Non-alkyl phenol based liquid phosphite masterbatches

Abstract

Embodiments of a formulation comprise: ethylene-based polymer; 4 to 10 wt. % alkylphenol-free liquid polymeric phosphite, wherein at least 80 % of the total phosphorus in the alkylphenol-free liquid polymeric phosphite are in the active phosphite form; greater than zero to 10 wt. % alkylphenol antioxidants; and greater than zero to less than 5 wt. % acid scavenger.

Description

NON-ALKYL PHENOL BASED LIQUID PHOSPHITE MASTERBATCHESCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 678,788 filed August 2, 2024, and U.S. Provisional Application Serial No. 63 / 701,692 filed October 1, 2024, the contents of which are incorporated in their entirety herein.TECHNICAL FIELD

[0002] The present disclosure generally relates to masterbatches of non-alkyl phenol based liquid phosphites.BACKGROUND

[0003] Plastics are used for a wide range of industrial applications, including packaging, construction, and wire and cable. Non-alkyl phenol based liquid phosphites are more frequently being utilized as antioxidants for plastics, as well as a potential substitute to fluoro-containing polymer processing aids. Alkylphenol-free liquid polymeric phosphites are known to be hydrolytically and oxidatively unstable, thus making polymer masterbatches is challenging.

[0004] Accordingly, a need exists for making polymer masterbatches of alkylphenol-free liquid polymeric phosphite having sufficient hydrolytic and oxidative stability.SUMMARY

[0005] Embodiments of the present disclosure address this need for masterbatches having higher concentrations of non-alkyl phenol based liquid phosphites while limiting undesired hydrolysis and oxidation.

[0006] According to one or more embodiments of the present disclosure, a formulation comprising: ethylene-based polymer; 4 to 10 wt. % alkylphenol-free liquid polymeric phosphite, wherein at least 80 % of the total phosphorus in the alkylphenol-free liquid polymeric phosphite are in active form; greater than zero to 10 wt. % alkylphenol antioxidants; and greater than zero to less than 5 wt. % acid scavenger.

[0007] Additional features and advantages will be set forth in the detailed description that follows and, in part, will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments described herein, including the detailed description, which follows in addition to the claims.

[0008] It is to be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter.DETAILED DESCRIPTION

[0009] As used in this disclosure, the term “polymer” may refer to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus embraces the term “homopolymer,” usually employed to refer to polymers prepared from only one type of monomer as well as “copolymer,” which refers to polymers prepared from two or more different monomers.

[0010] “Blend”, “polymer blend” and like terms mean a composition of two or more polymers. Such a blend may or may not be miscible. Such a blend may or may not be phase separated. Such a blend may or may not contain one or more domain configurations, as determined from transmission electron spectroscopy, light scattering, x-ray scattering, and any other method known in the art. Blends are not laminates, but one or more layers of a laminate may contain a blend. Such blends can be prepared as dry blends, formed in situ (e.g., in a reactor), melt blends, or using other techniques known to those of skill in the art.

[0011] As used in this disclosure, the term “polyethylene” or “ethylene-based polymer” may refer to polymers comprising greater than 50% by mole of units which have been derived from ethylene monomer. This includes polyethylene homopolymers or copolymers (meaning units derived from two or more comonomers). Common forms of ethylene-based polymer known in the art include Low Density Polyethylene (LDPE); Linear Low Density Polyethylene (LLDPE); Ultra Low Density Polyethylene (ULDPE); Very Low Density Polyethylene (VLDPE); single-site catalyzed Linear Low Density Polyethylene, including both linear and substantially linear low-density resins (m-LLDPE); Medium Density Polyethylene (MDPE); and High Density Polyethylene (HDPE).

[0012] The term “LLDPE”, includes both resin made using the traditional Ziegler-Natta catalyst systems and chromium-based catalyst systems as well as single-site catalysts, including, but not limited to, bis -metallocene catalysts (sometimes referred to as “m- LLDPE”), constrained geometry catalysts (CGC), and molecular catalysts. Resins include linear, substantially linear, or heterogeneous polyethylene copolymers or homopolymers. LLDPEs contain less long chain branching than LDPEs and includes the substantially linear ethylene polymers which are further defined in U.S. Patent 5,272,236, U.S. Patent 5,278,272, U.S. Patent 5,582,923 and US Patent 5,733,155; the homogeneously branched linear ethylene polymer compositions such as those in U.S. Patent No. 3,645,992; the heterogeneously branched ethylene polymers such as those prepared according to the process disclosed in U.S. Patent No. 4,076,698; and / or blends thereof (such as those disclosed in US 3,914,342 or US 5,854,045). The LLDPEs can be made via gasphase, solution-phase or slurry polymerization or any combination thereof, using any type of reactor or reactor configuration known in the art.

[0013] The term “HDPE” or “high density polyethylene” refers to ethylene-based polymers having densities greater than 0.945 g / cc, which are generally prepared with Ziegler-Natta catalysts, chrome catalysts or even metallocene catalysts.

[0014] As used herein, “polymeric phosphite” refers to polymeric compounds comprising phosphite, and is intended to be interpreted broadly so as to include what might be referred to as oligomeric species. As a non-limiting example, the polymeric phosphite may comprise molecules containing at least three, at least four, at least five, or at least six phosphite-containing units. As another non-limiting example, the polymeric phosphite may comprise molecules comprising 500 or less, 100 or less, 90 or less, 50 or less, 20 or less, 5 to 500, 5 to 100, 5 to 15, or 3 to 20 phosphite- containing units.

[0015] As used herein “fluoropolymer” refers to polymeric compounds comprising fluorine, and is intended to be interpreted broadly so as to include what might be referred to as oligomeric species. As a non-limiting example, the fluoropolymer may comprise molecules containing at least three, at least four, at least five, or at least six fluorine containing units. As another non-limiting example, the polymeric phosphite may comprise 500 or less, 100 or less, 90 or less, 50 or less, 20 or less, 5 to 500, 5 to 100, 5 to 15, or 3 to 20 fluoride-containing units.

[0016] As used herein, “essentially free of’ means comprising less than 50 ppmw.

[0017] Embodiments are directed to formulations comprising: ethylene-based polymer; 4 to 10 wt. % alkylphenol-free liquid polymeric phosphite, wherein at least 80 % of the total phosphorus in the alkylphenol-free liquid polymeric phosphite are in active form; greater than zero to 10 wt. % alkylphenol antioxidants; and greater than zero to less than 5 wt. % acid scavenger.

[0018] Various compositions are considered suitable for the ethylene-based polymer. In one or more embodiments, the ethylene-based polymer may comprise LLDPE, or HDPE. In embodiments, the ethylene-based polymer may comprise a melt index (E) of 0.5 g / 10 mins as measured according to ASTM D-1238 (190° C / 2.16 Kg). In embodiments, the ethylene-based polymer may comprise a melt index of from 0.01 to 5.0 g / 10 mins, 0.01 to 2.0 g / 10 mins, from 0.2 to 0.8 g / 10 mins, from 0.3 to 0.7 g / 10 mins, from 0.4 to 0.6 g / 10 mins, or from 0.45 to 0.55 g / 10 mins. In further embodiments, the ethylene-based polymer may comprise a density from 0.850 to 0.980 g / cc, from 0.875 to 0.925 g / cc, from 0.890 to 0.915 g / cc, or from 0.895 to 0.910 g / cc.

[0019] In one or more embodiments, the formulation may comprise at least 60 weight percent (wt.%) of ethylene-based polymer. In embodiments, the formulation may comprise at least 60 wt.%, at least 65 wt.%, at least 70 wt.%, at least 75 wt.%, at least 80 wt.%, at least 85 wt.%, at least 90 wt.%, at least 91 wt.%, or at least 92 wt.% ethylene-based polymer. In embodiments, the formulation may comprise from a minimum of 60.0 wt.%, 85.0 wt.%, 86.0 wt.%, 87.0 wt.%, 88.0 wt.%, 89.0 wt.%, 90.0 wt.%, 91.0 wt.%, or 92.0 wt.% to a maximum of 75.0 wt.%, 80.0 wt.%, 85.0 wt.%, 86.0 wt.%, 87.0 wt.%, 88.0 wt.%, 89.0 wt.%, 90.0 wt.%, 91.0 wt.%, 92.0 wt.%, 93.0 wt.%, 94.0 wt.%, 95.0 wt.%, or 96.0 wt.%.

[0020] In one or more embodiments, the alkylphenol-free liquid polymeric phosphite may be a liquid polymeric phosphite having Formula (I), wherein R1, R2, R3, and R4can be the same or different and independently selected from the group consisting of C1-22 alkyl, C2-22 alkenyl, C6-40 cycloalkyl, C6-40 cycloalkylene; R5is a C3-22 hydrocarbon diradical; and x ranges from 2 to 1,000.In some embodiments, R5 may include same moiety of at least one of R1, R2, R3, and R4. In some embodiments R1, R2, R3, and R4may have one of the hydrogens replaced to -OH group.

[0021]

[0022] In one or more embodiments, the alkylphenol-free liquid polymeric phosphite may be a liquid polymeric phosphite having Formula (la), wherein R1, R2, R3and R4can be the same or different and independently selected from the group consisting of C1-20 alkyl, C2-22 alkenyl, C6-40 cycloalkyl, C6-40 cycloalkylene,; and x ranges from 1 to 500. In some embodiments R1, R2, R3, and R4may have one of the hydrogens replaced to -OH group.

[0023]

[0024] In one or more embodiments, the formulation may include from 4 wt.% to 10 wt.% alkylphenol-free liquid polymeric phosphite. In embodiments, the formulation may comprise from a minimum of 4 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, or 9 wt.% to a maximum of 7 wt.%, 8 wt.%, 9 wt.%, or 10 wt.% alkylphenol-free liquid polymeric phosphite.

[0025] Moreover, the formulation includes at least 80 % of the total phosphorus in the alkylphenol-free liquid polymeric phosphite in active form. Without being limited by theory, at least 80 of the total phosphorus in active form indicates suitable activity in the masterbatch as well as suitable hydrolytic and oxidative stability. In further embodiments, at least 80%, at least 82%, at least 84%, at least 86%, at least 88%, at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, or at least 95% of the total phosphorus in the alkylphenol-free liquid polymeric phosphite are in active form.

[0026] In one or more embodiments, the formulation may include greater than zero to less than 10 wt.% alkylphenol antioxidants. In embodiments, the formulation may comprise from a minimum of 0.001 wt.%, 0.01 wt.%, 0.05 wt.%, 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 1.0 wt.%, 2.0 wt.%, 3.0 wt.%, 4.0 wt.%, 5.0 wt.%, 6.0 wt.%, 7.0 wt.%, 8.0 wt.%, or 9.0 wt.% to a maximum of 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 1.0 wt.%, 2.0 wt.%, 3.0 wt.%, 4.0 wt.%, 4.9 wt.%, 5.0 wt.%, 6.0 wt.%, 7.0 wt.%, 8.0 wt.%, 9.0 wt.%, or 10 wt.% alkylphenol antioxidants.

[0027] In one or more embodiments, the formulation may include greater than zero to less than 5 wt.% acid scavenger. In embodiments, the formulation may comprise from a minimum of 0.001 wt.%, 0.01 wt.%, 0.05 wt.%, 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 1.0 wt.%, 2.0 wt.%, 3.0 wt.%, or 4.0 wt.% to a maximum of 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 1.0 wt.%, 2.0 wt.%, 3.0 wt.%, 4.0 wt.%, or 4.9 wt.% acid scavenger. Various acid scavengers are considered suitable. In one embodiment, the acid scavenger comprises ZnO. Without being limited by theory, the acid scavenger may counteract any acid formation resulting from reactions with the alkylphenol-free liquid polymeric phosphite.

[0028] The acid scavenger and alkylphenol antioxidant may be delivered with the ethylenebased polymer, or it may be added separately.

[0029] Further optional additives are contemplated for the formulation. In some embodiments, a composition may include one or more other additives. Non limiting examples of suitable other additives include antioxidants, antistatic agents, stabilizing agents, nucleating agents, colorants, pigments, ultra violet (UV) absorbers or stabilizers, flame retardants, compatibilizers, plasticizers,fillers, processing aids, antifog additive, crosslinking agents (e.g., peroxides), and combinations thereof. In one or more embodiments, the formulation is free of fluoropolymer.

[0030] In one or more embodiments, the formulation is a masterbatch. In another embodiment, the formulation is a pellet.

[0031] The process for making the formulations comprise blending the ethylene-based polymer, the alkylphenol-free liquid polymeric phosphite, the alkylphenol antioxidant or antioxidants, and the acid scavenger at a temperature below 230 °C. These components may be added in various orders. In another embodiment, the blending occurs at a temperature below 200 °C. In a further embodiment, the alkylphenol-free liquid polymeric phosphite is provided neat, and the alkylphenol antioxidants and acid scavenger are delivered in a polymer masterbatch.

[0032] In another embodiment, the process comprises extruding the blend into polymer strands. In another embodiment, the process comprises cooling the cooled polymer strands. In yet another embodiment, the process further comprises pelletizing the polymer strands in a water bath.

[0033] ARTICLES

[0034] In one or more embodiments, an article may be produced from the formulations described herein. The articles may include films, for example, monolayer or multilayer films. Articles, which incorporate film, may include non-rigid packages, such as flexible packages, pouches, stand-up pouches, and the like. The articles may also include rigid packages, for example, wires and cable, piping, and the like. Articles may also include tubes or pipes or wires.

[0035] TEST METHODS

[0036] Melt Index (190 °C, 2.16 kg, "I2") Test Method: ASTM D 1238-13, Standard Test Method for Melt Flow Rates of Thermoplastics by Extrusion Plastometer, using conditions of 190 °C / 2.16 kilograms (kg). Results were reported in units of grams eluted per 10 minutes (g / 10 min.)

[0037] Density measurements were performed according to ASTM D4703. Measurements were made, according to ASTM D792, Method B, within one hour of sample pressing.

[0038] Phosphorus-31 Nuclear Magnetic Resonance (3*P NMR)

[0039] The percentage of phosphorus in the active phosphite form in the alkylphenol-free liquid polymeric phosphite, as-received, prior to making masterbatch pellets, was measured via 31P NMR. Samples were prepared in 10 mm NMR tubes using about 0.5 g of liquid phosphite in about 2.5 mL of solvent. The solvent was a 50 / 50 (wt. / wt.) mixture of xylenes and perchloroethylene, containing 120 ppm butylated hydroxytoluene (BHT) and stored over molecular sieve. 1H decoupled 3 IP NMR spectra were acquired using a Bruker 400 MHz spectrometer equipped with a 10 mm broadband observe probe. The data was acquired using a 20.6 second pulse repetition delay, 90-degree flip angles, inverse gated decoupling, 64 scans, at a sample temperature of 25°C. Phosphorus present as active phosphite was measured by integration of the region from about 129 to 146 ppm, and non-active was measured as the sum of all peak integrals from about 40 to -18 ppm. The spectra chemical shifts were referenced to roughly correspond to 0 ppm for phosphoric acid.

[0040] In produced masterbatch pellets, the wt.% of alkylphenol-free liquid polymeric phosphite and the percentage of phosphorus in the active phosphite form was measured via 3 IP NMR. Samples were prepared in 10 mm NMR tubes using about 0.22 g of pellets in about 2.5 mL of solvent. About 90 mg of a dilute solution (5.116 x 10’5mols P per g solution) of triphenylphosphate in xylenes was added as an internal 3 IP quantitation standard. The actual weights of pellets and internal standard were recorded to ± 1 mg. The solvent was a 50 / 50 (wt. / wt.) mixture of xylenes and perchloroethylene, containing 120 ppm butylated hydroxytoluene (BHT) and stored over molecular sieve. Samples were heated and mixed at 135 °C to dissolve. 1H decoupled 3 IP NMR spectra were acquired using a Bruker 600 MHz spectrometer equipped with a 10 mm multinuclear cry oprobe. The data was acquired using a 20.4 second pulse repetition delay, 90-degree flip angles, inverse gated decoupling, 64 scans, at a sample temperature of 120°C. Phosphorus present as active phosphite was measured by integration of the region from about 129 to 146 ppm, and non-active was measured as the sum of all peak integrals from about 40 to -18 ppm. The triphenylphosphate internal standard peak at about -20 ppm was integrated to enable quantitation of the total liquid phosphite, which was calculated using the known wt.% P of the liquid phosphite. The spectra chemical shifts were referenced to roughly correspond to 0 ppm for phosphoric acid.EXAMPLES

[0041] The following Examples are offered by way of illustration and are presented in a manner such that one skilled in the art should recognize are not meant to be limiting to the present disclosure as a whole or to the appended claims.

[0042] The following commercial compositions were used in the Examples below.

[0043] An LLDPE resin having ZnO scavenger (840 ppm) and alkylphenol antioxidant (1440 ppm) was utilized. The LLDPE has a density of 0.917 g / cc and a melt index (L) of 3.2 dg / min.

[0044] The alkylphenol antioxidant is octadecyl 3-(3,5-di-tert-butyl-4- hydroxyphenyljpropionate (CAS 2082-79-3).

[0045] Doverphos LGP12, which is available from the Dover Chemical Corporation is a liquid polymeric phosphite free of alkylphenols.

[0046] Compounding

[0047] These runs were compounded using a Coperion 26 Me 18 twin screw extruder (serial # 10008408). The extruder's Effective Power Rating is 35.2 (kW). The Effective Output Torque is 2X140 (Nm). The maximum output Speed is 1200 (min-1). The gearbox ratio is 1.815.

[0048] LLDPE was fed into the extruder feed throat of a K-Tron KXQ4 (KCM 3) feeder with a single coarse auger, and no agitator. The Doverphos LGP12 was injected into the extruder's 4th barrel block using a Zenith gear pump on a custom skid. The backpressure maintained on the pumps discharge side was approximately 500 PSI. The feeders where calibrated prior to use. Rate checks were performed on the Zenith gear pump to confirm oil feed rates.

[0049] The extruder's Barrel assembly stretches from zone 1 to zone 11. This barrel assembly consists of 11-barrel blocks. Total extruder barrel length is 1125 mm, therefore the total length of the extruder's processing section is 1125 mm. The barrel assembly is a 44 / 1 L / D. The Extruder's barrel inner diameter is 26 mm, while the screw diameter is 25.5 mm. The screw design was a mild screw with one melting and two dispersive mixing sections. The screw was 44 L / D with 3L / D of melting section and two mixing sections of 1 and 1.5 L / D, respectively, before the pumping section at the end of the screw design.

[0050] Table 1 - Extruder Specifications*N / A means not applicable

[0051] During the compounding process, nitrogen was injected at the feed throat. The gauge on the micro flow meter was set to 10-S.C.F.H. (standard cubic feet per hour). The residence time of the samples was controlled by the screw design, total feed rate, and RPM. Vacuum was not used for this experiment. There was no vent installed in the extruder barrel.

[0052] Strand Bath with Conair Cutter

[0053] Molten polymer was extruded through a 4 x 4 mm hole die. This die was equipped with twin heater rods, which created less resistance, lowering the pressure at the die face. The polymer strands were submerged into a chilled water bath, then quickly brought out of the water to minimize water contact. Next, the strands ascended from the bath and passed through an air block. After passing through the air block, the strands entered the Conair 304 strand pelletizer and were pelletized.

[0054] After a sample was collected, the sample was removed from the pelletizer and taken to a fume hood. Nitrogen wands were inserted into the pellet bags, and the samples were dried under nitrogen overnight. The following day, the samples were collected and sealed. The pellets were analyzed by 3 IP NMR to determine the wt.% TGP12 and the percentage of phosphorus present as active phosphite.

[0055] Table 2

[0056] LGP12, which has 95.5% of the total phosphorous in the active form prior to compounding, is reduced to less than 20% of the total phosphorous in the active form when compounded at a preparation temperature of 260 °C without presence of alkylphenol antioxidant and acid scavenger (Comparative Example 1). This reduction indicates significant hydrolysis. In contrast, Inventive example 3 maintains 84.2% of total phosphorous in the active form at the same temperature. Inventive examples l-2maintain greater than 90% active EGP12 after compounding when compounding at 190 and 220 °C.

[0057] The subject matter of the present disclosure has been described in detail and by reference to specific embodiments. It should be understood that any detailed description of a component or feature of an embodiment does not necessarily imply that the component or feature is essential to the particular embodiment or to any other embodiment. Further, it should be apparent to those skilled in the art that various modifications and variations can be made to the described embodiments without departing from the spirit and scope of the claimed subject matter.

[0058] It is noted that one or more of the following claims utilize the term “wherein” as a transitional phrase. For the purposes of defining the present technology, it is noted that this term is introduced in the claims as an open-ended transitional phrase that is used to introduce a recitation of a series of characteristics of the structure and should be interpreted in like manner as the more commonly used open-ended preamble term “comprising.”

[0059] It should be understood that where a first component is described as “comprising” a second component, it is contemplated that, in embodiments, the first component “consists” or “consists essentially of’ that second component. It should further be understood that where a first component is described as “comprising” a second component, it is contemplated that, in embodiments, the first component comprises at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or even at least 99% that second component (where % can be weight % or molar %).

[0060] It is also noted that recitations herein of “at least one” component, element, etc., should not be used to create an inference that the alternative use of the articles “a” or “an” should be limited to a single component, element, etc.

Claims

CLAIMS1. A formulation comprising: ethylene-based polymer;4 to 10 wt. % alkylphenol-free liquid polymeric phosphite, wherein at least 80 % of the total phosphorus in the alkylphenol-free liquid polymeric phosphite is in the active phosphite form; greater than zero to 10 wt. % alkylphenol antioxidants; and greater than zero to less than 5 wt. % acid scavenger.

2. The formulation of claim 1, wherein the formulation comprises at least 60 wt. % ethylene-based polymer.

3. The formulation of claim 1, wherein at least 90 % of the total phosphorus in the alkylphenol-free liquid polymeric phosphite is in the active phosphite form.

4. The formulation of any preceding claim, wherein the formulation is essentially free of fluoropolymer.

5. The formulation of any preceding claim, wherein the ethylene-based polymer comprises TTDPE or HDPE.

6. The formulation of any preceding claim, wherein the acid scavenger comprises ZnO.

7. The formulation of any preceding claim, wherein the formulation is a masterbatch.

8. The formulation of any preceding claim, wherein the formulation is a pellet.

9. A process for making the formulations of any preceding claim comprising: blending the ethylene-based polymer, the alkylphenol-free liquid polymeric phosphite, the alkylphenol antioxidants, and the acid scavenger at a temperature below 230 °C.

10. The process of claim 9, wherein the blending occurs at a temperature below 200 °C.

11. The process of claims 9 or 10, further comprising extruding the blend into polymer strands.

12. The process of claim 11, further comprising cooling the cooled polymer strands.

13. The process of claim 11, further comprising pelletizing the polymer strands in a water bath.

14. The process of any of claims 9 to 13, wherein the alkylphenol-free liquid polymeric phosphite is provided neat, and the alkylphenol antioxidants and acid scavenger are delivered in a polymer masterbatch.

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