CN103044717A - Method for preparing composite modified starch for biodegrading plastic - Google Patents
Method for preparing composite modified starch for biodegrading plastic Download PDFInfo
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- CN103044717A CN103044717A CN2012105361242A CN201210536124A CN103044717A CN 103044717 A CN103044717 A CN 103044717A CN 2012105361242 A CN2012105361242 A CN 2012105361242A CN 201210536124 A CN201210536124 A CN 201210536124A CN 103044717 A CN103044717 A CN 103044717A
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Abstract
The invention provides a method for preparing composite modified starch for biodegrading plastic, comprising: adding an activator in dry starch, for pretreatment under 95-100 DEG C for 30min; adding an esterification reagent into the starch after activation, for making esterification reaction under 120-125 DEG C for 1h, wherein the whole press is carried out in a solid phase state; adding a solid coupling agent into the material after esterification, for making a phase coating reaction in case of stirring under 125-130 DEG C for 40-50min, wherein the whole press is carried out in a solid phase state; cooling the material until to room temperature, screening the material with 60 mesh sieves, and then packaging the material to obtain the finished product.
Description
Technical field
The present invention relates to a kind of composite modified starch, particularly the preparation method of the composite modified starch of biodegradable plastic use.
Background technology
Along with the fast development of China's economy, the scale of oil synthetic plastics industry also enlarges rapidly, and plastic prod is applied to increasing industry.2010, world's plastics consumption was estimated as 3.28 hundred million tons, and the Chinese Plastics consumption is estimated also just will be above 5,600 ten thousand tons.Plastic prod provides convenience for industry, agricultural and daily life, has also produced a large amount of wastes simultaneously, and these wastes exist with solid form, and its source mostly is the Phthalates such as packing bag, beverage bottle, agricultural mulching.These volume of waste are large, the resolving time is very long, and degraded is very difficult in physical environment.The treatment process of plastic refuse (landfill, burning and recycling) is difficult to fundamentally solve " white pollution " that plastic garbage brings, and can not satisfy the needs of growing " environmental friendliness " consciousness of people.On the other hand, plastics are petroleum-based products, and the fluctuation of oil price also causes the unstable of plastic prod price.The day by day minimizing of current petroleum resources, the permanent development of plastics industry must be restricted.The finiteness of prospective oil and human consumption's unlimitedness, particularly recent international market oil price rises suddenly and sharply, and utilizes the degradable plastic of renewable resources, the friendly type of development environment to become the focus of global concern.
Degradative plastics can be degraded to carbonic acid gas and moisture under specific environment, can not give environment.The kind of degradative plastics is a lot, divides according to its degraded type, and multiple different kind is also arranged.Modal degradable plastics is mainly photodegradable plastics and biodegradable plastic two classes.Since the nineties in 20th century, be tending towards reducing for the research of photodegradable plastics, reason is because its product has run into obstacle in applying process.Photodegradable plastics is mainly used in the manufacturing mulch film, but the part of photodegradation film in placing into the soil is owing to without rayed, can't degrade; The degradation rate of photodegradable plastics depends on uitraviolet intensity, and different geographical position, weather condition etc. are larger on its degradation property impact; The production cost of photodegradable plastics is higher, does not possess competitive edge on price.
Degradable plastics is through development decades, and biodegradable plastic becomes its principal mode.And in the biodegradable plastic, starch plastics accounts for most of degradable plastics.
China's degradative plastics exploitation is started late, but development is very fast.From data report, China's biodegradable plastic mainly concentrates on and starch is carried out starch is to the filling research of plastics after graft modification and the modification, and the report aspect the development complete biodegradable plastics is less.
At present the research of bio-degradable plastics mainly concentrated on above the starch-based, biodegradable plastics.The starch-based, biodegradable plastics common are starch-filled plastic, full starch plastic and some biochemical synthetic polymers take starch as raw material.External product is all better at aspects such as mechanical property, biodegradabilities, but expensive.And the following problem of more domestic product ubiquities: use mechanical properties decrease; Production cost is higher; The degraded accuracy is difficult to control; Starch-base Degradable Plastic uses the starch of grain-production as raw material, industry occurs and strives conflicting of grain etc. with the people.
Summary of the invention
The object of the present invention is to provide a kind of biodegradable plastic preparation method of composite modified starch.Take starch as raw material, adopt dry method solid phase method complex denaturation operational path, prepare the biodegradable plastic composite modified starch.
Technical scheme of the present invention is as follows:
At first add activator and carry out pre-treatment in starch, then add esterifying agent and carry out esterification, add the solid coupling agent again, carry out the phase encapsulation reaction, reaction is rear processes, packs by cooling, screening, can obtain finished product.Detailed process is as follows:
1, in dry starch, adds activator, under 95-100 ℃, carried out activating pretreatment 30 minutes; Described starch is tapioca (flour) or yam starch.
2, the starch behind activating pretreatment adds esterifying agent, carries out esterification 1 hour under 120-125 ℃ of condition, and whole process is carried out under solid state shape;
3, the material after esterification adds the solid coupling agent again, carries out the phase encapsulation reaction under the state that stirs, and temperature of reaction is 125-130 ℃, and reaction times 40-50 minute, whole process was carried out under solid state shape; The purpose of activating pretreatment increases contact surface area and the contact frequency between solid chemicals and the starch molecule, improves the problem of dry method solid phase method reaction uniformity coefficient deficiency, improves reaction efficiency.
4, with reacted material cool to room temperature, then screening processing, cross 60 mesh sieves, packing can obtain finished product.
Above-described activator is sodium hydroxide or potassium hydroxide, and add-on is per 100 weight part cassava dry starch 0.3-2.0 parts, and the adding activator is solid state, add fashionable need to be with activator grinds powder;
Described esterifying agent is Trisodium trimetaphosphate or Sodium hexametaphosphate 99; The per 100 weight part cassava dry starch of add-on are 1-1.2 part; In starch molecule, add esterifying agent and access exactly esterified group and hydrophobic group.
Described solid coupling agent is Aluminate, titanic acid ester or boric acid ester, and the per 100 weight part dry starch of add-on are 2.5-3.5 part; Preferred Aluminate.
The composite modified starch that the present invention makes can with multiple high molecule plastic, raw materials such as ethylene/acrylic acid copolymer, ethylene/vinyl alcohol copolymer, polyvinyl alcohol adds softening agent, auxiliary agent blend, makes corresponding articles of biodegradable plastics material.
Below be the related data of solid coupling agent:
Aluminate, English name: aluminate coupling agent, structural formula is: (C3H7O) xAl (OCOR) m (OCOR﹠amp; Sup2; ) n (OAB) y fusing point: 60-90 ℃, heat decomposition temperature: 300 ℃ of solvabilities: be dissolved in industrial naptha, vinyl acetic monomer, toluene, turpentine wet goods, the Aluminate kind: can adopt SG-Al821 (distearyl acyl-oxygen sec.-propyl Aluminate), DL-411, DL-411AF, DL-411D, DL-411DF, anti-settling Aluminate ASA.ASA contain can with the group of active hydrogen reaction, thereby can with the mineral filler generation bonding action of hydroxyl, carboxyl or surface adsorption water, improve affinity and the bonding force of mineral filler and organic polymer, thereby produce result of prevention, also can improve bonding strength.
Titanate coupling agent has good coupling effect for thermal plastic polymer and dry filler; This class coupling agent can be used general formula: ROO (4-n) Ti (OX-R ' Y) n (n=2,3) expression; Wherein RO-is hydrolyzable short chain alkoxyl group, can react with the inorganics surface hydroxyl, thereby reach the purpose of chemical coupling; OX-can be carboxyl, alkoxyl group, sulfonic group, phosphorus base etc.
The boric acid ester outward appearance is white powdery or faint yellow particulate state, mineral filler (calcium carbonate, barium sulfate, talcum powder, aluminium hydroxide, white carbon black, wollastonite, potter's clay etc.) surface there is outstanding chemical modification effect, mineral filler after the modification and the consistency of macromolecular material are improved greatly, promoted the dispersiveness of mineral filler, and then improved inherence and the visual appearance of macromolecule material product, have inside and outside lubricated and plasticising performance concurrently.
Compared with prior art, substantive distinguishing features of the present invention and significant progress are:
1, utilizes tapioca (flour) or yam starch as main raw material, adopt the development and production of dry method solid phase method complex denaturation operational path.Particularly tapioca (flour) is the superior resources in Guangxi, belongs to renewable resources, and is cheap and easy to get.Through behind the complex denaturation, good with intermiscibilities such as macromolecule resin, PVC, softening agent, fillers, water resistance and mechanical property also are greatly improved.Can be widely used in injection moulding and the blown film of plastics, the plastics biological degradation is complete, environmentally safe.Because adopt the production of dry method solid phase method, the products production cost is low, and is easy and simple to handle, stable performance.This product all is better than domestic like product at aspects such as use properties, biodegradability, prices.Develop this product, to alleviating " white pollution " and petroleum resources scarcity positive meaning is arranged, have good economic benefit and social benefit.
2, the whole reaction process of the present invention all carries out under solid state shape, and is with short production cycle, easy and simple to handle.Add activator early stage in reaction, carry out under given conditions activating pretreatment, increased contact surface area and contact frequency between solid chemicals and the starch molecule, improved the problem of dry method solid phase method reaction uniformity coefficient deficiency, also significantly improved reaction efficiency.By phase parcel, esterification complex denaturation, in starch molecule, access esterified group and hydrophobic group, greatly improved the intermiscibility of product and macromolecule resin, PVC, softening agent, filler etc., water resistance and mechanical property also are significantly improved.This product main raw material is starch, and biological degradation is complete, environmentally safe.
3, the Guangxi cassava starch material is abundant, cheap, be the cassava modified starch production base, but production technology and the product of Guangxi modified starch are compared with external or domestic some advanced enterprises at present, exist the production technology high-tech content low, the deficiency such as range of product is single, added value is low.Abundant tapioca (flour) is raw material take Guangxi in the present invention, adopts the development and production of dry method solid phase method complex denaturation operational path, and behind phase parcel, esterification complex denaturation, product has very high water resistance and mechanical property.This product is good with intermiscibilities such as macromolecule resin, PVC, softening agent, fillers.
On the other hand, the present invention's research is to accelerating the deep processing of Guangxi cassava starch to hi-tech development, and also tool is of great significance.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
Below in conjunction with accompanying drawing, by embodiment the present invention is described in further detail again,
Shown in Fig. 1, the cassava dry starch at first adds activator and carries out pre-treatment, then adds esterifying agent and carries out esterification, adds the solid chemicals coupling agent again, carries out the phase encapsulation reaction, and reaction is rear processes, packs by cooling, screening, can obtain finished product.
Embodiment
Embodiment 1:
Take by weighing 100 weight part cassava dry starch, add 0.3 weight part activator solid sodium hydroxide (grinds powder), under 95-100 ℃, carried out activation treatment 30 minutes.And then add 1 weight part esterifying agent Trisodium trimetaphosphate, carried out esterification 1 hour under the 120-125 ℃ of condition.Toward through adding 2.5 weight part solid chemicals coupling agent titanic acid ester in the product of esterification, under well-beaten state, carry out the phase encapsulation reaction, temperature of reaction is 125-130 ℃, 50 minutes reaction times.By the cold wind treatment system, be cooled to below 30 ℃ at last, sieve processing after 60 mesh sieves, by quantitative package, get product.
Embodiment 2
Take by weighing 100 weight part cassava dry starch, add 0.8 weight part activator solid sodium hydroxide (grinds powder), under 95-100 ℃, carried out activation treatment 30 minutes.And then add 1.2 weight part esterifying agent Trisodium trimetaphosphates, carried out esterification 1 hour under the 120-125 ℃ of condition.Toward through adding 3.5 weight part solid chemicals coupling agent Aluminates in the product of esterification, under well-beaten state, carry out the phase encapsulation reaction, temperature of reaction is 125-130 ℃, 40 minutes reaction times.By the cold wind treatment system, be cooled to room temperature at last, sieve processing after 60 mesh sieves, by quantitative package, get product.
Embodiment 3
Take by weighing the tapioca (flour) of 100 weight parts, in the activator solid potassium hydroxide (grinds powder) that reaction is in earlier stage added 1. 0 weight parts, under 95-100 ℃, carried out activating pretreatment 30 minutes; Then add 1.2 weight part esterifying agent Sodium hexametaphosphate 99s, under 120-125 ℃ of condition, carried out esterification 1 hour; Add 3 weight part solid chemicals coupling agent boric acid esters again, carry out the phase encapsulation reaction under well-beaten state, temperature of reaction is 125-130 ℃, reaction times 40-50 minute; By the cold wind treatment system, be cooled to below 30 ℃ at last; Cross 60 mesh sieves and sieve processing, by quantitative package, get product.
Embodiment 4
Take by weighing the yam starch of 100 weight parts, reacting the activator solid sodium hydroxide (grinds powder) that adds 2.0 weight parts in earlier stage, under 95-100 ℃, carried out activating pretreatment 30 minutes; Then add 1.2 weight part esterifying agent Sodium hexametaphosphate 99s, under 120-125 ℃ of condition, carried out esterification 1 hour; Add 3.5 weight part solid chemicals coupling agent boric acid esters again, carry out the phase encapsulation reaction under well-beaten state, temperature of reaction is 125-130 ℃, reaction times 40-50 minute; By the cold wind treatment system, be cooled to below 30 ℃ at last; Cross 60 mesh sieves and sieve processing, by quantitative package, get product.
The biodegradable plastic provided by the invention preparation method of composite modified starch, its product is carried out Degrading experiment and Mechanics Performance Testing, testing location: the sugarcane field on the bright positive farm of Nanning carries out Degrading experiment, the time: 5 months, and from February, 2012-2012 year June.Test case is seen following table 1 and table 2.
Table 1 degradation property
| The name of an article | ? | Thickness (mm) | Mulching soil thickness (cm) | The degraded situation |
| Polyethylene | ? | 0.10 | 3 | Remain intact |
| Polyvinyl chloride | ? | 0.10 | 3 | Remain intact |
| Polypropylene | ? | 0.10 | 3 | Remain intact |
| The embodiment of the invention 1 | Starch content 30% | 0.10 | 3 | Become imperfect fragment |
| The embodiment of the invention 2 | Starch content 50% | 0.10 | 3 | Can not find fragment |
Table 1 has shown the degradation property that the present invention is good
Table 2 thin film mechanical performance
Table 2 has shown the mechanical property that the present invention is good.
Claims (4)
1. a biodegradable plastic is with the preparation method of composite modified starch, and it is characterized in that: by phase parcel, esterification complex denaturation, access simultaneously esterified group and hydrophobic group in starch molecule, preparation process is as follows:
(1) in dry starch, adds activator, under 95-100 ℃, carried out activating pretreatment 30 minutes; Described activator is oxyhydroxide, and the weight part that per 100 weight part dry starch add activator is 0.3-2.0;
(2) in the starch through (1) step activating pretreatment, add esterifying agent, under 120-125 ℃ of condition, carried out esterification 1 hour; Described esterifying agent is Trisodium trimetaphosphate or Sodium hexametaphosphate 99, and it is 1-1.2 that per 100 weight part dry starch add the esterifying agent weight part;
(3) add the solid coupling agent in (2) product in step, carry out the phase encapsulation reaction under well-beaten state, temperature of reaction is 125-130 ℃, reaction times 40-50 minute; Described solid coupling agent is Aluminate, titanic acid ester or boric acid ester, and the weight part that per 100 portions of dry starch add the solid coupling agent is 2.5-3.5;
(4) product with (3) step passes through the cold wind treatment system, is cooled to below 30 ℃;
(5) product in (4) step is crossed 60 mesh sieves and sieve processing, by quantitative package, get product.
2. biodegradable plastic as claimed in claim 1 is with the preparation method of composite modified starch, and it is characterized in that: described starch is tapioca (flour) or yam starch.
3. biodegradable plastic as claimed in claim 1 is with the preparation method of composite modified starch, and it is characterized in that: described oxyhydroxide is pulverous sodium hydroxide or potassium hydroxide.
4. biodegradable plastic claimed in claim 1 is characterized in that with the preparation method of composite modified starch: this composite modified starch energy and high molecule plastic, add softening agent, auxiliary agent blend, and make articles of biodegradable plastics material.
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Cited By (3)
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| CN108239174A (en) * | 2016-12-24 | 2018-07-03 | 湖南尔康制药股份有限公司 | A kind of sulfonation composite modified starch |
| CN109265937A (en) * | 2018-09-21 | 2019-01-25 | 袁志平 | The method for preparing the dedicated agricultural mulching of peanut using automobile-used acoustical cotton corner dead meal |
| CN109280297A (en) * | 2018-09-21 | 2019-01-29 | 袁志平 | A kind of dedicated anti-reflection enhancing master batch of agricultural booth teleblem and preparation method thereof |
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| CN108239174A (en) * | 2016-12-24 | 2018-07-03 | 湖南尔康制药股份有限公司 | A kind of sulfonation composite modified starch |
| CN109265937A (en) * | 2018-09-21 | 2019-01-25 | 袁志平 | The method for preparing the dedicated agricultural mulching of peanut using automobile-used acoustical cotton corner dead meal |
| CN109280297A (en) * | 2018-09-21 | 2019-01-29 | 袁志平 | A kind of dedicated anti-reflection enhancing master batch of agricultural booth teleblem and preparation method thereof |
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