YELLOWING-RESISTANT THERMOPLASTIC POLYURETHANE FOAM MATERIAL AND PREPARATION METHOD THEREOF

Abstract

A yellowing-resistant thermoplastic polyurethane (TPU) foam material and a preparation method thereof are provided. The yellowing-resistant TPU foam material includes a TPU prepared by subjecting an aliphatic diisocyanate, a chain extender, a polyol, an antioxidant, an ultraviolet (UV) absorber, and a UV light stabilizer to a reaction, where the TPU has a softening point of 90° C. to 160° C., a Shore hardness of 40 A to 98 A, and a melt index of 5 to 250 g/10 min. The prepared yellowing-resistant TPU foam material has excellent yellowing resistance, controllable foaming density, and uniform foam cell size.

Claims

1. A yellowing-resistant thermoplastic polyurethane (TPU) foam material, comprising a TPU prepared by subjecting an aliphatic diisocyanate, a chain extender, a polyol, an antioxidant, an ultraviolet (UV) absorber, and a UV light stabilizer to a reaction, wherein the TPU has a softening point of 90° C. to 160° C., a Shore hardness of 40 A to 98 A, and a melt index of 5 g/10 min to 250 g/10 min.

2. The yellowing-resistant TPU foam material according to claim 1, wherein the aliphatic diisocyanate comprises one or more from the group consisting of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI) or hydrogenated diphenylmethane diisocyanate (H.sub.12MDI), cyclohexyl dimethylene diisocyanate (H.sub.6XDI), and cyclohexyl diisocyanate.

3. The yellowing-resistant TPU foam material according to claim 1, wherein the chain extender comprises one or more from the group consisting of 1,2-ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, and cyclohexanedimethanol (CHDM).

4. The yellowing-resistant TPU foam material according to claim 1, wherein an amount of the antioxidant is 0% to 0.3% of a total amount of the TPU, and the antioxidant is a hindered phenol antioxidant or a phosphite antioxidant; an amount of the UV absorber is 0.5% to 1.5% of the total amount of the TPU, and the UV absorber is a benzotriazole UV absorber, a formamidine UV absorber, a triazine UV absorber, or a benzophenone UV absorber; and an amount of the UV light stabilizer is 0.5% to 4% of the total amount of the TPU, and the UV light stabilizer is a hindered amine light stabilizer.

5. The yellowing-resistant TPU foam material according to claim 1, wherein the polyol comprises one or more from the group consisting of a polycarbonate polyol, a polyester polyol, and a polyether polyol with a functionality of 1.9 to 2.1.

6. A preparation method of a yellowing-resistant TPU foam material, comprising: subjecting a TPU to a physical foaming process to obtain the yellowing-resistant TPU foam material.

7. The preparation method of the yellowing-resistant TPU foam material according to claim 6, wherein the physical foaming process comprises: adding the TPU, a physical foaming agent, and water to a pressure-resistant vessel to obtain a resulting mixture, and stirring the resulting mixture to form a suspension; heating the suspension, and maintaining a pressure to be 10 bar to 250 bar; and discharging the suspension in the pressure-resistant vessel into an atmospheric environment to obtain the yellowing-resistant TPU foam material.

8. The preparation method of the yellowing-resistant TPU foam material according to claim 6, wherein the physical foaming process comprises: adding the TPU into an extruder for melting, injecting a physical foaming agent into the extruder to obtain a resulting mixture, and keeping the resulting mixture under a pressure of 20 bar to 300 bar; and extruding through a die to obtain the yellowing-resistant TPU foam material.

9. The preparation method of the yellowing-resistant TPU foam material according to claim 6, wherein the physical foaming process comprises: adding the TPU into a pressure-resistant vessel, and injecting a physical foaming agent into the pressure-resistant vessel to obtain a resulting mixture; allowing a pressure to reach 10 bar to 350 bar and keeping the resulting mixture under the pressure for 1 h to 48 h; and heating the resulting mixture to obtain the yellowing-resistant TPU foam material.

10. The preparation method of the yellowing-resistant TPU foam material according to claim 7, wherein the physical foaming agent comprises one or more from the group consisting of nitrogen, carbon dioxide, air, methane, propane, butane, and pentane.

11. The yellowing-resistant TPU foam material according to claim 1, wherein the yellowing-resistant TPU foam material is used in a field of flexible foams including shoe materials, floor coverings, transportation parts, and toys.

12. The preparation method of the yellowing-resistant TPU foam material according to claim 8, wherein the physical foaming agent comprises one or more from the group consisting of nitrogen, carbon dioxide, air, methane, propane, butane, and pentane.

13. The preparation method of the yellowing-resistant TPU foam material according to claim 9, wherein the physical foaming agent comprises one or more from the group consisting of nitrogen, carbon dioxide, air, methane, propane, butane, and pentane.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0031] The principles and features of the present disclosure will be described below, and the examples given are used merely to explain the present disclosure, rather than limit the scope of the present disclosure.

[0032] A yellowing-resistant TPU foam material is provided, including a TPU prepared by subjecting an aliphatic diisocyanate, a chain extender, a polyol, an antioxidant, a UV absorber, and a UV light stabilizer to a reaction.

[0033] Specifically, the TPU is prepared as follows: an aliphatic diisocyanate, a polyol with a molar mass of 500 g/mol to 10,000 g/mol, and a chain extender with a molar mass of 50 g/mol to 500 g/mol are mixed, and a resulting mixture is subjected to a reaction at 150° C. to 200° C. through a one-pot method or a prepolymer method in an extrusion reaction extruder to produce the TPU.

[0034] A modulation index of each component in the above reaction for preparing the TPU is 80 to 110, which is specifically a ratio of a mole number of isocyanate in the aliphatic diisocyanate to a mole number of groups in the chain extender and polyol that are reactive to isocyanate.

[0035] The TPU has a softening point of 90° C. to 160° C., which is determined by the Shimadzu CFT-500 series rheometer; a Shore hardness of 40 A to 98 A, which is determined by the Shore A durometer; and a melt index of 5 to 250 g/10 min, which is obtained by a 5 kg load test at 210° C. according to ASTM D1238. The foam material has a yellowing resistance grade of 4.5 to 5, which is obtained at a lamp irradiation intensity of 0.77 W/m.sup.2/nm of a 340 nm UVA lamp according to ASDM-D1148 or a 300 h irradiation test according to HG/T3689-2001A. According to ISO 105-A02: 1993, the yellowing resistance grade is assessed under the standard light source D65, where grade 5 means that a material undergoes no yellowing, grade 4.5 means that a material only undergoes slight yellowing, and grade 1 means that a material undergoes very severe yellowing.

[0036] Specifically, the aliphatic diisocyanate may be HDI, IPDI, XDI or hydrogenated phenylmethane diisocyanate (H.sub.12MDI), cyclohexyl dimethylene diisocyanate (H.sub.6XDI), and cyclohexyl diisocyanate.

[0037] The chain extender may include an aliphatic, aromatic, or alicyclic glycol compound with a molar mass of 50 g/mol to 500 g/mol; specifically, the chain extender may be 1,2-ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, or CHDM with 2 to 14 C atoms, or the chain extender may be 2-hydroxyethyl ether, m-phenylene glycol bis(hydroxyethyl)ether, or 1,4-dihydroxymethylcyclohexane; and preferably, the chain extender may be 1,4-butylene glycol.

[0038] An amount of the antioxidant may be preferably 0% to 0.3% and more preferably 0% to 0.1% of a total amount of the TPU, and the antioxidant may be a hindered phenol antioxidant or a phosphite antioxidant, specifically Irganox1010, Irganox1076, Irganox1098, Irganox3114, Irganox126, Irgafos168, or Irgafos 618 of BASF. An amount of the UV absorber may be preferably 0.5% to 1.5% and more preferably 0.8% to 1.5% of the total amount of the TPU, and the UV absorber may be a benzotriazole UV absorber, a formamidine UV absorber, a triazine UV absorber, or a benzophenone UV absorber, specifically TinuvinP, Tinuvin327, Tinuvin328, Tinuvin329, Tinuvin234, Tinuvin312, TinuvinUV-1, or TinuvinUV-3 of BASF. An amount of the UV light stabilizer may be preferably 0.5% to 4% and more preferably 1% to 3% of the total amount of the TPU, and the UV light stabilizer may be a hindered amine light stabilizer, specifically Tinuvin571, Tinuvin770, Tinuvin622, Tinuvin944, or Tinuvin144.

[0039] The polyol may include one from the group consisting of a polycarbonate polyol, a polyester polyol, and a polyether polyol with a functionality of 1.9 to 2.1, or a mixture of two or more therefrom, where the polyether polyol may have a molar mass of 800 g/mol to 1,200 g/mol and the polyether polyol may have a molar mass of 500 g/mol to 2,000 g/mol.

[0040] Preferably, the polyol may be a polyether polyol with a functionality of 2. Specifically, the polyether polyol may be poly(ethylene glycol adipate) (PEA), poly(diethylene glycol adipate) (PDA), poly(butylene glycol adipate) (PBA), poly(propylene glycol adipate) (PPA), polypropylene glycol (PPG), or poly(tetramethylene ether)glycol (PTMEG); and preferably a mixture of PBA and PTMEG.

Example 1

[0041] A preparation method of a yellowing-resistant TPU foam material included: 30 kg of HDI, 11 kg of 1,4-butylene glycol, 100 kg of a mixture of PBA and PTMEG in a mass ratio of 1:1, a hindered phenol antioxidant, a benzotriazole UV absorber, and a hindered amine light stabilizer were added into a twin-screw reaction extruder and subjected to a reaction at 150° C. to 180° C. to obtain a TPU, where the benzotriazole UV absorber was TinuvinP and added at a specific amount 0.5% of a total amount of the TPU; the hindered amine light stabilizer was Tinuvin571 and added at a specific amount 0.5% of the total amount of the TPU; and the TPU particles had a softening point of 90° C., a Shore hardness of 40 A, and a melt index of 250 g/10 min;

[0042] 100 parts by weight of the TPU, 30 parts by weight of butane, and 300 parts by weight of water were added to a 500 L high-pressure reactor and then stirred to form a suspension; the suspension was heated to 100° C. and kept at a pressure of 10 bar; and then the suspension in the high-pressure reactor was discharged into an atmospheric environment and dried to obtain yellowing-resistant TPU foam material particles, where the TPU foam material particles had a density of 0.05 g/cm.sup.3 and a foam cell size of 10 m to 40 m;

[0043] the TPU foam material particles obtained above were filled into a mold with a length of 300 mm, a width of 250 mm, and a thickness of 50 mm; and 2 bar water vapor was used to compress by 10% along a thickness direction of the mold for bonding and molding of the TPU foam material particles to finally obtain a molded foam product. The obtained foam product was placed at 50° C. and 50% RH (humidity) for 2 h, then dried in a constant-temperature room at 80° C. for 2 h, and finally placed at 25° C. and 50% RH for 2 h to evaluate its performance.

Example 2

[0044] A preparation method of a yellowing-resistant TPU foam material included: 70 kg of IPDI, 15 kg of 1,4-butylene glycol, 100 kg of PTMEG, a hindered phenol antioxidant, a benzotriazole UV absorber, and a hindered amine light stabilizer were added into a twin-screw extruder and subjected to a reaction at 150° C. to 200° C. to obtain a TPU, where the hindered phenol antioxidant was Irganox1010 and added at a specific amount 0.05% of a total amount of the TPU; the benzotriazole UV absorber was Tinuvin 327 and added at a specific amount 0.8% of the total amount of the TPU; the hindered amine light stabilizer was Tinuvin 770 and added at a specific amount 1% of the total amount of the TPU; and the TPU particles had a softening point of 160° C., a Shore hardness of 98 A, and a melt index of 5 g/10 min;

[0045] 100 parts by weight of the TPU, 60 parts by weight of carbon dioxide, and 500 parts by weight of water were added to a 1,200 L high-pressure reactor and then stirred to form a suspension; the suspension was heated to 130° C., a pressure was controlled at 100 bar, and the suspension was kept at the temperature and the pressure for 180 min; and then the suspension in the high-pressure reactor was discharged into an atmospheric environment and dried to obtain yellowing-resistant TPU foam material particles, where the TPU foam material particles had a density of 0.5 g/cm.sup.3 and a foam cell size of 70 m to 100 m;

[0046] the TPU foam material particles obtained above were filled into a mold with a length of 300 mm, a width of 250 mm, and a thickness of 50 mm; and 2 bar water vapor was used to compress by 10% along a thickness direction of the mold for bonding and molding of the TPU foam material particles to finally obtain a molded foam product. The obtained foam product was placed at 50° C. and 50% RH for 2 h, then dried in a constant-temperature room at 80° C. for 2 h, and finally placed at 25° C. and 50% RH for 2 h to evaluate its performance.

Example 3

[0047] A preparation method of a yellowing-resistant TPU foam material included: 51 kg of hydrogenated XDI, 12 kg of 1,4-butylene glycol, 100 kg of PBA, a hindered phenol antioxidant, a benzotriazole UV absorber, and a hindered amine light stabilizer were added into a twin-screw extruder and subjected to a reaction at 150° C. to 200° C. to obtain a TPU, where the hindered phenol antioxidant was Irganox1076 and added at a specific amount 0.1% of a total amount of the TPU; the benzotriazole UV absorber was Tinuvin312 and added at a specific amount 1% of the total amount of the TPU; the hindered amine light stabilizer was Tinuvin622 and added at a specific amount 2% of the total amount of the TPU; and the TPU particles had a softening point of 125° C., a Shore hardness of 85 A, and a melt index of 100 g/10 min;

[0048] 100 parts by weight of the TPU, 30 parts by weight of nitrogen, and 500 parts by weight of water were added to a 1,000 L high-pressure reactor and then stirred to form a suspension; the suspension was heated to 130° C., a pressure was controlled at 70 bar, and the suspension was kept at the temperature and the pressure for 70 min; and then the suspension in the high-pressure reactor was discharged into an atmospheric environment and dried to obtain yellowing-resistant TPU foam material particles, where the TPU foam material particles had a density of 0.15 g/cm.sup.3 and a foam cell size of 100 m to 120 m;

[0049] the TPU foam material particles obtained above were filled into a mold with a length of 300 mm, a width of 250 mm, and a thickness of 50 mm; and 2 bar water vapor was used to compress by 10% along a thickness direction of the mold for bonding and molding of the TPU foam material particles to finally obtain a molded foam product. The obtained foam product was placed at 50° C. and 50% RH for 2 h, then dried in a constant-temperature room at 80° C. for 2 h, and finally placed at 25° C. and 50% RH for 2 h to evaluate its performance.

Example 4

[0050] A preparation method of a yellowing-resistant TPU foam material included: 45 kg of hydrogenated diphenylmethane diisocyanate, 10 g of 1,4-butylene glycol, 100 kg of PTMEG, a hindered phenol antioxidant, a benzotriazole UV absorber, and a hindered amine light stabilizer were added into a twin-screw extruder and subjected to a reaction at 150° C. to 200° C. to obtain a TPU, where the hindered phenol antioxidant was Irganox1098 and added at a specific amount 0.1% of a total amount of the TPU; the benzotriazole UV absorber was TinuvinUV-1 and added at a specific amount 1.5% of the total amount of the TPU; the hindered amine light stabilizer was Tinuvin944 and added at a specific amount 3% of the total amount of the TPU; and the TPU particles had a softening point of 145° C., a Shore hardness of 80 A, and a melt index of 50 g/10 mm;

[0051] 100 parts by weight of the TPU were added into a two-screw extruder for melting, and a screw temperature was controlled at 100° C. to 180° C.; then 50 parts by weight of nitrogen were injected at a tail end of the extruder through a booster pump, an extruder die temperature was controlled at 100° C., and a die pressure was controlled at 100 bar; and the material was subjected to extrusion foaming through a die, and then cut under water to obtain yellowing-resistant TPU foam material particles, where the TPU foam material particles had a density of 0.25 g/cm.sup.3 and a foam cell size of 70 m to 100 m;

[0052] the TPU foam material particles obtained above were filled into a mold with a length of 300 mm, a width of 250 mm, and a thickness of 50 mm; and 2 bar water vapor was used to compress by 10% along a thickness direction of the mold for bonding and molding of the TPU foam material particles to finally obtain a molded foam product. The obtained foam product was placed at 50° C. and 50% RH for 2 h, then dried in a constant-temperature room at 80° C. for 2 h, and finally placed at 25° C. and 50% RH for 2 h to evaluate its performance.

Example 5

[0053] A preparation method of a yellowing-resistant TPU foam material included: 65 kg of hydrogenated diphenylmethane diisocyanate, 12 kg of 1,4-butylene glycol, 100 kg of PTMEG, a hindered phenol antioxidant, a benzotriazole UV absorber, and a hindered amine light stabilizer were added into a twin-screw extruder and subjected to a reaction at 150° C. to 200° C. to obtain a TPU, where the hindered phenol antioxidant was Irgafos168 and added at a specific amount 0.3% of a total amount of the TPU; the benzotriazole UV absorber was TinuvinUV-3 and added at a specific amount 1.2% of the total amount of the TPU; the hindered amine light stabilizer was Tinuvin144 and added at a specific amount 4% of the total amount of the TPU; and the TPU particles had a softening point of 110° C., a Shore hardness of 90 A, and a melt index of 20 g/10 min;

[0054] 100 parts by weight of the TPU were added into a two-screw extruder for melting, and a screw temperature was controlled at 100° C. to 180° C.; then 30 parts by weight of carbon dioxide were injected at a tail end of the extruder through a booster pump, an extruder die temperature was controlled at 100° C., and a die pressure was controlled at 80 bar; and the material was subjected to extrusion foaming through a die, and then cut under water to obtain a yellowing-resistant TPU foam plate material with a thickness of 20 mm, where the TPU foam plate material had a density of 0.25 g/cm.sup.3 and a foam cell size of 100 m to 120 m;

[0055] The obtained foam plate material was placed at 50° C. and 50% RH for 2 h, then dried in a constant-temperature room at 80° C. for 2 h, and finally placed at 25° C. and 50% RH for 2 h to evaluate its performance.

Example 6

[0056] A preparation method of a yellowing-resistant TPU foam material included: 55 kg of IPDI, 15 kg of 1,4-butylene glycol, 100 kg of PTMEG, a hindered phenol antioxidant, a benzotriazole UV absorber, and a hindered amine light stabilizer were added into a twin-screw extruder and subjected to a reaction at 150° C. to 200° C. to obtain a TPU, where the hindered phenol antioxidant was Irgafos618 and added at a specific amount 0.15% of a total amount of the TPU; the benzotriazole UV absorber was Tinuvin234 and added at a specific amount 1.5% of the total amount of the TPU; the hindered amine light stabilizer was Tinuvin571 and added at a specific amount 2.5% of the total amount of the TPU; and the TPU particles had a softening point of 155° C., a Shore hardness of 88 A, and a melt index of 40 g/10 min;

[0057] 100 parts by weight of the TPU were added into a 200 L pressure-resistant vessel, and 100 parts by weight of nitrogen were injected into the pressure-resistant vessel to make a pressure in the pressure-resistant vessel reach 150 bar and maintain at the value for 48 h, such that the nitrogen reached a dissolution equilibrium inside the TPU and the physical foaming agent penetrated into the TPU; and then the material with dissolution equilibrium was heated in 140° C. water vapor for foaming to obtain yellowing-resistant TPU foam material particles, where the dissolution equilibrium indicated that the physical foaming agent was uniformly dispersed after entering the TPU, and the TPU foam material particles had a density of 0.22 g/cm.sup.3 and a foam cell size of 30 m to 60 m;

[0058] the TPU foam material particles obtained above were filled into a mold with a length of 300 mm, a width of 250 mm, and a thickness of 50 mm; and 2 bar water vapor was used to compress by 10% along a thickness direction of the mold for bonding and molding of the TPU foam material particles to finally obtain a molded foam product. The obtained foam product was placed at 50° C. and 50% RH for 2 h, then dried in a constant-temperature room at 80° C. for 2 h, and finally placed at 25° C. and 50% RH for 2 h to evaluate its performance.

[0059] The molded foam products prepared in Examples 1 to 6 were tested. A tensile strength, an elongation at break, a tearing strength, and a resilience were tested by a tensile machine. According to ASDM-D1148, a 340 nm UVA lamp was used to test at a lamp irradiation intensity of 0.77 W/m.sup.2/nm to obtain a yellowing resistance grade I; and according to HG/T3689-2001A, a 300 h irradiation test was conducted to obtain a yellowing resistance grade II. Specific test data were shown in the table below:

TABLE-US-00001 TABLE 1 Yellowing Yellowing Tensile Elon- Tearing resistance resistance strength gation strength Resil- Item grade I grade II (kPa) at break (kN/m) ience Example 1 4.5 5 1200 180% 15 58% Example 2 5 4.5 1100 170% 17 56% Example 3 4.5 5 1300 165% 12 60% Example 4 5 5 1050 175% 15 58% Example 5 4.5 4.5 1250 180% 10 57% Example 6 5 5 1300 180% 16 60% Infinergy 3-3.5 3-3.5 1200 170% 13 58% 32- 100U10 product

[0060] It can be seen from the data in the table that the TPU foam products prepared according to Examples 1 to 6 exhibit a yellowing resistance grade of 4.5 to 5 in a 300 h accelerated test, indicating a very prominent yellowing resistance, which is significantly better than that of the existing TPU foam products on the market; and the TPU foam products of the present disclosure also have excellent resilience and mechanical strength.

[0061] The above descriptions are merely preferred examples of the present disclosure, and are not intended to limit the present disclosure. Any modifications, equivalent replacements, improvements, and the like made within the spirit and principle of the present disclosure shall be all included in the protection scope of the present disclosure.