CN103044717B - A kind of preparation method of biodegradable plastic composite modified starch - Google Patents
A kind of preparation method of biodegradable plastic composite modified starch Download PDFInfo
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Abstract
A kind of biodegradable plastic method for preparing composite modified starch, is first in dry starch, add activator, carries out activating pretreatment 30 minutes at 95-100 DEG C; Then the starch after activating pretreatment adds esterifying agent, and under 120-125 DEG C of condition, carry out esterification 1 hour, whole process is carried out under solid state shape; Material again after esterification adds solids coupling agent again, and under the state stirred, carry out thing phase encapsulation reaction, temperature of reaction is 125-130 DEG C, reaction times 40-50 minute, and whole process is carried out under solid state shape; Finally by reacted material cool to room temperature, then sieve process, cross 60 mesh sieves, packaging, can obtain finished product.
Description
Technical field
The present invention relates to a kind of composite modified starch, the preparation method of the composite modified starch of particularly biodegradable plastic use.
Background technology
Along with the fast development of China's economy, the scale of oil synthetic plastics industry also expands rapidly, and plastic prod is applied to increasing industry.2010, world's plastics consumption was estimated as 3.28 hundred million tons, and Chinese Plastics consumption is estimated also just will more than 5,600 ten thousand tons.Plastic prod is industrial, agriculture and daily life provides conveniently, and also create a large amount of waste, these wastes exist in solid form, and its source mostly is the Phthalates such as packing bag, beverage bottle, agricultural mulching simultaneously.These volume of waste are large, the resolving time is very long, degrade very difficult in physical environment.The treatment process (landfill, burning and recycling) of plastic refuse is difficult to fundamentally to solve " white pollution " that plastic garbage brings, and can not meet the needs that people's growing " environmental friendliness " realize.On the other hand, plastics are petroleum-based products, and the fluctuation of oil price also causes the instability of plastic prod price.The minimizing day by day of current oil resource, the sustainable development of plastics industry must be restricted.The finiteness of prospective oil and the unlimitedness of human consumption, particularly recent international market oil price rises suddenly and sharply, and utilizes renewable resources, focus that the degradable plastic of development environment friendly has become global concern.
Degradative plastics under particular circumstances, can be degraded to carbonic acid gas and moisture, can not give environment.The kind of degradative plastics is a lot, divides, also have multiple different kind according to its degraded type.Modal degradable plastics is mainly photodegradable plastics and biodegradable plastic two class.From the nineties in 20th century, the research for photodegradable plastics is tending towards reducing, and reason is because its product encounters obstacle applying in process.Photodegradable plastics is mainly used in manufacture mulch film, but photodegradation film place into the soil in part due to without rayed, cannot degrade; The degradation rate of photodegradable plastics depends on uitraviolet intensity, and different geographical position, weather condition etc. are larger on the impact of its degradation property; The production cost of photodegradable plastics is higher, and price does not possess competitive edge.
Degradable plastics developed through decades, and biodegradable plastic becomes its principal mode.And in 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 carries out graft modification to starch and modified starch study the filling of plastics, and developing, the report in complete biodegradable plastics is less.
At present the research of bio-degradable plastics is mainly concentrated on above starch-based, biodegradable plastics.Starch-based, biodegradable plastics common are starch-filled plastic, full-starch plastic and some take starch as the biochemical synthetic polymer of raw material.External product is all better in mechanical property, biodegradability etc., but expensive.And the following problem of more domestic product ubiquities: use mechanical properties decrease; Production cost is higher; Degraded accuracy is difficult to control; Starch-base Degradable Plastic uses the starch of grain-production as raw material, occurs that industry strives conflicting of grain with people.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of biodegradable plastic composite modified starch.Take starch as raw material, adopt dry method solid phase method complex denaturation operational path, prepare biodegradable plastic composite modified starch.
Technical scheme of the present invention is as follows:
First in starch, add activator carry out pre-treatment, then add esterifying agent and carry out esterification, then add solids coupling agent, carry out thing phase encapsulation reaction, by cooling, screening process, packaging after reaction, can finished product be obtained.Detailed process is as follows:
1, in dry starch, add activator, at 95-100 DEG C, carry out activating pretreatment 30 minutes; Described starch is tapioca (flour) or yam starch.
2, the starch after activating pretreatment adds esterifying agent, and under 120-125 DEG C of condition, carry out esterification 1 hour, whole process is carried out under solid state shape;
3, the material after esterification adds solids coupling agent again, and under the state stirred, carry out thing phase encapsulation reaction, temperature of reaction is 125-130 DEG C, reaction times 40-50 minute, and whole process is carried out under solid state shape; The object of activating pretreatment increases the surface in contact sum contact frequency between solid chemicals and starch molecule, improves the problem of dry method solid phase method reaction uniformity coefficient deficiency, improves reaction efficiency.
4, by reacted material cool to room temperature, then sieve process, cross 60 mesh sieves, packaging, can obtain finished product.
Above-described activator is sodium hydroxide or potassium hydroxide, and add-on is every 100 weight part cassava dry starch 0.3-2.0 parts, and adding activator is solid state, and adding fashionablely needs activator grinds powder;
Described esterifying agent is Trisodium trimetaphosphate or Sodium hexametaphosphate 99; The every 100 weight part cassava dry starch of add-on are 1-1.2 part; In starch molecule, add esterifying agent access esterified group and hydrophobic group exactly.
Described solids coupling agent is Aluminate, titanic acid ester or boric acid ester, and the every 100 weight part dry starch of add-on are 2.5-3.5 part; Preferred Aluminate.
The composite modified starch that the present invention obtains can with the raw materials such as multiple high molecule plastic, such as ethylene/acrylic acid copolymer, ethylene/vinyl alcohol copolymer, polyvinyl alcohol, add softening agent, auxiliary agent be blended, make corresponding articles of biodegradable plastics material.
Below the related data of solids coupling agent:
Aluminate, English name: aluminatecouplingagent, structural formula is: (C3H7O) xAl (OCOR) m (OCOR & sup2; ) n (OAB) y fusing point: 60-90 DEG C, heat decomposition temperature: 300 DEG C of solvabilities: be dissolved in industrial naptha, vinyl acetic monomer, toluene, turpentine wet goods, Aluminate kind: SG-Al821 (distearyl acyl-oxygen sec.-propyl Aluminate), DL-411, DL-411AF, DL-411D, DL-411DF, anti-settling Aluminate ASA can be adopted.ASA contain can with the group of active hydrogen reaction, thus 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, thus produce result of prevention, also can improve bonding strength.
Titanate coupling agent, for thermal plastic polymer and dry filler, has good coupling effect; This kind of coupling agent can use general formula: ROO (4-n) Ti (OX-R ' Y) n (n=2,3) to represent; Wherein RO-is hydrolyzable lower alkyloxy, can react, thus reach the object of chemical coupling with mineral surfaces hydroxyl; OX-can be carboxyl, alkoxyl group, sulfonic group, phosphorus base etc.
Boric acid ester outward appearance is white powder or faint yellow particulate state, outstanding chemical modification effect is had to mineral filler (calcium carbonate, barium sulfate, talcum powder, aluminium hydroxide, white carbon black, wollastonite, potter's clay etc.) surface, the consistency of modified mineral filler and macromolecular material is improved greatly, facilitate the dispersiveness of mineral filler, and then improve inherence and the visual appearance of macromolecule material product, have inside and outside lubrication and plasticising performance concurrently.
Compared with prior art, substantive distinguishing features of the present invention and significant progress are:
1, utilize 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, cheap and easy to get.After complex denaturation, good with intermiscibilities such as macromolecule resin, PVC, softening agent, fillers, water resistance and mechanical property have also been obtained very large raising.Can be widely used in injection moulding and the blown film of plastics, plastics biological degradation is complete, environmentally safe.Owing to adopting dry method solid phase method to produce, products production cost is low, easy and simple to handle, stable performance.This product is all better than domestic like product in use properties, biodegradability, price etc.Develop this product, have positive meaning to alleviation " white pollution " and petroleum resources scarcity, there is good economic benefit and social benefit.
2, the whole reaction process of the present invention all carries out under solid state shape, with short production cycle, easy and simple to handle.Phase adds activator before the reaction, carries out activating pretreatment under given conditions, increases the surface in contact sum contact frequency between solid chemicals and starch molecule, improves the problem of dry method solid phase method reaction uniformity coefficient deficiency, also significantly increases reaction efficiency.Wrapped up mutually by thing, esterification complex denaturation, in starch molecule, access esterified group and hydrophobic group, substantially increase the intermiscibility of product and macromolecule resin, PVC, softening agent, filler etc., water resistance and mechanical property are also significantly improved.This product main raw material is starch, and biological degradation is complete, environmentally safe.
3, Guangxi cassava starch material enriches, cheap, be cassava modified starch production base, but the production technology of current Guangxi modified starch and product are compared with some advanced enterprises external or domestic, there is production technology high-tech content low, the deficiencies such as range of product is single, added value is low.The present invention for raw material with the abundant tapioca (flour) in Guangxi, adopts the development and production of dry method solid phase method complex denaturation operational path, wraps up mutually through thing, after esterification complex denaturation, product has very high water resistance and mechanical property.The intermiscibilities such as this product and macromolecule resin, PVC, softening agent, filler are good.
On the other hand, the present invention's research is to the deep processing of quickening Guangxi cassava starch to hi-tech development, and also tool is of great significance.
Accompanying drawing explanation
Fig. 1 is present invention process schema.
Below in conjunction with accompanying drawing, by embodiment, the present invention is described in further detail again,
Shown in Fig. 1, first cassava dry starch adds activator and carries out pre-treatment, then adds esterifying agent and carries out esterification, then add solid chemicals coupling agent, carries out thing phase encapsulation reaction, by cooling, screening process, packaging after reaction, can obtain finished product.
Embodiment
Embodiment 1:
Take 100 weight part cassava dry starch, add 0.3 weight part activator solid sodium hydroxide (grinds powder), at 95-100 DEG C, carry out activation treatment 30 minutes.And then add 1 weight part esterifying agent Trisodium trimetaphosphate, carry out esterification under 120-125 DEG C of condition 1 hour.In the product through esterification, add 2.5 parts by weight solids medicament coupling agent titanic acid ester, under well-beaten state, carry out thing phase encapsulation reaction, temperature of reaction is 125-130 DEG C, 50 minutes reaction times.Finally by cold wind treatment system, be cooled to less than 30 DEG C, carry out screening process after 60 mesh sieves, by quantitative package, get product.
Embodiment 2
Take 100 weight part cassava dry starch, add 0.8 weight part activator solid sodium hydroxide (grinds powder), at 95-100 DEG C, carry out activation treatment 30 minutes.And then add 1.2 weight part esterifying agent Trisodium trimetaphosphates, carry out esterification under 120-125 DEG C of condition 1 hour.In the product through esterification, add 3.5 parts by weight solids medicament coupling agent Aluminates, under well-beaten state, carry out thing phase encapsulation reaction, temperature of reaction is 125-130 DEG C, 40 minutes reaction times.Finally by cold wind treatment system, be cooled to room temperature, carry out screening process after 60 mesh sieves, by quantitative package, get product.
Embodiment 3
Take the tapioca (flour) of 100 weight parts, the phase adds the activator solid potassium hydroxide (grinds powder) of 1.0 weight parts before the reaction, carries out activating pretreatment 30 minutes at 95-100 DEG C; Then add 1.2 weight part esterifying agent Sodium hexametaphosphate 99s, under 120-125 DEG C of condition, carry out esterification 1 hour; Add 3 parts by weight solids medicament coupling agent boric acid esters again, under well-beaten state, carry out thing phase encapsulation reaction, temperature of reaction is 125-130 DEG C, reaction times 40-50 minute; Finally by cold wind treatment system, be cooled to less than 30 DEG C; Cross 60 mesh sieves and carry out screening process, by quantitative package, get product.
Embodiment 4
Take the yam starch of 100 weight parts, the phase adds the activator solid sodium hydroxide (grinds powder) of 2.0 weight parts before the reaction, carries out activating pretreatment 30 minutes at 95-100 DEG C; Then add 1.2 weight part esterifying agent Sodium hexametaphosphate 99s, under 120-125 DEG C of condition, carry out esterification 1 hour; Add 3.5 parts by weight solids medicament coupling agent boric acid esters again, under well-beaten state, carry out thing phase encapsulation reaction, temperature of reaction is 125-130 DEG C, reaction times 40-50 minute; Finally by cold wind treatment system, be cooled to less than 30 DEG C; Cross 60 mesh sieves and carry out screening process, by quantitative package, get product.
The preparation method of biodegradable plastic composite modified starch provided by the invention, Degrading experiment and Mechanics Performance Testing are carried out to its product, testing location: the sugarcane field on Ming Yang farm, Nanning carries out Degrading experiment, the time: 5 months, from June ,-2012 in February, 2012.Test case is shown in following table 1 and table 2.
Table 1 degradation property
| The name of an article | Thickness (mm) | Mulching soil thickness (cm) | 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 present invention 1 | Starch content 30% | 0.10 | 3 | Become imperfect fragment |
| The embodiment of the present invention 2 | Starch content 50% | 0.10 | 3 | Can not find fragment |
Table 1 shows the good degradation property of the present invention
Table 2 thin film mechanical performance
Table 2 shows the excellent mechanical property of the present invention.
Claims (2)
1. a preparation method for biodegradable plastic composite modified starch, is characterized in that: wrapped up mutually by thing, esterification complex denaturation, and in starch molecule, access esterified group and hydrophobic group, preparation process is as follows simultaneously:
(1) in dry starch, add activator, at 95-100 DEG C, carry out activating pretreatment 30 minutes; Described activator is oxyhydroxide, and the weight part that every 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 DEG C of condition, carry out esterification 1 hour; Described esterifying agent is Trisodium trimetaphosphate or Sodium hexametaphosphate 99, and it is 1-1.2 that every 100 weight part dry starch add esterifying agent weight part;
(3) in the product of (2) step, add solids coupling agent, carry out thing phase encapsulation reaction under well-beaten state, temperature of reaction is 125-130 DEG C, reaction times 40-50 minute; Described solids coupling agent is Aluminate, titanic acid ester or boric acid ester, and the weight part that every 100 portions of dry starch add solids coupling agent is 2.5-3.5;
(4) product of (3) step is passed through cold wind treatment system, be cooled to less than 30 DEG C;
(5) product of (4) step is crossed 60 mesh sieves and carry out screening process, by quantitative package, get product;
Described starch is tapioca (flour);
Described oxyhydroxide is pulverous sodium hydroxide or potassium hydroxide.
2. biodegradable plastic composite modified starch according to claim 1 is preparing the application in articles of biodegradable plastics material.
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| CN108239174B (en) * | 2016-12-24 | 2021-06-29 | 湖南尔康制药股份有限公司 | Sulfonated 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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| US5462983A (en) * | 1993-07-27 | 1995-10-31 | Evercorn, Inc. | Biodegradable moldable products and films comprising blends of starch esters and polyesters |
| CN1164662C (en) * | 2001-12-18 | 2004-09-01 | 广东三九生物降解塑料有限公司 | Starch-based biodegradable material and production method of its disposable tableware |
| CN101033262A (en) * | 2006-03-10 | 2007-09-12 | 四平帝达变性淀粉有限公司 | Method of preparing starch phosphate |
| CN1884363A (en) * | 2006-06-16 | 2006-12-27 | 孙付生 | Macromolecular compound PVB degradable plastic |
| CN102504455B (en) * | 2011-11-04 | 2013-11-06 | 山东省塑料研究开发中心 | Preparation method for composite full-degradable material |
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