the olefin polymerization catalyst are usually contacted by mixing in a suitable reactor outside the system ir- /hich α-olefin is to be polymerized and the catalyst thereby produced is subsequently introduced into the polymerization reactor. Alternatively, however, the catalyst components are introduced separately into the polymerization reactor or, if desired, two or all of the components are partially or completely mixed with each other (e.g. pre ixing selectivity control agent and the procatalyst) before they are introduced into the polymerization reactor.

The particular type of polymerization process utilized is not critical to the operation of the present invention and the polymerization processes now regarded as conventional are suitable in the process of the invention. The polymerization is conducted under polymerization conditions as a liquid phase or as a gas-phase process

utilizing some condensed monomer and employing a fluidized catalyst bed.

The polymerization conducted in the liquid phase employs as reaction diluent an added inert liquid diluent or alternatively a liquid diluent which comprises the olefins, i.e., propylene and butene-1, undergoing polymerization. Typical polymerization conditions include a reaction temperature from about 25°C to about 125°C, with temperatures from about 35°C to about 100°C being preferred, and temperatures from about 75°C to 90°C being most preferred, and a pressure sufficient to maintain the reaction mixture in a liquid phase. Such pressures are from about 150 psi to about 1200 psi, with pressures from about 250 psi to about 900 psi being preferred. The liquid phase reaction is operated in a batchwise manner or as a continuous or semi-continuous process. Subsequent to reaction, the polymer product is recovered by conventional procedures. The precise control of the polymerization conditions and reaction parameters of the liquid phase process are within the skill of the art.

As an alternate embodiment of the invention, the polymerization may be conducted in a gas phase process in the presence of a fluidized catalyst bed. One such gas phase process polymerization process is described in Goeke et al, U.S. Patent 4,379,759, incorporated herein by reference, involves a fluidized bed, gas phase reaction. A gas phase process typically involves charging to reactor an amount of preformed polymer particles, and lesser amounts of catalyst component. The olefins, i.e., propylene and butene-1, to be polymerized, are passed through the particle bed at a rate sufficient to initiate polymerization. The butene-1 molar content present in the gas mixture being continuously fed is from 3% to 25%, 5% to 20% being preferred and 7% to 20% being more preferred. The molar ratio of butene-1 to propylene in the gas mixture is from 0.03 to 0.33, a ratio from 0.05 to 0.25 being preferred, and a molar ratio from 0.08 to 0.15 being more preferred.

Upon passing through the .rticle bed, the unreacted gas is withdrawn from the reactor, pass? through a gas recycle loop and with make-up feed gas, -e again passed through the particle beds on a continuous basis. Copolymer particles are removed from the reactor and additional catalyst is provided to the reactor, often through the use of an inert transport gas such as nitrogen or argon. Polymerized olefin particles are collected at a rate substantially equivalent to its production. The reaction temperature is selected to be below the sintering temperature of the polymer particles and is controlled by an external heat exchanger in a gas cycle loop. Reaction temperatures from about 30°C to about 90°C may be used, with reaction temperatures from about 50°C to about 80°C being commonly used, reaction temperatures from 55°C to 75°C being more commonly used and temperatures from 55°C to 70°C being also used. The reaction pressure is generally from about 100 psi to about 600 psi although reaction pressures from about 150 psi to about 500 psi are preferred. The precise control of reaction conditions as well as the addition of catalyst and feed gas and the recycle of unreacted monomer is within the skill of the art.

In both the liquid phase and the gas-phase polymerization processes, molecular hydrogen is added to the reaction mixture as a chain transfer agent to regulate the molecular weight of the polymeric product. Hydrogen is typically employed for this purpose in a manner well known to persons skilled in the art. The precise control of reaction conditions, and the rate of addition of feed component and molecular hydrogen is broadly within the skill of the art.

The desired polymeric products are obtained as particulate matter formed by growth of polymer product on the polymer particles provided to the fluidized bed or as particles formed in the reactor. The polymer particles are removed from the reactor at a rate which is substantially equivalent to the rate of polymer production and the

particles are passed to a subsequent reaction zone or are finished by conventional methods prior to use.

The polymers produced according to this invention are random copolymers which are predominantly isotactic in structure. The random copolymers of the invention comprise from about 0.8% to about 20% by weight of butene-1. It is preferred that the random copolymer comprise 5% to 18% or 5% to 15% by weight of butene-1, with 7% to 14.5% or 6% to 14% by weight of butene-1 being more preferred. According to one embodiment of the present invention, in addition to the random copolymer resin, the polymer composition of the invention further comprises at least one additive and at least one clarifying agent such as calcium montanate, at least one polyolefin wax or combinations thereof. Calcium montanate is used in an amount ranging from 0.02% to 1.2% by weight of polymer resin composition, preferably 0.05% to 1.0% by weight, 0.1 to 0.5% being more preferred, with 0.15 to 0.3% being most preferred. The viscosity of the polyolefin wax used in the present invention is from 500 millipascal (m-Pa)-seconds to 2500 m-Pa-seconds (at 170°C) , and from 100 m-Pa-seconds to 2000 m-Pa-seconds being preferred. The polyolefin wax has an average particle size which is no more than 2000 μm. The amount of polyolefin wax added to the composition ranges from 0.02% to 1.2% by weight of polymer resin composition, preferably 0.05% to 1.0% by weight, with 0.1% to 0.5% being more preferred.

The polyolefin waxes used in the invention contain 2 to 3 carbon atoms. Suitable polyolefin waxes include polyethylene waxes such as POLY AX® 300 polyethylene wax which is available from Petrolite Corporation, and poly¬ propylene waxes, such as Polypropylene wax 230, which is available from Hoechst Celanese and combinations thereof. The preferred polyolefin wax is polypropylene wax.

The at least one additive is selected from a group of suitable additives which includes process stabilizers,

antioxidants, ultraviolet absorbers, acid neutralizing agents, such as magnesium aluminum hydroxycarbonate hydrate, and dispersants, which are conventionally employed in commercial polymers compositions and do not adversely affect the haze or transparency of the compositions.

Examples of antioxidants which can be used in the invention are bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, tris(2,4-di-butylpheny1)phosphite, 2,6-di-t- butyl-p-methylphenol,n-octadecyl-3- (4-hydroxy-3,5-di-tert- butylphenyl)propionate, tetrakis[me lene(3,5-di-t-butyl-4- hydroxyhydrocinnamate) ]methane, pem.aerythritol-tetrakis- (β- laurylthiopropionate) and distearyl thiodipropionate.

Typical examples of ultraviolet absorbers indues 2-hydroxy-4-n-octoxybenzophenone, 2-(2'-hydroxy-3* ,5•-di- tert-butylpheny1)-5-chlorobenzotriazole, dimethyl suc- cinate-2-(4-hydroxy-2,2,6,6-tetramethyl-l-piperidyl)ethanol condensate.

The polymer compositions of this invention have one or more of the following characteristics (A) to (G) : (A) An elongation at break, as measured according to ASTM D882, in the range of 600% to 2000%, preferably a range of 600% to 1500 %, a range from 700% to 1400% being more preferred, with a range from 650% to 950% being most preferred. When measurements are made according to JIS K630; as referenced in U.S. 4,168,361, which is incorporated by reference herein, the elongation at break is up to 15%.

(B) A low heat seal initiation temperature ("H.S.I.T.") , in the range from 90°C to 150°C, preferably a range from 100°C to 145°C, with a range from 105°C to 140°C being more preferred. The H.S.I.T. is determined by sealing a 1 mil film sample at 14.7 psi for about one second at a given temperature using a Sentinel Model 12-12A heat sealer with a 1/8 inch wide heater bar. The sealing temperature is increased at 5°C degree intervals until the seal does not separate when a force of approximately 50 g /in is applied to the seal (this measurement procedure is identified herein as "H.S.I.T./a") or a force of

approximately 500 g/in is applied in a peeling mode (this alternate procedure is identified herein as "H.S.I.T./b") . The H.S.I.T. is the minimum temperature at which the film seal does not break under the 50 g/in load (H.S.I.T./a) or the 500 g/in load (H.S.I.T./b) .

(C) A hexane extractable content at 50°C, as measured according to 21 C.F.R. §177.1520(c) (3.1 & 3.2), of up to 5.5%, preferably up to 3.5%, up to 2.6% being more preferred, and up to 2.0% being most preferred. (D) A xylene solubles content at 23°C, as measured according to 21 C.F.R. 177.1520, of up to 13%, preferably up to 6%, with up to 5% being more preferred, and up to 3% being most preferred.

(E) A modulus, as measured according to ASTM D882 (1% secant at 0.05 inches/min) , of at least 60,000 psi, preferably of at least 80,000 psi, with at least 100,000 psi being more preferred,

(F) A melting point from 120°C to 155°C, and

(G) A haze, as measured by ASTM D-1003, of up to 6%, with a haze of up to 3% being preferred, a haze of up to 2% being more preferred, and a haze of up to 1.8% being most preferred. Haze is a measure of transparency of the composition of the invention. Haze is measured as the percentage of light transmittance. The presence of various additives such as silica can adversely effect haze values if the particle size of the silica is larger than the wavelength of the light. Further, the thickness of the film has an effect on the haze value of the film, as film thickness increases, the haze value increases. (H) A gloss, as measured according to ASTM D-523

(60°C) , in the range from 110 to 150, with a gloss in the range from 140 to 150 being preferred, and

(I) A clarity, as measured according to D-1003, in the range from 20 to 80, with a range from 40 to 75 being preferred and from 50 to 75 being most preferred.

The polymer compositions as described above will have melt flows, as determined by a conventional test

procedure such as ASTM-D1238, Cond. L, of from about 0.8 dg/min to about 50 dg/min. A melt flow of from about 1 dg/min to about 25 dg/min being preferred and from about 3 dg/min to about 20 dg/min being more preferred. Optical properties of the copolymer composition are improved with higher melt flow.

As an alternative embodiment of the invention, the polymer compositions ar< _^ contacted at elevated temperatures, e.g., above 180°C, with peroxide. The treatment is termed "visbreaking" and the procedures thereof are within the skill of the art and can be used to increase the melt flow of the reactor polymer products as desired.

The visbroken polymer products of this invention are obtained by visbreaking the polymer compositions of the present invention that have a melt flow of at least 0.8 dg/min. The melt flow ratio of the resulting visbroken product to the starting non-visbroken polymer product is at least 2, a melt flow ratio of 5 is preferred, with a melt flow ratio of 8 being more preferred. The polymer compositions of the invention as well as the visbroken derivatives thereof are characterized by an excellent balance of improved low heat seal initiation tempers^ res, low hexane extractables, good stiffness and good optical properties, such as low haze, low yellowing and/or low bloom.

According to another embodiment of the invention, the polypropylene random copolymer composition incorporates an additive package comprising from 0.03% to 0.10% by weight of composition tetrakis[methylene(3,5-di-tert-buty ^" -4- hydroxyhy- ocinnamate) ]methane, from 0.05% to 0.11% by weight of bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and from 0.01% to 0.04% by weight of ;.agnesium aluminum hydroxy carbonate hydrate.

The polypropylene random copolymer composition of the invention may optionally incorporate other additives such as stabilizers, slip agents such as erucamide.

antioxidants, acid acceptors, antiblocking agents such as amorphous silica, nucleating agents, and dispersants.

The compositions of the invention are processed by conventional procedures used for the production of biaxially oriented or monoaxially oriented films, such as casting or film blowing methods. After fabrication, the film can be heat sealed by sealing jaws at a preset temperature, pressure and dwell time. The resulting product, such as polymer packaging film, sheet or container, has a lower heat seal initiation temperature, low hexane extractables and improved optical properties such as low haze and low yellowing. Unlike typical polymer film made of random polypropylene copolymers containing ethylene as the comonomer, the butene random copolymers of the invention exhibit low to no blooming after aging at room temperature.

Selection of the butene content to be incorporated into the random copolymer of the invention and selection of the melt flow of the copolymer for desired applications is within the skill of the art. The compositions of the invention are processed by conventional procedures used for thermoplastic materials such as extrusion, injection molding, thermoforming and related processes. Among particular applications for the compositions are the production of oriented or unoriented films by casting or film blowing methods. After fabri¬ cation, the film can be heat sealed by sealing jaws at a preset temperature, pressure and dwell time. The resulting film has lower heat seal initiation temperatures, low hexane, extractables and improved optical properties such as low haze, i.e., good transparency.

Other features, advantages and embodiments of the invention disclosed herein will be readily apparent to those exercising ordinary skill after reading the foregoing disclosure. In this regard, while specific embodiments of the invention have been described in detail, variations and modifications of these embodiments can be effected without

departing from the spirit and scope of the invention as described and claimed.

The invention described herein is illustrated, but not limited by the following Illustrative Embodiments and Comparative Examples. The following terms are used throughout the Illustrative Embodiments and Comparative

Examples:

SCA (Selectivity Control Agent) NPTMS (n-propyltrimethoxysilane) DIBDMS (Diisobutyldimethoxysilane)

PEEB (ethyl p-ethoxybenzoate) Illustrative Embodiment I

A. Preparation of Procatalyst No. 1

To a solution of 70 milliliters of titanium tetrachloride (120 grams, 0.64 mo_ in 3.7 liters of chlorobenzene are added, in succession, 180 milliliters of diisobutyl phthalate (187 grams, 0.67 mol) , 590 grams (5.2 mols) of magnesium diethoxide, and a solution of 4.7 liters of titanium tetrachloride (8100 grams, 43 mols) in 1.2 liters of chlorobenzene. A temperature of 20°C to 25°C is maintained during these additions. The resulting mixture is then heated to 110°C with stirring, the temperature being maintained for 1 hour. At the end of this time, the mixture is filtered while hot. A solid material is collected. The solid material is then slurried in a solution of 4.7 liters of titanium tetrachloride (8100 grams, 43 mols) in 1.2 liters of chlorobenzene at room temperature.

A solution of 45 grams (0.22 mol) of phthaloyl dichloride in 3.7 liters of chlorobenzene is added to the slurry at room temperature and the resulting slurry is then heated to

110°C with stirring, the temperature being maintained for

30 minutes. At the end of this time, the mixture is filtered while hot. A solid material is collected.

The solid material is reslurried in a solution of 4.7 liters of titanium tetrachloride (8100 grams, 43 mols) in 1.2 liters of chlorobenzene at room temperature. An additional 3.7 liters of chlorobenzene is then added to the

slurry at room temperature, and the resulting slurry is heated to 110°C with stirring, the temperature being maintained in 30 minutes. At the end of this time, the mixture is filtered while hot. A solid material is collected.

The solid material is reslurried once again in a solution of 4.7 liters of titanium tetrachloride (8100 grams, 43 mols) in 1.2 liters of chlorobenzene at room temperature. An additional 3.2 liters of chlorobenzene is then added to the slurry at room temperature, and the resulting slurry is heated to 110°C with stirring, the temperature being maintained for 30 minutes. At the end of this time, the mixture is filtered while hot. The residue is washed 6 times with 500 milliliter portions of hexane at 25°C and then dried under a nitrogen purge. The product weighs about 500 grams.

B. Preparation of Procatalyst No. 2

To a 50/50 solution (vol/vol) of 3558 liters of titanium tetrachloride and chlorobenzene, are added, in succession, 51 kg of diisobutyl phthalate, and 150 kg of magnesium diethoxide. A temperature of 20°C to 25°C is maintained during these additions. The resulting mixture is then heated to 110°C with stirring, the temperature being maintained for 1 hour. At the end of this time, the mixture is filtered while hot. A solid material is collected.

The solid material is then slurried in a 50/50 (vol/vol) solution of 3558 liters of titanium tetrachloride and chlorobenzene at room temperature. The resulting slurry is then heated to 110°C with stirring, the temperature being maintained for 60 minutes. At the end of this time, the mixture is filtered while hot. A solid material is collected.

The solid material is reslurried in 3558 liters of the 50/50 (vol/vol) solution. The resulting slurry is heated to 110°C with stirring and the temperature being maintained in 30 minutes. At the end of this time, the

mixture is filtered while hot. A solid material is collected.

The residue is washed 4 times with 3785 liter portions of isopentane at 25°C and then dried under a nitrogen purge.

C. Preparation of Procatalyst No. 3

To a 50/50 solution (vol/vol) of 2953 liters of titanium tetrachloride and chlorobenzene, are added, in succession, 50 kg of diisobutyl phthalate, and 231 kg of carbonized magnesium ethoxide. --. temperature of 20°C to 25°C is maintained during these additions. The resulting mixture is then heated to 110°C with stirring, the temperature being maintained for 1 hour. At the end of this time, the mixture is filtered while hot. A solid material is collected. The solid material is then slurried in a 50/509

(vol/vol) solution of 2953 liters of titanium tetrachloride and chlorobenzene at room temperature. The resulting slurry is then heated to 110°C with stirring, the temperature being maintained for 60 minutes. At the end of this time, the mixture is filtered while hot. A solid material is collected.

The solid material is reslurried in 2953 liters of the 50/50 (vol/vol) solution. The resulting slurry is heated to 110°C with stirring and the temperature being maintained in 30 minutes. At the end of this time, the mixture is filtered while hot. A solid material is collected.

The residue is washed once with 2271 liters of isopentane at 25°C and then dried under a nitrogen purge. D. Polymerization

The procatalyst of sections A, B, or C were continuously fed into a fluidized bed reactor as a 30% by weight dispersion in mineral oil. Simultaneously and continuously, triethylaluminum, as a 5% by weight solution in isopentane and a selectivity control agent ("SCA" = NPTMS or DIBDMS) as a 0.5 to 5 percent solution in isopentane, were introduced to the reactor. Sufficient hydrogen was

introduced to regulate the molecular weight of the polymer product. A small amount of nitrogen is also present. The partial pressure of propylene was from about 330 psi to about 380 psi. The polymerization temperature was 65°C and the residence time was 1.5-2 hours. The reactor products were recovered by conventional means. Illustrative Embodiment II

A. Film Casting of Polymer Product

Some of the polymer reactor products, produced according to Illustrative Embodiments I, were recovered by conventional means. Some of the recovered reactor products (propylene/butene-1 random copolymer with about 7% by weight butene-1 and melt flow of 3.4, as measured by ASTM D-1238 Cond. L) were mixed and pelletized with a base additive package of Irganox® 1010 (500 ppm) , Ultranox® 626 (800 ppm) , Hydrotalcite DHT-4A (200 ppm) and one of the following candidate agents:

1) Hoechst® pp wax 230 which is a polypropylene wax available from Hoechst Celanese, 2) Millad® 3905 nucleating agent available from Milliken Chemicals,

3) Millad® 3940 nucleating agent available from Milliken,

4) Millad® 3988 nucleating agent which is an unsymmetrical sorbitol derivative available from Milliken,

5) Mark® 2180 nucleating agent available from Witco Corporation,

6) Calcium montanate available from Hoechst Celanese, as Hostalub VP® CAW2, 7) Polywax® 3000 T6 which is a polyethylene wax available from Petrolite Corporation,

8) Vantalc® 6H talc available from R. T. Vanderbilt Company,

9) GP638R graphite available from Union Carbide, or 10) NC-4 which is sodium bis(para-tert-butylphenyl) phosphate available from Mitsui Toatsu Chemicals.

The pellets were extruded into 5 mil thick cast film using a 3/4 inch Brabender extruder (200°C melt temperature) with 8 inch wide die and Killion chill roll

(15°C) . Operating conditions for all polymer blends were the same.

Crystallization temperature (Tc) was measured using a Perkin Elmer Series 7 Differential Scanning

Calorimeter Ther al Analysis System. The polymer was melted at 220°C and then cooled at 10°C/minute. The exothermic peak temperature was recorded as the Tc.

The test results for the films produced are provided in Tables 1 and 2.

Table 1

PPM Level ²

0 1000 2000 3500 5000

AGENT % Haze

Millad® 3905 8.7 3.7 3.8 4.8 ——

Millad® 3940 8.7 2.4 2.3 2 —

Mark® 2180 8.7 7.7 8.2 10.3 —

NC4 8.7 1.8 3 2.7 —

Millad® 3988 8.7 3.3 2.7 1.6 —

Ca Montanate 8.7 1.7 1.7 — 1.7

PP wax ³ 8.7 1.7 1.6 — 1.6

Na Benzoate 8.7 16.6 16.4 24.4 —

PEWAX ⁴ 8.7 5.8 8.9 — 5.3

Vantalc 6H 8.7 15.9 17.1 — 20.5

Graphite (GP638R) 8.7 15.0 21.4 — —

'Table 1 presents % haze data as a function of the agent. ² Parts per million of agent used in polymer composition. ³ Polypropylene wax "Polyethylene wax

As noted in Table 1, the presence of sodium benzoate, talc or graphite tends to increase the haze (i.e., lower the transparency) of propylene-butene random copolymer.

Table 2 ¹

PPM LEVEL

0 1000 2000 3500 5000

AGENT Crvstallization Temperature. °C

Millad® 3905 103.8 103.8 112.3 112.0 —

Millad® 3940 103.8 111.0 115.8 116.0 —

Mark® 2180 103.8 115.7 116.3 117.1 —

NC-4 103.8 107.6 116.6 117.1 —

Millac ^" 3988 103.8 112.8 116.4 117.4 —

Ca Montanate 103.8 103.95 103.95 — 103.1

PP Wax ² 103.8 106.0 104.5 — 103.8

Na benzoate 103.8 114.1 115.9 115.3 —

PE Wax ³ 103.8 102.3 103.3 — 103.3

Vantalc® 6H 103.8 110.7 108.8 — 108.2

Graphite (GP638R) 103.8 107.1 108.4 — 109.8

'Crystallization temperature (T _c ) of propylene-butene random copolymer as a function of parts per million (PPM) level of agent in composition.

² Polypropylene wax

³ Polyethylene wax

As presented in Table 2, calcium montanate, poly¬ propylene wax and polyethylene wax generally did not nucleate the propylene-butene random copolymer.

B. Film Casting of Polymer Products

Some of the polypropylene products, produced according to Illustrative Embodiment I and Comparative

Examples I and II, were recovered by conventional means. Some of the recovered products were mixed with one of the following additives packages:

1) 1000 ppm of Irganox® 1010 hindered phenolic primary antioxidant available from Ciba Geigy Corporation, 1000 ppm of Irgafos® 168 phosphite secondary antioxidant available from Ciba Geigy Corporation, 400 ppm of Hydrotalcite DHT-4A acid neutralizer available from Kyowa Chemical Industry.

2) 500 ppm of Irganox® 1010, 800 ppm of Ultranox® 626 secondary phosphite stabilizer available from General Electric Specialty Chemicals and 200 ppm of Hydrotalcite DHT-4A.

3) 1000 ppm of Irganox® 1010, 1000 ppm of Irgafos® 168, 400 ppm of Hydrotalcite DHT 4A and 2000 ppm of Sylobloc® 250 which is a 1:1 by weight combination of amorphous silica and erucamide available from W.R. Grace.

4) 1000 ppm of Irganox® 1010, 1000 ppm of Irgafos® 168, and 500 ppm of Hydrotalcite DHT 4A.

After the recovered products were mixed with one of the above-described additive packages, the resultant mixture was visbroken with sufficient peroxide to obtain the desired melt flow product.

The visbroken polymer product pellets were cast into film according to one of the following procedures: i. The pellets were extruded into 0.005 inch thick cast film using a 3 inch diameter extruder (30:1 L/D ratio; 260°C melt temperature; speed of about 67 RPM; and head pressure of 2300 psi), a 42.5 inch wide die, and 18 inch diameter chill roll (24°C). ii. The pellets were extruded into cast films of various thickness using a 4% inch diameter extruder (30:1

L/D ratio; 264°C melt temperature; head pressure of 3000 psi) , 75 inch wide die and a 24 inch diameter chill roll.

iii. Pellets were extruded into 0.004 inch thick cast film using a 3/4 inch diameter Brabender extruder (24:1

L/D ratio; extruder speed of 67 RPM; melt temperature of

248°C; and head pressure of 500 psi) , an 8 inch wide die and a 10 inch diameter chill roll (25°C) . iv. Pellets were extruded into a 0.001 inch thick cast film using a 3/4 inch diameter extruder (25:1 L/D ratio) with an 8 inch wide die and a 10 inch diameter chill roll. The "melt point" (°C) is obtained from a differential scanning calorimetry curve for each polymer product produced.

The other properties of the random copolymer composition were measured as follows: Elongation (%) D-882

Melt Flow ASTM D1238.78 Cond. L

Haze ASTM D1003

Gloss (at 60°) ASTM D523

Modulus (1% secant at 0.05 ASTM D882 inches/min)

Tensile Strength at Break ASTM D882

The results of a series of polymerizations are shown in

Tables 3, 4, and 5.

Comparative Example I The same procedures used in Illustrative

Embodiment I(B) were repeated except ethylene was substituted for butene-1. The results of a series of polymerizations are shown in Tables 3, 4, and 5.

Comparative Example II A. Preparation of Procatalyst Component

The procatalyst was prepared by adding 200 kg magnesium diethoxide (50 mmol) to 4164 liters of a 50/50

(vol/vol) mixture of chlorobenzene/TiCl ₄ . After adding 88 kg of ethyl benzoate, the mixture was heated and stirred at 96°C for approximately 30 minutes, the mixture was then filtered. The filtrate was reslurried with 4164 liters of the 50/50 (vol/vol) mixture of titanium tetrachloride and chlorobenzene and then heated to 96°C with stirring. The temperature was maintained for 10 minutes. At the end of this time, the mixture was filtered hot.

The filtrate is reslurried in 4164 liters of the 50/50 mixture and 21 liters of benzoyl chloride. The resulting slurry is heated to 96°C with stirring for about 10 minutes. The mixture is filtered while hot.

The residue is washed four times with 5106 liter portions of isopentane at 25°C and then dried under a nitrogen purge.

B. Polymerization

Using the above-described procatalyst (section A) , propylene and ethylene were polymerized, in the same manner, as described in Illustrative Embodiment 1(C), except the selectivity control agent was PEEB.

The resulting copolymer products were cast into films of various thickness using the procedures as described in Illustrative Embodiment III(B) . The results are furnished in Tables 4 and 6.

TABLE 3 ³

Tensile Seal ⁴

Modulus Tensile Strength Elongation § Gloss Temp.

Sample (psi) § Break (psi) Break (psi) Haze Clarity § 60°C °C

A ¹ 72,600 5,900 893 4.1 42.0 136 135

B ² 58,800 5,100 828 3.9 22.8 134 135

'Butene random copolymer containing 7.5% by weight butene (Illustrative Embodiment 1(C))

² Ethylene random copolymer containing 3.7% by weight ethylene (Comparative Example 1)

³ Films were cast according to Procedure (i) of Illustrative Embodiment III (film is 0.005 inches thick) . t vo

"Determined by "H.S.I.T./a"

TABLE 4 ^e

"Polymer composition mixed and pelletized with Additive package 3 of Illustrative Embodiment

III(B) ^b Polymer composition mixed and pelletized with Additive package 1 of Illustrative Embodiment

III(B) Εthylene random containing 5.5% ethylene and have melt flow of 7 dg/min (See Comparative

Example II) ^d Average Film Thickness: .004" ^• Melting point as determined by DSC ^f Heat seal initiation temperature, by H.S.I.T./a ^g Films prepared according to Procedure (iii) of Illustrative Embodiment III(B)

TABLE 5"

Tensile Strength

1% Secant Modulus § Break Elongation Gloss § Thickness (xlOOO psi) (xlOOO ps-1) at Break Haze Clarity 60° (mils)

92.1 5.6 699 1.2 52 138 2.5

105.8 5.3 762 1.5 36 138 3.5

108.5 5.3 822 2.6 20 134 4.8

106.6 5.3 750 2.2 50 136 3,25

100.3 5.3 725 1.8 44 139 3.15

102.5 5.3 755 1.5 34 139 3.15 J

"Each random copolymer incorporates 7% wt butene and was cast into film according to Procedure (ii) of Illustrative Embodiment III(B)

TABLE 6°

Temp ^d MF* Butene Xylene Hexane DSC H.S.I.T. ^f

Sample SCA (°C) (dg/min) (% wt) Sol. (%) Sol. (%) (T _m °C) (°C)

1" DIBDMS 80 4.6 12.7 6.6 3.4 137 110

2" DIBDMS 80 3.0 13.6 9.0 4.8 136 108

3" DIBDMS 80 2.9 13.6 10.2 6.1 134 106

4" DIBDMS 65 2.8 12.9 8.1 4.7 137 107

5" DIBDMS 65 2.2 12.6 8.7 5.5 137 108

6" DIBDMS 65 2.2 13.2 9.3 5.9 136 107

7" NPTMS 80 2.8 11.9 6.1 3.1 137 109

8" NPTMS 80 2.8 12.2 6.1 3.0 137 108

9" NPTMS 65 2.6 12.6 6.1 4.0 137 107 ω

10* NPTMS 65 2.1 12.8 6.1 3.2 136 111 t

11" NPTMS 65 2.4 13.4 8.3 4.8 134 107

12" NPTMS 65 1.8 14.0 8.2 5.8 134 107

13 PEEB 65 — — 7.3 4.5 141 120

14 ^b PEEB 65 — — 9.2 5.5 134 115

15 ^b PEEB 65 — — 12.6 7.8 133 113

16 PEEB 65 — — 13.1 8.4 132 113

"Used procatalyst of Illustrative Embodiment 1(B) ^b) Used procatalyst of Comparative Example II (Samples 13, 14, 15 and 16 incorporating 3.8%.

5.5%,5.9% and 6.1% of ethylene, respectively) ^C) A11 samples were cast into film using Procedure (iv) of Illustrative Embodiment III(B). ^• "Reactor temperature ^e) Melt flow of powder °On one mil film, using 500 g/inch for H.S.I.T.

Illustrative Embodiment IV

Cast films were extruded from random copolymer compositions containing 7% by weight butene and additive package (1) or additive package (2) (see Illustrative Embodiment 111(B)). The rolls of film were stored at 21°C. After two weeks in storage, the ends of each roll were visually inspected for color using a rating scale of 1 to 5 (where 1 represents no yellowing present and 5 represents extreme or high yellowing) . The visual ratings of film rolls from the two formulations were as follows.

TABLE 7

Color Rating Film w/formulation (1) 4

Film w/formulation (2) 1.5