Thermoplastic polyurethane-containing composition

Abstract

A polymer composition can include a polymer produced from ethylene, one or more branched vinyl ester monomers, optionally vinyl acetate (VA), and a thermoplastic polyurethane (TPU). A method of making a polymer composition can include blending a thermoplastic polyurethane (TPU) and an ethylene-based polymer produced from ethylene, one or more branched vinyl ester monomers, and optionally vinyl acetate (VA); to form a blended mixture; and extruding the blended mixture to form the polymer composition.

Description

Background Technology

[0001] Thermoplastic polyurethane, or TPU, is a thermoplastic plastic produced by the reaction of macroglycol, diisocyanate, and short-chain diol. It exhibits both elastomer and thermoplastic properties. Due to its beneficial properties (such as high abrasion resistance, high shear strength, and high elasticity), thermoplastic polyurethane is used in a wide range of applications, including sporting goods, automotive, injection-molded components, soft-touch home furnishings, pipes and profiles, films and sheets, textiles, seals, and gaskets.

[0002] Traditionally, TPUs have followed a trend where decreasing hardness leads to a decrease in tensile properties, modulus, and strength. There remains a need in the field to develop polymers that can reduce hardness while maintaining tensile properties. Summary of the Invention

[0003] This summary is provided to introduce a series of concepts that will be further described in the following detailed description. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to help limit the scope of the claimed subject matter.

[0004] In one or more aspects, the embodiments disclosed in this specification relate to a polymer composition comprising: a polymer produced from ethylene, one or more branched vinyl ester monomers and optionally vinyl acetate; and thermoplastic polyurethane (TPU).

[0005] On the other hand, the embodiments disclosed in this specification relate to a method for producing a polymer composition comprising blending a thermoplastic polyurethane (TPU) polymer and a vinyl ester-containing copolymer to form a polymer composition, wherein the vinyl ester-containing copolymer comprises ethylene, one or more branched vinyl ester monomers, and optionally vinyl acetate.

[0006] In one or more aspects, the embodiments disclosed in this specification relate to an article of manufacture prepared from a polymer composition comprising: a polymer produced from ethylene, one or more branched vinyl ester monomers and optionally vinyl acetate; and thermoplastic polyurethane (TPU).

[0007] Other aspects and advantages of the claimed subject matter will become apparent from the following description and the appended claims. Attached Figure Description

[0008] Figure 1 This is a diagram illustrating the tensile data of TPU blends in one or more embodiments of this disclosure.

[0009] Figure 2 This is a diagram illustrating the tensile data of TPU blends in one or more embodiments of this disclosure.

[0010] Figure 3A These are atomic force micrographs of reference TPU blends.

[0011] Figure 3B These are atomic force micrographs of reference TPU blends.

[0012] Figure 3C These are atomic force micrographs of TPU blends from one or more embodiments of this disclosure.

[0013] Figure 3D These are atomic force micrographs of TPU blends from one or more embodiments of this disclosure.

[0014] Figure 3E These are atomic force micrographs of TPU blends from one or more embodiments of this disclosure. Detailed Implementation

[0015] In one aspect, the embodiments disclosed in this specification relate to polymer compositions comprising an ethylene-based polymer prepared from ethylene and one or more branched vinyl ester monomers, and a thermoplastic polyurethane (TPU). Such polymer compositions can allow for reduced hardness and improved tactile feel (compared to TPU alone), while maintaining tensile strength, a lower glass transition temperature (Tg), and higher abrasion resistance.

[0016] While EVA can be used to reduce the hardness of TPU-containing compositions, ethylene-based polymers blended with TPU, comprising at least ethylene and branched vinyl esters, can advantageously achieve this effect at lower dosages compared to EVA. In one or more embodiments, the polymer composition can be foamed to produce articles with a favorable combination of properties, such as low operating temperatures and better abrasion behavior than current solutions. Such polymer compositions can be used in a wide range of applications, including soles or shoe parts, films, tubing, fibers, cables, ear tags, motor components, automotive parts, hoses, belts, damping elements, handrails, furniture elements, ski boots, stoppers, rollers, ski goggles, powder coatings, antennas and antenna feet, handles, housings, switches, and cladding and cladding elements.

[0017] The polymer compositions according to this disclosure may include ethylene-based polymers comprising various proportions of ethylene and one or more branched vinyl esters. In some embodiments, the polymer composition may be prepared by reacting ethylene and branched vinyl esters in a high-pressure polymerization process in the presence of additional comonomers. In other embodiments, terpolymers may be similarly prepared by additionally adding vinyl acetate monomers. In one or more embodiments, the polymer composition may include polymers derived from monomers derived from petroleum and / or renewable sources.

[0018] polymer composition

[0019] The polymer compositions disclosed in this specification comprise suitable amounts of thermoplastic polyurethane and suitable amounts of a polymer produced from ethylene, one or more branched vinyl ester monomers, and optionally vinyl acetate. It is also contemplated that the polymer compositions disclosed in this specification may optionally include one or more of compatibilizers, crosslinking agents, foaming agents, accelerators, and elastomers.

[0020] Ethylene-based polymers

[0021] In one or more embodiments, the polymer compositions disclosed herein comprise suitable amounts of an ethylene-based polymer produced from ethylene, one or more branched vinyl ester monomers (as copolymers), and optionally vinyl acetate (as terpolymers). In some embodiments, the polymer composition comprises 5 wt% to 85 wt% (by weight) of an ethylene-based polymer produced from ethylene, one or more branched vinyl ester monomers, and optionally vinyl acetate. The polymer produced from ethylene, one or more branched vinyl ester monomers, and optionally vinyl acetate may be present in the polymer composition in amounts ranging from a lower limit of 0.5 wt%, 1 wt%, 2.5 wt%, 5 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, or 45 wt% and an upper limit of 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, and 85 wt%, wherein any lower limit may be combined with any mathematically compatible upper limit.

[0022] The polymer compositions according to this disclosure may include ethylene-based polymers comprising various proportions of ethylene and one or more branched vinyl esters. In some embodiments, the polymer composition may be prepared by reacting ethylene and branched vinyl esters in a high-pressure polymerization process in the presence of additional comonomers. In other embodiments, terpolymers may be similarly prepared by additionally adding vinyl acetate monomers. In one or more embodiments, the polymer composition may include polymers derived from monomers derived from petroleum and / or renewable sources.

[0023] Branched vinyl ester monomers

[0024] As described above, the polymer composition may include an ethylene-based polymer comprising a branched vinyl ester monomer. In one or more embodiments, the branched vinyl ester may comprise a branched vinyl ester generated from a mixture of isomers of branched alkyl acids. The branched vinyl esters according to this disclosure may have the general chemical formula (I): (I) Where R 1 R 2 and R 3 It has a total carbon number ranging from C3 to C20. In some embodiments, R 1 R 2 and R 3 In some embodiments, the chains may consist entirely of alkyl chains with different degrees of branching, or R 1 R 2 and R 3 A subset may be independently selected from the group consisting of hydrogen, alkyl or aryl groups in some embodiments.

[0025] In one or more embodiments, the branched vinyl ester may have the general chemical formula (II): (II) Where R 4 and R 5 Having a total carbon number of 6 or 7, and the polymer composition having a number-average molecular weight (Mn) of 5 kDa to 10,000 kDa obtained by GPC. n In one or more embodiments, R 4 and R 5 It can have a total carbon number of less than 6 or greater than 7, and the polymer composition can have an M value of up to 10,000 kDa. n In other words, when M n When R is less than 5 kDa, 4 and R 5 It can have a total carbon number of less than 6 or greater than 7, but if M nIf R is greater than 5 kDa, for example, in the range of 5 kDa to 10000 kDa, then 4 and R 5 It can include a total carbon number of 6 or 7. In a specific embodiment, R 4 and R 5 With a total carbon number of 7, M n It can be in the range of 5 kDa to 10000 kDa. Furthermore, in one or more specific embodiments, the branched vinyl ester according to formula (II) can be used in combination with vinyl acetate.

[0026] Examples of branched vinyl esters may include monomers having the following chemical structures (including their derivatives):

[0027] In one or more embodiments, the polymer composition may include a polymer derived from monomers derived from petroleum and / or renewable sources.

[0028] In one or more embodiments, the branched vinyl ester may comprise a mixture of monomers and comonomers containing vinyl esters such as neononanoic acid and neodecanoic acid. In some embodiments, the branched vinyl ester may comprise monomers available from Hexion TM Versatic obtained from chemical purchase TM Acid series tertiary carboxylic acids, including Versatic acid synthesized via Koch synthesis. TM Acid EH, Versatic TM Acid 9 and Versatic TM Acid 10.

[0029] According to this disclosure, ethylene-based polymers may contain ethylene, the ethylene being detected by proton nuclear magnetic resonance (NMR). 1 HNMR) and carbon-13 nuclear magnetic resonance (NMR) 13 The weight percentage range measured by C NMR is from a lower limit selected from one of 70 wt%, 75 wt%, and 80 wt% to an upper limit selected from one of 85 wt%, 90 wt%, 95 wt%, 99.9 wt%, and 99.99 wt%, where any lower limit can be paired with any upper limit.

[0030] According to this disclosure, ethylene-based polymers may contain vinyl ester monomers (e.g., vinyl ester monomers of formulas (I) and (II) above), wherein the vinyl ester monomer is... 1 H NMR and 13The weight percentage range measured by C NMR is from a lower limit selected from one of 0.01 wt%, 0.1 wt%, 1 wt%, 5 wt%, 10 wt%, 20 wt%, or 30 wt% to an upper limit selected from 50 wt%, 60 wt%, 70 wt%, 80 wt%, 89.99 wt%, or 90 wt%, where any lower limit can be paired with any upper limit.

[0031] The disclosed ethylene-based polymers may include vinyl acetate, which is obtained through... 1 H NMR and 13 The weight percentage range measured by C NMR is from a lower limit selected from one of 0.01 wt%, 0.1 wt%, 1 wt%, 2 wt%, 5 wt%, 10 wt%, 12 wt%, 15 wt%, 20 wt%, or 30 wt% to an upper limit selected from 20 wt%, 30 wt%, 33 wt%, 35 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt%, or 89.99 wt%, where any lower limit can be paired with any upper limit.

[0032] The number-average molecular weight (MnA) of ethylene-based polymers according to this disclosure, measured by gel permeation chromatography (GPC), is in kilodaltons (kDa). n The range can be a lower limit selected from one of 1 kDa, 5 kDa, 10 kDa, 15 kDa and 20 kDa to an upper limit selected from one of 40 kDa, 50 kDa, 100 kDa, 300 kDa, 500 kDa, 1000 kDa, 5000 kDa and 10000 kDa, where any lower limit can be paired with any upper limit.

[0033] According to the ethylene-based polymers of this disclosure, the weight-average molecular weight (Mn) in kilodaltons (kDa) is measured by GPC. w The range can be a lower limit selected from one of 1 kDa, 5 kDa, 10 kDa, 15 kDa and 20 kDa to an upper limit selected from one of 40 kDa, 50 kDa, 100 kDa, 200 kDa, 300 kDa, 500 kDa, 1000 kDa, 2000 kDa, 5000 kDa, 10000 kDa and 20000 kDa, where any lower limit can be paired with any upper limit.

[0034] According to the molecular weight distribution (MWD) of ethylene-based polymers as measured by GPC in this disclosure, which is defined as M w With M nThe ratio has a lower limit of any one of 1, 2, 5 or 10 and an upper limit of any one of 20, 30, 40, 50 or 60, wherein any lower limit can be paired with any upper limit.

[0035] In some embodiments, the ethylene-based polymer can be polymerized in the presence of one or more initiators for radical polymerization, which are capable of generating free radicals that initiate chain polymerization of comonomers and prepolymers in the reactant mixture. In one or more embodiments, the radical initiator may include a chemical substance that spontaneously degrades or degrades in response to stimuli such as temperature, pH, or other triggering factors to release free radicals.

[0036] In one or more embodiments, the free radical initiator may include: peroxides and bifunctional peroxides (e.g., benzoyl peroxide); dicumyl peroxide; di-tert-butyl peroxide; tert-butyl peroxide; tert-butyl 2-ethylhexanoate peroxide; tert-butyl neopentanoate peroxide; tert-butyl neodecanoate peroxide; tert-butyl benzoate peroxide; tert-butyl 2-ethylhexanoate peroxide; tert-butyl 3,5,5-trimethylhexanoate peroxide; tert-butyl benzoate peroxide; 2-ethylhexyl carbonate tert-butyl peroxide; 2,5-dimethyl-2,5-di(tert-butyl peroxide)hexane. hexane); 1,1-di(tert-butylperoxide)-3,3,5-trimethylcyclohexane; 2,5-dimethyl-2,5-di(tert-butylperoxide)hexyn-3; 3,3,5,7,7-pentamethyl-1,2,4-trioxacycloheptane; 4,4-di(tert-butylperoxide)valerate butyl ester; bis(2,4-dichlorobenzoyl)peroxide; bis(4-methylbenzoyl)peroxide; di(tert-butylperoxyisopropyl)benzene peroxide, etc.

[0037] Free radical initiators may also include benzoyl peroxide, 2,5-di(isopropylphenylperoxy)-2,5-dimethylhexane, 2,5-di(isopropylphenylperoxy)-2,5-dimethylhexyn-3,4-methyl-4-(tert-butylperoxy)-2-pentanol, 4-methyl-4-(tert-pentylperoxy)-2-pentanol, 4-methyl-4-(isopropylphenylperoxy)-2-pentanol, 4-methyl-4-(tert-butylperoxy)-2-pentanone, 4-methyl-4-(tert-pentylperoxy)-2-pentanone, 4-methyl-4-(isopropylphenylperoxy)-2-pentanone, and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane. 2,5-Dimethyl-2,5-di(tert-amylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-di(tert-amylperoxy)hexyne-3, 2,5-dimethyl-2-tert-butylperoxy-5-hydroperoxyhexane, 2,5-dimethyl-2-isopropylphenylperoxy-5-hydroperoxyhexane, 2,5-dimethyl-2- Tert-amylperoxy-5-hydroperoxyhexane, m / p-α,α-di[(tert-butylperoxy)isopropyl]benzene, 1,3,5-tris(tert-butylperoxyisopropyl)benzene, 1,3,5-tris(tert-amylperoxyisopropyl)benzene, 1,3,5-tris(cumylperoxyisopropyl)benzene, di[1,3-dimethyl-3-(tert-butylperoxy)butyl]carbonate, di[1,3-dimethyl-3-(tert-amylperoxy)butyl]carbonate, di[1,3-dimethyl-3-(isopropylphenylperoxy)butyl]carbonate, ditert-amyl peroxide, tert-amylisopropylphenyl peroxide, tert-butylisopropenyl peroxide, 2,4,6-tris(butylperoxy)-s-triazine, 1,3,5-tris[1-(tert-butylperoxy)-1-methylethyl]benzene, 1,3,5-tris[(tert-butylperoxy)-isopropyl]benzene, 1,3-dimethyl-3-(tert-butylperoxy)butanol, 1,3-dimethyl-3-(tert-amylperoxy)butanol, di(2-phenoxyethyl)peroxydicarbonate, di(4-tert-butylcyclohexyl)peroxydicarbonate, dimyristylperoxydicarbonate, dibenzyl 3-Isobomyl peroxydicarbonate, di(isobornyl)peroxydicarbonate, 3-isopropylphenylperoxy-1,3-dimethylbutyl methacrylate, 3-tert-butylperoxy-1,3-dimethylbutyl methacrylate, 3-tert-pentylperoxy-1,3-dimethylbutyl methacrylate, tris(1,3-dimethyl-3-tert-butylperoxybutoxy)vinylsilane, N-[1-{3-(1-methylvinyl)-phenyl)1-methylethyl]carbamate 1,3-Dimethyl-3-(t-butylperoxy)butyl N-[1-{3-(1-methylethenyl)-phenyl) 1-methylethyl]carbamate, N-[1-{3(1-methylethenyl)-phenyl}-1-methylethyl]carbamate, 1,3-dimethyl-3-(t-pentylperoxy)butyl N-[1-{3-(1-methylethenyl)-phenyl}-1-methylethyl]carbamate, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 4,4-di( Butyl tert-butylperoxy)valerate, ethyl 3,3-di(tert-butylperoxy)butanoate, 2,2-di(tert-butylperoxy)propane, 3,6,6,9,9-pentamethyl-3-ethoxycarbonylmethyl-1,2,4,5-tetraoxacyclononane, 1,4,4-bis(tert-butylperoxy)valerate (-buty 1-4,4-bis(t-butylperoxy)valerate, ethyl-3,3-di(tert-pentylperoxy)butyrate, benzoyl peroxide, OO-tert-butyl-O-hydro-monoperoxy-succinate, OO-tert-pentyl-O-hydro-monoperoxy-succinate, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane (or methyl ethyl ketone peroxide cyclic trimer), methyl ethyl ketone peroxide cyclic dimer, 3,3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-butyl perbenzoate, tert-butyl peroxyacetate (t-butylperoxy) Acetate), tert-butyl peroxy-2-ethylhexanoate, tert-amyl perbenzoate, tert-amyl peroxyacetate, tert-butyl peroxyisobutyrate, 3-hydroxy-1-dimethyl peroxy-2-hexanoate,1-Dimethyl tert-butyl ester, OO-tert-amyl-O-hydrogen-monoperoxy succinate, OO-tert-butyl-O-hydrogen-monoperoxy succinate, di-t-butyldiperoxyphthalate, tert-butylperoxy(3,3,5-trimethylhexanoate), 1,4-bis(t-butylperoxycarbonyl)cyclohexane, t-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxy-(cis-3-carboxyl)propionate, 3-methyl-3-tert-butylperoxybutyrate, OO-tert-butyl-O -Isopropylmonoperoxy carbonate (OO-t-butyl-O-isopropylmonoperoxy carbonate), OO-tert-butyl-O-(2-ethylhexyl)monoperoxy carbonate (OO-t-butyl-O-(2-ethyl hexyl)monoperoxy carbonate), 1,1,1-tris[2-(tert-butylperoxycarbonyloxy)ethoxymethyl]propane, 1,1,1-tris[2-(tert-pentylperoxycarbonyloxy)ethoxymethyl]propane, 1,1,1-tris[2-(isopropylphenylperoxycarbonyloxy)ethoxymethyl]propane, OO-tert-pentyl-O-isopropylmonoperoxy carbonate (OO-t-amyl-O-isopropylmonoperoxy) Carbonate, bis(4-methylbenzoyl) peroxide, bis(3-methylbenzoyl) peroxide, bis(2-methylbenzoyl) peroxide, didecanoyl peroxide, dilauryl peroxide, 2,4-dibromobenzoyl peroxide, succinic acid peroxide, dibenzoyl peroxide, bis(2,4-dichlorobenzoyl) peroxide and combinations thereof.

[0038] In one or more embodiments, the free radical initiator may include: an azo compound, such as azobisisobutyronitrile (AIBN), 2,2'-azobis(amidinylpropyl) dihydrochloride, etc.; an azoperoxide initiator containing a mixture of peroxide and azobisonitrile compound, such as 2,2'-azobis(2-methylpentanitrile), 2,2'-azobis(2-methylbutanitrile), 2,2'-azobis(2-ethylpentanitrile), 2-[(1-cyano-1-methylpropyl)azo]-2-methylpentanitrile, 2-[(1-cyano-1-ethylpropyl)azo]-2-methylbutanitrile, 2-[(1-cyano-1-methylpropyl)azo]-2-ethyl, etc.

[0039] In one or more embodiments, the radical initiator may include a carbon-carbon (“CC”) radical initiator, such as 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, 3,4-diethyl-3,4-diphenylhexane, 3,4-dibenzyl-3,4-dimethylhexane, 2,7-dimethyl-4,5-diethyl-4,5-diphenyloctane, 3,4-dibenzyl-3,4-diphenylhexane, etc.

[0040] In one or more embodiments, the ethylene-based polymer polymerization may include one or more radical initiators, wherein the weight percentage (wt%) of the one or more radical initiators in the total polymer mixture ranges from a lower limit selected from any one of 0.000001 wt%, 0.0001 wt%, 0.01 wt%, 0.1 wt%, 0.15 wt%, 0.4 wt%, 0.6 wt%, 0.75 wt%, and 1 wt% to an upper limit selected from any one of 0.5 wt%, 1.25 wt%, 2 wt%, 4 wt%, and 5 wt%, wherein any lower limit may be used in conjunction with any upper limit. Furthermore, the concentration of the radical initiator is expected to be more or less depending on the application of the final material.

[0041] In some embodiments, the ethylene-based polymer can be polymerized in the presence of one or more stabilizers that prevent the polymerization of monomers and comonomers in the feed line but do not impede polymerization in the reactor.

[0042] In one or more embodiments, the stabilizer may include nitroyl derivatives, such as 2,2,6,6-tetramethyl-1-piperidinoxy, 2,2,6,6-tetramethyl-4-hydroxy-1-piperidinoxy, 4-oxo-2,2,6,6-tetramethyl-1-piperidinoxy, 2,2,6,6-tetramethyl-4-amino-piperidinoxy, etc.

[0043] In one or more embodiments, the ethylene-based polymer may contain a stabilizer in a weight percentage (wt%) range selected from any of 0.000001 wt%, 0.0001 wt%, 0.01 wt%, 0.1 wt%, 0.15 wt%, 0.4 wt%, 0.6 wt%, 0.75 wt%, and 1 wt% to an upper limit selected from any of 0.5 wt%, 1.25 wt%, 2 wt%, 4 wt%, and 5 wt%, wherein any lower limit may be paired with any upper limit. Furthermore, the concentration of the stabilizer is expected to be higher or lower depending on the application of the final material.

[0044] In some embodiments, the ethylene-based polymer may be polymerized in the presence of a chain transfer agent. Examples of chain transfer agents may include propylene, ethane, propane, methane, trimethylamine, dimethylamine, chloroform, and carbon tetrachloride. The chain transfer agent may be present by weight (wt%) of the total polymeric mixture, ranging from a lower limit selected from one of 0.0000001 wt%, 0.000001 wt%, 0.001 wt%, 0.01 wt%, 0.02 wt%, 0.05 wt%, and 1.0 wt% to an upper limit selected from one of 2.0 wt%, 3.0 wt%, 4.0 wt%, and 5.0 wt%, wherein any lower limit may be used in conjunction with any upper limit.

[0045] In one or more embodiments, the ethylene-based polymer can be prepared in a reactor by polymerizing ethylene and one or more branched vinyl ester monomers. Methods for reacting the comonomers in the presence of a free radical initiator can include any suitable method in the art, including solution-phase polymerization, pressure-driven free radical polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization.

[0046] In some embodiments, the reactor may be a batch reactor or a continuous reactor with a pressure below 500 bar, referred to as a low-pressure polymerization system. In one or more embodiments, the reaction may be carried out in a low-pressure polymerization process, wherein ethylene and one or more vinyl ester monomers are polymerized in the liquid phase of an inert solvent and / or one or more liquid monomers.

[0047] In some embodiments, the polymerization may include an amount of free radical polymerization initiator from about 0.0001 mmol to about 0.01 mmol, the amount being calculated as the total amount of one or more free radical polymerization initiators per liter of polymerization zone volume. The amount of ethylene in the polymerization zone may depend primarily on the total reactor pressure in the range of about 20 bar to about 500 bar and the temperature in the range of about 20 °C to about 300 °C.

[0048] In one or more embodiments, the pressure in the reactor may be within the range of a lower limit of any one of 20 bar, 30 bar, 40 bar, 50 bar, 75 bar, or 100 bar to an upper limit of any one of 100 bar, 150 bar, 200 bar, 250 bar, 300 bar, 350 bar, 400 bar, 450 bar, or 500 bar, and the temperature in the reactor may be within the range of a lower limit of any one of 20 °C, 50 °C, 75 °C, or 100 °C to an upper limit of any one of 150 °C, 200 °C, 250 °C, or 300 °C, wherein any lower limit may be paired with any upper limit.

[0049] The polymerization mixture according to the polymerization process of this disclosure may include ethylene, one or more vinyl ester monomers, a free radical polymerization initiator, and optionally one or more inert solvents, such as tetrahydrofuran (THF), chloroform, dichloromethane (DCM), dimethyl sulfoxide (DMSO), dimethyl carbonate (DMC), hexane, cyclohexane, ethyl acetate (EtOAc), acetonitrile, toluene, xylene, diethyl ether, dioxane, dimethylformamide (DMF), benzene, or acetone. Ethylene-based polymers produced under low-pressure conditions can exhibit number-average molecular weights from 1 kDa to 300 kDa, weight-average molecular weights from 1 kDa to 1000 kDa, and MWDs from 1 to 60.

[0050] In some embodiments, comonomers and one or more free radical polymerization initiators are polymerized in a continuous or batch process at temperatures above 150 °C and pressures above 1500 bar (referred to as high-pressure polymerization systems) to produce ethylene-based polymers. For example, pressures greater than 1000 bar, 1100 bar, 1200 bar, 1500 bar, 1600 bar, 1700 bar, 1800 bar, 1900 bar, 2000 bar, 2100 bar, 2200 bar, 2300 bar, 2400 bar, 2500 bar, 3000 bar, 5000 bar, or 10000 bar can be used. Vinyl ester-containing copolymers (which can be copolymers and terpolymers) produced under high-pressure conditions can have a number-average molecular weight (Mn) from 1 kDa to 10000 kDa. n Weight-average molecular weight (M) from 1 kDa to 20,000 kDa w Molecular weight distribution (MWD) is determined by weight-average molecular weight (Mb) obtained through GPC. w ) and number-average molecular weight (M nThe ratio is obtained. The MWD of copolymers and terpolymers produced under high pressure conditions can range from 1 to 60. GPC experiments can be performed by analytical methods, such as gel permeation chromatography combined with triple detection, where the infrared detector IR5 and the four-bridge capillary viscometer are both from PolymerChar, and the octagonal light scattering detector is from Wyatt. A set of four columns (mixed bed, 13 μm, from Tosoh) can be used at a temperature of 140 °C. Experimental conditions can be: concentration of 1 mg / mL, flow rate of 1 mL / min, dissolution temperature and time of 160 °C and 90 min, respectively, and injection volume of 200 μL. The solvent used is TCB (trichlorobenzene) stabilized with 100 ppm BHT.

[0051] In some embodiments, the conversion rate during polymerization in low-pressure and high-pressure polymerization systems (defined as the weight or mass flow rate of the polymer produced divided by the weight or mass flow rate of the monomers and comonomers) may have a lower limit of any one of 0.01%, 0.1%, 1%, 2%, 5%, 7%, 10% and an upper limit of any one of 15%, 17%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60%, 70%, 80%, 90%, 99%, or 100%, wherein any lower limit may be paired with any upper limit.

[0052] thermoplastic polyurethane

[0053] TPU copolymers are block copolymers containing domains formed by the reaction of diisocyanates, chain extenders or short-chain diols, and polyols or long-chain diols. Any type of TPU copolymer known to those skilled in the art is applicable to this specification. Various types of TPU copolymers can be prepared by changing the ratios, structure, and / or molecular weights of the above-described reactive components to fine-tune the structure of the TPU copolymer to the desired final properties of the material.

[0054] The polymer compositions disclosed in this specification may comprise suitable amounts of thermoplastic polyurethane, ranging from a lower limit of one of 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, or 50 wt% and an upper limit of one of 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, 99 wt%, or 99.5 wt%, wherein any lower limit may be combined with any mathematically compatible upper limit.

[0055] The polymer compositions according to this disclosure may include thermoplastic polyurethanes, which may be based on polyesters (e.g., primarily derived from diesters) or polyethers (e.g., based on tetrahydrofuran (THF) ether, polyethylene glycol, or polypropylene glycol). Exemplary TPU copolymers are Epaflex Polyurethanes Srl (Italy), Epaline (Epaflex Polyurethanes Sr1.), Epacol (Epaflex Polyurethanes Srl), Pakoflex (Epaflex Polyurethanes Srl), Elastollan® (BASF, Michigan), Pearlthane® (Lubrizol, Ohio), Pearlthane® ECO (Lubrizol), Estane® (Lubrizol), Pellidine (Lubrizol), Desmopan (Covestro, Germany), New Power®, Irogran® (Huntsman, Texas), Avalon® (Huntsman), Exelast EC (Shin-Etsu Polymers Europe, Netherlands), Laripur (COIMSpA, Italy), Isothane (Greco), Zythane™ (Alliance Polymers & Services, Michigan), and TPU 95A (Ultimaker, Netherlands).

[0056] Compatibilizer

[0057] The polymer composition may also contain one or more compatibilizers to promote blending of the two polymer components. The polymer compositions disclosed in this specification may optionally include a compatibilizer in an amount ranging from a lower limit of 0 wt%, 2 wt%, or 4 wt% to an upper limit of 6 wt%, 8 wt%, or 10 wt%, wherein any lower limit may be combined with any mathematically compatible upper limit.

[0058] Suitable compatibilizers include: organic peroxides; compatibilized ethylene copolymers; compatibilizers comprising epoxy resins and styrene-based polymers; polycarbonate polyols; polybutadiene polyols; polysiloxane polyols, and combinations thereof.

[0059] Suitable organic peroxides include, but are not limited to, 3-hydroxy-1,1-dimethyl butyl peroxynedecanoate, α-isopropylphenyl peroxynedecanoate, tert-amyl peroxynedecanoate, tert-butyl peroxynedecanoate, 2-hydroxy-1,1-dimethyl butyl peroxyneheptanate, α-isopropylphenyl peroxyneheptanate, tert-butyl peroxyneheptanate, di(2-ethylhexyl) peroxydicarbonate, di(n-propyl) peroxydicarbonate, di(sec-butyl) peroxydicarbonate, tert-amyl peroxynepentanoate, and more. Tert-butyl perpentanoate, diisononoyl peroxide, di(dodecanoyl) peroxide, 3-hydroxy-1,1-dimethylbutyl peroxide-2-ethylhexanoate, didecanoyl peroxide, 2,2'-azobis(isobutyronitrile), di(3-carboxypropionyl) peroxide, 2,5-dimethyl-2,5-di-(2-ethylhexanoylperoxy)hexane, benzoyl peroxide, tert-pentyl peroxide-2-ethylhexanoate, tert-butyl peroxide-2-ethylhexanoate, tert-butyl peroxide-isobutyrate, peroxide (cis-3-carboxyl) tert-butyl acrylate, 1,1-di(tert-amylperoxy)cyclohexane, 1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1-di(tert-butylperoxy)cyclohexane, o-tert-amyl-o-(2-ethylhexyl) peroxycarbonate, o-tert-butyl-o-isopropyl peroxycarbonate, o-tert-butyl-o-(2-ethylhexyl) peroxycarbonate, polyester tetra(tert-butyl peroxycarbonate), 2,5-dimethyl-2,5-di-(benzoylperoxy)hexane, tert-amyl peroxyacetate, tert-amyl peroxybenzoate, tert-butyl pernonanoate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, di-tert-butyl dipperoxyphthalate, 2,2-di(tert-butylperoxy) Butane, 2,2-di-(tert-amylperoxy)propane, n-butyl 4,4-di-(tert-butylperoxy)valerate, ethyl 3,3-di-(tert-amylperoxy)butyrate, ethyl 3,3-di-(tert-butylperoxy)butyrate, dicumyl peroxide, α,α'-bis-(tert-butylperoxy)dicumyl peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, di(tert-amyl) peroxide, tert-butyl α-cumyl peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)-3-hexane, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-tripiperoxynonane and mixtures thereof.

[0060] Suitable compatibilizing ethylene copolymers are those having the formula EX, EY, or EXY, wherein E is ethylene, X is an α,β-olefinically unsaturated monomer derived from alkyl acrylates, alkyl methacrylates, alkyl vinyl ethers, carbon monoxide, sulfur dioxide, or mixtures thereof (wherein each alkyl group independently contains 1 to 8 carbon atoms), and Y is an α,β-olefinically unsaturated monomer containing reactive groups capable of forming covalent bonds with the TPU copolymer component and / or the branched vinyl ester copolymer component. In one embodiment, X is methyl acrylate, ethyl acrylate, ethyl methacrylate, or butyl acrylate. In one embodiment, Y is glycidyl methacrylate, ethyl glycidyl acrylate, or butyl glycidyl acrylate. An exemplary compatibilizer is an ethylene-methyl acrylate-glycidyl methacrylate (E-MA-GMA) terpolymer.

[0061] Suitable compatibilizers comprising epoxy resins and styrene-based polymers can be prepared by blending epoxy resins with styrene-based polymers. Specific epoxy resins used can be prepared by reacting an epoxide-containing compound (e.g., epichlorohydrin) with a polyhydroxy compound (e.g., glycerol or bisphenol) in the presence of an alkaline material sufficient to bind hydrochloric acid to form an epoxy-terminated prepolymer. Epoxides can also be prepared by epoxidizing polyolefins with a peroxidizing agent (e.g., peracetic acid). Various epoxy resins are commercially available with a wide range of epoxy content, molecular weight, softening point, and composition, and are also used in this specification. Suitable styrene-based polymers include, but are not limited to, homopolymers of styrene, α-methylstyrene, and p-methylstyrene; high-impact polystyrene modified with rubbery polymers (e.g., styrene-butadiene copolymer rubber, ethylene-propylene copolymer rubber); ethylene-propylene-diene terpolymer rubber; styrene-maleic anhydride copolymer; styrene-acrylonitrile copolymer; styrene-acrylonitrile-butadiene terpolymer; styrene-methyl methacrylate copolymer, etc. An exemplary compatibilizer is styrene-acrylonitrile (SA)-epoxy resin.

[0062] Suitable ethylene-acrylic acid copolymers include, but are not limited to, ethylene-acrylic acid copolymers, such as random terpolymers of ethylene, acrylate and maleic anhydride (Lotader family).

[0063] Suitable polycarbonate polyols include, but are not limited to, polycarbonate polyols such as: polycarbonate diols (e.g., polypropylene carbonate (PPC) diol) or polycarbonate triol; polycaprolactone polyols; alkoxylated polyols; and mixtures thereof. The polyol can be a diol, triol, tetraol, or any other polyol or combination thereof. An exemplary compatibilizer is polypropylene carbonate (PPC) diol.

[0064] Suitable polybutadiene polyols include, but are not limited to, those hydroxyl-functionalized polybutadienes with an average hydroxyl functionality of about 2 to about 3.

[0065] Suitable polysiloxane polyols include, but are not limited to, those polymers having a polysiloxane backbone with terminal or side-chain hydroxyl groups, such as polybutadiene polyols as described in U.S. Patent No. 5,916,992, the entire contents of which are incorporated herein by reference.

[0066] Crosslinking agent

[0067] The polymer composition according to this disclosure may include one or more crosslinking agents capable of generating free radicals during polymer processing. The polymer composition according to this disclosure may optionally include a crosslinking agent in the range of 0 to 10 wt%. The crosslinking agent may be present in amounts ranging from a lower limit of one of 0, 0.001 wt%, 0.01 wt%, 0.1 wt%, 1 wt%, 1.5 wt%, 2 wt%, and 3 wt% to an upper limit of one of 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%, wherein any lower limit may be combined with any mathematically compatible upper limit.

[0068] In one or more embodiments, the crosslinking agent may include: a bifunctional peroxide (e.g., benzoyl peroxide); dicumyl peroxide; di-tert-butyl peroxide; 00-tert-amyl-0-2-ethylhexyl monoperoxycarbonate; tert-butyl cumyl peroxide; tert-butyl 3,5,5-trimethylhexanoate peroxide; tert-butyl benzoate peroxide; 2-ethylhexyl carbonate tert-butyl peroxide; 2,5-dimethyl-2,5-di(tert-butyl peroxide)hexane. (tert-butylperoxide)hexane); 1,1-bis(tert-butylperoxide)-3,3,5-trimethylcyclohexane; 2,5-dimethyl-2,5-bis(tert-butylperoxide)hexyn-3; 3,3,5,7,7-pentamethyl-1,2,4-trioxacycloheptane; 4,4-bis(tert-butylperoxide)valerate butyl ester; bis(2,4-dichlorobenzoyl)peroxide; bis(4-methylbenzoyl)peroxide; bis(tert-butylperoxyisopropyl)benzene peroxide, etc.

[0069] Crosslinking agents may also include peroxides, such as benzoyl peroxide, 2,5-di(isopropylphenylperoxy)-2,5-dimethylhexane, 2,5-di(isopropylphenylperoxy)-2,5-dimethylhexyn-3,4-methyl-4-(tert-butylperoxy)-2-pentanol, butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-neopentate, tert-butyl peroxy-neopentate, tert-butyl peroxy-benzoate, tert-butyl peroxy-2-ethylhexanoate, 4-methyl-4-(tert-pentylperoxy)-2-pentanol, 4-methyl-4-(isopropylphenylperoxy)-2-pentanol, 4-methyl-4-(tert-butylperoxy)-2-pentanone, 4-methyl-4-(tert-pentylperoxy)-2-pentanone, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane. 2,5-Dimethyl-2,5-di(tert-pentylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-di(tert-pentylperoxy)hexyne-3, 2,5-dimethyl-2-tert-butylperoxy-5-hydroperoxyhexane, 2,5-dimethyl-2-isopropylphenylperoxy-5-hydroperoxyhexane 2,5-Dimethyl-2-tert-pentylperoxy-5-hydroperoxyhexane, m / p-α,α-di[(tert-butylperoxy)isopropyl]benzene, 1,3,5-tris(tert-butylperoxyisopropyl)benzene, 1,3,5-tris(tert-pentylperoxyisopropyl)benzene, 1,3,5-tris(cumylperoxyisopropyl)benzene, di[1,3-dimethyl-3-(tert-butylperoxy)butyl]carbonate, di[1,3-dimethyl-3-(tert-pentyl ...dimethylperoxy]carbon [3-(isopropylphenylperoxy)butyl] carbonate, di-tert-pentyl peroxide, tert-pentylisopropylphenyl peroxide, tert-butylisopropenyl peroxide, 2,4,6-tris(butylperoxy)-s-triazine, 1,3,5-tris[1-(tert-butylperoxy)-1-methylethyl]benzene, 1,3,5-tris[(tert-butylperoxy)-isopropyl]benzene, 1,3-dimethyl-3-(tert-butylperoxy)butanol, 1,3-dimethyl-3-(tert-pentylperoxy)butanol, di(2-phenoxyethyl) Peroxydicarbonate, di(4-tert-butylcyclohexyl)peroxydicarbonate, dimyristyl peroxydicarbonate, dibenzyl peroxydicarbonate, di(isobomyl)peroxydicarbonate, 3-isopropylphenylperoxy-1,3-dimethylbutyl methacrylate, 3-tert-butylperoxy-1,3-dimethylbutyl methacrylate, 3-tert-pentylperoxy-1,3-dimethylbutyl methacrylate, tri(1,3-Dimethyl-3-tert-butylperoxybutoxy)vinylsilane, N-[1-{3-(1-methylethenyl)-phenyl)-1-methylethyl]carbamate 1,3-dimethyl-3-(tert-butylperoxy)butyl N-[1-{3-(1-methylethenyl)-phenyl) 1-methylethyl]carbamate, N-[1-{3(1-methylvinyl)-phenyl}-1-methylethyl]carbamate 1,3-dimethyl-3-(tert-amylperoxy)butyl ester, N-[1-{3-(1-methylvinyl)-phenyl}-1-methylethyl]carbamate 1,3-dimethyl-3-(isopropylphenylperoxy))butyl ester, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-butylperoxy)cyclohexane, 4,4-di( Butyl tert-butylperoxy)valerate, ethyl 3,3-di(tert-butylperoxy)butanoate, 2,2-di(tert-butylperoxy)propane, 3,6,6,9,9-pentamethyl-3-ethoxycarbonylmethyl-1,2,4,5-tetraoxacyclononane, 1,4,4-bis(tert-butylperoxy)valerate (-buty 1-4,4-bis(t-butylperoxy)valerate, ethyl-3,3-di(tert-pentylperoxy)butyrate, benzoyl peroxide, OO-tert-butyl-O-hydro-monoperoxy-succinate, OO-tert-pentyl-O-hydro-monoperoxy-succinate, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane (or methyl ethyl ketone peroxide cyclic trimer), methyl ethyl ketone peroxide cyclic dimer, 3,3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-butyl perbenzoate, tert-butyl peroxy acetate, tert-butyl peroxy-2-hexanoate. hexanoate), tert-amyl perbenzoate, tert-amyl peroxyacetate, tert-butyl peroxyisobutyrate, 3-hydroxy-1-hexanoic acid peroxide,1-Dimethyl tert-butyl ester, OO-tert-amyl-O-hydrogen-monoperoxy succinate, OO-tert-butyl-O-hydrogen-monoperoxy succinate, di-t-butyl diperoxyphthalate, tert-butyl peroxy(3,3,5-trimethylhexanoate), 1,4-bis(t-butylperoxycarbonyl)cyclohexane, t-butylperoxy-3,5,5-trimethylhexanoate, tert-butyl peroxy-(cis-3-carboxyl)propionate, 3-methyl-3-tert-butylperoxybutyrate, OO-tert-butyl-O -Isopropylmonoperoxy carbonate (OO-t-butyl-O-isopropylmonoperoxy carbonate), OO-tert-butyl-O-(2-ethylhexyl)monoperoxy carbonate (OO-t-butyl-O-(2-ethyl hexyl)monoperoxy carbonate), 1,1,1-tris[2-(tert-butylperoxycarbonyloxy)ethoxymethyl]propane, 1,1,1-tris[2-(tert-pentylperoxycarbonyloxy)ethoxymethyl]propane, 1,1,1-tris[2-(isopropylphenylperoxycarbonyloxy)ethoxymethyl]propane, OO-tert-pentyl-O-isopropylmonoperoxy carbonate (OO-t-amyl-O-isopropylmonoperoxy) Carbonate, bis(4-methylbenzoyl) peroxide, bis(3-methylbenzoyl) peroxide, bis(2-methylbenzoyl) peroxide, didecanoyl peroxide, dilauryl peroxide, 2,4-dibromobenzoyl peroxide, succinic acid peroxide, dibenzoyl peroxide, bis(2,4-dichlorobenzoyl) peroxide and combinations thereof.

[0070] In one or more embodiments, the crosslinking agent may include: polyisocyanates, such as methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI); triallyl isocyanurate (TAIC), trimethylolpropane-tris-methacrylate (TRIM), triallyl cyanurate (TAC), trifunctional (meth)acrylate ester (TMA), N,N'-m-phenylene dimaleimide (PDM), poly(butadiene)diacrylate (PBDDA), and high vinyl poly(butadiene). Poly(butadiene), HVPBD, trans-polyoctenamer rubber (TOR) (Vestenamer®), and combinations thereof.

[0071] It is also envisioned that the polymer composition could contain dynamic crosslinks as a vitrifier, also known as a "covalent adaptive network," a type of chemically crosslinked polymer in which external stimuli (temperature, stress, pH, etc.) trigger bond exchange reactions, thereby allowing changes in the network topology while maintaining a constant number of bonds and crosslinks. The dynamic covalent bonds present in the vitrifier can undergo association exchange reactions, enabling changes in the network topology, and the material undergoes stress relaxation and flow even if the total number of bonds remains constant over time and does not fluctuate across all times and temperatures. A catalyst can facilitate the exchange reactions of the aforementioned dynamic crosslinks. In one or more embodiments, the catalyst is a metal salt selected from the group consisting of metal salts, metal oxides, metal alkoxides, metal acrylates, metal acetylacetonates, metal hydrides, and metal halides. Such metals may include, for example, zinc, tin, magnesium, cobalt, calcium, titanium, and zirconium.

[0072] elastomer

[0073] The polymer composition according to one or more embodiments of the present disclosure may include one or more elastomers.

[0074] The polymer composition according to this disclosure may optionally include an elastomer in the range of up to 60 wt%. The elastomer may be present in an amount ranging from a lower limit of one of 0, 5 wt%, 10 wt%, and 15 wt% to an upper limit of one of 20 wt%, 30 wt%, 40 wt%, 50 wt%, and 60 wt%, wherein any lower limit may be combined with any mathematically compatible upper limit.

[0075] The elastomers according to this disclosure may include one or more of natural rubber, synthetic rubber, or mixtures thereof. Representative synthetic rubber polymers include diene-based synthetic rubbers, such as homopolymers of conjugated diene monomers and copolymers and terpolymers of conjugated diene monomers with monovinyl aromatic monomers and trienes. Exemplary diene-based compounds include, but are not limited to: polyisoprene (IR), such as 1,4-cis-polyisoprene and 3,4-polyisoprene; chloroprene rubber; polystyrene; styrene-butadiene rubber (SBR); polybutadiene (BR); 1,2-vinyl-polybutadiene; butadiene-isoprene copolymers; butadiene-isoprene-styrene terpolymers; isoprene-styrene copolymers; styrene / isoprene / butadiene copolymers; styrene / isoprene copolymers, emulsion styrene-butadiene copolymers, solution styrene / butadiene copolymers; butyl rubber, such as isobutylene rubber; ethylene / propylene copolymers, such as ethylene propylene diene monomer (EPDM), ethylene propylene rubber (EPM), or ethylene-vinyl acetate (EVA); and blends thereof. Rubber components having branched structures formed by using multifunctional modifiers (e.g., tin tetrachloride) or multifunctional monomers (e.g., divinylbenzene) may also be used. Other suitable rubber components include nitrile rubber, acrylonitrile-butadiene rubber (NBR), silicone rubber (e.g., methyl vinyl silicone rubber, dimethyl silicone rubber, etc.), fluorinated elastomers, acrylic rubber (alkyl acrylate copolymers (ACM), such as ethylene acrylate rubber), epichlorohydrin rubber, chlorinated polyethylene rubber (e.g., chloroprene rubber), chlorosulfonated polyethylene rubber, hydrogenated nitrile rubber, hydrogenated isoprene-isobutylene rubber, tetrafluoroethylene-propylene rubber, and blends thereof.

[0076] foaming agent

[0077] The polymer compositions according to this disclosure may include one or more blowing agents to produce foamed polymer compositions and foams. The polymer compositions according to this disclosure may optionally include a blowing agent in the range of 0 to 20 wt%. The blowing agent may be present in amounts ranging from a lower limit of one of 0, 2 wt%, 4 wt%, 6 wt%, and 8 wt% to an upper limit of one of 10 wt%, 12 wt%, 14 wt%, 16 wt%, 18 wt%, and 20 wt%, wherein any lower limit may be combined with any mathematically compatible upper limit.

[0078] The blowing agent may be a solid, liquid, or gaseous blowing agent. In embodiments using a solid blowing agent, the blowing agent may be combined with the polymer composition in the form of powder or granules.

[0079] The foaming agents according to this disclosure may include chemical foaming agents that decompose at polymer processing temperatures, thereby releasing foaming gases (e.g., N2, CO, CO2, etc.). Examples of chemical foaming agents may include organic foaming agents, including hydrazides (e.g., toluenesulfonyl hydrazide), acyl hydrazides (e.g., oxobis(benzenesulfonyl hydrazide), diphenyl ether-4,4'-disulfonic acid hydrazide, etc.), nitrates, azo compounds (e.g., azodicarbonamide), cyanopentanoic acid, azobis(isobutyronitrile), N-nitroso compounds and other nitrogen-based materials, as well as other compounds known in the art.

[0080] Inorganic chemical foaming agents can include carbonates, such as sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, ammonium carbonate, etc., which can be used alone or in combination with weak organic acids (such as citric acid, lactic acid or acetic acid).

[0081] foaming accelerator

[0082] The polymer compositions according to this disclosure may include one or more foaming accelerators (also referred to as kickers) that enhance or initiate the action of a foaming agent by lowering the relevant activation temperature. For example, a foaming accelerator may be used if the selected foaming agent reacts or decomposes at temperatures above 170 °C (e.g., 220 °C or higher), where the surrounding polymer will degrade if heated to that activation temperature. The foaming accelerator may include any suitable foaming accelerator capable of activating the selected foaming agent. In one or more embodiments, suitable foaming accelerators may include cadmium salts, cadmium-zinc salts, lead salts, lead-zinc salts, barium salts, barium-zinc (Ba-Zn) salts, zinc oxide, titanium dioxide, triethanolamine, diphenylamine, sulfonated aromatic acids and their salts, etc.

[0083] The polymer compositions according to this disclosure may optionally include a foaming accelerator in the range of 0 to 5 wt%. The foaming accelerator may be present in amounts ranging from a lower limit of one of 0, 0.001 wt%, 0.1 wt%, 0.5 wt%, and 1 wt% to an upper limit of one of 2 wt%, 3 wt%, 4 wt%, and 5 wt%, wherein any lower limit may be combined with any mathematically compatible upper limit.

[0084] plasticizer

[0085] The polymer composition according to one or more embodiments may include a plasticizer. The plasticizer may be based on phthalates (e.g., DOP, DOA, DINP, DEHP, DPHP, DIDP, DIOP, DEP, DIBP, etc.), adipate-based (e.g., DEHA, DMAD, DBS, DBM, DIBM, etc.), bio-based (e.g., triethyl citrate, acetylated tributyl citrate, methyl ricinoleate, soybean oil, epoxidized soybean oil, other vegetable oils, etc.), trimellitate, azelaic acid ester, benzoate, sulfonamide, organophosphate, glycol and polyether, polymeric plasticizer, polybutene, etc.

[0086] wax

[0087] The polymer composition according to one or more embodiments may include waxes, such as paraffin wax, polyethylene wax, microcrystalline wax and nanocrystalline wax, natural wax (beeswax, carnauba wax, pure ceresin wax, etc.), petroleum wax, etc.

[0088] Fillers, nanofillers and additives

[0089] The polymer compositions according to this disclosure may include fillers, nanofillers, and additives that, when added to the polymer composition during blending, alter various physical and chemical properties. These fillers, nanofillers, and additives include one or more polymer additives, such as processing aids, lubricants, antistatic agents, clarifying agents, nucleating agents, β-nucleating agents, slip agents, antioxidants, compatibilizers, anti-acid agents, light stabilizers (e.g., HALS), IR absorbers, whitening agents, inorganic fillers, organic and / or inorganic dyes, antiblocking agents, processing aids, flame retardants, plasticizers, biocides, adhesion promoters, metal oxides, mineral fillers, flow aids, oils, antioxidants, antiozone agents, accelerators, and vulcanizing agents.

[0090] The polymer compositions according to this disclosure may contain one or more inorganic fillers, such as talc, glass fiber, marble dust, cement dust, clay, carbon black, feldspar, silica or glass, pyrolytic silica, silicates, calcium silicate, silica powder, glass microspheres, mica, metal oxide particles and nanoparticles (e.g., magnesium oxide, antimony oxide, zinc oxide), inorganic salt particles and nanoparticles (e.g., barium sulfate), wollastonite, alumina, aluminum silicate, titanium oxide, calcium carbonate, polyhedral oligomeric silsesquioxanes (POSS), or recycled EVA. As defined in this disclosure, recycled EVA may be derived from refractory material processed by at least one method (e.g., molding or extrusion), and subsequently ground or shredded from sprues, runners, flash, defective parts, etc. The polymer compositions according to this disclosure may include one or more nanofillers, such as single-walled carbon nanotubes, double-walled and multi-walled carbon nanotubes, nanocellulose, nanocrystalline cellulose, nanoclay, nanometal or ceramic particles, etc.

[0091] Bio-based carbon content

[0092] In one or more embodiments of the polymer composition, the polymer may contain at least a portion of bio-based carbon. Specifically, in one or more embodiments, the polymer composition may exhibit a bio-based carbon content of 1% to 100%, as determined by ASTM D6866-18 Method B. Some embodiments may include at least 1%, 5%, 10%, 20%, 40%, 50%, 60%, 80%, or 100% bio-based carbon. The total bio-based or renewable carbon in the polymer composition may be contributed by bio-based ethylene and / or bio-based vinyl acetate.

[0093] Properties of thermoplastic polymer compositions

[0094] When no crosslinking and / or foaming processes are performed (i.e., when melt blending), polymer compositions prepared by blending TPU components and ethylene-based polymers containing branched vinyl esters can have a content of approximately 0.9 g / cm³. 3 Approximately 1.7 g / cm 3 The density is measured using standard ASTM D1505. In particular, the density can be reduced by introducing copolymers or terpolymers containing branched vinyl esters relative to TPU.

[0095] In one or more embodiments, the polymer composition may have one or more glass transition temperatures (Tg) in the range of -100 °C to 180 °C. In one or more embodiments, the polymer composition may have one or more glass transition temperatures ranging from a lower limit of any one of -100 °C, -80 °C, -60 °C, -50 °C, -40 °C, -30 °C, -20 °C, -10 °C, or 0 °C to an upper limit of 10 °C, 20 °C, 30 °C, 40 °C, 50 °C, 80 °C, 100 °C, 150 °C, or 180 °C, wherein any lower limit may be paired with any upper limit. The polymer composition according to this disclosure may have at least one Tg in the range of -100 °C to 0 °C. In one or more embodiments, the polymer composition may exhibit at least a first Tg in the range of -100 °C to 0 °C and at least a second Tg in the range of 100 °C to 180 °C. The glass transition temperature can be measured according to ASTM D7028-07.

[0096] Polymer compositions according to one or more embodiments of this disclosure may have the following Shore A hardness range as determined by ASTM D2240: from the lower limit of one of 40 Shore A, 45 Shore A, 50 Shore A, 55 Shore A, 60 Shore A, 65 Shore A or 70 Shore A to the upper limit of 70 Shore A, 75 Shore A, 80 Shore A, 85 Shore A, 90 Shore A, 93 Shore A, 95 Shore A, 96 Shore A or 97 Shore A, wherein any lower limit may be paired with any upper limit.

[0097] Polymer compositions according to one or more embodiments of this disclosure may have the following Vicat softening temperature range as determined by ASTM D1525: from a lower limit of any one of 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, 110 °C or 115 °C to an upper limit of 120 °C, 125 °C, 130 °C, 135 °C, 140 °C, 145 °C, 150 °C, 155 °C, 160 °C, 165 °C, 170 °C, 175 °C, 180 °C, 185 °C, 190 °C or 200 °C, wherein any lower limit may be paired with any upper limit.

[0098] Polymer compositions according to one or more embodiments of this disclosure may have the following range of elastic modulus (M100) at 100% tensile strain as determined by ASTM D638: from the lower limit of any one of 300 psi, 400 psi, 500 psi, 600 psi, 700 psi, 800 psi, 900 psi, 1000 psi, 2000 psi, 3000 psi, 4000 psi or 5000 psi to the upper limit of 2000 psi, 4000 psi, 6000 psi, 7000 psi, 8000 psi, 9000 psi, 10000 psi, 20000 psi or 30000 psi, wherein any lower limit may be paired with any mathematically compatible upper limit.

[0099] In one or more embodiments, the polymer composition may have a lower glass transition temperature and higher abrasion resistance compared to a reference blend composition which is essentially composed of TPU and a reference EVA (with the same concentration and ethylene content of the ethylene-based polymer in the polymer composition).

[0100] In one or more embodiments, compared to a reference composition which is substantially composed of TPU, the polymer composition exhibits a reduction of at least 2% in Shore A hardness as measured by ASTM D2240 and an increase of at least 5% in elastic modulus (M100) at 100% tensile strain as measured by ASTM D638.

[0101] Products

[0102] The polymer compositions according to one or more embodiments of this disclosure can be used to produce a variety of polymer articles for a variety of end uses, particularly those in which a lower glass transition temperature, high abrasion resistance, and reduced hardness are desired while maintaining tensile properties. Furthermore, articles of the disclosed compositions are suitable for applications in the footwear industry, particularly soles, midsoles, outsoles, unisole, insoles, monobloc sandals, flip-flops, and sporting goods, and are also suitable for automotive products, furniture products, textile products, sports / recreation products, or consumer electronics products.

[0103] Exemplary articles include shoe soles or shoe parts, films, pipes, fibers, cables, ear tags, motor parts, automotive parts, hoses, belts, damping elements, handrails, furniture elements, ski boots, stop shocks, rollers, ski goggles, powder coatings, antennas and antenna feet, handles, housings, switch foams, adhesives, and cladding and cladding elements.

[0104] Method for preparing polymer compositions

[0105] In one or more embodiments, the polymer composition can be prepared by mixing in a conventional polymer processing condition in a conventional kneader, Banbury mixer, mixing roller, twin-screw extruder, press, etc., and then curing (or crosslinking) or curing plus foaming in a conventional foaming process (e.g., injection molding or compression molding).

[0106] It should also be understood that, when mixed with other components forming the polymer composition, the polymer composition can also be cured, for example, in the presence of a crosslinking agent (including those described above). For embodiments including foaming compositions, foaming and curing can be carried out in the presence of a foaming agent and a crosslinking agent, as well as optionally a foaming accelerator.

[0107] The polymer composition can be extruded using an extruder that can provide gas injection, or, in the case of a chemical blowing agent, the blowing agent can be mixed with the polymer fed into the extruder. Gas is injected into the extruder, or formed in the molten zone of the extruder through the thermal decomposition of the chemical blowing agent. The gas in the polymer (regardless of the gas source) forms bubbles that are distributed throughout the molten polymer. As the molten polymer eventually solidifies, the bubbles result in the formation of a cellular structure or foam material. In certain embodiments, the cellular structure of the foamed composition may be a closed-cell structure. In other embodiments, the cellular structure of the foamed composition may be an open-cell structure.

[0108] application

[0109] In one aspect, this disclosure relates to an article comprising a polymer composition. In some embodiments, the article may be an injection-molded article, a thermoformed article, a film, a foam, a blow-molded article, an additively manufactured article, a compression article, a co-extruded article, a laminated article, an injection blow-molded article, a rotational-molded article, an extruded article, a single-layer article, a multi-layer article, or a pultruded article, etc.

[0110] In some embodiments, articles comprising polymer compositions may be prepared by processes including but not limited to: extrusion molding, co-extrusion molding, extrusion coating, injection molding, compression blow molding, compression molding, injection blow molding, injection stretch blow molding, thermoforming, cast film extrusion, blown film extrusion, blown film process, foaming, extrusion blow molding, injection stretch blow molding, rotational molding, pultrusion, calendering, additive manufacturing, and lamination.

[0111] According to one or more embodiments of this disclosure, the polymer compositions can be used to produce a variety of polymer articles for a variety of end uses, particularly those requiring a low glass transition temperature, high abrasion resistance, and reduced hardness while maintaining tensile properties. Furthermore, articles of the disclosed compositions are suitable for applications in the footwear industry, particularly soles, midsoles, outsoles, unisole, insoles, monobloc sandals, flip-flops, and sporting goods, and are also suitable for automotive products, furniture products, textile products, sports / recreation products, or consumer electronics.

[0112] Exemplary articles include shoe soles or shoe parts, films, pipes, fibers, cables, ear tags, motor parts, automotive parts, hoses, belts, damping elements, handrails, furniture elements, ski boots, stop shocks, rollers, ski goggles, powder coatings, antennas and antenna feet, handles, housings, switch foams, adhesives, and cladding and cladding elements.

[0113] Example

[0114] The examples below are merely illustrative and should not be construed as limiting the scope of this disclosure.

[0115] Material

[0116] VeoVa TM 10 were purchased from Hampton. Estane® 2355-80AE (polyester-based TPU) and Estane® 2103-80AE (polyether-based TPU) were purchased from Lubrizol. HM728 was obtained from Braskem. G1651 was purchased from Kraton. Lotader AX8900 was purchased from SK Functional Polymer.

[0117] method

[0118] Shore A hardness was measured according to ASTM D2240.

[0119] The Vicat softening temperature was measured according to ASTM D1525.

[0120] Tensile data were measured at 20 °C and a crosshead speed of 2 in / min according to ASTM D638-98.

[0121] The morphology of the samples was examined using an atomic force microscope (Nanoscope VIII-Bruker). The cross-section of the bar's center was trimmed into a trapezoidal shape, and this region was cryogenically ultrathin-sectioned at -120 °C using a 35° diamond scalpel. These analyses were performed in tapping mode. Images were acquired using an antimony-doped (n) Si probe (f0 = 320 kHz, K = 42 N / m). Images were acquired at scan sizes of 20 µm, 5 µm, and 2 µm. The parameters used were: line integral gain and scaling gain of 0.2 and 2.0, scan rate of 0.2 Hz or 0.5 Hz, drive frequency of 20.0 mV, and amplitude setpoint of 8.0 nm.

[0122] Melt flow index is measured according to ASTM D1238.

[0123] The TPU blend of the present invention

[0124] Two different ethylene-based polymers (DV001A and DV001B) containing ethylene, vinyl acetate, and branched vinyl esters were prepared in a high-pressure industrial apparatus typically used for the production of EVA copolymers. DV001A contains 5.6 wt% branched vinyl ester (VeoVa). TM 10) and a terpolymer of 28.3 wt% vinyl acetate; DV001B is a terpolymer containing 9.3 wt% VeoVa TM A terpolymer of 10 and 24.1 wt% vinyl acetate (the remainder being ethylene). Typical reactor conditions used to produce the terpolymer samples are shown in Table 1.

[0125] Table 1

[0126] Two types of TPU were used as base materials to generate examples for testing. TPU 1 was a commercial-grade polyester-based TPU, Estane 2355-80AE, with a Shore A hardness of 85 and an MI of 7 g / 10 min (224 °C / 8.7 kg). TPU 2 was a commercial-grade polyether-based TPU, Estane 2103-85AE, with a Shore A hardness of 88 and an MI of 24 g / 10 min (224 °C / 8.7 kg).

[0127] Lotader AX8900 is used as a compatibilizer in blends. It is a commercial random ethylene-methyl acrylate-glycidyl methacrylate terpolymer, wherein the methyl acrylate content is 24 wt% and the glycidyl methacrylate content is 8 wt%.

[0128] Reference TPU blends

[0129] The comparative polymer used for modifying TPU is commercial-grade ethylene-vinyl acetate (EVA 1) HM 728, which has a vinyl acetate content of 28 wt% and a melt flow index (MFR) of 6 g / 10 min (190 °C / 2.16 kg).

[0130] The comparative polymer used for modifying TPU is a commercial linear triblock copolymer G1651 E based on styrene and ethylene / butene (SEB) polymers, which has a bound styrene content of 31.5 wt% and a solution viscosity of 1.5 Pa·s (as measured by KM06 at 25 °C on a 10% m / m solution in toluene).

[0131] Lotader AX8900 is used as a compatibilizer in blends. It is a commercial random ethylene-methyl acrylate-glycidyl methacrylate terpolymer, wherein the methyl acrylate content is 24 wt% and the glycidyl methacrylate content is 8 wt%.

[0132] Preparation of TPU blends

[0133] The materials used to produce the blends of the present invention and the comparative (reference) blends are listed in Table 2 below. The materials were dried overnight in a convection oven at 80 °C and then compounded in a 25 mm 30 L / D twin-screw co-rotating extruder (NFM) at 190 °C and 350 rpm to produce the blends.

[0134] Table 2

[0135] The compounded sample was dried overnight. The dried sample was then injection molded into ASTM D638 Type 1 stretch bar: 1 / 8 inch × 1 / 2 inch × 6 inches, with a barrel temperature of 204 °C, a packaging pressure of 750 psi, an injection speed of 2 inches / second, and a mold temperature of 10 °C.

[0136] Prior to testing, the molded samples were annealed at 80 °C for 24 hours, followed by annealing at 20 °C for 48 hours. The Vicat softening temperature (ASTM D1525), Shore A hardness (ASTM D2240), tensile properties (ASTM D638, at 2 in / min and 20 °C), and morphology of the samples were tested.

[0137] Table 3 below shows the results for Shore A hardness, elastic modulus (M100) at 100% tensile strain, and Vicat softening temperature of the samples listed in Table 2.

[0138] Table 3

[0139] Reference blends 1 and 2 show that, as expected, blending in EVA 1, SEB, and the terpolymer reduces the Shore A hardness of the TPU. This reduction in hardness typically corresponds to a decrease in Vicat temperature, as seen in reference blends 1 and 2. Surprisingly, novel blends 2 and 3 exhibit both improved Vicat temperature and reduced hardness compared to TPU alone (reference 1). The combination of the terpolymer, compatibilizer, and TPU unexpectedly leads to an increase in Vicat temperature. Novel blend 1, which does not contain a compatibilizer, however, produces a lower Shore A hardness and a higher Vicat hardness compared to reference blends 1 and 2, which contain SEB / EVA 1 and a compatibilizer. These results indicate that DV001A and DV001B have better compatibility with TPU compared to the SEB and EVA samples.

[0140] Figure 1 Tensile data for a sample based on TPU 1 are shown. Figure 2 Tensile data for samples based on TPU 2 are shown. Novel blends 2 and 3 exhibit higher stress at equivalent elongation than reference blends 1 and 2, and novel blend 2 outperforms the TPU 1 reference.

[0141] Figure 3A and Figure 3B AFM micrographs of reference blend 1 and reference blend 2 are shown respectively. Figures 3C to 3E AFM micrographs of novel blends 1, 2, and 3 are shown. AFM micrographs are phase signals that show differences in morphology / hardness within the blends. Brighter areas represent the harder TPU matrix, while darker areas are different modifiers. The smaller particle size of the modifiers in novel blends 2 and 3 demonstrates that DV001A and DV001B have better compatibility with TPU compared to SEB and EVA 1 used in the reference blend. This improved compatibility is a likely reason for the improved tensile and Vicat data.

[0142] Although only a few exemplary examples have been described in detail above, those skilled in the art will readily understand that many modifications can be made to the exemplary examples without substantially departing from the invention. Therefore, all such modifications are intended to be included within the scope of this disclosure as defined by the appended claims. In the claims, functional definitions are intended to cover structures described herein as performing the enumerated functions, encompassing not only structural equivalents but also equivalent structures. Thus, although nails and screws may not be structural equivalents, as nails employ a cylindrical surface to hold wooden parts together and screws employ a helical surface, nails and screws can be equivalent structures in the context of fastening wooden parts. The applicant’s explicit intent is not to invoke Section 112(f) of the U.S. Patent Act to limit any claim in this specification, except those claims that expressly use the phrase “means for…” in conjunction with the associated function.

Claims

1. A polymer composition comprising: 0.5 wt% to 45 wt% of ethylene-based polymers produced from ethylene, one or more branched vinyl ester monomers, and optionally vinyl acetate; and 55 wt% to 99.5 wt% thermoplastic polyurethane, in, The one or more branched vinyl ester monomers have a general formula (I) or a general formula (II): (AND); (II), Among them, R 1 and R 2 Independently selected from the group consisting of alkyl or aryl groups, R 3 Choose from the group consisting of hydrogen, alkyl, or aryl groups, and R 1 R 2 and R 3 It has a total carbon number ranging from C3 to C20. Among them, R 4 and R 5 Having a total carbon number of 6 or 7, Wherein, the thermoplastic polyurethane is a polyester-based thermoplastic polyurethane or a polyether-based thermoplastic polyurethane, and The ethylene-based polymer comprises 1 wt% to 30 wt% branched vinyl ester and 0 to 40 wt% vinyl acetate, with the remainder being ethylene.

2. The polymer composition according to claim 1 further comprises a compatibilizer in the range of 0 to 10 wt%.

3. The polymer composition according to claim 2, wherein, The compatibilizer is a reactive compatibilizer.

4. The polymer composition according to claim 2, wherein, The compatibilizer is selected from organic peroxides, ethylene copolymers, epoxy resins, ethylene-acrylic acid copolymers, styrene-based polymers, polycarbonate polyols, polybutadiene polyols, polysiloxane polyols, or combinations thereof.

5. The polymer composition according to claim 1, further comprising an elastomer.

6. The polymer composition according to claim 5, wherein, The elastomer includes natural rubber, synthetic rubber, or mixtures thereof.

7. The polymer composition according to claim 6, wherein, The synthetic rubber polymer is based on dienes, including homopolymers and copolymers of conjugated diene monomers, as well as terpolymers of the conjugated diene monomers with monovinyl aromatic monomers and trienes.

8. The polymer composition according to claim 1, wherein, The polymer composition is cross-linked.

9. The polymer composition according to claim 1, wherein, The polymer composition is dynamically cross-linked.

10. The polymer composition according to claim 1, wherein, The composition is foamed.

11. The polymer composition according to claim 1, wherein, The density of the polymer composition, as measured according to ASTM D1505, is in the range of 0.9 g / cm³. 3 Up to 1.7 g / cm 3 .

12. The polymer composition according to claim 1, wherein, Compared to a reference blend composition consisting essentially of the thermoplastic polyurethane and EVA with the same concentration and ethylene content as the ethylene-based polymer in the polymer composition, the polymer composition exhibits a lower glass transition temperature and higher abrasion resistance.

13. The polymer composition according to claim 1, wherein, The polymer composition has a Shore A hardness range of 50 Shore A to 96 Shore A as measured according to ASTM D2240.

14. The polymer composition according to claim 1, wherein, Compared to a reference composition which is substantially composed of the aforementioned thermoplastic polyurethane, the polymer composition exhibits a reduction of at least 2% in Shore A hardness as measured by ASTM D2240, and an increase of at least 5% in elastic modulus at 100% tensile strain as measured by ASTM D638.

15. The polymer composition according to claim 1, wherein, The polymer composition has an elastic modulus of at least 300 psi at 100% tensile strain, as measured by ASTM D638.

16. The polymer composition according to claim 1, wherein, The polymer composition has a Vicat softening temperature range of 70 °C to 200 °C, as measured according to ASTM D1525.

17. An article formed from the polymeric composition according to any one of claims 1-16.

18. The article of claim 17, wherein, The article is selected from the group consisting of shoe parts, films, pipes, fibers, cables, ear tags, motor parts, hoses, belts, damping elements, furniture elements, rollers, ski goggles, powder coatings, antennas and antenna feet, handles, housings, switch foams, adhesives, and cladding.

19. The article of claim 17, wherein, The article is prepared by a method selected from the group consisting of: injection molding, compression molding, extrusion molding, 3D printing, foaming and thermoforming.

20. A method for preparing a polymer composition according to any one of claims 1-16, comprising: Blend thermoplastic polyurethane and ethylene-based polymers to form blends; as well as The blend is extruded to form the polymer composition.

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