METHOD FOR PRODUCING POLYMERIC RING-OPENING PRODUCTS

Abstract

The invention relates to a method for adding a compound (A) to an H-functional starting compound (BH) in the presence of a catalyst, wherein the at least one compound (A) is selected from at least one group consisting of alkylene oxide (A-1), lactone (A-2), lactide (A-3), cyclic acetal (A-4), lactam (A-5), cyclic anhydride (A-6) and oxygen-containing heterocyclic compound (A-7) different from (A-1), (A-2), (A-3), (A-4) and (A-6), wherein the catalyst comprises an organic, n-protic Brnsted acid (C), wherein n2 and is an element of the natural numbers and the degree of protolysis D is 0<D<n, with n as the maximum number of transferable protons and D as the calculated proton fraction of the organic, n-protic Brnsted acid (C). The invention further relates to an n-protic Brnsted acid (C) having a degree of protolysis D of 0<D<n, wherein n is the maximum number of transferable protons, with n=2, 3 or 4, and D is the calculated proton fraction of the organic, n-protic Brnsted acid (C).

Claims

1. A process for addition of a compound (A) onto an H-functional starter compound (BH) in the presence of a catalyst, wherein the at least one compound (A) is selected from at least one group consisting of alkylene oxide (A-1), lactone (A-2), lactide (A-3), cyclic acetal (A-4), lactam (A-5), cyclic anhydride (A-6) and oxygen-containing heterocycle compound (A-7) distinct from (A-1), (A-2), (A-3), (A-4) and (A-6), characterized in that the catalyst comprises an organic, n-protic Bronsted acid (C), wherein n 2 and is an element of the natural numbers and the degree of protolysis D is 0<D<n where n is the maximum number of transferable protons and D is the calculated proton fraction of the organic, n-protic Bronsted acid (C) wherein the organic, n-protic Bronsted acid (C) has a calculated molar mass of 1200 g/mol.

2. The process as claimed in claim 1, wherein the compound (A) is selected from at least one group consisting of alkylene oxide (A-1), lactone (A-2), cyclic acetal (A-4) and cyclic anhydride (A-6).

3. The process as claimed in claim 1, wherein the organic, n-protic Bronsted acid (C) is a sulfonic acid.

4. The process as claimed in claim 1, wherein the maximum number of transferable protons n is n=2, 3 or 4.

5. The process as claimed in claim 4, wherein the degree of protolysis D for diprotic acids where n=2 is 0.2 to 1.9, for triprotic acids where n=3 is 0.3 to 2.8 and for tetraprotic acids where n=4 is 0.4 to 3.7.

6. The process as claimed in claim 1, wherein the organic, n-protic Bronsted acid (C) having the degree of protolysis 0<D<n is obtained by acid-base reactions with proton transfer by () addition of suitable amounts of suitable Bronsted bases (E) to the organic, n-protic Bronsted acids or () addition of suitable amounts of suitable Bronsted acids (EH) to the salts of the organic, n-protic Bronsted acids.

7. The process as claimed in claim 6, wherein the organic, n-protic Bronsted acid (C) having the degree of protolysis 0<D<n is obtained by acid-base reactions with proton transfer in step () by addition of Bronsted bases (E) having a pK.sub.b(E) of 10, preferably having a pK.sub.b(E) of 8 and very particularly preferably having a pK.sub.b(E) of 5 to the completely protonated sulfonic acids or () by addition of strong Bronsted acids (EH) having a pK.sub.s(EH) of 1 to the metal salt of a sulfonic acid.

8. The process as claimed in claim 1, wherein the at least one compound (A) is selected from the group consisting of ethylene oxide, propylene oxide, styrene oxide, allyl glycidyl ether, -caprolactone, propiolactone, -butyrolactone, -butyrolactone, -caprolactam, 1,3-dioxolane, 1,4-dioxane, tetrahydrofuran and 1,3,5-trioxane.

9. The process as claimed in claim 1, wherein the compound (BH) is one or more compounds and is selected from the group consisting of mono- or polyvalent alcohols, polyvalent amines, polyvalent thiols, amino alcohols, thio alcohols, hydroxy esters, polyether polyols, polyester polyols, polyester ether polyols, polyether carbonate polyols, polycarbonate polyols, polycarbonates, polyacetals, polymeric formaldehyde compounds, polyethyleneimines, polyetheramines, polytetrahydrofurans, 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 C1-C24 alkyl fatty acid esters containing on average at least 2 OH groups per molecule.

10. An n-protic Bronsted acid (C) having a degree of protolysis D of 0<D<n, wherein n is the maximum number of transferable protons where n=2, 3 or 4 and D is the calculated proton fraction of the organic, n-protic Bronsted acid (C), characterized in that the degree of protolysis D for diprotic acids where n=2 is 0.2 to 1.9, for triprotic acids where n=3 is 0.3 to 2.8 and for tetraprotic acids where n=4 is 0.4 to 3.7, wherein the organic, n-protic Bronsted acid (C) having the degree of protolysis 0<D<n is obtained by acid-base reactions with proton transfer by () addition of suitable amounts of at least one suitable Bronsted base (E) to the at least one organic, n-protic Bronsted acid, wherein the Bronsted base (E) contains at least one cation (F) selected from the group consisting of alkali metal-containing, alkaline earth metal-containing, metalloid-containing, transition metal-containing, lanthanoid metal-containing, aliphatic ammonium-containing and phosphonium-containing and sulfonium-containing cations or () addition of suitable amounts of at least one suitable Bronsted acid (EH) to the salt of the at least one organic, n-protic Bronsted acid, wherein the salts of the organic, n-protic Bronsted acid contains at least one cation (F) selected from the group consisting of alkali metal-containing, alkaline earth metal-containing, metalloid-containing, transition metal-containing, lanthanoid metal-containing, aliphatic ammonium-containing and phosphonium-containing and sulfonium-containing cations, wherein the n-protic Bronsted acid (C) is at least one sulfonic acid and wherein the at least one sulfonic acid is selected from the group consisting of 1,5-naphthalenedisulfonic acid, 2,6-naphthalenedisulfonic acid and 1,3-benzenedisulfonic acid, preferably 1,5-naphthalenedisulfonic acid, 2,6-naphthalenedisulfonic acid, and very particularly preferably 2,6-naphthalenedisulfonic acid.

11. The n-protic Bronsted acid (C) as claimed in claim 10, wherein the cation (F) is selected from the group consisting of lithium cation, sodium cation, potassium cation, rubidium cation, cesium cation, magnesium cation, calcium cation, strontium cation, barium cation, scandium cation, titanium cation, zinc cation, aluminum cation, aliphatic primary ammonium ions, aliphatic secondary ammonium ions, aliphatic tertiary ammonium ions, aliphatic quaternary ammonium ions, phosphonium ions, sulfonium ions and sulfoxonium ions, preferably from lithium cation, sodium cation, potassium cation, magnesium cation, calcium cation, quaternary ammonium ions and triphenylphosphonium ions and particularly preferably from sodium cation, potassium cation, magnesium cation and n-butylammonium ion.

12. The n-protic Bronsted acid (C) as claimed in claim 10, wherein the cation (F) is selected from the group consisting of lithium cation, sodium cation, potassium cation, rubidium cation, cesium cation, magnesium cation, calcium cation, strontium cation, barium cation, scandium cation, titanium cation, zinc cation, aluminum cation, aliphatic primary ammonium ions, aliphatic secondary ammonium ions, aliphatic tertiary ammonium ions, aliphatic quaternary ammonium ions, phosphonium ions, sulfonium ions and sulfoxonium ions, preferably from lithium cation, sodium cation, potassium cation, magnesium cation, calcium cation, quaternary ammonium ions and triphenylphosphonium ions and particularly preferably from sodium cation, potassium cation, magnesium cation and n-butylammonium ion.

13. The n-protic Bronsted acid (C) as claimed in claim 10, wherein the at least one Bronsted base (E) is selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, scandium hydroxide, titanium hydroxide, zinc hydroxide, aluminum hydroxide, aliphatic primary ammonium hydroxides, aliphatic secondary ammonium hydroxides, aliphatic tertiary ammonium hydroxides, aliphatic quaternary ammonium hydroxides, phosphonium hydroxides, aliphatic primary ammonium alkoxides, aliphatic secondary ammonium alkoxides, aliphatic tertiary ammonium alkoxides, aliphatic quaternary ammonium alkoxides, phosphonium alkoxides, butylithium, potassium tert-butoxide, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo(4.3.0)non-5-ene (DBN), primary aliphatic amines, secondary aliphatic amines, tertiary aliphatic amines, primary cycloaliphatic amines, secondary cycloaliphatic amines, tertiary cycloaliphatic amines and phosphonium alkoxides, preferably from sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, aliphatic quaternary ammonium alkoxides, phosphonium alkoxides, ammonia, triethylamine, trimethylamine, diethylamine, propylamine, methylamine, dimethylamine, ethylamine, ethylenediamine, 1,3-diaminopropanes, putrescine, 1,5-diaminopentane, hexamethylenediamine, 1,2-diaminopropanes, diaminocyclohexane, n-propylamine, di-n-propylamine, tri-n-propylamin, isopropylamine, diisopropylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, diisobutylamine, 2-aminobutane, 2-ethylhexylamine, di-2-ethylhexylamine, cyclohexylamine, dicyclohexylamine, dimethylaminopropylamine, triethylenediamine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1,5-diazabicyclo(4.3.0)non-5-ene (DBN), particularly preferably from sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, tetra(n-butyl)ammonium methoxide, tetra(n-butyl)ammonium ethoxide and tetra(n-butyl)ammonium isopropoxide.

14. The n-protic Bronsted acid (C) as claimed in claim 10, wherein the at least one Bronsted acid (EH) is selected from the group consisting of aliphatic fluorinated sulfonic acids, aromatic fluorinated sulfonic acids, trifluoromethanesulfonic acid, perchloric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, fluorosulfonic acid, bis(trifluoromethane)sulfonimide, hexafluorantimonic acid, pentacyanocyclopentadiene, picric acid, sulfuric acid, nitric acid, trifluoroacetic acid, methanesulfonic acid, paratoluenesulfonic acid, aromatic sulfonic acids and aliphatic sulfonic acids, preferably from trifluoromethanesulfonic acid, perchloric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, fluorosulfonic acid, bis(trifluoromethane)sulfonimide, hexafluorantimonic acid, pentacyanocyclopentadiene, picric acid, sulfuric acid, nitric acid, trifluoroacetic acid, methanesulfonic acid, paratoluenesulfonic acid, methanesulfonic acid and paratoluenesulfonic acid, particularly preferably from trifluoromethanesulfonic acid, perchloric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, bis(trifluoromethane)sulfonimide, pentacyanocyclopentadiene, sulfuric acid, nitric acid and trifluoroacetic acid.

15. (canceled)

16. Sulfonic acid as claimed in claim 10, wherein the degree of protolysis D is 0.8 to 1.8, preferably 1.1 to 1.7.

Description

EXAMPLES

[0133] The present invention is elucidated in detail by the figures and examples which follow, but without being limited thereto.

Compounds (A)

[0134] Ethylene oxide (3.0, purity99.9% by weight, Linde AG)
Propylene oxide (purity 99.9%, Chemogas GmbH)
Styrene oxide (purity 97%, Sigma-Aldrich Chemie GmbH)
Allyl glycidyl ether (purity 99%, Sigma-Aldrich Chemie GmbH)
1,3-Dioxolane (purity 99.8%, Sigma-Aldrich Chemie GmbH)
-Butyrolactone (purity 98%, Sigma-Aldrich Chemie GmbH)
-Caprolactone (purity 97%, Sigma-Aldrich Chemie GmbH)
Maleic anhydride (purity 99%, Sigma-Aldrich Chemie GmbH)
Tetrahydrofuran (absolute, purity 99.9%, Sigma-Aldrich Chemie GmbH)

Compounds (BH) Having at Least One Zerewitino-Active Hydrogen Atom

PEG:

[0135] Polyethylene glycol having a molecular mass of 1000 g/mol was obtained from Fluka. Before further use the commercially available product was dried over phosphorus pentoxide in a desiccator.

PET:

[0136] Polypropylene glycol (ARCOL POLYOL 1004) having an average molecular mass of 432 g/mol (hydroxyl number (OH number): 250-270 mg(KOH)/g) was obtained from Covestro AG. Before further use the available product was dried under high vacuum.

PC: CONVERGE Polyol 212-10, M=1000 g/mol:

[0137] Polycarbonate diol from Novomer Inc. CONVERGE Polyol 212-10 obtainable by reaction of CO2 and propylene oxide having an average molecular mass of 1000 g/mol, a CO2 fraction of about 40% by weight, an OH number of 112 mg(KOH)/g. Analysis of the starting material by proton resonance spectroscopy revealed a content of 3% by weight of cyclic propylene carbonate (cPC).

pFA: Paraformaldehyde (M=450 g/mol)

[0138] Paraformaldehyde (trade name: Granuform 96) was obtained from Ineos AG. The number-average molecular mass of the product is specified as 450 g/mol.

Employed Catalysts/Starting Materials Thereof

[0139] 1,3-Benzenedisulfonic acid disodium salt: 1,3-Na2-BDS (purity 94%, Sigma-Aldrich Chemie GmbH)
1,5-Naphthalenedisulfonic acid disodium salt: 1,5-Na2-NDS (purity 95%, Sigma-Aldrich Chemie GmbH)
2,6-Naphthalenedisulfonic acid disodium salt: 2,6-Na2-NDS (purity 97%, Sigma-Aldrich Chemie GmbH)
1,5-Naphthalenedisulfonic acid 1,5-NDS (purity 97%, Sigma-Aldrich Chemie GmbH)
Sulfuric acid: H.sub.2SO.sub.4 (purity 98%, Sigma-Aldrich Chemie GmbH)
Trifluoromethanesulfonic acid: CF.sub.3SO.sub.3H (purity 98%, Sigma-Aldrich Chemie GmbH)
Sodium triflate: NaOTf (purity 97%, Sigma-Aldrich Chemie GmbH)
Sodium hydrogensulfate: NaHSO.sub.4 (purity 90%, Sigma-Aldrich Chemie GmbH)
Para-toluenesulfonic acid: p-TSA (purity 98%, Sigma-Aldrich Chemie GmbH)
Fumaric acid C.sub.4H.sub.4O.sub.4: (purity 99%, Sigma-Aldrich Chemie GmbH)
Tetrabutylammonium methoxide solution: (n-Bu).sub.4N (OMe) (20% methanol solution, Sigma-Aldrich Chemie GmbH)
1,8-Diazabicyclo[5.4.0]undec-7-ene: DBU (purity 98%, Sigma-Aldrich Chemie GmbH)
Perfluorosulfonic acid membrane: Nation N117-type in a thickness of 0.007 inch with equivalent amount of sulfonyl groups of 0.91-1.11 mmol/g (manufacturer specifications for ion exchange capacity IEC), Sigma-Aldrich Chemie GmbH

Description of the Methods:

[0140] Gel permeation chromatography (GPC): The measurements were performed on an Agilent 1200 Series (G1310A Iso Pump, G1329A ALS, G1316A TCC, G1362A RID, G1365D MWD), detection by RID; eluent: tetrahydrofuran (GPC grade), flow rate 1.0 ml/min; column combination: PSS SDV precolumn 850 mm (5 m), 2PSS SDV linear S 8300 ml (5 m). Polystyrene of known molar mass from PSS Polymer Standards Service were used for calibration. The measurement recording and evaluation software used was the PSS WinGPC Unity software package. The GPC chromatograms were recorded in accordance with DIN 55672-1. The peak molecular weight (MPeak or M.sub.P for short) in the GPC chromatogram corresponds to the molar weight, according to calibration, at maximum detector signal.

[0141] The polydispersity index from weighted (M.sub.w) and number-average (M.sub.n) molecular weight from the gel permeation chromatography is defined as M.sub.w/M.sub.n.

[0142] .sup.1H-NMR spectroscopy (proton resonance spectroscopy): The measurements were performed using a Bruker AV400 instrument (400 MHz); the chemical shifts were calibrated relative to the solvent signal (CDCl.sub.3, =7.26 ppm); s=singlet, m=multiplet, bs=broadened singlet, kb=complex region.

[0143] .sup.13C NMR spectroscopy: The measurements were performed using a Bruker AV400 instrument (100 MHz); the chemical shifts were calibrated relative to the solvent signal (CDCl.sub.3, =77.16 ppm); HMBC: hetero multiple bond correlation.

[0144] The content of polyoxymethylene groups, polypropylene oxide groups and polyethylene oxide groups in the polyol component was determined using .sup.1H-NMR spectroscopy. The relative contents of the individual increments were determined by integration of the characteristic proton signals. These were also used for quantifying conversions. Characteristic signals of the compounds produced are:

[0145] .sup.1H NMR (300 MHz, CDCl.sub.3) =1.14 (m, 3H, methyl groups PO); 3.20-3.55 (m, 3H, ethylene groups PO); 3.73 (s, 4H, ethylene groups EO); 4.70-4.90 (m, 2H, methylene groups formaldehyde FA) ppm.

[0146] .sup.13C NMR (75 MHz, CDCl.sub.3) =17.4 (methyl groups PO); 66.9-67.5 (ethylene groups PO and EO); 75.5 (ethylene groups PO); 73.0 (ethylene groups PO and EO); 88.0-95.5 (methylene groups formaldehyde FA); 154.8 (carbonate) ppm.

Catalyst Synthesis

Synthesis of Catalyst C-1 Employable According to the Invention

[0147] To synthesize catalyst C-1 1.182 g of the 1,5-naphthalenedisulfonic acid disodium salt (3.556 mmol; 1.0 eq.) were suspended in 15 ml of absolute dichloromethane under inert conditions. With vigorous stirring, 0.19 ml of 98% sulfuric acid (3.556 mmol; 1.0 eq.) were added. After 10 minutes of stirring the solvent was removed under vacuum and the solid was dried under high vacuum over 4 hours.

[0148] The obtained catalyst was used in further reactions without further purification.

D=1.0

[0149] Alternatively, the catalyst C-1 may also be produced directly in the presence of the starter (BH) in analogous fashion with or without dichloromethane.

Synthesis of Catalyst C-2 Employable According to the Invention

[0150] To synthesize catalyst C-2 3.709 g of the 1,3-benzenedisulfonic acid disodium salt (13.158 mmol; 1.0 eq.) were suspended in 30 ml of absolute dichloromethane under inert conditions. With vigorous stirring, 0.70 ml of 98% sulfuric acid (13.158 mmol; 1.0 eq.) were added. After 10 minutes of stirring the solvent was removed under vacuum and the solid was dried under high vacuum over 4 hours.

[0151] The obtained catalyst was used in further reactions without further purification.

D=1.0

[0152] Alternatively, the catalyst C-2 may also be produced directly in the presence of the starter (BH) in analogous fashion with or without dichloromethane.

Synthesis of Catalyst C-3 Employable According to the Invention

[0153] To synthesize catalyst C-3 2.000 g of the 1,5-naphthalenedisulfonic acid disodium salt (6.019 mmol; 1.0 eq.) were suspended in 15 ml of absolute dichloromethane under inert conditions. With vigorous stirring, 0.898 ml of trifluoromethanesulfonic acid (1.535 g; 10.233 mmol; 1.7 eq.) were added. After stirring for 10 minutes the solvent was removed under vacuum.

[0154] The obtained catalyst C-3 was used in further reactions without further purification.

D=1.7

[0155] Alternatively, the catalyst C-3 may also be produced directly in the presence of the starter (BH) in analogous fashion with or without dichloromethane.

Synthesis of Catalyst C-4 Employable According to the Invention

[0156] Analogously to the preparation of catalyst C-3 the catalyst C-4 was produced with a degree of protonation D of D=1.3. The amount of the trifluoromethanesulfonic acid was employed according to the degree of protonation D=1.3.

D=1.3

[0157] Alternatively, the catalyst C-4 may also be produced directly in the presence of the starter (BH) in analogous fashion with or without dichloromethane.

Synthesis of Catalyst C-5 Employable According to the Invention

[0158] 1.171 g (3.525 mmol) of 2,6-naphthalenedisulfonic acid disodium salt were suspended in absolute dichloromethane and admixed with 0.41 ml (4.700 mmol; 0.705 g) of trifluoromethanesulfonic acid. The suspension was stirred over 20 minutes and subsequently concentrated under vacuum.

[0159] The obtained catalyst C-5 was used in further reactions without further purification.

D=1.3

[0160] Alternatively, the catalyst C-5 may also be produced directly in the presence of the starter (BH) in analogous fashion with or without dichloromethane.

Synthesis of Catalyst C-6 Employable According to the Invention

[0161] Analogously to the preparation of catalyst C-5 the catalyst C-6 was produced with a degree of protonation D of D=1.7. The amount of the trifluoromethanesulfonic acid was employed according to the degree of protonation D=1.7.

D=1.7

[0162] Alternatively, the catalyst C-6 may also be produced directly in the presence of the starter (BH) in analogous fashion with or without dichloromethane.

Synthesis of Catalyst C-7 Employable According to the Invention

[0163] To synthesize catalyst C-7 32 mg of fumaric acid (0.280 mmol; 1 eq) were dissolved in 0.47 ml of a solution of tetrabutylammonium methoxide (0.280 mmol; 20% in methanol; 1 eq). The obtained mixture was then concentrated to dryness.

[0164] The obtained catalyst C-7 was used in further reactions without further purification.

D=1.0

Synthesis of Catalyst C-8 Employable According to the Invention

[0165] Analogously to the preparation of catalyst C-7 the catalyst C-8 was produced, 1,5-naphthalenedisulfonic acid being employed as the diprotic acid instead of fumaric acid. The degree of protonation of the resulting catalyst C-8 is D=1.0.

TABLE-US-00001 TABLE 1 Production of the organic, n-protic Bronsted acid (C) as catalyst Step Step organic, salt of the n-protic organic, Bronsted n-protic Catalyst acid base (EH) Bronsted acid Acid (E) D n C-1 1,5-Na2-NDS H2SO4 1.0 2 C-2 1,3-Na2-BDS H2SO4 1.0 2 C-3 1,5-Na2-NDS CF3SO3H 1.7 2 C-4 1,5-Na2-NDS CF3SO3H 1.3 2 C-5 2,6-Na2-NDS CF3SO3H 1.3 2 C-6 2,6-Na2-NDS CF3SO3H 1.7 2 C-7 Fumaric acid (n-Bu).sub.4N 1.0 2 (OMe) C-8 1,5-NDS (n-Bu).sub.4N 1.0 2 (OMe)

Activity Tests

Example 1: Reaction of Styrene Oxide with pFA in the Presence of Catalyst C-1

[0166] In an inertized Schlenk flask with a magnetic stirrer 12.0 g of finely powdered paraformaldehyde (pFA, M=450 g/mol; 27.500 mmol; 1.00 eq) were suspended in 25 ml of absolute 1,3-dioxolane. The batch was heated to 50 C. and 119 mg of the catalyst C-1 were added with stirring (0.275 mmol; 0.01 eq). Over a period of 72 hours 38 ml of styrene oxide (330.000 mmol; 12 eq) were added dropwise to form a stable white solution. The reaction was monitored by NMR. To this end the crude product was dissolved in dichloromethane, separated from undissolved constituents by filtration and concentrated under vacuum.

[0167] The conversion of styrene oxide was 100%.

[0168] The number-average molecular weight M.sub.n was 1300 g/mol. The molecular weight distribution determined by GPC was monomodal.

[0169] The polydispersity index was 1.99.

Example 2: Reaction of Styrene Oxide with pFA in the Presence of Catalyst C-1

[0170] In an inertized Schlenk flask with a magnetic stirrer 44.0 g of finely powdered pFA (M=450 g/mol; 110.000 mmol; 1.00 eq) were suspended in 25 ml of absolute 1,3-dioxolane. The batch was heated to 50 C. and 474 mg of the catalyst C-1 were added with stirring (1.100 mmol; 0.01 eq). Over a period of 48 hours 151 ml of styrene oxide (132.000 mmol; 12 eq) were added dropwise to form a stable white solution. The reaction was monitored by NMR. To this end the crude product was dissolved in dichloromethane, separated from undissolved constituents by filtration and concentrated under vacuum.

[0171] The conversion of styrene oxide was 100%.

[0172] The number-average molecular weight M.sub.n was 1758 g/mol.

[0173] The molecular weight distribution determined by GPC was monomodal.

[0174] The polydispersity index was 1.90.

Example 3: (Comparative Example) Reaction of Styrene Oxide with PEG in the Presence of Sodium Hydrogensulfate as Catalyst

[0175] In an inertized Schlenk flask with a magnetic stirrer 550 mg of PEG (M=1000 g/mol; 0.550 mmol; 1.00 eq) were heated to 50 C. and 1 mg of sodium hydrogensulfate (0.006 mmol; 0.01 eq) were added with stirring. Subsequently 0.52 ml of styrene oxide were added (4.400 mmol; 8.00 eq) and the reaction mixture was heated to 50 C. over three hours.

[0176] The reaction product was analyzed by NMR spectroscopy without further purification.

[0177] No conversion of the employed styrene oxide was observed.

Example 4: Reaction of Propylene Oxide with PEG in the Presence of Catalyst C-5

[0178] 7.5 mg of 2,6-naphthalenedisulfonic acid disodium salt (0.021 mmol, 0.015 eq) were mixed with 1375 mg of PEG (M=1000 g/mol; 1.375 mmol; 1.00 eq) in an oven-dried pressure-resistant reaction vial. 4 mg of trifluoromethanesulfonic acid (0.028 mmol, 0.02 eq) were added and the mixture was thoroughly commixed at 60 C. At room temperature 0.77 ml of propylene oxide (11.000 mmol, 8.0 eq) were added, the reaction vessel was sealed and the contents were stirred at a temperature of 60 C. over 1.5 hours.

[0179] Further analysis was performed without workup of the reaction mixture.

[0180] The conversion of propylene oxide was 100%.

[0181] M.sub.n of the product was 1343 g/mol.

Example 5: Reaction of Propylene Oxide with pFA in the Presence of Catalyst C-4

[0182] 7.5 mg of 1,5-naphthalenedisulfonic acid disodium salt (0.021 mmol; 0.015 eq) were mixed with 550 mg of finely powdered pFA (M=450 g/mol; 1.375 mmol; 1.00 eq) in an oven-dried pressure-resistant reaction vial. 4 mg of trifluoromethanesulfonic acid (0.028 mmol; 0.02 eq) were added and the mixture was thoroughly commixed. From a total amount of 0.77 ml of propylene oxide (11.000 mmol; 8.0 eq) 0.3 ml were added and the mixture was thoroughly stirred. The addition of propylene oxide was subsequently completed, the reaction vessel was sealed and the mixture was stirred at a temperature of 70 C. over six hours.

[0183] Further analysis was performed without workup of the reaction mixture.

[0184] The conversion of propylene oxide was 100%.

[0185] M.sub.n of the product was 730 g/mol.

Example 6: Reaction of Propylene Oxide with pFA in the Presence of Catalyst C-5

[0186] 7.5 mg of 2,6-naphthalenedisulfonic acid disodium salt (0.021 mmol; 0.015 eq) were mixed with 550 mg of finely powdered pFA (M=450 g/mol; 1.375 mmol; 1.00 eq) in an oven-dried pressure-resistant reaction vial. 4 mg of trifluoromethanesulfonic acid (0.028 mmol; 0.02 eq) were added and the mixture was thoroughly commixed. From a total amount of 0.77 ml of propylene oxide (11.000 mmol; 8.0 eq) 0.3 ml were added and the mixture was thoroughly stirred. The addition of propylene oxide was subsequently completed, the reaction vessel was sealed and the mixture was stirred at a temperature of 70 C. over six hours.

[0187] Further analysis was performed without workup of the reaction mixture.

[0188] The conversion of propylene oxide was 100%.

[0189] M.sub.n of the product was 738 g/mol.

Example 7: Reaction of Allyl Glycidyl Ether with PEG in the Presence of Catalyst C-6

[0190] Under inert gas 2.4 mg of the catalyst 6 (0.004 mmol; 0.8 mol %) were mixed with 500 mg of PEG (M=1000 g/mol; 0.500 mmol; 1.00 eq) in an oven-dried Schlenk tube. At room temperature 0.24 ml of allyl glycidyl ether (2.000 mmol; 4.0 eq) were added, the reaction vessel was sealed and the contents were stirred at a temperature of 60 C. over 8 hours.

[0191] Further analysis was performed without workup of the reaction mixture.

[0192] The conversion of allyl glycidyl ether was 82%.

[0193] The number-average molecular weight M.sub.n was 1634 g/mol.

[0194] The molecular weight distribution determined by GPC was monomodal in the polymeric range.

[0195] The polydispersity index was 1.8.

Example 8: Reaction of Ethylene Oxide with PET in the Presence of Catalyst C-5

[0196] 1.171 g (3.525 mmol) of 2.6-naphthalenedisulfonic acid disodium salt were suspended in absolute dichloromethane and admixed with 0.41 ml (4.700 mmol; 0.705 g) of trifluoromethanesulfonic acid. The suspension was stirred over 10 minutes and subsequently concentrated under vacuum. The obtained white solid was then mixed with 10 g of PET (0.023 mol). The thus obtained suspension was transferred into a 2 L high-pressure reactor together with 91.5 g of PET (0.212 mol). The contents were pressurized with nitrogen (1 bar) and subsequently evacuated in three cycles to remove residual air. At a nitrogen pressure of 45 bar the reactor was heated to 45 C. and stirred at 200 rpm. Ethylene oxide 142.9 g (0.94 mol; 8 eq) was added at a rate of 2 ml/min and the reaction temperature was increased at 10 C./15 min until an internal temperature of 105 C. had been achieved (the exothermic reaction was observed above 90 C.). After cooling to 60 C. the ethylene oxide concentration in the gas phase was determined (below 5 ppm) and the reactor was decompressed.

[0197] The conversion of ethylene oxide was 100%. The proportion of secondary components was determined as 0.6% by weight.

[0198] The number-average molecular weight M.sub.n was 740 g/mol.

[0199] The molecular weight distribution determined by GPC was monomodal in the entire range.

[0200] The polydispersity index was 1.2.

Example 9: Reaction of Ethylene Oxide with pFA in the Presence of Catalyst C-5

[0201] 1.220 g (3.673 mmol) of 2,6-naphthalenedisulfonic acid disodium salt were suspended in absolute dichloromethane and admixed with 0.72 g (4.797 mmol) of trifluoromethanesulfonic acid. The suspension was stirred over 10 minutes and subsequently concentrated under vacuum. The obtained white solid was then mixed with 108 g of cPC. The thus obtained suspension was transferred. 105.8 g of pFA (M=450 g/mol, 0.235 mol) were then added. The contents were pressurized with nitrogen (1 bar) and subsequently evacuated in three cycles to remove residual air. At a nitrogen pressure of 45 bar the reactor was heated to 60 C. and stirred at 200 rpm. Ethylene oxide 142.8 g (0.94 mol, 8 eq) was added at a rate of 2 ml/min and the reaction temperature was increased at 10 C./15 min until an internal temperature of 105 C. had been achieved (the exothermic reaction was observed above 90 C.). After cooling to 60 C. the ethylene oxide concentration in the gas phase was determined (below 5 ppm) and the reactor was decompressed.

[0202] The conversion of ethylene oxide was 100%. The proportion of secondary components was determined as 8.6% by weight.

[0203] The number-average molecular weight M.sub.n was 1409 g/mol.

[0204] The molecular weight distribution determined by GPC was monomodal in the entire range.

[0205] The polydispersity index was 1.9.

Example 10: Reaction of 1,3-Dioxolane with pFA in the Presence of Catalyst C-2

[0206] 12 g of finely powdered pFA (0.030 mol; 1.0 eq) were suspended in 12 ml of absolute 1,3-dioxolane under inert conditions. The mixture was heated to 65 C. and the catalyst 2 (342 mg; 0.009 mol; 0.03 eq) was added. The reaction mixture was stirred over 7.5 hours. The product mixture was mixed in 40 ml of dichloromethane, separated from undissolved constituents by filtration and concentrated under vacuum.

[0207] Final weight: 10.2 g

[0208] The number-average molecular weight M.sub.n was 1953 g/mol.

[0209] The molecular weight distribution determined by GPC was monomodal.

[0210] The polydispersity index was 1.8.

Example 11: Reaction of Propylene Oxide with PC in the Presence of Catalyst C-5

[0211] 7.5 mg of 2,6-naphthalenedisulfonic acid disodium salt (0.021 mmol; 0.015 eq) were mixed with 4 mg of trifluoromethanesulfonic acid (0.028 mmol; 0.02 eq) in an oven-dried pressure-resistant reaction vial. 1375 mg of PC (M=1000 g/mol; 1.375 mmol; 1.00 eq) dissolved in 0.77 ml of propylene oxide (11.000 mmol, 8.0 eq) were added and thoroughly stirred. The reaction vessel was sealed and the mixture was stirred at a temperature of 75 C. over five hours.

[0212] Further analysis was performed without workup of the reaction mixture.

[0213] Complete conversion of the employed propylene oxide with negligible formation of cyclic propylene carbonate was observed. Formation of new cyclic propylene carbonate was determined by proton resonance spectroscopy and amounted to 2.7% of the alternating polycarbonate groups.

[0214] The number-average molecular weight M.sub.n was 1381 g/mol.

[0215] The molecular weight distribution determined by GPC was monomodal.

[0216] The polydispersity index was 1.3.

Example 12: (Comparative Example) Reaction of Propylene Oxide with PC in the Presence of 1,8-diazabicyclo[5.4.0]Undec-7-Ene (DBU) as Catalyst

[0217] 3 mg of 1,8-diazabicyclo[5.4.0]undec-7-ene (0.015 mmol; 0.015 eq) were initially charged in an oven-dried pressure-resistant reaction vial. 1375 mg of PC (M=1000 g/mol; 1.375 mmol; 1.00 eq) dissolved in 0.77 ml of propylene oxide (11.000 mmol, 8.0 eq) were added and thoroughly stirred. The reaction vessel was sealed and the mixture was stirred at a temperature of 75 C. over five hours.

[0218] The reaction product was analyzed by NMR spectroscopy without further purification.

[0219] Complete degradation of the polymer to cyclic propylene carbonate was observed. No conversion of employed propylene oxide into polymeric structures was observed.

Example 13: Reaction of Styrene Oxide with PEG in the Presence of Catalyst C-7

[0220] 10 mg of catalystr C-7 tetrabutylammonium hydrogenfumarate (0.028 mmol; 0.100 eq) were mixed with 275 mg of PEG (M=1000 g/mol; 0.275 mmol; 1.000 eq). The mixture was heated to 70 C. and 0.13 ml of styrene oxide (1.100 mmol, 4.0 eq) were added. The batch was stirred at 70 C. over 10 hours.

[0221] The reaction product was analyzed by NMR spectroscopy without further purification.

[0222] The conversion of employed styrene oxide was 28%.

[0223] An M.sub.n of 1135 g/mol was calculated from the NMR analysis.

Example 14 (Comparative Example): Reaction of Propylene Oxide with PEG in the Presence of Trifluoromethanesulfonic Acid as Catalyst

[0224] Initially charged in an oven-dried pressure-resistant reaction vial were 1375 mg of PEG (M=1000 g/mol; 1.375 mmol; 1.00 eq). 4 mg of trifluoromethanesulfonic acid (CF.sub.3SO.sub.3H, 0.028 mmol, 0.02 eq) were added and the mixture was thoroughly commixed at 60 C. At room temperature 0.77 ml of propylene oxide (11.000 mmol, 8.0 eq) were added, the reaction vessel was sealed and the contents were stirred at a temperature of 60 C. over 1.5 hours.

[0225] Further analysis was performed without workup of the reaction mixture.

[0226] The conversion of propylene oxide was 100%.

[0227] The molecular weight distribution determined by GPC was multimodal in the polymeric range and exhibited a high proportion of low molecular weight compounds. M.sub.n was 1292 g/mol.

Example 15 (Comparative Example): Reaction of Propylene Oxide with PC in the Presence of Trifluoromethanesulfonic Acid as Catalyst

[0228] Initially charged in an oven-dried pressure-resistant reaction vial were 4 mg of trifluoromethanesulfonic acid (0.028 mmol; 0.02 eq). 1375 mg of PC (M=1000 g/mol; 1.375 mmol; 1.00 eq) dissolved in 0.77 ml of propylene oxide (11.000 mmol, 8.0 eq) were added and thoroughly stirred. The reaction vessel was sealed and the mixture was stirred at a temperature of 75 C. over five hours.

[0229] Further analysis was performed without workup of the reaction mixture.

[0230] Complete conversion of the employed propylene oxide with severe formation of cyclic propylene carbonate was observed. Formation of new cyclic propylene carbonate was determined by NMR and amounted to 39% of the alternating polyethercarbonate groups.

[0231] The number-average molecular weight M.sub.n was 808 g/mol.

[0232] The molecular weight distribution determined by GPC exhibited high proportions of low molecular weight compounds.

[0233] The polydispersity index was 1.6.

Example 16 (Comparative Example): Reaction of Propylene Oxide with pFA in the Presence of Trifluoromethanesulfonic Acid as Catalyst

[0234] Initially charged in an oven-dried pressure-resistant reaction vial were 550 mg of finely powdered pFA (M=450 g/mol; 1.375 mmol; 1.00 eq). 4 mg of trifluoromethanesulfonic acid (0.028 mmol; 0.02 eq) were added and the mixture was thoroughly commixed. From a total amount of 0.77 ml of propylene oxide (11.000 mmol; 8.0 eq) 0.3 ml were added and the mixture was thoroughly stirred. The addition of propylene oxide was subsequently completed, the reaction vessel was sealed and the mixture was stirred at a temperature of 70 C. over six hours.

[0235] Further analysis was performed without workup of the reaction mixture.

[0236] The conversion of propylene oxide was 100%.

[0237] The molecular weight distribution determined by GPC was multimodal in the polymeric range and M.sub.n was 476 g/mol.

Example 17 (Comparative Example): Reaction of Propylene Oxide with PEG in the Presence of 2,6-Naphthalenedisulfonic Acid Disodium Salt as Catalyst

[0238] 7.5 mg of 2,6-naphthalenedisulfonic acid disodium salt (0.021 mmol, 0.015 eq) were mixed with 1375 mg of PEG (M=1000 g/mol; 1.375 mmol; 1.00 eq) in an oven-dried pressure-resistant reaction vial and the mixture was thoroughly commixed at 60 C. At room temperature 0.77 ml of propylene oxide (11.000 mmol, 8.0 eq) were added, the reaction vessel was sealed and the contents were stirred at a temperature of 60 C. over 1.5 hours.

[0239] Further analysis was performed without workup of the reaction mixture.

[0240] The conversion of propylene oxide was 0%.

Example 18 (Comparative Example): Reaction of Propylene Oxide with PEG in the Presence of 1,5-Naphthalenedisulfonic Acid Disodium Salt as Catalyst

[0241] 7.5 mg of 1,5-naphthalenedisulfonic acid disodium salt (0.021 mmol, 0.015 eq) were mixed with 1375 mg of PEG (M=1000 g/mol; 1.375 mmol; 1.00 eq) in an oven-dried pressure-resistant reaction vial and the mixture was thoroughly commixed at 60 C. At room temperature 0.77 ml of propylene oxide (11.000 mmol, 8.0 eq) were added, the reaction vessel was sealed and the contents were stirred at a temperature of 60 C. over 1.5 hours.

[0242] Further analysis was performed without workup of the reaction mixture.

[0243] The conversion of propylene oxide was 0%.

Example 19 Reaction of Styrene Oxide with PEG in the Presence of Catalyst C-8

[0244] In an inertized Schlenk flask with a magnetic stirrer 1375 mg of PEG (M=1000 g/mol; 1.375 mmol; 1.00 eq) were heated to 50 C. and 12 mg of catalyst 8 (0.020 mmol; 0.01 eq) were added with stirring. Subsequently 1.25 ml of styrene oxide were added (11.000 mmol; 8.00 eq) and the reaction mixture was heated to 50 C. over two hours.

[0245] The reaction product was analyzed by NMR spectroscopy without further purification.

[0246] Complete conversion of the employed styrene oxide was observed by NMR.

[0247] Mn of the product was 2209 g/mol.

Example 20 (Comparative Example): Reaction of Propylene Oxide with PEG in the Presence of Sulfuric Acid as Catalyst

[0248] Initially charged in an oven-dried pressure-resistant reaction vial were 3 mg of sulfuric acid, 98% (0.028 mmol; 0.02 eq). 1375 mg of PEG (M=1000 g/mol; 1.375 mmol; 1.00 eq) were added and at room temperature 0.77 ml of propylene oxide (11.000 mmol, 8.0 eq) were added, the reaction vessel was sealed and the contents were stirred at a temperature of 60 C. over 1.5 hours.

[0249] Further analysis was performed without workup of the reaction mixture.

[0250] The conversion of propylene oxide was 8%.

Example 21 (Comparative Example): Reaction of Propylene Oxide with PEG in the Presence of Sodium Hydrogensulfate as Catalyst

[0251] Initially charged in an oven-dried pressure-resistant reaction vial were 4 mg of sodium hydrogensulfate (NaHSO.sub.4, 0.028 mmol; 0.02 eq). 1375 mg of PEG (M=1000 g/mol; 1.375 mmol; 1.00 eq) were added and at room temperature 0.77 ml of propylene oxide (11.000 mmol, 8.0 eq) were added, the reaction vessel was sealed and the contents were stirred at a temperature of 60 C. over 1.5 hours.

[0252] Further analysis was performed without workup of the reaction mixture.

[0253] The conversion of propylene oxide was 0%.

Example 22 (Comparative Example): Reaction of Propylene Oxide with PEG in the Presence of Sodium Triflate as Catalyst

[0254] Initially charged in an oven-dried pressure-resistant reaction vial were 5 mg of sodium triflate (NaOTf, 0.028 mmol; 0.02 eq). 1375 mg of PEG (M=1000 g/mol; 1.375 mmol; 1.00 eq) were added and at room temperature 0.77 ml of propylene oxide (11.000 mmol, 8.0 eq) were added, the reaction vessel was sealed and the contents were stirred at a temperature of 60 C. over 1.5 hours.

[0255] Further analysis was performed without workup of the reaction mixture.

[0256] The conversion of propylene oxide was 0%.

Example 23 (Comparative Example): Reaction of Propylene Oxide with PEG in the Presence of Sodium Hydrogensulfate-Sodium Triflate Mixture as Catalyst

[0257] Initially charged in an oven-dried pressure-resistant reaction vial were 4 mg of sodium hydrogensulfate and 5 mg of sodium triflate (0.028 mmol; 0.02 eq). 1375 mg of PEG (M=1000 g/mol; 1.375 mmol; 1.00 eq) were added and at room temperature 0.77 ml of propylene oxide (11.000 mmol, 8.0 eq) were added, the reaction vessel was sealed and the contents were stirred at a temperature of 60 C. over 1.5 hours.

[0258] Further analysis was performed without workup of the reaction mixture.

[0259] The conversion of propylene oxide was 0%.

Example 24: Reaction of Propylene Oxide with PC in the Presence of Catalyst C-5

[0260] 150 mg of 2,6-naphthalenedisulfonic acid disodium salt (0.450 mmol; 0.015 eq) were suspended with 2 ml of absolute dichloromethane in an oven-dried glass flask. 90 mg of trifluoromethanesulfonic acid (0.600 mmol, 0.020 eq) were added with stirring. After stirring for thirty minutes the solvent was removed under vacuum. In a stainless steel reactor with a Teflon lining 30.000 g of PC (M=1000 g/mol, 30.000 mmol, 1.00 eq) of the PC were dissolved in 25 ml of absolute tetrahydrofuran. Subsequently the freshly produced catalyst was added and the reactor was sealed. At room temperature 7.000 g of propylene oxide (120.000 mmol, 4.00 eq) were added and heated to 75 C. with stirring. After a reaction time of two hours a further 7.000 g of propylene oxide were added, so that a total amount of 14.000 g (240.000 mmol, 8.00 eq) was added. After a total reaction time of 5 hours and 30 minutes the mixture was cooled to room temperature and the contents of the reactor were removed.

[0261] 58.0 g of a clear liquid were obtained and analyzed without further purification.

[0262] The conversion of propylene oxide was 100%.

[0263] The content of cyclic propylene carbonate determined based on proton resonance spectroscopy was 1.2% by weight based on employed polyether carbonate (the starting material used already contains 3.0% by weight of cyclic propylene carbonate). The proportion of cyclic ethers formed amounted to 8.2% by weight (based on the reaction mixture).

[0264] The number-average molecular weight M.sub.n was 1633 g/mol.

[0265] The polydispersity index was 1.3.

Example 25 (Comparative Example): Reaction of Propylene Oxide with PC in the Presence of Trifluoromethanesulfonic Acid as Catalyst

[0266] In a stainless steel reactor with a Teflon lining 30.000 g of PC (M=1000 g/mol, 30.000 mmol, 1.00 eq) were dissolved in 25 ml of absolute tetrahydrofuran. Subsequently 150 mg of trifluoromethanesulfonic acid (0.600 mmol, 0.02 eq) were added and the reactor was sealed. At room temperature 7.000 g of propylene oxide (120.000 mmol, 4.00 eq) were added and heated to 75 C. with stirring. After a reaction time of two hours a further 7.000 g of propylene oxide were added, so that a total amount of 14.000 g (240.000 mmol, 8.00 eq) was added. After a total reaction time of 5 hours and 30 minutes the mixture was cooled to room temperature and the contents of the reactor were removed.

[0267] The conversion of propylene oxide was 100%.

[0268] The formation of cyclic propylene carbonate determined based on proton resonance spectroscopy was 22.3% by weight based on employed polycarbonate polyol (the starting material used already contains 3.0% by weight of cyclic propylene carbonate). The proportion of cyclic ethers formed amounted to 13.1% by weight (based on the reaction mixture).

[0269] The number-average molecular weight M.sub.n was 1340 g/mol.

[0270] The polydispersity index was 1.4.

Example 26: Reaction of Maleic Anhydride with Propylene Oxide and PET in the Presence of Catalyst C-5

[0271] 300 mg of 2,6-naphthalenedisulfonic acid disodium salt (0.900 mmol; 0.015 eq) were suspended with 8 ml of absolute dichloromethane in an oven-dried glass flask. 180 mg of trifluoromethanesulfonic acid (1.200 mmol, 0.020 eq) were added with stirring. After stirring for thirty minutes the solvent was removed under vacuum. In a stainless steel reactor with a Teflon lining 26.000 g (60.000 mmol, 1.00 eq) of the PET polyol having a molecular weight of 432 g/mol were mixed with 11.769 g of maleic anhydride (120.000 mmol; 2.0 eq). Subsequently the freshly produced catalyst was added and the reactor was sealed. At a temperature of 80 C. a portionwise addition of altogether 28.000 g of propylene oxide (480.000 mmol, 8.00 eq) was performed over 3 hours. Once addition was complete the temperature was increased to 100 C. and the mixture was stirred for a further two hours. Subsequently the mixture was cooled to room temperature and the contents of the reactor were removed. The yellowish liquid was mixed with 40 ml of dichloromethane, filtered via a filter paper to remove undissolved maleic anhydride and subsequently concentrated under vacuum. 48.2 g of a clear light-yellow liquid were obtained (73%).

[0272] The conversion of propylene oxide determined based on proton resonance spectroscopy of the unfiltered crude product was 100%. The conversion of employed maleic anhydride was 94%.

[0273] The connectivity between incorporated maleic acid equivalents and polyether was demonstrated by 1H-13C-correlated magnetic resonance spectroscopy of the purified product.

[0274] The molecular weight MPeak was 1107 g/mol.

[0275] The polydispersity index was 1.3.

Example 27: Reaction of -Caprolactone (A-2) with Propylene Oxide (A-1) and PET in the Presence of Catalyst C-5

[0276] 300 mg of 2,6-naphthalenedisulfonic acid disodium salt (0.900 mmol; 0.015 eq) were suspended with 8 ml of absolute dichloromethane in an oven-dried glass flask. 180 mg of trifluoromethanesulfonic acid (1.200 mmol, 0.020 eq) were added with stirring. After stirring for thirty minutes the solvent was removed under vacuum. In a stainless steel reactor with a Teflon lining 26.000 g (60.000 mmol, 1.00 eq) of the PET polyol having a molecular weight of 432 g/mol were mixed with 13.697 g of -caprolactone (120.000 mmol; 2.0 eq). Subsequently the freshly produced catalyst was added and the reactor was sealed. At a temperature of 80 C. a portionwise addition of altogether 28.000 g of propylene oxide (480.000 mmol, 8.00 eq) was performed. After stirring for three hours at 80 C. and stirring for one hour at 100 C. the reaction was terminated. After cooling to room temperature the contents of the reactor were removed (66.4 g; 98%).

[0277] The conversion of propylene oxide determined based on proton resonance spectroscopy of the crude product was 100%. The conversion of employed -caprolactone was likewise 100%.

[0278] The molecular weight MPeak was 1349 g/mol.

[0279] The polydispersity index was 1.5.

Example 28: Reaction of Butyrolactone (A-2) with Propylene Oxide (A-1) and PET in the Presence of Catalyst C-5

[0280] 300 mg of 2,6-naphthalenedisulfonic acid disodium salt (0.900 mmol; 0.015 eq) were suspended with 8 ml of absolute dichloromethane in an oven-dried glass flask. 180 mg of trifluoromethanesulfonic acid (1.200 mmol, 0.020 eq) were added with stirring. After stirring for thirty minutes the solvent was removed under vacuum. In a stainless steel reactor with a Teflon lining 26.000 g (60.000 mmol, 1.00 eq) of the PET polyol having a molecular weight of 432 g/mol were mixed with 10.330 g of butyrolactone (120.000 mmol; 2.0 eq). Subsequently the freshly produced catalyst was added and the reactor was sealed. At a temperature of 80 C. a portionwise addition of altogether 28.000 g of propylene oxide (480.000 mmol, 8.00 eq) was performed. After stirring for three hours the reaction was terminated, cooled to room temperature and the contents of the reactor were removed. The yellowish liquid was mixed with 40 ml of dichloromethane, filtered via a filter paper and subsequently concentrated under vacuum. 54.5 g of a clear light-yellow liquid were obtained (84.0%).

[0281] The conversion of propylene oxide determined based on proton resonance spectroscopy of the unfiltered crude product was 100%. The conversion of employed butyrolactone was 77%.

[0282] The molecular weight MPeak was 1295 g/mol.

[0283] The polydispersity index was 1.3.

Example 29: Reaction of Tetrahydrofuran (A-7) with Propylene Oxide (A-1) and PET in the Presence of Catalyst C-5

[0284] 300 mg of 2,6-naphthalenedisulfonic acid disodium salt (0.900 mmol; 0.015 eq) were suspended with 8 ml of absolute dichloromethane in an oven-dried glass flask. 180 mg of trifluoromethanesulfonic acid (1.200 mmol, 0.020 eq) were added with stirring. After stirring for thirty minutes the solvent was removed under vacuum. In a stainless steel reactor with a Teflon lining 26.000 g (60.000 mmol, 1.00 eq) of the PET polyol having a molecular weight of 432 g/mol were mixed with 8.654 g of tetrahydrofuran (120.000 mmol; 2.0 eq). Subsequently the freshly produced catalyst was added and the reactor was sealed. At a temperature of 100 C. a portionwise addition of altogether 28.000 g of propylene oxide (480.000 mmol, 8.00 eq) was performed. After stirring for four and a half hours the reaction was terminated, cooled to room temperature and the contents of the reactor were removed. The yellowish liquid was mixed with 40 ml of dichloromethane, filtered via a filter paper and subsequently concentrated under vacuum. 48.3 g of a clear light-yellow liquid were obtained (77%).

[0285] The conversion of propylene oxide determined based on proton resonance spectroscopy of the unfiltered crude product was 100%. The conversion of employed tetrahydrofuran was 64%.

[0286] The connectivity between incorporated 1,4-dihydroxybutane equivalents and polyether was demonstrated by 1H-13C-correlated magnetic resonance spectroscopy of the purified product.

[0287] The molecular weight MPeak was 1132 g/mol.

[0288] The polydispersity index was 1.4.

Example 30: Reaction of 1,3-Dioxolane (A-4) with Propylene Oxide (A-1) and Paraformaldehyde (pFA) in the Presence of Catalyst C-5

[0289] 187 mg of 2,6-naphthalenedisulfonic acid disodium salt (0.563 mmol; 0.027 eq) were suspended with 0.5 ml of absolute dichloromethane in an oven-dried glass flask. 113 mg of trifluoromethanesulfonic acid were added with stirring. After five minutes of stirring the solvent was removed under vacuum and the pulverulent white solid was mixed with 15.000 g of finely powdered paraformaldehyde pFA (M=450 g/mol; 33.333 mmol; 1.00 eq). The obtained powder was added to a stainless steel reactor with a Teflon lining and therein suspended with 34 ml of absolute 1,3-dioxolane. Subsequently the reactor was sealed and with stirring heated to 60 C. and propylene oxide was added in 5 ml portions. Once 10 ml had been added over a period of 30 minutes the internal temperature of the reactor was increased to 70 C. The addition of propylene oxide was continued up to a total amount of 20 ml (300.000 mmol; 9.0 eq) and the mixture was stirred for a further 18 hours at 70 C.

[0290] Complete conversion of the employed propylene oxide was determined by proton magnetic resonance spectroscopy of the crude product mixture.

[0291] The obtained solution was mixed with 30 ml of dichloromethane, filtered and concentrated under vacuum. 42.3 g of a yellowish liquid were obtained.

[0292] The conversion of propylene oxide was 100%, the yield (including 1,3-dioxolane as comonomer) was 62%.

[0293] The content of formaldehyde determined based on proton resonance spectroscopy was 42% by weight.

[0294] The number-average molecular weight Mn was 1652 g/mol.

[0295] The polydispersity index was 1.5.

Example 31 (Comparative Example): Reaction of Propylene Oxide with PEG in the Presence of Perfluorosulfonic Acid Membrane (Nation N117)

[0296] 31 mg of perfluorosulfonic acid membrane of the type Nafion N117 comprising an equivalent amount of 0.91-1.11 mmol of sulfonyl groups per gram (0.028 mmol, 0.020 eq) were initially charged in an oven-dried pressure-resistant reaction vial with 1375 mg of PEG (M=1000 g/mol; 1.375 mmol; 1.00 eq). At room temperature 0.77 ml of propylene oxide (11.000 mmol, 8.0 eq) were added, the reaction vessel was sealed and the contents were stirred at a temperature of 60 C. over 1.5 hours.

[0297] Further analysis was performed without workup of the reaction mixture.

[0298] The conversion of propylene oxide was 16%.

TABLE-US-00002 TABLE 2 Test for activity of inventive and comparative catalyst systems with propylene oxide (A-1), PEG (BH), a reaction temperature of T = 60 C., a reaction time of t = 1.5 h, a molar ratio n(A-1)/n(BH) = 8. X (A-1) M.sub.n # Catalyst Organic n D [%] [g/mol] 21 comp. NaHSO4 no 2 1.0 0 22 comp. NaOTf yes 1 0 0 23 comp. NaHSO4/ yes 3 1.0 0 NaOTf 14 comp. CF3SO3H yes 1 1.0 100 .sup.1292.sup.a 18 comp. 1,5-Na2NDS yes 2 0 0 17 comp. 2,6-Na2NDS yes 2 0 0 4 C-5 yes 2 1.3 100 1343 20 comp. H2SO4 no 2 2.0 8 31 comp. Nafion yes 16 N117 .sup.amultimodal molecular weight distribution.

TABLE-US-00003 TABLE 3 Test for activity of inventive and comparative catalyst systems with styrene oxide (A-1), PEG (BH), a reaction temperature of T = 50 C., a reaction time of t = 2 h, a molar ratio (A-1)/n(BH) = 8. X (A-1) M.sub.n # Catalyst Organic n D [%] [g/mol] 19 C-8 yes 2 1.0 100 2209 3 comp. NaHSO.sub.4 no 2 1.0 0

TABLE-US-00004 TABLE 4 Test for activity of inventive catalyst system C-6 with AGE (A-1), PEG (BH), a reaction temperature of T = 60 C., a reaction time of t = 2 h, a molar ratio (A-1)/n(BH) = 4. X (A-1) M.sub.n # Catalyst Organic n D [%] [g/mol] 7 C-6 yes 2 1.7 82 1634

TABLE-US-00005 TABLE 5 Test for activity of inventive and comparative catalyst systems with propylene oxide (A-1), pFA (BH), a reaction temperature of T = 70 C., a reaction time of t = 6 h, a molar ratio (A-1)/n(BH) = 8. X (A-1) M.sub.n # Catalyst Organic n D [%] [g/mol] 5 C-4 yes 2 1.3 100 730 6 C-5 yes 2 1.3 100 738 16 comp. CF3SO3H yes 1 1.0 100 .sup.476.sup.a .sup.aMultimodal molecular weight distribution.

TABLE-US-00006 TABLE 6 Test for activity of inventive catalyst systems with styrene oxide (A-1), pFA (BH), a reaction temperature of T = 50 C., a molar ratio (A-1)/n(BH) = 12. X (A-1) M.sub.n # Catalyst Organic n D [%] [g/mol] 1 C-1 yes 2 1.0 100 1300 2 C-1 yes 2 1.0 100 1758

TABLE-US-00007 TABLE 7 Test for activity of the inventive catalyst system with 1,3-dioxolane (A-4), pFA (BH), a reaction temperature of T = 65 C., a molar ratio (A-4)/(BH) = 5.7. X (A-4) M.sub.n # Catalyst Organic n D [%] [g/mol] 10 C-2 yes 2 1.0 37* 1953 *1,3-dioxolane also solvent

TABLE-US-00008 TABLE 8 Test for activity and selectivity of inventive and comparative catalyst systems with propylene oxide (A-1), PC (BH), a reaction temperature of T = 75 C., a reaction time of t = 5 h, a molar ratio (A-1)/n(BH) = 8. cPC.sup.a) X (A-1) M.sub.n [% by # Catalyst Organic n D [%] [g/mol] weight] 11 C-5 yes 2 1.3 100 1381 2.7 15 comp. CF.sub.3SO.sub.3H yes 1 1.0 100 808 39.0 .sup.a)Formation of new cyclic propylene carbonate cPC, based on employed polycarbonate polyol PC, less 3% by weight of cPC from starter material.

TABLE-US-00009 TABLE 9 Test for activity of inventive catalyst system C-7 with styrene oxide (A-1), PEG (BH), a reaction temperature of T = 70 C., a molar ratio (A-1)/(BH) = 4. X (A-1) M.sub.n # Catalyst Organic n D [%] [g/mol] 13 C-7 yes 2 1.0 28 1135

TABLE-US-00010 TABLE 10 Copolymerization of propylene oxide (A-1) with comonomers (A-2, A-4, A-6 or A-7) in the presence of catalyst (C-5) at temperatures of 80-100 C. T M # Comonomers Catalyst Organic n D [ C.] [g/mol] 26 A-1, A-6 C-5 yes 2 1.3 80-100 1107 (M.sub.P) 27 A-1, A-2 C-5 yes 2 1.3 80 1349 (M.sub.P) 28 A-1, A-2 C-5 yes 2 1.3 80 1295 (M.sub.P) 29 A-1, A-7 C-5 yes 2 1.3 100 1132 (M.sub.P) 30 A-1, A-4 C-5 yes 2 1.3 60-70 1652 (M.sub.n)

TABLE-US-00011 TABLE 11 Test for activity and selectivity of inventive and comparative catalyst systems with alkylene oxide (A-1), H-functional starter compounds (BH) with molar ratio (A-1)/n(BH) = 8. Secondary X (A-1) Mn components # (A-1) (BH) Catalyst Solvent [%] [g/mol] PDI [% by weight] 11 PO PC C-5 100 1381 1.3 2.7.sup.a)/.sup.b) 15 comp. PO PC CF3SO3H 100 808 1.6 39.0.sup.a)/.sup.b) 24 PO PC C-5 THF 100 1633 1.3 1.2.sup.a)/8.2.sup.b) 25 comp. PO PC CF3SO3H THF 100 1340 1.4 22.3.sup.a)/13.1.sup.b) 8 EO PET C-5 100 740 1.2 .sup.0.sup.a)/0.6.sup.b) 9 EO pFA C-5 cPC 100 1409 1.9 .sup.0.sup.a)/8.6.sup.b) .sup.a)Formation of cyclic propylene carbonate (cPC), based on employed polycarbonate polyol, less 3% by weight of cPC from starter material. .sup.b)The proportion of secondary components without cPC based on the reaction mixture in % by weight.