CN102408588A - Full-biodegradable resin prepared from non-staple grain plant modified starch and preparation method thereof - Google Patents
Full-biodegradable resin prepared from non-staple grain plant modified starch and preparation method thereof Download PDFInfo
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- CN102408588A CN102408588A CN201110279356XA CN201110279356A CN102408588A CN 102408588 A CN102408588 A CN 102408588A CN 201110279356X A CN201110279356X A CN 201110279356XA CN 201110279356 A CN201110279356 A CN 201110279356A CN 102408588 A CN102408588 A CN 102408588A
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- Prior art keywords
- modified starch
- staple food
- starch
- food grain
- grain plant
- 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.)
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Links
- 229920000881 Modified starch Polymers 0.000 title claims abstract description 59
- 235000019426 modified starch Nutrition 0.000 title claims abstract description 59
- 239000004368 Modified starch Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920006167 biodegradable resin Polymers 0.000 title abstract 2
- 229920002472 Starch Polymers 0.000 claims abstract description 46
- 239000008107 starch Substances 0.000 claims abstract description 36
- 235000019698 starch Nutrition 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 235000013336 milk Nutrition 0.000 claims abstract description 7
- 239000008267 milk Substances 0.000 claims abstract description 7
- 210000004080 milk Anatomy 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 4
- 235000013339 cereals Nutrition 0.000 claims description 48
- 235000013305 food Nutrition 0.000 claims description 45
- 241000196324 Embryophyta Species 0.000 claims description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 235000012239 silicon dioxide Nutrition 0.000 claims description 13
- 229960001866 silicon dioxide Drugs 0.000 claims description 13
- 240000003183 Manihot esculenta Species 0.000 claims description 11
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 11
- 238000005453 pelletization Methods 0.000 claims description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- 235000019890 Amylum Nutrition 0.000 claims description 10
- 239000004970 Chain extender Substances 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 210000000481 breast Anatomy 0.000 claims description 6
- FQINETJTVSEXPE-UHFFFAOYSA-N butanedioic acid;butane-1,4-diol Chemical compound OCCCCO.OC(=O)CCC(O)=O FQINETJTVSEXPE-UHFFFAOYSA-N 0.000 claims description 6
- 150000007520 diprotic acids Chemical class 0.000 claims description 6
- 235000013312 flour Nutrition 0.000 claims description 6
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 6
- 239000004576 sand Substances 0.000 claims description 6
- 238000012546 transfer Methods 0.000 claims description 6
- BRGDDIPTNDBIGV-UHFFFAOYSA-N C(CCCO)O.C(CCC(=O)O)(=O)O.C(C1=CC=C(C(=O)O)C=C1)(=O)O Chemical compound C(CCCO)O.C(CCC(=O)O)(=O)O.C(C1=CC=C(C(=O)O)C=C1)(=O)O BRGDDIPTNDBIGV-UHFFFAOYSA-N 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 4
- 244000017020 Ipomoea batatas Species 0.000 claims description 4
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000009987 spinning Methods 0.000 claims description 4
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 3
- 229930195725 Mannitol Natural products 0.000 claims description 3
- 229910019213 POCl3 Inorganic materials 0.000 claims description 3
- 244000061456 Solanum tuberosum Species 0.000 claims description 3
- 235000002595 Solanum tuberosum Nutrition 0.000 claims description 3
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000011109 contamination Methods 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- 238000007791 dehumidification Methods 0.000 claims description 3
- 239000000594 mannitol Substances 0.000 claims description 3
- 235000010355 mannitol Nutrition 0.000 claims description 3
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- 229940056729 sodium sulfate anhydrous Drugs 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000000811 xylitol Substances 0.000 claims description 3
- 235000010447 xylitol Nutrition 0.000 claims description 3
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 3
- 229960002675 xylitol Drugs 0.000 claims description 3
- 240000002853 Nelumbo nucifera Species 0.000 claims description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 claims description 2
- 240000001085 Trapa natans Species 0.000 claims description 2
- 240000004922 Vigna radiata Species 0.000 claims description 2
- 235000010721 Vigna radiata var radiata Nutrition 0.000 claims description 2
- 235000011469 Vigna radiata var sublobata Nutrition 0.000 claims description 2
- VVLUUGNZSQRYFP-UHFFFAOYSA-N butane-1,4-diol;hexanedioic acid;terephthalic acid Chemical compound OCCCCO.OC(=O)CCCCC(O)=O.OC(=O)C1=CC=C(C(O)=O)C=C1 VVLUUGNZSQRYFP-UHFFFAOYSA-N 0.000 claims description 2
- JSZNQQVYIRVXQV-UHFFFAOYSA-N butanedioic acid;butane-1,4-diol;hexanedioic acid Chemical compound OCCCCO.OC(=O)CCC(O)=O.OC(=O)CCCCC(O)=O JSZNQQVYIRVXQV-UHFFFAOYSA-N 0.000 claims description 2
- 238000000855 fermentation Methods 0.000 claims description 2
- 230000004151 fermentation Effects 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 230000000813 microbial effect Effects 0.000 claims description 2
- 229920001592 potato starch Polymers 0.000 claims description 2
- 235000009165 saligot Nutrition 0.000 claims description 2
- 239000004033 plastic Substances 0.000 abstract description 6
- 229920003023 plastic Polymers 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 238000001125 extrusion Methods 0.000 abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract 4
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 2
- 239000001569 carbon dioxide Substances 0.000 abstract 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract 1
- 229920000747 poly(lactic acid) Polymers 0.000 abstract 1
- 239000004626 polylactic acid Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 230000006872 improvement Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000010168 coupling process Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 230000003413 degradative effect Effects 0.000 description 3
- 238000009775 high-speed stirring Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 229920008262 Thermoplastic starch Polymers 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 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
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004628 starch-based polymer Substances 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
-
- 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
- B29C48/92—Measuring, controlling or regulating
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92514—Pressure
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92923—Calibration, after-treatment or cooling zone
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a full-biodegradable resin prepared from non-staple grain plant modified starch and a preparation method thereof, which comprises the steps of firstly putting the non-staple grain plant starch into a reaction kettle, adding water to prepare starch milk, heating to a proper temperature, stirring and washing, then adding a chemical to perform modified grafting treatment on the starch in an aqueous solution, then performing water-powder separation by adopting a centrifugal method, then conveying the separated modified starch to an air flow drying system for dewatering and drying, then adding 100 parts of the dried modified starch into 5-50 parts of a compatilizer, 2-15 parts of an opening agent and 0-100 parts of polylactic acid, and 150-250 parts of a binary acid dihydric alcohol copolymer capable of being fully biodegraded to be uniformly mixed, putting the mixture into a double-screw double-exhaust double-screw extrusion molding machine set or a double-exhaust double-screw tabletting extrusion machine set, extruding and granulating or tabletting under a proper temperature and pressure to prepare a full-biodegradable special resin/material or sheet, the invention not only has the same using function as common plastic products, but also has complete biological decomposition performance, and can be quickly decomposed into carbon dioxide and water after being used and discarded, so that the carbon dioxide and the water are consumed by the environment.
Description
Technical field
The present invention relates to full biolysis resin of a kind of non-staple food grain plant modified starch making and preparation method thereof.
Background technology
Utilizing renewable resources to prepare biological decomposition material is an important channel; Use natural macromolecular materials such as starch, Mierocrystalline cellulose, chitin, pulullan polysaccharide, Sunlover 10 to be raw material, can obtain the biolysis plastic prod through various modifications and working method.Take all factors into consideration from the cost of material, workability, mechanical property etc., but starch---the biolysis polymkeric substance and the compound system thereof of natural decomposing macromolecular material and synthetic are the primary study development objects.China does not just have numerous enterprises to be engaged in this Products Development in research from last century; More representational technical matters has: maximum degradative plastics enterprise---the Danhai Co., Ltd., Tianjin of China's beginning of this century, and its technology method that adopts is: refinement → spinning oil oar → mixed coupling of starch cake → height → add mixed with resin → twin screw double flow extruding pelletization is ground in W-Gum → oil bath vacuum hydro-extraction → serialization; Former Nanjing Su Shi degradative resin chemical industry ltd adopts W-Gum → gelatinization → add compatilizer and mixes with each associated resin → twin screw double flow extruding pelletization; And the grand great new and high technology of Dongguan City development corporation, Ltd. adopts: W-Gum → height is mixed heat dehydration coupling → mix with associated resin → twin screw double flow extruding pelletization or compressing tablet; These enterprises adopt W-Gum; Two kinds nothing more than of the processing technology routines that starch is handled; The one, coupling method, the 2nd, gelatinization method.Corn is the staple food grain crop, uses W-Gum to exist the problem of striving grain with the people, and coupling method exists that the coupling graft(ing)degree is low, starch and the vector resin consistency is poor, product surface is coarse, be difficult to do meticulous film series products, and starch such as is prone to ooze out at problem; The gelatinization method will be used high amounts of solvents such as glycerine etc.; Tied up the material space; Cause starch content low, mechanical property is not high enough, and moisture-sensitive causes defectives such as its rerum natura and dimensional stability be not good enough; This several years University Of Tianjin, Sichuan University, the magnificent Science and Technology Ltd. in Wuhan etc. have also carried out corresponding research and development aspect thermoplastic starch, but the problems referred to above are still perplexing actual the application.
Summary of the invention
In order to overcome above-mentioned defective, the invention provides full biolysis resin of the low non-staple food grain plant modified starch making of a kind of cost and preparation method thereof.
The present invention for the technical scheme that solves its technical problem and adopt is: the full biolysis resin that a kind of non-staple food grain plant modified starch is made, its raw material are formed and are comprised following component and ratio of weight and number:
100 parts of non-staple food grain plant modified starches, 5～30 parts of compatilizers, 0～2 part of chainextender, 0～15 part of opening agent, 0～100 part of POLYACTIC ACID can complete biolytic diprotic acid divalent alcohol copolymers 150～250 parts.
As further improvement of the present invention, non-staple food grain plant modified starch is the compsn of a kind of in the non-staple food grain plant amylums such as cassava modified starch, mung bean modified starch, sweet potato modified starch, Ipomoea batatas modified starch, modified potato starch, water caltrop modified starch or lotus root modified starch or two kinds.
As further improvement of the present invention, compatilizer is the compsn of a kind of in sorbyl alcohol, Xylitol or the N.F,USP MANNITOL or two kinds.
As further improvement of the present invention, chainextender is a kind of in ADR-4268CS type or the ADR-4370 type chainextender.
As further improvement of the present invention, the opening agent is agent of silicon-dioxide opening or the agent of titanium oxide opening.
As further improvement of the present invention, POLYACTIC ACID is the polymkeric substance that the microbial method fermentation generates lactic acid.
As further improvement of the present invention, can complete biolytic diprotic acid divalent alcohol copolymers be the compsn of a kind of in Succinic Acid-butyleneglycol multipolymer, Succinic Acid-adipic acid-butyleneglycol multipolymer, terephthalic acid-Succinic Acid-butyleneglycol multipolymer, the terephthalic acid-adipic acid-butyleneglycol multipolymer or two kinds.
The preparation method of the full biolysis resin that a kind of non-staple food grain plant modified starch is made, it is characterized in that: it comprises the steps:
(1) gets the 100 portions of non-staple food grain plant of exsiccant modified starches;
(2) in the 100 portions of non-staple food grain plant of exsiccant modified starches, add 20～50 parts of compatilizers; 2～15 parts of opening agent; 0～100 part of POLYACTIC ACID; Can mix for 150～250 parts by complete biolytic diprotic acid divalent alcohol copolymers; The double gas of input twin screw extrudes in the grain-making machine group or the double gas of twin screw is extruded in the compressing tablet unit, and extruding pelletization or compressing tablet under 140～165 ℃ of melt temperatures and melt pressure 1～5 Mpa are processed full biolysis resin or sheet material that non-staple food grain plant modified starch is made.
As further improvement of the present invention, the preparation of non-staple food grain plant modified starch described in the step (1): fresh cassava (or other tuber crops) is cleaned (desilt, peeling), drop in the kibbler then and pulverize; Become tapioca(flour) (or other non-staple food grain plant amylum) through spinning (sieve and discharge the potato slag) again, again tapioca(flour) (or other non-staple food grain plant amylum) is advanced reaction kettle and add water furnishing milk of starch, the about 22.5～23.5Be of concentration; Add the Sodium sulfate anhydrous.min(99) of starch quality 2%, prevent starch pasting, using mass concentration is pH value to 10～11 that 5% dilute alkaline soln is transferred milk of starch; Stirred 30 minutes, and then under 40 ℃ of conditions, added 0.15% the POCl3 that accounts for starch quality; Reacted 30 minutes, and transferred pH value to 10.0～10.2 with 10% dilute hydrochloric acid solution again, keeping solution temperature is 40 ℃; In reaction kettle, slowly add the organic acid (maleic anhydride or organic acids such as acetic anhydride or adipic anhydride or octenyl succinic or Succinic anhydried) that accounts for starch quality 5.0%, treat that organic acid adds after, the dilute alkaline soln with 5% transfers the maintenance pH value constant; Continue reaction 15 minutes, transfer pH value to 6.5～6.8, termination reaction with 10% dilute hydrochloric acid solution again; Obtain the modified starch breast, the modified starch breast is crossed 200 mesh sieves, remove particulate contamination; Remove sand through sand cleaning machine; Outstanding stream washer washing starch, centrifugal dewatering again, the inlet air flow dehumidification system drying that dewaters, make modified starch after pack for use.
As further improvement of the present invention, opening agent described in the step (2) is agent of silicon-dioxide opening or the agent of titanium oxide opening, the preparation of agent of silicon-dioxide opening or the agent of titanium oxide opening: get 100 ㎏ (1250～3000 order) silicon dioxide powder or titanium dioxide powder and drop in the high cold mixed pot; Be stirred to material temperature rise to 105 ℃; Drop into 2 ㎏ aluminate coupling agents, restir drops into the hard ester acid of 1.5 ㎏ during to material temperature rise to 115 ℃; Restir is put into cold mixed pot during to material temperature rise to 125 ℃; Drop into 30 ㎏ Succinic Acid-butyleneglycol multipolymer when being cooled to below 50 ℃, stir, take the dish out of the pot after about ten minutes; Drop into and to extrude air-cooled tie rod pelletizing pack in the dual-screw pelletizer group, agent of silicon-dioxide opening or the agent of titanium oxide opening.
The invention has the beneficial effects as follows: because the present invention is in the source of making starch to the processing of starch; On the production line of modified starch, carry out; To have the sex change substitution value high for this reason, and sex change is thorough, does not stay the dead angle; The starch ester with long-chain organic molecule and the consistency of vector resin are improved greatly; Thereby also strengthened the addition of starch, form coupling method and gelatinization method incomparable technical superiority, and the Technology of the uniqueness that the present invention had; Functional materials blend such as the in addition complete again biocompatible agent of institute's modified starch ester that obtains, full biolysis resin, process have complete biodegradable property, high substitution of resources property, full biological decomposition material cheaply.Formation is from the plantation---industrial chain of starch---modified starch---starch plastic; The full biological decomposition material of the starch-based that makes has that bio-based content is high, thermoplasticity is good, good mechanical performance, weathering resistance stability are high, can farthest give play to the synergy and the hygienic safety of differing materials, form domestic and international degradative plastics industry exclusive production technology; The present invention has used non-staple food grain plant amylum; Do not strive grain, do not strive ground with grain with the people, the existing complete biolytic function of institute's product that obtains can play the effect (it is free from environmental pollution to degrade voluntarily after discarded) of environment protection again; Can also play substitution of resources, alleviate exhausted day by day petroleum resources; On the other hand; It has also supported agriculture prodn, and for the non-staple food grain plant amylum in rural area has found new market, it still is the part of low-carbon circular economy simultaneously; To promote Chinese national economy and social sustainable development, meet the requirement of construction " resource-conserving and environment-friendly society ".
Embodiment
In order to deepen to understanding of the present invention, will combine embodiment that the present invention is made further detailed description below, this embodiment only is used to explain the present invention, does not constitute the qualification to protection domain of the present invention.
At first, the preparation of non-staple food grain plant modified starch: with fresh cassava or other tuber crops are cleaned, desilt and peeling, drop in the kibbler then and pulverize, again through spinning; Sieve and discharge the potato slag, process tapioca(flour) or other non-staple food grain plant amylum, again tapioca(flour) or other non-staple food grain plant amylum are added reaction kettle and add water furnishing milk of starch, the about 22.5～23.5Be of concentration; Add the Sodium sulfate anhydrous.min(99) of starch quality 2%, prevent starch pasting, using mass concentration is pH value to 10～11 that 5% dilute alkaline soln is transferred milk of starch, stirs 30 minutes; Then under 40 ℃ of conditions, add 0.15% the POCl3 that accounts for starch quality, reacted 30 minutes; Transfer pH value to 10.0～10.2 with 10% dilute hydrochloric acid solution again, keeping solution temperature is 40 ℃, in reaction kettle, slowly adds the organic acid that accounts for starch quality 5.0%; After treating that organic acid adds, the dilute alkaline soln with 5% is transferred and is kept pH value constant, continues reaction 15 minutes; Transfer pH value to 6.5～6.8 with 10% dilute hydrochloric acid solution again, termination reaction obtains the modified starch breast; The modified starch breast is crossed 200 mesh sieves, remove particulate contamination, remove sand through sand cleaning machine; Outstanding stream washer washing starch, centrifugal dewatering again, the inlet air flow dehumidification system drying that dewaters, make non-staple food grain plant modified starch after pack for use.
Secondly, the preparation of agent of silicon-dioxide opening or the agent of titanium oxide opening: get 100 ㎏, 2000 purpose silicon dioxide powders or titanium dioxide powder and drop in the high cold mixed pot, high-speed stirring is to material temperature rise to 105 ℃; Drop into 2 ㎏ aluminate coupling agents, when high-speed stirring is to material temperature rise to 115 ℃ again, drop into the hard ester acid of 1.5 ㎏; Put into cold mixed pot when high-speed stirring is to material temperature rise to 125 ℃ again; Drop into 30 ㎏ Succinic Acid-butyleneglycol multipolymer when being cooled to below 50 ℃, stir, take the dish out of the pot after about ten minutes; Drop into and to extrude air-cooled tie rod pelletizing pack in the dual-screw pelletizer group, agent of silicon-dioxide opening or the agent of titanium oxide opening.
Embodiment one: get aforementioned dried non-staple food grain plant modified starch 100 ㎏, sorbyl alcohol 20 ㎏; Silicon-dioxide opening agent 10 ㎏, POLYACTIC ACID 30 ㎏, Succinic Acid-terephthalic acid-butyleneglycol copolymer 1 00 ㎏; Succinic Acid-adipic acid-butyleneglycol copolymer 1 00 ㎏ stirs; Take the dish out of the pot after about ten minutes, drop in the TE75 type dual-screw pelletizer group and extrude air-cooled tie rod pelletizing
Table one: dual-screw pelletizer group technological temperature table
| 1 group 125 ℃ | 2 groups 130 ℃ | 3 groups 135 ℃ | 4 groups 140 ℃ | 5 groups 140 ℃ | 6 groups 140 ℃ | 7 groups 135 ℃ |
| 8 groups 135 ℃ | 9 groups 135 ℃ | 10 groups 130 ℃ | 11 groups 125 ℃ | 12 groups 125 ℃ | 125 ℃ of die heads | 140 ℃ of melt actual temperatures |
After being heated to above-mentioned design temperature, be incubated 30 minutes, open main frame, the main control system electric current is about 200A, and melt pressure is controlled at 1 Mpa, the open vacuum gas barrier, and control vacuum tightness is about 0.08Mpa.Regulation and control metering feeding twin screw invariablenes turning speed is at 190 rev/mins, and adjustment tie rod pulling speed is about 25 meters/minute, after extruding tie rod and meeting required size requirements, tie rod is filled in be cut into cylindric particle of uniform size in the dicing machine.Metering pack packs again, make it to become the full biolysis of blown film level with full biolysis function resin dedicated/material.This pellet is poured in the inflation film manufacturing machine, about 130 ℃ of control blown film temperature, the control blow-up ratio is about 2, makes its blow molding for can complete biolytic tube film, this film is sent into that just can make in the bag machine can complete biolytic film bag product again.
Embodiment two: get aforementioned dried non-staple food grain plant modified starch 100 ㎏ and drop in the stirrer, drop into N.F,USP MANNITOL 25 ㎏ again, ADR-4268CS type chainextender 2 ㎏; POLYACTIC ACID 80 ㎏; Succinic Acid-butyleneglycol multipolymer 80 ㎏, Succinic Acid-terephthalic acid-butyleneglycol multipolymer 50 ㎏ stir, take the dish out of the pot after about ten minutes; Drop in the 75 type twin screw sheet material machine hoppers and extrude compressing tablet
Table two: twin screw sheet material unit technological temperature table
| 1 group 135 ℃ | 2 groups 140 ℃ | 3 groups 145 ℃ | 4 groups 145 ℃ | 5 groups 145 ℃ | 6 groups 150 ℃ | 150 ℃ of drapings |
| One 155 ℃ of moulds | 2 155 ℃ of moulds | 3 160 ℃ of moulds | 4 155 ℃ of moulds | 5 155 ℃ of moulds | 150 ℃ at elbow | 160 ℃ of melt actual temperatures |
After being heated to above-mentioned design temperature, be incubated 30 minutes, open main frame, the main control system electric current is about 210A, and melt pressure is controlled at 3 Mpa, the open vacuum gas barrier, and control vacuum tightness is about 0.08Mpa.Regulation and control metering feeding twin screw invariablenes turning speed is at 230 rev/mins; Will two of production thickness of product adjustment roll gap between the rod according to institute, adjustment calendering rod pulling speed is respectively 24 meters/minute, 24.1 meters/minute; 24.2 rice/minute; 24.3 rice/minute, adjustment T mould die gap, control sheet material transverse thick thinness deviation is between ± 0.02 mm.Intact in the extrusion sheet adjustment, after conforming to quality requirements, just get into during forcing machine extruding sheet molten mass and go up in the middle last item, through the typing of extruding postcooling, form the biodegradable sheet material.Again this sheet material is carried out plastic uptake or towards moulding, makes it to become the biodegradable packaging vessel according to required product mold.
Embodiment three: get aforementioned dried non-staple food grain plant modified starch 100 ㎏ and drop in the stirrer; Thereafter drop into Xylitol 22 ㎏, titanium oxide opening agent 15 ㎏, POLYACTIC ACID 50 ㎏; Succinic Acid-terephthalic acid-butyleneglycol multipolymer 50 ㎏, adipic acid-terephthalic acid-butyleneglycol copolymer 1 50 ㎏ stir; Take the dish out of the pot after about ten minutes, drop in the TE75 type dual-screw pelletizer group and extrude air-cooled tie rod pelletizing
Table three: dual-screw pelletizer group technological temperature table
| 1 group 140 ℃ | 2 groups 140 ℃ | 3 groups 145 ℃ | 4 groups 150 ℃ | 5 groups 150 ℃ | 6 groups 150 ℃ | 7 groups 155 ℃ |
| 8 groups 155 ℃ | 9 groups 155 ℃ | 10 groups 150 ℃ | 11 groups 145 ℃ | 12 groups 145 ℃ | 150 ℃ of die heads | 160 ℃ of melt actual temperatures |
After being heated to above-mentioned design temperature, be incubated 30 minutes, open main frame, the main control system electric current is about 210A, and melt pressure is controlled at 4Mpa, the open vacuum gas barrier, and control vacuum tightness is about 0.08Mpa.Regulation and control metering feeding twin screw invariablenes turning speed is at 220 rev/mins, and adjustment tie rod pulling speed is about 28 meters/minute, after extruding tie rod and meeting required size requirements, tie rod is filled in be cut into cylindric particle of uniform size in the dicing machine.Metering pack packs again, make it to become the full biolysis of slush molding level with full biolysis function resin dedicated/material.This pellet is poured in the blow moulding machine, about 140 ℃ of control mold temperature, just can make by the style of slush molding mould accordingly can complete biolytic hollow piece.
Embodiment four: get aforementioned dried non-staple food grain plant modified starch 100 ㎏ and drop in the stirrer, drop into N.F,USP MANNITOL 30 ㎏ thereafter, ADR-4268CS type chainextender 2 ㎏; POLYACTIC ACID 100 ㎏; Succinic Acid-butyleneglycol copolymer 1 00 ㎏, Succinic Acid-terephthalic acid-butyleneglycol multipolymer 60 ㎏ stir, take the dish out of the pot after about ten minutes; Drop in the TE75 type dual-screw pelletizer group and extrude air-cooled tie rod pelletizing
Table four: dual-screw pelletizer group technological temperature table
| 1 group 145 ℃ | 2 groups 145 ℃ | 3 groups 150 ℃ | 4 groups 150 ℃ | 5 groups 150 ℃ | 6 groups 150 ℃ | 7 groups 155 ℃ |
| 8 groups 155 ℃ | 9 groups 155 ℃ | 10 groups 160 ℃ | 11 groups 160 ℃ | 12 groups 160 ℃ | 160 ℃ of die heads | 165 ℃ of melt actual temperatures |
After being heated to above-mentioned design temperature, be incubated 30 minutes, open main frame, the main control system electric current is about 220A, and melt pressure is controlled at 5 Mpa, the open vacuum gas barrier, and control vacuum tightness is about 0.08Mpa.Regulation and control metering feeding twin screw invariablenes turning speed is at 220 rev/mins, and adjustment tie rod pulling speed is about 23 meters/minute, after extruding tie rod and meeting required size requirements, tie rod is filled in be cut into cylindric particle of uniform size in the dicing machine.The metering pack packs again; Make it to become the full biolysis of the injection grade with full biolysis function resin dedicated/material; This pellet is poured in the injection moulding machine, and control injection moulding temperature is about 160 ℃, and just can make by the style of injection mold accordingly can complete biolytic injection-molded item.
Claims (10)
1. full biolysis resin that non-staple food grain plant modified starch is made, it is characterized in that: its raw material is formed and is comprised following component and ratio of weight and number:
100 parts of non-staple food grain plant modified starches, 5～30 parts of compatilizers, 0～2 part of chainextender, 0～15 part of opening agent, 0～100 part of POLYACTIC ACID can complete biolytic diprotic acid divalent alcohol copolymers 150～250 parts.
2. the full biolysis resin that non-staple food grain plant modified starch according to claim 1 is made is characterized in that: described non-staple food grain plant modified starch is the compsn of a kind of in the non-staple food grain plant amylums such as cassava modified starch, mung bean modified starch, sweet potato modified starch, Ipomoea batatas modified starch, modified potato starch, water caltrop modified starch or lotus root modified starch or two kinds.
3. the full biolysis resin that non-staple food grain plant modified starch according to claim 1 is made is characterized in that: described compatilizer is the compsn of a kind of in sorbyl alcohol, Xylitol or the N.F,USP MANNITOL or two kinds.
4. the full biolysis resin that non-staple food grain plant modified starch according to claim 1 is made is characterized in that: described chainextender is a kind of in ADR-4268CS type or the ADR-4370 type chainextender.
5. the full biolysis resin that non-staple food grain plant modified starch according to claim 1 is made, it is characterized in that: described opening agent is agent of silicon-dioxide opening or the agent of titanium oxide opening.
6. the full biolysis resin that non-staple food grain plant modified starch according to claim 1 is made is characterized in that: described POLYACTIC ACID is the polymkeric substance that the microbial method fermentation generates lactic acid.
7. the full biolysis resin that non-staple food grain plant modified starch according to claim 1 is made is characterized in that: described can complete biolytic diprotic acid divalent alcohol copolymers be the compsn of a kind of in Succinic Acid-butyleneglycol multipolymer, Succinic Acid-adipic acid-butyleneglycol multipolymer, terephthalic acid-Succinic Acid-butyleneglycol multipolymer, the terephthalic acid-adipic acid-butyleneglycol multipolymer or two kinds.
8. the preparation method of the full biolysis resin made of a non-staple food grain plant modified starch, it is characterized in that: it comprises the steps:
(1) gets the 100 portions of non-staple food grain plant of exsiccant modified starches;
(2) in the 100 portions of non-staple food grain plant of exsiccant modified starches, add 20～50 parts of compatilizers; 2～15 parts of opening agent; 0～100 part of POLYACTIC ACID; Can mix for 150～250 parts by complete biolytic diprotic acid divalent alcohol copolymers; The double gas of input twin screw extrudes in the grain-making machine group or the double gas of twin screw is extruded in the compressing tablet unit, and extruding pelletization or compressing tablet under 140～165 ℃ of melt temperatures and melt pressure 1～5 Mpa are processed full biolysis resin or sheet material that non-staple food grain plant modified starch is made.
9. the preparation method of the full biolysis resin that non-staple food grain plant modified starch according to claim 8 is made is characterized in that: the preparation of non-staple food grain plant modified starch described in the step (1): with fresh cassava or other tuber crops are cleaned, desilt and peeling, drop in the kibbler then and pulverize; Through spinning, sieve and discharge the potato slag again, process tapioca(flour) or other non-staple food grain plant amylum; Again tapioca(flour) or other non-staple food grain plant amylum are added reaction kettle and add water furnishing milk of starch, the about 22.5～23.5Be of concentration adds the Sodium sulfate anhydrous.min(99) of starch quality 2%; Prevent starch pasting, using mass concentration is pH value to 10～11 that 5% dilute alkaline soln is transferred milk of starch, stirs 30 minutes; Then under 40 ℃ of conditions, add 0.15% the POCl3 that accounts for starch quality, reacted 30 minutes; Transfer pH value to 10.0～10.2 with 10% dilute hydrochloric acid solution again, keeping solution temperature is 40 ℃, in reaction kettle, slowly adds the organic acid that accounts for starch quality 5.0%; After treating that organic acid adds, the dilute alkaline soln with 5% is transferred and is kept pH value constant, continues reaction 15 minutes; Transfer pH value to 6.5～6.8 with 10% dilute hydrochloric acid solution again, termination reaction obtains the modified starch breast; The modified starch breast is crossed 200 mesh sieves, remove particulate contamination, remove sand through sand cleaning machine; Outstanding stream washer washing starch, centrifugal dewatering again, the inlet air flow dehumidification system drying that dewaters, make non-staple food grain plant modified starch after pack for use.
10. the preparation method of the full biolysis resin that non-staple food grain plant modified starch according to claim 8 is made, it is characterized in that: opening agent described in the step (2) is agent of silicon-dioxide opening or the agent of titanium oxide opening, the preparation of agent of silicon-dioxide opening or the agent of titanium oxide opening: get 100 ㎏, 1250～3000 purpose silicon dioxide powders or titanium dioxide powder and drop in the high cold mixed pot; Be stirred to material temperature rise to 105 ℃; Drop into 2 ㎏ aluminate coupling agents, restir drops into the hard ester acid of 1.5 ㎏ during to material temperature rise to 115 ℃; Restir is put into cold mixed pot during to material temperature rise to 125 ℃; Drop into 30 ㎏ Succinic Acid-butyleneglycol multipolymer when being cooled to below 50 ℃, stir, take the dish out of the pot after about ten minutes; Drop into and to extrude air-cooled tie rod pelletizing pack in the dual-screw pelletizer group, agent of silicon-dioxide opening or the agent of titanium oxide opening.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059530A (en) * | 2013-01-30 | 2013-04-24 | 唐山师范学院 | Composite material for producing disposable plastic products and preparation method of composite material |
| CN103865107A (en) * | 2014-03-26 | 2014-06-18 | 苏州汉丰新材料股份有限公司 | Preparation method and preparation device for fully-biodegradable resin prepared from non-staple-food-grain composite modified hydrophobic starch |
| CN105733206A (en) * | 2016-04-14 | 2016-07-06 | 苏州汉丰新材料股份有限公司 | Degradable material, application thereof for preparing hollow container and preparation method and device of hollow container |
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| CN1903922A (en) * | 2006-05-16 | 2007-01-31 | 广东上九生物降解塑料有限公司 | Fully biodegradable plastic resin and production method of film products thereof |
| CN1948374A (en) * | 2006-09-28 | 2007-04-18 | 浙江华发生态科技有限公司 | Biomass full degradable material and its preparation technology |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1903922A (en) * | 2006-05-16 | 2007-01-31 | 广东上九生物降解塑料有限公司 | Fully biodegradable plastic resin and production method of film products thereof |
| CN1948374A (en) * | 2006-09-28 | 2007-04-18 | 浙江华发生态科技有限公司 | Biomass full degradable material and its preparation technology |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103059530A (en) * | 2013-01-30 | 2013-04-24 | 唐山师范学院 | Composite material for producing disposable plastic products and preparation method of composite material |
| CN103059530B (en) * | 2013-01-30 | 2015-01-07 | 唐山师范学院 | Composite material for producing disposable plastic products and preparation method of composite material |
| CN103865107A (en) * | 2014-03-26 | 2014-06-18 | 苏州汉丰新材料股份有限公司 | Preparation method and preparation device for fully-biodegradable resin prepared from non-staple-food-grain composite modified hydrophobic starch |
| CN105733206A (en) * | 2016-04-14 | 2016-07-06 | 苏州汉丰新材料股份有限公司 | Degradable material, application thereof for preparing hollow container and preparation method and device of hollow container |
| CN105733206B (en) * | 2016-04-14 | 2018-11-06 | 苏州汉丰新材料股份有限公司 | The preparation method and preparation facilities of degradation material and its application and hollow container in preparing hollow container |
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