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    • 专利摘要:
    SINGLE-PHASE ACETYLED MAMMON COMPONENT, COMPOSITION, POLYMERIC COMPOSITION AND COATED CONDUCTOR This disclosure relates to a single-phase acetylated castor (SP-SCC) component. An acetylated castor component is purified to produce the SP-ACC which contains a reduced amount of insoluble components or no insoluble component in it. SP-ACC improves the performance of plasticizers of which it is a component.
    公开号:BR112012032469B1
    申请号:R112012032469-1
    申请日:2011-06-23
    公开日:2020-11-03
    发明作者:Bharat I. Chaudhary；Beate Sczekalla；Abhijit Ghoshdastidar；Yang Cheng；Prashant Tatake；Raymond M. Collins
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    History of the invention
    [0001] Plasticizers are compounds or mixtures of compounds that are added in polymeric resins to provide softness and flexibility. Phthalic acid diesters (also known as "phthalates") are plasticizers known in many flexible polymer products, such as polymer products formed from poly (vinyl chloride) (PVC) and other vinyl polymers. Examples of common phthalate plasticizers include diisononyl phthalate (DINP), diaryl phthalate (DAP), di-2-ethylhexyl phthalate (DEHP), dioctyl phthalate (DOP) and diisodecyl phthalate (DIDP). Other common plasticizers used for high temperature applications are trimellites and adipic polyesters. Mixtures of plasticizers are often used to obtain optimal properties.
    [0002] Recently, phthalate plasticizers have been intensively investigated by public interest groups that are concerned with the negative environmental effect of phthalates and potential adverse health effects of humans (especially children) exposed to phthalates.
    [0003] Consequently, there is a need for phthalate-free plasticizers for polymeric resins. There is also a need for phthalate-free plasticized polymers that have the same, or substantially the same chemical, mechanical and / or physical properties as those of polymers containing phthalate plasticizers. Summary of the invention
    [0004] The present disclosure relates to a single-phase acetylated castor (SP-ACC) component. An acetylated castor component is purified to remove insoluble components and produce the single stage acetylated castor component. The single-stage acetylated castor component improves the performance and properties of plasticizers of which it is a part.
    [0005] The present disclosure provides a component. In an embodiment, a single phase acetylated castor component is provided which contains less than about 0.2% by weight of insoluble components after exposure to 15 ° C for at least one week.
    [0006] The present disclosure provides a composition. In an embodiment, a composition is provided which includes a single phase acetylated castor component and an epoxidated fatty acid ester. The composition contains less than 0.2% by weight of insoluble components after exposure to 15 ° C for at least one week.
    [0007] The present disclosure provides a polymeric composition. In an embodiment, a polymeric composition is provided which includes a polymeric resin and a plasticizer composition. The plasticizer composition includes a single phase acetylated castor component and, optionally, an epoxidated fatty acid ester. The polymeric composition has a curve ejection index ("loop spew value") of 0-2 measured according to ASTM D 3291.
    [0008] Disclosure provides a driver. In an embodiment, a coated conductor is provided which includes a metallic conductor and a coating on the conductor. The coating includes a polymeric resin and a plasticizer composition. The plasticizer includes a single-phase acetylated castor component and, optionally, an epoxidated fatty acid ester.
    [0009] An advantage of the present disclosure is a bioplasticizer with reduced curve ejection or no curve ejection.
    [0010] An advantage of the present disclosure is a phthalate-free and / or lead-free bioplasticizer.
    [0011] An advantage of the present disclosure is a bioplasticizer that reduces greenhouse gases.
    [0012] An advantage of the present disclosure is a bioplasticizer that allows users to obtain LEED credits.
    [0013] An advantage of the present disclosure is a bioplasticizer that allows users to obtain carbon credits.
    [0014] An advantage of the present disclosure is a coating for wire and cable applications that is phthalate free and lead free.
    [0015] An advantage of the present disclosure is a phthalate-free bioplasticizer that produces little or no curve ejection when applied as a wire / cable coating. Detailed description of the invention
    [0016] The present disclosure relates to acetylated castor components of a single phase and compositions including them. The compositions provided herein are suitable for use as plasticizers in polymeric resins and in coating, and in particular insulation, of wires and cables.
    [0017] All references to the Periodic Table of Elements here will refer to the Periodic Table of Elements published and registered by CRC Press, Inc., 2003. Likewise, any references to a Group or Groups will be to a Group or Groups shown in this Table Periodic Table of Elements using the IUPAC system to number groups. Unless stated to the contrary, 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, process and product designs, polymers, catalysts, definitions (to the extent not inconsistent with any definitions provided herein) and general knowledge in the art.
    [0018] Any numerical range mentioned here, includes all values from the lower value to 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 higher value. As an example, if it is stated that the quantity of a component, or a value of a composition or physical property, such as, for example, quantity of a mixing component, softening temperature, melting index, etc., is between 100 and 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 in this report. For ranges containing values that are less than one, or containing fractional numbers greater than one (for example, 1.1, 1.5, etc.) a unit is considered to be 0.0001, 0.001, 0.01 or 0.1, when appropriate. For ranges containing single digit numbers less than ten (for example, 1 to 5), a unit is typically considered to be 0.1. These are just examples of what is specifically intended, and all possible combinations of numerical values between the minimum and maximum values listed will be considered to be expressly established in this patent application. Within this disclosure, numerical ranges are provided for, among other things, amounts of components in the composition and / or coating, additives, and various other components in the composition, and the various characteristics and properties that define these components.
    [0019] Unless specifically stated otherwise, when used with respect to a chemical compound, the singular includes all isomeric forms and vice versa (for example, "hexane" includes individually or collectively all hexane isomers). The terms - "compound" and "complex" - are used in such a way as to allow exchange and / or substitution to refer to organic, inorganic and organometallic compounds. The term "atom" refers to the smallest constituent of an element regardless of ionic state, that is, whether or not it has a partial charge or charge or whether it is attached to another atom. The term "amorphous" refers to a polymer lacking a crystalline melting point determined by differential scanning calorimetry (DSC) or an equivalent technique.
    [0020] 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" excludes 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.
    [0021] "Composition" and similar terms mean a combination or mixture of two or more components.
    [0022] "Mixture", "polymeric 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.
    [0023] The term "polymer" (and similar terms) is a macromolecular compound prepared by reacting (ie, polymerizing) monomers of the same or different types. "Polymer" includes homopolymers and copolymers.
    [0024] In an embodiment, the compositions disclosed here are free of phthalates. When used herein, the term "phthalate-free composition" is a phthalate-free composition or, conversely, is phthalate-free. A "phthalate" is a compost that includes the following structure (I):
    where R and R 'can be the same or different. Each of R and R 'is selected from a substituted / unsubstituted hydrocarbyl group having from 1 to 20 carbon atoms. When used herein, the terms - "hydrocarbyl" and "hydrocarbon" - refer to substituents containing only hydrogen and carbon atoms, including branched or unbranched, saturated or unsaturated, cyclic, polycyclic, fused, or acyclic species, and combinations thereof. Non-limiting examples of hydrocarbyl groups include alkyl, cycloalkyl, alkenyl, alkadienyl, cycloalkenyl, cycloalkylenyl, aryl, aralkyl, alkylaryl, and alkynyl groups. Each of positions 3, 4, 5, and 6 can be occupied by hydrogen or by another parcel.
    [0025] In an embodiment, the compositions disclosed here are lead free.
    [0026] In an incorporation, a single phase acetylated castor component is provided. When used here, a "single-phase acetylated castor component" is castor oil, castor wax, or a mixture thereof. The term "castor oil" is a colorless to light yellow viscous liquid obtained from castor / seed of the castor plant Ricinus communis. Castor oil is a triglyceride in which from about 85% by weight to about 95% by weight of the fatty acid chains are ricinoleic acid. When used herein, a "fatty acid" is a monocarboxylic acid composed of an aliphatic chain containing from 4 to 22 carbon atoms with a terminal carboxyl (COOH) group. The fatty acid may be saturated or unsaturated, branched or unbranched, and may or may not include one or more hydroxyl groups.
    [0027] A non-limiting composition representation of castor oil is provided in Representation (II) below. Representation of castor oil (II) composition


    [0028] Weight percentages based on the total weight of castor oil.
    [0029] The term "castor wax" or "castor wax" is hydrogenated castor oil, and is a high, brittle, hard melting wax of about 40% by weight to about 95% by weight of glyceryl trihydroxystearate. This wax is produced by hydrogenating castor oil, typically in the presence of a nickel catalyst. Castor wax (or castor wax) is odorless and insoluble in water. The castor wax can be castor oil partially or completely hydrogenated.
    [0030] The castor bean component is acetylated. When used herein, the term "acetylation" is the process of introducing an acetyl group into the molecule of a compound having -OH groups. In other words, acetylation replaces H of the -OH groups with CH3CO- groups. Acetylation may also occur with a fatty acid moiety having a hydroxyl group (i.e., the C12 -OH group of the ricinoleic acid moiety of a glyceride). Non-limiting examples of suitable acetylating reagents include acetic anhydride and acetyl chloride. Consequently, an "acetylated castor component" (or "ACC") is a castor component that has undergone an acetylation reaction. In other words, an acetylated castor component is the reaction product of a castor component and an acetylating reagent. In particular, the acetylated castor component can be an acetylated castor oil ("ACO") or an acetylated castor wax ("ACW") or mixtures thereof. ACW can be partially or completely hydrogenated.
    [0031] In an incorporation, ACC has a hydrogenation efficiency of about 95% to 99%. Efficiency is defined by the conversion of unsaturated double bonds into saturated bonds of oleic, linoleic and ricinoleic acids present in castor oil. Reduction of iodine content is a good measure of hydrogenation efficiency. The hydrogenation of the hydroxyl groups was found to form a keto-stearic acid. Keto-stearic acid affects the amount of insoluble in the final product and in a way corresponding to the clarity of the ACC. Preferably, the purification (as described below) decreases or removes any formed keto-stearic acid.
    [0032] Some, substantially all, or all groups of the castor bean component may be acetylated. Acetylation results in an acetylated castor component having fewer hydroxyl groups than the castor component. The acetylated castor component has a hydroxyl number from 0 to less than 15, or from 0 to less than 10, or from 0 to less than 5, or from 0 to less than 2, or 0.
    [0033] In an embodiment, the castor bean component is composed only of glyceryl trihydroxystearate. Consequently, the ACC can be acetylated glyceryl trihydroxystearate. In an embodiment, the acetylated glyceryl trihydroxystearate has a hydroxyl number from 0 to less than 15, or from 0 to less than 10, or from 0 to less than 5, or from 0 to less than 2, or 0.
    [0034] In another embodiment, the acetylated castor wax has a viscosity of about 100 mPa-s less than about 2000 mPa-s at 25 ° C.
    [0035] Non-limiting properties of the castor component and non-limiting incorporations of the acetylated castor component and a single-phase acetylated castor component are provided in Table 1 below. Table 1
    * Removed by cooling to 15 ° C for 1 week and filtering at 15 ° C to 25 ° C with 11 µm or larger filter paper. ** RT = room temperature.
    [0036] The complete or substantially complete acetylation of the ACC produces a liquid plasticizer composition with a viscosity suitable for use with polymeric resins and, in particular, with vinyl chloride resins. In an embodiment, applicants have surprisingly found a liquid ACW with a viscosity of about 100 mPa⋅s less than about 2000 mPa⋅s at 25 ° C. In another embodiment, ACW has a hydroxyl number from 0 to less than 15. In an additional embodiment, ACW has an iodine number from 0 to less than 40 g of I2 / 100 g.
    [0037] Applicants have also discovered a liquid ACO with a hydroxyl number from 0 to less than 5 that has a viscosity of about 50 mPa-s at less than 1000 mPa-s at 25 ° C. The ACO may also have an iodine number of about 40 g of I2 / 100 g to about 90 g of I2 / 100 g.
    [0038] In an embodiment, the acetylated castor component has an acid number of about 0 mg KOH / g to about 8 mg KOH / g.
    [0039] In an embodiment, the acetylated castor component has an APHA color of about 50 to less than about 3000, or about 50 to less than about 1000, or about 50 to less than about 500, or about 50 to less than about 300.
    [0040] In an incorporation, the ACC is a single-phase ACC. A "single-phase acetylated castor component" ("SP-ACC") is any of the above ACCs that is (1) exposed to a temperature of 5 ° C to 50 ° C, or 15 ° C, for at least at least three hours to a week, (2) subsequently subjected to a purification process (as described below), (3) then it is exposed to 15 ° C for at least one week, and (4) is filtered at 15-25 ° C with a filter paper of 11 µm or greater which collects less than 0.2% by weight of insoluble components in the filter paper. The SP-ACC is only (or substantially only) a liquid phase at room temperature. When used here, the term "insoluble component" is one or more compounds that separate ACC phase over time. ACC is a liquid at room temperature and the insoluble component separates from the phase of the liquid phase ACC as a solid phase. The insoluble component muddies the ACC, settles on the bottom and can lead to excessive ejection when using the ACC as a plasticizer. The lower the temperature, the more insoluble they will form. In addition, the degree of castor oil or castor wax used for acetylation also has an effect on the amount of insolubles formed, as well as on the color of the ACC.
    [0041] The SP-ACC is prepared by subjecting any of the previous ACCs to a purification process. When used here, a "purification process" is the application of one or more of the procedures following ACC: a filtration procedure, a centrifugation procedure, a sedimentation procedure, treatment with additives [such as silicon dioxide (SiO2) , aluminum oxide (AI2O3), activated carbon, perlite (naturally occurring amorphous silica volcanic rock), diatomaceous earth] and combinations thereof. Either of these procedures can optionally be performed at a temperature of 5 ° C to 50 ° C and maintained at this temperature for at least three hours. Additives can be used to assist the filtration step and can also result in the ACC color desirably lighter. The purification process removes partially or totally, any insoluble components present in the ACC and can also result in a desirable lighter color. The treatment of ACC with additives, followed by filtration, can also be carried out at temperatures as high as 150 ° C to result in a lighter color, without necessarily reducing the amount of insoluble matter. With the removal of the solid phase from the ACC and / or lighter color, the filtrate resulting from the purification process is the single phase ACC (SP-ACC). The SP-ACC is clear and has little, if any, turbidity. The SP-ACC can be an SP — ACW, an SP — ACO, and combinations thereof.
    [0042] In an incorporation, the amount of insoluble component (if any) in the SP-ACC is determined by filtering the SP-ACC at 15 ° C on 11 pm or greater filter paper, (the SP-ACC being exposed to 15 ° C for at least one week before this filtration). The amount of insoluble component deposited on the filter paper is less than 0.2% by weight. The weight percentage of the insoluble component is based on the total weight of the purified ACC (ie, the total weight of the SP-ACC before filtration on 11 [im or greater filter paper).
    [0043] In an embodiment, SP-ACC contains less than 0.2% by weight, or 0% by weight less than 0.2% by weight of insoluble component after being exposed to 15 ° C for at least one week , or for at least two weeks, or for at least one month, or for at least six months, or for at least 12 months (or for any other time interval).
    [0044] In an embodiment, SP-ACC contains from about 0% by weight to less than about 0.2% insoluble component. A non-limiting example of an SP-ACC is an SP-ACW provided in Table 1 above. SP-ACC is clear and advantageously does not produce any, or substantially none, ejection when used as a plasticizer or coplasticizer in polymeric compositions.
    [0045] In an embodiment, the insoluble component is composed of a mixture of acetylated triglycerides containing at least one saturated fatty acid. Table 2 below shows 3x non-limiting examples of individual components formed after saponification of the fatty acid insoluble component and methylation to form the esters. Table 2. Non-limiting examples of individual components of insoluble components after methylation ponification

    [0046] In one embodiment, the single-phase acetylated castor component has a turbidity of 0 NTU to 50 NTU, or 1.0 NTU to 50 NTU.
    [0047] In one embodiment, the acetylated castor component of a single phase has a color less than 500 APHA, or 50 APHA to 500 APHA, or 50 APHA less than 300 APHA.
    [0048] In an embodiment, the single-phase acetylated castor component has a hydroxyl number from 0 to less than 5 measured according to DIN 53402.
    [0049] In one embodiment, the single-phase acetylated castor component has a viscosity of less than 2000 mPa-s measured according to ASTM D 445 at 25 ° C.
    [0050] In one embodiment, the single-phase acetylated castor component has an iodine number from 0 to 3, or 3.
    [0051] Applicants surprisingly and unexpectedly discovered a single-phase acetylated castor (SP-ACC) component with (I) a low number of hydroxyls, (II) a low viscosity, (III) a low turbidity, ( IV) a low APHA color, and optionally, (V) a low iodine number that produces a plasticizer with excellent compatibility when added in polymeric resins (in particular, vinyl chloride resins). The present SP-ACC is phthalate free, lead free and provides a plasticizer that reproduces all, or substantially all, the properties provided by phthalate based plasticizers.
    [0052] The single phase acetylated castor component may comprise two or more incorporations disclosed herein.
    [0053] In an embodiment, a composition is provided that includes a mixture of (I) SP-ACC and (II) one or more esters of epoxidated fatty acids (EFA). The SP-ACC can be any SP-ACC (i.e., any SP-ACO, any SP-ACW, and combinations thereof) disclosed above without any limit with respect to the number of hydroxyls and / or viscosity. When used herein, the term "epoxidated fatty acid ester" is a compound with at least a portion of fatty acid that contains at least one epoxide group. An "epoxide group" is a three-membered cyclic ether (also called oxirane or alkylene oxide) in which an oxygen atom attaches to each of two carbon atoms that are already attached to each other. Non-limiting examples of epoxidized fatty acid esters include epoxidized soybean oil, epoxidized propylene glycol dioleate, epoxidized coconut oil, epoxidized flaxseed oil, epoxidized fatty acid methyl esters, epoxidized derivatives of each of the above, and any combination previous ones.
    [0054] The epoxidated fatty acid ester can be prepared in several ways. For example, natural oils can be used as raw materials. In this case, natural oils can be saponified in fatty acids and then esterified with alcohols. Then, the low molecular weight esters are epoxidized. The unsaturated ester can be epoxidized with a peracid.
    [0055] Alternatively, a glycidyl fatty acid ester can be prepared via or related substances. In another alternative, it is possible to transesterify the triglyceride with alcohols and then epoxide the unsaturated fatty ester with a peracid.
    [0056] In an embodiment, the epoxidated fatty acid ester can be any epoxidated C1-C14 fatty acid ester, including methyl, ethyl, propyl, butyl, and 2-ethylhexyl esters. In a further embodiment, the epoxidated fatty acid ester is an epoxide of a methyl fatty acid ester.
    [0057] A non-limiting example for the preparation of a fatty acid methyl ester epoxide begins with soybean oil which is transesterified with methanol to prepare the fatty acid methyl ester in the oil. Glycerol is removed from the reaction products due to insolubility. A solution of peracetic acid in ethyl acetate is used to epoxide the double bonds of fatty acids. Peracid is kept below 35% peracid and 35 ° C to prevent detonation. After completion, ethyl acetate and product acetic acid are removed via vacuum extraction.
    [0058] In an embodiment, the epoxidized fatty acid ester is epoxidized soy oil.
    [0059] The SP-ACC / EFA mixture can be referred to as a "composition", a "plasticizer composition", a "plasticizer", or an "SP-ACC / EFA plasticizer". The plasticizer composition can include from about 1% by weight to about 99% by weight of SP-ACC and from about 99% by weight to about 1% by weight of EFA, or from about 30% by weight at about 99% by weight of SP-ACC and from about 70% by weight to about 1% by weight of EFA (based on the total weight of the plasticizer composition).
    [0060] A "plasticizer composition" or plasticizer "is a substance that decreases modulus and tensile strength, and increases flexibility, elongation, impact resistance, and tear strength of the polymeric resin (typically a thermoplastic polymer) to which it is attached. A plasticizer can also decrease the melting point of the polymeric resin, decrease the glass transition temperature and improve the processability of the polymeric resin to which it is added.
    [0061] The plasticizer composition can include one or more SP-ACCs and / or one or more EFAs. In an embodiment, the plasticizer composition may include an SP-ACC having a hydroxyl number from 0 to less than 15, or from 0 to less than 10, or from 0 to less than 5, or from 0 to less than 2, or 0, and epoxidized soybean oil. In an additional embodiment, the SP-ACC of the plasticizer composition may have a hydroxyl number equal to zero and the plasticizer composition also includes epoxidized soybean oil.
    [0062] In an embodiment, the present plasticizer composition is a bioplasticizer composition. When used herein, the term "bioplasticizer composition" is a plasticizer composition composed of a plant-derived material. ACC and EFA are materials derived from vegetables (castor and soy, respectively). A bioplasticizer composition is advantageous because it reduces greenhouse gas emissions, and allows the user to obtain carbon and / or LEED (Leadership in Energy and Environmental Design) credits.
    [0063] In an embodiment, the plasticizer composition includes an SP-ACW with a viscosity of about 100 mPa-s to about 2000 mPa-s at 25 ° C, or from about 100 to about 500 mPa-s at 25 ° C. The SP-ACW can also have a hydroxyl number from 0 to less than 15, or from 0 to less than 10, or from 0 to less than 5, or from 0 to less than 2, or 0. The SP is mixed -ACW with any of the previous EFAs.
    [0064] In an embodiment, the plasticizer composition can include an SP-ACO with hydroxyl number from 0 to less than 15, or from 0 to less than 10, or from 0 to less than 5. The SP-ACO can also have a viscosity of 50 mPa-s at less than 1000 mPa-s at 25 ° C, or from about 100 to about 500 mPa-s at 25 ° C. The SP-ACO is mixed with any of the previous EFAs.
    [0065] In an embodiment, the plasticizer composition can include an SP-ACC, a first EFA, and a second EFA. The second EFA is different from the first EFA. In a further embodiment, the plasticizer composition includes an SP-ACC, ESO, and an epoxidized propylene glycol dioleate. In yet another embodiment, the plasticizer composition includes an SP-ACC, ESO, and an epoxidated fatty acid methyl ester.
    [0066] In an incorporation, the plasticizer composition is in one phase, that is, a liquid.
    [0067] Consequently, EFA alone or in combination with ACC can be subjected to any of the previous purification processes used to form SP-ACC. In an embodiment, EFA contains less than about 0.2% by weight, or 0% by weight less than about 0.2% by weight of insoluble components (when exposed to 15 ° C for a week). In another embodiment, the SP-ACC / EFA mixture contains less than 0.2% by weight, or 0% by weight less than about 0.2% by weight of insoluble components (when exposed to 15 ° C by a week) In another embodiment, the ACC / EFA mixture is purified and contains less than 0.2-s by weight, or 0% by weight less than about 0.2-O by weight of insoluble components (when exposed to 15 ° C for a week). The weight percentage is based on the total weight of the plasticizer composition.
    [0068] Although the composition of this disclosure is preferably phthalate free, the plasticizer composition may also comprise other known plasticizers including, but not limited to, phthalates (diisononyl phthalate, diallyl phthalate, di-2-ethyl phthalate) hexyl, dioctyl phthalate, diisodecyl phthalate and diisotridecyl phthalate), trimellites (such as trioctyl trimellate, triisononyl trimellate and triisodecyl trimellate), citrates, benzoates and adipic polyesters.
    [0069] The present plasticizer composition may comprise two or more embodiments disclosed herein.
    [0070] The present composition composed of SP-ACC alone or in combination with any EFA can be used in a variety of compositions or products. Non-limiting examples of applications suitable for the composition include cosmetic compositions / products, food compositions / products, and polymer compositions / products, soft thermoplastic polyolefins, profiles (gaskets), films, etc.
    [0071] The present disclosure provides a polymeric composition. In an embodiment, a polymeric composition is provided that includes a polymeric resin and the present plasticizer composition. The plasticizer composition can be any SP-ACC, any SP-ACC plasticizer, alone or in combination with any EFA disclosed herein. The compatibility of plasticizer in the polymeric composition is assessed by visual inspection of molded or extruded specimens aged at elevated temperatures (eg 113 ° C or 136 ° C) for defined time intervals (eg 7 days) or for a curve ejection test on molded specimens aged at a fixed temperature (eg 23 ° C). Curved ejection is measured according to ASTM D 3291: Standardized test method for compatibility of plasticizers of poly (vinyl chloride) plastics under compression. The polymeric composition has a curved ejection of 0-2, or 0-1, or 0 measured according to ASTM D 3291. The polymeric composition contains from about 1% by weight to about 99% by weight of the polymeric resin and from about 99% by weight to about 1% by weight of the plasticizer composition. The plasticizer composition can include from about 1% by weight to 99% by weight of SP-ACC and from about 99% by weight to about 1% by weight of EFA, or from 30% by weight at about 99% by weight of SP-ACC and from about 70% by weight to about 1% by weight of EFA. The weight percentage is based on the total weight of the polymeric composition.
    [0072] In an embodiment, the polymeric composition contains less than 0.2% by weight of insoluble components or 0% by weight less than 0.2% by weight of insoluble components. The weight percentage is based on the total weight of the polymeric composition.
    [0073] Non-limiting examples of suitable polymeric resins include polysulfides, polyurethanes, acrylics, epichlorohydrins, nitrile rubber, chlorosulfonated polyethylene, chlorinated polyethylene, polychloroprene, styrene / butadiene rubber, natural rubber, synthetic rubber, EPDM rubber, polymers a propylene based, ethylene based polymers, and vinyl chloride resins. When used herein, the term "propylene-based polymer" is a polymer that comprises a majority weight percentage of polymerized propylene monomer (based on the total amount of polymerizable monomers), and optionally, may comprise at least one polymerized comonomer. When used herein, the term "ethylene-based polymer" is a polymer that comprises a majority weight percentage of polymerized ethylene monomer (based on the total amount of polymerizable monomers), and optionally, can comprise at least one polymerized comonomer.
    [0074] When used herein, the term "vinyl chloride resin" is a vinyl chloride polymer, such as poly (vinyl chloride) (PVC), or a vinyl chloride copolymer such as vinyl chloride copolymer / vinyl acetate, vinyl chloride / vinylidene chloride copolymer, vinyl chloride / ethylene copolymer or a copolymer prepared by grafting vinyl chloride into an ethylene / vinyl acetate copolymer. The resin composition may also include a polymeric mixture of the vinyl chloride polymer or the vinyl chloride copolymer mentioned above with other miscible or compatible polymers including, but not limited to, chlorinated polyethylene, thermoplastic polyurethane, olefinic polymers such as a methacrylate polymer or acrylonitrile / butadiene / styrene polymer (ABS resin).
    [0075] In an embodiment, the vinyl chloride resin is poly (vinyl chloride).
    [0076] In an embodiment, the polymeric composition is a thermoplastic composition. When used herein, a "thermoplastic composition" is a polymeric composition that (1) has the ability to stretch beyond its original length and contracts substantially to its original length when released and (2) softens when exposed to heat and substantially returns to its original condition when cooled to room temperature.
    [0077] In an embodiment, the polymeric composition includes the polymeric resin and a plasticizer including one or more SP-ACC, optionally one or more EFA, and optionally a second EFA.
    [0078] In an embodiment, the polymeric composition includes PVC, an SP-ACC and optionally an EFA. The polymeric composition has a Shore hardness of about D10 to about D70, or about D20 to about D60.
    [0079] In one embodiment, the plasticizer composition has a solution temperature of about 140 ° C to about 200 ° C measured according to DIN 53408. Surprisingly, applicants have found that the plasticizer composition composed of SP-ACC and an EFA unexpectedly provides a plasticizer with low viscosity and low volatility, which is particularly suitable for high temperature wire and cable applications, and which does not migrate out of a thermoplastic polymer to which it is incorporated. In addition, the solution temperature (from 140 ° C to 200 ° C) for the present plasticizer composition is similar to the solution temperature of conventional high molecular weight plasticizers (typically between about 140 ° C and about 180 ° C ). In addition, the viscosity of the present plasticizer composition is less than the viscosity of conventional high molecular weight plasticizers, such as adipic polyester plasticizers. For example, adipic polyester plasticizers, known commercially as adipic polyesters ULTRAMOLL® IV and ULTRAMOLL® III (Lanxess products) have very high viscosity (approximately 6000 to 6500 mPa-s at 25 ° C). It is known that the lower the viscosity of a plasticizer, the faster it will be absorbed into powdered PVC. Hence, the present plasticizer compositions are absorbed into PVC at a faster rate than that of adipic polyester plasticizers, and even that of lower or similar viscosity trimellites. The present plasticizer composition exhibits an unexpected synergy between low viscosity and high molecular weight and produces safe and phthalate-free plasticized PVC with physical, chemical, and mechanical properties that satisfy and / or exceed the properties of PVC resins plasticized with conventional plasticizers of adipic polyester or with conventional phthalate based plasticizers or with conventional trimellate based plasticizers. Especially notable is the retention of tensile properties exhibited by the present composition after oven aging for 168 hours at temperatures as high as 136 ° C.
    [0080] The present polymeric composition exhibits the same or better flexibility and / or elongation when compared to polymeric resins containing conventional plasticizers of adipic polyester, phthalate, and / or trimellitate. In an embodiment, the present polymeric composition is a mixture of PVC and a SP-ACC / EFA plasticizer and has a Shore hardness of about D10 to about D70, or about D20 to about D60. Shore hardness is measured according to ASTM D 2240.
    [0081] In an embodiment, the polymeric composition is composed of a mixture of PVC and the SP-ACC / EFA plasticizer. The polymeric composition is molded on a plate. The plate has a tensile strength retention greater than about 70%, or greater than about 75%, after 168 hours of thermal aging at 113 ° C measured in dog bones cut from 30-milliliter-thick plates according to UL 1581 and ASTM D 638.
    [0082] In an incorporation the polymeric composition is composed of a mixture of PVC and the plasticizer of SP-ACC / EFA. The polymeric composition is molded on a plate. The plate has a tensile strength retention greater than about 70% after 168 hours of thermal aging at 136 ° C measured in dog bones cut from 30 milliliter thick plates according to UL 1581 and ASTM D 638.
    [0083] In an incorporation the polymeric composition is composed of a mixture of PVC and the plasticizer composition of SP-ACC / EFA. The polymeric composition is molded on a plate. The plate has an elongation retention greater than about 40% after 168 hours of thermal aging at 113 ° C measured in dog bones cut from 30 milliliter thick plates according to UL 1581 and ASTM D 638.
    [0084] In an incorporation the polymeric composition is composed of a mixture of PVC and the plasticizer composition of SP-ACC / EFA. The polymeric composition is molded on a plate. The plate has an elongation retention greater than about 40% after 168 hours of thermal aging at 136 ° C measured in dog bones cut from 30 milliliter-thick plates according to UL 1581 and ASTM D 638.
    [0085] Tensile strength and elongation by traction for specimens in the shape of dog bones (I) not aged and (II) thermally aged cut from compression molded plates according to ASTM D-638 are measured.
    [0086] Any of the foregoing polymeric compositions may include one or more of the following additives: a filler, an antioxidant, a flame retardant (antimony trioxide, molybdic oxide and hydrated alumina), a thermal stabilizer, an anti-dripping agent, a colorant , a lubricant, low molecular weight polyethylene, a hindered amine light stabilizer (having at least one secondary or tertiary amine group) ("HALS"), UV light absorbers (such as o-hydroxy phenyl triazines), agents curing agents, reinforcers and retardants, processing aids, coupling agents, antistatic agents, nucleating agents, sliding agents, viscosity controlling agents, tackiness agents, non-stick agents, surfactants, diluent oils, acid purgers, metal deactivators, and any combination thereof.
    [0087] In an embodiment, the present polymeric composition includes a filler. Non-limiting examples of appropriate fillers include calcium carbonate, calcined clay, lime, tile clay, magnesium silicate, barium sulfate, calcium sulfate, strontium sulfate, titanium dioxide, magnesium oxide, magnesium hydroxide, hydroxide calcium, hydrophilic fumed colloidal silica, hydrophobic fumed colloidal silica (surface treated), and any combination of the above. Non-limiting examples of calcined clay are: SATINTONE® SP-33 and POLYFIL® 70.
    [0088] In an embodiment, the polymeric composition includes an antioxidant. Non-limiting examples of suitable antioxidants include hindered phenols such as tetrakis [methylene (3,5-ditherciobutyl-4-hydroxyhydrocinamate)] methane, bis [(beta- (3,5- ditherciobutyl-4-hydroxy benzyl) sulfide) -methyl carboxy ethyl)], 4,4'-thio bis (2-methyl-6-terciobutyl phenol), 4,4'-thio bis (2-terciobutyl-5-methyl phenol), 2,2'-thio bis (4-methyl-6-terciobutyl phenol), and bis (3,5-ditherciobutyl-4-hydroxy) diethyl thio hydrocinamate; phosphites and phosphonites such as tris phosphite (2,4-ditherciobutyl phenyl) and ditherciobutyl phenylphonite; thiocompounds such as dilauryl dipropionate uncle, dimyristyl dipropionate uncle, and distearyl dipropionate uncle; various siloxanes; 2,2,4-trimethyl-1,2-dihydroquinoline polymerized, n, n'-bis (1,4-dimethyl pentyl-p-phenylenediamine), alkylated diphenylamines, 4,4'-bis (alpha, alpha- dimethyl benzyl) diphenylamine, diphenyl-p-phenylenediamine, mixed di-aryl-p-phenylenediamines, and other hindered amine stabilizers or antidegraders. Non-limiting examples of suitable antioxidants include TROPANOL® CA, VANOX® 1320, IRGANOX® 1010, IRGANOX® 245 and IRGANOX® 1076. The antioxidant (s) may be added to the plasticizer composition of this disclosure . Antioxidants can be used in amounts of 0.01 to 5% by weight, based on the weight of the polymeric composition.
    [0089] In an embodiment, the polymeric composition includes a thermal stabilizer. Non-limiting examples of suitable thermal stabilizers include lead-free mixed metal thermal stabilizers, lead stabilizers, organic thermal stabilizers, epoxides, monocarboxylic acid salts, phenolic antioxidants, organic phosphites, hydrotalcites, zeolites, perchlorates and / or betadicetones. Non-limiting examples of suitable betadicketones include dibenzoyl methane, palmitoyl benzoyl methane, stearoyl benzoyl methane and mixtures thereof. A non-limiting example of dibenzoyl methane is RHODIASTAB® 83. A non-limiting example of appropriate mixtures of palmitoyl benzoyl methane and stearoyl benzoyl methane is RHODIASTAB® 50. Non-limiting examples of lead-free mixed metal thermal stabilizers. Lead-free mixed metals include MARK® 6797, MARK® 6776 ACM, MARK® 6777 ACM, THERM-CHEK® RC215P, THERM-CHEK® 7208, NAFTOSAFE® EH-314, BAEROPAN® MC 90400 KA, BAEROPAN® MC 90400 KA / 1, BAEROPAN® MC8553 KA-ST 3-US, BAEROPAN® MC 9238 KA-US, BAEROPAN® MC 90249 KA, and BAEROPAN® MC 9754 KA. The thermal stabilizer can be added to the plasticizer composition of this disclosure. Thermal stabilizers can be used in amounts of 0.1 to 10% by weight, based on the weight of the composition.
    [0090] In an embodiment, the polymeric composition includes a lubricant. Non-limiting examples of suitable lubricants include stearic acid, metal salts of stearic acid, paraffin wax, and polyethylene glycols. Lubricants can be used alone or in combination.
    [0091] In an embodiment, the polymeric composition includes a processing aid. Non-limiting examples of suitable processing aids include 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; ethylene oxide polymers; copolymers of ethylene oxide and propylene oxide; vegetable waxes, oil waxes; nonionic surfactants; and polysiloxanes. Processing aids can be used in amounts of 0.05 to 5% by weight, based on the weight of the composition.
    [0092] In general, polymeric compositions are prepared according to dry mixing or wet mixing methods known to those skilled in the art of PVC compositions. The mixtures obtained from the mixing process can be further combined with a mixer such as a Banbury batch mixer, a Barrel continuous mixer, or a single or double screw extruder.
    [0093] In an embodiment, the present polymeric composition is prepared by absorbing the plasticizers of this disclosure in PVC powder to produce a dry mixture. Any appropriate method / apparatus can be used to prepare the dry mix including, but not limited to, Henschel mixer or tape mixer. The polymeric composition may contain additives other than PVC and plasticizer. Then, the dry mixture can be further combined (via melt extrusion, for example) and molded into any desired shape (film, pellet, etc.).
    [0094] With an optimum stabilizer and antioxidant package, the polymeric compositions are suitable for applications requiring long-term dry and wet insulating resistance testing at elevated temperatures, and other demand applications where temperatures are as high as 136 ° C .
    [0095] The present polymeric compositions may comprise two or more embodiments disclosed herein.
    [0096] The surprising properties of flexibility, low plasticizer volatility, low migration, low viscosity and / or high solution temperature displayed by the present polymeric composition make it well suited for wire and cable coating applications, and in particular applications on wires and cables at high temperature. Consequently, the present disclosure provides a coated metallic conductor. In an embodiment, a coated metallic conductor is provided which includes a metallic conductor and a coating on the metallic conductor. The coating is composed of the present polymeric composition which includes the polymeric resin and the present plasticizer composition. The polymeric resin of the coating can be any polymeric resin disclosed herein. The plasticizer composition can be any plasticizer composition composed of one or more SP-ACC, alone or mixed with one or more EFAs disclosed herein.
    [0097] When used here, "metallic conductor" is at least one metallic wire and / or at least one metallic cable. The coated metallic conductor can be flexible, semi-rigid, or rigid. The coating (also referred to as a "shirt" or a "wrapper" or an "insulation") is on the conductive metal or on another polymeric layer around the conductor. The coating includes the present composition. The composition can be any composition disclosed herein. When used here, "over" includes direct contact or indirect contact between the coating and the metallic conductor. "Direct contact" is a configuration whereby the coating immediately contacts the metallic conductor, without any intermediate layers and / or without any intermediate materials between the coating and the metallic conductor. "Indirect contact" is a configuration through which intermediate layers and / or intermediate structures and / or intermediate materials are located between the metallic conductor and or coating. The coating may cover or differently surround or involve, totally or partially, the metallic conductor. The coating may be the only component involving the metallic conductor. Alternatively, the coating may be a layer of a shirt or wrap around the metallic conductor.
    [0098] In an embodiment, the polymeric resin is a vinyl chloride resin such as PVC discussed above. The PVC is mixed with the plasticizer composition to form the coating. The coating may include additional components. In an embodiment, the coating includes from about 1% by weight to about 99% by weight or from about 20% by weight to about 80% by weight, or from about 30% by weight to about 70% by weight. weight of PVC, and from about 99% by weight to about 1% by weight, or from about 80% by weight to about 20% by weight, or from about 70-5 by weight to about 30% by weight of plasticizer composition. In a further embodiment, the coating contains from about 30% by weight to about 90% by weight of PVC and from about 70% by weight to about 10% by weight of the plasticizer composition.
    [0099] The plasticizer composition can be any plasticizer composition disclosed herein. In an embodiment, the SP-ACC present in the coating comprises less than 0.2% by weight of insoluble components. The SP-ACC present in the coating may have a hydroxyl index of 0 to less than 100, or 0 to less than 15, or 0 to less than 10, or 0 to less than 5, or 0 to less than 2, or 0. a hydroxyl index of 0 to less than 15, or 0 to less than 10, or 0 to less than 5, or 0 to less than 2, or 0.
    [0100] The coating can have any of the properties discussed above for the present composition. In an embodiment, the coated conductor passes the heat test measured according to UL-1581. In another embodiment, the plasticizer composition in the coating has a solution temperature of about 140 ° C to about 200 ° C. In another embodiment, the coating has a Shore hardness of about AIO to about A70 measured in accordance with ASTM D2240.
    [0101] Non-limiting examples of suitable coated metallic conductors include flexible wiring such as flexible wiring for consumer electronics, power cable, power charger wire for cell phones and / or computers, computer data strings, power strands , appliance wiring material, construction wiring, automotive wiring, and consumer electronics accessory cords.
    [0102] The present coated conductor may comprise two or more embodiments disclosed herein.
    [0103] The coated conductor, such as a coated wire or a coated cable (with an optional insulating layer), with a jacket comprising the composition disclosed herein can be prepared with various types of extruders, for example, single spindle types or double spindle. A description of a conventional extruder can be found in U.S. Patent No. 4,857,600. An example of co-extrusion and an extruder can be found in U.S. Patent No. 5,575,965. A typical extruder has a loading funnel at its upstream end and a die at its downstream end. The hopper feeds a barrel, which contains a spindle. At the downstream end, between the spindle end and the die, there is a screen and a carrier plate. The spindle portion is considered to be divided into three sections, the feed section, the compression section and the dosing section, and two zones, the rear heating zone and the frontal heating zone, the operating sections and zones from upstream to downstream. Alternatively, there may be multiple heating zones (more than two) along the axis operating from upstream to downstream. If there is more than one barrel, the barrels are connected in series. The length to diameter ratio of each barrel is in the range of about 15: 1 to about 30: 1.
    [0104] The wire and cable structures (ie, a coated metallic conductor) of this disclosure are made by extruding the present composition over a bundle of insulated conductors to form a jacket (or jacket) around the insulated conductors. The thickness of the jacket depends on the requirements of the desired end-use application. Typical jacket thickness is about 0.010 inch to about 0.200 inch, or about 0.015 inch to about 0.050 inch. The present composition can be extruded into the jacket of the previously prepared composition. Usually, the present composition is in the form of pellets to facilitate its feeding in the extruder. The wire or cable jacket or insulation can be extruded directly from the composition extruder without going through the separate pelletizing step of the present composition. This one-step composition / extrusion process would eliminate a heating history step for the composition.
    [0105] A nylon layer can also be extruded over the insulation, as in conventional THHN, THWN and THWN-2 structures.
    [0106] Below are non-limiting examples of incorporations of this disclosure.
    [0107] In an embodiment, a method is provided for making a coated conductor. Such a method comprises purifying a plasticizer composition comprising an acetylated castor component and optionally an epoxidated fatty acid ester, and forming a plasticizer composition with less than about 0.2% by weight of insoluble components. Purification can take place through filtration and / or centrifugation of the plasticizer composition. The method further comprises mixing the plasticizer composition with a polymeric resin to form a polymeric composition. The method includes coating a metallic conductor with the polymeric composition and forming a coated conductor.
    [0108] Disclosure provides a process. The process includes purifying an acetylated castor component and forming a single phase castor component having less than 0.2% by weight of insoluble components after exposure to 15 ° C for a week.
    [0109] In an incorporation, the purification step of the process is selected from filtration, centrifugation, sedimentation, treatment with additives [such as silicon dioxide (SiO2), aluminum oxide (AI2O3), activated carbon, perlite (amorphous silicon volcanic rock naturally occurring), diatomaceous earth] and combinations thereof.
    [0110] In an embodiment, the process includes exposing, before purifying, the acetylated castor component to a temperature of 5 ° C to 50 ° C for at least three hours, or for at least three hours to a week, or for at least at least three hours to two weeks, or for at least three hours to a month, or for at least three hours to six months, or for at least three hours to 12 months (any value between ranges).
    [0111] In an incorporation, the process includes treating the acetylated castor component with additives [such as silicon dioxide (SiO2), aluminum oxide (AI2O3), activated carbon, perlite (naturally occurring amorphous silicon volcanic rock), diatomaceous earth ], followed by filtration at temperatures as high as 150 ° C to result in a lighter color, without necessarily decreasing the amount of insoluble matter.
    [0112] In an embodiment, the process includes mixing the one-stage acetylated castor component with an epoxidized fatty acid ester and forming a plasticizer composition.
    [0113] In an embodiment, the process includes mixing the plasticizer composition with a polymeric resin, and forming a polymeric composition having a curve ejection value of 0-2, or 0-1, or 0.
    [0114] In an embodiment, the process includes coating the polymeric composition over a metallic conductor and forming a coated conductor. The polymeric composition includes a polymeric resin and the plasticizer composition.
    [0115] The process may comprise two or more incorporations disclosed herein. Testing methods
    [0116] acidity index (or "acid value") is a measure of the amount of free acid present in a compound. The acid number is the number of milligrams of potassium hydroxide required for the neutralization of free acid (fatty acid and / or other acid such as, for example, acetic acid) present in one gram of a substance. The acid number is determined according to the German standard DIN 53402 (mg KOH / g).
    [0117] APHA color is measured using a ColorQuest XE colorimeter, available from HunterLab, or equivalent; 20 mm transmission cell; HunterLab Universal software, version 4.10 or equivalent; black and white reference titles obtainable from HunterLab, or equivalent; the measured APHA color value of deionized water (Dl) is zero.
    [0118] Density is determined according to the German standard DIN 51 757 (g / cm3).
    [0119] Dynamic storage module (G ') and glass transition temperature (Tg) are determined by dynamic-mechanical analysis (DMA) using an AR1000N rheometer from TA Instruments with DMA templates. The specimen is in the form of a rectangular solid and is tested in stress mode. The temperature is varied from -100 ° C to + 160 ° C at an elevation rate of 5 ° C / min, and the test frequency is kept constant at 6.283 rad / s (1 Hz). The sample loss and storage module, as well as the tangent delta, are measured as a function of temperature. The glass transition temperature (Tg) of the maximum delta tangent measurement is determined. The dynamic storage module (G ') at -20 ° C is used as a measure of flexibility at low temperature. The storage and loss module of viscoelastic materials are measures of stored energy (representing the elastic portion) and energy dissipated as heat (representing the viscous portion).
    [0120] The hydroxyl index (or hydroxyl value) is an indication of the degree of acetylation and is a measure of the number of hydroxyls present in a polymer. The hydroxyl index is the number of milligrams of potassium hydroxide required to neutralize the hydroxyl groups in one gram of polymer. The hydroxyl index is determined according to the German standard DIN 53 240 (mg KOH / g).
    [0121] The iodine index is an indication of the degree of hydrogenation and is determined according to German Einheitsmethode DGF C-V 11a (53) (g of I2 / 100 g).
    [0122] Loop spew ejection is a measure according to ASTM D 32 91 that determines the compatibility of plasticizers in poly (vinyl chloride) plastics by calculating the amount of plasticizer that ejects due to the tension situation compression within a 180 ° circular curve. Briefly, using this test, specimens of plasticized poly (vinyl chloride) sheet are curved through an arc of approximately 180 ° and secured in a piece fixing device designed to keep them in the desired conformation. The specimens are kept at a controlled temperature (ie 23 ° C) and, at specified intervals, the specimen is removed, which is curved 180 ° in the opposite direction, and the mold inside the arc is examined for evidence of plasticizer ejection by visual inspection and cleaning the area with a dry index finger. Table 3 shows the classification of values for arc ejection. Table 3

    [0123] The compatibility of plasticizer in the polymeric composition is also assessed by visual inspection of molded or extruded specimens aged at elevated temperatures (eg 113 ° C or 136 ° C) at defined time intervals (eg 7 days ). The extruded specimens can be in the form of a wire (ie, extruded insulation on conductor).
    [0124] Shore hardness is determined according to ASTM D 2240.
    [0125] Solution temperature is the temperature at which a heterogeneous mixture of plasticizer and PVC resin is observed to change to a single phase. The temperature of the solution is determined by immersing 1 gram of PVC in 20 grams of plasticizer and gradually increasing the temperature until complete dissolution of the PVC is observed by observation under a microscope, according to the German standard DIN 53 408 (in ° Ç).
    [0126] The surface smoothness of coated conductors (extruded wires) is measured using a device for measuring surface roughness manufactured by Mitutoyo of Japan, according to ANSI / ASME B46.1.
    [0127] The mass loss temperature of 5% (° C) is determined using TG / DTA 220. The plasticizer sample is heated from room temperature to 600 ° C at 10K / min in an inert gas purge, and the apparent mass loss and thermal effects are recorded in thermograms. The higher the mass loss temperature of 5%, the lower the volatility.
    [0128] Tensile strength and tensile elongation (at 2 inches / min) are determined in non-aged samples, in samples aged at 113 ° C or 136 ° C for 168 hours according to ASTM D 638 in bone dog cut from molded plates or tubular insulation removed from coated conductors (extruded wires).
    [0129] Turbidity is measured using a LaMotte model 2020i turbidimeter, which measures both scattering and attenuation of light. This ISO model has a light emitting diode (LED) with a wavelength of 860 nm and a spectral bandwidth less than or equal to 60 nm. It uses a light detector placed at 90 ° from the light source to measure scattered light and a 180 ° detector to measure light attenuation. A third detector measures the intensity of the light source. This instrument is programmed to use light attenuation in high turbidity and light scattering in low turbidity. The measurements are performed in a nephelometric turbidity unit (NTU), which is a measure of the opacity, or on the other hand transparency, of a liquid. Turbidity is measured by detecting and quantifying the scattering of light by a liquid or a suspension. Turbidity is measured by the attenuation of a light beam or the spread of that light beam. The liquid whose turbidity will be measured is poured into a small glass bottle without distortion and optically transparent of 10 mL, in which, afterwards, the instrument is inserted and then closed with a cover lid. First, the instrument reads a small blank bottle, which is removed, and then the small bottle containing the sample is inserted, and a measured value is recorded in the chosen unit (NTU).
    [0130] The term "UL 1581" is a reference standard from Underwriters Laboratories for electrical wires, cables, and flexible cords. UL 1581 contains specific details for conductors, insulation, liners and other coatings, and for sample preparation methods, sample selection and packaging, and for measurements and calculations that are required in wire and cable standards.
    [0131] The viscosity is determined according to the ASTM D 445 standard, using Brookfield viscometer at 25 ° C and / or 40 ° C.
    [0132] Volumetric resistivity (Ohm-cm) is measured at 23 ° C with direct current of 500 volts, according to ASTM D257. Samples 3.5 inches in diameter are cut from molded plates 40 milliliters thick, and tested in a Hewlett Packard 16008A resistivity cell attached to a Hewlett Packard 4329A high resistance meter.
    [0133] The water content is determined according to the German standard DIN 51 777 (%).
    [0134] The retained weight (%) is measured after 7 days at 136 ° C in samples of 1.25 inches in diameter that are cut from molded plates 30 milliliters thick.
    [0135] Examples of the present disclosure are provided in order to illustrate it without limiting it. Examples A. One-stage acetylated castor component Example 1: One-stage acetylated castor wax sample (SP-ACW4) Preparation and separation of insoluble components by filtration
    [0136] Castor wax (728.5 g) and acetic anhydride (270 g) are loaded into a 2 L flask. The flask is fixed with a mechanical stirrer and a common distillery glassware in a preheated 115 ° C bath. . The temperature is maintained at 115 ° C for 6 hours. A vacuum of 800 to 150 mbar is used to remove residual acetic acid at a bath temperature of 115 ° C. A yellow liquid product (ACW4) is obtained. The properties of ACW 4 are as follows: Density at 25 ° C = 0.951 g / cm3; acid number = 1.4 mg KOH / g; iodine value = 3 g I2 / 100 g; hydroxyl number = 3.7 mg KOH / g; viscosity @ 25 ° C / 40 ° C = 330/145 mPa-s; solution temperature = 194.5 ° C; water content = 0.013% by weight.
    [0137] This liquid product (ACW4) is clear immediately after synthesis. A 100 g sample is maintained at 15 ° C for one week and purified using porous filter paper (comparable to Whatman's grade 43; 16 microns). A muddy product (0.36% by weight) is separated. The separated products are saponified, methylated and injected in a GC / MS system. The compositions are identified using the best combination from the NIST 2000 library (see Table 4 below). Table 4. Compositions of unfiltered liquid phase and separated product (deposit) after saponification and methylation

    [0138] The results show that the separated product is a mixture of mixed acetylated triglycerides containing at least one saturated fatty acid (mainly octadecanoic acid).
    [0139] The purified product (SP-ACW4) is clear, and does not become cloudy even after more than 14 months at room temperature (20 ° C-26 ° C), unlike unfiltered material (ACW4). After exposure to 15 ° C for one week, SP-AVW4 is filtered through 11 µm or larger filter paper. Less than 0.2% by weight of insoluble component is collected on the filter paper. Table 5 below shows the properties of SP-ACW4. Table 5. SP-ACW4 properties
    Example 2A: One-stage acetylated castor wax sample (SP-ACW5 (a)) - Preparation of insoluble components by centrifugation
    [0140] The properties of ACW 5 are as follows: Density at 25 ° C = 0.954 g / cm3; acid number = 2.3 mg KOH / g; iodine value = 1.5 g I2 / 100 g; hydroxyl number = 0 mg KOH / g; viscosity @ 25 ° C = 348 mPa-s; water content = 0.043% by weight. The acetylated castor wax (ACW5) is centrifuged at 20 ° C and 5000 gram-force for 8 minutes to precipitate denser insoluble components. Since the centrifuge required approximately 1 minute to reach full speed, this is considered equivalent to a full-scale disc stack centrifuge in production operating at 17,000 gram-force with a practical dwell time of 124 seconds. The waxy sediment is formed, reaching 1.33% of the original volume. The initial turbidity of this feed suspension measures 235 NTU. The supernatant liquid is decanted, and its turbidity measures 192 NTU. reflecting the precipitation of denser insoluble solids.
    [0141] ACW5 centrifugation at 5000 g-force and 20 ° C is repeated for 90 minutes. The resulting sediment constitutes 3.67% of the initial volume, and the turbidity of the decanted liquid SP-ACW5 (a) measures 38.3 NTU. Example 2B: One-stage acetylated castor wax sample (SP-ACW5 (b)) - Separation of insoluble components by filtration
    [0142] Acetylated castor wax (ACW5) is filtered at 20 ° C to remove insoluble components using Pall-Seitz composite, medium grade K100 lenticular filter. After 20 minutes, 35 g of filtrate is collected containing virtually no solids suspended from the 47 mm diameter filter disc using a maximum differential pressure of 30 psi. The turbidity of this SP-ACW5 (b) filtrate measures 1.8 NTU compared to 235 NTU of the original feed suspension. The color (APHA - 20 mm) of this SP-ACW5 (b) filtrate measures 256. Example 3: One-stage acetylated castor wax sample (SP-ACW6) Preparation and separation of insoluble components by filtration at 15 ° C
    [0143] A 50 mL glass bottle is filled with ACW5 which is preheated to 60 ° C overnight and homogenized in a 0.946 L bottle. The bottle is filled from the 5 gallon vat of Example 2 and is stored unfiltered on the laboratory bench top. The 50 mL bottle is weighed in a water bath at 15 ° C for 7 days. Perceptible fogging appears after about 1 hour at this temperature. After 7 days, the liquid is filtered under nitrogen pressure with a 1.2 µm Whatman GF / C glass microfiber filter to produce SP-ACW6. An insoluble collected amount of about 1.82% by weight was obtained. Purified ACW6 (SP-ACW6) is exposed to 15 ° C for one week, then filtered through 11 µm (or greater) paper that collects less than 0.2% by weight of insoluble component. Examples4a6: Samplesofacetylacetylate in one phase (SP-ACW7, SP-ACW8, SP-ACW9) -Preparation and color removal by contact with additives and filtration
    [0144] Acetylated castor wax (ACW5) is heated to 50 ° C. A different additive is added to a respective separate sample of ACW5: 5 wt% SiCt (ACW7), 5 wt% AI2O3 (ACW8), and 5 wt% activated carbon (ACW9). Each mixture is stirred overnight and subsequently filtered using qualitative Whatman grade 1 (11 µm) filter paper. Color (APHA - 20 mm) is measured using Hunter Lab's ColorQuest XE. The APHA value for deionized water is 0 (zero). Table 6 summarizes the experimental results. All three additives are effective in removing ACW5 color, resulting in a substantially lighter color, with the best performance being SiO2. Table 6. Treatment of acetylated castor wax with additives to decrease color
    B. Thermoplastic compositions: PVC mixtures and plasticizer composition
    [0145] Thermoplastic compositions made up of mixtures of poly (vinyl chloride) (PVC) with various plasticizer and additive compositions shown in Table 7 below are prepared. Table 7. Thermoplastic compositions
    BAEROPAN® MC 90249 KA = Thermal stabilizer (Baerlocher) Clay = filler clay SATINTONE® SP-33 (New England Resins & Pigments Corp.) ESO = epoxidized soybean oil PLAS-CHEK® 775 (Iron) IRGANOX® 1076 = impeded phenolic antioxidant (Ciba Chemicals) PVC = polyvinyl chloride homopolymer (OxyVinyls® 240F) Values =% by weight based on the total weight of the composition *% by weight based on the total weight of plasticizer. C. Thermoplastic compositions 7 and 8 (Mixtures 7 and 8)
    [0146] To prepare Mixtures 7 and 8, use the following procedure: -Preheat ACW and ESO plasticizers at 60 ° C for at least 60 minutes, shake before use and mix them to prepare the plasticizer composition . -Weigh individual ingredients. -First, prepare "dry mixes" by impregnating the plasticizer composition in PVC powder, and then preparing molten mixtures. -The following procedure is used to prepare "dry mixes": (a) Prepare "mix of solids" by mixing everything (except plasticizer and filler composition) in a container using a spatula. (b) Use a 40 cm3 Brabender mixing tank with sigma blades at 90 ° C and 40 rpm. (c) After 2 minutes of heating, add the solid mixture. Mix for 30 seconds. (d) Add plasticizer composition. Mix for 360 seconds (6 minutes). (e) Add clay filler. Mix for 60 seconds. (f) Stop and remove "dry mix". -The "dry mixes" are subsequently melted using the following procedure: (g) Use a 40 cm3 Brabender mixing tank with eccentric rotors at 40 rpm adjustment. (h) Add "dry mix" and mix at 180 ° C for 2 minutes.
    [0147] The mixing bowl mixing compositions are compression molded at 180 ° C for 5 minutes. The specimens are cut from molded plates of 30 milliliters thick to test all properties except volumetric resistivity. Hardness, weight, tensile strength / elongation (at 2 inches / min) are measured for un aged samples and samples aged at 113 ° C or 136 ° C for 168 hours, which were cut from 30 milliliter-thick plates . Thermally aged molded specimens are also visually examined for evidence of exudate (ejection) on the surface. Curved ejection is measured in specimens aged at room temperature for 48 hours. Volumetric resistivity is measured in specimens cut from 40-milliliter-thick plates. The results are given in Table 8.
    [0148] Table 8 provides properties of the various thermoplastic compositions. Table 8
    Shore (D) = Shore D Hardness ASTM D 2240; RT = room temperature; Ejection 113 ° C = Exudate (ejection) on the surface after 7 days at 113 ° C; Ejection 136 ° C = Exudate (ejection) on the surface after 7 days at 136 ° C; Ejection RT = Exudate (ejection) on the surface after 48 hours at room temperature; TE = tensile elongation (%), sample not aged, ASTM D 638; TER 113 ° C = Retention of elongation by traction (%), sample aged at 113 ° C for 168 hours; TER 136 ° C = Retention of elongation by traction (%), sample aged at 136 ° C for 168 hours; TS = tensile strength (psi), sample not aged, ASTM D 638; TSR = Retention of tensile strength (%), ASTM D 638; TSR 113 ° C = Retention of tensile strength (%), sample aged at 113 ° C for 168 hours; TSR 136 ° C = Retention of tensile strength (%), sample aged at 136 ° C for 168 hours; Resist. vol. = Volumetric resistivity (Ohm cm) @ 23 ° C; Weight retention = Weight retained (%) after 7 days @ 136 ° C.
    [0149] Both Mixtures 7 and 8 exhibited satisfactory properties before and after thermal aging. However, ACW4 or SP-ACW4 (Blend 8) results in less hardness (ie, increased plasticization efficiency) and less curve ejection than unpurified ACW4 (Blend 7).
    [0150] Specifically, it is intended that the present disclosure is not limited to the incorporations and illustrations contained herein, but includes modified forms of elements of different incorporations including portions of the incorporations and combinations of elements of different incorporations as being within the limits of the scope of the following claims.
    权利要求:
    Claims (13)
    [0001]
    1. Single-stage acetylated castor wax (SP-ACW), characterized by the fact that it has less than 0.2% by weight of insoluble components based on the total weight of SP-ACW after exposure to 15 ° C for at least one week, with (i) SP-ACW having an iodine number determined according to German Einheitsmethode DGF CV 11a (53) from 0 to less than 40 I2 / 100 g, a number of hydroxyls determined according to DIN 53402 from 0 to less than 15 and a turbidity determined according to the method of description from 1 NTU to 50 NTU, and the amount of insoluble component present is determined by filtering at 15 ° C-25 ° C with 11 filter paper | lm.
    [0002]
    2. Wax according to claim 1, characterized by the fact that it has a hydroxyl number from 0 to less than 5 as determined according to DIN 53402.
    [0003]
    3. Wax according to claim 1, characterized by the fact that it has a viscosity less than 2000 mPa-s as measured according to ASTM D 445 at 25 ° C.
    [0004]
    4. Wax, according to claim 1, characterized by the fact that it has a color less than 500 APHA, determined according to the method of the description.
    [0005]
    5. Composition, characterized by the fact that it comprises: - single-stage acetylated castor wax (SP-ACW) having an iodine number determined according to German Einheitsmethode DGF CV 11a (53) from 0 to less than 40 I2 / IOO g, a hydroxyl value determined according to DIN 53402 from 0 to less than 15, and a turbidity determined according to the method of the description from 1 NTU to 50 NTU; - an epoxidized fatty acid ester; and - the composition has less than 0.2% by weight of insoluble components based on the total weight of the SP-ACW, and after exposure to 15 ° C for at least one week, the amount of insoluble component present being determined by filtering in 15 ° C- 25 ° C with 11 µm filter paper.
    [0006]
    6. Composition according to claim 5, characterized by the fact that it comprises a single phase acetylated castor wax having less than 0.2% by weight of insoluble components after exposure to 15 ° C for at least one week, being that the amount of insoluble component present is determined by filtering at 15 ° C-25 ° C with 11 µm filter paper.
    [0007]
    7. Composition according to claim 5, characterized in that the epoxidated fatty acid ester is selected from the group consisting of epoxidized soybean oil, epoxidized propylene glycol dioleate, epoxidized coconut oil, epoxidized linseed oil, methyl esters epoxidized fatty acids, epoxidized derivatives of each of the above, and combinations thereof.
    [0008]
    8. Polymeric composition, characterized by the fact that it comprises: - a polymeric resin; - a plasticizer composition comprising the composition as defined in claim 5; and - the polymeric composition has a curve ejection index of 0-2 measured according to ASTM D 3291.
    [0009]
    9. Polymeric composition according to claim 8, characterized in that the plasticizer composition comprises less than 0.2% by weight of insoluble components after exposure to 15 ° C for at least one week, with the amount of insoluble component being present is determined by filtering at 15 ° C-25 ° C with 11 µm filter paper.
    [0010]
    10. Polymeric composition according to claim 8, characterized by the fact that the acetylated castor wax of a single phase comprises less than 0.2% by weight of insoluble components after exposure to 15 ° C for at least one week, being that the amount of insoluble component present is determined by filtering at 15 ° C-25 ° C with 11 µm filter paper.
    [0011]
    11. Coated conductor, characterized by the fact that it comprises: - a metallic conductor; and - a coating on the metallic conductor, the coating comprising a polymeric resin and a plasticizer composition comprising the composition as defined in claim 5.
    [0012]
    12. Coated conductor according to claim 11, characterized in that the polymeric composition comprises less than 0.2% by weight of insoluble components after exposure to 15 ° C for at least one week, with the amount of insoluble component present is determined by filtering at 15 ° C-25 ° C with 11 µm filter paper.
    [0013]
    13. Coated conductor according to claim 11, characterized by the fact that the acetylated castor wax of a single phase comprises less than 0.2% by weight of insoluble components after exposure to 15 ° C for at least one week, being that the amount of insoluble component present is determined by filtering at 15 ° C-25 ° C with 11 µm filter paper.
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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]|
    2019-10-29| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-06-02| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-11-03| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 23/06/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US12/821,556|2010-06-23|
    US12/821,556|US8552098B2|2009-09-30|2010-06-23|Purified acetylated derivatives of castor oil and compositions including same|
    PCT/US2011/041557|WO2011163434A1|2010-06-23|2011-06-23|Purified acetylated derivatives of castor oil and compositions including same|
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