CN113527842A - Low-temperature-resistant anti-freezing bionic bait and preparation method thereof - Google Patents
Low-temperature-resistant anti-freezing bionic bait and preparation method thereof Download PDFInfo
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- CN113527842A CN113527842A CN202110785755.7A CN202110785755A CN113527842A CN 113527842 A CN113527842 A CN 113527842A CN 202110785755 A CN202110785755 A CN 202110785755A CN 113527842 A CN113527842 A CN 113527842A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01K—ANIMAL HUSBANDRY; CARE OF BIRDS, FISHES, INSECTS; FISHING; REARING OR BREEDING ANIMALS, NOT OTHERWISE PROVIDED FOR; NEW BREEDS OF ANIMALS
- A01K85/00—Artificial bait for fishing
- A01K85/01—Artificial bait for fishing with light emission, sound emission, scent dispersal or the like
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
Abstract
The invention discloses low-temperature-resistant anti-freezing bionic bait and a preparation method thereof, bisphenol A type epoxy resin and a modifier are uniformly mixed, then the mixture is added into a double-screw extruder to be extruded and granulated to obtain modified epoxy resin, the modified epoxy resin, paraffin, a curing agent, a phagostimulant, a pigment and an antioxidant are uniformly mixed, then the mixture is added into the double-screw extruder to be melted and extruded into an injection molding machine, and injection molding is carried out to obtain the low-temperature-resistant anti-freezing bionic bait; the mechanical property of the bionic bait can be improved by adding the modifier, and meanwhile, the bisphenol A epoxy resin is modified by blending the modifier with the bisphenol A epoxy resin, so that the low-temperature resistance of the bisphenol A epoxy resin is improved, the low-temperature-resistant anti-freezing property of the bionic bait is greatly improved, the bionic bait can be normally used in a low-temperature water environment, cannot be damaged, the service life of the bionic bait is prolonged, and the development of bionic bait products is promoted.
Description
Technical Field
The invention relates to the field of bionic bait, in particular to low-temperature-resistant anti-freezing bionic bait and a preparation method thereof.
Background
As is well known, with the improvement of economic level of people, fishing is deeply favored by modern people as an outdoor activity, the bionic bait prepared from plastic for fishing has the effects of lifelike bionic fish, shrimp, insect and the like, can be used for a long time, does not need to replace bait and the like, is widely used by fishing enthusiasts, and the epoxy resin is an important thermosetting material, has better adhesion, corrosion resistance and stability, has excellent mechanical property and electrical insulation property, is widely used in the fields of electronic appliances, automobiles, coatings, adhesives, fiber reinforced composite material base materials and the like, and is an excellent raw material for preparing the bionic bait;
however, when the bionic bait is used for fishing under a low-temperature condition, after the bionic bait is immersed in low-temperature water, the epoxy resin has higher crosslinking density, so that the internal stress of the system is increased, and the epoxy resin is crisp, and has fatigue resistance and impact resistance performance, so that the service life of the existing bionic bait is greatly shortened after the bionic bait is used under the low-temperature environment, and economic loss is caused;
how to improve the poor low-temperature resistance and anti-freezing performance of the existing bionic bait is the problem to be solved by the invention.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide the low-temperature-resistant anti-freezing bionic bait and the preparation method thereof, wherein the preparation method comprises the following steps: the low-temperature-resistant anti-freezing bionic bait is prepared by adding bisphenol A type epoxy resin and a modifier into a high-speed mixer, uniformly mixing, adding into a double-screw extruder, carrying out melt extrusion, bracing, cooling, granulating and drying to obtain modified epoxy resin, adding the modified epoxy resin, paraffin, a curing agent, a phagostimulant, a pigment and an antioxidant into the high-speed mixer, uniformly mixing, adding into the double-screw extruder, carrying out melt extrusion into an injection molding machine, and carrying out injection molding, so that the low-temperature-resistant anti-freezing bionic bait is obtained, and the problem that the existing bionic bait is poor in low-temperature-resistant anti-freezing performance is solved.
The purpose of the invention can be realized by the following technical scheme:
the low-temperature-resistant anti-freezing bionic bait comprises the following components in parts by weight:
60-100 parts of bisphenol A epoxy resin, 4-12 parts of modifier, 1-3 parts of paraffin, 15-20 parts of curing agent, 0.1-3 parts of phagostimulant, 0.1-3 parts of pigment and 1-5 parts of antioxidant;
the low-temperature-resistant anti-freezing bionic bait is prepared by the following steps:
the method comprises the following steps: adding bisphenol A type epoxy resin and a modifier into a high-speed mixer, uniformly mixing, adding into a double-screw extruder, and carrying out melt extrusion, bracing, cooling, granulating and drying to obtain modified epoxy resin;
step two: adding the modified epoxy resin, the paraffin, the curing agent, the phagostimulant, the pigment and the antioxidant into a high-speed mixer, uniformly mixing, adding into a double-screw extruder, melting and extruding into an injection molding machine, and performing injection molding to obtain the low-temperature-resistant and anti-freezing bionic bait.
As a further scheme of the invention: the curing agent is an aliphatic amine curing agent; one or a mixture of two or more of vanillin, amino acid, ethyl lactate and coumarin as the phagostimulant in any proportion; the pigment is plant extracted pigment; the antioxidant is one or a mixture of two or more of antioxidant 168, antioxidant 1010, antioxidant 1024 and antioxidant 1076 in any proportion.
As a further scheme of the invention: the preparation process of the modifier comprises the following steps:
a1: adding a formaldehyde solution into a three-neck flask provided with a magnetic stirrer, a gas-guide tube, a constant-pressure dropping funnel and a reflux condenser tube, introducing nitrogen for protection, stirring and dropwise adding an anthranilic acid solution under the condition that the stirring speed is 500-800r/min, controlling the dropwise adding speed to be 1 drop/s, heating to reflux after the dropwise adding is finished, continuously stirring for reaction for 4-6 hours, cooling a reaction product to room temperature after the reaction is finished, standing for layering, collecting an organic layer, performing rotary evaporation to remove a solvent, and performing column chromatography separation and purification to obtain an intermediate 1;
the reaction principle is as follows:
a2: adding 3-chlorophthalic anhydride into a three-neck flask provided with a magnetic stirrer, a constant-pressure dropping funnel and a reflux condenser tube, then adding glacial acetic acid, stirring for 20-30min under the conditions that the temperature is 50-55 ℃ and the stirring speed is 300-500r/min, then dropwise adding a methylamine solution, controlling the dropwise adding speed to be 1-3mL/min, heating to reflux stirring reaction for 4-5h after the dropwise adding is finished, cooling to below 10 ℃ by using an ice water bath after the reaction is finished, carrying out vacuum filtration, and placing a filter cake in a vacuum drying box to be dried to constant weight to obtain an intermediate 2;
the reaction principle is as follows:
a3: adding the intermediate 2 and N, N-dimethylacetamide into a three-neck flask provided with a mechanical stirrer, stirring at the stirring rate of 300-500r/min until the intermediate 2 is completely dissolved, heating, adding triphenylphosphine and nickel chloride when the temperature reaches 80 ℃, stirring for dissolving, continuing to react for 10-30min, adding sodium iodide, continuing to stir for dissolving, keeping the temperature at 80-90 ℃, adding zinc powder, reacting for 5-6h at constant temperature, standing and layering the reaction product after the reaction is finished, taking the supernatant, adding the supernatant into methanol, stirring for 20-40min, filtering, sequentially washing the filter cake with methanol and n-hexane for 2-3 times, drying the filter cake, adding into dichloromethane, stirring until the organic matter is completely dissolved, filtering to remove zinc powder, and performing rotary evaporation on the filtrate to remove the solvent to obtain an intermediate 3;
the reaction principle is as follows:
a4: adding a sodium hydroxide solution into a three-neck flask provided with a mechanical stirrer and a constant-pressure dropping funnel, then adding an intermediate 3, stirring and gradually heating to boiling under the condition that the stirring speed is 100-200r/min, controlling the temperature rising speed to be 1-2 ℃/min, continuously stirring and reacting for 1-2h after all solids are dissolved, dropwise adding concentrated hydrochloric acid to adjust the pH of a reaction product to be 7-8 after the reaction is finished, then adding activated carbon to continuously boiling and reacting for 10-20min, filtering the reaction product after the reaction is finished, heating a filtrate to boiling, dropwise adding concentrated hydrochloric acid to adjust the pH of the reaction product to be 1-1.5, standing and cooling for 10-15h, filtering, washing a filter cake with distilled water for 2-3 times, and drying to constant weight to obtain an intermediate 4;
the reaction principle is as follows:
a5: adding the intermediate 1 and the intermediate 4 into a three-neck flask provided with a mechanical stirrer and a gas-guide tube, introducing nitrogen for protection, and stirring and reacting for 20-30h under the conditions that the temperature is 22-28 ℃, the stirring speed is 500-; and adding epoxy propanol into the intermediate 5, and continuously stirring for reacting for 20-30h to obtain the modifier.
The reaction principle is as follows:
as a further scheme of the invention: the mass fraction of the formaldehyde solution in the step A1 is 35-40%, the anthranilic acid alcohol solution is a solution formed by dissolving anthranilic acid in diethyl ether, the mass fraction of the anthranilic acid alcohol solution is 20-30%, and the molar ratio of the formaldehyde to the anthranilic acid alcohol is 1.0: 1.0-1.5.
As a further scheme of the invention: the dosage ratio of the 3-chlorophthalic anhydride, the glacial acetic acid and the methylamine solution in the step A2 is 0.19 mol: 110 mL: 20g, wherein the methylamine solution is prepared by mixing methylamine according to a mass ratio of 3: 7 dissolved in deionized water.
As a further scheme of the invention: the dosage ratio of the intermediate 2, N-dimethylacetamide, triphenylphosphine, nickel chloride, sodium iodide and zinc powder in the step A3 is 0.1 mol: 200mL of: 106 g: 13 g: 3 g: 7.0-8.0 g.
As a further scheme of the invention: the dosage ratio of the sodium hydroxide solution, the intermediate 3 and the activated carbon in the step A4 is 100 mL: 9 g: 1-3g, wherein the mass fraction of the sodium hydroxide solution is 20-25%, and the mass fraction of the concentrated hydrochloric acid is 35-37%.
As a further scheme of the invention: the molar ratio of intermediate 1 to intermediate 4 in step a5 was 1.0: 3.3, the mol ratio of the epoxy propanol to the intermediate 5 is 1.0: 3.0-7.0.
As a further scheme of the invention: a preparation method of the low-temperature-resistant anti-freezing bionic bait comprises the following steps:
the method comprises the following steps: weighing 60-100 parts of bisphenol A epoxy resin, 4-12 parts of modifier, 1-3 parts of paraffin, 15-20 parts of curing agent, 0.1-3 parts of phagostimulant, 0.1-3 parts of pigment and 1-5 parts of antioxidant according to parts by weight for later use;
step two: adding bisphenol A type epoxy resin and a modifier into a high-speed mixer, uniformly mixing, adding into a double-screw extruder, carrying out melt extrusion, bracing, cooling, granulating and drying to obtain the modified epoxy resin
Step three: adding the modified epoxy resin, the paraffin, the curing agent, the phagostimulant, the pigment and the antioxidant into a high-speed mixer, uniformly mixing, adding into a double-screw extruder, melting and extruding into an injection molding machine, and performing injection molding to obtain the low-temperature-resistant and anti-freezing bionic bait.
The invention has the beneficial effects that:
the invention relates to low-temperature-resistant anti-freezing bionic bait and a preparation method thereof.A bisphenol A type epoxy resin and a modifier are added into a high-speed mixer to be uniformly mixed, then the mixture is added into a double-screw extruder to be subjected to melt extrusion, bracing, cooling, grain cutting and drying to obtain a modified epoxy resin, the modified epoxy resin, paraffin, a curing agent, a phagostimulant, a pigment and an antioxidant are added into the high-speed mixer to be uniformly mixed, then the mixture is added into the double-screw extruder to be subjected to melt extrusion into an injection molding machine, and the injection molding is carried out to obtain the low-temperature-resistant anti-freezing bionic bait; the mechanical property of the bionic bait can be improved by adding the modifier, and meanwhile, the bisphenol A epoxy resin is modified by blending the modifier with the bisphenol A epoxy resin, so that the low-temperature resistance of the bisphenol A epoxy resin is improved, the low-temperature resistance and anti-freezing property of the bionic bait are greatly improved, the bionic bait can be normally used in a low-temperature water environment and cannot be damaged, the service life of the bionic bait is prolonged, and the development of bionic bait products is promoted;
the modifier is also prepared in the process of preparing the low-temperature-resistant antifreezing bionic bait, formaldehyde reacts with anthranilic alcohol to generate an intermediate 1, 3-chlorophthalic anhydride reacts with methylamine to generate an intermediate 2, the intermediate 2 reacts with each other to generate an intermediate 3, the intermediate 3 generates an intermediate 4 under the action of sodium hydroxide and hydrochloric acid, carboxyl on the intermediate 4 and hydroxyl on the intermediate 1 are subjected to esterification reaction to generate an intermediate 5, the intermediate 5 has a large amount of carboxyl which can react with hydroxyl on epoxy propanol and hydroxyl on bisphenol A epoxy resin, then an epoxy group on the epoxy propanol can be dehydrated and condensed with carboxyl on other intermediates 5 after ring opening, a macromolecular hyperbranched cross-linked structure is formed, and a hyperbranched polymer has a highly branched structure and is difficult to crystallize, the chains are not wound, the free volume of molecules is large, and therefore, the bionic bait still has good movement capacity in an ultralow-temperature environment, a large amount of unoccupied space is contained in a bisphenol A epoxy resin three-dimensional network, and free space still exists at low temperature, so that the low-temperature toughness of the bisphenol A epoxy resin can be increased, and on the other hand, the flexible chain segment in the hyperbranched polymer can improve the toughness and impact strength of the cured bisphenol A epoxy resin, so that the prepared bionic bait has good low-temperature-resistant anti-freezing performance and can be normally used in a low-temperature water environment.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the embodiment is a preparation method of a modifier, which comprises the following steps:
a1: adding a formaldehyde solution into a three-neck flask provided with a magnetic stirrer, an air guide pipe, a constant-pressure dropping funnel and a reflux condenser pipe, introducing nitrogen for protection, dropwise adding an anthranilic acid solution while stirring under the condition that the stirring speed is 500r/min, controlling the dropwise adding speed to be 1 drop/s, heating to reflux after dropwise adding, continuously stirring for reaction for 4 hours, cooling a reaction product to room temperature after the reaction is finished, standing for layering, collecting an organic layer, removing a solvent by rotary evaporation, and then separating and purifying by column chromatography to obtain an intermediate 1; controlling the mass fraction of the formaldehyde solution to be 35%, wherein the anthranilic alcohol solution is a solution formed by dissolving anthranilic alcohol in diethyl ether, and the mass fraction of the anthranilic alcohol solution is 20%, and the molar ratio of formaldehyde to anthranilic alcohol is 1.0: 1.0;
a2: adding 3-chlorophthalic anhydride into a three-neck flask provided with a magnetic stirrer, a constant-pressure dropping funnel and a reflux condenser tube, then adding glacial acetic acid, stirring for 20min under the conditions that the temperature is 50 ℃ and the stirring speed is 300r/min, then dropwise adding a methylamine solution, controlling the dropwise adding speed to be 1mL/min, heating to reflux and stirring for reaction for 4h after the dropwise adding is finished, cooling to below 10 ℃ by using an ice water bath after the reaction is finished, carrying out vacuum filtration, and placing a filter cake in a vacuum drying oven to be dried to constant weight to obtain an intermediate 2; controlling the dosage ratio of the 3-chlorophthalic anhydride, the glacial acetic acid and the methylamine solution to be 0.19 mol: 110 mL: 20g, wherein the methylamine solution is prepared by mixing methylamine according to a mass ratio of 3: 7 dissolving in deionized water to form a solution;
a3: adding the intermediate 2 and N, N-dimethylacetamide into a three-neck flask provided with a mechanical stirrer, stirring at a stirring speed of 300r/min until the intermediate 2 is completely dissolved, then heating, adding triphenylphosphine and nickel chloride when the temperature reaches 80 ℃, stirring to dissolve, continuing to react for 10min, then adding sodium iodide, continuing to stir to dissolve, keeping the temperature at 80 ℃, adding zinc powder, reacting for 5h at a constant temperature, standing and layering the reaction product after the reaction is finished, taking supernatant liquid, adding the supernatant liquid into methanol, stirring for 20min, filtering, washing a filter cake for 2 times by using methanol and N-hexane in sequence, drying the filter cake, adding the filter cake into dichloromethane, stirring until the organic matter is completely dissolved, filtering to remove the zinc powder, and rotationally evaporating the filtrate to remove the solvent to obtain an intermediate 3; controlling the dosage ratio of the intermediate 2, N-dimethylacetamide, triphenylphosphine, nickel chloride, sodium iodide and zinc powder to be 0.1 mol: 200mL of: 106 g: 13 g: 3 g: 7.0 g;
a4: adding a sodium hydroxide solution into a three-neck flask provided with a mechanical stirrer and a constant-pressure dropping funnel, then adding an intermediate 3, stirring and gradually heating to boiling under the condition that the stirring speed is 100r/min, controlling the temperature rising speed to be 1 ℃/min, continuously stirring and reacting for 1h after all solids are dissolved, dropwise adding concentrated hydrochloric acid to adjust the pH of a reaction product to be 7 after the reaction is finished, then adding activated carbon to continuously boiling and reacting for 10min, filtering the reaction product after the reaction is finished, heating a filtrate to boiling, dropwise adding concentrated hydrochloric acid to adjust the pH of the reaction product to be 1, standing and cooling for 10h, filtering, washing a filter cake with distilled water for 2 times, and drying to constant weight to obtain an intermediate 4; controlling the dosage ratio of the sodium hydroxide solution, the intermediate 3 and the active carbon to be 100 mL: 9 g: 1g, wherein the mass fraction of the sodium hydroxide solution is 20%, and the mass fraction of the concentrated hydrochloric acid is 35%;
a5: adding the intermediate 1 and the intermediate 4 into a three-neck flask provided with a mechanical stirrer and an air duct, introducing nitrogen for protection, and stirring and reacting for 20 hours at the temperature of 22 ℃ and the stirring speed of 500r/min to obtain an intermediate 5; adding epoxy propanol into the intermediate 5, and continuously stirring for reacting for 20 hours to obtain a modifier; the molar ratio of the intermediate 1 to the intermediate 4 is 1.0: 3.3, the mol ratio of the epoxy propanol to the intermediate 5 is 1.0: 3.0.
example 2:
the embodiment is a preparation method of a modifier, which comprises the following steps:
a1: adding a formaldehyde solution into a three-neck flask provided with a magnetic stirrer, an air guide tube, a constant-pressure dropping funnel and a reflux condenser tube, introducing nitrogen for protection, dropwise adding an anthranilic acid solution while stirring under the condition that the stirring speed is 800r/min, controlling the dropwise adding speed to be 1 drop/s, heating to reflux after dropwise adding, continuously stirring for reaction for 6 hours, cooling a reaction product to room temperature after the reaction is finished, standing for layering, collecting an organic layer, removing a solvent by rotary evaporation, and then separating and purifying by column chromatography to obtain an intermediate 1; controlling the mass fraction of the formaldehyde solution to be 40%, wherein the anthranilic alcohol solution is a solution formed by dissolving anthranilic alcohol in diethyl ether and having the mass fraction of 30%, and the molar ratio of formaldehyde to anthranilic alcohol is 1.0: 1.5;
a2: adding 3-chlorophthalic anhydride into a three-neck flask provided with a magnetic stirrer, a constant-pressure dropping funnel and a reflux condenser tube, then adding glacial acetic acid, stirring for 30min under the conditions that the temperature is 55 ℃ and the stirring speed is 500r/min, then dropwise adding a methylamine solution, controlling the dropwise adding speed to be 3mL/min, heating to reflux and stirring for reaction for 5h after the dropwise adding is finished, cooling to below 10 ℃ by using an ice water bath after the reaction is finished, carrying out vacuum filtration, and placing a filter cake in a vacuum drying oven to be dried to constant weight to obtain an intermediate 2; controlling the dosage ratio of the 3-chlorophthalic anhydride, the glacial acetic acid and the methylamine solution to be 0.19 mol: 110 mL: 20g, wherein the methylamine solution is prepared by mixing methylamine according to a mass ratio of 3: 7 dissolving in deionized water to form a solution;
a3: adding the intermediate 2 and N, N-dimethylacetamide into a three-neck flask provided with a mechanical stirrer, stirring at a stirring speed of 500r/min until the intermediate 2 is completely dissolved, then heating, adding triphenylphosphine and nickel chloride when the temperature reaches 80 ℃, stirring to dissolve, continuing to react for 30min, then adding sodium iodide, continuing to stir to dissolve, keeping the temperature at 90 ℃, adding zinc powder, reacting for 6h at a constant temperature, standing and layering the reaction product after the reaction is finished, taking supernatant liquid, adding the supernatant liquid into methanol, stirring for 40min, filtering, washing a filter cake for 3 times by using methanol and N-hexane in sequence, drying the filter cake, adding the filter cake into dichloromethane, stirring until the organic matter is completely dissolved, filtering to remove the zinc powder, and rotationally evaporating the filtrate to remove the solvent to obtain an intermediate 3; controlling the dosage ratio of the intermediate 2, N-dimethylacetamide, triphenylphosphine, nickel chloride, sodium iodide and zinc powder to be 0.1 mol: 200mL of: 106 g: 13 g: 3 g: 8.0 g;
a4: adding a sodium hydroxide solution into a three-neck flask provided with a mechanical stirrer and a constant-pressure dropping funnel, then adding an intermediate 3, stirring and gradually heating to boiling under the condition that the stirring speed is 200r/min, controlling the temperature rising speed to be 2 ℃/min, continuously stirring and reacting for 2h after all solids are dissolved, dropwise adding concentrated hydrochloric acid to adjust the pH of a reaction product to be 8 after the reaction is finished, then adding activated carbon to continuously boil for 20min, filtering the reaction product after the reaction is finished, heating a filtrate to boiling, dropwise adding concentrated hydrochloric acid to adjust the pH of the reaction product to be 1.5, standing and cooling for 15h, filtering, washing a filter cake with distilled water for 3 times, and drying to constant weight to obtain an intermediate 4; controlling the dosage ratio of the sodium hydroxide solution, the intermediate 3 and the active carbon to be 100 mL: 9 g: 3g, wherein the mass fraction of the sodium hydroxide solution is 25%, and the mass fraction of the concentrated hydrochloric acid is 37%;
a5: adding the intermediate 1 and the intermediate 4 into a three-neck flask provided with a mechanical stirrer and an air duct, introducing nitrogen for protection, and stirring and reacting for 30 hours at the temperature of 28 ℃ and the stirring speed of 800r/min to obtain an intermediate 5; adding epoxy propanol into the intermediate 5, and continuously stirring for reacting for 30h to obtain a modifier; the molar ratio of the intermediate 1 to the intermediate 4 is 1.0: 3.3, the mol ratio of the epoxy propanol to the intermediate 5 is 1.0: 7.0.
example 3:
the embodiment is a preparation method of low-temperature-resistant anti-freezing bionic bait, which comprises the following steps:
the method comprises the following steps: weighing 60 parts of bisphenol A epoxy resin, 4 parts of modifier from example 1, 1 part of paraffin, 15 parts of curing agent, 0.1 part of phagostimulant, 0.1 part of pigment and 1 part of antioxidant according to parts by weight for later use;
step two: adding bisphenol A type epoxy resin and a modifier into a high-speed mixer, uniformly mixing, adding into a double-screw extruder, carrying out melt extrusion, bracing, cooling, granulating and drying to obtain the modified epoxy resin
Step three: adding the modified epoxy resin, the paraffin, the curing agent, the phagostimulant, the pigment and the antioxidant into a high-speed mixer, uniformly mixing, adding into a double-screw extruder, melting and extruding into an injection molding machine, and performing injection molding to obtain the low-temperature-resistant and anti-freezing bionic bait.
Example 4:
the embodiment is a preparation method of low-temperature-resistant anti-freezing bionic bait, which comprises the following steps:
the method comprises the following steps: weighing 100 parts of bisphenol A epoxy resin, 12 parts of modifier from example 1, 3 parts of paraffin, 20 parts of curing agent, 3 parts of phagostimulant, 3 parts of pigment and 5 parts of antioxidant according to parts by weight for later use;
step two: adding bisphenol A type epoxy resin and a modifier into a high-speed mixer, uniformly mixing, adding into a double-screw extruder, carrying out melt extrusion, bracing, cooling, granulating and drying to obtain the modified epoxy resin
Step three: adding the modified epoxy resin, the paraffin, the curing agent, the phagostimulant, the pigment and the antioxidant into a high-speed mixer, uniformly mixing, adding into a double-screw extruder, melting and extruding into an injection molding machine, and performing injection molding to obtain the low-temperature-resistant and anti-freezing bionic bait.
Comparative example 1:
comparative example 1 differs from example 4 in that no modifier is added.
Comparative example 2:
comparative example 1 differs from example 4 in that a styrene-butadiene thermoplastic elastomer is used instead of the modifier.
The performances of the examples 3-4 and the comparative examples 1-2 are detected, the tensile property of the bionic bait is tested according to ASTM D638-2003, the compression property of the bionic bait is tested according to ASTM D695-2010, and the bending property of the bionic bait is tested according to ASTM D790-2010; the low-temperature environment is obtained by adopting a liquid nitrogen soaking method, a sample is soaked in liquid nitrogen, the temperature is kept for 20min under the environment with the temperature of 77K, then the sample is taken out, the test is completed in a short time, and the detection result is shown in the following table.
According to the data in the table, by comparing the example with the comparative example 1 and comparing the comparative example 2 with the comparative example, it can be known that the modifier and the styrene-butadiene thermoplastic elastomer in the invention improve the mechanical properties of the bionic bait, and improve the low-temperature anti-freezing performance of the bionic bait, but the modifier is more obvious and has better performance at low temperature.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (9)
1. The low-temperature-resistant anti-freezing bionic bait is characterized by comprising the following components in parts by weight:
60-100 parts of bisphenol A epoxy resin, 4-12 parts of modifier, 1-3 parts of paraffin, 15-20 parts of curing agent, 0.1-3 parts of phagostimulant, 0.1-3 parts of pigment and 1-5 parts of antioxidant;
the low-temperature-resistant anti-freezing bionic bait is prepared by the following steps:
the method comprises the following steps: adding bisphenol A type epoxy resin and a modifier into a high-speed mixer, uniformly mixing, adding into a double-screw extruder, and carrying out melt extrusion, bracing, cooling, granulating and drying to obtain modified epoxy resin;
step two: adding the modified epoxy resin, the paraffin, the curing agent, the phagostimulant, the pigment and the antioxidant into a high-speed mixer, uniformly mixing, adding into a double-screw extruder, melting and extruding into an injection molding machine, and performing injection molding to obtain the low-temperature-resistant and anti-freezing bionic bait.
2. The low-temperature-resistant anti-freezing bionic bait as claimed in claim 1, wherein the curing agent is an aliphatic amine curing agent; one or a mixture of two or more of vanillin, amino acid, ethyl lactate and coumarin as the phagostimulant in any proportion; the pigment is plant extracted pigment; the antioxidant is one or a mixture of two or more of antioxidant 168, antioxidant 1010, antioxidant 1024 and antioxidant 1076 in any proportion.
3. The low-temperature-resistant anti-freezing bionic bait as claimed in claim 1, wherein the modifier is prepared by the following steps:
a1: adding a formaldehyde solution into a three-neck flask provided with a magnetic stirrer, a gas-guide tube, a constant-pressure dropping funnel and a reflux condenser tube, introducing nitrogen for protection, stirring and dropwise adding an anthranilic acid solution under the condition that the stirring speed is 500-800r/min, controlling the dropwise adding speed to be 1 drop/s, heating to reflux after the dropwise adding is finished, continuously stirring for reaction for 4-6 hours, cooling a reaction product to room temperature after the reaction is finished, standing for layering, collecting an organic layer, performing rotary evaporation, and performing column chromatography separation and purification to obtain an intermediate 1;
a2: adding 3-chlorophthalic anhydride into a three-neck flask provided with a magnetic stirrer, a constant-pressure dropping funnel and a reflux condenser tube, then adding glacial acetic acid, stirring for 20-30min under the conditions that the temperature is 50-55 ℃ and the stirring speed is 300-500r/min, then dropwise adding a methylamine solution, controlling the dropwise adding speed to be 1-3mL/min, heating to reflux stirring reaction for 4-5h after the dropwise adding is finished, cooling to below 10 ℃ by using an ice water bath after the reaction is finished, carrying out vacuum filtration, and placing a filter cake in a vacuum drying box to be dried to constant weight to obtain an intermediate 2;
a3: adding the intermediate 2 and N, N-dimethylacetamide into a three-neck flask provided with a mechanical stirrer, stirring at the stirring rate of 300-500r/min until the intermediate 2 is completely dissolved, heating, adding triphenylphosphine and nickel chloride when the temperature reaches 80 ℃, stirring and dissolving, continuing to react for 10-30min, adding sodium iodide, continuing to stir and dissolve, keeping the temperature at 80-90 ℃, adding zinc powder, reacting at constant temperature for 5-6h, standing and layering the reaction product after the reaction is finished, taking supernatant liquid to add into methanol, stirring for 20-40min, filtering, washing the filter cake for 2-3 times with methanol and N-hexane in sequence, drying the filter cake, adding into dichloromethane, stirring and dissolving, filtering, and rotationally evaporating the filtrate to obtain an intermediate 3;
a4: adding a sodium hydroxide solution into a three-neck flask provided with a mechanical stirrer and a constant-pressure dropping funnel, then adding an intermediate 3, stirring and gradually heating to boiling under the condition that the stirring speed is 100-200r/min, controlling the temperature rising speed to be 1-2 ℃/min, continuously stirring and reacting for 1-2h after all solids are dissolved, dropwise adding concentrated hydrochloric acid to adjust the pH of a reaction product to be 7-8 after the reaction is finished, then adding activated carbon to continuously boiling and reacting for 10-20min, filtering the reaction product after the reaction is finished, heating a filtrate to boiling, dropwise adding concentrated hydrochloric acid to adjust the pH of the reaction product to be 1-1.5, standing and cooling for 10-15h, filtering, washing a filter cake with distilled water for 2-3 times, and drying to constant weight to obtain an intermediate 4;
a5: adding the intermediate 1 and the intermediate 4 into a three-neck flask provided with a mechanical stirrer and a gas-guide tube, introducing nitrogen for protection, and stirring and reacting for 20-30h under the conditions that the temperature is 22-28 ℃, the stirring speed is 500-; and adding epoxy propanol into the intermediate 5, and continuously stirring for reacting for 20-30h to obtain the modifier.
4. The low-temperature-resistant anti-freezing bionic bait as claimed in claim 3, wherein the mass fraction of the formaldehyde solution in the step A1 is 35-40%, the anthranilic alcohol solution is a solution prepared by dissolving anthranilic alcohol in diethyl ether, the mass fraction of the anthranilic alcohol is 20-30%, and the molar ratio of the formaldehyde to the anthranilic alcohol is 1.0: 1.0-1.5.
5. The low-temperature-resistant anti-freezing bionic bait as claimed in claim 3, wherein the dosage ratio of the 3-chlorophthalic anhydride, the glacial acetic acid and the methylamine solution in the step A2 is 0.19 mol: 110 mL: 20g, wherein the methylamine solution is prepared by mixing methylamine according to a mass ratio of 3: 7 dissolved in deionized water.
6. The low-temperature-resistant antifreezing bionic bait according to claim 3, wherein the dosage ratio of the intermediate 2, N-dimethylacetamide, triphenylphosphine, nickel chloride, sodium iodide and zinc powder in the step A3 is 0.1 mol: 200mL of: 106 g: 13 g: 3 g: 7.0-8.0 g.
7. The low-temperature-resistant anti-freezing bionic bait as claimed in claim 3, wherein the sodium hydroxide solution, the intermediate 3 and the activated carbon in the step A4 are used in a ratio of 100 mL: 9 g: 1-3g, wherein the mass fraction of the sodium hydroxide solution is 20-25%, and the mass fraction of the concentrated hydrochloric acid is 35-37%.
8. The low-temperature-resistant anti-freezing bionic bait according to claim 3, wherein the molar ratio of the intermediate 1 to the intermediate 4 in the step A5 is 1.0: 3.3, the mol ratio of the epoxy propanol to the intermediate 5 is 1.0: 3.0-7.0.
9. A preparation method of the low-temperature-resistant anti-freezing bionic bait is characterized by comprising the following steps:
the method comprises the following steps: weighing 60-100 parts of bisphenol A epoxy resin, 4-12 parts of modifier, 1-3 parts of paraffin, 15-20 parts of curing agent, 0.1-3 parts of phagostimulant, 0.1-3 parts of pigment and 1-5 parts of antioxidant according to parts by weight for later use;
step two: adding bisphenol A type epoxy resin and a modifier into a high-speed mixer, uniformly mixing, adding into a double-screw extruder, carrying out melt extrusion, bracing, cooling, granulating and drying to obtain the modified epoxy resin
Step three: adding the modified epoxy resin, the paraffin, the curing agent, the phagostimulant, the pigment and the antioxidant into a high-speed mixer, uniformly mixing, adding into a double-screw extruder, melting and extruding into an injection molding machine, and performing injection molding to obtain the low-temperature-resistant and anti-freezing bionic bait.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115537095A (en) * | 2022-04-13 | 2022-12-30 | 安徽宏飞钓具有限公司 | Luminous multi-section flexible bionic bait and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1149324A (en) * | 1955-04-11 | 1957-12-24 | Minnesota Mining & Mfg | Compositions based on epoxy resins and manufacturing process |
| JPH05320480A (en) * | 1992-05-25 | 1993-12-03 | Toray Ind Inc | Epoxy resin composition and epoxy resin composition for resin transfer molding |
| JP2011094104A (en) * | 2009-09-30 | 2011-05-12 | Kansai Paint Co Ltd | Epoxy resin composition and coating composition containing the same |
| CN104855349A (en) * | 2015-04-24 | 2015-08-26 | 界首市超强渔具有限公司 | Easily degradable environment-friendly soft color bionic fish bait |
| CN112442273A (en) * | 2020-11-25 | 2021-03-05 | 界首市兴隆渔具有限公司 | Composite material for preparing carbon fiber fishing rod and preparation method thereof |
-
2021
- 2021-07-12 CN CN202110785755.7A patent/CN113527842B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1149324A (en) * | 1955-04-11 | 1957-12-24 | Minnesota Mining & Mfg | Compositions based on epoxy resins and manufacturing process |
| JPH05320480A (en) * | 1992-05-25 | 1993-12-03 | Toray Ind Inc | Epoxy resin composition and epoxy resin composition for resin transfer molding |
| JP2011094104A (en) * | 2009-09-30 | 2011-05-12 | Kansai Paint Co Ltd | Epoxy resin composition and coating composition containing the same |
| CN104855349A (en) * | 2015-04-24 | 2015-08-26 | 界首市超强渔具有限公司 | Easily degradable environment-friendly soft color bionic fish bait |
| CN112442273A (en) * | 2020-11-25 | 2021-03-05 | 界首市兴隆渔具有限公司 | Composite material for preparing carbon fiber fishing rod and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115537095A (en) * | 2022-04-13 | 2022-12-30 | 安徽宏飞钓具有限公司 | Luminous multi-section flexible bionic bait and preparation method thereof |
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