Polymeric materials

Abstract

Formulations for processing polymeric materials, such as recycled polyolefins, are capable of combining relatively large amounts of recycled polyolefins, such as PCR, with virgin resin to obtain excellent mechanical properties, the formulations comprising a free radical generator and a branching agent. The free radical generator can be a peroxide, a hindered amine, a nitroxide, or a metal radical source, the branching agent can comprise moiety (I); or moiety (II); and can be selected from the group consisting of 1-dodecene, diethyl maleate, 1-hexadecene, 1-eicosene, methyl oleate, triphenylstyrene, 1,6-hexanediol dimethacrylate, and benzyl methacrylate.

Description

[0001] This invention relates to polymer materials, and more particularly (but not limited to) to polyolefins. Preferred embodiments relate to polymer materials comprising polyethylene and / or polypropylene; and / or such polymer materials comprising a relatively high content of recycled polyolefins [e.g., post-consumer resin (PCR) and / or post-industrial resin (PIR)].

[0002] Maximizing the amount of recycled polyolefins used in the production of new molded articles is becoming increasingly important. For example, PCR (which itself may contain a mixture of polyolefin resins and other polymers and organic or inorganic contaminations) can be blended with virgin resins to produce large quantities of polymer materials, which can then be melt-blended into pellets or granules, for example. These pellets or granules can then be extruded or injection-molded to produce new articles.

[0003] However, when the amount of recycled resin (e.g., PCR) increases beyond the nominal level (e.g., typically 25% by weight), the mechanical properties of the polymer material tend to decline, leading to processing challenges and potentially resulting in articles with relatively poor mechanical properties. For example, adding recycled resin can adversely affect key properties of the polymer material, such as melt flow, tensile strength, tensile modulus, elongation at break, flexural strength, flexural modulus, heat distortion temperature (HDT), Vicat softening temperature, and / or environmental stress cracking resistance (ESCR). If the PCR used has multiple thermal histories, it may form a gel or experience a decrease in molecular weight during processing due to chain breakage. The net effect is that the final application of polymer materials incorporating PCR can result in molded articles with product defects and excessive waste.

[0004] The use of recycled resin as described above can present certain challenges in ESCR. The risk is that if too high a content of recycled resin is used, the resulting molded articles may be prone to failure under sustained stress below the resin yield point.

[0005] Packaging of consumer goods (typically produced via extrusion blow molding) increasingly demands the use of higher PCR concentrations in production. However, higher PCR concentrations increase the risk of ESCR failure.

[0006] Some commercially available products are designed to address some of the problems described herein. For example, CaCO3 can be added. However, this provides limited improvement to key mechanical properties, and disadvantageously, very high addition amounts are required. Compatibiliser is known, but tends to require high addition amounts and tends to reduce the flexural strength of the finished product, thus limiting its application. Specialty resin grades are commercially available; however, their practicality decreases with increasing recycled content.

[0007] The purpose of the preferred embodiments of the present invention is to solve the above-mentioned problems.

[0008] The preferred embodiment of the present invention aims to enable the use of a greater amount of recycled polyolefins (e.g., PCR) without significantly negatively impacting the mechanical properties of the polyolefins (e.g., impact strength or flexural properties).

[0009] The preferred embodiment of the present invention aims to enable the use of a greater amount of recycled polyolefins (e.g., PCR) without significantly negatively impacting ESCR.

[0010] According to a first aspect of the invention, an formulation for treating polymer materials is provided, the formulation comprising:

[0011] (i) free radical generators; and

[0012] (ii) Branching agents.

[0013] Advantageously, the formulations described herein can be used to treat recycled polyolefins and enable relatively large quantities of recycled polyolefins (e.g., PCR) to bind with virgin resins, thereby obtaining excellent mechanical properties, including excellent ESCR resistance.

[0014] The free radical generator can be an organic or inorganic complex. For example, it can be an inorganic salt or a transition metal complex.

[0015] The free radical generator may be a thermal free radical initiator, a thermal cationic initiator, a photofree radical initiator, or a photocationic initiator. Preferably, the free radical generator is a thermal free radical initiator.

[0016] The free radical generator may be a substituted or unsubstituted phthalimide, peroxy ketal, alkyl or aryl peroxide, organic or inorganic free radical generator, a combination of one or more free radical generators, a polymeric free radical initiator, or an entity that generates free radicals through large particles (e.g., polystyrene or polytetrafluoroethylene).

[0017] The free radical generator may be a peroxide, hindered amine, nitrogen oxide, or metal free radical source.

[0018] Preferably, the free radical generator is stable and storeable at room temperature (25°C). Preferably, the free radical generator can be processed at 220°C, for example, at typical HDPE processing temperatures.

[0019] Preferably, the self-accelerating decomposition temperature (SADT) of the free radical generator is greater than 80°C. This can be determined by examining the free radical generator itself as described in Evaluation 2. Preferably, the t½ (half-life) of the free radical generator is in the range of 100-200°C, more preferably in the range of 100-150°C. Preferably, the free radical generator has the ability to initiate free radical polymerization.

[0020] The free radical generator, such as a peroxide, preferably has a decomposition temperature [which can be appropriately measured by differential scanning calorimetry (DSC)] of at least 100°C, for example, in the range of 100°C to 300°C.

[0021] The free radical generator is preferably a solid peroxide, and preferably has a relatively high half-life and SADT as described above. Generally, peroxides with relatively high molecular weights and large functional groups are thermally stable and therefore preferred. During melt processing (e.g., reactive extrusion), the preferred peroxide participates in the reaction by generating free radicals.

[0022] The free radical generator is preferably a peroxide.

[0023] The free radical generator may be a peroxide having alkyl or aryl substituents; or a peroxide having active functional groups selected from the following: acrylates, esters, ethers, diimides, and cyclic or acyclic hydrocarbons.

[0024] The free radical generator may be selected from: 1,1-di(tert-amylperoxy)cyclohexane, di(4-tert-butylcyclohexyl)peroxydicarbonate, benzoyl peroxide, 2,2-di(tert-butylperoxy)butane, dicerylperoxydicarbonate, 1,1-di(tert-butylperoxy)cyclohexane, acetylacetone peroxide, tert-butylperoxybenzoate, methyl ethyl ketone peroxide / cumyl hydroperoxide, cumyl hydroperoxide, methyl isobutyl ketone peroxide, methyl ethyl ketone peroxide, tert-amylperoxy-2-ethylhexyl carbonate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylperoxy-2-ethylhexyl carbonate, di(2,4-dichlorobenzoyl)peroxide, dicumyl peroxide, 2,5-di... Methyl-2,5-di(tert-butylperoxy)hexane, di(tert-butyl)peroxide, di(tert-butyl)peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyn-3, di(2-ethylhexyl)peroxydicarbonate, di(3,5,5-trimethylhexanoyl)peroxide, dilauroyl peroxide, dimyristyl peroxydicarbonate, tert-butylperoxy-2-ethylhexyl carbonate, tert-butylperoxy-2-ethylhexanoate, tert-pentylperoxy-2-ethylhexanoate, tert-butylperoxyneodecanate, tert-butylperoxy-3,5,5-trimethylhexanoate, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-butylperoxy)cyclohexane, di(4-tert-butylcyclohexyl) Peroxydicarbonate, dimyristyl peroxydicarbonate, acetylacetone peroxide, methyl ethyl ketone peroxide, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, acetylacetone peroxide, methyl ethyl ketone peroxide, acetylacetone peroxide, methyl ethyl ketone peroxide / cumyl hydroperoxide, methyl ethyl ketone peroxide / acetylacetone peroxide, tert-butyl peroxybenzoate, acetylacetone peroxide, methyl isobutyl ketone peroxide, methyl ethyl ketone peroxide, acetylacetone peroxide, tert-butyl peroxybenzoate, acetylacetone peroxide, peroxide dye concentrate, disuccinyl peroxide, tert-amyl hydroperoxide, tert-amyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethyl Hexyl carbonate, tert-amyl peroxyneopentate, tert-butyl hydroperoxide, tert-butyl peroxyacetate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexyl carbonate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxyneopentate, tert-butyl peroxyneopentate, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,4-bis(tert-butylperoxyisopropyl)benzene, tert-butyl cumyl peroxide, n-butyl-4,4-di(tert-butylperoxy)valerate, tert-butyl peroctanoate, tert-butyl peroxyneopentate, di-tert-butyl peroxide, α-cumyl peroxyneopentate, 3-hydroxy-1,1-Dimethylbutylperoxyneodecanate, bis(4-methylbenzoyl)peroxide, and 3,3,5,7,7-pentamethyl-1,2,4-trioxane-heptane.

[0025] The free radical generator may be a di(optionally substituted) alkyl peroxide. When optionally substituted, it may be substituted by a hydrocarbon portion (e.g., containing only hydrogen and carbon atoms), such as a phenyl portion. The free radical generator may be a dialkyl peroxide. The free radical generator may be selected from: dicumyl peroxide, 1,1-di(tert-butylperoxy)cyclohexane, tert-butylperoxybenzoate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 1-(anthraquinone-2-yl)ethylimidazolium carboxylate.

[0026] The free radical generator may contain one or more peroxide (OO) groups, which are combined only with portions containing only carbon and hydrogen atoms. The free radical generator may contain peroxide groups and formula -CR 50 R 51 R 52 A combination of parts, where R 50 R 51 and R 52 It is independently selected from phenyl and methyl, and the free carbon atom is preferably directly bonded to the oxygen atom of the peroxide group.

[0027] The preferred free radical generators have a t½ (half-life) in the range of 100-150°C. Preferred examples include: 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane, di(tert-butyl)peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, di(tert-butylperoxyisopropyl)benzene, tert-butylcumyl peroxide, di(tert-pentyl)peroxide, dicumyl peroxide, butyl 4,4-di(tert-butylperoxy)valerate, tert-butylperoxybenzoate, 2,2-di(tert-butylperoxy)butane, tert-pentylperoxybenzoate, and tert-butylperoxyacetate. tert-butylperoxy(2-ethylhexyl) carbonate, tert-butylperoxyisopropyl carbonate, tert-butylperoxy-3,5,5-trimethylhexanoate, 1,1-di(tert-butylperoxy)cyclohexane, tert-amylperoxyacetate, tert-amylperoxy(2-ethylhexyl) carbonate, 1,1-di(tert-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-di(tert-amylperoxy)cyclohexane, tert-butyl monoperoxymaleate, 1,1'-azobis(hexahydrobenzonitrile), bis(4-methylbenzoyl)peroxide, and 3,3,5,7,7-pentamethyl-1,2,4-trioxacycloheptane.

[0028] The free radical generator may be selected from 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and dicumyl peroxide.

[0029] The branching agent may be an olefin having internal or terminal C=C double bonds; and / or the branching agent may be conjugated or non-conjugated; and / or the olefin may be substituted or unsubstituted; and / or the molecular weight of the olefin may be in the range of 50-1500; and / or the olefin may have C4-C... 100 The carbon chain; and / or the olefin may be an oligomer or a low molecular weight polymer; and / or the olefin may be linear or branched; and / or the olefin may contain reactive groups, which may include epoxide, cyanide or oxazinone functional groups; and / or the olefin may be an alkyne and / or a liquid rubber, such as polyisobutylene or polybutadiene.

[0030] The branching agent may be an α-olefin or an activated olefin, for example, configured to react with a free radical source to generate a new covalent bond in an α-olefin or an activated olefin.

[0031] The branching agent may contain a portion of:

[0032] (I); or

[0033] part

[0034] (II)

[0035] When the branching agent includes part of formula I, it can be the following formula:

[0036] (III)

[0037] Where R 1 The portion representing a hydrogen atom or optional substitution may contain only carbon and hydrogen atoms and / or may contain a saturated or unsaturated hydrocarbon portion and / or may be an optionally substituted alkyl or alkenyl group and / or may contain one or more functional groups selected from the following: ether, nitro, ester, amide, and hydroxyl; and

[0038] R 2 The term indicates an optionally substituted portion, which may contain only carbon and hydrogen atoms and / or may contain a saturated or unsaturated hydrocarbon moiety and / or may be an optionally substituted alkyl or alkenyl group and / or may contain one or more functional groups selected from the following: ether, nitro, ester, amide, and hydroxyl; and / or

[0039] R 1 and R 2 Together, they defined the cyclic structure with optional substitution.

[0040] When the branching agent includes part of formula II, it can be the formula:

[0041] IV

[0042] in:

[0043] R 3 and R 4 Independently representing an optionally substituted alkyl or aryl group, or representing an ester group bonded via its carbonyl carbon to a partially IV alkenyl carbon atom. Optionally substituted alkyl groups can be optionally substituted C1-C... 10 Alkyl group. The alkyl group may be optionally substituted, for example, by ester moiety substitution. The aryl group may be optionally substituted, for example, an unsubstituted phenyl group; and

[0044] R 10 This indicates an optionally substituted alkyl or aryl group, or an ester group bonded via its carbonyl carbon to a portion of the alkenyl carbon atom of IV. Optionally substituted alkyl groups can be C1-C... 10 Alkyl group. The alkyl group may be optionally substituted, for example, by ester moiety. The aryl group may be optionally substituted, for example, by unsubstituted phenyl group.

[0045] When R 10 When representing a hydrogen atom, R 3 and R 4 Alkyl groups that can be substituted independently, such as substituted C1-C alkyl groups. 10 Alkyl group, or ester group, refers to an alkyl group bonded to a portion of the alkenyl carbon atom via its carbonyl carbon. The alkyl group may be optionally substituted independently, for example, by the ester portion.

[0046] In one implementation, R 3 R 4 and R 5 It can independently represent an optionally substituted (preferably unsubstituted) alkyl or aryl group. In embodiments, preferably, R 3 R 4 and R 5 At least one (preferably each) may independently represent an optionally substituted (preferably unsubstituted) aryl group, such as a phenyl group.

[0047] When R 10 When indicating an optionally substituted alkyl or aryl group, it preferably indicates an optionally substituted (preferably unsubstituted) aryl group, such as a phenyl group.

[0048] The branching agent may contain 4 to 100 carbon atoms, preferably 6 to 50 carbon atoms, and more preferably 10 to 30 carbon atoms.

[0049] The melting point of the branching agent may be greater than 10°C, for example, greater than 50°C or greater than 90°C; and the melting point may be less than 300°C or less than 200°C.

[0050] The boiling point of the branching agent may be greater than 150°C, for example, greater than 175°C; and the boiling point may be less than 400°C, less than 300°C, or less than 250°C. For the avoidance of doubt, the above boiling point refers to the boiling point of the branching agent alone. In some embodiments, the liquid carrier described below can serve to reduce the vapor pressure of the branching agent in the formulation.

[0051] When the branching agent comprises a portion of Formula I and / or a portion of Formula III, it may be an α-olefin. Preferred α-olefins comprise 6 to 30 carbon atoms, or 8 to 22 carbon atoms, or 10 to 25 carbon atoms.

[0052] The preferred α-olefin is 1-dodecene.

[0053] When the branching agent comprises a portion of Formula I and / or a portion of Formula III, it may be selected from: 4-vinylanisole, α-methylstyrene, 3-nitrostyrene, benzyl methacrylate, 1,1-stilbene, camphene, diacetone acrylamide, 1,9-decadiene, vinylcyclohexene, and eugenol. In some cases, when the branching agent comprises a portion of Formula III, it may be 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0054] When the branching agent contains a portion of formula IV, R 3 The following part can be selected.

[0055] (V);

[0056] Or alkyl, preferably linear alkyl, which is optionally substituted with an ester moiety; and

[0057] R 4 The derivative may be a moiety or alkyl group of formula (V), preferably a linear alkyl group, which may optionally be substituted with an ester moiety.

[0058] When the branching agent contains a portion of formula IV, R 3 and R 4 Can be selected independently

[0059] (V)

[0060] (VI); and

[0061] (VII)

[0062] in, Carbon represents the position of the double bond with the IV moiety, and n, m, and q are integers, preferably in the range of 1 to 10. In a preferred embodiment, n can be in the range of 1 to 3; m can be in the range of 2 to 10, preferably 4 to 9; and q can be in the range of 2 to 10, preferably 4 to 9.

[0063] When the branching agent contains a portion of formula IV, preferably, R 3 Or R 4 At least one comprising portion (V) or (VI) of the formula. When the branching agent comprises portion IV, preferably, R 3 and R 4 None of them are part of Equation VII.

[0064] Examples of compounds of formula IV include methyl oleate and diethyl maleate.

[0065] Examples of branching agents include 1-dodecene, diethyl maleate, 1-hexadecene, 1-eicosene, methyl oleate, triphenylene, 1,6-hexanediol dimethacrylate, and benzyl methacrylate.

[0066] The formulation may contain 0.0001 to 50.0% by weight of the free radical generating agent. The formulation may contain 1 to 10% by weight, preferably 1 to 8% by weight, more preferably 2 to 7% by weight of the free radical generating agent.

[0067] The total weight percentage of all free radical generators in the formulation can range from 0.0001 to 50.0% by weight. This total can range from 1 to 10% by weight, preferably 1 to 8% by weight, more preferably 2 to 7% by weight.

[0068] The formulation may contain 0.0001 to 99.0% by weight of the branching agent. The formulation may contain 1 to 50% by weight, preferably 5 to 30% by weight, more preferably 10 to 25% by weight of the branching agent.

[0069] The total weight percentage of all branching agents in the formulation can range from 0.0001 to 50.0% by weight.

[0070] The total may be in the range of 1 to 50% by weight, preferably 5 to 30% by weight, more preferably 10 to 25% by weight.

[0071] In the formulation, the ratio defined by the weight percentage of the free radical generator divided by the weight percentage of the branching agent can be in the range of 1:1 to 1:100, for example, in the range of 1:1 to 1:10.

[0072] In the formulation, the ratio defined by the sum of the weight percentages of all free radical generators divided by the sum of the weight percentages of all branching agents can be in the range of 1:1 to 1:100, for example, in the range of 1:1 to 1:10.

[0073] In one embodiment (A1), the formulation may not contain a carrier separate from the free radical generator and the branching agent (e.g., an inert component and / or a component provided to dissolve or disperse the free radical generator and / or branching agent, but which is not intended to react or form an active substance when the formulation is used to treat polyolefins). In this case, the total weight percentage of all free radical generators and all branching agents in the formulation may be at least 90% by weight, for example at least 94% by weight, at least 98% by weight, or at least 99% by weight.

[0074] In embodiment (A1), the branching agent may be selected as both a branching agent and a carrier of a free radical generator. In this case, the branching agent is preferably a liquid, and the free radical generator may be a liquid miscible with the branching agent, or a solid finely dispersed in the branching agent.

[0075] In embodiment (A1), the formulation may comprise 1 to 50% by weight of the free radical generator and 50 to 99% by weight of the branching agent. Preferably, the formulation comprises 10 to 50% by weight of the free radical generator and 50 to 90% by weight of the branching agent.

[0076] In the embodiment (A1), the formulation may comprise a total of 1 to 50% by weight of a free radical generator and a total of 50 to 99% by weight of a branching agent. Preferably, the formulation comprises a total of 10 to 50% by weight of a free radical generator and a total of 50 to 90% by weight of a branching agent.

[0077] In the embodiment (A1), the ratio defined by dividing the weight % of the free radical generator by the weight % of the branching agent can be in the range of 1:1 to 1:100, for example, in the range of 1:1 to 1:10.

[0078] In the embodiment (A1), the ratio defined by dividing the total weight % of all free radical generators by the total weight % of all branching agents can be in the range of 1:1 to 1:100, for example, in the range of 1:1 to 1:10.

[0079] The formulation described in the first aspect may be a liquid formulation or a solid formulation, such as a solid masterbatch. The formulation may comprise:

[0080] (i) the free radical generating agent;

[0081] (ii) the branching agent; and

[0082] (iii) Carrier.

[0083] Preferably, the free radical generator and the branching agent are dispersed in the carrier, preferably in a substantially uniform manner. Preferably, the free radical generator and the branching agent are compatible with the carrier.

[0084] Preferably, unless otherwise stated herein, references to “liquid” and “solid” refer to their state at 25°C and standard pressure (101325 Pa).

[0085] When the formulation is a liquid, the carrier is preferably a liquid. The boiling point of the carrier at 760 mm Hg (according to ASTM D1078) is in the range of 150 to 1150 °C, preferably in the range of 275 to 1000 °C or 275 to 500 °C. The viscosity of the carrier (measured using a Brookfield viscometer, rotor No. 2, 20 rpm, at 20 °C) is in the range of 50 to 3500 cP, more preferably in the range of 200 to 1800 cP.

[0086] The carrier may include a hydrocarbon-containing liquid. The carrier may contain one or more liquids, such as one or more hydrocarbon-containing liquids. The carrier may contain low molecular weight waxes. The carrier may contain triglycerides. The carrier may contain liquid rubber. The carrier may contain mineral oil. When the formulation is a liquid, preferably, the free radical generator is completely dissolved in the carrier at the concentration used, or it is itself a liquid. When the formulation is a liquid, preferably, the branching agent is completely dissolved in the carrier at the concentration used, or it is a liquid.

[0087] Examples of liquid rubbers include polyisobutylene with low Mw (e.g., 1000–2500) and / or viscosity in the range of 200–4750 cSt; polybutadiene (Mw 5000–10000); and ethylene-α-olefin copolymers (Mw 2700–16000). Generally, the viscosity range of the carrier is 400–50000 cps.

[0088] When the carrier comprises one or more liquids, it may contain one or more of the aforementioned carriers. For example, the carrier may comprise a mixture of mineral oil (e.g., 10 to 30 wt%) and polyisobutylene and / or liquid rubber (e.g., 70 to 90 wt%).

[0089] When the formulation is solid, the carrier may comprise a polyolefin and / or a thermoplastic elastomer (TPE). The carrier may include carriers typically used for solid masterbatches. The carrier may comprise a polyolefin, such as polyethylene (e.g., HDPE or LDPE) or polypropylene, a styrene block polymer [e.g., styrene-ethylene-butene-styrene (SEBS) or styrene-butadiene copolymer (SBC)], ethylene-vinyl acetate (EVA), or ethylene-propylene rubber (EPR).

[0090] The formulation (including the carrier) may contain 1 to 10% by weight, preferably 1 to 8% by weight, more preferably 2 to 7% by weight of the free radical generator.

[0091] The total weight percentage of all free radical generating agents in the formulation may be in the range of 1 to 10% by weight, preferably 1 to 8% by weight, more preferably 2 to 7% by weight.

[0092] The formulation (including the carrier) may contain 5 to 30% by weight, preferably 10 to 25% by weight, of the branching agent.

[0093] The total weight percentage of all branching agents in the formulation may be in the range of 5 to 30% by weight, more preferably 10 to 25% by weight.

[0094] In the formulation (containing the carrier), the ratio defined by the weight percentage of the free radical generator divided by the weight percentage of the branching agent can be in the range of 1:1 to 1:100, for example, in the range of 1:1 to 1:10.

[0095] In the formulation (containing the carrier), the ratio defined by the sum of the weight % of all free radical generators divided by the sum of the weight % of all branching agents can be in the range of 1:1 to 1:100, for example, in the range of 1:1 to 1:10.

[0096] The formulation may contain 50 to 94% by weight of the carrier, preferably 70 to 90% by weight of the carrier.

[0097] The sum of the weight percentages of all carriers in the formulation may be in the range of 50 to 94% by weight, preferably 70 to 90% by weight.

[0098] In the formulation, the ratio defined by dividing the weight percentage of all carriers by the sum of the weight percentages of all free radical generators may be in the range of 1 to 95 or 2 to 90.

[0099] In the formulation, the ratio defined by dividing the weight percentage of all carriers by the sum of the weight percentages of all branching agents can be in the range of 1 to 95 or 2 to 90.

[0100] The formulation may contain a radical mediator / polymerization inhibitor that is suitably capable of accepting or providing free radicals and preventing pre-reaction of monomers (e.g., branching agents). The radical mediator / polymerization inhibitor may contain a sterically hindered hydroxyl group. The radical mediator / polymerization inhibitor may be selected from: hydroquinone (e.g., monomethyl ether hydroquinone), TEMPO derivatives, lipophilic organic compounds (e.g., butylated hydroxytoluene (BHT)), copper(II) dibutyldithiocarbamate, cobalt 2-ethylhexanoate, and phenothiazines. Preferably, the radical mediator / polymerization inhibitor is selected from BHT, hydroquinone, and TEMPO.

[0101] The formulation may contain 0 to 5% by weight (e.g., 0.001 to 3% by weight) of the free radical mediator / polymerization inhibitor.

[0102] The formulation may contain a colorant, which may be a pigment. The formulation may contain a total of 0 to 50% by weight (e.g., 0 to 10% by weight) of the colorant. The colorant may be included to counteract any discoloration in the polymeric material to which the formulation may be added as described herein.

[0103] The formulation may contain an antioxidant / heat stabilizer. The antioxidant may be a phenol, phosphite, thioether, or organosulfur compound. The formulation may contain antioxidants / free radical scavengers / anti-crosslinking agents selected from the following: glutathione, lipoic acid, vitamins such as ascorbic acid (vitamin C), vitamin B, vitamin D, vitamin E, tocopherols (synthetic or natural, α-, γ-, δ-), vitamin acetate, water-soluble tocopherol derivatives, tocotrienols, water-soluble tocotrienol derivatives; melatonin, carotenoids including carotene, lutein, pycnogenol, glycosides, trehalose, polyphenols and flavonoids, quercetin, lycopene, lutein, selenium, nitric oxide, curcumin, 2-hydroxytetronic acid; hemp seed extract, synthetic antioxidants such as tert-butylhydroquinone, 6-amino-3-pyridinol, butylated hydroxyanisole, butylated hydroxytoluene, ethoxyquinone, tannins, propyl gallate, other gallate esters, Aquanox TMThe formulation may include: families of Irganox® and Irganox® B (including Irganox® 1010, Irganox® 1076, Irganox® 1330, and Irganox® 1035); the Irgafos® family; phenolic compounds with different chain lengths and different numbers of OH groups; enzymes with antioxidant properties (e.g., superoxide dismutase); herbal or plant extracts with antioxidant properties, such as St. John's wort, green tea extract, grape seed extract, rosemary, oregano extract, and mixtures, derivatives, analogs, or conjugated forms thereof. The formulation may contain antioxidants that are primary antioxidants with reactive OH or NH groups, such as hindered phenols or secondary aromatic amines; or secondary antioxidants, such as organophosphorus compounds or thiosynergists; or multifunctional antioxidants, hydroxylamines, or carbon-center radical scavengers, such as lactones or acrylated bisphenols. Antioxidants may be selected individually or used in any combination. Antioxidants can be used in combination with hydroperoxide decomposers.

[0104] The formulation may contain a total of 0.0001-50%, preferably less than 5% by weight, and more preferably 0.0001-2% by weight of antioxidants / heat stabilizers.

[0105] When the formulation is a liquid, it may contain a viscosity control agent. The viscosity control agent may be a surfactant and / or fumed silica. The viscosity control agent may be a wax, silica, povidone, carbomer, poloxamer, carboxymethyl cellulose, hydroxyethyl cellulose, or polyacrylic acid. The formulation may contain 0 to 50% by weight, 0.0001 to 50% by weight, 0.0001 to 5% by weight, or 0.0001 to 3% by weight of the viscosity control agent.

[0106] In some cases, the formulation may contain one or more fillers (e.g., inorganic fillers, such as CaCO3). Preferably, the formulation contains less than 1% by weight, less than 0.5% by weight, or less than 0.1% by weight of filler, such as inorganic fillers.

[0107] According to a second aspect of the invention, a mixture is provided, the mixture comprising:

[0108] (a) Polymer materials;

[0109] (b) Free radical generators or their residues;

[0110] (c) a branching agent or its residue; and, optionally (but preferably)

[0111] (d) Carrier.

[0112] Preferably, the mixture comprises the polymer material and the formulation as described in the first aspect. The mixture may contain residues of the free radical generator produced by heat treatment (e.g., reactive extrusion) of the mixture. The mixture may contain residues of the branching agent produced by heat treatment (e.g., reactive extrusion) of the mixture. When the carrier is unfunctionalized (e.g., it contains an oil such as mineral oil), the carrier is soluble in the polymer material. When the carrier is functionalized, the carrier may undergo pyrolysis or reaction, which is produced by heat treatment (e.g., reactive extrusion) of the mixture.

[0113] The polymer material preferably comprises one or more polyolefins. Preferably, it comprises at least two polyolefins from different sources and / or with different properties and / or performance. The polymer material preferably comprises polyethylene. It may contain 50 to 100% by weight of polyethylene. The polymer material preferably comprises recycled materials, such as PCR or PIR. It may contain polyethylene PCR, especially HDPE PCR. The polymer material preferably contains at least 25% by weight of recycled materials, such as PCR. The polymer material may contain 25 to 100% by weight, 25 to 75% by weight, or 25 to 50% by weight of recycled materials, such as PCR. The polymer material may contain up to 50% by weight of polypropylene (PP), such as 10 to 50% by weight of PP. The composition of the PCR may differ from each other. For example, the PCR may contain inorganic contaminants and / or may be contaminated by filler. For example, the PCR may contain up to 3% by weight of inorganic contaminants, such as 0.5 to 1% by weight of inorganic contaminants.

[0114] The polymer material may contain virgin polymers, such as virgin polyethylene, especially virgin HDPE. The polymer material preferably contains at least 25% by weight of virgin polymers. The polymer material may contain 25 to 75% by weight or 50 to 75% by weight of virgin polymers. In some cases, the polymer material may contain about 100% by weight of virgin polymers, such as PE.

[0115] The free radical generator, branching agent, and carrier may have any of the characteristics described in the first aspect.

[0116] The mixture may be in solid form, such as pellets or granules.

[0117] The mixture may contain at least 90% by weight, preferably at least 94% by weight, and more preferably at least 96% by weight of polyolefins. It may contain less than 99% by weight or less than 98% by weight of polyolefins. The mixture may contain at least 90% by weight, preferably at least 94% by weight, and more preferably at least 96% by weight of polyethylene. It may contain less than 99% by weight or less than 98% by weight of polyethylene.

[0118] According to the third aspect, products subjected to the following treatments [e.g., melt processing and / or reactions (e.g., reactive extrusion)] are provided:

[0119] (a) Polymer materials; and

[0120] (b) Free radical generators;

[0121] (c) a branching agent; and, optionally (but preferably)

[0122] (d) Carrier.

[0123] The product can be obtained by treating the polymer material with the formulation described in the first aspect (e.g., melt processing and / or reaction, such as reactive extrusion).

[0124] The product may be in the form of granules or pellets. Alternatively, the product may be in the form of a molded article, for example, produced by extrusion (such as extrusion blow molding), compression molding, or injection molding. The molded article may be a packaged article, such as a receptacle or container or sheet.

[0125] The polymer material, free radical generator, branching agent, and carrier may have any of the characteristics described in the first and / or second aspects.

[0126] According to a fourth aspect of the invention, a method for improving the mechanical properties of a polymer material, wherein the polymer material optionally comprises recycled polymer material, the method comprising:

[0127] (i) Select a polymer material first substance, wherein the first substance comprises a first polymer material and optionally includes recycled polymer material;

[0128] (ii) contacting the first substance with the formulation described in the first aspect and / or preparing the mixture described in the second aspect; and

[0129] (iii) The mixture generated in step (ii) by melt processing (e.g., by reactive extrusion).

[0130] The first polymer material may comprise a polyolefin, such as polyethylene and / or polypropylene. The first polymer material is preferably a non-recycled polymer material, such as not being PCR. The first polymer material may be a virgin polymer material, such as a virgin polyolefin. It may be virgin polyethylene or virgin polypropylene. Virgin polyethylene is preferred.

[0131] The first polymer material may contain at least 80 wt%, at least 90 wt%, or at least 95 wt% of virgin polyolefin. Alternatively, the first polymer material may contain at least 80 wt%, at least 90 wt%, or at least 95 wt% of virgin polyethylene; or the first polymer material may contain at least 80 wt%, at least 90 wt%, or at least 95 wt% of virgin polypropylene.

[0132] The recycled polymer material (if included) may include waste polymer material, PCR, or PIR. The recycled polymer material may include recycled polyolefins, such as recycled polyethylene and / or polypropylene. The recycled polymer material may include PCR.

[0133] The polymer material produced by this method may comprise 50 to 100% by weight of the first polymer material and 0 to 50% by weight of recycled polymer material. The polymer material produced by this method may comprise 50 to 80% by weight of the first polymer material and 20 to 50% by weight of recycled polymer material.

[0134] The polymer material produced by this method can be in the form of granules or pellets.

[0135] The polymer material can be in the form of molded articles, such as articles produced by extrusion (e.g., extrusion blow molding), compression molding, or injection molding. The molded article can be a packaging article, such as a storage container or shelf. The molded article can also be an extrusion blow molded article. The molded article can be a packaging article, such as a storage container or shelf, or sheet.

[0136] The method is preferably a method for improving the ESCR of the polymer material. For example, when the ESCR is determined according to the method described herein, it can be improved by at least 50%, preferably at least 100%, and more preferably at least 200%. Such a high percentage improvement is necessary to ensure that rHDPE can be used in higher-value applications such as consumer products.

[0137] According to the fifth aspect, molded articles, pellets, or granules are provided, the molded articles, pellets, or granules comprising a polymeric material, such as that described herein (e.g., comprising the first polymeric material and optionally the recycled polymeric material described in the fourth aspect), and trace amounts of one or more of the following:

[0138] Free radical generators or their residues as described herein;

[0139] As described herein, branching agents or their residues; and / or

[0140] As described in this article, the carrier or its residue.

[0141] By using the formulation described in the first aspect to appropriately modify the polymer material, for example, to make the branching agent used in the formulation part of the polymer backbone, a beneficial effect on mechanical properties is achieved. The reaction between the branching agent and the polymer backbone can be determined by analytical methods designed to analyze polymer fragments (e.g., pyrolysis GC-MS).

[0142] The presence / degradation of free radical generators and branching agents can be determined by LC-MS / GC-MS.

[0143] Preferably, the molded article contains trace amounts of the free radical generating agent or residues as described herein, as well as the branching agent or residues as described herein.

[0144] Any feature of any aspect of any invention described herein may be combined with any feature of any other invention described herein, with necessary modifications.

[0145] The specific embodiments of the present invention will be described below through examples.

[0146] The following materials will be mentioned below:

[0147] Native HDPE – refers to HDPE grade H055025 from Ineos;

[0148] PCR HDPE refers to commercially available recycled HDPE.

[0149] Luperox 101 refers to 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane from Arkema, CAS number 78-63-7, molecular weight: 290.4 g, melting point: 8℃, active oxygen: 11.1%;

[0150] Luperox 101XL45 refers to 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane from Sigma Aldrich, CAS number 78-63-7, which is blended with calcium carbonate and silica.

[0151] The following assessments were conducted:

[0152] Assessment 1 – Environmental Stress Cracking Test (ESCR)

[0153] Evaluation was conducted using a bending strip test under Condition B, according to ASTM D1693. Under Condition B, the bent test resin strip was immersed in a 10% Igepal® solution at 50°C. The strip was a plate-like material with dimensions L x B x thickness (4 cm x 1.5 cm x 3 mm). A 0.5 mm notch was cut into the strip to create stress points before immersion in the 50°C 10% Igepal® solution. Failure time was measured.

[0154] Evaluation 2 – Self-Accelerating Decomposition Temperature (SADT) Measurement

[0155] Place the test peroxide in an oven set to the test temperature. Start the timer when the peroxide temperature drops 2°C below the test temperature. Maintain the oven temperature constant for one week, or until a runaway event occurs. If the test (oven) temperature does not exceed 6°C within one week, the peroxide "passes". If the test (oven) temperature exceeds 6°C within one week, the peroxide "fails". Repeat the test in 5°C increments until failure is reached. The failure temperature is reported as the SADT of the peroxide. Additionally, secondary information regarding the severity of decomposition may be recorded.

[0156] Example 1 – General procedure for preparing HDPE granules from recycled HDPE.

[0157] Virgin HDPE and PCR HDPE (50:50 wt%) were mixed with a formulation containing a carrier, peroxide, and branching agent. After thorough mixing, the sample was processed in a twin-screw extruder at a nominal screw temperature of 230°C and a production rate of 15 kg / h to produce granules.

[0158] Example 2 – General procedure for compression molding or injection molding of granules.

[0159] The granules prepared in Example 1 were compression molded or injection molded to prepare the test specimens as described above. In the case of compression molding, the specimen was a compression-molded plate with dimensions L x B x thickness (20 cm x 15 cm x 3 mm). Furthermore, the compression-molded plate was die-punched into a rectangular specimen with dimensions L x B x thickness (4 cm x 1.5 cm x 3 mm). In the case of compression molding, injection molding was used to prepare a rectangular specimen with dimensions L x B x thickness (4 cm x 1.5 cm x 2 mm).

[0160] Examples 3 to 13 – Specific formulations used to prepare the granules

[0161] Following the procedure in Example 1, particles were prepared using the components listed in the table below, with the remainder consisting of virgin HDPE and PCR HDPE (50:50 weight percentage).

[0162]

[0163] Example 20 – Extrusion and Compression Molding Data of PCR from General Recycle Stream

[0164] Particles comprising a 50:50 mixture of EBM-grade virgin HDPE and PCR HDPE from a general recycled stream, with a baseline ESCR (F50) of 17 hours, were selected and compression molded as described in Example 2. ESCR and other properties were measured as described in Evaluation 1. The above were compared with particles produced and compression molded from the same HDPE (as described in Examples 1 and 2). The results are as follows:

[0165]

[0166] The table shows that by incorporating formulations, the key mechanical properties of HDPE resin remain almost unchanged, but advantageously, they have a significant impact on ESCR.

[0167] Example 21 – Compression Molding Data of Food Contact Grade PCR

[0168] Following the procedure in Example 20, food contact grade PCR was performed with a baseline ESCR (F50) of 15 hours. The results are shown in the table below:

[0169]

[0170] Food-grade PCR can be derived from closed-loop recovery streams, thus achieving higher purity, but its ESCR performance is typically lower due to the resin grades used in the market. It should be understood that by incorporating the formulation of Example 5, the ESCR of this food-contact resin can be increased by 120%.

[0171] Example 22 – Compression molding data of commercially available low ESCR grade virgin HDPE

[0172] Following the procedure in Example 20, low-quality native resin-grade PCR was performed, with a baseline ESCR (F50) of 8 hours. The results are shown in the table below:

[0173]

[0174] Example 23 – Injection Molding Data from PCR in a General Recycle Stream

[0175] Particles comprising a 50:50 mixture of EBM-grade virgin HDPE and PCR from a general recycled stream (baseline ESCR (F50) of 495 h) were injection molded as described in Example 2, and the ESCR was measured as described in Evaluation 1. The results, shown below, indicate that the presence of the short-chain branching agent provides a benefit compared to formulations containing only peroxides (Examples 7 and 8).

[0176]

[0177] Example 24 – Injection Molding Data of PCR with Low ESCR Benchmark Level

[0178] Following the procedure of Example 23, EBM-grade virgin HDPE and a 50:50 resin mixture from a general recycled stream (based on ESCR (F50) of 135 h) were injection molded, and the results are shown in the table below.

[0179]

[0180] Example 25 – Injection Molding Data for PCR with Low ESCR Baseline and Disubstituted Olefins as Branching Agents

[0181] Following the procedure of Example 23, EBM-grade virgin HDPE and a 50:50 resin mixture from a general recycled stream (based on ESCR(F50) of 147 h) were injection molded, and the results are shown in the table below.

[0182]

[0183] Examples 26-31 – Compression molding data using formulations containing alternating chain branching agents

[0184] The formulation was prepared according to the procedure described in Example 20, as shown in the table below, and the ESCR was evaluated as described in Evaluation 1.

[0185]

[0186] Example 32 – Injection Molding Data for Sheet PCR

[0187] A sheet containing 100% post-consumer recycled material (with a baseline ESCR (F50) of 17 hours) was injection molded as described in Example 2, and the ESCR was measured as described in Evaluation 1.

[0188]

[0189] Example 33 – Injection Molding Data for Sheet PCR

[0190] A sheet containing 100% post-consumer recycled material (with a baseline ESCR (F50) of 130 h) was injection molded as described in Example 2, and the ESCR was measured as described in Evaluation 1.

[0191]

[0192] Example 34 – Injection Molding Data of Food-Grade PCR

[0193] Pellet containing 100% food-grade post-consumer recycled material (with a baseline ESCR (F50) of 64 h) was injection molded as described in Example 2, and the ESCR was measured as described in Evaluation 1.

[0194]

[0195] Example 35 – Injection Molding Data of PCR at an ESCR Baseline Level

[0196] Following the procedure of Example 23, a 50:50 resin mixture of EBM-grade virgin HDPE and PCR from a general recycled stream (with a baseline ESCR (F50) of 215 h) was injection molded as described in Example 2, and the ESCR was measured as described in Evaluation 1.

[0197]

[0198] Example 36 – Injection Molding Data of PCR at an ESCR Benchmark Level

[0199] Following the procedure of Example 23, a 50:50 resin mixture of EBM-grade virgin HDPE and PCR from a general recycled stream (with a baseline ESCR (F50) of 281 h) was injection molded as described in Example 2, and the ESCR was measured as described in Evaluation 1.

[0200]

[0201] Example 37 – Injection Molding Data of PCR at an ESCR Baseline Level

[0202] Following the procedure of Example 23, a 50:50 resin mixture of EBM-grade virgin HDPE and PCR from a general recycled stream (with a baseline ESCR (F50) of 127 h) was injection molded as described in Example 2, and the ESCR was measured as described in Evaluation 1.

[0203]

[0204] Example 38 – Injection Molding Data of PCR with Low ESCR Baseline Levels

[0205] Following the procedure of Example 23, a 50:50 resin mixture of EBM-grade virgin HDPE and PCR from a general recycled stream (with a baseline ESCR (F50) of 88 h) was injection molded as described in Example 2, and the ESCR was measured as described in Evaluation 1.

[0206]

[0207] Example 39 – Injection Molding Data of Food Contact Grade PCR

[0208] Following the procedure of Example 23, a 50:50 resin mixture of EBM-grade virgin HDPE and food-contact grade PCR (with a baseline ESCR (F50) of 88 h) was injection molded as described in Example 2, and the ESCR was measured as described in Evaluation 1.

[0209]

[0210] Examples 40-43 – Compression Molding Data Using Formulations Containing Alternating Peroxides

[0211] Particles containing 100% virgin EBM-grade virgin HDPE (ESCR (F50) baseline: 8 h) were selected and compression molded as described in Example 2. The formulations in the table below were prepared as described above, and the ESCR was evaluated as described in Evaluation 1.

[0212]

[0213] Examples 44-45 – Compression molding data using food-grade PCR formulations

[0214] Particles containing 100% food-grade post-consumer recycled material (ESCR (F50) baseline: 11 h) were selected and compression molded as described in Example 2. The formulations in the table below were prepared as described above, and the ESCR was evaluated as described in Evaluation 1.

[0215]

[0216] Examples 46-47 – Compression Molding Data Using Universal PCR Reagents

[0217] Particles containing 100% general post-consumer recycled material (ESCR (F50) baseline: 29 h) were selected and compression molded as described in Example 2. The formulations in the table below were prepared as described above, and the ESCR was evaluated as described in Evaluation 1.

[0218]

[0219] This invention is not limited to the details of the embodiments described above. The invention extends to any new type or combination of features disclosed in this specification (including any appended claims, abstract, and drawings), or to any new type or combination of any method or process step so disclosed.

Claims

1. A formulation for treating polymer materials, said formulation comprising: (i) free radical generators; and (ii) Branching agents.

2. The formulation of claim 1, wherein the free radical generator is a peroxide, a hindered amine, a nitrogen oxide, or a metal free radical source.

3. The formulation of claim 1 or claim 2, wherein the free radical generating agent is a peroxide.

4. The formulation as claimed in any of the preceding claims, wherein the free radical generator is selected from: dicumyl peroxide, 1,1-di(tert-butylperoxy)cyclohexane, tert-butylperoxybenzoate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and 1-(anthraquinone-2-yl)ethylimidazolium carboxylate.

5. The formulation as claimed in any of the preceding claims, wherein the branching agent is an olefin containing an internal or terminal C=C double bond.

6. The formulation according to any one of the preceding claims, wherein the branching agent comprises a portion (I); or part (II)。 7. The formulation of claim 6, wherein: A) The branching agent comprises a portion of the following formula: (III) in: R 1 The portion representing a hydrogen atom or optional substitution, said portion comprising only carbon and hydrogen atoms and / or comprising a saturated or unsaturated hydrocarbon portion and / or an optionally substituted alkyl or alkenyl group and / or comprising one or more functional groups selected from the following: ether, nitro, ester, amide, and hydroxyl; and R 2 The portion representing a hydrogen atom or optional substitution, said portion comprising only carbon and hydrogen atoms and / or comprising a saturated or unsaturated hydrocarbon portion and / or an optionally substituted alkyl or alkenyl group and / or comprising one or more functional groups selected from the following: ether, nitro, ester, amide, and hydroxyl; or R 1 and R 2 Together, define the cyclic structure with optional substitution; or B) The branching agent comprises a portion of the following formula: IV in: R 3 and R 4 Independently representing an optionally substituted alkyl or aryl group, or representing an ester group bonded via its carbonyl carbon to a portion of the alkenyl carbon atom of IV; and R 10 It indicates an alkyl or aryl group that is optionally substituted, or an ester group that is bonded to a portion of the alkenyl carbon atom via its carbonyl carbon.

8. The formulation of claim 7, wherein when R 10 When representing a hydrogen atom, R 3 and R 4 Independently representing an optionally substituted alkyl group, such as an optionally substituted C1-C alkyl group. 10 Alkyl, or ester group, which is bonded by its carbonyl carbon to a portion of the alkenyl carbon atom of IV.

9. The formulation according to any one of the preceding claims, wherein the branching agent comprises 4 to 100, preferably 6 to 50, more preferably 10 to 30 carbon atoms; and / or The branching agent has a melting point greater than 10°C; and the melting point is less than 300°C or less than 200°C.

10. The formulation as claimed in any of the preceding claims, wherein the branching agent is an α-olefin, such as 1-dodecene; or the branching agent is selected from: 4-vinylanisole, α-methylstyrene, 3-nitrostyrene, benzyl methacrylate, 1,1-stilbene, camphene, diacetone acrylamide, 1,9-decadiene, vinylcyclohexene, and eugenol.

11. The formulation as claimed in any of the preceding claims, wherein the branching agent comprises a portion of the following formula: IV, in, R 3 and R 4 Selected independently from: (V) (VI); and (VII) in, Carbon indicates the position where it is bonded to a partial IV double bond, and n, m, and q are integers.

12. The formulation as claimed in any of the preceding claims, wherein the branching agent is selected from: 1-dodecene, diethyl maleate, 1-hexadecene, 1-eicosene, methyl oleate, triphenylene, 1,6-hexanediol dimethacrylate and benzyl methacrylate.

13. The formulation as claimed in any of the preceding claims, wherein the formulation comprises a carrier.

14. The formulation of claim 13, wherein the free radical generating agent is completely dissolved in the carrier and / or the branching agent is completely dissolved in the carrier, wherein, Optionally, the carrier comprises a hydrocarbon-containing liquid.

15. The formulation according to any one of claims 1 to 13, wherein the formulation is a solid, the solid optionally being selected from: polyolefins, styrene block polymers, ethylene-vinyl acetate (EVA) or ethylene propylene rubber (EPR).

16. The formulation as claimed in any of the preceding claims, wherein the formulation comprises: 1 to 10% by weight of the free radical generator; 1 to 50% by weight of the branching agent; 49 to 98% by weight of the carrier.

17. The formulation according to any one of claims 13 to 16, wherein: The total weight percentage of all free radical generators in the formulation is in the range of 0.01 to 2.0% by weight; The total weight percentage of all branching agents in the formulation is in the range of 0.01 to 2.0% by weight; The total weight percentage of all carriers in the formulation is in the range of 50% to 99.9% by weight.

18. The formulation as described in any of the preceding claims, wherein, In the formulation: The ratio defined by the weight percentage of the free radical generator divided by the weight percentage of the branching agent is in the range of 1:1 to 1:100, for example, in the range of 1:1 to 1:10; and / or The ratio defined by dividing the total weight percentage of all free radical generators by the total weight percentage of all branching agents is in the range of 1:1 to 1:100, for example, in the range of 1:1 to 1:

10.

19. The formulation of any one of the preceding claims, wherein the formulation comprises a radical mediator / polymerization inhibitor that is capable of accepting or providing free radicals and preventing pre-reaction of monomers.

20. A mixture comprising: (a) Polymer materials; (b) Free radical generators or their residues; (c) a branching agent or its residue; and, optionally (but preferably) (d) Carrier.

21. The mixture of claim 20, wherein the mixture comprises the polymer material and the formulation of any one of claims 1 to 19.

22. The mixture of claim 20 or claim 21, wherein the polymer material comprises one or more polyolefins.

23. The mixture of any one of claims 20 to 22, wherein the mixture comprises at least two different sources and / or polyolefins with different properties and / or performance.

24. The mixture of any one of claims 20 to 23, wherein the polymeric material comprises polyethylene.

25. The mixture of any one of claims 20 to 24, wherein the polymer material comprises recycled material, such as PCR or PIR.

26. The mixture of any one of claims 20 to 25, wherein the polymer material comprises at least 25% by weight of a virgin polymer.

27. The mixture of any one of claims 20 to 26, wherein the mixture is in solid form, such as pellets or granules.

28. Products that have undergone the following treatment: (a) Polymer materials; and (b) Free radical generators; (c) a branching agent; and, optionally (but preferably) (d) Carrier.

29. The product of claim 28, wherein the product is produced by treating the polymer material (e.g., melt processing and / or reaction) with an agent as described in any one of claims 1 to 19, and the product is in the form of granules or pellets or articles, such as containers or extruded sheets or films.

30. A method for improving the mechanical properties of a polymer material, wherein the polymer material optionally comprises recycled polymer material, the method comprising: (i) Select a first polymer material, wherein the first material comprises a first polymer material and optionally comprises recycled polymer material; (ii) contacting the first substance with the formulation of any one of claims 1 to 19 and / or with the mixture of any one of claims 20 to 27; and (iii) The mixture produced in the melt processing step (ii).

31. The method of claim 30, wherein the first polymer material comprises a polyolefin, such as polyethylene and / or polypropylene, and comprises at least 80% by weight of virgin polyolefin.

32. The method of claim 30 or claim 31, wherein the polymer material produced in the method comprises 50 to 100% by weight of the first polymer material and 0 to 50% by weight of recycled polymer material; and optionally, the polymer material produced in the method is in granule or pellet form.

33. The method of any one of claims 30 to 32, wherein the method is a method for improving the environmental stress cracking resistance (ESCR) of the polymer material.

34. A molded article, pellet, or granule, wherein the molded article, pellet, or granule comprises a polymeric material and trace amounts of one or more of the following: The free radical generator or its residue as described in any of the preceding claims; The branching agent or its residue as described in any of the preceding claims; and / or The carrier or its residue as described in any of the preceding claims; and / or The polymer material described herein contains a portion of the branching agent.

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