WO2023249580A1 - Procédé chimique de production d'un polyol - Google Patents

Procédé chimique de production d'un polyol Download PDF

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Publication number
WO2023249580A1
WO2023249580A1 PCT/TR2022/050817 TR2022050817W WO2023249580A1 WO 2023249580 A1 WO2023249580 A1 WO 2023249580A1 TR 2022050817 W TR2022050817 W TR 2022050817W WO 2023249580 A1 WO2023249580 A1 WO 2023249580A1
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WO
WIPO (PCT)
Prior art keywords
polyol
temperature
value
certain
reactor
Prior art date
Application number
PCT/TR2022/050817
Other languages
English (en)
Inventor
Emir TEMİZKAN
Original Assignee
Safaş Saf Plasti̇k Sanayi̇ Ve Ti̇caret Anoni̇m Şi̇rketi̇
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from TR2022/010512 external-priority patent/TR2022010512A2/tr
Application filed by Safaş Saf Plasti̇k Sanayi̇ Ve Ti̇caret Anoni̇m Şi̇rketi̇ filed Critical Safaş Saf Plasti̇k Sanayi̇ Ve Ti̇caret Anoni̇m Şi̇rketi̇
Priority to EP22851380.0A priority Critical patent/EP4326805A4/fr
Publication of WO2023249580A1 publication Critical patent/WO2023249580A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
    • C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/82—Post-polymerisation treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the invention relates to a chemical method for producing a polyol by using flexible polyurethane foam wastes to recover wastes that occur during the production of the flexible polyurethane foam into the system.
  • the recycled polyol is obtained by using the chemical recycling methods in order to recover wastes that occur during the production of the flexible polyurethane foam to the system.
  • one of the most widely used methods is to obtain a recycled foam by a physical recycling method by grinding the waste foam into small pieces and mixing with a bonding agent and applying pressure and steam.
  • the most widely used chemical recycling methods are glycolysis, aminolysis and acidolysis. Each of the listed methods has its own advantages and disadvantages.
  • the polyurethane foam materials that are divided into small pieces (scraps) are recycled into the polyol for reuse in that the glycol derivatives such as diethylene glycol and dipropylene glycol are used in the glycolysis, and the amine derivatives such as diethanolamine are used in the aminolysis, and the dicarboxylic acids are used in the acidolysis, as their names suggest.
  • the glycolysis method is carried out through the trans-esterification reaction by reacting the polyurethane foam with various diol compounds at high temperatures.
  • Another method, aminolysis is generally carried out by using the hydroxyl- and amino-derived compounds.
  • acidolysis the acidolysis reactions are carried out with various inorganic and organic acid types. In the acidolysis method, unlike the glycolysis, only one phase is obtained and no residue is produced. Therefore, the recovery yield of a recycled polyol is close to 100%.
  • the use of the excess amines and glycols at high rates during the process in the aminolysis and glycolysis methods causes the formation of two phases (polyol phase and excess product phase) after the reaction and then causes them to be subjected to a separation process.
  • a solvent since the acids and polyurethane wastes used in the acidolysis reaction are in a solid phase, a solvent must be added to the system to facilitate the reaction. The fact that this solvent is the base polyol used during the formation of the polyurethane foam facilitates the use of the obtained product (recycled polyol) instead of the base polyol used.
  • an esterification reaction is carried out by adding a bifunctional alcohol such as diethylene glycol to the system.
  • a bifunctional alcohol such as diethylene glycol
  • the catalyst used in the system should be reduced by at least 50%. Reducing the catalyst used during the formation of the flexible polyurethane foam at these rates (>50%) causes other problems such as unstable reactions or non-curing of the obtained flexible polyurethane.
  • the polyol obtained by the recycling method is described.
  • the polyurethane wastes are subjected to a reaction with the dicarboxylic acid, polyether polyol and free radical initiator at 170-210 °C.
  • the mixture obtained in the first step obtains an isocyanate-reactive polyol mixture with a short-chain diol or triol at 180- 230 °C.
  • the polyol mixture obtained is also given.
  • the oxidation reaction and the use of natural oil were not described in the document, and the technical impact of this novelty on the invention was not described.
  • PET polyol is obtained by using the polymeric fatty acids, polybasic acids, polyol and amine and used in the polyurethane foam.
  • the polymeric fatty acid ester was obtained from the oil and then this structure was modified with the alcohol.
  • the polymeric oil-modified polyester amine polyol was obtained by adding the carboxylic acid, DEG and PET wastes to the structure.
  • the acidolysis reaction is not described.
  • the fatty acids have been used for a different purpose.
  • the polyester polyol was obtained by the esterification method using PET wastes, dicarboxylic acid and DEG, and the obtained polyester polyol was used in the production of the polyurethane foam.
  • Said document is not related to the recycling of the flexible polyurethane wastes.
  • Said recyclable waste is PET waste.
  • the obtained polyol is not used in the production of the flexible polyurethane foam. Therefore, the obtained polyol is a product obtained for the rigid PUR foam systems.
  • the object of the invention is to realize a chemical method for producing a polyol by using the polyurethane foam wastes to recover the wastes that occur during the production of the flexible polyurethane foam into the system.
  • the polyol is reused by obtaining the polyol from the flexible polyurethane foam wastes by a chemical method.
  • the polyol obtained in said chemical method is produced using a natural oil, unlike the acidolysis method used in the state of the art.
  • an esterification step is not required to close the carboxylic acid bond in the disubstituted urea formed after the acidolysis reaction. In this way, there is no excess diol that increases the cross-linking in the flexible polyurethane foam system.
  • the palm oil which is the natural oil used, is converted to an epoxidized palm oil by means of the oxidizing agent, and then the epoxidized palm oil reacts with the carboxylic acid group in the disubstituted urea and is converted to a product with OH bond (polyol).
  • the polyol obtained from the flexible polyurethane foams contains a natural oil, it differs from the state of the art in terms of the usage amount and properties of the foam obtained.
  • the polyols obtained by the acidolysis method are used in the amount up to maximum 25% of the total polyol, and the hardness and closed cell amount of the obtained flexible polyurethane foam increases compared to the original foam, and the shrinkage occurs in the foam.
  • the method of the invention it has been observed that these negative effects are eliminated by using the palm oil and the higher amounts of the recycled polyol can be used.
  • Fig. 1 is the flow diagram of the method of the invention.
  • a method of the invention for producing a recycled polyol to recover the wastes that occur during the production of the flexible polyurethane foams (PUR) into the system comprises respectively the following steps:
  • the Base Polyol used in the first step of the method is a polyether triol (polyether polyol) with an OH value of 46-50 mgKOH/g and a molecular weight of 3000-3500 g/mol.
  • the base polyol does not react, it only acts as a solvent and increases the processability by reducing the viscosity. It is important here that the preferred polyol has the above-mentioned properties. Because the base polyol used is the same as the polyol already used in the production of the flexible PUR foam, and it is preferred to avoid the negative effects of the material used as a solvent after the process during the production of the flexible PUR.
  • the palm oil is used as the natural oil and has an iodine number of 57-65 gl/100 g of oil.
  • the iodine number indicated here is important. Because the iodine number and the double bond are directly proportional, and the number of the double bonds corresponding to this iodine number is 1.5-2.0 DB/mole of oil.
  • polyether polyol base polyol
  • natural oil comprising low double bond
  • anhydride is used in the first step of the method.
  • said natural oil is the palm oil with a value of 1.7 DB/mol.
  • the oxidizing agent used in the second step is used at a rate of 2% to 5% by weight, based on the total amount.
  • the oxygen (O2), ozone (O3), hydrogen peroxide (H2O2), inorganic peroxides or peroxy acids are used as the oxidation agents.
  • the temperature in the second step is 40 °C to 50 °C.
  • the oxidizing agent in the third step is dosed for 1 to 2 hours.
  • the temperature in the third step is not above 80 °C.
  • the time is 1 to 2 hours, and the temperature is 70 °C to 80 °C.
  • the temperature in the fifth step is 110 °C to 130 °C.
  • the flexible PUR foam wastes in the sixth step are at the rate of 38% to 42% by weight based on the total amount.
  • the flexible PUR foam wastes in the sixth step are added to the existing reagents for 2 to 3 hours.
  • the initial temperature in the same step is 120°C and the temperature of the reagents is increased from this temperature value to 200 °C to 220 °C.
  • the acid number is 2 mg KOH/g and the vacuum value is -0.8 atm.
  • the percentage of the water in the seventh step is 0.1%.
  • the cooling temperature value in the last step is 80 to 90 °C.
  • the amount of the base polyol used as a solvent is reduced to half, and the remaining amount is completed with the vegetable oil containing a low double bond ratio. It has been observed that the recycled polyol obtained in said studies can be used much more comfortably in the flexible polyurethane foam. In addition, the reductions were observed in the encountered problems and the structure of the obtained flexible polyurethane was improved. In the researches, it has been understood that a similar study has never been done before.
  • the use of the unsaturated vegetable oil during the acidolysis method of the invention prevents the formation of the closed cells and shrinkage in the foam by reducing the formation of cross-linking during the flexible polyurethane foam reaction of the polyol obtained during the reaction.
  • the unsaturation means the presence of the double bonds in the oil.
  • the vegetable oil to be used here has the characteristic of comprising the low double bonds. That is, the number of the double bonds per mole of oil is expected to be in the range of 1.5-2.0 (1.5-2.0 double bonds/mole of oil). If it does not contain any double bonds, it will not react in the foam, so it will cause the defects in the structure.
  • the cross-linking will increase as the functionality will increase and the use of the oil will not provide an advantage.
  • the palm oil with a value of 1.7 double bonds/mole of oil was preferably used as oil.
  • the reaction mechanism of the method is as follows: The double bonds in the oil firstly transform into the epoxy bonds, and then these epoxy bonds react with the acids remaining at the ends of the disubstituted polyurea structures, reducing the acidity and providing only the OH bonds in the reactor. In this way, there is no excess diol that increases the crosslinking in the foam. Thus, there is no need for an esterification reaction after the acidolysis reaction.
  • the reason for the oxidation reaction is that the anhydride and oil are firstly oxidized by an oxidation agent in the reactor.
  • the anhydride is oxidized, the monoperoxy dicarboxylic acids are formed. Since the monodicarboxylic acids are more reactive than the dicarboxylic acids, they accelerate the reaction and increase the yield.
  • the oil is oxidized, the double bonds are converted to the epoxy bonds and the formed epoxy bonds then react with the carboxylic acid bonds at the ends of the disubstituted ureas to form OH bonds, thus the esterification reaction is not required since the carboxylic acids are closed.
  • polyol polyether triol with OH value of 46-50 mgKOH/g and molecular weight of 3000- 3500 g/mol, equivalent weight: 1120-1220 g/mol
  • isocyanate structures 80:20 2, 4-2, 6 toluene diisocyanate, equivalent weight: 87 g/mol
  • Each 1 mole equivalent of the polyurethane is converted to 1 mole of the monoperoxy dicarboxylic acid as a result of the oxidation.
  • the recycled polyols obtained in the state of the art can be reused in the polyurethane at a maximum of 25%. However, thanks to the invention, this rate can go up to 45%.
  • the improvements were observed in the flexible PUR foam even at 45% of use in the invention, and it was observed that the standard flexible PUR foam properties were approached.
  • the reason for this is that instead of the polyether polyol added at the rate of 45-55%, natural oil (palm oil) containing 25-30% of the polyether polyol and 20-25% of the low double bond is used. Because with the use of the natural oil, the factors that will lead to the cross-linking of the system are reduced.
  • the reacted amounts were calculated stoichiometrically. Since the base polyol which is the auxiliary material is used to adjust the viscosity, the optimum value is adjusted. It was observed that the optimum value was achieved so that 38-42% of the total amount was waste, and it was not possible to use the recycled polyol obtained since the serious increases in viscosity occurred at higher rates.
  • the water content of the recycled polyol obtained should be less than 0.1%. The reason for this is that these are the acceptance criteria of all raw materials used in the production of the flexible PUR foam.
  • the polyol is produced from the recycled polyurethane scraps by the acidolysis reaction method.
  • the properties of the obtained polyol are given in Table-2:
  • Table 3 Technical properties of the polyurethane foam obtained in the experiments The correspondence of each definition in the columns given in Table-3 is explained below by numbering:
  • the standard value range is the range which is necessary when performing the quality control.
  • the foam with the standard polyol properties has been produced even when 45% of the recycled polyol is used. It was observed that the air permeability decreased when the polyol obtained by the earlier method was used at the rate of 25%, but even when the polyol obtained by the new method was used at the rate of 45%, the pores were more open. It was also observed that the hardness increased in the use of the polyol produced by the earlier method.
  • the invention is a method for producing a polyol, which is developed for use in the production of a polyurethane foam and is industrially applicable.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Abstract

L'invention concerne un procédé chimique de production d'un polyol à l'aide des déchets de mousse de polyuréthane pour récupérer les déchets qui sont produits pendant la production de la mousse de polyuréthane souple dans le système.
PCT/TR2022/050817 2022-06-24 2022-08-03 Procédé chimique de production d'un polyol WO2023249580A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP22851380.0A EP4326805A4 (fr) 2022-06-24 2022-08-03 Procédé chimique de production d'un polyol

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR2022010512 2022-06-24
TR2022/010512 TR2022010512A2 (tr) 2022-06-24 Ki̇myasal bi̇r poli̇ol üreti̇m yöntemi̇

Publications (1)

Publication Number Publication Date
WO2023249580A1 true WO2023249580A1 (fr) 2023-12-28

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4044046A (en) 1974-08-02 1977-08-23 Bridgestone Tire Company Limited Method for recovering polyol from a polyurethane
DE3435014A1 (de) * 1984-09-24 1986-03-27 Gunter Dr. 7080 Aalen Bauer Verfahren zur herstellung von polyolhaltigen fluessigkeiten aus polymerabfaellen
EP0682063A1 (fr) 1994-05-09 1995-11-15 Bayer Ag Procédé de préparation de composés contenant des groupes hydroxyles à partir de déchets de (polyuréthane) polyurés
DE19512778C1 (de) * 1995-04-05 1996-12-05 Gunter Prof Dr Bauer Verfahren zur Herstellung von isocyanatreaktiven Polyoldispersionen und deren Verwendung
WO2011035743A1 (fr) * 2009-09-22 2011-03-31 Institute Of Macromolecular Chemistry As Cr, V.V.I. Matière première pour la fabrication de polyuréthane et procédé pour sa préparation à partir de déchets de polyuréthane
US8030364B2 (en) 2004-10-11 2011-10-04 Do Gyun Kim Polyols and polyurethanes, polyurethaneforms using the same
US20190359788A1 (en) 2016-11-18 2019-11-28 H & S Anlagentechnik Gmbh Recycled polyol

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107722344B (zh) * 2017-11-03 2020-08-07 刘斌 一种回收食用油和废旧聚氨酯再利用的方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4044046A (en) 1974-08-02 1977-08-23 Bridgestone Tire Company Limited Method for recovering polyol from a polyurethane
DE3435014A1 (de) * 1984-09-24 1986-03-27 Gunter Dr. 7080 Aalen Bauer Verfahren zur herstellung von polyolhaltigen fluessigkeiten aus polymerabfaellen
EP0682063A1 (fr) 1994-05-09 1995-11-15 Bayer Ag Procédé de préparation de composés contenant des groupes hydroxyles à partir de déchets de (polyuréthane) polyurés
DE19512778C1 (de) * 1995-04-05 1996-12-05 Gunter Prof Dr Bauer Verfahren zur Herstellung von isocyanatreaktiven Polyoldispersionen und deren Verwendung
US8030364B2 (en) 2004-10-11 2011-10-04 Do Gyun Kim Polyols and polyurethanes, polyurethaneforms using the same
WO2011035743A1 (fr) * 2009-09-22 2011-03-31 Institute Of Macromolecular Chemistry As Cr, V.V.I. Matière première pour la fabrication de polyuréthane et procédé pour sa préparation à partir de déchets de polyuréthane
US20190359788A1 (en) 2016-11-18 2019-11-28 H & S Anlagentechnik Gmbh Recycled polyol

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
MARCOVICH, N. E. ET AL.: "Open cell semi-rigid polyurethane foams synthesized using palm oil-based bio-polyol", INDUSTRIAL CROPS AND PRODUCTS, vol. 102, 2017, pages 88 - 96, XP029989383, DOI: 10.1016/j.indcrop. 2017.03.02 5 *
POLACZEK ET AL.: "Open- cell polyurethane foams of very low density modified with various palm oil-based bio-polyols in accordance with cleaner production", JOURNAL OF CLEANER PRODUCTION, vol. 290, 2021, pages 125875, XP086494112, DOI: 10.1016/j.jclepro.2021.125875 *
See also references of EP4326805A4

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EP4326805A1 (fr) 2024-02-28
EP4326805A4 (fr) 2024-08-07

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