CN102504345A - Disposable controlled completely-degradable plastic packing bag and preparation method thereof - Google Patents
Disposable controlled completely-degradable plastic packing bag and preparation method thereof Download PDFInfo
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- 238000012856 packing Methods 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229920006238 degradable plastic Polymers 0.000 title claims abstract description 18
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- 239000008107 starch Substances 0.000 claims abstract description 51
- 235000019698 starch Nutrition 0.000 claims abstract description 50
- 238000002156 mixing Methods 0.000 claims abstract description 11
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- 239000000463 material Substances 0.000 claims description 22
- -1 polyoxyethylene Polymers 0.000 claims description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
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- 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
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a disposable controlled completely-degradable plastic packing bag, which is formed through melting, blending, extruding and film-blowing of components comprising in parts by weight: 20 to 45 parts of polyvinyl alcohol, 72 to 87 parts of starch, 10 to 20 parts of micromolecule plasticizer, 0.2 to 2 parts of modified inorganic nanometer additive, 0.1 to 1.5 parts of antioxidant, 0.5 to 3 parts of compatibilizer, 8 to 15 parts of inorganic filler, 0.1 to 1 part of ultraviolet absorber, and 0.1 to 1 part of pigment. The invention further discloses a preparation method of the plastic packing bag. The nanometer composite modifier in the packing bag adopts a micromolecule plasticizer easy to form a hydrogen bond with the starch, a certain amount of inorganic nanometer additives subject to surface treatment are added in the packing bag, so that after PVA (polyvinyl acetate) is modified by the nanometer composite modifier, the use amount of the molecule plasticizers is reduced greatly, the cost is lowed, the reduction of the mechanical property of a film is avoided, and the controlled completely-degradable film with excellent mechanical property and the use performance can be obtained.
Description
Technical field
The invention belongs to plastic packaging bag and preparing technical field thereof, controlled completely degradable plastic packing bag of particularly a kind of disposable use and preparation method thereof.
Background technology
Vilaterm (PE) at present commonly used and Vestolen PP 7052 (PP) plastic packaging bag are owing to light weight, advantage such as cheap, easy to use are widely used in the daily life.But it is when enriching and making things convenient for people's lives, because its staple is difficult to decomposition in physical environment, thereby has caused serious " white pollution " problem.Along with the Sustainable development of society, ecological environment problem has been brought up to the height of development strategy by national governments, and research and development fully biodegradable plastics are the important channels that solve " white pollution " problem that the plastic packaging bag waste brings.
Z 150PH (PVA) is endowed the performance of a lot of excellences because of having characteristics such as poly-hydroxy, strong hydrogen bonding; Simultaneously it also can be through non-petrochemical complex route synthetic, so under the exhausted day by day background of petroleum resources, this material has more important use value.According to scholarly forecast, the annual average rate of increase of whole world PVA film yield will reach 8～10% the coming years.Compare with other film, the PVA film not only has high transparent, oil-proofness, the high barrier properties of gas and in various degree water-soluble, what is more important, and PVA has in wet environment under the condition that bacterium exists can resolve into water and CO in 6 months fully
2Be Biodegradable Materials (Corti A; Solaro R; Chiellini E.Biodegradation of poly (vinylalcohol) in selected mixed microbial culture and relevant culture filtrate [J] Polymer Degradation Stability, 2002,75 (2): 447-458.).But the degraded of PVA is higher to the degraded environmental requirement, makes degradation speed still seem relatively slow, and can't artificially control.Moreover, also because the fusing point of PVA resin is higher relatively, generally at 210～280 ℃; And its thermal degradation temperature is lower; Promptly will begin the etherificate of dewatering, continue the then variable color thermal destruction gradually that heats up, thereby this character of PVA make it be difficult to carry out melt-processed at 170 ℃ of left and right sides PVA.In order to solve the problem that the PVA melting point resin is higher than its thermal degradation temperature, prior art generally is to reduce its fusing point through adding softening agent.Just disclose in the PVA thin film composition like JP77110782 and to have added content and reduce the fusing point of PVA as softening agent, made it realize the blowing film forming under condition of heat decomposition temperature being lower than greater than 40% water.But owing to have a large amount of water in this system, the resin that causes extruding bubbles easily, evenly moulding of film.CN 1368515A has then selected a kind of polymerisable amides monomer as extender plasticizer (addition is 0-5 part); Washiness with in the control resin exists with combined; Thereby effectively reduce the processing temperature of PVA resin; But this amides monomeric plasticizer has certain toxicity, unsuitable contact food and environmentfriendly products, and wherein also need be added with small molecules softening agent simultaneously up to 25 weight parts.As everyone knows, the heavy addition softening agent tends to reduce mechanical properties in films, and this type film is after placing for some time, and softening agent can be separated out at film surface, and these chemical reagent of separating out unavoidably can pollute packed article.
Starch is a kind of natural reproducible material, its aboundresources, cheap, and receive microbial attack easily, last metabolism is water and carbonic acid gas, thereby has the excellent biodegradability ability, is applicable to the material composition as biodegradable material.And are present one type of the most promising degradable plastics with its formed starch-based degrading plastics, it demonstrates huge development prospect in packaging field.Maddever research back proposes, and the degraded of starch-based polymer comprises two processes: on the one hand, starch is by microbial attack; Degraded disappears gradually; And in polymkeric substance, form porous destruction structure, cause the long-pending increase of polymer surfaces, thereby help the further natural decomposition of polymkeric substance; On the other hand, starch degradation can inspire the effect of prooxidant and autoxidator, can cut off macromolecular chain, and the relative molecular weight of polymkeric substance constantly is reduced to can be by the degree of microbial metabolism.These two processes are mutually promoted; Make the degradation speed of starch-based polymer accelerate (Maddever W J; Chapman G M.Modified starch based biodegradable plastics [C] .Annual Technical Conference Society of Plastics Engineers, 1989:1351-1355.).
With starch is the existing bibliographical information of complete biodegradable product of feedstock production.Utilize the plasticity-amylan to mix like CN 1640917A, extrude through high pressure and process the starch-base biodegradation material, use this material blowing film forming again with PE class material grafted monomer and initiator.Though the plasticity-starch content reaches 65～85% in this film,, cause this film contact soil just can be absorbed by soil basically after 1 year because PE matrix itself does not have degradation property.And be that the film of resin matrix also exists similar problem for the PP that employing itself does not have a degradation property.Thus; CN 101781448A proposes a kind of enhanced polylactic acid acid (the PLA)/starch blending system that can degrade fully; This co-mixing system has also strengthened its mechanical property and thermal property when increasing substantially POLYACTIC ACID and starch consistency, also kept the biodegradability of product simultaneously.But the POLYACTIC ACID relative cost is higher, is not suitable for large-scale application in the plastic packaging bag field.CN 200410037609 proposes a kind of packing film and mulch film of fully biodegradable again.By weight percentage, its system component is mainly: starch 30～60%, and ethylene acrylic acid co polymer (EAA) 20～30%, polycaprolactone 5～10%, Injecatable EVA Copolymer (EVA) 1～3%, and wherein the cost of polycaprolactone is also higher.Though CN101016397A discloses the preparation method of a kind of polyvinyl alcohol compound film and preparation method thereof and the composite nano-powder that is used to prepare polyvinyl alcohol compound film.It is said that this method can remedy the existing polyvinyl alcohol compound film poor mechanical property of starch and the defective that production energy consumption is big, throughput is low of adding.But still there are some problems in it: 1) (be at least 24wt% because of the plasticising dosage that adds is excessive; Be up to 38wt%), inevitably can make this type film after placing for some time, produce the problem that softening agent is separated out at film surface; This can make the mechanical properties decrease in film later stage on the one hand; Influence use properties, the chemical reagent of separating out on the other hand unavoidably can pollute packed article, also will increase cost simultaneously.2) amount of starch not high (having only 8.17-38wt%) because of adding so not only can make the cost of gained film still higher, also can influence the degradation rate of film to a certain extent.3) ZnO/SiO because of wherein being added
2The preparation process of composite granule is very complicated, and the cycle is long and institute's chemical reagent that uses is many, consumes greatly, and this can influence the throughput and the increase cost of film undoubtedly to a certain extent.
Other there are some researches show (Wang Yunfang etc., starch-based environment degradable high polymer material progress [J], material Leader; 2005,4:12-15), starch is when improving plastics degradable performance; Can cause the decline of its physical and mechanical properties on the one hand, make its processing difficulties, also exist wetting ability too strong on the other hand; And the consistency between most of resins for universal use is very poor, causes the mechanical property of material to decline to a great extent, thereby has hindered the widespread use of starch plastic in the industrialization promotion process.Therefore in order to guarantee the final use properties of starch plastics goods, general terms of settlement is to reduce the addition of starch, but can bring the cost of goods higher again like this, the problem that degradation speed is slower.
Summary of the invention
Deficiency to prior art; The purpose of this invention is to provide the controlled plastic packaging bag of degraded fully of a kind of disposable use, the characteristics of this packing bag have been to use high-load starch as matrix, and have added the nano assistant with photocatalytic activity of surface-treated; Not only can reduce cost greatly; Realize the controlled degraded fully of plastic wrapping bag product, have good physical and mechanical properties again concurrently simultaneously, can be used for supermarket shopping packing bag, electric equipment products packing bag etc.
Another object of the present invention provides a kind of film blowing method that melt extrudes for preparing the controlled plastic packaging bag of degrading fully of above-mentioned disposable use.
The controlled plastic packaging bag of degraded fully of disposable use provided by the invention, this packing bag is to extrude blown film by following raw material through melt blending to form by weight:
Wherein the modified inorganic nano assistant is to be formed by at least a the processing through the surperficial oleophylic modification of γ-aminopropyl methyldiethoxysilane in anatase-type nanometer titanium dioxide and the nano-cerium oxide; Its particle diameter is 1～100nm, and the thick 0.025-0.035mm of this film, transverse tensile strength are 12.42-25.60MPa; The cross break elongation is 300.03-661.87%; Transverse modulus of elasticity is 522.51-1, and 069.27MPa, longitudinal tensile strength are 17.81-30.22MPa; The longitudinal fracture elongation is 341.81-549.61%; Longitudinal modulus of elasticity is 659.68-736.77MPa, and soil buries and weightless be 9.27-12.53% in 40 days, and soil buries and weightlessly was 57.03-78.91% in 200 days.
The polymerization degree of contained Z 150PH >=1700 in the above-mentioned packing bag, alcoholysis degree are 99%.
Contained starch is at least a in Starch rice, W-Gum, green starch, Rhizoma Nelumbinis starch and the yam starch in the above-mentioned packing bag.
In the above-mentioned packing bag contained small molecules softening agent be relative molecular weight be 1000～4000g/mol the polyoxyethylene poly-oxygen propylene aether segmented copolymer (Prist, Poloxamer), at least a in triethyl citrate (TEC) and the ethanoyl tri-n-butyl citrate (ATBC).
Contained inhibitor is 2 in the above-mentioned packing bag, at least a in three grades of butyl of 6--4-methylphenol and two (3, three grades of butyl of 5--4-hydroxy phenyl) thioethers.Though the inhibitor according to the invention general oxidation inhibitor that is this area; But inhibitor can make macromolecule resin (being Z 150PH) that good hot-work stability is arranged in the course of processing, avoids because high temperature changes the color and luster, mechanical property of macromolecule resin etc. in hot procedure.
Contained expanding material is maleic anhydride or dodecyl cis-butenedioic anhydride in the above-mentioned packing bag; Mineral filler is at least a in lime carbonate, kaolin and the wollastonite.
Contained UV light absorber is at least a in 2-(4,6-phenylbenzene-1,3,5-triazines-2)-5-normal hexane oxygen base phenol and 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole in the above-mentioned packing bag.
Contained pigment is any in white titanium pigment, barium cadmium red, phthalocyanine blue, the carbon black etc. in the above-mentioned packing bag.
Preferred 30～the 50nm of particle diameter of contained anatase-type nanometer titanium dioxide and nano-cerium oxide nanoparticle in the above-mentioned packing bag.
The preparation method of the controlled completely degradable plastic packing bag of above-mentioned disposable use provided by the invention, the process step and the condition of this method are following:
(1) earlier 30～50 parts of inorganic nano auxiliary agents is dropped in the superhigh speed mixing machine; Stirred 10～30 minutes down at 3000～5000 rev/mins, divide 2-3 adding with 0.5～1.5 portion of mixed solution of silane coupling agent therebetween, after adding with 50～100 parts of absolute ethyl alcohols; Continuing ultra-high speed mixed 1.5～2 hours; Suction filtration then, powder is put into ball mill ball mill pulverizing at least 1 hour again in 100～120 ℃ of oven dry;
(2) the surface-modified inorganic nano assistant that obtains being passed through colloidal mill with 10～20 parts in small molecules softening agent for 0.2～2 part disperseed 1 hour at least;
(3) in 10～25 parts of 72～87 parts of mixture, starch, the Z 150PH and 0.5～1.5 part of input high-speed mixer of inhibitor with surface-modified inorganic nano assistant that obtains and small molecules softening agent; 60～80 ℃ of temperature; Rotating speed stirs 10～20min, discharging down for 100～200 rev/mins;
(4) gained Preblend is added in the twin screw extruder,, melt extrude granulation under the temperature 175～190 ℃ (this temperature is meant the temperature of twin screw extruder metering zone) and promptly get nano composite modifying agent 100～200 rev/mins of screw speeds;
(5) with 0.1～1 part of gained nano composite modifying agent, 1～5 part of Z 150PH, 0.5～3 part of expanding material, 5～8 parts of mineral fillers, 0.1～1 part of UV light absorber and pigment; Under normal temperature, stirring velocity 50-100 rev/min, mix; Extrude inflation film manufacturing machine through single screw rod then and under 175～190 ℃ of (this temperature is meant the temperature of single screw extrusion machine metering zone) processing temperatures, carry out hot melt extrusion-blown modling film forming, last bag, cutting, heat-sealing, print and pack.
Add each material umber be weight part, and inorganic nano auxiliary agent wherein is in anatase-type nanometer titanium dioxide or the nano-cerium oxide any, its particle diameter is 1～100nm, is preferably 30～50nm's.
The polyvinyl alcohol resin polymerization degree >=1700 described in the above preparation method, alcoholysis degree are 99%.
Starch described in the above preparation method is at least a in Starch rice, W-Gum, green starch, Rhizoma Nelumbinis starch and the yam starch.
Small molecules softening agent described in the above preparation method is that relative molecular weight is at least a in polyoxyethylene poly-oxygen propylene aether segmented copolymer, triethyl citrate and the ethanoyl tri-n-butyl citrate of 1000～4000g/mol.
Increasing reaction agent described in the above preparation method is maleic anhydride or dodecyl cis-butenedioic anhydride.
Mineral filler described in the above preparation method is at least a in lime carbonate, kaolin and the wollastonite.
Inhibitor described in the above preparation method is 2, at least a in three grades of butyl of 6--4-methylphenol and two (3, three grades of butyl of 5--4-hydroxy phenyl) thioethers.
UV light absorber described in the above preparation method is at least a in 2-(4,6-phenylbenzene-1,3,5-triazines-2)-5-normal hexane oxygen base phenol and 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole.
Pigment described in the above preparation method is any in white titanium pigment, barium cadmium red, phthalocyanine blue, the carbon black etc.
The present invention compared with prior art has the following advantages:
1, since the present invention provide nano composite modifying agent contained in the plastic packaging bag adopted be prone to form the small molecules softening agent of hydrogen bond with starch in; Add a certain amount of again through surface-treated inorganic nano auxiliary agent; Thereby after using its modified PVA; Not only can significantly reduce small molecules plasticizer dosage (only need to add 6.04-16.5wt%, reduced about 2.3-4 doubly), reduce cost than prior art CN101016397A; Avoid the mechanical properties decrease and the problem of separating out the pollution packed article in film later stage, and can also obtain possessing plastics film mechanical property and all good controlled complete biodegradable film of later stage use properties.
2, because the inorganic nano auxiliary agent through surface-treated that adds in the plastic packaging bag provided by the invention is the material with photocatalysis; Can be with the energy of sunshine as the chemical reaction energy derive, when UV-irradiation, photon energy reaches or when surpassing the photocatalyst material band-gap energy; Transition of electron from the valence band to the conduction band will take place in electronics; Become light induced electron, on valence band, produce corresponding hole simultaneously, form electron-hole pair; It is photo-generated carrier; And after photo-generated carrier moves to material surface rapidly, the oxygen and the moisture of active material surface adsorption on the one hand, photon-electron can generate ultra-oxygen anion free radical (O with the oxygen molecule reaction of surface adsorption on the other hand
2 -1), the hole then with the hydration OH of surface adsorption
-1Ionic reaction generates the extremely strong hydroxyl free radical hydroxyl of oxidisability, and (OH), the strong oxidizing property of hydroxyl can resolve into free of contamination CO with organism
2And water, finally reach the degraded purpose, thereby can obtain the plastic packaging bag of controlled complete biodegradable through the addition of control inorganic nano auxiliary agent.
3, owing to be added with modified inorganic nano assistant and small molecules softening agent in the plastic packaging bag provided by the invention; Thereby it not only can carry out nano modification to PVA; Guarantee that it has enough temperature regulation interval in the screw extrusion press extrusion; Make that thermooxidative degradation neither takes place PVA in this temperature range, material also can keep required flowability and shearing force, reaches the degree of mixedness of expection; And can also make the interpenetrating(polymer)networks of the molecular level that forms between the starch that finally obtains and the PVA, improve the mechanical property of modified product.
4, be the good non-toxic plasticizer of environmental-protecting performance owing to adding the small molecules softening agent in the plastic packaging bag provided by the invention; They not only have extremely low acute toxicity; Biological degradation at short notice simultaneously makes ecological cumulative risk be reduced to minimally, is used for medicine and medical device industry by food and drug administration (FDA) approval at present; And all be used for packaging material for food by permission in the U.S., Europe, Japan; Thereby both can avoid commercially available plastic packaging bag to use the worry (because of animal experiment has shown, DOP, DINP can cause injury of testis and a series of to hepatic and/or renal disadvantageous effect) of conventional plasticizers phthalic acid two (the 2-ethyl oneself) health risk that ester brought, and consumption is few; Effective, problem of environment also can not appear influencing.
5, owing to employed inorganic nano auxiliary agent in the plastic packaging bag provided by the invention is to carry out special organic surface treatment and dispersing technology in advance; When it uses as properties-correcting agent; Can improve the dispersiveness of nanoparticle in macromolecule resin; Improve the consistency and the bonding force of inorganic nano auxiliary agent and macromolecule resin, make its with macromolecule resin, inorganicly can in nanometer range, combine the chemical bonding force of formation between two-phase interface with organic phase; The interfacial effect of this nano assistant makes between it and the polymkeric substance and can produce more contact area simultaneously; Stress concentration effect in addition; Can produce more tiny crack and viscous deformation, can change more striking energy into heat absorption, thereby can bring into play the nano effect and the synergistic effect of inorganic nano auxiliary agent; Absorb more striking energy, the mechanical property of goods is improved thereupon.
6, because the present invention provides the composite modifier that has used starch and inorganic nano photochemical catalysis auxiliary agent to make in the plastic packaging bag; Thereby can realize that not only (addition is 45-69% to biodegradable, the high filling of starch; Increased about 1.8-5.5 doubly than prior art CN101016397A) reduce the function of plastic packaging bag cost; Also can act synergistically with photochemical catalysis inorganic nano auxiliary agent; Improve degradation rate, realize the complete controllable light catalysis-biological degradation of plastics, and the degraded product environmentally safe.The addition of starch and the contradiction between final use properties, cost and the degradation rate have also been solved simultaneously.
7, owing to adopted small molecules softening agent and nano assistant composite modified in the method for preparing plastic packaging bag provided by the invention; Thereby not only reduced the PVA melt processing temperature, and make melt-processed become possibility, help realizing large-scale industrial production; And process is simple; Technical maturity is easy to grasp, and is convenient to promote.
Description of drawings
Fig. 1 is the anatase type nano TiO of 30～50nm for the particle diameter that does not carry out surface-treated
2Particle amplifies 100,000 times transmission electron microscope shape appearance figure, the visible surface-treated anatase type nano TiO that do not carry out from figure
2Particle aggregation is serious.
Fig. 2 is the anatase type nano TiO of 30～50nm for the particle diameter of the present invention after surface-treated
2Particle amplifies 20,000 times sem photograph in the Z 150PH matrix.
Fig. 3 is the anatase type nano TiO of 30～50nm for the particle diameter of the present invention after surface-treated
2Particle amplifies 40,000 times sem photograph in the Z 150PH matrix.Anatase type nano TiO from Fig. 2,3 after the visible surface modification
2Particle has good dispersion state in the Z 150PH matrix.
Fig. 4 is the lateral tensile stress and the tension strain graphic representation of the controlled completely degradable plastic packing bag of disposable use provided by the invention, and wherein 1#, 2#, 3#, 4# curve are respectively the lateral tensile stress and the tension strain curve of embodiment 1,2,3,4 gained packing bags.
Fig. 5 is the longitudinal stretching stress and the tension strain graphic representation of the controlled completely degradable plastic packing bag of disposable use provided by the invention, and wherein 1#, 2#, 3#, 4# curve are respectively the longitudinal stretching stress and the tension strain curve of embodiment 1,2,3,4 gained packing bags.
Embodiment
Provide embodiment below so that foregoing of the present invention is done further to specify.But should this be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.Do not breaking away under the above-mentioned technological thought situation of the present invention, various replacements or change according to ordinary skill knowledge and customary means are made include within the scope of the invention.
In addition, what be worth explanation is, below the umber of the used material of each embodiment be weight part.
Be that the nano-cerium oxide of 30～50nm is put in the superhigh speed mixing machine for 50 parts earlier with particle diameter; Stirred 20 minutes down at 4000 rev/mins, the mixed solution with 80 parts of 1 part of γ-aminopropyl methyldiethoxysilane and absolute ethyl alcohols divides 3 addings therebetween, after adding; Continuing ultra-high speed mixed 1.5 hours; Suction filtration then, powder is put into ball mill ball mill pulverizing at least 1 hour again in 120 ℃ of oven dry.
With 0.2 part of nano assistant after the surface-treated that obtains and relative molecular weight is that 5 parts of 5 parts of 5 parts of polyoxyethylene poly-oxygen propylene aether segmented copolymers, the triethyl citrates of 1000g/mol and polyoxyethylene glycol that 5 parts in 10 parts of water of ethanoyl tri-n-butyl citrate, 10 parts of USP Kosher, relative molecular weight are 400g/mol disperseed 2 hours through colloidal mill; Then with 15 parts of 75 parts of W-Gums, 1799 Z 150PH, two (3; Three grades of butyl of 5--4-hydroxy phenyl) in 0.5 part of input high-speed mixer of thioether inhibitor; 80 ℃ of temperature; Rotating speed stirs 20min down for 100 rev/mins, and discharging gets final product melt extruding granulation in its adding twin screw extruder again.200 rev/mins of screw speeds, screw extrusion press is respectively distinguished temperature and is set at: 115 ℃ of feeding sections, 170 ℃ of compression sections, 190 ℃ of metering zones, 190 ℃ of head sections.
With above step gained composite modifier, 1799 20 parts of Z 150PH, 2-(4; 6-phenylbenzene-1,3,5-triazines-2)-1 part of 5-normal hexane oxygen base phenol, 3 parts of dodecyl cis-butenedioic anhydrides, 10 parts of kaolin and 0.5 part of adding planetary stirring machine of barium cadmium red in; At normal temperatures; Mix with 50 rev/mins, put into single screw rod then and extrude inflation film manufacturing machine and under 175 ℃, carry out hot melt blowing film forming, last bag, cutting, print and pack.The degradation property of prepared packing bag and physical and mechanical properties are seen table 1 and table 2 respectively.
Be that the anatase-type nanometer titanium dioxide of 30～50nm is put in the superhigh speed mixing machine for 30 parts earlier with particle diameter; Stirred 30 minutes down at 3000 rev/mins, the mixed solution with 50 parts of 0.5 part of γ-aminopropyl methyldiethoxysilane and absolute ethyl alcohols divides 3 addings therebetween, after adding; Continuing ultra-high speed mixed 2 hours; Suction filtration then, powder is put into ball mill ball mill pulverizing at least 1 hour again in 110 ℃ of oven dry.
Nano assistant after the surface-treated that obtains is passed through colloidal mill with 15 parts of ethanoyl tri-n-butyl citrates for 1 part to be disperseed 1 hour; Then with 10 parts of 40 parts of 40 parts of Starch rices, green starch, 1799 Z 150PH, 2; In three grades of butyl of 6--1 part of input high-speed mixer of 4-methylphenol inhibitor, 70 ℃ of temperature, rotating speed stirs 20min down for 120 rev/mins; Discharging gets final product melt extruding granulation in its adding twin screw extruder again.180 rev/mins of screw speeds, screw extrusion press is respectively distinguished temperature and is set at: 115 ℃ of feeding sections, 170 ℃ of compression sections, 180 ℃ of metering zones, 190 ℃ of head sections.
With above step gained composite modifier, 1799 20 parts of Z 150PH, 2-(4; 6-phenylbenzene-1,3,5-triazines-2)-0.5 part of 5-normal hexane oxygen base phenol, 1.5 parts of maleic anhydrides, 12 parts in lime carbonate and 0.2 part of adding planetary stirring machine of phthalocyanine blue in; At normal temperatures; Mix with 100 rev/mins, put into single screw rod then and extrude inflation film manufacturing machine and under 185 ℃, carry out hot melt blowing film forming, last bag, cutting, print and pack.The degradation property of prepared packing bag and physical and mechanical properties are seen table 1 and table 2 respectively.
Be that 40 parts of the anatase-type nanometer titanium dioxides of 30～50nm and the nano-cerium oxide of 30～50nm are put in the superhigh speed mixing machine for 10 parts with particle diameter earlier; Stirred 10 minutes down at 5000 rev/mins, the mixed solution with 100 parts of 1.5 parts of γ-aminopropyl methyldiethoxysilane and absolute ethyl alcohols divides 3 addings therebetween, after adding; Continuing ultra-high speed mixed 1.5 hours; Suction filtration then, powder is put into ball mill ball mill pulverizing at least 1 hour again in 110 ℃ of oven dry.
10 parts of 5 parts of polyoxyethylene poly-oxygen propylene aether segmented copolymers and ethanoyl tri-n-butyl citrates with 1.5 parts of nano assistants after the surface-treated that obtains and relative molecular weight being 1500g/mol disperseed 2 hours through colloidal mill; Then with 5 parts of 20 parts of 42 parts of 30 parts of Rhizoma Nelumbinis starch, yam starch, 1799 Z 150PH, 2499 Z 150PH, 2; Three grades of butyl of 6--1 part of 4-methylphenol and two (3; Three grades of butyl of 5--4-hydroxy phenyl) two kinds of inhibitors of 0.5 part of grade of thioether drop in the high-speed mixer; 60 ℃ of temperature; Rotating speed stirs 15min down for 150 rev/mins, and discharging can obtain the composite modifier master batch with melt extruding granulation in its adding twin screw extruder again.180 rev/mins of twin screw extruder screw speeds, screw extrusion press is respectively distinguished temperature and is set at: 115 ℃ of feeding sections, 170 ℃ of compression sections, 180 ℃ of metering zones, 185 ℃ of head sections.
1 part of gained composite modifier, 1799 20 parts of Z 150PH, 0.2 part of 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 1 part of maleic anhydride, 15 parts in lime carbonate and pigment titanium white are in planetary stirring machine; At normal temperatures; Mix with 60 rev/mins; Put into single screw rod then and extrude inflation film manufacturing machine and under 180 ℃ of processing temperatures, carry out hot melt blowing film forming, last bag, cut and pack.The degradation property of prepared packing bag and physical and mechanical properties are seen table 1 and table 2 respectively.
Be that 20 parts of anatase-type nanometer titanium dioxides and the particle diameter of 30～50nm is that the nano-cerium oxide of 30～50nm is put in the superhigh speed mixing machine for 20 parts earlier with particle diameter; Stirred 20 minutes down at 4000 rev/mins, the mixed solution with 80 parts of 1 part of γ-aminopropyl methyldiethoxysilane and absolute ethyl alcohols divides 3 addings therebetween, after adding; Continuing ultra-high speed mixed 2 hours; Suction filtration then, powder is put into ball mill ball mill pulverizing at least 1 hour again in 100 ℃ of oven dry.
With 2 parts of nano assistants after the surface-treated that obtains and 2.5 parts of ethanoyl tri-n-butyl citrates, relative molecular weight is that 2.5 parts of 5 parts of polyoxyethylene poly-oxygen propylene aether segmented copolymers and the triethyl citrates of 4000g/mol disperseed 1.5 hours through colloidal mill; Then with 10 parts of 47 parts of 40 parts of W-Gums, Rhizoma Nelumbinis starch, 1799 Z 150PH, 2; In three grades of butyl of 6--1.5 parts of input high-speed mixers of 4-methylphenol inhibitor; 60 ℃ of temperature; Rotating speed stirs 10min down for 200 rev/mins, and discharging gets final product melt extruding granulation in its adding twin screw extruder again.100 rev/mins of screw speeds, screw extrusion press is respectively distinguished temperature and is set at: 115 ℃ of feeding sections, 170 ℃ of compression sections, 175 ℃ of metering zones, 190 ℃ of head sections.
With above step gained composite modifier, 1799 10 parts of Z 150PH, 2-(4; 6-phenylbenzene-1; 3; 5-triazine-2)-0.05 part of 5-normal hexane oxygen base phenol and 0.05 part of 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 0.5 part of maleic anhydride, 8 parts of wollastonites and 0.1 part of adding planetary stirring machine of carbon black in, at normal temperatures, mix with 100 rev/mins; Put into single screw rod then and extrude inflation film manufacturing machine and under 190 ℃, carry out hot melt blowing film forming, last bag, cutting, print and pack.The degradation property of prepared packing bag and physical and mechanical properties are seen table 1 and table 2 respectively.
What be worth explanation is, the degradation property of above embodiment gained packing bag is tested according to GB/T 20197-2006, and the result sees table 1; The mechanical property of gained packing bag is tested according to GB/T 1040.3-2006, and the result sees table
Table 1
Table 2
Claims (10)
1. controlled completely degradable plastic packing bag of disposable use, this packing bag is to extrude blown film by following raw material through melt blending to form by weight:
Wherein the modified inorganic nano assistant is to be formed by at least a the processing through the surperficial oleophylic modification of γ-aminopropyl methyldiethoxysilane in anatase-type nanometer titanium dioxide and the nano-cerium oxide; Its particle diameter is 1～100nm, and the thick 0.025-0.035mm of this film, transverse tensile strength are 12.42-25.60MPa; The cross break elongation is 300.03-661.87%; Transverse modulus of elasticity is 522.51-1, and 069.27MPa, longitudinal tensile strength are 17.81-30.22MPa; The longitudinal fracture elongation is 341.81-549.61%; Longitudinal modulus of elasticity is 659.68-736.77MPa, and soil buries and weightless be 9.27-12.53% in 40 days, and soil buries and weightlessly was 57.03-78.91% in 200 days.
2. the controlled completely degradable plastic packing bag of disposable use according to claim 1, contained starch is at least a in Starch rice, W-Gum, green starch, Rhizoma Nelumbinis starch and the yam starch in this packing bag.
3. the controlled completely degradable plastic packing bag of disposable use according to claim 1 and 2, contained small molecules softening agent is that relative molecular weight is at least a in polyoxyethylene poly-oxygen propylene aether segmented copolymer, triethyl citrate and the ethanoyl tri-n-butyl citrate of 1000～4000g/mol in this packing bag.
4. the controlled completely degradable plastic packing bag of disposable use according to claim 1 and 2, contained expanding material is maleic anhydride or dodecyl cis-butenedioic anhydride in this packing bag.
5. the controlled completely degradable plastic packing bag of disposable use according to claim 1 and 2, contained mineral filler is at least a in lime carbonate, kaolin and the wollastonite in this packing bag.
6. the preparation method of the controlled completely degradable plastic packing bag of the described disposable use of claim 1, the process step and the condition of this method are following:
(1) earlier 30～50 parts of inorganic nano auxiliary agents is dropped in the superhigh speed mixing machine; Stirred 10～30 minutes down at 3000～5000 rev/mins, divide 2-3 adding with γ-0.5～1.5 portion of mixed solution of aminopropyl methyldiethoxysilane therebetween, after adding with 50～100 parts of absolute ethyl alcohols; Continuing ultra-high speed mixed 1.5～2 hours; Suction filtration then, powder is put into ball mill ball mill pulverizing at least 1 hour again in 100～120 ℃ of oven dry;
(2) the surface-modified inorganic nano assistant that obtains being passed through colloidal mill with 10～20 parts in small molecules softening agent for 0.2～2 part disperseed 1 hour at least;
(3) in 10～25 parts of 72～87 parts of mixture, starch, the Z 150PH and 0.5～1.5 part of input high-speed mixer of inhibitor with surface-modified inorganic nano assistant that obtains and small molecules softening agent; 60～80 ℃ of temperature; Rotating speed stirs 10～20min, discharging down for 100～200 rev/mins;
(4) gained Preblend is added in the twin screw extruder,, melt extrude granulation under 175～190 ℃ of the temperature and promptly get nano composite modifying agent 100～200 rev/mins of screw speeds;
(5) at normal temperatures with 0.1～1 part of gained nano composite modifying agent, 10～20 parts of Z 150PH, 0.5～3 part of expanding material, 5～8 parts of mineral fillers, 0.1～1 part of UV light absorber and pigment; Mix with rotating speed 50-100 rev/min; Extrude inflation film manufacturing machine through single screw rod then and under 175～190 ℃ of processing temperatures, carry out hot melt extrusion-blown modling film forming, last bag, cutting, heat-sealing, print and pack.
Add each material umber be weight part, and inorganic nano auxiliary agent wherein is at least a in anatase-type nanometer titanium dioxide and the nano-cerium oxide, its particle diameter is 1～100nm.
7. the preparation method of the controlled completely degradable plastic packing bag of disposable use according to claim 6, the starch described in this preparation method is at least a in Starch rice, W-Gum, green starch, Rhizoma Nelumbinis starch and the yam starch.
8. according to the preparation method of claim 6 or the controlled completely degradable plastic packing bag of 7 described disposable uses, the small molecules softening agent described in this preparation method is that relative molecular weight is at least a in polyoxyethylene poly-oxygen propylene aether segmented copolymer, triethyl citrate and the ethanoyl tri-n-butyl citrate of 1000～4000g/mol.
9. according to the preparation method of claim 6 or the controlled completely degradable plastic packing bag of 7 described disposable uses, the expanding material described in this preparation method is maleic anhydride or dodecyl cis-butenedioic anhydride.
10. according to the preparation method of claim 6 or the controlled completely degradable plastic packing bag of 7 described disposable uses, the mineral filler described in this preparation method is at least a in lime carbonate, kaolin and the wollastonite.
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| CN112457535A (en) * | 2020-11-30 | 2021-03-09 | 绍兴兆丽新材料科技有限公司 | Environment-friendly spicy cabbage packaging bag and preparation method thereof |
| CN112940428A (en) * | 2021-02-05 | 2021-06-11 | 中山市新领航塑化科技有限公司 | Biodegradable thermoplastic PVA/starch seedling raising cup and preparation method thereof |
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| CN114479393A (en) * | 2021-12-18 | 2022-05-13 | 太仓市缘福汽配有限公司 | Environment-friendly degradable plastic packaging bag and preparation process thereof |
| CN114891276A (en) * | 2022-05-25 | 2022-08-12 | 广东森士包装有限公司 | Environment-friendly beverage packaging bag and processing technology thereof |
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