Plastic resin modifier composition and method for preparing thermoplastic materials and articles using the same

Abstract

The present disclosure relates to thermoplastic resin modifier compositions, methods of converting the compositions into functional resins, and plastic articles prepared from the resins.

Description

Technical Field

[0001] The present disclosure relates to thermoplastic resin modifier compositions, methods of converting the compositions into functional resins, and plastic articles prepared from the resins. Background Art

[0002] Any discussion of the prior art in this specification should not be considered as an admission that such prior art is widely known or forms part of the common general knowledge in the field.

[0003] Existing technologies for imparting antifouling, antimicrobial, and antibiofilm properties to inanimate substrates to reduce adhesion and inhibit microbial growth / colonization are categorized into six general categories: (i) release kill, (ii) contact kill, (iii) controlled consumption coatings, (iv) self-polishing coatings, (v) fouling release coatings, and (vi) combinations of the above.

[0004] Technologies such as release-based killing involve immobilizing antimicrobial compounds to surfaces, which are released over time to provide an antimicrobial effect. Over time, such surfaces may lose their antimicrobial properties as the immobilized antimicrobial compounds are depleted. Immobilized antimicrobial compounds can also be harmful to the environment to which they are released.

[0005] Alternative technologies include minimizing microbial adhesion by creating biomimetic surface topography. However, the manufacturing process is complex and expensive, making it unsuitable for mass production in low-end industries. Further technologies utilize robust encapsulation, stimuli-responsive materials, solid supports, or even the bacteria themselves to trigger or maintain the release of the biocide from the carrier matrix. While having strong antimicrobial properties, these technologies rely on release-based killing, so their effectiveness decreases over time. Additional technologies rely on attached devices or external energy fields to impart antifouling properties to the substrate surface.

[0006] Recently, scalable coating and biocide-free technologies have been developed for producing inherently antimicrobial plastic formulations without affecting the physical properties of the modified substrate. However, the manufacturing methods involve the use of several nonionic surfactants consisting of short-chain aliphatic ethers, heterofunctional oligo(alkylene glycols), and polysorbates, which are susceptible to oxidative degradation and enhanced peroxide formation when combined with a thermal free-radical polymerization initiator in a single pot.

[0007] The present disclosure seeks to overcome or ameliorate at least some of the above-mentioned disadvantages. Summary of the Invention

[0008] In a first aspect, a thermoplastic resin modifier composition is provided, comprising, consisting of, or consisting essentially of:

[0009] (i) vinyl monomers;

[0010] (ii) copolymerizable anhydrides;

[0011] (iii) a thermal free radical polymerization initiator; and

[0012] (iv) Thermoplastic resins.

[0013] The vinyl monomer may be present in the composition in an amount between about 0.5% (w / w) and about 4% (w / w).

[0014] The copolymerizable anhydride may be present in the composition in an amount between about 0.5% (w / w) and about 4% (w / w).

[0015] The thermoplastic resin may be present in the composition in an amount between about 90% (w / w) and about 98% (w / w).

[0016] The thermal free radical polymerization initiator may be present in the composition in an amount between about 0.05% (w / w) and about 4% (w / w).

[0017] The vinyl monomer may contain one or more moieties having antibacterial, antiviral or antifouling properties.

[0018] The one or more moieties having antibacterial, antiviral or antifouling properties may be hydroxyl, amino or carboxyl groups.

[0019] The one or more moieties having antimicrobial, antiviral or antifouling properties can be natural peptides, N-substituted amides, squalene, tannins, saponins, flavonoids, alkaloids, steroids, lactones, lectins, lactams, pilicides, curlicides, alkyl glycosides, aminoglycosides, sugar-containing polymers, glycolipids, sugar esters, quaternary ammonium compounds, terpenes, terpenoids, fatty acids, fatty acid esters, alkylamines, alkylamine oxides, alcohol alkoxylates, nitroxides, halamines, diaryl ethers, xanthones, quinones, coumarins, polyacetylene, guanidines, halogens, phospho derivatives, sulfo derivatives, phenol derivatives, benzoic acid derivatives, organometallics, pyridinium derivatives, piperazine derivatives, pyrrolidone derivatives, aniline derivatives, biguanides and related compounds, oximes and related compounds, isothiazolinones and related compounds, indole derivatives, heteroazole derivatives, heteropyrroline derivatives, hydrazide-hydrazone derivatives, pyrans and related compounds, furans and related compounds, macrolides, tetracyclines, oxazolidinones, quinolones, amidoximes, amidoamines, triazoles, imidazoles, carbamates, dialdehydes, cyclic aldehydes, isothiocyanates, paraformaldehydes, cycloalkanoates, citrates, creosote, N-organodiazeniumdioxy-metal, sulfonamides, lincosamides, arsenic compounds, boron compounds, organochlorines, and polypropyleneimines.

[0020] The vinyl monomer can be a short chain olefin, styrene, alkyl acrylate, alkyl acrylate, vinyl acetate, vinyl alcohol, vinyl phenol, vinyl alkyl ether, vinyl halide, vinyl acetic acid, acrylonitrile, acrylamide, vinyl silane, vinyl sulfide, vinyl sulfone, vinyl sulfoxide, vinyl ethylene carbonate, vinyl pyrrolidone, vinyl carbazole, vinyl norbornene, unsaturated fatty acid or unsaturated fatty acid ester.

[0021] In one embodiment, the vinyl monomer is styrene, alpha-methylstyrene, vinyl naphthalene, isobutylene, vinyl norbornene, butyl vinyl ether, or 2-chloroethyl vinyl ether.

[0022] The thermoplastic resin modifier composition may include multiple vinyl monomers.

[0023] In some embodiments, the plurality of vinyl monomers may be selected from vinyl acetate, acrylamide, N-isopropylacrylamide, N-vinylpyrrolidone, N-hydroxymethylacrylamide, 2-methoxyethyl acrylate, furfuryl methacrylate, tetrahydrofurfuryl acrylate, 4-acryloylmorpholine, 2-N-morpholinoethyl methacrylate, acrylamidoglycolic acid, acrylonitrile, methacrylic acid, methyl methacrylate, 2-ethylhexyl acrylate, butyl acrylate, isobornyl methacrylate, 2-hydroxyethyl methacrylate, 2-aminoethyl methacrylate, 2-(dimethylamino)ethyl methacrylate, 3-methacryloyloxypropyltrimethoxysilane, 2-carboxyethyl acrylate, 2-azacycloheptaneethyl methacrylate, glycidyl methacrylate, allyl glycidyl ether, 2-vinylpyridine, 4-tert-butoxystyrene, and 4-vinylcatechol acetonide.

[0024] The copolymerizable anhydride may be an organic anhydride, such as maleic anhydride or tetrahydrophthalic anhydride.

[0025] The thermal radical polymerization initiator may be a peroxide or an azo compound.

[0026] In one embodiment, the free radical polymerization initiator may be a mixture of benzoyl peroxide and dicumyl peroxide.

[0027] Benzoyl peroxide and dicumyl peroxide may be present in a molar ratio of between about 20:80 and about 80:20.

[0028] The thermoplastic resin may be a medium to high flow homopolyolefin, a multi-block copolymer, a random copolymer, or a mixture thereof.

[0029] The thermoplastic resin may be an addition polymer, a polyolefin elastomer, a thermoplastic olefin, a thermoplastic vulcanizate, or a rubber.

[0030] The thermoplastic resin can be PE, PP, PB, COC, CBC, PCHE, PMP, PVB, PAN, NBR, EPR, PI, SEBS, SEPS, SBS, SIS, MBS, ABS, AES, HNBR, XNBR, ACM, IIR, ECO, EBA, EVA, EVOH, EAA, EMA, EPDM, ETFE, ECTFE, EVCL, CPE, OPE, TPEE, TPC, TPU, TPAE, PEBA, TSPCU, poly(ethylene-co-1-octene), poly(ethylene-co-1-hexene), poly(ethylene-co-1-butene), chloroprene rubber, olefin metathesis products, or any polymer compound having repeating units consisting of aliphatic-, cyclo- or aliphatic-alkyl, aliphatic-alkenyl or aliphatic-alkynyl groups containing at least one or more CH units in the main chain or side chain, or any combination thereof.

[0031] The thermoplastic resin modifier composition may further include an organic solvent.

[0032] The thermoplastic resin modifier composition may further include a deodorant.

[0033] The thermoplastic resin modifier composition may be free or substantially free of surfactants, such as nonionic surfactants.

[0034] In a second aspect, there is provided a method for preparing a modified thermoplastic resin composition, the method comprising, consisting of, or consisting essentially of:

[0035] (i) vinyl monomers;

[0036] (ii) copolymerizable anhydrides;

[0037] (iii) a thermal free radical polymerization initiator; and

[0038] (iv) thermoplastic resins combined to provide a mixture,

[0039] The mixture is then subjected to melt processing or solvent assisted solid phase polymerization.

[0040] The vinyl monomer may be present in the mixture in an amount between about 0.5% (w / w) and about 4% (w / w).

[0041] The copolymerizable anhydride may be present in the mixture in an amount between about 0.5% (w / w) and about 4% (w / w).

[0042] The thermoplastic resin may be present in the mixture in an amount between about 90% (w / w) and about 98% (w / w).

[0043] The thermal free radical polymerization initiator may be present in the mixture in an amount between about 0.05% (w / w) and about 4% (w / w).

[0044] Melt processing may include extrusion, molding, film blowing, spinning, stretching, pressing, kneading, rolling or thermoforming. In one embodiment, melt processing includes extrusion.

[0045] Each of the vinyl monomer, the copolymerizable anhydride, the thermal radical polymerization initiator and the thermoplastic resin may be as defined in the first aspect.

[0046] The mixture may further comprise an organic solvent.

[0047] The mixture may further comprise a deodorant.

[0048] The mixture may be free or substantially free of surfactants, such as nonionic surfactants.

[0049] The mixture may comprise only components (i) to (iv).

[0050] The modified thermoplastic resin composition may be subjected to surface treatment.

[0051] The surface treatment may be a treatment that imparts antifouling, oil-repellent, and / or water-repellent properties to the modified thermoplastic resin composition.

[0052] In a third aspect, there is provided a modified thermoplastic resin composition whenever prepared by the method of the second aspect.

[0053] In a fourth aspect, there is provided a method for preparing a functional resin composition, comprising combining the modified thermoplastic resin composition of the third aspect with one or more additives to form a mixture, and subjecting the mixture to melt processing.

[0054] One or more additives may be present in the composition in an amount between about 90% (w / w) and about 99% (w / w).

[0055] The one or more additives may include one or more compounds having antibacterial, antiviral or antifouling properties.

[0056] One or more compounds having antibacterial, antiviral or antifouling properties may be present in the composition in an amount between about 0.05% (w / w) and about 2% (w / w).

[0057] The one or more compounds having antibacterial, antiviral or antifouling properties may be a hydrophilic compound.

[0058] One or more of the compounds having antibacterial, antiviral or antifouling properties may be amphiphilic compounds.

[0059] The one or more compounds having antibacterial, antiviral or antifouling properties may be one or more alcohol ethoxylates.

[0060] The amphiphilic compound may have an HLB value greater than about 7.

[0061] The amphiphilic compound may have an HLB value between about 7 and about 20.

[0062] The one or more additives may include a core resin.

[0063] The core resin may be present in the composition in an amount between about 90% (w / w) and about 99% (w / w).

[0064] The one or more additives may include an antioxidant.

[0065] Melt processing may include extrusion, molding, film blowing, spinning, stretching, pressing, kneading, rolling, or thermoforming.

[0066] Melt processing may include extrusion.

[0067] In a fifth aspect, there is provided a functional resin composition prepared by the method of the fourth aspect.

[0068] In a sixth aspect, there is provided a method for producing a plastic article, comprising shaping the functional resin composition of the fifth aspect.

[0069] Shaping can be achieved by molding.

[0070] The molding may be injection molding, rotational molding, blow molding or compression molding.

[0071] In an embodiment of the sixth aspect, there is provided a method for preparing a plastic product, comprising:

[0072] (i) will:

[0073] (a) modified thermoplastic resin composition;

[0074] (b) core resin; and

[0075] (c) a compound selected from the group consisting of alcohol ethoxylates, alkylene oxides, and polyethylene glycols in combination to form a mixture;

[0076] (ii) subjecting the mixture to melt processing or solvent-assisted solid phase polymerization to provide a functional resin composition; and

[0077] (iii) shaping the functional resin composition to provide a plastic article,

[0078] And wherein the modified thermoplastic resin composition is prepared by mixing:

[0079] (d) vinyl monomers;

[0080] (e) copolymerizable anhydrides;

[0081] (f) a thermal free radical polymerization initiator; and

[0082] (g) a thermoplastic resin to form a mixture, and

[0083] (iv) by subjecting the mixture to melt processing or solvent-assisted solid phase polymerization.

[0084] In a mixture comprising (a), (b), and (c), component (a) may be present in an amount between about 0.5% (w / w) and about 3% (w / w), component (b) may be present in an amount between about 95% (w / w) and about 99% (w / w), and component (c) may be present in an amount between about 0.05% (w / w) and about 3% (w / w).

[0085] In a mixture comprising (d), (e), (f) and (g), component (d) may be present in an amount between about 0.5% (w / w) and about 5% (w / w), component (e) may be present in an amount between about 0.5% (w / w) and about 5% (w / w), component (f) may be present in an amount between about 0.05% (w / w) and about 3% (w / w), and component (g) may be present in an amount between about 90% (w / w) and about 99% (w / w).

[0086] The mixture comprising (d), (e), (f) and (g) may comprise only components (d), (e), (f) and (g).

[0087] The core resin may be polypropylene.

[0088] The polypropylene may be a polypropylene random copolymer.

[0089] In step (c), the compound may be an alcohol ethoxylate.

[0090] Alcohol ethoxylates may have the following general formula: RO(CH2CH2O) n H, where R is C 12 -C 14 alkyl and n=3 to 23.

[0091] Alcohol ethoxylates may have the following general formula: RO(CH2CH2O) n H, where R is C 12 -C 14 Alkyl and n=3 to 9.

[0092] The alcohol ethoxylates may have an HLB 10 value of between about 10 and 11.

[0093] Melt processing in steps (ii) and (iv) may include extrusion.

[0094] The mixture in step (i) may further comprise an antioxidant.

[0095] The vinyl monomer may be styrene.

[0096] The copolymerizable anhydride may be maleic anhydride.

[0097] The thermal radical polymerization initiator may be dicumyl peroxide.

[0098] The thermoplastic resin may be polypropylene.

[0099] The mixture of (d), (e), (f) and (g) may be free or substantially free of surfactant.

[0100] The shaping in step (iii) can be performed by molding.

[0101] The molding may be injection molding.

[0102] The plastic product may be a protein-resistant plastic product.

[0103] Plastic products can be antibacterial and / or antiviral.

[0104] In a seventh aspect, a method for producing a plastic article is provided, the method comprising combining the modified thermoplastic resin composition of the third aspect with one or more additives to form a masterbatch, combining the masterbatch with a core resin to form a mixture, and processing the mixture to form a plastic article.

[0105] In an eighth aspect, there is provided a method for producing a plastic article, comprising combining the modified thermoplastic resin composition of the third aspect with a masterbatch and a core resin to form a mixture, and processing the mixture to form a plastic article.

[0106] The masterbatch may contain one or more compounds having antibacterial, antiviral or antifouling properties.

[0107] The one or more compounds having antibacterial, antiviral or antifouling properties may be a hydrophilic compound.

[0108] One or more of the compounds having antibacterial, antiviral or antifouling properties may be amphiphilic compounds.

[0109] The amphiphilic compound may have an HLB value greater than about 7.

[0110] The amphiphilic compound may have an HLB value between about 7 and about 20.

[0111] In an embodiment of the eighth aspect, there is provided a method for preparing a plastic article, comprising:

[0112] (i) will:

[0113] (a) modified thermoplastic resin composition;

[0114] (b) core resin; and

[0115] (c) combining a masterbatch comprising an alcohol ethoxylate, an alkylene oxide, or a polyethylene glycol to form a mixture; and

[0116] (ii) shaping the mixture to provide a plastic article,

[0117] The modified thermoplastic resin composition is prepared by mixing:

[0118] (d) vinyl monomers;

[0119] (e) copolymerizable anhydrides;

[0120] (f) a thermal free radical polymerization initiator; and

[0121] (g) a thermoplastic resin to form a mixture, and

[0122] (iii) Prepared by subjecting a mixture of (d), (e), (f) and (g) to melt processing or solvent-assisted solid phase polymerization.

[0123] In a mixture comprising (a), (b), and (c), component (a) may be present in an amount between about 5% (w / w) and about 15% (w / w), component (b) may be present in an amount between about 80% (w / w) and about 95% (w / w), and component (c) may be present in an amount between about 1% (w / w) and about 7.5% (w / w).

[0124] In a mixture comprising (d), (e), (f) and (g), component (d) may be present in an amount between about 0.5% (w / w) and about 5% (w / w), component (e) may be present in an amount between about 2% (w / w) and about 10% (w / w), component (f) may be present in an amount between about 0.05% (w / w) and about 3% (w / w), and component (g) may be present in an amount between about 90% (w / w) and about 99% (w / w).

[0125] The masterbatch may further contain a core resin.

[0126] The masterbatch may be one prepared by melt mixing an alcohol ethoxylate, an alkylene oxide or a polyethylene glycol and a core material resin.

[0127] The core resin may be polypropylene.

[0128] The polypropylene may be a polypropylene random copolymer.

[0129] The core material resin may be a thermoplastic elastomer.

[0130] The masterbatch may comprise alcohol ethoxylate.

[0131] Alcohol ethoxylates may have the following general formula: RO(CH2CH2O) n H, where R is C 12 -C 14 Alkyl and n=3-9.

[0132] Alcohol ethoxylates may have the following general formula: RO(CH2CH2O) n H, where R is C 12 -C 14 Alkyl and n=5.

[0133] The alcohol ethoxylates may have an HLB value between 10 and 11.

[0134] The shaping in step (ii) can be performed by molding.

[0135] The molding may be injection molding.

[0136] Melt processing in step (iii) may comprise extrusion.

[0137] The vinyl monomer may be styrene.

[0138] The thermoplastic resin may be a thermoplastic elastomer.

[0139] The copolymerizable anhydride may be maleic anhydride.

[0140] The thermal radical polymerization initiator may be dicumyl peroxide.

[0141] The mixture of (d), (e), (f) and (g) may be free or substantially free of surfactant.

[0142] The plastic product may be a protein-resistant plastic product.

[0143] Plastic products can be antibacterial and / or antiviral.

[0144] In a ninth aspect, there is provided a plastic article obtained by the method of any one of the sixth to eighth aspects.

[0145] definition

[0146] The following are some definitions that may be helpful in understanding the description of the present disclosure. These are intended as general definitions and should in no way limit the scope of the present disclosure to only these terms, but are provided for a better understanding of the following description.

[0147] In this specification, unless the context requires otherwise, the word "comprise" or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers and steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.

[0148] The terms "a" and "an" are used herein to refer to one or more than one (ie, to at least one) of the grammatical object of the article. For example, "an element" means one element or more than one element.

[0149] In the context of this specification, the term "about" is understood to refer to a range of numbers that one skilled in the art would consider equivalent to the recited value in the context of achieving the same function or result.

[0150] Any numerical range described herein is intended to include all subranges of the same numerical precision contained within the range. For example, a range of 1.0 to 5.0 is intended to include all subranges between the stated minimum value of 1.0 and the stated maximum value of 5.0, i.e., having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 5.0, such as 2.1 to 4.5. Any maximum numerical limit described herein is intended to include all lower numerical limits contained therein, and any minimum numerical limit described herein is intended to include all higher numerical limits contained therein.

[0151] The term "substantially free" when used in reference to surfactant content means that surfactant comprises less than about 3% (w / w), or less than about 2% (w / w), or less than about 1% (w / w), or less than about 0.5% (w / w), or less than about 0.1% (w / w), or less than about 0.05% (w / w), or less than about 0.01% (w / w), or less than about 0.005% (w / w) of the mixture or composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0152] Figure 1 : A method of producing a plastic article according to an embodiment of the present disclosure.

[0153] Figure 2 : Protein binding capacity of a plastic article prepared according to one embodiment of the present disclosure compared to the protein binding capacity of commercially available plastic articles. DETAILED DESCRIPTION

[0154] The present inventor has developed a resin modifier composition and a functional resin composition based on a thermoplastic resin that can be used to prepare plastic products. The surface of the product can be adjusted to have antibacterial, antiviral and / or antifouling properties. The antibacterial, antiviral and / or antifouling properties are built into the surface and do not rely on the migration of microbicides, the use of surface coatings or the chemical loss of the product. In addition, the performance of the product is stable because the effectiveness of the antibacterial, antiviral and / or antifouling properties is minimally affected by the surface morphology of the product, the composition of the contact medium and the external environmental pressure (such as irradiation and high pressure sterilization and cleaning repetitive cycles). The product provides significant advantages that are superior to those of the prior art because they are not susceptible to delamination or wear and tear, and their antibacterial, antiviral and antifouling properties will not decrease over time.

[0155] Composition

[0156] In one aspect, a thermoplastic resin modifier composition is provided, comprising, consisting of, or consisting essentially of:

[0157] (i) vinyl monomers;

[0158] (ii) copolymerizable anhydrides;

[0159] (iii) a thermal free radical polymerization initiator; and

[0160] (iv) Thermoplastic resins.

[0161] The composition may comprise at least 85% (w / w), or at least 86% (w / w), or at least 87% (w / w), or at least 88% (w / w), or at least 89% (w / w), or at least 90% (w / w), or at least 91% (w / w), or at least 92% (w / w), or at least 93% (w / w), or at least 94% (w / w), or at least 95% (w / w), or at least 96% (w / w), or at least 97% (w / w), or at least 98% (w / w) of the thermoplastic resin. In some embodiments, the composition comprises between about 85% (w / w) and about 98% (w / w), or between about 86% (w / w) and about 98% (w / w), or between about 87% (w / w) and about 98% (w / w), or between about 88% (w / w) and about 98% (w / w), or between about 89% (w / w) and about 98% (w / w), or between about 90% (w / w) and about 98% (w / w), or between about 91% (w / w) and about 98% (w / w), or between about 92% (w / w) and about 98% (w / w), or between about 93% (w / w) and about 98% (w / w) of the thermoplastic resin.

[0162] The copolymerizable anhydride may be an organic anhydride of the following general formula (I), wherein R1 and R2 are organic residues.

[0163]

[0164] R1 and R2 and the carbon and central oxygen atom to which they are connected can form a ring structure.The ring structure can be monocyclic, dicyclic, tricyclic or tetracyclic.The limiting examples of organic anhydride comprises maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, naphthalenetetracarboxylic dianhydride and their isomorphous analogues, comprise maleimide (for example, maleimide, norbornene dicarboximide, N-ethoxycarbonyl maleimide, N-carbamoyl maleimide, N-phenylmaleimide, N-(4-carboxylphenyl) maleimide and the N-ethylmaleimide with different N-substituents), maleate (for example, dibutyl maleate and ricinoleic acid oxazoline maleate), fumaric acid, and anhydride, ester and the imide derivatives of citraconic acid and itaconic acid.

[0165] In one embodiment, vinyl monomer comprises one or more parts with antibacterial, antiviral or antifouling properties. Parts with antibacterial, antiviral or antifouling properties include, for example, hydroxyl, amino, carboxyl, ether, substituted ring, condensed ring and heterocyclic groups. Some parts are typical surfactant structures consisting of hydrophilic and hydrophobic units. Non-limiting examples of antibacterial and antiviral parts include, but are not limited to, natural peptides, N-substituted amides, squalene, tannins, saponins, flavonoids, alkaloids, steroids, lactones, lectins, lactams, antifungal agents, antifungal agents, alkyl glycosides, aminoglycosides, sugar-containing polymers, glycolipids, sugar esters, quaternary ammonium compounds, terpenes, terpenoids, fatty acids, fatty acid esters, alkylamines, alkylamine oxides, alcohol alkoxylates, nitroxides, halamines, diaryl ethers, xanthone, quinones, coumarins, polyacetylene, guanidines, halogens, phosphate derivatives, sulfonic acid derivatives, phenol derivatives, benzoic acid derivatives, organometallics, pyridinium derivatives, piperazine derivatives, Pyrrolidone derivatives, aniline derivatives, biguanides and related compounds, oximes and related compounds, isothiazolinones and related compounds, indole derivatives, heteroazole derivatives, heteropyrroline derivatives, hydrazide-hydrazone derivatives, pyrans and related compounds, furans and related compounds, macrolides, tetracyclines, oxazolidinones, quinolones, amidoximes, amidoamines, triazoles, imidazoles, carbamates, dialdehydes, cyclic aldehydes, isothiocyanates, paraformaldehydes, cycloalkanoates, citrates, creosote, N-organodiazeniumdioxy-metals, sulfonamides, lincosamides, arsenic compounds, boron compounds, organochlorines, and polypropyleneimines.

[0166] In some embodiments, the vinyl monomer is a short chain olefin, styrene, an alkyl acrylate, an alkyl acrylate, vinyl acetate, vinyl alcohol, vinyl phenol, vinyl alkyl ether, vinyl halide, vinyl acetic acid, acrylonitrile, acrylamide, vinyl silane, vinyl sulfide, vinyl sulfone, vinyl sulfoxide, vinyl ethylene carbonate, vinyl pyrrolidone, vinyl carbazole, vinyl norbornene, an unsaturated fatty acid, or an unsaturated fatty acid ester.

[0167] In alternative embodiments, the vinyl monomer is one or more of the following monomers:

[0168]

[0169] wherein R3 to R7 are independently selected from: H, C1-C 10 alkyl, phenyl, halogen, OH, cyano and OC1-C6 alkyl, and wherein each of the monomers optionally comprises one or more of the following or is conjugated to one or more of the following: natural peptides, N-substituted amides, squalene, tannins, saponins, flavonoids, alkaloids, steroids, lactones, lectins, lactams, antifungal agents, antifungal agents, alkyl glycosides, aminoglycosides, sugar-containing polymers, glycolipids, sugar esters, quaternary ammonium compounds, terpenes, terpenoids, fatty acids, fatty acid esters, alkylamines, alkylamine oxides, alcohol alkoxylates, nitroxides, halamines, diaryl ethers, xanthones, quinones, coumarins, polyacetylene, guanidines, halogens, phosphate derivatives, sulfonic acid derivatives, phenol derivatives, benzoic acid derivatives, organometallics, pyridinium derivatives, piperazine derivatives, pyrrolidone derivatives, aniline derivatives, biguanides and related compounds, oximes and related compounds, isothiazolinones and related compounds, indole derivatives, heteroazole derivatives, heteropyrroline derivatives, hydrazide-hydrazone derivatives, pyrans and related compounds, furans and related compounds, macrolides, tetracyclines, oxazolidinones, quinolones, amidoximes, amidoamines, triazoles, imidazoles, carbamates, dialdehydes, cyclic aldehydes, isothiocyanates, paraformaldehydes, cycloalkanoates, citrates, creosote, N-organodiazeniumdioxy-metals, sulfonamides, lincosamides, arsenic compounds, boron compounds, organochlorines, and polypropyleneimines, or any combination thereof.

[0170] Thermal free radical polymerization initiators are well known to those skilled in the art and include, for example, peroxides and azo compounds. Examples of suitable peroxides include diacyl peroxides (such as benzoyl peroxide and dilauroyl peroxide), dialkyl peroxides (such as di-t-butyl peroxide and dicumyl peroxide), peresters (such as t-butyl perbenzoate), ketone peroxides (such as methyl ethyl ketone peroxide), and the peroxides sold under the trade name and Examples of suitable azo compounds include azobisisobutyronitrile (AIBN), 1,1'-azobis(cyclohexanecarbonitrile) (ACHN) and the compounds sold under the trade name Vazo TM Commercial azo products sold or supplied by Vesta Chemicals and Fujifilm Wako Chemicals.

[0171] In addition to considering the reaction temperature and the specific thermoplastic resin modifier composition, the selection of a suitable thermal free radical polymerization initiator is based on several factors, including its oil / water solubility (relative to liquid vinyl monomer), efficiency factor, decomposition half-life, hydrogen abstractability, stability of primary free radicals, formation of decomposition byproducts, and susceptibility to induced / redox decomposition, which determine grafted versus non-grafted polymerization, thereby controlling the efficiency, extent, length, distribution, microstructure, and sequence of grafting of vinyl monomers and copolymerizable anhydrides onto the polymer backbone to prevent a number of possible side reactions that terminate in cage reactions, β-scissions, premature termination of free radicals / propagating chains, and chain transfer reactions to less reactive intermediates. Suppressing these side reactions can help prevent undesirable post-processing observations such as gel formation, discoloration, odor, blooming, and significant changes in the melt flow index and physical properties of the thermoplastic resin.

[0172] Peroxide-based initiators are generally more susceptible to grafting reactions and branch / crosslink formation via hydrogen abstraction or intramolecular back-biting of hydrocarbon species, but are less likely to form linear polymers than azo initiators. To achieve the grafting reaction, the total reaction time or residence time occurring within the melt processing equipment is preferably in the range of about 1 to 4 times the half-life of the initiator at the desired reaction temperature when determining the optimal conditions for heat treatment. While melt processing (such as reactive extrusion) can typically involve a temperature profile that gradually increases from the front (i.e., feed and transition zones) to the back (i.e., metering and die zones) of the screw extruder, using a mixed system of a shorter-lived initiator (such as benzoyl peroxide) and a longer-lived initiator (such as dicumyl peroxide) in a molar ratio of 20:80 to 80:20 in the composition can maintain high initiation efficiency and grafting yield throughout the polymer melt compounding process.

[0173] Organic peroxide-based initiators cover a wide range of decomposition half-lives and solubilities. The following is a list of general classes of peroxide-based initiators arranged in ascending order of decomposition half-life: peresters, peroxydicarbonates, alkyl peroxycarbonates, diacyl peroxides, perketals, ketone peroxides, peracids, dialkyl peroxides, hydroperoxides, and silyl peroxides.

[0174] In a preferred embodiment, the vinyl monomer is an electron donor having a high electron density double bond and a hydrophobic molecule by having at least one electron donor substituent, such as styrene, α-methylstyrene, vinyl naphthalene, isobutylene, vinyl norbornene, butyl vinyl ether, and 2-chloroethyl vinyl ether. When preparing the modified thermoplastic resin composition, the vinyl monomer tends to copolymerize with anhydrides, electron acceptors, and hydrophilic molecules to form alternating or random multi-block copolymers, which impart strong amphiphilicity.

[0175] The copolymers formed in the modified thermoplastic resin composition are anchored as multiple short branches on the thermoplastic resin backbone, resulting in a hair-like or comb-like structure. Therefore, they are surface active and will freely migrate to the surface when in contact with a dry or wet environment to produce a dirt-releasing and self-cleaning effect at the surface. Although they are covalently attached to the substrate, this does not cause any leaching problems.

[0176] The reactive and hydrolyzable anhydride moieties on the chemical grafts are bifunctional in nature. They can be used to capture and chemically bind to additive compounds with alcohols, amines, and nucleophiles, leading to some hyperbranched microstructures, and can be used to improve adhesion or compatibility with other polar thermoplastics, which can lead to toughened alloys. This approach is superior to the alternative use of commercial coupling agents such as acrylic modified polyolefins, polyolefin grafted maleic anhydride resins, polyolefin grafted glycidyl methacrylate resins, and some random copolymers of styrene, maleic anhydride, and N-phenylmaleimide, which are sold under the trade name (BYK), (Nippon PaperIndustries)、Polybond TM (ChemPoint), (Clariant), (EastmanChemicals), Exxelor TM (ExxonMobil), A- (Honeywell), Graftabond TM (Graft Polymer), (Polyscope Polymers), IP (Denka), (Polyram), Lustran (Styrolution), Amplify TM (Dow), (Arkema), (Arkema) and (DuPont) are available in various grades. Although the latter appears to be simpler, the two approaches produce different polymer microstructures. For the latter, the coupling agent, after dispersion in the matrix of the thermoplastic resin, provides only fixed reactive anchors of anhydride or carboxylic acid groups, rather than open protruding arms that can detach from the bulk matrix and create adaptive brush-like topologies in a short time scale using rapid surface reconstruction of hydrophobic / hydrophilic units or short chain segments, as in the present disclosure. Although the graft length is uncontrolled and polydisperse in nature, grafts with mixed chain lengths will significantly enhance the antifouling properties of the substrate surface by including a brush sublayer of shorter chains to prevent the adsorption of small solutes that can diffuse into the voids and interstices of the tethered brush and offset the adverse effects of the reduced surface density of longer chains.

[0177] The alternating tendency of graft copolymerization of vinyl monomers (as donors) and anhydrides (as acceptors) is related to the feed ratio and total monomer conversion of the thermoplastic resin modifier composition. If the total monomer conversion is less than 15%, alternating polymers can be obtained from feeds containing 30 to 70 mol% acceptor. If the total monomer conversion is greater than 80%, strictly alternating copolymers are typically obtained from equimolar or near-equimolar feed ratios. However, when using non-equimolar feeds, chain-to-chain composition deviations are unavoidable. In addition to controlling the feed ratio between the vinyl monomer and the anhydride of the thermoplastic resin modifier composition, three other conditions may favor the alternation of such a binary system and achieve higher grafting efficiency: (i) the product of the reactivity ratios (r1 and r2) of the two components falls between 0 and 1 (where r1 and r2 are non-zero and reasonably close to r1:r2 (r1 ≥ r2) not exceeding 60:1), more preferably close to zero; (ii) their e coefficients according to the Alfrey-Price Qe scheme (where Q represents the monomer reactivity (a measure of resonance stabilization) and e represents its polarization (a measure of polarity effect)) differ greatly and more preferably are large in magnitude and have opposite signs; and (iii) the reactivity of the vinyl monomer or anhydride toward the polymer macromolecular group of the thermoplastic resin is preferably greater than that of its counterpart, such as its ability to form a stable macromolecular group and the resulting free radical readily copolymerizes with its counterpart to produce a grafted molecular complex. For example, styrene is a preferred vinyl monomer that is capable of generating a stable styrene-based macromolecular group. Styrene and maleic anhydride (a typical donor-acceptor monomer pair with comparable Q coefficients) have been reported to have reactivity ratios, Q coefficients, and e coefficients of (0.04, 1, -0.8) and (0, 0.86, +3.69), respectively, and therefore have a strong tendency to produce alternating grafting at equimolar feed ratios.In principle, this is possible by using more than one type of vinyl monomer as a comonomer, such as vinyl acetate, acrylamide, N-isopropylacrylamide, N-vinylpyrrolidone, N-hydroxymethylacrylamide, 2-methoxyethyl acrylate, furfuryl methacrylate, tetrahydrofurfuryl acrylate, 4-acryloylmorpholine, 2-N-morpholinoethyl methacrylate, acrylamidoglycolic acid, acrylonitrile, methacrylic acid, methyl methacrylate, 2-ethylhexyl acrylate, butyl acrylate, isobornyl methacrylate, 2-hydroxyethyl methacrylate, 2-aminoethyl methacrylate, 2-(dimethylamino)ethyl methacrylate, 3-methacryloyloxypropyltrimethoxysilane, 2-carboxyethyl acrylate, 2-azepane ethyl methacrylate. Examples of the comonomers used include hydroxymethyl acrylamide, hydroxyethyl acrylate ...

[0178] In some embodiments, the thermoplastic resin is an addition polymer. Addition polymers are polymers formed by monomer connection in the absence of other products produced together, and are well known to those skilled in the art. In another embodiment, the thermoplastic resin is a polyolefin elastomer (POE). POE is an elastomer based on a polyethylene skeleton, and is also well known to those skilled in the art. In another embodiment, the thermoplastic resin containing olefins is rubber. Rubber can be natural rubber or synthetic rubber.

[0179] In some embodiments, thermoplastic resins include, but are not limited to, polyethylene (PE), polypropylene (PP), polybutylene (PB), cyclic olefin copolymer (COC), cyclic block copolymer (CBC), poly(cyclohexylethylene) (PCHE), polymethylpentene (PMP), polyvinyl butyral (PVB), polyacrylonitrile (PAN), nitrile rubber (NBR), ethylene propylene rubber (EPR), poly(ethylene-co-1-octene), poly(ethylene-co-1-hexene), poly(ethylene-co-1-butene), chloroprene rubber, polyisoprene (PI), poly(styrene-ethylene-butylene-styrene) (SEBS), poly(styrene-ethylene-propylene-styrene) (SEPS), poly(styrene-butadiene-styrene) (SBS), styrene-isoprene block copolymer (SIS), methyl methacrylate-butadiene-styrene (MBS), acrylonitrile butadiene styrene (ABS), acrylonitrile ethylene styrene polymer (AES), hydrogenated or carboxylated nitrile rubber (HNBR / XNBR ), acrylic rubber (ACM), isobutylene-isoprene rubber (IIR), epichlorohydrin rubber (ECO), ethylene butyl acrylate copolymer (EBA), ethylene vinyl acetate (EVA), ethylene vinyl alcohol (EVOH), ethylene acrylic acid (EAA), ethylene methyl acrylate (EMA), ethylene propylene diene monomer (EPDM), ethylene tetrafluoroethylene (ETFE), ethylene chlorotrifluoroethylene (ECTFE), ethylene vinyl chloride (EVCL), chlorinated or oxidized polyethylene (CPE / OPE), olefin metathesis products, thermoplastic elastomers of polyesters (TPEE), copolyesters (TPC), polyurethanes (TPU), polyamides (TPAE), polyether block amides (PEBA) or copolymers made of silicone, polycarbonate, polyether and / or polyurethane segments (TSPCU), or any polymer compound having, in the main chain or in the side chains, repeating units consisting of aliphatic-, cyclo- or aliphatic-alkyl, aliphatic-alkenyl or -aliphatic-alkynyl groups containing at least one or more CH units, including combinations thereof.

[0180] In a preferred embodiment, the thermoplastic resin is a medium to high flow homopolyolefin, multi-block copolymer and random copolymer, and blends of such copolymers derived from two or more monomeric substances, and exhibits a uniformly dispersed but small-sized domain morphology driven by phase separation and / or crystallization in a multiphase system. The melt flow index of the thermoplastic resin is more preferably 5 g / 10 min (190° C. / 2.16 kg) or above. It is well known that the impact and high gloss properties of thermoplastic resins depend on crystallinity. Crystallinity decreases with decreasing stereoregularity, and the material exhibits higher elasticity but less haze. Many methods are known for controlling phase separation and crystallization, such as by introducing stereo defects, by short chain branching, by introducing comonomers, and by adding nucleating agents to accelerate crystallization and increase the number of nuclei formed. The thermoplastic resin is preferably an amorphous or low crystalline grade of thermoplastic elastomers and polyalphaolefins. Most of these commercially available resins comprise primarily ethylene and / or propylene repeating units, examples being Vistamaxx, Exact, Optema, EMAC, EBAC, Notio, Tafmer, Vestoplast, Lutene, Lumicene, L-Modu, Versify, Engage, Elvax, Lotryl, Evatane, Elvaloy AC, Clyrell, Tafthren, Tefabloc, Kraton G, and the like.

[0181] Vinyl monomers, copolymerizable anhydrides, thermal free radical polymerization initiators, and other additives may not dissolve well in one another. This can be facilitated by mixing them in an organic solvent or solvent mixture at a weight ratio of about 1:3 to 1:2 relative to the copolymerizable anhydride and then compounding with the thermoplastic resin prior to melt processing. Solubility can be adjusted by adding one or more solvents of varying polarity and inertness to the initiator. Examples of solvents include carbon tetrachloride, isopropyl alcohol, tetrahydrofuran, ethyl acetate, benzene, toluene, methyl ethyl ketone, o-dichlorobenzene, dimethylformamide, N,N-dimethylacetamide, N,N-dimethylaniline, 4,N,N-trimethylaniline, dimethyl sulfoxide, triphenyl phosphite, tris(nonylphenyl) phosphite, caprolactam, liquid paraffin, odorless mineral spirits, isododecane, cumene, 1,3-diisopropylbenzene, cyclohexylbenzene, and some highly branched isohexadecanes. The type of solvent selected can, to a certain extent, regulate the polymerization and grafting of vinyl monomers and copolymerizable anhydrides onto the polymer backbone of the thermoplastic resin, depending on their polarity, polarizability, volatility, electron donating / withdrawing ability, and chain transfer constant. Solvents containing nitrogen, phosphorus, or sulfur atoms and derived from compounds such as amides, lactams, carbamates, amine oxides, phosphites, phosphates, phosphonates, phosphoramides, phosphine oxides, monosulfides, sulfoxides, aryl disulfides, and thiazolyl disulfides can act as electron donors for the electrophilic monomers or anhydrides, as well as inhibitors of crosslinking (gelation), degradation, and homopolymerization, but can also act as promoters of graft copolymerization. This effect can be promoted by the interaction of small doses of free radical / dioxygen scavengers, active chain transfer agents or co-catalysts with primary free radicals, monomeric free radicals and macromolecular groups, and the dosage range is about one-tenth to two-tenths parts by weight of the thermal free radical polymerization initiator, and the free radical / dioxygen scavengers, active chain transfer agents or co-catalysts such as p-benzoquinone, benzophenone, lithium phenyl-2,4,6-trimethylbenzoylphosphite, benzotriazole, hydroxyphenyltriazine, quinone methide, 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl, 2-cyano-2-propylbenzodisulfide, butylated hydroxytoluene, dipentamethylenethiuram tetrasulfide, tris(2,4-di-tert-butylphenyl)phosphite, octyltin mercaptide, octyltin carboxylate, dibutyl phthalate, stearamide, ascorbic acid, thiobarbituric acid, N-acetoxy-phthalimide, Zinc salts, iodonium salts, sulfonium salts and compounds derived from thiols, thioethers, thiocarbonates, thioesters, thiocarbamates, xanthates, sulfonylureas, alkoxyamines, imidazolylnitrones, polyunsaturated fatty acids, hindered phenols, hindered amines, organosilicon hydrides, organoboranes, alkylaluminums, persulfates, ylides, metal ylide complexes and transition metal complexes such as Sn(II), Sb(III), Pb(II), Bi(III), Fe(II), Ti(II), Ti(III), Mn(II), Mn(III) or Ge(II).

[0182] Deodorants may be present in an amount between 0.5% (w / w) and 1% (w / w) to absorb or neutralize traces of pungent odors resulting from unreacted / evaporated anhydrides or acids during melt processing, off-gassing of volatile impurities, and other reactions involving the functional groups of amines and sulfur components such as hydrogen sulfide, mercaptans, and thioethers. Suitable examples of deodorants include bentonite, activated carbon, metal-exchanged zeolites, potassium alum, silica gel, talc, alkaline adsorbents, mica, diatomaceous earth, and several other commercial products available on the market, such as TEGO containing zinc ricinoleate. Containing ethylene oxide reactive groups as well as RP 17.

[0183] The thermoplastic resin modifier composition can be prepared by combining a thermoplastic polymer resin (which can be in granular or powder form), a vinyl monomer (which can be in liquid or paste form), a copolymerizable anhydride, and a thermal free radical polymerization initiator in the following amounts:

[0184] Thermoplastic resin: about 90% (w / w) to about 98% (w / w)

[0185] Vinyl monomer: about 0.5% (w / w) to about 4% (w / w)

[0186] Copolymerizable anhydride: about 0.5% (w / w) to about 4% (w / w)

[0187] • Thermal free radical polymerization initiator: about 0.05% (w / w) to about 2% (w / w).

[0188] The resulting mixture can then be subjected to oscillatory shaking or mechanical stirring in a closed chamber. Mixing on a kilogram production scale can be performed more uniformly with the help of mixing, coating and size reduction equipment such as blade mixers, ribbon mixers, 3-dimensional drum mixers, Banbury mixers, dispersor kneaders, solid disc coaters, fluidized bed powder coaters, atomizers, spray coaters, cryogenic or non-cryogenic plastic pulverizers or ball mills, which are preferably equipped with temperature control and an inert gas supply to minimize shear heating effects.

[0189] The modified thermoplastic resin composition can then be prepared by melt processing the thermoplastic resin modifier composition. Melt processing can involve a complete cycle of heating (melting) and cooling (solidification), wherein the method includes four main modules: (a) feeding unit; (b) melting / conveying unit; (c) shaping / cooling unit; and (d) winding / granulation / forming unit. The solid resin in the form of particles or pellets can be ground into a fine powder to enhance the uniformity of mixing with other starting materials. If the machine is equipped with an automatic liquid feeder, a metering pump or can include any high-precision metering unit (which can be volumetric, optical and weight) for continuous production, the starting materials in solid and liquid form can be fed to the melting / conveying unit, such as a screw extruder, respectively. In the case of a large amount of liquid reagents, when the solid-liquid mixture settles over time in the feeding unit, dry mixing on the resin will cause liquid dripping. Since most vinyl monomers are soluble in non-polar organic solvents, porous organic modified inorganic products (such as clay, talc, zeolite, silica, aerogel, fly ash, blast furnace slag, volcanic ash, geopolymers, etc.), hollow carbon spheres, porous polymer-based media products such as Capatue TM Microporous foam, MP / XP, The superabsorbent may be a fine polypropylene fiber or a lightly cross-linked polyolefin copolymer containing one or more short-chain aliphatic hydrocarbons (e.g., ethylene, 1-hexene, 1-octene, 1-decene, etc.), styrene, and divinylbenzene units. In addition to extruders, highly localized rapid melting of thermoplastic resins using microwave radiation as a means of forming and welding and microwave-receptive additives (such as talc, zinc oxide, carbon black, carbon fibers, carbon nanotubes, polyethylene glycol, etc.) as a means of increasing the sensitivity of ordinary plastics to microwave treatment may be considered.

[0190] In some embodiments, the cooling unit is a circulating water bath for cooling and solidifying the molten extrudate from the screw extruder. If necessary, the liquid bath can be converted into a chemical bath of reagents and / or equipped with a surface modification and pH / temperature / oxidation-reduction potential control unit, such as a liquid plasma generator, an alkaline electrolyzer, a hydrogen-rich water generator, a reactive oxygen and nitrogen species (ROS / RNS) generator, a horn of an ultrasonic processor, etc. Examples of ROS / RNS include superoxide (O2·-), hydroxyl (·OH), peroxyl (RO2·) and alkoxy (RO-), as well as hypochlorous acid (HOCl), ozone (O3), singlet oxygen ( 1O2) and hydrogen peroxide (H2O2), which are non-free radicals. These non-free radicals are either oxidants or can be easily converted into free radicals. Nitrogen-containing oxidants include nitric oxide (NO·), peroxynitrite (ONOO·) and nitrogen dioxide (NO2). This additional process not only removes free residual compounds, but also adjusts the wettability of the produced thermoplastic resin (the thermoplastic resin is relatively hydrophobic) so that polar additives can be captured / deposited and more evenly dispersed in the solid matrix. An example is an ultrasonic liquid bath, which is prepared with inorganic metal salts (such as carboxylates, halides, nitrates, sulfides, etc.), alcohols (such as ethanol) and fatty acids / ammonium / polymeric compounds (such as ethanolamine, hexamethylenetetramine, oleic acid, polyvinyl alcohol, polyethylene glycol, polyvinyl pyrrolidone, etc.) used as precursors, co-solvents and end-capping agents, respectively, at a salt concentration of 0.1-1M, and forms a metal oxide nanostructured layer on the resin surface by ultrasonic chemical method. The bath pH can be adjusted to 5 to 8 by adding sodium hydroxide, ammonia, acetic acid or natural alkalizing mineral stone.

[0191] In another embodiment, the modified thermoplastic resin composition can be produced by solvent-assisted solid phase polymerization at lower processing temperatures rather than melt processing, particularly for soft and rubbery thermoplastics, temperature-sensitive or shear-sensitive viscous materials, all powder mixtures, wet pastes, emulsions, or manufacturing facilities where advanced processing equipment (such as underwater pelletizers, resonant acoustic mixers, ultrasonic homogenizers, centrifugal mixers, blenders, marumerizers, high shear pelletizers, barrel pelletizers, twin dome extruders, planetary roller extruders, and some specialized twin-screw extruders (including combinations of distributing / dispersing elements and screw profile / intermeshing design configurations)) may not be available.

[0192] The thermoplastic resin is placed in a porous sleeve mounted on a Soxhlet extractor and allowed to purify in an inert atmosphere with a heating bath of a preferably volatile solvent (such as carbon tetrachloride, hexane, petroleum ether, ether and toluene) in a receiving flask until the resin particles swell and approach saturation with the solvent without significant weight change. Unreacted monomers, soluble low molecular weight fractions and organic impurities can be removed in the washing process. Next, under a continuous nitrogen flow (10-30 ml s -1The swollen particles are immersed in an ether solution at a temperature of 23 to 30°C (±1°C) to absorb the vinyl monomer, copolymerizable anhydride, and thermal free radical polymerization initiator from a solution previously prepared with the desired weight composition of the three components. The initiator preferably exhibits a high self-accelerating decomposition temperature between 60 and 80°C with a decomposition half-life of approximately 1 hour. Examples of initiators that match such properties include AIBN, dilauroyl peroxide, and di(hexadecyl) peroxide dicarbonate. The ether solvent is allowed to drain during the soaking process until it is largely evaporated. The particles impregnated with the vinyl monomer, copolymerizable anhydride, and thermal free radical polymerization initiator are then heated to the 1-hour half-life temperature and reacted for 1 to 1.5 hours before being cooled to room temperature in an ice bath. The modified particles are collected and purified by Soxhlet extraction with ether for at least 8 hours in an inert gas environment to remove unreacted components and autopolymerization byproducts.

[0193] By combining the modified thermoplastic resin composition with one or more additives to form a mixture, and subjecting the mixture to melt treatment, the modified thermoplastic resin composition can be used to prepare a functional resin composition. In one embodiment, the one or more additives can be additives typically contained in a masterbatch. Suitable additives include, but are not limited to, catalysts, pigments, gloss enhancers, antioxidants, light stabilizers, impact modifiers, plasticizers, softeners, crosslinking agents, compatibilizers, fillers, antistatic agents, lubricants, anti-caking agents, anti-fogging agents, surfactants, flame retardants, optical clarifiers, rheology modifiers, and spices, as well as other processing aids, coupling agents, and reagents that are crucial to the physical properties of the core material constituting the plastic product. The modified thermoplastic resin composition can be surface pretreated with commercial spraying, brushing or internal washing durable waterproof products or surface finishing products (such as sold by Nikwax, Gear Aid, Ultratech International, Shi-Etsu, Huntsman, Texchem UK, Rust-Oleum NeverWet, Cytonix, Wuxi Shunye Technology, etc.) to impart waterproof / oil-proof and antifouling / dust-proof properties. One or more additives may include one or more compounds with antibacterial, antiviral or antifouling properties. Antibacterial, antiviral or antifouling properties can be imparted to the plastic article by vinyl monomers as described above and / or by including one or more compounds with antibacterial, antitoxic or antifouling properties in the functional resin composition.

[0194] Although the functional resin composition can be prepared in a single step by including one or more additives in the mixture of components used to prepare the modified thermoplastic resin composition, dividing the process into two steps avoids free radical-induced degradation of additives (such as compounds based on alkylene oxides or their adducts of alcohols, polyunsaturated fatty acids, acid esters, etc.) at high temperatures, which leads to auto-oxidation, discoloration and odor in the functional resin composition.

[0195] Method for producing plastic products

[0196] Figure 1 The method for preparing the plastic article according to the present disclosure is summarized. In one embodiment, the modified thermoplastic resin composition 100 is converted into a functional resin 101 by combining it with one or more additives. The functional resin 101 is then directly converted into a plastic article by forming (e.g., by molding).

[0197] In an alternative embodiment, the modified thermoplastic resin composition 100 is converted into a functional resin as a masterbatch (102) by proportionally increasing the content of its ingredients. The functional resin masterbatch 102 is then combined with an appropriate core resin 103 (which reflects the core / base plastic from which the plastic article will be produced) and melt-processed to form the plastic article. By utilizing this method, the functional resin masterbatch 102 can be dry-mixed with the core resin 103 before melt-processing to form the article. As a result, a core resin with a lower melting temperature (such as a polyolefin elastomer) can be used as a bulk carrier for the additives in the functional resin masterbatch 102 to minimize their chemical decomposition and by-product formation. In some embodiments, the ratio of core resin 103:functional resin masterbatch 102 is about 80 to 95 parts:5 to 20 parts.

[0198] In another embodiment, the modified thermoplastic resin composition 100 is combined with a masterbatch 104 and a core resin 103 and converted directly into a plastic article using melt processing. In some embodiments, the ratio of core resin 103:masterbatch 104:modified thermoplastic resin composition 100 is about 75 to 85 parts:5 to 15 parts:5 to 15 parts.

[0199] The core resin can be any plastic material from which it is desired to produce an article. In some embodiments, the core resin is one or more of the thermoplastic resins described above.

[0200] The present inventors have discovered that by varying the surface energy, graft length, spatial size and side group charge on the vinyl monomer, as well as the hardness of the resin modifier composition and the amount of the resin modifier composition present in the core material that will constitute the plastic article, the properties of the article can be finely tuned to differentially control the killing and / or repelling of microorganisms, viruses and the accumulation of residual biological materials from the surrounding medium (such as blood stains, spores, pollen, proteins, enzymes, nucleic acids, extracellular polymeric substances, metabolites and pathogenic agents (e.g., endotoxins and mycotoxins). It has been found that the killing and / or repelling effect The effects occur not only on flat and smooth surfaces of the article, but also on matte, curved, microporous and foam surfaces of the article. In addition, the killing and / or repelling effect is largely unaffected by environmental stresses (such as gamma ray / UV irradiation and repeated autoclave and cleaning cycles), making the article suitable not only for single use but also for reusable packaging, medical devices and plastic laboratory ware applications. These articles are also biocompatible and safe for food contact. Advantageously, the article does not require a surface coating and is therefore not prone to delamination.

[0201] The properties of the article are tunable, as the article can be antifouling, antibacterial and / or antiviral as follows:

[0202] Repels microorganisms without killing them;

[0203] Kills microorganisms but does not repel them;

[0204] Synergistically kill and repel microorganisms;

[0205] Removal of viruses and biological materials;

[0206] Inactivate infectious viruses.

[0207] In the case of bulk article preforms that may be made of a different type of material than the thermoplastic resin composition, the surrounding or target surface of the substrate may be decorated with the functional resin composition using insert molding, overmolding, multi-molding, hot melt lamination, or two-component co-extrusion processes to form a core-sheath or two-layer profile.

[0208] The inventors have discovered that, where protein resistance is desired, alcohol ethoxylates or alkylene oxide-derived compounds (including oligomers / polymers of ethylene glycol) can be included in the functional resin composition. The resulting plastic articles produced exhibit highly effective protein binding resistance.

[0209] Several mechanisms are at work to impart protein binding resistance to plastics, such as through the application of large excluded volume effects and entropic and osmotic repulsions caused by their lower surface in contact with the transport medium due to high conformational mobility, high hydration levels, and low interfacial free energy. To this end, an effective approach is to increase the hydrophilicity of the plastic substrate by incorporating hydrophilic additives, preferably superabsorbent polymers, which will exert a stealth effect by forming a durable and fast-acting hydration layer on the uppermost surface that exhibits limited or weak interactions with plasma proteins and, after covalent functionalization of the substrate with the additive, also exhibits low nonspecific cellular uptake. The above-mentioned additives (which should be easily hydrated / swelled, preferably water-soluble, and not very sensitive to pH and charged species) can be nonionic or charged species. Oligomers / polymers of ethylene glycol, at least one end of which is hydroxyl or methoxy terminated and the other end is anhydride-reactive or redox-active for binding to the plastic substrate, are preferred choices for nonionic hydrophilic additives. Other suitable examples include polyvinyl alcohol, polyallyl alcohol, polyvinyl formaldehyde, polyglycerol, polypeptides, pullulan, polypropylene sulfoxide, polycitrate glycol esters, polyvinyl pyrrolidone, hydroxyethyl cellulose, poly(3-ethyl-3-(hydroxymethyl)oxetane), acetals or acetal copolymers substituted with primary or secondary OH groups, polyglycidol, poly(N-isopropylacrylamide), poly(2-hydroxyethyl methacrylate), poly(N-[tris(hydroxymethyl)methyl]acrylamide), poly(2-methyl-2-oxazoline), poly(2-ethyl-2-oxazoline), polyphosphates and derivatives, and preferably exhibit (i) water solubility and a hydration number greater than zero; (ii) no net surface charge; (iii) a water contact angle of less than 65° on the solid surface or a surface tension greater than 30 dyn / cm after bulk modification; (iv) a chain length at least comparable to or greater than the size of the solute to be repelled; and (v) a higher ratio of hydrogen bond acceptors to hydrogen bond donors. Suitable examples of charged hydrophilic additives with the desired protein binding resistance are trimethylamine N-oxide, dimethylsulfonyl propionate, trigonelline, stachydrine, arsenobetaine, ectoine, phosphanyl (organyl) borane, amino acids (e.g. taurine, glycine, sarcosine, arginine), carnitine, ergothioneine and proline)-, or generally betaine-type zwitterions with a phosphonate group (PO3 - ), sulfonate (SO3 - ) and carboxylates (COO – ) and the terminal amino acid ( – OOC-C-NH3 +) of one or more pendant groups in phosphocholine, sulfobetaine, phosphobetaine, and carboxybetaine (which have both a positively charged amino group and a negatively charged carboxyl group on the α-carbon atom); or mixed-charge zwitterions containing balanced positively and negatively charged moieties in different monomeric units, or bonded to the same support or solid support (such as hectorite clay as an inherently doubly charged filler and disc-like particles that are positively charged on the edges and negatively charged on the surface), or through electrostatically assembled layers of oppositely charged polyelectrolytes comprising polyanions and polycations. Non-limiting examples of polyanions include polyacrylates (or carbomers), polystyrene sulfonates, poly(ethyleneoxy-4-butyric acid), poly(metaphosphoric acid), hyaluronic acid, polyglutamate, polyaspartate, polyalginate, caseinate, xanthan gum, gum arabic, carboxymethyl konjac glucomannan, k-carrageenan, pectin, carboxymethylcellulose, dextran sulfate, chondroitin sulfate, keratin sulfate, fucoidan, lignin sulfonate, carboxymethylated lignin, polyoxometalates, and L / S / FS series (Evonik Industries). Non-limiting examples of polycations include polyethyleneimine, poly(allylamine hydrochloride), polyvinylpyridine, polylysine, polyarginine, chitosan, gelatin, polyvinylamine, poly(tertiary amine), polyethyleneimine, polyamidoamine, polyquaternium, polyguanidine, and E / RL / RS series (Evonik Industries). Charged compounds are generally less thermally stable than non-ionic compounds. For longer processing times and processing temperatures exceeding 100°C, non-ionic compounds are preferred.

[0210] The present inventors have also discovered that adjusting the hydrophilic-lipophilic balance (HLB) or the logarithm of the 1-octanol-water partition coefficient (log P) of an additive can cause the plastic article to have a repellent effect, a killing / deactivating effect, or both, on approaching bacteria or viruses. This can be controlled by the HLB or log P value of the incorporated additive.

[0211] The additive may be an amphiphile, which is typically a linear molecule containing a polar head and a nonpolar tail separated by a number of spacer units of varying lengths and degrees of saturation, preferably a superdiffusion / superwetting agent that performs by rapid diffusion of aqueous solutions on low-energy hydrophobic surfaces, such as T-shaped trisiloxane polyoxyethylene ethers, more preferably a gemini surfactant, which is a biomimetic of components of phospholipid bilayer cell membranes, such as Gemsurf Alpha 142, a commercial product supplied by Chukyo-Yushi. Other commercial brands with similar gemini structures include Evonik Industries' and The higher the HLB value (or more negative log P value) of the additive, the greater the hydrophilicity and protein binding resistance of the plastic article after incorporation. Additives with HLB values greater than 7 (or log P values less than 4), and preferably penetration enhancers, such as fatty acid monoglycerides, fatty acid alkyl esters, disubstituted amides, N-alkyl substituted lactams, glycerol / sorbitan esters, glycol esters and sugar esters (whose carbon chain length is in the range of about 10-18 carbons), can interact with proteins or cells upon contact. Examples of commercial grade penetration enhancers include Montane TM 、 Atmer TM 、 and

[0212] Additives attached to the polymers of modified thermoplastic resin compositions are able to penetrate the bacterial cell membrane or algae / fungal cell wall, leading to microbial death due to mechanical stress and bending induced by the addition of additives exceeding a threshold concentration, and the subsequent disruption of the permeability of the cell membrane / wall. At HLB values between 10 and 16, the additives can act as both antifouling agents and biocides, resulting in a synergistic killing / deactivation and repellent effect. At higher HLB values approaching 20, the plastic becomes completely repellent and behaves similarly to hydrophilic additives. Common classes of nonionic surfactants include, but are not limited to, alcohol ethoxylates, alkylphenol ethoxylates, alkylaryl alkoxylates, alkylamine ethoxylates, ethoxylated fatty acid alkanolamides, ethoxylated fatty amines, alkyl alkoxylated phosphates, aryl alkoxylated phosphates, ethylene oxide (EO)-propylene oxide (PO) block copolymers, poloxamers (Pluronics), EO / PO alkoxylates, fatty alcohol ethoxylates, fatty acid ethoxylates, ethoxylated triglycerides, sorbitan / glyceride ethoxylates, alkyl glucosides, alkyl glucamides, alkyl glycerols, acyl glutamic acids, sugar fatty acid esters, dimethicone copolyols, polyether-modified polysiloxanes, ether-linked fluorosurfactants, or combinations thereof. Examples of amphoteric surfactants include, but are not limited to, alkylamine oxides, alkyl betaines, lecithins (a mixture of phosphatidylcholine, phosphatidylethanolamine, phosphatidylinositol, gangliosides, phosphatidic acid, phosphatidylglycerol, cardiolipin, and phosphatidylserine), sphingomyelins, and alkylamidopropyl betaines. Amphiphilic additives are preferably nonionic or salt-free amphoteric surfactants, rather than positively or negatively charged ionic detergents such as sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium cholate, sodium deoxycholate, benzalkonium chloride, alkyl ether sulfates, alkyl sulfates, alkylbenzenesulfonates, alpha olefin sulfonates, dialkyl sulfocarboxylates, phosphates, perfluorinated carboxylic acids, alkylamines, alkyl imidazolines, alkoxylated amines, and other quaternary ammonium and amino acid-based compounds. The nature of the interaction between proteins and surfactant molecules is electrostatic and hydrophobic. When ionic detergents are used as additives, the polar head of the molecule, if left unattached, can electrostatically bind to oppositely charged residues on the protein. Therefore, nonionic and amphoteric surfactants are milder and less prone to protein denaturation than ionic detergents, which are sometimes undesirable for certain applications as protein storage containers. Commercial grades of nonionic surfactants are primarily ethoxylated compounds, such as Triton TM -X, Montanox TM 、Dynol TM 、 Chemguard, Glycerox TM 、Unithox TM 、 and A few non-alkoxylated (no EO / PO) examples are from Arlacel TM 、 and Simulsol TM series. Surfactants with low toxicity levels such as low Gardner color (<2) and high bioregenerable carbon index, such as those biobased surfactants sold by Lankem, are preferred. Ethoxylated surfactants with more than 4 EO units (hydrophilic content) and a log P value of less than 3 are generally less favorable for bioaccumulation. Surfactants with low limiting surface tension at the aqueous critical micelle concentration and low critical micelle concentration are also preferred. These can be achieved by adding some low surface tension ends to the nonpolar tail of the surfactant, including but not limited to perfluoro and perfluoroalkyl substances (7 fluorocarbons or less because of lower bioaccumulation), highly branched hydrocarbons, siloxanes, organopolysilazanes, polycarbosilanes, polyhedral oligomeric silsesquioxanes, cholesterol or its structural analogs. In terms of the ascending order of the following surface tensions (CF3 < CF2 < CH3 < CH2 < phenyl), the ends preferably have a higher proportion of CF3 or CH3 groups, while accelerating the surface reorganization of the surfactant compound by adding methylene or ether bonds, thus compromising the flexibility of the nonpolar tail. The surfactant can additionally be combined with anticoagulants, antiplatelet agents, and coagulation factor inhibitors, such as fibrinogen, thrombin, factor XII, hirudin, lepirudin, bivalirudin, argatroban, dipyridamole, thrombomodulin, heparin, corn trypsin inhibitor, aspirin, warfarin, clopidogrel, prostacyclin, prostaglandin E2, fondaparinux, dabigatran, enoxaparin, elastin-like polypeptides, albumin, etc., to exert antithrombotic activity and prevent thrombosis.

[0213] Any one or more of the compounds described in paragraphs

[00157] to

[00161] above can be used as additives in masterbatches or functional resins as needed.

[0214] In another embodiment, an anti-biofilm, anti-viral agent, chemorepellent, bacterial metabolism regulator, metal chelator, Schiff base, carbohydrate binder, oxidative stress promoter, fatty acid synthesis, cell wall synthesis, DNA synthesis, protein synthesis, quorum sensing, c-di-GMP / c-di-AMP, ion channel, protease, other enzyme target, or proton pump inhibitor can be included as an additive to provide secondary protection of the plastic article to prevent microbial growth and / or viral activity at its surface.Such agents are primarily derived from biomass, naturally derived or biosynthesized compounds and include isosorbide mononitrate, S-nitrosothiol (which is a nitric oxide donor and can induce biofilm dispersion), ivermectin, dopamine hydrochloride, fusidic acid, kojic acid, fulvic acid, humic acid, furfural, lincosamides, pleuromutilins, streptogramins, ansamycins, lectins, β-lactams, methylglyoxal, sphingoid bases and fatty acids, ceramides, nucleoside analogs, pyroligneous acid, some phytochemical extracts such as cinnamaldehyde, allicin, iberin, allicene, linalool, citronellol, geraniol, eugenol, curcumin, coumarin, thymol, carvacrol, resveratrol, epigallocatechin gallate, N-acetylcysteine, α-mangostin, bakuchiol, paeoniflorin, urushiol, chloramphenicol, wagonin, spermine, paeoniflorin, panthenol, caffeic acid, ferulic acid, sinapic acid, linoleic acid acid, pterostilbene, caryophyllene, stigmasterol, β-sitosterol, licorice chalcone AE, echinatin, urushiol, quercetin, caffeine, menthol, vanillic acid, chlorogenic acid, salicylic acid, flavagline, ellagitannins, benzimidazole derivatives, hydroxamic acid derivatives, xanthophlls, dihydrochalcone, aurone derivatives, retinoic acid, guggulsterones, avenanthramides, glycosylated triterpenoid saponins, benzothiazoles, β-phenylethylamines, pyrethroids, meroterpenoids, anthraquinones, xanthones, fluorenones, nalenone), benzofurans, azaphilones, and some biosurfactants (such as lipopeptides, rhamnolipids, sophorolipids and microbial / algal exopolysaccharides), some venom peptides, such as polybia-CP, β-defensins, cathelicidins, mastoparans, some compounds isolated from marine organisms, such as indole alkaloids, bromotyrosine derivatives, furanones, morpholinones, tetrahydrofuran derivatives, phenyl ethers, benzene compounds, polyketides, some plant oils, such as castor oil, tung oil, camellia oil, linseed oil, neem oil, and some natural materials, such as benzoin, manuka honey, cork, ramie fiber and clove powder.

[0215] In some embodiments, a catalyst is included in a masterbatch or functional resin composition along with an additive to post-modify the modified thermoplastic resin composition. The catalyst can be a base, examples of which include triethylamine, imidazole, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo(5.4.0)undec-7-ene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and N-heterocyclic carbene compounds; or an acid, examples of which include stearic acid, diphenyl phosphate, methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, dibutyltin dilaurate, tin(II) 2-ethylhexanoate, zinc(II) acetate, and titanium(IV) butoxide. Urea, which decomposes in the melt upon heating, serves as an ammonia source for forming imines on the ketone or aldehyde moieties of the polymer in the modified thermoplastic resin composition, or for amidation of anhydrides or carboxylic acid moieties. Silylation agents such as hexamethyldisilazane (HMDS), 1,3-bis(trimethylsilyl)urea (BSU), and trimethylsilyl chloride (TMSCl) are used as adjuvants to cap and hydrophobize a portion of the alcohol and carboxylic acid moieties of the polymer and minimize their competing effects on catalyst activity. Chain extenders such as diols, diamines, and more preferably heterobifunctional species such as ethanolamine, isosorbide mono(methyl carbonate), p-maleimidophenyl isocyanate, 3-aminopropyltriethoxysilane, and polyethylene glycol monomethacrylate with two different end groups of any of alcohols, amines, halides, acyl halides, thiols, lipoic acid, carboxylic acids, carbonates, aldehydes, epoxies, isocyanates, acrylates, succinimidyl esters, maleimides, oxazolines, carbodiimides, silanes, and dipeptides may be included to enhance the polymer's chemoselectivity for specific functional groups of the additive. The flexibility of the chain extender can be controlled by the length of the spacer unit and the aliphatic / aromatic structure. Compatibilizers, preferably condensation plastics, can be incorporated into the composition to improve the miscibility of the core resin with the modified thermoplastic resin composition comprising hydrophilic and hydrophobic components and to provide a toughening effect.Suitable examples include polyamides, polyesters, polycarbonates, polyurethanes, poly(amino acids), poly(esteramides), poly(amidoamines), poly(ether-block-amides), polyurethaneureas, polyimides, polyisocyanurates, polycarbodiimides, silicone resins, phenolic resins, urea-formaldehyde resins, epoxy resins, more preferably bioplastics or biodegradable polymers such as polybutylene adipate terephthalate, polybutylene succinate, polylactic acid, poly(lactic-co-glycolic acid), polycaprolactone, poly(p-dioxanone), poly(glycolide-

[0014] Poly(ethylene glycol esters) are preferably poly(propylene glycol esters), poly(propylene glycol esters), poly(propylene glycol esters), poly(propylene glycol esters), poly(propylene glycol esters), poly(propylene glycol esters), poly(propylene glycol esters), poly(propylene glycol esters), poly(propylene glycol esters), poly(propylene glycol esters), poly(propylene glycol esters), poly(propylene glycol esters), poly(propylene glycol esters), poly(propylene glycol esters), poly(propylene glycol esters), poly(propylene glycol esters), poly(propylene glycol esters), poly(propylene glycol esters), poly(propylene glycol esters), poly(propylene glycol esters), poly(propylene glycol esters), poly(propylene glycol esters), poly(propylene glycol esters), poly(propylene glycol esters), poly(propylene glycol esters), poly(propylene glycol esters), poly(propylene glycol esters),

[0216] Example

[0217] The present disclosure is now further described by reference to the following non-limiting examples.

[0218] Example 1 - Production of modified thermoplastic resin composition (100)

[0219] Maleic anhydride (MA) and dicumyl peroxide (DCP), which are ground into powder before use, are stirred in styrene until the solids are partially dissolved. The resulting liquid dispersion is then added to particles of an olefin thermoplastic resin, and the resulting mixture is shaken in a drum at ambient temperature until the liquid suspension is evenly dispersed on the particles. The resin mixture is then melt-blended in a co-rotating twin-screw extruder. The temperature profile is set between 160° C. and 180° C., which is a common processing window for olefin thermoplastic resins. The filaments extruded from the die are stretched and solidified from the melt after cooling in water, and then cut into pellets to obtain a modified thermoplastic resin composition (100).

[0220] Example 2 - Conversion of Modified Thermoplastic Resin Composition (100) into Functional Resin (101)

[0221] The modified thermoplastic resin composition (100) is mixed with B 225 and alcohol ethoxylate (AEO-n) RO (CH2CH2O) n A liquid mixture of other additives of H (R = C12-14 alkyl and n = 3-23, spanning the full range of HLB values between 7 and 18) was melt compounded in a second extrusion pass under the same temperature profile as in Example 1 above to provide a functional resin (101) in pellet form.

[0222] Example 3 - Injection molding of plastic articles based on a mixture of a functional resin (101), or a modified thermoplastic resin composition (100), a masterbatch (104) and a core resin (103)

[0223] A masterbatch (104) carrying the desired additives is produced by extrusion under the same temperature profile as in Example 1. A mixture of the functional resin (101) or the modified thermoplastic resin composition (100) prepared by dry blending or melt blending, the masterbatch (104), and the core material resin (103) is fed into an injection molding machine, where they can be formed into various types of plastic products from a mold cavity.

[0224] Details of the plastic products are given in Table 1 below:

[0225] Table 1

[0226]

[0227]

[0228] The abbreviations in Table 1 are as follows:

[0229] AEO-5 – alcohol ethoxylate (AEO-n), also known as RO(CH2CH2O) n H, where R = C12-14 alkyl, n = 5, reported HLB value 10-11, and hydroxyl value 130-140 mg KOH / g (supplier: Shandong Usolf)

[0230] B225– B 225 (antioxidant)

[0231] DCP – dicumyl peroxide

[0232] HMDS – Hexamethyldisilazane

[0233] MA – Maleic anhydride

[0234] PA612 – Polyamide 6,12 ( 158NC010, Dupont)

[0235] PPH – Polypropylene Homopolymer (SKYLUX TM H530, DragonChem)

[0236] PPR-a – Polypropylene random copolymer (Clyrell RC5056, LyondellBasell)

[0237] PPR-b – Polypropylene random copolymer (Moplen RP6068, HMC Polymers)

[0238] PPO – Propylene-based olefin elastomer (Vistamaxx TM 6202, ExxonMobil)

[0239] SA – Stearic acid

[0240] TPE-a – Thermoplastic Elastomer (Kraiburg TPE K HTF8326 / 415)

[0241] TPE-b – Thermoplastic Elastomer (Kraiburg TPE K TF7AAC)

[0242] See Table 3 below for descriptions of footnotes 4-6 in Table 1

[0243] Example 4 - Protein Binding Properties of Plastic Articles Based on a Mixture of a Functional Resin (101) or a Modified Thermoplastic Resin Composition (100), a Masterbatch (104) and a Core Resin (103)

[0244] 1.5 mL standard centrifuge tubes were prepared by injection molding according to Example 3. The low retention performance of the tubes was compared with a commercial benchmark in terms of protein loss or recovery and with "blank" tubes as controls (ie, not inoculated with protein solution in the study). Figure 2 The results of experiments conducted at relatively short and long contact time scales, respectively, are summarized in Tables 2 and 3. It can be clearly concluded that one composition example, composition example 2, outperforms or is at least similar to the commercial benchmark in exhibiting low protein binding properties.

[0245] Figure 2The experiment was carried out as follows: bovine serum albumin (BSA) was used as a test protein. First, a concentrated 10 mg / mL BSA solution was freshly prepared by dissolving BSA (thin slices) in a 1x PBS buffer solution (pH 7.2-7.4). 200 microliters of BSA solution were transferred to 5 centrifuge tube samples with a pipette, covered and kept upright without stirring. After incubation at room temperature for 10 minutes, the BSA solution was slowly taken out from each sample with a pipette until there was no sign of solution residue. Then, 200 microliters of light green commercial bicinchoninic acid (BCA) assay reagent were added to each sample and control with a pipette and moderately shaken. The assay screening was determined by the color change of the sample solution from green to purple, which was proportional to the concentration of the protein residue. In the case of the commercial benchmark, the color became dark purple, while in the case of the centrifuge tube made from composition example 2, the color was light purple. The color in the "blank" test tube remained at the initial color of the BCA assay reagent.

[0246] The experiment of Table 2 was carried out as follows: human pooled serum (BF-ho-45, Bangfei Biological, 120 microliters) diluted with PBS buffer and then dispensed into a total of 12 sample tubes (1 ml for each sample, 3 samples for each sample type and storage condition) was used as a protein test subject. After storage at 4°C for 48 hours and 7 days, respectively, serum solutions were collected from the sample tubes and then quantified using a Bradford assay kit to calculate the amount of protein recovered from the sample tubes based on a standard curve of net absorbance measured at a given wavelength between 575nm and 615nm and serially diluted serum concentrations.

[0247] Table 2

[0248]

[0249] Example 5 - Antibacterial and antiviral properties of plastic articles based on a mixture of a functional resin (101) or a modified thermoplastic resin composition (100), a masterbatch (104) and a core resin (103)

[0250] Table 3 summarizes the antibacterial and antiviral properties of molded test samples of a batch of composition examples based on a mixture of a functional resin (101), or a modified thermoplastic resin composition (100), a masterbatch (104), and a core resin (103). These examples clearly show promising observations. In particular, composition example 2 synergistically exerts excellent killing / deactivation and repelling effects while also being shown to be biocompatible and safe for food contact.

[0251] Table 3

[0252]

[0253] 1 Bactericidal efficacy. Tested by an accredited laboratory in accordance with ISO 22196:2011 / JIS Z 2801:2010.

[0254] 2 Antibacterial efficacy. Tested by an accredited laboratory in accordance with T / GDPIA 1-2019 / ASTM WK66122 (as of October 2022, this work item standard has been accepted as ASTM E3371-22).

[0255] 3 Virucidal activity. Tested by an accredited laboratory according to ISO 21702:2019.

[0256] 4 Example 2 was confirmed to have passed food contact safety testing in accordance with US FDA 21CFR 177.1520(d)(1), (d)(3)(ii) & (d)(4)(ii) and EU No 10 / 2011 in terms of overall migration in three simulants: 3% (w / v) acetic acid aqueous solution, 10% (v / v) ethanol aqueous solution, and distilled olive oil (all at 70°C for 2 hours), as well as specific migration of heavy metals and primary aromatic amines in 3% (w / v) acetic acid aqueous solution under the same conditions. Maleic anhydride was also confirmed to remain within the specific migration limits specified in EU No. 10 / 2011 for aqueous and fatty food simulants under the same conditions. The sample (Example 3) also passed the acute systemic toxicity test in accordance with GB / T 16886.11-2011 and the in vitro hemolysis test in accordance with GB / T 16886.4-2003. All tests were performed by accredited laboratories. The melt index (230°C / 2.16 kg) of PPR-a and PPR-b is 10 and 1.1 g / 10 min, respectively. When the plastic substrate of (100) in Example 3 is changed from PPR-a to PPR-b, the antibacterial performance of (101) against Staphylococcus aureus is undoubtedly improved from 99.90% to 99.99% relative to PPR-b, as with (101). On the other hand, when the plastic substrate of (101) is replaced by a PPR with a much higher melt flow, such as Moplen RP348S with a melt index of 35 g / 10 min, the antibacterial performance of (101) against Staphylococcus aureus can reach 99.10% relative to the pure PPR of Moplen RP348S, thereby indicating that the compatibility between the substrates (which are not necessarily the same commercial model of PPR) between (100) and (101) is minimally affected.

[0257] 5Example 4 (no AEO-n in the composition) was able to demonstrate selectivity against Gram-positive bacteria (Staphylococcus aureus) and Gram-negative bacteria (Escherichia coli).

[0258] 6 The modified thermoplastic resin composition (100) can functionalize condensate plastics (such as polyamide) to have antimicrobial properties to a certain extent.

[0259] The citation of any reference herein is not to be construed as an admission that such reference is available as prior art to the present invention. Furthermore, reference in this specification to any prior publication (or information derived from a prior publication) or any known matter is not and should not be construed as an admission or permission or any form of suggestion that the prior publication (or information derived from a prior publication) or known matter forms part of the common general knowledge in the field of business to which this specification relates.

[0260] Those skilled in the art will appreciate that the disclosure described herein is susceptible to variations and modifications other than those specifically described. It is to be understood that the disclosure includes all such variations and modifications. The disclosure also includes all steps, features, compositions and compounds referred to or indicated in this specification, individually or collectively, and any and all combinations of two or more of said steps, features, compositions and compounds.

Claims

1. A thermoplastic resin modifier composition, comprising: (i) a vinyl monomer in an amount of 0.5% (w / w) to 4% (w / w); (ii) a copolymerizable anhydride in an amount of 0.5% (w / w) to 4% (w / w); (iii) a thermal free radical polymerization initiator in an amount of 0.05% (w / w) to 2% (w / w); and (iv) a thermoplastic resin in an amount of 90% (w / w) to 98% (w / w), optionally an organic solvent, and optionally a deodorant, The vinyl monomer is a short-chain olefin, styrene, alkyl acrylate, alkyl acrylate, vinyl acetate, vinyl alcohol, vinyl phenol, vinyl alkyl ether, vinyl halide, vinyl acetic acid, acrylonitrile, acrylamide, vinyl silane, unsaturated fatty acid or unsaturated fatty acid ester.

2. The thermoplastic resin modifier composition according to claim 1, wherein the vinyl monomer is styrene, α-methylstyrene, vinylnaphthalene, isobutylene, vinyl norbornene, butyl vinyl ether or 2-chloroethyl vinyl ether. 3 . The thermoplastic resin modifier composition according to claim 1 , comprising a plurality of vinyl monomers.

4. The thermoplastic resin modifier composition according to claim 3, wherein the plurality of vinyl monomers are selected from the group consisting of vinyl acetate, acrylamide, N-isopropylacrylamide, N-vinylpyrrolidone, N-hydroxymethylacrylamide, 2-methoxyethyl acrylate, furfuryl methacrylate, tetrahydrofurfuryl acrylate, 4-acryloylmorpholine, 2-N-morpholinoethyl methacrylate, acrylamidoglycolic acid, acrylonitrile, methacrylic acid, methyl methacrylate, 2-ethylhexyl acrylate, butyl acrylate, isobornyl methacrylate, 2-hydroxyethyl methacrylate, 2-aminoethyl methacrylate, 2-(dimethylamino)ethyl methacrylate, 3-methacryloyloxypropyltrimethoxysilane, 2-carboxyethyl acrylate, 2-azacycloheptaneethyl methacrylate, glycidyl methacrylate, allyl glycidyl ether, 2-vinylpyridine, 4-tert-butoxystyrene, and 4-vinylcatechol acetone.

5. The thermoplastic resin modifier composition according to any one of claims 1 to 2 and 4, wherein the copolymerizable acid anhydride is an organic acid anhydride.

6. The thermoplastic resin modifier composition according to claim 5, wherein the organic acid anhydride is maleic anhydride.

7. The thermoplastic resin modifier composition according to any one of claims 1 to 2, 4, and 6, wherein the thermal radical polymerization initiator is a peroxide or an azo compound.

8. The thermoplastic resin modifier composition according to claim 7, wherein the radical polymerization initiator is a mixture of benzoyl peroxide and dicumyl peroxide.

9. The thermoplastic resin modifier composition according to claim 8, wherein the benzoyl peroxide and the dicumyl peroxide are present in a molar ratio between 20:80 and 80:

20.

10. The thermoplastic resin modifier composition according to any one of claims 1 to 2, 4, 6, 8, and 9, wherein the thermoplastic resin is a medium to high flow homopolyolefin, a multi-block copolymer, a random copolymer, or a mixture thereof.

11. The thermoplastic resin modifier composition according to any one of claims 1 to 2, 4, 6, 8, and 9, wherein the thermoplastic resin is an addition polymer, a polyolefin elastomer, a thermoplastic olefin, a thermoplastic vulcanizate, or a rubber.

12. The thermoplastic resin modifier composition according to any one of claims 1 to 2, 4, 6, 8, and 9, wherein the thermoplastic resin is PE, PP, PB, COC, CBC, PCHE, PMP, PVB, PAN, NBR, EPR, PI, SEBS, SEPS, SBS, SIS, MBS, ABS, AES, HNBR, XNBR, ACM, IIR, ECO, EBA, EVA, EVOH, EAA, EMA, EPDM, ETFE, ECTFE, EVCL, CPE, OPE, TPEE, TPC, TPU, TPAE, PEBA, TSPCU, poly(ethylene-co-1-octene), poly(ethylene-co-1-hexene), poly(ethylene-co-1-butene), chloroprene rubber, olefin metathesis products, or any polymer compound having repeating units consisting of aliphatic-, cyclo-, or aliphatic-alkyl, aliphatic-alkenyl, or aliphatic-alkynyl groups containing at least one or more CH units in the main chain or side chains, or any combination thereof.

13. A method for preparing a modified thermoplastic resin composition, the method comprising: Will (i) a vinyl monomer in an amount of 0.5% (w / w) to 4% (w / w); (ii) a copolymerizable anhydride in an amount of 0.5% (w / w) to 4% (w / w); (iii) a thermal free radical polymerization initiator in an amount of 0.05% (w / w) to 2% (w / w); and (iv) a thermoplastic resin in an amount of 90% (w / w) to 98% (w / w) combining to provide a mixture, and subjecting the mixture to melt processing or solvent-assisted solid phase polymerization, The vinyl monomer is a short-chain olefin, styrene, alkyl acrylate, alkyl acrylate, vinyl acetate, vinyl alcohol, vinyl phenol, vinyl alkyl ether, vinyl halide, vinyl acetic acid, acrylonitrile, acrylamide, vinyl silane, unsaturated fatty acid or unsaturated fatty acid ester.

14. The method of claim 13, wherein melt processing comprises extrusion, molding, film blowing, spinning, stretching, pressing, kneading, rolling, or thermoforming.

15. The method of claim 14, wherein melt processing comprises extrusion.

16. The method according to claim 13, wherein the modified thermoplastic resin composition is subjected to a surface treatment.

17. The method according to claim 16, wherein the surface treatment is a treatment for imparting antifouling, oil-repellent and / or water-repellent properties to the modified thermoplastic resin composition.

18. A modified thermoplastic resin composition whenever prepared by the method according to any one of claims 13 to 17.

19. A method for preparing a functional resin composition, comprising combining the modified thermoplastic resin composition of claim 18 with one or more additives to form a mixture, and subjecting the mixture to melt processing.

20. The method of claim 19, wherein the one or more additives include one or more compounds having antibacterial, antiviral, or antifouling properties.

21. The method of claim 20, wherein the one or more compounds having antibacterial, antiviral or antifouling properties are hydrophilic compounds.

22. The method of claim 20, wherein the one or more compounds having antibacterial, antiviral or antifouling properties are amphiphilic compounds.

23. The method of claim 22, wherein the amphiphilic compound has an HLB value greater than 7.

24. The method of claim 22, wherein the amphiphilic compound has an HLB value between 7 and 20.

25. The method of any one of claims 19 to 24, wherein the one or more additives comprise a core resin.

26. The method of any one of claims 19 to 24, wherein the one or more additives comprises an antioxidant.

27. The method of any one of claims 19 to 24, wherein melt processing comprises extrusion, molding, film blowing, spinning, stretching, pressing, kneading, rolling or thermoforming.

28. The method of claim 27, wherein melt processing comprises extrusion.

29. A functional resin composition whenever prepared by the method according to any one of claims 19 to 28.

30. A method for producing a plastic product, comprising shaping the functional resin composition according to claim 29.

31. The method of claim 30, wherein forming is achieved by molding.

32. The method of claim 31 , wherein the molding is injection molding, rotational molding, blow molding, or compression molding.

33. A method for preparing a plastic product, comprising: (i) will (a) modified thermoplastic resin composition; (b) core resin; and (c) a compound selected from alcohol ethoxylates, alkylene oxides and polyethylene glycols combining to form a mixture; (ii) subjecting the mixture to melt processing or solvent-assisted solid phase polymerization to provide a functional resin composition; and (iii) shaping the functional resin composition to provide the plastic article, and wherein the modified thermoplastic resin composition is prepared by mixing (d) a vinyl monomer in an amount of 0.5% (w / w) to 4% (w / w); (e) a copolymerizable anhydride in an amount of 0.5% (w / w) to 4% (w / w); (f) a thermal free radical polymerization initiator in an amount of 0.05% (w / w) to 2% (w / w); and (g) a thermoplastic resin in an amount of 90% (w / w) to 98% (w / w) to form a mixture, and (iv) subjecting the mixture to melt processing, The vinyl monomer is a short-chain olefin, styrene, alkyl acrylate, alkyl acrylate, vinyl acetate, vinyl alcohol, vinyl phenol, vinyl alkyl ether, vinyl halide, vinyl acetic acid, acrylonitrile, acrylamide, vinyl silane, unsaturated fatty acid or unsaturated fatty acid ester.

34. The method of claim 33, wherein the core resin is polypropylene.

35. The method of claim 34, wherein the polypropylene is a polypropylene random copolymer.

36. The method of any one of claims 33 to 35, wherein in (c), the compound is an alcohol ethoxylate.

37. The method of claim 36, wherein the alcohol ethoxylate has the general formula: RO(CH2CH2O) n H, where R is C 12 -C 14 alkyl and n=3 to 23.

38. The method of claim 37, wherein the alcohol ethoxylate has the general formula: RO(CH2CH2O) n H, where R is C 12 -C 14 Alkyl and n=3 to 9.

39. The method of claim 36, wherein the alcohol ethoxylate has an HLB 10 value between 10 and 11.

40. A method according to any one of claims 33 to 35, 37, 38, 39, wherein the melt processing in steps (ii) and (iv) comprises extrusion.

41. The method of any one of claims 33 to 35, 37, 38, 39, wherein the mixture in step (i) further comprises an antioxidant.

42. The method of any one of claims 33 to 35, 37, 38, 39, wherein the vinyl monomer is styrene.

43. A method according to any one of claims 33 to 35, 37, 38, 39, wherein the shaping in step (iii) is performed by moulding.

44. The method of claim 43, wherein the molding is injection molding.

45. The method of any one of claims 33 to 35, 37, 38, 39, 44, wherein the plastic article is a protein-resistant plastic article.

46. A method of producing a plastic article comprising combining the modified thermoplastic resin composition of claim 18 with one or more additives to form a masterbatch, combining the masterbatch with a core resin to form a mixture, and processing the mixture to form the plastic article.

47. A method of producing a plastic article, comprising combining the modified thermoplastic resin composition of claim 18 with a masterbatch and a core resin to form a mixture, and processing the mixture to form the plastic article.

48. A method according to claim 46 or 47, wherein the masterbatch comprises one or more compounds having antibacterial, antiviral or antifouling properties.

49. The method of claim 48, wherein the one or more compounds having antibacterial, antiviral or antifouling properties are hydrophilic compounds.

50. The method of claim 49, wherein the one or more compounds having antibacterial, antiviral or antifouling properties are amphiphilic compounds.

51. The method of claim 50, wherein the amphiphilic compound has an HLB value greater than 7.

52. The method of claim 51, wherein the amphiphilic compound has an HLB value between 7 and 20.

53. A method for preparing a plastic product, comprising: (i) will (a) modified thermoplastic resin composition; (b) core resin; and (c) Masterbatches containing alcohol ethoxylates, alkylene oxides or polyethylene glycols combining to form a mixture; and (ii) shaping the mixture to provide the plastic article, wherein the modified thermoplastic resin composition is prepared by mixing (d) a vinyl monomer in an amount of 0.5% (w / w) to 4% (w / w); (e) a copolymerizable anhydride in an amount of 0.5% (w / w) to 4% (w / w); (f) a thermal free radical polymerization initiator in an amount of 0.05% (w / w) to 2% (w / w); and (g) a thermoplastic resin in an amount of 90% (w / w) to 98% (w / w) to form a mixture, and (iii) subjecting said mixture of (d), (e), (f) and (g) to melt processing or solvent-assisted solid phase polymerization, The vinyl monomer is a short-chain olefin, styrene, alkyl acrylate, alkyl acrylate, vinyl acetate, vinyl alcohol, vinyl phenol, vinyl alkyl ether, vinyl halide, vinyl acetic acid, acrylonitrile, acrylamide, vinyl silane, unsaturated fatty acid or unsaturated fatty acid ester.

54. The method of claim 53, wherein the core resin is polypropylene.

55. The method of claim 54, wherein the polypropylene is a polypropylene random copolymer.

56. The method of any one of claims 53 to 55, wherein the masterbatch comprises an alcohol ethoxylate.

57. The method of claim 56, wherein the alcohol ethoxylate has the general formula: RO(CH2CH2O) n H, where R is C 12 -C 14 Alkyl and n=3-9.

58. The method of claim 57, wherein the alcohol ethoxylate has the general formula: RO(CH2CH2O) n H, where R is C 12 -C 14 Alkyl and n=5.

59. The method of claim 56, wherein the alcohol ethoxylate has an HLB value between 10 and 11.

60. A method according to any one of claims 53 to 55, 57 to 59, wherein the shaping in step (ii) is performed by moulding.

61. The method of claim 60, wherein the molding is injection molding.

62. The method of any one of claims 53 to 55, 57 to 59, 61, wherein the melt processing in step (iii) comprises extrusion.

63. The method of any one of claims 53 to 55, 57 to 59, 61, wherein the vinyl monomer is styrene.

64. The method of any one of claims 53 to 55, 57 to 59, 61, wherein the mixture of (d), (e), (f), and (g) is free or substantially free of surfactant.

65. A plastic article whenever obtained by the method of any one of claims 33 to 64.

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