Non-polymer coupling agent formulations for wood polymer composites

Abstract

Non-polymer coupling agent formulations for producing wood polymer composites are provided, the non-polymer coupling agent formulations comprising at least one organic peroxide and a non-polymer bio-based additive, the non-polymer bio-based additive comprising at least one of a bio-based oil or a bio-based acid or a derivative of a bio-based oil or acid. The coupling agent formulations are capable of producing polymer matrix composites with improved strength and aging characteristics. The improved strength can be related to physical properties such as improved stiffness, toughness, or tensile strength. A masterbatch utilizing the non-polymer coupling agent formulations is provided as well as a method of making the masterbatch.

Description

Technical Field

[0001] This disclosure relates to nonpolymer coupling agent formulations for improving the compatibility and properties of polyolefin-wood matrix or wood product composites. Background Technology

[0002] One method for manufacturing wood-polymer composite decks involves melting and blending a combination of wood flour and polyethylene in an extruder to form boards that mimic wood. However, blends of wood flour and polyethylene are incompatible.

[0003] Poor compatibility between wood and various polymers or their blends leads to undesirable consequences such as cracking in composite boards, reduced physical properties, and increased water absorption. Water absorption diminishes the aging characteristics of the composite material (i.e., the retention of desired physical properties over time). One approach to this problem is to incorporate maleic anhydride-grafted polymers into wood filler-polymer matrix blends. Maleic anhydride-grafted polyethylene (MAH-g-PE) or maleic anhydride-grafted polypropylene (MAH-g-PP) polymers are referred to as polymer compatibilizers or polymer coupling agents. These additives include, for example, maleic acid-modified polyolefins, such as those from Chemitura. A series from DuPont. Series, from ExxonMobil Series and from Arkema series.

[0004] Coupling additives are needed to increase mechanical strength and reduce water absorption, especially for load-bearing applications, and even more specifically for such load-bearing applications exposed to the external environment, such as wood polymer composite panels for outdoor decks.

[0005] US 2017 / 0275462 discloses thermoplastic polymers, cellulose materials, and functional fillers. The functional fillers include inorganic microparticles treated with surface-treatment agents. These inorganic microparticles include calcium carbonate, kaolin, talc, magnesium hydroxide, and gypsum. The surface-treatment agents used to coat the inorganic microparticles are specialty acrylates (e.g., β-carboxyethyl acrylate, β-carboxyhexylmaleimide). The surface treatment also includes one or more fatty acids. Optional peroxide additives are disclosed, including dicumyl peroxide or 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, which can be added to high-density polyethylene (HDPE) polymers to promote crosslinking. Optional peroxides can be added to polypropylene (PP) to promote chain scission.

[0006] US 2014 / 0121307 discloses the use of modified lignin, hydroxypropyl lignin (HPL), HDPE, LDPE (low-density polyethylene), PP, and polystyrene. Hydrogen peroxide is blended with a polymer compatibilizer. The compatibilizer is a standard grafted MAH (MAH-g-PE) onto polyethylene or a copolymer of polyethylene in which the MAH is in the polymer chain (rather than grafted onto the chain).

[0007] US 2004 / 0126515 discloses the production of composite materials using a polyethylene polymer blended with wood particles. The polyethylene has a melt flow index (MFI) of less than about 2 g / 10 min. An adhesive is also disclosed, which is a polymer having an MFI greater than that of the polyethylene used in the wood-plastic composite. This adhesive is a carboxylic acid or anhydride substance chemically bonded to the polyethylene chains prior to its use in the wood-plastic composite. The application also discloses wood lignin and terpenes in the wood-plastic composite, which can cause undesirable foaming.

[0008] US 5,179,149 discloses the use of stand oil. Stand oil is a heat-treated polymerized natural oil that is chemically and physically distinct from non-polymerized natural oils. Stand oil is manufactured by polymerizing linseed oil, tung oil, soybean oil, fish oil, rapeseed oil, canola oil, or other natural oils or mixtures at high temperatures for several hours using an organic peroxide. The method for preparing stand oil involves heating the natural oil and organic peroxide in a reactor at 200°C to 280°C. The final material, referred to as stand oil intermediate, is ground into a powder and used to manufacture nonwoven products. In a further step, the stand oil intermediate is added to poly(ethylene propylene diene) terpolymer (EPDM), wood filler, PE, clay, and tert-butyl peroxybenzoate, mixed, and then pressed into sheets and cured at 140°C.

[0009] US 7,850,771 discloses a method for preparing aqueous emulsions of polyethylene wax, wood preservatives, and optional reagents (such as tung oil, linseed oil, acrylic acid, and organic acids) using azobisisobutyronitrile (AIBN) and hydrogen peroxide as free radical initiators, wherein azobisisobutyronitrile and hydrogen peroxide constitute the wood preservative composition. It also discloses the use of alkyl acrylates that can be cured with AIBN, hydrogen peroxide, or potassium persulfate.

[0010] US 2020 / 0056020 disclosed the preparation of a material containing a capstock and a core, wherein the core is composed of a bimodal polymer resin and a non-bio-based maleic anhydride.

[0011] There remains a need for cost-effective and easy-to-use coupling agents for wood polymer composites designed to serve as alternatives to conventional wood, particularly for outdoor applications such as decking. Summary of the Invention

[0012] Non-polymer coupling agent formulations for use in wood polymer composites comprise: a) at least one organic peroxide (at room temperature, which may or may not be functionalized), having a half-life of at least one hour, preferably at least three months, at 98°C; and b) at least one non-polymer bio-based additive. Information on the one-hour half-life of various organic peroxides is available at Arkema (Colombes Cedex). See the catalog of organic peroxides / polymers, and its entirety is incorporated herein for all purposes. Apart from half-life, the organic peroxides used in the non-polymer coupling agent formulations of this invention are solid in their pure state at 20°C and show no significant loss in peroxide determination for at least one month at the same temperature.

[0013] The b) at least one non-polymer bio-based additive is selected from the group consisting of: i) at least one natural oil or a derivative thereof; ii) at least one natural acid, a natural acid anhydride, or an ester thereof; iii) at least one natural solid compound; and iv) mixtures thereof. The non-polymer coupling agent formulation may also contain c) at least one sulfur-containing compound. The non-polymer coupling agent may also contain an allyl-containing compound.

[0014] This article also discloses nonpolymer coupling agent formulations in combination with masterbatches comprising one or more fillers, wood flour, sawdust, and / or powdered polyethylene or PE granules. Detailed Implementation

[0015] Unless otherwise specified, all percentages in this document are weight percentages.

[0016] As used herein, “polymer” means an organic molecule having a weight average molecular weight of more than 20,000 g / mol, preferably more than 50,000 g / mol, more preferably more than 150,000, as measured by gel permeation chromatography.

[0017] As used herein with respect to wood or wood product fillers for wood polymer composites, “dry” means when the wood filler is heated at 103°C until a constant mass of water, measured by weight loss as determined by thermogravimetric analysis, is achieved, including at most 0 wt% to 1 wt%, at most 2 wt%, but not exceeding 5 wt%. This method is described in Philipp Dietsch et al., “Methods to determine wood moisture and their applicability in monitoring concepts”; (Dr.-Ing., Research Associate and Chair of Timber Structures and Building Construction; Technical University of Munich, Germany; Journal of Civil Structural Health Monitoring; Vol. 5, pp. 115-127 (2015). Furthermore, a device from KJ Industries called the “Sawdust Moisture Meter TK100W” has a moisture measurement range of 0 wt% to 84 wt%. This device can be used to measure the moisture content of various woody materials, such as wood flour, sawdust, paillasse, and bamboo powder.

[0018] Reducing the moisture content of wood flour or sawdust is important because water inhibits or even prevents the bonding between wood fibers and polymers. Excessive water can also lead to undesirable porosity. Wood flour can have a moisture content (water) of 4 wt% to 6 wt% or higher. Preferably, the dried wood flour has a moisture content of less than 4 wt%, preferably about 3 wt%, more preferably about 2 wt%, more preferably about 1 wt%, and even more preferably about 0.5 wt% or lower.

[0019] Wood flour particle size ranges from 80 mesh to 40 mesh (180-425 μm). For example, particle sizes outside this typical range can also be considered, such as up to 20 mesh (850 μm or 0.85 mm diameter).

[0020] As used herein, the term "wood flour" refers to plant-based fibers and nanocrystals that can be derived from any source, including but not limited to hardwoods, softwoods, bamboo, rice husks, corn husks, flax, kenaf, recycled paper or waste paper, recycled cardboard or waste cardboard, and which can also be pulverized into particles with a consistency ranging from fine powder to particles up to 10 mm in size.

[0021] The terms “bio-based” and “natural” are used to refer to materials and their structural units found in nature, including, but not limited to, those that can be synthesized. In some embodiments, “bio-based” and “natural” further additionally refer to materials and compositions (in any way produced) derived from such bio-based and natural materials and structural units, including those synthesized artificially. The term “structural unit” as used means a natural portion that can be chemically modified to produce other compounds and products.

[0022] "Natural solids" refers to portions of the solid phase that are found in nature; natural solids include portions selected from the group consisting of: acid anhydrides (including chemically modified acid anhydrides), waxes (such as carnauba wax), minerals (such as aluminum sulfate, sodium aluminum sulfate, aluminum hydroxide, potassium aluminum sulfate, ammonium aluminum sulfate (alum), potassium aluminum sulfate, aluminum lactate, ferrous sulfate, and stannous chloride).

[0023] Natural oils as mentioned herein may include tung oil, oitica oil, castor oil, sorbitol esters (e.g., sorbitol tristearate, sorbitol monolaurate, sorbitol monooleate, sorbitol dioleate, sorbitol trioleate, sorbitol monolinoleate, sorbitol dilinoleate, sorbitol trilinoleate), polysorbate 80, ω-3, limonene, myrcene, and related natural terpenoids described below, and mixtures thereof. Preferred natural oils include tung oil, oitica oil, castor oil, polysorbate 80, sorbitol tristearate, sorbitol monolaurate, sorbitol dilinoleate, sorbitol monolinoleate, limonene, myrcene, and mixtures thereof. More preferred natural oils include tung oil, turmeric oil, polysorbate 80, sorbitol monolinoleate, sorbitol monooleate, sorbitol trioleate, limonene, and mixtures thereof. In some embodiments, the natural oil may have at least one carbon-carbon double bond that is reactive to free radicals, preferably two conjugated carbon-carbon double bonds, more preferably three or more conjugated carbon-carbon double bonds. In some embodiments, the natural oil may be fully saturated and have no carbon-carbon double bonds.

[0024] Chemically modified natural oils may include epoxidized soybean oil, epoxidized lecithin, epoxidized itaconic acid, diallyl epoxidized itaconic acid, epoxidized sorbitan dioleate, partially epoxidized limonene, partially epoxidized itaconic acid, partially epoxidized terpenes, partially epoxidized sorbitan dioleate, partially epoxidized sorbitan trioleate, or mixtures thereof. Partially epoxidized natural oils and epoxidized phospholipids are preferred. More preferably, they include partially epoxidized itaconic acid, partially epoxidized sorbitan dioleate, partially epoxidized limonene, and partially epoxidized sorbitan trioleate. Even more preferably, they include partially epoxidized itaconic acid and partially epoxidized limonene.

[0025] Non-polymer bio-based additives may include lecithin, various sugars, artificial sugars, oxidized sugars, sugar alcohols, phosphoproteins such as casein, or mixtures thereof. Lecithin and casein are preferred.

[0026] Non-polymer bio-based additives may include oleic acid derivatives, such as sorbitol monooleate, sorbitol dioleate, and sorbitol trioleate, or mixtures thereof. Sorbitol monooleate and sorbitol trioleate are preferred.

[0027] Non-polymeric natural solid compounds can include naturally occurring minerals such as alum, aluminum sulfate, aluminum hydroxide, potassium aluminum sulfate, sodium aluminum sulfate, boric acid, disodium tetraborate (also known as sodium borate or borax), ferrous sulfate, and stannous chloride.

[0028] Natural acids can include, for example, abietic acid, benzoic acid, itaconic acid, succinic acid, malonic acid, tannic acid, including their corresponding anhydride forms, as well as methyl esters of abietic acid and abalyn. Anhydrides can include, for example, itaconic anhydride, succinic anhydride, allyl succinic anhydride, isononenyl succinic anhydride, etc.

[0029] Organic peroxides may contain small amounts of high-boiling-point non-aromatic compounds, such as mineral oil or petroleum ether, which can be used as a safe diluent. Organic peroxide formulations may also contain polysorbate 80, polypropylene glycol, or mixtures thereof.

[0030] In some embodiments, at least one organic peroxide may be used with elemental sulfur and / or sulfur-containing compounds and at least one other coupling agent compound selected from natural oils, natural solids, acids, chemically modified oils, or active coagents. Such formulations may or may not be formulated as free-flowing powder masterbatches dispersed on the various inert fillers and / or powdered polymers described herein.

[0031] Blends of these natural oils and their derivatives, natural acids, natural acid anhydrides, esters of natural acids and natural acid anhydrides, natural solids, and / or at least one sulfur-containing compound and / or active auxiliaries with one or more organic peroxides are considered. Preferred are tert-amyl peroxide and tert-butyl peroxide.

[0032] In some embodiments, the organic peroxide formulation may contain at least one stabilizer, including, for example, but not limited to, at least one quinone compound or at least one nitrooxy compound or a combination thereof. In some embodiments, the peroxide formulation contains at least one quinone compound or at least one nitrooxy compound or a combination thereof, and may also contain at least one allyl compound or more preferably diallyl compound, and even more preferably triallyl compound as an active ingredient.

[0033] Other embodiments of blends containing at least one organic peroxide may contain, consist of, or consist substantially of: (i) epoxidized soybean oil and itaconic acid or malonic acid; (ii) epoxidized soybean oil, itaconic acid, and malonic acid; (iii) epoxidized soybean oil and zinc oxide or magnesium oxide, and itaconic acid and / or malonic acid.

[0034] The formulations of the present invention can be formulated as powder masterbatches, preferably free-flowing, dispersed on various inert fillers and / or powdered polymers described herein.

[0035] In some cases, functionalized organic peroxides can be selected from those room-temperature stable peroxides having carboxylic acid, one or more double bonds capable of reacting with free radicals, methoxy or hydroxyl functional groups (i.e., having a half-life of at least 1 hour at 98°C), such as tert-butylperoxymaleic acid (from Arkema). PNP-25). This carboxylic acid-functionalized organic peroxide can be blended with various additives disclosed herein, including acids (such as itaconic acid), their anhydrides, and / or their allyl esters. The nonpolymer coupling agent formulation may further comprise dried wood flour, dried sawdust, cellulose acetate butyrate powder, chlorinated polyethylene powder, chlorosulfonated polyethylene powder, and / or polyethylene powder or polyethylene granules to produce novel nonpolymer coupling agent masterbatches.

[0036] These coupling agent formulations can also be extended onto fillers or filler blends to provide free-flowing powder products or masterbatches. Non-limiting examples of such fillers include calcium carbonate, Burgess clay, precipitated silica, microcrystalline cellulose, cellulose acetate butyrate (CAB), calcium silicate, silica, fly ash, dried wood flour, dried sawdust, dried straw pellets / powder, polyethylene in powder or granular form, or mixtures thereof. Preferred are Burgess clay, precipitated calcium carbonate, precipitated silica, calcium silicate, microcrystalline cellulose, dried wood flour, dried sawdust, cellulose acetate butyrate, high-density polyethylene powder, polypropylene powder, and mixtures thereof. Most preferred are Burgess clay, precipitated silica, calcium silicate, high-density polyethylene powder, dried wood flour, dried sawdust, and mixtures thereof.

[0037] In one embodiment, a non-polymer coupling agent can completely replace the conventional polymer-grafted MAH compatibilizer in wood polymer composite formulations. In another embodiment, a non-polymer coupling agent formulation can partially replace the conventional polymer MAH coupling agent in existing wood polymer composites.

[0038] Non-polymer coupling agent formulations can be added to wood flour and polyethylene alone or as a masterbatch. This composition can then be melt-blended and extruded to form, for example, wood-polymer composite deck boards.

[0039] Organic peroxides

[0040] Suitable organic peroxides applicable to some embodiments of the present invention may be selected from room-temperature stable organic peroxides. Organic peroxides may be in liquid form, solid form, solid flakes, solid powder form extended on an inert filler, fusible solid form, or pourable paste form. These various peroxide forms can be used in the coupling agent compositions disclosed herein. Suitable organic peroxides may be able to decompose and form reactive free radicals when exposed to a heat source, such as in an extruder.

[0041] The organic peroxides suitable for certain embodiments of non-polymer coupling agent compositions for wood polymer composites may be selected from those peroxides having carboxylic acid, methoxy, or hydroxyl functional groups that are stable at room temperature. In the context of this disclosure, "room temperature stable" means an organic peroxide that has not decomposed after at least three months at 20°C, i.e., retains its measured value. In the context of this disclosure, a room temperature stable organic peroxide may be defined as having a half-life of at least 1 hour at 98°C. Exceptions to this rule apply to diacyl solid peroxides: non-limiting examples include dibenzoyl peroxide; dilauryl peroxide; 2,4-dichlorobenzoyl peroxide; or p-methyldibenzoyl peroxide, which are thermally stable at ambient temperature of 20°C but have a half-life of less than 1 hour at 98°C.

[0042] Non-limiting examples of suitable organic peroxide classes include diacid peroxides, peroxide esters, monoperoxide carbonates, peroxide ketals, hemiperoxide ketals, peroxide dicarbonates that are solid at ambient temperature (20°C), and dialkyl peroxide classes are also suitable, as are tert-butyl peroxide and tert-amyl peroxide classes. Furthermore, cyclic organic peroxides are considered, for example, those from Nouryon. 301 and 311 Peroxides. Suitable peroxides can be found in Jose Sanchez and Terry N., “Organic Peroxides”; Kirk Othmer Encyclopedia of Chemical Technology, 4th Edition, Volume 18, (1996), the disclosure of which is incorporated herein by reference in its entirety for all purposes. Thermally stable functionalized peroxides having carboxylic acids, hydroxyl groups and / or having radical-reactive unsaturated groups are also suitable. Organic peroxides may contain small amounts of mineral oil, mineral concentrate, or food-grade white mineral oil as a safe diluent.

[0043] Organic peroxides can also be extended on inert fillers (e.g., wood flour, sawdust, bamboo flour, straw, straw powder, rice husk, wheat straw, hemp, flax, peanut shell powder, waste paper, waste cardboard, Burgess clay, kaolin, calcium carbonate, silica, calcium silicate, and cellulose acetate butyrate), or used as peroxide masterbatches in powder or granule form on EPDM (ethylene propylene diene monomer rubber), EPM (ethylene propylene rubber), PE (polyethylene), HDPE (high-density polyethylene), PP (polypropylene), microcrystalline wax, and polycaprolactone, wherein the peroxide concentration can vary from 1 wt% to 80 wt%, preferably from 0.1 wt% to 60 wt%, and more preferably from 0.1 wt% to 40 wt%, depending on the application.

[0044] Non-limiting examples of suitable organic peroxides are: di-tert-butyl peroxide; tert-butylcumyl peroxide; tert-amylcumyl peroxide; dicumyl peroxide; 2,5-di(cumylperoxy)-2,5-dimethylhexane; 2,5-di(cumylperoxy)-2,5-dimethylhexyn-3; 4-methyl-4-(tert-butylperoxy)-2-pentanol; 4-methyl-4-(tert-amylperoxy)-2-pentanol; 4-methyl-4-(cumylperoxy)-2-pentanol; 4-methyl-4-(tert-butylperoxy)-2-pentanone; 4-methyl-4-(tert-amylperoxy)-2-pentanone; 4 -Methyl-4-(cumylperoxy)-2-pentanone; 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane; 2,5-dimethyl-2,5-di(tert-pentylperoxy)hexane; 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyn-3; 2,5-dimethyl-2,5-di(tert-pentylperoxy)hexyn-3; 2,5-dimethyl-2-di-tert-butylperoxy-5-hydroperoxyhexane; 2,5-dimethyl-2-cumylperoxy-5-hydroperoxyhexane; 2,5-dimethyl-2-tert-pentylperoxy-5-hydroperoxyhexane; meta / para-α,α-di( tert-Butylperoxy)isopropylbenzene; m-Di(tert-Butylperoxy)diisopropylbenzene; p-Di(tert-Butylperoxy)diisopropylbenzene; 1,3,5-Tris(tert-Butylperoxyisopropyl)benzene; 1,3,5-Tris(tert-Amylperoxyisopropyl)benzene; 1,3,5-Tris(cumylperoxyisopropyl)benzene; bis[1,3-dimethyl-3-(tert-Butylperoxy)butyl]carbonate; bis[1,3-dimethyl-3-(tert-Amylperoxy)butyl]carbonate; bis[1,3-dimethyl-3-(cumylperoxy)butyl]carbonate; bis-tert-Amylperoxide; tert-Amylcumylperoxide; tert-Butyl Peroxy-isopropenyl cumyl peroxide; tert-amylperoxy-isopropenyl cumyl peroxide; 2,4-diallyloxy-6-tert-butylperoxy-1,3,5-triazine; 2,4-diallyloxy-6-tert-amylperoxy-1,3,5-triazine; 2,4,6-tris(butylperoxy)-s-triazine; 1,3,5-tris[1-(tert-butylperoxy)-1-methylethyl]benzene; 1,3,5-tris-[(tert-butylperoxy)-isopropyl]benzene; 1,3-dimethyl-3-(tert-butylperoxy)butanol; 1,3-dimethyl-3-(tert-amylperoxy)butanol; and mixtures thereof. Exemplary solid, room-temperature stable peroxydicarbonates include, but are not limited to: di(2-phenoxyethyl) peroxydicarbonate; di(4-tert-butyl-cyclohexyl) peroxydicarbonate; dimyristyl peroxydicarbonate; dibenzyl peroxydicarbonate; and di(isobornyl) peroxydicarbonate. Solid diacyl peroxides include: dibenzoyl peroxide; 2,4-dichlorobenzoyl peroxide; and di(methylbenzoyl) peroxide.

[0045] Other dialkyl-type organic peroxides that can be used alone or in combination with other organic peroxides considered in this disclosure are those selected from the group represented by the following formulas:

[0046]

[0047] R4 and R5 can be independently located at the meta or para positions and can be the same or different, and are selected from hydrogen or straight-chain or branched alkyl groups having 1 to 6 carbon atoms. Dicumyl peroxide and isopropylcumyl peroxide are exemplary.

[0048] Other dialkyl peroxides may include, but are not limited to: 3-cumylperoxy-1,3-dimethylbutyl methacrylate; 3-tert-butylperoxy-1,3-dimethylbutyl methacrylate; 3-tert-amylperoxy-1,3-dimethylbutyl methacrylate; tris(1,3-dimethyl-3-tert-butylperoxybutoxy)vinylsilane; 1,3-dimethyl-3-(tert-butylperoxy)butylN-[1-{3-(1-methylvinyl)-phenyl}-1-methylethyl]carbamate; 1,3-dimethyl-3-(tert-amylperoxy)butylN-[1-{3-(1-methylvinyl)-phenyl}-1-methylethyl]carbamate; 1,3-dimethyl-3-(cumylperoxy)butylN-[1-{3-(1-methylvinyl)-phenyl}-1-methylethyl]carbamate.

[0049] Other variants of dialkyl peroxides containing two different peroxy groups with different chemical and / or thermal reactivity may be included in this invention. Non-limiting examples include 2,5-dimethyl-(2-hydroperoxy-5-tert-butylperoxy)hexane and 2,5-dimethyl-(2-hydroperoxy-5-tert-pentylperoxy)hexane.

[0050] Suitable compounds in the group consisting of disperoxyketal organic peroxides may include: 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane; 1,1-di(tert-pentylperoxy)-3,3,5-trimethylcyclohexane; 1,1-di(tert-butylperoxy)cyclohexane; 1,1-di(tert-pentylperoxy)cyclohexane; n-butyl 4,4-di(tert-pentylperoxy)valerate; ethyl 3,3-di(tert-butylperoxy)butyrate; 2,2-di(tert-pentylperoxy)propane; 3,6,6,9,9-pentamethyl-3-ethoxycarbonylmethyl-1,2,4,5-tetraoxane; n-butyl-4,4-bis(tert-butylperoxy)valerate; ethyl-3,3-di(tert-pentylperoxy)butyrate; and mixtures thereof.

[0051] Other organic peroxides that may be used according to at least one embodiment of this disclosure include benzoyl peroxide, OO-tert-butyl-O-hydro-monoperoxy-succinate, and OO-tert-pentyl-O-hydro-monoperoxy-succinate.

[0052] Exemplary cyclic ketone peroxides are compounds having the following general formulas (I), (II) and / or (III).

[0053]

[0054]

[0055] Among them, R1 to R 10 The groups are independently selected from the group consisting of hydrogen, C1 to C20 alkyl, C3 to C20 cycloalkyl, C6 to C20 aryl, C7 to C20 aralkyl, and C7 to C20 alkylaryl, which may include straight-chain or branched alkyl characteristics and each of R1 to R10 may be substituted by one or more groups selected from hydroxyl, C1 to C20 alkoxy, straight-chain or branched C1 to C20 alkyl, C6 to C20 aryloxy, halogen, ester, carboxyl, nitride, and amide.

[0056] Some non-limiting examples of suitable cyclic ketone peroxides include, but are not limited to: 3,6,9,triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane (or cyclic trimer of methyl ethyl ketone peroxide), cyclic dimer of methyl ethyl ketone peroxide, and 3,3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxane.

[0057] Non-limiting exemplary examples of peroxide esters include: 2,5-dimethyl-2,5-di(benzoylperoxy)hexane; tert-butylperbenzoate; tert-butylperoxyacetate; tert-butylperoxy-2-ethylhexanoate; tert-pentylperbenzoate; tert-pentylperoxyacetate; tert-butylperoxyisobutyrate; 3-hydroxy-1,1-dimethyltert-butylperoxy-2-ethylhexanoate; OO-tert-pentyl-O-hydro-monoperoxysuccinate; OO-tert-butyl-O-hydro-monoperoxysuccinate; di-tert-butyldisperoxyphthalate; tert-butylperoxy(3,3,5-trimethylhexanoate); 1,4-bis(tert-butylperoxycarbonyl)cyclohexane; tert-butylperoxy-3,5,5-trimethylhexanoate; tert-butyl-peroxy-(cis-3-carboxyl)propionate; 3-methyl-3-tert-butylperoxybutyrate allyl ester. Exemplary monoperoxycarbonates include: OO-tert-butyl-O-isopropyl monoperoxycarbonate; OO-tert-pentyl-O-isopropyl monoperoxycarbonate; OO-tert-butyl-O-(2-ethylhexyl)monoperoxycarbonate; OO-tert-pentyl-O-(2-ethylhexyl)monoperoxycarbonate; 1,1,1-tris[2-(tert-butylperoxy-carbonyloxy)ethoxymethyl]propane; 1,1,1-tris[2-(tert-pentylperoxy-carbonyloxy)ethoxymethyl]propane; 1,1,1-tris[2-(cumylperoxy-carbonyloxy)ethoxymethyl]propane; OO-tert-pentyl-O-isopropyl monoperoxycarbonate.

[0058] Other peroxides that can be used according to at least one embodiment of this disclosure include functionalized peroxy ester type peroxides: OO-tert-butyl-O-hydro-monoperoxysuccinate; OO-tert-pentyl-O-hydro-monoperoxysuccinate; OO-tert-pentylperoxymaleic acid and OO-tert-butylperoxymaleic acid.

[0059] In the practice of this invention, it is also suitable to use organic peroxy-branched oligomers containing at least three peroxy groups, which comprise compounds represented by the following structures:

[0060]

[0061] The sum of W, X, Y, and Z is 6 or 7. An example of this type of uniquely branched organic peroxide is tetrafunctional polyether tetra(tert-butyl peroxycarbonate). Examples of this type of peroxide are... JWEB50 (Arkema).

[0062] Exemplary organic peroxides of the semiperoxyketal class include: 1-methoxy-1-tert-pentylperoxycyclohexane; 1-methoxy-1-tert-butylperoxycyclohexane; 1-methoxy-1-tert-pentylperoxy-3,3,5-trimethylcyclohexane; 1-methoxy-1-tert-butylperoxy-3,3,5-trimethylcyclohexane. Examples of this type of peroxide are... V10 (Arkema) is 93% pure 1-methoxy-1,1-dimethylpropylperoxycyclohexane.

[0063] Exemplary diacyl peroxides include, but are not limited to: bis(4-methylbenzoyl) peroxide; bis(3-methylbenzoyl) peroxide; bis(2-methylbenzoyl) peroxide; decanoyl peroxide; dilauryl peroxide; 2,4-dibromobenzoyl peroxide; succinic acid peroxide; dibenzoyl peroxide; and bis(2,4-dichlorobenzoyl) peroxide. Imidoyl peroxides of the type described in PCT application publication WO 9703961A1 are also considered suitable for use and are incorporated herein by reference for all purposes.

[0064] Functionalized organic peroxides are suitable for use in non-polymer coupling agent formulations for wood polymer composites. A non-limiting example of a functionalized organic peroxide is tert-butylperoxymaleic acid. Non-limiting examples of functionalized peroxides are tert-butylperoxymaleic acid; tert-amylperoxymaleic acid; tert-butylperoxy-isopropenyl cumyl peroxide; tert-amylperoxy-isopropenyl cumyl peroxide; 4-methyl-4-(tert-butylperoxy)-2-pentanol; 4-methyl-4-(tert-amylperoxy)-2-pentanol; 4-methyl-4-(cumylperoxy)-2-pentanol; 2,5-dimethyl-(2-hydroperoxy-5-tert-butylperoxy)hexane and 2,5-dimethyl-(2-hydroperoxy-5-tert-amylperoxy)hexane; 2,4-diallyloxy-6-tert-butylperoxy-1,3,5-triazine; 2,4-diallyloxy-6-tert-amylperoxy-1,3,5-triazine; and mixtures thereof. Preferred organic peroxides include: tert-butylperoxymaleic acid; 1-methoxy-1-tert-pentylperoxycyclohexane; dilauroyl peroxide; tert-butylperoxy-2-ethylhexanoate; 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane; 1,1-di(tert-pentylperoxy)cyclohexane; 1,1-di(tert-butylperoxy)cyclohexane; tert-butylperoxy-3,5,5-trimethylhexanoate; tert-pentylperoxyacetate; tert-butylperoxyacetate; tert-pentylperbenzoate; tert-butylperbenzoate; OO-tert-butyl-O-isopropyl monoperoxycarbonate; OO-tert-pentyl-O-isopropyl monoperoxycarbonate; OO-tert-butyl-O-(2-ethylhexyl)monoperoxycarbonate; OO-tert-pentyl-O-(2-ethylhexyl)monoperoxycarbonate; dicumyl peroxide; JWEB-50, polyether polytert-butyl percarbonate (Arkema); 313, a complex mixture of peroxides containing <15 wt% tert-butylcumyl peroxide (Arkema); D-68, a complex mixture of dicumyl peroxide, di-tert-butylperoxydiisopropylbenzene and tert-butylcumyl peroxide (Arkema); D-446-B, a complex mixture of di-tert-butylperoxydiisopropylbenzene and tert-butylcumyl peroxide (Arkema); tert-butylcumyl peroxide; tert-butylperoxy-isopropenylcumyl peroxide; m / p-di-tert-butylperoxydiisopropylbenzene) and mixtures thereof.

[0065] More preferred peroxides are: tert-butylperoxymaleic acid; 1-methoxy-1-tert-pentylperoxycyclohexane; dilauroyl peroxide; tert-butylperoxy-2-ethylhexanoate; 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane; 1,1-di(tert-pentylperoxy)cyclohexane; 1,1-di(tert-butylperoxy)cyclohexane; tert-butylperoxy-3,5,5-trimethylhexanoate; tert-pentylperoxyacetate; tert-butylperoxyacetate; tert-pentylperbenzoate; tert-butylperbenzoate; OO-tert-butyl-O-isopropyl monoperoxycarbonate; OO-tert-pentyl-O-isopropyl monoperoxycarbonate; OO-tert-butyl-O-(2-ethylhexyl)monoperoxycarbonate; OO-tert-pentyl-O-(2-ethylhexyl)monoperoxycarbonate; dicumyl peroxide; 313, a complex mixture of peroxides containing <15 wt% tert-butylcumyl peroxide (Arkema); D-68, a complex mixture of dicumyl peroxide, di-tert-butylperoxydiisopropylbenzene and tert-butylcumyl peroxide (Arkema); tert-butylperoxy-isopropenylcumyl peroxide; m / p-di-tert-butylperoxydiisopropylbenzene) and mixtures thereof.

[0066] Even more preferred is: tert-butylperoxymaleic acid; LP, tert-butylperoxy-2-ethylhexanoate; 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane; 1,1-di(tert-pentylperoxy)cyclohexane; 1,1-di(tert-butylperoxy)cyclohexane; tert-butylperoxy-3,5,5-trimethylhexanoate; tert-pentylperbenzoate; tert-butylperbenzoate; OO-tert-butyl-O-isopropyl monoperoxycarbonate; OO-tert-pentyl-O-isopropyl monoperoxycarbonate; OO-tert-butyl-O-(2-ethylhexyl)monoperoxycarbonate; 313, a complex mixture of peroxides containing <15 wt% tert-butylcumyl peroxide (Arkema); D-68, a complex mixture of dicumyl peroxide, di-tert-butylperoxydiisopropylbenzene and tert-butylcumyl peroxide (Arkema); tert-butylperoxy-isopropenylcumyl peroxide; m / p-di-tert-butylperoxydiisopropylbenzene and mixtures thereof.

[0067] The peroxide used in this invention, or even more preferably: 231. TBEC, TAEC TAIC TBIC 531M80, P、Vul- 40KE V10 331M80, 533M75, Di- 40KE RTM, F40M-SP, F40-SP2, tert-butylperoxy-isopropenyl cumyl peroxide, 801 D16、Di- 40-SP2, Vul- 40-SP2, 101. HP101XLP, XL80 313、 D-68 D-446-B DTA and 130.

[0068] Non-polymer bio-based additives:

[0069] Non-limiting examples of suitable non-polymer bio-based additives included in non-polymer coupling agent formulations for wood polymer composites are those that may have at least some degree of unsaturation, i.e., carbon-carbon double bonds that are reactive to peroxide radicals. However, in some cases, bio-based additives may be saturated, i.e., those that do not contain radical-reactive double bonds. Non-limiting examples of saturated bio-based compounds are natural sugars, modified sugars known as artificial sweeteners, oxidized sugars, sugar alcohols, and organic acids such as malonic acid and tannic acid.

[0070] Organic molecules containing at least one carbon-carbon double bond can be used as non-polymer bio-based additives in non-polymer coupling agent formulations for wood polymer composites. Non-limiting specific examples of suitable unsaturated organic compounds include tung oil; arbutin; castor oil; lecithin; farnesene; limonene; oleate derivatives such as sorbitan monooleate, sorbitan dioleate, and sorbitan trioleate; arosin acid; abalin; itaconic acid; succinic acid; allyl succinic acid; and anhydrides of these acids. Preferred are tung oil, arbutin, castor oil, lecithin, limonene, arosin acid, itaconic acid, itaconic anhydride, succinic acid, succinic anhydride, allyl succinic acid, allyl succinic anhydride, sorbitan monooleate, sorbitan trioleate, and polysorbate 80.

[0071] Non-polymer bio-based additives such as itaconic acid, succinic acid, and allyl succinic acid can have excellent health, environmental, and safety properties, and are therefore preferred.

[0072] Alkyl esters of fatty acids from plant or animal sources containing at least one carbon-carbon double bond are suitable for use in embodiments of the invention disclosed herein. Such fatty acid esters may include C1 to C8 alkyl esters of C8-C22 fatty acids. In one embodiment, alkyl esters of fatty acids from vegetable oils, such as olive oil, peanut oil, corn oil, cottonseed oil, soybean oil, flaxseed oil, and / or coconut oil, are used. Flaxseed oil is preferred. In one embodiment, methyl soy oleate is used. In other embodiments, the alkyl ester may be selected from the group consisting of biodiesel and biodiesel derivatives. In another embodiment, the alkyl ester is a castor oil-based alkyl ester. The alkyl group present in the alkyl ester may be, for example, a C1-C6 straight-chain, branched, or cyclic aliphatic group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, cyclohexyl, etc. Alkyl esters may include mixtures of esters containing different alkyl groups. Non-polymer bio-based additives may be selected from fatty acids or derivatives thereof, monoglycerides, diglycerides, triglycerides, animal fats, animal oils, vegetable fats, or vegetable oils or combinations thereof. Examples of such non-polymer bio-based additives include, but are not limited to, linseed oil, soybean oil, cottonseed oil, ground nut oil, sunflower oil, rapeseed oil, canola oil, sesame oil, olive oil, corn oil, safflower oil, peanut oil, sesame oil, hemp oil, neat's food oil, whale oil, fish oil, castor oil, tall oil, and combinations thereof. Also suitable are algae oil, avocado oil, castor oil, linseed oil, fish oil, grapeseed oil, hemp oil, jalapeno oil, jojoba oil, mustard oil, dehydrated castor oil, palm oil, palm stearin, rapeseed oil, safflower oil, tall oil, olive oil, tallow, lard, chicken fat, linseed oil, linoleic acid oil, coconut oil, carnauba wax, and mixtures thereof. Linoleic acid oil, castor oil, and carnauba wax are preferred. The epoxidized form of any of the aforementioned natural oils can also be used in non-polymer coupling agent formulations of wood polymer composites. Partially epoxidized linoleic acid oil is preferred.

[0073] Naturally occurring terpenes and their derivatives are also suitable as non-polymer bio-based additives in non-polymer coupling agent formulations for wood polymer composites. Monoterpenes, monoterpenoids, modified monoterpenes, diterpenes, modified diterpenes, triterpenes, modified triterpenes, triterpenoid compounds, sesquiterpenes, modified sesquiterpenes, sesquiterpenoids, sesquiterpenoid-modified sesquiterpenes, sesquiterpenoid-modified sesquiterpenes, and oxygen-containing derivatives of sesquiterpenes are also non-limiting examples of suitable non-polymer bio-based additives that can be included in non-polymer coupling agent formulations for wood polymer composites. Non-limiting specific examples of such non-polymer bio-based additives include limonene, carvone, humulene, taxadiene, squalene, farnesene, farnesol, caffeol, coffee bean alcohol, cephalenene, taxadiene, retinol, retinaldehyde, phytol, geraniol, shark liver oil, licopene, ferrugicadiol, and tetraisoprene-curcumene, γ-carotene, α-carotene, and β-carotene. The epoxidized forms of these terpenes are also suitable.

[0074] Vitamins having at least one reactive carbon-carbon double bond can be used as non-polymer bio-based additives in certain embodiments of non-polymer coupling agent formulations for wood polymer composites. Non-limiting examples of these are vitamin K1 (menaquinone) and vitamin K2 (methylnaphthoquinone). In some embodiments, saturated vitamins having a desired hydrogen ablation capability can be used, capable of participating in organic peroxide reactions. Non-limiting examples of these saturated vitamins are vitamin B complex compounds, particularly folic acid, vitamin B12, vitamin B1 (thiamine), and vitamin K3 (menaquinone).

[0075] Other non-polymer bio-based additives that can be used in the non-polymer coupling agent formulations for wood polymer composites disclosed herein include raw honey, honey, glucose, fructose, sucrose, galactose, glycerol, and urea. Oxidized forms of these sugars are also suitable for some embodiments. For example, gluconic acid (oxidized glucose) and oxidized sucrose can also be used. In some embodiments, artificial sugars / sweeteners can be used. Non-limiting examples of these are saccharin, acesulfame potassium, aspartame, neotame, and sucralose. Certain amino acids can also be used as non-polymer bio-based additives in the non-polymer coupling agent formulations for wood polymer composites. Non-limiting examples of suitable amino acids are arginine, lysine, glutamine, histidine, cysteine, serotonin, tryptophan, asparagine, glutamic acid, glycine, aspartic acid, serine, and threonine.

[0076] Other non-polymer bio-based additives that can be included in non-polymer coupling agent formulations for wood polymer composites are, for example, blends of epoxidized bio-based oils with bio-derived itaconic acid or anhydrides. Unepoxidized bio-based oils can be used instead of epoxidized bio-based oils. Blends of epoxidized soybean oil with bio-based itaconic acid are useful. Other bio-based acids include, for example, natural acids such as rosin acid, including its corresponding anhydride form, malonic acid, and tannic acid. Abalin (methyl ester of rosin acid) is also included. Blends of epoxidized bio-based oils, bio-based oils (e.g., tung oil, limonene, arsenic oil), and di- or tri-functional acrylates and / or methacrylate active auxiliaries can be used in formulations, as can be marketed under trade names. and Those obtained from Sartomer. The latter are particularly preferred because they are bio-based.

[0077] Non-limiting examples of active additives include allyl methacrylate, triallyl cyanurate, and trimethylolpropane trimethacrylate (SR- ), trimethylolpropane triacrylate (SR- (1), zinc diacrylate, and zinc dimethacrylate. According to specific embodiments, the ratio (active agent: peroxide) of the one or more active agents to the one or more organic peroxides is between about 100:1 and 1:100; between 50:1 and 1:50; between 25:1 and 1:25; and between 10:1 and 1:10.

[0078] Pentaerythritol, with or without organic peroxides, can be used. Erythritol, sorbitol, mannitol, maltitol, lactitol, isomaltitol, xylitol, or other sugar alcohols can also be used.

[0079] Blends of zinc oxide, magnesium oxide, and / or calcium oxide with bio-based additives and the organic peroxides disclosed herein may be included in non-polymer formulations for use in wood polymer composites. Zinc di(itacinic acid) salts may be included in non-polymer coupling agent formulations for use in wood polymer composites.

[0080] Lecithin (i.e., a mixture of glycerophospholipids including phosphatidylcholine, phosphatidylethanolamine, phosphatidylinositol, phosphatidylserine, and phosphatidic acid) can be used in non-polymer coupling agent formulations for wood polymer composites. Sorbitol monooleate, sorbitol dioleate, and polysorbate 80 may also be included.

[0081] Other non-polymer bio-based additives or naturally occurring compounds that may be included in non-polymer coupling agent formulations for use in wood polymer composites are, for example, “natural solids” such as alum, aluminum sulfate, potassium aluminum sulfate, ammonium hydroxide, ammonium aluminum sulfate, boric acid and disodium tetraborate (also known as sodium borate or borax), aluminum lactate, ferrous sulfate, and stannous chloride.

[0082] Preferred natural solid additives used in the practice of this invention include potassium aluminum sulfate, ammonium aluminum sulfate, alum, allyl succinic anhydride, succinic anhydride, carnauba wax, casein, itaconic anhydride, and tung oil. More preferred natural solid additives for wood polymer composites include potassium aluminum sulfate, ammonium aluminum sulfate, alum, allyl succinic anhydride, succinic anhydride, carnauba wax, and itaconic anhydride.

[0083] In some embodiments, the nonpolymer coupling agent formulation for wood polymer composites may comprise both a nonpolymer bio-based additive (such as itaconic acid) having at least some degree of unsaturation and a nonpolymer bio-based “natural solid” additive (such as alum).

[0084] Non-polymer bio-based additions in non-polymer coupling agent formulations for wood polymer composites Amounts of agent and organic peroxide:

[0085] In some embodiments, the nonpolymer coupling agent formulation for wood polymer composites may comprise from 1% to 99% by weight of an organic peroxide and from 99% to 1% by weight of a nonpolymer bio-based additive.

[0086] According to specific embodiments, based on the total formulation, the at least one organic peroxide may be present in amounts ranging from 1 wt% to 95 wt%, or from 5 wt% to 95 wt%, 10 wt% to 90 wt%, or from 20 wt% to 99 wt%, or from 30 wt% to 90 wt%, or from 40 wt% to 75 wt%, or from 40 wt% to 70 wt%, or from 40 wt% to 65 wt%, or from 45 wt% to 80 wt%, or from 45 wt% to 75 wt%. The amount of 45 wt% to 70 wt%, or 45 wt% to 65 wt%, or 50 wt% to 98 wt%, or 50 wt% to 75 wt%, or 50 wt% to 70 wt%, or 50 wt% to 65 wt%, or 50 wt% to 60 wt%, or 1 wt% to 50 wt%, or 1 wt% to 40 wt%, or 1 wt% to 25 wt% is included in the nonpolymer coupling agent formulation for use in wood polymer composites.

[0087] According to specific embodiments, based on the total weight of the nonpolymer coupling agent formulation for wood polymer composites, the at least one nonpolymer bio-based additive may be included in the nonpolymer coupling agent formulation for wood polymer composites in an amount ranging from 95 wt% to 5 wt%, or from 90 wt% to 10 wt%, or from 99 wt% to 20 wt%, or from 90 wt% to 30 wt%, or from 75 wt% to 40 wt%, or from 70 wt% to 40 wt%, or from 65 wt% to 40 wt%, or from 80 wt% to 45 wt%, or from 75 wt% to 45 wt%, or from 70 wt% to 40 wt%, or from 65 wt% to 45 wt%, or from 98 wt% to 50 wt%, or from 75 wt% to 50 wt%, or from 70 wt% to 50 wt%, or from 65 wt% to 50 wt%, or from 60 wt% to 50 wt%.

[0088] The weight ratio of organic peroxide to non-polymer bio-based additives can be from 1:1000 to 1000:1, or from 1:100 to 100:1, or from 1:9 to 9:1, or from 4:5 to 5:4, or from 1:5 to 5:1, or from 1:1 to 1:2, or from 2:1 to 3:1, or from 1:9 to 1:1, or from 1:1 to 9:1, or from 2:1 to 1:1. The weight ratio of organic peroxide to additives can be from 1:40 to 1:1; 1:20 to 1:1; 1:10 to 1:1; 1:5 to 1:1; or 1:3 to 1:1.

[0089] Polymer matrix materials for wood polymer composites:

[0090] Suitable polymer matrix materials for wood polymer composites include, but are not limited to, polyethylene and ethylene copolymers, including but not limited to LLDPE (linear low-density polyethylene), HDPE (high-density polyethylene), and / or LDPE (low-density polyethylene). All of these preferably have a high melt flow index (MFI) of <40 g / 10 min, preferably <20 g / 10 min, more preferably <10 g / 10 min, more preferably <5 g / 10 min, even more preferably <1 g / 10 min, and most preferably <0.5 g / 10 min, at 190°C and under a 2.15 kg load, as described in test method ASTM 01238. The polyethylene used in this invention preferably has a high molecular weight, wherein for PE types including LDPE, LLDPE, MDPE (medium-density polyethylene), and HDPE or blends thereof from virgin or recycled sources, the molecular weight of the polyethylene grade starts from about 50,000 g / mol to 200,000 g / mol, and at most about 250,000 g / mol. Ultra-high molecular weight polyethylene (UHWMPE) (e.g., in recycled PE streams, with a molecular weight of 3,000,000 g / mol to 7,500,000 g / mol) may also be present. In some embodiments, polymers such as poly(vinyl chloride) and poly(vinyl acetate) may also be suitable as matrix materials in wood polymer composites.

[0091] Preferred polymer matrix materials for wood polymer composites include recycled polyethylene, wherein the recycled material may be a blend of UHMWPE, HDPE, MDPE, LDPE, LLDPE; or virgin grades of HDPE, LDPE, LLDPE.

[0092] The most preferred polymer matrix materials for wood polymer composites include UHMWPE, HDPE and MDPE.

[0093] Fillers for wood polymer composites:

[0094] Wood flour is a well-known filler in wood polymer composite decking. Wood flour is finely ground wood with a consistency comparable to sand or sawdust, but it can vary considerably, with particle sizes ranging from fine powder to approximately rice grain size. Most batches of wood flour consistently maintain the same consistency. Higher quality wood flour is made from hardwoods due to its durability and strength. Lower grades of wood flour can be made from non-sap-rich softwoods such as pine or fir. Better and / or more economical fillers are always needed to replace wood flour. Natural fillers that can be used in the practice of this invention include, but are not limited to, rice husk powder, straw powder, or fibers such as wheat straw, bamboo fiber, flax, jute, hemp, cellulose, groundwood, sawdust, palm fiber, bagasse, peanut shells, chitin, and kenaf fiber. Waste paper and paperboard can also be used alone or in combination with wood flour or sawdust. Wood flour can be produced from softwood, hardwood, or blends. Optionally, lignin is removed from the wood flour.

[0095] In some embodiments, sawdust or wood chips (byproducts or waste products consisting of fine particles of wood) may also be suitable as fillers in wood polymer composites.

[0096] Another filler is shredded recycled truck and / or bus tires. Worn tires can be ground into a powder suitable for use in this invention. The amount of shredded tires can be from 50 wt% to 1 wt% of the composite material.

[0097] An exemplary embodiment of the present invention includes milled recycled rubber tire filler with wood flour, polyethylene, at least one coupling agent, and at least one organic peroxide. Other fillers that can be used in combination with wood flour / sawdust include chlorinated polyethylene powder and chlorosulfonated polyethylene powder. In some embodiments, cellulose acetate butyrate (CAB) can be used as a filler. Preferred CAB grades will have an upper limit melting point of no higher than 160°C, preferably no higher than 150°C, even more preferably no higher than 145°C, and most preferably below 143°C. The most preferred grade of CAB that can be included as a filler has a butyryl content of approximately 52%. Non-limiting examples are: cellulose acetate butyrate (CAB-551-0.2) and (CAB-551-0.01) from Eastman Chemical Company.

[0098] Preferred fillers for wood polymer composites include wood flour made from hardwoods and / or softwoods (including blends). Other fillers that can be combined with wood flour are sawdust and fine wood chips. The most preferred filler includes wood flour made from hardwoods.

[0099] Improved features :

[0100] For example, the properties of wood polymer composites that can be improved or modified by including non-polymer coupling agent formulations for wood polymer composites may include, but are not limited to: improved compatibility between the polymer matrix and the wood filler, reduced water absorption, improved stiffness, improved impact resistance, improved compatibility with other polymers, improved compatibility with fillers, and allowing for the increased use of lower-cost ground recycled materials, such as paper, cardboard, waste carpet, tires, polyethylene plastic bags / bottles, and recycled PET containers. The use of recycled materials provides useful products while reducing waste streams.

[0101] For example, wood polymer composites containing non-polymer coupling agent formulations for wood polymer composites as disclosed herein can be more compatible with other polymers, allowing the polymer matrix to comprise polyethylene and another polymer. Other non-limiting examples of such polymers are poly(vinyl alcohol), polyacrylates, and copolymers of poly(vinyl alcohol) or polyacrylates. Resin (Arkema). Also considered is a small amount (<2 wt% to <1 wt%) of fluoropolymers, such as polyvinylidene fluoride (PVDF), for example... (Arkema) and PTFE.

[0102] Non-polymer coupling agent formulations for wood polymer composites can be in solid or liquid form, depending on the form of the organic peroxide and the non-polymer bio-based additive. Non-polymer coupling agent formulations for wood polymer composites can also be in masterbatch form.

[0103] Masterbatch :

[0104] A coupling agent masterbatch for wood polymer composites is provided. The coupling agent masterbatch for wood polymer composites may comprise, consist of, or substantially consist of: a) at least one organic peroxide; b) at least one non-polymer bio-based additive; and c) a carrier for the non-polymer coupling agent masterbatch. The at least one organic peroxide is a room-temperature organic peroxide and has a half-life of at least one hour at 98°C. The at least one non-polymer bio-based additive is selected from the group consisting of: i) at least one natural oil or a derivative thereof; ii) at least one natural acid, anhydride, including its ester; iii) natural acids; and iv) mixtures thereof. The at least one organic peroxide and the at least one non-polymer bio-based additive are as described above.

[0105] As is known in the art, a masterbatch is a concentrated mixture of non-polymer coupling agent formulations for use in wood polymer composites, which is added to a polymer matrix and wood fillers to process (blend) them into finished products such as decking.

[0106] Carriers for non-polymer coupling agent masterbatches:

[0107] The carrier for the coupling agent masterbatch used in wood polymer composites may comprise, consist of, or substantially consist of one or more of the polymer and / or wood filler components of the final wood polymer composite. For example, a non-polymer coupling agent formulation containing organic peroxides and bio-based additives, as described above, may be combined with wood flour, sawdust, polyethylene, calcium carbonate, synthetic calcium silicate, Burgess clay, precipitated silica, microcrystalline cellulose, fly ash, dried wood flour, dried sawdust, dried straw pellets, and combinations thereof. In some embodiments, the particulate material as the carrier may be preferred because the masterbatch can be prepared by blending a liquid formulation of organic peroxides and bio-based additives with the particulate material to form a free-flowing, non-agglomerating particulate masterbatch.

[0108] Non-limiting examples of suitable particulate carrier materials for masterbatches are polyethylene powder, granulated polyethylene, dried sawdust, dried wood flour, bamboo powder, hemp powder, kenaf fiber, waste paper, waste paperboard, cellulose acetate butyrate, and combinations thereof. Equally suitable are inert carriers, such as silica, fumed silica, precipitated silica, talc, calcium carbonate, clay, Burgess clay, kaolin, fly ash, powdered polyethylene, and granulated polyethylene.

[0109] In another embodiment, for example, the carrier material may comprise, consist of, or be substantially composed of low-melting-point waxes. Organic peroxides and bio-based additives can be melt-blended with the waxes, and the resulting masterbatch can then be granulated. Typically, only small amounts of these waxes are added, such that the final wood polymer composite contains less than 5 wt%, preferably less than 3 wt%, more preferably less than 1 wt% of low-melting-point waxes. Suitable waxes include, but are not limited to, bio-based waxes such as beeswax, soybean wax, myrica wax, candelilla wax, carnauba wax, castor wax, plant waxes, carnauba wax, rice bran wax, lanolin, etc. Others may include known non-bio-based petroleum-based waxes.

[0110] Depending on the dilution and desired concentration of the coupling agent formulation in the final wood polymer composite, the concentration, in wt%, of the organic peroxides and bio-based additives and / or other additives disclosed herein incorporated together in the masterbatch can be varied as needed. Non-limiting examples of suitable concentrations of organic peroxides and bio-based stabilizers in the masterbatch can range from 40 wt% to 65 wt%, or from 30 wt% to 75 wt%, or from 50 wt% to 70 wt%, or from 40 wt% to 50 wt%, depending on one or more peroxides, bio-based additives, and other additives selected for use in the masterbatch blend, but said ranges can also be from 1 wt% to 80 wt%, or from 2 wt% to 60 wt%, or from 5 wt% to 50 wt%, or from 10 wt% to 40 wt%.

[0111] Stabilizer for organic peroxides :

[0112] Non-polymer coupling agent formulations for wood polymer composites may contain, or consist of, at least one quinone compound, or substantially at least one of the organic peroxides. In some cases, if said at least one quinone compound is used as a stabilizer for the organic peroxide, at least one allyl compound, preferably triallyl, may also be included together with the organic peroxide. Non-limiting examples of allyl compounds are TAC (tracelyl cyanurate), TAIC (tracelyl isocyanurate), triallyl trimellitate, diallyl maleate, diallyl tartrate, diallyl phthalate, diallyl carbonate, allyl phenyl ether, allyl methacrylate, and higher molecular weight allyl methacrylate oligomers sold by Sartoma.

[0113] In some embodiments, at least one stabilizer or free radical scavenger may be selected from the group consisting of free nitro oxygen (e.g., 4-hydroxy-TEMPO) and quinones (such as mono-tert-butylhydroquinone (MTBHQ)). These stabilizers (referred to as free radical scavengers (i.e., any agent that interacts with and inactivates free radicals)) and any such agents as are known to those skilled in the art can be used. Other stabilizers include olive leaf oil (oleuropein), 1076、 1010, and vitamins K1, K2, and K3. As used herein, the term "quinone" includes both quinone and hydroquinone. Non-limiting examples of quinone include mono-tert-butylhydroquinone (MTBHQ), hydroquinone, hydroquinone monomethyl ether (HQMME) (also known as 4-methoxyphenol), mono-tert-pentylhydroquinone, hydroquinone bis(2-hydroxyethyl) ether, 4-ethoxyphenol, 4-phenoxyphenol, 4-(benzyloxy)phenol, 2,5-bis(morpholinomethyl)hydroquinone, and benzoquinone. Preferred stabilizers used in this invention include MTBHQ; HQMME; mono-tert-pentylhydroquinone, 1010 and 4-OH TEMPO. More preferred stabilizers include mono-tert-butylhydroquinone (MTBHQ), hydroquinone, and hydroquinone monomethyl ether (HQMME) (also known as 4-methoxyphenol). Even more preferred is the stabilizer MTBHQ.

[0114] Method for producing coupling agent masterbatch :

[0115] A method is provided for producing a coupling agent masterbatch for use in wood polymer composites. The method may include, consist of, or substantially consist of steps A) and B).

[0116] Step A) may include a combination of: a) at least one organic peroxide, and b) at least one non-polymer bio-based additive to form a coupling agent formulation for wood polymer composites, comprising, or substantially comprising, such a formulation.

[0117] The organic peroxides (a) have a half-life of at least one hour at 98°C, and the peroxide class or type is determined by direct peroxide analysis by gas or liquid chromatography, depending on the dilution solution kinetics. Solid organic peroxides and solid functionalized organic peroxides can exhibit environmental stability at 20°C so as not to lose any significant percentage determination for at least one month, preferably three months, as determined directly by titration, gas chromatography, or liquid chromatography according to the peroxide class.

[0118] The b) at least one non-polymer bio-based additive is selected from the group consisting of: i) at least one natural oil or a derivative thereof; ii) a natural acid; iii) a natural acid anhydride; iv) an ester of a natural acid and an anhydride; and v) a mixture thereof;

[0119] Optional additives may be selected from the group consisting of active auxiliaries; sulfur-containing compounds and / or elemental sulfur; and mixtures thereof.

[0120] Step B) may include combining a coupling agent formulation for wood polymer composites with at least one carrier in c) to form a coupling agent masterbatch for wood polymer composites, consisting of, or substantially consisting of.

[0121] According to certain embodiments of this disclosure, the coupling agent formulation for wood polymer composites may be in liquid form, and at least one carrier may be in solid particulate form. The solid particulates may be selected from the group consisting of polyolefins, particularly polyethylene (e.g., HDPE, LLDPE, MDPE, and LDPE). However, for some embodiments, ground solid polymer particulates from a mixed stream of recycled polymer waste may be considered. As is known in the art, polyethylene derived from plastic waste streams may contain other polymers besides polyethylene, such as polystyrene, polyethylene terephthalate, polypropylene, waste paper / paperboard. Other suitable solid particulates that may be used in some embodiments are calcium carbonate, Burgess clay, precipitated silica, microcrystalline cellulose, fly ash, dried wood flour, dried sawdust, dried straw pellets, recycled ground paper waste, recycled ground / shredded paperboard waste, recycled ground carpet fiber waste, recycled ground bus / truck tires, and combinations thereof. The solid particulates may be selected from the group consisting of particulate polyethylene (e.g., granular polyethylene directly from a gas-phase reactor), wood flour, or sawdust. In some embodiments of this disclosure, step B) may include mixing a liquid coupling agent formulation with at least one carrier in the form of solid particles to form a coupling agent masterbatch, such that the coupling agent masterbatch may be in the form of solid particles at 25°C. Therefore, the coupling agent masterbatch may be in the form of free-flowing solid particles.

[0122] According to another embodiment, steps A) and B) can be performed simultaneously, i.e., the at least one organic peroxide, the at least one non-polymer bio-based additive, and the at least one carrier material can be mixed together at the same time. For example, these steps A) and B) can be performed in a low-shear belt mixer (e.g., The process is carried out in a belt mixer to form a coupling agent masterbatch containing the aforementioned microparticles. It can also be done in a high-shear mixer. Various components are blended in a type of mixer to produce free-flowing powder masterbatch.

[0123] The at least one organic peroxide may be selected from those described above or mixtures thereof. The at least one non-polymer bio-based additive may be selected from those listed above or combinations thereof.

[0124] Combining step B) may include melt blending various components into the polymer. Melt blending can be carried out, for example, in a single-screw extruder, twin-screw extruder, ZSK mixer, Banbury mixer, Buss kneader, two-roll mill, or impeller mixer, or other suitable type of polymer melt blending equipment, to produce a coupling agent masterbatch. The blending time and temperature conditions of combining step B) can be selected such that the decomposition of the organic peroxide used does not exceed 4 wt%, preferably less than 2 wt%, more preferably less than 1 wt%.

[0125] Methods for producing wood polymer composites :

[0126] A method for producing a wood polymer composite material is provided. The method includes step I), which comprises, or substantially comprises, components A), B1), and C), to form a component mixture. A), B1), and C) comprise, or substantially comprise: A) a non-polymer coupling agent for wood polymer composites as disclosed herein, comprising, or substantially comprises; B1) a polymer matrix for wood polymer composites as disclosed above, comprising, or substantially comprises; and C) at least one filler selected from the foregoing, comprising, or substantially comprises. The method further includes step II), which comprises, or substantially comprises, the component mixture.

[0127] Alternative methods for producing wood polymer composites are also provided. These alternative methods are similar to the first method, but include the use of a coupling agent masterbatch, comprising, or substantially comprising, that of a coupling agent masterbatch. Specifically, step I) involves combining components A), B2), and C) to form a component mixture. A), B2), and C) comprise, comprise, or substantially comprise: A) a coupling agent masterbatch for wood polymer composites as disclosed herein, comprising, or substantially comprising; B2) a polymer matrix for wood polymer composites as disclosed above, comprising, or substantially comprising; and C) at least one filler selected from the foregoing, comprising, or substantially comprising. The alternative method also includes step II) of shaping the component mixture into a composite material, comprising, or substantially comprising, that of the composite material.

[0128] In both methods of forming wood polymer composites, the assembly step I) can be, for example, combining components A) the polymer matrix, C) the filler, and non-polymer coupling agent formulation B1) or coupling agent masterbatch B2) in the feed unit of an extruder. For example, the components can be metered into the extruder hopper such that the feed section of the extruder provides the majority of the assembly step. The assembly step may include dry-mixing the components, such as in a drum mixer, belt mixer, or high-shear mixer, and then feeding the dry mix into the extruder hopper. If the coupling agent formulation or coupling agent masterbatch is in liquid form, the liquid can be metered separately into the extruder feed unit, and the polymer matrix and filler can be directly combined into the extruder hopper, or dry-mixed separately. Other such methods are known in the art and can be used in some embodiments. For example, melt blending can be used, such as in a single-screw extruder, twin-screw extruder, ZSK mixer, Banbury mixer, Buss kneader, twin-roll mill, or impeller mixer, or other suitable polymer melt blending equipment, to combine components to produce a reaction mixture. The combination step can be part of a process for producing a finished product, such as die extrusion to form solid wood polymer composite panels, or using a roller mill to produce sheets for thermoforming processes, or using blown film processes or compression molding processes to produce various parts. In some embodiments, other processes known in the art can be performed, including injection molding, injection blow molding, thermoforming, or vacuum forming, to produce the finished product.

[0129] In any method of forming the composite material, the forming step II) can be, for example, extruding the component mixture through a die fixed to an extruder. The forming step can be, for example, thermoforming using a set of heated dies. Other anticipated forming methods include injection molding, calendering, blow molding, foaming, injection blow molding, vacuum forming, compression molding, and thermoforming. The composite material can be polymeric wood, for example, decking intended for outdoor environments. Other useful articles include, but are not limited to, cladding, wall panels, outdoor furniture, exterior decking, interior flooring, interior furniture, pallets, flooring, railings, fences, molded parts, decorative parts, window frames, door frames, landscaping timber, industrial stack supports, seawalls and piles, boatslips, and wall panels.

[0130] Other additives :

[0131] Bio-based fillers, non-bio-based fillers, and / or peroxide stabilizers (whether bio-based or not) may also be included in non-polymer coupling agent formulations for use in wood polymer composites. For example, calcium carbonate, talc, silica, fumed silica, precipitated silica, calcium carbonate, calcium silicate, diatomaceous earth, clay, Burgess clay, kaolin, fly ash, powdered polyethylene, or ground / powdered recycled bus or truck tires, ground / powdered recycled carpet fibers, ground recycled mixed polymer streams (which may contain small amounts of various polymers, including polypropylene or poly(ethylene propylene) copolymers or poly(ethylene octene) copolymers or LDPE, or HDPE, or LLDPE); chopped glass fibers, ground paper, ground cardboard, and / or ground waste particleboard.

[0132] Other additives known to those skilled in the art that can be included in wood polymer composite formulations may include, for example: colorants; mildew inhibitors; insecticides; fillers other than wood flour; antioxidants; light / UV stabilizers; foaming agents or bubbling agents; polymer flow aids; extrusion slip aids, such as erucamide; non-metallic lubricants, such as ethylene bis-stearimide; and Glycolube from Lonza. TM WP2200; TPW 113 and TPW 617 is a non-limiting example; fungicides, such as (from Zeneca AgProducts) and Processing aids; release agents; antioxidants; anti-blocking agents, etc. Suitable release agents known in the art include fatty acids; zinc, calcium, and magnesium salts of fatty acids (e.g., zinc stearate). Release agents and slip agents can be added in amounts less than about 5 wt% based on the total weight of the final wood polymer composite. When boric acid derivatives (such as zinc borate) are used at levels of 3 wt% to 5 wt%, they can effectively combat destructive brown rot fungi.

[0133] Non-polymer coupling agent formulations may further include at least one sulfur-containing compound as a co-curing agent. Non-limiting examples of such co-curing agents include disulfides, elemental sulfur, and sulfur-containing amino acids. The Vanderbilt Rubber Handbook, 13th edition, 1990, published by RT Vanderbilt Company, Inc. (whose entire disclosure is incorporated herein by reference for all purposes), lists many types of sulfur-containing compounds used for curing rubber. Non-limiting examples include monosulfides, 2-mercaptobenzothiazole (MBT), 2-2'-dithiobis(benzothiazole) (MBTS), disulfides, diallyl disulfides, polysulfides, and aryl polysulfide compounds such as pentylphenol polysulfides, for example… (Arkema). Specific examples include... 5. 3. 7. Mercaptobenzothiazole disulfide (MBTS) and zinc dialkyl dithiophosphate (ZDDP). Sulfur-containing amino acid compounds, such as cysteine, methionine, homocysteine, taurine, n-formylmethionine, and S-adenosyl homocysteine, are also included as co-curing agents. Organic peroxide formulations may contain at least one sulfur-containing compound, particularly at least one disulfide compound or elemental sulfur, or a combination thereof, as a co-curing agent.

[0134] The non-polymer coupling agent may further comprise an active auxiliary agent that can synergize with at least one of the organic peroxides. Crosslinking active auxiliaries have a function different from peroxides: not wanting to be bound by theory, active auxiliaries may be activated with the help of free radical initiators (such as organic peroxides). Thus, activated during the decomposition of the peroxide, it can then form crosslinking bridges with the polymer and thus integrate into the chain of the crosslinked polymer, unlike peroxides. Non-limiting examples of suitable active auxiliaries include compounds containing allyl, acrylic, methacrylic acid, and styrene. Monoallyl, diallyl, and triallyl compounds may be considered. Non-limiting examples include: allyl phenyl ethers, epoxidized allyl phenyl ethers, allyl methacrylate monomers and oligomers (such as those sold by Sartoma), diallyl maleate, diallyl disulfide, diallyl itaconic acid, diallyl tartrate, diallyl phthalate, trimethylolpropane diallyl ether, triallyl trimellitate, triallyl cyanurate, partially epoxidized triallyl cyanurate, triallyl isocyanurate, partially epoxidized triallyl isocyanurate, and trimethylolpropane triallyl ether. Other non-limiting examples of such active additives are: α-methylstyrene dimers, or poly(methyl methacrylate) dissolved in methyl methacrylate monomers (which may be named as...). (Originally obtained from Arkema). Considered in this disclosure The resin is used in conjunction with at least one organic peroxide formulation. It can also be used in combination with other components disclosed herein (e.g., natural oils, natural solids, sulfur compounds, other active additives, elemental sulfur and / or acids).

[0135] Any or all mixtures of these additives have been considered.

[0136] "Thick oils" made by polymerizing natural or bio-based oils are excluded from certain embodiments of the invention. These include polyester resins and those made using the various acids listed in the disclosure herein. Other exclusions from certain embodiments include water, which is added as a separate component to the formulation in amounts of about 5%, about 4%, about 3%, about 2%, about 1%, about 0.5%, or about 1000 ppm wt. Hydrogen peroxide is excluded. Inorganic peroxides are excluded. In the practice of the invention, it is undesirable to intentionally incorporate water or use additives diluted with a significant amount of water. AIBN (azobisisobutyronitrile) or azo initiators are excluded. Based on the total weight of organic peroxides and non-polymer bio-based additives, any or all of these compounds may be present in formulations of non-polymer coupling agents for wood polymer composites at levels not exceeding 5 wt%, 4 wt%, 3 wt%, 2 wt%, or 1 wt%. Preferably, none of these compounds are present in the formulation.

[0137] Standard test methods and equipment used in the implementation of this invention

[0138] ASTM D7031-11 (2019) is a standard guide for evaluating the mechanical and physical properties of wood-plastic composite products. This ASTM guide discloses over 38 test methods applicable to evaluating a wide range of performance characteristics of wood-plastic composite (WPC) products. This does not mean that all listed tests are necessary or appropriate for every application of wood-plastic composites as disclosed herein.

[0139] The following test methods are used: ASTM D6109-19 (2019) Test Methods for Flexural Properties of Unreinforced and Reinforced Plastic Lumber and Related Products; ASTM D6341-98 (1998) Test Method for Determination of the Linear Coefficient of Thermal Expansion of Plastic Lumber and Plastic Lumber Shapes Between 30°F and 140°F (34.4°C and 60°C); ASTM D4442-16 (2016) Test Methods for Direct Moisture Content Measurement of Wood and Wood-Based Materials; ASTM D4761-19(2019) Test Methods for Mechanical Properties of Lumber and Wood-Based Structural Materials (e.g., Modulus of Fracture: MOR)[Modulus of rupture: MOR]; ASTM D1238-13 (2013) Standard Test Method for Melt Flow Rates of Thermoplastics by Extrusion Plastometer (used to determine polyethylene Melt Flow Index - MFI); ASTM D5289-19a (2019) Standard Test Method for Rubber Property - Vulcanization Using Rotorless Cure Meters (can be used for polyethylene); and ASTM D4440-15 (2015) Standard Test Method for Plastics: Dynamic Mechanical Properties Melt Rheology.

[0140] The present invention further includes the following aspects:

[0141] Aspect 1: A method for producing a coupling agent masterbatch for wood polymer composites, the method comprising:

[0142] A) Combination:

[0143] a) at least one organic peroxide, wherein said organic peroxide has a half-life of at least one hour at 98°C; and

[0144] b) At least one non-polymer bio-based additive selected from the group consisting of: i) at least one natural oil or a derivative thereof; ii) at least one natural acid, anhydride or ester thereof; iii) at least one natural solid; and iii) mixtures thereof.

[0145] To form coupling agent formulations for use in wood polymer composites;

[0146] B) Combining the coupling agent formulation for wood polymer composites with at least c) a carrier to form the coupling agent masterbatch for wood polymer composites.

[0147] Aspect 2: According to the method of aspect 1, wherein the coupling agent formulation for wood polymer composites is in liquid form; the at least one carrier is in solid particulate form; and step B comprises mixing the liquid coupling agent formulation with the at least one solid particulate carrier to form the coupling agent masterbatch, wherein the coupling agent masterbatch is in solid particulate form at 25°C.

[0148] Aspect 3: The method described according to aspect 1 or 2, wherein steps A) and B) are performed simultaneously.

[0149] Aspect 4: The method according to any one of Aspects 1-3, wherein the at least one carrier in the form of solid particles is selected from the group consisting of polyolefins, polystyrene, calcium carbonate, Burgess clay, precipitated silica, microcrystalline cellulose, fly ash, dried wood flour, dried sawdust, dried straw particles, and combinations thereof.

[0150] Aspect 5: A method for producing a wood polymer composite material, the method comprising:

[0151] I) The combination includes the following components:

[0152] A) A non-polymer coupling agent for the wood polymer composite material according to any one of aspects 1-4;

[0153] B1) Polymer matrix; and

[0154] C) Packing material;

[0155] To form a mixture of components; and

[0156] II) The mixture of components is shaped into a composite material.

[0157] Aspect 6: The method for producing wood polymer composites according to aspect 5, wherein step I) further includes feeding components A), B1) and C) into an extruder, and step II) includes extruding through a die.

[0158] Aspect 7: A method for producing a wood polymer composite material, the method comprising:

[0159] I) The combination includes the following components:

[0160] A) Coupling agent masterbatch for wood polymer composites according to any one of aspects 1-6;

[0161] B2) Polymer matrix; and

[0162] C) Packing material;

[0163] To form a mixture of components; and

[0164] II) The mixture of components is shaped into a composite material.

[0165] Aspect 8: The method for producing wood polymer composites according to aspect 7, wherein step I) further includes feeding components A), B2) and C) into an extruder, and step II) includes extruding through a die.

[0166] abbreviations used in the examples

[0167] Novacom-P TM HFS2100P is a high-density polyethylene grafted with maleic anhydride from TWO H Chem.

[0168] Vul- 40KE is 40% by weight of bis(tert-butylperoxyisopropyl)benzene on inert filler (kaolin) (Arkema).

[0169] P stands for tert-butyl peroxybenzoate (Arkema).

[0170] 231 is 3,3,5-trimethyl-1,1-di(tert-butylperoxy)cyclohexane (Arkema).

[0171] TBEC is tert-butyl-(2-ethylhexyl)-monoperoxycarbonate (Arkema).

[0172] TAEC is tert-amyl-(2-ethylhexyl)-monoperoxycarbonate (Arkema).

[0173] MOR is the modulus of rupture.

[0174] MOE is the modulus of elasticity.

[0175] psi is pounds per square inch.

[0176] ksi is kilopounds per square inch.

[0177] Tests and Programs

[0178] Sample mixing procedure

[0179] Place the wood flour (40M1 hardwood 40 mesh, American Wood Fibers) in a stainless steel pan in a ventilated oven and heat at 110°C for 22–24 hours. Weigh the dried wood flour, high-density polyethylene, talc, zinc stearate, N,N'-ethylene bis-stearamide, and other ingredients (including peroxides and additives) on an open-air balance and place them into a 1-gallon polyethylene bag (total mass of materials for mixing = approximately 230 g). Seal the bag and shake it by hand (approximately 30 seconds) to provide initial mixing. Then transfer the contents of the bag to a brabender Intelli torque mixer (3-pack, 350cc premix bowls, Banbury blades, WinMix software) and mix at 150°C and 50 RPM until a stable torque measurement is achieved. Remove the material from the mixing bowls and then add it back to the mixing bowls and mix for a total of three minutes (50 RPM, 150°C). The material was then removed from the bowl and final compounded using a press (Carver 15-ton model 3893; 10 seconds at 10 ksi and 150°C).

[0180] Decorative panel preparation process

[0181] A thin sheet of metal (8”x8”x0.108”) was placed on an 8”x8”x0.035” stainless steel plate, and an 8”x8”x0.016” aluminum foil sheet was placed on top of it. An 8”x8”x0.125” stainless steel trim frame with an inner cavity of 6”x6” was placed on top of the aluminum foil. Approximately 90g of compounded wood-plastic composite was placed into the cavity of the trim frame, and then covered with the aluminum foil layer, the thin sheet of metal, and the stainless steel plate. The entire trim assembly was subjected to a pressure of 15 kpsi at 185°C for 13 minutes (WabashGenesis 30-ton G30H press). The trim frame and sample were removed from the press and allowed to cool to ≤35°C. Once cooled, rectangular strips (4”x0.5”) of the pressed material were cut from the trim (using a band saw) for flexural testing.

[0182] Physical property testing program

[0183] Three-point flexural testing was performed using an Instron 33R 4204 measuring instrument, according to ASTM D790. The Instron 33R 4204 includes a 2-inch span, a 500 N static force sensor, and a flexural rate of 0.5 in / min. The reported values ​​for modulus of rupture (MOR) and modulus of elasticity (MOE) were averaged between measurements taken from three to five samples cut from each test panel, with outliers (defined as exhibiting a deviation >5% from the average of the remaining measurements) excluded from the calculation.

[0184] Example

[0185] Comparison Example 1

[0186] A wood-plastic composite containing a contrast coupling agent. The mixture is prepared using the procedure outlined above, comprising 57 parts wood flour (40M1 hardwood 40 mesh wood flour, American Wood Fiber Company) and 32 parts high-density polyethylene (…). HDPE powder (ExxonMobil), 6 parts talc (magnesium silicate monohydrate, Alfa Aesar), 2 parts zinc stearate (Beantown Chemicals), 1 part N,N'-ethylidene bis-stearyl (Spectrum Chemicals), and 2 parts Novacom-P TM The composition of HFS2100P (coupling agent). Test panels were produced using the above procedure, and physical property tests revealed a modulus of rupture (MOR) of 3681 psi and a modulus of elasticity (MOE) of 499 ksi.

[0187] Examples 1-6 (of this invention)

[0188] Examples 1-6 include Vul- 40KE was used as an organic peroxide, and organic acid anhydrides (such as succinic anhydride, itaconic anhydride, and allyl succinic anhydride) were used as non-polymer bio-based additives. As shown in Table 1, physical property tests of Examples 1-6 showed that, relative to the reference system, Comparative Example 1, MOR and MOE increased (modulus increased by 15% to 102%).

[0189] Table 1

[0190]

[0191] Example 7-14 (of this invention):

[0192] Example 7-14 includes P, 231. TBEC, or TAEC was used as an organic peroxide, and acid anhydrides (such as itaconic anhydride or succinic anhydride) were used as non-polymer bio-based additives, as shown in Table 2. Physical property tests on Examples 7-14 showed that MOR and MOE were significantly increased (15%-72%) compared to Comparative Example 1.

[0193] Table 2

[0194]

[0195] Comparison Example 2-6

[0196] Comparative Examples 2-6 (Table 3) include itaconic anhydride or allyl succinic anhydride as non-polymer bio-based additives, but without organic peroxides. Physical property tests on Comparative Examples 2-6 showed a reduction in MOR (18% to 39% reduction compared to Comparative Example 1); Comparative Example 6 further showed a 19% reduction in MOE compared to Comparative Example 1.

[0197] Table 3

[0198]

[0199]

[0200] Examples 15-19 (of this invention):

[0201] Examples 15-19 include Vul- 40KE was used as an organic peroxide, and organic acids (such as itaconic acid or succinic acid) or oleate derivatives (such as sorbitan monooleate or sorbitan trioleate) were used as non-polymer bio-based additives, as shown in Table 4. Physical property tests on Examples 15-19 revealed a significant increase in MOR (6% to 92% increase relative to Comparative Example 1); Examples 15, 17, and 18 further showed a significant increase in MOE (8% to 11%) relative to Comparative Example 1.

[0202] Table 4

[0203]

[0204]

[0205] Examples 20-27 (of this invention)

[0206] Examples 20-27 (Table 5) include Vul- 40KE is used as an organic peroxide, and inorganic substances (such as potassium aluminum sulfate, borax (disodium tetraborate), or boric acid) are used as non-polymer bio-based additives. Physical property tests on Examples 20-27 show a significant increase in MOR and / or MOE compared to Comparative Example 1. Compared to the reference system, Examples 20-24 and 26-27 show an increase in MOR of 28%-107%, and Examples 21-25 and 27 show an increase in MOE of 5%-20%. Examples 22 and 23 show that inorganic substances can be combined with organic acids to provide further improvements in key physical properties. Examples 24-27 further show that the formulations of the present invention can contain polyethylene and another polymer (such as polyvinyl alcohol (PVA)), or polyethylene and silane additives (such as vinyltriethoxysilane and tetraethoxysilane).

[0207] Table 5

[0208]

[0209]

[0210] Comparison Example 7-11

[0211] Comparative Examples 7-11 include tannic acid, sorbitan monooleate, sorbitan trioleate, borax, or boric acid as non-polymer bio-based additives, but without organic peroxides. Physical property tests on Comparative Examples 7-11 showed that, compared to Comparative Examples 1 and Examples 15-27 containing organic peroxides, the MOR was lower and sometimes the MOE was lower.

[0212] Table 6

[0213]

[0214]

[0215] Examples 28-31 (of this invention)

[0216] Examples 28-31 include Vul- 40KE was used as an organic peroxide, and carnauba wax, casein, or castor oil were used as non-polymer bio-based additives, as shown in Table 7. Physical property tests on Examples 28-31 revealed a significant increase in MOR (7% to 38% increase relative to Comparative Example 1), and Examples 28-29 showed a significant increase in MOR (11% to 17% increase relative to Comparative Example 1).

[0217] Table 7

[0218]

[0219] Comparison Examples 12-14

[0220] Comparative Examples 12-14 include carnauba wax, casein, or castor oil as non-polymer bio-based additives, but without organic peroxides. Physical property tests on Comparative Examples 12-14 show a reduction in MOR compared to Comparative Example 1. Comparative Examples 12 and 15 further show a reduction in MOE compared to Comparative Example 1. (Comparative Example 1; Table 8).

[0221] Table 8

[0222] Comparison Example 12 Comparison Example 13 Comparison Example 14 wood flour 57 57 57 High-density polyethylene 32 32 32 talc 6 6 4 Zinc stearate 2 2 2 Ethylene distearamide 1 1 1 Brazilian carnauba wax 2 Casein 2 castor oil 4 Broken modulus (psi) 2901 2867 1892 Elastic modulus (ksi) 484 543 254

Claims

1. A non-polymer coupling agent formulation for use in wood polymer composites, the non-polymer coupling agent formulation comprising: a) at least one organic peroxide, wherein the organic peroxide is selected from the group consisting of di(tert-butylperoxyisopropyl)benzene; tert-butyl peroxybenzoate; 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane; 1,1-di(tert-butylperoxy)cyclohexane; 1,1-di(tert-pentylperoxy)cyclohexane; tert-butyl-(2-ethylhexyl)-monoperoxycarbonate; tert-pentyl-(2-ethylhexyl)-monoperoxycarbonate and mixtures thereof; and b) At least one nonpolymeric additive selected from the group consisting of natural acids, acid anhydrides and their esters; natural solids; and mixtures thereof, wherein (i) The ratio of the organic peroxide to the non-polymer additive by weight is from 1:2 to 1:9; (ii) Natural acids and their esters are selected from at least one of the group consisting of itaconic acid; succinic acid; allyl succinic acid; isononenyl succinic acid; and mixtures thereof; (iii) The anhydride of the natural acid is selected from at least one of the group consisting of succinic anhydride, itaconic anhydride, alkenyl succinic anhydride, isononenyl succinic anhydride, and mixtures thereof; and (iv) The natural solid is selected from at least one of the following groups, which consists of aluminum sulfate, potassium aluminum sulfate, ammonium aluminum sulfate, sodium aluminum sulfate, tetrasodium borate, boric acid, carnauba wax, casein, and mixtures thereof.

2. The non-polymer coupling agent formulation for wood polymer composites according to claim 1, wherein, The at least one organic peroxide comprises at least one functionalized organic peroxide.

3. The non-polymer coupling agent formulation for wood polymer composites according to any one of claims 1 to 2, further comprising at least one stabilizer selected from the group consisting of quinone compounds, nitrooxy compounds, and mixtures thereof.

4. The non-polymer coupling agent formulation for wood polymer composites according to claim 3, wherein, The at least one stabilizer is selected from the group consisting of mono-tert-butylhydroquinone (MTBHQ); hydroquinone; hydroquinone monomethyl ether (HQMME) (also known as 4-methoxyphenol); mono-tert-pentylhydroquinone; hydroquinone bis(2-hydroxyethyl) ether; 4-ethoxyphenol; 4-phenoxyphenol; 4-(benzyloxy)phenol; 2,5-bis(morpholinomethyl)hydroquinone; benzoquinone; 4-hydroxyTEMPO; and mixtures thereof.

5. The nonpolymer coupling agent formulation according to any one of claims 1 to 2, wherein it is a solid.

6. The nonpolymer coupling agent formulation according to any one of claims 1 to 2, further comprising a lubricant.

7. A coupling agent masterbatch for wood polymer composites, said coupling agent masterbatch comprising a non-polymer coupling agent formulation according to any one of claims 1 to 6; and c) At least one carrier for the nonpolymer coupling agent masterbatch.

8. The coupling agent masterbatch for wood polymer composites according to claim 7, wherein, c) The carrier for the at least one non-polymer coupling agent masterbatch is selected from the group consisting of polyethylene, calcium carbonate, Burgess clay, precipitated silica, microcrystalline cellulose, fly ash, wood flour, sawdust, straw pellets, rice husk, micro-particulate polyethylene, powdered polyethylene, granulated polyethylene, recycled polyethylene, and combinations thereof.

9. A wood polymer composite material, said wood polymer composite material being manufactured using a non-polymer coupling agent formulation for wood polymer composite materials according to any one of claims 1 to 6, comprising at least one polymer matrix; and at least one filler comprising at least one of wood particles, wood waste particles, wood flour, sawdust, rice husk powder, straw powder, straw fiber, wheat straw, bamboo fiber, flax, jute, hemp, cellulose, groundwood, palm fiber, bagasse, peanut shell, chitin, kenaf fiber, waste paper, paperboard, and mixtures thereof.

10. The wood polymer composite material according to claim 9, wherein, The at least one polymer matrix comprises polyolefins and / or recycled polyolefins.

11. The wood polymer composite material according to claim 9, wherein, The at least one polymer matrix comprises polyethylene and / or polypropylene polymers and copolymers.

12. The wood polymer composite material according to claim 9, wherein, The at least one polymer matrix comprises at least one nonpolar polymer selected from the group consisting of high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and mixtures thereof.

13. The wood polymer composite material according to any one of claims 9 to 12, wherein the wood polymer composite material is in the form of a deck, railing, fence, or wall panel.

14. A wood polymer composite material obtained from the following: a) At least one organic peroxide or its decomposition product, wherein the organic peroxide is selected from the group consisting of di(tert-butylperoxyisopropyl)benzene; tert-butyl peroxybenzoate; 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane; 1,1-di(tert-butylperoxy)cyclohexane; 1,1-di(tert-pentylperoxy)cyclohexane; tert-butyl-(2-ethylhexyl)-monoperoxycarbonate; tert-pentyl-(2-ethylhexyl)-monoperoxycarbonate and mixtures thereof. b) At least one non-polymer additive selected from the group consisting of: i) at least one natural acid, anhydride, or ester thereof; ii) at least one natural solid; and iii) mixtures thereof. c) At least one polymer matrix comprising at least one nonpolar polymer selected from the group consisting of high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), recycled polyethylene, and mixtures thereof; and d) At least one filler comprising at least one of calcium carbonate, Burgess clay, precipitated silica, fly ash, wood pellets, wood product pellets, wood flour, sawdust, rice husk powder, straw powder, straw fiber, wheat straw, bamboo fiber, flax, jute, hemp, cellulose, groundwood, palm fiber, bagasse, peanut shells, chitin, kenaf fiber, waste paper, paperboard, and mixtures thereof. in (i) The ratio of the organic peroxide to the non-polymer additive by weight is from 1:2 to 1:9; (ii) Natural acids and their esters are selected from at least one of the group consisting of itaconic acid; succinic acid; allyl succinic acid; isononenyl succinic acid; and mixtures thereof; (iii) The anhydride of the natural acid is selected from at least one of the group consisting of succinic anhydride, itaconic anhydride, alkenyl succinic anhydride, isononenyl succinic anhydride, and mixtures thereof; and (iv) The natural solid is selected from at least one of the following groups, which consists of aluminum sulfate, potassium aluminum sulfate, ammonium aluminum sulfate, sodium aluminum sulfate, tetrasodium borate, boric acid, carnauba wax, casein, and mixtures thereof.

15. The wood polymer composite material according to claim 14, wherein, The composite material is in the form of deck panels, railings, fences, or wall panels.

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