CN102634073B - Starch/polypropylene degradable composite material and preparation method thereof - Google Patents
Starch/polypropylene degradable composite material and preparation method thereof Download PDFInfo
- Publication number
- CN102634073B CN102634073B CN201210123934.5A CN201210123934A CN102634073B CN 102634073 B CN102634073 B CN 102634073B CN 201210123934 A CN201210123934 A CN 201210123934A CN 102634073 B CN102634073 B CN 102634073B
- Authority
- CN
- China
- Prior art keywords
- starch
- polypropylene
- weight parts
- composite material
- maleic anhydride
- 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
- 229920002472 Starch Polymers 0.000 title claims abstract description 145
- 239000008107 starch Substances 0.000 title claims abstract description 145
- 235000019698 starch Nutrition 0.000 title claims abstract description 145
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 117
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 117
- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- -1 polypropylene Polymers 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 41
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 239000003549 soybean oil Substances 0.000 claims description 34
- 235000012424 soybean oil Nutrition 0.000 claims description 34
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 30
- 229920005989 resin Polymers 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 26
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 25
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 13
- 238000005453 pelletization Methods 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 230000003068 static effect Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 4
- 229940126680 traditional chinese medicines Drugs 0.000 claims description 4
- 229920000881 Modified starch Polymers 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 abstract description 17
- 239000004033 plastic Substances 0.000 abstract description 17
- 239000004014 plasticizer Substances 0.000 abstract 2
- 235000015112 vegetable and seed oil Nutrition 0.000 abstract 2
- 239000008158 vegetable oil Substances 0.000 abstract 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000001746 injection moulding Methods 0.000 description 33
- 239000004902 Softening Agent Substances 0.000 description 25
- 239000003921 oil Substances 0.000 description 25
- 235000019198 oils Nutrition 0.000 description 25
- 235000013311 vegetables Nutrition 0.000 description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920006238 degradable plastic Polymers 0.000 description 4
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical compound C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 4
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 244000017020 Ipomoea batatas Species 0.000 description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 235000019483 Peanut oil Nutrition 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000000312 peanut oil Substances 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 229920002961 polybutylene succinate Polymers 0.000 description 2
- 239000004631 polybutylene succinate Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920001592 potato starch Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 210000000582 semen Anatomy 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229920008262 Thermoplastic starch Polymers 0.000 description 1
- 240000001085 Trapa natans Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000010816 packaging waste Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009165 saligot Nutrition 0.000 description 1
- 239000004628 starch-based polymer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 235000020238 sunflower seed Nutrition 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a starch/polypropylene degradable composite material comprising the following raw materials in percentage by weight: 50% to 70% of starch, 5% to 15% of vegetable oil plasticizer, 15% to 30% of polypropylene or modified polypropylene and 5% to 30% of compatilizer. According to the composite material, the compatilizer is used for improving the compatibility of the starch and polypropylene, the vegetable oil plasticizer is used for plasticizing the starch, and the performance of the plasticized starch is stable, so that the toughness and impact resistance of the starch/polypropylene degradable composite material are enhanced greatly, the performance of the composite material is stable, and the composite material is applicable to the field of plastic package materials, farm-oriented mulching films, disposable tableware and the like. The invention also discloses a preparation method of the starch/polypropylene degradable composite material. The starch/polypropylene degradable composite material is simple to prepare, easy to implement, operate and control, low in preparation cost and apt to industrial production, thus having wide application prospect.
Description
Technical field
The present invention relates to plastic material field, be specifically related to a kind of starch/polypropylene degradable composite material and preparation method thereof.
Background technology
Plastics industry develops rapidly, and its purposes has been penetrated into the every field of national economy, and purposes is very extensive.The annual waste plastic producing of China is about 5,000,000 tons, and wherein most of waste plastics are polypropylene (PP), polyethylene (PE) and polystyrene (PS) material, and these materials can not natural decomposition.Therefore, by PP material, PE material, disposable plastic packaging waste prepared by PS material and corresponding agricultural film and disposable tableware, will be deposited on soil because of its nondegradation if arbitrarily abandoned, thereby cause serious white pollution, and this potential pollution also can aggravate along with the accumulation of the increase of people's usage quantity and time simultaneously, China's white pollution is serious at present, relevant government department and social common concern are caused, relevant laws and regulations are put into effect, especially at European & American Market, the use of non-degradable plastics is subject to strict restriction.
Along with improving constantly of people's environmental consciousness, biodegradable environment-friendly material will receive increasing concern, the input of related industries chain and research and development forms, it is reported 2013, the biodegradable demand of the U.S. is by the market space that has 2,600,000,000 dollars, the demand of the current degradable plastics of China is also huge, it is 3,000,000 tons according to relevant industries analysis, but the degradable plastics of real meaning is as poly(lactic acid) (PLA), the very expensive and performance of the prices such as polyhydroxyalkanoate (PHA) and poly butylene succinate (PBS) has certain gap compared with conventional plastic as PP and PE, cause its traction developing in recent years not high, and starch plastics (is mainly that starch is to PP, the filling of PE and PS etc. conventional plastic and the composite degradable plastics that obtain), due to its be with the basis of traditional filling plastic blend on grow up, not only there is the performance of conventional plastic, and low price and there is biodegradability, the current accreditation that develops rapidly and enjoy industry member and market.
Although starch be can complete biodegradable natural high moleculer eompound, owing to there is notable difference with plastics in its structure, cause that consistency is poor between the two, thereby also limit in this respect it and further apply.At present, the method for improving plastics and starch consistency mainly comprises physically modified to starch and chemical modification, graft modification to plastics and adds suitable compatilizer.The introducing of compatilizer is that to use be at present the most also one of effective means.The compatilizer the most often using is multipolymer (EVA), polypropylene/shrink glyceral methacrylate (PP/GMA) grafts and starch/methyl acrylate graft copolymer etc. of ethylene-acrylic acid copolymer (EAA), ethene-vinyl acetate.Grand shrink glyceral methacrylate (GMA) and the starch-grafted thing of the GMA/ compatilizer as polypropylene/starch blending system that uses under initiator exists of the Chen Xian of Hunan University, use twin-screw extrusion to realize thermoplastification and starch and the polyacrylic blend increase-volume of starch, prepared the biodegradable polypropylene/starch blending material (the functional materials fifth phase in 2009 (40) volume) of excellent property.But this intermingling material does not add toughner, intermingling material is difficult to plasticizing and extrudes and can be highly brittle in twin screw.
In solving starch and polypropylene compatible, also need in addition to solve the too poor defect of toughness of whole compound system, because starch is rigid particles, general document and patent report are all it to be carried out to plasticizing fill, and the method for employing is to add the micromolecular compounds such as polyvalent alcohol, polyamine, hydramine or single sweet acid esters and starch to carry out melt blending to plastify.The use urea such as Yu and ethanolamine mixtures be as the softening agent of preparing thermoplastic starch, and in screw rod, carry out melt blending and extrude.Found through experiments in system after 15wt% urea and the composite use of 15wt% thanomin, after starch plasticizing with respect to using glycerine plasticized starch to there is better thermal characteristics and mechanical property (Carbohydrate Polymers 64 (2006) 267-273).But adopt small molecules to plastify starch, the starch performance of plasticizing is unstable, and small molecules is easily separated out and caused plasticized starch recrystallization to cause product performance to decline, and the starch non-refractory of small molecules plasticizing, the easy flavescence of product.Publication number is that the Chinese invention patent application of CN 101805463A discloses a kind of starch filled biodegradable polypropylene and preparation method thereof, this starch filled biodegradable polypropylene is by the starch of weight percent 30%～70%, 5%～15% softening agent, 10%～50% polypropylene, 0.5%～1% dispersion agent, 5%～8% toughner and 0.5%～1% photodegradable aid, although the mechanical property of this starch filled biodegradable polypropylene is better, but the softening agent using is one or both the mixture in sorbyl alcohol and glycerine, sorbyl alcohol and glycerine are small molecules softening agent, still there is above-mentioned problem.
Summary of the invention
The invention provides a kind of starch/polypropylene degradable composite material, starch and polypropylene under the improvement of compatilizer and vegetables oil softening agent, mechanical property excellence, anti-fold ability is strong, vegetables oil softening agent is difficult for separating out.
A kind of starch/polypropylene degradable composite material, made by the raw material of following weight percentage:
Starch 50%～70%;
Vegetables oil softening agent 5%～15%;
Polypropylene or modified polypropene 15%～30%;
Compatilizer 5%～30%.
The present invention improves starch and polyacrylic consistency by compatilizer, by vegetables oil softening agent, starch is plastified, the starch performance of plasticizing is stable, four kinds of raw materials can interact, make starch/polypropylene degradable composite material of the present invention under the higher prerequisite of starch content, embody excellent mechanical property.
As preferably, described starch/polypropylene degradable composite material, made by the raw material of following weight percentage:
Starch 50%～60%;
Vegetables oil softening agent 8%～12%;
Polypropylene or modified polypropene 15%～25%;
Compatilizer 15%～25%.
Described starch is one or both in native starch, treated starch.Described native starch is one or more in W-Gum, tapioca (flour), green starch, sweet potato starch, sweet potato starch, yam starch, wheat kind of starch, water caltrop starch, Rhizoma Nelumbinis starch.Described treated starch is one or more in the two starch of modified by maleic acid anhydride graft starch, phosphoric acid ester, Ultra Tex 2, the two starch adipates of acetylize, hydroxypropyl Staragel 90V.Described modified by maleic acid anhydride graft starch can specifically be selected maleic anhydride graft W-Gum.Starch can biological degradation, native starch be can complete biodegradable natural high moleculer eompound, consider from cost and the degradability of starch/polypropylene degradable composite material, not only cost is lower to select native starch, and degradability is good, consider from the mechanical property of starch/polypropylene degradable composite material, treated starch is more conducive to the raising of starch/polypropylene degradable composite material mechanical property in ensureing the certain degradation property of matrix material.
The present invention selects macromole vegetables oil softening agent to plastify starch, the starch performance of plasticizing is stable, macromole vegetables oil softening agent is difficult for separating out, be conducive to the raising of starch/polypropylene degradable composite material mechanical property, the particularly toughness of matrix material, and the starch of macromole vegetables oil softening agent plasticizing is high temperature resistant, and product is inhibited from yellowing.Described vegetables oil softening agent is one or more in soybean oil, peanut oil, Oleum Cocois, plam oil, oleum lini, Oleum Gossypii semen, Semen Maydis oil, sunflower seed oil, pine-seed oil, tung oil, Viscotrol C.Further preferably, described vegetables oil softening agent is soybean oil, the weight percentage of soybean oil is 10%, the soybean oil that employing weight percentage is 10% not only can be prepared starch/polypropylene degradable composite material of excellent performance, and relative other the oily costs of soybean oil are lower, and the production cost of starch/polypropylene degradable composite material is reduced greatly.
Described polypropylene can adopt commercially available prod, selects the commercially available general trade mark.Modified polypropene also can be selected the commercially available general trade mark, specifically can adopt maleic anhydride inoculated polypropylene, through maleic anhydride modified polypropylene, has better consistency with starch, has improved the consistency of polypropylene and starch.
Because structurally existing notable difference, two kinds of starch and polypropylene cause that consistency is not good between the two, the present invention improves starch and polyacrylic consistency by compatilizer, one or both in multipolymer (EVA), ethylene-acrylic acid copolymer (EAA) that described compatilizer is ethene-vinyl acetate.Further preferably, the multipolymer that described compatilizer is ethene-vinyl acetate, the multipolymer of ethene-vinyl acetate can very well improve starch and polyacrylic consistency.
The present invention also provides a kind of preparation method of starch/polypropylene degradable composite material, and preparation is simple, easy to implement, is easy to operate and control.
The preparation method of described starch/polypropylene degradable composite material, comprises the following steps:
Starch, vegetables oil softening agent, polypropylene and compatilizer are mixed, obtain mixed material; Or starch, vegetables oil softening agent, modified polypropene and compatilizer are mixed, obtain mixed material; Mixed material is added to tie rod, pelletizing after melt blending in twin screw extruder, obtains particulate state hybrid resin; Particulate state hybrid resin drying obtains starch/polypropylene degradable composite material after processing.
The screw slenderness ratio of described twin screw extruder is 35: 1～45: 1; The temperature of described melt blending is 160 DEG C～180 DEG C, and vegetables oil softening agent plastifies starch, and the starch performance of plasticizing is stable, and vegetables oil softening agent is difficult for separating out, raw material can be under 160 DEG C～180 DEG C comparatively high tempss melt extrusion.
Starch/polypropylene degradable composite material of the present invention is applicable to the fields such as Plastic Packaging Materials, agricultural mulching and disposable tableware, taking starch/polypropylene degradable composite material as starting material, produce plastic packaging film, agricultural mulching and disposable tableware by existing processing technology.
Compared with prior art, tool of the present invention has the following advantages:
In starch/polypropylene degradable composite material of the present invention, starch content is higher, make starch/polypropylene degradable composite material of the present invention there is good degradability, while adopting cheap, native starch that be easy to obtain, starch/polypropylene degradable composite material of the present invention still has good mechanical property and high thermal resistance, and degradability is better simultaneously.Vegetables oil softening agent can be decomposed by microorganism under given conditions, biodegradable.Thereby main raw material starch and the equal degradable of vegetables oil softening agent in starch/polypropylene degradable composite material of the present invention, make starch/polypropylene degradable composite material of the present invention have good degradability.
Starch/polypropylene degradable composite material of the present invention, improve starch and polyacrylic consistency by compatilizer, by vegetables oil softening agent, starch is plastified, the starch performance of plasticizing is stable, vegetables oil softening agent is difficult for separating out, and the starch of vegetables oil softening agent plasticizing is high temperature resistant, make raw material can be under 160 DEG C～180 DEG C comparatively high tempss melt extrusion, product is inhibited from yellowing, toughness and the shock resistance of starch/polypropylene degradable composite material of the present invention are strengthened greatly, stable performance simultaneously.Four kinds of raw materials of the present invention can interact, and make starch/polypropylene degradable composite material of the present invention under the higher prerequisite of starch content, embody excellent mechanical property and certain high thermal resistance.
Starch/polypropylene composite material of the present invention not only goes for the fields such as Plastic Packaging Materials, agricultural mulching and disposable tableware, and the last major part of starch/polypropylene composite material of the present invention can be decomposed by the microorganism in soil and absorb, environmental pollution is little, has good environmental benefit and social value.
The preparation method of starch/polypropylene degradable composite material of the present invention, preparation is simple, easy to implement, be easy to operate and control, preparation cost is cheap, excellent product performance and stable, be easy to suitability for industrialized production and there is good economic benefit, have broad application prospects.
Embodiment
Following examples further describe the present invention, but the present invention is not limited to these embodiment.
Preparation example 1
By the W-Gum of 60g, (weight percentage of moisture is 4.1%, Xingmao Corn Development Co., Ltd., Zhucheng), the maleic anhydride (traditional Chinese medicines reagent) of 2.6g, the N of 100mL, N-N,N-DIMETHYLACETAMIDE (DMAc, traditional Chinese medicines reagent) and 20mL toluene (traditional Chinese medicines reagent) be added in 250mL there-necked flask and stir, mechanical stirring 1h at 130 DEG C, the static upper strata solvent of removing, then add acetone to stir and wash away unreacted maleic anhydride, the static upper strata solvent of removing, again add the static upper strata solvent of removing of acetone, adding acetone to remove upper strata solvent carries out after 3 times altogether, filter, repeatedly rinse 3 times with acetone again, the modified corn starch obtaining is put into vacuum drying oven dry 12h at 80 DEG C, obtain 60g maleic anhydride graft W-Gum.
Embodiment 1
Take the raw material of following weight part:
Maleic anhydride graft W-Gum 55 weight parts prepared by preparation example 1, soybean oil (Aladdin reagent) 10 weight parts, maleic anhydride inoculated polypropylene (general purpose grade, Ningbo NengZhiGuang New Materials Science Co., Ltd, model is GPM200A) 10 weight parts, ethylene-vinyl acetate copolymer (Korea S Han Hua, model is 1317 types) 25 weight parts.
After maleic anhydride graft W-Gum 55 weight parts, soybean oil 10 weight parts, maleic anhydride inoculated polypropylene 10 weight parts and ethylene-vinyl acetate copolymer 25 weight parts are mixed, then (mixed material is 160 DEG C through excess temperature successively mixed material to be added to melt blending in twin screw extruder, 170 DEG C, 170 DEG C, 170 DEG C, 175 DEG C, 170 DEG C, 170 DEG C, the each interval of melt blending of 160 DEG C) rear tie rod, pelletizing, obtains particulate state hybrid resin; Particulate state hybrid resin, after the drying treatment that dewaters, obtains starch/polypropylene degradable composite material.The screw slenderness ratio of the twin screw extruder of selecting is 40: 1.
Starch/polypropylene degradable composite material obtained above is added to injection moulding in injection moulding machine, obtains goods batten.200 DEG C of injection moulding district temperature, template region temperature 45 C.
Embodiment 2
Take the raw material of following weight part:
Maleic anhydride graft W-Gum 55 weight parts prepared by preparation example 1, soybean oil (Aladdin reagent) 10 weight parts, maleic anhydride inoculated polypropylene (general purpose grade, Ningbo NengZhiGuang New Materials Science Co., Ltd, model is GPM200A) 20 weight parts, ethylene-vinyl acetate copolymer (Korea S Han Hua, model is 1317 types) 15 weight parts.
After maleic anhydride graft W-Gum 55 weight parts, soybean oil 10 weight parts, maleic anhydride inoculated polypropylene 20 weight parts and ethylene-vinyl acetate copolymer 15 weight parts are mixed, then (mixed material is 160 DEG C through excess temperature successively mixed material to be added to melt blending in twin screw extruder, 170 DEG C, 175 DEG C, 170 DEG C, 170 DEG C, 170 DEG C, 170 DEG C, the each interval of melt blending of 160 DEG C) rear tie rod, pelletizing, obtains particulate state hybrid resin; Particulate state hybrid resin, after the drying treatment that dewaters, obtains starch/polypropylene degradable composite material.The screw slenderness ratio of the twin screw extruder of selecting is 40: 1.
Starch/polypropylene degradable composite material obtained above is added to injection moulding in injection moulding machine, obtains goods batten.200 DEG C of injection moulding district temperature, template region temperature 45 C.
Embodiment 3
Take the raw material of following weight part:
Maleic anhydride graft W-Gum 55 weight parts prepared by preparation example 1, soybean oil (Aladdin reagent) 10 weight parts, polypropylene 20 (Exxon Mobils, model is 7684KN) weight part, ethylene-vinyl acetate copolymer (Korea S Han Hua, model is 1317 types) 15 weight parts.
After maleic anhydride graft W-Gum 55 weight parts, soybean oil 10 weight parts, polypropylene 20 weight parts and ethylene-vinyl acetate copolymer 15 weight parts are mixed, then (mixed material is 160 DEG C through excess temperature successively mixed material to be added to melt blending in twin screw extruder, 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 175 DEG C, 170 DEG C, the each interval of melt blending of 160 DEG C) rear tie rod, pelletizing, obtains particulate state hybrid resin; Particulate state hybrid resin, after the drying treatment that dewaters, obtains starch/polypropylene degradable composite material.The screw slenderness ratio of the twin screw extruder of selecting is 40: 1.
Starch/polypropylene degradable composite material obtained above is added to injection moulding in injection moulding machine, obtains goods batten.200 DEG C of injection moulding district temperature, template region temperature 45 C.
Embodiment 4
Take the raw material of following weight part:
Maleic anhydride graft W-Gum 60 weight parts prepared by preparation example 1, soybean oil (Aladdin reagent) 10 weight parts, polypropylene (Exxon Mobil, model is 7684KN) 15 weight parts, ethylene-vinyl acetate copolymer (Korea S Han Hua, model is 1317 types) 15 weight parts.
After maleic anhydride graft W-Gum 60 weight parts, soybean oil 10 weight parts, polypropylene 15 weight parts and ethylene-vinyl acetate copolymer 15 weight parts are mixed, then (mixed material is 160 DEG C through excess temperature successively mixed material to be added to melt blending in twin screw extruder, 170 DEG C, 175 DEG C, 170 DEG C, 175 DEG C, 170 DEG C, 160 DEG C, the each interval of melt blending of 160 DEG C) rear tie rod, pelletizing, obtains particulate state hybrid resin; Particulate state hybrid resin, after the drying treatment that dewaters, obtains starch/polypropylene degradable composite material.The screw slenderness ratio of the twin screw extruder of selecting is 40: 1.
Starch/polypropylene degradable composite material obtained above is added to injection moulding in injection moulding machine, obtains goods batten.200 DEG C of injection moulding district temperature, template region temperature 45 C.
Embodiment 5
Take the raw material of following weight part:
Maleic anhydride graft W-Gum 60 weight parts prepared by preparation example 1, soybean oil (Aladdin reagent) 10 weight parts, polypropylene (Exxon Mobil, model is 7684KN) 20 weight parts, ethylene-vinyl acetate copolymer (Korea S Han Hua, model is 1317 types) 10 weight parts.
After maleic anhydride graft W-Gum 60 weight parts, soybean oil 10 weight parts, polypropylene 20 weight parts and ethylene-vinyl acetate copolymer 10 weight parts are mixed, then (mixed material is 160 DEG C through excess temperature successively mixed material to be added to melt blending in twin screw extruder, 170 DEG C, 175 DEG C, 170 DEG C, 175 DEG C, 175 DEG C, 160 DEG C, the each interval of melt blending of 160 DEG C) rear tie rod, pelletizing, obtains particulate state hybrid resin; Particulate state hybrid resin, after the drying treatment that dewaters, obtains starch/polypropylene degradable composite material.The screw slenderness ratio of the twin screw extruder of selecting is 40: 1.
Starch/polypropylene degradable composite material obtained above is added to injection moulding in injection moulding machine, obtains goods batten.200 DEG C of injection moulding district temperature, template region temperature 45 C.
Embodiment 6
Take the raw material of following weight part:
Two starch (Zhangjiakou Shen Zhou starch Science and Technology Ltd.) 60 weight parts of phosphoric acid ester, soybean oil (Aladdin reagent) 10 weight parts, polypropylene (Exxon Mobil, model is 7684KN) 15 weight parts, ethylene-vinyl acetate copolymer (Korea S Han Hua, model is 1317 types) 15 weight parts.
After two phosphoric acid ester starch 60 weight parts, soybean oil 10 weight parts, polypropylene 15 weight parts and ethylene-vinyl acetate copolymer 15 weight parts are mixed, then (mixed material is 160 DEG C through excess temperature successively mixed material to be added to melt blending in twin screw extruder, 170 DEG C, 175 DEG C, 170 DEG C, 175 DEG C, 175 DEG C, 160 DEG C, the each interval of melt blending of 160 DEG C) rear tie rod, pelletizing, obtains particulate state hybrid resin; Particulate state hybrid resin, after the drying treatment that dewaters, obtains starch/polypropylene degradable composite material.The screw slenderness ratio of the twin screw extruder of selecting is 40: 1.
Starch/polypropylene degradable composite material obtained above is added to injection moulding in injection moulding machine, obtains goods batten.200 DEG C of injection moulding district temperature, template region temperature 45 C.
Embodiment 7
Take the raw material of following weight part:
Two starch adipate (Zhangjiakou Shen Zhou starch Science and Technology Ltd.) 60 weight parts of acetylize; soybean oil (Aladdin reagent) 10 weight parts; polypropylene (Exxon Mobil; model is 7684KN) 15 weight parts; ethylene-vinyl acetate copolymer (Korea S Han Hua, model is 1317 types) 15 weight parts.
After two acetylize starch adipate 60 weight parts, soybean oil 10 weight parts, polypropylene 15 weight parts and ethylene-vinyl acetate copolymer 15 weight parts are mixed, then (mixed material is 160 DEG C through excess temperature successively mixed material to be added to melt blending in twin screw extruder, 170 DEG C, 175 DEG C, 170 DEG C, 175 DEG C, 175 DEG C, 160 DEG C, the each interval of melt blending of 160 DEG C) rear tie rod, pelletizing, obtains particulate state hybrid resin; Particulate state hybrid resin, after the drying treatment that dewaters, obtains starch/polypropylene degradable composite material.The screw slenderness ratio of the twin screw extruder of selecting is 40: 1.
Starch/polypropylene degradable composite material obtained above is added to injection moulding in injection moulding machine, obtains goods batten.200 DEG C of injection moulding district temperature, template region temperature 45 C.
Embodiment 8
In embodiment 8, vegetables oil softening agent adopts peanut oil, and other are with embodiment 7.
Embodiment 7 is compared with embodiment 8, starch/polypropylene the degradable composite material that adopts soybean oil to prepare as vegetables oil softening agent has better properties, and from the marketization and industrialized angle, adopt soybean oil also more cheap, the production cost of starch/polypropylene degradable composite material is lower.
Embodiment 9
Take the raw material of following weight part:
Two starch adipate (Zhangjiakou Shen Zhou starch Science and Technology Ltd.) 58 weight parts of acetylize; soybean oil (Aladdin reagent) 12 weight parts; polypropylene (Exxon Mobil; model is 7684KN) 15 weight parts; ethylene-vinyl acetate copolymer (Korea S Han Hua, model is 1317 types) 15 weight parts.
After two acetylize starch adipate 58 weight parts, soybean oil 12 weight parts, polypropylene 15 weight parts and ethylene-vinyl acetate copolymer 15 weight parts are mixed, then (mixed material is 160 DEG C through excess temperature successively mixed material to be added to melt blending in twin screw extruder, 170 DEG C, 175 DEG C, 170 DEG C, 175 DEG C, 175 DEG C, 160 DEG C, the each interval of melt blending of 160 DEG C) rear tie rod, pelletizing, obtains particulate state hybrid resin; Particulate state hybrid resin, after the drying treatment that dewaters, obtains starch/polypropylene degradable composite material.The screw slenderness ratio of the twin screw extruder of selecting is 40: 1.
Starch/polypropylene degradable composite material obtained above is added to injection moulding in injection moulding machine, obtains goods batten.200 DEG C of injection moulding district temperature, template region temperature 45 C.
Embodiment 10
Take the raw material of following weight part:
Two starch adipate (Zhangjiakou Shen Zhou starch Science and Technology Ltd.) 58 weight parts of acetylize; soybean oil (Aladdin reagent) 8 weight parts; polypropylene (Exxon Mobil; model is 7684KN) 19 weight parts; ethylene-vinyl acetate copolymer (Korea S Han Hua, model is 1317 types) 15 weight parts.
After two acetylize starch adipate 58 weight parts, soybean oil 12 weight parts, polypropylene 15 weight parts and ethylene-vinyl acetate copolymer 15 weight parts are mixed, then (mixed material is 160 DEG C through excess temperature successively mixed material to be added to melt blending in twin screw extruder, 170 DEG C, 175 DEG C, 170 DEG C, 175 DEG C, 175 DEG C, 160 DEG C, the each interval of melt blending of 160 DEG C) rear tie rod, pelletizing, obtains particulate state hybrid resin; Particulate state hybrid resin, after the drying treatment that dewaters, obtains starch/polypropylene degradable composite material.The screw slenderness ratio of the twin screw extruder of selecting is 40: 1.
Starch/polypropylene degradable composite material obtained above is added to injection moulding in injection moulding machine, obtains goods batten.200 DEG C of injection moulding district temperature, template region temperature 45 C.
Embodiment 9, embodiment 10 are compared with embodiment 7, and the key distinction is the weight part of soybean oil, and visible in the time that the weight percentage of soybean oil is 10%, starch/polypropylene degradable composite material of preparation has better properties.
Embodiment 11
Take the raw material of following weight part:
(weight percentage of moisture is 4.1% to W-Gum, Xingmao Corn Development Co., Ltd., Zhucheng) 50 weight parts, soybean oil (Aladdin reagent) 10 weight parts, polypropylene (Exxon Mobil, model is 7684KN) 20 weight parts, ethylene-vinyl acetate copolymer (Korea S Han Hua, model is 1317 types) 20 weight parts.
After W-Gum 50 weight parts, soybean oil 10 weight parts, polypropylene 20 weight parts and ethylene-vinyl acetate copolymer 20 weight parts are mixed, then (mixed material is 165 DEG C through excess temperature successively mixed material to be added to melt blending in twin screw extruder, 165 DEG C, 170 DEG C, 170 DEG C, 170 DEG C, 165 DEG C, 160 DEG C, the each interval of melt blending of 160 DEG C) rear tie rod, pelletizing, obtains particulate state hybrid resin; Particulate state hybrid resin, after the drying treatment that dewaters, obtains starch/polypropylene degradable composite material.The screw slenderness ratio of the twin screw extruder of selecting is 40: 1.
Starch/polypropylene degradable composite material obtained above is added to injection moulding in injection moulding machine, obtains goods batten.200 DEG C of injection moulding district temperature, template region temperature 45 C.
Embodiment 12
Take the raw material of following weight part:
(weight percentage of moisture is 4.1% to W-Gum, Xingmao Corn Development Co., Ltd., Zhucheng) 55 weight parts, soybean oil (Aladdin reagent) 10 weight parts, polypropylene 20 weight part (Exxon Mobils, model is 7684KN), ethylene-vinyl acetate copolymer (Korea S Han Hua, model is 1317 types) 15 weight parts.
After W-Gum 55 weight parts, soybean oil 10 weight parts, polypropylene 20 weight parts and ethylene-vinyl acetate copolymer 15 weight parts are mixed, then (mixed material is 165 DEG C through excess temperature successively mixed material to be added to melt blending in twin screw extruder, 165 DEG C, 170 DEG C, 170 DEG C, 170 DEG C, 165 DEG C, 160 DEG C, the each interval of melt blending of 160 DEG C) rear tie rod, pelletizing, obtains particulate state hybrid resin; Particulate state hybrid resin, after the drying treatment that dewaters, obtains starch/polypropylene degradable composite material.The screw slenderness ratio of the twin screw extruder of selecting is 40: 1.
Starch/polypropylene degradable composite material obtained above is added to injection moulding in injection moulding machine, obtains goods batten.200 DEG C of injection moulding district temperature, template region temperature 45 C.
Starch/polypropylene degradable composite material of embodiment 1～10 preparation is carried out to impact property test (four groups of experiments are averaged for notch impact test, pendulum 5.5J) according to ASTM D256-2006, and its test result is as shown in table 1.Starch/polypropylene degradable composite material prepared embodiment 11～12 is carried out to shock resistance test (notch impact test according to ASTM D 256-2006, pendulum 5.5J, four groups of experiments are averaged), carry out the test (four groups of experiments are averaged) of elongation at break and tensile strength according to GB1040-2006, its test result is as shown in table 2.
Table 1
Table 2
| Embodiment | 11 | 12 |
| Shock strength (KJ/m 2) | 16.5 | 14.3 |
| Elongation at break (%) | 120 | 90 |
| Tensile strength (MPa) | 11 | 14 |
Claims (1)
1. a preparation method for starch/polypropylene degradable composite material, is characterized in that, comprises the following steps:
By the W-Gum of 60g, the maleic anhydride of 2.6g, the N of 100mL, N-N,N-DIMETHYLACETAMIDE and 20mL toluene are added in 250mL there-necked flask and stir, wherein, the weight percentage of the moisture of W-Gum is 4.1% and is produced by Xingmao Corn Development Co., Ltd., Zhucheng, maleic anhydride, N, N-N,N-DIMETHYLACETAMIDE and toluene all adopt traditional Chinese medicines reagent, mechanical stirring 1h at 130 DEG C, the static upper strata solvent of removing, then add acetone to stir and wash away unreacted maleic anhydride, the static upper strata solvent of removing, again add the static upper strata solvent of removing of acetone, adding acetone to remove upper strata solvent carries out after 3 times altogether, filter, repeatedly rinse 3 times with acetone again, the modified corn starch obtaining is put into vacuum drying oven dry 12h at 80 DEG C, obtain 60g maleic anhydride graft W-Gum,
Take the raw material of following weight part:
Maleic anhydride graft W-Gum 55 weight parts of preparation, soybean oil 10 weight parts, maleic anhydride inoculated polypropylene 10 weight parts, ethylene-vinyl acetate copolymer 25 weight parts, the general purpose grade product that the model that maleic anhydride inoculated polypropylene adopts Ningbo NengZhiGuang New Materials Science Co., Ltd to produce is GPM200A, soybean oil adopts Aladdin reagent, and the model that ethylene-vinyl acetate copolymer adopts Korea S Han Hua to produce is the product of 1317 types;
After maleic anhydride graft W-Gum 55 weight parts, soybean oil 10 weight parts, maleic anhydride inoculated polypropylene 10 weight parts and ethylene-vinyl acetate copolymer 25 weight parts are mixed, then mixed material is added in twin screw extruder to tie rod after melt blending, mixed material is 160 DEG C through excess temperature successively, 170 DEG C, 170 DEG C, 170 DEG C, 175 DEG C, 170 DEG C, 170 DEG C, the each interval of melt blending of 160 DEG C, pelletizing afterwards, obtains particulate state hybrid resin; Particulate state hybrid resin, after the drying treatment that dewaters, obtains starch/polypropylene degradable composite material, and the screw slenderness ratio of the twin screw extruder of selecting is 40:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210123934.5A CN102634073B (en) | 2012-04-25 | 2012-04-25 | Starch/polypropylene degradable composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210123934.5A CN102634073B (en) | 2012-04-25 | 2012-04-25 | Starch/polypropylene degradable composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102634073A CN102634073A (en) | 2012-08-15 |
| CN102634073B true CN102634073B (en) | 2014-08-13 |
Family
ID=46618656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210123934.5A Expired - Fee Related CN102634073B (en) | 2012-04-25 | 2012-04-25 | Starch/polypropylene degradable composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102634073B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103131150B (en) * | 2013-03-26 | 2015-06-17 | 无锡市隆道科技有限公司 | Polypropylene/polylactic acid/starch composite material and preparation method thereof |
| CN103408841B (en) * | 2013-08-28 | 2016-01-20 | 浙江池河科技有限公司 | A kind of polypropylene composite material and preparation method thereof |
| CN103937036A (en) * | 2014-04-23 | 2014-07-23 | 苏州羽帆新材料科技有限公司 | Environment-friendly plastic containing modified starch |
| CN104672611A (en) * | 2015-02-04 | 2015-06-03 | 苏州康华净化系统工程有限公司 | Folding and whitening resistant polypropylene material and preparation method thereof |
| CN107090166B (en) * | 2017-06-08 | 2019-01-01 | 四川新升塑胶实业有限公司 | A kind of environmentally-friendly plastic bottle |
| CN107805336A (en) * | 2017-11-20 | 2018-03-16 | 东莞市普凯塑料科技有限公司 | Absorb water master batch and preparation method thereof |
| CN108727642A (en) * | 2018-06-14 | 2018-11-02 | 安徽精良同硕塑膜科技股份有限公司 | A kind of waterproof and breathable degradable mulch and preparation method thereof |
| CN109265937A (en) * | 2018-09-21 | 2019-01-25 | 袁志平 | The method for preparing the dedicated agricultural mulching of peanut using automobile-used acoustical cotton corner dead meal |
| CN110894313B (en) * | 2019-11-08 | 2021-08-27 | 江苏中科成长环保科技有限公司 | Anti-freezing microwave-resistant starch-based tableware and preparation method thereof |
| CN111057274A (en) * | 2019-11-29 | 2020-04-24 | 湖南工业大学 | High-filling starch-based thermoplastic composite material and preparation method thereof |
| CN110804217A (en) * | 2019-12-10 | 2020-02-18 | 湖南工业大学 | High-filling starch masterbatch and preparation method thereof |
| CN111073143A (en) * | 2019-12-26 | 2020-04-28 | 苏州润佳高分子材料有限公司 | Polypropylene-polyethylene modified composite material for automobile |
| CN111892766B (en) * | 2020-07-01 | 2022-07-01 | 余姚市丹丹喷雾器有限公司 | PP material injection molding process and bottle cap prepared by same |
| CN111995820B (en) * | 2020-08-31 | 2022-11-25 | 余姚市宏邦包装有限公司 | Polypropylene material and preparation method thereof |
| CN114591628B (en) * | 2022-03-31 | 2023-11-03 | 马鞍山湖滨无纺布科技有限公司 | PP bottle beneficial to keeping activity of probiotics |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1184822A (en) * | 1996-12-08 | 1998-06-17 | 柏柳青 | Degradable plastic made of chemically linked systhetic high molecule-natural high molecle |
| CN101735483A (en) * | 2009-11-25 | 2010-06-16 | 马永亭 | Material for environmentally-friendly comb toothbrush and manufacturing process |
-
2012
- 2012-04-25 CN CN201210123934.5A patent/CN102634073B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1184822A (en) * | 1996-12-08 | 1998-06-17 | 柏柳青 | Degradable plastic made of chemically linked systhetic high molecule-natural high molecle |
| CN101735483A (en) * | 2009-11-25 | 2010-06-16 | 马永亭 | Material for environmentally-friendly comb toothbrush and manufacturing process |
Non-Patent Citations (2)
| Title |
|---|
| 相容剂对可生物降解聚丙烯/淀粉共混材料的影响;陈宪宏等;《功能材料》;20090520;第40卷(第5期);引言部分 * |
| 陈宪宏等.相容剂对可生物降解聚丙烯/淀粉共混材料的影响.《功能材料》.2009,第40卷(第5期), |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102634073A (en) | 2012-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102634073B (en) | Starch/polypropylene degradable composite material and preparation method thereof | |
| CN103131150B (en) | Polypropylene/polylactic acid/starch composite material and preparation method thereof | |
| CN103254597B (en) | PLA/PBAT biodegradable composite material and preparation method thereof | |
| WO2014032393A1 (en) | Fully biodegradable material and preparation method thereof | |
| CN103992517B (en) | One can be continuously produced fully-degradable starch base plastic alloy and preparation method thereof | |
| CN101781467B (en) | Biomass-synthetic plastic product and method for preparing same | |
| CN104119647B (en) | A kind of high-content of starch complete biodegradable composition and preparation method thereof | |
| CN103254596B (en) | PLA/PPC biodegradable composite material and preparation method thereof | |
| CN104072957B (en) | A kind of food grade biodegradable polylactic acid based composites and application thereof | |
| CN101165087B (en) | Nano composite biological degradation plastic and preparing method thereof | |
| KR101734561B1 (en) | Manufacturing Method of Polylactic acid composites composition | |
| CN103205021A (en) | Thermoplastic and PBAT blend and preparation method thereof | |
| CN112029154A (en) | Biodegradable material and preparation method thereof | |
| JP2018188656A (en) | Thermoplastic starch composition obtained from agricultural waste | |
| CN104693707A (en) | Polylactic acid/starch/fibrilia bio-based degradable composite material and preparation method thereof | |
| CN103965516A (en) | Fully biodegradable masterbatch and preparation method thereof | |
| CN102477216B (en) | Polybutylene succinate fully biodegradable material and preparation process thereof | |
| CN105038163A (en) | Fully-biodegradable material as well as preparation method and application thereof | |
| CN107513246A (en) | One kind is based on modified starch toughened thermoplastic composite and preparation method | |
| CN105219044A (en) | A kind of complete biodegradable heat-proof polylactic acid foam material and preparation method thereof | |
| CN108219406A (en) | A kind of flame retardant type Based Full-degradable Plastics Film and preparation method thereof | |
| CN107522904A (en) | A kind of Starch Based Biodegradable Plastics applied to packaging for foodstuff | |
| CN108929527A (en) | A kind of PBAT/ modified starch full-biodegradable film and its preparation method and application having both high ductibility and high obstructing performance | |
| CN103012856A (en) | Microcrystalline cellulose and polyvinyl alcohol reinforced starch-based full-biodegradable blending material and preparation method thereof | |
| CN103694646A (en) | Polyester/thermoplastic starch biodegradable composition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| ASS | Succession or assignment of patent right |
Owner name: WUXI LONDAO TECHNOLOGY CO., LTD. Effective date: 20120808 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Xiong Zhu Inventor after: Tan Diexi Inventor after: Zhu Jin Inventor after: Tang Zhaobin Inventor after: Zhang Chuanzhi Inventor after: Yang Yong Inventor after: Zhang Lisheng Inventor before: Xiong Zhu Inventor before: Zhu Jin Inventor before: Tang Zhaobin Inventor before: Zhang Chuanzhi Inventor before: Yang Yong Inventor before: Zhang Lisheng |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: XIONG ZHU ZHU JIN TANG ZHAOBIN ZHANG CHUANZHI YANG YONG ZHANG LISHENG TO: XIONG ZHU TAN YIXI ZHU JIN TANG ZHAOBIN ZHANG CHUANZHI YANG YONG ZHANG LISHENG |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20120808 Address after: No. 519 Road, 315201 Zhejiang Zhuang Zhenhai District of city of Ningbo Province Applicant after: Ningbo Institute of Material Technology and Engineering Chinese Academy of Scien Applicant after: Longdao Technology (Wuxi) Co., Ltd. Address before: No. 519 Road, 315201 Zhejiang Zhuang Zhenhai District of city of Ningbo Province Applicant before: Ningbo Institute of Material Technology and Engineering Chinese Academy of Scien |
|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140813 Termination date: 20170425 |