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CN112851990A - Method for preparing film-foam dual-medium modulation target by casting compounding - Google Patents

Method for preparing film-foam dual-medium modulation target by casting compounding Download PDF

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CN112851990A
CN112851990A CN202011636635.2A CN202011636635A CN112851990A CN 112851990 A CN112851990 A CN 112851990A CN 202011636635 A CN202011636635 A CN 202011636635A CN 112851990 A CN112851990 A CN 112851990A
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modulation
film
resorcinol
solution
formaldehyde
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CN112851990B (en
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吴小军
童维超
何智兵
尹强
徐嘉靖
朱方华
苏琳
李娃
张伟
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Laser Fusion Research Center China Academy of Engineering Physics
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/0427Coating with only one layer of a composition containing a polymer binder
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00Foams characterised by their properties
    • C08J2205/02Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
    • C08J2205/026Aerogel, i.e. a supercritically dried gel
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00Characterised 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
    • C08J2351/06Characterised 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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    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/06Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08J2361/12Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2461/00Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2461/04Condensation polymers of aldehydes or ketones with phenols only
    • C08J2461/06Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08J2461/12Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols

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  • Polymers & Plastics (AREA)
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Abstract

The invention discloses a method for preparing a film-foam dual-medium modulation target by casting compounding, which comprises the following steps: uniformly pouring a polypropylene grafted styrene solution on the surface of a modulation template with modulation patterns, keeping the modulation template horizontal, volatilizing a solvent at room temperature, and demoulding after the solvent is completely volatilized to obtain a modulation film with sinusoidal patterns with different periods and amplitudes on the surface; pouring resorcinol-formaldehyde sol solution on the surface of a modulation film, performing ultrasonic treatment on the surface of the modulation film to obtain resorcinol-formaldehyde gel, and adding the resorcinol-formaldehyde gel into isopropanolStanding for solvent exchange, and supercritical CO2And extracting and drying to obtain the polypropylene grafted styrene film and resorcinol-formaldehyde aerogel foam compounded dual-medium modulation target. The invention can prepare the double-medium composite modulation target sample with clear modulation patterns and tight combination between the polypropylene grafted styrene film and the low-density foam layer interface.

Description

Method for preparing film-foam dual-medium modulation target by casting compounding
Technical Field
The invention relates to a method for preparing a film-foam dual-medium modulation target by casting compounding.
Background
In the research of Inertial Confinement Fusion (ICF), in order to improve the Fusion success rate and energy gain of the target pellet, a precise decomposition experiment is required to carry out related simulation and research work, that is, a sinusoidal modulation pattern is introduced on the surface of the target pellet, surface density disturbance is artificially produced to simulate the non-uniformity of the surface of the target pellet, and the magnitude of the hydrodynamic instability is researched and estimated by measuring the time-space distribution nonlinear increase of the target density disturbance in the target ablation process by laser. With the development of physical diagnosis technology and the deepening of precise decomposition experimental research, the target type structure of related modulation targets tends to be diversified, and the target is expanded from the original simple single-medium planar modulation target to a double-medium composite modulation target. At present, many reports are reported on the experimental study of the hydrodynamic instability developed abroad based on various types of modulation targets, but the specific preparation method of the targets is rarely disclosed. In China, more research works are carried out on the aspect of single-medium plane modulation targets, and the preparation technology is mature; however, the research on the preparation of the dual-media composite modulation target is relatively less advanced, and the only related work is mainly focused on the composite preparation of the silica aerogel and the carbon aerogel, the polystyrene thin film and the carbon aerogel, and the polystyrene thin film and the metal, while the research on the thin film-foam dual-media modulation target is less advanced, and the composite preparation process needs to be researched and established.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the purpose of the present invention, there is provided a method for cast-compounding a film-foam dual media modulation target, comprising the steps of:
preparing a polypropylene grafted styrene solution with the concentration of 0.01-0.05 g/mL, uniformly pouring the polypropylene grafted styrene solution on the surface of a modulation template with sinusoidal patterns, keeping the modulation template horizontal, volatilizing a solvent at room temperature, and demoulding after the solvent is completely volatilized to obtain a modulation film with sinusoidal patterns with different periods and amplitudes on the surface;
step two, pouring the resorcinol-formaldehyde sol solution on the surface of the modulation film in the step one, performing ultrasonic treatment at 65-85 ℃ for 90-120 min to obtain resorcinol-formaldehyde gel on the surface of the modulation film, adding the resorcinol-formaldehyde gel into isopropanol, standing for solvent exchange, replacing the isopropanol every day for 3 days, and then performing supercritical CO2And extracting and drying to obtain the polypropylene grafted styrene film and resorcinol-formaldehyde aerogel foam compounded dual-medium modulation target.
Preferably, the preparation method of the polypropylene grafted styrene solution comprises the following steps: adding 20-25 parts by weight of polypropylene powder and 0.1-0.5 part by weight of benzoyl peroxide into supercritical CO2Introducing CO into the reactor2Using supercritical CO at a pressure of 15-25 MPa and a temperature of 38-40 deg.C2Swelling for 45-75 min, then decompressing at the speed of 0.2-0.4 MPa/min, adding 25-30 parts of styrene after decompressing, and introducing CO again2Stirring and reacting for 2-4 h under the pressure of 15-25 MPa and the temperature of 80-100 ℃, relieving pressure, washing a product with ethanol, and extracting in a Soxhlet extractor with chloroformTo constant weight to obtain polypropylene grafted styrene; adding the polypropylene grafted styrene into a mixed solvent of 1,2, 4-trichlorobenzene and N, N-dimethylformamide DMF, and stirring for dissolving to obtain a polypropylene grafted styrene solution with the concentration of 0.01-0.05 g/mL.
Preferably, the volume ratio of the 1,2, 4-trichlorobenzene to the DMF is 2-3: 1.
Preferably, in the first step, the surface of the obtained modulation film is treated by using low-temperature plasma, and the process is as follows: putting the modulation film into a cavity of a low-temperature plasma treatment instrument, opening a vacuum pump, introducing argon after the vacuum degree in the cavity is lower than 10Pa, and setting the argon flow to be 35-45 cm3And/min, adjusting the power of a high-frequency power supply to be 50-80W, and operating the pressure to be 30-60 Pa, and starting to perform low-temperature plasma modification on the surface of the modulation film for 5-10 s.
Preferably, the frequency of the ultrasonic wave is 55-65 kHz.
Preferably, the preparation method of the resorcinol-formaldehyde sol solution comprises the following steps: adding resorcinol, polyoxyethylene and nano-fibers into a formaldehyde solution with the volume concentration of 35-40%, uniformly stirring, then adding sodium carbonate, and stirring and dispersing to obtain the resorcinol-formaldehyde sol solution.
Preferably, the molar ratio of resorcinol to formaldehyde in the formaldehyde solution is 1: 1.5-2.5; the molar ratio of the resorcinol to the sodium carbonate is 1: 0.01-0.05; the mass ratio of the resorcinol to the polyoxyethylene is 1: 0.1-0.15; the mass ratio of the resorcinol to the nano-fibers is 1: 0.2-0.3.
Preferably, the nanofiber is a porous hollow nanofiber, and the preparation method of the porous hollow nanofiber comprises the following steps: adding polystyrene and polyethyleneimine into chloroform, and stirring for dissolving to obtain a shell solution; adding polyethyleneimine into methanol, and stirring for dissolving to obtain a nuclear layer solution; respectively inputting the shell layer solution and the core layer solution into an outer layer and an inner layer of a coaxial needle at constant flow rate, connecting the coaxial needle with a high-voltage electrostatic generator for electrostatic spinning, and receiving spun fibers by using a receiving device to obtain a core-shell fiber membrane; placing the core-shell fiber membrane in water for ultrasonic washing to remove polyethyleneimine to obtain a porous hollow nanofiber membrane; and (3) crushing the porous hollow nanofiber membrane, and sieving with a 200-300-mesh sieve to obtain the porous hollow nanofiber.
Preferably, the mass ratio of the polystyrene to the polyethyleneimine is 4-6: 1; the concentration of the shell layer solution is 8-18 wt%; the concentration of the nuclear layer solution is 6-15 wt%; the flow rate of the shell solution is 2-5 mL/h; the flow rate of the nuclear layer solution is 0.8-1.8 mL/h; the voltage of the high-voltage electrostatic generator is 12-25 kV; the receiving device is tin foil; the distance between the coaxial needle head and the receiving device is 12-15 cm; the ambient temperature of electrostatic spinning is 40-60 ℃; the inner diameter of the inner needle head of the coaxial needle head is 0.6-0.8 mm, and the inner diameter of the outer needle head is 1.2-1.8 mm.
Preferably, the frequency of ultrasonic washing is 30-40 kHz, and the time is 60-120 min.
The invention at least comprises the following beneficial effects: the preparation method comprises the steps of firstly obtaining a polypropylene grafted styrene modulation film with sinusoidal patterns by using a template casting method, then respectively carrying out casting compounding on foam sol on the surface of the modulation film, and preparing a dual-medium composite modulation target sample with clear modulation patterns and tight combination of the interface modulation patterns of the polypropylene grafted styrene film and a low-density foam layer by using the process.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 is a comparison of sinusoidal patterns on the surface of a modulation template and a film according to the present invention;
FIG. 2 is a graph of thickness control of a cast-on-cast modulated film according to the present invention;
FIG. 3 is a cross-sectional optical image of a cast composite film-foam dual media modulation target sample of the present invention;
FIG. 4 is a cross-sectional SEM image of a cast composite film-foam dual media modulation target sample of the present invention.
The specific implementation mode is as follows:
the present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
a method for preparing a film-foam dual-medium modulation target by casting compounding comprises the following steps:
preparing a polypropylene grafted styrene solution with the concentration of 0.03g/mL, uniformly pouring the polypropylene grafted styrene solution on the surface of a modulation copper template with modulation patterns, keeping the modulation copper template horizontal, volatilizing a solvent at room temperature, and demoulding after the solvent is completely volatilized to obtain a modulation film with sinusoidal patterns with different periods and amplitudes on the surface; the surface of the obtained modulation film is processed by adopting low-temperature plasma, and the process comprises the following steps: putting the modulation film into a cavity of a low-temperature plasma treatment instrument, opening a vacuum pump, introducing argon after the vacuum degree in the cavity is lower than 10Pa, and setting the argon flow to be 35cm3Min, adjusting the power of a high-frequency power supply to be 50W, and the operating pressure to be 30Pa, and beginning to perform low-temperature plasma modification on the surface of the modulation film for 5 s; the surface of the modulation film is subjected to low-temperature plasma treatment for a short time, so that the surface microscopic morphology of the modulation film is slightly changed, and the composite interface of the film-foam dual-medium modulation target sample can be tightly combined;
step two, pouring the resorcinol-formaldehyde sol solution on the surface of the modulation film in the step one, performing ultrasonic treatment at 65 ℃ for 90min to obtain resorcinol-formaldehyde gel on the surface of the modulation film, adding the resorcinol-formaldehyde gel into isopropanol, standing for solvent exchange, replacing the isopropanol every day for 3 days, and then performing supercritical CO2Extracting and drying to obtain a polypropylene grafted styrene film and resorcinol-formaldehyde (RF) aerogel foam compounded dual-medium modulation target; the frequency of the ultrasound is 55 kHz;
the preparation method of the polypropylene grafted styrene solution comprises the following steps: 20g of polypropylene powder and 0.1g of benzoyl peroxide were added to supercritical CO2Introducing CO into the reactor2Using supercritical CO at a pressure of 15MPa and a temperature of 38 DEG C2Swelling for 75min, then relieving pressure at 0.2MPa/min, adding 25g styrene after pressure relief, and introducing CO again2Stirring and reacting for 2 hours at the pressure of 15MPa and the temperature of 80 ℃, decompressing, washing a product by using ethanol, and extracting the product to constant weight by using chloroform in a Soxhlet extractor to obtain polypropylene grafted styrene; adding polypropylene grafted styrene into a mixed solvent of 1,2, 4-trichlorobenzene and DMF, and stirring for dissolving to obtain a polypropylene grafted styrene solution with the concentration of 0.03 g/mL; the volume ratio of the 1,2, 4-trichlorobenzene to the DMF is 2: 1;
the preparation method of the resorcinol-formaldehyde sol solution comprises the following steps: adding resorcinol, polyoxyethylene and nano-fibers into 35% formaldehyde solution, uniformly stirring, then adding sodium carbonate, and stirring and dispersing to obtain resorcinol-formaldehyde sol solution; the molar ratio of the resorcinol to the formaldehyde in the formaldehyde solution is 1: 2; the molar ratio of the resorcinol to the sodium carbonate is 1: 0.02; the mass ratio of the resorcinol to the polyoxyethylene is 1: 0.1; the mass ratio of the resorcinol to the nano-fibers is 1: 0.2;
the nanofiber is a porous hollow nanofiber, and the preparation method of the porous hollow nanofiber comprises the following steps: adding polystyrene and polyethyleneimine into chloroform, and stirring for dissolving to obtain a shell solution; adding polyethyleneimine into methanol, and stirring for dissolving to obtain a nuclear layer solution; respectively inputting the shell layer solution and the core layer solution into an outer layer and an inner layer of a coaxial needle at constant flow rate, connecting the coaxial needle with a high-voltage electrostatic generator for electrostatic spinning, and receiving spun fibers by using a receiving device to obtain a core-shell fiber membrane; placing the core-shell fiber membrane in water for ultrasonic washing to remove polyethyleneimine to obtain a porous hollow nanofiber membrane; crushing the porous hollow nanofiber membrane, and sieving with a 200-mesh sieve to obtain porous hollow nanofibers; the density of the foam can be obviously reduced by adopting the porous hollow nanofiber, and the porous hollow nanofiber has certain strength, so that the shrinkage of the volume of the foam can be prevented, and the foam is not easy to deform during drying;
the mass ratio of the polystyrene to the polyethyleneimine is 4: 1; the concentration of the shell layer solution is 8 wt%; the concentration of the core layer solution is 8 wt%; the flow rate of the shell layer solution is 2 mL/h; the flow rate of the nuclear layer solution is 1.5 mL/h; the voltage of the high-voltage electrostatic generator is 15 kV; the receiving device is tin foil; the distance between the coaxial needle head and the receiving device is 12 cm; the ambient temperature of electrostatic spinning is 40 ℃; the inner diameter of the inner needle head of the coaxial needle head is 0.6mm, and the inner diameter of the outer needle head is 1.2 mm; the ultrasonic washing frequency is 40kHz, and the time is 120 min;
adopting a Form Talysurf series 2 contact pin type step profiler to measure the surface profile and the film thickness of the modulation copper template and the modulation film; as a result, as shown in FIG. 1, the dimensional shrinkage of the modulation pattern on the surface of the modulation film is small (as shown in FIG. 1, the period T is 3% and the amplitude A is 6%), and the relief pattern on the surface of the modulation film is nearly ideal sinusoidal, i.e., the modulation pattern of the modulation copper template is substantially completely transferred to the surface of the polymer film. Meanwhile, the thickness of the modulation film can be accurately set according to the pouring volume of the solution, as shown in FIG. 2, the thickness of the modulation film is controllable within the range of 10-25 μm;
the density of the film-foam dual media conditioning target prepared in example 1 was tested to be 120mg/cm3(ii) a FIG. 3 is a cross-sectional image of a membrane-foam dual-media modulation target sample with tight bonding of the composite interface, complete and clear sinusoidal relief patterns, and no significant deformation; FIG. 4 is a cross-sectional SEM image of a film-foam dual media modulated target having a smoother surface pattern profile that better satisfies the requirements of ICF hydrodynamic instability experiments on the modulated target.
Example 2:
a method for preparing a film-foam dual-medium modulation target by casting compounding comprises the following steps:
step one, preparing a polypropylene grafted styrene solution with the concentration of 0.03g/mL, and uniformly pouring the polypropylene grafted styrene solution onMaintaining the level of the modulation copper template on the surface of the modulation copper template with modulation patterns, volatilizing the solvent at room temperature, and demoulding after the solvent is completely volatilized to obtain the modulation film with sinusoidal patterns with different periods and amplitudes on the surface; the surface of the obtained modulation film is processed by adopting low-temperature plasma, and the process comprises the following steps: putting the modulation film into a cavity of a low-temperature plasma treatment instrument, opening a vacuum pump, introducing argon after the vacuum degree in the cavity is lower than 10Pa, and setting the argon flow to be 40cm3Min, adjusting the power of a high-frequency power supply to 70W, adjusting the operating pressure to 45Pa, and beginning to perform low-temperature plasma modification on the surface of the modulation film for 8 s;
step two, pouring the resorcinol-formaldehyde sol solution on the surface of the prepared film in the step one, performing ultrasonic treatment at 85 ℃ for 120min to obtain resorcinol-formaldehyde gel on the surface of the prepared film, adding the resorcinol-formaldehyde gel into isopropanol, standing for solvent exchange, replacing the isopropanol every day for 3 days, and then performing supercritical CO2Extracting and drying to obtain a polypropylene grafted styrene film and resorcinol-formaldehyde aerogel foam compounded double-medium modulation target; the frequency of the ultrasound is 65 kHz;
the preparation method of the polypropylene grafted styrene solution comprises the following steps: 25g of polypropylene powder and 0.2g of benzoyl peroxide were added to supercritical CO2Introducing carbon dioxide into the reactor, and using supercritical CO at a pressure of 20MPa and a temperature of 40 DEG C2Swelling for 60min, then relieving pressure at 0.4MPa/min, adding 28g styrene after pressure relief, and introducing CO again2Stirring and reacting for 3 hours at the pressure of 20MPa and the temperature of 90 ℃, decompressing, washing a product by using ethanol, and extracting the product to constant weight by using chloroform in a Soxhlet extractor to obtain polypropylene grafted styrene; adding polypropylene grafted styrene into a mixed solvent of 1,2, 4-trichlorobenzene and DMF, and stirring for dissolving to obtain a polypropylene grafted styrene solution with the concentration of 0.03 g/mL; the volume ratio of the 1,2, 4-trichlorobenzene to the DMF is 3: 1;
the preparation method of the resorcinol-formaldehyde sol solution comprises the following steps: adding resorcinol, polyoxyethylene and nano-fibers into 35% formaldehyde solution, uniformly stirring, then adding sodium carbonate, and stirring and dispersing to obtain resorcinol-formaldehyde sol solution; the molar ratio of the resorcinol to the formaldehyde in the formaldehyde solution is 1: 2; the molar ratio of the resorcinol to the sodium carbonate is 1: 0.03; the mass ratio of the resorcinol to the polyoxyethylene is 1: 0.1; the mass ratio of the resorcinol to the nano-fibers is 1: 0.3;
the nanofiber is a porous hollow nanofiber, and the preparation method of the porous hollow nanofiber comprises the following steps: adding polystyrene and polyethyleneimine into chloroform, and stirring for dissolving to obtain a shell solution; adding polyethyleneimine into methanol, and stirring for dissolving to obtain a nuclear layer solution; respectively inputting the shell layer solution and the core layer solution into an outer layer and an inner layer of a coaxial needle at constant flow rate, connecting the coaxial needle with a high-voltage electrostatic generator for electrostatic spinning, and receiving spun fibers by using a receiving device to obtain a core-shell fiber membrane; placing the core-shell fiber membrane in water for ultrasonic washing to remove polyethyleneimine to obtain a porous hollow nanofiber membrane; crushing the porous hollow nanofiber membrane, and sieving with a 200-mesh sieve to obtain porous hollow nanofibers;
the mass ratio of the polystyrene to the polyethyleneimine is 5: 1; the concentration of the shell layer solution is 10 wt%; the concentration of the nuclear layer solution is 6 wt%; the flow rate of the shell layer solution is 2 mL/h; the flow rate of the nuclear layer solution is 1.5 mL/h; the voltage of the high-voltage electrostatic generator is 15 kV; the receiving device is tin foil; the distance between the coaxial needle head and the receiving device is 12 cm; the ambient temperature of electrostatic spinning is 40 ℃; the inner diameter of the inner needle head of the coaxial needle head is 0.8mm, and the inner diameter of the outer needle head is 1.5 mm; the ultrasonic washing frequency is 40kHz, and the time is 120 min;
the foam density of the film-foam dual media conditioning target prepared in example 1 was tested to be 121mg/cm3
Comparative example 1:
a method for preparing a film-foam dual-medium modulation target by casting compounding comprises the following steps:
step one, preparing a polypropylene grafted styrene solution with the concentration of 0.03g/mL, and homogenizing the polypropylene grafted styrene solutionUniformly pouring the mixture on the surface of a modulation template with modulation patterns, keeping the modulation template horizontal, volatilizing the solvent at room temperature, and demoulding after the solvent is completely volatilized to obtain a modulation film with sinusoidal patterns with different periods and amplitudes on the surface; the surface of the obtained modulation film is processed by adopting low-temperature plasma, and the process comprises the following steps: putting the modulation film into a cavity of a low-temperature plasma treatment instrument, opening a vacuum pump, introducing argon after the vacuum degree in the cavity is lower than 10Pa, and setting the argon flow to be 35cm3Min, adjusting the power of a high-frequency power supply to be 50W, and the operating pressure to be 30Pa, and beginning to perform low-temperature plasma modification on the surface of the modulation film for 5 s;
step two, pouring the resorcinol-formaldehyde sol solution on the surface of the modulation film in the step one, performing ultrasonic treatment at 65 ℃ for 90min to obtain resorcinol-formaldehyde gel on the surface of the modulation film, adding the resorcinol-formaldehyde gel into isopropanol, standing for solvent exchange, replacing the isopropanol every day for 3 days, and then performing supercritical CO2Extracting and drying to obtain a polypropylene grafted styrene film and resorcinol-formaldehyde aerogel foam compounded double-medium modulation target; the frequency of the ultrasound is 55 kHz;
the preparation method of the polypropylene grafted styrene solution comprises the following steps: mixing 25g of styrene and 0.1g of benzoyl peroxide, then adding 20g of polypropylene powder, introducing nitrogen to discharge oxygen, sealing, stirring and reacting at the temperature of 80 ℃ for 2 hours, washing a product with ethanol, and then extracting the product with chloroform in a Soxhlet extractor to constant weight to obtain polypropylene grafted styrene; adding polypropylene grafted styrene into a mixed solvent of 1,2, 4-trichlorobenzene and DMF, and stirring for dissolving to obtain a polypropylene grafted styrene solution with the concentration of 0.03 g/mL; the volume ratio of the 1,2, 4-trichlorobenzene to the DMF is 2: 1;
the preparation method of the resorcinol-formaldehyde sol solution comprises the following steps: adding resorcinol, polyoxyethylene and nano-fibers into 35% formaldehyde solution, uniformly stirring, then adding sodium carbonate, and stirring and dispersing to obtain resorcinol-formaldehyde sol solution; the molar ratio of the resorcinol to the formaldehyde in the formaldehyde solution is 1: 2; the molar ratio of the resorcinol to the sodium carbonate is 1: 0.02; the mass ratio of the resorcinol to the polyoxyethylene is 1: 0.1; the mass ratio of the resorcinol to the nano-fibers is 1: 0.2;
the nanofiber is a porous hollow nanofiber, and the preparation method of the porous hollow nanofiber comprises the following steps: adding polystyrene and polyethyleneimine into chloroform, and stirring for dissolving to obtain a shell solution; adding polyethyleneimine into methanol, and stirring for dissolving to obtain a nuclear layer solution; respectively inputting the shell layer solution and the core layer solution into an outer layer and an inner layer of a coaxial needle at constant flow rate, connecting the coaxial needle with a high-voltage electrostatic generator for electrostatic spinning, and receiving spun fibers by using a receiving device to obtain a core-shell fiber membrane; placing the core-shell fiber membrane in water for ultrasonic washing to remove polyethyleneimine to obtain a porous hollow nanofiber membrane; crushing the porous hollow nanofiber membrane, and sieving with a 200-mesh sieve to obtain porous hollow nanofibers;
the mass ratio of the polystyrene to the polyethyleneimine is 4: 1; the concentration of the shell layer solution is 8 wt%; the concentration of the core layer solution is 8 wt%; the flow rate of the shell layer solution is 2 mL/h; the flow rate of the nuclear layer solution is 1.5 mL/h; the voltage of the high-voltage electrostatic generator is 15 kV; the receiving device is tin foil; the distance between the coaxial needle head and the receiving device is 12 cm; the ambient temperature of electrostatic spinning is 40 ℃; the inner diameter of the inner needle head of the coaxial needle head is 0.6mm, and the inner diameter of the outer needle head is 1.2 mm; the ultrasonic washing frequency is 40kHz, and the time is 120 min;
the size shrinkage amplitude of the modulation pattern on the surface of the modulation film prepared by adopting the polypropylene grafted styrene solution of the comparative example is large, and the modulation pattern of the template cannot be completely transferred to the surface of the polymer film.
Comparative example 2:
a method for preparing a film-foam dual-medium modulation target by casting compounding comprises the following steps:
step one, preparing a polypropylene grafted styrene solution with the concentration of 0.03g/mL, uniformly pouring the polypropylene grafted styrene solution on the surface of a modulation template with modulation patterns, keeping the modulation template horizontal and volatilizing a solvent at room temperatureDemoulding after the solvent is completely volatilized to obtain a modulation film with sinusoidal patterns with different periods and amplitudes on the surface; the surface of the obtained modulation film is processed by adopting low-temperature plasma, and the process comprises the following steps: putting the modulation film into a cavity of a low-temperature plasma treatment instrument, opening a vacuum pump, introducing argon after the vacuum degree in the cavity is lower than 10Pa, and setting the argon flow to be 35cm3Min, adjusting the power of a high-frequency power supply to be 50W, and the operating pressure to be 30Pa, and beginning to perform low-temperature plasma modification on the surface of the modulation film for 5 s;
step two, pouring the resorcinol-formaldehyde sol solution on the surface of the modulation film in the step one, performing ultrasonic treatment at 65 ℃ for 90min to obtain resorcinol-formaldehyde gel on the surface of the modulation film, adding the resorcinol-formaldehyde gel into isopropanol, standing for solvent exchange, replacing the isopropanol every day for 3 days, and then performing supercritical CO2Extracting and drying to obtain a polypropylene grafted styrene film and resorcinol-formaldehyde aerogel foam compounded double-medium modulation target; the frequency of the ultrasound is 55 kHz;
the preparation method of the polypropylene grafted styrene solution comprises the following steps: 20g of polypropylene powder and 0.1g of benzoyl peroxide were added to supercritical CO2Introducing CO into the reactor2Using supercritical CO at a pressure of 15MPa and a temperature of 38 DEG C2Swelling for 75min, then releasing pressure at the speed of 0.2MPa/min, after pressure release, adding 25g of styrene, introducing carbon dioxide again, stirring and reacting for 2h at the temperature of 80 ℃ under the pressure of 15MPa, releasing pressure, washing a product with ethanol, and then extracting with chloroform in a Soxhlet extractor to constant weight to obtain polypropylene grafted styrene; adding polypropylene grafted styrene into a mixed solvent of 1,2, 4-trichlorobenzene and DMF, and stirring for dissolving to obtain a polypropylene grafted styrene solution with the concentration of 0.03 g/mL; the volume ratio of the 1,2, 4-trichlorobenzene to the DMF is 2: 1;
the preparation method of the resorcinol-formaldehyde sol solution comprises the following steps: adding resorcinol, polyoxyethylene and nano-fibers into 35% formaldehyde solution, uniformly stirring, then adding sodium carbonate, and stirring and dispersing to obtain resorcinol-formaldehyde sol solution; the molar ratio of the resorcinol to the formaldehyde in the formaldehyde solution is 1: 2; the molar ratio of the resorcinol to the sodium carbonate is 1: 0.02; the mass ratio of the resorcinol to the polyoxyethylene is 1: 0.1; the mass ratio of the resorcinol to the nano-fibers is 1: 0.2;
the preparation method of the nanofiber comprises the following steps: adding polystyrene into chloroform, and stirring and dissolving to obtain a spinning solution; inputting the spinning solution into a needle head, connecting the needle head with a high-voltage electrostatic generator to carry out electrostatic spinning, and receiving spun fibers by using a receiving device to obtain a fiber membrane; crushing the fiber membrane, and sieving with a 200-mesh sieve to obtain nano fibers;
the concentration of the spinning solution is 8 wt%; the flow rate of the spinning solution is 2 mL/h; the voltage of the high-voltage electrostatic generator is 15 kV; the receiving device is tin foil; the distance between the needle head and the receiving device is 12 cm; the ambient temperature of electrostatic spinning is 40 ℃; the inner diameter of the inner needle head of the needle head is 0.6 mm;
the foam density of the film-foam dual media conditioning target prepared in comparative example 2 was tested to be 142mg/cm3
Comparative example 3:
a method for preparing a film-foam dual-medium modulation target by casting compounding comprises the following steps:
step one, preparing a polypropylene grafted styrene solution with the concentration of 0.03g/mL, uniformly pouring the polypropylene grafted styrene solution on the surface of a modulation template with modulation patterns, keeping the modulation template horizontal, volatilizing a solvent at room temperature, and demoulding after the solvent is completely volatilized to obtain a modulation film with sinusoidal patterns with different periods and amplitudes on the surface; the surface of the obtained modulation film is processed by adopting low-temperature plasma, and the process comprises the following steps: putting the modulation film into a cavity of a low-temperature plasma treatment instrument, opening a vacuum pump, introducing argon after the vacuum degree in the cavity is lower than 10Pa, and setting the argon flow to be 35cm3Min, adjusting the power of a high-frequency power supply to be 50W, and the operating pressure to be 30Pa, and beginning to perform low-temperature plasma modification on the surface of the modulation film for 5 s;
step two, pouring the resorcinol-formaldehyde sol liquid into the step onePerforming ultrasonic treatment at 65 deg.C for 90min to obtain resorcinol-formaldehyde gel, adding resorcinol-formaldehyde gel into isopropanol, standing for solvent exchange, replacing isopropanol every day for 3 days, and performing supercritical CO2Extracting and drying to obtain a polypropylene grafted styrene film and resorcinol-formaldehyde aerogel foam compounded double-medium modulation target; the frequency of the ultrasound is 55 kHz;
the preparation method of the polypropylene grafted styrene solution comprises the following steps: 20g of polypropylene powder and 0.1g of benzoyl peroxide were added to supercritical CO2Introducing CO into the reactor2Using supercritical CO at a pressure of 15MPa and a temperature of 38 DEG C2Swelling for 75min, then relieving pressure at 0.2MPa/min, adding 25g styrene after pressure relief, and introducing CO again2Stirring and reacting for 2 hours at the pressure of 15MPa and the temperature of 80 ℃, decompressing, washing a product by using ethanol, and extracting the product to constant weight by using chloroform in a Soxhlet extractor to obtain polypropylene grafted styrene; adding polypropylene grafted styrene into a mixed solvent of 1,2, 4-trichlorobenzene and DMF, and stirring for dissolving to obtain a polypropylene grafted styrene solution with the concentration of 0.03 g/mL; the volume ratio of the 1,2, 4-trichlorobenzene to the DMF is 2: 1;
the preparation method of the resorcinol-formaldehyde sol solution comprises the following steps: adding resorcinol and polyoxyethylene into 35% formaldehyde solution, stirring uniformly, adding sodium carbonate, stirring and dispersing to obtain resorcinol-formaldehyde sol solution; the molar ratio of the resorcinol to the formaldehyde in the formaldehyde solution is 1: 2; the molar ratio of the resorcinol to the sodium carbonate is 1: 0.02; the mass ratio of the resorcinol to the polyoxyethylene is 1: 0.1;
the foam density of the film-foam dual media conditioning target prepared in comparative example 2 was tested to be 167mg/cm3
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.

Claims (10)

1. A method for preparing a film-foam dual-medium modulation target by casting compounding is characterized by comprising the following steps:
preparing a polypropylene grafted styrene solution with the concentration of 0.01-0.05 g/mL, uniformly pouring the polypropylene grafted styrene solution on the surface of a modulation template with sinusoidal patterns, keeping the modulation template horizontal, volatilizing a solvent at room temperature, and demoulding after the solvent is completely volatilized to obtain a modulation film with sinusoidal patterns with different periods and amplitudes on the surface;
step two, pouring the resorcinol-formaldehyde sol solution on the surface of the modulation film in the step one, performing ultrasonic treatment for 90-120 min at 65-85 ℃, obtaining resorcinol-formaldehyde gel on the surface of the modulation film, adding the resorcinol-formaldehyde aerogel into isopropanol, standing for solvent exchange, replacing the isopropanol every day for 3 days, and then performing supercritical CO2And extracting and drying to obtain the polypropylene grafted styrene film and resorcinol-formaldehyde aerogel foam compounded dual-medium modulation target.
2. The method for cast-compounding the thin film-foam dual media modulation target according to claim 1, wherein the polypropylene grafted styrene solution is prepared by: adding 20-25 parts by weight of polypropylene powder and 0.1-0.5 part by weight of benzoyl peroxide into supercritical CO2Introducing CO into the reactor2Using supercritical CO at a pressure of 15-25 MPa and a temperature of 38-40 deg.C2Swelling for 45-75 min, then decompressing at the speed of 0.2-0.4 MPa/min, adding 25-30 parts of styrene after decompressing, and introducing CO again2Stirring and reacting for 2-4 h at the pressure of 15-25 MPa and the temperature of 80-100 ℃, relieving pressure, washing a product with ethanol, and extracting the product with chloroform in a Soxhlet extractor to constant weight to obtain polypropylene grafted styrene; adding polypropylene grafted styrene into the mixture of 1,2, 4-trichlorobenzene and N, N-dimethylformamideStirring and dissolving in a solvent to obtain a polypropylene grafted styrene solution with the concentration of 0.01-0.05 g/mL.
3. The method for preparing the film-foam dual-medium modulation target by casting compounding according to claim 1, wherein the volume ratio of the 1,2, 4-trichlorobenzene to the DMF is 2-3: 1.
4. The method for preparing the film-foam dual-medium modulation target by casting compounding according to claim 1, wherein in the first step, the surface of the obtained modulation film is treated by low-temperature plasma, and the process comprises the following steps: putting the modulation film into a cavity of a low-temperature plasma treatment instrument, opening a vacuum pump, introducing argon after the vacuum degree in the cavity is lower than 10Pa, and setting the argon flow to be 35-45 cm3And/min, adjusting the power of a high-frequency power supply to be 50-80W, and operating the pressure to be 30-60 Pa, and starting to perform low-temperature plasma modification on the surface of the modulation film for 5-10 s.
5. The method for preparing the film-foam dual-medium modulation target according to claim 1, wherein the frequency of the ultrasonic wave is 55-65 kHz.
6. The method for preparing a film-foam dual-media modulation target according to claim 1, wherein the resorcinol-formaldehyde sol solution is prepared by the following steps: adding resorcinol, polyoxyethylene and nano-fibers into a formaldehyde solution with the volume concentration of 35-40%, uniformly stirring, then adding sodium carbonate, and stirring and dispersing to obtain the resorcinol-formaldehyde sol solution.
7. The method of cast compounding thin film-foam dual media formulation target of claim 6, wherein the molar ratio of resorcinol to formaldehyde in the formaldehyde solution is from 1: 1.5-2.5; the molar ratio of the resorcinol to the sodium carbonate is 1: 0.01-0.05; the mass ratio of the resorcinol to the polyoxyethylene is 1: 0.1-0.15; the mass ratio of the resorcinol to the nano-fibers is 1: 0.2-0.3.
8. The method for cast-compounding preparation of a thin film-foam dual media modulation target according to claim 6, wherein the nanofibers are porous hollow nanofibers prepared by a method comprising: adding polystyrene and polyethyleneimine into chloroform, and stirring for dissolving to obtain a shell solution; adding polyethyleneimine into methanol, and stirring for dissolving to obtain a nuclear layer solution; respectively inputting the shell layer solution and the core layer solution into an outer layer and an inner layer of a coaxial needle at constant flow rate, connecting the coaxial needle with a high-voltage electrostatic generator for electrostatic spinning, and receiving spun fibers by using a receiving device to obtain a core-shell fiber membrane; placing the core-shell fiber membrane in water for ultrasonic washing to remove polyethyleneimine to obtain a porous hollow nanofiber membrane; and (3) crushing the porous hollow nanofiber membrane, and sieving with a 200-300-mesh sieve to obtain the porous hollow nanofiber.
9. The method for preparing the film-foam dual-medium modulation target according to claim 8, wherein the mass ratio of the polystyrene to the polyethyleneimine is 4-6: 1; the concentration of the shell layer solution is 8-18 wt%; the concentration of the nuclear layer solution is 6-15 wt%; the flow rate of the shell solution is 2-5 mL/h; the flow rate of the nuclear layer solution is 0.8-1.8 mL/h; the voltage of the high-voltage electrostatic generator is 12-25 kV; the receiving device is tin foil; the distance between the coaxial needle head and the receiving device is 12-15 cm; the ambient temperature of electrostatic spinning is 40-60 ℃; the inner diameter of the inner needle head of the coaxial needle head is 0.6-0.8 mm, and the inner diameter of the outer needle head is 1.2-1.8 mm.
10. The method for preparing the film-foam dual-medium modulation target according to claim 8, wherein the ultrasonic washing frequency is 30-40 kHz, and the time is 60-120 min.
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