CN117362959A - Polylactic acid film and preparation method and application thereof - Google Patents
Polylactic acid film and preparation method and application thereof Download PDFInfo
- Publication number
- CN117362959A CN117362959A CN202311442076.5A CN202311442076A CN117362959A CN 117362959 A CN117362959 A CN 117362959A CN 202311442076 A CN202311442076 A CN 202311442076A CN 117362959 A CN117362959 A CN 117362959A
- Authority
- CN
- China
- Prior art keywords
- polylactic acid
- acid film
- polyvinyl alcohol
- zinc oxide
- oxide particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920006381 polylactic acid film Polymers 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 80
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 80
- 239000002245 particle Substances 0.000 claims abstract description 67
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000002156 mixing Methods 0.000 claims abstract description 36
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 29
- 239000004626 polylactic acid Substances 0.000 claims abstract description 29
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 28
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003063 flame retardant Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 46
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- 238000005520 cutting process Methods 0.000 claims description 16
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 9
- 238000000071 blow moulding Methods 0.000 claims description 8
- 230000001112 coagulating effect Effects 0.000 claims description 8
- 238000009792 diffusion process Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 6
- JSPBAVGTJNAVBJ-UHFFFAOYSA-N ethyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCC)OC1=CC=CC=C1 JSPBAVGTJNAVBJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 6
- -1 phenyl alkyl diphenyl phosphate Chemical compound 0.000 claims description 5
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 229920006280 packaging film Polymers 0.000 claims description 3
- 239000012785 packaging film Substances 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 8
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 239000002667 nucleating agent Substances 0.000 abstract description 3
- 230000003115 biocidal effect Effects 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 11
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 9
- 239000002105 nanoparticle Substances 0.000 description 9
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 239000002861 polymer material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- AOJJSUZBOXZQNB-VTZDEGQISA-N 4'-epidoxorubicin Chemical group O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@@H](O)[C@H](C)O1 AOJJSUZBOXZQNB-VTZDEGQISA-N 0.000 description 1
- 235000016068 Berberis vulgaris Nutrition 0.000 description 1
- 241000335053 Beta vulgaris Species 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention belongs to the technical field of polymers, and particularly relates to a polylactic acid film and a preparation method and application thereof. The polylactic acid film of the invention takes modified polyvinyl alcohol master batch and polylactic acid as main components, and has the advantage of biodegradability. The main component of the polylactic acid film is modified polyvinyl alcohol master batch which is prepared by blending modified zinc oxide particles with a polyvinyl alcohol solution, and the addition of the modified zinc oxide particles ensures that the prepared polylactic acid film has antibacterial and flame retardant properties, and the modified zinc oxide particles can also be used as nucleating agents to improve the crystallization property of polylactic acid, thereby improving the mechanical strength of the polylactic acid film. The components of the polylactic acid film also comprise a compatilizer which can promote the mutual permeation of the polylactic acid and the polyvinyl alcohol and improve the transparency of the polylactic acid film. The invention also provides a method for preparing the polylactic acid film, and the polylactic acid film prepared by the method has the advantages of antibiosis, flame retardance, high mechanical strength and high transparency, and is suitable for large-scale popularization and use.
Description
Technical Field
The invention belongs to the technical field of polymer films, and particularly relates to a polylactic acid film and a preparation method and application thereof.
Background
The petroleum-based polymer material is a polymer material prepared by taking petroleum as a raw material, and comprises polyethylene, polypropylene, polystyrene, polyvinyl chloride and the like. The petroleum-based polymer material has excellent physical properties and chemical stability, and is widely applied to the fields of packaging, construction, electronics, automobiles, medical treatment and the like. However, the large-scale use of petroleum-based polymeric materials also causes the problem of "white pollution".
Polylactic acid (PLA) is a thermoplastic aliphatic polyester, which is prepared from crops such as corn, beet, cassava and the like as raw materials by steps of fermentation, extraction, refining and the like to obtain lactic acid, and then, carrying out polymerization reaction to obtain the synthetic polymer material. Polylactic acid has biocompatibility and biological renewable capability which are comparable with those of natural high polymer materials, is the only completely biodegradable artificial high polymer material which can be produced in large scale at present, and has certain application in the technical field of packaging. But the pure polylactic acid film is brittle and has low transparency. And the limiting oxygen index of PLA is 21%, the molten drop phenomenon is easy to generate when burning, and the fire is easy to spread, namely the flame retardant property is poor. Therefore, how to improve the toughness, transparency and flame retardant ability of PLA films is still a hot subject of research, which is of great importance for broadening the application of PLA films.
Disclosure of Invention
The invention aims to provide a polylactic acid film which has high transparency, strong flame retardance and antibacterial property.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the polylactic acid film comprises the following components in parts by weight: 15-30 parts of modified polyvinyl alcohol master batch, 60-80 parts of polylactic acid, 4-8 parts of compatilizer and 1-5 parts of antioxidant; the modified polyvinyl alcohol master batch is prepared by blending modified zinc oxide particles with a polyvinyl alcohol solution.
Further, the modified zinc oxide particles are zinc oxide particles with surface grafted with a phosphorus-containing flame retardant; the modified zinc oxide particles have an average particle diameter of 10 to 20nm.
Further, the compatilizer is one of glycidyl ether oxypropyl trimethoxy silane, vinyl triethoxy silane and vinyl trimethoxy silane; the antioxidant is basf 1010.
The second purpose of the invention is to provide a preparation method of the polylactic acid film, which is simple, easy to operate and suitable for preparing the high-performance polylactic acid film.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the polylactic acid film comprises the following steps:
(1) Preparing modified zinc oxide particles: dissolving metal zinc salt and alkaline reagent in a volume ratio of 1 according to a mass ratio of 2:1: 1, magnetically stirring the ethanol aqueous solution in a constant-temperature water bath at 60-70 ℃ for 1-1.5 h to obtain a uniform and stable colloidal solution; transferring the colloid solution into a reaction kettle, adding phosphide with the amount of metal zinc salt and the like, reacting for 8-24 hours at 140-220 ℃, and performing centrifugal washing and vacuum drying to obtain modified zinc oxide particles;
(2) Preparing modified polyvinyl alcohol master batches: blending the modified zinc oxide particles prepared in the step (1) with a polyvinyl alcohol solution at the temperature of 95-100 ℃, filtering, defoaming, extruding, preparing a strand with the diameter of 0.2-1 mm by double diffusion molding of the extruded solution in a coagulating bath, cutting the strand, and drying to obtain modified polyvinyl alcohol master batches;
(3) Preparing a polylactic acid film: and (3) uniformly mixing the modified polyvinyl alcohol master batch prepared in the step (2) with polylactic acid, a compatilizer and an antioxidant, performing melt blending in a double-screw extruder, and performing extrusion molding, blow molding, traction stretching, edge cutting and coiling by a single-screw extruder to prepare the polylactic acid film.
Further, the metal zinc salt in the step (1) is one of zinc acetate, zinc chloride, zinc sulfate, zinc nitrate and zinc oxalate, the alkaline reagent is one of sodium hydroxide, ammonia water and ethanolamine, and the phosphide is one of phenyl alkyl diphenyl phosphate, ethyl diphenyl phosphate and oligomeric bisphenol A bis (diphenyl phosphate).
Further, the mass ratio of the modified zinc oxide particles to the polyvinyl alcohol in the step (2) is 1: (85-95), the solvent of the polyvinyl alcohol solution is N, N-dimethylformamide, and the concentration of the polyvinyl alcohol solution is 20wt%.
Further, the rotating speed of the double-screw extruder in the step (3) is 20-60 rpm/min, the screw temperature is 120-160 ℃, and the pressure is 5-15 MPa.
Further, the rotating speed of the single screw extruder in the step (3) is 100-120 rpm/min, the screw temperature is 160-230 ℃, and the pressure is 5-15 MPa.
The third object of the present invention is to provide a polylactic acid film for use as a packaging film.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the polylactic acid film is applied as a packaging film.
Compared with the prior art, the invention has the beneficial effects that:
1) The polylactic acid film takes modified polyvinyl alcohol master batches and polylactic acid as main components, so that the prepared polylactic acid film has the advantage of biodegradability;
2) The main component of the polylactic acid film is modified polyvinyl alcohol master batch which is prepared by blending modified zinc oxide particles and a polyvinyl alcohol solution, and the addition of the modified zinc oxide particles ensures that the prepared polylactic acid film has antibacterial and flame retardant properties, and the modified zinc oxide particles can also be used as nucleating agents, so that the crystallization property of polylactic acid is improved, and the mechanical strength of the polylactic acid film is improved;
3) The components of the polylactic acid film also comprise a compatilizer which can promote the mutual permeation of polylactic acid and polyvinyl alcohol and improve the transparency of the polylactic acid film;
4) The preparation method of the polylactic acid film comprises a solution blending mode, and the mode can improve the mixing uniformity of the modified zinc oxide particles and the polyvinyl alcohol and lay a foundation for the uniform dispersion in the polylactic acid in the later period;
5) The preparation method of the polylactic acid film also adds a double-screw extrusion process to perform low-temperature premelting mixing, and can more uniformly mix the modified polyvinyl alcohol master batch, the polylactic acid, the compatilizer and the antioxidant according to the formula proportion.
Drawings
Fig. 1 is an SEM image of the modified zinc oxide particles prepared in example 3.
Detailed Description
The technical scheme of the present invention will be further explained with reference to specific examples, comparative examples, test examples and drawings.
In the following examples, comparative examples and test examples, materials and preparation methods used are those conventionally used in the art unless otherwise specified.
The foregoing is illustrative of the preferred embodiments of the present invention and is not to be construed as limiting thereof, and various modifications and variations may be made by those skilled in the art without departing from the principles of the invention. Any modification, improvement, etc. should be considered as being within the scope of the present invention.
1. Examples
Example 1
A polylactic acid film consists of the following components: 15 parts of modified polyvinyl alcohol master batch, 80 parts of polylactic acid, 4 parts of glycidol ether oxypropyl trimethoxysilane and 1 part of basf 1010. Wherein the modified polyvinyl alcohol master batch is prepared by blending modified zinc oxide particles with a polyvinyl alcohol solution; the modified zinc oxide particles are zinc oxide particles with surface grafted with phosphorus-containing flame retardant, and the average particle diameter is 10-20 nm.
The preparation method of the polylactic acid film comprises the following steps:
(1) Preparing modified zinc oxide particles: zinc chloride and sodium hydroxide are mixed according to the mass ratio of 2:1 in a volume ratio of 1:1, magnetically stirring the mixture in an ethanol water solution in a constant-temperature water bath at 60 ℃ for 1h to obtain a uniform and stable colloidal solution; transferring the colloid solution into a hydrothermal reaction kettle, simultaneously adding phenyl alkyl diphenyl phosphate with the amount of substances such as zinc chloride, reacting for 24 hours at 140 ℃, centrifugally washing to be neutral, and vacuum drying at 80 ℃ to obtain modified zinc oxide nano particles with the average particle size of 10-20 nm;
(2) Preparing modified polyvinyl alcohol master batches: blending the modified zinc oxide particles prepared in the step (1) with an N, N-dimethylformamide solution of polyvinyl alcohol with the concentration of 20wt% at the temperature of 95 ℃, filtering, defoaming, extruding through a syringe, performing double diffusion molding on the solution in a coagulating bath to obtain filaments with the diameter of 0.5mm, and cutting and drying to obtain modified polyvinyl alcohol master batches, wherein the mass ratio of the modified zinc oxide particles to the polyvinyl alcohol is 1:85;
(3) Preparing a polylactic acid film: adding the modified polyvinyl alcohol master batch prepared in the step (2), polylactic acid, glycidol ether oxypropyl trimethoxy silane and basf 1010 into a material tank, fully mixing, conveying to a double-screw extruder, carrying out melt blending at the screw speed of 20rpm/min and the screw temperature of 120 ℃ and the pressure of 5MPa, conveying to a single-screw extruder, extruding at the screw speed of 100rpm/min and the screw temperature of 160 ℃ and the pressure of 5MPa, and carrying out blow molding, traction stretching, edge cutting and coiling to obtain the polylactic acid film.
Example 2
A polylactic acid film consists of the following components: 15 parts of modified polyvinyl alcohol master batch, 80 parts of polylactic acid, 4 parts of vinyl triethoxysilane and 5 parts of basf 1010. Wherein the modified polyvinyl alcohol master batch is prepared by blending modified zinc oxide particles with a polyvinyl alcohol solution; the modified zinc oxide particles are zinc oxide particles with surface grafted with phosphorus-containing flame retardant, and the average particle diameter is 10-20 nm.
The preparation method of the polylactic acid film comprises the following steps:
(1) Preparing modified zinc oxide particles: zinc sulfate and ammonia water are mixed according to the mass ratio of 2:1 in a volume ratio of 1:1, magnetically stirring the mixture in an ethanol water solution in a constant-temperature water bath at 60 ℃ for 1h to obtain a uniform and stable colloidal solution; transferring the colloid solution into a hydrothermal reaction kettle, simultaneously adding ethyl diphenyl phosphate with the amount of substances such as zinc sulfate, reacting for 12 hours at 200 ℃, centrifugally washing to be neutral, and vacuum drying at 80 ℃ to obtain modified zinc oxide nano particles with the average particle size of 10-20 nm;
(2) Preparing modified polyvinyl alcohol master batches: blending the modified zinc oxide particles prepared in the step (1) with an N, N-dimethylformamide solution of polyvinyl alcohol with the concentration of 20wt% at the temperature of 95 ℃, filtering, defoaming, extruding through a syringe, performing double diffusion molding on the solution in a coagulating bath to obtain filaments with the diameter of 0.5mm, cutting and drying to obtain modified polyvinyl alcohol master batches, wherein the mass ratio of the modified zinc oxide particles to the polyvinyl alcohol is 1:85;
(3) Preparing a polylactic acid film: adding the modified polyvinyl alcohol master batch prepared in the step (2), polylactic acid, vinyl triethoxysilane and basf 1010 into a material tank, fully mixing, conveying to a double-screw extruder, carrying out melt blending at the rotating speed of the double-screw extruder of 60pm/min and the screw temperature of 160 ℃ and the pressure of 10MPa, conveying to a single-screw extruder, extruding at the rotating speed of 120rpm/min and the screw temperature of 230 ℃ and the pressure of 10MPa, and carrying out blow molding, traction stretching, edge cutting and coiling to obtain the polylactic acid film.
Example 3
A polylactic acid film consists of the following components: 25 parts of modified polyvinyl alcohol master batch, 65 parts of polylactic acid, 8 parts of glycidol ether oxypropyl trimethoxysilane and 2 parts of basf 1010. Wherein the modified polyvinyl alcohol master batch is prepared by blending modified zinc oxide particles with a polyvinyl alcohol solution; the modified zinc oxide particles are zinc oxide particles with surface grafted with phosphorus-containing flame retardant, and the average particle diameter is 10-20 nm.
The preparation method of the polylactic acid film comprises the following steps:
(1) Preparing modified zinc oxide particles: zinc oxalate and ethanolamine are mixed according to the mass ratio of 2:1 in a volume ratio of 1:1, magnetically stirring the mixture in an ethanol water solution in a constant-temperature water bath at 60 ℃ for 1h to obtain a uniform and stable colloidal solution; transferring the colloid solution into a hydrothermal reaction kettle, simultaneously adding ethyl diphenyl phosphate with the amount of substances such as zinc oxalate, reacting for 8 hours at 220 ℃, centrifugally washing to be neutral, and vacuum drying at 80 ℃ to obtain modified zinc oxide nano particles with the average particle size of 10-20 nm;
(2) Preparing modified polyvinyl alcohol master batches: blending the modified zinc oxide particles prepared in the step (1) with an N, N-dimethylformamide solution of polyvinyl alcohol with the concentration of 20wt% at the temperature of 95 ℃, filtering, defoaming, extruding through a syringe, performing double diffusion molding on the solution in a coagulating bath to obtain a strand with the diameter of 1mm, and cutting and drying to obtain modified polyvinyl alcohol master batches, wherein the mass ratio of the modified zinc oxide particles to the polyvinyl alcohol is 1:90;
(3) Preparing a polylactic acid film: adding the modified polyvinyl alcohol master batch prepared in the step (2), polylactic acid, glycidol ether oxypropyl trimethoxy silane and basf 1010 into a material tank, fully mixing, conveying to a double-screw extruder, carrying out melt blending at the screw speed of 60rpm/min and the screw temperature of 160 ℃ and the pressure of 8MPa, conveying to a single-screw extruder, extruding at the screw speed of 120rpm/min and the screw temperature of 230 ℃ and the pressure of 8MPa, and carrying out blow molding, traction stretching, edge cutting and coiling to obtain the polylactic acid film.
Example 4
A polylactic acid film consists of the following components: 30 parts of modified polyvinyl alcohol master batch, 60 parts of polylactic acid, 5 parts of glycidol ether oxypropyl trimethoxysilane and 5 parts of basf 1010. Wherein the modified polyvinyl alcohol master batch is prepared by blending modified zinc oxide particles with a polyvinyl alcohol solution; the modified zinc oxide particles are zinc oxide particles with surface grafted with phosphorus-containing flame retardant, and the average particle diameter is 10-20 nm.
The preparation method of the polylactic acid film comprises the following steps:
(1) Preparing modified zinc oxide particles: zinc nitrate and ethanolamine are mixed according to the mass ratio of 2:1 in a volume ratio of 1:1, magnetically stirring the mixture in an ethanol water solution in a constant-temperature water bath at 60 ℃ for 1h to obtain a uniform and stable colloidal solution; transferring the colloid solution into a hydrothermal reaction kettle, simultaneously adding oligomeric bisphenol A bis (diphenyl phosphate) with the amount of substances such as zinc nitrate, reacting for 16 hours at 200 ℃, centrifugally washing to be neutral, and vacuum drying at 80 ℃ to obtain modified zinc oxide nano particles with the average particle diameter of 10-20 nm;
(2) Preparing modified polyvinyl alcohol master batches: blending the modified zinc oxide particles prepared in the step (1) with an N, N-dimethylformamide solution of polyvinyl alcohol with the concentration of 20wt% at the temperature of 95 ℃, filtering, defoaming, extruding through a syringe, performing double diffusion molding on the solution in a coagulating bath to obtain filaments with the diameter of 0.2mm, cutting and drying to obtain modified polyvinyl alcohol master batches, wherein the mass ratio of the modified zinc oxide particles to the polyvinyl alcohol is 1:95;
(3) Preparing a polylactic acid film: adding the modified polyvinyl alcohol master batch prepared in the step (2), polylactic acid, glycidol ether oxypropyl trimethoxy silane and basf 1010 into a material tank, fully mixing, conveying to a double-screw extruder, carrying out melt blending at the screw speed of 40rpm/min and the screw temperature of 150 ℃ and the pressure of 15MPa, conveying to a single-screw extruder, extruding at the screw speed of 110rpm/min and the screw temperature of 200 ℃ and the pressure of 8MPa, and carrying out blow molding, traction stretching, edge cutting and coiling to obtain the polylactic acid film.
2. Comparative example
Comparative example 1
Comparative example 1 provides a polylactic acid film and a preparation method thereof, and the specific preparation process is as follows:
(1) Preparing modified zinc oxide particles: zinc oxalate, ethanolamine and ethyl diphenyl phosphate are mixed according to the mass ratio of 2:1:2 is dissolved in the volume ratio of 1:1, magnetically stirring the mixture in an ethanol water solution in a constant-temperature water bath at 60 ℃ for 1h to prepare a mixed solution; then the mixed solution is moved into a hydrothermal reaction kettle to react for 8 hours at 220 ℃, centrifugally washed to be neutral, and dried in vacuum at 80 ℃ to obtain modified zinc oxide nano particles;
(2) Preparing modified polyvinyl alcohol master batches: blending the modified zinc oxide particles prepared in the step (1) with an N, N-dimethylformamide solution of polyvinyl alcohol with the concentration of 20wt% at the temperature of 95 ℃, filtering, defoaming, extruding through a syringe, performing double diffusion molding on the solution in a coagulating bath to obtain a strand with the diameter of 1mm, and cutting and drying to obtain modified polyvinyl alcohol master batches, wherein the mass ratio of the modified zinc oxide particles to the polyvinyl alcohol is 1:90;
(3) Preparing a polylactic acid film: adding the modified polyvinyl alcohol master batch prepared in the step (2), polylactic acid, glycidol ether oxypropyl trimethoxy silane and basf 1010 into a material tank, fully mixing, conveying to a double-screw extruder, carrying out melt blending at the screw speed of 60rpm/min and the screw temperature of 160 ℃ and the pressure of 8MPa, conveying to a single-screw extruder, extruding at the screw speed of 120rpm/min and the screw temperature of 230 ℃ and the pressure of 8MPa, carrying out blow molding, drawing, cutting edges and coiling to obtain the polylactic acid film. The other conditions were the same as in example 3.
Comparative example 2
Comparative example 2 provides a polylactic acid film and a preparation method thereof, and the specific preparation process is as follows:
(1) Preparing modified polyvinyl alcohol master batches: blending zinc oxide nano particles with the average particle size of 10-20 nm with an N, N-dimethylformamide solution of polyvinyl alcohol with the concentration of 20wt% at 95 ℃, filtering, defoaming, extruding through a syringe, double-diffusion forming the solution in a coagulating bath to obtain a strand with the diameter of 1mm, cutting and drying to obtain modified polyvinyl alcohol master batches, wherein the mass ratio of the zinc oxide nano particles to the polyvinyl alcohol is 1:90;
(2) Preparing a polylactic acid film: adding the polyvinyl alcohol master batch, the ethyl diphenyl phosphate, the polylactic acid, the glycidol ether oxypropyl trimethoxy silane and the basf 1010 which are prepared in the step (1) into a material tank, fully mixing, conveying to a double-screw extruder, carrying out melt blending at the rotating speed of 60rpm/min of the double-screw extruder and the screw temperature of 160 ℃ and the pressure of 8MPa, conveying to a single-screw extruder, extruding at the rotating speed of 120rpm/min of the single-screw extruder and the screw temperature of 230 ℃ and the pressure of 8MPa, and carrying out blow molding, traction stretching, edge cutting and coiling to prepare the polylactic acid film. The other conditions were the same as in example 3.
Comparative example 3
Comparative example 3 provides a polylactic acid film and a method for preparing the same, and example 3 is different in that: step (3) was carried out without adding modified polyvinyl alcohol master batch, and the other conditions were the same as in the preparation method of example 3.
Comparative example 4
Comparative example 4 provides a polylactic acid film and a method for preparing the same, which is different from example 3 in that: step (3) was carried out under the same conditions as in example 3 without adding glycidoxypropyl trimethoxysilane.
Comparative example 5
Comparative example 5 provides a polylactic acid film and a method for preparing the same, which is different from example 3 in that: step (3) was carried out without adding basf 1010, and the other conditions were the same as in the preparation method of example 3.
3. Test examples
The properties of the polylactic acid films prepared in examples 1 to 4 and comparative examples 1 to 5 were measured as follows:
(1) Film mechanical test: according to GB/T-1040.3-2006 test standard;
(2) Haze: according to GB/T-2410-2008 test standard;
(3) Antibacterial properties: using a film sticking method to test, and obtaining the antibacterial rate through counting and calculating;
(4) Limiting oxygen index: according to ASTM D2863-2008 test standard;
(5) Flame retardant properties: according to ASTM D635-2003 test standard. The performance results of the polylactic acid films obtained in examples 1 to 4 and comparative examples 1 to 5 are shown in Table 1.
TABLE 1
As can be seen from Table 1, compared with example 3, comparative example 1 adjusts the addition sequence of materials in the preparation process of the modified zinc oxide particles, and the prepared polylactic acid film has higher haze and lower elongation at break, which indicates that the addition sequence of materials can influence the performance of the modified zinc oxide particles, thereby influencing the performance of the polylactic acid film; comparative example 2 modified polyvinyl alcohol master batch is prepared by adopting unmodified zinc oxide nano particles, and the addition sequence of phosphide is adjusted to prepare a polylactic acid film, wherein the film has higher haze and lower elongation at break, which indicates that the addition sequence of phosphide and the structure of zinc oxide nano particles both affect the performance of the polylactic acid film; the polylactic acid film prepared in comparative example 3 has obviously reduced transparency, which indicates that the use of the compatilizer can improve the compatibility of polyvinyl alcohol and polylactic acid; the polylactic acid film prepared in the comparative example 4 has higher tensile strength, but has high haze and poor flame retardant effect, and does not have antibacterial capability; the mechanical property of the polylactic acid film material prepared in the comparative example 5 is obviously weakened, which indicates that the antioxidant can effectively reduce thermal degradation caused by high temperature. Therefore, the high-transparency flame-retardant antibacterial polylactic acid film is prepared by the synergistic effect of the modified polyvinyl alcohol master batch, the compatilizer and the antioxidant substance and the close coordination of the steps and the front and back connection, and the film has low production cost and is suitable for large-scale popularization and use.
In conclusion, the polylactic acid film disclosed by the invention takes the modified polyvinyl alcohol master batch and polylactic acid as main components, and has the advantage of biodegradability. The main component of the polylactic acid film is modified polyvinyl alcohol master batch which is prepared by blending modified zinc oxide particles with a polyvinyl alcohol solution, and the addition of the modified zinc oxide particles ensures that the prepared polylactic acid film has antibacterial and flame retardant properties, and the modified zinc oxide particles can also be used as nucleating agents to improve the crystallization property of polylactic acid, thereby improving the mechanical strength of the polylactic acid film. The components of the polylactic acid film also comprise a compatilizer which can promote the mutual permeation of the polylactic acid and the polyvinyl alcohol and improve the transparency of the polylactic acid film. The invention also provides a method for preparing the polylactic acid film, and the polylactic acid film prepared by the method has the advantages of antibiosis, flame retardance, high mechanical strength and high transparency, and is suitable for large-scale popularization and use.
The foregoing is illustrative of the preferred embodiments of the present invention and is not to be construed as limiting thereof, and various modifications and variations may be made by those skilled in the art without departing from the principles of the invention. Any modification, improvement, etc. should be considered as being within the scope of the present invention.
Claims (9)
1. The polylactic acid film is characterized by comprising the following components in parts by weight: 15-30 parts of modified polyvinyl alcohol master batch, 60-80 parts of polylactic acid, 4-8 parts of compatilizer and 1-5 parts of antioxidant; the modified polyvinyl alcohol master batch is prepared by blending modified zinc oxide particles with a polyvinyl alcohol solution.
2. The polylactic acid film according to claim 1, wherein the modified zinc oxide particles are zinc oxide particles having a surface grafted with a phosphorus-containing flame retardant; the modified zinc oxide particles have an average particle diameter of 10 to 20nm.
3. The polylactic acid film according to claim 1, wherein the compatibilizer is one of glycidoxypropyl trimethoxysilane, vinyltriethoxysilane, and vinyltrimethoxysilane; the antioxidant is basf 1010.
4. The method for producing a polylactic acid film according to any one of claims 1 to 3, comprising the steps of:
(1) Preparing modified zinc oxide particles: dissolving a metal zinc salt and an alkaline reagent in a volume ratio of 1 according to a mass ratio of 2:1: 1, magnetically stirring the ethanol aqueous solution in a constant-temperature water bath at 60-70 ℃ for 1-1.5 h to obtain a uniform and stable colloidal solution; transferring the colloid solution into a reaction kettle, adding phosphide with the amount of metal zinc salt and the like, reacting for 8-24 hours at 140-220 ℃, and performing centrifugal washing and vacuum drying to obtain modified zinc oxide particles;
(2) Preparing modified polyvinyl alcohol master batches: blending the modified zinc oxide particles prepared in the step (1) with a polyvinyl alcohol solution at the temperature of 95-100 ℃, filtering, defoaming, extruding, preparing a strand with the diameter of 0.2-1 mm by double diffusion molding of the extruded solution in a coagulating bath, cutting the strand, and drying to obtain modified polyvinyl alcohol master batches;
(3) Preparing a polylactic acid film: and (3) uniformly mixing the modified polyvinyl alcohol master batch prepared in the step (2) with polylactic acid, a compatilizer and an antioxidant, performing melt blending in a double-screw extruder, and performing extrusion molding, blow molding, traction stretching, edge cutting and coiling by a single-screw extruder to prepare the polylactic acid film.
5. The method according to claim 4, wherein the metal zinc salt in the step (1) is one of zinc acetate, zinc chloride, zinc sulfate, zinc nitrate and zinc oxalate, the alkaline agent is one of sodium hydroxide, ammonia water and ethanolamine, and the phosphide is one of phenyl alkyl diphenyl phosphate, ethyl diphenyl phosphate and oligomeric bisphenol A bis (diphenyl phosphate).
6. The method of producing a polylactic acid film according to claim 4, wherein the mass ratio of said modified zinc oxide particles to polyvinyl alcohol in said step (2) is 1: (85-95), the solvent of the polyvinyl alcohol solution is N, N-dimethylformamide, and the concentration of the polyvinyl alcohol solution is 20wt%.
7. The method of producing a polylactic acid film according to claim 4, wherein the twin-screw extruder in the step (3) has a rotational speed of 20 to 60rpm/min, a screw temperature of 120 to 160℃and a pressure of 5 to 15MPa.
8. The method of producing a polylactic acid film according to claim 4, wherein the single screw extruder in the step (3) has a rotational speed of 100 to 120rpm/min, a screw temperature of 160 to 230℃and a pressure of 5 to 15MPa.
9. The use of the polylactic acid film according to any one of claims 1 to 3, wherein the polylactic acid film is used as a packaging film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311442076.5A CN117362959A (en) | 2023-11-01 | 2023-11-01 | Polylactic acid film and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311442076.5A CN117362959A (en) | 2023-11-01 | 2023-11-01 | Polylactic acid film and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117362959A true CN117362959A (en) | 2024-01-09 |
Family
ID=89405731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311442076.5A Pending CN117362959A (en) | 2023-11-01 | 2023-11-01 | Polylactic acid film and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117362959A (en) |
-
2023
- 2023-11-01 CN CN202311442076.5A patent/CN117362959A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109853083B (en) | Water-soluble degradable fiber and preparation method thereof | |
| CN108570182B (en) | Glass fiber reinforced polypropylene alloy and preparation method thereof | |
| CN109294190A (en) | A kind of Degradable high polymer film and preparation method thereof | |
| CN109880180B (en) | Nano-cellulose/cellulose compound, reinforced polylactic acid 3D printing material and preparation method thereof | |
| CN114524959B (en) | Ceramic nanocellulose reinforced full-biodegradable material composite membrane and preparation method thereof | |
| CN114891331A (en) | Toughened polylactic acid/starch blending material and preparation method thereof | |
| CN102702655B (en) | Polyvinyl alcohol/high amylose biodegradable material and melting preparation method thereof | |
| CN114044973A (en) | Radiation-resistant PP electret melt-blown material and preparation process thereof | |
| CN116144187B (en) | Polylactic acid composite material and preparation method and application thereof | |
| CN112280260A (en) | High-barrier PLA/PBAT composite packaging film | |
| CN117362959A (en) | Polylactic acid film and preparation method and application thereof | |
| CN102926019B (en) | Hyperbranched polymer/polyethylene composite particle tangible micro-thin polypropylene fiber and preparation method thereof | |
| CN115286867A (en) | Nano compatibilized polypropylene polystyrene composition and preparation method thereof | |
| CN115558204A (en) | Low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material and preparation method thereof | |
| CN114891291A (en) | Antistatic packaging plastic film | |
| CN109423048A (en) | A kind of polyphenyl thioether material and preparation method thereof of organosilicon toughening modifying | |
| CN109553902B (en) | Transparent flame-retardant polyvinyl alcohol film and preparation method thereof | |
| CN108004782B (en) | Thermoplastic inorganic fiber for plastics and preparation method thereof | |
| CN109054748B (en) | Preparation method of modified fullerene material | |
| CN112194872A (en) | Composite material based on recycled plastic and preparation method thereof | |
| CN112574542A (en) | Environment-friendly plastic film and preparation method thereof | |
| CN117986829B (en) | Environment-friendly degradable high-strength composite plastic packaging bag | |
| CN115286907B (en) | Degradable heat-resistant flame-retardant plastic master batch and preparation method thereof | |
| CN118307852B (en) | Stretch-resistant starch-based material and preparation method thereof | |
| CN115536881B (en) | Preparation method of biodegradable PLA composite film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |