阅读说明：本技术 利用改性橡胶材料制备可生物降解型仿生鱼饵的方法 (Method for preparing biodegradable bionic bait by using modified rubber material ) 是由 马汝霖 段晓辉 赵冰冰 于 2019-11-13 设计创作，主要内容包括：本发明公开了一种利用改性橡胶材料制备可生物降解型仿生鱼饵的方法,涉及仿生鱼饵加工技术领域,包括以下步骤：(1)改性SBS的制备；(2)TPR材料的制备；(3)仿生鱼饵的制备。本发明采用单体接枝改性方法来赋予SBS可生物降解性,在SBS的化学结构中引入酰胺基和羟基,并通过玉米淀粉等助剂的组合制得TPR材料,利用该TPR材料制得的仿生鱼饵具有良好的生物降解性能,在发挥诱捕鱼虾后能够被环境降解,从而避免不可降解鱼饵存在的污染水体的问题。(The invention discloses a method for preparing biodegradable bionic bait by using a modified rubber material, which relates to the technical field of bionic bait processing and comprises the following steps: (1) preparing modified SBS; (2) preparing a TPR material; (3) and (3) preparing the bionic bait. According to the invention, a monomer graft modification method is adopted to endow SBS with biodegradability, amide groups and hydroxyl groups are introduced into the chemical structure of SBS, and the TPR material is prepared by combining auxiliaries such as corn starch and the like.)

1. The method for preparing the biodegradable bionic bait by using the modified rubber material is characterized by comprising the following steps of:

(1) preparation of modified SBS: dropwise adding a mixed solvent of toluene and carbon tetrachloride into an SBS thermoplastic elastomer until the mixed solvent is completely dissolved, adding an initiator and N-hydroxymethyl acrylamide, heating to 70-80 ℃, carrying out heat preservation reaction, carrying out reduced pressure concentration after the reaction is finished, recovering toluene and carbon tetrachloride, adding water into the concentrated residue, stirring, filtering, and drying filter residues to obtain modified SBS;

(2) preparation of TPR material: adding the modified SBS, the corn starch, the polypropylene, the nano calcium carbonate, the plasticizer and the pigment into an internal mixer, mixing, adding into a double-screw extruder, and performing melt extrusion and granulation to obtain TPR material particles;

(3) preparing the bionic bait: and pressing the TPR material particles into a mold cavity by a screw of an injection molding machine, and performing injection molding to obtain the bionic bait.

2. The method of claim 1, wherein: the volume ratio of the toluene to the carbon tetrachloride is 1:1, and the mass ratio of the SBS thermoplastic elastomer, the initiator and the N-hydroxymethyl acrylamide is 50:0.5-2: 5-15.

3. The method of claim 1, wherein: the initiator is benzoyl peroxide.

4. The method of claim 1, wherein: the average grain diameter of the nano calcium carbonate is 20 nm.

5. The method of claim 1, wherein: the plasticizer is selected from any one of tributyl citrate, trioctyl citrate, acetyl tributyl citrate and acetyl trioctyl citrate.

6. The method of claim 1, wherein: the banburying temperature is 130-140 ℃.

7. The method of claim 1, wherein: the extrusion temperature of the double-screw extruder is 160-170 ℃, the length-diameter ratio of the screw is 45-55:1, and the rotating speed of the screw is 100-300 rpm.

8. The method of claim 1, wherein: the injection temperature is 170-180 ℃, the injection pressure is 80-100MPa, the dwell time is 30-60s, and the preheating temperature of the mold cavity is 80-90 ℃.

9. The method of claim 1, wherein: the mass ratio of the modified SBS to the corn starch to the polypropylene to the nano calcium carbonate to the plasticizer to the pigment is 50:1-10:1-10:1-10:1-10: 0.5-3.

10. The method of claim 1, wherein: the pigment is plant extracted pigment.

The technical field is as follows:

the invention relates to the technical field of processing of bionic bait, in particular to a method for preparing biodegradable bionic bait by using a modified rubber material.

Background art:

in recent years, the application of artificial bionic bait is more and more extensive. The bionic bait is manufactured by utilizing the law that big fishes eat small fishes, and can float in water by utilizing the buoyancy of the bionic bait and the traction of a hook line. The fish hook on the bionic bait has strong killing power, the fish is difficult to escape once biting, and compared with the traditional bait, the bait omits the procedure of preparing the bait, thereby being popular with consumers.

At present, the bionic bait sold in the market is good in fishing effect, but is made of plastics with high strength, the degradation speed is very slow, and even the bionic bait cannot be degraded, the bait can cause environmental pollution after falling into water, and the bait is phagocytosed by fishes and then can cause great harm to the fishes. In order to solve the problem, people have recently developed degradable bionic bait, and PVA or polylactic acid is mostly used as a processing raw material. In order to develop a novel bionic bait material, the invention takes TPR material as raw material to prepare biodegradable bionic bait.

The invention content is as follows:

the technical problem to be solved by the invention is to provide a method for preparing biodegradable bionic bait by using a modified rubber material, the processing method is simple and convenient, and the prepared bionic bait has good biodegradability.

The technical problem to be solved by the invention is realized by adopting the following technical scheme:

the method for preparing the biodegradable bionic bait by using the modified rubber material comprises the following steps:

(1) preparation of modified SBS: dropwise adding a mixed solvent of toluene and carbon tetrachloride into an SBS thermoplastic elastomer until the mixed solvent is completely dissolved, adding an initiator and N-hydroxymethyl acrylamide, heating to 70-80 ℃, carrying out heat preservation reaction, carrying out reduced pressure concentration after the reaction is finished, recovering toluene and carbon tetrachloride, adding water into the concentrated residue, stirring, filtering, and drying filter residues to obtain modified SBS;

(2) preparation of TPR material: adding the modified SBS, the corn starch, the polypropylene, the nano calcium carbonate, the plasticizer and the pigment into an internal mixer, mixing, adding into a double-screw extruder, and performing melt extrusion and granulation to obtain TPR material particles;

(3) preparing the bionic bait: and pressing the TPR material particles into a mold cavity by a screw of an injection molding machine, and performing injection molding to obtain the bionic bait.

The volume ratio of the toluene to the carbon tetrachloride is 1:1, and the mass ratio of the SBS thermoplastic elastomer, the initiator and the N-hydroxymethyl acrylamide is 50:0.5-2: 5-15.

The initiator is benzoyl peroxide.

The average grain diameter of the nano calcium carbonate is 20 nm.

The plasticizer is selected from any one of tributyl citrate, trioctyl citrate, acetyl tributyl citrate and acetyl trioctyl citrate.

The banburying temperature is 130-140 ℃.

The extrusion temperature of the double-screw extruder is 160-170 ℃, the length-diameter ratio of the screw is 45-55:1, and the rotating speed of the screw is 100-300 rpm.

The injection temperature is 170-180 ℃, the injection pressure is 80-100MPa, the dwell time is 30-60s, and the preheating temperature of the mold cavity is 80-90 ℃.

The mass ratio of the modified SBS to the corn starch to the polypropylene to the nano calcium carbonate to the plasticizer to the pigment is 50:1-10:1-10:1-10:1-10: 0.5-3.

The pigment is plant extracted pigment. Including chlorophyll, lutein, carotene, capsanthin, crocin, anthocyanidin, etc.

The invention also carries out coating modification on the nano calcium carbonate, and further improves the biodegradability of the TPR material prepared by utilizing the original filling performance of the nano calcium carbonate to ensure the formability and the mechanical property of the bait, and the specific technical scheme is as follows:

the nano calcium carbonate is subjected to coating modification treatment, and the specific treatment method comprises the following steps: firstly heating hydroxyethyl cellulose to a melting point, preserving heat until the hydroxyethyl cellulose is completely melted, then adding nano calcium carbonate, uniformly mixing, then placing the mixture in an environment of 0 ℃ for freezing, and finally preparing the mixture into powder with the average particle size of 20nm by a pulverizer.

The mass ratio of the nano calcium carbonate to the hydroxyethyl cellulose is 1: 0.5-1.

The melting point of the hydroxyethyl cellulose is 288-290 ℃, and the hydroxyethyl cellulose is infiltrated into the nano structure of the calcium carbonate to form the inorganic-organic composite filler in a molten state, so that the novel filler has the dual characteristics of the nano calcium carbonate and the hydroxyethyl cellulose.

The invention also carries out heat treatment on the modified SBS so as to further optimize the biodegradation performance of the prepared bait, and the specific technical scheme is as follows:

(1) preparation of modified SBS: dropwise adding a mixed solvent of toluene and carbon tetrachloride into an SBS thermoplastic elastomer until the mixed solvent is completely dissolved, adding an initiator and N-hydroxymethyl acrylamide, heating to 70-80 ℃, carrying out heat preservation reaction, carrying out reduced pressure concentration after the reaction is finished, recovering toluene and carbon tetrachloride, adding water into the concentrated residue, stirring, filtering, and drying filter residues to obtain modified SBS;

(2) heat treatment of modified SBS: placing the modified SBS in a microwave reactor, performing microwave treatment, and transferring the modified SBS into a high-pressure reaction kettle for high-pressure treatment;

(3) preparation of TPR material: adding the modified SBS, the corn starch, the polypropylene, the nano calcium carbonate and the plasticizer which are subjected to heat treatment into an internal mixer, carrying out internal mixing, adding into a double-screw extruder, and carrying out melt extrusion and granulation to obtain TPR material particles;

(4) preparing the bionic bait: and pressing the TPR material particles into a mold cavity by a screw of an injection molding machine, and performing injection molding to obtain the bionic bait.

The microwave frequency of the microwave reactor is 2450MHz, the microwave power is 1000W, the pressure of the high-pressure reaction kettle is 5MPa, and the temperature is 0 ℃.

The thermal treatment optimizes the performance of the material through the change of temperature, the invention combines the microwave technology and the low-temperature high-pressure treatment technology, and utilizes the unique principle of the two technologies and the synergistic effect of the two technologies to further optimize the biodegradation performance of the modified SBS.

The remaining preparation conditions and parameters were as described above.

The invention has the beneficial effects that: in view of the existence of double bonds in the SBS molecular structure, the invention adopts a monomer grafting modification method to endow SBS with biodegradability (SBS belongs to a thermoplastic elastomer and can not be biodegraded in a short time), introduces acylamino and hydroxyl into the chemical structure of SBS, and prepares TPR material through the combination of auxiliaries such as corn starch and the like.

The specific implementation mode is as follows:

in order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.

The SBS thermoplastic elastomer in the following examples and comparative examples was obtained from Shanghai super spin Industrial science and technology, Inc., corn starch was obtained from Suzhou Hensharpening Industrial materials, Inc., polypropylene was obtained from secondary white PP from Kairy plastics manufacturing, Inc., nano calcium carbonate was obtained from Beijing German island science and technology, Inc., β -carotene was obtained from Tianxu food additives, Inc., Guangzhou city, and hydroxyethyl cellulose was obtained from HEC-30000, Shandong Chuoyao Biotechnology, Inc.