CN1125121C - Optically and biologically degradable plastics and its preparing process - Google Patents
Optically and biologically degradable plastics and its preparing process Download PDFInfo
- Publication number
- CN1125121C CN1125121C CN 00126615 CN00126615A CN1125121C CN 1125121 C CN1125121 C CN 1125121C CN 00126615 CN00126615 CN 00126615 CN 00126615 A CN00126615 A CN 00126615A CN 1125121 C CN1125121 C CN 1125121C
- Authority
- CN
- China
- Prior art keywords
- optically
- starch
- agent
- biologically degradable
- degradable plastics
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The present invention relates to optically and biologically degradable plastic which is characterized in that the components of the present invention comprises 80 to 100 (mass portions, the same below) of polyolefin, 0.05 to 5 of photosensitizer, 0.05 to 2 of degradation accelerating agent, 0.1 to 5 of optically stabilizing agent, 0.001 to 1 of free agent initiator, 0.01 to 5 of comonomer, 0.5 to 10 of self-oxidizing agent and 100 to 80 of modified starch. The present invention has the manufacturing method that 1) the modified starch is manufactured; 2) the polyolefin, the comonomer and the initiator are thoroughly mixed according to the proportion, are heated to 60 (+/-) 5 DEG C and are reacted for 0.5 hours to be manufactured into the modified polyolefin, then the modified starch in (1) is added in the polyolefin, the comonomer and the initiator, and the photosensitizer, the degradation accelerating agent, the optically stabilizing agent and the self-oxidizing agent are added to be thoroughly mixed; 3) all the component mixtures are granulated.
Description
The present invention relates to a kind of biodegradable plastic and manufacture method thereof, be suitable for making wrapping material, packaging material for food, agricultural mulching etc.
The method of disposal of plastic waste rubbish, be to adopt heap to bury in the past, burning and recycling etc., because all having difficulty separately, this several method seems not ideal enough, people tended to use the plastics that can degrade fully under field conditions (factors) to replace the plastics that widely used traditional synthesized polymer material is made in the last few years, by constantly seeking, these class plastics can be with making by the novel high polymer compound of chemosynthesis and biosynthetic means manufacturing, also can adopt natural resources, as starch, fiber is usually made, and makes but more generally traditional macromolecular material is carried out modification.Made degradable plastics, bio-degradable plastics and light, biodegradation plastic at present, these plastics have the scope of application separately to make and characteristics.Also exist on the whole and manufacture weak points such as height, degraded is uncontrollable, degraded is not thorough.What have is also inapplicable on mechanical property, and promoted extension has certain difficulty.Remain further to be improved.
Based on cost factor, chemical synthesis and biological synthesis process are not generally adopted, and the modification of traditional macromolecular material is subjected to very big attention.The method of modification has chemical method and physics method, because chemical method will increase extra modification cost, inventor's great majority are to use physically modified, can quickly complete degradable plastic be introduced to the market.
Physically modified is that all multi-functional compositions are admixed in traditional macromolecular material, reaches the modification purpose, and newly formed plastics can high-fallly under field conditions (factors) be separated.Widely popular is to polyolefinic modification, adds photoactive substance, degraded controlled substance, microbiological deterioration material in polyolefine, makes their uniform mixing, has promptly given polyolefine with all biodegradability.
Starch is the biodegradable thing that is widely applied, because its price is low, aboundresources, be reproducible natural resources, not only can be used as the microbiological deterioration additive, and being incorporated in the polyolefine for biodegradable packing material of all selecting of many inventors, but because the chemical structure and the polyolefine of starch are completely different, consistency is poor, without modification, be difficult to mix, exempt from by force for it, will cause the plastics strength degradation with the polyene hydrocarbon phase; Simultaneously, this simple blended plastics of discovery can not be degraded under field conditions (factors) fully in using reality, have only that part of degraded of starch, and fragmentation only takes place polyolefine, there is no the decline of actual molecular weight, and such plastics consequences for use are bad.Developed starch and compatible polyolefin modification technology for addressing these problems.
Consistency modification aspect has many efficient ways.For example starch and ethene, vinylformic acid connect skill, add coupling agent, starch coated lipophilicity compound etc. in starch.After adopting these measures, plastics are significantly improved aspect mechanical property, but still the shortcoming that exists polyolefine not degrade fully.And, be difficult to make very thin membrane product because starch granules is thicker.
Purpose of the present invention overcomes above-mentioned shortcoming exactly, adopts short-cut method that starch and polyolefine are carried out two modifications, adds the consistency monomer on the one hand in polyolefine, makes it to connect the skill copolymerization with polyolefine having in the presence of the radical initiator.The consistency monomer contains hydroxyl, can be further and the hydroxy esterification of starch, and make starch and polyolefine form the cross-link bond integrator, improve plastics intensity greatly.On the other hand the starch granules structure is improved, had in the presence of the softening agent polyvalent alcohol, reduce the starch granules diameter with suitable structure deteriorate agent, and make starch become not meltability starch, and complete and polyolefine fusion in melt-processed.The plastics of making like this make the molecular polyolefin splitting of chain become small molecules owing to starch is decomposed fully by microorganism, further eat for Institute of Micro-biology, become at last to nitrogen peroxide and water to melt in the Nature.
The present invention is a kind of light, biodegradation plastic.Wherein contain photosensitizers, photodegradation promotor, photostabilizer, by the consumption and the proportioning of regulating them.May command photodegradation inductive phase and degradation time.Also contain autoxidator and biodegradation agent, make plastics after finishing functions of use, according to still continuing degraded under the condition, reach fully with naturally and assimilate unglazed.
Biodegradation agent among the present invention is a treated starch, wherein contains coupling agent, softening agent, structure deteriorate agent and hydrophobizing agent, once finishes by simply being blended in the following process.
Plastic matrix is a modified polyolefin among the present invention, wherein contains comonomer and radical initiator.Connect the skill copolymerization through simple the mixing.
Degradable master batch of the present invention is that above-mentioned modified polyolefin is mixed with photosensitizers, photodegradation control agent, photodegradation promotor, photostabilizer, autoxidator and treated starch, melt extrudes particle again and makes.
Controllable light of the present invention, bio-degradable masterbatch are formed: polyolefine 80～100 (mass parts, down together), photosensitizers 0.05～5, degradation of promoter 0.05～2, photostabilizer 0.1～5, free agent initiator 0.001～1, comonomer 0.01～5, autoxidator 0.5～10, treated starch 100～80.
Described treated starch comprises: starch 100 (mass parts, down together), coupling agent 0.5～1.5, softening agent 0.5～1.5, structure deteriorate agent 0.5～1.5, hydrophobizing agent 0.5～1.5.
Polyolefine of the present invention is meant polyethylene, polypropylene, polystyrene, wherein chooses any one kind of them.
Photosensitizers of the present invention is ferrocene and derivative thereof, wherein chooses any one kind of them or two kinds.
Degradation of promoter of the present invention is the organic compound that comprises iron, chooses any one kind of them or two kinds as dithiocarbamic acid iron, iron stearate, ferric acetyl acetonade etc.
Photostabilizer of the present invention is meant oxidation inhibitor, UV light absorber, thermo-stabilizer, wherein a kind of or several combinations.As antioxidant 1010, antioxidant 1076, UV light absorber UV-TBS, UV light absorber UV-OPS, UV light absorber UV-BAO, UV light absorber UV-9, UV light absorber UV-24.Stablizer such as curing oxygen base base nickel formate derivative NN, a di-n-butyl two sulphur oxygen base nickel formates (photostabilizer NBC) etc.
Autoxidator of the present invention is meant lipid acid and metal-salt thereof, as oleic acid and salt, stearic acid and salt thereof, chooses any one kind of them or two kinds.
Polymer monomers of the present invention is meant the lipid acid that contains two keys, chooses any one kind of them as vinylformic acid, maleic acid, MALEIC ANHYDRIDE etc.
Radical initiator of the present invention is meant the azo compound, hydroperoxide, and as Diisopropyl azodicarboxylate, benzoyl peroxide is chosen one of them wantonly.
The used starch of the present invention is meant W-Gum, tapioca (flour), potato starch, Starch rice, one of them.
The used coupling agent of the present invention is meant that silicic acid is that coupling agent, titanic acid ester are that coupling agent, aluminic acid ester are coupling agent, chooses any one kind of them or two kinds as KH550, TC-T etc.
Starch softening agent of the present invention is meant aliph polyols and derivative thereof, as ethylene glycol, propylene glycol, poly-ethanol, glycerine, Sorbitol Powder etc., chooses any one kind of them.
Hydrophobizing agent of the present invention is meant stearic acid, cured, plant wet goods, chooses any one kind of them.
According to light of the present invention, biodegradation plastic manufacture method is that relevant component is mixed, and uses the forcing machine granulation then.
1, starch, coupling agent, softening agent, structure deteriorate agent are mixed by aforementioned ratio, make treated starch.
2, with polyolefine, comonomer and initiator in aforesaid ratio thorough mixing, heat 60 ℃ ± 5 ℃, reacted 0.5 hour, make modified polyolefin, then 1 treated starch is added wherein, add photosensitizers again, degradation of promoter, photostabilizer and autoxidator, thorough mixing.
3,,, be controllable light, biodegradation plastic master batch with the granulation of exhaust twin screw extruder with whole component mixtures.
The plastic master batch that is obtained can be processed film forming, section bar and various plastics, or mix back extruding pelletization, extrusion molding, blowing film forming again with polyolefine or other auxiliary agents with this master batch, because the auxiliary agent that is adopted is nontoxic, purposes is very extensive, can be used as non-returnable container material, agricultural film, shopping bag, refuse bag and food product pack, disposable tableware beverage bottle etc.According to the working conditions difference, can adjust above-mentioned auxiliary agent proportion scale, control degradation is induced constantly to be influenced plastics performance with degradation time and all can reach decomposition voluntarily, gradually with natural assimilation.Advantage of the present invention is that cost is low, practicality wide, degraded is complete.
Following example helps further to understand the present invention, but is not limited to this example.
Embodiment one
With 100 parts of W-Gums (mass parts, down with), 1 part of coupling agent KH550,1.5 parts of ethylene glycol, 1 part in urea, 1 part of co-blended of white oil until evenly.
With 100 parts of new LDPE (film grade)s (LDPE), put in the plastics mixer, stir, be warming up to 60 ℃ ± 5 ℃, add 0.5 part in vinylformic acid, 0.01 part of benzoyl peroxide, stirring reaction 30 minutes, then with 100 parts in above-mentioned treated starch mixture, 1 part of ferrocene, 0.5 part of great proficiency resin acid iron, 0.5 part in NN one second, n-butyl dithiocarbamate nickel, 0.5 part of antioxidant 1010,8 parts of oleic acid drop in the mixing machine in succession.Mixed 5～10 minutes.
Send the grain-making machine granulation with mixture.With the granulation of exhaust twin screw plastics extruder, extruder temperature: one section 80～110 ℃, two sections 110～140 ℃, three sections 120～150 ℃, four sections 125～145 ℃, 125～140 ℃ of head temperatures, 90～100 rev/mins of screw speeds are extruded pelletizing.The products obtained therefrom outward appearance is a white particle, particle diameter 4mm, density 18/cm
3, melting index 7g/10min confirms to have between polyethylene and starch chemicals to form through infrared absorption spectrum, and the cross section of sem observation film finds that because of hydrogen bond rupture between starch molecule, the starch granules diameter obviously is decreased to below the 5 μ m.
Embodiment two
100 parts of (mass parts of masterbatch that example one is made, down together), linear paper density polyethylene is 80 parts, density polyethylene mixes for 20 parts, drop in the blow moulding machine hopper, be warming up to and give fixed temperature after 1 hour, blow out 0.008～0.1mm film, wherein starch content is 25%, transparency is good, and its mechanical property surpasses national standard, reveals and puts all degradeds after open-air 120 days.
Light of the present invention, biodegradation plastic can be processed into other plastics, add to suit to can be made into expanded plastic behind the whipping agent, can do the redjustment and modification of all tubes to the present invention in actual applications, and product all can complete and assimilation naturally in 3～18 months.
Claims (10)
1, a kind of optically and biologically degradable plastics, it is characterized in that its component is: polyolefine 80～100 (mass parts, down together), photosensitizers 0.05～5, degradation of promoter 0.05～2, photostabilizer 0.1～5, free agent initiator 0.001～1, comonomer 0.01～5, autoxidator 0.5～10, treated starch 100～80.
2, optically and biologically degradable plastics according to claim 1, it is characterized in that described treated starch comprises: starch 100 (mass parts, down together), coupling agent 0.5～1.5, softening agent 0.5～1.5, structure deteriorate agent 0.5～1.5, hydrophobizing agent 0.5～1.5, used starch is meant W-Gum, tapioca (flour), potato starch, Starch rice, one of them, the used coupling agent of the present invention is meant that silicic acid is coupling agent, titanic acid ester is a coupling agent, the aluminic acid ester is a coupling agent, choose any one kind of them or two kinds, starch softening agent of the present invention is meant aliph polyols and derivative thereof, described aliph polyols and derivative thereof are ethylene glycol, propylene glycol, poly-ethanol, glycerine, Sorbitol Powder is chosen any one kind of them, and hydrophobizing agent of the present invention is a stearic acid, cured, vegetables oil is chosen any one kind of them.
3, optically and biologically degradable plastics according to claim 1 is characterized in that described polyolefine is meant polyethylene, polypropylene, polystyrene, wherein chooses any one kind of them.
4, optically and biologically degradable plastics according to claim 1 is characterized in that described photosensitizers is ferrocene and derivative thereof, wherein chooses any one kind of them or two kinds.
5, optically and biologically degradable plastics according to claim 1, it is characterized in that described degradation of promoter is the organic compound that comprises iron, the organic compound of described iron is dithiocarbamic acid iron, iron stearate, ferric acetyl acetonade is chosen any one kind of them or two kinds.
6, optically and biologically degradable plastics according to claim 1 is characterized in that described photostabilizer is meant oxidation inhibitor, UV light absorber, thermo-stabilizer, wherein a kind of or several combinations.
7, optically and biologically degradable plastics according to claim 1 is characterized in that described autoxidator is meant lipid acid and metal-salt thereof, and described lipid acid and metal-salt thereof are oleic acid and salt, stearic acid and salt thereof, choose any one kind of them or two kinds.
8, optically and biologically degradable plastics according to claim 1 is characterized in that described polymer monomers is meant the lipid acid that contains two keys, and described double bond containing lipid acid is that vinylformic acid, maleic acid, MALEIC ANHYDRIDE are chosen any one kind of them.
9, optically and biologically degradable plastics according to claim 1, it is characterized in that described radical initiator is meant the azo compound, hydroperoxide, described azo compound, hydroperoxide are Diisopropyl azodicarboxylate, benzoyl peroxide is chosen one of them wantonly.
10, a kind of manufacture method of optically and biologically degradable plastics is characterized in that:
(1), starch 100 (mass parts, down with), coupling agent 0.5～1.5, softening agent 0.5～1.5, structure deteriorate agent 0.5～1.5 are mixed, make treated starch;
(2), with polyolefine 80～100 (mass parts, comonomer 0.01～5 and initiator 0.001～1 thorough mixing down together),, heat 60 ℃ ± 5 ℃, reacted 0.5 hour, make modified polyolefin, the treated starch with (1) adds wherein then, adds photosensitizers 0.05～5 again, degradation of promoter 0.05～2, photostabilizer 0.1～5 and autoxidator 0.5～10, thorough mixing;
(3), with whole component mixtures, with the granulation of exhaust twin screw extruder, be controllable light, biodegradation plastic grain.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00126615 CN1125121C (en) | 2000-09-30 | 2000-09-30 | Optically and biologically degradable plastics and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00126615 CN1125121C (en) | 2000-09-30 | 2000-09-30 | Optically and biologically degradable plastics and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1289792A CN1289792A (en) | 2001-04-04 |
| CN1125121C true CN1125121C (en) | 2003-10-22 |
Family
ID=4591922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00126615 Expired - Fee Related CN1125121C (en) | 2000-09-30 | 2000-09-30 | Optically and biologically degradable plastics and its preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1125121C (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298777C (en) * | 2003-01-16 | 2007-02-07 | 天津市君怡商贸有限公司 | Thermal oxidative degradation-promoting mother particle used for plastics and its preparation method |
| NO324368B1 (en) * | 2003-04-23 | 2007-10-01 | Normors As | Process for preparing additive for thermoplastics and such prepared additive as well as thermoplastics containing such additive. |
| NO324545B1 (en) * | 2004-10-22 | 2007-11-19 | Nor X Industry As | Process for the manufacture of thermoplastics having an adjustable lifetime, mixing of additives for use in carrying out the process and thermoplastics so produced. |
| CN101831098B (en) * | 2010-04-20 | 2012-05-30 | 安徽广和投资担保集团有限公司 | Degradable agricultural film |
| CN102391557A (en) * | 2011-07-07 | 2012-03-28 | 宋旭 | High-filling controllable oxidative degradation packaging material and preparation method thereof |
| CN103059146A (en) * | 2013-02-05 | 2013-04-24 | 湘潭大学 | Starch surface treatment process |
| CN103980549A (en) * | 2014-05-31 | 2014-08-13 | 全椒祥瑞塑胶有限公司 | High-degradability plastic |
| CN104151687B (en) * | 2014-09-01 | 2016-09-14 | 苏州卓越工程塑料有限公司 | A kind of degradable injected plastics material |
| CN105075751B (en) * | 2015-07-27 | 2018-07-24 | 陆海荣 | A kind of double degradation environment protection mulches and preparation method thereof |
| CN105504362A (en) * | 2015-12-24 | 2016-04-20 | 江苏道勤新材料科技有限公司 | Degradable plastic |
| CN105885108A (en) * | 2016-04-25 | 2016-08-24 | 天津锦利程包装有限公司 | Circulating utilization type packing material |
| CN106117750A (en) * | 2016-07-28 | 2016-11-16 | 芜湖凯奥尔环保科技有限公司 | Photodegradable plastics thin film |
| CN106046505A (en) * | 2016-07-28 | 2016-10-26 | 芜湖凯奥尔环保科技有限公司 | Photodegradable plastic film |
| CN107033394A (en) * | 2017-05-18 | 2017-08-11 | 聂超 | A kind of biodegradable agricultural mulching new material and preparation method thereof |
| CN107163432A (en) * | 2017-05-27 | 2017-09-15 | 南通成山高分子材料有限公司 | A kind of degradation plastic |
| CN107417984A (en) * | 2017-06-27 | 2017-12-01 | 太仓市晨洲塑业有限公司 | A kind of Degradable environment-friendlyplastic plastic |
| CN111944226A (en) * | 2020-09-04 | 2020-11-17 | 苏州高松美姿自动化科技有限公司 | Photodegradable plastic packaging bag environment-friendly material and preparation method thereof |
| CN112267212A (en) * | 2020-10-15 | 2021-01-26 | 深圳市通产丽星股份有限公司 | Biodegradable polypropylene composite material, melt-blown non-woven fabric and application thereof |
| CN112280107A (en) * | 2020-11-05 | 2021-01-29 | 上海奥巴迪降解塑料有限公司 | Biodegradable polyolefin plastic composite additive in open land environment and preparation method and application thereof |
| CN112457615B (en) * | 2020-11-16 | 2022-12-02 | 深圳市正旺环保新材料有限公司 | Stretch-proof and easily-degradable plastic bag and preparation method thereof |
-
2000
- 2000-09-30 CN CN 00126615 patent/CN1125121C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1289792A (en) | 2001-04-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1125121C (en) | Optically and biologically degradable plastics and its preparing process | |
| US8389614B2 (en) | Biodegradable nanopolymer compositions and biodegradable articles made thereof | |
| CN1074435C (en) | Polynary degradable resin composition and its preparation process | |
| KR960012445B1 (en) | Biodegradable polyethylene composition coupled chemically by starch and process thereof | |
| Fomin et al. | Biodegradable polymers, their present state and future prospects | |
| US5861461A (en) | Biodegradable plastic composition, method for preparing thereof and product prepared therefrom | |
| CN1312318A (en) | Polynary composite for light and biological degraded plastic product and its use | |
| JPH04504731A (en) | Degradable lactide thermoplastic | |
| CN112341650A (en) | Compostable fully-degradable film and preparation method thereof | |
| CN100429263C (en) | Biological-degradable starch/polyester plastic completely and production thereof | |
| CN1051187A (en) | Biologically degradable cover film and preparation method thereof | |
| CN112538239A (en) | Straw capable of being completely biodegraded and preparation method thereof | |
| CN112341649A (en) | Fully biodegradable paper packaging waterproof film and preparation method thereof | |
| CN112430382A (en) | Compostable full-degradable disposable tableware and preparation method thereof | |
| CN107488298B (en) | Bio-based fully-degradable plastic master batch, preparation method and application thereof | |
| KR100368738B1 (en) | Bio-/photo-degradable agricultural mulch film composition, preparation thereof and formed product obtained from the same composition | |
| CN1785641A (en) | Production technology of comixed biodegradable material | |
| KR102579310B1 (en) | Biodegradable resin compositions including polyvinylalcohol and manufacturing methods thereof | |
| CN1590449A (en) | Additive composition for promoting degradation of plastics | |
| CN1284820C (en) | Starch-based biodegradable film material and its production method | |
| CN114836012B (en) | Completely biodegradable garbage bag film material and preparation method of garbage bag film | |
| KR20180119479A (en) | Multi-degradable polyolefin-based resin composition and manufacturing method of the composition | |
| CN1775856A (en) | Method for preparing composite biodegradable master batch | |
| CN1109062C (en) | Method for producing inorganic base material composite degradable plastic master batch | |
| CN1156154A (en) | Method for preparing biological degredation plastic composition and product prepared by said composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |