Polypropylene copolymer with high transparency and toughness

Abstract

Polypropylene polymer compositions having high transparency, in combination with excellent impact strength and optionally excellent stiffness properties, and methods of making such compositions are provided. Such polypropylene polymer compositions also have a low melt flow rate (e.g., 5 g / 10 min or less, or 4 g / 10 min or less).

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 344,193, filed on May 20, 2022, which is incorporated herein by reference in its entirety for any and all purposes.

[0003] field

[0004] The present technology generally relates to polypropylene polymer compositions having an improved balance of properties. More specifically, the polypropylene polymer compositions exhibit high clarity and toughness.

[0005] background

[0006] Polyolefins, such as polypropylene, are used in different demanding applications. Therefore, people are constantly looking for customized polymers that can meet the requirements of these applications. For example, heterophasic systems are known for their good impact behavior. Such heterophasic propylene copolymers contain a crystalline matrix, which is a propylene homopolymer or a random propylene copolymer, in which an elastomeric copolymer, such as a propylene / ethylene copolymer, is dispersed.

[0007] The present disclosure provides polypropylene compositions comprising heterophasic propylene copolymers having high clarity and high stiffness / toughness and corresponding methods for preparing such compositions. Such polypropylene compositions have an improved balance of properties compared to those disclosed in the prior art and are suitable for thermoforming and extrusion blow molding applications.

[0008] Overview

[0009] In general, the present disclosure relates to polypropylene polymer compositions having an improved balance of properties. For example, polypropylene polymer compositions prepared according to the present disclosure can be formulated to have high clarity, combined with excellent impact strength. For example, the polymer compositions described herein have relatively low haze values, while having excellent toughness properties. In addition, these polymer compositions can also exhibit excellent stiffness properties.

[0010] The polypropylene polymer compositions described herein are prepared by combining a first polymer phase comprising a polypropylene homopolymer or random copolymer with a second polymer phase comprising a rubbery propylene / ethylene copolymer. The selection of specific parameters for each polymer phase as described herein provides a polypropylene polymer composition having high clarity, combined with excellent impact strength and optionally excellent stiffness properties.

[0011] In one aspect, a polypropylene composition is provided, comprising:

[0012] (a) a first polymer phase comprising a polypropylene homopolymer or random copolymer, the polypropylene homopolymer or random copolymer optionally comprising one or more comonomers in an amount equal to or less than about 3 wt % based on the total weight of the propylene homopolymer or copolymer, the polypropylene homopolymer or random copolymer having a total cold xylene soluble content of about 2 wt % to about 6 wt % and having a melt flow rate of about 0.5 g / 10 min to about 3 g / 10 min; and

[0013] (b) a second polymer phase comprising a propylene / ethylene copolymer comprising ethylene in an amount less than about 18 weight percent based on the total weight of the propylene / ethylene copolymer;

[0014] wherein the ratio of the melt flow rate of the polypropylene homopolymer or random copolymer to the melt flow rate of the propylene / ethylene copolymer is greater than about 1.0; and

[0015] wherein the first polymer phase and the second polymer phase are combined to provide the polypropylene composition, the polypropylene composition having a melt flow rate of about 4 g / 10 min or less, an ethylene content of less than about 5 wt%, a total cold xylene soluble content of about 5 wt% to about 20 wt%, a haze of less than about 20% at 1 mm, an IZOD impact strength of greater than about 500 J / m at 23° C., a Gardner drop impact strength of greater than about 150 inch pounds at 0° C., and a flexural modulus of greater than or equal to about 800 MPa.

[0016] In some embodiments, the first polymer phase comprises a crystalline matrix comprising a polypropylene homopolymer or a random copolymer. In some embodiments, the polypropylene composition comprises a heterophasic propylene copolymer.

[0017] In some embodiments, the first polymer phase comprises a polypropylene homopolymer or a random copolymer, and the polypropylene homopolymer or the random copolymer comprises one or more comonomers, and the amount of the comonomer is based on the total weight of the propylene homopolymer or the copolymer. About 0 weight % to about 3 weight %. In some embodiments, the first polymer phase comprises a polypropylene homopolymer or a random copolymer with a total cold xylene soluble content of about 2.5 weight % or about 4.8 weight %. In some embodiments, the first polymer phase comprises a polypropylene homopolymer or a random copolymer with a melt flow rate of about 0.5g / 10min to about 1.5g / 10min. In some embodiments, the propylene / ethylene copolymer present in the second polymer phase comprises butene.

[0018] In some embodiments, the polypropylene composition has a melt flow rate of about 0.5g / 10min to about 1.5g / 10min. In some embodiments, the polypropylene composition has an ethylene content of about 2% by weight to about 4.5% by weight. The polypropylene composition has a total cold xylene soluble content of about 7% by weight or about 12% by weight. In some embodiments, the polypropylene composition has a haze of about 5% to about 15% at 1mm. In some embodiments, the polypropylene composition has an IZOD impact strength of about 500J / m to about 900J / m at 23°C. In some embodiments, the polypropylene composition has a Gardner drop impact strength of about 150 inch pounds to about 350 inch pounds at 0°C. In some embodiments, the polypropylene composition has a flexural modulus of about 800MPa to about 1300MPa.

[0019] In another aspect, a polypropylene composition is provided, comprising:

[0020] (a) a first polymer phase comprising a polypropylene homopolymer or random copolymer, the polypropylene homopolymer or random copolymer optionally comprising one or more comonomers in an amount equal to or less than about 1 wt % based on the total weight of the propylene homopolymer or copolymer, the polypropylene homopolymer or random copolymer having a total cold xylene soluble content of less than about 4 wt % and having a melt flow rate of about 2 g / 10 min to about 5 g / 10 min; and

[0021] (b) a second polymer phase comprising a propylene / ethylene copolymer comprising ethylene in an amount less than about 18 weight percent based on the total weight of the propylene / ethylene copolymer;

[0022] wherein the ratio of the melt flow rate of the polypropylene homopolymer or random copolymer to the melt flow rate of the propylene / ethylene copolymer is greater than about 1.0; and

[0023] wherein the first polymer phase and the second polymer phase are combined to provide the polypropylene composition, the polypropylene composition having a melt flow rate of about 5 g / 10 min or less, an ethylene content of less than about 3.5 wt%, a total cold xylene soluble content of about 5 wt% to about 15 wt%, a haze of less than about 20% at 1 mm, an IZOD impact strength of greater than about 200 J / m at 23°C, and a flexural modulus of greater than or equal to about 1100 MPa.

[0024] In some embodiments, the first polymer phase comprises a polypropylene homopolymer or a random copolymer, and the polypropylene homopolymer or the random copolymer comprises one or more comonomers, and the amount of the comonomer is based on the gross weight of the propylene homopolymer or the copolymer from about 0.5 wt % to about 1 wt %. In some embodiments, the first polymer phase comprises a polypropylene homopolymer or a random copolymer with a total cold xylene soluble content of about 1 wt % or about 3 wt %. In some embodiments, the first polymer phase comprises a polypropylene homopolymer or a random copolymer with a melt flow rate of about 2g / 10min to about 4g / 10min. In some embodiments, the propylene / ethylene copolymer present in the second polymer phase comprises butene.

[0025] In some embodiments, the polypropylene composition has a melt flow rate of about 2g / 10min to about 4g / 10min. In some embodiments, the polypropylene composition has an ethylene content of about 2% by weight to about 3.5% by weight. In some embodiments, the polypropylene composition has a total cold xylene soluble content of about 5.5% by weight or about 12% by weight. In some embodiments, the polypropylene composition has a haze of about 10% to about 20% at 1mm. In some embodiments, the polypropylene composition has an IZOD impact strength of about 200J / m to about 900J / m at 23°C. In some embodiments, the polypropylene composition has a flexural modulus of about 1200MPa to about 1600MPa.

[0026] In any embodiment, the second polymer phase comprises a propylene / ethylene copolymer comprising ethylene in an amount from about 10 wt% to about 18 wt% based on the total weight of the propylene / ethylene copolymer.

[0027] In any embodiment, the ratio of the melt flow rate of the polypropylene homopolymer or random copolymer to the melt flow rate of the propylene / ethylene copolymer is from about 1.0 to about 3.0.

[0028] In any embodiment, the polypropylene composition has a Gardner drop impact strength at 23°C of greater than about 150 inch pounds.

[0029] In any embodiment, the polypropylene composition further comprises one or more nucleating agents, antacids, and antioxidants. In some embodiments, the one or more nucleating agents are present in an amount of about 5000 ppm or less.

[0030] In any embodiment, the one or more comonomers present in the polypropylene homopolymer or random copolymer comprises ethylene.

[0031] In another aspect, there is also provided a molded article formed from any of the polypropylene compositions described herein. In some embodiments, the molded article is an extrusion blow molded article.

[0032] In another aspect, there is also provided a process for preparing any one of the polypropylene compositions described herein by sequential polymerization in the presence of a Ziegler-Natta catalyst, wherein:

[0033] preparing a first polymer phase in a first gas phase reactor, and

[0034] transferring the first polymer phase to a second gas phase reactor comprising a second polymer phase;

[0035] Therein, the first polymer phase is combined with the second polymer phase to provide a polypropylene composition.

[0036] In another aspect, there is also provided a method of preparing any of the polypropylene compositions described herein, comprising:

[0037] feeding propylene and optionally one or more comonomers into a first reactor; feeding a catalyst mixture comprising (1) a Ziegler-Natta catalyst, (2) a cocatalyst, and (3) an external donor into the first reactor;

[0038] contacting the propylene with the catalyst mixture under first polymerization conditions to polymerize the propylene and optionally one or more comonomers to form a first polymer phase comprising a propylene homopolymer or copolymer;

[0039] transferring at least a portion of the first polymer phase to a second reactor; and

[0040] feeding additional propylene and ethylene into the second reactor to form a second polymer phase;

[0041] Therein, the first polymer phase is combined with the second polymer phase to provide the polypropylene composition.

[0042] Other features and aspects of the disclosure are discussed in more detail below.

[0043] Details

[0044] Various embodiments are described below. It should be noted that the specific embodiments are not intended as an exhaustive description or as a limitation to the broader aspects discussed herein. An aspect described in conjunction with a specific embodiment is not necessarily limited to that embodiment and can be practiced with any other one or more embodiments.

[0045] As used herein, "about" will be understood by one of ordinary skill in the art and will vary to some extent depending on the context in which it is used. If the use of the term is unclear to one of ordinary skill in the art, "about" will mean up to + or - 10% of the particular term, given the context in which it is used.

[0046] Unless otherwise specified herein or clearly contradicted by context, the terms "one" and "a kind of" and "the" and similar indicators used in the context of describing elements (especially in the context of the following claims) should be interpreted as covering the singular and plural. Unless otherwise specified herein, the enumeration of the numerical ranges herein is only intended to serve as a shorthand for referring to each individual value falling within the range one by one, and each individual value is incorporated into this specification as if it is enumerated one by one in this article. Unless otherwise specified herein or otherwise clearly contradicted by context, all methods described herein can be performed in any suitable order. Unless otherwise specified, the use of any and all examples or exemplary wordings (such as "such as") provided herein is intended only to better illustrate the embodiments, rather than to limit the scope of the claims. The wording in the specification should not be interpreted as indicating that any unclaimed element is essential.

[0047] Typically, alkyl, alkenyl, aryl or ether groups (such as alkyl) defined below can be substituted, wherein one or more bonds with hydrogen atoms contained therein are replaced with bonds with non-hydrogen or non-carbon atoms. Substituent groups also include groups in which one or more bonds with one or more carbon or hydrogen atoms are replaced with one or more bonds (including double bonds or triple bonds) with heteroatoms. Thus, unless otherwise stated, substituted groups will be replaced by one or more substituents. In some embodiments, substituted groups are replaced by 1,2,3,4,5 or 6 substituents. Examples of substituents include: halogen (i.e., F, Cl, Br, and I); hydroxy; alkoxy, alkenyloxy, alkynyloxy, aryloxy, aralkyloxy, heterocyclooxy, and heterocycloalkoxy; carbonyl (oxo); carboxyl; ester; carbamate; oxime; hydroxylamine; alkoxyamine; aralkyloxyamine; thiol; sulfide; sulfoxide; sulfone; sulfonyl; sulfonamide; amine; N-oxide; hydrazine; hydrazide; hydrazone; azide; amide; urea; amidine; guanidine; enamine; imide; isocyanate; isothiocyanate; cyanate; thiocyanate; imine; nitro; nitrile (i.e., CN); and the like.

[0048] As used herein, "alkyl" includes straight and branched chain alkyl groups having 1 to about 20 carbon atoms, and usually 1 to 12 carbon atoms, or in some embodiments 1 to 8 carbon atoms. As used herein, "alkyl" includes cycloalkyl groups defined as follows. Alkyl groups may be substituted or unsubstituted. Alkyl groups may be substituted one or more times. Alkyl groups may be substituted twice or more. Examples of straight chain alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. Examples of branched chain alkyl groups include, but are not limited to, isopropyl, sec-butyl, tert-butyl, neopentyl, isopentyl, and 1-cyclopentyl-4-methylpentyl. Representative substituted alkyl groups may be substituted one or more times by, for example, amino, thio, hydroxyl, cyano, alkoxy, and / or halogen groups such as F, Cl, Br, and I groups. As used herein, the term haloalkyl group is an alkyl group having one or more halogen groups. In some embodiments, haloalkyl refers to a perhaloalkyl group.

[0049] Alkenyl is a straight chain, branched or cyclic hydrocarbon radical having 2 to about 20 carbon atoms and further comprising at least one double bond. In some embodiments, alkenyl has 1 to 12 carbon atoms, or generally 1 to 8 carbon atoms. Alkenyl can be substituted or unsubstituted. Alkenyl includes, for example, vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl, cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl and especially hexadienyl. Alkenyl can be substituted similarly to alkyl. Divalent alkenyl, i.e., alkenyl with two points of attachment, includes but is not limited to CH-CH=CH2, C=CH2 or C=CHCH3.

[0050] As used herein, "aryl" or "aromatic" groups are cyclic aromatic hydrocarbons that do not contain heteroatoms. Aryl includes monocyclic, bicyclic and polycyclic systems. Thus, aryl includes, but is not limited to, phenyl, azulenyl, heptalenyl, biphenylene, indacenyl, fluorenyl, phenanthrenyl, triphenylene, pyrenyl, naphthyl, chrysene, biphenyl, anthracenyl, indenyl, dihydroindenyl, pentalenyl and naphthyl. Aryl with one or more alkyl groups may also be referred to as alkaryl. In some embodiments, aryl contains 6-14 carbons in the ring portion of the group, and in other embodiments contains 6 to 12 or even 6-10 carbon atoms. The phrase "aryl" includes groups containing fused rings, such as fused aromatic-aliphatic ring systems (e.g., dihydroindenyl, tetrahydronaphthyl, etc.). Aryl can be substituted or unsubstituted.

[0051] The term "alkoxy" refers to an (alkyl)O- group, wherein alkyl is as defined herein.

[0052] The term "cycloalkyl" refers to a monocyclic or polycyclic aliphatic non-aromatic group, wherein each atom (i.e., skeleton atom) forming the ring is a carbon atom. In some embodiments, cycloalkyl is a spirocyclic or bridging compound. In some embodiments, cycloalkyl is optionally fused with an aromatic ring, and the point of attachment is located on the carbon of a non-aromatic ring carbon atom. Cycloalkyl includes a group with 3 to 10 ring atoms. In some embodiments, cycloalkyl is selected from cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cyclooctyl, spiro [2.2] pentyl, norbornyl and bicyclo [1.1.1] pentyl. In some embodiments, cycloalkyl is C3-C6 cycloalkyl. In some embodiments, cycloalkyl is a monocyclic cycloalkyl. Monocyclic cycloalkyl includes but is not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Multicyclic cycloalkyl groups include, for example, adamantyl, norbornyl (ie, bicyclo[2.2.1]heptanyl), norbornenyl, decalinyl, 7,7-dimethyl-bicyclo[2.2.1]heptanyl, and the like.

[0053] The term "propylene / ethylene copolymer" as used herein is a copolymer containing a major weight percentage of propylene monomer with ethylene monomer as a minor component and does not exhibit a well-defined melting peak. A random copolymer is a polymer having individual repeating units of the comonomer present in a random or statistical distribution in the polymer chain, which can be defined as crystalline because it exhibits a well-defined melting peak.

[0054] As used herein, melt flow rate (MFR) is measured according to ASTM D 1238 test method at 230° C. using a 2.16 kg weight for propylene-based polymers. When measuring samples before pelletization (powder MFR), the polymer is mixed with antioxidants and antacids in a manner known to those skilled in the art before measuring the MFR to avoid degradation during the measurement.

[0055] Cold xylene solubles (XS) are defined as the weight percentage of the resin remaining in the solution after the polypropylene resin sample is dissolved in hot xylene and the solution is cooled to 25°C. A 90-minute settling time is used according to ASTM D5492-98, which is also referred to as the gravimetric XS method, and is also referred to as the "wet method" in this article. The procedure includes weighing 2 grams of sample and dissolving the sample in 200 milliliters of o-xylene in a 400 milliliter flask with a 24 / 40 joint. The flask is connected to a water-cooled condenser, and the contents are stirred and heated to reflux under nitrogen (N2), and then kept at reflux for another 30 minutes. The solution is then cooled in a temperature-controlled water bath at 25°C for 90 minutes to crystallize the xylene-insoluble portion. Once the solution is cooled and the insoluble portion is precipitated from the solution, the separation of the xylene-soluble portion (XS) and the xylene-insoluble portion (XI) is achieved by filtering through 25 micron filter paper. 100 ml of filtrate is collected in a pre-weighed aluminum pan, and o-xylene is evaporated from the 100 ml of filtrate under a nitrogen stream. Once the solvent evaporates, the pan and contents are placed in a 100°C vacuum oven for 30 minutes or until dry. The pan is then cooled to room temperature and weighed. The xylene soluble portion is calculated as XS (wt %) = [(m3-m2)*2 / m1]*100, where m1 is the original weight of the sample used, m2 is the weight of the empty aluminum pan, and m3 is the weight of the pan and residue (here and elsewhere in the disclosure, the asterisk * indicates that the identified term or value is multiplied). XS can also be measured according to the Viscotek method as follows: 0.4 g of polymer is dissolved in 20 ml of xylene at 130°C under stirring for 60 minutes. The solution is then cooled to 25°C, and the insoluble polymer portion is filtered out after 90 minutes. The filtrate was analyzed by flow injection polymer analyzer using a Viscotek ViscoGEL H-100-3078 column with THF mobile phase flowing at 1.0 ml / min. The column was coupled to a Viscotek Model 302 triple detector array with light scattering, viscometer and refractometer detectors operating at 45°C. TM Polystyrene standards maintain instrument calibration. Homopolymers (e.g. Dow 5D98) are used as reference materials to ensure that the Viscotek instrument wet methods defined in the next paragraph return identical results and can therefore be used interchangeably.

[0056] As the primary method, the ethylene content of random ethylene copolymers and ethylene / propylene copolymers was measured using Fourier transform infrared (FTIR), which is similar to the method using 13The relationship and agreement between the measurements made using these two methods are described, for example, in JR Paxson, JC Randall, "Quantitative Measurement of Ethylene Incorporation into Propylene Copolymers by Carbon-13 Nuclear Magnetic Resonance and Infrared Spectroscopy," Analytical Chemistry, Vol. 50, No. 13, November 1978, 1777-1780.

[0057] The MFR of the second phase is calculated using the following equation

[0058]

[0059] Where MFR P2 refers to the MFR of the ethylene / propylene copolymer prepared in the second phase), MFR c refers to the MFR of the composition measured before granulation (powder MFR), MFR P1 refers to the MFR of the first phase and f1 refers to the amount of phase 1 in the composition.

[0060] Flexural modulus is measured according to ASTM D790-10 Method A at 1.3 mm / min using Type 1 specimens conforming to ASTM 3641 and molded according to ASTM D4101.

[0061] IZOD impact strength is measured according to ASTM D 256 on samples molded according to ASTM D4101.

[0062] The Gardner impact test was measured according to ASTM D5420.

[0063] Haze was measured according to ASTM test D1003, procedure A, using a BYK Gardner Haze-Gard Plus 4725 on 1 mm thick injection molded specimens.

[0064] Polypropylene polymer composition

[0065] The present disclosure relates to polypropylene polymer compositions with improved property balance, such as high transparency with excellent impact strength and optionally excellent stiffness properties. These polypropylene polymer compositions also have a low melt flow rate (e.g., 5 g / 10 min or less or 4 g / 10 min or less). Such polypropylene polymer compositions described herein include heterophasic polypropylene copolymers, which are prepared by combining a first polymer phase comprising a polypropylene homopolymer or a random copolymer with a second polymer phase comprising a rubbery propylene / ethylene copolymer. The selection of specific parameters of each polymer phase as described herein provides a polypropylene polymer composition with high transparency, excellent impact strength (particularly at room temperature) in combination, and optionally excellent stiffness properties. Specifically, the polypropylene polymer compositions described herein have a low haze of less than about 20%, an IZOD impact strength of greater than about 200 J / m at 23°C, and a flexural modulus of at least about 800 MPa.

[0066] The present disclosure recognizes that in order to obtain a polypropylene polymer composition having a low melt flow rate, having high clarity, combined with excellent impact strength and optionally excellent stiffness properties, a specific combination of parameters described for the first and second polymer phases is required. Specifically, low to no comonomer content (e.g., ethylene content) in the first polymer phase and low (less than 18 wt%) ethylene content in the second polymer phase provide high stiffness / toughness and high clarity. Such parameters provide a polypropylene composition having a low ethylene content (e.g., less than about 5 wt%).

[0067] The polypropylene composition described herein can have high transparency and high toughness. In one aspect, a polypropylene composition is provided, comprising:

[0068] (a) a first polymer phase comprising a polypropylene homopolymer or random copolymer, the polypropylene homopolymer or random copolymer optionally comprising one or more comonomers in an amount equal to or less than about 3 wt % based on the total weight of the propylene homopolymer or copolymer, the polypropylene homopolymer or random copolymer having a total cold xylene soluble content of about 2 wt % to about 6 wt % and having a melt flow rate of about 0.5 g / 10 min to about 3 g / 10 min; and

[0069] (b) a second polymer phase comprising a propylene / ethylene copolymer comprising ethylene in an amount less than about 18 weight percent based on the total weight of the propylene / ethylene copolymer;

[0070] wherein the ratio of the melt flow rate of the polypropylene homopolymer or random copolymer to the melt flow rate of the propylene / ethylene copolymer is greater than about 1.0; and

[0071] wherein the first polymer phase and the second polymer phase are combined to provide a polypropylene composition having a melt flow rate of about 4 g / 10 min or less, an ethylene content of less than about 5 wt%, a total cold xylene soluble content of about 5 wt% to about 20 wt%, a haze of less than about 20% at 1 mm, an IZOD impact strength of greater than about 500 J / m at 23°C, a Gardner drop impact strength of greater than about 150 inch pounds at 0°C, and a flexural modulus of greater than or equal to about 800 MPa.

[0072] In any embodiment, the first polymer phase comprises a crystalline matrix comprising a polypropylene homopolymer or a random copolymer. In any embodiment, the polypropylene composition comprises a heterophasic propylene copolymer. In some embodiments, butene may also be present in the second polymer phase. In some embodiments, the propylene / ethylene copolymer present in the second polymer phase comprises butene.

[0073] The first polymer phase comprising a polypropylene homopolymer or random copolymer may optionally include one or more comonomers in an amount equal to or less than about 3 wt % based on the total weight of the propylene homopolymer or copolymer. In some embodiments, the first polymer phase comprises a polypropylene homopolymer or random copolymer comprising one or more comonomers in an amount of about 0 wt % to about 3 wt %, including about 0 wt %, about 0.5 wt %, about 1.0 wt %, about 1.5 wt %, about 2.0 wt %, about 2.5 wt %, and about 3.0 wt %, based on the total weight of the propylene homopolymer or copolymer.

[0074] The first polymer phase may include about 2 wt % to about 6 wt %, including about 2.1 wt %, about 2.2 wt %, about 2.3 wt %, about 2.4 wt %, about 2.5 wt %, about 2.6 wt %, about 2.7 wt %, about 2.8 wt %, about 2.9 wt %, about 3.0 wt %, about 3.1 wt %, about 3.2 wt %, about 3.3 wt %, about 3.4 wt %, about 3.5 wt %, about 3.6 wt %, about 3.7 wt %, about 3.8 wt %, about 3.9 wt %, about 4.0 wt %. %, about 4.1 wt %, about 4.2 wt %, about 4.3 wt %, about 4.4 wt %, about 4.5 wt %, about 4.6 wt %, about 4.7 wt %, about 4.8 wt %, about 4.9 wt %, about 5.0 wt %, about 5.1 wt %, about 5.2 wt %, about 5.3 wt %, about 5.4 wt %, about 5.5 wt %, about 5.6 wt %, about 5.7 wt %, about 5.8 wt %, about 5.9 wt %, and about 6.0 wt %. In some embodiments, the first polymer phase comprises a polypropylene homopolymer or random copolymer having a total cold xylene solubles content of about 2.5 wt % or about 4.8 wt %.

[0075] The first polymer phase may have a phase range of about 0.5 g / 10 min to about 3 g / 10 min, including about 0.5 g / 10 min, about 0.6 g / 10 min, about 0.7 g / 10 min, about 0.8 g / 10 min, about 0.9 g / 10 min, about 1.0 g / 10 min, about 1.1 g / 10 min, about 1.2 g / 10 min, about 1.3 g / 10 min, about 1.4 g / 10 min, about 1.5 g / 10 min, about 1.6 g / 10 min, about 1.7 g / 10 min, about 1.8 g / 10 min, about 1.9 g / 10 min, about 2.0 g / 10 min, about 2.1 g / 10 min, about 2.2 g / 10 min, about 2.3 g / 10 min, about 2.4 g / 10 min, about 2.5 g / 10 min, about 2.6 g / 10 min, about 2.7 g / 10 min, about 2.8 g / 10 min, about 2.9 g / 10 min, about 3. In some embodiments, the first polymer phase comprises a polypropylene homopolymer or random copolymer having a melt flow rate of about 0.5 g / 10min to about 1.5 g / 10min. In some embodiments, the first polymer phase comprises a polypropylene homopolymer or random copolymer having a melt flow rate of about 0.9 g / 10min.

[0076] The polypropylene composition can have a melt flow rate of 4 g / 10 min or less, including about 0.5 g / 10 min, about 1 g / 10 min, about 1.5 g / 10 min, about 2 g / 10 min, about 2.5 g / 10 min, about 3 g / 10 min, about 3.5 g / 10 min, and about 4 g / 10 min. In some embodiments, the polypropylene composition has a melt flow rate of about 0.5 g / 10 min to about 1.5 g / 10 min.

[0077] The polypropylene composition can have an ethylene content of less than 5 wt%, including about 0.5 wt%, about 1 wt%, about 1.5 wt%, about 2 wt%, about 2.5 wt%, about 3 wt%, about 3.5 wt%, about 4 wt%, about 4.5 wt%, and about 5 wt%. In some embodiments, the polypropylene composition has an ethylene content of about 2 wt% to about 4.5 wt%.

[0078] The polypropylene composition can have a total cold xylene soluble content of about 5 wt % to about 20 wt %, including about 5 wt %, about 6 wt %, about 7 wt %, about 8 wt %, about 9 wt %, about 10 wt %, about 11 wt %, about 12 wt %, about 13 wt %, about 14 wt %, about 15 wt %, about 16 wt %, about 17 wt %, about 18 wt %, about 19 wt %, and about 20 wt %. In some embodiments, the polypropylene composition has a total cold xylene soluble content of about 7 wt % or about 12 wt %.

[0079] The polypropylene composition can have a haze of less than about 20% at 1 mm, including about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16%, about 17%, about 18%, about 19%, and about 20%. In some embodiments, the polypropylene composition has a haze of about 5% to about 15% at 1 mm.

[0080] The polypropylene composition may have an IZOD impact strength of greater than about 500 J / m, including about 500 J / m, about 525 J / m, about 575 J / m, about 600 J / m, about 625 J / m, about 650 J / m, about 675 J / m, about 700 J / m, about 725 J / m, about 750 J / m, about 775 J / m, about 800 J / m, about 825 J / m, about 850 J / m, about 875 J / m, and about 900 J / m at 23° C. In some embodiments, the polypropylene composition has an IZOD impact strength of about 500 J / m to about 900 J / m at 23° C.

[0081] The polypropylene composition can have a Gardner drop impact strength of greater than about 150 inch pounds at 0° C., including about 150 inch pounds, about 175 inch pounds, about 200 inch pounds, about 225 inch pounds, about 250 inch pounds, about 275 inch pounds, about 300 inch pounds, about 325 inch pounds, and about 350 inch pounds. In some embodiments, the polypropylene composition has a Gardner drop impact strength of about 150 inch pounds to about 350 inch pounds at 0° C.

[0082] The polypropylene composition can have a flexural modulus greater than or equal to about 800 MPa, including about 800 MPa, about 825 MPa, about 850 MPa, about 870 MPa, about 900 MPa, about 925 MPa, about 950 MPa, about 975 MPa, about 1000 MPa, about 1025 MPa, about 1050 MPa, about 1075 MPa, about 1100 MPa, about 1125 MPa, about 1150 MPa, about 1175 MPa, about 1200 MPa, about 1225 MPa, about 1250 MPa, about 1275 MPa, and about 1300 MPa. In some embodiments, the polypropylene composition has a flexural modulus of about 800 MPa to about 1300 MPa.

[0083] The polypropylene composition described herein can have high transparency, high toughness and high stiffness. In another aspect, a polypropylene composition is provided, comprising:

[0084] (a) a first polymer phase comprising a polypropylene homopolymer or random copolymer, the polypropylene homopolymer or random copolymer optionally comprising one or more comonomers in an amount equal to or less than about 1 wt % based on the total weight of the propylene homopolymer or copolymer, the polypropylene homopolymer or random copolymer having a total cold xylene soluble content of less than about 4 wt % and having a melt flow rate of about 2 g / 10 min to about 5 g / 10 min; and

[0085] (b) a second polymer phase comprising a propylene / ethylene copolymer comprising ethylene in an amount less than about 18 weight percent based on the total weight of the propylene / ethylene copolymer;

[0086] wherein the ratio of the melt flow rate of the polypropylene homopolymer or random copolymer to the melt flow rate of the propylene / ethylene copolymer is greater than about 1.0; and

[0087] wherein the first polymer phase and the second polymer phase are combined to provide a polypropylene composition having a melt flow rate of about 5 g / 10 min or less, an ethylene content of less than about 3.5 wt %, a total cold xylene soluble content of about 5 wt % to about 15 wt %, a haze of less than about 20% at 1 mm, an IZOD impact strength of greater than about 200 J / m at 23° C., and a flexural modulus of greater than or equal to about 1100 MPa.

[0088] The first polymer phase comprising a polypropylene homopolymer or random copolymer may optionally include one or more comonomers in an amount equal to or less than about 1 wt%, including about 0.1 wt%, about 0.2 wt%, about 0.3 wt%, about 0.4 wt%, about 0.5 wt%, about 0.6 wt%, about 0.7 wt%, about 0.8 wt%, about 0.9 wt%, and about 1 wt%, based on the total weight of the propylene homopolymer or copolymer. In some embodiments, the first polymer phase comprises a polypropylene homopolymer or random copolymer comprising one or more comonomers in an amount of about 0.5 wt% to about 1 wt%, based on the total weight of the propylene homopolymer or copolymer.

[0089] The first polymer phase comprises a polypropylene homopolymer or random copolymer that can have a total cold xylene soluble content of less than about 4 wt%, including about 0.5 wt%, about 1 wt%, about 1.5 wt%, about 2 wt%, about 2.5 wt%, about 3 wt%, about 3.5 wt%, and about 4 wt%. In some embodiments, the first polymer phase comprises a polypropylene homopolymer or random copolymer having a total cold xylene soluble content of about 1 wt% to about 3 wt%.

[0090] The first polymer phase comprises a polypropylene homopolymer or random copolymer that can have a melt flow rate of about 2 g / 10 min to about 5 g / 10 min, including about 2 g / 10 min, about 2.5 g / 10 min, about 3 g / 10 min, about 3.5 g / 10 min, about 4 g / 10 min, about 4.5 g / 10 min, and about 5 g / 10 min. In some embodiments, the first polymer phase comprises a polypropylene homopolymer or random copolymer having a melt flow rate of about 2 g / 10 min to about 4 g / 10 min.

[0091] The polypropylene composition can have a melt flow rate of about 5 g / 10 min or lower, including about 0.5 g / 10 min, about 1 g / 10 min, about 1.5 g / 10 min, about 2 g / 10 min, about 2.5 g / 10 min, about 3 g / 10 min, about 3.5 g / 10 min, about 4 g / 10 min, about 4.5 g / 10 min and about 5 g / 10 min. In some embodiments, the polypropylene composition has a melt flow rate of about 2 g / 10 min to about 4 g / 10 min.

[0092] The polypropylene composition can have an ethylene content of less than about 3.5 wt%, including about 0.5 wt%, about 1 wt%, about 1.5 wt%, about 2 wt%, about 2.5 wt%, about 3 wt%, and about 3.5 wt%. In some embodiments, the polypropylene composition has an ethylene content of about 2 wt% to about 3.5 wt%.

[0093] The polypropylene composition can have a total cold xylene soluble content of about 5 wt % to about 15 wt %, including about 5 wt %, about 5.5 wt %, about 6 wt %, about 6.5 wt %, about 7 wt %, about 7.5 wt %, about 8 wt %, about 8.5 wt %, about 9 wt %, about 9.5 wt %, about 10 wt %, about 10.5 wt %, about 11 wt %, about 11.5 wt %, about 12 wt %, about 12.5 wt %, about 13 wt %, about 13.5 wt %, about 14 wt %, about 14.5 wt %, and about 15 wt %. In some embodiments, the polypropylene composition has a total cold xylene soluble content of about 5.5 wt % or about 12 wt %.

[0094] The polypropylene composition can have a haze of less than about 20% at 1 mm, including about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16%, about 17%, about 18%, about 19%, and about 20%. In some embodiments, the polypropylene composition has a haze of about 10% to about 20% at 1 mm.

[0095] The polypropylene composition may have a thermal conductivity greater than about 200 J / m at 23° C., including about 200 J / m, about 225 J / m, about 250 J / m, about 275 J / m, about 300 J / m, about 325 J / m, about 375 J / m, about 400 J / m, about 425 J / m, about 450 J / m, about 475 J / m, about 500 J / m, about 525 J / m In some embodiments, the polypropylene composition has an IZOD impact strength of about 200 J / m to about 900 J / m at 23° C. In some embodiments, the polypropylene composition has an IZOD impact strength of about 200 J / m to about 600 J / m at 23° C.

[0096] Polypropylene composition can have and be greater than or equal to about 1200MPa, comprise about 1200MPa, about 1225MPa, about 1250MPa, about 1275MPa, about 1300MPa, about 1325MPa, about 1350MPa, about 1375MPa, about 1400MPa, about 1425MPa, about 1450MPa, about 1475MPa, about 1500MPa, about 1525MPa, about 1550MPa, about 1575MPa and the flexural modulus of about 1600MPa.In some embodiments, polypropylene composition has the flexural modulus of about 1200MPa to about 1500MPa.In some embodiments, polypropylene composition has the flexural modulus of about 1200MPa to about 1600MPa.

[0097] The second polymer phase can comprise a propylene / ethylene copolymer comprising ethylene in an amount of less than about 18 wt %, including about 1 wt %, about 2 wt %, about 3 wt %, about 4 wt %, about 5 wt %, about 6 wt %, about 7 wt %, about 8 wt %, about 9 wt %, about 10 wt %, about 11 wt %, about 12 wt %, about 13 wt %, about 14 wt %, about 15 wt %, about 16 wt %, about 17 wt %, and about 18 wt %, based on the total weight of the propylene / ethylene copolymer. In any embodiment, the second polymer phase comprises a propylene / ethylene copolymer comprising ethylene in an amount of about 10 wt % to about 18 wt %, based on the total weight of the propylene / ethylene copolymer.

[0098] The ratio of the melt flow rate of the polypropylene homopolymer or random copolymer to the melt flow rate of the propylene / ethylene copolymer can be greater than about 1.0, including about 1.0, about 1.5, about 2.0, about 2.5 and about 3.0. In any embodiment, the ratio of the melt flow rate of the polypropylene homopolymer or random copolymer to the melt flow rate of the propylene / ethylene copolymer is from about 1.0 to about 3.0.

[0099] In any embodiment, the polypropylene composition has a Gardner drop impact strength at 23°C of greater than about 150 inch pounds, including about 150 inch pounds, about 175 inch pounds, about 200 inch pounds, about 225 inch pounds, about 250 inch pounds, about 275 inch pounds, about 300 inch pounds, about 325 inch pounds, and about 350 inch pounds.

[0100] In any embodiment, the one or more comonomers present in the polypropylene homopolymer or random copolymer are ethylene, butene, 1-hexene, and 1-octene. In some embodiments, the one or more comonomers present in the polypropylene homopolymer or random copolymer are ethylene.

[0101] The polypropylene composition of the present disclosure may contain various other additives and ingredients. For example, the polypropylene composition may include nucleating agents, mold release agents, lubricants, anti-caking agents, UV stabilizers, heat stabilizers, colorants / coloring agents, etc. In one embodiment, the polymer composition may contain antioxidants, such as hindered phenol antioxidants. The polymer composition may also contain antacids. For example, the polymer composition may contain antacids and antioxidants. The polymer composition may also contain acid scavengers. Each additive may be generally present in an amount less than about 3% by weight, such as in an amount less than about 2% by weight, such as in an amount less than about 1% by weight, such as in an amount less than about 0.5% by weight, and generally present in the polymer composition in an amount greater than about 0.001% by weight. In any embodiment, the polypropylene composition further includes one or more of nucleating agents, antacids, and antioxidants.

[0102] In one embodiment, the polypropylene composition may further contain a nucleating agent. A nucleating agent may be added to further improve the transparency properties of the composition. For example, the nucleating agent may include a compound that is capable of generating a gel network within the composition.

[0103] In one embodiment, the nucleating agent may comprise a sorbitol compound, such as a sorbitol acetal derivative. In one embodiment, for example, the nucleating agent may comprise dibenzyl sorbitol.

[0104] For the sorbitol acetal derivative that can be used as an additive in some embodiments, the sorbitol acetal derivative is represented by formula (I):

[0105]

[0106] wherein R1-R5 comprise the same or different groups selected from hydrogen and C1-C3 alkyl.

[0107] In some embodiments, R1-R5 are hydrogen, such that the sorbitol acetal derivative is 2,4-dibenzylidene sorbitol ("DBS"). In some embodiments, R1, R4 and R5 are hydrogen, and R2 and R3 are methyl, such that the sorbitol acetal derivative is 1,3:2,4-di-p-methyldibenzylidene-D-sorbitol ("MDBS"). In some embodiments, R1-R4 are methyl and R5 is hydrogen, such that the sorbitol acetal derivative is 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol ("DMDBS"). In some embodiments, R2, R3 and R5 are propyl (-CH2-CH2-CH3), and R1 and R4 are hydrogen, such that the sorbitol acetal derivative is 1,2,3-trideoxy-4,6:5,7-bis-O-(4-propylphenylmethylene)nonanol ("TBPMN").

[0108] Other embodiments in which nucleating agents may be used include 1,3:2,4-dibenzylidene sorbitol, 1,3:2,4-bis(p-methylbenzylidene)sorbitol, di(p-methylbenzylidene)sorbitol, di(p-ethylbenzylidene)sorbitol, bis(5',6',7',8'-tetrahydro-2-naphthylidene)sorbitol.

[0109] In one embodiment, the nucleating agent may also include bisamides, such as benzyltriamide. The above nucleating agents may be used alone or in combination.

[0110] When one or more nucleating agents are present in a polymer composition, they are generally added in an amount greater than about 200ppm, such as in an amount greater than about 1,800ppm, such as in an amount greater than about 2,000ppm, such as in an amount greater than about 2,200ppm. One or more nucleating agents are generally present in an amount less than about 8,000ppm, such as less than about 6,000ppm, such as less than about 5,000ppm. The amount of nucleating agent present in the composition may depend on various factors, including the type of nucleating agent used. In some embodiments, one or more nucleating agents are present in an amount of about 5000ppm or less.

[0111] A variety of polymerization methods and procedures can be used to produce the first phase polymer and the second phase polymer. In one embodiment, a Ziegler-Natta catalyst is used to produce two polymers. For example, olefin polymerization can occur in the presence of a catalyst system comprising a catalyst, an internal electron donor, a cocatalyst, and an optional external electron donor. An olefin of formula CH2=CHR, wherein R is hydrogen or a hydrocarbon group having 1 to 12 atoms, can be contacted with the catalyst system under suitable conditions to form a polymer product. Copolymerization can occur during the process steps to produce the heterogeneous composition of the present disclosure. The polymerization process can be carried out in the gas phase using a fluidized bed or stirred bed reactor using known techniques, or in the slurry phase using an inert hydrocarbon solvent or diluent or a liquid monomer.

[0112] In one embodiment, the first phase polymer and the second phase polymer can be produced in a two-stage process, which includes a first stage and a second stage, wherein the first stage prepares a propylene random copolymer of a continuous polymer phase, and wherein the second stage produces an ethylene-propylene copolymer. The first stage polymerization can be carried out in one or more bulk reactors or one or more gas phase reactors. The second stage polymerization can be carried out in one or more gas phase reactors. The second stage polymerization is usually carried out directly after the first stage polymerization. For example, the polymer product recovered from the first polymerization stage can be directly transferred to the second polymerization stage. Produce a heterophasic copolymer composition.

[0113] In another aspect, there is also provided a method for preparing any one of the polypropylene compositions described herein by sequential polymerization in the presence of a Ziegler-Natta catalyst, wherein:

[0114] preparing a first polymer phase in a first gas phase reactor, and

[0115] transferring the first polymer phase to a second gas phase reactor containing a second polymer phase;

[0116] Therein, the first polymer phase is combined with the second polymer phase to provide a polypropylene composition.

[0117] In another aspect, there is also provided a method for preparing any of the polypropylene compositions described herein, comprising:

[0118] feeding propylene and optionally one or more comonomers into a first reactor; feeding a catalyst mixture comprising (1) a Ziegler-Natta catalyst, (2) a cocatalyst, and (3) an external donor into the first reactor;

[0119] contacting propylene with the catalyst mixture under first polymerization conditions to polymerize propylene and optionally one or more comonomers to form a first polymer phase comprising a propylene homopolymer or copolymer;

[0120] transferring at least a portion of the first polymer phase to a second reactor; and

[0121] feeding additional propylene and ethylene into a second reactor to form a second polymer phase;

[0122] Wherein, the first polymer phase is combined with the second polymer phase to provide a polypropylene composition. In some embodiments, the second polymer phase may further include butene. In some embodiments, additional propylene and ethylene are fed into the second reaction and also include feeding butene to form the second polymer phase.

[0123] In one embodiment of the present disclosure, the polymerization is carried out in the presence of a stereoregular olefin polymerization catalyst.

[0124] In one embodiment, the catalyst comprises a procatalyst composition comprising a titanium moiety (eg, titanium chloride), a magnesium moiety (eg, magnesium chloride), and at least one internal electron donor.

[0125] The procatalyst precursor may include (i) magnesium, (ii) a transition metal compound of Group IV-VII of the periodic table, (iii) (i) or a halide, oxyhalide, and / or alkoxide of (i) and / or (ii), and (iv) a combination of (i), (ii) and (iii). Non-limiting examples of suitable procatalyst precursors include halides, oxyhalides, and alkoxides of magnesium, manganese, titanium, vanadium, chromium, molybdenum, zirconium, hafnium, and combinations thereof.

[0126] In one embodiment, the procatalyst precursor contains magnesium as the sole metal component. Non-limiting examples include anhydrous magnesium chloride and / or its alcohol adducts, magnesium alkoxides and / or aryloxides, mixed alkoxymagnesium halides and / or carboxylated magnesium dialkoxides or aryloxides.

[0127] In one embodiment, the primary catalyst precursor is an alcohol adduct of anhydrous magnesium chloride. Anhydrous magnesium chloride adduct is generally defined as MgCl2-nROH, wherein n has a range of 1.5-6.0, preferably 2.5-4.0, and most preferably 2.8-3.5 moles of total alcohol. ROH is a C1-C4 alcohol, straight or branched, or a mixture of alcohols. Preferably, ROH is ethanol or a mixture of ethanol and higher alcohols. If ROH is a mixture, the molar ratio of ethanol to higher alcohol is at least 80:20, preferably 90:10, and most preferably at least 95:5.

[0128] In one embodiment, a substantially spherical MgCl2-nEtOH adduct may be formed by a spray crystallization process. In one embodiment, the spherical MgCl2 precursor has an average particle size (Malvern d50 ).

[0129] In one embodiment, the procatalyst precursor contains a transition metal compound and a magnesium metal compound. The transition metal compound has the general formula TrX x , where Tr is a transition metal and X is a halogen or C 1-10 Tr can be a Group IV, V or VI metal. In one embodiment, Tr is a Group IV metal such as titanium. X can be a chloride, bromide, C 1-4 Alkoxide or phenoxide, or a mixture thereof. In one embodiment, X is chloride.

[0130] The precursor composition may be prepared by chlorinating the aforementioned mixed magnesium compound, titanium compound or mixture thereof.

[0131] In one embodiment, the precursor composition is of the formula MgdTi(OR e ) f X g A mixed magnesium / titanium compound wherein R e is an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms or COR', wherein R' is an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms; each OR e The groups are the same or different; X is independently chlorine, bromine or iodine; d is 0.5 to 56; or 2-4, or 3; f is 2 to 116, or 5 to 15; and g is 0.5 to 116, or 1 to 3.

[0132] According to the present disclosure, the above-described procatalyst precursor is combined with at least one internal electron donor. The internal electron donor may include a substituted phenylene aromatic diester.

[0133] In one embodiment, the first internal electron donor comprises a substituted phenylene aromatic diester having the following structure (I):

[0134]

[0135] Among them, R1-R 14 Same or different. R1-R 14 Each is selected from hydrogen, a substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a heteroatom, and combinations thereof. 14 Not hydrogen.

[0136] In one embodiment, the substituted phenylene aromatic diester can be any substituted phenylene aromatic diester as disclosed in US Patent Application Serial No. 61 / 141,959, filed December 31, 2008, the entire contents of which are incorporated herein by reference.

[0137] In one embodiment, the substituted phenylene aromatic diester may be any substituted phenylene aromatic diester disclosed in WO12088028 filed on December 20, 2011, the entire contents of which are incorporated herein by reference.

[0138] In one embodiment, at least one (or two, or three, or four) R groups among R1-R4 are selected from substituted hydrocarbon groups having 1 to 20 carbon atoms, unsubstituted hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, heteroatoms, and combinations thereof.

[0139] In one embodiment, R5-R 14 At least one (or some or all) R groups in R5-R9 are selected from substituted hydrocarbon groups having 1 to 20 carbon atoms, unsubstituted hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, heteroatoms, and combinations thereof. 10 -R 14 At least one of the following is selected from the group consisting of a substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a heteroatom, and combinations thereof.

[0140] In one embodiment, at least one of R1-R4 and R5-R 14 At least one of R1-R4, at least one of R5-R9 and R 10 -R 14 At least one of the following is selected from the group consisting of a substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a heteroatom, and combinations thereof.

[0141] In one embodiment, any consecutive R groups among R1-R4, and / or any consecutive R groups among R5-R9 and / or R 10 -R 14 Any consecutive R groups in may be connected to form an inter- or intra-cyclic structure. The inter- / inter-cyclic structure may or may not be aromatic. In one embodiment, the inter- / inter-cyclic structure is a C5 or C6 membered ring.

[0142] In one embodiment, at least one of R1-R4 is selected from a substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and combinations thereof. 14 At least one of may be a halogen atom or an alkoxy group having 1 to 20 carbon atoms. Optionally, R1-R4, and / or R5-R9, and / or R 10 -R 14 Can be linked to form an inter-cyclic structure or an intra-cyclic structure. The inter-cyclic structure and / or the intra-cyclic structure may or may not be aromatic.

[0143] In one embodiment, R1-R4, and / or R5-R9, and / or R 10 -R 14 Any consecutive R groups in may be members of a C5-C6 membered ring.

[0144] In one embodiment, structure (I) includes R1, R3 and R4 are hydrogen. R2 is selected from substituted hydrocarbon groups having 1 to 20 carbon atoms, unsubstituted hydrocarbon groups having 1 to 20 carbon atoms, and combinations thereof. 14 Same or different, and R5-R 14 Each is selected from hydrogen, a substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogen, and combinations thereof.

[0145] In one embodiment, R2 is selected from C1-C8 alkyl, C3-C6 cycloalkyl, or substituted C3-C6 cycloalkyl. R2 can be methyl, ethyl, n-propyl, isopropyl, tert-butyl, isobutyl, sec-butyl, 2,4,4-trimethylpentan-2-yl, cyclopentyl and cyclohexyl.

[0146] In one embodiment, structure (I) includes R2 which is methyl, and R5-R 14 Each of is hydrogen.

[0147] In one embodiment, structure (I) includes R2 which is ethyl, and R5-R 14 Each of is hydrogen.

[0148] In one embodiment, structure (I) includes R2 which is tert-butyl, and R5-R 14 Each of is hydrogen.

[0149] In one embodiment, structure (I) includes R2 which is ethoxycarbonyl, and R5-R 14 Each of is hydrogen.

[0150] In one embodiment, structure (I) includes R2, R3 and R4, each of which is hydrogen, and R1 is selected from substituted hydrocarbon groups having 1 to 20 carbon atoms, unsubstituted hydrocarbon groups having 1 to 20 carbon atoms, and combinations thereof; R5-R 14 are the same or different and are each selected from hydrogen, a substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogen, and combinations thereof.

[0151] In one embodiment, structure (I) includes R1 which is methyl, and R5-R 14 Each of is hydrogen.

[0152] In one embodiment, structure (I) includes R2 and R4, which are hydrogen, and R1 and R3 are the same or different. R1 and R3 are each selected from substituted hydrocarbon groups having 1 to 20 carbon atoms, unsubstituted hydrocarbon groups having 1 to 20 carbon atoms, and combinations thereof. 14 Same or different, and R5-R 14 Each is selected from a substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogen, and combinations thereof.

[0153] In one embodiment, structure (I) includes R1 and R3 which are the same or different. R1 and R3 are each selected from C1-C8 alkyl, C3-C6 cycloalkyl, or substituted C3-C6 cycloalkyl. 14 Same or different, and R5-R 14 Each is selected from hydrogen, C1-C8 alkyl and halogen. Non-limiting examples of suitable C1-C8 alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl and 2,4,4-trimethylpent-2-yl. Non-limiting examples of suitable C3-C6 cycloalkyl include cyclopentyl and cyclohexyl. In a further embodiment, R5-R 14 At least one of them is C1-C8 alkyl or halogen.

[0154] In one embodiment, structure (I) includes R1 which is methyl and R3 which is tert-butyl. 14 Each of is hydrogen.

[0155] In one embodiment, structure (I) includes R1 and R3, which are isopropyl. R2, R4 and R5-R 14 Each of is hydrogen.

[0156] In one embodiment, structure (I) includes R1, R5 and R 10Each of (which is methyl) and R3 (which is tert-butyl). R2, R4, R6-R9 and R 11 -R 14 Each of is hydrogen.

[0157] In one embodiment, structure (I) includes R1, R7 and R 12 Each of (which is methyl) and R3 (which is tert-butyl). R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 and R 14 Each of is hydrogen.

[0158] In one embodiment, structure (I) includes R1 which is methyl and R3 which is tert-butyl. 12 Each of R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 and R 14 Each of is hydrogen.

[0159] In one embodiment, structure (I) includes R1, R5, R7, R9, R 10 , R 12 and R 14 Each of R2, R4, R6, R8, R 11 and R 13 In one embodiment, structure (I) includes R1 (which is methyl) and R3 (which is tert-butyl). R5, R7, R9, R 10 , R 12 and R 14 Each of R2, R4, R6, R8, R 11 and R 13 Each of is hydrogen.

[0160] In one embodiment, the substituted phenylene aromatic diester has structure (II), which includes R1 (which is methyl) and R3 (which is tert-butyl). R2 and R4 are each hydrogen. R8 and R9 are members of a C6-membered ring to form a 1-naphthoyl group. 13 and R 14 is a member of a C6-membered ring to form another 1-naphthoyl group. Structure (II) is provided below.

[0161]

[0162] In one embodiment, the substituted phenylene aromatic diester has structure (III), which includes R1 (which is methyl) and R3 (which is tert-butyl). R2 and R4 are each hydrogen. R6 and R7 are members of a C6-membered ring to form a 2-naphthoyl group. 12 and R 13 is a member of a C6-membered ring to form a 2-naphthoyl group. Structure (III) is provided below.

[0163]

[0164] In one embodiment, structure (I) includes R1 which is methyl and R3 which is tert-butyl. 12 Each is an ethoxy group. 10 , R 11 , R 13 and R 14 Each of is hydrogen.

[0165] In one embodiment, structure (I) includes R1 which is methyl and R3 which is tert-butyl. 12 Each of R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 and R 14 Each of is hydrogen.

[0166] In one embodiment, structure (I) includes R1 which is methyl and R3 which is tert-butyl. 12 Each of R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 and R 14 Each of is hydrogen.

[0167] In one embodiment, structure (I) includes R1 which is methyl and R3 which is tert-butyl. 12 Each of R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 and R 14 Each of is hydrogen.

[0168] In one embodiment, structure (I) includes R1 which is methyl and R3 which is tert-butyl. 12 Each of R2, R4, R5, R6, R8, R9, R 10 , R 11, R 13 and R 14 Each of is hydrogen.

[0169] In one embodiment, structure (I) includes R1 which is methyl and R3 which is tert-butyl. 11 and R 12 Each of R2, R4, R5, R8, R9, R 10 , R 13 and R 14 Each of is hydrogen.

[0170] In one embodiment, structure (I) includes R1 which is methyl and R3 which is tert-butyl. 11 and R 13 Each of R2, R4, R5, R7, R9, R 10 , R 12 and R 14 Each of is hydrogen.

[0171] In one embodiment, structure (I) includes R1 which is methyl and R3 which is tert-butyl. 14 Each of is a fluorine atom.

[0172] In one embodiment, structure (I) includes R1 which is methyl and R3 which is tert-butyl. 12 R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 and R 14 Each of is hydrogen.

[0173] In one embodiment, structure (I) includes R1 which is methyl and R3 which is tert-butyl. 12 Each of R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 and R 14 Each of is hydrogen.

[0174] In one embodiment, R1 (which is methyl) and R3 (which is tert-butyl). 12 Each is an ethoxy group. 10 , R 11 , R 13 and R 14 Each of is hydrogen.

[0175] In one embodiment, structure (I) includes R1 which is methyl and R3 which is tert-butyl. 12 Each is diethylamino. R2, R4, R5, R6, R8, R9, R 10 , R 11 , R 13 and R 14 Each of is hydrogen.

[0176] In one embodiment, structure (I) includes R1 which is methyl and R3 which is 2,4,4-trimethylpentan-2-yl. 14 Each of is hydrogen.

[0177] In one embodiment, structure (I) includes R1 and R3, each of which is sec-butyl. R2, R4 and R5-R 14 Each of is hydrogen.

[0178] In one embodiment, the substituted phenylene aromatic diester has the structure (IV) wherein R1 and R2 are members of a C6-membered ring to form a 1,2-naphthyl group. 14 Each of is hydrogen. Structure (IV) is provided below.

[0179]

[0180] In one embodiment, the substituted phenylene aromatic diester has the structure (V) wherein R2 and R3 are members of a C6-membered ring to form a 2,3-naphthyl group. 14 Each of is hydrogen. Structure (V) is provided below.

[0181]

[0182] In one embodiment, structure (I) includes R1 and R4, each of which is methyl. R2, R3, R5-R9 and R 10 -R 14 Each of is hydrogen.

[0183] In one embodiment, structure (I) includes R1 which is methyl. R4 is isopropyl. R2, R3, R5-R9 and R 10 -R 14 Each of is hydrogen.

[0184] In one embodiment, structure (I) includes R1, R3 and R4, each of which is isopropyl. R2, R5-R9 and R 10 -R 14 Each of is hydrogen.

[0185] In one embodiment, R1 and R4 are each selected from methyl, ethyl and vinyl. R2 and R3 are each selected from hydrogen, secondary alkyl or tertiary alkyl, wherein R2 and R3 are not hydrogen at the same time. In other words, when R2 is hydrogen, R3 is not hydrogen (and vice versa).

[0186] In one embodiment, a second internal electron donor may be used, which typically includes a polyether that may coordinate in a bidentate manner. In one embodiment, the second internal electron donor is a substituted 1,3-diether of structure VI:

[0187]

[0188] Where R1 and R2 are the same or different, methyl, C2-C 18 Straight or branched alkyl, C3-C 18 Cycloalkyl, C4-C 18 Cycloalkyl-alkyl, C4-C 18 Alkyl-cycloalkyl, phenyl, silicone, C7-C 18 Arylalkyl, or C7-C 18 alkylaryl group; and R1 or R2 may also be a hydrogen atom.

[0189] In one embodiment, the second internal electron donor may include a 1,3-diether having a cyclic or polycyclic structure VII:

[0190]

[0191] wherein R1, R2, R3 and R4 are as described for R1 and R2 of structure VI, or may be combined to form one or more C5-C7 fused aromatic or non-aromatic ring structures, optionally containing heteroatoms of N, O or S. Specific examples of the second internal electron donor include 4,4-bis(methoxymethyl)-2,6-dimethylheptane, 9,9-bis(methoxymethyl)fluorene or mixtures thereof.

[0192] By further reaction (halogenation) with an inorganic halide compound, preferably a titanium halide compound, and incorporation of an internal electron donor, the precursor is converted into a solid procatalyst.

[0193] One suitable method of halogenating the precursor is to react the precursor with a tetravalent titanium halide at elevated temperature, optionally in the presence of a hydrocarbon or halohydrocarbon diluent. The preferred tetravalent titanium halide is titanium tetrachloride.

[0194] The obtained main catalyst composition can usually contain titanium in an amount of about 0.5 wt % to about 6 wt %, such as about 1.5 wt % to about 5 wt %, such as about 2 wt % to about 4 wt %. Solid catalysts can usually contain magnesium in an amount greater than about 5 wt %, such as in an amount greater than about 8 wt %, such as in an amount greater than about 10 wt %, such as in an amount greater than about 12 wt %, such as in an amount greater than about 14 wt %, such as in an amount greater than about 16 wt %. In the catalyst, magnesium is contained in an amount less than about 25 wt %, such as in an amount less than about 23 wt %, such as in an amount less than about 20 wt %. The inner electron donor can be present in the catalyst composition in an amount less than about 30 wt %, such as in an amount less than about 25 wt %, such as in an amount less than about 22 wt %, such as in an amount less than about 20 wt %, such as in an amount less than about 19 wt %. The inner electron donor is usually present in an amount greater than about 5 wt %, such as in an amount greater than about 9 wt %.

[0195] In one embodiment, the main catalyst composition is combined with a cocatalyst to form a catalyst system. The catalyst system is a system that forms an olefin-based polymer when contacted with an olefin under polymerization conditions. The catalyst system may optionally include an external electron donor, an activity limiting agent and / or various other components.

[0196] As used herein, a "cocatalyst" is a substance that is capable of converting a primary catalyst into an active polymerization catalyst. Cocatalysts may include hydrides, alkylates or arylates of aluminum, lithium, zinc, tin, cadmium, beryllium, magnesium and combinations thereof. In one embodiment, the cocatalyst is a hydrocarbyl aluminum cocatalyst represented by the formula R3Al, wherein each R is an alkyl, cycloalkyl, aryl or hydride group; at least one R is a hydrocarbyl group; two or three R groups may be joined in a cyclic group to form a heterocyclic structure; each R may be the same or different; and each R as a hydrocarbyl group has 1 to 20 carbon atoms, and preferably has 1 to 10 carbon atoms. In another embodiment, each alkyl group may be linear or branched, and such a hydrocarbyl group may be a mixed group, i.e., the group may contain alkyl, aryl and / or cycloalkyl groups. Non-limiting examples of suitable groups are: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, 2-methylpentyl, n-heptyl, n-octyl, isooctyl, 2-ethylhexyl, 5,5-dimethylhexyl, n-nonyl, n-decyl, isodecyl, n-undecyl, n-dodecyl.

[0197] Non-limiting examples of suitable hydrocarbyl aluminum compounds are as follows: triisobutylaluminum, tri-n-hexylaluminum, diisobutylaluminum hydride, di-n-hexylaluminum hydride, isobutylaluminum dihydride, n-hexylaluminum dihydride, diisobutylhexylaluminum, isobutyldihexylaluminum, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, tri-n-dodecylaluminum. In one embodiment, the preferred cocatalyst is selected from triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, diisobutylaluminum hydride and di-n-hexylaluminum hydride, and the most preferred cocatalyst is triethylaluminum.

[0198] In one embodiment, the co-catalyst is of formula R n AlX 3-n The hydrocarbyl aluminum compound represented by wherein n=1 or 2, R is an alkyl group, and X is a halide or an alkoxide. Non-limiting examples of suitable compounds are as follows: methylaluminoxane, isobutylaluminoxane, diethylaluminum ethoxide, diisobutylaluminum chloride, tetraethyldialuminoxane, tetraisobutyldialuminoxane, diethylaluminum chloride, ethylaluminum dichloride, methylaluminum dichloride, and dimethylaluminum chloride.

[0199] In one embodiment, the catalyst composition includes an external electron donor. As used herein, an "external electron donor" is a compound added independently of the formation of the primary catalyst and contains at least one functional group capable of donating a pair of electrons to a metal atom. Without being bound by any particular theory, it is believed that the external electron donor enhances the stereoselectivity of the catalyst (i.e., reduces the xylene-soluble material in the resonance peak polymer).

[0200] In one embodiment, the external electron donor may be selected from one or more of the following: alkoxysilanes, amines, ethers, carboxylates, ketones, amides, carbamates, phosphines, phosphates, phosphites, sulfonates, sulfones, and / or sulfoxides.

[0201] In one embodiment, the external electron donor is an alkoxysilane. Alkoxysilane has the general formula: SiR m (OR') 4-m (I), wherein R at each occurrence is independently hydrogen or a hydrocarbon or amino group optionally substituted with one or more substituents containing one or more heteroatoms of Groups 14, 15, 16 or 17, excluding hydrogen and halogen, said R' containing up to 20 atoms; R' is C 1-4 and m is 0, 1, 2 or 3. In one embodiment, R is C 6-12 Aryl, alkyl or aralkyl, C 3-12 Cycloalkyl, C 3-12 Branched alkyl, or C 3-12 Cyclic or non-cyclic amino group, R' is C 1-4alkyl, and m is 1 or 2. Non-limiting examples of suitable silane compositions include dicyclopentyldimethoxysilane, di-tert-butyldimethoxysilane, methylcyclohexyldimethoxysilane, methylcyclohexyldiethoxysilane, ethylcyclohexyldimethoxysilane, diphenyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldimethoxysilane, diisobutyldimethoxysilane, diisobutyldiethoxysilane, isobutylisopropyldimethoxysilane, di-n-butyldimethoxysilane, cyclopentyltrimethoxysilane, isopropyltrimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, diethylaminotriethoxysilane, cyclopentylpyrrolidinedimethoxysilane, bis(pyrrolidine)dimethoxysilane, bis(perhydroisoquinoline)dimethoxysilane, and dimethyldimethoxysilane. In one embodiment, the silane composition is dicyclopentyldimethoxysilane (DCPDMS), methylcyclohexyldimethoxysilane (MChDMS), diisopropyldimethoxysilane (DIPDMS), n-propyltrimethoxysilane (NPTMS), diethylaminotriethoxysilane (DATES) or n-propyltriethoxysilane (PTES), and any combination thereof.

[0202] In one embodiment, the external donor may be a mixture of at least two alkoxysilanes. In a further embodiment, the mixture may be dicyclopentyldimethoxysilane and methylcyclohexyldimethoxysilane, dicyclopentyldimethoxysilane and tetraethoxysilane, or dicyclopentyldimethoxysilane and n-propyltriethoxysilane.

[0203] In one embodiment, the external electron donor is selected from one or more of the following: benzoate and / or diol ester. In another embodiment, the external electron donor is 2,2,6,6-tetramethylpiperidine. In yet another embodiment, the external electron donor is a diether.

[0204] In one embodiment, the catalyst composition includes an activity limiting agent (ALA). As used herein, an "activity limiting agent" ("ALA") is a material that reduces the activity of the catalyst at high temperatures (i.e., temperatures above about 85°C). ALA inhibits or otherwise prevents polymerization reactor anomalies and ensures the continuity of the polymerization process. Typically, the activity of Ziegler-Natta catalysts increases as the reactor temperature increases. Ziegler-Natta catalysts also typically maintain high activity near the melting point temperature of the produced polymer. The heat generated by the exothermic polymerization reaction can cause the polymer particles to form agglomerates and can ultimately lead to interruptions in the continuity of the polymer production process. ALA reduces catalyst activity at elevated temperatures, thereby preventing reactor anomalies, reducing (or preventing) particle agglomeration, and ensuring the continuity of the polymerization process.

[0205] The activity limiting agent can be a carboxylate, a diether, a poly (alkylene glycol), a poly (alkylene glycol) ester, a glycol ester and a combination thereof. The carboxylate can be aliphatic or aromatic monocarboxylic acid esters or polycarboxylic acid esters. The limiting examples of suitable monocarboxylic acid esters include ethyl benzoate and methyl benzoate, ethyl p-methoxybenzoate, methyl p-ethoxybenzoate, ethyl p-ethoxybenzoate, ethyl acrylate, methyl methacrylate, ethyl acetate, ethyl p-chlorobenzoate, hexyl p-aminobenzoate, isopropyl cyclohexanoate, n-pentyl toluate, ethyl cyclohexanoate and propyl pivalate.

[0206] In one embodiment, the external electron donor and / or the activity limiting agent can be added to the reactor separately. In another embodiment, the external electron donor and the activity limiting agent can be pre-mixed together and then added to the reactor in the form of a mixture. More than one external electron donor or more than one activity limiting agent can be used in the mixture. In one embodiment, the mixture is dicyclopentyldimethoxysilane and isopropyl myristate, dicyclopentyldiethoxysilane and polyethylene glycol laurate, dicyclopentyldimethoxysilane and isopropyl myristate and polyethylene glycol dioleate, methylcyclohexyldimethoxysilane and isopropyl myristate, n-propyltrimethoxysilane and isopropyl myristate, dimethyldimethoxysilane and methylcyclohexyldimethoxysilane and isopropyl myristate, dicyclopentyldimethoxysilane and n-propyltriethoxysilane and isopropyl myristate, and dicyclopentyldimethoxysilane and tetraethoxysilane and isopropyl myristate, and combinations thereof.

[0207] In one embodiment, the catalyst composition includes any of the foregoing external electron donors in combination with any of the foregoing activity limiting agents.

[0208] The catalyst system as described above has been found to be particularly well suited for producing the heterophasic polymer compositions of the present disclosure.

[0209] Due to the physical properties of the polypropylene compositions of the present disclosure, the compositions described herein are well suited for thermoforming and extrusion blow molding applications.

[0210] The invention thus generally described will be more readily understood by reference to the following examples, which are provided by way of illustration and are not intended to be limiting of the invention. Example

[0211] Example 1

[0212] Various heterophasic polypropylene copolymer samples were prepared and tested for various properties, including impact strength and haze. The heterophasic copolymers were generally prepared using the above methods in combination with the above catalysts. Specifically, the example resins were prepared in a dual reactor gas phase fluidized bed pilot plant. The Ziegler-Natta catalyst (from WR Grace) was used to prepare the example resins. C601 catalyst), cocatalyst (triethylaluminum (Teal)), external donor (from WR Grace D8700 donor) and propylene are fed to the first reactor. For Examples 2-4, ethylene is also fed to the first reactor. For all examples, the first reactor also has a hydrogen feed for controlling the polymer first phase melt flow rate. The total reactor pressure is kept constant by nitrogen feed. In the first reactor, the polymer phase ethylene content is controlled by adjusting the ethylene / propylene gas phase molar ratio, the melt flow rate is controlled by adjusting the hydrogen / propylene gas phase molar ratio, and the cold xylene solubles are controlled by adjusting the cocatalyst / external donor molar ratio. The reactor temperature is maintained at 65°C.

[0213] The first polymer phase powder was transferred from the first gas phase reactor to the second gas phase reactor, also maintained at 65° C. The second reactor had ethylene and propylene feeds to control the second phase composition by controlling the propylene / ethylene gas phase molar ratio, and had hydrogen feed to control the melt flow rate by controlling the hydrogen / ethylene gas phase molar ratio. As with the first reactor, nitrogen was fed to maintain a constant reactor pressure.

[0214] The additive package was mixed with the neat polymer produced in the reactor using a twin screw extruder. The additive package included 1000 ppm of pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate); 1000 ppm of tris(2,4-di-tert-butylphenyl)phosphite; 180 ppm of an acid scavenger DHT-4A (obtained from Kisuma); 2000 ppm of glycerol monostearate; and 4000 ppm of a nucleating agent (commercially available from Milliken under the trade name 8000). Samples were prepared according to ASTM test D4101 to produce samples for testing. The test method used was as described above.

[0215] The following table shows the following polypropylene compositions prepared and their following properties.

[0216] Table 1

[0217]

[0218] Phase 1 = first polymer phase

[0219] Table 2

[0220]

[0221]

[0222] Phase 1 = first polymer phase

[0223] When Composition 1 and Composition 2 are compared to Comparative Example 1 (a material outside the range of ethylene / propylene copolymers disclosed in the specification), Compositions 1 and 2 show higher toughness and comparable haze.

[0224] When Composition 3 and Composition 4 are compared to Comparative Example 2 (a material outside the range of ethylene / propylene copolymers disclosed in the specification), Compositions 3 and 4 show higher stiffness and similar haze and toughness.

[0225] When comparing Composition 1 and Composition 4 to Comparative Example 3, Compositions 1 and 4 exhibited similar stiffness / toughness at room temperature with slightly lower stiffness, but improved haze.

[0226] Paragraph 1. A polypropylene composition comprising:

[0227] (a) a first polymer phase comprising a polypropylene homopolymer or random copolymer, the polypropylene homopolymer or random copolymer optionally comprising one or more comonomers in an amount equal to or less than about 3 wt %, based on the total weight of the propylene homopolymer or copolymer, having a total cold xylene soluble content of from about 2 wt % to about 6 wt %, and having a melt flow rate of from about 0.5 g / 10 min to about 3 g / 10 min; and

[0228] (b) a second polymer phase comprising a propylene / ethylene copolymer comprising ethylene in an amount less than about 18 weight percent based on the total weight of the propylene / ethylene copolymer;

[0229] wherein the ratio of the melt flow rate of the polypropylene homopolymer or random copolymer to the melt flow rate of the propylene / ethylene copolymer is greater than about 1.0; and

[0230] wherein the first polymer phase and the second polymer phase are combined to provide a polypropylene composition having a melt flow rate of about 4 g / 10 min or less, an ethylene content of less than about 5 wt%, a total cold xylene soluble content of about 5 wt% to about 20 wt%, a haze of less than about 20% at 1 mm, an IZOD impact strength of greater than about 500 J / m at 23°C, a Gardner drop impact strength of greater than about 150 inch pounds at 0°C, and a flexural modulus of greater than or equal to about 800 MPa.

[0231] Paragraph 2. A polypropylene composition comprising:

[0232] (a) a first polymer phase comprising a polypropylene homopolymer or random copolymer, the polypropylene homopolymer or random copolymer optionally comprising one or more comonomers in an amount equal to or less than about 1 wt %, based on the total weight of the propylene homopolymer or copolymer, having a total cold xylene soluble content of less than about 4 wt %, and having a melt flow rate of about 2 g / 10 min to about 5 g / 10 min; and

[0233] (b) a second polymer phase comprising a propylene / ethylene copolymer comprising ethylene in an amount less than about 18 weight percent based on the total weight of the propylene / ethylene copolymer;

[0234] wherein the ratio of the melt flow rate of the polypropylene homopolymer or random copolymer to the melt flow rate of the propylene / ethylene copolymer is greater than about 1.0; and

[0235] wherein the first polymer phase and the second polymer phase are combined to provide a polypropylene composition having a melt flow rate of about 5 g / 10 min or less, an ethylene content of less than about 3.5 wt%, a total cold xylene soluble content of about 5 wt% to about 15 wt%, a haze of less than about 20% at 1 mm, an IZOD impact strength of greater than about 200 J / m at 23°C, and a flexural modulus of greater than or equal to about 1100 MPa.

[0236] Paragraph 3. The polypropylene composition of paragraph 1 or 2, wherein the first polymer phase comprises a crystalline matrix comprising a polypropylene homopolymer or a random copolymer.

[0237] Paragraph 4. The polypropylene composition according to any of paragraphs 1 to 3, wherein the polypropylene composition comprises a heterophasic propylene copolymer.

[0238] Paragraph 5. The polypropylene composition of any of paragraphs 1 and 3-4, wherein the first polymer phase comprises a polypropylene homopolymer or random copolymer comprising one or more comonomers in an amount of about 0 wt% to about 3 wt% based on the total weight of the propylene homopolymer or copolymer.

[0239] Paragraph 6. The polypropylene composition of any of paragraphs 1 and 3-5, wherein the first polymer phase comprises a polypropylene homopolymer or random copolymer having a total cold xylene solubles content of about 2.5 wt% or about 4.8 wt%.

[0240] Paragraph 7. The polypropylene composition of any of paragraphs 1 and 3-6, wherein the first polymer phase comprises a polypropylene homopolymer or random copolymer having a melt flow rate of about 0.5 g / 10 min to about 1.5 g / 10 min.

[0241] Paragraph 8. The polypropylene composition of any of paragraphs 1 and 3-7, wherein the polypropylene composition has a melt flow rate of about 0.5 g / 10 min to about 1.5 g / 10 min.

[0242] Paragraph 9. The polypropylene composition of any of paragraphs 1 and 3-8, wherein the polypropylene composition has an ethylene content of about 2 wt% to about 4.5 wt%.

[0243] Paragraph 10. The polypropylene composition of any of paragraphs 1 and 3-9, wherein the polypropylene composition has a total cold xylene solubles content of about 7 wt% or about 12 wt%.

[0244] Paragraph 11. The polypropylene composition of any of paragraphs 1 and 3-10, wherein the polypropylene composition has a haze of about 5% to about 15% at 1 mm.

[0245] Paragraph 12. The polypropylene composition of any of paragraphs 1 and 3-11, wherein the polypropylene composition has an IZOD impact strength at 23°C of about 500 J / m to about 900 J / m.

[0246] Paragraph 13. The polypropylene composition of any of paragraphs 1 and 3-12, wherein the polypropylene composition has a Gardner drop impact strength at 0°C of about 150 inch pounds to about 350 inch pounds.

[0247] Paragraph 14. The polypropylene composition of any of paragraphs 1 and 3-13, wherein the polypropylene composition has a flexural modulus of about 800 MPa to about 1300 MPa.

[0248] Paragraph 15. The polypropylene composition of any of paragraphs 2-4, wherein the first polymer phase comprises a polypropylene homopolymer or random copolymer comprising one or more comonomers in an amount of about 0.5 wt% to about 1 wt% based on the total weight of the propylene homopolymer or copolymer.

[0249] Paragraph 16. The polypropylene composition of any of paragraphs 2-4 and 15, wherein the first polymer phase comprises a polypropylene homopolymer or random copolymer having a total cold xylene solubles content of from about 1 wt% to about 3 wt%.

[0250] Paragraph 17. The polypropylene composition of any of paragraphs 2-4 and 15-16, wherein the first polymer phase comprises a polypropylene homopolymer or random copolymer having a melt flow rate of about 2 g / 10 min to about 4 g / 10 min.

[0251] Paragraph 18. The polypropylene composition of any of paragraphs 2-4 and 15-17, wherein the polypropylene composition has a melt flow rate of about 2 g / 10 min to about 4 g / 10 min.

[0252] Paragraph 19. The polypropylene composition of any of paragraphs 2-4 and 15-18, wherein the polypropylene composition has an ethylene content of about 2 wt% to about 3.5 wt%.

[0253] Paragraph 20. The polypropylene composition of any of paragraphs 2-4 and 15-19, wherein the polypropylene composition has a total cold xylene solubles content of about 5.5 wt% or about 12 wt%.

[0254] Paragraph 21. The polypropylene composition of any of paragraphs 2-4 and 15-20, wherein the polypropylene composition has a haze at 1 mm of about 10% to about 20%.

[0255] Paragraph 22. The polypropylene composition of any of paragraphs 2-4 and 5-21, wherein the polypropylene composition has an IZOD impact strength at 23°C of about 200 J / m to about 900 J / m.

[0256] Paragraph 23. The polypropylene composition of any of paragraphs 2-4 and 5-22, wherein the polypropylene composition has a flexural modulus of about 1200 MPa to about 1600 MPa.

[0257] Paragraph 24. The polypropylene composition of any of paragraphs 1-23, wherein the second polymer phase comprises a propylene / ethylene copolymer comprising ethylene in an amount of about 10 wt% to about 18 wt% based on the total weight of the propylene / ethylene copolymer.

[0258] Paragraph 25. The polypropylene composition of any of paragraphs 1 to 24, wherein the ratio of the melt flow rate of the polypropylene homopolymer or random copolymer to the melt flow rate of the propylene / ethylene copolymer is from about 1.0 to about 3.0.

[0259] Paragraph 26. The polypropylene composition of any of paragraphs 1-25, wherein the polypropylene composition has a Gardner drop impact strength at 23°C of greater than about 150 inch pounds.

[0260] Paragraph 27. The polypropylene composition of any of paragraphs 1 to 26, wherein the polypropylene composition further comprises one or more of a nucleating agent, an antacid, and an antioxidant.

[0261] Paragraph 28. The polypropylene composition of Paragraph 27, wherein the one or more nucleating agents are present in an amount of about 5000 ppm or less.

[0262] Paragraph 29. The polypropylene composition of any of paragraphs 1 to 28, wherein the one or more comonomers present in the polypropylene homopolymer or random copolymer comprises ethylene.

[0263] Paragraph 30. A molded article formed from the polypropylene composition of any of paragraphs 1-29.

[0264] Paragraph 31. The molded article of paragraph 30, wherein the molded article is an extrusion blow molded article.

[0265] Paragraph 32. A process for preparing the polypropylene composition of any of paragraphs 1 to 29 by sequential polymerization in the presence of a Ziegler-Natta catalyst, wherein:

[0266] preparing a first polymer phase in a first gas phase reactor, and

[0267] transferring the first polymer phase to a second gas phase reactor comprising a second polymer phase;

[0268] Therein, the first polymer phase is combined with the second polymer phase to provide a polypropylene composition.

[0269] Paragraph 33. A method for preparing the polypropylene composition of any of paragraphs 1-29, comprising:

[0270] feeding propylene and optionally one or more comonomers into a first reactor; feeding a catalyst mixture comprising (1) a Ziegler-Natta catalyst, (2) a cocatalyst, and (3) an external donor into the first reactor;

[0271] contacting the propylene with the catalyst mixture under first polymerization conditions to polymerize the propylene and optionally one or more comonomers to form a first polymer phase comprising a propylene homopolymer or copolymer;

[0272] transferring at least a portion of the first polymer phase to a second reactor; and

[0273] feeding additional propylene and ethylene into a second reactor to form a second polymer phase;

[0274] Therein, the first polymer phase is combined with the second polymer phase to provide a polypropylene composition.

[0275] While certain embodiments have been shown and described, it should be understood that changes and modifications may be made therein in accordance with ordinary skill in the art without departing from the technology in its broader aspects as defined in the following claims.

[0276] The embodiments exemplarily described herein may be suitably implemented in the absence of any one or more elements, one or more limitations not specifically disclosed herein. Thus, for example, the terms "comprise", "include", "contain", etc. should be interpreted broadly and not restrictively. In addition, the terms and expressions adopted herein have been used as descriptive and not restrictive terms, and in the use of these terms and expressions, it is not intended to exclude any equivalents of the features shown and described or parts thereof, but it is recognized that various modifications may be possible within the scope of the claimed technology. In addition, the phrase "essentially consisting of..." will be understood to include those elements specifically enumerated and those additional elements that do not substantially affect the basic and novel features of the claimed technology. The phrase "consisting of..." excludes any element that is not specified.

[0277] The present disclosure is not limited to the aspects of the specific embodiments described in this application. As will be apparent to those skilled in the art, many modifications and variations can be made without departing from its spirit and scope. In addition to those listed herein, functionally equivalent methods and compositions within the scope of the present disclosure will be apparent to those skilled in the art from the above description. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is limited only by the terms of the appended claims and the full range of equivalents to which these claims are entitled. It is to be understood that the present disclosure is not limited to specific methods, reagents, compounds, compositions or biological systems, which are of course variable. It is also to be understood that the terms used herein are only used to describe specific embodiments and are not intended to constitute limitations.

[0278] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

[0279] As will be understood by those skilled in the art, for any and all purposes, particularly in providing a written description, all ranges disclosed herein also include any and all possible subranges and combinations of subranges thereof. Any enumerated range can be easily identified as fully describing and enabling the same range to be split into at least two equal parts, three equal parts, four equal parts, five equal parts, ten equal parts, etc. As a non-limiting example, each range discussed herein can be easily split into lower 1 / 3, middle 1 / 3 and upper 1 / 3, etc. It will also be understood by those skilled in the art that all words such as "at most", "at least", "greater than", "less than" include the enumerated numerical values ​​and refer to the ranges that can be subsequently split into subranges as discussed above. Finally, as will be understood by those skilled in the art, a range includes each individual member.

[0280] All publications, patent applications, issued patents, and other documents mentioned in this specification are incorporated herein by reference, just as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated herein by reference in its entirety. Definitions contained in text incorporated by reference are excluded to the extent they conflict with definitions in this disclosure.

[0281] Other embodiments are set forth in the following claims.

Claims

1. A polypropylene composition comprising: (a) a first polymer phase comprising a polypropylene homopolymer or random copolymer, the polypropylene homopolymer or random copolymer optionally comprising one or more comonomers in an amount equal to or less than about 3 wt %, based on the total weight of the propylene homopolymer or copolymer, having a total cold xylene soluble content of from about 2 wt % to about 6 wt %, and having a melt flow rate of from about 0.5 g / 10 min to about 3 g / 10 min; and (b) a second polymer phase comprising a propylene / ethylene copolymer comprising ethylene in an amount less than about 18 weight percent based on the total weight of the propylene / ethylene copolymer; in, The ratio of the melt flow rate of the polypropylene homopolymer or random copolymer to the melt flow rate of the propylene / ethylene copolymer is greater than about 1.0; and wherein the first polymer phase and the second polymer phase are combined to provide the polypropylene composition, the polypropylene composition having a melt flow rate of about 4 g / 10 min or less, an ethylene content of less than about 5 wt%, a total cold xylene soluble content of about 5 wt% to about 20 wt%, a haze of less than about 20% at 1 mm, an IZOD impact strength of greater than about 500 J / m at 23° C., a Gardner drop impact strength of greater than about 150 inch pounds at 0° C., and a flexural modulus of greater than or equal to about 800 MPa.

2. A polypropylene composition comprising: (a) a first polymer phase comprising a polypropylene homopolymer or random copolymer, the polypropylene homopolymer or random copolymer optionally comprising one or more comonomers in an amount equal to or less than about 1 wt %, based on the total weight of the propylene homopolymer or copolymer, having a total cold xylene soluble content of less than about 4 wt %, and having a melt flow rate of about 2 g / 10 min to about 5 g / 10 min; and (b) a second polymer phase comprising a propylene / ethylene copolymer comprising ethylene in an amount less than about 18 weight percent based on the total weight of the propylene / ethylene copolymer; in, The ratio of the melt flow rate of the polypropylene homopolymer or random copolymer to the melt flow rate of the propylene / ethylene copolymer is greater than about 1.0; and wherein the first polymer phase and the second polymer phase are combined to provide the polypropylene composition, the polypropylene composition having a melt flow rate of about 5 g / 10 min or less, an ethylene content of less than about 3.5 wt%, a total cold xylene soluble content of about 5 wt% to about 15 wt%, a haze of less than about 20% at 1 mm, an IZOD impact strength of greater than about 200 J / m at 23°C, and a flexural modulus of greater than or equal to about 1100 MPa.

3. The polypropylene composition according to claim 1 or 2, wherein the first polymer phase comprises a crystalline matrix comprising a polypropylene homopolymer or a random copolymer.

4. The polypropylene composition according to any of claims 1-3, wherein the polypropylene composition comprises a heterophasic propylene copolymer.

5. The polypropylene composition of any one of claims 1 and 3-4, wherein the first polymer phase comprises a polypropylene homopolymer or random copolymer comprising one or more comonomers in an amount of about 0 wt% to about 3 wt%, based on the total weight of the propylene homopolymer or copolymer.

6. The polypropylene composition of any one of claims 1 and 3-5, wherein the first polymer phase comprises a polypropylene homopolymer or random copolymer having a total cold xylene soluble content of about 2.5 wt% or about 4.8 wt%.

7. The polypropylene composition of any one of claims 1 and 3-6, wherein the first polymer phase comprises a polypropylene homopolymer or random copolymer having a melt flow rate of about 0.5 g / 10 min to about 1.5 g / 10 min.

8. The polypropylene composition according to any one of claims 1 and 3-7, wherein the polypropylene composition has a melt flow rate of about 0.5 g / 10 min to about 1.5 g / 10 min.

9. The polypropylene composition of any one of claims 1 and 3-8, wherein the polypropylene composition has an ethylene content of about 2 wt% to about 4.5 wt%.

10. The polypropylene composition according to any one of claims 1 and 3-9, wherein the polypropylene composition has a total cold xylene solubles content of about 7 wt.-% or about 12 wt.-%.

11. The polypropylene composition of any one of claims 1 and 3-10, wherein the polypropylene composition has a haze of about 5% to about 15% at 1 mm.

12. The polypropylene composition according to any one of claims 1 and 3-11, wherein the polypropylene composition has an IZOD impact strength at 23°C of about 500 J / m to about 900 J / m.

13. The polypropylene composition of any one of claims 1 and 3-12, wherein the polypropylene composition has a Gardner drop impact strength at 0°C of about 150 inch pounds to about 350 inch pounds.

14. The polypropylene composition of any one of claims 1 and 3-13, wherein the polypropylene composition has a flexural modulus of about 800 MPa to about 1300 MPa.

15. The polypropylene composition of any one of claims 2-4, wherein the first polymer phase comprises a polypropylene homopolymer or random copolymer comprising one or more comonomers in an amount of about 0.5 wt% to about 1 wt%, based on the total weight of the propylene homopolymer or copolymer.

16. The polypropylene composition of any one of claims 2-4 and 15, wherein the first polymer phase comprises a polypropylene homopolymer or random copolymer having a total cold xylene solubles content of about 1 wt% to about 3 wt%.

17. The polypropylene composition of any one of claims 2-4 and 15-16, wherein the first polymer phase comprises a polypropylene homopolymer or random copolymer having a melt flow rate of about 2 g / 10 min to about 4 g / 10 min.

18. The polypropylene composition according to any one of claims 2-4 and 15-17, wherein the polypropylene composition has a melt flow rate of about 2 g / 10 min to about 4 g / 10 min.

19. The polypropylene composition of any one of claims 2-4 and 15-18, wherein the polypropylene composition has an ethylene content of about 2 wt% to about 3.5 wt%.

20. The polypropylene composition according to any one of claims 2-4 and 15-19, wherein the polypropylene composition has a total cold xylene solubles content of about 5.5 wt.-% or about 12 wt.-%.

21. The polypropylene composition according to any one of claims 2-4 and 15-20, wherein the polypropylene composition has a haze at 1 mm of about 10% to about 20%.

22. The polypropylene composition according to any one of claims 2-4 and 5-21, wherein the polypropylene composition has an IZOD impact strength at 23°C of about 200 J / m to about 900 J / m.

23. The polypropylene composition according to any one of claims 2-4 and 5-22, wherein the polypropylene composition has a flexural modulus of about 1200 MPa to about 1600 MPa.

24. The polypropylene composition of any one of claims 1-23, wherein the second polymer phase comprises a propylene / ethylene copolymer comprising ethylene in an amount of about 10 wt% to about 18 wt%, based on the total weight of the propylene / ethylene copolymer.

25. The polypropylene composition of any one of claims 1-24, wherein the ratio of the melt flow rate of the polypropylene homopolymer or random copolymer to the melt flow rate of the propylene / ethylene copolymer is from about 1.0 to about 3.

0.

26. The polypropylene composition of any one of claims 1-25, wherein the polypropylene composition has a Gardner drop impact strength at 23°C of greater than about 150 inch pounds.

27. The polypropylene composition according to any one of claims 1 to 26, wherein the polypropylene composition further comprises one or more of a nucleating agent, an antacid and an antioxidant.

28. The polypropylene composition of claim 27, wherein the one or more nucleating agents are present in an amount of about 5000 ppm or less.

29. The polypropylene composition according to any one of claims 1 to 28, wherein the one or more comonomers present in the polypropylene homopolymer or random copolymer comprises ethylene.

30. A molded article formed from the polypropylene composition of any one of claims 1 to 29.

31. The molded article according to claim 30, wherein the molded article is an extrusion blow molded article.

32. A process for preparing a polypropylene composition according to any one of claims 1 to 29 by sequential polymerization in the presence of a Ziegler-Natta catalyst, wherein: preparing a first polymer phase in a first gas phase reactor, and transferring the first polymer phase to a second gas phase reactor containing a second polymer phase; Therein, the first polymer phase is combined with the second polymer phase to provide a polypropylene composition.

33. A process for preparing a polypropylene composition according to any one of claims 1 to 29, comprising: feeding propylene and optionally one or more comonomers into a first reactor; feeding a catalyst mixture comprising (1) a Ziegler-Natta catalyst, (2) a cocatalyst, and (3) an external donor into the first reactor; contacting the propylene with the catalyst mixture under first polymerization conditions to polymerize the propylene and optionally one or more comonomers to form a first polymer phase comprising a propylene homopolymer or copolymer; transferring at least a portion of the first polymer phase to a second reactor; and feeding additional propylene and ethylene into the second reactor to form a second polymer phase; Therein, combining the first polymer phase with the second polymer provides a polypropylene composition.

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