Thermoplastic polyurethane matrix resin

Abstract

The invention relates to a thermoplastic polyurethane matrix resin composition, comprising at least one C.sub.3-8 alkane diol, at least one alkoxylated aromatic diol and at least one polyisocyanate. Furthermore, the present invention relates to a fiber-reinforced composite comprising a cured thermoplastic polyurethane polymer matrix according to the present invention and a fiber material. Moreover, a method for the manufacture of the fiber-reinforced composite according to the present invention and use of the composition or the fiber-reinforced composite in railway vehicles, automotive vehicles, aircraft vehicles, boats, space vehicles, motorbikes, bicycles, sporting goods, helmets, functional clothing, shoes, construction parts in bridges and buildings or wind turbine blades are described.

Claims

1. A thermoplastic polyurethane matrix resin composition, comprising (i) at least one C.sub.3-8 alkane diol of formula (I) ##STR00004## wherein R.sub.1, R.sub.1′, R.sub.2, R.sub.2′, R.sub.3 and R.sub.3′ are independently selected from H and substituted or unsubstituted C.sub.1-4 alkyl, n is 0, 1, 2 or 3, and if n is 0, 2 or 3, at least one of R.sub.1, R.sub.1′, R.sub.2 and R.sub.2′ is substituted or unsubstituted C.sub.1-4 alkyl; (ii) at least one polyisocyanate; and (iii) 5 to 75 wt. % of at least one alkoxylated aromatic diol relative to the total weight of the thermoplastic polyurethane resin composition; wherein the diols in the thermoplastic polyurethane matrix resin composition consist of the at least one C.sub.3-8 alkane diol of formula (I) and the at least one alkoxylated aromatic diol.

2. The composition according to claim 1, wherein (a) n=0; or (b) R.sub.1′ or R.sub.2′ or both are H; or (c) R.sub.1 and/or R.sub.2 are selected from methyl and ethyl; or (d) any combination of (a), (b) and (c).

3. The composition according to claim 1, wherein the at least one C.sub.3-8 alkane diol is a vicinal diol with n=0.

4. The composition according to claim 1, wherein the at least one C.sub.3-8 alkane diol of formula (I) is selected from the group consisting of 2,3-butane diol, 2,3-pentane diol, 2,3-hexane diol, 3,4-hexane diol, 1,2-propane diol, 1,3-propane diol, 1,2-butane diol, 1,2-pentane diol, 1,2-hexane diol and combinations thereof.

5. The composition according to claim 1, wherein a molar ratio of the OH groups of the combined components (i) and (iii) to the NCO groups of said polyisocyanate (ii) is from 2:1 to 1:2.

6. The composition according to claim 1, wherein the at least one polyisocyanate is selected from the group consisting of 4,4′-diphenylmethanediisocyanate, 2,4′-diphenylmethanediisocyanate, polymeric 4,4′-diphenylmethanediisocyanate, polymeric 2,4′-diphenylmethanediisocyante and combinations thereof.

7. The composition according to claim 1, wherein the at least one polyisocyanate comprises 10 wt. % to 70 wt. % polymeric MDI based on the total weight of polyisocyanates in the composition.

8. The composition according to claim 1, wherein the at least one alkoxylated aromatic diol is a compound of formula (II) ##STR00005## wherein Rx is selected from CH.sub.2, CH(CH.sub.3) and C(CH.sub.3).sub.2, in the m block Ry is H and Rz is methyl or Ry is methyl and Rz is H, in the m′ block Ry is H and Rz is methyl or Ry is methyl and Rz is H, and n, n′, m and m′ are values such that n+n′+m+m′=1 to 20.

9. The composition according to claim 8, wherein n+n′+m+m′=1 to 8.

10. The composition according to claim 1, wherein the thermoplastic polyurethane matrix resin composition further comprises at least one auxiliary substance.

11. The composition according to claim 1, being a two-component composition, wherein a first component comprises the at least one polyisocyanate and a second component comprises the at least one C.sub.3-8 alkane diol and the at least one alkoxylated aromatic diol, the two parts being stored separately and mixed to initiate a curing reaction.

12. Cured reaction products of the composition according to claim 1.

13. A fiber-reinforced composite comprising: cured reaction products of a thermoplastic polyurethane matrix resin composition, comprising (i) at least one C3-8 alkane diol of formula (I) ##STR00006## wherein R1, R1′, R2¬, R2′, R3 and R3′ are independently selected from H and substituted or unsubstituted C.sub.1-4 alkyl, n is 0, 1, 2 or 3, and if n is 0, 2 or 3, at least one of R1, R1′, R2 and R2′ is substituted or unsubstituted C1-4 alkyl; (ii) at least one polyisocyanate; and (iii) 5 to 75 wt. % of at least one alkoxylated aromatic diol relative to the total weight of the thermoplastic polyurethane resin composition, and more than 30% by volume of a fiber material based on the total volume of the fiber-reinforced composite, wherein the cured reaction products surround fibers of the fiber material.

14. A method for the manufacture of a fiber-reinforced composite, comprising: providing an external mold comprising the fiber material; providing a fiber material; disposing the fiber material in the mold; fluidly sealing the mold around the fiber material disposed therein; providing a thermoplastic polyurethane matrix resin composition, comprising (i) at least one C3-8 alkane diol of formula (I) ##STR00007## wherein R.sub.1, R1′, R2¬, R2′, R3 and R3′ are independently selected from H and substituted or unsubstituted C.sub.1-4 alkyl, n is 0, 1, 2 or 3, and if n is 0, 2 or 3, at least one of R1, R1′, R2 and R2′ is substituted or unsubstituted C1-4 alkyl: (ii) at least one polyisocyanate; and (iii) 5 to 75 wt. % of at least one alkoxylated aromatic diol relative to the total weight of the thermoplastic polyurethane resin composition introducing the thermoplastic polyurethane matrix resin composition into the closed mold, wherein the thermoplastic polyurethane matrix resin composition surrounds fibers of the fiber material; and curing the thermoplastic polyurethane matrix resin composition in the mold at a temperature above room temperature.

15. The method of claim 14 wherein the thermoplastic polyurethane matrix resin composition in the mold is cured at a temperature of up to 140° C.

16. The method of claim 14 wherein the thermoplastic polyurethane matrix resin composition in the mold is cured at a temperature from 60 to 120° C.

17. The method of claim 14 wherein the thermoplastic polyurethane matrix resin composition is introduced into the closed mold under pressure.

18. The method of claim 14 being resin transfer molding (RTM).

19. An article selected from a railway vehicle, an automotive vehicle, an aircraft vehicle, a boat, a space vehicle, a motorbike, a bicycle, a sporting good, an exercise equipment, a cell phone housing, a laptop housing, a helmet, a piece of clothing, a shoe, a construction part in a bridge, a construction part in a building or a wind turbine blade comprising a fiber material embedded in the cured reaction products of the composition according to claim 1.

Description

EXAMPLES

Example 1: Thermoplastic Polyurethane Matrix Resin Composition

(1) TABLE-US-00001 Equivalent Weighed weight Equivalent portion OH No. Raw material [g/eq] [eq] [g] number 1 1,2-propane diol 38.05 1.02 38.71 2 Ethoxylated 200 0.234 46.78 280.5 bisphenol A 3 mixture of 4,4′-MDI 125.0 0.627 78.41 and 2,4-MDI 4 mixture of 128.8 0.627 80.8 isomers of MDI and polymeric MDI with 11.6% polymer-MDI Tg: 118° C.

Example 2: Thermoplastic Polyurethane Matrix Resin Composition

(2) TABLE-US-00002 Equivalent Weighed weight Equivalent portion OH No. Raw material [g/eq] [eq] [g] number 1 Ethoxylated 200 0.1 20.01 280.5 bisphenol A 2 2,3-butane diol 45.06 0.1 4.51 3 mixture of 4,4′-MDI 125.0 0.20 25.00 and 2,4-MDI Tg: 88° C.

Example 3: Thermoplastic Polyurethane Matrix Resin Composition

(3) TABLE-US-00003 Equivalent Weighed weight Equivalent portion OH No. Raw material [g/eq] [eq] [g] number 1 Ethoxylated 200 0.1 20.01 280.5 bisphenol A 2 1,2-butane diol 45.06 0.1 4.51 3 mixture of 4,4′-MDI 125.0 0.20 25.00 and 2,4-MDI Tg: 83° C.

Example 4: Thermoplastic Polyurethane Matrix Resin Composition

(4) TABLE-US-00004 Equivalent Weighed weight Equivalent portion OH No. Raw material [g/eq] [eq] [g] number 1 Ethoxylated 200 0.1 20.01 280.5 bisphenol A 2 1,2-propane diol 38.05 0.1 3.81 3 mixture of 4,4′-MDI 125.0 0.20 25.00 and 2,4-MDI Tg: 85° C.

Example 5: Thermoplastic Polyurethane Matrix Resin Composition

(5) TABLE-US-00005 Equivalent Weighed weight Equivalent portion OH No. Raw material [g/eq] [eq] [g] number 1 Ethoxylated 200 0.1 20.01 280.5 bisphenol A 2 1,3-propane diol 38.05 0.1 3.81 3 mixture of 4,4′-MDI 125.0 0.20 25.00 and 2,4-MDI Tg: 83° C.

Example 6: Thermoplastic Polyurethane Matrix Resin Composition

(6) TABLE-US-00006 Equivalent Weighed weight Equivalent portion OH No. Raw material [g/eq] [eq] [g] number 1 Ethoxylated 200 0.1 20.01 280.5 bisphenol A 2 1,3-butane diol 45.06 0.1 4.51 3 mixture of 4,4′-MDI 125.0 0.20 25.00 and 2,4-MDI Tg: 83° C.

Comparative Example 1: Thermoplastic Polyurethane Matrix Resin Composition

(7) TABLE-US-00007 Equivalent Weighed weight Equivalent portion OH No. Raw material [g/eq] [eq] [g] number 1 Ethoxylated 200 0.1 20.01 280.5 bisphenol A 2 1,4-butane diol 45.06 0.1 4.51 3 mixture of 4,4′-MDI 125.0 0.20 25.00 and 2,4-MDI Tg: 78° C.

Comparative Example 2: Thermoplastic Polyurethane Matrix Resin Composition

(8) TABLE-US-00008 Equivalent Weighed weight Equivalent portion OH No. Raw material [g/eq] [eq] [g] number 1 Ethoxylated 200 0.1 20.01 280.5 bisphenol A (Dianol 240) 2 mixture of 4,4′-MDI 125.0 0.1 12.50 and 2,4-MDI Tg: 70° C.