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.
Plasticizer
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 D60™ (available from The Dallas Group of America, Inc), Pure Flow B80™ (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., PF60™, 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.
Polymeric Composition
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.
Additives
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.
Coated Conductor
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.
APHA Color Measurement
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
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.
Chromatographic Analyses
The samples were analyzed using a gas chromatography (“GC”) system with the following conditions:
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.
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.
This application is a divisional of U.S. patent application Ser. No. 14/370,883, which was a National Stage of International Application No. PCT/US2013/023362 filed on Jan. 28, 2013, which claimed priority from U.S. Provisional Patent Application No. 61/596,432 filed on Feb. 8, 2012 entitled “PLASTICIZER COMPOSITIONS AND METHODS FOR MAKING PLASTICIZER COMPOSITIONS,” the teachings of each of which are incorporated by reference herein, as if reproduced in full hereinbelow.
Number | Name | Date | Kind |
---|---|---|---|
2397592 | Blades | Apr 1946 | A |
2403215 | Foster | Jul 1946 | A |
2458484 | Terry et al. | Jan 1949 | A |
2500918 | Rueter et al. | Mar 1950 | A |
2618622 | Grummit et al. | Nov 1952 | A |
2666752 | Grummit et al. | Jan 1954 | A |
3138566 | Arnold | Jun 1964 | A |
3409580 | Alzner | Nov 1968 | A |
3639318 | Tijunelis et al. | Feb 1972 | A |
3668091 | French et al. | Jun 1972 | A |
3712875 | Tijunelis | Jan 1973 | A |
3778465 | Bamstorf | Dec 1973 | A |
3780140 | Hammer | Dec 1973 | A |
3868341 | Sauer et al. | Feb 1975 | A |
3872187 | Fath | Mar 1975 | A |
3891694 | Mills et al. | Jun 1975 | A |
4083816 | Frankel et al. | Apr 1978 | A |
4346145 | Choi et al. | Aug 1982 | A |
4421886 | Worschech et al. | Dec 1983 | A |
4426477 | Yasumatsu et al. | Jan 1984 | A |
4556694 | Wallace | Dec 1985 | A |
4605694 | Walker | Aug 1986 | A |
4612192 | Scheuffgen et al. | Sep 1986 | A |
4613533 | Loomis et al. | Sep 1986 | A |
4627993 | Loomis | Dec 1986 | A |
4670494 | Semenza, Jr. | Jun 1987 | A |
4689429 | Mertz | Aug 1987 | A |
4857600 | Gross et al. | Aug 1989 | A |
5225108 | Bae et al. | Jul 1993 | A |
5227417 | Kroushl, III | Jul 1993 | A |
5246783 | Spenadel et al. | Sep 1993 | A |
5270366 | Hein | Dec 1993 | A |
5278236 | Case et al. | Jan 1994 | A |
5430108 | Schlosberg et al. | Jul 1995 | A |
5454806 | Shinonome | Oct 1995 | A |
5464903 | Hofmann | Nov 1995 | A |
5466267 | Baillargeon et al. | Nov 1995 | A |
5575965 | Caronia et al. | Nov 1996 | A |
5736605 | Oshima | Apr 1998 | A |
5756570 | Hoch et al. | May 1998 | A |
5886072 | Linsky et al. | Mar 1999 | A |
6063846 | Weng et al. | May 2000 | A |
6114425 | Day et al. | Sep 2000 | A |
6274750 | Sato et al. | Aug 2001 | B1 |
6417260 | Weng et al. | Jul 2002 | B1 |
6437170 | Thil et al. | Aug 2002 | B1 |
6451958 | Fan et al. | Sep 2002 | B1 |
6495033 | Talboom | Dec 2002 | B1 |
6496629 | Ma et al. | Dec 2002 | B2 |
6608142 | Weng et al. | Aug 2003 | B1 |
6706815 | Marchand et al. | Mar 2004 | B2 |
6714707 | Rossi et al. | Mar 2004 | B2 |
6734241 | Nielsen et al. | May 2004 | B1 |
6797753 | Benecke et al. | Sep 2004 | B2 |
6849694 | Hata | Feb 2005 | B2 |
6949597 | Nielsen et al. | Sep 2005 | B2 |
7700675 | Bueno de Almeida et al. | Apr 2010 | B2 |
8557139 | Eaton | Oct 2013 | B2 |
20020013396 | Benecke et al. | Jan 2002 | A1 |
20040122159 | Mhetar et al. | Jun 2004 | A1 |
20050090590 | Nielsen et al. | Apr 2005 | A1 |
20050203230 | Kadakia et al. | Sep 2005 | A1 |
20060025544 | Koube et al. | Feb 2006 | A1 |
20060276575 | Hamaguchi et al. | Dec 2006 | A1 |
20070100049 | Ishizuka | May 2007 | A1 |
20070135562 | Freese et al. | Jun 2007 | A1 |
20080200595 | Hinault et al. | Aug 2008 | A1 |
20080227993 | Zuckerman | Sep 2008 | A1 |
20090149585 | De Quadros Junior et al. | Jun 2009 | A1 |
20090149586 | De Quadros Junior et al. | Jun 2009 | A1 |
20090312478 | Hasegawa et al. | Dec 2009 | A1 |
20100010127 | Barki et al. | Jan 2010 | A1 |
20100256278 | Harada et al. | Oct 2010 | A1 |
20110076502 | Chaudhary et al. | Mar 2011 | A1 |
20110272174 | Chaudhary | Nov 2011 | A1 |
20130005937 | Cramail et al. | Jan 2013 | A1 |
Number | Date | Country |
---|---|---|
1188445 | Jun 1985 | CA |
1341681 | Mar 2002 | CN |
101108982 | Jan 2006 | CN |
101070510 | Nov 2007 | CN |
101376631 | Mar 2009 | CN |
101591588 | Dec 2009 | CN |
101824193 | Sep 2010 | CN |
101914219 | Dec 2010 | CN |
0192961 | Sep 1986 | EP |
0358179 | Mar 1990 | EP |
0364717 | Apr 1990 | EP |
0 393 813 | Oct 1990 | EP |
0473915 | Mar 1992 | EP |
0565984 | Oct 1993 | EP |
0986606 | Mar 2000 | EP |
1218443 | Jul 2002 | EP |
1361039 | Nov 2003 | EP |
1624014 | Feb 2006 | EP |
2070977 | Jun 2009 | EP |
2245089 | Nov 2010 | EP |
1437722 | May 1966 | FR |
499931 | Jan 1939 | GB |
790314 | Feb 1958 | GB |
910543 | Nov 1962 | GB |
934689 | Aug 1963 | GB |
1022920 | Apr 1964 | GB |
1102506 | Feb 1968 | GB |
1341623 | Dec 1973 | GB |
2155021 | Sep 1985 | GB |
S44-007131 | Mar 1969 | JP |
S61-016950 | Jan 1986 | JP |
04-059851 | Feb 1992 | JP |
H04-085354 | Mar 1992 | JP |
H04-261452 | Sep 1992 | JP |
2000-319468 | Nov 2000 | JP |
2003-064233 | Mar 2003 | JP |
2003-297149 | Oct 2003 | JP |
2004311064 | Nov 2004 | JP |
2010-042669 | Feb 2010 | JP |
9730115 | Aug 1997 | WO |
0114466 | Mar 2001 | WO |
0198404 | Dec 2001 | WO |
2004052977 | Jun 2004 | WO |
2007006489 | Jan 2007 | WO |
2008081330 | Jul 2008 | WO |
2008081332 | Jul 2008 | WO |
2008122364 | Oct 2008 | WO |
2009102877 | Aug 2009 | WO |
WO 2009102877 | Aug 2009 | WO |
2011041380 | Apr 2011 | WO |
2011041388 | Apr 2011 | WO |
2011041372 | Apr 2011 | WO |
2011041380 | Apr 2011 | WO |
2011041388 | Apr 2011 | WO |
2013003225 | Jan 2013 | WO |
Entry |
---|
CN 101376631 A, 03-2009m Derwent Ab. |
PCT/US2010/050699 International Search Report and Written Opinion, dated Nov. 8, 2010. |
PCT/US2011/035143 International Search Report and Written Opinion, dated Aug. 30, 2011. |
PCT/US2011/041557 International Search Report and Written Opinion, dated Sep. 7, 2011. |
PCT/US2011/045653 International Search Report and Written Opinion, dated Oct. 8, 2011. |
PCT/US2012/043740 International Search Report and Written Opinion, dated Jan. 28, 2013. |
PCT/US2012/055070 International Search Report and Written Opinion, dated Dec. 10, 2012. |
Danisco, Grindsted Soft-n-Safe brochure 2007/2008. |
Barnicoat, C.R. 1945. Reactions and properties of annatto as a cheese colour. Part II. J. Dairy Res. 14: 59-63. |
Bizzari, S.N. et al (2003), Plasticizers. CEH Marketing Research Report, 38-64, Retrieved from http://www.sriconsulting.com. |
Campanella A. et al.; High Yield Epoxidation of Fatty Acid Methyl Esters with Performic Acid Generated In Situ; Chemical Engineering Journal, 144 (2008) 466-475 (Elsevier B.V.). |
Chuanshang Cai, et al.; Studies on the Kinetics of In Situ Epoxidation of Vegetable Oils; Eur. J. Lipid Sci. Technol., 2008, 110, 341-346 (Wiley-VCH GmbH & Co. KGaA, Weinheim). |
Corrigan, Brian Oil purification, filtration and reclamation, Iron Age (1947) 159(14). |
Danisco, Grindsted Soft-n-Safe brochure pp. 1-8, 2007/2008. |
Du G., et al., Catalytic Epoxidation of Methyl Linoleate, JAOCS, vol. 81, No. 4 (2004). |
Freedman, F., Butterfield, R., and Pryde, E.H. Transesterification Kinetics of Soybean Oil. JAOCS, 63(10) p. 1375 (1986). |
Gan, L. H., et al (1994) Epozidized esters of palm olein as plasticizers for poly (vinyl chloride). European Polymer Journal, 31(8), 719-724. |
Greenspan, F. P. et al (1953) Epoxy fatty acid ester plasticizers. Indstrial and Engineering Chemistry, 445(12), 2722-2726. |
Greenspan, F.P. et al (1956), Epoxy fatty acid ester plasticizers. Preparartion and properties, The Journal of the American Oil Chemists Society, 33, 391-394. |
Grummitt O. and Fleming H. Acetylated Castor Oil Industrial and Engineering Chemistry, vol. 37, No. 5, May 1945, pp. 485-491. |
Haas, Michael J. Improving the Economics of biodiesel production through the use of low value lipids as feedstocks: vegetable oil soapstock, Fuel Processing Technology 86 p. 1087-96 (2005). |
Jensen, R.G. Purification of Triglycerides with an Aluminca Column, Lipids, 451-452 (1966). |
Morgenstern, B. “Epoxidized Fatty Acid Esters as Plasticizers for PVC” dated Apr. 22, 2005. |
Morgenstern, B. Epoxidized Fatty Acid Esters as Plasticizers for PVC, presented at the 7th Freiberg Polymer Conference, Apr. 21 and 22, 2005. |
Morgenstern, B. Use of Modified Fatty Acid Esters as Plasticizers for PVC, dated Sep. 12, 2003. |
Opposition to patent EP2245089, Dated Jan. 9, 2013. |
Orellana-Coca et al., Lipase Mediated Simultaneious Esterification and Epoxidation of Oleic Acid for the Production of Alkylepoxystearates. Journal of Molecular Catalysis B: Enzymatic 44 (2007) 133-137. |
Stuart, A et al., Polym. Bull. (2010) 65:589-598. |
Rehberg, C. et. Al. Plasticizers from Lactic Esters and Biabasic Acids Ind. Eng. Chem., 1952, 44 (9), pp. 2191-2195. |
Santacesaria E. et al.; A Biphasic Model Describing Soybean Oil Epoxidation with H2O2 in a Fed-Batch Reactor; Chemical Engineering Journal, vol. 173, Issue 1, Sep. 1, 2011, pp. 198-209 (Elsevier B.V.). |
Sen{hacek over (z)}ana S. et al.; Kinetics of In Situ Epoxidation of Soybean Oil in Bulk Catalyzed by Ion Exchange Resin; Journal of the American Oil Chemists' Society, vol. 78, No. 7 (2001) 725-731 (AOCS Press). |
Sheehan, J et al. “A Look Back at the U.S. Department of Energy's Aquatic Species Program: Biodiesel from Algae”, National Renewable Energy Laboratory, Colorado, Jul. 1998, pp. 1-294. |
Taylor, D. R. Proceedings of the World Conference on oilseed technology and utilization, Adsorptive Purification, American Oil Chemists Society, Champaing, 1992, p. 152-165. |
Tekin A., and Hammond E. Factors Affecting the Electrical Resistivity of Soybean Oil, JAOCS, vol. 75(6) 1998. |
XP002657062 Vertellus Performance Materials Inc.; Flexricin P-8 Technical Data Sheet, Nov. 2006. |
XP002669860, Thomson Scientific, Mar. 13, 2009, London, GB. |
PCT/ US2009/033935, International Preliminary Report on Patentability, dated Aug. 26, 2010. |
PCT/US2009/033935 International Search Report and Written Opinion dated May 18, 2009. |
PCT/US2010/050654 International Search Report and Written Opinion dated Nov. 9, 2010. |
PCT/US2010/050676 International Search Report and Written Opinion dated Jan. 12, 2011. |
PCT/US2010/050690 International Preliminary Report on Patentability, dated Jan. 12, 2012. |
PCT/US2010/050690 International Search Report and Written Opinion, dated Aug. 2, 2011. |
PCT/US2011/035143 International Search Report and Written Opinion, dated Aug. 26, 2011. |
PCT/US2011/041557 International Preliminary Report on Patentability, dated Aug. 31, 2012. |
PCT/US2011/041557 International Search Report and Written Opinion, dated Sep. 5, 2011. |
PCT/US2011/045653 International Search Report and Written Opinion, dated Oct. 7, 2011. |
PCT/US2012/043740 International Search Report and Written Opinion, dated Jan. 23, 2013. |
PCT/US2012/055070 International Search Report and Written Opinion dated Dec. 3, 2012. |
PCT/US2013/023362 International Search Report and Written Opinion, dated Mar. 28, 2013. |
PCT/US2013/023362, International Preliminary Report on Patentability, dated Aug. 12, 2014. |
PCT/ US2009/033935, International Preliminary Report on Patentability, dated May 27, 2009. |
PCT/ US2009/033935, International Preliminary Report on Patentability, dated May 18, 2009. |
PCT/US2010/050654 International Search Report and Written Opinion, dated Nov. 12, 2010. |
PCT/US2010/050690 International Search Report and Written Opinion, dated Jan. 1, 2012. |
PCT/US2010/050690 International Preliminary Report on Patentability, dated Jan. 24, 2012. |
Number | Date | Country | |
---|---|---|---|
20170088695 A1 | Mar 2017 | US |
Number | Date | Country | |
---|---|---|---|
61596432 | Feb 2012 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 14370883 | US | |
Child | 15335532 | US |