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WO2013034539A1 - Polyols de polycarbonate - Google Patents

Polyols de polycarbonate Download PDF

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Publication number
WO2013034539A1
WO2013034539A1 PCT/EP2012/067192 EP2012067192W WO2013034539A1 WO 2013034539 A1 WO2013034539 A1 WO 2013034539A1 EP 2012067192 W EP2012067192 W EP 2012067192W WO 2013034539 A1 WO2013034539 A1 WO 2013034539A1
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WIPO (PCT)
Prior art keywords
polyol
sum
group
range
weight
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PCT/EP2012/067192
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English (en)
Inventor
Evgeny Avtomonov
Olaf Fleck
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Bayer Intellectual Property Gmbh
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Publication of WO2013034539A1 publication Critical patent/WO2013034539A1/fr

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    • 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
    • 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
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C08G64/305—General preparatory processes using carbonates and alcohols

Definitions

  • the present invention relates to highly thermally and hydrolytically resistant polycarbonate polyols and their use for the production of polyurethanes, in particular dispersions and thermoplastic polymers.
  • Polycarbonate polyols prepared from aliphatic polyalcohols, mainly from ⁇ , ⁇ -alkane diols, for example 1 ,4-butanediol, 1,5-pentanediol, 1 ,6-hexanediol etc. are sold as polyols which can be used for the preparation of polyurethanes, for example thermoplastic polyurethanes, fibers, polyurethane foams, polyurethane dispersions for coatings, adhesives, binders for leather and textile applications as well as sealants, building up flexible segments which have excellent resistance to thermal aging, hydrolysis, light and oxidative degradation. This resistance is due to the fact that carbonate linkages in the polymer chain exhibit extremely high chemical stability.
  • Thermoplastic polyurethanes in particular are used for injection molding applications and, accordingly, have to withstand high temperatures as well, whereas polyurethane dispersions as well as coatings, adhesives, sealants as well as artificial textiles and leather made of such dispersion have to withstand hydrolysis upon storage and during the service lifetime.
  • JP 2005-054034 A is concerned with a method for producing a polyol composition which facilitates the control of reaction, such as in the urethanization reaction, and is useful as a raw material for paint, adhesives, synthetic and artificial leathers, polyurethane elastomers, polyamide elastomers, active energy ray-curable resins and the like.
  • This method for producing the polyol composition comprises reacting a polyhydric alcohol with polycarboxylic acids or carbonate compounds in the presence of a titanium compound to obtain a polyol and adding a phosphite diester into the resulting polyol, or adding a phosphite diester and an inorganic phosphorus compound and/or an acid phosphate into the resulting polyol.
  • US 2006/052572 Al relates to a process for preparing oligocarbonate polyols having a number average molecular weight of 500 to 5000 g/mol by reacting organic carbonates and aliphatic polyols in the presence of a metal acetylacetonate catalyst based on a metal which has an atomic number in the Periodic Table of the Elements of 39, 57, 59 to 69 or 71.
  • This patent application also relates to the oligocarbonate polyols obtained by this process.
  • EP 1 288 241 Al describes special aliphatic polycarbonate polyols which are manufactured with the aid of especially pure ⁇ , ⁇ -pentane and/or -hexane diols having very high content of primary hydroxyl groups. These polycarbonate polyols are, according to the teaching of EP-A 1 288 241 , advantageous for thermoplastic polyurethanes. The content of the primary hydroxyl groups of these aliphatic polycarbonate polyols is determined from the thermally cleaved organic substances which are obtained in a vacuum upon thermal treatment of a polycarbonate polyol specimen at 160 to 200 °C and subsequently analyzed by chromatography for secondary group containing alcohols.
  • the amount of cleaved organic substances corresponds to approximately 10% of the whole terminal alcohol groups, thus demonstrating the insufficient thermal stability of polycarbonate polyols in the temperature range of 160 to 200 °C.
  • Such polycarbonate polyols therefore cannot be used for polyurethanes having excellent thermal stability.
  • an object of the present invention is to provide novel mixtures of polycarbonate polyols which can be used for the preparation of polyurethanes in general and thermoplastic polyurethanes and polyurethane dispersions in particular that show excellent resistance to high temperatures, light and oxidative degradation as well as resistance to hydrolysis.
  • a mixture comprising a polycarbonate polyol with a decomposition temperature of > 180 °C at > 0.1 mbar to ⁇ 1 mbar which is based on at least two different diols selected from the group consisting of C 4 , Cs and e diols, the mixture having an altogether low amount of amines and/or ammonium ions, alkali metal atoms and/or ions, earth alkali metal atoms and/or ions, metals and/or ions of the 13 th through 15 th Group of the Periodic Table of the Elements (i.e.
  • the pH value of the 10 weight-% slurry of this mixture in water lies in the range from > 5.0 to ⁇ 8.0.
  • R2 represents an unsubstituted or substituted, linear or branched alkylene unit having 5 carbon atoms in the main chain in the polyol and
  • R3 represents an unsubstituted or substituted, linear or branched alkylene unit having 6 carbon atoms in the main chain in the polyol;
  • amines (R4)3N wherein R4 represents, independent of each other, H or a Ci to C30 alkyl group or a e to C30 arylalkyl group and/or ammonium ions (R5)4N + , wherein R5 represents, independent of each other, H or a Ci to C30 alkyl group or a e to C30 arylalkyl group and
  • metal atoms and/or metal ions and/or metal compounds comprising metal in the respective oxidation state selected from the group consisting of Li, Li + , Na, Na + , K, K + , Ca, Ca 2+ , Sr, Sr 2+ , Mg, Mg 2+ , Ba, Ba 2+ , Al, Al 3+ , Ga, Ga 3+ , In, In 3+ , Tl, Tf, Ge, Ge 2+ , Ge 4+ , Sn, Sn 4+ , Pb,
  • the main chain in the polyol is identical to the main chain that is directly binding to two adjacent carbonate moieties.
  • the aforementioned polyols with their low content of impurities (d) and (e) display a good thermal stability.
  • the sum of the weight contents of the recurring groups (a), (b) and (c) present in the polyol is in the rang e o f > 50 weight-% to ⁇ 100 weight-%>.
  • terminal groups -R1/2/3-OH are also not included.
  • Ci to C30 alkyl group may also be linear or branched and unsubstituted or substituted. The same holds true for the e to C30 arylalkyl group.
  • the polycarbonate polyol is a polyol with an average amount of hydroxyl groups per molecule (hydroxy functionality or fee) ranging from > 1 .90 to ⁇ 2.10, preferably > 1.93 to ⁇ 2.07, most preferably > 1.95 to ⁇ 2.05.
  • the polycarbonate may optionally contain > 0 to ⁇ 10 weight-% of at least a polyvalent alcohol such as, for example, 2,2,2-trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol and their ethoxylated and/or propoxylated analogues, sugar derivatives, branched polyalkylene glycols having a molecular weight from > 92 to ⁇ 1000 g/mol.
  • the fragments of the branching polyalcohols are not considered to be a part of recurring units.
  • the number average molecular weight of the polycarbonate polyol is generally in the range from > 300 to ⁇ 20,000 g/mol, more preferably in the range from > 400 to ⁇ 10,000 g/mol, even more preferably in the range from > 500 to ⁇ 5,000 g/mol as can be determined by GPC (at 25 °C, THF solution, according to polystyrene standard), by the estimation of the OH-number (titration methods) and subsequent calculation of the molecular weight, by 'H-NMR spectroscopy (3 ⁇ 4 nuclear magnetic resonance spectroscopy) by estimating the relation of the hydroxyl and/or adjacent alkylene end groups with the alkylene groups forming the polymer backbone.
  • the terminal groups of the polycarbonate polyol can conveniently be determined by measuring the OH-number of the polycarbonate polyol or analyzing the polycarbonate polyol by 'H-NMR.
  • the hydroxy number of a substance is the amount (mg) of potassium hydroxide (KOH) which corresponds to the molar equivalent hydroxyl groups of the polymer determined by titration techniques, for example by reacting the polymer with acetic anhydride and titration of the acetic acid formed from this reaction by potassium hydroxide solution.
  • the OH-number of the polyols range from > 5 mg KOH/g polycarbonate polyol to ⁇ 380 mg KOH / g polycarbonate polyol, more preferably from > 10 mg KOH/g polycarbonate polyol to ⁇ 300 mg KOH, and even more preferably from > 35 mg KOH/g polycarbonate polyol to ⁇ 250 mg KOH.
  • the decomposition temperature is defined as the temperature at which the weight of a measured sample of polycarbonate polyol decreases by at least 0.1 weight-%, that is, the weight of the sample becomes less than 99.9 weight- % during heating under reduced pressure for at least 4 hours, assuming the weight of the measured sample at the start of measurement to be 100 weight-%.
  • the polycarbonate polyol has a decomposition temperature of > 200 °C at a pressure of 1 mbar. More preferably the polycarbonate polyol has a decomposition temperature of > 210 °C at a pressure of 1 mbar. Even more preferably, the polycarbonate polyol has a decomposition temperature of > 180 °C at a pressure of 0.1 mbar. Particularly preferably, the polycarbonate polyol has a decomposition temperature of > 200 °C at a pressure of 0.1 mbar.
  • the polyol comprises terminal hydroxyl groups and at least two different recurring units selected from the group consisting of (a), (b) and (c).
  • the latter is to be understood as the polyol having at least a recurring unit (a) and a recurring unit (b) or the respective combinations (a)/(c), (b)/(c) or (a)/(b)/(c) within its molecule. It is also contemplated that there may be different individual groups (a), (b) and/or (c) within the molecule, for example in the case of different isomers of the respective alcohols used for the preparation of the polycarbonate polyol.
  • the term unsubstituted or substituted, linear or branched alkylene unit denotes a multivalent, preferably divalent saturated hydrocarbon chain having the respective amount of carbon atoms.
  • Preferred branched alkylene groups have one or two branches, preferably one branch such as a methyl or ethyl group.
  • the carbon atoms in the branch(es) are included in the total count of carbon atoms for the substituents Rl , R2 and R3.
  • Examples for further substituents include F, CI, Br, I, CN, CF 3 , OCF 3 and SCF 3 .
  • the content of metal atoms, metal ions and metal compounds is, for example, quantitatively or semi- quantitatively determined by inductively-coupled plasma atomic emission spectroscopy (ICP-AES) using, for example, a Spectroflame P instrument (Spectro, Germany) Alternatively the ICP-MS could be used especially if lower concentrations have to be determined. Any other quantitative analysis capable of determining very low amounts of metals may, of course, be used.
  • the quantitative trace analysis of amines may be conducted using coupled chromatography-mass spectrometry like GC-MS or HPLC-MS or HPLC-MS/MS depending on the specific target amine. A suitable pre-treatment of the sample depending on the analytical method used has to be established. Any other quantitative analysis capable of determining the relevant amounts of amines may, of course, be used.
  • the metal atoms and/or metal ions and/or metal compounds comprising metal in the respective oxidation state as mentioned under (e) are selected from the group consisting of Li, Li + , Na, Na + , K, K + , Ca, Ca 2+ , Mg, Mg 2+ , Al, Al 3+ , Ti, Ti 3+ , Ti 4+ , Sn, Sn 4+ , Pb, Pb 4+ , Sb, Sb 3+ , Sb 5+ , Bi and Bi 3+ . It is preferred that in the mixture the sum of the weight contents of (d) and (e) is in the range of > 0.1 ppm to ⁇ 10 ppm in relation to the total weight of the polycarbonate polyol.
  • the pH of the polycarbonate polyol comprising mixture is measured as a 10 weight- % slurry of the mixture comprising polycarbonate polyol which was obtained by vigorous agitation of the mixture with deionized water at room or at elevated temperature of up to 95 °C for 30 minutes under an inert atmosphere, cooling the slurry down to room temperature, if necessary, and making the pH measurement of the aqueous phase at room temperature.
  • this pH value lies in a range of > 5.5 to ⁇ 7.5.
  • Rl represents -(03 ⁇ 4)4-.
  • R2 represents -(CEh ⁇ - and/or -(CH2)2-(CHCH 3 )-(CH2)2-
  • R3 represents -(CH 2 )2-(CHCH 3 )-(CH 2 )2- and/or -(CH 2 ) 6 -.
  • Rl represents -(CEh ⁇ -
  • R2 represents -(CEh ⁇ - and/or -(CH 2 )2-(CHCH 3 )-(CH 2 )2-
  • R3 represents -(CH 2 )2-(CHCH 3 )-(CH 2 )2- and/or -(CH 2 ) 6 -.
  • the polycarbonate polyol may be obtained from 1 ,4-butanediol, 1 ,5-pentanediol, 3-methyl- 1 ,5-pentandiol and 1 ,6-hexanediol, respectively.
  • Another embodiment of the invention relates to a mixture comprising a polycarbonate polyol, the polyol having a decomposition temperature of > 180 °C at > 0.1 mbar to ⁇ 1 mbar and comprising terminal hydroxyl groups and at least two different recurring units selected from the group consisting of:
  • Rl represents an unsubstituted or substituted, linear or branched alkylene unit having 4 carbon atoms in the main chain in the polyol and
  • R2 represents an unsubstituted or substituted, linear or branched alkylene unit having 5 carbon atoms in the main chain in the polyol;
  • the sum of the weight contents of the recurring groups (a) and (b) present in the polyol is ⁇ 100 weight- % and the ratio of the sum of the recurring groups (a) to the sum of the recurring groups (b) is in the range of 1 :99 to 99: 1 ;
  • amines (R4) 3 N wherein R4 represents, independent of each other, H or a Ci to C 3 o alkyl group or a Ce to C 3 o arylalkyl group and/or ammonium ions (R5)4N + , wherein R5 represents, independent of each other, H or a Ci to C 3 o alkyl group or a Ce to C 3 o arylalkyl group and
  • metal atoms and/or metal ions and/or metal compounds comprising metal in the respective oxidation state selected from the group consisting of Li, Li + , Na, Na + , K, K + , Ca, Ca 2+ , Sr, Sr 2+ , Mg, Mg 2+ , Ba, Ba 2+ , Al, Al 3+ , Ga, Ga 3+ , In, In 3+ , Tl, ⁇ , Ge, Ge 2+ , Ge 4+ , Sn, Sn 4+ , Pb, Pb 2+ , Pb 4+ , Sb, Sb 3+ , Sb 5+ , Bi, Bi 3+ , Ti, Ti 3+ , Ti 4+ , Zr, Zr 4+ , Hf, Hf 4 *, V, V 2+ , V 3+ , V 4+ , V 5+ , Nb, Nb 3+ , Nb 5+ , Ta, Ta 3+ , Ta 5+ , Cr, Cr 2+ ,
  • the ratio of the sum of the recurring groups (a) to the sum of the recurring groups (b) is in the range of 10:90 to 90: 10, more preferably in the range of 30:70 to 70:30.
  • Another embodiment of the invention relates to a mixture comprising a polycarbonate polyol, the polyol having a decomposition temperature of > 180 °C at > 0.1 mbar to ⁇ 1 mbar and comprising terminal hydroxyl groups and at least two different recurring units selected from the group consisting of:
  • Rl represents an unsubstituted or substituted, linear or branched alkylene unit having 4 carbon atoms in the main chain in the polyol and
  • R3 represents an unsubstituted or substituted, linear or branched alkylene unit having 6 carbon atoms in the main chain in the polyol;
  • the sum of the weight contents of the recurring groups (a) and (c) present in the polyol is ⁇ 100 weight-% and the ratio of the sum of the recurring groups (a) to the sum of the recurring groups (c) is in the range of 1 :99 to 99: 1 ;
  • amines (R4)3N wherein R4 represents, independent of each other, H or a Ci to C30 alkyl group or a Ce to C30 arylalkyl group and/or ammonium ions (R5)4N + , wherein R5 represents, independent of each other, H or a Ci to C30 alkyl group or a Ce to C30 arylalkyl group and
  • metal atoms and/or metal ions and/or metal compounds comprising metal in the respective oxidation state selected from the group consisting of Li, Li + , Na, Na + , K, K + , Ca, Ca 2+ , Sr, Sr 2+ , Mg, Mg 2+ , Ba, Ba 2+ , Al, Al 3+ , Ga, Ga 3+ , In, In 3+ , Tl, Tf , Ge, Ge 2+ , Ge 4+ , Sn, Sn 4+ , Pb, Pb 2+ , Pb 4+ , Sb, Sb 3+ , Sb 5+ , Bi, Bi 3+ , Ti, Ti 3+ , Ti 4+ , Zr, Zr 4+ , Hf, Hf 4 *, V, V 2+ , V 3+ , V 4+ , V 5+ , Nb, Nb 3+ , Nb 5+ , Ta, Ta 3+ , Ta 5+ , Cr, Cr 2+ ,
  • Another embodiment of the invention relates to a mixture comprising a polycarbonate polyol, the polyol having a decomposition temperature of > 180 °C at > 0.1 mbar to ⁇ 1 mbar and comprising terminal hydroxyl groups and at least two different recurring units selected from the group consisting of:
  • R2 represents an unsubstituted or substituted, linear or branched alkylene unit having 5 carbon atoms in the main chain in the polyol and
  • R3 represents an unsubstituted or substituted, linear or branched alkylene unit having 6 carbon atoms in the main chain in the polyol;
  • the sum of the weight contents of the recurring groups (b) and (c) present in the polyol is ⁇ 100 weight-% and the ratio of the sum of the recurring groups (b) to the sum of the recurring groups (c) is in the range of 1 :99 to 99: 1 ;
  • amines (R4)3N wherein R4 represents, independent of each other, H or a Ci to C30 alkyl group or a e to C30 arylalkyl group and/or ammonium ions (R5)4N + , wherein R5 represents, independent of each other, H or a Ci to C30 alkyl group or a e to C30 arylalkyl group and
  • metal atoms and/or metal ions and/or metal compounds comprising metal in the respective oxidation state selected from the group consisting of Li, Li + , Na, Na + , K,
  • the ratio of the sum of the recurring groups (b) to the sum of the recurring groups (c) is in the range of 10:90 to 90:10, more preferably in the range of 30:70 to 70:30.
  • the sum of the recurring groups (a) to the sum of the recurring groups [(b) and (c)] is in the range of 1 :99 to 99:1, more preferably in the range of 10:90 to 90: 10, most preferably in the range of 30:70 to 70:30, with the sum of the recurring groups (b) to the sum of the recurring groups (c) being in the range of 1 :99 to 99: 1.
  • the sum of the recurring groups [(a) and (b)] to the sum of the recurring groups (c) is in the range of 1 :99 to 99:1, more preferably in the range of 10:90 to 90: 10, most preferably in the range of 30:70 to 70:30, with the sum of the recurring groups (a) to the sum of the recurring groups (b) being in the range of 1 :99 to 99: 1.
  • the sum of the recurring groups [(a) and (c)] to the sum of the recurring groups (b) is in the range of 1 :99 to 99: 1, more preferably in the range of 10:90 to 90: 10, most preferably in the range of 30:70 to 70:30, with the sum of the recurring groups (a) to the sum of the recurring groups (c) being in the range of 1 :99 to 99: 1.
  • the sum of contents of metal ions and metal atoms selected from the group consisting of Li, Li + , Na, Na + , K, K + , Ca, Ca 2+ , Mg, Mg 2+ , Al, Al 3+ , Ti, Ti 3+ , Ti 4+ , Sn, Sn 4+ , Pb, Pb 4+ personally Sb, Sb 3+ , Sb 5+ , Bi and Bi 3+ is in the range > 0.1 ppm to ⁇ 10 ppm in relation to the total weight of the polycarbonate polyol.
  • Preferred herein is a range of > 0.1 ppm to ⁇ 5 ppm in relation to the total weight of the polycarbonate polyol.
  • the invention is directed to a method for the preparation of a polycarbonate polyol as recited in one or more of claims 1 to 7, comprising the steps of:
  • (III) optionally, a polyvalent alcohol; while removing a low molecular by-product formed from (II) from the reaction system, to thereby obtain a polycarbonate prepolymer; and
  • the main chain is identical to the main chain that is directly binding to two adjacent hydro xyl groups.
  • the main chain would in each case have 5 carbon atoms.
  • At least two different diols are selected from the group consisting of (al), (bl) and (cl).
  • This is to be understood as that at least a polyol (al) and a polyol (bl) or the respective combinations (al)/(cl), (bl)/(cl) or (al)/(bl)/(cl) are employed.
  • unsubstituted or substituted, linear or branched alkylene unit denotes a multivalent, preferably divalent saturated hydrocarbon chain having the respective amount of carbon atoms.
  • Preferred branched alkylene groups have one or two branches, preferably one branch such as a methyl or ethyl group.
  • the carbon atoms in the branch(es) are included in the total count of carbon atoms for the substituents Rl, R2 and R3.
  • substituents include F, Cl, Br, I, CN, CF 3 , OCF 3 and SCF 3 .
  • carbonate compounds (II) above include phosgene, diphosgene, dialkyl carbonates, such as dimethyl carbonate, diethyl carbonate and dibutyl carbonate; alkylene carbonates, such as ethylene carbonate, 1 ,2-propylene carbonate and trimethylene carbonate; and diaryl carbonates, such as diphenyl carbonate.
  • dialkyl carbonates, alkylene carbonates and diaryl carbonates are preferred. Even more preferred are dialkyl and alkylene carbonates.
  • the amount of the carbonate compound (II) there is no particular limitation. However, preferably the molar ratio of the carbonate compound (II) to the total molar amount of the diol (I) is in the range from 20 : 1 to 1 : 20, more preferably in the range form 10 :1 to 1 : 10.
  • the diols (I) and the carbonate compound (II) are mixed together, and the resultant mixture is subjected to a polymerization reaction, to thereby obtain a polycarbonate prepolymer.
  • the main reactions involved in the polymerization reaction are the condensation reaction, namely, the reaction of the compound of diols (I) with the carbonate compound (II), upon which the nucleophilic substitution reaction at the carbonate center of the carbonate compound (II) the nucleophilic hydroxyl groups of the diols (I) and optionally of the compounds (III) takes place.
  • the condensation reaction namely, the reaction of the compound of diols (I) with the carbonate compound (II), upon which the nucleophilic substitution reaction at the carbonate center of the carbonate compound (II) the nucleophilic hydroxyl groups of the diols (I) and optionally of the compounds (III) takes place.
  • dialkyl or alkylene carbonates as compound (II) it is a transesterification reaction which proceeds under formation of the hydroxyl group-containing by-product which is cleaved from the carbonate compound (II).
  • the transesterification reaction is an equilibrium reaction, when the hydroxyl group-containing by-product accumulates in the reaction system, the polymerization does not advance satisfactorily. Therefore, it is provided that the polymerization reaction is performed while removing the low molecular hydroxyl group-containing by-product from the reaction system.
  • the polymerization reaction of the step (1) is performed with carbonate compounds different from phosgene or diphosgene in the following manner: a vapor containing the hydroxyl group-containing by-product which is produced during the polymerization reaction, is generated, and the vapor thus generated is condensed to obtain a condensate, and at least a part of the thus obtained condensate is removed from the reaction system.
  • the polymerization reaction is performed at sufficiently high temperature or/and under reduced pressure.
  • a method for increasing the efficiency of the removal of the hydroxyl group-containing by-product especially after achieving considerable conversion rates, a method may be adopted in which an inert gas (such as nitrogen, argon, helium, carbon dioxide and a lower hydrocarbon gas) which does not have an adverse effect on the polymerization reaction, is introduced into the reaction system so that the hydroxyl group-containing by-product is removed in a form entrained by the inert gas.
  • an inert gas such as nitrogen, argon, helium, carbon dioxide and a lower hydrocarbon gas
  • the polymerization reaction is performed in a reactor equipped with a fractionating column.
  • the separating capability thereof is important.
  • a fractionating column is used which generally has a number of theoretical plates of 5 or more, preferably 7 or more.
  • a fractionating column is used generally in such a form as equipped, at its top, with an appropriate reflux condenser.
  • the reflux condenser is used for condensing the vapor ascending inside of the fractionating column, to form a condensate, and for causing at least a part of the condensate to flow down inside of the fractioning column, back to the reactor.
  • Such a fractionating column is advantageous in that the vapor containing the hydroxyl group-containing by-product (which ascends inside of the fractionating column) and the condensate (which flows down inside of the fractionating column) contact each other in a counter flow, thereby causing the hydroxyl group-containing byproduct in the condensate to move into the vapor, and also causing the diols (I) and the carbonate compound (II) in the vapor to move into the condensate, to thereby facilitate the efficient removal of the hydroxyl group-containing by-product from the reaction system.
  • the polymerization reaction is performed by using the reactor as mentioned above, while generating a vapor containing the hydroxyl group-containing by-product, and the generated vapor is condensed into a condensate by means of a reflux condenser, followed by removal of a part of the obtained condensate as a distillate from the reaction system while causing the residue of the condensate to flow down inside of the fractioning column, back to the reactor.
  • the throughput is important to appropriately control the amount of the vapor (containing the hydroxyl group-containing by-product) which ascends inside of the fractionating column per unit time (i.e., it is important to appropriately control the so-called "throughput").
  • the throughput is too small, the rate of removal of the hydroxyl group-containing by-product becomes low and hence the reaction time becomes long.
  • the throughput is too large, the efficiency of the reaction is decreased, due to, for example, the distillation of the diols (I). Therefore, it is preferred that the throughput is as great as possible, as long as the efficiency of the reaction is not decreased.
  • the control of the reflux ratio and throughput is performed by appropriately controlling the temperature and pressure for the reaction.
  • the appropriate control of the reflux ratio and throughput is extremely advantageous in that the polymerization reaction can be completed in a relatively short time, thereby improving not only the productivity of the polycarbonate polyol but also the quality thereof.
  • the reaction temperature in the step (1) is preferably in the range of from 80 to 180 °C, more preferably from 110 to 170 °C.
  • the rate of the transesterification reaction becomes low and hence the reaction time becomes long.
  • the pressure for the reaction is preferably in the range of from 0.1 mbar to 15 bar (not included into consideration is the pressure which can by set up by any inert component such as an inert gas).
  • the polymerization reaction in the step (1) is terminated when the conversion of diol has reached 50 to 95 %.
  • the removal of the compounds resulting from the residual leaving groups of the carbonate compound (II), the compounds of general formula HO-R-OH (I) and optionally compounds of the component (III) from the reaction system is performed by evaporation and hence, in the step (2), the polymerization reaction is generally performed under reduced pressure.
  • the contents (reaction mixture) of the reactor are heated under reduced pressure to effect a self-condensation reaction while removing to the outside of the reaction system a vapor being generated which is comprised mainly of the compounds resulting from the residual leaving groups of the carbonate compound (II), diols (I) and optionally compounds of the component (III).
  • the step (2) for efficiently removing the compounds resulting from the residual leaving groups of the carbonate compound (II), diols (I) and optionally compounds of the component (III) as they are separated from the polycarbonate polyol being produced, it is preferred that the vapor comprised mainly of the compounds resulting from the residual leaving groups of the carbonate compound (II), diols (I) and optionally compounds of the component (III) is directly removed from the reaction system to the outside, without using a fractionating column or the like.
  • the reaction mixture obtained in the step (1) is caused to flow down in the form of a thin film in the evaporator, thereby evaporating off the compounds resulting from the residual leaving groups of the carbonate compound (II), diols (I) and optionally compounds of the component (III) while performing the reaction in the step (2).
  • step (2) the polycarbonate prepolymer obtained in the step (1) is subjected to a self-condensation reaction, thereby producing the polycarbonate polyol of the present invention. Since this self- condensation reaction is a transesterification, as the reaction proceeds, the diols (I), carbonate compounds (II) and, optionally, compounds of the component (III) are eliminated from the terminals of the polycarbonate polyol being produced. Since the transesterification reaction is an equilibrium reaction, when the diols (I) and optionally compounds of the component (III) accumulate in the reaction system, the polymerization does not satisfactorily advance.
  • the polymerization reaction is performed while removing the diols (I) and optionally compounds of the component (III) from the reaction system.
  • step (2) generally, the reaction mixture obtained in the step (1), as such, namely without being purified, is subjected to a self-condensation reaction.
  • the reaction mixture may contain unreacted diols (I) or unreacted carbonate compound (II) or optionally compounds of the component (III); however, these unreacted substances are removed either in the depressurization operation immediately upon initiation of the reaction in the step (2) or at the early stage of the reaction in the step (2).
  • step (2) the reaction temperature is preferably in the range of from 125 °C to 180 °C, more preferably from 130 °C to 170 °C and the step (2) takes place under reduced pressure, that is below 1 bar.
  • the pressure for the reaction in the step (2) is generally in the range of from 0.1 mbar to 500 mbar, more preferably in the range of from 0.1 to 100 mbar.
  • the polymerization reaction and the self-condensation reaction are performed in the presence of a catalyst.
  • the catalyst can be appropriately selected from compounds capable of catalyzing transesterification reactions.
  • Typical catalysts for the synthesis of polycarbonate polyols can be selected from the group consisting of amines (R4)3N, wherein R4 represents, independent of each other, H or a Ci to C30 alkyl group or a Ce to C30 arylalkyl group and/or ammonium ions (R5)4N + , wherein R5 represents, independent of each other, H or a Ci to C30 alkyl group or a Ce to C30 arylalkyl group, alkali metal compounds such as oxides, hydroxides, carbonates, carboxylates, alkoxides, amides, ketonates, aldonates, aldoimides, ketoimides, earth alkali metal compounds such as oxides, hydroxides, carbonates, carboxylates, alkoxides, amides
  • ketonate compounds of the transition metals of the 3rd Group of the Periodic Table of the Elements are preferred catalysts for the preparation of the polycarbonate polyols starting from diols (I), dialkyl carbonates or/and alkylene carbonates (II) and optional polyalcohols according to component (III).
  • Even more preferred catalysts are ketonates of rare earth metals.
  • Particularly preferable are purified and free of water Y and Yb ketonates, such as Y and Yb acetylacetonates.
  • the amount of catalyst is preferably in the range of from 1 ppm to 10000 ppm by weight, more preferably 10 ppm to 1000 ppm by weight, based on the total weight of the alcohol containing components (I) and optionally (III) charged into the reactor.
  • step (3) of the process of the preparation of the polycarbonate polyols the crude polycarbonate polyol obtained after steps (1) and (2) may need to be purified so that polycarbonate polyol mixtures are obtained with the proviso that the sum of the weight contents of amines (R4)3N, wherein R4 represents, independent of each other, H or a Ci to C30 alkyl group or a Ce to C30 arylalkyl group and/or ammonium ions (R5)4N + , wherein R5 represents, independent of each other, H or a Ci to C30 alkyl group or a Ce to C30 arylalkyl group, metal atoms and/or metal ions and/or metal compounds comprising metal in the respective oxidation state selected from the group consisting of Li, Li + , Na, Na + , K, K + , Ca, Ca 2+ , Sr, Sr 2+ , Mg, Mg 2+ , Ba, Ba 2+ , Al, Al 3+ , Ga, Ga
  • This purification step can be done by simple separation of the mixture comprising polycarbonate polyol from the catalyst by filtration, extraction, washing, chromatography, ion exchange and others known to the man skilled in the art.
  • Rl represents -(CH 2 )4-.
  • R2 represents -(CH 2 ) 5 - and/or -(CH 2 )2-(CHCH 3 )-(CH 2 )2-.
  • R3 represents -(CH 2 )2-(CHCH 3 )-(CH 2 )2- and/or -(CH 2 ) 6 -.
  • Rl represents -(CH 2 )4-
  • R2 represents -(CH 2 ) 5 - and/or -(CH 2 ) 2 -(CHCH 3 )-(CH 2 ) 2 -
  • R3 represents -(CH 2 ) 2 -(CHCH 3 )-(CH 2 ) 2 - and/or -(CH 2 ) 6 -
  • the polycarbonate polyol may be obtained from 1 ,4-butanediol, 1,5-pentanediol, 3-methyl-l,5- pentandiol and 1,6-hexanediol, respectively.
  • the present invention is directed to the use of a mixture according to the invention for the preparation of polyurethane polymers (this also includes polyurethane-co-polyurea polymers).
  • the mixture of the present invention is advantageous for various uses, such as a raw material for thermoplastically formable polyurethanes (such as thermoplastic elastomers) used for producing various shaped articles (for example, a spandex, which is a polyurethane elastomeric fiber); a component for a coating material or an adhesive; and a polymeric plasticizer.
  • a raw material for thermoplastically formable polyurethanes such as thermoplastic elastomers
  • a spandex which is a polyurethane elastomeric fiber
  • a component for a coating material or an adhesive for example, a polyurethane elastomeric fiber
  • a polymeric plasticizer for the preparation of polyurethane polymer dispersions is contemplated which after film formation may show excellent resistance to hydrolysis, light and oxid
  • thermoplastic polyurethanes are obtained from the mixture according to the invention and at least one polyisocyanate and, optionally, from other difunctional alcohols, difunctional amines, monoalcohol-monoamines, difunctional thiols, water as chain extenders as well as optionally from monofunctional alcohols, monofunctional amines, and monofunctional thiols as chain terminating reagents.
  • Aqueous polyurethane dispersions are obtained from at least one polycarbonate polyol mixture according to the invention, at least a polyisocyanate, optionally, at least one hydrophilic compound chosen from the group of difunctional polyethylene oxide alcohols or/and monoalkoxylated, for example but not limited to monomethoxylated, monofunctional polyethylene oxide alcohols with a numb er average mo lecular weight o f les s than 3000 g/mo l, such as for examp le monomethoxypolyethylene glycol 750 (MPEG 750), Desmophen® LB25 (Bayer), difunctional alcohols or/and monofunctional alcohols, carrying ionic or potentially ionic groups, such as for example but not limited to, di(hydroxymethyl)propionic acid, di(hydroxymethyl)butanoic acid, monohydroxypivalic acid, difunctional or/and monofunctional alcohols, carrying sulphonic acid or sulphonate groups, difunctional or/and monofunctional amines (or/
  • the weight averaged particle size d50 of such polyurethane dispersions is typically in the range from 5 to 2000 nm, preferably from 15 to 1000 nm.
  • the particle size distribution can vary from narrow to broad and maybe monomodal, bimodal and polymodal.
  • D50-value means that 50 weight- % of all particles of the dispersions have particle size below this value and the other 50 weight- % of the particles have a particle size above this value.
  • the width of the particle size distribution is defined as U90-value which is the ratio of (d90 dl0)/d50. This value typically varies from 0.01 to 100. The smaller this value, the narrower the particle size distribution.
  • polyisocyanates used for producing the thermoplastic elastomers of the presently claimed invention include conventional aromatic diisocyanates, such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (TDI), diphenylmethane-4,4'-diisocyanate (MDI), naphthalene- 1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'- biphenylene diisocyanate, crude TDI, hydrogenated TDI (H6TDI), polymethylenepolyphenyl isocyanate, crude MDI, xylylene diisocyanate (XDI) and phenylene diisocyanate; conventional aliphatic diisocyanates, such as 4,4'-methylenebis(cyclohexyl) diisocyanate (hydrogenated MDI), hexan
  • polyurethane-co-polyurea polyurethane-co-polyurea
  • a urethane-forming technique known in the art may be employed.
  • the polycarbonate polyol of the presently claimed invention is reacted with an organic polyisocyanate in the presence or absence of a solvent under atmospheric pressure at a temperature of from room temperature to 200 °C to form polyurethane.
  • solvents include dimethylformamide, diethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, acetone, methyl ethyl ketone, methyl isobutyl ketone, dioxane, cyclohexanone, benzene, toluene and ethyl cellosolve.
  • a chain extender or/and chain terminating agent may be added to the reaction system either before initiating the reaction or during the reaction.
  • the process includes a step of dispersing the polyurethane or a polyurethane solution after the optional chain extension or/and chain termination step or during this step.
  • chain extending reagents bearing potential ionic groups are used to render the polyurethane polymer dispersible in water it is necessary to transform these potentially ionic groups partially or completely into ionic groups by reacting them with suitable bases, such as for example amines, alkali metal hydroxides, alkali metal carbonates and the like.
  • suitable bases such as for example amines, alkali metal hydroxides, alkali metal carbonates and the like.
  • This neutralization step can take place prior to dispersion step or parallel to dispersion step. It is also possible to use external ionic or non-ionic surfactants to make dispersions.
  • the dispersion of polyurethane polymer in water takes place with the aid of high shear forces such as agitation, high speed agitation, high pressure homogenization and other methods known to the man skilled in the art.
  • the optional organic solvent can either remain in the dispersion or be removed by an appropriate method. The removal of the optional organic solvent can take place partially or completely prior to dispersion step, during the dispersion step or after the dispersion step. Also mixtures of different solvents can be used. It is also possible to use radical polymerisable vinylic monomers as solvents and to remove these monomers from the polyurethane dispersion by radical polymerization to form certain amount of polyvinylic dispersion along with polyurethane dispersion.
  • Suitable radical polymerisable vinylic monomers are for example styrene, (meth)acrylic acid esters, vinylalcohol ethers and esters and the like.
  • Thermoplastic polyurethanes and polyurethane dispersions comprising inventive polycarbonate polyol may contain further additives typical for these products such as thermal and UV-light stabilizers, antioxidants, antimicrobial and antibacterial additives, lubricants, pigments and inorganic fillers, foaming and antifoaming agents, flame retardants and the like.
  • Thermoplastic polyurethanes and polyurethane dispersions comprising inventive polycarbonate polyols can be advantageously used for injection molding applications and, accordingly, have to withstand high temperatures as well, whereas polyurethane dispersions as well as coatings, adhesives, sealants as well as artificial textiles and leather made of such dispersion have to withstand hydrolysis upon storage and during the service lifetime.
  • the present invention is also directed towards a thermoplastic polyurethane obtained from a mixture according to the invention and at least a polyisocyanate.
  • the polycarbonate polyols of the present inventions possess enhanced thermal stability and hydrolysis resistance.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention porte sur un mélange comprenant un polyol de polycarbonate présentant une température de décomposition ≥ 180°C à une pression de ≥ 0,1 mbar à ≤ 1 mbar, qui est à base d'au moins deux diols différents choisis dans le groupe constitué par les diols en C4, en C5 et en C6, le mélange ayant une quantité somme toute faible d'amines et/ou d'ions ammonium, d'atomes et/ou d'ions de métal alcalin, d'atomes et/ou d'ions de métal alcalinoterreux, de métaux et/ou d'ions des groupes 13 à 15 du tableau périodique des éléments (c'est-à-dire de métaux provenant des groupes du bore, du carbone et de l'azote) et d'atomes et/ou d'ions de métal de transition des groupes 4 à 12 du tableau périodique des éléments par rapport au poids total du polyol de polycarbonate. En outre, la valeur de pH d'une suspension épaisse à 10 % en poids de ce mélange dans de l'eau se situe dans la plage de ≥ 5,0 à ≤ 8,0. La présente invention porte également sur l'utilisation de ces polyols pour la production de polyuréthanes, en particulier de dispersions et de polymères thermoplastiques.
PCT/EP2012/067192 2011-09-07 2012-09-04 Polyols de polycarbonate WO2013034539A1 (fr)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN107987268A (zh) * 2017-12-07 2018-05-04 万华化学集团股份有限公司 一种使用双催化剂生产聚碳酸酯多元醇的合成方法

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EP1288241A1 (fr) 2000-05-24 2003-03-05 Asahi Kasei Kabushiki Kaisha Diol de polycarbonate ayant une forte concentration de terminaux oh
JP2004220018A (ja) * 2002-12-26 2004-08-05 Hokushin Ind Inc クリーニングブレード部材
JP2005054034A (ja) 2003-08-01 2005-03-03 Kuraray Co Ltd ポリオール組成物の製造方法
US20060052572A1 (en) 2004-09-04 2006-03-09 Steffen Hofacker Metal acetylacetonates as transesterification catalysts
US20060293468A1 (en) * 2005-06-23 2006-12-28 Bayer Materialscience Ag Polymer blend based on polycarbonate polyols
WO2012010527A2 (fr) * 2010-07-20 2012-01-26 Bayer Materialscience Ag Polycarbonate polyol hautement résistant d'un point de vue thermique et hydrolytique

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Publication number Priority date Publication date Assignee Title
EP1288241A1 (fr) 2000-05-24 2003-03-05 Asahi Kasei Kabushiki Kaisha Diol de polycarbonate ayant une forte concentration de terminaux oh
US20030176622A1 (en) * 2000-05-24 2003-09-18 Mitsuo Konishi Polycarbonate diol having high proportion of primary terminal oh
JP2004220018A (ja) * 2002-12-26 2004-08-05 Hokushin Ind Inc クリーニングブレード部材
JP2005054034A (ja) 2003-08-01 2005-03-03 Kuraray Co Ltd ポリオール組成物の製造方法
US20060052572A1 (en) 2004-09-04 2006-03-09 Steffen Hofacker Metal acetylacetonates as transesterification catalysts
US20060293468A1 (en) * 2005-06-23 2006-12-28 Bayer Materialscience Ag Polymer blend based on polycarbonate polyols
WO2012010527A2 (fr) * 2010-07-20 2012-01-26 Bayer Materialscience Ag Polycarbonate polyol hautement résistant d'un point de vue thermique et hydrolytique

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107987268A (zh) * 2017-12-07 2018-05-04 万华化学集团股份有限公司 一种使用双催化剂生产聚碳酸酯多元醇的合成方法
CN107987268B (zh) * 2017-12-07 2020-08-04 万华化学集团股份有限公司 一种使用双催化剂生产聚碳酸酯多元醇的合成方法

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