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CN-122011584-A - Bio-based degradable buffer composite material prepared based on waste gas column bags and preparation method thereof

CN122011584ACN 122011584 ACN122011584 ACN 122011584ACN-122011584-A

Abstract

The invention provides a bio-based degradable buffer composite material prepared based on waste gas column bags and a preparation method thereof, wherein the preparation raw materials comprise 35-45 parts of waste gas column bag reclaimed materials, 18-25 parts of polylactic acid, 12-18 parts of polymethyl ethylene carbonate, 8-12 parts of poly (butylene adipate-terephthalate), 2-4 parts of chitosan-based ternary grafting compatilizer, 3-6 parts of polycaprolactone-coated modified hollow glass beads, 0.4-0.8 part of epoxy chain extender, 0.5-1.5 parts of polyolefin elastomer, 1-3 parts of epoxy soybean oil, 0.5-1.2 parts of lubricant, 0.2-0.6 parts of antioxidant and 0.3-0.7 part of heat stabilizer. The invention realizes the resource utilization of the waste gas column bag, reduces the cost, has excellent buffering, mechanical, blocking and processing performances, and has the advantages of synergistic improvement of toughness, rigidity and impact resistance, good interface compatibility and excellent degradability.

Inventors

  • Mao Longlong
  • ZHANG JINLING

Assignees

  • 浙江东方万象新材料有限公司

Dates

Publication Date
20260512
Application Date
20260309

Claims (10)

  1. 1. The bio-based degradable buffer composite material prepared based on the waste gas column bag is characterized by comprising, by weight, 35-45 parts of waste gas column bag reclaimed materials, 18-25 parts of polylactic acid, 12-18 parts of polymethyl ethylene carbonate, 8-12 parts of poly (butylene adipate-terephthalate), 2-4 parts of chitosan-based ternary grafting compatilizer, 3-6 parts of polycaprolactone coated modified hollow glass beads, 0.4-0.8 part of epoxy chain extender, 0.5-1.5 parts of polyolefin elastomer, 1-3 parts of epoxidized soybean oil, 0.5-1.2 parts of lubricant, 0.2-0.6 part of antioxidant and 0.3-0.7 part of heat stabilizer.
  2. 2. The bio-based degradable buffer composite material prepared based on the waste gas column bag, which is disclosed in claim 1, is characterized in that the lubricant is one of calcium stearate or erucamide, the antioxidant is formed by compounding an antioxidant 1010 and an antioxidant 168 according to a mass ratio of 1:1-1:2, and the heat stabilizer is formed by compounding triphenyl phosphite and zinc stearate according to a mass ratio of 1:1-2:1.
  3. 3. The bio-based degradable buffer composite material prepared based on the waste gas column bag is characterized in that the preparation raw materials of the chitosan-based ternary grafting compatilizer comprise, by weight, 4-6 parts of chitosan, 2-4 parts of anhydrous citric acid, 1-2 parts of a dopamine derivative, 0.5-0.7 part of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 0.2-0.4 part of N-hydroxysuccinimide and 0.1-0.3 part of a processing stabilizer, wherein the dopamine derivative is prepared by mixing the dopamine hydrochloride and glycerol monostearate according to a molar ratio of 1:1.2-1:1.5 through transesterification, and the processing stabilizer is prepared by compounding an antioxidant 1010 and an antioxidant 168 according to a mass ratio of 1:1-1:2.
  4. 4. The bio-based degradable buffer composite material prepared based on the waste gas column bag as claimed in claim 3, wherein the preparation method of the chitosan-based ternary grafting compatilizer comprises the following steps: 1) Dispersing chitosan into an acetic acid aqueous solution with the volume fraction of 0.8-1.2%, wherein the consumption of the acetic acid aqueous solution is 40-50 times of the mass of the chitosan, and stirring at the temperature of 20-30 ℃ at the rotating speed of 300-500 r/min for 30-60 min until the chitosan is completely dissolved; 2) Adding anhydrous citric acid, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide into the solution obtained in the step 1), stirring at a rotating speed of 200-400 r/min at 25-30 ℃ for reaction for 16-20 h, pouring the reaction solution into excessive acetone for precipitation, filtering, taking the precipitate, washing with ethanol for 2-4 times, and then vacuum drying to constant weight at 38-42 ℃ under the conditions of gauge pressure of-0.08 to-0.09 MPa to obtain anhydrous citric acid grafted chitosan; 3) Dissolving anhydrous citric acid grafted chitosan in 2-morpholinoethanesulfonic acid buffer solution, wherein the dosage of the 2-morpholinoethanesulfonic acid buffer solution is 35-45 times of the mass of the anhydrous citric acid grafted chitosan, adding a processing stabilizer, stirring and activating at 20-30 ℃ at a rotating speed of 300-500 r/min for 25-30 min, adding a dopamine derivative, and continuing stirring and reacting for 18-24 h; 4) Centrifuging the reaction liquid obtained in the step 3) at the rotating speed of 9000-10000 r/min for 10-20 min, discarding the supernatant, re-dispersing the precipitate with deionized water, centrifuging, repeating the centrifugal washing for 3-5 times, and vacuum drying to constant weight under the condition of 50-60 ℃ and gauge pressure of-0.08 to-0.09 MPa to obtain the chitosan-based ternary grafting compatilizer.
  5. 5. The bio-based degradable buffer composite material prepared based on the waste gas column bag as claimed in claim 1, wherein the preparation method of the dopamine derivative is characterized in that dopamine hydrochloride and glycerol monostearate are added into anhydrous toluene according to a molar ratio of 1:1.2-1:1.5, p-toluenesulfonic acid with mass fraction of 0.5-1.0% is added, vacuum reflux reaction is carried out for 4-5 h under the conditions of 80-90 ℃ and gauge pressure of-0.095 MPa, and after the solvent is removed by reduced pressure distillation, ethanol is recrystallized and purified to obtain the dopamine derivative.
  6. 6. The bio-based degradable buffer composite material prepared based on the waste gas column bag, which is disclosed in claim 1, is characterized in that the preparation raw materials of the polycaprolactone coated modified hollow glass microsphere comprise, by weight, 9-11 parts of hollow glass microsphere, 0.8-1.2 parts of 3-aminopropyl triethoxysilane, 0.4-0.6 parts of 3-hydroxypropyl trimethoxysilane, 18-22 parts of epsilon-caprolactone, 0.04-0.06 parts of stannous octoate and 90-110 parts of toluene.
  7. 7. The bio-based degradable buffer composite material prepared based on the waste gas column bag as claimed in claim 6, wherein the preparation method of the polycaprolactone coated modified hollow glass microsphere comprises the following steps: (1) Vacuum drying the hollow glass beads for 5-7 h at the temperature of 118-122 ℃ and the pressure of minus 0.08-minus 0.09 MPa; (2) Taking 40-50% of the total weight of toluene, adding dried hollow glass beads, dispersing for 10-20 min under the conditions of ultrasonic power of 200-400W and frequency of 20-40 kHz, simultaneously dripping 3-aminopropyl triethoxysilane and 3-hydroxypropyl trimethoxysilane at the speed of 2-4 mL/min, stirring and reacting for 3-5 h at the rotating speed of 200-400 r/min under the conditions of 78-82 ℃ and gauge pressure of-0.02-0.03 MPa after all dripping is finished, washing the product for 2-3 times by toluene, and vacuum drying to constant weight under the conditions of 98-102 ℃ and gauge pressure of-0.08-0.09 MPa to obtain amino-hydroxyl difunctional modified hollow glass beads; (3) Adding amino-hydroxyl difunctional modified hollow glass beads into the rest toluene, dispersing for 25-35 min under the ultrasonic conditions of 200-400W of ultrasonic power and 20-40 kHz of frequency, adding epsilon-caprolactone and stannous octoate, and reacting for 8-12 h under the conditions of nitrogen protection, 110-120 ℃ reflux and 200-400 r/min; (4) And (3) cooling the reaction liquid obtained in the step (3) to 20-30 ℃, filtering, washing with n-hexane for 2-4 times, and vacuum drying for 20-28 h under the conditions of 48-52 ℃ and gauge pressure of-0.08 to-0.09 MPa to obtain the polycaprolactone-coated modified hollow glass microsphere.
  8. 8. The bio-based degradable buffer composite prepared based on the waste gas column bag according to claim 1, wherein the weight average molecular weight of the polylactic acid is 9×10 4 ~11×10 4 Da, the weight average molecular weight of the polymethyl ethylene carbonate is 8×10 4 ~12×10 4 Da, the weight average molecular weight of the poly (butylene adipate-terephthalate) is 15×10 4 ~20×10 4 Da, and the weight average molecular weight of the polyolefin elastomer is 20×10 4 ~30×10 4 Da.
  9. 9. A method for preparing the bio-based degradable buffer composite material prepared based on the waste gas column bag according to any one of claims 1 to 8, comprising the following steps: S1, raw material pretreatment, namely weighing polylactic acid, polymethyl ethylene carbonate, poly (butylene adipate-terephthalate), polyolefin elastomer and waste gas column bag reclaimed materials according to a proportion, and respectively carrying out vacuum drying for 4-6 hours under the conditions of 78-82 ℃ and minus 0.08-0.09 MPa until the moisture content is less than or equal to 0.05%; s2, premixing, namely adding the raw material pretreated in the step S1, a chitosan-based ternary grafting compatilizer, polycaprolactone coated modified hollow glass beads, an epoxy chain extender, epoxidized soybean oil, a lubricant, an antioxidant and a heat stabilizer into a high-speed mixer, and stirring and mixing at a rotating speed of 600-800 r/min for 8-12 min at 20-30 ℃ to obtain a premix; S3, melt extrusion granulation, namely adding the premix obtained in the step S2 into a co-rotating double-screw extruder, controlling the temperature of each region to be 165-170 ℃ in a feeding section, 180-185 ℃ in a conveying section, 170-175 ℃ in a melting section, 170-175 ℃ in a homogenizing section and 165-170 ℃ in a head section, wherein the screw rotating speed is 250-350 r/min, the vacuum degree of a vacuum exhaust port is-0.08 to-0.09 MPa, and performing melt blending, extrusion, cooling and water cooling, and then granulating to obtain composite material master batches; And S4, molding, namely vacuum drying the composite master batch obtained in the step S3 for 3-5 hours under the conditions of 75-85 ℃ and gauge pressure of-0.08-0.09 MPa, adding the dried composite master batch into an injection molding machine, and molding under the conditions of the temperature of a charging barrel of 175-190 ℃, the temperature of a mold of 25-40 ℃, the injection pressure of 60-85 MPa, the pressure maintaining pressure of 40-60 MPa, the pressure maintaining time of 15-30S and the cooling time of 25-40S to obtain the bio-based degradable buffer composite material.
  10. 10. The preparation method of the bio-based degradable buffer composite material based on the waste gas column bag, which is characterized in that the waste gas column bag reclaimed material is subjected to sorting, crushing, alkali washing, water washing and drying, and then is subjected to melt extrusion granulation by a single screw extruder, wherein the alkali washing adopts sodium hydroxide solution with the mass fraction of 0.8-1.2%, and the alkali washing is performed for 10-20 min at 55-65 ℃.

Description

Bio-based degradable buffer composite material prepared based on waste gas column bags and preparation method thereof Technical Field The invention relates to the technical field of packaging materials, in particular to a bio-based degradable buffer composite material prepared based on waste gas column bags and a preparation method thereof. Background With the rapid development of the express logistics industry, the air column bags are widely used as high-efficiency buffer packaging materials, but most of the air column bags are made of non-degradable materials such as polypropylene, a large number of waste air column bags are difficult to degrade naturally after use, white pollution is formed, and meanwhile, the waste air column bags are low in recycling rate, so that resource waste is caused. At present, the demand of the buffer packaging field on degradable materials is increasingly urgent, and polyester degradable plastics become an important direction for replacing traditional non-degradable buffer materials due to good degradation performance, but single degradable resin has the problems of unbalanced rigidity and toughness, insufficient buffer performance, higher raw material cost and the like, and is difficult to meet the use demand of actual packaging scenes. In the prior art, although an attempt is made to compound the waste plastic reclaimed material with the degradable resin to prepare the buffer material so as to realize waste recycling and reduce cost, the polarity difference between the waste gas column bag reclaimed material and the degradable resin is large, the interface bonding force between the waste gas column bag reclaimed material and the degradable resin is weak, the phase separation phenomenon is easy to occur, the mechanical property and the buffer property of the composite material are obviously reduced, meanwhile, most of composite systems do not carry out cooperative optimization aiming at the buffer property and the degradation property, and are difficult to meet the practical industrial application requirements of the buffer packaging material, and the recycling of the waste gas column bag and the industrialized popularization of the degradable buffer material are limited. Disclosure of Invention Aiming at the problems in the prior art, the invention provides a bio-based degradable buffer composite material prepared based on waste gas column bags and a preparation method thereof. In order to achieve the above purpose, the invention is realized by the following technical scheme: The invention discloses a bio-based degradable buffer composite material prepared based on waste gas column bags, which is prepared from the following raw materials of 35-45 parts of waste gas column bag reclaimed materials, 18-25 parts of polylactic acid, 12-18 parts of polymethyl ethylene carbonate, 8-12 parts of poly (butylene adipate-terephthalate), 2-4 parts of chitosan-based ternary grafting compatilizer, 3-6 parts of polycaprolactone coated modified hollow glass beads, 0.4-0.8 part of epoxy chain extender, 0.5-1.5 parts of polyolefin elastomer, 1-3 parts of epoxy soybean oil, 0.5-1.2 parts of lubricant, 0.2-0.6 parts of antioxidant and 0.3-0.7 part of heat stabilizer. By adopting the technical scheme, the waste gas column bag reclaimed material can be introduced to realize recycling of waste gas column bags, reduce the raw material cost and provide basic toughness and water resistance for materials, polylactic acid provides rigid support for materials, polymethyl ethylene carbonate has excellent toughness and gas barrier property, carbonate bonds in molecular chains are easy to generate hydrolysis reaction, poly (butylene adipate-terephthalate) can promote the flexibility and elongation at break of materials, chitosan-based ternary grafted compatilizer can effectively improve the interfacial binding force between polar bio-based resin and non-polar waste gas column bag reclaimed materials, inhibit phase separation of systems, simultaneously have the dual functions of metal chelation and degradation promotion, polycaprolactone coated modified hollow glass microspheres can disperse stress and absorb impact energy through the synergistic effect of a hollow structure and a polymer coating layer, improve the buffer property of the materials and reduce the density of the materials, after the polylactic acid coating layer is subjected to biodegradation, pores generated by degradation of the polylactic acid coated layer are mutually communicated with original holes of the hollow glass microspheres, can provide effective mass transfer paths for adhesion of microorganisms and permeation of moisture, accelerate the whole biodegradation of composite materials, and can play roles of the epoxy resin and the epoxy resin, can promote the expansion of the epoxy resin coated epoxy resin and the epoxy resin, can realize the expansion of the polyester chain has the catalytic expansion and the mechanical property of