CN1205346A - Controllable light biological whole degradation plastic - Google Patents
Controllable light biological whole degradation plastic Download PDFInfo
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- CN1205346A CN1205346A CN 98100450 CN98100450A CN1205346A CN 1205346 A CN1205346 A CN 1205346A CN 98100450 CN98100450 CN 98100450 CN 98100450 A CN98100450 A CN 98100450A CN 1205346 A CN1205346 A CN 1205346A
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Abstract
A multifunctional, controllable, photo- and bio-degradable plastics is prepared from modified starch, polyolefine or PVC resin and photodegradating agent. After the plastics as master material is mixed with PE, a ground-covering film can be made by blowing, whose thickness is 0.008-0.014 mm, whose starch content is 20% and whose degradable rate is 100% in 120 days. It can also be used to make other plastic bags such as garbage bag. Its advantages are simple process.
Description
The present invention relates to a kind of is the controllable light biological whole degradation plastic of main raw material with auxiliary agents such as starch, polyolefine, degradation agentss.
At present, the plastics industry product has obtained application more and more widely.Because existing plastics can not decompose in physical environment voluntarily, a large amount of plastic garbages has caused serious white pollution to environment.Agricultural mulching plastics particularly, a large amount of residual films can cause soil compaction, and the liquid manure circulation is not smooth, has had a strong impact on the growth of farm crop.In addition, be used for packing in addition in a large number, the plastics of aspects such as food and drink, day by day seriously prestige is being assisted the human existence space, has become the pressing issues of World Focusing.Just the plastic degradation technology of studying at present has photodegradation and biological degradation two classes; Photodegradable plastics mainly adds photosensitizers, and the photosensitizers that uses costs an arm and a leg at present, increased cost, product price is higher than existing plastic sheeting for farm use, and buries the ground part owing to absorb ultraviolet not enough, cause degradation rate to reach on 1 year, still cause soil pollution, be difficult to apply.All kinds of starch biodegradation plastics, because starch can be degraded by Institute of Micro-biology, plastic sheeting for farm use goods particularly, be retained in natural decomposition in the soil, need not reclaim, and starch is again natural synthetic under effect of sunlight by green plants, is a kind of renewable resources, be a kind of better technology that solves degradative plastics by way of.As the present starch of suitability for industrialized production--EAA (ethene--acrylic copolymer), its product degradation rate is 70～80%, and mechanical property reaches 85% of existing plastics, and product price is still expensive.China Hua Zhong Agriculture University trial-produces successfully and the biological degradation agricultural mulching of small-scale production (treated starch--PE), ground film thickness 0.014 ± 0.001mm, its physicals, mechanical property all are higher than national standard (SC369--84), starch content reaches 16% in the product, is a kind of preferably in the present like product.But the mechanism of degradation of this product is the immersion by microorganism, makes long molecule chain break and causes the degraded of starch plastic.Therefore its degradation rate is subjected to the influence, particularly ground of the factors such as content, fertility of metallic salt in soil humidity, temperature and pH value and the soil to carry out cover, and light divides degraded just more difficult, thereby certain limitation is arranged in agricultural mulching is applied.
It is incomplete to the objective of the invention is to overcome the existing degraded of degradative plastics of the prior art, degradation rate is paid no attention to and is thought of the higher shortcoming of price, and developing the light harvesting biological degradation that a kind of price is lower than existing degradative plastics is the controllable light biological whole degradation plastic of one.
The present invention is on the basis of the mechanism of degradation of comprehensive light, biodegradable plastic and existing degraded starch plastics resin, selected for use and obtained processing aids such as the properties-correcting agent lower, photodegradable aid, initiator, coupling agent easily with price, through lot of experiments, developed successfully light harvesting, biological degradation is the controllable degradation starch plastic resin of one, it is that main raw material and auxiliary chemicals are processed into treated starch, Plastic Resin.Be a kind of processing masterbatch and calendared sheet that contains 40～56% starch plastic goods, the prescription of masterbatch is formed (weight %) and is:
Treated starch 48～56
Polyolefine or polyvinyl chloride (PVC) 38～46
Oleic acid 4.1～5.1
Whiteruss 0.5～0.6
Tween 0.10～0.19
Glycerine 0.5～0.6
This masterbatch can be processed into master batch with ordinary method, is processed into the degredation plastic goods with master batch and corresponding Plastic Resin raw material blend then; The prescription of calendared sheet is formed (weight %):
Treated starch 40.69
Polyolefine (PVC) 54.18
Whiteruss 0.55
Oleic acid 3.89
Tween 0.14
Glycerine 0.55
Also can add auxiliary agents such as whipping agent according to a conventional method according to purposes, be processed into foam sheet, be used for the processing of all types of plastic goods.
Described treated starch, be 100 parts of the W-Gums (weight) of selecting the oven dry back for use and passing through 100～120 mesh sieves, preheating 7～10 minutes, add the titanic acid ester coupling agent of 1～1.5 part (weight), the ferrocene of 0.16～0.21 part (weight), under 105 ℃～110 ℃ temperature, through high-speed mixing, reacted 5～10 minutes and make, water content should＜1% in the treated starch.
Described polyolefins, polyvinyl chloride (PVC) RESINS are meant the PVC of polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC) that can be processed into plastics according to a conventional method or the former material of calendared sheet that has prepared;
Described oleic acid is meant vaccenic acid--9--liquid (CH
3-(CH
2)
7CH-(CH
2)
7COOH;
Tween is meant any in tween 20, tween-30, Tween-40, the tween-80;
The concrete steps of processing masterbatch are:
Form to add treated starch, polyolefine or PVC (squeezing, annotate, blow the class starting material according to the product requirement input) by prescription in mixing machine, start mixed 5 minutes, added tween, whiteruss, oleic acid, glycerine blend behind the mixing 10 minutes.Discharging behind the inspection material mixing.Enter the tablets press granulation then, make controllable degradation starch plastic resin master batch product.
Adopt controllable light biological whole degradation plastic of the present invention, mix mutually with corresponding Plastic Resin, producing and manufacturing technique routinely and equipment can be made into blowing, calendering, hollow, foaming, injecting products; As non-returnable containers such as farmland film, refuse bag, food bag, shopping bag, food product pack, mess-tin, beverage bag, bottle, bowl, disposable tablecloth, pastry casees.Therefore has multifunctional usage.
Controllable light biological whole degradation plastic master batch of the present invention is with the advantage of the mixed mutually film that is processed into of corresponding Plastic Resin with photodegradation film and Biodegradable film; Agricultural mulching 0.008～0.014mm as the blowing that is mixed with this masterbatch and PE resin.Starch content accounts for 20% mulch film, good transmittance, its physical and mechanical properties has all been carried out the field experiment in autumn simultaneously above like product and state-set standard (table 1), all be degraded at 120 days molecular weight 500 following visual inspections less than small-particle, degradation rate is 100%; And but the blowing starch content is 23～30%, blow molded products such as the refuse bag of thick 0.02～0.1mm, handbag; PE, the PVC calendared sheet of processing can be processed into non-returnable container (bottle, bowl, box etc.) goods.Product after testing, its mechanics, reason all meet or exceed the level of similar plastics for performance.Selected raw material all is based on the product that domestic production is easy to get, the starch content height, and cost is lower; Even be lower than polyolefinic commercial value; Masterbatch manufacture craft flow process is simple, utilizes domestic existing production and processing plastic goods equipment to produce, and need not the flower great amount of investment and purchases new production unit, adds this and very easily promotes.As existing mulch film factory, blown film factory, calendared sheet factory, plastic containers factory bottle blowing machine, blow moulding machine, Packing Machine etc. can all kinds of degredation plastic goods of processing.
Example 1
Get the raw materials ready:
White cornstarch: outward appearance is pure white glossy, no people's flavor, no sand and impurity; After testing: little branch＜13%; Acid rate OT＜20%; Ash content＜0.1; Protein＜0.3%; 4 of spots, cm
2Fineness 100 mesh sieve percent of pass 99.9%; Whiteness 440NM blue streak reflection＞97.5%.Above-mentioned starch is put into 105 ℃～115 ℃ oven dry of dryer, be lower than 1% to water content, and cross 120 mesh sieves and take by weighing 200Kg.
Titanic acid ester (KL-T951 Shijiazhuang City chemical industry four factories product) 3Kg
Ferrocene (Tm173 ℃～174 ℃ Lanzhou 504 factories produce) 0.4Kg.
The W-Gum that last art drying is sieved drops into constant temperature in 105 ℃～115 ℃ Hot mixer (produce through flag plastics machinery factory Fuxin, GRH500 Liaoning), added main metatitanic acid vinegar, ferrocene after running up 9 minutes, after the high-speed mixing 5 minutes, check that material is up to mixing, feel is loose, water content＜1% gets final product discharging, makes treated starch.The product sampling detects at 1736cm with red spectral
-1(peak is levied in hesitating of starch conversion) locates strong sharp-pointed absorption peak.
Example 2
Example 1 treated starch (being cooled to room temperature) 202.28Kg is dropped in the mixing machine, drop into LLDPE176.2Kg, start mixed 5 minutes, added tween-80 0.56Kg, whiteruss 2.2Kg, oleic acid 16.56, glycerine 2.2Kg behind the mixing, mixed 10 minutes up to mixing, i.e. discharging.Drop into granulation unit (SJ120) forcing machine hopper (deoxygenation formula forcing machine) then, heat up; 115 ℃ ± the 5c in one district, 130 ℃ ± 5 ℃ in 125 ± 5, three districts, two districts, 125 ℃ ± 5 ℃ in four districts, constant temperature 1 little started shooting in the back in 120 ℃ ± 5 ℃ temperature in five districts back up to standard extruded slivering → air-cooled pelletizing, sieves and is processed into degraded starch-PE master batch.Outward appearance: white garden cylindricality particle, diameter 4mm, density (23 ℃) 0.10g/cm
3
Melt index (LLKEP) 1.2g/10 minute.
Example 3
Method steps replaces LLDPE, is processed into degraded starch-the PP master batch with PP with example 2.Outward appearance two white garden cylindricalitys, particle diameter is 4mm, density: 1.0g/cm
3Solution index: 5g/10 minute.
Example 4
Throw LLDPE (blowing level) 100Kg, the common mixing machine of LDPE2F1.5B 30Kg of the master batch 100Kg of example 2 productions, mix the hopper that drops into blow moulding machine, controlled temperature, 115 ℃ ± the 5c in one district, 130 ℃ ± 5 ℃ in 125 ± 5, three districts, two districts, 125 ℃ ± 5 ℃ in four districts, 120 ℃ ± 5 ℃ in five districts, 140 ℃ ± 5 ℃, 130 ℃ ± 5 ℃ constant temperature of head started start in 1 hour, were blow molded into film thickness at 0.08mm, and starch content is 21% water white farmland mould.
Example 5
After the former material PVC54.18Kg of calendared sheet that get the treated starch 40.69Kg, the whiteruss 0.55Kg that make by example 1 method, oleic acid 3.89Kg, industry glycerol 0.55Kg, has prepared stirs in high-speed mixer, dropped into two rollers mixing (mixing between 126 ℃ of preliminary rollers, 140 ℃ on the roller in back) 30 minutes, discharging refining in five roll calendars goes out calendared sheet, 165 ℃ ± 5 ℃ of calendared sheet use temperatures.
Example 6
Take by weighing the treated starch 40.46Kg, industrial tween 80 .14Kg, the whiteruss 0.55Kg that make by example 1 method, oleic acid 4.14Kg, industry glycerol 0.55Kg, the PVC54.15Kg mixing masterbatch that has prepared, stearic acid zincification 2.5Kg, zinc oxide 6.8Kg mixing in mixing machine, enter two roller mixing rolls, adding maleic rubber 25Kg, blowing agent AC 25Kg carries out mixing, enter three roller refinings again, add crosslink agent DCP 1.5Kg simultaneously, refining in flakes → mold pressing is crosslinked → be foamed into blank → moulded from foam → cooling forming suddenly.
Claims (4)
1, a kind of is the controllable light biological whole degradation plastic that main raw material is processed into treated starch, Plastic Resin, it is characterized in that containing the processing masterbatch or the calendared sheet of plastics of the starch of 40～56% (weight).Described treated starch is to be formed 105 ℃～115 ℃ reactions by 100 orders that the sieve～titanium ester acid of 120 purpose W-Gums (weight) adding in 100 fens, 1～1.5% (weight) and the ferrocene of 0.16～0.21 minute (weight); Described Plastic Resin is meant any of polyethylene, polypropylene, polystyrene, polyvinyl chloride of the conventional method processing that is used for plastics.
2, controllable light biological whole degradation plastic as claimed in claim 1 is characterized in that described masterbatch composition (weight %) is: treated starch 48～56 polyolefine 38～46 oleic acid 4.1～5.1 whiterusss 0.5～0.6 tween 0.10～0.19 glycerine 0.5～0.6
Described polyolefine is meant in the polyethylene, polypropylene of available conventional method processing plastic goods any.
3, controllable light biological whole degradation plastic as claimed in claim 2 is characterized in that described polyolefine is meant the polyvinyl chloride of available conventional method processing plastic goods, any replacement in the Expandable Polystyrene (EPS).
4, controllable light biological whole degradation plastic as claimed in claim 1 is characterized in that the composition (weight %) of described calendared sheet is: treated starch 40.69 polyolefine 54.18 whiterusss 0.55 oleic acid 3.89 tweens 0.14 glycerine 0.55
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98100450 CN1205346A (en) | 1998-02-25 | 1998-02-25 | Controllable light biological whole degradation plastic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98100450 CN1205346A (en) | 1998-02-25 | 1998-02-25 | Controllable light biological whole degradation plastic |
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| CN1205346A true CN1205346A (en) | 1999-01-20 |
Family
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|---|---|---|---|
| CN 98100450 Pending CN1205346A (en) | 1998-02-25 | 1998-02-25 | Controllable light biological whole degradation plastic |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805463A (en) * | 2010-04-16 | 2010-08-18 | 深圳市科聚新材料有限公司 | Starch filled biodegradable polypropylene and preparation method thereof |
| CN105330954A (en) * | 2015-12-14 | 2016-02-17 | 民勤县邦德贸易有限公司 | Weather-proof resin master batch for agricultural plastic mulching film synthesis and preparation method |
| CN108976740A (en) * | 2017-05-31 | 2018-12-11 | 中国石油化工股份有限公司 | A kind of controlled degradation PVC composition and preparation method |
| CN111660640A (en) * | 2020-06-22 | 2020-09-15 | 长沙银腾塑印包装有限公司 | Degradable packaging product |
-
1998
- 1998-02-25 CN CN 98100450 patent/CN1205346A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805463A (en) * | 2010-04-16 | 2010-08-18 | 深圳市科聚新材料有限公司 | Starch filled biodegradable polypropylene and preparation method thereof |
| CN101805463B (en) * | 2010-04-16 | 2013-04-17 | 安徽科聚新材料有限公司 | Starch filled biodegradable polypropylene and preparation method thereof |
| CN105330954A (en) * | 2015-12-14 | 2016-02-17 | 民勤县邦德贸易有限公司 | Weather-proof resin master batch for agricultural plastic mulching film synthesis and preparation method |
| CN108976740A (en) * | 2017-05-31 | 2018-12-11 | 中国石油化工股份有限公司 | A kind of controlled degradation PVC composition and preparation method |
| CN111660640A (en) * | 2020-06-22 | 2020-09-15 | 长沙银腾塑印包装有限公司 | Degradable packaging product |
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