CN114106506A - PP/PA6 porous composite material and preparation method thereof - Google Patents

PP/PA6 porous composite material and preparation method thereof Download PDF

Info

Publication number
CN114106506A
CN114106506A CN202111613741.3A CN202111613741A CN114106506A CN 114106506 A CN114106506 A CN 114106506A CN 202111613741 A CN202111613741 A CN 202111613741A CN 114106506 A CN114106506 A CN 114106506A
Authority
CN
China
Prior art keywords
composite material
preparation
modified
supercritical
porous composite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202111613741.3A
Other languages
Chinese (zh)
Other versions
CN114106506B (en
Inventor
肖晖
黄伟
王经逸
林鸿裕
詹迎旭
吕明旭
刘东斌
徐炜斌
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Liming Vocational University
Original Assignee
Liming Vocational University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Liming Vocational University filed Critical Liming Vocational University
Priority to CN202111613741.3A priority Critical patent/CN114106506B/en
Publication of CN114106506A publication Critical patent/CN114106506A/en
Application granted granted Critical
Publication of CN114106506B publication Critical patent/CN114106506B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/08—Supercritical fluid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/14—Copolymers of propene
    • 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
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention discloses a PP/PA6 porous composite material which comprises the following raw materials in parts by weight: 50-70 parts of PP, 30-50 parts of PA6 resin, 5-8 parts of epoxy chain extender, 3-7 parts of compatilizer, 20-35 parts of modified AF fiber, 0.4-0.6 part of foam stabilizer and 3-15 parts of modified nano nucleating agent. The invention also discloses a preparation method of the PP/PA6 porous composite material, which comprises the steps of sequentially carrying out melting, extrusion granulation and gas-assisted mould opening and closing microcellular foaming injection molding on the PP/PA6 composite material to obtain the composite material, wherein the prepared PP/PA6 porous composite material has good melt formability, high foaming multiplying power, high closed cell rate and uniform and moderate size; the tensile strength is high, and the comprehensive mechanical property is good; low density, light weight and good use performance.

Description

PP/PA6 porous composite material and preparation method thereof
Technical Field
The invention relates to the technical field of foamed plastics, in particular to a PP/PA6 porous composite material and a preparation method thereof.
Background
The polypropylene (PP) has excellent comprehensive performance, but has poor melt strength and narrow foaming temperature range in the processing process, so that the application of the PP in the field of injection micro-foaming is limited; nylon 6(PA6) has excellent molding and processing properties, but has high water absorption, so that the dimensional stability and mechanical properties of products are poor. The composite material prepared by blending PP and PA6 is complementary in performance, can exert excellent performance of the material, achieves the aim of toughening PP, improves the wear resistance and impact resistance of the PP, and simultaneously reduces the water absorption rate and material cost of PA 6.
Microcellular foaming requires that the cell structure size is controlled at the micron or even submicron level, and the obtained foam material has better strength and performance. The nano particles play a nucleating role in the foaming of the PP/PA6 composite material, so that heterogeneous nucleation of the PP/PA6 composite material is dominant. However, the premise of good cell morphology is that the dispersibility of the nanoparticles is good, and only under the condition of good dispersibility, the material can obtain a uniform cell structure with large density and small size. In addition, the mechanical properties and the service performance of the foamed composite material such as tensile strength, tear strength and the like are poor, and the further development of the PP/PA6 foamed material is limited to a certain extent.
Disclosure of Invention
The invention aims to provide a PP/PA6 porous composite material which has the characteristics of excellent mechanical strength, sound insulation, heat insulation, impact resistance and the like and can be widely applied to the fields of food packaging, aerospace, automobile manufacturing, marine transportation, wind power generation, biological scaffolds and the like.
The invention aims to provide a preparation method of a PP/PA6 porous composite material, which solves the problem that the existing foaming process has poor foam cell nucleation effect and causes poor performance of the foaming material.
In order to achieve the above purpose, the solution of the invention is:
the PP/PA6 porous composite material comprises the following raw materials in parts by weight:
Figure BDA0003435861980000021
the modified AF fiber is obtained by sequentially carrying out oil removal and Friedel-crafts reaction treatment, and the modified nano nucleating agent is nano silicon dioxide treated by a silane coupling agent or nano calcium carbonate treated by the silane coupling agent.
The PP is block copolymerization PP or random copolymerization PP, the epoxy chain extender is one or more of ADR-4468, ADR-4368 and KL-E4370, the compatilizer is one of maleic anhydride grafted polypropylene (PP-g-MAH), maleic anhydride grafted styrene-butadiene copolymer (SEBS-g-MAH) and maleic anhydride grafted ethylene-olefin copolymer (POE-g-MAH), the cell stabilizer is one or two of isobutyl polymethacrylate and n-butyl polymethacrylate, and the silane coupling agent is one of KH550, KH570 and KH 602.
A preparation method of a PP/PA6 porous composite material comprises the following steps:
step 1, drying PP, PA6 and a nano nucleating agent for later use, wherein the nano nucleating agent is nano silicon dioxide or nano calcium carbonate;
and 2, carrying out modification treatment on the AF fiber:
oil removal operation: soaking AF fibers in sodium dodecyl benzene sulfonate water solution, performing ultrasonic treatment for 0.5-1 h, filtering the obtained mixture through a nano-filtration membrane, washing for 3-5 times, and drying for later use;
the Friedel-crafts reaction operation is as follows: soaking the deoiled AF fiber in epoxy chloropropane, vacuumizing, filling nitrogen, repeating for many times, keeping inert atmosphere, keeping condensation reflux of a reaction system at 110-130 ℃ for 0.5-1 h, and adding AlCl into the system for many times3Reacting for 8-10 h to obtain a modified AF crude product;
and (3) purification operation: then washing the modified AF crude product with ethanol, treating the modified AF crude product in NaOH solution at 50-70 ℃ for 1-2 hours, washing the modified AF crude product with distilled water, drying the modified AF crude product to obtain modified AF fibers, and sealing the modified AF fibers for later use;
and 3, modifying the dried nano nucleating agent: fully mixing a silane coupling agent and absolute ethyl alcohol in a volume ratio of 1: 3-1: 5 under an ultrasonic condition to obtain a mixed solution, and mixing the mixed solution and a nano nucleating agent in a high-speed mixer for 20-30 min to obtain a modified nano nucleating agent;
step 4, stirring PP, PA6, an epoxy chain extender, a compatilizer, modified AF fibers, a cell stabilizer and a modified nano nucleating agent into powder at a high speed according to the formula proportion to obtain premixed resin;
step 5, feeding the premixed resin material into a double-screw extruder for melting, blending, extruding, granulating and drying to obtain mixed resin plastic;
step 6, adding mixed resin plastic and supercritical CO into a charging barrel of an injection molding machine2Fluid production to Polymer/supercritical CO2Homogeneous melt;
step 7, finally adopting a gas-assisted open-close die microcellular foaming injection molding process to carry out the step 6 on the obtained polymer/supercritical CO2Homogeneous melt processAnd carrying out secondary foaming to obtain the PP/PA6 porous composite material.
In the step 1, the nano nucleating agent and the PP are dried for 4 hours in vacuum at 80 ℃, and the PA6 is dried for 4 hours in vacuum at 100 ℃.
In the step 2, the mass usage ratio of the AF fiber to the sodium dodecyl benzene sulfonate melt is 1: 5-1: 15; the AF fiber and AlCl3The mass and dosage ratio of (A) to (B) is 7: 1-10: 1.
In the step 3, the adding amount of the silane coupling agent is 1% of the mass of the nano nucleating agent, and the rotating speed of the high-speed mixer is 100-300 r/min.
In the step 5, the working temperature of the double-screw extruder is 180-230 ℃, the screw rotating speed is 80-140 r/min, the feeding speed is 1.5-3 kg/h, and the drying temperature is 60-100 ℃.
In step 6, the polymer/supercritical CO2The preparation process of the homogeneous melt comprises the following steps: firstly, the mixed resin plastics are heated and melted in a charging barrel of an injection molding machine, and then supercritical CO is injected into the charging barrel2And shearing and mixing the fluid for 2-6 s by using a screw to obtain the polymer/supercritical fluid homogeneous melt.
In step 6, supercritical CO2The dosage of the fluid is 0.5-1.0% of the mass of the mixed resin plastic, and the shearing speed is 60-100 r/min.
In step 7, the secondary foaming operation comprises: closing the injection mold by injecting the polymer/supercritical CO into the cavity of the injection mold2Homogeneous melt, then injecting quantitative high-pressure auxiliary gas, applying short pressure maintaining to the melt, maintaining the high-pressure auxiliary gas, then removing the high-pressure auxiliary gas, and realizing the secondary foaming process of the melt under the pressure relief condition.
In step 7, the high-pressure auxiliary gas is N2Or Ar, the pressure of the high-pressure auxiliary gas is 3 standard atmospheric pressures, and the polymer/supercritical CO is2The injection speed of the homogeneous melt is 40-80 mm/s, the foaming temperature is 190-250 ℃, the pressure of the short pressure maintaining is 40-70 MPa, and the pressure maintaining time is 10-30 s.
After the technical proposal is adopted, the utility model has the advantages that,according to the preparation method of the PP/PA6 porous composite material, the molecular weight and the branching degree of PA6 are improved by using the epoxy chain extender, the PP and the PA6 subjected to chemical chain extension are blended, the melt strength of the composite material is improved under the action of the compatilizer, and supercritical CO can be achieved2Foaming requirements; the PP/PA6 porous composite material with high mechanical property is prepared by matching the cell stabilizer, the modified nano nucleating agent and the modified AF fiber.
The preparation method of the PP/PA6 porous composite material has the following beneficial effects:
(1) firstly, the unmodified PA6 molecular chain is straight-chain, the melt strength is low during melting, the cell wall of the cell is easy to break under the stretching force generated in the growth process of the cell, and sufficient strength is difficult to maintain to restrict the gas to realize the growth of the cell;
(2) secondly, the modified AF fiber is introduced into a PP/PA6 foaming system to be used for reinforcing the composite foaming material, the AF fiber is jointly treated by adopting ultrasonic oscillation and sodium dodecyl benzene sulfonate aqueous solution, grease can be removed completely, and the fibers are not entangled; the deoiled AF fibers are subjected to Friedel-crafts reaction treatment, so that the surface roughness and the surface polarity of the AF fibers are improved, the interface bonding effect of the AF fibers and a resin matrix is effectively improved, the stress can be effectively transmitted to the fibers, and the effect of enhancing the mechanical property of the composite foaming material is achieved;
(3) moreover, the nano nucleating agent has large specific surface area, high surface energy and obvious filling effect, but is easy to generate agglomeration to influence the mechanical property of the composite material; meanwhile, the introduction of the modified nano nucleating agent is beneficial to promoting the nucleation of bubbles, improving the appearance of the bubbles and obtaining a uniform and independent closed-cell foaming structure;
(4) finally, the mixture is used in combinationThe gas-assisted open-close mold microcellular foaming injection molding process, as shown in figure 1, reduces polymer/supercritical CO2The injection amount for filling the mold cavity with homogeneous melt (hereinafter abbreviated as melt) is also reduced, and the bad cells generated in the melt filling process are eliminated, so that the foaming gas is dissolved into the melt again, and the sample is uniformly foamed on the whole after secondary foaming.
Drawings
FIG. 1 is a schematic drawing of the foaming process of the present invention, wherein the process a represents the closing of the injection mold and the process b represents the injection of polymer/supercritical CO2Homogeneous melt, wherein the process c represents injecting high-pressure auxiliary gas, and the process d represents opening the die for secondary foaming;
FIG. 2 is a process flow diagram of the present invention;
FIG. 3 is a scanning electron microscope image of the foamed material prepared by the present invention, in which a) is the composite foamed material prepared in example 3, and b) is the composite foamed material prepared in comparative example 4.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
The PP/PA6 porous composite material comprises the following raw materials in parts by weight:
Figure BDA0003435861980000061
the modified AF fiber is obtained by sequentially carrying out oil removal and Friedel-crafts reaction treatment, and the modified nano nucleating agent is nano silicon dioxide treated by a silane coupling agent or nano calcium carbonate treated by the silane coupling agent.
The PP is block copolymerization PP or random copolymerization PP, the epoxy chain extender is one or more of ADR-4468, ADR-4368 and KL-E4370, the compatilizer is one of maleic anhydride grafted polypropylene (PP-g-MAH), maleic anhydride grafted styrene-butadiene copolymer (SEBS-g-MAH) and maleic anhydride grafted ethylene-olefin copolymer (POE-g-MAH), the cell stabilizer is one or two of isobutyl polymethacrylate and n-butyl polymethacrylate, and the silane coupling agent is one of KH550, KH570 and KH 602.
A preparation method of a PP/PA6 porous composite material comprises the following steps:
step 1, drying PP, PA6 and a nano nucleating agent for later use, wherein the nano nucleating agent is nano silicon dioxide or nano calcium carbonate;
and 2, carrying out modification treatment on the AF fiber:
oil removal operation: soaking AF fibers in sodium dodecyl benzene sulfonate water solution, performing ultrasonic treatment for 0.5-1 h, filtering the obtained mixture through a nano-filtration membrane, washing for 3-5 times, and drying for later use;
the Friedel-crafts reaction operation is as follows: soaking the deoiled AF fiber in epoxy chloropropane, vacuumizing, filling nitrogen, repeating for many times, keeping inert atmosphere, keeping condensation reflux of a reaction system at 110-130 ℃ for 0.5-1 h, and adding AlCl into the system for many times3Reacting for 8-10 h to obtain a modified AF crude product;
and (3) purification operation: then washing the modified AF crude product with ethanol, treating the modified AF crude product in NaOH solution at 50-70 ℃ for 1-2 hours, washing the modified AF crude product with distilled water, drying the modified AF crude product to obtain modified AF fibers, and sealing the modified AF fibers for later use;
and 3, modifying the dried nano nucleating agent: fully mixing a silane coupling agent and absolute ethyl alcohol in a volume ratio of 1: 3-1: 5 under an ultrasonic condition to obtain a mixed solution, and mixing the mixed solution and a nano nucleating agent in a high-speed mixer for 20-30 min to obtain a modified nano nucleating agent;
step 4, stirring PP, PA6, an epoxy chain extender, a compatilizer, modified AF fibers, a cell stabilizer and a modified nano nucleating agent into powder at a high speed according to the formula proportion to obtain premixed resin;
step 5, feeding the premixed resin material into a double-screw extruder for melting, blending, extruding, granulating and drying to obtain mixed resin plastic;
step 6, adding mixed resin plastic into a charging barrel of the injection molding machine and adding the mixed resin plastic into the charging barrelBoundary CO2Fluid production to Polymer/supercritical CO2Homogeneous melt;
step 7, finally adopting a gas-assisted open-close mold microcellular foaming injection molding process to carry out polymer/supercritical CO2And carrying out secondary foaming on the homogeneous melt to obtain the PP/PA6 porous composite material.
In the step 1, the nano nucleating agent and the PP are dried for 4 hours in vacuum at 80 ℃, and the PA6 is dried for 4 hours in vacuum at 100 ℃.
In the step 2, the mass usage ratio of the AF fiber to the sodium dodecyl benzene sulfonate melt is 1: 5-1: 15; the AF fiber and AlCl3The mass and dosage ratio of (A) to (B) is 7: 1-10: 1.
In the step 3, the adding amount of the silane coupling agent is 1% of the mass of the nano nucleating agent, and the rotating speed of the high-speed mixer is 100-300 r/min.
In the step 5, the working temperature of the double-screw extruder is 180-230 ℃, the screw rotating speed is 80-140 r/min, the feeding speed is 1.5-3 kg/h, and the drying temperature is 60-100 ℃.
In step 6, the polymer/supercritical CO2The preparation process of the homogeneous melt comprises the following steps: firstly, the mixed resin plastics are heated and melted in a charging barrel of an injection molding machine, and then supercritical CO is injected into the charging barrel2And shearing and mixing the fluid for 2-6 s by using a screw to obtain the polymer/supercritical fluid homogeneous melt.
In step 6, the supercritical CO2The dosage of the fluid is 0.5-1.0% of the mass of the mixed resin plastic, and the shearing speed is 60-100 r/min.
In step 7, the secondary foaming operation comprises: closing the injection mold by injecting the polymer/supercritical CO into the cavity of the injection mold2Homogeneous melt, then injecting quantitative high-pressure auxiliary gas, applying short pressure maintaining to the melt, maintaining the high-pressure auxiliary gas, then removing the high-pressure auxiliary gas, and realizing the secondary foaming process of the melt under the pressure relief condition.
In step 7, the high-pressure auxiliary gas is N2Or Ar, the pressure of the high-pressure auxiliary gas is 3 targetsQuasi-atmospheric pressure, said polymer/supercritical CO2The injection speed of the homogeneous melt is 40-80 mm/s, the foaming temperature is 190-250 ℃, the pressure of the short pressure maintaining is 40-70 MPa, and the pressure maintaining time is 10-30 s.
The epoxy chain extender, the compatilizer and the silane coupling agent used in the invention are all commercial products.
The prepared PP/PA6 porous composite material is subjected to the following performance tests:
(1) tensile property:
the test is carried out on an Shimadzu universal electronic testing machine according to the IOS1926-2009 standard, the tensile speed is 50mm/min, the specification of a spline is 170.0 multiplied by 10.0 multiplied by 2.5mm, the clamping distance is 115.0 +/-0.1 mm, and the gauge distance is 50.0 +/-0.1 mm. The test takes the average of 3 test results.
(2) And (3) testing the bending strength:
the test is carried out on an Shimadzu universal electronic tester according to the GB/T9341-2000-one standard, the specification of a spline is 80.0 multiplied by 10.0 multiplied by 2.5mm, the radius of a press head of a clamp is 5.0 +/-0.1 mm, and the test speed is 1 mm/min. The test takes the average of 5 test results.
(3) And (3) testing impact strength:
the test is carried out on a Shenzhen Sansi longitudinal and transverse plastic pendulum bob impact tester according to the GB/T1043.1-2008 standard, the specification of a spline is 80.0 multiplied by 10.0 multiplied by 50.0mm, an A-shaped notch is adopted, the depth of the notch is 2.00mm, the included angle is 45 degrees, the experimental mode is a simply supported beam, the nominal energy is 15J, the span is 62.00mm, and the falling angle of the experimental pendulum bob is 150 degrees. The test takes the average of 5 test results.
(4) Density of foamed sample (. rho.)f)：
According to the standard of ASTM D792-00, according to the principle of drainage method, samples of 5 different positions of the porous composite material with the specification of 1.5 multiplied by 1.0cm are measured on a precision electronic balance, and the average value is calculated. The measurement parameter calculation formula is as follows:
ρf＝(a×ρw)/a+w-b)
wherein a is the mass of the foamed sample in the air, b is the mass of the foamed sample immersed in the water together with the metal cap, w is the mass of the metal cap immersed in the water, and ρ iswAs the density of water at room temperature, 1g/mL was taken.
(5) Foaming sample multiplying power:
the foaming ratio reflects the degree of weight reduction of the sample, and the larger the ratio is, the higher the degree of weight reduction is. The foaming sample magnification is the density of the base material/the density of the foaming sample.
(6) Sample average cell diameter and cell density:
and (3) observing the foam appearance of the foaming sample by a scanning electron microscope, carrying out metal spraying treatment on the impact section of the processed and molded impact sample, and observing under the electron microscope. And analyzing the electron microscope image of the cell morphology by using Imag-Pro analysis software, and calculating the average diameter and density of the cells.
Firstly, material preparation
Example 1
A preparation method of a PP/PA6 porous composite material is shown in figure 2 and comprises the following steps:
step 1, firstly, drying nano silicon dioxide and PP for 4 hours at 80 ℃, and drying PA6 for 4 hours at 100 ℃;
and 2, carrying out modification treatment on the AF fiber:
the oil removing operation is as follows: soaking 25g of AF fiber in 150mL of 1% sodium dodecyl benzene sulfonate aqueous solution, performing ultrasonic treatment for 0.5h at the ultrasonic frequency of 80MHz, filtering the obtained mixture by using a nano-filtration membrane, washing for 5 times, and drying at 80 ℃ for 2h for later use;
the Friedel-crafts reaction operation is as follows: soaking the deoiled AF fiber in 50mL of epoxy chloropropane, vacuumizing, filling nitrogen, repeating for three times, keeping inert atmosphere, keeping condensation reflux of a reaction system at 120 ℃ for 0.5h, and adding AlCl into the system for five times3Reacting for 8 hours to obtain a modified AF crude product, AF fibers and AlCl3The mass and dosage ratio of (1) to (9);
and (3) purification operation: then washing the crude modified AF product by ethanol, treating the crude modified AF product in NaOH solution at 60 ℃ for 1.5h, washing the crude modified AF product by distilled water, drying the crude modified AF product at 80 ℃ to obtain modified AF fibers, and sealing the modified AF fibers for later use;
and 3, modifying the dried nano silicon dioxide: fully mixing a silane coupling agent and absolute ethyl alcohol in a volume ratio of 1:4 under an ultrasonic condition to obtain a mixed solution, mixing the mixed solution and a nano nucleating agent in a high-speed mixer at a rotating speed of 100r/min for 20min to obtain modified nano silicon dioxide, wherein the addition amount of the silane coupling agent is 1% of the mass of the nano silicon dioxide;
step 4, stirring 50g of PP (brand F401), 50g of PA6 (brand FG7301NC010), 8g of ADR-4468 (brand basf 4468), 3g of PP-g-MAH (brand P353), 20g of modified AF fiber, 0.4g of polyisobutyl methacrylate and 8g of modified nano-silica into powder at the rotating speed of 250r/min according to the formula proportion to obtain premixed resin;
step 5, feeding the premixed resin material into a double-screw extruder for melting, blending, extruding, granulating and drying at the temperature of 80 ℃ to obtain mixed resin plastic, wherein the working temperature range of the double-screw extruder is 180-230 ℃, the screw rotating speed is 100r/min, and the feeding speed is 1.5 kg/h;
step 6, heating and melting the mixed resin plastic in a charging barrel of an injection molding machine, and injecting supercritical CO accounting for 0.7 percent of the mass of the mixed resin plastic into the charging barrel2Mixing the fluid for 5s at a shearing speed of 100r/min by a screw to obtain a polymer/supercritical fluid homogeneous melt;
step 7, closing the injection mold of the injection molding machine, and injecting the polymer/supercritical CO into the cavity of the injection mold2Homogeneous melt, then injecting quantitative high-pressure auxiliary gas, applying short pressure maintaining to the melt, maintaining the high-pressure auxiliary gas, finally removing the high-pressure auxiliary gas, and realizing the secondary foaming process of the melt under the pressure relief condition;
in step 7, the high-pressure auxiliary gas is N2The pressure of the high pressure assist gas is 3 atm, polymer/supercritical CO2The injection speed of the homogeneous melt is 70mm/s, the foaming temperature is 210 ℃, the pressure of the short pressure maintaining is 60MPa, and the pressure maintaining time is 20 s.
Example 2
The difference from embodiment 1 is that, in this embodiment:
step 4, stirring 70g of PP, 40g of PA6, 6g of ADR-4368, 3g of PP-g-MAH, 20g of modified AF fiber, 0.4g of polyisobutyl methacrylate and 8g of modified nano-silica into powder at the rotating speed of 250r/min according to the formula ratio to obtain premixed resin;
other procedures refer to the preparation method of example 1.
Example 3
The difference from embodiment 1 is that, in this embodiment:
step 4, stirring 70g of PP, 50g of PA6, 5g of ADR-4368, 3g of PP-g-MAH, 30g of modified AF fiber, 0.4g of polyisobutyl methacrylate and 8g of modified nano-silica into powder at the speed of 250r/min according to the formula ratio to obtain premixed resin;
step 5, feeding the premixed resin material into a double-screw extruder for melting, blending, extruding, granulating and drying at 100 ℃ to obtain mixed resin plastic, wherein the working temperature range of the double-screw extruder is 180-230 ℃, the screw rotating speed is 100r/min, and the feeding speed is 1.5 kg/h;
step 6, heating and melting the mixed resin plastic in a charging barrel of an injection molding machine, and injecting supercritical CO accounting for 0.7 percent of the mass of the mixed resin plastic into the charging barrel2Mixing the fluid for 4s at a shearing speed of 100r/min by a screw to obtain a polymer/supercritical fluid homogeneous melt;
step 7, closing the injection mold of the injection molding machine, and injecting the polymer/supercritical CO into the cavity of the injection mold2Homogeneous melt, then injecting quantitative high-pressure auxiliary gas, applying short pressure maintaining to the melt, maintaining the high-pressure auxiliary gas, finally removing the high-pressure auxiliary gas, and realizing the secondary foaming process of the melt under the pressure relief condition;
in step 7, the high-pressure auxiliary gas is N2The pressure of the high pressure assist gas is 3 atm, polymer/supercritical CO2The injection speed of the homogeneous melt is 80mm/s, the foaming temperature is 230 ℃, the pressure of the short pressure maintaining is 60MPa, and the pressure maintaining time is 23 s.
Other procedures refer to the preparation method of example 1.
Example 4
The difference from embodiment 3 is that, in this embodiment:
step 4, stirring 70g of PP, 50g of PA6, 5g of ADR-4368, 3g of PP-g-MAH, 30g of modified AF fiber, 0.4g of polyisobutyl methacrylate and 8g of modified nano-silica into powder at the rotating speed of 200r/min according to the formula ratio to obtain premixed resin;
step 5, feeding the premixed resin material into a double-screw extruder for melting, blending, extruding, granulating and drying at 85 ℃ to obtain mixed resin plastic, wherein the working temperature range of the double-screw extruder is 180-230 ℃, the screw rotating speed is 100r/min, and the feeding speed is 1.5 kg/h;
step 6, heating and melting the mixed resin plastic in a charging barrel of an injection molding machine, and injecting supercritical CO accounting for 0.9 percent of the mass of the mixed resin plastic into the charging barrel2Mixing the fluid for 4s at a shearing speed of 100r/min by a screw to obtain a polymer/supercritical fluid homogeneous melt;
step 7, closing the injection mold of the injection molding machine, and injecting the polymer/supercritical CO into the cavity of the injection mold2Homogeneous melt, then injecting quantitative high-pressure auxiliary gas, applying short pressure maintaining to the melt, maintaining the high-pressure auxiliary gas, finally removing the high-pressure auxiliary gas, and realizing the secondary foaming process of the melt under the pressure relief condition;
in step 7, the high-pressure auxiliary gas is N2The pressure of the high pressure assist gas is 3 atm, polymer/supercritical CO2The injection speed of the homogeneous melt is 85mm/s, the foaming temperature is 240 ℃, the pressure of the short pressure maintaining is 60MPa, and the pressure maintaining time is 30 s.
Other procedures refer to the preparation method of example 3.
Example 5
The difference from embodiment 3 is that, in this embodiment:
step 4, stirring 70g of PP, 50g of PA6, 5g of ADR-4368, 7g of PP-g-MAH, 25g of modified AF fiber, 0.6g of polyisobutyl methacrylate and 15g of modified nano-silica into powder at the rotating speed of 250r/min according to the formula ratio to obtain premixed resin;
step 5, feeding the premixed resin material into a double-screw extruder for melting, blending, extruding, granulating and drying at 90 ℃ to obtain mixed resin plastic, wherein the working temperature range of the double-screw extruder is 180-230 ℃, the screw rotating speed is 100r/min, and the feeding speed is 3.0 kg/h;
step 6, heating and melting the mixed resin plastic in a charging barrel of an injection molding machine, and injecting supercritical CO accounting for 0.7 percent of the mass of the mixed resin plastic into the charging barrel2Mixing the fluid for 4s at a shearing speed of 100r/min by a screw to obtain a polymer/supercritical fluid homogeneous melt;
step 7, closing the injection mold of the injection molding machine, and injecting the polymer/supercritical CO into the cavity of the injection mold2Homogeneous melt, then injecting quantitative high-pressure auxiliary gas, applying short pressure maintaining to the melt, maintaining the high-pressure auxiliary gas, finally removing the high-pressure auxiliary gas, and realizing the secondary foaming process of the melt under the pressure relief condition;
in step 7, the high-pressure auxiliary gas is N2The pressure of the high pressure assist gas is 3 atm, polymer/supercritical CO2The injection speed of the homogeneous melt is 80mm/s, the foaming temperature is 230 ℃, the pressure of the short pressure maintaining is 60MPa, and the pressure maintaining time is 30 s.
Other procedures refer to the preparation method of example 3.
Example 6
The difference from embodiment 3 is that, in this embodiment:
in step 7, polymer/supercritical CO2The injection speed of homogeneous melt is 60mm/s, the foaming temperature is 230 ℃, the pressure of short pressure maintaining is 60MPa, and the pressure maintaining time is 26 s.
Other procedures refer to the preparation method of example 3.
Comparative example 1
The preparation process of example 3 was repeated with the amounts of the respective components, except that: modified AF fibers are not added in the formula.
Comparative example 2
The preparation process of example 3 was repeated with the amounts of the respective components, except that: in the oil removing operation of the step 2: soaking the AF fiber in absolute ethyl alcohol, mechanically stirring for 0.5-1 h, washing the obtained mixture for 5 times, and drying for later use.
Comparative example 3
The preparation process of example 3 was repeated with the amounts of the respective components, except that: step 2, the AF fiber is modified without adopting Friedel-crafts reaction, and is replaced by the following steps: and (3) treating the surface of the deoiled AF fiber by adopting NaOH solution at the temperature of 80 ℃ to modify the AF fiber.
Comparative example 4
The preparation process of example 3 was repeated with the amounts of the respective components, except that: modified nano silicon dioxide is not added in the formula.
Comparative example 5
The process of example 3 was repeated with the amounts of the respective components, except that: epoxy chain extender is not added in the formula.
Comparative example 6
The process of example 3 was repeated with the amounts of the respective components, except that: and step 6, performing injection molding by adopting a conventional foaming injection molding process (full injection method) without using high-pressure auxiliary gas.
Comparative example 7
The process of example 3 was repeated with the amounts of the respective components, except that: step 3 is omitted, and the nano silicon dioxide is not modified by using a silane coupling agent.
Second, performance test
The PP/PA6 porous composite materials prepared in examples 1-6 and comparative examples 1-7 were subjected to relevant performance tests, and the results are shown in tables 1 and 2.
TABLE 1 PP/PA6 porous composite Performance test data
Figure BDA0003435861980000161
Figure BDA0003435861980000171
According to the invention, PP is added to modify PA6, PP-g-MAH is used as a compatilizer, and a modified nano nucleating agent, a cell stabilizer and modified AF fibers are used in a matching manner to prepare the PP/PA6 porous composite material with high mechanical property. As can be seen from Table 1, when the prepared PP: PA6: PP-g-MAH: ADR-4368 and modified AF fiber 70:50:3:5:30, the melt temperature in the secondary foaming is 230 ℃, the injection speed is 80mm/s, and the supercritical CO is adopted2The amount of fluid is 0.7%, the obtained composite material has small foam pore size in the whole foaming window of 6.8-9.6 μm and high cell density of 5.46 × 109cell/cm3The foaming ratio at the same foaming temperature is as high as 26.2 times.
TABLE 2 PP/PA6 porous composite Performance test data
Figure BDA0003435861980000172
As can be seen from Table 2, in comparative example 2, the mechanical stirring method is adopted to remove oil, lubricating oil is lost on the surface of the AF fiber, static electricity is easily generated by surface friction, the length-diameter ratio of the AF fiber is large, the fibers are easily entangled, the AF fiber dispersed in the resin matrix can be regarded as holes caused by impurities to destroy the ordered structure among bubbles, and the prepared foam material has poor mechanical property; in the comparative example 3, alkali treatment modification is adopted, due to the blocking effect of a benzene ring, the amido bond of the AF fiber is not hydrolyzed completely in an alkali solution, the middle modification effect of the AF fiber is not obvious, uneven reactants are easily attached to the surface, the roughness is larger, and the mechanical property of the foaming material is reduced to some extent; the modified AF fiber obtained by matching with the surfactant for ultrasonic oil removal and Friedel-crafts reaction modification in the embodiment 3 can effectively improve the interface bonding effect of the modified AF fiber and a resin matrix, so that stress can be effectively transmitted to the fiber, and the bending strength and the impact strength of the obtained composite material are obviously improved.
Comparative example 6 adopts a conventional foaming process, the prepared material has uneven foam pores, and example 3 adopts a gas-assisted mold opening and closing microcellular foaming injection molding process, so that the injection amount for filling the mold cavity with the melt is reduced, bad foam pores generated during filling are eliminated, the foaming size is uniform, and the foaming ratio is high.
Comparative example 4 does not use the modified nano nucleating agent, as shown in fig. 3, the pore size of the foam material is distributed between 50.9 and 83.2 μm, and the partial pore size is about 300 μm, compared with example 3, the mechanical property of the foam material is reduced by about 40%. Therefore, the addition of the modified nano nucleating agent can improve the foaming ratio of the foaming material and reinforce the mechanical property to a certain extent.
The above embodiments and drawings are not intended to limit the form and style of the present invention, and any suitable changes or modifications thereof by those skilled in the art should be considered as not departing from the scope of the present invention.

Claims (10)

1. A PP/PA6 porous composite material is characterized in that: the composite material comprises the following raw materials in parts by weight:
Figure FDA0003435861970000011
the modified AF fiber is obtained by sequentially carrying out oil removal and Friedel-crafts reaction treatment, and the modified nano nucleating agent is nano silicon dioxide treated by a silane coupling agent or nano calcium carbonate treated by the silane coupling agent.
2. The PP/PA6 cellular composite material according to claim 1, wherein: the PP is block copolymerization PP or random copolymerization PP, the epoxy chain extender is one or more of ADR-4468, ADR-4368 and KL-E4370, the compatilizer is one of maleic anhydride grafted polypropylene, maleic anhydride grafted styrene-butadiene copolymer and maleic anhydride grafted ethylene-olefin copolymer, the cell stabilizer is one or two of polyisobutyl methacrylate and n-butyl polymethacrylate, and the silane coupling agent is one of KH550, KH570 and KH 602.
3. The preparation method of the PP/PA6 porous composite material as claimed in claim 1, wherein the preparation method comprises the following steps: the method comprises the following steps:
step 1, drying PP, PA6 and a nano nucleating agent for later use, wherein the nano nucleating agent is nano silicon dioxide or nano calcium carbonate;
and 2, carrying out modification treatment on the AF fiber:
oil removal operation: soaking AF fibers in sodium dodecyl benzene sulfonate water solution, performing ultrasonic treatment for 0.5-1 h, filtering the obtained mixture through a nano-filtration membrane, washing for 3-5 times, and drying for later use;
the Friedel-crafts reaction operation is as follows: soaking the deoiled AF fiber in epoxy chloropropane, vacuumizing, filling nitrogen, repeating for many times, keeping inert atmosphere, keeping condensation reflux of a reaction system at 110-130 ℃ for 0.5-1 h, and adding AlCl into the system for many times3Reacting for 8-10 h to obtain a modified AF crude product;
and (3) purification operation: then washing the modified AF crude product with ethanol, treating the modified AF crude product in NaOH solution at 50-70 ℃ for 1-2 hours, washing the modified AF crude product with distilled water, drying the modified AF crude product to obtain modified AF fibers, and sealing the modified AF fibers for later use;
and 3, modifying the dried nano nucleating agent: fully mixing a silane coupling agent and absolute ethyl alcohol in a volume ratio of 1: 3-1: 5 under an ultrasonic condition to obtain a mixed solution, and mixing the mixed solution and a nano nucleating agent in a high-speed mixer for 20-30 min to obtain a modified nano nucleating agent;
step 4, stirring PP, PA6, an epoxy chain extender, a compatilizer, modified AF fibers, a cell stabilizer and a modified nano nucleating agent into powder at a high speed according to the formula proportion to obtain premixed resin;
step 5, feeding the premixed resin material into a double-screw extruder for melting, blending, extruding, granulating and drying to obtain mixed resin plastic;
step 6, adding mixed resin plastic and supercritical CO into a charging barrel of an injection molding machine2Fluid production to Polymer/supercritical CO2Homogeneous melt;
step 7, finally adopting a gas-assisted open-close die microcellular foaming injection molding process to carry out the step 6 on the obtained polymer/supercritical CO2And carrying out secondary foaming on the homogeneous melt to obtain the PP/PA6 porous composite material.
4. The preparation method of the PP/PA6 porous composite material, according to claim 3, wherein the preparation method comprises the following steps: in the step 2, the mass usage ratio of the AF fiber to the sodium dodecyl benzene sulfonate melt is 1: 5-1: 15; the AF fiber and AlCl3The mass and dosage ratio of (A) to (B) is 7: 1-10: 1.
5. The preparation method of the PP/PA6 porous composite material, according to claim 3, wherein the preparation method comprises the following steps: in the step 3, the adding amount of the silane coupling agent is 1% of the mass of the nano nucleating agent, and the rotating speed of the high-speed mixer is 100-300 r/min.
6. The preparation method of the PP/PA6 porous composite material, according to claim 3, wherein the preparation method comprises the following steps: in the step 5, the working temperature of the double-screw extruder is 180-230 ℃, the screw rotating speed is 80-140 r/min, the feeding speed is 1.5-3 kg/h, and the drying temperature is 60-100 ℃.
7. The preparation method of the PP/PA6 porous composite material, according to claim 3, wherein the preparation method comprises the following steps: in step 6, the polymer/supercritical CO2The preparation process of the homogeneous melt comprises the following steps: firstly, the mixed resin plastics are heated and melted in a charging barrel of an injection molding machine, and then supercritical CO is injected into the charging barrel2And shearing and mixing the fluid for 2-6 s by using a screw to obtain the polymer/supercritical fluid homogeneous melt.
8. The preparation method of the PP/PA6 porous composite material, according to claim 7, wherein the preparation method comprises the following steps: in step 6, supercritical CO2The using amount of the fluid is 0.5-1.0% of the mass of the mixed resin plastic, and the shearing speed is 60-100 r/min.
9. The preparation method of the PP/PA6 porous composite material, according to claim 3, wherein the preparation method comprises the following steps: in step 7, the secondary foaming operation comprises: closing the injection mold and injecting the polymer/supercritical CO into the cavity2Homogeneous melt, then injecting quantitative high-pressure auxiliary gas, applying short pressure maintaining to the system, maintaining the high-pressure auxiliary gas, then removing the high-pressure auxiliary gas, and realizing the secondary foaming process of the melt under the pressure relief condition.
10. The preparation method of the PP/PA6 porous composite material, according to claim 9, wherein the preparation method comprises the following steps: in step 7, the high-pressure auxiliary gas is N2Or Ar, the pressure of the high-pressure auxiliary gas is 3 standard atmospheric pressures, and the polymer/supercritical CO is2The injection speed of the homogeneous melt is 40-80 mm/s, the foaming temperature is 190-250 ℃, the pressure of the short pressure maintaining is 40-70 MPa, and the pressure maintaining time is 10-30 s.
CN202111613741.3A 2021-12-27 2021-12-27 PP/PA6 porous composite material and preparation method thereof Active CN114106506B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111613741.3A CN114106506B (en) 2021-12-27 2021-12-27 PP/PA6 porous composite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111613741.3A CN114106506B (en) 2021-12-27 2021-12-27 PP/PA6 porous composite material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114106506A true CN114106506A (en) 2022-03-01
CN114106506B CN114106506B (en) 2023-10-03

Family

ID=80363247

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111613741.3A Active CN114106506B (en) 2021-12-27 2021-12-27 PP/PA6 porous composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114106506B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115926260A (en) * 2022-12-28 2023-04-07 湖北格霖威新材料科技有限公司 Preparation method of degradable high-strength closed-cell polylactic acid foam material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060049539A1 (en) * 2002-10-18 2006-03-09 Yoeng-Baeg Choi Microcellular foamed fiber, and a process of preparing for the same
CN103981692A (en) * 2014-06-03 2014-08-13 陕西科技大学 Method for organically modifying surface of aramid fiber (ARF)
CN109485993A (en) * 2018-09-12 2019-03-19 合肥华聚微科新材料有限责任公司 A kind of true micropore injection moulding forming polypropylene foamed material and preparation method thereof
CN111087805A (en) * 2019-12-27 2020-05-01 华润化学材料科技股份有限公司 Supercritical fluid continuous extrusion high-performance recyclable PA (polyamide) foam material and preparation method thereof
CN113652029A (en) * 2021-08-23 2021-11-16 金发科技股份有限公司 Micro-foaming polypropylene composition and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060049539A1 (en) * 2002-10-18 2006-03-09 Yoeng-Baeg Choi Microcellular foamed fiber, and a process of preparing for the same
CN103981692A (en) * 2014-06-03 2014-08-13 陕西科技大学 Method for organically modifying surface of aramid fiber (ARF)
CN109485993A (en) * 2018-09-12 2019-03-19 合肥华聚微科新材料有限责任公司 A kind of true micropore injection moulding forming polypropylene foamed material and preparation method thereof
CN111087805A (en) * 2019-12-27 2020-05-01 华润化学材料科技股份有限公司 Supercritical fluid continuous extrusion high-performance recyclable PA (polyamide) foam material and preparation method thereof
CN113652029A (en) * 2021-08-23 2021-11-16 金发科技股份有限公司 Micro-foaming polypropylene composition and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MENGLONG XU: "Determination of modified polyamide 6’s foaming windows by bubble growth simulations based on rheological measurements", 《JOURNAL OF APPLIED POLYMER SCIENCE》, pages 48138 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115926260A (en) * 2022-12-28 2023-04-07 湖北格霖威新材料科技有限公司 Preparation method of degradable high-strength closed-cell polylactic acid foam material
CN115926260B (en) * 2022-12-28 2024-01-26 湖北格霖威新材料科技有限公司 Preparation method of degradable high-strength closed-cell polylactic acid foaming material

Also Published As

Publication number Publication date
CN114106506B (en) 2023-10-03

Similar Documents

Publication Publication Date Title
CN111286070B (en) Supercritical fluid injection-molded foamed polylactic acid foam material and preparation method thereof
JP6351574B2 (en) Foam molding
CN111087805B (en) Supercritical fluid continuous extrusion high-performance recyclable PA (polyamide) foam material and preparation method thereof
CN108530752B (en) Micro-foaming continuous long glass fiber reinforced polypropylene composite material and preparation method and application thereof
CN103756124A (en) Polypropylene foaming material, production and preparation method of product
CN114015109B (en) Preparation method of nylon foaming material with high melt strength
WO2006043609A1 (en) Polyvinylidene fluoride resin powder for melt molding and process for producing molding from the resin powder
CN114106506A (en) PP/PA6 porous composite material and preparation method thereof
CN112608553A (en) Plant fiber reinforced polypropylene composite material and preparation method thereof
CN112940468A (en) Polylactic acid-based foaming particles and preparation method thereof
CN110229372A (en) Low molding energy consumption polypropylene foamed particles of one kind and preparation method thereof
CN112759825B (en) Fiber reinforced polypropylene composition, foamed polypropylene composite material and preparation method thereof
CN112029190A (en) Micro-foaming polypropylene material and preparation method thereof
CN107987453A (en) One kind injection grade polypropylene/polyamide micro foaming composite material and preparation method thereof
CN113980384A (en) Long glass fiber reinforced polypropylene composite material and preparation method and application thereof
CN105694206A (en) Method for producing long-glass-fiber-reinforced polypropylene foaming injection product by using water as foaming agent
CN111286117B (en) Method for forming open-cell polymer foam material by micropore injection molding and product
CN110256840B (en) Preparation method of foamed nylon plate
CN110128741B (en) Polyolefin foam material and preparation method thereof
CN115505161B (en) Nylon mould pressing foaming material and preparation method thereof
CN111019240B (en) Polypropylene composite material for injection molding foaming and preparation method thereof
CN105291340A (en) Water foaming injection method by using super absorbent resin as carrier
CN109265825A (en) A kind of polypropylene or polypropylene composite foaming product and preparation method thereof
Zhou et al. Toughening effect of bamboo flour/polypropylene foamed composite
CN109897315A (en) A kind of preparation method of maleated polypropylene micro nanometer fiber/polyvinyl alcohol foam material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant