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    • 专利摘要:
    composition and wire or cable compositions based on pvc resin are provided which include biochemical plasticizers as main plasticizers. the compositions include pvc resin, a compatibilizer, one or more biochemical plasticizers and, optionally, a thermoplastic elastomer impact modifier. biochemical plasticizers are present in substantial quantities and, in some embodiments, are the only plasticizers present in the compositions.
    公开号:BR112012028732B1
    申请号:R112012028732
    申请日:2011-05-04
    公开日:2020-04-07
    发明作者:I Chaudhary Bharat
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    “COMPOSITION AND WIRE OR CABLE
    Field of the invention [001] This invention relates to compositions of poly (vinyl chloride) (PVC). In one aspect, the invention relates to PVC compositions comprising biochemical plasticizers as major plasticizers while in another aspect, the invention relates to such compositions that are free of non-biochemical plasticizers.
    History of the invention [002] PVC compositions are well known in the art (see, for example, US Patent Nos. 6,063,846 and 6,608,142 and US Patent Publication No. 2005/0203230), and typically, comprise PVC and at least one other polymer, for example, a polyolefin, a styrenic polymer, etc. Since many of these other polymers are typically non-miscible or otherwise incompatible with PVC, these compositions often also include a compatibilizer, for example, chlorinated polyethylene. PVC compositions that do not contain a plasticizer tend to be rigid and are suitable for the manufacture of rigid products such as tubes and pipes in general. PVC compositions that include a plasticizer tend to be flexible and are suitable in applications such as coating and insulation of wires and cables, and medical device components. Examples of such compositions include the FLEXALLOY® products obtainable from Teknor Apex.
    [003] Phthalic acid diesters (also known as phthalates) are known plasticizers for PVC and other vinyl polymers. Examples of common phthalate plasticizers include isononyl phthalate (DINP), diaryl phthalate (DAP), 2-ethylhexyl phthalate (DEHP), phthalate
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    2/29 dioctyl (DOP) and diisodecyl phthalate (DIDP). Other common plasticizers used for high temperature applications are trimellites and adipic polyesters. Often, mixtures of plasticizers are used to obtain optimal properties. Recently, phthalate plasticizers have been scrutinized by public interest groups that are concerned with the negative environmental impact of phthalates and potential adverse health effects of humans (especially children) exposed to phthalates.
    [004] Flexible PVC compositions prepared with plasticizers derived from renewable sources (ie biochemical plasticizers) are an alternative to petrochemical-based plasticizers. However, biochemical plasticizers may in some respects be inferior to compositions prepared with plasticizers that are not derived from renewable sources (for example, phthalate plasticizers and trimellites) because they are insufficiently incompatible with PVC or because they have unsatisfactory aging properties thermal. These disadvantages have limited the use of biochemical plasticizers, such as epoxidized soybean oil, to plasticizers, lubricants or secondary stabilizers, which are present only in small amounts in PVC-based compositions.
    Summary of the invention [005] One aspect of the invention provides compositions comprising a poly (vinyl chloride) resin, a compatibilizer, and one or more biochemical plasticizers. In certain embodiments the compositions comprise 20 to 80 weight percent poly (vinyl chloride) resin, based on the total weight of the composition, from 1 to 30 percent weight
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    3/29 weight of a compatibilizer, based on the total weight of the composition, and from 5 to 60 percent by weight of biochemical plasticizers, based on the total weight of the composition. In some of such compositions, biochemical plasticizers comprising at least 50 weight percent of the total plasticizer content of the composition. In some embodiments, the compositions comprise at least 15 weight percent biochemical plasticizer based on the total weight of the composition.
    [006] In some embodiments, the compositions are substantially free of phthalate-based plasticizers. This includes compositions that are substantially free of any non-biochemical plasticizers.
    [007] In some embodiments, the compositions also comprise a thermoplastic elastomer. In such embodiments, biochemical plasticizers comprise epoxidated fatty acid methyl ester, the thermoplastic elastomer is an olefinic block copolymer, and the compatibilizer comprises a chlorinated polyethylene. In such embodiments, the composition may have a retention of tensile elongation at break of at least 25% after thermal aging for 168 hours at 113 ° C, determined by ASTM D 638.
    [008] In some embodiments, biochemical plasticizers comprise an acetylated castor wax and an epoxidized soybean oil and the compatibilizer comprises a chlorinated polyethylene. In these embodiments, the composition may exhibit a small or better nominal arc ejection capacity at 23 ° C, determined by ASTM D 3291.
    [009] Another aspect of the invention provides wires and cables comprising a coating layer or a layer
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    4/29 insulator comprising a composition according to this invention.
    Brief description of the drawing [010] Figure 1 shows a graph of the dynamic module as a function of temperature for the inventive sample and comparative sample of Example 1.
    Detailed description of the preferred embodiment [011] The present invention provides compositions based on PVC resin that include biochemical plasticizers as main plasticizers. The compositions include PVC resin, one or more biochemical plasticizers and, optionally, a thermoplastic elastomer impact modifier. Biochemical plasticizers are present in substantial amounts in the compositions and, in some embodiments, are the only plasticizers present in the compositions. The use of biochemical plasticizers is advantageous because, in relation to more conventional plasticizers based on petrochemicals, such as phthalates or trimellites, biochemical plasticizers are environmentally more convenient and derived from renewable sources.
    [012] The present compositions overcome certain problems that have prevented several biochemical plasticizers from being used as the main plasticizer in compositions based on PVC resin. For example, some embodiments of the compositions have sufficiently low tensile strengths and sufficiently high tensile strength at break to make them suitable for use as primary plasticizers (or as the only plasticizers) in applications where flexible PVC resins are desirable or required. In addition, these compositions with improved aging properties
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    5/29 thermal (for example, improved elongation retention by tensile strength) in relation to compositions that include the same biochemical plasticizers as main plasticizers (or as the only plasticizers), but which do not have the appropriate thermoplastic elastomer and compatibilizer.
    [013] In other embodiments, the compositions provide improved compatibility of biochemical plasticizer, measured by an arc ejection test, over compositions that include the same biochemical plasticizers as main plasticizers (or as the only plasticizers), but which do not have appropriate compatibilizer. In addition, less biochemical plasticizer is required to achieve a given level of hardness.
    [014] Applications of the present compositions include coating and insulation of wires and / or cables, pipes, coatings, films, foams, and automotive, medical, building and construction materials, pumps, shoes, gasket, hoses, ropes, seals, and applications installation of sealing strips (on windows, doors, etc.).
    Biochemical plasticizers [015] Plasticizer is a substance that decreases modulus and tensile strength, and increases flexibility, elongation, impact resistance, and resistance to rupture of PVC resin, decreases the glass transition temperature and improves the processability of PVC resin. PVC to which it is added.
    [016] Biochemical plasticizers are plasticizers that are derived from renewable natural raw materials, such as plant oils. The compositions can include a single biochemical plasticizer or a mixture of two or more biochemical plasticizers. The publication of a patent application
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    6/29
    No. 2010/0010127 describes biochemical plasticizers (bioplasticizers) and methods for their production.
    [017] Epoxidized vegetable oils, such as epoxidized soybean oil and epoxidized linseed oil, are examples of biochemical plasticizers that can be included in the present compositions. For the purposes of this disclosure, a plasticizer is epoxidized if it contains at least one epoxide group. An epoxide group is a cyclic three-membered ether (also called oxirane or alkylene oxide) in which an oxygen atom is attached to each of two carbon atoms already linked together.
    [018] Fatty acid esters derived from vegetable oils, such as methyl esters of epoxidized fatty acids, are other examples of suitable biochemical plasticizers. Fatty acid esters can be derived from the reaction of an alcohol with fatty acids derived from renewable sources, such as plant oils. Epoxidized soy fatty acid esters are examples of suitable biochemical plasticizers belonging to this group.
    [019] Waxes and oils derived from acetylated plants form another class of biochemical plasticizers that can be included in the present compositions. Acetylated castor wax is an example of a suitable wax. Acetylated castor waxes, oils and other commercially obtainable derivatives include FLEXRICIN® P-8 and PARICIN® 8, obtainable from Vertellus Specialties, Inc. and GRINDSTED SOFT-NSAFE, obtainable from Danisco.
    [020] One or more biochemical plasticizers are used as main plasticizers in the present compositions. For the purposes of this disclosure, plasticizers are major plasticizers if they have compatibility or
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    7/29 sufficient miscibility in the resin composition in which they may be the majority or even the only plasticizers in the composition. Consequently, in some embodiments, biochemical plasticizers account for at least 50 percent by weight of the total plasticizer in the composition. In some embodiments of the compositions, biochemical plasticizers account for at least 90 percent by weight of the total plasticizer in the composition. Epoxidized derivatives of vegetable oils, acetylated derivatives of vegetable oils and mixtures thereof are particularly useful as biochemical plasticizers.
    [021] The compositions contain significant amounts of biochemical plasticizers. For example, in some embodiments, the compositions include 5 to 60 weight percent biochemical plasticizer, based on the total weight of the composition. This includes incorporations in which the composition includes from 7 to 50 weight percent of biochemical plasticizer, based on the total weight of the composition, and also includes an incorporation in which the composition includes 10 to 40 weight percent of biochemical plasticizer, based on the total weight of the composition.
    [022] In some embodiments, the compositions are free of plasticizers derived from petrochemicals, such as phthalates, trimellites, and adipic esters. when used herein, the term “phthalate-free composition is a phthalate-free composition. A “phthalate is a compound that includes the following structure (I):
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    8/29
    (D in which R and R 'may be the same or different. Each of R and R' is selected from a substituted / unsubstituted hydrocarbyl group having 1 to 20 carbon atoms. When used herein, the terms hydrocarbyl and hydrocarbon refer to substituents containing only carbon and hydrogen atoms, including cyclic, polycyclic, fused, or branched or unbranched, saturated or unsaturated acyclic species, and combinations thereof Non-limiting examples of hydrocarbyl groups include alkyl, cycloalkyl, alkenyl, alkenyl groups , cycloalkenyl, cycloalkylienyl, aryl, aralkyl, alkylaryl, and alkynyl, each of positions 3, 4, 5, and 6 can be occupied by hydrogen or by another parcel.
    [023] In some embodiments, the compositions are substantially free of non-biochemical plasticizers. A non-biochemical plasticizer-free composition is considered if the composition is free of non-biochemical plasticizer, or if the amount of non-biochemical plasticizer present in the composition is considered insignificant for the effectiveness of the composition.
    Poly (vinyl chloride) resins [024] The poly (vinyl chloride) resin (also referred to as a vinyl chloride polymer) component of the present compositions is a solid, high molecular weight polymer that can be a poly homopolymer (chloride of
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    9/29 vinyl) or a vinyl chloride copolymer having copolymerized units of one or more additional monomers. A commercially obtainable example of a PVC homopolymer is OXY VINYLS 240F, obtainable from Oxy Vinyls, LP. When present, comonomers will typically account for up to 20 weight percent of the copolymer. Examples of suitable comonomers include C 2 -C 6 olefins, for example, ethylene and propylene; vinyl esters of C 2 -C 4 normal or branched chain carboxylic acids, such as vinyl acetate, vinyl propionate, and vinyl 2-ethylhexanoate; vinyl halides, for example, vinyl fluoride, vinylidene fluoride or vinylidene chloride; vinyl ethers, such as vinyl methyl ether and butyl vinyl ether; vinyl pyridine; unsaturated acids, for example, maleic acid, fumaric acid, methacrylic acid and its mono- or diesters with C1-C 10 mono- or di-alcohols; maleic anhydride, maleic acid imide as well as maleic acid imide N-substitution products with aromatic, cycloaliphatic and optionally branched aliphatic substituents; acrylonitrile and styrene. They are also suitable for use in grafted vinyl chloride copolymer compositions. For example, they can be used as the component vinyl chloride polymer, ethylene copolymers, such as ethylene / vinyl acetate copolymers, and ethylene elastomers, such as EPDM (copolymers comprising copolymerized units of ethylene, propylene and dienes) and EPR (copolymers comprising copolymerized units of ethylene and propylene) that are grafted with vinyl chloride.
    [025] Typically, the compositions will include 20 to 80 weight percent poly (vinyl chloride) resin, based on the total weight of the composition. This includes incorporations
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    10/29 in which the composition includes 25 to 75 weight percent poly (vinyl chloride) resin, based on the total weight of the composition and also includes embodiments in which the composition includes 30 to 60 weight percent poly (vinyl chloride) resin, based on the total weight of the composition.
    Thermoplastic elastomers [026] Optionally, the compositions include one or more thermoplastic elastomers that can act as impact modifiers. The inclusion of such elastomers may be desirable if we intend to use the composition in an application that requires significant flexibility. An elastomer is a rubber-like polymer that can be stretched at least twice its original length and that returns very quickly to approximately its original length when the force exerted for the stretch is released. An elastomer has an elastic modulus less than or equal to about 68.95 MPa (10,000 psi) and an elongation usually greater than 200% in the non-reticulated state at room temperature using the ASTM D638-72 method. A thermoplastic elastomer (TPE) is a material that has the properties of an elastomer, but which can be processed as a thermoplastic. TPEs are generally prepared by special block copolymerization or by grafting polymerization or by mixing two polymers. In each case the thermoplastic elastomer contains at least two segments, one of which is thermoplastic and the other is elastomeric.
    [027] Thermoplastic polyolefin elastomers are examples of thermoplastic elastomers that are suitable for use in the present composition. Polyolefin, PO and similar terms mean a polymer derived from olefins
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    11/29 simple. Polyolefin elastomers such as ethylene / alpha-olefin copolymers are ethylene copolymers with at least one C3-C8 alpha-olefin copolymer (preferably an aliphatic alpha-olefin), and optionally, a polyene comonomer, for example, a diene conjugate, a non-conjugated diene, a triene, etc. Examples of C3-C8 alpha-olefins include propene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1octene. Alpha-olefin may also contain a cyclic structure such as cyclohexane or cyclopentane, resulting in an alpha-olefin such as 3-cyclohexyl-1-propene (allylcyclohexane) and vinyl cyclohexane. Although not alphaolefins in the classic sense of the term, for the purposes of this invention, certain cyclic olefins, such as norbornene and related olefins, are alpha-olefins and can be used in place of some or all of the alpha-olefins described above. Similarly, styrene and related olefins (e.g., alpha-methyl-styrene, etc.) are alpha-olefins for the purposes of this invention. Exemplary copolymers include copolymers of ethylene / propylene, ethylene / butene, ethylene / 1octene, ethylene / 5-ethylidene-2-norbornene, ethylene / 5-vinyl-2-norbornene, ethylene / 1,7-octadiene, ethylene / 7-methyl-1 , 6octadiene, ethylene / styrene and ethylene / 1,3,5-hexathriene.
    [028] If the present compositions include a thermoplastic elastomer, they will generally comprise an amount less than or equal to 40 weight percent thermoplastic elastomer, based on the total weight of the composition. This includes compositions that include no more than 35 weight percent thermoplastic elastomer and further includes compositions with no more than 30 weight percent, based on the total weight of the composition. Typical ranges of weight percentages of thermoplastic elastomer in compositions, based on weight
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    12/29 of the total composition are 10 to 40 weight percent, 15 to 35 weight percent and 20 to 30 weight percent.
    [029] FLEXALLOY®, obtainable from Teknor Apex, is an example of a mixture of PVC resin, thermoplastic elastomer and commercially obtainable compatibilizer.
    Compatibilizer [030] Compatibilizers are used to improve the miscibility of PVC resin and other component polymers, such as thermoplastic elastomers. However, in the present compositions, the compatibilizer can also serve to match the biochemical plasticizers with the PVC resin to a point sufficient to allow them to serve as the main plasticizers, or in some cases, as the only plasticizers in the compositions. Therefore, in the present compositions the compatibilizers are useful even in the absence of the component thermoplastic elastomer.
    [031] Compatibilizers can also act in compositions as impact modifiers. For the sake of clarity, the weight percentages of thermoplastic elastomers mentioned above do not include any thermoplastic elastomeric compatibilizers.
    [032] Examples of suitable compatibilizers include, but are not limited to, chlorinated polyolefins, ethylene / vinyl acetate copolymers, ethylene / methyl acrylate copolymers, ethylene / butyl acrylate copolymers, ethylene / acetate / monoxide polymers carbon, ethylene / acrylate / carbon monoxide terpolymers, poly (vinyl fluoride), poly (tetramethylene oxide), glutarimide copolymers, thermoplastic polyurethane, and chlorinated polyurethane. The chlorinated polyolefin component of
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    The compositions may be, for example, (a) a chlorinated polyethylene homopolymer, (b) a chlorinated copolymer containing copolymerized units of (I) ethylene and (II) a copolymerizable monomer, or (c) a combination thereof . Representative chlorinated olefinic polymers include (a) chlorinated ethylene homopolymers and (b) chlorinated ethylene copolymers and at least one ethylenically unsaturated monomer selected from the group consisting of C 3 -C 10 mono-alpha-olefins; C1-C12 alkyl esters of C3-C20 monocarboxylic acids; unsaturated C3-C20 monocarboxylic or dicarboxylic acids; anhydrides of unsaturated C4-C8 dicarboxylic acids; and vinyl esters of saturated C2-C18 carboxylic acids. Grafted chlorinated copolymers are also included. Specific examples of suitable polymers include chlorinated polyethylene (CPE); chlorinated ethylene / vinyl acetate copolymers; chlorinated ethylene / acrylic acid copolymers; chlorinated ethylene / methacrylic acid copolymers; chlorinated ethylene / methyl acrylate copolymers; chlorinated ethylene / methyl methacrylate copolymers; chlorinated ethylene / n-butyl methacrylate copolymers; chlorinated ethylene / glycidyl methacrylate copolymers; grafted copolymers of chlorinated ethylene and maleic anhydride; and chlorinated copolymers of ethylene with propylene, butane, 3-methyl-1-pentene, or octene. Copolymers can be dipolymers, terpolymers, or copolymers of a larger order. The preferred chlorinated olefinic copolymers are chlorinated polyethylene and chlorinated ethylene / vinyl acetate copolymers. An example of a commercially obtainable chlorinated polyethylene compatibilizer is CPE TYRIN® 4211P, obtainable from The Dow Chemical Company.
    [033] When using CPE as the compatibilizer, you prefer
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    14/29 if the CPE has a chlorine content of about 5% to about 50% by weight. The higher the chlorine content of the CPE, the better its miscibility or compatibility with PVC. Typically, compositions contain 1 to 30 weight percent compatibilizer, based on the total weight of the composition. This includes compositions that include 2 to 20 weight percent compatibilizer, based on the total weight of the composition, and further includes compositions that include 3 to 16 weight percent compatibilizer, based on the total weight of the composition.
    Additional fillers and additives [034] Additionally, compositions can include fillers. Particularly useful fillers include silica, clay, titanium dioxide, talc, calcium carbonate, and other mineral fillers. The compositions may additionally contain other composition ingredients such as thermal and light stabilizers, blowing agents, lubricants, pigments, dyes, processing aids, antioxidants, cross-linking agents, flame retardants, anti-dripping agents, curing agents, reinforcers and retardants, coupling agents, antistatic agents, nucleating agents, gliding agents, tackiness agents, non-stick agents, surfactants, diluent oils, acid purgers, metal deactivators, and the like. The use of such additional components allows the compositions to be designed for use in various applications. Particularly useful composition ingredients include thermal stabilizers of tin, lead, barium / zinc and calcium / zinc. If fillers and additives are present, they will typically account for no more than about 15 weight percent of the
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    15/29 composition, based on the total weight of the composition. This includes compositions that include no more than 10 weight percent and no more than 5 weight percent fillers and additives, based on the total weight of the composition.
    Composition properties
    Flexibility and thermal aging [035] The combination of PVC resin, appropriate compatibilizer, biochemical plasticizer and, optionally, thermoplastic elastomer can provide a composition that is sufficiently flexible, measured by tensile strength and tensile strength, for use in a variety of applications , such as wire and cable applications, where flexibility is desirable. Consequently, some embodiments of the compositions have a tensile strength less than or equal to 4000 psi, measured according to ASTM D638. This includes compositions having a tensile strength less than or equal to 3500 psi, less than or equal to 3000 psi, less than or equal to 2500 psi, less than or equal to 2000 psi, and even less than or equal to 1000 psi. These compositions can also have an elongation at break, measured according to ASTM D638, of at least 100%, at least 200%, at least 300%, or at least 400%. Measures of dog bones cut from plates of 30 milliliters thick according to UL 1581 are performed.
    [036] In some embodiments, the compositions have improved thermal aging properties over a composition that includes PVC resin and biochemical plasticizers in the absence of appropriate compatibilizers and thermoplastic elastomers. For example, a PVC resin-based composition that includes a combination of epoxidized fatty acid methyl ester and epoxidized soybean oil as the only plasticizers has a high tensile strength
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    16/29 and a lower tensile elongation retention after thermal aging, as illustrated in the comparative sample of Example 1, below. However, including suitable thermoplastic compatibilizers and elastomers, the tensile strength and thermal aging properties of the compositions can be significantly improved, as illustrated in the inventive samples of Example 1, below. Therefore, in some embodiments, the compositions have a tensile elongation retention of at least 20%, at least 40%, or even at least 60% after thermal aging at 113 ° C for 168 hours. For these same compositions, the inclusion of the biochemical plasticizer and the compatibilizer provides a reduced increase in tensile strength after thermal aging. Consequently, some incorporations of the compositions have an increase in tensile strength less than or equal to 190% after thermal aging at 113 ° C for 168 hours. This includes compositions that have an increase in tensile strength less than or equal to 140% after thermal aging at 113 ° C for 168 hours and also include compositions that have an increase in tensile strength less than or equal to 120% after thermal aging at 113 ° C for 168 hours.
    Plasticizer compatibility [037] In some embodiments, an appropriate combination of compatibilizer and biochemical plasticizer makes it possible to incorporate biochemical plasticizer into the PVC resin with improved compatibility to provide a composition with greater flexibility than that of a comparable composition without the appropriate compatibilizer. For example, a PVC resin-based composition that includes acetylated castor wax and epoxidized soy oil and appropriate compatibilizers can
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    17/29 exhibit improved compatibility over a composition that includes only PVC resin and biochemical plasticizers, as illustrated in Example 2, below.
    [038] Improved compatibility can be determined by an arc ejection test at room temperature (23 ° C) and / or after thermal aging. For the purposes of this disclosure, arc ejection is measured according to ASTM D 3291: Standard test method for plasticizer compatibility in poly (vinyl chloride) plastics under compression that determines the compatibility of plasticizers in poly (chloride plastics) vinyl) calculating the amount of plasticizers that is ejected due to the compressive stress strain within a 180 ° circular arc. Briefly, using this method, specimens of plasticized poly (vinyl chloride) sheet are folded through an arc of approximately 180 ° and attached to a template designed to keep them in the desired conformation. At specified time intervals, a specimen is removed, folded 180 ° in the opposite direction, and the former is examined within the arch for evidence of plasticizer ejection by visual inspection and cleaning the area with a dry index finger. Ejection can be classified as: (1) Completely arc dry = none / 0; (2) Slippery with small amounts of oily substances inside the arch = small / 1; (3) Slippery with moderate amounts of oily substances inside the arch = moderate / 2; and (4) Slippery with large amounts of oily substances inside the arc = consistent / dripping / 3.
    Shore hardness;
    [039] The present compositions can be characterized by their Shore hardness values as a measure of
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    18/29 flexibility. For the purposes of this disclosure, Shore hardness is measured according to ASTM D2240. The Shore A scale can be used for “softer” PVC resin compositions (for example, compositions that include an elastomer impact modifier). Thus, some embodiments of the compositions have a Shore A hardness less than or equal to 75. This includes compositions having a Shore A hardness less than or equal to 70 and also includes compositions having a Shore A hardness less than or equal to 65. The scale is used Shore D for softer PVC resin compositions. Thus, some embodiments of the compositions have a Shore D hardness less than or equal to 55. This includes compositions having a Shore D hardness less than or equal to 50 and further includes compositions having a Shore D hardness less than or equal to 45.
    Composition [040] In general, polymeric compositions are prepared according to conventional dry mixing or wet mixing methods known to those skilled in the PVC composition technique. The mixtures obtained from the mixing process can also be composed with a mixer such as a Banbury batch mixer, a Farrel continuous mixer, or a one or two spindle extruder.
    [041] In an embodiment, the present polymeric composition is prepared by absorbing the biochemical plasticizers in PVC powder to prepare a dry mixture. Any method / apparatus may be used to prepare the dry mix including, but not limited to, a Brabender mixer, a Henschel mixer or a tape mixer. The polymeric composition may contain other additives in addition to PVC and the biochemical plasticizer. Then, the dry mixture can be further composed
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    19/29 (for example, via melt extrusion) and molded into any desired shape (film, pellet, etc.).
    Articles [042] Another aspect of the invention provides articles, such as molded or extruded articles, comprising one or more compositions of the present invention.
    [043] Items include insulation and coatings for wires and cables. Thus, in some embodiments, the article includes a metallic conductor and a coating on the metallic conductor to provide an insulated wire capable of transmitting electrical energy. When used here, a metallic conductor is at least one metallic component used to transmit electrical energy and / or electrical signals. Frequently, wire flexibility is desired, so that the metallic conductor can have a solid cross section or preferably be composed of rows of smaller wires that provide increased flexibility for the given total conductor diameter. Often, cables are composed of several components such as multiple insulated wires formed in an inner core and then surrounded by a cable cover system providing protection and cosmetic appearance. The cable cover system can incorporate metallic layers such as shields or thin metal sheets, and typically has a polymeric layer on the surface. The one or more polymeric layers in the protective / cosmetic cable jacket are often referred to as cable jacket. For some cables, the sheath is just a layer of polymeric sheath surrounding a cable core. There are also some cables having a single layer of polymer surrounding the conductors, performing both the insulation and the coating function. The present compositions
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    20/29 can be used as or in polymeric components in a range
    complete in products of wires and cables, including cables in energy like in applications electrical communication or in optical fiber. Examples[044] The examples next illustrate incorporations in
    methods for preparing thermoplastic elastomer compositions according to the present invention.
    Example 1
    Materials and methods [045] The following materials are used in the comparative samples (CS) and in the inventive samples (IS) of Example 1. The PVC resin is OXY-VINYLS® 240F, a poly (vinyl chloride) homopolymer obtainable by Oxy Vinyls, LP. The epoxidated fatty acid methyl ester (e-FAME) is VIKOFLEX® 7010, an epoxidized soy fatty acid ester obtainable from Arkema, Inc. The epoxidized soy oil is PLAS-CHEK® 775, obtainable from Ferro Corp. The thermoplastic elastomers are: AFFINITY® EG8150, an ethylene / octene copolymer, and an olefinic block copolymer (OBC) with a melting index of 0.5 g / 10 min, a density of 0. 866 g / cm3, a soft block / hard block ratio of 89/11, and 18 molar percent of ethylene in the soft block. Both elastomers are obtainable from The Dow Chemical Company. The compatibilizer is TYRIN® 2348P, a chlorinated polyethylene obtainable from The Dow Chemical Company. The additives included in the composition are: HUBERCARB® Q1T, a calcium carbonate obtainable from Akrochem Corp .; MARK® 6797, a calcium / zinc thermal stabilizer, obtainable from Chemtura; and IRGANOX® 1076, a phenolic antioxidant, obtainable from Ciba Specialty Chemicals. Table 1 shows the formulation of the comparative sample and the inventive samples.
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    Table 1 - Formulations of CS 1 and IS 1-3
    CS 1 IS 1 IS 2 IS 3 PVC (OXY-VINYLS 240F) 63.7 33, 7 33, 7 33, 7 TYRIN CM2348P10 16 16 AFFINITY EG815020 26VIKOLEX 7010 24 24 12 12 OBC HUBERCARB Q1T 6, 4 6, 4 6, 4 6, 4 PLAS-CHEK 775 3, 5 3, 5 3, 5 3, 5 MARK 6797 2, 1 2, 1 2, 1 2, 1 IRGANOX 1076 0, 3 0, 3 0, 3 0, 3 TOTAL (% by weight) 100 100 100 100
    [046] The batches of the comparative sample and the inventive samples are prepared by mixing the ingredients in a rotating drum in a 40 cm Brabender mixer set at 40 rpm. The mixer is not purged with nitrogen. Mixing is carried out by adding polymers and other ingredients, and mixing at 175 ° C for 5 minutes. The resulting compositions are removed from the mixer and they are molded by compression into 30-milliliter-thick plates at 175 ° C for 5 minutes.
    Properties [047] Tensile strength and elongation (or elongation) are measured by breaking tensile strength in specimens at a rate of 2 inches / min, according to ASTM D638. Tensile strength and elongation are measured in three non-aged samples, three samples aged at 113 ° C for 168 hours, and three samples aged at 136 ° C for 168 hours. Then, the tensile strength retention and the elongation retention by traction (as a percentage) are calculated for the aged samples.
    [048] Shore A hardness of non-aged samples is measured according to ASTM D2240. The module is measured using dynamic-mechanical analysis from -100 ° C to + 160 ° C (at
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    5 ° C / min).
    [049] Figure and Table 2 show the data.
    Table 2 - Properties of the formulations in Table 1
    Not Aged Retention percentage after 168 h at 113 ° C Retention percentage after 168 h at 136 ° C Shore A CS 1 82.8 AT AT IS 1 60, 8 AT AT IS 2 74.8 AT AT IS 3 70, 3 AT AT Tensile strength (psi) CS 1 2778 213 216 IS 1 617 187 208 IS 2 911 114 115 IS 3 820 127 130 Elongation by traction (%) CS 1 325 1 4 IS 1 326 26 15 IS 2 409 47 29 IS 3 346 67 33
    Results [050] Comparative sample 1, which includes e-FAME and epoxidized soybean oil as the only plasticizers, but does not include a compatibilizer or elastomer, exhibits a distinct deterioration in tensile properties after thermal aging at elevated temperatures. In contrast, the inventive samples 1 to 3, which include the same biochemical plasticizers in addition to a compatibilizer and polyolefinic elastomers, are softer and result in better flexibility at low temperature, as well as dramatically improving the tensile elongation retention after thermal aging.
    Example 2
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    23/29
    Materials and methods [051] The following materials are used in the comparative samples (CS) and in the inventive samples (IS) of Example 2. The PVC resin is OXY-VINYLS® 240F, a homopolymer of poly (vinyl chloride) obtainable by Oxy Vinyls, LP. The epoxidized soybean oil is PLAS-CHEK® 775, obtainable from Ferro Corp. The acetylated castor wax (ACW) is prepared as described below. The compatibilizer is TYRIN® 4211P, a chlorinated polyethylene obtainable from The Dow Chemical Company. The additives included in the composition are: SATINTONE® SP-33, a calcined aluminum silicate obtainable from BASF Corp .; BAEROPAN® MC 90249 KA, a mineral stabilizer, obtainable from Baerlocher GmbH; and IRGANOX® 1076, a phenolic antioxidant, obtainable from Ciba Specialty Chemicals. Table 3 shows the specific formulations of the comparative sample and the inventive samples.
    Table 3 - Formulations of CS 2 and IS 4-6
    CS 2 IS 4 IS 5 IS 6 PVC (OXY-VINYLS 240F) 63, 0 58.0 53.0 48, 0 ACW 13, 7 13, 7 13, 7 13, 7 SATINTONE® SP-33 clay 6, 4 6, 4 6, 4 6, 4 PLAS-CHEK 775 13, 6 13, 6 13, 6 13, 6 BAEROPAN® MC 90249 KA 3.0 3.0 3.0 3.0 IRGANOX® 1076 0, 3 0, 3 0, 3 0, 3 TYRIN® 4211P5.0 10, 0 15, 0 TOTAL (% by weight) 100 100 100 100
    [052] The acetylated castor wax (ACW) is prepared as follows. Castor wax (3700 g) is loaded into a 5 L (liter) reactor. A mechanical stirrer and common distillery glassware are fixed to the reactor and heated by an external bath at a temperature of 100 ° C. After melting the castor wax, acetic anhydride (1233 g) is added. The temperature drops to 84 ° C and increases to 115 ° C due to the exothermic reaction. The reaction temperature is maintained at 115 ° C (inside) for about 8 hours. A vacuum pressure of 800 to 150 mbar is used
    Petition 870190132121, of 12/12/2019, p. 32/41
    24/29 to remove acetic acid until the acid number is less than 3 mg KOH / g. A liquid product (ACW) is obtained. Table 4 shows the properties of the resulting ACW.
    Table 4 - Properties of acetylated castor wax
    PropertyAppearance at room temperature Yellow liquid Iodine number (IV) 4 Acidity Index (AN) 2.4 Number of hydroxyls (OHN) 0 Solution temperature (° C) 194 Percentage by weight of water 0.03 Viscosity at 25 ° C 345 Viscosity at 40 ° C 150 Density (g / cm 3 ) 0.953
    [053] Table 4 measures AN = acid number (mg KOH / g) per DIN 53402; density (@ 25 ° C) is measured by DIN 51757; IV = number of iodine (g of I2 / 100 g) is determined by Deutsche Einheitsmethode DGF C-V 11a (53) or from a technical data sheet; OHN = number of hydroxyls (mg KOH / g) according to DIN 53240; the solution temperature (° C) is measured by DIN 53408; viscosity (mPas) is measured by ASTM D445 Brookfield 25 ° C, 40 ° C; and wt% of water is measured by DIN 51777.
    [054] The comparative sample and the inventive samples are prepared as follows. Epoxidized soy oil and ACW are heated to 60 ° C for 1 hour, stirred and mixed in a 50/50 weight percentage concentration. Then, a mixture of solids is formulated by mixing all dry ingredients, except the biochemical plasticizers and the clay filler, in a container using a spatula. Using a 40 cm 3 Brabender mixer with sigma blades at 90 ° C and 40 rpm, the solids are mixed for 30 seconds. Then, the biochemical plasticizers are added and mixing continues for 360 seconds (6 minutes). Then, add to
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    25/29 aryl charge and mixing continues for 60 seconds. Then, the mixer is turned off and the resulting dry mixture is removed.
    [055] Then, the dry mixture is mixed by melting using a 40 cm3 Brabender mixer with eccentric rotors at 40 rpm, at 180 ° C for 120 seconds. The batches of the resulting composition are molded by compression into 30-milliliter-thick plates at 180 ° C for 5 minutes.
    Properties [056] Tensile strength and tensile elongation at rupture in specimens are measured at a rate of 2 inches / min, according to ASTM D638. Tensile strength and elongation are measured in three un aged samples, three samples aged at 113 ° C for 168 hours, and three samples aged at 136 ° C for 168 hours. Then, tensile strength retention (TSR) and tensile elongation retention (TER) (as a percentage) are calculated for aged samples.
    [057] Shore D hardness of non-aged samples is measured according to ASTM D2240.
    [058] Arc ejection is measured for samples stored for 48 hours at 23 ° C according to ASTM D3291.
    [059] Ejection is also measured by visually inspecting 1-inch diameter samples aged for 7 days at 113 ° C and 136 ° C.
    Results:
    [060] Table 5 shows the data from Example 2. Inventive sample 4 (containing 5% by weight CPE) generally exhibits less plasticizer ejection than comparative sample 2 (ie improved plasticizer compatibility inventive sample 4 by adding the
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    26/29 compatibilizer). Inventive samples 5 and 6 (containing, respectively, 10% by weight of CPE and 15% by weight of CPE) exhibit relatively better performance, based on the arc ejection test. Inventive samples 4 to 6 are also softer (flexible) than comparative sample 2, indicating that the amount of plasticizer can be reduced to achieve the same hardness as the comparative sample, which would result in less plasticizer ejection at elevated temperatures.
    Table 5 - Properties of the formulations in Table 3
    CS 2 IS 4 IS 5 IS 6 Shore D 45.2 ± 0.6 42, 9 ± 0.4 41.0 ± 0.8 37.3 ± 0.1 Non-aged TS, psi 3623 ± 72 3211 ± 114 2078 ± 269 1102 ± 176 TSR (%) after aging at 113 ° C for 168 hours 97 ± 3 92 ± 4 91 ± 13 118 ± 13 TSR (%) after aging at 136 ° C for 168 hours 91 ± 5 94 ± 3 96 ± 8 111 ± 16 Non-aged TE (%) 266 ± 12 252 ± 2 195 ± 18 108 ± 77 TER (%) after aging at 113 ° C for 168 hours 96 ± 2 100 ± 0 94 ± 14 138 ± 367 TSR (%) after aging at 136 ° C for 168 hours 76 ± 12 91 ± 1 80 ± 11 108 ± 318 Arc ejection @ room temperature M s VS N Arc ejection test voltage bleaching N N s M Ejection after aging at 113 ° C M N H M Ejection after aging at 136 ° C N N s s
    N = none; VS = much little; S = little; M = moderate and H = consistent and. [061] All the references The Table Periodic From Elements on here will concern The Table Periodic From Elements published and registered, per CRC Press, Inc., 2003. Equally , any references to a Group or Groups will be to a Group or Groups shown in this table Periodical of Elements using the IUPAC system for number groups. Saved
    Petition 870190132121, of 12/12/2019, p. 35/41
    27/29 if stated otherwise, implicit in context, or customary in the technique, all parts and percentages are based on weight and all test methods are current as of the filing date of this disclosure. For United States patent practice purposes, the contents of any patent, patent application, or publication referred to herein are hereby incorporated by reference in their entirety (or the equivalent US version thereof is also incorporated by reference) especially with respect to the dissemination of synthetic techniques, definitions (to the extent not inconsistent with any definitions provided herein) and general knowledge of the technique.
    [062] In this disclosure, the numerical ranges are approximate and, therefore, may include values outside the range, s target if indicated differently. The numerical ranges include all values of the same, including the lower value and the upper value, in increments of one unit, as long as there is a separation of at least two units between any lower value and any upper value. As an example, if a composition, physical or other property, such as, for example, molecular weight, melt index, etc., is 100 to 1000, it is intended that all individual values, such as 100, 101, 102, etc., and sub-ranges, such as 100 to 144, 155 to 170, 197 to 200, etc., are expressly listed. For ranges containing values less than one (1) or containing fractional numbers greater than one (1) (for example, 1.1, 1.5, etc.), a unit is considered to be 0.0001, 0.001 or 0.1, when appropriate. For ranges containing single-digit numbers less than ten (for example, 1 to 5), a unit is considered to be 0.1. These are just examples of what
    Petition 870190132121, of 12/12/2019, p. 36/41
    28/29 is specifically intended, and all possible combinations of numerical value between the minimum value and the maximum value listed, are considered to be expressly stated in this disclosure.
    [063] The terms, comprising, including, having and its derivatives are not intended to exclude the presence of any additional component, step or procedure, whether or not it is specifically disclosed. In order to avoid any doubt, all compositions claimed through the use of the term comprising may include any additive, adjuvant, or compound, polymeric or not, additional, unless otherwise stated. In contrast, the term, consisting essentially of excluding any other component, step or procedure from the scope of any subsequent mention, except those that are not essential to operability. The term consisting of excludes any component, step or procedure not specifically described or listed. Unless otherwise stated, the term or refers to members listed individually as well as in any combination.
    [064] Composition and similar terms mean a combination or mixture of two or more components. Mixture and similar terms mean a mixture of two or more polymers, as well as mixtures of polymers with various additives. Such a mixture may or may not be miscible. Such a mixture may or may not be separated by phases. Such a mixture may or may not contain one or more domain configurations, determined from electronic transmission spectroscopy, light scattering, X-ray scattering, and any other method known in the art.
    [065] When used with respect to a chemical compound,
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    29/29 unless specifically indicated to the contrary, the singular includes all isomeric forms and vice versa (for example, hexane individually or collectively includes all hexane isomers). The terms compound and complex are used in order to allow exchange and / or substitution to refer to organic, inorganic and organometallic compounds. The term polymer (and similar terms) is a macromolecular compound prepared by reacting (i.e., polymerizing) monomers of the same or different types. Polymer includes homopolymers and copolymers.
    [066] Although the invention has been described in considerable detail by the previous examples and reference to the drawings, these details are for the purpose of illustration and not to be construed as a limitation of the spirit and scope of the invention as it is described in the appended claims.
    权利要求:
    Claims (8)
    [1]
    1. Composition, characterized by the fact of understanding:
    - 20 to 80 weight percent poly (vinyl chloride) resin, based on the total weight of the composition;
    - 1 to 30 weight percent of a compatibilizer, based on the total weight of the composition; and
    - 10 to 40 weight percent, based on the total weight of the composition, of biochemical plasticizers including epoxy derivatives of vegetable oils, acetylated derivatives of vegetable oils or mixtures thereof, biochemical plasticizers comprising at least 50 weight percent of the content total plasticizers in the composition; the composition being free of phthalate-based plasticizers and non-biochemical plasticizers; and the term "biochemical plasticizers as used here means derived from plant oils.
    [2]
    2. Composition according to claim 1, characterized in that it comprises at least 15 weight percent biochemical plasticizer based on the total weight of the composition.
    [3]
    3. Composition according to claim 1, characterized by the fact that it also comprises a thermoplastic elastomer.
    [4]
    4. Composition, according to claim 1, characterized by the fact that the biochemical plasticizers comprise an epoxidized derivative of vegetable oil and the compatibilizer comprises a chlorinated polyethylene.
    [5]
    5. Composition according to claim 1, characterized by the fact that it has a retention of tensile elongation at break of at least 25% after thermal aging for 168 hours at 113 ° C, as determined by ASTM D 638.
    [6]
    6. Composition according to claim 1, characterized
    Petition 870190132121, of 12/12/2019, p. 39/41
    2/2 because the biochemical plasticizers comprise an acetylated derivative of vegetable oil and an epoxy derivative of vegetable oil, and the compatibilizer comprises a chlorinated polyethylene.
    [7]
    7. Composition according to claim 1, characterized by the fact that it exhibits a nominal arc ejection capacity at 23 ° C small or better, as determined by ASTM D 3291.
    [8]
    8. Wire or cable, characterized by the fact that it comprises a coating layer or an insulating layer comprising the composition as defined in claim 1.
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-09-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-02-18| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-04-07| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 04/05/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US33284810P| true| 2010-05-10|2010-05-10|
    PCT/US2011/035143|WO2011143028A1|2010-05-10|2011-05-04|Flexible pvc compositions made with plasticizers derived from renewable sources|
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