CN112920501A - Nylon elastomer composite material foam and preparation method thereof - Google Patents
Nylon elastomer composite material foam and preparation method thereof Download PDFInfo
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- CN112920501A CN112920501A CN202110349832.4A CN202110349832A CN112920501A CN 112920501 A CN112920501 A CN 112920501A CN 202110349832 A CN202110349832 A CN 202110349832A CN 112920501 A CN112920501 A CN 112920501A
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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
- C08J9/06—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 chemical blowing agent
- C08J9/10—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 chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
- C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
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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
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
Abstract
The invention discloses a nylon elastomer composite material foam and a preparation method thereof. The nylon elastomer composite foam is formed from raw materials comprising: the composite material, the cross-linking agent, the foaming agent and the foaming auxiliary agent are mixed according to the mass ratio of 100: 0.5-5: 0.5-5: 0.5 to 8; wherein the composite material is formed by the following raw materials: the rubber composition comprises a nylon elastomer, an ethylene-vinyl acetate copolymer and a compatilizer, wherein the mass ratio of the nylon elastomer to the ethylene-vinyl acetate copolymer to the compatilizer is 5-70: 30-95: 0.5-3. The nylon elastomer composite material foam not only keeps the excellent comprehensive performance of the nylon elastomer, but also simplifies the nylon elastomer foaming and forming process, and the obtained nylon elastomer composite material foam has the advantages of good cold resistance, high toughness, higher foam melt strength, uniform foam holes, small density, small compression deformation and large rebound resilience, and has wide application prospect in the field of soles.
Description
Technical Field
The invention relates to a nylon elastomer composite material foam and a preparation method thereof.
Background
Nylon elastomers, also known as thermoplastic polyamide elastomers (TPAE), are linear block copolymers composed of polyamide hard segments and polyamide soft segments. The nylon elastomer can adapt to various use environments due to the fact that the mechanical property of the nylon elastomer can be changed by adjusting the proportion of the soft segment to the soft segment, and is an elastomer with a good prospect. Particularly in the field of footwear, the excellent cold resistance, lighter weight and good toughness of nylon elastomers have led to their widespread use in shoe sole support members, foamed midsoles and the like. However, the nylon elastomer can only be processed by a supercritical method at present, and the foamed product is usually in the shape of beads and is not suitable for being used as a foamed midsole of shoes. If the shoe insole is to be manufactured into a shoe insole for use, more processing steps are needed, and the process is complicated and unstable. Therefore, the development of a novel nylon elastomer composite material foam and a preparation method thereof can not only retain the excellent comprehensive performance of the nylon elastomer to enable the nylon elastomer to be used as a foaming insole of shoes, but also simplify the process, so that the nylon elastomer is very necessary to be more easily foamed and formed.
Disclosure of Invention
In view of the above, it is an object of the present invention to provide a nylon elastomer composite foam. The nylon elastomer composite material foam not only keeps the excellent comprehensive performance of the nylon elastomer, but also simplifies the nylon elastomer foaming and forming process, and the obtained nylon elastomer composite material foam has the advantages of good cold resistance, high toughness, higher foam melt strength, uniform foam holes, small density, small compression deformation and large rebound resilience, and has wide application prospect in the field of soles.
Another object of the present invention is to provide a method for preparing a nylon elastomer composite foam. The method has simple steps and good stability, and solves the problem of poor compatibility when the nylon elastomer and the ethylene vinyl acetate copolymer (EVA) are blended.
The invention adopts the following technical scheme to achieve the purpose.
The invention provides a nylon elastomer composite foam which is formed by the following raw materials: the composite material, the cross-linking agent, the foaming agent and the foaming auxiliary agent are mixed according to the mass ratio of 100: 0.5-5: 0.5-5: 0.5 to 8;
wherein the composite material is formed by the following raw materials: the rubber composition comprises a nylon elastomer, an ethylene-vinyl acetate copolymer and a compatilizer, wherein the mass ratio of the nylon elastomer to the ethylene-vinyl acetate copolymer to the compatilizer is 5-70: 30-95: 0.5-3.
In certain embodiments, the nylon elastomer composite foam of the present invention is formed from raw materials consisting of: the composite material, the cross-linking agent, the foaming agent and the foaming auxiliary agent are mixed according to the mass ratio of 100: 0.5-5: 0.5-5: 0.5 to 8; preferably, the mass ratio of the composite material to the cross-linking agent to the foaming auxiliary agent is 100: 0.5 to 3: 0.5-3: 1-5; more preferably, the mass ratio of the composite material, the cross-linking agent, the foaming agent and the foaming auxiliary agent is 100: 0.8-1.6: 1.6-1.8: 1 to 2. In certain embodiments, the composite material is formed from raw materials consisting of: the rubber composition comprises a nylon elastomer, an ethylene-vinyl acetate copolymer and a compatilizer, wherein the mass ratio of the nylon elastomer to the ethylene-vinyl acetate copolymer to the compatilizer is 5-70: 30-95: 0.5-3; preferably, the mass ratio of the nylon elastomer to the ethylene-vinyl acetate copolymer to the compatilizer is 5-40: 60-95: 0.5-3; more preferably, the mass ratio of the nylon elastomer to the ethylene-vinyl acetate copolymer to the compatilizer is 10-40: 60-90: 0.8-1.2. The invention sets the ethylene vinyl acetate copolymer (EVA), the nylon elastomer, the compatilizer, the cross-linking agent, the foaming agent and the foaming auxiliary agent in the dosage range, so that the obtained nylon elastomer composite material foam not only keeps the excellent comprehensive performance of the nylon elastomer, but also simplifies the foaming forming process of the nylon elastomer and overcomes the defect of poor mechanical property of the ethylene vinyl acetate copolymer.
The ethylene-vinyl acetate copolymer (EVA) of the present invention has a Vinyl Acetate (VA) content of 20 to 50 wt%, preferably 24 to 40 wt%, and more preferably 26 to 32 wt%. The ethylene-vinyl acetate copolymer with appropriate content of vinyl acetate is selected to be compounded with the nylon elastomer to prepare the nylon elastomer composite material foam, so that the comprehensive performance of the foam can be improved.
The nylon elastomer is a copolymer nylon elastomer consisting of polyamide elastomer hard segments and polyamide elastomer soft segments, wherein the polyamide elastomer hard segments comprise at least one of polyamide 6, polyamide 11, polyamide 12, polyamide 66, polyamide 610, polyamide 1010, polyamide 1011, polyamide 1012, polyamide 1210, polyamide 1211, polyamide 1212, polyamide 1213, polyamide 1311, polyamide 1312 and polyamide 1313; the polyamide elastomer soft segment comprises at least one of polytetrahydrofuran ether, polyethylene glycol, polypropylene glycol and polytetramethylene glycol. Preferably, the polyamide elastomer hard segment is selected from any one of polyamide 6, polyamide 1012 and polyamide 12; the polyamide elastomer soft segment is selected from polytetrahydrofuran (molecular weight is 1000-2000). According to the invention, the nylon elastomer with the hardness similar to that of the ethylene-vinyl acetate copolymer is selected, and the rich variety and the good mechanical property of the nylon elastomer are introduced into the ethylene-vinyl acetate copolymer, so that the problem of poor compatibility when the ethylene-vinyl acetate copolymer and the nylon elastomer are blended is solved, the defect of poor mechanical property of the ethylene-vinyl acetate copolymer is improved, and the obtained nylon elastomer composite material foam has better cold resistance, rebound resilience and toughness.
The compatilizer comprises at least one of maleic anhydride, zinc acetate, ethylene-vinyl acetate grafted glycidyl methacrylate EVA-g-GMA, maleic anhydride grafted ethylene-1-octene copolymer POE-g-MAH, maleic anhydride grafted ethylene propylene diene monomer EPDM-g-MAH, maleic anhydride grafted styrene-ethylene-butadiene-styrene block copolymer SEBS-g-MAH, maleic anhydride grafted acrylonitrile-butadiene-styrene copolymer ABS-g-MAH and maleic anhydride grafted polystyrene PS-g-MAH. Preferably, the compatilizer is any one selected from ethylene-vinyl acetate grafted glycidyl methacrylate EVA-g-GMA, zinc acetate, maleic anhydride grafted ethylene propylene diene monomer EPDM-g-MAH and maleic anhydride grafted ethylene-1-octene copolymer POE-g-MAH. The compatilizer is selected to solve the problem of poor compatibility when Ethylene Vinyl Acetate (EVA) and nylon elastomer are blended, and the composite material with good compatibility can be obtained after blending extrusion by a double-screw extruder.
The cross-linking agent comprises at least one of dicumyl peroxide, di-tert-butylperoxydiisopropylbenzene, amino silane coupling agent and epoxy silane coupling agent; preferably, it is any one of dicumyl peroxide, di-t-butylperoxydiisopropylbenzene, an aminosilane coupling agent and an epoxysilane coupling agent. According to one embodiment of the invention, the crosslinking agent is dicumyl peroxide. According to another embodiment of the invention, the crosslinking agent is di-tert-butylperoxydiisopropylbenzene. According to a further embodiment of the invention, the cross-linking agent is an aminosilane coupling agent. According to yet another embodiment of the invention, the cross-linking agent is an epoxy silane based coupling agent. The cross-linking agent can improve the rheological property and the physical and mechanical properties of the nylon elastomer composite material foam, so that the resilience and the toughness of the nylon elastomer composite material foam are improved.
The foaming agent comprises at least one of p-toluenesulfonyl semicarbazide, azo foaming agent, dinitroso pentamethine tetramine and 4, 4' -oxo-diphenyl sulfonyl hydrazide; preferably, the blowing agent is any one of p-toluenesulfonyl semicarbazide, azo blowing agent, dinitrosopentamethylenetetramine, and 4, 4' -oxybis-benzenesulfonylhydrazide. According to one embodiment of the invention, the blowing agent is p-toluenesulfonyl semicarbazide. According to another embodiment of the invention, the blowing agent is azodicarbonamide. According to a further embodiment of the invention, the blowing agent is dinitrosopentamethylenetetramine. According to yet another embodiment of the present invention, the blowing agent is 4, 4' -oxybis-benzenesulfonylhydrazide. By adopting the foaming agent, the nylon elastomer composite material is easier to foam and form, the foaming time is shortened, and the foaming process is simplified.
The foaming auxiliary agent comprises at least one of an activating agent, a nucleating agent, a cell regulator, an antioxidant, a coloring agent, a softening agent, an anti-wear agent and a melamine harmful tail gas absorbent. The activator, the nucleating agent, the cell regulator, the antioxidant, the coloring agent, the softener, the wear-resisting agent and the melamine harmful tail gas absorbent all adopt raw materials commonly used in the field. For example, the activating agent comprises at least one of zinc compound, stearate, glycol, urea, binary lead titanate and binary lead phosphite; the nucleating agent comprises at least one of talcum powder, mica, white carbon black, nano montmorillonite, nano titanium dioxide, nano calcium carbonate, microcrystalline cellulose, a carbon nano tube and graphene; the cell regulator comprises at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and sodium lauryl sulfate; the wear-resisting agent comprises a mixture of silicone oil and EVA, wear-resisting silica gel and the like; the antioxidant comprises at least one of antioxidant 1010, antioxidant 1076 and antioxidant 164; the coloring agent comprises phthalocyanine green G5319, scarlet powder 3132, etc.; the softener comprises at least one of naphthene, coal tar and fatty acid; the melamine harmful tail gas absorbent comprises melamine and the like. The wear-resisting agent is added, so that the wear-resisting property of the nylon elastomer composite material foam can be further improved, and the mechanical property is not reduced. The foam density of the nylon elastomer composite material can be further reduced by adding the foam cell regulator, and the fineness of the foam cells is improved. The nucleating agent is added to accelerate the forming speed of the nylon elastomer composite material foam and improve the fineness of foam cells.
The invention also provides a preparation method of the nylon elastomer composite material foam, which comprises the following steps:
1) blending and extruding the ethylene-vinyl acetate copolymer, the nylon elastomer and the compatilizer by a double-screw extruder to obtain a composite material;
2) uniformly mixing the composite material with a cross-linking agent, a foaming agent and a foaming auxiliary agent through an open mill to obtain a pre-foamed sheet;
3) placing the pre-foamed sheet into a mold for foaming to obtain a coarse foamed material;
4) and placing the coarse foaming material into the mold again for foaming to obtain the nylon elastomer composite material foam.
According to the preparation method of the present invention, preferably, in step 1), the extrusion temperature of the twin-screw extruder is: 140-210 ℃ in the first zone, 160-210 ℃ in the second zone, 170-230 ℃ in the third to sixth zones, 160-220 ℃ in the seventh zone, 160-210 ℃ in the eighth zone, and the rotation speed of the screw is 100-250 r/min. More preferably, the temperature of the first zone is 150-190 ℃, the temperature of the second zone is 165-200 ℃, the temperature of the third zone to the sixth zone is 175-220 ℃, the temperature of the seventh zone is 170-210 ℃, the temperature of the eighth zone is 170-205 ℃, and the rotating speed of the screw is 100-200 r/min.
According to the preparation method provided by the invention, preferably, in the step 2), the roll spacing of the open mill is 2-7 mm, the linear speed of a front roll is 9-15 m/min, the speed ratio is 1.0-1.4, and the temperature of a roller is 50-90 ℃. More preferably, the roll spacing of the open mill is 3-6 mm, the linear speed of a front roll is 10-14 m/min, the speed ratio is 1.1-1.3, and the temperature of a roller is 60-75 ℃.
According to the preparation method of the invention, preferably, in the step 3), the pressure of the mold is 5-20 MPa, the temperature is 145-240 ℃, the temperature and pressure are kept for 3-15 min, and the mold is vacuumized after the pressure is kept for 1 min. More preferably, the pressure of the mold is 9-18 MPa, the temperature is 150-210 ℃, the heat preservation and pressure maintaining are carried out for 7-9 min, and the mold is vacuumized after the pressure maintaining is carried out for 1 min. By setting the parameter range, the pre-foamed sheet can be quickly foamed, and the foaming efficiency is improved. The abrasive may be a foamed abrasive commonly used in the art.
According to the preparation method provided by the invention, preferably, in the step 4), the mold is kept at normal pressure, the temperature is 100-190 ℃, and foaming is carried out for 10-70 min. More preferably, the mould is kept at normal pressure, the temperature is 120-180 ℃, and foaming is carried out for 20-60 min. By adopting the secondary foaming process, the coarse foaming material is further fully foamed, and the mould is only used at normal pressure, so that the production cost is reduced, and the mould loss is reduced.
The invention introduces the ethylene-vinyl acetate copolymer into the nylon elastomer, so that the obtained nylon elastomer composite material foam keeps the excellent comprehensive performance of the nylon elastomer, has good cold resistance, has performance attenuation of less than 20 percent at the temperature of minus 55 ℃, high toughness, higher foam melt strength, uniform foam holes, small density, small compression shape and large resilience. The invention also simplifies the foaming forming process of the nylon elastomer and solves the problems of complexity and instability of the existing foaming forming process of the nylon elastomer.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the scope of the present invention is not limited thereto.
Sources and specifications of raw materials used in examples and comparative examples:
ethylene-vinyl acetate copolymer (the content of vinyl acetate is 20-40 wt% respectively): purchased from taiwan tai-plast, china.
Nylon 6 elastomer (soft segment polyethylene glycol 1500): purchased from Zhejiang heart-source science and technology, Inc.
Nylon 11 elastomer (soft segment polytetrahydrofuran 2000): purchased from arkema, france.
Nylon 1012 elastomer (soft segment polytetrahydrofuran 2000): boxing Ri-liter plastication Co.
Nylon 1313 elastomer (soft block polytetrahydrofuran 2000): purchased from Zhejiang heart-source science and technology, Inc.
Maleic anhydride-grafted ethylene-1-octene copolymer (POE-g-MAH): available from Dongguan plastic materials Co.
Maleic anhydride grafted ethylene propylene diene monomer (EPDM-g-MAH): purchased from Shanghai Plastic materials, Inc., of Dongguan.
Ethylene-vinyl acetate grafted glycidyl methacrylate (EVA-g-GMA): the self-made material is prepared according to the method recorded in Xuluo, Yuan Long, Lu Stroke, Jun. EVA-g-GMA and the influence thereof on the performances of PLA/PHBV blends, the reports of materials science and engineering, 2017 and 35 (05).
Epoxy silane coupling agent: purchased from Kjen chemical Co., Ltd.
Aminosilane-based coupling agent: purchased from Kjen chemical Co., Ltd.
The performance test method of the product comprises the following steps:
the density and the aperture are tested according to GB/T533-.
The resilience was tested according to GB/T10652-2001.
The toughness was tested according to GB/T528-.
The foam melt strength was tested according to GB/T3682-.
Cold resistance was tested according to ASTM D1052-2009.
Compression set was tested as per HG/T2876-.
Example 1
The preparation method of the nylon elastomer composite foam of the embodiment comprises the following steps:
1) 100g of nylon 6 elastomer (soft segment is polyethylene glycol 1500), 900g of EVA (the content of vinyl acetate is 20wt percent) and EVA-g-GMA10g are blended and extruded by a double-screw extruder to obtain the composite material. Wherein the extrusion temperature is: 190 ℃ in the first area, 200 ℃ in the second area, 220 ℃ in the third to sixth areas, 210 ℃ in the seventh area and 205 ℃ in the eighth area; the screw speed was 100 revolutions per minute.
2) And mixing 250g of the composite material, 2g of dicumyl peroxide, 4g of p-toluenesulfonyl semicarbazide, 1g of antioxidant 1010, 1g of white carbon black and 0.5g of softener coal tar on an open mill to obtain a pre-foamed sheet. Wherein the roll gap of the open mill is 3mm, the linear velocity of the front roll is 10m/min, the speed ratio is 1.1, and the temperature of the roller is 70 ℃.
3) And (3) putting 200g of the pre-foamed sheet into a foaming mold at 210 ℃, pressurizing under 15MPa for 1min, vacuumizing the mold, and keeping for 8min to obtain the coarse foaming material.
4) And (3) putting the coarse foaming material into a foaming mould at 180 ℃ again for secondary foaming, and keeping the temperature at normal pressure for 60min to obtain the nylon elastomer composite material foam.
Example 2
The preparation method of the nylon elastomer composite foam of the embodiment comprises the following steps:
1) 200g of nylon 11 elastomer (soft segment is polytetrahydrofuran 2000), 800g of EVA (ethylene vinyl acetate content is 26 wt%) and 12g of zinc acetate are blended and extruded by using a double-screw extruder to obtain the composite material. Wherein the extrusion temperature is: 170 ℃ in the first zone, 180 ℃ in the second zone, 190 ℃ in the third to sixth zones, 185 ℃ in the seventh zone and 180 ℃ in the eighth zone; the screw speed was 150 rpm.
2) 250g of composite material, 2g of di-tert-butylperoxy diisopropylbenzene, 4.5g of dinitroso pentamethylene tetramine, 1g of antioxidant 1010, 1g of nano calcium carbonate and 0.5g of melamine are mixed on an open mill to obtain a pre-foamed sheet. Wherein the roll gap of the open mill is 4mm, the linear velocity of the front roll is 11m/min, the speed ratio is 1.2, and the temperature of the roller is 60 ℃.
3) And (3) putting 200g of the pre-foamed sheet into a foaming mold at 190 ℃, pressurizing at 18MPa for 1min, vacuumizing the mold, and keeping for 9min to obtain the coarse foaming material.
4) And (3) placing the coarse foaming material into a foaming mold at 170 ℃ again for secondary foaming, and keeping the temperature at normal pressure for 40min to obtain the nylon elastomer composite material foam.
Example 3
The preparation method of the nylon elastomer composite foam of the embodiment comprises the following steps:
1) 300g of nylon 1012 elastomer (soft segment is polytetrahydrofuran 1000), 700g of EVA (ethylene vinyl acetate content is 36 wt%) and 8g of EPDM-g-MAH are blended and extruded by using a double-screw extruder to obtain the composite material. Wherein the extrusion temperature is: 150 ℃ in the first zone, 165 ℃ in the second zone, 175 ℃ in the third to sixth zones, 170 ℃ in the seventh zone and 170 ℃ in the eighth zone; the screw speed was 200 rpm.
2) 250g of the composite material, 4g of epoxy silane coupling agent, 4.5g of 4, 4' -oxybis-benzenesulfonyl hydrazide, 1g of sodium dodecyl sulfate, 2g of mica and 2g of wear-resistant agent silica gel are mixed on an open mill to obtain a pre-foamed sheet. Wherein the roll gap of the open mill is 6mm, the linear velocity of the front roll is 14m/min, the speed ratio is 1.2, and the temperature of the roller is 75 ℃.
3) And (3) putting 200g of the pre-foamed sheet into a foaming mold at 150 ℃, pressurizing under 9MPa for 1min, vacuumizing the mold, and keeping for 6min to obtain the coarse foaming material.
4) And (3) putting the coarse foaming material into a foaming mold at 120 ℃ again for secondary foaming, and keeping the temperature at normal pressure for 20min to obtain the nylon elastomer composite material foam.
Example 4
The preparation method of the nylon elastomer composite foam of the embodiment comprises the following steps:
1) 400g of nylon 1313 elastomer (with a soft segment of polytetrahydrofuran 2000), 600g of EVA (with a vinyl acetate content of 48 wt%) and 10g of POE-g-MAH are blended and extruded by using a double-screw extruder to obtain the composite material. Wherein the extrusion temperature is: 170 ℃ in the first zone, 175 ℃ in the second zone, 185 ℃ in the third to sixth zones, 180 ℃ in the seventh zone and 180 ℃ in the eighth zone; screw rotation speed: 180 revolutions per minute.
2) Mixing 250g of the composite material, 2.2g of the amino silane coupling agent, 4.5g of azodicarbonamide, 1g of the antioxidant 1010, 1g of the nano calcium carbonate, 1g of the zinc oxide and 1g of the zinc stearate on an open mill to obtain the pre-foamed sheet. Wherein the roll spacing of the open mill is 5mm, the linear velocity of the front roll is 11m/min, the speed ratio is 1.3, and the temperature of the roller is 65 ℃.
3) And (3) putting 200g of the pre-foamed sheet into a foaming mold at 180 ℃, pressurizing at 11MPa for 1min, vacuumizing the mold, and keeping for 7min to obtain the coarse foaming material.
4) And (3) putting the coarse foaming material into a foaming mould at 160 ℃ again for secondary foaming, and keeping the temperature at normal pressure for 30min to obtain the nylon elastomer composite material foam.
Comparative example 1
The preparation method of the polyamide elastomer foam material of the comparative example comprises the following steps:
mixing 1000g of polyamide elastomer (polyamide 66 and polypropylene glycol copolymer elastomer), 600g of citric acid, 25g of talcum powder, 10g of antioxidant 1098, 20g of unsaturated fatty acid zinc, 30g of dicumyl peroxide and 20g of 2- (2-hydroxy-5-methylphenyl) benzotriazole uniformly, adding the mixture into a double-screw extruder, controlling the rotating speed of a screw of the extruder to be 150 revolutions per minute, controlling the working temperature of the extruder to be 230 ℃, extruding and granulating to prepare required precursor particles for foaming, wherein the diameter of the precursor particles is 3 mm; adding the prepared precursor for foaming into a high-pressure reaction kettle, starting stirring, heating to 150 ℃, introducing carbon dioxide to enable the pressure in the kettle to reach 25 MPa, keeping the temperature and the pressure for 0.5 hour, quickly relieving pressure through a pressure relief device, and cooling and shaping to obtain the polyamide elastomer foaming material.
Example 1～4 the results of the performance tests of the resulting nylon elastomer composite foam and the nylon elastomer foamed particles of comparative example 1 are shown in table 1.
Table 1 results of performance testing
By way of example 1～4 compared with the process steps and product performance test results of the comparative example 1, the method for preparing the nylon elastomer composite foam has the advantages of simple steps and easy processing, and the obtained nylon elastomer composite foam has the advantages of good cold resistance, high toughness, higher foam melt strength, uniform foam holes, small density, small compression shape and large resilience. Therefore, the method simplifies the foaming and forming process of the nylon elastomer, retains the excellent comprehensive performance of the nylon elastomer, and the obtained nylon elastomer composite material foam can be widely used as a foaming insole of a shoe.
The present invention is not limited to the above-described embodiments, and any variations, modifications, and substitutions which may occur to those skilled in the art may be made without departing from the spirit of the invention.
Claims (10)
1. A nylon elastomer composite foam characterized by being formed from raw materials comprising: the composite material, the cross-linking agent, the foaming agent and the foaming auxiliary agent are mixed according to the mass ratio of 100: 0.5-5: 0.5-5: 0.5 to 8;
wherein the composite material is formed by the following raw materials: the rubber composition comprises a nylon elastomer, an ethylene-vinyl acetate copolymer and a compatilizer, wherein the mass ratio of the nylon elastomer to the ethylene-vinyl acetate copolymer to the compatilizer is 5-70: 30-95: 0.5-3.
2. The nylon elastomer composite foam of claim 1, wherein the ethylene vinyl acetate copolymer has a vinyl acetate VA content of 20 wt% to 50 wt%.
3. The nylon elastomer composite foam of claim 1, wherein the nylon elastomer is a copolymerized nylon elastomer consisting of polyamide elastomer hard segments and polyamide elastomer soft segments, wherein the polyamide elastomer hard segments comprise at least one of polyamide 6, polyamide 11, polyamide 12, polyamide 66, polyamide 610, polyamide 1010, polyamide 1011, polyamide 1012, polyamide 1210, polyamide 1211, polyamide 1212, polyamide 1213, polyamide 1311, polyamide 1312, and polyamide 1313; the polyamide elastomer soft segment comprises at least one of polytetrahydrofuran ether, polyethylene glycol, polypropylene glycol and polytetramethylene glycol.
4. The nylon elastomer composite foam of claim 1, wherein the compatibilizer comprises at least one of maleic anhydride, zinc acetate, ethylene-vinyl acetate grafted glycidyl methacrylate (EVA-g-GMA), maleic anhydride grafted ethylene-1-octene copolymer (POE-g-MAH), maleic anhydride grafted ethylene propylene diene monomer (EPDM-g-MAH), maleic anhydride grafted styrene-ethylene-butadiene-styrene block copolymer (SEBS-g-MAH), maleic anhydride grafted acrylonitrile-butadiene-styrene copolymer (ABS-g-MAH), and maleic anhydride grafted polystyrene (PS-g-MAH).
5. The nylon elastomer composite foam of claim 1, wherein the crosslinking agent comprises at least one of dicumyl peroxide, di-t-butylperoxydiisopropylbenzene, an aminosilane-based coupling agent, and an epoxysilane-based coupling agent;
the foaming agent comprises at least one of p-toluenesulfonyl semicarbazide, azo foaming agent, dinitroso pentamethine tetramine and 4, 4' -oxo-bis-benzenesulfonyl hydrazide;
the foaming auxiliary agent comprises at least one of an activating agent, a nucleating agent, a cell regulator, an antioxidant, a coloring agent, a softening agent, an anti-wear agent and a melamine harmful tail gas absorbent.
6. A method of preparing the nylon elastomer composite foam of any one of claims 1 to 5, comprising the steps of:
1) blending and extruding the ethylene-vinyl acetate copolymer, the nylon elastomer and the compatilizer by a double-screw extruder to obtain a composite material;
2) uniformly mixing the composite material with a cross-linking agent, a foaming agent and a foaming auxiliary agent through an open mill to obtain a pre-foamed sheet;
3) placing the pre-foamed sheet into a mold for foaming to obtain a coarse foamed material;
4) and placing the coarse foaming material into the mold again for foaming to obtain the nylon elastomer composite material foam.
7. The preparation method according to claim 6, wherein in the step 1), the extrusion temperature of the twin-screw extruder is: 140-210 ℃ in the first zone, 160-210 ℃ in the second zone, 170-230 ℃ in the third to sixth zones, 160-220 ℃ in the seventh zone, 160-210 ℃ in the eighth zone, and the rotation speed of the screw is 100-250 r/min.
8. The preparation method of claim 6, wherein in the step 2), the roll gap of the open mill is 2-7 mm, the linear speed of a front roll is 9-15 m/min, the speed ratio is 1.0-1.4, and the temperature of a roller is 50-90 ℃.
9. The preparation method according to claim 6, wherein in the step 3), the pressure of the mold is 5 to 20MPa, the temperature is 145 to 240 ℃, the temperature and pressure are kept for 3 to 15min, and the mold is vacuumized after the pressure is kept for 1 min.
10. The preparation method according to claim 6, wherein in the step 4), the mold is kept at normal pressure, the temperature is 100-190 ℃, and the foaming is carried out for 10-70 min.
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Inventor after: Pan Kai Inventor after: Deng Jianping Inventor after: Huang Guotao Inventor after: Gui Yuan Inventor after: Li Yucai Inventor after: Wu Xin Inventor after: Wang Cao Inventor before: Pan Kai Inventor before: Deng Jianping Inventor before: Huang Guotao Inventor before: Gui Yuan Inventor before: Li Yucai Inventor before: Wu Xin Inventor before: Feng Xinxing Inventor before: Wang Cao |