CN111205610A - Novel PLA and preparation method thereof - Google Patents
Novel PLA and preparation method thereof Download PDFInfo
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- CN111205610A CN111205610A CN202010178420.4A CN202010178420A CN111205610A CN 111205610 A CN111205610 A CN 111205610A CN 202010178420 A CN202010178420 A CN 202010178420A CN 111205610 A CN111205610 A CN 111205610A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- 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
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- C08L2201/06—Biodegradable
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a novel PLA, which comprises the following raw materials: polylactic acid, lignosulfonate, epichlorohydrin, modified antibacterial agent, linear low-density polyethylene, polyvinyl alcohol, polycarbonate, pentaerythritol, suberic acid, diphenylmethane diisocyanate, dioctyl phthalate, a silane coupling agent KH-570, bamboo fiber, potato starch, montmorillonite, konjac glucomannan, calcium carbonate, liquid paraffin, ethylene ethyl acrylate, glycerol and fatty acyl diethanolamine. The invention also discloses a preparation method of the novel PLA. The novel PLA prepared by the invention has excellent antibacterial property and mechanical strength.
Description
Technical Field
The invention belongs to the technical field of preparation of novel PLA, and particularly relates to novel PLA and a preparation method thereof.
Background
Polycarbonate (PLA) is a new type of bio-based and renewable biodegradable material made using starch feedstock proposed from renewable plant resources (e.g., corn, tapioca, etc.). The starch raw material is saccharified to obtain glucose, the glucose and certain strains are fermented to prepare high-purity lactic acid, and polycarbonate with certain molecular weight is synthesized by a chemical synthesis method. The biodegradable plastic has good biodegradability, can be completely degraded by microorganisms in the nature under specific conditions after being used, finally generates carbon dioxide and water, does not pollute the environment, is very beneficial to environmental protection, and is a well-known environment-friendly material.
The Chinese patent document "a PLA composite material (application publication No. CN 104927323B)" discloses a PLA composite material, which comprises the following raw materials in parts by weight: 40-65 parts of Polycarbonate (PLA), 10-20 parts of anhydrous sodium sulfate, 15-30 parts of polyethylene terephthalate (PET), 5-10 parts of a toughening agent, 0.2-0.6 part of a stabilizer, 2-6 parts of a plasticizer and 0.4-1 part of a lubricant. The PLA composite material improves the toughness and heat resistance of the polycarbonate material, has good molding processability, and enables the polycarbonate material to have a wider application range. The antibacterial property of the novel PLA can not meet the requirement in practical use.
Disclosure of Invention
The invention aims to provide a novel PLA and a preparation method thereof, and aims to solve the problem of how to optimize components, dosage, methods and the like on the basis of a degradable novel PLA disclosed in a patent application document 'a PLA composite material (application publication number: CN 104927323B'), and improve the antibacterial and water absorption properties of the novel PLA.
In order to solve the technical problems, the invention adopts the following technical scheme:
a novel PLA comprises the following raw materials: polylactic acid, lignosulfonate, epichlorohydrin, modified antibacterial agent, linear low-density polyethylene, polyvinyl alcohol, polycarbonate, pentaerythritol, suberic acid, diphenylmethane diisocyanate, dioctyl phthalate, a silane coupling agent KH-570, bamboo fiber, potato starch, montmorillonite, konjac glucomannan, calcium carbonate, liquid paraffin, ethylene ethyl acrylate, glycerol and fatty acyl diethanolamine;
the weight ratio of the lignosulfonate to the epichlorohydrin, the modified antibacterial agent to the linear low-density polyethylene to the polycarbonate to the dioctyl phthalate to the silane coupling agent KH-570 is (12-24) to (4-9) to (5-10) to (8-14) to (4-8) to (4-9) to (1-3);
the modified antibacterial agent comprises the following raw materials in parts by weight: 10-20 parts of chitin fiber, 4-8 parts of bamboo fiber, 3-9 parts of polyvinylpyrrolidone, 8-16 parts of deionized water, 2-6 parts of sodium chloride, 1-4 parts of defoaming agent, 3-6 parts of aluminum nitrate, 2-5 parts of hexamethylene diamine and 1-4 parts of diammonium hydrogen phosphate.
Further, the weight ratio of the lignosulfonate to the epichlorohydrin to the modified antibacterial agent to the linear low-density polyethylene to the polycarbonate to the dioctyl phthalate to the silane coupling agent KH-570 is 17.8: 6.8: 7.3: 11.3: 5.9:6.2: 2.2.
Further, the feed comprises the following raw materials in parts by weight: 80-120 parts of polylactic acid, 12-24 parts of lignosulfonate, 4-9 parts of epichlorohydrin, 5-10 parts of modified antibacterial agent, 8-14 parts of linear low-density polyethylene, 15-25 parts of polyvinyl alcohol, 4-8 parts of polycarbonate, 4-8 parts of pentaerythritol, 3-6 parts of suberic acid, 2-5 parts of diphenylmethane diisocyanate, 4-9 parts of dioctyl phthalate, 4-3 parts of silane coupling agent KH-5701, 9-16 parts of bamboo fiber, 4-8 parts of potato starch, 2-6 parts of montmorillonite, 1-5 parts of konjac glucomannan, 4-7 parts of calcium carbonate, liquid paraffin, ethylene ethyl acrylate, glycerol and fatty acyl diethanolamine.
Further, the modified antibacterial agent is prepared by the following process: uniformly mixing chitin fiber, bamboo fiber, polyvinylpyrrolidone and deionized water, grinding, heating, preserving heat, adding sodium chloride and a defoaming agent, stirring, continuously heating, preserving heat, adding aluminum nitrate and hexamethylenediamine, uniformly mixing, heating in a water bath, cooling to room temperature, adding diammonium hydrogen phosphate, uniformly mixing, aging, filtering, washing, drying, calcining, and cooling to room temperature to obtain the antibacterial modification auxiliary agent.
The invention provides a preparation method of novel PLA, which comprises the following steps:
s1: drying lignosulfonate, dissolving with 10mol/L NaOH solution, heating in water bath, stirring, heating to 70-80 deg.C, adding epichlorohydrin, mixing, refluxing and stirring at 70-75 deg.C for 4-6 hr, washing to pH 7, vacuum drying at 100-110 deg.C to obtain the final product
；
S2: pentaerythritol, suberic acid and polycarbonate are mixed evenly and put under nitrogenUnder the environment, the polycondensation reaction is carried out for 2 to 4 hours at the temperature of 150-
；
S3, feeding the materials
Adding polylactic acid, linear low density polyethylene and polyvinyl alcohol, mixing uniformly, cooling, washing to neutrality, and finally performing solid-liquid separation to obtain the material
；
S4, mixing the materials
Mixing with diphenylmethane diisocyanate, calcium carbonate, bamboo fiber, potato starch, montmorillonite, konjac glucomannan, liquid paraffin, silane coupling agent KH-570, ethyl ethylene acrylate, glycerol, and fatty acyl diethanolamine to obtain material
；
S5, mixing the materials
Modified antimicrobial agents and materials
Mixing uniformly to obtain the novel PLA.
The invention has the following beneficial effects:
(1) as can be seen from the data of examples 1-3 and comparative example 9, the antibacterial properties of the novel PLA prepared in examples 1-3 are significantly higher than those of the novel PLA prepared in comparative example 9; meanwhile, as can be seen from the data of examples 1 to 3, example 1 is the most preferred example.
(2) As can be seen from the data of example 1 and comparative examples 1-8, lignosulfonate, epichlorohydrin, modified antimicrobial, linear low density polyethylene, polycarbonate, dioctyl phthalate, silane coupling agent KH-570 play a synergistic role in the preparation of the antimicrobial agent, which improves the antimicrobial properties of the novel PLA in the preparation of the novel PLA; this is: lignosulfonate, epichlorohydrin, modified antibacterial agent, linear low-density polyethylene, polycarbonate, dioctyl phthalate and silane coupling agent KH-570 are used as a reinforcing system, polycarbonate is used as porous degradable water-absorbing filler, the porous degradable water-absorbing filler has good water absorption and biocompatibility, the use safety of novel PLA is guaranteed, the surface of the polycarbonate contains a large number of hydroxyl groups, the polycarbonate is grafted to the linear low-density polyethylene under the grafting effect of the silane coupling agent KH-570, the surface of the linear low-density polyethylene contains rich unsaturated bonds, the polycarbonate can be attached to the linear low-density polyethylene, and the degradation of the linear low-density polyethylene can be accelerated due to the grafting of the polycarbonate by utilizing the biocompatibility and degradability of the polycarbonate, the application of the modified PLA in the preparation of the novel PLA further improves the degradation performance of the novel PLA. The polycarbonate generates an acidic environment after hydrolysis, the acidic environment can inhibit the activity of the respiring enzyme of bacteria so as to inhibit the growth of the bacteria, thereby killing the bacteria, and the excellent antibacterial reinforcing performance of the reinforcing system is endowed by utilizing the antibacterial sterilization performance of the polycarbonate. Wherein the added modified antibacterial agent is prepared by uniformly mixing 3, 4-dihydroxybenzaldehyde, sodium hexametaphosphate, diphenylmethane diisocyanate, 15-25% by mass of silver nitrate solution, dibutyltin dilaurate, acetic acid and methanol, standing at normal temperature, adding sodium borohydride, uniformly mixing, stirring, carrying out suction filtration to obtain a precipitate, dialyzing the precipitate in hydrochloric acid solution, and carrying out freeze drying to obtain a material a; the preparation method comprises the steps of uniformly mixing a silane coupling agent KH-560, polyethylene glycol and sodium bisulfite, adding a material a, uniformly mixing, heating, keeping the temperature, stirring, and cooling to room temperature to obtain the product, wherein the antibacterial performance of 3, 4-dihydroxybenzaldehyde, the adhesive performance of polyethylene glycol and diphenylmethane diisocyanate, and dibutyltin dilaurate are used as catalysts, the combination of 3, 4-dihydroxybenzaldehyde and sodium borohydride is realized under the grafting action of the silane coupling agent KH-560, the antibacterial performance of the novel PLA is effectively improved when the preparation method is applied to the preparation of the novel PLA, sodium groups on lignosulfonate are replaced by hydroxyl groups of sodium hydroxide, the epoxidation treatment of lignosulfonate is realized through the combination of the hydroxyl groups and epoxy groups of epoxy chloropropane, and the graft modification effect of the silane coupling agent KH-570 is realized, the stable combination of the lignosulfonate and the linear low-density polyethylene is realized, so that the mechanical strength of the linear low-density polyethylene is improved, and the epoxidized lignosulfonate is utilized to wrap unsaturated bonds on the surface of the linear low-density polyethylene, so that the density of a surface net structure of the linear low-density polyethylene is improved.
Konjac glucomannan is natural high-molecular soluble dietary fiber, and has water retention property, so that the whole novel PLA can be kept in a relatively dry state, the microstructure of the konjac glucomannan is more complex due to the high-molecular fiber structure of the konjac glucomannan, the konjac glucomannan is added into the preparation of the novel PLA, the unsaturated bond on the surface of the polylactic acid is connected with the hydroxyl on the surface of the konjac glucomannan under the grafting effect of a silane coupling agent KH-570, the graft modification of the polylactic acid by the high-molecular material is realized, and the konjac glucomannan is wrapped on the surface of the polylactic acid to realize a compact high-molecular fiber film layer and is applied to the preparation of the novel PLA, so that the novel PLA is more flexible and is not easy to break, the degradability of the konjac glucomannan is high, and the white pollution can be reduced. Montmorillonite and potato starch form hydrogen bonds, and under the grafting action of silane coupling agent KH-570, the combination of the hydrogen bonds and linear low-density polyethylene is realized, the surface net density of the linear low-density polyethylene is further increased, the tensile strength of the novel PLA is enhanced, the surface grafting modification is carried out on bamboo fibers through the silane coupling agent KH-570, one end of the silane coupling agent KH-570 is a polar bond, and the other end of the silane coupling agent KH-570 is a non-polar end, the connection of the bamboo fibers and the linear low-density polyethylene is realized through grafting, and after the bamboo fibers are connected with the linear low-density polyethylene, the interface contact angle is increased, so that the surface tension is reduced, the wettability of the fiber surface is improved, the compatibility of the interface is improved, and the montmorillonite is applied to the preparation of the novel PLA, the montmorillonite is an inorganic substance with a large number of hydroxyl groups on the surface, while the potato starch and the, the inorganic matters and organic matters containing hydroxyl are grafted to the linear low-density polyethylene, the reinforcing materials are degradable and are attached to the surface of the linear low-density polyethylene after grafting, and the grafted degradable reinforcing materials further accelerate the degradation of the linear low-density polyethylene, so that the degradation performance of the novel PLA is improved.
(3) As can be seen from the data of comparative examples 10 to 12, when the weight ratio of lignosulfonate, epichlorohydrin, modified antibacterial agent, linear low density polyethylene, polycarbonate, dioctyl phthalate, silane coupling agent KH-570 was out of the range of (12-24): 4-9): 5-10): 8-14): 4-8): 4-9): 1-3, the antibacterial performance values of the novel PLA obtained were very different from those of examples 1 to 3 and were much smaller than those of examples 1 to 3. In the invention, lignosulfonate, epichlorohydrin, a modified antibacterial agent, linear low-density polyethylene, polycarbonate, dioctyl phthalate and a silane coupling agent KH-570 are added as a reinforcing system, in the preparation of the novel PLA controlled in the examples 1-3, lignosulfonate, epichlorohydrin, a modified antibacterial agent, linear low-density polyethylene, polycarbonate, dioctyl phthalate and the silane coupling agent KH-570 are added in the weight ratio of (12-24) to (4-9) to (5-10) to (8-14) to (4-8) to (4-9) to (1-3), so that lignosulfonate and linear low-density polyethylene are used as main raw materials in the reinforcing system, and the basic component of the lignosulfonate is a benzyl propane derivative and has a structure with a hydrophobic skeleton of C6-C3, a sulfonic group and other hydrophilic groups, the lignosulfonate is a polar material, the polyolefin is a non-polar material, the dioctyl phthalate is added, the bonding force between the lignosulfonate and the linear low-density polyethylene is increased, the compatibility between the lignosulfonate and the linear low-density polyethylene is improved, the epoxidation of the lignosulfonate by epoxy chloropropane is realized under the catalytic action of sodium hydroxide, a sodium group on the lignosulfonate is replaced by a hydroxyl group of the sodium hydroxide, the epoxidation of the lignosulfonate is realized by the combination of the hydroxyl group and an epoxy group of the epoxy chloropropane, and the stable combination of the lignosulfonate and the linear low-density polyethylene is realized under the grafting and changing action of a silane coupling agent KH-570, so that the mechanical strength of the linear low-density polyethylene is improved, the epoxidized lignosulfonate is utilized to wrap unsaturated bonds on the surface of linear low-density polyethylene, so that the density of a network structure on the surface of the linear low-density polyethylene is improved, the mechanical strength of the linear low-density polyethylene is further enhanced, the surfaces of the modified antibacterial agent and the polycarbonate also contain a large amount of hydroxyl groups, the modified antibacterial agent and the polycarbonate are combined with the unsaturated bonds on the surface of the linear low-density polyethylene under the grafting effect of a silane coupling agent KH-570, the antibacterial property of the linear low-density polyethylene is enhanced by utilizing the synergistic effect of the modified antibacterial agent and the antibacterial property of the polycarbonate, the beneficial mechanical strength and the antibacterial property of a reinforcing system are further endowed, and the prepared novel PLA has excellent mechanical strength and antibacterial property.
Detailed Description
In order to facilitate a better understanding of the invention, the following examples are given to illustrate, but not to limit the scope of the invention.
In the examples, the novel PLA comprises the following raw materials in parts by weight: 80-120 parts of polylactic acid, 12-24 parts of lignosulfonate, 4-9 parts of epichlorohydrin, 5-10 parts of modified antibacterial agent, 8-14 parts of linear low-density polyethylene, 15-25 parts of polyvinyl alcohol, 4-8 parts of polycarbonate, 4-8 parts of pentaerythritol, 3-6 parts of suberic acid, 2-5 parts of diphenylmethane diisocyanate, 4-9 parts of dioctyl phthalate, 4-3 parts of silane coupling agent KH-5701, 9-16 parts of bamboo fiber, 4-8 parts of potato starch, 2-6 parts of montmorillonite, 1-5 parts of konjac glucomannan, 4-7 parts of calcium carbonate, 2-5 parts of liquid paraffin, 4-8 parts of ethylene acrylic acid ethyl ester, 3-9 parts of glycerol and 3-9 parts of fatty acyl diethanolamine.
The modified antibacterial agent is prepared by the following process: uniformly mixing 10-20 parts of chitin fiber, 4-8 parts of bamboo fiber, 3-9 parts of polyvinylpyrrolidone and 8-16 parts of deionized water in parts by weight, grinding, heating, preserving heat, adding 2-6 parts of sodium chloride and 1-4 parts of defoaming agent, stirring, continuously heating, preserving heat, adding 3-6 parts of aluminum nitrate and 2-5 parts of hexamethylenediamine, uniformly mixing, heating in a water bath, cooling to room temperature, adding 1-4 parts of diammonium hydrogen phosphate, uniformly mixing, aging, filtering, washing, drying, calcining, and cooling to room temperature to obtain the antibacterial modification aid.
The invention provides a preparation method of novel PLA, which comprises the following steps:
s1: drying lignosulfonate, dissolving with 10mol/L NaOH solution, heating in water bath, stirring, heating to 70-80 deg.C, adding epichlorohydrin, mixing, refluxing and stirring at 70-75 deg.C for 4-6 hr, washing to pH 7, vacuum drying at 100-110 deg.C to obtain the final product
；
S2: pentaerythritol, suberic acid and polycarbonate are evenly mixed, and polycondensation reaction is carried out for 2 to 4 hours at the temperature of 180 ℃ under the nitrogen environment to obtain the material
；
S3, feeding the materials
Adding polylactic acid, linear low density polyethylene and polyvinyl alcohol, mixing uniformly, cooling, washing to neutrality, and finally performing solid-liquid separation to obtain the material
；
S4, mixing the materials
Mixing with diphenylmethane diisocyanate, calcium carbonate, bamboo fiber, potato starch, montmorillonite, konjac glucomannan, liquid paraffin, silane coupling agent KH-570, ethylene ethyl acrylate, and glycerolMixing with fatty acid diethanol amide to obtain the material
；
S5, mixing the materials
Modified antimicrobial agents and materials
Mixing uniformly to obtain the novel PLA.
Example 1
The novel PLA comprises the following raw materials in parts by weight: 100 parts of polylactic acid, 18 parts of lignosulfonate, 6.5 parts of epoxy chloropropane, 7.5 parts of modified antibacterial agent, 11 parts of linear low-density polyethylene, 20 parts of polyvinyl alcohol, 6 parts of polycarbonate, 6 parts of pentaerythritol, 4.5 parts of suberic acid, 3.5 parts of diphenylmethane diisocyanate, 6.4 parts of dioctyl phthalate, KH-5702.3 parts of silane coupling agent, 13 parts of bamboo fiber, 5.8 parts of potato starch, 4.9 parts of montmorillonite, 2.8 parts of konjac glucomannan, 5.2 parts of calcium carbonate, 3.3 parts of liquid paraffin, 5.8 parts of ethylene ethyl acrylate, 6.3 parts of glycerol and 5.8 parts of fatty acyl diethanolamine.
The modified antibacterial agent is prepared by the following process: uniformly mixing 15 parts of chitin fiber, 6 parts of bamboo fiber, 6 parts of polyvinylpyrrolidone and 12 parts of deionized water in parts by weight, grinding, heating, preserving heat, adding 4 parts of sodium chloride and 2.5 parts of defoaming agent, stirring, continuously heating, preserving heat, adding 4.5 parts of aluminum nitrate and 3.5 parts of hexamethylenediamine, uniformly mixing, heating in a water bath, cooling to room temperature, adding 2.5 parts of diammonium hydrogen phosphate, uniformly mixing, aging, filtering, washing, drying, calcining, and cooling to room temperature to obtain the antibacterial modification aid.
The invention provides a preparation method of novel PLA, which comprises the following steps:
s1: drying lignosulfonate, dissolving with 10mol/L NaOH solution, heating in water bath, stirring, heating to 76 deg.C, adding epichlorohydrin, mixing, and heating to 73 deg.CRefluxing and stirring at constant temperature for 5.2h, washing until pH is 7, and vacuum drying at 106 deg.C to obtain material
；
S2: pentaerythritol, suberic acid and polycarbonate are evenly mixed, and polycondensation reaction is carried out for 2.9 hours at the temperature of 116 ℃ in the nitrogen environment to obtain the material
；
S3, feeding the materials
Adding polylactic acid, linear low density polyethylene and polyvinyl alcohol, mixing uniformly, cooling, washing to neutrality, and finally performing solid-liquid separation to obtain the material
；
S4, mixing the materials
Mixing with diphenylmethane diisocyanate, calcium carbonate, bamboo fiber, potato starch, montmorillonite, konjac glucomannan, liquid paraffin, silane coupling agent KH-570, ethyl ethylene acrylate, glycerol, and fatty acyl diethanolamine to obtain material
；
S5, mixing the materials
Modified antimicrobial agents and materials
Mixing uniformly to obtain the novel PLA.
Example 2
The novel PLA comprises the following raw materials in parts by weight: 80 parts of polylactic acid, 24 parts of lignosulfonate, 4 parts of epoxy chloropropane, 10 parts of modified antibacterial agent, 8 parts of linear low-density polyethylene, 25 parts of polyvinyl alcohol, 4 parts of polycarbonate, 8 parts of pentaerythritol, 3 parts of suberic acid, 5 parts of diphenylmethane diisocyanate, 4 parts of dioctyl phthalate, KH-5703 parts of silane coupling agent, 9 parts of bamboo fiber, 8 parts of potato starch, 2 parts of montmorillonite, 5 parts of konjac glucomannan, 4 parts of calcium carbonate, 5 parts of liquid paraffin, 4 parts of ethylene ethyl acrylate, 9 parts of glycerol and 3 parts of fatty acyl diethanol amine.
The modified antibacterial agent is prepared by the following process: uniformly mixing 10 parts of chitin fiber, 8 parts of bamboo fiber, 3 parts of polyvinylpyrrolidone and 16 parts of deionized water in parts by weight, grinding, heating, preserving heat, adding 2 parts of sodium chloride and 4 parts of defoaming agent, stirring, continuously heating, preserving heat, adding 3 parts of aluminum nitrate and 5 parts of hexamethylenediamine, uniformly mixing, heating in a water bath, cooling to room temperature, adding 1 part of diammonium hydrogen phosphate, uniformly mixing, aging, filtering, washing, drying, calcining, and cooling to room temperature to obtain the antibacterial modification aid.
The invention provides a preparation method of novel PLA, which comprises the following steps:
s1: drying lignosulfonate, dissolving with 10mol/L NaOH solution, heating in water bath, stirring, heating to 70 deg.C, adding epichlorohydrin, mixing, refluxing at 75 deg.C for 4 hr, washing to pH 7, and vacuum drying at 110 deg.C to obtain the final product
；
S2: pentaerythritol, suberic acid and polycarbonate are evenly mixed, and polycondensation reaction is carried out for 4 hours at the temperature of 150 ℃ in the nitrogen environment to obtain the material
；
S3, feeding the materials
Adding polylactic acid and linear low-density polyethyleneMixing alkene and polyvinyl alcohol uniformly, cooling, washing to be neutral, and finally carrying out solid-liquid separation to obtain a material
；
S4, mixing the materials
Mixing with diphenylmethane diisocyanate, calcium carbonate, bamboo fiber, potato starch, montmorillonite, konjac glucomannan, liquid paraffin, silane coupling agent KH-570, ethyl ethylene acrylate, glycerol, and fatty acyl diethanolamine to obtain material
；
S5, mixing the materials
Modified antimicrobial agents and materials
Mixing uniformly to obtain the novel PLA.
Example 3
The novel PLA comprises the following raw materials in parts by weight: 120 parts of polylactic acid, 12 parts of lignosulfonate, 9 parts of epoxy chloropropane, 5 parts of modified antibacterial agent, 14 parts of linear low-density polyethylene, 15 parts of polyvinyl alcohol, 8 parts of polycarbonate, 4 parts of pentaerythritol, 6 parts of suberic acid, 2 parts of diphenylmethane diisocyanate, 9 parts of dioctyl phthalate, KH-5701 parts of silane coupling agent, 16 parts of bamboo fiber, 4 parts of potato starch, 6 parts of montmorillonite, 1 part of konjac glucomannan, 7 parts of calcium carbonate, 2 parts of liquid paraffin, 8 parts of ethylene ethyl acrylate, 3 parts of glycerol and 9 parts of fatty acyl diethanol amine.
The modified antibacterial agent is prepared by the following process: uniformly mixing 20 parts of chitin fiber, 4 parts of bamboo fiber, 9 parts of polyvinylpyrrolidone and 8 parts of deionized water in parts by weight, grinding, heating, preserving heat, adding 6 parts of sodium chloride and 1 part of defoamer, stirring, continuously heating, preserving heat, adding 6 parts of aluminum nitrate and 2 parts of hexamethylenediamine, uniformly mixing, heating in a water bath, cooling to room temperature, adding 4 parts of diammonium hydrogen phosphate, uniformly mixing, aging, filtering, washing, drying, calcining, and cooling to room temperature to obtain the antibacterial modification aid.
The invention provides a preparation method of novel PLA, which comprises the following steps:
s1: drying lignosulfonate, dissolving with 10mol/L NaOH solution, heating in water bath, stirring, heating to 80 deg.C, adding epichlorohydrin, mixing, refluxing at 70 deg.C for 6 hr, washing to pH 7, and vacuum drying at 100 deg.C to obtain the final product
；
S2: pentaerythritol, suberic acid and polycarbonate are evenly mixed, and polycondensation reaction is carried out for 2 hours at the temperature of 180 ℃ in the nitrogen environment to obtain the material
；
S3, feeding the materials
Adding polylactic acid, linear low density polyethylene and polyvinyl alcohol, mixing uniformly, cooling, washing to neutrality, and finally performing solid-liquid separation to obtain the material
；
S4, mixing the materials
Mixing with diphenylmethane diisocyanate, calcium carbonate, bamboo fiber, potato starch, montmorillonite, konjac glucomannan, liquid paraffin, silane coupling agent KH-570, ethyl ethylene acrylate, glycerol, and fatty acyl diethanolamine to obtain material
；
S5, mixing the materials
Modified antimicrobial agents and materials
Mixing uniformly to obtain the novel PLA.
Comparative example 1
Essentially the same procedure as in example 1, except that the starting materials for the preparation of the novel PLA were devoid of lignosulfonate, epichlorohydrin, modified antimicrobial, linear low density polyethylene, polycarbonate, dioctyl phthalate, silane coupling agent KH-570.
Comparative example 2
Essentially the same procedure as in example 1, except that the lignosulfonate was absent from the feedstock for making the novel PLA.
Comparative example 3
Essentially the same procedure as in example 1, except that epichlorohydrin was absent from the starting material for the preparation of the novel PLA.
Comparative example 4
Essentially the same procedure as in example 1, except that the modified antimicrobial agent was absent from the raw materials used to make the novel PLA.
Comparative example 5
Essentially the same procedure as in example 1, except that the linear low density polyethylene was absent from the feedstock used to make the novel PLA.
Comparative example 6
Essentially the same procedure as in example 1 was followed, except that polycarbonate was absent from the starting material for the preparation of the novel PLA.
Comparative example 7
Essentially the same procedure as in example 1 was followed, except that the dioctyl phthalate was absent from the starting material used to prepare the novel PLA.
Comparative example 8
Essentially the same procedure as in example 1, except that the silane coupling agent KH-570 was absent from the starting material used to prepare the novel PLA.
Comparative example 9
The degradable novel PLA prepared in the patent application document 'a PLA composite material (application publication number: CN 104927323B)'.
Comparative example 10
The procedure was substantially the same as in example 1 except that the starting materials for the preparation of the novel PLA were 11 parts of lignosulfonate, 10 parts of epichlorohydrin, 4 parts of modified antibacterial agent, 15 parts of linear low-density polyethylene, 3 parts of polycarbonate, 10 parts of dioctyl phthalate and 0.8 part of silane coupling agent KH-570.
Comparative example 11
The procedure was substantially the same as in example 1 except that the starting materials for the preparation of the novel PLA were 26 parts of lignosulfonate, 3 parts of epichlorohydrin, 12 parts of modified antibacterial agent, 7 parts of linear low-density polyethylene, 9 parts of polycarbonate, 3 parts of dioctyl phthalate and 5 parts of silane coupling agent KH-570.
Comparative example 12
The procedure was substantially the same as in example 1 except that the starting materials for the preparation of the novel PLA were 26 parts of lignosulfonate, 3 parts of epichlorohydrin, 11 parts of modified antibacterial agent, 7 parts of linear low-density polyethylene, 9 parts of polycarbonate, 3 parts of dioctyl phthalate and 4 parts of silane coupling agent KH-570.
The products prepared in examples 1-3 and comparative examples 1-12 are subjected to antibacterial property and water absorption property tests, degradation tests are carried out according to the standard GB/T20197-2006, mechanical property tests are carried out according to GB/T1040.3-2006, antibacterial property tests are carried out according to the national standard GBT21510-2008, and the results are shown in the following table:
| experimental groups | Sterilizing rate/%) | Tensile strength/MPa | Elongation at break/% | Weight loss after burying in soil/120 d (%) |
| Example 1 | 99.64 | 68.4 | 796.2 | 89.6 |
| Example 2 | 98.83 | 68.1 | 794.3 | 88.4 |
| Example 3 | 98.41 | 67.9 | 786.1 | 84.3 |
| Comparative example 1 | 33.12 | 38.9 | 384.6 | 67.1 |
| Comparative example 2 | 94.23 | 61.2 | 781.6 | 83.1 |
| Comparative example 3 | 93.35 | 60.8 | 774.3 | 82.9 |
| Comparative example 4 | 94.63 | 59.1 | 771.6 | 81.2 |
| Comparative example 5 | 95.68 | 63.4 | 769.2 | 81.6 |
| Comparative example 6 | 97.4 | 58.4 | 762.4 | 82.1 |
| Comparative example 7 | 96.7 | 64.7 | 766.3 | 81.3 |
| Comparative example 8 | 96.3 | 62.8 | 769.1 | 80.7 |
| Comparative example 9 | 22.45 | 37.1 | 376 | 61.2 |
| Comparative example 10 | 46.9 | 43.5 | 396.7 | 70.3 |
| Comparative example 11 | 42.8 | 44.8 | 402.5 | 71.2 |
| Comparative example 12 | 49.6 | 43.7 | 401.1 | 69.1 |
From the above table, it can be seen that:
(1) as can be seen from the data of examples 1-3 and comparative example 9, the antibacterial properties of the novel PLA prepared in examples 1-3 are significantly higher than those of the novel PLA prepared in comparative example 9; meanwhile, as can be seen from the data of examples 1 to 3, example 1 is the most preferred example.
(2) As can be seen from the data of example 1 and comparative examples 1-8, lignosulfonate, epichlorohydrin, modified antimicrobial, linear low density polyethylene, polycarbonate, dioctyl phthalate, silane coupling agent KH-570 play a synergistic role in the preparation of the antimicrobial agent, which improves the antimicrobial properties of the novel PLA in the preparation of the novel PLA; this is: lignosulfonate, epichlorohydrin, modified antibacterial agent, linear low-density polyethylene, polycarbonate, dioctyl phthalate and silane coupling agent KH-570 are used as a reinforcing system, polycarbonate is used as porous degradable water-absorbing filler, the porous degradable water-absorbing filler has good water absorption and biocompatibility, the use safety of novel PLA is guaranteed, the surface of the polycarbonate contains a large number of hydroxyl groups, the polycarbonate is grafted to the linear low-density polyethylene under the grafting effect of the silane coupling agent KH-570, the surface of the linear low-density polyethylene contains rich unsaturated bonds, the polycarbonate can be attached to the linear low-density polyethylene, and the degradation of the linear low-density polyethylene can be accelerated due to the grafting of the polycarbonate by utilizing the biocompatibility and degradability of the polycarbonate, the application of the modified PLA in the preparation of the novel PLA further improves the degradation performance of the novel PLA. The polycarbonate generates an acidic environment after hydrolysis, the acidic environment can inhibit the activity of the respiring enzyme of bacteria so as to inhibit the growth of the bacteria, thereby killing the bacteria, and the excellent antibacterial reinforcing performance of the reinforcing system is endowed by utilizing the antibacterial sterilization performance of the polycarbonate. Wherein the added modified antibacterial agent is prepared by uniformly mixing 3, 4-dihydroxybenzaldehyde, sodium hexametaphosphate, diphenylmethane diisocyanate, 15-25% by mass of silver nitrate solution, dibutyltin dilaurate, acetic acid and methanol, standing at normal temperature, adding sodium borohydride, uniformly mixing, stirring, carrying out suction filtration to obtain a precipitate, dialyzing the precipitate in hydrochloric acid solution, and carrying out freeze drying to obtain a material a; the preparation method comprises the steps of uniformly mixing a silane coupling agent KH-560, polyethylene glycol and sodium bisulfite, adding a material a, uniformly mixing, heating, keeping the temperature, stirring, and cooling to room temperature to obtain the product, wherein the antibacterial performance of 3, 4-dihydroxybenzaldehyde, the adhesive performance of polyethylene glycol and diphenylmethane diisocyanate, and dibutyltin dilaurate are used as catalysts, the combination of 3, 4-dihydroxybenzaldehyde and sodium borohydride is realized under the grafting action of the silane coupling agent KH-560, the antibacterial performance of the novel PLA is effectively improved when the preparation method is applied to the preparation of the novel PLA, sodium groups on lignosulfonate are replaced by hydroxyl groups of sodium hydroxide, the epoxidation treatment of lignosulfonate is realized through the combination of the hydroxyl groups and epoxy groups of epoxy chloropropane, and the graft modification effect of the silane coupling agent KH-570 is realized, the stable combination of the lignosulfonate and the linear low-density polyethylene is realized, so that the mechanical strength of the linear low-density polyethylene is improved, and the epoxidized lignosulfonate is utilized to wrap unsaturated bonds on the surface of the linear low-density polyethylene, so that the density of a surface net structure of the linear low-density polyethylene is improved.
Konjac glucomannan is natural high-molecular soluble dietary fiber, and has water retention property, so that the whole novel PLA can be kept in a relatively dry state, the microstructure of the konjac glucomannan is more complex due to the high-molecular fiber structure of the konjac glucomannan, the konjac glucomannan is added into the preparation of the novel PLA, the unsaturated bond on the surface of the polylactic acid is connected with the hydroxyl on the surface of the konjac glucomannan under the grafting effect of a silane coupling agent KH-570, the graft modification of the polylactic acid by the high-molecular material is realized, and the konjac glucomannan is wrapped on the surface of the polylactic acid to realize a compact high-molecular fiber film layer and is applied to the preparation of the novel PLA, so that the novel PLA is more flexible and is not easy to break, the degradability of the konjac glucomannan is high, and the white pollution can be reduced. Montmorillonite and potato starch form hydrogen bonds, and under the grafting action of silane coupling agent KH-570, the combination of the hydrogen bonds and linear low-density polyethylene is realized, the surface net density of the linear low-density polyethylene is further increased, the tensile strength of the novel PLA is enhanced, the surface grafting modification is carried out on bamboo fibers through the silane coupling agent KH-570, one end of the silane coupling agent KH-570 is a polar bond, and the other end of the silane coupling agent KH-570 is a non-polar end, the connection of the bamboo fibers and the linear low-density polyethylene is realized through grafting, and after the bamboo fibers are connected with the linear low-density polyethylene, the interface contact angle is increased, so that the surface tension is reduced, the wettability of the fiber surface is improved, the compatibility of the interface is improved, and the montmorillonite is applied to the preparation of the novel PLA, the montmorillonite is an inorganic substance with a large number of hydroxyl groups on the surface, while the potato starch and the, the inorganic matters and organic matters containing hydroxyl are grafted to the linear low-density polyethylene, the reinforcing materials are degradable and are attached to the surface of the linear low-density polyethylene after grafting, and the grafted degradable reinforcing materials further accelerate the degradation of the linear low-density polyethylene, so that the degradation performance of the novel PLA is improved.
(3) As can be seen from the data of comparative examples 10 to 12, when the weight ratio of lignosulfonate, epichlorohydrin, modified antibacterial agent, linear low density polyethylene, polycarbonate, dioctyl phthalate, silane coupling agent KH-570 was out of the range of (12-24): 4-9): 5-10): 8-14): 4-8): 4-9): 1-3, the antibacterial performance values of the novel PLA obtained were very different from those of examples 1 to 3 and were much smaller than those of examples 1 to 3. In the invention, lignosulfonate, epichlorohydrin, a modified antibacterial agent, linear low-density polyethylene, polycarbonate, dioctyl phthalate and a silane coupling agent KH-570 are added as a reinforcing system, in the preparation of the novel PLA controlled in the examples 1-3, lignosulfonate, epichlorohydrin, a modified antibacterial agent, linear low-density polyethylene, polycarbonate, dioctyl phthalate and the silane coupling agent KH-570 are added in the weight ratio of (12-24) to (4-9) to (5-10) to (8-14) to (4-8) to (4-9) to (1-3), so that lignosulfonate and linear low-density polyethylene are used as main raw materials in the reinforcing system, and the basic component of the lignosulfonate is a benzyl propane derivative and has a structure with a hydrophobic skeleton of C6-C3, a sulfonic group and other hydrophilic groups, the lignosulfonate is a polar material, the polyolefin is a non-polar material, the dioctyl phthalate is added, the bonding force between the lignosulfonate and the linear low-density polyethylene is increased, the compatibility between the lignosulfonate and the linear low-density polyethylene is improved, the epoxidation of the lignosulfonate by epoxy chloropropane is realized under the catalytic action of sodium hydroxide, a sodium group on the lignosulfonate is replaced by a hydroxyl group of the sodium hydroxide, the epoxidation of the lignosulfonate is realized by the combination of the hydroxyl group and an epoxy group of the epoxy chloropropane, and the stable combination of the lignosulfonate and the linear low-density polyethylene is realized under the grafting and changing action of a silane coupling agent KH-570, so that the mechanical strength of the linear low-density polyethylene is improved, the epoxidized lignosulfonate is utilized to wrap unsaturated bonds on the surface of linear low-density polyethylene, so that the density of a network structure on the surface of the linear low-density polyethylene is improved, the mechanical strength of the linear low-density polyethylene is further enhanced, the surfaces of the modified antibacterial agent and the polycarbonate also contain a large amount of hydroxyl groups, the modified antibacterial agent and the polycarbonate are combined with the unsaturated bonds on the surface of the linear low-density polyethylene under the grafting effect of a silane coupling agent KH-570, the antibacterial property of the linear low-density polyethylene is enhanced by utilizing the synergistic effect of the modified antibacterial agent and the antibacterial property of the polycarbonate, the beneficial mechanical strength and the antibacterial property of a reinforcing system are further endowed, and the prepared novel PLA has excellent mechanical strength and antibacterial property.
The above description should not be taken as limiting the invention to the embodiments, but rather, as will be apparent to those skilled in the art to which the invention pertains, numerous simplifications or substitutions may be made without departing from the spirit of the invention, which shall be deemed to fall within the scope of the invention as defined by the claims appended hereto.
Claims (5)
1. A novel PLA is characterized by comprising the following raw materials: polylactic acid, lignosulfonate, epichlorohydrin, modified antibacterial agent, linear low-density polyethylene, polyvinyl alcohol, polycarbonate, pentaerythritol, suberic acid, diphenylmethane diisocyanate, dioctyl phthalate, a silane coupling agent KH-570, bamboo fiber, potato starch, montmorillonite, konjac glucomannan, calcium carbonate, liquid paraffin, ethylene ethyl acrylate, glycerol and fatty acyl diethanolamine;
the weight ratio of the lignosulfonate to the epichlorohydrin, the modified antibacterial agent to the linear low-density polyethylene to the polycarbonate to the dioctyl phthalate to the silane coupling agent KH-570 is (12-24) to (4-9) to (5-10) to (8-14) to (4-8) to (4-9) to (1-3);
the modified antibacterial agent comprises the following raw materials in parts by weight: 10-20 parts of chitin fiber, 4-8 parts of bamboo fiber, 3-9 parts of polyvinylpyrrolidone, 8-16 parts of deionized water, 2-6 parts of sodium chloride, 1-4 parts of defoaming agent, 3-6 parts of aluminum nitrate, 2-5 parts of hexamethylene diamine and 1-4 parts of diammonium hydrogen phosphate.
2. The novel PLA according to claim 1, wherein the weight ratio of the lignosulfonate, the epichlorohydrin, the modified antibacterial agent, the linear low density polyethylene, the polycarbonate, the dioctyl phthalate, the silane coupling agent KH-570 is 17.8: 6.8: 7.3: 11.3: 5.9:6.2: 2.2.
3. The novel PLA according to claim 1, which comprises the following raw materials in parts by weight: 80-120 parts of polylactic acid, 12-24 parts of lignosulfonate, 4-9 parts of epichlorohydrin, 5-10 parts of modified antibacterial agent, 8-14 parts of linear low-density polyethylene, 15-25 parts of polyvinyl alcohol, 4-8 parts of polycarbonate, 4-8 parts of pentaerythritol, 3-6 parts of suberic acid, 2-5 parts of diphenylmethane diisocyanate, 4-9 parts of dioctyl phthalate, 4-3 parts of silane coupling agent KH-5701, 9-16 parts of bamboo fiber, 4-8 parts of potato starch, 2-6 parts of montmorillonite, 1-5 parts of konjac glucomannan, 4-7 parts of calcium carbonate, 2-5 parts of liquid paraffin, 4-8 parts of ethylene acrylic acid ethyl ester, 3-9 parts of glycerol and 3-9 parts of fatty acyl diethanolamine.
4. The novel PLA of claim 1, wherein the modified antimicrobial agent is prepared by a process comprising: uniformly mixing chitin fiber, bamboo fiber, polyvinylpyrrolidone and deionized water, grinding, heating, preserving heat, adding sodium chloride and a defoaming agent, stirring, continuously heating, preserving heat, adding aluminum nitrate and hexamethylenediamine, uniformly mixing, heating in a water bath, cooling to room temperature, adding diammonium hydrogen phosphate, uniformly mixing, aging, filtering, washing, drying, calcining, and cooling to room temperature to obtain the antibacterial modification auxiliary agent.
5. A process for the preparation of a novel PLA according to any of the claims 1-4, characterized in that it comprises the following steps:
s1: drying lignosulfonate, dissolving with 10mol/L NaOH solution, heating in water bath, stirring, heating to 70-80 deg.C, adding epichlorohydrin, mixing, refluxing and stirring at 70-75 deg.C for 4-6 hr, washing to pH 7, vacuum drying at 100-110 deg.C to obtain the final product
；
S2: pentaerythritol, suberic acid and polycarbonate are evenly mixed, and polycondensation reaction is carried out for 2 to 4 hours at the temperature of 180 ℃ under the nitrogen environment to obtain the material
；
S3, feeding the materials
Adding polylactic acid, linear low density polyethylene and polyvinyl alcohol, mixing uniformly, cooling, washing to neutrality, and finally performing solid-liquid separation to obtain the material
；
S4, mixing the materials
Mixing with diphenylmethane diisocyanate, calcium carbonate, bamboo fiber, potato starch, montmorillonite, konjac glucomannan, liquid paraffin, silane coupling agent KH-570, ethyl ethylene acrylate, glycerol, and fatty acyl diethanolamine to obtain material
；
S5, mixing the materials
Modified antimicrobial agents and materials
Mixing uniformly to obtain the novel PLA.
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| CN111748185A (en) * | 2020-07-21 | 2020-10-09 | 苏州环诺新材料科技有限公司 | Antibacterial plant fiber toughened PLA composite material and preparation method thereof |
| CN112877880A (en) * | 2021-01-11 | 2021-06-01 | 浙江大能纺织印染有限公司 | Preparation method of fragrant antibacterial collagen fiber cotton blended dyed knitted fabric |
| CN113068883A (en) * | 2021-04-02 | 2021-07-06 | 陕西科技大学 | Antibacterial mask chip and preparation method thereof |
| CN113583369A (en) * | 2021-08-20 | 2021-11-02 | 三峡大学 | Composite membrane compositions containing novel modifiers |
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| CN109385915A (en) * | 2018-10-26 | 2019-02-26 | 长沙浩然医疗科技有限公司 | A kind of antibacterial underwear material and preparation method thereof |
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| CN111748185A (en) * | 2020-07-21 | 2020-10-09 | 苏州环诺新材料科技有限公司 | Antibacterial plant fiber toughened PLA composite material and preparation method thereof |
| CN112877880A (en) * | 2021-01-11 | 2021-06-01 | 浙江大能纺织印染有限公司 | Preparation method of fragrant antibacterial collagen fiber cotton blended dyed knitted fabric |
| CN113068883A (en) * | 2021-04-02 | 2021-07-06 | 陕西科技大学 | Antibacterial mask chip and preparation method thereof |
| CN113068883B (en) * | 2021-04-02 | 2024-02-13 | 陕西科技大学 | Antibacterial mask chip and preparation method |
| CN113583369A (en) * | 2021-08-20 | 2021-11-02 | 三峡大学 | Composite membrane compositions containing novel modifiers |
| CN114262989A (en) * | 2021-12-28 | 2022-04-01 | 江苏德邦卫生用品有限公司 | Preparation method of degradable environment-friendly non-woven fabric |
| CN116874912A (en) * | 2023-07-29 | 2023-10-13 | 深圳市品创源实业有限公司 | Degradable film and preparation method thereof |
| CN116874912B (en) * | 2023-07-29 | 2024-05-28 | 深圳市品创源实业有限公司 | Degradable film and preparation method thereof |
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