WO2016115257A2 - Plastifiants produits à partir d'acides polycycliques ou d'acides gras dimères - Google Patents

Plastifiants produits à partir d'acides polycycliques ou d'acides gras dimères Download PDF

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WO2016115257A2
WO2016115257A2 PCT/US2016/013256 US2016013256W WO2016115257A2 WO 2016115257 A2 WO2016115257 A2 WO 2016115257A2 US 2016013256 W US2016013256 W US 2016013256W WO 2016115257 A2 WO2016115257 A2 WO 2016115257A2
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acid
composition
alcohol
ester
ether
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PCT/US2016/013256
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WO2016115257A3 (fr
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Brian J. Albert
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Lawter, Inc.
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
    • C08L93/04—Rosin

Definitions

  • Plasticizers are added to materials to modify their physical properties, increase the plasticity (a non-reversible deformation of a material in response to an applied force), or increase the fluidity.
  • Materials that are commonly plasticized are: polymers, inks, paints, concrete, and gypsum, among others.
  • ASTM defines plasticizers as substances that are incorporated into plastics or elastomers to increase its flexibility, workability, or distensibility.
  • Plasticizers are often plasticized to alter their physical properties of the product during processing, as well as in the final product. Common properties that are altered for processing include: viscosity, dispersion, lubricity, flow, release, tack, incorporation rate for fillers, and temperature range. Properties of the final product that are affected by plasticizers are hardness, elongation, temperature range, flame resistance, antistatic performance, swelling tendency, and improved flexible lifetime. Plasticizers are often classified as primary or secondary; the former affects the properties of the final product by solvating the polymer and lowering the glass transition temperature (Tg), whereas the latter affects the processing properties by acting as a diluent for the polymer.
  • Tg glass transition temperature
  • heterocyclyloxy, and heterocyclylalkoxy groups carbonyls (oxo); carboxyls; esters;
  • alkyl groups include straight chain and branched alkyl groups having from 1 to about 40 carbon atoms, and typically from 1 to 20 carbons or, in some embodiments, from 1 to 12 carbon atoms.
  • alkyl groups include cycloalkyl groups as defined below. Alkyl groups may be substituted or unsubstituted. Examples of straight chain alkyl groups include methyl, ethyl, n-propyl, n- butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups.
  • Cycloalkyl groups are cyclic alkyl groups such as, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.
  • the cycloalkyl group has 3 to 8 ring members, whereas in other embodiments the number of ring carbon atoms range from 3 to 5, 6, or 7. Cycloalkyl groups may be substituted or unsubstituted.
  • Alkenyl groups or alkenes are straight chain, branched, or cyclic alkyl groups having 2 to about 30 carbon atoms, and further including at least one double bond. In some embodiments alkenyl groups have from 1 to 20 carbons, or, typically, from 1 to 10 carbon atoms. Alkenyl groups may be substituted or un substituted. Alkenyl groups include, for instance, vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl, cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, and hexadienyl groups among others.
  • aryl groups contain 6 to 14 carbons, and in others from 6 to 12 or even 6 to 10 carbon atoms in the ring portions of the groups.
  • aryl groups includes groups containing fused rings, such as fused aromatic-aliphatic ring systems (e.g., indanyl, tetrahydronaphthyl, and the like).
  • Aryl groups may be substituted or unsubstituted.
  • Compounds described herein may include isomeric forms including conformational, constitutional, functional, positional isomers, stereoisomers and tautomers.
  • a "plasticizer,” or “plasticizing agent” is a compound or an additive that imparts flexibility to a rigid or tough material, e.g., a polymer.
  • polycyclic as used herein generally refers to a compound that is composed of two or more ring systems.
  • a ring system is formed from a group of atoms which together form a continuous loop.
  • non-polycyclic based plasticizer is a plasticizer which does not have a polycyclic group.
  • free of other dimer fatty acid based plasticizers indicates that the composition does not contain any dimer fatty acid based plasticizers other than those specifically described.
  • a composition including a polymer and a plasticizer is described herein, as well as a process for preparing the composition and methods of using the composition.
  • the plasticizers are highly compatible with a variety of polymers and are capable of enhancing the flexibility and adding dimensional stability to the compositions of the polymer.
  • the plasticizers of the present technology may be used with several types of polymers including thermoplastic, thermoset, or elastomeric polymers, and in various compositions wherein plasticizers are required or as an alternative for conventional plasticizers.
  • the plasticizers may be prepared by the condensation of suitable carboxylic acids with alcohols, optionally in presence of a catalyst.
  • a composition including a polymer and a plasticizer, where the plasticizer includes a polycyclic acid ester.
  • the plasticizer includes a resin acid ester.
  • the plasticizer may include an ester of resin acids that may be derived from gum rosin, tall oil rosin, or wood rosin.
  • Resin acids include mixtures of a variety of different isomers of monocarboxylic tricyclic resin acids usually containing around 20 carbon atoms.
  • Illustrative resin acids may individually include, but are not limited to abietic acid, abieta- 7, 13-dien-18-oic acid, 13-isopropylpodocarpa-7,13-dien-15-oic acid, neoabietic acid, dehydroabietic acid, tetrahydroabietic acid, palustric acid, levopimaric acid, pimaric acid (pimara-8(14), 15-dien-18-oic acid), isopimaric acid, sandaracopimaric acid, pimaradienoic acid, communic acid, dehydropimaric acid, and secodehydroabietic acid.
  • resin acid derivatives e.g., maleopimaric acid, fumaropimaric acid
  • the resin acid is abietic acid, neoabietic acid, palustric acid, levopimaric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, pimaradienoic acid, communic acid, dehydropimaric acid, secodehydroabietic acid, maleopimaric acid, or fumaropimaric acid.
  • the acid is abietic acid.
  • the esters of these acids may be included in the plasticizer composition.
  • Suitable alcohols may have at least 1, 4, 8, 16, 24, or 36 carbon atoms. In some embodiments, the alcohol has from about 1 to about 8 carbon atoms, about 8 to about 16 carbon atoms, about 16 to about 24 carbon atoms, about 24 to about 30 carbon atoms, about 30 to about 36 carbon atoms, or about 36 to about 42 carbon atoms, and ranges between any two of these values or less than any one of these values. In the case of polyols, one or more resin acids may react with a single polyol molecule. In some embodiments, the alcohol has about 8 to about 36 carbon atoms. In other embodiments, the alcohol has about 16 to about 36 carbon atoms. In some embodiments, the alcohol is a C 4 or greater alcohol.
  • the plasticizer may include esterifi cation products of resin acids and higher alcohols.
  • Illustrative higher alcohols include, but are not limited to butanol,
  • pentaerythritol tri(ethylene glycol), lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, cyclohexanedimethanol, furandimethanol, and the like or a combination of any two or more thereof.
  • a method of preparing a rosin-based plasticizer which includes contacting a resin acid with an alcohol, optionally in the presence of a catalyst.
  • Suitable resin acids and alcohols are as described herein.
  • Suitable esterification catalysts known in the art may be used to improve the rate of esterification reaction.
  • Suitable catalysts include, but are not limited to, Cr, Cu, Pd, Pt, and Ni, catalysts, compounds based on sulfur, phosphorous, and iodine, Bransted acids, such as sulfuric acid, ⁇ -toluenesulfonic acid, benzenesulfonic acid, naphthalene sulfonic acid, hydrochloric acid, hydrobromic acid, and phosphoric acid; Bransted acid or metal salts of acidic ion- exchange resins; heterogeneous catalysts, such as acidic clays and zeolites; and metallic and organometallic compounds based on Li, Mg, Al, Ca, B, Ba, Bi, Ca, Cr, Cu, Hf, In, Pd, Pt, Ti, Sb, Zn, Zr, Sn, and the like or a combination of any two or more thereof.
  • the catalyst is selected from sulfuric acid, ⁇ -toluenesulfonic acid, Ca, Zn, Ti, Sn,
  • the resin may be hydrogenated or diproportionated before, during or after the esterification reaction in order to improve the coloration of the resin esters. It is hypothesized that disproportionation converts the resin acid to dihydroabietic acid and dehydroabietic acid, which are more oxidatively stable and hence provide better coloration. Disproportionation can be conducted in presence of a suitable catalyst based on e.g., Pd, Pt, S, P, and I. [0038] The amount of catalyst required for the esterification of the resin acid depends on such variables as the type and amount of alcohol and resin acid, presence or absence of an azeotroping agent to remove the water formed, etc.
  • the catalyst if present, can be incorporated for example, at a concentration of about 0.001 wt%, about 0.01 wt%, about 0.02 wt%, about 0.05 wt%, about 0.1 wt%, about 0.5 wt%, about 1.0 wt%, about 2 wt%, about 5 wt%, about 10.0 wt%, about 15.0 wt%, about 20.0 wt%, about 30.0 wt%, and ranges between any two of these values or less than any one of these values.
  • the amount of resin acid or a derivative thereof and alcohol used to prepare the resin acid ester may vary depending on the type of alcohol used in the reaction.
  • the alcohol is added in an amount ranging from about 0.01 % to about 90 % by weight of the total weight of the resin acid ester. This includes
  • the amount ranges from about 10 % to about 90 %, from about 20 % to about 80 %, from about 30% to about 75 %, from about 40% to about 70 %, and from about 50 % to about 60 % of the total weight of the resin acid ester composition, and ranges between any two of these values or less than any one of these values.
  • the alcohol may constitute from about 0.01 wt%, about 10 wt%, about 20 wt%, about 30 wt%, about 40 wt%, about 50 wt%, about 60 wt%, about 70 wt%, about 80 wt%, about 90.0 wt%, and ranges between any two of these values or less than any one of these values.
  • the resin acid ester includes about 20 wt% to about 50 wt% of the alcohol.
  • the reaction can be conducted for a period of about 1 min to about 60 min, about 1 h to about 5 h, about 5 h to about 8 h, about 8 h to about 15 h, about 15 h to about 25 h, about 25 h to about 40 h, about 40 h to about 60 h, about 60 h to about 80 h, about 80 h to about 100 h, and ranges between and including any two of these values.
  • the reaction of resin acid with an alcohol is conducted at a temperature of about 240 °C to about 260 °C for about 10 h to about 50 h.
  • the reaction of producing the resin acid ester may further include addition of one or more additives.
  • the additive is a nucleating agent, a branching agent, a chain extender, an antioxidant, a stabilizing agent, a coloring agent, and the like. Additives may also be added before or during or after the esterification reaction to impart requisite property to the resulting plasticizer.
  • the water formed during esterification of the resin acid may be removed using suitable methods.
  • the esterification reaction may be carried out at a temperature sufficiently high enough so that the water formed in the reaction is removed as it is formed, or the water formed during the esterification may be continuously removed as an azeotropic mixture by distillation with benzene, xylene, or toluene.
  • the method includes contacting the resin acid and an alcohol with a dienophile.
  • Suitable dienophiles include, but are not limited to, unsaturated organic acids, anhydrides, esters, alkenes, unsaturated cyclic compounds, alkynes, aromatic compounds having unsaturated substituents, and the like, or a combination of two or more thereof.
  • the dienophile is maleic anhydride, acrylic acid, fumaric acid, methacrylic acid, crotonic acid, itaconic acid, glutaconic acid, citraconic acid, mesconic acid, cinnamic acid, alpha-methyl cinnamic acid, propiolic acid, acetylene dicarboxylic acid, esters of any thereof, acrylamide, or acrylonitrile.
  • the dimer fatty acid may be obtained from fatty acids rich in unsaturation and polyunsaturation.
  • Suitable sources for fatty acids may include, but are not limited to, pine trees, sunflower oils, tall oil fatty acids, soybean oils, corn oils, safflower oils, palm oils, palm kernel oils, cottonseed oils, olive oils, lard, rapeseed oil, fish oils, algal oil, or other naturally occurring or fermented sources of unsaturated fatty acids.
  • Illustrative fatty acids may include, but are not limited to, palmitic acid, stearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidic acid, eicosenoic acid, erucic acid, calendic acid, catalpic acid, myristoleic acid, eladic acid, vaccenic acid, sapienic acid, linoeladic acid, eichopentaenoic acid, docosohexenoic acid, punicic acid, pinolenic acid, arachidonic acid, capric acid, lauric acid, myristic acid, behenic acid, lignoceric acid, cerotic acid, or other C10-C30 mono- or poly-unsaturated fatty acid.
  • the composition of the present technology includes a plasticizer which includes an esterification product of a dimer fatty acid and an alcohol.
  • a fatty acid having one or more double bonds may react with another fatty acid to form a dimer fatty acid.
  • the dimer fatty acid may be derived from unsaturated fatty acids, such as, but not limited to, tall oil fatty acid, a soybean oil, a sunflower oil, a rapeseed oil, fish oil, algal oil, or other naturally occurring or fermented sources of unsaturated fatty acids.
  • unsaturated fatty acids may be palmitoleic, oleic, linoleic, linolenic, eicosenoic, erucic acid, or other C12-C30 mono- or poly-unsaturated fatty acid, or a combination of any two or more thereof.
  • the dimer fatty acid is a C5-C100 dimer fatty acid.
  • the dimer fatty acid is a C15 dimer fatty acid, a C20 dimer fatty acid, a C 24 dimer fatty acid, a C 36 dimer fatty acid, or a combination of any two or more thereof.
  • the dimer fatty acid is a C 36 dimer fatty acid.
  • the dimer fatty acid may be hydrogenated.
  • Illustrative dimer fatty acids are represented by the following formulas I-
  • each of R 1 , R 2 , R 5 and R 6 is independently a C1-C20 alkyl, C2-C20 alkenyl, or a C2-C20 alkynyl group; each of R 3 and R 4 is independently a Ci- C 2 o alkylene. Any of the alkyl, alkenyl, alkyleneyl, or alkynyl groups may be
  • the dimer fatty acid is a acyclic, monocyclic, bicyclic or an aromatic dimer fatty acid represented by the following formulas:
  • unsymmetrical dimer fatty acids may form from a mixture of fatty acids with different sizes and location of double bonds. These not so symmetrical dimer fatty acids can also be represented by above general formulas as well.
  • the dimer fatty acids may react with a variety of alcohols to produce esters that can be used as plasticizers.
  • the alcohols, catalysts, and methods described herein, which may be used to produce resin acid based plasticizers, may also be used to produce dimer fatty acid based plasticizers. These esters have a wide range of solubility factors to match those of various polymers, depending on alcohols used.
  • dimer fatty acids are diacids, they may react with two or more alcohol groups in the same polyol to form a ring structure. Alternatively they may react with two or more different alcohol groups.
  • Illustrative esters wherein each dimer acid reacts with two or more, identical or non-identical alcohols, R 7 OH, may be represented by formulas VIII-XIV:
  • each of R 1 , R 2 , R 5 and R 6 is independently a C 1 -C 20 alkyl, C 2 -C 20 alkenyl, or a C 2 -C 2 o alkynyl group; each of R 3 and R 4 are independently a C 1 -C 20 alkylene; and each R 7 is independently a C 1 -C36 alcohol residue.
  • Any of the alkyl, alkenyl, alkyleneyl, or alkynyl groups may be unsubstituted or substituted and they may be linear, cyclic, or branched.
  • each of R 1 , R 2 , R 5 and R 6 is independently a C 1 -C 20 alkyl group. In some embodiments, each of R 1 , R 2 , R 5 and R 6 is independently a C 1 -C 12 alkyl group. In some embodiments, each of R 1 , R 2 , R 5 and R 6 is independently a Ci-C 8 alkyl group. In some embodiments, each of R 1 , R 2 , R 5 and R 6 is independently a C 2 -C 20 alkenyl group. In some embodiments, each of R 1 , R 2 , R 5 and R 6 is independently a C 2 -Ci 2 alkenyl group.
  • each of R 1 , R 2 , R 5 and R 6 is independently a C 2 -C 8 alkenyl group. In some embodiments, each of a R 1 , R 2 , R 5 and R 6 is independently a Ci- C9 alkyl group. In some embodiments, R 5 is a C 1 -C 12 alkenyl group. In some
  • each of a R 1 , R 2 , R 5 and R 6 is independently a ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl group.
  • R 5 is a 2-octenyl group.
  • each R 7 is independently the residue of a C 2 to C 36 optionally substituted, linear or branched aliphatic alcohol. In some embodiments, each R 7 is independently the residue of a C 8 to C 36 linear or branched aliphatic alcohol. In some embodiments, each R is independently a straight or branched chain C 8 -C 36 alkyl or alkenyl group. In some embodiments, each R 7 independently is a C 8 -C 36 alkyl group. In other embodiments, each R 7 independently is a Ci 6 -C 3 6 alkyl group.
  • each R 8 is independently the residue of a C 8 to C 36 linear or branched aliphatic alcohol. In some embodiments, each R 8 is independently a straight or branched chain C 8 -C 36 alkylene or alkenylene. In some embodiments, each R 8 independently is a C 8 -C 36 alkylene. In other embodiments, each of R 8 independently is a Ci6-C 36 alkylene.
  • the solubility factor of dimer fatty acid esters can be tuned to match the requirements of the appropriate polymer.
  • high molecular weight can be achieved due to the diacid core of the plasticizer, and therefore, high biorenewable content, very low volatility and low migration are observed.
  • the amount of dimer fatty acid and alcohol used to prepare the dimer fatty acid ester may vary depending on the type of alcohol used in the reaction.
  • the alcohol is added in an amount ranging from about 0.01 % to about 90 % by weight of the total weight of the dimer fatty acid ester. This includes embodiments in which the amount ranges from about 10 % to about 90 %, from about 20 % to about 80 %, from about 30% to about 75 %, from about 40% to about 70 %, and from about 50 % to about 60 % of the total weight of the dimer fatty acid ester composition, and ranges between any two of these values or less than any one of these values. In some
  • the alcohol may constitute from about 0.01 wt%, about 10 wt%, about 20 wt%, about 30 wt%, about 40 wt%, about 50 wt%, about 60 wt%, about 70 wt%, about 80 wt%, about 90.0 wt%, and ranges between any two of these values or less than any one of these values.
  • the dimer fatty acid ester includes about 20 wt% to about 50 wt% of the alcohol.
  • the dimer fatty acid ester may be prepared by using suitable methods known in the art.
  • the dimer fatty acid can be reacted with a suitable alcohol at a suitable temperature for a sufficient amount of time, optionally in the presence of a catalyst, to obtain the dimer fatty acid ester.
  • Suitable esterification conditions can be employed for the preparation of the dimer fatty acid ester.
  • the reaction can be conducted at a temperature of about 400 °C or below, about 350 °C or below, about 300 °C or below, about 250 °C or below, about 100 °C or below, about 50 °C or below, about 40 °C or below, at about 35 °C or below, at about 30 °C or below, at about 25 °C or below or at about 20 °C or below, and ranges between and including any two of these values.
  • the reaction can be conducted for a period of about 1 min to about 60 min, about 1 h to about 5 h, about 5 h to about 8 h, about 8 h to about 15 h, about 15 h to about 25 h, about 25 h to about 40 h, about 40 h to about 60 h, about 60 h to about 80 h, about 80 h to about 100 h, and ranges between and including any two of these values.
  • the reaction of dimer fatty acid with an alcohol is conducted at a temperature of about 175 °C to about 225 °C for about 30 min to about 10 h.
  • the reaction of producing the dimer fatty acid ester may further include addition of one or more additives.
  • the additive is a nucleating agent, branching agent, chain extender, antioxidant, plasticizers, stabilizing agent, a coloring agent, or other additives. Additives may also be added before or during or after the esterification reaction to impart requisite property to the resulting plasticizer.
  • a composition may include a polymer and a plasticizer, wherein the plasticizer may include a dimer fatty acid ester.
  • the dimer fatty acid ester is an esterification product of an alcohol and a dimer fatty acid.
  • the composition is free of other dimer fatty acid based plasticizers.
  • the dimer fatty acid is hydrogenated before, during, or after the esterification reaction.
  • Suitable alcohols for the esterification of dimer fatty acids are as described herein for resin acids.
  • the alcohol may be an aliphatic alcohol, either a monool or a polyol.
  • the alcohol is a linear alcohol, a branched alcohol, a cycloaliphatic alcohol, an ether alcohol, a polyether alcohol, an aromatic alcohol, or a halogenated alcohol.
  • Illustrative alcohols include, but not limited to ethylene glycol, propylene glycol, glycerol, pentaerythritol, sucrose, neopentylglycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, butanediol, hexanediol, trimethylolethane, trimethylolpropane, erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbital, galactitol, fucitol, iditol, inositol, mallitol, lactitol, 1-octanol, 2-ethyl-l-hexanol, 1- nonanol, isononanol, 1-decanol, propylheptanol, isodecanol, 1-unde
  • the plasticizer may include esterification products of dimer fatty acids and higher alcohols.
  • Illustrative higher alcohols include, but are not limited to butanol, pentaerythritol, tri(ethylene glycol), lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, cyclohexanedimethanol, furandimethanol, and the like or a combination of any two or more thereof.
  • a method of preparing a dimer fatty acid plasticizer is provided, which includes contacting a dimer fatty acid with an alcohol, optionally in the presence of a catalyst. Suitable dimer fatty acids and alcohols are as described herein.
  • Suitable catalysts include, but are not limited to, Cr, Cu, Pd, Pt, and Ni, catalysts, compounds based on sulfur, phosphorous, and iodine, Bransted acids, such as sulfuric acid, ⁇ -toluenesulfonic acid, benzene sulfonic acid, naphthalene sulfonic acid,
  • hydrochloric acid, hydrobromic acid, and phosphoric acid Bransted acid or metal salts of acidic ion-exchange resins; heterogeneous catalysts, such as acidic clays and zeolites; and metallic and organometallic compounds based on Li, Mg, Al, Ca, B, Ba, Bi, Ca, Cr, Cu, Hf, In, Pd, Pt, Ti, Sb, Zn, Zr, Sn, and the like or a combination of any two or more thereof.
  • the catalyst is selected from sulfuric acid, ⁇ -toluenesulfonic acid, Ca, Zn, Ti, Sn, Zr, and Mg.
  • the dimer fatty acids may be fully or partially hydrogenated in the presence of a catalyst such as e.g., Pd, Pt, Cr, Cu, or Ni.
  • the amount of catalyst required for the esterification of the dimer fatty acid depends on such variables as the type and amount of alcohol and dimer fatty acid, presence or absence of an azeotroping agent to remove the water formed, etc.
  • the catalyst if present, can be incorporated for example, at a concentration of about 0.001 wt%, about 0.01 wt%, about 0.02 wt%, about 0.05 wt%, about 0.1 wt%, about 0.5 wt%, about 1.0 wt%, about 2 wt%, about 5 wt%, about 10.0 wt%, about 15.0 wt%, about 20.0 wt%, about 30.0 wt%, and ranges between any two of these values or less than any one of these values.
  • the water formed during the esterification of the dimer fatty acid may be removed using suitable methods.
  • the esterification reaction may be carried out at a temperature sufficiently high enough so that the water formed in the reaction is removed as fast as it is formed or the water formed during the esterification may be continuously removed as an azeotropic mixture by distillation with benzene, xylene, or toluene.
  • the method further includes contacting the dimer fatty acid and alcohol with a dienophile.
  • Suitable dienophiles include, but are not limited to, unsaturated organic acids, anhydrides and esters, alkenes, unsaturated cyclic compounds, alkynes, aromatic compounds having unsaturated substituents, and the like or a combination of any two or more thereof.
  • the plasticizer including the resin acid ester or the dimer fatty acid ester may have a melting point in the range of about -40°C to about 120°C. This includes from about -30°C to about 110°C, about -20°C to about 100°C, about -10°C to about 90°C, about 0°C to about 80°C, about 10°C to about 70°C, about 20°C to about 60°C, about 30°C to about 50°C, about 35°C to about 45°C, ranges between any two of these values or less than any one of these values. In some embodiments, the plasticizers may have a melting point of less than about 80°C.
  • the plasticizer may have a melting point of less than 50°C. In other embodiments, the plasticizer may have a melting point of less than 40°C. In some embodiments, the plasticizer may have a melting point of less than 25°C.
  • Suitable polymers or the polymers utilized in any of the above compositions, or which may be plasticized by any of the above plasticizers may include any organic polymer, such as for example, plastics and elastomers.
  • the polymer may include one or more of a polyvinyl chloride (PVC), a polyester, a polyacrylate, a polymethacrylate, a polystyrene, a vinylacetate, a polyurethane, a polyamide, a poly(ester amide), a polybutene, a
  • PVC polyvinyl chloride
  • polyester a polyacrylate, a polymethacrylate, a polystyrene, a vinylacetate, a polyurethane, a polyamide, a poly(ester amide), a polybutene, a
  • the polymer includes a polyvinyl chloride, a poly(styrene-butadiene) rubber, a polystyrene block co-polymer, an ethylene-vinylacetate copolymer, a vinyl chloride-vinyl acetate copolymer, or a ethylene acrylic elastomer (AEM).
  • AEM ethylene acrylic elastomer
  • the mass loss for the composition of the present technology may be measured over a period of about 10 min, about 20 min, about 40 min, about lh , about 4h, about 8h, about 12h, about 24h, about 48h, about 72h, or about 168h. In some
  • the mass loss for the composition of the present technology is measured over a period of about 24 h or more.
  • the mass loss for the composition of the present technology may be measured at a temperature of about 50°C to about 250 °C. This includes, a temperature of about 60°C, about 70°C, about 80°C, about 90°C, about 100°C, about 110°C, about 120°C, and about 180 °C or ranges between any two of these values or less than any of these values.
  • a plasticizer In order for a plasticizer to be effective with a polymer, it must be compatible. In other words, the plasticizer should not phase separate from the polymer during processing, or after forming the final product. Compatibility has been quantified by Hansen and Hildebrand as solubility factor or solubility parameter ( ⁇ ), which refers to the ability of one material to dissolve into another. The closer the solubility factors are, the more readily a solution will form. Generally, for the sake of compatibility, the polymers and plasticizers have solubility factors that do not differ from each other considerably. Solubility factors have been described by Hansen as energies from the dispersion, dipolar intermolecular, and hydrogen bonding forces.
  • the solubility factor of the composition within the temperature range of 150° to 300° C may be on the order of magnitude of about 5 to about 30 cal 1/2 cm “3 ' 2 . This includes a solubility factor of from about 6.0 cal 1/2 cm “3/2 to about 25 cal 1/2 cm “3/2 , about 7.0 cal 1/2 cm "3/2 to about 20
  • the terephthalate ester, 1,2-cyclohexane dicarboxylate ester, trimellitate ester, adipate ester, citrate ester, or benzoate ester plasticizer comprises an ester of a C 4 - Ci3 aliphatic alcohol or C2-C9 polyol.
  • Rosin derivatives are generally solids at ambient temperature.
  • the plasticizers of the present technology e.g., the resin acid ester plasticizers and the dimer fatty acid ester plasticizers, may be unexpectedly liquid at low temperatures.
  • the plasticizers of the present technology may be a liquid well below ambient temperature.
  • the plasticizer, as a neat material may be a liquid at -30°C. In some embodiments, the plasticizer, as a neat material, may be a liquid at -10°C. In some embodiments, the plasticizer, as a neat material, may be a liquid at 10°C. In some embodiments, the plasticizer, as a neat material, may be a liquid at 25°C. In some embodiments, the plasticizer, as a neat material, may be a liquid at 30°C.
  • an article which includes the compositions described herein.
  • an article which includes a composition including a polymer and a plasticizer, wherein the plasticizer includes a polycyclic ester.
  • an article which includes a composition including a polymer and a plasticizer, wherein the plasticizer includes a resin ester.
  • an article which includes a composition including a polymer and a plasticizer, wherein the plasticizer includes a dimer fatty acid ester.
  • an article may include the dimer fatty acid based composition, the rosin based composition, or the combinations of both thereof.
  • the polymer may be polyvinyl chloride.
  • the article may include any suitable article which includes a polymer and a plasticizer.
  • the article may include any article which includes polyvinyl chloride and a plasticizer which includes a polycyclic ester.
  • Illustrative articles include, but are not limited to, adhesive compositions; sealant compositions; lamination materials, ophthalmic products such as lenses; flooring underlayment and matting;
  • industrial products such as linears for landfill; consumer products such as floor tiles; automotive parts, such as tires, bumpers, gaskets, fan belts, wiper blades, linears, vibration-dampening mounts, underbody coating, insulation and trim; sports utilities such as artificial turf and track; playground surfaces; mats and pads; ball cores; building products such as roofing membranes, roofing shingles or roofing felt; modified EPDM roofing membranes; modified neoprene articles; tiles or tile backings; carpet backings; asphalt sealers, asphalt underlayment or reinforcement, and asphalt concrete road surfacing material; crack filler for asphalt and cement; concrete modification; sound proofing materials; acoustic underlayment; shoe soles; linears; covers; and other molded products.
  • the article includes pressure-sensitive adhesives, hotmelt adhesives, sealants, films, inks, paints, varnishes, flooring materials, foam materials, footwear materials, gaskets, cosmetic materials, dental materials, roofing materials, tires, wire coatings, or cable coatings.
  • plasticizers exhibit several advantage compared to conventional plasticizers or conventionally plasticized
  • compositions For example, because higher alcohols may be utilized to produce the plasticizers, the choice of alcohol is greatly expanded. The greater pool of potential plasticizers leads to a better way to produce a plasticized polymer by which the solubility factor of the polymer can be matched with one or more plasticizers that are shown to have compatible solubility factors. This allows for the tuning of the plasticizer solubility factor for compatibility with a wide range of polymers such as PVC, styrene block copolymers, polyamides, ethylene-vinyl acetate (EVA), and others (to be expanded upon later).
  • the alcohols used to produce plasticizers from rosin and dimer fatty acid have high enough molecular weight to impart a high molecular weight ester plasticizer for low volatility and migratory properties.
  • Embodiment A A composition comprising a polymer and a plasticizer, wherein the plasticizer comprises a polycyclic ester.
  • Embodiment B The composition of Embodiment A, wherein the polycyclic ester is a rosin ester.
  • Embodiment C The composition of Embodiment A or B, wherein tthe plasticizer is an ester of resin acid, a dehydrogenated resin acid; a monohydrogenated, a dihydrogenated resin acid, a maleated resin acid, a fumarated resin acid, a
  • Embodiment E The composition of any one of Embodiments A-D, wherein the plasticizer is an ester of an abietic acid, a hydrogenated abietic acid, a disproportionated abietic acid, or a combination of any two or more thereof.
  • Embodiment F The composition of any one of Embodiments A-E, wherein the polycyclic ester comprises the esterification product of a resin acid or a derivative thereof, and an alcohol.
  • Embodiment G The composition of any one of Embodiments A-F, wherein the alcohol is a monool or a polyol.
  • Embodiment H The composition of any one of Embodiments A-G, wherein the alcohol is a linear alcohol, a branched alcohol, an aliphatic alcohol, a cycloaliphatic alcohol, an ether alcohol, a polyether alcohol, an aromatic alcohol, or a halogenated alcohol.
  • the alcohol is a linear alcohol, a branched alcohol, an aliphatic alcohol, a cycloaliphatic alcohol, an ether alcohol, a polyether alcohol, an aromatic alcohol, or a halogenated alcohol.
  • Embodiment I The composition of any one of Embodiments A-H, wherein the alcohol is methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, s-butanol, t- butanol, amyl alcohol, i-amyl alcohol, neopentyl alcohol, n-hexanol, glycerol,
  • pentaerythritol ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, butanediol, cyclohexanedimethanol,
  • Embodiment K The composition of any one of Embodiments A- J, wherein the alcohol is a C 8 -C 36 alcohol.
  • Embodiment L The composition of any one of Embodiments A-K, wherein the alcohol is a C16-C36 alcohol.
  • Embodiment M The composition of any one of Embodiments A-L, wherein the alcohol is 1-octanol, 2-ethyl-l-hexanol, 1-nonanol, isononanol, 1-decanol, propylheptanol, isodecanol, 1-undecanol, 1-dodecanol, 2 -butyl- 1-octanol, isododecanol, 1- tridecanol, isotridecanol, 1-tetradecanol, 1-hexadecanol, 2-hexyl-l-decanol, 1-octadecanol, 2-octyl- 1-decanol, 2-hexyl- 1-dodecanol, isostearyl alcohol, 2-decyl- 1-tetradecanol, 2- dodecyl- 1-hexadecanol, 2-tetradecyloctade
  • Embodiment N The composition of any one of Embodiments A-M, wherein the resin acid or a derivative thereof is abietic acid, neoabietic acid, palustric acid, levopimaric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, pimaradienoic acid, communic acid, dehydropimaric acid, secodehydroabietic acid, maleopimaric acid, or fumaropimaric acid, or a combination of any two or more thereof.
  • the resin acid or a derivative thereof is abietic acid, neoabietic acid, palustric acid, levopimaric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, pimaradienoic acid, communic acid, dehydropimaric acid, secodehydroabietic acid, maleopimaric acid, or fumaropimaric acid, or a combination of any two or more thereof.
  • Embodiment P The composition of any one of Embodiments A-O, wherein the plasticizer has a melting point of less than 50°C.
  • Embodiment Q The composition of any one of Embodiments A-P, wherein the plasticizer has a melting point of less than 25°C.
  • Embodiment R The composition of any one of Embodiments A-Q, wherein the polymer comprises a polyvinyl chloride, a polyester, a polyacrylate, a polymethacrylate, a polystyrene, a vinylacetate, a polyethylene, a polyurethane, a polyamide, a poly(ester amide), a polybutene, a polybutadiene, a polyisoprene, a polychloroprene, a nitrile rubber, a polycarbonate, an epoxy, a nitrocellulose, a chlorinated polyethylene, an ethylene propylene diene monomer rubber, or an ethylene propylene rubber, or a copolymer of any two or more thereof.
  • the polymer comprises a polyvinyl chloride, a polyester, a polyacrylate, a polymethacrylate, a polystyrene, a vinylacetate, a polyethylene, a polyurethane,
  • Embodiment U The composition of any one of Embodiments A-T, wherein the composition exhibits a mass loss of less than 3 wt% at 110°C over a time period of 24 hours.
  • Embodiment W The composition of any one of Embodiments A-V, wherein a value of a solubility factor of the polymer differs from a value of a solubility factor of the plasticizer by 1.5 cal 1/2 cm ⁇ 3/2 or less.
  • Embodiment X The composition of any one of Embodiments A-W, wherein the solubility factor of the polymer is about 9.5 cal 1/2 cm ⁇ 3/2 and differs from a value of a solubility factor of the plasticizer by 1.5 cal 1/2 cm ⁇ 3/2 or less.
  • Embodiment Y The composition of any one of Embodiments A-W, wherein the solubility factor of the polymer is about 9.5 cal 1/2 cm ⁇ 3/2 and differs from a value of a solubility factor of the plasticizer by 1.5 cal 1/2 cm ⁇ 3/2 or less.
  • Embodiment BB The composition of any one of Embodiments A-AA, wherein the plasticizer comprises a dimer fatty acid ester.
  • Embodiment CC A composition comprising a polymer and a plasticizer, wherein the plasticizer comprises a dimer fatty acid ester.
  • Embodiment DD The composition of Embodiment CC, wherein the dimer fatty acid ester comprises a esterification product of a dimer fatty acid and an alcohol, wherein: the alcohol is represented by R 7 OH, the dimer fatty acid is a C 28 or more molecule, and the dimer fatty acid ester is represented by formula VIII, IX, X, XI, XII, XIII, XIV, isomers thereof, or a combination of any two or more thereof; wherein: each of R 1 , R 2 , R 5 and R 6 independently is an optionally substituted, linear or branched, C1-C20 alkyl, C2-C20 alkenyl, or a C2-C20 alkynyl group; each of R 3 , R 4 , independently is a an optionally substituted, linear or branched, Ci- C20 alkylene; and each R 7 is independently a Ci-C 36 alcohol residue.
  • the alcohol is represented by R 7 OH
  • Embodiment EE The composition of any one of Embodiments CC-DD, wherein: each of R 1 , R 2 , R 3 , R 4 , and R 6 independently is an linear C 1 -C 2 0 alkyl; R 5 is a C 2 -C 2 0 alkenyl;
  • R 1 and R 2 are the same in formulas VIII, XI and XII, independently; R 3 and R 4 are the same in formula VIII-XIV, independently; and R 5 or R 6 has two more carbon atoms than Rl .
  • R 1 and R 2 are the same C 8 alkyl in formula VIII and C 5 alkyl in formula XI and
  • R 1 in formulas X, X, XIII, and XIV is a C 6 alkyl; R 3 and R 4 are the same C 7 alkyl in formula VIII-XIV; and R 5 is 2-alkene in formula IX and X.
  • Embodiment GG The composition of any one of Embodiments CC-FF, wherein the alcohol is a monool or a polyol.
  • Embodiment FIH The composition of any one of Embodiments CC-GG, wherein the alcohol is an aliphatic alcohol, ether monool, polyether monool, or polyol.
  • Embodiment JJ The composition of any one of Embodiments CC-II, wherein the alcohol is butanol, pentaerythritol, tri(ethylene glycol), lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, cyclohexanedimethanol, or furandimethanol.
  • the alcohol is butanol, pentaerythritol, tri(ethylene glycol), lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, cyclohexanedimethanol, or furandimethanol.
  • Embodiment KK The composition of any one of Embodiments CC-JJ, wherein the alcohol is a C 8 or less alcohol.
  • Embodiment MM The composition of any one of Embodiments CC-LL, wherein the alcohol is a C 8 -C 36 alcohol.
  • Embodiment NN The composition of any one of Embodiments CC-MM, wherein the alcohol is a Ci6-C 36 alcohol.
  • Embodiment OO The composition of any one of Embodiments CC-NN, wherein the dimer fatty acid is derived from unsaturated fatty acids.
  • Embodiment PP The composition of any one of Embodiments CC-OO, wherein the unsaturated fatty acids is a tall oil fatty acid, a soybean oil, a sunflower oil, a rapeseed oil, fish oil, algal oil, or other naturally occurring or fermented sources of unsaturated fatty acids.
  • unsaturated fatty acids is a tall oil fatty acid, a soybean oil, a sunflower oil, a rapeseed oil, fish oil, algal oil, or other naturally occurring or fermented sources of unsaturated fatty acids.
  • Embodiment QQ The composition of any one of Embodiments CC-PP, wherein the unsaturated fatty acids is palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, erucic acid, and other Ci 2 -C 30 mono- or poly-unsaturated fatty acid, or a combination of any two or more thereof.
  • Embodiment RR The composition of any one of Embodiments CC-QQ, wherein the dimer fatty acid is a C15-C50 dimer fatty acid, a C 2 o-C 45 dimer fatty acid, a C 25 - C 4 o dimer fatty acid, a C 3 o-C 40 dimer fatty acid, or a C 36 dimer fatty acid.
  • the dimer fatty acid is a C15-C50 dimer fatty acid, a C 2 o-C 45 dimer fatty acid, a C 25 - C 4 o dimer fatty acid, a C 3 o-C 40 dimer fatty acid, or a C 36 dimer fatty acid.
  • Embodiment SS The composition of any one of Embodiments CC-RR, wherein the dimer fatty acid comprises about 1 wt% to about 99 wt% of trimer fatty acid.
  • Embodiment TT The composition of any one of Embodiments CC-SS, wherein the dimer fatty acid is a C 36 dimer fatty acid.
  • Embodiment UU The composition of any one of Embodiments CC-TT, wherein the plasticizer has a melting point of less than 50°C.
  • Embodiment VV The composition of any one of Embodiments CC-UU, wherein the plasticizer has a melting point of less than 25°C.
  • Embodiment WW The composition of any one of Embodiments CC-VV, wherein the polymer comprises a polyvinyl chloride, a polyester, a polyacrylate, a polymethacrylate, a polystyrene, a vinylacetate, a polyethylene, a polyurethane, a polyamide, a poly(ester amide), a polybutene, a polybutadiene, a polyisoprene, a polychloroprene, a nitrile rubber, a polycarbonate, an epoxy, a nitrocellulose, a chlorinated polyethylene, an ethylene propylene diene monomer rubber, or an ethylene propylene rubber, or a copolymer of any two or more thereof.
  • the polymer comprises a polyvinyl chloride, a polyester, a polyacrylate, a polymethacrylate, a polystyrene, a vinylacetate, a polyethylene, a polyurethan
  • Embodiment XX The composition of any one of Embodiments CC-WW, wherein the polymer comprises a polyvinyl chloride, a poly(styrene-butadiene) rubber, a polystyrene block co-polymer, an ethylene- vinylacetate copolymer, a vinyl chloride- vinyl acetate copolymer, or an ethylene-acrylic elastomer.
  • the polymer comprises a polyvinyl chloride, a poly(styrene-butadiene) rubber, a polystyrene block co-polymer, an ethylene- vinylacetate copolymer, a vinyl chloride- vinyl acetate copolymer, or an ethylene-acrylic elastomer.
  • Embodiment ZZ The composition of any one of Embodiments CC-YY, wherein the composition exhibits a mass loss of less than 3 wt% at 110°C over a time period of 24 hours.
  • Embodiment AAA The composition of any one of Embodiments CC-ZZ, wherein the composition exhibits a mass loss of less than 5 wt% at 175°C over a time period of 168 hours.
  • Embodiment CCC The composition of any one of Embodiments CC-
  • plasticizer has a solubility factor of from about 7.5 cal 1/2 cm ⁇ 3/2 to about 10.5 cal 1/2 cm- 3/2 .
  • Embodiment DDD The composition of any one of Embodiments CC-
  • the value of the solubility factor of the polymer is about 9.5 cal 1/2 cm ⁇ 3/2 and differs from a value of a solubility factor of the plasticizer by 1.5 cal 1/2 cm ⁇ 3/2 or less.
  • Embodiment FFF The composition of any one of Embodiments CC-EEE, wherein the plasticizer further comprises a second plasticizer comprising phthalate ester, terephthalate ester, 1,2-cyclohexane dicarboxylate ester, trimellitate ester, succinate ester, glutarate ester, adipate ester, azelate ester, sebacate ester, citrate ester, fatty ester, epoxidized fatty ester, polycyclic ester, benzoate ester, a phosphate ester, or a combination of any two or more thereof.
  • a second plasticizer comprising phthalate ester, terephthalate ester, 1,2-cyclohexane dicarboxylate ester, trimellitate ester, succinate ester, glutarate ester, adipate ester, azelate ester, sebacate ester, citrate ester, fatty ester, epoxidized fatty ester, polycyclic este
  • Embodiment GGG The composition of any one of Embodiments CC-FFF, wherein the second plasticizer comprises phthalate ester, terephthalate ester, 1,2- cyclohexane dicarboxylate ester, trimellitate ester, adipate ester, citrate ester, or a benzoate ester plasticizer comprising an ester of a C4-C 13 aliphatic alcohol or C2-C9 polyol.
  • GGG wherein the plasticizer, as a neat material, is a liquid at 25°C.
  • Embodiments A-EEE Embodiments A-EEE.
  • Embodiment KKK The article of Embodiment JJJ, wherein the polymer is polyvinyl chloride.
  • Embodiment LLL The article of any one of Embodiments JJJ-KKK, which is a pressure-sensitive adhesive, hotmelt adhesive, sealant, film, ink, paint, varnish, flooring material, foam material, footwear material, gasket, cosmetic material, dental material, roofing material, tire, wire coating, or cable coating.
  • Embodiment MMM A method of preparing a rosin-based plasticizer, the method comprising: contacting a resin acid with an alcohol, optionally in the presence of a catalyst.
  • Embodiment NNN The method Embodiment MMM, further comprising contacting the resin acid and the alcohol with a dienophile.
  • Embodiment OOO The method of any one of Embodiments MMM-NNN, wherein the dienophile is maleic anhydride, acrylic acid, fumaric acid, methacrylic acid, crotonic acid, itaconic acid, glutaconic acid, citraconic acid, mesconic acid, cinnamic acid, alpha-methyl cinnamic acid, propiolic acid, acetylene dicarboxylic acid, esters of any thereof, acrylamide, acrylonitrile, or a mixture of any two or more thereof.
  • the dienophile is maleic anhydride, acrylic acid, fumaric acid, methacrylic acid, crotonic acid, itaconic acid, glutaconic acid, citraconic acid, mesconic acid, cinnamic acid, alpha-methyl cinnamic acid, propiolic acid, acetylene dicarboxylic acid, esters of any thereof, acrylamide, acrylonitrile, or
  • Embodiment PPP A method of preparing a dimer fatty acid plasticizer, the method comprising: contacting a dimer fatty acid with an alcohol, optionally in the presence of a catalyst.
  • Embodiment QQQ The method of Embodiment PPP, further comprising contacting the dimer fatty acid and the alcohol with a dienophile.
  • Example 2 Preparation of a dimer fatty ester of tri(ethylene glycol) monoethyl ether (plasticizer).
  • Dimer fatty acid (Empol 1012, BASF, 287 g) and tri(ethylene glycol) monoethyl ether (187 g) were added to a 2 liter 3-necked round bottom flask at ambient temperature.
  • the flask was placed into a heating mantle, fitted with a thermocouple probe, nitrogen sparge tube, overhead stirrer, and a Dean-Stark trap with a condenser mounted on top of it.
  • the mixture was sparged with nitrogen (0.25 L/min) and heated to 200°C over a period of 1 hour.
  • dibutyltin oxide catalyst (0.46 g) at 95°C. After 28 hours at 200°C, the mixture was stripped under vacuum (30 in. of Hg) for 0.5 hours. After vacuum stripping, the mixture was cooled to ambient
  • Example 3 Preparation and fusing of PVC films.
  • Example 5 Procedure for Preparing, Curing, and Heat- Aging of ethylene acrylic elastomer (AEM) compounds.
  • AEM compounds were prepared by combining the components in Table 5 and mixing them in a Banbury internal mixer. Mixing was completed on a 2 roll mill, and then the samples were then press-cured for 11 min at 180°C. Dumbell specimens were cut from the slab. The specimens were heat aged in a forced air oven preheated to 175°C for 168 hours according to ASTM D573. The physical properties were measured according to ASTM D412 (tensile and elongation), ASTM D2240 (hardness), and ASTM D3418 (Tg).
  • Table 1 shows the mass loss values for 3 resin acid ester based as well as 4 non-resin acid ester based plasticizers over 48 hours at 110°C. These data indicates that resin acid ester based plasticizer have generally lower mass loss.
  • Table 2 shows the mass loss values for a dimer fatty acid ester in comparison to a trimellitate ester at 175°C. This data indicates that the dimer fatty acid ester plasticizer has lower mass loss than a low volatility trimellitate plasticizer.
  • Table 3 shows the mass loss values for 3 PVC films with resin acid ester based plasticizer as well as 4 PVC films with non-resin acid ester based plasticizers over 168 hours at 70°C.
  • Table 4 shows the mass loss values for 3 PVC films with resin acid ester based plasticizer, 1 PVC film plasticized with a mixture of resin acid ester and dimer fatty acid ester, and 4 PVC films with non-resin acid ester based plasticizers over 72 hours at 110°C. These data indicates that resin acid ester based plasticizer have generally lower mass loss. Additionally, the concept of blending of a resin acid ester and dimer fatty acid ester plasticizers in a PVC matrix was demonstrated.
  • Table 5 describes the formulations used to prepare the AEM rubber in
  • Table 6 shows the properties of the AEM rubber specimens after heat aging for 168 hours at 175°C.
  • Vulcofac ® ACT 55 (DBU 2.0 2.0 2.0
  • Tri(2-ethyl-l-hexyl) trimellitate was employed as the plasticizer.
  • c Prepared Dimer fatty acid ester of tri(ethylene glycol) monoethyl ether was employed as the plasticizer.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • Anti-Oxidant Or Stabilizer Compositions (AREA)
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Abstract

L'invention concerne une composition comprenant un plastifiant à base d'ester d'acide résinique ou à base d'ester d'acide gras dimère, et un polymère.
PCT/US2016/013256 2015-01-14 2016-01-13 Plastifiants produits à partir d'acides polycycliques ou d'acides gras dimères WO2016115257A2 (fr)

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CN106432960A (zh) * 2016-09-30 2017-02-22 广西民族大学 一种新型钇钙锌复合热稳定剂及其制备方法
WO2017152188A1 (fr) * 2016-03-04 2017-09-08 Ingevity South Carolina, Llc Compositions d'acide gras et d'ester d'acide de colophane destinées à une utilisation comme agents plastifiants dans des formulations d'adhésifs et procédés d'utilisation associés
WO2020074945A1 (fr) * 2018-10-12 2020-04-16 Dic Corporation Plastifiant pour résine de chlorure de vinyle, composition de résine de chlorure de vinyle, fil électrique et matériau d'intérieur de véhicule
US10842729B2 (en) 2017-09-13 2020-11-24 Living Proof, Inc. Color protectant compositions
US10927234B2 (en) 2018-01-17 2021-02-23 Kraton Polymers U.S. Llc PVC plasticizers and methods for making thereof
US10987300B2 (en) 2017-09-13 2021-04-27 Living Proof, Inc. Long lasting cosmetic compositions
WO2021240247A1 (fr) 2020-05-29 2021-12-02 Industrias Alen, S.A. De C.V. Formulations de type cire de matières d'origine naturelle et leur procédé de préparation
WO2022035138A1 (fr) * 2020-08-10 2022-02-17 주식회사 엘지화학 Composition de plastifiant à base de citrate d'acétyle et composition de résine la comprenant
US11622929B2 (en) 2016-03-08 2023-04-11 Living Proof, Inc. Long lasting cosmetic compositions
US12029805B2 (en) 2018-11-19 2024-07-09 Living Proof, Inc. Properties for achieving long-lasting cosmetic performance

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US2585222A (en) * 1949-02-25 1952-02-12 Nat Southern Products Corp Vinyl resin plasticized with a mixture of a monohydric alcohol ester of the maleic anhydride adduct of rosin acid and a monohydric alcohol ester of a fatty acid
US2577734A (en) * 1951-01-31 1951-12-11 Minnesota Mining & Mfg Plasticized polyvinyl acetate emulsion
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JP5436251B2 (ja) * 2010-02-08 2014-03-05 富士フイルム株式会社 デヒドロアビエチン酸重合体、成形体、デヒドロアビエチン酸重合体の製造方法、及びデヒドロアビエチン酸化合物

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WO2017152188A1 (fr) * 2016-03-04 2017-09-08 Ingevity South Carolina, Llc Compositions d'acide gras et d'ester d'acide de colophane destinées à une utilisation comme agents plastifiants dans des formulations d'adhésifs et procédés d'utilisation associés
US11814557B2 (en) 2016-03-04 2023-11-14 Ingevity South Carolina, Llc Fatty acid and rosin acid ester compositions for use as plasticizers in adhesive formulations and associated methods of use
US11622929B2 (en) 2016-03-08 2023-04-11 Living Proof, Inc. Long lasting cosmetic compositions
CN106432960A (zh) * 2016-09-30 2017-02-22 广西民族大学 一种新型钇钙锌复合热稳定剂及其制备方法
US10842729B2 (en) 2017-09-13 2020-11-24 Living Proof, Inc. Color protectant compositions
US10987300B2 (en) 2017-09-13 2021-04-27 Living Proof, Inc. Long lasting cosmetic compositions
US11707426B2 (en) 2017-09-13 2023-07-25 Living Proof, Inc. Color protectant compositions
US10927234B2 (en) 2018-01-17 2021-02-23 Kraton Polymers U.S. Llc PVC plasticizers and methods for making thereof
TWI778152B (zh) * 2018-10-12 2022-09-21 日商迪愛生股份有限公司 氯乙烯樹脂用之塑化劑、氯乙烯樹脂組成物、電線及車輛內裝材料
CN112888732A (zh) * 2018-10-12 2021-06-01 Dic株式会社 氯乙烯树脂用增塑剂、氯乙烯树脂组合物、电线和车辆内装材料
KR102532017B1 (ko) 2018-10-12 2023-05-15 디아이씨 가부시끼가이샤 염화비닐 수지용 가소제, 염화비닐 수지 조성물, 전선, 및 차량 내장재
KR20210053942A (ko) * 2018-10-12 2021-05-12 디아이씨 가부시끼가이샤 염화비닐 수지용 가소제, 염화비닐 수지 조성물, 전선, 및 차량 내장재
WO2020074945A1 (fr) * 2018-10-12 2020-04-16 Dic Corporation Plastifiant pour résine de chlorure de vinyle, composition de résine de chlorure de vinyle, fil électrique et matériau d'intérieur de véhicule
US12029805B2 (en) 2018-11-19 2024-07-09 Living Proof, Inc. Properties for achieving long-lasting cosmetic performance
WO2021240247A1 (fr) 2020-05-29 2021-12-02 Industrias Alen, S.A. De C.V. Formulations de type cire de matières d'origine naturelle et leur procédé de préparation
WO2022035138A1 (fr) * 2020-08-10 2022-02-17 주식회사 엘지화학 Composition de plastifiant à base de citrate d'acétyle et composition de résine la comprenant
CN115698155A (zh) * 2020-08-10 2023-02-03 株式会社Lg化学 乙酰柠檬酸酯类增塑剂组合物和包含其的树脂组合物
CN115698155B (zh) * 2020-08-10 2024-03-29 株式会社Lg化学 乙酰柠檬酸酯类增塑剂组合物和包含其的树脂组合物
JP7483295B2 (ja) 2020-08-10 2024-05-15 エルジー・ケム・リミテッド アセチルシトレート系可塑剤組成物およびこれを含む樹脂組成物

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