CN118440481A - Preparation process of cellulose toughened modified polylactic acid composite material - Google Patents
Preparation process of cellulose toughened modified polylactic acid composite material Download PDFInfo
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- CN118440481A CN118440481A CN202410896097.2A CN202410896097A CN118440481A CN 118440481 A CN118440481 A CN 118440481A CN 202410896097 A CN202410896097 A CN 202410896097A CN 118440481 A CN118440481 A CN 118440481A
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- China
- Prior art keywords
- polylactic acid
- cellulose
- composite material
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- polycaprolactone
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 83
- 239000001913 cellulose Substances 0.000 title claims abstract description 83
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 68
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920000742 Cotton Polymers 0.000 claims abstract description 35
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 28
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 28
- 239000002667 nucleating agent Substances 0.000 claims abstract description 26
- 238000005507 spraying Methods 0.000 claims abstract description 22
- 239000004014 plasticizer Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000000314 lubricant Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000000543 intermediate Substances 0.000 claims description 13
- UYXTWWCETRIEDR-UHFFFAOYSA-N Tributyrin Chemical compound CCCC(=O)OCC(OC(=O)CCC)COC(=O)CCC UYXTWWCETRIEDR-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- VLPFTAMPNXLGLX-UHFFFAOYSA-N trioctanoin Chemical compound CCCCCCCC(=O)OCC(OC(=O)CCCCCCC)COC(=O)CCCCCCC VLPFTAMPNXLGLX-UHFFFAOYSA-N 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 6
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 229940093609 tricaprylin Drugs 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 235000019359 magnesium stearate Nutrition 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 239000012620 biological material Substances 0.000 description 9
- 238000002791 soaking Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- 229920006238 degradable plastic Polymers 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000010902 straw Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 238000006957 Michael reaction Methods 0.000 description 1
- 206010038731 Respiratory tract irritation Diseases 0.000 description 1
- 244000138286 Sorghum saccharatum Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 229920003064 carboxyethyl cellulose Polymers 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- -1 hydroxyl ions Chemical class 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 229940097139 perfect choice Drugs 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000008104 plant cellulose Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/02—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin
- D06M14/04—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin of vegetal origin, e.g. cellulose or derivatives thereof
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation process of a cellulose toughening modified polylactic acid composite material, which belongs to the technical field of high polymer materials and comprises the steps of pretreatment, hydrolysis, grafting and the like of cotton fibers to obtain modified cellulose; and then spraying the modified cellulose-doped polylactic acid, polycaprolactone, a plasticizer, a nucleating agent and a lubricant on the surfaces of polylactic acid and polycaprolactone by a spraying method, and finally uniformly mixing the modified cellulose-doped polylactic acid, the polycaprolactone, the plasticizer, the nucleating agent and the lubricant, then putting the mixture into an internal mixer for blending, and drying the obtained blend at room temperature by a vacuum oven, so that the compatibility of cellulose and polymers is greatly improved, and the probability of cellulose agglomeration is reduced, and the polylactic acid composite material with high toughness and high heat resistance is prepared.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a preparation process of a cellulose toughening modified polylactic acid composite material.
Background
Polylactic acid is derived from renewable non-grain crops (such as cassava, sweet sorghum, plant cellulose and the like), is derived from nature, can be completely degraded by microorganisms in nature after being used, finally generates carbon dioxide and water, does not pollute the environment, and is very beneficial to protecting the natural environment. Polylactic acid has good solvent resistance, no toxicity and no irritation, good biocompatibility, biodegradability and high strength, can be used for being decomposed and absorbed by organisms, is dampproof, oil-grease-resistant and has good air permeability, certain bacteria resistance, flame retardance and ultraviolet resistance, good plasticity and easy processing and forming, is suitable for being processed by various methods such as extrusion, molding, casting forming, melt spinning, solution spinning, blow molding and the like, and is a perfect choice for simultaneously solving the problems of resources and environment as the demands of people on plastics are more and more increased. Although polylactic acid has many advantages, the current polylactic acid resin commodity still has the disadvantages of brittleness, poor toughness, insufficient heat resistance and the like.
Cellulose is a polysaccharide polymer compound widely existing in the nature, has the advantages of being renewable, degradable, nontoxic, environment-friendly, easy to modify, low in cost and the like, and has great potential application value due to the characteristics. In theory, cellulose is taken as natural long fibers, and can be dispersed in a polymer matrix by doping, so that the internal friction of the matrix is increased, and the mechanical property, particularly the tensile property, of the material is improved, and the application value of the material is improved. But untreated cellulose has extremely large molecular weight, multiple surface hydroxyl groups and extremely stable structure, and often cannot be compatible with a polymer matrix, so that the untreated cellulose damages the internal regular structure of the polymer, and the overall mechanical property is reduced. Therefore, in order to disperse cellulose well in a matrix, it is necessary to surface-modify it. For example, CN107011640B discloses a cellulose toughened modified polylactic acid composite material and a preparation method thereof, the modified polylactic acid composite material is prepared from polylactic acid and modified cellulose, wherein the modified cellulose is at least one of methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, carboxyethyl cellulose or carboxymethyl cellulose modified by diphenylmethane diisocyanate, but MDI has certain toxicity, and long-term or high-concentration exposure can cause problems of respiratory tract irritation, skin allergy and the like, and the modified cellulose is not suitable for being used in food packaging and degradable plastic straws, and the problem of heat resistance of the polylactic acid is not solved.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a preparation process of a cellulose toughening modified polylactic acid composite material, which is characterized in that cotton fibers are modified and then respectively blended with polylactic acid and polycaprolactone for modification, so that the compatibility of cellulose and polymers is greatly improved, the probability of cellulose agglomeration is reduced, and the polylactic acid composite material with high toughness and high heat resistance is prepared.
The invention is realized by the following technical scheme: a preparation process of a cellulose toughening modified polylactic acid composite material comprises the following steps:
S1, 10-20 parts by mass of cotton fibers are taken, dried in an oven at 100-120 ℃ for 6-12 hours to remove free water, soaked in 10-25% NaOH aqueous solution by mass fraction, continuously soaked for 6-12 hours after ultrasonic treatment for 30-60 minutes and filtered, and then 50-60% NaOH aqueous solution by mass fraction is added again and heated to 150-160 ℃ and stirred continuously until the dissolution rate of the cotton fibers is more than or equal to 80%, and undissolved parts are filtered to obtain cellulose carbanion intermediates;
s2, slowly adding an acetone solution of triallyl isocyanurate into a cellulose carbanion intermediate filtrate, stirring for a long time at 50-60 ℃, dropwise adding 1mol/L acetic acid into the system after reacting for 5-10 hours, maintaining the pH value to be 9-10, continuing the reaction for 5-10 hours to obtain modified cellulose sediment, centrifugally washing, and re-dispersing the modified cellulose sediment in 10-20 parts of water to obtain modified cellulose dispersion;
S3, spraying 60-70% of the obtained modified cellulose dispersion liquid on the surface of 80-100 parts of polylactic acid in a spraying method, solidifying for 20-30min at the temperature of 110-120 ℃, spraying the rest modified cellulose on the surface of 20-50 parts of polycaprolactone in the same method, solidifying for 20-30min at the temperature of 110-120 ℃, mixing uniformly polylactic acid doped with the modified cellulose, polycaprolactone, 5-10 parts of plasticizer, 2-5 parts of nucleating agent and 1-3 parts of lubricant, then putting into an internal mixer, blending for 2-10 min at the temperature of 155-170 ℃ and the rotating speed of 60-90 r/min, and drying the obtained blend in a vacuum oven at room temperature.
The blend can be formed by injection molding, blow molding, extrusion and other processing techniques after being crushed by a crusher.
According to the invention, the cotton fiber is firstly subjected to the pretreatment of drying and then is soaked in alkali liquor with lower mass concentration for the first time and is subjected to ultrasonic treatment, so that colloid and impurities on the surface of the cotton fiber can be removed, the cotton fiber is swelled, the wetting performance of the cotton fiber is improved, and the subsequent reaction of the cotton fiber is facilitated. And (3) carrying out high-temperature treatment by using alkali liquor with higher mass concentration for the second time, hydrolyzing cellulose of cotton fibers, generating cellulose carbanion intermediate, dissolving the cellulose carbanion intermediate in a solvent, carrying out reversible addition reaction, namely Michael reaction, on the cellulose carbanion intermediate and triallyl isocyanurate, and increasing the grafting rate of the triallyl isocyanurate by continuously and slightly dropwise adding hydroxyl ions generated by consuming acetic acid.
Preferably, the polylactic acid is L-polylactic acid, and the intrinsic viscosity of the L-polylactic acid ranges from 2 dL/g to 4dL/g.
Preferably, the polycaprolactone has an intrinsic viscosity ranging from 0.75 to 2.25 dL/g.
The test of the intrinsic viscosity is available according to the standard GB/T10247-2008 test.
Preferably, the cotton fiber is natural cotton or absorbent cotton.
Preferably, the polylactic acid and polycaprolactone in the step S3 are dried for 2-5 hours at 100-120 ℃ before being treated by a spraying method.
Preferably, in the step S1, the dosage of 10% -25% of NaOH aqueous solution is added until the cotton fibers are completely submerged, and the dosage of 50% -60% of NaOH aqueous solution is 1.5-2 times of the volume of the cotton fibers.
Preferably, the acetone solution of the triallyl isocyanurate in the step S1 is prepared by dissolving 3-5 parts by mass of triallyl isocyanurate in 10-20 parts by mass of acetone.
Preferably, the plasticizer is selected from one or more of tributyrin, tricaprylin, and tricaprylin.
Preferably, the lubricant is selected from one or more of calcium stearate and magnesium stearate.
Preferably, the nucleating agent is at least one selected from hydrazide nucleating agents and tetrapod-like zinc oxide whiskers; the hydrazide nucleating agent is selected from TMC-306 and TMC-300.
More preferably, the nucleating agent is selected from two kinds of hydrazide nucleating agents and tetrapod-like zinc oxide whiskers, and the mass ratio of the hydrazide nucleating agent to the tetrapod-like zinc oxide whiskers is 1: (1-3).
Compared with the prior art, the invention has the beneficial effects that:
The invention provides a preparation process of a cellulose toughening modified polylactic acid composite material, which is characterized in that cotton fibers are subjected to pretreatment and grafting modification and then are blended with polylactic acid and polycaprolactone in a spraying manner, so that the compatibility of cellulose with polylactic acid and polycaprolactone is greatly improved, and the probability of cellulose agglomeration is reduced. In addition, the polylactic acid composite material is also added with components and additives such as polycaprolactone, nucleating agent, plasticizer and the like which are also doped with modified cellulose, so that the elongation at break and the heat deformation temperature of the polylactic acid composite material can be effectively improved, and the polylactic acid composite material with high toughness and high heat resistance is prepared, and is particularly suitable for the fields of manufacturing food packages, degradable plastic straws and the like.
Drawings
FIG. 1 is a schematic diagram of the mechanism of hydrolytic grafting of cellulose;
FIG. 2 is an infrared spectrum of cellulose, triallyl isocyanurate, modified cellulose.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used, unless otherwise specified, are commercially available.
The following description will be made of the raw materials used in examples and comparative examples:
Polylactic acid 1, namely, L-polylactic acid with the intrinsic viscosity of 2.5dL/g and model PLLA-25, which is purchased from Boli biological materials in Shenzhen city;
polylactic acid 2, namely, L-polylactic acid with the intrinsic viscosity of 4dL/g and model PLLA-40, which is purchased from the Boli biological material in Shenzhen market;
Polylactic acid 3, namely, L-polylactic acid with the intrinsic viscosity of 1.5dL/g and model PLLA-15, which is purchased from the Boli biological material in Shenzhen city;
Polylactic acid 4, namely L-polylactic acid with the intrinsic viscosity of 5dL/g and model PLLA-50, which is purchased from the Boli biological material in Shenzhen market;
The polylactic acid 5 is racemized polylactic acid with the intrinsic viscosity of 2.5dL/g and the model PDLLA-25, and is purchased from Boli biological materials in Shenzhen city;
Polycaprolactone 1 with an intrinsic viscosity of 1dL/g and model PCL-10, which is purchased from Shenzhen Boli biological material;
polycaprolactone 2 with an intrinsic viscosity of 2dL/g and model PCL-20, which is purchased from Shenzhen Boli biological material;
polycaprolactone 3 with an intrinsic viscosity of 0.5dL/g and model PCL-05, which is purchased from Boli biological materials in Shenzhen city;
polycaprolactone 4 with an intrinsic viscosity of 3.5dL/g and model PCL-35, which is purchased from Boli biological materials in Shenzhen city;
cotton fiber: fine cotton wool, hunan of the producing area;
triallyl isocyanurate: 99%, senfeida;
diphenylmethane diisocyanate: 98%, sigma-Aldrich;
Plasticizer 1: tributyrin, 99%, sigma-Aldrich;
plasticizer 2: glyceryl tricaprylate, 99%, sigma-Aldrich;
Plasticizer 3: dioctyl phthalate, shandong Jian Xin Fang;
nucleating agent 1: four needle zinc oxide whisker, 98%, wuhan Kemicin;
nucleating agent 2: hydrazide nucleating agent, TMC-306, shanxi province chemical institute;
and (3) a lubricant: magnesium stearate, commercially available;
the raw materials of the components used in each of the examples and comparative examples of the present invention were all commercially available raw materials unless otherwise specified, and the raw materials of the components used in each of the parallel experiments were all the same.
Example 1
The preparation process of the cellulose toughening modified polylactic acid composite material comprises the following steps in parts by weight:
S1, 10 parts by mass of cotton fibers are taken and dried in a baking oven at 120 ℃ for 8 hours to remove free water, then 10% by mass of NaOH aqueous solution is used for soaking until the cotton fibers are completely submerged, ultrasonic treatment is carried out for 60 minutes, then soaking is continued for 6 hours, filtration is carried out, 55% by mass of NaOH aqueous solution with the mass fraction of 10% being twice the volume of the NaOH aqueous solution is added again, heating is carried out to 155 ℃ and stirring is carried out continuously until the dissolution rate of the cotton fibers is more than or equal to 80%, and undissolved parts are filtered, thus obtaining cellulose carbanion intermediates;
S2, slowly adding an acetone solution of triallyl isocyanurate into a cellulose carbanion intermediate filtrate, stirring for a long time at 55 ℃, dropwise adding 1mol/L acetic acid into the system after reacting for 10 hours, maintaining the pH value to be 9-10, continuing the reaction for 5 hours to obtain a modified cellulose precipitate, centrifugally washing, and re-dispersing the modified cellulose precipitate in 10-20 parts of water to obtain a modified cellulose dispersion; in order to improve the grafting rate, adding triallyl isocyanurate to be excessive, wherein an acetone solution of the triallyl isocyanurate is prepared by dissolving 5 parts by mass of triallyl isocyanurate in 20 parts by mass of acetone, wherein a mechanism diagram of cellulose carbanion intermediate generated by hydrolysis of cellulose by NaOH and nucleophilic addition reaction with the triallyl isocyanurate is shown in the figure 1; FIG. 2 shows the IR spectra of cellulose, triallyl isocyanurate and modified cellulose, wherein, after cotton fiber is hydrolyzed by NaOH and grafted by triallyl isocyanurate, the characteristic peak of carbonyl appears at 1732cm < -1 > position, which proves the successful grafting modification.
S3, spraying 70% of the obtained modified cellulose dispersion liquid on 80 parts by mass of polylactic acid 1 surface in a spraying manner, then solidifying for 30min at 120 ℃, spraying the rest modified cellulose on 50 parts by mass of polycaprolactone 1 surface in the same manner, solidifying for 30min at 120 ℃, finally uniformly mixing polylactic acid 1 doped with modified cellulose, polycaprolactone 1, 10 parts by mass of plasticizer 1, 2.5 parts by mass of nucleating agent 2 and 3 parts by mass of lubricant, then putting into a Hak internal mixer, blending for 10min at 166 ℃ and a rotating speed of 80r/min, drying the obtained blend in a vacuum oven at room temperature, crushing the blend by a crusher, and performing injection molding processing to obtain the cellulose toughening modified polylactic acid composite material.
Example 2
S1, taking 20 parts by mass of cotton fibers, drying in a 100 ℃ oven for 8 hours to remove free water, soaking in 25% NaOH aqueous solution by mass fraction, carrying out ultrasonic treatment for 30 minutes, continuously soaking for 12 hours, filtering, adding 55% NaOH aqueous solution by mass fraction again, heating to 155 ℃ and continuously stirring until the dissolution rate of the cotton fibers is more than or equal to 80%, and filtering undissolved parts to obtain cellulose carbanion intermediates;
S2, slowly adding an acetone solution of triallyl isocyanurate into a cellulose carbanion intermediate filtrate, stirring for a long time at 55 ℃, dropwise adding 1mol/L acetic acid into the system after reacting for 5 hours, maintaining the pH value to be 9-10, continuing the reaction for 8 hours to obtain a modified cellulose precipitate, centrifugally washing, and re-dispersing the modified cellulose precipitate in 10-20 parts of water to obtain a modified cellulose dispersion; the acetone solution of triallyl isocyanurate is prepared by dissolving 3 parts by mass of triallyl isocyanurate in 10 parts by mass of acetone;
S3, spraying 70% of the obtained modified cellulose dispersion liquid on 100 parts by mass of polylactic acid 1 surface in a spraying manner, then solidifying for 30min at 120 ℃, spraying the rest modified cellulose on 30 parts by mass of polycaprolactone 1 surface in the same manner, solidifying for 30min at 120 ℃, drying polylactic acid and polycaprolactone for 4 hours at 100 ℃ before spraying treatment, finally uniformly mixing 1 part by mass of plasticizer 1, 1 part by mass of nucleating agent 2 and 1 part by mass of lubricant, putting into a Hark internal mixer, blending for 10min at 166 ℃ at the rotating speed of 80r/min, drying the obtained blend at room temperature by a vacuum oven, crushing the blend by a crusher, and performing injection molding to obtain the cellulose toughening modified polylactic acid composite material.
Examples 3 to 18
The preparation method is the same as in example 2, except that the components used or the parts by mass of the added components are different, and the specific components and the formulation of the parts by mass are shown in table 1.
TABLE 1 Components and parts by weight of examples 1-18
Table 1, below
Comparative example 1
Compared with the embodiment 2, the difference is that 20 parts of cotton fiber is taken in the step S1, and is directly added with 55 percent NaOH aqueous solution with mass fraction to heat to 155 ℃ without pretreatment, and the mixture is continuously stirred until the dissolution rate of the cotton fiber is more than or equal to 80 percent, and undissolved parts are filtered to obtain cellulose carbanion intermediate; the remaining steps are the same.
Comparative example 2
S1, taking 20 parts of cotton fibers, drying in a 100 ℃ oven for 8 hours to remove free water, soaking in 25% NaOH aqueous solution by mass fraction, carrying out ultrasonic treatment for 30 minutes, continuously soaking for 12 hours, filtering, adding 55% NaOH aqueous solution by mass fraction again, heating to 155 ℃ and continuously stirring until the dissolution rate of the cotton fibers is more than or equal to 80%, and filtering undissolved parts to obtain cellulose carbanions;
S2, spraying 70% of the obtained cellulose carbanion on the surface of 100 parts of polylactic acid 1 in a spraying manner, curing for 30min at 120 ℃, spraying the rest of the cellulose carbanion on the surface of 30 parts of polycaprolactone 1 in the spraying manner, curing for 30min at 120 ℃, mixing uniformly polylactic acid 1 doped with modified cellulose, polycaprolactone 1, 5 parts of plasticizer 1,1 part of nucleating agent 2 and 1 part of lubricant, putting into a Hak internal mixer, blending for 5min at 166 ℃ and the rotating speed of 80r/min, and drying the obtained blend in a vacuum oven at room temperature to obtain the cellulose toughening modified polylactic acid composite material.
Comparative example 3
The difference compared to example 2 is that triallyl isocyanurate in step S2 is replaced by diphenylmethane diisocyanate.
Comparative example 4
In comparison with example 2, the difference is that the modified cellulose obtained in the step S3 is sprayed on the surface of 100 parts of polylactic acid 1 in the form of a spray method and then cured at 120℃for 30 minutes.
Comparative example 5
In comparison with example 2, the difference is that the modified cellulose obtained in the step S3 is sprayed on 100 parts of the polylactic acid 1 surface in the form of a spray method and then cured for 30 minutes at 120℃without polycaprolactone.
Comparative example 6
In comparison with example 2, the difference is that no plasticizer is added.
Comparative example 7
In comparison to example 2, the difference is that no nucleating agent is added.
Comparative example 8
Compared with the example 2, the modified cellulose in the step S3 is obtained by directly and uniformly mixing the modified cellulose with the polylactic acid 1, the polycaprolactone 1, the plasticizer 1, the nucleating agent and the lubricant.
The polylactic acid composite materials prepared in examples 1 to 18 and comparative examples 1 to 8 were subjected to the following performance test, and the results are shown in Table 2, respectively.
1. Tensile strength: the products of the examples and comparative examples were tested according to ISO 527-2, a stretch rate of 50mm/min;
2. elongation at break: the products of the examples and comparative examples were tested according to ISO 527-2, a stretch rate of 50mm/min;
3. Heat distortion temperature: the products of the examples and comparative examples were tested based on ASTM D648 under conditions of 0.45MPa,6.4mm on side;
Table 2 performance testing of examples and comparative examples
From the examples and comparative examples, the cellulose toughened and modified polylactic acid composite material prepared by the preparation process provided by the invention has the tensile strength of more than or equal to 100MPa, the elongation at break of more than or equal to 102%, the heat distortion temperature of more than or equal to 85 ℃, and meets the use requirements of food packaging and degradable plastic straws.
From examples 2-5 and 8-9, it can be seen that when the intrinsic viscosity of polylactic acid and polycaprolactone is within a certain range, the mechanical property and heat resistance of the prepared polylactic acid composite material are better, when the intrinsic viscosity range is too small, the mechanical strength of the composite material is insufficient, and when the intrinsic viscosity range is too large, the dispersibility of modified cellulose and other auxiliary agents is poor, and the overall performance of the material is poor.
It can be seen from examples 2, 10 and 11 that when the plasticizer is selected from tributyrin and tricaprylin, the mechanical properties and heat resistance of the polylactic acid composite material are better, and meanwhile, tributyrin and tricaprylin belong to biomass materials, are more green and safer than conventional plasticizers such as DOP, and meet the use requirements of food packaging and degradable plastic straws.
From examples 12-16, it can be seen that the organic nucleating agent has better effects on the mechanical properties and heat resistance of polylactic acid when the organic nucleating agent is selected from the combination of hydrazides and tetrapod-shaped zinc oxide whiskers.
Examples 2, 17 and 18 show that when the triallyl isocyanurate content is low, the mechanical properties and heat resistance are improved well by increasing the triallyl isocyanurate content, but when the triallyl isocyanurate content is increased to a certain extent, the grafting rate of cellulose is difficult to be improved more obviously, and the mechanical properties and heat resistance tend to be stable.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (10)
1. The preparation process of the cellulose toughening modified polylactic acid composite material is characterized by comprising the following steps of:
S1, 10-20 parts by mass of cotton fibers are taken, dried in an oven at 100-120 ℃ for 6-12 hours to remove free water, soaked in 10-25% NaOH aqueous solution by mass fraction, continuously soaked for 6-12 hours after ultrasonic treatment for 30-60 minutes and filtered, and then 50-60% NaOH aqueous solution by mass fraction is added again and heated to 150-160 ℃ and stirred continuously until the dissolution rate of the cotton fibers is more than or equal to 80%, and undissolved parts are filtered to obtain cellulose carbanion intermediates;
s2, slowly adding an acetone solution of triallyl isocyanurate into a cellulose carbanion intermediate filtrate, stirring for a long time at 50-60 ℃, dropwise adding 1mol/L acetic acid into the system after reacting for 5-10 hours, maintaining the pH value to be 9-10, continuing the reaction for 5-10 hours to obtain modified cellulose sediment, centrifugally washing, and re-dispersing the modified cellulose sediment in 10-20 parts of water to obtain modified cellulose dispersion;
S3, spraying 60-70% of the obtained modified cellulose dispersion liquid on the surface of 80-100 parts of polylactic acid in a spraying method, solidifying for 20-30min at the temperature of 110-120 ℃, spraying the rest modified cellulose on the surface of 20-50 parts of polycaprolactone in the same method, solidifying for 20-30min at the temperature of 110-120 ℃, mixing uniformly polylactic acid doped with the modified cellulose, polycaprolactone, 5-10 parts of plasticizer, 2-5 parts of nucleating agent and 1-3 parts of lubricant, then putting into an internal mixer, blending for 2-10 min at the temperature of 155-170 ℃ and the rotating speed of 60-90 r/min, and drying the obtained blend in a vacuum oven at room temperature.
2. The process for preparing a composite material according to claim 1, wherein the polylactic acid is a levorotatory polylactic acid, and the intrinsic viscosity of the levorotatory polylactic acid ranges from 2 dl/g to 4dl/g.
3. The process for preparing a composite material according to claim 1, wherein the polycaprolactone has an intrinsic viscosity in the range of 0.75 to 2.25 dL/g.
4. The process for preparing a composite material according to claim 1, wherein the cotton fiber is natural cotton or absorbent cotton.
5. The process for preparing a composite material according to claim 1, wherein the polylactic acid and polycaprolactone are dried at 100-120 ℃ for 2-5 hours before being treated by spraying in step S3.
6. The process for preparing the composite material according to claim 1, wherein the amount of the 10% -25% NaOH aqueous solution added in the step S1 is 1.5-2 times the volume of the cotton fiber until the cotton fiber is completely submerged.
7. The process for preparing a composite material according to claim 1, wherein the acetone solution of triallyl isocyanurate in the step S1 is prepared by dissolving 3-5 parts by mass of triallyl isocyanurate in 10-20 parts by mass of acetone.
8. The process for preparing a composite material according to claim 1, wherein the plasticizer is one or more selected from the group consisting of tributyrin, tricaprylin and tricaprylin; the lubricant is one or more selected from calcium stearate and magnesium stearate.
9. The process for preparing the composite material according to claim 1, wherein the nucleating agent is at least one selected from the group consisting of hydrazide nucleating agents selected from the group consisting of TMC-306 and TMC-300, and tetrapod-like zinc oxide whiskers.
10. The process for preparing a composite material according to claim 9, wherein the nucleating agent is selected from two kinds of hydrazide nucleating agents and tetrapod-like zinc oxide whiskers, and the mass ratio of the hydrazide nucleating agent to the tetrapod-like zinc oxide whiskers is 1: (1-3).
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