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CN114687041B - Processing technology of rapidly-degraded plastic woven bag - Google Patents

Processing technology of rapidly-degraded plastic woven bag Download PDF

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Publication number
CN114687041B
CN114687041B CN202210444671.1A CN202210444671A CN114687041B CN 114687041 B CN114687041 B CN 114687041B CN 202210444671 A CN202210444671 A CN 202210444671A CN 114687041 B CN114687041 B CN 114687041B
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starch
carbon black
white carbon
parts
woven bag
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CN114687041A (en
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武淼源
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Shouguang Caiyuan Plastics Co ltd
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Shouguang Caiyuan Plastics Co ltd
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    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/283Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads synthetic polymer-based, e.g. polyamide or polyester fibres
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/42Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments
    • D01D5/426Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments by cutting films
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/06Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/18Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D1/00Woven fabrics designed to make specified articles
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D13/00Woven fabrics characterised by the special disposition of the warp or weft threads, e.g. with curved weft threads, with discontinuous warp threads, with diagonal warp or weft
    • D03D13/008Woven fabrics characterised by the special disposition of the warp or weft threads, e.g. with curved weft threads, with discontinuous warp threads, with diagonal warp or weft characterised by weave density or surface weight
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/292Conjugate, i.e. bi- or multicomponent, fibres or filaments
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/40Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads
    • D03D15/44Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads with specific cross-section or surface shape
    • D03D15/46Flat yarns, e.g. tapes or films
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00Physical properties
    • D10B2401/02Moisture-responsive characteristics
    • D10B2401/021Moisture-responsive characteristics hydrophobic
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00Physical properties
    • D10B2401/06Load-responsive characteristics
    • D10B2401/063Load-responsive characteristics high strength
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00Physical properties
    • D10B2401/12Physical properties biodegradable
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00Industrial
    • D10B2505/10Packaging, e.g. bags
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)

Abstract

The invention discloses a processing technology of a rapidly-degraded plastic woven bag, which belongs to the field of plastic woven bags and comprises the steps of preparing modified starch, preparing modified nano white carbon black, preparing flat filaments and weaving. The woven bag prepared by the invention has high tensile strength, the warp tensile load is 1292-1315N/50 mm, and the weft tensile load is 1275-1287N/50 mm; the woven bag prepared by the method has good water resistance, the plastic woven bag is cut into square samples with 61mm and 61mm, the square samples are dried for 24 hours at 50 ℃, weighed, the samples are immersed into distilled water at 23 ℃ and taken out after 24 hours, the surface water is rapidly wiped by clean dry cloth, and the water absorption rate is calculated to be 0.12-0.14%.

Description

Processing technology of rapidly-degraded plastic woven bag
Technical Field
The invention relates to a processing technology of a rapidly degradable plastic woven bag, and belongs to the field of plastic woven bags.
Background
The degradable plastic is plastic which can meet the use requirements of various performances, has unchanged performances in the storage period, and is degraded into substances harmless to the environment under natural environment conditions after being used, and is also called as the environmentally degradable plastic.
The plastic product with the starch content of over 51 percent, called starch-based plastic, is prepared by adopting plant starch as a main raw material, modifying and plasticizing the plant starch by a chemical and physical process method, extruding and forming the plant starch, can be decomposed by microorganisms, is finally decomposed into water and carbon dioxide, and can greatly reduce the pollution to the environment.
The starch-based plastic has wide application prospect, rich starch sources, low price, repeated regeneration, large starch conservation amount in China and high utilization rate, and meanwhile, the plastic pollution in China is serious, and the starch-based plastic is an excellent substitute for the traditional plastic products, so that the starch can be fully utilized, and the environmental pollution can be reduced.
If the degradation performance of the starch-based plastic is required to be improved, the degradation speed of the starch-based plastic in the soil in nature is improved, the starch content needs to be improved, and the plastic contains 70-80% of starch, so that the plastic has good degradation performance, but the water resistance of the final plastic product can be reduced along with the rising of the starch content, and the water absorption rate is high, so that the water resistance of the plastic with high starch content is improved due to the poor water resistance of the starch, and the application range of the plastic in daily life can be widened.
CN107814955a discloses a water-resistant starch-based biodegradable plastic master batch and a preparation method thereof, which can improve the water resistance of starch-based plastics, but the prepared starch-based plastic master batch reduces the water absorption rate of 24 hours to about 4%, but the starch content is lower, and the highest starch content is only less than 30%.
CN111363205a discloses a starch-based degradable plastic with good heat resistance and a manufacturing method thereof, wherein the starch content is 50% at most, the water absorption rate for 24 hours is 0.15% at the lowest, the performance is close to that of a plastic product without starch, but the tensile strength is lower, and the tensile strength of the optimal scheme is 28.6MPa.
In summary, the existing starch-based plastics have low tensile strength while improving the water resistance, and cannot improve the water resistance and the tensile strength at the same time.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and the plastic woven bag is prepared by preparing modified starch and preparing modified nano white carbon black, so that the water resistance of the starch-based plastic woven bag is improved and the tensile strength of the starch-based plastic woven bag is improved.
In order to solve the technical problems, the invention adopts the following technical scheme:
a processing technology of a rapidly degradable plastic woven bag comprises the steps of preparing modified starch, preparing modified nanometer white carbon black, preparing flat filaments and weaving.
The following is a further improvement of the above technical scheme:
the step of preparing modified starch comprises preliminary modification and subsequent modification;
mixing starch and formamide, controlling the temperature to be 50-60 ℃, controlling the stirring speed to be 300-400r/min, controlling the ultrasonic frequency to be 75-85kHz, carrying out ultrasonic stirring for 25-35min, cooling after stirring, reducing the temperature to 4-6 ℃, slowly dropwise adding concentrated sulfuric acid-ammonium sulfate-n-butanol solution with the dropwise adding speed of 25-35mL/min, controlling the stirring speed to be 400-500r/min after the dropwise adding is completed, carrying out stirring for 13-20min, regulating the pH to be 7.2-7.5 by using sodium hydroxide, dialyzing for 22-25h by using distilled water, precipitating by using ethanol, and centrifugally drying to obtain the primary modified starch.
The molecular weight of the starch is 7000-9000;
the mass ratio of the starch to the formamide is 1:9-11;
in the concentrated sulfuric acid-ammonium sulfate-n-butanol solution, the mass ratio of the concentrated sulfuric acid to the ammonium sulfate to the n-butanol is 10-20:1.5-3:2-6;
the mass ratio of the concentrated sulfuric acid-ammonium sulfate-n-butanol solution to the starch is 30-40:1.
The subsequent modification comprises the steps of mixing the primary modified starch with a mixed solvent, regulating the pH to 8.3-8.6 by using a sodium hydroxide solution, adding isophorone diisocyanate and p-sulfonyl isocyanate, keeping the temperature to be 60-70 ℃, keeping the stirring speed to be 1500-2000r/min, stirring for 120-180min, cooling to room temperature, and precipitating by using absolute ethyl alcohol to obtain the modified starch.
The mass ratio of the primary modified starch to the mixed solvent is 1:13-17;
the mixed solvent comprises the following components in parts by mass: 8-12 parts of formamide, 1.8-2.2 parts of methanol and 0.9-1.1 parts of ethylene glycol;
the mass ratio of isophorone diisocyanate to primary modified starch is 1:45-55;
the mass ratio of the p-sulfonyl isocyanate to the primary modified starch is 1:60-80.
Mixing the nano white carbon black with a nitric acid solution, adding hydrogen peroxide, keeping the stirring speed at 500-600r/min, stirring for 40-50min, filtering, drying to no water, placing in a muffle furnace, controlling the temperature at 450-550 ℃, calcining for 110-130min, cooling to room temperature to obtain the preliminary modified nano white carbon black, mixing the preliminary modified nano white carbon black with absolute ethyl alcohol, stirring to uniformly disperse the preliminary modified nano white carbon black, adding vinyl trimethoxy silane, 2, 6-tertiary butyl-4-methylphenol and trioctyl ester, keeping the stirring speed at 1200-1500r/min, stirring for 70-90min, filtering, and drying to obtain the modified nano white carbon black.
The particle size of the nano white carbon black is 100-120nm;
the mass concentration of the nitric acid solution is 17-21%;
the mass concentration of the hydrogen peroxide is 13-25%;
the mass ratio of the nano white carbon black to the nitric acid solution to the hydrogen peroxide is 0.8-1.2:4.5-5.5:0.8-1.2;
the mass ratio of the vinyl trimethoxy silane to the preliminary modified nano white carbon black is 1:15-20;
the mass ratio of the 2, 6-tertiary butyl-4-methylphenol to the preliminary modified nano white carbon black is 1:40-50;
the mass ratio of the trioctyl ester to the preliminary modified nano white carbon black is 1:60-70.
The step of preparing the flat yarn comprises the steps of mixing modified starch, modified nano white carbon black, vulcanized lignin, plasticizer, paraffin, isopropyl trioleate acyloxy titanate, polycarbonate and polypropylene, controlling the extrusion temperature to be 155-165 ℃, controlling the extrusion pressure to be 6.0-7.0MPa, extruding by an extruder, cutting and stretching to obtain the starch-based plastic flat yarn.
The starch-based plastic flat filament comprises the following raw materials in parts by mass: 105-130 parts of modified starch, 4-6 parts of modified nano white carbon black, 4-6 parts of vulcanized lignin, 1.8-2.2 parts of plasticizer, 1.8-2.2 parts of paraffin, 0.8-1.2 parts of isopropyl trioleate acyloxy titanate, 8-12 parts of polycarbonate and 15-25 parts of polypropylene;
the plasticizer consists of glycerin and hexanediol, and the mass ratio of the plasticizer to the hexanediol is 1.5-2.5:1;
the molecular weight of the polycarbonate is 15000-25000;
the molecular weight of the polypropylene is 80000-120000.
The step of knitting is that starch-based plastic flat wires are sent into a knitting machine, knitting warp density is 55-65 pieces/100 mm, knitting weft density is 55-65 pieces/100 mm, a blank bag is obtained, and the blank bag is covered and sewn to obtain a plastic woven bag.
The embryo bag starch content of the plastic woven bag is 70.42-75.86wt%.
Compared with the prior art, the invention has the following beneficial effects:
the woven bag prepared by the invention has high tensile strength, the warp tensile load is 1292-1315N/50 mm, and the weft tensile load is 1275-1287N/50 mm (GB/T8946-2013);
the woven bag prepared by the method has good water resistance, the plastic woven bag is cut into square samples with the length of 61mm and the length of 61mm, the square samples are dried for 24 hours at 50 ℃, weighed, the samples are immersed into distilled water at 23 ℃ and taken out after 24 hours, the surface water is rapidly wiped by clean dry cloth, the water absorption is calculated, and the water absorption is 0.12-0.14% (GB/T1034-2008);
the woven bag prepared by the invention has good thermal stability, and the temperature is raised at 10 ℃/min, so that the thermal weight loss performance is tested, and the thermal weight loss temperature is 309-317 ℃;
the woven bag prepared by the invention has good degradation performance, and the degradation performance is tested by a soil burying method, and the weight loss rate in 180 days is 74.2-75.8%;
the woven bag prepared by the method has good stripping performance, printing ink is not easy to strip, the plastic woven bag is cut into square samples with 100mm x 100mm, and the stripping rate is tested by using adhesive tape with the stripping strength of 6.5N/15mm and is 1.34-1.45% (GB/T21661-2008).
Detailed Description
Example 1
(1) Preparation of modified starch
a. Preliminary modification
Mixing starch and formamide, controlling the temperature to 55 ℃, controlling the stirring speed to 350r/min, controlling the ultrasonic frequency to 80kHz, performing ultrasonic stirring for 30min, cooling after stirring, slowly dropwise adding concentrated sulfuric acid-ammonium sulfate-n-butanol solution to 5 ℃, controlling the stirring speed to 450r/min after dropwise adding is completed, stirring for 15min, adjusting the pH to 7.3 by using sodium hydroxide, dialyzing for 24h by using distilled water, precipitating by using ethanol, centrifuging and drying to obtain primary modified starch;
the molecular weight of the starch is 8500;
the mass ratio of the starch to the formamide is 1:10;
in the concentrated sulfuric acid-ammonium sulfate-n-butanol solution, the mass ratio of the concentrated sulfuric acid to the ammonium sulfate to the n-butanol is 15:2:5;
the mass ratio of the concentrated sulfuric acid-ammonium sulfate-n-butanol solution to the starch is 35:1;
b. subsequent modification
Mixing the primary modified starch with a mixed solvent, regulating the pH to 8.5 by using a sodium hydroxide solution, adding isophorone diisocyanate and p-sulfonyl isocyanate, keeping the temperature at 65 ℃, keeping the stirring speed at 1800r/min, stirring for 150min, cooling to room temperature, and precipitating by using absolute ethanol to obtain modified starch;
the mass ratio of the primary modified starch to the mixed solvent is 1:15;
the mixed solvent comprises the following components in parts by mass: 10 parts of formamide, 2 parts of methanol and 1 part of ethylene glycol;
the mass ratio of isophorone diisocyanate to primary modified starch is 1:50;
the mass ratio of the p-sulfonyl isocyanate to the primary modified starch is 1:70.
(2) Preparation of modified nano white carbon black
Mixing nano white carbon black with a nitric acid solution, adding hydrogen peroxide, keeping the stirring speed at 550r/min, stirring for 45min, filtering, drying until no water exists, placing in a muffle furnace, controlling the temperature at 480 ℃, calcining for 120min, cooling to room temperature to obtain preliminary modified nano white carbon black, mixing the preliminary modified nano white carbon black with absolute ethyl alcohol, stirring to uniformly disperse the preliminary modified nano white carbon black, adding vinyl trimethoxy silane, 2, 6-tertiary butyl-4-methylphenol and trioctyl ester, keeping the stirring speed at 1400r/min, stirring for 80min, filtering, and drying to obtain modified nano white carbon black;
the particle size of the nano white carbon black is 110nm;
the mass concentration of the nitric acid solution is 20%;
the mass concentration of the hydrogen peroxide is 15%;
the mass ratio of the nano white carbon black to the nitric acid solution to the hydrogen peroxide is 1:5:1;
the mass ratio of the vinyl trimethoxy silane to the preliminary modified nano white carbon black is 1:17;
the mass ratio of the 2, 6-tertiary butyl-4-methylphenol to the preliminary modified nano white carbon black is 1:45;
the mass ratio of the trioctyl ester to the preliminary modified nano white carbon black is 1:65.
(3) Flat yarn
Mixing modified starch, modified nano white carbon black, vulcanized lignin, plasticizer, paraffin, isopropyl trioleate acyloxy titanate, polycarbonate and polypropylene, controlling the extrusion temperature to 160 ℃, controlling the extrusion pressure to 6.5MPa, extruding by an extruder, cutting and stretching to obtain starch-based plastic flat filaments;
the starch-based plastic flat filament comprises the following raw materials in parts by mass: 110 parts of modified starch, 5 parts of modified nano white carbon black, 5 parts of vulcanized lignin, 2 parts of plasticizer, 2 parts of paraffin, 1 part of isopropyl trioleate acyloxy titanate, 10 parts of polycarbonate and 20 parts of polypropylene;
the plasticizer consists of glycerin and hexanediol, and the mass ratio of the plasticizer to the hexanediol is 2:1;
the molecular weight of the polycarbonate is 20000;
the molecular weight of the polypropylene is 100000.
(4) Braiding
Feeding the starch-based plastic flat filaments into a braiding machine, braiding the plastic flat filaments with a warp density of 60 pieces/100 mm and a weft density of 60 pieces/100 mm to obtain a blank bag, and covering and sewing the blank bag to obtain a plastic braided bag;
the embryo bag starch content of the plastic woven bag is 75.86wt%.
The woven bag prepared in example 1 has high tensile strength, a warp tensile load of 1315N/50 mm and a weft tensile load of 1287N/50 mm (GB/T8946-2013);
the woven bag prepared in example 1 has good water resistance, the plastic woven bag is cut into square samples with 61mm and 61mm, the square samples are dried for 24 hours at 50 ℃, weighed, the samples are immersed into distilled water at 23 ℃ and taken out after 24 hours, the surface water is rapidly wiped by clean dry cloth, and the water absorption is calculated to be 0.12% (GB/T1034-2008);
the woven bag prepared in the embodiment 1 has good thermal stability, and is heated at 10 ℃/min to test the thermal weight loss performance, and the thermal weight loss temperature is 317 ℃;
the woven bag prepared in the embodiment 1 has good degradation performance, and the degradation performance is tested by a soil burying method, and the weight loss rate in 180 days is 75.8%;
the woven bag prepared in example 1 was good in ink peeling property, the printing ink was not easily peeled off, the plastic woven bag was cut into square samples of 100mm x 100mm, and the peeling rate was measured using an adhesive tape having a peeling strength of 6.5N/15mm and a peeling rate of 1.34% (GB/T21661-2008).
Example 2
(1) Preparation of modified starch
a. Preliminary modification
Mixing starch and formamide, controlling the temperature to be 50 ℃, controlling the stirring speed to be 300r/min, controlling the ultrasonic frequency to be 85kHz, carrying out ultrasonic stirring for 35min, cooling after stirring, slowly dropwise adding concentrated sulfuric acid-ammonium sulfate-n-butanol solution to the mixture to the temperature of 4 ℃, controlling the stirring speed to be 400r/min after dropwise adding, stirring for 20min, regulating the pH to be 7.2 by using sodium hydroxide, dialyzing the mixture for 22h by using ethanol, precipitating the mixture, and centrifugally drying the mixture to obtain primary modified starch;
the molecular weight of the starch is 7000;
the mass ratio of the starch to the formamide is 1:9;
in the concentrated sulfuric acid-ammonium sulfate-n-butanol solution, the mass ratio of the concentrated sulfuric acid to the ammonium sulfate to the n-butanol is 10:1.5:2;
the mass ratio of the concentrated sulfuric acid-ammonium sulfate-n-butanol solution to the starch is 30:1;
b. subsequent modification
Mixing the primary modified starch with a mixed solvent, regulating the pH to 8.3 by using a sodium hydroxide solution, adding isophorone diisocyanate and p-sulfonyl isocyanate, keeping the temperature at 60 ℃, keeping the stirring speed at 1500r/min, stirring for 180min, cooling to room temperature, and precipitating by using absolute ethyl alcohol to obtain modified starch;
the mass ratio of the primary modified starch to the mixed solvent is 1:13;
the mixed solvent comprises the following components in parts by mass: 8 parts of formamide, 1.8 parts of methanol and 0.9 part of ethylene glycol;
the mass ratio of isophorone diisocyanate to primary modified starch is 1:45;
the mass ratio of the p-sulfonyl isocyanate to the primary modified starch is 1:60.
(2) Preparation of modified nano white carbon black
Mixing nano white carbon black with a nitric acid solution, adding hydrogen peroxide, keeping the stirring speed at 500r/min, stirring for 50min, filtering, drying until no water exists, placing in a muffle furnace, controlling the temperature at 450 ℃, calcining for 130min, cooling to room temperature to obtain preliminary modified nano white carbon black, mixing the preliminary modified nano white carbon black with absolute ethyl alcohol, stirring to uniformly disperse the preliminary modified nano white carbon black, adding vinyl trimethoxy silane, 2, 6-tertiary butyl-4-methylphenol and trioctyl ester, keeping the stirring speed at 1200r/min, stirring for 90min, filtering, and drying to obtain modified nano white carbon black;
the particle size of the nano white carbon black is 100nm;
the mass concentration of the nitric acid solution is 17%;
the mass concentration of the hydrogen peroxide is 13%;
the mass ratio of the nano white carbon black to the nitric acid solution to the hydrogen peroxide is 0.8:4.5:0.8;
the mass ratio of the vinyl trimethoxy silane to the preliminary modified nano white carbon black is 1:15;
the mass ratio of the 2, 6-tertiary butyl-4-methylphenol to the preliminary modified nano white carbon black is 1:40;
the mass ratio of the trioctyl ester to the preliminary modified nano white carbon black is 1:60.
(3) Flat yarn
Mixing modified starch, modified nano white carbon black, vulcanized lignin, plasticizer, paraffin, isopropyl trioleate acyloxy titanate, polycarbonate and polypropylene, controlling the extrusion temperature to 155 ℃, controlling the extrusion pressure to 6.0MPa, extruding by an extruder, cutting and stretching to obtain starch-based plastic flat filaments;
the starch-based plastic flat filament comprises the following raw materials in parts by mass: 105 parts of modified starch, 4 parts of modified nano white carbon black, 4 parts of vulcanized lignin, 1.8 parts of plasticizer, 1.8 parts of paraffin, 0.8 part of isopropyl trioleate acyloxy titanate, 8 parts of polycarbonate and 15 parts of polypropylene;
the plasticizer consists of glycerin and hexanediol, and the mass ratio of the plasticizer to the hexanediol is 1.5:1;
the molecular weight of the polycarbonate is 15000;
the molecular weight of the polypropylene was 80000.
(4) Braiding
Feeding the starch-based plastic flat filaments into a braiding machine, braiding the plastic flat filaments with a warp density of 55 pieces/100 mm and a weft density of 55 pieces/100 mm to obtain a blank bag, and covering and sewing the blank bag to obtain a plastic braided bag;
the embryo bag starch content of the plastic woven bag is 74.79wt%.
The woven bag prepared in example 2 has high tensile strength, a warp tensile load of 1307N/50mm and a weft tensile load of 1275N/50mm (GB/T8946-2013);
the woven bag prepared in example 2 has good water resistance, the plastic woven bag is cut into square samples with 61mm and 61mm, the square samples are dried for 24 hours at 50 ℃, weighed, the samples are immersed into distilled water at 23 ℃ and taken out after 24 hours, the surface water is rapidly wiped by clean dry cloth, and the water absorption is calculated to be 0.13% (GB/T1034-2008);
the woven bag prepared in the embodiment 2 has good thermal stability, and is heated at 10 ℃/min to test the thermal weight loss performance, and the thermal weight loss temperature is 309 ℃;
the woven bag prepared in the embodiment 2 has good degradation performance, and the degradation performance is tested by a soil burying method, and the weight loss rate in 180 days is 74.2%;
the woven bag prepared in example 2 was good in ink peeling property, the printing ink was not easily peeled off, the plastic woven bag was cut into square samples of 100mm x 100mm, and the peeling rate was tested using an adhesive tape having a peeling strength of 6.5N/15mm and a peeling rate of 1.37% (GB/T21661-2008).
Example 3
(1) Preparation of modified starch
a. Preliminary modification
Mixing starch and formamide, controlling the temperature to be 60 ℃, controlling the stirring speed to be 400r/min, controlling the ultrasonic frequency to be 75kHz, carrying out ultrasonic stirring for 25min, cooling after stirring, slowly dropwise adding concentrated sulfuric acid-ammonium sulfate-n-butanol solution at the speed of 35mL/min, controlling the stirring speed to be 500r/min after dropwise adding, stirring for 13min, regulating the pH to be 7.5 by using sodium hydroxide, dialyzing for 25h by using distilled water, precipitating by using ethanol, centrifuging and drying to obtain primary modified starch;
the molecular weight of the starch is 9000;
the mass ratio of the starch to the formamide is 1:11;
in the concentrated sulfuric acid-ammonium sulfate-n-butanol solution, the mass ratio of the concentrated sulfuric acid to the ammonium sulfate to the n-butanol is 20:3:6;
the mass ratio of the concentrated sulfuric acid-ammonium sulfate-n-butanol solution to the starch is 40:1;
b. subsequent modification
Mixing the primary modified starch with a mixed solvent, regulating the pH to 8.6 by using a sodium hydroxide solution, adding isophorone diisocyanate and p-sulfonyl isocyanate, keeping the temperature at 70 ℃, keeping the stirring speed at 2000r/min, stirring for 120min, cooling to room temperature, and precipitating by using absolute ethyl alcohol to obtain modified starch;
the mass ratio of the primary modified starch to the mixed solvent is 1:17;
the mixed solvent comprises the following components in parts by mass: 12 parts of formamide, 2.2 parts of methanol and 1.1 parts of ethylene glycol;
the mass ratio of isophorone diisocyanate to primary modified starch is 1:55;
the mass ratio of the p-sulfonyl isocyanate to the primary modified starch is 1:80.
(2) Preparation of modified nano white carbon black
Mixing nano white carbon black with a nitric acid solution, adding hydrogen peroxide, keeping the stirring speed at 600r/min, stirring for 40min, filtering, drying until no water exists, placing in a muffle furnace, controlling the temperature at 500 ℃, calcining for 110min, cooling to room temperature to obtain preliminary modified nano white carbon black, mixing the preliminary modified nano white carbon black with absolute ethyl alcohol, stirring to uniformly disperse the preliminary modified nano white carbon black, adding vinyl trimethoxy silane, 2, 6-tertiary butyl-4-methylphenol and trioctyl ester, keeping the stirring speed at 1500r/min, stirring for 70min, filtering, and drying to obtain modified nano white carbon black;
the particle size of the nano white carbon black is 120nm;
the mass concentration of the nitric acid solution is 21%;
the mass concentration of the hydrogen peroxide is 25%;
the mass ratio of the nano white carbon black to the nitric acid solution to the hydrogen peroxide is 1.2:5.5:1.2;
the mass ratio of the vinyl trimethoxy silane to the preliminary modified nano white carbon black is 1:20;
the mass ratio of the 2, 6-tertiary butyl-4-methylphenol to the preliminary modified nano white carbon black is 1:50;
the mass ratio of the trioctyl ester to the preliminary modified nano white carbon black is 1:70.
(3) Flat yarn
Mixing modified starch, modified nano white carbon black, vulcanized lignin, plasticizer, paraffin, isopropyl trioleate acyloxy titanate, polycarbonate and polypropylene, controlling the extrusion temperature to be 165 ℃, controlling the extrusion pressure to be 7.0MPa, extruding by an extruder, cutting and stretching to obtain starch-based plastic flat filaments;
the starch-based plastic flat filament comprises the following raw materials in parts by mass: 130 parts of modified starch, 6 parts of modified nano white carbon black, 6 parts of vulcanized lignin, 2.2 parts of plasticizer, 2.2 parts of paraffin, 1.2 parts of isopropyl trioleate acyloxy titanate, 12 parts of polycarbonate and 25 parts of polypropylene;
the plasticizer consists of glycerin and hexanediol, and the mass ratio of the plasticizer to the hexanediol is 2.5:1;
the molecular weight of the polycarbonate is 25000;
the molecular weight of the polypropylene was 120000.
(4) Braiding
Feeding the starch-based plastic flat filaments into a braiding machine, braiding the plastic flat filaments with a warp density of 65 filaments/100 mm and a weft density of 65 filaments/100 mm to obtain a blank bag, and covering and sewing the blank bag to obtain a plastic braided bag;
the embryo bag starch content of the plastic woven bag is 70.42wt%.
The woven bag prepared in example 3 has high tensile strength, a warp tensile load of 1292N/50 mm and a weft tensile load of 1286N/50 mm (GB/T8946-2013);
the woven bag prepared in example 3 has good water resistance, the plastic woven bag is cut into square samples with 61mm and 61mm, the square samples are dried for 24 hours at 50 ℃, weighed, the samples are immersed into distilled water at 23 ℃ and taken out after 24 hours, the surface water is rapidly wiped by clean dry cloth, and the water absorption is calculated to be 0.14% (GB/T1034-2008);
the woven bag prepared in the embodiment 3 has good thermal stability, and is heated at 10 ℃/min to test the thermal weight loss performance, and the thermal weight loss temperature is 313 ℃;
the woven bag prepared in the embodiment 3 has good degradation performance, and the degradation performance is tested by a soil burying method, and the weight loss rate in 180 days is 74.8%;
the woven bag prepared in example 3 was good in ink peeling property, the printing ink was not easily peeled off, the plastic woven bag was cut into square samples of 100mm x 100mm, and the peeling rate was measured using an adhesive tape having a peeling strength of 6.5N/15mm and a peeling rate of 1.45% (GB/T21661-2008).
Comparative example 1
Based on the example 1, the subsequent modification step in the step of preparing modified starch is omitted, the preliminary modified starch is directly used for preparing flat filaments in the step of preparing flat filaments, and the rest steps are the same, so that the woven bag is prepared.
The woven bag prepared in comparative example 1 had a warp tensile load of 958N/50 mm and a weft tensile load of 873N/50 mm (GB/T8946-2013);
the woven bag prepared in comparative example 1 was tested for water resistance, a plastic woven bag was cut into square samples with 61mm by 61mm, dried at 50 ℃ for 24 hours, weighed, the samples were immersed in distilled water at 23 ℃ for 24 hours, then taken out, the surface water was rapidly wiped with clean dry cloth, weighed, and the water absorption was calculated to be 2.86% (GB/T1034-2008);
the woven bag prepared in comparative example 1 was tested for thermal stability, and the thermal weight loss performance was tested at a temperature of 256 ℃ at a temperature of 10 ℃/min;
the woven bag prepared in comparative example 1 has degradation performance tested by a soil burying method, and the weight loss rate of 180 days is 68.51%;
the woven bag prepared in comparative example 1 was cut into square samples of 100mm x 100mm, and the woven bag was tested for peeling rate using an adhesive tape having a peeling strength of 6.5N/15mm, and peeling rate was 3.85% (GB/T21661-2008).
Comparative example 2
Based on the embodiment 1, the step of preparing modified nano white carbon black is omitted, unmodified nano white carbon black is directly used for preparing flat filaments in the step of preparing flat filaments, and the rest steps are the same, so that the woven bag is prepared.
The woven bag prepared in comparative example 2 has a warp tensile load of 1015N/50 mm and a weft tensile load of 955/N/50 mm (GB/T8946-2013);
the woven bag prepared in comparative example 2 was tested for water resistance, the plastic woven bag was cut into square samples with 61mm by 61mm, dried at 50 ℃ for 24 hours, weighed, the samples were immersed in distilled water at 23 ℃ for 24 hours, then taken out, the surface water was rapidly wiped with clean dry cloth, weighed, and the water absorption was calculated to be 1.71% (GB/T1034-2008);
the woven bag prepared in comparative example 2 was tested for thermal stability, and tested for thermal weight loss performance at a temperature of 284 ℃ at a temperature of 10 ℃/min;
the woven bag prepared in comparative example 2 has degradation performance tested by a soil burying method, and the weight loss rate of 180 days is 71.2%;
the woven bag prepared in comparative example 2 was cut into square samples of 100mm x 100mm, and the woven bag was tested for peel strength using an adhesive tape having a peel strength of 6.5N/15mm and a peel strength of 2.31% (GB/T21661-2008).

Claims (6)

1. The processing technology of the rapidly-degradable plastic woven bag is characterized by comprising the steps of preparing modified starch, preparing modified nano white carbon black, preparing flat filaments and weaving;
the step of preparing modified starch comprises preliminary modification and subsequent modification;
mixing starch and formamide, controlling the temperature to be 50-60 ℃, controlling the stirring speed to be 300-400r/min, controlling the ultrasonic frequency to be 75-85kHz, carrying out ultrasonic stirring for 25-35min, cooling to 4-6 ℃ after stirring, slowly dropwise adding concentrated sulfuric acid-ammonium sulfate-n-butanol solution at the dropwise adding speed of 25-35mL/min, controlling the stirring speed to be 400-500r/min after dropwise adding, stirring for 13-20min, regulating the pH to be 7.2-7.5 by using sodium hydroxide, dialyzing for 22-25h by using distilled water, precipitating by using ethanol, and centrifugally drying to obtain the primary modified starch;
mixing the primary modified starch with a mixed solvent, regulating the pH to 8.3-8.6 by using a sodium hydroxide solution, adding isophorone diisocyanate and p-sulfonyl isocyanate, keeping the temperature at 60-70 ℃, keeping the stirring speed at 1500-2000r/min, stirring for 120-180min, cooling to room temperature, and precipitating by using absolute ethyl alcohol to obtain modified starch;
the mixed solvent comprises the following components in parts by mass: 8-12 parts of formamide, 1.8-2.2 parts of methanol and 0.9-1.1 parts of ethylene glycol;
mixing nano white carbon black with nitric acid solution, adding hydrogen peroxide, keeping the stirring speed at 500-600r/min, stirring for 40-50min, filtering, drying to be free of moisture, controlling the temperature at 450-550 ℃, calcining for 110-130min, cooling to room temperature to obtain preliminary modified nano white carbon black, mixing the preliminary modified nano white carbon black with absolute ethyl alcohol, stirring to uniformly disperse the preliminary modified nano white carbon black, adding vinyl trimethoxy silane, 2, 6-tertiary butyl-4-methylphenol and trioctyl ester, keeping the stirring speed at 1200-1500r/min, stirring for 70-90min, filtering, and drying to obtain modified nano white carbon black;
the step of preparing the flat yarn comprises the steps of mixing modified starch, modified nano white carbon black, vulcanized lignin, plasticizer, paraffin, isopropyl trioleate acyloxy titanate, polycarbonate and polypropylene, controlling the extrusion temperature to be 155-165 ℃, controlling the extrusion pressure to be 6.0-7.0MPa, extruding, cutting and stretching to obtain the starch-based plastic flat yarn.
2. The process for manufacturing the rapidly degradable plastic woven bag according to claim 1, wherein the process comprises the following steps of:
the molecular weight of the starch is 7000-9000;
the mass ratio of the starch to the formamide is 1:9-11;
in the concentrated sulfuric acid-ammonium sulfate-n-butanol solution, the mass ratio of the concentrated sulfuric acid to the ammonium sulfate to the n-butanol is 10-20:1.5-3:2-6;
the mass ratio of the concentrated sulfuric acid-ammonium sulfate-n-butanol solution to the starch is 30-40:1.
3. The process for manufacturing the rapidly degradable plastic woven bag according to claim 1, wherein the process comprises the following steps of:
the mass ratio of the primary modified starch to the mixed solvent is 1:13-17;
the mass ratio of isophorone diisocyanate to primary modified starch is 1:45-55;
the mass ratio of the p-sulfonyl isocyanate to the primary modified starch is 1:60-80.
4. The process for manufacturing the rapidly degradable plastic woven bag according to claim 1, wherein the process comprises the following steps of:
the particle size of the nano white carbon black is 100-120nm;
the mass concentration of the nitric acid solution is 17-21%;
the mass concentration of the hydrogen peroxide is 13-25%;
the mass ratio of the nano white carbon black to the nitric acid solution to the hydrogen peroxide is 0.8-1.2:4.5-5.5:0.8-1.2;
the mass ratio of the vinyl trimethoxy silane to the preliminary modified nano white carbon black is 1:15-20;
the mass ratio of the 2, 6-tertiary butyl-4-methylphenol to the preliminary modified nano white carbon black is 1:40-50;
the mass ratio of the trioctyl ester to the preliminary modified nano white carbon black is 1:60-70.
5. The process for manufacturing the rapidly degradable plastic woven bag according to claim 1, wherein the process comprises the following steps of:
the starch-based plastic flat filament comprises the following raw materials in parts by mass: 105-130 parts of modified starch, 4-6 parts of modified nano white carbon black, 4-6 parts of vulcanized lignin, 1.8-2.2 parts of plasticizer, 1.8-2.2 parts of paraffin, 0.8-1.2 parts of isopropyl trioleate acyloxy titanate, 8-12 parts of polycarbonate and 15-25 parts of polypropylene;
the plasticizer consists of glycerin and hexanediol, and the mass ratio of the plasticizer to the hexanediol is 1.5-2.5:1;
the molecular weight of the polycarbonate is 15000-25000;
the molecular weight of the polypropylene is 80000-120000.
6. The process for manufacturing the rapidly degradable plastic woven bag according to claim 1, wherein the process comprises the following steps of:
the step of knitting is that starch-based plastic flat wires are knitted, knitting warp density is 55-65 pieces/100 mm, knitting weft density is 55-65 pieces/100 mm, a embryo bag is obtained, and the embryo bag is covered and stitched to obtain a plastic woven bag.
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