FURANDICARBOXYLIC ACID-CONTAINING POLYESTERS

Abstract

The invention relates to polyesters consisting of: A) an acid component composed of: a1) 25 to 100 mol % based on the components a1) and a2) of 2,5-furandicarboxylic acid or its esters or mixtures thereof a2) 0 to 75 mol % based on the components a1) and a2) of an aliphatic C.sub.4-C.sub.36-dicarboxylic acid or its esters or mixtures thereof and a3) 1 to 10 mol % based on the components a1) to a3) of a sulfonate-containing compound, wherein the mol percentages of the components a1) to a3) sum to 100, and B) a diol component composed of: b1) 98 to 100 mol % based on the components a1) to a3) of component A of a C.sub.2- to C.sub.12-alkanediol or mixtures thereof and b2) 0 to 2 mol % based on the components a1) to a3) of a branching agent comprising at least 3 functional groups; and optionally further components.

The invention further relates to the production of the polyesters and the use thereof and also to aqueous dispersions and polyester mixtures comprising these polyesters.

Claims

1. A polyester consisting of: A) an acid component composed of: a1) 25 to 100 mol % based on the components a1) and a2) of 2,5-furandicarboxylic acid or its esters or mixtures thereof a2) 0 to 75 mol % based on the components a1) and a2) of an aliphatic C.sub.4-C.sub.36-dicarboxylic acid or its esters or mixtures thereof and a3) 1 to 10 mol % based on the components a1) to a3) of a sulfonate-containing compound, wherein the mol percentages of the components a1) to a3) sum to 100, and B) a diol component composed of: b1) 98 to 100 mol % based on the components a1) to a3) of component A of a C.sub.2- to C.sub.12-alkanediol or mixtures thereof and b2) 0 to 2 mol % based on the components a1) to a3) of a branching agent comprising at least 3 functional groups; and C) optionally also one or more components selected from: c1) an ether-containing dihydroxyl compound of formula I
HO[(CH.sub.2).sub.nO].sub.mH(I) in which n represents 2, 3 or 4 and m represents an integer from 2 to 250, c2) a hydroxycarboxylic acid of formula IIa or IIb ##STR00005## in which p represents an integer from 1 to 1500 and r represents an integer from 1 to 4 and G represents a radical selected from the group consisting of phenylene, (CH.sub.2).sub.q, wherein q represents an integer from 1 to 5, C(R)H and C(R)HCH.sub.2, wherein R represents a methyl or ethyl c3) an amino-C.sub.2- to C.sub.12-alkanol or at least one amino-C.sub.5- to C.sub.10-cycloalkanol or mixtures thereof c4) a diamino-C.sub.1- to C.sub.a-alkane c5) a 2,2-bisoxazoline of general formula III ##STR00006## wherein R.sup.1 represents a single bond, a (CH.sub.2).sub.z-alkylene group, where z=2, 3 or 4, or a phenylene group c6) an aminocarboxylic acid selected from the group consisting of caprolactam, 1,6-aminocaproic acid, laurolactam, 1,12-aminolauric acid and 1,11-aminoundecanoic acid or mixtures of c1) to c6) wherein the components b1) and b2) and optionally c1), c3) and c4) sum to 100 mol % and the components a1) to a3) and optionally c5) sum to 100 mol % and D) 0% to 4% by weight based on the components A and B and optionally C of a component d1) at least one di- or oligo-functional molecule selected from the group consisting of isocyanate and isocyanurate.

2. The polyester according to claim 1, comprising 0.1% to 4% by weight based on the components A, B and optionally C of a component d1).

3. The polyester according to claim 2, wherein component d1) is 1,6-hexamethylene diisocyanate.

4. The polyester according to any of claims 1 to 3, comprising 0.01 to 1 mol % based on the components a1) to a3) of glycerol (b2).

5. The polyester according to any of claims 1 to 4, comprising 5 to 10 mol % based on the components a1) to a3) of an isophthalic acid-5-sulfonic acid sodium salt (a3).

6. The polyester according to any of claims 1 to 4, comprising 1 to 4.5 mol % based on the components a1) to a3) of an isophthalic acid-5-sulfonic acid sodium salt (a3).

7. The polyester according to any of claims 1 to 6, wherein 100 mol % based on the components a1) and a2) of a 2,5-furandicarboxylic acid or its esters or mixtures thereof are employed.

8. The polyester according to claim 7, wherein component b1) is ethylene glycol.

9. The polyester according to any of claims 1 to 5, comprising 50 to 75 mol % based on the components a1) and a2) of a 2,5-furandicarboxylic acid or its esters or mixtures thereof and 25 to 50 mol % based on the components a1) and a2) of an aliphatic C.sub.4-C.sub.36-dicarboxylic acid or its esters or mixtures thereof.

10. The polyester according to claim 9, wherein component b1) is 1,4-butanediol.

11. An aqueous dispersion comprising a polyester according to claim 5 or claims 7 to 10 to the extent that they refer back to claim 5.

12. The use of the polyesters according to any of claims 1 to 10 for producing fibers, films and moldings.

13. The use of the aqueous dispersion according to claim 11 for paper coating or for impregnation of a nonwoven fabric or article.

14. A process for producing the polyesters according to any of claims 1 to 10, wherein dimethyl 2,5-furandicarboxylate is employed as component a1) and isophthalic acid dimethyl ester-5-sulfonic acid sodium salt is employed as component a3).

15. A polyester mixture comprising: i) 5% to 95% by weight based on the polyester mixture of a polyester according to any of claims 1 to 10, ii) 95% to 5% by weight based on the polyester mixture of at least one or more components selected from the group consisting of: a polyester produced from an aliphatic dicarboxylic acid and an aliphatic diol; polycaprolactone, starch, cellulose, polyhydroxyalkanoate, polyglycolic acid and polylactic acid.

Description

EXAMPLES

[0128] General Procedure for Producing the Aromatic Polyesters According to the Invention

[0129] To produce polyesters 1 to 9 and polyester 1a, 92 mol % of 2,5-dimethylfurandicarboxylic acid (2,5-dimethylfuranate DM-FDCA) and 8 mol % of dimethyl sodium sulfoisophthalic acid (DMNaSIP), 130 mol % of diol and the amounts of glycerol specified below were mixed together with the amounts of tetrabutyl orthotitanate specified below (TBOT). The reaction mixture was heated to a temperature of 180 C. and reacted at this temperature for 2 h. The temperature was then increased to 240 C. and excess diol was distilled off under vacuum over a period of 2 h. The amounts of hexamethylene diisocyanate (HDI) specified below were then added slowly over 10 min at 240 C.

Example 1

[0130] 92.2 g (92 mol %) of 2,5-dimethylfuranate; 12.8 g (8 mol %) of DMNaSIP; 43.9 g (130 mol %) of ethylene glycol; 0.1 g of glycerol; 0.07 g of TBOT; 0.83 g of HDI

[0131] Glass transition temperature (Tg): 87 C., viscosity number (VN): 87, elastic modulus: 2900 MPa, yield stress: 78 MPa

Example 1a

[0132] 92.2 g (92 mol %) of 2,5-dimethylfuranate; 12.8 g (8 mol %) of DMNaSIP; 43.9 g (130 mol %) of ethylene glycol; 0.1 g of glycerol; 0.07 g of TBOT;

[0133] Tg: 87 C., VN: 55, elastic modulus: 2860 MPa, yield stress: 46 MPa

Example 2

[0134] 92 mol % of 2,5-dimethylfuranate; 8 mol % of DMNaSIP; 130 mol % of diethylene glycol; 0.11 g of glycerol; 0.08 g of TBOT; 0.85 g of HDI

[0135] Tg: 45 C., VN: 105

Example 3

[0136] 92 mol % of 2,5-dimethylfuranate; 8 mol % of DMNaSIP; 130 mol % of 1,4-butanediol; 0.1 g of glycerol; 0.07 g of TBOT; 0.84 g of HDI

[0137] Tg: 38 C., VN: 93

Example 4

[0138] 92 mol % of 2,5-dimethylfuranate; 8 mol % of DMNaSIP; 130 mol % of 1,6-hexanediol; 0.11 g of glycerol; 0.08 g of TBOT; 0.85 g of HDI

[0139] Tg: 10 C., VN: 83

Example 5

[0140] 92 mol % of 2,5-dimethylfuranate; 8 mol % of DMNaSIP; 130 mol % of 1,8-octanediol; 0.11 g of glycerol; 0.08 g of TBOT; 0.85 of HDI

[0141] Tg: 8 C., VN: 98

Example 6

[0142] 92 mol % of 2,5-dimethylfuranate; 8 mol % of DMNaSIP; 130 mol % of neopentyl glycol; 0.11 g of glycerol; 0.08 g of TBOT; 0.85 g of HDI

[0143] Tg: 43 C., VN: 92

Example 7

[0144] 92 mol % of 2,5-dimethylfuranate; 8 mol % of DMNaSIP; 130 mol % of 1,4-cyclohexanedimethanol; 0.08 g of glycerol; 0.06 g of TBOT; 0.87 g of HDI

[0145] Tg: 95 C., VN: 72

Example 8

[0146] 92 mol % of 2,5-dimethylfuranate; 8 mol % of DMNaSIP; 130 mol % of triethylene glycol; 0.11 g of glycerol; 0.08 g of TBOT; 0.86 g of HDI

[0147] Tg: 11 C., VN: 76

Example 9

[0148] 92 mol % of 2,5-dimethylfuranate; 8 mol % of DMNaSIP; 130 mol % of tetraethylene glycol; 0.11 g of glycerol; 0.08 g of TBOT; 0.86 g of HDI

[0149] Tg: 4 C., VN: 81

[0150] General Procedure for Producing the Aliphatic-Aromatic Polyesters:

[0151] To produce polyesters 10 to 16, 68/62 mol % of 2,5-dimethylfurandicarboxylic acid (2,5-dimethylfuranate) and 2/8 mol % of dimethyl sodium sulfoisophthalic acid (DMNaSIP), 130 mol % of 1,4-butanediol and 0.1% by weight of glycerolbased on the polyesterwere mixed together with 0.07 g of tetrabutyl orthotitanate (TBOT) (100 ppm of Ti). The reaction mixture was heated to a temperature of 180 C. and reacted at this temperature for 1 h. 30 mol % of aliphatic dicarboxylic acid were then added and the mixture was reacted for a further 1 h. The temperature was then increased to 240 C. and excess dihydroxyl compound was distilled off under vacuum over a period of 2 h. 0.8% by weight of hexamethylene diisocyanate (HDI)based on the polyesterwere then added slowly over 10 min at 240 C.

Example 10

[0152] 62.6 g (68 mol %) of 2,5-dimethylfuranate; 3.0 g (2 mol %) of DMNaSIP; 30.3 g (30 mol %) of sebacic acid; 58.5 g (130 mol %) of 1,4-butanediol;

[0153] Melting point (Tm): 128 C., Tg: 9 C., VN 167

Example 11

[0154] 57.0 g (62 mol %) of 2,5-dimethylfuranate; 11.8 g (8 mol %) of DMNaSIP; 30.3 g (30 mol %) of sebacic acid; 58.5 g (130 mol %) of 1,4-butanediol;

[0155] Tm: 120 C., Tg: 1 C., VN: 154

Example 12

[0156] 68 mol % of 2,5-dimethylfuranate; 2 mol % of DMNaSIP; 30 mol % of adipic acid; 130 mol % of 1,4-butanediol;

[0157] Tm: 129 C., Tg: 5 C., VN 145

Example 13

[0158] 68 mol % of 2,5-dimethylfuranate; 2 mol % of DMNaSIP; 30 mol % of dodecanedioic acid; 130 mol % of 1,4-butanediol;

[0159] Tm: 129 C., Tg: 12 C., VN 163

Example 14

[0160] 68 mol % of 2,5-dimethylfuranate; 2 mol % of DMNaSIP; 30 mol % of brassylic acid; 130 mol % of 1,4-butanediol;

[0161] Tm: 130 C., Tg: 13 C., VN 151

Example 15

[0162] 68 mol % of 2,5-dimethylfuranate; 2 mol % of DMNaSIP; 30 mol % of 1,18-C.sub.18-dicarboxylic acid; 130 mol % of 1,4-butanediol;

[0163] Tm: 133 C., Tg: 3 C., VN 173

Example 16

[0164] 68 mol % of 2,5-dimethylfuranate; 2 mol % of DMNaSIP; 30 mol % of 1,36-C.sub.36-dicarboxylic acid; 130 mol % of 1,4-butanediol;

[0165] Tm: 137 C., Tg: 33 C., VN 189

[0166] Film Composting Test

[0167] 10 g of polymer were dissolved in 50 ml of hexafluoroisopropanol at 20 C. This polymer solution was poured onto a Petri dish and solvent was evaporated in a fume hood. Films (thickness: about 30 m) were obtained.

[0168] The films were then buried in compost at a depth of 1-2 cm in matured compost from a commercial composting facility (sieved (sieve size: 1 cm) in a Tupperware container and this is closed with a lid. This was incubated in a heating cabinet at 58 C. At regular intervals, drinking water is poured on the compost in order to keep the compost sufficiently moist. After 2 and 4 weeks, film samples were weighed.

[0169] Film Composting Test

[0170] 10 g of polymer were dissolved in 50 ml of hexafluoroisopropanol at 20 C. This polymer solution was poured onto a Petri dish and solvent was evaporated in a fume hood. Films (thickness: about 30 m) were obtained.

[0171] The films were then buried in compost at a depth of 1-2 cm in matured compost from a commercial composting facility (sieved (sieve size: 1 cm) in a Tupperware container and this is closed with a lid. This was incubated in a heating cabinet at 58 C. At regular intervals, drinking water is poured on the compost in order to keep the compost sufficiently moist. After 2 and 4 weeks, film samples were weighed.

TABLE-US-00001 TABLE 1 Examples V-A A B V-C C V-D D DM-FDCA* 100 98 92 70 68 70 68 DM-Na-SIP* 0 2 8 0 2 0 2 Adipic acid* 30 30 Sebacic acid* 30 30 Ethylene glycol* 100 100 100 1,4-Butanediol 100 100 100 100 Weight (initial)** 100 100 100 100 100 100 100 Weight (after 2 99 95 87 72 61 66 50 weeks)** Weight (after 4 99 89 73 50 31 45 21 weeks)** *= % by weight **= %