WO2012083149A1 - Produit de réaction issu de la déshydratation du sorbitol - Google Patents

Produit de réaction issu de la déshydratation du sorbitol Download PDF

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WO2012083149A1
WO2012083149A1 PCT/US2011/065448 US2011065448W WO2012083149A1 WO 2012083149 A1 WO2012083149 A1 WO 2012083149A1 US 2011065448 W US2011065448 W US 2011065448W WO 2012083149 A1 WO2012083149 A1 WO 2012083149A1
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composition
weight
reaction product
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PCT/US2011/065448
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Timothy Walter Abraham
Donald Michael Ference
Wei Zhang
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Cargill, Incorporated
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Publication of WO2012083149A1 publication Critical patent/WO2012083149A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems

Definitions

  • This invention relates to polyois made from the reaction product resulting from the acid-cata!yzed dehydration of a sugar aicohol (alditol). !n some particular embodiments, the reaction product comprises from 30-60% percent by weight isosorbide.
  • isosorbide which is a 6-carbon and heteroatom containing bicyclic ring compound with fused rings. It is formed by the removal of two water mo!ecules by dehydration of sorbitol. During the first dehydration step the sorbitol is converted to sorbitan; and during the second dehydration step the sorbitan is converted to isosorbide.
  • the final reaction mixture resulting from the dehydration typically contains greater than 70% percent isosorbide, which is typically purified to at least 99% through distillation to obtain high purity isosorbide that can be used in pharmaceutical and polymer applications.
  • Purified isosorbide is a crystalline solid having a meiting point of about 61 to 63°C This high purity isosorbide typically is distributed in solid crystalline form.
  • a sugar alcohol such as sorbitol
  • a dehydration reaction can undergo intramolecular cyc!lization through a dehydration reaction to obtain a reaction product that typically is a liquid at room temperature (25°C).
  • the cyclization reaction can be catalyzed or uncatalyzed.
  • acid or base catalysts are utilized, preferably an acid is utilized to catalyze the reaction.
  • the invention is a composition comprising a reaction product of the acid catalyzed dehydration of sorbitol, wherein the reaction product comprises from about 30 to about 60 weight percent isosorbide and has an AV of 2,0 or less. Typically, in this embodiment the reaction product comprises at least 2 percent by weight oligomers.
  • the invention is a composition suitable for use in the manufacture of a polyurethane, the composition comprising:
  • the invention is a process for the production of a liquid po!yol that wi!l remain a iiquid at 25°C, the process comprising:
  • step (b) removing water from the reaction mixture formed during step (a);
  • a liquid reaction product comprising from about 30 to about 60 percent by weight isosorbide (preferably from about 35 to 58 percent by weight isosorbide), at least 2 percent by weight oligomers (preferably at least 3 percent by weight), and having a viscosity of less than about 130 Pa.s at 25°C (preferably less than 100 Pa.s at 25°C), a hydroxy! number of from about 800 to about 1 100 mg KOH/gram; and
  • Iiquid polyol having an acid value (AV) of 2.0 or less, preferably 1.5 or less, and more preferably 1.0 or less.
  • FIG. 1 is a graph showing k-Factor versus time for polyisocyanurate foams made with compositions comprising the reaction product of the invention.
  • polyol refers to a molecule having an average of greater than 1 .0 hydroxyl groups per molecule (i.e. a number average hydroxyl functionality (Fn) of greater than 1.0). A polyol may also include functionality other than hydroxy! groups.
  • “Hydroxyl number” (OH#) is a measure of the hydroxy! (-OH) groups present in a material. It is reported in units of mg KOH/gram and is measured according to the procedure of AST E1899-02; with the modification that 5 ml of Tetrahydrofuran is used to initially dissolve the material instead of acetonitrile.
  • Nn Numberer average molecular weight
  • Fn is the number average hydroxyl functionality expressed in number of hydroxyl groups per polyol molecule. Fn is calculated using the equation:
  • Oligomers for purposes of this invention refers to molecules containing one or more intermolecular ether linkages that are formed during the dehydration process.
  • Intermolecular ether linkages can be formed between two sorbitol molecules, between a sorbitol and a sorbitan molecule, between two sorbitan molecules, between two isosorbide molecules, between a sorbitol molecule and an isosorbide molecule, between an isosorbide molecule and a sorbitan molecule, etc.
  • Isosorbide and sorbitan which only include intramolecular ether linkages are not considered oligomers for purposes of this invention.
  • Acid Value (AV) is determined according to the standard lUPAC method 2.201 , with the modification that distilled water is used as the solvent. Acid Value is reported in units of mg KOH/gram of material.
  • Viscosity is measured using a AR 2000 Rheometer available from TA Instruments inc. Measurement conditions are: cone and plate measuring system, gap distance of 150 ⁇ , plate diameter of 25 mm, cone angle of 5 degree and temperature of 25°C.
  • Isocyanate index refers to a measure of the stoichiometric balance between the equivalents of isocyanate groups used, to the equivalents of active hydrogens present from polyols, water, and other isocyanate- reactive components.
  • An isocyanate index of 100 means enough isocyanate groups are provided to be able to theoretically react with all the active hydrogen groups present in the formulation.
  • An isocyanate index of 200 means there are two (2) times the isocyanate groups needed to react with all the active hydrogen groups present in the formulation.
  • PIR foam for purposes of this invention refers to a polyurethane foam that results from the reaction of methylenediphenyldiisocyanate (MDI) and a polyol with an isocyanate index above 150.
  • the catalysts utilized typically vary from commonly used polyurethane foam catalysts.
  • the catalysts utilized for P!R foams promote the trimerization reaction to form isocyanurates. Examples of these catalysts typically are metal salts (preferably Group I metal salts, such as potassium acetate and potassium octoate).
  • Examples of other PiR catalysts are amine-based isocyanate trimerization catalysts, for example DABCO T R available from Air Products.
  • the PIR foams typically are stiffer than polyurethane foams made with a lower isocyanate index.
  • the PIR foams typically are more chemically and thermally stable than non PIR polyurethane foams.
  • the isocyanate index utilized for PIR foams typically is less than 500.
  • the isocyanate index utilized to make PIR foams is from 200 to 300.
  • the density of PIR foams can be adjusted depending on the overall physical properties desired in the foams.
  • molecular weight refers to number average molecular weight.
  • K-factor is measured in accordance with the procedures of ASTM- C518-04. K-factor is reported in units of watts per kelvin-meter (W/Kxrn).
  • Sorbitol is widely available and can be readily dehydrated to form a bicyciic ring structure.
  • Sorbitol C 6 H 8 (OH)6) is a six carbon sugar alcohol that is typically made by the hydrogenation of a glucose containing composition.
  • the glucose containing composition contains at least 40 percent by weight glucose, sometimes at least 50 percent by weight glucose, and often the composition contains at least 90 percent by weight glucose, for example at least 95 percent by weight glucose.
  • Sorbitol can also be obtained in a mixture by the hydrogenation of a composition obtained from the hydrolysis of sucrose.
  • unrefined sugar from sugar cane and/or sugar beets can be hydrolyzed and then hydrogenated to obtain a composition typically containing from about 40 to 80 percent by weight sorbitol (the remainder typically comprising from 20 to 60 percent by weight mannitol and other materials).
  • high fructose corn syrup obtained by the enzymatic conversion of glucose can be hydrogenated to a composition comprising sorbitol and mannitol.
  • Isosorbide can be obtained from a double dehydration reaction of a sorbitol molecule.
  • Isosorbide is a bicyclic fused ring molecule having the chemical formula: ⁇ 6 ⁇ 0 ⁇ .
  • the reaction to form isosorbide is an intramolecular cycleiization.
  • the dehydration reaction may be catalyzed or uncataSyzed, Both acid and base catalysts may be utilized.
  • the reaction preferably is catalyzed with an acid, which can be an inorganic or organic acid.
  • the acid catalyst may also be a homogeneous or heterogeneous catalyst.
  • the latter includes a homogeneous catalyst (eg. sulfuric acid) immobilized on a solid support (eg. Silica, alumina, zeolites, etc.).
  • inorganic acid catalysts that may be utilized include sulfurous, sulfuric, hydrochloric, hydrofluoroboric, phosphoric, and hypophorous acids.
  • organic acid catalysts examples include p- toluenesulfonic acid and trtf!uoromethanesulfonic acid.
  • base catalysts examples include sodium hydroxide, potassium hydroxide and sodium carbonate.
  • the catalyst typically comprises from 0.001 to 5 weight percent of the reactive mixture, preferably from about 0.01 to 2.0 percent by weight of the reactive mixture, and more preferably from 0.03 to 1.0 percent by weight of the reactive mixture and sometimes from 0.05 to 0.5 percent by weight of the reactive mixture.
  • the reaction typically is carried out at temperatures from 100°C to 195°C, from 120°C to 190°C, or from 130°C to 180°C, for example, 130°C to 165°C,
  • the pressure of the reaction typically is from a slight vacuum to a pressure of 150 to 250 torr, preferably less than 200 torr, and sometimes from 30 to 100 torr. Water is removed during the reaction in order to promote/enhance the formation of the reaction product. As described above, a slight vacuum typicaily is applied to the reactor in order to enhance the removal of water.
  • the reaction typically is carried out until the desired isosorbide content is obtained. Then the reaction typically is stopped. Methods known to one of skill in the art can be utilized to stop the reaction.
  • the temperature can be reduced below the reaction temperature.
  • an additive can be introduced that stops the reaction.
  • an agent can be introduced to stop or greatly reduce the reaction.
  • a base compound can be introduced to neutralize the acid catalyst.
  • an acid compound can be introduced to neutralize the base catalyst.
  • the additive can be utilized in connection with lowering the temperature, in order to obtain the desired concentration of isosorbide. !n an alternative aspect, no additive is utilized, but the addition of heat is removed from the reaction before the reaction is comp!ete and the reaction continues as the residual heat is removed until the desired final isosorbide content is reached in the reaction product.
  • the desired level of isosorbide typically is from 30 to 60 percent by weight, preferably from 35 to 58 percent by weight, more preferably from 35 to 55 and in some instances from 40 to 50 percent by weight isosorbide of the reaction product.
  • the inventors have found that the viscosity of the reaction product decreases as the weight percent of the isosorbide increases. However, the inventors have surprisingly found that if the weight percent of the isosorbide is maintained below a certain level that crystallization within the reaction product when it is cooled to room temperature (25°C) can be prevented or minimized. This provides a composition that can be readily handled for a variety of end-use applications.
  • the amount of isosorbide is measured using liquid chromatography as further described below.
  • the amount of isosorbide present during the reaction does not need to be measured directly, instead, the amount of water removed may be used to estimate how far the reaction has progressed. By carrying out several test manufacturing runs, correlations can be developed that relate the amount of isosorbide present in the reaction product to the amount of water removed from the reactor. Also, the amount of weight loss from the reactor can be monitored in order to determine the degree of isosorbide formation and this information can be used to determine when to stop adding heat to the reaction (and/or when to begin cooling the reaction and/or when to add a catalyst kill agent to the reaction).
  • the reaction product typically has a viscosity of 130 Pa.s or less at 25°C, preferably 100 Pa.s or less, and more preferably 60 Pa.s or less at 25°C, and in some instances 50 Pa.s or less, for example 40 Pa.s or iess at 25°C.
  • the reaction product typically has from about 30 to 60 percent by weight isosorbide as determined by liquid chromatography analysis, preferably from 35 to 58 percent by weight, and more preferably from 35 to 55 percent by weight.
  • the reaction product is substantially free of visible crystals at room temperature.
  • substantially free of visible crystals it is meant that the solution is substantially a single phase homogeneous liquid, which lacks visible haze or turbidity when visually inspected. Additionally, if substantial crystals are present in the reaction product, the overall liquid may appear to be crystal free, but the surface of the reaction product will often appear to be rough or non-smooth.
  • the reaction product is substantially free of crystals visible to the naked eye for at least 8 hours after the reaction is complete.
  • the reaction product is substantially free of crystals for 10, 20, 30, 60, 90 days at 25°C after being produced.
  • a diluent polyol as described more fully below and/or water may be added to the reaction product.
  • the isosorbide content of the reaction product may be higher.
  • the isosorbide content may be from 60 to 80 percent by weight (for example from 65 to 75 percent by weight) in the reaction product.
  • the isosorbide content is high enough that the reaction product may crystallize to form a solid at room temperature (25°C), However, the reaction product when mixed with a diluent polyol may remain liquid for a sufficient period of time to enable a polyisocyanurate foam to be made utilizing the composition containing the reaction product.
  • the composition containing the reaction product may be heated prior to use to dissolve any crystals to enable the reaction product being utilized to manufacture a polyurethane article, such as a polyisocyanurate foam.
  • the reaction product comprising a high isosorbide content can be blended with a reaction product comprising a lower isosorbide content to provide a blended reaction product, which has the preferred isosorbide content described above.
  • the reaction product typically has at least 2 percent by weight oligomers, preferably at least 3 percent by weight oligomers, and may have at least 5, 7, 9 percent by weight, sometimes at least 10 percent by weight, for example at least 15 percent by weight oligomers based on the weight of the reaction product. While not intending to be bound by theory, it is believed that the high levels of oligomers may enhance the reaction products tendency to remain a liquid at room temperature.
  • the reaction product typically has a hydroxyl number of 1200 mg KOH/gram or less, preferably less than 1 100 mg KOH/gram, and in some instances less than 1000 mg KOH/gram. In some aspects, the reaction product has a hydroxyl number from 800 to 1 100 mg KOH/gram, sometimes from 850 to 1000 mg
  • the reaction product typically comprises residual water, typically less than 5 percent by weight residual water. For some applications (such as
  • polyisocyanurate foams it may be preferable to limit the amount of water in the reaction product to 2 percent by weight or less, sometimes 1.5 percent by weight or less, and in some instances less than 1.0 percent by weight or less, for example, 0.7 percent by weight or less.
  • the reaction product may be aikoxylated using, for example, ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof in accordance with methods known to one of skill in the art to further lower the viscosity of the reaction product.
  • hydroxyl number for these type of polyols typically wil! be from 200 to 800 mg KOH/gram, for example from 210 to 400 mg KOH/gram and preferably from 220 to 250 mg KOH/gram, and when the alkoxy groups make up from 5 to 10 percent by weight of the reaction product, the hydroxyl number will typically be from 750 to 1000 mg KOH/gram.
  • the reaction product can be utiiized neat or a diiuent polyol (as described below) may be added to the reaction product.
  • a diluent polyol as described below is added to the reaction product to provide a composition where isosorbide is less likely to crystallize from the composition, and also to reduce the viscosity. This enables the composition to remain liquid at room temperature (25°C).
  • the diluent polyol preferably is a liquid at room temperature (25°C) and typically has a molecular weight of from 40 to 500 Daltons, preferably 50 to 300 Daltons, and more preferably from 60 to 200 Daltons.
  • diluent polyols that can be utilized in the invention include, for example: glycols, polyethylene glycol, diethylene glycol, 1 ,3 propanediol, poly(1 ,3-propanediol),1 ,4 butanediol, poly(1 ,4-butanediol), polypropylene glycol, dipropylene glycol, glycerol, polyglycerol, 1 ,4-dihydroxycyclohexane, propylene glycol, ethylene glycol, and mixtures thereof.
  • glycols polyethylene glycol, diethylene glycol, 1 ,3 propanediol, poly(1 ,3-propanediol),1 ,4 butanediol, poly(1 ,4-butanediol), polypropylene glycol, dipropylene glycol, glycerol, polyglycerol, 1 ,4-dihydroxycyclohexane, propy
  • the diluent polyol utilized has a number average hydroxy! functionality (Fn) of less than 4, and preferably has a number average hydroxyl functionality of from 2 to 3.
  • the diluent polyol is liquid at 25°C, and has a viscosity less than 10 Pa.s at 25°C, preferably less than 8 Pa.s, and more preferably less than 5 Pa.s at 25°C, and sometimes less than 1 Pa.s at 25°C, for example less than 0.5 Pa.s or less than 0.2 Pa.s at 25°C. Water may also be added to the reaction product, either alone or together with a diluent poiyo!.
  • the water typically is at levels of 2% by weight or less, preferably 1.5% by weight or less, and sometimes 1.0% by weight or less of the composition containing the reaction product and any diluent present (including water).
  • the viscosity typically is 30 Pa-s or less at 25°C, preferably 20 Pa.s or less, and more preferably 15 Pa.s or less at 25°C, and in some instances 10 Pa.s or less at 25°C.
  • diethylene glycol preferably is utilized.
  • Another preferred diluent polyol is polyethylene glycol having a molecular weight from 106 to 200 Daltons, and a viscosity from 0.05 to 0.07 Pa.s at 25°C.
  • the weight ratio of diluent polyol to sorbitol typically is from 1 :99 to 40:60, from 5:95 to 30:70, preferably from 5:95 to 25:75, and more preferably from 7:93 to 20:80.
  • the resulting material typically has a hydroxyl number of 1300 mg KOH/gram or less, preferably less than 1250 mg KOH/gram, and more preferably less than 1200 mg KOH/gram, and in some instances less than 1000 mg KOH/gram.
  • reaction products can be utilized in a variety of end-use applications.
  • the reaction product can be used in manufacture of polyesters and polyurethanes.
  • the reaction products can be utilized in foam applications and in coatings, adhesives, sealants, and elastomers (CASE) type applications, in one particular preferred embodiment, the reaction product is utilized in the manufacture of rigid polyurethane foams. In another particular preferred embodiment, the reaction product is utilized in the production of polyisocyanurate foams.
  • Terate®4020 an aromatic polyester polyol available from Invista. in the tables referred to as Terate ⁇ 4020.
  • Glycerol USP grade having a viscosity at 25°C of 0.88 Pa.s, an OH# of 1829 mg KOH/gram, a molecular weight of 92 Daitons, and an Fn of 3, available from Cargill, Incorporated.
  • GLY Glycerol
  • a series of six standard solutions containing isosorbide and sorbitol are prepared in ultra high pure (UHP) water.
  • the six standard solutions contain 8000, 4000, 2000, 1000, 500, and 200 ppm of isosorbide, and 100 ppm, 50 ppm, 25 ppm, 12.5 ppm, 6.25 ppm and 2.5 ppm of sorbitol respectively.
  • the individual solutions were injected into the chromatograph, and standard curves (i.e. concentrations for a given response) were generated for isosorbide and sorbitol based on the area under the peaks as determined from the chromatagrams.
  • the standard curve for isosorbide was used to estimate the sorbitan concentration, since a highly pure sorbitan sample was unavailable.
  • the oligomers present in each experimental sample was determined based on the retention times and response of the high molecular weight compounds shown In the chromatograms, and a percentage reported for these oligomers based on the area under the high molecular weight component peaks relative to the area under all the peaks in the chromatogram.
  • Example 1 Dehydration of sorbitol at 135°C with 0.5 % by weight p-Toiuene sulfonic acid
  • a medium vacuum of about 200-300 mbar is applied, and the temperature is maintained from 130-140 lC for another 20 minutes until 99% of the water that was in the sorbitol solution was stripped out.
  • 1.75 grams (6.3 grams for Sample 1 -2 and 25.3 grams for Sample 1-3) of p-Toluenesulfonic acid ("PTA") is charged to the flask.
  • PTA p-Toluenesulfonic acid
  • the flask is maintained at 130-140 lC with agitation and a nitrogen sparge and with no vacuum for one hour, followed by at 130-140 lC under vacuum of about 200 mbar with agitation and a nitrogen sparge until the reaction has continued to a point where a reaction product having the isosorbide levels indicated in Table 1 will be obtained once cooled.
  • the extent of the reaction is determined by measuring the weight loss from the flask. Once the reaction has reached the extent desired, the flask is cooled to below 100°C and then the resulting reaction product is transferred to a glass container and stored at room temperature (25°C). The resulting reaction products have the physical and chemical properties indicated in Table 1.
  • Example 2 dehydration of sorbitol at 135°C with 1. 0 % by weight p- Toluenesulfonic acid (PTA) in a larger scale reactor design:
  • the reactor consists of a 190 liter 304 Stainless Steel pressure vessel, jacketed for cooling with chilled water and an internal coil for heating with hot oil.
  • the reactor contains a mechanical agitator driven by a 1 horsepower air powered motor for continual agitation of the reactive mixture.
  • the overhead condenser is a shell and tube heat exchanger with cooling water on the shell side and located in between the vacuum pump and the reactor. The overhead condenser condenses vapors into liquid, which then gravity feeds into a 23 liter condensate receiver. When desired, vacuum is pulled on the reactor, through the overhead condenser by the vacuum pump.
  • a dry ice trap is installed between the outlet of the overhead condenser and the inlet of the vacuum pump to condense any vapors not condensed at the cooling water temperature.
  • the resulting reaction product is unloaded through a Stainless Steel Filter with a 50 micron Polyester Filter Element.
  • the oil heater is set to maintain the reactor temperature at 130 °C.
  • the vacuum pump is started and gradually establishes a vacuum of ⁇ 150 mmHg.
  • the overhead sight giass is observed for foaming and air is bled into the pump when necessary to minimize foaming.
  • the reactor is cooled to 75°C and the product product filtered through into a drum through a 50 micron fiiter.
  • Example 3 Dehydration of sorbitol at 160°C with 0.14 % by weight sulfuric acid
  • a medium vacuum of about 200-300 mbar is applied, and the temperature is maintained from 130-140 iC for another 20 minutes until 99% of the water that was in the sorbitol solution was stripped out.
  • 1.43-1 .53 grams of 1 : 1 sulfuric acid in water are charged to the flask.
  • a Vigreux distillation column is inserted between the water collector and the flask.
  • the flask is maintained at 160 lC under vacuum of about 130-150 mbar with agitation and a nitrogen sparge until the reaction has continued to a point where a reaction product having the isosorbide levels indicated in Table 2 will be obtained once cooled.
  • the extent of the reaction is
  • the flask is cooled to below 100°C and then the resulting reaction product is transferred to a glass container and stored at room temperature (25°C).
  • the resulting reaction products have the content profile measured by HPLC as indicated in Table 2. All the samples of Table 2 had less than 1 percent by weight water. The entire reaction typically takes from between 0.5 and 2 hours, depending on the desired final isosorbide weight percent in the reaction product.
  • Example 3 All products from Example 3 (3-1 to 3-6) were blended with four different diluent polyols of EG, DEG, PG and glycerol at two different levels of 5% and 10%, and the viscosity of the blends are displayed in Table 6, and the crystallization study by seeding are given in Table 3.
  • the acid value of the reaction product may be lowered further by the addition of a base to the reaction product.
  • a base such potassium hydroxide and sodium hydroxide are utilized.
  • the use of such a base may lower the acid value of the reaction product below that obtained from the acid catalyzed reaction, for example !ess than 2 mg KOH/gram, preferably less than 1.5 mg KOH/gram, more preferably less than 1.0 mg KOH/gram, and in some instances less than 0.5 mg KOH/gram.
  • an acid value (AV) less than 1.5, 1 .0 or 0,5 mg KOH/gram can readily be obtained.
  • Samples 1 -2, 1-3 and 3-1 to 3-6 are seeded with isosorbide crystals (99% pure) as follows:
  • the rough surface may indicate that higher levels of crystals may eventually develop.
  • Samples 1-2 and 1 -3 were blended with solvents of DEG, glycerol, and a mixture of 50% DEG and 50% glycerol at three different diluent polyol levels of 5%, 10% and 15%.
  • the blends contain approximately 1 percent or less by weight water.
  • the viscosity of the blends is given in Table 4, and the crystallization study by seeding is shown in Table 5.
  • Table 4 shows the viscosities for Samples 1 -2 and 1 -3 with various diluent polyol added.
  • Table 6 shows the viscosities for Samples 3-1 to 3-6 both as neat products (i.e. no diluent polyol added) and with various diluent polyol added. This example shows that !iquid polyols of the invention can be obtained that exhibit relatively low values for viscosity as set forth in Tables 4 and 6
  • the percent by weight isosorbide in the reaction product is from 30 to 60 percent by weight, preferably from 35 to 58 percent by weight, more preferably from 35 to 55 percent by weight and in some instances from 40 to 50 percent by weight.
  • the inventors have surprisingly discovered that a suitable reaction product can be obtained by blending a first reaction product having an isosorbide content greater than desirable with a reaction product having a lesser isosorbide content.
  • the resulting reaction product has the isosorbide content in the preferred ranges described above and also exhibits the desirable characteristics exhibited by a reactor grade reaction product that when made has a simi!ar isosorbide content.
  • reaction products of Examples 1 and/or 2 could be blended in sufficient amounts with reaction products similar to Samples 3-1 , 3-2, and 3-3 to obtain a blended reaction product that has an isosorbide content from 30 to 60 percent by weight, preferably from 35 to 58 percent by weight, more preferably 35 to 55 percent by weight, and in some instances from 40 to 50 percent by weight.
  • the formulation containing the inventive polyol ⁇ Runs 2-5) reacts slower than the control formulation (Run 1 ) and therefore requires higher levels of catalysts and surfactant as set forth in Table 7. All other components in Runs 2-5 remained at the same level as in the control Run 1.
  • the Isocyanate Index was fixed at 200, targeting a 32 kg/m 3 Density foam for all Runs.
  • the inventive polyol in the polyol formulation with a isocyanate index typically from 150 to 300 (for example 180 to 260); and obtain a PI foam having compressive strength in the Y Direction of at least 150 (preferably at least 180) kilopascals, an initial k-Factor of less than 0.027 (preferably less than 0.026).
  • the compressive strength in the X Direction is at least 100 (preferably at least 120) kilopascals
  • the compressive strength in the Z Direction is at least 100

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Abstract

L'invention concerne un produit de réaction issu d'une déshydratation catalysée acide du sorbitol. Le produit de réaction a un pourcentage en poids d'isosorbide compris entre 30 et 60 et a une valeur acide inférieure ou égale à 2,0. Selon certains aspects, le sorbitol peut être obtenu par hydrogénation d'une composition contenant du glucose. Selon d'autres aspects, le produit de réaction peut comprendre au moins 2 % en poids d'oligomères. Le produit de réaction peut être approprié à la fabrication de mousse de polyisocyanurate. Selon certains aspects, le produit de réaction peut être mélangé à des polyols de diluant, tels que des diols, des glycols, l'éthylène glycol, le diéthylène glycol, le dipropylène glycol, le propylène glycol, le polyéthylène glycol, le polypropylène glycol et des mélanges de ceux-ci.
PCT/US2011/065448 2010-12-17 2011-12-16 Produit de réaction issu de la déshydratation du sorbitol WO2012083149A1 (fr)

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WO2014070369A1 (fr) * 2012-10-31 2014-05-08 Archer Daniels Midland Company Hydrogénation de produits de type isohexide en vue d'une amélioration de couleur
FR3021329A1 (fr) * 2014-05-26 2015-11-27 Roquette Freres Substrat methanogene pour la fabrication de biogaz.
US9266898B2 (en) 2010-12-17 2016-02-23 Cargill, Incorporated Reaction product from the co-dehydration of a sugar alcohol and a polyol
CN105967347A (zh) * 2010-11-29 2016-09-28 捷通国际有限公司 泡沫材料水处理系统
EP2933256B1 (fr) 2012-12-14 2019-05-22 Samyang Corporation Procédé d'élaboration d'un alcool d'anhydrosucre au moyen d'hydrol
US10414859B2 (en) 2014-08-20 2019-09-17 Resinate Materials Group, Inc. High recycle content polyester polyols

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US9266898B2 (en) 2010-12-17 2016-02-23 Cargill, Incorporated Reaction product from the co-dehydration of a sugar alcohol and a polyol
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CN106414455A (zh) * 2014-05-26 2017-02-15 罗盖特公司 用于沼气生产的产甲烷生物体底物
JP2017524657A (ja) * 2014-05-26 2017-08-31 ロケット フレールＲｏｑｕｅｔｔｅ Ｆｒｅｒｅｓ バイオガス生成のためのメタン発酵基質
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