METHOD FOR PRODUCING A POLYESTER-POLYETHER POLYOL BLOCK COPOLYMER

Abstract

The present invention relates to a process for preparing a polyester-polyether polyol block copolymer by reaction of an H-functional starter substance with lactone in the presence of a catalyst to afford a polyester followed by reaction of the polyester from step i) with alkylene oxides in the presence of a catalyst (B), wherein the lactone is a 4-membered lactone. The invention further relates to the polyester-polyether polyol block copolymer obtainable by the present process.

Claims

1. A process for producing a polyester-polyether polyol block copolymer, comprising: i) reacting an H-functional starter substance with lactone to afford a polyester; and ii) reacting the polyester from step i) with an alkylene oxide in the presence of a catalyst (B); wherein the lactone comprises a 4-membered lactone.

2. The process as claimed in claim 1, wherein step i) is performed in the presence of a catalyst (A).

3. The process as claimed in claim 2, wherein the catalyst (A) comprises an amine (A), a double metal cyanide (DMC) catalyst (A) or a Brønsted-acidic catalyst (A).

4. The process as claimed in claim 3, wherein the catalyst (A) comprises a double metal cyanide (DMC) catalyst (A) and the double metal cyanide (DMC) catalyst (A) comprises an organic complex ligand, wherein the organic complex ligand is one or more compounds and comprises tert-butanol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, ethylene glycol mono-tert-butyl ether and 3-methyl-3-oxetanemethanol, or a mixture thereof.

5. The process as claimed in claim 1, wherein the H-functional starter substance comprises an H-functional starter compound having one or more free carboxyl groups and/or functional starter compound having one or more free hydroxyl groups.

6. The process as claimed in claim 5, wherein the H-functional starter substance comprises an H-functional starter compound having one or more free carboxyl groups a monobasic carboxylic acid, a polybasic carboxylic acid, a carboxyl-terminated polyester, a carboxyl-terminated polycarbonate, a carboxyl-terminated polyether carbonate, a carboxyl-terminated polyether ester carbonate polyol, a carboxyl-terminated polyether, or a mixture thereof.

7. The process as claimed in claim 6, wherein the H-functional starter compound having one or more free carboxyl groups comprises methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, lactic acid, fluoroacetic acid, chloroacetic acid, bromoacetic acid, iodoacetic acid, difluoroacetic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, oleic acid, salicylic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, citric acid, trimesic acid, fumaric acid, maleic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and trimellitic acid, acrylic acid, methacrylic acid, or a mixture thereof.

8. The process as claimed in claim 1, wherein the 4-membered lactone comprises propiolactone, β-butyrolactone, β-isovalerolactone, β-caprolactone, β-isocaprolactone, β-methyl-β-valerolactone, diketene, preferably propiolactone, β-butyrolactone, or a mixture thereof.

9. The process as claimed in any of claim 1, wherein the catalyst (B) comprises a tertiary amine (B), a double metal cyanide (DMC) catalyst (B) or a Brønsted-acidic catalyst (B).

10. The process as claimed in claim 1, wherein the alkylene oxide comprises ethylene oxide and/or propylene oxide.

11. The process as claimed in claim 3, wherein the double metal cyanide (DMC) catalyst (A) is identical to the double metal cyanide (DMC) catalyst (B) and is added in step i).

12. The process as claimed in claim 1, wherein the process is performed without addition of a solvent.

13. A polyester obtained by the process as claimed in claim 1.

14. A polyester-polyether polyol block copolymer obtained by the process as claimed in claim 1.

15. A polyurethane polymer obtained by reaction of a polyisocyanate with the polyester-polyether polyol block copolymer as claimed in claim 14.

Description

EXAMPLES

[0194] The present invention is elucidated in detail by the figures and examples which follow, but without being limited thereto.

[0195] Starting Materials Used

[0196] Cyclic Lactones

[0197] β-Propiolactone (purity 98.5%, Ferak Berlin GmbH)

[0198] Epoxides

[0199] Propylene oxide (99.5%, Sigma Aldrich)

[0200] H-Functional Starter Substance PPG-1000 (propylene oxide-based polyether having an average molecular weight of 1000 g/mol) Adipic acid (Sigma-Aldrich, BioXtra, 99.5% (HPLC)) 15

[0201] Catalysts

[0202] All examples employed a DMC catalyst produced according to example 6 in WO 01/80994 A1.

[0203] Solvent

[0204] THF (Fisher Scientific GPC Grade)

[0205] Description of the Methods:

[0206] .sup.1H NMR

[0207] The conversion of the monomer was determined by .sup.1H NMR (Bruker DPX 400, 400 MHz; pulse program zg30, relaxation time D 1: 10 s, 64 scans). Each sample was dissolved in deuterated chloroform. The relevant resonances in the .sup.1H NMR (relative to TMS=0 ppm) and the assignment of the area integrals (A) are as follows: [0208] poly(hydroxypropionate) (=polypropiolactone) with resonances at 4.38 (2H) and 2.66 (2H) [0209] β-propiolactone with resonances at 4.28 (2H) and 3.54 (2H) [0210] poly(propylene oxide) with resonances at 3.60-3.20 (3H) and 1.12 (3H) [0211] propylene oxide with resonances at 2.98 (1H), 2.75 (1H), 2.43 (1H) and 1.32 (3H)

[0212] The conversion of the respective monomer is determined as an integral of a suitable polymer signal divided by the sum of a suitable polymer signal and monomer signal. All signals are referenced to 1H.

[0213] Thermogravimetric Analysis

[0214] The samples were analyzed according to DIN EN ISO/IEC 17025 using a TGA/SDTA851e instrument from Mettler-Toledo GmbH. Measurement was carried out between 30° C. to 600° C. at a heating rate of 10° C./min in air (50.0 mL/min).

Example 1: Preparation of a Polyester-Polyether Polyol Block Copolymer (Having a PET-PES-PET Block Copolymer Structure) by Block Copolymerization of Propiolactone and Propylene Oxide Via DMC Catalysis

[0215] THF (50.0 g), DMC catalyst (3000 ppm based on the total mass of starter and β-lactone) and adipic acid (1.46 g, 10.0 mmol, 1.00 eq.) are initially charged into a 300 mL steel reactor. The reactor is purged with N.sub.2. β-Propiolactone (18.5 g, 257 mmol, 25.7 eq.) is then continuously fed into the reactor over 120 min at 130° C. The mixture is stirred for a further 120 min at 130° C. Propylene oxide (10.0 g, 172 mmol, 17.2 eq.) is then continuously fed into the reactor over 60 minutes. The mixture is stirred for a further 180 min at 130° C. The conversions are determined from the reaction solution by .sup.1H NMR. Volatile components are subsequently removed under vacuum. The copolymer is investigated for thermal stability by TGA analysis.

Example 2: Preparation of a Polyester-Polyether Polyol Block Copolymer (Having a PET-PES-PET Block Copolymer Structure) by Block Copolymerization of Propiolactone and Propylene Oxide Via DMC Catalysis

[0216] THF (50.0 g), DMC catalyst (3000 ppm based on the total mass of starter and β-lactone) and adipic acid (2.92 g, 20.0 mmol, 1.00 eq.) are initially charged into a 300 mL steel reactor. The reactor is purged with N.sub.2. β-Propiolactone (17.1 g, 237 mmol, 11.9 eq.) is then continuously fed into the reactor over 120 min at 130° C. The mixture is stirred for a further 120 min at 130° C. Propylene oxide (40.0 g, 689 mmol, 34.5 eq.) is then continuously fed into the reactor over 90 minutes. The mixture is stirred for a further 180 min at 130° C. The conversions are determined from the reaction solution by .sup.1H NMR. Volatile components are subsequently removed under vacuum. The copolymer is investigated for thermal stability by TGA analysis.

Example 3 (Comparative): Preparation of a Polyester-Polyether Polyol Block Copolymer (Having a PES-PET-PES Block Copolymer Structure) by Polymerization of Propiolactone onto a Polymeric Propylene Oxide-Based Polyether by DMC Catalysis

[0217] THF (50.0 g), DMC catalyst (3000 ppm based on the total mass of starter and β-lactone) and PPG-1000 (10.0 g, 10.0 mmol, 1.00 eq.) are initially charged into a 300 mL steel reactor. The reactor is purged with N.sub.2. β-Propiolactone (20.0 g, 276 mmol, 27.6 eq.) is then continuously fed into the reactor over 120 min at 130° C. The mixture is stirred for a further 120 min at 130° C. The conversions are determined from the reaction solution by .sup.1H NMR. Volatile components are subsequently removed under vacuum. The copolymer is investigated for thermal stability by TGA analysis.

TABLE-US-00001 TABLE 1 Polyether ester block copolymers from β-lactones and propylene oxide via DMC catalysis H-funct. Block Starter x(cat) MW.sub.target m(PET)/ MW [g/mol] X(lactone) X(PO) No. structure.sup.[a] Lactone Epoxide substance Solvent [ppm] [g/mol] m(PES) Outer block [%] [%] Ex. 1 PET-PES-PET bPL PO Adipic acid THF 3000 3000 0.5 PET: 500 100 100 Ex. 2 PET-PES-PET bPL PO Adipic acid THF 3000 3000 2 PET: 1000 100 100 Ex. 3 PES-PET-PES bPL — PPG-1000 THF 3000 3000 0.5 PES: 1000 100 100 (comp.) .sup.[a]PES: polyester block (bPL-based), PET: polyether block (PO-based)

TABLE-US-00002 TABLE 2 Decomposition temperatures T.sub.d of the polyether ester block copolymers from β-lactones and propylene oxide via DMC catalysis Block T.sub.d(1.0%) T.sub.d(5.0%) No. structure.sup.[a] [° C.] .sup.[b] [° C.] .sup.[b] Ex. 1 PET-PES-PET 165 245 Ex. 2 PET-PES-PET 167 234 Ex. 3 (comp.) PES-PET-PES 122 191 .sup.[a]PES: polyester block (bPL-based), PET: polyether block (PO-based); .sup.[b] TGA determined temperature at 1% or 5% mass loss