CN105601977A - Modified polyamide-6 microcellular foam material and preparation method thereof - Google Patents
Modified polyamide-6 microcellular foam material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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- 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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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
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- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
The invention discloses a modified polyamide-6 microcellular foam material and a preparation method thereof. The preparation method of the modified polyamide-6 microcellular foam material includes the steps of (1), premixing polyamide-6, a chain extender and an antioxidant so as to obtain a premixed material; (2), subjecting the premixed material to melt blending, extrusion pelletization and drying so as to obtain a modified base material; (3), placing the modified base material in supercritical CO2 to be subjected to swelling and osmosis at a T1 temperature, decreasing the temperature to a foaming temperature T2, holding, relieving pressure to normal pressure and cooling so as to obtain the modified polyamide-6 microcellular foam material, wherein T1 ranges from 230 DEG C to 250 DEG C, and T2 ranges from 205 DEG C to 225 DEG C. The prepared modified polyamide-6 microcellular foam material is small in aperture size and large in cell density, the expanded volume of the modified polyamide-6 microcellular foam material is 3.0-20 times of the volume of raw materials, the melt strength of the modified base material is high, and accordingly the modified polyamide-6 microcellular foam material has promising application prospect in the field of automobile materials.
Description
Technical field
The present invention relates to Material Field, relate in particular to a kind of modified polyamide-6 material and preparation method thereof.
Background technology
Polyamide (polyamide, PA), is commonly called as nylon, not only has good mechanical property and betterElectrical property, also there are a series of excellent properties such as wear-resisting, resistance to solvent, corrosion-resistant, oil resistant, now send outThe macromolecular material that generate is output maximum in five large-engineering plastics, purposes is the widest, product is maximum, and gatherAcid amides-6 (PA6) conduct wherein most important kind is widely used in automobile, machinery, chemical industry, electricityThe fields such as device, building, packaging. Automobile is the market of the important and rapid growth of plastics, is also polyamide-6Maximum application market, current lightweight is the inexorable trend of automobile industry development, and automotive material light weightChange is to realize the light-weighted effective way of car load. Foam cellular plastic is a kind of novel taking gas as fillerComposite, is introduced in the technology of preparing of automotive material, ensureing under the prerequisite of material key property,Significantly alleviate product weight, be conducive to automobile lightweight, there are wide market prospects. But,Due to polyamide-6th, a kind of strand is the semi-crystalline polymer of linear structure, in molten state processIn conventionally show lower melt strength, being difficult to resist the violent stretching of bearing in abscess growth course shouldPower, the abscess having generated also can further break and merging, thereby can not get desirable polyamide-6Micro-foaming material. Domestic Shandong becomes happy and auspicious ancestor's victory man to wait people [ChengxiangLuetal.ChemicalModificationofPolyamide6ByChainExtensionwithTerephthaloyl-biscaprolactam，JournalofMacromolecularScience，PartB：Physics，2010，50：2，350-362；ZongShengnanetal.ModificationEffectsComparisonofBisoxazolineandEpoxyTypeChainExtenderonNylon6，EngineeringPlasticsApplication, 2014,42 (12), 29-33] chemical chain extension to polyamide-6Done system research, prepared high-viscosity polyamide-6, its molecular weight improves, and mechanical property is improved; StateOuter Lih-ShengTurng [the Lih-ShengTurngetal.Microstructureand of seminarCrystallographyinMicrocellularInjectionMoldedPloyamide-6Nanocomposite andNeatResin，PolymerEngineeringandScience，2005，45，52-61；Lih-ShengTurngetal.StudyofInjectionMoldedMicrocellularPloyamide-6Nanocomposites, PolymerEngineeringandScience, 2004,44,673-686] to polyamidesMicro-foaming of amine-6 nano composite material has been carried out large quantity research and has successfully been obtained mechanical property excellencePolyamide-6 microcellular foam; Zotefoamsplc successfully realizes has high temperature resistant, oil resistant, goodThe contour performance of chemical stability polyamide-6 foamed plastics (Commercially producing N), but itsFor cross-linked polymer, cannot recycling; Chinese patent CN103540123A is by epoxy functionalizedThe chain extender of changing and the chain extender composition of acid absorbent are used for reclaiming modified nylon, and its modified effect is brightAobvious, with low cost.
In the time that producing, foamed gas whether there is chemical change as criteria for classification, traditional polymer foamingMethod can be divided into physical blowing method and chemical blowing process conventionally. Though the application of chemical blowing process is very generalTime, but along with the raising to plastics recovery and product properties cost ratio etc. require after environmental protection, consumption,With CO2、N2, the physical blowing agent such as butane and pentane is that main physical blowing method earns widespread respect. EspeciallyIt entered after the nineties in last century, with supercritical fluid (CO2、N2) etc. be physical blowing agent, carry outPolymer micro foaming technology has obtained develop rapidly. Adopt supercritical CO2As physical blowingAgent, not only source is abundant, low price, environmental friendliness, meets the environmental requirement of increasingly stringent, andSupercritical CO2Saturation time in polymer is short, and nucleation rate is high, the foamed plastics abscess obtainingSize is less, and hole density is larger.
So far, although most plastics can pass through the rational physics of employing or CBAMethod successfully foams, but for the foaming process of polyamide-6, still faces a lot of challenges, whereinOne of be exactly melt strength low problem in polyamide-6 under high temperature, abscess cannot be given birth to smoothly in meltProgress and occur breaking of cell wall and subsiding of abscess. Therefore, raising foaming polyamide-6 base-materialMelt strength is the prerequisite that polyamide-6 success is foamed to prevent that abscess from breaking, and chemical chain extension method is due to itTechnological process is easy, react the advantage such as fast, effective is considered to improve polyamide-6 melt viscosity and moltenThe important means of body intensity.
Summary of the invention
Object of the present invention is difficult to because its melt strength is low in order to overcome existing polyamide-6 exactlyPrepare the defect of microcellular plastics, and a kind of modified polyamide-6 microcellular foam material and preparation thereof are providedMethod. Preparation method of the present invention is passable by introduce long chain branched on the molecular backbone of polyamide-6Effectively improve molecular entanglement probability in polymer melt, thereby improve its melt strength, and then utilizeModified polyamide-6 base-material of this high fondant-strength carries out supercritical CO2Melt foaming, the micropore of preparingThe aperture size of expanded material is little, and hole density is large.
The present invention solves the problems of the technologies described above by the following technical programs.
The preparation method who the invention provides a kind of modified polyamide-6 microcellular foam material, it comprises followingStep:
(1) polyamide-6, chain extender and antioxidant are carried out to premix, obtain premix material;
(2) premix material is carried out to melt blending, then extruding pelletization, dry, obtains modified base material;
(3) modified base material is placed in to supercritical CO2In, at T1Under temperature conditions, carry out swelling infiltration,Then be cooled to blowing temperature T2, insulation, then pressure release is to normal pressure, and cooling, can obtain modification polyamidesAmine-6 microcellular foam material; T1Be 230～250 DEG C, T2It is 205～225 DEG C.
Wherein, the mass ratio of described polyamide-6, chain extender and antioxidant is preferably 100:(0.1～10): (0.3～0.8) is more preferably 100: (0.883～5): (0.4～0.6).
Wherein, described polyamide-6 can be conventional commercialization polyamide-6 product using in this area, thisInvention preferably adopts purchased from commercialization polyamide-6 in BASF Co., Ltd.
Wherein, described chain extender can be the conventional various polyfunctional group chain extenders that use in this area, thisBright preferably 2,2 '-bis-(2-oxazoline) (being BOZ), a phenyl-diformyl dicaprolactam (being IBC) andProduct grade is one or more in KL-E4370 chain extender (being EP).
Wherein, described antioxidant can be the conventional various antioxidants that use in this area, and the present invention is preferredBe four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, be commonly called as antioxidant 1010.
Wherein, before polyamide-6, chain extender and the antioxidant of step (1) carry out premix,Polyamide-6, chain extender and antioxidant are dried respectively goodly; Described dry temperature preferablyBe 80～90 DEG C, the dry time is preferably 12～14 hours.
In step (1), described premix generally refers to each component mixed fully, comprise butBe not limited to realize by modes such as stirrings.
In step (2), described melt blending is preferably realized on Haake torque rheometer, instituteThe rotor speed of the Haake torque rheometer of stating is preferably 45～55 revs/min, and described melting altogetherMixed temperature is preferably 230～250 DEG C.
Preferably, the crystallization temperature of the modified base material obtaining in step (2) is 190～200 DEG C, under low frequencyMelt complex viscosity be 800～60000PaS (tested by dynamic shear rheological, 240 DEG C of probe temperatures,Test frequency 0.1～100rad/s), testing result is as shown in Figure 6.
In step (3), the pressure of described swelling infiltration is preferably 15～25MPa.
In step (3), the time of described swelling infiltration is preferably 20～30 minutes; Described guarantorThe time of temperature is preferably 10～20 minutes.
In step (3), described T1Be preferably 235～240 DEG C, described T2Be preferably210～220℃。
In step (3), described supercritical CO2Can be the supercritical CO of this area routine2, generalRefer to: temperature is the CO higher than 7.38MPa higher than 31.1 DEG C, pressure2Fluid, comprises supercriticalityCO2, for example, temperature is the CO that 210 DEG C, pressure are 15MPa2Fluid.
In step (3), described pressure release refers to quick pressure releasing, by the high pressure CO in supercriticality2By decompressor, as pressure reduction control valve, moment step-down rapidly; In the present invention, the speed of described pressure releaseRate is preferably 100～400MPa/s.
In step (3), blowing temperature T2Selection principle as follows: be to ensure polyamide-6 strand toolsThere are enough locomitivities, can be in foaming, the melt viscosity of polyamide-6 and melt strength are againBe enough to maintain the form of abscess; CO simultaneously2At this temperature, also can reach enough degree of supersaturations.
In step (3), described is cooling preferably for being cooled to 0～25 DEG C.
The present invention also provides a kind of modified polyamide-6 microporous foam material being made by above-mentioned preparation methodMaterial.
The volume of modified polyamide-6 microcellular foam material obtaining is under these conditions compared with raw material (polyamide-6) 3.0～20 times of volumetric expansions, and the aperture of expanded material be 1.5～15 μ m (be preferably 1.5～10 μ m),Hole density is (1.5～25) × 109Individual/cm3。
The present invention carries out chain extending reaction to obtain high fondant-strength by chemical chain extender and polyamide-6 raw materialPolyamide-6 modified materials, then, taking it as base-material, utilize supercritical CO2Under higher temperature conditionsSwelling infiltration is carried out in polyamide-6, make CO2Can fully be dissolved in the matrix of polyamide-6, at heightUnder temperature condition, supercritical CO2Diffusion rate in polyamide-6 is faster, can eliminate again simultaneouslyAll crystalline regions in the matrix of polyamide-6, keep, after certain hour, reducing rapidly temperature, make polyamide-6Melt strength increases, then makes the supercritical CO in the matrix of polyamide-6 by quick pressure releasing2Reach satietyAnd state, thereby nucleation foaming obtains modified polyamide-6 microcellular foam material.
Meeting on the basis of this area general knowledge, above-mentioned each optimum condition, can be combined, i.e. get Ben FaBright each preferred embodiments.
Agents useful for same of the present invention and raw material be commercially available obtaining all.
Positive progressive effect of the present invention is:
(1) the present invention is taking polyamide-6 of chemical chain extension modification as raw material, by controlling foaming processKey variables, have prepared polyamide-6 expanded material with microcellular structure.
(2) aperture size of the microcellular foam material that the present invention makes is little, and hole density is large.
(3) volume of the microcellular foam material that the present invention makes compared with raw material volumetric expansion up to 3.0～20 times,Have a wide range of applications in automotive material field.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the sample section of embodiment 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of the sample section of embodiment 2.
Fig. 3 is the scanning electron microscope (SEM) photograph of the sample section of embodiment 3.
Fig. 4 is the scanning electron microscope (SEM) photograph of the sample section of embodiment 4.
Fig. 5 is the scanning electron microscope (SEM) photograph of the sample section of embodiment 5.
Fig. 6 is the performance of DSR figure of raw material and modified base material.
Detailed description of the invention
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention toAmong described scope of embodiments. The experimental technique of unreceipted actual conditions in the following example, according to oftenRule method and condition, or select according to catalogue.
Analysis test method is as follows:
Scanning electron microscope analysis
Adopt SEM (SEM) to analyze the tangent plane of foamed polymer material sample,To investigate hole density and the pore size of foamed polymer material. Analytical instrument is Japanese JOEL companyJSM-6360LV type ESEM, has indicated multiplication factor and size in figure. Can be analyzed by SEM photoExpanded material average pore size and cell density. From SEM photo, add up micropore number n (> 100), reallyDetermine photo area (cm2)，ρ0For the density of the sample that do not foam, ρfFor the density of foaming sample, hole densityThe estimation of employing following formula:
Business-like polyamide-6 are purchased from BASF Co., Ltd.
Chain extender KL-E4370 is purchased from Shanxi Province petrochemical industry research institute (Co., Ltd).
Embodiment 1
Business-like polyamide-6, chain extender 2,2 '-bis-(2-oxazoline) and antioxidant 1010 are at 85 DEG C of barsVacuum drying 12 hours under part, and with the abundant premix of following mass fraction:
Polyamide-6100 part
0.883 part of chain extender
0.5 part, antioxidant
The material of premix, through Haake torque rheometer melt blending, is prepared modified polyamide-6 material.The rotor speed of Haake torque rheometer is 50 rpms, and melt temperature is 240 DEG C. Extrudate warpGranulation, is dried and obtains modified polyamide-6 base-material, for follow-up analysis and foaming.
Dry above-mentioned modified polyamide-6 base-material is placed in autoclave and sealing, wherein modification polyamidesAmine-6 binder volume is not more than one of percentage of autoclave volume, to guarantee that it has enough foaming spaces to send outSoak type. Use subsequently low pressure CO2Purge autoclave 3 times by clean air displacement in still, by autoclave literTemperature to 235 DEG C, boost to 25MPa, swelling 20 minutes to guarantee complete melting and the CO of polyamide-62Completely saturated in the matrix of polyamide-6; Then be cooled to 215 DEG C, then maintain 10 minutes to reachNew equilibrium state. By pressure reduction control valve, still internal pressure was down to often with the speed moment of 300MPa/sPress, to induce abscess nucleation, growth. Foaming sample is cooled to 0 DEG C, makes abscess sizing, it is cutFace carries out scanning analysis. Aperture 2.0～15.0 μ m of polyamide-6 foaming sample as shown in Figure 1, hole density3.6×109Individual/cm3, expanded material expands approximately 3.1 times compared with volume of raw material. Expanded material is broken without cell wallSplitting the phenomenon of subsiding with abscess occurs.
Embodiment 2
Acyl in business-like polyamide-6, chain extender 2,2 '-bis-(2-oxazoline) and a phenyl-diformyl two are ownThe vacuum drying 12 hours under 85 DEG C of conditions of amine and antioxidant 1010, and fully pre-with following mass fractionMixed.
The material of premix, through Haake torque rheometer melt blending, is prepared modified polyamide-6 material.The rotor speed of Haake torque rheometer is 50 rpms, and melt temperature is 240 DEG C. Extrudate warpGranulation, the dry base-material that is improved, for follow-up analysis and foaming.
Dry above-mentioned modified polyamide-6 base-material is placed in autoclave and sealing, wherein modification polyamidesAmine-6 binder volume is not more than one of percentage of autoclave volume, to guarantee that it has enough foaming spaces to send outSoak type. Use subsequently low pressure CO2Purge autoclave 3 times by clean air displacement in still, by autoclave literTemperature to 235 DEG C, boost to 25MPa, swelling 20 minutes to guarantee complete melting and the CO of polyamide-62Completely saturated in the matrix of polyamide-6; Then be cooled to 215 DEG C, then maintain 20 minutes to reachNew equilibrium state. By pressure reduction control valve, still internal pressure was down to often with the speed moment of 200MPa/sPress, to induce abscess nucleation, growth. Foaming sample is cooled to 0 DEG C, makes abscess sizing, it is cutFace carries out scanning analysis. Aperture 1.5～10.0 μ m of polyamide-6 foaming sample as shown in Figure 2, hole density 2.5×1010Individual/cm3, expanded material expands approximately 10.5 times compared with volume of raw material. Expanded material is without cell wallBreak and the abscess phenomenon of subsiding occurs.
Embodiment 3:
Business-like polyamide-6, chain extender KL-E4370 and antioxidant 1010 are true under 85 DEG C of conditionsEmpty dry 12 hours, and with the abundant premix of following mass fraction.
Polyamide-6100 part
5 parts of chain extenders
0.6 part, antioxidant
The material of premix, through Haake torque rheometer melt blending, is prepared modified polyamide-6 material.The rotor speed of Haake torque rheometer is 50 rpms, and melt temperature is 240 DEG C. Extrudate warpGranulation, is dried and obtains modified base material, for follow-up analysis and foaming.
Dry above-mentioned modified polyamide-6 base-material is placed in autoclave and sealing, wherein modification polyamidesAmine-6 binder volume is not more than one of percentage of autoclave volume, to guarantee that it has enough foaming spaces to send outSoak type. Use subsequently low pressure CO2Purge autoclave 3 times by clean air displacement in still, by autoclave literTemperature to 240 DEG C, boost to 15MPa, swelling 30 minutes to guarantee complete melting and the CO of polyamide-62Completely saturated in the matrix of polyamide-6; Then be cooled to 210 DEG C, then maintain 10 minutes to reachNew equilibrium state. By pressure reduction control valve, still internal pressure was down to often with the speed moment of 400MPa/sPress, to induce abscess nucleation, growth. Foaming sample is cooled to 25 DEG C, makes abscess sizing, it is cutFace carries out scanning analysis. Aperture 8.5～13.0 μ m of polyamide-6 foaming sample as shown in Figure 3, hole density2.0×109Individual/cm3, expanded material expands approximately 14.5 times compared with volume of raw material. Expanded material is without cell wallBreak and the abscess phenomenon of subsiding occurs.
Embodiment 4:
Business-like polyamide-6, chain extender KL-E4370 and antioxidant 1010 are true under 85 DEG C of conditionsEmpty dry 12 hours, and with the abundant premix of following mass fraction.
Polyamide-6100 part
5 parts of chain extenders
0.5 part, antioxidant
The material of premix, through Haake torque rheometer melt blending, is prepared modified polyamide-6 material.The rotor speed of Haake torque rheometer is 50 rpms, and melt temperature is 240 DEG C. Extrudate warpGranulation, is dried and obtains modified base material, for follow-up analysis and foaming.
Dry above-mentioned modified polyamide-6 base-material is placed in autoclave and sealing, wherein modification polyamidesAmine-6 binder volume is not more than one of percentage of autoclave volume, to guarantee that it has enough foaming spaces to send outSoak type. Use subsequently low pressure CO2Purge autoclave 3 times by clean air displacement in still, by autoclave literTemperature to 240 DEG C, boost to 25MPa, swelling 30 minutes to guarantee complete melting and the CO of polyamide-62Completely saturated in the matrix of polyamide-6; Then be cooled to 220 DEG C, then maintain 20 minutes to reachNew equilibrium state. By pressure reduction control valve, still internal pressure was down to often with the speed moment of 300MPa/sPress, to induce abscess nucleation, growth. Foaming sample is cooled to 20 DEG C, makes abscess sizing, it is cutFace carries out scanning analysis. Aperture 5.5～7.0 μ m of polyamide-6 foaming sample as shown in Figure 4, hole density4.3×109Individual/cm3, expanded material expands approximately 12.7 times compared with volume of raw material. Expanded material is without cell wallBreak and the abscess phenomenon of subsiding occurs.
Embodiment 5:
Business-like polyamide-6, chain extender KL-E4370 and antioxidant 1010 are true under 85 DEG C of conditionsEmpty dry 12 hours, and with the abundant premix of following mass fraction.
Polyamide-6100 part
5 parts of chain extenders
0.4 part, antioxidant
The material of premix, through Haake torque rheometer melt blending, is prepared modified polyamide-6 material.The rotor speed of Haake torque rheometer is 50 rpms, and melt temperature is 240 DEG C. Extrudate warpGranulation, is dried and obtains modified base material, for follow-up analysis and foaming.
Dry above-mentioned modified polyamide-6 base-material is placed in autoclave and sealing, wherein modification polyamidesAmine-6 binder volume is not more than one of percentage of autoclave volume, to guarantee that it has enough foaming spaces to send outSoak type. Use subsequently low pressure CO2Purge autoclave 3 times by clean air displacement in still, by autoclave literTemperature to 240 DEG C, boost to 20MPa, swelling 30 minutes to guarantee complete melting and the CO of polyamide-62Completely saturated in the matrix of polyamide-6; Then be cooled to 215 DEG C, then maintain 10 minutes to reachNew equilibrium state. By pressure reduction control valve, still internal pressure was down to often with the speed moment of 400MPa/sPress, to induce abscess nucleation, growth. Foaming sample is cooled to 20 DEG C, makes abscess sizing, it is cutFace carries out scanning analysis. Aperture 8.5～10.0 μ m of polyamide-6 foaming sample as shown in Figure 5, hole density2.2×109Individual/cm3, expanded material expands approximately 14.0 times compared with volume of raw material. Expanded material is without cell wallBreak and the abscess phenomenon of subsiding occurs.
Fig. 6 is the performance of DSR figure of polyamide-6 raw material and modified polyamide-6 base-material, in figureThe modified base material of the corresponding embodiment 1 of BOZ modified polyamide-6 base-material, IBC&BOZ modified polyamide-6The modified base material of the corresponding embodiment 2 of base-material, the modification of the corresponding embodiment 3 of EP modified polyamide-6 base-materialBase-material. As can be seen from the figure,, than polyamide-6 raw material, the complex viscosity of modified base material obtains brightAobvious raising, and present to some extent shear shinning characteristic, show that polyamide-6 raw material is through chemical modificationRear its melt strength gets a promotion, the especially viscoplasticity of EP modified polyamide-6 base-material in embodiment 3Performance the best. The result of embodiment 4 and embodiment 5 is with embodiment 3.
Claims (10)
1. a preparation method for modified polyamide-6 microcellular foam material, it comprises the steps:
(1) polyamide-6, chain extender and antioxidant are carried out to premix, obtain premix material;
(2) premix material is carried out to melt blending, then extruding pelletization, dry, obtains modified base material;
(3) modified base material is placed in to supercritical CO2In, at T1Under temperature conditions, carry out swelling infiltration,Then be cooled to blowing temperature T2, insulation, then pressure release is to normal pressure, and cooling, can obtain modification polyamidesAmine-6 microcellular foam material; T1Be 230～250 DEG C, T2It is 205～225 DEG C.
2. preparation method as claimed in claim 1, is characterized in that, described polyamide-6, expansionThe mass ratio of chain agent and antioxidant is 100: (0.1～10): (0.3～0.8) is preferably 100:(0.883～5)∶(0.4～0.6)。
3. preparation method as claimed in claim 1, is characterized in that, described chain extender is 2,2 '-Two (2-oxazolines), a phenyl-diformyl dicaprolactam and product grade are one in KL-E4370 chain extenderKind or multiple;
Described antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester;
Before polyamide-6, chain extender and the antioxidant of step (1) carry out premix, by polyamide-6,Chain extender and antioxidant are dried respectively; Described dry temperature is preferably 80～90 DEG C, dryTime be preferably 12～14 hours.
4. preparation method as claimed in claim 1, is characterized in that, in step (2), describedMelt blending is realized on Haake torque rheometer, the rotor speed of described Haake torque rheometerBe 45～55 revs/min, the temperature of described melt blending is 230～250 DEG C;
The crystallization temperature of the modified base material obtaining in step (2) is 190～200 DEG C, and melt complex viscosity is800～60000Pa·S。
5. preparation method as claimed in claim 1, is characterized in that, in step (3), describedThe pressure of swelling infiltration is 15～25MPa;
In step (3), the time of described swelling infiltration is 20～30 minutes; Described insulation timeBetween be 10～20 minutes.
6. preparation method as claimed in claim 1, is characterized in that, in step (3), describedT1Be 235～240 DEG C, described T2It is 210～220 DEG C.
7. preparation method as claimed in claim 1, is characterized in that, in step (3), describedThe speed of pressure release is 100～400MPa/s.
8. preparation method as claimed in claim 1, is characterized in that, in step (3), describedBe cooled to and be cooled to 0～25 DEG C.
9. the modification polyamides being made by the preparation method as described in any one in claim 1～8Amine-6 microcellular foam material.
10. modified polyamide-6 as claimed in claim 9 microcellular foam material, is characterized in that, instituteThe aperture of modified polyamide-6 microcellular foam material of stating is 1.5～15 μ m, and hole density is (1.5～25) × 109Individual/cm3。
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