CN114479397A - Vinasse-based fully-degradable membrane, and preparation method and application thereof - Google Patents
Vinasse-based fully-degradable membrane, and preparation method and application thereof Download PDFInfo
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- CN114479397A CN114479397A CN202210259490.1A CN202210259490A CN114479397A CN 114479397 A CN114479397 A CN 114479397A CN 202210259490 A CN202210259490 A CN 202210259490A CN 114479397 A CN114479397 A CN 114479397A
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- 239000012528 membrane Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 45
- 238000002156 mixing Methods 0.000 claims abstract description 31
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 26
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 23
- 240000008042 Zea mays Species 0.000 claims abstract description 18
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims abstract description 18
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims abstract description 18
- 235000005822 corn Nutrition 0.000 claims abstract description 18
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000001110 calcium chloride Substances 0.000 claims abstract description 16
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 16
- 239000004014 plasticizer Substances 0.000 claims abstract description 15
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 15
- 239000008158 vegetable oil Substances 0.000 claims abstract description 15
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 14
- 229920002472 Starch Polymers 0.000 claims abstract description 14
- 239000001913 cellulose Substances 0.000 claims abstract description 14
- 229920002678 cellulose Polymers 0.000 claims abstract description 14
- 235000010980 cellulose Nutrition 0.000 claims abstract description 14
- 239000000314 lubricant Substances 0.000 claims abstract description 14
- 239000002121 nanofiber Substances 0.000 claims abstract description 14
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims abstract description 14
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims abstract description 14
- 239000000661 sodium alginate Substances 0.000 claims abstract description 14
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 14
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 14
- 239000008107 starch Substances 0.000 claims abstract description 14
- 235000019698 starch Nutrition 0.000 claims abstract description 14
- 239000005452 food preservative Substances 0.000 claims abstract description 7
- 235000019249 food preservative Nutrition 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 50
- 238000003756 stirring Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000001125 extrusion Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 13
- 239000010902 straw Substances 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 238000010008 shearing Methods 0.000 claims description 8
- 238000010345 tape casting Methods 0.000 claims description 8
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 7
- 238000010096 film blowing Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 6
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 6
- 239000000523 sample Substances 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 5
- 238000007906 compression Methods 0.000 claims description 5
- 230000006835 compression Effects 0.000 claims description 5
- 235000012343 cottonseed oil Nutrition 0.000 claims description 5
- 239000002385 cottonseed oil Substances 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 235000021388 linseed oil Nutrition 0.000 claims description 5
- 239000000944 linseed oil Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 235000012424 soybean oil Nutrition 0.000 claims description 5
- 239000003549 soybean oil Substances 0.000 claims description 5
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 4
- 235000013773 glyceryl triacetate Nutrition 0.000 claims description 4
- 229960002622 triacetin Drugs 0.000 claims description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- WCDDVEOXEIYWFB-VXORFPGASA-N (2s,3s,4r,5r,6r)-3-[(2s,3r,5s,6r)-3-acetamido-5-hydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-4,5,6-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@@H]1C[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](C(O)=O)O[C@@H](O)[C@H](O)[C@H]1O WCDDVEOXEIYWFB-VXORFPGASA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- -1 fatty acid ester Chemical class 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229940014041 hyaluronate Drugs 0.000 claims description 2
- 230000001954 sterilising effect Effects 0.000 abstract description 8
- 238000004804 winding Methods 0.000 abstract description 6
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 5
- 238000007789 sealing Methods 0.000 abstract description 3
- 230000004888 barrier function Effects 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 238000001514 detection method Methods 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 55
- 239000000047 product Substances 0.000 description 28
- 235000013339 cereals Nutrition 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 108090000623 proteins and genes Proteins 0.000 description 8
- 102000004169 proteins and genes Human genes 0.000 description 8
- 230000002195 synergetic effect Effects 0.000 description 8
- 230000000844 anti-bacterial effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 5
- 229940072056 alginate Drugs 0.000 description 5
- 235000010443 alginic acid Nutrition 0.000 description 5
- 229920000615 alginic acid Polymers 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 230000002070 germicidal effect Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000004089 microcirculation Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 108060006613 prolamin Proteins 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000512259 Ascophyllum nodosum Species 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 208000003643 Callosities Diseases 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 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 description 1
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 206010020649 Hyperkeratosis Diseases 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- 241000186660 Lactobacillus Species 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920013643 Mirel Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000199919 Phaeophyceae Species 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 239000001087 glyceryl triacetate Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000003102 growth factor Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229940039696 lactobacillus Drugs 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 235000012015 potatoes Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/466—Bio- or photodegradable packaging materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/04—Alginic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2489/00—Characterised by the use of proteins; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2499/00—Characterised by the use of natural macromolecular compounds or of derivatives thereof not provided for in groups C08J2401/00 - C08J2407/00 or C08J2489/00 - C08J2497/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a vinasse-based fully-degradable membrane, and a preparation method and application thereof. The vinasse-based fully degradable film comprises a component A, a component B and a component C; the component A comprises: vinasse, plasticizer, polyvinyl alcohol and corn bran; the component B comprises: acetate starch, sodium alginate, cellulose nanofiber and calcium chloride; the component C comprises: epoxidized vegetable oils, lubricants, and polyhydroxyalkanoates. The vinasse-based fully-degradable film is prepared by matching various bio-based raw materials with fully-degradable resin, and can completely meet the requirements of practical application indexes of a stretch winding film, a food preservative film and a shopping bag by adjusting different mixing ratios of the various raw materials. After practical application and detection, the vinasse-based fully-degradable membrane disclosed by the invention is obviously superior to similar products sold in the market in appearance performance, physical and mechanical properties, sealing strength, automatic sterilization, barrier property and the like, and is simple in process implementation and suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of fully-degradable polymers, and particularly relates to a vinasse-based fully-degradable film, and a preparation method and application thereof.
Background
The distiller's grains are roughly divided into white spirit distiller's grains and brewer's grains, and are products rich in protein, having a certain alcoholic strength, and rich in growth factors, methionine, cystine, crude fiber, yeast, lactobacillus and the like after being brewed from five-grain coarse cereals such as potatoes, beans, sorghum, corns, wheat, sticky rice and the like.
According to statistics, the vinasse yield of China exceeds one hundred million tons. However, until now, the utilization of distillers grains was in the low-value conversion of feed, fuel, and fertilizer. How to convert the vinasse which is a recyclable and renewable resource derived from food into an application material with high added value is an important environmental protection strategy which extremely accords with the green sustainable development of China. At present, most of the known technologies have indexes such as mechanical property, water repellency and flame retardance lower than those of petroleum-based plastics aiming at composite materials converted from vinasse, and the price of the composite materials is extremely high, so that the requirements of customers are difficult to meet, and meanwhile, the application and the expansion of downstream products are limited.
Therefore, the technical scheme of the invention is provided.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a vinasse-based fully-degradable membrane, and a preparation method and application thereof. The vinasse-based fully-degradable film is prepared by scientifically matching various biological-based raw materials with fully-degradable resin, and can completely meet the requirements of practical application indexes of a stretch winding film, a food preservative film or a shopping bag by adjusting different mixing ratios of the raw materials. In addition, the inventor also confirms that the vinasse-based full-degradable membrane can be completely decomposed into carbon dioxide and water and other organic matters which are beneficial to improving the soil microcirculation in the soil with appropriate relative humidity and relative temperature.
The invention adopts the scheme that the invention provides the vinasse-based full-degradable membrane which comprises a component A, a component B and a component C; wherein, the component A comprises the following raw materials: vinasse, plasticizer, polyvinyl alcohol and corn bran; the component B comprises the following raw materials: acetate starch, sodium alginate, cellulose nanofiber and calcium chloride; the component C comprises the following raw materials: epoxidized vegetable oils, lubricants, and polyhydroxyalkanoates.
Preferably, the component A comprises the following raw materials in parts by mass: vinasse: 30-50 parts of a plasticizer: 5-15 parts of polyvinyl alcohol: 10-30 parts of corn bran: 5-15 parts of a solvent; the component B comprises the following raw materials in parts by mass: acetate starch: 3-5 parts of sodium alginate: 3-5 parts of cellulose nano-fibers: 2-3 parts and calcium chloride: 1-5 parts; the component C comprises the following raw materials in parts by mass: epoxy vegetable oil: 2-6 parts of a lubricant: 1-3 parts of polyhydroxy fatty acid ester: 50-70 parts.
Preferably, the component A comprises the following raw materials in parts by mass: vinasse: 40 parts of plasticizer: 10 parts of polyvinyl alcohol: 20 parts and corn bran: 10 parts of (A); the component B comprises the following raw materials in parts by mass: acetate starch: 4 parts of sodium alginate: 4 parts of cellulose nano-fibers: 2.5 parts and calcium chloride: 3 parts of a mixture; the component C comprises the following raw materials in parts by mass: epoxy vegetable oil: 4 parts of lubricant: 2 parts and polyhydroxyalkanoate: 60 parts.
For the purpose of understanding the present invention, the raw materials used in the present invention will be described.
Preferably, the vinasse is: one or a combination of both of distiller's grains or brewer's grains containing water at 60% in fresh state, free from mold and having a predetermined alcohol content (usually about 35% in the distiller's grains) is commercially available.
Preferably, the plasticizer is a combination of at least three of glycerol, propylene glycol, polyethylene glycol, glycerol triacetate and sorbitol in any mass ratio, and is commercially available.
Preferably, the polyvinyl alcohol is: the unit product after instant dissolution and expansion is creatively and tightly combined with water molecules and a small amount of residual ethanol in the vinasse under the stirring state at the temperature of 30-100 ℃ for rapid alcoholysis, the alcoholysis rate can reach more than 96%, and the unit product effectively forms interface combination reaction with other materials, thereby realizing the aim of plasticizing and toughening the materials by a one-step method. The polyvinyl alcohol grades in the invention are respectively as follows: 100-27 parts of polyvinyl alcohol, 100-35 parts of polyvinyl alcohol and 100-60 parts of polyvinyl alcohol in any mass ratio, and can be obtained commercially.
Preferably, the corn bran is a main byproduct in corn starch processing, and the protein content is more than 60%, wherein approximately 50% of the protein is prolamin. The inventor finds that the corn bran, residual ethanol in the distiller's grains and the alcohol-based component in the plasticizer are modified in a synergistic reaction mode, and the protein in the corn bran can form prolamin under the condition of temperature-controlled high-speed stirring. The alcohol soluble protein not only has unique film forming property, but also has antibacterial, antioxidant and degradation properties, and has a water repellent function because of containing a large amount of hydrophobic amino acid, and can be obtained commercially.
Preferably, the acetate starch is corn modified starch with good film forming property, high viscosity and high clarity, and the acetate starch can form a mutual synergistic effect when being mixed with other raw materials, not only can generate antioxidant performance, but also can enable a target product to be exposed to low temperature for long-term storage, is a low-cost stabilizer and can be obtained commercially.
Preferably, the sodium alginate is a byproduct obtained after iodine and mannitol are extracted from brown algae such as kelp or gulfweed, and is nontoxic and odorless. The inventor researches and discovers that the calcium phosphate can effectively perform synergistic reaction with water molecules and other components including calcium ions in the material, quickly form gel under extremely mild conditions, have unique film-forming property, can improve the tensile strength, the automatic sterilization function and the thermal stability of the target product, and can be commercially obtained.
Preferably, the cellulose nanofiber is a functional additive, has good compatibility and high crystallinity. Under extremely mild conditions, the material can fully and rapidly permeate into the molecular structure of the raw material, and form a net structure, so that the mutual synergistic reaction among materials is effectively promoted, the content of carboxyl in the materials is increased, and the tensile elasticity of the target product is improved. The specific application indexes of the cellulose nano-fiber are as follows: diameter: 80-100 nm, length: 5-20 μm, purity: 99.9%, crystallinity: not less than 85%, solid content: not less than 5 percent, and can be obtained commercially.
Preferably, the calcium chloride is a powder with extremely strong water absorption, and can be used as a drying agent, a microorganism inhibitor and a curing agent according to the characteristics of the calcium chloride. The research of the inventor finds that particularly after calcium chloride reacts with the sodium alginate, alginate fiber with flame retardant property is generated, and the alginate fiber forms interface combination with other raw materials related to the invention, so that the tensile strength and the flame retardant property of the target product can be effectively improved, and the alginate fiber can be obtained commercially.
Preferably, the epoxidized vegetable oil is a combination of epoxidized soybean oil, epoxidized cottonseed oil and epoxidized linseed oil in any mass ratio. The research of the inventor finds that the combination of the three epoxy vegetable oils and the raw materials of the invention have synergistic reaction, not only can play a role in plasticizing the raw materials, but also can effectively improve the weather resistance of the target product of the invention, and can be obtained commercially.
Preferably, the lubricant is a combination of barium hyaluronate and oleamide with the mass ratio of 1:1, and is commercially available.
Preferably, the polyhydroxyalkanoate is a natural high-molecular fully biodegradable material synthesized by a plurality of microorganisms, and has extremely high film-forming property. The research of the inventor finds that the material has excellent compatibility with various raw materials, can improve the gas barrier property of the target product, has extremely high elasticity and cohesiveness, is preferably Mirel (F1006) made in America, and can be obtained commercially.
Based on the same technical concept, the invention also provides a preparation method of the vinasse-based fully-degradable membrane, which comprises the following steps:
(1) mixing vinasse, a plasticizer, polyvinyl alcohol and corn bran, and then heating and stirring to obtain a mixture a;
(2) adding acetate starch, sodium alginate, cellulose nanofiber and calcium chloride into the mixture a, mixing, heating and stirring to obtain a mixture b;
(3) the mixture b is devillicate to realize shearing, friction, dispersion, reaction, compression, melting, exhaust and plasticization, and after the devillicate, the mixture b is dried and subjected to superfine grinding to obtain multi-protomer mixture micro powder;
(4) mixing the epoxy vegetable oil, the lubricant and the polyhydroxyalkanoate to obtain a mixture c; mixing the mixture c and the multi-pathogen mixture micro powder, heating and stirring, and then extruding and granulating to obtain particle master batches;
(5) and (3) forming the particle master batches into a film by tape casting or film blowing, and obtaining the vinasse-based fully-degradable film after the film forming process is finished.
Preferably, in the step (3), a three-screw straw devillicating and brooming machine is adopted for the devillicating and brooming; the diameter of a screw of the three-screw straw devillicating and brooming machine is 270mm, the length-diameter ratio is 10:1, the rotating speed of the screw is 400r/min, and the interval temperature is as follows: a first area: 75 ℃ and a second zone: 85 ℃, three zones: 95 ℃ and four zones: 105 ℃ and five zones: 115 ℃ and six regions: the vacuum degree of each section is 0.04-0.08 MPa at 90 ℃.
Preferably, in the step (4), a three-screw extrusion granulator is adopted for the extrusion granulation; the diameter of a screw of the three-screw extrusion granulator is 80mm, the length-diameter ratio is 30:1, the rotating speed of the screw is 400r/min, and the interval temperature is as follows: a first area: 100 ℃ and a second zone: 110 ℃, three zones: 115 ℃ and four zones: 120 ℃ and five zones: 125 ℃ and six zones: 130 ℃ and seven regions: 120 ℃, eight regions 110 ℃, and probe: the vacuum degree of each section is 0.03MPa at 100 ℃.
Preferably, in the step (5), the equipment adopted by the cast film forming process is a casting machine; the screw rotating speed of the casting machine is 60-110 r/min, and the interval temperature is as follows: a first area: 80 ℃ and a second zone: 100 ℃, three zones: 120 ℃ and four zones: 140 ℃ and five regions: the linear velocity is 4-8 m/min at 120 ℃.
Preferably, in the step (5), the film blowing machine is adopted as the equipment for the film forming process; the rotating speed of a screw of the film blowing machine is 40-80 r/min, and the interval temperature is as follows: a first area: 90 ℃ and a second zone: 110 ℃, three zones: 130 ℃ and four zones: the linear velocity is 4-8 m/min at 150 ℃.
Based on the same technical concept, the invention further provides application of the vinasse-based fully-degradable film in preparation of stretch winding films, food preservative films or shopping bags.
The invention has the beneficial effects that:
the preparation method of the vinasse-based fully-degradable membrane is prepared by scientific compatibility and synergistic reaction of various bio-based raw materials including vinasse, creatively utilizes ethanol components in the vinasse and proteins in corn bran to perform synergistic reaction to form alcohol soluble protein with an antibacterial effect, the alcohol soluble protein is fully compatible with other raw materials to form interface combination, and the alcohol soluble protein with the antibacterial effect is generated through reaction; in addition, alginate reacts with calcium chloride in the materials to generate alginate fibers with antibacterial and flame retardant effects, and the derivative substances generated by the raw materials in the synergistic reaction process greatly improve the mechanical properties of the target membrane product. And the vinasse-based fully-degradable film can generate various target indexes required by different types of film products by adjusting different mixing ratios of various raw materials, so that the practical application of a stretch winding film, a food preservative film or a shopping bag can be completely met. In addition, the practical application process of the target membrane product by the inventor has determined that in soil with appropriate relative humidity and relative temperature, the vinasse-based fully-degradable membrane can be completely decomposed into carbon dioxide and water within 180 days, and other organic matters which are beneficial to improving the soil microcirculation.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
The embodiment provides a preparation method of a vinasse-based fully-degradable membrane, which comprises the following steps:
(1) mixing 30kg of brewer's grains, 5kg of plasticizer (combination of glycerol, propylene glycol and polyethylene glycol in any mass proportion), 10kg of polyvinyl alcohol (combination of 100-27 parts of polyvinyl alcohol, 100-35 parts of polyvinyl alcohol and 100-60 parts of polyvinyl alcohol in any mass proportion) and 5kg of corn bran, putting into a temperature-controlled stirrer (preferably: a SRL-W800 horizontal high-speed mixer set produced by Ohio mechanical science and technology Limited, Zhang hong Kong), fully and uniformly mixing all the raw materials of the component A at a stirring mixing speed of 200r/min under a temperature-controlled state of 80 ℃, and obtaining a mixture a until the surfaces of the brewer's grains are coated with a film layer and have dispersibility;
(2) 3kg of acetate starch, 3kg of sodium alginate, 2kg of cellulose nanofiber (preferably: 80nm in diameter, 5 μm in length, 99.9% in purity, 85% in crystallinity and 5% in solid content) and 1kg of calcium chloride are mixed and added into the mixture a to completely fuse the component A and the component B together, so that the surface temperature of the two groups of raw materials is strictly controlled at 100 ℃, the stirring speed is 200r/min, and the mixture is stirred and mixed until no steam exists on the surface of the material, when the surface of the material to be mixed has obvious glossiness and is provided with more flaky elastomers, the material to be mixed has good compatibility, and various material interfaces also form firm combination and generate great activity. Confirming that the material graft copolymerization process step is finished, discharging and cooling for later use to obtain a mixture b;
(3) conveying the mixture b to a 270-type parallel three-screw straw devillicating and fibrillating machine, wherein the screw diameter of the 270-type parallel three-screw straw devillicating and fibrillating machine is as follows: 270mm, the length-diameter ratio of 10:1, and three screws which are arranged in parallel and rotate in the same direction; the rotating speed of the screw is 400r/min, and the interval temperature is as follows: a first area: 75 ℃ and a second zone: 85 ℃, three zones: 95 ℃ and four zones: 105 ℃ and five zones: 115 ℃ and six regions: the vacuum degree of each section was 0.04MPa at 90 ℃. The mixture b is arranged in a body cavity of the 270 type parallel three-screw straw devillicating and fibrillating machine, the processes of shearing, friction, dispersion, reaction, compression, melting, exhausting and plasticizing are realized along with three screws rotating in the same direction, and then the mixture is discharged from a discharge port of the devillicating and fibrillating machine, at the moment, the surface of the material has higher strength and toughness and the characteristic of a fish scale-shaped structure with plasticity, and the completion of the material melting, plasticizing and modifying process step can be determined;
(4) then, the materials which are melted, plasticized and modified are primarily crushed and then are dried in vacuum, aiming at the characteristics of the melted, plasticized and modified materials, the selected vacuum dryer is an SZG double-cone vacuum dryer produced by Jinxiang drying equipment, Inc. of Changzhou, in the drying process, the materials are completely exposed in a vacuum state in a drying cavity, and in a very short time, the moisture in the materials and in a surface structure is fully dried to be below 4 percent, so that the drying step is determined to be finished;
and continuously putting the dried material into an airflow superfine pulverizer, wherein the airflow superfine pulverizer is selected from the following components: the super little rubbing crusher of explosion-proof air current of QLM20 type of Shandong's production of Xin powder equipment Limited company, the super little rubbing crusher index advantage of air current can promote and strengthen the homogeneity and the physical stability of the material particle diameter behind the miropowder, makes the material very easily reach the average particle size and is: the raw material micro powder is obtained after the production is finished according to the requirement of 400 meshes;
(5) mixing 2kg of epoxidized vegetable oil (a combination of epoxidized soybean oil, epoxidized cottonseed oil and epoxidized linseed oil in any mass ratio), 1kg of lubricant (a combination of barium stearate and oleamide in a mass ratio of 1: 1) and 50kg of polyhydroxyalkanoate to obtain a mixture c; mixing the raw material micro powder and the mixture c according to the mass ratio of 3:7, and stirring and mixing at 100 ℃ and 200r/min until the surface of the polyhydroxyalkanoate is uniformly coated into powder; then conveying the mixture to a reverse triangular three-screw extrusion granulator set, extruding the materials into strips in the granulator set through a die after melting, shearing, dispersing, reacting, compressing and exhausting, stretching along with the rotation of a conveying steel chain, cooling by multiple wind points, and then granulating to obtain granular master batches; the inverted triangle-shaped three-screw extrusion granulator set is an 80-type inverted triangle-shaped three-screw extrusion granulator set produced by Beijing Zhongxing innovative plastic machinery manufacturing Co., Ltd, the screw diameter is 80mm, the length-diameter ratio is 30:1, the screw rotating speed is 400r/min, and the interval temperature is as follows: a first area: 100 ℃ and a second zone: 110 ℃, three zones: 115 ℃ and four zones: 120 ℃ and five zones: 125 ℃ and six zones: 130 ℃ and seven regions: 120 ℃, eight zones 110 ℃, and probe: the vacuum degree of each section is 0.03MPa at 100 ℃;
(6) carrying out tape casting film forming on the particle master batches by adopting a tape casting machine, wherein the rotating speed of a screw of the tape casting machine is 60r/min, and the interval temperature is as follows: a first area: 80 ℃ and a second zone: 100 ℃, three zones: 120 ℃ and four zones: 140 ℃ and five regions: and (3) at the temperature of 120 ℃, and the linear velocity is 4m/min, thus obtaining the vinasse-based fully degradable membrane.
The vinasse-based fully-degradable film obtained in the embodiment can be used for preparing a stretch winding film.
Example 2
The embodiment provides a preparation method of a vinasse-based fully-degradable membrane, which comprises the following steps:
(1) mixing 50kg of vinasse (the combination of brewer's grains and white spirit vinasse in any mass proportion), 15kg of plasticizer (the combination of polyethylene glycol, glyceryl triacetate and sorbitol in any mass proportion), 30kg of polyvinyl alcohol (the combination of 100-27 parts of polyvinyl alcohol, 100-35 parts of polyvinyl alcohol and 100-60 parts of polyvinyl alcohol in any mass proportion) and 15kg of corn bran, putting into a temperature-controlled stirrer (preferably: an SRL-W800 horizontal high-speed mixing unit produced by Ohio mechanical science and technology Limited, Zhang harbor), and fully and uniformly mixing all the raw materials of the component A at a stirring and mixing speed of 200r/min under a temperature-controlled state of 80 ℃, and obtaining a mixture a until the surfaces of vinasse particles are coated with a film layer and have dispersibility;
(2) 5kg of acetate starch, 5kg of sodium alginate, 3kg of cellulose nanofiber (preferably: the diameter: 100nm, the length: 20 μm, the purity: 99.9%, the crystallinity: 87%, and the solid content: 6%) and 5kg of calcium chloride are mixed and added into the mixture a to completely fuse the component A and the component B together, so that the surface temperature of the two groups of raw materials is strictly controlled at 100 ℃, the stirring speed is 200r/min, and the mixture is stirred and mixed until no steam exists on the surface of the material, when the surface of the material to be mixed has obvious glossiness and is provided with more flaky elastomers, the material to be mixed has good compatibility, and various material interfaces also form firm combination and generate great activity. Confirming that the material graft copolymerization process step is finished, discharging and cooling for later use to obtain a mixture b;
(3) conveying the mixture b to a 270-type parallel three-screw straw devillicating and fibrillating machine, wherein the screw diameter of the 270-type parallel three-screw straw devillicating and fibrillating machine is as follows: 270mm, the length-diameter ratio of 10:1, and three screws which are arranged in parallel and rotate in the same direction; the rotating speed of the screw is 400r/min, and the interval temperature is as follows: a first area: 75 ℃ and a second zone: 85 ℃, three zones: 95 ℃ and four zones: 105 ℃ and five zones: 115 ℃ and six regions: the vacuum degree of each section is 0.08MPa at 90 ℃. The mixture b is arranged in a body cavity of the 270 type parallel three-screw straw devillicating and fibrillating machine, the processes of shearing, friction, dispersion, reaction, compression, melting, exhaust and plasticization are realized along with three screws rotating in the same direction, and then the mixture is discharged from a discharge port of the devillicating and fibrillating machine, at the moment, the surface of the material has higher strength and toughness and the characteristic of a fish scale-shaped structure with plasticity, and the process step of melting, plasticizing and modifying the material can be determined to be completed;
(4) then, the material which is melted, plasticized and modified is primarily crushed and then is dried in vacuum, aiming at the characteristics of the melted, plasticized and modified material, the selected vacuum dryer is an SZG double-cone vacuum dryer produced by Jinxiang drying equipment, Inc. in Changzhou city, during the drying process, the material is completely exposed in a vacuum state in a drying cavity, and the moisture in the material and in a surface structure is fully dried to be below 4 percent in a very short time, so that the drying is determined to be completed;
and continuously putting the dried material into an airflow superfine pulverizer, wherein the airflow superfine pulverizer is selected from the following components: the QLM20 type explosion-proof airflow superfine pulverizer produced by Shandong Jingxin powder equipment Limited company has the index advantages that the uniformity and the physical stability of the particle size of the pulverized material can be improved and strengthened, so that the material can easily reach the requirement of 400 meshes of average particle size, and the raw material micropowder is obtained after the process is finished;
(5) mixing 6kg of epoxidized vegetable oil (a combination of epoxidized soybean oil, epoxidized cottonseed oil and epoxidized linseed oil in any mass ratio), 3kg of lubricant (a combination of barium stearate and oleamide in a mass ratio of 1: 1) and 70kg of polyhydroxyalkanoate to obtain a mixture c; mixing the raw material micro powder and the mixture c according to a mass ratio of 4:6, and stirring and mixing at 100 ℃ and 200r/min until the surface of the polyhydroxyalkanoate is uniformly coated into powder; then conveying the mixture to a reverse triangular three-screw extrusion granulator set, extruding the materials into strips in the granulator set through a die after melting, shearing, dispersing, reacting, compressing and exhausting, stretching along with the rotation of a conveying steel chain, cooling by multiple wind points, and then granulating to obtain granular master batches; the inverted triangle-shaped three-screw extrusion granulator set is an 80-type inverted triangle-shaped three-screw extrusion granulator set produced by Beijing Zhongxing innovative plastic machinery manufacturing Limited company, the diameter of a screw is 80mm, the length-diameter ratio is 30:1, the rotating speed of the screw is 400r/min, and the interval temperature is as follows: a first area: 100 ℃ and a second zone: 110 ℃, three zones: 115 ℃ and four zones: 120 ℃ and five zones: 125 ℃ and six zones: 130 ℃ and seven regions: 120 ℃, eight regions 110 ℃, and probe: the vacuum degree of each section is 0.03MPa at 100 ℃;
(6) performing tape casting on the particle master batches by using a tape casting machine to form a film, wherein the rotating speed of a screw of the tape casting machine is 110r/min, and the interval temperature is as follows: a first area: 80 ℃ and a second zone: 100 ℃, three zones: 120 ℃ and four zones: 140 ℃ and five regions: and (3) at 120 ℃, and the linear velocity is 8m/min, thus obtaining the vinasse-based fully-degradable membrane.
The vinasse-based fully-degradable film obtained in the embodiment can be used for preparing food preservative films.
Example 3
The embodiment provides a preparation method of a vinasse-based fully-degradable membrane, which comprises the following steps:
(1) mixing 40kg of distiller's grains, 10kg of plasticizer (a combination of glycerol, propylene glycol, polyethylene glycol and glycerol triacetate in any mass proportion), 20kg of polyvinyl alcohol (a combination of 100-27 parts of polyvinyl alcohol, 100-35 parts of polyvinyl alcohol and 100-60 parts of polyvinyl alcohol in any mass proportion) and 10kg of corn bran, putting into a temperature-controlled stirrer (preferably: a SRL-W800 horizontal high-speed mixing unit produced by Ohio mechanical science and technology Limited in Zhang hong Kong), and fully and uniformly mixing all the raw materials of the component A at a stirring mixing speed of 200r/min under a temperature-controlled state of 80 ℃, and obtaining a mixture a until the surfaces of the distiller's grains are coated with a film layer and have dispersibility;
(2) 4kg of acetate starch, 4kg of sodium alginate, 2.5kg of cellulose nanofibers (the diameter: 90nm, the length: 12 mu m, the purity: 99.9%, the crystallinity: 88% and the solid content: 7%) and 3kg of calcium chloride are mixed and added into the mixture a to completely fuse the component A and the component B together, so that the surface temperature of the two groups of raw materials is strictly controlled at 100 ℃, the stirring speed is 200r/min, and the mixture is stirred and mixed until no steam exists on the surface of the material, when the surface of the material to be mixed has obvious glossiness and more flaky elastomers, the material to be mixed has good compatibility, and various material interfaces have firm combination and generate great activity. Confirming that the material graft copolymerization process step is finished, discharging and cooling for later use to obtain a mixture b;
(3) conveying the mixture b to a 270-type parallel three-screw straw devillicating and fibrillating machine, wherein the screw diameter of the 270-type parallel three-screw straw devillicating and fibrillating machine is as follows: 270mm, the length-diameter ratio of 10:1, and three screws which are arranged in parallel and rotate in the same direction; the rotating speed of the screw is 400r/min, and the interval temperature is as follows: a first area: 75 ℃ and a second zone: 85 ℃, three zones: 95 ℃ and four zones: 105 ℃ and five zones: 115 ℃ and six regions: the vacuum degree of each section is 0.06MPa at 90 ℃. The mixture b is arranged in a body cavity of the 270 type parallel three-screw straw devillicating and fibrillating machine, the processes of shearing, friction, dispersion, reaction, compression, melting, exhaust and plasticization are realized along with three screws rotating in the same direction, and then the mixture is discharged from a discharge port of the devillicating and fibrillating machine, at the moment, the surface of the material has higher strength and toughness and the characteristic of a fish scale-shaped structure with plasticity, and the process step of melting, plasticizing and modifying the material can be determined to be completed;
(4) then, the materials which are melted, plasticized and modified are primarily crushed and then are dried in vacuum, aiming at the characteristics of the melted, plasticized and modified materials, the selected vacuum dryer is an SZG double-cone vacuum dryer produced by Jinxiang drying equipment, Inc. of Changzhou, during the drying process, the materials are completely exposed in a vacuum state in a drying cavity, and the moisture in the materials and in a surface structure is fully dried to be below 4 percent in a very short time, so that the drying is determined to be finished;
and continuously putting the dried material into an airflow superfine pulverizer, wherein the airflow superfine pulverizer is selected from the following components: the QLM20 type explosion-proof airflow superfine pulverizer produced by Shandong Jingxin powder equipment Limited company has the index advantages that the uniformity and the physical stability of the particle size of the pulverized material can be improved and strengthened, so that the material can easily reach the requirement of 400 meshes of average particle size, and the raw material micropowder is obtained after the process is finished;
(5) mixing 4kg of epoxidized vegetable oil (a combination of epoxidized soybean oil, epoxidized cottonseed oil and epoxidized linseed oil in any mass ratio), 2kg of lubricant (a combination of barium stearate and oleamide in a mass ratio of 1: 1) and 60kg of polyhydroxyalkanoate to obtain a mixture c; mixing the raw material micro powder and the mixture c according to a mass ratio of 5:5, and stirring and mixing at 100 ℃ and 200r/min until the surface of the polyhydroxyalkanoate is uniformly coated into powder; then conveying the mixture to a reverse triangular three-screw extrusion granulator set, extruding the materials into strips in the granulator set through a die after melting, shearing, dispersing, reacting, compressing and exhausting, stretching along with the rotation of a conveying steel chain, cooling by multiple wind points, and then granulating to obtain granular master batches; the inverted triangle-shaped three-screw extrusion granulator set is an 80-type inverted triangle-shaped three-screw extrusion granulator set produced by Beijing Zhongxing innovative plastic machinery manufacturing Limited company, the diameter of a screw is 80mm, the length-diameter ratio is 30:1, the rotating speed of the screw is 400r/min, and the interval temperature is as follows: a first area: 100 ℃ and a second zone: 110 ℃, three zones: 115 ℃ and four zones: 120 ℃ and five zones: 125 ℃ and six zones: 130 ℃ and seven regions: 120 ℃, eight regions 110 ℃, and probe: the vacuum degree of each section is 0.03MPa at 100 ℃;
(6) will granule master batch adopts inflation film manufacturing machine to carry out the blown film membrane, inflation film manufacturing machine's screw rod rotational speed is 40r/min, and interval temperature is: a first area: 90 ℃ and a second zone: 110 ℃, three zones: 130 ℃ and four zones: and (3) at 150 ℃, and the linear velocity is 4m/min, thus obtaining the vinasse-based fully-degradable film.
The vinasse-based fully-degradable film obtained in the embodiment can be used for preparing shopping bags.
The vinasse-based fully-degradable film obtained in example 1 of the invention can be used for preparing a stretch winding film, and in order to verify the effect, the film is compared with similar products sold in the market, and the results are shown in table 1.
TABLE 1 physical mechanical Properties
In addition, in order to show the bactericidal effect, 50. mu.L of the E.coli suspension was applied to the surface of the film of the sample to be tested, and after 10min, 20min, and 30min, respectively, the bactericidal rate was measured, and the results are shown in Table 2. (the same below)
TABLE 2 germicidal Effect
As can be seen from tables 1 and 2, the physical properties and the sterilization effects of the vinasse-based fully-degradable film obtained in the embodiment 1 of the invention are obviously superior to those of similar products sold in the market, and the excellent level is achieved; in addition, through field tests of the inventor, the viscosity of the stretch wrap film obtained in the embodiment 1 is superior to that of the similar products sold in the market, and the stretch wrap film can wrap goods products more tightly and more firmly; finally, especially the oxygen permeability coefficient and the water vapor permeability coefficient, the example 1 is less than the similar products sold on the market, which shows that in the process of wrapping goods by the stretch wrap film, the external water vapor, oxygen and other gases are more difficult to permeate, and the effect of the tightness of the wrapping is better than that of the similar products sold on the market.
The vinasse-based fully-degradable film obtained in example 2 of the invention can be used for preparing food preservative films, and in order to verify the effect, the vinasse-based fully-degradable film is compared with similar products sold in the market, and the results are shown in tables 3, 4 and 5.
TABLE 3 appearance test results
TABLE 4 physical and mechanical Properties requirements
TABLE 5 germicidal Effect
As can be seen from tables 3, 4 and 5, the appearance, physical and mechanical properties and sterilization effect of the vinasse-based fully-degradable membrane obtained in example 2 of the invention are obviously superior to those of the similar products sold in the market. Especially the oxygen and carbon dioxide gas transmission deviation is obviously smaller in example 2 than the similar products sold in the market, which shows that the product stability is higher
The vinasse-based fully degradable film obtained in example 3 of the invention can be used for preparing shopping bags, and the results are shown in tables 6, 7 and 8 by comparing the film with similar products sold in the market for verifying the effect.
TABLE 6 physical and mechanical Properties
TABLE 7 sealing Strength
TABLE 8 germicidal Effect
| Group of | Sterilizing rate/10 min | Sterilizing rate/20 min | Sterilizing rate/30 min |
| Example 3 | 40.1％ | 81.2％ | 93.3％ |
| The same kind of products sold in the market | 0 | 0 | 0 |
As can be seen from tables 6, 7 and 8, the physical and mechanical properties, sealing strength and sterilization effect of the vinasse-based fully-degradable membrane obtained in the embodiment 3 of the invention are obviously superior to those of similar products sold in the market; especially the oxygen and carbon dioxide gas permeation deviation, the example 3 is obviously smaller than the similar products on the market, which shows that the product stability is higher.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. The vinasse-based fully degradable membrane is characterized by comprising a component A, a component B and a component C; wherein, the component A comprises the following raw materials: vinasse, plasticizer, polyvinyl alcohol and corn bran; the component B comprises the following raw materials: acetate starch, sodium alginate, cellulose nanofiber and calcium chloride; the component C comprises the following raw materials: epoxidized vegetable oils, lubricants, and polyhydroxyalkanoates.
2. The vinasse-based fully degradable membrane of claim 1, wherein the component A comprises the following raw materials in parts by mass: lees: 30-50 parts of a plasticizer: 5-15 parts of polyvinyl alcohol: 10-30 parts of corn bran: 5-15 parts; the component B comprises the following raw materials in parts by mass: acetate starch: 3-5 parts of sodium alginate: 3-5 parts of cellulose nano-fibers: 2-3 parts and calcium chloride: 1-5 parts; the component C comprises the following raw materials in parts by mass: epoxy vegetable oil: 2-6 parts of a lubricant: 1-3 parts of polyhydroxy fatty acid ester: 50-70 parts.
3. The vinasse-based fully degradable membrane of claim 2, wherein the component A comprises the following raw materials in parts by mass: vinasse: 40 parts of plasticizer: 10 parts of polyvinyl alcohol: 20 parts and corn bran: 10 parts of (A); the component B comprises the following raw materials in parts by mass: acetate starch: 4 parts of sodium alginate: 4 parts of cellulose nano-fiber: 2.5 parts and calcium chloride: 3 parts of a mixture; the component C comprises the following raw materials in parts by mass: epoxy vegetable oil: 4 parts of lubricant: 2 parts and polyhydroxyalkanoate: 60 parts.
4. The vinasse-based full-degradable film according to any one of claims 1 to 3, wherein the vinasse is one or a combination of two of distiller's grains and brewer's grains; the plasticizer is a combination of at least three of glycerol, propylene glycol, polyethylene glycol, glycerol triacetate and sorbitol; the epoxidized vegetable oil is a combination of epoxidized soybean oil, epoxidized cottonseed oil and epoxidized linseed oil; the lubricant is a combination of barium stearate and oleamide; the weight ratio of the barium hyaluronate to the oleamide is 1: 1.
5. The preparation method of the vinasse-based fully degradable membrane as claimed in any one of claims 1 to 4, wherein the preparation method comprises the following steps:
(1) mixing vinasse, a plasticizer, polyvinyl alcohol and corn bran, and then heating and stirring to obtain a mixture a;
(2) adding acetate starch, sodium alginate, cellulose nanofiber and calcium chloride into the mixture a, mixing, heating and stirring to obtain a mixture b;
(3) the mixture b is devillicate to realize shearing, friction, dispersion, reaction, compression, melting, exhaust and plasticization, and after the devillicate, the mixture b is dried and subjected to superfine grinding to obtain multi-protomer mixture micro powder;
(4) mixing the epoxy vegetable oil, the lubricant and the polyhydroxyalkanoate to obtain a mixture c; mixing the mixture c and the multi-pathogen mixture micro powder, heating and stirring, and then extruding and granulating to obtain particle master batches;
(5) and (3) forming the particle master batches into a film by tape casting or film blowing, and obtaining the vinasse-based fully-degradable film after the film forming process is finished.
6. The method for preparing the vinasse-based fully degradable membrane according to claim 5, wherein in the step (3), the devillicating and brooming are carried out by adopting a three-screw straw devillicating and brooming machine; the diameter of a screw of the three-screw straw devillicating and brooming machine is 270mm, the length-diameter ratio is 10:1, the rotating speed of the screw is 400r/min, and the interval temperature is as follows: a first area: 75 ℃ and a second zone: 85 ℃, three zones: 95 ℃ and four zones: 105 ℃ and five zones: 115 ℃ and six regions: the vacuum degree of each section is 0.04-0.08 MPa at 90 ℃.
7. The method for preparing the vinasse-based fully degradable film according to claim 5, wherein in the step (4), a three-screw extrusion granulator is adopted for the extrusion granulation; the diameter of a screw of the three-screw extrusion granulator is 80mm, the length-diameter ratio is 30:1, the rotating speed of the screw is 400r/min, and the interval temperature is as follows: a first area: 100 ℃ and a second zone: 110 ℃, three zones: 115 ℃ and four zones: 120 ℃ and five zones: 125 ℃ and six zones: 130 ℃ and seven regions: 120 ℃, eight regions 110 ℃, and probe: the vacuum degree of each section is 0.03MPa at 100 ℃.
8. The method for preparing the vinasse-based fully degradable membrane according to claim 5, wherein in the step (5), the equipment adopted by the casting film forming process is a casting machine; the screw rotating speed of the casting machine is 60-110 r/min, and the interval temperature is as follows: a first area: 80 ℃ and a second zone: 100 ℃, three zones: 120 ℃ and four zones: 140 ℃ and five regions: the linear velocity is 4-8 m/min at 120 ℃.
9. The preparation method of the vinasse-based fully-degradable film according to claim 5, wherein in the step (5), the equipment adopted in the film blowing process is a film blowing machine; the rotating speed of a screw of the film blowing machine is 40-80 r/min, and the interval temperature is as follows: a first area: 90 ℃ and a second zone: 110 ℃, three zones: 130 ℃ and four zones: the linear velocity is 4-8 m/min at 150 ℃.
10. Use of the whole vinasse-based degradable film according to any one of claims 1 to 3 in the preparation of stretch wrap films, food preservative films or shopping bags.
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| CN116410606A (en) * | 2023-03-21 | 2023-07-11 | 杭州靡特洛新材料科技有限公司 | Preparation method and application of high-performance water-soluble controllable biomass-based thermoplastic film |
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| CN113248875A (en) * | 2021-03-29 | 2021-08-13 | 上海昶法新材料有限公司 | Fully-degradable shopping bag film and preparation method thereof |
| CN113278265A (en) * | 2021-06-25 | 2021-08-20 | 华东理工大学 | Degradable lignin-based composite agricultural mulching film and preparation method thereof |
| CN113773559A (en) * | 2021-09-08 | 2021-12-10 | 广州绿徽新材料研究院有限公司 | Biodegradable composite modified film bag particle material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113248875A (en) * | 2021-03-29 | 2021-08-13 | 上海昶法新材料有限公司 | Fully-degradable shopping bag film and preparation method thereof |
| CN113278265A (en) * | 2021-06-25 | 2021-08-20 | 华东理工大学 | Degradable lignin-based composite agricultural mulching film and preparation method thereof |
| CN113773559A (en) * | 2021-09-08 | 2021-12-10 | 广州绿徽新材料研究院有限公司 | Biodegradable composite modified film bag particle material and preparation method thereof |
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| CN116410606A (en) * | 2023-03-21 | 2023-07-11 | 杭州靡特洛新材料科技有限公司 | Preparation method and application of high-performance water-soluble controllable biomass-based thermoplastic film |
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