CN103865106A - Biodegradable plastic with high starch content and preparation method of biodegradable plastic - Google Patents
Biodegradable plastic with high starch content and preparation method of biodegradable plastic Download PDFInfo
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- CN103865106A CN103865106A CN201410125992.0A CN201410125992A CN103865106A CN 103865106 A CN103865106 A CN 103865106A CN 201410125992 A CN201410125992 A CN 201410125992A CN 103865106 A CN103865106 A CN 103865106A
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Abstract
The invention discloses a biodegradable plastic with high starch content and a preparation method of the biodegradable plastic. The preparation method comprises the steps: with corn starch, potato starch and other natural plant starches as main raw materials, completely biodegradable polyvinyl alcohol as a main toughening agent and polyethylene glycol as an auxiliary toughening agent, adding an environment-friendly composite plasticizer and a processing acid, and mixing all the components to obtain the biodegradable plastic with high starch content. The biodegradable plastic with high starch content, prepared by the invention, contains at most 90wt% of starch, has favorable plasticity and machinability, and can be prepared into products such as pipes, sheets, profiles, films, vessels, foamed base materials and the like with various shapes by using the traditional polymer forming and machining method.
Description
Technical field
The invention belongs to biodegradable plastic and the preparing technical field thereof of high-content of starch, be specifically related to a kind of biodegradable plastic and preparation method of high-content of starch.
Background technology
In recent years, environmental problem and energy dilemma that a lot of petroleum-type synthesized polymer materials bring are day by day serious, and for the long-term harmonious development of environment and economy, global each state has all strengthened research and the dynamics of investment to degradative plastics.Develop biodegradable environmentally-friendly plastic and can fundamentally alleviate " white pollution " problem while save energy effectively.Compared with other biological degradation polyalcohol, starch has the advantages such as wide material sources, cheap and fully biodegradable, thereby has consequence in Biodegradable material field.
The full-starch plastics of early-stage development is by ative starch and simple mixing of petroleum resinoid matrix obtaining goods, starch content is 5～30wt%, because the main component of such plastics remains petroleum base resin, it is century-old on degradable needs that this part resin reaches, and is therefore eliminated very soon; Develop starch/synthetic polymer blended plastic the nineties in 20th century, by ative starch is carried out physics or chemical modification process after again with resin graft-blending, starch content can reach 60wt%, but the processing characteristics of this plastics and use properties are all not ideal enough, and, expensive 2～3 times than existing petroleum-based plastics of its costs.Although alleviated to a certain extent the pollution of plastic refuse to environment, because resin matrix used remains non-degradable resin, therefore fundamentally do not solve " white pollution " problem.(Qiu Weiyang, Wang Feidi, Qiu Xianhua etc. starch plastic present situation and development prospect, polymer circular, 2000,4:77～82; Guo Zhenyu, Hu Shiwei, fourth work is bright etc. the progress of Starch-base Degradable Plastic, additives for plastics, 2011,6:16～21)
For overcoming the deficiency of above-mentioned two kind of starch degradative plasticss, simultaneously also in order to prepare the starch plastics of Wholly-degradable truly, people started to attempt preparing the biological heat plasticity degradative plastics of high-content of starch in recent years, guarantee the content of starch higher (70～100wt%) in material, a small amount of other materials that simultaneously add also can be degradable.Its final purpose is to make material have the character of Plastic Resin, both can carry out thermoplastic processing, again can be fast, fully in physical environment, degrade.Meanwhile, because starch can obtain from the farm crop such as corn, wheat, sweet potato and potato, and this measure also can open up starch high value added product market, can effectively promote rural economy fast development.Therefore, the biological plastics of high-content of starch, after direct full-starch plastics and commixed type starch plastic are eliminated in succession, becomes the focus in starch plastics area research, is also to have most one of biodegradable plastic of development prospect.
At present abroad, SUMITOMO CHEMICAL Itochu, Warner-lambert company of the U.S. and Italian Novamont company etc. declare successfully to work out the biological plastics of starch-containing amount at 90%～100% high-content of starch, fully biodegradable in one month to 1 year and do not stay any vestige, pollution-free, can be used for manufacturing various containers, Bottle & Can, film and refuse bag etc.The research of related fields is with the comparatively forward position of research of Japan, Italy and the U.S. in the world.But due at present high cost or modified technique complexity, not yet realize large-scale application (He little Wei, Luo Zhigang. the progress of starch-based degradable plastics, food research and development, 2005,26 (5): 196～200; Qiu Weiyang, Qiu Xianhua, explains the literary composition that continues. domestic Biodegradable starch plastic status and prospectives, 2003,31 (4): 1～3).And the research of the domestic starch plastic to fully biodegradable rests on fundamental research or laboratory stage more, Jin You minority unit claims that Development and Production goes out the thermoplastic starch plastic of fully biodegradable, can be for the production of film, sheet material, but still fewer about the report of its industrialization and product application aspect.Application number is respectively 200310111110.7,
201010104693.0, to select modified starch be main raw material for 200410011338.3 Chinese patent, successfully prepared the Starch-base Degradable Plastic of starch content >=80wt% in conjunction with graft reaction or other kinds softening agent, but because selected starch material is the modified starch of natural plant starch gained after denaturing treatment, thereby increase to a certain extent the technology degree of dependence to raw material itself, make the technological process of preparation more complicated, also increased cost simultaneously.
Accordingly, the present invention prepares the biodegradable plastic of high-content of starch by a kind of novel more simple and effective approach, utilize a kind of novel compound Plasticising system directly natural plant starch to be carried out to plasticization and modification, and the toughness reinforcing synergy to starch in conjunction with multiple toughner effectively, thereby effectively reduce " bring back to life " " migration " phenomenon of phenomenon and small molecules softening agent of starch that conventional plasticizers causes, realize the optimization of the biological plastics performance of high-content of starch.
Summary of the invention
The object of the invention is the defects such as and presently used partially modified auxiliary agent inadequate environmental protection higher for the difficult plasticizing of the biological plastics of current high-content of starch, difficult processing, product poor mechanical property, poor water resistance, cost, non-degradable, a kind of biodegradable plastic that adopts the prepared high-content of starch of NEW TYPE OF COMPOSITE Plasticising system is provided;
Another object of the present invention is to provide the preparation method of the biodegradable plastic of this high-content of starch.
The present invention solves its technical problem and takes following technical scheme to realize:
A kind of biodegradable plastic of high-content of starch, comprise the processing aid of natural plant starch, major-minor two kinds of toughner, environmental protection class composite elasticizer and environmental protection, its weight fraction is than as follows: the processing aid 1～4wt% of natural plant starch 70～90wt%, major-minor two kinds of toughner 1～15wt%, environmental protection class composite elasticizer 1～20wt%, environmental protection.
And described natural plant starch is W-Gum, yam starch, konjak starch, pea starch, tapioca (flour), sweet potato starch one or more in rice starch early.
And described major-minor two kinds of toughner can be formulated in any proportion, wherein, the polyvinyl alcohol that main toughner is Wholly-degradable, its polymerization degree scope is 500～2400, alcoholysis degree is 88%～99%; Auxiliary toughner is the polyoxyethylene glycol of Wholly-degradable, and its molecular weight is 2000～20000.
And, described environmental protection class composite elasticizer is to be configured and form in any proportion by alcohol acid compounds, glycerine, sorbyl alcohol and polyoxyethylene glycol, wherein, alcohol acid compounds is one or more in citric acid, oxyacetic acid, oxyacetic acid, hydroxybutyric acid, glycolic acid, lactic acid, oxysuccinic acid, tartrate, and the molecular weight that is used as the polyoxyethylene glycol of softening agent is 200～2000.
And, the processing aid of described environmental protection comprises lubricant, tensio-active agent, coupling agent, oxidation inhibitor and whipping agent, wherein, lubricant is epoxy soybean oil, aliphatic carboxylic acid, aliphatic amide, aliphatic carboxylic acid metal-salt, one or more in whiteruss, tensio-active agent is polysorbate60, tween 80, one or more in sodium lauryl sulphate, coupling agent is silane coupling agent, titante coupling agent, one or more in aluminate coupling agent, oxidation inhibitor is 1010, 168, 626, one or more in DTBHQ and 264, whipping agent is ethylene glycol, water, in citric acid/carbonate mixture one or more.
A preparation method for the biodegradable plastic of high-content of starch, comprises that step is as follows:
(1) raw material is prepared; Each material of mark ratio is as follows by weight: the processing aid 1～4wt% of natural plant starch 70～90wt%, major-minor two kinds of toughner 1～15wt%, environmental protection class composite elasticizer 1～20wt%, environmental protection, wherein, major-minor two kinds of toughner can be formulated in any proportion, main toughner is the polyvinyl alcohol of Wholly-degradable, the polyoxyethylene glycol that auxiliary toughner is Wholly-degradable; Wherein, the processing aid of environmental protection comprises lubricant, tensio-active agent, coupling agent, oxidation inhibitor and whipping agent;
(2) natural plant starch and the polyvinyl alcohol that contains polyoxyethylene glycol are placed in high-speed mixer at the temperature of 60～90 ℃ and 30～95 ℃ and mix respectively 1～40min and 1～40min with environmental protection class composite elasticizer, lubricant respectively, powder is taken out in cooling, can obtain the just first mixed thing of mixed thing and polyvinyl alcohol of natural plant starch;
(3) by the natural plant starch obtaining in (2) just the first mixed thing of mixed thing and polyvinyl alcohol be placed in respectively and at 65～70 ℃ of temperature and at 65～80 ℃ of temperature, leave standstill 30～72h time and 0.5～4h;
(4) natural plant starch after leaving standstill in (3) is just joined to high-speed mixer together with the first mixed thing of mixed thing and polyvinyl alcohol, add the processing aid of environmental protection class composite elasticizer and environmental protection simultaneously, mix 3～30min time at 20～70 ℃ of temperature after, cooling is taken out, and obtains natural plant starch/polyvinyl alcohol pre-composition of elementary plasticizing;
(5) natural plant starch/polyvinyl alcohol pre-composition of gained in (4) is directly joined in Banbury mixer or twin screw extruder and further shear blend, obtain the biodegradable plastic particle of the good high-content of starch of final plasticity-through granulation;
(6) by the biodegradable plastic particle of the high-content of starch of gained in (5) through extruding, the moulding process of injection moulding, blowing, hot pressing prepares tubing, sheet material, profiled material, film, container, foamed substrate product.
And the temperature of Banbury mixer is 80～160 ℃ in described step (4), the banburying time is 0.5～2h, Banbury mixer rotating speed 10～80r/min; The temperature of described twin screw extruder is 50～200 ℃, and the time is 0～30min, screw speed 10～120r/min.
Advantage of the present invention and positively effect are:
1, the present invention be directed to natural plant starch and carry out the biodegradable plastic that high-content of starch is prepared in direct plastication modification.With take treated starch compared with raw material, the preparation technology of this method is more simple, cost is cheaper.Owing to can selecting all natural plant starch on the market, and the high-content of starch can reach 90wt%, and its price is even low by 20%～50% than the price of common plastics, all has very tempting price competitiveness outward at Present Domestic, thereby there is larger market potential, also more easily apply.
2, the biodegradable plastic of the prepared high-content of starch of the present invention, compared with many traditional starch plasticses, the raw material using in these plastics and each analog assistant all belong to totally biodegradable type, not containing any nondegradable petroleum base resin composition, be totally biodegradable plastics truly, thereby have more and have broad application prospects.
3, the preparation technology of the biodegradable plastic of above-mentioned high-content of starch provided by the present invention is simple, is easy to control, and less demanding to equipment, can industrialization, and reduced investment.
4, the biodegradable plastic of the prepared high-content of starch of the present invention can be through extruding, injection moulding, blown film, hot pressing etc. be prepared into all kinds of tubing, sheet material, profiled material, film, container, foamed substrate etc., effectively widened the range of application of the biodegradable plastic of high-content of starch.
5, the biodegradable plastic of the prepared high-content of starch of the present invention has good thermoplasticity and processibility, the mechanical property of various product is very excellent, its tensile strength, elongation at break are very high, alternative traditional petroleum-based plastics is as the use of resin in association area such as polyethylene (PE), polypropylene (PP), be expected to solve veritably the problem of " white pollution ", there are wide market outlook.
6, because the preparation technology of the biodegradable plastic of high-content of starch provided by the invention is very simple and easy, be applicable to the machine-shaping device of all traditional petroleum-based plastics, thereby production cost is low, production efficiency is high, simply controlled, equipment and instrument complexity, technology controlling and process difficulty, the operating process of effectively having avoided prior art to cause be various, produce the problems such as line length.
Embodiment
Below the invention process is further described, following examples are descriptive, are not determinate, can not limit protection scope of the present invention with this.
Embodiment 1
The biodegradable plastic of high-content of starch and a preparation method, component and preparation method that this biodegradable plastic comprises by quality are as follows:
(1) taking 45kg W-Gum, 0.5kg glycerine, 0.4kg polyoxyethylene glycol (PEG) 200,0.05kg stearic acid, 0.1kg Magnesium Stearate, 0.1kg epoxy soybean oil joins successively in the large high-speed mixing machine that has been preheated to 70 ℃ and mixes 10min in mixing machine, stirring at low speed is also cooled to room temperature, discharging, packing, obtain just mixed thing of W-Gum.Simultaneously, take 2kg polyvinyl alcohol (PVA) 1788,0.5kg, PEG4000,0.1kg glycerine, 0.1kgPEG200,0.05kg stearic acid join successively in the miniature high-speed mixing machine of 30 ℃ and mix 6min, and stirring at low speed is also cooled to room temperature, discharging, packing, obtain just mixed thing of PVA.
(2) by the W-Gum obtaining in (1) just mixed thing and PVA just mixed thing be placed in respectively at 50 ℃ and 70 ℃ standing 24h and 1h separately;
(3) by the W-Gum after leaving standstill in (2), just mixed thing and PVA just join high-speed mixer together with mixed thing, add 1kg citric acid, 0.10kg polysorbate60,0.075kg Silane coupling agent KH550,0.05kg antioxidant 1010 simultaneously, mix 10min at 30 ℃ after, cooling is taken out, and obtains W-Gum/PVA pre-composition of elementary plasticizing;
(4) W-Gum/PVA pre-composition of gained in (3) is directly joined in Banbury mixer or twin screw extruder and further shear blend, directly extruding pelletization, obtains the biodegradable plastic particle of the good high-content of starch of final plasticity-;
(5) the biodegradable plastic particle of the high-content of starch of gained in (4) is made to all kinds of films and wallpaper substrate product through blow moulding process respectively.
Embodiment 2
The biodegradable plastic of high-content of starch and a preparation method, component and preparation method that this biodegradable plastic comprises by quality are as follows:
(1) taking 40kg yam starch, 3.1kg glycerine, 1.1kgPEG200,0.55kg sorbyl alcohol, 0.05kg whiteruss, 0.08kg stearic acid, 0.1kg amine hydroxybenzene joins successively in the large high-speed mixing machine that has been preheated to 60 ℃ and mixes 15min in mixing machine, stirring at low speed is also cooled to room temperature, discharging, packing, obtain just mixed thing of yam starch.Simultaneously, take in the miniature high-speed mixing machine that 0.4kgPVA2092,0.1kgPEG2000,3.025kg glycerine, 1.025kgPEG200,0.02kg stearic acid join 70 ℃ successively and mix 3min, stirring at low speed is also cooled to room temperature, and discharging, packing obtain just mixed thing of PVA.
(2) the first batch mixing of the yam starch obtaining in (1) and PVA is placed in respectively at 55 ℃ and 68 ℃ and leaves standstill separately 36h and 0.5h;
(3) yam starch after leaving standstill in (2) is joined to high-speed mixer together with the first batch mixing of PVA, add 0.2kg citric acid, 0.125kg polysorbate60,0.10kg silane coupling agent KH560,0.025kg antioxidant 1010 simultaneously, mix 30min at 20 ℃ after, cooling is taken out, and obtains yam starch/PVA pre-composition of elementary plasticizing;
(4) yam starch/PVA pre-composition of gained in (3) is directly joined in Banbury mixer or twin screw extruder and further shear blend, directly extruding pelletization, obtains the biodegradable plastic particle of the good high-content of starch of final plasticity-.
(5) the biodegradable plastic particle of the high-content of starch of gained in (4) is made to all kinds of films and wallpaper substrate product through blow moulding process respectively.
Embodiment 3
The biodegradable plastic of high-content of starch and a preparation method, component and preparation method that this biodegradable plastic comprises by quality are as follows:
(1) taking the two hard acid amides (EBS) of 38.3kg pea starch, 3.25kg glycerine, 0.04kgPEG400,0.10kg epoxy soybean oil, 0.08kg stearic acid, 0.05kg ethylene joins successively in the large high-speed mixing machine that has been preheated to 75 ℃ and mixes 12min in mixing machine, stirring at low speed is also cooled to room temperature, discharging, packing, obtain just mixed thing of pea starch.Simultaneously, take 0.75kgPVA1795,0.5kgPEG8000,1.3kg glycerine, 0.01kgPEG400,0.02kg stearic acid joins the miniature high-speed mixing machine mixing 2min that has been preheated to 52 ℃ successively, stirring at low speed is also cooled to room temperature, and discharging, packing obtain just mixed thing of PVA.
(2) the first batch mixing of the pea starch obtaining in (1) and PVA is placed in respectively at 60 ℃ and 78 ℃ and leaves standstill separately 48h and 3h;
(3) pea starch after leaving standstill in (2) is joined to high-speed mixer together with the first batch mixing of PVA, add 0.2kg citric acid, 0.15 oxysuccinic acid, 0.1kg tween 80,0.14kg titante coupling agent, 0.03kg oxidation inhibitor DTBHQ simultaneously, mix 10min at 40 ℃ after, cooling is taken out, and obtains pea starch/PVA pre-composition of elementary plasticizing;
(4) pea starch/PVA pre-composition of gained in (3) is directly joined in Banbury mixer or twin screw extruder and further shear blend, directly extruding pelletization, obtains the biodegradable plastic particle of the good high-content of starch of final plasticity-.
(5) the biodegradable plastic particle of the high-content of starch of gained in (4) is made to all kinds of films and wallpaper substrate product through blow moulding process.
Embodiment 4
The biodegradable plastic of high-content of starch and a preparation method, component and preparation method that this biodegradable plastic comprises by quality are as follows:
(1) taking 41.5kg yam starch, 3.0kg glycerine, 0.75kg sorbyl alcohol, 0.065kgPEG400,0.25kg whiteruss, 0.095kg stearic acid, 0.1kg epoxy soybean oil joins successively in the large high-speed mixing machine that has been preheated to 78 ℃ and mixes 15min in mixing machine, stirring at low speed is also cooled to room temperature, discharging, packing, obtain just mixed thing of yam starch.Simultaneously, take 2kgPVA1799,1.5kgPEG6000,0.05kg sorbyl alcohol, 0.035kgPEG400,0.02kg stearic acid joins successively in the miniature high-speed mixing machine that has been preheated to 85 ℃ and mixes 2min, stirring at low speed is also cooled to room temperature, and discharging, packing obtain just mixed thing of PVA.
(2) the first batch mixing of the yam starch obtaining in (1) and PVA is placed in respectively at 65 ℃ and 82 ℃ and leaves standstill separately 60h and 0.5h;
(3) yam starch after leaving standstill in (2) is joined to high-speed mixer together with the first batch mixing of PVA, add 0.175kg citric acid, 0.175 glycolic acid, 0.1kg sodium lauryl sulphate, 0.07kg aluminate coupling agent, 0.06kg antioxidant 264 simultaneously, mix 18min at 25 ℃ after, cooling is taken out, and obtains yam starch/PVA pre-composition of elementary plasticizing;
(4) yam starch/PVA pre-composition of gained in (3) is directly joined in Banbury mixer or twin screw extruder and further shear blend, directly extruding pelletization, obtains the biodegradable plastic particle of the good high-content of starch of final plasticity-.
(5) in apparatus for blow moulding, carry out foamed blow moldedly online by joining together with the biodegradable plastic particle of high-content of starch of gained in (4) and citric acid/sodium bicarbonate mixture of 0.05kg, make the expansion type wallpaper substrate product that all kinds of proportion is lower.
Embodiment 5:
The biodegradable plastic of high-content of starch and a preparation method, component and preparation method that this biodegradable plastic comprises by quality are as follows:
(1) taking 40kg konjak starch, 0.75kg sorbyl alcohol, 3.0kg glycerine, 0.17kgPEG600,0.15kg whiteruss, 0.095kg epoxy soybean oil joins successively in the large high-speed mixing machine that has been preheated to 85 ℃ and mixes 20min in mixing machine, stirring at low speed is also cooled to room temperature, discharging, packing, obtain just mixed thing of konjak starch.Simultaneously, take in the miniature high-speed mixing machine that 3.4kgPVA2092,0.1kgPEG6000,0.5kg sorbyl alcohol, 0.08kgPEG600,0.02kg epoxy soybean oil join 60 ℃ successively and mix 5min, stirring at low speed is also cooled to room temperature, and discharging, packing obtain just mixed thing of PVA.
(2) the first batch mixing of the konjak starch obtaining in (1) and PVA is placed in respectively at 68 ℃ and 80 ℃ and leaves standstill separately 72h and 1.5h;
(3) konjak starch after leaving standstill in (2) is joined to high-speed mixer together with the first batch mixing of PVA, add 0.5kg oxysuccinic acid, 1kg tartrate, 0.05kg polysorbate60,0.1kg Silane coupling agent KH550,0.05kg oxidation inhibitor DTBHQ simultaneously, mix 3min at 70 ℃ after, cooling is taken out, and obtains konjak starch/PVA pre-composition of elementary plasticizing;
(4) konjak starch/PVA pre-composition of gained in (3) is directly joined in Banbury mixer or twin screw extruder and further shear blend, directly extruding pelletization, obtains the biodegradable plastic particle of the good high-content of starch of final plasticity-.
(5) the biodegradable plastic particle of the high-content of starch of gained in (4) is made to the blister-type container that all kinds of proportion is lower through injection moulding and vacuum suction moulding.
Embodiment 6:
The biodegradable plastic of high-content of starch and a preparation method, component and preparation method that this biodegradable plastic comprises by quality are as follows:
(1) taking 20.5kg yam starch, 17kg W-Gum, 2.20kg glycerine, 1.20kg sorbyl alcohol, 0.1kgPEG1000,0.05kg calcium stearate, 0.085kg stearic acid, 0.1kg epoxy soybean oil joins successively in the large high-speed mixing machine that has been preheated to 90 ℃ and mixes 35min in mixing machine, stirring at low speed is also cooled to room temperature, discharging, packing, obtain just mixed thing of potato/W-Gum.Simultaneously, take 3.8kgPVA1788,2.2kgPEG8000,2.1kg glycerine, 0.1kgPEG1000,0.04kg stearic acid joins successively in the miniature high-speed mixing machine that has been preheated to 95 ℃ and mixes 2min, stirring at low speed is also cooled to room temperature, and discharging, packing obtain just mixed thing of PVA.
(2) the first batch mixing of the potato/W-Gum obtaining in (1) and PVA is placed at 70 ℃ and leaves standstill separately 30h and 2h;
(3) potato/W-Gum after leaving standstill in (2) is joined to high-speed mixer together with the first batch mixing of PVA, add 0.3kg oxysuccinic acid, 0.05kg sodium lauryl sulphate, 0.10kg Silane coupling agent KH550,0.025kg irgasfos 168 simultaneously, mix 8min at 40 ℃ after, cooling is taken out, and obtains yam starch/corn/PVA pre-composition of elementary plasticizing;
(4) potato/W-Gum/PVA pre-composition of gained in (3) is directly joined in Banbury mixer or twin screw extruder and further shear blend, directly extruding pelletization, obtains the biodegradable plastic particle of the good high-content of starch of final plasticity-.
(5) by joining together with the biodegradable plastic particle of high-content of starch of gained in (4) and the ethylene glycol of 0.05kg, in hot-press forming device, to carry out online foaming heat molded, makes the foamed substrate that all kinds of proportion is lower.
Embodiment 7
The biodegradable plastic of high-content of starch and a preparation method, component and preparation method that this biodegradable plastic comprises by quality are as follows:
(1) taking 27kg yam starch, 9.5kg pea starch, 3.15kg glycerine, 0.15kg sorbyl alcohol, 0.08kgPEG2000,0.15kg Magnesium Stearate, 0.15kg stearic acid, 0.15kg epoxy soybean oil joins successively in the large high-speed mixing machine that has been preheated to 78 ℃ and mixes 30min, stirring at low speed is also cooled to room temperature, discharging, packing, obtain just mixed thing of potato/pea starch.Simultaneously, take 5.5kgPVA1792,0.5kgPEG4000,2.10kg glycerine, 0.02kgPEG2000,0.05kg stearic acid joins successively in the miniature high-speed mixing machine that has been preheated to 58 ℃ and mixes 15min, stirring at low speed is also cooled to room temperature, and discharging, packing obtain just mixed thing of PVA.
(2) the first batch mixing of the potato/pea starch obtaining in (1) and PVA is placed at 68 ℃ and leaves standstill separately 40h and 4h;
(3) potato/pea starch after leaving standstill in (2) is joined to high-speed mixer together with the first batch mixing of PVA, add 0.5kg tartrate, 0.25kg sodium lauryl sulphate, 0.20kg titante coupling agent, 0.05kg oxidation inhibitor 626 simultaneously, mix 3min at 30 ℃ after, cooling is taken out, and obtains yam starch/pea/PVA pre-composition of elementary plasticizing;
(4) potato/pea starch/PVA pre-composition of gained in (3) is directly joined in Banbury mixer or twin screw extruder and further shear blend, directly extruding pelletization, obtains the biodegradable plastic particle of the good high-content of starch of final plasticity-.
(5) carry out online foam shaping by extrusion by joining in extrusion equipment together with the biodegradable plastic particle of high-content of starch of gained in (4) and the ethylene glycol of 0.05kg, make the extrusion foaming sheet material that all kinds of proportion is lower.
Embodiment 8
The biodegradable plastic of high-content of starch and a preparation method, component and preparation method that this biodegradable plastic comprises by quality are as follows:
(1) taking 20kg sweet potato starch, 15kg W-Gum, 4.45kg glycerine, 0.20kgPEG800,0.12kg stearic acid, 0.15kg amine hydroxybenzene joins successively in the large high-speed mixing machine that has been preheated to 70 ℃ and mixes 35min in mixing machine, stirring at low speed is also cooled to room temperature, discharging, packing, obtain just mixed thing of Ipomoea batatas/W-Gum.Simultaneously, take 5.0kgPVA2292,0.5kgPEG20000,2.30kg glycerine, 0.05kgPEG800,0.08kg stearic acid joins successively in the miniature high-speed mixing machine that has been preheated to 45 ℃ and mixes 35min, stirring at low speed is also cooled to room temperature, and discharging, packing obtain just mixed thing of PVA.
(2) the first batch mixing of the Ipomoea batatas/W-Gum obtaining in (1) and PVA is placed in respectively at 68 ℃ and 75 ℃ and leaves standstill separately 50h and 0.8h;
(3) Ipomoea batatas/W-Gum after leaving standstill in (2) is joined to high-speed mixer together with the first batch mixing of PVA, add 0.25kg hydroxybutyric acid, 0.75kg citric acid, 0.27kg sodium lauryl sulphate, 0.17kg aluminate coupling agent, 0.05kg antioxidant 264 simultaneously, mix 4min at 45 ℃ after, cooling is taken out, and obtains Ipomoea batatas/W-Gum/PVA pre-composition of elementary plasticizing;
(4) Ipomoea batatas/W-Gum/PVA pre-composition of gained in (3) is directly joined in Banbury mixer or twin screw extruder and further shear blend, directly extruding pelletization, obtains the biodegradable plastic particle of the good high-content of starch of final plasticity-.
(5) carry out online foam shaping by extrusion by joining in extrusion equipment together with the biodegradable plastic particle of high-content of starch of gained in (4) and citric acid/sodium carbonate mixture of 0.05kg, make the extrusion foaming sheet material that all kinds of proportion is lower.
Claims (7)
1. the biodegradable plastic of a high-content of starch, it is characterized in that: comprise the processing aid of natural plant starch, major-minor two kinds of toughner, environmental protection class composite elasticizer and environmental protection, its weight fraction is than as follows: the processing aid 1～4wt% of natural plant starch 70～90wt%, major-minor two kinds of toughner 1～15wt%, environmental protection class composite elasticizer 1～20wt%, environmental protection.
2. the biodegradable plastic of a kind of high-content of starch according to claim 1, is characterized in that: described natural plant starch is W-Gum, yam starch, konjak starch, pea starch, tapioca (flour), sweet potato starch one or more in rice starch early.
3. the biodegradable plastic of a kind of high-content of starch according to claim 1, it is characterized in that: described major-minor two kinds of toughner can be formulated in any proportion, wherein, main toughner is the polyvinyl alcohol of Wholly-degradable, its polymerization degree scope is 500～2400, and alcoholysis degree is 88%～99%; Auxiliary toughner is the polyoxyethylene glycol of Wholly-degradable, and its molecular weight is 2000～20000.
4. the biodegradable plastic of a kind of high-content of starch according to claim 1, it is characterized in that: described environmental protection class composite elasticizer is to be configured and form in any proportion by alcohol acid compounds, glycerine, sorbyl alcohol and polyoxyethylene glycol, wherein, alcohol acid compounds is one or more in citric acid, oxyacetic acid, oxyacetic acid, hydroxybutyric acid, glycolic acid, lactic acid, oxysuccinic acid, tartrate, and the molecular weight that is used as the polyoxyethylene glycol of softening agent is 200～2000.
5. the biodegradable plastic of a kind of high-content of starch according to claim 1, it is characterized in that: the processing aid of described environmental protection comprises lubricant, tensio-active agent, coupling agent, oxidation inhibitor and whipping agent, wherein, lubricant is epoxy soybean oil, aliphatic carboxylic acid, aliphatic amide, aliphatic carboxylic acid metal-salt, one or more in whiteruss, tensio-active agent is polysorbate60, tween 80, one or more in sodium lauryl sulphate, coupling agent is silane coupling agent, titante coupling agent, one or more in aluminate coupling agent, oxidation inhibitor is 1010, 168, 626, one or more in DTBHQ and 264, whipping agent is ethylene glycol, water, in citric acid/carbonate mixture one or more.
6. according to the preparation method of the biodegradable plastic of a kind of high-content of starch described in claim 1～5, it is characterized in that comprising that step is as follows:
(1) raw material is prepared; Each material of mark ratio is as follows by weight: the processing aid 1～4wt% of natural plant starch 70～90wt%, major-minor two kinds of toughner 1～15wt%, environmental protection class composite elasticizer 1～20wt%, environmental protection, wherein, major-minor two kinds of toughner can be formulated in any proportion, main toughner is the polyvinyl alcohol of Wholly-degradable, the polyoxyethylene glycol that auxiliary toughner is Wholly-degradable; Wherein, the processing aid of environmental protection comprises lubricant, tensio-active agent, coupling agent, oxidation inhibitor and whipping agent;
(2) natural plant starch and the polyvinyl alcohol that contains polyoxyethylene glycol are placed in high-speed mixer at the temperature of 60～90 ℃ and 30～95 ℃ and mix respectively 1～40min and 1～40min with environmental protection class composite elasticizer, lubricant respectively, powder is taken out in cooling, can obtain the just first mixed thing of mixed thing and polyvinyl alcohol of natural plant starch;
(3) by the natural plant starch obtaining in (2) just the first mixed thing of mixed thing and polyvinyl alcohol be placed in respectively and at 65～70 ℃ of temperature and at 65～80 ℃ of temperature, leave standstill 30～72h time and 0.5～4h;
(4) natural plant starch after leaving standstill in (3) is just joined to high-speed mixer together with the first mixed thing of mixed thing and polyvinyl alcohol, add the processing aid of environmental protection class composite elasticizer and environmental protection simultaneously, mix 3～30min time at 20～70 ℃ of temperature after, cooling is taken out, and obtains natural plant starch/polyvinyl alcohol pre-composition of elementary plasticizing;
(5) natural plant starch/polyvinyl alcohol pre-composition of gained in (4) is directly joined in Banbury mixer or twin screw extruder and further shear blend, obtain the biodegradable plastic particle of the good high-content of starch of final plasticity-through granulation;
(6) by the biodegradable plastic particle of the high-content of starch of gained in (5) through extruding, the moulding process of injection moulding, blowing, hot pressing prepares tubing, sheet material, profiled material, film, container, foamed substrate product.
7. the preparation method of the biodegradable plastic of a kind of high-content of starch according to claim 6, is characterized in that: in described step (4), the temperature of Banbury mixer is 80～160 ℃, and the banburying time is 0.5～2h, Banbury mixer rotating speed 10～80r/min; The temperature of described twin screw extruder is 50～200 ℃, and the time is 0～30min, screw speed 10～120r/min.
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| CN105694318A (en) * | 2015-09-18 | 2016-06-22 | 安徽柒柒塑业有限公司 | Biodegradable polyvinyl alcohol thin film |
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Application publication date: 20140618 |