CN1546563A - Total-starch type biodegradable plastic - Google Patents
Total-starch type biodegradable plastic Download PDFInfo
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- CN1546563A CN1546563A CNA2003101111107A CN200310111110A CN1546563A CN 1546563 A CN1546563 A CN 1546563A CN A2003101111107 A CNA2003101111107 A CN A2003101111107A CN 200310111110 A CN200310111110 A CN 200310111110A CN 1546563 A CN1546563 A CN 1546563A
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Abstract
A total-starch type biodegradable plastic by using dialdehyde starch whose oxidization degree is no less than 40% as the fundamental and principal raw material, through blended refining with long chain non-saturated carboxylic acid or acid anhydrides grafted and modified compositions, degradable aliphatic polyester or hydroxy acid blending component, organic peroxides initiating agent, polyhydric alcohol esters plasticizing agent, polyhydric alcohols and/or their esters compound stabilizing agent, higher hydrocarbons, aliphatic acids and their esters or polyamides compound lubricating agent.
Description
Technical field
The present invention relates to the biodegradable plastic that a kind of starch content surpasses 80% full starch-type, specifically is that the dialdehyde starch with oxidisability 〉=40% is the degradable plastic fully of fundamental sum main raw material.
Background technology
Plastics have become material most widely used on the our times, and various plastics have also related generally to social production and various fields in life, have occupied consequence.Solving developing resource-constrained of boundary's plastics industry and serious two hang-ups of ecological environmental pollution, the development and application to degradable plastics has been proposed.At present more have report and and the degradable plastics that comes into operation mainly be starch plastic.Currently reported starch plastic, mainly be filled-type starch plastic and starch plastics, starch content in its goods low (10～30%), all the other main components are still the macromolecule component that is difficult to degrade, therefore its degradability is poor, and the too late traditional macromolecule component plastics ideal of mechanical property, and price is also than the conventional plastic height.Therefore from actual service condition, still can not fundamentally solve " white pollution " problem.For this reason, people have strengthened the improved research of starch plastics, so that starch content increase in the material, good mechanical performance, can carry out thermoplastic processing, and the novel starch plastics that can reach fast, fully in environment, degrade.
People such as Wu Zhang Yong are in " plastics science and technology " 2003 (2): report among the 59-63 that present starch-based degradable plastics includes starch filled plastics, starch blending plastics and full starch plastic three classes.Wherein, starch filled plastics mainly are meant with starch filled as general-purpose plastics such as PE, PP, its starch addition＜30%, and degradation rate is slow and not exclusively, can cause secondary pollution.As publication number be the employing reported of the Chinese patent literature of CN1237596A and CN1296988A all be to make starch master batch earlier, then master batch is added to process in the resin again to obtaining the degradative plastics goods with certain proportion, what starch content was the highest in the degradative plastics goods is no more than 30%.This degradative plastics all is difficult to satisfy service requirements on biological degradability and mechanical property.Publication number is that the Chinese patent literature of CN1415651A has been reported a kind of " preparation method of starch-type complete degradable plastic ", and the starch content in its starch plastic can reach 30-60%, and certain raising has been arranged.Because the minimum standard of the starch content in the degraded starch plastics of approving usually in the world fully is 80% at present, and the starch content in this starch plastic the highest also only be 60%, still contain the polyvinyl resin about 40%, therefore degradation effect is not fine, and required degradation time is longer, and its mechanical property and ordinary resin plastics also have big gap.Simultaneously, it has also used the photosensitizers that contains heavy metal, and is influential to the use of product, and degraded product also has certain influence to environment.Though existing indivedual bibliographical informations have full biodegradable starch-plastics, the goods poor mechanical property does not reach the index of conventional plastic far away, can not satisfy service requirements.
The starch blending plastics mostly are gel starch and resin alloy forms, and mainly are the consistencies that increases starch and resin.Publication number is the so-called full starch plastic that the Chinese patent literature of CN1255508A and CN1137439A is reported, there are not thermoplastic property, intensity and stretching not enough and can only be used to make material by what steps such as heat of stirring is molded were made starch and xanthan gum etc. exactly as thick products such as cutlery boxs, can not be used for the processing of other plastics, the processing of particularly thin goods such as film, handbag etc., that as was expected yet is good for degradation effect, the comprehensive use properties of these full starch plastics can not be satisfactory, also do not applied up till now.
Full starch plastic then is based on starch, adds an amount of degradability additive, and what obtain is biological whole degradation plastic.Its principle is starch molecule allosteric and disordering, forms the starch-resin with thermoplastic property, and thermoplastic starch plastic therefore is otherwise known as.
Summary of the invention
At above-mentioned situation, the present invention will provide a kind of starch content can surpass 80% full starch-type biodegradable plastic, make it have excellent biodegradability, can be in a short time rapidly fully Degradation and Transformation be CO
2And H
2O can also have the ideal mechanical property simultaneously, the transparency height, and the processing characteristics excellence, adaptability is good, can be used for manufacturing in the usual way multiple disposable plastic goods commonly used.
Full starch-type biodegradable plastic of the present invention, be that dialdehyde starch with oxidisability 40% is the fundamental sum main raw material, with the graft modification composition and the degradable aliphatic polyester of long-chain unsaturated carboxylic acid or anhydrides or the alcohol acids mixture components is mixing forms, be in its composition form of weight part
90～95 parts of dialdehyde starchs,
1.0～3.0 parts of long-chain unsaturated carboxylic acid or acid anhydrides composition graft modification agent,
0.1～1.0 part of organic peroxide evocating agent,
1.0～5.0 parts in polyol ester compound softening agent,
0.5～3.0 part of polyvalent alcohol and/or its ester cpds stablizer,
0.1～2.0 part of lubricant,
2.0～6.0 parts of degradable aliphatic polyester or alkyd composition mixture components.
In the starch plastic of traditional form, what starch was adopted is in simple physics plasticising mode starch to be handled, for example that small molecules plasticity compositions such as glycerine, ethylene glycol and starch is mixed, reaches the plasticising purpose with the high-speed stirring mixing then.In the above-mentioned full starch-type degradable plastics of the present invention, used starch then is to adopt starch is carried out dialdehyde starch (DAS) after oxidative deformation is handled, promptly with the Periodic acid that starch had height specificity oxygenizement and sodium salt thereof the C with glycan molecule in its starch
2-C
3Carbon bond interrupts, and respectively its two hydroxyl oxygen is changed into aldehyde radical, is the maximum and the widest class modified starch of purposes of present consumption, and has realized large-scale industrial production at present.Dialdehyde starch is a kind of poly aldehyde cpd, though it still maintains the original shape of starch granules, but owing to contain a lot of easily aldehyde radical functional groups of reaction in the molecule, therefore have very high chemically reactive and excellent physical and biochemical property, in fields such as papermaking, process hides, building materials, weaving, medicine, food, demonstrated important purposes.Particularly because dialdehyde starch has changed starch structure, eliminated crystalline texture up hill and dale, thereby made starch can possess thermoplasticity, the modes such as blend commonly used in the plastic working, hot pressing that can be suitable for are handled, and obtain corresponding articles.
As the dialdehyde starch of the fundamental sum main component in the full starch-type biodegradable plastic of the present invention, can obtain through oxide treatment by any in the present starch commonly used.For example, can be by W-Gum, any in wheat starch, pea starch, the tapioca (flour) obtains dialdehyde starch through above-mentioned oxide treatment.Wherein, the oxidisability of said dialdehyde starch, promptly after the oxidation in the dialdehyde starch molecule-CHO and oxidation before in the molecule-ratio of OH, though height ratio hangs down.For example, test-results shows, when the oxidisability of dialdehyde starch can reach extraordinary effect greater than 80% the time.But the too high then Chang Yi of oxidisability makes the unnecessary increase of cost and makes complicated operationization.Test-results shows, when the oxidisability of dialdehyde starch reaches 40%～60%, can obtain satisfied practical function equally fully, and the hydroxyl of handling in the starch of back is few, makes crystalline texture obtain effective processing, the thermoplastic property ideal.If but oxidisability is low excessively, then, bigger disadvantageous effect can be arranged to thermoplasticity because the crystallization of ative starch can not get effective processing.
Because the dialdehyde starch of the fundamental sum main component in degradable plastics of the present invention has had thermoplastic property, can handle according to modes such as blend commonly used in the plastic working, hot pressing, therefore adopting on the basis of dialdehyde starch as the fundamental sum main component, other various complementary composition also can and/or be handled according to the selection of the usual manner in plastic working at present.For example:
The graft modification thing of described long-chain unsaturated carboxylic acid or anhydrides composition can be selected in dodecenylsuccinic acid acid anhydride commonly used, maleic anhydride (cis-butenedioic anhydride), hendecene base Succinic anhydried, the octadecenic acid etc. one or more for use.The test-results demonstration, wherein best with the effect of dodecenylsuccinic acid acid anhydride, but its price is higher; The active height of maleic anhydride, but volatility is also high.Therefore be good to select two kinds of mixed forms of using usually, can obtain good comprehensive benefit.
Described organic peroxide evocating agent can be selected for use as in commonly used dicumyl peroxide (DCP), benzoyl peroxide (BPO), ditertiary butyl peroxide (DTBP) and the lauroyl peroxide etc. one or more.Generally can only use a kind of, and comparatively commonly used with DCP.But, also can adopt the form of selecting two kinds of initiators to use with simultaneously in case of necessity in order to improve initiating activity and efficient.
Described polyol ester class aldehyde cpd softening agent, can as commonly used Polycizer W 260, hexanodioic acid two (2-ethylhexyl) ester (DOA), dibutyl phthalate, glycerine, ethylene glycol etc. in select one or more form for use.Wherein, the molecular weight of Polycizer W 260, hexanodioic acid two (2-ethylhexyl) ester (DOA), dibutyl phthalate is bigger, is the primary plasticizer of plastic material; Polycizer W 260, hexanodioic acid two (2-ethylhexyl) ester (DOA) consistency are good, but volatility is big; The dibutyl phthalate plasticization effect is good, and stability is also better.Test-results shows that two or more softening agent are mixed to be used as selecting generally speaking, though some trouble, how comparatively desirable plasticization effect is.
The stablizer of described organic compound or polyalcohols can be selected as 1, a kind of in the stablizer commonly used such as two (beta-amino butenoic acid) esters of 4-butyleneglycol, two (beta-amino butenoic acid) esters of thio-diethylene glycol, Sionit, tetramethylolmethane.Test-results shows that the stabilising effect of these stablizers is similar, thereby can select arbitrarily.
Described lubricant can be one or more mixtures in hydro carbons, lipid acid and ester class, the fatty acid amide etc. commonly used in the plastic working.For example, can be whiteruss (white oil), polyethylene wax, stearic acid, stearic amide etc.Wherein, whiteruss (white oil), polyethylene wax belong to the olefines lubricant, in plastics-production, often be used, but its general large usage quantity; And the high lubricating effect of constituents such as stearic acid, stearic amide, consumption is few, but price is then higher relatively.Therefore, can adopt wherein 2～3 kinds of common forms of using of selection usually.
Described degradable aliphatic polyester or alcohol acids material intermingling material are as in existing report and the materials such as polycaprolactone (PCL), polyglycolic acid (PGA) polyvinyl alcohol (PVA), urethane (PU) or vegetable fibre comparatively commonly used one or more.Wherein caprolactone (PCL), polyglycolic acid (PGA) polyvinyl alcohol (PVA) can improve the water tolerance and the oil-proofness of material, and urethane (PU) can improve the intensity and the elasticity of material, and vegetable fibre can increase the intensity of material.
The full starch-type biodegradable plastic of above-mentioned form, preparation can adopt method currently reported and that use to prepare.For example can there be the double screw rod extruder that places of report to finish mixing, reaction and granulation process by in the above-mentioned document said each material composition to material more.
Because above-mentioned full starch plastic is to be main raw material with starch through the dialdehyde starch of oxide treatment rear oxidation degree 〉=40%, active high, easily and other material generation grafting, crosslinking reaction, and possess plastic working handling properties such as thermoplasticity and blend, hot pressing, can with can biodegradable polymkeric substance, after polycaprolactone (PCL), polyvinyl alcohol (PVA), polyglycolic acid different substances blend such as (PGA), can obtain improving its mechanical property and have a water resisting property, the resin material of different qualities such as oil-proofness.Not only do not have fully in the material to degrade as polyethylene (PE), polypropylene ordinary resins such as (PP), and starch content wherein increases substantially, and surpassed 80%, having met is a kind of full starch plastic at present in the world.The starch content that has reached the complete degraded starch plastics of approving usually in the world fully is 80% minimum standard.Therefore can have excellent biodegradability, can fully be become CO rapidly in a short time by microbial transformation
2And H
2O.
Simultaneously, the mechanical property excellence of above-mentioned products obtained therefrom, tensile strength, elongation at break and flexural strength height, the transparency height can replace common polythene (PE), polypropylene (PP) resin to use fully, and have good thermoplastic processability, and adaptability is good.Resin can directly become polytype disposable plastic goods such as sheet material such as cutlery box, cup dish, flowerpot, office appliance and film, packing bag by processes such as extrusion molding, blowing, injection mouldings.
Because the raw material overwhelming majority is a renewable resources starch, adds that technical process is brief, therefore to compare with present common degradative plastics, production cost significantly reduces, and comparable common plastics and other starch plastic price are low more than 30%.
The embodiment of form is described in further detail foregoing of the present invention again by the following examples.But the scope that should at this point not be interpreted as the above-mentioned theme of the present invention only limits to following example.Do not breaking away under the above-mentioned technological thought situation of the present invention, all various modifications, replacement or changes of making according to ordinary skill knowledge and customary means, all being considered as is scope of the present invention.
Embodiment
Embodiment 1
Raw material and weight part consumption:
Oxidisability is 90 parts of 40%～60% dialdehyde starchs,
3.0 parts of dodecenylsuccinic acid acid anhydrides,
0.2 part of DCP (initiator),
5.0 parts of Polycizer W 260s,
1,2.0 parts of two (beta-amino butenoic acid) esters of 4-butyleneglycol,
2.0 parts of whiterusss,
3.0 parts of PCL.
The dialdehyde starch in the raw material wherein can be with reference to can be with reference to the method preparation of patent GB943664 " Process for oxidationof starch ".
By the usual manner of plastic working, the mixed fusion of high-speed stirring under 150 ℃ of-180 ℃ of temperature with PCL in the raw material and Polycizer W 260.Be about to add initiator DCP, properties-correcting agent dodecenylsuccinic acid acid anhydride, stablizer 1 when fusion finishes, two (beta-amino butenoic acid) esters of 4-butyleneglycol and lubricant whiteruss make the complete fusion of material and evenly mixed.Add dialdehyde starch then and in the high-speed mixer of routine, mix reaction jointly, blowing and be cooled to 30 ℃ of-40 ℃ of pulverizing after 20-30 minute.
Material after pulverizing is sent in the double screw rod extruder,, carried out mixing granulator in 145 ℃-190 ℃.Wherein: the fs temperature is set to: 145 ℃-170 ℃ of one to three district's temperature, 150 ℃-190 ℃ of four to six district's temperature, 140 ℃-180 ℃ of seven to nine district's temperature, and ten to 125 ℃-150 ℃ of No.12 District temperature; The temperature of subordinate phase is provided with 130 ℃-160 ℃ of one to three district's temperature, 110 ℃-150 ℃ in four districts, five districts.The rotating speed of main frame and feeding machine is respectively 100-300 rev/min and 10-30 rev/min, vacuum tightness 0.02-0.08MPa.Three reaction zone pressures of fs remain on 0.5-10MPa, residence time of material 2-20 minute.The blend material enters the subordinate phase forcing machine, and residence time of material 2-10 minute, head pressure remained 0.5-10MPa.Through subordinate phase extrude mixing after granulation, promptly obtain all starch biodegradation Plastic Resin.
This full starch-resin is blow molded into the packing bag of 0.02mm with usual manner, and its main performance index detects as shown in the table:
The main performance index of membrane product
| The QB/T2461-99 standard | Measured value of the present invention | |
| Tensile strength (Mpa) | 〉=10 | 〉=12 |
| Elongation at break (%) | 〉=100 | 〉=300 |
| Biological degradability | Rate of weight loss 〉=10% | Rate of weight loss 〉=90% is complete biodegradable, and degraded product is CO 2And H 2O. |
Embodiment 2
Each component and weight part consumption:
95 parts of dialdehyde starchs (with example 1),
2.0 parts of maleic anhydrides,
0.6 part of BPO,
4.0 parts of hexanodioic acid two (2-ethylhexyl) esters (DOA),
3.0 parts of Sionits,
1.0 parts of polyethylene waxs,
5.0 parts of PGA.
By operating, obtain corresponding all starch biodegradation Plastic Resin with same feed way and the condition of example 1.
Embodiment 3
Each component and weight part consumption:
92 parts of dialdehyde starchs (identical) with example 1,
1.0 parts of octadecenic acids,
1.0 parts of DCP/BPO (1: 1),
2.0 parts of glycerine/ethylene glycol (1: 1),
1.5 parts of tetramethylolmethanes,
1.5 parts of stearic acid,
6.0 parts on PVA/ vegetable fibre (1: 1).
By operating, obtain corresponding all starch biodegradation Plastic Resin with same feed way and the condition of example 1.
Claims (10)
1. full starch-type biodegradable plastic, it is characterized in that the dialdehyde starch with oxidisability 40% is the fundamental sum main raw material, with the graft modification composition and the degradable aliphatic polyester of long-chain unsaturated carboxylic acid or anhydrides or the alcohol acids mixture components is mixing forms, be in its composition form of weight part
90～95 parts of dialdehyde starchs,
1.0～3.0 parts of long-chain unsaturated carboxylic acid or acid anhydrides composition graft modification agent,
0.1～1.0 part of organic peroxide evocating agent,
1.0～5.0 parts in polyol ester compound softening agent,
0.5～3.0 part of polyvalent alcohol and/or its ester cpds stablizer,
0.1～2.0 part of lubricant,
2.0～6.0 parts of degradable aliphatic polyester or alkyd composition mixture components.
2. full starch-type biodegradable plastic as claimed in claim 1 is characterized in that said dialdehyde starch can be by W-Gum, and any in wheat starch, pea starch, the tapioca (flour) handled the dialdehyde starch that obtains through oxidative deformation.
3. full starch-type biodegradable plastic as claimed in claim 1, what it is characterized in that said long-chain unsaturated carboxylic acid or acid anhydrides composition graft modification agent can be in dodecenylsuccinic acid acid anhydride, maleic anhydride (cis-butenedioic anhydride), hendecene base Succinic anhydried, the octadecenic acids etc. is at least a.
4. full starch-type biodegradable plastic as claimed in claim 1, what it is characterized in that said organic peroxide evocating agent can be in dicumyl peroxide, benzoyl peroxide, ditertiary butyl peroxide or the lauroyl peroxide is at least a.
5. full starch-type biodegradable plastic as claimed in claim 1, what it is characterized in that said polyol ester compound softening agent can be in Polycizer W 260, hexanodioic acid two (2-ethylhexyl) ester, dibutyl phthalate, glycerine, the ethylene glycol is at least a.
6. full starch-type biodegradable plastic as claimed in claim 1, it is characterized in that said polyvalent alcohol and/or its ester cpds stablizer can be Sionit, tetramethylolmethane, 1, at least a in two (beta-amino butenoic acid) esters of two (beta-amino butenoic acid) esters of 4-butyleneglycol or thio-diethylene glycol.
7. full starch-type biodegradable plastic as claimed in claim 1, what it is characterized in that said lubricant can be in higher hydrocarbons, lipid acid and ester class or the amides is at least a.
8. full starch-type biodegradable plastic as claimed in claim 7, what it is characterized in that said higher hydrocarbons, lipid acid and ester class thereof or amides lubricant can be in whiteruss, polyethylene wax, stearic acid, the stearic amides is at least a.
9. full starch-type biodegradable plastic as claimed in claim 1, what it is characterized in that said degradable aliphatic polyester or alkyd composition intermingling material can be in polycaprolactone, polyglycolic acid, polyvinyl alcohol, urethane or the vegetable fibres is at least a.
10. as the described full starch-type biodegradable plastic of one of claim 1 to 9, the oxidisability that it is characterized in that said dialdehyde starch is 40%～60%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101111107A CN1303154C (en) | 2003-12-05 | 2003-12-05 | Total-starch type biodegradable plastic |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101111107A CN1303154C (en) | 2003-12-05 | 2003-12-05 | Total-starch type biodegradable plastic |
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| CN1546563A true CN1546563A (en) | 2004-11-17 |
| CN1303154C CN1303154C (en) | 2007-03-07 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1928283A1 (en) * | 2005-09-09 | 2008-06-11 | Leopold Looijé | Disposable vase |
| CN100429263C (en) * | 2004-11-18 | 2008-10-29 | 成都新柯力化工科技有限公司 | Biological-degradable starch/polyester plastic completely and production thereof |
| CN103146033A (en) * | 2013-03-08 | 2013-06-12 | 太仓协乐高分子材料有限公司 | Method for producing biodegradable plastic |
| CN103408803A (en) * | 2013-07-18 | 2013-11-27 | 吴江市利达上光制品有限公司 | Full-starch degradable plastic |
| CN104558700A (en) * | 2014-12-31 | 2015-04-29 | 成都新柯力化工科技有限公司 | Preparing method of bioplastic master batch |
| CN106243682A (en) * | 2016-08-02 | 2016-12-21 | 安徽美翔塑业有限公司 | A kind of starch polyurethane is blended garment bag and preparation method thereof |
| CN108395583A (en) * | 2018-03-27 | 2018-08-14 | 诸城兴贸玉米开发有限公司 | A kind of degradable starch-based fresh food package sheet material raw material and preparation method thereof |
| CN111234321A (en) * | 2020-03-31 | 2020-06-05 | 宁波普莱斯帝金属制品有限公司 | Preparation method of starch/polylactic acid composite material capable of being rapidly degraded |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039648C (en) * | 1991-08-01 | 1998-09-02 | 诺瓦蒙特股份公司 | Biodegradable polymeric compositions based on starch and thermoplastic polymers |
| CN1058736C (en) * | 1994-05-27 | 2000-11-22 | 北京市星辰现代控制工程研究所 | Preparing method for biodegradation compound and its use |
-
2003
- 2003-12-05 CN CNB2003101111107A patent/CN1303154C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100429263C (en) * | 2004-11-18 | 2008-10-29 | 成都新柯力化工科技有限公司 | Biological-degradable starch/polyester plastic completely and production thereof |
| EP1928283A1 (en) * | 2005-09-09 | 2008-06-11 | Leopold Looijé | Disposable vase |
| CN103146033A (en) * | 2013-03-08 | 2013-06-12 | 太仓协乐高分子材料有限公司 | Method for producing biodegradable plastic |
| CN103408803A (en) * | 2013-07-18 | 2013-11-27 | 吴江市利达上光制品有限公司 | Full-starch degradable plastic |
| CN104558700A (en) * | 2014-12-31 | 2015-04-29 | 成都新柯力化工科技有限公司 | Preparing method of bioplastic master batch |
| CN106243682A (en) * | 2016-08-02 | 2016-12-21 | 安徽美翔塑业有限公司 | A kind of starch polyurethane is blended garment bag and preparation method thereof |
| CN108395583A (en) * | 2018-03-27 | 2018-08-14 | 诸城兴贸玉米开发有限公司 | A kind of degradable starch-based fresh food package sheet material raw material and preparation method thereof |
| CN111234321A (en) * | 2020-03-31 | 2020-06-05 | 宁波普莱斯帝金属制品有限公司 | Preparation method of starch/polylactic acid composite material capable of being rapidly degraded |
| CN111234321B (en) * | 2020-03-31 | 2021-11-12 | 深圳市富恒新材料股份有限公司 | Preparation method of starch/polylactic acid composite material capable of being rapidly degraded |
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|---|---|
| CN1303154C (en) | 2007-03-07 |
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