CN110540745A - High-elasticity environment-friendly bionic bait material and preparation method thereof - Google Patents
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
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- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
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Abstract
The invention discloses a high-elasticity environment-friendly bionic bait material which is prepared from the following raw materials in parts by weight: 58-65 parts of modified TPU, 19-23 parts of auxiliary elastomer, 6.5-8.5 parts of plasticizer, 0.2-0.3 part of antioxidant and 0.05-0.1 part of mildew preventive; the invention also discloses a preparation method of the bionic bait material. The modified TPU is used as the main material of the bionic bait material, and the auxiliary elastomer is added, so that the obtained bionic bait material has high elasticity, and the adopted raw materials are all biodegradable environment-friendly materials, so that the bionic bait material meets the requirement on the environment-friendly performance; and by modifying the TPU, the processing performance of the TPU can be enhanced, and the reinforcing filler and the fish luring agent can be uniformly distributed in the material, so that the effects of enhancing the mechanical property and doubly inducing fish are achieved, the high-elasticity environment-friendly bionic bait material is obtained, has wide use performance and is suitable for the field of fishing gears.
Description
Technical Field
The invention belongs to the technical field of bionic bait, and particularly relates to a high-elasticity environment-friendly bionic bait material and a preparation method thereof.
background
In the traditional fishing, different baits are generally placed on a fishhook positioned at the tail end of a hook line according to different fishes, when the baits are swallowed, the fishes get on the hook, the method needs to continuously replace the baits, and the fishes are easy to slip. In recent years, artificial bionic bait has been developed, which has the appearance of small fish, can float in water by utilizing the buoyancy of the bait and the traction of a hook line, is vivid by arranging necessary decorations such as patterns, colors and the like on the appearance of the bait, enables big fish in water to swallow, and successfully lifts the big fish by utilizing a fishhook fixed outside the bait.
the Chinese patent with the patent number of CN201810693320.8 discloses a biodegradable bionic bait material and a preparation method thereof, wherein the bionic bait material is prepared from the following materials in parts by mass: 40-70 parts of TPU, 10-20 parts of auxiliary elastomer, 10-20 parts of natural degradation material and 5-15 parts of environment-friendly plasticizer; the natural degradable material is one or a mixture of corn starch, grain fine powder, cassava powder, cornstarch and flour, the fish luring agent is specifically one or a compound of L-alanine, L-arginine, L-aspartic acid, glycine, L-leucine, 5 '-guanylic acid, 5' -inosinic acid, dimethyl disulfide and dimethyl disulfide, and the bionic bait material has the advantage of easy biodegradation. The TPU is a high molecular elastic polymer, and has the advantage of degradability, but the natural degradable material is a biological high molecular, the fish luring agent is an inorganic substance, the compatibility among the substances is not very good, the performance of the bionic bait material prepared by blending can be influenced, and the raw materials can not play corresponding roles, so that the bionic bait can not meet the existing use requirements.
Disclosure of Invention
the invention aims to provide a high-elasticity environment-friendly bionic bait material and a preparation method thereof, wherein modified TPU is adopted as a main material of the bionic bait material, and an auxiliary elastomer is added, so that the obtained bionic bait material has high elasticity, and the adopted raw materials are all biodegradable environment-friendly materials, so that the bionic bait material meets the requirement on the environment-friendly performance; and by modifying the TPU, the processing performance of the TPU can be enhanced, and the reinforcing filler and the fish luring agent can be uniformly distributed in the material, so that the effects of enhancing the mechanical property and doubly inducing the fish are achieved, the high-elasticity environment-friendly bionic bait material is obtained, has wide use performance and is suitable for the field of fishing gears.
the purpose of the invention can be realized by the following technical scheme:
A high-elasticity environment-friendly bionic bait material is prepared from the following raw materials in parts by weight: 58-65 parts of modified TPU, 19-23 parts of auxiliary elastomer, 6.5-8.5 parts of plasticizer, 0.2-0.3 part of antioxidant and 0.05-0.1 part of mildew preventive.
Further, the auxiliary elastomer is one or a mixture of more of polyhydroxyalkanoate, polylactic acid, poly (ethyl-propyl-hydroxy propionate) and poly (octyl glycol citrate).
Further, the plasticizer is glycerol or epoxidized soybean oil.
Further, the modified TPU is prepared by the process of:
(1) dissolving L-alanine in distilled water to prepare a modified solution with the mass fraction of 20%, heating to 66-68 ℃, and preserving heat to obtain the modified solution;
(2) Dispersing 0.5g of nano calcium carbonate into 160mL of absolute ethyl alcohol at 150-;
(3) Dehydrating polytetrahydrofuran diol at 110 deg.C for 5-6 h; adding 5-6mg of modified nano calcium carbonate into 50mL of 1, 4-butanediol, and performing ultrasonic dispersion for 1h to obtain a modified nano calcium carbonate mixed solution for later use;
(4) Adding the dried polytetrahydrofuran diol, the modified nano calcium carbonate mixed solution and the bismuth neodecanoate into a beaker, uniformly stirring and mixing at 300r/min, slowly adding the diphenylmethane diisocyanate, increasing the rotation speed to 500r/min, stirring for 30-40min, putting into a nitrogen-protected 120 ℃ oven, and curing for 8h to obtain the modified polyurethane.
A preparation method of a high-elasticity environment-friendly bionic bait material comprises the following steps:
step S1, mixing the modified TPU, the auxiliary elastomer, the plasticizer, the antioxidant and the mildew preventive, and then carrying out blending and banburying in a banbury mixer for 11-13min, wherein the mixing temperature is kept at 135 ℃ of 128 ℃, and after mixing, a double-screw extruder is adopted for melt extrusion, bracing, cooling, cutting and drying to obtain a composite material for later use;
Wherein the extrusion temperature of the double-screw extruder is 155-;
s2, performing injection molding on the composite material prepared in the step S1 by adopting an injection molding machine according to a corresponding mold to obtain the bionic bait material;
Wherein the injection temperature of the injection molding machine is 145-180 ℃, the injection pressure is 80-100MPa, the pressure maintaining time is 30-40s, and the mold temperature is 90-110 ℃.
the invention has the beneficial effects that:
The modified TPU is used as a main material of the bionic bait material and is obtained by copolymerizing modified nano calcium carbonate, the modified nano calcium carbonate is modified by L-alanine, L-alanine molecules migrate to the surface of nano calcium carbonate particles from a liquid phase main body to generate an insoluble salt precursor, then carboxyl (-COOH) on the L-alanine molecules react with Ca2+ on the surface of the nano calcium carbonate particles to generate insoluble salt (Ca (COOR)2), and the insoluble salt precursor migrates to the surface of the calcium carbonate particles to be adsorbed and grown on the surfaces of the calcium carbonate particles to coat the calcium carbonate particles to obtain the modified nano calcium carbonate; l-alanine molecules are grafted on the surface of the modified nano calcium carbonate; on one hand, the modified nano calcium carbonate particles are well dispersed in the matrix, so that the filling system is in a lower shear viscosity in the processing process, and the processing performance of the TPU is improved; meanwhile, hydrogen bond action is formed between active groups such as-COOH, -NH2 on the surface of the modified nano calcium carbonate and carbamate groups on a TPU molecular chain and carbonyl groups on a soft segment, so that the bonding performance of the nano calcium carbonate and a TPU matrix can be enhanced, the molecular chains are tighter, and the thermal stability of the TPU is improved; moreover, the interaction of the nano calcium carbonate particles and the TPU improves the interface bonding strength of the material, and when the TPU is subjected to external stress, two phases connected by the nano calcium carbonate particles absorb impact energy and prevent the diffusion of microcracks through the plastic deformation of the particle-matrix, so that the mechanical performance of the TPU is improved; on the other hand, the L-alanine is uniformly distributed in the material by the nano calcium carbonate grafted with the L-alanine, and the L-alanine is a natural fish luring agent, so that the bionic fish bait not only can attract fish by the shape of the bionic fish bait but also can induce the fish through the L-alanine when the L-alanine is uniformly distributed in the bionic fish bait material, and the effect of double fish induction is achieved;
the modified TPU is used as the main material of the bionic bait material, and the auxiliary elastomer is added, so that the obtained bionic bait material has high elasticity, and the adopted raw materials are all biodegradable environment-friendly materials, so that the bionic bait material meets the requirement on the environment-friendly performance; and by modifying the TPU, the processing performance of the TPU can be enhanced, and the reinforcing filler and the fish luring agent can be uniformly distributed in the material, so that the effects of enhancing the mechanical property and doubly inducing fish are achieved, the high-elasticity environment-friendly bionic bait material is obtained, has wide use performance and is suitable for the field of fishing gears.
Detailed Description
the technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood 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.
A high-elasticity environment-friendly bionic bait material is prepared from the following raw materials in parts by weight: 58-65 parts of modified TPU, 19-23 parts of auxiliary elastomer, 6.5-8.5 parts of plasticizer, 0.2-0.3 part of antioxidant and 0.05-0.1 part of mildew preventive;
The auxiliary elastomer is one or a mixture of more of polyhydroxy fatty acid ester, polylactic acid, polyhydroxy propionic acid-glycolide and poly citric acid octyl diol ester;
The plasticizer is glycerol or epoxidized soybean oil;
the modified TPU is prepared by the process of:
(1) Dissolving L-alanine in distilled water to prepare a modified solution with the mass fraction of 20%, heating to 66-68 ℃, and preserving heat to obtain the modified solution;
(2) dispersing 0.5g of nano calcium carbonate into 160mL of absolute ethyl alcohol at 150-;
(3) Dehydrating polytetrahydrofuran diol at 110 deg.C for 5-6 h; adding 5-6mg of modified nano calcium carbonate into 50mL of 1, 4-butanediol, and performing ultrasonic dispersion for 1h to obtain a modified nano calcium carbonate mixed solution for later use;
(4) Adding the dried polytetrahydrofuran diol, the modified nano calcium carbonate mixed solution and the bismuth neodecanoate into a beaker, uniformly stirring and mixing at 300r/min, slowly adding the diphenylmethane diisocyanate, increasing the rotation speed to 500r/min, stirring for 30-40min, putting into a nitrogen-protected 120 ℃ oven, and curing for 8h to obtain modified polyurethane;
Wherein the mass ratio of the polytetrahydrofuran diol to the mixed solution of the modified nano calcium carbonate to the diphenylmethane diisocyanate to the bismuth neodecanoate is 10:5-6:18-19: 0.1;
Transferring L-alanine molecules from a liquid phase main body to the surface of the nano calcium carbonate particles to generate an insoluble salt precursor, then reacting carboxyl (-COOH) on the L-alanine molecules with Ca2+ on the surface of the nano calcium carbonate particles to generate insoluble salt (Ca (COOR)2), transferring the insoluble salt precursor to the surface of the calcium carbonate particles, adsorbing and growing on the surface of the calcium carbonate particles, and coating the calcium carbonate particles to obtain modified nano calcium carbonate; l-alanine molecules are grafted on the surface of the modified nano calcium carbonate; on one hand, the modified nano calcium carbonate particles are well dispersed in the matrix, so that the filling system is in a lower shear viscosity in the processing process, and the processing performance of the TPU is improved; meanwhile, hydrogen bonds are formed between active groups such as-COOH, -NH2 on the surface of the modified nano calcium carbonate and carbamate groups on a TPU molecular chain and carbonyl groups on a soft segment, so that the bonding performance of the nano calcium carbonate and a TPU matrix can be enhanced, the molecular chains can be tighter, and the thermal stability of the TPU can be improved; moreover, the interaction of the nano calcium carbonate particles and the TPU improves the interface bonding strength of the material, and when the TPU is subjected to external stress, two phases connected by the nano calcium carbonate particles absorb impact energy and prevent the diffusion of microcracks through the plastic deformation of the particle-matrix, so that the mechanical performance of the TPU is improved; on the other hand, the L-alanine is uniformly distributed in the material by grafting the L-alanine nano calcium carbonate, and the L-alanine is a natural fish luring agent, so that the bionic fish bait not only can attract fish by the shape of the bionic fish bait but also can induce the fish through the L-alanine when the L-alanine nano calcium carbonate is uniformly distributed in the bionic fish bait material, and the effect of double fish induction is achieved;
the preparation method of the high-elasticity environment-friendly bionic bait material comprises the following steps:
step S1, mixing the modified TPU, the auxiliary elastomer, the plasticizer, the antioxidant and the mildew preventive, and then carrying out blending and banburying in a banbury mixer for 11-13min, wherein the mixing temperature is kept at 135 ℃ of 128 ℃, and after mixing, a double-screw extruder is adopted for melt extrusion, bracing, cooling, cutting and drying to obtain a composite material for later use;
Wherein the extrusion temperature of the double-screw extruder is 155-;
S2, performing injection molding on the composite material prepared in the step S1 by adopting an injection molding machine according to a corresponding mold to obtain the bionic bait material;
Wherein the injection temperature of the injection molding machine is 145-180 ℃, the injection pressure is 80-100MPa, the pressure maintaining time is 30-40s, and the mold temperature is 90-110 ℃.
example 1
a high-elasticity environment-friendly bionic bait material is prepared from the following raw materials in parts by weight: 58 parts of modified TPU, 19 parts of auxiliary elastomer, 6.5 parts of plasticizer, 0.2 part of antioxidant and 0.05 part of mildew preventive;
the preparation method of the high-elasticity environment-friendly bionic bait material comprises the following steps:
Step S1, mixing the modified TPU, the auxiliary elastomer, the plasticizer, the antioxidant and the mildew preventive, and then carrying out blending and banburying in a banbury mixer for 11min, wherein the mixing temperature is kept at 128 ℃, and after mixing, a double-screw extruder is adopted for carrying out melt extrusion, bracing, cooling, cutting and drying to obtain a composite material for later use;
wherein the extrusion temperature of the double-screw extruder is 155 ℃, the length-diameter ratio L/D of the screw is 50:1, and the rotation speed of the screw is 120 RPM;
S2, performing injection molding on the composite material prepared in the step S1 by adopting an injection molding machine according to a corresponding mold to obtain the bionic bait material;
Wherein the injection molding temperature of the injection molding machine is 145 ℃, the injection molding pressure is 80MPa, the pressure maintaining time is 30s, and the mold temperature is 90 ℃.
example 2
a high-elasticity environment-friendly bionic bait material is prepared from the following raw materials in parts by weight: 60 parts of modified TPU, 21 parts of auxiliary elastomer, 7.5 parts of plasticizer, 0.25 part of antioxidant and 0.08 part of mildew preventive;
the preparation method of the high-elasticity environment-friendly bionic bait material comprises the following steps:
step S1, mixing the modified TPU, the auxiliary elastomer, the plasticizer, the antioxidant and the mildew preventive, and then carrying out blending and banburying in a banbury mixer for 12min, keeping the mixing temperature at 132 ℃, and after mixing, carrying out melt extrusion, bracing, cooling, cutting and drying by using a double-screw extruder to obtain a composite material to be used;
Wherein the extrusion temperature of the double-screw extruder is 165 ℃, the length-diameter ratio L/D of the screw is 56:1, and the rotation speed of the screw is 220 RPM;
s2, performing injection molding on the composite material prepared in the step S1 by adopting an injection molding machine according to a corresponding mold to obtain the bionic bait material;
Wherein the injection molding temperature of the injection molding machine is 160 ℃, the injection molding pressure is 90MPa, the pressure maintaining time is 35s, and the mold temperature is 100 ℃.
example 3
a high-elasticity environment-friendly bionic bait material is prepared from the following raw materials in parts by weight: 65 parts of modified TPU, 23 parts of auxiliary elastomer, 8.5 parts of plasticizer, 0.3 part of antioxidant and 0.1 part of mildew preventive;
the preparation method of the high-elasticity environment-friendly bionic bait material comprises the following steps:
Step S1, mixing the modified TPU, the auxiliary elastomer, the plasticizer, the antioxidant and the mildew preventive, and then carrying out blending and banburying in a banbury mixer for 13min, keeping the mixing temperature at 135 ℃, and after mixing, carrying out melt extrusion, bracing, cooling, cutting and drying by using a double-screw extruder to obtain a composite material to be used;
wherein the extrusion temperature of the double-screw extruder is 175 ℃, the length-diameter ratio L/D of the screw is 62:1, and the rotation speed of the screw is 360 RPM;
S2, performing injection molding on the composite material prepared in the step S1 by adopting an injection molding machine according to a corresponding mold to obtain the bionic bait material;
wherein the injection temperature of the injection molding machine is 180 ℃, the injection pressure is 100MPa, the dwell time is 30-40s, and the mold temperature is 110 ℃.
comparative example 1
the modified TPU starting material from example 1 was changed to the ordinary TPU, and the rest of the preparation was unchanged.
comparative example 2
The modified TPU in example 1 is changed into the ordinary TPU, and the nano calcium carbonate and the L-alanine (the same amount of the corresponding components in example 1 are added) are added into the raw materials, and the rest preparation process is not changed.
The bionic bait materials prepared in examples 1-3 and comparative examples 1-2 were subjected to the following performance tests: testing the melt viscosity at 180 ℃; testing the tensile strength; testing the thermal decomposition temperature (characteristic decomposition temperature with 10% loss of mass); the biodegradation performance was tested and the test results are shown in the following table:
| Example 1 | example 2 | example 3 | comparative example 1 | Comparative example 2 | |
| melt viscosity/pas at 180 DEG C | 2000 | 1980 | 2050 | 2300 | 2350 |
| Tensile strength/MPa | 42.8 | 43.1 | 42.5 | 31.7 | 33.4 |
| thermal decomposition temperature/. degree.C | 316.8 | 317.3 | 316.9 | 307.5 | 309.8 |
| 40d biodegradation Rate/%) | 46.5 | 45.9 | 47.2 | - | - |
| 80d biodegradation Rate/%) | 80.6 | 79.8 | 81.5 | - | - |
| 120d biodegradation Rate/% | 97.8 | 96.9 | 98.9 | - | - |
As can be seen from the table, the melt viscosity at 180 ℃ of the bionic bait material prepared in the examples 1-3 is 2050 Pa.s at 1980, and compared with the comparative examples 1 and 2, the modified TPU can reduce the melt viscosity of the common TPU, so that the processing performance is improved; it can be seen from the table that the tensile strength of the bionic bait material prepared in the examples 1 to 3 is 42.5 to 43.1MPa, and the thermal decomposition temperature is 316.8 to 317.3 ℃, which shows that the bionic bait material prepared in the invention has good mechanical properties and high thermal stability, compared with the comparative example 2, the effect of directly adding the filler into the TPU matrix is not good, and the modified TPU nano calcium carbonate has interaction with the matrix and can be uniformly dispersed, so that the mechanical properties and the thermal stability of the TPU matrix are improved; it can be seen from the table that the 40d degradation rate, the 80d degradation rate and the 120d degradation rate of the bionic bait material prepared in examples 1-3 reach over 45.9%, 79.8% and 96.9%, respectively, which indicates that the bionic bait material prepared by the invention can be biodegraded and has high environmental protection characteristics.
the foregoing is merely exemplary and illustrative of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the invention as defined in the accompanying claims.
Claims (5)
1. A high-elasticity environment-friendly bionic bait material is characterized by being prepared from the following raw materials in parts by weight: 58-65 parts of modified TPU, 19-23 parts of auxiliary elastomer, 6.5-8.5 parts of plasticizer, 0.2-0.3 part of antioxidant and 0.05-0.1 part of mildew preventive.
2. the high-elasticity environment-friendly bionic bait material as claimed in claim 1, wherein the auxiliary elastomer is one or a blend of more of polyhydroxyalkanoate, polylactic acid, polyhydroxypropionic acid-glycolide, and polycitraconic glycol ester.
3. The high-elasticity environment-friendly bionic bait material as claimed in claim 1, wherein the plasticizer is glycerol or epoxidized soybean oil.
4. the high-elasticity environment-friendly bionic bait material as claimed in claim 1, wherein the modified TPU is prepared by the following method:
(1) Dissolving L-alanine in distilled water to prepare a modified solution with the mass fraction of 20%, heating to 66-68 ℃, and preserving heat to obtain the modified solution;
(2) dispersing 0.5g of nano calcium carbonate into 160mL of absolute ethyl alcohol at 150-;
(3) dehydrating polytetrahydrofuran diol at 110 deg.C for 5-6 h; adding 5-6mg of modified nano calcium carbonate into 50mL of 1, 4-butanediol, and performing ultrasonic dispersion for 1h to obtain a modified nano calcium carbonate mixed solution for later use;
(4) adding the dried polytetrahydrofuran diol, the modified nano calcium carbonate mixed solution and the bismuth neodecanoate into a beaker, uniformly stirring and mixing at 300r/min, slowly adding the diphenylmethane diisocyanate, increasing the rotating speed to 500r/min, stirring for 30-40min, putting into a nitrogen-protected 120 ℃ oven, and curing for 8h to obtain the modified polyurethane.
5. a preparation method of a high-elasticity environment-friendly bionic bait material is characterized by comprising the following steps:
step S1, mixing the modified TPU, the auxiliary elastomer, the plasticizer, the antioxidant and the mildew preventive, and then carrying out blending and banburying in a banbury mixer for 11-13min, wherein the mixing temperature is kept at 135 ℃ of 128 ℃, and after mixing, a double-screw extruder is adopted for melt extrusion, bracing, cooling, cutting and drying to obtain a composite material for later use;
wherein the extrusion temperature of the double-screw extruder is 155-;
s2, performing injection molding on the composite material prepared in the S1 by adopting an injection molding machine according to a corresponding mold to obtain the bionic bait material;
Wherein the injection temperature of the injection molding machine is 145-180 ℃, the injection pressure is 80-100MPa, the pressure maintaining time is 30-40s, and the mold temperature is 90-110 ℃.
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| CN111393860A (en) * | 2020-04-30 | 2020-07-10 | 安徽宏飞钓具有限公司 | Quickly degradable bionic bait for sea fishing and production process thereof |
| CN114479199A (en) * | 2022-01-20 | 2022-05-13 | 四川大学 | Full-biodegradable bionic bait and preparation method thereof |
| CN115710384A (en) * | 2022-11-28 | 2023-02-24 | 界首市超强渔具有限公司 | Starch-based bionic bait |
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Application publication date: 20191206 |