CN115785392A - Polyurethane elastomer, foaming material and application thereof - Google Patents

Abstract

The invention provides a polyurethane elastomer, which is prepared from raw materials including isocyanate-terminated polyamide prepolymer, diisocyanate, polyether polyol or polyester polyol and a chain extender. The invention also provides a foaming composition comprising the polyurethane elastomer, a foaming material and application thereof. The polyurethane elastomer provided by the invention introduces the polyamide chain segment formed by diisocyanate and aliphatic dicarboxylic acid into the molecular chain, so that the property of the molecular chain of the polyurethane elastomer is obviously improved, and the foaming material prepared by using the polyurethane elastomer provided by the invention can obviously improve various performances of the foaming material. The polyurethane elastomer and the foaming material thereof provided by the invention also have the advantages of simple and convenient process, strong operability, low manufacturing cost and the like, so that the polyurethane elastomer and the foaming material thereof are very suitable for large-scale industrial production and have very important industrial value and economic value.

Description

A kind of polyurethane elastomer and its foaming material and application

technical field

The invention relates to the field of polyurethane foam materials, in particular to a polyurethane elastomer, a polyurethane elastomer foam material obtained from the polyurethane elastomer, and applications thereof.

Background technique

The technology of preparing TPU foam material by foaming thermoplastic polyurethane elastomer (TPU) with inert gas (such as carbon dioxide, nitrogen, alkanes, etc.) is known. For example, Chinese patent CN 101370861A discloses a thermoplastic polyurethane elastomer with a Shore hardness of 44-84A and a filler extruded together, suspended and impregnated in a high-pressure fluid, and then prepared thermoplastic polyurethane elastomer expanded particles, and then prepared A method for preparing foamed material products by molding foamed particles in a mold. 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 extruded foamed thermoplastic polyurethane elastomer particles is as follows: mix the materials and extrude pellets to obtain beads suitable for foaming; then put the above beads into a special foaming extruder and foam them through a die Afterwards, it is pelletized under water to obtain product particles, and then the prepared foam particles are molded in a mold to prepare foam material products. The thermoplastic polyurethane elastomer foaming 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 shoe materials, packaging, and home furnishing. 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 High resilience performance, but after the hardness of TPU foam material is increased, its resilience performance will usually decrease.

In recent years, another thermoplastic elastomer foam, polyether polyamide elastomer (PEBA) foam, has gained a lot of attention. For example, Chinese patent CN 107629448A discloses a preparation method of polyetheramide foamed particles with a sandbag structure block. After mixing and granulating polyether polyamide elastomers, modifiers, fillers, and coupling agents, supercritical Foaming A foamed material is prepared. Chinese patent CN108884253A discloses a polyether polyamide block copolymer elastomer composed of polyamide 11 block, polyamide 12 block, polyamide 6 or polyamide 6.10 rigid block and polyether block foam material. Chinese patent CN 111117215A discloses a supercritical foaming material composed of at least two kinds of polyamide elastomers, antioxidants and nucleating agents. Compared with thermoplastic polyurethane elastomer foams, polyether polyamide elastomer foams have higher resilience and lower density, however, polyether polyamide elastomer foams have insufficient tear resistance , causing the shoe material made of it to be easily worn under the condition of friction and collision; in addition, the polyether polyamide elastomer material has a higher cost, which limits its mass application.

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

Therefore, it is an urgent problem to be solved in this field to develop a foam material with low density, high tear strength, better rebound performance under high hardness, and good resistance to cyclic compression. .

Contents of the invention

In order to make up for the deficiencies in the prior art, an object of the present invention is to provide a polyurethane elastomer, the polyurethane foam prepared by it has significantly improved overall performance, including lower density, higher tear strength , while increasing the hardness, it can still maintain a good rebound performance, and the manufacturing cost is not high, and the practicability is strong.

Another object of the present invention is to provide a polyurethane elastomer foam composition and a polyurethane elastomer foam material obtained therefrom.

Another object of the present invention is to provide the use of the polyurethane elastomer foaming composition and the polyurethane elastomer foaming material.

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

Wherein, the isocyanate-terminated polyamide prepolymer is prepared by reacting diisocyanate A2 with aliphatic dicarboxylic acid, and its number average molecular weight is 1000-5000 g/mol; the diisocyanate A2 is selected from aliphatic and/or Alicyclic diisocyanate, wherein the aliphatic dicarboxylic acid is selected from α, ω-aliphatic straight-chain dicarboxylic acids with 4 to 20 carbon atoms.

In the polyurethane elastomer provided by the present invention, carbon dioxide is removed through the reaction of the isocyanate group of the diisocyanate A2 and the carboxyl group of the aliphatic dicarboxylic acid, thereby forming the polyamide prepolymer terminated by the isocyanate, which has the following general The structure shown in the formula:

Among them, _R1 represents the residue of the aliphatic dicarboxylic acid except the carboxyl group, _R2 represents the residue of the diisocyanate A2 except the isocyanate group, n represents the polyamide prepolymer capable of making the isocyanate-terminated polyamide reach the required number average molecular weight value.

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, it also includes diisocyanate A2 and aliphatic Polyamide segment obtained by reaction of dicarboxylic acid. The introduction of the polyamide chain segment enhances the rigidity of the hard segment of the molecular chain of the polyurethane elastomer, and strengthens the phase separation effect of the hard segment and the soft segment, thereby enabling the foamed material prepared by the polyurethane elastomer to have a higher hardness. Still has excellent resilience properties. The introduction of polyamide segments can also increase the melt strength of polyurethane elastomers, making it possible to prepare foams with lower densities. In addition, the polyamide segment and the polyurethane segment in the molecular chain of the polyurethane elastomer provided by the present invention have different melting peaks. Pressure (or temperature) keeps one of the chain segments in a crystalline state and plays a role in supporting the shape, while the other chain segment is in a molten state, so that the foaming material can obtain a better bonding effect, so that the The foamed material product prepared by the polyurethane elastomer has higher tear strength. Moreover, compared with the mixed foaming material of thermoplastic polyurethane elastomer and polyether polyamide elastomer, the rebound performance of the foaming material obtained in the present invention will not be significantly reduced after long-term cyclic compression test.

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 2500g/mol, about 3000g/mol, about 3500g/mol, about 4000g/mol, about 4500g/mol, about 5000g/mol or any combination of molecular weight intervals. In some preferred embodiments, the number average molecular weight of the isocyanate-terminated polyamide prepolymer may be 1000-2000 g/mol.

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

In the polyurethane elastomer provided by the present invention, the number average molecular weight (Mn) of the polyurethane elastomer may be 100,000 to 200,000 g/mol, including but not limited to about 100,000 g/mol, about 110,000 g/mol, about 120,000 g/mol, and about 130,000 g /mol, about 140,000g/mol, about 150,000g/mol, about 160,000g/mol, about 170,000g/mol, about 180,000g/mol, about 190,000g/mol, about 200,000g/mol or any combination of molecular weight intervals. In some preferred embodiments, the number average molecular weight of the polyurethane elastomer may be 120000-150000 g/mol.

In the polyurethane elastomer provided by the present invention, the diisocyanate A2 can be selected from common aliphatic and/or alicyclic diisocyanates 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), bicyclic Hexylmethane 2,2-diisocyanate, dicyclohexylmethane 2,4-diisocyanate, dicyclohexylmethane 4,4-diisocyanate (H ₁₂ MDI), 1,4-bis(isocyanatomethyl)cyclohexane , 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), cyclohexane-1,4-diisocyanate, 1-methyl-cyclohexane 2,4-diisocyanate, 1-methyl- One or more of 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 ) in one or more.

In the polyurethane elastomer provided by the present invention, the aliphatic dicarboxylic acid can be selected from common α, ω-aliphatic straight-chain dicarboxylic acids with 4 to 20 carbon atoms in the field, including but not limited to succinic acid Acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid, 1,13- One or more of tridecanedioic acid and 1,14-tetradecanedioic acid. In some preferred embodiments, the aliphatic dicarboxylic acid can be selected from α,ω-aliphatic straight-chain dicarboxylic acids with 6 to 10 carbon atoms, such as adipic acid, suberic acid, decanoic acid, Diacid etc.

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 may be 1.05 to 1.5:1, including but Not limited to molar ratio intervals of 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 thereof. The resulting prepolymer can be formed into an isocyanate-terminated prepolymer by means of an excess of diisocyanate A2. In some preferred embodiments, the molar ratio of reactive groups (-NCO):(-COOH) may be 1.1˜1.3:1.

In the polyurethane elastomer provided by the present invention, the isocyanate-terminated polyamide prepolymer can be prepared through the following process: aliphatic dicarboxylic acid is dissolved in a solvent that does not react with diisocyanate A2, and then an excess of Diisocyanate A2, heat up to 80-280°C (for example, heat up to 100-150°C) for reflux reaction, continuously stir during the reaction to discharge carbon dioxide, and remove the solvent and unreacted raw materials under reduced pressure after the reaction to prepare the isocyanate End-capped polyamide prepolymers.

Wherein, 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, cyclic Hexanone, dimethyl sulfoxide, sulfolane, etc.

In the polyurethane elastomer provided by the present invention, the diisocyanate A1 can be selected from one or more of common aliphatic, alicyclic, and aromatic diisocyanates 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- One or more of diisocyanate and dicyclohexylmethane 4,4-diisocyanate (H ₁₂ MDI ). In some preferred embodiments, the diisocyanate A1 can be selected from diphenylmethane 4,4-diisocyanate (MDI), pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI) one or more of .

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

In the polyurethane elastomer provided by the present invention, the polyether polyol can be prepared by reacting an initiator with a 2- to 6-membered epoxy compound, wherein the initiator used can be a common small molecule polyol in the art , one or more of small molecule polyamines, small molecule alcohol amines, including but not limited to water, propylene glycol, glycerin, trimethylolpropane, ethylenediamine, pentaerythritol, xylitol, triethylenediamine, sorbitol One or more of alcohol, ethylene glycol, bisphenol A, toluenediamine; the epoxy compound used includes but not limited to one or more of ethylene oxide, propylene oxide, tetrahydrofuran. In some preferred embodiments, the polyether polyol can be selected from polyethylene glycol prepared by the reaction of ethylene oxide and ethylene glycol, polypropylene glycol prepared by the reaction of propylene oxide and propylene glycol, water and tetrahydrofuran ( THF) reaction of polytetramethylene ether glycol (PTMEG), THF and ethylene oxide or THF and propylene oxide reaction product copolyether, etc. In some more preferred embodiments, the polyether polyol may be selected from polytetramethylene ether glycol (PTMEG).

In the polyurethane elastomer provided by the present invention, the polyester polyol may be selected from one or more of alkyd polyester polyols, polycaprolactone polyols, and polycarbonate polyols common in the art.

The alkyd polyester polyol of the present invention can be prepared by esterification or transesterification of dibasic alcohols and dibasic carboxylic acids, dibasic carboxylic acid anhydrides or dibasic carboxylic acid esters in the art, and its acid value It may be 0-1.0 mgKOH/g, Preferably it may be 0.1-0.5 mgKOH/g.

The alkyd polyester polyol of the present invention can be made of aliphatic and/or aromatic diols with 2 to 12 carbon atoms common in the art and aliphatic and/or aromatic diols with 4 to 15 carbon atoms Dibasic carboxylic acid, dibasic carboxylic acid anhydride or dibasic carboxylic acid ester reaction.

Wherein, the dihydric alcohol includes but not limited to ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol (BDO), 1,5- Pentylene glycol (PDO), 1,6-hexanediol (HDO), 2,2-dimethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, decanediol, dodecanediol One or more in; said dibasic carboxylic acid, dibasic carboxylic acid anhydride and dibasic carboxylic acid ester include but not limited to phthalic acid, phthalic anhydride, dimethyl phthalate, terephthalic acid Dimethyl formate, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, isophthalic acid, terephthalic acid, cyclic One or more of adipic acid, phthalic anhydride, tetrahydrophthalic anhydride.

In some preferred embodiments, the dibasic alcohol can be selected from ethylene glycol and/or 1,4-butanediol; the dibasic carboxylic acid, dibasic carboxylic acid anhydride and dibasic carboxylic acid ester can be selected from One or more of diacid, phthalic anhydride, tetrahydrophthalic anhydride. In some more preferred embodiments, the alkyd polyester polyol may be selected from polybutylene adipate.

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 can be 1.0 to 3.0:1 , for example, may be 1.02˜2.0:1.

The polycaprolactone polyol described in the present invention can be prepared from common ε-caprolactone monomers and initiators in the field under the action of a catalyst.

The polycarbonate polyol of the present invention can be prepared by the common phosgene method, carbon dioxide regulated copolymerization method, ring-opening polymerization method of cyclic carbonate or transesterification method in the field.

The polycarbonate polyols described in the present invention are preferably prepared by transesterification of diols and carbonates common in the art, wherein the diols include but are not limited to 1,2-ethylene glycol, 1, One or more of 4-butanediol (BDO), 1,5-pentanediol (PDO), 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.

In the polyurethane elastomer provided by the present invention, the chain extender can be a common type in the field, especially a small molecule chain extender that is common in the field, and its molecular weight can be 50-500 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, new One or more of pentanediol. In some more preferred embodiments, the chain extender may be selected from one or more of ethylene glycol, 1,4-butanediol, and 1,6-hexanediol.

The polyurethane elastomer provided by the present invention can be prepared through the following process: first, the polyether polyol or polyester polyol and the chain extender are pre-heated and mixed in the reactor (for example, the temperature is raised to 80-150 ° C), and then the isocyanate The end-blocked polyamide prepolymer and diisocyanate A1 are heated and mixed in another container (for example, the temperature is raised to 100-150° C.), the obtained mixture is added to the reactor and stirred for reaction, and the obtained reactant is cured and heat-treated ( For example, heat treatment at a temperature of 80-120° C. for 10-20 h), and grinding to obtain the polyurethane elastomer in granular form.

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

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

In the foaming composition provided by the present invention, the additives used can be any kind commonly used in the field of polyurethane foaming materials, and can be selected by those skilled in the art according to requirements such as application occasions and material properties. Described antioxidant includes but not limited to antioxidant 1010, antioxidant 168, antioxidant 1098 etc.; Described UV auxiliary agent includes but not limited to antiultraviolet agent UV312, ultraviolet absorber UV326 etc.; Nucleating agents include but are not limited to calcium carbonate, talc powder, silicon dioxide, zeolite, montmorillonite, carbon black, kaolin, wollastonite, diatomaceous earth, mica flakes, titanium dioxide, etc., preferably calcium carbonate, talc powder, One or more of montmorillonite and kaolin, the average particle size of the foaming nucleating agent can be 0.01-10 μm, for example, it can be 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 of the foam nucleating agent The particle diameter is more preferably 0.05 to 5 μm.

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

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 Class or hydrochlorofluorocarbon blowing agent. In some preferred embodiments, nitrogen and/or carbon dioxide can be used as the blowing agent.

The foaming material provided by the present invention can be prepared by common polyurethane foaming material preparation methods in the art, including but not limited to the following methods:

1) Mix the polyurethane elastomer with one or more additives, extrude and granulate to prepare polyurethane elastomer expandable particles, then mix the polyurethane elastomer expandable particles with a foaming agent, and then rapidly increase the temperature to The foaming agent is released by the high pressure or rapid reduction of the pressure to prepare polyurethane elastomer foamed particles; then the prepared polyurethane elastomer foamed particles are molded in a mold to obtain foamed material products.

2) Mix and extrude the polyurethane elastomer with one or more additives to make a sample of a specific shape, fully impregnate the prepared sample in a foaming agent, and then quickly reduce the pressure or increase the temperature High releases the blowing agent to prepare foamed articles.

3) After mixing the polyurethane elastomer with one or more additives, fully mix it with a foaming agent in a molten state, and then prepare foamed beads of the polyurethane elastomer by underwater cutting, and the beads are in Foam molding in the mold to prepare foam material products.

A fourth aspect of the present invention provides the polyurethane elastomer foaming composition described in any one of the above technical solutions or the polyurethane elastomer foaming material described in any one of the above technical solutions in the preparation of the following products: shoe soles Materials, mattresses, gymnastics mats, liners, automotive interior or exterior components, automotive trim elements, soundproofing materials, cushioning materials, bicycle saddles, toys, tires and tire components, surface coverings for athletic fields, gymnasiums or paths, One or more of vibration materials and packaging materials.

The technical solution provided by the invention has the following advantages:

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

The polyurethane elastomer and its foaming material provided by the invention not only have excellent performance, but also have the advantages of simple process, strong operability, and low manufacturing cost, so they are very suitable for large-scale industrial production and have very important industrial value and economical value. value.

Detailed ways

The technical solutions of the present invention will be described in further detail below in conjunction with specific embodiments.

The chemicals used in the examples of the present invention and comparative examples are all commercial products unless otherwise specified, and the purity is industrial grade.

The percentages used in the examples of the present invention and comparative examples are mass percentages unless otherwise specified.

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

The performance test method of the foamed material prepared in the embodiment of the present invention and comparative example is as follows:

(1) Density: Tested with the method recorded in ASTM D792-2013;

(2) Hardness: Tested with Asker C hardness tester;

(3) Tensile strength and elongation at break: tested by the method recorded in ISO 1798-2008;

(4) Delamination tear strength: tested by the method recorded in ISO 20875-2018;

(5) Pendulum resilience: test with the method recorded in DIN 53512, the thickness of the sample is 20mm;

(6) Compression set: test with the method recorded in ISO 1856-2018;

(7) Durability test of foamed materials: first use MTS-831 elastic material testing machine - elastic body test system to carry out compression fatigue test on the material, the constant load is 1500N, the frequency is 1.41Hz, the number of cycles is 100,000 times, the compression fatigue After the end, test the pendulum rebound performance of the material with the method recorded in DIN 53512.

Example 1

(1) Add 2920g of adipic acid and 15L of solvent N,N-dimethylformamide into a 30L reaction kettle, add 3528g of hexamethylene diisocyanate (HDI) after the adipic acid is completely dissolved, and heat up 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 at the same time. After the reaction was completed, the temperature was raised to 160°C to remove the solvent and unreacted raw materials by vacuuming, and the isocyanate-terminated polyamide prepolymer was prepared. , the number average molecular weight is 5000g/mol, and the weight is 4100g.

(2) Add 200g 1,4-butanediol and 6500g PTMEG (number average molecular weight 2000g/mol) into a 30L reactor, stir and disperse evenly and heat up to 100°C; weigh 2050g in another separate container (1) Prepare the isocyanate-terminated polyamide prepolymer and 1265g 4,4-diphenylmethane diisocyanate (MDI), heat up to 120°C and mix well, add the obtained mixture into the reaction kettle, and stir quickly React for 60 seconds, then pour the reactant into a polytetrafluoroethylene mold at 100°C, and put it into a heat oven at 100°C for heat treatment for 15 hours after the reactant solidifies. 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 143245 g/mol and a weight of 9600 g.

(3) 5Kg of polyurethane elastomer particles prepared by the above step (2) are mixed with 50g of nucleating agent calcium carbonate (average particle size is 0.5 μm), 15g of antioxidant 1010, 5g of ultraviolet absorber UV326 and then extruded and granulated Expandable polyurethane elastomer particles with a diameter of 1-2mm, twin-screw extruder (Nanjing Ruiya, aspect ratio 44) 1-11 zone temperature is 165°C, 170°C, 175°C, 180°C, 185°C, 190°C ℃, 195℃, 195℃, 190℃, 185℃, 180℃.

(4) Put the foamable polyurethane elastomer particles and water obtained in the previous step into a foaming kettle with stirring according to the mass ratio of 1:3, and pour in carbon dioxide as a foaming agent. Saturation for 1 hour, and then release the pressure to prepare polyurethane elastomer foamed particles. The foamed particles were dried at a temperature of 40° C., and then matured at room temperature for one week before being used in the next step.

(5) The polyurethane elastomer foamed particles are molded in steam molding equipment (Kurt Aisha, K68HP), the steam pressure is 0.27MPa (140.1°C), and a 20mm thick polyurethane elastomer foam material molded product is prepared, placed After 24 hours, various performance tests were carried out, and the test results are shown in Table 1.

Example 2

(1) Add 2088g of suberic acid and 15L of solvent N,N-dimethylformamide into a 30L reactor, and add 4716g of dicyclohexylmethane 4,4-diisocyanate (H ₁₂ MDI ), heated up to 120°C, reacted for 6 hours under stirring, condensed and refluxed the evaporated solvent and reactants, and discharged the carbon dioxide generated by the reaction at the same time. The terminal polyamide prepolymer has a number average molecular weight of 1000 g/mol and a weight of 5400 g.

(2) Add 731g 1,4-butanediol and 5760g polybutylene adipate (number average molecular weight is 2000g/mol) in the 30L reactor, stir and disperse evenly and heat up to 100 ℃; Weigh 1000g of the isocyanate-terminated polyamide prepolymer prepared in step (1) and 2500g of 4,4-diphenylmethane diisocyanate (MDI), heat up to 120°C and mix well, and add the obtained mixture to the reaction In the kettle, react for 60s under rapid stirring, then pour the reactant into a polytetrafluoroethylene mold at 100°C, and after the reactant solidifies, put it into a hot oven at 100°C for heat treatment for 15h. 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 138123 g/mol and a weight of 9550 g.

(3) 5Kg of polyurethane elastomer particles prepared by the above step (2) are mixed with 50g of nucleating agent calcium carbonate (average particle size is 0.5 μm), 15g of antioxidant 1010, 5g of ultraviolet absorber UV326 and then extruded and granulated Expandable polyurethane elastomer particles with a diameter of 1-2mm, twin-screw extruder (Nanjing Ruiya, aspect ratio 44) 1-11 zone temperature is 165°C, 170°C, 175°C, 180°C, 185°C, 190°C ℃, 195℃, 195℃, 190℃, 185℃, 180℃.

(4) Put the foamable polyurethane elastomer particles and water obtained in the previous step into a foaming kettle with stirring according to the mass ratio of 1:3, and pour in carbon dioxide as a foaming agent. Saturation for 1 hour, and then release the pressure to prepare polyurethane elastomer foamed particles. The foamed particles were dried at a temperature of 40° C., and then matured at room temperature for one week before being used in the next step.

(5) The polyurethane elastomer foamed particles are molded in steam molding equipment (Kurt Aisha, K68HP), the steam pressure is 0.21MPa (134.1°C), and a 20mm thick polyurethane elastomer foam material molded product is prepared, placed After 24 hours, various performance tests were carried out, and the test results are shown in Table 1.

Example 3

(1) Add 4040g of sebacic acid and 10L of solvent dimethyl sulfoxide (DMSO) into a 30L reaction kettle, add 3696g of pentamethylene diisocyanate (PDI) after the sebacic acid is completely dissolved, and heat up to 120°C, Stirring and reacting for 6 hours, the evaporated solvent and reactants were condensed and refluxed, and the carbon dioxide produced by the reaction was discharged at the same time. After the reaction was completed, the temperature was raised to 160°C to remove the solvent and unreacted raw materials in a vacuum, and an isocyanate-terminated polyamide prepolymer was prepared. The number average molecular weight was 1500 g/mol, and the weight was 5400 g.

(2) Add 513g of 1,4-butanediol and 7683g of PTMEG (the number average molecular weight is 2000g/mol) into a 30L reactor, stir and disperse evenly and heat up to 100°C; weigh 3000g in another separate container (1) Prepare the isocyanate-terminated polyamide prepolymer and 3345g 4,4-diphenylmethane diisocyanate (MDI), heat up to 120°C and mix well, add the obtained mixture into the reaction kettle, and stir rapidly React for 60 seconds, then pour the reactant into a polytetrafluoroethylene mold at 100°C, and put it into a heat oven at 100°C for heat treatment for 15 hours after the reactant solidifies. 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 133659 g/mol and a weight of 13200 g.

(3) 5Kg of polyurethane elastomer particles prepared by the above step (2) are mixed with 50g of nucleating agent calcium carbonate (average particle size is 0.5 μm), 15g of antioxidant 1010, 5g of ultraviolet absorber UV326 and then extruded and granulated Expandable polyurethane elastomer particles with a diameter of 1-2mm, twin-screw extruder (Nanjing Ruiya, aspect ratio 44) 1-11 zone temperature is 165°C, 170°C, 175°C, 180°C, 185°C, 190°C ℃, 195℃, 195℃, 190℃, 185℃, 180℃.

(4) Put the foamable polyurethane elastomer particles and water obtained in the previous step into a foaming kettle with stirring according to the mass ratio of 1:3, and pour in carbon dioxide as a foaming agent. Saturation for 1 hour, and then release the pressure to prepare polyurethane elastomer foamed particles. The foamed particles were dried at a temperature of 40° C., and then matured at room temperature for one week before being used in the next step.

(5) The polyurethane elastomer foamed particles are molded in steam molding equipment (Kurt Aisha, K68HP), the steam pressure is 0.24MPa (137.2°C), and a 20mm thick polyurethane elastomer foam material molded product is prepared, placed After 24 hours, various performance tests were carried out, and the test results are shown in Table 1.

Example 4

(1) Add 2920g of adipic acid and 15L of solvent dimethyl sulfoxide (DMSO) into a 30L reactor, add 4032g of hexamethylene diisocyanate (HDI) after the adipic acid is completely dissolved, and heat up to 120°C. Stirring and reacting for 6 hours, the evaporated solvent and reactants were condensed and refluxed, and the carbon dioxide produced by the reaction was discharged at the same time. After the reaction was completed, the temperature was raised to 160°C to remove the solvent and unreacted raw materials in a vacuum, and an isocyanate-terminated polyamide prepolymer was prepared. The number average molecular weight was 1300 g/mol, and the weight was 4800 g.

(2) Add 459g 1,4-butanediol and 6600g PTMEG (number-average molecular weight: 2000g/mol) to a 30L reactor, stir to disperse evenly and heat up to 100°C; weigh 2600g in another separate container (1) Prepare the isocyanate-terminated polyamide prepolymer and 1600g 4,4-diphenylmethane diisocyanate (MDI), heat up to 120°C and mix well, add the obtained mixture into the reaction kettle, and stir rapidly React for 60 seconds, then pour the reactant into a polytetrafluoroethylene mold at 100°C, and put it into a heat oven at 100°C for heat treatment for 15 hours after the reactant solidifies. 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 136391 g/mol and a weight of 10850 g.

(3) 5Kg of polyurethane elastomer particles prepared by the above step (2) are mixed with 50g of nucleating agent calcium carbonate (average particle size is 0.5 μm), 15g of antioxidant 1010, 5g of ultraviolet absorber UV326 and then extruded and granulated Expandable polyurethane elastomer particles with a diameter of 1-2mm, twin-screw extruder (Nanjing Ruiya, aspect ratio 44) 1-11 zone temperature is 165°C, 170°C, 175°C, 180°C, 185°C, 190°C ℃, 195℃, 195℃, 190℃, 185℃, 180℃.

(4) Put the foamable polyurethane elastomer particles and water obtained in the previous step into a foaming kettle with stirring according to the mass ratio of 1:3, and pour in carbon dioxide as a foaming agent. Saturation for 1 hour, and then release the pressure to prepare polyurethane elastomer foamed particles. The foamed particles were dried at a temperature of 40° C., and then matured at room temperature for one week before being used in the next step.

(5) The polyurethane elastomer foamed particles are molded in steam molding equipment (Kurt Aisha, K68HP), the steam pressure is 0.23MPa (136.2°C), and a 20mm thick polyurethane elastomer foam material molded product is prepared, placed After 24 hours, various performance tests were carried out, and the test results are shown in Table 1.

Example 5

(1) Add 2920g of adipic acid and 15L of solvent dimethyl sulfoxide (DMSO) into a 30L reactor, add 4032g of hexamethylene diisocyanate (HDI) after the adipic acid is completely dissolved, and heat up to 120°C. Stirring and reacting for 6 hours, the evaporated solvent and reactants were condensed and refluxed, and the carbon dioxide produced by the reaction was discharged at the same time. After the reaction was completed, the temperature was raised to 160°C to remove the solvent and unreacted raw materials in a vacuum, and an isocyanate-terminated polyamide prepolymer was prepared. The number average molecular weight was 1300 g/mol, and the weight was 4800 g.

(2) Add 602g of 1,6-hexanediol and 6600g of PTMEG (the number average molecular weight is 2000g/mol) into a 30L reactor, stir and disperse evenly and heat up to 100°C; weigh 2600g in another separate container (1) Prepared isocyanate-terminated polyamide prepolymer and 1677g dicyclohexylmethane 4,4-diisocyanate (H ₁₂ MDI), warming up to 120°C and mixing evenly, adding the resulting mixture to the reaction kettle, and quickly React under stirring for 60s, then pour the reactant into a polytetrafluoroethylene mold at 100°C, and put the reactant into a heat oven at 100°C for heat treatment for 15h after solidification. 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 140021 g/mol and a weight of 10732 g.

(3) 5Kg of polyurethane elastomer particles prepared by the above step (2) are mixed with 50g of nucleating agent calcium carbonate (average particle size is 0.5 μm), 15g of antioxidant 1010, 5g of ultraviolet absorber UV326 and then extruded and granulated Expandable polyurethane elastomer particles with a diameter of 1-2mm, twin-screw extruder (Nanjing Ruiya, aspect ratio 44) 1-11 zone temperature is 165°C, 170°C, 175°C, 180°C, 185°C, 190°C ℃, 195℃, 195℃, 190℃, 185℃, 180℃.

(4) Put the foamable polyurethane elastomer particles and water obtained in the previous step into a foaming kettle with stirring according to the mass ratio of 1:3, and pour in carbon dioxide as a foaming agent. Saturation for 1 hour, and then release the pressure to prepare polyurethane elastomer foamed particles. The foamed particles were dried at a temperature of 40° C., and then matured at room temperature for one week before being used in the next step.

(5) The polyurethane elastomer foamed particles are molded in steam molding equipment (Kurt Aisha, K68HP), the steam pressure is 0.16MPa (128.1°C), and a 20mm thick polyurethane elastomer foam material molded product is prepared, placed After 24 hours, various performance tests were carried out, and the test results are shown in Table 1.

Example 6

(1) Add 2920g of adipic acid and 15L of solvent dimethyl sulfoxide (DMSO) into a 30L reactor, add 4032g of hexamethylene diisocyanate (HDI) after the adipic acid is completely dissolved, and heat up to 120°C. Stirring and reacting for 6 hours, the evaporated solvent and reactants were condensed and refluxed, and the carbon dioxide produced by the reaction was discharged at the same time. After the reaction was completed, the temperature was raised to 160°C to remove the solvent and unreacted raw materials in a vacuum, and an isocyanate-terminated polyamide prepolymer was prepared. The number average molecular weight was 1300 g/mol, and the weight was 4800 g.

(2) Add 316.2g of ethylene glycol and 6600g of PTMEG (the number average molecular weight is 2000g/mol) to a 30L reactor, stir and disperse evenly and heat up to 100°C; weigh 2600g of step (1) in another separate container The prepared isocyanate-terminated polyamide prepolymer and 1075g hexamethylene diisocyanate (HDI) were heated up to 120°C and mixed uniformly. The resulting mixture was added to the reactor and reacted for 60s under rapid stirring, and then the reactant Pour it into a polytetrafluoroethylene mold at 100°C. After the reactant is solidified, put it into a hot oven at 100°C 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 138109 g/mol and a weight of 9953 g.

(3) 5Kg of polyurethane elastomer particles prepared by the above step (2) are mixed with 50g of nucleating agent calcium carbonate (average particle size is 0.5 μm), 15g of antioxidant 1010, 5g of ultraviolet absorber UV326 and then extruded and granulated Expandable polyurethane elastomer particles with a diameter of 1-2mm, twin-screw extruder (Nanjing Ruiya, aspect ratio 44) 1-11 zone temperature is 165°C, 170°C, 175°C, 180°C, 185°C, 190°C ℃, 195℃, 195℃, 190℃, 185℃, 180℃.

(4) Put the foamable polyurethane elastomer particles and water obtained in the previous step into a foaming kettle with stirring according to the mass ratio of 1:3, and pour in carbon dioxide as a foaming agent. Saturation for 1 hour, and then release the pressure to prepare polyurethane elastomer foamed particles. The foamed particles were dried at a temperature of 40° C., and then matured at room temperature for one week before being used in the next step.

(5) The polyurethane elastomer foamed particles are molded in steam molding equipment (Kurt Aisha, K68HP), the steam pressure is 0.13MPa (124.1°C), and a 20mm thick polyurethane elastomer foam material molded product is prepared, placed After 24 hours, various performance tests were carried out, and the test results are shown in Table 1.

Example 7

(1) Add 2920g of adipic acid and 15L of solvent dimethyl sulfoxide (DMSO) into a 30L reactor, add 4032g of hexamethylene diisocyanate (HDI) after the adipic acid is completely dissolved, and heat up to 120°C. Stirring and reacting for 6 hours, the evaporated solvent and reactants were condensed and refluxed, and the carbon dioxide produced by the reaction was discharged at the same time. After the reaction was completed, the temperature was raised to 160°C to remove the solvent and unreacted raw materials in a vacuum, and an isocyanate-terminated polyamide prepolymer was prepared. The number average molecular weight was 1300 g/mol, and the weight was 4800 g.

(2) Add 459g 1,4-butanediol and 6600g PTMEG (number-average molecular weight: 2000g/mol) to a 30L reactor, stir to disperse evenly and heat up to 100°C; weigh 2600g in another separate container (1) Prepare the isocyanate-terminated polyamide prepolymer and 986g pentamethylene diisocyanate (PDI), heat up to 120°C and mix uniformly, add the resulting mixture into the reactor, react under rapid stirring for 60s, and then The reactant was poured into a polytetrafluoroethylene mold at 100° C., and after the reactant solidified, it was put into a heat oven at 100° C. for heat treatment for 15 hours. After the heat treatment, the resulting 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 139,371 g/mol and a weight of 9,745 g.

(3) 5Kg of polyurethane elastomer particles prepared by the above step (2) are mixed with 50g of nucleating agent calcium carbonate (average particle size is 0.5 μm), 15g of antioxidant 1010, 5g of ultraviolet absorber UV326 and then extruded and granulated Expandable polyurethane elastomer particles with a diameter of 1-2mm, twin-screw extruder (Nanjing Ruiya, aspect ratio 44) 1-11 zone temperature is 165°C, 170°C, 175°C, 180°C, 185°C, 190°C ℃, 195℃, 195℃, 190℃, 185℃, 180℃.

(4) Put the foamable polyurethane elastomer particles and water obtained in the previous step into a foaming kettle with stirring according to the mass ratio of 1:3, and pour in carbon dioxide as a foaming agent. Saturation for 1 hour, and then release the pressure to prepare polyurethane elastomer foamed particles. The foamed particles were dried at a temperature of 40° C., and then matured at room temperature for one week before being used in the next step.

(5) The polyurethane elastomer foamed particles are molded in steam molding equipment (Kurt Aisha, K68HP), the steam pressure is 0.14MPa (125.5°C), and a 20mm thick polyurethane elastomer foam material molded product is prepared, placed After 24 hours, various performance tests were carried out, and the test results are shown in Table 1.

Example 8

(1) Add 2920g of adipic acid and 15L of solvent dimethyl sulfoxide (DMSO) into a 30L reactor, add 4032g of hexamethylene diisocyanate (HDI) after the adipic acid is completely dissolved, and heat up to 120°C. Stirring and reacting for 6 hours, the evaporated solvent and reactants were condensed and refluxed, and the carbon dioxide produced by the reaction was discharged at the same time. After the reaction was completed, the temperature was raised to 160°C to remove the solvent and unreacted raw materials in a vacuum, and an isocyanate-terminated polyamide prepolymer was prepared. The number average molecular weight was 1300 g/mol, and the weight was 4800 g.

(2) Add 252g of ethylene glycol and 5748g of PTMEG (the number average molecular weight is 2000g/mol) to a 30L reactor, stir and disperse evenly and heat up to 100°C; weigh 3500g in another separate container and prepare by step (1) The isocyanate-terminated polyamide prepolymer and 500g of hexamethylene diisocyanate (HDI) were heated to 120°C and mixed uniformly. The resulting mixture was added to the reactor and reacted for 60s under rapid stirring, and then the reactant was poured Put it into a polytetrafluoroethylene mold at 100°C. After the reactant is solidified, put it into a hot oven at 100°C for heat treatment for 15h. After the heat treatment, the resulting 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 134,245 g/mol and a weight of 9,643 g.

(3) 5Kg of polyurethane elastomer particles prepared by the above step (2) are mixed with 50g of nucleating agent calcium carbonate (average particle size is 0.5 μm), 15g of antioxidant 1010, 5g of ultraviolet absorber UV326 and then extruded and granulated Expandable polyurethane elastomer particles with a diameter of 1-2mm, twin-screw extruder (Nanjing Ruiya, aspect ratio 44) 1-11 zone temperature is 165°C, 170°C, 175°C, 180°C, 185°C, 190°C ℃, 195℃, 195℃, 190℃, 185℃, 180℃.

(4) Put the foamable polyurethane elastomer particles and water obtained in the previous step into a foaming kettle with stirring according to the mass ratio of 1:3, and pour in carbon dioxide as a foaming agent. Saturation for 1 hour, and then release the pressure to prepare polyurethane elastomer foamed particles. The foamed particles were dried at a temperature of 40° C., and then matured at room temperature for one week before being used in the next step.

(5) The polyurethane elastomer foamed particles are molded in steam molding equipment (Kurt Aisha, K68HP), the steam pressure is 0.13MPa (124.1°C), and a 20mm thick polyurethane elastomer foam material molded product is prepared, placed After 24 hours, various performance tests were carried out, and the test results are shown in Table 1.

Example 9

(1) Add 2920g of adipic acid and 15L of solvent dimethyl sulfoxide (DMSO) into a 30L reactor, add 4032g of hexamethylene diisocyanate (HDI) after the adipic acid is completely dissolved, and heat up to 120°C. Stirring and reacting for 6 hours, the evaporated solvent and reactants were condensed and refluxed, and the carbon dioxide produced by the reaction was discharged at the same time. After the reaction was completed, the temperature was raised to 160°C to remove the solvent and unreacted raw materials in a vacuum, and an isocyanate-terminated polyamide prepolymer was prepared. The number average molecular weight was 1300 g/mol, and the weight was 4800 g.

(2) Add 800g of ethylene glycol and 4000g of PTMEG (the number average molecular weight is 2000g/mol) into a 30L reactor, stir and disperse evenly and heat up to 100°C; weigh 3484g in another separate container to prepare by step (1) The isocyanate-terminated polyamide prepolymer and 1715g of hexamethylene diisocyanate (HDI) were heated to 120°C and mixed uniformly. The resulting mixture was added to the reactor and reacted for 60s under rapid stirring, and then the reactant was poured Put it into a polytetrafluoroethylene mold at 100°C. After the reactant is solidified, put it into a hot oven at 100°C for heat treatment for 15h. 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 142103 g/mol and a weight of 9754 g.

(3) 5Kg of polyurethane elastomer particles prepared by the above step (2) are mixed with 50g of nucleating agent calcium carbonate (average particle size is 0.5 μm), 15g of antioxidant 1010, 5g of ultraviolet absorber UV326 and then extruded and granulated Expandable polyurethane elastomer particles with a diameter of 1-2mm, twin-screw extruder (Nanjing Ruiya, aspect ratio 44) 1-11 zone temperature is 165°C, 170°C, 175°C, 180°C, 185°C, 190°C ℃, 195℃, 195℃, 190℃, 185℃, 180℃.

(4) Put the foamable polyurethane elastomer particles and water obtained in the previous step into a foaming kettle with stirring according to the mass ratio of 1:3, and pour in carbon dioxide as a foaming agent. Saturation for 1 hour, and then release the pressure to prepare polyurethane elastomer foamed particles. The foamed particles were dried at a temperature of 40° C., and then matured at room temperature for one week before being used in the next step.

(5) The polyurethane elastomer foamed particles are molded in steam molding equipment (Kurt Aisha, K68HP), the steam pressure is 0.13MPa (124.1°C), and a 20mm thick polyurethane elastomer foam material molded product is prepared, placed After 24 hours, various performance tests were carried out, and the test results are shown in Table 1.

Comparative example 1

(1) Add 459g of 1,4-butanediol and 6600g of PTMEG (the number average molecular weight is 2000g/mol) into a 30L reactor, stir and disperse evenly and raise the temperature to 100°C; weigh 2100g of 4 , 4-diphenylmethane diisocyanate (MDI), heated up to 120°C, added to the reaction kettle, reacted for 60s under rapid stirring, then poured the reactant into a polytetrafluoroethylene mold at 100°C, and waited for the reactant to solidify , placed in a hot oven at 100°C for heat treatment for 15h. 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 143203 g/mol and a weight of 8342 g.

(2) 5Kg of polyurethane elastomer particles prepared by the above steps (1) are mixed with 50g of nucleating agent calcium carbonate (average particle size is 0.5 μm), 15g of antioxidant 1010, 5g of ultraviolet absorber UV326 and then extruded and granulated Expandable polyurethane elastomer particles with a diameter of 1-2mm, twin-screw extruder (Nanjing Ruiya, aspect ratio 44) 1-11 zone temperature is 165°C, 170°C, 175°C, 180°C, 185°C, 190°C ℃, 195℃, 195℃, 190℃, 185℃, 180℃.

(3) Put the foamable polyurethane elastomer particles and water obtained in the previous step into a foaming kettle with stirring according to the mass ratio of 1:3, and pour carbon dioxide into it as a foaming agent. Saturation for 1 hour, and then release the pressure to prepare polyurethane elastomer foamed particles. The foamed particles were dried at a temperature of 40° C., and then matured at room temperature for one week before being used in the next step.

(4) Polyurethane elastomer foamed particles are molded in steam molding equipment (Kurt Aisha, K68HP), the steam pressure is 0.34MPa (146°C), and a 20mm thick polyurethane elastomer foamed material molded product is prepared, placed After 24 hours, various performance tests were carried out, and the test results are shown in Table 1.

Comparative example 2

(1) Add 459g 1,4-butanediol and 6600g PTMEG (number average molecular weight: 2000g/mol) into a 30L reactor, stir to disperse evenly and heat up to 100°C; weigh 1411.2g in another separate container Hexamethylene diisocyanate (HDI), heated up to 120°C, added to the reaction kettle, reacted for 60s under rapid stirring, then poured the reactant into a polytetrafluoroethylene mold at 100°C, after the reactant solidified, put Heat treatment in a hot oven at 100°C 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 141511 g/mol and a weight of 7567 g.

(2) 5Kg of polyurethane elastomer particles prepared by the above steps (1) are mixed with 50g of nucleating agent calcium carbonate (average particle size is 0.5 μm), 15g of antioxidant 1010, 5g of ultraviolet absorber UV326 and then extruded and granulated Expandable polyurethane elastomer particles with a diameter of 1-2mm, twin-screw extruder (Nanjing Ruiya, aspect ratio 44) 1-11 zone temperature is 165°C, 170°C, 175°C, 180°C, 185°C, 190°C ℃, 195℃, 195℃, 190℃, 185℃, 180℃.

(3) Put the foamable polyurethane elastomer particles and water obtained in the previous step into a foaming kettle with stirring according to the mass ratio of 1:3, and pour carbon dioxide into it as a foaming agent. Saturation for 1 hour, and then release the pressure to prepare polyurethane elastomer foamed particles. The foamed particles were dried at a temperature of 40° C., and then matured at room temperature for one week before being used in the next step.

(4) The polyurethane elastomer foamed particles are molded in steam molding equipment (Kurt Aisha, K68HP), the steam pressure is 0.12MPa (122.7°C), and a 20mm thick polyurethane elastomer foam material molded product is prepared, placed After 24 hours, various performance tests were carried out, and the test results are shown in Table 1.

Table 1 Performance test results of polyurethane elastomer foam moldings

Table 1 result shows, with respect to the foam material that does not introduce the foam material that the polyurethane elastomer of polyamide segment is prepared in the molecular chain (as comparative example 1,2), the polyurethane elastomer foam material provided by the present invention has significantly lower Higher density and higher hardness without sacrificing other aspects of performance, especially rebound performance. In addition, the polyurethane elastomer foam material provided by the present invention has almost no reduction in rebound performance after a long-term cyclic compression test, and has good durability.

Therefore, the polyurethane elastomer foaming material provided by the present invention has excellent comprehensive properties, can meet the needs of various application occasions, and thus has great industrial applicability.

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

The embodiments described in the present invention are only for exemplary purposes, and are not intended to limit the protection scope of the present invention. Those skilled in the art can make various other replacements, changes and improvements within the scope of the present invention. Therefore, the present invention does not Be limited by the embodiments described above, and only by the claims.

Claims (10)

1. The polyurethane elastomer is characterized by comprising the following raw materials in parts by mass: 5-50 parts of isocyanate-terminated polyamide prepolymer, 2-40 parts of diisocyanate A1, 30-100 parts of polyether polyol or polyester polyol and 1-10 parts of chain extender;

wherein the isocyanate-terminated polyamide prepolymer is prepared by reacting diisocyanate A2 with aliphatic dicarboxylic acid, and the number average molecular weight of the isocyanate-terminated polyamide prepolymer is 1000-5000 g/mol; the diisocyanate A2 is selected from aliphatic and/or alicyclic diisocyanate, and the aliphatic dicarboxylic acid is selected from alpha, omega-aliphatic straight chain dicarboxylic acid with 4-20 carbon atoms.

2. The polyurethane elastomer according to claim 1, wherein the polyurethane elastomer is prepared from the following raw materials in parts by mass: 10-35 parts of isocyanate-terminated polyamide prepolymer, 5-35 parts of diisocyanate A1, 40-80 parts of polyether polyol or polyester polyol and 2-8 parts of chain extender; and/or

The number average molecular weight of the polyurethane elastomer is 100000 to 200000g/mol, preferably 120000 to 150000g/mol.

3. The polyurethane elastomer according to claim 1 or 2, wherein 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 (isocyanatomethyl) cyclohexane, 1, 3-bis (isocyanatomethyl) cyclohexane, cyclohexane-1, 4-diisocyanate, 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-dodecanedioic acid, 1, 13-tridecanedioic acid and 1, 14-tetradecanedioic acid.

4. A polyurethane elastomer according to any of claims 1-3, characterised 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.

5. A polyurethane elastomer according to any one of the claims 1-4 characterised in, that said diisocyanate A1 is selected from one or more of aliphatic, cycloaliphatic, aromatic diisocyanates, preferably from one or more of diphenylmethane 2, 2-diisocyanate, diphenylmethane 2, 4-diisocyanate, diphenylmethane 4, 4-diisocyanate, naphthylene 1, 5-diisocyanate, toluene 2, 4-diisocyanate, toluene 2, 6-diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane 2, 4-diisocyanate, dicyclohexylmethane 4, 4-diisocyanate.

6. A polyurethane elastomer according to any one of claims 1-5, characterised in that the polyether polyol or polyester polyol has a number average molecular weight of 500-10000 g/mol, preferably 700-4000 g/mol;

preferably, the polyether polyol is prepared by reacting an initiator with a 2-6 membered epoxy compound, wherein the initiator is selected from one or more of water, propylene glycol, glycerol, trimethylolpropane, ethylenediamine, pentaerythritol, xylitol, triethylene diamine, 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; the polyether polyol is preferably selected from polytetramethylene ether glycol; and/or

The polyester polyol is selected from one or more of alkyd polyester polyol, polycaprolactone polyol and polycarbonate polyol; the polyester polyol is preferably selected from alkyd polyester polyols obtained by reacting an aliphatic and/or aromatic diol having 2 to 12 carbon atoms with an aliphatic and/or aromatic dicarboxylic acid having 4 to 15 carbon atoms, a dicarboxylic acid anhydride or a dicarboxylic acid ester, and is more preferably polybutylene adipate.

7. A polyurethane elastomer according to any one of claims 1-6 wherein 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 bis (hydroxyethyl) ether, neopentyl glycol.

8. A polyurethane elastomer foaming composition comprising the polyurethane elastomer according to any one of claims 1 to 7;

preferably, the polyurethane elastomer foaming composition further comprises one or more of an antioxidant, a UV auxiliary agent, a foaming nucleating agent and a filler;

more preferably, the polyurethane elastomer foaming composition comprises the following components in parts by mass: 500 to 2000 parts of the polyurethane elastomer as claimed in any one of claims 1 to 7, 5 to 20 parts of a foam nucleating agent, 1 to 10 parts of an antioxidant and 0.1 to 5 parts of a UV auxiliary agent.

9. A polyurethane elastomer foam material, which is prepared from the polyurethane elastomer foam composition according to claim 8 under the action of a foaming agent;

preferably, the blowing agent is selected from nitrogen, carbon dioxide, alkanes, chlorofluorocarbons, hydrochlorocarbons, hydrofluorocarbons or hydrochlorofluorocarbon blowing agents.

10. Use of the polyurethane elastomer foam composition of claim 8 or the polyurethane elastomer foam of claim 9 in the preparation of: one or more of a sole material, a mattress, a gymnastic mat, a liner, an automotive interior or exterior component, an automotive trim element, an acoustic insulation material, a cushioning material, a bicycle saddle, a toy, a tire and tire component, a surface covering for an athletic field, stadium or path, a vibration damping material, a packaging material.