CN110862638B - Method for preparing biodegradable bionic bait by using modified rubber material - Google Patents
Method for preparing biodegradable bionic bait by using modified rubber material Download PDFInfo
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/006—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01K—ANIMAL HUSBANDRY; AVICULTURE; APICULTURE; PISCICULTURE; FISHING; REARING OR BREEDING ANIMALS, NOT OTHERWISE PROVIDED FOR; NEW BREEDS OF ANIMALS
- A01K85/00—Artificial bait for fishing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental Sciences (AREA)
- Marine Sciences & Fisheries (AREA)
- Animal Husbandry (AREA)
- Biodiversity & Conservation Biology (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
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.
Description
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 chemical technology, Inc., corn starch was obtained from Suzhou Hensharzier Chemicals, Inc., polypropylene was obtained from secondary white PP from Kairry plastics manufacturing, Inc., nano calcium carbonate was obtained from Beijing German island technology, Inc., beta-carotene was obtained from Tianxu food additives, Inc., Guangzhou, and hydroxyethyl cellulose was obtained from HEC-30000, Shandong Chuoyao Biotechnology, Inc.
Example 1
(1) Preparation of modified SBS: dropwise adding a mixed solvent of toluene and carbon tetrachloride in a volume ratio of 1:1 into 50g of SBS thermoplastic elastomer until the mixed solvent is completely dissolved, adding 1g of initiator and 11g N-hydroxymethyl acrylamide, heating to 75 ℃, keeping the temperature and reacting for 8 hours, concentrating under reduced pressure after the reaction is finished, recovering toluene and carbon tetrachloride, adding 200mL of water into a concentrated residue, stirring, filtering, and drying filter residues to obtain modified SBS;
(2) preparation of TPR material: adding 50g of the modified SBS, 8g of corn starch, 5g of polypropylene, 4g of nano calcium carbonate with the average particle size of 20nm, 4g of trioctyl citrate and 0.8g of beta-carotene into an internal mixer, carrying out internal mixing at the temperature of 135 ℃ for 15min, adding the mixture into a double-screw extruder after internal mixing, and carrying out melt extrusion and granulation to obtain TPR material particles, wherein the extrusion temperature of the double-screw extruder is 165 ℃, the length-diameter ratio of a screw is 50:1, and the rotation speed of the screw is 250 rpm;
(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, wherein the injection molding temperature is 170 ℃, the injection molding pressure is 85MPa, the pressure maintaining time is 30s, and the preheating temperature of the mold cavity is 85 ℃.
Example 2
The same as example 1 except that the nano calcium carbonate in example 1 was replaced with the coated and modified nano calcium carbonate.
Coating modification treatment of nano calcium carbonate: heating 2g of hydroxyethyl cellulose to a melting point, preserving heat until the hydroxyethyl cellulose is completely melted, adding 4g of nano calcium carbonate, uniformly mixing, freezing the mixture at 0 ℃ for 3 hours, and finally preparing the mixture into powder with the average particle size of 20nm by a pulverizer.
Example 3
The modified SBS obtained in step (1) of example 1 was heat-treated, and then a TPR material was prepared, the specific operation of the heat treatment being as follows, with the remainder being the same as in example 1.
Heat treatment of modified SBS: : placing the modified SBS in a microwave reactor, wherein the microwave frequency is 2450MHz, the microwave power is 1000W, and the microwave treatment time is 5min, transferring the modified SBS into a high-pressure reaction kettle for high-pressure treatment after the microwave treatment, wherein the pressure of the high-pressure reaction kettle is 5MPa, the temperature is 0 ℃, and the high-pressure treatment time is 30 min.
Comparative example 1
The same procedure as in example 1 was repeated except that the nano calcium carbonate in example 1 was replaced with a mixture of nano calcium carbonate and hydroxyethyl cellulose at a mass ratio of 2: 1.
Comparative example 2
The SBS thermoplastic elastomer modification treatment process of step (1) of example 1 was omitted, and the remainder was the same as in example 1.
Bionic bait was prepared by using the above examples and comparative examples, respectively, and the biodegradability of the bait was measured in accordance with GB/T19811-.
D1＝[(m1-m2)/m1]×100％
D1-the degree of disintegration of the bait, expressed in%;
m1-total dry solids of bait dosed at the start of the test in g;
m2total dry solids of the bait, in g, collected after the test.
TABLE 1 biodegradability of the bait according to the invention
As can be seen from table 1, the technical effect of significantly enhancing the biodegradability of the prepared bait can be achieved by modifying the SBS thermoplastic elastomer, coating and modifying the nano calcium carbonate, and thermally treating the modified SBS.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
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: 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.
2. The method of claim 1, wherein: the initiator is benzoyl peroxide.
3. The method of claim 1, wherein: the average grain diameter of the nano calcium carbonate is 20 nm.
4. 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.
5. The method of claim 1, wherein: the banburying temperature is 130-140 ℃.
6. 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.
7. 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 ℃.
8. 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.
9. The method of claim 1, wherein: the pigment is plant extracted pigment.
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