CN101608045B - Controllable light/biodegradation plastic material - Google Patents
Controllable light/biodegradation plastic material Download PDFInfo
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- CN101608045B CN101608045B CN2009100232718A CN200910023271A CN101608045B CN 101608045 B CN101608045 B CN 101608045B CN 2009100232718 A CN2009100232718 A CN 2009100232718A CN 200910023271 A CN200910023271 A CN 200910023271A CN 101608045 B CN101608045 B CN 101608045B
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- plastic material
- controllable light
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- acrylic acid
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Abstract
The invention discloses a controllable light/biodegradation plastic material, made of a polymer compound. The polymer compound comprises the following components and by weight part: 20 to 40 parts of polyvinyl alcohol, 5 to 25 parts of polyol, 0 to 10 parts of borax, 20 to 40 parts of ethylene acrylic acid copolymer, 5 to 15 parts of organic aldehyde compound and 0.05 to 0.5 part of photosensitizer. The invention fulfills the double functions of biodegradation and light degradation, mainly applies photocatalysis degradation to the ethylene acrylic acid copolymer which is difficult to carry out the biodegradation, and mainly carries out microbial degradation on the polyvinyl alcohol.
Description
Technical field
The present invention relates to a kind of controllable light/biodegradation plastic material, belong to the International Classification of Patents C08J5/00 technical field that " contains the manufacturing of the goods or the formed material of polymer substance ".
Background technology
Along with quantity of plastics grows with each passing day, produce a large amount of plastic refuses.Because it is difficult to degraded (common plastics could be degraded fully) in the time in 200～400 years, white pollution has become the worldwide public hazards of current harm social environment, has seriously hindered the sustainable development of social economy and environment.In order to solve this serious social concern, more and more scholars is advocated the development and application degradative plastics, and regards it as solve this world-famous puzzle desirable approach.Become competitively hot of research and development of countries in the world at present, many developed countries, the rules that limit the use of or forbid non-degradative plastics have all successively been formulated as the U.S., Japan, Germany etc., research and development plan and measure that many countries have also formulated degradative plastics, thereby make degradative plastics obtain developing rapidly in these areas, in the North America with annual 17% speed increment; In Europe then with annual 59% speed increment.In China, the also support on the just consideration policy and come into effect the tentative policy that degradative plastics substitutes common plastics in some areas of relevant department is as Wuhan, Guangzhou, Shenzhen and other places.
The degradative plastics of research can be divided into four classes, photodegradable plastics, biodegradable plastic, photo bio degradative plastics and water degradative plastics in the world at present.
Biodegradable plastic is meant under certain condition, can be under the effect of microorganism or enzyme and the plastic material that decomposes.Be characterized in: store convenient transportation, keep dry, need lucifuge, applied range not only can be used for agricultural mulching, also can be used for field of medicaments.The mechanism of degradation of biodegradable plastic, promptly the process digested and assimilated by effects such as bacterium, moulds of biodegradable plastic is biophysics and biochemical reaction.Behind the microbial attack plastics component, because thereby the growth of biomass cells makes polymeric components hydrolysis, ionization or protonated generation mechanical destruction, split into the oligopolymer fragment, polymer molecular structure is constant, and this is the biophysics effect of polymkeric substance and the degradation process that takes place.Non-soluble polymer is decomposed for fungi or bacterium excretory enzyme or oxidative degradation becomes water-soluble fragment, generates new micromolecular compound until finally resolving into carbonic acid gas and water, and this degraded mode belongs to the biochemical degradation mode.
Study the more starch plastics that has at present: its manufacture method mainly contains two kinds: the one, and blend.Because starch and Polymer Structure and polarity differ too big, thereby consistency is poor, obtain starch plastics again with polymer blending after need handling starch.Mix with polyethylene, polyvinyl alcohol, polypropylene, polystyrene as starch, can make plastic sheeting for farm use and wrapping material.Canada St.Lawreace starch company has researched and produced a kind of treated starch Ecostar master batch, can make biodegradable plastic with polyethylene, polypropylene, polystyrene, polyvinyl alcohol and polyurethane comixing, and can come the control degradation time by the content of regulating the Ecostar master batch, the polyethylene film that contains 15%Ecostar that makes as the said firm, degraded only needs six months, and containing the polyethylene film of 6%Ecostar, its degradation time then needs 3～5 years.The starch plastics of USDA exploitation is that moisture 40%～60% gelling starch is added among the EAA (ethylene-acrylic acid), mixes and makes agricultural mulching.The 2nd, copolymerization such as starch and unsaturated monomer such as vinylbenzene, ethene, propylene, vinyl cyanide, vinylformic acid and ester class thereof and the degraded polypropylene that obtains.The starch plastics of exploitation mainly contains at present: starch graft acrylic acid methyl esters, butyl acrylate, vinylbenzene etc.U.S. Purde university develops starch-grafted polystyrene and adopts cationic polymerization, molecular weight and rerum natura all can effectively be controlled, wherein starch-containing 20%～30% starch-grafted polymkeric substance has the similar character of common polystyrene, can be used as bottle, film etc.
Summary of the invention
The purpose of this invention is to provide a kind of biological degradation that is easy to, and can effective photodegradative controllable light/biodegradation plastic material, overcome the deficiencies in the prior art.
Implementation procedure of the present invention is as follows:
A kind of controllable light/biodegradation plastic material is made by polymeric composition, it is characterized in that each component of polymeric composition and weight part are:
Polyvinyl alcohol 20-40
Polyvalent alcohol 5-25
Borax 0-10
Ethylene-acrylic acid copolymer 20-40
Organic aldehyde compound 5-15
Photosensitizers 0.05-0.5
Described polyvinyl alcohol alcoholysis degree is 85%～100%.
Described polyvalent alcohol is selected from glycerol, sorbyl alcohol, ethylene glycol, propylene glycol, butyleneglycol, pentanediol, glycol ether or triglycol.
The content 10%～30% of AA in the described ethylene-acrylic acid copolymer.
Described organic aldehyde compound is selected from formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde or oxalic dialdehyde.
Described photosensitizers is selected from benzophenone, Acetyl Acetone cobalt, neodecanoic acid zirconium, hydrogen phthalate cerium or stearate, stearate such as molysite, rare-earth salts, cerium salt etc.
Advantage of the present invention and positively effect: (1) the present invention gives full play to biological degradation and photodegradation dual function, and mainly use photodegradation and handle for being difficult for biodegradable ethylene-acrylic acid copolymer, and for polyvinyl alcohol, main biodegrade.By dual degradation treatment, reach elimination " white " and pollute, the effect of protection environment.(2) the present invention adds ethylene-acrylic acid copolymer, can improve the water resistance and the intensity of degradative plastics.(3) technology of the present invention is simple, and degradation effect is obvious, is easy to suitability for industrialized production.
Embodiment
The present invention will be further described below in conjunction with embodiment.
The biological degradation experimental technique: sample grinds, weighs behind 50 ℃ of dry 24h, adds 100 times of distilled water, transfer pH to 4.6 with 1mol/L HCl, add Ye Huamei 1% and saccharifying enzyme 4% under 30 ℃ of magnetic agitation, the residue behind the enzymolysis washes surperficial gelatinization thing, weighs behind 50 ℃ of dry 24h.Measure different enzymolysis time degraded percentage ratios.
The photocatalytic degradation experimental technique: the plastic sample parallel suspend is in 25W ultraviolet ageing case, and the sample spacing is not less than 10mm, gets one time sample, the appearance change of viewing film in per 1 hour.
Embodiment 1:
Polyvinyl alcohol 25
Butyleneglycol 10
Ethylene-acrylic acid copolymer 15
Butyraldehyde 7
Photosensitizers cerium stearate 0.3
In high-speed mixer, with polyvinyl alcohol, glycerol and acetaldehyde mix stir 20 minutes after, heat temperature raising to 120 ℃ was kept 10 minutes, added ethylene-acrylic acid copolymer, cerium stearate salt, heat temperature raising to 160 ℃ was kept 20 minutes, carried out granulation.
The biodegradable plastic of preparation carried out enzymolysis 36 hours, and degree of degradation is 70.5%.
After the uv light exposure 30 hours, biodegradable plastic flavescence occurs, becomes fragile.
Embodiment 2:
Polyvinyl alcohol 40
Glycerol 15
Ethylene-acrylic acid copolymer 30
Propionic aldehyde 10
Photosensitizers benzophenone 0.15
Photosensitizers Acetyl Acetone cobalt 0.15
The preparation method is similar to Example 1.
The biodegradable plastic of preparation carried out enzymolysis 36 hours, and degree of degradation is 74.6%.
After the ultraviolet radiation 20 hours, biodegradable plastic flavescence occurs, becomes fragile.
Experimental studies have found that use benzophenone, Acetyl Acetone cobalt, neodecanoic acid zirconium, hydrogen phthalate cerium or lipid acid iron separately, uv light exposure is after 30 hours, biodegradable plastic flavescence just occurs, becomes fragile, degradation with aging.And use benzophenone and Acetyl Acetone cobalt complex photosensitizer, and only need i.e. degraded in 20 hours, illustrate that these two kinds of photodegradable aids have synergistic effect, ethylene-acrylic acid copolymer is had good Degradation.The weight ratio of further discovering photosensitizers benzophenone and Acetyl Acetone cobalt is to have good photochemical catalysis effect in 3: 1～1: 3.
Embodiment 3:
Polyvinyl alcohol 30
Sorbyl alcohol 15
Borax 5
Ethylene-acrylic acid copolymer 25
Oxalic dialdehyde 8
Iron stearate 0.3
Embodiment 4:
With the degradative plastics material of embodiment 2 preparation through ultraviolet radiation biodegrade experiment after 25 hours, enzymolysis 36 hours, degree of degradation is 90.7%.
Claims (6)
1. a controllable light/biodegradation plastic material is made by polymeric composition, it is characterized in that each component of polymeric composition and weight part are:
Polyvinyl alcohol 20-40
Polyvalent alcohol 5-25
Borax 0-10
Ethylene-acrylic acid copolymer 20-40
Organic aldehyde compound 5-15
Photosensitizers 0.05-0.5
Described photosensitizers is selected from benzophenone, Acetyl Acetone cobalt, neodecanoic acid zirconium, hydrogen phthalate cerium, cerium stearate, iron stearate.
2. according to the described controllable light/biodegradation plastic material of claim 1, it is characterized in that: the polyvinyl alcohol alcoholysis degree is 85%～100%.
3. according to the described controllable light/biodegradation plastic material of claim 1, it is characterized in that: polyvalent alcohol is selected from glycerol, sorbyl alcohol, ethylene glycol, propylene glycol, butyleneglycol, pentanediol, glycol ether or triglycol.
4. according to the described controllable light/biodegradation plastic material of claim 1, it is characterized in that: the content 10%～30% of AA in the ethylene-acrylic acid copolymer.
5. according to the described controllable light/biodegradation plastic material of claim 1, it is characterized in that: described organic aldehyde compound is selected from formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde or oxalic dialdehyde.
6. according to the described controllable light/biodegradation plastic material of claim 1, it is characterized in that: photosensitizers is benzophenone and Acetyl Acetone cobalt, and its weight ratio is 3: 1～1: 3.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009100232718A CN101608045B (en) | 2009-07-10 | 2009-07-10 | Controllable light/biodegradation plastic material |
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| CN2009100232718A CN101608045B (en) | 2009-07-10 | 2009-07-10 | Controllable light/biodegradation plastic material |
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| CN101608045A CN101608045A (en) | 2009-12-23 |
| CN101608045B true CN101608045B (en) | 2010-12-29 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103289265B (en) * | 2013-02-28 | 2015-08-12 | 章磊 | A kind of Novel photo-biodegradable plastic material |
| CN104017315A (en) * | 2013-02-28 | 2014-09-03 | 章磊 | Novel photo-biodegradable plastic material |
| CN104031302B (en) * | 2013-03-04 | 2016-07-06 | 中国科学院过程工程研究所 | A kind of controllable oxidization biodegradable plastic master batch and preparation method thereof |
| CN111718551A (en) * | 2020-07-08 | 2020-09-29 | 浙江晟祺实业有限公司 | Preparation process of degradable packaging material based on biological matrix |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4692494A (en) * | 1980-12-15 | 1987-09-08 | Colgate-Palmolive Company | Water soluble films of polyvinyl alcohol and polyacrylic acid and packages comprising same |
| CN1099399A (en) * | 1993-08-24 | 1995-03-01 | 北京华新淀粉降解树脂制品有限公司 | Biodegradable composition containing starch and its producing method and its use |
| CN1309145A (en) * | 2000-11-23 | 2001-08-22 | 西安科技学院 | Fully degradable multifunctional film |
| CN1847294A (en) * | 2006-03-15 | 2006-10-18 | 赵小英 | Biodegradable plastic alloy and its prepn process |
| CN1980991A (en) * | 2004-07-12 | 2007-06-13 | 宝洁公司 | Packaged composition for the delivery of said composition into an aqueous medium |
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- 2009-07-10 CN CN2009100232718A patent/CN101608045B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4692494A (en) * | 1980-12-15 | 1987-09-08 | Colgate-Palmolive Company | Water soluble films of polyvinyl alcohol and polyacrylic acid and packages comprising same |
| CN1099399A (en) * | 1993-08-24 | 1995-03-01 | 北京华新淀粉降解树脂制品有限公司 | Biodegradable composition containing starch and its producing method and its use |
| CN1309145A (en) * | 2000-11-23 | 2001-08-22 | 西安科技学院 | Fully degradable multifunctional film |
| CN1980991A (en) * | 2004-07-12 | 2007-06-13 | 宝洁公司 | Packaged composition for the delivery of said composition into an aqueous medium |
| CN1847294A (en) * | 2006-03-15 | 2006-10-18 | 赵小英 | Biodegradable plastic alloy and its prepn process |
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