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
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4202—Two or more polyesters of different physical or chemical nature
• • 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
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
  • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
  • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
  • C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
• • 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
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
  • C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
• • 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
  • C08J11/16—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 inorganic material
• • 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
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
• • 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
  • C08G2110/0025—Foam properties rigid
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

• the invention concerns the method for producing secondary polyols via recycling waste polyisocyanurate (PIR) foams and their use.
• PIR waste polyisocyanurate
• PIR foams practically replaced polyurethane (PUR) foams, which had been used earlier, as they have better thermoinsulating properties and fire resistance. Waste produced during the production and mainly after the service life of PIR foam poses serious problem for both, the environment and the production itself, apart from the economic waste caused by the disposal of valuable PIR polymers.
• polyester polyols used currently in the production of PIR and PUR foams are received by similar recycling methods, mainly by the alcoholysis of waste polyesters, pofyethyleneterephta!ate (PET) from bottles and its production waste. These methods are described in patent files: US4439550 A, US4048104 A, US4506090A, EP2565226A1, US4701477A, US4469824, US4559370, JPS59105015.
• the method for producing secondary polyols is solved by recycling secondary raw materials containing waste polyisocyanurate (PIR) foams, i.e. waste coming from the production of PIR foams and PIR foams after their life span.
• Waste PIR foams are first mixed with polyester based polymers and subjected to controlled glycerolysis in microwave field where they undergo mixed catalytic depolymerization.
• Polyester based polymers are meant mainly waste polyethyteneterephtalate (PET) from e.g.
• Controlled glycerolysis means the process of depolymerization of polymer mixture under predetermined conditions i.e. the contents of particular components in the mixture, the reaction temperature and time.
• the principle of invention lies in processing the mixed catalytic depolymerization with alkali metal carboxylate based catalyzer having the chainlength C6-C20. preferably C 6 -C 12 , and/or with organic guanidine and amidine superbases and their mixtures present in glycerol, at concentrations 0,1 up to 1,0 mol.f 1 .
• the catalyzers solved in glycerol can possibly be alkali metal carboxylate based salts, e.g. potassium 2-ethyihexanoate, potassium decanoate etc., in amounts 0,10 up to 0,40 %mol.
• Organic superbase can be e.g.
• TMG tetramethykjuanidine
• TMG triazabicyclodecene etc.
• Mixed catalytic depolymerization proceeds in two stages, in the first stage the depolymerization of polyester takes place in alcoholyzing agent - glycerol and in the second stage the depolymerization of PIR foams proceeds in the mixture of residual agent and oligoesters and polyols formed in the first stage.
• the reaction mixture subjected to mixed catalytic depolymerization contains 15 to 30 wt % of waste PIR foams having the isocyanurate index higher than 2, turner 20 to 40 wt % of polyesters, preferably waste potyethyleneterephtalates, and 40 to 60 wt % of glycerol.
• This reaction mixture can possibly contain also side admixtures and impurities in amounts up to 10 wt %.
• the polyester component contains for example waste ground PET from bottles with residual parts of PVC and paper labels.
• the principle of invention lies also in carrying out the mixed catalytic depolymerization at temperatures from 180 up to 300 °C, preferably 200 to 270 °C, applying microwave heating to the reactive mixture from microwave generator at working frequency 0,8 to 3 GHz for the time period max. 1 hour, depending on the generator power.
• the principle of invention lies also in depriving the product of mixed catalytic depolymerization from eventual coarse mechanical impurities by filtration, centrifugation or decantation prior to its cooling.
• the principle of invention lies also in utilization of secondary polyols produced by the method introduced in this patent application.
• the mixture of virgin (primary) and recycled (secondary) polyol is used for the preparation of new polyisocyanurate foams.
• the content of secondary polyol in this mixture ranges within 5 - 25 wt %.
• tower addition would lead to insufficient valuation of recycled polyols, higher addition could in some cases negatively affect the quality of produced PIR foams.
• the production method itself, it is the method utilizing the glycerolysis of the mixture of secondary raw materials in the microwave field, where the main components are linear polyester and waste polyisocyanurate thermoinsulating foams (PIR).
• PIR thermoinsulating foams
• the utilization of microwave heating brings about substantial shortening of reaction time, which significantly contributes to the improvement of economic balance of the process.
• the catalyzer from the group of alkali metal carboxytates having the chainlength mentioned above or from the group of organic superbases is required.
• the glycerolysis i.e. the alcoholysis with glycerol was selected due to excellent physical-chemical properties of glycerol, mainly due to high ability to absorb microwave field and high boiling point, which enables non-pressure operation at temperatures required for the preparation of polyol.
• alkali metal carboxylates having the chainlength Ce-Ci2 show the highest activity during the depolymerization. They also work as compatibility agents or surfactants for the polymer of low polarity and polar molecules of glycerol during initial phase of depolymerization. The start of reaction is accelerated and formed reaction mixture is stabilized during the storage. Potassium salts are preferably used due to simultaneous catalytic activity in the process of isocyanates trimerisation, the main process in polyisocyanurate polymers preparation. Hence the presence of depolymerization catalyzer in prepared secondary polyol does not affect the production process of PIR materials.
• organic guanidine and amidine superbases Another group of catalyzers exhibiting strong activity in the depolymerization process are organic guanidine and amidine superbases.
• organic superbases are decomposed to carboxyl salts due to the reaction with carbon dioxide liberated during the depolymerization.
• reaction mixture is formed by hard thermal insulation pofyisocyanurate foam with the isocyanurate index value of 2.5, consisting of modified MDI and polyester polyol.
• the polyester component is formed by secondary ground bottle polyethyleneterephtalate.
• the reaction environment is anhydrous glycerol with the purity of 99 %.
• PIR foam was ground to particles smaller than 2 mm in diameter and compounded with dear, colorless PET with floccuie diameter smaller than 4 mm, after which the mixture was subjected to mixed catalytic depolymerization in the microwave field, during which secondary polyol in the form of homogeneous liquid product was formed by alcoholysis and transesterification reactions.
• the reaction mixture which was subjected to mixed catalytic depotymerization, contained 20 wL % waste PIR foams, 30 wt. % waste polyethyleneterephthalate and 50 wt. % glycerol.
• Glycerol in this example contained 0.35 mol % 2-ethyl sodium-hexanoate (total chain length C 8 ).
• Mixed catalytic depotymerization proceeded in two phases, at first polyester was depolymerized in alcoholysis agent - glycerol, followed by the depotymerization of PIR foams in the mixture of remaining agent and oligoesters and polyols formed in the first phase.
• reaction mixture 30 g were heated by the microwave generator with working frequency of 2.45 GHz and continuously stirred (1000 rev.min -1 ). Complete depotymerization was reached at 250°C after 360 s at absorbed heating power of 125 W.
• the product was a secondary polyol in the form of clear viscous liquid with the following properties:
• PIR foam was ground to particles smaller than 2 mm and compounded with clear colorless PET with floccule diameter smaller than 4 mm, after which this mixture was subjected to controlled glycerolysis by mixed catalyttcal depotymerization in microwave field, in the same way as in example 1.
• the reaction mixture in this example consisted of 23 wt % waste PIR foams, 27 wt % waste polyethyleneterepthalate and also 50 wt % glycerol.
• glycerol contained 0.35 mol % 2-ethyl sodium hexanoate.
• reaction mixture 30 g were heated by microwave generator with working frequency of 2.45 GHz and continuous stirred (1000 rev.min -1 ).
• the product was secondary polyol in the form of clear viscous liquid with the following properties:
• the method for producing secondary polyols according to the fourth invention example was carried out in the same way as in example 1 with the exception that the reaction mixture, which was subjected to mixed cata!ytical depolymerization, consisted of 20 wt. % waste PIR foams, 30 wt. % waste fraction from recycled PET bottles, composed of colour mix PET particles with traces of PVC and paper labels with 97,2 % total PET amount and with the maximum floccule diameter smaller than 8 mm and also 50 wt % glycerol.
• glycerol contained 0.35 mol% 2-ethyl sodium hexanoate, and 30 g of reaction mixture were heated by microwave generator with working frequency of 2.45 GHz and continuously stirred (1000 rev.min -1 ). Complete depolymerization was reached after 360 s at absorbed heating power of 125 W.
• the deporymerization product was filtered at 150 *C through glass filter with the pore size d ⁇ 10 pm and secondary polyol was gained as a product, free from mechanical impurities, in the form of viscous liquid with the following properties
• Secondary polyol produced according to example 1 replaced 5, 10 and 15 wt. % of virgin polyol in the manufacturing of heat-insulating PIR foam with identical composition as PIR material used in the process of manufacturing secondary polyol.
• the properties of foam prepared in such way were compared to those of standard foam without this polyol addition.

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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)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
• Polyurethanes Or Polyureas (AREA)

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• 2014
  • 2014-12-22 CZ CZ2014-945A patent/CZ2014945A3/cs not_active IP Right Cessation
• 2015
  • 2015-12-18 WO PCT/CZ2015/000152 patent/WO2016101938A1/en not_active Ceased
  • 2015-12-18 EP EP15834632.0A patent/EP3259309A1/en not_active Withdrawn

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