EP4326805A1 - Chemical method for producing a polyol - Google Patents

Chemical method for producing a polyol

Info

Publication number
EP4326805A1
EP4326805A1 EP22851380.0A EP22851380A EP4326805A1 EP 4326805 A1 EP4326805 A1 EP 4326805A1 EP 22851380 A EP22851380 A EP 22851380A EP 4326805 A1 EP4326805 A1 EP 4326805A1
Authority
EP
European Patent Office
Prior art keywords
polyol
temperature
value
certain
reactor
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP22851380.0A
Other languages
German (de)
French (fr)
Other versions
EP4326805A4 (en
Inventor
Emir TEMIZKAN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Safas Saf Plastik Sanayi Ve Ticaret AS
Original Assignee
Safas Saf Plastik Sanayi Ve Ticaret AS
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
Application filed by Safas Saf Plastik Sanayi Ve Ticaret AS filed Critical Safas Saf Plastik Sanayi Ve Ticaret AS
Publication of EP4326805A1 publication Critical patent/EP4326805A1/en
Publication of EP4326805A4 publication Critical patent/EP4326805A4/en
Pending legal-status Critical Current

Links

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.

Landscapes

  • 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

The invention relates to 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.

Description

CHEMICAL METHOD FOR PRODUCING A POLYOL
Technical Field
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.
Prior Art
When considering the recycling of the flexible polyurethane foam, it is seen that this can be achieved by many methods. It is possible to reuse the flexible polyurethane foam wastes by using the physical or chemical recycling methods.
Therefore, in the state of the art, 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. In addition, 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. Of these, 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. In another method, 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%.
On the other hand, 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. In addition, 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. However, in order to close the carboxylic acid groups (-COOH) at the end of the disubstituted polyurea structures formed at the end of the acidolysis reaction, an esterification reaction is carried out by adding a bifunctional alcohol such as diethylene glycol to the system. As a result, the ester bonds are formed in the system and even the unreacted glycol remains.
When we look at the studies carried out in this way, it has been seen that although the recycled polyol has been successfully obtained, this product creates some problems when used during the formation of the flexible polyurethane foam. For this reason, the products obtained in the state of the art are mostly used in the production of the rigid polyurethane foam. The biggest problem encountered during the production of the flexible polyurethane foam is that even when maximum 25% of the required polyol is used from the obtained recycled polyol, it causes the closed cell formation in the system, acceleration of the reaction and shrinkage in the obtained flexible PUR foam. It is thought that the biggest reason for this is that the alcohol (such as DEG) added to the system for the esterification reaction does not react and remains in the environment. In order to prevent the shrinkage, 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.
In the patent document no. US2019/0359788A1 in the state of the art, the polyol obtained by the recycling method is described. In the first step of the method described in said document, the polyurethane wastes are subjected to a reaction with the dicarboxylic acid, polyether polyol and free radical initiator at 170-210 °C. In the second step, the mixture obtained in the first step obtains an isocyanate-reactive polyol mixture with a short-chain diol or triol at 180- 230 °C. In said document, the polyol mixture obtained is also given. However, 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.
In another document US8030364B2 in the state of the art, it is described that PET polyol is obtained by using the polymeric fatty acids, polybasic acids, polyol and amine and used in the polyurethane foam. In the method described in the document, firstly, the polymeric fatty acid ester was obtained from the oil and then this structure was modified with the alcohol. Then, the polymeric oil-modified polyester amine polyol was obtained by adding the carboxylic acid, DEG and PET wastes to the structure. However, in the method described in the document, the acidolysis reaction is not described. Also, the fatty acids have been used for a different purpose. On the other hand, 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. On the other hand, 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.
In another patent document EP0682063A1 in the state of the art, it is described that the polyol is obtained from the polyurethane wastes with the diol or polyol with a low molecular weight and urea or carbamic acid.
In another document no US4044046 in the state of the art, it is described that the polyol is obtained from the polyurethane wastes at 200 °C by using the diol- and phosphate-based materials.
When the documents in the state of the art are examined, the natural oil component used in the polyol production method by the acidolysis from the flexible PUR foam wastes is not described.
Summary of the Invention
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.
With the invention, 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. Thus, 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).
In addition, since 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. According to the researches, 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. However, in 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.
Description of the Figures:
Fig. 1 is the flow diagram of the method of the invention.
Description of the References in the Figures
For a better understanding of the invention, the description of the numbers in the figures is given below:
BP- Base Polyol
PUR- Polyurethane Foam Wastes
DY- Natural Oil
AN- Anhydride
A- Acidolysis
OA- Oxidizing agent
GDP- Recycled polyol
Detailed Description 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:
- adding the base polyol, natural oil and anhydride to the reactor in the first step
- heating the reagents in the first step by increasing the temperature to a certain temperature value in the second step - dosing the oxidizing (or oxidation) agent into the reactor for a certain period of time and performing a cooling in the third step so that the temperature does not rise above a certain value, since the reaction is exothermic
- continuing the reaction at a certain time and temperature after dosing in the fourth step
- heating the existing reagents by increasing the temperature to a certain value after the oxidation reaction is over in the fifth step
- adding the flexible PUR foam wastes to the existing reagents over a period of time and meanwhile, heating the existing reagents by increasing the temperature from an initial temperature to the certain temperature values in a controlled manner in the sixth step
- applying a certain value of vacuum to the reactor when the acid number falls below a certain value and continuing the vacuum until the water content in the reactor drops below a certain percentage in the seventh step
- cooling the reactor to a certain temperature and obtaining the recycled polyol in the eighth step.
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. During the acidolysis, 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.
In addition, 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.
Based on the total amount, 25% to 30% by weight of polyether polyol (base polyol), 20% to 25% by weight of the natural oil comprising low double bond and 4% to 8% by weight of anhydride are used in the first step of the method. In the preferred embodiment of the invention, 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.
In the fourth step, 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. In addition, the flexible PUR foam wastes in the sixth step are added to the existing reagents for 2 to 3 hours. In addition, 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.
In the seventh step, the acid number is 2 mg KOH/g and the vacuum value is -0.8 atm. In addition, 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.
In the method for producing the recycled polyol of the invention, 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. In the use of the vegetable oils containing more double bonds than 2.0 double bonds/mole of oil, the cross-linking will increase as the functionality will increase and the use of the oil will not provide an advantage. Thus, 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. When 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. When 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.
The 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) used in the production of the standard flexible polyurethane foam and the isocyanate structures (80:20 2, 4-2, 6 toluene diisocyanate, equivalent weight: 87 g/mol) are given in Scheme-I.
Scheme I The reaction scheme (Scheme II) in the method of the invention is as follows, and the oxidation reaction of anhydride and oil takes place firstly among the components added to the reactor. The molecular weight calculation of the amount of the flexible PUR waste used is given below.
1170 g/mol + 87 g/mol = 1257 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.
For each 1 mole equivalent of the polyurethane waste, 1 mole equivalent of the anhydride (monoperoxy dicarboxylic acid) is reacted. For each 1 mole equivalent of the disubstituted urea, 0.6 moles of the epoxidized oil should be reacted. However, an excess of 10-25% of the epoxidized oil is used in the reaction.
Scheme III: The flexible Polyurethane (PUR) wastes and monoperoxy dicarboxylic acid are reacted and the disubstituted urea and recycled polyol and CO2 are released.
Scheme III
Scheme IV: After the first reaction, the disubstituted urea reacts with the epoxidized oil released as a result of the oxidation of the palm oil and the recycled polyol is obtained.
Scheme IV
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%. In addition, contrary to the systems in the prior art, which showed shrinkage even at 25% of use, 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. In the reaction, the double bonds were epoxidized by the oxidizing agent and then reacted with the carboxylic acid group in the substituted urea to form a polyol, thus the esterification reaction was not required. Thus, the negative effects of the unreacted alcohols used in the esterification are avoided with the invention.
Initial formulation:
Table 1 : Recycled polyol recipe
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.
In the state of the art, 40% of the flexible PUR waste is used during the reaction of the recycled polyol which can be used at a maximum of 25%. Considering these amounts, instead of 100 parts of the base polyol, 10 parts of the flexible PUR waste are added to the flexible PUR foam. The usage amount of the recycled polyol obtained with the invention can be increased from 25% to 45%. During the acidolysis reaction, 40% of the flexible PUR waste can be used again. Thus, instead of 100 parts of the base polyol, 18 parts of the flexible PUR waste are added to the flexible PUR foam. In other words, it is seen with this invention that it is possible to use more than 80% of the waste amount used in the prior art.
The calculations for the flexible PUR foam formulation obtained using the recycled polyol are given below.
Scraps amount/total amount of polyol: 0.25 x 0.40 x 100= 10% (the state of the art)
Scraps amount/total amount of polyol: 0.45 x 0.40 x 100= 18% (with the invention) Since the OH value of the base polyol used in the standard flexible PUR foam production is 46-50 mg KOH/g, the OH value of the recycled polyol obtained is 45-50 mg KOH/g (same as the base polyol) so it facilitates the use the recycled polyol during the flexible PUR foam 5 production.
It is desired that 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.
10
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 2: Technical properties of polyol
15
Many physical parameters such as density, hardness, compression set, resilience, tensile strength, elongation at break and air permeability are in the region of the control samples.
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:
(1) The standard value range is the range which is necessary when performing the quality control.
(2) These are the properties of the polyurethane foam normally produced without using the recycled polyol.
(3) These are the properties of the polyurethane foam obtained using 25% of the polyol obtained by the acidolysis without using oil.
(4) These are the properties of the polyurethane foam obtained using 45% of the polyol obtained by the invention.
Considering the properties of the foam, 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 more the recycled polyol is used in the flexible PUR foam, the higher the recovery rate of the scraps (wastes) is. Therefore, it is important to increase the amount of usage. Besides, the cost of the recycled polyol is very economical compared to the base polyol used in the flexible PUR foam. Again, thanks to the invention, with the increase in the amount of the recycled polyol used in the flexible PUR foam, it has become possible to produce more economically the flexible PUR foam of the same standard and quality.
Industrial Applicability of the Invention
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.
The invention is not limited to the above exemplary embodiments, and the person skilled in the art can readily present other different embodiments of the invention. These should be considered within the protection scope of the invention claimed by the claims.

Claims

CLAIMS A method for producing a recycled polyol to recover the scraps (or wastes) that occur during the production of the flexible polyurethane foams (PUR) into the system, characterized in that it comprises respectively the following steps:
- adding the base polyol, natural oil and anhydride to the reactor in the first step
- heating the reagents in the first step by increasing the temperature to a certain temperature value in the second step
- dosing the oxidizing agent into the reactor for a certain period of time and performing a cooling in the third step so that the temperature does not rise above a certain value, since the reaction is exothermic
- continuing the reaction at a certain time and temperature after dosing in the fourth step
- heating the existing reagents by increasing the temperature to a certain value after the oxidation reaction is over in the fifth step
- adding the flexible PUR foam wastes to the existing reagents over a period of time and meanwhile, heating the existing reagents by increasing the temperature from an initial temperature to the certain temperature values in a controlled manner in the sixth step
- applying a certain value of vacuum to the reactor when the acid number falls below a certain value and continuing the vacuum until the water content in the reactor drops below a certain percentage in the seventh step
- cooling the reactor to a certain temperature and obtaining the recycled polyol in the eighth step. The method according to claim 1 , characterized in that the base polyol used in the first step is a polyether triol with an OH value of 46-50 mgKOH/g and a molecular weight of 3000-3500 g/mol. The method according to claim 2, characterized in that the natural oil used in the first step is a palm oil with an iodine number of 57-65 gl/100 g and a value of 1.5- 2.0 DB/mol.
4. The method according to claim 3, characterized in that the natural oil in the first step of the method is a palm oil with a value of 1.7 DB/mol.
5. The method according to claim 4, characterized in that based on the total amount, 25% to 30% by weight of polyether polyol (base polyol), 20% to 25% by weight of the natural oil comprising low double bond and 4% to 8% by weight of anhydride are used in the first step.
6. The method according to claim 5, characterized in that an oxidizing agent used in the second step is used at a rate of 2% to 5% by weight, based on the total amount.
7. The method according to claim 6, characterized in that the temperature in the second step is 40 °C to 50 °C.
8. The method according to claim 7, characterized in that the temperature in the third step is not above 80 °C.
9. The method according to claim 8, characterized in that the temperature value in the fifth step is 110 °C to 130 °C.
10. The method according to claim 9, characterized in that the PUR foam wastes in the sixth step are at the rate of 38% to 42% by weight based on the total amount and are added to the existing reagents for 2 to 3 hours.
11. The method according to claim 10, characterized in that the initial temperature in the sixth step is 120°C and the temperature of the reagents is increased from this temperature value to 200 °C to 220 °C.
12. The method according to claim 11 , characterized in that the acid number in the seventh step is 2 mg KOH/g.
13. The method according to claim 12, characterized in that the vacuum value in the seventh step is -0.8 atm. The method according to claim 13, characterized in that the percentage of the water in the seventh step is below 0.1%. The method according to claim 14, characterized in that the cooling temperature value in the last step is 80 to 90 °C.
EP22851380.0A 2022-06-24 2022-08-03 Chemical method for producing a polyol Pending EP4326805A4 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR2022010512 2022-06-24
PCT/TR2022/050817 WO2023249580A1 (en) 2022-06-24 2022-08-03 Chemical method for producing a polyol

Publications (2)

Publication Number Publication Date
EP4326805A1 true EP4326805A1 (en) 2024-02-28
EP4326805A4 EP4326805A4 (en) 2024-08-07

Family

ID=89380340

Family Applications (1)

Application Number Title Priority Date Filing Date
EP22851380.0A Pending EP4326805A4 (en) 2022-06-24 2022-08-03 Chemical method for producing a polyol

Country Status (2)

Country Link
EP (1) EP4326805A4 (en)
WO (1) WO2023249580A1 (en)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5117297A (en) 1974-08-02 1976-02-12 Bridgestone Tire Co Ltd Horiooruo horiuretanjugobutsukara kaishusuruhoho
DE3435014C2 (en) * 1984-09-24 1986-10-09 Gunter Dr. 7080 Aalen Bauer Process for the production of polyol-containing liquids by converting polymer waste
DE4416322A1 (en) 1994-05-09 1995-11-16 Bayer Ag Process for the preparation of compounds containing hydroxyl groups from (polyurethane) polyurea waste
DE19512778C1 (en) * 1995-04-05 1996-12-05 Gunter Prof Dr Bauer Prodn. of isocyanate-reactive poly:ol dispersion from waste polyurethane
KR101168766B1 (en) 2004-10-11 2012-07-26 김효성 Polyols and Polyurethanes and Polyurethane Foams Using the Same
CZ2009620A3 (en) * 2009-09-22 2011-04-06 Ústav makromolekulární chemie AV CR, v.v.i. Raw material for producing polyurethanes and process for preparing thereof from waste polyurethane
DE102016122276A1 (en) 2016-11-18 2018-05-24 H & S Anlagentechnik Gmbh recycling polyol
CN107722344B (en) * 2017-11-03 2020-08-07 刘斌 Method for recycling edible oil and waste polyurethane

Also Published As

Publication number Publication date
WO2023249580A1 (en) 2023-12-28
EP4326805A4 (en) 2024-08-07

Similar Documents

Publication Publication Date Title
US10611879B2 (en) Polyester polyols from thermoplastic polyesters and dimer fatty acids
EP3212687B1 (en) High recycle content polyester polyols from hydroxy-functional ketal acids, esters or amides
US4551517A (en) Two-component polyurethane adhesive
EP3259299B1 (en) High recycle content polyols from thermoplastic polyesters and lignin or tannin
WO2016153711A1 (en) Photocurable compositions for three-dimensional printing
US3663515A (en) Process of preparation of polycaprolactone polyesters and polyurethane elastomers therefrom
JP2008535789A (en) New polyols derived from vegetable oils using oxidation processes
KR20190123286A (en) Sustainable and energy-curable polyester polyols and coatings or rigid foams therefrom
JPS6084327A (en) Low viscosity aromatic polyol and manufacture
Simón et al. Sustainable polyurethanes: Chemical recycling to get it
JPWO2008123323A1 (en) Method for producing polyol and the polyol
CN108314770A (en) Carbon dioxide-base aqueous polyurethane dispersion, preparation method and carbon dioxide-base waterborne polyurethane pressure-sensitive adhesives
EP4326805A1 (en) Chemical method for producing a polyol
US5508312A (en) Process for the production of compounds containing hydroxyl groups from (polyurethane) polyurea waste materials
US6780962B2 (en) (Meth)acrylic ester binders from glycolyzed aromatic polyesters
JP3889858B2 (en) Urethane / unsaturated organooligomer and process for producing the same
JP2006001865A (en) Hydroxyalkoxy compound derived from polymerized fats and oils
AU2019410411A1 (en) Compact polyurethane
KR20020034654A (en) Process for preparing depolymerized polyol
US5952436A (en) Process for making water-resistant polyetherester resins and thermosets
US4789719A (en) Manufacture of block polyester polyols, and polyurethanes derived therefrom
CN118146495A (en) Boric acid polyether polyol, preparation method and method for preparing polyurethane sealant by using boric acid polyether polyol
JPH08510281A (en) Method for producing polyaddition or polycondensation product
JP2020059789A (en) Resin composition and article formed from resin composition
EP4130083A1 (en) Polyol composition

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20230210

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

RIN1 Information on inventor provided before grant (corrected)

Inventor name: EROGLU, GULDEN

Inventor name: AKSU, YAPRAK

Inventor name: TEMIZKAN, EMIR

RIN1 Information on inventor provided before grant (corrected)

Inventor name: TEMIZKAN, EMIR

A4 Supplementary search report drawn up and despatched

Effective date: 20240710

RIC1 Information provided on ipc code assigned before grant

Ipc: C08L 75/04 20060101ALI20240704BHEP

Ipc: C08G 18/82 20060101ALI20240704BHEP

Ipc: C08J 11/04 20060101AFI20240704BHEP

RIN1 Information on inventor provided before grant (corrected)

Inventor name: YAPRAK AKSU

Inventor name: GUELDEN EROGLU

Inventor name: TEMIZKAN, EMIR