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WO1999054380A1 - Dispositif de production d'alcools de polyester, et alcools de polyester - Google Patents

Dispositif de production d'alcools de polyester, et alcools de polyester Download PDF

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Publication number
WO1999054380A1
WO1999054380A1 PCT/EP1999/002603 EP9902603W WO9954380A1 WO 1999054380 A1 WO1999054380 A1 WO 1999054380A1 EP 9902603 W EP9902603 W EP 9902603W WO 9954380 A1 WO9954380 A1 WO 9954380A1
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WO
WIPO (PCT)
Prior art keywords
polyester
glycol
mixture
glycols
alcohols
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.)
Ceased
Application number
PCT/EP1999/002603
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German (de)
English (en)
Inventor
Gerhard Behrendt
Andreas Lobeda
Martin Pohl
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.)
Havel Chemie AG
Original Assignee
Havel Chemie AG
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 Havel Chemie AG filed Critical Havel Chemie AG
Priority to AU39270/99A priority Critical patent/AU3927099A/en
Publication of WO1999054380A1 publication Critical patent/WO1999054380A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
    • C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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 relates to a process for the production of polyester alcohols and polyester alcohols which are produced by this process, according to the preamble of claim 1.
  • polyesters primarily polyethylene terephthalate (PET)
  • alcoholysis is generally carried out with monoalcohols or dialcohols such as glycols at elevated temperature, catalysts often being added to the reaction mixture in order to achieve acceptable reaction times. If the reaction is carried out without a catalyst, longer reaction times and / or higher temperatures are generally required. So z.
  • PET fiber waste with different amounts of ethylene glycol is converted to oligomeric diols in the presence of zinc acetate at temperatures between 170 ° C and 200 ° C in about 10 hours.
  • zinc acetate With adipic acid and toluenesulfonic acid, these further become polyesters converted.
  • the excess of ethylene glycol leads to a depolymerization up to the stage of bis (2-hydroxyethyl) terephthalate and its reaction with adipic acid.
  • the depolymerization of the PET can be accelerated by the reaction under pressure and the addition of typical transesterification catalysts, so that the process can be carried out on a large technical scale.
  • the main goal of these depolymerization processes is the recovery of dimethyl terephthalate, see e.g. B. DE 26 57 044 and US 5051528. Since the PET wastes in the melt of bis- (2-hydroxyethyl) terephthalate or of oligomers or their mixtures dissolve relatively quickly and with prolonged exposure to temperature up to an oligomer melt takes place, this is then condensed back into the polymer. In order to obtain salable products, clean and pretreated waste with a known composition and origin is required for glycolysis.
  • EP 0113507 describes the production of polyester alcohols on two different polyester waste streams.
  • the process relates to a waste stream from dimethyl terephthalate production, which consists of dimethyl terephthalate and the by-products of the substituted benzene, while the second waste stream consists of residues from the production of PET.
  • the first waste stream is reacted with an alkylene glycol and the two streams are then reacted together, so that a polyester polyol is produced therefrom.
  • EP 0154079 describes a process for the production of terephthalate polyols in which PET waste is reacted with glycols and the ethylene glycol formed during the reaction is distilled off.
  • Higher functional alcohols e.g. B. N-methylglucoside, triethanolamine, diethanolamine or glycerol can be added.
  • Polyester polyols produced by these processes generally have a viscosity which is too high for machine processing, so that it is desirable to obtain polyester polyols based on terephthalic acid with a lower viscosity and the same good properties.
  • a serious deficiency of the previously known processes and the OH-functional products produced thereafter is therefore their high viscosity, which makes processing in polyurethane systems with conventional technology difficult or even impossible.
  • a disadvantage of all processes is that they only use primary materials for the implementation and can therefore only work economically if high-quality and pure end products are produced.
  • the object of the invention is to provide a process for the production of polyester alcohols with a wide viscosity range by transesterification using waste materials and polyester alcohols and their use.
  • polyester wastes are reacted with a resin containing hydroxyl and ester groups in the presence of the organometallic compounds they contain at elevated temperature in one reaction step.
  • the resin containing hydroxyl and ester groups used according to the invention is an oligohydroxyester-containing mixture which is formed as an undesirable by-product in the case of polyester condensation and which currently has to be disposed of as waste.
  • This mixture containing oligohydroxy esters is generally a highly viscous to solid distillation product from polyester production at room temperature, in which a substantial proportion of organometallic compounds are dissolved as residues of transesterification catalysts.
  • the mixture containing oligohydroxy esters has a different composition due to the production conditions of the polyester and essentially consists of low molecular weight esters of dicarboxylic acids, for PET it is terephthalic acid and glycols, for PET it is ethylene glycol and / or diethylene glycol, from free ethylene glycol, diethylene glycol and de ⁇ ren higher homologues, such of organometallic compounds.
  • a typical composition of a mixture containing oligohydroxy esters, which can be obtained in the production of PET, is e.g. B .:
  • polyester alcohols prepared according to the invention further glycols and / or triols or tetrols, di- and / or polycarboxylic acids or their anhydrides can be added to the reaction mixture.
  • reaction mixture to control the properties of the reaction product, and thus also the plastics made therefrom, higher-functional alcohols, for. B. glycerol, trimethylolpropane, pentaerythritol and / or hexanetriol, with the aim of producing branched polyester alcohols.
  • the ratio of the polyester is preferably too
  • Oligohydroxyesters are between 0.1: 1 and 1: 0.1, the range between 0.5: 1 and 1: 0.5 is particularly preferred. Furthermore, a reaction mixture is preferred in which the ratio of PET to oligohydroxyester is between 0.6: 1 and 1: 0.6 and which also contains between 5 and 50% by mass of a glycol, in particular diethylene glycol, oligoethylene glycol or dipropylene glycol .
  • an aliphatic dicarboxylic acid and / or its anhydrides is additionally added to the glycolysis mixture of glycols, oligoesters and / or polyethylene terephthalate during the transesterification reaction.
  • the viscosity of polyols based on polyethylene terephthalate can be significantly reduced by the fact that during the reaction with glycols, the transesterification or glycolysis, apart from glycols and / or oligoesters, a certain one, but distinctly compared to terephthalic acid a smaller molar amount of adipic acid or of another aliphatic dicarboxylic acid or its anhydrides is added.
  • the viscosities found without this addition are in the range of 15,000 to 350,000 Pas (20 ° C) based on literature and based on our own experience. For processing such polyester polyols on foams However, viscosities below 5000 mPas (20 ° C) are required.
  • the viscosity can be reduced to 1,000 mPas (20 ° C) by adding aliphatic dicarboxylic acids in certain proportions, which are calculated on the polyethylene terephthalate.
  • Advantageous quantitative ratios of polyethylene terephthalate to aliphatic dicarboxylic acid are in particular in the range from 5 to 25% by weight of the latter. This means a molar ratio of terephthalic acid or another aromatic di- or tricarboxylic acid to aliphatic dicarboxylic acid in a ratio between 12.5: 1 and 2.5: 1. In particular, the range between 10: 1 and 4: 1 is found to be advantageous because the viscosity can be easily regulated in it by adding the aliphatic dicarboxylic acid.
  • the polyester alcohols are prepared in one or more stages. The number of stages is primarily dependent on the type of starting materials and the desired speed of implementation.
  • a glycol, a glycol mixture or an oligoester condensate or a mixture of glycols and oligoester condensates is placed in a reaction vessel and heated to a first reaction temperature. At this temperature, which is generally between 150 and 220 ° C, the polyethylene terephthalate in the form of shredded material, chips, granules, ground material or powder is then added and dissolved. After complete dissolution, the temperature is raised to the second reaction temperature, which is generally between 180 and 280 ° C. lies.
  • the aliphatic dicarboxylic acid is added in several steps, small amounts of water being drawn off via a condenser. Depending on the dicarboxylic acid to be added, two to ten dosing steps are required. A dosage in four stages which lie in the first half of the total reaction time is preferred. The duration of the reaction at the second reaction temperature is between three and twelve hours, with reaction times of four to eight hours being preferred.
  • the multi-stage process can in turn be a two-stage, three-stage or four-stage method.
  • a higher number of process stages (cascades) is not favorable for economic reasons, but an infinite number of stages are possible for carrying out the process.
  • the multi-stage process is used in particular when a high percentage of polyethylene terephthalate is to be incorporated and / or when this polyethylene terephthalate is contaminated by other plastics or contains them for various reasons. Of these processes, the two-step process is particularly preferred.
  • the two-stage process can be operated in two basic embodiments.
  • the application of these process variants is primarily dependent on the starting material available.
  • polyethylene terephthalate waste is used in particular. These can be used as pure regrind (e.g. from beverage bottles) or as made with other plastics. mixed shredder goods are available.
  • the glycol mixture or the mixture of glycols and oligoester condensate are placed in a reaction extruder at temperatures between 150 and 200 ° C. and the polyethylene terephthalate waste is metered in by a separate feed.
  • the processing with residence times of 0.5 to 5 minutes and the high shear forces of the extruder screw (s) achieve a homogenization of the reaction mixture.
  • the non-soluble or dispersible plastic parts are separated by means of a screening device when leaving the extruder.
  • the homogeneous mixture is placed in a second reaction vessel and heated to temperatures of 180 to 280 ° C in this. As soon as the reaction temperature is reached, the aliphatic dicarboxylic acid is metered in in several proportions, as has been described for the one-step process.
  • the glycol or the mixture of glycols and / or oligoester condensates are placed in a first reaction vessel and heated to a predetermined dissolution temperature between 150 and 250 ° C. and then the polyester, in particular polyethylene terephthalate waste, is added in the desired ratio. The mixture is stirred at reaction temperatures of 150 to 250 ° C until the polyester has completely dissolved. Other polymers can disperse or suspend in the solution. Some of the foreign plastics contained in the polyester waste, especially PVC and styrene polymers, will remain unchanged in the 10
  • the transesterification is carried out at temperatures between 180 and 280 ° C within 3 to 12 hours.
  • the reaction temperature is reached, the aliphatic dicarboxylic acid is metered in in several steps, as has been described for the one-step process.
  • the polyester alcohols produced according to the invention are filled directly into storage or storage containers without further processing.
  • the essential product data are the hydroxyl number (OHZ) and the viscosity.
  • the OHZ is between 125 and 400, the viscosity between 1200 and 12,000 mPas (20 ° C) depending on the embodiment of the process.
  • Suitable glycols for the process are ethylene glycol and its oligomers, especially diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols with an average molecular weight of 200, 300, 400, 600, 800, 1000; Propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycols with an average molecular weight of 200, 300, 400, 600, 800, 1000; 1,4-butanediol, polybutylene glycols of average molecular weights between 200 and 1000 and 1,6-hexanediol.
  • Suitable aliphatic dicarboxylic acids are in particular adipic acid, furthermore malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, fumaric acid, maleic acid, azelaic acid, cyclohexanedicarboxylic acids or the anhydrides of the acids 11
  • Oligohydroxyester condensates are an undesirable by-product of polyester condensations and are currently being disposed of as waste. They are generally highly viscous to solid distillation products from polyester production at room temperature, in which a substantial proportion of organometallic compounds are dissolved as residues of transesterification catalysts. Due to the production conditions of the polyesters, the oligoester condensates have a different composition and essentially consist of low molecular weight esters of dicarboxylic acid, for PET of terephthalic acid, with the glycols, for PET, ethylene glycol and / or diethylene glycol, free ethylene glycol, diethylene glycol and their higher homologues, organometallic compounds such. B. of titanium, antimony, bismuth, germanium, magnesium, calcium, lead, zinc, tin or cobalt, and free dicarboxylic acid, in PET terephthalic acid.
  • the oligohydroxy esters are used for the polyester alcohols, in particular in relation to the polyester between 1: 4 and 4: 1 and the glycol or glycol mixture from 2: 7: 1 to 7: 2.5: 0.5. Since these areas are very large and allow many variants, some typical relationships are described in the examples. However, these are not to be seen as the limits of the possible variations, since these are determined solely by the required properties of the polyester alcohols. 12
  • the process according to the invention enables linear and branched polyester alcohols with hydroxyl numbers from 150 to 600 and viscosities (at 20 ° C.) from 3000 to 500,000 mPas to be produced, which have an increased aromatic content compared to previous products. This means that they can be used in particular for high-quality and flame-retardant polyurethanes.
  • polyester alcohols according to the invention are advantageously used for the production of rigid polyisocyanate foams.
  • unsaturated dicarboxylic acids maleic acid, fumaric acid
  • unsaturated polyester alcohols can be produced, which can be used advantageously in the production of paints, coatings and adhesives.
  • a major advantage of the invention is that polyester waste, in particular PET, polybutylene terephthalate, etc., with other waste, in particular the condensation residues from polyester synthesis, from glycerol production (glycerol pitch), from trimethylolpropane production (TMP pitch) or from the polyether synthesis (distilled glycol mixture) can be converted into high-quality raw materials without additional catalysts and, to a greater extent, new glycols having to be used for the synthesis, so that there is an ecological as well as an economic progress. Furthermore, by using the method according to the invention, in particular the polycondensation residues not previously used with the therein 13
  • the polyols produced by the process according to the invention are notable for high stability during storage and good miscibility with the additives in polyurethane systems.
  • the reason for these desired good properties is the broad molar mass distribution achieved by the production process according to the invention, both of the terephthalate esters themselves and of the alkylene glycol units arranged in them.
  • the degree of polymerization of PET is in the order of 90 to 100, that of the oligohydroxy esters is 2 to 4. Due to the transesterification, with the participation of the organometallic catalyst residues contained in the oligohydroxy esters, the alkylene glycols present in it result in rapid chain cleavage on the ester groups and thereby causes a reduction in the degree of polymerization.
  • the process according to the invention and the products according to the invention can moreover be produced in a wide viscosity range by different ratios of the starting materials.
  • the viscosity set depends on the intended use.
  • the viscosity for the production of rigid foams should be in the range of 4,000 to 10,000 mPas (20 ° C), while that for coatings and lacquers can be in the range up to 25,000, that for hot melt adhesives up to 100,000.
  • One area of application of great interest is rigid polyurethane and polyisocyanurate foams.
  • viscosities of around 3,000 mPas (20 ° C) are required, which cannot be achieved using the previous methods.
  • the process according to the invention even allows viscosities below 1000 mPas (20 ° C.) to be set.
  • Example 1 The approach of Example 1 is repeated with the following amounts:
  • the reaction is also carried out at 220 ° C., however, this temperature is maintained for 3 hours after the PET addition has ended.
  • the product is a highly viscous syrup with a hydroxyl number of 189 mg KOH / g and a viscosity of 165,000 mPas (20 ° C).
  • Example 1 The approach of Example 1 is repeated with the following amounts:
  • the reaction is also carried out at 220 ° C., however, this temperature is held for 3 hours after the addition of PET has ended and the pressure is then applied at 200 bar.
  • the product is a viscous liquid with a hydroxyl number of 253 mg KOH / g and a viscosity of 22,000 mPas (20 ° C).
  • Example 3 The approach of Example 3 is repeated with 1.15 kg of diethylene glycol, but otherwise under the same conditions.
  • the product is a viscous liquid with a hydroxyl number of 326 mg KOH / g and a viscosity of 11,600 mPas (20 ° C).
  • PET waste 2.20 2.50 2.80 3.00
  • Example 3 The approach of Example 3 is carried out with the following composition:
  • reaction is completed within 3.5 hours at 230 ° C. after the PET addition has ended.
  • the product has a hydroxyl number of 307 mg KOH / g and a viscosity of 42,000 mPas (20 ° C).
  • Example 6 The approach of Example 6 is repeated, but 0.44 kg of triethylolpropane (TMP) are used instead of the glycerol pitch. The reaction is otherwise carried out under the same conditions.
  • TMP triethylolpropane
  • the product is a highly viscous liquid with a hydroxyl number of 301 mg KOH / g and a viscosity of 38,600 mPas (20 ° C).
  • the reaction is completed within 3.5 hours at 230 ° C. after the PET addition has ended.
  • the product has a hydroxyl number of 341 mg KOH / g and a viscosity of 28,700 mPas (20 ° C).
  • reaction is completed within 3.5 hours at 230 ° C. after the PET addition has ended.
  • the product has a hydroxyl number of 385 mg KOH / g and a viscosity of 11,350 mPas (20 ° C).
  • Example 1 a batch is carried out as follows: 0.58 kg of maleic anhydride and 1.30 kg of diethylene glycol are added to 2.05 kg of melted oligohydroxyester at 80 ° C. and the temperature is raised to 150 ° C. Now 1.75 kg of polyester waste (from shredded films and fibers) are added within 1.5 hours and the temperature is slowly increased to 220 ° C. The reaction is brought to an end within 3 hours while slowly raising the temperature to 228 ° C. While the temperature is slowly rising 19
  • Example 13 Repetition of the batch from example 1 with 10% by weight of aliphatic dicarboxylic acid
  • oligohydroxyester 2.2 kg are placed in a 6 1 stirred reactor with heating, thermometer, stirrer, column with column head and condensate discharge, cooler and inert gas flushing and melted.
  • a clear, highly viscous product is obtained at 65 ° C.
  • 320 g of dipropylene glycol and 120 g of adipic acid are added to this.
  • the temperature is raised to 190 ° C. and held at this temperature for one hour.
  • 2.0 kg of PET waste obtained by crushing beverage bottles
  • the temperature is slowly increased to 220 ° C. and water of reaction formed is drawn off at the top of the column.
  • the temperature is held at 220 ° C for a further two hours until no more water is produced.
  • the pressure in the reactor is then reduced to 100 mbar in order to remove water residues and volatile components.
  • a clear, viscous liquid with a hydroxyl number of 319 mg KOH / g and a viscosity of 4,680 mPas (20 ° C.) is obtained.
  • Example 17 Preparation of a PET polyol according to the invention
  • the temperature is raised to 215 ° C during the addition. After the addition has ended, the mixture is stirred at 215-220 ° C. for 3.5 hours. No distillation products are detected in the nitrogen stream. At the end of the reaction time, the pressure is reduced to 100 mbar and volatile constituents are distilled off (23 ml); then it is cooled to 130 ° C. and filled through a filter.
  • the PET polyol has a hydroxyl number of 316 and a viscosity of 4,950 mPas (20 ° C).

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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)
  • General Chemical & Material Sciences (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne un procédé de production d'alcools de polyester, et des alcools de polyester produits selon ce procédé selon la revendication 1. L'invention a pour objet de développer un procédé de production d'alcools de polyester, ayant une large plage de viscosité, par réestérification à l'aide de matières déchets. Pour ce faire, on fait réagir en une opération les déchets de polyester avec une résine contenant des groupes hydroxyl et ester en présence des composés métalloorganiques inhérents et éventuellement de glycols et/ou d'acides dicarboxiliques aliphatiques à des températures élevées. La résine contenant des groupes hydroxyl et ester utilisée est un mélange contenant de l'oligohydroxyester qui est obtenu sous forme de sous produit indésirable lors de condensations de polyester et qui doit être éliminé.
PCT/EP1999/002603 1998-04-16 1999-04-16 Dispositif de production d'alcools de polyester, et alcools de polyester Ceased WO1999054380A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU39270/99A AU3927099A (en) 1998-04-16 1999-04-16 Method for producing polyester alcohols, and polyester alcohols

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19817538.8 1998-04-16
DE19817538 1998-04-16
DE19915128.8 1999-03-25
DE19915128 1999-03-25

Publications (1)

Publication Number Publication Date
WO1999054380A1 true WO1999054380A1 (fr) 1999-10-28

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DE (1) DE19918650A1 (fr)
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1082375A4 (fr) * 1998-03-27 2001-05-02 Swig Pty Ltd Conversion amelioree de polyethylene terephtalate contamine en polybutylene terephtalate decontamine
DE102007063442A1 (de) 2007-12-21 2009-07-16 Gt Elektrotechnische Produkte Gmbh Verfahren zur Herstellung von aromatischen Polyesterpolyolen und diese Polyole
WO2010115532A1 (fr) 2009-04-09 2010-10-14 Bayer Materialscience Ag Polyesterpolyols obtenus à partir d'acide téréphtalique et d'oligo (oxydes d'alkylène)
CN104177901A (zh) * 2014-08-20 2014-12-03 新盾汽车材料（石家庄）有限公司 一种高速列车专用原子灰及其制备方法
CN109851763A (zh) * 2018-12-28 2019-06-07 沈阳化工研究院有限公司 一种锂电池铝塑膜外层胶黏剂的制备方法
US10336925B2 (en) 2015-09-08 2019-07-02 Resinate Materials Group, Inc. Polyester polyols for reactive hot-melt adhesives
JP2020514428A (ja) * 2016-12-23 2020-05-21 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 高い引裂き伝播強度を有する熱可塑性ポリウレタン

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10019081A1 (de) * 2000-04-11 2001-10-25 Enretec Polychemie Entsorgungs Verfahren zur Aufbereitung von bunten und gemischten Polyester-Abfällen
DE102008054940A1 (de) 2007-12-21 2009-07-02 Gt Elektrotechnische Produkte Gmbh Neue Polyurethan-Vergussmassen und Verfahren zu ihrer Herstellung

Citations (3)

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EP1082375A4 (fr) * 1998-03-27 2001-05-02 Swig Pty Ltd Conversion amelioree de polyethylene terephtalate contamine en polybutylene terephtalate decontamine
DE102007063442A1 (de) 2007-12-21 2009-07-16 Gt Elektrotechnische Produkte Gmbh Verfahren zur Herstellung von aromatischen Polyesterpolyolen und diese Polyole
WO2010115532A1 (fr) 2009-04-09 2010-10-14 Bayer Materialscience Ag Polyesterpolyols obtenus à partir d'acide téréphtalique et d'oligo (oxydes d'alkylène)
US8334035B2 (en) 2009-04-09 2012-12-18 Bayer Materialscience Ag Polyester polyols from terephthalic acid and oligoalkylene oxides
CN104177901A (zh) * 2014-08-20 2014-12-03 新盾汽车材料（石家庄）有限公司 一种高速列车专用原子灰及其制备方法
US10336925B2 (en) 2015-09-08 2019-07-02 Resinate Materials Group, Inc. Polyester polyols for reactive hot-melt adhesives
JP2020514428A (ja) * 2016-12-23 2020-05-21 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 高い引裂き伝播強度を有する熱可塑性ポリウレタン
JP2023014142A (ja) * 2016-12-23 2023-01-26 ビーエーエスエフ ソシエタス・ヨーロピア 高い引裂き伝播強度を有する熱可塑性ポリウレタン
CN109851763A (zh) * 2018-12-28 2019-06-07 沈阳化工研究院有限公司 一种锂电池铝塑膜外层胶黏剂的制备方法

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