CN1478808A - Starch base trielement system complete biodegradation film and blow moulding film forming method - Google Patents
Starch base trielement system complete biodegradation film and blow moulding film forming method Download PDFInfo
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- CN1478808A CN1478808A CNA021417563A CN02141756A CN1478808A CN 1478808 A CN1478808 A CN 1478808A CN A021417563 A CNA021417563 A CN A021417563A CN 02141756 A CN02141756 A CN 02141756A CN 1478808 A CN1478808 A CN 1478808A
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Abstract
A fully biodegradable three-element starch-base film is prepared from starch-polyvinyl alcohol-polyaliphatic biol bicarboxylate or EAA, the three-element plasticizer, reinforcing agent, and modifier through mixing, reaction, granulating, and blow moulding. Its advantages are good mechanical performance, high resistance to high or low temp and water, and short microbial degradation time (6 months).
Description
The present invention relates to a kind of film of fully biodegradable and use the film forming method of common blow moulding machine blowing.When people sought ' white pollution ' that polyethylene, polypropylene, polystyrene, polyvinyl chloride that degradable mulch film and wrapping material are on the rise with redemption bring, initial exploration was exactly biodegradable starch and organic acid or ester to be incorporated into go in the common polyethylene film or approach by photoxidation reaches this purpose.Because no matter be photodegradation, biological degradation or light/bio-degradable all are the processes of an oxidation, and it finally is to become acid or ester and be decomposed into CO
2With water with back to nature.So polyethylene/polycaprolactone, polyethylene type, starch-polyethylene acrylic acid-polyethylene degradative membrane and Light ?lysis Film are come out one after another.But find that this class film only starch can be degraded and polyethylene can not be by microbiological degradation.Therefore this class film has experienced the process of cooling, and generation is the research and development of a series of organic acids or ester, as Biopol, this is the multipolymer of hydroxybutyric acid and hydroxypentanoic acid, the ester of poly(lactic acid) (PLA), polycaprolactone (PCL), polycarbonate and aliphatic dicarboxylic acid and dibasic alcohol polycondensation is for another example come out one after another as Japan ' Bionolle ' etc., and is also very effective really, unique weak point is too expensive, can not be used for general wrapping material and mulch film.
U.S. F, H, Otey etc. have developed the film (Ind of a kind of polyvinyl alcohol-starch-polyvinyl chloride type, Eng.Chem.Prod.Res.Dev.1980,19,592-595), this film starch-containing 60%, about polyvinyl alcohol 15%, polyvinyl chloride colloidal sol coated is improved the water-resistant capacity of film on polyvinyl alcohol-starch film.This film almost do not have wet tenacity, and the introducing of polyvinyl chloride is disadvantageous to degraded under the situation of coated polyvinyl chloride not.It is the Biodegradable films (MP1991 that the modified polyvinyl alcohol of 70% starch and 30% prepares that Italy Ferruxxi company uses its relative quantity, 100,9, P7), be called Meter-Bi, have the ability of degraded fully, and price is relatively low, be listed in one of three famous in the world big fully biodegradable plastics brands, two classes are the Biopol of Britain ICI in addition, the Novon of the U.S. (being close to full starch).But it is temperature tolerance that Meter-Bi has the weakness of a maximum, and weather resisteant and water tolerance have limited its use range inadequately and seriously, can not be beyond 0-50 ℃ as it, use under low temperature, high temperature and the high humidity environment condition beyond the relative humidity 30-80%.
The objective of the invention is to overcome Meter-Bi weather-proof, heatproof and water-fast aspect defective, to widen the use range of such film, provide a kind of its use range wide more than Meter--Bi, the film of complete biodegradable in a short time again, and provide the common blow moulding machine blowing of a kind of use film forming method.
The present invention realizes by following measure:
This prescription contains starch, polyvinyl alcohol, di-carboxylic acid (as maleic anhydride, hexanodioic acids etc.) ester of same dibasic alcohol (as ethylene glycol) polycondensation, compatilizer, softening agent, strengthening agent, cold-resistance agent etc. are through blending reaction, granulation, the blowing film forming also can be passed through the T connector film extrusion.
Starch and polyvinyl alcohol, poly-di-carboxylic acid binary alcohol esters are the main body of film, starch is biodegradable inductor, and with polyvinyl alcohol good consistency is arranged, can increase the content of starch in film greatly, this is that general polyethylene addition type degradative plastics is difficult to accomplish.Polyvinyl alcohol has biodegradation character, and can be used as soil improvement agent, and the film dry strength might as well.But starch/polyvinyl alcohol film wet tenacity is poor, and water tolerance is bad, introduces poly-di-carboxylic acid binary alcohol ester and mainly is in order to improve the water tolerance of film, particularly high temperature water resistance and improve the kindliness of film.Just " Bionolle " of the advantage of Meter-Bi with Japan combined, and the two key fatty amide one hexanodioic acid glycol ester ternary built plasticising consistency systems of use glycerine-N, N, three effects are greatly arranged, the one, play plasticising, lubrication, the 2nd, in order to improve the weathering resistance of film, particularly improve the low-temperature performance of film, the 3rd, lay the foundation with the over-all properties that improves film for introducing a spot of polyethylene in order to improve the consistency of ternary system, particularly N, the two key fatty amides of N '.And the introducing of strengthening agent and Wet Strength Resin all improves a lot the tensile strength of film and wet tenacity, its tensile strength can reach the above even 30MPa of 20MPa, 12Mpa height than Meter--Bi, more than the enforcement of these measures make starch-polyvinyl alcohol film no matter at weather resisteant, all there is very big improvement temperature tolerance and water tolerance aspect than Meter--Bi. make it can be near the use range of polyethylene film.
Concrete prescription of the present invention (weight percentage)
| Starch | 30-65％ | Polyvinyl alcohol | 10-30％ |
| Poly-di-carboxylic acid glycol ester class | 10-30％ | Composite softening agent | 10-20％ |
| Strengthening agent | 0.1-0.4％ | Wet Strength Resin | 0.5-1.5％ |
| Polyethylene | 0-10％ | Defoamer | 0.1-0.3％ |
Starch used in the present invention is a kind of in W-Gum, potato starch, tapioca (flour), lotus root starch or the high amylose starch;
Polyvinyl alcohol used in the present invention is PVA-1799 or PVA-1999;
Polyester used in the present invention is the ester of maleic anhydride and ethylene glycol or hexanodioic acid and ethylene glycol polycondensation or EAA etc.;
Softening agent used in the present invention is glycerine-polyester polyol (as the polycondensation ester of Succinic Acid to certain herbaceous plants with big flowers diacid and ethylene glycol) two strong fatty amides of NN ';
Strengthening agent used in the present invention is potassium aluminium sulfate, alkali type aluminium oxide, borax, water glass etc.;
Wet Strength Resin used in the present invention is Wet Strength Resin APE;
Polyethylene used in the present invention is LLDPE and general LLDPE pellet
Defoamer used in the present invention is tributyl phosphate or silicone oil;
This is a general-purpose plastics processing high speed mixer to invent employed mixer;
Tablets press used in the present invention is short 45 types or 65 type list screw pelletizers of length-to-diameter ratio;
Blow moulding machine used in the present invention is general three sections screw rod blow moulding machines, is convenient to promote.Also can use T connector processing film forming or sheet material.
The present invention is prepared by the following method:
Blend → granulation → blowing → goods
Before blend, make maleic anhydride or hexanodioic acid and ethylene glycol carry out esterifying polycondensation earlier, get polycondensation product.(also can use Potassium Persulphate to make the maleic anhydride autohemagglutination certainly, also can use ceric ammonium nitrate to make maleic anhydride and starch connect the skill copolymerization).
When blend, add polyvinyl alcohol, starch earlier in mixer, stir, adding strengthening agent soluble in water, Wet Strength Resin etc. again mixes with the PVA/ starch material, add again in the two strong fatty amides of glycerine-NN-polyester polyol ternary softening agent of the polycondensation product of above maleic anhydride or hexanodioic acid and ethylene glycol and preparation by a certain percentage, the poly-di-carboxylic acid glycol ester mixed solution of this softening agent is added in the above PVA/ starch compound, stir evenly, blend composition granulation in 45 or 65 type single screw extrusion machines, each section temperature is roughly:
Barrel zone temperature: one section 60-70 ℃
Two sections 110-120 ℃
Three sections 120-130 ℃
Die head is taken over: 110-120 ℃
Die head: 95-105 ℃
Pellet can be blown film forming on common blow moulding machine.Mold temperature is roughly:
Machine Jian Wendu: one section 120-125 ℃
Two sections 130-140 ℃
Three sections 140-150 ℃
Shake the head adapter: 110-120 ℃
Die head: 105-118 ℃
Prepared film bag on bag machine, the sealing temperature of its sealing machine are 150-160 ℃, and pressure is: 2Kg/cm
2
The prepared film of the present invention, mechanical property be tensile strength at 20Mpa-30Mpa, extension at break is 140-200%; Young's modulus is 130-400Mpa;
This class film is measured through the carbon dioxide releasing amount assay method when starch content is 30% left and right sides, and the biological degradation rate in the time of four months reaches as high as more than 85%, and starch content to be about 60% film inspect by ready samples by the degradation experiment of the world and domestic standard.This class film is through trying the shop in the field, its surface is corroded and blackening by bacterium and Institute of Micro-biology fully in the time of two months, degraded substantially fully about half a year.
The prepared film of the present invention mainly can be used as shopping bag, and refuse bag and packing bag also can be used as mulch film.Mter-Bi generally can not be beyond 0-50 ℃; Relative humidity is used under low temperature, high temperature and high humidity environment beyond the 30-80%, and the prepared film of the present invention generally can use under the envrionment conditions that the PE film can be used, and its water tolerance, temperature tolerance and anti-inclining property are better than Meter-Bi.
The embodiment of the invention:
(example 1): take by weighing PVA350 part, 500 parts of starch change even in temperature material machine.Take by weighing 230 parts in water, in water, add 3 parts of potassium aluminium sulfates, 10 parts of Wet Strength Resin APE, 3 parts of defoamers under agitation, will mix with starch and PVA in this aqueous solution adding mixer.The ratio that takes by weighing the two key fatty amides of polyester polyol, glycerine and NN ' again is 2: 8: 6 160 parts of mixed solutions, stirs down, and adding has in the mixer of above-mentioned material, stirs evenly high-speed stirring 2 minutes.In length-to-diameter ratio is granulation in 25: 1 the 45 type single screw extrusion machines, machine Jian Wendu is one section: 60-70 ℃, two sections: 100-110 ℃, three sections: 115-120 ℃, die head is taken over: 105-110 ℃, and granulation under head: the 95-100 ℃ condition, blowing film forming on common blow moulding machine, mold temperature: one section of machine barrel: 120-125 ℃, two sections: 125-135 ℃, three sections: 135-145 ℃.Die head is taken over: 110-120 ℃, head: 105-115 ℃, prepared film is used for bag.
(example 2): take by weighing PVA150 part, 580 parts of starch stir evenly in mixer.Take by weighing 200 parts of water again, add 10 parts of 3 parts of alkali type aluminium oxides and Wet Strength Resins in the water, 2 parts of defoamers, the aqueous solution adds in the mixer in the lump.The ratio that takes by weighing the two strong fatty amides of NN ', glycerine and polyester polyol is 6: 8: 3 170 parts in a softening agent.Add 150 parts of the polycondensates of polymaleic anhydride and ethylene glycol in this, add in the lump in the mixer, material is stirred evenly.Granulation and blowing process are with example 1, and the film of gained is at 2Kg/cm
2Pressure, temperature are bag on 150-160 ℃ the sealing machine.
(example 3): take by weighing PVA150 part, 550 parts of starch stir evenly in mixer, take by weighing 200 parts of water again, add 3 parts of boraxs, 10 parts of Wet Strength Resins, 2 parts of defoamers in the water.This aqueous solution is added in mixer, take by weighing polyester polyol, glycerine, ethylene glycol bisthioglycolate methyl alcohol ratio and be 3: 10: 5 180 parts in softening agent, add EAA130 part in this, add in the lump in the mixer, material stirs evenly.Granulation and blowing process are with example 1.
(example 4): take by weighing 120 parts of acid polyethylenes, starch places mixer for 580 parts, stir evenly, take by weighing 220 parts in water, add 3 parts in alum, Wet Strength Resin APE10 part, 2 parts of defoamers are in water, add under stirring at low speed in the mixer, the ratio that takes by weighing the two strong fatty amides of NN ', glycerine, polyester polyol (adipate glycol polyester) is 6: 9: 3 180 parts of mixed liquid, adds 150 parts of poly-adipate glycol polycondensation esters in this plasticiser system.Under agitation, it is added in the mixer, carry out granulation and blowing after material stirs evenly, granulation and blowing process are with example 1.
(example 5): take by weighing PVA180 part, 520 parts of starch place mixer, take by weighing 200 parts in water, add 3 parts of water glass, 10 parts of Wet Strength Resins, 2 parts of defoamers are in water, under stirring at low speed, this aqueous solution is added in mixer, takes by weighing NN ' fatty amide: glycerine: the ratio of ethylene glycol adipate(EGA) is 5: 6: 5 160 parts of softening agent mixed solutions, add EAA130 part in this softening agent, the softening agent mixed solution that will be added with EAA adds in the mixer, material stir evenly and the blowing process the same.
(example 6): take by weighing PVA200 part, 600 parts of starch, put with mixer in, stir evenly, take by weighing 200 parts in water, in water, add 3 parts of boraxs, 10 parts of Wet Strength Resins, 2 parts of defoamers will stir evenly in this aqueous solution adding mixer, take by weighing glycerine: the two key fatty amides of NN ': the ratio of polyester polyol is 6: 6: 5 170 parts of mixed solutions, add 80 parts of EVA (EVA content is 33%) in this, under agitation, this mixed solution is added in the mixer, material stirs evenly, and granulation and blown film process are the same.
(example 7): take by weighing PVA160 part, 560 parts of starch place mixer, take by weighing 200 parts in water, add 3 parts of boraxs in water, 12 parts of Wet Strength Resins, and 1 part of defoamer adds this aqueous solution in the mixer, takes by weighing glycerine: adipate glycol fat; The two key fatty amide ratios of NN ' are 8: 4: 6 180 parts of softening agent mixed solutions, add 120 parts of the polycondensates of maleic anhydride and ethylene glycol, under agitation add in the mixer, and after material stirred evenly, its granulation and blowing process were the same.
(example 8): take by weighing PVA150 part, 550 parts of starch stir evenly in mixer, add 200 parts of entry, add 3 parts of boraxs, 12 parts of Wet Strength Resins in water; 2 parts of defoamers, under agitation, this aqueous solution is added in the mixer, stir evenly, take by weighing the two key fatty amides of NN ': glycerine: the ratio of polyester polyol is 8: 6: 4 180 parts of mixed solutions, and 160 parts in the mixture that adds EAA: PE and be 2: 1 stirs down this softening agent mixed solution is added in mixer in softening agent, stir evenly, granulation and blowing process are the same.
(example 9): take by weighing PVA150 part, 520 parts of starch place mixer, stir evenly, and take by weighing 200 parts in water.3 parts of boraxs are soluble in water, and this aqueous solution is added in mixer, take by weighing the two key fatty amides of NN ': glycerine: the ratio of polyester polyol is 8: 6: 4 160 parts of mixed solutions, adds EVA; The ratio of PE be 2: 1 150 parts in mixture in softening agent, again this mixture is added in mixer, stir, granulation and blowing process are the same.
Claims (6)
1, a kind of film of fully biodegradable, its prescription (weight percentage):
Starch 30-65％ Polyvinyl alcohol 10-30％
Poly-di-carboxylic acid glycol ester class 10-30％ Composite softening agent 10-20％
Strengthening agent 0.1-0.4％ Wet Strength Resin 0.5-1.5％
Polyethylene 0-10％ Defoamer 0.1-0.3％
2, according to claim 1, the ester that it is characterized in that poly-di-carboxylic acid and dibasic alcohol polycondensation is the ester of maleic anhydride and ethylene glycol or hexanodioic acid and ethylene glycol polycondensation;
3, according to claim 1, it is characterized in that softening agent is glycerine-polyester polyol (by the ester of Succinic Acid to certain herbaceous plants with big flowers diacid and ethylene glycol polycondensation) the two key fatty amide of DH-NN ' ternary built system of different ratios;
4, according to claim 1, it is characterized in that strengthening agent is a potassium aluminium sulfate, alkali type aluminium oxide, one or both in borax or the water glass;
5, according to claim 1, it is characterized in that its dispersion agent and defoamer are tributyl phosphate, silicone oil or polyacrylate;
6, as the preparation method of the said Biodegradable films of claim 1, comprising:
Carry out the polycondensation of fat dicarboxylic acid and dibasic alcohol, get polycondensation product 1., earlier;
2., add polyvinyl alcohol, starch in mixer, stir, adding strengthening agent soluble in water, Wet Strength Resin etc. again mixes with the PVA/ starch material, add again in the two strong fatty amides of glycerine-NN-polyester polyol ternary softening agent of the polycondensation product of above maleic anhydride or hexanodioic acid and ethylene glycol and preparation by a certain percentage, the poly-di-carboxylic acid glycol ester mixed solution of this softening agent is added in the above PVA/ starch compound, stir evenly, compound is used for granulation;
3., granulation in single screw extrusion machine, it is characterized in that:
Prilling temperature: one section 60-70 ℃ of machine barrel
Two sections 100-110 ℃
Three sections 120-130 ℃
The film head is taken over: 110-115 ℃
The film head; 95-105 ℃
4., pellet blowing film forming on common blow moulding machine, also can be on T connector film extrusion, it is characterized in that the extruder screw length-to-diameter ratio is 20-25: 1.
Mold temperature is:
One section of machine barrel: 125-130 ℃
Two sections: 130-140 ℃
Three sections: 135-145 ℃
The film head is taken over: 110-120 ℃
Film head: 100-115 ℃
5., prepared film bag on bag machine, it is characterized in that sealing machine bag temperature is 150-160 ℃, pressure 2kg/cm
2
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA021417563A CN1478808A (en) | 2002-08-26 | 2002-08-26 | Starch base trielement system complete biodegradation film and blow moulding film forming method |
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| CNA021417563A CN1478808A (en) | 2002-08-26 | 2002-08-26 | Starch base trielement system complete biodegradation film and blow moulding film forming method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1293137C (en) * | 2005-03-31 | 2007-01-03 | 方墉 | Total biodegradable film and preparation method |
| CN1297599C (en) * | 2004-04-27 | 2007-01-31 | 胡靖� | Utterly biodegradable packaging film and mulch film |
| CN1315927C (en) * | 2005-07-21 | 2007-05-16 | 同济大学 | Green degradable resin and production thereof |
| CN101225206B (en) * | 2008-02-01 | 2010-06-02 | 成都新柯力化工科技有限公司 | Polyvinyl alcohol modified biological material and preparation method |
| CN105237813A (en) * | 2014-07-08 | 2016-01-13 | 蒋永清 | Formula of degradable mulching film for paddy field and preparation method for formula |
| CN107880360A (en) * | 2017-12-05 | 2018-04-06 | 佛山君帝环保科技有限公司 | A kind of environment-friendly shopping bag |
-
2002
- 2002-08-26 CN CNA021417563A patent/CN1478808A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297599C (en) * | 2004-04-27 | 2007-01-31 | 胡靖� | Utterly biodegradable packaging film and mulch film |
| CN1293137C (en) * | 2005-03-31 | 2007-01-03 | 方墉 | Total biodegradable film and preparation method |
| CN1315927C (en) * | 2005-07-21 | 2007-05-16 | 同济大学 | Green degradable resin and production thereof |
| CN101225206B (en) * | 2008-02-01 | 2010-06-02 | 成都新柯力化工科技有限公司 | Polyvinyl alcohol modified biological material and preparation method |
| CN105237813A (en) * | 2014-07-08 | 2016-01-13 | 蒋永清 | Formula of degradable mulching film for paddy field and preparation method for formula |
| CN107880360A (en) * | 2017-12-05 | 2018-04-06 | 佛山君帝环保科技有限公司 | A kind of environment-friendly shopping bag |
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