EP3259309A1 - Method for producing secondary polyols and their use - Google Patents
Method for producing secondary polyols and their useInfo
- Publication number
- EP3259309A1 EP3259309A1 EP15834632.0A EP15834632A EP3259309A1 EP 3259309 A1 EP3259309 A1 EP 3259309A1 EP 15834632 A EP15834632 A EP 15834632A EP 3259309 A1 EP3259309 A1 EP 3259309A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- foams
- pir
- waste
- polyol
- polyols
- 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.)
- Withdrawn
Links
- 229920005862 polyol Polymers 0.000 title claims abstract description 54
- 150000003077 polyols Chemical group 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229920000582 polyisocyanurate Polymers 0.000 claims abstract description 57
- 239000011495 polyisocyanurate Substances 0.000 claims abstract description 56
- 239000006260 foam Substances 0.000 claims abstract description 48
- 239000002699 waste material Substances 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 229920000728 polyester Polymers 0.000 claims abstract description 21
- 239000011541 reaction mixture Substances 0.000 claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 238000004064 recycling Methods 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- -1 alkali metal carboxylate Chemical class 0.000 claims abstract description 9
- 239000004032 superbase Substances 0.000 claims abstract description 9
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012263 liquid product Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims abstract description 4
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920002601 oligoester Polymers 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 2
- 238000006136 alcoholysis reaction Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 229920002635 polyurethane Polymers 0.000 description 9
- 239000004814 polyurethane Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 150000007525 superbases Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 4
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 3
- GTBXAGPZKPTPEJ-UHFFFAOYSA-N CC[Na].CCCCCC(O)=O Chemical compound CC[Na].CCCCCC(O)=O GTBXAGPZKPTPEJ-UHFFFAOYSA-N 0.000 description 3
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- 239000006261 foam material Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000034659 glycolysis Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- QDIGBJJRWUZARS-UHFFFAOYSA-M potassium;decanoate Chemical compound [K+].CCCCCCCCCC([O-])=O QDIGBJJRWUZARS-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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.
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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CZ2014-945A CZ2014945A3 (cs) | 2014-12-22 | 2014-12-22 | Způsob výroby sekundárních polyolů a jejich použití |
| PCT/CZ2015/000152 WO2016101938A1 (en) | 2014-12-22 | 2015-12-18 | Method for producing secondary polyols and their use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP3259309A1 true EP3259309A1 (en) | 2017-12-27 |
Family
ID=55352976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP15834632.0A Withdrawn EP3259309A1 (en) | 2014-12-22 | 2015-12-18 | Method for producing secondary polyols and their use |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP3259309A1 (cs) |
| CZ (1) | CZ2014945A3 (cs) |
| WO (1) | WO2016101938A1 (cs) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113354863B (zh) * | 2021-07-08 | 2023-05-26 | 山东东特环保科技有限公司 | 一种废旧聚氨酯的降解方法、一种聚氨酯保温材料 |
| ES2958484A1 (es) * | 2022-07-14 | 2024-02-09 | Univ Murcia | Procedimiento de despolimerizacion de poliuretano |
| ES3043584T3 (en) * | 2022-10-10 | 2025-11-25 | Polykey Polymers S L | Low-temperature organocatalyzed depolymerization of poly(ethylene terephthalate) |
| EP4389809A1 (en) | 2022-12-23 | 2024-06-26 | Sipchem InnoVent SA | Apparatus and method for depolymerizing polycondensation polymers |
Family Cites Families (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3708440A (en) * | 1972-02-14 | 1973-01-02 | Upjohn Co | Reclaiming scrap polyisocyanurate foam with an aliphatic diol and a dialkanolamine |
| US4048104A (en) | 1976-08-05 | 1977-09-13 | Freeman Chemical Corporation | Polyisocyanate prepolymers from scrap polyester and polyurethane foam products obtained therefrom |
| US4159972A (en) | 1977-10-17 | 1979-07-03 | Ford Motor Company | Dissolution of polyurethane foams and re-use of the products therefrom |
| US4316992A (en) | 1981-02-23 | 1982-02-23 | Ford Motor Company | Process for polyol recovery from polyurethane foam comprising alcohol and steam hydrolysis |
| US4444919A (en) | 1982-11-22 | 1984-04-24 | Texaco Inc. | Use of polyethylene terephthalate liquid waste streams containing glycols as rigid polyol extenders |
| US4439550A (en) | 1982-11-22 | 1984-03-27 | Texaco Inc. | Aromatic polyols made from recycled polyethylene terephthalate waste streams, alkylene glycol and dibasic acid waste streams |
| US4701477A (en) | 1983-07-13 | 1987-10-20 | Chardonol, Division Of Freeman Corporation | Low viscosity aromatic polyols and methods for their preparation |
| US4506090A (en) | 1983-07-15 | 1985-03-19 | Texaco Inc. | Aromatic polyols made from polyethylene terephthalate scrap, glycols and aromatic carbonyl-containing compounds |
| US4469824A (en) | 1983-11-18 | 1984-09-04 | Texaco, Inc. | Liquid terephthalic ester polyols and polyisocyanurate foams therefrom |
| US4559370A (en) | 1984-05-25 | 1985-12-17 | Blanpied Robert H | Copolyester polyol resins, polyol blends comprising the same, and resultant polyisocyanurate foams |
| JP3265084B2 (ja) | 1993-11-01 | 2002-03-11 | 三井化学株式会社 | 硬質ポリイソシアヌレートフォーム廃棄物からポリオールを得る方法 |
| DE19643057A1 (de) * | 1996-10-18 | 1998-04-23 | Basf Ag | Verfahren zur Herstellung von Polyisocyanuratschaumstoffen mit verminderter Wärmeleitfähigkeit |
| US20050096482A1 (en) * | 2002-02-01 | 2005-05-05 | Ryozo Tamada | Method of depolymerizing polyethylene terephthalate and process for producing polyester resin |
| KR20040024064A (ko) | 2002-09-13 | 2004-03-20 | 김영미 | 폴리우레탄폼 폐기물의 화학적 분해에 의해 얻어진 재생 폴리올과 hfc계 발포제를 이용한 폴리이소시아누레이트 폼의 제조. |
| JP4680266B2 (ja) * | 2005-12-09 | 2011-05-11 | 財団法人くまもとテクノ産業財団 | ポリエステルの解重合方法、および当該解重合方法を用いたポリエステルモノマーの回収方法 |
| DE102006039057A1 (de) * | 2006-08-19 | 2008-02-21 | Bayer Materialscience Ag | Verfahren zur Herstellung von Polyolen und/oder Polyaminen aus Polyurethanen, Polyurethanharnstoffen und Polyharnstoffen |
| DE102006058400A1 (de) * | 2006-12-07 | 2008-06-12 | Recyclit Gmbh | Verfahren zur Herstellung neuer flammgeschützter Polyurethane |
| CZ299908B6 (cs) * | 2007-07-13 | 2008-12-29 | Ústav chemických procesu Akademie ved CR | Zpusob chemické depolymerace odpadního polyethylentereftalátu |
| CZ301686B6 (cs) | 2007-08-23 | 2010-05-26 | Ústav makromolekulární chemie AV CR, v.v.i. | Zpusob recyklace odpadních polyurethanových pen |
| CN101538358B (zh) * | 2009-04-29 | 2011-08-31 | 福建兴宇树脂有限公司 | 一种用于聚氨酯鞋底聚酯多元醇的微波合成方法 |
| RO128141B1 (ro) | 2011-06-23 | 2016-02-26 | Institutul Naţional De Cercetare-Dezvoltare Pentru Chimie Şi Petrochimie - Icechim | Procedeu de obţinere a unor poliester-eter polioli aromatici din deşeuri de polietilentereftalat (pet) şi poliester-eter polioli aromatici încorporând deşeuri de polietilentereftalat şi materiale regenerabile, obţinuţi prin respectivul procedeu |
| CN103342791A (zh) * | 2013-07-25 | 2013-10-09 | 北京市建筑工程研究院有限责任公司 | 一种pu/pir泡沫塑料废料生产多元醇的制备方法 |
-
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
Also Published As
| Publication number | Publication date |
|---|---|
| CZ305739B6 (cs) | 2016-02-24 |
| WO2016101938A1 (en) | 2016-06-30 |
| CZ2014945A3 (cs) | 2016-02-24 |
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