CN109517352B - Flame-retardant P L A-based degradable food packaging material and preparation method thereof - Google Patents

Flame-retardant P L A-based degradable food packaging material and preparation method thereof Download PDF

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CN109517352B
CN109517352B CN201811450655.3A CN201811450655A CN109517352B CN 109517352 B CN109517352 B CN 109517352B CN 201811450655 A CN201811450655 A CN 201811450655A CN 109517352 B CN109517352 B CN 109517352B
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邓琪
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Vanjoin Wuhan New Material Co ltd
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
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    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
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    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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    • C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
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    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
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    • Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
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Abstract

The invention discloses a flame-retardant P L A-based degradable food packaging material and a preparation method thereof, wherein the flame-retardant P L A-based degradable food packaging material comprises the following components, by weight, 45-65 parts of polylactic acid, 25-35 parts of sepiolite fiber, and polyvinyl alcohol (PVA)/silicon dioxide (SiO)2) 10-25 parts of composite rubber material, 0.5-1.5 parts of plasticizer and 0.8-2 parts of dispersant. The food packaging material prepared by the invention is green and environment-friendly, can be biologically degraded, and adopts sepiolite fiber and PVA/SiO2The composite sizing material synergistically modifies the polylactic acid, so that the mechanical property of the composite material is improved, and the prepared food packaging material is high in heat insulation and flame retardance.

Description

Flame-retardant P L A-based degradable food packaging material and preparation method thereof
Technical Field
The invention relates to the technical field of plastic product production, in particular to a flame-retardant P L A-based degradable food packaging material and a preparation method thereof.
Background
Polylactic acid is a novel environment-friendly biodegradable material developed in recent years, the raw material of the polylactic acid is a renewable natural resource, and the polylactic acid has low energy consumption, good environment friendliness, biocompatibility, mechanical property and processability, is an ideal petroleum substitute product, has wide application prospect, and has been widely applied in industries such as biology, medicine, textile, packaging, electronic and electrical appliances, automobile manufacturing and the like.
Sepiolite is a fibrous hydrous magnesium-rich silicate clay mineral, mainly contains silicon and magnesium, and has a theoretical structural formula of Mg8Si12O30(OH)4(H2O)4·8H2And O. The crystal structure of sepiolite has the transitional characteristics of layers and chains: the upper and lower silicon-oxygen tetrahedrons sandwich a layer of magnesium-oxygen octahedron, the two layers of magnesium-oxygen octahedrons are alternately arranged to form a 2: 1 layered structure unit, and pore channels parallel to bonds are arranged between the two layers of silicon-oxygen tetrahedrons. Gas phase ignition typically occurs in the combustible air mixture adjacent to the condensed phase, and the rate of oxygen entering the condensed phase may affect the rate of polymer cracking. The oxygen isolation effect of the sepiolite with blanket effect is very effective for inhibiting the thermal cracking and burning of the polymer, and the mechanical property, the flame retardance and the like of the composite material are improved after the sepiolite is compounded with the polylactic acid.
Chinese patent CN 107868993A discloses a flame-retardant polylactic acid fiber fabric and a preparation method thereof, which comprises the following steps: preheating sepiolite, sequentially adding titanate, azodicarbonamide and epoxidized soybean oil under stirring, adding oxidized polyethylene wax, continuously stirring, adjusting the pH value of the system to 7.5-7.9 by using sodium hydroxide, and feeding the system into an extruder for extrusion to obtain a prefabricated material; mixing polylactic acid, the prefabricated material, zeolite powder, medical stone powder, mica powder, berberine and butter, feeding the mixture into a melt spinning machine, spinning through circular spinneret orifices, and spinning to obtain the flame-retardant polylactic acid fiber fabric. The flame-retardant polylactic acid fiber fabric prepared by the invention has good flame retardant property, good tensile strength and toughness, good humidity resistance and wide application prospect, and can be widely applied to fiber fabric fabrics. However, the process method is complex in preparation, needs more raw materials, is high in cost and is not beneficial to large-scale industrial production.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a flame-retardant P L A-based degradable food packaging material and a preparation method thereof, wherein the processed sepiolite fiber and PVA/SiO are adopted2The composite sizing material synergistically modifies the polylactic acid, not only improves the mechanical property of the composite material, but also is preparedThe obtained food packaging material has strong heat insulation and flame retardance. The composite material prepared by the method has higher economic benefit and social value.
The flame-retardant P L A-based degradable food packaging material comprises the following raw materials in parts by weight:
45-65 parts of polylactic acid, 5-15 parts of sepiolite fiber and PVA/SiO210-25 parts of composite rubber material, 0.5-1.5 parts of plasticizer and 0.25-0.5 part of dispersant.
The sepiolite fiber is prepared by ball milling, and the particle size of the sepiolite fiber is 5-30 μm.
The sepiolite fiber with the particle size of 5-30 mu m is selected, so that the smoothness and the attractiveness of the surface of a food packaging material formed by the sepiolite fiber and polylactic acid are ensured, the surface contact area of the sepiolite fiber with small particle size and other substances is increased, the interfacial reaction activity with other substances is increased, and the reaction rate is improved.
The sepiolite fiber is prepared by acid activation and phenyl triethoxysilane surface modification.
The natural sepiolite ore has high impurity content and narrow pore passage, so that the specific surface area is low, when the natural sepiolite ore is applied to a composite material, the natural sepiolite ore needs to be purified, modified and the like, the sepiolite fiber is purified by hydrochloric acid, the magnesium is mainly removed, and impurities such as sodium ions, potassium ions, calcium ions and the like can be removed. The activation mechanism of the sepiolite is as follows: h+By substitution of Mg in the skeleton2+So that the-Si-O-Mg-O-Si-bond is converted into two-Si-O-H-bonds, and the internal channel of the sepiolite is opened, thereby increasing the specific surface area and the micropore volume. Meanwhile, the phenyltriethoxysilane is adopted for surface modification, so that the hydrophilicity is maintained under the condition of not changing the crystal structure of the phenyltriethoxysilane, and the compatibility and the dispersibility with the subsequent composite sizing material are improved.
The preparation method of the flame-retardant P L A-based degradable food packaging material comprises the following preparation steps of PVA/SiO2The preparation steps of the composite sizing material are as follows: taking 1-5 parts of Na2SiO3Dissolving in 50 parts of deionized water, stirring until completely dissolving to obtain Na2SiO3Adding the aqueous solution at 60 deg.C slowly to a concentration of 5-25%40-80 parts of PVA aqueous solution, stirring while dripping, continuing stirring for 1h after dripping is finished, and adjusting the pH value of the solution to be neutral to obtain PVA/SiO2And (3) compounding the rubber material.
PVA has the characteristics of biocompatibility, mechanical property, biodegradability and the like due to the characteristic of strong hydrogen bonds of polyhydroxy group, but has poor flame retardant property, the application of PVA is seriously influenced, and PVA and SiO are mixed2Compounded to form a composite sizing material, realizes the performance complementation and optimization, and is applied to PVA/SiO2In the composite sizing material, SiO2The network takes PVA as branch and is in semi-network interpenetrating state, and SiO is generated when combustion occurs2Will peel off from the rubber to form small white spherical particles, and the inside of the composite rubber material forms a spherical aggregate structure. The compact structure can effectively prevent flame from spreading, oxygen from spreading and internal combustible gas from overflowing.
When the composite sizing material is adsorbed on the surface of the sepiolite fiber, PVA is attached to the surface of the fiber through hydrogen bonds, and the main component of the fiber is SiO2When the fibers are blended with a composite sizing material, SiO2The oxygen atoms with negative charges can absorb hydrogen atoms with positive charges in water molecules to generate Si-OH, and the Si-OH in the composite sizing material reacts with the Si-OH in the fibers to form Si-OH-Si so that the composite sizing material is attached to the surfaces of the fibers.
The plasticizer is one of epoxidized soybean oil, triethyl citrate, glycerol and polyethylene glycol.
Although the plasticizer is added in a small amount in the invention, the secondary valence bonds among polymer molecules are weakened, so that the mobility of polymer molecular chains is increased, the plasticity of the polymer is increased, the brittleness of the polymer is reduced, and the elongation, the flexibility and the flexibility are improved.
The dispersing agent is one or more of barium stearate, zinc stearate, calcium stearate, cadmium stearate, magnesium stearate and copper stearate.
The selected dispersant can regulate the mobility of each particle in the whole composite system, improve the dispersibility of the particles and prevent the particles from agglomerating.
The preparation method of the flame-retardant P L A-based degradable food packaging material comprises the following steps:
(1) the sepiolite fiber is modified by firstly using acid and then adding silane coupling agent for modification.
Specifically, weighing the ball-milled sepiolite fibers according to the parts by weight, adding the sepiolite fibers into a hydrochloric acid solution with the concentration of 10%, heating and stirring the mixture at 80 ℃ for 2 hours, sequentially washing the mixture by using absolute ethyl alcohol and deionized water until the mixture is neutral, and drying the mixture for later use. Adding 100 parts of isopropanol into the sepiolite fibers, stirring for 10min, ultrasonically dispersing for 30min, adding 0.5-1.5 parts of phenyltriethoxysilane, stirring for 2h at 80 ℃, sequentially washing with absolute ethyl alcohol and deionized water, and drying for later use.
(2) Weighing PVA/SiO in parts by weight2And (3) adding the sepiolite fibers treated in the step (1) into the composite sizing material, stirring for 3 hours, placing in a vacuum drying oven at 85 ℃ for drying for 12 hours, and taking out for later use.
The invention firstly adopts PVA/SiO2The composite sizing material is blended with the sepiolite to ensure that the PVA/SiO2The composite sizing material is adhered to the sepiolite fibers, is dried and then is added into a polylactic acid system, so that the components can be uniformly dispersed, and the mechanical property of the packaging material is improved.
(3) And (3) preparing a packaging material, namely mixing the product obtained in the step (2) with polylactic acid, a plasticizer and a dispersing agent according to a certain proportion to prepare the packaging material.
Specifically, the polylactic acid, the plasticizer and the dispersing agent are weighed according to the parts by weight, the composite material obtained in the step (2) is added into a high-speed mixer, a double-screw extruder is adopted after uniform mixing, melting, bar stretching, cooling and grain cutting are carried out, the prepared granules are added into a tabletting machine to be pressed into a film, and the flame-retardant P L A-based degradable food packaging material is obtained.
The flame-retardant P L A-based degradable food packaging material prepared by adopting the technical scheme has the following advantages:
1. the invention adopts the processed sepiolite fiber and PVA/SiO2The composite sizing material synergistically modifies the polylactic acid, so that the polymer can promote a carbon layer on the surface of the material during combustionThe formation and stabilization of the polymer are reduced, the release of heat during combustion is reduced, and the heat fed back to the surface of the polymer is reduced, so that the thermal cracking of the matrix is inhibited, and the flame retardance of the composite material is improved.
2. The invention adds polylactic acid and polyvinyl alcohol biodegradable materials into the raw materials, has simple production process, does not generate three wastes, meets the requirement of environmental protection and has larger economic benefit and social value.
Detailed Description
The following examples are further illustrative of the present invention.
Example 1
The preparation method of the flame-retardant P L A-based degradable food packaging material comprises the following steps:
(1) taking 10 parts of ball-milled sepiolite fibers, adding the ball-milled sepiolite fibers into a hydrochloric acid solution with the concentration of 10%, heating and stirring the mixture at 80 ℃ for 2 hours, sequentially washing the mixture by using absolute ethyl alcohol and deionized water until the mixture is neutral, and drying the mixture for later use. Adding 100 parts of isopropanol into the sepiolite fibers, stirring for 10min, ultrasonically dispersing for 30min, adding 0.5-1.5 parts of phenyltriethoxysilane, stirring for 2h at 80 ℃, sequentially washing with absolute ethyl alcohol and deionized water, and drying for later use.
(2) Taking 10 parts of PVA/SiO2And (3) adding the sepiolite fibers treated in the step (1) into the composite sizing material, stirring for 3 hours, placing in a vacuum drying oven at 85 ℃ for drying for 12 hours, and taking out for later use.
(3) And (3) adding 45 parts of polylactic acid, 0.5 part of epoxidized soybean oil, 0.25 part of barium stearate and zinc stearate into the composite material obtained in the step (2), adding the composite material into a high-speed mixer, uniformly mixing, melting, extruding and bracing, cooling and granulating by using a double-screw extruder, adding the prepared granules into a tabletting machine, and pressing into a film to obtain the flame-retardant P L A-based degradable food packaging material.
Example 2
The preparation method of the flame-retardant P L A-based degradable food packaging material comprises the following steps:
(1) adding 15 parts of ball-milled sepiolite fibers into a 10% hydrochloric acid solution, heating and stirring at 80 ℃ for 2 hours, sequentially washing with absolute ethyl alcohol and deionized water until the mixture is neutral, and drying for later use. Adding 100 parts of isopropanol into the sepiolite fibers, stirring for 10min, ultrasonically dispersing for 30min, adding 0.5-1.5 parts of phenyltriethoxysilane, stirring for 2h at 80 ℃, sequentially washing with absolute ethyl alcohol and deionized water, and drying for later use.
(2) Taking 15 parts of PVA/SiO2And (3) adding the sepiolite fibers treated in the step (1) into the composite sizing material, stirring for 3 hours, placing in a vacuum drying oven at 85 ℃ for drying for 12 hours, and taking out for later use.
(3) And (3) adding 50 parts of polylactic acid, 0.7 part of epoxidized soybean oil, 0.3 part of barium stearate and zinc stearate into the composite material obtained in the step (2), adding into a high-speed mixer, uniformly mixing, melting, extruding into strips, cooling and granulating by using a double-screw extruder, adding the prepared granules into a tabletting machine, and pressing into a film to obtain the flame-retardant P L A-based degradable food packaging material.
Example 3
The preparation method of the flame-retardant P L A-based degradable food packaging material comprises the following steps:
(1) adding 15 parts of ball-milled sepiolite fibers into a 10% hydrochloric acid solution, heating and stirring at 80 ℃ for 2 hours, sequentially washing with absolute ethyl alcohol and deionized water until the mixture is neutral, and drying for later use. Adding 100 parts of isopropanol into the sepiolite fibers, stirring for 10min, ultrasonically dispersing for 30min, adding 0.5-1.5 parts of phenyltriethoxysilane, stirring for 2h at 80 ℃, sequentially washing with absolute ethyl alcohol and deionized water, and drying for later use.
(2) Taking 20 parts of PVA/SiO2And (3) adding the sepiolite fibers treated in the step (1) into the composite sizing material, stirring for 3 hours, placing in a vacuum drying oven at 85 ℃ for drying for 12 hours, and taking out for later use.
(3) And (3) adding 55 parts of polylactic acid, 0.8 part of epoxidized soybean oil, 0.35 part of barium stearate and zinc stearate into the composite material obtained in the step (2), adding into a high-speed mixer, uniformly mixing, melting, extruding into strips, cooling and granulating by using a double-screw extruder, adding the prepared granules into a tabletting machine, and pressing into a film to obtain the flame-retardant P L A-based degradable food packaging material.
Example 4
The preparation method of the flame-retardant P L A-based degradable food packaging material comprises the following steps:
(1) adding 15 parts of ball-milled sepiolite fibers into a 10% hydrochloric acid solution, heating and stirring at 80 ℃ for 2 hours, sequentially washing with absolute ethyl alcohol and deionized water until the mixture is neutral, and drying for later use. Adding 100 parts of isopropanol into the sepiolite fibers, stirring for 10min, ultrasonically dispersing for 30min, adding 0.5-1.5 parts of phenyltriethoxysilane, stirring for 2h at 80 ℃, sequentially washing with absolute ethyl alcohol and deionized water, and drying for later use.
(2) 25 portions of PVA/SiO are taken2And (3) adding the sepiolite fibers treated in the step (1) into the composite sizing material, stirring for 3 hours, placing in a vacuum drying oven at 85 ℃ for drying for 12 hours, and taking out for later use.
(3) And (3) adding 60 parts of polylactic acid, 0.9 part of epoxidized soybean oil, 0.4 part of barium stearate and zinc stearate into the composite material obtained in the step (2), adding into a high-speed mixer, uniformly mixing, melting, extruding into strips, cooling and granulating by using a double-screw extruder, adding the prepared granules into a tabletting machine, and pressing into a film to obtain the flame-retardant P L A-based degradable food packaging material.
Comparative example 1
The preparation method of the flame-retardant P L A-based degradable food packaging material comprises the following steps:
(1) taking 20 parts of PVA/SiO2And (3) drying the composite rubber material in a vacuum drying oven at 85 ℃ for 12h, and taking out for later use.
(2) And (3) adding 55 parts of polylactic acid, 0.8 part of epoxidized soybean oil, 0.35 part of barium stearate and zinc stearate into the composite material obtained in the step (2), adding into a high-speed mixer, uniformly mixing, melting, extruding into strips, cooling and granulating by using a double-screw extruder, adding the prepared granules into a tabletting machine, and pressing into a film to obtain the flame-retardant P L A-based degradable food packaging material.
Comparative example 2
The preparation method of the flame-retardant P L A-based degradable food packaging material comprises the following steps:
(1) adding 15 parts of ball-milled sepiolite fibers into a 10% hydrochloric acid solution, heating and stirring at 80 ℃ for 2 hours, sequentially washing with absolute ethyl alcohol and deionized water until the mixture is neutral, and drying for later use. Adding 100 parts of isopropanol into the sepiolite fibers, stirring for 10min, ultrasonically dispersing for 30min, adding 0.5-1.5 parts of phenyltriethoxysilane, stirring for 2h at 80 ℃, sequentially washing with absolute ethyl alcohol and deionized water, and drying for later use.
(2) And (2) taking 55 parts of polylactic acid, 0.8 part of epoxidized soybean oil, 0.35 part of barium stearate and zinc stearate, adding the processed sepiolite fibers obtained in the step (1), adding the sepiolite fibers into a high-speed mixer, uniformly mixing, melting, extruding into strips, cooling and granulating by using a double-screw extruder, adding the prepared granules into a tabletting machine, and pressing into a film to obtain the flame-retardant P L A-based degradable food packaging material.
Comparative example 3
The preparation method of the flame-retardant P L A-based degradable food packaging material comprises the following steps:
adding 55 parts of polylactic acid, 0.8 part of epoxidized soybean oil, 0.35 part of barium stearate and zinc stearate into a high-speed mixer, uniformly mixing, melting, extruding into strips, cooling and granulating by using a double-screw extruder, adding the prepared granules into a tabletting machine, and pressing into a film to obtain the flame-retardant P L A-based degradable food packaging material.
The tensile strength, elongation at break, impact strength and material limiting oxygen index were determined according to GB/T1040-1992, GB/T1040.1-2006, GB/T1043-1993 and GB/T2406-1993, and the results are shown in Table 1:
TABLE 1
Figure BDA0001886630570000061
As shown in Table 1, the flame-retardant P L A-based degradable food packaging materials prepared in examples 1-4 have good mechanical properties and limited oxygen index, and the highest oxygen indexThe limit oxygen index can reach 31 percent, and the flame retardance is strong. While comparative examples 1-3 show that sepiolite fibers or PVA/SiO are not added2When the rubber material is compounded, all the properties of the composite material are reduced, and when the rubber material and the rubber material are not added, the mechanical property and the flame retardance of the composite material are the worst, which indicates that the sepiolite fiber or PVA/SiO2The addition of the composite sizing material improves the mechanical property and the flame resistance of the polylactic acid composite material.
All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Claims (7)

1. The flame-retardant P L A-based degradable food packaging material is characterized by comprising the following raw materials, by weight, 45-65 parts of polylactic acid, 5-15 parts of sepiolite fiber and PVA/SiO210-25 parts of composite rubber material, 0.5-1.5 parts of plasticizer and 0.25-0.5 part of dispersant; the PVA/SiO2The preparation steps of the composite sizing material are as follows: taking 1-5 parts of Na2SiO3Dissolving in 50 parts of deionized water, stirring until completely dissolving to obtain Na2SiO3Slowly adding the aqueous solution into 5-25% PVA aqueous solution while stirring, continuously stirring after the dropwise addition is finished, and adjusting the pH value of the solution to be neutral to obtain PVA/SiO2And (3) compounding the rubber material.
2. The flame-retardant P L A-based degradable food packaging material according to claim 1, wherein the sepiolite fibers are ball-milled sepiolite fibers, and the particle size of the sepiolite fibers is 5-30 μm.
3. The flame-retardant P L A-based degradable food packaging material of claim 1, wherein the sepiolite fiber is acid-activated and surface-modified with phenyltriethoxysilane.
4. The flame-retardant P L A-based degradable food packaging material of claim 1, wherein the plasticizer is one of epoxidized soybean oil, triethyl citrate, glycerol and polyethylene glycol.
5. The flame-retardant P L A-based degradable food packaging material of claim 1, wherein the dispersant is one or more of barium stearate, zinc stearate, calcium stearate, cadmium stearate, magnesium stearate and copper stearate.
6. The preparation method of the flame retardant P L A-based degradable food packaging material according to any one of claims 1-5, wherein the preparation method comprises the steps of (1) sepiolite fiber modification treatment, first acid treatment and then silane coupling agent addition modification;
(2) weighing PVA/SiO in parts by weight2Adding the sepiolite fibers treated in the step (1) into the composite sizing material, stirring for 3 hours, placing the mixture in a vacuum drying oven at 85 ℃ for drying for 12 hours, and taking out the mixture for later use;
(3) and (3) preparing a packaging material, namely mixing the product obtained in the step (2) with polylactic acid, a plasticizer and a dispersing agent according to a certain proportion to prepare the packaging material.
7. The preparation method of the flame-retardant P L A-based degradable food packaging material according to claim 6, wherein the method in step (1) comprises the steps of weighing ball-milled sepiolite fibers in parts by weight, adding the ball-milled sepiolite fibers into a hydrochloric acid solution with a concentration of 10%, heating and stirring at 80 ℃ for 2 hours, sequentially washing with absolute ethyl alcohol and deionized water until the sepiolite fibers are neutral, drying for later use, adding 100 parts of isopropanol, stirring for 10 minutes into the sepiolite fibers, ultrasonically dispersing for 30 minutes, adding 0.5-1.5 parts of phenyltriethoxysilane, stirring at 80 ℃ for 2 hours, sequentially washing with absolute ethyl alcohol and deionized water, and drying for later use.
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