Thermoplastic polyurethane elastomer foaming material, polyurethane foaming sheet material and preparation method and application of thermoplastic polyurethane elastomer foaming material and polyurethane foaming sheet material

Abstract

The invention discloses a thermoplastic polyurethane elastomer foam material, a polyurethane foam sheet and a preparation method and application thereof, the thermoplastic polyurethane elastomer foam material is prepared from the following raw materials: 1) polyisocyanate, 2) polyol, 3) a chain extender, 4) an antioxidant, 5) a light stabilizer and 6) polyvinyl pyridine, the components are put into a twin-screw extruder for reaction and extrusion, and the thermoplastic polyurethane elastomer foam material is obtained. And carrying out underwater granulation to obtain the thermoplastic polyurethane elastomer foaming material. According to the supercritical foaming composite material, the content of each raw material is optimized, the advantages of each raw material are fully exerted, the raw materials complement each other, and the product quality is improved. The density of the foam material can reach 0.09-0.1 g / cm < 3 >, the foam hole size is small and uniform, the 180-degree tear can reach 4.5 Kn / m, the vertical resilience is 65-85%, the mechanical property is good, the resilience performance is excellent, and the foam material has ultra-light property and good mechanical use performance.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer foaming materials, and particularly relates to a thermoplastic polyurethane elastomer foaming material. Background Art

[0002] Thermoplastic polyurethane elastomer (TPU) is a polymer composed of flexible soft segments and rigid hard segments. It has rubber elasticity at low temperatures and can be plasticized and molded after the temperature is raised. TPU has excellent mechanical properties, such as a wide adjustable range of hardness, good mechanical properties, oil resistance, wear resistance, etc. Therefore, it is extremely important and extensive in the field of industrial applications.

[0003] Thermoplastic polyurethane elastomer foaming material is a type of material that has received relatively much attention in the footwear industry at present. It combines aesthetics and stability and has excellent performance. It is composed of multiple elastic and very light TPU foaming balls aggregated together, and is also known as "popcorn" in the industry. The particles contain a large number of microporous structures inside, and a large amount of gas is wrapped inside the pores. These closed bubbles endow the foaming particles with properties such as low density, high resilience, and flexibility; it is processed into the required finished product by steam molding process. At the same time, the outermost layer is slightly melted and adhered stably, so that the internal pore structure is not affected. It combines the double advantages of TPU and foam materials, overcomes the disadvantages of conventional TPU raw materials such as large weight and poor shock absorption performance, and has many advantages such as light weight, strong air permeability, excellent resilience performance, good compression performance, good low-temperature resistance, and environmental protection, wear resistance, and yellowing resistance.

[0004] CN109867946A uses a composition of thermoplastic polyurethane elastomer and polyolefin graft copolymer, and uses an environmentally friendly supercritical carbon dioxide foaming method to foam, obtaining polyurethane foaming particles with good molding, but the foam will become hard at -15°C and is prone to wrinkling and cracking.

[0005] CN111303548A uses PS and TPU, a mixture of nano calcium carbonate, calcium phosphate, and zinc dimethacrylate as a nucleating agent, zinc peroxide as a crosslinking agent, and random polystyrene maleic anhydride as a dispersant to prepare a supercritical foaming composite material, improving the quality of the product, with high tensile strength and good mechanical properties.

[0006] CN113980338A uses thermoplastic polyurethane elastomer, hyperbranched polyimide, and a supramolecular foaming improver containing a cyclic structure to foam by supercritical carbon dioxide molding. The sole material made from it has excellent low-temperature bending resistance and has the characteristics of low density, high resilience, and excellent mechanical properties.

[0007] The addition of inorganic rigid particles can improve the mechanical properties of polymer materials; however, for foamed materials, due to their special microscopic cell structure, the addition of inorganic rigid particles is often difficult to disperse uniformly in the system. The foamed materials prepared have a relatively large density and uneven cell sizes. Especially for materials such as shoe materials that are in a state of long-term movement and bending, the specific use scenarios lead to a sharp increase in the tendency of inorganic particles in the reinforcing material to agglomerate and precipitate. Secondly, some thermoplastic elastomers have a linear molecular structure and low crystallinity, resulting in poor solvent resistance, poor creep resistance, and poor high-temperature thermal stability, which limits their popularization in the foaming field. They have poor resilience, are prone to irreversible deformation during use, affecting their application; and have poor foaming effects, such as large and uneven cell sizes and low foaming ratios. Summary of the Invention

[0008] In view of the above problems existing in the prior art, the present invention provides a thermoplastic polyurethane elastomer foamed material and a preparation method thereof. Polyvinylpyridine is added during the synthesis of TPU, and micro-crosslinking is carried out through hydrogen bonds. Then, a thermoplastic polyurethane foamed material is prepared by supercritical CO2 foaming. The foamed material has a uniform crosslinking network distribution, small and uniform cell sizes, and low density. Due to the acid-base responsiveness of vinylpyridine, the obtained product has good solvent and hydrolysis resistance, high midsole bending stiffness, excellent mechanical properties, and can achieve large-scale continuous production.

[0009] The technical solution of the present invention to solve the above problems is as follows:

[0010] A thermoplastic polyurethane elastomer foamed material, comprising raw materials in the following mass percentages:

[0011] 1) Polyisocyanate: 15% - 50%;

[0012] 2) Polyol: 40% - 75%;

[0013] 3) Chain extender: 5% - 15%;

[0014] 4) Antioxidant: 0.1% - 4%;

[0015] 5) Light stabilizer: 0.5% - 6%;

[0016] And 6) polyvinylpyridine accounting for 10% - 70% of the total mass of components 1) - 5).

[0017] As a preferred solution, the polyvinylpyridine used has one or more of the following structural schematic formulas:

[0018]

[0019] Polyvinylpyridine - Structural formula 1, Polyvinylpyridine - Structural formula 2, Polyvinylpyridine - Structural formula 3

[0020] wherein X1 and X2 are respectively: -H, -CH3, -C2H5;

[0021] X3, X4, X5, and X6 are respectively: -H, -CH3, -C2H5, -Cl, -F, -OCH3, -OH, -COOH;

[0022] The R group is: -H, -CH3, -C2H5, -NH2, -Cl, =O, -SO3.

[0023] As a preferred embodiment, the number - average molecular weight of the polyvinylpyridine is preferably 1000 - 1000000 g / mol, more preferably 10000 - 500000 g / mol.

[0024] As a preferred embodiment, the polyol is selected from one or more of polyester polyol, polyether polyol, polycarbonate polyol, and polycaprolactone polyol.

[0025] As a preferred embodiment, the polyester polyol is formed by the reaction of a saturated dicarboxylic acid and a saturated diol (wherein the molar ratio of the hydroxyl group of the diol to the carboxyl group of the dicarboxylic acid is 1.0 - 1.5, preferably 1.1 - 1.3). The saturated dicarboxylic acid conforms to the following structural formula: HOOC - C n H 2n -C00H, wherein n is a natural number from 2 to 20, preferably n = 2, 4, or 8; the diol conforms to the following structural formula OH - C x H 2x -OH, wherein x is a natural number from 2 to 8, preferably x = 2 or 4 (corresponding to butanediol and hexanediol respectively), such as polyethylene glycol adipate, polybutylene glycol adipate, polyhexylene glycol adipate, etc. The number - average molecular weight (Mn) of the polyester polyol described in the present invention is 500 - 6000 g / mol, preferably 800 - 3000 g / mol.

[0026] As a preferred embodiment, the polyether polyol is selected from one or more of polyethylene oxide diol, polypropylene oxide diol, and polytetramethylene glycol; the molecular weight of the polyether polyol is 500 - 6000 g / mol, more preferably 800 - 3000 g / mol.

[0027] As a preferred embodiment, the polycarbonate polyol is prepared by transesterification of a small - molecule diol with dimethyl carbonate, diphenyl carbonate, etc. Common small - molecule diols include ethylene glycol, butanediol, neopentyl glycol, hexanediol, etc.; the preferred molecular weight range is 500 - 6000 g / mol, more preferably 1000 - 4000 g / mol.

[0028] As a preferred embodiment, the polycaprolactone polyol is prepared by ring-opening polymerization of ε-caprolactone with the addition of a catalyst and an initiator. Commonly used initiators include ethylene glycol, butanediol, hexanediol, diethylene glycol, neopentyl glycol, etc.; the preferred molecular weight range is 500 - 6000 g / mol, and more preferably 800 - 3000 g / mol.

[0029] As a preferred embodiment, the chain extender is one or more of diols or diamines. Among them, the diol is preferably an aliphatic small molecule diol with the general formula HO-C a H 2a -OH, where a is a natural number from 1 to 10, preferably a = 2, 4, 6, corresponding to ethylene glycol, butanediol, and hexanediol respectively. The diamine is an aliphatic small molecule diamine, such as 1,3-propanediamine, 1,4-butanediamine, p-phenylenediamine, benzidine, 3,3'-dimethyl-4,4-biphenyldiamine.

[0030] As a preferred embodiment, the polyisocyanate is selected from one or more of aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates, such as 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), phenylene-1,4-diisocyanate (PPDI), naphthalene diisocyanate (NDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (H 12 MDI), 1,4-cyclohexane diisocyanate (CHDI), pentamethylene diisocyanate (PDI); preferably one or more of hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI), and 4,4'-diphenylmethane diisocyanate (MDI).

[0031] As a preferred embodiment, in the present invention, the antioxidant is selected from one or more of hindered phenol antioxidants, hindered amine antioxidants, and phosphite antioxidants.

[0032] As a preferred embodiment, in the present invention, the light stabilizer is selected from one or two of UV absorbers and hindered amine light stabilizers.

[0033] As a preferred embodiment, the present invention also provides a method for preparing a thermoplastic polyurethane elastomer foaming material, which comprises the following steps:

[0034] 1) Polyisocyanate, polyol, chain extender, antioxidant, and light stabilizer are added to a twin-screw extruder for reaction. The length-diameter ratio of the extruder screw is 50 - 120:1, preferably a co-rotating double-threaded intermeshing screw with a length-diameter ratio of 50 - 75:1.

[0035] 2) The extruder is divided into 10 - 14 temperature zones, and the temperature range is 80 - 250 °C. Among them, the temperature of the mixing zone of the extruder is preferably 80 - 170 °C, the temperature of the reaction zone is preferably 100 - 300 °C, and the temperature of the conveying zone is preferably 80 - 250 °C.

[0036] 3) Polyvinylpyridine is added at the 2 / 3 position of the extruder. The temperature of the screen changer, melt pump, start-up valve, and die head of the twin-screw extruder is preferably 100 - 250 °C.

[0037] 4) The melt is granulated underwater at 5 - 50 °C, and then fully cured in a silo. After the moisture is qualified, a thermoplastic polyurethane elastomer is obtained.

[0038] As a preferred embodiment, the present invention also provides a method for preparing a polyurethane foam board, which includes the following steps: adding the thermoplastic polyurethane elastomer into an autoclave, impregnating it with supercritical CO2, performing penetration and swelling to reach an equilibrium state, forming a polymer-supercritical fluid homogeneous system, and then extruding through a die and cooling for shaping.

[0039] Preferably, the temperature of the autoclave is 60 - 250 °C, more preferably 120 - 220 °C; the gauge pressure of the autoclave is 5 - 30 MPa, more preferably 8 - 20 MPa; the pressure of CO2 is 9 - 12 Mpa, and the impregnation time of CO2 is 0.1 - 3 hours, more preferably 0.5 - 2 hours; the pressure release rate is 0.5 - 30 MPa / s, more preferably 5 - 10 MPa / s.

[0040] Preferably, the forming process conditions include: the gauge pressure for foaming is 10 - 30 MPa, more preferably 15 - 25 MPa; the mass of supercritical CO2 is 1 - 30% of the mass of the thermoplastic polyurethane melt, more preferably 5 - 15%; the die temperature is 80 - 220 °C, more preferably 100 - 180 °C; the die gauge pressure is 10 - 30 MPa, more preferably 15 - 25 MPa.

[0041] The thermoplastic polyurethane foam board of the present invention can be applied in the fields of automotive interiors, bedding, seats, and shoe materials.

[0042] Compared with the prior art, the present invention has the following advantages:

[0043] (1) The foaming thermoplastic polyurethane elastomer prepared by the present invention has excellent foaming performance and melt-welding molding performance, and can be used to prepare thermoplastic polyurethane foam products after foaming, or directly prepare thermoplastic polyurethane foam products in one step. Compared with the foamed thermoplastic polyurethane elastomer beads, the transportation and storage costs are greatly saved.

[0044] (2) The foaming thermoplastic polyurethane elastomer provided by the present invention connects polyvinylpyridine through hydrogen bonding. The types of property improvers are simple and the addition method is concise. The preparation method provided by the present invention has low requirements for equipment, and the preparation method is simple and easy for industrial manufacturing.

[0045] (3) Due to the addition of polyvinylpyridine, the crystals of the thermoplastic polyurethane elastomer provided by the present invention are denser, and the blowing agent inside the prepared foaming thermoplastic polyurethane elastomer is difficult to escape. It is a foaming material with high resilience and low shrinkage. The density of the foaming material prepared by the present invention is 0.09 - 0.1 g / cm 3 , the foaming size is controllable, the cell structure is uniform, and the cell diameter is 10 - 100 um; the resilience rate reaches 65% - 85%, and the retention rate of hydrolysis resistance can reach more than 85% after 1 month.

[0046] (4) The insole prepared from the polyurethane foaming board has small compression deformation and high resilience, and high wearing comfort. It broadens the application field of polyurethane foaming materials. Description of the Drawings

[0047] Figure 1 It is the SEM diagram of the corresponding foaming board in the specific embodiment. Specific Embodiment

[0048] In order to be able to understand the technical features and content of the present invention in detail, the preferred embodiments of the present invention will be described in more detail below. Although the preferred embodiments of the present invention are described in the examples, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments described herein.

[0049] Raw Materials and Sources

[0050] Raw material Grade Manufacturer information Polybutylene adipate diol 2000 PBA2000 Wanhua Chemical Group Co., Ltd. Polybutylene adipate diol 1000 PBA1000 Wanhua Chemical Group Co., Ltd. Polycaprolactone diol 2000 PLACCEL200 Daicel (China) Investment Co., Ltd. Hexamethylene diisocyanate HDI Wanhua Chemical Group Co., Ltd. Diphenylmethane diisocyanate MDI Wanhua Chemical Group Co., Ltd. Pentamethylene diisocyanate PDI Wanhua Chemical Group Co., Ltd. 1,4-Butanediol BDO Wanhua Chemical Group Co., Ltd. Antioxidant Irganox 1010 BASF (China) Co., Ltd. Ultraviolet absorber UV-329 Rianlon Co., Ltd. Poly(4-vinylpyridine) P4VP Shanghai Macklin Biochemical Co., Ltd. Poly(2-vinylpyridine) P2VP Shanghai Macklin Biochemical Co., Ltd. Poly(4-vinylpyridine) sulfonate P4VP-SO3 Shanghai Macklin Biochemical Co., Ltd.

[0051] Testing Methods and Standards

[0052]

[0053] Comparative Example 1

[0054] 49.40 kg of HDI, 20.60 kg of BDO, 130.0 kg of PBA2000, 1.04 kg of Irganox 1010, and 1.04 kg of UV-329 were put into a twin-screw reactive extruder with a length-to-diameter ratio of 52:1 for reaction. The extruder was divided into 14 temperature zones with a temperature range of 80 - 250 °C. Among them, the temperature of the mixing zone of the extruder was 100 - 140 °C, the temperature of the reaction zone was 150 - 200 °C, the temperature of the conveying zone was 160 - 200 °C, and the screw speed was set at 200 rpm.

[0055] The above-mentioned thermoplastic polyurethane foaming material was obtained by underwater pelletizing, and the above product was marked as T1;

[0056] The obtained T1 thermoplastic polyurethane foaming material particles were added into an autoclave, and carbon dioxide was introduced to impregnate the TPU particles. The temperature of the autoclave was 120 °C, the pressure was 15 MPa, and the impregnation time was 3 hours; after impregnation, the material in the autoclave was discharged into the atmospheric environment at a pressure release rate of 10 MPa / s to obtain foamed particles. The foamed particles were prepared into a 300 mm * 200 mm * 20 mm foamed board ET-1 by compression molding for performance testing and standby.

[0057] Comparative Example 2

[0058] 73.34 kg of MDI, 21.66 kg of BDO, 105.0 kg of PBA2000, 1.04 kg of Irganox 1010, and 1.04 kg of UV-329 were put into a twin-screw reactive extruder with a length-to-diameter ratio of 52:1 for reaction. The extruder was divided into 14 temperature zones with a temperature range of 80 - 250 °C. Among them, the temperature of the mixing zone of the extruder was 100 - 140 °C, the temperature of the reaction zone was 150 - 200 °C, the temperature of the conveying zone was preferably 160 - 200 °C, and the screw speed was set at 200 rpm.

[0059] The above-mentioned thermoplastic polyurethane foaming material was obtained by underwater pelletizing, and the above product was marked as T2;

[0060] The obtained T2 thermoplastic polyurethane foaming material particles were added into an autoclave, and carbon dioxide was introduced to impregnate the TPU particles. The temperature of the autoclave was 120 °C, the pressure was 15 MPa, and the impregnation time was 3 hours; after impregnation, the material in the autoclave was discharged into the atmospheric environment at a pressure release rate of 10 MPa / s to obtain foamed particles. The foamed particles were prepared into a 300 mm * 200 mm * 20 mm foamed board ET-2 by compression molding for performance testing and standby

[0061] Comparative Example 3

[0062] 49.40 kg of HDI, 20.60 kg of BDO, 130.0 kg of PTMEG2000, 1.04 kg of Irganox 1010, and 1.04 kg of UV-329 were fed into a twin-screw reactive extruder with a length-to-diameter ratio of 52:1 for reaction. The extruder was divided into 14 temperature zones with a temperature range of 80 - 250 °C. Among them, the temperature in the mixing zone of the extruder was 100 - 140 °C, the temperature in the reaction zone was 150 - 200 °C, and the temperature in the conveying zone was 160 - 200 °C. The screw speed was set at 200 rpm

[0063] The above-mentioned thermoplastic polyurethane foaming material was obtained by underwater pelletizing, and the above product was marked as T3;

[0064] The obtained T3 thermoplastic polyurethane foaming material particles were added into an autoclave, and carbon dioxide was introduced to impregnate the TPU particles. The temperature in the autoclave was 120 °C, the pressure was 15 MPa, and the impregnation time was 3 hours; after impregnation, the materials in the autoclave were discharged into the atmospheric environment at a pressure release rate of 10 MPa / s to obtain foamed particles. The foamed particles were prepared into a 300 mm * 200 mm * 20 mm foamed board ET-3 by compression molding and tested for performance for standby.

[0065] Comparative Example 4

[0066] 53.21 kg of HDI, 16.78 kg of BDO, 130.0 kg of PBA1000, 1.04 kg of Irganox 1010, and 1.04 kg of UV-329 were fed into a twin-screw reactive extruder with a length-to-diameter ratio of 52:1 for reaction. The extruder was divided into 14 temperature zones with a temperature range of 80 - 250 °C. Among them, the temperature in the mixing zone of the extruder was 100 - 140 °C, the temperature in the reaction zone was 150 - 200 °C, and the temperature in the conveying zone was 160 - 200 °C. The screw speed was set at 200 rpm

[0067] The above-mentioned thermoplastic polyurethane foaming material was obtained by underwater pelletizing, and the above product was marked as T4;

[0068] The obtained T4 thermoplastic polyurethane foaming material particles were added into an autoclave, and carbon dioxide was introduced to impregnate the TPU particles. The temperature in the autoclave was 120 °C, the pressure was 15 MPa, and the impregnation time was 3 hours; after impregnation, the materials in the autoclave were discharged into the atmospheric environment at a pressure release rate of 10 MPa / s to obtain foamed particles. The foamed particles were prepared into a 300 mm * 200 mm * 20 mm foamed board ET-4 by compression molding and tested for performance for standby.

[0069] Comparative Example 5

[0070] Mix the obtained thermoplastic polyurethane foam material T1 and 80 kg of poly(4-vinylpyridine) with a molecular weight of 100,000, label it as T5, then add it to an autoclave, and introduce carbon dioxide to impregnate the TPU particles. The temperature of the autoclave is 120 °C, the pressure is 15 MPa, and the impregnation time is 3 hours. After impregnation, discharge the material in the autoclave into the atmospheric environment at a pressure release rate of 10 MPa / s to obtain foamed particles. Prepare a 300 mm * 200 mm * 20 mm foamed board ET-5 by compression molding of the foamed particles, and test its performance for standby.

[0071] Example 1

[0072] Put 49.40 kg of HDI, 20.60 kg of BDO, 130.0 kg of PBA2000, 1.04 kg of Irganox 1010, and 1.04 kg of UV-329 into a twin-screw reactive extruder with a length-to-diameter ratio of 52:1 for reaction. Add 80 kg of poly(4-vinylpyridine) with a number-average molecular weight of 100,000 to the 9th zone of the extruder and melt it with TPU. The extruder is divided into 14 temperature zones, and the temperature range is 80 - 250 °C. Among them, the temperature of the mixing zone of the extruder is 100 - 140 °C, the temperature of the reaction zone is 150 - 200 °C, the temperature of the conveying zone is 160 - 200 °C, and the screw speed is set at 200 rpm.

[0073] Obtain the thermoplastic polyurethane foam material through underwater pelletization, and label the above product as T6;

[0074] Add the obtained thermoplastic polyurethane foam material particles T6 to an autoclave, introduce carbon dioxide to impregnate the TPU particles. The temperature of the autoclave is 120 °C, the pressure is 15 MPa, and the impregnation time is 3 hours. After impregnation, discharge the material in the autoclave into the atmospheric environment at a pressure release rate of 10 MPa / s to obtain foamed particles. Prepare a 300 mm * 200 mm * 20 mm foamed board ET-6 by compression molding of the foamed particles, and test its performance for standby.

[0075] Example 2

[0076] Put 49.40 kg of HDI, 20.60 kg of BDO, 130.0 kg of PBA2000, 1.04 kg of Irganox 1010, and 1.04 kg of UV-329 into a twin-screw reactive extruder with a length-to-diameter ratio of 52:1 for reaction. Add 80 kg of poly(2-vinylpyridine) with a number-average molecular weight of 100,000 to the 9th zone of the extruder and melt it with TPU. The extruder is divided into 14 temperature zones, and the temperature range is 80 - 250 °C. Among them, the temperature of the mixing zone of the extruder is 100 - 140 °C, the temperature of the reaction zone is 150 - 200 °C, the temperature of the conveying zone is 160 - 200 °C, and the screw speed is set at 200 rpm.

[0077] The above-mentioned thermoplastic polyurethane foaming material is obtained by underwater granulation, and the above product is marked as T7;

[0078] The obtained T7 thermoplastic polyurethane foaming material particles are added into an autoclave, and carbon dioxide is introduced to impregnate the TPU particles. The temperature of the autoclave is 120 °C, the pressure is 15 MPa, and the impregnation time is 3 hours; after impregnation, the material in the autoclave is discharged into the atmospheric environment at a pressure release rate of 10 MPa / s to obtain foamed particles. The foamed particles are prepared into a 300 mm * 200 mm * 20 mm foamed board ET-7 by compression molding, and the performance is tested for standby.

[0079] Example 3

[0080] 49.40 kg of HDI, 20.60 kg of BDO, 130.0 kg of PBA2000, 1.04 kg of Irganox 1010, and 1.04 kg of UV-329 are put into a twin-screw reactive extruder with a length-diameter ratio of 52:1 for reaction. 80 kg of poly-4-vinylpyridine derivative with a number-average molecular weight of 100,000 is added to the 9th zone of the extruder and melted with TPU. The extruder is divided into 14 temperature zones, and the temperature range is 80 - 250 °C. Among them, the temperature of the mixing zone of the extruder is 100 - 140 °C, the temperature of the reaction zone is 150 - 200 °C, the temperature of the conveying zone is 160 - 200 °C, and the screw speed is set at 200 rpm.

[0081] The above-mentioned thermoplastic polyurethane foaming material is obtained by underwater granulation, and the above product is marked as T8;

[0082] The obtained T8 thermoplastic polyurethane foaming material particles are added into an autoclave, and carbon dioxide is introduced to impregnate the TPU particles. The temperature of the autoclave is 120 °C, the pressure is 15 MPa, and the impregnation time is 3 hours; after impregnation, the material in the autoclave is discharged into the atmospheric environment at a pressure release rate of 10 MPa / s to obtain foamed particles. The foamed particles are prepared into a 300 mm * 200 mm * 20 mm foamed board ET-8 by compression molding, and the performance is tested for standby.

[0083] Example 4

[0084] 49.40 kg of HDI, 20.60 kg of BDO, 130.0 kg of PBA2000, 1.04 kg of Irganox 1010, and 1.04 kg of UV-329 were fed into a twin-screw reactive extruder with a length-to-diameter ratio of 52:1 for reaction. 20 kg of poly(4-vinylpyridine) with a molecular weight of 100,000 was added to the 9th zone of the extruder and melted with TPU. The extruder was divided into 14 temperature zones with a temperature range of 80 - 250 °C. Among them, the temperature of the mixing zone of the extruder was 100 - 140 °C, the temperature of the reaction zone was 150 - 200 °C, and the temperature of the conveying zone was 160 - 200 °C. The screw speed was set at 200 rpm.

[0085] The above-mentioned thermoplastic polyurethane foaming material was obtained by underwater pelletizing, and the above product was marked as T9;

[0086] The obtained T9 thermoplastic polyurethane foaming material particles were added into an autoclave, and carbon dioxide was introduced to impregnate the TPU particles. The temperature of the autoclave was 120 °C, the pressure was 15 MPa, and the impregnation time was 3 hours; after impregnation, the material in the autoclave was discharged into the atmospheric environment at a pressure release rate of 10 MPa / s to obtain foamed particles. The foamed particles were prepared into a 300 mm * 200 mm * 20 mm foamed board ET-9 by compression molding and tested for performance for standby.

[0087] Example 5

[0088] 49.40 kg of HDI, 20.60 kg of BDO, 130.0 kg of PBA2000, 1.04 kg of Irganox 1010, and 1.04 kg of UV-329 were fed into a twin-screw reactive extruder with a length-to-diameter ratio of 52:1 for reaction. 140 kg of poly(4-vinylpyridine) with a molecular weight of 100,000 was added to the 9th zone of the extruder and melted with TPU. The extruder was divided into 14 temperature zones with a temperature range of 80 - 250 °C. Among them, the temperature of the mixing zone of the extruder was 100 - 140 °C, the temperature of the reaction zone was 150 - 200 °C, and the temperature of the conveying zone was 160 - 200 °C. The screw speed was set at 200 rpm.

[0089] The above-mentioned thermoplastic polyurethane foaming material was obtained by underwater pelletizing, and the above product was marked as T10;

[0090] The obtained T10 thermoplastic polyurethane foaming material particles were added into an autoclave, and carbon dioxide was introduced to impregnate the TPU particles. The temperature of the autoclave was 120 °C, the pressure was 15 MPa, and the impregnation time was 3 hours; after impregnation, the material in the autoclave was discharged into the atmospheric environment at a pressure release rate of 10 MPa / s to obtain foamed particles. The foamed particles were prepared into a 300 mm * 200 mm * 20 mm foamed board ET-10 by compression molding and tested for performance for standby.

[0091] Example 6

[0092] 49.40 kg of HDI, 20.60 kg of BDO, 130.0 kg of PBA2000, 1.04 kg of Irganox 1010, and 1.04 kg of UV-329 were put into a twin-screw reactive extruder with a length-to-diameter ratio of 52:1 for reaction. 80 kg of poly(4-vinylpyridine) with a molecular weight of 10,000 was added to the 9th zone of the extruder and melted with TPU. The extruder was divided into 14 temperature zones with a temperature range of 80 - 250 °C. Among them, the temperature of the mixing zone of the extruder was 100 - 140 °C, the temperature of the reaction zone was 150 - 200 °C, the temperature of the conveying zone was 160 - 200 °C, and the screw speed was set at 200 rpm.

[0093] The thermoplastic polyurethane foaming material was obtained by underwater pelletizing, and the above product was marked as T11;

[0094] The obtained T11 thermoplastic polyurethane foaming material particles were added to an autoclave, and carbon dioxide was introduced to impregnate the TPU particles. The temperature of the autoclave was 120 °C, the pressure was 15 MPa, and the impregnation time was 3 hours; after impregnation, the material in the autoclave was discharged into the atmospheric environment at a pressure release rate of 10 MPa / s to obtain foamed particles. The foamed particles were prepared into a 300 mm * 200 mm * 20 mm foamed board ET-11 by compression molding and tested for performance for standby.

[0095] Example 7

[0096] 49.40 kg of HDI, 20.60 kg of BDO, 130.0 kg of PBA2000, 1.04 kg of Irganox 1010, and 1.04 kg of UV-329 were put into a twin-screw reactive extruder with a length-to-diameter ratio of 52:1 for reaction. 80 kg of poly(4-vinylpyridine) with a molecular weight of 500,000 was added to the 9th zone of the extruder and melted with TPU. The extruder was divided into 14 temperature zones with a temperature range of 80 - 250 °C. Among them, the temperature of the mixing zone of the extruder was 100 - 140 °C, the temperature of the reaction zone was 150 - 200 °C, the temperature of the conveying zone was 160 - 200 °C, and the screw speed was set at 200 rpm.

[0097] The thermoplastic polyurethane foaming material was obtained by underwater pelletizing, and the above product was marked as T12;

[0098] Add the obtained T12 thermoplastic polyurethane foamed material particles into an autoclave, introduce carbon dioxide to impregnate the TPU particles with carbon dioxide. The temperature of the autoclave is 120 °C, the pressure is 15 MPa, and the impregnation time is 3 hours. After impregnation, discharge the materials in the autoclave into the atmospheric environment at a pressure release rate of 10 MPa / s to obtain foamed particles. Prepare a 300 mm * 200 mm * 20 mm foamed board ET-12 by compression molding of the foamed particles, and test the performance for standby.

[0099] Example 8

[0100] Put 73.34 kg of MDI, 21.66 kg of BDO, 105.0 kg of PBA2000, 1.04 kg of Irganox 1010, and 1.04 kg of UV-329 into a twin-screw reactive extruder with a length-diameter ratio of 52:1 for reaction. Add 80 kg of poly-4-vinylpyridine with a molecular weight of 100,000 into the 9th zone of the extruder to melt with TPU. The extruder is divided into 14 temperature zones, and the temperature range is 80 - 250 °C. Among them, the temperature of the mixing zone of the extruder is 100 - 140 °C, the temperature of the reaction zone is 150 - 200 °C, the temperature of the conveying zone is 160 - 200 °C, and the screw speed is set at 200 rpm.

[0101] Obtain the thermoplastic polyurethane foamed material through underwater pelletization, and mark the above product as T13;

[0102] Add the obtained T13 thermoplastic polyurethane foamed material particles into an autoclave, introduce carbon dioxide to impregnate the TPU particles with carbon dioxide. The temperature of the autoclave is 120 °C, the pressure is 15 MPa, and the impregnation time is 3 hours. After impregnation, discharge the materials in the autoclave into the atmospheric environment at a pressure release rate of 10 MPa / s to obtain foamed particles. Prepare a 300 mm * 200 mm * 20 mm foamed board ET-13 by compression molding of the foamed particles, and test the performance for standby.

[0103] Example 9

[0104] Put 49.40 kg of HDI, 20.60 kg of BDO, 130.0 kg of PTMEG2000, 1.04 kg of Irganox 1010, and 1.04 kg of UV-329 into a twin-screw reactive extruder with a length-diameter ratio of 52:1 for reaction. Add 80 kg of poly-4-vinylpyridine with a molecular weight of 100,000 into the 9th zone of the extruder. The extruder is divided into 14 temperature zones, and the temperature range is 80 - 250 °C. Among them, the temperature of the mixing zone of the extruder is 100 - 140 °C, the temperature of the reaction zone is 150 - 200 °C, the temperature of the conveying zone is 160 - 200 °C, and the screw speed is set at 200 rpm.

[0105] The above-mentioned thermoplastic polyurethane foamed material is obtained by underwater granulation, and the above product is marked as T14;

[0106] Add the obtained T14 thermoplastic polyurethane foamed material particles into an autoclave, introduce carbon dioxide to impregnate the TPU particles. The temperature of the autoclave is 120 °C, the pressure is 15 MPa, and the impregnation time is 3 hours; after impregnation, discharge the material in the autoclave into the atmospheric environment at a pressure release rate of 10 MPa / s to obtain foamed particles. Prepare a 300 mm * 200 mm * 20 mm foamed board ET-14 by compression molding and reserve it for performance testing.

[0107] Example 10

[0108] Put 53.21 kg of HDI, 16.78 kg of BDO, 130.0 kg of PBA1000, 1.04 kg of Irganox 1010, and 1.04 kg of UV-329 into a twin-screw reactive extruder with a length-diameter ratio of 52:1 for reaction. Add 80 kg of poly-4-vinylpyridine with a molecular weight of 100,000 in the 9th zone of the extruder. The extruder is divided into 14 temperature zones, and the temperature range is 80 - 250 °C. Among them, the temperature of the mixing zone of the extruder is 100 - 140 °C, the temperature of the reaction zone is 150 - 200 °C, the temperature of the conveying zone is 160 - 200 °C, and the screw speed is set at 200 rpm.

[0109] The above-mentioned thermoplastic polyurethane foamed material is obtained by underwater granulation, and the above product is marked as T15;

[0110] Add the obtained T15 thermoplastic polyurethane foamed material particles into an autoclave, introduce carbon dioxide to impregnate the TPU particles. The temperature of the autoclave is 120 °C, the pressure is 15 MPa, and the impregnation time is 3 hours; after impregnation, discharge the material in the autoclave into the atmospheric environment at a pressure release rate of 10 MPa / s to obtain foamed particles. Prepare a 300 mm * 200 mm * 20 mm foamed board ET-15 by compression molding and reserve it for performance testing.

[0111] Table 1: Performance Testing of Thermoplastic Polyurethane Elastomers

[0112]

[0113] Table 2: Performance Testing of Foamed Boards

[0114]

[0115]

[0116] As can be seen from the data in the table, compared with the conventional thermoplastic polyurethane elastomer foaming material, the foaming material with polyvinylpyridine introduced has similar hardness, but the tensile strength, resilience and hydrolysis resistance are improved greatly. Similarly, compared with the foam products of conventional thermoplastic polyurethane foaming, the resilience performance of the foam products with polyvinylpyridine added is greatly improved, and the 180° delamination tear is also significantly improved, and the product performance meets the performance requirements of high resilience and high support.

[0117] The embodiments of the present invention have been described above. The above description is an elaboration of the present invention, not all of the present invention, and is not limited to the disclosed embodiments. Many modifications and changes are obvious to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A thermoplastic polyurethane elastomer foaming material, comprising raw materials in the following mass percentages: 1) Polyisocyanate: 15% - 50%; 2) Polyol: 40% - 75%; 3) Chain extender: 5% - 15%; 4) Antioxidant: 0.1% - 4%; 5) Light stabilizer: 0.5% - 6%; And 6) Polyvinylpyridine in an amount of 10% - 70% relative to the total mass of components 1) - 5).

2. The material according to claim 1, wherein The polyvinylpyridine described above has one or more of the following structural schematic formulas: wherein X1 and X2 are respectively: -H, -CH3, -C2H5; X3, X4, X5, and X6 are respectively: -H, -CH3, -C2H5, -Cl, -F, -OCH3, -OH, -COOH; R is: -H, -CH3, -C2H5, -NH2, -Cl, =O, -SO3.

3. The material according to claim 1 or 2, wherein The number-average molecular weight of the polyvinylpyridine described above is 1,000 - 1,000,000, preferably 10,000 - 500,000.

4. The material according to any one of claims 1 - 3, wherein The polyisocyanate is selected from one or more of aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates, preferably one or more of 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, phenylene-1,4-diisocyanate, naphthalene diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, and pentamethylene diisocyanate.

5. The material according to any one of claims 1 - 4, wherein The polyol is selected from one or more of polyester polyols, polyether polyols, polycarbonate polyols, and polycaprolactone polyols.

6. The material according to claim 5, wherein The number-average molecular weight of the polyester polyol described above is 500 - 6,000, preferably 800 - 3,000; The number-average molecular weight of the polyether polyol described above is 500 - 6,000, preferably 800 - 3,000; The number-average molecular weight of the polycarbonate polyol is 500 - 6,000, preferably 1,000 - 4,000; The number-average molecular weight of the polycaprolactone polyol is 500 - 6,000, preferably 800 - 3,000.

7. The material according to any one of claims 1 - 6, wherein The chain extender is one or more of diols or diamines, preferably one or more of ethylene glycol, butanediol, hexanediol, 1,3-propanediamine, 1,4-butanediamine, p-phenylenediamine, benzidine, and 3,3'-dimethyl-4,4-biphenylenediamine.

8. A method for preparing the material according to any one of claims 1 - 7, comprising the following steps: (1) Adding polyisocyanate, polyol, chain extender, antioxidant, and light stabilizer to a twin - screw extruder for reaction. The length - to - diameter ratio of the extruder screw is 50 - 120:1, preferably a co - rotating double - headed threaded meshing screw with a length - to - diameter ratio of 50 - 75:1; (2) The extruder is divided into 10 - 14 temperature zones, and the temperature range is 80 - 250°C. Among them, the temperature of the mixing zone of the extruder is preferably 80 - 170°C, the temperature of the reaction zone is preferably 100 - 300°C, and the temperature of the conveying zone is preferably 80 - 250°C; (3) Adding polyvinylpyridine at 2 / 3 of the extruder. The temperature of the screen changer, melt pump, start - up valve, and die head of the twin - screw extruder is preferably 100 - 250°C; (4) The melt is granulated underwater at 5 - 50 °C, and then fully cured in a silo. After the moisture is qualified, a thermoplastic polyurethane elastomer is obtained.

9. A method for preparing a polyurethane foam board, comprising the following steps: The thermoplastic polyurethane elastomer foaming material described in any one of claims 1 - 7 is added to an autoclave, impregnated with supercritical CO2 carbon dioxide, subjected to penetration and swelling to reach an equilibrium state, forming a polymer-supercritical fluid homogeneous system, and then extruded through a die and cooled to form a shape.

10. Application of the thermoplastic polyurethane foam board according to claim 9 in the fields of automotive interiors, bedding, seats, and shoe materials.

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