• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    “POLYOL POLYESTER AROMATIC, E, COMPOSITION TO PREPARE POLYURETHANE FOAM” Aromatic polyester polyols with high functionality, moderate viscosity and high aromatic content are revealed as the only polyol in the production of polyurethane foams without the use of any polyether polyol. This unique combination of properties makes them suitable for use as the only polyol in the production of polyurethane foams. With reduced flame retardants, these foams based on a single aromatic polyol can have E-84 class one fire properties. The aromatic polyester polyols of this invention are characterized with a functionality greater than 2.8 at the same time with a moderate viscosity ranging from 4,000-10,000 cps to 25 C. A high-performance polyester polyol typical of the present invention has a hydroxyl number in the range 320-400, viscosity 4,000-10,000 cps at 25 C, functionality greater than 2.8 and percentage content of phenyl greater than 14.75.
    公开号:BR112014025257B1
    申请号:R112014025257-2
    申请日:2013-04-02
    公开日:2020-12-29
    发明作者:David J. Shieh
    申请人:Huntsman International Llc；
    IPC主号:
    专利说明:

    [0001] This application claims priority benefit for U.S. provisional application No. 61 / 622,293, filed on April 10, 2012, which is hereby incorporated by reference in its entirety. FIELD OF THE INVENTION
    [0002] The present invention relates to certain aromatic polyester polyols suitable for use in making polyurethane foam, and methods for preparing such polyols. In particular, the invention concerns aromatic polyester polyols with high functionality (greater than 2.8) and moderate viscosity (less than about 10,000 cps). The present invention further relates to polyurethane foams produced from such compositions based on high functionality polyester polyol, and to methods for preparing such polyurethane foams. BACKGROUND OF THE INVENTION
    [0003] Most of the aromatic polyester polyols used in the production of polyurethane (PU) foams have low functionality in the 2-2.5 range. As functionality increases to 2.5, so does viscosity. Typical viscosity of an aromatic polyester polyol with a functionality approaching 2.5 is above 10,000 cps, too high to be used as a single source of polyol, due to the viscosity limitations of PU foam production equipment. Thus, they are combined with high-functional / low-viscosity polyether polyols to produce commercially valuable PU foams.
    [0004] Aromatic polyester polyols have been used in polyurethane and polyisocyanurate foams for some time. U.S. Patent Nos. 4,604,410 and 4,701,477 disclose a method for producing rigid polyurethane and polyisocyanurate foams that require reacting an excess of an organic polyisocyanate with an etherified modified aromatic polyol. The etherified modified aromatic polyol is prepared by digesting recycled poly (alkylene terephthalate) (PET) polymers with a low molecular weight polyol, such as diethylene glycol. The resulting product is then mixed with a low molecular weight polyol, such as alpha methyl glycoside. The intermediate product is etherified with propylene oxide and / or ethylene oxide.
    [0005] U.S. Patent No. 4,469,824 provides a method for producing liquid terephthalic esters that are used as polyol extenders in rigid polyurethane foams and as the only component polyol in polyisocyanurate foams. Terephthalic esters are produced to remain in a liquid form by reacting recycled poly (ethylene terephthalate) (PET) with diethylene glycol and one or more oxyalkylene glycols. Ethylene glycol is then removed from the reaction to produce an ester mixture that is free of solids upon rest. Due to the solubility limit, a maximum of 5% alpha-methyl glycoside can be added to increase the functionality of the resulting product.
    [0006] US Patent No. 4,644,019 discloses a method for preparing isocyanurate foam which is similar to the methods disclosed above, but this method includes reacting an alkylphenol ethoxylate, preferably nonylphenol with the poly (ethylene terephthalate) while being digested .
    [0007] U.S. Patent No. 5,360,900 discloses a method for producing high functionality and a high aromatic content at conventional viscosity by combining ethoxylated methyl glycoside or propoxylated methyl glycoside with a poly (ethylene terephthalate) based polyester.
    [0008] None of the polyols described above can be used as the only polyol in the production of polyurethane foams because they do not have sufficiently high functionality. The present invention provides a series of highly functional polyester polyols to meet the challenge. SUMMARY OF THE INVENTION
    [0009] The present invention concerns a new and surprisingly useful class of aromatic polyester polyols suitable for use in the manufacture of polyurethane foams. The present invention further relates to polyol-based compositions prepared using such polyols and a blowing agent. The present invention further concerns polyurethane foams produced from such polyol based compositions, and methods for preparing such polyurethane foams.
    [00010] The polyols of this invention have moderate viscosity, very high functionality, and high aromatic content. This unique combination of properties makes them suitable for use as the only polyol in the production of polyurethane foams. None of the polyether polyols are present in the formulation. With minimal amount of flame retardants, the foam based on this unique aromatic polyester polyol can have a class E-84 fire properties rating. The aromatic polyester polyols of this invention are characterized with a functionality in the range of 2.8 to 3.2 while having a moderate viscosity ranging from 4,000-10,000 cps at 25 C. A typical high-performance polyester polyol of the present invention has a hydroxyl number in the range 320-400, viscosity from 4,000 -10,000 cps at 25 C. Typically, functionality will vary from 2.8 to 3.2 and the percentage phenyl content will range from 14.75 to 19.58.
    [00011] The inventive polyol is prepared by transesterification or esterification of a mixture comprising: 34-66% w / w glycols, 24 - 34% w / w terephthalate source, 0-17% w / w glycerin, glycerin refined, crude glycerin, 0-14% w / w pentaerythriol, dipentaerythriol, tripentaerythriol, 0-5% w / w methyl glycoside, 0-10% w / w sorbitol, 0-15% w / w vegetable oil natural, modified natural vegetable oil such as epoxidized soybean oil or pine oil fatty acid.
    [00012] This invention also provides a composition for preparing PU foam. The typical formulation for a PU foam used in spray applications comprises two components: an A side comprising a polyisocyanate and a B side, comprising a mixture of multiple ingredients including catalysts, surfactant, flame retardant, blowing agent and mostly a polyol component consisting essentially of the high viscosity, aromatic, polyester polyol of this invention. Typically, the polyol component will be 65-80% (w / w) of the B-side component. The polyol component does not include any contribution from the polyethers.
    [00013] A further aspect of the invention provides a method of applying a polyurethane foam comprising the steps of: providing a side A component comprising polyisocyanate and a side B component comprising catalysts, surfactant, flame retardants, blowing and mostly a polyol component consisting essentially of high-functionality aromatic polyester polyol, of inventive moderate viscosity, preparing a surface on which to apply the foam; react the components of side A and side B; and apply the reaction components to a surface. The method of forming a PU foam is advantageously applied to a surface of a roof, a structural wall, an insulated cavity, a storage tank or a process vessel. DETAILED DESCRIPTION OF THE INVENTION
    [00014] The previous formulation of the typical technology for a PU foam used in spray applications is shown in Table 1. This type of application requires two components: an A side, a polyisocyanate and a B side, a mixture of multiple ingredients including an aromatic polyester polyol and polyether polyol.
    [00015] The A-side polyisocyanate component of the formulations of the present invention preferably includes that known to those skilled in the art, and is not intended to limit the A-side component to that specifically illustrated here. For example, the A-side polyisocyanate component of the formulations of the present invention can be advantageously selected from organic polyisocyanates, modified polyisocyanates, isocyanate-based prepolymers, and mixtures thereof. This may include aliphatic and cycloaliphatic isocyanates, but aromatic and especially multifunctional aromatic isocyanates are preferred, and polyphenyl polymethylene polyisocyanates (PMDI) is above all preferred. Such preferred commercially available PMDI products include Mondur.RTM. MR Lite from Bayer Corporation, Rubinate.RTM. M from Huntsman Corporation, and the like. PMDI in any of its forms is the polyisocyanate above all preferred for use with the present invention.
    [00016] The requirements for a successful B side are: (1) be visually clear; (2) have stable reactivity for a period of time; (3) have adequate operating viscosity. Subsequently, the polyurethane (PU) foam is generated from the reaction of equal volume one to one on side B and side A, by means of a high pressure spray equipment with proportional heating and measuring capabilities. The spray PU foam must: (1) be dimensionally stable (2) has minimal compressive and tensile strength and a nominal density of two pounds; (3) must have class E-84 I fire property classified for use as internal insulation. Class E-84 I classification is based on foam burning results with flame spread less than or equal to 25 and smoke density less than or equal to 450. The biggest challenge for formulators is to have less smoke density or equal to 450 for your PU foams.
    [00017] The balanced formulation of the typical B side side technology in table 1 meets all the requirements mentioned above. With details, the aromatic polyester polyol is Terol 256 (manufactured and sold by Oxid LP); polyethers are a combination of JEFFOL R470X and Carpol GSP 280 in a weight percentage of 15 and 8 respectively. Flame retardant 1 is tris phosphate (1-chloro-2-propyl (TCPP) and Flame retardant 2 is PHT4diol, a brominated anhydrous polyol. The surfactant is a silicon-based cell regulator. breath are water and HFC 245FA (1,1,1,3,3-pentafluorpropane) with a weight percentage of 2.2 and 8 respectively.

    [00018] Other blowing agents that can be used include 365mfc / 227 (a mixture of 1,1,1,3,3-pentafluorbutane and 1,1,1,2,3,3,3-heptafluorpropane from Solvay), Solstice ™ - 1233zd (E) (Honeywell trans-1-chloro-3,3,3-trifluorpropane) and FEA-1100 (DuPont Hexafluoro-2-butene). The B-side component includes at least one amine catalyst. Commercially available amine catalysts suitable for the present invention include Policat.RTM. 9, PolicatRTM. 12, and Dabco.RTM. BL-19 from Air Products .; Toyocat DM 70 from Tosoh Specialty Chemicals USA, Inc. Surfactants such as these are commercially available as LK-443 and Dabco.RTM. Air Products DC-193, and the like can also be used in the present invention. In addition, flame retardants such as Great Lakes PHT-4 Diol, Akzo-Nobel Fyrol.RTM.PCF, ICL Industrial Fyrol 6 and the like can be used in the B-side component of the present invention.
    [00019] Preferably, the ratio of isocyanates: volume B is 1: 1. Although not desired, a 10% deviation from this ratio is tolerated. Glossary / definition: Polyol functionality - The average number of reactive group per mole of polyol. It is determined by average molecular weight by the number of polyol (Mn) divided by weight of equivalent polyol (Eqwt). Mn can be measured by gel permeation chromatography (GPC) or steam pressure osmometry (VPO). Eqwt can be obtained by 56,100 divided by the number of polyol hydroxyl. There are many ways to determine the polyol hydroxyl number, the most popular being wet method titration. Aromaticity - Terephthalate means a phenyl group with 4 hydrogen attachments and 2 carbonyl group, the molecular weight is 132. Phenyl means a benzene ring with four hydrogen attachments, molecular weight is 76. Blowing Agent (BA) solubility - It is a measurement of how many grams of BA in 100 grams of polyol before reaching the saturation point (the solution becomes cloudy), expressed as parts per hundred parts of polyol (pphpp). Compressive strength - And based on ASTM D 1621-73, a measure of the foam's ability to resist axially directed thrust force. Dimensional stability - And based on ASTM D2126-87, a measurement of the foam's ability to retain its precise shape in different temperature and humidity environments. Classification is given for the aged foam. A is the best and D or below is unacceptable. Green resistance - A measurement of the foam's ability to resist force before complete curing occurs. Foam with greater general functionality would experience less recess (penetration) than foam with less functionality of the same density and reactivities. SDR - The average smoke density of foam (three burns) from the smoke box. Jeffol R470X, R425X - A Mannich-based polyether polyol produced by Huntsman. Caprol GSP 280 - A sucrose / glycerin-based polyether polyol produced by E.R. Carpenter. DM 70 - Toyocat DM70 is an amine polyurethane catalyst from Tosoh USA DC 193 - A silicon based cell regulator from Air Products BL 17 - An amine polyurethane catalyst from Air Products PC 9 - An amine polyurethane catalyst from Air Products Crude glycerin - collected from the biodiesel process, normally contains water, glycerin, free fatty acid, fatty acid methyl ester, soap, ash and a transesterification catalyst such as potassium hydroxide. Percentage of Polyol Solids - is determined by Universal Centrifuge (3,000 rpm for 15 minutes) for 50% solvent and 50% polyol sampler.
    [00020] Table 2 summarizes the advantages and disadvantages of each ingredient in the formulation of the previous technology on side B. Terol 256 is aromatic-based polyester with hydroxyl number of 265, viscosity of 11,000 cps at 25 C and functionality of 2.3 . Jeffol-470X is an aromatic amine with hydroxyl number of 470, viscosity of 10,000 cps at 25 C and functionality of 3.10. GSP 280 is a polyether polyol based on propylene oxide initiated with sucrose / glycerin with hydroxyl number of 280, viscosity of 3,000 cps at 25 C and functionality of 7.0. TCPP is tris phosphate (l-chloro-2-propyl with a viscosity of 65 cps at 25 C. It contains 9.5% phosphate and 32% chlorine. PHT4diol is a brominated polyester polyol (ester of tetrabromophthalic acid) with number of hydroxyl of 215 and viscosity of 100,000 cps at 25 C. It contains 46% of bromine.HFC 245 is 1,1,1,3,3 - pentafluorpropane.

    [00021] Terol 256 provides the main aromaticity / phenyl to suppress smoke density and increase coal formation of PU foam, but, it lacks the functionality, so polyester polyol can no longer be used due to the resulting PU foam does not meet the standard of dimensional stability and compressive strength. Polyether polyols provide functionality for the foam, but, they also increase the density of smoke due to their propylene oxide content.
    [00022] In terms of the fire properties of the foam, TCPP stops the spread of the flame over the foam creating a thermal protective charcoal. Chlorine in TCPP and bromine in PHT4 diol undergo thermal degradation and release radicals of chloride and bromide that reduce the flame spread of the gas phase and evolution of the smoke. Another advantage of TCPP is that it reduces the viscosity of the B side. However, it also acts as a plasticizer and actually impairs the dimensional stability as well as the mechanical properties of the foam. To meet the classification of an E84 class, foams from the prior art they need both TCPP and PHT4diol (correct reason) in the formulation.
    [00023] The cost structure of each ingredient in descending order is PHT4diol, TCPP, polyether polyols and aromatic polyester polyols. Formulators would prefer to use more aromatic polyester, less flame retardants, and no polyether polyol. Thus, PU foams will have better fire properties and lower cost, but unless the aromatic polyester polyol has high functionality this could not be achieved until the polyols of this invention are developed.
    [00024] With the new polyester HF polyol composition of this invention, a new side B can be formulated as the following table 3:

    [00025] Subsequently, the polyurethane foam produced on the B side according to table 3 and polyisocyanate can meet the current requirement for PU spray foam.
    [00026] Oxid has developed a series of highly functional polyester polyols to meet the challenge. A typical high-functionality polyester (HF) polyol has a hydroxyl number ranging from 320-400, a viscosity of 4,000-10,000 cps at 25 C, a functionality greater than 2.8 and a percentage of phenyl content greater than 14.75 (typically a terephthalate content (TERE) greater than 25.62. Table 4 shows a typical transesterification formulation or direct esterification to produce the inventive HF polyester polyol.

    [00027] In a broad sense, glycols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol and polypropylene glycol.
    [00028] Glycerin includes petroleum-based, plant-based, animal-based, raw and refined grade of recycled biodiesel.
    [00029] Pentaerythriol (PE) includes source of mono, technical, di-pentaerythriol, tripentaerythriol and by-product of manufacturing PE.
    [00030] Methyl glycoside includes alpha / beta methyl glycoside.
    [00031] TER.E is terephthalate and it comes from poly (ethylene terephthalate) (PET), industrial recycled PET, post consumer PET, terephthalic acid (TA), industrial recycled TA (Aromatic carboxylic acid by-product), italic anhydride, isophthalic acid and metaphalic acid.
    [00032] Natural oil / fatty acid includes castor oil, palm oil, cotton oil, soybean oil, corn oil, linseed oil, tung oil, pine oil fatty acid, dimer oil and trimer oil. Modified oil includes epoxidized natural oil.
    [00033] We also know that trimethylpropane (TMP) and sorbitol can be used to replace glycerin or PE in this application.
    [00034] The following examples illustrate the present invention, and are not intended to limit the scope of the invention in any way. EXAMPLE 1
    [00035] Researchers first added 113 grams of diethylene glycol, 1,359 grams of triethylene glycol, 566 grams of tetraethylene glycol, 426 grams of glycerin, 1,917 grams of poly (ethylene terephthalate) and 4 grams of Tyzor TE (a titanate chelate of triethanolamine) in a 5 liter 4-neck glass jar that is equipped with a reflux condenser, separation column, suspended receiver and a thermocouple.
    [00036] Researchers then heat the pot to 450 degrees F (232.2 ° C) and maintain the pot's temperature at 450 degrees F (232.2 ° C) for 2 hours. Then, the pot is allowed to cool below 250 degrees F (121.1 ° C).
    [00037] When the temperature reaches 250 degrees F (121.1 ° C), researchers add 154 grams of mono PE and 412 grams of castor oil. The pot is heated to 460 degrees F (237.8 ° C) with vacuum pressure at 150 mm Hg. The return to receipt ratio is set at three to one. Researchers continue the reactive distillation process until the theoretical amount, 599 grams of ethylene glycol, is distilled from the reaction mixture.
    [00038] The polyol produced according to the previous transesterification method has the following properties: Hydroxyl number 313; Acid number 0.50; Viscosity at 77 degrees F (25 ° C). 9,400 cps. Hydroxyl number went up to 333 adding some diethylene glycol. The final properties are as follows: Hydroxyl number 333; Acid number 0.50; Viscosity at 77 degrees F (25 ° C). 7,800 cps. Polyol appearance Clear amber liquid Polyol functionality according to calculation 3.0 Phenyl in polyol 17.45 Solubility of HFC 245fa in pphpp 30 Solubility of Solstice ™ - 1233zd (E) in pphpp 32.9 Solubility of FEA-1100 in pphpp 13.3 The polyol is labeled DS-16059-1. EXAMPLE 2
    [00039] Researchers first add 218 grams of diethylene glycol, 1.376 grams of triethylene glycol, 571 grams of tetraethylene glycol, 223 grams of glycerin, 1,827 grams of poly (ethylene terephthalate) and 4 grams of Tyzor TE (a titanate chelate of triethanolamine) in a 5 liter 4-neck glass jar that is equipped with a reflux condenser, separation column, suspended receiver and a thermocouple.
    [00040] Researchers then heat the pot to 450 degrees F (232.2 ° C) and maintain the pot's temperature at 450 degrees F (232.2 ° C) for 2 hours. Next, the researchers will let the pot cool down to 250 degrees F (121.1 ° C).
    [00041] When the temperature reaches 250 degrees F (121.1 ° C), researchers add 259 grams of mono PE and 403 grams of castor oil. The pot is heated to 460 degrees F (237.8 ° C) with vacuum pressure at 150 mm Hg. The return to receipt ratio is set at three to one. Researchers continue the reactive distillation process until the theoretical amount, 571 grams of ethylene glycol, is distilled from the reaction mixture.
    [00042] The polyol produced according to the previous transesterification method has the following properties: Hydroxyl number 333; Acid number 0.40; Viscosity at 77 degrees F (25 ° C). 4,600 cps. Polyol appearance Clear amber liquid Polyol functionality according to calculation 2.9 Phenyl in polyol 16.79 HFC 245fa solubility in pphpp 31 Solstice ™ solubility - 1233zd (E) in pphpp 34 FEA-1 100 pphpp solubility 14 The polyol is labeled DS-16060-1. EXAMPLE 3
    [00043] Researchers first add 49 grams of diethylene glycol, 884 grams of triethylene glycol, 1,153 grams of tetraethylene glycol, 358 grams of glycerin, 1,707 grams of poly (ethylene terephthalate) and 4 grams of Tyzor TE (a titanate chelate of triethanolamine) in a 5 liter 4-neck glass jar that is equipped with a reflux condenser, separation column, suspended receiver and a thermocouple.
    [00044] The researchers then heat the pot to 450 degrees F (232.2 ° C) and maintain the pot's temperature at 450 degrees F (232.2 ° C) for 2 hours. The researchers then allowed the pot to cool to 250 degrees F (121.1 ° C).
    [00045] When the temperature reaches 250 degrees F (121.1 ° C), the researchers add 132 grams of mono PE. The pot is heated to 460 degrees F (237.8 ° C) with vacuum pressure at 150 mm Hg. The return to receipt ratio is set at three to one. The researchers continue the reactive distillation process until the theoretical amount, 534 grams of ethylene glycol, is distilled from the reaction mixture.
    [00046] The polyol produced according to the previous transesterification method has the following properties: Hydroxyl number 333; Acid number 0.40; Viscosity at 77 degrees F (25 ° C). 5.211 cps. Polyol appearance Light amber liquid Polyol functionality according to calculation 2.8 Phenyl in polyol 18.02 HFC 245fa solubility in pphpp 23 Solstice ™ solubility - 1233zd (E) in pphpp 24 FEA-1 100 pphpp solubility 11 The polyol is labeled DS-16063-1. EXAMPLE 4
    [00047] Researchers first add 225 grams of diethylene glycol, 1,227 grams of triethylene glycol, 500 grams of tetraethylene glycol, 201 grams of glycerin, 1,629 grams of poly (ethylene terephthalate) and 4 grams of Tyzor TE (a titanate chelate) triethanolamine) in a 5 liter glass jar with 4 necks that is equipped with a reflux condenser, separation column, suspended receiver and a thermocouple.
    [00048] The researchers then heat the pot to 450 degrees F (232.2 ° C) and maintain the pot's temperature at 450 degrees F (232.2 ° C) for 2 hours. The researchers then allowed the pot to cool to 250 degrees F (121.1 ° C).
    [00049] When the temperature reaches 250 degrees F (121.1 ° C), the researchers add 256 grams of tech PE which is a mixture of about 90% monopentaerythritol and 10% dipentaerythriol and 472 grams of castor oil. The pot is heated to 460 degrees F (237.8 ° C) with vacuum pressure at 150 mm Hg. The return to receipt ratio is set at three to one. The researchers continue the reactive distillation process until the theoretical amount, 509 grams of ethylene glycol, is distilled from the reaction mixture.
    [00050] The polyol produced according to the previous transesterification method has the following properties: Hydroxyl number 333; Acid number 0.40; Viscosity at 77 degrees F (25 ° C). 4,272 cps. Polyol appearance Light amber liquid Polyol functionality according to calculation 2.8% Phenyl in polyol 16.12 HFC 245fa solubility in pphpp 33 Solstice ™ solubility - 1233zd (E) in pphpp 35.8 FEA-1 100 pphpp solubility 11.8 The polyol is labeled DS-16067-1. EXAMPLE 5
    [00051] The researchers first add 576 grams of diethylene glycol, 760 grams of triethylene glycol, 757 grams of C236 (C236 is a product of 2 moles of propylene oxide added to 1 mole of mixtures of ethylene glycol and diethylene glycol in the ratio in weight of approximately 80 to 20), and 1,397 grams of poly (ethylene terephthalate) and 4 grams of Tyzor TE (a triethanolamine titanate chelate) in a 5-liter 4-neck glass jar that is equipped with a reflux condenser , separation column, suspended receiver and a thermocouple.
    [00052] The researchers then heat the pot to 450 degrees F (232.2 ° C) and maintain the pot's temperature at 450 degrees F (232.2 ° C) for 2 hours. The researchers then let the pot cool down to 250 degrees F (121.1 ° C).
    [00053] When the temperature reaches 250 degrees F (121.1 ° C), the researchers add 334 grams of tech PE and 363 grams of castor oil. The pot is heated to 460 degrees F (237.8 ° C) with vacuum pressure at 150 mm Hg. The return to receipt ratio is set at three to one. The researchers continue the reactive distillation process until the theoretical amount, 437 grams of ethylene glycol, is distilled from the reaction mixture.
    [00054] The polyol produced according to the previous method has the following properties: Hydroxyl number 341; Acid number 0.30; Viscosity at 77 degrees F (25 ° C). 4,285 cps. Polyol appearance Clear amber liquid Polyol functionality according to the calculation 2.8 Phenyl in polyol 14.75 HFC 245fa solubility in pphpp 38,4 FEA-1100 solubility in pphpp 23,5 Water solubility in pphpp 21,2 The polyol is labeled as DS-16017. EXAMPLE 6
    [00055] Researchers first add 740 grams of diethylene glycol, 1,304 grams of tripropylene glycol 353 grams of glycerin, and 1,573 grams of poly (ethylene terephthalate) and 4 grams of Tyzor TE (a triethanolamine titanate chelate) in a pot of 5 liters glass of 4 necks that is equipped with reflux condenser, separation column, suspended receiver and a thermocouple.
    [00056] The researchers then heat the pot to 450 degrees F (232.2 ° C) and maintain the pot's temperature at 450 degrees F (232.2 ° C) for 2 hours. The researchers then let the pot cool down to 250 degrees F (121.1 ° C).
    [00057] When the temperature reaches 250 degrees F (121.1 ° C), the researchers add 175 grams of tech PE and 346 grams of castor oil. The pot is heated to 460 degrees F (237.8 ° C) with vacuum pressure at 150 mm Hg. The return to receipt ratio is set at three to one. The researchers continue the reactive distillation process until the theoretical amount, 437 grams of ethylene glycol, is distilled from the reaction mixture.
    [00058] The polyol produced according to the previous method has the following properties: Hydroxyl number 400; Acid number 0.50; Viscosity at 77 degrees F (25 ° C). 5.976 cps. Polyol appearance Light amber liquid Polyol functionality according to calculation 2.9% phenyl in polyol 15.57 HFC 245fa solubility in pphpp 34 FEA-1 100 pphpp solubility 29.2 The polyol is labeled DS- 16073-400 -1. EXAMPLE 7
    [00059] The researchers first add 282 grams of diethylene glycol, 424 grams of triethylene glycol, 1,406 grams of TPG, 387 grams of glycerin, 1,646 grams of poly (ethylene terephthalate) and 4 grams of Tyzor TE (a chelate of titanate of triethanolamine) in a 5 liter 4-neck glass jar that is equipped with a reflux condenser, separation column, suspended polyol receiver and a thermocouple.
    [00060] The researchers then heat the pot to 450 degrees F (232.2 ° C) and maintain the pot's temperature at 450 degrees F (232.2 ° C) for 2 hours. The researchers then let the pot cool down to 250 degrees F (121.1 ° C).
    [00061] When the temperature reaches 250 degrees F (121.1 ° C), the researchers add 119 grams of tech PE. The pot is heated to 460 degrees F (237.8 ° C) with vacuum pressure at 150 mm Hg. The return to receipt ratio is set at three to one. The researchers continue the reactive distillation process until the theoretical amount, 514 grams of ethylene glycol, is distilled from the reaction mixture.
    [00062] The polyol produced according to the previous transesterification method has the following properties: Hydroxyl number 363; Acid number 0.50; Viscosity at 77 degrees F (25 ° C). 6,190 cps. Appearance Light amber liquid Polyol functionality as per calculation 2.8% phenyl in polyol 17.37 Solubility of HFC 245fa in pphpp 33 Solubility of Solstice ™ - 1233zd (E) in pphpp 35 Solubility of FEA-1100 in pphpp 28 O polyol is labeled DS-16078
    [00063] EXAMPLE 8
    [00064] The researchers load 6,197 grams of crude glycerin in a 10-liter pot that is equipped with a reflux condenser, separation column, suspended receiver and a thermocouple. Crude glycerin contains 23% water as suppliers suggest. Heat the pot to 350 degrees F with a 10 mm Hg vacuum to remove water and light. Collect condensation at 188 degrees F, pot temperature and top temperature at the top of the column at 123 degrees F. The total collected top product is 173 grams.
    [00065] The researchers heat the pot to 430 degrees with a 10 mm Hg vacuum. The equilibrium reaches 380 degrees F (193.3 ° C) with a 10 mm Hg vacuum. The top temperature is 181 degrees C. A total of 5,700 grams of clear refining glycerin is collected with a hydroxyl number of 1,694.6 and a water percentage of 0.7. This glycerin is called refining glycerin.
    [00066] Researchers first add 238 grams of diethylene glycol, 966 grams of triethylene glycol, 698 grams of tetraethylene glycol, 383 grams of refining glycerin produced from experiment 8, 1.687 grams of poly (ethylene terephthalate) and 4 grams of Tyzor TE (a triethanolamine titanate chelate) in a 5 liter 4-neck glass jar that is equipped with a reflux condenser, separation column, suspended receiver and a thermocouple.
    [00067] The researchers then heat the pot to 450 degrees F (232.2 ° C) and maintain the pot's temperature at 450 degrees F (232.2 ° C) for 2 hours. The researchers then let the pot cool down to 250 degrees F (121.1 ° C).
    [00068] When the temperature reaches 250 degrees F (121.1 ° C), the researchers add 162 grams of tech PE and 190 grams of soy oil. The pot is heated to 460 degrees F (237.8 ° C) with vacuum pressure at 150 mm Hg. The return to receipt ratio is set at three to one. The researchers continue the reactive distillation process until the theoretical amount, 527 grams of ethylene glycol, is distilled from the reaction mixture.
    [00069] The polyol produced according to the transesterification method 350; 0.50; 8,494 cps. Appearance Light amber liquid Polyol functionality as per calculation 2.8 Phenyl in polyol 17.59 HFC 245fa solubility in pphpp 25 Solstice ™ solubility - 1233zd (E) in pphpp 27 The polyol is labeled DS-16105-1 EXAMPLE 9
    [00070] Researchers first add 250 grams of diethylene glycol, 721 grams of triethylene glycol, 1,077 grams of tetraethylene glycol, 655 grams of glycerin, 1,748 grams of poly (ethylene terephthalate) and 4 grams of Tyzor TE (a titanate chelate) triethanolamine) in a 5 liter glass jar with 4 necks that is equipped with a reflux condenser, separation column, suspended receiver and a thermocouple.
    [00071] The researchers then heat the pot to 450 degrees F (232.2 ° C) and maintain the pot's temperature at 450 degrees F (232.2 ° C) for 2 hours. The researchers then let the pot cool down to 250 degrees F (121.1 ° C).
    [00072] When the temperature reaches 250 degrees F (121.1 ° C), the researchers add 206 grams of soy oil. The pot is heated to 460 degrees F (237.8 ° C) with vacuum pressure at 150 mm Hg. The return to receipt ratio is set at three to one. The researchers continue the reactive distillation process until the theoretical amount, 547 grams of ethylene glycol, is distilled from the reaction mixture.
    [00073] The polyol produced according to the previous method has the following properties: Hydroxyl number 380; Acid number 0.50; Viscosity at 77 degrees F (25 ° C). 5.561 cps. Appearance Light amber liquid Polyol functionality as per calculation 2.85 Phenyl in polyol 17.31 HFC 245fa solubility in pphpp 24 The polyol is labeled DS-16115-1 EXAMPLE 10
    [00074] The researchers first add 276 grams of diethylene glycol, 935 grams of methylene glycol, 676 grams of tetraethylene glycol, 370 grams of refining glycerin produced from experiment 8 and 1,633 grams of poly (ethylene terephthalate) and 4 grams of Tyzor TE (a triethanolamine titanate chelate) in a 5 liter 4-neck glass jar that is equipped with a reflux condenser, separation column, suspended receiver and a thermocouple.
    [00075] The researchers then heat the pot to 450 degrees F (232.2 ° C) and maintain the pot's temperature at 450 degrees F (232.2 ° C) for 2 hours. The researchers then let the pot cool down to 250 degrees F (121.1 ° C).
    [00076] When the temperature reaches 250 degrees F (121.1 ° C), the researchers add 185 grams of methyl glycoside and 185 grams of soy oil. The pot is heated to 460 degrees F (237.8 ° C) with vacuum pressure at 150 mm Hg. The return to receipt ratio is set at three to one. The researchers continue the reactive distillation process until the theoretical amount, 517 grams of ethylene glycol, is distilled from the reaction mixture.
    [00077] The polyol produced according to the previous transesterification method has the following properties: Hydroxyl number 350; Acid number 0.4; Viscosity at 77 degrees F (25 ° C) 11,800 cps. Appearance Light amber liquid The number of polyol hydroxyl rose to 375.5 per post addition of diethylene glycol. Hydroxyl number 375.50; Acid number 0.38; Viscosity at 77 degrees F (25 ° C) 6,950 cps. Polyol functionality as per calculation 2.8 Phenyl in polyol 16.62 Solubility of HFC 245fa in pphpp 29 Solubility of Solstice ™ 1233zd (E) in pphpp 30 The polyol is labeled DS-16116-3 EXAMPLE 11
    [00078] Researchers first add 1,396 grams of triethylene glycol, 701 grams of tetraethylene glycol, 384 grams of glycerin, and 1,695 grams of poly (ethylene terephthalate) and 4 grams of Tyzor TE (a triethanolamine titanate chelate) in one 5 liter glass jar with 4 necks that is equipped with reflux condenser, separation column, suspended receiver and a thermocouple.
    [00079] The researchers then heat the pot to 450 degrees F (232.2 ° C) and maintain the pot's temperature at 450 degrees F (232.2 ° C) for 2 hours. The researchers then let the pot cool down to 250 degrees F (121.1 ° C). When the temperature reaches 250 degrees F (121.1 ° C), the researchers add 163 grams of tech PE and 191 grams of epoxidized soy oil. The pot is heated to 460 degrees F (237.8 ° C) with vacuum pressure at 150 mm Hg. The return to receipt ratio is set at three to one. The researchers continue the reactive distillation process until the theoretical amount, 530 grams of ethylene glycol, is distilled from the reaction mixture.
    [00080] The polyol produced according to the transesterification method 350; 0.5; 8,677 cps. Appearance Light amber liquid Polyol functionality as per calculation 2.95 Phenyl in polyol 16.77 HFC 245fa solubility in pphpp 27 The polyol is labeled DS-16117-1 EXAMPLE 12
    [00081] Researchers first add 251 grams of diethylene glycol, 1,018 grams of triethylene glycol, 735 grams of tetraethylene glycol, 403 grams of glycerin, 1,537 grams of terephthalic acid and 4 grams of Tyzor TE (a triethanolamine titanate chelate) in a 5 liter 4-neck glass jar that is equipped with a reflux condenser, separation column, suspended receiver and a thermocouple.
    [00082] The researchers then heat the pot to 450 degrees F (232.2 ° C) and maintain the pot's temperature to 450 degrees F (232.2 ° C) for 2 hours. The researchers then let the pot cool down to 250 degrees F (121.1 ° C).
    [00083] When the temperature reaches 250 degrees F (121.1 ° C), the researchers add 171 grams of tech PE and 201 grams of soy oil. The pot is heated to 460 degrees F (237.8 ° C) with vacuum pressure at 150 mm Hg. The return to receipt ratio is set at three to one. The researchers continue the reactive distillation process until the theoretical amount, 315 grams of water is distilled from the reaction mixture.
    [00084] The polyol produced according to the previous direct esterification method has the following properties: Hydroxyl number 350; Acid number 0.5; Viscosity at 77 degrees F (25 ° C). 9,409 cps. Appearance Light amber liquid Polyol functionality as per calculation 2.9 Phenyl in polyol 17.59 HFC 245fa solubility in pphpp 25 The polyol is labeled DS-16118-1 EXAMPLE 13
    [00085] The researchers first add 254 grams of diethylene glycol, 1,032 grams of triethylene glycol, 745 grams of tetraethylene glycol, 407 grams of refining glycerin produced from experiment 8, 1,728 grams of poly (ethylene terephthalate) and 4 grams of Tyzor TE (a triethanolamine titanate chelate) in a 5 liter 4-neck glass jar that is equipped with a reflux condenser, separation column, suspended receiver and a thermocouple.
    [00086] The researchers then heat the pot to 450 degrees F (232.2 ° C) and maintain the pot's temperature at 450 degrees F (232.2 ° C) for 2 hours. The researchers then let the pot cool down to 250 degrees F (121.1 ° C).
    [00087] When the temperature reaches 250 degrees F (121.1 ° C), the researchers add 174 grams of tech PE and 200 grams of soy oil. The pot is heated to 460 degrees F (237.8 ° C) with vacuum pressure at 150 mm Hg. The return to receipt ratio is set at three to one. The researchers continue the reactive distillation process until the theoretical amount, 540 grams of ethylene glycol, is distilled from the reaction mixture.
    [00088] The polyol produced according to the previous transesterification method has the following properties: Hydroxyl number 365; Acid number 0.50; Viscosity at 77 degrees F (25 ° C). 7,323 cps. Appearance Light amber liquid Polyol functionality as per calculation 2.85% phenyl in polyol 17.1 Solubility of HFC 245fa in pphpp 25 Solubility of Solstice 1 Ml233zd (E) in pphpp 27 The polyol is labeled DS-16126-1 Example 14
    [00089] Researchers first add 293 grams of diethylene glycol, 994 grams of methylene glycol, 689 grams of tetraethylene glycol, 1,716 grams of poly (ethylene terephthalate) and 4 grams of Tyzor TE (a triethanolamine titanate chelate) in one 5 liter glass jar with 4 necks that is equipped with reflux condenser, separation column, suspended receiver and a thermocouple.
    [00090] The researchers then heat the pot to 450 degrees F (232.2 ° C) and maintain the pot's temperature at 450 degrees F (232.2 ° C) for 2 hours. The researchers then let the pot cool down to 250 degrees F (121.1 ° C).
    [00091] When the temperature reaches 250 degrees F (121.1 ° C), the researchers add 175 grams of tech PE, 222 grams of soy oil and 558 grams of crude glycerin with 15.5% water as determined by Titrator Karl Fisher. The pot is heated to 460 degrees F (237.8 ° C) with vacuum pressure at 150 mm Hg. The return to receipt ratio is set at three to one. The researchers continue the reactive distillation process until the theoretical amount, 536 grams of ethylene glycol and 86.49 grams of water, is distilled from the reaction mixture. The polyol was cooled to about 160 to 170 degrees F and was filtered through a 25 micron filter bag (Filter Specialists, Inc - BPONG25P2pWE).
    [00092] The polyol produced according to the previous transesterification method has the following properties: Hydroxyl number Acid number Viscosity at 77 degrees F (25 ° C). Percentage of solid Appearance The polyol is labeled DS-16180-C
    [00093] Table 5 - Summary of weight percentage of functionality improvements and natural or modified oil one in each polyol example:
    Note: (1) Example 3 and 7 do not use any oil; (2) Example 5 contains PE 90 (technical grade) and castor oil only; (3) Example 9 contains glycerin and SBO only; (4) Example 10 contains MG (replacing PE) glycerin and SBO; (5) Example 11 uses epoxidized soy oil (replacing castor oil and soy); (6) Example 12 uses crude glycerin directly.
    [00094] The main improvements in functionality are glycerin and PE. The examples show that the high functionality polyol can be produced using only PE or glycerin (according to examples 5 and 9). However, with PE and glycerin, polyol appears to be more robust. Castor oil and epoxidate are used to reduce polyol viscosity. They have some functionality but provide very little improvement in blowing agent solubility. Soy oil is primarily used to reduce viscosity and to improve the blowing agent's solubility. Unfortunately, soybean oil does not provide any functionality. Examples 3 and 7 do not contain any kind of oil. We achieve the desired viscosity by employing a high loading of high molecular weight glycols.
    [00095] Oxid recently acquired a smoke box, an instrument for detecting smoke density of foam. Although the size of the foam sampler is only one cubic inch, the results (SDR) of burning the box can be correlated with the actual E-84 tunnel test smoke density. For example, Oxid was able to purchase foam samplers that were tested in the E-84 tunnel. The first is a phenolic foam with a smoke density of less than 50 (which is determined by E-84); the second is stock foam on a 300 index polyisocyanurate roll with an average smoke density of 190 from two reliable E-84 tunnel testing facilities; the third is spray foam from the current commercial two-pound wall cavity as described in table 1; the fourth is a roof foam with a smoke density of 600. These foams are carefully cut into many one-cubic-inch foams. The repeated burning of these foams in the smoke box is carried out. The following table 6 presents the results. Table 6:

    [00096] If plotted, the data in Table 6 clearly shows that SD 200 to 650 of E84 vs. Smoke box SDR has almost linear correlation.
    [00097] Table 7 shows the polyol composition of the experiment according to Example 2:

    [00098] Five polyurethane and control foams are prepared in the laboratory based on the formula in table 8 below: Table 8: Formula for HFC245fa / water wall cavity spray

    * Jeffol 470X has 8.1% polyol phenyl
    [00099] As previously mentioned, the control foam meets all requirements for commercial application. The control foam SDR value is 36.25. Based on the correlation in Table 6, which has about 400 - 450 E-84 tunnel test. (Note: Smoke Box SDR value is a laboratory test of foam density property of one cubic inch foam. The correlation is only for the purpose of rating the smoke property of the E84 test foam. We do not predict the actual number the density of burning smoke from E-84 large-scale spray foam due to many other factors being involved.) PBW1 foam with 100% polyester polyol and 0% flame retardants is 20.46 which is almost equivalent the smoke density of 190 from E84. Four percent of PHT4diol and TCPP respectively added to the B mixture, the SDR value of PBW2 foam increases to 27.68 as expected. When four percent of PHT4diol is replaced by TCPP, the SDR value of PBW3 foam increases to 33.87. TCPP generates more smoke than PHT4diol. When 5 percent of Carpol GSP 280 is added to the B mixture, the SDR value of PBW4 increases further to 40.69. When ten percent of Carpol GSP 280 is added to the mix, the PBW5 foam SDR decreases slightly (perhaps due to more crosslink density). However, the polyether generates smoke. Based on the previous results, it seems to us that the phenyl content (aromaticity) of the B mixture is the most important parameter for the smoke density of the foam.
    [000100] In other words, 100 percent polyester as a polyol alone in the blend of B without any polyether and flame retardant is the best method for suppressing the smoke density of the polyurethane foam. Unfortunately, polyurethane foam is organic material that needs some flame retardant, especially phosphorus, to prevent the flame from spreading during burning. Therefore, with respect to foam flame spread and optimal processing viscosity, we recommend seven or ten percent of TCPP to be included in the formulation as PBW3 in Table 8. Clearly, PBW3 does not contain any PHT4diol and its foam has less smoke density (SDR = 33.87) of which the control foam (SDR = 36.25).
    [000101] The following is another example. Table 9 shows the polyol composition of the experiment in example 1:


    [000102] Table 10: Formula for HFC245fa / water wall cavity spray based on the polyol of example 1


    [000103] Again, the 100% polyester polyol as PBW1 in table 10 generates the least smoke among five formulations. The more TCPP and PHT4diol in the formulation, the greater the increase in foam SDR. Table 11: Formula for SolStice ™ -1233zd (E) / water wall cavity spray


    [000104] Replacing HFC 245FA with Solstice -1233zd (E), the SDR of polyurethane foams based on these two polyols appears to be close. In the case of the polyol of example 1, with 8 percent TCPP, PBW3 in table 10 is 33.75 and PBW1 in table 11 is 36.56. In the case of the polyol of example 2, with 0 percent flame retardants, PBW2 in table 9 is 20.46 and PBW2 in table 11 is 23.81. Example 3 contains PE and glycerin but not castor oil. Its foam smoke property is in line with the polyol in Example 1 and Example 2. Table 12:
    Table 13


    [000105] With 8 percent TCPP, PBW3 in table 13 has viscosity of 993 cps at 25 ° C and SDR value of 35.52.
    [000106] The polyol of example 4 has the composition as in table 14. Table 14
    Table 15: Formula for HFC245fa / water wall cavity spray based on the polyol of example 4

    * Jeffol 425, a Mannich-based polyether polyol from Huntsman has 7.73% phenyl in polyol.
    [000107] Again, we observed the dominant effect of phenyl (aromaticity) in the B mixture on the smoke density of the foam. Obviously, more castor oil does not increase more smoke. Compared to GSP 280, the Jeffol 425X created less smoke.
    [000108] In examples 5, 6 and 7, we added C236 as well as Tripropylene glycol to increase the solubility of FEA 1100 polyol. The polyol as example 6 has 29 pphpp of FEA1 100 solubility and the polyol as example 7 has 28 pphpp of solubility FEA1 100. Pphpp means parts per hundred parts of polyol. The foam example from polyol example 7 is shown in table 16.


    [000109] Table 17: Formula for water / HFC245fa and water / sprinkling of FEA1100 wall cavity based on the polyol of example 7


    [000110] PBW1 in table 17 has excellent dimensional stability. The smoke density based on SDR value is high but controllable. TPG in the polyol provides plenty of solubility of FEA 1100 in the B mixture.
    Table 19: HFC245fa wall cavity spray / water formula based on the polyol of example 8


    [000111] Although examples 8 and 10 polyol contain refined glycerin; they behave as if they contain pure glycerin. Nature's oil is believed to increase the smoke density of the foam. However, the SDR value of PBW1 in table 19 shows that five percent of soy oil in the polyol appears to be fine. Again, clearly, not containing PHT4diol, PBW1 foam has a lower SDR than the control foam. Table 20: HFC245fa wall cavity spray / water formula based on example 9

    [000112] The polyol of example 9 contains 16.34 percent glycerin and no PE. The dimensional stability of PBW1 in table 20 is not as good as in the others, but acceptable. The smoke will be on the marginal line. Example 10 polyol containing about 5% MG appears to be fine with a hydroxyl value of 375 and a viscosity of 6,950 cps at 77 F.
    [000113] The polyol of example 12 produced by the direct esterification method has the same results as example 8 which is produced by the transesterification method has in terms of hydroxyl number, acid number, viscosity and solubility of HFC245FA. Comparative Example 1
    [000114] Terol 925 (supplied by Oxid LP) is a polyester polyol of high aromatic content, high functionality. It has been found that Terol 925 is used in spray formulations that require a Class I rating of E-84 using 245fa. The typical properties of Terol 925 are as follows: Hydroxyl number 305; Viscosity at 25 C 11,500 cps; Acid number 1.0; Phenyl content about 21.9, Nominal functionality 2.45.
    [000115] Table 21 shows the formulation of PUR foam and physical properties of foams based on Terol 925 (comparative example 1) and polyol of example 13. Table 21:



    [000116] As shown, the loading of PBW1 and PBW2 polyol ester from table 21 is the same. The viscosity of the B-side of PBW1 is 1,744 cps, which is much higher than typical desirable viscosity for typical handling. The comparative polyol has a higher reaction rate than example 13. However, in terms of foam properties in terms of compressive strength, green resistance and dimensional stability, example 9 is much superior to comparative polyol - Terol 925. Without polyether polyol, T925 would have difficulties in providing the much needed physical properties for the foam. Example 13 and other HF polyols as a polyol alone in the B mixture would provide the physical properties for polyurethane spray foam. Due to its higher aromaticity, Terol 925 has less smoke density than the polyol of Example 13. Comparative Example 2 Table 22:


    [000117] A 100% polyether foam (Jeffol 470X and GSP 280) is prepared based on the formulation's PBW1 in table 22. As expected, the foam has excellent physical properties, including dimensional stability of classification A, minimal indentation of green resistance . However, the smoke density is very high which is almost twice the foams based on our new polyester.
    [000118] Based on the polyol formulation excluding examples 5, 6 and 7 mentioned above, 3,000 pounds of polyol were produced in a pilot plant, labeled XO 12009. The typical polyol properties are in table 23.

    [000119] We sprayed several commercial wall and roof polyurethane foams in Canada using aromatic polyester polyol XO 12009. The E-84 tunnel tests were conducted at Exova in Toronto, Canada.
    [000120] The formulation used to prepare the foam samples evaluated as shown below:

    The processing conditions are observed below in table 25

    Sprinkling One pass of 4 Two passes of one Two passes of foam inch inch inch The physical properties of foams based on XO 12009 are in table 26:
    [000121] The fire properties of XO 12009 polyol based foams are excellent as predicted. These HFC365mfc / 227 foams and blown water (with / without a touch of HFC 245fa) are able to easily obtain an E-84 class rating.
    权利要求:
    Claims (9)
    [0001]
    1. Aromatic polyester polyol essentially free from polyether polyol, characterized by the fact that it is suitable as the only polyol in the production of polyurethane foams that have a E-84 tunnel fire test grade rating, said polyester polyol aromatic having a range of functionality from 2.8 to 3.2 and a moderate viscosity ranging from 4,000-10,000 cps at 25 ° C inclusive, prepared by transesterification or esterification of a mixture comprising: 1.9-66% w / w of a glycol, 24-34% w / w terephthalate source, 5.02-17% w / w glycerin, 3.14-14% w / w pentaerythriol, 0-5% w / w methyl glycoside, 0- 10% w / w sorbitol, and 0-15% w / w natural vegetable oil, modified natural vegetable oil or derived from the fatty acid of natural vegetable oil.
    [0002]
    2. Aromatic polyester polyol according to claim 1, characterized by the fact that the glycol is ethylene glycol, polyethylene glycol, propylene glycol or polypropylene glycol.
    [0003]
    3. Aromatic polyester polyol according to claim 1, characterized by the fact that the terephthalate source is derived from poly (ethylene terephthalate) (PET), industrial recycled PET, post-consumer PET, terephthalic acid (TA), TA industrial recycled material (BACA), phthalic anhydride, isophthalic acid or metaphalic acid.
    [0004]
    4. Aromatic polyester polyol according to claim 1, characterized by the fact that the natural vegetable oil is castor oil, palm oil, cotton oil, soybean oil, corn oil, pine oil, linseed oil or tung oil.
    [0005]
    5. Aromatic polyester polyol, according to claim 1, characterized by the fact that it has a hydroxyl number in the range of 320-400 inclusive, and percentage percentage of phenyl (w / w) in the range of 14.75 to 19, 58.
    [0006]
    6. Composition for preparing polyurethane foam, characterized by the fact that it comprises: a component on side A comprising a polyisocyanate; and a B-side component comprising catalyst, surfactant, flame retardant, blowing agent and the aromatic polyester polyol as defined in claim 1.
    [0007]
    7. Composition according to claim 6, characterized by the fact that the polyol component has 65-80% w / w of the B-side component.
    [0008]
    8. Composition according to claim 6, characterized by the fact that the volume ratio of component from side A to component from side B is 1: 1.
    [0009]
    9. Composition according to claim 6, characterized by the fact that the blowing agent is water, pentafluorpropane, pentafluorbutane, heptafluorpropane, chloro-trifluorpropane, hexafluor-2-butene, pentanes or combinations thereof.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112014025257B1|2020-12-29|aromatic polyester polyol, and, composition for preparing polyurethane foam
    US20100298453A1|2010-11-25|Board stock foam having biobased content
    JP5547722B2|2014-07-16|Method for producing rigid polyisocyanurate foam using natural oil polyol
    BRPI0912463B1|2019-10-01|Process for preparing a rigid foam
    BRPI0904276A2|2010-07-20|rigid polyisocyanurate foam and processes for the production and use thereof
    CN106146783A|2016-11-23|A kind of Freon-free flame-retardant polyurethane for solar water heater insulation hard bubbles compositions
    Li et al.2016|Preparation and properties of rigid polyurethane foam based on modified castor oil
    US20200140601A1|2020-05-07|Flame retarded polyurethane foam
    ES2770854T3|2020-07-03|Polyurethane foam from highly functional polyisocyanate
    ES2774784T3|2020-07-22|Flame retardant polyol
    JP4032855B2|2008-01-16|Rigid polyurethane foam composition and foam
    JP2014162813A|2014-09-08|New polyether polyol and flexible polyurethane foam product obtained using the same
    Czupryński et al.2006|Studies on Effect of Tri |, Tri | and Tri | Borates on Thermal and Heat Properties of Rigid Polyurethane‐Polyisocyanurate Foams
    JP2015083692A|2015-04-30|Polyol compositions, resin blend compositions, spray compositions, and methods of using each, and methods of making each
    CN106519157A|2017-03-22|Structure flame retardant rosin-based polyhydric alcohol for hard polyurethane foam and preparation method and application thereof
    JP5866839B2|2016-02-24|Rigid polyurethane foam composition
    JP5403898B2|2014-01-29|Polyol composition for spray foamed rigid polyurethane foam and method for producing spray foamed rigid polyurethane foam
    BR112020020776A2|2021-01-26|mixture, pu foam or rigid pu-pir and insulation board for roof or wall application
    PL234199B1|2020-01-31|Method for producing ecological polyols from the waste after transesterification of vegetable oils and method for manufacturing stiff polyurethane foams
    同族专利:
    公开号 | 公开日
    US20150051304A1|2015-02-19|
    RU2014145022A|2016-06-10|
    CA2869739C|2020-08-11|
    EP2836534A1|2015-02-18|
    CN104379630B|2018-05-29|
    CN104379630A|2015-02-25|
    RU2629941C2|2017-09-05|
    CA2869739A1|2013-10-17|
    US9809674B2|2017-11-07|
    WO2013154874A1|2013-10-17|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4604410A|1983-07-13|1986-08-05|Chardonol Corporation|Manufacturing of rigid foam using etherified modified aromatic polyols|
    US4701477A|1983-07-13|1987-10-20|Chardonol, Division Of Freeman Corporation|Low viscosity aromatic polyols and methods for their preparation|
    US4469824A|1983-11-18|1984-09-04|Texaco, Inc.|Liquid terephthalic ester polyols and polyisocyanurate foams therefrom|
    US4644019A|1985-10-28|1987-02-17|Texaco Inc.|Modified terephthalic ester polyols and rigid foams therefrom|
    US5360900A|1993-08-12|1994-11-01|Oxid, Inc.|Aromatic polyester polyol|
    US6133329A|1999-03-31|2000-10-17|Oxid L.P.|Aromatic polyester polyols made from a natural oil|
    AU2002315173A1|2001-06-15|2003-01-02|Stepan Company|Phthalate polyester polyol-based compositions and high dimensionally stable all water-blown spray polyurethane foam derived therefrom|
    US20040059011A1|2002-07-19|2004-03-25|Barber Thomas Allan|Aromatic polyester polyols|
    RU2236422C1|2003-04-29|2004-09-20|Закрытое акционерное общество "Блокформ" - Дочернее общество ОАО "Полимерсинтез"|Method for production of polyester-polyols and rigid foamed plastics based thereon|
    US7560526B2|2006-03-21|2009-07-14|Oxid, L.P.|Polyol with high cyclopentane solubility|
    CN101851328B|2010-06-12|2011-09-07|常州市康宏装饰材料有限公司|High-functionality polyester polyol and preparation method thereof|
    WO2012041709A1|2010-09-29|2012-04-05|Dow Global Technologies Llc|High functionality aromatic polyesters, polyol blends comprising the same and resultant products therefrom|
    WO2012072540A1|2010-12-02|2012-06-07|Basf Se|Polyester polyols based on aromatic dicarboxylic acids|
    US20120202907A1|2011-02-05|2012-08-09|Kurt Kurple|Lignin based polyol from black liquor and glycerine|CA2701044C|2007-09-28|2018-02-27|Stepan Company|Aromatic polyester polyols and aromatic polyester polyol blends containing biorenewable components and methods of making|
    CN103881074B|2014-01-23|2016-01-06|单成敏|A kind of preparation method of biomass polyester polyvalent alcohol|
    CN103755936B|2014-01-23|2016-02-03|单成敏|A kind of preparation method of biomass phthalic anhydride polyol|
    EP3140333B1|2014-05-05|2019-02-27|Resinate Materials Group, Inc.|Polyester polyols from thermoplastic polyesters and dimer fatty acids|
    EP3183281A1|2014-08-20|2017-06-28|Resinate Materials Group, Inc.|High recycle content polyester polyols|
    US9951171B2|2014-08-20|2018-04-24|Resinate Materials Group, Inc.|Polyester polyols from recycled polymers and waste streams|
    US9850400B2|2014-08-20|2017-12-26|Resinate Materials Group, Inc.|Digestion of keratin|
    US10414859B2|2014-08-20|2019-09-17|Resinate Materials Group, Inc.|High recycle content polyester polyols|
    WO2016028841A1|2014-08-20|2016-02-25|Resinate Materials Group, Inc.|Digestion of keratin|
    US9890243B2|2014-10-29|2018-02-13|Resinate Materials Group, Inc.|Polymeric plasticizer compositions|
    US9580546B2|2014-10-29|2017-02-28|Resinate Materials Group, Inc.|Polymeric plasticizer compositions|
    EP3250631B1|2015-01-30|2021-03-24|Resinate Materials Group, Inc.|Integrated process for treating recycled streams of pet and ptt|
    US10336879B2|2015-02-24|2019-07-02|Achilles Corporation|Rigid polyurethane foam|
    WO2016153780A1|2015-03-20|2016-09-29|Resinate Materials Group, Inc.|Cycloaliphatic polyester polyols from thermoplastic polyesters|
    US9522976B2|2015-03-20|2016-12-20|Resinate Materials Group, Inc.|Cycloaliphatic polyester polyols from thermoplastic polyesters|
    EP3283545A1|2015-04-14|2018-02-21|Resinate Materials Group, Inc.|Polyester polyols with increased clarity|
    US9676893B2|2015-09-23|2017-06-13|International Business Machines Corporation|Polyurethane materials formed from epoxidized plant oils|
    WO2017058504A1|2015-10-02|2017-04-06|Resinate Materials Group, Inc.|High performance coatings|
    US20190225734A1|2016-07-08|2019-07-25|Resinate Materials Group, Inc.|Sustainable polyol blends for high-performance coatings|
    US10131758B2|2016-07-25|2018-11-20|Accella Polyurethane Systems, Llc|Polyurethane foam-forming compositions, methods of making low density foams using such compositions, and foams formed therefrom|
    US10155837B2|2016-07-29|2018-12-18|Resinate Materials Group, Inc.|Sustainable polyester polyol compositions|
    JP2019536830A|2016-09-12|2019-12-19|レジネート マテリアルズ グループ、インコーポレイテッド|Polyphenol alkoxylates and coatings including blends|
    US10479859B2|2017-10-18|2019-11-19|Talaco Holdings, LLC|Aromatic polyester polyether polyols, polyurethanes made therefrom and building materials comprising same|
    CN109468728B|2018-12-26|2020-05-12|安正时尚集团股份有限公司|Bamboo fiber fabric|
    CN109824873A|2019-01-25|2019-05-31|江苏康宏新材料有限公司|It is a kind of for full water foamed polyester polyol and preparation method thereof|
    JP2021120445A|2019-03-29|2021-08-19|ユニチカ株式会社|Recycled polyester resin and method for producing recycled polyester resin|
    WO2021011226A1|2019-07-12|2021-01-21|Dow Global Technologies Llc|Metal polyols for use in a polyurethane polymer|
    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2020-02-11| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-10-20| B09A| Decision: intention to grant|
    2020-12-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 02/04/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261622293P| true| 2012-04-10|2012-04-10|
    US61/622293|2012-04-10|
    PCT/US2013/035017|WO2013154874A1|2012-04-10|2013-04-02|High functional polyester polyols|
    [返回顶部]