CN114350008B - Nylon foaming plate with high foaming multiplying power and preparation method thereof - Google Patents
Nylon foaming plate with high foaming multiplying power and preparation method thereof Download PDFInfo
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- CN114350008B CN114350008B CN202210014559.4A CN202210014559A CN114350008B CN 114350008 B CN114350008 B CN 114350008B CN 202210014559 A CN202210014559 A CN 202210014559A CN 114350008 B CN114350008 B CN 114350008B
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Abstract
The invention relates to a nylon foaming plate with high foaming multiplying power and a preparation method thereof; the preparation method comprises the following preparation steps: mixing the PA6 resin and the first additive to obtain a first component; mixing the thermoplastic resin with a second additive to obtain a second component; adopting serial equipment of a double-screw extruder and a single-screw extruder, adding a first component from a main feeding port of the double-screw extruder, adding a second component from a side feeding port of the double-screw extruder, mixing the first component and the second component through the double-screw extruder, then entering the single-screw extruder, extruding the discharged material through a plate die opening, cooling, shaping and cutting to obtain a nylon plate to be foamed; placing the nylon plate to be foamed into an autoclave, adding a foaming agent, and adopting a dual-gradient high-temperature swelling permeation and isothermal decompression method to prepare the nylon foamed plate with high foaming multiplying power.
Description
Technical Field
The invention relates to the technical field of foaming sheet material preparation, in particular to a nylon foaming sheet material with high foaming multiplying power and a preparation method thereof.
Background
Polyurethane has high strength, high heat resistance, high fatigue resistance, chemical resistance and good oil resistance, and is widely applied to various parts. The closed-cell nylon foam material has excellent heat insulation, noise reduction and other performances, and compared with the traditional polypropylene, polyethylene and polystyrene foam materials, the closed-cell nylon foam material has outstanding high-temperature resistance, compression resistance and retraction elasticity, and is expected to be fully utilized in the fields of automobile high-speed rail interior trim parts, household electrical appliance parts, instrument panels, automobile intake manifolds and the like. At present, general polyamide has lower relative molecular mass, about less than two tens of thousands, low relative viscosity, difficult preparation of foaming materials, nylon belongs to semi-crystalline polymers, and compared with amorphous polymers, the structure of cells after the melting of crystal areas in the foaming process is more difficult to control, so that the phenomena of cell collapse and fracture occur, and the mechanical property and appearance of the foaming materials are greatly influenced.
CN 112851998A discloses a preparation method of a high-magnification nylon 6 foaming material, nylon 6 with high melt strength is obtained through modification of a chain extender, the purpose of adjusting foaming performance is achieved through adjusting crystallization behavior by taking PTFE as an additive, and the high-magnification nylon 6 foaming material is prepared by adopting a high-temperature soaking low-temperature isothermal decompression method.
CN 111087805A discloses a preparation method of a supercritical fluid continuous extrusion high-performance recyclable PA foam material, and the PA foam material with fine cells is obtained by a double-screw serial single-screw method, and the foaming ratio is about 10 times.
CN 110256840A discloses a preparation method of foamed nylon sheet, nylon is melt-modified by toughening agent, nucleating agent, cross-linking agent, etc., and added into plasticizing extrusion equipment of stretching rheology, the nylon is melt-plasticized by a flow field which is mainly changed by stretching deformation, and the foaming agent is decomposed to generate gas, and the gas is extruded by a sheet mouth die to obtain the foamed nylon sheet, but the technology uses chemical foaming agent with chemical residue, and the final foaming multiplying power is about 2 times.
Accordingly, the present invention has been made in view of the above problems, and it is highly desirable to provide a method for producing a nylon foam sheet having a high foaming ratio.
Disclosure of Invention
The invention aims to provide a nylon foaming sheet material with high foaming multiplying power and a preparation method thereof, and solves the technical problems that the existing general polyamide in the prior art has low relative molecular weight, about below twenty thousands and low relative viscosity, and is difficult to meet the preparation of foaming materials through the design of the preparation method of the nylon foaming sheet material with high foaming multiplying power.
The invention provides a preparation method of a nylon foaming sheet material with high foaming multiplying power, which comprises the following preparation steps:
mixing the PA6 resin and the first additive to obtain a first component; mixing the thermoplastic resin with a second additive to obtain a second component;
adopting serial equipment of a double-screw extruder and a single-screw extruder, adding a first component from a main feeding port of the double-screw extruder, adding a second component from a side feeding port of the double-screw extruder, mixing the first component and the second component through the double-screw extruder, then entering the single-screw extruder, extruding the discharged material through a plate die opening, cooling, shaping and cutting to obtain a nylon plate to be foamed;
placing a nylon plate to be foamed into an autoclave, adding a foaming agent, and adopting a dual-gradient high-temperature swelling permeation isothermal decompression method to prepare a nylon foaming plate with high foaming multiplying power;
the dual-gradient high-temperature swelling permeation is carried out by filling a main foaming agent at 200-235 ℃ for swelling permeation, and then heating to 240-250 ℃ for filling an auxiliary foaming agent for swelling permeation;
the first additive includes a cross-linking agent and the second additive includes a compatibilizing agent.
Preferably, the nylon plate to be foamed is placed in an autoclave, and the supercritical CO is filled at the temperature of 200-235 ℃ and the pressure of 10-20MPa 2 As main foaming agent, preserving heat for 0.5-1.5h, swelling and penetrating, heating to 240-250deg.C, maintaining pressure at 40-60MPa, and filling supercritical N 2 And (3) taking the nylon foam board as a foaming auxiliary agent, preserving heat for 0.5-1.5h, rapidly releasing pressure to normal pressure, and cooling to obtain the nylon foam board with high foaming multiplying power.
Preferably, the first additive further comprises at least one of a nucleating agent, an antioxidant, a lubricant, an anti-uv agent, and a compatibilizer; the second additive is at least one of an antioxidant, an anti-ultraviolet agent and a lubricant.
Preferably, the first component comprises 100 parts by weight of PA6 resin and 6-20 parts by weight of a first additive; the second component comprises 2-5 parts of thermoplastic resin and 0.5-3 parts of second additive.
Preferably, the first additive comprises 3-8 parts of cross-linking agent, 0.1-1 part of nucleating agent, 0.5-2 parts of antioxidant, 2-5 parts of ABS resin and 0.5-3 parts of compatilizer; the second additive is 0.5-3 parts of compatilizer.
Preferably, the relative viscosity of the PA6 resin is 2.8-3.4;
the cross-linking agent is at least one of maleic anhydride, isocyanate-like (MDI) and polyfunctional epoxy compounds.
The thermoplastic resin is ABS resin or PEI resin;
the nucleating agent is magnesium oxide (MgO), silicon dioxide (SiO) 2 ) At least one of Talc (Talc), montmorillonite (MMT) and nanowhisker.
The antioxidant is a compound of hindered phenol antioxidants and phosphite antioxidants or a compound of amine antioxidants and phosphite antioxidants;
the compatilizer is at least one of maleic anhydride grafted polystyrene, styrene-acrylonitrile-maleic anhydride grafted copolymer, maleic anhydride grafted ABS, maleic anhydride grafted styrene-ethylene-butylene linear triblock copolymer and ethylene-acrylonitrile-maleic anhydride ternary random copolymer.
Preferably, the thermoplastic resin is ABS resin; the ABS resin is a mixture of ABS and a graft copolymer of styrene-acrylonitrile-maleic anhydride.
Preferably, the residence time of the material in the twin-screw extruder is 2min; the residence time of the material in the single screw extruder was 1.5min.
Preferably, the nylon plate to be foamed is dried before being foamed, and the nylon plate to be foamed is placed in an autoclave after the moisture in the nylon plate to be foamed is less than 200 ppm.
The invention also provides a high-expansion-ratio nylon foam board, which is prepared by adopting the preparation method of the high-expansion-ratio nylon foam board.
Compared with the prior art, the nylon foaming sheet material with high foaming multiplying power and the preparation method thereof provided by the invention have the following steps:
1. according to the preparation method of the nylon foaming plate with high foaming rate, the nylon is used for preparing the foaming plate, the foaming plate has higher temperature and pressure, and the foaming plate with the foaming rate being more than 20 times can be obtained by adopting the higher temperature and pressure as foaming conditions.
2. The preparation method of the nylon foaming sheet material with high foaming multiplying power provided by the invention selects supercritical CO 2 Supercritical N as the main blowing agent 2 As CO-blowing agent, because supercritical CO is produced at relatively low temperatures and pressures 2 Can reach a soaking saturation state with the nylon plate sample, and only when the temperature and the pressure are increased, N 2 Can enter into the resin plate to reach saturation by supercritical N 2 As a foaming agent, the problem that the nylon foam material with high foaming rate is contracted in the placing process after cooling can be solved.
3. The preparation method of the nylon foaming sheet material with high foaming multiplying power provided by the invention is characterized in that a compound cross-linking agent system is adopted, a double-screw extruder and single-screw extruder are simultaneously adopted to connect equipment in series, the cross-linking agent is subjected to cross-linking reaction with resin by controlling the proportioning composition and the consumption of the cross-linking agent and the adding time of each component resin, the reaction speed of maleic anhydride is relatively high, the reaction of maleic anhydride is mainly carried out in the double-screw stage, other cross-linking agents are simultaneously carried out, the adding content of the maleic anhydride cross-linking agent and the length-diameter ratio of the double-screw equipment are controlled, the effect that after materials pass through the double screws, the maleic anhydride cross-linking agent is reacted completely and reaches a certain cross-linking degree is realized, after a melt is pushed into the single screw connected in series, the epoxy or isocyanate cross-linking agent and the resin are continuously reacted, so that the melt viscosity and the cross-linking degree are further increased, and finally the higher cross-linking degree is reached, and the cross-linking degree can reach 40% -60%.
Detailed Description
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of a nylon foaming sheet material with high foaming multiplying power, which comprises the following preparation steps:
s1) mixing PA6 resin and a first additive to obtain a first component; mixing the thermoplastic resin with a second additive to obtain a second component;
s2) adopting serial equipment of a double-screw extruder and a single-screw extruder, adding a first component from a main feeding port of the double-screw extruder, adding a second component from a side feeding port of the double-screw extruder, mixing the first component and the second component through the double-screw extruder, then entering the single-screw extruder, extruding the discharged material through a plate die, cooling, shaping and cutting to obtain a nylon plate to be foamed;
s3) placing the nylon plate to be foamed into an autoclave, adding a foaming agent, and preparing the nylon foamed plate with high foaming multiplying power by adopting a dual-gradient high-temperature swelling permeation isothermal decompression method;
the dual-gradient high-temperature swelling permeation is carried out by filling a main foaming agent at 200-235 ℃ for swelling permeation, and then heating to 240-250 ℃ for filling an auxiliary foaming agent for swelling permeation;
the first additive includes a cross-linking agent and the second additive includes a compatibilizing agent.
Specifically, nylon plate to be foamed is placed in an autoclave, and supercritical CO is filled at the temperature of 200-235 ℃ and the pressure of 10-20MPa 2 As main foaming agent, preserving heat for 0.5-1.5h, swelling and penetrating, heating to 240-250deg.C, maintaining pressure at 40-60MPa, and filling supercritical N 2 And (3) taking the nylon foam board as a foaming auxiliary agent, preserving heat for 0.5-1.5h, rapidly releasing pressure to normal pressure, and cooling to obtain the nylon foam board with high foaming multiplying power.
Specifically, the first additive further comprises at least one of a nucleating agent, an antioxidant, a lubricant, an anti-ultraviolet agent, and a compatibilizer; the second additive is at least one of an antioxidant, an anti-ultraviolet agent and a lubricant.
Specifically, the first component comprises 100 parts by weight of PA6 resin and 6-20 parts by weight of a first additive; the second component comprises 2-5 parts of thermoplastic resin and 0.5-3 parts of second additive.
Specifically, the first additive comprises 3-8 parts of cross-linking agent, 0.1-1 part of nucleating agent, 0.5-2 parts of antioxidant, 2-5 parts of ABS resin and 0.5-3 parts of compatilizer; the second additive is 0.5-3 parts of compatilizer.
Specifically, the relative viscosity of the PA6 resin is 2.8-3.4;
the cross-linking agent is at least one of maleic anhydride, isocyanate-like (MDI) and polyfunctional epoxy compounds.
The thermoplastic resin is ABS resin or PEI resin;
the nucleating agent is magnesium oxide (MgO), silicon dioxide (SiO) 2 ) At least one of Talc (Talc), montmorillonite (MMT) and nanowhisker.
The antioxidant is a compound of hindered phenol antioxidants and phosphite antioxidants or a compound of amine antioxidants and phosphite antioxidants;
the compatilizer is at least one of maleic anhydride grafted polystyrene, styrene-acrylonitrile-maleic anhydride grafted copolymer, maleic anhydride grafted ABS, maleic anhydride grafted styrene-ethylene-butylene linear triblock copolymer and ethylene-acrylonitrile-maleic anhydride ternary random copolymer.
Specifically, the thermoplastic resin is ABS resin; the ABS resin is a mixture of ABS and a graft copolymer of styrene-acrylonitrile-maleic anhydride.
Specifically, the residence time of the material in the twin-screw extruder is 2min; the residence time of the material in the single screw extruder was 1.5min.
Specifically, the nylon plate to be foamed is dried before being foamed, and the nylon plate to be foamed is placed in an autoclave after the moisture in the nylon plate to be foamed is less than 200 ppm.
Specifically, the anti-ultraviolet agent is at least one of nano titanium dioxide, zinc oxide, phenyl salicylate, benzotriazole and phosphoric triamide.
Specifically, the processing temperature of the thermoplastic resin is in the range of 190-250 ℃, and the thermoplastic resin is preferably ABS resin; the ABS resin is the mixture of ABS and styrene-acrylonitrile-maleic anhydride grafted copolymer.
Specifically, the residence time of the material in the twin-screw extruder is 2min; the residence time of the material in the single screw extruder was 1.5min.
Specifically, the main feeding port and the side feeding port of the double-screw extruder are both provided with weightlessness scales.
Specifically, the twin-screw extruder has an aspect ratio (L/D) of 40 to 60, and the single-screw extruder has an aspect ratio (L/D value) of 30.
Specifically, the melt index (220 ℃ C., 10 kg) of the ABS resin is 1-5g/10min.
Specifically, the nylon plate to be foamed is dried, and the nylon plate to be foamed is placed in an autoclave after the moisture in the nylon plate to be foamed is less than 200 ppm.
The invention also provides a high-expansion-ratio nylon foam board, which is prepared by adopting the preparation method of the high-expansion-ratio nylon foam board.
According to the preparation method of the nylon foaming plate with high foaming rate, the nylon is adopted to prepare the foaming plate, the foaming plate has higher temperature and pressure, and the foaming plate with the foaming rate being more than 20 times can be obtained by adopting the higher temperature and pressure as foaming conditions; selecting supercritical CO 2 Supercritical N as the main blowing agent 2 As CO-blowing agent, because supercritical CO is produced at relatively low temperatures and pressures 2 Can reach a soaking saturation state with the nylon plate sample, and only when the temperature and the pressure are increased, N 2 Can enter into the resin plate to reach saturation by supercritical N 2 As a foaming agent, the problem that the nylon foam material with high foaming rate is contracted in the placing process after cooling can be solved.
The preparation method of the nylon foaming sheet material with high foaming multiplying power provided by the invention is characterized in that a compound cross-linking agent system is adopted, a double-screw extruder and single-screw extruder are simultaneously adopted to connect equipment in series, the cross-linking agent is subjected to cross-linking reaction with resin by controlling the proportioning composition and the consumption of the cross-linking agent and the adding time of each component resin, the reaction speed of maleic anhydride is relatively high, the reaction of maleic anhydride is mainly carried out in the double-screw stage, other cross-linking agents are simultaneously carried out, the adding content of the maleic anhydride cross-linking agent and the length-diameter ratio of the double-screw equipment are controlled, the effect that after materials pass through the double screws, the maleic anhydride cross-linking agent is reacted completely and reaches a certain cross-linking degree is realized, after a melt is pushed into the single screw connected in series, the epoxy or isocyanate cross-linking agent and the resin are continuously reacted, so that the melt viscosity and the cross-linking degree are further increased, and finally the higher cross-linking degree is reached, and the cross-linking degree can reach 40% -60%.
Example 1
Preparation of high expansion ratio nylon foaming plate (sample 1)
101 100 parts by weight of PA6 resin (YH 800, balm petrochemical) and 5 parts by weight of a first additive are mixed to obtain a first component; mixing 5 parts of thermoplastic resin and 1 part of a second additive to obtain a second component; specifically, the first additive comprises a mixture of 0.5 parts of a nucleating agent, 0.5 parts of an antioxidant, and 4 parts of a crosslinking agent; the second additive is 1 part of compatilizer.
102 Adopting serial equipment of a double-screw extruder and a single-screw extruder, adding a first component from a main feeding port of the double-screw extruder, adding a second component from a side feeding port of the double-screw extruder, mixing the first component and the second component through the double-screw extruder, then entering the single-screw extruder, extruding the discharged material through a plate die opening, cooling, shaping and cutting to obtain a nylon plate to be foamed;
103 Placing the nylon plate to be foamed into an autoclave, adding a foaming agent, and adopting a dual-gradient high-temperature swelling permeation isothermal decompression method to prepare a nylon foaming plate with high foaming multiplying power;
the dual-gradient high-temperature swelling permeation is carried out by filling supercritical CO at 230 ℃ under 20MPa 2 As main foaming agent, preserving heat for 1.0h, swelling and penetrating, heating to 250deg.C, maintaining pressure at 50MPa, and filling supercritical N 2 As auxiliary foaming agent, preserving heat for 0.5hThe pressure was quickly released to normal pressure, and after cooling, a nylon foam sheet material with a high expansion ratio was obtained (sample 1).
The relative viscosity of the PA6 resin of this example is 2.8-3.4.
The crosslinker of this example was 2 parts maleic anhydride crosslinker (SMA 2025, polyscope) and 2 parts multifunctional epoxy crosslinker (ADR 4368, selected from basf company, germany), wherein the maleic anhydride crosslinker had a maleic anhydride content of 25%.
The thermoplastic resin of this embodiment is an ABS resin.
The nucleating agent of this example is SiO 2 (Hangzhou intelligent titanium) particle size of 20 μm.
The antioxidant in this embodiment is a complex of hindered phenol antioxidants and phosphite antioxidants or a complex of amine antioxidants and phosphite antioxidants.
The compatibilizing agent of this example is SAM-010 manufactured by the well-known polymer Co., ltd.
The residence time of the material in the twin-screw extruder in this example was 2min; the residence time of the material in the single screw extruder was 1.5min.
The main feeding port and the side feeding port of the double-screw extruder are both provided with weightlessness scales.
The twin-screw extruder of this example had an aspect ratio (L/D) of 56 and the single-screw extruder had an aspect ratio (L/D value) of 30.
The heating section of the twin-screw extruder of this example had 10 sections, the first section temperature was set at 150-190℃and the other sections were set at 220-250 ℃.
The melt index (220 ℃ C., 10 kg) of the ABS resin of this example was 1-5g/10min. Preferably, the nylon sheet to be foamed is dried, and the nylon sheet to be foamed is placed in an autoclave after the moisture in the nylon sheet to be foamed is less than 200 ppm.
The performance parameters of the high expansion ratio nylon foam board of sample 1 are shown in Table 1.
Example two
The preparation process of the nylon sheet to be foamed (sample 2) is the same as that of sample 1, except that:
sample 2Oven drying, placing in autoclave, and charging supercritical CO at 230deg.C 2 As main foaming agent, the pressure is 10MPa, the temperature is kept for 1h, swelling and permeation are carried out, then the temperature is raised to 250 ℃, the pressure is 50MPa, and supercritical N is filled 2 And (3) taking the nylon foam board as a foaming aid, preserving heat for 1h, rapidly releasing pressure to normal pressure, and cooling to obtain the nylon foam board with high foaming multiplying power.
Sample 2 high expansion ratio nylon foam board performance parameters are shown in table 1.
Example III
The preparation of sample 3 is identical to that of sample 1, except that:
drying nylon plate to be foamed, placing in an autoclave, and charging supercritical CO at 230 DEG C 2 As main foaming agent, the pressure is 20MPa, the temperature is kept for 0.5h, swelling and permeation are carried out, then the temperature is raised to 250 ℃, the pressure is 50MPa, and supercritical N is filled 2 And (3) taking the nylon foam board as a foaming aid, preserving heat for 1h, rapidly releasing pressure to normal pressure, and cooling to obtain the nylon foam board with high foaming multiplying power.
Sample 3 high expansion ratio nylon foam board performance parameters are shown in table 1.
Example IV
The preparation of sample 4 was identical to that of sample 1, except that:
the crosslinking agent was 3 parts of maleic anhydride crosslinking agent (SMA 2025, polyscope) and 1 part of isocyanate crosslinking agent (HDI-90 SB, selected from Asahi Kabushiki Kaisha Co., ltd.), wherein the maleic anhydride content in the maleic anhydride crosslinking agent was 25%.
Sample 4 high expansion ratio nylon foam board performance parameters are shown in table 1.
Control 2 was prepared, the procedure for preparing control 2 was the same as for sample 4, except that:
drying nylon plate to be foamed, placing in an autoclave, and charging supercritical CO at 230 DEG C 2 As a main foaming agent, the pressure is 20MPa, the pressure is quickly released to normal pressure after heat preservation for 1.5 hours, and the nylon foaming plate with high foaming multiplying power is obtained after cooling; the performance parameters of the high expansion ratio nylon foam board of the control sample 2 are shown in table 1.
Example five
The preparation of sample 5 was identical to that of sample 4, except that:
drying nylon plate to be foamed, placing in an autoclave, and charging supercritical CO at 225 deg.C 2 As main foaming agent, the pressure is 20MPa, the temperature is kept for 1h, swelling and permeation are carried out, then the temperature is raised to 250 ℃, the pressure is 40MPa, and supercritical N is filled 2 And (3) taking the nylon foam board as a foaming aid, preserving heat for 0.5h, rapidly releasing pressure to normal pressure, and cooling to obtain the nylon foam board with high foaming multiplying power.
Sample 5 high expansion ratio nylon foam board performance parameters are shown in table 1.
Example six
The preparation of sample 6 was identical to that of sample 4, except that:
drying nylon plate to be foamed, placing in an autoclave, and charging supercritical CO at 225 deg.C 2 As main foaming agent, the pressure is 20MPa, the temperature is kept for 1h, swelling and permeation are carried out, then the temperature is raised to 245 ℃, the pressure is 60MPa, and supercritical N is filled 2 And (3) taking the nylon foam board as a foaming aid, preserving heat for 0.5h, rapidly releasing pressure to normal pressure, and cooling to obtain the nylon foam board with high foaming multiplying power.
Comparative example 1
The procedure for the preparation of control 1 was identical to that of sample 1, except that:
drying nylon plate to be foamed, placing in an autoclave, and charging supercritical CO at 230 DEG C 2 As a main foaming agent, the pressure is 20MPa, the pressure is quickly released to normal pressure after heat preservation for 1.5 hours, and the nylon foaming plate with high foaming multiplying power is obtained after cooling; the performance parameters of the high expansion ratio nylon foam board of the comparative sample 1 are shown in Table 1.
Comparative example 2
The procedure for the preparation of control 2 was identical to that of sample 4, except that:
drying nylon plate to be foamed, placing in an autoclave, and charging supercritical CO at 230 DEG C 2 As a main foaming agent, the pressure is 20MPa, the pressure is quickly released to normal pressure after heat preservation for 1.5 hours, and the product is obtained after coolingTo a nylon foaming plate with high foaming multiplying power; the performance parameters of the high expansion ratio nylon foam board of the comparative sample 1 are shown in Table 1.
The foaming ratio of the samples 1-6 is obviously higher than that of the control sample 1 and the control sample 2, and the foaming board with the foaming ratio being more than 20 times is obtained.
The obtained nylon plate of the sample 4-6 has obviously reduced crosslinking degree, and has better stability compared with the sample 1-3, which indicates that the selection of the crosslinking agent has larger influence on the whole system.
Table 1 nylon sheet performance parameters.
From the data in Table 1, it is clear that the nylon foamed sheet with high foaming ratio prepared by the method of the invention has large foaming cell size under the condition of ensuring equivalent crosslinking degree, can obtain higher foaming ratio, and has obvious technical effect by expanding the foaming ratio by about 1 time.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A preparation method of a nylon foaming plate with high foaming multiplying power is characterized by comprising the following steps: the preparation method comprises the following preparation steps:
mixing the PA6 resin and the first additive to obtain a first component; mixing the thermoplastic resin with a second additive to obtain a second component;
adopting serial equipment of a double-screw extruder and a single-screw extruder, adding a first component from a main feeding port of the double-screw extruder, adding a second component from a side feeding port of the double-screw extruder, mixing the first component and the second component through the double-screw extruder, then entering the single-screw extruder, extruding the discharged material through a plate die opening, cooling, shaping and cutting to obtain a nylon plate to be foamed;
placing a nylon plate to be foamed into an autoclave, adding a foaming agent, and adopting a dual-gradient high-temperature swelling permeation isothermal decompression method to prepare a nylon foaming plate with high foaming multiplying power;
the dual-gradient high-temperature swelling permeation is carried out by filling a main foaming agent at 200-235 ℃ for swelling permeation, and then heating to 240-250 ℃ for filling an auxiliary foaming agent for swelling permeation;
the main foaming agent is supercritical CO 2 The auxiliary foaming agent is supercritical N 2 ；
The first additive comprises a cross-linking agent and the second additive comprises a compatibilizer; the cross-linking agent is a compound cross-linking agent of maleic anhydride and isocyanate-like or a compound cross-linking agent of maleic anhydride and a polyfunctional epoxy compound.
2. The method for preparing the nylon foaming sheet material with high foaming ratio according to claim 1, which is characterized in that: placing nylon plate to be foamed in an autoclave, at 200-235deg.C and 10-20MPa, and charging supercritical CO 2 As main foaming agent, preserving heat for 0.5-1.5h, swelling and penetrating, heating to 240-250deg.C, maintaining pressure at 40-60MPa, and filling supercritical N 2 And (3) taking the nylon foam board as a foaming auxiliary agent, preserving heat for 0.5-1.5h, rapidly releasing pressure to normal pressure, and cooling to obtain the nylon foam board with high foaming multiplying power.
3. The method for preparing the nylon foaming sheet material with high foaming ratio according to claim 1, which is characterized in that: the first additive further comprises at least one of a nucleating agent, an antioxidant, a lubricant, an anti-uv agent, and a compatibilizer; the second additive further comprises at least one of an antioxidant, an anti-uv agent, and a lubricant.
4. The method for preparing the nylon foam board with high foaming ratio according to claim 3, which is characterized in that: the first component comprises 100 parts by weight of PA6 resin and 6-20 parts by weight of a first additive; the second component comprises 2-5 parts of thermoplastic resin and 0.5-3 parts of second additive.
5. The method for preparing the nylon foaming sheet material with high foaming ratio according to claim 4, which is characterized in that: the first additive is 3-8 parts of cross-linking agent, 0.1-1 part of nucleating agent and 0.5-2 parts of antioxidant, and the second component comprises 2-5 parts of ABS resin and 0.5-3 parts of compatilizer.
6. The method for preparing the nylon foaming sheet material with high foaming ratio according to claim 5, which is characterized in that:
the relative viscosity of the PA6 resin is 2.8-3.4;
the cross-linking agent is a compound cross-linking agent of maleic anhydride and isocyanate-like or a compound cross-linking agent of maleic anhydride and a multifunctional epoxy compound;
the thermoplastic resin is ABS resin or PEI resin;
the nucleating agent is at least one of magnesium oxide (MgO), silicon dioxide (SiO 2), talcum powder (Talc), montmorillonite (MMT) and nano whisker;
the antioxidant is a compound of hindered phenol antioxidants and phosphite antioxidants or a compound of amine antioxidants and phosphite antioxidants;
the compatilizer is at least one of maleic anhydride grafted polystyrene, styrene-acrylonitrile-maleic anhydride grafted copolymer, maleic anhydride grafted ABS, maleic anhydride grafted styrene-ethylene-butylene linear triblock copolymer and ethylene-acrylonitrile-maleic anhydride ternary random copolymer.
7. The method for preparing the nylon foaming sheet material with high foaming ratio according to claim 5, which is characterized in that: the thermoplastic resin is ABS resin; the ABS resin is a mixture of ABS and a graft copolymer of styrene-acrylonitrile-maleic anhydride.
8. The method for preparing the nylon foaming sheet material with high foaming ratio according to claim 1, which is characterized in that:
the retention time of the materials in the double-screw extruder is 2min; the residence time of the material in the single screw extruder was 1.5min.
9. The method for preparing the nylon foaming sheet material with high foaming ratio according to claim 1, which is characterized in that: drying the nylon plate to be foamed before foaming, and placing the nylon plate to be foamed in an autoclave after the moisture in the nylon plate to be foamed is less than 200 ppm.
10. A high-expansion nylon foam board, which is characterized in that the high-expansion nylon foam board is prepared by the preparation method of the high-expansion nylon foam board as claimed in any one of claims 1 to 9.
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| CN110256840B (en) * | 2019-05-14 | 2022-04-19 | 广东星联科技有限公司 | Preparation method of foamed nylon plate |
| TW202108696A (en) * | 2019-06-28 | 2021-03-01 | 日商東洋紡股份有限公司 | Polyamide resin composition for foam molding and foam molded body |
| CN111087805B (en) * | 2019-12-27 | 2022-10-25 | 华润化学材料科技股份有限公司 | Supercritical fluid continuous extrusion high-performance recyclable PA (polyamide) foam material and preparation method thereof |
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