CN112812561B - Preparation method of detachable floating layer material for fish sperm freezing liquid nitrogen fumigation frame - Google Patents
Preparation method of detachable floating layer material for fish sperm freezing liquid nitrogen fumigation frame Download PDFInfo
- Publication number
- CN112812561B CN112812561B CN202110251980.2A CN202110251980A CN112812561B CN 112812561 B CN112812561 B CN 112812561B CN 202110251980 A CN202110251980 A CN 202110251980A CN 112812561 B CN112812561 B CN 112812561B
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- liquid nitrogen
- fiber honeycomb
- honeycomb cloth
- layer material
- 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.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to the field of material preparation, and the detachable floating layer material for a fish sperm freezing liquid nitrogen fumigation frame prepared by the invention is a polyimide foam composite material foamed in cells of carbon fiber honeycomb cloth; the polyimide material combines the advantages of low carbon fiber density, good thermal stability and the like, and the prepared composite material has excellent low-temperature dimensional stability and lower dimensional shrinkage rate under the condition of liquid nitrogen and ultralow temperature; the carbon fiber honeycomb cloth can be subjected to cross-linking reaction with a polyimide material in a foaming process after being subjected to surface amino modification, so that the acting force between the foam material and the carbon fiber cloth is increased, and a better skeleton effect can be achieved; the use of carbon fiber honeycomb cloth enables the coefficient of heat conductivity of material to obtain promoting, and the material can reach thermal balance rapidly in the liquid nitrogen, for liquid nitrogen fumigation frame provides stable buoyancy, guarantees the stability of stifling height, is favorable to improving the repeatability of stifling effect.
Description
Technical Field
The invention relates to the field of material preparation, in particular to a preparation method of a detachable floating layer material for a fish sperm freezing liquid nitrogen fumigation frame.
Background
The ultralow temperature cryopreservation of the fish sperms can solve a plurality of problems in the fish breeding process, and the optimization of the cryopreservation step and the selection of the cryopreservation liquid are very important for reducing the freezing damage such as ice crystal damage, solute damage and the like of the sperms in the low temperature cryopreservation process. Mature products of sperm freezing liquid nitrogen fumigation frames or similar carriers are rare at present, so that most of teams who carry out related work adopt self-made supports or carriers to carry out liquid nitrogen fumigation, and the problems of unstable fumigation effect, unsatisfactory repeatability of a cooling scheme and the like exist. The company designs a liquid nitrogen fumigating frame for freezing fish sperms, wherein a detachable floating layer material is required to be used in the device, and the material needs to be immersed in liquid nitrogen for a long time in the using process to adjust the cooled height of a sample.
CN108570194A provides a preparation method of a buoyancy material, comprising: (1) mixing a resin base material weighed in advance with expanded polystyrene particles to obtain a mixture; (2) adding the mixture into a mold, sealing the mold, and vacuumizing the interior of the mold; after the inside of the mold reaches a specified vacuum degree, applying specified pressure to the mixture in the mold until the mixture in the mold keeps no volume deformation for at least 20 minutes under the specified pressure, wherein the specified pressure is 1-5 MPa; (3) and solidifying the mixture together with the mould under a specified pressure to obtain the buoyancy material. According to the preparation method of the buoyancy material provided by the embodiment of the invention, the buoyancy material is prepared by utilizing the expanded polystyrene particles and the thermosetting resin; because the price of the expanded polystyrene particles is low, the market price is 20-25 yuan/kg, which is far lower than the prices of hollow glass microspheres, hollow resin microspheres and the like, the preparation cost of the buoyancy material can be reduced.
CN110003617A relates to a preparation method of a high-performance solid buoyancy material, and belongs to the technical field of materials. According to the invention, iron chloride is mixed into sodium silicate for cross-linking molding and pyrolysis, pores formed in the sodium silicate in the pyrolysis and iron particles formed in the pores are used as catalysts, nanofibers grow in situ in a hollow glass microsphere matrix, the root of each fiber is embedded in the matrix, the head of each fiber extends out of the matrix and is tightly combined with the matrix without gaps, and the fibers are used as fillers to prepare the high-performance solid buoyancy material; the method adopts a vacuum impregnation method to prepare the high-performance solid buoyancy material, has simple equipment, is easy to control conditions, and obtains the high-performance solid buoyancy material with uniform quality, high filling rate of the hollow glass beads and good heat resistance.
CN109397599A provides a preparation method of a solid buoyant material, comprising: (1) obtaining a raw material mixture for preparing a solid buoyant material; (2) the raw material mixture is rammed and molded under the vacuum condition to obtain a blank body; (3) and curing the blank to obtain the solid buoyancy material. The preparation method of the solid buoyancy material provided by the invention is an innovative process of ramming and molding under a vacuum condition, and unexpectedly finds that the solid buoyancy material prepared by the molding process has lower water absorption rate and improves the quality of products.
In order to ensure that the liquid nitrogen fumigation effect is stable and the cooling scheme has strong repeatability, the floating layer material must keep good dimensional stability under the low-temperature condition to ensure the stability of the fumigation height and ensure the fumigation effect, and the buoyancy materials prepared by the above patents and the prior art cannot meet the use requirements.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a detachable floating layer material for a fish sperm freezing liquid nitrogen fumigation frame.
A preparation method of a detachable floating layer material for a fish sperm freezing liquid nitrogen fumigation frame comprises the following steps:
adding 28.6-35.2 parts by mass of 4, 4-diaminodiphenyl ether and 3.2-4.8 parts by mass of 1, 4-diamino-2, 5-divinylbenzene into 46.7-52.8 parts by mass of an organic solvent, stirring and mixing for 30-60min, adding 40.2-48.4 parts by mass of pyromellitic dianhydride into a reaction kettle, controlling the temperature to be 35-55 ℃, stirring and reacting for 3-6h to obtain a polyimide acid solution, and then carrying out spray drying to obtain polyimide precursor powder; then putting the modified carbon fiber honeycomb cloth into a foaming mold, uniformly dispersing polyimide precursor powder into each cell of the carbon fiber honeycomb, and closing the mold; then foaming in an oven, wherein the temperature rise procedure of the oven is 100-120 ℃ for 10-30 min; 180 ℃ and 200 ℃ for 20-40 min; 240 ℃ and 260 ℃ for 10-30 min; 270 ℃ and 290 ℃ for 20-30 min; the obtained material is irradiated and crosslinked, and the temperature is reduced to room temperature, so that the detachable floating layer material for the fish sperm freezing liquid nitrogen fumigation frame can be obtained. The modified carbon fiber honeycomb cloth is guanamine grafted carbon fiber honeycomb cloth and is treated according to the following scheme:
adding 10-15 parts of carbon fiber honeycomb cloth into 100-180 parts of deionized water according to the mass parts, adding 0.1-0.5mol/L oxidant and 0.2-0.6mol/L nitric acid, slowly heating to 70-90 ℃, stirring and reacting for 60-180min, taking out the carbon fiber honeycomb cloth after the reaction is finished, washing with deionized water, and drying to obtain oxidized carbon fiber honeycomb cloth; adding oxidized carbon fiber honeycomb cloth into 50-80 parts of N, N-dimethylformamide, adding 8-24 parts of thionyl chloride, stirring and mixing uniformly, heating to 100-120 ℃ in a closed reaction kettle, and reacting for 3-6h to obtain the impurity-containing acyl chlorinated carbon fiber;
and taking out the carbon fiber honeycomb cloth after the completion, cleaning the carbon fiber honeycomb cloth, adding the carbon fiber honeycomb cloth into 40-60 parts of pyridine, adding 4-8 parts of vinyl guanamine, heating to 50-70 ℃, reacting for 5-10 hours, taking out the carbon fiber honeycomb cloth after the completion, cleaning and drying the carbon fiber honeycomb cloth to obtain the guanamine grafted carbon fiber honeycomb cloth.
The guanamine grafted carbon fiber honeycomb cloth belt is provided with vinyl, the polyimide acid solution is provided with divinylbenzene, the foamed material is irradiated and crosslinked to obtain a more stable structure, and the prepared composite material has excellent low-temperature dimensional stability and lower dimensional shrinkage rate under the condition of liquid nitrogen and ultralow temperature.
The reaction mechanism equation is shown as follows:
the oxidant is potassium persulfate or ammonium persulfate or benzoyl peroxide.
The length of the side of the cell of the carbon fiber honeycomb cloth is 6-12 mm.
The spray drying is carried out at 120-170 ℃.
The organic solvent is N-methylacetamide or N, N-dimethylacetamide.
In the irradiation crosslinking process, the energy of an electron accelerator is 1-3MeV, and the irradiation dose is 40-50 Mrad.
The detachable floating layer material provides stable buoyancy for the fish sperm freezing liquid nitrogen fumigating frame in liquid nitrogen.
The invention relates to a detachable floating layer material for a fish sperm freezing liquid nitrogen fumigation frame, which is a polyimide foam composite material foamed in cells of carbon fiber honeycomb cloth; the polyimide material has the advantages of high wear resistance, high temperature resistance and small thermal deformation coefficient, and the invention combines the advantages of low carbon fiber density, good thermal stability and the like, so that the prepared composite material has very excellent low-temperature dimensional stability and lower dimensional shrinkage rate under the condition of liquid nitrogen and ultralow temperature; the carbon fiber honeycomb cloth can generate a cross-linking reaction with the polyimide material in the foaming process after being subjected to surface amino modification, so that the acting force between the foam material and the carbon fiber cloth is increased, a better skeleton effect can be achieved, and the polyimide material is prevented; the use of carbon fiber honeycomb cloth enables the coefficient of heat conductivity of material to obtain promoting, and the material can reach thermal balance rapidly in the liquid nitrogen, for liquid nitrogen fumigation frame provides stable buoyancy, guarantees the stability of stifling height, is favorable to improving the repeatability of stifling effect.
Drawings
FIG. 1 is a Fourier infrared spectrum of a detachable floating layer material for a fish sperm-freezing liquid nitrogen fumigation rack prepared in example 2:
at 1500/1607cm-1An absorption peak of benzene ring skeleton is present nearby, and is 1689cm-1The absorption peak of the amide at 1375cm is a telescopic absorption peak near the carbonyl group-1The absorption peak of the amide near the carbon-nitrogen single bond is 2962cm-1The expansion absorption peak of carbon-hydrogen bond exists nearby, which shows pyromellitic dianhydride, 4-diaminodiphenyl ether and 4, 4-diaminodiphenyl etherThe phenyl ether undergoes imidization, and the ester group is converted into an amide group; at 1252cm-1An absorption peak of ether bond at 3508/3396cm-1A stretching absorption peak of a nitrogen-hydrogen bond exists nearby, which indicates that the 4, 4-diaminodiphenyl ether participates in the reaction.
Detailed Description
The invention is further illustrated by the following specific examples:
according to GB/T24148.9-2014 plastic, unsaturated polyester resin (UP-R) part 9: total volume shrinkage determination precautions the total volume shrinkage of the float layer materials in the various embodiments of the present invention in liquid nitrogen (atmospheric pressure, -196 ℃) was determined; the floating layer material sample is made into a disc-shaped sample with the radius of 5cm and the thickness of 2cm, and the heat conductivity coefficient of the disc-shaped sample is measured by a DR-1 heat conductivity coefficient measuring instrument.
Example 1
A preparation method of a detachable floating layer material for a fish sperm freezing liquid nitrogen fumigation frame comprises the following steps:
adding 28.6kg of 4, 4-diaminodiphenyl ether and 3.2kg of 1, 4-diamino-2, 5-divinylbenzene into 46.7kg of organic solvent, stirring and mixing for 30min, adding 40.2kg of pyromellitic dianhydride into a reaction kettle, controlling the temperature to be 35 ℃, stirring and reacting for 3h to obtain polyimide acid solution, and then carrying out spray drying to obtain polyimide precursor powder; then putting the modified carbon fiber honeycomb cloth into a foaming mold, uniformly dispersing polyimide precursor powder into each cell of the carbon fiber honeycomb, and closing the mold; then foaming in an oven, wherein the temperature rise program of the oven is 100 ℃ for 10 min; at 180 ℃ for 20 min; at 240 ℃ for 10 min; at 270 ℃ for 20 min; the obtained material is irradiated and crosslinked, and the temperature is reduced to room temperature, so that the detachable floating layer material for the fish sperm freezing liquid nitrogen fumigation frame can be obtained.
The modified carbon fiber honeycomb cloth is processed according to the following scheme: adding 10kg of carbon fiber honeycomb cloth into 100kg of deionized water, adding 0.1mol/L oxidant and 0.2mol/L nitric acid, slowly heating to 70 ℃, stirring for reacting for 60min, taking out the carbon fiber honeycomb cloth, washing with deionized water, and drying to obtain oxidized carbon fiber honeycomb cloth; adding oxidized carbon fiber honeycomb cloth into 50kg of N, N-dimethylformamide, adding 8kg of thionyl chloride, stirring and mixing uniformly, heating to 100 ℃ in a closed reaction kettle, and reacting for 3 hours to obtain the acyl chlorinated carbon fiber containing impurities;
and taking out the carbon fiber honeycomb cloth after the completion, cleaning the carbon fiber honeycomb cloth, adding the carbon fiber honeycomb cloth into 40-kg of pyridine, adding 4kg of vinyl guanamine, heating to 50 ℃, reacting for 5 hours, taking out the carbon fiber honeycomb cloth after the completion, cleaning and drying the carbon fiber honeycomb cloth to obtain the guanamine grafted carbon fiber honeycomb cloth.
The oxidant is potassium persulfate.
The length of the side of the cell of the carbon fiber honeycomb cloth is 12 mm.
The spray drying is carried out at 120 ℃.
The organic solvent is N-methylacetamide.
The detachable floating layer material provides stable buoyancy for the fish sperm freezing liquid nitrogen fumigating frame in liquid nitrogen.
In the irradiation crosslinking process, the energy of an electron accelerator is 1MeV, and the irradiation dose is 40 Mrad.
Example 2
A preparation method of a detachable floating layer material for a fish sperm freezing liquid nitrogen fumigation frame comprises the following steps:
adding 32.4kg of 4, 4-diaminodiphenyl ether and 3.8kg of 1, 4-diamino-2, 5-divinylbenzene into 50.6kg of organic solvent, stirring and mixing for 40min, adding 44.4kg of pyromellitic dianhydride into a reaction kettle, controlling the temperature to be 45 ℃, stirring and reacting for 5h to obtain polyimide acid solution, and then carrying out spray drying to obtain polyimide precursor powder; then putting the modified carbon fiber honeycomb cloth into a foaming mold, uniformly dispersing polyimide precursor powder into each cell of the carbon fiber honeycomb, and closing the mold; then foaming in an oven, wherein the temperature rise program of the oven is 10 ℃ for 20 min; 190 ℃ for 30 min; at 250 ℃ for 20 min; at 280 ℃ for 25 min; the obtained material is irradiated and crosslinked, and the temperature is reduced to room temperature, so that the detachable floating layer material for the fish sperm freezing liquid nitrogen fumigation frame can be obtained.
The modified carbon fiber honeycomb cloth is processed according to the following scheme:
adding 12kg of carbon fiber honeycomb cloth into 140kg of deionized water, adding 0.3mol/L oxidant and 0.4mol/L nitric acid, slowly heating to 80 ℃, stirring for reaction for 120min, taking out the carbon fiber honeycomb cloth, washing with deionized water, and drying to obtain oxidized carbon fiber honeycomb cloth; adding oxidized carbon fiber honeycomb cloth into 60kg of N, N-dimethylformamide, adding 16kg of thionyl chloride, stirring and mixing uniformly, heating to 110 ℃ in a closed reaction kettle, and reacting for 4 hours to obtain the acyl chlorinated carbon fiber containing impurities;
and taking out the carbon fiber honeycomb cloth after the completion, cleaning the carbon fiber honeycomb cloth, adding the carbon fiber honeycomb cloth into 45kg of pyridine, adding 6kg of vinyl guanamine, heating to 59 ℃, reacting for 7 hours, taking out the carbon fiber honeycomb cloth after the completion, cleaning and drying the carbon fiber honeycomb cloth to obtain the guanamine grafted carbon fiber honeycomb cloth. The oxidant is ammonium persulfate.
The length of the side of the cell of the carbon fiber honeycomb cloth is 10 mm.
The spray drying is carried out at 150 ℃.
The organic solvent is N, N-dimethylacetamide.
The detachable floating layer material provides stable buoyancy for the fish sperm freezing liquid nitrogen fumigating frame in liquid nitrogen.
In the irradiation crosslinking process, the energy of an electron accelerator is 1.5MeV, and the irradiation dose is 45 Mrad.
Example 3
A preparation method of a detachable floating layer material for a fish sperm freezing liquid nitrogen fumigation frame comprises the following steps:
adding 35.2kg of 4, 4-diaminodiphenyl ether and 4.8kg of 1, 4-diamino-2, 5-divinylbenzene into 52.8kg of organic solvent, stirring and mixing for 60min, adding 48.4kg of pyromellitic dianhydride into a reaction kettle, controlling the temperature to be 55 ℃, stirring and reacting for 6h to obtain polyimide acid solution, and then carrying out spray drying to obtain polyimide precursor powder; then putting the modified carbon fiber honeycomb cloth into a foaming mold, uniformly dispersing polyimide precursor powder into each cell of the carbon fiber honeycomb, and closing the mold; then foaming in an oven, wherein the temperature rise program of the oven is 120 ℃ for 30 min; at 200 ℃ for 40 min; at 260 ℃ for 30 min; 290 ℃ for 30 min; the obtained material is irradiated and crosslinked, and the temperature is reduced to room temperature, so that the detachable floating layer material for the fish sperm freezing liquid nitrogen fumigation frame can be obtained.
The modified carbon fiber honeycomb cloth is processed according to the following scheme:
adding 15kg of carbon fiber honeycomb cloth into 180kg of deionized water, adding 0.5mol/L oxidant and 0.6mol/L nitric acid, slowly heating to 90 ℃, stirring for reacting for 180min, taking out the carbon fiber honeycomb cloth, washing with deionized water, and drying to obtain oxidized carbon fiber honeycomb cloth; adding oxidized carbon fiber honeycomb cloth into 80kgN, N-dimethylformamide, adding 24kg of thionyl chloride, stirring and mixing uniformly, heating to 120 ℃ in a closed reaction kettle, and reacting for 6 hours to obtain the acyl chlorinated carbon fiber containing impurities;
and taking out the carbon fiber honeycomb cloth after the completion, cleaning the carbon fiber honeycomb cloth, adding the carbon fiber honeycomb cloth into 60kg of pyridine, adding 8kg of vinyl guanamine, heating to 70 ℃, reacting for 10 hours, taking out the carbon fiber honeycomb cloth after the completion, cleaning and drying the carbon fiber honeycomb cloth to obtain the guanamine grafted carbon fiber honeycomb cloth. The oxidant is benzoyl peroxide.
The length of the side of the cell of the carbon fiber honeycomb cloth is 12 mm.
The spray drying is carried out at 170 ℃.
The organic solvent is N, N-dimethylacetamide.
The detachable floating layer material provides stable buoyancy for the fish sperm freezing liquid nitrogen fumigating frame in liquid nitrogen.
In the irradiation crosslinking process, the energy of an electron accelerator is 3MeV, and the irradiation dose is 50 Mrad.
The thermal conductivity and the total volume shrinkage after liquid nitrogen cooling of the float layer materials prepared in the above examples are shown in the following table:
| total volume shrinkage (%) | Thermal conductivity (W/(m.k)) | |
| Example 1 | 1.14 | 8.84×10-2 |
| Example 2 | 0.91 | 8.97×10-2 |
| Example 3 | 0.86 | 9.21×10-2 |
Comparative example 1
A preparation method of a detachable floating layer material for a fish sperm freezing liquid nitrogen fumigation frame comprises the following steps:
adding 28.6kg of 4, 4-diaminodiphenyl ether and 3.2kg of 1, 4-diamino-2, 5-divinylbenzene into 46.7kg of organic solvent, stirring and mixing for 30min, adding 40.2kg of pyromellitic dianhydride into a reaction kettle, controlling the temperature to be 35 ℃, stirring and reacting for 3h to obtain polyimide acid solution, and then carrying out spray drying to obtain polyimide precursor powder; then uniformly dispersing the polyimide precursor powder in a foaming mold, and closing the mold; then foaming in an oven, wherein the temperature rise program of the oven is 100 ℃ for 10 min; at 180 ℃ for 20 min; at 240 ℃ for 10 min; at 270 ℃ for 20 min; the obtained material is irradiated and crosslinked, and the temperature is reduced to room temperature, so that the detachable floating layer material for the fish sperm freezing liquid nitrogen fumigation frame can be obtained.
The spray drying is carried out at 120 ℃.
The organic solvent is N-methylacetamide.
In the irradiation crosslinking process, the energy of an electron accelerator is 1MeV, and the irradiation dose is 40 Mrad.
The detachable floating layer material provides stable buoyancy for the fish sperm freezing liquid nitrogen fumigating frame in liquid nitrogen.
Comparative example 2
A preparation method of a detachable floating layer material for a fish sperm freezing liquid nitrogen fumigation frame comprises the following steps:
adding 28.6kg of 4, 4-diaminodiphenyl ether and 3.2kg of 1, 4-diamino-2, 5-divinylbenzene into 46.7kg of organic solvent, stirring and mixing for 30min, adding 40.2kg of pyromellitic dianhydride into a reaction kettle, controlling the temperature to be 35 ℃, stirring and reacting for 3h to obtain polyimide acid solution, and then carrying out spray drying to obtain polyimide precursor powder; then putting the carbon fiber honeycomb cloth into a foaming mould, uniformly dispersing polyimide precursor powder into each cell of the carbon fiber honeycomb, and closing the mould; then foaming in an oven, wherein the temperature rise program of the oven is 100 ℃ for 10 min; at 180 ℃ for 20 min; at 240 ℃ for 10 min; at 270 ℃ for 20 min; the obtained material is irradiated and crosslinked, and the temperature is reduced to room temperature, so that the detachable floating layer material for the fish sperm freezing liquid nitrogen fumigation frame can be obtained.
The spray drying is carried out at 120 ℃.
The organic solvent is N-methylacetamide.
In the irradiation crosslinking process, the energy of an electron accelerator is 1MeV, and the irradiation dose is 40 Mrad.
The detachable floating layer material provides stable buoyancy for the fish sperm freezing liquid nitrogen fumigating frame in liquid nitrogen.
Comparative example 3
A preparation method of a detachable floating layer material for a fish sperm freezing liquid nitrogen fumigation frame comprises the following steps:
adding 28.6kg of 4, 4-diaminodiphenyl ether into 46.7kg of organic solvent, stirring and mixing for 30min, adding 40.2kg of pyromellitic dianhydride into a reaction kettle, controlling the temperature to be 35 ℃, stirring and reacting for 3h to obtain polyimide acid solution, and then carrying out spray drying to obtain polyimide precursor powder; then putting the modified carbon fiber honeycomb cloth into a foaming mold, uniformly dispersing polyimide precursor powder into each cell of the carbon fiber honeycomb, and closing the mold; then foaming in an oven, wherein the temperature rise program of the oven is 100 ℃ for 10 min; at 180 ℃ for 20 min; at 240 ℃ for 10 min; at 270 ℃ for 20 min; and (3) irradiating and crosslinking the material obtained at room temperature, and cooling to room temperature to obtain the detachable floating layer material for the fish sperm freezing liquid nitrogen fumigation frame.
The modified carbon fiber honeycomb cloth is guanamine grafted carbon fiber honeycomb cloth. The following scheme is adopted for treatment:
adding 10kg of carbon fiber honeycomb cloth into 100kg of deionized water, adding 0.1mol/L oxidant and 0.2mol/L nitric acid, slowly heating to 70 ℃, stirring for reacting for 60min, taking out the carbon fiber honeycomb cloth, washing with deionized water, and drying to obtain oxidized carbon fiber honeycomb cloth; adding oxidized carbon fiber honeycomb cloth into 50kgN, N-dimethylformamide, adding 8kg of thionyl chloride, stirring and mixing uniformly, heating to 100 ℃ in a closed reaction kettle, reacting for 3 hours, and reacting for 3 hours to obtain the acyl chlorinated carbon fiber containing impurities;
and taking out the carbon fiber honeycomb cloth after the completion, cleaning the carbon fiber honeycomb cloth, adding the carbon fiber honeycomb cloth into 40-kg of pyridine, adding 4kg of vinyl guanamine, heating to 50 ℃, reacting for 5 hours, taking out the carbon fiber honeycomb cloth after the completion, cleaning and drying the carbon fiber honeycomb cloth to obtain the guanamine grafted carbon fiber honeycomb cloth. The oxidant is potassium persulfate.
The oxidant is potassium persulfate.
The length of the side of the cell of the carbon fiber honeycomb cloth is 12 mm.
The spray drying is carried out at 120 ℃.
The organic solvent is N-methylacetamide.
In the irradiation crosslinking process, the energy of an electron accelerator is 1MeV, and the irradiation dose is 40 Mrad.
The detachable floating layer material provides stable buoyancy for the fish sperm freezing liquid nitrogen fumigating frame in liquid nitrogen.
The thermal conductivity and the total volume shrinkage test results after liquid nitrogen cooling of the float layer material prepared in the above comparative example are shown in the following table:
| total volume shrinkage (%) | Thermal conductivity (W/(m.k)) | |
| Comparative example 1 | 4.82 | 8.42×10-2 |
| Comparative example 2 | 2.71 | 8.81×10-2 |
| Comparative example 3 | 1.63 | 8.73×10-2 |
Claims (8)
1. A preparation method of a detachable floating layer material for a fish sperm freezing liquid nitrogen fumigation frame comprises the following steps: adding 28.6-35.2 parts by mass of 4,4' -diaminodiphenyl ether and 3.2-4.8 parts by mass of 1, 4-diamino-2, 5-divinylbenzene into 46.7-52.8 parts by mass of an organic solvent, stirring and mixing for 30-60min, adding 40.2-48.4 parts by mass of pyromellitic dianhydride into a reaction kettle, controlling the temperature to be 35-55 ℃, stirring and reacting for 3-6h to obtain a polyimide solution, and then carrying out spray drying to obtain polyimide precursor powder; then putting the modified carbon fiber honeycomb cloth into a foaming mold, uniformly dispersing polyimide precursor powder into each cell of the carbon fiber honeycomb, and closing the mold; then foaming in an oven, wherein the temperature rise procedure of the oven is 100-120 ℃ for 10-30 min; 180 ℃ and 200 ℃ for 20-40 min; 240 ℃ and 260 ℃ for 10-30 min; 270 ℃ and 290 ℃ for 20-30 min; the obtained material is irradiated and crosslinked, and the temperature is reduced to room temperature, so that the detachable floating layer material for the fish sperm freezing liquid nitrogen fumigation frame can be obtained.
2. The preparation method of the detachable floating layer material for the fish sperm freezing liquid nitrogen fumigation frame as claimed in claim 1, is characterized in that: the modified carbon fiber honeycomb cloth is guanamine grafted carbon fiber honeycomb cloth and is treated according to the following scheme:
adding 10-15 parts of carbon fiber honeycomb cloth into 100-180 parts of deionized water according to the mass parts, adding 0.1-0.5mol/L oxidant and 0.2-0.6mol/L nitric acid, slowly heating to 70-90 ℃, stirring and reacting for 60-180min, taking out the carbon fiber honeycomb cloth after the reaction is finished, washing with deionized water, and drying to obtain oxidized carbon fiber honeycomb cloth; adding oxidized carbon fiber honeycomb cloth into 50-80 parts of N, N-dimethylformamide and 8-24 parts of thionyl chloride, stirring and mixing uniformly, heating to 100-120 ℃ in a closed reaction kettle, and reacting for 3-6h to obtain the acyl chlorinated carbon fiber honeycomb cloth containing impurities;
and taking out the carbon fiber honeycomb cloth after the completion, cleaning the carbon fiber honeycomb cloth, adding the carbon fiber honeycomb cloth into 40-60 parts of pyridine, adding 4-8 parts of vinyl guanamine, heating to 50-70 ℃, reacting for 5-10 hours, taking out the carbon fiber honeycomb cloth after the completion, cleaning and drying the carbon fiber honeycomb cloth to obtain the guanamine grafted carbon fiber honeycomb cloth.
3. The preparation method of the detachable floating layer material for the fish sperm freezing liquid nitrogen fumigation frame as claimed in claim 2, wherein the method comprises the following steps: the oxidant is potassium persulfate or ammonium persulfate or benzoyl peroxide.
4. The preparation method of the detachable floating layer material for the fish sperm freezing liquid nitrogen fumigation frame as claimed in claim 2, wherein the method comprises the following steps: the length of the side of the cell of the carbon fiber honeycomb cloth is 6-12 mm.
5. The preparation method of the detachable floating layer material for the fish sperm freezing liquid nitrogen fumigation frame as claimed in claim 1, is characterized in that: the spray drying is carried out at 120-170 ℃.
6. The preparation method of the detachable floating layer material for the fish sperm freezing liquid nitrogen fumigation frame as claimed in claim 1, is characterized in that: the organic solvent is N-methylacetamide or N, N-dimethylacetamide.
7. The preparation method of the detachable floating layer material for the fish sperm freezing liquid nitrogen fumigation frame as claimed in claim 1, is characterized in that: the detachable floating layer material provides stable buoyancy for the fish sperm freezing liquid nitrogen fumigating frame in liquid nitrogen.
8. The preparation method of the detachable floating layer material for the fish sperm freezing liquid nitrogen fumigation frame as claimed in claim 1, is characterized in that: in the irradiation crosslinking process, the energy of an electron accelerator is 1-2MeV, and the irradiation dose is 40 Mrad.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110251980.2A CN112812561B (en) | 2021-03-08 | 2021-03-08 | Preparation method of detachable floating layer material for fish sperm freezing liquid nitrogen fumigation frame |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110251980.2A CN112812561B (en) | 2021-03-08 | 2021-03-08 | Preparation method of detachable floating layer material for fish sperm freezing liquid nitrogen fumigation frame |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112812561A CN112812561A (en) | 2021-05-18 |
| CN112812561B true CN112812561B (en) | 2022-04-19 |
Family
ID=75863018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110251980.2A Active CN112812561B (en) | 2021-03-08 | 2021-03-08 | Preparation method of detachable floating layer material for fish sperm freezing liquid nitrogen fumigation frame |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112812561B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117776752B (en) * | 2023-12-25 | 2024-07-02 | 宜兴市新立织造有限公司 | Honeycomb foam sandwich bearing/heat insulation composite material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4407980A (en) * | 1982-09-27 | 1983-10-04 | John Gagliani | Closed cell polyimide foams and methods of making same |
| US5514444A (en) * | 1994-06-17 | 1996-05-07 | Hexcel Corporation | Fiber reinforced polyimide honeycomb for high temperature applications |
| CN101130632A (en) * | 2007-08-08 | 2008-02-27 | 北京航空航天大学 | Polyimide froth in situ filling honeycomb composite material |
| CN105017769A (en) * | 2014-04-21 | 2015-11-04 | 中国科学院化学研究所 | Cellular reinforcement thermosetting hard closed-cell polyimide foam composite material as well as preparation method and application thereof |
| CN105820571A (en) * | 2016-05-10 | 2016-08-03 | 河北科技大学 | Carbon fiber honeycomb reinforced polyimide foam material and preparation method thereof |
| CN109553905A (en) * | 2018-11-24 | 2019-04-02 | 浙江中科恒泰新材料科技有限公司 | A kind of preparation method of the polymethacrylimide foam composite material of enhancing |
-
2021
- 2021-03-08 CN CN202110251980.2A patent/CN112812561B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4407980A (en) * | 1982-09-27 | 1983-10-04 | John Gagliani | Closed cell polyimide foams and methods of making same |
| US5514444A (en) * | 1994-06-17 | 1996-05-07 | Hexcel Corporation | Fiber reinforced polyimide honeycomb for high temperature applications |
| CN101130632A (en) * | 2007-08-08 | 2008-02-27 | 北京航空航天大学 | Polyimide froth in situ filling honeycomb composite material |
| CN105017769A (en) * | 2014-04-21 | 2015-11-04 | 中国科学院化学研究所 | Cellular reinforcement thermosetting hard closed-cell polyimide foam composite material as well as preparation method and application thereof |
| CN105820571A (en) * | 2016-05-10 | 2016-08-03 | 河北科技大学 | Carbon fiber honeycomb reinforced polyimide foam material and preparation method thereof |
| CN109553905A (en) * | 2018-11-24 | 2019-04-02 | 浙江中科恒泰新材料科技有限公司 | A kind of preparation method of the polymethacrylimide foam composite material of enhancing |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112812561A (en) | 2021-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112812561B (en) | Preparation method of detachable floating layer material for fish sperm freezing liquid nitrogen fumigation frame | |
| CN108383101B (en) | Preparation method of polyacrylonitrile-based three-dimensional macroporous carbon block | |
| CN101876009A (en) | Method for preparing ceramic particle reinforced foamed aluminum-matrix composite material | |
| CN102702562A (en) | Preparation method for thermoplastic polyimide foaming particle and formed body thereof | |
| CN109850870A (en) | A kind of high-strength carbon aeroge and its preparation method and application | |
| CN105542335B (en) | Resistant to elevated temperatures acid imide polyvinyl chloride alloy structural foam and preparation method thereof | |
| CN106832384A (en) | A kind of ketone foamed material of lateral group polyarylether containing phthalein and preparation method thereof | |
| CN106478124A (en) | A kind of preparation method of porous charcoal heat-insulation composite material | |
| CN108912380B (en) | Method for preparing high-rate polymer foam by using PMMA/PVDF blend under low-pressure condition | |
| CN113817212A (en) | Benzoxazine nitrile resin sandwich structure foam and preparation method thereof | |
| WO2018171118A1 (en) | Composite thermal insulation material having antibacterial effect, and preparation method therefor | |
| CN101811885B (en) | Method for preparing foam carbon by using furan resin | |
| CN110303158A (en) | A kind of novel method for preparing foamed aluminium | |
| CN112476929A (en) | Supercritical fluid low-temperature secondary foaming process | |
| CN111004456B (en) | Light-weight high-strength heat-resistant polyvinyl chloride foam material and preparation method thereof | |
| CN104804190A (en) | Flame-retardant polyimide foam material comprising honeycomb core space structure, and preparation method | |
| US20220185981A1 (en) | Low-temperature supercritical foaming process | |
| CN110553470A (en) | Supercritical drying method for preparing ultra-low density aerogel and product prepared by same | |
| CN112940334B (en) | Preparation method of high-thermal-insulation high-compression-resistance low-density heat-resistant composite epoxy foam | |
| CN109535729A (en) | A kind of preparation method of the silicon rubber foam with high apparent mass | |
| CN110921648B (en) | One-step preparation method of light high-strength microspheric phenolic resin-based carbon foam | |
| CN115232351B (en) | Preparation method of silicone rubber foam material | |
| CN113929955B (en) | Hard polyimide foam and preparation method thereof | |
| CN114132937A (en) | Preparation method of large-block silicon dioxide aerogel | |
| CN102219212B (en) | Manufacture method for molded part of foamed active electrical carbon 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 |