Thermoplastic polyurethane

Abstract

The present invention relates to thermoplastic polyurethanes obtainable or obtained by reaction of at least one polyisocyanate composition, at least one chain extender (KV1) of general formula (I) and one further chain extender (KV2) selected from the group consisting of compounds having at least two isocyanate-reactive groups having a molecular weight of <500 g/mol, and at least one polyol composition. The present invention further relates to a production process for such thermoplastic polyurethanes and to the use of a thermoplastic polyurethane according to the invention or of a thermoplastic polyurethane obtainable or obtained by a process according to the invention for producing extrusion products, films and molded articles.

Claims

1. A thermoplastic polyurethane obtained by reaction of at least a polyisocyanate composition; hydroxyquinone bis(2-hydroxyethyl)ether as a first chain extender; a polyol composition; and a second chain extender, wherein the second chain extender has at least two isocyanate-reactive groups and has a molecular weight of <500 g/mol, and the second chain extender is a compound of general formula (II): ##STR00014## wherein A is O, N(R3), S, or CH.sub.2, Q is O, N(R3), S, or CH.sub.2, R1 is CH.sub.2—(CH.sub.2).sub.n—OH, CH(CH.sub.3)—CH.sub.2—OH, or OH, R2 is CH.sub.2—(CH.sub.2).sub.n—OH, CH(CH.sub.3)—CH.sub.2—OH, CH.sub.2—CH(CH.sub.3)—OH, or OH, n is 0, 1, 2, 3, 4, 5 or 6, and R3 is CH.sub.3, or CH.sub.2—CH.sub.3, wherein a molar ratio of hydroquinone bis(2-hydroxyethyl)ether to the second chain extender is in a range of 9:1 to 19:1; and the polyol present in the polyol composition is a polyetherol.

2. The thermoplastic polyurethane according to claim 1, wherein said polyetherol is a polytetrahydrofuran having a number-average molecular weight Mn in a range from 500 g/mol to 5000 g/mol.

3. The thermoplastic polyurethane according to claim 1, wherein said polyetherol comprises a polytetrahydrofuran having a number-average molecular weight Mn in a range from 1501 g/mol to 3000 g/mol and a polytetrahydrofuran having a number-average molecular weight Mn in a range from 500 g/mol to 1500 g/mol.

4. The thermoplastic polyurethane according to claim 1, wherein the polyisocyanate composition comprises an isocyanate selected from the group consisting of 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 1,5-naphthylene diisoctanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate and 2,4′-diphenylmethane diisocyanate.

5. The thermoplastic polyurethane according to claim 1, wherein the polyisocyanate composition comprises a mixture of 4,4′-diphenylmethane diisocyanate and 2,4′-diphenylmethane diisocyanate.

6. A process for producing a thermoplastic polyurethane, the process comprising: reacting polyisocyanate composition; hydroxyquinone bis(2-hydroxyethyl)ether as a first chain extender; a polyol composition; and a second chain extender, wherein the second chain extender has at least two isocyanate-reactive groups and has a molecular weight of <500 g/mol and the second chain extender is a compound of general formula (II): ##STR00015## wherein A is O, N(R3), S, or CH.sub.2, Q is O, N(R3), S, or CH.sub.2, R1 is CH.sub.2—(CH.sub.2).sub.n—OH, CH(CH.sub.3)—CH.sub.2—OH, or OH, R2 is CH.sub.2—(CH.sub.2).sub.n—OH, CH(CH.sub.3)—CH.sub.2—OH, CH.sub.2—CH(CH.sub.3)—OH, or OH, n is 0, 1, 2, 3, 4, 5 or 6, and R3 is CH.sub.3, or CH.sub.2—CH.sub.3, wherein a molar ratio of hydroquinone bis(2-hydroxyethyl)ether to the second chain extender is in a range of 9:1 to 19:1; and the polyol present in the polyol composition is a polyetherol.

7. An article, comprising the thermoplastic polyurethane according to claim 1, wherein the article is an extrusion product, a film or a molded article.

8. The article according to claim 7, wherein the article is an extrusion product or a film, and the extrusion product or the film is reinforced with fillers.

9. An article, comprising the thermoplastic polyurethane according to claim 1, wherein the article is a foamed film, a foamed molding, foamed particles or particle foams obtained therefrom.

10. The article according to claim 9, wherein the article is reinforced with fillers.

11. The thermoplastic polyurethane according to claim 1, where A and Q are each independently O, N(R3),or S.

12. The thermoplastic polyurethane according to claim 1, wherein said second chain extender is resorcinol bis(2-hydroxyethyl)ether.

13. The thermoplastic polyurethane according to claim 1, wherein said thermoplastic polyurethane has a room temperature tensile strength of 51 MPa to 52 MPa.

14. The thermoplastic polyurethane according to claim 1, wherein said thermoplastic polyurethane has a room temperature elongation at break of 510% to 520%.

15. The thermoplastic polyurethane according to claim 1, wherein an amount of said second chain extender is 5 to 10% based on a total amount of chain extender.

16. The process according to claim 6, wherein an amount of said second chain extender is 5 to 10% based on a total amount of chain extender.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) FIGS. 1A-1D show hoses produced from a thermoplastic polyurethane, wherein the thermoplastic polyurethane consists of PTHF1000 and the specified hard phase and has a shore hardness of 98A. The materials were produced on a pilot reaction extruder.

(2) FIG. 1A and FIG. 1B show a hose made of a thermoplastic polyurethane comprising an HQEE-MDI hard phase.

(3) FIG. 1C and FIG. 1D show a hose made of a thermoplastic polyurethane comprising TPU comprising an HQEE/HER-MDI hard phase.

(4) The examples which follow are intended to illustrate the invention but are in no way intended to restrict the subject matter of the present invention.

EXAMPLES

(5) 1 The Following Input Materials were Used:

(6) PTHF 1000: Polytetramethylene oxide (PTHF) Mw 1000 g/mol PTHF 650: Polytetramethylene oxide (PTHF) Mw 650 g/mol PTHF 2000: Polytetramethylene oxide (PTHF) Mw 2000 g/mol HQEE: Hydroquinone bis(2-hydroxyethyl)ether 4,4′-MDI: 4,4′-diphenylmethane diisocyanate TODI: 3,3′-dimethyl-4,4′-di isocyanatobiphenyl HER: Resorcinol bis(2-hydroxyethyl)ether 1,4-Butanediol Irganox 1010 FF (CAS No. 6683-19-8) and 1098 (CAS No. 23128-74-7)
2 Synthesis of the Polyurethanes

2.1 Polyurethane Based on HQEE, 4,4-MDI and PTHF (Comparative Example)

(7) 800.00 g of PolyTHF1000 together with 238.84 g of HQEE were weighed into a 2 L tinplate can and briefly blanketed with nitrogen. The can was sealed with a suitable lid and heated to about 120° C. in a heating cabinet. The liquid components in the can were mixed with a propeller stirrer on a lift. Subsequently 7.81 g of Irganox 1010 FF and 7.81 g of Irganox 1098 were added and the mixture was stirred. The temperature of the mixture was carefully adjusted to 108° C. with a hot air gun. Addition of 505.1 g of 4,4′-MDI was carried out at 108° C. ( ). The MDI had a temperature of 45° C. Commixing was effected using a propeller stirrer at 200 rpm. Upon reaching 110° C. the reaction mixture was poured into a Teflon dish. The Teflon dish was situated on a hotplate at 125° C. The solid slab was removed from the hotplate after 10 min and then heat treated in a heating cabinet at 80° C. for 24 h. The cooled slab was comminuted in a cutting mill. The resulting granulate was dried at 110° C. for 3 h. 2 mm and 6 mm test specimens were produced by injection molding methods.

2.2 Polyurethane Based on an HQEE and 1,4-Butanediol Mixture (Example 1)

(8) 800.00 g of PolyTHF1000 together with 235.49 g of HQEE and 11.96 g of HER and 2.19 g of 1,4-butanediol were weighed into a 2 L tinplate can and briefly blanketed with nitrogen. The can was sealed with a suitable lid and heated to about 120° C. in a heating cabinet. The liquid components in the can were mixed with a propeller stirrer on a lift. Subsequently 7.81 g of Irganox 1010 FF and 7.81 g of Irganox 1098 were added and the mixture was stirred. The temperature of the mixture was carefully adjusted to 108° C. with a hot air gun. Addition of 508.18 g of 4,4′-MDI was carried out at 108° C. ( ). The MDI had a temperature of 45° C. Commixing was effected using a propeller stirrer at 200 rpm. Upon reaching 110° C. the reaction mixture was poured into a Teflon dish. The Teflon dish was situated on a hotplate at 125° C. The solid slab was removed from the hotplate after 10 min and then heat treated in a heating cabinet at 80° C. for 24 h. The cooled slab was comminuted in a cutting mill. The resulting granulate was dried at 110° C. for 3 h. 2 mm and 6 mm test specimens were produced by injection molding methods.

2.3 Example 2

(9) Production was carried out by the same production process as described in connection with example 1 but 5% 1,4-butanediol was used. The input materials are summarized in table 1.

2.4 Example 3

(10) Production was carried out by the same production process as described in connection with example 1 but 10% 1,4-butanediol was used. The input materials are summarized in table 1.

2.5 Polyurethane Based on an HQEE and HER Mixture (Example 4)

(11) 800.00 g of PolyTHF1000 together with 227.18 g of HQEE and 11.96 g of HER were weighed into a 2 L tinplate can and briefly blanketed with nitrogen. The can was sealed with a suitable lid and heated to about 120° C. in a heating cabinet.

(12) The liquid components in the can were mixed with a propeller stirrer on a lift. Subsequently 7.81 g of Irganox 1010 FF and 7.81 g of Irganox 1098 were added and the mixture was stirred.

(13) The temperature of the mixture was carefully adjusted to 108° C. with a hot air gun. Addition of 506.72 g of 4,4′-MDI was carried out at 108° C. The MDI had a temperature of 45° C. Commixing was effected using a propeller stirrer at 200 rpm. Upon reaching 110° C. the reaction mixture was poured into a Teflon dish. The Teflon dish was situated on a hotplate at 125° C.

(14) The solid slab was removed from the hotplate after 10 min and then heat treated in a heating cabinet at 80° C. for 24 h. The cooled slab was comminuted in a cutting mill. The resulting granulate was dried at 110° C. for 3 h. 2 mm and 6 mm test specimens were produced by injection molding methods.

2.6 Example 5

(15) Production was carried out by the same production process as described in connection with example 4 but 10% HER was used. The input materials are summarized in table 1.

2.7 Example 6

(16) Production was carried out by the same production process as described in connection with example 4 but 50% HER was used. The input materials are summarized in table 1.

2.8 Polyurethane Based on an HQEE and PTHF Mixture (Example 7)

(17) 760.00 g of PolyTHF2000 and 40.00 g of PolyTHF650s together with 268.52 g of HQEE were weighed into a 2 L tinplate can and briefly blanketed with nitrogen. The can was sealed with a suitable lid and heated to about 120° C. in a heating cabinet.

(18) The liquid components in the can were mixed with a propeller stirrer on a lift. Subsequently 7.68 g of Irganox 1010 FF and 7.68 g of Irganox 1098 were added and the mixture was stirred.

(19) The temperature of the mixture was carefully adjusted to 108° C. with a hot air gun. Addition of 451.23 g of 4,4′-MDI was carried out at 108° C. The MDI had a temperature of 45° C. Commixing was effected using a propeller stirrer at 200 rpm. Upon reaching 110° C. the reaction mixture was poured into a Teflon dish. The Teflon dish was situated on a hotplate at 125° C.

(20) The solid slab was removed from the hotplate after 10 min and then heat treated in a heating cabinet at 80° C. for 24 h. The cooled slab was comminuted in a cutting mill. The resulting granulate was dried at 110° C. for 3 h. 2 mm and 6 mm test specimens were produced by injection molding methods.

2.9 Example 8

(21) Production was carried out by the same production process as described in connection with example 7 but 10% PolyTHF650s was used. The input materials are summarized in table 1.

2.10 Example 9

(22) Production was carried out by the same production process as described in connection with example 7 but 20% PolyTHF650s was used. The input materials are summarized in table 1.

(23) TABLE-US-00001 TABLE 1 Employed compounds Example 2 Example 3 Example 5 Example 6 Example 8 Example 9 PolyTHF 1000 800.00 g 800.00 g 800.00 g 800.00 g 1,4-Butanediol  5.50 g  11.14 g PolyTHF 2000 720.00 g 640.00 g PolyTHF 650s  80.00 g 160.00 g HQEE 229.95 g 220.54 g 215.22 g 119.57 g 271.61 g 277.81 g HER  23.91 g 119.57 g 4,4-MDI 510.40 g 514.18 g 506.72 g 506.72 g 465.66 g 494.53 g Irganox 1010 FF  7.81 g  7.81 g  7.81 g  7.81 g  7.76 g  7.94 g Irganox 1098  7.81 g  7.81 g  7.81 g  7.81 g  7.76 g  7.94 g

2.11 Variation of the HQEE/HER Ratio (Examples 10 to 18)

(24) The examples were produced analogously to example 1. The ratio of the chain extenders was varied according to table 2.

(25) TABLE-US-00002 TABLE 2 Mixing ratios for examples 10 to 18 HS proportion Test Example Reactants [%] sheets Index Example 10 PTHF1000, HQEE + 35.0% translucent 1000 HER (9.5:0.5) and MDI Example 11 PTHF1000, HQEE + 35.0% translucent 1000 HER (9:1) and MDI Example 12 PTHF1000, HQEE + 35.0% transparent 1000 HER (5:5) and MDI Example 13 PTHF1000, HQEE + 35.0% transparent 1000 HER (8.5:1.5) and MDI Example 14 PTHF1000, HQEE + 35.0% transparent 1000 HER (8:2) and MDI Example 15 PTHF1000, HQEE + 35.0% transparent 1000 HER (7.5:2.5) and MDI Example 16 PTHF1000, HQEE + 35.0% transparent 1000 HER (7:3) and MDI Example 17 PTHF1000, HQEE + 35.0% transparent 1000 HER (6.5:3.5) and MDI Example 18 PTHF1000, HQEE + 35.0% transparent 1000 HER (5.5:4.5) and MDI
3 Mechanical Properties

(26) 3.1 The measured values summarized in tables 3a and 3b were obtained from injection molded sheets/from extrusion products of the obtained polyurethanes.

(27) TABLE-US-00003 TABLE 3a Mechanical properties Elongation at break Tensile Elongation strength at break Example Shore hardness RT 80° C. (RT) 80° C. number [Shore A] [Shore D] [MPa] [MPa] [%] [%] Example 1 95 53 54 26 490 630 Example 2 95 53 51 20 520 620 Example 3 94 51 42 19 500 590 Comparative 95 52 34 18 480 640 example 1

(28) TABLE-US-00004 TABLE 3b Mechanical properties Compression set Tear 72 h/ 24 h/ 24 h/ propagation 23° C./ 70° C./ 100° C./ Example resistance Abrasion Density 30 min 30 min 30 min number [N/mm] [mm.sup.3] [g/cm.sup.3] [%] [%] [%] Example 1 105 34 1.144 15 27 41 Example 2 100 43 1.144 16 31 46 Example 3  94 47 1.142 15 33 46 Com-  88 61 1.144 22 30 43 parative example 1

(29) 3.2 The measured values summarized in tables 4a and 4b were obtained from injection molded sheets/extrusion products of the obtained polyurethanes according to examples 10 to 18.

(30) TABLE-US-00005 TABLE 4a Mechanical properties Elongation at break Tensile Elongation strength at break Example Shore hardness RT 80° C. (RT) 80° C. number [Shore A] [Shore D] [MPa] [MPa] [%] [%] Example 10 — 52 52 16 520 650 Example 11 — 52 51 16 510 680 Example 12 — 46 48 14 480 750 Example 13 94 50 36 17 460 640 Example 14 93 50 38 15 470 540 Example 15 93 48 38 14 470 500 Example 16 91 48 42 16 460 580 Example 17 91 47 38 14 460 500 Example 18 89 45 45 16 460 510

(31) TABLE-US-00006 TABLE 4b Mechanical properties Compression set Tear prop- 72 h/ 24 h/ 24 h/ agation 23° C./ 70° C./ 100° C./ Example resistance Abrasion Density 30 min 30 min 30 min number [N/mm] [mm.sup.3] [g/cm.sup.3] [%] [%] [%] Example 10 90 43 1.144 16 32 31 Example 11 90 46 1.143 16 15 35 Example 12 82 35 1.143 15 20 46 Example 13 92 50 1.143 11 34 47 Example 14 89 45 1.142 11 26 50 Example 15 86 46 1.142 19 29 49 Example 16 93 39 1.141 21 32 43 Example 17 95 38 1.143 20 33 46 Example 18 86 37 1.143 16 31 50

(32) 3.3 The following properties of the obtained polyurethanes were determined by the recited methods: Hardness: DIN ISO 7619-1 Tensile strength and elongation at break: DIN 53504 Tear propagation resistance: DIN ISO 34-1, B (b) Abrasion measurement: DIN ISO 4649 Density: DIN EN ISO 1183-1, A Compression set DIN ISO 815
4 Extrusion Quality

(33) The images reproduced in FIGS. 1A-1D show the different hose extrusion qualities of a TPU consisting of PTHF 1000, the recited hard phase and a shore hardness of 98A produced on a pilot reaction extruder. Materials obtained by manual casting had a comparable appearance.

(34) Hoses were produced from the materials of comparative example 1 and example 5. Hose production was carried out using a 45 mm single-screw extruder from Arenz (3-zone screw, compression ratio 1:2.5). The hoses had dimensions of 8.2 mm×5.8 mm.

(35) FIG. 1A and FIG. 1B show a hose made of a thermoplastic polyurethane comprising an HQEE-MDI hard phase (according to comparative example 1).

(36) FIG. 1C and FIG. 1D show a hose made of a thermoplastic polyurethane comprising TPU comprising an HQEE/HER-MDI hard phase (according to example 5).

CITED LITERATURE

(37) WO 2006/082183 A1 EP 0 922 552 A1 WO 98/56845 “Kunststoffhandbuch”, volume 7, “Polyurethane”, Carl Hanser Verlag, 3rd edition, 1993, chapter 3.1 “Kunststoffhandbuch”, volume VII, edited by Vieweg and Höchtlen, Carl Hanser Verlag, Munich, 1966 (pp. 103-113) WO 2007/118827 A1 EP 0 922 552 A1 WO 2006/082183 A1 WO2014/198779 A1 WO 2007/082838 A1 WO 94/20568 A1