Random copolymer polypropylene compositions

Abstract

Compositions that include a random copolymer polypropylene that comprises at least one alpha- olefin co-monomer, a clarifier, and a nucleator that is not a clarifier.

Description

24T&I0025-WO-ORD 1RANDOM COPOLYMER POLYPROPYLENE COMPOSITIONSCROSS REFERENCE TO RELATED APPLICATIONS

[0001] None.FIELD

[0002] The present disclosure generally relates to compositions that comprise random copolymer polypropylene (random copolymer polypropylene (RCP) compositions). More specifically, the present disclosure relates to random copolymer polypropylene compositions comprising a particular clarifier based formulation.BACKGROUND

[0003] Polypropylene is a thermoplastic polymer that is used in a wide range of applications such as packaging, textiles, stationery, plastic parts, containers, laboratory equipment, and automotive components. The suitability of polypropylene for these application is, at least in part, due to its superior mechanical properties, optical performance, and excellent processability. However, polypropylene has some inherent limitations such as lack of transparency caused by low nucleation density and slow crystallization rate.

[0004] Transparency of a polymer is directly related to the morphology formed during solidification of the polymer from a melt of raw materials. Solidification in semi-crystalline polymers like polypropylene takes place via a crystallization process that forms crystalline lamellae / spherulitic superstructures. Spherulitic structures growing into sizes comparable to the wavelength of light (approximately 500 nm) cause variations in refractive index of such polymers. Variations in refractive index, in turn, can increase the scattering of light, which is usually manifested by an increase of haze. Another important factor that determines the optical properties of polymers like polypropylene is temperature variation during the process of making the polymer. Temperature variations can cause major variations of the time scales during which solidification takes place. Such variations can cause internal stresses and ultimately give rise to changes in the dimension or / and shape of the final product. To enhance crystallization rate of the polymer and to minimize dimensional changes, nucleating agents (nucleators) are added to the polymer. The24T&I0025-WO-ORD 2 nucleating agents provide additional sites from which crystallization is initiated. Typically, nucleating agent particles are non-soluble in the polymer with particle sizes in the micron range.

[0005] The haze value of polypropylene compositions is typically improved by adding clarifying agents (clarifiers) which assemble into nano-sized fibrils whenever the temperature of the polymer melt is reduced. Ideally, this process takes place before the nascent polymer crystallizes. Clarifiers also act as nucleating agents, causing a substantial reduction in spherulite size, and because of their dimensions, these clarifiers do not contribute to light scattering in the final product. Usually, clarifying agents are mixed with polypropylene in the compounding step. The resulting clarified polypropylene materials are used in applications that require highly transparent articles.BRIEF SUMMARY

[0006] Disclosed herein are random copolymer polypropylene compositions comprising a particular clarifier based formulation that creates an advantageous combination of physical properties, including crystallization temperature at wide range of cooling rates, flow-enhanced crystallization kinetics, and exceptionally low haze performance at lower light wavelength due to controlled crystalline morphology. For example, the disclosed random copolymer polypropylene compositions provide a significant improvement in the crystallization (solidification) temperature and kinetics over conventional polypropylene compositions.

[0007] Some configurations of the disclosure include a composition that comprises a random copolymer polypropylene that comprises at least one alpha-olefin co-monomer, wherein the at least one alpha-olefin co-monomer is 1-5 wt. % of the random copolymer polypropylene, wherein the poly dispersity index of the random copolymer polypropylene in the composition is 2-15 Mw / Mn. The composition further comprises a clarifier and a nucleator that is not a clarifier, wherein the combined concentration of the clarifier and the nucleator that is not a clarifier in the composition is in a range of 1700-4300 ppm and wherein the concentration of the clarifier in the composition is 65-91 wt. % of the combined concentration of the clarifier and nucleator that is not a clarifier. The composition has the following properties: a) a peak crystallization temperature in a range of 40 °C to 100 °C measured via flash DSC under cooling rate above 100 °C / sec; b) a peak crystallization temperature of 10 °C to 50 °C higher than a peak crystallization temperature24T&I0025-WO-ORD 3 of the composition with the clarifier and without the nucleator that is not a clarifier, measured via flash DSC under a cooling rate in the range from 0.15 °C / secto 100 °C / sec; c) a peak crystallization temperature in a range of 70 °C to 100 °C, measured via flash DSC under a cooling rate in the range of 40-100 °C / sec; and d) a haze value in a range of 5% to 20% at a wavelength of 400 nm as per ASTM 1003 on a sample with a thickness of 1 mm and a haze value in a range of 2% to 11% at a wavelength of 550 nm, measured on a sample with a thickness of 1 mm.

[0008] In some configurations of the disclosure, (i) the clarifier comprises: a sorbitol, lithium 2,2'-methylene-bis(4,6-di-tert-butulphenyl) phosphate, or combination thereof; and (ii) the nucleator that is not a clarifier comprises a derivative of a carboxylic acid or its salt, a salt of a substituted aromatic heterocyclic phosphate, a salt of bicycle [2.2.1] heptane di carb oxy late, y- quinacridone, calcium pimelate, N,N-dicyclohexyl-2,6-naphthalene dicarboxamide, or combinations thereof.

[0009] The following includes definitions of various terms and phrases used throughout this specification.

[0010] The terms “about” or “approximately” are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting aspect the terms are defined to be within 10%, preferably, within 5%, more preferably, within 1%, and most preferably, within 0.5% of the relevant value(s).

[0011] For the purposes of this disclosure, “X, Y, and / or Z” can be construed as X only, Y only, Z only, or any combination of two or more items X, Y, and Z (e.g., XYZ, XY, XZ, YZ).

[0012] The terms “wt. %”, “vol. %” or “mol. %” refer to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume, or the total moles of material that includes the component. In a non-limiting example, 10 moles of component in 100 moles of the material is 10 mol. % of component.

[0013] The term “substantially” and its variations are defined to include ranges within 10%, within 5%, within 1%, or within 0.5% of the relevant value(s).24T&I0025-WO-ORD 4

[0014] The terms “inhibiting” or “reducing” or “preventing” or “avoiding” or any variation of these terms, when used in the claims and / or the specification, include any measurable decrease or complete inhibition to achieve a desired result.

[0015] The term “effective,” as that term is used in the specification and / or claims, means adequate to accomplish a desired, expected, or intended result.

[0016] The use of the words “a” or “an” when used in conjunction with the term “comprising,” “including,” “containing,” or “having” in the claims or the specification may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.”

[0017] The words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0018] The process of the present disclosure can “comprise,” “consist essentially of,” or “consist of’ particular ingredients, components, compositions, etc., disclosed throughout the specification.

[0019] The term “primarily,” as that term is used in the specification and / or claims, means greater than any of 50 wt. %, 50 mol. %, and 50 vol. %. For example, “primarily” may include 50.1 wt. % to 100 wt. % and all values and ranges there between, 50.1 mol.% to 100 mol.% and all values and ranges there between, or 50.1 vol. % to 100 vol. % and all values and ranges there between.

[0020] A disclosure of a numerical range in the specification and / or claims, is a disclosure of any range or value within the disclosed range. For example, a disclosure of a range of 1 to 10 includes ranges of 1 to 5, 5 to 10, 3 to 8, 5 to 6, 5.5 to 6.4 and so on; and includes values 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1.1 2.2, 3.3, 4.9, 5.8, 6.7, and so on.

[0021] Other objects, features and advantages of the present disclosure will become apparent from the following figures, detailed description, and examples. It should be understood, however,24T&I0025-WO-ORD 5 that the figures, detailed description, and examples, while indicating specific embodiments of the disclosure, are given by way of illustration only and are not meant to be limiting. Additionally, it is contemplated that changes and modifications within the spirit and scope of the disclosure will become apparent to those skilled in the art from this detailed description. In further embodiments, features from specific embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In further embodiments, additional features may be added to the specific embodiments described herein.BRIEF DESCRIPTION OF THE DRAWINGS

[0022] For a more complete understanding, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:

[0023] FIG. 1 A shows a graph comparing crystallization temperature of a conventional random copolymer polypropylene composition with crystallization temperature of an example of the present random copolymer polypropylene compositions, according to aspects of the disclosure.

[0024] FIG. IB shows a graph comparing haze properties of a conventional random copolymer polypropylene composition with haze properties of an example of the present random copolymer polypropylene compositions, according to aspects of the disclosure.

[0025] FIG. 2A shows a Transmission Electron Microscopy (TEM) image of random copolymer polypropylene composition with a clarifier (sorbitol).

[0026] FIG. 2B shows a Transmission Electron Microscopy image of a random copolymer polypropylene composition without clarifier.

[0027] FIG. 3 shows a comparison of crystallization temperatures of a conventional random copolymer polypropylene composition with crystallization temperatures of an example of the present random copolymer polypropylene compositions, according to aspects of the disclosure.

[0028] FIG. 4 shows a graph of crystallization half-time for a conventional random copolymer polypropylene composition and an example of the present random copolymer polypropylene24T&I0025-WO-ORD 6 compositions, according to aspects of the disclosure, as a function of different isothermal crystallization temperatures.

[0029] FIG. 5 shows a graph illustrating the effect of temperature on the isothermal crystallization of a conventional random copolymer polypropylene composition and on an example of the present random copolymer polypropylene compositions, according to aspects of the disclosure, at shear rate of 0.05s'1.

[0030] FIG. 6A shows Transmission Electron Microscopy images of a conventional random copolymer polypropylene composition.

[0031] FIG. 6B shows an example of the present random copolymer polypropylene compositions, according to aspects of the disclosure.DETAILED DESCRIPTION

[0032] Random copolymer propylene has advantageous properties such as improved stiffness / impact, sterilization characteristics, but also has the deficiencies such as relatively slow crystallization kinetic that causes increased opacity and reduced dimensional stability. Thus, there is a need to develop random copolymer polypropylene compositions with improved crystallization kinetics that result in, for example, reduction of cycle time for injection molding, without compromising the composition’s optical properties (e.g., haze).

[0033] In aspects of this disclosure, a clarifier formulation is introduced in random copolymer polypropylene to cause an increase of crystallization temperature at a wide range of cooling rates and enhancement of the crystallization kinetics, which results in unexpectedly exceptional optical properties (very low haze values at lower wavelength ranges).

[0034] The properties of random copolymer polypropylene are highly dependent on its crystalline morphology, which is affected by various factors, such as processing conditions (temperature, flow-fields and pressure), preparation procedure (product dimensions, wall thickness) and composition (stabilizers, filler particles). Adding nucleating agents to semicrystalline polymers like random copolymer polypropylene allows for tailoring of their properties24T&I0025-WO-ORD 7 by controlling the solidification process of the polymer resin, i.e., by controlling the formation of the semi-crystalline morphology.

[0035] The increase in crystallization temperature of the random copolymer polypropylene caused by the presence of nucleating agents, presents obvious advantages with regard to processing condition as it allows for shorter cycle times and thus significant energy saving. The increase in the number of sites from which crystal growth is initiated (nucleation density) also affects the polymer’s optical, mechanical, and thermomechanical properties. Nucleating agents control the polymer morphology over a wide range of length scales ranging from several nm (crystal structure, polymorphism), to tens of nm (lamellae dimensions, melting / crystallization temperature), up to hundreds of microns (spherulitic superstructures, optical properties).

[0036] Clarifying agents are a sub-group of nucleating agents that improve the optical properties of a polymer. Even though the mechanisms by which these additives impart transparency are understood on a general level, there are many aspects related to the formation of the clarifying particles from the melt that are not fully understood. Formation of the primary fibrils does not occur instantaneously as it is time dependent and limited by diffusion of the clarifier, which dissolves in a polymer melt. Moreover, keeping the clarifier containing polymer for extended time in a melt state can reduce clarifier efficiency due to agglomeration of the primary fibrils.

[0037] Transparency characteristics of polymers are quantified with respect to their transmittance by haze and clarity. Haze refers to the part of the total amount of transmitted light that is scattered at angles higher than 2.5°. A high value of haze signifies a loss of contrast of an object viewed through the material. Clarity refers to the ability of a material to transmit fine details of an artifact and is more difficult to assess.

[0038] In the art, clarifying agents (clarifiers) and nucleating agents (nucleators) are used to improve the transparency or crystallization kinetics of random copolymer polypropylene. However, the addition of nucleating agents in random copolymer polypropylene usually results in negative performance when it comes to clarity. Therefore, it is essential to find the ideal concentrations for clarifying agents or nucleating agents in the random copolymer polypropylene matrix to improve their nucleation and clarifying efficiency. Typically, clarifier or nucleating24T&I0025-WO-ORD 8 agents are separately used, but not in combination, as the mixture may lead to a compromise of the overall haze values of the random copolymer polypropylene.

[0039] The term “nucleator” (NA), as that term is used in the specification and / or claims, means an additive dispersed in a polymer as a foreign particulate, acting as heterogeneous nuclei, which increases the rate of crystallization of the polymer and reducing the free energy needed for the formation of the critical nucleus hence resulting in increased solidification rates, which will decrease the injection molding cycle time, as compared to when the nucleator is not present. A “nucleator” can yield crystals of the a, P, y type or a combination thereof. A “nucleator,” does not dissolve in a polymer melt upon heating and does not form a fibrillar network upon cooling from the melt.

[0040] The following is a non-exhaustive list of examples of nucleators: (a) inorganic nucleators, such as silica, clay and talc; (b) derivatives of carboxylic acid and their salts, such as sodium and lithium benzoate, bicyclo [2.2.1] heptane dicarboxylic acid derivatives; (c) organophosphorus derivatives and their salts, such as sodium 2,2’-methylene-bis(4,6-di-tert- butylphenyl) phosphate; and (d) polymers, such as polyvinylcyclohexane (PVCH), polytetrafluoroethylene (PTFE), and polyamide (PA).

[0041] The term “clarifier” as that term is used in the specification and / or claims, means an additive that enhances the clarity and optical properties of a polymer such as polypropylene (PP) and random copolymer polypropylene, by reducing haze and improving transparency. Clarifiers are designed to disperse or dissolve in the polymer melt upon heating and, upon cooling, form submicron-sized (i.e., less than one micron) fibrillar networks within the polymer matrix. This fibrillar fiber typically have diameter in nanoscale. These networks, are often comprised of particles smaller than 0.5 pm, act as clarifying agents, significantly increasing nucleation density and result in smaller spherulites, generally smaller than 1.5 pm. This reduction in spherulite size improves the optical properties of the polymer by decreasing haze — defined as the percentage of light scattered at angles above 2.5° relative to the incident light — while simultaneously increasing clarity. High clarity in the polymers permits improved resolution of objects viewed through the material, as less light is scattered.24T&I0025-WO-ORD 9

[0042] The following is a non-exhaustive list of examples of clarifiers, according to aspects of this disclosure: dibenzylidene sorbitol (DBS), bis (4-methylbenzylidene) sorbitol (MDBS) (e.g., Geniset® MD), bis (4-ethylbenzylidene) sorbitol (EDBS), bis (3,4- dimethylbenzylidene) sorbitol (DMDBS) (e.g., Geniset® DXR), l,2,3-tridesoxy-4,6:5,7-bis-O-[(4-propylphenyl) methylene]- nonitol lithium 2,2 ' -methylene-bis(4,6-di-tert-butulphenyl) phosphate, dibenzylidene xylonic acid, 4,4’- dimethyldibenzylidene xylonic acid methyl hydrazide, and 2,4,8, 10-Tetra(tert-butyl)- 6-hydroxy-12H-dibenzo[d,g]dioxaphosphocin 6-oxide, sodium salt (NA-71).

[0043] It should be understood that all clarifiers are nucleators, but not all nucleators are clarifiers. The examples of nucleators provided in the paragraph below are not clarifiers based on the description of clarifiers in the two paragraphs above, specifically the requirement of the ability to form submicron-sized fibrillar networks within the polymer matrix. The nucleators provided in the paragraph below will not form submicron-sized fibrillar networks within the polymer matrix and therefore, such nucleators are not also clarifiers.

[0044] The following is a non-exhaustive list of examples of nucleators that are not clarifiers, according to aspects of this disclosure: poly(tetrafhioroethylene) (PTFE), poly (vinylcyclohexane) (PVCH), polyamide (PA), PET or functionalized polypropylene, aluminum-monohydroxy-bis-(p- tert-butyl benzoate), bicyclo heptane-2, 3 -dicarboxylic acid sodium salt, cis-l,2-cyclohexane dicarboxylic acid (e.g., Hyperform® HPN® 600ei), 1,4-phenylenebisamides, N,N’ -di cycloh exyl- 2,6-naphthalindicarboxamid, N,N‘-dicyclohexylterephthaldiamid; sodium-2,2’-methylene-bis (4,6-di-tert-butylphenyl) phosphate, aluminumhydroxy -bis [2,2’-methylene-bis (4,6-di-tert- butylphenyl) phosphate], y-Quinacridone, trans-chinacridone, chinacrionchinone, organic blue pigment based on phtalocyanines, dibenzylidene-L-gulonic amide, dibenzylidene-L-gulonic alkyl amide, dibenzylidene-L-gulonic acid methyl ester, cyanuric acid, uracil, unmodified and chemically modified talc, surfactant-modified clays based on Dolomite, montmorillonite, carbon nanotubes, graphene oxide, and graphite.

[0045] In some aspects of the compositions disclosed herein, the composition comprises a random copolymer polypropylene that comprises at least one alpha-olefin co-monomer, wherein the at least one alpha-olefin co-monomer is 1-5 wt. %, or any value or range included therein, including ranges 1.5-4.5 wt. %, 2.0-4.0 wt. %, 2.5-3.5 wt. %, 1-1.5 wt. %, .1.5-2.0 wt. %, 2.0-24T&I0025-WO-ORD 102.5 wt. %, 2.5-3.0 wt. %, 3.0-3.5 wt. %, 3.5-4.0 wt. %, 4.0-4.5 wt. %, and 4.5-5 wt. % of the random copolymer polypropylene; wherein the polydispersity index of the random copolymer polypropylene in the composition is 2-15 Mw / Mn, or any value or range included therein, including ranges 3-14 Mw / Mn, 4-13 Mw / Mn, 5-12 Mw / Mn, 6-11 Mw / Mn, 7-10 Mw / Mn, 8-9 Mw / Mn, 2-3 Mw / Mn, 3-4 Mw / Mn, 4-5 Mw / Mn, 5-6 Mw / Mn, 6-7 Mw / Mn, 7-8 Mw / Mn, 8-9 Mw / Mn, 9-10 Mw / Mn, 10-11 Mw / Mn, 11-12 Mw / Mn, 12-13 Mw / Mn, 13-14 Mw / Mn, and 14- 15 Mw / Mn. Poly dispersity index, as that term is used in the specification and / or claims, means weight average molecular weight (Mw) divided by number average molecular weight (Mn) (i.e., poly dispersity index = Mw / Mn).

[0046] In some aspects, the random copolymer polypropylene composition further comprises a clarifier and a nucleator that is not a clarifier, wherein the combined concentration of the clarifier and the nucleator that is not a clarifier in the composition is in a range of 1700-4300 ppm, or any value or range included therein, including ranges 1800-4200 ppm, 1900-4100 ppm, 2000-4000 ppm, 2100-3900 ppm, 2200-3800 ppm, 2300-3700 ppm, 2400-3600 ppm, 2500-3500 ppm, 2600-3400 ppm, 2700-3300 ppm, 2800-3200 ppm, 2900-3100 ppm, 1700-1800 ppm, 1800- 1900 ppm, 1900-2000 ppm, 2000-2100 ppm, 2100-2200 ppm, 2200-2300 ppm, 2300-2400 ppm, 2400-2500 ppm, 2500-2600 ppm, 2600-2700 ppm, 2700-2800 ppm, 2800-2900 ppm, 2900- 3000 ppm, 3000-3100 ppm, 3100-3200 ppm, 3200-3300 ppm, 3300-3400 ppm, 3400-3500 ppm, 3500-3600 ppm, 3600-3700 ppm, 3700-3800 ppm, 3800-3900 ppm, 3900-4000 ppm, 4000- 4100 ppm, and 4100-4200 ppm, and 4200-4300 ppm, and wherein the concentration of the clarifier in the composition is 65-91 wt. % or any value or range included therein, including ranges 67-88 wt. %, 69-86 wt. %, 71-84 wt. %, 73-82 wt. %, 75-80 wt. %, 77-78 wt. %, 65-67 wt. %, 67-69 wt. %, 69-71 wt. %, 71-73 wt. %, 73-75 wt. %, 75-77 wt. %, 77-79 wt. %, 79-81 wt. %, 81-83 wt. %, 83-85 wt. %, 85-87 wt. %, 87-89 wt. %, and 89-90 wt. % of the combined concentration of the clarifier and the nucleator that is not a clarifier.

[0047] In some configurations, the random copolymer polypropylene composition has the following properties: a) a peak crystallization temperature of above 40 °C or any value or range included therein, including ranges 40-45 °C, 45-50 °C, 50-55 °C, 55-60 °C, 60-65 °C, 65-70 °C, 70-75 °C, 75-80 °C, 80-85 °C, 85-90 °C, 90-95 °C, and 95-100 °C, measured via flash DSC under cooling rate above 100 °C / sec; b) a peak crystallization temperature of 10 °C to 50 °C higher24T&I0025-WO-ORD 11 than a peak crystallization temperature of the composition with the clarifier and without the nucleator that is not a clarifier, measured via flash DSC under a cooling rate in the range from 0.15 °C / sec to 100 °C / sec or any value or range included therein, including ranges 5 °C / sec to 95 °C / sec, 10 °C / sec to 90 °C / sec, 15 °C / sec to 85 °C / sec, 20 °C / sec to 80 °C / sec, 25 °C / sec to 75 °C / sec, 30 °C / sec to 70 °C / sec, 35 °C / sec to 65 °C / sec, 40 °C / sec to 60 °C / sec, 45 °C / sec to 55 °C / sec, 0.15 °C / sec to 5 °C / sec, 5 °C / sec to 10 °C / sec, 10 °C / sec to 15 °C / sec, 15 °C / sec to 20 °C / sec, 20 °C / sec to 25 °C / sec, 25 °C / sec to 30 °C / sec, 30 °C / sec to 35 °C / sec, 35 °C / sec to 40 °C / sec, 40 °C / sec to 45 °C / sec, 45 °C / sec to 50 °C / sec, 50 °C / sec to 55 °C / sec, 55 °C / sec to 60 °C / sec, 60 °C / sec to 65 °C / sec, 65 °C / sec to 70 °C / sec, 70 °C / sec to 75 °C / sec, 75 °C / sec to 80 °C / sec, 80 °C / sec to 85 °C / sec, 85 °C / sec to 90 °C / sec, 90 °C / sec to 95 °C / sec, and 95 °C / sec to 100 °C / sec; c) a peak crystallization temperature of more than 70 °C or any value or range included therein, including ranges 70-75 °C, 75-80 °C, 80-85 °C, 85-90 °C, 90-95 °C, and 95-100 °C, measured via flash DSC under a cooling rate in the range of 40-100 °C / sec or any value or range included therein, including ranges 40-45 °C, 45-50 °C, 50-55 °C, 55-60 °C, 60-65 °C, 65-70 °C, 70-75 °C, 75- 80 °C, 80-85 °C, 85-90 °C, 90-95 °C, and 95-100 °C; and d) a haze value of less than 20% or any value or range included therein including 5-10%, 10-15%, 15-20% at a wavelength of 400 nm as per ASTM 1003 on a sample with a thickness of 1 mm and a haze value in a range of 2-4%, 4-8%, 8-10%, and 10-11% at a wavelength of 550 nm, measured on a sample with a thickness of 1 mm.

[0048] In some configurations, components comprised in the random copolymer polypropylene composition can include (i) the clarifier comprising: a sorbitol, lithium 2,2 ' -methylene-bis(4,6- di-tert-butulphenyl) phosphate, or combination thereof; and / or (ii) the nucleator that is not a clarifier comprising a derivative of a carboxylic acid or its salt, a salt of a substituted aromatic heterocyclic phosphate, a salt of bicycle [2.2.1] heptane dicarboxylate, y-quinacridone, calcium pimelate, N,N-dicyclohexyl-2,6-naphthalene dicarboxamide, or combinations thereof. With respect to the nucleator that is not a clarifier, the derivative of a carboxylic acid or its salt can comprise calcium 1,2-cy cl ohexanedi carboxylic acid and / or the salt a of a substituted aromatic heterocyclic phosphate comprises sodium 2,2 ' -methylene-bis-(4,6-di-t- butylphenylene)phosphate.24T&I0025-WO-ORD 12

[0049] In some configurations, the random copolymer polypropylene composition can comprise bis (3,4- dimethylbenzylidene) sorbitol (DMDBS) as clarifier and cis-l,2-cyclohexane dicarboxylic acid as nucleator that is not a clarifier.

[0050] In some configurations, the random copolymer polypropylene composition can comprise 2,4,8, 10-Tetra(tert-butyl)-6-hydroxy-12H-dibenzo[d,g]dioxaphosphocin 6-oxide, sodium salt (NA-71) as clarifier and cis-l,2-cyclohexane dicarboxylic acid as nucleator that is not a clarifier.

[0051] In some configurations, the random copolymer polypropylene composition can comprise one or more of the following list of nucleators that are not clarifiers: polytetrafluoroethylene) (PTFE), poly (vinylcyclohexane) (PVCH), polyamide (PA), PET or functionalized polypropylene, aluminum-monohydroxy-bis-(p-tert-butyl benzoate), bicyclo heptane-2,3-dicarboxylic acid sodium salt, cis-l,2-cyclohexane dicarboxylic acid, 1,4- phenylenebisamides, N,N’ -dicyclohexyl-2,6-naphthalindicarboxamid, N,N‘ - dicyclohexylterephthaldiamid; sodium-2,2’-methylene-bis (4,6-di-tert-butylphenyl) phosphate, aluminumhydroxy -bis [2,2’-methylene-bis (4,6-di-tert-butylphenyl) phosphate], y-Quinacridone, trans-chinacridone, chinacrionchinone, organic blue pigment based on phtalocyanines, dibenzylidene-L-gulonic amide, dibenzylidene-L-gulonic alkyl amide, dibenzylidene-L-gulonic acid methyl ester, cyanuric acid, uracil, unmodified and chemically modified talc, surfactant- modified clays based on Dolomite, montmorillonite, carbon nanotubes, graphene oxide, and graphite.

[0052] In some configurations, the random copolymer polypropylene composition can comprise one or more of the following list of clarifiers: dibenzylidene sorbitol (DBS), bis (4- methylbenzylidene) sorbitol (MDBS), bis (4-ethylbenzylidene) sorbitol (EDBS), bis (3,4- dimethylbenzylidene) sorbitol (DMDBS), l,2,3-tridesoxy-4,6:5,7-bis-O-[(4-propylphenyl) methylene]-nonitol(a) nonitol and sorbitol based acetals and (b) lithium 2,2 ' -methylene-bis(4,6- di-tert-butulphenyl) phosphate, and dibenzylidene xylonic acid, 4,4 ’ - dimethyldibenzylidene xylonic acid methyl hydrazide.24T&I0025-WO-ORD 13

[0053] In some configurations, the random copolymer polypropylene composition can comprise a clarifier that comprises bis (3,4- dimethylbenzylidene) sorbitol (DMDBS) and a nucleator that is not a clarifier that comprises cis-l,2-cyclohexane dicarboxylic acid.

[0054] In some configurations, the random copolymer polypropylene composition can have a half crystallization time of less than 0.3 sec measured at an isothermal crystallization temperature in the range of 50-90 °C or any value or range included therein, including ranges 50-55 °C, 55- 60 °C, 60-65 °C, 65-70 °C, 70-75 °C, 75-80 °C, 80-85 °C, 85-90 °C, 90-95 °C, and 95-100 °C.

[0055] In some configurations, the random copolymer polypropylene composition can have a maximum shear stress growth coefficient at a shear rate of 0.05 s'1and an isothermal temperature of (Tm+Tc) / 2, where Tm and Tc are the peak melting and crystallization temperatures, respectively, measured by DSC at a heating and cooling rate of 10 °C / min, respectively, reached at a time of less than 50 sec. or any value or range included therein, including ranges 2-10 sec, 5- 10 sec, 10-15 sec, 15-20 sec, 20-25 sec, 25-30 sec, 35-40 sec, and 45-49 sec.

[0056] In some configurations, the random copolymer polypropylene composition can have a melt flow rate in the range of 0.1-200 g / 10 min or any value or range included therein, including ranges 10-190 g / 10 min, 20-180 g / 10 min, 30-170 g / 10 min, 40-160 g / 10 min, 50-150 g / 10 min, 60-140 g / 10 min, 70-130 g / 10 min, 80-120 g / 10 min, 90-110 g / 10 min, 10-20 g / 10 min, 20-30 g / 10 min, 30-40 g / 10 min, 40-50 g / 10 min, 50-60 g / 10 min, 60-70 g / 10 min, 70-80 g / 10 min, 80-90 g / 10 min, 90-100 g / 10 min, 100-110 g / 10 min, 110-120 g / 10 min, 120-130 g / 10 min, BO- MO g / 10 min, 140-150 g / 10 min, 150-160 g / 10 min, 160-170 g / 10 min, 170-180 g / 10 min, 180- 190 g / 10 min, and 190-200 g / 10 min, measured at 230 °C and 2.16 Kg load. The random copolymer polypropylene can be peroxide shifted to achieve a desired melt flow rate.

[0057] In some configurations, the at least one alpha-olefin co-monomer of the random copolymer polypropylene composition can comprise ethylene. And in some configurations, the random copolymer polypropylene composition can comprise 2.0-4.0 wt. % or any value or range included therein, including ranges 2.5-3.5 wt. %, 2.0-2.5 wt. %, 2.5-3.0 wt. %, 3.0-3.5 wt. %, and 3.5-4.0 wt. % ethylene as the at least one alpha-olefin co-monomer. In some configurations, the at least one alpha-olefin co-monomer of the random copolymer polypropylene composition can have one or more of the following (1) a melt flow rate in the range of 10-100 g / 10 min or any24T&I0025-WO-ORD 14 value or range included therein, including ranges 20-90 g / 10 min, 30-80 g / 10 min, 40-70 g / 10 min, 50-60 g / 10 min, 10-20 g / 10 min, 20-30 g / 10 min, 30-40 g / 10 min, 40-50 g / 10 min, 50-60 g / 10 min, 60-70 g / 10 min, 70-80 g / 10 min, 80-90 g / 10 min, and 90-100 g / 10 min, measured at 230 °C and 2.16 Kg load and (2) yellowness index in a range of -12 to -3 or any value or range included therein, including ranges -11 to -4, -10 to -5, -9 to -6, -8 to -7, -11 to -10, -10 to -9, -9 to -8, -8 to -7, -7 to -6, -6 to -5, -5 to -4 and -4 to -3.

[0058] In some configurations, the random copolymer polypropylene composition can comprise 1300 to 3600 ppm or any value or range included therein, including ranges 1400 to 3500 ppm, 1500 to 3400 ppm, 1600 to 3300 ppm, 1700 to 3200 ppm, 1800 to 3100 ppm, 1900 to 3000 ppm, 2000 to 2900 ppm, 2100 to 2800 ppm, 2200 to 2700 ppm, 2300 to 2600 ppm, 2400 to 2500 ppm, 1400 to 1500 ppm, 1500 to 1600 ppm, 1600 to 1700 ppm, 1700 to 1800 ppm, 1800 to 1900 ppm, 2000 to 2100 ppm, 2100 to 2200 ppm, 2300 to 2400 ppm, 2500 to 2600 ppm, 2600 to 2700 ppm, 2700 to 2800 ppm, 2800 to 2900 ppm, 3000 to 3100 ppm, 3100 to 3200 ppm, 3200 to 3300 ppm, 3300 to 3400 ppm, 3400 to 3500 ppm, and 3500 to 3600 ppm of the clarifier (e.g., any of the clarifiers described herein).

[0059] In some configurations, the random copolymer polypropylene composition can comprise 400 to 700 ppm or any value or range included therein, including ranges 450 to 650 ppm, 500 to 600 ppm, 450 to 500 ppm, 500 to 550 ppm, 550 to 600 ppm, 600 to 650 ppm, and 650 to 700 ppm of the nucleator that is not a clarifier (e.g., any of the nucleators that are not clarifiers described herein).

[0060] In some configurations, the random copolymer polypropylene composition comprises a plurality of alpha-olefin comonomers. A non-exhaustive list of examples of such alpha-olefin comonomers are propene, butene, and pentene. In some configurations, the random copolymer polypropylene composition comprises unimodal or bimodal molecular weight distribution. In some configurations, the random copolymer polypropylene composition comprises of 11.0 ppm to 25.0 ppm or any value or range included therein, including ranges 12.0 ppm to 24.0 ppm, 13.0 ppm to 23.0 ppm, 14.0 ppm to 22.0 ppm, 15.0 ppm to 21.0 ppm, 16.0 ppm to 20.0 ppm, 17.0 ppm to 19.0 ppm, 11.0 ppm to 12.0 ppm, 12.0 ppm to 13.0 ppm, 13.0 ppm to 14.0 ppm, 14.0 ppm to 15.0 ppm, 15.0 ppm to 16.0 ppm, 16.0 ppm to 17.0 ppm, 17.0 ppm to 18.0 ppm, 18.0 ppm to 19.024T&I0025-WO-ORD 15 ppm, 19.0 ppm to 20.0 ppm, 20.0 ppm to 21.0 ppm, 21.0 ppm to 22.0 ppm, 22.0 ppm to 23.0 ppm, 23.0 ppm to 24.0 ppm, 24.0 ppm to 25.0 ppm, of one or more pigment(s).

[0061] In aspects of this disclosure, an article of the random copolymer polypropylene composition is comprised in one or more of the following: a building component, cladding, laminate, membrane, pipe, a component of an appliance, an automotive component, a health care or medical product, a syringe, biomedical hose, bottle, a component or product used in a rigid packaging application or a flexible packaging application, a component or product used in a telecom duct application, a component or product produced by injection molding, extrusion, thermoforming, compression molding, injection compression molding, or other polymer molding process.

[0062] Referring now to FIG. 1 A, disclosed is a graph comparing crystallization temperature of a conventional random copolymer polypropylene composition with crystallization temperature of an example of a present random copolymer polypropylene composition. The conventional random copolymer polypropylene composition comprised 1 to 5 wt.% ethylene as a comonomer. The example of the present random copolymer propylene compositions comprised 3.0 to 3.5 wt. % of ethylene comonomer. Approximately 90 to 110 nanogram of random copolymer propylene was measured against the empty reference pan using a Flash DSC 2 from Mettler-Toledo under a nitrogen gas flow at 20 ml / min. The samples were heated from -85 C to 250 °C at 150 K / s and each sample was hold for 60 sec at 250 °C. Different cooling rates were deployed to follow the crystallization temperature of random copolymer propylene at different cooling rates.

[0063] Referring now to FIG. IB, disclosed is a graph comparing haze properties of a conventional random copolymer polypropylene composition with haze properties of an example of the present random copolymer polypropylene compositions, according to aspects of the disclosure. The conventional random copolymer polypropylene composition comprised polypropylene with ethylene as comonomer and a clarifier agent. The example of the present random copolymer propylene compositions comprised polypropylene with ethylene as comonomer and a clarifying formulation described in this disclosure. The injection molding for haze measurement samples was carried out using KraussMaffei injection molding machine having24T&I0025-WO-ORD 16 clamping force of 50T. The haze samples were prepared and tested as per the ASTM 1003, using Perkin Elmer Lambda 950 with integrating sphere spectrometer having wall thickness of 1.0 mm.

[0064] It should be noted that the example of the random copolymer polypropylene compositions, according to aspects of the disclosure provides a significant improvement in the crystallization (solidification) temperature and kinetics (FIG. 1 A), while with respect to the optical clarity at wavelength of 700 nm there is a significant improvement in the low wavelength range (400-650 nm) (FIG. IB). It should also be noted that the example of the present random copolymer polypropylene compositions would crystallize polypropylene at a fast cooling rate of 1500K / s or higher, whereas conventional random copolymer polypropylene composition is effective up to cooling rate of about 100 to 150K / s. These unique features of the example of the present random copolymer polypropylene compositions are envisioned to have significant consequences on processes such as injection molding with improved cycle time for thicker and thinner parts while achieving excellent balance of optical and mechanical properties.

[0065] FIG. 2A and FIG. 2B illustrate the effect of a clarifier in a polymer. FIG. 2A shows Transmission Electron Microscopy (TEM) images that present the fibrillar morphology associated with a clarifying additive formulation of a sorbitol based clarifier (2000 ppm) in a random copolymer polypropylene composition. FIG. 2B shows the random copolymer polypropylene composition without added clarifier and thus the TEM images do not show the fibrillary morphology under similar imaging conditions.

[0066] In some aspects of the disclosure, a mixture of clarifying and nucleating agents in a specific ratio is provided in polypropylene to speed up the crystallization kinetics of the polypropylene, while also reducing the haze of the resulting composition. To the inventors’ knowledge, conventionally, no random copolymer polypropylene composition has demonstrated nucleation effects that can shift the crystallization temperature of polypropylene at higher cooling rates (above 200K / s) without deteriorating optical properties. Disclosed herein are clarifier formulations where the crystallization temperature of random copolymer polypropylene at a cooling rate above 200K / s without deterioration in the optical properties of the resulting random copolymer polypropylene composition.24T&I0025-WO-ORD 17

[0067] FIG. 3 shows crystallization temperatures for an example of the present random copolymer polypropylene compositions, at different cooling rates. The example of the present random copolymer propylene compositions comprised polypropylene with ethylene as comonomer and a clarifying formulation described in this disclosure. The example of the present random copolymer polypropylene compositions is shown to have higher crystallization temperatures compared with the conventional random copolymer polypropylene composition. The conventional random copolymer polypropylene composition comprised polypropylene with ethylene as comonomer and a clarifying agent. The example of the present random copolymer polypropylene compositions promotes crystallization of polypropylene even at very high crystallization rates such as 500k / s, 750k / s or lOOOk / s, rates at which the conventional random copolymer polypropylene composition would show little or no crystallinity. Approximately 90 to 110 nanogram of random copolymer polypropylene was measured against the empty reference pan using a Flash DSC 2 from Mettler-Toledo under a nitrogen gas flow at 20 ml / min. The samples were heated from -85 °C to 250 °C at 150 K / s and sample was held for 60 sec at 250 °C. Different cooling rates were deployed to follow the crystallization temperature of random copolymer polypropylene at different cooling rates.

[0068] The example of the present random copolymer polypropylene composition has shown promising results as it provides higher crystallization temperatures and promotes crystallization of polypropylene even at very high cooling rates. The crystallization behavior observed through Flash DSC shows that the example of the present random copolymer polypropylene compositions has a double bell-shaped curve, especially in the region of 40° C to 120° C isothermal crystallization condition (FIG. 4). This indicates a distinct effect of the example of the present random copolymer polypropylene compositions on the crystallization kinetics of polypropylene. On the other hand, the conventional random copolymer polypropylene composition showed effectiveness in enhancing crystallization kinetics till 50° C. The region below 40° C is dominated by polypropylene self-nucleation and influenced by the clarifier.

[0069] Further investigation using rheological measurements has shown subtle differences on the effect of flow on the crystallization kinetics of polypropylene. These changes represent the processing characteristics of polypropylene during different molding conditions. The example of the present random copolymer polypropylene composition has shown faster crystallization (FIG.24T&I0025-WO-ORD 185), with a specific hump at time of approximately 10 sec, while the conventional random copolymer polypropylene composition shows a time of approximately 220 sec. This hump represents the start of crystallization of polypropylene. Faster crystallization is preferred under flow to minimize the cycle time for processes such as injection molding.

[0070] Another distinct effect of the example of the present random copolymer polypropylene compositions has been observed on haze related to the change of the morphology. FIG. IB showcases the haze values as a function of wavelength of light in the visible region, while FIG. 6A and 6B presents the respective transmission electron microscopy images of the samples. As indicated from FIG. IB, a significant decrease in the haze value, especially in the low wavelength region, is a unique feature of the innovative composition. The TEM images in FIG. 6A and 6B indicate the specific orientation in the example of the present random copolymer polypropylene compositions (FIG. 6B) compared to the conventional random copolymer polypropylene composition (FIG. 6A). The TEM images indicate unexpected orientation in the example of the present random copolymer polypropylene compositions, which could explain the enhancement in the optical properties. This is most likely due to the reduction in the dimension of crystalline domain.EXAMPLE

[0071] Samples of formulations were prepared and tested as follows.Process of making clarified random copolymer polypropylene compositionsMaterials

[0072] The samples were produced using a pilot scale extruder. A random copolymer polypropylene with a co-monomer (C2) content of about 3.0 wt%- 3.5 wt% (SABIC® PP QR6731K) was used as the base resin grade (comparative example). A standard antioxidant stabilization package was used for both the example of the present random copolymer polypropylene compositions as well as the comparative examples (conventional random copolymer polypropylene compositions). This grade has a melt flow rate (MFR) of 25 gram / 10 min as measured at 230 °C and 2.16 Kg load. The clarifier additive package used for preparing the example of the present random copolymer polypropylene compositions is shown in Table 1,24T&I0025-WO-ORD 19 which demonstrates the positive synergy in examples 1 to 4, and non-working examples in examples 5 to 10.Compounding

[0073] The samples were compounded on a pilot-scale twin-screw co-rotating extruder, KraussMaffei, ZE25A, which has a polyolefin compounding screw design. The extruder is capable of a throughput ranging from 15-25 kg / h and a maximum screw speed of 1000 rpm. The barrel of the extruder is 32 mm in diameter with a length over outside diameter (L / D) ratio of 40. The barrel is segmented into 8 temperature-controlled zones starting after the feeding zone (50 °C). The eight-zone temperature was set between 190 to 230 °C, endings with the die zone.

[0074] The samples were physically prepared and dry mixed in a plastic bottle and then transferred to the feeder. The temperature zones were set starting at 180 °C in zone 1 and increased to 230 °C in the die zone, with temperature intervals of 6 °C between zones 2 to 7. The strand that came out of the three die holes, was quenched in a water bath before being collected and pelletized.Injection Molding

[0075] The injection molding for haze measurement samples was carried out using KraussMaffei having clamping force of 50T. The haze samples were prepared and tested as per the ASTM 1003.Flash Differential Scanning Calorimetry (Flash-DSC)

[0076] Flash DSC experiments were performed on a Flash DSC 2 from Mettler-Toledo. The purge gas used in the experiments was nitrogen at a flow rate of 20 ml / min. The heating rate was constant at 150 K / s, while the cooling rate was varied up to 10000 K / sec to investigate the dependency on cooling rate and the crystallization kinetics. The sample masses used were 90 to 110 nanograms per sample, and the data is presented in FIG. 1.

[0077] Isothermal experiments were performed to determine half time of crystallization. The exothermal crystallization peaks were recorded during isothermal segments of 50 seconds at various temperatures covering the range -40 to 125 °C.24T&I0025-WO-ORD 20

[0078] Most traditional experimental methods that probe crystallization of polypropylene are disadvantageous in that temperature gradients achievable in lab-based experiments strongly differ from those encountered in industrially relevant processes, which can be as high as 1000 °C / s. These values were encountered within those regions of the final products that were in contact with the cooled mold and cause rapid cooling of the material near its glass temperature. These aspects become highly relevant in, for example, injection-molding processes and rigid packaging applications where thickness of the product is rather low. In these cases, cooling rates throughout the product can be very high and thus limiting or even preventing crystallization in the final product. Besides causing inferior mechanical properties, incomplete crystallization can cause dimensional changes that result in shrinkage or warpage of the final product.

[0079] Therefore, it can be important to control crystallization behavior of polypropylene based resins under industrially relevant conditions where high throughput rates imply rapid changes in the applied temperature profiles. Crystallization of a polymer melt takes place on pre-existing nuclei that are either forming spontaneously in the melt (homogeneous nucleation) or exist in the form of highly dispersed solid particles that are added to the resin to provide additional surfaces from which the crystallization can start (heterogeneous nucleation).

[0080] In literature, studies on nucleating efficiency of specific components are mostly based on results of non-isothermal crystallization experiments using standard DSC, with changes in crystallization temperature Tc being used as an indicator for the efficiency of the nucleating system. Although there are models describing the change in crystallinity in this case, they are often limited in applicability owing to the specific crystallization conditions (deep, instead of shallow quench conditions).

[0081] On the other hand, fast scanning calorimetry offers the possibility to study crystallization kinetics under industrially relevant conditions. The main advantage of these experiments is the possibility to apply very high cooling rates to separate contributions related to homogeneous nucleation, i.e., resin specific, from those induced by heterogeneous nucleation, i.e. the contribution arising from nucleating agents or clarifiers added to the resin sample. Although a large number of studies have been published on non-nucleated polymer resins, few studies have addressed crystallization kinetics of industrially relevant, nucleated resins.24T&I0025-WO-ORD 21Haze Measurements:

[0082] The haze studies were performed using Perkin Elmer Lambda 950 with integrating sphere spectrometer. The measurement was conducted as per ASTM 1003, having wall thickness of 1.0 mm.

[0083] Haze measurements in the visible region (400-700nm) were carried out on a BYK Gartner hazemeter. All other wavelength dependent haze measurements were carried out on a Perkin Elmer Lambda 950 UV Vis NIR spectrophotometer equipped with a 150 mm integrating sphere. The reflectance standard was placed in the holder and a background scan was taken. The sample plaques having 1.0 mm thickness were produced as the sample preparation method described in ASTM 1003 and were purged with an air blower to free the surfaces of dust.TEM measurements:

[0084] Rectangular samples with dimensions 1 cm X 0.5 cm were cut from the compression molded samples and subsequently blocked using a sharp scalpel, to get analysis area of approximately 0.1 mm x 1 mm. Typically, the samples with narrow widths of 0.1-0.2 mm are preferred, in order to reduce the force on the diamond knife used for the final cutting (microtomy) and thereby to reduce the chattering effect (wave-like folds in the sample). Microtomy or fine slicing of the samples was performed with a Leica Ultracut UCT microtome, cooled by liquid nitrogen. For a cryo-microtomy process, the ultramicrotome was equipped with an anti-static device. The sample cutting for the random polypropylene copolymer compositions was done by a modified process which eschewed the steps of using sucrose solution for sample picking, instead using an ethanol-wetted Cu TEM grid. The as-prepared TEM grids were imaged as-is, without any heavy metal staining. These grids were transferred into an electron microscope for imaging. In summary, the LEICA microtome settings were optimized for the best sample cutting conditions. For the polypropylene compositions, the best imaging of the samples were achieved when they were cut at -140 C to -160 C. For imaging in the bright field mode, FEI Tecnai T12 operated at 120kV, was used. Images were recorded at low magnifications of 3900-9700X.Shear Rheometry:24T&I0025-WO-ORD 22

[0085] An Anton Paar rotational rheometer (MCR 302e) was used to study the shear rheology of samples. Polypropylene pellets were melted at the temperature of 180 °C and then were pressed in a compression molding apparatus to produce sheets of thickness of about 1 mm. The shear induced crystallization behavior of polymers was examined in simple shear flow using the parallel plate geometry with plates of 25 mm in diameter. These experiments were confined to the temperature region between the crystallization and the melting peaks found in the DSC thermograms under the heating and cooling cycles. This temperature range is of great importance in Flow Induce Crystallization (FIC) due to the tendency of molecules to crystallize and reorient. Thermal and flow histories of the samples were eliminated by heating up each test specimen to 180 °C (around 30 °C above melting peak temperature) for 10 minutes prior to cooling at the rate of 30 °C / min to the desired temperature and experimental testing. Fast and accurate cooling is crucial to reach the desired crystallization temperature without any temperature undercooling that would lead into premature crystallization. The Peltier system of the rheometer was used for this study since it can employ higher cooling rates more precisely compared to those of the convection oven system. The influence of several parameters such as temperature, deformation and deformation rates (shear) on the crystallization kinetics of the random polypropylene copolymer were studied at shear rates up to 1 s'1. Higher shear rates cause severe edge fracture. The temperature selected for these FIC crystallization experiments was the (Melting temperature (Tm)+ Crystallization Temperature (Tc)) / 2 for a fair comparison as to the effect of temperature (T) on the induction time for the onset of crystallization.

[0086] The results of the above tests are shown in Table 1, which shows the realization of positive synergy of clarifier and nucleator (examples 1-4).Table 124T&I0025-WO-ORD 23

[0087] In the context of the present disclosure, at least the following 17 aspects are described. Aspect l is a composition comprising a random copolymer polypropylene that comprises at least one alpha-olefin co-monomer, wherein the at least one alpha-olefin co-monomer is 1-5 wt. % of the random copolymer polypropylene, wherein the poly dispersity index of the random copolymer polypropylene in the composition is 2-15 Mw / Mn; a clarifier; a nucleator that is not a clarifier, wherein the combined concentration of the clarifier and the nucleator that is not a clarifier in the composition is in a range of 1700-4300 ppm and wherein the concentration of the clarifier in the composition is 65-91 wt. % of the combined concentration of the clarifier and nucleator that is not a clarifier; wherein the composition has the following properties: a) a peak crystallization temperature in a range of 40 °C to 100 °C measured via flash DSC under cooling rate above 100 °C / sec; b) a peak crystallization temperature of 10 °C to 50 °C higher than a peak crystallization temperature of the composition with the clarifier and without the nucleator that is not a clarifier, measured via flash DSC under a cooling rate in the range from 0.15 °C / sec to 100 °C / sec; c) a peak crystallization temperature of in a range of 70 °C to 100 °C, measured via flash DSC under a cooling rate in the range of 40-100 °C / sec; and d) a haze value in a range of 5% to 20% at a wavelength of 400 nm as per ASTM 1003 on a sample with a thickness of 1 mm and a haze value in a range of 2% to 11% at a wavelength of 550 nm, measured on a sample with a thickness of 1 mm. Aspect 2 is the composition of Aspect 1 , wherein (i) the clarifier comprises: a sorbitol, lithium 2,2 ' -methylene-bis(4,6-di-tert-butulphenyl) phosphate, or combination thereof; and (ii) the nucleator that is not a clarifier comprises a derivative of a carboxylic acid or its salt, a salt of a substituted aromatic heterocyclic phosphate, a salt of bicycle [2.2.1] heptane di carb oxy late, y- quinacridone, calcium pimelate, N,N-dicyclohexyl-2,6-naphthalene dicarboxamide, or combinations thereof. Aspect 3 is the composition of Aspect 2, wherein the derivative of a carboxylic acid or its salt comprises calcium 1,2-cyclohexanedicarboxylic acid. Aspect 4 is the composition of Aspect 2, wherein the salt a of a substituted aromatic heterocyclic phosphate comprises sodium 2,2 ' -methylene-bis-(4,6-di-t-butylphenylene)phosphate. Aspect 5 is the composition of any of Aspects 1 to 4, wherein the composition has a half crystallization time of less than 0.3 sec measured at an isothermal crystallization temperature in the range of 50-90 °C. Aspect 6 is the composition of any of Aspects 1 to 5, wherein the composition has a maximum shear stress growth coefficient at a shear rate of 0.05 s-1 and an isothermal temperature of (Tm+Tc) / 2, where Tm and Tc are the peak melting and crystallization temperatures, respectively,24T&I0025-WO-ORD 24 measured by DSC at a heating and cooling rate of 10 °C / min, respectively, reached at a time in a range of 2 sec to 50 sec. Aspect 7 is the composition of any of Aspects 1 to 6, wherein the melt flow rate of the composition is in the range of 0.1-200 g / 10 min, measured at 230 °C and 2.16 Kg load. Aspect 8 is the composition of any of Aspects 1 to 7, wherein the at least one alpha-olefin co-monomer comprises ethylene. Aspect 9 is the composition of any of Aspects 1 to 8, wherein the composition comprises 2-4 wt. % ethylene as the at least one alpha-olefin co-monomer. Aspect 10 is the composition of any of Aspects 1 to 9, wherein the composition has a melt flow rate in the range of 10-100 g / 10 min, measured at 230 °C and 2.16 Kg load. Aspect 11 is the composition of any of Aspects 1 to 10, wherein the composition has yellowness index in a range of -12 to -3.0. Aspect 12 is the composition of any of Aspects 1 to 11, wherein the composition comprises 1300 to 3600 ppm of the clarifier. Aspect 13 is the composition of any of aspects 1 to 12, wherein the composition comprises 400 to 700 ppm of the nucleator that is not a clarifier. Aspect 14 is the composition of any of Aspects 1 to 13, wherein the composition comprises a plurality of alpha-olefin comonomers. Aspect 15 is an article comprising the composition of any of Aspects 1 to 14, wherein the article is comprised in one or more of the following: a building component, cladding, laminate, membrane, pipe, a component of an appliance, an automotive component, a health care or medical product, a syringe, biomedical hose, bottle, a component or product used in a rigid packaging application or a flexible packaging application, a component or product used in a telecom duct application, a component or product produced by inj ection molding, extrusion, thermoforming, compression molding, injection compression molding, or other polymer molding process. Aspect 16 is the composition of any of Aspects 1 to 15, wherein the random copolymer polypropylene composition comprises bis (3,4- dimethylbenzylidene) sorbitol (DMDBS) as clarifier and cis-l,2-cyclohexane di carboxylic acid as nucleator that is not a clarifier. Aspect 17 is the composition of any of Aspects 1 to 16, wherein the random copolymer polypropylene composition can comprise 2,4,8, 10-Tetra(tert-butyl)-6-hydroxy-12H- dibenzo[d,g]dioxaphosphocin 6-oxide, sodium salt (NA-71) as clarifier and cis-l,2-cyclohexane dicarboxylic acid as nucleator that is not a clarifier.

[0088] Although embodiments of the present application and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the embodiments as defined by the24T&I0025-WO-ORD 25 appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the above disclosure, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.

Claims

24T&I0025-WO-ORD 26CLAIMS1. A composition comprising: a random copolymer polypropylene that comprises at least one alpha-olefin co-monomer, wherein the at least one alpha-olefin co-monomer is 1-5 wt. % of the random copolymer polypropylene; wherein the poly dispersity index of the random copolymer polypropylene in the composition is 2-15 Mw / Mn; a clarifier; a nucleator that is not a clarifier, wherein the combined concentration of the clarifier and the nucleator that is not a clarifier in the composition is in a range of 1700-4300 ppm and wherein the concentration of the clarifier in the composition is 65-91 wt. % of the combined concentration of the clarifier and nucleator that is not a clarifier; wherein the composition has the following properties: a) a peak crystallization temperature in a range of 40 °C to 100 °C measured via flash DSC under cooling rate above 100 °C / sec; b) a peak crystallization temperature of 10 °C to 50 °C higher than a peak crystallization temperature of the composition with the clarifier and without the nucleator that is not a clarifier, measured via flash DSC under a cooling rate in the range from 0.15 °C / sec to 100 °C / sec; c) a peak crystallization temperature of in a range of 70 °C to 100 °C, measured via flash DSC under a cooling rate in the range of 40-100 °C / sec; and d) a haze value in a range of 5% to 20% at a wavelength of 400 nm as per ASTM 1003 on a sample with a thickness of 1 mm and a haze value in a range of 2% to 11% at a wavelength of 550 nm, measured on a sample with a thickness of 1 mm.

2. The composition of claim 1, wherein(i) the clarifier comprises: a sorbitol, lithium 2,2 ' -methylene-bis(4,6-di-tert- butulphenyl) phosphate, or combination thereof; and(ii) the nucleator that is not a clarifier comprises a derivative of a carboxylic acid or its salt, a salt of a substituted aromatic heterocyclic phosphate, a salt of bicycle [2.2.1] heptane24T&I0025-WO-ORD 27 dicarboxylate, y-quinacridone, calcium pimelate, N,N-dicyclohexyl-2,6-naphthalene dicarboxamide, or combinations thereof.

3. The composition of any of claims 1 to 2, wherein the composition has a half crystallization time of less than 0.3 sec measured at an isothermal crystallization temperature in the range of 50-90 °C.

4. The composition of any of claims 1 to 3, wherein the composition has a maximum shear stress growth coefficient at a shear rate of 0.05 s'1and an isothermal temperature of (Tm+Tc) / 2, where Tm and Tc are the peak melting and crystallization temperatures, respectively, measured by DSC at a heating and cooling rate of 10 °C / min, respectively, reached at a time in a range of 2 sec to 50 sec.

5. The composition of any of claims 1 to 4, wherein the melt flow rate of the composition is in the range of 0.1-200 g / 10 min, measured at 230 °C and 2.16 Kg load.

6. The composition of any of claims 1 to 5, wherein the at least onealpha-olefin comonomer comprises ethylene.

7. The composition of any of claims 1 to 6, wherein the composition comprises 2-4 wt. % ethylene as the at least one alpha-olefin co-monomer.

8. The composition of any of claims 1 to 7, wherein the composition has a melt flow rate in the range of 10-100 g / 10 min, measured at 230 °C and 2.16 Kg load.

9. The composition of any of claims 1 to 8, wherein the composition has yellowness index in a range of -12 to -3.0.

10. The composition of any of claims 1 to 9, wherein the composition comprises 1300 to 3600 ppm of the clarifier.24T&I0025-WO-ORD 28 11. The composition of any of claims 1 to 10, wherein the composition comprises 400 to 700 ppm of the nucleator that is not a clarifier.

12. The composition of any of claims 1 to 11, wherein the composition comprises a plurality of alpha-olefin comonomers.

13. An article comprising the composition of any of claims 1 to 12, wherein the article is comprised in one or more of the following: a building component, cladding, laminate, membrane, pipe, a component of an appliance, an automotive component, a health care or medical product, a syringe, biomedical hose, bottle, a component or product used in a rigid packaging application or a flexible packaging application, a component or product used in a telecom duct application, a component or product produced by injection molding, extrusion, thermoforming, compression molding, injection compression molding, or other polymer molding process.

Images