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    • 专利摘要:
    halogen free flame retardant composition and article the present invention relates to a halogen free flame retardant composition comprising weight percent based on the weight of the composition: a. 20-60% tpu / si-g-eva polymer blend where si-g-eva is cross-linked, b. 1 to 25% organic phosphate ester, c. 30 to 60% metal hydrate, and the. 0.1 to 10% of epoxidized novolac. optionally, the compositions may additionally comprise, by weight percent based on the weight of the composition, one or more of: e. 0.01 to 0.5% anti-drip agent, f. 0.1 to 2% additive, and g. 0.1 to 5% load.
    公开号:BR112012029894B1
    申请号:R112012029894-1
    申请日:2010-05-24
    公开日:2019-06-25
    发明作者:Wilson Xiao Wei Yan；Given Jing Chen；Lotus Hua Huang；David Hong Fei Guo
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION The invention relates to thermoplastic polyurethane (TPU) composites. In one embodiment, the invention relates to TPU composites which are halogen-free and flame retardant while in another aspect the invention relates to TPU copolymers which are halogen-free, flame retardant and comprise a copolymer of crosslinked silane grafted ethylene vinyl acetate.
    BACKGROUND OF THE INVENTION Halogen-free flame retardant (HFFR) thermoplastic polyurethane (TPU) compositions are replacing halogen-containing flame retardant TPU compositions in a number of applications, including, but not limited to, the insulation and protective liners for the wire and cable associated with personal electronic devices. These HFFR TPU compositions may provide excellent flame retardant performance and mechanical properties including excellent flexibility. In addition, these HFFR TPU compositions may meet the requirements of thermal deformation tests (UL-1581) at 150 ° C, which is particularly important in some applications and generally not obtainable with a non-crosslinked polyolefin polymer matrix. However, such HFFR TPU compositions are not without their limitations and comparatively with HFFR polyolefin compositions, often prove more expensive and exhibit insulation resistance (IR), poor smoke density and higher material density failures. The ethylene vinyl acetate copolymer (EVA) has good compatibility with the TPU and also exhibits good flexibility. EVA with a low vinyl acetate content (30 percent by weight (w / w%) or less) exhibits higher electrical resistance and lower material density than the TPU. EVA is also less expensive than the TPU, and does not contain a benzene structure in its molecular structure (aromatic structures contribute to the smoke density of a product). Thus, EVA appears at first glance to be a suitable compound to blend with the TPU without sacrificing the mechanical property and flexibility of the TPU. However, the thermal deformation performance of the TPU is destroyed when formulating it with EVA and thus HFFR TPU / EVA compositions fail to pass thermal deformation specifications that require a deformation ratio lower than 50% at 150 ° C .
    SUMMARY OF THE INVENTION In one embodiment, the invention is a halogen-free flame retardant composition comprising a thermoplastic polyurethane (TPU) and a crosslinked ethylene vinyl acetate copolymer silane grafted (Si-g-EVA). In one embodiment, the TPU / Si-g-EVA composition further comprises one or more additives or fillers, such as an anti-drip agent, an antioxidant, a UV stabilizer, processing aids and / or a metal oxide such as titanium dioxide.
    In one embodiment, the invention is a TPU / Si-g-EVA HFFR composition comprising a weight percent based on the weight of the composition: A. 20 to 60% TPU / Si-g-EVA polymer blend wherein Si -EG-EVA is crosslinked, B. 5 to 20% organic phosphate ester, C. 30 to 60% metal hydrate, and D. 0.1 to 10% carbonaceous forming agent.
    In one embodiment, the TPU / Si-g-EVA polymer blend comprises 50-95% w / w TPU and 5 to 50% w / w Si-g-EVA based on the weight of the blend, i.e. , TPU plus Si-g-EVA. In one embodiment, the TPU / Si-g-EVA HFFR composition further comprises in percent by weight based on the weight of the composition, one or more of: Ε. 0.01 to 0.5% w / w of anti-drip agent, F. 0.1 to 2% of additive, and G. 0.1 to 5% of filler.
    In one embodiment, the TPU / Si-g-EVA compositions of this invention are manufactured as insulation products and other cover products for wires and cables, or other various parts or components for use in the manufacture of automobiles, building materials and constructions , artificial leather, household appliances, textiles, furniture and information technology devices. These various products may be manufactured by one or more disparate methods including extrusion, foaming and molding. The present application comprises the following items: A TPU / Si-g-EVA HFFR composition comprising a weight percent based on the weight of the composition: A. 20 to 60% TPU / Si-g-EVA polymer blend where the Si-g-EVA is crosslinked, B. 1 to 25% organic phosphate ester, C. 30 to 60% metal hydrate, and D. 0.1 to 10% epoxidized novolak. 2. The composition of item 1 in which the polymer blend comprises 50-95% w / w TPU and 5 to 50% w / w Si-g-EVA based on the weight of the TPU / Si- g-EVA. 3. The composition of items 1 or 2 in which Si-g-EVA comprises a vinyl acetate content of 10-70% w / w based on the weight of the EVA copolymer. The composition of any of the foregoing, further comprising a silane content of 0.5-10% w / w based on the weight of the EVA copolymer. The composition of any one of the preceding items, wherein the phosphate ester is at least one of resorcinol bis (diphenyl phosphate) and bis (diphenyl phosphate) of bisphenol-A (BPADP) and is present in a amount of 5 to 20% w / w. The composition of any one of the preceding items, wherein the metal hydrate is at least one of aluminum trihydroxide (ATH) and magnesium hydroxide and is present in an amount of 35 to 55% w / w. The composition of any one of the foregoing, further comprising at least one of an anti-drip agent, an antioxidant, a UV stabilizer, a processing aid and a filler. The composition of any of the foregoing in which the TPU is at least one polyester-based polyether-based polyester and is present in an amount of 60 to 90% w / w based on the weight of the polymer blend of TPU / Si-g-EVA. An article comprising the composition of any one of the preceding items. 10. The item of item 9 in the form of a cover for wires or cables.
    BRIEF DESCRIPTION OF THE DRAWINGS The invention will now be further described with reference to the accompanying drawings, which Figures 1A-1F are atomic force microscopy images of TPU samples 8-10 and mixtures of crosslinked Si-g-EVA.
    Detailed description of the invention Unless otherwise stated, implied by the context, or customary in the art, all parts and percentages are weight based and all test methods are current as of the date of filing of this disclosure. For the purposes of the United States patent practice, the content of any patent, application or patent publication is fully incorporated by reference (or its U.S. version is hereby incorporated by reference), especially with respect to the disclosure of definitions, are not inconsistent with any definitions specifically provided in this disclosure) and general knowledge in the art.
    The numeric ranges in this descriptive are approximate, so they may include values outside the range, unless otherwise noted. Numeric ranges include all values from and including the lower and upper values in increments of one unit, provided there is a separation of at least two units between any lower value and any higher value. As an example, if a compositional, physical, or other property, such as, for example, molecular weight, melt index, etc., is from 100 to 1000, then all individual values, such as 100, 101, 102, etc., and sub-bands, such as 100 to 144, 155 to 170, 197 to 200, etc., are expressly enumerated. For ranges containing values that are less than one or containing fractional numbers greater than one (eg, 1,1,1,5, etc.), a unit is considered to be 0.0001, 0.001, 0.01 or 0.1, as appropriate. For bands containing single digit numbers smaller than ten (eg, 1 to 5), a unit is typically considered to be 0.1. These are only examples of what is intended, and all possible combinations of numerical values between the lowest value and the highest value listed, should be considered as having been expressly stated in this disclosure. Numerical ranges are provided in this disclosure for, among other things, the amounts of components in the composition and / or coating, additives, and various other components in the composition, and the various characteristics and properties by which these components are defined. Numeric ranges are provided within this descriptive for, among other things, the amount of the components in the composition. "Wire" and similar terms mean a single filament of conductive material, eg, copper or aluminum, or a single fiber-optic filament. "Cable" and similar terms mean at least one wire or fiber optic within a cover, e.g., an insulation cover, or an outer protective jacket. Typically, a cable comprises two or more wires or optical fibers connected together, typically in a common insulation cover and / or protective jacket. The individual threads or fibers within the jacket may be bare, covered or insulated. Cables in combination may contain both electric wires and optical fibers. Cable, etc. can be designed for low, medium or high voltage applications. Typical cable designs are shown in U.S. Patent Nos. 5,246,783, 6,496,629 and 6,714,707. "Composition", and similar terms, mean a mixture or mixture of two or more components. "Polymer blend", and similar terms mean a mixture of two or more polymers. Such a mixture may or may not be miscible. Such a mixture may or may not be separated in phases. Such a mixture may or may not contain one or more domain configurations as determined by transmission electron spectroscopy, light scattering, X-ray scattering, and any other method known in the art. The term "polymer" (and similar terms) is a macromolecular compound prepared by reacting (i.e., polymerizing) monomers of the same or different types. "Polymers" includes homopolymers and interpolymers. "Interpolymer" means a polymer prepared by the polymerization of at least two different monomers. This generic term includes copolymers, generally used to refer to polymers prepared from two different monomers, and polymers prepared from more than two different monomers, eg, terpolymers, tetrapolymers, and the like. "Olefin-based polymer" and similar terms means a polymer comprising, in the polymerized form, a major percentage of an olefin, for example ethylene or propylene, based on the total weight of the polymer. Non-limiting examples of olefin-based polymers include polymers based on ethylene and polymers based on propylene. "Halogen-free", and similar terms means that the compositions of this invention are without or substantially free of halogen content, ie contain less than 2000 mg / kg halogen as measured by ion chromatography (IC) or a similar analytical method . A halogen content of less than this amount is considered inconsequential to the efficacy of many products, e.g., a wire or cable sheath, made with the compositions of this invention. "Ambient conditions" and similar terms mean a temperature of 23 ° C and atmospheric pressure. "Catalytic amount" means an amount of catalyst necessary to promote the cross-linking of an ethylene-vinylsilane polymer to a detectable level, preferably at a commercially acceptable level. Quot; crosslinkedquot ;, " cured ", and the like terms mean that the polymer, before or after being shaped into an article, has been subjected to or exposed to a treatment which induced crosslinking and has extractable with xylene or decalene of less than or equal to 90 percent by weight (i.e., a gel content greater than or equal to 10 percent by weight).
    Specific Embodiments The thermoplastic polyurethane used in the practice of this invention is the reaction product of a polyisocyanate (typically a diisocyanate), one or more polymeric diol (s), and optionally one or more difunctional chain extender . "Thermoplastic" as used herein describes a polymer which (1) has the ability to be stretched beyond its original length and retracts to substantially its original length when released, and (2) softens when exposed to heat and substantially returns to condition when cooled to room temperature. The TPU may be prepared by prepolymer, quasi-polymer, or direct methods. The isocyanate forms a hard segment in the TPU and may be an aromatic, aliphatic, or cycloaliphatic isocyanate and combinations of two or more of these compounds. A non-limiting example of a structural unit derived from a diisocyanate (OCN-R-NCO) is represented by formula (I): wherein R is an alkylene, cycloalkylene, or arylene group. Representative examples of these isocyanates can be found in U.S. Patent Nos. 4,385,133, 4,522,975, and 5,167,899. Non-limiting examples of suitable diisocyanates include 4,4'-diisocyanatodiphenyl-1-methane, p-phenylene diisocyanate, 1,3-bis (isocyanatomethyl) -cyclohexane, 1,4-diisocyanate-cyclohexane , hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethyl-4-4'-biphenyl diisocyanate, 4,4'-diisocyanate dicyclohexylmethane diisocyanate, 2,4-toluene, and 4,4'-diisocyanate diphenylmethane. The polymer diol forms soft segments in the resulting TPU. The polymer diol may have a number average molecular weight in the range of, for example, 200 to 10,000 g / mol. More than one polymer diol may be employed. Non-limiting examples of suitable polymer diols include polyether diols (producing a "polyether TPU"); polyester polyols (producing a "polyester TPU"); polycarbonates (producing a "polycarbonate TPU"); hydroxy terminated polybutadienes; hydroxy-terminated polybutadiene-acrylonitrile copolymers; hydroxy terminated copolymers of dialkyl siloxane and alkylene oxides, such as ethylene oxide, propylene oxide, natural oil diols, and any combination thereof. One or more of the above polymer diols may be blended with an amine terminated polyether or an amino terminated polybutadiene-acrylonitrile copolymer. The difunctional chain extender may be straight and branched chain aliphatic diols having 2 to 10 carbon atoms, inclusive, in the chain. Illustrative of such diols are ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, and the like; 1,4-cyclohexanedimethanol; hydroquinone bis (hydroxyethyl) ether; cyclohexylene diols (1,4-, 1,3-, and 1,2- isomers, isopropylidene bis (cyclohexanols); diethylene glycol, dipropylene glycol, ethanolamine. N-methyl-diethanolamine, and the like; and mixtures of any of the foregoing. As noted earlier, in some cases, minority proportions (less than 20 equivalent percent) of the difunctional extender may be replaced by trifunctional extenders, without departing from the thermoplasticity of the resulting TPU; illustrative of such extenders are glycerol, trimethylolpropane, and the like. The chain extender is incorporated into the polyurethane in amounts determined by the specific selection of the reactant components, the desired amounts of the hard and soft segments, and the index sufficient to provide good mechanical properties such as modulus and tear strength. The polyurethane compositions may contain, for example, from 2 to 25, preferably from 3 to 20, and more preferably from 4 to 18,% w / w, of the extender component.
    Optionally, small amounts of compounds having monohydroxyl functionality or monoamine functionality, often referred to as "chain parators", may be used to control molecular weight. Illustrative of such chain parters are propanols, butanols, pentanols and hexanols. When used, chain halbers will typically be present in amounts of 0.1 to 2 percent by weight of the entire reaction mixture leading to the polyurethane composition.
    The equivalent proportions of polymer diol for said extender may vary considerably depending on the desired hardness for the TPU product. In general terms, the equivalent ratios fall within the respective range of from about 1: 1 to about 1:20, preferably from about 1: 2 to about 1:10. At the same time, the overall ratio of isocyanate equivalents to equivalents of active hydrogen containing materials is within the range of from 0.90: 1 to 1.10: 1, and preferably from 0.95: 1 to 1.05: 1.
    In one embodiment, the TPU is at least one polyether-based or polyester-based polyurethane. Polyether-based TPU compositions are preferred. In one embodiment, the TPU has a Shore A hardness of 70-95 as measured according to ASTM D-1238.
    Non-limiting examples of suitable TPUs include the commercially available PELLETHANEMR thermoplastic polyurethane elastomers from Lubrizol Corporation, ESTANEMR thermoplastic polyurethanes, CARBOTHANEmr thermoplastic polyurethanes, TECOPHILICmr thermoplastic polyurethanes, TECOPLASTMR thermoplastic polyurethanes, and TECOTHANEMR thermoplastic polyurethanes, all commercially available from Noveon, ELASTQLLAN® thermoplastic polyurethanes and other commercially available thermoplastic polyurethanes from BASF; and commercially available thermoplastic polyurethanes from Bayer, Huntsman, The Lubrizol Corporation and Merquinsa. The TPU typically comprises at least 50, more typically at least 55, and more typically at least 60,% w / w of the TPU / Si-g-EVA blend. The TPU typically comprises no more than 95, more typically no more than 93 and still more typically no more than 90,% w / w of the halogen-free TPU composition. Ethylene vinyl acetate is a well known polymer and is commercially available readily, e.g., ELVAX® EVA resins from DuPont. The vinyl acetate content of the EVA resins used in the practice of this invention may vary widely, but typically the minimum vinyl acetate content is at least 10, typically at least 12, and still more typically at least 15% /P. The maximum vinyl acetate content in the EVA resins in the practice of this invention may also vary widely but typically is not greater than 70, more typically not greater than 50 and still more typically not greater than 30,% w / w. The EVA copolymer used in the practice of this invention is grafted with silane. Any silane that effectively grafts into or crosses the EVA may be used in the practice of this invention, and those described by the following formula are exemplary: wherein R1 is a hydrogen atom or a methyl group; x and y are 0 or 1 with the proviso that when x is 1, y will be 1; n is an integer from 1 to 12 inclusive, preferably from 1 to 4, and each R "is independently a hydrolyzable organic group such as an alkoxy group having 1 to 12 carbon atoms (e.g., methoxy, ethoxy, (e.g., phenoxy), an aryloxy group (e.g., benzyloxy), an aliphatic acyloxy group having 1 to 12 carbon atoms (e.g., formyloxy, acyloxy, propanoyloxy ), amino or substituted amino groups (alkylamino, arylamino), or a lower alkyl group having from 1 to 6 carbon atoms inclusive, with the proviso that not more than one of the three R "groups is an alkyl. Such silanes are grafted onto a suitable ethylene polymer by the use of a suitable amount of organic peroxide. Additional ingredients such as heat and light stabilizers, pigments, etc., may also be included in the EVA and silane compound. However, the crosslinking reaction typically is effected by moisture-induced reaction between the grafted silane groups, water permeating the polymer mass in the atmosphere or a water bath or sauna. The process step during which the lattices are created is commonly referred to as the "cure phase" and the process itself is commonly referred to as "cure".
    Suitable silanes include unsaturated silanes comprising an ethylenically unsaturated hydrocarbyl group, such as a vinyl, allyl, isopropenyl, butenyl, cyclohexenyl, or gamma (meth) acryloxy allyl group, and a hydrolyzable group such as, for example, a hydrocarbyloxy group , hydrocarbyloxy, or hydrocarbylamino. Examples of hydrolyzable groups include methoxy, ethoxy, formyloxy, acetoxy, propionyloxy, and alkyl or arylamino groups. Preferred silanes are the unsaturated alkoxy silanes which can be grafted onto the polymer. Such silanes and their method of preparation are more fully described in U.S. Patent No. 5,266,627 to Meverden, et al. Vinyl trimethoxy silane (VTMS), vinyl triethoxy silane, vinyl triacethoxy silane, gamma- (meth) acryloxy silane and mixtures of these silanes are the preferred silane crosslinkers for use in this invention. The amount of silane crosslinker used in the practice of this invention may vary widely depending on the nature of the polymer, silane, processing or reactor conditions, grafting efficiency, the final application, and the like, but is typically at least less 0.5, preferably at least 0.7,% w / w, based on the weight of the EVA, is used. Considerations of convenience and economy are two of the major limitations on the maximum amount of silane crosslinker used in the practice of this invention, and typically the maximum amount of silane crosslinking agent will not exceed 5, preferably not exceed 3 percent by weight. The silane crosslinker is grafted onto the polymer by any conventional method, typically in the presence of a free radical initiator, eg, peroxides and azo compounds, or by ionizing radiation, etc. Organic initiators are preferred, such as any of the peroxide initiators, for example, dicumyl peroxide, di-t-butyl peroxide, t-butyl perbenzoate, benzoyl peroxide, cumene hydroperoxide, t-butyl peroctoate, methyl ethyl ketone peroxide, 2,5-dimethyl-2,5-di (t-butyl peroxy) hexane, lauryl peroxide, and tert-butyl peracetate. A suitable azo compound is 2,2-azobisisobutyronitrile. The amount of initiator may vary but will typically be present in an amount of at least 0.04, preferably at least 0.06, parts per hundred parts of resin (phr). Typically, the initiator does not exceed 0.15, preferably does not exceed about 0.10 phr. The weight ratio of silane crosslinking agent may also vary widely, but the weight ratio of crosslinker initiator is from 10: 1 to 500: 1, preferably from 18: 1 to 250: 1. As used in parts per hundred resin or phr, "resin" means the olefinic polymer.
    While any conventional method can be used to graft the silane into the polyolefin polymer, a preferred method is to mix the two with the initiator in the first stage of the reactor extruder, such as a Buss washer. The grafting conditions may vary, but the melting temperatures are typically between 160 and 260øC, preferably between 190 and 230øC, depending on the residence time and the starter half life. Si-g-EVA typically comprises at least 5, more typically at least 10, and still more typically at least 15,% w / w, of the TPU / Si-g-EVA polymer blend. Si-g-EVA typically comprises not more than 40, and still more typically no more than 30,% w / w, of the TPU / Si-g-EVA polymer blend.
    The blend component of TPU / Si-g-EVA polymers of the compositions of this invention comprises two phases, which taken together, form the base matrix of the other components, phosphate esters, metal hydrates, etc., of the TPU / polymer blend of TPU / Si-g-EVA HFFR. The blend may be formed in any convenient manner, one of which is to cross-link the Si-g-EVA polymer blend under ambient conditions, e.g., 20 to 30øC and 40 to 60% relative humidity, in the presence of (i) any of the many known catalysts to promote crosslinking of the silane grafted compounds (e.g., SILINKmr DFDA-5488 commercially available from The Dow Chemical Company) and, (ii) the TPU. The components of the blend are simply mixed with one another using formulation equipment (e.g., a Haake mixer or a twin screw extruder) and conventional protocols. Water in any form is optional for the crosslinking process. The TPU / Si-g-EVA blend component of the compositions of this invention may comprise one or more free halogen polymers, thermoplastics other than TPU, and EVA. These other optional polymers include, but are not limited to, polyethylene, polypropylene, ethylene- or propylene copolymer, styrenic block copolymer, and the like. These other polymers may be dispersed, continuously or discontinuously with the TPU, in the Si-g-EVA or both. If present, the one or more polymer (s) will typically be present in an amount of 1 to 50, more typically 2 to 30 and still more typically 5 to 20,% w / w , based on the combined weight of the blend of polymers, ie, TPU, Si-g-EVA and other polymer (s). If present, these other polymer (s) will typically be blended with the TPU and Si-g-EVA after the polymer blend has been formed. The TPU / Si-g-EVA blend typically comprises at least 20, more typically at least 30, and still more typically at least 40,% w / w of the TPU / Si-g-EVA HFFR composition. Si-g-EVA typically comprises not more than 60, more typically not more than 55 and still more preferably not more than 50,% w / w, of the TPU / Si-g-EVA HFFR composition. Organic Phosphate Ester The organic phosphate esters useful in the practice of this invention include both aromatic and aliphatic phosphate esters and their polymers. Examples of aliphatic phosphate flame retardants include trimethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, monoisodecyl phosphate and 2-acryloyloxyethyl acid phosphate. Examples of aromatic phosphate esters include trixylenyl phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyldiphenyl phosphate, xylenyldiphenyl phosphate, and diphenyl-2-methacryloyloxyethyl phosphate. Examples of bis (phosphate aromatic esters) include resorcinol bis (diphenylphosphate), resorcinol bis (dixilenyl phosphate), resorcinol bis (dicresyl phosphate), hydroquinone bis (dixilenyl phosphate), bis (diphenylphosphate) bisphenol-A (BPADP) and tetrakis (2,6-dimethylphenyl) -1,3-phenylene bisphosphate. These phosphate esters may be used alone or in combination with each other. Preferred organic phosphate esters include RDP and BPADP, alone or in combination with one another. The organic phosphate ester typically comprises at least 1, more typically at least 5, and still more typically at least 10,% w / w of the TPU / Si-g-EVA HFFR composition. The organic phosphate ester typically comprises no more than 25, more typically no more than 20 and still more typically no more than 15,% w / w of the TPU / Si-g-EVA HFFR composition.
    Metallic Hydrate Preferred metal hydrates for use in the practice of this invention include, but are not limited to, aluminum trihydroxide (also known as ATH or aluminum trihydrate) and magnesium hydroxide (also known as magnesium dihydroxide). The metal hydrate may be naturally occurring or synthetic, and they may be used alone or in combination with one another and / or with other inorganic flame retardants, e.g., calcium carbonate, silica, etc., typically in amounts reduced. The metal hydrate typically comprises at least 30, more typically at least 35, and still more typically at least 40,% w / w of the TPU / Si-g-EVA HFFR composition. The metal hydrate typically comprises no more than 60, more typically no more than 55 and still more typically no more than 50, w / w% of the TPU / Si-g-EVA HFFR composition.
    The TPU / Si-g-EVA HFFR composition includes one or more carbon residue forming agents in order to minimize dripping during combustion. In some embodiments, the carbonaceous former is an epoxidized novolak resin. Epoxidized novolak resins are the reaction product of epichlorohydrin and a polymer of phenol novolac in an organic solvent. Non-limiting examples of suitable organic solvents include acetone, methyl ethyl ketone, methyl amyl ketone, and xylene. The epoxidized novolak resin may be a liquid, a semi-solid, a solid or a combination of two or more physical states of material. The carbonaceous former is typically used in an amount of 0.1 to 10% w / w based on the total weight of the composition. This includes embodiments in which the agent is used in an amount ranging from 1 to 3% w / w based on the total weight of the composition, and additionally includes embodiments where the agent is used in an amount ranging from 1.5 to 2% w / w, based on the total weight of the composition.
    Optional Anti-Drip Agent In one embodiment, the TPU / Si-g-EVA HFFR composition further comprises an anti-drip agent. Examples include, without limitation, one or more of triglycidyl isocyanurate and fluorine based resins, such as polytetrafluoroethylene, tetrafluoroethylene and hexafluoropropylene copolymers, tetrafluoroethylene fluoride carbide and perfluoroalkyl vinyl ether, polyvinylidene fluoride resins, and the like.
    If present, the anti-drip agent will typically comprise at least 0.01, more typically at least 0.05 and still more typically at least 0.07% w / w of the TPU / Si-g-EVA HFFR composition. If present, the anti-drip agent will typically comprise not more than 2, more typically not more than 1.5 and still more typically no more than 1% w / w of the TPU / Si-g-EVA HFFR composition.
    Additives and Optional Loads The TPU / Si-g-EVA HFFR composition may optionally also contain additives and / or fillers. Representative additives include, but are not limited to, antioxidants, processing adjuvants, colorants, ultraviolet stabilizers (including UV absorbers), antistatic agents, nucleating agents, glidants, plasticizers, lubricants, viscosity controlling agents, anti-blocking, surfactants, extender oils, acid scavengers, and metal deactivators. If present, these additives are typically used in a conventional manner and in conventional amounts, e.g., from 0.01% w / w to less or up to 10% w / w or more, based on the total weight of the composition.
    Representative fillers include, but are not limited to, various metal oxides, e.g., titanium dioxide, metal carbonates such as magnesium carbonate and calcium carbonate; sulfides and metal sulfates such as molybdenum disulphide and barium sulfate; metal borates such as barium borate, barium metaborate, zinc borate and zinc metaborate; metal anhydrides such as aluminum anhydride; clays such as diatomite, kaolin and montmorillonite; huntita; celite; asbestos; ground minerals; and lithopone. If present, these additives will typically be used in a conventional manner and in conventional amounts, e.g., from 5% w / w or less to 50% w / w or more based on the weight of the composition.
    Suitable UV light stabilizers include hindered amine light stabilizers (HALS) and UV absorbing additives (UVA). Representative HALS which may be used in the composition include, but are not limited to, TINUVIN® XT 850, TINUVIN® 622, TINUVIN® 770, TINUVIN® 144, SANDUVOR® PR-31 E Chimassorb 119 FL. TINUVIN® 770 is bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, has a molecular weight of about 480 grams / mole, is commercially available from Ciba (now part of BASF), and has secondary amine groups. TINUVIN® 144 is bis- (1,2,2,6,6-pentamethyl-4-piperidinyl) -2-n-butyl-2- (3,5-di-tert-butyl-4-hydroxybenzyl) , has a molecular weight of about 685 grams / mole, contains tertiary amines, and is also commercially available from Ciba. SANDUVOR® PR-31 is propanedioic acid, [(4-methoxyphenyl) methylene] bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester, has a molecular weight of about 529 grams / mol, contains tertiary amines, and is commercially available from Clairant Chemicals (India). Chimassorb 119 FL or Chimassorb 119 is 10% w / w dimethyl succinate polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 90% w / w N, N ' [1,2-ethanediylbis [[[4,6-bisbutyl (1,2,2,6,6-pentamethyl-4-piperidinyl) amino] -1,3,5-triazin-2-yl] imino] 3,1-propanediyl]] bis [Î ± ', N' -dibutyl-N 'N' -bis (1,2,2,6,6-pentamethyl-4-piperidinyl)] - 1, and is commercially available of Ciba, Inc. Representative UV absorbing additives include types of benzotriazole such as Tinuvin 326 and Tinuvin 328 commercially available from Ciba Inc. HALS mixtures and UVA additives are also effective.
    Examples of antioxidants include, but are not limited to, hindered phenols such as tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) methane; bis (β-tert-butylhydroxybenzyl) methylcarboxyethyl, 4,4'-thiobis (2-methyl-6-di-tert-butylphenol), 4,4'-thiobis (2-tert- 2,2'-thiobis (4-methyl-6-tert-butylphenol), and thiodiethylene bis (3,5-di-tert-butyl-4-hydroxy) cinnamate, phosphites and phosphonites such as such as tris (2,4-di-tert-butyl-4-phenyl) phosphite, and di-tert-butylphenyl phosphonite, such compounds as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, various siloxanes; , 2,4-trimethyl-1,2-dihydroquinoline, n, n'-bis (1,4-dimethylpentyl-p-phenylenediamine), alkylated diphenylamines, 4,4'-bis (alpha, alpha-dimethylbenzyl ) diphenylamine, diphenyl-p-phenylenediamine, mixed di-aryl-p-phenylenediamines, and other antidegradants or hindered amine stabilizers. Antioxidants may be used, for example, in amounts of 0.1 to 5% w / w with based on the weight of the composition.
    Examples of processing aids include, but are not limited to, metal salts of carboxylic acids such as zinc stearate or calcium stearate; fatty acids such as stearic acid, oleic acid or erucic acid; fatty amides such as stearamide, oleamide, erucamide, or N, N'-ethylene bis-stearamide; polyethylene wax; oxidized polyethylene wax; polymers of ethylene oxide; copolymers of ethylene oxide and propylene oxide; vegetable waxes; oil waxes; nonionic surfactants; silicone fluids and polysiloxanes.
    Formulation / Fabrication The formulation of the compositions of this invention may be made by standard means known to those skilled in the art. Examples of formulation equipment are internal batch mixers, such as a Haake, Banbury or Bolling internal mixer. Alternatively, continuous single or double screw mixers may be used, such as a Farrel continuous mix, a Werner and Pfleiderer double screw mixer, or a Buss continuous kneading extruder. The type of mixer used and the operating conditions of the mixer will affect composition properties such as viscosity, volumetric resistivity, and the smoothness of the extruded surface.
    In one embodiment, the TPU / Si-g-EVA HFFR composition is prepared by pre-drying TPU pellets at a temperature of 80 to 100øC, preferably 90-95øC for at least 6 hours under vacuum, preferably for 6 hours. to 10 hours. The dried TPU is then formulated with Si-g-EVA and cross-linking catalyst at a temperature of from 160 to 220øC, preferably from 160 to 200øC. Alternatively, and preferably, the dried TPU pellets are formulated with Si-g-EVA and cross-linking catalyst at a temperature under ambient conditions. The polymer blend once prepared, the flame retardants and optional carbonaceous and antifouling agents, additives and fillers are mixed with the blend using conventional formulation equipment and temperatures of 160 to 220øC, preferably 160ø to 200 ° C.
    In some embodiments, the additives are added as a premix masterbatch. Such masterbatches are commonly formed by dispersing the additives, separately or together, a small amount of the TPU, or, if the TPU is in combination with another resin, e.g. a polyethylene or polypropylene, with a small amount of the other resin. The masterbatches are suitably formed by melt formulation methods.
    In one embodiment, the TPU / Si-g-EVA HFFR composition of this invention may be applied as a cover to a cable, e.g., such as a blanket or insulation layer, in known amounts and by methods known (for example, with the equipment and methods described in U.S. Patents 5,246,783 and 4,144,202). Typically, the polymer composition is prepared in a reactor extruder equipped with a cable blanking die and after the components of the composition are formulated, the composition is extruded onto the cable as the cable is pulled through the die. Coating is typically subjected to a curing period that occurs at temperatures from ambient to but below the melting point of the composition until the article has achieved the desired degree of cross-linking. The cure can start in the extruder-reactor.
    Other articles may be prepared from the polymer compositions of this invention, particularly under conditions of high pressure and / or high humidity, including fibers, strips, tapes, pipes, pipes, weathercocks, seals, gaskets, foams, shoes and bellows . Items are manufactured using known equipment and techniques.
    The HFFR TPU / Si-g-EVA compositions of this invention exhibit satisfactory flame resistance performance without using halogenated flame retardants and thus removing environmental and health problems in the combustion of the compositions. The HFFR TPU / Si-g-EVA compositions of this invention also meet the requirements of the thermal deformation test at a temperature as high as 150 ° C which is not achieved with the use of a mixture of uncrosslinked TPU and EVA as the matrix base for organic flame retardant phosphates. The base matrix exhibits improved flexibility relative to a polypropylene matrix, and lower density relative to an EVA-free TPU matrix. The TPU / Si-g-EVA HFFR compositions also exhibit lower smoke density and insulation resistance comparable to, if not greater than, a HFFR TPU com. The invention is described more fully by way of the following examples. Unless otherwise noted, all parts and percentages are by weight.
    Specific Achievements Materials PELLETHANEM® 2103-90 AE polyester thermoplastic polyurethane (commercially available from Lubrizol); density = 1.14 g / cm 3 per ASTM D792; MI 7 g / 10 min per ASTM D1238). Prior to use the TPU samples are pre-dried at 90øC for at least 6 hours under vacuum.
    ELVAX® 265 ethylene vinyl acetate copolymer (28% vinyl acetate content, density 0.951 g / cm 3 per ASTM D 1238. Prior to use the EVA samples are pre-dried at 50 ° C for at least 6 hours under vacuum The peroxide is 2.5 (di-tert-butylperoxy) -2,5-diethylhexane (LUPEROX® 101 commercially available from Aldrich) having a purity of 90% and density of 0.877 g / cm3. Aldrich) having a purity of 97% and density of 0.971 g / cm 3 is used as received.
    Masterbatch of SILINKMR AC DFDA-5488 catalyst is obtained from The Dow Chemical Company (comprising a sulphonic acid catalyst, a functionalized ethylene polymer and a linear low density polyethylene (LLDPE).
    Resorcinol bis (diphenyl phosphate) (RDP) is obtained from Supresta, having a grade name FYROFLEX® RDP. The epoxidized novolak is selected as solvent free DEN438 with epoxy equivalent weight (EEW) of 176-181 (commercially available from The Dow Chemical Company). Aluminum trihydrate (ATH) with a low apparent density of 0.2 - 0.5 g / cm 3 is obtained from SHOWA Chemical, Japan.
    According to Table 1, a mixture of liquid VTMS and peroxide is added to dried EVA pellets, and the liquid component in the pellets is allowed to soak under ambient conditions for 30 minutes with the aid of a Double roller mixer. A grafting of the polymers obtained in a Haake laboratory scale mixer (Haake Polylab OS RheoDrive 7, Thermo Scientific) with closed blending space is conducted. The mixing time is fixed at 4.5 minutes with a rotational speed of 50 revolutions per minute (rpm). The mixing temperature is set at 190 ° C. Silane-grafted EVA is cut into small pellets for further processing.
    Table 1 Si-g-EVA Formulations
    Formulation Process 1. Master Batch Formulation of Si-g-EVA Catalyst According to table 2, TPU and Si-g-EVA are charged together to the Haake mixer under a shear rate of 60 rpm and at a temperature of 180 ° C. After 2-3 minutes the master batch of AC catalyst is added and formulated for an additional 5 minutes. The resulting polymer blend is plated and cut into small pieces and then placed in an ASTM room at a set temperature of 23 ± 1 ° C and 50 + 5% relative humidity to cure.
    Table 2 TPU / EVA Crosslinked Polymer Blends TPU Compositions / Si-g-EVA HFFR Compositions
    Inventive Samples 11-17 The cured polymer samples 11-17 obtained in step 1 are optionally dried at 90øC under vacuum for 6 hours, then formulated with flame retardant (FR) chemicals in the Haake mixer. The cured polymer samples from step 1 are charged into the mixing chamber at a shear rate of 60 rpm and a temperature of 180øC for plastification. After 2 minutes, a mixture of ATH, RDP and epoxidized novolac is added within 2 minutes and formulated for an additional 6 minutes.
    Comparative Samples 5-7 Samples 5-7 of TPU, EVA, or Si-g-EVA are charged together in the Haake mixer at a shear rate of 60 rpm and at a temperature of 180øC. After 2-3 minutes, a mixture of ATH, RDP and epoxidized novolac is added within 2 minutes and formulated for an additional 6 minutes.
    Assays The polymer compounds made in step 1 (samples 8-10) and the formulation of step 2 shown above are pressed to plates using a compression molder at 180-185 ° C. Plates having a thickness of about 1.5 mm are then subjected to a cold press under the same pressure and at room temperature for 5 minutes. The samples are then used in the following tests. 1. Thermal Deformation The thermal deformation test is conducted according to UL 1581-2001. For each formulation, two or three parallel sample plates are placed in an oven and preheated to 150øC for one hour. The preheated samples are then pressed with the same charge at 150 ° C for one hour. Thereafter, the pressed samples without weight removal are placed in an ASTM chamber with a temperature set at 23øC for an additional hour. The change in thickness of the sample plates is recorded and the rate of thermal deformation is calculated according to HD% = (D0-Di) / D0 * 100%, where D represents the original thickness of the sample and Dx represents the thickness of the sample after the deformation process. The mean strain ratios for the two parallel samples are taken. 2. Tensile Assays The tensile tests were conducted on an INSTRON® 5565 tensile tester. Plates are cut in bell shape using a dot matrix cutter. The tensile tests are performed according to ASTM D638 at room temperature. The speed is 50 mm / min. 3. Electron Microscopy (AFM) Morphology Investigation Samples are first microtomed using a diamond knife at -120 ° C in a LEICAMR UC6 microtome equipped with an FC6 cryo-disconnector chamber, and then images are obtained in a V nanoscope (S / N NS5-226) using an AFM Dimension 3100 Large Sample (Vecco, Inc., Santa Barbara, CA. S / n: 366 #).
    4. FR Performance The VW-1 mimetized FR test is conducted in a UL94 chamber. The test body is limited to 200 mm by 2.7 mm by 1.9 mm. The test body is hung in the jaw with the longitudinal axis vertically applying a load of 50 g on the lower end. A paper marker (2 cm by 0.5 cm) is applied to the top of the wire. The distance from the bottom of the flame (highest point of the burner) to the bottom of the marker is 18 cm. The flame is applied continuously for 45 seconds. Post-flame time (AFT), wire length without carbon residue (UCL) and percent marker area without carbon residue (marker without carbon residue) are recorded during and after combustion. Any of the following phenomena occurring will be considered as "no go": 1. Cotton under the test specimen burned. 2. The scorer burned; 3. Dripping with the flame.
    Polymer mixtures containing TPU, silane-g-EVA and master batch of SILINK® DFDA-55488 curing catalyst were prepared according to the formulations shown in Table 3. Samples are cured under ambient conditions for 24 hours prior to the test. For all three samples, the thermal deformation at 150 ° C is lower than 25%. The tensile stress is greater than 20 MPa and the tensile stress is greater than 550%. Typically specifications for personal electronic wire and cable applications require an effective tensile stress greater than 8.3 MPa and elongation greater than 150%. In some key applications a thermal deformation ratio at 150 ° C of less than 50% is required. Crosslinked TPU / EVA blends exhibit very positive results over requirements. The morphology of the inventive polymer blends is shown in Figures 1A-1F. The polymer blend of Example 8 is shown in Figures 1A and 1D, the blend of Example 9 is shown in Figures 1B and 1E, and the polymer blend of Example 10 is shown in Figures 1C and 1F. Figures 1D-1F are figures 1A-1C, respectively, except that with a larger amplification. The light color shows the TPU phase while the dark color shows the EVA crosslinked phase. The TPU is illustrated as the continuous matrix with EVA domain dispersed in all cases. The crosslinked EVA exhibits good compatibility with the TPU array and is well distributed in the TPU array. It has been found that for samples 8 and 9 the domain size of the crosslinked EVA is generally lower than 5 microns (Âμm).
    Table 3 Results of Tensile Tests and Thermal Deformation The standard deviation indicates the standard deviation of the test results for effective tensile stress and tensile elongation.
    Preparation of FR Composition The crosslinked TPU / Si-g-EVA blends are further used to formulate FR compositions with ATH, RDP and epoxidized novolak (reported in Table 4). With different loadings of vinyltrimethoxysilane (VTMS), peroxide and DFDA-5488, the level of crosslinking of the dispersed Si-g-EVA varies. Comparative example 1 (shown in Table 5) is a blend of TPU / EVA. Comparative examples 2-4 are mixtures of TPU / Si-g-EVA. All comparative examples did not have the ambient curing catalyst and thus, the EVA component will not be substantially cross-linked. Loading of EVA (or crosslinked Si-g-EVA or Si-g-EVA) in the inventive examples and comparative examples are in the same range of 8-9% by weight of the FR composition.
    In general, the improvement in thermal deformation performance is significant when substantial cross-linking is introduced as shown in the examples. For all of the inventive examples the thermal deformation is generally lower than 30% compared to 100% thermal deformation in the comparative examples. In addition, the flame retardancy performance in all of the inventive examples is excellent and goes through the stringent VW-1 tests. The effective tensile tension is about 7 MPa for most of the inventive examples and the elongation is greater than 150%. All examples are prepared by a laboratory scale Haake blending process. Generally, the tensile properties of the inventive examples could be improved by double screw extrusion. In sum, the inventive FR compositions achieve superior thermal deformation performance, excellent FR performance and the effective tensile stress at about 7 MPa and elongation greater than 150%.
    Table 4 Composition Materials of TPU / Si-g-EVA Compositions ________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________ of the preferred embodiments, this detail is for the primary purpose of illustration only. Many variations and modifications may be made by one skilled in the art without departing from the spirit and scope according to the description and appended claims.
    权利要求:
    Claims (10)
    [1]
    A halogen-free flame retardant composition comprising in weight percent of the composition: A. 20 to 60% blend of TPU / Si-g-EVA polymers wherein the Si-g-EVA is cross-linked, B. 1 to 25% organic phosphate ester, C. 30 to 60% metal hydrate, and D. 0.1 to 10% epoxidized novolac.
    [2]
    Composition according to Claim 1, characterized in that the polymer blend comprises 50-95% w / w TPU and 5 to 50% w / w Si-g-EVA, based on the blend weight of TPU / Si-g-EVA polymers.
    [3]
    Composition according to Claim 2, characterized in that Si-g-EVA comprises a vinyl acetate content of 10-70% w / w based on the weight of the EVA copolymer.
    [4]
    Composition according to Claim 3, characterized in that Si-g-EVA comprises a silane content of 0.5-10% w / w based on the weight of the EVA copolymer.
    [5]
    Composition according to Claim 4, characterized in that the organic phosphate ester is at least one of bis (diphenyl phosphate) of resorcinol (RDP) and bis (diphenyl phosphate) of bisphenol-A (BPADP) and is present in an amount of 5 to 20% w / w.
    [6]
    Composition according to Claim 5, characterized in that the metal hydrate is at least one of aluminum trihydroxide (ATH) and magnesium hydroxide and is present in an amount of 35 to 55% w / w.
    [7]
    Composition according to Claim 6, characterized in that it comprises at least one of an anti-drip agent, an antioxidant, a UV stabilizer, a processing aid and a filler.
    [8]
    Composition according to claim 7, characterized in that the TPU is at least one of a polyether-based polyether and polyester-based polyurethane and is present in an amount of 60 to 90% w / w based on weight of the TPU / Si-g-EVA polymer blend.
    [9]
    A article, characterized in that it comprises the composition as defined in claim 1.
    [10]
    The article according to claim 9, characterized in that it is in the form of a cover for wires or cables.
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    同族专利:
    公开号 | 公开日
    CA2798662A1|2011-12-01|
    EP2576694A4|2014-03-12|
    CN103261324A|2013-08-21|
    JP5559427B2|2014-07-23|
    EP2576694B1|2015-01-21|
    TW201144417A|2011-12-16|
    KR20130108094A|2013-10-02|
    US9318240B2|2016-04-19|
    JP2013533898A|2013-08-29|
    US20130059943A1|2013-03-07|
    MX2012013563A|2013-01-24|
    BR112012029894A2|2017-07-11|
    EP2576694A1|2013-04-10|
    CN103261324B|2014-12-10|
    CA2798662C|2017-05-23|
    WO2011147068A1|2011-12-01|
    KR101825242B1|2018-02-02|
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-05-07| B09A| Decision: intention to grant|
    2019-06-25| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 24/05/2010, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 24/05/2010, OBSERVADAS AS CONDICOES LEGAIS |
    优先权:
    申请号 | 申请日 | 专利标题
    PCT/CN2010/073106|WO2011147068A1|2010-05-24|2010-05-24|HALOGEN-FREE, FLAME RETARDANT COMPOSITION COMPRISING CROSSLINKED SILANE-g-EVA|
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