CN115160654A - Modified cellulose acetate fiber capable of being degraded by microorganisms and preparation method thereof - Google Patents
Modified cellulose acetate fiber capable of being degraded by microorganisms and preparation method thereof Download PDFInfo
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- CN115160654A CN115160654A CN202210818126.4A CN202210818126A CN115160654A CN 115160654 A CN115160654 A CN 115160654A CN 202210818126 A CN202210818126 A CN 202210818126A CN 115160654 A CN115160654 A CN 115160654A
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- 229920002301 cellulose acetate Polymers 0.000 title claims abstract description 150
- 239000000835 fiber Substances 0.000 title claims abstract description 54
- 244000005700 microbiome Species 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 61
- 229920006221 acetate fiber Polymers 0.000 claims abstract description 57
- 150000001242 acetic acid derivatives Chemical class 0.000 claims abstract description 34
- 125000005456 glyceride group Chemical group 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000004367 Lipase Substances 0.000 claims abstract description 17
- 102000004882 Lipase Human genes 0.000 claims abstract description 17
- 108090001060 Lipase Proteins 0.000 claims abstract description 17
- 235000019421 lipase Nutrition 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000000945 filler Substances 0.000 claims abstract description 15
- 239000004014 plasticizer Substances 0.000 claims abstract description 15
- 229920000229 biodegradable polyester Polymers 0.000 claims abstract description 11
- 239000004622 biodegradable polyester Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 11
- 230000009471 action Effects 0.000 claims abstract description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 51
- 239000002245 particle Substances 0.000 claims description 50
- 239000000463 material Substances 0.000 claims description 47
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 44
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 40
- KMZHZAAOEWVPSE-UHFFFAOYSA-N 2,3-dihydroxypropyl acetate Chemical compound CC(=O)OCC(O)CO KMZHZAAOEWVPSE-UHFFFAOYSA-N 0.000 claims description 34
- 235000013312 flour Nutrition 0.000 claims description 29
- 239000002023 wood Substances 0.000 claims description 29
- RYMZZMVNJRMUDD-HGQWONQESA-N simvastatin Chemical group C([C@H]1[C@@H](C)C=CC2=C[C@H](C)C[C@@H]([C@H]12)OC(=O)C(C)(C)CC)C[C@@H]1C[C@@H](O)CC(=O)O1 RYMZZMVNJRMUDD-HGQWONQESA-N 0.000 claims description 23
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 21
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 21
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 21
- 235000011187 glycerol Nutrition 0.000 claims description 18
- 235000003642 hunger Nutrition 0.000 claims description 11
- 230000037351 starvation Effects 0.000 claims description 11
- 230000005484 gravity Effects 0.000 claims description 10
- UYRCGIIFXRGHKH-UHFFFAOYSA-N (2-acetyloxy-3-hydroxypropyl) benzoate Chemical compound CC(=O)OC(CO)COC(=O)c1ccccc1 UYRCGIIFXRGHKH-UHFFFAOYSA-N 0.000 claims description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 6
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 claims description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Polymers OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 5
- 229920000954 Polyglycolide Polymers 0.000 claims description 5
- 229920001432 poly(L-lactide) Polymers 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 229920006238 degradable plastic Polymers 0.000 claims description 4
- UXDDRFCJKNROTO-UHFFFAOYSA-N Glycerol 1,2-diacetate Chemical compound CC(=O)OCC(CO)OC(C)=O UXDDRFCJKNROTO-UHFFFAOYSA-N 0.000 claims description 3
- 235000013773 glyceryl triacetate Nutrition 0.000 claims description 3
- 229910010272 inorganic material Inorganic materials 0.000 claims description 3
- 229960002622 triacetin Drugs 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- XYZZKVRWGOWVGO-UHFFFAOYSA-N Glycerol-phosphate Chemical compound OP(O)(O)=O.OCC(O)CO XYZZKVRWGOWVGO-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229920006167 biodegradable resin Polymers 0.000 claims description 2
- 229940114081 cinnamate Drugs 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 150000002484 inorganic compounds Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000693 micelle Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 230000000813 microbial effect Effects 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 238000010008 shearing Methods 0.000 abstract description 3
- 102000004190 Enzymes Human genes 0.000 abstract description 2
- 108090000790 Enzymes Proteins 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 241001391944 Commicarpus scandens Species 0.000 abstract 1
- 238000007599 discharging Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 238000001878 scanning electron micrograph Methods 0.000 description 14
- 229920001606 poly(lactic acid-co-glycolic acid) Polymers 0.000 description 13
- 238000001035 drying Methods 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- -1 compatilizer Substances 0.000 description 9
- GFPSCFPBWQWHFU-UHFFFAOYSA-N C(C)(=O)OCC(O)CO.C1(=CC=CC=C1)C(=O)O Chemical compound C(C)(=O)OCC(O)CO.C1(=CC=CC=C1)C(=O)O GFPSCFPBWQWHFU-UHFFFAOYSA-N 0.000 description 8
- 239000000523 sample Substances 0.000 description 7
- 238000006065 biodegradation reaction Methods 0.000 description 5
- 239000002361 compost Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 238000010309 melting process Methods 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010561 standard procedure Methods 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002054 inoculum Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PIVAHSKWRZDGSD-UHFFFAOYSA-N (2-formyloxy-3-hydroxypropyl) acetate Chemical compound CC(=O)OCC(CO)OC=O PIVAHSKWRZDGSD-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000012345 acetylating agent Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002327 glycerophospholipids Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- 239000013642 negative control Substances 0.000 description 1
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- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000013641 positive control Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
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Images
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-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/10—Esters of organic acids, i.e. acylates
- C08L1/12—Cellulose acetate
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention relates to a modified cellulose acetate fiber capable of being degraded by microorganisms and a preparation method thereof, belonging to the technical field of modification of high polymer materials. The modified cellulose acetate fiber capable of being degraded by microorganisms comprises the following raw materials in parts by weight: 50-75 parts of cellulose acetate, 15-25 parts of biodegradable polyester, 2-15 parts of glyceride plasticizer, 1-5 parts of compatilizer, 4-10 parts of lipase, 1-5 parts of high-specific-gravity inorganic substance and 1-5 parts of filler. According to the invention, the high proportion of the acetate fiber is realized in the blending, melting and mixing process through the acetate fiber high proportion technology and the special enzyme treatment technology, the macromolecular chains are easy to break under the shearing action to form micro-holes and micro-cracks, and the number of hydroxyl groups on the surface of the acetate fiber is increased, so that the microorganism can easily enter the modified acetate fiber to convert the long-chain molecular structure into the short-chain molecular structure in the microbial degradation process of the modified acetate fiber, and the effect of improving the biodegradability of the acetate fiber is realized.
Description
Technical Field
The invention belongs to the technical field of modification of high polymer materials, and particularly relates to a modified cellulose acetate fiber capable of being degraded by microorganisms and a preparation method thereof.
Background
Acetate fiber, also known as cellulose acetate, is one of the earlier developed chemical fibers in the world, and has been invented by bayer corporation in 1904 for over 100 years. The cellulose acetate is a thermoplastic resin prepared by using acetic acid as a solvent and acetic anhydride as an acetylating agent and performing esterification reaction on cellulose pulp under the action of a catalyst, has excellent physical and mechanical properties and chemical properties, is widely applied to the fields of cigarettes, textiles, glasses, biological medicines and the like, is used as a raw material for producing disposable articles such as cigarette filters, films, adhesive tapes and the like, becomes an indispensable important product in modern industry, and has the second highest yield in the world production total amount of all regenerated cellulose fibers, which is only inferior to viscose.
The wide application of the ethyl acetate disposable product also brings pollution to the waste of the acetate fiber product, although the cellulose acetate has certain biodegradability, in order to improve the mechanical property of the product in the preparation process of the disposable product, substances such as a plasticizer and the like are added, so that the acetate product is difficult to degrade, and heavy burden is brought to the environment and ecology.
Disclosure of Invention
The invention aims to improve the hydrolysis capacity of an acetate fiber product in the microbial degradation process, and provides a modified acetate fiber capable of being degraded by microorganisms and a preparation method thereof.
In a first aspect, the modified cellulose acetate fiber provided by the invention adopts the following technical scheme:
a modified cellulose acetate fiber capable of being degraded by microorganisms comprises the following raw materials in parts by weight: 50-75 parts of cellulose acetate, 15-25 parts of biodegradable polyester, 2-15 parts of glyceride plasticizer, 1-5 parts of compatilizer, 4-10 parts of lipase, 1-5 parts of high-specific-gravity inorganic substance and 1-5 parts of filler.
Furthermore, the modified cellulose acetate fiber comprises, by weight, 55-70 parts of cellulose acetate, 18-20 parts of biodegradable polyester, 4-12 parts of a glyceride plasticizer, 1-2 parts of a compatilizer, 4-6 parts of lipase, 1-3 parts of a high-specific-gravity inorganic substance and 2-4 parts of a filler.
Still further, the high specific gravity inorganic compound is barium sulfate.
Further, the lipase is Lipex 100L or Lipex 50T.
By adopting the technical scheme, the cellulose acetate is added with the inorganic substance with high specific gravity to carry out high specific gravity treatment, the specific gravity of the cellulose acetate is improved, the added lipase hydrolyzes acetyl on the surface of the cellulose acetate, the number of hydroxyl groups on the surface of the cellulose acetate is improved, the cellulose acetate is easier to break in the blending and melting process, and then micropockets and microcracks are formed on the cellulose acetate, microorganisms enter the modified cellulose acetate through the micropockets and the microcracks more easily in the microbial degradation process, the long-chain molecular structure in the cellulose acetate is decomposed into a short-chain molecular structure, and the cellulose acetate also has better biodegradability even if the substances such as a plasticizer are added.
Further, the cellulose acetate is a cellulose acetate micelle;
optionally, the biodegradable polyester is one of poly-L-lactide, polyglycolide or polyglycolide.
By adopting the technical scheme, the poly-L-lactide, the polyglycolide and the poly-glycolide-lactide have good biocompatibility, high permeability, mechanical property and biodegradability, and the substances are added into the cellulose acetate, so that the density of micro-holes and micro-cracks of the cellulose acetate in the blending and melting process can be increased, the specific surface area of the cellulose acetate is further increased, and the degradation of the cellulose acetate by microorganisms is facilitated.
Still further, the glycerin-based plasticizer is selected from two or more of glycerol acetate, glycerol diacetate, glycerol triacetate, glycerol phosphate, glycerol benzoate acetate, triglyceride trimellitate, and glycerol hydrogenated rosin;
optionally, the compatibilizer is one of tetraisopropyl titanate, tetrabutyl titanate, or tetraethyl titanate;
optionally, the filler is one or more of wood flour, carbonate, sulfate, silicate, and cinnamate, and the filler has an average particle size of 6500 to 8500 mesh.
By adopting the technical scheme, the glyceride plasticizer can destroy the strong hydrogen bond acting force in the cellulose acetate, and increase the flexibility of the macromolecular chains in the cellulose acetate, so that the macromolecular chains of the cellulose acetate are easier to generate a shearing action in the blending and melting process, the macromolecular parts of the cellulose acetate are broken to form small molecular chains, and then micro-holes and micro-cracks are formed in the cellulose acetate;
the compatilizer increases the viscosity of the overall formula of the modified cellulose acetate, and simultaneously reduces the thermal decomposition temperature of the cellulose acetate/biodegradable polyester, so that the interior of the cellulose acetate is heated unevenly, the microscopic unevenness of the internal structure of the cellulose acetate is further increased, and the hydrolysis of the cellulose acetate is facilitated;
the filler is selected from inorganic powder, the average particle size of the filler is 6500-8500 meshes, and the addition of the filler can increase the mutual friction and collision among materials in the blending and melting process, so that macromolecular chains of the acetate fiber are more easily broken, and further more micro holes and micro cracks are formed.
In a second aspect, the present invention provides a method for preparing any of the above-mentioned modified cellulose acetate fibers with microbial degradation, which adopts the following technical scheme:
the preparation method of the modified cellulose acetate fiber capable of being degraded by microorganisms comprises the following steps:
s1, uniformly stirring and mixing the cellulose acetate, the biodegradable polyester, the glyceride plasticizer, the compatilizer, the lipase, the high-specific-gravity inorganic matter and the filler to prepare a mixed material;
s2, adding the mixed material into an internal mixer by a starvation feeding method for mixing, so that the mixed material is subjected to multiple actions of two sections of opposite-rotation-direction screw ridges of a rotor and the wall of a mixing chamber;
and S3, extruding the mixed material after mixing, and cooling and forming.
Further, in the S1, the cellulose acetate and the biodegradable resin are subjected to vacuum drying treatment at 45-55 ℃ for 11-13h.
Furthermore, in the S2, the mixing temperature is 50-55 ℃, the rotating speed is 50-70r/min, and the time is 5-10min.
By adopting the technical scheme, the internal mixer is used for mixing the mixed materials, the cellulose acetate is subjected to multiple actions of two sections of opposite rotating direction spiral edges of the rotor and the wall of the mixing chamber in the mixing section, strong dispersion mixing and distribution mixing of the mixed materials are realized at high shear rate, and micro holes and micro cracks are formed in the cellulose acetate under the combined action of inorganic matters with high specific gravity and lipase.
In a third aspect, the degradable plastic product provided by the invention adopts the following technical scheme:
a degradable plastic product is prepared from any one of the above-mentioned modified cellulose acetate fibers capable of being degraded by microbes and/or the modified cellulose acetate fibers prepared by the preparation method of any one of the above-mentioned modified cellulose acetate fibers capable of being degraded by microbes.
Has the advantages that:
biodegradable polyester, glyceride plasticizer, compatilizer, lipase, high-specific-gravity inorganic matter and filler are added into cellulose acetate, high-specific gravity technology and enzyme treatment technology of the cellulose acetate are adopted, so that high-specific gravity of the cellulose acetate is realized in the blending, melting and mixing process, the number of hydroxyl groups on the surface of the cellulose acetate is increased, then a macromolecular chain of the cellulose acetate is more easily broken under the shearing action, micro holes and micro cracks are formed inside the cellulose acetate, and microbes can enter the inside of the cellulose acetate through the micro holes and the micro cracks inside the cellulose acetate to hydrolyze long-chain molecules in the microbial degradation process, so that the biodegradability of the cellulose acetate is improved.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings will be briefly introduced, and it is apparent that the drawings in the following description relate only to some embodiments of the present invention and are not limiting to the present invention.
FIG. 1 is an SEM image of a cross-section of cellulose acetate gel at 1200 magnification;
FIG. 2 is an SEM image of a cross section of a modified cellulose acetate fiber provided in example 1 of the present invention, at 1200 times magnification;
FIG. 3 is an SEM image of a cross-section of a modified cellulose acetate fiber provided in example 2 of the present invention, at 1200 times magnification;
FIG. 4 is an SEM image of a cross-section of a modified cellulose acetate fiber provided in example 3 of the present invention, at 1200 times magnification;
FIG. 5 is an SEM image of a cross-section of a modified cellulose acetate fiber provided in example 4 of the present invention, at 1200 times magnification;
FIG. 6 is an SEM image of a cross-section of a modified cellulose acetate fiber provided in example 5 of the present invention, at 1200 times magnification;
FIG. 7 is an SEM image of a cross-section of a modified cellulose acetate fiber provided in example 6 of the present invention, at 1200 magnifications.
Detailed Description
The reagents and sources used in the present invention are as follows:
lipex 100L, lipex T is provided for Shanghai Hengchen industry Co.
Example 1
The embodiment provides a modified cellulose acetate fiber capable of being degraded by microorganisms, which comprises the following raw materials in parts by weight: 65 parts of cellulose acetate colloidal particles, 20 parts of poly (lactide-co-glycolide), 2 parts of glycerol acetate, 2 parts of hydrogenated rosin glycerol ester, 2 parts of tetraisopropyl titanate, 6 parts of Lipex 100L, 1 part of barium sulfate and 2 parts of wood flour, wherein the average particle size of the wood flour is 6500 meshes.
The embodiment also provides a preparation method of the modified cellulose acetate fiber capable of being degraded by microorganisms, which comprises the following steps:
s1, respectively placing cellulose acetate colloidal particles and poly (lactide-co-glycolide) in a vacuum drying oven, and drying at 50 ℃ for 12 hours;
s2, uniformly mixing the dried cellulose acetate colloidal particles, poly (glycolide-co-lactide), acetin, hydrogenated rosin glyceride, tetraisopropyl titanate, lipex 100L, barium sulfate and wood flour to obtain a mixed material;
s3, feeding the mixed material into a feeding section through a feeding port of an internal mixer, and feeding the mixed material by a starvation feeding method;
s4, entering a mixing section under the spiral conveying of a feeding section of the internal mixer, wherein the mixing temperature is 55 ℃, the mixing time is 10min, the rotating speed is 100r/min when the temperature does not reach 55 ℃, and the rotating speed is reduced to 60r/min when the temperature reaches the set temperature;
s5, conveying the mixed material to a discharging section, and extruding through a discharging opening.
Fig. 1 is an SEM image of a cross section of cellulose acetate gel particles, and fig. 2 is an SEM image of a cross section of modified cellulose acetate fibers provided in this example. As can be seen from the comparison between FIG. 1 and FIG. 2, the internal structure of the cellulose acetate colloidal particles is a regular lamellar structure, and the stacking between the lamellar layers is compact and has stronger acting force, so that the cellulose acetate colloidal particles are difficult to degrade; the modified cellulose acetate fiber provided by the embodiment has a non-uniform internal structure, has micro-holes and micro-cracks, and is beneficial to microorganisms entering the interior of the cellulose acetate to hydrolyze long-chain molecules.
Example 2
The embodiment provides a modified cellulose acetate fiber capable of being degraded by microorganisms, which comprises the following raw materials in parts by weight: 65 parts of cellulose acetate colloidal particles, 20 parts of poly (lactide-co-glycolide), 3 parts of glycerol acetate, 3 parts of hydrogenated rosin glycerol ester, 1 part of tetraisopropyl titanate, 4 parts of Lipex 100L, 2 parts of barium sulfate and 2 parts of wood flour, wherein the average particle size of the wood flour is 6500 meshes.
The embodiment also provides a preparation method of the modified cellulose acetate fiber capable of being degraded by microorganisms, which specifically comprises the following steps:
s1, respectively placing cellulose acetate colloidal particles and poly (lactide-co-glycolide) in a vacuum drying oven, and drying at 50 ℃ for 12 hours;
s2, uniformly mixing the dried cellulose acetate colloidal particles, poly (glycolide-co-lactide), acetin, hydrogenated rosin glyceride, tetraisopropyl titanate, lipex 100L, barium sulfate and wood flour to obtain a mixed material;
s3, feeding the mixed material into a feeding section through a feeding port of an internal mixer, and feeding the mixed material by a starvation feeding method;
s4, entering a mixing section under the spiral conveying of a feeding section of the internal mixer, wherein the mixing temperature is 55 ℃, the mixing time is 10min, the rotating speed is 100r/min when the temperature does not reach 55 ℃, and the rotating speed is reduced to 60r/min when the temperature reaches the set temperature;
s5, conveying the mixed material to a discharging section, and extruding through a discharging opening.
Fig. 3 is an SEM image of a cross section of the modified cellulose acetate provided in this example. As can be seen from the comparison between fig. 3 and fig. 2, the internal structure of the modified acetate fiber provided in this embodiment has more micro-cavities compared to the modified acetate fiber in embodiment 1, and the distribution of the micro-cavities is more uniform, which indicates that the increase of the usage amount of the glyceride plasticizer and the barium sulfate is beneficial to forming more and uniformly distributed micro-cavities inside the acetate fiber, thereby avoiding the problem of forming mechanical defect points due to more micro-cavities and micro-cracks in the local position of the acetate fiber, and improving the biodegradability of the acetate fiber, and at the same time, making the acetate fiber have better mechanical properties.
Example 3
The embodiment provides a modified cellulose acetate fiber capable of being degraded by microorganisms, which comprises the following raw materials in parts by weight: 60 parts of cellulose acetate colloidal particles, 20 parts of poly (lactide-co-glycolide), 2 parts of glycerol acetate, 3 parts of hydrogenated rosin glycerol, 3 parts of glycerol benzoate acetate, 2 parts of tetraisopropyl titanate, 6 parts of Lipex 100L, 2 parts of barium sulfate and 2 parts of wood flour, wherein the average particle size of the wood flour is 6500 meshes.
The embodiment also provides a preparation method of the modified cellulose acetate fiber capable of being degraded by microorganisms, which specifically comprises the following steps:
s1, respectively placing cellulose acetate colloidal particles and poly (lactide-co-glycolide) in a vacuum drying oven, and drying at 50 ℃ for 12 hours;
s2, uniformly mixing the dried cellulose acetate colloidal particles, poly (glycolide-co-lactide), glycerol acetate, hydrogenated rosin glycerol, benzoic acid glycerol acetate, tetraisopropyl titanate, lipex 100L, barium sulfate and wood flour to obtain a mixed material;
s3, feeding the mixed material into a feeding section through a feeding port of an internal mixer, and feeding the mixed material by a starvation feeding method;
s4, entering a mixing section under the spiral conveying of a feeding section of the internal mixer, wherein the mixing temperature is 55 ℃, the mixing time is 10min, the rotating speed is 100r/min when the temperature does not reach 55 ℃, and the rotating speed is reduced to 60r/min when the temperature reaches the set temperature;
s5, conveying the mixed material to a discharging section, and extruding through a discharging opening.
Fig. 4 is an SEM image of a cross section of the modified cellulose acetate provided in this example. It can be known from comparison between fig. 4 and fig. 2 and 3 that, compared with the modified acetate fibers provided in embodiments 1 and 2, the modified acetate fiber provided in this embodiment has more micro-holes and micro-cracks inside thereof, so as to form a more regular lamellar structure, which indicates that, on the premise of keeping the addition amount of lipase unchanged, the addition amount of the glyceride formate plasticizer is increased by adding the glycerol acetate formate, and the addition amount of barium sulfate is increased, which is beneficial to simultaneously forming micro-cracks and micro-holes inside the acetate fiber, so as to prepare the modified acetate fiber with a more regular internal structure, and while improving the microbial degradability of the acetate fiber, the acetate fiber also has better mechanical properties.
Example 4
The embodiment provides a modified cellulose acetate fiber capable of being degraded by microorganisms, which comprises the following raw materials in parts by weight: 60 parts of cellulose acetate colloidal particles, 18 parts of poly (glycolide-co-lactide), 3 parts of glycerol acetate, 4 parts of hydrogenated rosin glycerol ester, 3 parts of glycerol benzoate acetate, 2 parts of tetraisopropyl titanate, 5 parts of Lipex 100L, 3 parts of barium sulfate and 2 parts of wood flour, wherein the average particle size of the wood flour is 6500 meshes.
The embodiment also provides a preparation method of the modified cellulose acetate fiber capable of being degraded by microorganisms, which specifically comprises the following steps:
s1, respectively placing cellulose acetate colloidal particles and poly (glycolide-lactide) in a vacuum drying oven, and drying for 12 hours at 50 ℃;
s2, uniformly mixing the dried cellulose acetate colloidal particles, poly (glycolide-co-lactide), glycerol acetate, hydrogenated rosin glycerol, benzoic acid glycerol acetate, tetraisopropyl titanate, lipex 100, barium sulfate and wood flour to obtain a mixed material;
s3, feeding the mixed material into a feeding section through a feeding port of an internal mixer, and feeding the mixed material by a starvation feeding method;
s4, entering a mixing section under the spiral conveying of a feeding section of the internal mixer, wherein the mixing temperature is 55 ℃, the mixing time is 10min, the rotating speed is 100r/min when the temperature does not reach 55 ℃, and the rotating speed is reduced to 60r/min when the temperature reaches the set temperature;
s5, conveying the mixed material to a discharging section, and extruding through a discharging opening.
Fig. 5 is an SEM image of a cross section of the modified cellulose acetate fiber provided in this example. As can be seen from a comparison between fig. 5 and fig. 4, compared with the modified acetate fiber provided in example 3, the modified acetate fiber provided in this embodiment has the inner micro-cavities uniformly distributed between the lamellar structures, which facilitates the microorganisms to enter between the lamellar structures inside the cellulose acetate to hydrolyze the acetate fiber.
Example 5
The embodiment provides a modified cellulose acetate fiber capable of being degraded by microorganisms, which comprises the following raw materials in parts by weight: 60 parts of cellulose acetate colloidal particles, 18 parts of poly (lactide-co-glycolide), 3 parts of glycerol acetate, 2 parts of hydrogenated rosin glycerol ester, 5 parts of benzoic acid glycerol acetate, 2 parts of tetraisopropyl titanate, 5 parts of Lipex 100L, 2 parts of barium sulfate and 4 parts of wood flour, wherein the average particle size of the wood flour is 6500 meshes.
The embodiment also provides a preparation method of the modified cellulose acetate fiber capable of being degraded by microorganisms, which specifically comprises the following steps:
s1, respectively placing cellulose acetate colloidal particles and poly (lactide-co-glycolide) in a vacuum drying oven, and drying at 50 ℃ for 12 hours;
s2, uniformly mixing the dried cellulose acetate colloidal particles, poly (glycolide-co-lactide), glycerol acetate, hydrogenated rosin glycerol, benzoic acid glycerol acetate, tetraisopropyl titanate, lipex 100L, barium sulfate and wood flour to obtain a mixed material;
s3, feeding the mixed material into a feeding section through a feeding port of an internal mixer, and feeding the mixed material by a starvation feeding method;
s4, entering a mixing section under the spiral conveying of a feeding section of an internal mixer, wherein the mixing temperature is 55 ℃, the mixing time is 10min, the rotating speed is 100r/min when the temperature does not reach 55 ℃, and the rotating speed is reduced to 60r/min when the temperature reaches the set temperature;
s5, conveying the mixed material to a discharging section, and extruding through a discharging opening.
Fig. 6 is an SEM image of a cross section of the modified cellulose acetate fiber provided in this example. As can be seen from comparison between fig. 6 and fig. 5, compared with the modified acetate fiber provided in example 4, the micro-cavities inside the modified acetate fiber provided in this embodiment are uniformly distributed between the lamellar structures, which is beneficial for microorganisms to enter between the lamellar structures inside the cellulose acetate to hydrolyze the acetate fiber, and thus the biodegradability of the modified acetate fiber can be further improved.
Example 6
The embodiment provides a modified cellulose acetate fiber capable of being degraded by microorganisms, which comprises the following raw materials in parts by weight: 60 parts of cellulose acetate colloidal particles, 20 parts of poly (lactide-co-glycolide), 3 parts of glycerol acetate, 3 parts of hydrogenated rosin glycerol, 2 parts of glycerol benzoate acetate, 2 parts of tetraisopropyl titanate, 5 parts of Lipex 100L, 2 parts of barium sulfate and 3 parts of wood flour, wherein the average particle size of the wood flour is 6500 meshes.
The embodiment also provides a preparation method of the modified cellulose acetate fiber capable of being degraded by microorganisms, which specifically comprises the following steps:
s1, respectively placing cellulose acetate colloidal particles and poly (lactide-co-glycolide) in a vacuum drying oven, and drying at 50 ℃ for 12 hours;
s2, uniformly mixing the dried cellulose acetate colloidal particles, poly (glycolide-co-lactide), glycerol acetate, hydrogenated rosin glyceride, benzoic acid glycerol acetate, tetraisopropyl titanate, lipex 100L, barium sulfate and wood flour to obtain a mixed material;
s3, feeding the mixed material into a feeding section through a feeding port of an internal mixer, and feeding the mixed material by a starvation feeding method;
s4, entering a mixing section under the spiral conveying of a feeding section of the internal mixer, wherein the mixing temperature is 55 ℃, the mixing time is 10min, the rotating speed is 100r/min when the temperature does not reach 55 ℃, and the rotating speed is reduced to 60r/min when the temperature reaches the set temperature;
s5, conveying the mixed material to a discharging section, and extruding through a discharging opening.
Fig. 7 is an SEM image of a cross section of the modified cellulose acetate fiber provided in this example. As can be seen from comparison between fig. 7 and fig. 6, compared with the modified acetate fiber provided in example 5, the micro-cavities inside the modified acetate fiber provided in this embodiment are uniformly distributed between the lamellar structures, which facilitates the microorganisms to enter between the lamellar structures inside the cellulose acetate to hydrolyze the acetate fiber.
Example 7
The difference between the embodiment and embodiment 1 is that the modified cellulose acetate fiber capable of being degraded by microorganisms comprises the following raw materials in parts by weight: 65 parts of cellulose acetate colloidal particles, 20 parts of poly-L-lactide, 2 parts of glycerol diacetate, 2 parts of glycerol triacetate, 2 parts of tetrabutyl titanate, 6 parts of Lipex 50T, 1 part of barium sulfate and 2 parts of calcium carbonate, wherein the average particle size of the calcium carbonate is 8500 meshes; in the preparation process of the modified acetate fiber, when the temperature does not reach 55 ℃, the rotating speed is 100r/min, and when the temperature reaches the set temperature, the rotating speed is reduced to 50r/min.
Example 8
The difference between the embodiment and the embodiment 1 is that the modified cellulose acetate fiber capable of being degraded by microorganisms comprises the following raw materials in parts by weight: 65 parts of cellulose acetate colloidal particles, 20 parts of polyglycolide, 2 parts of trimellitic acid triglyceride, 2 parts of phosphoglyceride, 2 parts of tetraethyl titanate, 6 parts of Lipex 50T, 1 part of barium sulfate and 2 parts of a barium sulfate salt, wherein the average particle size of the barium sulfate salt is 6500 meshes; in addition, in the preparation process of the modified acetate fiber, the mixing temperature in S2 is 50 ℃ and the mixing time is 5min, when the temperature does not reach 50 ℃, the rotating speed is 100r/min, and when the temperature reaches the set temperature, the rotating speed is reduced to 70r/min.
Example 9
The difference between the embodiment and embodiment 1 is that the modified cellulose acetate fiber capable of being degraded by microorganisms comprises the following raw materials in parts by weight: 65 parts of cellulose acetate colloidal particles, 20 parts of poly-L-lactide, 2 parts of trimellitic acid triglyceride, 2 parts of hydrogenated rosin glyceride, 2 parts of tetrabutyl titanate, 6 parts of Lipex 50T, 1 part of barium sulfate and 2 parts of calcium silicate, wherein the average particle size of the calcium silicate is 8500 meshes.
Comparative example 1
The comparative example provides a modified cellulose acetate fiber which comprises the following raw materials in parts by weight: 68 parts of cellulose acetate colloidal particles, 18 parts of poly (lactide-co-glycolide), 3 parts of glycerol acetate, 4 parts of hydrogenated rosin glycerol ester, 3 parts of benzoic acid glycerol acetate, 2 parts of tetraisopropyl titanate and 2 parts of wood flour, wherein the average particle size of the wood flour is 6500 meshes.
The comparative example also provides a preparation method of the modified acetate fiber, which comprises the following steps:
s1, respectively placing cellulose acetate colloidal particles and poly (lactide-co-glycolide) in a vacuum drying oven, and drying at 50 ℃ for 12 hours;
s2, uniformly mixing the dried cellulose acetate colloidal particles, poly (glycolide-co-lactide), acetic glyceride, hydrogenated rosin glyceride, benzoic acid acetic glyceride, tetraisopropyl titanate and wood flour to obtain a mixed material;
s3, feeding the mixed material into a feeding section through a feeding port of an internal mixer, and feeding the mixed material by a starvation feeding method;
s4, entering a mixing section under the spiral conveying of a feeding section of the internal mixer, wherein the mixing temperature is 55 ℃, the mixing time is 10min, the rotating speed is 100r/min when the temperature does not reach 55 ℃, and the rotating speed is reduced to 60r/min when the temperature reaches the set temperature;
s5, conveying the mixed material to a discharging section, and extruding through a discharging opening.
Comparative example 2
The comparative example provides a modified acetate fiber, which comprises the following raw materials in parts by weight: 65 parts of cellulose acetate colloidal particles, 18 parts of poly (lactide-co-glycolide), 3 parts of glycerol acetate, 4 parts of hydrogenated rosin glycerol ester, 3 parts of benzoic acid glycerol acetate, 2 parts of tetraisopropyl titanate, 3 parts of barium sulfate and 2 parts of wood flour, wherein the average particle size of the wood flour is 6500 meshes.
The comparative example also provides a preparation method of the modified acetate fiber, which specifically comprises the following steps:
s1, respectively placing cellulose acetate colloidal particles and poly (glycolide-lactide) in a vacuum drying oven, and drying for 12 hours at 50 ℃;
s2, uniformly mixing the dried cellulose acetate colloidal particles, poly (glycolide-co-lactide), acetic glyceride, hydrogenated rosin glyceride, benzoic acid acetic glyceride, tetraisopropyl titanate, barium sulfate and wood flour to obtain a mixed material;
s3, feeding the mixed material into a feeding section through a feeding port of an internal mixer, and feeding the mixed material by a starvation feeding method;
s4, entering a mixing section under the spiral conveying of a feeding section of an internal mixer, wherein the mixing temperature is 55 ℃, the mixing time is 10min, the rotating speed is 100r/min when the temperature does not reach 55 ℃, and the rotating speed is reduced to 60r/min when the temperature reaches the set temperature;
s5, conveying the mixed material to a discharging section, and extruding through a discharging opening.
Comparative example 3
The comparative example provides a modified acetate fiber, which comprises the following raw materials in parts by weight: 63 parts of cellulose acetate colloidal particles, 18 parts of poly (glycolide-co-lactide), 3 parts of glycerol acetate, 4 parts of hydrogenated rosin glycerol ester, 3 parts of glycerol benzoate acetate, 2 parts of tetraisopropyl titanate, 5 parts of Lipex 100L and 2 parts of wood flour, wherein the average particle size of the wood flour is 6500 meshes.
The comparative example also provides a preparation method of the modified acetate fiber, which specifically comprises the following steps:
s1, respectively placing cellulose acetate colloidal particles and poly (glycolide-lactide) in a vacuum drying oven, and drying for 12 hours at 50 ℃;
s2, uniformly mixing the dried cellulose acetate colloidal particles, poly (glycolide-co-lactide), glycerol acetate, hydrogenated rosin glycerol, benzoic acid glycerol acetate, tetraisopropyl titanate, lipex 100L and wood flour to obtain a mixed material;
s3, feeding the mixed material into a feeding section through a feeding port of an internal mixer, and feeding the mixed material by a starvation feeding method;
s4, entering a mixing section under the spiral conveying of a feeding section of the internal mixer, wherein the mixing temperature is 55 ℃, the mixing time is 10min, the rotating speed is 100r/min when the temperature does not reach 55 ℃, and the rotating speed is reduced to 60r/min when the temperature reaches the set temperature;
s5, conveying the mixed material to a discharging section, and extruding through a discharging opening.
Examples of the experiments
1. Mechanical property experiment of modified acetate fiber
After drying the cellulose acetate crumb and the modified acetate fibers provided in examples 1 to 6, a 0.5mm thick sheet sample and a 40mm by 5mm by 1mm rectangular sample bar were obtained by injection molding at 100 ℃ under 100 MPa.
The tensile property of the sample is tested by referring to the national standard GB/T1040-1992 plastic tensile property test method, the gauge length of the sample strip is 25mm, and the selected tensile speed is 50mm/min. The results of the mechanical property tests of cellulose acetate crumb and the modified acetate fibers provided in examples 1-6 are shown in table 1:
TABLE 1 mechanical Properties of modified acetate fibers
As can be seen from Table 1, the modified acetate fibers prepared in examples 1 to 6 have good biodegradability and good mechanical properties.
2. Biodegradation Performance test of modified cellulose acetate fibers
The modified cellulose acetate fibers provided by the cellulose acetate colloidal particles, example 4 and comparative examples 1-3 are subjected to biodegradation performance tests according to the ASTM D5338-92 standard method, which specifically comprises the following steps:
s1, composting: using a mixture of 1:1 horse manure and municipal domestic waste as a compost inoculum, performing fermentation treatment, and screening by using a 5mm mesh sieve to remove large-block-shaped various impurities and small organisms;
s2, sample treatment: the compost, cellulose acetate colloidal particles, the modified acetate fibers provided by example 4 and comparative examples 1-3 are dried, then 100g of the modified acetate fibers provided by example 4 and comparative examples 1-3 and 600g of the compost are respectively and fully mixed and placed in reagent bottles, and simultaneously 100mL of water is added into each bottle, and the mixture is stirred uniformly, so that the mixture is fully wetted but does not agglomerate. Three replicates were set for each sample, and analytically pure starch was used for the positive control samples. The negative control adopts a blank sample (namely only compost inoculum is loaded);
s3, biodegradation experiment: (1) Covering a rubber plug with an air pipe after sample loading, connecting an air inlet pump and an air flow meter, placing a temperature-controllable water bath after checking that each part is airtight, conveying humidified air to a compost container, keeping the flow at 50mL/min, keeping the relative humidity in the container at about 90%, and changing the temperature in the container according to a standard method in the whole test period, wherein the temperature is changed according to the standard method for 0-1 day 35 ℃,2-5 days 58 ℃,6-34 days 50 ℃ and 35-57 days 35 ℃;
(2) Measuring CO evolution once a day 2 Amount, calculated as the percent biodegradation of the modified acetate fibers provided in example 4 and comparative examples 1-3, resulting in cellulose acetate crumb, the results are shown in table 2:
TABLE 2 percent biodegradation of modified acetate fibers
As can be seen from table 2, the modified cellulose acetate provided in example 4 has significantly improved biodegradability compared to the existing cellulose acetate colloidal particles; compared with the comparative example 3, the addition of the high specific gravity inorganic compound barium sulfate can obviously improve the biodegradability of the acetate fiber; example 4 compared with comparative example 2, it is clear that the addition of lipase can improve the biodegradability of acetate fiber; meanwhile, as can be seen from example 4 in comparison with comparative examples 1 to 3, both barium sulfate and lipase act synergistically: compared with the method that barium sulfate or lipase is independently added into the acetate fibers to modify the acetate fibers, the effect of improving the biodegradability of the acetate fibers is more obvious when the barium sulfate or the lipase is simultaneously added into the acetate fibers, and a better modification effect is realized, so that the modified acetate fibers with excellent biodegradability are prepared.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the foregoing embodiments may be combined in any suitable manner without contradiction. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. The modified cellulose acetate fiber capable of being degraded by microorganisms is characterized by comprising the following raw materials in parts by weight: 50-75 parts of cellulose acetate, 15-25 parts of biodegradable polyester, 2-15 parts of glyceride plasticizer, 1-5 parts of compatilizer, 4-10 parts of lipase, 1-5 parts of high-specific-gravity inorganic substance and 1-5 parts of filler.
2. The modified cellulose acetate fiber capable of being degraded by microorganisms according to claim 1, wherein the modified cellulose acetate fiber comprises, by weight, 55-70 parts of cellulose acetate, 18-20 parts of biodegradable polyester, 4-12 parts of glyceride plasticizer, 1-2 parts of compatilizer, 4-6 parts of lipase, 1-3 parts of high specific gravity inorganic substance and 2-4 parts of filler.
3. The modified cellulose acetate fiber according to claim 1, wherein the high specific gravity inorganic compound is barium sulfate.
4. The modified cellulose acetate that is biodegradable according to claim 1, wherein the lipase is Lipex 100L or Lipex 50T.
5. The microbially degradable modified acetate fiber according to claim 1, wherein said cellulose acetate is a cellulose acetate micelle;
optionally, the biodegradable polyester is one of poly-L-lactide, polyglycolide or poly-glycolide-lactide.
6. The microbially degradable modified acetic acid fiber according to claim 1, wherein the glycerin-based plasticizer is selected from two or more of glycerol acetate, glycerol diacetate, glycerol triacetate, glycerol phosphate, glycerol benzoate acetate, glycerol trimellitate and glycerol hydrogenated rosin;
optionally, the compatibilizer is one of tetraisopropyl titanate, tetrabutyl titanate, or tetraethyl titanate;
optionally, the filler is one or more of wood flour, carbonate, sulfate, silicate, and cinnamate, and the filler has an average particle size of 6500 to 8500 mesh.
7. The method for preparing the modified cellulose acetate fiber which is biodegradable by microorganism according to any one of claims 1 to 6, characterized by comprising the steps of:
s1, uniformly stirring and mixing the cellulose acetate, the biodegradable polyester, the glyceride plasticizer, the compatilizer, the lipase, the high-specific-gravity inorganic matter and the filler to prepare a mixed material;
s2, adding the mixed material into an internal mixer for mixing by a starvation feeding method, so that the mixed material is subjected to multiple actions of two sections of opposite-rotation-direction screw ridges of a rotor and the wall of a mixing chamber;
and S3, extruding the mixed material after mixing, and cooling and forming.
8. The method for preparing a modified cellulose acetate fiber that is biodegradable by microorganisms according to claim 7, wherein in S1, the cellulose acetate and the biodegradable resin are dried under vacuum at 45 to 55 ℃ for 11 to 13 hours.
9. The method for preparing the modified cellulose acetate fiber capable of being degraded by microorganisms according to claim 7, wherein in S2, the mixing temperature is 50-55 ℃, the rotation speed is 50-70r/min, and the time is 5-10min.
10. A degradable plastic product, wherein the degradable plastic product is made from the modified cellulose acetate fiber that is biodegradable by microorganism according to any one of claims 1 to 6 and/or the modified cellulose acetate fiber that is obtained by the method for producing the modified cellulose acetate fiber that is biodegradable by microorganism according to any one of claims 7 to 9.
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Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1154119A (en) * | 1995-03-31 | 1997-07-09 | 大赛璐化学工业株式会社 | Cellulose acetate having excellent physical strength and process for preparing the same |
| WO2000029460A1 (en) * | 1998-11-13 | 2000-05-25 | Daicel Chemical Industries, Ltd. | Aliphatic copolymer, production process, aliphatic polyester resin composition, various uses, coating composition, and agricultural or horticultural particulate composition comprising degradable coating film |
| CN1354777A (en) * | 1999-06-07 | 2002-06-19 | 伊斯曼化学公司 | Agricultural mulch films with triggered degradation |
| CN102505030A (en) * | 2011-10-12 | 2012-06-20 | 江南大学 | Method for improving photocatalysis and biodegradation performances of cellulose acetate |
| CN102585297A (en) * | 2012-01-18 | 2012-07-18 | 姚岚 | Biodegradable cellulose acetate plastic and preparation method thereof |
| CN104195589A (en) * | 2014-08-21 | 2014-12-10 | 成都新柯力化工科技有限公司 | Preparation method and application of nano barium sulphate |
| CN106220894A (en) * | 2016-03-17 | 2016-12-14 | 仇颖莹 | A kind of method utilizing modified ramie to prepare high-temperature resistant friction material |
| CN106336575A (en) * | 2016-09-22 | 2017-01-18 | 苏州佰思科节能环保科技有限公司 | Easily degradable polypropylene environment-friendly material and preparation method thereof |
| CN106398107A (en) * | 2016-08-29 | 2017-02-15 | 芜湖众力部件有限公司 | High-wear resistance degradable modified plastic and making method thereof |
| CN107709457A (en) * | 2015-06-12 | 2018-02-16 | 卡比奥斯公司 | biodegradable polyester composition and application thereof |
| US20200199354A1 (en) * | 2017-08-31 | 2020-06-25 | Carbiolice | Biodegradable polyester article comprising enzymes |
| WO2020205415A1 (en) * | 2019-03-29 | 2020-10-08 | Eastman Chemical Company | Polymers, articles, and chemicals made from high concentrated recycle derived syngas |
| CN112795179A (en) * | 2019-11-13 | 2021-05-14 | 杭州如墨科技有限公司 | Preparation method of thermoplastic high-specific-gravity composite material |
| US20210244088A1 (en) * | 2020-02-10 | 2021-08-12 | Acetate International, Llc | Degradable cellulose ester |
| CN114364731A (en) * | 2019-09-03 | 2022-04-15 | Rj索尔特有限责任公司 | Biodegradable products and method of production |
| CN114450311A (en) * | 2019-09-27 | 2022-05-06 | 伊士曼化工公司 | Cellulose ester compositions derived from synthesis gas from the recovery of cellulose ester components |
-
2022
- 2022-07-13 CN CN202210818126.4A patent/CN115160654A/en active Pending
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1154119A (en) * | 1995-03-31 | 1997-07-09 | 大赛璐化学工业株式会社 | Cellulose acetate having excellent physical strength and process for preparing the same |
| WO2000029460A1 (en) * | 1998-11-13 | 2000-05-25 | Daicel Chemical Industries, Ltd. | Aliphatic copolymer, production process, aliphatic polyester resin composition, various uses, coating composition, and agricultural or horticultural particulate composition comprising degradable coating film |
| CN1354777A (en) * | 1999-06-07 | 2002-06-19 | 伊斯曼化学公司 | Agricultural mulch films with triggered degradation |
| CN102505030A (en) * | 2011-10-12 | 2012-06-20 | 江南大学 | Method for improving photocatalysis and biodegradation performances of cellulose acetate |
| CN102585297A (en) * | 2012-01-18 | 2012-07-18 | 姚岚 | Biodegradable cellulose acetate plastic and preparation method thereof |
| CN104195589A (en) * | 2014-08-21 | 2014-12-10 | 成都新柯力化工科技有限公司 | Preparation method and application of nano barium sulphate |
| CN107709457A (en) * | 2015-06-12 | 2018-02-16 | 卡比奥斯公司 | biodegradable polyester composition and application thereof |
| US20180142097A1 (en) * | 2015-06-12 | 2018-05-24 | Carbios | Biodegradable polyester composition and uses thereof |
| CN106220894A (en) * | 2016-03-17 | 2016-12-14 | 仇颖莹 | A kind of method utilizing modified ramie to prepare high-temperature resistant friction material |
| CN106398107A (en) * | 2016-08-29 | 2017-02-15 | 芜湖众力部件有限公司 | High-wear resistance degradable modified plastic and making method thereof |
| CN106336575A (en) * | 2016-09-22 | 2017-01-18 | 苏州佰思科节能环保科技有限公司 | Easily degradable polypropylene environment-friendly material and preparation method thereof |
| US20200199354A1 (en) * | 2017-08-31 | 2020-06-25 | Carbiolice | Biodegradable polyester article comprising enzymes |
| WO2020205415A1 (en) * | 2019-03-29 | 2020-10-08 | Eastman Chemical Company | Polymers, articles, and chemicals made from high concentrated recycle derived syngas |
| CN114364731A (en) * | 2019-09-03 | 2022-04-15 | Rj索尔特有限责任公司 | Biodegradable products and method of production |
| CN114450311A (en) * | 2019-09-27 | 2022-05-06 | 伊士曼化工公司 | Cellulose ester compositions derived from synthesis gas from the recovery of cellulose ester components |
| CN112795179A (en) * | 2019-11-13 | 2021-05-14 | 杭州如墨科技有限公司 | Preparation method of thermoplastic high-specific-gravity composite material |
| US20210244088A1 (en) * | 2020-02-10 | 2021-08-12 | Acetate International, Llc | Degradable cellulose ester |
Non-Patent Citations (1)
| Title |
|---|
| M.R. CALIL ETAL.: ""Enzymatic degradation of poly (e-caprolactone) and celluloseacetate blends by lipase and a-amylase"" * |
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