CN115505161A - Nylon mould pressing foaming material and preparation method thereof - Google Patents
Nylon mould pressing foaming material and preparation method thereof Download PDFInfo
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- CN115505161A CN115505161A CN202110697578.7A CN202110697578A CN115505161A CN 115505161 A CN115505161 A CN 115505161A CN 202110697578 A CN202110697578 A CN 202110697578A CN 115505161 A CN115505161 A CN 115505161A
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- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
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Abstract
The invention discloses a nylon mould pressing foaming material and a preparation method thereof, wherein the method comprises the following steps: (1) Mixing a nylon material, a chain extender, a nucleating agent and an antioxidant, and then, carrying out melt blending extrusion to obtain a nylon plate blank; (2) Placing a nylon plate blank in a foaming cavity of a primary compression molding die for heating, injecting a high-pressure supercritical fluid into the foaming cavity when the nylon plate blank is molten, so that the high-pressure supercritical fluid is diffused and dissolved in the nylon plate blank and is locked for a preset time, and then opening the die for pressure relief to obtain a nylon pre-foaming material; (3) And placing the nylon pre-foaming material in a foaming cavity of a secondary compression molding mould, opening the mould to release pressure after locking gas for a preset time under normal pressure and heating, and obtaining the nylon compression molding foaming material. The density of the nylon mould pressing foaming material is 0.08-1.0 g/cm 3 The foaming multiplying power is 5-20 times, the size of the foam hole is 50-200 um, the yield is more than or equal to 95%, and the closed-cell rate is more than 95%; the tensile strength is more than 1.0MPa.
Description
Technical Field
The invention belongs to the field of nylon foaming materials, and particularly relates to a nylon mould pressing foaming material and a preparation method thereof.
Background
The foam forming process generally comprises 3 stages: 1) Injecting gas to dissolve in the polymer melt to form a saturated homogeneous system; 2) The internal and external pressure difference formed by rapid pressure relief drives the formation of bubble nucleus hot spots and heterogeneous formation of nucleating agents into hot spot nuclei; 3) The growth of bubble nucleus and the solidification and shaping of the bubble body.
If the melt strength is too low in the PA foaming process, the balance between the gas pressure generated by decomposition due to foaming and the viscosity and elasticity of the material is difficult to achieve, and the phenomena of foam cell collapse, rupture, combination and the like can be caused by tiny resistance in foaming, namely, the foam wall can not maintain certain strength, so that effective bubbles can not be formed, and special attention must be paid to controlling the elasticity of the melt to ensure the normal production.
The nylon extrusion foaming molding is limited by factors such as low melt strength, semi-crystallinity of materials, high process control requirement of the extrusion process, high requirement of extrusion foaming molding equipment and the like, and the foam materials with uniform and continuous performance and stable foam holes are difficult to prepare. The size of the foam sheet product extruded by the extrusion foaming molding porous strip foam die head is single flat plate shape, and the surface needs to be planed, so that the foam surface is rough and not smooth, and the like.
Therefore, the existing techniques for preparing foamed materials are still under investigation.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide a nylon molded foam material and a preparation method thereof, compared with common foam materials with the same density, the nylon molded foam material prepared by the method has the density of less than or equal to 100kg/m at least 3 ) The mechanical property is high, and the temperature resistance can reach 205 ℃ while the weight is greatly reduced; meanwhile, the obtained nylon mould pressing foaming material has extremely strong energy absorption, buffering and shock resistance and excellent chemical resistance, is breathable, washable and reusable, the yield of finished products can reach more than 95%, the closed cell rate is more than or equal to 95%, and the foaming multiplying power is 5-20 times.
In one aspect of the invention, a method of making a nylon molded foam is provided. According to an embodiment of the invention, the method comprises:
(1) Mixing nylon, a chain extender, a nucleating agent and an antioxidant, and then, carrying out melt blending and extrusion to obtain a nylon plate blank;
(2) Placing the nylon plate blank in a foaming cavity of a primary compression molding mold for heating, injecting a high-pressure supercritical fluid into the foaming cavity after the nylon plate blank is melted, so that the high-pressure supercritical fluid is diffused and dissolved in the nylon plate blank and is locked for a first preset time, and then opening the mold for pressure relief to obtain a nylon pre-foaming material;
(3) And placing the nylon pre-foaming material in a foaming cavity of a secondary compression molding mould, locking gas at normal pressure and under heating for a second preset time, and then opening the mould to relieve pressure so as to obtain the nylon compression molding foaming material.
According to the method for preparing the nylon mould pressing foaming material, the nylon, the chain extender, the nucleating agent and the antioxidant are mixed and then are melted, blended and extruded, the storage modulus, the loss modulus and the complex viscosity of the nylon are increased along with the increase of the addition amount, the loss factor is reduced along with the increase of the addition amount, the addition of the chain extender can effectively improve the melt strength of the nylon and improve the foaming property of the nylon, the phenomenon of obvious weakening along with the processing time is avoided, and the phenomena of foam collapse, foam breakage and foam combination in the foaming process are effectively prevented; forming a large amount of low potential energy points on the interface between melts by a nucleating agent in the foaming process to form a large amount of uniform nucleating hot points, so as to be beneficial to obtaining a nylon mould pressing foaming material with higher magnification later, then placing the nylon Long Banpi obtained by melt blending extrusion into a foaming cavity of a primary mould pressing forming mould for heating, injecting high-pressure supercritical fluid into the foaming cavity when a nylon plate blank is molten, so that the high-pressure supercritical fluid is dispersed and dissolved in the nylon plate blank and locks the high-pressure supercritical fluid for a first preset time, then opening the mould for pressure relief, finally placing the obtained nylon pre-foaming material into a foaming cavity of a secondary mould pressing forming mould for releasing the mould after locking gas at normal pressure and under heating for a second preset time, namely, carrying out foaming by two times of mould pressing, firstly controlling the size of the foaming material by means of primary mould pressing foamingThe foaming material is prepared at a proper expansion volume ratio (2-5 times), then the pre-foaming material is moved into a secondary compression molding die, the normal pressure is set and the pre-foaming material is heated, so that the gas remained in the pre-foaming material is slowly released, the size of the foaming material is gradually expanded to the size (the foaming ratio is 5-20 times) designed according to the formula, and the phenomena of hole breaking and tearing of a foaming plate caused by the violent expansion of one-time foaming are solved. Meanwhile, compared with the phenomenon that the size of a foam plate product extruded by a traditional extrusion foaming molding porous strip foam die head is single flat plate shape, and the surface of the foam plate product needs to be planed, so that the surface of the foam is rough and not smooth, the nylon mould pressing foaming material obtained by the invention has a smooth surface. Therefore, compared with common foam materials with the same density, the nylon molded foam material prepared by the method has the density of less than or equal to 100kg/m at the lowest 3 ) The mechanical property is high, and the temperature resistance can reach 205 ℃ while the weight is greatly reduced; meanwhile, the obtained nylon mould pressing foaming material has extremely strong energy absorption, buffering and shock resistance and excellent chemical resistance, is breathable, washable and reusable, the yield of finished products can reach more than 95%, the closed cell rate is more than or equal to 95%, and the foaming multiplying power is 5-20 times.
In addition, the method for preparing the nylon molded foam material according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the present invention, in step (1), the mass ratio of the nylon, the chain extender, the nucleating agent and the antioxidant is 100: (0.5-2): (0.5-2): (0.5-1).
. Thus, a nylon molded foam having excellent characteristics such as a high expansion ratio and a high closed cell ratio can be obtained.
In some embodiments of the invention, in step (1), the nylon comprises at least one of PA6, PA66, PA610, PA612, PA12, PA1212, PA56, TPAE, and MXD 6.
In some embodiments of the invention, in step (1), the chain extender comprises at least one of a homoisocyanate, a multifunctional epoxy resin, and triglycidyl isocyanurate. Therefore, the melt strength of the nylon is effectively improved, the foaming property of the nylon is improved, the phenomenon of obvious weakening along with the processing time is avoided, and the phenomena of foam collapse, foam hole breakage and foam hole combination in the foaming process are effectively prevented.
In some embodiments of the invention, in step (1), the nucleating agent comprises at least one of silica, talc, sodium montanate, magnesium oxide, and aluminum oxide. Therefore, a large number of low potential energy points are formed at the interface between the melts in the foaming process, and a large number of uniform nucleation hot points are formed, so that the nylon mould pressing foaming material with higher multiplying power can be obtained subsequently.
In some embodiments of the invention, in step (1), the antioxidant comprises at least one of antioxidant 1098, antioxidant 1216, antioxidant 626, and antioxidant S9228.
In some embodiments of the present invention, in step (1), the nylon mat has a thickness of 10 to 20mm and a width of 200 to 250mm.
In some embodiments of the present invention, in the step (1), at least one of a high temperature resistant lubricant and a compatibilizer is further added, and the high temperature resistant lubricant is used in an amount of 0.2 to 0.5 parts by weight and the compatibilizer is used in an amount of 0.5 to 1 parts by weight, based on 100 parts by mass of the nylon. Therefore, the phenomena of thermal degradation, melt fracture and surface roughness of the melt caused by high temperature and shearing can be improved, the fluidity of the melt is improved, the extruded and discharged surface is smoother, the forming of the foaming material is facilitated, and the uniform, stable and size-controllable foam holes can be formed.
In some embodiments of the present invention, the high temperature resistant lubricant comprises at least one of polyester wax, montanic acid wax, and PETs, and the compatibilizer comprises at least one of MA-SEBS, SMA, and POE-g-MAH. Thereby facilitating the formation of uniform, stable, size-controlled cells.
In some embodiments of the present invention, in the step (2), the nylon mat is placed in a foaming cavity of the one-time molding die at a pressure of 6 to 15MPa and a temperature of 210 to 270 ℃ to melt the nylon mat.
In some embodiments of the present invention, in the step (2), the first predetermined time is 10 to 25min.
In some embodiments of the present invention, in the step (2), the nylon pre-foamed material has an expansion ratio of 2 to 5 times.
In some embodiments of the present invention, in step (2), the high-pressure supercritical fluid includes at least one of cyclopentane, N2, and CO2, and the physical blowing agent is used in an amount of 1.5 to 3 parts by weight based on 100 parts by mass of the nylon.
In some embodiments of the invention, in step (3), the nylon pre-foamed material is placed in a foaming cavity of the secondary compression molding die, and gas is locked at a temperature of 210-270 ℃ for 10-30 min under normal pressure.
In a second aspect of the invention, a nylon molded foam is provided. According to the embodiment of the invention, the nylon molded foaming material is prepared by adopting the method. Therefore, compared with common foam materials with the same density, the nylon molded foam material prepared by the method disclosed by the application (the density is less than or equal to 100kg/m at the lowest) 3 ) The mechanical property is high, and the temperature resistance can reach 205 ℃ while the weight is greatly reduced; meanwhile, the obtained nylon mould pressing foaming material has extremely strong energy absorption, buffering and shock resistance and excellent chemical resistance, is breathable, washable and reusable, the yield of finished products can reach more than 95%, the closed cell rate is more than or equal to 95%, and the foaming multiplying power is 5-20 times.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic flow chart of a method for preparing a nylon molded foam material according to one embodiment of the present invention.
Detailed Description
The following detailed description of the embodiments of the present invention is intended to be illustrative, and not to be construed as limiting the invention.
In one aspect of the invention, a method of making a nylon molded foam is provided. According to an embodiment of the invention, with reference to fig. 1, the method comprises:
s100: mixing nylon, chain extender, nucleating agent and antioxidant, and then melting, blending and extruding
In the step, nylon, a chain extender, a nucleating agent and an antioxidant are uniformly mixed, are metered by a weight-loss feeding system and then are added into a double-screw extruder for melt blending, are extruded by a specially designed slit structure die head, and are cooled and shaped to obtain a nylon plate blank with the thickness of 10-20mm and the width of 200-250mm. The inventor finds that the storage modulus, the loss modulus and the complex viscosity of the nylon are increased along with the increase of the addition amount, the loss factor is reduced along with the increase of the addition amount, the addition of the chain extender can effectively improve the melt strength of the nylon and improve the foaming property of the nylon, the phenomenon of obvious weakening is avoided along with the processing time, and the phenomena of foam collapse, foam hole breakage and foam hole combination in the foaming process are effectively prevented; the nucleating agent forms a large number of low potential energy points at the interface between melts in the foaming process, and forms a large number of uniform nucleating hot points, thereby being beneficial to obtaining the nylon mould pressing foaming material with higher multiplying power in the follow-up process.
Further, the mass ratio of the nylon, the chain extender, the nucleating agent and the antioxidant is 100: (0.5-2): (0.5-2): (0.5-1). The inventor finds that if the chain extender is added too high, the melt is in a gel state, similar to a rubber state, the color is also darkened, and the extrusion is not facilitated; if the addition of the chain extender is too low, the growth of foam cannot be supported, and the foam collapse phenomenon is caused; meanwhile, if the nucleating agent is added too much, agglomeration can be formed, which is not beneficial to the formation of a uniform cell structure; if the addition of the nucleating agent is too low, an ideal nucleating effect cannot be achieved, heterogeneous nucleating points are few, and a compact foam structure cannot be formed; if the addition amount of the antioxidant exceeds 1 part by weight, the antioxidant stabilizing effect is not increased any more, and a precipitation phenomenon exists; if the antioxidant is added too low, the oxidability of the material cannot be effectively reduced, and the material is discolored and degraded. According to one embodiment of the invention, the nylon comprises at least one of PA6, PA66, PA610, PA612, PA12, PA1212, PA56, TPAE and MXD6, preferably a combination of PA6 and TPAE, and the proportion of TPAE is not more than 20% of the combined mass of PA6 and TPAE. The inventors found that PA6 has high strength and stiffness, low friction, excellent chemical and abrasion resistance, but is brittle; the PA6 and the TPAE are blended, TPAE elastomer particles are dispersed in a PA6 matrix to form a stress concentration point, and the stress concentration point can absorb a large amount of external energy, remarkably improve the notch impact strength, low-temperature impact and processability of the PA6 and play a role of a foam material toughening agent; and under the condition that the proportion of TPAE is not more than 20 parts by weight, TPAE particles also play a role of nucleating agent in the crystallization process of PA6, so that the crystallization rate of PA6 is promoted, and the formation of a cell structure in the foaming process is facilitated. Preferably, the mass ratio of the nylon, the chain extender, the nucleating agent and the antioxidant is 100: (0.5-2): (0.5-2): (0.5-1).
Further, the chain extender includes, but is not limited to, at least one of a Homoisocyanate (HDI), a polyfunctional epoxy resin (ADR 4468), and triglycidyl isocyanurate (TGIC); the nucleating agent includes, but is not limited to, at least one of silica, talc, sodium montanate, magnesium oxide, and aluminum oxide, and preferably sodium montanate. The inventor finds that the long-chain linear saturated sodium montanate takes the chain length of C28-C32 as the main component and is used as a nylon nucleating agent, on one hand, the long-chain linear saturated sodium montanate and nylon end groups carry out branching chemical reaction to form micromolecule heterogeneous nucleation, so that the crystallization efficiency and the thermal deformation temperature of nylon are improved, uniform and compact cell nucleation points are formed, and the preparation of a foam material with lower density is facilitated; on the other hand, the sodium montanate has very strong polar centers and very long nonpolar carbon chains, and the part compatible with the plastic in polarity in the structure of the sodium montanate plays a role in internal lubrication, and the part incompatible with the plastic in polarity plays a role in external lubrication and demolding, so that the fluidity in the extrusion process and the demolding performance between a melt and equipment are improved and improved, and the gas expansion foaming processing period of 10 percent in the mould pressing foaming process is shortened. The antioxidant comprises at least one of antioxidant 1098, antioxidant 1216, antioxidant 626 and antioxidant S9228.
According to another embodiment of the present invention, at least one of the high temperature resistant lubricant and the compatibilizer may be further added in the above step, for example, nylon, the chain extender, the nucleating agent, and the antioxidant are mixed with the high temperature resistant lubricant and the compatibilizer and then are melt blended and extruded. The inventor finds that the high-temperature-resistant lubricant is added, so that the phenomena of thermal degradation, melt fracture and surface roughness of the melt caused by high temperature and shearing can be improved, the fluidity of the melt in the extrusion process is improved, and the demolding performance between the melt and equipment is improved. Preferably, the high-temperature-resistant lubricant is polyester wax, montanic acid wax or PETs; the compatilizer can be compounded by one or more of MA-SEBS, SMA and POE-g-MAH, and preferably the SMA is adopted. The inventor finds that SMA is a styrene-maleic anhydride graft copolymer, and the molecular chain contains more MA groups, so that the SMA can perform amidation reaction with PA6 and esterification reaction with TPAE, and the interfacial compatibility of TPAE and PA6 can be obviously improved; meanwhile, the tensile strength and the bending strength of the foam material of the blending system are reduced along with the increase of the TPAE content, and the compatilizer SMA is added to play a role in improving the action force of the phase interface between the blends while ensuring that the foam material prepared by the compression molding of the rear section has high toughness, so that the foam material is ensured to have higher tensile strength and bending strength.
Further, the high temperature-resistant lubricant is used in an amount of 0.2 to 0.5 parts by weight, and the compatibilizer is preferably used in an amount of 0.5 to 1 part by weight, based on 100 parts by mass of the nylon. The inventor finds that if the adding amount of the high-temperature lubricant is too low, the high-temperature lubricant cannot play a role in lubrication, and the melt is relatively coarse in a high-temperature state; and if the adding amount of the high-temperature lubricant is too high, the melt strength of the melt is reduced, and the gas support of the cells is not facilitated. If the addition amount of the compatilizer is too high, plasticization is caused, the mechanical property and the modulus of the nylon base material are reduced, and in addition, agglomeration and steric effect are generated; if the addition amount of the compatibilizer is too low, the incompatible two polymers cannot be bonded together by virtue of intermolecular bonding force.
S200: placing the nylon plate blank in a foaming cavity of a primary compression molding mold for heating, and injecting high-pressure supercritical fluid into the foaming cavity when the nylon plate blank is molten
In the step, the obtained nylon plate blank is placed in a foaming cavity of a primary compression molding die to be processed at the pressure of 6-15 MPa and the temperature of 210-270 ℃, and high-pressure supercritical fluid is injected into the foaming cavity when the nylon plate blank is melted, so that the high-pressure supercritical fluid is diffused and dissolved in the nylon plate blank, the high-pressure supercritical fluid is locked for 10-25 min, and then the die is opened to release the pressure, so that the nylon pre-foaming material with the foaming multiplying power of 2-5 times is obtained.
Further, according to an embodiment of the present invention, the physical blowing agent includes, but is not limited to, cyclopentane, N 2 And CO 2 At least one of; and the amount of the nylon physical blowing agent is 1.5 to 3 parts by weight based on 100 parts by mass of the nylon physical blowing agent. The inventor finds that if the addition amount of the physical foaming agent is too high, the redundant foaming agent does not participate in the cell growth process due to the limited solubility of the foaming agent in the nylon plate blank; if the addition amount of the physical foaming agent is too low, the foaming ratio is low, and the weight reduction is not obvious.
S300: placing the nylon pre-foaming material in a foaming cavity of a secondary compression molding mould, locking gas at normal pressure and under heating for a second preset time, and then opening the mould to relieve pressure
In the step, the obtained nylon pre-foaming material is placed in a foaming cavity of a secondary compression molding die, gas is locked at the temperature of 210-270 ℃ for 10-30 min under normal pressure, then the die is opened to release pressure, and cooling and shaping are carried out, thus finally obtaining the nylon compression molding foaming material with high multiplying power and more than or equal to 95% of closed pore rate. Specifically, the density of the nylon mould pressing foaming material is 0.08-1.0 g/cm 3 The foaming multiplying power is 5-20 times, the size of the foam hole is 50-200 um, and the yield is more than or equal to 95 percent. The nylon molded foaming material is prepared according to GBT10799-2008 standardThe material closed porosity is more than 95%; the nylon molded foam has a tensile strength greater than 1.0MPa according to ASTM C297.
In the process of the traditional foam compression molding, in order to reduce the density, namely improve the foaming rate, the using amount of the foaming agent is increased to be the same as that of the foaming agent used in the two-time compression molding, when the foaming material is subjected to pressure relief and mold stripping, foaming gas can be instantly released, cells grow up, the volume of the foaming material is instantly expanded by 10-20 times relative to the volume in the mold, and the foaming material is broken and torn due to the violent expansion in the process, so that the foaming quality of the foaming material is poor. In the application, two-time mould pressing is adopted for foaming, the size of the foaming material is controlled at a proper expansion volume ratio (2-5 times) by virtue of one-time mould pressing foaming, then the pre-foaming material is moved into a secondary mould pressing forming mould, the normal pressure is set and the pre-foaming material is heated, so that the gas remained in the pre-foaming material is slowly released, the size of the foaming material is gradually expanded to the size (5-20 times) designed according to the formula, and the phenomena of hole breaking and tearing of the foaming plate caused by one-time foaming violent expansion are solved. Meanwhile, compared with the phenomenon that the size of a foam plate product extruded by a traditional extrusion foaming molding porous strip foam die head is single flat plate shape, and the surface of the foam plate product needs to be planed, so that the surface of the foam is rough and not smooth, the nylon mould pressing foaming material obtained by the invention has a smooth surface.
In a second aspect of the invention, a nylon molded foam is provided. According to the embodiment of the invention, the nylon molded foaming material is prepared by adopting the method. Therefore, compared with common foam materials with the same density, the nylon molded foam material prepared by the method disclosed by the application (the density is less than or equal to 100kg/m at the lowest) 3 ) The mechanical property is high, and the temperature resistance can reach 205 ℃ while the weight is greatly reduced; meanwhile, the obtained nylon mould pressing foaming material has strong energy absorption, buffering and shock resistance and excellent chemical resistance, is breathable, washable and reusable, the yield of finished products can reach more than 95 percent, the closed cell rate is more than or equal to 95 percent, and the foaming multiplying power is 5 to 20 times, so that the nylon mould pressing foaming material has the advantages of strong energy absorption, buffering and shock resistance, and excellent chemical resistance, and is breathable, washable and reusable, and the finished product yield can reach more than 95 percent, and the closed cell rate is more than or equal to 95 percent, so that the nylon mould pressing foaming material has the foaming multiplying power of 5 to 20 times, thereby the nylon mould pressing foaming material has the advantages of high strength, good sealing property and good sealing propertyThe method can be practically applied to production and manufacturing, generates economic benefits, and can be widely applied to a plurality of fields of automobiles, aerospace, product protection, industrial parts, oceans, buildings, military affairs, medical treatment, sports, leisure and the like. It should be noted that the features and advantages described above for the method of preparing the nylon molded foam material are also applicable to the nylon molded foam material, and are not described herein again.
The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.
The following are specific descriptions of the raw materials in the examples and comparative examples:
PA6: lO13B, japan UBE chemical co;
TPAE: TPAE X3533, arkema, france;
styrene-maleic anhydride graft copolymer (SMA): SMA-020, a new material of elevated molecules of Nantong Ribes;
HDI: the smoke bench is luxurious;
ADR 4468: basf;
TGIC: an avastin reagent;
sodium montanate salt: craine Licomont CaV 102;
SiO 2 (Sia): manufactured by Cabot corporation, usa, industrial products;
antioxidant 1098, antioxidant 1216: manufactured by reserva air-jacarat machine corporation;
antioxidant S9228: doverPhos chemical, doverPhos, USA;
a double-screw extruder: keplong STS-50MC11;
extrusion die head for slit-structured sheet materials: the width is 200mm, and the thickness is 10mm.
Example 1
The method for preparing the nylon foaming product comprises the following steps:
(1) Comprises 100 weight portions of PA6, 1 weight portion of ADR4468 and 0.5 weight portion of SiO 2 Adding the components of 0.5 weight part of antioxidant 1098, 0.3 weight part of antioxidant 626, 0.5 weight part of SMA and 0.5 weight part of PETs into an extruder, melting at 220 ℃, extruding by a die head, cooling and shaping to obtain a PA6 slab with the thickness of 12mm and the width of 210 mm;
(2) Placing the obtained nylon plate blank into a foaming cavity with a specific shape between an upper half mold and a lower half mold of a flat press, respectively setting the pressure within the range of 10MPa and the temperature within 225 ℃, injecting 2 parts by weight of CO from an air inlet pipe after the materials are melted 2 Completely dissolving and diffusing the high-pressure fluid into the nylon plate blank, locking gas for 15min, opening the die to relieve pressure, forming cell cores, and expanding the gas to obtain the PA6 pre-foaming material with the foaming ratio of 4 times;
(3) Taking out the nylon pre-foaming material from the primary compression molding mold, placing in a secondary compression molding foaming mold, setting the pressure at normal pressure and temperature at 225 deg.C, locking gas for 20min, opening the mold, releasing pressure, performing secondary compression foaming, cooling, and shaping to obtain 105kg/m 3 PA6 foamed articles.
Example 2
The method for preparing the nylon foaming product comprises the following steps:
(1) Comprises 85 weight parts of PA6, 15 weight parts of TPAE, 1 weight part of ADR4468 and 0.5 weight part of SiO 2 Adding the components of 0.5 part by weight of antioxidant 1098, 0.3 part by weight of antioxidant 626, 0.5 part by weight of SMA and 0.5 part by weight of PETs into an extruder, melting at 220 ℃, extruding by a die head, cooling and shaping to obtain a PA6/TPAE slab with the width of 210mm and the thickness of 12 mm;
(2) Placing the obtained nylon plate blank into a foaming cavity with a specific shape between an upper half mold and a lower half mold of a flat press, respectively setting the pressure within the range of 10MPa and the temperature within 225 ℃, injecting 2 parts by weight of CO from an air inlet pipe after the materials are melted 2 The high-pressure fluid is completely dissolved and diffused into the nylon plate blank, the gas is locked for 15min, the mould is opened to release the pressure, the foam holes are nucleated, and the gas is expanded to obtain PA6/TPAE with the foaming ratio of 4 timesA pre-foamed material;
(3) Taking out the nylon pre-foaming material from the primary compression molding mold, placing in a secondary compression molding foaming mold, setting the pressure at normal pressure and temperature at 225 deg.C, locking gas for 20min, opening the mold, releasing pressure, performing secondary compression molding foaming, cooling, and shaping to obtain 100kg/m 3 PA6/TPAE foamed articles.
Example 3
The method for preparing the nylon foaming product comprises the following steps:
(1) Adding the components comprising 100 parts by weight of PA66, 0.5 part by weight of ADR4468, 1 part by weight of SiO2, 0.8 part by weight of antioxidant 1098, 0.2 part by weight of antioxidant 626, 1 part by weight of MA-SEBS and 0.5 part by weight of PETs into an extruder, melting at 220 ℃, extruding by a die head, cooling and shaping to obtain a PA66 slab with the width of 210mm and the thickness of 12 mm;
(2) Placing the obtained nylon plate blank in a foaming cavity with a specific shape between an upper half mold and a lower half mold of a flat press, respectively setting the pressure within the range of 10MPa and the temperature at 265 ℃, injecting 2% CO from an air inlet pipe after the materials are melted 2 Completely dissolving and diffusing the high-pressure fluid into the nylon plate blank, locking gas for 15min, opening the die to relieve pressure, forming cell cores, and expanding the gas to obtain the nylon pre-foaming material with the foaming ratio of 4 times;
(3) Taking out the foamed material from the primary molding and forming mold, placing in a secondary molding and foaming mold, setting the pressure at normal pressure and temperature at 265 deg.C, locking gas for 20min, opening the mold, releasing pressure, performing secondary molding and foaming, cooling to obtain 117Kg/m 3 PA66 foamed articles.
Example 4
The method for preparing the nylon foaming product comprises the following steps:
(1) Adding the components comprising 100 parts by weight of PA12, 1 part by weight of ADR4468, 1 part by weight of Talc, 0.8 part by weight of antioxidant 1098, 0.2 part by weight of antioxidant 626, 0.5 part by weight of MA-SEBS and 0.2 part by weight of polyester wax into an extruder, melting at 220 ℃, extruding by a die head, cooling and shaping to obtain a PA12 slab with the width of 210mm and the thickness of 12 mm;
(2) Placing the obtained nylon plate blank into a foaming cavity with a specific shape between an upper half mold and a lower half mold of a flat press, respectively setting the pressure within the range of 10MPa and the temperature within the range of 260 ℃, and injecting 3 parts by weight of N from an air inlet pipe after the materials are melted 2 Completely dissolving and diffusing the high-pressure fluid into the nylon plate blank, locking gas for 15min, opening the die to relieve pressure, forming cell cores, and expanding the gas to obtain the PA12 pre-foaming material with the foaming ratio of 4 times;
(3) Taking out the foamed material from the primary molding forming mold, placing in a secondary molding foaming forming mold, setting the pressure at normal pressure and temperature at 260 deg.C, locking gas for 20min, opening the mold, releasing pressure, performing secondary molding foaming, cooling, and shaping to obtain 121kg/m 3 PA12 foamed articles.
Example 5
The method for preparing the nylon foaming product comprises the following steps:
(1) Adding the components comprising 100 parts by weight of PA56, 1 part by weight of ADR4468, 1 part by weight of Licomont CaV 102 (sodium montanate), 1 part by weight of antioxidant 1098, 0.5 part by weight of SMA and 0.3 part by weight of polyester wax into an extruder, melting at the temperature of 220 ℃, extruding by a die head, cooling and shaping to obtain a PA56 slab with the width of 210mm and the thickness of 12 mm;
(2) Placing the obtained nylon plate blank into a foaming cavity with a specific shape between an upper half mold and a lower half mold of a flat-plate press, respectively setting the pressure within the range of 10MPa and the temperature within the range of 250 ℃, and injecting 1.5 parts by weight of CO from an air inlet pipe after the materials are melted 2 Completely dissolving and diffusing the high-pressure fluid into the nylon plate blank, locking gas for 15min, opening the die to relieve pressure, forming cell cores, and expanding the gas to obtain the PA56 pre-foaming material with the foaming ratio of 5 times;
(3) Taking out the foamed material from the primary molding forming mold, placing in a secondary molding foaming forming mold, setting the pressure at normal pressure and temperature at 250 deg.C, locking gas for 20min, opening the mold, releasing pressure, performing secondary molding foaming, cooling, and shaping to obtain 104kg/m 3 PA56 foamed articles.
Example 6
The method for preparing the nylon foaming product comprises the following steps:
(1) Adding the components comprising 100 parts by weight of PA1212, 2 parts by weight of HDI, 1 part by weight of Licomont CaV 102 (sodium montanate), 0.5 part by weight of antioxidant 1216, 0.5 part by weight of SMA and 0.2 part by weight of montanic acid wax into an extruder, melting at the temperature of 220 ℃, extruding by a die head, cooling and shaping to obtain a PA1212 slab with the width of 210mm and the thickness of 12 mm;
(2) Placing the obtained nylon plate blank into a foaming cavity with a specific shape between an upper half die and a lower half die of a flat press, respectively setting the pressure within the range of 6MPa and the temperature at 210 ℃, injecting 1.5 parts by weight of cyclopentane from an air inlet pipe after the materials are melted, completely dissolving and diffusing the high-pressure fluid into the nylon plate blank, locking gas for 15min, opening the die to relieve pressure, forming cell nuclei, and expanding the gas to obtain a PA1212 pre-foaming material with the foaming magnification of 4 times;
(3) Taking out the foamed material from the primary compression molding mold, placing in a secondary compression molding foaming mold, setting the pressure at normal pressure and temperature at 210 deg.C, locking gas for 20min, opening the mold, releasing pressure, performing secondary compression molding foaming, cooling, and shaping to obtain 113kg/m 3 PA1212 foamed article.
Example 7
The method for preparing the nylon foaming product comprises the following steps:
(1) Adding the components comprising 100 parts by weight of PA610, 1 part by weight of TGIC, 0.8 part by weight of MgO, 0.5 part by weight of antioxidant 1216, 0.8 part by weight of POE-g-MAH and 0.2 part by weight of montanic acid wax into an extruder, melting at 220 ℃, extruding by a die head, cooling and shaping to obtain a PA610 slab with the width of 210mm and the temperature of 12 mm;
(2) Placing the obtained nylon plate blank into a foaming cavity with a specific shape between an upper half mold and a lower half mold of a flat press, respectively setting the pressure within the range of 8MPa and the temperature within the range of 230 ℃, injecting 2 parts by weight of CO from an air inlet pipe after the materials are melted 2 The high-pressure fluid is completely dissolved and diffused into the nylon plate blank, gas is locked for 15min, the mould is opened to release pressure, foam cells are nucleated, and the gas is expanded to obtain the PA610 pre-foaming material with the foaming ratio of 4 times;
(3) From one-time compression molding dieTaking out the foamed material, placing in a secondary molding foaming forming mold, setting the pressure at normal pressure and temperature at 230 deg.C, locking gas for 20min, opening the mold, releasing pressure, performing secondary molding foaming, cooling, and shaping to obtain 110kg/m 3 PA610 foamed articles.
Example 8
The method for preparing the nylon foaming product comprises the following steps:
(1) Adding the components comprising 100 parts by weight of TPAE, 1 part by weight of TGIC, 0.5 part by weight of MgO, 0.5 part by weight of antioxidant 1216, 0.2 part by weight of antioxidant 9228, 0.8 part by weight of POE-g-MAH and 0.5 part by weight of PETs into an extruder, melting at 220 ℃, extruding by a die head, cooling and shaping to obtain a TPAE plate blank with the width of 210mm and the thickness of 12 mm;
(2) Placing the obtained nylon plate blank into a foaming cavity with a specific shape between an upper half mold and a lower half mold of a flat press, respectively setting the pressure within the range of 10MPa and the temperature within 220 ℃, injecting 2 parts by weight of CO from an air inlet pipe after the materials are melted 2 Completely dissolving and diffusing the high-pressure fluid into the nylon plate blank, locking gas for 15min, opening the die to relieve pressure, forming cell cores, and expanding the gas to obtain the TPAE pre-foaming material with the foaming ratio of 4 times;
(3) Taking out the foaming material from the primary compression molding mold, placing in a secondary compression molding foaming mold, setting the pressure at normal pressure and temperature at 220 deg.C, locking gas for 20min, opening the mold, releasing pressure, performing secondary compression molding foaming, cooling, and shaping to obtain 108kg/m 3 TPAE foamed articles.
Example 9
The method for preparing the nylon foaming product comprises the following steps:
(1) Adding the components comprising 100 parts by weight of MXD6, 1 part by weight of TGIC, 2 parts by weight of Talc, 0.5 part by weight of antioxidant 1216, 0.2 part by weight of antioxidant 9228, 0.8 part by weight of POE-g-MAH and 0.5 part by weight of PETs into an extruder, melting at 220 ℃, extruding by a die head, cooling and shaping to obtain an MXD6 slab with the width of 210mm and the temperature of 12 mm;
(2) Placing the obtained nylon plate blank between an upper half die and a lower half die of a flat press to obtain a special-shaped hairIn the bubble cavity, the pressure is set within the range of 20MPa, the temperature is set as 230 ℃, and 3 parts by weight of N is injected from an air inlet pipe after the materials are melted 2 Completely dissolving and diffusing high-pressure fluid into a nylon plate blank, locking gas for 15min, opening the die to relieve pressure, forming cell cores, and expanding the gas to obtain the MXD6 pre-foamed material with the foaming ratio of 4 times;
(3) Taking out the foamed material from the primary molding forming mold, placing in a secondary molding foaming forming mold, setting the pressure at normal pressure and temperature at 230 deg.C, locking gas for 20min, opening the mold, releasing pressure, performing secondary molding foaming, cooling, and shaping to obtain 119kg/m 3 MXD6 foamed articles.
Example 10
The method for preparing the nylon foaming product comprises the following steps:
(1) Comprises 100 weight portions of PA612, 2 weight portions of HDI and 0.5 weight portion of SiO 2 Adding the components of 0.5 weight part of antioxidant 1098, 0.2 weight part of antioxidant 626, 0.5 weight part of SMA and 0.5 weight part of PETs into an extruder, melting at 220 ℃, extruding by a die head, cooling and shaping to obtain a PA612 slab with the width of 210mm and the thickness of 12 mm;
(2) Placing the obtained nylon plate blank into a foaming cavity with a specific shape between an upper half mold and a lower half mold of a flat press, respectively setting the pressure within the range of 25MPa and the temperature at 265 ℃, and injecting 2 parts by weight of CO from an air inlet pipe after the materials are melted 2 The high-pressure fluid is completely dissolved and diffused into the nylon plate blank, gas is locked for 15min, the mould is opened to release pressure, foam cells are nucleated, and the gas is expanded to obtain the PA612 pre-foaming material with the foaming ratio of 4 times;
(3) Taking out the foamed material from the primary molding and forming mold, placing in a secondary molding and foaming mold, setting the pressure at normal pressure and temperature at 265 deg.C, locking gas for 20min, opening the mold, releasing pressure to perform secondary molding and foaming, cooling to obtain 115kg/m 3 PA612 foamed article.
Comparative example
The method for preparing the nylon foaming product comprises the following steps:
(1) Adding components comprising 85 parts by weight of PA6, 15 parts by weight of TPAE, 1 part by weight of ADR, 0.5 part by weight of SiO2, 0.5 part by weight of antioxidant 1098, 0.3 part by weight of antioxidant 626, 0.5 part by weight of SMA and 0.5 part by weight of PETs into an extruder, melting at 220 ℃, extruding through a die head, cooling and shaping to obtain a PA6 plate blank with the width of 210mm and the thickness of 12 mm;
(2) Placing the nylon plate blank in a foaming cavity with a specific shape between an upper half mold and a lower half mold of a flat press, respectively setting the pressure to be 10MPa and the temperature to be 220 ℃, injecting 2 parts by weight of CO from an air inlet pipe after the materials are melted 2 Locking gas for 20min, opening the die to relieve pressure, expanding the gas, cooling and shaping to obtain the density of 110kg/m 3 The PA6/TPAE foamed article of (1).
Evaluation:
1. the nylon foamed articles obtained in examples 1 to 10 and comparative example were evaluated for density, expansion ratio, flexural strength, tensile strength, compressive strength and closed cell ratio;
2. the performance evaluation method of the nylon foaming product comprises the following steps:
foam density: ISO 845
Foaming ratio: ratio of density of material after foaming to density before foaming
Bending strength: GB/T8812-88
Tensile strength: ASTM C297
Compressive strength: ISO 844
Closed pore rate: GB/T10799-2008
The test results of the nylon foamed articles obtained in examples 1 to 10 and comparative example are shown in Table 1.
TABLE 1 Performance data for the nylon foamed articles obtained in examples 1-10 and comparative examples
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method for preparing a nylon molded foam material, comprising:
(1) Mixing nylon, a chain extender, a nucleating agent and an antioxidant, and then, melting, blending and extruding to obtain a nylon plate blank;
(2) Placing the nylon plate blank in a foaming cavity of a primary compression molding mold for heating, injecting a high-pressure supercritical fluid into the foaming cavity after the nylon plate blank is melted, so that the high-pressure supercritical fluid is diffused and dissolved in the nylon plate blank and is locked for a first preset time, and then opening the mold for pressure relief to obtain a nylon pre-foaming material;
(3) And placing the nylon pre-foaming material in a foaming cavity of a secondary compression molding mould, locking gas at normal pressure and under heating for a second preset time, and then opening the mould to relieve pressure so as to obtain the nylon compression molding foaming material.
2. The method according to claim 1, wherein in the step (1), the mass ratio of the nylon, the chain extender, the nucleating agent and the antioxidant is 100: (0.5-2): (0.5-2): (0.5-1).
3. The method according to claim 1 or 2, wherein in step (1), the nylon comprises at least one of PA6, PA66, PA610, PA612, PA12, PA1212, PA56, TPAE, and MXD 6;
optionally, in step (1), the chain extender comprises at least one of a homoisocyanate, a multifunctional epoxy resin, and triglycidyl isocyanurate;
optionally, in step (1), the nucleating agent comprises at least one of silica, talc, sodium montanate, magnesium oxide;
optionally, in step (1), the antioxidant comprises at least one of antioxidant 1098, antioxidant 1216, antioxidant 626, and antioxidant S9228.
4. The method according to claim 1, wherein in the step (1), the nylon mat has a thickness of 10 to 20mm and a width of 200 to 250mm.
5. The method as set forth in claim 1, wherein at least one of a high temperature resistant lubricant and a compatibilizer is further added in step (1), the high temperature resistant lubricant being used in an amount of 0.2 to 0.5 parts by weight and the compatibilizer being used in an amount of 0.5 to 1 parts by weight, based on 100 parts by mass of the nylon material.
6. The method of claim 5, wherein the high temperature resistant lubricant comprises at least one of polyester wax, montanic acid wax, and PETs;
the compatilizer comprises at least one of MA-SEBS, SMA and POE-g-MAH.
7. The method according to claim 1, wherein in step (2), the nylon mat is placed in a foaming cavity of the one-time molding die at a pressure of 6 to 15MPa and a temperature of 210 to 270 ℃ to melt the nylon mat;
optionally, the first predetermined time is 10-25 min;
optionally, the foaming ratio of the nylon pre-foaming material is 2-5 times.
8. The method of claim 1, wherein in step (2), the high pressure supercritical fluid comprises cyclopentane, N 2 And CO 2 And the amount of the physical blowing agent is 1.5 to 3 parts by weight based on 100 parts by mass of the nylon.
9. The method according to claim 1, wherein in step (3), the nylon pre-foamed material is placed in a foaming cavity of the secondary molding die, and gas is locked at a temperature of 210-270 ℃ for 10-30 min under normal pressure.
10. A nylon molded foam, characterized in that it is prepared by the process of claims 1-9.
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