CN115505161B - 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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- CN115505161B CN115505161B CN202110697578.7A CN202110697578A CN115505161B CN 115505161 B CN115505161 B CN 115505161B CN 202110697578 A CN202110697578 A CN 202110697578A CN 115505161 B CN115505161 B CN 115505161B
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- 238000005187 foaming Methods 0.000 title claims abstract description 209
- 239000004677 Nylon Substances 0.000 title claims abstract description 160
- 229920001778 nylon Polymers 0.000 title claims abstract description 160
- 239000000463 material Substances 0.000 title claims abstract description 117
- 238000003825 pressing Methods 0.000 title abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 238000000748 compression moulding Methods 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 54
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 39
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 38
- 239000012530 fluid Substances 0.000 claims abstract description 28
- 239000002667 nucleating agent Substances 0.000 claims abstract description 21
- 239000004970 Chain extender Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000001125 extrusion Methods 0.000 claims description 16
- 239000006261 foam material Substances 0.000 claims description 14
- 239000000314 lubricant Substances 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- YKIBJOMJPMLJTB-UHFFFAOYSA-M sodium;octacosanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O YKIBJOMJPMLJTB-UHFFFAOYSA-M 0.000 claims description 10
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 8
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims description 7
- 229920006121 Polyxylylene adipamide Polymers 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 5
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 230000037228 dieting effect Effects 0.000 claims 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims 1
- 239000006260 foam Substances 0.000 abstract description 20
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- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 4
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- 230000003313 weakening effect Effects 0.000 description 3
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 2
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- 229910052681 coesite Inorganic materials 0.000 description 2
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- 238000006731 degradation reaction Methods 0.000 description 2
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- 229920001971 elastomer Polymers 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
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- 238000010008 shearing Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
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- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
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- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
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- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
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- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- 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
- B29C69/02—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 of moulding techniques only
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
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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
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J9/0028—Use of organic additives containing nitrogen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J9/0038—Use of organic additives containing phosphorus
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
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- C08J2203/08—Supercritical fluid
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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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
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- C08J2377/02—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
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- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
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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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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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
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
- C08J2491/06—Waxes
Abstract
The invention discloses a nylon mould pressing foaming material and a preparation method thereof, wherein the method comprises the following steps: (1) Mixing nylon material, chain extender, nucleating agent and antioxidant, and melt blending and extruding to obtain nylon plateBlank; (2) Heating a nylon slab in a foaming cavity of a one-time compression molding die, injecting high-pressure supercritical fluid into the foaming cavity after the nylon slab is melted, so that the high-pressure supercritical fluid is diffused and dissolved in the nylon slab, and opening the die and releasing pressure after locking the high-pressure supercritical fluid for a preset time to obtain a nylon pre-foaming material; (3) And placing the nylon pre-foaming material into a foaming cavity of a secondary compression molding die, locking gas under normal pressure and heating for a preset time, and then opening the die to release pressure to obtain 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 holes is 50-200 um, the yield is more than or equal to 95%, and the closed porosity is more than 95%; the tensile strength is greater than 1.0MPa.
Description
Technical Field
The invention belongs to the field of nylon foaming materials, and particularly relates to a nylon compression molding foaming material and a preparation method thereof.
Background
The foam molding process generally includes 3 stages: 1) Injecting gas to dissolve in the polymer melt to form a saturated homogeneous system; 2) The driving force of the internal and external pressure difference formed by rapid pressure relief forms a bubble nucleus hot spot and the nucleating agent is out of phase to form a hot spot nucleus; 3) The growth of bubble nuclei and the solidification and shaping of bubbles.
If the intensity of the melt is too low in the foaming process of the PA, the balance between the pressure of the gas generated by decomposition generated by foaming and the viscosity and elasticity of the material is difficult to achieve, and the tiny resistance in the foaming process can lead to the phenomena of foam cell collapse, cracking, merging and the like of the foam material, namely the foam wall can not maintain a certain intensity, so that effective bubbles can not be formed, so that special attention must be paid to control the elasticity of the melt so as to ensure that the production is carried out normally.
Nylon extrusion foaming molding is limited by factors such as low melt strength, semicrystalline materials, high technological control requirements in the extrusion process, high requirements on extrusion foaming molding equipment and the like, and it is difficult to prepare foam materials with uniform and continuous properties and stable cells. The size of the extruded foam sheet product of the extrusion foaming molding porous strip foam die head is single flat plate shape, and the surface of the extruded foam sheet product needs to be planed, so that the phenomena of rough and unsmooth foam surface and the like are caused.
Therefore, the existing technology for preparing the foaming material needs to be explored.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, an object of the present invention is to provide a nylon molding foaming material and a method for preparing the same, wherein the nylon molding foaming material prepared by the method of the present invention has a density of at least 100kg/m 3 ) The mechanical property is higher, 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 shockproof performances and excellent chemical resistance, is breathable, washable and reusable, and has a finished product yield of more than 95%, a closed pore rate of more than or equal to 95% and a foaming multiplying power of 5-20 times, so that the method can be practically applied to production and manufacturing and produce economic benefits, and can be widely applied to various fields of automobiles, aerospace, product protection, industrial parts, oceans, buildings, military, medical treatment, sports, leisure and the like.
In one aspect of the invention, a method of making a nylon compression 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 extrusion to obtain a nylon slab;
(2) Heating the nylon slab in a foaming cavity of a one-time compression molding die, injecting high-pressure supercritical fluid into the foaming cavity after the nylon slab is melted, so that the high-pressure supercritical fluid is diffused and dissolved in the nylon slab, and opening the die to release pressure after locking the high-pressure supercritical fluid for a first preset time so as to obtain a nylon pre-foaming material;
(3) And placing the nylon pre-foaming material into a foaming cavity of a secondary compression molding die, locking gas under normal pressure and heating for a second preset time, and then opening the die and releasing pressure 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 subjected to melt blending extrusion, so 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 of the nylon 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 foamability of the nylon, and no obvious weakening phenomenon exists along with the processing time, so that the phenomena of foam collapse, foam cell breakage and foam cell merging 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 to form a large number of uniform nucleation hot spots, so that a nylon compression molding foaming material with higher multiplying power is obtained later, then the nylon Long Banpi obtained by melt blending extrusion is placed in a foaming cavity of a primary compression molding mold for heating, when a nylon slab is melted and high-pressure supercritical fluid is injected into the foaming cavity, the high-pressure supercritical fluid is enabled to be diffused and dissolved in the nylon slab and locked for a first preset time, then the mold is opened for pressure relief, finally the obtained nylon pre-foaming material is placed in the foaming cavity of a secondary compression molding mold for normal pressure and locked for a second preset time after being heated, namely, the foaming material is subjected to pressure relief through twice compression molding, the size of the foaming material is controlled to be 2-5 times of an appropriate expansion volume ratio through primary compression molding foaming, then the pre-foaming material is placed in the secondary compression molding mold for setting and heating, the gas remained in the pre-foaming material is released slowly, and then the size of the foaming material is expanded gradually to be 5 times of a foaming hole according to the designed size of the foaming material, and the problem of the foaming material is solved, and the problem of tearing of a foaming plate is solved. Meanwhile, compared with the traditional extrusion foaming molding porous strip foaming die head extrusion foam board product, the size of the product is single flat plate shape, the product needs to be planed, the phenomenon that the surface of the foam is rough and not smooth is caused, and the like, the surface of the nylon mould pressing foaming material obtained by the invention is smooth. Thus, compared with common foam materials with the same density, the nylon mould prepared by the method of the application is moldedFoam material (with minimum density less than or equal to 100 kg/m) 3 ) The mechanical property is higher, 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 shockproof performances and excellent chemical resistance, is breathable, washable and reusable, and has a finished product yield of more than 95%, a closed pore rate of more than or equal to 95% and a foaming multiplying power of 5-20 times, so that the method can be practically applied to production and manufacturing and produce economic benefits, and can be widely applied to various fields of automobiles, aerospace, product protection, industrial parts, oceans, buildings, military, medical treatment, sports, leisure and the like.
In addition, the method for preparing the nylon compression molding foaming material according to the above embodiment of the present invention may have the following additional technical features:
in some embodiments of the 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, the nylon mould pressing foaming material with excellent characteristics of high foaming multiplying power, high closed pore rate and the like can be prepared.
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 polyfunctional epoxy resin, and triglycidyl isocyanurate. Therefore, the melt strength of the nylon is effectively improved, the foamability of the nylon is improved, no obvious weakening phenomenon exists along with the processing time, and the phenomena of foam collapse, foam cell breakage and foam cell merging 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 spots are formed, so that the nylon mould pressing foaming material with higher multiplying power can be obtained later.
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 invention, in step (1), the nylon slabs have a thickness of 10-20mm and a width of 200-250mm.
In some embodiments of the present invention, in step (1), at least one of a high temperature resistant lubricant and a compatibilizer is further added 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 part by weight based on 100 parts by weight of the nylon. Therefore, the phenomena of thermal degradation, melt fracture and surface roughness of the melt caused by over-high temperature and shearing can be improved, the fluidity of the melt is improved, the surface of the extruded material is smoother, and the method is beneficial to forming foaming materials and forming uniform and stable foam cells with controllable sizes.
In some embodiments of the invention, the high temperature resistant lubricant comprises at least one of a polyester wax, a montan acid wax, and PETs, and the compatibilizer comprises at least one of MA-SEBS, SMA, and POE-g-MAH. Thereby helping to form uniform, stable, size-controllable cells.
In some embodiments of the present invention, in step (2), the nylon slabs are placed in a foaming cavity of the primary compression molding die at a pressure of 6 to 15MPa and a temperature of 210 to 270 ℃ so that the nylon slabs are melted.
In some embodiments of the invention, in step (2), the first predetermined time is 10 to 25 minutes.
In some embodiments of the invention, in step (2), the nylon pre-expanded material has a foaming 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 present invention, in step (3), the nylon pre-foaming material is placed in a foaming cavity of the secondary compression molding mold to lock gas at a temperature of 210 to 270 ℃ for 10 to 30 minutes under normal pressure.
In a second aspect of the invention, the invention provides a nylon compression molded foam. According to the embodiment of the invention, the nylon mould pressing foaming material is prepared by adopting the method. Thus, compared with the common foam material with the same density, the nylon mould pressing foam material prepared by the method (the density is less than or equal to 100kg/m at the lowest) 3 ) The mechanical property is higher, 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 shockproof performances and excellent chemical resistance, is breathable, washable and reusable, and has a finished product yield of more than 95%, a closed pore rate of more than or equal to 95% and a foaming multiplying power of 5-20 times, so that the method can be practically applied to production and manufacturing and produce economic benefits, and can be widely applied to various fields of automobiles, aerospace, product protection, industrial parts, oceans, buildings, military, medical treatment, sports, leisure and the like.
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 foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic flow chart of a method for preparing a nylon compression molded foam according to one embodiment of the invention.
Detailed Description
The following detailed description of the embodiments of the invention is intended to be illustrative of the invention and is not to be taken as limiting the invention.
In one aspect of the invention, a method of making a nylon compression molded foam is provided. Referring to fig. 1, according to an embodiment of the present invention, the method includes:
s100: nylon, chain extender, nucleating agent and antioxidant are mixed and then are melt, blended and extruded
In the step, nylon, a chain extender, a nucleating agent and an antioxidant are uniformly mixed, and are added into a double-screw extruder for melt blending after being metered by a weight loss feeding system, and are extruded by a specially designed slit structure die head, and a nylon slab with the thickness of 10-20mm and the width of 200-250mm is obtained after cooling and shaping. The inventor finds that the storage modulus, the loss modulus and the complex viscosity of nylon are increased along with the increase of the addition amount, the loss factor of the nylon 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 foamability of the nylon, and the phenomena of collapse, cell breakage and cell merging in the foaming process are effectively prevented without obvious weakening along with the processing time; the nucleating agent forms a large number of low potential energy points at the interface between melts in the foaming process to form a large number of uniform nucleation hot spots, thereby being beneficial to obtaining the nylon mould pressing foaming material with higher multiplying power subsequently.
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 gel-like, similar to rubber, and the color is also deep, which is not beneficial to extrusion; if the chain extender is added too low, the growth of foam cannot be supported, so that the foam collapse phenomenon is caused; meanwhile, if the nucleating agent is excessively added, agglomeration is formed, and the formation of uniform cell structures is not facilitated; if the addition of the nucleating agent is too low, the ideal nucleating effect cannot be obtained, heterogeneous nucleation points are few, and a compact foam structure cannot be formed; if the addition amount of the antioxidant exceeds 1 part by weight, the antioxidation 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 TPAE is no 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 great brittleness; the PA6 and the TPAE are blended, and TPAE elastomer particles are dispersed in a PA6 matrix to form a stress concentration point which can absorb a large amount of external energy, so that the notch impact strength, low-temperature impact and processability of the PA6 are obviously improved, and the effect of a foam material toughening agent is achieved; and under the condition that the TPAE illumination ratio is not more than 20 parts by weight, the TPAE particles also play the role of a nucleating agent in the crystallization process of the PA6, promote the crystallization rate of the PA6 and facilitate the formation of a cell structure in the foaming process. Preferably, the mass ratio of the nylon to the chain extender to the nucleating agent to 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 isocyanate (HDI), polyfunctional epoxy (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, preferably sodium montanate. The inventor finds that long-chain linear saturated sodium montanate takes chain length C28-C32 as a main component and is used as a nylon nucleating agent, on one hand, the long-chain linear saturated sodium montanate reacts with a nylon end group to form micromolecule heterogeneous nucleation, so that the crystallization efficiency and the heat 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 a very strong polar center and a very long nonpolar carbon chain, the part compatible with plastics in polarity in the structure plays a role in internal lubrication, and the part incompatible with plastics in polarity plays a role in external lubrication and demolding, so that the fluidity of the extrusion process and the demolding property between a melt and equipment are improved and improved, and the gas expansion foaming processing period of the compression molding foaming process is shortened by 10%. The antioxidants include at least one of antioxidant 1098, antioxidant 1216, antioxidant 626, and antioxidant S9228.
According to a further embodiment of the present invention, at least one of a high temperature resistant lubricant and a compatibilizer may be added in the above steps, for example, nylon, a chain extender, a nucleating agent, an antioxidant, and the high temperature resistant lubricant and the compatibilizer are mixed and melt blended and extruded. The inventor finds that adding the high-temperature resistant lubricant can improve the phenomena of thermal degradation, melt fracture and surface roughness of the melt caused by over-high temperature and shearing, improve the fluidity of the melt in the extrusion process and improve the mold release between the melt and equipment. Preferred high temperature resistant lubricants are polyester waxes, montan acid waxes or PETs; the compatilizer can be one or more of MA-SEBS, SMA, POE-g-MAH, preferably SMA. The inventor finds that the SMA is a styrene-maleic anhydride graft copolymer, and the molecular chain contains more MA groups, so that the SMA can be subjected to amidation reaction with PA6 or esterification reaction with TPAE, and therefore, the interfacial compatibility of the TPAE and the 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 addition of the compatilizer SMA plays a role in improving the interfacial force between the blends while ensuring the high toughness of the foam material prepared by the later-stage compression molding, 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 weight 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 rough at a high temperature; if the addition amount of the high-temperature lubricant is too high, the melt strength of the melt is reduced, and the support of the gas by the foam cells is not facilitated. If the addition amount of the compatilizer is too high, plasticization is caused, the mechanical property and modulus of the nylon base material are reduced, and in addition, agglomeration and steric effect are generated; if the amount of the compatibilizing agent is too low, the two incompatible polymers cannot be caused to bond together by intermolecular bonding forces.
S200: heating the nylon slab in the foaming cavity of the one-step compression molding mold, and injecting high-pressure supercritical fluid into the foaming cavity after the nylon slab is melted
In the step, the obtained nylon slab is placed in a foaming cavity of a one-time compression molding die for treatment under the pressure of 6-15 MPa and the temperature of 210-270 ℃, high-pressure supercritical fluid is injected into the foaming cavity after the nylon slab is melted, so that the high-pressure supercritical fluid is diffused and dissolved in the nylon slab, and the die is opened for pressure relief after the high-pressure supercritical fluid is locked for 10-25 min, so that the nylon pre-foaming material with the foaming multiplying power of 2-5 times is obtained.
Further, according to one 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 (a) and (b); and is used in an amount of 1.5 to 3 parts by weight based on 100 parts by weight of the nylon physical blowing agent. The inventor finds that if the addition amount of the physical foaming agent is too high, the excessive foaming agent does not participate in the cell growth process due to the limited solubility of the foaming agent in the nylon slab; 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 into a foaming cavity of a secondary compression molding die, locking gas under normal pressure and heating for a second preset time, and opening the die to release 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, the die is opened for pressure relief, cooling and shaping are carried out, and finally the nylon compression molding foaming material with high multiplying power and closed hole rate of more than or equal to 95% is obtained. 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 holes is 50-200 um, and the yield is more than or equal to 95%. According to GBT10799-2008 standard, the closed porosity of the nylon mould pressing foaming material is more than 95%; the nylon compression molded foam has a tensile strength of greater than 1.0MPa according to ASTM C297 standard.
In the traditional foam compression molding, a one-time compression molding foaming process is adopted, in order to reduce the density, namely to improve the foaming rate, and when the using amount of the foaming agent is increased to be the same as that of the two-time compression molding foaming agent, when the foaming material is released and taken out of the mold, foaming gas is instantaneously released, and foam holes grow up, so that the volume of the foaming material is 10-20 times compared with that of the foaming material in the mold, and the foaming material is broken and torn due to intense expansion in the process, so that the foaming quality of the foaming material is poor. In the application, the foaming is carried out by adopting twice mould pressing, the size of the foaming material is controlled to be 2-5 times of proper expansion volume ratio by virtue of once mould pressing foaming, then the pre-foaming material is moved into a twice mould pressing forming mould, normal pressure is set and heated, so that the gas remained in the pre-foaming material is slowly released, the size of the foaming material is gradually expanded to be the size designed according to the formula (5-20 times of expansion ratio), and the phenomena of hole and tearing of the foaming plate caused by the fierce expansion of once foaming are solved. Meanwhile, compared with the traditional extrusion foaming molding porous strip foaming die head extrusion foam board product, the size of the product is single flat plate shape, the product needs to be planed, the phenomenon that the surface of the foam is rough and not smooth is caused, and the like, the surface of the nylon mould pressing foaming material obtained by the invention is smooth.
In a second aspect of the invention, the invention provides a nylon compression molded foam. According to the embodiment of the invention, the nylon mould pressing foaming material is prepared by adopting the method. Thus, compared with the common foam material with the same density, the nylon mould pressing foam material prepared by the method (the density is less than or equal to 100kg/m at the lowest) 3 ) The mechanical property is higher, 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 shockproof performances and excellent chemical resistance, is breathable, washable and reusable, and has a finished product yield of more than 95%, a closed pore rate of more than or equal to 95% and a foaming multiplying power of 5-20 times, so that the method can be practically applied to production and manufacturing and produce economic benefits, and can be widely applied to various fields of automobiles, aerospace, product protection, industrial parts, oceans, buildings, military, medical treatment, sports, leisure and the like. It should be noted that the features and advantages described above for the method for preparing the nylon molding foaming material are equally applicable to the nylon molding foaming material, and are not described herein.
The following detailed description of embodiments of the invention is provided for the purpose of illustration only and is not to be construed as limiting the invention. In addition, all reagents employed in the examples below are commercially available or may 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 is a specific description of the raw materials in the examples and comparative examples:
PA6: lO13B, japanese UBE chemical Co., ltd;
TPAE: TPAE X3533, france Achroma;
styrene-maleic anhydride graft copolymer (SMA): SMA-020, a new material of raised molecules in the south tongri;
HDI: the smoke table is in a everlasting state;
ADR 4468: basf;
TGIC: ala Ding Shiji;
montanic acid sodium salt: kelaien Licomont CaV 102;
SiO 2 (Sia): industry products manufactured by Cabot corporation, cabot, usa;
antioxidant 1098, antioxidant 1216: manufactured by riskiba machine company;
antioxidant S9228: doverPhos, duofu chemical, USA;
twin screw extruder: keplon STS-50MC11;
slit structure sheet extrusion die: wide width 200mm and thick width 10mm.
Example 1
The method for preparing the nylon foaming product comprises the following steps:
(1) Will contain 100 weight parts of PA6, 1 weight part of ADR4468 and 0.5 weight part of SiO 2 Adding components including 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 through a die head, and cooling and shaping to obtain a PA6 plate blank with the thickness of 12mm and the width of 210 mm;
(2) Placing the obtained nylon slab in 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 a range of 10MPa, setting the temperature at 225 ℃, 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 slab,locking gas for 15min, opening the mould, releasing pressure, nucleating cells, and expanding the gas to obtain the PA6 pre-foaming material with the foaming multiplying power of 4 times;
(3) Taking out the nylon pre-foaming material from the one-time compression molding mold, placing the nylon pre-foaming material into a two-time compression molding mold, setting the pressure in a normal pressure state, setting the temperature at 225 ℃, locking the gas for 20min, opening the mold, releasing pressure, performing the second compression molding foaming, and cooling and shaping to obtain 105kg/m 3 PA6 foamed article.
Example 2
The method for preparing the nylon foaming product comprises the following steps:
(1) Will contain 85 parts by weight of PA6, 15 parts by weight of TPAE, 1 part by weight of ADR4468 and 0.5 part by weight of SiO 2 Adding components including 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 through a die head, and cooling and shaping to obtain a PA6/TPAE slab with the width of 12mm and the width of 210 mm;
(2) Placing the obtained nylon slab in 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 a range of 10MPa, setting the temperature at 225 ℃, 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 a nylon plate blank, gas is locked for 15min, the die is opened, the pressure is released, the cells are nucleated, and the gas is expanded to obtain the PA6/TPAE pre-foaming material with the foaming multiplying power of 4 times;
(3) Taking out the nylon pre-foaming material from the one-time compression molding mold, placing the nylon pre-foaming material into a two-time compression molding mold, setting the pressure in a normal pressure state, setting the temperature at 225 ℃, locking the gas for 20min, opening the mold, releasing pressure, performing the second compression molding foaming, and 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 including 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 through a die head, and cooling and shaping to obtain a PA66 slab with the width of 12mm and the width of 210 mm;
(2) Placing the obtained nylon slab in 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 a range of 10MPa, setting the temperature at 265 ℃, and injecting 2% CO from an air inlet pipe after the materials are melted 2 Completely dissolving and diffusing high-pressure fluid into a nylon slab, locking gas for 15min, opening a die, releasing pressure, nucleating cells, and expanding the gas to obtain a nylon pre-foaming material with the foaming multiplying power of 4 times;
(3) Taking out the foaming material from the one-time compression molding mold, placing the foaming material into a two-time compression molding foaming mold, setting the pressure at a normal pressure state, setting the temperature at 265 ℃, locking the gas for 20min, opening the mold, releasing the pressure, performing the second compression molding foaming, and cooling and shaping to obtain 117Kg/m 3 PA66 foamed article.
Example 4
The method for preparing the nylon foaming product comprises the following steps:
(1) Adding the components including 100 weight parts of PA12, 1 weight part of ADR4468, 1 weight part of Talc, 0.8 weight part of antioxidant 1098, 0.2 weight part of antioxidant 626, 0.5 weight part of MA-SEBS and 0.2 weight part of polyester wax into an extruder, melting at 220 ℃, extruding through a die head, and cooling and shaping to obtain a PA12 slab with the width of 12mm and the width of 210 mm;
(2) Placing the obtained nylon slab in 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 a range of 10MPa, setting the temperature at 260 ℃, and injecting 3 parts by weight of N 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 a die, releasing pressure, nucleating cells, and expanding the gas to obtain a PA12 pre-foaming material with the foaming multiplying power of 4 times;
(3) Taking out the foaming material from the primary compression molding die, placing the foaming material into the secondary compression molding foaming die, setting the pressure at a normal pressure state, setting the temperature at 260 ℃, locking the gas for 20min, opening the die, releasing the pressure, performing secondary compression molding foaming, and cooling and shaping to obtain 121kg/m 3 PA12 foamed article.
Example 5
The method for preparing the nylon foaming product comprises the following steps:
(1) Adding the components including 100 weight parts of PA56, 1 weight part of ADR4468, 1 weight part of Licom CaV 102 (montanic acid sodium salt), 1 weight part of antioxidant 1098, 0.5 weight part of SMA and 0.3 weight part of polyester wax into an extruder, melting at 220 ℃, extruding through a die head, and cooling and shaping to obtain a PA56 plate blank with the width of 12mm and 210 mm;
(2) Placing the obtained nylon slab in 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 a range of 10MPa, setting the temperature at 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 high-pressure fluid into a nylon plate blank, locking gas for 15min, opening a die, releasing pressure, nucleating cells, and expanding the gas to obtain a PA56 pre-foaming material with 5 times of foaming multiplying power;
(3) Taking out the foaming material from the one-time compression molding mold, placing the foaming material into a two-time compression molding foaming mold, setting the pressure in a normal pressure state, setting the temperature at 250 ℃, locking the gas for 20min, opening the mold, releasing the pressure, performing the second compression molding foaming, and cooling and shaping to obtain 104kg/m 3 PA56 foamed article.
Example 6
The method for preparing the nylon foaming product comprises the following steps:
(1) Adding 100 parts by weight of PA1212, 2 parts by weight of HDI, 1 part by weight of Licom 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 220 ℃, extruding through a die head, and cooling and shaping to obtain a PA1212 slab with the width of 12mm and the width of 210 mm;
(2) Placing the obtained nylon slab in 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 a range of 6MPa, setting the temperature at 210 ℃, injecting 1.5 parts by weight of cyclopentane from an air inlet pipe after materials are melted, completely dissolving and diffusing high-pressure fluid into the nylon slab, locking gas for 15min, opening the die for pressure relief, nucleating cells, and expanding the gas to obtain a PA1212 pre-foaming material with a foaming multiplying power of 4 times;
(3) Taking out the foaming material from the primary compression molding die, placing the foaming material into the secondary compression molding foaming die, setting the pressure at normal pressure, setting the temperature at 210 ℃, locking the gas for 20min, opening the die, releasing the pressure, performing secondary compression molding foaming, and 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 including 100 weight parts of PA610, 1 weight part of TGIC, 0.8 weight part of MgO, 0.5 weight part of antioxidant 1216, 0.8 weight part of POE-g-MAH and 0.2 weight part of montanic acid wax into an extruder, melting at 220 ℃, extruding through a die head, and cooling and shaping to obtain a PA610 slab with the width of 210mm and the length of 12 mm;
(2) Placing the obtained nylon slab in 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 a range of 8MPa, setting the temperature at 230 ℃, and injecting 2 parts by weight of CO 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 a die, releasing pressure, nucleating cells, and expanding the gas to obtain a PA610 pre-foaming material with the foaming multiplying power of 4 times;
(3) Taking out the foaming material from the primary compression molding die, placing the foaming material into the secondary compression molding foaming die, setting the pressure at a normal pressure state, setting the temperature at 230 ℃, locking the gas for 20min, opening the die, releasing the pressure, performing secondary compression molding foaming, and cooling and shaping to obtain 110kg/m 3 PA610 foamed article.
Example 8
The method for preparing the nylon foaming product comprises the following steps:
(1) Adding the components including 100 weight parts of TPAE, 1 weight part of TGIC, 0.5 weight part of MgO, 0.5 weight part of antioxidant 1216, 0.2 weight part of antioxidant 9228, 0.8 weight part of POE-g-MAH and 0.5 weight part of PETs into an extruder, melting at 220 ℃, extruding through a die head, and cooling and shaping to obtain a TPAE slab with the width of 12mm and the width of 210 mm;
(2) Placing the obtained nylon slab in 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 a range of 10MPa, setting the temperature to 220 ℃, and injecting 2 parts by weight of CO 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 a mold, releasing pressure, nucleating cells, and expanding the gas to obtain a TPAE pre-foaming material with the foaming multiplying power of 4 times;
(3) Taking out the foaming material from the one-time compression molding mold, placing the foaming material into a two-time compression molding foaming mold, setting the pressure in a normal pressure state, setting the temperature at 220 ℃, locking the gas for 20min, opening the mold, releasing the pressure, performing the second compression molding foaming, and 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 including 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 ℃ and extruding through a die head, and cooling and shaping to obtain an MXD6 slab with the width of 12mm and the width of 210 mm;
(2) Placing the obtained nylon slab in 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 a range of 20MPa, setting the temperature at 230 ℃, and injecting 3 parts by weight of N 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 a die, releasing pressure, nucleating cells, and expanding the gas to obtain an MXD6 pre-foaming material with the foaming multiplying power of 4 times;
(3) Taking out the foaming material from the one-time compression molding mold, placing the foaming material into a two-time compression molding foaming mold, setting the pressure at a normal pressure state, setting the temperature at 230 ℃, locking the gas for 20min, opening the mold, releasing the pressure, performing the second compression molding foaming, and cooling and shaping to obtain 119kg/m 3 MXD6 foamed article.
Example 10
The method for preparing the nylon foaming product comprises the following steps:
(1) Will contain 100 parts by weight of PA612, 2 parts by weight of HDI, 0.5 part by weight of SiO 2 Adding components including 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 through a die head, and cooling and shaping to obtain a PA612 plate blank with the width of 12mm and the width of 210 mm;
(2) Placing the obtained nylon slab in 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 a range of 25MPa, setting the temperature at 265 ℃, and injecting 2 parts by weight of CO 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 a die, releasing pressure, nucleating cells, and expanding the gas to obtain a PA612 pre-foaming material with the foaming multiplying power of 4 times;
(3) Taking out the foaming material from the primary compression molding die, placing the foaming material into a secondary compression molding foaming die, setting the pressure at a normal pressure state, setting the temperature at 265 ℃, locking the gas for 20min, opening the die, releasing the pressure, performing secondary compression molding foaming, and cooling and shaping to obtain 115kg/m 3 PA612 foamed article.
Comparative example
The method for preparing the nylon foaming product comprises the following steps:
(1) Adding the components including 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, and cooling and shaping to obtain a PA6 plate blank with the width of 12mm and the width of 210 mm;
(2) Placing nylon plate embryo into a foaming cavity with a specific shape between an upper half mould and a lower half mould of a flat press, respectively setting the pressure to 10MPa, the temperature to 220 ℃, and injecting 2 parts by weight of CO from an air inlet pipe after the materials are melted 2 Locking gas for 20min, opening the mould for pressure relief, expanding the gas, cooling and shaping to obtain the density of 110kg/m 3 PA6/TPAE foamed article of (c).
Evaluation:
1. the nylon foamed articles obtained in examples 1 to 10 and comparative examples 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
Flexural strength: GB/T8812-88
Tensile strength: ASTM C297
Compressive strength: ISO 844
Closed porosity: GB/T10799-2008
The nylon foamed articles obtained in examples 1 to 10 and comparative example were tested and the results are shown in Table 1.
TABLE 1 Performance data for Nylon foam articles obtained in examples 1-10 and comparative example
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means 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 present invention. In this specification, schematic representations of the above terms are not necessarily directed 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, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (6)
1. A method for preparing a nylon compression molding foaming material, which is characterized by comprising the following steps:
(1) Mixing nylon, a chain extender, a nucleating agent and an antioxidant, and then carrying out melt blending extrusion to obtain a nylon slab;
(2) Heating the nylon slab in a foaming cavity of a one-time compression molding die, injecting high-pressure supercritical fluid into the foaming cavity after the nylon slab is melted, so that the high-pressure supercritical fluid is diffused and dissolved in the nylon slab, and opening the die to release pressure after locking the high-pressure supercritical fluid for a first preset time so as to obtain a nylon pre-foaming material;
(3) Placing the nylon pre-foaming material into a foaming cavity of a secondary compression molding die, and opening the die and releasing pressure after locking gas for a second preset time under normal pressure and heating so as to obtain a nylon compression molding foaming material;
in the step (2), placing the nylon slab in a foaming cavity of the primary compression molding die, and melting the nylon slab at the temperature of 210-270 ℃ under the pressure of 6-15 MPa;
in the step (3), the nylon pre-foaming material is placed in a foaming cavity of the secondary compression molding die, and gas is locked at the temperature of 210-270 ℃ under normal pressure;
in the step (1), the mass ratio of the nylon to the chain extender to the nucleating agent to the antioxidant is 100: (0.5-2): (0.5-2): (0.5-1);
in step (1), the nylon comprises at least one of PA6, PA66, PA610, PA612, PA12, PA1212, PA56, TPAE, and MXD 6;
in step (1), the chain extender comprises at least one of a homoisocyanate, a polyfunctional epoxy resin, and triglycidyl isocyanurate;
in step (1), the nucleating agent comprises at least one of silicon dioxide, talcum powder, sodium montanate and magnesium oxide;
in step (1), the antioxidant comprises at least one of antioxidant 1098, antioxidant 1216, antioxidant 626, and antioxidant S9228;
in the step (1), at least one of a high-temperature-resistant lubricant and a compatilizer is further added, wherein the high-temperature-resistant lubricant is used in an amount of 0.2-0.5 parts by weight and the compatilizer is used in an amount of 0.5-1 parts by weight based on 100 parts by weight of the nylon material;
the high temperature resistant lubricant comprises at least one of polyester wax, montan acid wax, and PETs;
the compatilizer comprises at least one of MA-SEBS, SMA and POE-g-MAH.
2. The method of claim 1, wherein in step (1), the nylon slabs have a thickness of 10 to 20mm and a width of 200 to 250mm.
3. The method of claim 1, wherein the first predetermined time is 10-25 minutes;
optionally, the foaming ratio of the nylon pre-foaming material is 2-5 times.
4. The method of claim 1, wherein in step (2), the high pressure supercritical fluid comprises cyclopentane, N 2 And CO 2 And the high-pressure supercritical fluid is used in an amount of 1.5 to 3 parts by weight based on 100 parts by weight of the nylon.
5. The method of claim 1, wherein the second predetermined time is 10-30 min.
6. A nylon compression molding foam material, characterized in that the nylon compression molding foam material is prepared by the method of any one of claims 1-5.
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