CN102504346A - Starch based nanometer photocatalytic composite degrading modifying agent and preparation method thereof - Google Patents
Starch based nanometer photocatalytic composite degrading modifying agent and preparation method thereof Download PDFInfo
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- CN102504346A CN102504346A CN2011103547825A CN201110354782A CN102504346A CN 102504346 A CN102504346 A CN 102504346A CN 2011103547825 A CN2011103547825 A CN 2011103547825A CN 201110354782 A CN201110354782 A CN 201110354782A CN 102504346 A CN102504346 A CN 102504346A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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Abstract
The invention discloses a starch based nanometer photocatalytic composite degrading modifying agent. The modifying agent is prepared by carrying out melt blending on the following raw materials, wherein the raw materials comprise, by weight, 72-87 parts of starch, 10-25 parts of polyvinyl alcohol, 10-20 parts of a small molecular plasticizer, 0.2-2 parts of a modified inorganic nanometer additive, and 0.5-1.5 parts of an antioxidant, wherein the modified inorganic nanometer additive is prepared by carrying out a surface lipophilic modification treatment on at least a material selected from anatase type nano-titanium dioxide, mixed crystal type nano-titanium dioxide and nano-cerium oxide through a silane coupling agent. The present invention further discloses a preparation method for the starch based nanometer photocatalytic composite degrading modifying agent. According to the present invention, the starch based nanometer photocatalytic composite degrading modifying agent of the present invention is adopted to modify the polymer material, such that the complete biodegradability can be achieved; the high content starch is added to the system, such that the cost of the final product can be substantially reduced; with the added nanometer additive, it is ensured that the product has good physical and mechanical properties; the agent and the method of the present invention can be used for modifying preparations of various disposable plastic products, mulch films, supermarket plastic packaging bags, and the like.
Description
Technical field
The invention belongs to the properties-correcting agent and the preparing technical field thereof that are used for plastics, particularly a kind of environment-friendly type that can be used for improving the plastics degradation property is degraded starch base nano-photo catalytic composite degradation properties-correcting agent and preparation method thereof fully.
Background technology
The Along with people's growth in the living standard, the quickening of rhythm of life, the consumption of disposable plastic goods grows with each passing day; And the use of a large amount of plastics; Bringing to people efficiently simultaneously,, brought serious " white pollution " in physical environment to human ecological environment because it is difficult to decompose.China forbids producing, selling and uying thickness less than 0.025 millimeter plastic shopping bag (being called for short the super-thin plastic shopping bag) on June 1st, 2008; Plastic shopping bag paid utilization system is carried out in commodity retail places such as all supermarkets, market, country fair, must not provide free plastic shopping bag without exception; To enlarge the scope that the restriction plastics bag uses simultaneously, comprise places such as restaurant, hospital.But these administrative measures can not be eliminated the plastic garbage pollution on the environment fully.Therefore, the completely degradable plastic that research and development can degrade in environment, can be dissolved by the environment assimilation, degradation rate is controlled has become one of important topic that national governments advocate and researcher is made earnest efforts.
At present, by the method branch of the controlled completely degradable plastic of preparation, mainly comprise synthesizing to have biodegradable novel plastic and utilize two kinds of starch and existing plastic blend modifications.Wherein synthetic exploratory workload with biodegradable novel plastic is big, and risk is high, and the biodegradable novel plastic that develops often complex process, cost is higher, is unsuitable for large-scale promotion.Test through pilot scale like major part; Got into the complete degradation polymer of bio-based in suitability for industrialized production stage: POLYACTIC ACID (PLA), polycaprolactone (PCL), poly butylene succinate (PBS), aliphatic polycarbonate, aliphatic/aromatic copolyesters and their blend etc., commercialization process and the fancy price because of material applications makes it can't be accepted to become the major obstacle of its development of restriction by market exactly.
Being seen quite a few degradable plastic product in current market all belongs to and utilizes starch and existing plastic blend modification to obtain.Starch is a kind of biomass renewable resource of natural cheapness, also is a kind of poly-hydroxy natural high moleculer eompound.Starch receives microbial attack easily, but last metabolism is water and carbonic acid gas, thereby has the excellent biodegradability ability, is applicable to the material composition as biodegradable material.The starch-based degrading plastics are present one type of the most promising degradable plasticss, and it demonstrates huge development prospect in packaging field.Research like Maddever is just pointed out; The degraded of starch-based polymer comprises two processes: on the one hand; Starch in the material is at first by microbial attack, and degraded disappears gradually, and in polymkeric substance, forms 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.).But regrettably this type degradable plastic product belongs to the degraded of crumbling property, promptly removes the rest part of destarching and still can not degrade fast and degraded fully.That is to say it can be under the certain environment condition with some cycles in deterioration, be fragmented into and relatively be prone to the fragment or the broken end of being dissolved by environment, but to degrade fully, also need, and the speed of degraded far is unable to catch up with the generation speed of Plastic wastes again through for a long time.Secondly, owing to have the strong hydrogen bonding effect between starch molecule, be difficult to forming process.
CN 1640917A utilizes the plasticity-amylan to mix with Vilaterm (PE) type material grafted monomer and initiator, extrudes through high pressure and processes the starch-base biodegradation material, uses this material blowing film forming again.Though the plasticity-starch content because PE matrix itself does not have degradation property, causes this film contact soil just can part to be absorbed by soil after 1 year up to 65～85% in this film.And adopt PP is that the film of resin matrix also exists similar problem.
Through years development, develop into the Z 150PH (PVA) that to degrade fully, POLYACTIC ACID (PLA), poly butyric ester etc. from Vilaterm, Vestolen PP 7052, the PS of part degraded with the synthetic materials of starch blending.A kind of enhanced polylactic acid acid (Poly (lactic acid) that can degrade is fully disclosed like CN 101781448A; PLA)/the starch blending system; This system is when increasing substantially POLYACTIC ACID and starch consistency; Also strengthen its mechanical property and thermal property, also kept the biodegradability of product simultaneously.But the relative cost of used POLYACTIC ACID is higher, is not suitable for large-scale application in disposable use field of plastic products.
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
Primary and foremost purpose of the present invention is the deficiency to prior art, and a kind of starch-based nano-photo catalytic composite degradation properties-correcting agent is provided, and this properties-correcting agent both can improve the plastics degradation property, was unlikely to influence the plastics physical and mechanical properties again.
Another object of the present invention provides a kind of preparation method of above-mentioned starch-based nano-photo catalytic composite degradation properties-correcting agent.
Starch-based nano-photo catalytic composite degradation properties-correcting agent provided by the invention is made up of through melt blending following raw material 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, mixed crystal type nanometer titanium dioxide and the nano-cerium oxide; Its particle diameter is 1～100nm, preferred 20～50nm.
Contained mixed crystal type nanometer titanium dioxide is meant that this nano titanium oxide is to be made up of anatase-type nanometer titanium dioxide and rutile type nano titanic oxide in the above-mentioned starch-based nano-photo catalytic composite degradation properties-correcting agent, and anatase-type nanometer titanium dioxide wherein is at least 75%.
Contained starch is at least a in Starch rice, W-Gum, green starch, Rhizoma Nelumbinis starch and the yam starch in the above-mentioned starch-based nano-photo catalytic composite degradation properties-correcting agent.
In the above-mentioned starch-based nano-photo catalytic composite degradation properties-correcting agent 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 specially four (β-(3 in the above-mentioned starch-based nano-photo catalytic composite degradation properties-correcting agent; The 5-di-tert-butyl-hydroxy phenyl) pentaerythritol ester, 2 propionic acid); 2 '-methylene-bis (4-methyl-6-tert butyl phenol), 4; At least a in 4 '-thiobis-(the 6-tertiary butyl-3-methylphenol), 2, three grades of butyl of 6--4-methylphenol and two (3, three grades of butyl of 5--4-hydroxy phenyl) thioethers.
The preparation method of above-mentioned starch-based nano-photo catalytic composite degradation properties-correcting agent provided by the invention, the process step and the condition of this method are following:
(1) earlier the inorganic nano auxiliary agent is put in the superhigh speed mixing machine for 30～50 parts by weight; 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 get final product 100～200 rev/mins of screw speeds.
Add each material umber be weight part, and inorganic nano auxiliary agent wherein is at least a in anatase-type nanometer titanium dioxide, mixed crystal type nanometer titanium dioxide and the nano-cerium oxide, particle diameter is 1～100nm, preferred 20～50nm.Mixed crystal type nanometer titanium dioxide is meant that this nano titanium oxide is to be mixed by the nano titanium oxide of Detitanium-ore-type and two kinds of crystal formations of rutile-type to constitute, but the nano titanium oxide of the Detitanium-ore-type in the mixed crystal type nanometer titanium dioxide described in the above preparation method is at least 75%.
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.
The polymerization degree of the Z 150PH described in the above preparation method >=1700, alcoholysis degree are 99%.
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.
Inhibitor described in the above preparation method is specially four (β-(3; The 5-di-tert-butyl-hydroxy phenyl) pentaerythritol ester, 2 propionic acid); 2 '-methylene-bis (4-methyl-6-tert butyl phenol), 4; At least a in 4 '-thiobis-(the 6-tertiary butyl-3-methylphenol), 2, 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.
As everyone knows; The Z 150PH molecule is because of containing a large amount of hydroxyls, and the reactive force that intermolecular existence is very strong can form a large amount of intramolecularly and intermolecular ydrogen bonding; Cause fusing point very high (230 ℃) and very approaching with its decomposition temperature (240 ℃); PVA is very big to water sensitivity in addition, be difficult to thermoplastic method processing, therefore big limitations its range of application.But because of the environment-friendly type that can be used for improving the plastics degradation property provided by the invention fully degraded starch base nano composite modifying agent to have adopted relative molecular weight be that polyoxyethylene poly-oxygen propylene aether segmented copolymer, triethyl citrate (TEC) and the ethanoyl tri-n-butyl citrate (ATBC) etc. of 1000～4000g/mol are prone to form the softening agent of the small molecules of hydrogen bond as starch with starch; Add a certain amount of simultaneously through surface-treated inorganic nano auxiliary agent; After using its modified PVA; Can not only obtain possessing the controlled complete biodegradable film of plastics film mechanical property and use properties, and cost is close with common plastic film.Especially wherein the inorganic nano auxiliary agent that contains not only can carry out nano modification to PVA; Guarantee that it has enough temperature regulation interval in twin-screw extruder extrusion process; Make that PVA neither degrades in this temperature range, material also can keep required flowability and shearing force, reaches the blending speed and the degree of mixedness of expection; And can also make the interpenetrating(polymer)networks of the molecular level that forms between starch and the PVA, finally improve the mechanical property of modified product.
Secondly, the inorganic nano-particle of interpolation through changing the PVA aggregated structure, can improve thermostability and the facile hydrolysis property of PVA on the one hand.Because of discovering, nanoparticle has the effect of heterogeneous nucleation agent for the crystal polymer thing, and crystallization rate is improved greatly, fills a spot of nanoparticle and can cause PVA spherocrystal particle tiny, even, when crystallisation process carries out under comparatively high temps; Improve with nanoparticle content, the nucleus that then forms is just many more, and spherulite size is just more little, thereby has played the effect that improves the PVA thermostability.Nanoparticle also can promote the nucleation crystallization rate of PVA spherocrystal at the PVA crystallization initial stage on the other hand, and can hinder growing up of PVA spherocrystal latter stage in crystallization, makes the PVA micritization, and crystallite causes surrender and is ductile failure as little discrete particles in amorphous matrix.So nanoparticle to the above-mentioned synergy of PVA crystalline, can make polymkeric substance produce well toughness reinforcing and reinforced effects with an amount of interpolation nanoparticle.Simultaneously; After in polymkeric substance, adding the modified Nano particle, the interfacial effect of nanoparticle makes between it and the polymkeric substance can produce more contact area, because stress concentration effect; Can produce more tiny crack and viscous deformation; Change more striking energy into heat absorption, thereby absorb more striking energy, the mechanical property of goods can be improved thereupon.
The 3rd; Since the inorganic nano-particle that the present invention adopts be through a large amount of testing sieves of the inventor select to ultraviolet ray have broadband, long-acting strong absorbent can anatase-type nanometer titanium dioxide, mixed crystal type nanometer titanium dioxide and nano-cerium oxide; Thereby can utilize their to absorb the ultraviolet degradation that photocatalysis that the ultraviolet ray back produced promotes macromolecular material such as PVA; Thereby improve the degradation rate of macromolecular material; And, finally reach the controlled effect of degrading fully that makes the outdoor plastics goods through itself and the biodegradable synergy of starch.
The 4th; Though the surface-area of nanoparticle itself is big, surface energy is high, and the valence bond of particle surface is in the height undersaturated condition; Be highly susceptible to reuniting and absorption; In case reunite, common mechanical stirring means are difficult to again open it, disperse, and the dust dispersion quality of disperse phase in matrix is the importance of this type of decision composite materials property.Disperse not goodly, not only the performance of nano material itself also can influence the modification result less than normal performance, the over-all properties phenomenon of " not advancing counter moving back " occurs.But because nanoparticle used in the present invention is to carry out special organic surface treatment and dispersing technology in advance; Thereby when using as properties-correcting agent; Improved the dispersiveness of nanoparticle in macromolecule resin; The consistency and the bonding force of inorganic nano auxiliary agent and macromolecule resin have been improved; Make nanoparticle and macromolecule resin, inorganicly in nanometer range, combine, make to form chemical bonding force between two-phase interface, thereby can bring into play the nano effect and the synergistic effect of inorganic nano auxiliary agent with organic phase.Both can avoid the performance of nano material itself to can not get normal performance, influence modification result's problem, and make the production of nano-material modified starch-base biodegradation matrix material have practical value again.
Moreover, the present invention also has the following advantages:
1, because the composite modifier that starch that the present invention adopts and inorganic nano photochemical catalysis auxiliary agent make; Not only can realize the high filling of starch; Reduce cost, also can act synergistically, realize the complete controlled degradation of plastics with photochemical catalysis inorganic nano auxiliary agent; And the degraded product environmentally safe, thereby be the friendly product of a kind of novel environmental.
2, because the present invention is the starch-based nano composite modifying agent that can improve the plastics degradation property for preparing through extrusion by melting; Thereby it is simple not only to prepare process; Easy handling; Help realizing the large-scale industrial production application, and this properties-correcting agent also can be used for the modification of multiple plastics.
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, visible its serious agglomeration from figure.
Fig. 2 amplifies 7.27 ten thousand times transmission electron microscope shape appearance figure for the nano-cerium oxide particle that does not carry out surface-treated, and visible its reunion is also very serious from figure.
Fig. 3 is that the inorganic nano auxiliary agent after the inventive method surface-treated amplifies the ESEM shape appearance figure of 20,000 times dispersion state in composite modifier, and the nanoparticle from figure after the visible surface modification is uniformly dispersed in composite modifier.
Fig. 4 is the infrared test spectrogram of PVA/ anatase-type nanometer titanium dioxide matrix material; Solid line and dotted line are respectively not add anatase-type nanometer titanium dioxide and added anatase-type nanometer titanium dioxide ir spectra afterwards among the figure; Can find out that from test result the dotted line spectral line is at 500-750cm
-1Between the absorption peak of Ti-O-Ti in the very wide anatase-type nanometer titanium dioxide has appearred.
Fig. 5 is the uv-visible absorption spectroscopy figure of pure PVA and starch-based nano-photo catalytic composite degradation properties-correcting agent provided by the invention; In the scope of 200～400nm; Pure PVA film does not have to absorb to UV-light basically, and the highest ultraviolet absorptivity that has added the composite degradation properties-correcting agent of inorganic nano auxiliary agent has reached 0.59.
Fig. 6 is the secondary temperature elevation melting curve part of differential scanning calorimeter figure of polyvinyl alcohol composite material of having added the anatase-type nanometer titanium dioxide of different content.
Fig. 7 is the decrease temperature crystalline curved portion of differential scanning calorimeter figure of polyvinyl alcohol composite material of having added the anatase-type nanometer titanium dioxide of different content; Can find out from Fig. 6 and Fig. 7; Raising along with the anatase-type nanometer titanium dioxide addition; The Tc of matrix material raises to some extent, and fusing point then slightly reduces, and this has just greatly improved the melt-processable of Z 150PH.
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 each embodiment and the used material of application examples be weight part.
Be that the anatase-type nanometer titanium dioxide of 30～50nm and the nano-cerium oxide of 30～50nm are put in the superhigh speed mixing machine for each 25 parts with particle diameter earlier; Stirred 30 minutes down at 3000 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 2 hours; Suction filtration then, powder is put into ball mill ball mill pulverizing at least 1 hour again in 100 ℃ of oven dry.
Nano assistant after the surface-treated that obtains is passed through colloidal mill with 20 parts of triethyl citrates for 2 parts to be disperseed 2 hours; Then with 80 parts of Starch rices, 1799 15 parts of Z 150PH and four (β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid) in 1 part of input high-speed mixer of pentaerythritol ester inhibitor, 80 ℃ of temperature, rotating speed stirs 20min down for 100 rev/mins; Discharging gets final product melt extruding granulation in its adding twin screw extruder again.150 rev/mins of screw speeds, screw extrusion press is respectively distinguished temperature and is set at: 115 ℃ of feeding sections, 150 ℃ of compression sections, 175 ℃ of metering zones, 180 ℃ of head sections.
Be that the nano-cerium oxide of 30～50nm is put in the superhigh speed mixing machine for 30 parts earlier with particle diameter; Stirred 20 minutes down at 4000 rev/mins, the mixed solution with 50 parts of 0.5 part of γ-aminopropyl methyldiethoxysilane and absolute ethyl alcohols divides 2 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.
7 parts of 3 parts of polyoxyethylene poly-oxygen propylene aether segmented copolymers and ethanoyl tri-n-butyl citrates with 1 part of nano assistant after the surface-treated that obtains and relative molecular weight being 1000g/mol disperseed 1.5 hours through colloidal mill; Then with 17 parts of 30 parts of 50 parts of W-Gums, green starch, 1799 Z 150PH and 2; 2 '-methylene-bis (4-methyl-6-tert butyl phenol) 0.5 part of input high-speed mixer of inhibitor in; 70 ℃ of temperature; Rotating speed stirs 20min down for 150 rev/mins, and discharging gets final product melt extruding granulation in its adding twin screw extruder again.120 rev/mins of screw speeds, screw extrusion press is respectively distinguished temperature and is set at: 110 ℃ of feeding sections, 160 ℃ of compression sections, 180 ℃ of metering zones, 185 ℃ of head sections.
Embodiment 3 (embodiment 3 of corresponding packing bag)
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 2000g/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.
Embodiment 4
Be that the anatase-type nanometer titanium dioxide of 30～50nm is put in the superhigh speed mixing machine for 40 parts earlier with particle diameter; Stirred 30 minutes down at 3500 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 110 ℃ of oven dry.
With 1 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, triethyl citrates and the ethanoyl tri-n-butyl citrates of 1500g/mol disperseed 1 hour through colloidal mill; Then with 27 parts of 30 parts of W-Gums, 30 parts of yam starchs, green starch, 1799 10 parts of Z 150PH, four (β-(3; The 5-di-tert-butyl-hydroxy phenyl) 0.5 part of pentaerythritol ester, 2 propionic acid); 2 '-0.5 part of methylene-bis (4-methyl-6-tert butyl phenol) and 2, three kinds of inhibitors of three grades of butyl of 6--4-methylphenol and two (3, three grades of butyl of 5--4-hydroxy phenyl) 0.5 part of grade of thioether drop in the high-speed mixer; 80 ℃ of temperature; Rotating speed stirs 20min down for 200 rev/mins, and discharging gets final product melt extruding granulation in its adding twin screw extruder again.90 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.
Embodiment 5
Earlier be mixed crystal type nanometer titanium dioxide (P25 that German Evonik Degussa company produces, the specific surface area 50 ± 15m of 20～30nm with particle diameter
2/ g, wherein anatase-type nanometer titanium dioxide content is 80%) 50 parts put in the superhigh speed mixing machine, stirred 15 minutes down at 4000 rev/mins; Mixed solution with 100 parts of 1.5 parts of γ-aminopropyl methyldiethoxysilane and absolute ethyl alcohols divides 2 addings therebetween; After adding, continue ultra-high speed and mixed 1.5 hours, then suction filtration; Powder is put into ball mill ball mill pulverizing at least 1 hour again in 120 ℃ of oven dry.
With 16 parts of 0.2 part of nano assistant after the surface-treated that obtains and triethyl citrates and relative molecular weight is that 4 parts of the polyoxyethylene poly-oxygen propylene aether segmented copolymers of 4000g/mol disperseed 1.5 hours through colloidal mill; Then with 10 parts of 40 parts of 47 parts of W-Gums, yam starch, 1799 Z 150PH, 2; 2 '-methylene-bis (4-methyl-6-tert butyl phenol) 1 part of inhibitor and four (β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid) in 0.5 part of input high-speed mixer of pentaerythritol ester inhibitor, 65 ℃ of temperature, rotating speed stirs 10min down for 150 rev/mins; Discharging gets final product melt extruding granulation in its adding twin screw extruder again.120 rev/mins of screw speeds, screw extrusion press is respectively distinguished temperature and is set at: 110 ℃ of feeding sections, 160 ℃ of compression sections, 180 ℃ of metering zones, 185 ℃ of head sections.
Embodiment 6
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.
Embodiment 7
Earlier be mixed crystal type nanometer titanium dioxide (P25 that German Evonik Degussa company produces, the specific surface area 50 ± 15m of 20～30nm with particle diameter
2/ g, wherein anatase-type nanometer titanium dioxide content is 80%) 50 parts put in the superhigh speed mixing machine, stirred 20 minutes down at 4000 rev/mins; Mixed solution with 80 parts of 1 part of γ-aminopropyl methyldiethoxysilane and absolute ethyl alcohols divides 2 addings therebetween; After adding, continue ultra-high speed and mixed 1.5 hours, then suction filtration; 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 10 parts of 5 parts of polyoxyethylene poly-oxygen propylene aether segmented copolymers, ethanoyl tri-n-butyl citrates and the triethyl citrates of 1000g/mol disperseed 2 hours through colloidal mill; Then with 75 parts of W-Gums, 1799 15 parts of Z 150PH, four (β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid) in 0.5 part of input high-speed mixer of pentaerythritol ester 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.
Application examples 1
With embodiment 6 gained composite modifiers, 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 thickness of prepared packing bag is 0.035mm; It is 19.65MPa that mechanical property records its transverse tensile strength according to GB/T 1040.3-2006 standard; The cross break elongation is 558.47%; Transverse modulus of elasticity is 650.12MPa; Longitudinal tensile strength is 26.63MPa, and the longitudinal fracture elongation is 491.13%, and longitudinal modulus of elasticity is 699.58MPa; Degradation property according to GB/T 19227-2003 test is: it is 10.14% that soil buries 40 days weightlessness, and it is 62.16% that soil buries 200 days weightlessness.
Application examples 2
In embodiment 7 gained composite modifiers, 22 parts of Z 150PH, 2-hydroxyl-1 part of 4-methoxy benzophenone and 1 part of adding planetary stirring machine of maleic anhydride of 1799; At normal temperatures; Mix with 70 rev/mins; Put into single screw rod then and extrude inflation film manufacturing machine and under 175 ℃, carry out hot melt blowing film forming, cut at last and pack.The thickness of prepared mulch film is 0.012mm; It is 14.1MPa that mechanical property records its transverse tensile strength according to GB/T 1040.3-2006 standard, and longitudinal tensile strength is 15.9MPa; It is 83.1% that transmittance records it according to GB/T 2410-80 standard; Degradation property records its soil according to GB/T20197-2006, and to bury 30 days weightlessness be 11.67%, and it is 38.69% that soil buries 120 days weightlessness.
Claims (10)
1. starch-based nano-photo catalytic composite degradation properties-correcting agent, this properties-correcting agent is made up of through melt blending following raw material 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, mixed crystal type nanometer titanium dioxide and the nano-cerium oxide, and its particle diameter is 1～100nm.
2. starch-based nano-photo catalytic composite degradation properties-correcting agent according to claim 1, the starch described in this properties-correcting agent are at least a in Starch rice, W-Gum, green starch, Rhizoma Nelumbinis starch and the yam starch.
3. starch-based nano-photo catalytic composite degradation properties-correcting agent according to claim 1 and 2, the small molecules softening agent described in this properties-correcting agent are 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.
4. starch-based nano-photo catalytic composite degradation properties-correcting agent according to claim 1 and 2, the anatase-type nanometer titanium dioxide in the mixed crystal type nanometer titanium dioxide described in this properties-correcting agent is at least 75%.
5. starch-based nano-photo catalytic composite degradation properties-correcting agent according to claim 3, the anatase-type nanometer titanium dioxide in the mixed crystal type nanometer titanium dioxide described in this properties-correcting agent is at least 75%.
6. the preparation method of the described starch-based nano-photo catalytic of claim 1 a composite degradation properties-correcting agent, the process step and the condition of this method are following:
(1) earlier the inorganic nano auxiliary agent is put in the superhigh speed mixing machine for 30～50 parts; 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 extrudes granulation under 175～190 ℃ of the temperature and get final product 100～200 rev/mins of screw speeds,
Add each material umber be weight part, and inorganic nano auxiliary agent wherein is in anatase-type nanometer titanium dioxide, mixed crystal type nanometer titanium dioxide or the nano-cerium oxide any.
7. the preparation method of starch-based nano-photo catalytic composite degradation properties-correcting agent 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 7 described starch-based nano-photo catalytic composite degradation properties-correcting agent, 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 7 described starch-based nano-photo catalytic composite degradation properties-correcting agent, the anatase-type nanometer titanium dioxide in the mixed crystal type nanometer titanium dioxide described in this preparation method is at least 75%.
10. the preparation method of starch-based nano-photo catalytic composite degradation properties-correcting agent according to claim 8, the anatase-type nanometer titanium dioxide in the mixed crystal type nanometer titanium dioxide described in this preparation method is at least 75%.
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