CN106947117A - Fiber reinforcement starch foaming tableware of complete biodegradable and preparation method thereof - Google Patents
Fiber reinforcement starch foaming tableware of complete biodegradable and preparation method thereof Download PDFInfo
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- CN106947117A CN106947117A CN201710309478.6A CN201710309478A CN106947117A CN 106947117 A CN106947117 A CN 106947117A CN 201710309478 A CN201710309478 A CN 201710309478A CN 106947117 A CN106947117 A CN 106947117A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
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- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47G—HOUSEHOLD OR TABLE EQUIPMENT
- A47G19/00—Table service
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
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- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/125—Water, e.g. hydrated salts
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/142—Compounds containing oxygen but no halogen atom
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
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- C08J2203/10—Water or water-releasing compounds
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- C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/20—Ternary blends of expanding agents
- C08J2203/204—Ternary blends of expanding agents of chemical foaming agent and physical blowing agents
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- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
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- C08J2467/00—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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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C08L2203/14—Applications used for foams
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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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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The present invention relates to biodegradation material, and in particular to fiber reinforcement starch foaming tableware of a kind of complete biodegradable and preparation method thereof.The foaming plastic tableware is divided into inside and outside two layers, is divided into inside and outside two layers, wherein, outer layer is made up of each component of following mass percent：50~82% tapiocas, 5~20% biodegradable chopped fibers, 5~10% biodegradable toughening agent, 1~3% compatilizer, 5~10% foaming agents, 1~5% insulation agent and 1~2% releasing agent.Above component is uniformly mixed, after hot-forming, then sprayed biological degradable film, obtain the fiber reinforcement starch foaming tableware of complete biodegradable.Tableware intensity height, rigidity is big, and good toughness, expansion ratio is high, and foaming aperture is small, and thermal insulation is good, and water and oil-resistant is good, and all material energy complete biodegradable, is the optimal selection for substituting expanded polystyrene (EPS) tableware.
Description
Technical field
The present invention relates to biological degradable tableware, and in particular to a kind of fiber reinforcement starch foaming tableware of complete biodegradable
And preparation method thereof.
Background technology
It is well known that foaming plastic tableware is earliest using aboard, due to discarded plastic garbage to Along Railway it is ecological with
And landscape causes heavy damage, the Ministry of Railways of China completely forbids in May nineteen ninety-five and uses foaming plastic tableware in Railways Stations car.Pass
The one time foam tableware of system, mainly using polystyrene PS resins as raw material, melts by high-temperature heating in an extruder
Foaming agent butane etc. is added after melting and carries out extrusion pulling-on piece.After sheet material winding, placed in the moist environment of ventilation after health again
Carry out reheating plastics sucking moulding, the various Dining tools being made such as mess-tin, soup bowl, instant noodle bowl, fresh tray etc..China was once
One time foam tableware is included in into technique in 1999,2005 and 2011 three times to fall behind or product backwardness catalogue.
The Sheng of catering trade rises, the fast development of especially various fast foods, is provided to disposable plastic tableware huge
The market demand, the sight for having attracted numerous investors sharp.Under the promoting that the Ministry of Railways proposes " being moulded with paper generation " slogan earliest,
The enterprise of a large amount of moulded pulp set for dining is occurred in that after 1996.But, because moulded pulp set for dining is in health and performance
On easily go wrong, technical difficulty is big, and product yield is low, Difficulty.According to selective examination display, moulded pulp set for dining is much all
Hygienic requirements is not met, permeability, infiltration, deformation and to bond the phenomenons such as rice serious.
In addition, after disposable plastic foaming plastic tableware use, due to food residual, it is difficult to clean, even if cleaning will also result in
The waste of water resource, and water source secondary pollution.Therefore, disposable plastic foaming plastic tableware basically can not be recycled, and be filled out
It can not also be degraded after burying, a certain degree of pollution is suffered to soil and water source.1999 Nian Yuan State Economic and Trade Commission require, in 2000
The foaming plastic tableware that " backward products " are listed in because of severe contamination environment will be eliminated before the end of the year in China.So far, once
Property foaming plastic tableware starts progressively to withdraw from the market.
Also many be turned on " environment protecting tableware ", " degradative tableware " or " urban environmental protection " non-foamed plastic tableware at present exist
Domestic many areas are largely used, because the product is mainly common plasticses, add a large amount of inorganic mineral inserts such as calcium carbonate
Or add after a part of starch, thus acetic acid residue severe overweight, and cutlery box disintegration, remaining plastic composition will not still drop
Solution, the harm that these plastic flakes are caused to environment is bigger.
Disposable foamed plastic tableware is made in starch, the white pollution that non-degradable foamed plastic is brought can have both been solved, after use
Starch foaming tableware be also used as fertilizer or feed, and asking for starch production capacity surplus can also be alleviated to a certain extent
Topic, is the outlet that starch have found an environmental protection, the road of a sustainable development is also have found for urban development.
The A of CN 106496652 disclose a kind of disposable tableware of starch foaming, and it is by the modified beautiful of 86-93 parts by weight
Rice starch, the stearic acid release agent zinc of 0.8-1.2 parts by weight, the accelerator potassium sorbate of 0.2-0.4 parts by weight, 1.5-2 weight
The thickener Sodium Polyacrylate of part, the stabilizer of 45-53 parts by weight, the water of some parts by weight are mixed and obtained after compound,
Obtained through hot-forming；Content of starch of the present invention is high, greatly reduces production cost, using cornstarch as primary raw material, utilizes
Tea Polyphenols is modified to it, and is aided with the obtained foaming snack box of a variety of function additives, will not be produced after the starch foaming tableware is heated
Raw any toxic component, and can change into the material being easily degraded under field conditions (factors), safety and environmental protection can effective environmental protection.
Sodium Polyacrylate is added in above-mentioned system, the material is common high molecular materials, it is impossible to biodegradable, have impact on its ring of degrading
Guarantor property；And wood pulp cellulose is added, wood pulp cellulose can influence its expansion ratio, and the recyclability of wood pulp cellulose can not show a candle to form sediment
Powder；Above all the invention does not carry out waterproof and oilproof processing to material at all, causes material not have water and oil-resistant, it is difficult to
As tableware.
The A of CN 105254930 disclose a kind of biodegradable foaming snack box, are made up of the raw material of following parts by weight：
100-110 parts of green starch, 8-12 parts of sulfosalicylic acid, 15-20 parts of vinylacetate, 18-22 parts of bentonite, maltodextrin
15-20 parts, 13-18 parts of polyvinyl alcohol, 12-16 parts of carboxymethyl cellulose, 10-15 parts of nano-calcium carbonate, 10-15 parts of sesbania gum,
8-12 parts of palm-kernel oil, 8-12 parts of urea, 6-10 parts of antiseptic, 6-10 parts of butylated hydroxy anisole, dodecyl sodium sulfate 5-8
Part, 40-50 parts of ethanol, 200-300 parts of water.It will not produce any toxic component after the made foaming plastic tableware of the present invention is heated, and
The material being easily degraded can be changed under natural conditions, safety and environmental protection can effective environmental protection；The antibacterial wherein added in addition
Agent has higher antibacterial effect, greatly improves the health rank of cutlery box.The invention is made using the method for extrusion sheet plastic uptake
Standby foaming snack box, but specific aim means, expansion ratio are not taken to foaming process it is difficult to ensure that；Polyethylene is introduced in system
Alcohol non-biodegradable substances, influence its biological degradability；And it is also added into the dangerous substances such as urea and ethanol；Simultaneously
The cost of green starch is too high, also waterproof and oilproof processing is not carried out to tableware, it is difficult to promote.
The A of CN 105273240 disclose a kind of natural degradation starch foaming material and its production technology, using following technical side
Case：Its raw material is as follows by mass percentage：Starch 68-75%, string 12-18%, blowing promotor 15-28% and the demoulding are helped
Agent 7-13%；It uses starch for main material, is fabricated to disposable material, so that using the disposable made, it has
Can substituted for plastic disposable product, realize nature degradable, pollution-free, environmental protection and energy saving.But the invention is also without to tableware
Waterproof and oilproof processing is carried out, is equally difficult to be used as tableware.
The A of CN 103937035 and the A of CN 103951852 also individually disclose high strength starch-based degrading environment-friendly materials, but
Polyvinyl alcohol non-biodegradable substances are all introduced in their systems, it is impossible to complete biodegradable.
From this, the document at present on starch foaming tableware focuses mostly in the substantial amounts of wood pulp cellulose of addition and addition
The materials such as polyvinyl alcohol, so not only make it that the high foamability of starch can not be realized, biological degradability also is difficult to ensure, and
These documents do not carry out waterproof and oilproof processing to tableware, it is difficult to as tableware.
Therefore, develop a kind of with low cost, excellent performance and the tableware of energy complete biodegradable is significant.
The content of the invention
It is an object of the invention to provide a kind of high foamability, foaming aperture is small, thermal insulation is good, high intensity, high tenacity, anti-
The fiber reinforcement starch foaming tableware of the good complete biodegradable of water grease proofness；Present invention simultaneously provides its preparation method.
The fiber reinforcement starch foaming tableware of complete biodegradable of the present invention, is divided into inside and outside two layers, wherein, outer layer
It is made up of each component of following mass percent：50~82% tapiocas, 5~20% biodegradable chopped fibers, 5~10% lifes
Thing degraded toughener, 1~3% compatilizer, 5~10% foaming agents, 1~5% insulation agent and 1~2% releasing agent.
Wherein：
Described tapioca is unmodified ative starch, and mesh number is 50~150 mesh.
Described biodegradable chopped fiber is polylactic acid short-fiber, polyhydroxyalkanoate chopped fiber or the short fibre of polyglycolic acid
One or more in dimension, the biodegradable a diameter of 10~100D of chopped fiber, length is 10~50mm.
Described biodegradable toughening agent is the powder worn into after biodegradable plastic is cooled down through liquid nitrogen, mesh number 100~500
Mesh.
Described biodegradable plastic is poly terephthalic acid tetramethylene adipate, poly butylene succinate, poly- third
Support the one or more in carbonic ester.
Described compatilizer is one kind in monoethanolamine, diethanol amine or triethanolamine.
Described foaming agent is made up of water, long chain fatty acids, sodium acid carbonate, and their mass ratio is 6~8:1~2:1~
2, long chain fatty acids are one kind in laurate, palmitic acid, stearic acid, oleic acid or erucic acid.
Described insulation agent is zinc-magnesium aluminium carbonate form hydrotalcite, and molecular formula is ZnMg3Al2(OH)12CO3·mH2O, zinc-magnesium
Al mole ratio is 1:3:2, mesh number is 4500~5500 mesh.
Described releasing agent is glycerin monostearate, and mesh number is 50~150 mesh.
Described internal layer is Biodegradable film, and the material of Biodegradable film is poly terephthalic acid adipic acid butanediol
One kind in ester, polypropylene carbonate, PLA, poly butylene succinate, polyhydroxyalkanoate or polyglycolic acid.
The preparation method of the fiber reinforcement starch foaming tableware of described complete biodegradable is：Successively by tapioca,
Biodegradable chopped fiber, biodegradable toughening agent, insulation agent are added in agitator, and 10~15min is stirred under normal temperature, are added compatible
15~20min is stirred under agent, normal temperature, foaming agent and releasing agent is added, added after being well mixed at 40~60 DEG C in mould, in
20~60s is hot-forming at 180~250 DEG C, finally the Biodegradable film of 5~20 μm of coating thickness again, obtains complete biology
The fiber reinforcement starch foaming tableware of degraded.
The present invention introduces biodegradable chopped fiber, biodegradable toughening agent, compatilizer, foaming using tapioca as raw material
The materials such as agent, insulation agent, releasing agent.
It is well known that after simple starch gelatinization crosslinking, its mechanical strength and toughness are all poor, and it is not water-fast also intolerant to
Oil.If starch is made into tableware, it is necessary to solve two key issues, one is activeness and quietness, and two be that the waterproof for solving starch is prevented
Oiliness energy.We have selected tapioca first, because amylopectin content is high in tapioca, and starch molecule amount is high,
So make it that intensity and toughness after starch gelatinization will be better than other starch, more important point is tapioca not grain
Food, it is to avoid the situation of " striving grain with people ".The biodegradable chopped fiber of present invention selection goes to strengthen starch, and non-selected traditional wood
Pulp fibres, one is, because biodegradable chopped fiber can melt under heat effect, to be fused into one completely with starch, cooling and shaping
A supporting network is formed afterwards, so as to play humidification, two be because wood pulp cellulose is in process of production along with water pollution
And the waste of water resource, and the recyclability of wood pulp and bad.
While biodegradable short fiber reinforced gelatinized starch, certain toughening effect can also be played, but also needs to draw
Enter the preferably biodegradable powder of toughness, to its further toughness reinforcing.Using powder quickly mixed with starch system beneficial to toughener
Close uniform, it is also possible that its rapid melting in forming process, fuses into one with starch, play excellent toughening effect.Cause
This, the present invention have selected the preferable different materials of toughness in biodegradable plastic as toughener, for example poly terephthalic acid oneself
Succinate adipate, poly butylene succinate, polypropylene carbonate.
And the purpose foamed has two, one is reduction product grammes per square metre, reduces cost, and two be to improve its thermal insulation.In heating
Under effect, gelatinization cross-linking reaction can both occur with starch for water, can also vaporize so that starch foaming, but due to water and starch
Very well, therefore, the steam in abscess is difficult stable existence to dissolubility.Long chain fatty acids mostly come from naturally, and it is used as food
Using very safe, but it is acid weaker, with sodium bicarbonate be difficult to react under normal temperature, but can just occur under heat effect
And reaction, release carbon dioxide.The releasing of carbon dioxide can not only make it that starch obtains high expansion ratio, while with two
The exclusion of carbonoxide, so as to accelerate the evaporation of steam, shortens shaping time and molding cycle, improves production efficiency.And
And traditional PS foaming plastic tableware, it is in butane foaming, process of producing product and releases substantial amounts of butane, pollutes environment, butane is easy
There is potential safety hazard in combustion property material, production.And the foaming system that we select is food additives, we using vapor and
The carbon dioxide of releasing is reacted to realize foaming, safety non-toxic.
After starch gelatinization crosslinking, performance is more crisp, after foaming, fragility increase, although we introduce biodegradable chopped fiber
Improve toughness with toughener, but because chopped fiber and toughener are all polyester constructions, the compatibility with starch is poor, so being
The further toughness for improving product, we introduce compatilizer-monoethanolamine again, monoethanolamine has hydroxyl and amino structure, it
Can form strong hydrogen bond action with the hydroxyl of starch, while also can with the terminal hydroxy group of biodegradable plastic, end carboxyl and
Ester group on molecular backbone forms strong hydrogen bond action, and the end carboxyl of amido and biodegradable plastic at high temperature can also
React, generate amido link, therefore, monoethanolamine can be obviously improved the phase between biodegradable chopped fiber and toughener and starch
Capacitive, so as to further improve toughness of products.
Tableware should also have preferable thermal insulation in addition to intensity and toughness.Although foaming structure imparts starch meal
The certain heat-proof quality of tool, but in order to further improve its thermal insulation, the present invention introduces zinc-magnesium aluminium carbonate into system again
Type hydrotalcite, the material is usually used in the plumper of polyvinyl chloride, and we have been found that it can after it is used for into starch foaming system
Effect of heat insulation is improved, this is due to that zinc-magnesium al mole ratio is 1:3:The microcosmic of 2 hydrotalcites above has stratiform misconstruction, in heat
Transmittance process in, the gap in its stratiform misconstruction serve hinder heat transfer effect, this improves heat-insulated
Effect.
Substantial amounts of hydroxyl is present on starch molecular chain so that its compatibility with metal very well, therefore, in process of production
Easily there are considerable sticking problems, for the ease of being stripped after shaping, improve production efficiency, the present invention introduces food-grade into system again
The compatibility of surfactant glycerin monostearate GMS, GMS and starch very well, certain plasticizing can also be played to starch
Effect.
The problem of finally needing and solve is to carry out waterproof and oilproof processing to starch dishware.In order to realize its water and oil-resistant,
Of the invention and non-selected non-degradable common plasticses, but have selected complete biodegradable plastics and be sprayed on tableware inner surface, reach
Preferable waterproof and oilproof performance is arrived.
Beneficial effects of the present invention are as follows：
(1) present invention can realize the enhancing of foaming plastic tableware, its can be improved again tough by introducing biodegradable chopped fiber
Property, and the high foamability of starch is not influenceed.
(2) present invention can not only obtain height by introducing the foaming system that water, long chain fatty acids, sodium acid carbonate are constituted
Expansion ratio, can also shorten molding cycle, and foaming system used is food grade additives, safety non-toxic.
(3) because foaming can make it that the fragility of starch increases, therefore, we introduce the toughener of complete biodegradable, carry
The toughness of high product, improves its performance, for the ease of being well mixed with system, and the toughener that the present invention is selected is powder
Shape.
(4) in order to improve the compatibility of biodegradable chopped fiber and toughener and starch, we add alcohol into system
Amine, toughness is further improved by improving compatibility.
(5) the releasing agent glycerin monostearate that system is used is also environment-protecting and non-poisonous food additives.
(6) by the method for spraying, one layer of complete biodegradable film is sprayed in foaming plastic tableware inner surface, is not only realized
Waterproof and oilproof, nor affects on overall biological degradability.
(7) the starch foaming tableware for preparing of the present invention not only can be in complete biodegradable under natural environment, but also can
Using the fertilizer nutrient as plant.
In addition, in order to reach more preferable mixed effect, we are preferred mixing method.Due to tapioca, biodegradation
Chopped fiber, toughener, insulation agent are solid constituent, therefore, are first well mixed these solid constituents at normal temperatures, so protect
Demonstrate,prove in the case of well mixed, do not destroyed fibre structure.Then the compatilizer of liquid is added, the process of mixing is stirred just
It is the process that hydrogen bond action occurs between material, so can obtains mixing the material being more uniformly distributed, and the phase between material
Capacitive is improved.The foaming agent and releasing agent of liquid are eventually adding, foaming agent and releasing agent material can be evenly spread to
In, fibre structure will not be destroyed again, will not also destroy the hydrogen bond structure formed.
To sum up, the present invention is using tapioca as raw material, by introducing biodegradable chopped fiber, biodegradable toughening agent, phase
Hold a series of materials such as agent, foaming agent, insulation agent, releasing agent, obtain the tableware of complete biodegradable.The tableware intensity is high, just
Property big, good toughness, expansion ratio is high, and foaming aperture is small, and thermal insulation is good, and water and oil-resistant is good, and all material can be completely
Biodegradation, is the optimal selection for substituting expanded polystyrene (EPS) tableware.
Embodiment
The present invention is described further with reference to embodiments.
Embodiment 1
By 50% tapioca (50 mesh), 20% polylactic acid short-fiber (50D, 25mm), 10% poly butylene succinate
Powder (100 mesh), the hydrotalcite ZnMg of 5%5000 mesh3Al2(OH)12CO3·mH2O is sequentially added in agitator, is stirred under normal temperature
10min, adds under 3% diethanol amine, normal temperature and stirs 15min, be eventually adding 10% foaming agent (water/stearic acid/sodium bicarbonate=
8/1/1 mass ratio), the glycerin monostearate of 2%100 mesh be uniformly mixed at 40 DEG C after add mould in, at 180 DEG C
40s is hot-forming, finally the poly terephthalic acid tetramethylene adipate film of 10 μm of coating thickness again, obtains completely biological drop
The fiber reinforcement starch foaming tableware of solution.
Embodiment 2
By 60% tapioca (100 mesh), 15% polylactic acid short-fiber (100D, 10mm), 10% poly terephthalic acid oneself
Succinate adipate powder (500 mesh), the hydrotalcite ZnMg of 3%5500 mesh3Al2(OH)12CO3·mH2O sequentially adds agitator
In, 10min is stirred under normal temperature, adds under 3% triethanolamine, normal temperature and stirs 15min, 8% foaming agent (water/palm fibre is eventually adding
The mass ratio of palmitic acid acid/sodium bicarbonate=6/2/2), the glycerin monostearate of 1%50 mesh add mould after being uniformly mixed at 60 DEG C
In tool, 20s is hot-forming at 250 DEG C, finally the polypropylene carbonate film of 20 μm of coating thickness again, obtains complete biodegradable
Fiber reinforcement starch foaming tableware
Embodiment 3
By 82% tapioca (150 mesh), 5% polyglycolic acid chopped fiber (10D, 50mm), 5% poly terephthalic acid oneself two
Sour butanediol ester powder (300 mesh), the hydrotalcite ZnMg of 1%4500 mesh3Al2(OH)12CO3·mH2O is sequentially added in agitator,
Stir 10min under normal temperature, add under 1% monoethanolamine, normal temperature and stir 15min, be eventually adding 5% foaming agent (water/oleic acid/
The mass ratio of sodium bicarbonate=7/2/1), the glycerin monostearate of 1%150 mesh add mould after being uniformly mixed at 50 DEG C
In, 60s is hot-forming at 220 DEG C, finally the poly butylene succinate film of 5 μm of coating thickness again, obtains completely biological drop
The fiber reinforcement starch foaming tableware of solution.
Embodiment 4
By 75% tapioca (100 mesh), 5% poly- 3,4 hydroxybutyric acid ester copolymer chopped fiber (60D, 20mm), 8% gather
Trimethylene polycarbonate powder (200 mesh), the hydrotalcite ZnMg of 2%5000 mesh3Al2(OH)12CO3·mH2O is sequentially added in agitator,
Stir 10min under normal temperature, add under 2% diethanol amine, normal temperature and stir 15min, be eventually adding 6% foaming agent (water/erucic acid/
The mass ratio of sodium bicarbonate=7/1/2), the glycerin monostearate of 2%100 mesh add mould after being uniformly mixed at 45 DEG C
In, 30s is hot-forming at 210 DEG C, finally the poly terephthalic acid tetramethylene adipate film of 15 μm of coating thickness again, obtains
The fiber reinforcement starch foaming tableware of complete biodegradable.
Comparative example 1
By 55% tapioca (50 mesh), 20% polylactic acid short-fiber (50D, 25mm), 10% poly butylene succinate
Powder (100 mesh) is sequentially added in agitator, and 10min is stirred under normal temperature, is added under 3% diethanol amine, normal temperature and is stirred
15min, be eventually adding 10% foaming agent (water/stearic acid/sodium bicarbonate=8/1/1 mass ratio), 2%100 mesh monostearate it is sweet
Grease is added in mould after being uniformly mixed at 40 DEG C, and 40s is hot-forming at 180 DEG C, finally 10 μm of coating thickness again
Poly terephthalic acid tetramethylene adipate film, obtains the fiber reinforcement starch foaming tableware of complete biodegradable.
Comparative example 2
By 63% tapioca (100 mesh), 15% polylactic acid short-fiber (100D, 10mm), 10% poly terephthalic acid oneself
Succinate adipate powder (500 mesh), the hydrotalcite ZnMg of 3%5500 mesh3Al2(OH)12CO3·mH2O sequentially adds agitator
In, 10min is stirred under normal temperature, 8% foaming agent (water/palmitic acid/sodium bicarbonate=6/2/2 mass ratio), the list of 1%50 mesh is added
Tristerin is added in mould after being uniformly mixed at 60 DEG C, and 20s is hot-forming at 250 DEG C, and thickness is finally sprayed again
The polypropylene carbonate film of 20 μm of degree, has obtained the fiber reinforcement starch foaming tableware of complete biodegradable.
Comparative example 3
By 50% tapioca (50 mesh), 20% polylactic acid short-fiber (50D, 25mm), 10% poly butylene succinate
Powder (100 mesh), the hydrotalcite ZnMg of 5%5000 mesh3Al2(OH)12CO3·mH2O, 3% diethanol amine, 10% foaming agent (water/
The mass ratio of stearic acid/sodium bicarbonate=8/1/1), the glycerin monostearate of 2%100 mesh, after being uniformly mixed at 40 DEG C plus
Enter in mould, 40s is hot-forming at 180 DEG C, finally the poly terephthalic acid tetramethylene adipate of 10 μm of coating thickness is thin again
Film, obtains the fiber reinforcement starch foaming tableware of complete biodegradable.
Comparative example 4
By 60% tapioca (100 mesh), 15% polylactic acid short-fiber (100D, 10mm), 10% poly terephthalic acid oneself
Succinate adipate powder (500 mesh), the hydrotalcite ZnMg of 3%5500 mesh3Al2(OH)12CO3·mH2O, 3% triethanolamine,
8% foaming agent (water/palmitic acid/sodium bicarbonate=6/2/2 mass ratio), the glycerin monostearate of 1%50 mesh, are stirred at 60 DEG C
Added after well mixed in mould, 20s is hot-forming at 250 DEG C, finally the polypropylene carbonate film of 20 μm of coating thickness again,
Obtain the fiber reinforcement starch foaming tableware of complete biodegradable.
For the ease of performance comparison, we select traditional PS foaming plastic tableware to enter with embodiment of the present invention 1-4, comparative example 1-4
Row performance comparison, traditional PS foaming is butane foaming.
Utilize 10*10cm2Number of times when folding 90 degree of foamed board is broken, to characterize its toughness；Utilize 100 DEG C of hot water
The difference of the temperature of tableware bottom outer surface and water temperature after 5min in tableware is poured into, to represent its heat-proof quality；Utilize 100 DEG C of heat
Water and 100 DEG C of thermocolours draw oil not pour into tableware, its leakage scenarios are observed after 24h, to characterize its waterproof and oilproof performance, specifically
It is shown in Table 1.
The performance data table of table 1
As can be seen from Table 1, the intensity of the fiber reinforcement starch foaming tableware of embodiment 1-4 complete biodegradable is high,
Compressive strength is in more than 3.2MPa；Rigidity is big, good toughness, and folding times are more than 30 times during fracture；Expansion ratio is high, 15.5
More than times, foaming aperture is small, is less than 13 μm；Adiabatic temperature difference is more than 66 DEG C, and thermal insulation is good；Nothing is oozed after hot water deep fat 24h
Leakage situation occurs, and water and oil-resistant is good.
By embodiment 1 and comparative example 1 as can be seen that ratio containing insulation agent is free of the heat-insulated effect of starch foaming tableware of insulation agent
Fruit is more preferably.
By embodiment 2 and comparative example 2 as can be seen that starch foaming tableware toughness of the ratio containing compatilizer without compatilizer and
Compressive strength is more preferable.
By embodiment 1 and comparative example 3 as can be seen that the sequencing of charging influences the toughness and pressure of starch foaming tableware
Contracting intensity, the toughness and compressive strength of the starch foaming tableware of embodiment 1 is higher.
By embodiment 2 and comparative example 4 as can be seen that the sequencing of charging influences the toughness and pressure of starch foaming tableware
Contracting intensity, the toughness and compressive strength of the starch foaming tableware of embodiment 2 is higher.
Claims (10)
1. a kind of fiber reinforcement starch foaming tableware of complete biodegradable, it is characterised in that：It is divided into inside and outside two layers, wherein, outside
Layer is made up of each component of following mass percent：50~82% tapiocas, 5~20% biodegradable chopped fibers, 5~10%
Biodegradable toughening agent, 1~3% compatilizer, 5~10% foaming agents, 1~5% insulation agent and 1~2% releasing agent.
2. the fiber reinforcement starch foaming tableware of complete biodegradable according to claim 1, it is characterised in that：Para arrowroot
Powder is unmodified ative starch, and mesh number is 50~150 mesh.
3. the fiber reinforcement starch foaming tableware of complete biodegradable according to claim 1, it is characterised in that：Biology drop
Solution chopped fiber is the one or more in polylactic acid short-fiber, polyhydroxyalkanoate chopped fiber or polyglycolic acid chopped fiber, raw
The thing degraded a diameter of 10~100D of chopped fiber, length is 10~50mm.
4. the fiber reinforcement starch foaming tableware of complete biodegradable according to claim 1, it is characterised in that：Biology drop
Solution toughener is the powder worn into after biodegradable plastic is cooled down through liquid nitrogen, the mesh of mesh number 100~500；Biodegradable plastic is poly-
One or more in terephthalic acid (TPA) tetramethylene adipate, poly butylene succinate, polypropylene carbonate.
5. the fiber reinforcement starch foaming tableware of complete biodegradable according to claim 1, it is characterised in that：Compatilizer
For one kind in monoethanolamine, diethanol amine or triethanolamine.
6. the fiber reinforcement starch foaming tableware of complete biodegradable according to claim 1, it is characterised in that：Foaming agent
It is made up of water, long chain fatty acids, sodium acid carbonate, their mass ratio is 6~8:1~2:1~2, long chain fatty acids be laurate,
One kind in palmitic acid, stearic acid, oleic acid or erucic acid.
7. the fiber reinforcement starch foaming tableware of complete biodegradable according to claim 1, it is characterised in that：Insulation agent
For zinc-magnesium aluminium carbonate form hydrotalcite, molecular formula is ZnMg3Al2(OH)12CO3·mH2O, zinc-magnesium al mole ratio is 1:3:2, mesh number
For 4500~5500 mesh；Releasing agent is glycerin monostearate, and mesh number is 50~150 mesh.
8. the fiber reinforcement starch foaming tableware of complete biodegradable according to claim 1, it is characterised in that：Internal layer is
Biodegradable film.
9. the fiber reinforcement starch foaming tableware of complete biodegradable according to claim 8, it is characterised in that：Biology drop
The material of degrading film is poly terephthalic acid tetramethylene adipate, polypropylene carbonate, PLA, poly-succinic acid-butanediol
One kind in ester, polyhydroxyalkanoate or polyglycolic acid.
10. a kind of preparation side of the fiber reinforcement starch foaming tableware of any described complete biodegradable of claim 1~9
Method, it is characterised in that：Tapioca, biodegradable chopped fiber, biodegradable toughening agent, insulation agent are added into agitator successively
In, 10~15min is stirred under normal temperature, adds and 15~20min is stirred under compatilizer, normal temperature, foaming agent and releasing agent are added, 40
At~60 DEG C be well mixed after add mould in, it is hot-forming in 20~60s at 180~250 DEG C, finally again coating thickness 5~
20 μm of Biodegradable film, obtains the fiber reinforcement starch foaming tableware of complete biodegradable.
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| CN111690177A (en) * | 2019-03-13 | 2020-09-22 | 北京绿态美景环保科技有限公司 | Preparation method of starch foaming disposable tableware and packaging product |
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| CN113382665A (en) * | 2018-10-15 | 2021-09-10 | 丹尼米尔生物塑料有限公司 | Biopolymer-coated fiber food service article |
| EA038718B1 (en) * | 2019-12-30 | 2021-10-08 | федеральное государственное автономное образовательное учреждение высшего образования "Южно-Уральский государственный университет (национальный исследовательский университет)" | Biodegradable dishware production method |
| CN114102955A (en) * | 2020-08-31 | 2022-03-01 | 天津科技大学 | Method for preparing foamed polylactic acid by adopting normal-temperature foaming technology |
| CN114634717A (en) * | 2022-04-21 | 2022-06-17 | 河北工程大学 | Plant fiber-based biodegradable tableware and preparation method thereof |
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| CN112679924A (en) * | 2020-12-15 | 2021-04-20 | 浙江金晟环保股份有限公司 | PHA (polyhydroxyalkanoate) disposable snack box capable of being rapidly degraded and preparation method thereof |
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