Polypropylene polymer compositions and articles made therefrom

Abstract

To provide a polymer composition containing a salt of a branched alkylphosphonic acid which functions as a nucleating agent for polymers.SOLUTION: A polymer composition comprising (a) a polypropylene polymer, (b) a salt of a branched alkylphosphonic acid, wherein the branched alkylphosphonic acid comprises a branched alkyl group selected from the group consisting of tert-butyl, tert-pentyl, and neopentyl, (c) a metal salt of a fatty acid, and (d) a synthetic hydrotalcite, wherein the ratio of the weight of the branched alkylphosphonic acid present in the polymer composition to the combined weight of the metal salt of a fatty acid and the synthetic hydrotalcite present in the polymer composition is from 1:1 to 1:4.SELECTED DRAWING: None

Description

Technical field of the invention

[0001] This application relates to polymer compositions, such as polypropylene polymer compositions, containing salts of branched alkylphosphonic acids. The salts of branched alkylphosphonic acids function as nucleating agents for the polymer. Background

[0002] Polyolefins are a particularly versatile group of polymer resins. They are semicrystalline polymers. When cooled relatively slowly (such as occurs during the production of molded plastic parts), polyolefins contain amorphous regions in which the polymer chains are randomly arranged and crystalline regions in which the polymer chains are in an ordered configuration. In these crystalline regions of polyolefins, the polymer chains align into domains commonly referred to as "crystalline lamellae." Under normal processing conditions, as a polyolefin polymer cools from the molten state, the crystalline lamellae grow radially in all directions. This radial growth results in the formation of spherulites, which are spherical, semicrystalline regions composed of multiple crystalline lamellae interrupted by amorphous regions. The size of the spherulites is affected by several parameters and can range from hundreds of nanometers to millimeters in diameter. When the size of the spherulites is significantly larger than the wavelength of visible light, they scatter visible light passing through the polymer. This scattering of visible light results in a hazy appearance commonly referred to as "polymer haze" or simply "haze." While significant levels of polymer haze may be acceptable in some applications, there are certain applications (e.g., storage containers) where consumers desire relatively clear plastics and therefore require correspondingly low haze levels.

[0003]

[0003] Several nucleating agents for thermoplastic polymers are known in the art. These nucleating agents generally function by forming nuclei or providing sites for the formation and / or growth of crystals in the thermoplastic polymer as it solidifies from the molten state. The nuclei or sites provided by the nucleating agent allow crystals to form in the cooled polymer at higher temperatures and / or at a faster rate than crystals would form in a virgin, non-nucleated thermoplastic polymer. This effect may allow the processing of nucleated thermoplastic polymer compositions at shorter cycle times than virgin, non-nucleated thermoplastic polymers.

[0004] Some nucleating agents are capable of reducing the spherulite size of certain polymers (e.g., polypropylene) to such an extent that the haze of the polymer is significantly and appreciably reduced (i.e., the scattering of visible light passing through the polymer is reduced). Such nucleating agents are highly beneficial because they allow the polymer to be used in applications where lower haze levels are needed or at least desired. In addition to such optical property improvements, desirable nucleating agents can also improve other physical properties of the polymer, such as stiffness or impact resistance. Such improvements also broaden the number of applications or end uses for which the nucleated polymer is suitable. And while many nucleating agents can provide one of these physical property improvements, relatively few nucleating agents can provide a desirable combination of two or more physical property enhancements.

[0005] In view of the above, there remains a need for a nucleating agent for thermoplastic polymers, such as polypropylene, that provides a desirable combination of low haze and high stiffness. The additives and polymer compositions described herein are intended to address such a need. BRIEF SUMMARY OF THE INVENTION

[0006] In a first aspect, the present invention provides a polymer composition comprising: (a) a polypropylene polymer; and (b) a salt of a branched alkylphosphonic acid.

[0007] In a first aspect, the present invention provides a polymer composition comprising: (a) a polypropylene polymer; and (b) a salt of a branched alkylphosphonic acid.

[0008] The polymer composition can include any suitable polypropylene polymer. In a preferred embodiment, the polypropylene polymer is selected from the group consisting of polypropylene homopolymers (e.g., atactic polypropylene homopolymer, isotactic polypropylene homopolymer, and syndiotactic polypropylene homopolymer), polypropylene copolymers (e.g., polypropylene random copolymers), polypropylene impact copolymers, and mixtures thereof. Suitable polypropylene copolymers include, but are not limited to, random copolymers prepared from the polymerization of propylene in the presence of a comonomer selected from the group consisting of ethylene, but-1-ene (i.e., 1-butene), and hex-1-ene (i.e., 1-hexene), with ethylene being particularly preferred. In such polypropylene random copolymers, the comonomer can be present in any suitable amount, but is typically present in an amount of less than about 10% by weight (e.g., from about 0.5% to about 10% by weight, or from about 1% to about 7% by weight). Suitable polypropylene impact copolymers include, but are not limited to, those produced by the addition of a copolymer selected from the group consisting of ethylene-propylene rubber (EPR), ethylene-propylene-diene monomer (EPDM), polyethylene, and plastomer to a polypropylene homopolymer or a polypropylene random copolymer. In such polypropylene impact copolymers, the copolymer can be present in any suitable amount, but is typically present in an amount of about 5 to about 25 weight percent. Suitable polypropylene impact copolymers also include, but are not limited to, copolymers made by the polymerization of propylene and ethylene using one or more Zeigler-Natta catalysts. Such polypropylene impact copolymers generally have a heterophase structure with an amorphous ethylene-propylene copolymer dispersed within a semi-crystalline polypropylene homopolymer or copolymer matrix. The polypropylene polymer may be branched or crosslinked, for example, resulting from the addition of additives that increase the melt strength of the polymer.

[0009]

[0009] As noted above, the polymer composition also includes a salt of a branched alkyl phosphonic acid. As used herein, the term "branched alkyl phosphonic acid" refers to a phosphonic acid of formula (C):

[0010] [ka]

[0011] In formula (C), R 101 is a branched alkyl group. The salt of branched alkylphosphonic acid can contain any suitable cation. In a preferred embodiment, the salt of branched alkylphosphonic acid contains one or more cations selected from the group consisting of Group 1 element cations, Group 2 element cations, and Group 12 element cations. In a preferred embodiment, the salt of branched alkylphosphonic acid contains Group 1 element cations, preferably two sodium cations. In another preferred embodiment, the salt of branched alkylphosphonic acid contains Group 2 element cations. In a particularly preferred embodiment, the salt of branched alkylphosphonic acid contains calcium cations.

[0012] The branched alkyl phosphonic acid can include any suitable branched alkyl group (i.e., R 101can be any suitable branched alkyl group). In a preferred embodiment, the branched alkyl phosphonic acid comprises a branched alkyl group selected from the group consisting of isopropyl, sec-butyl, isobutyl, tert-butyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, sec-isopentyl, pentan-3-yl, and 2-methylbutyl. In another preferred embodiment, the branched alkyl phosphonic acid comprises an alkyl group having a branch point located at the alpha-carbon or beta-carbon relative to the phosphorus atom, with a branch point at the alpha-carbon being particularly preferred. In a preferred embodiment, the branched alkyl phosphonic acid comprises a tertiary alkyl group (i.e., an alkyl group comprising four non-hydrogen substituents, e.g., three alkyl groups, and at least one carbon atom attached to the phosphorus atom). In a preferred embodiment, the branched alkyl phosphonic acid comprises a branched alkyl group selected from the group consisting of tert-butyl, tert-pentyl, and neopentyl. In a particularly preferred embodiment, the branched alkyl phosphonic acid comprises a tert-butyl group (i.e., R 101 is tert-butyl). Thus, in a particularly preferred embodiment, the salt of the branched alkylphosphonic acid is the calcium salt of tert-butylphosphonic acid (i.e., calcium t-butylphosphonate or calcium t-butylphosphonate monohydrate).

[0013] The salt of branched alkylphosphonic acid can have any suitable specific surface area (e.g., BET specific surface area). In a preferred embodiment, the salt of branched alkylphosphonic acid has a specific surface area of ​​about 20 m 2 In another preferred embodiment, the salt of branched alkylphosphonic acid has a BET specific surface area of ​​about 30 m 2The salts of branched alkylphosphonic acid have a BET specific surface area of ​​1 / g or more. The BET specific surface area of ​​the salts of branched alkylphosphonic acid can be measured by any suitable technique. Preferably, the BET specific surface area of ​​the salts of branched alkylphosphonic acid is measured according to ISO standard 9277:2010, entitled "Determination of the Specific Surface Area of ​​Solids by Gas Adsorption - BET method," using nitrogen as the adsorption gas. The salts of branched alkylphosphonic acid disclosed herein generally have a layered structure that can be exfoliated using techniques known in the art. Exfoliation of such a layered structure increases the BET specific surface area of ​​the salts of branched alkylphosphonic acid, thereby aiding dispersion. Physical methods for increasing the BET specific surface area of ​​the salts of branched alkylphosphonic acid include air jet milling, pin milling, hammer milling, and grinding milling. Improved dispersion and surface area can also be achieved by more rigorous mixing and extrusion methods, such as high-intensity mixing and twin-screw extrusion. Thus, salts of branched alkylphosphonic acids that do not have the desired BET specific surface area can be exfoliated using these and other known techniques until the desired BET specific surface area is achieved.

[0014] The polymer composition can contain any suitable amount of the salt of branched alkyl phosphonic acid. In a preferred embodiment, the salt of branched alkyl phosphonic acid is present in the polymer composition in an amount of about 50 parts per million (ppm) or greater, based on the total weight of the polymer composition. In another preferred embodiment, the salt of branched alkyl phosphonic acid is present in the polymer composition in an amount of about 75 ppm or greater, about 100 ppm or greater, about 150 ppm or greater, about 200 ppm or greater, or about 250 ppm or greater, based on the total weight of the polymer composition. The salt of branched alkyl phosphonic acid is preferably present in the polymer composition in an amount of about 10,000 ppm or less, based on the total weight of the polymer composition. In preferred embodiments, the salt of branched alkylphosphonic acid is present in the polymer composition in an amount of about 5,000 ppm or less, about 4,000 ppm or less, about 3,000 ppm or less, about 2,000 ppm or less, about 1,500 ppm or less, about 1,250 ppm or less, or about 1,000 ppm or less, preferably based on the total weight of the polymer composition.Thus, in a series of preferred embodiments, the salt of branched alkylphosphonic acid is present in an amount of from about 50 ppm to about 10,000 ppm (e.g., from about 50 ppm to about 5,000 ppm, from about 50 ppm to about 4,000 ppm, from about 50 ppm to about 3,000 ppm, from about 50 ppm to about 2,000 ppm, from about 50 ppm to about 1,500 ppm, from about 50 ppm to about 1,250 ppm, or from about 50 ppm to about 1,000 ppm), from about 75 ppm to about 10,000 ppm (e.g., from about 75 ppm to about 5,000 ppm, from about 75 ppm to about 4,000 ppm, about 75 ppm to about 3,000 ppm, about 75 ppm to about 2,000 ppm, about 75 ppm to about 1,500 ppm, about 75 ppm to about 1,250 ppm, or about 75 ppm to about 1,000 ppm), about 100 ppm to about 10,000 ppm (for example, about 100 ppm to about 5,000 ppm, about 100 ppm to about 4,000 ppm, about 100 ppm to about 3,000 ppm, about 100 ppm to about 2,000 ppm, about 100 ppm to about 1,500 ppm, about 100 ppm to about 1,250 ppm, or about 100 ppm to about 1 ,000 ppm), about 150 ppm to about 10,000 ppm (for example, about 150 ppm to about 5,000 ppm, about 150 ppm to about 4,000 ppm, about 150 ppm to about 3,000 ppm, about 150 ppm to about 2,000 ppm, about 150 ppm to about 1,500 ppm, about 150 ppm to about 1,250 ppm, or about 150 ppm to about 1,000 ppm), about 200 ppm to about 10,000 ppm (for example, about 200 ppm to about 5,000 ppm, about 200 ppm to about 4,000 ppm, about 200 ppm to about 3,000 ppm, about 2 The carboxylic acid or carboxylic acid salt is present in the polymer composition in an amount of from about 00 ppm to about 2,000 ppm, from about 200 ppm to about 1,500 ppm, from about 200 ppm to about 1,250 ppm, or from about 200 ppm to about 1,000 ppm, from about 250 ppm to about 10,000 ppm (e.g., from about 250 ppm to about 5,000 ppm, from about 250 ppm to about 4,000 ppm, from about 250 ppm to about 3,000 ppm, from about 250 ppm to about 2,000 ppm, from about 250 ppm to about 1,500 ppm, from about 250 ppm to about 1,250 ppm, or from about 250 ppm to about 1,000 ppm).When the polymer composition comprises more than one salt of branched alkyl phosphonic acid, each salt of branched alkyl phosphonic acid can be present in the polymer composition in one of the amounts described above, or the total amount of all salts of branched alkyl phosphonic acid present in the polymer composition can fall within one of the ranges described above. Preferably, when the polymer composition comprises more than one salt of branched alkyl phosphonic acid, the total amount of all salts of branched alkyl phosphonic acid present in the polymer composition falls within one of the ranges described above.

[0015]

[0013] Salts of branched alkylphosphonic acids suitable for use in the compositions of the present invention can be prepared by any suitable process. For example, salts can be prepared by reacting a branched alkylphosphonic acid with a metal base, such as a metal hydroxide (e.g., calcium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide) or a metal oxide (e.g., calcium oxide or zinc oxide) in an aqueous medium. Salts of branched alkylphosphonic acids prepared by such processes can be hydrates (e.g., calcium t-butylphosphonate monohydrate). Such hydrate salts can be dehydrated by heating the salt to a sufficiently high temperature, but many such dehydrated salts (e.g., calcium t-butylphosphonate) are sufficiently unstable to rehydrate when exposed to atmospheric moisture.

[0016] The polymer compositions of the present invention may contain other polymer additives in addition to the salts of branched alkylphosphonic acids described above. Suitable additional polymer additives include antioxidants (e.g., phenolic antioxidants, phosphite antioxidants, and combinations thereof), antiblocking agents (e.g., amorphous silica and diatomaceous earth), pigments (e.g., organic and inorganic pigments) and other colorants (e.g., dyes and polymeric colorants), fillers and reinforcing agents (e.g., glass, glass fiber, talc, calcium carbonate, and magnesium oxysulfate whiskers), nucleating agents, clarifying agents, acid scavengers (e.g., metal salts of fatty acids, such as metal salts of stearic acid, and hydrotalcite-like materials), polymer processing additives (e.g., fluoropolymer processing additives), polymer crosslinkers, slip agents (e.g., fatty acid amide compounds obtained from the reaction of fatty acids with ammonia or amine-containing compounds), fatty acid ester compounds (e.g., fatty acid ester compounds obtained from the reaction of fatty acids with hydroxyl-containing compounds, such as glycerol, diglycerol, and combinations thereof), polymer modifiers (e.g., hydrocarbon resin modifiers, such as ExxonMobil Corporation under the trade name Oppera™), and combinations of the foregoing.

[0017] In a preferred embodiment, the polymer composition further comprises one or more acid scavengers. As noted above, suitable acid scavengers include metal salts of fatty acids and hydrotalcite-like materials (e.g., synthetic hydrotalcites). Suitable metal salts of fatty acids include C 12 ~C 22 Fatty acids (e.g., saturated C 12 ~C 22Examples of suitable acid scavengers include, but are not limited to, metal salts of fatty acids, such as stearic acid. In a preferred embodiment, the acid scavenger is selected from the group consisting of calcium, zinc, potassium, and lanthanum stearates, with zinc stearate being particularly preferred. Suitable hydrotalcite-like materials for use as acid scavengers include, but are not limited to, the synthetic hydrotalcite materials (CAS No. 11097-59-9) sold by Kisuma Chemicals under the trade names "DHT-4A" and "DHT-4V."

[0018] The branched alkyl phosphonic acid salt and the acid scavenger can be present in the polymer composition in any suitable relative amounts. For example, the branched alkyl phosphonic acid salt and the acid scavenger can be present in the polymer composition in a ratio (branched alkyl phosphonic acid salt to acid scavenger) of about 10:1 to about 1:10, based on the weight of the branched alkyl phosphonic acid salt and the acid scavenger in the polymer composition. More preferably, the branched alkyl phosphonic acid salt and the acid scavenger are present in the polymer composition in a ratio of about 4:1 to about 1:4, about 3:1 to about 1:3 (e.g., about 3:1 to about 1:1 or about 3:1 to about 2:1), about 1:1 to about 1:4, or about 1:1 to about 1:3, based on the weight of the branched alkyl phosphonic acid salt and the acid scavenger in the polymer composition. In a particularly preferred embodiment, the salt of branched alkyl phosphonic acid and the acid scavenger are present in the polymer composition in a ratio of about 2:1 based on the weight of the salt of branched alkyl phosphonic acid and the acid scavenger in the polymer composition (e.g., about 2 parts by weight of calcium t-butyl phosphonate monohydrate to 1 part by weight of zinc stearate). In another particularly preferred embodiment, the salt of branched alkyl phosphonic acid and the acid scavenger are present in the polymer composition in a ratio of about 3:1 based on the weight of the salt of branched alkyl phosphonic acid and the acid scavenger in the polymer composition (e.g., about 3 parts by weight of calcium t-butyl phosphonate monohydrate to 1 part by weight of zinc stearate).

[0019] As mentioned above, the polymer composition of the present invention may contain other nucleating agents in addition to the salts of branched alkylphosphonic acids described above. Suitable nucleating agents include 2,2'-methylene-bis-(4,6-di-tert-butylphenyl)phosphates (e.g., sodium 2,2'-methylene-bis-(4,6-di-tert-butylphenyl)phosphate or hydroxyaluminum bis(2,2'-methylene-bis-(4,6-di-tert-butylphenyl)phosphate), bicyclo[2.2.1]heptane-2,3-dicarboxylates (e.g., disodium bicyclo[2.2.1]heptane-2,3-dicarboxylate or calcium bicyclo[2.2.1]heptane-2,3-dicarboxylate), cyclohexane-1,2-dicarboxylates (e.g., calcium cyclohexane-1,2-dicarboxylate), and the like. Examples of suitable carboxylates include, but are not limited to, monobasic cyclohexane-1,2-dicarboxylate (e.g., calcium, aluminum monobasic cyclohexane-1,2-dicarboxylate, dilithium cyclohexane-1,2-dicarboxylate, or strontium cyclohexane-1,2-dicarboxylate), glycerolates (e.g., zinc glycerolate), phthalates (e.g., calcium phthalate), phenylphosphonates (e.g., calcium phenylphosphonate), and combinations thereof. In the case of bicyclo[2.2.1]heptane-2,3-dicarboxylates and cyclohexane-1,2-dicarboxylates, the carboxylate moieties may be configured in either the cis or trans configuration, with the cis configuration being preferred.

[0020] As mentioned above, the polymer composition of the present invention can also contain a clarifying agent. Suitable clarifying agents include, but are not limited to, trisamides and acetal compounds, which are condensation products of polyhydric alcohols and aromatic aldehydes. Suitable trisamide clarifying agents include, but are not limited to, amide derivatives of benzene-1,3,5-tricarboxylic acid, derivatives of N-(3,5-bis-formylamino-phenyl)-formamide (e.g., N-[3,5-bis-(2,2-dimethyl-propionylamino)-phenyl]-2,2-dimethyl-propionamide), derivatives of 2-carbamoyl-malonamide (e.g., N,N'-bis-(2-methyl-cyclohexyl)-2-(2-methyl-cyclohexylcarbamoyl)-malonamide), and combinations thereof. As mentioned above, the clarifying agent can be an acetal compound, which is the condensation product of polyhydric alcohols and aromatic aldehydes. Suitable polyhydric alcohols include acyclic polyols such as xylitol and sorbitol, and acyclic deoxypolyols (e.g., 1,2,3-trideoxynonitol or 1,2,3-trideoxynon-1-enitol). Suitable aromatic aldehydes typically contain a single aldehyde group, with the remaining positions on the aromatic ring either unsubstituted or substituted. Thus, suitable aromatic aldehydes include benzaldehyde and substituted benzaldehydes (e.g., 3,4-dimethyl-benzaldehyde or 4-propyl-benzaldehyde). The acetal compounds produced by the above reaction may be monoacetal, diacetal, or triacetal compounds (i.e., compounds containing one, two, or three acetal groups, respectively), with diacetal compounds being preferred. Suitable acetal-based clarifying agents include, but are not limited to, those disclosed in US Pat. Nos. 5,049,605; 7,157,510; and 7,262,236.

[0021] The polymer composition of the present invention can be produced by any suitable method or process. For example, the polymer composition can be produced by simple mixing of the individual components of the polymer composition (e.g., the polymer, the salt of branched alkylphosphonic acid, and other additives, if present). The polymer composition can also be produced by mixing the individual components under high shear or high intensity mixing conditions. The polymer composition of the present invention can be provided in any form suitable for use in further processing to produce articles of manufacture from the thermoplastic polymer composition. For example, the thermoplastic polymer composition can be provided in the form of a powder (e.g., a free-flowing powder), flakes, pellets, prills, tablets, agglomerates, etc.

[0022] The polymer composition of the first aspect of the invention can take the form of a masterbatch composition designed for addition or dropwise addition to a new polymer (e.g., a non-nucleated polypropylene polymer). In such an aspect, the polymer composition generally contains a higher amount of the salt of branched alkyl phosphonic acid than a thermoplastic polymer composition intended for use in forming an article of manufacture without further dilution or addition to a new thermoplastic polymer. For example, the salt of branched alkyl phosphonic acid can be present in such a polymer composition in an amount of about 0.5 wt. % or more (e.g., about 1 wt. % or more or about 2 wt. % or more). The maximum amount of salt in the masterbatch is limited only by manufacturing and processing considerations, but the amount is typically about 50 wt. % or less. Thus, in a series of preferred embodiments, the salt of branched alkylphosphonic acid is present in an amount of about 0.5 wt % to about 50 wt % (e.g., about 0.5 wt % to about 40 wt %, about 0.5 wt % to about 30 wt %, about 0.5 wt % to about 25 wt %, about 0.5 wt % to about 20 wt %, about 0.5 wt % to about 15 wt %, about 0.5 wt % to about 10 wt %, about 0.5 wt % to about 5 wt %, or about 0.5 wt % to about 4 wt %), about 1 wt % to about 50 wt % (e.g., about 1 wt % to about 40 wt %, about 1 wt % to about 30 wt %), based on the total weight of the polymer composition. The additives may be present in the masterbatch in an amount of about 1% to about 25% by weight, about 1% to about 20% by weight, about 1% to about 15% by weight, about 1% to about 10% by weight, about 1% to about 5% by weight, or about 1% to about 4% by weight, or about 2% to about 50% by weight (e.g., about 2% to about 40% by weight, about 2% to about 30% by weight, about 2% to about 25% by weight, about 2% to about 20% by weight, about 2% to about 15% by weight, about 2% to about 10% by weight, about 2% to about 5% by weight, or about 2% to about 4% by weight). In such masterbatch compositions, additional additives contained therein may likewise be present in higher amounts intended to provide the desired concentration upon lowering the masterbatch composition into fresh polymer.

[0023] The polymer compositions of the present invention are believed to be useful in the manufacture of thermoplastic polymer articles of manufacture. The polymer compositions of the present invention may be formed into desired thermoplastic polymer articles of manufacture by any suitable technique, such as injection molding (e.g., thin-wall injection molding, multi-component molding, overmolding, or 2K molding), blow molding (e.g., extrusion blow molding, injection blow molding, or injection stretch blow molding), extrusion (e.g., fiber extrusion, tape (e.g., slit tape) extrusion, sheet extrusion, film extrusion, cast film extrusion, pipe extrusion, extrusion coating, or foam extrusion), thermoforming, rotational molding, film blowing (blown film), film casting (cast film), compression molding, extrusion compression molding, extrusion compression blow molding, etc. Thermoplastic polymer articles made using the polymer compositions of the present invention may be composed of multiple layers (e.g., multilayer blown or cast film, or multilayer injection-molded article), with one or any suitable number of the multiple layers containing the polymer composition of the present invention.

[0024] The polymer compositions of the present invention can be used to manufacture any suitable article of manufacture, including, but not limited to, medical devices (e.g., pre-filled syringes for retort applications, intravenous supply containers, and blood collection devices), food packaging, liquid containers (e.g., containers for beverages, medicines, personal care compositions, shampoos, etc.), clothing cases, microwaveable items, shelving, cabinet doors, machine parts, automotive parts, sheets, pipes, tubing, rotational molded parts, blow molded parts, films, fibers, etc.

[0025] The following examples further illustrate the above subject matter but, of course, should not be construed as in any way limiting its scope.

[0026] Example 1 This example demonstrates the preparation of a polymer composition according to the present invention and certain physical properties of thin-walled injection molded parts made with such a polymer composition.

[0027] Several polymer compositions were prepared using different commercially available polypropylene resins. The sample labeled "1A" was prepared using LyondellBasell's Pro-fax 6301 polypropylene homopolymer, reported to have a melt flow rate of 12 g / 10 min. The sample labeled "1B" was prepared using Lanzhou's HPP SF-40, reported to have a melt flow rate of 60 g / 10 min. The sample labeled "1C" was prepared using Luoyang's HPP Q / SH3210, reported to have a melt flow rate of 80 g / 10 min. The sample labeled "1D" was prepared using Sinopec Tianjin's PPH-M70, reported to have a melt flow rate of 70 g / 10 min. All samples were stabilized with 500 ppm Irganox® 1010 antioxidant and 1,000 ppm Irgafos® 168 antioxidant, both available from BASF. Some polymer compositions further contained calcium t-butylphosphonate monohydrate ("CaTBP"), zinc stearate ("ZnSt"), and the acid scavenger calcium stearate ("CaSt"), and / or DHT-4V from Kisuma Chemicals. The amounts of these additional ingredients are listed in the table below.

[0028] Each of the polymer compositions was prepared by high-intensity mixing of the polypropylene resin and additives and melt compounding the mixture using a Deltaplast single-screw extruder. The extruder screw speed was set at 126 rpm. The first zone of the extruder barrel was set at 200°C, the second zone of the extruder barrel was set at 215°C, and zones three through six of the extruder barrel were all set at 230°C. After melt compounding, each extrudate was chopped into pellets for further processing.

[0029] The extruded pellets of each polymer composition were then injection molded into 16 U.S. fluid ounce (470 mL) deli cups in a Husky injection molding machine with all barrels set at 220°C, an injection speed of 140 mm / s, a back pressure of 50 psi (0.14 MPa), and mold cooling water set at 45°C. The deli cups had a circular bottom with a diameter of 3.637 inches (92.38 mm), a circular opening at the top with a rim whose inner edge was 4.266 inches (108.4 mm) in diameter and whose outer edge was 4.612 inches (117.1 mm) in diameter. The wall thickness of the deli cups was 26 mils (0.66 mm).

[0030] After molding, the deli cups were tested to determine several physical properties. Compression top load was measured according to ASTM D2659. Haze was measured according to ASTM D1003. Crystallization behavior, specifically the crystallization half-time (T 1 / 2 ) and crystallization temperature (T c ) was measured using a differential scanning calorimeter. The crystallization half-time was measured at 140°C and the crystallization temperature was measured at a heating rate of 20°C / min. The results of these measurements are reported in Tables 1-4 below.

[0031] [Table 1]

[0032] [Table 2]

[0033] [Table 3]

[0034] [Table 4]

[0035] As can be seen from the data in Tables 1-4 above, calcium t-butylphosphonate monohydrate ("CaTBP") was effective in nucleating all polypropylene polymers. These nucleation effects are evident from the shorter crystallization half-times, higher crystallization temperatures, higher compressed top loads, and lower haze values ​​exhibited by all of the polymer compositions containing CaTBP compared to their respective control polymers (i.e., polypropylene resins without CaTBP). Furthermore, these results demonstrate that polymer compositions containing a synthetic hydrotalcite acid scavenger (e.g., DHT-4V) exhibited slightly better nucleation compared to polymer compositions containing calcium stearate as an acid scavenger. Again, this better nucleation is evident from the shorter crystallization half-times, higher crystallization temperatures, higher compressed top loads, and lower haze values ​​exhibited by polymer compositions containing DHT-4V compared to polymer compositions containing calcium stearate.

[0036] Example 2 This example demonstrates the preparation of polymer compositions according to the present invention and certain physical properties of thermoformed articles made with such polymer compositions.

[0037] The polymer compositions were made using Polypropylene 3371 resin from Total Energies, which has a reported melt flow rate of 2.8 g / 10 min. Certain polymer compositions were nucleated with an acid scavenger, such as calcium t-butylphosphonate monohydrate ("CaTBP") used in conjunction with zinc stearate ("ZnSt") and calcium stearate ("CaSt"). The amounts of CaTBP and acid scavenger used in each polymer composition are listed in the table below. The 3371 resin and additives were high-intensity mixed using a Henschel mixer prior to melt compounding, as described below.

[0038] The polymer composition was melt compounded in a Werner & Pfleiderer zsk-40 twin-screw extruder with a screw diameter of 40 mm and an L / D ratio of 37. The temperature of the first zone of the extruder barrel was set at 165°C, and the temperatures of the second to sixth zones of the extruder barrel and the die zone were set at 175°C. The extruder speed was set at 400 rpm, with a total output of approximately 55 kg / h. The polymer strands exiting the extruder die were cooled in a water bath and chopped into pellets using a pelletizer.

[0039] The pelletized polymer composition was then thermoformed into drinking cups using a Reifenhaeuser Model AT-20-G1 sheet line in conjunction with an iLLig RDM54K thermoformer. The extruder of the sheet line was set at 230°C, the die zone was set at 250°C, and the die gap was 1.5 mm. The screw speed was approximately 72 rpm. The sheet exiting the die was transferred to a set of three stacked chill rolls set at 65°C, 75°C, and 65°C. The sheet exiting the chill rolls was 1.9 mm thick. The sheet was then indexed through the heating section of the thermoformer, set at 165°C, where it was heated just below the melting temperature of the polymer composition. The sheet then passed through the forming section, where it was thermoformed into drinking cups, which were then trimmed from the sheet and ejected from the thermoformer. The resulting drinking cups had a base diameter of approximately 60 mm, a top edge diameter of approximately 94 mm, and a height of approximately 140 mm.

[0040] Specimens of the extruded sheets and thermoformed drinking cups were obtained for the optical and physical property testing described below. Haze and clarity were measured according to ASTM D1003 using a BYK Hazegard Haze Meter. For thermoformed drinking cups, haze measurements were taken in an area 76.2 mm from the bottom of the cup and 25.4 mm from the top edge. Gloss was measured using a BYK Single Angle Gloss Meter, Microgloss 20°. Measurements were taken from both sides of the specimen, and the results were averaged to obtain an average gloss, reported in gloss units.

[0041]

[0035] The thermal properties of the specimens were measured by differential scanning calorimetry using a Mettler Toledo differential scanning calorimeter (DSC) unit (DSC3+STAR system) and analyzed by Mettler STARe evaluation software. For crystallization temperature measurement, the specimens were heated from 50°C to 220°C at a rate of 20°C / min to remove all thermal history. After the specimens were held at 220°C for 2 minutes to equilibrate, they were cooled to 50°C at a rate of 20°C / min to investigate the crystallization behavior. The crystallization temperature (T c ) is reported as the peak value on the cooling curve. For the crystallization half-time measurement, the specimen was heated from 50 °C to 220 °C at a rate of 20 °C / min to remove all thermal history, held at 220 °C for 2 minutes to equilibrate, then cooled at a rate of 300 °C / min to 135 °C and held at that temperature for 30 minutes. The crystallization half-time was calculated from the DSC curve using software.

[0042]

[0036] Test specimens for flexural modulus testing were cut from the extruded sheets using a Type 1 dogbone cutting die as described in ASTM D638-10. Test specimens were obtained from both the machine and transverse directions. The specimens were then conditioned at approximately 23°C and approximately 50% relative humidity for at least 40 hours. Flexural modulus testing was performed in accordance with ASTM D790-10 using an MTS Criterion Model 43 electromechanical testing system equipped with a three-point flexure bending setup (Model 642.01A). The depth of beam movement was recorded to calculate strain. The 1% secant modulus was calculated based on the stress-to-strain ratio when 1% strain was reached.

[0043] Cup ovality is a parameter that indicates the difference in cup diameter measured in the machine direction (parallel to the direction in which the sheet exits the die) and the cross direction (perpendicular to the direction in which the sheet exits the die). Thermoformed cups are measured using a vernier caliper to measure the difference in the diameter of the cup in the machine direction (D MD ) and transverse (D TD The cup ovality, reported in mils, was calculated using the following formula: Cup ovality = (DMD -D TD ) x 1000 Edge shrinkage is a parameter that indicates the difference between the diameter of the edge of a thermoformed cup and the diameter of the corresponding portion of the mold from which the cup was made. The diameter of the mold was 3.7427 inches. The average diameter of the cup edge (D avg ) was measured using a spring tension band (in inches). Cup lip shrinkage, reported in mils, was calculated using the following formula: Edge shrinkage = (3.7427-D avg )×1000.

[0044] The compressive strength of the sidewall of a thermoformed cup was measured using a probe to determine its resistance to deflection. The cup was positioned horizontally on its side using a cup fixture attached to the platen of an MTS Criterion Model 43 electromechanical test system. The probe, moving at a constant vertical speed of 25 mm / min, pressed vertically downward against the sidewall of the cup to achieve a total wall deflection distance of 10 mm. Once the desired total wall deflection distance was reached, the resulting resistance was recorded as the sidewall force. Top-load compression (ASTM D2659) of a thermoformed cup was measured by inverting the cup and mechanically forcing it downward until resistance to buckling failure of the cup was detected. The cup was placed edge-down on the fixed base of the MTS Criterion Model 43 electromechanical test system. A vented base allowed air to escape from the interior of the cup as it was compressed. The upper compression plate, moving at a constant speed of 50 mm / min, pressed down on the cup until collapse was detected. The peak force recorded at the time of collapse was reported as the top load.

[0045] [Table 5]

[0046] [Table 6]

[0047] [Table 7]

[0048] [Table 8]

[0049] As can be seen from the data in Tables 5-8, calcium t-butylphosphonate monohydrate ("CaTBP") was effective in nucleating 3371 resin, even at loadings as low as 100 ppm. While some physical properties (e.g., sidewall and top load) of drinking cups made from nucleated resins did not show consistent improvements at all loading levels compared to non-nucleated resins, crystallization temperature, crystallization half-time, flexural modulus, and optical properties were consistently improved for both sheets and cups at all loading levels for CaTBP. For example, the addition of just 100 ppm of CaTBP reduced the haze of extruded sheets by approximately 7 haze units, increased clarity from only 12.6% to over 95%, and increased average gloss by 13 gloss units. Furthermore, in thermoformed drinking cups, the addition of CaTBP reduced shrinkage (less edge shrinkage) compared to non-nucleated resins, and the shrinkage that did occur was more isotropic in nature, as evidenced by substantially reduced ovality values.

[0050] Example 3 This example demonstrates the preparation of polymer compositions according to the present invention and certain physical properties of thermoformed articles made with such polymer compositions.

[0051] The polymer compositions were made using Total Energies Polypropylene 3371 resin as described in Example 2. Certain polymer compositions were nucleated with an acid scavenger, such as calcium t-butylphosphonate monohydrate ("CaTBP") used in conjunction with zinc stearate ("ZnSt") and calcium stearate ("CaSt"). The amounts of CaTBP and acid scavenger used in each polymer composition are listed in the table below. The 3371 resin and additives were high intensity mixed and melt compounded in the same manner as the polymer compositions of Example 2.

[0052] The pelletized polymer composition was then thermoformed into portion cups using the same equipment and conditions (except as noted below) used in Example 2. To produce the extruded sheet, the screw speed of the sheet line extruder was set at approximately 42-45 rpm. The sheet exiting the chill roll was 1.2 mm thick. Different dies were attached to the thermoformer to produce portion cups with a base diameter of 78 mm, a top edge diameter of 94 mm, and a height of 54 mm.

[0053] Specimens of the extruded sheet and thermoformed portion cups were obtained for optical and physical property testing as described in Example 2. For the thermoformed portion cups, haze measurements were taken in an area 25.4 mm from the bottom of the cup and 19 mm from the top edge.

[0054] [Table 9]

[0055] [Table 10]

[0056] [Table 11]

[0057] [Table 12]

[0058] The data in Tables 9-12 further confirm that salts of branched alkyl phosphonic acid, specifically calcium t-butyl phosphonate monohydrate ("CaTBP"), were effective in nucleating 3371 resin. The nucleated resin showed consistent improvements in optical and physical properties in both the sheet and thermoformed portion cups.

[0059] Example 4 This example demonstrates the preparation of polymer compositions in accordance with the present invention and the improved physical properties exhibited by injection-molded articles made from such polymer compositions. Specifically, this example demonstrates the effect of BET specific surface area on the nucleation performance of salts of branched alkylphosphonic acids.

[0060] Seven polymer compositions were prepared for the injection molding runs described herein. Sample 4A was non-nucleated Pro-fax 6301 polypropylene homopolymer manufactured by LyondellBasell. Samples 4B-4G were made from a mixture of Pro-fax 6301, 1,000 ppm calcium t-butylphosphonate monohydrate ("CaTBP"), 500 ppm zinc stearate ("ZnSt"), 300 ppm Irganox® 1010 antioxidant, and 600 ppm Irgafos® 168 antioxidant. The BET specific surface area of ​​each CaTBP used in Samples 4B-4G is listed in Table 13 below. The BET specific surface area of ​​the nucleating agent samples was measured according to ISO standard 9277:2010, titled "Determination of the Specific Surface Area of ​​Solids by Gas Adsorption - BET method," using nitrogen as the adsorption gas. Samples 4B-4G were separately mixed, melt compounded, and pelletized as described in Example 1.

[0061] A portion of each polymer composition was injection molded into ASTM bent bars according to ASTM D4101-11 using a 40 ton Arburg injection molding machine. Another portion of each polymer composition was injection molded into ISO shrink plaques according to ISO 294 using a 55 ton Arburg injection molding machine. Finally, another portion of each polymer composition was injection molded into 77 mm long, 50 mm wide, 1.27 mm (50 mil) thick plaques on the 40 ton Arburg injection molding machine.

[0062] Heat deflection temperature (HDT) was measured on the injection-molded ASTM flexural bars described above in accordance with ASTM D648-07 (using a stress of 0.4555 MPa). Notched Izod impact was measured on an Instron 9050 pendulum impact tester in accordance with ASTM D256-10 using injection-molded ASTM flexural bars trimmed and notched as specified in ASTM D256-10. Thermal properties of the specimens were measured by differential scanning calorimetry using a Mettler Toledo differential scanning calorimeter (DSC) unit (DSC3+STAR system) as described in Example 2, except that the specimens were held at a temperature of 140°C during testing, and analyzed using Mettler STARe evaluation software.

[0063] Flexural modulus was measured according to ASTM D790-10 using an MTS Criterion Model 43 electromechanical testing system equipped with a three-point flexure setup (Model 642.01A). The bending bars were conditioned for at least 40 hours at approximately 23°C and approximately 50% relative humidity prior to testing. Bidirectional flexural modulus (machine direction (MD) and transverse direction (TD)) was also measured according to ASTM D790-10. Specimens for bidirectional flexural modulus, conditioned as described above, were trimmed from injection-molded ISO shrink plaques. For MD measurements, 9.2 mm of material was trimmed from the TD axis (leaving 50.8 mm [2 inches] in the TD direction) and the load was applied perpendicular to the machine direction. For TD measurements, 9.2 mm of material was trimmed from the MD axis (leaving 50.8 mm [2 inches] in the MD direction) and the load was applied parallel to the machine direction.

[0064] Shrinkage of injection molded ISO shrinkage plaques was measured according to ISO 294, with the plaques conditioned for at least 48 hours at about 23°C and about 50% relative humidity before testing. Shrinkage in the machine and transverse directions was calculated using the following formulas:

[0065]

number

[0066] In the formula, MD mоld is the dimension of the die in the machine direction, MD specimen is the specimen dimension in the machine direction, and TD mоld is the horizontal dimension of the mold, and TD specimen is the specimen dimension in the cross direction. The isotropy index, a measure of how uniformly the part shrunk, was calculated by dividing the shrinkage in the machine direction by the shrinkage in the cross direction.

[0067]

number

[0068]

[0051] The results of the above measurements are shown in Tables 13, 14 and 15 below.

[0069] [Table 13]

[0070] [Table 14]

[0071] [Table 15]

[0072] The data in Tables 14 and 15 further confirm that salts of branched alkyl phosphonic acid, specifically calcium t-butyl phosphonate monohydrate ("CaTBP"), were effective in nucleating polypropylene polymers, specifically 6301 resin. For example, the crystallization temperatures of all nucleated samples were at least 7°C higher than the non-nucleated controls. Furthermore, the crystallization half-times of the nucleated samples were all less than 11 minutes, which is much faster than the non-nucleated resin. Faster crystallization rates (slower crystallization half-times) were generally observed for polymer compositions nucleated with CaTBP, which has a lower BET specific surface area.

[0073] The data in Table 14 also demonstrate the substantial improvement in physical properties that can be achieved by nucleation with a salt of alkylphosphonic acid, specifically calcium t-butylphosphonate monohydrate ("CaTBP"). All of the nucleated samples exhibited an increase in flexural modulus of over 300 MPa compared to the non-nucleated polymer. Furthermore, the heat deflection temperatures of the nucleated resins were all at least 17°C higher than those of the non-nucleated polymer. The impact strength of the nucleated polymer was at least 16 J / m higher than that of the non-nucleated polymer.

[0074] The data in Table 15 illustrate the same point. In fact, the improvement in flexural modulus obtained with the nucleated polymer compositions was even more evident when measuring bidirectional stiffness. In these measurements, both the MD and TD flexural moduli increased by approximately 400 MPa over the values ​​obtained with the non-nucleated resins. Also, while the MD shrinkage of the nucleated resins was slightly higher than that of the non-nucleated resins, the MD and TD shrinkage of each nucleated resin were closer to each other than those of the non-nucleated resins. This resulted in shrinkage of the nucleated resins that was much more isotropic (i.e., has an isotropy index closer to 1) than that of the non-nucleated resins. With an isotropy index closer to 1, articles made from the nucleated resins are expected to exhibit less warpage / distortion compared to articles made from the non-nucleated resins.

[0075] Example 5 This example demonstrates the preparation of a polymer composition according to the present invention and certain physical properties of injection molded parts made with such polymer compositions.

[0076] Two polymer compositions were prepared for the injection molding runs described herein. Sample 5A was a non-nucleated Prime Polypro J707P polypropylene block copolymer manufactured by Prime Polymer. The resin's reported melt flow rate was 30 g / 10 min at 230° C. Polypro J707P is an antistatic impact copolymer that exhibits high impact and toughness properties. Sample 5B was made from a mixture of Polypro J707P, 1,000 ppm calcium t-butylphosphonate monohydrate ("CaTBP"), 500 ppm zinc stearate ("ZnSt"), 500 ppm Irganox® 1010 antioxidant, and 1,000 ppm Irgafos® 168 antioxidant. Sample 5B was mixed, melt compounded, and pelletized as described in Example 1.

[0077] Portions of Samples 5A and 5B were injection molded into ASTM flexural bars and ISO shrink plaques as described in Example 4. The resulting bars were then used to measure thermal properties, flexural modulus, two-way flexural modulus, heat deflection temperature, notched Izod impact, shrinkage, and isotropy as described in Example 4. The results of these measurements are shown below in Tables 16 and 17.

[0078] [Table 16]

[0079] [Table 17]

[0080] The data in Tables 16 and 17 demonstrate that salts of branched alkyl phosphonic acid (specifically, calcium t-butyl phosphonate monohydrate ("CaTBP")) were effective in nucleating polypropylene impact copolymers, such as Polypro J707P resin. These nucleation effects are evident from the increased crystallization temperature, dramatic reduction in crystallization half-time, improved flexural modulus, and increased heat deflection temperature. The flexural modulus improvements obtained with the nucleated polymer compositions were even more evident when measuring bidirectional stiffness. In these measurements, the flexural modulus increased by 300-380 MPa. Also, although the shrinkage of the nucleated resin was slightly higher than that of the non-nucleated resin, the isotropy index was significantly closer to 1, meaning that articles made from the nucleated resin exhibited less warpage / distortion compared to articles made from the non-nucleated resin.

[0081] Example 6 This example demonstrates the preparation of a polymer composition according to the present invention and certain physical properties of injection molded parts made with such polymer compositions.

[0082] Two polymer compositions were prepared for the injection molding runs described herein. Sample 6A is SA849S manufactured by LyondellBasell. The resin has a reported melt flow rate of 11 g / 10 min at 230° C. SA849S is a polypropylene random copolymer. Sample 6B was made from a mixture of SA849S, 1,000 ppm calcium t-butylphosphonate monohydrate ("CaTBP"), 500 ppm zinc stearate ("ZnSt"), 500 ppm Irganox® 1010 antioxidant, and 1,000 ppm Irgafos® 168 antioxidant. Sample 6B was mixed, melt compounded, and pelletized as described in Example 1.

[0083] Portions of Samples 6A and 6B were injection molded into 1.27 mm (50 mil) plaques as described above in Example 4. The resulting plaques were used to measure flexural modulus as described above in Example 4. Haze and clarity were measured on the 50 mil plaques as described above.

[0084] [Table 18]

[0085] The data in Table 18 demonstrate that salts of branched alkyl phosphonic acid (specifically, calcium t-butyl phosphonate monohydrate ("CaTBP")) were effective in nucleating polypropylene random copolymers, such as SA849S resin. The haze of the nucleated resin was less than half that of the non-nucleated resin. Also, the clarity of the nucleated resin was increased compared to the non-nucleated resin. Finally, the flexural modulus of the nucleated resin was more than 100 MPa higher than that of the non-nucleated resin.

[0086]

[0063] All references cited in this specification, including publications, patent applications, and patents, are hereby incorporated by reference to the same extent as if each reference was individually and specifically indicated to be incorporated by reference and was set forth in its entirety herein.

[0087]

[0064] In the context of describing the subject matter of this application (particularly in the context of the claims below), the use of the terms "a," "an," and "the," and similar referents, are to be construed to encompass both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms "comprising," "having," "including," and "containing" are to be construed as open-ended terms (i.e., meaning "including, but not limited to"), unless otherwise stated. The recitation of ranges of values ​​herein is merely intended to be a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated, and each separate value is incorporated herein as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples or exemplary language (e.g., "for example") presented herein is intended merely to better clarify the subject matter of the present application and does not limit the scope of the subject matter unless otherwise claimed. No language herein should be construed as indicating any non-claimed element as essential to the practice of the subject matter described herein.

[0088] Preferred embodiments of the subject matter, including the best mode known to the inventors for carrying out the claimed subject matter, are described herein. Variations of the preferred embodiments may become apparent to those of skill in the art upon reading the foregoing description. The inventors anticipate that skilled artisans will employ such variations as appropriate, and the inventors intend that the subject matter described herein may be practiced otherwise than as specifically described herein. Accordingly, this disclosure includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by this disclosure unless otherwise indicated herein or clearly contradicted by context.

Claims

1. (a) a polypropylene polymer; and (b) Salts of branched alkylphosphonic acids A polymer composition comprising:

2. 10. The polymer composition of claim 1, wherein the polypropylene polymer is selected from the group consisting of polypropylene homopolymer, polypropylene random copolymer, polypropylene impact copolymer, and mixtures thereof.

3. 3. The polymer composition of claim 1 or claim 2, wherein the polypropylene polymer is selected from the group consisting of polypropylene homopolymer, polypropylene random copolymer, and mixtures thereof.

4. 4. The polymer composition of claim 1, wherein the salt of the branched alkylphosphonic acid comprises one or more cations selected from the group consisting of Group 1 element cations, Group 2 element cations, and Group 12 element cations.

5. 5. The polymer composition of claim 4, wherein the salt of the branched alkylphosphonic acid comprises a Group 2 element cation.

6. 6. The polymer composition of claim 5, wherein the salt of the branched alkylphosphonic acid comprises a calcium cation.

7. 7. The polymer composition of any one of claims 1 to 6, wherein the branched alkyl phosphonic acid comprises a branched alkyl group selected from the group consisting of isopropyl, sec-butyl, isobutyl, tert-butyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, sec-isopentyl, pentan-3-yl, and 2-methylbutyl.

8. The polymer composition of any one of claims 1 to 7, wherein the branched alkyl phosphonic acid comprises a tertiary alkyl group.

9. 8. The polymer composition of claim 7, wherein the branched alkyl phosphonic acid comprises a branched alkyl group selected from the group consisting of tert-butyl, tert-pentyl, and neopentyl.

10. 10. The polymer composition of any one of claims 1 to 9, wherein the salt of the branched alkyl phosphonic acid is a salt of tert-butyl phosphonic acid.

11. 11. The polymer composition of any one of claims 1 to 10, wherein the salt of the branched alkyl phosphonic acid is the calcium salt of tert-butyl phosphonic acid.

12. The salt of the branched alkylphosphonic acid is 20m ２ The polymer composition according to any one of claims 1 to 10, having a BET specific surface area of ​​1 / g or more.

13. The salt of the branched alkylphosphonic acid is 30 m ２ The polymer composition of claim 12 having a BET specific surface area of ​​1 / g or more.

14. 14. The polymer composition of any one of claims 1 to 13, wherein the salt of the branched alkyl phosphonic acid is present in the polymer composition in an amount of from about 50 parts per million to about 5,000 parts per million, based on the total weight of the polymer composition.

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