CN113943489B - Foaming material composition and foaming material - Google Patents
Foaming material composition and foaming material Download PDFInfo
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- CN113943489B CN113943489B CN202111360161.8A CN202111360161A CN113943489B CN 113943489 B CN113943489 B CN 113943489B CN 202111360161 A CN202111360161 A CN 202111360161A CN 113943489 B CN113943489 B CN 113943489B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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Abstract
The invention provides a foaming material composition and a foaming material, wherein the foaming material composition comprises the following components in percentage by mass: 10 to 90 percent of segmented copolymer, 4 to 84 percent of thermoplastic polyurethane elastomer, 1 to 25 percent of polyurethane ionomer and 0.1 to 5 percent of foaming nucleating agent. The foaming material composition is prepared by compounding three polymers, namely a block copolymer, a thermoplastic polyurethane elastomer and a polyurethane ionomer, and matching a foaming nucleating agent, so that the obtained foaming material has the characteristics of light weight, high resilience and low compression permanent deformation; meanwhile, the foaming material has excellent comprehensive mechanical properties such as tear resistance, tensile property and the like, is low in preparation cost and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of foaming materials, and particularly relates to a foaming material composition and a foaming material.
Background
The Thermoplastic Polyurethane (TPU) elastomer foam material product 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, packaging, living homes and the like. In the preparation process of the TPU elastomer foaming material, a high-pressure fluid physical foaming method is usually adopted to obtain foaming TPU particles, and then the foaming TPU particles are subjected to steam compression molding to obtain a foaming product. For example, CN103642200A discloses a foamed thermoplastic polyurethane bead comprising 100 parts of TPU particles, 1 to 10 parts of cell size stabilizer, 1 to 35 parts of melt viscosity modifier; these beads are prepared by impregnating thermoplastic polyurethane particles comprising a cell size stabilizer and a melt viscosity modifier in an aqueous suspension with a volatile blowing agent and then foaming. CN103804890A discloses an extrusion foaming thermoplastic polyurethane elastomer particle, comprising 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; then mixing the above beadsAnd putting the granules into a special foaming extruder, and carrying out underwater granulation after foaming through an oral mold to obtain product granules. Currently, the density of TPU elastomer foaming materials used as sole materials is generally 0.15 to 0.2g/cm 3 The resilience performance is about 60 percent, and the defects of high density and insufficient elasticity exist.
Thermoplastic polyamide block copolymer elastomer (PEBA) foam is another foam for shoe materials developed after TPU elastomers. For example, CN109971025A discloses a polyamide elastomer foam material, which is prepared by the following steps: mixing and extruding a polyamide elastomer, a melt viscosity regulator, a foam cell nucleating agent and a foaming auxiliary agent to obtain foaming particles; and mixing the foaming particles, the surfactant and the chemical foaming agent in a reaction kettle, and then heating for foaming to obtain the polyamide elastomer foaming material. CN111117215A discloses a thermoplastic elastomer foamed shoe material, which comprises the following raw materials: 100 parts of modified polyamide elastomer, 0.1-0.5 part of antioxidant and 0-10 parts of nucleating agent; wherein the modified polyamide elastomer comprises at least two polyamide elastomers; the foaming shoe material is prepared by a supercritical fluid foaming technology, and has higher foaming ratio and better elasticity. The thermoplastic polyamide block copolymer elastomer foam has a lower density (0.1 g/cm) than the TPU elastomer foam 3 About) and better resilience (about 80%); however, thermoplastic polyamide block copolymer elastomer foams have insufficient tear resistance and high cost, thereby limiting their widespread use.
Therefore, the development of a foaming material with low density, higher resilience and better tear resistance is a problem to be solved in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a foaming material composition and a foaming material, wherein the foaming material composition is prepared by compounding a segmented copolymer, a thermoplastic polyurethane elastomer and a polyurethane ionomer, so that the foaming material has low density and high resilience, meanwhile, the tear resistance is obviously improved, the manufacturing cost is low, and the foaming material composition is suitable for large-scale production.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a foam material composition, which comprises the following components by mass:
in the foaming material composition provided by the invention, the block copolymer, the thermoplastic polyurethane elastomer and the polyurethane ionomer are compounded, and the foaming nucleating agent is matched, so that the obtained foaming material has the characteristics of low density, light weight and high rebound resilience (about 80 percent of rebound resilience); wherein the introduction of the polyurethane ionomer enhances the melt strength of the foam composition, helping to reduce the density of the foam; moreover, the ionic bond of the polyurethane ionomer can improve the interaction force between molecular chain segments in the foaming material composition and the foaming material, so that the tear resistance of the foaming material is obviously improved, and the foaming material is endowed with better tensile strength and lower compression permanent set through the mutual cooperation of the components.
The content of the block copolymer in the foam material composition is 10 to 90% by mass, for example, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or 85%, and specific values therebetween are not exhaustive, and for reasons of brevity and conciseness, the invention does not include the specific values included in the range, preferably 20 to 80%, and more preferably 30 to 70%.
The content of the thermoplastic polyurethane elastomer in the foam material composition is 4 to 84% by mass, for example, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% or 80%, and specific values therebetween are not limited to the space and the conciseness, and the invention does not exhaustive list of specific values included in the range, preferably 12 to 72%, and more preferably 20 to 60%.
The polyurethane ionomer is present in the foam composition in an amount of 1 to 25% by weight, for example, 2%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22% or 24% by weight, and specific values therebetween, for reasons of brevity and clarity, are not exhaustive, and the range includes specific values, preferably 3 to 20%, and more preferably 5 to 15%.
In the foam material composition, the content of the foaming nucleating agent is 0.1 to 5% by mass, for example, 0.2%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, 3.5%, 4%, 4.5% or 4.8%, and specific values between the above-mentioned values are not limited to space and simplicity, and the invention does not list the specific values included in the range, preferably 0.2 to 3%, and more preferably 0.3 to 2%.
Preferably, the block copolymer comprises at least one hard segment and at least one soft segment.
Preferably, the hard segments in the block copolymer are selected from polyamide segments and/or polyester segments.
Preferably, the polyamide segments are obtained by polymerization of omega-amino acids or lactams
Or obtained by polycondensation of dibasic acid and diamine
Preferably, the lactam comprises any one or a combination of at least two of caprolactam, undecanolactam or dodecanolactam.
Preferably, the dibasic acid comprises any one of adipic acid, sebacic acid, undecanedioic acid or dodecanedioic acid, or a combination of at least two thereof; the diamine comprises any one or the combination of at least two of hexamethylene diamine, decamethylene diamine, undecane diamine or dodecane diamine.
Preferably, the polyamide segment comprises any one of polyamide 6, polyamide 11, polyamide 12, polyamide 66, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, polyamide 1111 or polyamide 1212, or a combination of at least two thereof.
Preferably, the polyester segment comprises polyalkylene terephthalate, obtained by polymerizing terephthalic acid with a diol.
Preferably, the diol comprises any one of ethylene glycol, butylene glycol or hexylene glycol or a combination of at least two thereof, and is further preferably butylene glycol.
In the present invention, the propylene glycol, butylene glycol and hexylene glycol include all the isomer forms available in the prior art, unless otherwise specified. Illustratively, the propylene glycol includes 1, 2-propylene glycol and/or 1, 3-propylene glycol; the butanediol comprises any one of 1, 2-butanediol, 1, 3-butanediol or 1, 4-butanediol or a combination of at least two of the two; the hexanediol comprises any one of 1, 2-hexanediol, 1, 5-hexanediol or 1, 6-hexanediol or a combination of at least two of the foregoing.
Preferably, the soft block in the block copolymer is selected from any one of polyether block, polysiloxane block or polyolefin block or a combination of at least two of them, and further preferably polyether block.
Preferably, the polyether segment is obtained by reacting an initiator with an epoxy compound containing 2 to 6 (e.g., 2, 3, 4, 5 or 6) carbon atoms.
Preferably, the initiator is selected from any one of water, small-molecule polyol, small-molecule polyphenol, small-molecule polyamine or small-molecule alcohol amine or the combination of at least two of the above; further preferably any one or a combination of at least two of water, propylene glycol, glycerin, trimethylolpropane, ethylenediamine pentaerythritol, xylitol, triethylene diamine, sorbitol, ethylene glycol, bisphenol a, and toluene diamine; still more preferably any one or a combination of at least two of water, propylene glycol or glycerol.
Preferably, the epoxide is selected from any one of ethylene oxide, propylene oxide and Tetrahydrofuran (THF) or a combination of at least two thereof.
Preferably, the polyether segment comprises any one of or a combination of at least two of polyoxyethylene ether, polyoxypropylene ether, polytetramethylene ether, tetrahydrofuran-propylene oxide copolyether and tetrahydrofuran-ethylene oxide copolyether, and further preferably polytetramethylene ether.
Preferably, the polyether segment has a number average molecular weight (M) n ) The average molecular weight is 500 to 10000, and may be 700, 900, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 5000, 6000, 7000, 8000, 9000 or the like, for example, and more preferably 700 to 4000.
The shore hardness of the block copolymer is preferably 30A to 80D, and may be, for example, 35A, 40A, 45A, 50A, 55A, 60A, 65A, 70A, 75A, 80A, 85A, 90A, 95A, 60D, 65D, 70D, or 75D, more preferably 60A to 60D, and still more preferably 80A to 95A.
Preferably, the thermoplastic polyurethane elastomer is selected from any one of polyester type thermoplastic polyurethane elastomer, polyether type thermoplastic polyurethane elastomer, polycaprolactone type thermoplastic polyurethane elastomer or polycarbonate type thermoplastic polyurethane elastomer or a combination of at least two thereof.
In the present invention, the Thermoplastic Polyurethane (TPU) elastomer is obtained by polymerizing a polyisocyanate, a polyol, and a chain extender.
Preferably, the polyisocyanate is any one or a combination of at least two of an aromatic polyisocyanate, an aliphatic polyisocyanate, or an alicyclic polyisocyanate, more preferably 4,4 '-diphenylmethane diisocyanate (4, 4' -MDI), 2,4 '-diphenylmethane diisocyanate (2, 4' -MDI), 2 '-diphenylmethane diisocyanate (2, 2' -MDI), xylylene Diisocyanate (XDI), 1, 5-Naphthalene Diisocyanate (NDI), p-phenylene diisocyanate (PPDI), toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), 1, 4-cyclohexyl diisocyanate (CHDI), hexamethylene Diisocyanate (HDI), decane-1, 10-diisocyanate, or dicyclohexylmethane-4, 4 '-diisocyanate (H12 MDI), and still more preferably 4,4' -diphenylmethane diisocyanate and/or hexamethylene diisocyanate.
Preferably, the polyol is selected from any one of polyester polyol, polyether polyol, polylactone polyol or polycarbonate polyol or a combination of at least two thereof, and is further preferably polyester polyol and/or polyether polyol.
Preferably, the polyester polyol is prepared by esterification or ester exchange reaction of dihydric alcohol and dicarboxylic acid, dicarboxylic acid anhydride or dicarboxylic ester.
Preferably, the polyester polyol has a number average molecular weight (M) n ) The average molecular weight is 500 to 10000, and may be 600, 800, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 6000, 7000, 8000, 9000 or 9500, for example, more preferably 700 to 5000, and still more preferably 750 to 4000.
The acid value of the polyester polyol is preferably 0 to 1.0mg KOH/g, and may be, for example, 0.1mg KOH/g, 0.2mg KOH/g, 0.3mg KOH/g, 0.4mg KOH/g, 0.5mg KOH/g, 0.6mg KOH/g, 0.7mg KOH/g, 0.8mg KOH/g, or 0.9mg KOH/g, and the like, and more preferably 0.1 to 0.5mg KOH/g.
Preferably, the polyether polyol is obtained by reacting an initiator with an epoxy compound containing 2 to 6 (e.g. 2, 3, 4, 5 or 6) carbon atoms.
Preferably, the initiator is selected from any one of water, small molecule polyol, small molecule polyphenol, small molecule polyamine or small molecule alcohol amine or the combination of at least two of the water, the small molecule polyol, the small molecule polyphenol, the small molecule polyamine and the small molecule alcohol amine; further preferably any one or a combination of at least two of water, propylene glycol, glycerin, trimethylolpropane, ethylenediamine pentaerythritol, xylitol, triethylene diamine, sorbitol, ethylene glycol, bisphenol a, and toluene diamine; still more preferably any one or a combination of at least two of water, propylene glycol or glycerol.
Preferably, the epoxide is selected from any one of ethylene oxide, propylene oxide and Tetrahydrofuran (THF) or a combination of at least two thereof.
Preferably, the polyether polyol comprises any one or a combination of at least two of polyoxyethylene ether, polyoxypropylene ether, polytetramethylene ether glycol, tetrahydrofuran-propylene oxide copolyether and tetrahydrofuran-ethylene oxide copolyether, and is further preferably polytetramethylene ether glycol.
Preferably, the polyether polyol has a number average molecular weight (M) n ) The average molecular weight is 500 to 10000, and may be 700, 900, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 5000, 6000, 7000, 8000, 9000 or the like, for example, and more preferably 700 to 4000.
Preferably, the polylactone polyol is polycaprolactone polyol and is prepared from an epsilon-caprolactone monomer and an initiator under the initiation action of a catalyst.
Preferably, the number average molecular weight (M) of the polycaprolactone polyol n ) The molecular weight is 500 to 3000, for example, 700, 900, 1000, 1200, 1500, 1800, 2000, 2200, 2500, 2800, etc., and more preferably 1000 to 2000.
Preferably, the polycarbonate polyol can be synthesized by adopting a phosgene method, a carbon dioxide regulation copolymerization method, a cyclic carbonate ring-opening polymerization method or an ester exchange method; the polycarbonate polyol has a number average molecular weight (M) n ) The molecular weight is 500 to 4000, and may be, for example, 800, 1000, 1200, 1500, 1800, 2000, 2200, 2500, 2800, 3000, 3500 or the like, and more preferably 1000 to 3000.
Preferably, the chain extender is a polyol having 2 to 10 (e.g., 2, 3, 4, 5, 6, 7, 8, 9 or 10) carbon atoms, and more preferably any one or a combination of at least two 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, glycerol monoallyl ether, trimethylolpropane monoallyl ether, or glycerol monoacrylate.
Preferably, the mass of the chain extender is 3 to 25%, for example, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, or 24%, and preferably 5 to 20%, based on 100% of the total mass of the polyisocyanate and the polyol.
The shore hardness of the thermoplastic polyurethane elastomer is preferably 30A to 70D, and may be, for example, 35A, 40A, 45A, 50A, 55A, 60A, 65A, 70A, 75A, 80A, 85A, 90A, 95A, 60D, 65D, or 68D, more preferably 55A to 98A, and still more preferably 70A to 95A.
Preferably, the polyurethane ionomer is polymerized from a polyisocyanate, a polyol, an ionic monomer, and optionally a chain extender.
Wherein, the polyisocyanate, the polyol and the chain extender of the polyurethane ionomer have the same range as the polyisocyanate, the polyol and the chain extender in the thermoplastic polyurethane elastomer, and the description is omitted for the sake of brevity.
Preferably, the mass of the polyisocyanate is 10 to 45%, for example, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, or 44%, etc., more preferably 15 to 40%, still more preferably 20 to 35%, based on 100% by mass of the total mass of the polyisocyanate, the polyol, the ionic monomer, and the chain extender; the polyol may be, for example, 45%, 50%, 52%, 55%, 58%, 60%, 62%, 65%, 68%, 70%, 72%, 75%, 80%, 83% or the like by mass, preferably 50% to 80%, more preferably 55% to 75%; the ionic monomer may be present in an amount of 1 to 15% by mass, for example, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or the like, more preferably 2 to 12%, and still more preferably 3 to 10%; the mass of the chain extender may be, for example, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%, more preferably 0.5% to 8%, and still more preferably 1% to 5%, in an amount of 0.1% to 10%.
Preferably, the ionic monomer is a diol containing at least one ionic group in a molecule, and the ionic group includes any one of a carboxyl group, a sulfonic group, a phosphoric group, or a hypophosphorous group, or a combination of at least two of them.
Preferably, the ionic monomer comprises any one of 2, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid, polyethylene oxide dihydroxy sulfonate or polypropylene oxide dihydroxy sulfonate or a combination of at least two of the foregoing.
Preferably, the polymerization temperature is in the range of 160 ℃ to 220 ℃, for example 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃ or 215 ℃, and specific values therebetween, for reasons of brevity and conciseness, are not exhaustive and specific values encompassed by the scope of the invention are not intended.
Preferably, the number average molecular weight of the polyurethane ionomer is 10000 to 250000, for example 15000, 20000, 30000, 40000, 50000, 60000, 80000, 100000, 120000, 150000, 180000, 200000, 220000 or 240000, and specific values therebetween, which are not meant to be limiting to space and for the sake of brevity, the present invention is not exhaustive of the specific values included in the ranges.
Preferably, the foaming nucleating agent comprises any one or a combination of at least two of calcium carbonate, talcum powder, silica, zeolite, montmorillonite, carbon black, kaolin, wollastonite, diatomite, mica sheet or titanium dioxide, and further preferably any one or a combination of at least two of calcium carbonate, talcum powder, montmorillonite or kaolin.
Preferably, the foam nucleating agent has an average particle diameter of 0.01 to 10 μm, and for example, may be 0.03 μm, 0.05 μm, 0.08 μm, 0.1 μm, 0.3 μm, 0.5 μm, 0.8 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 7 μm or 9 μm, and specific values therebetween are limited to space and simplicity, and the present invention does not exhaustive list specific values included in the range, and further preferably 0.05 to 5 μm.
Preferably, the foaming material composition also comprises an organic filler and/or an inorganic filler.
Preferably, the foaming material composition further comprises an antioxidant.
In a second aspect, the present invention provides a method for preparing a foam composition according to the first aspect, the method comprising: and melting and blending the block copolymer, the thermoplastic polyurethane elastomer, the polyurethane ionomer and the foaming nucleating agent, and then extruding to obtain the foaming material composition.
Preferably, the temperature of the extrusion is 170 to 220 ℃, for example 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃ or 215 ℃, and the specific values therebetween are limited for brevity and conciseness, and the invention is not exhaustive of the specific values included in the ranges.
Preferably, the extrusion further comprises a granulation step.
In a third aspect, the present invention provides a foamed material prepared from the foamed material composition according to the first aspect.
Preferably, the foamed material is prepared by a method comprising: and melting the particles of the foaming material composition, mixing the particles with a foaming agent, and injecting the mixture into a mold for molding to obtain the foaming material.
Preferably, the foamed material is prepared by a method comprising: mixing the particles of the foaming material composition with a foaming agent, and decompressing to obtain foaming particles; and forming the foaming particles in a mould to obtain the foaming material.
Preferably, the blowing agent is carbon dioxide.
Preferably, the means of mixing is an autoclave or an extruder; the mixing is carried out in an autoclave, the particles of the expanded material composition being impregnated with the blowing agent under pressure; the mixing is carried out in an extruder and the particles of the foamable composition are melted and mixed with a blowing agent.
Preferably, the density of the foaming material is 0.05-0.12 g/cm 3 E.g. 0.06g/cm 3 、0.07g/cm 3 、0.08g/cm 3 、0.09g/cm 3 、0.1g/cm 3 Or 0.11g/cm 3 And specific points between the above points, are not exhaustive of the specific points encompassed by the scope of the invention, for the sake of brevity and conciseness.
Compared with the prior art, the invention has the following beneficial effects:
in the foaming material composition provided by the invention, the block copolymer, the thermoplastic polyurethane elastomer and the polyurethane ionomer are compounded and matched with the foaming nucleating agent, so that the density of the obtained foaming material is 0.09-0.11 g/cm 3 The rebound resilience is more than or equal to 79 percent, the compression permanent deformation is less than 20 percent, and the composite material has the characteristics of light weight, high rebound resilience and low compression permanent deformation; moreover, the tearing strength of the foaming material can reach more than 8N/mm, the tensile strength is more than 2.5MPa, the elongation at break is more than 190%, and the foaming material has excellent comprehensive mechanical properties such as tearing resistance and tensile property, is low in preparation cost and is suitable for industrial production.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
Preparation example 1
A polyurethane ionomer is a carboxylic acid type polyurethane ionomer and is obtained by polymerizing 4,4 '-diphenylmethane diisocyanate (4, 4' -MDI), polytetramethylene ether glycol (PTMG-1000), 2-dimethylolpropionic acid (Perstorp) and 1, 4-Butanediol (BDO); the preparation method comprises the following steps: PTMG-1000, BDO, 4'-MDI and 2, 2-dimethylolpropionic acid are respectively heated to 76 ℃, 46 ℃, 70 ℃ and 80 ℃, the mass proportions of PTMG-1000 parts by weight, BDO 1 parts by weight, 4' -MDI 25 parts by weight and 2, 2-dimethylolpropionic acid 7 parts by weight are respectively sent into a double screw extruder by a casting machine, the temperature of a screw rod of the extruder is controlled to be 160 ℃ in the first zone, 170 ℃ in the second zone, 175 ℃ in the third zone, 180 ℃ in the fourth zone, 185 ℃ in the fifth zone, 190 ℃ in the sixth zone, 195 ℃ in the seventh zone, 190 ℃ in the eighth zone, the temperature of a die head is controlled to be 200 ℃, and the carboxylic acid type polyurethane is prepared by underwater grain cutting; dissolving the obtained carboxylic acid type polyurethane in acetone, adding zinc acetate (the mass ratio of the zinc acetate to the carboxylic acid type polyurethane is 0.1.
Preparation example 2
A polyurethane ionomer is a sulfonic polyurethane ionomer and is obtained by polymerizing polybutylene adipate (PBA-2000), 4' -MDI, polypropylene glycol sulfonate (SPPG, guangzhou Xingusai chemical technology Co., ltd.) and BDO; the preparation method comprises the following steps: respectively heating PBA-2000, BDO, 4'-MDI and SPPG to 76 ℃, 46 ℃, 70 ℃ and 80 ℃, respectively feeding the PBA-2000, BDO 1, 4' -MDI and SPPG in mass ratio of 75 parts by weight, 4 parts by weight and 4 parts by weight of the PBA-2000, the BDO 1, the PBA-2000 and the SPPG into a double-screw extruder by using a casting machine, respectively controlling the screw temperature of the extruder to be 170 ℃ in a first zone, 180 ℃ in a second zone, 185 ℃ in a third zone, 190 ℃ in a fourth zone, 195 ℃ in a fifth zone, 200 ℃ in a sixth zone, 205 ℃ in a seventh zone, 200 ℃ in an eighth zone, controlling the die head temperature to be 200 ℃, and preparing the sulfonated polyurethane ionomer by underwater grain cutting.
Example 1
The embodiment provides a foaming material composition, which comprises the following components in percentage by mass:
wherein the block copolymer is a polyamide-polyether block copolymer (akoma Pebax 4533, hardness 45D); the TPU elastomer is Wanhua chemical WHT-8170RV, and the hardness is 70A.
The embodiment also provides a foaming material, which is prepared from the foaming material composition in the embodiment by the following specific method:
(1) Putting the block copolymer, the TPU elastomer, the carboxylic acid type polyurethane ionomer and the calcium carbonate into a double-screw extruder according to the formula amount, extruding and granulating at the temperature of 170 ℃ in a first zone, 180 ℃ in a second zone, 185 ℃ in a third zone, 190 ℃ in a fourth zone, 195 ℃ in a fifth zone, 200 ℃ in a sixth zone, 195 ℃ in a seventh zone and 190 ℃ in an eighth zone to obtain particles of the foaming material composition;
(2) Adding the particles obtained in the step (1) into a high-pressure kettle, introducing carbon dioxide to impregnate the particles, wherein the temperature of the high-pressure kettle is 120 ℃, the pressure is 15MPa, and the impregnation time is 3h; after impregnation, discharging the materials in the high-pressure kettle into the atmospheric environment at a pressure release rate of 10MPa/s to obtain foamed particles;
(3) Putting the foamed particles obtained in the step (2) into steam forming equipment, and introducing 3kg/cm 2 Forming for 180s; then circulating water is introduced to cool the mould for about 60 seconds, so that the temperature of the mould is reduced to below 50 ℃, and the mould is vacuumized for 10 seconds to remove the moisture on the surface of the sample; and opening the die, taking out a sample, namely the foaming material, and carrying out performance test after the sample is placed for 24 hours.
Example 2
The embodiment provides a foaming material composition, which comprises the following components in percentage by mass:
wherein the block copolymer is a poly 12 lactam-polyether block copolymer (Wawa chemistry, 45D durometer); the TPU elastomer is Wanhua chemical WHT-A9583, and the hardness is 95A.
The embodiment also provides a foaming material, which is prepared from the foaming material composition in the embodiment, and the specific method is as follows:
(1) Putting the block copolymer, the TPU elastomer, the sulfonic acid type polyurethane ionomer and the talcum powder into a double-screw extruder according to the formula ratio, and extruding and granulating at the extrusion temperature of 170 ℃ in a first region, 180 ℃ in a second region, 185 ℃ in a third region, 190 ℃ in a fourth region, 195 ℃ in a fifth region, 200 ℃ in a sixth region, 195 ℃ in a seventh region, 190 ℃ in an eighth region and 185 ℃ in a ninth region to obtain particles of the foaming material composition;
(2) Adding the particles obtained in the step (1) into an autoclave, introducing carbon dioxide to impregnate the particles with the carbon dioxide, wherein the temperature of the autoclave is 120 ℃, the pressure is 15MPa, and the impregnating time is 3h; after impregnation, discharging the materials in the high-pressure kettle into the atmospheric environment at the pressure release rate of 10MPa/s to obtain foamed particles;
(3) Putting the foaming particles obtained in the step (2) into steam forming equipment, and introducing 3kg/cm 2 Forming for 180s; then circulating water is introduced to cool the mould for about 60s, so that the temperature of the mould is reduced to below 50 ℃, and the mould is vacuumized for 10s to remove the moisture on the surface of the sample; and opening the mold, taking out a sample, namely the foaming material, and carrying out performance test after the sample is placed for 24 hours.
Example 3
The embodiment provides a foaming material composition, which comprises the following components in percentage by mass:
wherein the block copolymer is a poly 12 lactam-polyether block copolymer (Wawa chemistry, 45D durometer); the TPU elastomer is Wanhua chemical WHT-1190 and has the hardness of 90A.
The embodiment also provides a foaming material, which is prepared from the foaming material composition in the embodiment, and the specific method is as follows:
(1) Putting the block copolymer, the TPU elastomer, the carboxylic acid type polyurethane ionomer and the calcium carbonate into a double-screw extruder according to the formula ratio, wherein the extrusion temperature is 175 ℃ in a first zone, 185 ℃ in a second zone, 190 ℃ in a third zone, 195 ℃ in a fourth zone, 200 ℃ in a fifth zone, 205 ℃ in a sixth zone, 200 ℃ in a seventh zone, 195 ℃ in an eighth zone and 190 ℃ in a ninth zone, and extruding and granulating to obtain particles of the foaming material composition;
(2) Adding the particles obtained in the step (1) into a high-pressure kettle, introducing carbon dioxide to impregnate the particles, wherein the temperature of the high-pressure kettle is 120 ℃, the pressure is 15MPa, and the impregnation time is 3h; after impregnation, discharging the materials in the high-pressure kettle into the atmospheric environment at the pressure release rate of 10MPa/s to obtain foamed particles;
(3) Putting the foaming particles obtained in the step (2) into steam forming equipment, and introducing 3kg/cm 2 Forming for 180s; then introduced into the circulationCooling the mould by circulating water for about 60s to reduce the temperature of the mould to below 50 ℃, vacuumizing for 10s, and removing the moisture on the surface of the sample; and opening the mold, taking out a sample, namely the foaming material, and carrying out performance test after the sample is placed for 24 hours.
Example 4
The embodiment provides a foaming material composition, which comprises the following components in percentage by mass:
wherein the block copolymer is a polyamide-polyether block copolymer (akoma Pebax 2533, hardness 77A); the TPU elastomer is Wanhua chemical WHT-8190RV and has the hardness of 90A.
The embodiment also provides a foaming material, which is prepared from the foaming material composition in the embodiment by the following specific method:
(1) Putting the block copolymer, the TPU elastomer, the sulfonic polyurethane ionomer and the talcum powder into a double-screw extruder according to the formula ratio, and extruding and granulating at the extrusion temperature of 175 ℃ in a first area, 185 ℃ in a second area, 190 ℃ in a third area, 195 ℃ in a fourth area, 200 ℃ in a fifth area, 205 ℃ in a sixth area, 200 ℃ in a seventh area, 195 ℃ in an eighth area and 190 ℃ in a ninth area to obtain particles of the foaming material composition;
(2) Adding the particles obtained in the step (1) into a high-pressure kettle, introducing carbon dioxide to impregnate the particles, wherein the temperature of the high-pressure kettle is 120 ℃, the pressure is 15MPa, and the impregnation time is 3h; after impregnation, discharging the materials in the high-pressure kettle into the atmospheric environment at a pressure release rate of 10MPa/s to obtain foamed particles;
(3) Putting the foaming particles obtained in the step (2) into steam forming equipment, and introducing 3kg/cm 2 Forming for 180s; then circulating water is introduced to cool the mould for about 60 seconds, so that the temperature of the mould is reduced to below 50 ℃, and the mould is vacuumized for 10 seconds to remove the moisture on the surface of the sample; and opening the mold, taking out a sample, namely the foaming material, and carrying out performance test after the sample is placed for 24 hours.
Example 5
The embodiment provides a foaming material composition, which comprises the following components in percentage by mass:
wherein the block copolymer is polyether ester block copolymer (DuPont)
6646, hardness 66D); the TPU elastomer is Wanhua chemical WHT-8185RV and has the hardness of 85A.
The embodiment also provides a foaming material, which is prepared from the foaming material composition in the embodiment, and the specific method is as follows:
(1) Putting the block copolymer, the TPU elastomer, the carboxylic acid type polyurethane ionomer and the calcium carbonate into a double-screw extruder according to the formula ratio, wherein the extrusion temperature is 195 ℃ in a first zone, 200 ℃ in a second zone, 205 ℃ in a third zone, 210 ℃ in a fourth zone, 215 ℃ in a fifth zone, 220 ℃ in a sixth zone, 215 ℃ in a seventh zone, 210 ℃ in an eighth zone and 205 ℃ in a ninth zone, and extruding and granulating to obtain particles of the foaming material composition;
(2) Adding the particles obtained in the step (1) into an autoclave, introducing carbon dioxide to impregnate the particles with the carbon dioxide, wherein the temperature of the autoclave is 120 ℃, the pressure is 15MPa, and the impregnating time is 3h; after impregnation, discharging the materials in the high-pressure kettle into the atmospheric environment at a pressure release rate of 10MPa/s to obtain foamed particles;
(3) Putting the foamed particles obtained in the step (2) into steam forming equipment, and introducing 3kg/cm 2 Forming for 180s; then circulating water is introduced to cool the mould for about 60s, so that the temperature of the mould is reduced to below 50 ℃, and the mould is vacuumized for 10s to remove the moisture on the surface of the sample; and opening the mold, taking out a sample, namely the foaming material, and carrying out performance test after the sample is placed for 24 hours.
Example 6
The embodiment provides a foaming material composition, which comprises the following components in percentage by mass:
wherein the block copolymer is polyether ester block copolymer (DuPont)
4069, hardness 40D); the TPU elastomer is Wanhua chemical WHT-1185 with the hardness of 85A.
The embodiment also provides a foaming material, which is prepared from the foaming material composition in the embodiment by the following specific method:
(1) Putting the block copolymer, the TPU elastomer, the carboxylic acid type polyurethane ionomer and the talcum powder into a double-screw extruder according to the formula ratio, and extruding and granulating at the extrusion temperature of 185 ℃ in a first area, 190 ℃ in a second area, 195 ℃ in a third area, 205 ℃ in a fourth area, 210 ℃ in a fifth area, 215 ℃ in a sixth area, 210 ℃ in a seventh area, 205 ℃ in an eighth area and 200 ℃ in a ninth area to obtain particles of the foaming material composition;
(2) Adding the particles obtained in the step (1) into an autoclave, introducing carbon dioxide to impregnate the particles with the carbon dioxide, wherein the temperature of the autoclave is 120 ℃, the pressure is 15MPa, and the impregnating time is 3h; after impregnation, discharging the materials in the high-pressure kettle into the atmospheric environment at the pressure release rate of 10MPa/s to obtain foamed particles;
(3) Putting the foaming particles obtained in the step (2) into steam forming equipment, and introducing 3kg/cm 2 Forming for 180s; then circulating water is introduced to cool the mould for about 60s, so that the temperature of the mould is reduced to below 50 ℃, and the mould is vacuumized for 10s to remove the moisture on the surface of the sample; and opening the mold, taking out a sample, namely the foaming material, and carrying out performance test after the sample is placed for 24 hours.
Example 7
The embodiment provides a foaming material composition, which comprises the following components in percentage by mass:
wherein the block copolymer is a polyamide-polyether block copolymer (akoma Pebax 5533, hardness 55D); the TPU elastomer is Wanhua chemical WHT-8180RV and has the hardness of 80A.
The embodiment also provides a foaming material, which is prepared from the foaming material composition in the embodiment, and the specific method is as follows:
(1) Putting the block copolymer, the TPU elastomer, the carboxylic acid type polyurethane ionomer and calcium carbonate into a double-screw extruder according to the formula ratio, and extruding and granulating at the extrusion temperature of 180 ℃ in a first zone, 185 ℃ in a second zone, 190 ℃ in a third zone, 195 ℃ in a fourth zone, 200 ℃ in a fifth zone, 205 ℃ in a sixth zone, 200 ℃ in a seventh zone, 195 ℃ in an eighth zone and 190 ℃ in a ninth zone to obtain particles of the foaming material composition;
(2) Adding the particles obtained in the step (1) into a high-pressure kettle, introducing carbon dioxide to impregnate the particles, wherein the temperature of the high-pressure kettle is 120 ℃, the pressure is 15MPa, and the impregnation time is 3h; after impregnation, discharging the materials in the high-pressure kettle into the atmospheric environment at the pressure release rate of 10MPa/s to obtain foamed particles;
(3) Putting the foamed particles obtained in the step (2) into steam forming equipment, and introducing 3kg/cm 2 Forming for 180s; then circulating water is introduced to cool the mould for about 60s, so that the temperature of the mould is reduced to below 50 ℃, and the mould is vacuumized for 10s to remove the moisture on the surface of the sample; and opening the mold, taking out a sample, namely the foaming material, and carrying out performance test after the sample is placed for 24 hours.
Example 8
The embodiment provides a foaming material composition, which comprises the following components in percentage by mass:
wherein the block copolymer is a poly 12 lactam-polyether block copolymer (Wawa chemistry, hardness 35D); the TPU elastomer is Wanhua chemical WHT-8195RV, and the hardness is 95A.
The embodiment also provides a foaming material, which is prepared from the foaming material composition in the embodiment, and the specific method is as follows:
(1) Putting the block copolymer, the TPU elastomer, the carboxylic acid type polyurethane ionomer and the talcum powder into a double-screw extruder according to the formula ratio, and extruding and granulating at the extrusion temperature of 185 ℃ in a first area, 190 ℃ in a second area, 195 ℃ in a third area, 200 ℃ in a fourth area, 205 ℃ in a fifth area, 210 ℃ in a sixth area, 205 ℃ in a seventh area, 200 ℃ in an eighth area and 195 ℃ in a ninth area to obtain particles of the foaming material composition;
(2) Adding the particles obtained in the step (1) into a high-pressure kettle, introducing carbon dioxide to impregnate the particles, wherein the temperature of the high-pressure kettle is 120 ℃, the pressure is 15MPa, and the impregnation time is 3h; after impregnation, discharging the materials in the high-pressure kettle into the atmospheric environment at the pressure release rate of 10MPa/s to obtain foamed particles;
(3) Putting the foamed particles obtained in the step (2) into steam forming equipment, and introducing 3kg/cm 2 Forming for 180s; then circulating water is introduced to cool the mould for about 60s, so that the temperature of the mould is reduced to below 50 ℃, and the mould is vacuumized for 10s to remove the moisture on the surface of the sample; and opening the die, taking out a sample, namely the foaming material, and carrying out performance test after the sample is placed for 24 hours.
Comparative example 1
The comparative example provides a foam composition comprising the following components in parts by weight:
65 parts of block copolymer
TPU elastomer 25 parts
2 parts of talcum powder;
wherein the block copolymer is polyether ester block copolymer (DuPont)
4069, hardness 40D); the TPU elastomer is Wanhua chemical WHT-1185 with the hardness of 85A.
The comparative example also provides a foaming material which is prepared from the foaming material composition in the comparative example, and the specific method is as follows:
(1) Putting the block copolymer, the TPU elastomer and the talcum powder into a double-screw extruder according to the formula ratio, extruding at the temperature of 185 ℃ in a first area, 195 ℃ in a second area, 200 ℃ in a third area, 205 ℃ in a fourth area, 210 ℃ in a fifth area, 215 ℃ in a sixth area, 210 ℃ in a seventh area, 205 ℃ in an eighth area and 200 ℃ in a ninth area, and extruding and granulating to obtain particles of the foaming material composition;
(2) Adding the particles obtained in the step (1) into an autoclave, introducing carbon dioxide to impregnate the particles with the carbon dioxide, wherein the temperature of the autoclave is 120 ℃, the pressure is 15MPa, and the impregnating time is 3h; after impregnation, discharging the materials in the high-pressure kettle into the atmospheric environment at a pressure release rate of 10MPa/s to obtain foamed particles;
(3) Putting the foamed particles obtained in the step (2) into steam forming equipment, and introducing 3kg/cm 2 Forming for 180s; then circulating water is introduced to cool the mould for about 60s, so that the temperature of the mould is reduced to below 50 ℃, and the mould is vacuumized for 10s to remove the moisture on the surface of the sample; and opening the mold, taking out a sample, namely the foaming material, and carrying out performance test after the sample is placed for 24 hours.
Comparative example 2
The comparative example provides a foam composition comprising the following components in parts by weight:
47 parts of block copolymer
42 parts of TPU elastomer
1 part of calcium carbonate;
wherein the block copolymer is a polyamide-polyether block copolymer (akoma Pebax 5533, hardness 55D); the TPU elastomer is Wanhua chemical WHT-8180RV and has the hardness of 80A.
The comparative example also provides a foaming material, which is prepared from the foaming material composition in the comparative example, and the specific method is as follows:
(1) Putting the block copolymer, the TPU elastomer and the calcium carbonate into a double-screw extruder according to the formula ratio, extruding and granulating at the extrusion temperature of 180 ℃ in a first zone, 185 ℃ in a second zone, 190 ℃ in a third zone, 195 ℃ in a fourth zone, 200 ℃ in a fifth zone, 205 ℃ in a sixth zone, 200 ℃ in a seventh zone and 195 ℃ in an eighth zone to obtain particles of the foaming material composition;
(2) Adding the particles obtained in the step (1) into a high-pressure kettle, introducing carbon dioxide to impregnate the particles, wherein the temperature of the high-pressure kettle is 120 ℃, the pressure is 15MPa, and the impregnation time is 3h; after impregnation, discharging the materials in the high-pressure kettle into the atmospheric environment at a pressure release rate of 10MPa/s to obtain foamed particles;
(3) Putting the foamed particles obtained in the step (2) into steam forming equipment, and introducing 3kg/cm 2 Forming for 180s; then circulating water is introduced to cool the mould for about 60 seconds, so that the temperature of the mould is reduced to below 50 ℃, and the mould is vacuumized for 10 seconds to remove the moisture on the surface of the sample; and opening the die, taking out a sample, namely the foaming material, and carrying out performance test after the sample is placed for 24 hours.
Comparative example 3
The comparative example provides a foam composition comprising the following components in parts by weight:
wherein the block copolymer is a poly 12 lactam-polyether block copolymer (Wawa chemistry, 45D durometer); the TPU elastomer is Wanhua chemical WHT-1190 and has the hardness of 90A.
The comparative example also provides a foaming material which is prepared from the foaming material composition in the comparative example, and the specific method is as follows:
(1) Putting the block copolymer, the TPU elastomer, the carboxylic acid type polyurethane ionomer and calcium carbonate into a double-screw extruder according to the formula ratio, and extruding and granulating at the temperature of 185 ℃ in a first zone, 190 ℃ in a second zone, 195 ℃ in a third zone, 200 ℃ in a fourth zone, 205 ℃ in a fifth zone, 210 ℃ in a sixth zone, 205 ℃ in a seventh zone, 200 ℃ in an eighth zone and 195 ℃ in a ninth zone to obtain particles of the foaming material composition;
(2) Adding the particles obtained in the step (1) into a high-pressure kettle, introducing carbon dioxide to impregnate the particles, wherein the temperature of the high-pressure kettle is 120 ℃, the pressure is 15MPa, and the impregnation time is 3h; after impregnation, discharging the materials in the high-pressure kettle into the atmospheric environment at the pressure release rate of 10MPa/s to obtain foamed particles;
(3) Putting the foamed particles obtained in the step (2) into steam forming equipment, and introducing 3kg/cm 2 Forming for 180s; then the circulating water is introduced for cooling the mould for about 60s to ensure that the mould is cooledReducing the temperature to below 50 ℃, vacuumizing for 10s, and removing the moisture on the surface of the sample; and opening the mold, taking out a sample, namely the foaming material, and carrying out performance test after the sample is placed for 24 hours.
The foams provided in examples 1 to 8 and comparative examples 1 to 3 were tested for their properties and compared with commercially available TPU foams, commercially available thermoplastic polyester elastomer (TPEE) foams and commercially available Polyamide Elastomer (PEBA) foams by the following methods:
(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) Tear strength: the test was carried out according to the method described in ISO 8067-2008;
(5) Ball rebound resilience: the test was carried out by the method described in ISO 8307-2007;
(6) Compression set: testing by the method described in ISO 1856-2018;
the test results are shown in table 1:
TABLE 1
As is clear from the data in Table 1, the foams provided in examples 1 to 8 of the present invention had densities of 0.09 to 0.11g/cm 3 The rebound resilience is 79-82%, the compression permanent deformation is reduced to 9-19%, and the composite material has the characteristics of light weight, high rebound resilience and low compression permanent deformation; moreover, the tearing strength of the foaming material can reach more than 8N/mm, the tensile strength is more than 2.5MPa, the elongation at break is more than 190%, and the foaming material has excellent comprehensive mechanical properties such as tearing resistance and tensile property. Therefore, the block copolymer, the TPU elastomer and the polyurethane ionomer are compounded, so that the foaming material has excellent performances in the aspects of density, tear strength, rebound resilience, compression permanent deformation, tensile strength and the like, and has remarkable comprehensive performanceIs superior to commercially available TPU foaming materials, TPPE foaming materials and nylon elastomer foaming materials, has lower manufacturing cost, and is suitable for large-scale industrial production.
Comparative examples 1 and 2, which do not contain polyurethane ionomer, result in a foamed material having a high density, a reduced tear strength, and significantly reduced resilience, compression set, and tensile properties; the content of polyurethane ionomer in comparative example 3 was too high, resulting in too high hardness of the foamed material and a significant decrease in resilience.
The applicant states that the present invention is described by the above examples to describe the foaming composition and the foaming material of the present invention, but the present invention is not limited to the above examples, that is, the present invention is not limited to the above examples. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (19)
1. The foaming material composition is characterized by comprising the following components in percentage by mass:
the block copolymer comprises at least one hard segment and at least one soft segment;
the hard segment in the block copolymer is selected from a polyamide segment and/or a polyester segment; the soft block in the block copolymer is selected from any one of polyether block, polysiloxane block or polyolefin block or the combination of at least two of the polyether block, the polysiloxane block and the polyolefin block;
the polyurethane ionomer is polymerized from a polyisocyanate, a polyol, an ionic monomer, and optionally a chain extender;
the mass of the ionic monomer is 1-15% based on 100% of the total mass of the polyisocyanate, the polyol, the ionic monomer and the chain extender;
the ionic monomer comprises any one of 2, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid, polyethylene oxide dihydroxy sulfonate or polypropylene oxide dihydroxy sulfonate or the combination of at least two of the two;
the number average molecular weight of the polyurethane ionomer is 10000-250000.
2. The foam composition of claim 1, wherein the polyamide segments comprise any one of polyamide 6, polyamide 11, polyamide 12, polyamide 66, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, polyamide 1111, or polyamide 1212, or a combination of at least two thereof.
3. The foam composition of claim 1, wherein the polyester segments comprise polyalkylene terephthalate.
4. The foam composition of claim 1, wherein the soft block of the block copolymer is a polyether block.
5. The foam composition as claimed in claim 1 or 4, wherein the polyether segment comprises any one or a combination of at least two of polyoxyethylene ether, polyoxypropylene ether, polytetramethylene ether, tetrahydrofuran-propylene oxide copolyether and tetrahydrofuran-ethylene oxide copolyether.
6. The foam composition of claim 1, wherein the block copolymer has a shore hardness of 30A to 80D.
7. The foam composition as claimed in claim 6, wherein the Shore hardness of the block copolymer is 60A to 60D.
8. The foam composition according to claim 1, wherein the thermoplastic polyurethane elastomer is selected from any one of polyester type thermoplastic polyurethane elastomer, polyether type thermoplastic polyurethane elastomer, polycaprolactone type thermoplastic polyurethane elastomer, or polycarbonate type thermoplastic polyurethane elastomer, or a combination of at least two thereof.
9. The foam composition of claim 1, wherein the thermoplastic polyurethane elastomer has a shore hardness of 30A to 70D.
10. The foam composition as claimed in claim 9, wherein the thermoplastic polyurethane elastomer has a shore hardness of 55A to 98A.
11. The foam material composition according to claim 1, wherein the mass of the polyisocyanate is 10 to 45%, the mass of the polyol is 40 to 85%, the mass of the ionic monomer is 1 to 15%, and the mass of the chain extender is 0.1 to 10%, based on 100% of the total mass of the polyisocyanate, the polyol, the ionic monomer, and the chain extender.
12. The foam material composition as claimed in claim 1, wherein the foam nucleating agent comprises any one or a combination of at least two of calcium carbonate, talc, silica, zeolite, montmorillonite, carbon black, kaolin, wollastonite, diatomaceous earth, mica flakes or titanium dioxide.
13. The foam composition of claim 12, wherein the foam nucleating agent is any one or a combination of at least two of calcium carbonate, talc, montmorillonite or kaolin.
14. The foam material composition according to claim 1, wherein the foam nucleating agent has an average particle diameter of 0.01 to 10 μm.
15. The foam composition according to claim 14, wherein the foam nucleating agent has an average particle diameter of 0.05 to 5 μm.
16. A method for preparing the foam composition of any one of claims 1 to 15, wherein the method comprises: and melting and blending the block copolymer, the thermoplastic polyurethane elastomer, the polyurethane ionomer and the foaming nucleating agent, and then extruding to obtain the foaming material composition.
17. A foamed material produced from the foamed material composition according to any one of claims 1 to 15.
18. The foamed material of claim 17, wherein the foamed material is prepared by a method comprising: mixing the particles of the foaming material composition with a foaming agent, and decompressing to obtain foaming particles; and forming the foaming particles in a mould to obtain the foaming material.
19. Foam according to claim 17 or 18, wherein the density of the foam is 0.05 to 0.12g/cm 3 。
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2231411A1 (en) * | 1972-06-27 | 1974-01-10 | Bayer Ag | COMPOSITE MATERIALS AND METHOD FOR THEIR PRODUCTION |
| CN1537129A (en) * | 2001-07-27 | 2004-10-13 | ÷��������ѧ�г�����˾ | Ionomer polyurethane thermoplastic |
| CN107090070A (en) * | 2017-05-11 | 2017-08-25 | 东莞泰康泡绵有限公司 | A kind of hydrophilic polyurethane bubble silk floss and preparation method thereof |
| CN107459637A (en) * | 2017-08-25 | 2017-12-12 | 华南理工大学 | Low molecule amount and the poly butylene succinate ionomer of high melt viscosity and its preparation and the microcellular foam material based on it and application |
| CN110343286A (en) * | 2019-06-17 | 2019-10-18 | 华南理工大学 | A kind of poly butylene succinate ionomer foam and the preparation method and application thereof |
| CN110974998A (en) * | 2019-12-27 | 2020-04-10 | 青岛科技大学 | Degradable polyurethane foam dressing and preparation method thereof |
-
2021
- 2021-11-17 CN CN202111360161.8A patent/CN113943489B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2231411A1 (en) * | 1972-06-27 | 1974-01-10 | Bayer Ag | COMPOSITE MATERIALS AND METHOD FOR THEIR PRODUCTION |
| CN1537129A (en) * | 2001-07-27 | 2004-10-13 | ÷��������ѧ�г�����˾ | Ionomer polyurethane thermoplastic |
| CN107090070A (en) * | 2017-05-11 | 2017-08-25 | 东莞泰康泡绵有限公司 | A kind of hydrophilic polyurethane bubble silk floss and preparation method thereof |
| CN107459637A (en) * | 2017-08-25 | 2017-12-12 | 华南理工大学 | Low molecule amount and the poly butylene succinate ionomer of high melt viscosity and its preparation and the microcellular foam material based on it and application |
| CN110343286A (en) * | 2019-06-17 | 2019-10-18 | 华南理工大学 | A kind of poly butylene succinate ionomer foam and the preparation method and application thereof |
| CN110974998A (en) * | 2019-12-27 | 2020-04-10 | 青岛科技大学 | Degradable polyurethane foam dressing and preparation method thereof |
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