CN109517352A - A kind of flame retardant type PLA base degradable food packaging material and preparation method thereof - Google Patents

A kind of flame retardant type PLA base degradable food packaging material and preparation method thereof Download PDF

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CN109517352A
CN109517352A CN201811450655.3A CN201811450655A CN109517352A CN 109517352 A CN109517352 A CN 109517352A CN 201811450655 A CN201811450655 A CN 201811450655A CN 109517352 A CN109517352 A CN 109517352A
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parts
packaging material
flame retardant
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retardant type
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CN109517352B (en
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邓琪
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Wan Zhuo (wuhan) New Material Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/46—Applications of disintegrable, dissolvable or edible materials
    • B65D65/466—Bio- or photodegradable packaging materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/10—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Abstract

The invention discloses a kind of flame retardant type PLA base degradable food packaging material and preparation method thereof, the component comprising following parts by weight: 45-65 parts of polylactic acid, 25-35 parts of sepiolite fibre, polyvinyl alcohol (PVA)/silica (SiO2) 10-25 parts of Composite rubber material, 0.5-1.5 parts of plasticizer, 0.8-2 parts of dispersing agent.The packaging material for food that the present invention is prepared is environmentally protective, biodegradable, using sepiolite fibre and PVA/SiO2Composite rubber material modified synergic polylactic acid, not only increases the mechanical performance of composite material, and the packaging material for food being prepared is heat-insulated, anti-flammability is strong.

Description

A kind of flame retardant type PLA base degradable food packaging material and preparation method thereof
Technical field
The present invention relates to plastic products production technical field more particularly to a kind of degradable food packagings of flame retardant type PLA base Material and preparation method thereof.
Background technique
Polylactic acid is a kind of novel environmental friendly Biodegradable material developed in recent years, raw material be it is renewable from Right resource, and low energy consumption and has good environment friendly, biocompatibility, mechanical performance and processing performance, is ideal Oil replacement product, there is broad prospect of application, and in biology, medicine, weaving, packaging, electronic apparatus and automobile system It the industries such as makes to be widely applied.However as other high molecular materials, polylactic acid has the shortcomings that inflammable, and limit oxygen refers to Number (LOI) is only 20, and is burnt with molten drop phenomenon, and fire hazard is larger, strongly limits its application range, it is therefore desirable to right Its progress is flame-retardant modified, to extend its application range.
Sepiolite is a kind of aqueous rich magnesium silicate clay mineral of threadiness, and main chemical compositions are silicon and magnesium, theory knot Structure formula is Mg8Si12O30(OH)4(H2O)4·8H2O.The crystal structure of sepiolite has the transition feature of stratiform and chain: on Lower two layers of oxygen-octahedron presss from both sides one layer of magnesia octahedron, and the two arrangement alternate with each other forms 2: 1 layered structure units, arranges therebetween The duct parallel with key is arranged, this structure plays the humidification of similar skeleton to polymer, to the segmentation effect of polymer Lead to the change of polymer mechanical property with discontinuous effect, meanwhile, sepiolite fibre reticular structure limits polymer molecular chain Flowing so that prevent the intensity of a fire sprawling and reduce drippage.Gas phase is ignited usually mixed in the combustible Industry air of neighbouring condensed phase It closes and occurs in object, and the speed that oxygen enters condensed phase may will affect the speed of polymer cracking.Sepiolite forms blanket The oxygen barrier effect of effect is highly effective to the thermal cracking and burning that inhibit polymer, and composite material is improved after compound with polylactic acid Mechanical property, anti-flammability etc..
Chinese patent CN 107868993A discloses a kind of flame-proof polylactic acid fabric lining and preparation method thereof, including such as Lower step: sepiolite is preheated, and titanate esters, azodicarbonamide, epoxidized soybean oil are sequentially added under stirring, and stirring adds Enter oxidized polyethylene wax, continue to stir, be 7.5-7.9 with sodium hydroxide regulation system pH value, feeding extruder squeezes out to obtain pre- System material；Polylactic acid, prefabricated material, zeolite powder, medical stone powder, mica powder, berberine, butter are mixed, are sent into melt spinning machine Through round spinneret orifice spinning, weaving obtains flame-proof polylactic acid fabric lining.The present invention prepares obtained flame-retardant polylactic acid fiber fabric Flame retardant property is good, has good tensile strength and toughness, humidity resistance is good, has a extensive future, and can be widely used in fiber In fabric.But process preparation is complicated, required raw material is more, higher cost, is unfavorable for large-scale industry metaplasia It produces.
Summary of the invention
In order to solve the deficiencies in the prior art, it is an object of that present invention to provide a kind of degradable food packets of flame retardant type PLA base Package material and preparation method thereof, using sepiolite fibre and PVA/SiO after treatment2The poly- cream of Composite rubber material modified synergic Acid, not only increases the mechanical performance of composite material, and the packaging material for food being prepared is heat-insulated, anti-flammability is strong.The party The composite material that method is prepared has high economic benefit and social value.
Flame retardant type PLA base degradable food packaging material of the invention be include following raw material composition:
45-65 parts of polylactic acid, 5-15 parts of sepiolite fibre, PVA/SiO210-25 parts of Composite rubber material, plasticizer 0.5-1.5 Part, 0.25-0.5 parts of dispersing agent.
The sepiolite fibre is the sepiolite fibre after ball milling, and the partial size of sepiolite fibre is 5-30 μm.
Selecting partial size is 5-30 μm of sepiolite fibre, is on the one hand to guarantee its packaging material for food formed with polylactic acid Surface smoothness and aesthetics, on the other hand, the sepiolite fibre of small particle and the contact surface area of other substances increase, and increase Add and other material interface reactivities, raising reactivity.
The sepiolite fibre is the modified sepiolite fibre of acid activation and phenyl triethoxysilane surface.
Natural sepiolite mine impurity content is high, and aretation causes specific surface area lower, when being applied to composite material, palpus First pass through purification and modification etc. processing, using hydrochloric acid to sepiolite fibre carry out purification processes, main de-magging, also can remove sodium, The impurity such as potassium, calcium ion.Its activating mechanism to sepiolite are as follows: H+Replace the Mg in skeleton2+, turn-Si-O-Mg-O-Si- key Two-Si-O-H- keys are turned to, sepiolite inner passage is opened, and increases specific surface area and Micropore volume volume.Meanwhile it using Phenyl triethoxysilane is surface modified modification, in the case where not changing its crystal structure, remains hydrophily, improves Compatibility, dispersibility with subsequent Composite rubber material.
Preparing the flame retardant type PLA base degradable food packaging material includes following preparation step: PVA/SiO2Compound adhesive Expect preparation step are as follows: take 1-5 parts of Na2SiO3It is dissolved in 50 parts of deionized water, stirring is until be completely dissolved to obtain Na2SiO3 It is slowly added in the PVA aqueous solution that concentration is 5-25%40-80 parts at 60 DEG C, stirs when being added dropwise, is added dropwise by aqueous solution After the completion, continue to stir 1h, adjusting solution ph is neutral to get arriving PVA/SiO2Composite rubber material.
PVA makes it have biocompatibility, mechanical property and biodegradable due to the characteristics of its polyhydroxy strong hydrogen bonding The features such as property, but its poor flame retardant properties, its application is seriously affected, by PVA and SiO2It is compounded to form Composite rubber material, realizes performance Complementary and optimization, in PVA/SiO2In Composite rubber material, SiO2Network is in half network interpenetrating state using PVA as branch, when burning, SiO2It can therefrom be stripped out, form the spherical little particle of white, the structure of spheroidal aggravation is formed inside Composite rubber material. This close structure can effectively prevent the spilling of the sprawling of flame, the propagation of oxygen and internal fuel gas.
When Composite rubber material is adsorbed on sepiolite fibre surface, PVA is attached to fiber surface by hydrogen bond, fiber it is main Ingredient is SiO2, when fiber is blended with Composite rubber material, SiO2In electronegative oxygen atom can be positively charged in adsorbed water molecule hydrogen it is former Son and there is Si-OH, the Si-OH in Composite rubber material reacts with the Si-OH in fiber, formed Si-OH-Si so that compound Sizing material is attached to fiber surface.
The plasticizer is one of epoxidized soybean oil, triethyl citrate, glycerol and polyethylene glycol.
Although additive amount is less in the present invention for plasticizer, the secondary bond between each polymer molecule is weakened, from And increase the mobility of polymer molecular chain, increase the plasticity of polymer, reduce the brittleness of polymer, improve elongation, Flexibility and flexibility.
The dispersing agent is barium stearate, zinc stearate, calcium stearate, cadmium stearate, magnesium stearate and copper stearate One of or it is a variety of.
The selected dispersing agent of the present invention can adjust the motility of each particle in the entire compound system of formation, improve its point Property is dissipated, prevents particle from reuniting.
Flame retardant type PLA base degradable food packaging material of the invention the preparation method comprises the following steps:
(1) silane coupling agent is added later and is modified first using acid processing for sepiolite fiber modified processing.
It is added in the hydrochloric acid solution that concentration is 10% specifically, weighing the sepiolite fibre after ball milling by weight, At 80 DEG C after heating stirring 2h, washing successively is carried out with dehydrated alcohol and deionized water until neutrality, is dried for standby.Take 100 parts After ultrasonic disperse 30min, 0.5-1.5 parts of three second of phenyl is added after above-mentioned sepiolite fibre stirring 10min is added in isopropanol After oxysilane stirs 2h at 80 DEG C, is successively washed, be dried for standby with dehydrated alcohol and deionized water.
(2) PVA/SiO is weighed by weight2Composite rubber material, the sepiolite being added in step (1) after processing thereto are fine Dimension after stirring 3h, is placed in 85 DEG C of vacuum ovens dry 12h, takes out spare.
The present invention is first by PVA/SiO2Composite rubber material is blended with sepiolite, so that PVA/SiO2Composite rubber material is viscous It is attached on sepiolite fibre, by drying, then adds it in polylactic acid system, each component can be made to be uniformly dispersed, Improve the mechanical performance of packaging material.
(3) prepared by packaging material, the product that step (2) is obtained, by a certain percentage with polylactic acid, plasticizer and dispersing agent Mixing, prepares packaging material.
Specifically, weighing polylactic acid, plasticizer and dispersing agent by weight, and composite wood obtained in step (2) is added Material is added in high-speed mixer, uses double screw extruder after mixing, is melted, squeezes out tie rod, cooling, pelletizing, then Pellet obtained addition tablet press machine is pressed into film, obtains flame retardant type PLA base degradable food packaging material.
Had using the preparation-obtained flame retardant type PLA base degradable food packaging material of above technical scheme following excellent Point:
1, the present invention is using treated sepiolite fibre and PVA/SiO2Composite rubber material modified synergic polylactic acid, so that poly- The formation and stabilization of material surface layer of charcoal can be promoted in burning by closing object, the release of heat when reducing burning, feedback to polymerization The heat on object surface is reduced, therefore the thermal cracking of matrix is inhibited, and improves the fire-retardant property of composite material.
2, the present invention joined polylactic acid, polyvinyl alcohol Biodegradable material in the feed, and production process is simple, It is generated without " three wastes ", meets environmentally protective requirement, there is biggish economic benefit and social value.
Specific embodiment
The following examples are further described to of the invention.
Embodiment 1
A kind of flame retardant type PLA base degradable food packaging material, preparation method includes the following steps:
(1) it takes 10 parts of sepiolite fibres after ball milling to be added in the hydrochloric acid solution that concentration is 10%, is heated at 80 DEG C After stirring 2h, washing successively is carried out with dehydrated alcohol and deionized water until neutrality, is dried for standby.100 parts of isopropanols are taken, are added After above-mentioned sepiolite fibre stirring 10min, after ultrasonic disperse 30min, 0.5-1.5 parts of phenyl triethoxysilane is added 80 After stirring 2h at DEG C, is successively washed, be dried for standby with dehydrated alcohol and deionized water.
(2) 10 parts of PVA/SiO are taken2The sepiolite fibre in step (1) after processing is added thereto, stirs for Composite rubber material After mixing 3h, it is placed in 85 DEG C of vacuum ovens dry 12h, is taken out spare.
(3) 45 parts of polylactic acid, 0.5 part of epoxidized soybean oil and 0.25 part of barium stearate and zinc stearate are taken, and step is added (2) composite material obtained in is added in high-speed mixer, uses double screw extruder after mixing, is melted, squeezed out Tie rod, cooling, pelletizing, then pellet obtained addition tablet press machine is pressed into film, obtain the degradable packaging for foodstuff material of flame retardant type PLA base Material.
Embodiment 2
A kind of flame retardant type PLA base degradable food packaging material, preparation method includes the following steps:
(1) it takes 15 parts of sepiolite fibres after ball milling to be added in the hydrochloric acid solution that concentration is 10%, is heated at 80 DEG C After stirring 2h, washing successively is carried out with dehydrated alcohol and deionized water until neutrality, is dried for standby.100 parts of isopropanols are taken, are added After above-mentioned sepiolite fibre stirring 10min, after ultrasonic disperse 30min, 0.5-1.5 parts of phenyl triethoxysilane is added 80 After stirring 2h at DEG C, is successively washed, be dried for standby with dehydrated alcohol and deionized water.
(2) 15 parts of PVA/SiO are taken2The sepiolite fibre in step (1) after processing is added thereto, stirs for Composite rubber material After mixing 3h, it is placed in 85 DEG C of vacuum ovens dry 12h, is taken out spare.
(3) 50 parts of polylactic acid, 0.7 part of epoxidized soybean oil and 0.3 part of barium stearate and zinc stearate are taken, and step is added (2) composite material obtained in is added in high-speed mixer, uses double screw extruder after mixing, is melted, squeezed out Tie rod, cooling, pelletizing, then pellet obtained addition tablet press machine is pressed into film, obtain the degradable packaging for foodstuff material of flame retardant type PLA base Material.
Embodiment 3
A kind of flame retardant type PLA base degradable food packaging material, preparation method includes the following steps:
(1) it takes 15 parts of sepiolite fibres after ball milling to be added in the hydrochloric acid solution that concentration is 10%, is heated at 80 DEG C After stirring 2h, washing successively is carried out with dehydrated alcohol and deionized water until neutrality, is dried for standby.100 parts of isopropanols are taken, are added After above-mentioned sepiolite fibre stirring 10min, after ultrasonic disperse 30min, 0.5-1.5 parts of phenyl triethoxysilane is added 80 After stirring 2h at DEG C, is successively washed, be dried for standby with dehydrated alcohol and deionized water.
(2) 20 parts of PVA/SiO are taken2The sepiolite fibre in step (1) after processing is added thereto, stirs for Composite rubber material After mixing 3h, it is placed in 85 DEG C of vacuum ovens dry 12h, is taken out spare.
(3) 55 parts of polylactic acid, 0.8 part of epoxidized soybean oil and 0.35 part of barium stearate and zinc stearate are taken, and step is added (2) composite material obtained in is added in high-speed mixer, uses double screw extruder after mixing, is melted, squeezed out Tie rod, cooling, pelletizing, then pellet obtained addition tablet press machine is pressed into film, obtain the degradable packaging for foodstuff material of flame retardant type PLA base Material.
Embodiment 4
A kind of flame retardant type PLA base degradable food packaging material, preparation method includes the following steps:
(1) it takes 15 parts of sepiolite fibres after ball milling to be added in the hydrochloric acid solution that concentration is 10%, is heated at 80 DEG C After stirring 2h, washing successively is carried out with dehydrated alcohol and deionized water until neutrality, is dried for standby.100 parts of isopropanols are taken, are added After above-mentioned sepiolite fibre stirring 10min, after ultrasonic disperse 30min, 0.5-1.5 parts of phenyl triethoxysilane is added 80 After stirring 2h at DEG C, is successively washed, be dried for standby with dehydrated alcohol and deionized water.
(2) 25 parts of PVA/SiO are taken2The sepiolite fibre in step (1) after processing is added thereto, stirs for Composite rubber material After mixing 3h, it is placed in 85 DEG C of vacuum ovens dry 12h, is taken out spare.
(3) 60 parts of polylactic acid, 0.9 part of epoxidized soybean oil and 0.4 part of barium stearate and zinc stearate are taken, and step is added (2) composite material obtained in is added in high-speed mixer, uses double screw extruder after mixing, is melted, squeezed out Tie rod, cooling, pelletizing, then pellet obtained addition tablet press machine is pressed into film, obtain the degradable packaging for foodstuff material of flame retardant type PLA base Material.
Comparative example 1
A kind of flame retardant type PLA base degradable food packaging material, preparation method includes the following steps:
(1) 20 parts of PVA/SiO are taken2Composite rubber material is placed in 85 DEG C of vacuum ovens dry 12h, takes out spare.
(2) 55 parts of polylactic acid, 0.8 part of epoxidized soybean oil and 0.35 part of barium stearate and zinc stearate are taken, and step is added (2) composite material obtained in is added in high-speed mixer, uses double screw extruder after mixing, is melted, squeezed out Tie rod, cooling, pelletizing, then pellet obtained addition tablet press machine is pressed into film, obtain the degradable packaging for foodstuff material of flame retardant type PLA base Material.
Comparative example 2
A kind of flame retardant type PLA base degradable food packaging material, preparation method includes the following steps:
(1) it takes 15 parts of sepiolite fibres after ball milling to be added in the hydrochloric acid solution that concentration is 10%, is heated at 80 DEG C After stirring 2h, washing successively is carried out with dehydrated alcohol and deionized water until neutrality, is dried for standby.100 parts of isopropanols are taken, are added After above-mentioned sepiolite fibre stirring 10min, after ultrasonic disperse 30min, 0.5-1.5 parts of phenyl triethoxysilane is added 80 After stirring 2h at DEG C, is successively washed, be dried for standby with dehydrated alcohol and deionized water.
(2) 55 parts of polylactic acid, 0.8 part of epoxidized soybean oil and 0.35 part of barium stearate and zinc stearate are taken, and step is added (1) sepiolite fibre obtained in after processing is added in high-speed mixer, uses double screw extruder after mixing, It melted, squeeze out tie rod, cooling, pelletizing, then pellet obtained addition tablet press machine is pressed into film, obtaining flame retardant type PLA base can Degradation packaging material for food.
Comparative example 3
A kind of flame retardant type PLA base degradable food packaging material, preparation method includes the following steps:
55 parts of polylactic acid, 0.8 part of epoxidized soybean oil and 0.35 part of barium stearate and zinc stearate are taken, high-speed mixer is added In, double screw extruder is used after mixing, is melted, squeezes out tie rod, cooling, pelletizing, then pellet obtained is added Tablet press machine is pressed into film, obtains flame retardant type PLA base degradable food packaging material.
According to GB/T1040-1992, GB/T1040.1-2006, GB/T1043-1993 and GB/T 2406-1993, carry out Tensile strength, elongation at break, impact strength and the detection of material limits oxygen index (OI), the results are shown in Table 1:
Table 1
As shown in Table 1, the flame retardant type PLA base degradable food packaging material that embodiment 1-4 is prepared has preferable Mechanical performance and limit oxygen index, upper limit (UL) oxygen index (OI) can reach 31%, and anti-flammability is strong.Comparative example 1-3 is not it is found that ought simultaneously Sepiolite fibre or PVA/SiO is added2When Composite rubber material, composite material various aspects of performance is declined, when the two does not add Added-time, the mechanical property and anti-flammability of composite material are worst, illustrate sepiolite fibre or PVA/SiO2The addition of Composite rubber material mentions The high mechanical performance and anti-fire of lactic acid composite material.
Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without making creative work The every other embodiment obtained, shall fall within the protection scope of the present invention.

Claims (8)

1. a kind of flame retardant type PLA base degradable food packaging material, it is characterised in that: be made of the raw material of following parts by weight: poly- 45-65 parts of lactic acid, 5-15 parts of sepiolite fibre, PVA/SiO210-25 parts of Composite rubber material, 0.5-1.5 parts of plasticizer, dispersing agent 0.25-0.5 parts.
2. a kind of flame retardant type PLA base degradable food packaging material as described in claim 1, it is characterised in that: the sea Afrodite fiber is the sepiolite fibre after ball milling, and the partial size of sepiolite fibre is 5-30 μm.
3. a kind of flame retardant type PLA base degradable food packaging material as described in claim 1, it is characterised in that: the sea Afrodite fiber is the modified sepiolite fibre of acid activation and phenyl triethoxysilane surface.
4. a kind of flame retardant type PLA base degradable food packaging material as described in claim 1, it is characterised in that: described PVA/SiO2Composite rubber material preparation step are as follows: take 1-5 parts of Na2SiO3It is dissolved in 50 parts of deionized water, stirring is until completely molten Solution obtains Na2SiO3Aqueous solution is slowly added in the PVA aqueous solution that concentration is 5-25%, stirs, drip when being added dropwise Cheng Hou continues to stir, and adjusting solution ph is neutral to get arriving PVA/SiO2Composite rubber material.
5. a kind of flame retardant type PLA base degradable food packaging material as described in claim 1, it is characterised in that: the increasing Modeling agent is one of epoxidized soybean oil, triethyl citrate, glycerol and polyethylene glycol.
6. a kind of flame retardant type PLA base degradable food packaging material as described in claim 1, it is characterised in that: point Powder is one of barium stearate, zinc stearate, calcium stearate, cadmium stearate, magnesium stearate and copper stearate or a variety of.
7. a kind of preparation method of flame retardant type PLA base degradable food packaging material as claimed in any one of claims 1 to 6, It is characterized in that: the following steps are included: silane coupling agent is added first using acid processing in (1) sepiolite fiber modified processing later It is modified；
(2) PVA/SiO is weighed by weight2The sepiolite fibre in step (1) after processing is added thereto, stirs for Composite rubber material After mixing 3h, it is placed in 85 DEG C of vacuum ovens dry 12h, is taken out spare；
(3) prepared by packaging material, and the product that step (2) is obtained mixes by a certain percentage with polylactic acid, plasticizer and dispersing agent It closes, prepares packaging material.
8. a kind of preparation method of flame retardant type PLA base degradable food packaging material as claimed in claim 7, feature exist In: the method for step (1) is to weigh the sepiolite fibre after ball milling by weight the hydrochloric acid solution that concentration is 10% is added In, at 80 DEG C after heating stirring 2h, washing successively is carried out with dehydrated alcohol and deionized water until neutrality, is dried for standby, takes After ultrasonic disperse 30min, 0.5-1.5 parts of phenyl is added after above-mentioned sepiolite fibre stirring 10min is added in 100 parts of isopropanols After triethoxysilane stirs 2h at 80 DEG C, is successively washed, be dried for standby with dehydrated alcohol and deionized water.
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