Patent Application
20150005420
Various embodiments of the present invention relate to plasticizers derived from natural oils (e.g., oils derived from biological sources). Other aspects of the invention concern a process for producing such plasticizers.
Plasticizers are compounds or mixtures of compounds that are added to polymer resins to impart softness and flexibility. Phthalic acid diesters (also known as “phthalates”) are known plasticizers in many flexible polymer products, such as polymer products formed from polyvinyl chloride (“PVC”) and other vinyl polymers. Examples of common phthalate plasticizers include di-isononyl phthalate, diallyl phthalate, di-2-ethylhexyl-phthalate, dioctyl phthalate, and diisodecyl phthalate. Other common plasticizers, used for high temperature applications, are trimellitates and adipic polyesters. Mixtures of plasticizers are often used to obtain optimum properties.
Phthalate plasticizers have recently come under intense scrutiny by public interest groups that are concerned about the negative environmental impact of phthalates and potential adverse health effects in humans (especially children) exposed to phthalates.
Epoxidized methyl ester of soybean oil (e.g., epoxidized fatty acid methyl ester, or “eFAME”) can be used as a plasticizer for polyvinyl chloride (“PVC”) and other polymers (natural rubber, acrylate, etc.) or alternately, it can be used as a primary or secondary plasticizer in a plasticizer blend (such as with epoxidized soybean oil (“ESO”)). However, eFAME often contains various impurities that may cause color in plasticized compositions. Accordingly, improvements in such plasticizers are desired.
One embodiment is a plasticizer composition comprising: a first plasticizer comprising epoxidized fatty acid alkyl esters; and a second plasticizer comprising an epoxidized natural oil, wherein said first plasticizer comprises fatty acid dimers in a concentration of less than 0.1 weight percent based on the entire weight of said first plasticizer.
Another embodiment is a method for producing a treated plasticizer, said method comprising:
Various embodiments of the present invention concern plasticizers derived from natural oils. In one or more embodiments, the plasticizer includes an epoxidized natural oil (“eNO”). Additionally, the plasticizer includes a natural oil that has been epoxidized and esterified forming epoxidized fatty acid alkyl esters (“eFAAE”). In preparing such plasticizers, the eNO, eFAAE, and/or combinations thereof can undergo one or more color treatment processes. Such plasticizers can be employed with a variety of polymeric resins and in the making of various articles of manufacture.
The present disclosure provides a plasticizer composed of an epoxidized fatty acid alkyl ester and an epoxidized natural oil. A plasticizer is a substance that can lower the modulus and tensile strength, and increase flexibility, elongation, impact strength, and tear strength of a polymeric resin (typically a thermoplastic polymer) to which it is added. A plasticizer may also lower the melting point of the polymeric resin, which lowers the glass transition temperature and enhances processability of the polymeric resin to which it is added. In an embodiment, the present plasticizer is a phthalate-free plasticizer, or is otherwise void or substantially void of phthalate.
The plasticizer includes an epoxidized fatty acid alkyl ester. The alkyl moiety of the ester may be, for example, a methyl group, an ethyl group, a propyl group, or a 2-ethylhexyl group. In an embodiment, the epoxidized fatty acid alkyl ester is an epoxidized fatty acid methyl ester (or “eFAME”). An “epoxidized fatty acid methyl ester” is a C4-C24 (saturated or unsaturated) carboxylic acid methyl ester with at least one epoxide group. An “epoxide group” is a three-member cyclic ether (also called oxirane or an alkylene oxide) in which an oxygen atom is joined to each of two carbon atoms that are already bonded to each other. Epoxidation reactions are typically performed with percarboxylic acids or other peroxy compounds.
The present plasticizer also includes an epoxidized natural oil (“eNO”). A “natural oil,” as used herein, is an oil composed of fatty acid triglycerides and derived from a microbe (algae, bacteria), a plant/vegetable, and/or a seed. In an embodiment, natural oil includes genetically-modified natural oil. In another embodiment, the natural oil excludes petroleum-derived oil. Non-limiting examples of suitable natural oils include beef tallow oil, canola oil, castor oil, corn oil, fish oil, linseed oil, palm oil, rapeseed oil, safflower oil, soybean oil, sunflower oil, tall oil, tung oil, and any combination thereof.
The term “epoxidized natural oil,” as used herein, is a natural oil wherein at least one fatty acid moiety contains at least one epoxide group. Epoxidation may occur by way of reaction of the natural oil with percarboxylic acid and/or other peroxy compounds.
Non-limiting examples of suitable eNO include epoxidized algae oil, epoxidized beef tallow oil, epoxidized canola oil, epoxidized castor oil, epoxidized corn oil, epoxidized fish oil, epoxidized linseed oil, epoxidized palm oil, epoxidized rapeseed oil, epoxidized safflower oil, epoxidized soybean oil, epoxidized sunflower oil, epoxidized tall oil, epoxidized tung oil, and any combination thereof.
In an embodiment, the epoxidized natural oil is an epoxidized soybean oil (“eSO”).
In an embodiment, the plasticizer contains relative amounts of eNO (e.g., eSO) to eFAAE (e.g., eFAME) in a weight ratio in the range of from greater than (“>”) 0:less than (“<”) 100 to <100:>0, more typically from 10:90 to 90:10, more typically from 20:80 to 80:20, and even more typically from 30:70 to 70:30. Weight ratios are based on total weight of the plasticizer.
In an embodiment, the plasticizer can undergo one or more color-reducing treatment processes. Such color-reducing treatment processes include distillation, filtration, treatment with a peroxide, and mixtures of two or more thereof.
In an embodiment, the color-reducing treatment includes distilling the above-described eFAAE (e.g., eFAME) prior to combining it with the eNO. Conventional distillation techniques are employed. For example, distillation can be performed with a wiped film evaporator (“WFE”) and a condenser. In an embodiment, the distillation is performed employing a WFE at a temperature ranging from 120 to 180° C., from 140 to 170° C., or from 150 to 160° C. The condenser can have a temperature of 20° C.
In an embodiment, the color-reducing treatment includes filtering at least a portion of the eNO, the eFAAE, and/or the blended plasticizer composition. Conventional filtration techniques are employed. Illustrative examples of suitable filter media include Magnesol D-60™ (available from The Dallas Group of America, Inc), Pure Flow B-80™ (available from Oil Dri Corporation of America), activated alumina (available from Sigma-Aldrich or Delta adsorbents), fuller's earth clay (available from Sigma-Aldrich), and perlite (e.g., PF-60™, available from The Schundler Company). In an embodiment, the plasticizer or blended plasticizer is stirred with the filtration medium for a time (e.g., 60 minutes) at elevated temperature (e.g., 40° C.). As used herein, the term “elevated temperature” denotes any temperature greater than ambient temperature. Thereafter, the mixture is filtered using, for example, a 1 micrometer (“μm”) filter paper over an 11 μm filter paper, applying vacuum to accelerate filtration.
In an embodiment, the color-reducing treatment includes contacting at least a portion of the eNO, the eFAAE, and/or the blended plasticizer composition with a peroxide. In various embodiments, the plasticizer or plasticizer blend can be treated with peroxide solution at a concentration of from 1 to 3 wt % based on the combined weight of the peroxide solution and plasticizer. The mixture can then be stirred for a time (e.g., 60 minutes). The peroxide can be any peroxide known in the art. Peroxides generally have a structure R1OOR2, where R1 and R2 can be the same or different, and can be hydrogen, aliphatic, or aromatic groups. In various embodiments, the peroxide solution can be hydrogen peroxide (“H2O2”). The peroxide solution can be, for example, a 30% by weight aqueous solution.
In various embodiments, the eFAAE (e.g., eFAME) of the treated plasticizer comprises fatty acid dimers in a concentration of less than 0.1, less than 0.05, or less than 0.02 weight percent based on the entire weight of the eFAAE. Fatty acid dimer content can be determined by chromatographic analyses, as described in the Test Procedures below. Fatty acid dimers include molecules having two combined fatty acid aliphatic chains. The fatty acid aliphatic chains can be saturated, unsaturated, and/or epoxidized. Non-limiting examples of fatty acid dimers include molecules having structures such as:
In various embodiments, the eFAAE (e.g., eFAME) of the treated plasticizer comprises fatty acid trimers in a concentration of less than 0.1, less than 0.05, or less than 0.02 weight percent based on the entire weight of the eFAAE. Fatty acid trimer content can be determined by chromatographic analyses, as described in the Test Procedures below. Fatty acid trimers include molecules having three combined fatty acid aliphatic chains (e.g., triglycerides). The fatty acid aliphatic chains can be saturated, unsaturated, and/or epoxidized. Non-limiting examples of fatty acid trimers include molecules having structures such as:
In various embodiments, the eFAAE (e.g., eFAME) of the treated plasticizer comprises a combined concentration of fatty acid dimers and fatty acid trimers in total amount of less than 0.1, less than 0.05, or less than 0.02 weight percent based on the entire weight of the eFAAE.
In various embodiments, the treated eFAAE, the treated eNO, and/or the treated combination thereof can have an American Public Health Association (“APHA”) color index value of less than 100, less than 90, less than 80, less than 70, less than 60, less than 50, less than 40, or less than 30 upon heat aging at 190° C. for 60 minutes. Heat aging is performed according to the procedure described in the following Examples. APHA color is determined according to ASTM standards E1209 and E313.
The present disclosure provides a polymeric composition. In an embodiment, a polymeric composition is provided which includes a polymeric resin and the present plasticizer as disclosed above.
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, propylene-based polymers, ethylene-based polymers, and vinyl chloride resins. The term, “propylene-based polymer,” as used herein, is a polymer that comprises a majority weight percent polymerized propylene monomer (based on the total amount of polymerizable monomers), and optionally may comprise at least one polymerized comonomer. The term, “ethylene-based polymer,” as used herein, is a polymer that comprises a majority weight percent polymerized ethylene monomer (based on the total weight of polymerizable monomers), and optionally may comprise at least one polymerized comonomer.
The term “vinyl chloride resin,” as used herein, is a vinyl chloride polymer, such as polyvinyl chloride (“PVC”), or a vinyl chloride copolymer such as vinyl chloride/vinyl acetate copolymer, vinyl chloride/vinylidene chloride copolymer, vinyl chloride/ethylene copolymer or a copolymer prepared by grafting vinyl chloride onto ethylene/vinyl acetate copolymer. The vinyl chloride resin can also include a polymer blend of the above-mentioned vinyl chloride polymer or vinyl chloride copolymer with other miscible or compatible polymers including, but not limited to, chlorinated polyethylene, thermoplastic polyurethane, olefin polymers such as a methacryl polymer or acrylonitrile-butadiene-styrene polymer.
In an embodiment, the vinyl chloride resin is PVC.
In an embodiment, the polymeric composition includes from 40 wt % to 50 wt % PVC, from 5 wt % to 20 wt % eFAAE, from 5 wt % to 20 wt % eNO, and from greater than 0 wt % to 35 wt % filler.
The polymeric composition may include one or more of the following optional additives: a filler, a flame retardant, a heat stabilizer, an anti-drip agent, a colorant, a lubricant, a low molecular weight polyethylene, a hindered amine light stabilizer, a UV light absorber, a curing agent, a booster, a retardant, a processing aid, a coupling agent, an antistatic agent, a nucleating agent, a slip agent, a viscosity control agent, a tackifier, an anti-blocking agent, a surfactant, an extender oil, an acid scavenger, a metal deactivator, and any combination thereof.
In an embodiment, the polymeric composition includes PVC, the present plasticizer, a filler (calcium carbonate, clays, silica, and any combination thereof), metal soap stabilizers (zinc stearate or mixed metal stabilizers containing Ca, Zn, Mg, Sn, and any combination thereof), a phenolic or related antioxidant, and a processing aid.
The present disclosure provides a coated conductor. The coated conductor includes a conductor and a coating on the conductor, the coating formed from the polymeric composition described above.
A “conductor,” as used herein, is one or more wire(s) or fiber(s) for conducting heat, light, and/or electricity. The conductor may be a single-wire/fiber or a multi-wire/fiber and may be in strand form or in tubular form. Non-limiting examples of suitable conductors include metals such as silver, gold, copper, carbon, and aluminum. The conductor may also be optical fiber made from either glass or plastic.
The coated conductor may be flexible, semi-rigid, or rigid. The coating (also referred to as a “jacket” or a “sheath” or “insulation”) is on the conductor or on another polymeric layer around the conductor.
As used herein, the term “and/or,” when used in a list of two or more items, means that any one of the listed items can be employed by itself or any combination of two or more of the listed items can be employed. For example, if a composition is described as containing components A, B, and/or C, the composition can contain A alone; B alone; C alone; A and B in combination; A and C in combination; B and C in combination; or A, B, and C in combination.
“Natural oil” means an oil derived from one or more biological sources (e.g., seeds, vegetables, fish, animal fats, bacteria, or algae), as opposed to an oil derived from petroleum or other mineral source.
“Epoxidation” means a process of forming an epoxide, also known as an oxirane or alkylene oxide.
“Fatty acid” means a carboxylic acid composed of an aliphatic chain typically containing 4 to 24 carbon atoms with a terminal carboxyl group (—COOH). The fatty acid can be saturated or unsaturated, branched or unbranched, and may or may not include one or more hydroxyl group(s).
“Epoxidized fatty acid ester” means a compound with at least one fatty acid ester moiety which contains at least one epoxide group.
“Wire” means a single strand of conductive metal, e.g., copper or aluminum, or a single strand of optical fiber.
“Cable” means at least one wire or optical fiber within a sheath (e.g., an insulation covering or a protective outer jacket). Typically, a cable is two or more wires or optical fibers bound together, typically in a common insulation covering and/or protective jacket. The individual wires or fibers inside the sheath may be bare, covered or insulated. Combination cables may contain both electrical wires and optical fibers. The cable can be designed for low, medium, and/or high voltage applications. Typical cable designs are illustrated in U.S. Pat. Nos. 5,246,783, 6,496,629 and 6,714,707.
Measure liquid color according to ASTM standards E1209 and E313 using a BYK Gardner LCS III™ instrument and measure in APHA units. Set up the bench-top instrument and perform calibration check to insure the instrument is working within specifications. Measure sample color using the protocol listed below:
Heat each plasticizer sample in a type II convection oven at 190° C. Collect samples at time intervals indicated in the following Examples and rest on a table top to cool. After 24 hours, measure APHA values of each sample.
Distillation Method for eFAME: Samples 1a-e
Employing a 2 inch molecular still, degas the sample under the following conditions:
Use the residue stream from Pass 1 as feed for the distillation in Pass 2.
Employing a 2 inch molecular still, degas the sample under the following conditions:
Use the residue stream from Pass 1 as feed for the distillation in Pass 2.
A Baur DTL C™ oil tester is used to measure electrical performance. Before testing each fluid, the dielectric test cell is thoroughly cleaned with Heptane. The empty cell is then calibrated to obtain the empty cell capacitance and check for contamination. The cell is filled with the test fluid and heated to the appropriate test temperature, typically 25° C. The εr and tan δ are measured first according to ASTM D924, in which the test voltage is 2000 V (1000V/mm). The direct current resistivity is measured after εr/tan δ so as to prevent any effects of polarization on the following measurements. The resistivity is measured per ASTM D1169, in which 500 V of positive polarity is first applied and the resistivity measured followed by a discharging of the cell and subsequent measurement with negative polarity. The data is then reported as an average of the two readings.
The samples were analyzed using a gas chromatography (“GC”) system with the following conditions:
Instrument: Agilent 6890 GC™
Column: RTx-Biodiesel TG™ (Restek), 15 m×0.32 mm×0.1-μm film
Injection: Split, Restek precision double wool liner
Injection Volume: 1.0 μL
Detection: flame ionization (FID)
Carrier Gas: He
Carrier Pressure: 8 psi, constant pressure
Split flow: 123 mL/min
Split ratio: 40
Hydrogen: 30 mL/min
Air: 350 mL/min
Makeup: 25 mL/min
Injector Temp: 340° C.
Detector Temp: 350° C.
Temperature Program: Initial Temp: 60° C. for 1 min.
Ramp Rate: 15° C./min
Final Temp: 350° C. for 20 min
Data System: Thermo Atlas v 8.2
With a sample size of 100 mL, stir the sample with the filtration medium for 60 minutes at 40° C. Thereafter, filter the solution using a 1 micrometer (“μm”) filter paper over an 11 μm filter paper, applying vacuum to accelerate filtration. Filtration media are as follows:
As indicated below, add either 1 or 3 wt % of 30% hydrogen peroxide (H2O2) solution to the neat plasticizer sample and stir for about 60 minutes with a magnetic stir bar and stirrer. Weight percent of hydrogen peroxide is based on the combined weight of the neat plasticizer sample and the hydrogen peroxide. Perform reaction in a jar.
Sample 1 Comp is an undistilled eFAME comparative sample. Distill eFAME Samples 1a through 1e according to procedure outlined above. Prior to distillation, the epoxidized samples are prepared according to the following general procedure for epoxidation. If the starting raw material is a fatty acid methyl ester (“FAME”), then epoxidation leads to eFAME; if the starting raw material is soybean oil, then epoxidation leads to ESO.
Typically ester or soybean oil, peroxide, and formic acid are combined in 1:2:0.5 proportions, respectively. 50 g of ester (or soybean oil) and corresponding amount of formic acid are weighed in a 3-necked round-bottomed flask (“RBF”) equipped with a mechanical stirrer, condenser and a dropper for controlled addition of H2O2. The mixture of ester and formic acid are stirred at a speed of 400 rpm at 30° C. Calculated amount of hydrogen peroxide (30 or 50 wt %) is added at the rate of 10 mL/hr and then slowly increasing the rate to the required flow rate depending on the exothermicity of the reaction. Addition is generally completed within an hour. The reaction temperature is then raised to 40 or 50° C. and the reaction is continued until the oxirane oxygen value does not increase further. Stirring is stopped and layers are separated. Oil layer is first washed with water followed by dilute potassium hydroxide and again with water or brine. The oil layer is then dried under vacuum.
Sample 2 Comp is an undistilled TeFAME comparative sample. Distill TeFAME Samples 2a through 2e according to the procedure outlined above. The TeFAME samples are prepared according to the following general procedure. Oleic acid (60 g), methanol or any other alcohol (33.92 g), and sulfuric acid (1 wt % of acid, 0.6 g) are weighed in a 2 necked RBF equipped with condenser and temperature sensor. The reaction mixture is heated in an oil batch at 65° C. under nitrogen flow for 6 hours. In some reactions water may form during the reaction, which can be azeotropically removed using toluene. After the reaction, the mixture is washed with water and potassium carbonate to remove unreacted oleic acid, followed by wash with water or brine. Excess alcohol is removed using a rotary evaporator. The final product is dried under vacuum.
Following distillation, analyze each sample for color according to the procedure outlined above.
Heat age each sample as prepared in Example 1 according to the heat aging procedure outlined above. Analyze each sample for color according to the procedure outlined above.
All distilled samples show decreased color upon heat aging as compared to undistilled control samples, particularly at longer aging times (e.g., 60 minutes).
Analyze each sample as prepared in Example 1 according to the electrical performance testing procedure outlined above.
Distillation of the eFAME and TeFAME samples increased insulation resistance in all samples except for 2e.
Prepare samples for injection as follows: weigh 100 μL of sample and 100 μL of pentadecane internal standard into a vial. Add approximately 5 mL of tetrahydrofuran (“THF”) and mix the resulting solution thoroughly. Place an aliquot of this solution in a 2-mL autosampler vial and analyze using the GC conditions and Samples 1 Comp and 1a-e, described above.
n.d.b
aWeight percents reported as an average of two injections
bNot detected
Employing a blend of ESO and eFAME plasticizers, each prepared according to the procedure outlined in Example 1, prepare five filtered samples according to the procedure outlined above and employing the following weight ratios:
Analyze each sample for color according to the procedure outlined above. Sample 3 Comp is an unfiltered comparative sample with a 50/50 wt/wt blend of ESO and eFAME.
Samples treated with Magnesol D 60™, Pure Flow B-80™ and activated alumina show a decline in initial color.
Heat age each sample as prepared in Example 5 according to the heat aging procedure outlined above. Analyze each sample for color according to the procedure outlined above.
All samples showed significant reduction in color formulation during elevated thermal aging cycle with up to 60% reduction in color after 40 minutes of aging at 190° C.
Prepare the following samples according to the peroxide treatment described above. Samples 4 Comp, 5 Comp, and 6 Comp are left untreated as comparative samples. Weight percent of peroxide is based on combined weight of H2O2 solution and plasticizer.
Heat age each sample according to the heat aging procedure outlined above. Analyze each sample for color according to the procedure outlined above.
Color improvements can be seen during initial cycle of heat aging (i.e., up to 60 minutes) at 190° C. for samples 4a, 4b, and 5, in comparison to comparative samples 4 Comp and 5 Comp. Color improvements are seen over a longer period of the heat aging cycle for sample 6 in comparison to comparative sample 6 Comp.
The present application claims the benefit of U.S. Provisional Application No. 61/596,432, filed on Feb. 8, 2012.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US13/23362 | 1/28/2013 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 61596432 | Feb 2012 | US |
