CN115785392A - Polyurethane elastomer, foaming material and application thereof - Google Patents
Polyurethane elastomer, foaming material and application thereof Download PDFInfo
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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
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 application of the polyurethane elastomer foam material.
Background
The technology of foaming thermoplastic polyurethane elastomers (TPU) with inert gases (e.g., carbon dioxide, nitrogen, alkanes, etc.) to make TPU foams is known. For example, chinese patent CN 101370861A discloses a method for preparing a foamed material product by extruding a thermoplastic polyurethane elastomer with shore hardness of 44-84A and a filler, suspending and impregnating the extruded thermoplastic polyurethane elastomer and the filler in a high-pressure fluid, preparing foamed particles of the thermoplastic polyurethane elastomer, and molding the foamed particles in a mold. Chinese patent CN 103804890A discloses a method for extruding foamed thermoplastic polyurethane elastomer particles, which comprises 100 parts of thermoplastic polyurethane elastomer, 0.01-0.5 part of foaming nucleating agent and 0.01-0.2 part of antioxidant; the preparation method of the extrusion foaming thermoplastic polyurethane elastomer particles comprises the following steps: mixing the materials, extruding and granulating to obtain beads suitable for foaming; and then putting the beads into a foaming special extruder, carrying out underwater granulation after foaming through a mouth die to obtain product particles, and then forming the prepared foamed particles in a die to prepare a foamed material product. The thermoplastic polyurethane elastomer foam material prepared by the method has the characteristics of light weight, softness, comfort, good rebound resilience, good physical and mechanical properties and the like, and is widely applied to sports shoe materials, packages, living homes and the like. However, TPU foam materials also have some disadvantages, and existing TPU foam materials have the disadvantage of insufficient strength after further reduction of density, and in addition, in some application occasions, the TPU foam materials are required to have higher hardness and higher resilience, but the resilience of the TPU foam materials is usually reduced after the hardness is increased.
In recent years, polyether Polyamide Elastomer (PEBA) foam, another thermoplastic elastomer foam, has gained a great deal of attention. For example, chinese patent CN 107629448A discloses a method for preparing block polyetheramide foamed particles with sandbag structure, which comprises mixing and granulating polyether polyamide elastomer, modifier, filler and coupling agent, and then carrying out supercritical foaming to prepare a foamed material. Chinese patent CN108884253A discloses a foamed material of polyether polyamide block copolymer elastomer consisting of polyamide 11 blocks, polyamide 12 blocks, polyamide 6 or polyamide 6.10 rigid blocks and polyether blocks. Chinese patent CN 111117215A discloses a supercritical foaming material of an elastomer composition consisting of at least two polyamide elastomers, an antioxidant and a nucleating agent. Compared with a thermoplastic polyurethane elastomer foaming material, the polyether polyamide elastomer foaming material has higher resilience and lower density, but the tear resistance of the polyether polyamide elastomer foaming material is insufficient, so that a shoe material made of the polyether polyamide elastomer foaming material is easy to wear under the condition of friction and collision; in addition, polyether polyamide elastomer materials have a higher cost, thereby limiting their use in large quantities.
Other patents disclose foams of polyurethane elastomer/polyether polyamide elastomer compositions. For example, chinese patent CN 108250734A discloses a method for preparing Pebax/TPU blended foam material, which adopts a weight ratio of Pebax to TPU of 10: and (3) extruding and granulating the mixture of 90-90. Chinese patent CN 113943489A discloses a foaming material composition and a preparation method of a foaming material, wherein 10-90% of block copolymer, 4-84% of thermoplastic polyurethane elastomer, 1-25% of polyurethane ionomer and 0.1-5% of foaming nucleating agent are mixed and granulated, and then a foaming agent is adopted for foaming to prepare the foaming material. The composite foaming material prepared by the blending method has poor durability due to the problem of compatibility among components, and the resilience performance is easy to reduce after long-term cyclic reciprocating compression.
Therefore, it is an urgent problem in the art to develop a foaming material having low density, high tear strength, better resilience under high hardness, and good resistance to cyclic reciprocating compression.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a polyurethane elastomer, and a polyurethane foam material prepared from the polyurethane elastomer has obviously improved comprehensive properties, including lower density, higher tearing strength, improved hardness, good resilience, low manufacturing cost and strong practicability.
It is another object of the present invention to provide a polyurethane elastomer foam composition and a polyurethane elastomer foam obtained therefrom.
Still another object of the present invention is to provide the polyurethane elastomer foaming composition and the use of the polyurethane elastomer foaming material.
The first aspect of the invention provides a polyurethane elastomer, which comprises 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.
In the polyurethane elastomer provided by the invention, carbon dioxide is removed by the reaction of the isocyanate group of diisocyanate A2 and the carboxyl group of aliphatic dicarboxylic acid, so as to form the isocyanate-terminated polyamide prepolymer, which has the structure shown in the following general formula:
wherein R is 1 Denotes a residue of an aliphatic dicarboxylic acid except a carboxyl group, R 2 Denotes a residue of diisocyanate A2 from which an isocyanate group is removed, and n denotes a number that enables the isocyanate terminated polyamide prepolymer to attain a desired number average molecular weight.
The molecular chain composition of the polyurethane elastomer provided by the invention comprises a polyamide chain segment obtained by reacting diisocyanate A2 and aliphatic dicarboxylic acid, in addition to a polyurethane hard segment formed by reacting macromolecular polyester or polyether soft segment, diisocyanate A1 and a chain extender. The introduction of the polyamide chain segment enhances the rigidity of a hard segment of a polyurethane elastomer molecular chain and enhances the phase separation effect of the hard segment and a soft segment, so that the foaming material prepared from the polyurethane elastomer still has excellent resilience performance under higher hardness. The introduction of polyamide segments also increases the melt strength of the polyurethane elastomer, making it possible to prepare foamed materials having a lower density. In addition, the polyamide chain segment and the polyurethane chain segment in the molecular chain of the polyurethane elastomer provided by the invention have different melting peaks, and in the steam forming process of the foaming material prepared from the polyurethane elastomer, one chain segment can keep a crystalline state and play a role in supporting the shape by selecting proper steam pressure (or temperature), and the other chain segment is in a molten state, so that the foaming material obtains a better bonding effect, and a foaming material product prepared from the polyurethane elastomer has higher tearing strength. Moreover, compared with the mixed foaming material of the thermoplastic polyurethane elastomer and the polyether polyamide elastomer, the resilience of the foaming material obtained by the invention is not obviously reduced after long-term cyclic reciprocating compression test.
In the polyurethane elastomers provided herein, the isocyanate-terminated polyamide prepolymer may have a number average molecular weight (Mn) of 1000 to 5000g/mol, including but not limited to a molecular weight range of about 1000g/mol, about 1500g/mol, about 2000g/mol, about 2500g/mol, about 3000g/mol, about 3500g/mol, about 4000g/mol, about 4500g/mol, about 5000g/mol, or any combination thereof. In some preferred embodiments, the isocyanate-terminated polyamide prepolymer may have a number average molecular weight of 1000 to 2000g/mol.
In the polyurethane elastomer provided by the invention, the preparation raw materials further comprise the following components 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.
In the polyurethane elastomer provided by the present invention, the number average molecular weight (Mn) of the polyurethane elastomer may be 100000 to 200000g/mol, including but not limited to a molecular weight range of about 100000g/mol, about 110000g/mol, about 120000g/mol, about 130000g/mol, about 140000g/mol, about 150000g/mol, about 160000g/mol, about 170000g/mol, about 180000g/mol, about 190000g/mol, about 200000g/mol or any combination thereof. In some preferred embodiments, the polyurethane elastomer may have a number average molecular weight of 120000 to 150000g/mol.
In the polyurethane elastomer provided by the present invention, the diisocyanate A2 may be selected from aliphatic and/or cycloaliphatic 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 (isocyanatomethyl) cyclohexane, 1, 3-bis (isocyanatomethyl) cyclohexane (HXDI), cyclohexane-1, 4-diisocyanate, 1-methyl-cyclohexane-2, 6-diisocyanate. In some preferred embodiments, the diisocyanate A2 may be selected from the group consisting of Pentamethylene Diisocyanate (PDI), hexamethylene Diisocyanate (HDI), dicyclohexylmethane 4, 4-diisocyanate (H) 12 MDI).
In the polyurethane elastomer provided by the invention, the aliphatic dicarboxylic acid can be selected from alpha, omega-aliphatic linear chain dicarboxylic acids with 4-20 carbon atoms, which are common in the field, and include but are not limited to 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. In some preferred embodiments, the aliphatic dicarboxylic acid may be selected from alpha, omega-aliphatic linear dicarboxylic acids having 6 to 10 carbon atoms, such as adipic acid, suberic acid, sebacic acid, and the like.
The polyurethane elastomer provided by the present invention may have a molar ratio of the diisocyanate A2 to the reactive group of the aliphatic dicarboxylic acid (-NCO) — COOH) of 1.05 to 1.5, including but not limited to a molar ratio interval of about 1.05. 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 reactive groups (-NCO) — COOH) may be 1.1 to 1.3.
In the polyurethane elastomer provided by the invention, the isocyanate-terminated polyamide prepolymer can be prepared by the following processes: dissolving aliphatic dicarboxylic acid in a solvent which does not react with diisocyanate A2, adding excessive diisocyanate A2, heating to 80-280 ℃ (for example, heating to 100-150 ℃) to perform reflux reaction, continuously stirring in the reaction process to discharge carbon dioxide, and removing the solvent and unreacted raw materials under reduced pressure after the reaction is finished, thereby preparing the isocyanate-terminated polyamide prepolymer.
Wherein, the solvent can be selected from polar organic solvents which are not reacted with diisocyanate A2 and are common in the field, including but not limited to N, N-dimethylformamide, N-dimethylacetamide, cyclohexanone, dimethyl sulfoxide, sulfolane and the like.
In the polyurethane elastomer provided by the present invention, the diisocyanate A1 may be selected from one or more of aliphatic, alicyclic and aromatic diisocyanates commonly used 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 (H) 12 MDI). In some preferred embodiments, the diisocyanate A1 may be selected from one or more of diphenylmethane 4, 4-diisocyanate (MDI), pentamethylene Diisocyanate (PDI), hexamethylene Diisocyanate (HDI).
In the polyurethane elastomer provided by the present invention, the polyether polyol or polyester polyol may be selected from the general kinds in the art. In some preferred embodiments, the polyether polyol or polyester polyol may have a number average molecular weight (Mn) of 500 to 10000g/mol, including but not limited to a molecular weight range of about 500g/mol, about 1000g/mol, about 2000g/mol, about 3000g/mol, about 4000g/mol, about 5000g/mol, about 6000g/mol, about 8000g/mol, about 10000g/mol, or any combination thereof. In some more preferred embodiments, the polyether polyol or polyester polyol may have a number average molecular weight of 700 to 4000g/mol. In some further preferred embodiments, the polyether polyol or polyester polyol may have a number average molecular weight of 1000 to 3000g/mol.
In the polyurethane elastomer provided by the 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 small molecular polyol, small molecular polyamine and small molecular alcohol amine which are common in the field, and comprises but is not limited to one or more of water, propylene glycol, glycerol, trimethylolpropane, ethylenediamine, pentaerythritol, xylitol, triethylene diamine, 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, tetrahydrofuran. In some preferred embodiments, the polyether polyol may be selected from polyethylene glycol prepared by reacting ethylene oxide with ethylene glycol, polypropylene glycol prepared by reacting propylene oxide with propylene glycol, polytetramethylene ether glycol (PTMEG) prepared by reacting water with Tetrahydrofuran (THF), copolyethers of the reaction products of THF with ethylene oxide or THF with propylene oxide, and the like. In some more preferred embodiments, the polyether polyol may be selected from polytetramethylene ether glycol (PTMEG).
In the polyurethane elastomer provided by the invention, the polyester polyol can be selected from one or more of alkyd polyester polyol, polycaprolactone polyol and polycarbonate polyol which are commonly used in the field.
The alkyd polyester polyol can be prepared by esterification or ester exchange reaction of common dihydric alcohol and dicarboxylic acid, dicarboxylic acid anhydride or dicarboxylic ester in the field, and the acid value of the alkyd polyester polyol can be 0-1.0 mgKOH/g, preferably 0.1-0.5 mgKOH/g.
The alkyd polyester polyol can be prepared by reacting common aliphatic and/or aromatic diol with 2-12 carbon atoms with aliphatic and/or aromatic dicarboxylic acid, dicarboxylic anhydride or dicarboxylic ester with 4-15 carbon atoms in the field.
Wherein the dihydric alcohol includes, but is not limited to, one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-butylene glycol, 1, 4-butylene glycol (BDO), 1, 5-Pentanediol (PDO), 1, 6-Hexanediol (HDO), 2-dimethyl-1, 3-propylene glycol, 1, 4-cyclohexanedimethanol, decanediol, 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, tetrahydrophthalic anhydride.
In some preferred embodiments, the glycol may be selected from ethylene glycol and/or 1, 4-butanediol; the dicarboxylic acid, dicarboxylic acid anhydride and dicarboxylic acid ester may be one or more selected from adipic acid, phthalic anhydride and tetrahydrophthalic anhydride. In some more preferred embodiments, the alkyd polyester polyol may be selected from polybutylene adipate.
In the preparation process of the alkyd polyester polyol, the molar ratio of the dihydric alcohol to the dicarboxylic acid, dicarboxylic anhydride or dicarboxylic ester may be 1.0 to 3.0, and for example, may be 1.02 to 2.0.
The polycaprolactone polyol can be prepared from an epsilon-caprolactone monomer and an initiator which are common in the field under the initiation action of a catalyst.
The polycarbonate polyol can be prepared by a phosgene method, a carbon dioxide regulation copolymerization method, a cyclic carbonate ring-opening polymerization method or an ester exchange method which are common in the field.
The polycarbonate polyol of the present invention is preferably prepared by transesterification of a diol and a carbonate, which are common in the art, wherein the diol includes, but is not limited to, one or more of 1, 2-ethanediol, 1, 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 invention, the chain extender can be a common chain extender in the field, especially a common micromolecule chain extender in the field, and the molecular weight of the chain extender can be 50-500 g/mol. In some preferred embodiments, the chain extender may be a small molecule diol or diamine chain extender as is common in the art, including but not limited to 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. In some more preferred embodiments, the chain extender may be selected from one or more of ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol.
The polyurethane elastomer provided by the invention can be prepared by the following processes: firstly, heating polyether polyol or polyester polyol and a chain extender in a reactor to mix uniformly (for example, heating to 80-150 ℃) in advance, then heating isocyanate-terminated polyamide prepolymer and diisocyanate A1 to mix uniformly (for example, heating to 100-150 ℃) in another container, adding the obtained mixture into the reactor to stir and react, curing and heat treating the obtained reactant (for example, heat treating at 80-120 ℃ for 10-20 hours), and grinding to obtain the granular polyurethane elastomer.
In a second aspect, the present invention provides a polyurethane elastomer foaming composition comprising a polyurethane elastomer according to any one of the above embodiments.
The foaming composition provided by the invention can also comprise one or more additives which are common in the field besides the polyurethane elastomer, and the additives comprise but are not limited to one or more of an antioxidant, a UV auxiliary agent, a foaming nucleating agent and a filler. In some preferred embodiments, the polyurethane elastomer foaming composition may include, in parts by mass: 500-2000 parts of polyurethane elastomer, 5-20 parts of foaming nucleating agent, 1-10 parts of antioxidant and 0.1-5 parts of UV auxiliary agent. In some more preferred embodiments, the polyurethane elastomer foaming composition may include, in parts by mass: 800-1500 parts of the polyurethane elastomer, 8-15 parts of a foaming nucleating agent, 1-5 parts of an antioxidant and 0.5-2 parts of a UV (ultraviolet) auxiliary agent.
In the foaming composition provided by the invention, the used additive can be any kind commonly used in the field of polyurethane foaming materials, and can be selected by a person skilled in the art according to the requirements of application occasions, material properties and the like. The antioxidant includes, but is not limited to, antioxidant 1010, antioxidant 168, antioxidant 1098, and the like; the UV auxiliary agent includes but is not limited to an ultraviolet resistant agent UV312, an ultraviolet absorbent UV326 and the like; the foaming nucleating agent includes but is not limited to calcium carbonate, talcum powder, silica, zeolite, montmorillonite, carbon black, kaolin, wollastonite, diatomite, mica sheet, titanium dioxide powder and the like, preferably one or more of calcium carbonate, talcum powder, montmorillonite and kaolin, the average particle size of the foaming nucleating agent can be 0.01-10 μm, for example, the average particle size of the foaming nucleating agent 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 a particle size interval which can be any combination, and the average particle size of the foaming nucleating agent is further preferably 0.05-5 μm.
The third aspect of the present invention provides a polyurethane elastomer foam material, which is prepared from the polyurethane elastomer foam composition according to any one of the above technical schemes under the action of a foaming agent.
In the foaming material provided by the invention, the foaming agent can be any kind 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 blowing agent may employ nitrogen and/or carbon dioxide.
The foaming material provided by the invention can be prepared by a preparation method of a polyurethane foaming material common in the field, and the preparation method comprises the following steps:
1) Mixing the polyurethane elastomer with one or more additives, extruding and granulating to prepare polyurethane elastomer foamable particles, mixing the polyurethane elastomer foamable particles with a foaming agent, and releasing the foaming agent by quickly increasing the temperature or quickly reducing the pressure to prepare polyurethane elastomer foamed particles; and then the prepared polyurethane elastomer foaming particles are molded in a mold, thereby obtaining a foaming material product.
2) The polyurethane elastomer is mixed with one or more additives and extruded to prepare a sample with a specific shape, the prepared sample is put into a foaming agent to be fully impregnated, and then the foaming agent is released through rapid reduction of pressure or rapid increase of temperature to prepare a foaming material product.
3) Mixing the polyurethane elastomer with one or more additives, fully mixing the mixture with a foaming agent in a molten state, cutting the mixture under water to prepare the foamed beads of the polyurethane elastomer, and foaming and molding the beads in a mold to prepare the foamed material product.
The fourth aspect of the present invention provides the use of the polyurethane elastomer foam composition according to any one of the above technical aspects or the polyurethane elastomer foam material according to any one of the above technical aspects in the preparation of the following products: 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, gym or pathway, a vibration damping material, a packaging material.
The technical scheme provided by the invention has the following advantages:
the polyurethane elastomer provided by the invention introduces a 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. The foaming material prepared by the polyurethane elastomer can obviously improve the comprehensive properties of the foaming material, including lower density, excellent tear resistance, higher hardness, good resilience and durability. Based on excellent material performance, the polyurethane elastomer foam material provided by the invention can meet the requirements of various application occasions, so that the polyurethane elastomer foam material is wide in application field and strong in practicability.
The polyurethane elastomer and the foaming material thereof provided by the invention have the advantages of excellent performance, 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.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following specific examples.
The chemicals used in the examples of the present invention and comparative examples were all commercially available products with a purity of industrial grade unless otherwise specified.
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 of the present invention and the comparative examples were number average molecular weights, as measured by gel permeation chromatography, and the solvent was N, N-dimethylformamide.
The method for testing the properties of the foamed materials prepared in the examples and comparative examples of the present invention was as follows:
(1) Density: testing was performed according to the method described in ASTM D792-2013;
(2) Hardness: testing by adopting an Asker C hardness tester;
(3) Tensile strength and elongation at break: testing was performed according to the method described in ISO 1798-2008;
(4) The delamination tear strength: testing is carried out according to the method recorded in ISO 20875-2018;
(5) Pendulum rebound resilience: the test was carried out in accordance with DIN 53512, with a specimen thickness of 20mm;
(6) Compression set: testing by the method described in ISO 1856-2018;
(7) Testing the durability of the foaming material: firstly, an MTS-831 elastic material testing machine-an elastomer testing system is adopted to carry out compression fatigue testing on the material, the constant load is 1500N, the frequency is 1.41Hz, the cycle number is 100,000, and the pendulum rebound performance of the material is tested by the method recorded in DIN 53512 after the compression fatigue is finished.
Example 1
(1) Adding 2920g of adipic acid and 15L of solvent N, N-dimethylformamide into a 30L reaction kettle, adding 3528g of Hexamethylene Diisocyanate (HDI) after the adipic acid is completely dissolved, heating to 120 ℃, reacting for 6h under stirring, condensing and refluxing evaporated solvent and reactants, simultaneously discharging carbon dioxide generated by the reaction, heating to 160 ℃ after the reaction is finished, vacuumizing to remove the solvent and unreacted raw materials, and preparing the isocyanate-terminated polyamide prepolymer, wherein the number average molecular weight is 5000g/mol, and the weight is 4100g.
(2) Adding 200g of 1, 4-butanediol and 6500g of PTMEG (the number average molecular weight is 2000 g/mol) into a 30L reaction kettle, stirring and dispersing uniformly, and heating to 100 ℃; in another separate container, 2050g of the isocyanate terminated polyamide prepolymer prepared in step (1) and 1265g of 4, 4-diphenylmethane diisocyanate (MDI) were weighed, heated to 120 ℃ and mixed uniformly, the resulting mixture was added to a reaction kettle, reacted for 60s with rapid stirring, then the reactants were poured into a polytetrafluoroethylene mold at 100 ℃ and, after the reactants were cured, placed in a hot oven at 100 ℃ for heat treatment for 15h. After the heat treatment, the resulting product was cooled, ground in a grinder, and cut into small pellets to obtain thermoplastic polyurethane elastomer particles having a number average molecular weight of 143245g/mol and a weight of 9600g.
(3) 5Kg of the polyurethane elastomer particles prepared in the step (2) are mixed with 50g of nucleating agent calcium carbonate (with the average particle size of 0.5 mu m), 15g of antioxidant 1010 and 5g of ultraviolet absorbent UV326, and then extruded and granulated to prepare foamable polyurethane elastomer particles with the diameter of 1-2mm, wherein the temperature of a 1-11 region of a double screw extruder (44, length-diameter ratio of Nanjing Ruiya) is 165 ℃,170 ℃,175 ℃,180 ℃,185 ℃,190 ℃,195 ℃,190 ℃,185 ℃ and 180 ℃.
(4) Mixing the foamable polyurethane elastomer particles obtained in the last step and water according to the ratio of 1:3, pouring the mixture into a foaming kettle with a stirrer, filling carbon dioxide serving as a foaming agent, saturating the mixture for 1 hour at the pressure of 15MPa and the temperature of 120 ℃, then decompressing the mixture to prepare polyurethane elastomer foaming particles, drying the foaming particles at the temperature of 40 ℃, and curing the foaming particles for one week at normal temperature until the foaming particles are used in the next step.
(5) The polyurethane elastomer foamed particles were molded in a steam molding apparatus (Kortermasa, K68 HP) with a steam pressure of 0.27MPa (140.1 ℃), a polyurethane elastomer foamed material molded product of 20mm thickness was prepared, and various performance tests were performed after being left for 24 hours, and the test results are shown in Table 1.
Example 2
(1) 2088g of suberic acid and 15L of N, N-dimethylformamide as a solvent were charged into a 30L reactor, and 4716g of dicyclohexylmethane 4, 4-diisocyanate (H) was added after the suberic acid was completely dissolved 12 MDI), heating to 120 ℃, reacting for 6h under stirring, condensing and refluxing the evaporated solvent and reactants, simultaneously discharging carbon dioxide generated by the reaction, heating to 160 ℃ after the reaction is finished, vacuumizing to remove the solvent and unreacted raw materials, and preparing the isocyanate-terminated polyamide prepolymer, wherein the number average molecular weight is 1000g/mol, and the weight is 5400g.
(2) 731g of 1, 4-butanediol and 5760g of polybutylene adipate (number average molecular weight of 2000 g/mol) were added into a 30L reaction kettle, stirred and dispersed uniformly, and heated to 100 ℃; weighing 1000g of the isocyanate-terminated polyamide prepolymer prepared in the step (1) and 2500g of 4, 4-diphenylmethane diisocyanate (MDI) in another separate container, heating to 120 ℃ and uniformly mixing, adding the obtained mixture into a reaction kettle, reacting for 60s under rapid stirring, pouring reactants into a polytetrafluoroethylene mold at 100 ℃, and after the reactants are cured, putting the polytetrafluoroethylene mold at 100 ℃ into a hot oven for heat treatment for 15h. After the heat treatment, the resultant was cooled, ground in a grinder, and cut into small pellets to obtain thermoplastic polyurethane elastomer particles having a number average molecular weight of 138123g/mol and a weight of 9550g.
(3) 5Kg of the polyurethane elastomer particles prepared in the step (2) are mixed with 50g of nucleating agent calcium carbonate (with the average particle size of 0.5 mu m), 15g of antioxidant 1010 and 5g of ultraviolet absorbent UV326, and then extruded and granulated to prepare foamable polyurethane elastomer particles with the diameter of 1-2mm, wherein the temperature of a 1-11 region of a double screw extruder (44, length-diameter ratio of Nanjing Ruiya) is 165 ℃,170 ℃,175 ℃,180 ℃,185 ℃,190 ℃,195 ℃,190 ℃,185 ℃ and 180 ℃.
(4) Mixing the foamable polyurethane elastomer particles obtained in the last step and water according to the ratio of 1:3, pouring the mixture into a foaming kettle with a stirrer, filling carbon dioxide serving as a foaming agent, saturating the mixture for 1 hour at the pressure of 15MPa and the temperature of 120 ℃, then decompressing the mixture to prepare polyurethane elastomer foaming particles, drying the foaming particles at the temperature of 40 ℃, and curing the foaming particles for one week at normal temperature until the foaming particles are used in the next step.
(5) The polyurethane elastomer foamed particles were molded in a steam molding apparatus (Kortermasa, K68 HP) under a steam pressure of 0.21MPa (134.1 deg.C) to prepare a polyurethane elastomer foamed material molded article having a thickness of 20mm, and the molded article was left to stand for 24 hours to conduct various performance tests, the test results of which are shown in Table 1.
Example 3
(1) Adding 4040g of sebacic acid and 10L of solvent dimethyl sulfoxide (DMSO) into a 30L reaction kettle, adding 3696g of Pentamethylene Diisocyanate (PDI) after the sebacic acid is completely dissolved, heating to 120 ℃, reacting for 6h under stirring, condensing and refluxing evaporated solvent and reactants, simultaneously discharging carbon dioxide generated by the reaction, heating to 160 ℃ after the reaction is finished, vacuumizing to remove the solvent and unreacted raw materials, and preparing the isocyanate-terminated polyamide prepolymer, wherein the number average molecular weight is 1500g/mol, and the weight is 5400g.
(2) Adding 513g of 1, 4-butanediol and 7683g of PTMEG (the number average molecular weight is 2000 g/mol) into a 30L reaction kettle, stirring and dispersing uniformly, and heating to 100 ℃; weighing 3000g of the isocyanate terminated polyamide prepolymer prepared in the step (1) and 3345g of 4, 4-diphenylmethane diisocyanate (MDI) in a separate container, heating to 120 ℃ and uniformly mixing, adding the obtained mixture into a reaction kettle, reacting for 60s under rapid stirring, pouring reactants into a polytetrafluoroethylene mold at 100 ℃, and after the reactants are cured, putting the polytetrafluoroethylene mold at 100 ℃ into a hot oven for heat treatment for 15h. After the heat treatment was completed, the resultant was cooled, ground in a grinder, and cut into small pellets to obtain thermoplastic polyurethane elastomer particles having a number average molecular weight of 133659g/mol and a weight of 13200g.
(3) 5Kg of the polyurethane elastomer particles prepared in the step (2) above, 50g of nucleating agent calcium carbonate (average particle size of 0.5 μm), 15g of antioxidant 1010 and 5g of ultraviolet absorbent UV326 were mixed and extruded for granulation to prepare foamable polyurethane elastomer particles with a diameter of 1-2mm, wherein the temperature in the 1-11 zone of a twin-screw extruder (44 length-diameter ratio, nanjing Ruiya, is 165 ℃,170 ℃,175 ℃,180 ℃,185 ℃,190 ℃,195 ℃,190 ℃,185 ℃ and 180 ℃.
(4) Mixing the foamable polyurethane elastomer particles obtained in the last step and water according to the ratio of 1:3, pouring the mixture into a foaming kettle with a stirrer, filling carbon dioxide serving as a foaming agent, saturating the mixture for 1 hour at the pressure of 15MPa and the temperature of 120 ℃, then decompressing the mixture to prepare polyurethane elastomer foaming particles, drying the foaming particles at the temperature of 40 ℃, and curing the foaming particles for one week at normal temperature until the foaming particles are used in the next step.
(5) The polyurethane elastomer foamed particles were molded in a steam molding apparatus (Kortermasa, K68 HP) with a steam pressure of 0.24MPa (137.2 ℃), a polyurethane elastomer foamed material molded product of 20mm thickness was prepared, and various performance tests were performed after being left for 24 hours, with the test results shown in Table 1.
Example 4
(1) Adding 2920g of adipic acid and 15L of solvent dimethyl sulfoxide (DMSO) into a 30L reaction kettle, adding 4032g of Hexamethylene Diisocyanate (HDI) after the adipic acid is completely dissolved, heating to 120 ℃, reacting for 6h under stirring, condensing and refluxing evaporated solvent and reactants, simultaneously discharging carbon dioxide generated by the reaction, heating to 160 ℃ after the reaction is finished, vacuumizing to remove the solvent and unreacted raw materials, and preparing the isocyanate-terminated polyamide prepolymer, wherein the number average molecular weight is 1300g/mol, and the weight is 4800g.
(2) Adding 459g of 1, 4-butanediol and 6600g of PTMEG (the number average molecular weight is 2000 g/mol) into a 30L reaction kettle, stirring and dispersing uniformly, and heating to 100 ℃; in another separate container, 2600g of the isocyanate terminated polyamide prepolymer prepared in step (1) and 1600g of 4, 4-diphenylmethane diisocyanate (MDI) were weighed, heated to 120 ℃ and mixed uniformly, the resulting mixture was added to a reaction kettle, reacted for 60s with rapid stirring, then the reactants were poured into a 100 ℃ polytetrafluoroethylene mold, and after the reactants were cured, placed in a 100 ℃ heat oven for heat treatment for 15h. After the heat treatment, the resulting product was cooled, ground in a grinder, and cut into small pellets to obtain thermoplastic polyurethane elastomer particles having a number average molecular weight of 136391g/mol and a weight of 10850g.
(3) 5Kg of the polyurethane elastomer particles prepared in the step (2) are mixed with 50g of nucleating agent calcium carbonate (with the average particle size of 0.5 mu m), 15g of antioxidant 1010 and 5g of ultraviolet absorbent UV326, and then extruded and granulated to prepare foamable polyurethane elastomer particles with the diameter of 1-2mm, wherein the temperature of a 1-11 region of a double screw extruder (44, length-diameter ratio of Nanjing Ruiya) is 165 ℃,170 ℃,175 ℃,180 ℃,185 ℃,190 ℃,195 ℃,190 ℃,185 ℃ and 180 ℃.
(4) Mixing the foamable polyurethane elastomer particles obtained in the last step and water according to the ratio of 1:3, pouring the mixture into a foaming kettle with a stirrer, filling carbon dioxide serving as a foaming agent, saturating the mixture for 1 hour at the pressure of 15MPa and the temperature of 120 ℃, then decompressing the mixture to prepare polyurethane elastomer foaming particles, drying the foaming particles at the temperature of 40 ℃, and curing the foaming particles for one week at normal temperature until the foaming particles are used in the next step.
(5) The polyurethane elastomer foamed particles were molded in a steam molding apparatus (Kortermasa, K68 HP) under a steam pressure of 0.23MPa (136.2 deg.C) to prepare a polyurethane elastomer foamed material molded article having a thickness of 20mm, and various performance tests were carried out after being left for 24 hours, and the test results are shown in Table 1.
Example 5
(1) Adding 2920g of adipic acid and 15L of solvent dimethyl sulfoxide (DMSO) into a 30L reaction kettle, adding 4032g of Hexamethylene Diisocyanate (HDI) after the adipic acid is completely dissolved, heating to 120 ℃, reacting for 6h under stirring, condensing and refluxing evaporated solvent and reactants, simultaneously discharging carbon dioxide generated by the reaction, heating to 160 ℃ after the reaction is finished, vacuumizing to remove the solvent and unreacted raw materials, and preparing the isocyanate-terminated polyamide prepolymer, wherein the number average molecular weight is 1300g/mol, and the weight is 4800g.
(2) 602g of 1, 6-hexanediol and 6600g of PTMEG (number average molecular weight of 2000 g/mol) are added into a 30L reaction kettle, stirred and dispersed uniformly, and the temperature is raised to 100 ℃; in a separate vessel 2600g of the isocyanate-terminated polyamide prepolymer prepared in step (1) and 1677g of dicyclohexylmethane 4, 4-diisocyanate (H) were weighed out 12 MDI), heating to 120 ℃, uniformly mixing, adding the obtained mixture into a reaction kettle, reacting for 60s under rapid stirring, pouring reactants into a polytetrafluoroethylene mold at 100 ℃, and placing the polytetrafluoroethylene mold into a thermal oven at 100 ℃ for thermal treatment for 15h after the reactants are solidified. After the heat treatment was completed, the resultant was cooled, ground in a grinder, and cut into small particles to obtain thermoplastic polyurethane elastomer particles having a number average molecular weight of 140021g/mol and a weight of 10732g.
(3) 5Kg of the polyurethane elastomer particles prepared in the step (2) are mixed with 50g of nucleating agent calcium carbonate (with the average particle size of 0.5 mu m), 15g of antioxidant 1010 and 5g of ultraviolet absorbent UV326, and then extruded and granulated to prepare foamable polyurethane elastomer particles with the diameter of 1-2mm, wherein the temperature of a 1-11 region of a double screw extruder (44, length-diameter ratio of Nanjing Ruiya) is 165 ℃,170 ℃,175 ℃,180 ℃,185 ℃,190 ℃,195 ℃,190 ℃,185 ℃ and 180 ℃.
(4) Mixing the foamable polyurethane elastomer particles obtained in the previous step and water according to the ratio of 1:3, pouring the mixture into a foaming kettle with a stirrer, filling carbon dioxide serving as a foaming agent, saturating the mixture for 1 hour at the pressure of 15MPa and the temperature of 120 ℃, then decompressing the mixture to prepare polyurethane elastomer foaming particles, drying the foaming particles at the temperature of 40 ℃, and curing the foaming particles for one week at normal temperature until the foaming particles are used in the next step.
(5) The polyurethane elastomer foamed particles were molded in a steam molding apparatus (Kortermasa, K68 HP) under a steam pressure of 0.16MPa (128.1 deg.C) to prepare a polyurethane elastomer foamed material molded article having a thickness of 20mm, and various performance tests were carried out after standing for 24 hours, and the test results are shown in Table 1.
Example 6
(1) Adding 2920g of adipic acid and 15L of solvent dimethyl sulfoxide (DMSO) into a 30L reaction kettle, adding 4032g of Hexamethylene Diisocyanate (HDI) after the adipic acid is completely dissolved, heating to 120 ℃, reacting for 6h under stirring, condensing and refluxing evaporated solvent and reactants, simultaneously discharging carbon dioxide generated by the reaction, heating to 160 ℃ after the reaction is finished, vacuumizing to remove the solvent and unreacted raw materials, and preparing the isocyanate-terminated polyamide prepolymer, wherein the number average molecular weight is 1300g/mol, and the weight is 4800g.
(2) Adding 316.2g of ethylene glycol and 6600g of PTMEG (the number average molecular weight is 2000 g/mol) into a 30L reaction kettle, stirring and dispersing uniformly, and heating to 100 ℃; 2600g of isocyanate-terminated polyamide prepolymer prepared in step (1) and 1075g of Hexamethylene Diisocyanate (HDI) were weighed in another separate vessel, heated to 120 ℃ and mixed uniformly, the resulting mixture was added to a reaction kettle, reacted for 60s with rapid stirring, then the reactant was poured into a 100 ℃ polytetrafluoroethylene mold, and after the reactant was cured, placed in a 100 ℃ heat oven for heat treatment for 15h. After the heat treatment, the resulting product was cooled, ground in a grinder, and cut into small pellets to obtain thermoplastic polyurethane elastomer particles having a number average molecular weight of 138109g/mol and a weight of 9953g.
(3) 5Kg of the polyurethane elastomer particles prepared in the step (2) are mixed with 50g of nucleating agent calcium carbonate (with the average particle size of 0.5 mu m), 15g of antioxidant 1010 and 5g of ultraviolet absorbent UV326, and then extruded and granulated to prepare foamable polyurethane elastomer particles with the diameter of 1-2mm, wherein the temperature of a 1-11 region of a double screw extruder (44, length-diameter ratio of Nanjing Ruiya) is 165 ℃,170 ℃,175 ℃,180 ℃,185 ℃,190 ℃,195 ℃,190 ℃,185 ℃ and 180 ℃.
(4) Mixing the foamable polyurethane elastomer particles obtained in the last step and water according to the ratio of 1:3, pouring the mixture into a foaming kettle with a stirrer, filling carbon dioxide serving as a foaming agent, saturating the mixture for 1 hour at the pressure of 15MPa and the temperature of 120 ℃, then decompressing the mixture to prepare polyurethane elastomer foaming particles, drying the foaming particles at the temperature of 40 ℃, and curing the foaming particles for one week at normal temperature until the foaming particles are used in the next step.
(5) The polyurethane elastomer foamed particles were molded in a steam molding apparatus (Kortermasa, K68 HP) with a steam pressure of 0.13MPa (124.1 deg.C), a polyurethane elastomer foamed material molded article having a thickness of 20mm was prepared, and various performance tests were carried out after being left for 24 hours, and the test results are shown in Table 1.
Example 7
(1) Adding 2920g of adipic acid and 15L of solvent dimethyl sulfoxide (DMSO) into a 30L reaction kettle, adding 4032g of Hexamethylene Diisocyanate (HDI) after the adipic acid is completely dissolved, heating to 120 ℃, reacting for 6h under stirring, condensing and refluxing evaporated solvent and reactants, simultaneously discharging carbon dioxide generated by the reaction, heating to 160 ℃ after the reaction is finished, vacuumizing to remove the solvent and unreacted raw materials, and preparing the isocyanate-terminated polyamide prepolymer, wherein the number average molecular weight is 1300g/mol, and the weight is 4800g.
(2) 459g of 1, 4-butanediol and 6600g of PTMEG (the number average molecular weight is 2000 g/mol) are added into a 30L reaction kettle, stirred and dispersed uniformly, and the temperature is raised to 100 ℃; 2600g of isocyanate-terminated polyamide prepolymer prepared in step (1) and 986g of Pentamethylene Diisocyanate (PDI) are weighed in another separate container, heated to 120 ℃ and mixed uniformly, the obtained mixture is added into a reaction kettle and reacted for 60s under rapid stirring, then the reactants are poured into a polytetrafluoroethylene mold with 100 ℃, and after the reactants are solidified, the mixture is placed into a hot oven with 100 ℃ for heat treatment for 15h. After the heat treatment, the resultant was cooled, ground in a grinder, and cut into small pellets to obtain thermoplastic polyurethane elastomer particles having a number average molecular weight of 139371g/mol and a weight of 9745g.
(3) 5Kg of the polyurethane elastomer particles prepared in the step (2) are mixed with 50g of nucleating agent calcium carbonate (with the average particle size of 0.5 mu m), 15g of antioxidant 1010 and 5g of ultraviolet absorbent UV326, and then extruded and granulated to prepare foamable polyurethane elastomer particles with the diameter of 1-2mm, wherein the temperature of a 1-11 region of a double screw extruder (44, length-diameter ratio of Nanjing Ruiya) is 165 ℃,170 ℃,175 ℃,180 ℃,185 ℃,190 ℃,195 ℃,190 ℃,185 ℃ and 180 ℃.
(4) Mixing the foamable polyurethane elastomer particles obtained in the last step and water according to the ratio of 1:3, pouring the mixture into a foaming kettle with a stirrer, filling carbon dioxide serving as a foaming agent, saturating the mixture for 1 hour at the pressure of 15MPa and the temperature of 120 ℃, then decompressing the mixture to prepare polyurethane elastomer foaming particles, drying the foaming particles at the temperature of 40 ℃, and curing the foaming particles for one week at normal temperature until the foaming particles are used in the next step.
(5) The polyurethane elastomer foamed particles were molded in a steam molding apparatus (Kortermasa, K68 HP) under a steam pressure of 0.14MPa (125.5 deg.C) to prepare a polyurethane elastomer foamed material molded article having a thickness of 20mm, and various performance tests were carried out after standing for 24 hours, and the test results are shown in Table 1.
Example 8
(1) Adding 2920g of adipic acid and 15L of solvent dimethyl sulfoxide (DMSO) into a 30L reaction kettle, adding 4032g of Hexamethylene Diisocyanate (HDI) after the adipic acid is completely dissolved, heating to 120 ℃, reacting for 6h under stirring, condensing and refluxing evaporated solvent and reactants, simultaneously discharging carbon dioxide generated by the reaction, heating to 160 ℃ after the reaction is finished, vacuumizing to remove the solvent and unreacted raw materials, and preparing the isocyanate-terminated polyamide prepolymer, wherein the number average molecular weight is 1300g/mol, and the weight is 4800g.
(2) 252g of ethylene glycol and 5748g of PTMEG (the number average molecular weight is 2000 g/mol) are added into a 30L reaction kettle, stirred and dispersed uniformly, and the temperature is raised to 100 ℃; weighing 3500g of the isocyanate terminated polyamide prepolymer prepared in step (1) and 500g of Hexamethylene Diisocyanate (HDI) in another separate container, heating to 120 ℃ and mixing uniformly, adding the obtained mixture into a reaction kettle, reacting for 60s under rapid stirring, pouring the reactants into a polytetrafluoroethylene mold at 100 ℃, and after the reactants are cured, putting the polytetrafluoroethylene mold at 100 ℃ for heat treatment for 15h. After the heat treatment was completed, the resultant was cooled, ground in a grinder, and cut into small pellets to obtain thermoplastic polyurethane elastomer particles having a number average molecular weight of 134245g/mol and a weight of 9643g.
(3) 5Kg of the polyurethane elastomer particles prepared in the step (2) are mixed with 50g of nucleating agent calcium carbonate (with the average particle size of 0.5 mu m), 15g of antioxidant 1010 and 5g of ultraviolet absorbent UV326, and then extruded and granulated to prepare foamable polyurethane elastomer particles with the diameter of 1-2mm, wherein the temperature of a 1-11 region of a double screw extruder (44, length-diameter ratio of Nanjing Ruiya) is 165 ℃,170 ℃,175 ℃,180 ℃,185 ℃,190 ℃,195 ℃,190 ℃,185 ℃ and 180 ℃.
(4) Mixing the foamable polyurethane elastomer particles obtained in the last step and water according to the ratio of 1:3, pouring the mixture into a foaming kettle with a stirrer, filling carbon dioxide serving as a foaming agent, saturating the mixture for 1 hour at the pressure of 15MPa and the temperature of 120 ℃, then decompressing the mixture to prepare polyurethane elastomer foaming particles, drying the foaming particles at the temperature of 40 ℃, and curing the foaming particles for one week at normal temperature until the foaming particles are used in the next step.
(5) The polyurethane elastomer foamed particles were molded in a steam molding apparatus (Kortermasa, K68 HP) under a steam pressure of 0.13MPa (124.1 deg.C) to prepare a polyurethane elastomer foamed material molded article having a thickness of 20mm, and various performance tests were carried out after being left for 24 hours, and the test results are shown in Table 1.
Example 9
(1) Adding 2920g of adipic acid and 15L of solvent dimethyl sulfoxide (DMSO) into a 30L reaction kettle, adding 4032g of Hexamethylene Diisocyanate (HDI) after the adipic acid is completely dissolved, heating to 120 ℃, reacting for 6h under stirring, condensing and refluxing evaporated solvent and reactants, simultaneously discharging carbon dioxide generated by the reaction, heating to 160 ℃ after the reaction is finished, vacuumizing to remove the solvent and unreacted raw materials, and preparing the isocyanate-terminated polyamide prepolymer, wherein the number average molecular weight is 1300g/mol, and the weight is 4800g.
(2) Adding 800g of ethylene glycol and 4000g of PTMEG (the number average molecular weight is 2000 g/mol) into a 30L reaction kettle, uniformly stirring and dispersing, and heating to 100 ℃; 3484g of the isocyanate terminated polyamide prepolymer prepared in step (1) and 1715g of Hexamethylene Diisocyanate (HDI) were weighed in a separate container, heated to 120 ℃ and mixed uniformly, the resulting mixture was added to a reaction vessel, reacted for 60s with rapid stirring, then the reactants were poured into a polytetrafluoroethylene mold at 100 ℃ and, after the reactants were cured, placed in a hot oven at 100 ℃ for heat treatment for 15h. After the heat treatment was completed, the resultant was cooled, ground in a grinder, and cut into small particles to obtain thermoplastic polyurethane elastomer particles having a number average molecular weight of 142103g/mol and a weight of 9754g.
(3) 5Kg of the polyurethane elastomer particles prepared in the step (2) are mixed with 50g of nucleating agent calcium carbonate (with the average particle size of 0.5 mu m), 15g of antioxidant 1010 and 5g of ultraviolet absorbent UV326, and then extruded and granulated to prepare foamable polyurethane elastomer particles with the diameter of 1-2mm, wherein the temperature of a 1-11 region of a double screw extruder (44, length-diameter ratio of Nanjing Ruiya) is 165 ℃,170 ℃,175 ℃,180 ℃,185 ℃,190 ℃,195 ℃,190 ℃,185 ℃ and 180 ℃.
(4) Mixing the foamable polyurethane elastomer particles obtained in the last step and water according to the ratio of 1:3, pouring the mixture into a foaming kettle with a stirrer, filling carbon dioxide serving as a foaming agent, saturating the mixture for 1 hour at the pressure of 15MPa and the temperature of 120 ℃, then decompressing the mixture to prepare polyurethane elastomer foaming particles, drying the foaming particles at the temperature of 40 ℃, and curing the foaming particles for one week at normal temperature until the foaming particles are used in the next step.
(5) The polyurethane elastomer foamed particles were molded in a steam molding apparatus (Kortermasa, K68 HP) under a steam pressure of 0.13MPa (124.1 deg.C) to prepare a polyurethane elastomer foamed material molded article having a thickness of 20mm, and various performance tests were carried out after being left for 24 hours, and the test results are shown in Table 1.
Comparative example 1
(1) 459g of 1, 4-butanediol and 6600g of PTMEG (the number average molecular weight is 2000 g/mol) are added into a 30L reaction kettle, stirred and dispersed uniformly, and the temperature is raised to 100 ℃; in another independent container, 2100g of 4, 4-diphenylmethane diisocyanate (MDI) is weighed, heated to 120 ℃, added into a reaction kettle, reacted for 60s under rapid stirring, then poured into a polytetrafluoroethylene mold with the temperature of 100 ℃, and placed into a thermal oven with the temperature of 100 ℃ for heat treatment for 15h after the reactants are solidified. After the heat treatment, the resulting product was cooled, ground in a grinder, and cut into small pellets to obtain thermoplastic polyurethane elastomer particles having a number average molecular weight of 143203g/mol and a weight of 8342g.
(2) 5Kg of the polyurethane elastomer particles prepared in the step (1) are mixed with 50g of nucleating agent calcium carbonate (with the average particle size of 0.5 mu m), 15g of antioxidant 1010 and 5g of ultraviolet absorbent UV326, and then extruded and granulated to prepare foamable polyurethane elastomer particles with the diameter of 1-2mm, wherein the temperature of a 1-11 region of a double screw extruder (44, length-diameter ratio of Nanjing Ruiya) is 165 ℃,170 ℃,175 ℃,180 ℃,185 ℃,190 ℃,195 ℃,190 ℃,185 ℃ and 180 ℃.
(3) Mixing the foamable polyurethane elastomer particles obtained in the previous step and water according to the ratio of 1:3, pouring the mixture into a foaming kettle with a stirrer, filling carbon dioxide serving as a foaming agent, saturating the mixture for 1 hour at the pressure of 15MPa and the temperature of 120 ℃, then decompressing the mixture to prepare polyurethane elastomer foaming particles, drying the foaming particles at the temperature of 40 ℃, and curing the foaming particles for one week at normal temperature until the foaming particles are used in the next step.
(4) The polyurethane elastomer foamed particles were molded in a steam molding apparatus (Coulter Elisa, K68 HP) under a steam pressure of 0.34MPa (146 deg.C) to prepare a polyurethane elastomer foamed material molded article having a thickness of 20mm, and the molded article was left to stand for 24 hours to conduct various performance tests, the test results of which are shown in Table 1.
Comparative example 2
(1) Adding 459g of 1, 4-butanediol and 6600g of PTMEG (the number average molecular weight is 2000 g/mol) into a 30L reaction kettle, stirring and dispersing uniformly, and heating to 100 ℃; weighing 1411.2g of Hexamethylene Diisocyanate (HDI) in another separate container, heating to 120 ℃, adding into the reaction kettle, reacting for 60s under rapid stirring, pouring the reactant into a polytetrafluoroethylene mold at 100 ℃, and after the reactant is cured, putting into a thermal oven at 100 ℃ for thermal treatment for 15h. After the heat treatment, the resultant was cooled, ground in a grinder, and cut into small pellets to obtain thermoplastic polyurethane elastomer particles having a number average molecular weight of 141511g/mol and a weight of 7567g.
(2) 5Kg of the polyurethane elastomer particles prepared in the step (1) are mixed with 50g of nucleating agent calcium carbonate (with the average particle size of 0.5 mu m), 15g of antioxidant 1010 and 5g of ultraviolet absorbent UV326, and then extruded and granulated to prepare foamable polyurethane elastomer particles with the diameter of 1-2mm, wherein the temperature of a 1-11 region of a double screw extruder (44, length-diameter ratio of Nanjing Ruiya) is 165 ℃,170 ℃,175 ℃,180 ℃,185 ℃,190 ℃,195 ℃,190 ℃,185 ℃ and 180 ℃.
(3) Mixing the foamable polyurethane elastomer particles obtained in the previous step and water according to the ratio of 1:3, pouring the mixture into a foaming kettle with a stirrer, filling carbon dioxide serving as a foaming agent, saturating the mixture for 1 hour at the pressure of 15MPa and the temperature of 120 ℃, then decompressing the mixture to prepare polyurethane elastomer foaming particles, drying the foaming particles at the temperature of 40 ℃, and curing the foaming particles at normal temperature for one week for next use.
(4) The polyurethane elastomer foamed particles were molded in a steam molding apparatus (Kortermasa, K68 HP) with a steam pressure of 0.12MPa (122.7 ℃), and a polyurethane elastomer foamed material molded article of 20mm thickness was prepared, and various performance tests were performed after being left for 24 hours, with the test results shown in Table 1.
TABLE 1 molded article Performance test results for polyurethane elastomer foam
The results in Table 1 show that the polyurethane elastomer foams provided by the present invention have a significantly lower density and a higher hardness than foams made from polyurethane elastomers without polyamide segments incorporated into the molecular chains (comparative examples 1 and 2), while these do not sacrifice other properties, in particular resilience. In addition, the resilience performance of the polyurethane elastomer foam material provided by the invention is hardly reduced after long-term cyclic reciprocating compression test, and the polyurethane elastomer foam material has good durability.
Therefore, the polyurethane elastomer foam material provided by the invention has excellent comprehensive performance, can meet the requirements of various application occasions, and has very industrial practicability.
Unless otherwise defined, all terms used herein have the meanings commonly understood by those skilled in the art.
The described embodiments of the present invention are for illustrative purposes only and are not intended to limit the scope of the present invention, and those skilled in the art may make various other substitutions, alterations, and modifications within the scope of the present invention, and thus, the present invention is not limited to the above-described embodiments but 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211648505.XA CN115785392A (en) | 2022-12-21 | 2022-12-21 | Polyurethane elastomer, foaming material and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211648505.XA CN115785392A (en) | 2022-12-21 | 2022-12-21 | Polyurethane elastomer, foaming material and application thereof |
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| CN202211648505.XA Pending CN115785392A (en) | 2022-12-21 | 2022-12-21 | Polyurethane elastomer, foaming material and application thereof |
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| CN (1) | CN115785392A (en) |
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