Polyurethane elastomer and foaming material and use thereof

Abstract

The present invention provides a polyurethane elastomer, the raw materials for its preparation include isocyanate-terminated polyamide prepolymer, diisocyanate, polyether polyol or polyester polyol and chain extender. The present invention also provides a foaming composition, a foaming material and uses thereof comprising the polyurethane elastomer. The polyurethane elastomer provided by the present invention introduces a polyamide segment formed by diisocyanate and an aliphatic dicarboxylic acid into its molecular chain, thereby significantly improving the properties of the polyurethane elastomer molecular chain, and the foaming material prepared using the polyurethane elastomer of the present invention can significantly improve its multiple performances. The polyurethane elastomer and its foaming material provided by the present invention also have the advantages of simple process, strong operability, low manufacturing cost, etc., and are therefore very suitable for large-scale industrial production and have very important industrial and economic value.

Description

Technical Field

[0001] The invention relates to the field of polyurethane foam materials, in particular to a polyurethane elastomer and a polyurethane elastomer foam material obtained from the polyurethane elastomer and uses thereof. Background Art

[0002] The technology of preparing thermoplastic polyurethane elastomer (TPU) foamed material by foaming with inert gas (such as carbon dioxide, nitrogen, alkane, etc.) is known. For example, Chinese patent CN 101370861A discloses a method of preparing thermoplastic polyurethane elastomer foam particles by extruding a thermoplastic polyurethane elastomer with a Shore hardness of 44-84A and a filler, suspending and impregnating the thermoplastic polyurethane elastomer in a high-pressure fluid, and then molding the prepared foamed particles in a mold to prepare a foamed material product. Chinese patent CN 103804890A discloses a method for extruding foamed thermoplastic polyurethane elastomer particles, including 100 parts of thermoplastic polyurethane elastomer, 0.01-0.5 parts of foaming nucleating agent, and 0.01-0.2 parts of antioxidant; the preparation method of the extruded foamed thermoplastic polyurethane elastomer particles is: mixing the materials and then extruding and granulating to obtain beads suitable for foaming; then the beads are put into a special foaming extruder, foamed through a die, and then underwater pelletized to obtain product particles, and then the prepared foamed particles are molded in a mold to prepare a foamed material product. The thermoplastic polyurethane elastomer foam material prepared by these methods has the characteristics of light weight, softness, comfort, good resilience, good physical and mechanical properties, etc., and is widely used in sports shoes, packaging, and home furnishings. However, TPU foam materials also have some disadvantages. The existing TPU foam materials will have the disadvantage of insufficient strength after the density is further reduced. In addition, in some applications, TPU foam materials are required to have higher hardness and higher rebound performance. However, after the hardness of TPU foam materials is increased, their rebound performance will usually be reduced.

[0003] In recent years, another thermoplastic elastomer foam material, polyether polyamide elastomer (PEBA) foam material, has received a lot of attention. For example, Chinese patent CN 107629448A discloses a method for preparing block polyether amide foam particles with a sandbag structure, wherein a polyether polyamide elastomer is mixed with a modifier, a filler, and a coupling agent for granulation, and then supercritically foamed to prepare a foam material. Chinese patent CN108884253A discloses a foam material of a polyether polyamide block copolymer elastomer composed of a block of polyamide 11, a block of polyamide 12, a rigid block of polyamide 6 or polyamide 6.10, and a polyether block. Chinese patent CN 111117215A discloses a supercritical foam material of an elastomer composition composed of at least two polyamide elastomers, an antioxidant, and a nucleating agent. Compared with thermoplastic polyurethane elastomer foam materials, polyether polyamide elastomer foam materials have higher resilience and lower density. However, the tear resistance of polyether polyamide elastomer foam materials is insufficient, causing the shoe materials made of them to be easily worn in the case of friction and collision. In addition, polyether polyamide elastomer materials have higher costs, which limits their large-scale applications.

[0004] Some other patents disclose foaming materials of polyurethane elastomer / polyether polyamide elastomer compositions. For example, Chinese patent CN 108250734A discloses a method for preparing a Pebax / TPU blended foaming material, which uses a mixture of Pebax and TPU with a weight ratio of 10:90-90:10 to prepare a foaming material by supercritical foaming after extrusion granulation. Chinese patent CN113943489A discloses a foaming material composition and a method for preparing a foaming material, which uses 10-90% block copolymer, 4-84% thermoplastic polyurethane elastomer, 1-25% polyurethane ionomer, 0.1-5% foaming nucleating agent, mixed and granulated, and then foamed with a foaming agent to prepare a foaming material. The composite foaming material prepared by the above blending method has poor durability due to the compatibility problem between the components, and the rebound performance is easily reduced after long-term cyclic reciprocating compression.

[0005] Therefore, developing a foam material with low density, high tear strength, better resilience under high hardness, and good resistance to cyclic reciprocating compression is an urgent problem to be solved in the art. Summary of the invention

[0006] In order to make up for the deficiencies in the prior art, an object of the present invention is to provide a polyurethane elastomer, and the polyurethane foam material prepared therefrom has significantly improved comprehensive properties, including lower density, higher tear strength, and can still maintain good rebound performance while improving hardness, and the manufacturing cost is not high and the practicality is strong.

[0007] Another object of the present invention is to provide a polyurethane elastomer foaming composition and a polyurethane elastomer foaming material obtained therefrom.

[0008] Another object of the present invention is to provide uses of the polyurethane elastomer foaming composition and the polyurethane elastomer foaming material.

[0009] The first aspect of the present invention provides a polyurethane elastomer, wherein the raw materials for its preparation include, by mass: 5 to 50 parts of isocyanate-terminated polyamide prepolymer, 2 to 40 parts of diisocyanate A1, 30 to 100 parts of polyether polyol or polyester polyol, and 1 to 10 parts of chain extender;

[0010] Among them, the isocyanate-terminated polyamide prepolymer is prepared by the reaction of diisocyanate A2 and aliphatic dicarboxylic acid, and its number average molecular weight is 1000-5000 g / mol; the diisocyanate A2 is selected from aliphatic and / or alicyclic diisocyanates, and the aliphatic dicarboxylic acid is selected from α, ω-aliphatic straight-chain dicarboxylic acids with 4 to 20 carbon atoms.

[0011] In the polyurethane elastomer provided by the present invention, carbon dioxide is removed by reacting the isocyanate group of the diisocyanate A2 with the carboxyl group of the aliphatic dicarboxylic acid, thereby forming the isocyanate-terminated polyamide prepolymer, which has a structure as shown in the following general formula:

[0012]

[0013] Wherein, R1 represents a residue of an aliphatic dicarboxylic acid without a carboxyl group, R2 represents a residue of a diisocyanate A2 without an isocyanate group, and n represents a value that enables the isocyanate-terminated polyamide prepolymer to reach a desired number average molecular weight.

[0014] In the molecular chain composition of the polyurethane elastomer provided by the present invention, in addition to the polyurethane hard segment formed by the reaction of macromolecular polyester or polyether soft segment, diisocyanate A1 and chain extender, a polyamide segment obtained by the reaction of diisocyanate A2 and aliphatic dicarboxylic acid is also included. The introduction of the polyamide segment enhances the rigidity of the hard segment of the polyurethane elastomer molecular chain, strengthens the phase separation effect of the hard segment and the soft segment, so that the foaming material prepared by the polyurethane elastomer still has excellent resilience at a higher hardness. The introduction of the polyamide segment can also increase the melt strength of the polyurethane elastomer, so that it can prepare a foaming material with lower density. In addition, the polyamide segment and the polyurethane segment in the polyurethane elastomer molecular chain provided by the present invention have different melting peaks. In the process of steam forming of the foaming material prepared by the polyurethane elastomer, one of the segments can be kept in a crystalline state by selecting a suitable steam pressure (or temperature), and the other segment is in a molten state, thereby enabling the foaming material to obtain a better bonding effect, so that the foaming material product prepared by the polyurethane elastomer has a higher tear strength. Moreover, compared with the mixed foaming material of thermoplastic polyurethane elastomer and polyether polyamide elastomer, the resilience performance of the foaming material obtained by the present invention will not be significantly reduced after a long-term cyclic reciprocating compression test.

[0015] In the polyurethane elastomer provided by the present invention, the number average molecular weight (Mn) of the isocyanate-terminated polyamide prepolymer can be 1000-5000 g / mol, including but not limited to about 1000 g / mol, about 1500 g / mol, about 2000 g / mol, about 2500 g / mol, about 3000 g / mol, about 3500 g / mol, about 4000 g / mol, about 4500 g / mol, about 5000 g / mol or any combination of molecular weight intervals. In some preferred embodiments, the number average molecular weight of the isocyanate-terminated polyamide prepolymer can be 1000-2000 g / mol.

[0016] In the polyurethane elastomer provided by the present invention, its preparation raw materials may further include, by mass, 10 to 35 parts of isocyanate-terminated polyamide prepolymer, 5 to 35 parts of diisocyanate A1, 40 to 80 parts of polyether polyol or polyester polyol and 2 to 8 parts of chain extender.

[0017] In the polyurethane elastomer provided by the present invention, the number average molecular weight (Mn) of the polyurethane elastomer can be 100000-200000 g / mol, including but not limited to about 100000 g / mol, about 110000 g / mol, about 120000 g / mol, about 130000 g / mol, about 140000 g / mol, about 150000 g / mol, about 160000 g / mol, about 170000 g / mol, about 180000 g / mol, about 190000 g / mol, about 200000 g / mol or any combination of molecular weight intervals. In some preferred embodiments, the number average molecular weight of the polyurethane elastomer can be 120000-150000 g / mol.

[0018] In the polyurethane elastomer provided by the present invention, the diisocyanate A2 can be selected from aliphatic and / or alicyclic diisocyanates commonly used in the art, including but not limited to tri-, tetra-, penta-, hexa-, hepta-, octamethylene diisocyanate, 2-methyl-pentamethylene 1,5-diisocyanate, 2-ethyl-butylene 1,4-diisocyanate, isophorone diisocyanate (IPDI), dicyclohexylmethane 2,2-diisocyanate, dicyclohexylmethane 2,4-diisocyanate, dicyclohexylmethane 4,4-diisocyanate (H 12 MDI), 1,4-bis(isocyanate methyl)cyclohexane, 1,3-bis(isocyanate methyl)cyclohexane (HXDI), cyclohexane-1,4-diisocyanate, 1-methyl-cyclohexane 2,4-diisocyanate, 1-methyl-cyclohexane 2,6-diisocyanate. In some preferred embodiments, the diisocyanate A2 can be selected from pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane 4,4-diisocyanate (H 12 MDI) or more.

[0019] In the polyurethane elastomer provided by the present invention, the aliphatic dicarboxylic acid can be selected from α,ω-aliphatic straight-chain dicarboxylic acids with carbon atoms of 4 to 20 commonly used in the art, including but not limited to succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid, 1,13-tridecanedioic acid, 1,14-tetradecanedioic acid. In some preferred embodiments, the aliphatic dicarboxylic acid can be selected from α,ω-aliphatic straight-chain dicarboxylic acids with carbon atoms of 6 to 10, such as adipic acid, suberic acid, sebacic acid, etc.

[0020] In the polyurethane elastomer provided by the present invention, the molar ratio of the diisocyanate A2 to the reactive group (-NCO): (-COOH) of the aliphatic dicarboxylic acid can be 1.05 to 1.5:1, including but not limited to about 1.05:1, about 1.1:1, about 1.2:1, about 1.3:1, about 1.4:1, about 1.5:1, or any combination of molar ratio intervals. The resulting prepolymer can be formed into an isocyanate-terminated prepolymer by an excess of diisocyanate A2. In some preferred embodiments, the molar ratio of the reactive group (-NCO): (-COOH) can be 1.1 to 1.3:1.

[0021] In the polyurethane elastomer provided by the present invention, the isocyanate-terminated polyamide prepolymer can be prepared by the following process: dissolving an aliphatic dicarboxylic acid in a solvent that does not react with diisocyanate A2, then adding an excess of diisocyanate A2, heating to 80 to 280° C. (for example, heating to 100 to 150° C.) for reflux reaction, stirring continuously during the reaction to discharge carbon dioxide, and removing the solvent and unreacted raw materials under reduced pressure after the reaction is completed, thereby preparing the isocyanate-terminated polyamide prepolymer.

[0022] The solvent can be selected from common polar organic solvents in the art that do not react with diisocyanate A2, including but not limited to N,N-dimethylformamide, N,N-dimethylacetamide, cyclohexanone, dimethyl sulfoxide, sulfolane, etc.

[0023] In the polyurethane elastomer provided by the present invention, the diisocyanate A1 can be selected from one or more of the aliphatic, alicyclic and aromatic diisocyanates commonly found in the art, including but not limited to diphenylmethane 2,2-diisocyanate, diphenylmethane 2,4-diisocyanate, diphenylmethane 4,4-diisocyanate (MDI), naphthylene 1,5-diisocyanate (NDI), toluene 2,4-diisocyanate, toluene 2,6-diisocyanate (TDI), pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane 2,4-diisocyanate, dicyclohexylmethane 4,4-diisocyanate (HDI), diisocyanate (D ... 12 In some preferred embodiments, the diisocyanate A1 can be selected from one or more of diphenylmethane 4,4-diisocyanate (MDI), pentamethylene diisocyanate (PDI), and hexamethylene diisocyanate (HDI).

[0024] In the polyurethane elastomer provided by the present invention, the polyether polyol or polyester polyol can be selected from the common types in the art. In some preferred embodiments, the number average molecular weight (Mn) of the polyether polyol or polyester polyol can be 500-10000 g / mol, including but not limited to about 500 g / mol, about 1000 g / mol, about 2000 g / mol, about 3000 g / mol, about 4000 g / mol, about 5000 g / mol, about 6000 g / mol, about 8000 g / mol, about 10000 g / mol or any combination of molecular weight intervals. In some more preferred embodiments, the number average molecular weight of the polyether polyol or polyester polyol can be 700-4000 g / mol. In some further preferred embodiments, the number average molecular weight of the polyether polyol or polyester polyol can be 1000-3000 g / mol.

[0025] In the polyurethane elastomer provided by the present invention, the polyether polyol can be prepared by reacting an initiator with a 2-6-membered epoxy compound, wherein the initiator used can be one or more of the small molecule polyols, small molecule polyamines, and small molecule alcoholamines commonly used in the art, including but not limited to one or more of water, propylene glycol, glycerol, trimethylolpropane, ethylenediamine, pentaerythritol, xylitol, triethylenediamine, sorbitol, ethylene glycol, bisphenol A, and toluene diamine; the epoxy compound used includes but is not limited to one or more of ethylene oxide, propylene oxide, and tetrahydrofuran. In some preferred embodiments, the polyether polyol can be selected from polyethylene glycol obtained by reacting ethylene oxide with ethylene glycol, polypropylene glycol obtained by reacting propylene oxide with propylene glycol, polytetramethylene ether glycol (PTMEG) obtained by reacting water with tetrahydrofuran (THF), and copolyethers of the reaction products of THF and ethylene oxide or THF and propylene oxide. In some more preferred embodiments, the polyether polyol may be selected from polytetramethylene ether glycol (PTMEG).

[0026] In the polyurethane elastomer provided by the present invention, the polyester polyol can be selected from one or more of the alkyd polyester polyols, polycaprolactone polyols and polycarbonate polyols commonly used in the art.

[0027] The alkyd polyester polyol of the present invention can be prepared by esterification or transesterification of a diol commonly used in the art with a dicarboxylic acid, a dicarboxylic acid anhydride or a dicarboxylic acid ester, and its acid value can be 0-1.0 mgKOH / g, preferably 0.1-0.5 mgKOH / g.

[0028] The alkyd polyester polyol of the present invention can be prepared by reacting aliphatic and / or aromatic diols having 2 to 12 carbon atoms commonly used in the art with aliphatic and / or aromatic dicarboxylic acids, dicarboxylic acid anhydrides or dicarboxylic acid esters having 4 to 15 carbon atoms.

[0029] Among them, the diols include but are not limited to one or more of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol (BDO), 1,5-pentanediol (PDO), 1,6-hexanediol (HDO), 2,2-dimethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, decanediol, and dodecanediol; the dicarboxylic acids, dicarboxylic acid anhydrides, and dicarboxylic acid esters include but are not limited to one or more of phthalic acid, phthalic anhydride, dimethyl phthalate, dimethyl terephthalate, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, phthalic anhydride, and tetrahydrophthalic anhydride.

[0030] In some preferred embodiments, the diol can be selected from ethylene glycol and / or 1,4-butanediol; the dicarboxylic acid, dicarboxylic acid anhydride and dicarboxylic acid ester can be selected from one or more of adipic acid, phthalic anhydride and tetrahydrophthalic anhydride. In some more preferred embodiments, the alkyd polyester polyol can be selected from polybutylene adipate.

[0031] During the preparation of the alkyd polyester polyol of the present invention, the molar ratio of the diol to the dicarboxylic acid, dicarboxylic acid anhydride or dicarboxylic acid ester may be 1.0 to 3.0:1, for example, 1.02 to 2.0:1.

[0032] The polycaprolactone polyol of the present invention can be prepared from ε-caprolactone monomers and initiators commonly used in the art under the initiation of a catalyst.

[0033] The polycarbonate polyol of the present invention can be prepared by the phosgene method, carbon dioxide regulated copolymerization method, cyclic carbonate ring-opening polymerization method or ester exchange method commonly used in the art.

[0034] The polycarbonate polyol of the present invention is preferably prepared by an ester exchange method using diols and carbonates commonly used in the art, wherein the diols include but are not limited to one or more of 1,2-ethylene glycol, 1,4-butanediol (BDO), 1,5-pentanediol (PDO), and 1,6-hexanediol (HDO), preferably 1,4-butanediol and / or 1,5-pentanediol; the carbonates include but are not limited to dimethyl carbonate and / or diethyl carbonate, preferably dimethyl carbonate.

[0035] In the polyurethane elastomer provided by the present invention, the chain extender can be a common type in the art, especially a small molecule chain extender common in the art, and its molecular weight can be 50 to 500 g / mol. In some preferred embodiments, the chain extender can be a small molecule diol or diamine chain extender common in the art, including but not limited to ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,3-butanediol, 1,5-pentanediol, 1,4-cyclohexanediol, hydroquinone di(hydroxyethyl) ether, one or more of neopentyl glycol. In some more preferred embodiments, the chain extender can be selected from one or more of ethylene glycol, 1,4-butanediol, and 1,6-hexanediol.

[0036] The polyurethane elastomer provided by the present invention can be prepared by the following process: firstly, the polyether polyol or polyester polyol and the chain extender are preheated and mixed in a reactor (for example, heated to 80-150° C.), then the isocyanate-terminated polyamide prepolymer and the diisocyanate A1 are heated and mixed in another container (for example, heated to 100-150° C.), the obtained mixture is added to the reactor for stirring reaction, the obtained reactant is cured and heat-treated (for example, heat-treated at a temperature of 80-120° C. for 10-20 hours), and the polyurethane elastomer in particle form is obtained after grinding.

[0037] The second aspect of the present invention provides a polyurethane elastomer foaming composition, which comprises the polyurethane elastomer described in any one of the above technical solutions.

[0038] In the foaming composition provided by the present invention, in addition to the polyurethane elastomer, one or more common additives in the art may also be included, including but not limited to one or more of antioxidants, UV additives, foaming nucleating agents, and fillers. In some preferred embodiments, the polyurethane elastomer foaming composition may include, by mass: 500 to 2000 parts of the polyurethane elastomer described in any one of the above technical solutions, 5 to 20 parts of foaming nucleating agents, 1 to 10 parts of antioxidants, and 0.1 to 5 parts of UV additives. In some more preferred embodiments, the polyurethane elastomer foaming composition may include, by mass: 800 to 1500 parts of the polyurethane elastomer described in any one of the above technical solutions, 8 to 15 parts of foaming nucleating agents, 1 to 5 parts of antioxidants, and 0.5 to 2 parts of UV additives.

[0039] In the foaming composition provided by the present invention, the additives used can be any common types in the field of polyurethane foam materials, and can be selected by those skilled in the art according to the application, material properties and other requirements. The antioxidant includes but is not limited to antioxidant 1010, antioxidant 168, antioxidant 1098, etc.; the UV additive includes but is not limited to anti-ultraviolet agent UV312, ultraviolet absorber UV326, etc.; the foaming nucleating agent includes but is not limited to calcium carbonate, talc, silicon dioxide, zeolite, montmorillonite, carbon black, kaolin, wollastonite, diatomaceous earth, mica flakes, titanium dioxide, etc., preferably one or more of calcium carbonate, talc, montmorillonite, kaolin, the The average particle size of the foaming nucleating agent can be 0.01 to 10 μm, for example, about 0.03 μm, about 0.05 μm, about 0.08 μm, about 0.1 μm, about 0.3 μm, about 0.5 μm, about 0.8 μm, about 1 μm, about 2 μm, about 3 μm, about 4 μm, about 5 μm, about 7 μm, about 9 μm or any combination of particle size intervals. The average particle size of the foaming nucleating agent is further preferably 0.05 to 5 μm.

[0040] The third aspect of the present invention provides a polyurethane elastomer foam material, which is prepared from the polyurethane elastomer foam composition described in any one of the above technical solutions under the action of a foaming agent.

[0041] In the foaming material provided by the present invention, the foaming agent can be any type commonly used in the field of polyurethane foaming materials, including but not limited to nitrogen, carbon dioxide, alkanes, chlorofluorocarbons, hydrochlorocarbons, hydrofluorocarbons or hydrochlorofluorocarbons. In some preferred embodiments, the foaming agent can be nitrogen and / or carbon dioxide.

[0042] The foam material provided by the present invention can be prepared by a common polyurethane foam material preparation method in the art, including but not limited to the following methods:

[0043] 1) The polyurethane elastomer is mixed with one or more additives and extruded to form granules to prepare polyurethane elastomer foamable particles, and then the polyurethane elastomer foamable particles are mixed with a foaming agent, and then the foaming agent is released by rapidly increasing the temperature or rapidly reducing the pressure to prepare polyurethane elastomer foamed particles; and then the prepared polyurethane elastomer foamed particles are molded in a mold to obtain a foamed material product.

[0044] 2) The polyurethane elastomer is mixed with one or more additives and extruded to prepare a sample of a specific shape, the prepared sample is fully immersed in a foaming agent, and then the foaming agent is released by rapidly reducing the pressure or rapidly increasing the temperature to prepare a foamed material product.

[0045] 3) After the polyurethane elastomer is mixed with one or more additives, the mixture is fully mixed with a foaming agent in a molten state, and then foamed beads of the polyurethane elastomer are prepared by underwater pelletizing. The beads are foamed and formed in a mold to prepare a foamed material product.

[0046] The fourth aspect of the present invention provides the use of the polyurethane elastomer foam composition described in any one of the above technical solutions or the polyurethane elastomer foam material described in any one of the above technical solutions in the preparation of the following products: one or more of sole materials, mattresses, gymnastics mats, pads, automotive interior or exterior components, automotive decorative elements, sound insulation materials, cushioning materials, bicycle saddles, toys, tires and tire parts, surface coverings of athletic fields, gymnasiums or paths, vibration-damping materials, and packaging materials.

[0047] The technical solution provided by the present invention has the following advantages:

[0048] The polyurethane elastomer provided by the present invention introduces a polyamide segment formed by diisocyanate and aliphatic dicarboxylic acid into its molecular chain, thereby significantly improving the properties of the polyurethane elastomer molecular chain. The foaming material prepared using the polyurethane elastomer of the present invention can significantly improve its comprehensive performance, including lower density, excellent tear resistance, higher hardness, good resilience and durability. Based on the excellent material properties, the polyurethane elastomer foaming material provided by the present invention can meet the needs of various application occasions, and thus has a wide range of application fields and strong practicality.

[0049] The polyurethane elastomer and the foamed material thereof provided by the present invention have the advantages of excellent performance, simple process, strong operability, low manufacturing cost, etc., and are therefore very suitable for large-scale industrial production and have very important industrial and economic value. DETAILED DESCRIPTION

[0050] The technical solution of the present invention is further described in detail below in conjunction with specific embodiments.

[0051] Unless otherwise specified, the chemicals used in the examples and comparative examples of the present invention are all commercially available products with industrial grade purity.

[0052] The percentages used in the embodiments and comparative examples of the present invention are all mass percentages unless otherwise specified.

[0053] The molecular weights used in the examples and comparative examples of the present invention are all number average molecular weights, tested by gel permeation chromatography, and the solvent is N,N-dimethylformamide.

[0054] The performance testing methods of the foaming materials prepared in the embodiments and comparative examples of the present invention are as follows:

[0055] (1) Density: tested according to the method described in ASTM D792-2013;

[0056] (2) Hardness: tested using an Asker C hardness tester;

[0057] (3) Tensile strength and elongation at break: tested according to the method described in ISO 1798-2008;

[0058] (4) Delamination tear strength: tested according to the method described in ISO 20875-2018;

[0059] (5) Pendulum resilience: tested according to the method described in DIN 53512, with a sample thickness of 20 mm;

[0060] (6) Compression set: tested according to the method described in ISO 1856-2018;

[0061] (7) Durability test of foamed materials: The materials were first subjected to compression fatigue test using MTS-831 ​​elastic material testing machine - elastomer testing system, with a constant load of 1500 N, a frequency of 1.41 Hz, and a cycle number of 100,000 times. After the compression fatigue test, the pendulum rebound performance of the materials was tested using the method described in DIN 53512.

[0062] Example 1

[0063] (1) 2920 g of adipic acid and 15 L of N,N-dimethylformamide solvent were added to a 30 L reactor. After the adipic acid was completely dissolved, 3528 g of hexamethylene diisocyanate (HDI) was added. The temperature was raised to 120° C. and the mixture was stirred for 6 h. The evaporated solvent and reactants were condensed and refluxed. The carbon dioxide generated by the reaction was discharged. After the reaction was completed, the temperature was raised to 160° C. and the solvent and unreacted raw materials were removed by vacuum to prepare an isocyanate-terminated polyamide prepolymer with a number average molecular weight of 5000 g / mol and a weight of 4100 g.

[0064] (2) Add 200g of 1,4-butanediol and 6500g of PTMEG (number average molecular weight of 2000g / mol) to a 30L reactor, stir and disperse evenly, and heat to 100°C; weigh 2050g of the isocyanate-terminated polyamide prepolymer prepared in step (1) and 1265g of 4,4-diphenylmethane diisocyanate (MDI) in another separate container, heat to 120°C and mix evenly, add the obtained mixture to the reactor, react for 60s under rapid stirring, and then pour the reactant into a polytetrafluoroethylene mold at 100°C. After the reactant is solidified, place it in a hot oven at 100°C for heat treatment for 15h. After the heat treatment, the obtained product is cooled, ground in a grinder, and cut into small particles to obtain thermoplastic polyurethane elastomer particles with a number average molecular weight of 143245g / mol and a weight of 9600g.

[0065] (3) 5 kg of the polyurethane elastomer particles prepared in the above step (2) were mixed with 50 g of nucleating agent calcium carbonate (average particle size of 0.5 μm), 15 g of antioxidant 1010, and 5 g of ultraviolet absorber UV326, and then extruded and granulated to prepare foamable polyurethane elastomer particles with a diameter of 1-2 mm. The temperatures of zones 1-11 of the twin-screw extruder (Nanjing Ruiya, aspect ratio 44) were 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 195°C, 190°C, 185°C, and 180°C.

[0066] (4) The foamable polyurethane elastomer particles obtained in the previous step and water are put into a foaming kettle with stirring in a mass ratio of 1:3, and carbon dioxide is injected as a foaming agent. The mixture is saturated at a pressure of 15 MPa and a temperature of 120° C. for 1 h, and then the pressure is released to prepare polyurethane elastomer foamed particles. The foamed particles are dried at a temperature of 40° C. and then aged at room temperature for one week before use in the next step.

[0067] (5) The polyurethane elastomer foam particles were molded in a steam molding device (Kurt Essar, K68HP) at a steam pressure of 0.27 MPa (140.1°C) to prepare a 20 mm thick polyurethane elastomer foam material molding. After standing for 24 hours, various performance tests were performed. The test results are shown in Table 1.

[0068] Example 2

[0069] (1) Add 2088 g of suberic acid and 15 L of N,N-dimethylformamide solvent to a 30 L reactor. After the suberic acid is completely dissolved, add 4716 g of dicyclohexylmethane 4,4-diisocyanate (H 12MDI), heated to 120°C, reacted for 6 hours under stirring, the evaporated solvent and reactants were condensed and refluxed, and the carbon dioxide produced by the reaction was discharged. After the reaction was completed, the temperature was raised to 160°C and the solvent and unreacted raw materials were removed by vacuum to prepare an isocyanate-terminated polyamide prepolymer with a number average molecular weight of 1000 g / mol and a weight of 5400 g.

[0070] (2) Add 731g of 1,4-butanediol and 5760g of polybutylene adipate (number average molecular weight of 2000g / mol) to a 30L reactor, stir and disperse evenly, and heat to 100°C; weigh 1000g of the isocyanate-terminated polyamide prepolymer prepared in step (1) and 2500g of 4,4-diphenylmethane diisocyanate (MDI) in another separate container, heat to 120°C and mix evenly, add the obtained mixture to the reactor, react for 60s under rapid stirring, then pour the reactant into a polytetrafluoroethylene mold at 100°C, and after the reactant is solidified, place it in a 100°C hot oven for heat treatment for 15h. After the heat treatment, the obtained product is cooled, ground in a grinder, and cut into small particles to obtain thermoplastic polyurethane elastomer particles with a number average molecular weight of 138123g / mol and a weight of 9550g.

[0071] (3) 5 kg of the polyurethane elastomer particles prepared in the above step (2) were mixed with 50 g of nucleating agent calcium carbonate (average particle size of 0.5 μm), 15 g of antioxidant 1010, and 5 g of ultraviolet absorber UV326, and then extruded and granulated to prepare foamable polyurethane elastomer particles with a diameter of 1-2 mm. The temperatures of zones 1-11 of the twin-screw extruder (Nanjing Ruiya, aspect ratio 44) were 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 195°C, 190°C, 185°C, and 180°C.

[0072] (4) The foamable polyurethane elastomer particles obtained in the previous step and water are put into a foaming kettle with stirring in a mass ratio of 1:3, and carbon dioxide is injected as a foaming agent. The mixture is saturated at a pressure of 15 MPa and a temperature of 120° C. for 1 h, and then the pressure is released to prepare polyurethane elastomer foamed particles. The foamed particles are dried at a temperature of 40° C. and then aged at room temperature for one week before use in the next step.

[0073] (5) The polyurethane elastomer foam particles were molded in a steam molding device (Kurt Essar, K68HP) at a steam pressure of 0.21 MPa (134.1°C) to prepare a 20 mm thick polyurethane elastomer foam material molding. After standing for 24 hours, various performance tests were performed. The test results are shown in Table 1.

[0074] Example 3

[0075] (1) In a 30L reactor, 4040g of sebacic acid and 10L of dimethyl sulfoxide (DMSO) were added. After the sebacic acid was completely dissolved, 3696g of pentamethylene diisocyanate (PDI) was added. The temperature was raised to 120°C and the reaction was stirred for 6 hours. The evaporated solvent and reactants were condensed and refluxed, and the carbon dioxide produced by the reaction was discharged. After the reaction was completed, the temperature was raised to 160°C and the solvent and unreacted raw materials were removed by vacuum to prepare an isocyanate-terminated polyamide prepolymer with a number average molecular weight of 1500g / mol and a weight of 5400g.

[0076] (2) Add 513 g of 1,4-butanediol and 7683 g of PTMEG (number average molecular weight of 2000 g / mol) to a 30 L reactor, stir and disperse evenly, and heat to 100° C.; weigh 3000 g of the isocyanate-terminated polyamide prepolymer prepared in step (1) and 3345 g of 4,4-diphenylmethane diisocyanate (MDI) in another separate container, heat to 120° C. and mix evenly, add the obtained mixture to the reactor, react for 60 seconds under rapid stirring, and then pour the reactant into a polytetrafluoroethylene mold at 100° C. After the reactant is solidified, place it in a hot oven at 100° C. for heat treatment for 15 hours. After the heat treatment, the obtained product is cooled, ground in a grinder, and cut into small particles to obtain thermoplastic polyurethane elastomer particles with a number average molecular weight of 133659 g / mol and a weight of 13200 g.

[0077] (3) 5 kg of the polyurethane elastomer particles prepared in the above step (2) were mixed with 50 g of nucleating agent calcium carbonate (average particle size of 0.5 μm), 15 g of antioxidant 1010, and 5 g of ultraviolet absorber UV326, and then extruded and granulated to prepare foamable polyurethane elastomer particles with a diameter of 1-2 mm. The temperatures of zones 1-11 of the twin-screw extruder (Nanjing Ruiya, aspect ratio 44) were 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 195°C, 190°C, 185°C, and 180°C.

[0078] (4) The foamable polyurethane elastomer particles obtained in the previous step and water are put into a foaming kettle with stirring in a mass ratio of 1:3, and carbon dioxide is injected as a foaming agent. The mixture is saturated at a pressure of 15 MPa and a temperature of 120° C. for 1 h, and then the pressure is released to prepare polyurethane elastomer foamed particles. The foamed particles are dried at a temperature of 40° C. and then aged at room temperature for one week before use in the next step.

[0079] (5) The polyurethane elastomer foam particles were molded in a steam molding device (Kurt Essar, K68HP) at a steam pressure of 0.24 MPa (137.2°C) to prepare a 20 mm thick polyurethane elastomer foam material molding. After standing for 24 h, various performance tests were performed. The test results are shown in Table 1.

[0080] Example 4

[0081] (1) 2920 g of adipic acid and 15 L of dimethyl sulfoxide (DMSO) were added to a 30 L reactor. After the adipic acid was completely dissolved, 4032 g of hexamethylene diisocyanate (HDI) was added. The temperature was raised to 120° C. and the mixture was stirred for 6 h. The evaporated solvent and reactants were condensed and refluxed. The carbon dioxide generated by the reaction was discharged. After the reaction was completed, the temperature was raised to 160° C. and the solvent and unreacted raw materials were removed by vacuum to prepare an isocyanate-terminated polyamide prepolymer with a number average molecular weight of 1300 g / mol and a weight of 4800 g.

[0082] (2) Add 459g of 1,4-butanediol and 6600g of PTMEG (number average molecular weight of 2000g / mol) to a 30L reactor, stir and disperse evenly, and heat to 100°C; weigh 2600g of the isocyanate-terminated polyamide prepolymer prepared in step (1) and 1600g of 4,4-diphenylmethane diisocyanate (MDI) in another separate container, heat to 120°C and mix evenly, add the obtained mixture to the reactor, react for 60s under rapid stirring, then pour the reactant into a polytetrafluoroethylene mold at 100°C, and after the reactant is solidified, place it in a hot oven at 100°C for heat treatment for 15h. After the heat treatment, the obtained product is cooled, ground in a grinder, and cut into small particles to obtain thermoplastic polyurethane elastomer particles with a number average molecular weight of 136391g / mol and a weight of 10850g.

[0083] (3) 5 kg of the polyurethane elastomer particles prepared in the above step (2) were mixed with 50 g of nucleating agent calcium carbonate (average particle size of 0.5 μm), 15 g of antioxidant 1010, and 5 g of ultraviolet absorber UV326, and then extruded and granulated to prepare foamable polyurethane elastomer particles with a diameter of 1-2 mm. The temperatures of zones 1-11 of the twin-screw extruder (Nanjing Ruiya, aspect ratio 44) were 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 195°C, 190°C, 185°C, and 180°C.

[0084] (4) The foamable polyurethane elastomer particles obtained in the previous step and water are put into a foaming kettle with stirring in a mass ratio of 1:3, and carbon dioxide is injected as a foaming agent. The mixture is saturated at a pressure of 15 MPa and a temperature of 120° C. for 1 h, and then the pressure is released to prepare polyurethane elastomer foamed particles. The foamed particles are dried at a temperature of 40° C. and then aged at room temperature for one week before use in the next step.

[0085] (5) The polyurethane elastomer foam particles were molded in a steam molding device (Kurt Essar, K68HP) at a steam pressure of 0.23 MPa (136.2°C) to prepare a 20 mm thick polyurethane elastomer foam material molding. After standing for 24 h, various performance tests were performed. The test results are shown in Table 1.

[0086] Example 5

[0087] (1) 2920 g of adipic acid and 15 L of dimethyl sulfoxide (DMSO) were added to a 30 L reactor. After the adipic acid was completely dissolved, 4032 g of hexamethylene diisocyanate (HDI) was added. The temperature was raised to 120° C. and the mixture was stirred for 6 h. The evaporated solvent and reactants were condensed and refluxed. The carbon dioxide generated by the reaction was discharged. After the reaction was completed, the temperature was raised to 160° C. and the solvent and unreacted raw materials were removed by vacuum to prepare an isocyanate-terminated polyamide prepolymer with a number average molecular weight of 1300 g / mol and a weight of 4800 g.

[0088] (2) Add 602 g of 1,6-hexanediol and 6600 g of PTMEG (number average molecular weight of 2000 g / mol) to a 30 L reactor, stir and disperse them evenly, and heat to 100° C.; weigh 2600 g of the isocyanate-terminated polyamide prepolymer prepared in step (1) and 1677 g of dicyclohexylmethane 4,4-diisocyanate (H 12 MDI), heated to 120°C and mixed evenly, the obtained mixture was added to the reactor, reacted for 60 seconds under rapid stirring, and then poured into a 100°C polytetrafluoroethylene mold. After the reactant was solidified, it was placed in a 100°C hot oven for heat treatment for 15 hours. After the heat treatment, the obtained product was cooled, ground in a grinder, and cut into small particles to obtain thermoplastic polyurethane elastomer particles with a number average molecular weight of 140021g / mol and a weight of 10732g.

[0089] (3) 5 kg of the polyurethane elastomer particles prepared in the above step (2) were mixed with 50 g of nucleating agent calcium carbonate (average particle size of 0.5 μm), 15 g of antioxidant 1010, and 5 g of ultraviolet absorber UV326, and then extruded and granulated to prepare foamable polyurethane elastomer particles with a diameter of 1-2 mm. The temperatures of zones 1-11 of the twin-screw extruder (Nanjing Ruiya, aspect ratio 44) were 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 195°C, 190°C, 185°C, and 180°C.

[0090] (4) The foamable polyurethane elastomer particles obtained in the previous step and water are put into a foaming kettle with stirring in a mass ratio of 1:3, and carbon dioxide is injected as a foaming agent. The mixture is saturated at a pressure of 15 MPa and a temperature of 120° C. for 1 h, and then the pressure is released to prepare polyurethane elastomer foamed particles. The foamed particles are dried at a temperature of 40° C. and then aged at room temperature for one week before use in the next step.

[0091] (5) The polyurethane elastomer foam particles were molded in a steam molding device (Kurt Essar, K68HP) at a steam pressure of 0.16 MPa (128.1°C) to prepare a 20 mm thick polyurethane elastomer foam material molding. After standing for 24 h, various performance tests were performed. The test results are shown in Table 1.

[0092] Example 6

[0093] (1) 2920 g of adipic acid and 15 L of dimethyl sulfoxide (DMSO) were added to a 30 L reactor. After the adipic acid was completely dissolved, 4032 g of hexamethylene diisocyanate (HDI) was added. The temperature was raised to 120° C. and the mixture was stirred for 6 h. The evaporated solvent and reactants were condensed and refluxed. The carbon dioxide generated by the reaction was discharged. After the reaction was completed, the temperature was raised to 160° C. and the solvent and unreacted raw materials were removed by vacuum to prepare an isocyanate-terminated polyamide prepolymer with a number average molecular weight of 1300 g / mol and a weight of 4800 g.

[0094] (2) Add 316.2 g of ethylene glycol and 6600 g of PTMEG (number average molecular weight of 2000 g / mol) to a 30 L reactor, stir and disperse evenly, and heat to 100° C.; weigh 2600 g of the isocyanate-terminated polyamide prepolymer prepared in step (1) and 1075 g of hexamethylene diisocyanate (HDI) in another separate container, heat to 120° C. and mix evenly, add the obtained mixture to the reactor, react for 60 seconds under rapid stirring, and then pour the reactant into a 100° C. polytetrafluoroethylene mold. After the reactant is solidified, place it in a 100° C. hot oven for heat treatment for 15 hours. After the heat treatment, the obtained product is cooled, ground in a grinder, and cut into small particles to obtain thermoplastic polyurethane elastomer particles with a number average molecular weight of 138109 g / mol and a weight of 9953 g.

[0095] (3) 5 kg of the polyurethane elastomer particles prepared in the above step (2) were mixed with 50 g of nucleating agent calcium carbonate (average particle size of 0.5 μm), 15 g of antioxidant 1010, and 5 g of ultraviolet absorber UV326, and then extruded and granulated to prepare foamable polyurethane elastomer particles with a diameter of 1-2 mm. The temperatures of zones 1-11 of the twin-screw extruder (Nanjing Ruiya, aspect ratio 44) were 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 195°C, 190°C, 185°C, and 180°C.

[0096] (4) The foamable polyurethane elastomer particles obtained in the previous step and water are put into a foaming kettle with stirring in a mass ratio of 1:3, and carbon dioxide is injected as a foaming agent. The mixture is saturated at a pressure of 15 MPa and a temperature of 120° C. for 1 h, and then the pressure is released to prepare polyurethane elastomer foamed particles. The foamed particles are dried at a temperature of 40° C. and then aged at room temperature for one week before use in the next step.

[0097] (5) The polyurethane elastomer foam particles were molded in a steam molding device (Kurt Essar, K68HP) at a steam pressure of 0.13 MPa (124.1°C) to prepare a 20 mm thick polyurethane elastomer foam material molding. After standing for 24 hours, various performance tests were performed. The test results are shown in Table 1.

[0098] Example 7

[0099] (1) 2920 g of adipic acid and 15 L of dimethyl sulfoxide (DMSO) were added to a 30 L reactor. After the adipic acid was completely dissolved, 4032 g of hexamethylene diisocyanate (HDI) was added. The temperature was raised to 120° C. and the mixture was stirred for 6 h. The evaporated solvent and reactants were condensed and refluxed. The carbon dioxide generated by the reaction was discharged. After the reaction was completed, the temperature was raised to 160° C. and the solvent and unreacted raw materials were removed by vacuum to prepare an isocyanate-terminated polyamide prepolymer with a number average molecular weight of 1300 g / mol and a weight of 4800 g.

[0100] (2) Add 459 g of 1,4-butanediol and 6600 g of PTMEG (number average molecular weight of 2000 g / mol) to a 30 L reactor, stir and disperse evenly, and heat to 100° C.; weigh 2600 g of the isocyanate-terminated polyamide prepolymer prepared in step (1) and 986 g of pentamethylene diisocyanate (PDI) in another separate container, heat to 120° C. and mix evenly, add the obtained mixture to the reactor, react for 60 seconds under rapid stirring, and then pour the reactant into a polytetrafluoroethylene mold at 100° C. After the reactant is solidified, place it in a hot oven at 100° C. for heat treatment for 15 hours. After the heat treatment, the obtained product is cooled, ground in a grinder, and cut into small particles to obtain thermoplastic polyurethane elastomer particles with a number average molecular weight of 139371 g / mol and a weight of 9745 g.

[0101] (3) 5 kg of the polyurethane elastomer particles prepared in the above step (2) were mixed with 50 g of nucleating agent calcium carbonate (average particle size of 0.5 μm), 15 g of antioxidant 1010, and 5 g of ultraviolet absorber UV326, and then extruded and granulated to prepare foamable polyurethane elastomer particles with a diameter of 1-2 mm. The temperatures of zones 1-11 of the twin-screw extruder (Nanjing Ruiya, aspect ratio 44) were 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 195°C, 190°C, 185°C, and 180°C.

[0102] (4) The foamable polyurethane elastomer particles obtained in the previous step and water are put into a foaming kettle with stirring in a mass ratio of 1:3, and carbon dioxide is injected as a foaming agent. The mixture is saturated at a pressure of 15 MPa and a temperature of 120° C. for 1 h, and then the pressure is released to prepare polyurethane elastomer foamed particles. The foamed particles are dried at a temperature of 40° C. and then aged at room temperature for one week before use in the next step.

[0103] (5) The polyurethane elastomer foam particles were molded in a steam molding device (Kurt Essar, K68HP) at a steam pressure of 0.14 MPa (125.5°C) to prepare a 20 mm thick polyurethane elastomer foam material molding. After standing for 24 hours, various performance tests were performed. The test results are shown in Table 1.

[0104] Example 8

[0105] (1) 2920 g of adipic acid and 15 L of dimethyl sulfoxide (DMSO) were added to a 30 L reactor. After the adipic acid was completely dissolved, 4032 g of hexamethylene diisocyanate (HDI) was added. The temperature was raised to 120° C. and the mixture was stirred for 6 h. The evaporated solvent and reactants were condensed and refluxed. The carbon dioxide generated by the reaction was discharged. After the reaction was completed, the temperature was raised to 160° C. and the solvent and unreacted raw materials were removed by vacuum to prepare an isocyanate-terminated polyamide prepolymer with a number average molecular weight of 1300 g / mol and a weight of 4800 g.

[0106] (2) Add 252g of ethylene glycol and 5748g of PTMEG (number average molecular weight of 2000g / mol) to a 30L reactor, stir and disperse evenly, and heat to 100°C; weigh 3500g of the isocyanate-terminated polyamide prepolymer prepared in step (1) and 500g of hexamethylene diisocyanate (HDI) in another separate container, heat to 120°C and mix evenly, add the obtained mixture to the reactor, react for 60s under rapid stirring, then pour the reactant into a 100°C polytetrafluoroethylene mold, and after the reactant is solidified, place it in a 100°C hot oven for heat treatment for 15h. After the heat treatment, the obtained product is cooled, ground in a grinder, and cut into small particles to obtain thermoplastic polyurethane elastomer particles with a number average molecular weight of 134245g / mol and a weight of 9643g.

[0107] (3) 5 kg of the polyurethane elastomer particles prepared in the above step (2) were mixed with 50 g of nucleating agent calcium carbonate (average particle size of 0.5 μm), 15 g of antioxidant 1010, and 5 g of ultraviolet absorber UV326, and then extruded and granulated to prepare foamable polyurethane elastomer particles with a diameter of 1-2 mm. The temperatures of zones 1-11 of the twin-screw extruder (Nanjing Ruiya, aspect ratio 44) were 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 195°C, 190°C, 185°C, and 180°C.

[0108] (4) The foamable polyurethane elastomer particles obtained in the previous step and water are put into a foaming kettle with stirring in a mass ratio of 1:3, and carbon dioxide is injected as a foaming agent. The mixture is saturated at a pressure of 15 MPa and a temperature of 120° C. for 1 h, and then the pressure is released to prepare polyurethane elastomer foamed particles. The foamed particles are dried at a temperature of 40° C. and then aged at room temperature for one week before use in the next step.

[0109] (5) The polyurethane elastomer foam particles were molded in a steam molding device (Kurt Essar, K68HP) at a steam pressure of 0.13 MPa (124.1°C) to prepare a 20 mm thick polyurethane elastomer foam material molding. After standing for 24 hours, various performance tests were performed. The test results are shown in Table 1.

[0110] Example 9

[0111] (1) 2920 g of adipic acid and 15 L of dimethyl sulfoxide (DMSO) were added to a 30 L reactor. After the adipic acid was completely dissolved, 4032 g of hexamethylene diisocyanate (HDI) was added. The temperature was raised to 120° C. and the mixture was stirred for 6 h. The evaporated solvent and reactants were condensed and refluxed. The carbon dioxide generated by the reaction was discharged. After the reaction was completed, the temperature was raised to 160° C. and the solvent and unreacted raw materials were removed by vacuum to prepare an isocyanate-terminated polyamide prepolymer with a number average molecular weight of 1300 g / mol and a weight of 4800 g.

[0112] (2) Add 800g of ethylene glycol and 4000g of PTMEG (number average molecular weight of 2000g / mol) to a 30L reactor, stir and disperse evenly, and heat to 100°C; weigh 3484g of the isocyanate-terminated polyamide prepolymer prepared in step (1) and 1715g of hexamethylene diisocyanate (HDI) in another separate container, heat to 120°C and mix evenly, add the obtained mixture to the reactor, react for 60s under rapid stirring, then pour the reactant into a 100°C polytetrafluoroethylene mold, and after the reactant is solidified, place it in a 100°C hot oven for heat treatment for 15h. After the heat treatment, the obtained product is cooled, ground in a grinder, and cut into small particles to obtain thermoplastic polyurethane elastomer particles with a number average molecular weight of 142103g / mol and a weight of 9754g.

[0113] (3) 5 kg of the polyurethane elastomer particles prepared in the above step (2) were mixed with 50 g of nucleating agent calcium carbonate (average particle size of 0.5 μm), 15 g of antioxidant 1010, and 5 g of ultraviolet absorber UV326, and then extruded and granulated to prepare foamable polyurethane elastomer particles with a diameter of 1-2 mm. The temperatures of zones 1-11 of the twin-screw extruder (Nanjing Ruiya, aspect ratio 44) were 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 195°C, 190°C, 185°C, and 180°C.

[0114] (4) The foamable polyurethane elastomer particles obtained in the previous step and water are put into a foaming kettle with stirring in a mass ratio of 1:3, and carbon dioxide is injected as a foaming agent. The mixture is saturated at a pressure of 15 MPa and a temperature of 120° C. for 1 h, and then the pressure is released to prepare polyurethane elastomer foamed particles. The foamed particles are dried at a temperature of 40° C. and then aged at room temperature for one week before use in the next step.

[0115] (5) The polyurethane elastomer foam particles were molded in a steam molding device (Kurt Essar, K68HP) at a steam pressure of 0.13 MPa (124.1°C) to prepare a 20 mm thick polyurethane elastomer foam material molding. After standing for 24 hours, various performance tests were performed. The test results are shown in Table 1.

[0116] Comparative Example 1

[0117] (1) Add 459 g of 1,4-butanediol and 6600 g of PTMEG (number average molecular weight of 2000 g / mol) to a 30 L reactor, stir and disperse evenly, and heat to 100 ° C; weigh 2100 g of 4,4-diphenylmethane diisocyanate (MDI) in another separate container, heat to 120 ° C, add to the reactor, react for 60 seconds under rapid stirring, and then pour the reactant into a 100 ° C polytetrafluoroethylene mold. After the reactant is solidified, put it into a 100 ° C hot oven for heat treatment for 15 hours. After the heat treatment, the obtained product is cooled, ground in a grinder, and cut into small particles to obtain thermoplastic polyurethane elastomer particles with a number average molecular weight of 143203 g / mol and a weight of 8342 g.

[0118] (2) 5 kg of the polyurethane elastomer particles prepared in the above step (1) were mixed with 50 g of a nucleating agent, calcium carbonate (with an average particle size of 0.5 μm), 15 g of an antioxidant 1010, and 5 g of an ultraviolet absorber UV326, and then extruded and granulated to prepare foamable polyurethane elastomer particles with a diameter of 1-2 mm. The temperatures in zones 1-11 of a twin-screw extruder (Nanjing Ruiya, aspect ratio 44) were 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 195°C, 190°C, 185°C, and 180°C.

[0119] (3) The foamable polyurethane elastomer particles obtained in the previous step and water are put into a foaming kettle with stirring in a mass ratio of 1:3, and carbon dioxide is injected as a foaming agent. Saturation is carried out at a pressure of 15 MPa and a temperature of 120° C. for 1 hour, and then the pressure is released to prepare polyurethane elastomer foamed particles. The foamed particles are dried at a temperature of 40° C. and then matured at room temperature for one week before use in the next step.

[0120] (4) The polyurethane elastomer foam particles were molded in a steam molding device (Kurt Essar, K68HP) at a steam pressure of 0.34 MPa (146°C) to prepare a 20 mm thick polyurethane elastomer foam material molding. After standing for 24 hours, various performance tests were performed. The test results are shown in Table 1.

[0121] Comparative Example 2

[0122] (1) Add 459 g of 1,4-butanediol and 6600 g of PTMEG (number average molecular weight of 2000 g / mol) to a 30 L reactor, stir and disperse evenly, and heat to 100 ° C; weigh 1411.2 g of hexamethylene diisocyanate (HDI) in another separate container, heat to 120 ° C, add to the reactor, react for 60 seconds under rapid stirring, and then pour the reactant into a 100 ° C polytetrafluoroethylene mold. After the reactant is solidified, put it into a 100 ° C hot oven for heat treatment for 15 hours. After the heat treatment, the obtained product is cooled, ground in a grinder, and cut into small particles to obtain thermoplastic polyurethane elastomer particles with a number average molecular weight of 141511 g / mol and a weight of 7567 g.

[0123] (2) 5 kg of the polyurethane elastomer particles prepared in the above step (1) were mixed with 50 g of a nucleating agent, calcium carbonate (with an average particle size of 0.5 μm), 15 g of an antioxidant 1010, and 5 g of an ultraviolet absorber UV326, and then extruded and granulated to prepare foamable polyurethane elastomer particles with a diameter of 1-2 mm. The temperatures in zones 1-11 of a twin-screw extruder (Nanjing Ruiya, aspect ratio 44) were 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 195°C, 190°C, 185°C, and 180°C.

[0124] (3) The foamable polyurethane elastomer particles obtained in the previous step and water are put into a foaming kettle with stirring in a mass ratio of 1:3, and carbon dioxide is injected as a foaming agent. Saturation is carried out at a pressure of 15 MPa and a temperature of 120° C. for 1 hour, and then the pressure is released to prepare polyurethane elastomer foamed particles. The foamed particles are dried at a temperature of 40° C. and then matured at room temperature for one week before use in the next step.

[0125] (4) The polyurethane elastomer foam particles were molded in a steam molding device (Kurt Essar, K68HP) at a steam pressure of 0.12 MPa (122.7°C) to prepare a 20 mm thick polyurethane elastomer foam material molding. After standing for 24 hours, various performance tests were performed. The test results are shown in Table 1.

[0126] Table 1 Performance test results of polyurethane elastomer foam moldings

[0127]

[0128] The results in Table 1 show that, compared with the foamed material prepared from the polyurethane elastomer without introducing the polyamide segment into the molecular chain (such as Comparative Examples 1 and 2), the polyurethane elastomer foamed material provided by the present invention has significantly lower density and higher hardness, without sacrificing other properties, especially the resilience. In addition, the resilience of the polyurethane elastomer foamed material provided by the present invention is almost not reduced after a long-term cyclic reciprocating compression test, and has good durability.

[0129] Therefore, the polyurethane elastomer foam material provided by the present invention has excellent comprehensive performance, can meet the needs of various application occasions, and is therefore very industrially practical.

[0130] Unless otherwise defined, the terms used in the present invention have the meanings commonly understood by those skilled in the art.

[0131] The embodiments described in the present invention are for illustrative purposes only and are not intended to limit the scope of protection of the present invention. Those skilled in the art may make various other substitutions, changes and improvements within the scope of the present invention. Therefore, the present invention is not limited to the above embodiments, but is only limited by the claims.

Claims

1. A polyurethane elastomer, characterized in that: The raw materials for preparing the polyurethane elastomer include, by mass: 5 to 50 parts of isocyanate-terminated polyamide prepolymer, 2 to 40 parts of diisocyanate A1, 30 to 100 parts of polyether polyol or polyester polyol, and 1 to 10 parts of chain extender; Among them, the isocyanate-terminated polyamide prepolymer is prepared by the reaction of diisocyanate A2 and aliphatic dicarboxylic acid, and its number average molecular weight is 1000-5000 g / mol; the diisocyanate A2 is selected from aliphatic and / or alicyclic diisocyanates, and the aliphatic dicarboxylic acid is selected from α, ω-aliphatic straight-chain dicarboxylic acids with 4 to 20 carbon atoms.

2. The polyurethane elastomer according to claim 1, characterized in that The raw materials for preparing the polyurethane elastomer include, by mass: 10 to 35 parts of isocyanate-terminated polyamide prepolymer, 5 to 35 parts of diisocyanate A1, 40 to 80 parts of polyether polyol or polyester polyol and 2 to 8 parts of chain extender; and / or The number average molecular weight of the polyurethane elastomer is 100,000 to 200,000 g / mol.

3. The polyurethane elastomer according to claim 2, characterized in that The number average molecular weight of the polyurethane elastomer is 120,000 to 150,000 g / mol.

4. The polyurethane elastomer according to claim 1, characterized in that The diisocyanate A2 is selected from one or more of tri-, tetra-, penta-, hexa-, hepta-, octamethylene diisocyanate, 2-methyl-pentamethylene 1,5-diisocyanate, 2-ethyl-butylene 1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane 2,2-diisocyanate, dicyclohexylmethane 2,4-diisocyanate, dicyclohexylmethane 4,4-diisocyanate, 1,4-bis(isocyanate methyl)cyclohexane, 1,3-bis(isocyanate methyl)cyclohexane, cyclohexane-1,4-diisocyanate, 1-methyl-cyclohexane 2,4-diisocyanate, and 1-methyl-cyclohexane 2,6-diisocyanate; and / or The aliphatic dicarboxylic acid is selected from one or more of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,11-undecanedioic acid, 1,12-dodecanedioc acid, 1,13-tridecanedioc acid, and 1,14-tetradecanedioic acid.

5. The polyurethane elastomer according to claim 1, characterized in that The molar ratio of the diisocyanate A2 to the reactive groups (-NCO):(-COOH) of the aliphatic dicarboxylic acid is 1.05 to 1.5:

1.

6. The polyurethane elastomer according to claim 5, characterized in that The molar ratio of the diisocyanate A2 to the reactive groups (-NCO):(-COOH) of the aliphatic dicarboxylic acid is 1.1 to 1.3:

1.

7. The polyurethane elastomer according to any one of claims 1 to 6, characterized in that: The diisocyanate A1 is selected from one or more of aliphatic, alicyclic and aromatic diisocyanates.

8. The polyurethane elastomer according to claim 7, characterized in that: The diisocyanate A1 is selected from one or more of diphenylmethane 2,2-diisocyanate, diphenylmethane 2,4-diisocyanate, diphenylmethane 4,4-diisocyanate, naphthyl 1,5-diisocyanate, toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane 2,4-diisocyanate, and dicyclohexylmethane 4,4-diisocyanate.

9. The polyurethane elastomer according to any one of claims 1 to 6, characterized in that: The number average molecular weight of the polyether polyol or polyester polyol is 500 to 10000 g / mol.

10. The polyurethane elastomer according to claim 9, characterized in that: The number average molecular weight of the polyether polyol or polyester polyol is 700 to 4000 g / mol.

11. The polyurethane elastomer according to claim 9, characterized in that: The polyether polyol is prepared by reacting an initiator with a 2- to 6-membered epoxy compound, wherein the initiator is selected from one or more of water, propylene glycol, glycerol, trimethylolpropane, ethylenediamine, pentaerythritol, xylitol, triethylenediamine, sorbitol, ethylene glycol, bisphenol A, and toluene diamine, and the epoxy compound is selected from one or more of ethylene oxide, propylene oxide, and tetrahydrofuran; and / or The polyester polyol is selected from one or more of alkyd polyester polyol, polycaprolactone polyol and polycarbonate polyol.

12. The polyurethane elastomer according to claim 11, characterized in that The polyether polyol is selected from polytetramethylene ether glycol.

13. The polyurethane elastomer according to claim 11, characterized in that The polyester polyol is selected from alkyd polyester polyol, which is prepared by reacting aliphatic and / or aromatic diols having 2 to 12 carbon atoms with aliphatic and / or aromatic dicarboxylic acids, dicarboxylic acid anhydrides or dicarboxylic acid esters having 4 to 15 carbon atoms.

14. The polyurethane elastomer according to claim 13, characterized in that The polyester polyol is selected from polybutylene adipate.

15. The polyurethane elastomer according to any one of claims 1 to 6, characterized in that: The chain extender is selected from one or more of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,3-butanediol, 1,5-pentanediol, 1,4-cyclohexanediol, hydroquinone di(hydroxyethyl) ether, and neopentyl glycol.

16. A polyurethane elastomer foaming composition, characterized in that: The invention comprises the polyurethane elastomer according to any one of claims 1 to 15.

17. The polyurethane elastomer foaming composition according to claim 16, characterized in that: The polyurethane elastomer foaming composition further comprises one or more of an antioxidant, a UV additive, a foaming nucleating agent, and a filler.

18. The polyurethane elastomer foaming composition according to claim 17, characterized in that: The polyurethane elastomer foaming composition comprises, by mass: 500 to 2000 parts of the polyurethane elastomer according to any one of claims 1 to 15, 5 to 20 parts of a foaming nucleating agent, 1 to 10 parts of an antioxidant and 0.1 to 5 parts of a UV additive.

19. A polyurethane elastomer foam material, characterized in that: The polyurethane elastomer foaming composition is prepared by using a foaming agent.

20. The polyurethane elastomer foam material according to claim 19, characterized in that: The blowing agent is selected from nitrogen, carbon dioxide, alkanes, chlorofluorocarbons, hydrochlorocarbons, hydrofluorocarbons or hydrochlorofluorocarbon blowing agents.

21. Use of the polyurethane elastomer foam composition according to any one of claims 16 to 18 or the polyurethane elastomer foam material according to claim 19 or 20 in the preparation of one or more of the following products: sole materials, mattresses, gymnastics mats, pads, automotive interior or exterior components, sound insulation materials, cushioning materials, bicycle saddles, toys, tires, surface coverings of athletic fields, gymnasiums or paths, vibration-damping materials, and packaging materials.

22. Use of the polyurethane elastomer foam composition according to any one of claims 16 to 18 or the polyurethane elastomer foam material according to claim 19 or 20 in the preparation of automobile decorative elements or tire parts.

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