WO2007092407A2 - Méthode de préparation de polyglycérol et d'éthers mixtes - Google Patents

Méthode de préparation de polyglycérol et d'éthers mixtes Download PDF

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Publication number
WO2007092407A2
WO2007092407A2 PCT/US2007/003085 US2007003085W WO2007092407A2 WO 2007092407 A2 WO2007092407 A2 WO 2007092407A2 US 2007003085 W US2007003085 W US 2007003085W WO 2007092407 A2 WO2007092407 A2 WO 2007092407A2
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acid
glycerol
metal catalyst
polyglycerol
containing compound
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PCT/US2007/003085
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WO2007092407A3 (fr
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Daniel Wayne Lemke
Scott Nivens
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Cargill, Incorporated
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Publication of WO2007092407A2 publication Critical patent/WO2007092407A2/fr
Publication of WO2007092407A3 publication Critical patent/WO2007092407A3/fr
Priority to US12/221,608 priority Critical patent/US20080306211A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/13—Saturated ethers containing hydroxy or O-metal groups
    • C07C43/135—Saturated ethers containing hydroxy or O-metal groups having more than one ether bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives

Definitions

  • the present invention relates to an improved method of making polyglycerol and mixed ethers of polyols such as glycerol.
  • Polyglycerol manufacturers have generally focused on one of two paths in the synthesis of polyglycerol from glycerol.
  • glycerol is directly polymerized using a condensation catalyst. This process is described, for example, in U.S. Patent No. 3,637,774.
  • polymerization of glycerol, diglycerol, or polyglycerol is accomplished with the use of epichlorohydrin. This process is described, for example, in U.S. Patent No. 4,960,953.
  • the epichlorohydrin process is capable of producing high quality polyglycerol, the process has several drawbacks.
  • the process requires a high capital investment in equipment since it must be conducted in an explosion-proof facility that is capable of handling epichlorohydrin, which is flammable and a carcinogen.
  • Post- reaction processing is also extensive, typically including, for example, solid-liquid extraction to remove the crystalline salt byproduct, followed by ion exchange, dehydration, and short path distillation.
  • the epichlorohydrin process also requires significant process control, including close control and monitoring of the addition of the epichlorohydrin in order to control the heat of the reaction.
  • the direct process also suffers from several drawbacks.
  • the rate of reaction is controlled, at least in part, by the ability of the process equipment to effectively remove the water that is formed during the reaction (i.e., "water of reaction").
  • the process equipment typically includes a large multi-plate packed distillation column with recycle, which functions to separate the water of reaction as a distillate from the reacting glycerol and polyglycerol,
  • both the temperature and the level of vacuum in the process must be closely controlled and adjusted as the reaction proceeds.
  • the process control operator is continuously adjusting the equipment in order to keep just enough glycerol refluxing in the packed column in order to drive the removal of the water of reaction, while at the same time preventing a sudden batch foam over. This problem is especially prevalent when the rate of generation of water of reaction is high, for example, at the beginning of the reaction.
  • the invention provides a method of reacting glycerol to form polyglycerol or mixed ethers of glycerol or other alcohols (e.g., polyols).
  • the method comprises reacting glycerol in the presence of a fatty acid-containing compound and a metal catalyst to form polyglycerol.
  • the method comprises reacting glycerol and/or an alcohol in the presence of a fatty acid-containing compound and a metal catalyst to form a mixed ether.
  • the addition of the fatty acid-containing compound allows the reduction of the metal catalyst to a level of about one third or less of the level that is typically used in glycerol condensation reactions, without negatively affecting the rate of the reaction.
  • the presence of the fatty acid-containing compound acts as an effective in-process defoaming agent; in certain implementations, this can provide enough lipophillic character to the reaction mixture that the water of reaction may be removed without having to reflux the glycerol.
  • some methods of the invention can greatly simplify the manufacture of polyglycerol and ethers of glycerol, essentially allowing standard etherif ⁇ cation or esterification equipment to be used, and without the need for a large packed distillation column, associated distillation and recycle equipment, and complex in-process computer control.
  • FIG. 1 is a representative reaction scheme for the production of polyglycerol.
  • FIG. 2 is representative reaction scheme for the production of a mixed ether of glycerol using pentaerythritol.
  • FIG. 3 is a representative reaction scheme for the production of a mixed ether of glycerol using a fatty alcohol.
  • FIG. 4 is a chromatograph trace of polyglycerol.
  • FIG. 5 is a chromatograph trace of the mixed ether of glycerol of Example 4.
  • FIG. 6 is a graph showing certain in-process data for the reaction of Example 4.
  • the invention provides an improved method of making polyglycerol or mixed polyol ethers, such as mixed polyol ethers of glycerol or other alcohols (e.g., polyols).
  • the method comprises polymerizing glycerol in the presence of a fatty acid-containing material and a metal catalyst to form polyglycerol.
  • one such method comprises combining: (i) glycerol (typically about 20-99 %wt., more preferably about 75-98 %wt.); (ii) a fatty acid-containing material (e.g., fatty acid, fatty ester, polycarboxylic acid, or triglyceride) (typically about 0.2-20 %wt., more preferably about 0.5-5 %wt.); and (iii) a metal catalyst (e.g., an alkali metal catalyst)
  • glycerol typically about 20-99 %wt., more preferably about 75-98 %wt.
  • a fatty acid-containing material e.g., fatty acid, fatty ester, polycarboxylic acid, or triglyceride
  • a metal catalyst e.g., an alkali metal catalyst
  • the reaction is conducted under an inert atmosphere, such as under a sparge of nitrogen, and at a reduced pressure, for example, from about 140 mmHg to about 300 mmHg.
  • a representative reaction scheme for the production of polyglycerol is shown in FIG. 1.
  • the method comprises forming a mixed ether of a polyol (e.g., glycerol) by reacting a polyol and an alcohol in the presence of a fatty acid-containing material and a metal catalyst. More specifically, the method comprises combining: (i) a polyol (e.g., glycerol) (typically about 20-99 %wt., more preferably about 75-98 %wt.); ( ⁇ ) an alcohol (e.g., fatty alcohol or polyol) (typically about 1-80 %wt., more preferably 10-30 %wt.); (iii) a fatty acid-containing material (e.g., fatty acid, fatty ester, poly-carboxylic acid, or triglyceride) (typically about 0.2-20 %wt., more preferably about 0.5-5 %wt); and (iii) a metal catalyst (e.g., an alkali metal catalyst) (typically about
  • pentaerythritol is shown being reacted with glycerol to form a mixed ether of glycerol.
  • FIG. 3 a fatty alcohol is shown being reacted with glycerol to form a mixed ether of glycerol.
  • the methods of the invention make use of a metal catalyst to promote the reaction of glycerol or other polyol.
  • the metal catalyst comprises a salt (e.g., a hydroxide) of a group IA metal (i.e., an alkali metal) or a salt of a group IIA metal (i.e., an alkaline earth metal).
  • metal catalysts include sodium metal, potassium metal, potassium hydroxide (KOH), sodium hydroxide (NaOH), calcium hydroxide (Ca(OHa)), tin oxylate, and the like. Also useful are carbonate, acetate, phosphate, sulfate, alkoxylate, or oxide salts of the metals. Mixtures may also be used.
  • the metal catalyst is potassium hydroxide (KOH).
  • the metal catalyst is typically added in an amount ranging from about 0.1 %wt. to about 2 %wt., more typically ranging from about 0.2 %wt. to about 0.5 %wt. of the total weight of the reacta ⁇ ts.
  • the methods of the invention are conducted in the presence of a minor amount of a fatty acid-containing compound.
  • the fatty acid-containing compound functions to reduce the amount of metal catalyst that is needed to conduct the reaction and additionally acts as an in-process defoaming agent.
  • the presence of the fatty acid-containing compound allows the reaction to be conducted using a conventional etherif ⁇ cation or esterification apparatus, which typically includes a stainless steel or glass- lined kettle equipped with heating, agitation, an over heat condenser, a receiver, an inert gas (sparge and purge) and a vacuum control). That is, the reaction can be conducted without the need for a large packed distillation column, associated distillation and recycle equipment, and advanced in-process computer control equipment.
  • fatty acids examples include fatty acids, fatty esters, and mixtures thereof.
  • Fatty esters include both fatty esters of monofunctional alcohols (e.g., fatty esters of methanol, ethanol, and the like) and fatty esters of polyfunctional alcohols (e.g., fatty esters of glycerol, sorbitol, and the like).
  • Fatty esters of glycerol include, for example, glycerides, such as monoglycerides, diglycerides, triglycerides, and mixtures thereof.
  • the acyl portion of the fatty acid or acyl portion of the fatty ester has a carbon chain length ranging from about 2 to about 30 carbon atoms, more typically about 8 to about 18 carbon atoms.
  • the acyl portion may be saturated, unsaturated, branched, cyclic, or substituted.
  • fatty acids include Iauric acid, stearic acid, isostearic acid, oleic acid, palmitic acid, behenic acid, myristic acid, caprylic acid, capric acid, caproic acid, arachidic acid, myristoleic acid, linoleic acid, linolenic acid, licaneic acid, ricinoleic acid, eleostearic acid, and erucic acid.
  • Fatty esters that contain any of these fatty acids may also be suitable.
  • the glyceride may be hydrogenated, non-hydrogenated, fractionated, or may be a combination of different glycerides.
  • triglyceride oils include soybean oil, coconut oil, canola oil, corn oil, palm oil, Unseed oil, tallow, lard, sunflower oil, and the like. Fractions and hydrogenated versions of the triglyceride oils may also be used.
  • Exemplary triglyceride oils include alkali refined sunflower and coconut oils.
  • diacid compounds for example, having a carbon chain length ranging from about 2 to about 40 carbon atoms.
  • Representative examples include adipic acid, oxalic acid, malonic acid, succinic acid, gluconic acid, pimelic, phthalic acid, sebacic acid, azelaic acid, trimellitic acid, and dimer fatty acids. Acid anhydrides may also be used.
  • the use of a diacid compound results in the formation of a product that is stable as a homogeneous single phase. This allows and end-user to use the product without mixing prior to use.
  • the use of diacids which do not form monoglycerides, results in improved processing since monoglycerides tend to distill which may cause the condenser to become fouled or plug.
  • the use of Ca(OH) 2 metal catalyst along with a diacid results in the formation of a product that is lighter in color and is substantially free of haze.
  • the methods of the invention are conducted in the presence of a minor amount of a fatty acid-containing compound, for example, about 50 %wt. or less, about 40 %wt. or less, about 30 % wt. or less, or about 20 %wt. or less of the reactive mixture.
  • a minor amount of a fatty acid-containing compound for example, about 50 %wt. or less, about 40 %wt. or less, about 30 % wt. or less, or about 20 %wt. or less of the reactive mixture.
  • the fatty acid-containing composition is present in an amount ranging from about 0.2 %wt. to about 20 %wt. of the reactive mixture.
  • the fatty acid- containing composition is present in an amount ranging from about 0.5 %wt. to about 5 %wt. of the reactive mixture.
  • a second alcohol is included in the reactive mixture along with glycerol.
  • the addition of a second alcohol results in the formation of mixed ethers of glycerol.
  • Useful alcohols may be monofunctional alcohols (e.g., a fatty alcohol) or polyfunctional alcohols (i.e., polyols).
  • Representative examples of alcohols include trimethylol propane, pentaerythritol, manitol, stearyl alcohol, sorbitol, ricinoleic acid, polyethylene glycol, polypropylene glycol, butane diol, hexane diol, and the like.
  • the reaction is conducted at a temperature ranging from about 200 0 C to about 250 0 C 5 more typically ranging from about 210 0 C to about 240 0 C.
  • the reaction is conducted under a reduced pressure, for example, ranging from about 140 mmHg to about 300 mmHg.
  • the preferred reaction pressure typically ranges from about 10 mmHg to about 60 mmHg greater than the vapor pressure of glycerol at the temperature of the reaction. That is, if the vapor pressure of glycerol is about 145 mmHg at 230 0 C, then a preferred range for the reaction pressure would be about 155 mmHg to about 205 mmHg.
  • the reactive composition is heated to the target reaction temperature (e.g., about 230 0 C).
  • the target reaction temperature e.g., about 230 0 C
  • vacuum is applied and the level of vacuum is set according to the desired batch temperature as described above.
  • the pressure is about 400 mmHg; when the batch temperature reaches about 160 0 C to about 190 0 C, the pressure is about 300 mmHg; when the batch temperature reaches about 190 0 C to about 210 0 C, the pressure is about 250 mmHg; and when the batch temperature reaches about
  • the pressure is about 160 to 200 mmHg.
  • reaction may be monitored, for example, by hydroxyl value, refractive index, viscosity, gas chromatography, or other suitable technique.
  • the reaction is considered to be complete, as measured by gas chromatography, when the area count of free glycerol is between about 20% to about 40% of total area count of the gas
  • free (i.e., unreacted) glycerol may be left in the product or may be distilled out, for example, to a level of about 3 %wt. or less in the final product.
  • the reaction kettle is typically cooled to about 210 0 C or less and a vacuum of about 10 mmHg or less is applied. Steam stripping may also be used to remove unreacted glycerol. Gas chromatography or other analytical technique may be used to monitor the stripping process.
  • the mixture is typically cooled under vacuum to a temperature of about 80 0 C.
  • the final product can then filtered, for example, by passing it through a 10-micron sock at about 60 0 C to about 80 0 C.
  • polyglycerol formed according to the method of the invention comprises about 75 %wt. or more of diglycerol, triglycerol, and tetraglycerol species, and comprises less than about 10 %wt. of polyglycerol species of hexaglycerol and greater.
  • this distribution is in accordance with the requirements set by the European and Japanese governments for polyglycerols that are used in the food and cosmetic products, (see, e.g., CAS no.25618-55-7).
  • the polyglycerol is polymerized to a higher degree of conversion than described above. Typically, as the glycerol level is depleted, the level of cyclic polyglycerol that is formed increases. In some embodiments, the cyclic polyglycerol ranges from about 5 %wt. to about
  • the presence of the fatty acid-containing compound in the reaction mixture typically results in the formation of ester functional groups in some of the polyglycerol compounds prepared in accordance with the method of the invention.
  • the polyglycerol may be distilled in order to separate the pure polyol fraction from the ester-containing fraction.
  • the polyglycerols comprising at least some ester-containing species are acceptable in view of the fact that many industrially important end-uses for polyglycerol include the subsequent conversion of the polyglycerol into an ester.
  • the presence of the fatty acid-containing compound causes the final polyglycerol product to exhibit some phase separation upon setting.
  • the phase separation can be reversed with slight mixing to yield a homogeneous mixture.
  • the addition of small amount of water typically provides a clear and phase stable mixture.
  • the fatty acid-containing compound allows the reduction of the metal catalyst to a level of about one third or less of the level that is typically used in glycerol condensation reactions, without negatively affecting the rate of the reaction.
  • the presence of the fatty acid-containing compound also acts as an effective in- process defoaming agent; in certain implementations, this can provide enough lipophillic character to the reaction mixture that the water of reaction may be removed without having to reflux the glycerol.
  • some methods of the invention can greatly simplify the manufacture of polyglycerol and ethers of glycerol, essentially allowing standard etherif ⁇ cation or esterif ⁇ cation equipment (e.g., stainless steel or glass lined kettle equipped with heating, agitation, over heat condenser, receiver, inert gas, and vacuum control) to be used. That is, some embodiments of the invention may be conducted without the need for a large packed distillation column, associated distillation and recycle equipment, and complex in-process computer control equipment. In some embodiments, it is desirable to include an in-line demister or cyclone in order to minimize glycerol loss due to entrapment.
  • standard etherif ⁇ cation or esterif ⁇ cation equipment e.g., stainless steel or glass lined kettle equipped with heating, agitation, over heat condenser, receiver, inert gas, and vacuum control
  • GC method for polyglycerol determination A 10-50 mg sample of polyglycerol was derivatized with 1 ml of silylating reagent (hexamethyldisilazane (HMDS): trimethylchlorosilane (TMCS): pyridine, 3:1:9 from Supelco, Inc. of Bellefonte, Pa.) following Supelco's recommended procedure.
  • silylating reagent hexamethyldisilazane (HMDS): trimethylchlorosilane (TMCS): pyridine, 3:1:9 from Supelco, Inc. of Bellefonte, Pa.
  • the polyglycerol distribution was determined by gas chromatography using a DB- 5HT capillary column (30 m x 0.32 mm ⁇ D x 0.1 mm film thickness), available from J & W Scientific Inc. of Folsom, Calif., and an HP Series 5890 Chromatograph equipped with an FID detector.
  • the splitter was set at 20: 1 and the FID set with flow rates of 30 ml/min hydrogen; 30 mi/min purge gas; and 300 ml/min air.
  • the conditions for the column were: helium carrier gas (6-8 lbs column head pressure); injector temperature (375°C); detector temperature (375°C); temperature program (70-375 0 C at 10°C/min ramp, 5 min at 100 0 C and 5 min at 375°C); and a 1 ⁇ l injection volume. To avoid overloading the column, attempts were made to keep the total area count within the range of 3 - 8,000,000.
  • Helium was the carrier gas and the inlet pressure was 48.2 psi in the constant flow mode at 1.5 mL/min. The split ratio was approximately 10: 1.
  • the injector and detector temperatures were 325°C.
  • the mass spectra were collected using an Agilent quadrapole mass spectrometer with source temperature of 230° C and voltage of 70 eV. A full scan was performed from 15 to 700 Daltons.
  • Hydoxyl value was measured in accordance with AOCS Cd 13— 60.
  • Acid Value Acid value was measure in accordance with AOCS Te 2a — 64 (97). 5. Ash: Ash was measured in accordance with Ca I l - 55 (03) using a 2 gram sample.
  • Moisture was measured in accordance with AOCS Ca 2e - 84 (97).
  • Density was measure in accordance with ASTM D 1475.
  • Example 1 Preparation of Polyglycerol Using Potassium Hydroxide: Into a two liter four neck flask was placed USP glycerol (99.7%, 1,195 g, 99.6 %wt.) and potassium hydroxide pellets (4.8 g, 0.4 %wt). The flask was fitted with an agitator, nitrogen sparge, horizontal condenser connected to a four inch vertical offset, 500 mL receiver and temperature and vacuum control. Nitrogen sparge was set at a medium flow; the agitator was turned on and the mixture heated to 230 0 C at a rate of 1.5°C/min. At 230 0 C, the vacuum was ramped to 160mmHg over a one-hour period. When the vacuum of 160 mraHg was achieved, the batch was sampled periodically and analyzed by GC. After 24 hours at 23O 0 C the reaction was stopped because the Hydroxyl Value did not drop below 1500 and the GC showed that
  • Example 2 Preparation of Polyglycerol Using High Oleic Sunflower Oil, Potassium Hydroxide, Fresh Glycerol and Recovered Glycerol:
  • the reaction vessel used consisted of a 10,000 gallon stainless steal reactor equipped with a vertical twelve inch diameter fifteen foot packing filled demister column with an overhead condenser, nitrogen sparge-purge, receiver and four stage jet vacuum system. Careful monitoring of the demister column showed that it was not capable of fractionating condensation codistillation mixtures (i.e., glycerol water mixtures). When no attention was given to the column the vapor temperature readily rose to within a few degrees of the kettle temperature signifying that the vapor was an aspirated kettle mixture and not a codistillation product of glycerol and water.
  • the reactor was charged with USP glycerol (99.7%, 30,280 kg, 96.6 %wt.), high oleic sunflower oil (928 kg, 3.0 %wt.) and potassium hydroxide pellets (124 kg, 0.4 %wt).
  • USP glycerol 99.7%, 30,280 kg, 96.6 %wt.
  • high oleic sunflower oil 928 kg, 3.0 %wt.
  • potassium hydroxide pellets 124 kg, 0.4 %wt
  • Prep 2 For this reaction the nitrogen sparge was set at 2 cfrn. The reactor was charged with USP glycerol (99.7%, 21,970 kg, 75.9 %wt.), recycled glycerol (6,000 kg, 20.7 %wt, from Prep 1), high oleic sunflower oil (869 kg, 3.0 %wt.) and potassium hydroxide pellets (116 kg, 0.4 %wt). The mixture was heated to 230 0 C. The condenser cooling water was set at 50 0 C. When the temperature reached 120 0 C the vacuum was ramped to 400 mmHg. At 230 0 C, the vacuum was ramped to 160 mmHg over six hours. After ten hours at 160 mmHg, the batch was sampled, and was then sampled every two hours thereafter. The in- process data is shown in TABLE 2-4.
  • Example 3 Preparation of Polyglycerol Using Adipic Acid, Potassium Hydroxide, and Fresh Glycerol: Into a two liter four neck flask fitted with nitrogen sparge, condenser, receiver and vacuum capabilities was placed glycerol (99.7%, 1529 g, 99.2 %wt.); adipic acid (7.65 g, 0.50 %wt); and potassium hydroxide pellets (4.56 g, 0.30 %wt). Nitrogen sparge was set at a medium flow. The mixture was heated to 230 0 C at a rate of 1.5°C/min. At 230 0 C, the vacuum was ramped to 160 mmHg.
  • the final composition was as follows: glycerol (32.2 %); cyclic diglycerol (2.9 %); diglycerol (29.4%); cyclic triglycerol (1.6%); triglycerol (17.6%); cyclic tetraglycerol (0.2 %); tetraglycerol (7.5%); pentaglycerol (4.7%); hexaglycerol (0.9%); heptaglycerol and higher ( ⁇ 1%).
  • Example 4 Preparation of Mixed Polyglycerol Polyol (pentaerythritol): Into a 50 gallon pilot reactor was placed USP glycerol (99.7%, 410 lbs., 77.3 %wt), alkali refined deodorized sunflower oil (16.2 lbs., 3.1 %wt.), technical grade pentaerythritol (230, 19.2 %wt.) and potassium hydroxide pellets (2.2 lbs. 0.4 %wt). The same equipment set up and procedure as seen in Example 1 was followed. The reaction was stopped after 16 hours at 230 0 C. The composition of the reaction mixture and Hydroxyl Values can be seen in FIG. 6.
  • the reaction temperature was decreased to 208 0 C and the vacuum increased to 5 mmHg.
  • the composition was as follows: glycerol (2.4 %); cyclic diglycerol (2 %); diglycerol (22.1%); cyclic triglycerol ( ⁇ 0.2%); triglycerol (16.1%); cyclic tetraglycerol
  • FIG. 5 is a chromatograph of the product of Example 4 with a chromatograph of polyglycerol over-laid to assist in distinguishing the glycerol-pentaerythritol peaks from the polyglycerol peaks. 130.9 lbs of glycerol was recovered, which was 24.5 %wt. of the total charge. Note: the vacuum was reduced to as low as ] 21 mmHg and held below 150 mmHg in an effort to determine the limits of the process. As a result, excessive glycerol was lost to the receiver during the reaction.
  • Example 5 Preparation of Mixed Poiyglycerol Fatty Alcohol. Charge USP glycerol (99.7%, 928 g, 77.3 %wt.), alkali refined deodorized sunflower oil (37 g, 3.1 %wt.), oleyl alcohol (230, 19.2 %wt.) and potassium hydroxide pellets (4.8 g, 0.4 %wt.) in a two-liter, four-neck flask. Following the same equipment set up and procedure as seen in Example 1, stop the reaction after 16 hours at 230 0 C. The water of reaction will contain about 10 %wt. glycerol.
  • the product will have a Hydroxyl Value of about 917, a viscosity of about 1100 cP @ 60 0 C and about 1 Gardner in color. Decrease the reaction temperature to about 208°C and increase the vacuum to about 5 mmHg. After 7 hours the composition will be generally as follows: glycerol (2.4 %); cyclic diglycerol (2 %); diglycerol ( 22.1%); cyclic triglycerol ( ⁇ 0.2%); triglycerol (16.1%); cyclic tetraglycerol ( ⁇ 0.1 %); tetraglycerol ( 6.3%); pentaglycerol ( 4.9%); hexaglycerol ( 1.1%); heptaglycerol and higher ( ⁇ 1%); pentaerythritol (17.7%); glycerol-oley alcohol (13.1%); two glycerol-oley alcohol (9.1%); three glycerol-oley alcohol (4.0%); four glycerol-oley
  • the final analysis shows a Hydroxyl Value of about 732, viscosity of about 2200 cP @60°C and 2+ Gardner in color. About 220 g of glycerol, 18.2 %wt. of total charge, will be recovered.

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Abstract

L'invention concerne une méthode de réaction de glycérol destinée à former un polyglycérol ou des éthers mixtes de glycérol ou d'autres alcools (p. ex. des polyols). Dans quelques modes de réalisation, la méthode consiste à réagir un glycérol en présence d'un composé contenant de l'acide gras et d'un catalyseur métallique pour former un polyglycérol. Dans d'autres modes de réalisation, la méthode consiste à réagir un glycérol et/ou un alcool en présence d'un composé contenant de l'acide gras et d'un catalyseur métallique pour former un éther mixte.
PCT/US2007/003085 2006-02-06 2007-02-06 Méthode de préparation de polyglycérol et d'éthers mixtes WO2007092407A2 (fr)

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WO2012082157A3 (fr) * 2010-12-16 2012-08-16 Rhodia Operations Procédé de préparation d'éthers de polyglycérol d'alcools gras
WO2012119711A1 (fr) * 2011-03-06 2012-09-13 Heraeus Precious Metals Gmbh & Co. Kg Procédés pour améliorer les paramètres électriques dans des condensateurs contenant pedot/pss sous la forme d'un électrolyte solide par du polyglycérol
WO2012123777A1 (fr) * 2011-03-17 2012-09-20 University Of Ottawa Procédés pour la fabrication de polyglycérol
WO2015051733A1 (fr) * 2013-10-11 2015-04-16 Rhodia Operations Composition de tensioactif comprenant un composé d'éther et son procédé de préparation catalytique
CN104629039A (zh) * 2015-03-12 2015-05-20 佛山市西伦化工有限公司 环氧聚醚醇硬脂酸酯及其生产工艺
CN104650339A (zh) * 2015-03-12 2015-05-27 佛山市西伦化工有限公司 环氧聚醚醇及其生产工艺
KR101810646B1 (ko) 2015-12-30 2017-12-20 한국과학기술연구원 직쇄형 폴리글리세롤의 제조방법
EP3305279A1 (fr) 2016-10-05 2018-04-11 Johnson & Johnson Consumer Inc. Composition de polymère absorbant le rayonnement ultraviolet
WO2018065341A1 (fr) 2016-10-05 2018-04-12 Basf Se Composition polymère absorbant les rayons ultraviolets
US10278910B2 (en) 2012-06-28 2019-05-07 Johnson & Johnson Consumer Inc. Sunscreen compositions containing an ultraviolet radiation-absorbing polymer
WO2019192943A1 (fr) 2018-04-04 2019-10-10 Basf Se Utilisation d'une composition absorbant les rayonnements ultraviolets comme stabilisant lumière pour un article polymère artificiel façonné
WO2019192982A1 (fr) 2018-04-04 2019-10-10 Basf Se Utilisation d'une composition polymère absorbant le rayonnement ultraviolet (uvrap) comme agent absorbant les uv dans un revêtement pour matières non vivantes et non kératiniques
US10874603B2 (en) 2014-05-12 2020-12-29 Johnson & Johnson Consumer Inc. Sunscreen compositions containing a UV-absorbing polyglycerol and a non-UV-absorbing polyglycerol
CN114685263A (zh) * 2020-12-31 2022-07-01 中国石油化工股份有限公司 一种二聚酸的制备方法及装置

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WO2012082157A3 (fr) * 2010-12-16 2012-08-16 Rhodia Operations Procédé de préparation d'éthers de polyglycérol d'alcools gras
US20120215031A1 (en) * 2010-12-16 2012-08-23 Rhodia Operations Process for making polyglycerol ethers of fatty alcohols
US9035104B2 (en) 2010-12-16 2015-05-19 Rhodia Operations Process for making polyglycerol ethers of fatty alcohols
US9502183B2 (en) 2011-03-06 2016-11-22 Heraeus Precious Metals Gmbh & Co. Kg Method for improving the electrical parameters in capacitors containing PEDOT/PSS as a solid electrolyte by polyglycerol
WO2012119711A1 (fr) * 2011-03-06 2012-09-13 Heraeus Precious Metals Gmbh & Co. Kg Procédés pour améliorer les paramètres électriques dans des condensateurs contenant pedot/pss sous la forme d'un électrolyte solide par du polyglycérol
CN103429796A (zh) * 2011-03-06 2013-12-04 赫劳斯贵金属有限两和公司 借助聚甘油提高包含pedot/pss作为固体电解质的电容器的电参数的方法
WO2012123777A1 (fr) * 2011-03-17 2012-09-20 University Of Ottawa Procédés pour la fabrication de polyglycérol
US8704005B2 (en) 2011-03-17 2014-04-22 University Of Ottawa Methods for making polyglycerol
CN102516038A (zh) * 2011-11-18 2012-06-27 浙江师范大学 一种多聚甘油的生产方法
US10278910B2 (en) 2012-06-28 2019-05-07 Johnson & Johnson Consumer Inc. Sunscreen compositions containing an ultraviolet radiation-absorbing polymer
US9884799B2 (en) 2013-10-11 2018-02-06 Rhodia Operations Surfactant composition comprising ether compound and catalytic process for manufacturing thereof
WO2015051733A1 (fr) * 2013-10-11 2015-04-16 Rhodia Operations Composition de tensioactif comprenant un composé d'éther et son procédé de préparation catalytique
US10874603B2 (en) 2014-05-12 2020-12-29 Johnson & Johnson Consumer Inc. Sunscreen compositions containing a UV-absorbing polyglycerol and a non-UV-absorbing polyglycerol
CN104629039A (zh) * 2015-03-12 2015-05-20 佛山市西伦化工有限公司 环氧聚醚醇硬脂酸酯及其生产工艺
CN104650339A (zh) * 2015-03-12 2015-05-27 佛山市西伦化工有限公司 环氧聚醚醇及其生产工艺
KR101810646B1 (ko) 2015-12-30 2017-12-20 한국과학기술연구원 직쇄형 폴리글리세롤의 제조방법
US10596087B2 (en) 2016-10-05 2020-03-24 Johnson & Johnson Consumer Inc. Ultraviolet radiation absorbing polymer composition
WO2018065341A1 (fr) 2016-10-05 2018-04-12 Basf Se Composition polymère absorbant les rayons ultraviolets
US10874597B2 (en) 2016-10-05 2020-12-29 Johnson & Johnson Consumer Inc. Ultraviolet radiation absorbing polymer composition
EP3305279A1 (fr) 2016-10-05 2018-04-11 Johnson & Johnson Consumer Inc. Composition de polymère absorbant le rayonnement ultraviolet
US11046814B2 (en) 2016-10-05 2021-06-29 Basf Se Ultraviolet radiation absorbing polymer composition
WO2019192943A1 (fr) 2018-04-04 2019-10-10 Basf Se Utilisation d'une composition absorbant les rayonnements ultraviolets comme stabilisant lumière pour un article polymère artificiel façonné
WO2019192982A1 (fr) 2018-04-04 2019-10-10 Basf Se Utilisation d'une composition polymère absorbant le rayonnement ultraviolet (uvrap) comme agent absorbant les uv dans un revêtement pour matières non vivantes et non kératiniques
US11773277B2 (en) 2018-04-04 2023-10-03 Basf Se Use of an ultraviolet radiation absorbing polymer composition (UVRAP) as an UV absorbing agent in a coating for non-living and non-keratinous materials
US11981793B2 (en) 2018-04-04 2024-05-14 Basf Se Use of an ultraviolet radiation absorbing composition as a light stabilizer for a shaped artificial polymer article
CN114685263A (zh) * 2020-12-31 2022-07-01 中国石油化工股份有限公司 一种二聚酸的制备方法及装置
CN114685263B (zh) * 2020-12-31 2024-05-07 中国石油化工股份有限公司 一种二聚酸的制备方法及装置

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