Polyurethane with delayed relaxation behaviour for compression products

Abstract

The invention relates to medical aids, in particular compression products, such as compression stockings or bandages. More specifically, the invention relates to compression products comprising fibre forming polyurethane polymers showing a delayed continuous relaxation behaviour. The invention furthermore relates to polyurethane polymers containing N-diol and corresponding quaternised polyurethane polymers, to a process of producing the polyurethane polymers, to blends with elastane, as well as to uses.

Claims

1. A compression product comprising an elastic component or material, the elastic component or material having a delayed continuous relaxation behavior, the elastic material being capable of applying a compression or a supporting force or a local pressure to a part of the body of a subject, the elastic material furthermore being capable of passing through a first phase during which the material is expanded, a second phase during which the component or material relaxes without recovering its original shape, and a third phase during which the component or material recovers its original shape with successive deceleration, wherein relaxation is self-initiated in the absence of an external stimulus, wherein the relaxation behavior is delayed in time as compared to an elastic component or material not containing N-diol, wherein the elastic component or material comprises: (a) a non-quaternized polyurethane (PU) polymer containing N-diol (PU-N); and/or (b) a quaternized polyurethane (PU) polymer or ionomer containing quaternized N-diol (PU-N+); and, optionally, (c) elastane.

2. The compression product according to claim 1, which is selected from the group consisting of a compression hosiery, a compression stocking, sock, knee sock, tights, panty hose, maternity panty hose, a compression knee guard, a compression arm sleeve, a compression waist attachment, belt or girdle, a compression bandage, a body-supporting bandage, an orthosis, a prosthesis liner, a compression wound dressing, a compression plaster or patch, and a compression garment.

3. The compression product according to claim 1, comprising an elastic component or material comprising a non-quaternized PU polymer and, optionally, elastane.

4. A method of providing compression to a subject in need of such compression, wherein said method comprises applying to a body part of the subject a compression product according to claim 1 in a field of phlebology, orthopaedics, foot care, surgery, post-surgery care, trauma management, wound care, or sports; or for treatment or prevention or management of impaired musco-venous pump performance, compromised venous circulation, venous insufficiency, oedema, phlebitis, thrombosis, venous embolism, lymphoedema, ulcer, aching legs, varicose veins, spider veins, or the “economy class syndrome” (ECS).

5. A polyurethane (PU) polymer having a delayed continuous relaxation behavior, wherein relaxation is initiated autonomously or spontaneously in the absence of an external stimulus, wherein the PU polymer contains at least one N-diol monomer component, and wherein the relaxation behavior is delayed in time as compared to a PU polymer not containing N-diol.

6. The polyurethane (PU) polymer according to claim 5, which is a non-quaternized PU polymer (PU-N).

7. The polyurethane (PU) polymer according to claim 5, which is a quaternized PU polymer (PU-N+) or a quaternized PU ionomer (PU-N+).

8. The polyurethane (PU) polymer according to claim 5, wherein the N-diol monomer component is derived from bis(2-hydroxyethyl)-3,3′-((2-(dimethylamino)ethyl)azanediyl)-dipropionate or N′,N′-bis(3-(2-hydroxyethoxy)-3-oxopropyl)-N,N-dimethylethylendiamine.

9. The polyurethane (PU) polymer according to claim 5, comprising a first molecular unit consisting of a N-diol monomer component and an isocyanate monomer component, a second molecular unit consisting of a 1,4-butanediol monomer component and an isocyanate monomer component, and a third molecular unit consisting of a P(THF) monomer component and an isocyanate component.

10. The polyurethane (PU) polymer according to claim 9, the relative amounts of N-diol, P(THF) and 1,4-butanediol monomer components being about 50:25:25%.

11. The polyurethane (PU) polymer according to claim 7, wherein the quaternized PU polymer or ionomer comprises an amount of quaternized N-containing groups of up to about 15% of ionic groups, related to the total moles of the PU polymer.

12. The polyurethane (PU) polymer according to claim 5, having a glass transition temperature T.sub.g of between about 20 and 60° C.

13. A blend comprising: (a) a non-quaternized polyurethane (PU) polymer containing N-diol (PU-N) having a delayed continuous relaxation behavior, wherein the relaxation behavior is delayed in time as compared to a PU polymer not containing N-diol; and/or (b) a quaternized polyurethane (PU) polymer or ionomer containing quaternized N-diol (PU-N+) having a delayed continuous relaxation behavior, wherein the relaxation behavior is delayed in time as compared to a PU polymer not containing N-diol; and (c) elastane.

14. The blend according to claim 13, comprising between about 5 and 40% (by weight) non-quaternized PU polymer, and between about 60 and 95% (by weight) elastane.

15. A method for producing a compression product; an elastic component or material; an elastic fibre, filament, thread, or yarn; or a compressive base fabric; wherein said method comprises the use of a polyurethane (PU) polymer having a delayed continuous relaxation behavior, wherein relaxation is initiated autonomously or spontaneously in the absence of an external stimulus or the use of a blend according to claim 13.

16. A process for producing a polyurethane (PU) polymer containing N-diol, the PU polymer containing at least one N-diol monomer component, the PU polymer having a delayed continuous relaxation behavior, wherein the relaxation behavior is delayed in time as compared to a PU polymer not containing N-diol, the process comprising the steps of: (i) Preparation of a quaternizable N-diol; (ii) Preparation of a PU polymer containing the quaternizable N-diol as produced in step (i); and, optionally, (iii) Quaternization of the PU polymer produced in step (ii).

17. The process according to claim 16, wherein the N-diol monomer component is derived from bis(2-hydroxyethyl)-3,3′-((2-(dimethylamino)ethyl)azanediyl)-dipropionate or N′,N′-bis(3-(2-hydroxyethoxy)-3-oxopropyl)-N,N-dimethylethylendiamine.

18. A polyurethane (PU) polymer containing N-diol produced in accordance with the process according to claim 16, wherein the PU polymer has a delayed continuous relaxation behavior, wherein the relaxation behavior is delayed in time as compared to a PU polymer not containing N-diol.

Description

(1) Below, the invention will be illustrated further by means of the following examples taking into account the accompanying figures, in which:

(2) FIG. 1 shows diagrams (A) and (B) illustrating a phase of active elongation (1), a phase of immediate relaxation (2), and a phase of successive compression (3), which a polyurethane (PU) polymer containing N-diol (PU-N or PU-N+) passes through in the course of elongation—relaxation, and eventually recovery of original shape.

(3) FIG. 2 shows phases (1) to (3) (see FIG. 1) in relation to an application procedure by a user (here: donning/doffing a compression stocking).

(4) FIG. 3 illustrates the relaxation behaviour of (A) elastane and (B) a conventional polyurethane polymer not containing N-diol (50% P(THF), 50% BD).

(5) FIG. 4 shows a reaction scheme illustrating the chemical synthesis of a N-diol from 2-dimethylaminoethylamine (DMAE) and 2-hydroxyethylacrylate (HEA).

(6) FIG. 5 shows a reaction scheme illustrating the chemical synthesis of PU-N from N-diol, 1,4-butanediol (BD), poly(tetrahydrofuran) (P(THF)), and methylene diisocyanate (MDI).

(7) FIG. 6 shows a reaction scheme illustrating the quaternisation of PU-N using 1-bromobutane, resulting in the production of PU-N+.

(8) FIG. 7 shows the analysis by GPC (eluent: THF) of samples of PU-N+ composed of different ratios of monomers.

(9) FIG. 8 shows the analysis by TGA (25-800° C., 10 K/min, N.sub.2) of samples of PU-N+ composed of different ratios of monomers.

(10) FIG. 9 shows the analysis by GPC (eluent: THF) of samples of PU-N+ produced by different sequences of addition of monomers.

(11) FIG. 10 shows the analysis by TGA (25-800° C., to K/min, N.sub.2) of samples of PU-N produced by different sequences of addition of monomers.

(12) FIG. 11 illustrates the principle of quaternisation of the alkylamino group contained in PU-N+.

(13) FIG. 12 shows the analysis by TGA (25-800° C., 10o K/min, air) of samples of PU-N and PU-N+.

(14) FIG. 13 shows analyses by DMTA of elastane (A), PU-N(B), (D), and PU-N+ (C), (E). E′ [Pa]=dynamic modulus, tan δ=mechanic loss factor, T.sub.g=glass transition temperature.

(15) FIG. 14 shows results from stress-strain tests with elastane (A) or PU-N+ (B).

(16) FIG. 15 shows results from stress-strain tests with elastane (A) or PU-N+ blended with 30% elastane (B).

(17) FIG. 16 illustrates the relaxation behaviour of PU-N(A) and PU-N+ (B-D) having a quaternization degree of 29% (B), 9% (C), or 5% (D).

(18) FIG. 17 shows a microscopic image (500× magnification) of α PU-N+ (i. e. quarternized polymer) spun into a filament that has been powdered with a suitable powder, e. g. SiO.sub.2, to prevent sticking to the filament.

(19) FIG. 18 shows results from stress-strain-tests with filaments of PU-N+.

(20) FIG. 19 illustrates the relaxation behaviour of PU-N+ filaments

EXAMPLES

(21) Briefly, Examples 1 and 2 relate to the preparation of N-diol containing PU polymer, Example 5 relates to the preparation of corresponding quaternised PU polymer. Generally, the preparation processes described, i.e. developed on a laboratory scale, are suitable for being processed to industrial-scale.

(22) Examples 3 and 4 describe the characterisation of N-diol containing PU polymers in regard to molecular mass and decomposition temperature; Example 6 describes the characterisation of quaternised PU polymers.

(23) Examples 7 and 8 make comparisons of N-diol containing PU polymers and elastane in regard to glass transition temperature (T.sub.g) and tensile strength (modulus of elasticity, fracture strain).

(24) Example 9 relates to blends of N-diol containing PU polymers and elastane, and describes their tensile strengths.

(25) Examples 10 and 11 describe the relaxation behaviour of N-diol-containing PU polymers and of blends with elastane, respectively.

(26) In Table 16, characterising features of exemplary polymer samples described and discussed in some of the examples below, are summarized.

Example 1: Preparation of N-Diol

(27) Chemicals

(28) N,N-Dimethylethylendiamine (DMEA): CAS: 108-00-9, Acros, distilled before use; 2-hydroxyethylacrylate (HEA): CAS: 818-61-1, TCI, >95%; THF: technical grade, dried and distilled before use; Et.sub.2O: technical grade, dried and distilled before use.

(29) TABLE-US-00001 Chemical M [g .Math. mol.sup.−1] n [mol] M [g] D [g .Math. cm.sup.−3] V [ml] eq. DMEA 88.15 0.594 48.42 0.807 60 1 HEA 116.12 1.099 127.57 1.106 115.3 2 THF 72.11 1.23 88.9 0.889 100 2.1
Procedure

(30) 115.3 ml (1.099 mol) HEA and 100 ml THF were taken in a 500 ml 3-neck-round-bottom flask under inert gas (argon) at room temperature (20±2° C.). 60 ml (0.594 mol) DMEA was added to this solution drop-wise. The mixture was stirred at 45° C. in an oil bath for 24 h. After this time, the solvent was removed and the left over (yellowish liquid) was extracted with Et.sub.2O (4×100 ml Et.sub.2O, product is not soluble in Et.sub.2O). The product was dried in vacuum at 50° C. Yield: 132 g, 75%.

(31) The product was characterised by 1H-NMR spectroscopy.

(32) A reaction scheme is shown in FIG. 4.

Example 2: Preparation of Polyurethane (PU) Polymer Containing N-Diol (PU-N)

(33) Chemicals

(34) 1,4-Butanediol (BD): CAS: 110-63-4, distilled before use; Poly(THF) 1000: CAS: 25190-60-1, M.sub.n (number average molar mass)=1,000 g/mol, Merck; 4,4′-diphenylmethanediisocyanate (MDI): CAS: 101-68-8, >97%, TCI; dibutyltin dilaurate (DBTL): CAS: 77-58-7, Sigma-Aldrich;

(35) THF: technical grade, dried and distilled before use.

(36) Reaction 1:

(37) TABLE-US-00002 Chemicals M [g .Math. mol.sup.1] n [mol] M [g] D [g .Math. cm.sup.−3] V [ml] eq. N-Diol (as 320.19 0.00448 1.435 0.5 synthesized in Example 1) Poly(THF) 1,000 0.00896 8.96 1 1000 BD 90.12 0.00448 0.404 1.02 0.396 0.5 MDI 250.25 0.01874 4.69 1.05 2.08 DBTL 631.56 1.22 .Math. 10.sup.−4 0.077 1.066 0.0726 0.5 wt % THF 72.11 0.247 17.78 0.889 20 27.5
Reaction 2:

(38) TABLE-US-00003 Chemicals M [g .Math. mol.sup.−1] n [mol] M [g] D [g .Math. cm.sup.−3] V [ml] eq. Diol 320.19 0.00896 2.87 1 (PH16N-6) Poly(THF) 1,000 0.00448 4.48 0.5 1000 BD 90.12 0.00448 0.404 1.02 0.396 0.5 MDI 250.25 0.01874 4.69 1.05 2.08 DBTL 631.56 0.985 .Math. 10.sup.−4 0.06 1.066 0.0563 0.5 wt% abs. THF 72.11 0.247 17.78 0.889 20 27.5

(39) TABLE-US-00004 Chemicals M [g .Math. mol.sup.−1] n [mol] M [g] D [g .Math. cm.sup.−3] V [ml] eq. Diol 320.19 0.00448 1.435 0.5 (PH16N-6) Poly(THF) 1000 0.00448 448 0.5 1000 BD 90.12 0.00896 0.808 1.02 0.792 1 MDI 250.25 0.01874 4.69 1.05 2.08 DBTL 631.56 0.903 .Math. 10.sup.−4 0.057 1.066 0.0535 0.5 wt% abs. THF 72.11 0.247 17.78 0.889 20 27.5
Procedure

(40) MDI and DBTL were mixed with 20 ml dried THF in 100 ml nitrogen flask under argon. The solution was cooled in an ice bath. N-Diol und BD were added dropwise to this cooled solution within 10 min. After addition was finished, the mixture was stirred for 30 min at room temperature. After this, poly(THF) was added dropwise and stirred for further 1 h. Afterwards, the reaction contents were heated at 50° C. (oil bath temperature) for 2 h. Afterwards, the polymer formed was precipitated in MeOH and dried at 50° C. in vacuum. Yield: 89%.

(41) A reaction scheme is shown in FIG. 5.

Example 3: Comparison of Different Ratios of Monomers

(42) PU-N synthesis as described in Example 2 was carried out based on ratios of monomers given in Table 1 below.

(43) TABLE-US-00005 TABLE 1 Sample N-Diol/eq. P(THF)/eq. BD/eq. MDI/eq. PH18N-6 1 0 0 1.04 (Comp. sample) PH21N-6 1 0 1 2.08 (Comp. sample) PH15D-6 0 1 1 2.08 (Comp. sample) PH23N-6 0.5 1 0.5 2.08 PH24N-6 1 0.5 0.5 2.08 PH18J-7 0.5 0.5 1 2.08 eq. = equivalent

(44) Samples containing the PU-N product were analysed by GPC (FIG. 7) and TGA (FIG. 8).

(45) Gel permeation chromatography (GPC) was used for molar mass determination (instrument: Agilent Technologies 1200 Series/1260 Infinity; column 1: PSS SDV 5 μm 100000; column 2: PSS SDV 5 μm 10000; column 3: PSS SDV 5 μm 1000; column 4: PSS SDV 5 μm 100; detector 1: Waters 486 UV; detector 2: Techlab Shodex RI; eluent: THF; flow rate: 1.0 ml/min; column temperature: 40° C.; calibration standard: polystyrene).

(46) Thermogravimetric analysis (TGA) was used to determine the thermal stability. A Netzsch TG 209 F1 Libra was used. Samples were heated from 25 to 800° C. in Al.sub.2O.sub.3-pans. Ca. 5-10 mg polymers were measured with a balance and put in a sample-pan. Whole measurement was done under air with a heating rate of 10° C./min. The temperature at which the weight loss started is mentioned as degradation temperature.

(47) As shown in FIG. 7, the molecular mass of PU contained in comparison samples PH18N-6 (100% N-diol) and PH21N-6 (50% N-diol, 50% BD) turned out to be too low. The highest molecular mass was shown by comparison sample PH15D-6 (50% P(THF), 50% BD).

(48) Amongst PU-N samples PH24N-6 (50% N-diol, 25% P(THF), 25% BD), PH23N-6 (25% N-diol, 50% P(THF), 25% BD), and PH18J-7 (25% N-diol, 25% P(THF), 50% BD), the molecular mass increased with the amount of P(THF) and BD.

(49) The results to be seen from FIG. 7 are summarised in Table 2 below.

(50) TABLE-US-00006 TABLE 2 Sample Mn [g/mol] D PH18N-6 3.3 .Math. 10.sup.3 1.4 PH21N-6 5.7 .Math. 10.sup.3 1.9 PH15D-6 7.5 .Math. 10.sup.4 1.8 PH23N-6 2.3 .Math. 10.sup.3 2.1 PH24N-6 1.6 .Math. 10.sup.3 2.2 PH18J-7 3.1 .Math. 10.sup.3 2.0 Mn = molar mass; D = molecular mass [Da]

(51) As shown in FIG. 8, an increased amount of P(THF) or BD resulted in a higher decomposition temperature.

(52) The results to be seen from FIG. 8 are summarised in Table 3 below.

(53) TABLE-US-00007 TABLE 3 Sample 5% decomposed [° C.] PH18N-6 199 PH21N-6 219 PH15D-6 307 PH23N-6 278 PH24N-6 213 PH18J-7 246

Example 4: Comparison of Different Sequences of Addition of Monomers

(54) PU-N synthesis as described in Example 2 was carried out by adding first N-diol+P(THF) and subsequently BD (option 1), or by adding first N-diol+BD and subsequently P(THF) (option 2).

(55) Option 1: PH23N-6, PH24N-6, PH18J-7

(56) (i) MDI+DBTL in abs. THF, cooling down on ice (ii) Adding N-diol+P(THF) (in drops), stirring 30 min at room temperature (iii) Adding BD (in drops)
Option 2: PH12D-6, PH16J-7, PH17J-7 (i) MDI+DBTL in abs. THF, cooling down on ice (ii) Adding N-diol+BD (in drops), stirring 30 min at room temperature (iii) Adding P(THF) (in drops)

(57) The ratios of monomers were as given in Table 4 below.

(58) TABLE-US-00008 TABLE 4 Sample N-Diol/eq. P(THF)/eq. BD/eq. MDI/eq. PH23N-6 0.5 1 0.5 2.08 PH12D-6 PH24N-6 1 0.5 0.5 2.08 PH16J-7 PH18J-7 0.5 0.5 1 2.08 PH17J-7

(59) Samples containing the PU-N product were analysed by GPC (FIG. 9) and TGA (FIG. 10).

(60) As shown in FIG. 9, addition of P(THF) after BD (option 2) resulted in a higher molar mass.

(61) The results to be seen from FIG. 9 are summarised in Table 5 below.

(62) TABLE-US-00009 TABLE 5 Sample Mn [g/mol] D PH23N-6 2.3 .Math. 10.sup.4 2.1 PH12D-6 4.3 .Math. 10.sup.4 2.1 PH24N-6 1.6 .Math. 10.sup.4 2.2 PH16J-7 3.1 .Math. 10.sup.4 1.7 PH18J-7 3.1 .Math. 10.sup.4 2.0 PH17J-7 4.0 .Math. 10.sup.4 1.6 Mn = molar mass; D = molecular mass [Da]

(63) As to be seen from FIG. 10, the sequence of addition of monomers virtually showed no effect on the decomposition temperature.

(64) The results to be seen from FIG. 10 are summarised in Table 6 below.

(65) TABLE-US-00010 TABLE 6 Sample 5% Decomposition [° C.] PH23N-6 278 PH12D-6 271 PH24N-6 213 PH16J-7 221 PH18J-7 246 PH17J-7 251

Example 5: Quaternisation of the N-Diol Containing PU Polymer

(66) Chemicals

(67) PU-N(as produced in Example 2); 1-bromobutane: CAS. 105-65-9, Merck, >98%; THF: technical grade, distilled before use.

(68) Reaction

(69) TABLE-US-00011 M [g .Math. n D [g .Math. Chemicals mol.sup.−1] [mol] M [g] cm.sup.−3] V [ml] PU-N 10 1-Bromobutane 137.03 0.047 6.4 1.28 5 THF 72.11 0.889 30
Procedure

(70) 10 g PU-N was dissolved in 30 ml THF at 60° C. 5 ml 1-bromobutane was added. The reaction mixture was stirred at 60° C. for different time intervals to change the degree of quaternisation. The quaternised polymer was precipitated in hexane and dried at 50° C. in vacuum. Yield: 96%.

(71) The product PU-N+ was characterised by 1H-NMR spectroscopy.

(72) A reaction scheme is shown in FIG. 6, and FIG. 11 further illustrates the principle of quaternisation.

(73) The extent of quaternisation is exemplarily summarized in Table 7 below.

(74) TABLE-US-00012 TABLE 7 Quaternisation Sample PU [%] PH06M-7_ PH16J-7_PU 29 PU-N+_24 h (50% N-diol, 25% P(THF), 25% BD) PH07M-7_ PH17J_PU 16 PU-N+_24 h (25% N-diol, 25% P(THF), 50% BD) PH07F-8_PU-N+ (50% N-diol, 25% P(THF), 25% BD 5

Example 6: Characterization of the Quaternised PU Polymer (PU-N+)

(75) Samples containing non-quaternised or quaternised PU polymer (i.e. PU-N or PU-N+) were analysed by TGA (FIG. 12). As shown, quaternisation did not affect the decomposition temperature.

(76) The results to be seen from FIG. 12 are summarised in Table 8 below.

(77) TABLE-US-00013 TABLE 8 Sample 5% Decomposition [° C.] PH16J-7_PU 221 (50% N-diol, 25% P(THF), 25% BD) PH06M-7_PU-N+_24 h 224 (29% quarternized) PH17J-7_PU 251 (25% N-diol, 25% P(THF), 50% BD) PH07M-7_PU-N+_24 h 246 (16% quaternised)

Example 7: Dynamic-Mechanical Thermoanalysis (DMTA)

(78) Samples containing non-quaternised PU or quaternised PU polymer (i.e. PU-N or PU-N+) were analysed by DMTA; elastane served for comparison (FIG. 13).

(79) For DMTA, a Rheometric Scientific DMTA instrument was used.

(80) In contrast to elastane (FIG. 13A), the PU polymer samples showed glass transition temperatures (T.sub.g) of above 0° C., regardless of whether they were quaternised or not.

(81) As furthermore shown, an increased amount of BD resulted in a higher glass transition temperature (FIG. 13B: T.sub.g=40° C.; FIG. 13D: T.sub.g=55° C.).

(82) Finally, quaternisation of PU-N(resulting in PU-N+) induced an increase in the glass transition temperatures observed with the non-quaternised PU-N(FIG. 13C: T.sub.g1=70° C., i.e. >40° C.; FIG. 13E: T.sub.g1=70° C., i.e. >55° C.).

Example 8: Stress-Strain Test

(83) Mechanical properties of the produced PU polymers were tested. For that purpose, samples of non-quaternised PU or quaternised PU polymer (i.e. PU-N or PU-N+) were analysed by a strain-stress test (tensile testing); elastane served for comparison.

(84) For testing, a Zwick/Noell BT1-FR 0.5TN.D14 machine was used (pre-load: 0.01 N/mm test rate: 50 mm/min). Sample preparation: 1 g PU (PU-N or PU-N+) was dissolved in to ml HFIP (hexafluoroisopropanol) and dropped on a glass plate for making a film. The film was dried at room temperature for 24 h followed by drying at 45° C. in vacuum for 24 h. The films were cut to the dimensions (W: 5 mm, L: ≥40 mm) for mechanical testing.

(85) As shown in FIG. 14, PU-N+ (FIG. 14B) showed a strain behaviour different from that of elastane (FIG. 14A).

(86) Furthermore, quaternisation induced a decrease in fracture strain, as shown in Table 9 below.

(87) TABLE-US-00014 TABLE 9 E.sub.mod Fracture strain Sample [MPa] dL [%] Ratio of monomers Elastane 2.4 3,403 PH15D-6_PU 12.5 1,566 50% P(THF), 50% BD PH16J-7_PU 37 1,388 50% N-Diol, 25% P(THF), 25% BD PH06M-7_ 154 796 50% N-Diol, 25% P(THF), PU-N.sup.+ 25% BD 29% quaternisation PH17J-7_PU 95 1,025 25% N-Diol, 25% P(THF), 50% BD PH07M-7_ 98 780 25% N-Diol, 25% P(THF), PU-N.sup.+ 50% BD 16% quaternisation E.sub.mod = modulus of elasticity; dL = delta length; % = weight %; film thickness: 180 ± 20 μm

Example 9: PU Polymer/Elastane Blends

(88) The produced PU polymers were blended with elastane (commercially available). Mechanical properties were tested using a strain-stress test as described in Example 8.

(89) As shown in FIG. 15, a blend of 70% PU-N+ and 30% elastane (FIG. 15B) showed a strain behaviour different from that of elastane (FIG. 15A).

(90) Furthermore, fracture strain and modulus of elasticity measured with different PU-N+/elastane blends are given in Table 10 below.

(91) TABLE-US-00015 TABLE 10 E.sub.mod Fracture strain Sample [MPa] dL [%] Ratio of monomers Elastane 2.4 3,403 PH06M-7_PU-N.sup.+ 154 796 50% N-Diol, 25% P(THF), 25% BD 29% quaternised PH07M-7_PU-N.sup.+ 98 780 25% N-Diol, 25% P(THF), 50% BD 29% quaternised Blend_10% 3.4 3,044 10% PH06M-7_PU-N.sup.+ + PH06M-7_PU-N.sup.+ 90% elastane Blend_30% 7.1 2,413 30% PH06M-7_PU-N.sup.+ + PH06M-7_PU-N.sup.+ 70% elastane Blend_50% 15 1,601 50% PH06M-7_PU-N.sup.+ + PH06M-7_PU-N.sup.+ 50 elastane Blend_70% 31 1,097 70% PH06M-7_PU-N.sup.+ + PH06M-7_PU-N.sup.+ 30% elastane Blend_10% 3.4 3,060 10% PH07M-7_PU-N.sup.+ + PH07M-7_PU-N.sup.+ 90% elastane Blend_30% 6 2,331 30% PH07M-7_PU-N.sup.+ + PH07M-7_PU-N.sup.+ 70% elastane Blend 50% 14 1,710 50% PH07M-7_PU-N.sup.+ + PH07M-7_PU-N.sup.+ 50% elastane Blend 70% 39 1,301 70% PH07M-7_PU-N.sup.+ + PH07M-7_PU-N.sup.+ 30% elastane E.sub.mod = modulus of elasticity; dL= delta length; % = weight%; film thickness: 160 ± 20 μm

(92) For comparison, fracture strain and modulus of elasticity measured with different PU-N(i.e. non-quaternised)/elastane blends are given in Table 11 below.

(93) TABLE-US-00016 TABLE 11 Fracture E.sub.mod strain Sample [MPa] dL [%] Ratio of monomers PH02M-7_PU 50% N-Diol, 25% P(THF), 25% BD Blend_10% 3.7 3,262 10% PH02M-7_PU + PH02M-7_PU 90% elastane Blend_30% 5.2 2,900 30% PH02M-7_PU + PH02M-7_PU 70% elastane Blend_50% 5.5 2,325 50% PH02M-7_PU-N + PH02M-7_PU 50% elastane Blend_70% 6.8 2,492 70% PH02M-7_PU-N + PH02M-7_PU 30% elastane Blend_90% 8.8 1,544 90% PH02M-7_PU-N + PH02M-7_PU 10% elastane E.sub.mod = modulus of elasticity; delta length; % = weight %; film thickness: 140 ± 10 μm

Example 10: Relaxation Behaviour

(94) A sample of non-quaternised PU (PU-N) or of corresponding quaternised PU (PU-N+), 29% quaternisation, was stretched from 10 mm (original sample length) to 40 mm (FIGS. 16A, 16B). Upon release, both samples recovered their original sample lengths in about 6 hours. In doing so, approximately 180% recovery was achieved in about 5 min, after which the remaining 120% was recovered much more slowly. In this respect, the relaxation behaviour of PU-N and PU-N+ was almost the same.

(95) Similarly, samples of PU-N+ having different degrees of quaternisation, namely 9% or 5%, were stretched from 10 mm to 50 mm (FIGS. 16C, 16D). Upon release, 300% and 280% of the original sample length was recovered immediately, and further 140% and 160% was recovered after 5 min, respectively. Thus, approximately 90% total recovery was achieved within about 5 min.

(96) Thus, the relaxation behaviour depends, at least partially, on the degree of quaternisation.

(97) The results to be seen from FIG. 16 are summarized in Table 12 below.

(98) TABLE-US-00017 TABLE 12 Immediate Relaxation 1 Relaxation 2 Ratio of Sample relax. [%] [%/time] [%/time] monomers PH16J-7_PU 100 80/5 min 120/6 h 50% N-diol, 25% P(THF), 25% BD PH06M-7_PU- 80 100/5 min 120/6 h 50% N-diol, 25% N+ P(THF), 25% BD (derived from 29% PH16J-7_PU quaternisation PH23M-7_PU- 300 140/5 min 60/60 min 50% N-diol, 25% N+ P(THF), 25% BD (derived from 9% PH02M-7_PU) quaternisation PH30M-7_PU- 280 160/5 min 60/6o mm 50% N-diol, 25% N+ P(THF), 25% BD (derived from 5% PH02M-7_PU) quaternisation

Example 11: Relaxation Behaviour of PU Polymer/Elastane Blends

(99) Non-quaternised PU (PU-N) or corresponding quaternised PU (PU-N+) having different degrees of quaternisation (29%, 9% or 5%) were blended with elastane (commercially available), respectively. Samples were subjected to stretching-and-release similar to the description in Example 10 (stretching of samples from 10 to 50 mm).

(100) The results are summarized in Tables 13 to 15 below.

(101) TABLE-US-00018 TABLE 13 Blends of PU-N (PH02M-7_PU; 50% N-diol, 25% P(THF), 25% BD) and elastane. Immediate PU-N Elastane relaxation Relaxation 1 Relaxation 2 [wt %] [wt %] [%] [%/time] [%/time] 10 90 450 30/5 min 20/10-20 min 30 70 430 40/5 min 30/10-20 min 50 50 420 50/5 min 30/2 h 70 30 410 60/5 min 30/3 h 90 10 390 80/5 min 30/6 h

(102) Firstly, admixture of elastane to PU-N altered the relaxation behaviour of the individual PU-N and of elastane.

(103) As to be seen from Table 13, the blends showed approximately 80 to 90% total recovery immediately after release, depending on the relative amounts of PU-N and elastane. Recovery of the remaining 10 to 20% took about 15 min to 6 hours, also depending on the relative amounts of PU-N and elastane. More generally, increased relative amounts of PU-N resulted in an increase in total relaxation time.

(104) TABLE-US-00019 TABLE 14 Blends of PU-N+, 29% quaternisation (PH06M-7_PU-N+; 50% N-diol, 25% P(THF), 25% BD) and elastane. Immediate PU-N+ Elastane relaxation Relaxation 1 Relaxation 2 [wt %] [wt %] [%] [%/time] [%/time] 10 90 440 20/5 min 40/30-60 min 30 70 400 40/5 min 60/2 h 50 50 340 100/5 mm 60/3 h 70 30 280 120/5 min 100/6 h

(105) As to be seen from Table 14, increased relative amounts of PU-N+ resulted in an increase of total relaxation time. Furthermore, compared to non-quaternised PU-N (Table 13), PU-N+ was associated with increased total relaxation times. Apart from that, PU-N+ with a high degree of quaternisation (29%) does not provide any particular advantage over non-quaternised PU-N when used in blends with elastane.

(106) TABLE-US-00020 TABLE 15 Blends of PU-N+, 9% quaternisation (PH23M-7_PU-N+; 50% N-diol, 25% P(THF), 25% BD) and elastane. Immediate PU-N+ Elastane relaxation Relaxation 1 Relaxation 2 [wt %] [wt %] [%] [%/time] [%/time] 50 50 390 80/5 min 30/30-60 min 60 40 350 100/5 min 50/30-60 min 70 30 380 90/5 min 30/30-60 min

(107) As to be seen from Table 15, blends with PU-N+ having a lower degree of quaternisation (here: 9%) showed relaxation times of about 30 min to 1 h for all tested compositions. Apart from that, the relaxation behaviour is very similar to that of blends with non-quaternised PU-N, i.e. approximately 80% total recovery was achieved immediately.

(108) TABLE-US-00021 TABLE 16 Blends of PU-N+, 5% quaternisation (PH30M-7_PU-N+; 50% N-diol, 25% P(THF), 25% BD) and elastane. Immediate PU-N+ Elastane relaxation Relaxation 1 Relaxation 2 [wt %] [wt %] [%] [%/time] [%/time] 50 50 390 70/5 min 40/30-60 min 60 40 380 80/5 min 40/30-60 min 70 30 380 80/5 min 40/30-6o min

(109) As to be seen from Table 16, the relaxation behaviour of blends with PU-N+ having a low degree of quaternisation (here: 5%) is very similar to that of blends with PU-N+, 9% quaternisation (Table 15), and of non-quaternised PU-N (Table 13).

(110) TABLE-US-00022 TABLE 17 Number T.sub.g or T.sub.g1/T.sub.g2, Degradation dL [%] N- Degree of average [° C.] temperature (pre-load: 0.01 Diol:P(THF):BD quaternisation molar mass (from [° C.] E.sub.mod N/mm; speed: Sample (molar ratio) [%] Mn [g/mol] DMTA) (from TGA) [MPa] σ.sub.M [MPa] 50 mm/min) Elastan 0 7.54 .Math. 10.sup.4 −50 243 2.4 27 3,403 PH15D−6_PU 0:1:1 0 3.06 .Math. 10.sup.4 −25 230 12.5 33 1,566 PH16J−7_PU 1:0.5:0.5 0 40 185 37 35 1,388 PH06M−7_PU-N + 1:0.5:0.5 24 h/29% 40/70 182 154 42 796 (derived from PH16J−7_PU) PH23M−7_PU-N + 1:0.5:0.5 90 min/9% 29 12 968 (derived from PH02M−7_PU) PH30M−7_PU-N + 1:0.5:0.5 45 min/5% 12 11 1,056 (derived from PH02M−7_PU) Blend_30% 4 19 3,082 PH16J−7_PU + 70% elastane Blend_50% 4.9 19 2,629 PH16J−7_PU + 50% elastane Blend_70% 5.9 16 2,412 PH16J−7_PU + 30% elastane Blend_10% 3.7 28 3,262 PH02M−7_PU + 90% elastane Blend_30% 5.2 28 2,900 PH02M−7_PU + 70% elastane Blend_50% 5.5 20 2,325 PH02M−7_PU + 50% elastane Blend_70% 6.8 21 2,492 PH02M−7_PU + 30% elastane Blend_90% 8.8 16 1,544 PH02M−7_PU + 10% elastane Blend_50% 6.3 15 1,896 PH23M−7_PU-N + 50% elastane Blend_60% 9.9 18 2,067 PH23M−7_PU-N + 40% elastane Blend_70% 10.5 15 1,990 PH23M−7_PU-N + 30% elastane Blend_50% 6.2 14 1,800 PH30M−7_PU-N + 50% elastane Blend_60% 7.2 16 2,187 PH30M−7_PU-N + 40% elastane Blend_70% 8.8 13 1,951 PH30M−7_PU-N + 30% elastane

Example 12: Polymer Fibres/Filaments

(111) A sample of quaternised PU polymer (PU-N+) (PH07F-8_PU-N+=50% N-Diol, 25% P(THF)25% BD, 5% quaternised (5% N+)) was milled to a powder using an ultra-centrifugal mill ZM200. The milling machine had a sieve with pore diameter of 1 mm. Machine with any other pore diameter can also be used and sieve diameter is not important. Idea was to convert a mass of the polymer into a powder that can be easily fed to extruder for making filaments. Thereafter it was spun as a mono-filament using a twin screw extruder (process 11 from Thermo Scientific). The extruding filaments were continuingly passed through a trough having SiO2 powder to prevent any residual stickiness/tackiness of the filament and allowed storage of the filament, when it has been wound up into a roll without sticking to each other). Using this set up, the melt spinning of the PU ionomer into a mono-filament is easy, and a large scale production is possible.

(112) An exemplary microscopical image of such filament is shown in FIG. 17 (500× magnification). The filaments are not transparent and have an opaque surface.

(113) Mechanical properties of the spun filament were tested. For that purpose, the produced filament(s) were analyzed by a strain-stress test (tensile testing). For testing, a Zwick/Noell BT1FR0.5TN.D14 machine was as used. (Preload: 0.1 kPa, test rate: 50 mm/min). The filament had a diameter of 280+/−30 Gm, and the filament was subjected to tensile testing

(114) The following results were achieved:

(115) TABLE-US-00023 Fracture E.sub.mod/ strain dL F (max)/ Sample MPa [%] MPa Monomer ratio PH07F-8_PU- 2,5 1100 29 50% N-Diol, 25% P(THF), N.sup.+_filament_with 25% BD, 5% N.sup.+ SiO.sub.2_powder
E.sub.mod=modulus of elasticity; d.sub.L=delta length; %=weight percent; filament diameter=208+−30 μm

(116) The results of the strain-stress test are shown in FIG. 18.

(117) The relaxation behavior of such filaments are shown in FIG. 19. For such relaxation behavior, a filament of quaternised polyurethane polymer was stretched from 10 mm (original filament length) to 50 mm. Upon release, the filament recovered its original sample length in approximately 35-65 min.

(118) In summary, in this example, the inventors have shown that polyurethane-ionomer can be reproducibly spun into filaments the tackiness of which can be prevented by dusting with SiO.sub.2-powder or a similar powder or a suitable oil. The powder does not interfere with the relaxation behavior.