EP4017900A1 - Verfahren zur herstellung von polyethercarbonatalkoholen - Google Patents

Verfahren zur herstellung von polyethercarbonatalkoholen

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Publication number
EP4017900A1
EP4017900A1 EP20751583.4A EP20751583A EP4017900A1 EP 4017900 A1 EP4017900 A1 EP 4017900A1 EP 20751583 A EP20751583 A EP 20751583A EP 4017900 A1 EP4017900 A1 EP 4017900A1
Authority
EP
European Patent Office
Prior art keywords
carbonate
catalyst
cyclic
polyether
functional starter
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Withdrawn
Application number
EP20751583.4A
Other languages
German (de)
English (en)
French (fr)
Inventor
Aurel Wolf
Stefan WESTHUES
Mike SCHÜTZE
Christoph Gürtler
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.)
Covestro Deutschland AG
Covestro Intellectual Property GmbH and Co KG
Original Assignee
Covestro Deutschland AG
Covestro Intellectual Property GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from EP19192407.5A external-priority patent/EP3783045A1/de
Application filed by Covestro Deutschland AG, Covestro Intellectual Property GmbH and Co KG filed Critical Covestro Deutschland AG
Publication of EP4017900A1 publication Critical patent/EP4017900A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2648—Alkali metals or compounds 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
    • 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
    • C08G18/44—Polycarbonates
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • C08G64/0208—Aliphatic polycarbonates saturated
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C08G64/305—General preparatory processes using carbonates and alcohols
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds

Definitions

  • the present invention relates to a process for the production of polyether carbonate alcohols, preferably polyether carbonate polyols, by catalytic addition of cyclic carbonates to a functional starter substance.
  • cyclic carbonates such as cyclic ethylene carbonate or propylene carbonate can be used as monomers in the production of polyether carbonate alcohols.
  • Titanium compounds such as titanium dioxide or titanium tetrabutoxide (EP 0 343 572), tin compounds such as tin dioxide or dibutyltin oxide (DE 2 523 352), or alkali metal carbonates or acetates (DE 1 495 299 A1 or Vogdanis) are usually used as catalysts for this reaction , L .; Heitz, W., Die Makromolekulare Chemie, Rapid Communications 1986, 7 (9), 543-547).
  • alkali metal carbonates or acetates but also sodium dihydrogen phosphate
  • sodium dihydrogen phosphate are known as alternative catalysts (Pawlowski, P .; Rokicki, G. Synthesis of oligocarbonate diols from ethylene carbonate and aliphatic diols catalyzed by alkali metal salts. Polymer 2004, 45, 3125 -3137).
  • the disadvantage of sodium dihydrogen phosphate as a catalyst for the addition of cyclic carbonates to H-functional starter substances is the lower conversion compared to, for example, alkali metal carbonates.
  • No. 3,248,414 A discloses that in the production of polyether carbonate alcohols by addition of cyclic carbonates onto H-functional starter substances, Na ', PCL can be used as a catalyst.
  • An effect of other tribasic phosphates on the conversion of cyclic carbonates and the proportion of incorporated CCE groups is not disclosed in US Pat. No. 3,248,414 A.
  • the object on which the present invention is based was therefore to provide a process for the preparation of polyether carbonate alcohols with a catalyst containing a phosphorus Provide oxygen bond, which leads to a high conversion of the cyclic carbonates and a high proportion of built-in C0 2 groups.
  • the technical object is achieved by a process for the production of polyether carbonate alcohols by addition of cyclic carbonate onto a functional starter substance in the presence of a catalyst, characterized in that a tribasic alkali or alkaline earth metal phosphate is used as the catalyst, the alkali metal is selected from potassium or cesium.
  • an H-functional starter substance and cyclic carbonate can first be placed in the reactor. It is also possible for only a partial amount of the H-functional starter substance and / or a partial amount of cyclic carbonate to be initially taken in the reactor. If appropriate, the amount of catalyst required for the ring-opening polymerization is then added to the reactor. The order in which they are added is not critical.
  • the reactor can also first be filled with the catalyst and then an H-functional starter substance and cyclic carbonate. Alternatively, the catalyst can also first be suspended in an H-functional starter substance and then the suspension can be filled into the reactor.
  • the catalyst is preferably used in an amount such that the content of catalyst in the resulting reaction product is 10 to 50,000 ppm, particularly preferably 250 to 30,000 ppm and most preferably 1000 to 25,000 ppm.
  • the catalyst content is preferably determined by elemental analysis with optical emission spectrometry by means of inductively coupled plasmas (ICP-OES).
  • the resulting mixture of (a) a portion of H-functional starter substance, (b) catalyst and (c) cyclic carbonate is added at a temperature of 30 ° C to 120 ° C, particularly preferably from 40 ° C to 100 ° C inert gas (for example argon or nitrogen) introduced.
  • inert gas for example argon or nitrogen
  • an inert gas for example argon or nitrogen
  • the catalyst can be added in solid form or as a suspension in the cyclic carbonate, in an H-functional starter substance or in a mixture of the above.
  • a subset of the H-functional starter substances and cyclic carbonate is initially charged in a first step and, in a subsequent second step, the temperature of the subset of H-functional starter substance and the cyclic carbonate is 40 ° C to 120 ° C, preferably 40 ° C to 100 ° C and / or the pressure in the reactor is reduced to less than 500 mbar, preferably 5 mbar to 100 mbar, where appropriate, an inert gas stream (for example of argon or nitrogen) is applied and part of the catalyst is bi-functional Starter substance is added in the first step or immediately thereafter in the second step.
  • an inert gas stream for example of argon or nitrogen
  • the resulting reaction mixture is then heated, for example, at a temperature of 110 ° C. to 220 ° C., preferably 130 ° C. to 200 ° C., particularly preferably 140 ° C. to 180 ° C., with an inert gas stream (for example of argon or nitrogen, for example ) is passed through the reactor.
  • an inert gas stream for example of argon or nitrogen, for example
  • the reaction is continued until no more gas evolution is observed at the set temperature.
  • the reaction can also be carried out under pressure, preferably at a pressure of 50 mbar to 100 bar (absolute), particularly preferably 200 mbar to 50 bar (absolute), particularly preferably 500 mbar to 30 bar (absolute).
  • the remaining amount of H-functional starter substance and / or cyclic carbonate is metered into the reactor continuously. It is possible to meter in the cyclic carbonate at a constant metering rate or to increase or decrease the metering rate gradually or stepwise or to add the cyclic carbonate in portions.
  • the cyclic carbonate is preferably added to the reaction mixture at a constant metering rate.
  • the cyclic carbonate or the H-functional starter substances can be metered in simultaneously or sequentially via separate meterings (additions) in each case or via one or more meterings, the H-functional starter substances being metered in individually or as a mixture.
  • the cyclic carbonates can be used individually or as mixtures in the process.
  • the cyclic carbonate used is preferably cyclic propylene carbonate (cPC), cyclic ethylene carbonate (cEC) or a mixture of the two, with particular preference only cyclic ethylene carbonate being used.
  • the polyether carbonate alcohols can be produced in a batch, semi-batch or continuous process.
  • the polyether carbonate alcohols are preferably prepared in a continuous process, which involves both a continuous copolymerization and a continuous one Adding the H-functional starter substance includes.
  • the invention therefore also relates to a process in which egg-functional starter substance, cyclic carbonate and catalyst are continuously metered into the reactor and the resulting reaction mixture (containing the reaction product) is continuously removed from the reactor.
  • the catalyst is preferably suspended or dissolved in egg-functional starter substance and added continuously.
  • continuous can be defined as the mode of adding a relevant catalyst or reactant such that a substantially continuous effective concentration of the catalyst or reactants is maintained.
  • the supply of the catalyst and the reactants can be carried out really continuously or in relatively closely spaced increments.
  • a continuous addition of starter can be genuinely continuous or take place in increments. It would not deviate from the present method to add a catalyst or reactants incrementally in such a way that the concentration of the added materials falls essentially to zero for some time before the next incremental addition. It is preferred, however, that the catalyst concentration be maintained at substantially the same concentration during the major part of the course of the continuous reaction and that initiator be present during the major part of the copolymerization process.
  • Suitable H-functional starter substances which can be used are compounds with H atoms active for the alkoxylation, which have a number average molecular weight according to DIN55672-1 up to 10,000 g / mol, preferably up to 5000 g / mol and particularly preferably up to 2500 g / mol.
  • Groups with active H atoms which are active for the alkoxylation are, for example, -OH (water, alcohols), -NH2 (primary amines), -NH- (secondary amines), -SH and -CO2H, with -OH - NH2 and -CO2H being preferred -OH is particularly preferred.
  • PolyTHF ® from BASF polytetrahydrofuranamines, polyether thiols, polyacrylate polyols, castor oil, the mono- or diglyceride of ricinoleic acid, monoglycerides of fatty acids, chemically modified mono-, di- and / or triglycerides of fatty acids, and C 1 -C 24 alkyl fatty acid esters, which contain on average at least 2 OH groups per molecule and water is used.
  • it is in the C 1 -C 24 alkyl fatty acid ester which contain OH-groups per molecule on average at least 2 to commercial products such as Lupranol Balance ® (Fa.
  • Alcohols, amines, thiols and carboxylic acids can be used as monofunctional starter substances.
  • the following can be used as monofunctional alcohols: methanol, ethanol, 1-propanol,
  • Possible monofunctional amines are: butylamine, tert-butylamine, pentylamine, hexylamine, aniline, aziridine, pyrrolidine, piperidine, morpholine.
  • carboxylic acids formic acid, acetic acid, propionic acid, butyric acid, acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, aromatic carboxylic acids such as benzoic acid, terephthalic acid, tetrahydrophthalic acid, phthalic acid or isophthalic acid, such as palmitic acid, fatty acids Linolenic acid.
  • Polyhydric alcohols suitable as H-functional starter substance are, for example, dihydric alcohols (such as, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-butenediol, 1,4-butynediol, neopentyl glycol, 1 , 5-pentanediol, methylpentanediols (such as 3-methyl-1,5-pentanediol), 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, bis (hydroxymethyl) - cyclohexanes (such as 1,4-bis (hydroxymethyl) cyclohexane, triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol
  • the H-functional starter substance can also be selected from the substance class of polyether polyols which have a molecular weight M n according to DIN55672-1 in the range from 18 to 8000 g / mol and a functionality of 2 to 3. Preference is given to polyether polyols which are built up from repeating ethylene oxide and propylene oxide units, preferably with a proportion of 35 to 100% propylene oxide units, particularly preferably with a proportion of 50 to 100% propylene oxide units. These can be random copolymers, gradient copolymers, alternating or block copolymers of ethylene oxide and propylene oxide.
  • the H-functional starter substance can also be selected from the substance class of polyester polyols. At least difunctional polyesters are used as polyester polyols. Polyester polyols preferably consist of alternating acid and alcohol units.
  • the acid components used are, for example, succinic acid, maleic acid, maleic anhydride, adipic acid, phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or mixtures of the acids and / or anhydrides mentioned.
  • As alcohol components for. B.
  • ethanediol 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis (hydroxymethyl) cyclohexane, diethylene glycol, Dipropylene glycol, trimethylolpropane, glycerol, pentaerythritol or mixtures of the alcohols mentioned are used. If dihydric or polyhydric polyether polyols are used as the alcohol component, polyester ether polyols are obtained which can also serve as starter substances for the production of the polyether carbonate polyols.
  • polycarbonate diols can be used as H-functional starter substance, which are prepared, for example, by reacting phosgene, dimethyl carbonate, diethyl carbonate or diphenyl carbonate and difunctional alcohols or polyester polyols or polyether polyols.
  • polycarbonates can be found e.g. B. in EP-A 1359177.
  • polyether carbonate polyols can be used as H-functional starter substance.
  • polyether carbonate polyols obtainable by the process according to the invention described here are used. These polyether carbonate polyols used as H-functional starter substances are prepared beforehand in a separate reaction step for this purpose.
  • the H-functional starter substance generally has a functionality (ie number of H atoms active for the polymerization per molecule) of 1 to 8, preferably 1 to 3.
  • the H-functional starter substance is used either individually or as a mixture of at least two H-functional starter substances.
  • the H-functional starter substance is particularly preferably at least one compound selected from the group consisting of water, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol , 2-methylpropane-l, 3-diol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, polyether carbonate polyols with a molecular weight M n according to DIN55672-1 in the range of 150 to 8000 g / mol with a functionality of 2 to 3 and polyether polyols with a molecular weight M n according to DIN55672-1 in the range from 150 to 8000 g / mol and
  • the H-functional starter substance is preferably chosen so that a polyether carbonate polyol, i.e. a polyether carbonate alcohol with a functionality of 2 or more, is obtained as the polyether carbonate alcohol.
  • a tribasic alkali metal or alkaline earth metal phosphate is used as the catalyst.
  • the alkali metals of the catalyst are preferably selected from sodium, potassium or cesium, particularly preferably from sodium and potassium.
  • the alkaline earth metals of the catalyst are preferably selected from calcium and magnesium.
  • the catalyst is particularly preferably a tribasic alkali metal phosphate.
  • polyether carbonate alcohols obtained by the process according to the invention can be processed further to form polyurethanes, for example by reaction with di- and / or polyisocyanates.
  • detergent formulations such as for textile or surface cleaning, drilling fluids, fuel additives, ionic and non-ionic surfactants, dispersants, lubricants, process chemicals for paper or textile production, cosmetic formulations, such as in skin or sun protection cream or to find hair care products.
  • the proportion of built-in CO2 in the resulting polyether carbonate alcohol (CCF content) was determined by means of H-N1VIR spectroscopy (Bruker, AV III HD 600, 600 MHz; pulse program zg30, waiting time dl: 10 s, 64 scans). Each sample was dissolved in deuterated chloroform.
  • F (4.37-4.21) area of resonance at 4.37-4.21 ppm for polyether carbonate alcohol.
  • F (4, 19-4.07) area of resonance at 4.19-4.07 ppm for polyether carbonate alcohol (The sum of F (4.37-4.21) and F (4, 19-4.07) corresponds to 4 protons)
  • N [(4, 37-4, 2l) + F (4, 19-4, 07)] x 88 + F (3, 8 - 3, 55) x 44 (II)
  • the factor 88 results from the sum of the molar masses of CO2 (molar mass 44 g / mol) and that of ethylene oxide (molar mass 44 g / mol), the factor 44 results from the molar mass of ethylene oxide.
  • the weight fraction (in% by weight) of CO2 in the polyether carbonate alcohol was calculated according to formula (III):
  • F (1.78 - 1.29) normalized area of the resonance at 1.78 - 1.29 ppm for 1,6-hexanediol (defined as 8 protons)
  • F (4.36 - 3.20) normalized area of the resonance at 4.36 - 3.20 ppm for polyether carbonate alcohol and 1.6 -Hexanediol (remaining 4 protons).
  • H-functional starter substance e.g. 1,6-hexanediol: 12 H
  • Glycerin Sigma-Aldrich 99%, anhydrous
  • Example 1 Preparation of polyether carbonate alcohols by ring-opening polymerization of cyclic ethylene carbonate in the presence of 1,6-hexanediol as starter and K3PO4 as catalyst
  • a 500 mL four-necked glass flask was equipped with a reflux condenser, KPG stirrer, thermal sensor, nitrogen inlet and gas outlet / gas outlet with pressure relief valve. Then 200 g of cyclic ethylene carbonate, 34.25 g of 1,6-hexanediol and 2.41 g of K 3 PO 4 were weighed out. 10 L / h of nitrogen was passed in for 30 minutes, the suspension being stirred at 300 rpm. The suspension was then gradually heated to 180 ° C. The resulting gas stream was drained through a bubble counter after the reflux condenser.
  • reaction mixture was kept at the set temperature until the evolution of gas came to a standstill.
  • the CCh fraction built into the polyether carbonate alcohol was determined using the methods described above by means of 'H-NMR spectroscopy.
  • Example 2 Preparation of polyether carbonate alcohols by ring-opening polymerization of cyclic ethylene carbonate in the presence of 1,6-hexanediol as starter and NasPCü as catalyst
  • Example 3 Preparation of polyether carbonate alcohols by ring-opening polymerization of cyclic ethylene carbonate in the presence of H2O as starter and K3PO4 as catalyst
  • Example 4 Preparation of polyether carbonate alcohols by ring-opening polymerization of cyclic ethylene carbonate in the presence of 1-dodecanol as starter and K3PO4 as catalyst
  • reaction was carried out analogously to Example 1, 1-dodecanol (30.2 g) being used as a starter instead of 1,6-hexanediol and the amount of cEC being halved to 100 g cEC.
  • Example 5 Preparation of polyether carbonate alcohols by ring-opening polymerization of cyclic ethylene carbonate in the presence of 1-hexadecanol as starter and K3PO4 as catalyst
  • reaction was carried out analogously to Example 1, 1-hexadecanol (39.3 g) being used as starter instead of 1,6-hexanediol and the amount of cEC being halved to 100 g cEC.
  • Example 6 Preparation of polyether carbonate alcohols by ring-opening polymerization of cyclic ethylene carbonate in the presence of glycerol as starter and K3PO4 as catalyst
  • Example 7 Preparation of polyether carbonate alcohols by ring-opening polymerization of cyclic ethylene carbonate in the presence of 1,6-hexanediol as starter and NaH2PO4 as catalyst
  • Example 8 Preparation of polyether carbonate alcohols by ring-opening polymerization of cyclic ethylene carbonate in the presence of 1,6-hexanediol as starter and Na 2 HPC> 4 as catalyst
  • Example 9 Preparation of polyether carbonate alcohols by ring-opening polymerization of cyclic ethylene carbonate in the presence of 1,6-hexanediol as starter and H3PO4 as catalyst
  • Example 10 Preparation of polyether carbonate alcohols by ring-opening polymerization of cyclic ethylene carbonate in the presence of 1,6-hexanediol as starter and NaiPiO ? as a catalyst
  • Example 11 Preparation of polyether carbonate alcohols by ring-opening polymerization of cyclic propylene carbonate in the presence of 1,6-hexanediol as starter and K3PO4 as catalyst
  • a 500 mL four-necked glass flask was equipped with a reflux condenser, KPG stirrer, thermal sensor, nitrogen inlet and gas outlet / gas outlet with pressure relief valve.
  • 200 g of cyclic propylene carbonate, 34.25 g of 1,6-hexanediol and 2.08 g of K 3 PO 4 were then weighed out.
  • 10 L / h of nitrogen was passed in for 30 minutes, the suspension being stirred at 300 rpm.
  • the suspension was then gradually heated to 180 ° C.
  • the resulting gas stream was drained through a bubble counter after the reflux condenser.
  • the reaction mixture was kept at the set temperature until the evolution of gas came to a standstill.
  • the CCh content built into the polyether carbonate alcohol was determined by means of 'H-NMR spectroscopy.
  • Example 12 Preparation of polyether carbonate alcohols by ring-opening polymerization of cyclic propylene carbonate in the presence of 1,6-hexanediol as starter and NasPCü as catalyst
  • Example 13 Preparation of polyether carbonate alcohols by ring-opening polymerization of cyclic propylene carbonate in the presence of H2O as starter and K3PO4 as catalyst
  • Example 14 Preparation of polyether carbonate alcohols by ring-opening polymerization of cyclic propylene carbonate in the presence of 1,6-hexanediol as starter and Na 2 HP04 as catalyst
  • reaction was carried out analogously to Example 11, Na2HPO4 (1.39 g) being used instead of K3PO4 as a catalyst and a reaction temperature of 220 ° C.
  • Table 1 shows the properties of the polyether carbonate alcohols which were produced by the addition of cyclic ethylene carbonate onto an egg-functional starter substance. It can be seen that the use of the catalysts of the invention leads to the incorporation of C0 2 groups with a high conversion of cyclic ethylene carbonate. Examples 1 and 3 to 6 according to the invention all have conversions of 99% cyclic ethylene carbonate, examples 2 and 7 to 10 having a conversion of less than 81% cyclic ethylene carbonate without a catalyst according to the invention. Table 2:
  • Table 2 shows the properties for the polyether carbonate alcohols which were produced by adding cyclic propylene carbonate to an egg-functional starter substance. It can also be seen here that the use of the catalysts according to the invention (Examples 11 and 13) leads to a high conversion of cyclic propylene carbonate compared to a catalyst not according to the invention (Examples 12 and 14).

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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)
  • Polyesters Or Polycarbonates (AREA)
EP20751583.4A 2019-08-19 2020-08-12 Verfahren zur herstellung von polyethercarbonatalkoholen Withdrawn EP4017900A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP19192407.5A EP3783045A1 (de) 2019-08-19 2019-08-19 Verfahren zur herstellung von polyethercarbonatpolyolen
EP20158920 2020-02-24
PCT/EP2020/072580 WO2021032554A1 (de) 2019-08-19 2020-08-12 Verfahren zur herstellung von polyethercarbonatalkoholen

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EP4017900A1 true EP4017900A1 (de) 2022-06-29

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EP (1) EP4017900A1 (zh)
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EP4293065A1 (de) * 2022-06-14 2023-12-20 Covestro Deutschland AG Polymere enthaltend einen polyethercarbonat-haltigen block, herstellungsverfahren dafür und verwendung der polymere als tensid
DE102023000396A1 (de) 2023-02-09 2024-08-14 Covestro Deutschland Ag Verfahren zur Herstellung von Polyethercarbonatalkoholen

Family Cites Families (9)

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Publication number Priority date Publication date Assignee Title
US3248414A (en) * 1963-01-16 1966-04-26 Pittsburgh Plate Glass Co Method of preparing high molecular weight polycarbonates
DE1495299A1 (de) 1963-05-09 1969-01-02 Huels Chemische Werke Ag Verfahren zur Herstellung linearer Polycarbonate
US3689462A (en) * 1971-05-19 1972-09-05 Ppg Industries Inc Process for preparing polycarbonates
DE2523352A1 (de) 1975-05-27 1976-12-09 Bayer Ag Verfahren zur herstellung aliphatischer polycarbonate
DE68927281T2 (de) 1988-05-26 1997-03-06 Daicel Chem Polycarbonatdiolzusammensetzung und Polyurethankunststoff
DE10219028A1 (de) 2002-04-29 2003-11-06 Bayer Ag Herstellung und Verwendung von hochmolekularen aliphatischen Polycarbonaten
EP2548905A1 (de) * 2011-07-18 2013-01-23 Bayer MaterialScience AG Verfahren zur Aktivierung von Doppelmetallcyanidkatalysatoren zur Herstellung von Polyetherpolyolen
RU2668974C2 (ru) 2013-08-02 2018-10-05 Ковестро Дойчланд Аг Способ получения простых полиэфиркарбонатполиолов
EP3219741A1 (de) * 2016-03-18 2017-09-20 Covestro Deutschland AG Verfahren zur herstellung von polyethercarbonatpolyolen

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